WASTES 2011 BookofProceedings

BOOK OF
PROCEEDINGS
OF
BOOK
PROCEEDINGS
Book of Proceedings of the 1st International Conference:
WASTES: Solutions, Treatments and Opportunities
EDITION
CVR Centro para a valorizao de Resduos
AUTHORS
Fernando Castro, Cndida Vilarinho, Joana Carvalho
COVER DESIGN
Rui Ferreira
CVR Centro para a Valorizao de Resduos

Campus de Azurm da Universidade do Minho
4800-058 Guimares ISBN
978-989-97429-1-8
Telef.: +351 253 510 020

Fax: +351 253 510 029
http://www.cvresiduos.pt
e-mail: geral@cvresiduos.pt October 2011
ORGANIZING COMMITTEE
Cndida Vilarinho [U. Minho, Portugal] Joana Carvalho [CVR, Portugal]
Fernando Castro [U. Minho, Portugal] Jorge Arajo [CVR, Portugal]
Rute Arajo [CVR, Portugal]
SCIENTIFIC COMMITTEE
Fernando Castro, Universidade do Minho, CVR, Portugal (Chair)
Ana Andrs, Universidad de Cantabria, Spain
Ana Maria Segades, Universidade de Aveiro, Portugal
Ange Nzihou, Ecole de Mines de Albi, France
Antnio Brito, Universidade do Minho, Portugal
Antnio Correia, Universidade do Minho, Portugal
Antnio Jos Roque, LNEC Laboratrio Nacional de Engenharia Civil, Portugal
Antnio Roca, Universita de Barcelona, Spain
Cndida Vilarinho, Universidade do Minho, CVR, Portugal
Carlos Bernardo, Universidade do Minho, Portugal
Carlos Franco, LNEG Laboratrio Nacional de Energia e Geologia, Portugal
Carlos Nogueira, LNEG Laboratrio Nacional de Energia e Geologia, Portugal
Derek Greedy, Warwickshire County Council, United Kingdom
Eduardo Ferreira, Universidade do Minho, CEBio, Portugal
Enzo Favoino, Scuola Agraria del Parco di Monza, Italy
Felipe Macias Vasquez, Universidade de Santiago de Compostela, Spain
Fernanda Margarido, Instituto Superior Tcnico, Lisboa
Fernando Leite, LIPOR, Portugal

Francisca Puertas Maroto, CSIC Instituto de Ciencias de la Construccin Eduardo Torroja, Spain
Ibrahim Gulyurtlu, LNEG Laboratrio Nacional de Energia e Geologia, Portugal
Javier Viguri, Universita de Cantabria, Spain
Joana Carvalho, CVR Centro para a Valorizao de Resduos, Portugal
Joo A. Labrincha, Universidade de Aveiro, Portugal
Jos Cardona, Resinorte, Portugal
Jos Carlos Teixeira, Universidade do Minho, CEBio, Portugal
Jos Cavalheiro, Universidade do Porto, Portugal
Jos Fernando Juc, CETENE, Brasil
Jos M. P. Vieira, Universidade do Minho, Ordem dos Engenheiros, Portugal
Jos Teixeira, Universidade do Minho, Portugal
Lus Marinheiro, APESB, Portugal
Madalena Alves, Universidade do Minho, Portugal
Manuel Afonso Magalhes da Fonseca Almeida, Universidade do Porto, Portugal
Mrio Russo, Instituto Politcnico de Viana do Castelo, Portugal
Montserrat Cruells, Universita de Barcelona, Spain
Pablo Kroff, Simbiente, Chile
Patrick Sharrock, IUT de Castres, France
Paulo Ramsio, Universidade do Minho, Portugal
Pedro Machado, Braval, Portugal
Regina Monteiro, Universidade Nova de Lisboa, Portugal
Rosrio Tavares de Oliveira, Universidade do Minho, Portugal
Said Jalali, Universidade do Minho, Portugal
Teresa Vieira, Universidade de Coimbra, Portugal
Wilson Acchar, UFRN - Universidade Federa do Rio Grande do Norte, Brasil

SPONSORS & PARTNERS
GOLD SPONSOR
SILVER SPONSOR
BRONZE SPONSOR
PARTNERS
EXIBITORS
Index
Plenary Lecture I 8
Session 1.1 10
Session 2.1 36
Session 1.2 62
Session 2.2 92
Session 3.1 117
Keynote Lecture I 142

Session 1.3 144
Session 2.3 165
Session 1.4 196
Session 2.4 222
Keynote Lecture II 251
Poster Session 255
Plenary Lecture II 515

Session 1.5 518
Session 2.5 547
Session 3.2 572
Session 1.6 603
Session 2.6 622
Keynote Lecture III 646

Session 1.7 650
Session 2.7 681
Session 3.3 713
Session 1.8 738
Session 2.8 757
Keynote Lecture IV 781

13th September
Plenary Lecture I
( European strategies for the management of
biowaste: systems for separate collection and
technological trends. )
Enzo Favoino
8
Professor Enzo Favoino [Scuola Agraria del Parco di Monza, Italy]
Biography
Is with Scuola Agraria del Parco di Monza, where he coordinates the Working Group on
Composting and Integrated Waste Management. He and his team have helped many
Governmental Institutions and Local Authorities to implement waste management schemes,
with a particular reference to options for the management of biowaste.
Favoino is involved across Europe and the world in scientific and technical issues related to
optimisation of schemes for source segregation, process management, improvement of
existing plants, marketing of composted products, role of mechanical-biological treatment for
residual waste. They have widely contributed to the development of source separation and
composting in many Countries. He has frequently taken part as an invited expert in meetings,
workshops, organised by the European Commission on Sustainable Waste Management and
Source Separation.
He is currently Chair of the WG on Biological Treatment at ISWA International Solid Waste

Association; hes also Vice-Chair and Member of the Board of ECN-European Compost
Network.
9
13th September
Session 1.1
( RECYCLING OF MATERIALS 1 )
Chairman: Fernando Castro
10
St
1 International Conference
September 12th 14th 2011
SORPTION STUDIES OF Zn AND Cu BY COMPOST

1 2 3,* 4,*
J.R.M. Martinho , B.G. Campos , I.P.L. Brs and M.E.F Silva
1 Departamento de Ambiente, Escola Superior de Tecnologia e Gesto de Viseu, Viseu, Portugal,
email: jmartinho.monitar@gmail.com
2 Departamento de Ambiente, Escola Superior de Tecnologia e Gesto de Viseu, Viseu, Portugal
email: bruno_amb@webmail.ipv.pt
email: ipbras@estv.ipv.pt
email: beta@estv.ipv.pt
* Authors share leader authorship
ABSTRACT
The main purpose of the present work was to evaluate the feasibility of different
composts to operate as sorbents for heavy metals (Cu and Zn) removal from wastewater.
Three composts obtained from municipal solid wastes (MWS), sludge sewage (SS) and
poultry manure (PM), were selected as potential sorbents. Kinetic tests were conducted
in order to assess the equilibrium time necessary to remove Zn and Cu ions from
aqueous samples. Batch sorption assays were performed to determine the metal-binding
ability of composts, starting with equivalent amount of sorbent in different initial metal
concentrations. Equilibrium concentrations were evaluated and the amount of sorbed
metal per mass of sorbent was quantified.
For the three composts, the maximum time necessary to reach the equilibrium was 240
minutes. The SS proved to be the compost with highest removal capability for the both
assessed metals. Three sorption models, the Linear, Freundlich and Langmuir
equilibrium isotherms, were fitted to the experimental data. The Freundlich and Langmuir
isotherms were found to well represent the sorption data. The maximum sorption
2+
capacities of metal ions onto SS compost were 13.7 mg/g for Zn and 15.7 mg/g for
2+
Cu . The compost less suitable for the initial purpose was MWS, which showed a
2+ 2+
sorption of 6.8 mg/g for Zn and 11.1 mg/g for Cu . These results can be correlated with
the composts surface properties namely with the cation exchange capacity (CEC).
Keywords: compost; zinc; copper; sorption; equilibrium isotherms; cation exchange capacity
INTRODUCTION
Composting is one of the methods mostly used for organic solid wastes recycling. The compost is
mainly used as a soil conditioner due to the carbon and nitrogen content. However, compost
production has increased rapidly over the past decade resulting in a large increase in its
availability. In fact, many producers came across difficulties in finding markets for the compost.
Alternative uses will have to be found for compost to maintain this recycling advantage. Compost is
a mixture of organic and inorganic matter and the organic matter can be divided into two classes:
non-humic substances and humic substances [1]. This characteristic allows the compost to interact
with different pollutants in water and therefore be seen as barrier to the dispersion of pollutants in
the environment. Heavy metals are important environmental pollutants. The presence of metal ions
in effluent of many industries has been proven to be hazardous and input a threat to the
environment. The metal ions like copper, lead, mercury, cadmium and chromium are known toxic in
nature, non-biodegradable and tend to accumulate in living organisms, causing various diseases
and disorders [2].
Several treatment methodologies have being suggested for heavy metals mitigation in the
environment like, chemical precipitation, membrane filtration, ion exchange, carbon adsorption, and
11
co-precipitation/adsorption. Nevertheless, the search of cost effective alternative technologies or
sorbents for metals treatment from contaminated waste streams is needed. Natural materials that
are available in large quantities, or even certain waste products from industrial or agricultural
operations, may have potential as inexpensive sorbents [3]. In a review paper, Ho et al [4] reported
materials like peat, wood, pine bark, banana pith, rice bran, soybean and cottonseed hulls, peanut
shells, hazelnut shell, rice husk, sawdust, wool, orange peel, compost and leaves.
Keeping this in mind, the main objective of the present work was to evaluate the feasibility of
different composts operate as sorbents to capture heavy metals from wastewater. The focus of the
present paper was to present some laboratory data highlighting the Zn and Cu sorption by different
composts commercialized in Portugal.
MATERIALS AND METHODS

Three composts commercialized in Portugal, municipal solid wastes (MWS), sludge sewage (SS)
and poultry manure (PM), were selected as potential sorbents to capture heavy metals in
wastewater. The composts were oven dried at 55C for 24h and then sieved to #10 mesh (2 mm)
particle size to perform the sorption batch tests. Physical and chemical composts characterization
was previous reported [5]. Cation exchange capacity (CEC) was evaluated using the sodium
acetate method [6]. All experiments were carried out at 18-22C. The solutions pH was adjusted to
56 with HNO3 (1%) or NaOH (1%).The sorption kinetic of single metal ion (Zn or Cu) was
conducted by mixing 2 g of compost with 200 mL of 200 mg/L metal ion solution in a beaker.
Samples were collected at required time intervals. Metal ion solutions were prepared by dissolving
the corresponding sulphate salts in water. The equilibrium batch experiments were carried out,
separately for each metal, in beakers with 100mL solutions, with concentrations ranging from 0 to
250mg/L. The composts amount for each assay was 1g, and the beakers were shacked in a
continuous rotary mixer for 5 h. The reaction mixtures were analyzed with an atomic absorption
spectrophotometry (Perkin Elmer A Analyst 300) for cation concentration.
RESULTS AND DISCUSSION

The physical and chemical composts characteristics are extremely important to understand the
metals sorption behaviour. Table 1 has the data reported by Vaz-Moreira et al. for the composts
under evaluation [5].
Table 1 Physical and chemical composts characterization.

Compost MSW SS PM
pH 5.6 4.2 9.0
-1
Electric Conductivity [mS cm ] 10.9 1.6 7.6
Moisture [%] 45.5 59.6 24.7
Organic matter content [%] 73.3 82.4 46.8
CEC [meq/g] 3.3 3.9 3.5
Zn [mg/kg dry matter] 820 637 646
Cu [mg/kg dry matter] 285 299 86
Ni [mg/kg dry matter] 61 38 19
Cd [mg/kg dry matter] 1.3 1.9 1.2
Cr [mg/kg dry matter] 213 62.3 30
Pb [mg/kg dry matter] 219 79 149
The cation exchange capacity (CEC) is related with the amount of cations that a material can hold
on its negative charged groups or Lewis base functional groups at the compost surface. These
active sites are responsible for the electrostatic interactions between positive charged bivalent
12
cations and the solid surface. The organic matter should increase the CEC. Humic and fulvic acids
+
should be responsible for this pH decreasing because when the surface structures released H to
the solution, the conjugated bases will be available to interact with metals in solution. Looking to
the higher organic matter content and CEC, 82.4% and 3.9 meq/g, respectively, is possible to
reach the same evidence. The higher conductivity revealed by the MSW compost is probably
related to the fact that is has also the higher content in heavy metals and therefore less capability
to interact with exogenous cations. That is probably the fact that responsible for the lower CEC, 3.3
meq/g. PM compost has higher pH hence has higher CEC but low organic matter content. At the
same time, it can be seen that it has high electric conductivity.
Kinetics
The sorption kinetics is very important to evaluate the mechanisms that are evolved in the metal
species retention by the composts and to acknowledge the time necessary for the system reach
the equilibrium. The experimental data from assays performed with Cu and Zn were fitted with first
and second order kinetics models [7]. The appropriate method to represent the experimental data
was assessed by the error between the experimental and the theoretical data attained by each
model.
From the error analysis for each model (data not shown) it was clear that the second order model
had better adjustment to the experimental data. In Fig. 1 and 2 it can be seen the kinetics
nd
experimental data and the 2 order kinetic model adjustment for Cu and Zn, respectively.
18
16
q (mg Cu/g compost)
14
12
10
8 MSW
6 SS
4 PM
2
0
0 60 120 180 240 300
t (min)
Figure 1 Sorption kinetics of Cu in different composts with the second order model adjustment.
The time necessary to reach the equilibrium is attained when the sorption capacity over time (q t)
does not change above 5% [8]. The time necessary to Cu/composts systems achieve equilibrium
was approximately 180 minutes, except for PM compost where the time required was superior, 240
minutes. The equilibrium plateau was higher for SS suggesting greater affinity from Cu to this
compost.
16
14
12
q (mg Zn/g compost)
10 MSW
8 SS
6 PM
4
2
0
0 60 120 180 240 300
t (min)
Figure 2 Sorption kinetics of Zn in the different composts with the second order model
adjustment.
13
The experimental data for the Zn sorption systems exhibit higher variability, with the theoretical
models presenting poor correlation. With the SS and PM composts, the time necessary to attain
the equilibrium was 120 minutes. The Zn/MSW sorption system revealed higher variability probably
due to experimental errors. The sorption capacity of Zinc sorption is higher for SS compost. By the
data drawn is possible to state that MSW and PM composts have similar behaviour.
The kinetics assay showed that the Cu and Zn retention by MSW compost was around 60% and
46%, respectively. The SS compost revealed 80% of Cu removal and 60% of Zn and the PM
around 60% and 50% for Cu and Zn, respectively. Regarding the CEC for each compost it is
possible to made a relationship with the sorption capacity, that is, the compost who presented
higher sorption has higher CEC.
Sorption equilibrium
To understand the possible mechanisms that play an important role in the metals sorption by
composts, the Langmuir, Freundlich and Linear mathematical models [7] were fitted to the
experimental data. The model selection can be evaluated by the correlation coefficient or by the
error associated to the residuals between the experimental data and the mathematical model. In
the present work the criterion followed was the error as suggested by Tseng et al. [9].
The equilibrium experimental data were fitted by the isotherm equations mentioned above (data not
shown). The method more suitable to represent the experimental results is represented in Fig. 3 for
each compost. Langmuir isotherm is able to describe well the sorption of Cu by MSW compost,
while the Freundlich isotherm represents the data for Cu sorption by SS and PM composts.
Nevertheless, while the sorption is favorable for SS compost, with 1/n value equal to 0.32, the
same parameter for Cu/PM sorption system is 1.46, showing an unfavorable sorption process.
For Zn sorption, the procedure was analogous to Cu equilibrium data analysis. In Fig. 4 we can see
that the best model to represent the Zn sorption by MSW and PM compost was the Langmuir
model and for SS compost was the Freundlich model. In this case, the 1/n value (0.42) represent a
favourable sorption.
16
MSW
12
SS
PM
qe (mg/g)
8
Langumir
4 Freundlich
Freundlich
0
0 50 100
Ce (mg/L)
Figure 3 Equilibrium data for Cu sorption in diferent composts and the isotherm models that best
adjust to the experimental data.
14
12
10
MSW
8
SS
qe (mg/g)
6 PM
Langmuir
4
Freundlich
2
Langumir
0
0 40 80 120 160 200 240
Ce (mg/L)
Figure 4 Equilibrium data for Zn sorption in diferent composts and the isotherm models that best
adjust to the experimental data.
The typical behaviour of the Langmuir isotherm is connected with sorption on external surfaces of
microporous solids, in which the limiting value of sorption corresponds to the formation
of a monomolecular sorbed layer. According with the experimental results, we can conclude that
the MSW compost should belong to this kind of sorbents once the saturation Langmuir model fitted
the Cu and Zn experimental equilibrium results. The equation representing the Freundlich isotherm
predicts that the amount of solute sorption always increases due to the formation of multi layers
and is usually the case of non porous solids or with macroporous. The limited is achieved when
occurs capillary condensation. The typical behaviour represented by this model was characteristic
of SS compost for both metals sorption. The PM compost did not reveal a coherent performance. In
the study of Cu sorption the isotherm was unfavorable, with the Freundlich parameter 1/n being
above 1. Gilbert et al [10] mentioned that the equilibrium could be represented by a linear
distribution of cations on vegetal compost. Evaluating the equilibrium distribution (data not shown)
none of the assays performed in the present work followed the linear isotherm equation, suggesting
that the sorption potential does not increase uniformly with the solute concentration. These model
is usually appropriated to describe systems where the solute concentration is low and for solid
surfaces with poor sorption potential.
Looking for the composts sorption behaviour, is possible to notice that the three composts retain
with higher extension Cu rather than Zn. Table 2 describe the maximum sorption capacity for the
composts under evaluation. Ulmanu et al [11], report data in the same order of magnitude by
compost obtained from mowed garden grass. These results were expected regarding data
achieved with different experimental conditions reported by Ho et al [4] and Grimes et al [1], with
sorption materials like tree fern and vegetal compost (green and domestic waste). The metals
interaction with the compost surface chemical structures can be seen as complexation reactions,
stabilised by electronic effects that are strongly dependent to the ionic potential; that is, the charge
to radius ratio of bivalent metals from the periodic table fourth period, known as the Irving Williams
series.
Table 2 Maximum sorption capacity of each compost for Cu and Zn.

qmax Cu (mg/g) qmax Zn (mg/g)
MSW 11.1 6.8
SS 15.7 13.7
PM 13.1 9.0
SS compost has higher capability for these metals sorption. The maximum sorption of Cu and Zn
achieved by SS were: 15.7 and 13.7 mg/g respectively. Regarding the values of CEC reported
earlier, the sorption behaviour is consistent with the cation exchange capacity, that is, the sorption
increases with the CEC. The physical and chemical characteristics of sorbents and sorbats are
15
closely related with the sorption extent. Grimes et al [1], reported that the copper sorption by
compost of green and household wastes depends on both the organic and the inorganic fraction of
the sorbent. Sewage sludge compost has higher organic matter content (82.3 %), lower pH (4.9)
and higher CEC (3.9). The carboxylic and phenolic groups, characteristic of the compost organic
matter, are closely related to the electrostatic interactions between the bivalent soluble cations
2+ 2+
(Cu and Zn ) and the surface structures. The low pH of SS compost also suggest the release of
+
H to the solution and the formation of carboxylate bases with negative charge, establishing strong
links with metals positive charges. Regarding the PM and MSW composts, the former had higher
sorption capacity but lower organic matter content, although it CEC was higher. This phenomenon
can be explained by the fact that the PM compost has high lignin content, as mentioned Bailey et
al. [3] and lignin has a high sorption capacity, due in part to the poly phenols and other functional
groups at the surface. So, it is possible to realize that the sorption interactions are closely related
with these parameters.
CONCLUSIONS
2+ 2+
The present work has studied the sorption of heavy metal cations, Cu and Zn , from aqueous
solutions onto three composts commercialized in Portugal. For the three composts, the maximum
time necessary to reach the equilibrium was 240 minutes. The composts have shown their ability to
sorb the metals with various efficiencies, which was higher for the compost with higher organic
matter content and CEC. The SS compost confirmed higher capacity to capture both heavy metal,
2+ 2+
with maximum sorption capacities of 13.7 mg/g for Zn and 15.7 mg/g for Cu . The compost less
2+
suitable for the initial purpose was MWS, which showed a sorption of 6.8 mg/g for Zn and 11.1
2+ 2+ 2+
mg/g for Cu . For the three composts, Cu was retaining with higher extension than Zn .
REFERENCES
[1] S. Grimes, G. Taylor, J. Cooper, The availability and binding of heavy metals in compost
derived from household waste, Journal of Chemical Technology and Biotechnology 74
(1999) 1125-1130.
[2] WHO, Guidelines for Drinking Water Quality, World Health Organization, Geneva, 2006.
[3] S. Bailey, T. Olin, M. Bricka, D. Adrian, A review of potentially low-cost sorbents for heavy
metals, Water Resources, 33 (1998) 2469-2479.
[4] Y. Ho, C. Huang, H. Huang, Equilibrium sorption isotherm for metal ions on tree fern, Process
Biochemistry 37 (2002) 14211430.
[5] I. Vaz-Moreira, M. E. Silva, C.M. Manaia, O.C.P. Nunes, Diversity of Bacterial Isolates from
Commercial and Homemade Composts, Microb Ecol 55 (2008) 714722.
[6] W. Thompson, P. Leege, P. Millner, M.E. Watson, Test Methods for the Examination of
Composts and Composting, The US Composting Council, US Government Printing Office,
2001.
[7] D. O. Cooney Adsorption design for wastewater treatment, Boca Raton: Lewis Publishers, 1998.
[8] I. P. L. Brs, Utilizao de Casca de Pinheiro como adsorvente para remoo de
pentaclorofenol de guas contaminadas, Dissertao de Doutoramento, FEUP, Porto, 2005.
[9] R. Tseng, F. Wu, R. Juang, Liquid-phase adsorption of dyes and phenols using pinewood-
based activated carbons, Carbon, 41,(2003) 487495.
[10] O. Gilbert, J. Pablo, J. Cortina, C. Ayora, Sorption studies of Zn(II) and Cu(II) onto vegetal
compost used on reactive mixtures for in situ treatment of acid mine drainage, Water
Research 39 (2005) 2827-2838.
[11] M. Ulmanu, E. Maran, Y. Fernadez, L. Castrilln, I. Anger, A. Dumitriu, Removal of copper
and cadmium ions from diluted aqueous solutions by low cost and waste material
adsorbents, Water, Air, and Soil Pollution 142 (2003) 357373.
16
1St International Conference
WASTE POLYMERS RECYCLING IN HIGH PERFORMANCE ASPHALT

MIXTURES
1 2 3 4
H.M.R.D. Silva , A.V. Machado , J.R.M. Oliveira and L.M.B. Costa
1 C-TAC, University of Minho, 4800-058 Guimares, Portugal, hugo@civil.uminho.pt
2 I3N / IPC, University of Minho, 4800-058 Guimares, Portugal, avm@dep.uminho.pt
3 C-TAC, University of Minho, 4800-058 Guimares, Portugal, joliveira@civil.uminho.pt
4 Dpt. Civil Eng., University of Minho, 4800-058 Guimares, Portugal, a48253@alunos.uminho.pt
ABSTRACT
Building a road pavement requires large amounts of constituent materials, whose
extraction can lead to the devastation of natural resources and causes negative impacts
on the environment. As aggregates comprise nearly 90% of asphalt mixtures, their partial
substitution by waste thermosetting polymers (12 million tons of waste polymers are
presently mislaid into landfills, every year, in Europe) can be considered as a sustainable
technology, given that an equivalent performance can be assured. Thus, this study aims
on evaluating possible advantages of introducing polyethylene based wastes in asphalt
mixtures, namely high density polyethylene (HDPE) and cross-linked polyethylene (PEX),
incorporating HDPE as a bitumen modifier and PEX as partial substitute of the
aggregates. The laboratory tests carried out in this work showed that the use of HDPE
significantly improves the behavior of the asphalt binder/mixture. The use of PEX
considerably decreases the density of the mixtures, which can be attractive to lighten
structures. The mixtures with PEX have similar performance to the conventional one in
terms of water sensitivity, improving the permanent deformation resistance and reducing
the temperature susceptibility. In brief, the mixtures incorporating waste polymers could
be considered a good technical and environmental alternative for paving works.
Keywords: Waste polymer recycling; Polyethylene; Polymer modified binder; Asphalt performance
INTRODUCTION
Presently, in Europe, 12 million tons of waste polymers are mislaid into landfills every year [1].
Most of these polymers have a very simple process of recycling, but the mechanical recycling
generally does not work for thermosetting polymers and elastomers, because these polymers do
not melt. Since they cannot be reprocessed, their reuse may be possible by taking advantage of
their potential as aggregates that can be incorporated in road pavements.
In fact, building a road pavement requires a large amount of constituent materials, whose
extraction can lead to the devastation of natural resources and cause negative impacts on the
environment. As aggregates comprise nearly 90% of asphalt mixtures, their partial substitution by
waste thermosetting polymers can be considered as a sustainable technology, given that an
equivalent performance can be assured [2].
Thus, this study aims on evaluating the possible advantages of introducing polyethylene based
wastes in asphalt binders and mixtures by using different processes of incorporation. The materials
used were high density polyethylene (HDPE) and cross-linked polyethylene (PEX), the first as a
bitumen modifier and the second as partial substitute of the aggregates.
Polymers can be applied in asphalt mixtures as bitumen modifiers or as partial substitute of the
aggregates, and they could also be used as an aggregate coating layer [3]. Among polymers that
may be used in asphalt mixtures, the most used are thermoplastics and elastomers [4], namely
polyethylene based polymers, as well as EVAs, SBS and SBR polymers. According to several
authors [5, 6] the use of recycled polymers or waste polymers rather than new is possible and most
valuable, which leads to ecological and possibly to economic benefits.
17
MATERIALS AND ASPHALT MIXTURES PRODUCTION CONDITIONS
Selection of Polymer Wastes
The aim of this study is to use a polymer residue that exists in high amounts in order to replace the
aggregates in asphalt mixtures, so that their use is feasible, which presents properties that might
be advantageous to the asphalt mixture. According to information gathered from local companies
for solid waste collection and processing, cross-linked polyethylene (PEX) wastes are present in
large quantities and have low commercial value due to their low demand (Fig. 1a). The
polyethylene in PEX was crosslinked in order to become inert, because it is used in hot water pipes
or electrical cable sheathing at high service temperatures. Actually, in this study PEX was selected
to be used as aggregate in asphalt mixtures, because its crosslinked chains do not melt.
The crosslink process can be more or less effective, thus being important to determine the GEL
content of the PEX residue used in this study. The results indicated that the GEL content is 54%,
which is the percentage of crosslinked material that does not melt. In fact, some part of the used
PEX can melt into the bitumen, thus modifying the binder during the production of asphalt mixtures.
Thus, this study also evaluated, comparatively, the bitumen modification with wasted HDPE (high
density polyethylene), which is another polyethylene based plastic that melts completely (Fig. 1b).
(a) (b)
Fig. 1 Polymer wastes used in this study: (a) PEX and (b) HDPE
PEX waste is presented in a flake shape (Fig. 1a). Its original dimensions, as it was provided,
ranged from 0.5 to 10.0 mm. However, due to its lamellar form totally different from that of typical
aggregates, which can reduce the mechanical strength of asphalt mixtures, it was decided to
mechanically grind the PEX particles (less lamellar particles were obtained with dimensions from
3
0.5 to 4.0 mm). PEX density was also determined (EN 12697-5 standard), being 938.6 kg/m .
HDPE waste (Fig. 1b) is provided with dimensions between 0.5 and 10.0 mm. Since HDPE will be
used for bitumen modification, its dimensions can influence de digestion time and the efficiency of
the modification process. Thus, the initial dimensions of HDPE were intentionally reduced to 0.5 to
4.0 mm, by using the same mechanical grinder, in order to improve the modification process.
Binder Characterization
All the work of binders and mixtures characterization was developed with a single 50/70
commercial bitumen. The HDPE modified binders were prepared at 180 C for two percentages of
polymer (3 and 6%) using several digestion times (0.5, 1.0, 1.5 and 2.0 hours).
The PEX waste used in this study is not totally crosslinked, thus being necessary to evaluate its
possible interaction with the bitumen during the production of asphalt mixtures. In order to carry out
that evaluation, the binder was prepared using the production conditions obtained in the Marshall
mix design of the AC 14 Surf 50/70 conventional mixture, i.e. binder content (BC) of 5.0%, together
with a PEX percentage of 5.0% (volume ratio between PEX and the all aggregates) determined to
properly adjust the grading curve of the mixture with PEX. The binders modified with the melted
part of PEX were produced for a 2 min digestion time (production time for asphalt mixtures), and
then a metal mesh was used to filter out the binder, sorting out the crosslinked PEX particles.
In order to classify the binders used in this study, their basic properties were obtained through the
EN 12591 standard, namely by carrying out penetration (EN 1426) and softening point (EN 1427)
tests. The evolution of the penetration at 25 C and softening point of the 50/70 bitumen and the
binders modified with 3 and 6% HDPE with the increase of the digestion time is presented in Fig. 2.
18
60 65.0
Ring & Ball temperature [C]

Penetration [0.01 mm]
50
60.0
40
30 55.0
20
50.0
10
50/70 3% HDPE 6% HDPE 50/70 3% HDPE 6% HDPE
0 45.0
30 60 90 120 30 60 90 120
Digestion time [min] Digestion time [min]
Fig. 2 Evolution of the penetration and ring and ball temperature with the digestion time
As expected, the higher changes in the properties of the binder were caused by the increase in the
quantity of HDPE used (from 3 to 6%). In fact, the binder with 6% HDPE could be classified as a
20/30 binder, increasing the softening point by 13 C. The digestion time (30 to 120 min) has little
influence in the properties of the binders. The selection of the HDPE modified binder to be used in
the following phases (6% HDPE and 60 min of digestion time) of the work was based in these
results, as well as on the observation of the binders during their production.
Next, the basic properties of the modified binder obtained by the introduction of PEX as aggregate
were determined (Table 1). The filtered binder was obtained after 2 min digestion time at 180 C.
Table 1 Comparison between the base properties of binders modified with HDPE and PEX
Type of Type and % Pen Pen Pen A&B A&B A&B
bitumen of polymer [dmm] [dmm] [%] [C] [C] [%]
None 58.1 0.0 0.0 51.1 0.0 0.0
PEX 37.1 -21.0 36.0 53.7 2.6 5.0
50/70
3% HDPE 41.7 -16.4 28.0 55.2 4.1 8.0
6% HDPE 27.9 -30.2 52.0 62.6 11.5 22.5
It was observed that only a small part of the SOL content of PEX have melted into the bitumen,
probably because the digestion time used was very short (2 min). The penetration results showed
that the binder obtained after the mixture with PEX is similar to a HDPE binder modified with 3 to
6% of polymer. The softening point results demonstrated a lower modification grade obtained after
the mixture with PEX, even inferior to that obtained with 3% HDPE.
Definition of the Mixtures Production Conditions
The selection of the temperatures to be used in the production of the conventional and modified
(PEX and HDPE) mixtures, was based on the reference of EN 12697-35 standard and on the
properties of the binders previously presented. Thus, the conventional mixture was produced at
150 C, while the polymer modified mixtures were produced at 165 C (PEX) and 180 C (HDPE).
The conventional mixture (AC14 surf 50/70) was designed according to the grading envelope
presented in the national attachment of NP EN 13108-1 standard. By changing the quantities of
each aggregate fraction used in the conventional mixture (Table 2), it was possible to define a
grading curve that fell inside the limits of the referred envelope (also used in the mixture with HDPE
modified binder). However, the grading curve and the quantities used in the mixture with PEX were
inevitably adjusted (Table 2) because the PEX waste was applied as a partial substitute of the
aggregates (volume ratio of 5%, corresponding to 1.8% in weight due to the low density of PEX).
Table 2 Materials and quantities used to produce the different asphalt mixtures
Asphalt Type of Aggregates used in the mixture [%]
Mixture binder Fraction 6/14 Fraction 4/6 Fraction 0/4 Filler PEX (milled)
Conventional 50/70 46.0 13.0 39.3 1.7 -
HDPE 50/70+6%HDPE 46.0 13.0 39.3 1.7 -
PEX 50/70 46.5 11.3 38.6 1.8 1.8
19
Next, the optimum binder content of the conventional mixture (5.0%) was determined through the
Marshall mix design method, and this value was maintained in the mixtures with HDPE and PEX in
order to allow their comparison. Due to the high quantity of polymer waste used in the mixtures with
PEX, which partially interacts with the bitumen, it was decided that a complementary study should
be carried out according to the national appendix of NP EN 13108-1 standard, namely by using
higher binder contents (5.0, 5.5 and 6.0%). In the complementary study, the water sensitivity of the
mixtures was evaluated according to EN 12697-12 (Table 3). This test comprises the assessment
of the indirect tensile strength (ITS), carried out according to EN 12697-23, of two identical groups
of specimens conditioned in different environments (dry and wet), and the evaluation of the ratio
(ITSR) between the average strength results of both groups of specimens. The air voids content
(EN 12697-8) of the specimens and the deformation on rupture were also determined.
Table 3 Results of the complementary mix design tests used for the PEX modified mixtures
Evaluated property BC = 5.0% BC = 5.5% BC = 6.0%
Air voids content Vv [%] 5.0 2.9 1.3
Water sensitivity ITSR [%] 47.0 57.0 61.0
Indirect tensile strength ITS dry [kPa] 1655.4 1824.3 1985.6
Mean deformation of dry specimens [mm] 2.4 2.7 2.5
As expected, the mixture with a binder content of 5.0% had higher air voids content, and as result
presented higher water sensitivity in comparison with the other mixtures. Although the Marshall mix
design have shown an optimum binder content of 5.0%, the results of this complementary study for
the mixtures with PEX indicate a higher binder content. Thus, in the following part of the work, two
mixtures with PEX will be produced and characterized with binder contents of 5.0 and 5.5%.
PERFORMANCE OF ASPHALT MIXTURES PRODUCED WITH WASTED POLYMERS
This study consists in the comparative evaluation of the mechanical performance of three mixtures
with identical composition, which were produced with different constituent materials, namely a
conventional mixture, another with HDPE modified binder and the third with PEX substituting part
of the aggregates (Fig. 3). The mixtures with PEX were produced with two binder contents (5.0 and
5.5%). Thus, the four mixtures studied in this phase of the work were the following ones:
- Mix A: conventional mixture with 5.0% of a 50/70 bitumen;
- Mix B: mixture with 5.0% of a 50/70 bitumen modified with 6% HDPE;
- Mix C1: modified mixture using milled PEX as aggregate, with 5.0% of a 50/70 bitumen;
- Mix C2: modified mixture using milled PEX as aggregate, with 5.5% of a 50/70 bitumen.
Fig. 3 Specimens of mixtures C1 and C2 using PEX as aggregates
The maximum density (EN 12697-5) and the bulk density (EN 12697-6) of the asphalt mixtures
were determined in order to determine their air voids content (EN 12697-8), as follows:
3
- Mix A: maximum density of 2442 kg/m and air voids content of 2.0%;
3
- Mix B: maximum density of 2430 kg/m and air voids content of 3.0%;
3
- Mix C1: maximum density of 2373 kg/m and air voids content of 3.0%;
3
- Mix C2: maximum density of 2353 kg/m and air voids content of 2.5%.
The properties of the mixtures with PEX are different from those of the conventional mixture,
especially the maximum density that is much lower due to the low density of PEX. The use of this
20
lighten mixtures with PEX can be useful in the transport and in the application on lighten structures
(e.g. bridges). Finally, it was observed that the air voids content of the several mixtures is similar.
Water Sensitivity
All mixtures were tested for water sensitivity according to EN 12697-12 standard, previously
mentioned, and the results obtained for the mixtures under study can be observed in Fig. 4.
100 5 ITSd [kPa]

ITSR [%] Vv [%] 2000 5
90
Deformation [mm]
Deformation [mm]
80 4 4
70 1500
ITSR [%]
60 3
Vv [%]
3
ITSd [kPa]
50 1000
40 2 2
30
20 1 500
1
10
0 0 0 0
Mix A - Mix B - 6% Mix C1 - Mix C2 - Mix A - Mix B - 6% Mix C1 - Mix C2 -
Unmodified HDPE PEX PEX Unmodified HDPE PEX PEX
(BC=5.0%) (BC=5.5%) (BC=5.0%) (BC=5.5%)
Fig. 4 Water sensitivity results of the studied mixtures
The mixture with the HDPE modified binder presented better performance than the conventional
mixture, whereas the performance of the mixtures with PEX was similar to that of the conventional
mixture (mix C2 was slightly less sensitive to water due to its higher binder content).
Permanent Deformation Resistance
In this study, the determination of the resistance to permanent deformation was carried out using
the Wheel-Tracking Test or WTT (EN 12697-22). The susceptibility of the mixtures to deform was
assessed by measuring the rut depth formed by repeated passes of a loaded wheel at 50 C. The
evolution of the rut depth (mm) in air of the studied mixtures with the number of load cycles at
50 C is presented in Fig. 5, as well as the mean wheel-tracking slope (WTS AIR ), in air, which is the
result typically used to rank the permanent deformation performance of asphalt mixtures.
No of cycles
10 100 1000 10000
0.1
Rut depth (mm)
1.0
Mix A - Unmodified
Mix B - 6% HDPE
Mix C1 - PEX (BC=5.0%)
Mix C2 - PEX (BC=5.5%)
10.0
Fig. 5 Evolution of the permanent deformation of the studied mixtures in the WTT
By analyzing the results of this test it was concluded that the mixtures with polyethylene, used as
binder modifier (HDPE) or as partial substitute of the aggregates (PEX) (including mixture C2 with
a BC of 5.5%), are much more resistant to permanent deformation than conventional mixture.
Stiffness Modulus
The structural performance of the pavements is directly related to the mechanical behavior of the
bituminous mixtures, which can be characterized through the stiffness modulus and phase angle.
In this work, these properties were obtained by using the four-point bending beam test, with a
21
repetitive sinusoidal loading configuration, as stated in EN 12697-26. The frequency sweep (0.1 to
10 Hz) tests were carried out at 20 C. The variation of the stiffness modulus and phase angle of
the studied mixtures with the frequency, at 20 C, is presented in Fig. 6.
7000 50.0
Mix A Mix B
Stiffness modulus [MPa]
6000
Mix C1 Mix C2 40.0
Phase angle []
5000
4000 30.0
3000 20.0
2000
Mix A Mix B
10.0
1000
Mix C1 Mix C2
0 0.0
0.1 1 10 0.1 1 10
Frequency [Hz] Frequency [Hz]
Fig. 6 Stiffness modulus and phase angle results of the studied mixtures
The evolution of the stiffness moduli with the frequency is similar for all studied mixtures. The
mixture with HDPE (mix B) was the one with higher modulus in consequence of the higher viscosity
of the modified binder. The conventional mixture was the one with lower modulus, because the use
of PEX as partial substitute of the aggregates also increased the stiffness modulus of the mixtures,
including in the mix C2 with a higher binder content. The phase angle of the asphalt mixtures with
polyethylene based wastes (PEX and HDPE) is clearly lower than that of the conventional mixture,
revealing a less viscous behaviour of those mixtures and explaining their higher rutting resistance.
CONCLUSIONS
The main conclusions of this work were the following:

- Several polymer wastes can be used in asphalt mixtures as binder modifiers or as partial
substitutes of the aggregates, and the PEX wastes emerged as one of the best solutions due to
their low commercial value (HDPE was also selected as a polyethylene based waste alternative);
- The HDPE waste greatly changed the properties of the binder, and the use of PEX waste as
aggregates also modifies the bitumen;
- The use of polyethylene based polymers has the advantage of lighten the asphalt mixtures,
especially when using PEX, and simultaneously can maintain (water sensitivity) or improve
(rutting resistance and stiffness modulus) the performance of those mixture.
- Briefly, the use of PEX / HDPE wastes could be considered a good alternative for paving works.
Acknowledgments
The authors would like to thank Gintegral, Cepsa and Bezerras companies for supplying the
materials for this study, which was concluded with the support given by the Portuguese Foundation
for Science and Technology (FCT) in the scope of the Strategic Project UI 4047 20112012.
References
[1] EUPC, The Compelling Facts About Plastics 2009, Info on http://www.plasticsconverters.eu/
[2] H.L. Robinson, Polymers in asphalt, Smithers Rapra Technology, United Kingdom, 2005.
[3] R. Vasudevan, R. Velkennedy, A. Ramalinga, S. Sekar, B. Sundarakannan, Utilization of waste
polymers for flexible pavement and easy disposal of waste polymers, Int. J. Pavement
Research and Technology 3 (1), 2010, 34-42.
[4] J. Read, D. Whiteoak, The Shell Bitumen handbook, Thomas Telford Publ., London, 2003.
[5] S. Hnsloglu, E. Agar, Use of waste high density polyethylene as bitumen modifier in asphalt
concrete mix, Materials Letters 58, 2004, 267-271.
[6] S.E. Zoorob, L.B. Suparma, Laboratory design and investigation of the properties of
continuously graded AC containing recycled plastics aggregate replacement, Cement &
Concrete Composites 22, 2000, 233-242.
22
SUSTAINABLE APPLICATION OF CONSTRUCTION AND DEMOLITION

RECYCLED MATERIALS (C&DRM) IN ROAD INFRASTRUCTURES
1 2 3 4 5 6
A.C. Freire , J.M. Neves , A.J. Roque , I.M. Martins , M.L. Antunes , G. Faria
1
Laboratrio Nacional de Engenharia Civil, Lisboa, Portugal, acfreire@lnec.pt
2
Instituto Superior Tcnico, Lisboa, Portugal, neves@civil.ist.utl.pt
3
Laboratrio Nacional de Engenharia Civil, Lisboa, Portugal, aroque@lnec.pt
4
Laboratrio Nacional de Engenharia Civil, Lisboa, Portugal, imartins@lnec.pt
5
Laboratrio Nacional de Engenharia Civil, Lisboa, Portugal, mlantunes@lnec.pt
6
Laboratrio Nacional de Engenharia Civil, Lisboa, Portugal, gfaria@lnec.pt
ABSTRACT
The use of Construction and Demolition Recycled Materials (C&DRM) in road pavements
is envisaged as a solution with environmental and economic benefits. Their application as
unbound granular materials in pavement layers (base, sub-base and capping layers) also
has the advantage to allow the incorporation of large quantities of those materials, from
different origins.
The generalised application of C&DRM in road construction is however still limited by
some knowledge gaps, deriving from the lack of information concerning the mechanical
and environmental performance of these materials and from the limited experience with
their practical application in road construction.
A research project, SUPREMA, aiming to contribute to the sustainable implementation of
C&DRM in road pavements, by improving the knowledge concerning the mechanical and
environmental behaviour of these materials when placed as aggregates in unbound
pavement layers, is being developed by the National Laboratory for Civil Engineering
(LNEC), in cooperation with Technical University of Lisbon (IST), over three years.
This paper discusses the detailed objectives and methodology of the research project
and presents some of its early results, in particular the ones concerning the C&DRM
potential pollution.
Keywords: Sustainability; demolition and recycled materials; road infrastructures
INTRODUCTION
Construction activities usually generate large amounts of waste. The annual overall waste
production, among the European Union members, is being estimated in 850 million tons [ 1]. This
waste derives from different sources and processes, namely cleaning of the work site and
earthworks, discarded materials during construction and demolition operations, as well as
maintenance and rehabilitation of existing constructions.
Due to the increasing shortage of space for landfill implementation and the increased costs
associated with waste control regulations, with higher demands for environmental protection, the
most desirable alternative is the reduction in construction and demolition waste volumes, by means
of their reuse and recycling. According to the new Waste Framework Directive, 2008/98/EC [ 2] a
target of 70% recycling of C&D waste is to be achieved by 2020. In Europe, with an aggregate
demand about 3 billion tons/year, only 6% supply come from recycled aggregates [ 3].
The main purpose of the project SUPREMA Sustainable Application of Construction and
Demolition Recycled Materials (C&DRM) in Road Infrastructures is to respond to the issues
raised by the national and international technical community through the development of the
research lines concerning the application of C&DRM as recycled aggregates in road pavement
base and sub-base layers and in capping layers. The work plan includes a specific experimental
programme, comprising laboratory and in situ tests on a reference natural aggregate and several
23
selected C&DRM: crushed concrete, crushed mixed concrete, crushed reclaimed asphalt and
milled reclaimed asphalt.
This paper presents some early results, namely those regarding geometrical and physical
properties of the selected aggregates and in particular the ones concerning the C&DRM potential
pollution.
Geometrical and physical assessment

The characterization of C&DRM samples selected in this project was done in accordance with the
applicable European Standards, namely for the geometrical, physical and mechanical assessment,
and following the Portuguese LNEC Specification E473 [ 4], applicable to C&DRM recycled
aggregates for unbound granular layers. The European Standards EN 933-11 [ 5] specify the
methodology to identify and estimate the relative proportions of constituent materials.
Environmental assessment
Nowadays, regardless the use of C&DRM on road infrastructures could attain a satisfactory
mechanical performance, the environmental concern regarding the potential contamination of
surface and groundwater forces the appraisal of the release of dangerous substances through
evaluation of the leaching behaviour of those materials. To achieve this objective laboratorial and in
situ leaching tests were proposed in this project.
Portuguese LNEC Specifications E473 and E474 [ 8], concerning the use of recycled aggregates in
unbound road layers, requires that the release of dangerous substances is assessed through EN
12457-4 [ 8 ] LNEC-E474, Guide for the use of recycled materials coming from construction and
demolition waste in embankment and capping layer of transport infrastructures, LNEC (2009) (in
Portuguese).
[ 9] and that the limits on leaching comply with those of the Council Decision on the acceptance of
waste at landfills, 2003/33/EC [ 10] (transposed to the Portuguese DL 183/2009 of 10 August)
regarding waste for disposal in inert landfill, being these criteria also adopted by other European
countries [ 11].
Leaching tests according to EN 1744-3 [ 12] were also foreseen in the project owing to the fact that
European Standard EN 13242 [ 13], regarding aggregates for unbound and hydraulically bound
materials for use in civil engineering works and road construction, refers that water soluble
constituents of these aggregates should be assessed through this procedure. This test was
specifically for unbound aggregates and it intend to be used with their real particle size distribution
unless it surpasses 32 mm, in which case size reduction must be carried on. For this test there are
no defined criteria to assess the leaching results although an approach is to compare it with those
obtained with natural aggregates.
The leaching tests according to EN 12457-4 and EN 1744-3 were developed to evaluate the short
term release of contaminants. They have similar liquid to solid ratio, 10:1, and leaching time, 24h,
but differ on the path used to prepare the test portion, on the particle size distribution, up to 10 mm
and up to 32 mm, respectively, and on the type of agitation. The principle behind both tests is that
equilibrium or near equilibrium conditions between solid and liquid phases were achieved
throughout the test although some controversy exists on this subject [ 14].
Other leaching tests that will be performed include tests in column with up-flow percolation in
accordance to CEN/TS 14405 [ 15], and in situ test using lysimeters. These tests intend to
measure the release of pollutants on real or near real conditions and to compare it with the
outcome from the other leaching tests. It should be emphasized that results from leaching tests
may be conservative, preventing the recycling of some waste, or non conservative, contributing to
pollution of the environment. Comparison of the results of CEN laboratory leaching tests with
lysimeter tests indicates that column tests provide the most detailed simulation of the actual
leaching behaviour of the waste under normal circumstances [ 16]. The results of the ongoing
project will be an important contribution to assess the adequacy of the current classification on the
environmental hazard of some construction and demolition waste flows based on leaching tests
conducted in accordance with EN 12457-4.
24
Crushed mixed concrete (Figure 2a), crushed reclaimed asphalt (Figure 2b) and milled reclaimed
asphalt (Figure 2c) from construction and demolition wastes were used as recycled aggregates and
limestone was used as a natural aggregate (Figure 2d). Tests on crushed concrete are still being
carried on.
(a) (b) (c) (d)

Figure 1 Tested materials
The constituents of coarse recycled aggregates were classified according to EN 933-11 by hand
sorting particles of different constituents, exception made to the floating particles, and expressing
the proportion as a percentage by mass. For the floating particles content the result is expressed
as a volume by mass.
The grain size distribution was determined according to NP EN 933-1, by the sieving method with
washing aggregate for remove clay particles and others aggregate finer particles, exception made
to the milled reclaimed asphalt that was analysed without aggregate washing. Particle density and
water absorption were determined according to NP EN 1097-6 [ 7].
The leaching tests were performed on two replicates of representative samples of the different
materials following the methodologies of EN 12457-4 and EN 1744-3. The eluates were filtrated
over a 0.45 m filter and the pH and conductivity were measured and then were acidified with ultra-
pure nitric acid before assessing heavy metals concentration by graphite furnace atomic absorption
spectrophotometry. Chlorides and sulphates were quantified by titration and gravimetry and
dissolved organic carbon was evaluated by wet oxidation.
MAIN RESULTS
Constituents
The constituents of the studied recycled aggregates are listed on Table 1. According to the
constituents proportions crushed mixed concrete belong to class C of recycled aggregates covered
by the Portuguese LNEC Specification E473. For reclaimed asphalt materials the proportion of
constituents does not allow them to fit in any class of this specification.
Table 1 Classification of constituents

Crushed mixed Crushed reclaimed Milled reclaimed
Constituents
concrete asphalt asphalt
Rc [%] 60 6.2 0.0
Ru [%] 24 29 0.0
Ra [%] 12 64 99
Rb [%] 3.7 0.9 0.0
Rg [%] 0.0 0.0 0.0
X [%] 0.1 0.0 0.8
3
FL [cm /g] 0.0 0.0 0.0
Legend: Rc - Concrete, concrete products, mortar, concrete masonry units;
Ru - Unbound aggregate, natural stone, hydraulically bound aggregate;
Rb - Clay masonry units (i.e. bricks and tiles), calcium silicate masonry units, aerated non-floating concrete;
Ra - Bituminous materials; Rg - Glass; X - Other: Cohesive (i.e. clay and soil), miscellaneous: metals (ferrous and nonferrous),
non-floating wood, plastic and rubber, gypsum plaster; FL - Floating particles.
25
Geometrical and physical tests
The results of grain size distribution performed on C&DRM analysed and the requirements of the
Portuguese Road Administration (EP) [ 17] for recycled aggregates to be used in unbound granular
layers are presented on Figure 2.
Grain size distribution of crushed reclaimed asphalt and crushed mixed concrete are similar and
are mostly inside the grading envelope presented by the Portuguese Road Administration.
The milled reclaimed asphalt sample presents a grain size distribution outside the envelope, having
particles of a smaller size.
Figure 2 - Grain size distribution for material and Portuguese guidelines for grading [ 17]
The results of particle density and water absorption tests performed on the three recycled
aggregates are presented on Table 2.
Table 2 - Density and water absorption results

Size Crushed Crushed Milled
Parameter particle mixed reclaimed reclaimed
Apparent particle density 2.604 2.501 2.502
[Mg/m ]
Particle density on a saturated and

3
4.0 / 31.5 2.443 2.456 2.470

surface-dried basis
Particle density on an oven-dried basis 2.343 2.426 2.448
Apparent particle density 2.496 2.324 2.403
[Mg/m ]
Particle density on a saturated and

3
0.063 / 4.0 2.396 2.272 2.344

surface-dried basis
Particle density on an oven-dried basis 2.329 2.234 2.303
4.0 / 31.5 4.3 1.2 0.88
[%]
Water absorption
0.063 / 4.0 2.9 1.7 1.8
The obtained values for particle density are slightly lower than those usually obtained for natural
materials, especially those in the 0.063/4.0 size particle. Regarding the water absorption, the
values obtained for the reclaimed asphalt aggregates, are within the range of values usually
observed for the natural materials. The values obtained for the crushed mix concrete are higher
than those obtained for natural materials.
Leaching tests
The results of leaching tests performed on the studied materials are presented on Table 3 along
with the waste acceptance thresholds for disposal of waste in landfill for inert waste of the Council
Decision 2003/33/EC.
None of the evaluated contaminants content is superior to the limits of the acceptance criteria. For
the metallic determinants, all belonging to List I and List II of dangerous substances of the Directive
2006/11/EC [ 18], the results were far below the targets for inert waste, exception made to
26
chromium on crushed mixed concrete that is approximately 4 times lower than the limit. It should
be emphasized that the very low release of the contaminants on the short term for the different
C&DRM evidence the feasibility of their use as alternative materials in road construction.
Table 3 Leaching results

Crushed Crushed Milled
Parameter Natural Inert waste
mixed reclaimed reclaimed
[mg/kg, dry matter] aggregate threshold
pH 11.29 10.95 9.67 7.90
Cadmium, Cd <0.005 <0.005 <0.005 <0.005 0.04
Chromium, Cr 0.126 0.046 <0.01 <0.01 0.5
Lead, Pb <0.024 <0.024 <0.024 <0.024 0.5
Zinc, Zn 0.010 <0.006 <0.006 0.035 4
Copper, Cu 0.045 0.030 <0.014 <0.014 2
Nickel, Ni <0.026 <0.026 <0.026 <0.026 0.4
-
Chloride, Cl 44 35 35 44 800
2-
Sulphate, SO4 267 124 13 145 1000
Dissolved organic
46 71 94 71 500
carbon, C
Table 4 list the results of the evaluated parameters on the eluates obtained from the four different
materials on the leaching test according to EN 1744-3. The release of Cd, Pb and Ni is below the
- 2-
limits of quantification in all aggregates and the contents of Cr, Zn, Cu, Cl and SO4 are higher on
recycled aggregates when compared with natural aggregate, with some exceptions on milled
reclaimed asphalt. The own pH of all eluates is lesser in this leaching test and this factor strongly
- 2-
influence the release of chemical species As a general trend Zn, Cl and SO4 contents in the
leaching according to EN 1744-3 are higher in relation to those released on the leaching according
to EN 12457-4 while Cr and Cu contents are lower.
Table 4 Leaching results

Parameter Crushed mixed Crushed reclaimed Milled reclaimed Natural
[mg/kg, dry matter] concrete asphalt asphalt aggregate
pH 9.96 8.12 8.14 6.86
Cadmium, Cd <0.005 <0.005 <0.005 <0.005
Chromium, Cr 0.103 0.022 <0.01 <0.01
Lead, Pb <0.024 <0.024 <0.024 <0.024
Zinc, Zn 0.035 0.023 0.053 0.021
Copper, Cu 0.022 0.016 <0.014 <0.014
Nickel, Ni <0.026 <0.026 <0.026 <0.026
-
Chloride, Cl 53 53 35 35
2-
Sulphate, SO4 343 163 17.5 159
FINAL CONSIDERATIONS
The project SUPREMA, currently underway at LNEC, in cooperation with IST, intends to study the
application of C&DRM as recycled aggregates in road pavement base and sub-base layers and in
capping layers.
The work plan includes laboratory and in situ tests on a reference natural aggregate and several
selected C&DRM: crushed concrete, crushed mixed concrete, crushed reclaimed asphalt and
milled reclaimed asphalt.
Some geometrical and physical characteristics have been determined, allowing the framework of
the materials under study, to be compared with natural materials.
The first results from laboratorial leaching tests suggest that the construction and demolition
recycled materials from this study do not pose an environmental risk, as it is sometimes overstated.
27
Further conclusions on this subject will be withdrawn when all the laboratory and in situ tests,
namely the mechanical and the leaching tests, envisaged on this project, were completed.
ACKNOWLEDGEMENTS
The authors acknowledge the financial support of R&D project PTDC/ECM/100931/2008
SUPREMA Sustainable application of Construction and Demolition Recycled Materials (C&DRM)
in Road Infrastructures funded by Fundao para a Cincia e a Tecnologia (FCT), from
Portuguese Ministry of Science, Technology and Higher Education.
Acknowledgements are also due to Ambigroup, SGPS, SA for providing the studied materials
(crushed mixed concrete, crushed reclaimed asphalt and natural aggregate) as well as Teodoro
Gomes Alho S.A. for the supply of the milled reclaimed asphalt.
References
[1] ETC/SCP working paper 2/2009: EU as a Recycling Society. Present recycling levels of
Municipal Waste and Construction & Demolition Waste in the EU (2009).
[2] Directive 2008/98/EC of the European Parliament and the Council of 19 November 2008
on Waste and Repealing certain Directives. (Text with EEA relevance). Official Journal of European
Union L312/3 of 22 November 2008.
[3] Annual review 2010-2011 of the European Aggregates Association (2011). Information on
http://www.uepg.eu.
[4] LNEC-E473, Guide for the use of recycled aggregates in unbound pavement layers, LNEC
(2009) (in Portuguese).
[5] EN 933-11, Tests for geometrical properties of aggregates Part 11: Classification test for
the constituents of coarse recycled aggregate. CEN (2009, incorporating corrigendum November
2009).
[6] NP EN 933-1:2000 (Ed. 1), Ensaios das propriedades geomtricas dos agregados. Parte
1: Anlise granulomtrica. Mtodo de peneirao.
[7] NP EN 1097-6:2003 (Ed. 1), Ensaios das propriedades mecnicas e fsicas dos
agregados. Parte 6: Determinao da massa volmica e da absoro de gua.
[8] LNEC-E474, Guide for the use of recycled materials coming from construction and
demolition waste in embankment and capping layer of transport infrastructures, LNEC (2009) (in
Portuguese).
[9] EN 12457-4, Characterization of waste. Leaching. Compliance test for leaching of granular
waste materials and sludges Part 4: One stage batch test at a liquid to solid ratio of 10l/kg for
materials with particle sizes below 10 mm (without or with size reduction). CEN (2002).
[ 10 ] Council Decision 2003/33/EC of 19 December 2002 establishing criteria and procedures
for the acceptance of waste at landfills pursuant to Article 16 of and Annex II to Directive
1999/31/EC. Official Journal of European Union L11/27 of 16 January 2003.
[ 11 ] S. Bhmer et al., Aggregates case study, Final report, Umweltbundesamt (2008).
Information on http://www.umweltbundesamt.at.
[ 12 ] EN 1744-3, Tests for chemical properties of aggregates Part 3: Preparation of eluates by
leaching of aggregates. CEN (2002).
[ 13 ] EN 13242, Aggregates for unbound and hydraulically bound materials for use in civil
engineering work and road construction. CEN (2002+A1:2007).
[ 14 ] van der Sloot, H. A. & Mulder, E., Test methods to assess environmental properties of
aggregates in different applications: The role of EN 1744-3, Energieonderzoek Centrum Nederland,
ECN-C-02-011 (2002).
[ 15 ] CEN/TS 14405, Characterization of waste - Leaching behaviour tests Up-flow percolation
test (under specified conditions). CEN (2004).
[ 16 ] ALT-MAT, Alternative materials in road construction. Project Funded by European
th
Commission under the Transport RTD Programme of the 4 Framework Programme, 1998/1999.
[ 17 ] EP Caderno de Encargos Tipo Obra 14.03 Pavimentao, Estradas de Portugal S.A.,
Fevereiro 2009.
28
[ 18 ] Directive 2006/11/EC of the European Parliament and the Council of 15 February 2006 on
pollution caused by certain dangerous substances discharged into the aquatic environment of the
Community (Codified version). (Text with EEA relevance). Official Journal of European Union
L64/52 of 4 March 2006.
29
ASPHALT MIXTURES PRODUCED WITH 100% RECLAIMED MATERIALS
1 2 3
J.R.M. Oliveira , H.M.R.D. Silva and C.M.G. Jesus
1 C-TAC, University of Minho, 4800-058 Guimares, Portugal, joliveira@civil.uminho.pt
2 C-TAC, University of Minho, 4800-058 Guimares, Portugal, hugo@civil.uminho.pt
3 Dept. of Civil Eng., University of Minho, 4800-058 Guimares, Portugal, c.jesus@civil.uminho.pt
ABSTRACT
The environmental and economic benefits of using Reclaimed Asphalt Pavement (RAP)
material in hot mix asphalt (HMA) applications could be pushed up to the limit, by
producing totally recycled HMAs (100% RAP), but the performance of this alternative
must be satisfactory. In fact, these mixtures could possibly present a lower performance
due to the behaviour of the aged binder, which loses its lighter fractions with time. In
order to improve the mixture properties, a binder rejuvenator should be used. Thus, in the
present study, the utilization of a used motor oil as a rejuvenator was evaluated. This
would allow the modification of the aged binder, restoring some of its original properties
and promoting an adequate performance of the mixture.
The optimal amount of oil was determined by conventional bitumen tests, using the
achievement of a bitumen with a penetration grade above, as the selection criterion for
the definition of the amount of oil.
Once the amount of rejuvenator (oil) was defined, laboratory specimens were prepared
and tested for water sensitivity, permanent deformation, stiffness and fatigue, in order to
confirm that the totally recycled mixture will perform as good as a conventional mixture
used for comparison purposes.
Keywords: Asphalt recycling; Binder rejuvenation; 100% RAP; Asphalt mix performance
INTRODUCTION
In order to contribute towards a sustainable development, Road Authorities are beginning to adopt
alternative materials to be applied on their infrastructures. Furthermore, the rehabilitation of the
existing pavements is also being more often considered in a closed cycle, where the old material
(usually know as Reclaimed Asphalt Pavement, RAP) is seen as a product for the new layers,
rather than a waste material [1]. Several studies have been carried out in the past [2, 3, 4] with high
content of recycled asphalt (up to 60%), which is mainly limited by practical issues related to the
production of the mixtures in the asphalt plant.
According to Riebesehl and Nlting [5], the environmental and economic benefits of using RAP in
hot mix asphalt (HMA) applications could be pushed up to the limit, by producing totally recycled
HMAs (100% RAP). However, in order to assure that this type of mixture can be seen by the Road
Authorities as a true alternative, its performance must be as good as that of conventional mixtures.
In fact, these mixtures may present a lower performance due to the loss of the lighter fractions of
the aged binder. In order to improve the mixture properties, a rejuvenator has to be used.
Rejuvenation of bitumen is simple in principle, consisting on the replacement of the oils lost during
the aging process, and on the rebalancing of the bitumen composition. However, this is not
generally possible, as it would require sophisticated extraction, testing and remodelling of the
binder in the road pavement [6]. The used oil was selected for this study because a similar material
has already been used as rejuvenator in previous studies [7]. In addition, it would allow the
recycling of asphalt mixtures with exclusive use of reclaimed materials, which is the main objective
of this study.
30
MATERIAL CHARACTERISATION
In the present study, RAP material was used as the main component of the mixture. However,
since the binder usually present in this type of material is too hard for a conventional bituminous
mixture, a used oil was also used to rejuvenate the binder and improve its properties. In order to
determine the amount of additive that should be added to the mixture (to improve its properties), a
new binder (10/20 pen grade), with properties similar to those of the RAP binder (penetration of
10 x 0,1 mm) was used in this particular part of the study, as it would be impracticable to extract
the necessary amount of aged binder from the RAP to run the series of tests.
The optimum amount of additive that should be used was determined by means of conventional
bitumen tests. The criterion used was the obtainment of a bitumen of a higher penetration grade (in
this case, the bitumen should reach a 20/30 pen grade, since it was previously classified as a
10/20 pen bitumen). The penetration and ring and ball test results are shown in Fig. 1.
70 80
RAP binder
75
Penetration at 25 C (dmm)
60 10/20 bitumen
R&B temperature (C)

70
50 10/20 + Oil
65
40 60
55
30
50
20 45 RAP binder
40 10/20 bitumen
10
35 10/20 + Oil
0 30
0 1 2 3 4 5 6 7 8 9 10 11 12 0 1 2 3 4 5 6 7 8 9 10 11 12
Rejuvenator (%) Rejuvenator (%)
Fig. 1 Penetration and softening point (R&B) test results of bitumen with different percentages of
rejuvenator
As presented in Figure 1, the minimum amount of rejuvenator necessary to modify the aged binder
and achieve a 20/30 penetration grade (corresponding to the shaded areas, as specified in EN
12591) was 5%. This was the additive content used in the remainder of the study.
The grading of the RAP material was evaluated according to EN 933-1 standard. The RAP material
was also incinerated, according to the EN 12697-39 standard, in order to burn the bitumen and to
evaluate the grading of the aggregates constituting the RAP (according to the EN 12697-2), so as
to determine whether it fits within the grading envelope of a conventional surface course mixture
(AC 14 surf), as illustrated in Fig. 2.
100
AC 14 Surf - Upper limit
90
AC 14 Surf - Lower limit
80
Percentage passing
Aggregates in RAP
70
Used RAP - Grading
60
50
40
30
20
10
0
0.01 0.1 1 10 100
Sieve size (mm)
Fig. 2 RAP and its aggregates grading curves outside AC 14 surf envelope
31
The RAP aggregates have an excess of fines and a low percentage of coarse material. This is due
to the milling process or the wearing of the surface layer from which the RAP was extracted.
Excessive fines may cause permanent deformation problems, although this is not expected in this
study because the binder of the RAP is very hard, increasing the rutting resistance. Thus, the
influence of failing to meet the aggregates grading envelope on the performance of the mixture
needs to be verified.
PERFORMANCE OF STUDIED MIXTURES

In order to confirm that the totally recycled mixture will perform as good as a conventional mixture,
water sensitivity, permanent deformation, stiffness modulus and fatigue tests were performed on
both mixtures and the results are presented below.
Water sensitivity
The evaluation of the water sensitivity is essential when studying asphalt recycled mixtures, since
this property is directly related to the performance and durability of these materials during the road
pavement life. The evaluation of this property is determined in Europe by the EN 12697-12
standard. According to this standard, two groups of three specimens are tested for the indirect
tensile strength (ITS) after a different conditioning period. In that period, one group is kept dry and
the other is immersed in water, in order to determine the influence of the water on the weakening of
the bond between aggregates and binder and, consequently, on the strength of the mixture.
Following the determination of the ITS of each specimen, it is possible to calculate the average
value of each group and the indirect tensile strength ratio (ITSR), which corresponds to the ratio
between the ITS of the wet group (ITSw) and the dry group (ITSd) of specimens. In the present
study, the indirect tensile test was carried out according to the EN 12697-23 standard, after a
volumetric characterization of the specimens (to determine the voids content, which significantly
influences the results), as presented in Fig. 3.
ITSR Voids content

100% 4.0%
Voids content (%)
90% 3.0%
ITSR (%)
80% 2.0%
70% 1.0%
60% 0.0%
CONV RAP - OIL
Type of mixture
Fig. 3 Results water sensitivity tests (ITSR vs. air voids content)
Overall, it was found that both mixtures had very good water sensitivity results, although the
conventional mixture (produced with a 35/50 pen grade bitumen) was slightly more sensitive to the
presence of water (lower ITSR due to its higher voids content). The recycled mixture with
incorporation of a rejuvenator (RAP - OIL) showed a better performance (durability), mainly due to
the low volume of voids, which in turn is related to the high amount of fines previously mentioned.
Permanent Deformation
The rut resistance of asphalt mixtures may be assessed, in comparative terms, by the analysis of
wheel tracking test results, plotted in a graph deformation vs. number of cycles. Fig. 4 represents
the results of the recycled mixture and a conventional mixture produced with a 35/50 pen bitumen.
32
0.0
0.5 CONV
1.0 RAP - OIL
Rut depth (mm)
1.5
2.0
2.5
3.0
3.5
4.0
0 2000 4000 6000 8000 10000
Number of cycles
Fig. 4 Wheel tracking tests results of both mixtures carried out in air, at 50 C
The permanent deformation performance of both mixtures is similar, as can be observed from
Fig. 4, although the 100% recycled mixture still showed a slightly better behaviour. One of the main
parameters used to assess the rut resistance of bituminous mixtures is the wheel tracking slope
th th
(WTSair) measured between the 5000 and the 10000 cycles. In this study, the recycled mixture
3
presented a WTSair of 0.14 [mm/10 cycles] while the conventional mixture used for comparison
3
presented a WTSair of 0.16 [mm/10 cycles].
Stiffness Modulus
The stiffness modulus and phase angle were obtained using the four-point bending beam test, with
a repetitive sinusoidal loading configuration, as specified in the EN 12697-26 standard. A frequency
sweep (0.1 to 10 Hz) test was used to determine the response of the material to different loading
frequencies. The tests were carried out at 20 C and the results are presented in Fig. 4.
7000 50.0
CONV
6000
Stiffness modulus (MPa)
RAP - OIL 40.0

5000
Phase angle ()
30.0
4000
3000
20.0
2000 CONV
10.0
1000 RAP - OIL
0 0.0
0.1 1 10 0.1 1 10
Frequency (Hz) Frequency (Hz)
Fig. 5 Stiffness modulus and phase angle for different frequencies at 20 C
As can be observed in Fig. 5, the recycled mixture is less susceptible to the loading frequency
which is typical of mixtures with aged binders, since the stiffness modulus variation is smaller than
in the case of the conventional mixture and the phase angle is significantly lower than that of the
conventional mixture, for any frequency tested. These results are in accordance with those
obtained in the rut resistance tests, where the recycled mixture has shown a good performance,
even at a high temperature (which is equivalent to lower frequencies in the stiffness modulus tests).
33
Fatigue Cracking Resistance
The fatigue life equations at 20 C of the conventional AC 14 Surf 35/50 (CONV) and the 100%
recycled (RAP - OIL) mixtures are presented in Fig. 6, in order to evaluate the difference between
the fatigue resistance of totally recycled and new asphalt mixtures.
1000
RAP - OIL
= 1421.9 N -0.134
R = 0.9922
Microstrain ()
100 CONV
= 3473.5 N -0.252
RAP - OIL R = 0.9961
CONV
10
1.0E+03 1.0E+04 1.0E+05 1.0E+06 1.0E+07
Number of cycles (N)
Fig. 6 Fatigue cracking resistance of both mixtures assessed at 20 C
Based on the results presented in Fig. 6, it was possible to conclude that the recycled mixture
presented a better performance than the conventional mixture.
The high fatigue resistance of the 100% recycled mixture can result from its high content of fines
(the quantity of mastic filling material increases), which are present in the RAP due to the milling
operation of the bituminous mixture from the road pavement. This fact could also have led to rutting
problems if the hardened bitumen of the recycled mixtures was not so stiff. This unexpected high
fatigue resistance result has already been noted by other authors [8], who concluded that the aged
binder in RAP formed a stiffer layer coating the RAP aggregate particles. This layered system
helped to reduce the stress concentration within the mixtures and the aged binder mastic layer was
actually serving as a cushion layer in between the hard aggregate and the soft binder mastic.
The parameters specified in EN 12697-24 (N100 and 6), which are normally used to evaluate the
fatigue performance of bituminous mixtures, were estimated from the fatigue life equations of Fig. 6
and are presented in Table 1.
Table 1 N100 and 6 parameters estimated from the fatigue life equations
-6
Asphalt mixture N100 [No. cycles] 6 [10 ]
RAP - OIL 3.78E+08 222.1
CONV 1.30E+06 106.8
As previously mentioned, the rejuvenators increase the fatigue life of recycled mixtures due to the
combined effect of the reduction on the penetration grade of the binder and the slight increase on
the binder content of such mixtures. In this case, those factors associated with a higher content of
fines greatly enhanced the flexibility of the recycled mixture, thus increasing the fatigue cracking
resistance of the mixture.
CONCLUSIONS
The main conclusions that can be drawn from this study of an innovative mixture, totally recycled
from old and distressed road pavement materials, are the following:
The content of rejuvenator (OIL) was defined by the minimum amount that could change
the grade of the aged binder from 10/20 to 20/30 pen grade (this was assessed by means
of penetration and softening point tests), resulting in an optimum content of 5%;
34
All properties of the 100% recycled mixture evaluated in this work (water sensitivity, rutting
resistance, stiffness and fatigue resistance) showed better results than those of a
conventional asphalt mixture, and this surprisingly good result could be a consequence of
the higher content of fines and the higher stiffness of the binder, associated with the
increased flexibility given by the rejuvenator;
The performance based analysis carried out in this work may be used to obtain and
validate the composition of 100% recycled mixtures that can be implemented in real
pavements, even without complying with the empirical specifications (e.g., grading
envelope) usually applied in road pavement works;
In summary, the total recycling technology can be used to produce mixtures with a
performance as good as conventional asphalt mixtures, provided that adequate storing and
handling conditions are assured during the production stage.
Acknowledgements
The authors would like to acknowledge the support given by the Portuguese Foundation for
Science and Technology to the Territory, Environment and Construction Centre, through the
Strategic Project- UI 4047 20112012. Thanks are also due to the Companies Gabriel Couto S.A.
(for the supply of RAP), CEPSA (for the supply of the 35/50 pen grade bitumen) and Bezerras
Quarry (for the supply of new aggregates).
References
th
[1] R. Hassan, Feasibility of Using High Rap Contents in Hot Mix Asphalt, 13 International
Flexible Pavements Conference, Australian Asphalt Pavement Association, Queensland,
Australia, 2009.
[2] C. Celauro, B. Celauro, G. Boscaino, Production of innovative, recycled and high-
performance asphalt for road pavements, Resources, Conservation and Recycling. 54(6)
(2010), 337-347.
[3] P.A.A. Pereira, J.R.M. Oliveira, L.G. Picado-Santos, Mechanical characterisation of hot mix
recycled materials, International Journal of Pavement Engineering, 5(4) (2004), 211-220.
[4] G. Valds, F. Prez-Jimnez, R. Mir, A. Martnez, R. Botella, Experimental study of
recycled asphalt mixtures with high percentages of reclaimed asphalt pavement (RAP).
Construction and Building Materials, 25(3) (2011), 1289-1297
[5] G. Riebesehl, M. Nlting, Unlocking the full technical potential of RAP, Petersen Asphalt
Research Conference, Western Research Institute, Laramie, USA, 2009.
[6] G. Holleran, T. Wieringa, J. Tailby Rejuvenation Treatments for Aged Pavements, New
Zealand Transport Agency Conf., New Zealand, 2005.
[7] R. Romera, A. Santamaria, J. Pena, M. Munoz, M. Barral, E. Garcia, et al, Rheological
aspects of the rejuvenation of aged bitumen, Rheol. Acta, 45(4) (2006), 474-478.
[8] B.S. Huang, G.Q. Li, D. Vukosavjevic, X. Shu, B.K. Egan. Laboratory investigation of mixing
hot-mix asphalt with reclaimed asphalt pavement. Transportation Research Record 1929
(2005), 37-45.
35
13th September
Session 2.1
( MUNICIPAL SOLID WASTES )
Chairman: Joana Carvalho
36
ESTIMATING THE CARBON FOOTPRINT OF MUNICIPAL SOLID WASTE

MANAGEMENT IN THE REGION OF CANTABRIA, NORTHERN SPAIN
a
E. Cifrian, A. Andrs, J.R. Viguri
Dpt. Chemical Engineering and Inorganic Chemistry, ETSIIT, University of Cantabria, Santander,
Spain
email: vigurij@unican.es
ABSTRACT
Human activity is increasing the concentration in the atmosphere of greenhouse gases.
This is expected to result in a significant warming of the earths surface and other
associated changes in climate within the next few decades. The greenhouse gases
(GHG) that are making the largest contribution to global warming are carbon dioxide
(CO2), methane (CH4) and nitrous oxide (N2O). All three are produced during the
management and disposal of wastes. Local climate action has been identified as a vital
contributor to global mitigation of greenhouse gases emission. Carbon footprint (CF)
being a quantitative expression of GHG emissions from an activity helps in emission
management and evaluation of mitigation measures. The concept of CF has permeated
and is being commercialized in all the areas of life and economy, but there is little
coherence in definitions and calculation of CF among the studies. In this work the CF tool
has been applied to measure the environmental impact of the municipal solid waste
management in the region of Cantabria, Northern Spain. All steps of the waste
management have been taken in account: collection, transport, processing and final
treatment, for the period 20052009. The results showed a continuous decrease of the
Carbon Footprint of the waste management throughout the years.
Keywords: Municipal solid waste; carbon footprint; management; greenhouse gases; recycling;
composting; incineration; landfilling
INTRODUCTION
Municipal solid waste (MSW) generation and management (collection, transfer, transport,
processing and treatment) contributes to environmental problems and health effects including
depletion of non-renewable resources, habitat destruction, water bodies, air and soil pollution,
disamenity effects, noise and accidents. Additionally, MSW management activities generate
emissions of greenhouse gases (GHG), primarily carbon dioxide of biogenic origin (biogenic CO2),
methane (CH4), carbon dioxide of fossil origin (fossil CO 2) and nitrous oxide (N2O) with an
important contribution to the global climate change problem [1-3].
Increasing attention is being paid by managers and planners to achieving a sustainable approach
to waste management and integrating strategies that will produce the best practicable option,
taking into account economic, technical and regulatory aspects, and paying particular attention to
environmental issues [4].
The formulation of the problem, the implementation of management plans and the involvement of
all relevant stakeholders are important steps in the use of system assessment tools to the decision
making in the area of MSW management; a database that can store and manage internal and
external information, the algorithms necessary for the analysis and an interface for communication
with the user, are the fundamental characteristics in the decision making process. Databases of
these decision support tools include abundant detailed primary data, different levels of aggregated
quantitative data, information to obtain indicators and index, as well as analytical tools to obtain
specific indicators as carbon footprint calculators among others [5].
37
The carbon footprint (CF) is an indicator of environmental impact, subcomponent of ecological
footprint (EF), that is estimated by calculating the embodied life cycle energy and greenhouse gas
(GHG) emissions associated with a consumption activity and which aims to make the activity more
sustainable. CF complements individual waste management indicators and together other systems
and tools, leads to support decision making and policy analyses assessing waste management
technologies and strategies under the global change impacts [6,7]. The concept not only enables
companies and administration to demonstrate their efforts to reduce GHG emissions, but also
improves consumer awareness of the issue.
Some authors have addressed the issue of carbon footprint and emissions accounting in the
management of waste: the paper of Scheutz, et al [8], serves as introduction for more detailed
research publications providing a technology-based assessment of quantitative GHG emissions
from different waste management technologies; the review paper of Friedrich and Trois [9],
summarize and compare the quantification of GHG emissions from different municipal waste
management processes in developing and developed countries, with particular emphasis on the
African continent; previous measures of the MSW management CF have been done studying
different policy scenarios [10] or as contribution in a municipal services context [11,12].
In the present paper a specific analysis of the carbon footprint (CF) of the MSW management is
reported. The information of the CF would be used as a reference for decision-making and
implementing useful tools for enhancing the MSW management at the regional level.
METHODOLOGY
To calculate the carbon footprint of the municipal solid waste management the emission factors
obtained in the study of Smith et al [1] have been used; these emission factors identified have been
supported by later works such as Friedrich, et al [9], Astrup, et al [13], Gentil, et al [14], among
others. The key aspects of the GHG accounting in waste management is the waste type and
composition, the GHGs accounted and their assigned Global Warming Potential (GWP), the time
period covered and the boundaries of the studied system with other sectors.
The GHG emissions considered relevant for this paper are biogenic CO 2, fossil CO2, CH4, N2O and
CF4. Other greenhouse gases like CFC, HCFA or HFC have not been taken in account, because
they do not appear in the life cycle of the MSW streams considered.
The reporting mechanism is based on one year of emissions data. The global warming potential
(GWP100) is a factor that allows the concentrations of greenhouse gases to be expected in terms
of the amount of CO2 that would have the same global warming impact. The GWP of biogenic CO2
is zero and CO2 from fossil sources is assigned a value of unity. CH4, N2O and CF4 are,
respectively 21, 310 and 6500 times more potent in global warming terms than the same mass of
CO2 (over a 100 year horizon)[13]. In line with the IPCC default methodology for waste, all
greenhouse gas fluxes are treated as though they take place instantaneously.
The model developed by Smith and coworkers [1] obtain many emission factors (in units of kg CO 2
e/t waste) which take into account all the phases that have any impact in the emissions of GHGs.
In the present work, the model includes four phases in MSW management for each different kind of
management (Figure 1); this model does not include the non-greenhouse gas impacts of waste
management options and the emissions from plant construction.
RESULTS
The Municipal Solid Waste Management model implemented in the region of Cantabria can be
divided in five steps: i) municipal collection from household, ii) transfer the MSW collected, iii)
sorting the materials, iv) transport the sorted materials to the final treatment, and v) final treatment
Four different waste streams are collected separately: mixed waste, paper & cardboard, glass
packaging and light packaging. The particular management of each waste stream is shown in
Figure 2.
38
Figure 1. Boundaries of the MSW Management system to apply the CF model
Figure 2. Cantabria Municipal Solid Waste Management System
39
The Carbon Footprint of the collection, transfer, and transport has been calculated for the MSW
management model of the region. To each final treatment, landfill, composting, incineration,
recycling of glass packaging, recycling of paper and cardboard and recycling of light packaging
waste, a proportional quantity of the route travelled has been assigned, e.g. the kilometres of the
collection of mixed waste, has be assigned to all the final treatments due to different quantities of
this mixed waste have been sent to each treatment. Those transports of the different streams from
MBT plant to the different final treatments (composting, incineration and landfilling), have been
defined as intern transport and they have not been considered in this study due to all these
facilities are located in the same environmental complex.
The results obtained to the Carbon Footprint of transports, in unit of tons of CO2 equivalent, are
presented in Figure 3; it can be observed that the main contribution of the transport carbon footprint
in the year 2005 is the transport to landfill. This contribution has decrease over the years to stay at
a value that represents the 29% of total emissions. The second and the third CF in importance are
associated with the transport of materials to the final treatments recycling of paper and cardboard
and incineration, which represent the 24% and 22% of the total CF of transport respectively, and its
values had increased over the years. The impact of the transports to the other three final
treatments represents less than 10% each one. The total emission of GHG of the transport of MSW
in 2005 was 2.358 tCO2e (7,0 kg CO2e/tMSW), increasing this quantity in 2009 to 2.637 tCO2e (7,3
kg CO2e/tMSW), mainly due to the intensification in the selective collection of fractions to recycling.
These values are according to the range of 5-50 kg CO2e/t MSW reported by Eisted, et al [15].
3.000
2.500
Landfilling
2.000
Incineration
tCO2e/year
1.500 Composting
1.000 Recycling of GP
Recycling of P&C
500
Recycling of LP
0
2005 2006 2007 2008 2009
Figure 3. Carbon Footprint associated to the total transport of the MSW to each final treatment
The Carbon Footprint calculated to the management of the Municipal Solid Waste taking into
account the emissions of GHG produced in the process, the disposal of the waste, the use of the
materials derived from waste and the emissions avoided is presented in Table 1.
Table 1. Carbon Footprint associated to the final treatments of MSW.
Final MSW quantity [thousands t/year] CF [t CO2 e/year]

Treatment 2005 2006 2007 2008 2009 2005 2006 2007 2008 2009
Landfilling 267,1 221,0 191,4 157,2 153,0 117.719 97.402 84.356 69.283 67.432
Incineration 0 65,4 94,0 113,9 116,9 0 21.653 22.454 23.054 22.813
Composting 38,6 39,9 478,0 47,0 42,3 -888 -918 -1.103 -1.081 -973
Recycling 29,9 34,9 39,2 41,1 39,7 -19.816 -22.602 -24.229 -26.521 -26.978
Total [tCO2 e] 97.016 95.536 81.477 64.735 62.294
Table 1 shows that the main contribution is associated to the landfilling; a decreasing of 43% is
observed for this contribution between 2005 and 2009, due to increasing quantities of waste are
now being diverted to incineration with energy recovery, and to MBT before landfilling to recover
recyclables and reduce the organic content by aerobic composting. Furthermore, landfill CH 4
40
emissions are stabilizing due to increase landfill CH 4 recovery, decrease landfilling and decrease
waste generation as a result of specific local waste management decisions including recycling,
policy, plans and programs initiatives and local socio-economic conditions. The magnitude of
avoided GHG emissions benefits from recycling is highly dependent on the specific materials
involved, the recovery rates for those materials, local options for managing materials and specific
fossil fuel avoided [2]. In the present work, the contribution of recycling and composting to the total
GHG emissions is negative, increasing the avoided emissions between 2005 and 2009 in a 35%.
Figure 4 shows the total CF of the MSW management including the transport.
160.000
120.000 Transport
Landfilling
80.000
t CO2e
Incineration
40.000
Composting
0
Recycling
-40.000
2005 2006 2007 2008 2009
Figure 4. Total Carbon Footprint associated to the MSW management
As it is observed in Figure 4, in the total Carbon Footprint of the MSWM the transport of the
materials just represent the 4% of total GHG emissions. The evolution of the total CF is
represented in Figure 5 and shows a general improvement in the CF trend, even more when is
expressed in tCO2/tMSW. The mitigation of GHG emissions from waste must be addressed in the
context of integrated management, and in Cantabria, the changes in the management system
applied during the period 2005-2009 have succeeded in mitigating emissions in a 35%, from values
of 99.373 tCO2e (294,4 kgCO2e/tMSW) to 64.931 tCO2e (179,0 kgCO2e/tMSW).
125.000 400
100.000
300
kg CO 2e/t MSW
75.000
t CO2e
200
50.000
CF 100
25.000
CF/MSW
0 0
2005 2006 2007 2008 2009
Figure 5. Evolution of the Total Carbon Footprint [tCO2e and tCO2e/tMSW] of the Cantabria MSWM
CONCLUSIONS
A Carbon Footprint (CF) model has been applied to the MSW management system in Cantabria
region to facilitate comparing and to develop time series of the CF to track progress of climate
change mitigation strategies.
The results show that due to the intensification in the selective collection of fractions to recycling,
the Carbon Footprint of the transport of MSW has increase from 2.358 tCO2e in 2005 to 2.637
tCO2e in 2009. This CF only represents the 4% of the Total Carbon Footprint of the MSWM, which
decrease during the period 2005-2009 from values of 99.373 tCO2e (294,4 kgCO2e/tMSW) to
64.931 tCO2e (179,0 kgCO2e/tMSW). The main contribution to the CF is associated to the
landfilling (decreasing in the period 2005-2009 in a 43%); the mitigation of GHG emissions was due
41
to increasing quantities of waste to landfill were diverted to incineration, as well as to MBT before
landfilling to recover recyclables and reduce the organic content by an aerobic composting.
From results of the total Carbon Footprint it is suggested that priority actions to reduce emissions of
GHG would consider the decrease of MSW generation and its decoupling from economic growth,
through actions like promotion of the responsible and equitable consumption patterns; increasing
diversion of biowaste from landfilling; increasing the material recovery rate to the targets and
increase compost production in a subproduct marketable framework; and, minimising transport
distances during collection and transportation by the optimization of the routes and sorting and
treatment plants localization, among others.
Acknowledgments
This work has been supported by a R+D+I project entitled Establishing the set of indicators for
sustainable resource and waste flow in the Region of Cantabria between the Government of
Cantabria and University of Cantabria, Spain. Eva Cifrian was funded by the University of
Cantabria on a PhD fellowship.
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(Eds), Climate Change 2007: Mitigation. Contribution of Working Group 3 to the Fourth
Assessment Report of the Intergovernmental Panel on Climate Change, IPCC, Cambridge
University Press, Cambridge, UK, 2007.
[3] ISWA, Waste and Climate Change. ISWA White paper. International solid waste association.
Denmark, 2009
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decision model for urban solid waste management, Waste Management 24 (2004) 277295.
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[7] A. Pires, G. Martinho, N.B. Chang, Solid waste management in European countries: A review
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[10] D. Browne, B. ORegan, R. Moles, Use of carbon footprinting to explore alternative household
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waste management strategies in Ottawa, Ontario, Canada, Resour. Conserv. Recycl. 52
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[13] T. Astrup, T. Fruergaard, T.H. Christensen, Recycling of plastic: Accounting of greenhouse
gases and global warming contributions. Waste Manage. Res. 27 (2009) 763-772.
[14] E. Gentil, T.H. Christensen, E. Aoustin, Greenhouse gas accounting and waste management.
Waste Manage. Res. 27 (2009) 696-706
[15] R. Eisted, A.W. Larsen, T.H. Christensen, Collection, transfer and transport of waste:
accounting of greenhouse gases and global warming contribution. Waste Manage. Res. 27
(2009) 738745
42
FOOD WASTE ORIGINATING FROM THREE DIFFERENT SOURCES:

CHARACTERIZATION AND POTENTIAL USE AS ANIMAL FEEDSTUFF
1, 2 3 4
Chen Ting Jin Yiying , Li Huan and Meng Xiao
1 School of Environment, Tsinghua University, Beijing 100084, China.
chenting07@mails.tsinghua.edu.cn
2 School of Environment, Tsinghua University, Beijing 100084, China. supcql@gmail.com
3 Research Center for Environmental Engineering and Management, Graduate School at
Shenzhen, Tsinghua University, Tsinghua Campus, University Town, Shenzhen (518055), China.
sunpace@vip.163.com
4 School of Environment, Tsinghua University, Beijing 100084, China. meng_xiao1357@sina.com
ABSTRACT
Three different fractions of food waste were evaluated as potential animal feedstuffs. For
each source of waste (campus dining hall waste (CW), restaurant waste (RW) and
household waste (HW)), samples were obtained from campus of Tsinghua University,
restaurants and dustbin in community, Beijing. The chemical composition, microbiological
characterization and mineral content were determined for every waste fraction.
The analyzed food waste presented low dry matter content (from 14% to 32%), and a
more balanced composition. Generally, the CW and RW studied presented free of toxic
heavy metals pollutant, but the presence of toxic concentrations of metals contaminants in
HW was higher than legislation permitted values in animal feeding. From a microbiological
standpoint, the absence of mycotoxins and certain pathogenic microorganisms shows the
safety of food waste source, however, the over standard colony of E.coil, molds and yeast
were detected. A heat treatment was essential to ensure microbiological quality and
reduce the moisture content for facilitating the waste conservation and treatment.
The results obtained in this research indicated that, some of food waste fractions (such as
campus dining hall waste or restaurant waste, which was proved without contamination)
had significant potential as alternatives to typical raw materials used in animal feeds in
China, based on according with the feedstuffs legislation in force related to animal feed
and effective management.
Keywords: Characterization; Food waste; Animal feedstuff
INTRODUCTION
With the rapid industrialization, economic development and urbanizationHuge amount of food
wastes are generated in China, which is the single-largest component of the waste Stream,
reaching over 50% for most cities. Because of the typical characters, such as the moisture content
is about 74-90% [1], 3% oil content, etc., the traditional treatment, like landfill or incineration isnt
suitable to food waste. Therefore, the government began promoting resource recycling from food
waste, among which, feed to animal is an effective way to alleviate the food crisis. It is report, the
food demand is expected to increase due to population growth and a more luxurious consumption,
but 32% of the world yielded grains [17] and up to 68% of the grains used by developed countries
[14] are being fed to livestock, which could also be used for food [15].
Feeding food waste to livestock is not a recent innovation. It has been practiced throughout the
world and is often concentrated around metropolitan centers [2, 3]. In addition, the digestibility, the
nutritive value of food waste has been researched since over 40 years ago [18, 19]. And then, the
43
economic advantages [2, 4] and the processing of food waste, such as dehydration, pelleting,
and(or) extrusion [5, 20] also been studied.
The food waste includes uneaten food and food preparation leftovers. It can be categorized as
originating from four primary sources: raw material, food processing, post processing, and post
consumer. Most food processing and post processing waste are belongs to industry waste, not
including in the study. Generally, food waste from campus dining hall waste (CW), restaurant waste
(RW) and household waste (HW) mainly comprise post consume food and a spot of raw material
produced with cooking, but was different in ingredient proportion and production place. CW and RW
are generated in relative concentrated sites and collect easily, but the collection of HW is
comparative sporadic. Hence, these facts make some difference among food waste originating from
diverse sources.
Just like other countries, use of food waste as a component for feeding domestic animals like pigs
and chicken in China, has lasted for a long time. However, there are few studies in china on the
characterization of food waste. And there are significant difference in diet between china and other
countries, especially for west countries. This causes the different food waste and different core
problems of recycling it. In addition, food waste may be contaminated with paper, plastics, razors,
heavy metals and other substances, which affect the quality of waste and even the adequate
recycling procedures.
The quantification and identification of the waste chemical and physical characterization, the
contaminations constitute the first main steps in deciding alternatives of deal with waste. The main
aim of this paper is to propose a characterization of the different fractions of food waste in order to
evaluate its application as feedstuffs. The study was conducted to accomplish the following
objectives: (a) To determine the nutritive value of the collected waste from different sources. (b) To
evaluate the feasibility for use of this waste as feedstuffs in animal diets according to their
composition and the legislation in force.
Samples
The study was carried out using food waste from different sources. This waste was categorized in
different fractions, which were collected from:
campus dining hall waste (CW) - campus of Tsinghua University,
restaurant waste (RW) - restaurants
household waste (HW) - dustbin in community
From mid March 2010 to the end of December 2011, samples of different food wastes were
collected from small establishments distributed in the city of Beijing, China once a week. On each
collection day, three samples were taken for laboratory analysis, their weight being large enough to
represent the FW waste collected by waste plastic barrel with 22 liter capacity, during a 4-h period
as long as it was generated in the afternoon.
Since the food waste as collected from original sources contained some considerable impurities,
mainly paper, plastics and wood. Artificial separation was used to prepare the food waste for
characterization. The raw waste was separated to remove the coarse contaminants and then flowed
into a mincer for size reduction and homogenization. At each sampling, approximately 2kg (wet
weight) of food waste were stored at 4 C until analyzed. The homogenized samples were manually
mixed once again and triplicate samples were each analyzed twice to measure the sampling and
analytical error.
Chemical composition analysis

The food waste samples were analyzed for dry matter (DM), crude protein(CP), Ether extract (EE),
crude fiber (CF), nitrogen-free extractives (NFE) and ash. Dry matter DM was determined by
drying the sample to a constant weight in an oven at 105. A method for the quantitative analysis of
the different macronutrients, including crude protein(CP), Ether extract (EE), crude fiber (CF), ash
and nitrogen-free extractives (NFE), accorded to the method of the Weende or proximate analysis,.
based on the Weende analysis that was developed in 1860 by Henneberg and Stohmann in
Germany.
44
Microbiological analysis
The food waste was tested for the most important pathogen, especially for animal feed, such as
Salmonella, enterobaceria (E.coil), listeria, staphylococcus aureus, molds and yeast, total microbial
counts. The pathogen examination rely on the national voluntary standard of feed in the lab, except
some special pathogen like Salmonella, which was tested by the Comprehensive Test Center of
Chinese Academy of Inspection and Quarantine (CAIQTEST) with the approval of China National
Accreditation Service for Conformity Assessment (CNAS). Besides these, The Aflatoxin B1 (AFB1),
which is one of the most harmful for avian culture among all currently known mycotoxins, was
analyzed by the standard method in food (CCITI-VM-0026) by CAIQTEST.
Mineral content analysis

Following EPA method 200.7 from the US Environmental Protection Agency [21], the mineral
content (Ca, P, K, Na, Mg, Fe, Zn, Mn, Cu, and C) of the samples was determined in the laboratory
by inductively couple plasma (ICP), (Thermo IRIS, USA), after a microwave digestion (MARS, CEM
Corporation, USA), and for some trace contaminated heavy metal, such as Arsenic (As), cadmium
(Cd), mercury (Hg), lead (Pb) and chromium (Cr) content was measured by ICP-MS [6, 7].
Statistical analysis
Analysis of Variance (ANOVA) was used to examine the significance differences of the
characteristics of food wastes. To compare the average concentrations, Fishers least significant
difference (Fishers LSD) was calculated using 95% confidence level. All correlation equations and
coefficients were obtained using Excel (Microsoft, 2007).
Chemical composition of waste

The different fractions of the food waste had a low dry matter content, with a high coefficient of
variation, that varied from 14% to 32% for all cases (22.8% CW, 21.2% RW and 31.8% HW). The
statistical analysis showed no significant differences between the CW and RW at a 99% confidence
level (Fig. 1).
On a dry matter basis, each fractions of food waste studied was high in nutrient value. In a word, the
CW and RW was more nutrient than HW, comparing the ether extract and protein content. the CW
and RW had relatively high protein (25.5%-28.6%), NFE (30.6%-31.6%) and ether extract
(28.1%-31.5%) contents. These values were in accordance with those reported by other authors [8,
16, 18, 22]. High nutrient values in CW and RW just because these waste was composed mainly of
plate waste, which contains major residual food cooked for human, few raw cooking material was
including, especially for the CW. And remains of scraps were also responsible for the high relative
protein content (>20%) in CW and RW. HW basically consisted of vegetable fractions and few
uneaten meat, had a high content of NFE as well as ash, probably due to the presence of inorganic
substances such as salt, sand and other residues not removed previously.
55% CW RW HW
50%
Nutritional Composition Percent
45% * * *
*
40%
35%
30%
25%
20%
15%
10%
5%
0%
DM CP EE CF NFE Ash
45
Fig.1. Nutritional composition of food waste of different sources (% on a dry matter basis).The data
were expressed as means the standard deviations (n = 28). The symbols * and indicate the
two-waste ANOVA wasnt significant.
Whatever, food waste fractions of CW, RW and HW were moderately high in protein, high in fat, and
relatively low in crude fiber and ash, and had a more balanced composition, regardless of ether
extract, protein content, NFE or ash. The relatively high protein and fat contents and the low fiber
and ash contents are desirable in animal feedstuff. However, the presence of plant-derived
materials such as legume seeds, melon seeds, oilseeds, peels, leaves, root tubers and grain in
some some food waste fractions (especially in HW) could be a hinderance for using them as animal
feed if anti-nutritional factors usual in these types of materials [9] were not inactivated. The common
processing techniques like dry and wet heating and soaking with water have been widely and
successfully used to reduce the concentration of anti-nutrients in plant feeds [10-12]. The heat
treatment undergone by CW, RW and HW before their collection (due to cooking) and the heat
treatment proposed in Section 3.2 to reduce the microbiological and the moisture contents in all
types of studied wastes coincide with these techniques, and so it may be safe to conclude that the
effects of anti-nutritional factors are minimized after the treatments, though altering the chemical
nature and decreasing the nutritional quality ofproteins and carbohydrates were founded [23, 24].
Microbiological analysis
Microbial analysis of food waste samples (Table 1.) indicated the present of high numbers of
bacteria including molds and yeast, E.coil and Staphylococcus aureus, but the absence of some
typical pathogens. The similar results of the microbiologic studies were also described by Sancho et
al. [13]. In general, the high number of microbial counts in food waste could be justified by internal
and external factors. Food waste fractions were products with high moisture contents that contain
microflora that could easily affect it, in addition municipal solid waste ( CW, RW and HW were
included) had fractions with a high intrinsic microbial contamination (such as high organic content).
Contamination can also be explained by external factors such as inappropriate handling and
storage or inadequate treatment. Some bacteria, especially some microorganisms capable of
transmitting infectious disease such as BSE ( Bovine Spongiform Encephalopathy ), might infect
animal through animal feed ingestion and then be likely transferred to human consumers. For
example, molds and yeasts are fungi; they love moist habitats and organic source. They can
produce other secondary metabolites such as antibiotics and mycotoxins, which is harmful to animal
and human health. Moreover, animals fed fungal colonized/ mycotoxic feed are not only at risk for
developing mycotoxins, their meat and their fat, constitute another vehicle for human exposure to
excessive mycotoxin intake.
Hence, an adequate heat treatment of food waste fractions assures enough microbiological
reduction to be considered innocuous [8, 14]. Moreover, heat treatment was also adequate to dry
food waste to a moisture content of 10%, which is usually used in animal feed.
a
Table.1. Results of microbiological analysis of food waste
b
Origanism CW RE HW Standard
C C C C
Salmonella ND ND ND ND
d
E.coil 8.65E+02 1.56E+04 1.93E+04 ND
C C C
Listeria ND ND ND -
e e d
Staphylococcus aureus 6.67% PR 25%PR 57.10% 10 cfu/g
Molds and yeast 1.98E+05 5.31E+05 3.50E+06 <2.00E+04

Total microbial count 3.10E+04 6.89E+06 2.10E+06 <2.00E+06
C C C
AFB1 ND ND ND <10
46
a
The column represents estimated number of colony forming units/g of sample
b
Expressed on a base of the most strict claim of the hygienic standard for feed of the People's
Republic of China national voluntary standard [25]
c
Not detected above background
d
According to the microbiological specifications for materials used as animal feedstuffs [26]
e
Positive rate of staphylococcus aureus
Mineral content in food waste
CW RW HW CW RW HW
5.0 4.71 8
7 10 10
Trace Elements Content (ppm)

Macro-element Content (%)
4.5 6 4.32 5
4.0 2.77 5 2.0 3.34 4.16 5
4 0.1
4
2.90 2.81 0.5 3.00
1.8
3.5 2.27 3 0
2 1.08
3.0 0.64 0.99
1 -5
2.5 0.18
1.05 1.77
2.0 0.20 -10
0.11
1.5 0.15 0.088 0.099
-15
2
0.51
06
1.0 0.10
0.
0.36
0. 030
8
0.5 -20
02
0.05
0.
0.0 0.00 -25
Ca P Na As Hg Cd Cr Pb
(a) Macro-minerals (b) Trace Elements

Fig. 2 Mineral content (mean SD) of food waste of different sources (based on the dry matter).
The red solid line () indicated the most strict claim of the hygienic standard for feed of the People's
Republic of China national voluntary standard [25]
The mineral content of the food waste fractions was showed in Fig. 2. Although macro-minerals
such as calcium, phosphorous, and sodium were found in all wastes, the highest values were
obtained for RW, except for Na in CW. So RW was a good source not only of protein but also of
minerals. The ratio of Ca: P in feedstuffs has special relevance in animal nutrition, because an
adequate ratio is a determinant for the optimal absorption and utilization of both minerals [27]. The
ratios Ca: P found with the waste fractions studied were respective 2.06, 2.66 and 6.31 for CW, RW
and HW, which were out of the recommended range from 0.9:1 to 1.4:1 depending on the animal
[28]. However, it must be pointed out that the sodium content in food waste was comparatively
higher (2.77-2.90), due to a high salt content in Chinese diet habit. This could limit the amount of
food waste that could be included in feed. But, salt is commonly added to some animal diets, such
as pig, thus the high salt content of food waste could replace salt supplementation.
The average concentrations of As, Hg, Cd, Cr and Pb (trace elements) were relatively low and were
in accordance with data reported by Garca et al. [8] for biodegradable municipal solid waste.
According to the strictest claim of the hygienic standard for feed of the People's Republic of China
national voluntary standard [25] (Fig. 2), the content of heavy metals can be accepted on a basis of
animal safe. This is likely due to heavy metals containing in the food waste mainly come from food.
It indicated the heavy metal and AFB1 background of food waste is low.
Whereas, the high amount of heavy metals at whiles was observed in food waste, especially for
HW. This might be due to the presence of inorganic substances like cans, sand, metals or other
particles. And for CW and RW, none of undesirable elements in animal feed were found to exceed
the maximum levels allowed by the legislation (Fig. 2) at normal time. However, the content of lead
in campus dining and household wastes exceeded the maximum value, probably due to contact with
materials made of lead like cans or pipes as well as Hg in restaurant waste. The relatively high
concentrations of these elements in food waste could make its inclusion in animal diets difficult.
Thus the exogenous pollutants should be avoided as possible during the collection, transport and
treatment of food waste.
47
CONCLUTION
The results of this research revealed that most of the food waste fractions studied had a high
nutritional value as indicated by their overall profile. CW and RW could be considered the most
interesting food wastes with potential use as animal feedstuffs, since they presented a better
balanced and complete composition. To reduce the concentration of anti-nutrients in plant feeds
including in the food waste, heat treatment was necessary, as well as for ensuring the
microbiological quality used in the feed and reducing the moisture content. However, food waste
fractions studied (RW and HW) contained undesirable substances (Pb and Hg) that do not permit
their inclusion in feed rations because of extrinsic contamination. Hence, the exogenous pollutants
should be avoided during the process of food waste used in feed stuff as possible.
In conclusion, considering the waste characters, the food waste fractions studied were a highly
desirable feedstuff for animal. But owing to the high MC (80%), certain microbial risk and extrinsic
contamination, it is very necessary to develop effective dry and sterilization technologies for human
and animal health, based on scientific management.
ACKNOWLEDGEMENT
This research was supported by National Key Project of Scientific and Technical Supporting
Programs of China (NO. 2009BAC64B06).
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49
ENVIRONMENTAL ASSESSMENT OF THE INTEGRATED WASTE

MANAGEMENT SYSTEM OF LIPOR USING ECOLOGICAL FOOTPRINT AND
LIFE CYCLE ASSESSMENT
1 2 3 1
M. Herva , N. Arajo Barros , B. Neto and E. Roca
1 Sustainable Processes and Products Engineering Group, Dpt. of Chemical Engineering, School
of Engineering, University of Santiago de Compostela, Spain. Emails: marta.herva@usc.es;
enrique.roca@usc.es
2 Dpt. of Audit, Sustainability and Total Quality, LIPOR, Portugal. Email: nuno.barros@lipor.pt
3 CEMUC, Dpt. of Metallurgical and Materials Engineering, Faculty of Engineering, University of
Porto, Portugal. Email: belmira.neto@fe.up.pt
ABSTRACT
This paper presents the preliminary results of the environmental evaluation of the waste
treatment processes carried out at LIPOR (Intermunicipal Waste Management of Greater
Porto Portugal), conducted by the combined application of Ecological Footprint (EF)
and Life Cycle Assessment (LCA). The Integrated Waste Management System (IWMS) at
LIPOR includes several treatment units as the separation of several materials for
valorization, the incineration of waste with energy recovery, composting of the organic
fraction and landfilling of pre-treated waste. Results were presented on the basis of 1 kg
of waste treated at each treatment facility. The composting plant presents the larger EF,
while the energy recovery plant show to have the smallest net EF due to the important
contribution of the counter footprint term. However, the analysis performed using EF does
not evaluate the potential environmental impact associated to the air emissions released
at the energy recovery plant. The impact associated to air emissions was assessed by
LCA throughout the CML impact assessment methodology. The results show that the
emission of hydrogen fluoride has the most relevant potential damage with a large
contribution to toxicity categories, particularly to the marine ecotoxicity. The
complementary application of EF and LCA resulted very beneficial to achieve a more
comprehensive and meaningful analysis of the processes that take part at LIPOR.
Keywords: Ecological footprint; Life cycle assessment; Integrated waste management; Urban
waste
INTRODUCTION
Economic and human population growth, as well as changes in lifestyles and in consumption
patterns, has been the main driver to a progressive increase in the wastes generation (particularly
due to the extensive packaging uses). One of the major challenges for municipalities in the 21st
century is to collect, recycle, treat and dispose of increasing quantities of urban solid waste [1]. A
sustainable management of municipal solid waste (MSW) regards all phases of impact from
planning, design, operation and decommissioning [2]. Waste causes several impacts in the
environment, as the pollution of air, soil, surface and ground water. In addition, valuable space is
taken up by landfills and poor waste management causes risks to public health [3]. The impact in
the environment, together with the economic constraints associated to the management, are
usually the driving force to identify solutions for the reduction of the problems caused by urban
wastes [4].
The waste hierarchy defined in the Directive 2008/98/EC establishes priorities to be considered in
waste prevention and management legislation and policies: 1) prevention; 2) preparing for re-use;
3) recycling; 4) other recovery, e.g. energy recovery; and 5) disposal. This Directive also addresses
the possibility of altering the defined hierarchy for specific situations, if justified by a life-cycle
50
thinking study [5]. This indicates that analytical tools are needed to evaluate the overall
environmental burdens of waste management systems [6]. Typically, and given its life cycle
approach, LCA has currently been applied worldwide to evaluate environmental problems
associated to the MSW [7]. However, LCA is not the only methodology available to assess the
environmental burdens associated to MSW treatment processes. Some studies consider the
complementary perspectives, also based in a life-cycle inventory, of material flows analysis and the
ecological footprint [1].
This work presents an assessment of the environmental performance of LIPOR, which is the inter-
municipal waste management system located in Porto (Portugal) responsible for the management
and treatment of the MSW produced in the eight partner municipalities. The environmental
assessment of the Integrated Waste Management System (IWMS) of LIPOR was conducted by a
complementary use of Ecological Footprint (EF) and Life Cycle Assessment (LCA).

This section describes the waste treatment processes as well as the environmental evaluation
methodologies used.
Description of the waste treatment processes at LIPOR

LIPOR implemented an integrated system for MSW that included the separation of several
materials for valorization (Sorting Plant), composting of the organic fraction (Composting Plant) and
incineration of waste with energy recovery (Energy Recovery Plant). In addition, a sanitary landfill
is used to dispose previously treated waste, untreated waste as well as the ashes formed during
incineration. The waste flows treated at the different treatment plants for the time frame considered
is presented in Table 1.
Table 1. Annual waste streams treated or deposited by the existing treatment processes at LIPOR
[8].
Parameter 2007 2008 2009 Units

Population (inhabitants) 972,301 972,301 970,704
Waste streams
Sorting Plant (SP) 49,884 55,470 59,966 [t]
Composting Plant (CP) 30,730 37,146 42,215 [t]
Energy Recovery Pant (ERP) 419,389 383,553 398,392 [t]
Landfill 27,185 63,308 39,339 [t]
Total 527,188 539,477 539,912 [t]
An infrastructure for the selective separation and collection of wastes is made available to the
region citizens. At the LIPORs Sorting Plant (SP) a complementary separation is carried out. Here
the materials from the previous collection are treated again for a more selective sorting. Afterwards
they are baled and sent to several materials recycling plants. The biowaste recovery takes place in
-1
the Composting Plant (CP) that can process nearly 60.000 t yr of organic waste. The collection of
the organic fraction of the MSW takes place at removal circuits implemented by LIPOR that include
the producers of large amounts of organic waste (e.g., restaurants, hypermarkets, markets). This is
also complemented by local initiatives of home composting. The main purpose of the Energy
Recovery Plant (ERP) is the thermal treatment of MSW that do not have recovery potential through
the previously described treatment processes. The thermal treatment aims at recovering wastes
endogenous energy for the production of electricity under controlled conditions. The incineration
takes place at high temperatures (1000C to 1200C) under oxygen saturated conditions. The
incineration plant is energetically self-sufficient, sending about 90% of its energy production to the
Portuguese National Electrical Network. The air emissions released during the combustion process
undergo a rigorous monitoring system control. The gases are filtered and neutralized before sent to
51
the atmosphere. The resulting ashes are stabilized and, together with the slag, are deposited at the
LIPORs sanitary landfill.
Environmental evaluation methodologies

EF is used to assess the area required to supply energy and materials to the activities taking place
at LIPOR. The component method, based on life-cycle data for each individual component involved
in calculations, was applied and the mutually exclusive use of land approach was adopted [9].
Hence, individual EFs were calculated for each flow from the inventory (in a yearly basis) and were
later aggregated, according to Eq. 1 and Eq. 2, respectively.
(1)
(2)
Where EFi is the area required for the component i; NPi, EVi and EPi are the natural productivity,
embodied energy and energy productivity (associated to fossil fuel) for element i; Fj is the
equivalence factor for land type j. Equivalence factors translate a specific land type (i.e. cropland,
pasture, forest, fishing ground) into a universal unit of biologically productive area, generally a
global hectare [10].
LCA is used to assess the environmental impacts associated to the emission of air pollutants
released during the activities that take place at the ERP. It is conducted following the framework
defined by the ISO 14040:2006 [11] and using the impact assessment methodology defined by
CML 2010 [12]. Characterization and normalization stages were carried out using Eq. 3 and Eq. 4,
respectively.
(3)
Where Ct is the overall impact for the category t. Ct units depend on the impact category
considered. As is the amount of emission s released, Wst is the characterization factor for the
emission s within the category t.
(4)
Where Cnt is the normalized value for the impact category t and Nt is the normalization factor. The
Cnt is unitless.
The inventory data used refers to 2007-2009 and the functional unit is 1 kg of MSW treated at each
treatment plant unit [8]. Due to the lack of information readily available in the literature, the activities
of transport and wastewater treatment, as well as the activities associated to the biogas plant
recently implemented, were not considered in the analysis.
RESULTS
The Fig. 1 summarizes the calculated results for the relative EF values. The Composting Plant
(CP) presents the largest values for the period considered. The contribution of energy consumption
is here preponderant. The second largest value for the EF is associated to the general activities,
but for this case the materials have the largest contribution. By contrast, the ERP presents the
smallest EF, followed by the EF value for the sanitary landfill (these preliminary results account for
the materials and energy consumed but do not consider the building and the landfill areas). Only
the gross footprint is presented in Fig. 1. However, the analysis considered the Counter Footprint
(CF) related to the electricity generation (in ERP) and the compost produced (in CP).
Water consumption in the different waste treatment plants is analyzed independently because it is
not adequately assessed by the EF (Fig. 2). Tap water is the main source of water, although water
52
from ground level is also used at ERP and in the general activities. The energy recovery clearly has
the larger contribution in terms of water requirements. Large quantities of water are also used in
the general facilities at LIPOR. However, when analyzing the relative flows, the relevance of CP
increased and the resulting value is being comparable to the general activities consumption and
similar to the ERP (Fig.2).
0,35
0,30
Materials
0,25
Energy
EF (gm2 kg-1)
0,20
1
0,15
0,10
0,05
0,00
2007
2008
2009
2007
2008
2009
2007
2008
2009
2007
2008
2009
2007
2008
2009
ERP Landfill CP SP General
ERP: Energy Recovery Plant CP: Composting Plant SP: Sorting Plant
General: activities in administrative buildings of LIPOR
Fig. 1. EF estimates for the four waste treatment processes and general activities of LIPOR.
0,6
Tap water Water catchments 1
0,5
Water consumption (m3 kg-1)
0,4
0,3
0,2
0,1
0
2007
2008
2009
2007
2008
2009
2007
2008
2009
2007
2008
2009
2007
2008
2009
ERP Landfill CP SP General
Fig. 2. Water consumption at the different plants of LIPOR.
The LCA results allow us to conclude that the system evaluated contributes to eight impact
categories, namely, global warming, acidification, eutrophication, photochemical oxidation, human
toxicity, fresh water aquatic ecotoxicity, marine aquatic ecotoxicity and terrestrial ecotoxicity (Fig. 3
and Fig. 4). The global warming impact category is not included in the characterization step results
(Fig. 3) because the data available is expressed in total CO2 equivalent emissions and thus do not
allow for the assessment of the partial contribution of the different greenhouse gases to the GWP
category.
The detailed analyses of the emissions underlining these results show that the hydrogen fluoride
(HF) is the pollutant that more significantly affects the toxicity (this is valid for the categories: HTP,
FAETP, MAETP and TETP). The risk phrases R26/27/28 are associated to this pollutant, meaning
53
that this gas is very toxic by inhalation, contact with skin and when swallowed [13]. The most
relevant contribution to acidification and eutrophication is due to emission of nitrogen oxides. In
addition, sulfur dioxide together with carbon monoxide is the main responsible for the
photochemical oxidation category. Particulates and hydrogen chloride do not show a significant
contribution to any of the impact categories.
110%
100%
90%
80%
70%
60%
50%
40%
30%
20%
10%
0%
AP
HTP
EP
AP
HTP
EP
AP
HTP
EP
FAETP
MAETP
FAETP
MAETP
FAETP
MAETP
TETP
TETP
TETP
POCP
POCP
POCP
2007 2008 2009
Dioxins CO Particulates SO22
HF NOx HCl 1
AP: Acidification Potential HTP: Human Toxicity Potential

POCP: Photochemical Oxidation Potential EP: Eutrophication Potential
FAETP: Fresh water Aquatic EcoToxicity Potential MAETP: Marine Aquatic EcoToxicity Potential
TETP: Terrestrial EcoToxicity Potential
Fig. 3. Impact assessment associated to the release of air emissions at the ERP. Characterization
stage.
The results from the normalization stage (Fig. 4) show that a larger value is obtained for the marine
aquatic ecotoxicity. The GWP100 is the second most important category and it is followed by
acidification and eutrophication. In summary, it is possible to conclude that hydrogen fluoride
(contributing to MAETP) and NOx emissions (contributing to AP and EP) are the air emissions
responsible for a larger potential damage to the environment.
4E-10
3,5E-10 2007
2008
3E-10
2009
2,5E-10 1
2E-10
1,5E-10
1E-10
5E-11
0
GWP100 AP HTP POCP EP FAETP MAETP TETP
Fig. 4. Impact assessment of air emissions released at the ERP. Normalization stage.
54
CONCLUSIONS
This paper evaluated the environmental performance of the waste treatment plants included in the
IWMS of LIPOR. The complementary application of EF and LCA revealed that the composting
plant presented the major contribution to the environmental impact considering the amount of
waste treated. Meanwhile, ERP was found as very beneficial due to the low gross EF and the large
Counter Footprint CF. This is due to the comparatively large amount of electricity produced that is
supplied to the national electricity network (90% of the total energy produced is injected to the
national network). Nevertheless, this conclusion must be considered cautiously given the
environmental impacts associated to the air pollutants released during ERP activities and the large
amount of water consumption needed in comparison to other waste treatment alternatives.
The potential toxic effects due to hydrogen fluoride emissions were found to be significant. This
means that the measures to reduce these emissions should be identified. At the end, it is possible
to conclude that the application of complementary environmental evaluation methods, as EF and
LCA was found necessary and useful to adequately evaluate treatment processes taking place at
an integrated urban waste management system.
The use of this evaluation processes can even become an important tool for planning future
facilities and waste management strategies that can be more efficient and environmental friendly.
Acknowledgements
This work has been supported by the Spanish Government (Science and Innovation Ministry)
through the Project INDIE (CTM2010-18893), ERDF included. Marta Herva wishes to thank the
University of Santiago de Compostela for her pre-doctoral contract.
References
[1] F. Cherubini, S. Bargigli, S. Ulgiati, Life cycle assessment (LCA) of waste management
strategies: landfilling, sorting plant and incineration, Energy 34 (2009) 2116-2123.
[2] A. Pires, G. Martinho, N.-B. Chang, Solid waste management in European countries: A review
of systems analysis techniques, J. Environ. Manage. 92 (2011) 1033-1050.
[3] Environmental Protection Agency, Europes environment, The fourth assessment, Copenhagen,
Denmark, 2007 (ISBN: 978-92-9167-932-4).
[4] J.K. Seadon, Sustainable waste management systems, J. Clean. Prod. 18 (2010) 1639-1651.
[5] Directive 2008/98/EC of the European Parliament and of the Council of 19 November 2008 on
waste and repealing certain Directives, Off. J. EU L 312 (2008) 3-30.
[6] B. Thomas, F. McDougall, F., International expert group on life cycle assessment for integrated
waste management, J. Clean. Prod. 13 (2005) 321-326.
[7] J. Cleary, LCA of municipal solid waste management systems: A comparative analysis of
selected peer-reviewed literature, Environ. Int. 35 (2009) 1256-1266.
[8] LIPOR, Sustainability report (in Portuguese), 2007-2009. Information on www.lipor.pt.
[9] C. Monfreda, M. Wackernagel, D. Deumling, Establishing national natural capital accounts
based on detailed EF and biological capacity assessments, Land Use Policy 21 (2004) 231
246.
[10] J. Kitzes, A. Peller, S. Goldfinger, M. Wackernagel, Current methods for calculation National
Ecological Footprint Account, Sci. Environ. Sustain. Soc. 4 (2007) 1-9.
[11] ISO 14040 Standards, International Organization for Standardization, 2006. Information on
www.iso.org.
[12] CML (Institute of Environmental Sciences), Database CML-IA, version 3.7, 2010, Leiden
University, The Netherlands. Information on http://cml.leiden.edu/software/data-cmlia.html.
[13] ESIS, European chemical Substances Information System. Information on
http://ecb.jrc.ec.europa.eu/esis/.
55
HOUSEHOLD WASTE MANAGEMENT IN THE UK: CURRENT PRACTICES

AND CHALLENGES
1a 1 1 1 2
C. Cole , M. Osmani , M.A. Quddus , A.D. Wheatley and K.Kay
1
Department of Civil and Building Engineering, Loughborough University, Loughborough, LE11 3TU
2
Charnwood Borough Council, Southfield Road, Loughborough, LE11 2TN
a
email: Christine.Cole@charnwood.gov.uk
ABSTRACT
The UKs reliance on landfill sites for waste disposal has been addressed in recent years
with the Landfill Directive and Landfill Tax. This has encouraged Local Authorities to seek
alternative methods of treating household waste, introducing and expanding kerbside
collections of recyclates and organic waste.
This paper assesses current household waste management practices and challenges in
the UK. Drivers and instruments for change and various approaches to kerbside waste
collections are discussed. The current household waste management challenges in the
UK are identified, including the division of responsibility for household waste
management between various Local Authorities and Government Departments and the
methods available to tackle these issues.
The research revealed adopting an integrated management system for household waste
to comply with legislation and behavioural attitudes towards recycling and waste
reduction activities are obstacles facing Local Authorities. Conversely, segregation of
household waste by material is increasing, with separate kerbside collections for
recyclates, organic waste and bulky waste collections, some of which is selected for
reuse. The challenge now is to improve the yield of recyclates, reach people that do not
segregate their waste for recycling and increase the quantity of material from participating
householders with imaginative ways for reuse and recycling.
Keywords: household waste; integrated waste management; challenges; UK.
INTRODUCTION
This paper is part of an ongoing research project that aims to improve the efficiency and
effectiveness of household waste collections. The UK has traditionally relied on disposal at landfill
sites whilst the rest of Europe has used incineration [1]. The environmental concerns regarding the
use of landfill are well documented, as are concerns about the long term impact of the high
temperature residues from incineration. The move towards more sustainable approaches to
household waste management, with waste increasingly seen as a resource, has seen widespread
changes in kerbside collection methods to encourage separation of waste for recycling, reuse and
bio-treatment.
This paper examines household waste management drivers, current practices and challenges
within the United Kingdom (UK) context.
WASTE MANAGEMENT DRIVERS FOR CHANGE

Several drivers exist to force changes to the way household waste is managed, including political,
legislative and financial measures (Table 1). These are likely to encourage a move towards more
sustainable waste management practices that include recycling and waste prevention.
56
Table 1. Drivers for change in household waste management [2].
Drivers Instruments
European waste policies and strategies (e.g. Waste Framework
Directive, (2008/98/EC) & Landfill Directive, (1999/31/EC)
UK waste policies and strategies (e.g. recycling targets for Local
Legislative and
Authorities)
political drivers
Environmental legislation (both at European and National levels)
Employment legislation , Health and Safety legislation
Bans on landfilling certain substances
Financial Increasing cost of landfill disposal (e.g. Landfill Tax escalator,
drivers LATs)
Legislative and policy drivers

The key waste management EU Directives are the Waste Framework Directive (revised 2008)
covering regulation, handling and movement of waste and the Landfill Directive, 1999 and Waste
Incineration Directive, 2000, covering particular types of waste treatment and disposal. There are
also Directives that specifically target single waste streams, for example Waste Electrical and
Electronic Equipment Directive, Waste Batteries and Accumulators Directive and the End of Life
Vehicles Directive.
Waste management is a devolved responsibility in the UK; with separate waste strategies for
Wales, Scotland, Northern Ireland and England. Each has different objectives and targets and an
increasing diversification of strategy is becoming evident. However, all take account of the Waste
Framework Directives Waste Hierarchy, with waste reduction, recovery of resources and potential
energy in preference to using disposal at landfill sites.
Financial drivers
The main financial driver to reduce the use of waste disposal is Landfill Tax, an escalating fiscal
measure, currently 56 per tonne, paid in addition to disposal costs set by the landfill operator and
Landfill Allowance Trading Scheme (LATs). LATs expose Local Authorities to fines of 150 per
tonne if allowances for landfill disposal are exceeded, but are due to be withdrawn in 2013. These
combined financial measures shape local waste management policy, making recycling and reuse
economically viable options [3] and providing Local Authorities with an incentive to encourage
householders to recycle and compost waste [4].
HOUSEHOLD WASTE MANAGEMENT PRACTICES

Local Authorities have a statutory duty under The Environmental Protection Act, 1990 to collect and
dispose of household waste, but can determine frequency of collections, size of containers,
materials collected for recycling and whether or not organic waste is collected separately.
Significant variations in collection systems now exist across the UK [4, 5], with some Local
Authorities simply complying with legislation and offering separate collections of two recyclable
materials; while others collect waste as many as nine separate containers.
Household waste composition

Waste composition analysis can establish the type and quantity of materials present in waste,
allowing collections and waste treatment technologies to be tailored to suit waste arisings [6,7,8].
Although carried out before the widespread introduction of kerbside collections of recyclable
materials, several UK household waste composition studies found consistency in the main
materials found in the waste analysed [8]; these are shown in Table 2.
With a UK average national recycling rate of 39.7% in 2009/10 [9], there are still opportunities to
increase recycling and bio-processing of household waste. In particular, the biodegradable wastes,
food, kitchen and garden waste need special attention, as well as paper and cardboard, in order to
meet the Landfill Directive and reduce the amount of biodegradable waste going to landfill.
57
Table 2. UK household waste composition [8].
Material % present
Kitchen and garden 35-38 %
Paper and cardboard 23-25 %
Plastics 8-10 %
Glass 6-7 %
Metals 3-5 %
Local Authority household waste collection performance

The Waste Duty of Care Regulation requires all waste transfers to be recorded from point of origin
to final disposal point, ensuring an auditable trail exists for waste movements in the UK. Local
Authorities report waste movements on a quarterly basis to Department for Environment, Food and
Rural Affairs (Defra), who report progress towards national targets and trends in waste generation,
treatment and disposal. Data on waste generation is useful for design and operation of collection
services, identifying the point of waste generation and recycling and composting performance in
different geographical areas.
In 2009/10 Local Authorities in the UK collected 23.7 million tonnes of waste, 12.5 million tonnes of
this waste was landfilled. Household waste generated in 2009/10 was equivalent to 457kg per
person per year, with 181kg recycled and 275kg disposed of [5]. Data on waste generation trends
is useful for design and operation of collection services, identifying recycling and composting
opportunities, the point of waste generation and enabling comparisons between performance in
different geographical areas.
Individual Local Authorities performances are reported annually by Defra. The top performing
recycling Local Authorities in 2009/10 are shown in Table 3, which reveals differing approaches to
targets for collection of recyclates and organic waste. For instance, Staffordshire Moorlands District
Council collected high proportions of organic waste (42.6%) and relatively low amounts of
recyclates (19.2%); whilst South Oxfordshire District Council reversed this and collected relatively
high levels of recyclates (35.5%) and lower amounts of organic waste (25.9%). The different
approaches taken may also reflect the varying availability of treatment and disposal facilities.
Table 3. Recycling and composting performance of top ten UK Local Authorities 2009/10.
Percentage of
Position in Recyclable Organic
household
league table materials waste
Local Authority waste recycled,
for recycling collected collecte
reused or
performance (%) d (%)
composted
1 Staffordshire Moorlands District Council 61.84% 19.2% 42.6%
2 South Oxfordshire District Council 61.4% 35.5% 25.9%
3 Rochford District Council 61.2% 27.4% 33.8%
4 Cotswold District Council 60.4% 25.8% 34.6%
5 Stratford-on-Avon District Council 58.6% 27.2% 31.4%
6 South Hams District Council 57.2% 27.4% 29.8%
7 East Lindsey District Council 56.3% 27.1% 29.2%
8 Teignbridge District Council 56.2% 20.8% 35.4%
9 Rutland County Council 55.8% 31.4% 24.4%
10 Huntingdonshire District Council 55.5% 25.6% 29.9%
Kerbside waste collections Recyclates and organic waste

The easiest ways to treat mixed household waste are incineration and landfill [10]. To recover
recyclates and treat biodegradable waste separation is needed. For this to be successful at source,
householders need to engage in the process [11]. Collection services with complex sorting
processes had lower participation rates [12]; binary sorting, simply separating recyclable materials
from residual waste found to be more popular than multiple sorting [13]. Established processes
exist for sorting paper, cardboard, glass and metals. These materials are frequently collected for
58
recycling [14]. The mass density of these materials may be a factor when choosing materials for
collection, with them contributing to weight based recycling targets.
The high proportion of food waste present in household waste (Table 2) and its density, (on
3
average, 341kg/m ) [15] supports separate collections of food waste for bio-treatment both to assist
in meeting weight based targets and reduce the amount of biodegradable waste sent to landfill.
Bulky waste
Bulky waste items are often collected separately due to being more randomly distributed than
regular household waste; enabling some items to be recovered for reuse. Furniture reuse projects,
seek to extend the functional life of products, primarily for social benefits, providing low cost usable
furniture; the environmental benefits of diverting the waste from landfill being secondary [16].The
weight of materials recovered is usually low but can assist with reuse targets at relatively little cost.
HOUSEHOLD WASTE MANAGEMENT CHALLENGES IN THE UK

The key challenges in household waste management are the division of responsibility for waste
collection, treatment and disposal between Local Authorities and Government Departments, lack of
participation and behavioural attitudes of householders, as well as the practical issues of sorting
waste. Separating waste for recycling is a step which some householders are not prepared to
undertake. Yet their behaviour and resulting performance are necessary to reach challenging
targets [17]. The environmentally aware are easy to engage, but other sections of the public are
more challenging, even in the best performing areas approx 20% of households do not use
recycling collection services [18]. Changing behaviour remains one of the biggest challenges to
successful recycling collection services.
Division of responsibility
The responsibility for household waste management is divided at a local level between Waste
Collection Authorities, the District and Borough Councils and Waste Disposal Authorities, the
County Councils. Unitary Authorities have the responsibility for both collection and disposal of
household waste. A similar division of responsibility occurs at a national level between the
Department for Environment, Food & Rural Affairs (Defra), the Government Department
responsible for waste policy, strategy and monitoring and the Environment Agency (EA) , the UK
Government Agency responsible for licensing and regulating waste collection and disposal, see
Table 4.
Table 4. UK responsibilities for waste [2].

Organisational Activities and jurisdiction Act creating responsibility
Role
responsibilities
Department for
Sets general waste policy and has Policy EU Directive
Environment, Food &
monitoring and reporting role maker
Rural Affairs (Defra)
Licenses waste collection
Environment Agency General Environmental Protection Act
companies, waste carriers and
(EA) regulator (1990)
waste disposal and treatment sites
Waste
District / Borough Responsible for collecting Environmental Protection Act
Collection
Council municipal solid waste and recycling (1990) sections 45,46-7, &49
Authority
Environmental Protection Act
Responsible for disposal of Waste
(1990) section 51,
County Council municipal solid waste collected by Disposal
Waste & Emissions Trading
Waste Collection Authorities Authority
Act, 2003
Waste Environmental Protection Act
Unitary / Metropolitan
Responsible for collection and Collection (1990) sections 45,46-7, 49
Borough Council
disposal of Municipal Solid Waste &Disposal & 51, Waste & Emissions
Authority Trading Act, 2003
Separating responsibility and costs for waste collection and disposal prevents holistic approaches
to household waste management. This unhelpful division makes policy making and operational
issues functions of separate authorities with differing incentives [17]. Waste Disposal Authorities
59
procure disposal, treatment and recycling facilities for waste collections in which they have limited
input [18] however, some authorities work together on strategy and service delivery [19].
Waste prevention challenges
It is a challenge at Local Authority level to realize the priority position that waste prevention has in
the EU Waste Framework Directive. This priority is not always as obvious at Local Authority level,
where local waste policies are often biased towards recycling and disposal [20], making work in this
area more challenging. Sustainable waste management should focus on limiting the impact of
waste on the environment and reducing waste arisings [7]. Various initiatives operate nationally
targeting either particular waste streams or groups, different approaches are shown in Table 5 [21].
Table 5. Waste prevention activities [21].

Criteria Classification
Waste stream By material (paper, glass etc)
By product (packaging, nappies)
By source (household, industry)
By point of use (big events)
Target group Retail
Industry
Public administration
Householders
Instruments Regulation (licensing, laws, product standards)
Economic (subsidies, taxes, charges)
Collaborative agreements(certification, labeling)
Service and infrastructure (repairing, second hand shops)
Communications (presenting information, delivering options)
Purpose Reduction at source (complete avoidance, optimization of processes)
Substitution (refillable containers more environmentally friendly options )
Reuse (increasing product life by using second hand goods)
Waste prevention work is difficult, involving a greater behavioural change than participation in
recycling activities. Consumers are often unable to see links between waste and their purchasing
habits and are unwilling to reduce personal consumption. With 35-38% of household waste being
organic waste a national education programme, Love Food Hate Waste was initiated. This aims to
reduce food waste by educating the public about the correct storage of food, menu planning and
using left-over ingredients, but there is little quantitative data available regarding performance [21].
Whilst persuading consumers to change purchasing habits is challenging, retailers have also
resisted waste reduction projects, often seeing them as expensive and impacting negatively on
sales. However, the Courtauld Commitment, a grocery retail group working with the Government
funded Waste and Resource Action Programme (WRAP) focuses on resource efficiency,
minimizing packaging and reducing waste in the food sales and manufacturing sector [22], claims
to have avoided 520,000 tonnes of packaging between 2005 and 2009. Projects like this are
necessary to raise awareness in household waste management; significant reductions in
packaging waste can have an immediate impact on the generation of household waste.
Conclusion
Significant volumes of waste, diminishing landfill space and concerns about resource efficiency
make household waste management a priority in EU and UK environmental policy, this has been
passed down to local levels to act upon. A major factor in improving national recycling rates and
the UK reaching the 2010 target to reduce landfill disposal set in the EU Landfill Directive
(1999/31/EC) has been the change in collection practices which has seen the introduction and
expansion of kerbside collections of recyclable materials and organic waste collections.
To meet the challenge to further increase recycling rates Local Authorities must ensure full
recovery of all recyclable materials by changing behaviour patterns, engaging non-recyclers and
improving the quantity of waste recycled by people already participating. Additionally, the difficult
60
area of waste prevention needs addressing. With various target groups, target waste streams and
different messages this requires specialist communications involving a wide group of stakeholders.
To operate fully integrated waste management services with the cooperation of all parties
responsible for household waste the collection, transport and disposal of each material and
treatment and disposal options will be made in accordance with the Waste Hierarchy. This will
involve waste prevention programmes, recovery of as many recyclable materials as possible,
treating organic waste separately and producing energy from waste treatment in preference to
landfill.
References
[1] Wollmann,H.,& Marcou,G., The Provision Of Public Services In Europe, Between State, Local
Government & Market, Cheltenham, Edward Elgar Publishing Ltd, 2010.
[2] Energy & Utility Skills, 2010, The UK Waste Management And Recycling Industry 2010 Labour
Market Investigation, Solihull, Energy & Utility Skills
[3] Costa,I., Massard,G., & Agarwal,A., Waste Management Policies For Industrial Symbiosis
Development: Case Studies In European Countries, J.Cleaner Production,18 (2010) 815-822
[4] Muhle,S., Balsam,I., & Cheesman,C.R., Comparison of Carbon Emissions Associated with
Municipal Solid Waste Management in Germany and the UK, Resources, Conservation and
Recycling, 54 (2010) 11, 793-801
[5] Emery,A.,Davies,A.,Griffiths,A.&Williams,K.,Environmental& Economic Modelling: A Case Study
of Municipal Solid Waste Management Scenarios in Wales, Res,Cons&Rec, 49 (2007) 244-263
[6] Dangi,M.B., Pretz,C.R., Urynowicz,M.A., Gerow,K.G. & Reddy,J.M., Municipal Solid Waste
Generation In Kathmandu, Nepal, J. Env Management, 92 (2011) 240-249
[7] Demirbas,A., Waste Management, Waste Resource Facilities and Waste Conversion
Processes, Energy Conversion and Management, 52(2011)1280-1287
[8] Burnley,S.J., A Review Of Municipal Solid Waste Composition In The United Kingdom, Waste
Management, 27 (2007) 1274-1285
[9] Defra, (2010) Municipal Waste Statistics, 2009/2010, London, Defra
[10] Eriksson,O., Carlsson Reich,M., Frostell,B., Bjorklund,A., Assefa,G., Sundqvist,J.O.,
Granath,J., Baky,A., & Thyselius,L., Municipal Solid Waste Management From A Systems
Perspective, Journal of Cleaner Production, 13(2005)241-252
[11] Shaw,P.J., Lyas,J.K., Maynard,S.J. & van Vugt, M., On The Relationship Between Set-Out
Rates and Participation Ratios as a Tool for Enhancement of Kerbside Household Waste
Recycling, J of Env Management, 83(2007)34-43
[12] Oom do Valle, P., Reis, E., Menezes, J., Rebelo, E., Behaviour Determinants of Household
Recycling Participation, Environment and Behaviour, 36 (2004) 505
[13] Martin,M., Williams,I.D., & Clark,M., Social, Cultural And Structural Influences On Household
Waste Recycling: A Case Study, Resources, Conservation and Recycling, 48 (2006) 357-395
[14] den Boer,J.,den Boer,E.,&Jager,J.,LCA-IWM:A Decision Support Tool For Sustainability
Assessment Of Waste Management Systems,Waste Management,27(2007)1032-1045
[15] Iriate,A., Gabarrell,X. & Rieradevall,J.,LCA of Selective Waste Collection Systems in Dense
Urban Areas, Waste Management, 29 (2009) 903-914
[16] Curran,A. & Williams,I.,The Role of Furniture and Appliance Re-Use Organisations in England
and Wales, Resources, Conservation and Recycling, 54 (2010) 692-703
[17] Bulkeley, H., Watson,M., Hudson,R., & Weaver,P.,Governing Municipal Waste: Towards a
New Analytical Framework, J of Env Policy and Planning, 7-1(2005)1-23
[18] Harder,M.K., & Woodard,R., Systematic Studies of Shop and Leisure Voucher Incentives for
Household Recycling, Resources, Conservation and Recycling, 51 (2007)723-753
[19] Slater,R.,Frederickson,C.,Wield,D.&Potter,S.,A Critical Evaluation of Partnerships in Municipal
Waste Management in England, Res, Cons &Recycling, 51(2007)643-664
[20] Mazzantti,M.,&Zoboli,R.,Waste Generation, Waste Disposal and Policy Effectiveness:
Evidence on Decoupling from the European Union, Res, Cons & Rec 52(2008)10,1221-1234
[21] Salhofer,S.,Obersteiner,G.,Schneider, F.,Lebersorger,S., Potentials for the Prevention of
Municipal Solid Waste, Waste Management, 28 (2008) 245-259
[22] Jamasb,T.,Nepal,R., Issues & Options In Waste Management: A Social Cost-Benefit Analysis
of Waste-To-Energy In The UK, Resources, Conservation & Recycling,54 (2010)1341-1352
61
13th September
Session 1.2
Chairman: Ana Segades
62
SUSTAINABILITY APPRAISAL OF PARTICLEBOARD PRODUCTION WITH

RECYCLED WOOD WASTE BY ECOLOGICAL FOOTPRINT
1 1 1 1
A.M. Saravia , M. Herva , C. Garca-Diguez and E. Roca
1 Sustainable Processes and Products Engineering Group, Department of Chemical Engineering,
University of Santiago de Compostela, Campus Vida, 15705 Santiago de Compostela (Spain).
(albamarisela.saravia@usc.es, marta.herva@usc.es, carlos.garcia.dieguez@usc.es,
enrique.roca@usc.es).
ABSTRACT
The aim of this work was to assess the environmental sustainability of particleboard
production with recycled wood waste using the ecological footprint (EF).
The data was collected from a factory located in Spain and grouped into three selected
categories: material resources, energy resources and waste production. They were
converted into global hectares of land (gha) to evaluate the contribution of each one
regarding the environmental sustainability of the overall process.
The main contribution to EF was the material resources category followed by energy
consumption mainly due to heat supply, and finally the EF of wastes. To establish
comparisons, the EF for other scenarios increasing the ratio of recycled wood employed
was estimated, observing that this parameter strongly influenced the EF of the
particleboard production process. The EF significantly decreased from 0.93 to 0.003
-3
gham due to substitution of roundwood by wooden wastes particleboard for the
different scenarios analysed.
These results suggest that the effort for improving environment sustainability in this
industry should be mainly focused on material resources category, although it is
necessary a deeper study on types and ratios of recycled material used and their
influence in particleboards quality.
Keywords: Ecological Footprint; Particleboard; Recycled wood waste.
INTRODUCTION
The Ecological Footprint (EF) is a sustainability indicator that estimates the amount of bio-
productive land required to produce resources and absorb wastes in a given system. In recent
years, the EF has been applied in a variety of fields, i.e., policy-making, production processes,
environmental evaluations and research projects [1]. The EF of an activity, such as producing a
good, is calculated by summing the EF of all of the material and energy consumed and waste
generated during that activity [2]. No previous works regarding the application of the EF
methodology to evaluate environmental sustainability in the particleboard production industry were
found in peer-reviewed scientific literature.
The wood-based panels sector covers a variety of panel products that can be divided into three
main types of products: fibreboard, particleboard and plywood/veneer sheets. Fibreboard and
particleboard can also be sub-divided into panels with different properties and uses, such as:
hardboard, medium density fibreboard (MDF), chipboard and oriented strand board (OSB).
Fibreboard and particleboard are reconstituted panels manufactured from wood chips that can
come from a variety of sources. Plywood/veneer sheets are manufactured from industrial
roundwood usually made from roundwood of large size [3]. In Spain, pine is the main wooden
specie used to produce particles, but poplar and eucalyptus are also employed. In recent years,
recycled materials from wood and other industries (e.g.,plastic, rubber) are being used as raw
material [4]. In fact, particleboard can be manufactured at industrial level entirely with recycled
wood [5].
63
In this work, the EF was used to assess the environmental performance of a particleboard
production process that uses recycled wood waste as a fraction of raw material. The aims of this
study were: i) to evaluate the environmental sustainability of particleboard process production for
current usage of resources, and ii) to evaluate and to quantify the effect on EF of increasing
recycled wooden waste content in the raw material.
Process description, system boundaries and functional unit

The sustainability of a particleboard production process was studied appraising the ecological
footprint (EF) for data collected in a factory located in Spain. The study was a gate to gate analysis,
in which the system boundaries were defined by the raw material entering the factory and the
produced particleboard. The thicknesses, widths and lengths of the produced panels ranged from 8
to 45 mm, from 1220 to 2440 mm and from 2440 to 4880 mm, respectively. The selected functional
3
unit was 1 m of particleboard produced.
In this factory, the particleboard is produced by mechanical reduction of the raw material into small
particles; the chips are dried and screened to obtain a homogeneous material. Further, the chips
are blended with urea-formaldehyde resin, paraffin and additives. The particles are laid into a mat
to be hot-pressed into a panel; after pressing, the panel is cooled and trimmed and the board is
sanded or planed. This can be packaged and sold as final product or can be sent to an additional
line to obtain other finished products (melamine or veneered board).
Raw material is mainly wood from pine (75%), black poplar (10%), mixed wood (5%) and recycled
wood waste (10%). Recycled wood waste comprises mainly external industrial wastes in form of
woodchips as well as wastes recovered from the process. Secondary materials are chemical
products (Urea-formaldehyde resin, paraffin, ammonium nitrate, urea and ammonium bicarbonate)
and water. Energy demand is supplied by electricity from an external company and fossil fuels.
Two fuels are burned for thermal energy supply: natural gas and biomass in form of wooden dust
waste from the production process.
Among the generated non-wood wastes, the hazardous ones comprise packages contaminated
with dangerous substances, containers that were in contact with chemical products, adhesives or
dissolvent, batteries, fluorescent lamps, batteries, mineral oils and oil filters.
EF estimation
To estimate the EF of the particleboard production process, the component approach based on life
cycle inventory was employed [6]. The data were grouped into three selected categories: material
resources (raw material, secondary materials and water), energy resources (fossil fuels, electricity
and heat supply) and wastes generated in process. The EFs corresponding to material and energy
inputs were estimated using Eq. 1.
Vi EV
Ai ,k Fj i Fj (1)
j NPi j EPi
Where, Ai,k is the required area expressed in global hectares of land (gha) for each stream i
belonging to the main category k (energy or material resources). Vi are the consumption/generation
values corresponding to the functional unit and EVi are these values expressed in energy units.
The former are divided by the natural productivity (NPi), while the latter are divided by the energy
productivity (EPi) in order to express them in space units. These values are then multiplied by an
equivalence factor (Fj) which normalizes and homogenizes the different kinds of land (j) with
regards to their productivity [7]. In the current study, four different types of land, namely CO2 uptake
land, primary cropland, grazing land and forest, were affected.
The EF of wastes, including both hazardous and non-hazardous wastes, was calculated following
Herva et al. [1].
After calculating the individual EFs for input and output flows, they were aggregated to estimate the
3
total EF of 1 m of particleboard produced according to Eq. 2.
64
EF Ai EFwastes (2)
i
The factors used to estimate the EF are summarised in Table 1. Secondary materials were
converted into energy units using the corresponding energy intensity factor. The EF of electricity
depends on the generation mix which is shown in Table 2.
Table 1. Natural (NPi) and energy productivities (EPi)and equivalence factors (Fj) used in the EF
estimation.
3 -1 -1 1
Stream NPi [m ha yr ] Ref. Land type Fj
Wooden species 1.99 [8] Forest 1.26
Water consumption 1500 [8] Forest 1.26
Energy intensity
-1
[MJt ]
Secondary materials
Urea/Formaldehyde resin 3.10 [9] CO2 uptake 1.26
Paraffin 4.89 [9] CO2 uptake 1.26
Ammonium nitrate 1.16 [9] CO2 uptake 1.26
Urea 29.3 [9] CO2 uptake 1.26
Ammonium bicarbonate 1.16 [9] CO2 uptake 1.26
-1 -1
EPi [GJha yr ]
Energy sources
Fossil fuels 49.8 [10] CO2 uptake 1.26
Natural gas 65.50 [10] CO2 uptake 1.26
Electricity from
Hydroelectric 15,000 [8] Grazing land 0.46
Combined cycles/cogeneration 65.5 [10] CO2 uptake 1.26
Thermal coal-fuel/nuclear 50.00 [10] CO2 uptake 1.26
Renewables
Wind 60,000 [8] Grazing land 0.46
Mini-hydroelectric 200 [8] Primary cropland 2.51
Thermal solar 40,000 [8] Primary cropland 2.51
1
Reference [7].
Table 2. Electricity generation mix [11,12].

Electricity from % Generation
Hydroelectric 14.75
Combined cycles/cogeneration 31.47
Thermal coal-fuel 3.20
Nuclear 34.95
Renewables
Wind 14.74
Mini-hydroelectric 0.86
Thermal solar 0.03
Additionally to the EF assessment of the real production process, a sensitivity analysis was carried
out varying the ratio of recycled wood used as raw material from 0% to 100%. The same
consumption of material inputs (raw/secondary materials and water) and generated wastes was
considered. The energy consumption varied because different quantities of energy for processing
were needed depending on the ratio of recycled wood material employed. Recycled wood arrives
at the plant mostly in form of chips and, consequently, there is lower electricity consumption in
debarking and chipping stages when roundwood is substituted by recycled wood waste. Besides,
the heat energy demand for the drying process of chips from roundwood is 80% higher than that for
recycled wood. This is mainly due to the moisture content, which is 60% for roundwood and 15%
65
for recycled wood [13]. The drying of raw material has the highest requirements of energy (75% of
-3
total energy) [14]. It was estimated that the drying process consumes 1945.87 MJm particleboard
-3
when particleboard is produced by roundwood and only 389.17 MJm particleboard when is
produced by recycled wood material.
Inventory: Particleboard Production

3
The inventory of the process based on the functional unit (1 m of particleboard produced) is shown
in Table 3.
The energy demand for particleboard manufacturing, which includes all fuels and electricity, was
-3
2823.82 MJm particleboard (heat supply demand 84.5%, electricity 13.5% and fossil fuel 2%).
Thermal energy was provided by wooden dust (48.2%) and natural gas (51.8%). Wooden dust
provided a 40.8% of the total energy use.
Table 3. Inventory data of the particleboard production process.

INPUTS Units Values OUTPUTS Units Values
3
Material resources Product: Particleboard (*) [m ] 1
3
Wood raw materials [m ] 1.41 Wastes
Secondary materials Wood waste [kg] 57.58
Adhesive (U/F resin) [kg] 76.82 Hazardous [kg] 0.12
Paraffin [kg] 6.36 Urban waste [kg] 0.05
Ammonium nitrate [kg] 2.83
Urea [kg] 5.99
Ammonium
[kg] 0.04
bicarbonate
3
Water [m ] 0.09
Energy resources
Fuel Oil [L] 1.53
Electricity [MWh] 0.11
Heat supply [MWh] 0.66
(*) Functional Unit.
As regard other assessed scenarios, the total energy requirements ranged from 3017.38 to
-3
1081.78 MJm particleboard for 0% and 100% of recycled wood ratio introduced as raw material,
respectively.
EF evaluation
The EF of the particleboard production process was estimated using the inventory data in Table 3
The results are shown in Fig. 1 and 2. Among the selected categories, the highest EF contribution
corresponded to material resources (95.3% of total EF). This was mainly due to raw material
(99.99%) with the following distribution: pinewood 83%, black poplar 11% and mixed wood 6%.
The EF of wood material is strongly related to bioproductive area needed for forest. EF
corresponding to secondary materials was lower than 0.1 of the total EF. The EF value was mainly
due to the consumption of ureaformaldehyde resin (59.5%), urea (33.6%), paraffin (6.9%), and
ammonium nitrate and ammonium bicarbonate (less than 0.01 % for each one).
The energy consumption category is the second contributor to the total EF but only with 4.7% of
total. EF of natural gas burned for thermal energy supply represents nearby 66% within this
category, meanwhile electricity was 30.3% and the lowest contribution was for fossil fuel (3.6%).
Although heat supply accounts for 84.5% of total energy consumption, the corresponding EF
represents a lower percentage (66%), indicating a strong dependence between the type of
resources used and its environmental impact. Hence, the EF proved as a sensitive indicator to the
different sources of energy employed in the factory, providing lower values for cleaner sources
such as natural gas (the main fuel used for heat supply) and higher values for less environmentally
friendly fuels (e.g. coal, fuel oil).
66
The contribution of non-wood wastes to the EF of the process is very low (nearly 0.1%). The major
contribution within this category is due to hazardous wastes (80.15%) followed by urban waste
(19.85%).
-3
The overall results of the EF assessment yielded a figure of 0.85 gham for the manufacturing
process, as it can be observed in Fig. 1.
The EF of the process considering different contents of recycled wood in the raw material showed
a decreasing tendency as the ratio of recycled wood increases (Fig.1). A strong reduction of the EF
-3
of the process was observed, from 0.93 gham when raw material was only roundwood to 0.003
-3
gham when particleboard was manufactured entirely with recycled wood wastes.
The EF by subcategories excluding raw material can be seen in Fig. 2. EF of heat supply and
electricity diminishes as the ratio of recycled wood increases. The former decreases faster than the
latter because more energy is avoided in the drying process. When the recycled material is 80%,
the EF of thermal energy is slightly lower than EF of electricity. At higher values of percentage of
recycled wood used, there is not EF associated with heat supply because not more natural gas is
consumed and the burning of wood dust provides all the requirements of thermal energy.
1.0 Current
EF [gham-3 particleboard]
0.9 process Total

0.8
0.7 Material resources
0.6
Energy
0.5
0.4 Non-wood wastes from process
0.3
0.2
0.1
0.0
0 10 20 30 40 50 60 70 80 90 100
Recycled wood waste as raw material (%)
Fig 1. EF of particleboard production process by categories varying raw material composition
0.030
Heat supply
EF [gham-3 particleboard]
0.025
Electricity
0.020
Fossil fuels
0.015 Non-wood wastes from process
0.010 Water
0.005
0.000
0 10 20 30 40 50 60 70 80 90 100
Recycled wood waste as raw material (%)
Fig. 2. EF by subcategories excluding wood raw materials.
It is remarkable the important dependency of the process EF with the different wood raw material
recycled ratios. A significant reduction in the amount of natural resources used led to a lower
pressure on the environment. This is well quantified by means of the EF. However, this result
should be taken with caution, since other important aspects of using recycled materials (technical,
economic, or logistical issues), in terms of industrial feasibility, would have to be evaluated.
It is important to point out, as it is suggested by other authors [15,16], that it may be feasible to
apply other non-wood wastes, such as plastic or rubber from tires, as raw material in the
67
manufacture of particleboard, maintaining its functional properties. As these alternatives have
different requirements of resources, they must be evaluated for a more comprehensive knowledge
of their environmental sustainability.
CONCLUSIONS
In this study, the effect on environmental sustainability of using wood waste as raw material for
particleboard production has been quantified by means of the Ecological Footprint (EF). The
approach involves the main material and energy resources as well as generated wastes in a gate
to gate analysis using data from a Spanish factory.
The total EF was strongly influenced by round wood resource use, where pine, the main
component of particleboard, was the main contributor.
The estimated EF of particleboard production process suggests that the effort for improving
environment sustainability in this industry should be mainly focused on material resources
category, although it is necessary a deeper study on type and ratios of used recycled wood and its
influence in produced particleboard quality. Evaluating other alternatives for the production process
of particleboard and/or other finished products based on it would be needed to establish a more
comprehensive analysis of the environmental performance of this process.
Another positive aspect associated to the use of wastes by this industry is the avoided EF of waste
treatment process which has not been evaluated. All these aspects should be taken into account to
improve the sustainability assessment in this industrial sector.
References
[1] M. Herva, R. Hernando, E.F. Carrasco, E. Roca, Development of a methodology to assess the
footprint of wastes, J. Hazard. Mater. 180 (2010) 264-273.
[2] J. Kitzes, M. Wackernagel, Answers to common questions in Ecological Footprint accounting,
Ecol. Indic. 9 (2009) 812-817.
[3] UNECE/FAO, European Forest Sector Outlook Study 1960-2000-2020 Main Report, UN-
Publications, ECE/TIM/SP/20, 2005.
[4] AITIM, Productos de Madera para la Arquitectura. Electronic book, Spain, 2008.
[5] J.B. Wilson, Life-Cycle Inventory of Particleboard in Terms of Resources, Emissions, Energy
and Carbon, Wood Fiber Sci. 42(CORRIM Special Issue) (2010) 90106.
[6] C. Monfreda, M. Wackernagel, D. Deumling, Establishing national capital accounts based on
detailed Ecological Footprint and biological capacity assessments, Land Use Policy 21 (2004)
231-246.
[7] B. Ewing, S. Goldfinger, A. Oursler, A. Redd, D. Moore, M. Wackernagel, The Ecological
Footprint Atlas 2010, Global Footprint Network, Oakland, 2010.
[8] J.L. Domnech, Gua metodolgica para el clculo de la huella ecolgica corporativa,
Terceros Encuentros Internacionales sobre "Desarrollo Sostenible y Poblacin, Universidad
de Mlaga, Espaa, 2006.
[9] Ecoinvent database, Versin 2.2, 2011.
[10] P. Coto-Milln, J.L. Domnech Quesada, M. Mateo Mantecn, Research Letter. Corporate
Ecological Footprint: New Conversion Factors, Res. Lett. Ecol. (2008) 1-4.
[11] IBERDROLA, Informacin Complementaria del Informe de Sostenibilidad 2009, Electronic
book, 2009.
[12] IBERDROLA RENOVABLES S.A., Resultados 2009. Informe Trimestral, Electronic book,
2009.
[13] R. Sathre, L. Gustavsson, Energy and carbon balances of wood cascade chains, Resour.
Conserv. Recycl. 47 (2006) 332355.
[14] FAO, Energy conservation in the mechanical forest industries. FAO Forestry paper 93, Rome,
1990.
[15] M. Chaharmahali, M. Tajvidi, S.K. Najafi, Mechanical Properties of Wood Plastic Composite
Panels Made From Waste Fiberboard and Particleboard, Polym. Compos. 29 (2008) 606-610.
[16] N. Ayrilmis, U. Buyuksari, E. Avci, Utilization of Waste Tire Rubber in the Manufacturing of
Particleboard, Mater. Manuf. Process 24 (2009) 688692.
68
THE RECYCLING OF BAYER ELECTROFILTER FINES FOR NEW APPLICATIONS.

1 1 2 1
B. Fernndez , J. Ayala , J. Sancho and P. Garca
1Escuela de Minas de Oviedo
2Residuos. Principado de Asturias.
C/ Independencia, 13 - 33004 Oviedo
Abstract
Aluminum is the second most used metal after iron due to its singular properties that
makes its alloys useful in many applications. Despite of its great importance, the
obtaining processes (Bayer_Hall-Heroult tandem) produce an important environmental
impact. Generated waste and pollutants should be minimized and treated.
The laboratory of Metallurgy of the Escuela de Minas de Oviedo is investigating the

uses of industry wastes from alumina/aluminum industry since over 30 years. This
paper presents one of the research lines followed for the recycling of electrostatic filter
fines from alumina calcination furnace, to produce industrial quality aluminum sulfate,
alums and abrasives and an alternatively as a material for the elimination of heavy
metals from the industrial aqueous solutions, waste water or natural surface mineral
leachings.
Keywords: Electro-filter Fines, Bayer, Alumina, Metallurgical waste, Recycling, Waste water,
Natural surface mineral leaching.
INTRODUCTION
Electro-filter fines is a residue generated in considerable amounts (betwen 5-8% of the final alumina
product) in the last stage of the Bayer Process, during the aluminum hydroxide calcination. The residue is
a mixture of alumina and different hydrates that have not completed their calcinations process. Due to its
small particle size, the dust leaves the fluid bed calciner by its upper part and is collected in the electrofilter
device, avoiding to be in the final alumina product, that will be in that case of bad quality for electrolytic cell
bath solution [1-4].
Electrofilter fines, with an annual output of 80.000-100.000 tons for a 1,2 millions tons alumina plant, has
been tested for some different applications: Calcinations fines with residual alumina, has been recycled to
the digesters and also they were used as raw material for alpha alumina production used in the refractory
industry, after heat treatment at 1400C, with not so much success. So, they are in many cases stored
indefinitely in the red mud pool as another waste.
It is therefore evident the need of the treatment of fines for a better raw materials economy (sustainability),
also avoiding an environmental problem. The laboratory of Metallurgy of the Escuela de Minas de Oviedo,
has been studying alternatives to this outside storage, trying to find viable alternatives to the residue. In
this context, this paper presents different alternatives for treating this waste generated for yielding products
with market value or using it for the fixation of heavy metals from natural or industrial waters. [5-7].
69
MATERIALS AND METHOD
Materials
The electrofilter fines used for this study were produced in the Spanish plant of San Ciprin.
This waste is a heterogeneous product consisting of aluminum trihydrate, transition aluminas
and alpha alumina that has to be managed. The analysis of a sample of the product presents a
composition of about 90% of aluminum oxide, 16% of which is alpha alumina and the rest is
gibbsite and transition aluminas.
Table 1
Chemical Analysis of dry electrofilter fines
Component (wt %)
Na2O K2O MgO Fe2O3 Al2O3 CaO Moisture MOI LOI
0.50 0.21 0.06 0.19 89 0.03 2.25 8 .0 1.95
MOI (moisture on heating to 300C), LOI (lost on heating from 300-1200C).
Methodology:
The whole utilization of the Bayer electro-filter dust produced to obtain different commercial
products takes place at different stages. Figure 1 shows a flow-diagram of the manufacturing
process for three products: aluminum sulphate, abrassive and alum.
Methods for obtaining aluminum sulfate solution with commercial specifications, from different
residues from aluminum industry, have been developed successfully in the Ctedra of
Metallurgy, several years ago. For their production, and after analyzing the original waste, an
acid leaching at 90 C is made as follows Eq. 1
Al2O3. n H2O + 3 H2SO4 = Al2(SO4)3 + (3 + n) H2O (1)
The mixture is stirred to get the dissolution of the aluminium trihydrate. As an example, the
production of 1000 ml of commercial characteristics aluminium sulphate solution uses 875 g of
industrial sulphuric acid and 375 g of the initial sample. This product has as its main field of use
as coagulant for drinking water treatment. Recovery of aluminium is low, as only hydrate is
digested.
Another possibility is an sulphuric acid dry attack at high temperature in oven, so that transition
alumina could be also attacked. Starting with 80 g of initial sample and 320 g of sulfuric acid,
the mixture treated at 300C in oven for half an hour, is subsequent leached with 800 ml of
water, producing 1000 g commertial solution, plus 13 g of alpha alumina, that could be used as
abrasive because its fineness ( less than 5 m) .
It can be associated the two different attacks for producing aluminium sulfate, alum, and
abrasive alumina. The flow-theet for this tandem process is described in the Fig. 1. After the first
treatment where aluminium sulfate is produced, residual aluminas are processed by sulfation.
Solid masse is water leached and the solution produced is used for potassium alum production
with a high yielding (90%) Eq. 2
70
Al2(SO4)3 + H2SO4 + 2 KOH + 22 H2O = 2 AlK(SO4)2 . 12 H2O (2).
Metals can be removed from different waters using materials as fly ash, due to the pH
modification made by the residual lime content. The Bayer electrofilter fines exhibit capacity for
heavy metals fixation dissolved in surface or industrial waters. Also it is due to the residual
aluminium hydroxide they have that can variate the pH of the solutions as well as the alumina
2
(beta) capacity of adsorption in its surface as their high specific surface (50 m /g). Some tests
++
with copper has been carried out successfully, having a fixation capacity between 2 to 5 Cu
grams per kilo of fines, with the enormous advantage of recovering the copper with an acid
++
solution, leaving the fines residua with less than 1ppm of Cu . Ni and Cd have a similar
behaviour than copper, and also are fixed on the fine material.
71
Conclusions
The aim of the companies management systems is in general, and particularly in aluminium
industries, to minimize the amount of waste being sent for disposal. With the treatments outlined
above, products with added-value were obtained from Bayer electrofilter fines, using very
simple techniques and cheap reagents, thus getting a correct environmental management of
waste generated in the Aluminium industry. Also this residue can be used for heavy metals
fixation leaving different industrial or surface water in condition of purity for being incorporate to
rivers.
References
[1] J.P Sancho., L.F Verdeja. and A. Ballester, 2000. Metalurgia Extractiva Vol 2. Madrid Ed.
Sntesis. 181190.
[2] M.P. Garca, J.M. Ayala and J.P. Sancho, The use of Bayer alumina fines for other
industrial purpose (1993), Light Met. (1991), pp. 195201.
[3] J.P. Sancho, La Metalurgia del Aluminio, Aluminium Verlag., Dusseldorf (1992), pp. 6365.
[4] J.P. Sancho Martnez, J. Ayala Espina, M.P. Garca Coque, B. Fernndez Prez and D.
Costales Alonso, The sulphuric acid leaching of Bayer electrofilter fines: a practical
kinetical approach, J. Met. (2006), pp. 5863 August 2006.
[5] J. Sancho, M.P. Garcia, M-F Garcia, J. Ayala and L.F. Verdeja - The posible use of Bayer
process cyclone fines for manufacture of abrasives.. Rev Metal. Madrid 38 (2002) 433
442.
[6] J. Ayala, F. Blanco, P. Garca, P. Rodriguez and J. Sancho . Asturian fly ash as a heavy
metals removal material. Fuel. Volume 77, Issue 11, September 1998, Pages 1147-1154.
[7] J.L. Vega Farfn, J.M. Ayala, L.F. Verdejas, J.P. Sancho, J.G. Iglesias, J. Loredo and F.
Tamargo, Bentonites as a material controlling contamination related to zinc
hydrometallurgy. Iron control and disposal. Second International Symposium on Iron
Control in Hydrometallurgy, Ottawa, Canada (1996).
72
EVALUATION OF PELLETS PRODUCED WITH UNDERGROWTH TO BE

USED AS BIOFUEL
1a 1b 1c
N.L. Mustelier , J. Cavalheiro , M.F.Almeida
1 University of Porto
Faculty of Engineering of Porto University
Dpt. of Metallurgical and Materials Engineering, University of Porto, Porto, Portugal,
Rua Dr. Roberto Frias, s/n 4200-465 Porto PORTUGAL
a niubis@fe.up.pt, b jcavalheiro@netcabo.pt; c mfa@fe.up.pt
ABSTRACT
Many European countries are developing the use of pellets or wood briquettes for the
supplying of local energy. Many industries are being forced to replace fossil fuels by
biomass because of its neutrality in relation to CO2 emissions, thus creating an
interesting market for pellets. In Portugal, the most common undergrowth includes:
esteva (Cistus Ladanifer), tojo (Ulex Europaeus), giesta (Sarothamus Scoparius), feto
(Pteridium aquilium) and silva (Rubus ulmifolius). These undergrowth specimen are
attractive due to the large volume available, but are not usually used for making pellets.
It is possible to prevent large fires cleaning the forests, but this is an expensive task that
could be compensated if the undergrowth can have some commercial value. The aim of
this work is to obtain pellets with standard properties and evaluate the parameters that
can qualify the performance of these pellets: moisture content, particle size distribution,
high heating value, height of flame and burning time, pressure and temperature of the
pelletizing process and mechanical durability. The results showed that the apparent
density varies around 1260 kg/m3. The moisture content of different pellet varied
between 2.79 and 7.46%, ash content was less than 3%, the calorific value is between
16-18kJ/kg, the durability results respect the values recommended by standards. After
ignition the flame increases to an average height of 25 mm. The total burning time was in
all cases dominated by the cinder combustion without visible flame and the total complete
burning time varied between 400 and 600 s.
Keywords: Biomass, undergrowth, pellets, biofuel.
INTRODUCTION
The production of energy from vegetable biomass constituted an important component, initially
valuing the forest, agricultural residues and agro industrial already existing and subsequently giving
more importance to the production of biomass for energy purposes. Many industries are being
forced to replace fossil fuels by biomass because of its neutrality in relation to CO2 emissions, thus
creating an interesting market for pellets [1]. The basic properties of pellets such as moisture
content, bulk and single pellet densities, compression strength and durability (abrasion resistance)
depend on both the raw material composition and the pelletizing process variables [2,3]. In
Portugal, a development program is being conducted for efficient exploitation of renewable energy
resources. The most common Portuguese undergrowth includes: Esteva, Tojo, Giesta, Feto and
Silva. This undergrowth invades the forest spaces and the absence of clean soil due to high costs
greatly increases the risk of large-scale fires. These specimen are attractive due to the large
volume available, but are not usually used for making pellets. [4] The aim of this work is to obtain
pellets with standard properties and evaluate the parameters that can qualify the performance of
these pellets: moisture content, particle size distribution, high heating value, height of flame and
burning time, pressure and temperature of the pelletizing process and mechanical durability. Some
samples were submitted to a torrefaction treatment.
73
MATERIALS AND EXPERIMENTAL PROCEDURE
Different Iberian species had been studied as: Feto, Giesta, Tojo, Silva e Esteva, more frequent
species of undergrowth in used Portugal. The raw material was collected in the region of Serra do
Caldeiro, Santa Justa and Pias, in the summer of 2010 (23/7), winter (15/1) and spring (05/05)
2011. The material was collected in the wild and fresh, stored in plastic bags. All raw materials
were dried at a temperature of 110 C to constant mass and have been obtained proximate
analysis. Proximate analysis was performed on the biomass samples to determine the weight
fractions of volatile, ash, and fixed carbon contents. The ASTM Standard Test Method for
Proximate Analysis of Wood Charcoal (D 1762-82) was used for vegetable residues.
The pelletizing process was first simulated on laboratorial scale using small amounts of each
vegetal specimen which was pressed in a heated mould. Some samples were submitted to a
torrefaction treatment. After the laboratorial screening, the selected material was processed using a
pellet mill to prepare pellets with 6 mm of diameter. The drying temperature was 105C. The matrix
was pre-heated to approx. 150 C before processing and a pressure of 10 Kgf/cm2. All samples
were produced under the same laboratory conditions. Pellets were produced without any additives.
In a second simulation were produced pellets in industrial pelletizer at the Centre for Waste
Recovery (CVR), University of Minho, pellets were obtained with identical results to the laboratory
process.
Torrefied pellet are the new products that result from combining the torrefaction and pelletization
techniques, and they are still in the pilot stage of production in other countries. The process was
conducted in a tube furnace with a heating temperature up to 230 C for 30 minutes, after which it
3
was made a stage for 30 minutes at this temperature. A nitrogen flow of 0, 34 cm /min was used to
avoid combustion of the biomass. An inflamed lamp with the flame it is placed in the exit extremity
of the gases for guarantee their burning. The cooling of the biomass is made naturally.
Physical characteristics of feedstock and pellets

Dimensions and apparent density: From each kind of samples 10 pellets were randomly
selected for determination of single pellet density; each one of the pellets was measured weight,
length and diameter. The volume and the average apparent density were calculated.
Moisture content (w.b.) was measured by weighing a fuel sample about 100 g before and after
drying at 1032C to a constant weight according to CEN/TS 14774-2. Three samples from the
cooled pellets were used in each determination.
The ash content (% dry wt) was determined according to methods of loss on ignition at 550C
based on the CENT/TS 14918:2005 standard and were used 3 sample de 100g from raw
material and 4 samples from pellets.
Gross calorific value (MJ/kg): Three samples from feedstock, pellets and torrefied pellets were
selected to determine gross calorific value by using a bomb calorimeter heat of oxygen
according to the standard CEN/TS 14918:2005.
Chemical Analysis of ashes was obtained following CENT/TS 15290:2006.
The mechanical durability will be evaluated using tumbling device similar to the ASAE S 269.4
following CEN/TS 15210:2005 standard. The rotation speed is fixed to 50 rpm for 10 min. A 100
g sample closed inside a box was tumbled for 500 rotations before being sieved manually with a
3.36mm round hole sieve according to ISO 3310.2. The pellets used for this test were produced
in industrial pelletizer at the Centre for Waste Recovery (CVR), University of Minho. The
durability is expressed as the percentage in mass of the pellets remaining on the sieve to the
total sample weight.
Thermochemical characteristics of pellets: The pellets were adjusted to a mass of 0.5000.001
g and a length of 8.00.1 mm, depending of the initial pellet density for the different pellet kind
used. To determine the time for the pyrolysis and char combustion phases respectively, single
pellets were completely combusted. The characteristics of combustion was carried out with the
aid of a small support burning manufactured by hand where the pellet is fully supported on the
bottom and sides of the same. In this characterization we assessed the initial time of pyrolysis,
flaming pyrolysis time and char combustion time as well as the curve of the flame behaviour and
maximum height reached.
74
Table 1 shows the proximate analysis results of the biomass in nature. All the moisture content was
high, with the exception of Esteva. The species presented high volatile matter content between 66
and 78%. The ash content varies between 3.3 and 4.3 %. Fixed carbon content of 30.3% of Feto is
quite different of Giesta with 16.8%. Gross calorific values of all of the species are similar, around
18MJ/kg.
Table 1 - Proximate analysis of biomass

Biomass - Vegetal residues
Proximate analysis
F G T S E
Moisture (% wb) 51,17 46,06 45,95 50,71 12,60
Ash (% dry wt) 3,46 4,36 3,27 3,46 3,52
Volatile matter (% dry wt) 66,28 78,84 73,20 74,98 71,92
Fixed carbon (% dry wt) 30,26 16,80 23,52 21,57 24,56
Gross calorific value (MJ/kg) 18,76 19,35 18,47 17,82 18,63
Average of three replicates
In this evaluation is verified than the vegetable residues in nature present high volatile matter
content, which is more than 66%. The quantity of volatiles in biomass fuels is high and usually
varies between 76 and 86wt% (d.b.) in woody biomass [5]. This high proportion of volatiles results
the major part of the biomass fuel being vaporised before homogeneous gas-phase combustion
reactions take place. The amount of volatile matter therefore strongly influences the thermal
decomposition and combustion behaviour of solid fuels [6]. This can be observed on the results
obtained with feedstock Giesta.
The particle size distribution for all species is similar and with size recommended by small scale
pellet furnace manufacturer. Only the Giesta presented a discontinuity in the distribution, with 15%
of the material retained in the 3mm sieve but with 75% fine particles less than 0.85 mm. The
particles size as well as distribution influence in the combustion behaviour of pellets. The
development of automatic biomass heating systems with performance similar to oil or gas fired
heating systems was only possible because of market introduction of pellets with uniform size and
shape [7].
The produced pellets have 6, 8 e 10 mm of diameter but for the different characterizations were
realized using only the 6 mm pellets. The diameter of these pellets was in the range 5.86mm, and
the length varies from 9 to 12mm. The apparent density of pellets is in a range between 1274 and
1018 kg/m3 (see Table 2). The pellets PG, PT, PS and PE have similar densities with the denser
3
pellets PF. A guiding value 600 kg/m for the apparent density of wood pellets is specified in the
Swedish standard. The results show that the samples analysed have an apparent density between
this values.
Torrefied pellets hold the highest bulk density among all the test materials from both ways of
measurement. The measured apparent density is between 1187, 82 - 956, 42 kg/m3; it suggests
that torrefied pellets can have logistical advantage compared to untreated pellets, due to their
higher density
The moisture content of solid biomass influences the calorific value and the combustion efficiency.
The guiding value from ONORM M 7135 and DIN plus is below 10%, while DIN 51731 states the
moisture content should be below 12% [8]. The average moisture content of commercially
produced pellets varies between 10-12%. All the pellets produced in the different species showed
values ranging from standard established varying of 2,79 to 7,46%. (Table 2)
75
Table 2 - Quality parameter of pellets
Moisture Ash Gross calorific
Density Lenght Durability
content content value
Sample
(% wt) (% dry (MJ/Kg) (Kg/m3) (mm) (<3 mm % wt)
** ** ** ** ** **
PF Avg 7,46 1,38 1,33 1,69 16,16 21,71 1018,44 956,42 9,57 8,67 98,10 96,50
SD 1,23 0,19 0,15 0,32 0,02 0,04 6,10 2,40 1,1 1,8 0,5 0,15
PG Avg 2,79 1,55 1,57 1,74 17,44 21,42 1274,48 962,80 11,83 9,33 97,07 94,50
SD 0,39 0,24 0,03 0,66 0,06 0,06 2,80 10,80 2,1 0,5 0,3 0,06
PT Avg 6,05 1,25 2,83 1,88 16,08 20,45 1259,69 1096,00 10,14 8,17 98,43 97,00
SD 0,28 0,30 0,46 0,29 0,04 0,02 4,70 4,00 0,9 1,2 0,6 0,08
PS Avg 4,14 0,08 2,71 1,62 16,40 20,19 1252,72 1174,03 10,50 8,17 98,50 97,05
SD 0,36 0,05 0,30 0,08 0,08 0,05 8,80 6,50 0,5 0,8 0,8 0,36
PE Avg 5,39 1,38 2,27 2,66 16,51 20,65 1266,01 1187,82 10,33 10,33 99,37 96,46
SD 0,06 0,06 0,04 0,6 0,10 0,03 5,60 18,40 0,5 0,5 1,2 0,1
** Pellets with torrefaction
The results obtained for the pellets produced with torrefaction shows than the content moisture is
reduced considerably when compared with untreated pellets. The moisture content of torrefied
biomass is very limited by standard, varying from 1% to 6%. The moisture content of torrefied
biomass is very limited due to the dehydration reactions during the torrefaction reaction.
Destruction of OH groups in the biomass by dehydration reactions causes the loss of capacity to
form hydrogen bonds with water. In addition, non-polar unsaturated structures are formed which
makes the torrefied biomass hydrophobic [9].
The ash content in biomass is highly variable. On Table 3 can be observed that is possible to
attribute a typical range of the content of ash the biomass originated from undergrowth, with a
small variation of the content of ash in each type of biomass. The pellets produced with Feto and
Giesta were that presented smaller values compared to the pellets produced with the Tojo that
present higher values to around 2,83%. The high values can be explained primarily by mineral
impurities present in the bush stems that are strongly projected to the upper leaves during heavy
rains which can contribute to increase ash contents.
During burning the presence of high levels of ash originates normally high emission of particles
and formation of slags that clogs the burning systems Without contamination with ground mineral
spashs the ash is inside acceptable limits (1- 3% for normal quality). In order to maintain a high
operating comfort for end users in the residential heating sector, high ash content must be avoided.
[10]. According to results, the torrefied pellets presents ash content 50% lower than untreated
pellets, which means that the contaminating inorganic particles can be separed during the
manipulation of the torrefied material.
The differences in the values of gross calorific value GCV, dry basis, found among the samples
tested biomass, ranged from 16,80 MJ/kg and 17,44 MJ / kg (variation 3.6%). These values show
is interesting and sufficiently high to justify the use of waste energy plant. The small variation
between the values of the GCV, it also indicates that other species of plant biomass, the values of
GCV may be within this range.
25,00
20,00 4,36
3,46 3,46 3,52

3,27
15,00
Tcinzas (%)
Pc (MJ/kg)
10,00
17,44
16,16 16,08 16,40 16,51
5,00
0,00
PF PG PT PS PE
Tipos de Pellets
Fig. 2 - Gross calorific value and ash content in the different pellets.
76
The pellets PG had the highest gross calorific value of all the pellets tested probably due to the
highest values of volatile matters presents in the raw materials. The ash content can be seen in
Fig. 2. Torrefied pellets shows higher calorific value ranging from 20-22MJ/Kg due to the fact that
during torrefaction, biomass loses relatively more oxygen and hydrogen compared to carbon.
Subsequently, the calorific value of the product increases.
According to Table 3, all biomass pellets had a durability value above 97,5%, indicating that the
pellets were very durable. Among the five types of biomass, pellets PG had the lowest durability
value. Low pellet durability is not desirable as it can cause problems during transport and with
pellet feeding systems, increasing dust emissions, and an increased risk of fire explosion during
pellet handling and storage. Regarding the durability of the torrefied pellets was found that the
value is not enough to achieve the standard levels (higher than 97, 5%).The torrefied biomass also
becomes more porous with a volumetric density of 9561100 kg/m3. It is more fragile as it loses its
mechanical strength, making it easier to grind or pulverize.
The conversion times during the combustion of the pellets produced with undergrowth, is shown in
Fig. 3. The total conversion time was in all species dominated by the char combustion phase.
600
500
Time inicial pyrolysis

Conversion time (s)
400
Time flaming pyrolysis

300
Char combustion
200 Total conversion time
100
0
PC PF PG PT PS PE
Fig. 3 Comparison of conversion times during the combustion of the pellet.
After initial smoldering for nearly 1 min, the pellets started to burn, lasting for 1,5 min with flame.
The incandescence lasted for 4 to 7 min. This behaviour is due to the overlap of devolatilization
and char combustion, where the volatiles burn as gas products, whereas the fixed carbon burns
slowly [11, 12]. Among all, the PE pellets had the best time of combustion and a more complete
combustion during the visual information. The length of the flame was initially 25 cm high and
decreased continuously until it died down. Except for a few traces of smoke observed initially, the
samples burned without smoke. The greater height of the flame was reached by pellets PG, which
exhibit the higher volatile content and the lowest by the pellets PS, which have also an high volatile
content.
In the chemical analysis of ashes, Si, Ca, Mg, K, Na and P are the major ash-forming elements
occurring in biomass fuels being present in biomass in the form of oxides. Their concentration
ranges are shown in Table 3.
Table 3 - Chemical composition of the ashes of different kinds of pellets evaluated

Pellets SiO2 Fe2O3 TiO2 P2O5 Al2O3 CaO MgO SO3 Na2O K2O CuO ZnO C S Cl
PF 24,00 0,53 0,00 7,97 0,91 15,50 6,86 4,75 2,47 28,50 0,02 0,14 4,10 1,90 6,86
PG 0,02 2,38 0,24 11,90 5,34 22,40 7,65 5,25 8,90 14,80 0,08 0,44 3,40 2,10 3,05
PT 14,10 2,72 0,42 6,07 8,16 16,40 8,71 6,00 10,70 21,70 0,06 0,24 3,90 2,40 3,71
PS 3,27 0,86 0,01 8,31 1,89 46,30 9,33 3,13 1,12 18,20 0,02 0,18 7,60 1,25 1,30
PE 4,06 1,15 0,07 8,72 2,45 41,30 9,99 3,60 0,86 20,60 0,03 0,17 6,90 1,45 1,72
PC1 3,86 2,06 0,14 1,08 1,47 16,40 3,52 0,38 1,31 5,99 0,03 0,17 62,10 0,15 0,03
PC2 9,07 3,28 0,19 2,09 4,73 17,20 5,59 0,80 1,35 6,56 0,02 0,08 48,70 0,32 0,06
BC 33,50 2,90 0,32 1,85 4,52 38,30 2,67 1,30 0,44 6,87 0,01 0,04 6,10 0,52 1,08
PC 1 PC 2 - Commercial Pellets BC- Commercial Briquettes
77
The highest concentrations typically present in the species studied are Si, P, Ca, K. In general, the
levels are set upon by the standard. The K2O content is higher in species assessed, compared with
commercial pellets and briquettes, the values ranging between 14,80 to 28,50%. According to the
norm, values must be under a 7%. The chlorine content samples investigated has been detected to
vary between 2, 4 and 1, 25% and the sulphur content varies between 1,72 - 6,86%. Increased
concentrations of the elements Cl and S can be the result of a chemical contamination by, e.g.
insecticides, adhesives, glues, lacquer, dyestuff or wood preservatives in the raw material or a
result of the use of additives. The concentrations of these elements should be limited due to their
negative influences on the combustion process. High amounts of S and Cl can cause problems
regarding emissions (HCl and SOx), deposit formation and corrosion. Furthermore, Cl influences
the formation of dioxins and furans (PCDD/F). Minor ash-forming elements occurring in various
biomass fuels are Fe, Al, and heavy metals.
CONCLUSIONS
The results showed that it is possible to produce pellets of undergrowth with physical and
thermochemical characteristics similar to the existing in the market in the present time. The
biomass of vegetable waste from the undergrowth, presents technical characteristics appropriate
for its use of energy. The pellet showed up strong and durables with high density makes them
easier handle, transport and store. Physical and fuel characteristics of torrefied biomass was
superior compared to that of untreated biomass. More research is needed on the effects of raw
material characteristics, seasonal variations, collection and storage of raw material as well as
manufacturing process in order to design a production line which would produce pellets with the
required quality established by norms while considering the specific application of pellets. Finally
the use of undergrowth to produce heating pellets can be an important contribution to introduce the
undergrowth in the value chain with positive effects on the economy of forest.
REFERENCES
[1]Junginger, M et al. (2008) Developments in international bioenergy trade. BIOMASS &
BIOENERGY 32 (8): 717-729 Aug.
[2] Rhn C, Gref R, Sjstrm M, Wsterlund I. 2005Effects of raw material moisture content,
densification pressure and temperature on some properties of Norway spruce pellets. Fuel
Processing Technology;87:11-6.
[3] P. Lehtikangas, (2001) Quality properties of pelletised saw dust, logging residues and bark,
Biomass and Bioenergy 20 351-360.
[4] Brs, A. M., Miranda, F., Hiplito, L. & Dias, L. S. (2006) Biomassa e produo de energia. O
Minho, a Terra e o Homem DRAEDM. 51: 23-30
[5] Dan Bergstrm, Samuel Israelsson, Marcus hman, Sten-Axel Dahlqvist, Rolf Grefa, Christoffer
Boman, Iwan Wsterlund. (2008) Effects of raw material particle size distribution on the
characteristics of Scots pine sawdust fuel pellets. Fuel processing technology 89 1324-1329.
[6] Timothy V., Larson et al. 1994Wood smoke emissions and non-cancer respiratory effects. Ann
Rev. Pub. Health, 15: 133-156
[7] Pallav Purohit, Arun Kumar Tripathi, Tara Chandra Kandpal. 2006. Energetics of coal
substitution by briquettes of agricultural residues. Energy 3, 13211331
[8] Peksa-Blanchard M, Dolzan P, Grassi A, Heinimo J, Junginger M, Ranta T, et al. IEA
Bioernergy Task 40-Global wood pellets markets and industry: policy drivers, market status and
raw material potential. IEA Task Nov 2007; 40.
[9] Ayla Uslu, Andre P.C. Faaij, P.C.A. Bergman. (2008) Pre-treatment technologies, and their
effect on international bioenergy supply chain logistics. Techno-economic evaluation of torrefaction,
fast pyrolysis and pelletisation. Energy 33 1206 1223
[10] hman M, Boman C, Hedman H, Nordin A, Bostrm D. 2004Slagging tendencies of wood
pellet ash during combustion in residential pellet burners. Biomass and Bioenergy;27:585-96.
[11] Jaakko, J., J. Martti, and L. Linna. 1993. Simultaneous pyrolysis and char combustion. Fuel 72:
599609.
[12] Mansaray, K. G., and A. E. Ghaly. 1997. Physical and thermochemical properties of rice husk.
Energy Sources 19:9891004.
78
St
Universidade do Minho, Guimares, Portugal
CHALLENGE IN THE CONSTRUCTION INDUSTRY IN BRAZIL: HOW TO

BRING RECYCLED AGGREGATES ON THE MARKET
1,a 1
Lima, F.M. , Nocito G.
1
Research ; Technology Mineral Center, CETEM,Rio de Janeiro, Brazil
a
flima@cetem.gov.br
ABSTRACT
This work aims to study the feasibility of construction, implementation and operation of
recycling plants for construction and demolition waste (CDW). The research is based
on empirical work on the characterization and qualification of CDW in three Brazilian
cities: Maca(RJ), Macei(AL) and So Paulo(SP). Technology options are proposed
by the layout of recycling plants as well as the measures to create a market for
recycled aggregates still nascent. The establishment of this market is fundamental to
solve many problems: the irregular discharge of CDW in illegal dumps, the increasing
use of the volumes of licensed landfill with recyclable material; aggravation of the
environmental conflicts between sand and gravel producers against the neighboring
populations and early exhaustion of the deposits of these minerals.
Keywords: construction & demolition waste; recycling; recycled aggregates market.
INTRODUCTION
CDW offers a wide variety of materials by the intrinsic variability in their composition. Brazilian
cities have an urban structure with different constructive patterns. One objective was to study
the regional variations of these compositions. Another objective was to study the crushing
behavior by means of using two types of crushers that were installed in a pilot scale plant.
The results were simulated in layouts of plants to study the economic feasibility of recycling in
different cities.
Methodology
The following steps were adopted:
Representative sample definition;
Diagnostic and selection of the main areas of discharge and CDW collectors;
Collection proceedings, preparation and sample reduction;
Collection and classification of the three cities samples;
The samples were crushed in two types of crushers: jaw and impact;
samples were classified according to their density "d" in three quality levels: HQ-High Quality
(d> 2.2), MQ-Medium Quality (1.9 <d <2.2) and LQ-Low Quality (d <1.9);
Layout studies of the CDW management central facilities
Economic feasibility of the facilities
RESULTS
Sink Float Tests

Reserchers from USP [1] in trials with mixed waste found that those wich dn 2.2 exhibit
characteristics similar to natural aggregate when used as recycled aggregates, withstanding
pressures of 50 Mpa. These tests were conducted in sink and float . In the diagram below
transcribed densities used in these tests.
79
Cut Densities
Cities sampling
Pierre Gy formula: representative primary sampling buckets.
Q x 100 x
Ql f h d3
M
Sa 2
M min=322 tons= 225 m =51 buckets
Sampling lasted six months. The research work considered the debris already deposited and
those coming from corporate bucket enterprise. We collected 51 buckets for the city of Maca,
26 Macei and 26 So Paulo. In the latter was considered a single region because the size of
the city.
Sink and float tests with debris fraction from the prismatic stock pile.
CDW Qualities
Macei: coastal city of northeastern Brazil with constructive pattern with clay and mortar.
Maca: today the capital of the oil extraction industry. Twenty years ago was a fishing village
and a harbor of sugar from Campos.
So Paulo: Brazils largest city. The debris came from a central region, post-industrial area.
Factories disable by industrial decentralization. Is the scenario more like the industrial cities in
Europe.
The result shows the regional economic diversity of Brazil.
80
All Mineral Batch JIG
100
So Paulo
80 Maca
Massa acumulada (% kg/kg)
Macei
60
40
20
1,5 1,6 1,7 1,8 1,9 2 2,1 2,2 2,3 2,4
Massa especfica aparente (kg/dm)
Graphic 2. Washability curves
ALL MINERAL JIG. TEST WITH HIGH QUALITY DEBRIS
Graphic 3. Washability Curves
The washability curves in both JIGS were predictable with the empirical density tests.
Crushers test
Almost all the recycled aggregate is used for sub-base and base pavement. The challenge is to
create market for higher value applications, such as non-structural concrete. The adjustment
grain size (particle size) is essential to ensure the possibility of using recycled aggregate in
construction activities.
The products generated by the impact crusher and the crusher jaw were: coarse aggregate (-
25.4 + 4.8 mm) and fine aggregate (-4.8 mm). It does not depend on the type of crusher
:impact or jaw.
81
HQ-Jaw MQ-Jaw LQ-Jaw LQ-Jaw
HQ-Imp MQ-Jaw
Graphic 4. This graphic shows the quality of the products generated in the 3 cities by the two
types of crushers: impact and jaw
Feasibility of the CDW recycling plants

The bucket with rubble passes through a visual inspection in order to reject the contaminant
materials and also buckets with very heterogeneous materials. The load is placed in a stock pile
where occurs a manual picking up, which separates the non-mineral fractions as plastic, glass,
wood,a.s.o. Mineral fraction is taken by retro excavators to the feeder, followed by the crushing
step, where there will be a size reduction operation; and a magnetic separation of ferrous
metals followed by particle size separation .
Recycled products in Brazil are mostly coarse aggregates and crusher fines are used in landfills
and paving. The recycled aggregates in countries where recycling are an industrial subsector
are of high quality, being used as non-structural concrete and mortar.
To establish a disposal fee that enables the economic viability of an enterprise not only
economic variables were analyzed as the Minimum Rate of Attractiveness / (EBA), Internal Rate
of Return (IRR), Net Present Value (NPV), payback, costs production, overhead, operating
income, but also established some assumptions based on actual conditions under which the
project is located. Although fundamental, were not considered the learning costs` for the
formation of recycled aggregates market. Only the costs of operating a recycling plant have
been considered and CDW transport costs for both the landfill and for recycling, are considered
the same
Based on these concepts in economic and market conditions, it has been proposed to run
circuits of unit operations so as to produce three types of products with different applications:
1. Coarse aggregate - low added value, mainly used for paving sub-base and embankments.
2. Crusher fines - average value, mainly used as a basis for concrete paving and non-
structural concrete
3. Fine sand and recycled washed gravel - high value, mainly used in the manufacture of
structural concrete and mortar, respectively, but the market still incipient.
For each category a specific circuit was simulated with different production and number of
employees and equipment for each specific case. Research was conducted in prices, rates of
wages, cost of land, the selling price of these aggregates in the market, cost estimates of water
and electricity, as well as percentage of rejects. Some assumptions were common to the three
cases:
Size of plant: 50t / h. Land Price: $ 50.00 / m2
Labor: was divided into qualified and unqualified manager, with wages of $ 3,000.00 R $
1,200.00 and $ 5,000.00 respectively, including charges.
Electricity: $ 0.35 / kWh, and water: $ 1.75 / m3
Gradient of growth, due to the acceleration of the volume of work to attend the World Cup,
Olympics and real estate: 10% pa
Planning horizon: 10 years
Minimum rate of attractiveness, considering the Selic rate at 12.25% per year: 14.00% pa
Percentage of waste that is not processed: 20%, to $ 15.00 for final disposal.
82
Sales price of coarse aggregate,crusher fine, washed sand and gravel recycled: R $ 17.00 /
m3, $ 20.00 / m3 U.S. $ 40.00 / m3 and $ 30.00 / m3, respectively.
No funding and the only sources of revenue are the sale of products and the disposal fee
charged for every bucket that comes into the plant.
Based on these premises, a sensitivity analysis of IRR was carried out to check the minimum
disposal price which cancels the net present value and makes the project economically viable.
The circuit used to produce just coarse aggregate is simple, relying on picking up and feeding
operations, which requires less space and fewer employees. To get the crusher run, it is
imperative to add an impact crusher and a set of sieves to the previous circuit, requiring larger
area and more employees. As for obtaining fine washed sand and gravel recycled more
complex unit operations are required , such as jigging, a Vertical Shaft Impact crusher, binders
and spiral. The circuit is shown below in Figure 2:
Figure 2 Simplified Circuit for obtaining recycled fine sand and gravel.
Based on the assumptions and projections for the three circuits was possible to predict what
minimum rate of discharge would make the business viable, ie, the net present value would be
zero. The result is shown in the following table:
Table 1. Comparative table of three circuits analyzed
Circ. Area/ Main Products Main use Unitary Waste

employees equipment and cost and deposition
prices (in payback charge
thousand (VPL=0)
reais)
83
2
1 15.000m 1 Feeder (200), Coarse sub-bed R$14,89/t R$36,28/
2 technical 1 belt conveyor aggregate paving and 6.11 bucket
staff hand selection (100%) earthwork years
8 labor (150), 1
intensive magnetic
workers separator (150)
1 manager
2
2 20.000m 1+ 1 crusher 1(40%)+ 1+ paving R$17,61/t R$44,16/
3 technical (380), sieve Crusher bed 6 years bucket
staff (150) fine (60%)
10 labor
intensive
workers
1 manager
2
3 20.000m 1+2+ 1 1(20%)+ 2 1+2+ R$22,70/t R$31,85/
5 technical Secondary (30%)+ fine Concrete . bucket
staff crusher (550), sand and mortar 5.9 years
15 labor 1 jig (350), 1 washed sand
intensive crusher VSI (20%),
workers (220), 1 sorter recycled
1 manager (200), 1 spiral gravel
(140), 2 sieve (30%)
By analyzing this table we can see that circuit # 3 is the best option, despite its unit cost of
processing to be higher, because it involves more expensive equipment, greater number of
employees, with a higher initial investment, the amount of revenue generated is larger.
In cities like Rio de Janeiro, where the price of disposal in landfills is currently $ 15.00 / bucket,
the deployment of these plants is economically unfeasible.
CONCLUSIONS
The study shows that in Brazil the urban infrastructure and buildings generate a construction
and demolition waste with sharp regional differences due to variation in construction patterns .
In this way the construction and demolition waste has distinct values for recycling purposes.
The use of recycled aggregates ranges from base or sub base for paving up to the substitution
of natural gravel in non-structural concrete.
To strengthen the nascent market of recycled aggregates it is recommended to build recycling
plants with layouts according to regional differences.
For the establishment of recycling companies government measures are still needed to
increase the price of disposal when compared to the cost of processing CDW.
References
[1] ngulo, S. C.;Carrijo P. M.;Figueiredo A. D.;Chaves A.P.,John V. M.: On the classification of
mixed construction and demolition waste aggregate by porosity and its impact on the
mechanical performance of concrete. Material and Structure , May 2009.
[2]ngulo S.C. ET AL.2005. Anlise comparativa da tecnologia de processamento na
reciclagem da frao mineral dos resduos de construo e demolio In:XXI Encontro
Nacional de Tratamento de Minrios e metalurgia Extrativa, p.305-312.
[3]Chaves, A.P. Teoria e Prtica do Tratamento de Minrios, 2 Edio, Ed. Signus, So
Paulo
[4] Buntenbach, S. et al. 1997. Wet Processing of Demolition Rubble> Aufbereitungs-technik
38 n3, p.130-138.
[5] Muller, A; Wienke ,L Measurements and models for gravity concentration of C&D waste
through jigging. In: International RILEM Conference on the use of recycled materials in building
and structures, 2004.Proceedings.Elsevier Publications, 2004. V1. P. 115-122.
84
TYRE RUBBER WASTES BASED CONCRETE: A REVIEW.

1 2 3
F.Pacheco Torgal , A. Shasavandi and S. Jalali
1 Research Unit C-TAC, University of Minho, Guimares, torgal@civil.uminho
2 Research Unit C-TAC, University of Minho, Guimares, arman.sh@civil.uminho
3 Research Unit C-TAC, University of Minho, Guimares, said@civil.uminho
ABSTRACT
The volume of tyre rubber wastes is increasing at a fast rate. An estimated 1000 million
tyres reach the end of their useful lives every year and 5000 millions more are expected
to be discarded in a regular basis by the year 2030. Up to now a small part is recycled
and millions of tyres are just stockpiled, landfilled or buried. This paper reviews research
published on the performance of concrete containing tyre rubber wastes. It discusses the
effect of waste treatments, the size of waste particles and the waste replacement volume
on the fresh and hardened properties of concrete.
Keywords: Tyre rubber wastes; concrete; properties; durability
INTRODUCTION
Tyre rubber wastes represents a major environmental problem of increasing relevance. An
estimated 1000 million tyres reach the end of their useful lives every year. At present enormous
quantities of tyres are already stockpiled (whole tyre) or landfilled (shredded tyre), 3000 millions
inside EU and 1000 millions in the US [1]. By the year 2030 the number of tyres from motor
vehicles is expect to reach 1200 million representing almost 5000 millions tyres to be discarded in
a regular basis. Tyre landfilling is responsible for a serious ecological threat. Mainly waste tyres
disposal areas contribute to the reduction of biodiversity also the tyres hold toxic and soluble
components [2]. Secondly although waste tyres are difficult to ignite this risk is always present.
Once tyres start to burn down due to accidental causes high temperature take place and toxic
fumes are generated besides the high temperature causes tyres to melt, thus producing an oil that
will contaminate soil and water. In Wales a tyre dump with 10 million tyres has been burning
continuously for nine years [3]. The implementation of the Lanfill Directive 1999/31/EC and the End
of Life Vehicle Directive 2000/53/EC banned the landfill disposal of waste tyres creating the driving
force behind the recycling of these wastes. Still millions of tyres are just being buried all over the
world. Tyre rubber wastes are already used for paving purposes, however, it can only recycle a
part of these wastes [4]. Another alternative are artificial reef formation but some investigation have
already questioned the validity of this option [5]. Tyre waste can also be used in cement kilns for
energetic purposes and to produce carbon black by tyre pyrolisis [6], a thermal decomposition of
these wastes in the absence of oxygen in order to produce by-products that have low economic
viability. Some research has already been conducted on the used of waste tyre as aggregate
replacement in concrete showing that a concrete with enhanced toughness and sound insulation
properties can be achieved. Rubber aggregates are obtained from waste tyres using two different
technologies: mechanical grinding at ambient temperature or cryogenic grinding at a temperature
below the glass transition temperature. The first method generates chipped rubber to replace
coarse aggregates. As for the second method it usually produce crumb rubber to replace fine
aggregates. In this work the most relevant knowledge about the properties and the durability of
concrete containing tyre rubber wastes will be reviewed. Furthermore it discusses the effect of
waste treatments, the size of waste particles and the waste replacement volume on the fresh and
hardened properties of concrete. Investigations carried out so far reveal that tyre waste concrete is
specially recommended for concrete structures located in areas of severe earthquake risk and also
for applications submitted to severe dynamic actions like railway sleepers. This material can also
85
be used for non load-bearing purposes such as noise reduction barriers. Investigations about
rubber waste concrete show that concrete performance is very dependent on the waste
aggregates. Further investigations are needed to clarify for instance which are the characteristics
that maximize concrete performance.
FRESH CONCRETE PROPERTIES

Workability
Albano et al. [9] replace fine aggregates by 5% and 10% of scrap rubber waste (particle sizes of
0.29mm and 0.59mm) reporting a decreased of 88% in concrete slump. Bignozzi & Sandrolini [10]
used scrap-tyre (0.5 to 2mm) and crumb-tyre (0.05 to 0.7mm) to replace 22.2% and 33.3% of fine
aggregates in self-compacting concretes referring that the introduction of the rubber particles does
not influence the workability in a significant way if the superplasticizer also increases. Skripkiunas
et al. [11] used crumbed rubber to replace 23 kg of fine aggregates in concretes with 0.6% of a
policarboxile superplasticizer by cement mass obtaining the same workability of the reference
concrete. Other authors [12] used crumb rubber tyres (0.075 to 4.75mm) in the concrete to replace
sand in various percentages (20%, 40%, 60% and 100%). These authors stated that increasing
rubber waste content decreases the concrete slump (Table 1).
Table 1 Slump performance according to crumb rubber content [12]

Rubber content (%) Slump (mm)
0 75
20 61
40 36
60 18
80 10
100 5
Freitas et al. [13] used scrap-tyre (0.15 to 4.8mm) in the replacement of sand reporting a slump
decrease along with the increase of scrap-tyre content. However, these authors used 1% by
cement mass of an unknown plasticizer in the mixtures with tire wastes, so the workability
reduction is probably related to the low performance of the plasticizer. Topu & Bilir [14] studied the
influence of rubber waste with a maximum dimension of 4mm in self-compacting concretes noticing
that rubber replacing sand increase concrete workability which is due to the presence of viscosity
3
agents even to a volume of 180kg/m . Aiello & Leuzzi [15] used tyre shreds (Fig. 1) to replace fine
and coarse aggregates (10mm to 25mm) with 1% by cement mass of a plasticizer observing
increase workability with tire shreds content.
Fig.1 Rubber particle during the mixture of concrete [25]
86
Guneyisi [16] used crumb rubber waste to replace sand in self-compacting concretes in different
percentages (5, 15 and 25) and using also a polycarboxylic superplasticizer with different amounts.
This author noticed that the mixture with 25% of rubber waste although containing 4% by cement
mass of the superplasticizer did not achieved the target slump flow of 750mm 50mm. He also
reported that adding fly ash helps to lower the amount of superplasticizer in the mixtures with high
rubber waste content. Although the majority of investigations show that rubber aggregates lead to a
decrease in concrete workability some authors reported the no workability loss and others even
observed the opposite behaviour this means that workability is very dependent on the
characteristics of the rubber aggregates. Future investigations should study what rubber wastes
could be used to produce self-compacting concretes.
HARDENED CONCRETE PROPERTIES

Compressive strength
Guneyisi et al. [17] mentioned that the strength of concretes containing silica fume, crumb rubber
and tyre chips decreases with rubber content. These authors suggest that it is possible to produce
a 40MPa concrete replacing a volume of 15% of aggregates by rubber waste. Ghaly & Cahill [18]
studied the use of different percentage of rubber in concrete (5%, 10%, and 15%) by volume also
noticing that as rubber content increase leads to a reduction of compressive strength. Valadares
[19] studied the performance of concretes with the same volume replacement of rubber wastes
confirming the decrease of compressive strength. Ganjian et al. [20] also confirmed the decrease in
compressive strength for increase rubber content. However, these authors obtained a slight
increase in compressive strength when 5% of chipped rubber replaced the coarse aggregates
probably due to a better grading of the mixture. This finding had already caught the attention of
other authors [21,22]. Snelson et al. [23] used concretes with shredded tyre chips (15 to 20mm) for
aggregate replacement in several percentages (2.5%, 5% and 10%) reporting a loss in
compressive strength. The results show that the rubber mixtures also containing pulverised fuel
ash as partial cement replacement presented major compressive strength loss. This means that
the low adhesion between the cement paste and the rubber waste becomes even lower if
admixtures with low pozzolanic activity are used. Aiello & Leuzzi [15] used tyre shreds to replace
fine and coarse aggregates concluding that the size of the rubber particles have a major influence
on the compressive strength. When coarse aggregates are replaced by the tyre particles the
compressive strength loss is much more profound when compared to the compressive strength
loss of concretes in which fine aggregates were replaced by rubber particles (Table 2).
Table 2 Compressive strength of concrete with aggregates replaced

by rubber particles [15]
Mixture Compressive strength Compressive strength
(MPa) decrease (%)
Reference concrete with rubber waste 45.8 -
replacing coarse aggregates (W/B=0.52)
25% rubber vol. 23.9 47.8
50% rubber vol. 20.9 54.4
75% rubber vol. 17.4 61.9
Reference concrete with rubber waste 27.1 -

replacing fine aggregates (W/B=0.60)
15% rubber vol. 24.0 11.6
30% rubber vol. 20.4 24.7
50% rubber vol. 19.5 28.3
75% rubber vol. 17.1 37.1
These results contradict the ones presented by Valadares [19] and that may be related to the origin
of the wastes used in each case (car, truck or motorcycle) being that different origin may possess
different chemical compositions leading to different adhesion between the cement paste and the
rubber waste. Vieira et al. [8] studied three types of rubber waste and three volume percentages
(2.5%; 5% and 7.5%) reporting that the best mechanical performance was obtained using just 2.5%
87
of the tire rubber with 2.4mm. Several authors mentioned the use of pretreatments of rubber waste
to increase the adhesion between the cement paste such as the use of a 10% NaOH saturated
solution to wash the rubber surface during 20 minutes [24,25]. Raghavan et al. [26] confirms that
the immersion of rubber in NaOH aqueous solution could improve the adhesion leading to a high
strength performance of concrete rubber composites. The NaOH removes zinc stearate from the
rubber surface, an additive responsible for the poor adhesion characteristics, enhancing the
surface homogeneity [27].Segre et al. [28] mention several pretreatments to improve that the
adhesion of rubber particles like acid etching, plasma and the use of coupling agents. Cairns et al.
[5] used rubber aggregates coated with a thin layer of cement paste (Fig.2).
Fig.2 20 mm rubber aggregate particles: a) Plain; b) Coated with cement paste [5]
Oikonomou et al. [29] mentioned that the use of SBR latex enhances the adherence between the
rubber waste and the cement paste. Chou et al. [30] suggest the pretreatment of crumb rubber with
organic sulfur stating it can modify the rubber surface properties increasing the adhesion between
the waste and the cement paste. Investigations about rubber waste concrete show a compressive
strength loss with waste content increase. Further investigations are needed on this subject,
especially to comprehend if different kinds of rubber behave in a similar manner to the same
treatment.
TOUGHNESS
Concrete composites containing tyre rubber waste are known for their high toughness [31], having
a high energy absorption capacity. The ASTMC1018-97 [32] defines several toughness indexes (I5,
I10 and I20) as the area under load-deflection curve of a flexural specimen for different times of
deflection after crack initiation related to area under the same curve up to the crack initiation. Some
authors [33] report a 63.2% increase in the damping ratio (self capacity to decrease the amplitude
of free vibrations) for concrete containing 20% rubber particles. Other authors [34,35] confirmed the
high damping potential of rubber waste concrete. They mentioned that concrete with ground rubber
shows a 75.3% increase in the damping ratio and a 144% for crushed rubber concrete (Fig.6).
Fioriti et al. [36] mentioned that concrete paving blocks containing 8% of tyre rubber waste (have a
resistant impact of almost 300% when compared to the reference concrete. These means that tyre
waste concrete maybe specially recommended for concrete structures located in areas of severe
earthquake risk and also for the production of railway sleepers.
MODULUS OF ELASTICITY
Since the concrete with rubber waste has low compressive strength and a correlation exists
between compressive strength and the modulus of elasticity it is expected they also possess lower
modulus of elasticity. However, Skripkiunas et al. [21] compared concretes with similar
compressive strength (a reference one and another with 3.3% of crumb rubber) obtaining different
static modulus of elasticity, 29.6 GPa versus 33.2GPa for the reference concrete just 11% higher.
The explanation for this behaviour is related to the low modulus of elasticity of rubber waste [37].
Other authors [38] report a decrease in the modulus of elasticity of 40% when the same percentage
reduction takes place for compressive strength. Khaloo et al. [39] confirmed that the inclusion of
tyre rubber particles leads to a high ductility concrete. Zheng et al. [34,35] mentioned that the
88
crumb rubber (80%<2,62mm) has a lower influence in the modulus of elasticity than the crushed
rubber (15-40mm). Other authors [40] studied the modulus of elasticity of concrete columns with
two different sizes of crumb rubber (0.6 and 1mm) reporting an increase in the ductility
performance up to 90%. Those authors mentioned that crumb rubber concrete columns can
undergo twice the lateral deformation before failure compared to the reference concrete columns.
Mohammed [41] confirmed that concrete slabs containing crumb rubber with a finesses modulus of
2.36 shows a higher ductility behaviour which fulfill the ductility requirements of Eurocode 4 [42].
DURABILITY
Since rubber waste concrete has lower compressive strength than reference concrete it is
expected that is behaviour under fast mechanical degradation actions could also be lower. Topu &
Demir [43] mentioned that a high volume replacement of sand by rubber waste (1-4mm) has lower
durability performance assessed by freeze-thaw exposure, seawater immersion and high
temperature cycles. According to them the use of a 10% replacement is feasible for regions without
harsh environmental conditions. Ganjian et al. [20] studied the durability of concrete containing
scrap-tyre wastes assessed by water absorption and water permeability revealing that a
percentage replacement of just 5% is associated with a more permeable concrete (36% increase)
but not a more porous one. Increasing the rubber percentage replacement to 10% doubles the
concrete water permeability which means this kind of concrete cannot be used for applications
where water pressure is present like underwater columns. The durability of rubber waste concrete
is a subject that needs further investigations. How different wastes influence durability parameters
and most importantly how waste treatment can enhance the concrete durability are questions that
must be addressed.
CONCLUSIONS
Tyre rubber wastes represent a serious environmental issue that needs to be addressed with
urgency by the scientific community. Investigations carried out so far reveal that tyre waste
concrete is specially recommended for concrete structures located in areas of severe earthquake
risk and also for applications submitted to severe dynamic actions like railway sleepers. This
material can also be used for non load-bearing purposes such as noise reduction barriers.
Investigations about rubber waste concrete show that concrete performance is very dependent on
the waste aggregates. Further investigations are needed to clarify for instance which are the
characteristics that maximize concrete performance. Nevertheless, future investigations should
clarify which treatments can maximize concrete performance being responsible for the lowest
environmental impact.
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41 (2007)1209-1220.
[5] R. Cairns, H. Kew, M. Kenny,The use of recycled rubber tyres in concrete construction. Final
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89
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[14] I. Topu, T. Bilir, Experimental investigation of some fresh and hardened properties of
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[31] G. Li, G. Garrick, J. Eggers, C. Abadie, M. Stubblefield, S. Pang, Waste tire fiber modified
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[33] M. Balaha, A. Badawy, M. Hashish, Effect of using ground waste tire rubber as fine aggregate
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[34] L. Zheng, S. Huo, Y. Yuan, Experimental investigation on dynamic properties of rubberized
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91
13th September
Session 2.2
( INNOVATIVE WASTE TREATMENT TECHNOLOGIES 1 )
Chairman: Pablo Kroff
92
REMOVAL OF PHOSPHATES FROM A SYNTHETIC WASTEWATER USING

BIOMASS ASHES
1 1 1 1
A.Morujo , R.Barbosa , N. Lapa and B. Mendes
1 Universidade Nova de Lisboa, Faculdade de Cincias e Tecnologia, Departamento de Cincias e
Tecnologia da Biomassa, Ed. Departamental, Piso 3, Gab. 377, Campus da Caparica. 2829-516
Caparica, Portugal.
E-mail: ncsn@fct.unl.pt
ABSTRACT
The discharge of excessive concentrations of phosphorus in treated wastewaters leads to
environmental problems such as eutrophication of natural water bodies. This work
studied the phosphate removal potential from a synthetic wastewater of biomass ashes
(bottom and fly ashes).
Ca, Al and Fe were the metals with higher expression in both types of biomass ashes,
making them suitable materials for phosphate sorption. Results showed good removal
efficiencies of phosphates without introducing significant amounts of metals in the treated
wastewater. Fly ashes were more efficient than bottom ashes, since they required a
smaller mass of ash to achieve a phosphate removal higher than 99%.
Ecotoxicological assays showed that the addition of biomass ashes did not contribute to
any degree of toxicity to the synthetic wastewater.
The results suggest that the use of biomass ashes could be a promising solution for the
removal of phosphates in the wastewater treatment.
Keywords: Biomass ashes; Wastewater; Phosphate removal; Heavy metals.
INTRODUCTION
Phosphorus is an essential nutrient in aquatic environments. But, when discharged in high
concentrations in treated wastewaters, it stimulates the growth of photosynthetic algae and toxic
cyanobacteria leading to eutrophication problems [1,2,3]. The European Union established the
concentrations of 1 and 2 mg P/L as the limit values of total phosphorus for the discharge of
effluents coming from urban wastewater treatment plants. However, some countries followed
stricter limit values to control eutrophication (0.5-0.8 mg P/L) [4].
Several techniques, such as biological and chemical treatments, have been widely investigated to
remove phosphates from wastewaters [1,2,3]. Adsorption is one of the techniques comparatively
more useful and economical. The application of low cost and widely available materials in P-
adsorption has been gaining great interest [2,3].
Recently, Portugal has been investing in the implementation of new technologies for renewable
electricity production, such as forest biomass power plants. The technologies used to produce
electricity from forest biomass also produce solid wastes - fly and bottom ashes - that must be
recycled or disposed of properly.
Compared to coal y ashes in which signicant research has already been done, the use of
biomass ashes for wastewater treatment is not widely reported. The characteristics of biomass
ashes are quite diverse depending on the type of biomass, soil and biomass harvesting method [5].
Nevertheless, the presence of several strongly active metals, such as Ca, Al and Fe, makes
biomass ashes a suitable material for phosphate sorption [1,6,7].
The aim of this work was to study the phosphate removal potential of biomass ashes (fly and
bottom ashes) through batch studies applied to a synthetic wastewater.
93
Biomass ashes origin and characterisation

Two types of biomass ashes were used fly and bottom ashes. These biomass ashes were
collected in a Portuguese biomass power plant that produces electricity by burning eucalyptus and
pine bark in a Bubbling Fluidized Bed Combustor (BFBC). Bottom ashes were collected in the
bottom of BFBC and fly ashes were collected in bag filters. Only sand is used in this BFBC as bed
material.
Both ashes were characterized for their particle size distribution. The size fractionation was made
using the following meshes: 20, 50, 200, 500, 850, 2000, 4000 and 10000 m. The screening was
performed mechanically using a Retsch AS-200 sieve (ISO 3310-2 [8]).
Each of the biomass ash samples was submitted to a microwave acidic digestion with nitric acid
and hydrochloric acid (3:1 v/v) (Milestone Ethos 1600 microwave digestion system), in closed
vessels with temperature control (USEPA Method 3051A [9]). The acidic digested samples were
filtered through glass fiber filters to remove the insoluble solid fraction.
The biomass ashes were also subjected to a leaching test according to the European standard EN
12457-2 [10]. This test was performed in a single batch extraction cycle of 24 hours, with deionized
water, at L/S ratio of 10 L/kg and constant temperature of 201C. The eluates were filtered and
preserved for further characterization.
The acid digested samples and the eluates were characterized for the following parameters: Al, As,
Ba, Ca, Cd, Cr, Cu, Fe, Hg, K, Mg, Mo, Na, Ni, P, Pb Sb, Se and Zn (APHA/AWWA/WEF [11]).
Phosphate standard solution synthetic wastewater

The phosphate standard solution, named as synthetic wastewater, used in the P-removal batch
assays was prepared by dissolving a stock solution of Na2HPO4.12H2O to the desired
concentration. The P-removal batch tests were carried out with an initial phosphate equivalent
concentration of 20 mg P/L and a pH value of 8.5.
P-removal batch assays

P-removal batch assays were conducted as follows: 500 ml of phosphate standard solution was
added to glass jars. Known amounts of fly and bottom ashes (Table 1) were then added to each
phosphate solution. The mixtures were stirred for a period time of 1 min, at 100 rpm, followed by a
slow stirring period of 15 min, at 40 rpm, and a final settling period of 30 min. These batch assays
were performed at constant temperature of 201C.
Table 1 Amounts of ashes used in the P-removal batch assays.
Samples Ratio Solid/Liquid (S/L) [g/L]

Fly Ashes 0.084 0.17 0.33 0.67 1.34 3.35 6.69 13.38 26.76 53.53
Bottom Ashes 0.57 1.13 2.26 4.52 9.05 18.10 36.20 72.39
The supernatants were filtered through a 0.45 m nitrate cellulose membrane. 100 ml of the filtered
solution was preserved for analysis of phosphate (colorimetric method using a Shimadzu UV-120-
11 spectrophotometer) and 50 ml was preserved for quantification of Al, Ca, Fe, Ba and Sb (atomic
absorption spectrometric method by using a Thermo-Unicam ATI 939 AAS) [11]. Al, Ca and Fe
were quantified because they are the predominant elements involved in P-adsorption processes.
Ba and Sb were quantified due to the fact of being the heavy metals that leached more significantly
from both ashes.
Toxicity assays
Three filtered supernatants resulting from the P-removal batch assays, corresponding to the
lowest, intermediate and highest phosphate removal rates were submitted to toxicity assays. The
phosphate standard solution, without any addition of biomass ashes, was also tested for toxicity as
control.
94
Toxicity assessment was conducted by using two toxicity tests comprising the luminescent bacteria
Vibrio scheri and the micro-crustacean Artemia franciscana.
The cultivation of luminescent bacteria and toxicity evaluation was performed according to the

Microtox test (ISO 11348-3) [12]. The Microtox test measures the light output of the marine
luminescent bacteria V. scheri, after its exposure to supernatants samples. The toxicity of the
supernatants was performed by using the Whole Effluent Toxicity (WET) protocol, after a pH
adjustment to a value of 8.0.
Toxic effects of supernatants on A. franciscana was determined by using the protocol described in
the standardized toxicity test kit Artoxkit M, provided by MicroBioTests Inc. (Belgium). After adding
the nauplii to the test wells, previously filled with 1 ml of the corresponding diluted supernatant, the
plates were covered and incubated at 25C, in the dark, for 24h. The counting of immobile nauplii
in each test well allowed evaluating the toxicity of the supernatants.
Fractionation of biomass ashes

Figure 1 shows the particle size distribution of biomass ashes (bottom and fly ashes).
Fig. 1 - Particle size distribution of biomass ashes (bottom and fly ashes) (% w/w db).
The more representative fractions of fly ashes were the size fraction interval of 20-50 m (48.0%
w/w db), followed by the size fraction interval of 50-200 m (36.3% w/w db). In what concerns the
bottom ashes, the most representative fractions were the size fraction interval of 850-2000 m
(34.9% w/w db) followed by the size fraction interval of 500-850 m (24.1% w/w db).
Chemical characterization of the acidic digested samples and eluates

Table 2 shows the results of the chemical characterization of acidic digested samples and eluates
of biomass ashes (fly and bottom ashes).
In the acidic digested samples of fly ashes, the concentrations of Cd, Pb, Hg, Mo and Ni were
below the Quantification Limits (QL). The metals that showed the lowest concentrations (<1 mg/kg)
were Sb, As and Se. Cu, Cr, Ba, Na, Zn and P also presented low concentrations, but more
significant than those already mentioned above, ranging between 33.1 mg/kg and 1,953 mg/kg.
The main metals present in the acidic digested samples of fly ashes were Fe (13,527 mg/kg), K
(17,529 mg/kg), Mg (22,317 mg/kg) and Al (24,273 mg/kg). Calcium was the metal that showed the
highest concentration in the acidic digested sample of fly ashes (258,577 mg/kg).
In what concerns the eluates of fly ashes, the concentrations of Cd, Cr, Fe, Pb, Hg, Mo, Ni, Se and
Zn were below the QL. The concentrations of Sb, As, Cu, Mg, K, Al and P were relatively low
(3.40 mg/kg), which resulted in low percentages of solubilization apart from Cu (2.99%) and K
(6.46%). Although Ca was the element with the highest concentration, as in the acidic digested
samples, with a concentration of 15,436 mg/kg, it has shown a relatively small percentage of
solubilization (5.97%). The concentrations of Ba and Na, 50.30 mg/kg and 337.5 mg/kg,
95
respectively, were lower than the concentration of Ca. However, these two metals have shown
higher percentages of solubility than Ca, 14.98% and 17.28% respectively.
Table 2 Chemical characterization of the acidic digested samples and eluates of biomass ashes
(fly and bottom ashes) (values expressed in dry basis).
Fly ashes Bottom ashes

Chemical element Acidic % Acidic %
Eluate Eluate
Digested solubilization Digested solubilization
Al (mg/kg) 24,273 3.40 0.01 2,892 3.39 0.12
Sb (g/kg) 1.79 0.0044 0.25 0.745 0.0065 0.88
As (g/kg) 6,273 8.9 0,14 798 <3.2 -
Ba (mg/kg) 336 50.30 14.98 102 4.66 4.55
Cd (mg/kg) <13.4 <0.32 - <12.6 <0.32 -
Ca (mg/kg) 258,577 15,436 5.97 260,854 11,413 4.38
Cr (mg/kg) 48.6 <0.5 - <19.6 <0.5 -
Cu (mg/kg) 33.1 0.99 2.99 <16.1 <0.41 -
Fe (mg/kg) 13,527 <0.6 - 2,327 <0.6 -
Pb (mg/kg) <41.9 <1.0 - <33.5 <1.0 -
Mg (mg/kg) 22,317 0.175 0.001 4,627 0.495 0.01
Hg (g/kg) <503 <12.0 - <470 <12.0 -
Mo (mg/kg) <41.1 <0.98 - <38.4 1.98 5.16
Ni (mg/kg) <26.4 <0.63 - <24.7 <0.63 -
K (mg/kg) 17,529 1,132 6.46 3,419 104 3.06
Se (g/kg) 1,612 <9.1 - 3,101 <9.1 -
Na (mg/kg) 1,953 337.5 17.28 283 13.68 4.84
Zn (mg/kg) 142 <0.13 - 30.3 <0.13 -
P (mg/kg) 1,554 1.02 0.07 516 1.88 0.37
In the acidic digested samples of bottom ashes, the concentrations of Cd, Cu, Cr, Pb, Hg, Mo and
Ni were below the QL. Differently from fly ashes, Cu and Cr have shown concentrations below the
QL. Similarly to what was observed for the acidic digested sample of fly ashes, Sb, As and Se were
the metals that showed the lowest concentrations (<1 mg/kg). Despite of having higher
concentrations than the previous metals, Zn, Ba, Na and P have shown low concentrations,
ranging from 30.3 mg/kg up to 516 mg/kg. Comparing to fly ashes, these four metals have shown
lower concentrations in bottom ashes. Fe (2,327 mg/kg), Al (2,892 mg/kg), K (3,419 mg/kg) and Mg
(4,627 mg/kg) were the major metals present in the bottom ashes. Similar results were found in fly
ashes although in lower concentrations. Ca was once again the element with the highest
concentration of 260,854 mg/kg.
The concentrations of As, Cd, Cu, Cr, Fe, Pb, Hg, Ni, Se and Zn in the eluates of bottom ashes
were below the QL. Sb, Mg, Al and P have shown low concentrations (3.39 mg/kg), as it was
registered for fly ashes, which resulted in a percentage of solubilization below 1%. Although having
different concentrations, Ba (4.66 mg/kg), Na (13.68 mg/kg), K (104 mg/kg) and Ca (11,413 mg/kg)
had relatively similar percentages of solubilization. The concentrations of Ba, Na and K in the
eluates of bottom ash were significantly lower than in the eluates of fly ashes. Consequently, the
percentages of solubilization were smaller than in fly ashes.
P-removal batch assays

Figure 2 shows the P-removal efficiencies from the synthetic wastewater as a function of the
increasing S/L ratio of bottom and fly ashes.
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Fig. 2 - P-removal efficiencies as a function of S/L ratio of bottom and fly ashes.
The highest removal percentages of phosphates (99%) were achieved in the dosages of fly and
bottom ashes of 3.35 and 18.10 g/L, respectively. Fly ashes needed about 6 times less mass than
the bottom ash to achieve the same high removal percentage of phosphates.
The use of both biomass ashes did not cause any contamination of heavy metals in the treated
effluent. The concentrations of Sb (0.3 g/L), Ba (0.16 mg/L) and Fe (0.06 mg/L) present in the
supernatants were always below the QL, except the supernatant in which the maximum dosage of
fly ashes (53.53 g/L) was applied where a Ba concentration of 1.19 mg/L was determined. In what
concerns to Ca, its concentration in the treated wastewater increased with the increasing dosage of
both fly and bottom ashes. The maximum concentration of Ca present in the supernatants after the
treatment with fly ashes was of 157.04 mg/L and in the treatment with bottom ashes was of 108.79
mg/L. The concentration of Al also tended to increase with the increasing dosage of ashes. The
maximum concentration of Al present in the supernatants after the treatment with fly ashes was of
6.97 mg/L and after the treatment with bottom ashes was of 2.34 mg/L.
Ecotoxicological characterization of the supernatants

The results of the ecotoxicological characterization of the supernatants are summarized in Table 3.
Table 3 Ecotoxicological characterization of three supernatants produced in the P-removal batch

assays
V. fischeri A. franciscana
Supernatants
EC50-30 min EC50-24 h
Synthetic wastewater (Control) 99% 90%
Fly ash addition of 0.084 g/l 99% 90%
Bottom ash addition of 0.57 g/l 99% 90%
The synthetic wastewater without any addition of biomass ashes presented an EC50-30 min higher
than 99% for V. fischeri and an EC50-24 h higher than 90% for A. franciscana. These data indicate
that the synthetic wastewater had no toxicity for both bioindicators tested.
97
The population of V. fischeri exposed to the supernatants resulting from the addition of fly ashes
had an EC50-30 min above 99%. For A. franciscana, the EC50-24h was greater than 90%.
Therefore, it was possible to conclude that the supernatants produced with the three dosages of fly
ashes tested did not show any level of toxicity for both bioindicators.
Similarly, the supernatants produced after the treatment with bottom ashes presented an EC50-30
min above 99% for V. fischeri and an EC50-24 h higher than 90% for A. franciscana. Hence, it must
be concluded that the dosages of bottom ashes applied did not cause any toxicity to the synthetic
wastewater.
CONCLUSIONS
Ca, Al, Fe, Mg and K were the metals with higher expression in fly and bottom ashes, while the
elements that presented the highest leaching rates were Ca, K, Na and Ba.
Experimental data have shown good removal efficiencies of phosphorus from the synthetic
wastewater, in certain dosages, without introducing significant amounts of metals in the treated
wastewater.
Comparing the two types of biomass ashes used in this study, fly ashes were more efficient than
bottom ashes to remove phosphates, requiring 6 times less mass of ash to achieve a phosphate
removal higher than 99%.
The ecotoxicological tests performed in the supernatants that resulted from three different dosages
of bottom and fly ashes had demonstrated that the synthetic wastewater treatment with these
ashes had not contributed to any degree of toxicity to the wastewater.
The experimental data suggest that the use of these types of ashes could be a promising solution
for the removal of phosphates from wastewaters, being necessary to apply these assays to real
wastewaters to test the P-removal efficiencies in a more complex matrix.
References
[1] K. Xu, T. Deng, J. Liu, W. Peng, Study on the phosphate removal from aqueous solution using
modied y ash, Fuel, 89 (2010) 3668-3674.
[2] S.G. Lu, S.Q. Bai, L. Zhu and H.D. Shan, Removal mechanism of phosphate from aqueous
solution by fly ash, J. Hazard. Mater. 161 (2009) 95101
[3] A. Ugurlu, B. Salman, Phosphorus removal by fly ash, Environ. Int. 24 (1998) 911918.
[4] S. Hussain et al., Orthophosphate removal from domestic wastewater using limestone and
granular activated carbon, Desalination 271 (2011) 265-272.
[5] M. Ahmaruzzaman, A review on the utilization of fly ash, Progress in Energy and Combustion
Science 36 (2010) 327363.
[6] P. Pengthamkeerati, T. Satapanajaru, P. Chularuengoaksorn, Chemical modication of coal y
ash for the removal of phosphate from aqueous solution, Fuel 87 (2008) 2469-2476.
[7] D. G. Grubb, M. S. Guimaraes, R. Valencia, Phosphate immobilization using an acidic type F fly
ash, J. Hazard. Mater. 76 (2000) 217236.
[8] ISO Standard, ISO 3310-2 - Test sieves - Technical requirements and testing - Part 2: Test
sieves of perforated metal plate, 1999.
[9] USEPA, Method 3051A - Microwave assisted acid digestion of sediments, sludges, soils and
oils, Revision 1, February (2007), 30 pp.
[10] CEN, Characterization of waste leaching - Compliance test for leaching of granular waste
materials and sludges - Part 2: one stage batch test at a liquid to solid ratio of 10 l/kg for materials
with particle size below 4 mm (without or with size reduction) (EN 12457-2), European Committee
for Standardization, Brussels, 2002, 27 pp.
[11] APHA/AWWA/WEF, Standard methods for the examination of water and wastewater, twenty-
first ed., American Public Health Association, Washington, 2005.
[12] ISO Standard Water Quality, ISO 11348-3 - Water quality determination of the inhibitory
effect of water samples on the light emission of Vibrio fischeri (luminescent bacteria test) Part 3:
method using freeze-dried bacteria, Genve, 2003, 12 pp.
98
SMALL SIZED PILOT SCALE EXPERIMENTS ON THE RECOVERY COOPER

AND NICKEL HYDROXIDE FROM GALVANIC SLUDGE
1 2 3
M.C. Vilarinho , F. Castro and A. Ribeiro
1 University of Minho/ CT2M, candida@dem.uminho.pt.

2 University of Minho/ CT2M, fcastro@ dem.uminho.pt.
3 CVR Centre for Waste Valorization, aribeiro@cvresiduos.pt.
ABSTRACT
The present work, carried out within the project VALMETAIS, proposes a
hydrometallurgical process for copper and nickel recovery from galvanic sludges
produced by Ni/Cr plating plants. The procedure has been developed on laboratory scale
and the results validation was verified in a small sized pilot scale.
The project starts with a leaching process of sludge in sulphuric acid solution in three
stages followed by copper cementation step, using iron scrap as precipitating agent. It
was found that metals dissolution was almost completed for the three stages of leaching
process. Extraction rates of 99% for Cu and Ni were achieved under the leaching. The
solid residue separated from the leaching solution is mostly constituted by gypsum
(CaSO4), and presents heavy metal content below 1%. Copper cementation process was
performed at a pH of 2. Such pH level led to insignificant precipitation of other metals
present in the leaching solution, particularly chromium. The recovery rate of copper is
about 99% with a purity grade of 99% which enables its application as a commercial
product. Nickel hydroxide precipitation was performed by adding sodium hydroxide
solution. Results showed a successfully nickel hydroxide extraction obtaining 99% with a
purity grade of more than 98%.
These evidences demonstrate the high potential of this methodology to treat and derive
economic benefits from galvanic sludge. The end products cooper and nickel can be
applied as a commercial product generating a profit and the gypsum based sludge from
the leaching process can be reutilized as component of construction materials.
Keywords: Galvanic sludge, Hydrometallurgical process; Metals recovery; Pilot scale experiments
INTRODUCTION
Industrial units of surface metal plating generate wastewaters that need to be treated to produces
good quality water to be recycled into the process. During the wastewater treatment, usually by
physical-chemical methods, significant amounts of sludge are produced. For nickel and chromium
plating processes the resulting sludge is classified as hazardous waste according to Council
Decision 2000/532/CE and represents a potential source of environmental contamination. This
classification is due to the high concentration of mobile/leachable species, such as heavy and/or
transition metals like chromium and nickel [1,2]. In fact, besides water (typical solids content is
under 40%) and some soluble salts, the galvanic sludge is composed of metallic species and
additives and its composition dependent of the processing conditions [3,4]. These sludges are
frequently sent to landfills with no valorization or economic benefits. This is clearly the least
desirable option from both the environmental and economical points of view. For that reason
available alternatives or appropriate routes that enable the valorization of those wastes with
material recovery must be developed.
Different studies have been carried out in order to develop possible technologies for the chemical
fixation of galvanic sludges in clay based ceramic materials, such as common formulations for tiles
and bricks. The main mechanism for the inertization of phases with high levels of heavy metals in
ceramic matrixes was described by Magalhes et al [5,6]. Alternatives technologies for
99
stabilization/solidification of galvanic sludges by asphalt emulsions [7] and the incorporation in
Portland cement clinker [8,9] and silica and feldspar [10] have also been attempted and developed.
Despite these technologies enable the formation of an effective physical and chemical barrier
which reduces the leachibility of the soluble elements, they do not allow the recovery of valuable
metals present in galvanic sludges. Several treatments routes have been proposed in literature to
recover valuable metals contained in those sludges focused on pyrometallurgical or
hydrometallurgical processes. The pyrometallurgical route is based on chemical reactions at high
temperatures and allows recovery rates from 40 and 60% for the target elements Zn, Ni and Cu
[11]. However, these processes present strong constraints since they can only be implemented to
treat wastes within a confined composition regarding a maximum and a minimum content of
selected elements [12]. Additionally the high energy consumption and the need of cleaning
systems and collecting gases make the technique less attractive in relation to the
hydrometallurgical route [13]. Hydrometallurgical processes for sludge valorization have been
proposed by several authors [14-17]. Their works are related with acid or alkaline leaching,
followed by distinct operations for metals recovery namely by solvent extraction (using di-(2-
ethylhexyl)-phosphoric acid (D2EHPA) and bis-(2,4,4-trimethylpentyl)-phosphinic acid
(Cyanex272)) and by electrowinning processes. Although the technologies summarized above are
feasible processes for the management of galvanic sludges it is of great relevance the search and
development of new technically and economically sound alternatives for the treatment and
valorization of those sludges to recover valuable products as well as the optimization of the
operating conditions under which all the steps of a valorization process should be performed.
In this context the project VALMETAIS aimed to develop a process in laboratory scale and validate
the results in a pilot scale for a new hydrometallurgical process to recover nonferrous metals, like
nickel and copper, from galvanic sludges and to decrease the hazardous character and amount of
the remaining waste before final disposal. The hydrometallurgical solution proposed is based in
sequential steps undertaken with lower operational costs than those required for the traditional
extraction processes of solvent extraction and electrowinnning. The technical and economic
feasibility of the whole developed process evaluated at a pilot scale allowed the establishment of
an integrated solution able to be implemented in industry. This project was sponsored by the
QREN (Quadro de Referncia Estratgico Nacional) and CVR - Centro para a Valorizao de
Resduos and W2V, S.A., as the technical partners for the Project. This work presents the most
relevant results of copper and nickel hydroxide recovery from galvanic sludges in a small sized pilot
scale.
HYDROMETALLURGICAL PROCESS TO RECOVER COOPER AND NICKEL HYDROXIDE

The hydrometallurgical process to recover nonferrous metals like copper and nickel hydroxide
comprises different procedural steps, such as:
a. Leaching of galvanic sludge;
b. Recovery of copper by cementation;
c. Elimination of impurities;
d. Recovery of nickel hydroxide.
The experiments of this work were realized in a small sized pilot scale (figure 1). This pilot scale
was built and its materials were selected according to the specifications identified in laboratory
scale methodology. Thus, this pilot scale comprises all steps to leaching of galvanic sludge and for
the recovery of copper and nickel hydroxide.
100
a) b)
Figure 1- Overview of the pilot plant: a) real representation; b) SolidWorks representation
METHODS AND MATERIALS
Characterization of galvanic sludge

For this study galvanic sludge produced by the physico-chemical treatment of wastewaters
generated in an industrial unit of Ni/Cr plating were collected. Sludges have been characterized for
their physic-chemical properties. The chemical composition of dried samples was determined by X-
ray fluorescence (XRF, X Unique II Philips).
Methodology
The process begins with the leaching phase of galvanic sludges realized in three steps at room
temperature and atmospheric pressure under constant agitation. The acid leaching for the
dissolution of constituent metals of galvanic sludges was accomplished with sulphuric solutions.
During leaching test cakes were collected and analyzed by X-ray Fluorescence Spectrometry
(XRF).
In order to recover the copper from the obtained solution, a subsequent process of cementation
has been studied with iron craps at room temperature and atmospheric pressure. For that
operation, the solution obtained from the sulphuric acid leaching with a pH 2.0 was used. The
chemical composition of the obtained cement was observed by SEM and determined by XFR.
Recovery of nickel hydroxide occurs for its precipitation through the solution concentrate in nickel
and frees of others elements. For this was added a sodium hydroxide solution. The chemical
composition of precipitated cake has been determined by XFR.
Small sized pilot scale

The cylindrical agitation tank has a diameter of 350mm and 500 mm in height, with a volume
capacity of 30 L. All tanks are constructed in galvanized iron with 3mm thickness and coated with
cid resistant painting. Mixing is promoted by a rotational engine (BONFIGLIOLI, model BN 71B6)
connected to a horizontal shaft with three propellers in stainless steel to prevent corrosion induced
by acid solutions. To adjust the speed of the propellers it was used a frequency converter
(OMRON, model V1000) coupled to the engine. The filter tank has twice the volume capacity of the
agitation tank and has a perforate plate to filter the solutions.
The cementation tank was built in the same materials as agitation reactor and has two main
components: an upper tank and a bottom tank. In the first tank the re-circulated solution contact the
iron straps and in second tank the cooper precipitates. The re-circulation of the solutions is ensured
by a pneumatic membrane pump (VERSA MATIC, model E8PP6XPP9).
RESULTS
Table 1 shows the chemical composition of the selected galvanic sludge collected in an industrial
unit of Ni/Cr. The results showed that galvanic sludges have high contents of valuable metals such
101
as Cu and Ni, 6.0% and 9.9% respectively. Cr is also present in high contents and Ca to,
consequence of the chemical physical process applied to the wastewater treatment. At the same
time several other elements are present like Cr, Fe, P etc and their presence interferes on the
leaching process through their co-dissolution together with the valuable metals, reducing the purity
of the resulting liquor leach.
Table 1 - Chemical composition (FRX) of dried sludge (wt%)

Elements Results [%]
Ca 9,1
Cr 13,6
Cu 6,0
Fe 3,9
Cl 0,4
K 0,1
Mg 0,5
Na 2,1
Ni 9,9
Pb 0,1
Zn 0,01
Al 0,1
P 8,0
S 2,5
Si 0,1
Sn 0,2
Sr 0,04
Leaching of galvanic sludge

Table 2 shows the chemical composition of the cake filtered and collected after leaching process in
three steps. The results showed that cake is basically formed by CaSO4 (gypsum) and the others
elements are in residual values. This evidence proves that sulphuric acid leaching allows to
dissolve almost all the initial present metals.
Table 2 - Chemical composition (FRX) of dried cake (wt%)

Ca 33,4
Cr 0,3
Cu 0,03
Fe 0,06
Ni 0,01
Sn 0,01
Al 0,04
P 0,7
S 24,5
Si 0,03
others 0,05
Recovery of copper by cementation

Table 3 shows the chemical composition of the cement collected after cementation step with iron
scraps. The results showed a purity grade of 99% in cooper and an extraction yield of 99%.This
high purity confirmed the efficiency of cementation with iron scraps. Figure 2 illustrate the obtained
cement with 99% of copper in SEM determination and real overview.
102
Table 3 - Chemical composition (FRX) of dried cement (wt%)
Al 0,1
Cr 0,02
Cu 99
Fe 0,01
P 0,17
S 0,7
Si 0,04
a) b)
Figure 2- Cement obtained by cementation with iron craps: a) SEM determination; b) real overview
Recovery of nickel hydroxide

Table 4 shows the chemical composition of the collected and filtered cake after nickel hydroxide
recovery step. The results showed a purity grade of 98% in nickel hydroxide. Results also
demonstrated an extraction yield of 99% which prove the adopted methodology.
Table 4 - Chemical composition (FRX) of dried nickel hydroxide

recovery process (wt%)
Cu 0,01
Ni(OH)2 >98
Mg 0,8
Al 0,2
P 0,1
Si 0,5
CONCLUSION
From the experimental work developed in the pilot scale it can be concluded that sulphuric acid
proved to be an efficient leaching media for the first step of a hydrometallurgical process to recover
the valuable metals present in galvanic sludges. Extraction rates of 99% for Ni and Cu were
achieved for the studied operating conditions. In the final of leaching process the galvanic sludges
are converted into a material essentially constituted by gypsum. Thus is eliminated the need for
landfill as hazardous waste which reduce the cost for its management. Gypsum can be also reused
as raw-material in the production of construction materials.
The cementation procedure with iron scraps promotes with success the recovery of Cu from
sulphuric leaching solutions with pH of 2 achieving 99% of extraction. Cement with a purity grade of
99% of cooper was obtained, which has a substantial commercial value.
The nickel hydroxide recovery step with a solution concentrate in nickel achieved an extraction
yield of 99% and a purity grade of more than 98%. These results prove the efficiency of the
methodology selected in this work.
Due to these factors it can be concluded that the methodology studied in this work besides
presenting a way to treat galvanic sludge, presents also an added value through the
commercialization and reuse of the products formed along the process.
103
Acknowledgement: The authors acknowledge to QREN (NORTE-01-0202-FEDER-005509) for
the financial support granted.
REFERENCES
[1] A.M. Bernardes, I. Bohlinger, W. Wuth, Thermal treatment of galvanic sludges for
environmental compatibility, J.O.M. (1996) 59-62.
[2] L. Magalhes, J.E. Silva, F.P. Castro, Labrincha J.A, Physical and chemical characterization
of metal finishing industrial wastes, Journal of Environmental Management 75 (2005) 157-
166.
[3] F.P Castro, Ecoinertinertization of metallurgical wastes by stabilization in ceramic
products, Technical Report CRAFT Project no. BE-S2-2260 (1999).
[4] J.M. Magalhes, Inertizao de lamas galvnicas por incorporao em materiais cermicos:
estudo dos mecanismos reaccionais, Tese de Doutoramento, Universidade do Minho
(2002).
[5] J.M. Magalhes, J.E. Silva, F.P. Castro, J.A. Labrincha, Kinetic study of the immobilization of
galvanic sludge in clay-based matrix, Journal of Hazardous Materials B121 (2005) 6978.
[6] M. Magalhes, J.E. Silva, F.P. Castro, J.A. Labrincha, Effect of experimental variables on
the inertization of galvanic sludges in clay-based ceramics, Journal of Hazardous Materials
106B (2004) 139-147.
[7] V. Bednarik, M. Vondruska, M. Koutny , Stabilization/solidification of galvanic sludges by
asphalt emulsions, Journal of Hazardous Materials B122 (2005) 139145.
[8] D.C.R. Espinosa, J.A.S. Tenrio, Laboratory study of galvanic sludges influence on the
clinkerization process Resources, Conservation and Recycling 31 (2000) 7182.
[9] P.G. Ract, D.C.R. Espinosa, J.A.S. Tenrio, Determination of Cu and Ni incorporation ratios
in Portland cement clinker, Waste Management 23 (2003) 281285.
[10] A.C. Silva, S.R.H. Castanho Silicate glasses obtained from fine silica powder modified with
galvanic waste addition, Journal non Cryst. Solids 308 (2004) 211-217.
[11] G. Rossini, A.M. Bernardes, Galvanic sludge metals recovery by pyrometallurgical and
hydrometallurgical treatment, Journal of Hazardous Materials 131 (2006) 210216.
[12] R.N. Szente, O.W. Bender, R.A. Shroeter, Treating electroplating residues with thermal
plama, J.O.M. (1998) 32-35.
[13] M.K. Jha, V. Kumar, R.J. Singh, Review of hydrometallurgical recovery of zinc from
industrial wastes, Resour. Conserv. Recycl. 33 (2001) 122.
[14] F. Veglio, R. Quaresima, P. Fornari, S. Ubaldini, Recovery of valuable metals from electronic
and galvanic industrial wastes by leaching and electrowinning, Waste Management 23
(2003) 245252.
[15] H.P. Rajcevic, A hydrometallurgical process for the treatment of industrial wastes, Plant.
Surface Finishing (1990) 22-25.
[16] J.E. Silva, A.P. Paiva, D. Soares, A. Labrincha, F. Castro, Solvent extraction to the recovery
of heavy metals from galvanic sludge, Journal of Hazardous Materials B120 (2005) 113-118.
[17] J.E. Silva, D. Soares, A.P. Paiva, J.A. Labrincha, F. Castro, Leaching behaviour of a
galvanic sludge in sulphuric acid and ammoniacal media, Journal of Hazardous Materials
B121 (2005) 195202.
104
UTILIZATION OF BIOMASS AT THE RECYCLING OF HEAVY METAL

CONTAINING WASTES
1 2
T. Griessacher and J. Antrekowitsch
1 Christian Doppler Laboratory for Optimization and Biomass Utilization at the Recycling of Heavy
Metals, University of Leoben, Franz-Josef-Str. 18, 8700 Leoben, Austria,
thomas.griessacher@unileoben.ac.at
juergen.antrekowitsch@unileoben.ac.at
ABSTRACT
Metal production and recycling industries are typically characterized by a high demand on
energy. Besides this, at the reduction processes necessary in metallurgy additionally high
amounts of reducing agents are used in this field of industry. Normally this high demand
on carbon is covered by fossil carbonaceous materials, which results in high amounts of
greenhouse gas emissions, which enhance the global warming.
In this paper two options of substitution of fossil reducing agents in heavy metals
recycling processes are described. Therefore biomass is converted into metallurgical
charcoal inside a special carbonization reactor and used as carbon-neutral reductant.
Furthermore the by-product pyrolysis gas is used as reducing agent for the recycling of
heavy metal containing residues. With such a replacement of fossil materials the CO 2-
footprint of nowadays dirty industry sectors like heavy metal recycling can be dramatically
reduced.
Keywords: Biomass; charcoal; reduction agent; heavy metals, recycling
INTRODUCTION
In a lot of industrial processes, wastes are produced beside to the target products. These wastes,
especially from metals production and recycling processes, often contain heavy metals and for that
reason are declared as hazardous waste due to the partly leachable character of the heavy metals.
This is why the land filling of such wastes is also restricted or forbidden in almost all Western
countries. Only with some special post-treatment steps, like stabilization or inertization, which
inevitably entails costs, such residues can be deposited. Nevertheless, the disposal capacities in
Europe constantly decrease, which additionally led to enhancing disposal costs [1-5].
On the other hand, the partly high contents of heavy metals like Pb, Zn, Cu, Fe, etc. in these
industrial wastes represent a value, especially at the high metal prices at the moment, which is
often lost if such residues are simply dumped. In particular, residues from steel industry, like
electric arc furnace dusts, or residues from foundry industry, like cupola furnace dusts, can be
called secondary raw materials due to their high contents in e.g. Zn, Cu, etc. and therefore their
high value [5,6].
These two factors, legal regulations on the one hand and high values on the other hand, led to an
enhanced interest and also an enhanced recycling of such residues and wastes in the last years.
This can be seen in a growing number of new developed recycling processes for such materials.
These recycling processes with the target of heavy metals recovery are in nearly all cases based
on the carbothermal reduction of the oxidic wastes. Therefore in the majority of cases high
temperatures and huge amounts of carbon carriers are needed. Due to the fact, that in these
recycling processes typically fossil carbonaceous materials are used to cover the demand on
carbon, this industry sector is responsible for huge amounts of emissions of anthropogenic CO2
[5,6].
105
However, the environmental legislation, especially in Europe, has implemented strict limitations and
regulations concerning the emissions of greenhouse gases. E.g., the Kyoto-Protocol prescribes a
reduction of greenhouse gases in the European Union by 8 % in the years 2008 to 2012, relative to
the emissions of 1990. After 2012 a European emissions trading system is planned, which should
restrict the emission of greenhouse gases further [7]. For that reason energy and reducing
intensive industry sectors like the recycling of industrial wastes are forced to reduce or substitute
their fossil based carbonaceous materials by carbon-neutral alternatives. Due to the fact, that the
reduction of the carbon demand in such industry fields is due to operational requirements hardly
possible, a complete new way of saving greenhouse gas emissions has to be found. One option
therefore is the utilization of biomass in the so called heavy industry, not only as heat carrier, but
also as chemical reducing agent. Therefore it is necessary, in contrast to a thermal usage, to
convert the biomass into high-quality charcoal in special carbonization reactors. This charcoal has
to fulfill the operational requirements of the metallurgical process, like high carbon content, certain
reactivity, etc. The properties of this biological reducing agent should be as similar as possible as
that from fossil reducing agents used at the moment. The by-product of the charcoal production
process, the pyrolysis gas, can also be used as chemical reducing agent, instead of a simple
combustion to produce heat and power. This alternative utilization of the pyrolysis gas can help to
enhance the economics of the whole process [8,9].
CHARCOAL IN METALLURGICAL PROCESSES

The tradition of carbon-neutral fuels and reducing agents in metallurgy is very old. Since the
ancient humans used charcoal for different applications. Small pits with charcoal were used to
smelt different ores to manufacture metallic goods. Also the iron and steel production was in former
years based on the utilization of charcoal in their bloomery and shaft furnaces, since the production
of coke was developed [10].
Nowadays the biggest amount of charcoal is used for cooking, especially in developing countries,
and for barbecuing. There are only some few examples, where charcoal is used in metallurgical
processes. One example is the iron and steel industry in Brazil, where charcoal is used in mini
blast furnaces, due to the lower strength of charcoal. The reason therefore is the low availability of
coal and coke in Brazil. Another example is the production of ferroalloys in electric low shaft
furnaces where charcoal is often used as chemical reducing agent due to its high reactivity and
therefore fast reaction. These two examples show the technical feasibility of the utilization of
carbon-neutral charcoal in metallurgical processes [10-12].
However, charcoal has very often only low qualities, which is founded in the production process,
which is almost always very simple. Typically for the production of charcoal kilns made of earth,
brick or metal are used, which are normally operated at temperature between 400 and 500 C in a
batch-wise mode. The so produced charcoal does not meet the requirements of special
metallurgical processes. Therefore it will be necessary to adapt existing processes or develop new
ones which then can be used for the production of metallurgical charcoal. So, a charcoal with
properties as similar as possible as fossil coke should be producable. Furthermore the specific
properties for each single application can be set in a certain range by changing the carbonization
parameters. E.g. a charcoal for a slag reduction process will need a higher reactivity than a
charcoal for a rotary kiln. Depending on the feedstock material, the carbonization parameters and
the operational options, a customized charcoal production will be possible [10-12].
EXPERIMENTAL WORK AND PROCEDURE

As already mentioned, the target of the investigations described in this paper is the substitution of
fossil based reducing agents in heavy metal recycling processes by carbon-neutral alternatives.
Therefore charcoal was produced at different conditions in a continuous operating reactor. This
charcoal was then used for reduction experiments, where heavy metals from electric arc furnace
dust were recycled. Furthermore, the by-product from the carbonization experiments, the pyrolysis
gas, was directly used for the recycling of another heavy metal containing residue, a Waelz slag.
106
Lab-scale charcoal production
For the production of the metallurgical charcoal, different kinds of biomasses, especially agricultural
residues, were carbonized in a special twin-screw reactor. This reactor is externally and electrically
heated and completely gas-tight. The complete experimental setup, which is shown in Fig. 1,
consists of a feeding bin, a charcoal bin, the reactor itself, the heating, the motor, the controller, the
gas analyzer and the off-gas system. The executed experiments included the carbonization at
different temperatures (up to 900 C) and different retention times (up to 3 h). Also various kinds of
biomasses were tested. Due to the good availability and therefore a good and stable price
situation, the focus was on agricultural and forestry residues like different tree cuttings, fruit stones,
marc, etc. The results of these investigations as well as the total experimental procedure are
explained elsewhere [13].
Fig. 1: Experimental setup for a continuous charcoal production
Rotary kiln experiments with charcoal as reducing agent

These experiments were carried out in a lab-scale rotary kiln and should show the potential of
charcoal as carbon-neutral reducing agent in the recycling of electric arc furnace dusts. The used
rotary kiln, which is shown in Fig. 2, has a heated length of 750 mm and a diameter of 80 mm. The
maximum temperature of the furnace is 1300 C. For the experiments electric arc furnace dust and
charcoal were mixed together with a carbon surplus of 10 % relative to the stoichiometric value
calculated for zinc and iron oxides. With these mixtures and the help of some water micro-pellets (d
= 1 5 mm) were produced, which then were fed into the kiln. Beside charcoal, also petroleum
coke as standard reducing agent for such processes was tested, to have a reference as standard.
The temperature and the retention time used, were 1100 C and 2 hours, respectively. After each
experiment the resulting slag was analyzed concerning their zinc, iron and sulfur content to get
some information about the reduction efficiency of each single reducing agent.
Fig. 2: Rotary kiln for the reduction experiments with charcoal in cold state and in operation
107
The results of the reduction experiments are listed in Table 1, where the higher achievable
reduction rates of charcoal in comparison to petroleum coke can be seen. The reason therefore is
the higher reactivity of the charcoal, which is a result of the much higher porosity and surface area
of the charcoals. So it was possible to lower the zinc content in the remaining slag to about 0.1 %
with charcoal as reducing agent, whereas with petroleum coke still 2.3 % of zinc remained in the
slag. Furthermore the iron metallization was also higher at the reduction experiments with charcoal.
The lower sulfur contents are a result of the very low sulfur content in the charcoals, whereas
petroleum coke has S contents up to 8 %.
All these results show the very high potential of charcoal as substitute for fossil based reducing
agents like petroleum coke or anthracite in metallurgical processes like the recycling of electric arc
furnace dusts. Although the charcoals show a very good performance in the examined
experiments, it has to be kept in mind, that the changed properties of this carbon-neutral reducing
agent will also have an influence on the whole metallurgical process and therefore maybe causes
some problems. The influence of these changed properties like higher porosity and higher reactivity
have to be investigated in further experiments.
Table 1: Chemical composition of the slag as well as achieved reduction rates at the reduction
experiments in the rotary kiln
Slag resulting from Zn red. Fe red.
Zn [%] Fetot. [%] Femet. [%] Fe2+ [%] S [%]
the reduction of rate rate
Charcoal from fruit
tree cuttings 0.10 58.4 48.0 7.5 1.36 99.66 82.19
Charcoal from cork
oak cuttings 0.04 60.6 45.0 13.9 1.08 99.86 74.20
Charcoal from olive
stones 0.12 58.0 43.9 11.2 1.09 99.59 75.69
Petroleum coke 2.28 56.1 40.0 12.8 2.28 97.44 71.30
Retort kiln experiments with pyrolysis gas as reducing agent

In these experiments an alternative way of utilization of the by-product pyrolysis gas from the
charcoal production should be shown. Typically the pyrolysis gas is post-combusted. One part of
the heat is used to keep the reactor on temperature; the other part is used for the production of
heat and power. In this examination the way of material instead of thermal processing of this by-
product should be investigated.
The experimental setup used for the trials is illustrated in Fig. 3. It is a combination of the
carbonization reactor mentioned before and a retort reactor, heated in a resistance furnace. Inside
the retort, which was gas-proof sealed, the heavy metal containing residue was placed in a gas-
purgeable sample holder. The reactor, which was heated externally, additionally consisted of an
insulated gas supply, a gas distributor, to guarantee a uniform flow, the reduction part of the retort,
the condenser unit, which was the upper part of the retort and a gas outlet. The pyrolysis gas used
for the reduction was directly re-directed to the bottom of the retort with the help of insulated tubes,
where it flowed constantly through the residue and reduced the zinc and iron oxides in the slag.
The pyrolysis gas itself shows very high contents in hydrogen and carbon monoxide (see Table 2),
especially when high carbonization temperatures are chosen. The gases used for this testing
series were produced with different kind of biomasses at retention times of 2 and 3 h, respectively
and at a constant carbonization temperature of 900 C. The kind of biomass itself does not have a
big influence on the chemical composition of the pyrolysis gas.
Table 2: Composition of the pyrolysis gas in cleaned condition (without tars)

Carbonization temperature [C] Retention time [h] CO [Vol-%] CO2 [Vol-%] CH4 [Vol-%] H2 [Vol-%]
600 2 25.27 33.20 14.41 14.66
750 2 23.62 26.01 14.25 29.42
900 2 29.28 18.64 10.53 36.78
For each reduction experiment 1.0-1.5 kg of heavy metal containing residue, in this case a Waelz
slag, was put into the basket, which was positioned in the retort. Then the gas condenser was
arranged on the retort and gas-proof sealed. Afterwards the retort was brought on temperature and
108
the carbonization was started. At each experiment 5 kg of biomass were carbonized. The gases
emitted during the carbonization flowed continuously through the gas pipe and further through the
retort with the Waelz slag inside. The temperature of the retort was varied between 1000 and 1100
C in 50 C steps. After each experiment the retort was purged with nitrogen to prevent the re-
oxidation of the reduced iron until the reactor cooled to room temperature.
Fig. 3: Experimental setup of the reduction experiments with pyrolysis gas
For the described experimental series, Waelz slag was used as heavy metal containing residue
with a zinc content of 4.62 % and an iron content of 35.5 %. This Waelz slag was mixed with
carbon in form of charcoal with an amount of 0.5 stoichiometrical based on the Zn- and Fe-oxide
content to enhance the reduction of the iron oxides inside the Waelz slag. The chemical analysis of
the remaining slag after the reduction experiments with pyrolysis gas are listed in Table 3. The zinc
reduction rate from Table 3 is calculated by the ratio of the zinc content in the slag after the
experiment and the original Waelz slag, whereas the iron metallization rate is the ratio of the
metallic iron to total iron content inside the remaining slag.
Table 3: Chemical composition and achievable reduction rates of the reduced Waelz slag
Trial Nr. 1 2 3 4 5 6
Temperature [C] 1000 1050 1100 1000 1050 1100
Time [min] 120 120 120 180 180 180
Zn [%] 0.49 0.03 0.08 0.1 0.03 0.02
Pb [%] 0.04 0.03 0.04 0.04 0.04 0.04
Fe2+ [%] 16.1 0.4 16.8 17.1 11.3 14.7
Femet. [%] 24.7 39.3 23.5 23.3 30.7 26.7
Feges. [%] 41.3 43.8 40.9 40.8 42.6 41.8
Zn-reduction rate [%] 89.4 99.3 98.3 97.8 99.3 99.6
Fe-metallization rate [%] 59.8 89.7 57.5 57.1 72.1 63.9
It can be seen, that it was possible to reduce the total amount of zinc oxide and the biggest parts of
the iron oxides. That means that per ton of Waelz slag 45 kg of zinc can be recovered and the
remaining slag can be named as sponge iron due to the high metallization rate. So the residue,
Waelz slag, can be converted into a saleable product for the iron and steel industry, especially at
high iron metallization rates, which can help to solve a lot of disposal problems and to save costs.
The reduction temperature and reduction time does not have an influence on the results of these
experiments. Due to the fact that the gas compositions at all experiments were nearly constant, the
only influencing parameters on the process are the gas amount as well as the tar composition and
amount. Unfortunately, these parameters were not measureable with the used equipment. But it
109
could be seen, that the kind of biomass, which was carbonized, has an influence on the achievable
reduction rates of the Waelz slag. For example, the gas from olive tree cuttings shows the highest
reduction potential, although this kind of biomass has lower volatile contents as others. However, it
could be shown that the reduction and therefore the recycling of Waelz slag with the help of
pyrolysis gas is technical feasible.
SUMMARY AND CONLUSION

The recycling of different kinds of metal-containing residues with its high carbon demand is still a
big emitter of anthropogenic CO2-emissions at present, due to the usage of fossil carbonaceous
materials. Because of environmental regulations now and in the following years, which are for sure
combined with additional costs, the industry is forced to find some alternative ways to reduce their
CO2-footprint. One option is the substitution of fossil raw materials by carbon-neutral ones based
on biomass.
In this paper the technical feasibility of two possible ways of substitution of fossil coke in the
recycling of heavy metal containing residues by charcoal on the one hand and pyrolysis gas on the
other hand are shown. Of course the economics of such new processes depend on many factors,
like biomass availability and price, costs for biomass conversion, effectiveness of the carbon-
neutral reducing agent but also on the development of carbon taxes as well as additional costs
from environmental legislation in future. All these points can help to start an environmental
revolution in typically dirty industries and save huge amounts of greenhouse gas emissions.
References
[1] J. Rtten, Ist der Wlzprozess fr EAF-Staub noch zeitgem? Stand der Technik und
Herausforderungen, Heft 118 der Schriftenreihe der GDMB, 2. Seminar Vernetzung von Zink
und Stahl (2009) 137-149.
[2] G. Strohmeier, J.E. Bonestell, Steelworks residues and the Waelz kiln treatment of electric
arc furnace dust, Iron and Steel Engineer 4 (1996) 87-90.
[3] Forschungsgesellschaft fr Straen- und Verkehrswesen, Merkblatt ber die Verwendung
von Metallhttenschlacken im Straenbau - Report FSGV-Nr. 639 - FGSV Verlag GmbH,
Cologne (1999)
[4] Ministerium fr Umwelt und Naturschutz, Landwirtschaft und Verbraucherschutz und des
Ministeriums fr Verkehr, Energie und Landesplanung des Bundeslandes Nordrhein-
Westfalen, Anforderungen an die Gteberwachung und den Einsatz von
Metallhttenschlacken im Straen- und Erdbau - Report IV - 3 - 953-26308 IV 8 1573-
30052 (2004)
[5] J. Antrekowitsch, Complex heavy metal containing wastes: between landfilling and recycling,
Proc. of EMC 1 (2009) 3-13.
[6] J. Rtten, Application of pyrometallurgical processes on resource recycling of steel mill dust.
- Paper presented at the 55th GDMB Zinc Experts Committee Meeting, Balen, Belgium
(2007)
[7] M. Anderl et al., Klimaschutzbericht 2010 - Report REP-0267, Umweltbundesamt GmbH,
Vienna (2010)
[8] A. Bandi et al., Renewable Energy in: Landolt-Brnstein, Energy Technologies, Subvolume
C, Springer-Verlag, Berlin Heidelberg-New York, 2006, p. 414.
[9] V. Strezov, T. J. Evans, P. F. Nelson, Carbonization of Biomass Fuels in: M.D. Brenes
(Eds.), Biomass and Bioenergy: New Research, Nova Science Publisher Inc., 2006, pp. 91-
123.
[10] J.A. Antal Jr., M. Grnli, The Art, Science, and Technology of Charcoal Production, Ind. Eng.
Chem. Res. 42 (2003) 1619-1640.
[11] R. Siemons, Industrial Charcoal Production - FAO TCP/CRO/3101 (A) Development of a
sustainable charcoal industry, North-West Croatia Regional Energy Agency (2008)
[12] M. Grnli, Industrial Production of Charcoal - Norwegian University of Science and
Technology (2005)
[13] T. Griessacher, Alternative Reducing Agents in the Recycling of Heavy Metal-Containing
Residues, Proc. of EMC 4 (2011) 1349-1361.
110
SEPARATION OF PLASTICS BY JIGGING
1a 1b 1c
Pita, F. A. , Rodrigues, N. , Castilho, A.
1
Geosciences Centre, Department of Earth Sciences, Faculty of Sciences and Technology,
University of Coimbra, Largo Marques de Pombal, 3000-272 Coimbra, Portugal
a b c
fpita@ci.uc.pt ; nelsonr@ci.uc.pt, amcaltil@ci.uc.pt
Abstract
Plastics are possibly the components of the Municipal Solid Wastes that are most difficult
to recycle. This fact results from the difficulty in separating and differentiating plastic
types. In recent years, several studies have tried to adapt mineral processing methods to
plastic separation. One of these methods is gravity separation (specially jigging) where
the separation is based upon density differences between materials.
Three bi-component plastic mixtures have been tested in a jig, with the objective of
getting a sunk fraction cleaned from Polystyrene (PS). The effect of particle shape and
particle size has been analysed in five size fractions (1-1.4 mm, +1.4-2 mm, +2-2.8 mm,
+2.8-4 mm and +4-5.6 mm).
The tests lasted long enough to overflow most of the PS. However, the results show that
the quality of the jigging separation varies with the mixture and it depends on size and
shape of the particles. In the case of particles with more regular shapes, a separation
improvement has been verified with size. For lamellar particles the influence of particle
size was minimal.
Jigging proved to be a good method, but the separation of a bi-component mixture will
have better results if the lower density plastic, that overflows, has lamellar shape and if
the higher density plastic, that sinks, has spherical shape.
Keywords: Plastic; recycling; jigging separation; particle size; particle shape.
INTRODUCTION
In the last decades plastic has acquired a greater importance in peoples lives, contributing to the
improvement of their life standards. Traditional materials (such as glass, metals and wood) have
been replaced by plastic equivalents. The wider use results from its lower price, versatility and
excellent properties. The world consumption has been growing yearly and it is expected that it will
grow at an annual rate of 5%. The same tendency has been observed in Portugal and the plastic
consumption has increased about 5% per year. The enhanced use of plastics is responsible for
their percentage on the Municipal Solid Wastes (MSW), which is now about 11% in weight.
With time, plastics have acquired a negative reputation due to its difficult decomposition. In a
landfill they will remain unaltered due to light and oxygen absence. However, when properly
collected and processed, the plastics can be valued through recycling and/or energy recovery.
Almost all the plastic materials are recyclable, but for the recycling to be possible it is necessary to
separate the different types of plastics.
In recent years several studies have attempted to adapt mineral processing methods to plastic
separation [1-13]. One of these processes is gravity separation (specially jigging) where the
separation is based upon density differences of materials. Jigging is a gravity concentration method
that takes place in a pulsating bed. A mixture of solid-water is placed in a perforated vessel at the
bottom (jig), through which are forced vertical currents of water, ascending and descending. The
action of those currents either expands (ascending currents) or compacts (descending currents)
the pulsating bed. The particles stratification is based on density differences between the
constituent particles of the mixture. The heavier particles move downwards, and they stay inside
the jigging cell, while the lighter particles go upwards and they eventually overflow.
111
In the present study the separation of three plastic mixtures by jigging was analysed to verify the
influence of the size and the shape of particles.

For this study four types of granulated plastics have been used. Three recycling companies
supplied the plastics: PS (Polystyrene) and PMMA (Polymethyl methacrylate) from Daniel Morais;
PET (Polyethylene Terephtalate) from Logociclo-Selenis and PVC (Polyvinyl Chloride) from
Micronipol. The densities of these plastics, measured in the laboratory, are shown in Table 1.
Table 1 - Plastic densities.

3
Types of plastic Density [g/cm ]
PS 1.047
PMMA 1.204
PET 1.372
PVC 1.326
In order to analyze the influence of particle size in the separation, the weight of five size fractions
(+1-1.4, +1.4-2, +2-2.8, +2.8-4 and +4-5.6 mm) was measured.
The shape of the particles was described by the shape factor F=Dmin/Dmax (where Dmin and Dmax
represent the smaller and the larger particle diameters). PMMA particles have more regular
shapes, similar to small spheres. However, PET particles have usually lamellar shapes, or even
slightly wavy for particle sizes greater than 2 mm, which might increase the difficulties of
penetration in the jigging bed. PVC particles present a more regular shape than PET particles.
Particle shapes for the plastic types and the size fractions are shown in Fig.1.
0,8
0,6 PS
PM M A
F-shape
0,4 P VC
P ET
0,2
0,0
1-1.4 1.4-2 2-2.8 2.8-4 4-5.6
Particle size (m m )
Fig. 1. Shape factor of the different plastics in five size fractions.
The tests were done in a Denver jig with a rectangular section with 10x15x10 cm. The objective
was to obtain a sunk as cleaned as possible from PS. Since this type of plastic has a lower density
than the other three plastics, PS is overflowed and the others are kept inside the jigging cell.
The jigging separations were tested in three bi-component mixtures: PS+PMMA, PS+PET,
PS+PVC, contributing each plastic with 50% of the weight. The particles used had a size between
1 and 5.6 mm. The jigging tests were lasted long enough to overflow as much PS as possible.
The quality of the plastic separation was measured by the efficiency of separation, defined by
Schulz as =RP1-RP2 (where is the efficiency, RP1 is the recovery of plastic 1 in the floated and
RP2 is the recovery of plastic 2 in the floated) [14].
PS+PMMA mixture
112
The recovery and the grade in the PS+PMMA mixture (floated and sunk) were measured in five
size fractions (Fig. 2 and 3). The PMMA recovery in the sunk increased with particle size: from
69.4% for the finer fraction to 94.6% for the coarser. As a consequence, the PS grade in the floated
fraction increased with particle size. For the finer fraction (1-1.4mm) the PS grade in the floated
was 76.5% and the PMMA grade in the sunk was 99.3%, and for the coarser fraction (4-5.6 mm) it
has been obtained a floated with a grade of 94.8% in PS and a sunk with a grade of 99.6% in
PMMA. So, the sunk is a product almost pure in PMMA.
For PMMA particles the finer fraction is at the uppermost part of the jigging bed, while the coarser
fractions are in the lower strata.
100 100
Floated recovery (%)
Floated grade (%)

PS PS
80 80
PM M A PM M A
60 60
40 40
20 20
0 0
1-1.4 1.4-2 2-2.8 2.8-4 4-5.6 1-1.4 1.4-2 2-2.8 2.8-4 4-5.6
Particle size (m m ) Particle size (m m )
Fig. 2. Influence of particle size in the recovery and grade of the floated (concentrated of PS) in the
separation of the PS+PMMA mixture.
100 100
Sunk recovery (%)
Sunk grade (%)
80 PS 80 PS
PM M A PM M A
60 60
40 40
20 20
0 0
1-1.4 1.4-2 2-2.8 2.8-4 4-5.6 1-1.4 1.4-2 2-2.8 2.8-4 4-5.6
Fig. 3. Influence of particle size in the recovery and grade of the sunk (concentrated of PMMA) in the
separation of the PS+PMMA mixture.
PS+PET mixture
The recovery and the grades of PS and PET in the jigging separation have similar results for all
size fractions (Fig.4 and 5). PET recovery in the floated showed slightly lower values for the
medium sizes. The floated had a grade of about 77% in PS. For the five fractions it has been
obtained a sunk with a PET grade of 99.5%.
100 100
Floated grade (%)
80 PS 80 PS
P ET P ET
60 60
40 40
20 20
0 0
1-1.4 1.4-2 2-2.8 2.8-4 4-5.6 1-1.4 1.4-2 2-2.8 2.8-4 4-5.6
113
separation of the PS+PET mixture.
100 100
Sunk recovery (%)
80 PS PS
Sunk grade (%)

80
P ET P ET
60 60
40 40
20 20
0 0
1-1.4 1.4-2 2-2.8 2.8-4 4-5.6 1-1.4 1.4-2 2-2.8 2.8-4 4-5.6
Fig. 5. Influence of particle size in the recovery and grade of the sunk (concentrated of PET) in the
separation of the PS+PET mixture.
PS+PVC mixture
Fig. 6 and 7 illustrate the influence of the particle size in the recovery and grade of the PS+PVC
mixture. The recovery of PVC in the sunk increases with particle size and the opposite happens in
the floated, with less recoveries and grades. For the coarser fraction it was possible to obtain a
sunk with a grade of 99.5% in PVC and a floated with a grade of 91.2% in PS, but for the finer
fraction the sunk has a grade of 99.6% in PVC and the floated has a grade of 82.5% in PS. Those
figures shows that in order to get a better jigging separation it should be used a mixture with
particles coarser then 2.8mm.
100 100
Floated grade (%)
PS PS
80 80
P VC P VC
60 60
40 40
20 20
0 0
1-1.4 1.4-2 2-2.8 2.8-4 4-5.6 1-1.4 1.4-2 2-2.8 2.8-4 4-5.6
separation of the PS+PVC mixture.
100 100
Sunk recovery (%)
PS PS
80 80
Sunk grade (%)
P VC P VC
60 60
40 40
20 20
0 0
1-1.4 1.4-2 2-2.8 2.8-4 4-5.6 1-1.4 1.4-2 2-2.8 2.8-4 4-5.6
Fig. 7. Influence of particle size in the recovery and grade of the sunk (concentrated of PVC) in the
separation of the PS+PVC mixture.
Efficiency of the separations

The total efficiency of jigging separations of the three mixtures presents the following order:
(PS+PET) < (PS+PMMA) (PS+PVC) (Fig. 8).
114
100
Separation efficiency (%)

80
60
40 P S+P M M A
P S+P ET
20 P S+P VC
0
1-1.4 1.4-2 2-2.8 2.8-4 4-5.6
Particle size (m m )
Fig. 8. Influence of the particle size in the efficiency of the jigging separation for all the plastic mixtures.
The efficiency of separation of PS+PMMA mixture shows an improvement with the increase of the
particle size up to 95% for the coarser fraction, probably because the mass of PMMA particles
increase and that coarser particle have a more regular shape. For the PS+PVC mixture the
efficiency increasing with particle size is observed, but less sharply. For all particle sizes the quality
of separation is reasonable, having a separation efficiency of 90% for the coarser fraction (Fig.8).
However, particle size seems to have minimum influence on the separation efficiency of the
PS+PET mixture (Fig. 8). The three intermediate size fractions have a separation efficiency of
approximately 73%, which is inferior than the efficiency obtained for the PS+PMMA and the
PS+PVC mixtures, plus, increasing particle size does not lead to improved results, probably due to
the lamellar shape of PET particles.
As a gravity separation process is based in the density differences, it would be expectable that the
PS+PET mixture presented the best results, because PET is more dense (Table 1). On the other
hand, it would be expectable that the PS+PMMA mixture presented the worst results, because
PMMA has a density close to PS. However, PS+PET mixture has the lowest separation efficiency.
So, those results can not be explained by the density differences.
Particle shape also conditioning the jigging separation and varies from almost spherical (PMMA) to
lamellar (PET) with the following regularity order: PET < PVC < PS < PMMA.
The separation efficiency order of the three mixtures is more similar to the regularity order of the
particles than their densities. PVC has a better efficiency of separation than PET, because it has a
higher density and presents a shape more regular than PET and the good results for PMMA can be
explained through its spherical shape. The lamellar particles of PET are more easily entrained
through the washing water in the jigging process, so the floated obtained are less pure in PS.
CONCLUSIONS
The quality of the jigging separation of plastics is good. The results obtained in the laboratory show
that PS grade in the sunk was less than 1% for all the plastic mixtures, even though the tests lasted
long enough to make overflow most of the PS. In spite of this, the separation varies with the
mixture type and it depends on the density, size and shape of the particles.
The PS+PMMA and PS+PVC mixtures gave the best results. For a PS+PMMA mixture, the results
show that the separation clearly improves with the particles size. In fact, for the coarser fraction (4-
5.6 mm) the floated had a grade of 94.8% in PS, while for the finer fraction the PS grade was
76.5%.The PS+PET mixture gave the worst results. The sunk was almost pure in PET, but the
floated had a PS grade of just 77%. In the PS+PVC mixture, the separation improved with
increasing particles size. The PS grade in the floated was 91.2% for the coarser fraction and
82.5% for the finer fraction.
The particle size is an important factor in the jigging process. In the jigging separation of ores,
vertical granulometric stratification occurs inside the jigging bed. The larger particles are in the
uppermost strata and the smallest are in the lower ones [15]. For the plastics, whose density is only
slightly greater than water, the behaviour is different. During the bed expansion the finer particles
115
are more easily elevated in the jigging bed than the coarser, so finer particles of plastic are more
likely to overflow.
The shape of the particles also plays an important role. It has been verified that, for plastic particles
with a more regular shape the separation was better with the increase in the particles size and, on
contrary, for lamellar particles (PET) the influence of the particles size was minimal. Although PET
is the denser plastic, the PET+PS mixture led to a less selective separation. It seems that particles
of lamellar shape overflow more easily (PET) than the spherical shaped ones (PMMA or even
PVC).
Since the floated of the three mixtures is not pure in PS, multiple jigging separations would have to
be implemented to obtain a better separation.
The results obtained show that these mechanical separation techniques have a good potential to
come into use in the separation of plastics, taking into account the low recycling rates of plastics
and the difficulty in the manual separation.
Acknowledgements
The authors thank the companies Daniel Morais, Logociclo-Selenis and Micronipol for the supply of
plastic samples.
References
[1] E. Agante, M.T. Carvalho, F. Duro, T. Brtolo, Separation of PET, PVC and PS using gravity
concentration and froth flotation. Proceedings of the Global Symposium on Recycling, Waste
Treatment and Clean Technology (REWAS'04), Madrid, Spain (2004), 1691-1700.
[2] G. Dodbida, J. Sadaki, K. Okaya, A. Shibayama, T. Fujita, The use of air tabling and
triboelectric separation for separating a mixture of three plastics, Minerals Engineering. 18
(2005), 1350-1360.
[3] G. Ferrara, P. Bevilacqua, L De Lorenzi, M. Zanin, The influence of particle shape on the
dynamic dense medium separation of plastics, International Journal Mineral of Processing. 59
(2000), 225-235.
[4] N. Fraunholcz, Separation of waste plastics by froth flotation, Review, Part I, Minerals
Engineering. 17 (2004), 261-268.
[5] M. Ito, M. Tsunekawa, E. Ishida, K. Kawai, T. Takahashi, N. Abe, N Hiroyoshi, Reverse jig
separation of shredded floating plastics - separation of polypropylene and high density
polyethylene, International Journal Mineral of Processing. 97 (2010), 96-99.
[6] R.D. Pascoe, Y.Y. Hou, Investigation of the importance of particle shape and surface wettability
on the separation of plastics in a LARCOMEDS separator, Minerals Engineering. 12 (1999),
423-431.
[7] R.D. Pascoe, Investigation of Hydrocyclones for the separation of shredded fridge plastics,
Waste Management. 26 (2006), 1126-1132.
[8] Y. Kuwayama, M. Ito, N Hiroyoshi, M. Tsunekawa, Jig separation of crushed automobile
shredded residue and its evaluation by float and sink analysis, Journal of Material Cycles and
Waste Management.. (2011).
[9] G.M. Richard, M. Mario, T. Javier, T. Susana, Optimization of the recovery of plastics for
recycling by density media separation cyclones, Resources, Conservation and Recycling. 55
(2011), 472-482.
[10] H. Shen, R.J. Pugh and E. Forssberg, A Review of plastics recycling and the flotation of
plastics, Resources, Conservation and Recycling. 25 (1999), 85-109.
[11] H. Shen, E. Forssberg, and R.J. Pugh, Selective flotation separation of plastics by particle
control, Resources, Conservation and Recycling. 33 (2001), 37-50.
[12] J. Shibata, S. Matsumoto, H. Yamamoto, E. Lusaka, Flotation separation of plastics using
selective depressants, International Journal Mineral of Processing. 48 (1996), 127-134.
[13] T. Tsunekawa, B. Naoi, S. Ogawa, K. Hori, N. Hiroyoshi, M. Ito, T. Hirajima, Jig separation of
plastics from scrapped copy machines, International Journal Mineral of Processing. 76 (2005),
67-74.
[14] N.F. Schulz, Separation efficiency, Transactions SME/AIME. 247 (1970), 81-87.
[15] B.A. Wills, Mineral Processing Technology, first ed., Pergamon Press, Oxford, 1979.
116
13th September
Session 3.1
( SOCIAL FACTORS AND EDUCATION ON WASTE
MANAGEMENT / LEGISLATIVE AND POLICY
FRAMEWORK )
Chairman: Jorge Arajo
117
EVALUATION THE INHABITANTS PARTICIPATION IN SEPARATION AT

SOURCE BY WASTE CHARACTERIZATION
1 2 3 4
K. Rousta , M.K. Moghadam , P.H. Karimkhani , T. Richards
1 Kamran Rousta, Resource Recovery, University of Bors, Sweden, Kamran.Rousta@hb.se
2 Mitra Kaeni Moghadam, University of Bors, Sweden, mitra_kaeni@yahoo.com
3 Parima Haji Karimkhani, University of Bors, Sweden, parima_hk@yahoo.com
4 Tobias Richards, Resource Recovery, University of Bors, Sweden, Tobias.Richards@hb.se
ABSTRACT
In Bors, a modern municipality solid waste management (MSWM) has been established
since 1988 which is working based on separation at source. The citizens of Bors have a
central role in the fulfilment of the sustainable goals for the MSWM by separating several
waste fractions at their home.
There are many factors such as education, convenience, information, responsibility, attitude,
culture, etc. which affect the citizens recycling behaviour as well as their participation in
separation at source. The goal of the present study was to identify the guidelines for further
research in inhabitants recycling behaviour. Therefore, evaluation of the present situation
regarding wastes sorting at source was considered. This study analysed the collected waste
in black and white bags in three different neighbourhoods in Bors. The household waste in
these areas were collected randomly from different types of dwelling and households in
spring 2010 and characterized into 21 different fractions based on its origin. This study
measured how active the inhabitants were in a source separation system. The results
identified some barriers and drivers in the system which can affect the citizens participation
in source separation. The results of the study also showed some factors such as
convenience and situational, culture and the type of distributed information which needs to
be investigated further. A comparison of the results from this study with a previous one from
2000, showed both improvements and declination in different areas during these ten years.
Keyword: Solid waste management, Bors, recycling behaviour, source separation, waste
characterization
INTRODUCTION
Due to the rapid growing of waste production worldwide, treating various streams of waste, e.g.
industrial, agricultural and household waste, become serious issues for each municipality [1]. For
waste treatment, sustainable and environmental friendly methods should be applied to minimize the
environmental impact. To reach a sustainable waste management it is necessary to design and apply
a system which moves towards the top of the waste hierarchy, Fig. 1. The 3Rs in waste hierarchy,
Reduce and Reuse (source reduction), and Recycle (recycling), show the main strategies in waste
management regarding to their importance and desirability [1,2]. Fuel production (e.g. biogas and
bioethanol) and energy recovery comes next and as the last choice, when there is no other option;
some waste such as hazardous waste can go for waste disposal [2]. Frequent steps in a waste
treating organization are: collecting from waste production location, transporting to pre-treating or
processing facility, and disposing the remained part. The waste can be compressed, sorted,
separated, dried, packed or stored in the pre-treatment step and thereby get prepared for future
processing or transportation. It is common to collect the household waste once a week in Europe and
it depends on the amount of waste production per inhabitant in that area and waste collection facilities
of the municipality [3]. There are many methods to establish a waste management system for a
community and it can be tailor-made for each community [4]. The selection of system can be based on
e.g. participating of the inhabitant, sorting at source, and technology. Separation at source is one of
the most effective ways to facilitate reuse of material in a solid waste management system [4].
Applying waste separation at source in MSWM puts the inhabitants in a key position in which the
system is working more efficient by low cost in the collection system [5].
118
Fig. 1. Waste management hierarchy [4].
Bors, a city in the south west of Sweden with about 100,000 inhabitants has applied a MSWM for
households based on separation at source which is called the Bors system in Sweden [6]. Since
1992 this system has decreased the total amount of landfilling from 100 ton to less than 10 ton per
year in 2010 which was mostly soil [7]. In the Bors system, there are two plastic bags for the
separation of biodegradable and combustible waste, black and white respectively (Fig. 2). All food
waste go to the black one and the light plastic, the small papers, different wastes which are not sorted
in the sorting place should be put in the white bags [6].
Fig. 2. Black bags; organic food waste and white bags; combustible waste.
Approximately 80 recycling facilities for collecting the packaging with producer reasonability is present
in the city. They consist of six-chamber-recycling stations for recycling newspaper, paper, plastic,
glass and metal packaging and are placed in each neighbourhood. There are also boxes for collecting
small batteries [8]. These stations are managed through the producer responsibility, which means that
producers of e.g. electronics, batteries, papers and packages must provide means for recycling.
The city of Bors has also five recycling centres. Two of them are in the main city of Bors, while the
others are in the smaller communities Viskafors, Dalsjfors and Fristad. These centres are responsible
for collecting electronic waste, hazardous waste, bulky waste, used furniture and landfill fraction. The
inhabitants are responsible to carry these types of waste to these stations without paying any fees.
In such a system, the inhabitants play very essential roles in the waste management. All solid waste
should be sorted at source by them. Therefore, studies on the recycling behaviour and understanding
the barriers and opportunities in this field can help the decision makers to develop the system as much
as possible towards sustainability. The present study was done to identify the guidelines for further
research in the inhabitants recycling behaviour. Therefore, evaluation of the present situation
regarding wastes sorting at source in black and white bags was considered. This study analyses the
collected waste in black and white bags in three different neighbourhoods in Bors in order to
compare the recycling behaviour in these three districts as well as finding the important factors for
further research in this field.
METHODS AND MATERIALS

During week 14-21, 2010, waste samples from three selected areas, Hestra, Kristineberg and Norrby,
in Bors were collected. These three areas were the same areas which were used in a previous study
119
and consist of 120 villas in Hestra, 339 flats in Kristineberg and 144 flats in Norbby. Since there was
no long holiday or any national day during this period of time, waste generation during this season
were stable and could be considered generally acceptable for most of the year. The selected unit was
wheeled bin for both houses and apartment blocks. Independent random sample (IRS) was used for
villas and houses, and stratified sampling used for apartment buildings where each flat constitutes a
stratum. If the filling in a wheeled bin was less than 50% it was not representative of the multi-housing
unit. Instead, another bin was selected randomly.
The collection analysis was preceded by weighting the bags using an electronic wave balance
(TANITA model BSE, capacity 50 kg 0.05 kg) with a measurement accuracy of 50 grams. The
numbers of black and white bags were counted, and the weights of bags were recorded. It is important
to note that this study was limited to pick analyze of the black and white plastic bags. The other
fractions of the waste which could be generated and transferred to the recycling stations were not
considered. In total, 2440 kg of waste were analyzed and sorted into 21 different fractions (Table 1).
Table 1. Numbers and weights of the samples from different districts

Hestra Kristineberg Norrby
Black White Black White Black White
Number 273 501 239 607 259 582
Weight [kg] 370.2 436.2 252.1 517.6 317.6 545.6
Total Weight [kg] 806.4 769.7 863.2
These 21 fractions were classified in four categories:

1) Hazardous waste: bulb, battery, electronic waste and other hazardous waste
2) Recyclable waste: soft and hard plastic, cardboard, paper, paper packaging, multilayer
packaging, metal packaging, metal packaging with deposit, glass packaging, glass
packaging with deposit, PET and metal scrap
3) Combustible waste: other food packaging, diapers and tissues, combustible trash and others
4) Food waste: any food waste
RESULTS
Three main evaluations were made, 1) evaluate the proportion of the fractions in white and black bags,
2) analyze the different type of recyclable material in white bags and 3) comparison of the results with
the previous study in 2000.
Waste Fractions Related to Black and White bags

Figs. 3 and 4 show the proportion of each four categories in white and black bags in the three areas.
Sorting of waste in the black bags in all three areas is acceptable for the biogas production process. In
Hestra almost 90% of the bag contents were food waste whereas in Norrby it came down to 75% and
in Kristineberg 80%. The amount of recyclable materials in the black bags for Kristineberg and Norrby
are larger than Hestra. The combustible fractions, which should not be sorted in black bags for all
three areas are about 12%. However, the result from the white bags was not pleasing. 15% to 30% of
food waste was placed in the white bags in different areas where Norrby was the worst. About 35% of
recyclable materials were found in white bags in which only the combustible waste should be placed.
120
100% 100%
90% 90%
80% 80%
70% 70% Hazardous

Hazardous
Waste
60% Waste 60%
Recyclabe
50% Recyclabe 50%
Waste
Waste
40% 40% Combustible
Food Waste Waste
30% 30%
20% 20% Food Waste

Combustible
10% Waste 10%
0% 0%
Fig. 3. Proportion of four categories in Fig. 4. Proportion of four categories in

white bags. black bags.
In the Fig. 5, the total waste fractions both in white and black bags are shown.
100%
90%
80%
70%
60%
Hazardous Waste
50% Recyclabe Waste
40% Combustible Waste
Food Waste
30%
20%
10%
0%
Hestra Kristineberg Norrby
Fig. 5. Proportion of four categories in total waste generation (white and black bags).
The results showed that all three areas generated more or less the same fractions of waste with
different levels of sorting and less than 1% of the total waste in black and white bags was hazardous
waste.
Recyclable Materials in White bags

The high amounts of recyclable material in the white bags were further analyzed. Fig. 6 shows the
proportion of each fraction of recyclable materials in the white bags. Almost no packaging with deposit
was found. The most fractions in all three districts were plastic, paper (including newspapers and
advertisement papers), multilayer and paper packaging. Hestra showed less papers and Norrby had
less multilayer and paper packaging in comparison to the other districts. The amount of metal
packaging and metal scrap was more than 5% in all areas. The Hestra area showed the lowest
fraction of glass packaging and cardboard.
121
40%
35%
30%
25%
20%
15%
10% Hestra
5%
Kristineberg
0%
Norrby
Fig. 6. Proportion of material in recyclable waste in white bags
Comparing Classification of Fractions with Previous Study in 2000

The new results from this investigation with respect to the manual sorting in white bags were
compared with the previous case study which was performed in the year 2000. In the last study only
the fractions in the white bags were analyzed [9]. Therefore, Fig. 7 shows the proportion of four
categories only in the white bags in 2000 and in 2010.
The results showed that Hestra had a good improvement regarding reduction of the food waste in the
white bags. However, there was no obvious improvement in Norrby. The amount of recyclable material
in the white bags was more or less the same as 10 years ago.
100%
90%
80%
70%
60%
50%
Hazardous waste
40%
30% Recyclable waste
20%
Combustible waste
10%
0% Food waste
Fig. 7. Comparison of fractions in white bags between 2000 and 2010
DISCUSION
The results show that the problem of mixing food waste and combustible waste in the two different
plastic bags is worst in Norrby, moderate in Kristineberg and Hestra is better than the others. By
looking at the immigrants background statistics in these three districts, Norrby with 25% has more than
Kristineberg with 20% and Hestra with 8% [10]. This can express the need of information for sorting
122
guides in different languages. Also all three areas put about 35% recyclable materials in the white
bags which it is not desirable. The main reason can be the lack of information for inhabitants in how to
sort their waste. In other words, the available information system does not work properly. Comparing
the results with the previous study in 2000 can be another evidence for this, because the amount of
the recycling materials in white bags is more or less the same as in 2010.
Logistics and access to recycling station should be considered as motivation factors for recycling
behavior [11]. A good system should facilitate a better participation for the citizens. The convenience
factors can motivate the people to participate in the sorting system. For example, the results from this
study show that the most recyclable parts in the white bags are plastic, paper, paper and glass
packaging. There are two main reasons for that. The first one can be the distance and the access to
recycling stations. The other reason is that these fractions have just a small part of the total waste
generation that the people do not care to sort them [12].
Even the type of houses can affect to sorting behavior. There are enough inside spaces to have
sorting bags for different recyclable fractions in villas (type of houses in Hestra) where there are not in
flats (type of the houses in Kristineberg and Norrby). Meanwhile based on the legislation in Bors,
houses with inadequate sorting are going to be punished by extra fees [6]. Where each villa has its
own waste bin, it is easy to identify which waste belongs to which villa but for the multi flats this is not
possible. This legislation can be one of the reasons that Hestra sort better than the others. The results
also showed that there are no PET, aluminum cans and glass packaging with deposit in the bags. The
return systems, which is available in Sweden and works based on deposit, is the main reason. More
than 90% of such material goes to recycling each year in Sweden [13]. This can prove that economical
incentives can play a major role to motivate the people to participate in the recycling system.
CONCLUSION
The results of this study are guidelines for future research in order to modify the waste management
system in Bors towards the top of the waste hierarchy. Based on these results and discussion, it can
be concluded that the factors such as information, convenience, and economical incentives are
important to motivate the citizens to participate in the waste separation system.
References
[1] Stehlk, P., Efficient waste processing and waste to energy: challenge for the future. Clean
Technologies and Environmental Policy, 2009. 11(1): p. 7-9.
[2] Gertsakis, J. and H. Lewis, Sustainability and the waste management hierarchy. Retrieved on
January, 2003. 30: p. 2008.
[3] Johansson, A., et al., Report: Waste refinery in the municipality of Boras. Waste Management &
Research, 2007. 25(3): p. 296.
[4] Tchobanoglous, G., Integrated solid waste management: engineering principles and management
issues (ISE)(paper). 1993.
[5] Suchada, P., et al. The role of formal and informal sectors in solid waste management of
developing countries. in Ninth International Waste Management and Landfill Symposium S.
Margherita di Pula, Cagliari. 2003. Italy.
[6] BEM. Bors Energi och Milj. 2010 [cited 2010 17.07]; Available from: http://www.borasem.se/.
[7] Carter, S., Bors Energi och Milj. Personal Communication. 2011: Bors.
[8] Lagerkvist, A., Academic research on solid waste in Sweden 1994-2003. Waste management,
2006. 26(3): p. 277-283.
[9] Milj, B.E.., Pick Analysis of household waste in Bors Spring 2000.
[10] Lindqvist, M. Immigrant background in different areas in Bors 2010. Statistics Sweden 2011
[cited 2011 01.05]; Available from:
http://www.boras.se/download/18.556ed85e13074032f618000703/11sf19.pdf.
[11] Martin, M., I.D. Williams, and M. Clark, Social, cultural and structural influences on household
waste recycling: A case study. Resources, Conservation and Recycling, 2006. 48(4): p. 357-395.
[12] Norborg, K. Recycling in Sweden, Report 2011. GFK Custom service, Avfall Sverige Swedish
Waste Management 2011 [cited 2011 01.05]; Available from:
http://www.mynewsdesk.com/se/pressroom/avfall_sverige/document/view/attitydundersoekning-
om-aatervinning-2011-13202.
[13] Pantamera. Pantamera. 2011 [cited 2011 01.05]; Available from:
http://www.pantamera.nu/start.asp.
123
st
WASTE MANAGEMENT AS PART OF A BROADER SYSTEMS APPROACH TO

PRODUCTION AND CONSUMPTION
1 2 3
Singh J. , Frostell B. and Wennersten R.
1 Department of Industrial Ecology, Teknikringen 34 KTH, Stockholm 11428, jagdeep@kth.se
2 Department of Industrial Ecology, Teknikringen 34 KTH, Stockholm 11428, frostell@kth.se
3 Department of Industrial Ecology, Teknikringen 34 KTH, Stockholm 11428, rw@kth.se
ABSTRACT
Rapid economic growth, urbanization and increasing population have caused materially
intensive resource consumption to increase and consequently the release of large amounts
of waste in the environment. In the future, to manage resources and wastes sustainably,
waste management requires a more systems oriented approach. Hence, it becomes
important to explore the gaps between current production, consumption and waste
management practices in order to have transition towards sustainable waste management.
In this paper, some key challenges to waste management systems are highlighted in a
global context and a broader systems approach to the waste management problem is
discussed.
Keywords: waste, waste management, challenges, systems approach
INTRODUCTION
In the last few decades, rapid economic development and urbanization has resulted in substantial
improvements in well-being for large fractions of the world population. At the same time, we have
seen increased materially intensive resource consumption and consequently the release of large
amounts of waste to the environment [1-3].
Waste is regarded as by-products or end products of the production and consumption process
respectively [4]. In the product consumption chain, the resources entering into the human
environment are being processed, transformed, used and discarded to nature in the form of solid,
liquid and gaseous wastes. An integrated approach to waste management (WM) requires the
accounting and controlling of all kinds of emissions (gaseous) and wastes (solid and liquid). So the
widest possible definition of integrated waste management system could be given as it is a
process of change, in which the concept of waste management is gradually broadened to
eventually include the necessary control of gaseous, liquid and solid material flows in the human
environment, emphasizing precautionary actions [5]. However, to limit the scope of the study, only
solid waste streams are included in this paper.
WM practices differ from region to region depending upon economic development; consequently
the limitations and challenges for a particular waste management system (WMS) are also different
from operation and planning perspectives. It becomes very important to identify the challenges to a
particular WMS in order to have transition towards a more sustainable system. In this paper, we
have highlighted some of the key challenges to the current WMS in a global perspective and a
broader systems approach to waste management is proposed.
WASTE MANAGEMENT (SCENARIO) IN A GLOBAL CONTEXT
Waste: Definition, characterization, composition and its development

There are several definitions of the term waste. Wastes can be considered, as those materials no
longer required by an individual, institution or industry. However, certain wastes may eventually
become resources valuable to others, once they are removed from the waste stream. According to
European Union directives on waste, waste is defined as any substance or object which the holder
discards or intends or is required to discard [4]. The categorization of various types of wastes,
based on its source, varies greatly among waste studies, and some sources are commonly
excluded, such as industrial, construction and demolition, and municipal services [6]. For simplicity,
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the wastes are normally categorized into different categories such as: municipal solid waste
(MSW), industrial waste, agricultural waste, hazardous waste, e-wastes, etc.
Municipal solid waste

MSW is generated from households, offices, hotels, shops, schools and other institutions. The
major components are food waste, paper, plastic, rags, metal and glass, small quantities of
hazardous waste, such as electric light bulbs, batteries, automotive parts and discarded medicines
and chemicals [6].
The waste composition of MSW varies from country to country depending on factors such as
geographical location, the populations standard of living, energy source, and climate. Figure 1
shows the estimated rise in amount of yearly municipal waste generated in the different regions of
the world over the last three decades and the composition of municipal solid waste in different
countries. MSW constitutes the most complex solid waste stream as compared to homogeneous
waste streams from industry, agriculture, etc.
Estimated yearly generated MSW Composition of municipal wastes in various countries
100 Others
700
600 Percentage composition 80
[million tonnes]
waste amount
Metal
500 60
Glass
400
40
300 Plastic
200 20
Paper
100 0
0 Compos
1990 2000 2010 table
North America EU 15 Asia
Fig.1 Estimated amounts of yearly municipal waste generated and composition of municipal solid
waste in different countries. Sources: [6-8]
Industrial waste
Industrial waste encompasses a wide range of materials of varying environmental toxicity.
Typically, this range includes paper, packaging materials, waste from food processing, oils,
solvents, resins, paints and sludges, glass, ceramics, stones, metals, plastics, rubber, leather,
wood, cloth, straw, abrasives, etc. The composition of industrial wastes in a country depends on
the nature of the industrial base. The absence of a regularly up-dated and systematic database on
industrial solid waste has the consequence that still the exact rates of generation are largely
unknown [6, 8].
Hazardous wastes
With rapid development in agriculture, industry, commerce, hospital and health-care facilities,
consumption of various chemicals has increased; these processes produce a large amount of
hazardous waste [8]. The types, quantities and sources of hazardous waste vary significantly from
country to country and are influenced by the extent and diversity of industrial activity. Treatment
and disposal of hazardous waste is often difficult and very costly. This has made ocean dumping
and export to countries with less strict regulations an attractive option.
Electronic waste or e-waste

The use of electrical and electronic equipment (EEE) has increased exponentially in recent
decades. Although, per-capita production rate in populous developing countries such as China and
India is still relatively low and estimated to be less than 1 kilogram (kg) waste electric and
electronic equipment (WEEE) per capita per year, but the absolute volume of end-of-life products
generated in these countries is already significant [9-11].
Electronics products are becoming more and more complex. Although the concentration of metals
is decreasing in the products, the recovery of metals after dismantling is also decreasing [12].
Electronic waste recycling in developing countries like China and India is mainly motivated by the
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recovery of valuable precious metals (mainly gold, silver, and palladium) with wet chemical
processes, involving highly toxic substances such as mercury and cyanide. These works are done
by untrained people, resulting in a high impact on their health and the environment. In contrast to
this practice, in Europe, valuable metals from relevant e-waste fractions are recovered efficiently in
large industrial integrated smelters and refineries with profit margins allowing for environmentally
safe handling of the critical substances [13].
Agricultural waste and residues

The expanding agricultural production has resulted in increased quantities of livestock waste,
agricultural crop residues and agro-industrial by-products. For example, since 1960, as a result of
rises in productivity, there have been corresponding increases in the volumes of crop residues and
animal manure requiring disposal. Among the countries in the ESCAP nations (United Nations
Economic and Social Commission for Asia and the Pacific), China produces the largest quantities
of agricultural waste and crop residues followed by India [6]. In the developing countries, crop
residues are used as feed stock for animals and excessive residues not suitable for any use, are
usually burnt in open air [8].
CHALLENGES TO THE GLOBAL WASTE MANAGEMENT SYSTEM
Increasing waste quantities

The waste generation rates are affected by socioeconomic development, degree of industrialization
and climate of the region. Generally, the greater the economic prosperity and the higher
percentage of urban population, the greater the amount of waste produced. It is evident from figure
1 that the amount of waste in Asia is increasing at a very fast rate because of economic
development and increasing urbanization. Whereas, in high income countries growth has
stabilized, with the fact that per capita waste (kg/person/day) generated is very high in such
countries as compared to low and middle income countries (see table 1) and still it is increasing,
although at very low rate. The waste quantities and compositions not only vary between countries,
but also between individual cities and communities within a city depending upon the economic
situation of the particular community (see table1 and figure1).
Table1. Daily waste generation rates [kg/person/day] in large and medium size cities: a global
perspective
Waste amount (mixed) [Kg] Low income middle income High income
countries* countries* countries*
Large Cities (>500000 residents) 0,5 to 0,75 0,55 to 1,1 0,75 to 2,2
Medium Cities(100000 to 500000 residents) 0,35 to 0,65 0,45 to 0,75 0,65 to 1,5
Source: The World Bank, 2010 [14]. *Classification based on income levels: Low income countries
(UD$510), middle income countries (510US$5,884), High income countries
(5,884US$40,090)
Simple waste management practices in rapidly growing economies

Usually, local municipalities are responsible for managing the waste generated in a city or town.
Yet in many countries, private organizations work with the municipalities in order to carry out waste
management activities [15-19]. There are many differences in the way WM activities are performed
in different countries. In high income countries, WM includes highly industrialized recycling
activities, high-tech mechanized machinery, sanitary landfills with gas and leachate collection and
treatment facilities etc. In low and middle income countries, the solutions used for waste
management still to a great extent are end of pipe solutions. Open dumping is prevalent in such
countries and there is a lack of controlled sanitary landfills. Indeed, approximately 90 % of MSW is
disposed of in ordinary and simple landfills [16]. The present situation is deteriorating at a very fast
rate due to increasing urbanization and increasing waste amounts (cf. figure 1). It is becoming
increasingly difficult to get public approval for development of new landfill sites and at economically
acceptable distances from a collection area.
Due to lack of planning and other pressing factors such as landfill area scarcity etc. municipalities
opt for unsustainable practices, for example solid waste incineration has been given a top priority
over other waste disposal methods although it is much more expensive [15, 17]. The stringency of
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legislation on waste management practices also varies in different countries. In low and middle
income countries, legislation is less stringent as compared to the high income countries. There is a
strong need to develop infrastructure for waste management and implementation of more stringent
legislation in these countries.
Environmental awareness and participation of people in WM

The level of environmental awareness among actors plays an important role in the consumption-
use-disposal chain. Environmental awareness motivates consumers towards a sustainable
behaviour such as judicial use of the products (resources), responsible disposal etc. This directly
affects waste sorting and hence affects the overall efficiency of the WMS. In low and middle
income countries, one of the reasons for a lack of environmental awareness could be the
inadequate educational institutions. But studies show that there is a strong concern among people
for a clean environment and the belief that learning, information and awareness campaigns are
important drivers to behaviour change [20]. However, this does not necessarily translate into an
increased participation in recycling or reuse initiatives. In high income countries, people consider
the disposal of waste as a significant environmental concern, but it is not an issue at the forefront of
their minds. Consequently there is often a poor participation. There is also a lack of understanding
about how waste problems are linked to global issues such as climate change, which is an issue
that people are particularly aware of and concerned about. The challenge is to successfully make
the association between peoples waste disposal behaviour and global concerns in the same way
as they have linked climate change to car use and local flooding [21].
Lack of resources and well organized institutions

The reason, low and middle income countries rely on low technology solutions is that there is lack
of inadequate manpower, financial resources, absence of well-organized institutions and
infrastructure required for effectively carrying out various activities for MSW [19]. There is also lack
of formal waste collection systems in such countries. As such the informal sectors for waste
collection are highly active. Indeed, there are twice as many people in the informal sector as those
in the formal sector [22]. Unfortunately, these informal waste collection systems make it more
difficult to regulate and implement an efficient and standardized waste treatment system.
Lack of Intellectual resources

In high income countries, much emphasis is now on understanding WM as a system. Resources
are allocated on collecting and analyzing the waste related information for example waste quantity,
composition etc., by using computer based simulations programs, which is not common in low and
middle income countries. In low income countries, most efforts are still devoted to resolve basic
institutional, operational and management issues. In such countries, there is a lack of attention
towards development of the intellectual resources.
The literature survey suggests a map of the waste management system in different parts of the
world as presented in table 2. The number of plus sign indicates the intensity of a particular issue.
Table 2. An attempt to map the waste management in different parts of the World
Issue Low income middle income High income
countries countries countries
Increasing waste quantities ++ +++ +
Simple waste management practices +++ ++ +
Environmental awareness & participation of people
in WM + ++ +++
Lack of resources and well organized institutions +++ ++ +
Lack of intellectual resources +++ ++ +
Lack of links between production, consumption &
WMS +++ +++ ++
Overall seriousness of existing problems in the
production, consumption and WMS + ++ +++
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THE WASTE MANAGEMENT SYSTEM AS PART OF A BROADER SYSTEMS APPROACH TO
PRODUCTION AND CONSUMPTION
The technological developments have mainly been taking place in the production sectors, guided
by economic aims. But in recent decades, we have witnessed emerging discussions on
sustainability leading to increased consumer awareness about products environmental
performance, cleaner production possibilities and industrial symbiosis. Still, the focus is
predominantly on the individual product or system in isolation rather than on a more coherent
systems approach; where production, consumption and the WMS should be considered together.
There need to be a stronger coherence between production, consumption and WM. It requires to
identify the various links, mechanisms, processes, and stakeholders etc. throughout the production,
consumption and WM chain. In this development, it would be pertinent to address the following key
issues:
How shall products be designed to improve ecocycling (reuse, recycle and disposal) when
discarded?
How may the use of resources be minimized throughout the system?
How may a stronger interaction be established among various stakeholders throughout a
products life cycle?
The production consumption and waste management chains are active at local as well as
global levels. How to incorporate these systems globally?
It appears that the traditional reductionist approaches to WM leads to short term solutions rather
than long term sustainability thinking [23]. The WMS is a dynamic system which consists of many
actors, internal loops, processes etc. There is a need to identify positive drivers and mechanisms
among different actors. This requires information flow between different actors and systems (see
Figure 2).
Figure 2. Different system interactions, processes and information flow in a broader system.
CONCLUSIONS
Our main conclusions from this survey are:
Due to the inextricable link between GDP and waste generation, there is a steady increase in
waste amount in the world. This presents a big challenge for current development and especially
for the current desire of continued economic growth.
1. On a per capita basis, it could be argued that the waste related problems are higher in high
income countries than low and middle income ones despite a more advanced WMS.
128
2. Lack of resources, well organized institutions and less stringent legislation are barriers to
improved WM in low and middle income countries.
3. Rapidly Increasing per capita waste amounts in middle income countries indicate that the
current system is not yet on a sustainable trajectory.
4. Despite of environmental concerns, waste issues are not at the forefront of peoples minds.
There is thus a need to develop a stronger coherence between the currently rather isolated working
systems: production, consumption and WM. This requires identifying positive drivers and
mechanisms among different actors.
References
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environment Based on the Consumption Level Difference of China's Provinces or
Autonomous Regions, China Population, Resources and Environment, 18 (2008) 121-127.
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[3] O. Blanchard, Energy consumption and modes of industrialization: Four developing
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[5] Anonymous, Elaboration of a Regional Strategy on Integrated Waste Management, United
Nations 1991.
[6] What a Waste: Solid Waste Management in Asia. Washington, The World Bank, 1999.
[7] Information on: http://www.oecd.org
[8] Information on: www.unescap.org
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Review, 25 (2005) 436-458.
[10] B. H. Robinson, E-waste: An assessment of global production and environmental impacts,
Science of The Total Environment, 408 (2009) 183-191.
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electrical and electronic wastes, Waste Management, 31 (2011) 714-730.
[12] C. Hageluken, Improving metal returns and eco-efficiency in electronics recycling, in 2006
IEEE International Symposium on Electronics and the Environment, San Francisco 2006.
[13] D. Rochat, et al., Optimal Recycling for Printed Wiring Boards (PWBs) in India, in R'07
Recovery of Materials and Energy for Resource Efficiency, Davos, Switzerland, 2007.
[14] Information on: http://data.worldbank.org/country
[15] J. Jin, et al., Solid waste management in Macao: Practices and challenges, Waste
Management, 26 (2006) 1045-1051.
[16] D. Q. Zhang, et al., Municipal solid waste management in China: Status, problems and
challenges, Journal of Environmental Management, 91 (2010) 1623-1633.
[17] R. Bai and M. Sutanto, The practice and challenges of solid waste management in
Singapore, Waste Management, 22 (2002) 557-567.
[18] T. Hazra and S. Goel, Solid waste management in Kolkata, India: Practices and
challenges, Waste Management, 29 (2009) 470-478.
[19] S. Kumar, et al., Assessment of the status of municipal solid waste management in metro
cities, state capitals, class I cities, and class II towns in India: An insight, Waste
Management, 29 (2009) 883-895.
[20] L. Mbeng, et al., Assessing Public Attitudes and Behaviour to Household Waste
Management in Cameroon to Drive Strategy Development: A Q Methodological Approach,
Sustainability, 1 (2009) 556-572.
[21] Public Attitudes Towards Recycling and Waste Management, MORI Social Research
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[22] The World Bank, Waste Management in China: Issues and Recommendations, Urban
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129
HOUSEHOLD ORGANIC WASTE SOURCE SEPARATION: OPERATIONAL

ASPECTS AND BEHAVIOUR FACTORS INFLUENCING SEPARATION
F.S. Vitor
Servios Municipalizados de gua e Saneamento de Loures, Diviso de Resduos Slidos
Rua Ilha da Madeira, 2, 2674-504 Loures, Portugal
Tel.: +351.219.838.620; Fax.: +351.219.838.629
E-mail: filomenus@gmail.com
ABSTRACT
Planning convenient separate collection systems requires taking into consideration the
characteristics of the type of waste, as well as the characteristics of the residential area.
Understanding citizens recycling behaviour, determining significant differences between
recyclers and non-recyclers and establishing how this information can improve separate
collection systems become more convenient, is also important in planning future recycling
programs with high participation rates.
Data from the daily collection system helped characterizing and evaluating aspects
related to the biowaste separation activity.
This study focuses on households organic waste source separation and separate
collection and aims to examine the most important operational aspects and evaluate
which factors influence biowaste recycling behaviour.
Outcomes reveal that non-recycling families are very similar to recycling families in what
concerns their socio-demographics characteristics, situational conditions and in their
evaluation of the MSW management service. Their differences are related with the
variables reflecting specific attitudes towards the biowaste separation behaviour, social
norms, importance assigned to the separate collection, perceived behavioural control,
belief in personal effort to achieve separate collection benefits, information on biowaste
and knowledge about the existence and purpose of the biowaste container.
Some operational improvements concerning the separate collection system and the
communication strategy are suggested.
Keywords: biowaste; recycling behaviour; organic waste; household separate collection.
INTRODUCTION
Biodegradable municipal waste (BMW) management is one of the current challenges of a
sustainable urban waste management and has been, over the past years, a crucial concern for
local and national authorities. The current Portuguese and European environmental policy in BMW
management and the most recent Waste Framework Directive (2008/98/CE) are a driving force for
increasing organic waste (biowaste) recovery. The experience of several countries with high
biowaste diversion rates (e.g. Germany, Austria, Denmark, Netherlands) shows that separate
collection is an essential requirement for large-scale biowaste recovery and contributes for a good
quality final product. The waste separation behaviour is, therefore, fundamental to the success of
biowaste recovery systems.
When conceiving and implementing convenient and successful biowaste separate collection
systems its necessary to take into consideration the characteristics of this type of waste (easy
decomposition, high moisture content and high density), as well as the characteristics of the
residential area (type of housing, population density, climate, existing waste collection system) [1].
Understanding citizens recycling behaviour, determining significant differences between recyclers
and non-recyclers and establishing how this information can improve separate collection systems
130
become more convenient, is also important in planning future recycling programs with high
participation rates.
This study [2] focuses on households organic waste source separation and separate collection and
aims to examine the most important operational aspects and evaluate which factors influence
biowaste recycling behaviour.
CASE STUDY
The study area consists of a high-density residential district with 211 multi-residential high-rise
buildings, called Urbanizao da Portela, located in Lisbon Metropolitan Area, in the municipality of
Loures. It is a suburb community with 15.441 inhabitants and 5.106 families spread over an area of
2
only 0,95 km (Fig. 1).
It is a very homogeneous population with regard to socio-demographic characteristics, with a high
level of education (41% have higher education), high proportion of potentially active population
(77% between 15 and 64 years old) and low elder-child ratio (81) compared with the national
average. The average household size is 3 persons.
The area is also very homogeneous in terms of urban and building characteristics and operational
conditions of the MSW collection system.
Population is served by a kerbside waste collecting system (i.e. building to building), which allows
families to separate their wastes into 5 different streams: 1) paper and cardboard (since 1996); 2)
glass packaging (1999); 3) metal and plastic packaging (1999); 4) organic waste (2005); 5) residual
unsorted waste.
Families dispose their wastes in appropriate collective containers located in designated areas for
waste container storage in each building (Fig. 2). Nevertheless, many of the buildings still have
garbage chutes located in each floor for residual unsorted waste disposal. Residual unsorted waste
and biowaste must be placed in plastic or paper bags before being deposited inside the containers.
Users are responsible for ensuring waste container hygiene and for placing them outside the
building to be collected. Building janitors, who in most cases live in the building, usually perform
this task.
Municipal solid waste (MSW) collection is held between 11.00pm and 6.00am. When this study
was conducted, residual unsorted waste was collected five times a week, organic waste six times
and recyclables weekly. Currently, as a result of an improvement measure suggested in the study,
unsorted waste and biowaste are collected on alternate days, each three times a week.
Biowaste household collection was implemented in Urbanizao da Portela in 2005, by Servios
Municipalizados de Loures (SMAS Loures) in a partnership with Valorsul, under the scope of
Program + Valor, a biodegradable waste separate collection and recovery program in the north of
Lisbon Metropolitan Area. The municipal authority (SMAS Loures) is responsible for the biowaste
collection and transport for treatment in the anaerobic digestion Valorsul facility: Biodegradable
Waste Processing Plant (ETVO).
Separate organic waste collection implementation was preceded by an intensive communication
campaign by the local municipal authorities. This campaign involved: 1) direct mailings to all
households; 2) invitations to all condominium administrators to a succession of informative
meetings with the objective of clarifying doubts and mobilizing participants. Their participation was
crucial at this stage as they were the link between SMAS Loures and the population and they had
an important role in increasing membership among the residents of their building. When collection
started, 73% of the buildings had already joined the project; 3) free distribution of household
containers for biowaste separation in kitchens, for all families interested; 4) free distribution of 120
liters brown containers for biowaste deposits and collection, at all buildings interested. Brown
containers were assigned to all buildings where there was at least one family interested in
participating; 5) distribution of brochures, posters and stickers for containers with the procedures
and separation rules (Fig. 3).
The communication strategy regarding the biowaste collection system allowed all residents to have
access to the same information and the same conditions for joining the program. All these aspects,
that could influence participation in biowaste separation, had small variation, allowing a better
isolation of the variables that can determine separation behaviour.
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Fig. 3 - Educational stickers,
brown container for collection
and domestic container for
Fig. 1 - Study area Fig. 2 - MSW containers separation
BIOWASTE SEPARATION AND COLLECTION ACTIVITY CHARACTERIZATION

Data from the collection system (between 2005 and 2007) were used in characterizing and
evaluating aspects related to the daily biowaste separation activity, namely:
Program membership: The majority of the buildings (87%) joined the separate collection program in
2005. Currently, around 95% of the buildings have biowaste containers. After the program
implementation phase, the greater membership periods corresponded in time with local marketing
actions (December 2005, October and December 2007). During these periods there were also a
greater number of families joining separate collection (measured in requests for domestic
container). Comparing the different types of buildings, it was found that buildings with smaller
storage conditions for waste containers (lack of designated areas for storage or garage) were the
most resistant in joining the program.
Quantities collected: It was not possible to calculate the diversion rate and efficiency nor the
performance of the domestic biowaste collection system, because the collection route is not
exclusive for domestic producers (which in the period of the study accounted for 86% of all the
route collection locations), but also includes large producers (like canteens, restaurants,
supermarkets and markets). The average daily amount of biowaste collected varied from 2.322 kg
in 2005 to 2.163 kg in 2007, reflecting a slight descending trend. During the study period, there was
a clear decrease in the daily amounts collected during the summer months (July and August),
corresponding to the households holidays. In relation to the daily variation throughout the week, the
minimum average quantities are collected on Wednesdays and the maximum on Sundays (due to
the collection stop in Saturday) and Thursdays.
Collection Participation: Based on records made by the waste collection teams about the daily
presentation of the biowaste container for collection in each building, it was possible to calculate:
- Each building, on average, places the biowaste container for collection 16 days a month, that is, 4
days per week;
- 67% of the buildings, on average, place the biowaste container for collection every day (varying
from 28% to 95%);
- The participation rate of existing buildings (in the study area) is 78% (ranging between 56% and
88%) (considering a minimum frequency of placement of the container for collection of 2 times per
week);
- The participation rate of the buildings joining the program (with brown container) is 90% (ranging
between 74% and 100%) (considering a minimum frequency of placement of the container for
collection 2 times per week);
It was not possible to calculate participation rates at the household level because in multi-family
buildings the container is shared by several families. The study also verified that building
characteristics (existence for designated areas for waste container storage and number of
households) influences the participation frequency on biowaste separate collection.
Requests and Complaints: Requests received at the customer service of SMAS Loures were
mainly for joining the biowaste separate collection program and for demanding biowaste containers
(88%). The remaining requests concerned container replacements and repairs and demands for
more information. The number of complaints received was not significant (0,002 complaints per
year per family in 2006 and 0,004 complaints per year per family in 2007).
Biowaste contamination: Biowaste received in ETVO should not be contaminated with more than
11% by weight with other types of waste and should have a biodegradable waste content above
132
72%. There are also limits to the presence of some specific contaminants, including plastics
(5,7%). Of the samples analyzed by Valorsul during the period of the study it was found that plastic
is the most common contaminant, especially plastic film, due to the generalized utilization of plastic
bags for waste conditioning. Biowaste contamination (visible) is also registered by the waste
collection teams, which in 2007 identified an average of 1,3 buildings per day with contaminants.
Household separate collection evaluation: All aspects of the biowaste separate collection system
tested were evaluated positively (overall rating of 3,95 on a scale of 1 to 5), except the information
received on biowaste (2,88). Items with more favorable assessment referred to the supply of a
domestic container for biowaste separation (4,5), simplicity of using the brown container (4,29)
and collection frequency (4,16). Hygiene of the brown container and neighbors participation
were also evaluated positively (4,00 and 3,73 respectively).
FACTORS INFLUENCING BIOWASTE SEPARATION BEHAVIOUR

The main investigation tool was a face-to-face household survey applied to a sample of 97 families
living in 51 buildings, conducted between June and July 2007. Recycling behaviour was measured
by self-report, given the impossibility of observing the separation behaviour of the respondents.
The study aimed to identify and assess the recycling behavioural differences between different
buildings and groups of families. Depending on their answers and context, the families were
classified in three groups: 1) SRO group: families who separate their organic waste; 2) NRO_CC
group: families who do not participate in organic waste separation, in spite of living in buildings with
convenient brown containers available; 3) NRO_SC group: families who neither separate organic
waste, nor live in buildings with organic waste containers available. The distinction between
NRO_CC and NRO_SC intended to assess if the lack of convenient containers in the building for
the disposal of organic wastes was a cause for non-participation or a consequence of households
situational conditions or characteristics.
Several research hypotheses were established, based on previous research, taking into
consideration the three study groups and seeking to evaluate their characteristics and differences.
The methods used were statistical inference, chi-square ( 2) for sampling frequencies and analysis
of variance (on-way ANOVA) for the sampling averages. The minimum level of significance
accepted was p <0,05.
In general, the three groups in question are very homogeneous with respect to their socio-
demographic characteristics, because no significant differences were identified with regard to their
gender, age, socio-economic status, family structure, presence of children in household and time of
residence in the neighbourhood. The only significant difference identified was in the education level
of individuals NRO_SC, lower when compared to SRO ( 2(1)=14,18; p<0,000) and NRO_CC ( 2
(1)=5,01; p<0,05).
The first significant differences identified between groups concern their situational conditions. The
presence of a building janitor is significantly less frequent in buildings where NRO_SC families live
when compared to SRO ( 2(1)=10,10; p<0,005) and NRO_CC ( 2(1)=10,10; p<0,05). Since no
differences were detected between groups SRO and NRO_CC, this means that the presence of a
building janitor, with the tasks of cleaning MSW containers and placing them for collection, does
not directly influence households separation behaviour, but it can have a negative impact on
buildings joining the biowaste separate collection system (translated in the absence of a request for
the brown container). On the other hand, contrary to what one might expect, the presence of
condominium administrator living in the building does not appear to influence either joining the
collection system, or participating in biowaste separation. Another important aspect concerns the
use of garbage chutes for unsorted waste disposal, which is significantly lower in SRO families
when compared with the two groups not participating in biowaste separation, NRO_CC ( 2(1)=7,70;
2
p<0,01) and NRO_SC ( (1)=6,92; p<0,01). SRO families separate the majority of the waste they
produce using the building containers, which means that they are less dependent on using the
garbage chute for the disposal of their household waste.
Concerning the information and knowledge variables, results depend on the analysed aspect.
Individuals involved in biowaste separation (SRO), when compared with those not participating,
NRO_CC and NRO_SC, showed higher results regarding received information on separate organic
waste collection ( 2(1)=12,97; p<0,000 and 2(1)=10,20; p<0,005), number of sources of
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information indicated (F(2)=8,54; p<0,000) and knowledge about the existence (Fisher: p<0,05 and
p<0,005) and purpose ( 2(1)=9,85; p<0,005 and 2(1)=18,31; p<0,000) of the brown container . On
the other hand, the type of information source referred and the knowledge demonstrated about
biowaste treatment, as well as about the final products of this treatment, are similar in all three
groups. The overall index of knowledge about separate biowaste collection and recovery system
(built on the basis of four knowledge items: existence and purpose of brown container, biowaste
treatment and final products) only reveals significant differences between NRO_SC and SRO
groups (F(2)=5,81; p<0,005), but not compared with the NRO_CC group.
The most important differences between families that separate biowaste and the two groups not
participating in separation are on the evaluation and opinion variables. In fact, recyclers (SRO),
compared to the other groups, have greater perceived neighbours participation on biowaste
separation (F(2)=55,96; p<0,000) and assign greater importance to the existence of a separate
collection system (F(2)=5,83; p<0,005). Moreover, they have higher perceived behavioural control
(F(2)=7,05; p<0,005) and most believe in the importance of their personal efforts to achieve the
benefits of separate collection (F(2)=64,61; p<0,000).
Furthermore, contrary to what one might expect, the three groups did not reveal significant
differences in the awareness of the advantages conferred to the biowaste separate collection
system and in the quality assessment of the MSW management service, with respect to various
aspects, including the biowaste separate collection. The overall quality assessment index on MSW
management service was based on seven items related to urban cleaning, commingled and
separate waste collection.
Concerning the NRO respondents availability to start biowaste separation, although more
NRO_SC mention being willing to begin when compared to NRO_CC, this difference is not
significant. However, when questioned about what they need to get started, NRO_SC individuals
differ significantly from NRO_CC ( 2(1)=13,00; p<0,005). NRO_SC, as expected, refer more often
to the need of a brown container, and most of NRO_CC individuals indicate personal reasons,
initiative, information or greater biowaste production. NRO_SC never referred to the lack of storage
space or container to separate at home, unlike the individuals NRO_CC.
In conclusion, the main differences between the two groups that have similar socio-demographic
characteristics and equivalent situational conditions (e.g. SRO and NRO_CC), are related to the
variables that reflect specific attitudes towards the biowaste separation behaviour (i.e. social
norms; importance assigned to the biowaste separate collection system; perceived behavioural
control; belief in personal effort), information on biowaste and knowledge about the existence and
purpose of the brown container, which confirms Ajzens Theory of Planned Behavior. NRO_CC
households are sceptical toward biowaste separate collection and show less positive attitudes.
Compared to the other two groups, the NRO_SC group shows a lower education, less frequent
presence of building janitors living in the building and being responsible for maintaining and
cleaning the waste containers, and lower perceived neighbours participation. As reasons for not
participating, the majority of NRO_SC referred to the lack of appropriate collection equipment in the
building; 60% of these households stated that they are willing to participate and 67% indicated that
they just need the brown container to begin. This indicates that many of these families are potential
participants.
OPERATIONAL IMPROVEMENTS OF BIOWASTE SEPARATE COLLECTION SYSTEM

The outcomes of the study [2] suggested some operational improvements regarding the separate
collection system and the communication strategy:
Reduce the collection frequency for biowaste and unsorted waste from six and five days a week
respectively, to three times a week each, in alternate days. The fact that each building puts its
container for collection an average of four times a week and that almost 50% of the biowaste
separating families participates a maximum of three times a week, seemed to indicate that the
collection frequency was over dimensioned and it was possible to reduce it. This measure was
implemented in 2010 and there were no reports of inconvenience for users.
The existence and use of garbage chutes for unsorted waste disposal significantly reduces the
participation in biowaste separation. Some households indicated this aspect as a reason for not
separating (included in the answer "It takes a lot of work"). And some individuals suggested that
closing garbage chutes would increase the participation in separate collection. Implementing a
134
communication campaign for the promotion of garbage chutes closure could be a measure to
consider for the increase of family participation in recycling. Such a campaign should be well
planned and well reasoned in addressing the various disadvantages of this type of garbage
disposal, in order to avoid resistance by the residents.
Brown containers should be installed in all buildings even without being requested, as a measure to
increase participation in biowaste separate collection. This should be duly accompanied by
informative sessions as to their purpose and acceptable materials. The existence of brown
container can help increase households perception about their neighbours participation, which in
turn may promote their greater involvement. It can also operate as a source of information and help
increase the awareness and knowledge about the separate collection system.
Target audience for communication campaigns: Socio-demographic attributes examined did not
distinguish between recyclers and non-recyclers. Therefore, in this case, it is not relevant to plan
awareness campaigns for a specific target audience, based on this type of segmentation. On the
other hand, building janitors proved to be an essential element for the success of the separate
collection system, influencing the building admission to the system and promoting the project.
Therefore, communication campaigns should focuses preferentially in building janitors or
condominium administrators, in buildings where families do not participate because they have no
means to do so (no organic waste container available). Subsequently, they should be directed to
the families living in buildings with low participation rates. In this case, the campaigns directed at
individuals in the group NRO_CC, less interested, sceptical, and with less favourable attitudes
about the separation behaviour, should have more specialized ("chirurgical") content.
Sources of information: Considering the assessment made by SRO families about the biowaste
separate collection system, the information received was the only aspect negatively evaluated.
Therefore, new ways to inform and motivate households to change or continue their separation
behaviour should be found. Local street actions, in specific locations closer to the population, seem
to have a positive effect on building and family membership. This kind of action also seems to be
preferred by individuals and was stated by some households as a good way to increase
participation. The distribution of compost and visits to the Biodegradable Waste Processing Plant of
Valorsul are good alternative ways of spreading the message about the value of biowaste.
Households also referred the demonstration of what is made from separated waste as a good way
to increase participation.
Information content: Providing information that clarifies the separate collection process, identifying
the waste components to be separated and in what containers they should be deposited, not
forgetting to refer to the uncommon materials and those not accepted for recovery, allows
individuals to separate in a more efficient way. Future communication campaigns and its
information content should aim at reinforcing the motives given as reasons to participate and
neutralize those reported as reasons for not doing so. On one hand, the advantages of biowaste
recovery should be presented in terms of the environmental benefits of its treatment and final
products (for which the respondents have demonstrated low levels of knowledge). Also the sense
of civic duty should be clarified, specifically, the fact that it is the personal responsibility of each
citizen to contribute to the solution of a problem that is caused by all. On the other hand, the
statistics of family and building involvement and participation and the evolution of the quantities
collected should be advertised. This will help to establish the idea that there are already many
families involved and reduce the perception that only a few people participate. The perception of
difficulty in participating should also be contradicted by messages that clarify the specific tasks that
participants must perform, in order to make them easier from their point of view and demonstrate
how easy it is to separate biowaste.
REFERENCES
[1] ACRRGSR, Gesto dos resduos domsticos biodegradveis - Que perspectivas para as
autoridades locais europeias? Associao das Cidades e Regies para Reciclagem e Gesto
Sustentvel dos Recursos, Lipor, 2005.
[2] F. S. Vitor, Factores determinantes para a recolha selectiva de resduos orgnicos de origem
domstica: Caso de estudo da Urbanizao da Portela, Tese de mestrado apresentada na
Faculdade de Cincias e Tecnologia da Universidade Nova de Lisboa, Lisboa, 2008.
135
ASSESSEMENT OF MUNICIPAL WASTE OPERATORS: ADAPTING THE

ASSESSMENT FRAMEWORK TO A NEW REGULATORY CONTEXT
1 2 3
J. Silva , M. Nunes and D. Alves
1
Engineering Department Waste Sector, ERSAR Entidade Reguladora dos Servios de guas
e Resduos (The Water and Waste Services Regulation Authority)
Centro Empresarial Torres de Lisboa, Rua Toms da Fonseca, Torre G 8 Piso, 1600-209 Lisbon,
Portugal. geral@ersar.pt
2
Engineering Department Waste Sector, ERSAR, Portugal
3
Strategic Projects Department, ERSAR, Portugal
ABSTRACT
The first generation of performance indicators is a fundamental tool for the regulation of
the quality of the service and an essential component of the regulatory model. The
application of this evaluation tool contributed to the successful structuring and regulation
of municipal waste management services in Portugal as public visibility of the results
stimulate operators to improve the quality of their service.
This fruitful experience along with new legal requirements determined the need to adapt
this evaluation tool to address the whole municipal waste sector and to deliver a global
perspective of the sector. As a result, a new framework assessment has been prepared
to evaluate the service provided by municipal waste operators. The second generation of
quality of service indicators is thus the result of the experience gathered over seven years
with the application of a comprehensive evaluation process (2004-2010). This paper
illustrates the main strategic guidelines as well as the approach adapted for the new
assessment framework.
Keywords: regulation of waste services, quality of service, performance indicators, benchmarking.
INTRODUCTION
Municipal waste management services include both retail and bulk components, though these two
components are often provided by different operators. Retail services include the collection of
municipal waste which is provided by municipalities, as it is the responsibility of the local
administration to provide the service for municipal waste collection. Bulk services include municipal
waste treatment operations and are provided by regional operators, namely: state-owned regional
companies (under concession contracts), association of municipalities or intermunicipal companies.
The main purpose for the creation of these regional companies was to ensure the implementation
of joint solutions gathering several municipalities, especially when the required investments in the
bulk exceeded the technical, financial and management capacities of the municipalities, given the
complexity of the situations to be addressed.
In terms of market structure and for the bulk component, a legal framework has been drawn up for
the management of municipal waste in the public sphere, not only for economic reasons, but also
due to the strategic importance attributed to bulk services, with the national political agenda for the
sector. The aim was to create scale economies, both in regard to investment and operation, with a
positive outcome in the tariffs for these services.
As mentioned above, municipal waste management encompasses the retail activity of collection
and transportation by municipal systems, while the bulk activity is carried out through the regional
systems which are responsible for temporary storage, sorting, recovery and disposal of municipal
waste. Figure 1 illustrates the distribution of retail and bulk services in Portugal. These services are
undertaken by different operators according to its classification.
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According to Figure 1, in bulk services, concessions cover approximately two-thirds of the
population, and 52% of utility operators are run according to this model, while in the retail services
municipalities are mainly responsible for the service and cover the majority of the of population. In
retail services, 82% of the population is served under direct management models, and delegated
management models account for a further 16% of the population [1].
Bulk service Retail service
Figure 1. Distribution of municipal waste operators in Portugal in 2010.
In bulk services, about 60% of the market is held mainly by State owned concessions, through the
public holding company (guas de Portugal, S.G.P.S.) [1]. The remaining activity of this service is,
with very few exceptions, totally done by municipalities. In fact, private participation occurs only in
minor holdings in the share capital of multimunicipal concessions and intermunicipal companies.
In terms of the share capital of companies responsible for municipal waste management bulk
services, in 2009, this accounted to ca. 92 million euros, whereas 40% held by the State through
companies owned by the public holding. State holds the majority of shares in multimunicipal
concessions, whilst the municipalities hold 57% of the capital in the sector [1].
THE REGULATION OF MUNICIPAL WASTE SERVICES IN PORTUGAL
The Regulation Authority

The Portuguese regulatory model comprises an independent regulation authority The Water and
Waste Services Regulation Authority (ERSAR) responsible for ensuring both the quality and the
affordability of service provision. The Portuguese regulation authority for public water supply, urban
wastewater and municipal waste management is a government appointed body created in 1997
with administrative and financial autonomy. According to ERSARs statutes, its scope covers water
supply, wastewater and municipal waste services. Such activities are a structural part of public
service, being vital to the general welfare, public health and overall safety of the population, as well
as to the economic activities and the environment protection.
This sector-specific regulatory agency has undergone an organizational restructuring in 2009 and
was renamed as The Water and Waste Services Regulation Authority (ERSAR). Decree-Law nr.
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277/2009, of October 2, materialized the replacement of IRAR by ERSAR, strengthening the
regulation authority powers by increasing its regulatory intervention to all municipal waste
operators, and by normalizing regulatory procedures. The creation of ERSAR has resulted in the
expansion of its regulatory functions to all the operators, regardless of their ownership, in order to
cover entities that are part of the local administration in terms of customer protection issues. The
new regulatory context resulted in increased intervention from the regulation authority which
overviews now the activity of 252 retail operators responsible for the collection and transport of
municipal waste and 23 regional operators responsible for the treatment and disposal of municipal
waste. ERSAR faces currently a new challenge: to strengthen structural regulation, economic
regulation and quality of service regulation within the previously non-regulated sector.
The Regulatory Model

It is ERSARs priority to consolidate a clear and effective regulation policy, taking into account the
regulation practice in other fields in Portugal and internationally. Such is vital for every agent at this
sector, mainly the operators, so that they know in advance the regulation model rules and may
safely decide upon their actions.
The regulatory model for the public water supply, urban wastewater services and municipal solid
waste management services follows two major guide lines, the first being at the structural
regulation level of the sector, and the second at the operators level [2]. The direct intervention of
ERSAR at the operators level includes economic and quality of service regulation, in order to
promote adequate performance of the operators. In association to the economic regulation, the
quality of service regulation is an effective way of promoting an adequate balance between price
and quality of the service provided to the users.
The main objective of regulation is to protect the interests of consumers by promoting the quality of
service rendered by the operators and guaranteeing socially acceptable pricing, materialized in the
following principles: essentialness, indispensability, universality, equity, reliability, cost efficiency
and affordability associated with the quality of the service. However, this should be carried out
while safeguarding the financial viability and best interest of the operators, irrespective of their
status public or private, municipal or multimunicipal taking into account the consolidation of
the economic sector while also contributing to the implementation of the policies defined by the
government.
The regulatory model implemented by ERSAR is designed in order to accomplish with the following
objectives:
Global sustainability of the sector, through the application of an adequate national strategy,
legal framework, existence of reliable and updated information;
Social sustainability, protecting user interests as far as the service accessibility and affordability
of the service and the quality of the service provided;
Sustainability of the operators, namely through the economical, structural and human
resources;
Environmental sustainability, within the use and preservation of natural resources and pollution
prevention.
The existing quality of service assessment framework

ERSAR is regulating the quality of service provided by municipal waste operators under
concession contracts since 2004 through the application of an assessment framework. This tool
enables the evaluation of operators performance and benchmarks the resulting data against the
results of similar operators based in different geographic areas [3]. The results of these evaluations
are given public disclosure in Volume 3 of the Annual Report for the Water and Waste Sector in
Portugal (RASARP).
The project initially carried out by IRAR and the National Laboratory of Civil Engineering (LNEC),
aimed at the definition of an evaluation system through the application of 20 performance indicators
(PI) to measure operators performance. Three groups of PI were defined related to: 1) protection
of the user interests; 2) sustainability of the operator; and 3) environmental sustainability. Twenty
PI have been set for each of the services: water supply, wastewater treatment and municipal waste
management. These sets of PI are a fundamental tool for ERSAR to implement the quality of
service regulation, as an essential component of its regulatory model.
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SECOND GENERATION FOR QUALITY OF SERVICE ASSESSMENT
The second generation of quality of service indicators reflects the adjustment to the regulatory
scope brought by Decree-Law nr. 194/2009, which enabled a direct intervention of the regulation
authority over the whole waste sector. As a result the number of operators included in the quality of
service regulation framework increased significantly, rising from 17 operators providing bulk
services under concessions only to ca. 275 operators providing retail and bulk services, regardless
of the applicable management model. Second generation of quality of service indicators is thus
presented as the response to the above challenges.
The new set of quality of service indicators was developed by ERSAR in collaboration with LNEC
and constitutes a comprehensive revision of the former set of indicators having in mind a broader
scope of application. During the development process special attention has been drawn over the
ISO 24500 standards, referring to the assessment of water supply and wastewater treatment
services [4]. Despite municipal waste services are not within the scope of these standards its
driving principles can suit waste services. The new assessment framework is designed to include
all operators providing municipal waste services keeping a similar structure within the former
evaluation process.
The application of ISO 24500 principles ensuring that operators provide acceptable and
sustainable services to end-users and relate to environmentally sound practices, resulted on the
following objectives and criteria [4]:
Adequate user/provider interface: the evaluation is based on the criteria for service coverage
and affordability, as well as, on the quality of service provided to users;
Sustainability of the service: the evaluation is based on the criteria for economic and financial
sustainability of the service, infrastructural sustainability and human resources sustainability;
Environmental sustainability: the evaluation is based on the criteria for efficient use of
environmental resources and efficient pollution prevention.
The process must be regarded as a natural transition to accommodate the changes in the new
regulatory context and at the same time specifically address the evaluation of retail services. The
following aspects were crucial to the development of the new assessment framework and
summarize the main differences to the first generation performance indicators:
The indicators are organised according to the principles in the ISO 24500, which require the
definition of the objectives and the applicable evaluation criteria for each of the corresponding
performance indicators.
The assessment framework for municipal waste operators aims at the evaluation of the quality
of the service delivered to users and not at the operators performance.
The scope of evaluation has been defined to cover retail and bulk services in a balanced and
unbiased structure.
Simplification of the evaluation process by reducing the number of indicators from 20 to 16 and
focusing on critical aspects of the evaluation.
Critical aspects such as service coverage and affordability to the service are targeted for
evaluation.
Reference values for evaluation purposes are calculated according to best references available.
The definition of reliability levels for the data collected for assessment of municipal waste
operators is clearly defined and all data reported by the operators must fulfil these criteria.

The second generation of quality of service assessment indicators for municipal waste
management services consists of a set of 16 indicators to evaluate the operators on a yearly basis.
Prior to the evaluation, data reported by operators must be validated by ERSAR to verify its
reliability. ERSAR is thus responsible for auditing the operators in order to verify if the correct
procedures for data collection are implemented and if the reported data is reliable.
Table 1 presents the second generation of quality of service indicators organized within the above
mentioned objectives and criteria. The definition of these indicators was subject to public
disclosure. Bringing stakeholders together motivated the discussion and triggered the presentation
of criticisms, suggestions and comments. The new assessment framework will be fully applicable
from August 2011.
139
Table 1. Second generation of municipal waste management quality of service indicators
Objective: Adequate user/provider interface

RU01 - Service coverage (%) b/r
Criterion Service coverage and affordability RU02 - Selective collection coverage (%) b/r
RU03 - Affordability to the service (%) b/r
RU04 - Waste containers cleaning (-) b/r
Criterion Quality of service provided to users
RU05 - Replies to written complaints (%) b/r
Objective: Sustainability of the service
Criterion Economic and financial sustainability RU06 - Full cost recovery (-) b/r
RU07 - Packaging waste recycling (%) b/r
RU08 - Organic recovery (%) b
RU09 - Incineration (%) b
Criterion Infrastructural sustainability RU10 - Landfill use (%) b
RU11 - Collection vehicles replacement b/r
(km/vehicle)
3
RU12 - Collection vehicles use [kg/(m .year)] r
3
Criterion Human resources sustainability RU13 - Personnel (nr./10 ton) b/r
Objective: Environmental Sustainability
Criterion Efficient use of environmental
RU14 - Efficient use of energy (kWh/ton; tep/ton) b/r
resources
RU15 - Leachate quality after treatment (%) b
Criterion Efficient pollution prevention RU16 - Greenhouse gas emissions b/b/r
(kgCO2/ton)
Notes: b - bulk service assessment only; r - retail service assessment only; b/r both bulk and retail
assessment.
The indicators cover both the retail and bulk services being the assessment of bulk services
performed with 15 indicators while the assessment of retail services includes 12 indicators. An
effort was done in order to simplify the assessment framework by reducing the number of indicators
and at the same time designing new indicators to evaluate retail operators. The new assessment
framework brings five new indicators and some innovation over specific aspects of the quality of
the service. The indicators on affordability to the service, waste containers cleaning, collection
vehicles replacement, collection vehicles use and greenhouse gas emissions are new indicators,
which bring light over aspects of the quality of service that will be evaluated for the first time. The
greenhouse gas emissions indicator is a good example on how to bring together an innovative
approach and a growing environmental concern. Such indicator is a proof that the quality of service
assessment does not need to specifically concentrate on the service provision itself but rather to
understand the global aspects and interactions of the service.
The use of such an assessment tool enables the comparison of the results between similar
operators and carrying benchmarking analysis. For this purpose it is essential to have in mind that
the use of indicators requires a careful interpretation of the results to ensure that the corresponding
evaluations are sensibly addressed, in order to take into account any exogenous factors that may
affect (and potentially drive) the operators performance. The results are to be reported and made
public on a yearly basis, as this encourages operators to provide an improved service, aiming to
achieve a better performance.
Table 2 provides useful information on the second generation of the quality of service evaluation
tool as well as its main expectations. The SWOT analysis presented emphasizes on the relevant
factors supporting the evaluation process defined by ERSAR.
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Table 2. SWOT analysis for the second generation quality of service indicators evaluation tool.
Strengths Weaknesses
- Performance Indicators provide a quantitative - Data collection procedures can be time
measurement to assess quality of service; consuming;
- The quality of service assessment tool drives - The significant increase on the operators under
operators to implement data collection the quality of service assessment framework
procedures as well as reporting on a consistent and its differences in size and capacity require
basis; special attention;
- It accounts for a true culture of concise, reliable - The use of PI requires a careful interpretation of
and easily readable information for all the results to ensure that any exogenous factors
stakeholders; do not affect the operators performance.
- It allows the dissemination of information to the
end-users of the services.
Opportunities Threats
- The increased regulatory intervention of ERSAR - The complexity of the evaluation process
addressing all the operators within the municipal assessing 275 operators.
waste sector; - Data validation requires auditing the operators
- The improvement of the quality of the service which is an exhausting process.
provided by operators;
- The increasing presence of private operators in
the waste sector requires innovative instruments
for the regulation of the quality of the service;
- The need to achieve an efficient price good
quality of service at affordable prices is
becoming an important issue.
CONCLUSIONS
Several factors accounted for the development of the second generation of quality of service
indicators. Among these, changes in the regulatory context arising from new legal requirements
played a decisive role. The new regulatory context strengthened the competences of the regulation
authority and enlarged the scope of quality of service regulation to all operators providing municipal
waste services in Portugal. As a result, the second generation quality of service evaluation tool has
been redesign to assess the quality of the service provided by retail operators. For this purpose
new indicators were included to specifically address the evaluation of retail services. In addition,
the implementation of procedures and practices for data validation in order to confirm if the data
reported by the operators fulfils the reliability criteria has been defined as a priority.
This process accounts to a true culture of concise, reliable and easily readable information for all
stakeholders, as public visibility of the results is an effective way to stimulate operators to improve
the quality of their service.
REFERENCES
[1] ERSAR (2010). Relatrio Anual do Sector de guas e Resduos em Portugal. Entidade
Reguladora dos Servios de guas e Resduos 2009, ISSN 1647-9238.
[2] IRAR (2009). Sistema de avaliao da qualidade dos servios de guas e resduos prestados
aos utilizadores, 1. Gerao do sistema de indicadores de qualidade de servio. Lisboa
(Portugal). Instituto Regulador de guas e Resduos, 175 p. ISBN 978-989-95392-8-0.
[3] Almeida, J. and Nunes, M. (2007). Assessment of waste operators performance: The
Portuguese case. Proceedings Sardinia 2007, Eleventh International Waste Management and
Landfill Symposium, CISA publisher.
[4] Carvalho E., Nunes M. and Alves D. (2010). Assessement of municipal waste operators
performance in Portugal since 2004. Proceedings Venice 2010, Third International Waste to
Energy International Symposium, CISA publisher.
[5] ERSAR/LNEC (2010). Guia de avaliao da qualidade dos servios de guas e resduos
prestados aos utilizadores, 2. Gerao do sistema de indicadores. Verso preliminar
publicada em http://www.ersar.pt.
141
13th September
Keynote Lecture I
( Mechanical-Biological Treatment (MBT). role,
technologies, goals, and performances in thee
European regulatory and operational context )
Enzo Favoino
142
Professor Enzo Favoino [Scuola Agraria del Parco di Monza, Italy]
Biography
Is with Scuola Agraria del Parco di Monza, where he coordinates the Working Group on
Composting and Integrated Waste Management. He and his team have helped many
Governmental Institutions and Local Authorities to implement waste management schemes,
with a particular reference to options for the management of biowaste.
Favoino is involved across Europe and the world in scientific and technical issues related to
optimisation of schemes for source segregation, process management, improvement of
existing plants, marketing of composted products, role of mechanical-biological treatment for
residual waste. They have widely contributed to the development of source separation and
composting in many Countries. He has frequently taken part as an invited expert in meetings,
workshops, organised by the European Commission on Sustainable Waste Management and
Source Separation.
He is currently Chair of the WG on Biological Treatment at ISWA International Solid Waste

Association; hes also Vice-Chair and Member of the Board of ECN-European Compost
Network.
143
13th September
Session 1.3
Chairman: Joo Labrincha
144
MODELLING CERAMIC PROPERTIES OF TRIAXIAL CERAMIC BODIES

CONTAINING E-WASTE USING MIXTURE DESIGN OF EXPERIMENTS
1 1 1 2
S.L. Correia , F. N. Stafford , M. Tomiyama , A. M. Segades
1
Centre of Technological Sciences, State University of Santa Catarina (UDESC) 89219-710
Joinville, SC, Brazil, sivaldo@joinville.udesc.br
2
Department of Ceramics & Glass Engineering (CICECO), University of Aveiro, 3810-193 Aveiro,
Portugal, segadaes@ua.pt
ABSTRACT
In the present study, mixture design of experiments was used to model dried modulus of
rupture, linear firing shrinkage and water absorption of triaxial ceramic bodies containing e-
waste from discarded and grinded printed circuit board. Seven formulations containing
clay mixture, a phyllite rock and e-waste powder were selected and used in the
experiments design. The methodology of mixture design proved to be a useful tool for
planning and analysing experiments on the influence of raw materials on technological
properties of ceramic triaxial bodies. Although the e-waste incorporated to ceramic body
decreases the dried modulus of rupture, it contributes to promoting lower water
absorption and can be used as alternative fluxing raw material, while relieving the
environmental pressure set on the disposal of waste electrical/electronic equipment.
Keywords: E-waste; Modelling; Ceramic material; Ceramic properties.
INTRODUCTION
Waste electronic and electrical equipment (WEEE) has become a serious problem due the huge
amount of waste being scrapped every day. The printed circuit boards (PCB), which are part of the
e-waste, contain different kind of materials such as metal, oxides and organic polymers. Many
researchers have studied different ways to obtaining and processing obsolete or discarded PCB
pieces [1-4], and its application in different materials, either as filler in polymer matrix composites
[5, 6] or asphalt reinforcement [7].
In ceramics industry, given the high volume of materials processed, there is a largest consume of
natural raw materials, but has also capacity and potential to make significant contributions to
solving problems associated with other industries wastes. From this point of view the selection and
beneficiation of those wastes can turn them into properly to be used in ceramic mixtures as an inert
or fluxing material [8].
Final quality of industrial ceramic products, such as floor and wall tiles, requires the dried and fired
properties control of the manufactured pieces. Modulus of rupture of dried and fired linear
shrinkage and water absorption are commonly used as a process control parameter in industrial
ceramics. These properties depend on the raw materials and the milling/mixing, compaction and
firing conditions [9]. If processing conditions are kept constant, such properties will only depend on
the raw materials.
The design of mixture experiments is a special case of response surface methodologies, which
assume that a given mixture property depends only on the component fractions (Xi, summing up to
unity), and not on the overall amount of the mixture. In a system with q independent components,
there will be (q-1) independent composition variables Xi. The response function f can be expressed
in its canonical form as a low degree polynomial [10].
This work describes the use of the design of mixture experiments methodology to calculate a
regression model relating dried modulus of rupture, fired linear shrinkage and water absorption of
triaxial ceramic bodies, with the proportions of raw materials (clay, phyllite rock and e-waste
powder) under constant processing conditions. The model so obtained can then be used to select
145
the best combination of those raw materials to produce a ceramic body with specified physical-
mechanical properties.
METHODOLOGY
Materials
The raw materials used were two clays (A and B), phyllite rock and a waste from printed circuit
boards (e-waste). Clays and phyllite were supplied by Paran Minerao Ltda. (Tijucas do Sul,
Paran, Brazil) and the e-waste was supplied by University of Joinville (UNIVILLE, Joinville, Santa
Catarina, Brazil). The chemical composition of the raw materials was determined by X-ray
fluorescence (XRF) and crystalline phases present were identified by X-ray diffraction (XRD). A
mixture of the two clays (40.0 wt. % of clay A + 60.0 wt. % of clay B) was used. The e-waste
powder was obtained by grinding of discarded green printed circuit boards.
Methods
A {3,2} centroid simplex-lattice design was used to define the mixtures of these raw materials that
should be investigated. Seven mixtures were obtained using the Statistica 7.1 software - StatSoft
Inc., 2007. Each mix was processed following a modified procedure of ceramic industry: wet
grinding (residue left in a 325 mesh sieve below 3 wt.%), drying (24 h), moisturizing (7.00.5 wt.%,
dry basis), granulation, uniaxial pressing at 40 MPa (EMIC, 30 ton hydraulic press), test piece
drying (1105 C until constant weight) and firing at 1180 C for 2 h (heating at 5 C/min) and
natural cooling.
The dried modulus of rupture (DMoR) was determined in three-point bending tests (EMIC 30 ton
3
test machine), using test bars (70 x 40 x 10 mm ). For each mixture, the final test result was taken
as the average of the measurements carried out on ten test bars.
The linear firing shrinkage (LFS) was calculated from the change in length (measured with Mitutoyo
callipers with a resolution of 0.05 mm), upon firing, of the flat test pieces. Water absorption (WA)
was determined via boiling in water for 2 h, using a digital scale Denver DE 100A digital analytical
scale with a resolution of 1 mg. For each mixture, the property final value was taken as the average
of all test pieces evaluated (ten for linear shrinkage, five for water absorption).
The results were used to iteratively calculate the coefficients of the regression equations, until
statistically relevant models and response surfaces were obtained, relating the DMoR, LFS and
WA with the proportions of the clay mixture, phyllite and e-waste powder present in the unfired
mixture. The calculations were carried out with Statistica 7.1. StatSoft Inc., 2007).
Characterization of raw materials and mixture compositions

The XRD analysis results (XRD) coupled with XRF analysis showed that, in the clay mixture,
quartz, kaolinite and muscovite form the major phases. Phyllite rock presents quartz, kaolinite and
potash feldspar as main phases. On the other hand, the e-waste powder contains silica, light and
heavy metal alloys (lithium, magnesium, zinc, iron, cadmium, etc.) and polymeric organic materials.
The distinctive roles that clays, phyllite and e-waste might play during ceramic processing were
used to establish the limits of 40 to 80 wt. % of clay, 20 to 60 wt. % of phyllite and 0 to 40 wt. % of
e-waste, thus creating a restricted composition triangle of pseudo-components, Table 1 and Fig. 1,
on which a {3,2} simplex lattice (6 points) was set. To these original six points, a central point was
added (centroid simplex).
Measured properties and models for DMoR, LFS and WA

Having a measured value for the response properties at specific coordinates (Table 1), a
regression equation can be sought for each property. For both DMoR and LFS properties, a
second-degree polynomial [10] was found to be statistically the most adequate, with a significance
level up to 9%. However, for WA, a first-degree polynomial [10] was found to be statistically
significant at the level of 2%:
146
Table 1. Composition of design mixtures and corresponding measured values of dried modulus of
rupture, linear firing shrinkage and water absorption.
Design Weight fractions DMoR LFS WA
mixture Clay mix Phyllite E-waste [MPa] [%] [%]
1 0.80 0.20 0.00 4.020.06 7.440.31 8.110.38
2 0.40 0.60 0.00 4.210.05 6.280.42 5.950.39
3 0.40 0.20 0.40 3.920.09 10.690.89 0.050.01
4 0.60 0.40 0.00 4.060.05 6.800.38 7.720.35
5 0.60 0.20 0.20 3.830.06 8.850.28 3.290.41
6 0.40 0.40 0.20 3.890.03 10.100.42 0.270.03
7 0.53 0.33 0.14 3.900.07 8.880.16 2.070.10
Fig. 1. Triaxial system of clay mix, phyllite and e-waste and the region studied (grey triangle).
DMoR = 4.07X1 + 4.81X2 + 5.73X3 1.27X1X2 3.29X1X3 4.23X2X3 (1)

LFS = 7.92X1 + 5.17X2 + 7.68X3 + 41.79X2X3 (2)
WA = 9.51X1 + 2.18X2 14.06X3 (3)
In Eq.s (1) to (3), X1 is the clay mix fraction, X2 is the phyllite fraction and X3 is the e-waste fraction
(i.e. original component fractions). Table 2 gives the major statistical properties relevant for
variance analysis of the regressions, using the nomenclature commonly found in the relevant texts
2
[10] (p value and coefficient of multiple determination, R ).
Table 2. Major statistical properties relevant for variance analysis.

2
Response property p value R
DMoR 0.0910 0.9982
LFS 0.0008 0.9979
WA 0.0200 0.8530
147
Contour plots
Fig. 2 shows the projection of the calculated response surface (in pseudo-components) onto the
composition triangle [11-13], as constant property contours (contour plot) for the DMoR.
Fig. 2. Constant contour plot, expressed in pseudo-components, for the DMoR vs. composition.
Fig. 2 reveals that both clay mix and phyllite (x1 and x2 pseudo-components, respectively)
contribute to increase DMoR. As clay mix and phyllite present mineralogical composition containing
clay minerals, quartz and feldspar, an efficient compacting effect can be achieved using those raw
materials due to their different particle size [9]. Fig. 2 also reveals that e-waste (x3 pseudo-
component) has a harmful effect on DMoR probably due to it contains polymeric organic materials
which do not improve compacting effect on green ceramic body. Nevertheless, high DMoR values
(e.g. DMoR higher than 3.90 MPa, which indicates efficient green processing conditions) can be
reached within a reasonably forgiving composition area, corresponding to clay mixture contents, in
pseudo-components, from 0 to 98 wt. %, phyllite above 50 wt. % and e-waste below 50 wt.%. The
correspondent original component fractions can be calculated by Eq. (4) to (6) for clay mixture (X1),
phyllite (X2) and e-waste (X3) as a function of pseudo-component fractions (x1, x2 and x3) [10].
Those results show that keeping constant raw material properties and process conditions, mixtures
containing 40 to 79 wt. % of clay mixture, phyllite above 40 wt. % and e-waste below 20 wt. %
(original components) could produce green ceramic bodies with DMoR higher than 3.90 MPa.
X1 = 0.40x1 + 0.40 (4)

X2 = 0.40x2 + 0.20 (5)
X3 = 0.40x3 (6)
Fig. 3 is the constant contour plot for the LFS. It can be seen that the e-waste (X3) contributes to
increase the LFS. Fig. 3 reveals that lower firing shrinkage values (e.g. lower than 9.0 %, which is
desired for adequate sintering and optimising ceramic bodies production) can be reached within a
reasonably forgiving composition area, corresponding to e-waste contents below 20 wt.%, phyllite
contents higher than 20 wt. % and clay mixture contents above 40 wt.% (all fractions as original
components). Those results reveal that the e-waste powder can be acting as a fluxing agent thus
contributing to improve the liquid phase sintering process and enhanced fired technological
properties [14-16]. The fluxing effect for the e-waste can better be checked when studying the WA
results.
Fig. 4 shows the projection of the calculated water absorption surface (WA) onto the composition
triangle (in pseudo-components), i.e. constant water absorption contour plot. In this case, it can be
148
seen that WA is mostly controlled by the clay/e-waste ratio. As it has been discussed about the
LFS, the WA behaviour confirms that the e-waste can surely be regarded as a fluxing material [14-
16]. Fig. 4 also shows that WA values below 2.0 % can easily be reached for pseudo-clay/pseudo-
e-waste ratios below 35/50 and pseudo-phyllite content up to 50 wt. %, which translates into
mixtures with <54 wt. % clay mixture, 20 wt. %< phyllite <40 wt. %, and >20 wt. % e-waste, as
original components. The lowest water absorption values (model predicted zero) were found for
compositions with high e-waste and phyllite contents and low clay content.
Fig. 3. Constant contour plot, expressed in terms of pseudo-components, for the LFS vs.
composition.
Fig. 4. Constant contour plot, expressed in pseudo-components, for the WA vs. composition.
149
CONCLUSIONS
Design of mixture experiments and response surface methodologies were used to calculate
regression models relating dried modulus of rupture, linear firing shrinkage and water absorption with
clay mixture, phyllite rock and e-waste contents. Joint use of the models enabled the selection of the
best combination of those raw materials that produces, under constant processing conditions, a
ceramic body with specified properties.
The results obtained also showed that e-waste promotes lower water absorption and can be used
as alternative fluxing raw material, while relieving the environmental pressure set on the disposal of
waste electrical/electronic equipment.
ACKNOWLEDGEMENTS
The authors appreciate the financial support received from the Brazilian Research Agency CAPES
(F. N. Stafford, Master scholarship) and are thankful to Paran Minerao Ltda (Tijucas do Sul,
Paran, Brazil) and University of Joinville (Joinville, Santa Catarina, Brazil) for providing the raw
materials used.
REFERENCES
[1] J. Guo, Z. Xu, Recycling of non-metallic fractions from waste printed circuit boards: a review, J.
Hazard. Mater. 168 (2009) 567-90.
[2] L. Long, S. Sun, S. Zhong, Using vacuum pyrolysis and mechanical processing for recycling
waste printed circuit boards, J. Hazard. Mater. 177 (2010) 626-32.
[3] Y. Zheng, Z. Shen, S. Ma, A novel approach to recycling of glass fibers from nonmetal
materials of waste printed circuit boards, J. Hazard. Mater. 170 (2009) 978-982.
[4] J. Guo, J. Li, Q. Rao, Z. Xu, Phenolic molding compound filled with nonmetals of waste PCBs,
Environ. Sci. Tech. 42 (2008) 624-28.
[5] J. Guo, Y. Tang, Z. Xu, Wood plastic composite produced by nonmetals from pulverized waste
printed circuit boards, Environ. Sci. Tech. 44 (2010) 463-68.
[6] J. Guo, S. Wang, Z. Xu, Asphalt modified with nonmetals separated from pulverized waste
printed circuit boards, Environ. Sci. Tech. 43 (2009) 503-08.
[7] M. Peng, X. Dong, D. Guanchong, Products made from nonmetallic materials reclaimed from
waste printed circuit boards: reuse of recovered non-metallic, Tsinghua Sci. Tech.12 (2007)
276-83.
[8] A.M. Segades, Use of phase diagrams to guide ceramic production from wastes, Adv. Appl.
Ceram., 105 (2006) 46-54.
[9] J. S. Reed, Introduction to the Principles of Ceramics Processing, second ed., Wiley and Sons,
New York, 1993.
[10] J. A. Cornell, Experiments with Mixtures: Designs, Models and the Analysis of Mixture Data,
third ed., Wiley and Sons, New York, 2002.
[11] S.L. Correia, K.A.S. Curto, D. Hotza, A.M. Segades, Using statistical techniques to model the
flexural strength of dried triaxial ceramic bodies, J. Eur. Ceram. Soc. 24 (2004) 2813-2818.
[12] S.L. Correia, D. Hotza, A.M. Segades, Effect of raw materials on linear shrinkage, Am.
Ceram. Soc. Bull. 83 (2004) 9101-9108.
[13] S.L. Correia, D. Hotza, A.M. Segades, Simultaneous optimisation of linear firing shrinkage
and water absorption of triaxial ceramic bodies using experiments design, Ceram. Int. 30
(2004) 917-922.
[14] W.M. Carty, U. Senapati, Porcelain raw materials, processing, phase evolution and
mechanical behavior, J. Am. Ceram. Soc. 81 (1998) 3-20.
[15] R. Gennaro, P. Cappelletti, G. Cerri, G. Gennaro, M. Dondi, G. Guarini, A. Langella, D. Naimo,
Influence of zeolites on the sintering and technological properties of porcelain stoneware tiles,
J. Eur. Ceram. Soc. 23 (2003) 2237-2245.
[16] A. Tucci, L. Esposito, E. Rastelli, C. Palmonari, E. Rambaldi, Use of soda-lime scrap-glass as
a fluxing agent in a porcelain stoneware tile mix, J. Eur. Ceram. Soc. 24 (2004) 83-92.
150
MECHANICAL PROPERTIES AND DURABILITY OF CONCRETE WITH

PARTIAL REPLACEMENT OF PORTLAND CEMENT BY CERAMIC WASTES
1 2 3
F.Pacheco Torgal , A. Shahsavandi and S. Jalali
1 Research Unit C-TAC, University of Minho, Guimares, torgal@civil.uminho
2 Research Unit C-TAC, University of Minho, Guimares, arman.sh@civil.uminho
3 Research Unit C-TAC, University of Minho, Guimares, said@civil.uminho
ABSTRACT
The ceramic industry is known to generate large amounts of calcined-clay wastes each
year. So far a huge part is used in landfills. Reusing these wastes in concrete could be a
win-win situation. For one hand by solving the ceramic industry waste problem and at the
same time leading to a more sustainable concrete industry by reducing the use of non
renewable resources like cement and aggregates and avoiding environmental problems
related to land filled wastes. This paper examines the feasibility of using ceramic wastes
in concrete. Results show that concrete with 20% cement replacement although it has
minor strength loss possess increase durability performance. Results also shows that
concrete mixtures with ceramic aggregates perform better than the control concrete
mixtures concerning compressive strength and chloride diffusion.
Keywords: Concrete; ceramic wastes; mechanical properties; durability performance
INTRODUCTION
In Europe the amount of wastes in the different production stages of the ceramic industry reaches
some 3 to 7% of its global production meaning millions of tons of calcined-clays per year that are
just land filled [1]. With increasing restrictions on landfills in European Union area, the cost of
deposition will increase and the industries will have to find ways for reusing their wastes. Although
the reutilization of ceramic wastes and has been practiced, the amount of wastes reused in that
way is still negligible. Hence, the need for its application in other industries is becoming absolutely
vital. Construction industry as the end user of almost all the ceramic materials is well posed to
solve this environmental problem which is partly its own. The nature of construction industry,
especially the concrete industry, is such that ceramic wastes can be used safely with no need for
dramatic change in production and application process. On one hand, the cost of deposition of
ceramic waste in landfill will be saved and, on the other, raw materials and natural resources will be
replaced, thus saving energy and protecting the environment. According to some authors the best
way for the construction industry to become a more sustainable one is by using wastes from other
industries as building materials [2,3]. The production of cement requires high energy input (850
kcal per kg of clinker) and implies the extraction of large quantities of raw materials from the earth
(1,7 tonnes of rock to produce 1 tonne of clinker). On the other hand the production of one tonne of
cement generates 0,55 tonnes of chemical CO 2 and requires an additional 0,39 tonnes of CO 2 in
fuel emissions, accounting for a total of 0,94 tonnes of CO 2 [4]. Therefore, the replacement of
cement in concrete by ceramic wastes represents a tremendous saving of energy and has
important environmental benefits. Several authors already confirmed the pozzolanic reactivity of
ceramic wastes [5-7], nevertheless, research carried out so far by reusing ceramic wastes in
concrete are scarce and do not evaluate concrete durability performance which is a key issue. On
the other hand, recent research in the field of reusing ceramic aggregates in concrete are scarce
and do not evaluate concrete durability performance [8,9]. Consequently the aim of this research
project is the assessment of the properties and durability of of ceramic waste based concrete.
151
Experimental work
Materials and concrete mix design
The chemical compositions of ceramic pastes were analysed and results obtained are reported in
Table 1. The silica and alumina are the most significant oxides present in the ceramic pastes. The
variation of proportion of the silica and alumina is due to the clay used. It should be noted that the
red paste shows high proportion of iron oxide responsible for the red colour of the products.
Ceramic wastes were crushed with a jaw crusher to make the ceramic aggregate. Thus, by using
this system to crush ceramic wastes it is possible obtain coarse aggregates, fine aggregates and
ceramic powder that after sieving can be used without additional work and with minimal cost
implications.
Table 1 - Chemical composition of ceramic pastes

Type Si02 Al203 Fe203 Ca0 Mg0 Na20 K20 Ti02
Red paste twice fired ceramic 51.7 18.2 6.1 6.1 2.4 0.2 4.6 0.8
White paste once-fired
58.0 18.0 1.0 8.3 0.6 0.2 1.2 0.8
ceramic
White paste for twice -fired
59.8 18.6 1.7 5.5 3.5 1.6 2.5 0.4
ceramic
Red paste for stoneware tile 29.1 20.3 7.7 1.2 1.1 0.4 4.2 0.9
White paste for stoneware tile
65.0 21.3 1.3 0.2 0.3 2.5 3.7 0.2
White paste for sanitary ware 65.8 22.2 0.6 0.1 0.1 1.0 3.5 0.3
At laboratory scale the ceramic wastes were grounded with a ball mill with metal balls to obtain
ceramic powder. The ceramic powders with a particle size 75m were chosen for the partial
substitution of cement. The coarse aggregate and the coarse sand used in the concrete mixes with
cement replacement by ceramic powder were crushed granite aggregates. For the production of
concrete samples in phase A, Portland cement, CEM I-32.5, complying with the NP EN 197-
1:2001was used along with both natural sand and granite aggregates. The concrete mixes were
determined using the Faury method, applying a computer programme [10,11]. A mix design, with
2 2
characteristic strength fc=25N/mm and a target mean strength fm=30 N/mm was studied. Four
mixes with 20% replacement of cement by ceramic powder were also prepared. Each one is
named after the source of the ceramic waste: CB (ceramic bricks); WSTF (White stoneware twice-
fired); SW (sanitary ware); WSOF (White stoneware twice-fired). The compositions of the concrete
mix used in phase A are described in Table 2.
Table 2-Concrete mix proportions per cubic meter of concrete used in phase A
Control mix Concrete mixtures with ceramic wastes
Portland Cement 350.0 Kg. Portland Cement 280.0 Kg.
Coarse aggregate 1084.0 Kg. Ceramic waste powder 70.0 Kg.
Fine sand 135.4 Kg. Coarse aggregate 1084.0 Kg.
Coarse sand 564.0 Kg. Fine sand 135.4 Kg.
Water 218.5 l Coarse sand 564.0 Kg.
W/C 0.6 Water 218.5 l
The equivalent ceramic aggregate concrete for each mix was obtained by replacing the natural
aggregates with an equal volume of crushed ceramic, everything else remained the same. To have
a direct comparison of concrete made with crushed-ceramic aggregate with conventional concrete,
two corresponding mixes were prepared one replacing natural sand by ceramic sand (MCS) and
other where coarse granite aggregate where replaced by ceramic coarse aggregate (MCCA). The
ceramic aggregates were soaked in water for 24 hr and then air-dried to a saturated surface dry
condition before mixing with other ingredients. For the production of concrete samples in phase B,
Portland cement, CEM I-42.5, complying with the NP EN 197-1:2001was used. The concrete mixes
were determined using the Faury method, applying a computer programme. The compositions of
the concrete mix used in phase B are described in Table 3.
152
Table 3 - Concrete mix proportions per cubic meter of concrete in phase B
Materials Control MCS- Mix with MCCA- Mix with ceramic
ceramic sand coarse aggregate
CEM-II 42,5 350 350 350
Sand 861 - 861
Ceramic sand - 729 -
Coarse aggregate 958 958 -
Ceramic coarse aggregate - - 820
Water 175 175 175
W/C 0,5 0,5 0,5
Experimental procedures
The compressive strength was determinate following the NP EN 12390-3:2003. The specimens
were conditioned at a temperature equal to 18 1 C cured under water until they have reached
3
the testing ages. Tests were performed on 100x100x100 mm specimens. Compressive strength
for each mixture was obtained from an average of 3 cubic specimens determined at the age of
7,14, 28, 56 and 90 days of curing.
Durability aging test

The aging test performed is composed by twelve cycles; each cycle has 4 steps and one
conditioning period (Table 4).
Table 4-Durability aging test phases

Principal phase
Exposure Temperature Relative Humidity Duration
Dry Heat 752 C 45% 90 min
Cold -102 C --- 90 min
Wet Heat 552 C 95% 90 min
Cold -102 C --- 90 min
Conditioning phase
Conditioning 232 C 50% 960 min
The different phases have been selected to simulate dry heat, cold weather and wet heat and cold.
Further the rapid change of temperature from 75C to 10C and then from 10C to 55C and
dropping quickly to 10C in each cycle to simulate the thermal shock that concrete can suffer.
Following the curing period, all the specimens were weighed and half of the specimens were
submitted to twelve cycles of aging 24 hours long each, the remaining specimens were kept in the
curing chamber at constant 21C. All specimens were subjected to compressive strength test.
Using ceramic powder as partial replacement of cement

Compressive strength,
The results obtained indicate, as expected, large differences in early curing ages and smaller
differences at long curing ages (Fig. 1). The concrete mixture with 20% of CB waste has the
highest mechanical performance for all ceramic wastes which means it has higher pozzolanic
reactivity. The concrete mixture with WSOF wastes has the worst mechanical performance at early
ages, representing 74,8% of control strength for 7 days curing.
153
45
40 Control
Compressive strength (MPa) 35
CB
30
25
WSTF
20
15
SW
10
5 WSOF
0
0 14 28 42 56 70 84 98
Curing days
Figure 1 Compressive strength at different curing ages.
For 28 days curing that concrete mixture has almost 80% of the control strength index. However,
for 90 days curing the compressive strength activity index of the WSOF mixture reaches 90,4%.For
long curing ages concrete mixtures with 20% cement replacement has minor the strength loss.
Since higher curing temperatures increase the rate of pozzolanic activity pre-fabrication industry
may be an ideal way to their employment. This is because higher curing temperatures are used in
concrete pre-fabrication for accelerated demoulding.
Durability performance
As for the durability aging test (Fig.2), results indicate that all mixtures without exception have
higher durability performance which confirms the positive impact of the ceramic additions.
52
Durability aging test - Compressive
strength before and after
49
46
43
Control CB WSTF SW WSOF
Concrete mix
Figure 2 Compressive strength: Before and after the durability aging test
Using ceramic aggregates replacing traditional aggregates

The results obtained (Fig. 3) indicate that the strength is higher for concrete with both replacements
coarse ceramic aggregate (MCCA) and ceramic sand (MCS) than control concrete with traditional
aggregates.
154
60
50 Control
Compressive strength (MPa)

40
30 MCS
20
10 MCCA
0
0 14 28 42 56 70 84 98
Curing days
Figure 3 Compressive strength
This behaviour is opposite to the one obtained by others using low percentage crushed brick
aggregates [12,13]. One explanation for that may be due to the fact that they used brick
aggregates with a water absorption level between 16% and 19%, which is much higher than the
water absorption of the ceramic aggregates used in the present investigation. Another explanation
relates to the fact that ceramic aggregates are used in a pre-saturated state they can provide water
for cement hydration. Nevertheless, the strength performance is higher for concrete mixtures with
ceramic sand beyond 14 days curing. As for concrete mixtures with coarse ceramic aggregate a
maximum strength level is attained at 28 days curing.
Durability performance
As for the durability aging test (Fig.4) compressive strength reduction is higher for ceramic based
concrete.
58
Durability aging test - Compressive
53
strength before and after
48
43
38
Control MCS MCCA
Concrete mix
Figure 4 Compressive strength: Before and after the durability aging test
Nevertheless, compressive strength after the aging test is still higher in ceramic based concrete.
Therefore, the replacement of traditional sand in concrete by ceramic sand represents important
environmental benefits. Avoids the extraction of large quantities of raw materials from the earth,
avoid energy costs and also landfill problems.
155
CONCLUSIONS
Results show that concrete with ceramic waste powder although has minor strength loss possess
increase durability performance. Results also show that replacement of traditional sand by ceramic
sand is a good option because does not imply strength loss and has superior durability
performance. As for the replacement of traditional coarse aggregates by ceramic coarse
aggregates, the results are promising but require further investigations.
References
[1] M. Fernandes, A. Sousa, A. Dias, Environmental impact and emissions trade. Ceramic industry.
A case study. Portuguese Association of Ceramic Industry APICER (2004)
[2] P. K. Metha, Reducing the environment impact of concrete. Concrete can be durable and
environmentally friendly. Concr Inter 10 (2001)
[3] C. Meyer, The greening of the concrete industry. Construction and Building Materials (2009)
[4] E. Gartner, EIndustrially interesting approaches to low-CO2 cements. Cem Concr Res 34 (2004)
1489-1498.
[5] F. Puertas, I. Garcia-Diaz, A. Barba, M. Gazulla, M. Palacios, M. Gomez, S.Martinez-Ramirez,
Ceramic wastes as alternative raw materials for Portland cement clinker production. Cem
Concr Compos 30 (2008) 798-805.
[6] A. Naceri, M. Hamina, Use of waste brick as a partial replacement of cement in mortar. Waste
Manag 29 (2009) 2378-2384.
[7] A. Lavat, M. Trezza, M. Poggi, Characterization of ceramic roof tile wastes as pozzolanic
admixture. Waste Manag 29 (2009) 1666-1674.
[8] H. Binici, Effect of crushed ceramic and basaltic pumice as fine aggregates on concrete mortar
properties. Constr Build Mat 21 (2007) pp.1291-1197.
[9] P. Cachim, Mechanical properties of brick aggregate concrete. Constr Build Mat 23 (2009)
pp.1292-1297.
[10] J. Faury, Beton. Influence de ses constituents inerts. Regles adopter pour sa meilheure
composition. Sa confection et son transport sur les chantier. 3rd ed. Paris, Dunod (1958).
[11] J. Loureno, J. Coutinho, Automatic calculations for concrete mix selection. Faury and
Bolomey methods. Technical documents, Coimbra (1986)
[12] J. de Brito, A.Pereira, J. Correia, J.- Mechanical behaviour of non-structural concrete made
with recycled ceramic aggregates. Cem Concr Compos 27 (2005) 429-433.
[13] J. Khatib, Properties of concrete incorporating fine recycled aggregate. Cem Concr Res 35
(2005) 763-769.
156
THERMAL BEHAVIOR OF ICB OBTAINED FROM DEMOLITIONS
1 2
L. Gil , P. Silva
1 Laboratrio Nacional de Energia e Geologia, Unidade de Engenharia de Produto, Estrada do
Pao do Lumiar, 1649-038 Lisboa, Portugal, luis.gil@lneg.pt
2 Laboratrio Nacional de Energia e Geologia, Unidade de Engenharia de Produto, Estrada do
Pao do Lumiar, 1649-038 Lisboa, Portugal, paulo.silva@lneg.pt
ABSTRACT
This work shows preliminary tests made with Insulation corkboard (ICB) obtained from
the demolition of the cold chambers of DOCAPESCA. This company (the biggest
European company working in the fishing industry) is a state-owned company that
manages fishing port facilities and first sale fish markets all over Portugal. They have
local headquarters in all the major ports and, in the Lisbon area. The demolition work
(carried out by the company Demotri S.A.) started in March 2011, and ICB samples were
th
obtained in March 30 . The results are in line with previous results with ICB from other
demolition sources and are a proof of ICB durability.
Keywords: Insulation corkboard; demolition; recycling
INTRODUCTION
ICB is a product made of granules of cork which are expanded (steambacked) in autoclaves and
agglomerated together by pressure and temperature (>300C) without any exogenous glue. The
characteristics of ICB (standards NP 67 and ISO 2219) are:
-3
Apparent density < 140 kg.m
-1 -1
Thermal conductivity coefficient () < 0.042 W.m .K ;
This agglomerate is exclusively made of cork granules (mainly from winter virgin cork) of a larger
size (usually 5-20 mm) than those used in composition cork. The granules are bonded by their own
resins in molds defined by the autoclave walls. ICB is a completely natural product since its
agglomeration process is due to cork natural resins and to the granules expansion, without using
any glues or additives or other materials then cork [1].
The demolition work (carried out by the company Demotri S.A.) started in March 2011, and ICB
th
samples were obtained in March 30 (see Fig. 1). The area is going to be re-qualified by
Administrao do Porto de Lisboa S.A. for the event Volvo Ocean Race in 2012.
The total amount of ICB obtained by demolition is going to be quantified and sent to an ICB
production company where after separation of impurities and grinding it is going to be used to
produce re-granulated expanded cork e.g. for light weight concrete.
157
Fig. 1 Cold chamber wall with ICB insulation.
EXPERIMENTAL PART
3
The samples (see Fig. 2) belong to the cold stores (overall capacity of 62 000 m , prepared for
hundreds of tons of fish daily) for frozen fish products, with a big chamber for common storage and
16 smaller chambers for private storage. These buildings were initially built at the end of the 50s
and rebuilt in 1970, so the collected ICB was used for 41 years. Two samples were selected:
- sample A from the insulation of an interior cold corridor (for product transportation), 1 layer
with a thickness of 15 cm;
- sample B from cold storage chamber, two layers of 15 cm + 10 cm.
The thermal conductivity coefficient was measured using the fluximeter method with an Apparatus
ANACON TCA8 hot plate (37,7C), cold plate (10C), according to the International Standard ISO
8301:1991.
Fig. 2 ICB material obtained from demolition.
158
The results (average of 3 test specimens) were as in Table 1.
Table 1 Thermal conductivity coefficient from different ICB demolition samples

-3
Sample Apparent density [Kg.m ] Thermal conductivity
coefficient
-1 -1
[W.m .K ]
A 100 0.0389
B 134 0.0407
If we use the equation Eq. 1 for ICB thermal conductivity (see e.g. [1]):
-4 -1 -1
= (220 + 1.36 ) X 10 W.m .K (1)
-1 -1
the foreseen for sample A and B is, respectively, of 0.0356 and 0.0404 W.m .K .
CONCLUSIONS
It can be concluded that, after several decades of intensive use in heavy conditions, ICB shows a
thermal behavior similar or better than the specified for ICB in relevant standards. This is in line
with previous results with ICB from other demolition sources [2][3] and it is a proof of ICB durability.
References
[1] L. Gil, Technical Manual. Cork as a building material, ed. APCOR, St M Lamas, 2007.
[2] L. Gil, Life time of insulation cork board, Proceedings of International Conference on
Application of Life Cycle Assessment in Agriculture, Food and Non-Food Agro-Industry and
Forestry: Achievements and Prospects, Brussels, (1996), p. 333-334.
[3] L. Gil, Life extension of insulation corkboard, Proceedings of World Renewable Energy
Congress VII, Cologne, (2002), p. 705.
159
THE RECYCLING OF COPPER MILL SCALE FOR COPPER POWDER

PRODUCTION
B. Fernndez1, J. Ayala1, J. Sancho2 and P. Garca1

1Escuela de Minas de Oviedo
2Residuos. Principado de Asturias.
C/ Independencia, 13 - 33004 Oviedo
Abstract
Copper is the third most used metal in the world behind steel and aluminium and can
be recycled without losing its quality as well as contributing in this way at the care of
the environment. Electrolytic copper lamination generates a waste product called mill
scale, which contains a very significant amount of Cu in oxides forms. This paper
presents the results obtained in the laboratory for the study and recycling of copper
mill scale produced in a local wire drawing plant. In particular, we present the results
in the development of a method for treating this product for use as feedstock in the
production of copper powder
Keywords: mill scale, cooper powder, electrolysis
Introduction
Copper producers all around the world are facing continuously increasing demands both
economically and environmentally. Electrolytic copper lamination generates a waste product
called mill scale, which contains a very significant amount of Cu in oxides forms. Nowadays, this
industry is seeking alternative ways to exploit this byproduct, eliminating this way, costs of
elimination and pollution
This paper tries to develop a method of using the mill scale residue as raw material for the
production of copper powder, due to this byproduct contain a high concentration of copper
among several other impurities.
Copper powder is widely used in electronics and powder metallurgy. There are four commercial
ways to produce copper powder: oxidation reduction, atomization, electrolytic and wet
metallurgical methods. Among these methods, electrolytic method is an ideal one due to its
simple process flow sheet, low energy consumption, high output, easy control and low
environmental pollution [1-5].
Since the powder production process is essentially identical that of electrolytic refining of blister
copper in that a copper anode dissolves and is reduced at the cathode. However, deposit
160
conditions varied for obtaining copper as a powder instead of the adhesive metal layer that
general is obtained by electrowinning[6-7]
The electrolytic preparation of copper powder requires the deposit to be powder or spongy, this
is encouraged by high current densities. Electrocrystallisation has two stages, nucleation and
growth, for smooth cathodes growth is enhanced over nucleation but the converse is true for
powder production where each nucleus is a powder particle. Therefore, the key to changing the
particle size of the copper powder is changing the relative rates of nucleating and crystal
growth.
Properties of metal powder deposited on the cathode depend on various parameters such as
concentration of ions, pH, bath temperature, current density, presence of additives in the
electrolyte, etc. [8-10] A number of studies on the effects of various parameters on the
electrowinning
of copper from their sulphate solutions have been reported .
This paper presents the effect of various parameters on the electrowinning of copper powder
from mill scale byproduct. Properties of the electrowon copper powders have also been
evaluated.
Experimental method
First an initial characterization of the waste (Table 1) was done. Moisture content, lubricants,
chemical analysis by EDTA and atomic absorption, mineralogical analysis, particle size and
morphological parameters were calculated, too.(Figure 1) After this, it was determined the
leaching conditions required to obtain a sulphate copper solution that, once conditioned with
optimal features, allows to recover the copper as fine powder of electrolytic cooper.
Table 1. Chemical analysis of mill scale.
[%] Moisture [%] Lubricant [%] Cu [%] Fe
6.67 0.2 90 0.03
Unit 5 microns X 170
161
Figure 1. SEM of the mill scale
For the mill scale acid leaching, sulfuric acid was used, followed by a filtration. Dissolution of
this waste with sulfuric acid, is characterized by the natural cuprite dismutation . Dismutation
+
reaction can be described quantitatively by two simultaneous reactions involving both H and
the hydrolytic adsorption of the acid sulfuric
There are varied solutions of copper sulphate to obtain electrolytic copper powder. For example,
the amount of copper in the electrolyte may vary between 10 - 35 g / l and the sulfuric acid
concentration in excess, between 60 - 160g / l , depending on the efficiency and characteristics
of copper powder desired.
In our case the initial solution was set around 19 to 20 grams of Cu per liter and concentrations
of sulfuric acid added in excess, in g / l, were varied. The influence of excess acid in the
dissolution of copper at room temperature, and the leaching time to achieve the required
concentration, were studied
To perform the tests, we used a pyrex glass where the sample of mill scale was mixed with the
acid solution and subjected to a stirring mixture with a speed of 500 rpm. We worked with 36
grams of mill scale and different amounts of acid from 90 to 200 g / l.
To control the process, 5 ml of solution were extracted each 15 minutes to analyze the copper
content of the sample with EDTA, calculated in this way, the concentration and the percentage
of Cu extracted.
Finally, the electrolysis was carried out at room temperature, with a lead anode and a titanium
cathode. The electrolyte had a concentration of 20 g Cu / l, 140 g H 2SO4 /l and 1 g of glucose as
refiner. We worked with a current intensity of 7 amps, a voltage of 4V, with a current density of
2
501 A/m and a sweep time of 30 minutes
After the electrolysis, we proceeded to wash the copper with 0.1% benzoic acid, due to the
easily oxidized of the powder in contact with air. This way permits to remove the electrolyte that
remains attached to copper powder and its stabilization. Finally, copper was filtered and dried
in an inert atmosphere of N2, at 150 C
Copper powder obtained was characterized. We obtained a final product with 99.94% Cu and
with an oxygen content of 0.13%. The copper powder has a dendritic morphology with round
grains, with most of the particles of less than 45 microns and submitting a bulk density of 1.33
3 2
g/cm , very good fluidity and a surface area of 2000 cm / g.(Table 2)
The electrolytic preparation of copper powder is favoured by a low concentration of ion metal
and a high concentration of acid in the electrolyte, in addition to a high current density at the
162
cathode. Although these conditions lead to a metal powder deposit, it is necessary to control
other variables to produce a copper powder with commercial properties. These other factors
include the type and amount of agent added, the temperature and velocity of electrolyte, type
and size of anode and cathode, the distance between the electrodes and the scanning range of
dust.
Unit 5 microns X 10000
Figure 2. SEM of the mill scale
Table 2. Characteristics of the copper powder obtained.
Sieving
> 63 microns 18%
63 to 45 microns 27.7%
<45 micron 53.5%
Bulk Density g/cm2 1.33
Fluency seg/50 grams 40
Surface area cm2/ g 2000
CONCLUSIONS.
It has found a method of using the mill scale residue as raw material for the production of
copper powder. This waste has a copper content of 90%. When it is leached with sulphuric acid,
concentrations between 90 and 200 g / l produce a rapid dismutation of cuprite in 15 minutes.
90 minutes longer it would be necessary to achieve a concentration of 20g / l necessary to
make the electrolysis.
Electrolytic copper powder obtained with this solution once aconditioned with glucose and a
sweep time of 30 minutes, has a copper content of 99.94% and 0.13% of oxygen.
163
Finally, it is important to point out that the copper powder obtained has a dendritic morphology
with round grains, with most of the particles of less than 45 microns and submitting a bulk
3 2
density of 1.33 g/cm , very good fluidity and a surface area of 2000 cm / g.
References
[1] J.P Sancho Martnez.; J Ayala Espina.; M.P Garca Coque.; B Fernndez Prez.; D.
Costales Alonso. Sulphuric acid leaching of Bayer electrofilter fines, a practical kinetic
approach. JOM. August (2006) 58- 63.
[2] J.P. Sancho Martnez; J. Ayala Espina.; M.P .Garca Coque.; B. Fernndez Prez. Leaching
behaviour of a Bayer electrofilter fines in sulphuric acid. Hydrometallurgy 96 (2009) 35 41.
[3] S. Espiari., F. Rashchi, S.K Sadrmezhaad. Hydrometallurgical treatment of tailings with high
zinc content. Hydrometallurgy 82 (2006) 54 62.
[4] C. Li, B. Liang, S.P. Chen, Combined milling-dissolution of Panzhihua ilmenite in sulphuric
acid. Hydrometallurgy 82 (2006) 93 99.
[5] S. Wang. Recovery copper using a combination of electrolytic cells. JOM (2002) 51 -54.
[6] Archana Agrawal, Sarita Kumari, D. Bagchi, V. Kumar and B.D. Pandey. Recovery of copper
powder bleed from copper electrolyte of an Indian smelter by electrolysis. Mineral Engineering
20, 1(2007) 95 -97.
[7] Juanqin Xue, Qlan Wu, Zhaoqi Wang and Shefeng Yi. Function of additives in electrolytic
preparation of copper powder. Hydrometallurgy 82, 3-4, (2006) 154 156.
[8] Jinhe Sun, Yan Jung, Yougzhong Jia, Monique Titllard, Claude Belin. Mechanism of
preparing ultrafine copper powder by polypol process. Material letters 59 (2005) 3933- 3936
[9] He Feng, Zhang Zhengyi, Xiao Yaofu, Wang Wuxiang, Han Yafang, Wang Run.; A new
electrolytic method of preparing ultrafine metallic powders. J. of Matrials Processing
Technology, 137 (2003) 201 -203.
[10] Bin Zhao, Zhijie Liu, Zongtao Zhang, Liming Hu Improvement of Oxidation Resistance of
Ultrafine Copper Powders by Phosphating Treatment Journal of Solid State Chemistry, 130, 1,
1997, 157-160
164
13th September
Session 2.3
( INNOVATIVE WASTE TREATMENT TECHNOLOGIES 2 )
Chairman: Fernanda Margarido
165
ADSORPTION PROCESS ONTO AN INNOVATIVE EGGSHELL-DERIVED

LOW-COST ADSORBENT IN SIMULATED EFFLUENT AND REAL
INDUSTRIAL EFFLUENTS
1 2
J. Carvalho , A. Ribeiro, J. Graa, J. Arajo, C. Vilarinho and F. Castro
1 CVR Centre for Waste Valorization/CT2M, jcarvalho@cvresiduos.pt
3 CVR Centre for Waste Valorization, jessicagraca@live.com.pt
4 CVR Centre for Waste Valorization, jaraujo@cvresiduos.pt.
5 University of Minho/CT2M, candida@ dem.uminho.pt.
6 University of Minho/CT2M, fcastro@ dem.uminho.pt.
ABSTRACT
As the current global trend towards more stringent environmental standards, technical
applicability and cost-effectiveness became key factors in the selection of adsorbents for
water and wastewater treatment. Adsorption is by far the most versatile and widely used
method for the removal of pollutants due to its high removal capacity and ease of
operation at large scale. Recently, various low-cost adsorbents derived from agricultural
waste, industrial by-products or natural materials, have been intensively investigated. In
this respect, the eggshells from egg-breaking operations constitute significant waste
disposal problems for the food industry, so the development of value-added by-products
from this waste is to be welcomed. The egg processing industry is very competitive, with
low profit margins due to global competition and cheap imports. Additionally, the costs
associated with the egg shell disposal (mainly on landfill sites) are significant, and
expected to continue increasing as landfill taxes increase. The aim of the present was to
provide an overview on the adsorption process both on simulated and real effluents onto
eggshell-derived adsorbent. This was accomplished by analyzing the uptake potential for
selected contaminants. Real wastewater effluents were studied to determine the
effectiveness of this low cost adsorbent. Results obtained shown that eggshell can
remove several pollutants from different types of aqueous systems, with great efficiency.
Keywords: Eggshell by-products, Low-cost adsorbents, Adsorption, Wastewater treatment
INTRODUCTION
The presence of toxic contaminants in aqueous streams, arising from the
discharge of untreated effluents into water bodies, is one of the most important
environmental issues in the field of waste management [1,2]. With the rapid
increase in population and growth of industrialization all around the world, quality
of both surface and ground water is deteriorating day by day. Treatment of
industrial wastewater is increasingly necessary with respect to international
regulations which mandated the reduction of different compounds in the cleaned
water. Various methods are available for the removal of toxic pollutants from water
and wastewater including reverse osmosis, ion exchange, precipitation, electro-
dialysis, adsorption etc. Among these, adsorption is by far the most versatile and
widely used method for the removal of pollutants due to its high removal capacity
and ease of operation at large scale [3-7]. Activated carbon has been the most
versatile adsorbent for the removal of various compounds from aqueous solutions.
166
However, high cost of activated carbon restricts its application, prompting an
increased research interest into the production of low-cost alternatives to the
commonly used activated carbon. Recently, various approaches have been
studied for the development of cheaper and effective adsorbents. These low-cost
adsorbents include natural materials, biosorbents, and waste materials resulting
from industry and agricultural activities. Although many research works have been
done recently to find the potential of using various agricultural-derived alternative
adsorbents, so far no efforts have been made to obtain an overview of a specific
adsorbent derived from poultry by-products the eggshell waste in terms of their
removal performance, adsorption capacity, and cost effectiveness. Additionally,
despite the fact that industrial effluents contain several pollutants simultaneously,
little attention has been paid to adsorption of pollutants from mixtures. Considering
this, the aim of the present work is to evaluate the adsorption ability of the eggshell
low-cost adsorbent on both simulated and real industrial effluents.
State of Art
The porous nature of eggshell makes it an attractive material to be employed as
an adsorbent. The eggshell typically consists of ceramic materials which are
arranged in a three-layered structure, namely the cuticle on the outer surface, a
spongy (calcareous) layer and an inner lamellar (or mammillary) layer. The spongy
and mammillary layers form a matrix composed of protein fibers bonded to calcite
(calcium carbonate), representing more than 90% of the material. The two layers
are also constructed in such a manner that there are numerous circular openings
(pores). The utilization of the eggshell and ESM by-products has started over 1970
with the development of several studies aiming at the calcium supplement and
other nutrition sources from the albumin, membrane and matrix of the eggshell,
which was processed by crushing and milling to obtain fine particles (flours) for
animal use. Several researches have been conducted to evaluate the adsorption
ability of eggshell as low cost adsorbent, in artificial wastewater with mono or multi
components. This studies demonstrated the effectiveness of this adsorbent in the
removal of heavy metals [3,11-16], phenolic compounds [17], dyes [10,18-21] and
pesticides [22]. Nevertheless, the optimization of variable parameters such
adsorbent dose and contact time [16] remains to be investigated. Arunlertaree and
colleagues [23] investigated the removal of lead from manufacturing wastewater
by adsorption onto eggshell powder. They have conducted several batch studies
at unadjusted pH, reaching the reduction of lead concentration to values below
quality standards. Later on, Park and collaborators [24] studied the adsorption of
chromium, cadmium and lead from a real electroplating wastewater treatment
facility. They identified calcined eggshell as a good adsorbent for treatment of
acidic wastewater with a considerable uptake of heavy metals, as result of
eggshell neutralization capacity. In the present paper we assess the adsorption
capacity of eggshell powder to remove organic and inorganic compounds from
both simulated wastewater and different types of real wastewater effluents,
comparing the adsorption capacity of eggshell in different operating conditions.
167
Adsorption measurement
The adsorption capacity was calculated by determining the final concentration at
equilibrium, according to Eq, 1
qe =((C0-Ce)*V)/m (1)
where qe (mg/g) is the solute adsorption capacity per gram of eggshell, C 0 and Ce
(mg/L) are the concentration at initial and equilibrium, respectively, V (L) is the
volume and m (g) is the mass of eggshell used.
Sorbent
The sorbent used in the present paper was eggshell powder, collected from a local
hatchery waste. Shells were washed with distilled water and the membrane was
recovered by hand. They were left in distilled water overnight. After complete
removal of the organic fraction, shell was washed again. Afterwards, the material
were dried at 105C for 24h, milled and calcined at 1000C for 2h.
Concentration of pollutants
The concentration of organic matter was determinate by measuring chemical
oxygen demand (COD), by closed reflux method. The concentration of aluminum
(Al) and copper (Cu) was given by atomic adsorption spectrometry (AAS),
whereas aluminium was measured by nitrous oxide acetylene and, copper and
sodium were determining by Air-acetylene flame method [25].
Preparation of simulated solutions

The copper solution was prepared from stock solution of CuSO 4.5H2O (Merck) by
dissolution in distilled water. The blue methylene solutions were performed from
powder blue methylene (C.I. 52015, Merck), by dissolution in distilled water.The
chloride solutions were prepared from stock sodium chloride solution, NaCl, by
dissolution in distilled water.HCl (0.1N), H2SO4 (0.1N) and NaOH (0.1N) solutions
were used to adjust pH values.
Real wastewater system

Three different types of wastewater effluents were analyzed. Removal of organic
matter was assessed in municipal wastewater from unit treatment facilities and
from landfill leachates, collected from a local landfill plant. Adsorption of aluminium
was studied in the wastewater effluent from an aluminium anodizing plant. The
samples were recovered in proper containers and stored at 4C [25].
Wastewater effluents composition
Table I. Characterization of diferent types of wastewater used in the present paper.

Municipal Leachate Anodizing
pH 7.75 8.38 13.04
CQO [mg/L] 579 5760
Metals
168
Al [mg/L] 870
Experimental batch procedures
To determine the optimized operating conditions for pollutants removal of the
different wastewater samples, batch studies were carried out with eggshell powder
in a 100 mL beaker of aqueous solution, with agitation and pH control. All batch
adsorption studies were conducted at room temperature. To determine the effect
of eggshell dosage on the copper and chloride removal, 1, 3, 5 or 8 g/L of eggshell
powder were added to each set of experiments. To evaluate copper uptake, the
initial concentration was 60 mg/L and for the chloride removal 300 mg/L was used.
For the adsorption studies of methylene blue, at initial concentration of 5 mg/L, a
range of concentrations varying from 10 to 80 g/L of eggshell powder was used.
To determine the removal of organic matter from real wastewater effluents,
dosages of eggshell in the range of 5 to 20 g/L were used. Fort the removal of
aluminium, eggshell powder concentrations varied from 1 to 8 g/L.
Adsorption studies at simulated aqueous system

The adsorption capacity of eggshell, for copper and chloride removal, as function
of the adsorbent dosage, is shown in Figure 1. It can be stated that the adsorption
capacity of eggshell is proportional to eggshell concentration and the best
adsorption capacity corresponding at eggshell amount of 1g/L, both for copper and
chloride. It is clear that eggshell possesses more affinity to copper than chloride,
revealed by the higher value of adsorption capacity found for copper. However, for
the higher concentrations of eggshell powder, the removal of both copper and
chloride is comparable.
Accordingly, similar results correlating the adsorption capacity with eggshell
concentration were obtained by Ghazy and colleagues [12], who demonstrated
that Cr (III) uptake decreases with the increasing eggshell concentration.
Figure 2 presents the adsorption capacity of eggshell to remove methylene blue as

function of adsorbent amount. The best results obtained for the methylene blue
removal were found at an eggshell concentration of 10 g/L. Nevertheless, it worth
to be noted that the adsorption capacity is considerable lower than the one
obtained for copper and chloride. This could be explained as the eggshell
membrane is constructed of a fibrous network of proteins with positively charged
surface produced by the basic side chains of the amino acids arginine and lysine.
It is not, thus, unreasonable to attribute the adsorption of the dye to electrostatic
attraction of oppositely charged species. Considering that methylene blue is a
basic dye, this fact would explain its poor adsorption by the eggshell powder [10].
169
Figure 1. Eggshell adsorption capacity to remove copper (Cu) and Figure 2. Eggshell adsorption capacity to methylene blue as a function
chloride (Cl) as a function of adsorbent amount, at inicial concentration of adsorbent amount, at inicial concentration of methylene blue of 5
of Cu of 60mg/L and Cl of 300 mg/L, both at pH 6. mg/L at pH 8.
Adsorption studies at real aqueous system

The adsorption capacity for organic matter, measured as COD (mg/L) versus
eggshell concentration is shown in Figure 3. The studies were performed at
different pH values considering the importance of this parameter in adsorption
process. It is demonstrated that at pH 5, COD removal is higher than the one
obtained at unadjusted pH. It was also found that the higher COD adsorption was
obtained at 150 mg/L of eggshell powder (not published). For these concentrations
of eggshell, the adsorption capacity appears to be similar and independent of the
pH adjust. In an industrial process, pH adjustment involves the addition of
chemicals thereby increasing the costs of the process and also implying additional
treatment of the final solution [23]. For this reason, the studies of COD removal
from unit treatment facilities were carried out at unadjusted pH. Figure 3 reveals
that adsorption capacity of eggshell is higher for low range COD than for higher
ones.
Figure 3. Eggshell adsorption capacity to remove organic matter, Figure 4. Eggshell adsorption capacity to remove aluminum
measure as CQO (mg/L), as a function of adsorbent amount, at initial (mg/L) as a function of adsorbent amount, at inicial
concentration of CQO 5760 mg/L for municipal wastewaterl and CQO concentration of Al 870 mg/L.
579 mg/L for the landfill leachate.
Figure 4 shows the adsorption capacity for aluminium from electroplating

wastewater effluent, as a function of eggshell concentration, for different values of
pH. The pH 4.5 is justified by the speciation curve of aluminum, according to figure
5. At this value of pH, aluminium is found in soluble form, allowing its removal
through adsorption. The best adsorption capacity is obtained at unadjusted pH
170
with 1 g/L of eggshell. It appears that for higher concentrations of eggshell, a
suddenly decrease of adsorption capacity is found. For 1 g/L of eggshell, is a small
theres a slight difference between adsorption at unadjusted pH and pH 4.5.
Figure 5. The speciation curve for aluminum [26].
CONCLUSIONS
The results showed that eggshell by-product may be a promising adsorbent for
several types of pollutants present in wastewater effluents. For the adsorption of
copper and chloride, it was demonstrated that a maximum adsorption capacity
was reached when using 1 g/L of eggshell powder. It was also observed that the
eggshell adsorbent has a better affinity for copper than for chloride. Regarding the
adsorption of methylene blue, the results showed a smaller affinity. The studies
involving real wastewater effluents, illustrated the potential of eggshell as a
substitute of traditional adsorbents. Concerning the removal of organic matter,
from two specific effluents, with higher and low charge of organic matter, results
demonstrated a good adsorption capacity for the two cases, without requiring a
change on the operating conditions. Additionally, the results obtained for the
adsorption of aluminium, prove that eggshell works as an effective adsorbent in
wastewater from anodizing plants. From the evidences of all the performed
experiments, it is possible to conclude that calcined eggshell is a promising
adsorbent for the removal of some types of water pollutants.
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[24] H.J. Park, S.W. Jeong, J.K Yang, B.G. Kim, S.M. Lee, Removal of heavy metals using waste eggshell, J. Envir. Sci. 19
(2007) 14361441.
[25] L. Clescer, A. Greenberg, A. Eaton, Standard methods for the examination of water and wastewater, 20th ed, American
Public Health Association, Washington, 1998.
[26] R.A. Yokel, P.J. McNamara, Intestinal Aluminum Absorption and Bioavailability from Representative Aluminum
Species, Annual Report, 2006.
172
INSPECTING CLEANLINESS AT BOTTEL BANK SITES THROUGH A PDA
1
Ph. Alen
1 Ph. Alen Quality & Control Manager Fost Plus rue Martin V BE-1200 Bruxelles
philippe.alen@fostplus.be
ABSTRACT
Fost Plus is the Belgian Green Dot organization who organizes, promotes and
coordinates the collection and recycling of glass generally through bottle banks. Fost Plus
finances the emptying, cleaning and maintenance of the bottle banks, and of those sites.
Regular checks are performed. To improve the controls objectivity, Fost Plus has
developed a Methodology Tool for Assessing Cleanliness. Three criteria are monitored:
cleanliness of the sites, state of the bottle banks and cleanliness of the bottle banks.
Demonstrative pictures and additional descriptions for each score are used in the
methodology. Recently, Fost Plus has decided to develop a central web-based
application to improve the accessibility of the results and to track the corrective actions.
Furthermore, the intermunicipalities can perform auto-controls using a PDA. This PDA
includes a GPS, a phone connection and a camera. The application allows quotations,
takes a picture of the findings and downloads those results within the day to the internet
website. All the partners concerned by those results will be able to consult them, and, if
needed, to take in short term corrective actions. Once those actions implemented, the
operator can update the status of the site, so that each partner can follow the compliance
evolution.
Keywords:
Bottle banks
Methodology Tool for Assessing Cleanliness
Personal Digital Assistant (PDA)
Web-based application
FOST PLUS
Fost Plus is the Green Dot organization who organizes, promotes and coordinates in Belgium the
collection, sorting and recycling of household packaging waste. Fost Plus deals with three streams:
Paper and cardboard, PMD (Plastic bottles and flasks, Metal packaging, Drink cartons) and glass.
The collection of these waste fractions is organised in collaboration with about 30
intermunicipalities.
COLLECTION SCHEME OF GLASS

The collection of used glass containers generally goes through bottle banks (78%), a part is
collected via container parks (6%), and the remaining amount is collected door to door. The glass
is separated in two colors: clear (45%) and colored (55%) fraction.
173
Fig.1 Sorting rules for glass collection in Belgium
FINANCING
Fost Plus finances the emptying, cleaning and maintenance of the bottle banks, and the cleaning
and the maintenance of the sites of those bottles banks.
Fig. 2 Contract (financing) and material flows
174
OPERATIONS
More than 8000 bottle bank sites are operational with approximately 14.000 bottle banks. The
operations which have to be performed as described in the specifications are: the emptying of the
bottle banks, the cleaning of the bottle bank sites and the cleaning and maintenance of the bottle
banks. Those may be done by the intermunicipality or by a private subcontractor. Fost Plus
finances also the reinforcement of the ground beneath the bottle bank if necessary. This
reinforcement facilitates its maintenance and its attractiveness.
CONTRACTUAL OBLIGATIONS
In accordance with the specifications, the bottle banks have to be emptied at least at the level of
75%. The emptying frequency is determined by the collector. The bottle banks have to be in good
condition at all time. Bottle banks are cleaned at least four times a year. Defects have to be
repaired as soon as possible with a maximum delay of one week after notification. Bottle bank sites
have to be cleaned once a week and within 24 hours after notification.
CONTROL ON BOTTLE BANK SITES

Besides the recycling results (30kg/inhabitant), Fost Plus focuses on the delivery of a good service
to the population. Therefore, regular checks of the bottle banks are performed. In case the
contractual obligation are not fulfilled, infractions have to be solved within 24 hours to 7 days,
depending of the type of problem. The network of each intermunicipality is controlled four times a
year (once every three months) by Fost Plus. This represents 40% of the bottle bank sites on a
yearly base. Reports of those controls are sent to the concerned intermunicipality (and where
appropriate, its subcontractors) within 24 hours. Penalties can be applied when the initial observed
non conformities are not solved within the contractual agreed period (normally one week).
METHODOLOGY TOOL FOR ASSESSING CLEANLINESS

To improve the controls objectivity by the different controllers and to ensure an equal interpretation
of the results by all the implicated partners, Fost Plus has developed a Methodology Tool for
Assessing Cleanliness supporting objective registration and allowing equal interpretation of the
results.
Three criteria are monitored using scores from perfect to very bad: cleanliness of the sites, state of
the bottle banks and cleanliness of the bottle banks. Demonstrative pictures and additional
descriptions for each score of all three criteria are used in the methodology to give the user better
guidance.
175
Fig. 3 Demonstrative pictures and additional descriptions for each score
Fig. 4 Overview of the scores for each of the three criterias (+ basement)
PDA AND WEB-BASED APPLICATION

Recently, Fost Plus has decided to develop a central web-based application to improve the
accessibility of the results and to track the corrective actions.
Furthermore, the intermunicipalities can perform auto-controls using a PDA (Personal Digital
Assistant).
This PDA includes a GPS, a phone connection and a camera, and saves the exact position of the
bottle bank sites.
176
The application allows the quotation of the cleanliness of the sites, the condition of the bottle banks
and the cleanliness of the bottle banks through a drop down menu, takes a picture of the findings
and downloads those results within the day to the internet website.
Fig. 5 Internet website pictures related to a control
All the partners concerned by those results will be able to consult them, and, if needed, to take in
short term corrective actions. Once those actions implemented, the operator can update the status
of the site, so that each partner can follow the compliance evolution.
Fig. 6 Overview of all the sites and their status (open actions)
177
This tool will allow our partners to realize their own controls on their bottle banks network and to
share their information. This will increase possibilities of controls, follow up, and the services and
positive recycling image to the population.
Further information about the Methodology Tool for Assessing Cleanliness, the Personal Digital
Assistant (PDA) and Web-based application are available on demand at Fost Plus.
178
THE CYCLIC TRIAXIAL TEST AS TOOL TO QUANTIFY COARSE NON-

CONVENTIONAL MATERIALS RESPONSE
1 2
N. Arajo and A. Gomes Correia
1 Assistant Professor, C-TAC, School of Engineering, University of Minho, Campus de Azurm,
4800-056 Guimares, Portugal. E-mail: nuno@civil.uminho.pt. Phone (+351) 253 510 200. Fax:
(+351) 253 510 217
2 Professor, C-TAC, School of Engineering, University of Minho, Campus de Azurm, 4800-056
Guimares, Portugal. E-mail: agc@civil.uminho.pt. Phone (+351) 253 510 200. Fax: (+351)
253 510 217
ABSTRACT
Sustainable waste management requires efficient dealing to protect landfill and reduce
waste deposits. For that it becomes necessary to improve material characterization, using
performance based tests, to estimate waste reuse as construction material. Several
mechanical tests exist which make possible to use numerical tools to estimate reversible
and irreversible behaviour of non-conventional coarse material, as industrial waste. From
the available tests, the large-scale cyclic triaxial test is commonly used since it is the
simple one to implement and allows the study of the irreversible behaviour, an import
factor for materials to be used in roadway and railway infrastructures. The large-scale
cyclic triaxial test is an equipment that exists on several important laboratories, in Europe,
USA and Asia. This paper describes a large cyclic triaxial test facility developed at Centre
for Waste Valorisation (Campus of University of Minho), able to study coarse
aggregates/waste materials with grain size particles up to 50 mm.
Keywords: laboratory testing, large-scale cyclic triaxial test, mechanical characterization
INTRODUCTION
Attending that waste minimization and effective and sustainable waste management are basic
principles of the European Environmental Legislation and Strategy [1], and also that construction
industry is the major solid waste generator in the world, the stream of construction and demolition
waste must be dealt attending the available landfill space for disposal and the dangerous
substances contained in it. These wastes, as those of several other industries (e.g., the steel
industry) can be efficiently re-use as construction material if an accurate characterization of their
properties is available. As example, waste from the steel industry are proved to be suitable for use
as aggregate in concrete [2], as aggregates in stone mastic asphalt mixtures [3], or as subgrade
and sub-base or base course aggregate in transportation infrastructures [4].
The mechanical behaviour of these wastes, in particular those used as aggregate in transportation
infrastructures, may be classified by mean of empirical tests commonly used in geomaterials.
However, studies have shown that this type of classification is not reliable to predict numerical
behaviour of non-conventional and also for conventional materials [5]. Since granular materials
play an important role in road and railway infrastructures, laboratory procedures must be improved
and used in replacement of the empirical test [6]. These procedures must be performed over the
entire grain size and reproducing the stresses induced during construction and life service. The
most common laboratory techniques able to correctly quantify the mechanical behaviour of non-
conventional materials are: triaxial test, shear test, and hollow cylinder. Among those, the cyclic
triaxial test is the most common since it can cover the small strain domain observed during live
service, but also the large strain domain imposed during construction [7].
179
The cyclic triaxial test, together with an European standard [8], allows an accurate quantification on
the elastic and plastic behaviour of the materials. Attending that non-conventional material may
have particles with large dimension, a large-scale triaxial chamber is required for testing. This
equipment is fundamental for the accurate mechanical characterization of non-conventional
material (as well as conventional material) in order to allow its re-use as construction material.
MECHANICAL LABORATORIAL APPROACHES

The classical empiric classification of the materials is obsolete since it is fundamental to determine
the mechanical parameters that control the behaviour of the materials for use in numerical design
methods. This study needs to be done at a laboratory level on the selected material before they are
used in construction, most especially for the case of waste materials, in which few or none
experience exists.
The simulation of loading conditions is complex. For example, when simulating a road loading
condition, the stress applied on a certain element comprises of two components, respectively the
shear and normal stress. At beginning, with the applied load far from the study element, the
horizontal shear stress is the dominant stress component, but as the wheel approaches the
position above the element the horizontal shear stress lessens and the vertical and horizontal
normal stresses become the dominant ones. To reproduce such complex loading conditions, the
equipment must be able to attend principal stress amplitude and orientation, which can be induce
by natural phenomenon (such as an earthquake), or in engineering work (such as traffic load Fig.
1.a, or a slope Fig. 1.b).
(a) stresses (b)
x
v v

h x h
P
pavement P
subgrade

Fig. 1. Stress rotation induced by (a) traffic load or (b) a slope foundation (after [9])
The amplitude/rotation of the principal stresses can be simulated in laboratory by means of eight
types of mechanical tests, respectively: triaxial tests, plane strain triaxial, true triaxial, hollow
cylinder triaxial, torsional triaxial, simple shear, directional shear cell and hollow cylinder torsional.
To control stress evolution, the amplitude of the three principal stresses (1, 2 and 3) and their
rotation () is required. The hollow cylinder torsional is the only equipment able to control all four
parameters, since it is able to applied controlled axial load, torsion, internal pressure and external
pressure. It is an apparatus that allows the rotation of the principal stresses. With the exception of
the directional shear cell, all other are unable to reorient the principal stresses. The triaxial test and
plane strain triaxial are only able to control the amplitude of the minimum and maximum principal
stress (3 and 1), being the true triaxial, hollow cylinder triaxial and torsional triaxial also able to
control the intermediary principal stress (2). The simple shear does not work with principal
stresses since it induces rupture by shearing at constant stress. To resume and clarify all these
tests capacities, Table 1 is given to resume controlled parameters and to illustrate the controlled
actions of each one.
Table 1. Available mechanical tests and controlled parameters (after [9])

Test name Controlled parameters Test schema
1
Triaxial test 1 and 3
3 3
180
1
Plane strain triaxial 1 and 3

3
1
True triaxial 1, 2 and 3 2

3
z
Pe
Pi
Hollow cylinder triaxial 1, 2 and 3
z
T
Torsional triaxial 1, 2 and 3 r r
z
xz
Simple shear z and xz
xy
x
Directional shear cell 1, 3 and
y
T
F
Pe
Hollow cylinder torsional 1, 2, 3 and Pi
From all these tests, the triaxial test is the most appealing, despite being unable to control the
intermediary principal stress (2) and orientation. It consists on a test simple to implement than the
hollow cylinder and it allow the study from the small to large stress domain. The use of cyclic
loading make also possible to study irreversible behaviour. And, to allow the simulation of 2, it can
be updated to control specimen torsion, making it possible to modify existing systems to torsional
triaxial ones.
AVAILABLE LARGE-SCALE TRIAXIAL APPARATUS

Testing of coarse aggregates or industrial wastes requires large experimental devices since the
size of the sample has to be at least 6 greater than the maximum grain diameter. From the 90s,
the triaxial chamber dimensions achieved considered grow. One can enumerate several of this
large-scale triaxial apparatus at: the University of Catalua (Spain) for specimen up to 300 mm
diameter, the University of Tokyo (Japan) for specimen up to 1500 mm diameter, the GeoDelft
(Netherlands) for specimen up to 400 mm diameter, the University of Karlsruhe (Germany) for
specimen up to 800 mm diameter, the University of Berkeley (EUA) for specimen up to 915 mm
diameter, the University of Nantes (France) for specimen up to 1000 mm, the Missouri Institute of
Science and Technology (EUA) for specimen up to 420 mm diameter, the University of Nottingham
(UK) for specimens up to 300 mm diameter, the University of Chile (Chile) for specimens up to
1000 mm diameter, the Norwegian University of Science and Technology (Norway) for specimens
181
up to 500 mm diameter, and the Laboratrio Nacional de Engenharia Civil (Portugal) for
specimens up to 300 mm diameter.
CVRS TRIAXIAL APPARATUS SYSTEM

The evaluation of the behaviour of geomaterials (or coarse industrial waste) in fundamental to
reduce maintenance cost and to protect landfill resources. Also attending that the unique national
large-scale is out-of-date, the Civil Engineering Department at University of Minho developed, in
cooperation with the Centre for Waste Valorisation, a large-scale cyclic triaxial apparatus to study
materials with grain size curves up to 50 mm (Fig. 2). The system was developed to allow the
execution of test procedure described in [8]. The large-scale cyclic triaxial system now available at
Centre for Waste Valorisation (at University of Minho), allows two testing procedures: (a) cyclic
variation of the deviatoric stress with constant confining pressure, and (b) sync variation of the
deviatoric and confining pressure. Two testing configurations are possible, designated in Table 2
as Conf. 1 and Conf. 2, respectively for samples with 150 mm or 300 mm diameter. The second
configuration (Conf. 2) is mainly intended for the classification of materials with particles bellow 50
mm (i.e., many of the non-conventional materials).
Table 2. Main characteristics of the testing facility

Parameter Conf. 1 Conf.2
Maximum axial load (N) 50 kN 200 kN
Maximum confining pressure (3) 400 kPa 400 kPa
Maximum axial displacement () 50 mm 100 mm
Cyclic axial load amplitude (at 1Hz) [0.4, 10] kN [1.7, 45] kN
Cyclic confining pressure amplitude (at 1Hz) [25, 400] kPa [25, 400] kPa
Cyclic axial displacement amplitude (at 1Hz) [10, 2500] m [20, 5000] m
Monotonic test velocity [0.01, 1] mm/min [0.01, 1] mm/min
Sample height 300 mm 600 mm
Sample diameter 150 mm 300 mm
pressure transducer
(a) (b) (c)
182
(d) (e) (f)
Fig. 2. CVRs triaxial apparatus: (a) 300 mm specimen diameter triaxial chamber, (b) specimen
mold, (c) top pressure transducer, (d) hydraulic group, (e) assembled chamber and (f) global large-
scale triaxial system
The use of this device was susceptible to promote a steel industry waste in a new construction
material, actually a commercial product [10], and its capacity to simulate stress trajectories distinct
from the classical q/p=3, allows a better representation of the loading conditions. As an ongoing
project, accelerometers are being used to improve specimen instrumentation. Other details
regarding this new system can be found at [11].
CONCLUSION
The reuse of industrial waste protects landfill resources and can even be a profitable resource. But
for that performance-based laboratorial characterization is needed to allow the use of numerical
models. Several types of mechanical tests are available to replace classical empiric methods. From
all them, the cyclic triaxial test is usually adopt, for its simplicity and capacity to study both
reversible and irreversible behaviour. Due to the lack of this type of facility and expertise, the
Department of Civil Engineering at University of Minho and the Centre for Waste Valorisation set-
up a large-scale cyclic triaxial apparatus, able to apply synchronize variation of axial load and
confining pressure. This equipment was presented in this study and is operational.
ACKNOWLEDGEMENTS
This study has been carried out under the framework of the strategic plan (2011-2012) of Territory,
Environment and Construction Centre (C-TAC/UM), PEst-OE/ECI/UI4047/2011, approved by the
Portuguese Foundation for Science and Technology (FCT).
REFERENCES
[1] Fatta, D., Papadopoulos, A., Avramikos, E., Sgourou, E., Moustakas, K., Kourmoussis, F.,
Mentzis, A. and Loizidou, M., Generation and management of construction and demolition
waste in Greece an existing challenge, Resources Conservation & Rec., 40 (2003) 81-91.
[2] Maslehuddin, M., Sharif, A.M., Shameem, M., Ibrahim, M. and Barry, M.S., Comparison of
properties of steel slag and crushed limestone aggregate concretes, Construction and Building
Materials, 17 (2003) 105-12.
[3] Wu, S., Xue, Y., Ye, Q. and Chen, Y., Utilization of steel slag as aggregates for stone mastic
asphalt (SMA) mixtures, Building and environment, 42 (2007) 2580-2585.
[4] Gomes Correia, A., Reis Ferreira, S., Roque, A. and Cavalheiro, A., Portuguese steel slags. A
new geomaterial, 17th International Conference on Soil Mechanics and Geotechnical
Engineering 5-9 October, Alexandria, Egypt (2009) 15-18.
183
[5] Gomes Correia, A. and Lacasse, S., Technical session 2e: marine & transportation
geotechnical engineering, 16th ICSMGE, 12-16 September, Osaka, Japan, (2005) 3045-3067.
[6] Gomes Correia, A. e Gillet, S., A large triaxial test apparatus for study of granular materials
under repeated loading used at LNEC, EUROFLEX93, 20-22 September, Lisbon, Portugal,
(1993) 45-64.
[7] Gomes Correia, A. and Biarez, J., Stiffness properties of materials to use in pavements and
rail track design, 12th European Conference on Soil Mechanics and Geotechnical Engineering
- Geotechnical Engineering for Transportation Infrastructure, 7-12 July, Amsterdam, The
Netherlands, (1999) 1245-1250.
[8] CEN, European Committee for Standardization. EN 13286-7: Unbound and hydraulically
bound mixtures Part 7: Cyclic loading triaxial test for unbound mixtures, (2004).
[9] Azevedo, J., Desenvolvimento de um equipamento hollow cylinder torsional para solos, PhD
thesis, University of Rio Grande do Sul, Porto Alegre, (2008).
[10] Reis Ferreira, S., Comportamento mecnico e ambiental de materiais granulares: aplicao
s escrias de aciaria nacionais, PhD thesis, University of Minho, Guimares (2010).
[11] Gomes, Correia, A, Arajo, N. and Reis Ferreira, S., A large precision triaxial apparatus for
study geomaterials under cyclic loading, 12CNG, 26-29 April, Guimares, Portugal (2010)
1125-1130.
184
CHARACTERIZATION OF THE LEACHATE FOR OPTIMIZATION OF A CO-

DIGESTION PROCESS
1,a 1
Dumas S. , Morau D.
1
Dpt. of Physic and Mathematical Engineering for Energy and Environment, University of La Runion
a
severine.dumas@yahoo.fr
ABSTRACT
Waste production is ever increasing and it is important to valorize it. Among the possible
processes is digestion. This study shouws the example of valorization by using the
process co-digestion optimized by adding leachates. The study also shows the
characterization of injected leachates : making near spectrum, physic-chemical analyses
and the development of calibration methods of the following parameters : COD, BOD, Nt,
TOC. The results show :
-clear spectral differences,
-a large geneity of the values obtained for physic-chemical parameters studed, the
resulting agglomerates for the mixed organic waste / sludge,
-prediction of Nt is not satisfactory, whereas it was for the after parameters: TOC,
COD/BOD.
Keywords: Leachate; Co-digestion; Near-infrared spectroscopy, calibration;
INTRODUCTION
The increase in the population on the island of Reunion island (1 million in 2025) goes hand in
hand with the increase in urban waste (sludge, fermentable fraction of the household refuse, green
waste) and agricultural. The limited surface of Reunion (2520 km), its insularity and its insularity
make impossible the export of waste. The current processes of valorization of waste such as
digestion are possible ways, but their optimization is necessary. This optimization passes by an
improvement of the methanogen yield. The leachate seems to be a good compromise but requires
an expert knowledge on its characteristics, to be included in a process of digestion.
MATERIALS AND METHOD

With this intention we set up 10 bioreactors and currently collected 50 leachates. According to the
references, we chose:
-for a mixture of waste 50% of liquid/50% of solid,
-for a weekly recovery of the leachates,
-for the choice of following waste : liquid manure of pig, residuary liquor, mud of purification plant
for waste liquid, bleaches on grass, and organic waste for solid waste.
Each digestate used in digestion being different (V = 5 or 10 L), we put forth the assumption that
the characterization of the leachate was to be the most complete possible, in order to carry out the
best possible choice during the injection in the process of digestion. This is why we have:
-determined the physicochemical parameters (COD, BOD, TOC, Nt) for each leachate obtained,
with HACH LANGE micro-methods (spectrometer DR5000)
-carried out spectra in the infra-red close relation (spectrometer FOSS NIR (1100-2500 nm),
module BEVERAGE, software WINISI) and of the tests of calibration of the TOC, COD/BOD and Nt
were carried out within sight of the publications of [1, 2].
185
The results presented show the interest of the characterization and the use of the infra-red close
relation. Indeed, the analyses present a great heterogeneity of the results. This is very interesting
because it gives us the possibility to vary the tests of incorporation in the process of digestion.
Figure 1 : spectrums all leachates
Figure 2 : spectrums leachates obtained at different days from mixed identical wastes
186
Figure 3 : spectrums four leachates obtained the same day from different mixed wastes.
We can observe from figures one clear spectral difference. We selected as spectral windows
following areas :
- 1100 - 1390,4
- 1550 - 1912,4
- 2016 - 2250,4
A total of 219 selected wavelengths.
The results of the physicochemical analyses obtained on the 50 leachates: BOD, COD, TOC, Nt
show an important heterogeneity of the values obtained, that is for the same mixture of waste or
not. The mixtures containing sludge did not give a leachate, but we noted the formation of
agglomerates.
Figure 4 gathers the results of the first tests of calibration for COT, COD/BOD and Nt. It is noticed
that the prediction of Nt is not satisfactory (0,513) whereas the first results show an interest for the
prediction of the three other parameters (good agreements between values laboratory and
predicted values, RSQ : TOC 0,956 ; COD 0,935 ; COD/BOD 0,953).
187
Figure 4 : results of modeling
188
CONCLUSION
This study shows:
- The choice for the mixture of waste introduced into the bioreactors influences the
physicochemical properties of the leachate obtained and on the production of leachate,
- the evolution in the time of the leachate obtained for the same mixture of waste,
- its spectroscopy NIR can be used to characterize leachate,
- calibrations seem possible.
The initial results of calibration after addition of leachate in the acidogen phase process of co-
digestion are good, interesting, show the advantage of using the Near and demonstrate the need to
continue.
PERSPECTIVES
Several goals for the rest of our work :
-Improve the signal reducing background noise by adjusting the electrode gap
-Continue the production of leachate
-Optimize the calibration methods
-Repeating the addition of leachate to confirm the results
-Perform tests of adding leachate at different stages of the anaerobic digestion process by making
a reasoned choice of leachate ton be included.
References
[1] Pascoa, R.N.M., Lopes J., Lima J.L.F.C.In situ NIR monitoring of activated dairy sludge
wastewater treatment processes, Journal of Near Infrared Spectroscopy, 16(4), (2008) 409-
419.
[2] Ward A.J.,Bruni E., Lykkegaard M.K., Feilberg A., Adamsen A.P.S., Jensen A.P., Poulsen A.K.
Real time monitoring of a biogas digester with gas chromatography, near-infrared
spectrosocpy, and membrane-inlet mass spectrometry, Bioresource Technology, 102(5),
(2011) 4098-4103.
189
USAGE & ATTITUDES ON WASTE PAPER RECYCLING OF UNIVERSITY

STUDENTS AND ITS ECONOMIC EFFECTS IN TURKEY
1 2 3
H. Zulfikar , N. Beken and B. Engin
1 Faculty of Economics, Istanbul University-Beyazit Branch,34452,Istanbul-Turkey,
zulfikar@istanbul.edu.tr
nalbeken@istanbul.edu.tr
b.engin@istanbul.edu.tr
ABSTRACT
Paper, with a lot of use in industry and cultural fields, is one of the most important items
of need. Development in the paper industry is considered to be one of the decisive
elements in the country's industrial and cultural development level. Per capita paper
consumption is considered as a measure of countries' levels of development. Paper and
cardboard are mainly used in the recycling of solid wastes. Waste paper is very important
for the world economy. The main substance of the paper pulp is obtained from trees.
When used papers are recycled, the need for raw materials diminishes. Environmental
pollution is important for the use of waste as raw materials. Industrial and domestic
wastes are the sources of waste paper. When waste papers are recycled, air and water
pollution are prevented and a saving is made in water and energy consumption. Our
study was influenced by such themes and a survey was conducted among the students
from various universities representing Istanbul and Turkey. In this study, the total paper
demand of students, usage and attitudes on waste paper of students, economic
evaluation, and economic effects of paper waste recycling, as well as the level of
environmental awareness were examined.
Keywords: Waste paper recycling; statistical estimations; economic effect; environmental

awareness, environmental statistics
INTRODUCTION
Paper& board have a specific importance amongst all the recyclable solid wastes. Due to the fiber
loss at each separate use, waste paper which can at most be used only for 5 times, loses 5-30 %
in quantity while being recycled [1,2]. Industrial and domestic wastes comprise the sources for
waste paper [3]. Recycling of waste papers serve both to the prevention of air and water pollution
and economization of water and energy consumption [4.5,]. There is an explicit difference between
the treatment processes of recyclable wastes in developing and developed countries. In most
developed countries, the improvement of recycling is usually a market driven domestic market
phenomenon. The fact that the product life span hence the quantity of related wastes are both low
in developing countries leads to the low quality and quantity in the supply of secondary products.
Therefore, a raw material shortfall comes into question in the field of recycling [6]. Waste paper
constitutes the major raw material for paper manufacturing in our country. The total quantity of
waste paper collected in Turkey increased to 1.796 tonnes in 2007 and 1.840 tonnes in 2008.This
corresponds to a recycling ratio of 43 % for the year 2008 [7]. Together with the increase in the
ratio of waste paper use in paper industry, there has arised a waste paper market.. In Turkey, out
of the collected waste paper, fluting and test liner cardboards (corrugated cardboard sector
external package boxes for white appliances), chromo board and etc. are manufactured. As it can
be seen herebelow, this constitutes a significant topic which deserves to be dealt with from the
perspective of university students behaviour and attitude.
1
190
GOAL AND SCOPE
The importance of information gathering, informing and information management is evident in
environmental management. Studying the relationship with environmental consciousness and
current information level of young people, especially university students with high levels of
adaptation to innovation and knowledge flexibility, has a special importance in strategic decision
making processes. Therefore, throughout this study the environmental consciousness, the
information level, opinion and thoughts, behaviour and attitude of the young people pursuing higher
education, regarding solid waste, paper and cardboard wastes and recycling have been tried to be
identified. By doing this, effective environmental policy establishment and implementation together
with reaching rational outcomes at socio-economic and socio-cultural decision making processes
will be enabled. Statistics based analyses play a significant role in the formation of accurate
communication strategies and efficient and scientific environmental management strategy based
particularly on data gathered from environmental pollution, environmental consciousness and
related behaviour and attitude. To be able to make rational assessments on environment,
communication and economy, to pass beyond conventional approaches to realize the partial supply
and demand analyses at perceptional level, solid waste and paper and board wastes management,
the recycling of these wastes, and provision of scientific subsidy with environmental consciousness
for the adequacy and efficiency of the particular share to be allocated from within the national
income are all amongst the subgoals of the study. The study was realized with a total number of
447 students pursuing higher education at associate, degree and post-graduate levels in state and
foundation universities based in Istanbul. Istanbul, as a city comprising the 18 % of the total
population, 13,42 % of the total number of households, 8 % of the state universities, 4 % of the
foundation universities, It would be possible to use the outcomes of the study to come up with
nation-wide assumptions from certain perspectives. Within this scope, between April 11 May 20,
2011, a total number of 8 faculties, 2 vocational schools and 18 departments out of 3 state, 3
foundation universities and 1 foundation vocational school were selected. Eventually, the results
have been obtained through one of the quantitative research methods; face-to-face interview
technique, applied on 447 students, 419 of whom were coming from state and 28 coming from
foundation universities, 24 of whom were masters and PhD students with the rest being associate
and degree level students.
METHODS
Research Model and Sampling Method

The research has been carried out through face-to-face interview technique by employing
quantitative question form, combining both descriptive and analytical research methods. A question
form consisting of a total number of 43 questions which would also be used on the same target
audience for another subgoal and for this particular study, questions regarding environmental
consciousness, solid and paper & board wastes, recycling and expenditures have been evaluated.
Additionally the existing questions have been examined in the demographic breakdowns. Also the
data obtained by measuring different scales have been converted into percentages, to secure
efficiency in the comparison, evaluation and interpretation.
In the sampling design Multi-stage Sampling Method has been used and the method in question
has been applied with a 4 - stage process.
The sample size was determined as n=474 by tolerable error as e=0.045 with 95 % confidence
level. Nationwide and Istanbul city distributions of some of the variables taken into consideration
while determining the sample group are presented in Fig. 1 below.
2
191
Fig. 1. Nationwide and Istanbul City Distributions on the Basis of Certain Variables [%]
Statsitical Analyses and Tests

The statistical tests and techniques required for the results representation of the population,
internal and external validity and confidence were taken into consideration, while Cronbachs alpha
coefficient was preferred for the scales consistency and confidence tests, t test was preferred for
the comparison of two population estimates and related parametric significances.
Additionally, in group comparisons like faculties, disciplines and classes ANOVA and The Mann
Whitney U tests were used while chi-squared test was preferred for distribution conformity and
dependence tests where siginificance level was taken as 0.05 (p=0.05). Besides, in analyzing the
relation between some variables, pearson and spearman correlation analyses and regression
analyses were done and the results were evaluated at p0.05 level. For statistical tests and
analyses SPSS version 17 and PASW version 18 statistic programmes were used.
FINDINGS AND EVALUATIONS
General Evaluations
First of all, students were asked to evaluate 20 different topics/probable problems regarding
environment and its related fields under different headings. The evaluations of the students on
these different problems were measured and converted into percentages by using scales are
shown in Table 1. In Table 1, the values representing some variables are observed in percentages.
Table 1. Opinions on Environment and Other Problems Based on Certain Variables [%]
TOPICS / PROBABLE INFORMATION RISK LEVEL [%] CURRENT ANXIETY FUTURE ANXIETY
PROBLEMS LEVEL [%] LEVEL [%] LEVEL [%]
Nuclear Risks 60,08 80,81 81,65 78,75
Chemical Risks 59,82 80,03 77,9 79,41
Air Pollution 75,68 80,93 81,7 82,61
Lake, River and Sea Pollution 73.76 82,15 83,37 81,56
Solid Wastes 64,93 75,64 78,19 78,11
Soil Polllution 66,26, 77,26 77,91 76,29
Water Pollution 76,43 83,66 84,97 84,08
Unemployment 69,49 83,52 80,85 77,77
Alcohol 65,92 50,67 55,02 61,94
Drugs 61,25 77,25 72,76 71,05
Cigarette 70,12 64,21 69,19 64,25
Terror 72,62 86,41 86,31 72,77
Inflation 65,61 67,82 66,4 64,51
Traffic 75,35 73,72 71,92 72,76
Food Based Risks 67,02 77,64 75,16 74,6
Poverty 74,1 80,82 78,59 77,64
AIDS 57,53 65,26 68,13 66,47
Moral decay 68,27 74,06 73,54 76,86
Mobile Phones 74,38 66,32 66,57 73,73
Conflicts of political ineterests 73,75 79,34 78,16 82,52
As it may be seen on Table 1, amongst all the problems, the first three problems that the students
are least informed about have been identified as AIDS (57.53%), chemical risks (59.83 %) and
nuclear risks (60.08 %). Nonetheless, while the risk perception and anxiety levels of the students
for AIDS are again at low levels, risk and anxiety levels for chemical and nuclear hazards have
been identified at high and even above average levels.When the analysis was realized at lower
levels, the alcohol consumption problem was bearing rather higher risks for state university
students (55.44 %) while that particular problem was at lower risk levels (46.88 %) for foundation
university students.
3
192
In the next sub-title the 20 problems on which the students were asked to present their opinions,
were analyzed under the headings problems related with the environment and other
problems(economic, political and social problems) within the scope of 4 different variables.
Fig.2 Perception Levels Related to Environmental and Other Problems on the Basis of Different
Variables [%]
As it can be seen on Fig.2, the perception levels may not always be formed with information level.
When the evaluations are realized under the headings environmental problems and other
problems, significant differences have been analyzed between these two problem groups. When
the group values are lined up, it was determined that the two groups were different and that there
were no significant relations between the groups (p0.05). Thus, despite the fact that the students
information levels regarding environmental problems are lower when compared to their information
levels regarding other problems, the fact that their risk and anxiety levels have reached a
significantly high level, is observed as a natural consequence of this (p0.05). In other words, due
to intellectual consciousness and related reasons, it is probable that the students have perceived
the environmental problems with more risk and anxiety. Additionally when the topic was looked into
from the perspective of environmental problems (refer with fig.3), it was only the headings called air
pollution and water shortage where any kind of statistical difference was observed between the
students information level and risk perceptions(p0.05). The reason why there is no significant
difference despite the existence of high levels, seems probably to arise from the fact that these
problems are either more visible or appreciable. While the environmental problems that the
students are least informed about with a significant difference from the average (p0.05) are
chemical risks (59.82 %) and nuclear risks (60.08%) respectively, environmental problems that
they perceive to be the least risky with a significant difference from the average are solid wastes
2
(75.64%) and soil pollution (77.26%) respectively. (Regression Analysis, R =0.87, Adjusted
2
R =0.82, F=17.38, p=0.006<0.05 DW=1.71). Nonetheless, it was analyzed that only the risk
2
perception has an effect on the current anxiety level.( Regression Analysis, R =0.87, Adjusted
2
R =0.82 , F=17.38, p=0.006<0.05 DW=1.71, =0.82 %).
Fig. 3.Information and risk perception levels regarding environmental problems [%]
Evaluations on Solid Waste and Paper & Board Wastes
4
193
It was observed that the concept of solid waste does not evoke anything or does not mean
anything in one out of every six students (5.44 %) When the term solid waste is used, paper &
board was remembered by the foundation university students at a level of (71.43 %) which was
(41.29 %) higher than that of the state university students (p0.05). The concept of solid waste,
due to its importance on environmental pollution and paper&board concepts rank similarly in the
minds of the students at 82.2 % level (R=0.822). This high connection is a feature which can prove
to be effective for perceptional change in waste management. As a matter of fact, when the
importance perception of solid wastes in environmental pollution is increased by 1 point ( 1 %), this
leads to an increase of 1.82 points( 1.82 %) in the importance perception of paper&board, whereas
a 1 point increase in paper&board importance perception only leads to an increase of half point.
Fig. 4. Perception levels related to paper-board on the basis of certain variables [%]
It was observed that the students have a sense of importance above their actual information level
regarding environment or paper-board wastes (fig.4). Despite this, their anxiety level for the
particular harm caused by paper-board wastes is below their interest and importance perceptions
and seem to be in parallel with their low information levels. Thus, as a result of the relation
analyses no statistically significant relation was observed between information and interest together
with information and importance giving (p0.05). On the contrary, between information and anxiety
significant and strong relations were observed (p0.05). in a negative sense which indicates that
the anxiety will decrease when the information level increases (R=-0.749), and, between
importance giving and anxiety, when importance giving increases, anxiety will also increase.
Besides, seen that a 1 % increase in information level will decrease the anxiety level by 2.26%
2
(R =0.561, F=7.669, p=0.032<0.05). Nevertheless, a 1 % increase in importance giving level leads
2
to approximately 0.5 % (0.533 %) increase in anxiety level. (R =0.656, F=11.448, p=0.015<0.05).
Recycling
When asked for spontaneous answers as to which solid wastes can be recycled, one in every 4
university students (26 %), denoting a very high students populace, either was able to say nothing
at all or simply did not give an answer.This ratio corresponds to an approximate number of 1 million
(917,627) university students in Turkey. Amongst the respondents even statistically significant most
remembered paper&board wastes are expressed at 64.21 % which is a very low ratio
corresponding to 47,51 % within the total. The subsequent solid wastes mentioned, on the other
hand, are, plastic at very low ratios (43.4 %), glass (38,7 %), metal (21,7 %) and battery-
accumulator (15,44 %). Amongst all the solid wastes, it was observed that the kinds of waste which
are said to be recycled spontaneously and in an assisted manner are paper&board and glass, with
the former reaching above the average remembering level and the latter remaining at the limit
value (refer with fig.5). The average information level regarding recycling (43,69 %) is also at a very
low ratio. Thus the aided remembering percentage of paper & board waste to be recycled
increased to 78,46 % in comparison to the spontaneous remembering rate. This significant
increase (p<0.05) can serve as an indicator of even the concerned waste type to be recycled not to
be sufficiently present in the agenda of the students. Another piece of information is that it was
discovered that the average paper&board waste collection efforts and the level of participation in
these efforts are differentiated from battery (42,51%) and glass (29,31 %) waste collection ratios
5
194
Fig. 5,Spontaneous-aided remembering rates for solid wastes and their distance to mean [%]
with a significant advantage (p<0.05) and increased to 74,27 %. It was observed that the average
participation level for this particular activity was realized at a rate of 55.1 % and that one in every
two persons has taken part in it.
CONCLUSION
In this study environmental consciousness and behaviour and attitudes of the university students
from Istanbul and its environs regarding solid wastes, paper & board wastes and their recycling
have been examined. In our study, under the heading of environment and other problems, upon the
analysis of the students information and opinions, it was observed that their information level
regarding environmental problems were low whereas their risk and anxiety levels were highIn other
words, it was discovered that the anxiety level was not knowledge-based. The fact that the
students attending either state or foundation universities also led to different evaluations. When the
spontaneous remembering rate regarding the sorts of solid wastes in particular was taken into
consideration, differences were observed between state and foundation universities together with
social science and science students. Foundation university and social sciences students seem to
remember more types of waste at higher levels and instead of plastic wastes, they position
paper&board wastes at the uppermost place. Solid wastes and domestic wastes are perceived 40
% different from one another. When the field of education shifts from science to social disciplines
and further to fine arts, the importance perceptions of paper&board wastes increase in parallel.
References
[1] A. S. Weinberg, D. N. Pellow, A. Schnaiberg, Urban Recycling and the Search for
Sustainable Community Development, e-book , Princeton University
Press,NJ,USA,2000.
[2] M.Dougall, F.R. White,,P.R.Franke, Integrated Solid Management: A Life Cycle
Inventory,Wiley, e-book , England,2008.
[3] J.Gutberlet,Recovering Resources-Recycling Citizenship: Urban Poverty Reduction in Latin
America, e-book, Ashgate,2008.
[4] E. Samakovlis, Revaluing the Hierarchy of Paper Recycling, Energy Economics,26 (2004)
101-122.
[5] C. Berglund, P. Sderholm, M. Nilsson, A Note on Inter-countr7y Diffrences in Waste
PaperRecovery and Utilization,Resources,Conservation and Recycling, 34 (2002) 175-191.
[6] V. K. Sharma, P. van Beukering, B. Nay, Enviromental and economic Policy Analysis of
Waste Paper trade and Recycling in India, Resources, Conservation and Recycling 21 (
1997) 55-70.
[7] Information on http:// www.donkasan.com.tr
[8] R. J. Birn, The Effective Use of Marketing Research, Kogan Page Ltd, London,1999.
[9] S. K. Thompson, Sampling, John Wiley&Sons,Inc., New York, 1992.
[10] H. Kohler,Statistics for Business and Economics,HarperCollins College Publishers,Chicago,
1994.
6
195
13th September
Session 1.4
Chairman: Antnio Roque
196
NEW RECYCLING APPROACHES FOR THERMOSET POLYMERIC

COMPOSITE WASTES
AN EXPERIMENTAL STUDY ON POLYESTER BASED CONCRETE
MATERIALS FILLED WITH FIBRE REINFORCED PLASTIC RECYCLATES -
1 1 1 2 2 2
M.C.S. Ribeiro , A. Fiza , M.L. Dinis , A.C.M. Castro , F.G. Silva , J.P. Meixedo and
2
M.R. Alvim
1 FEUP Faculty of Engineering of University of Porto, Rua Dr. Roberto Frias, Porto, Portugal;
cribeiro@inegi.up.pt, afiuza@fe.up.pt and mldinis@fe.up.pt
2 ISEP - School of Engineering, Polytechnic of Porto, Rua Dr. Antnio Bernardino de Almeida,
4200-072 Porto, Portugal; ana.meira.castro@eu.ipp.pt, fgs@isep.ipp.pt, jme@isep.ipp.pt and
mario.alvim@alto.com.pt
ABSTRACT
In this study, a new waste management solution for thermoset glass fibre reinforced
polymer (GFRP) based products was assessed. Mechanical recycling approach, with
reduction of GFRP waste to powdered and fibrous materials was applied, and the
prospective added-value of obtained recyclates was experimentally investigated as raw
material for polyester based mortars. Different GFRP waste admixed mortar formulations
were analyzed varying the content, between 4% up to 12% in weight, of GFRP powder
and fibre mix waste. The effect of incorporation of a silane coupling agent was also
assessed. Design of experiments and data treatment was accomplished through
implementation of full factorial design and analysis of variance ANOVA. Added value of
potential recycling solution was assessed by means of flexural and compressive loading
capacity of GFRP waste admixed mortars with regard to unmodified polymer mortars.
The key findings of this study showed a viable technological option for improving the
quality of polyester based mortars and highlight a potential cost-effective waste
management solution for thermoset composite materials in the production of sustainable
concrete-polymer based products.
Keywords: Thermoset Fibre Reinforced Polymer; Recycling; Concrete-polymer composites
INTRODUCTION
The development and applications of thermoset polymeric composites, namely fibre reinforced
polymers (FRP), have shifted in the last decades more and more into the mass market. FRP
materials are generally made of glass (GFRP), carbon (CFRP), aramide (AFRP) or basalt (BFRP)
fibres dispersed in an organic matrix, usually polyester resin, widely used in several fields, from
building to aeronautic and military applications [1-2]. The high strength to weight ratio, low
maintenance, corrosion resistance, design flexibility and tailor made properties made up FRP
based materials an interesting alternative to steel, metals and other similar materials [3]. Despite of
all of these advantages, the increasing production and consume also lead to an increasing amount
of FRP wastes, either end-of-life products or scrap generated by the manufacturing process itself.
Whereas thermoplastic FRPs can be easily recycled, by remelting and remoulding, recyclability of
thermosetting FRPs constitutes a more difficult task due to inherent cross-linked nature of resin
matrix. To date, most of the thermoset based FRP waste is being incinerated or landfilled, leading
to negative environmental impacts and supplementary added costs to FRP producers and
suppliers. Further, in the near future, due to increasing severity and restrictions of waste
management legislations, FRP suppliers risk losing their market share to metals and other
industries if they cannot ensure that their FRP products and components can be reused or recycled
197
at the end of their life cycle [4]. This actual framework is putting increasing pressure on the industry
to address the options available for FRP waste management, being an important driver for applied
research undertaken cost efficient recycling methods. In spite of this, research on recycling
solutions for thermoset composites is still at an elementary stage. Thermal and/or chemical
recycling processes, with partial fibre and energy recovering, have been proposed mostly for CFRP
composites due to inherent economic value of carbon fibre reinforcement; whereas for GFRP
based products, mechanical recycling by means of milling and grinding processes, with reduction
to fibrous and/or powdered products, has been considered a more viable recycling method [5].
The most extensive research work has been carried out either on bulk (BMC) and sheet moulding
compounds (SMC), or on Portland cement concrete, in which mechanically-recycled GFRP wastes
have been incorporated either as reinforcement, aggregate or filler replacement [6-7]. Though, at
the moment, few solutions in the reuse of GFRP recyclates into added value products are being
explored. Seeking filling this gap, in this study, a new waste management solution for thermoset
GFRP based products was assessed. Mechanical recycling approach was applied and the
potential added value of obtained recyclates was experimentally investigated as raw material for
polyester based mortars. The use of a cementless mortar as host material for the recyclates,
instead of conventional Portland cement based mortars, presents an important asset in avoiding
the eventual imcompatibility problems arisen from alkalis silica reaction between glass fibres and
cementious matrix binder. In addition, due to hermetic nature of resin binder, polymer based
concrete materials present greater ability for incorporating recycled waste products [8].
Applied GFRP waste material was supplied by a local pultrusion manufacturing company (Alto,
Perfis Pultrudidos Lda.), and it was proceeding from the shredding of the leftovers resultant from
the cutting and assembly processes of GFRP pultrusion profiles. Currently, these leftovers, jointly
with non-conform products and crap resulting from the manufacturing process itself, are landfilled
with an estimated cost of 80 per ton which represents for this company on an average cost of
3500 per year. Thus, besides the manifest environmental benefits, a viable and feasible solution
for these wastes would also conduct to significant economic advantages.
EXPERIMENTS AND PROCEDURES

Polymer mortar (PM) specimens were prepared by mixing an unsaturated polyester resin (20%
w/w) with different sand aggregates/GFRP waste ratios. Processed GFRP wastes were used as
partial substitute for sand aggregates at the proportion of 4%, 8% and 12% in weight of total mass.
Plain mortar specimens were also casted and tested in order to compare mechanical and
functional properties over those of GFRP waste admixed mortars. Mix design of plain formulation
was in accordance with previous works carried out by Ribeiro and Ribeiro et al. [8-9]. In order to
investigate the effect of an adhesion promoter, a second series of experiments was carried out in
which 1% of active silane coupling agent by weight of resin was added to all formulations in
analysis.
Raw Materials and Characterization

Commercially available unsaturated polyester resin (Aropol FS3992), with a styrene content of
42%, was applied as polymer binder. Polymerization process was induced by cobalt octoate (0.5
phr) and 50% methyl ethyl ketone peroxide solution (2.0 phr). An organofunctional silane chemical
solution (Dow Corning Z-6032), with 40% of active silane in methanol, was applied as adhesion
promoter of resin binder to inorganic sand aggregates and GFRP recyclates. Z-6032, when
applied, was previously mixed with polyester resin binder prior sand and GFRP recyclates addition.
A siliceous foundry sand (slica content > 99.0%), with rather uniform particle size and an average
diameter of 245 m was used as fine aggregate. Detailed characterization of applied foundry sand
can be found elsewhere (9).
GFRP wastes, supplied by the local pultrusion manufacturing company, were further processed in
a heavy duty cutting mill laboratory unit (Type SM2000, Retsch). Obtained mechanically-recycled
products, illustrated in Fig.1, consist in a mix of powdered and fibrous material with different
quantities of varying length of glass fibres and bulk particulate material. Particle size distribution
GFRP recyclates, obtained by sieving and laser diffraction techniques, revealed a range of
particles size (or fibre diameter) between 1.5 m up to 2500 m, an average diameter of 950 m,
and a fineness modulus of 2.69.
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Experimental Plan and Testing
Eight different PM formulations were investigated varying the content of both GFRP waste
admixture (0%, 4%, 8% and 12% of total mass) and silane coupling agent (0% and 1% by weight of
resin content), hereinafter designated, respectively, by material factors W and S. Experimental
1 1
trials are presented in Table 1 and correspond to a two-factor (4 x2 ) full factorial design. PM
formulations, with the specified mix proportions were casted into standard prismatic moulds (40 x
40 x 160 mm3) according to RILEM recommendation CPT PC-2:1995 (1995). For each formulation,
four prismatic specimens were casted. All test specimens were allowed to cure 24 hours at 30C /
50% RH, and then post-cured at 80C for 3 hours, before being tested in bending and compression
at room temperature. PM specimens were tested in three-point bending up to failure at the loading
rate of 1 mm.min-1, over a span length of 100 mm, according to RILEM CPT PCM-8 standard test
method (1995). One of the two leftover parts of each broken specimen in bending, were tested
-1
afterwards in compression at the loading rate of 1.25 mm.min , following the procedure described
in UNE 83821 standard (1992). Both testing set-ups are shown in Fig.1.
a) b) c) d)
Fig. 1. a) GFRP wastes; b) Mechanically-recycled GFRP waste; c) and d) Mechanical test set-ups.
Mechanical Test Results

For each PM formulation, obtained flexural and compressive strengths are detailed in Table 1.
Presented values represent the average mechanical properties obtained for the four replicates and
correspondent standard deviations. The main effects of each material factor, and the interaction
effect between the two factors, are highlighted in response graphics displayed in Fig. 2. Response
graphics allow the evaluation of the relative importance of each factor, or interaction, in a much
easier way than the numeric values of effects. For principal effects, the interpretation of response
graphics is straightforward: each point represents the average response for a certain level of the
factor and the numeric value of the effect is the difference between the set of points; the higher the
difference, the higher the influence of the factor. The interaction is graphically defined by the
parallelism between the set of lines: the smaller the parallelism, the higher the interaction [10].
Table 1. Mechanical test results for mix design formulations of PMs.

Mix Resin Foundry GFRP Silane Flexural Compressive
Trials Binder Sand Waste Agent Strength Strength
[%] [%] [%] [%] [MPa] [MPa]
1. W 0-0 20 80 0 0 25.17 0.74 76.89 0.89
2. W 4-0 20 76 4 0 27.74 0.31 83.27 2.02
3. W 8-0 20 72 8 0 26.29 0.99 86.22 2.12
4. W 12-0 20 68 12 0 26.18 0.51 82.81 2.91
5. WS 0-1 20 80 0 1 36.00 0.53 81.29 0.74
6. WS 4-1 20 76 4 1 40.35 0.93 97.52 1.00
7. WS 8-1 20 72 8 1 41.70 1.81 104.69 0.66
8. WS 12-1 20 68 12 1 39.28 1.44 82.42 2.42
199
Fig. 2. Response graphs of main and interaction effects with respect to both mechanical strengths.
Analysis of Variance ANOVA

Analyses of variance for the properties in study are given in Tables 2 and 3 in terms of sum of
squares (SS), degrees of freedom (DF), mean squares values (MS) and F-test values for a
significance level of 5%. Obtained calculated values allow assessing the relative significance of
each factor and interaction on target responses of the experiment. The F-test statistic, F0, is
calculated as the ratio between the mean of squares of the group (factor or interaction) and the
mean of squares of the random error. The percentage of contribution, in the last columns, indicates
the relative influence of the factor and/or interaction on the global variation observed, and it is
derived from the expected value of the variance due exclusively to that factor or interaction [9-10].
Table 2. Analysis of Variance for Flexural Strength Data.

Source of Variation SS DF MS F0 Fcrit Cont.
[MPa2] [MPa2] Values Values P [%]
Factor S Silane content 1342.07 1 1342.07 629.74 4.75 92.29
Factor W Waste content 62.99 3 21.00 9.85 3.49 3.90
Interaction SW 21.28 3 7.09 3.33 3.49 1.02
Error 25.57 12 2.13 - - -
Total 1451.92 31 - - - -
Table 3. Analysis of Variance for Compressive Strength Data.

Source of Variation SS DF MS F0 Fcrit Cont.
[MPa2] [MPa2] Values Values P [%]
Factor S Silane content 714.23 1 714.23 139.75 4.75 28.68
Factor W Waste content 1283.13 3 427.71 83.69 3.49 51.28
Interaction SW 413.57 3 137.86 26.97 3.49 16.11
Error 61.33 12 5.11 - - -
Total 2472.26 31 - - - -
Effect of Material GFRP Waste Content

Experimental test results, presented in Table 1, show that the partial replacement of sand
aggregates by milled GFRP waste recyclates in polyester based mortars has an incremental effect
on both flexural and compressive strengths of modified mortars, regardless of GFRP waste content
and silane coupling agent addition. Though, the effect of GFRP waste on mechanical strength is
clearly more pronounced regarding compressive behavior than flexural performance, as displayed
200
in responses graphics of the main effect of this factor (Factor W) and confirmed by analysis of
variance: a) Slops of lines of compressive strength response graphic are sharper, in opposition with
the smooth slopes occurring for flexural strength response (see Fig. 2); b) The contribution of this
factor to global variance of compressive strength of PMs is higher than 50%, whereas for flexural
strength, the contribution does not reach 4% (see Tables 2 and 3).
Although the global improvement effect of GFRP recyclates incorporation on mechanical strength
of resultant modified PMs, two distinct trends were observed for this effect according to the amount
of waste addition (or sand replacement): up to 8% content and above that value.
Up to 8% content in waste addition, in general, loading capacities of PMs increase with increasing
addition of GFRP waste. Once again, this feature is more pronounced with regard to compressive
behaviour. Average compressive strength increases of 14% and 21% corresponding to the
addition, respectively, of 4% and 8% in weight of GFRP waste, were observed with regard to
waste-free PMs. The almost linear increase of compressive strength with GFRP waste content
might be attributed to a more continuous particle size distribution of the mix sand/waste particles.
The contribution of GFRP waste powder to filler fraction of sand aggregates, leading to an inferior
void volume for dry-packed aggregate, has a relevant role in this feature. Generally, aggregates
mixtures with the maximum bulk density lead to higher strength materials, due to improved
aggregate agglomeration. In flexural, this trend, the linear increase of loading capacity with
increase addition of GFRP waste, is not so clear. Average increases on bending capacity of 11%
and 10% were found, respectively, for 4% and 8% in weight of GFRP waste additions. It was
expected that fibrous fraction of GFRP waste would have a significant reinforcing effect, leading to
a higher improvement on flexural behaviour. Although this expected flexural improvement did
actually occur for test series modified with silane coupling agent, in which progressive increases of
12% and 16% on bending strength were noticed for respectively WS4-1 and WS8-1 test
formulations; slight decrease on flexural strength was observed for silane-free test series, when
GFRP waste content was increased from 4% to 8%, and this tendency was kept for further addition
amounts of waste (W12-0). In the mixing process of GFRP modified PMs, some tendency for the
agglomeration of waste fibres was observed, hindering somehow a perfect homogenization of the
mixture. This feature, more notorious as higher the waste content, led to a non-homogeneous
distribution of GFRP waste fibres, and might be a possible explanation for obtained results.
Another contributing factor might be the presence of larger particles on GFRP recyclates, which
tend to be stress raisers, acting as failure initiation sites. Further, being true this assumption, this
weakness would be more critical under tensile than under compressive stresses. This subject
should be clarified in posterior study that will focus on microstructure analysis of mortar specimens.
Above 8% content in waste addition, slight decreases on both flexural and compressive strengths
occur with regard to PM formulations with lower contents of GFRP waste, but even so, mechanical
strengths remain higher than those of plain mortars. It must be stressed that resin content was kept
constant to 20% in weight in all formulations; and, as larger amounts of sand were replaced by
GFRP waste throughout W and WS test series, from 0% to 12%, overall specific surface area of
aggregates was progressively increased. Thus, the higher specific surface area of GFRP waste
particles as regards to sand particles, requiring higher binder contents for a proper wettability and
cohesive bonding, is for certain the main reason for observed turning point.
Effect of Material Factor Silane Coupling Agent

As already expected, the incorporation of silane coupling agent had a significant improvement
effect on mechanical strength of PM formulations. S factors effect is especially remarkable with
regard to flexural strength response, contributing with more than 92% for the global variance. The
numeric value of this effect on flexural strength is 12.9 MPa, which means that, in average, PMs
with incorporation of 1% silane, regardless of GFRP waste content, present a flexural strength
higher in 12.9 MPa over silane-free PMs. The inherent contribution of silane coupling agent as
adhesion promoter at interface, between resin matrix and both sand aggregates and glass fibres
waste, improving the organic-inorganic phase bridge, is for certain the main reason for the
observed strong effect of this factor on flexural strength response of PMs. With regard to
compressive strength response, a minor contribution for global variance was observed (29%),
prevailing the GFRP waste content as the most influencing and significant factor. As only two levels
of variation were considered for this factor, 0% and 1%, no considerations could be done regarding
the linear or quadratic effect of silane content addition on mechanical properties of PMs.
201
Effect of Interaction between Factors
According to F-test results of analysis of variance, for a significance level of 5%, there is no
significant interaction between GFRP waste content and adhesion promoter with regard to flexural
strength response. Calculated F0 value is less than Fcrit, and thus the null hypothesis is accepted,
which means that the groups are not significantly different, i.e., the interaction is not significant. The
almost absence of interaction is graphically visualized by the similar slopes of the set of lines
corresponding to 0%, 4%, 8% and 12% waste test series on interaction response graphic (Fig. 2).
A different scenario was found for the effect of this interaction on compressive strength response.
Interaction between the analyzed main factors contributes with 16% for global variance of
compressive strength which cannot be disregarded. The effect of this interaction is mainly due to
dissimilar behaviours of W and WS test series when GFRP waste content is increased from 8% to
12%. Drop of compressive strength is very pronounced for PMs with incorporation of silane agent
(21 MPa in average) and mostly smooth for those without adhesion promoter (3 MPa in average).
CONCLUSIONS
With basis on obtained results, the following conclusions may be drawn:
For the trial formulations analyzed in this study, the partial replacement of sand aggregates by
GFRP waste materials has an incremental effect on both flexural and compressive strengths of
resultant PMs, regardless of the GFRP waste content and silane coupling agent addition.
Both material factors have a significant positive effect on mechanical behavior of modified PMs;
though, whereas GFRP waste content is the more influencing factor on compressive strength
response, contributing with 51% to global variance of this property; 92% of the global variance of
flexural strength response is due to silane coupling agent addition.
The interaction between the two factors has no significant effect on flexural strength of PM
formulations; however, this interaction cannot be disregarded with respect to compressive
response, especially for GFRP waste contents above 8% (w/w).
8% in weight of GFRP waste content constitutes the turning point value on materials behavior
trend for both analyzed properties.
The findings of this study showed a viable technological option for improving the quality of GFRP
filled polymer mortars, thus opening a door to selective recycling of GFRP waste and its use in the
production of concrete-polymer based products.
Acknowledgements
The financial support of ADI, Agncia de Inovao, under QREN, Quadro de Referncia de
Estratgia Nacional (ON.2) Program is gratefully acknowledged.
References
[1] J.W. Chin, Materials aspects of Fiber-Reinforced Polymer Composites, NISTIR 5888, 1996.
[2] V.M. Karbhari, Use of Composite Materials in Civil Infrastructures in Japan, International
Technology Research Institute, Maryland,1998.
[3] T. Starr and J. Ketel, Composites, in T. Starr (Ed.), Pultrusion for Engineers, Woodhead
Publishing Limited, Cambridge, 2000.
[4] A. Conroy, S. Alliwell and T. Reynolds, Composites recycling in the construction industry,
Comp. Part A, 37 (2006) 1216-1222.
[5] S. Pimenta and S.T. Pinho, Recycling carbon fibre reinforced polymers for structural
applications: Technology review and market outlook, Waste Management, 30 (2011) 378-392.
[6] P. Asokan, M. Osmani and A.D.F. Price, Assessing the recycling potential of glass fibre
reinforced plastic waste in concrete and cement composites, Jour. Clean Prod., 17 (2009) 821-829.
[7] F. Tittarelli and G. Moriconi, Use of GRP industrial by-products in cement based composites,
Cement & Concrete Composites, 32 (2010) 219-225.
[8] M.C.S Ribeiro, New polymer mortar formulations: Development, characterization and
applications forms, Ph.D. Thesis, Faculty of Engineering of University of Porto, Porto, 2006.
[9] M.C.S. Ribeiro, C.M.L. Tavares, M. Figueiredo, A.A. Fernandes and A.J.M. Ferreira, Bending
characteristics of resin concretes, Materials Research, 6 (2003) 247-254.
[10] D.C. Montgomery, Design and Analysis of Experiments, John Wiley & Sons Inc., NY , 2001.
202
VALORIZATION OF POULTRY LITTER AND PAPER MILL SLUDGE BY

COMPOSTING AND BY PRODUCTION OF LIGHTWEIGHT AGGREGATE
1 2 3
P.N. Biscaia , A.P. Gomes and J. Labrincha
1
RCD, SA Resduos de Construo e Demolio, SA, Figueira da Foz, Portugal,
biscaia.paulo@mail.com
2
Dpt. of Environment and Planning, University of Aveiro, Aveiro, Portugal, pgomes@ua.pt
3
Dpt. of Ceramics and Glass Engineering, University of Aveiro, Aveiro, Portugal, jal@ua.pt
ABSTRACT
The present work deals with two abundant kinds of wastes: sludge from secondary
treatment of wastewater from pulp mills and poultry litter waste. The main goal of the
study is to analyze two forms of valorization: organic valorization in the production of
compost by co-composting, and, material valorization in the production of lightweight
aggregates.
Regarding the experimental co-composting assays and the corresponding results, can be
concluded that: i) the predominance of mesophilic or thermofilic did not influenced in a
significant way the flow of the process; ii) the different mixtures attained satisfactory
degrees of OM stabilization (36%); iii) the final compost kept the nitrogen. The maturated
composts did not exert fitotoxicity and their metal analysis revealed lower levels than
those established in the regulations.
The rehearsals of incorporation two organic residues (poultry litter and compost) based
on clay and the analysis of the corresponding results claim that: i) there are no
constraints on the level of preparation of materials and the conditions of burning; ii) the
incorporation tested by 3,5 and 10% in mass, results in lightweight aggregates with best
performance of resistance/lightness; iii) the aggregates produced with the mixture of clay
and compost reveals a higher balance between density, absorption of water and
resistance to compression.
Keywords: Composting poultry litter sludge lightweight aggregates

List the keywords covered in your paper. Leave one space above the keywords
INTRODUCTION
It is common to find geographic areas where large quantities of organic waste from industrial
activities and agro-industrial, which can be managed in an integrated way through valorization
processes, avoiding landfill disposal. An example is the huge amounts of sludge from secondary
treatment of wastewater from pulp mills, the poultry litter waste and also the seasonal production of
grape stalk, that are at present a serious problem of waste management to the producers.
The solutions found to solve this problem have been, to date, the landfill and direct deposition on
agricultural land bordering the production facilities.
The valorization of biodegradable waste is important in terms of environmental sustainability, since
It may play a relevant role in the diversion of the non-stabilized organic matter currently sent to
landfill. Simultaneously the valorization of biodegradable waste decisively contributes to the
implementation of landfill directive (DL n 183/2009, the portuguese regulation), which establishes
the legal regime of the deposition of waste in landfills and limits in the near future, the deposition of
biodegradable organic matter in landfills .
Despite the poultry waste, the sludge and the stalk, are being subjected to organic valorization
through direct application on the ground, this solution is not always within reach of producers. The
intensive and continuous production of some of these wastes in a geographical region of little
dimension, exceeds the capacity of regional agriculture to absorb these materials.
203
On the other hand, the intensive deposition of waste in the soil, can cause public health problems
and environmental issues, particularly those relating to the release of odours, the formation of
surface runoff and leachate, mobilizing contaminants and intermediates of decomposition of
organic matter, resulting in pollution in surface water and groundwater.
In this context arises the need to find alternatives for valorization of biodegradable organic matter,
associated with economic opportunities to create a product for the national market. Among other
advantages, it will allow the reuse of waste on a scale significantly higher than the regional level.
For the residues considered, this work aims to analyze two forms of valorization: organic
valorization in the production of compost by co-composting, and, material valorization in the
production of lightweight aggregates.
These biodegradable waste are produced in the same geographical area (central coast of
Portugal), therefore, they may be subject of an integrated management system so that the physico-
chemical properties of the materials complement each other, forming a substrate balanced from the
composting point of view. The characteristics of composting the poultry litter waste [1] may to fill
the needs of structuring agent and absorbing moisture in the composting of sludge from secondary
treatment of wastewater from pulp mills [2].
On the one hand, using co-composting, will be determined the most appropriate mixing ratio for the
three types of waste, the operating conditions for a better degree of stabilization and will be
evaluated the quality of the compost produced, in order to take advantage of organic matter and
nutrients in agriculture.
On the other hand, taking into account the characteristics of waste, and mixtures of compounds
obtained after degradation, will be tested the possible use of these materials in the design of
lightweight aggregates.
The interest of incorporation of organic residues (poultry litter and the compost from the
degradation of the mixture composed of wastewater sludge from paper mill industry and poultry
litter) as expansive agents of lightweight aggregates of expanded clay, usually used in building
construction, is to contribute to achieve alternative ways in the massive use of a natural resource,
clay.
Previous studies have shown that sludge from paper mill industry lead to good results as an
alternative raw material in the production of lightweight aggregates [3]. However, its high moisture
content causes energy difficulties in the initial phase of the production process (burning). Co-
composting of sludge with poultry waste is also a drying process that produces a drier material than
the original sludge and could enable the production of lightweight aggregates with clay base,
reducing the energy constraint.
EXPERIMENTAL PROCEDURE
Laboratorial set up, monitoring and analytical methods of the co-composting trials
A battery of four batch, isothermal, temperature-controlled reactors was used to carry out the
degradation process. A hot water bath and a cryostat provided the heat source and sink,
respectively, for maintaining the isothermal conditions within the reactor.
The laboratory-scale pilot reactor assembly is shown diagrammatically in Fig. 1.
3
Four stainless-steel cylindrical reactors (of 3.53 dm of internal volume) (A), connected in parallel.
One thermal control unit (B) for temperature control in the reactors with Pt100 probes (C), inserted
in the composting mixture; it is the centre of the complete automatic control of the whole assembly.
One measuring unit (D), consisting of four needle-valve rotameters, a mass flow meter and 17
electromagnetically operated three-way valves; operation of this unit can be either totally automatic
through the control unit (E), or totally manual, as wished.
Gas analysis: CO2 analyzer (F) Vaisala meter CARBOCAPGMM111 Module CO2 (range 0...20
3 -1
% v/v) and Mass flow meter (G) Aalborg mass flow meter in the range of 0...2000 cm min NPT.
A microcomputer (H) for real-time data acquisition and storage.
The details of the assembly are described in [4].
During each essay were monitored the gaseous, liquid and solid phases.
The flow of gases was measured and analyzed for CO2 evolution based on entering and
exhausting air flows, after moisture removal through a condensation column with a permutation
liquid at 10C and an exsiccating material.
Leachate was collected at the bottom of the reactors for volume quantification and subsequent
control of the solid phase moisture.
204
On the solid phase was monitored the temperature reaction inside the reactor using thermocouples
type K placed in the covers of the reactors until half height and linked to an electronic multiplexing
circuit. Samples were taken periodically to determinate moisture, organic content and pH. To that
purpose it was necessary to cool the reactors and open them, homogenize the bulk and take
representative samples. At the end of the process were analyzed, also, the metal content and the
Kjedhal nitrogen content. After a month of maturation it was evaluated de index of germination and
grow of the composts obtained. These parameters were determined through the described
methods in Table 1.
A
Reactors
Measuring unit of the F

B gaseous phase
CO2 analyzer
Thermal automatic
control unit E G
C
Automatic control unit Mass flow meter
Pt100 probes
Computer
Figure 1, schematic equipment assembly in composting: the instructions in black, the thermal
control in blue, the paths of gas flow in green, signal acquisition and storage of data in orange.
Table 1, analytical methods for chemical characterization.

Parameter Analytical method
Moisture, M Dry in oven at 105 C, 24h (3 replicates)
Organic matter, OM Incineration at 600C for 2 hours (3 replicates)
3
Agitation of 5g of wet sample in 0,5 dm of distilled water for 20 min and
pH
analysis of supernatant by potentiometry with glass electrode
Acid digestion followed by distillation in alkaline environment of 1g of wet
Kjeldhal nitrogen, N
sample (3 replicates). Application note AN300/09 from FOSS
Carbon, C Elemental analysis and estimate by the ratio of OM divided by 2
Metals Atomic absorption spectroscopy flame preceded by acid digestion (nitric
(Cd, Cr, Cu, Ni, Pb, Zn) acid / sulfuric acid) of 1g of ground (<1mm) dry sample. 3030G of SMEWW
Relative production of biomass of ryegrass, Lolium multifolium, in two
Index of germination and
proportions of compost and peat, 25:75 and 50:50, in a period of 15 days (3
growth, IG
replicates).
The experience of composting consisted of six trials of co-composting, with the aim of studying the
parameters, mixing ratio of the wastes and temperature of reaction. Another test was done for
comparison with poultry waste alone. The operating conditions are presented in Table 2.
Table 2, operating conditions of the co-composting trials. Designations S, to sludge, P, to poultry

litter and s, to grape stalks
Trial: SP1_45 SPs1_45 SP1_55 SPs1_55 SP2_45 SPs2_45 P_45
Substrate S:P S:P:s S:P S:P:s S:P S:P:s P
Substrate
composition % db
30:70 27:63:10 30:70 27:63:10 58:42 53:40:7 100
Temperature [C] 45 45 55 55 45 45 45
Dry mass [g] 520 567 514 570 474 485 559
Moisture [% wb] 75.6 75.3 75.6 75.3 68.9 69.3 70.1
205
Experimental procedure to obtain lightweight aggregates
The mixtures referred to in this stage of the work are listed in table 3 They are based on clay and
may contain oil, at a rate of 1% by weight of clay, while common agent expanding (composition of
reference C+Oil). Alternatively, it used poultry litter and compost (SP1_45) obtained in the
composting trials, with a ratio of incorporation of 3% organic matter, in each.
Table 3, composition of the mixtures under study (C+Oil, C+Poultry C+Comp).

Type of mixture Composition
C+OiL Clay with oil (1%) - Standard, prepared by the company that provides the clay
C+Poultry Clay without oil and with poultry litter
C+Comp Clay without oil and with compost from trial SP1_45
The mineralogical composition and thermal behaviour of the clay was determined by performing,
respectively, analysis of X-ray diffraction (XRD), differential thermal (DTA) and gravimetric (TG).
The preparation of the mixtures began with the fragmentation and manual screening of organic
material (poultry litter and compost) in a mesh of 250 m. The different components were mixed up
with the aid of a manual extruder in order to obtain the desired mixture and moisture of around
20%.
Balls with a mass of about 2.5 g were manually shaped and dried in an oven at 130 C for 2 hours.
There followed a passage of about two hours in an oven at 230 C and then rapid transfer to the
oven that was already in the firing temperature, 1180 C. After a period of 15 minutes spent in the
oven at 1180 C, the balls were removed from the furnace and abruptly cooled when placed at
room temperature.
The aggregates obtained were subjected to several tests in order to determine its bulk density (),
water absorption capacity (WA), and compressive strength (m), according to the procedure
described in Biscaia [4].
RESULTS AND DISCUTION

Waste characterization
The three types of waste materials used in this study were characterized according to the
parameters in Table 4. It is worth noting the significant difference in moisture content of poultry litter
and sludge. We also see that these materials have different concentrations of the metals analyzed,
resulting in a dilution effect when mixtures were made. The different pH values allowed to obtain
mixtures with buffering effect. Both, the poultry litter and the sludge were rich in nitrogen.
Table 4, chemical characteristics of the waste materials.

Parameter Poultry litter Sludge Grape stalks
pH 9.48 6.75 3.76
Moisture, M [% m/m wet basis] 28.4 90.2 / 77.50 73.2
Organic matter, OM [% m/m dry basis] 80.90 75.83 93.56
Nitrogen Kjeldhal, N [% m/m dry basis] 2.563 5.151 0.9890
Carbon, C [% m/m dry basis] 39.3 48.8
Cadmium, Cd [mg/kg dry basis] < QL * < QL *
Chromium, Cr [mg/kg dry basis] 3 19
Copper, Cu [mg/kg dry basis] 32 15
Nickel, Ni [mg/kg dry basis] 2 12
Lead, Pb [mg/kg dry basis] < QL * 4
Zinc, Zn [mg/kg dry basis] 110 30
* QL Quantifiable limit.
From now on, % m/m wet basis will be % wb, % m/m dry basis will be % db and mg/kg dry basis will be mg/kg db
Results of co-composting trials

The progress of the reaction could be assessed by the CO2 evolution, resulting from the
microbiological degradation of the biodegradable compounds. To calculate the carbon released as
CO2 during composting, CO2 accumulated volume, was used Eq. 1, where yCO2 is CO2 molar
206
fraction in the dry exhaustion gas, Qe is exhaustion volumetric dry flow rate, t is time of reaction
and n is the instant of reading of the different parameters.
3
The flow rate was set at three levels: 0.8, 0.5 and 0.3 dm NPT, according to reaction time: 0-50 h
50-400 h and 400-end, respectively, so that the CO2 content in exhaust gas wasnt more than 8%
v/v.
n (y CO 2n Q e n 1 + y CO 2 Q e n )(t [dm NPT ]

VCO 2 =
n =1
1
2
n
n t n 1 ) 3
(1)
As shown in Fig. 2 the progress curves of CO2 released is similar for all trials, however, stands out
the mixture SPs1_45 with the higher volume of CO2 generated. Mixtures SP2_45 and SP1_55
have released lower amounts of CO2 and less than poultry litter alone. The isothermal condition of
45C and/or the presence of grape stalks as structural agent increases the release of CO2 and
facilitates the gas exchanges.
SP1_45 SPs1_45 SP1_55 SPs1_55 SP2_45 SPs2_45 P_45
300
Volume of CO2 [dm3 PTN]
250
200
150
100
50
0
0 100 200 300 400 500 600
Reaction time [hour]
Figure 2, volume of accumulated CO2 during the reaction time for the different co-composting trials.
During and at the end of each experiment, the degraded material was analyzed in order to assess
the degree of degradation of OM. Some quality parameters were also analysed. Table 5
summarizes the results of the final of the process.
Table 5, final characterization of the composted substrata.

SP1_45 SPs1_45 SP1_55 SPs1_55 SP2_45 SPs2_45 P_45
Reaction time [h] 511 511 511 511 537 537 538
Dry mass [g] 314 344 290 387 287 294 352
Moisture, M [% wb] 67.7 68.7 51.6 46.6 71.9 67.6 63.3
Organic matter, OM [% db] 71.0 73.2 71.5 71.6 70.5 72.4 75.88
Nitrogen Kjeldhal, N [% db] 3.5 3.7 2.5 2.4 4.8 4.5 3.2
pH 9.34 9.18 9.44 9.51 9.01 9.29 9.76
3
Volume of CO2, VCO2 [dm ] 192 255 138 184 163 196 189
Conversion of OM, (XOM)t [%] 37.0 37.1 37.9 34.7 36.5 36.8 33.6
(C/N)end 10 10 14 15 7 8 12
(C N)end (C N)initial 0.78 0.76 1.07 1.14 0.61 0.67 0.80
Cd [mg/kg db] ND ND ND ND ND ND ND
Pb [mg/kg db] ND ND ND ND ND ND ND
Cu [mg/kg db] 32 39 31 42 29 37 29
Cr [mg/kg db] <QL <QL <QL <QL 26 19 <QL
Ni [mg/kg db] 21 21 22 21 25 24 17
Zn [mg/kg db] 164 214 169 175 112 171 169
IG (25:75 / 50:50) 1.18/1.07 1.18/1.01 1.07/1.09 1.05/0.96 1.12/1.01 1.13/1.04
207
The degree of degradation of OM, (XOM)t , at a moment t, was determinate by Eq. 2 (took into
account the mass loss due to sampling for monitoring analysis), relating the mass of the initial OM,
(MOM)0 and the mass of OM at a moment t, (MOM)t .
(MOM )0 (MOM )t
(XOM )t = 100 (2)
(MOM )0
There are no significant differences in the degree of conversion of OM among the different trials,
leading to an average of 36%. The poultry litter proved to be a good basis for co-composting with
sludge, resulting stabilized mixtures with about 70% of OM.
It is observed (Table 5) that the parameter C/N ratio has values consistent with those
recommended in the literature, in all trials. However, it is possible to verify that the tests conducted
at 55C show a depletion of nitrogen in the compost, comparing to the starting material, as
evidence the quotient of (C/N)end/(C/N)initial. The composts showed percentages of nitrogen between
2.4 and 4.8% db, values consistent with market products.
The results of the determination of heavy metals in compost (Table 5) revealed that it presented
satisfactory level of quality, according to regulation (Decision 2006/799/EC and DL 276/2009 the
portuguese regulation), for this parameter.
The results of the phytotoxicity bioassays showed that both tests with 25% or 50% mature compost
incorporation, had values of germination and growth rate (IG) above 0.9, regardless of operating
conditions. Thus, according to recommended in the literature, the composts could be applied to the
soil, while substrate for cultures support.
It would be important to carry out bacteriological analysis on the compost, in this case it was not
possible.
Results of lightweight aggregates experiments

The observation and interpretation of results from difractograma ray analysis (XRD), it was found
that the clay used in the experiments (C+OiL, C+Poultry, C+Comp) consists of kaolinite (clay
mineral of hydrated aluminosilicate), muscovite (mica) and sanidine (feldspar).
The differential thermal analysis (DTA) and gravimetric (TG), allowed to know the thermal behavior
of clay in the levels of temperature, T: T 150C, 150<T450C, 450<T850C, corresponding to
mass loss and T>850 C, corresponding to a mild increase in mass resulting from the oxidation of
iron.
The quality of the aggregates can be determined by the values of its density, porosity / water
absorption and mechanical strength and is a combination of lower values of density and high
mechanical strength values [5,6].
Table 6 presents the physical and mechanical properties of aggregates produced with the mixtures,
C+OiL, C+Poultry and C+Comp.
It is observed that in all aggregates produced is smaller than the theoretical value of reference,
3
0.7 g/m . However, the aggregates obtained with the incorporation of wastes are between 30 and
40% denser than the aggregate of the standard mixture (C+OiL).
The percentage of WA indicates the degree of open porosity of aggregates and allows foreseeing
the waterproofing ability of lightweight aggregates under study. Fig. 3, shows the expected inverse
relationship between and the WA, for the aggregates with waste incorporated and the standard
aggregate.
Tabela 6, physical and mechanical characteristics of aggregates produced.

3
Type of mixture Bulk density, [g/cm ] Water absortion, WA [%] Compressive strength, m [MPa]
C+OiL 0,36 38,12 0,15
C+Poultry 0,58 28,03 0,64
C+Comp 0,54 25,73 0,60
Fig. 4, shows the expected direct relationship between and the m, for the aggregates, in the
three cases studied, the trade-off between and m is more balanced when the aggregates
incorporate waste. These present values of m within the range of values recommended by
industrial specifications (0.6 to 2.2 MPa).
208
50 0,8
]
m [MPa
Water absortion capacity - WA [%]
0,7
40 C+Poultry
C+Oil 0,6 C+Comp
Resistance to compression -
30 0,5
C+Poultry
C+Comp 0,4
20
0,3
0,2
10 C+Oil
0,1
0 0
0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,2 0,3 0,4 0,5 0,6 0,7 0,8
Density - [g/cm 3] 3
Density - [g/cm ]
Figura 3, relationship between water absorption (WA) Figura 4, relationship between density and
and the density for the lightweight aggregates study compressive strength for the lightweight aggregate
(C+OIL; C+Poultry; C+Comp). study (C+OIL; C+Poultry; C+Comp).
CONCLUSIONS
The work shows that it is possible the valorization of the sludge from secondary treatment of
wastewater from pulp mills and of the poultry litter waste, by co-composting and in the production
of lightweight aggregates.
The testing laboratory scale under forced ventilation, indicate that the co-composting meets
appropriate conditions of moisture, nutrients, pH and granulometry. The temperature control
preferably near 45C, allows the preservation of nitrogen in finished compost.
Through the co-composting is possible to produce compost with quality to be applied to the soil
benefiting plant growth and with potential to be marketed.
It was found to be possible to carry out successfully, the incorporation of poultry litter waste and
compost (resulting from the degradation of the mixture of sludge and poultry litter), while expansive
agents, in training the expanded clay lightweight aggregates for application in construction.
The aggregate produced from the mixture of clay and compost shows a better balance between
density, water absorption and compressive strength.
The advantageous incorporation of the compost becomes interesting, because this is a stabilized
material (odourless), with controlled humidity, allowing the recovery of sludge, which in its raw
state, has excessive moisture content, making difficult the production process of lightweight
aggregates.
References
[1] A.P. Gomes, M.I. Nunes, C.C. Vitoriano, E. Pedrosa, Co-Composting of Biowaste and Poultry
Waste, World Congress ISWA/APESB, Lisbon, CD-room (2009) 10 pp.
[2] T. Marche, et al, Chemical changes during composting of a paper mill sludge-hardwood
sawdust mixture. Geoderma, 116 (2003) 345-356.
[3] S. Pinto, M. Almeida, A.M.S. Correia, J.A. Labrincha, V.M. Ferreira, K. Rosenbom, Study of
the environmental impact of lightweight aggregates production incorporating cellulose industrial
residues. Proc. RILEM 2004 - Conference on the Recycled Materials in Building and Structures,
November 9-11. Spain, Barcelona, 2 (2004b) 771-77.
[4] P.N. Biscaia, Valorizao de resduo de avirio, engao e lamas. Compostagem e produo
de agregados leves. Tese de Mestrado. Departamento de Ambiente e Ordenamento, Universidade
de Aveiro, pp 115 (2010).
[5] E. Fakhfalk, O. Barros, M. Medhioub, F. Rocha, C. Gomes, J. Marques, J. Coroado, F. Kooli,
F.E. Zargouni, F. Jamoussi, Comparative Appraisal of Tunisian and Portuguese Smectitic Clays as
Raw Materials for the Production of Light Weight Aggregates. Clay Science 12 Supplement, 2
(2004) 113-118.
[6] M.A. Monteiro, F. Raupp-Pereira, V.M. Ferreira, M. Dondi, J.A. Labrincha, Lightwheight
aggregates based on industrial wastes. Industrial Ceramics, 25(3) (2005) 71-77.
209
PRODUCTION OF BIOETHANOL FROM BREWERY SPENT GRAINS

1,a 2,a 3,a 4,a
N.S. Caetano , A.L. Nunes , A.M. Mendes , T.M. Mata
1 School of Engineering (ISEP), Polytechnic Instit. of Porto (IPP), Porto, Portugal, nsc@isep.ipp.pt
2 Faculty of Engineering, University of Porto (FEUP), Porto, Portugal, eq03030@fe.up.pt
3 Faculty of Engineering, University of Porto (FEUP), Porto, Portugal, mendes@fe.up.pt
4 Faculty of Engineering, University of Porto (FEUP), Porto, Portugal, tmata@fe.up.pt
a LEPAE Laboratory for Process, Environmental and Energy Engineering
ABSTRACT
This study aims to evaluate the possibility of producing bioethanol from brewery spent
grains with a focus on the pretreatment and enzymatic hydrolysis for the conversion of
biomass to fermentable sugars. Results show that the alkali pretreatment promoted the
conversion of polysaccharides to only one type of sugar (glucose) with a low yield, while
the acid pretreatment promoted the conversion of cellulose and hemicellulose to three
kinds of sugar (glucose, xylose and arabinose), being xylose the sugar in the highest
concentration.
For the hydrolysis of the pretreated biomass, the activity of several enzymes (Viscozyme
L, Ultraflo L, Glucanex 100g and Ban 480L, from Novozymes) was assessed, being
Viscozyme L the one that produced the largest amount of sugars (with a volume of
enzyme/amount of biomass ratio of 100 L/1 g at 50 C, for a contact time of 30 min and
50 rpm stirring speed) with 33% conversion of brewery spent grains to fermentable
sugars.
Finally, Saccharomyces cerevisiae was used to ferment the sugars (all glucose and only
one small fraction of xylose) into ethanol. A yield of 4.21 g ethanol/100 g brewery spent
grains, with 32.5% fermentation efficiency was obtained showing that brewery spent
grains is a promising material for bioethanol production.
Keywords: Bioethanol, biomass pretreatment, brewery spent grains, enzymatic hydrolysis
INTRODUCTION
Depletion of fossil fuels due to the increase of energy needs for transportation along with the
climate implications of their combustion emissions, promoted the need for more sustainable fuels
[1]. Regarding the transportation sector, biodiesel and bioethanol are the most important biofuels in
the current European Union (EU) strategy of renewable energy, aiming at least 20% of the EU
energy consumption coming from renewable sources by the end of 2020 [2]. They can be used
instead or as a blend with diesel and gasoline, respectively, thus contributing to several nations fuel
independency from a few exporting countries.
Bioethanol production is commonly done using sugarcane (Brazil) or corn (USA) but it raises social
and economic problems since these are also used for feeding purposes. Thus the need for other
sugars sources that are inexpensive and more sustainable is increasing, targeting the attention to
lignocellulosic residual materials that still contain significant amounts of underutilized sugars [3].
The brewery industry produces a biological waste that has an interesting value as feedstock for
bioethanol production. This is the brewery spent grains (BSG), a lignocellulosic material rich in
cellulose and hemicelluloses [4] that can provide a source of sugars for the production of
bioethanol via fermentation [5, 6]. At present, BSG is being used in animal nutrition with a very low
economic return. However, it is starting to draw the researchers attention into the investigation of
alternative and more interesting applications such as substrate for enzyme production [7,8] or
microorganism cultivation [8], inexpensive magnetic adsorbent for the removal of water-soluble
dyes [9], activated carbon produced from BSG lignin for metal, phenolic compounds or color
210
adsorption [10] energy production either through direct combustion or fermentation into biogas [11],
production of ferulic [12,13] and p-coumaric [13] acids for usage in food industry, production of
xylitol (a sweetener that can replace sucrose in the food industry) from BSG hydrolysates [14],
production of ethanol from BSG sugars [6, 7, 15] or even for the production of organic acids, amino
acids, vitamins, or other added-value bioproducts using glucose or xylose as substrates [4]. Most
industrial processes use Saccharomyces cerevisiae for sugar fermentation but this yeast is not
able to ferment pentoses. For this reason White and collaborators [6] investigated and compared
the use of Pichia stipitis and Kluyveromyces marxianus yeasts for sugar fermentation, concluding
that Pichia stipitis was the best one to perform this sugar fermentation to alcohol. Also, Xiros and
coworkers [7] studied the ability of Fusarium oxysporum mesophilic fungus to ferment xylose from
alkali pretreated SBG to ethanol, having concluded that it is a very promising way to convert
pentose sugars to ethanol. Owing to the achieved bioconversion yield of 65 g/kg dry matter these
authors suggested the study of other ways of pretreatment in order to make the process
commercially interesting.
This study aims to evaluate the possibility of producing bioethanol from BSG, as a higher added
value solution for this brewerys organic waste management. Two steps of the complete process
were studied in detail, pretreatment and enzymatic hydrolysis, in order to provide the highest
conversion of biomass to fermentable sugars.
The Raw Material Brewery Spent Grain

Most of the starch contained in the wheat grains is converted to fermentable sugars during
mashing and lautering processes in brewing beer. Thus the resulting waste material is composed
of grain husks and other residual compounds such as protein and fibers. Brewery spent grain is
considered to be a lignocellulosic material with 20% protein, 70% fibers (mainly cellulose,
arabinoxylose (hemicellulose) and lignin) and 10% lipids (% by dry matter weight) [4, 7].
The BSG used in this work (Figure 1) was collected from the biggest local brewery, UNICER S.A.,
and was immediately characterized for its humidity content of 69.9%, as determined by a Standard
Method [16], using an oven (Brinder) at 105 C. Samples for the work were kept frozen until they
were used. An ash content of 4.0% (dry matter weight) was determined according to the open
crucible Standard Method [16] using a furnace (Nabertherm, B150) at 550 C for 3h. The lipid
content of BSG was evaluated after 4h Soxhlet extraction to a value of 11.0% (dry weight).
Cellulose content was determined according to NP EN ISO 6865 [17], to a value of 12.4% (dry
weight). A higher heating value of 5570 kcal/kg dry BSG was determined using a calorimeter (Parr,
6772), according to ASTM D5865-10 standard [18].
Figure 1 - BSG particles: left photo as collected from the brewery; right photo after oven drying
Pretreatment Screening and Optimization

For the pretreatment screening, BSG (50 g dry) was mixed either with 500 mL of a 10% NaOH
solution (w/v) or with 500 mL of a 1% H2SO4 solution (v/v). The mixture was heated at 85 C, for
24h, using a thermostatic bath (Selecta, Unitronic-OP) or at 120-130 C, for 10 min, using a
stainless steel autoclave (Parr, model 5100). At the end of the pretreatment, in order to perform
hydrolysis the sludge was neutralized to a pH of 4.9-5.0 with H2SO4/NaOH before enzyme addition.
After identifying that the acid pretreatment would be the best one, the experiment was repeated but
211
temperature conditions were varied to 55, 70, 85 C (with a 24 h contact time) and to 130 C (with a
10 min contact time).
Enzymatic Hydrolysis
For the screening step of the best pretreatment process, hydrolysis of pretreated BSG was
performed under the same experimental conditions, using Viscozyme L (from Novozymes A/S
(Bagsvd, Denmark)), a commercial enzyme preparation of fungal mixed carbohydrase,
containing -glucanase, cellulase, etc., with a declared activity of 100 FBG/g. For each 50 mL of
the liquid fraction resulting from the pretreatment, 417 L of enzyme were used. Hydrolysis took
place at a pH of 4.9 and a temperature of 40 C under constant stirring of 50 rpm, for 30 min. At
this process end, the resulting product was filtered through fiber glass filters (Sterlitech, 0.2 m)
and the filtrate volume was registered. Samples were analyzed by HPLC for sugar quantification.
Enzyme Selection
Selection of the best suited enzyme for polysaccharide hydrolysis was done based on the
availability of commercial enzyme preparations and the characteristics of the raw BSG. Four
preparations were tested: Ultraflo L, Glucanex 100g, Ban 480L and Viscozyme L (all from
Novozymes A/S (Bagsvd, Denmark)). Each assay was run at the recommended conditions of
temperature and pH, with an enzyme load of 834 L/50 mL of the pretreatment product, except
Glucanex that is in the solid form, where 1 g/50 mL was used. Experimental conditions are
resumed in Table 1, together with a brief enzyme description.
Table 1 Experimental conditions of enzymatic hydrolysis performed on 50 ml of pretreatment

product for 30 min
Enzyme Activity Composition Temperature (C) Enzyme Load (L) pH
-glucanase,
Xylanase,
Viscozyme L 100 FBG/g 50 834 5.1
Cellulase,
Hemicellulase
-glucanase
Ultraflo L 3550 FXU/g 50 834 6.0
xylanase
Bacterial -amylase
Ban 480L 480 KNU/g 60 834 6.2
1,4--glucanase
Glucanex 100g 100 BGXU/g 1-3;1-6 -glucanase 75 1,0618 4.5
FBG/g - Fungal -glucanase; FXU/g - Farbe Xylanase Unit/g;
BGXU/g - Botrytis P-glucan unit/g; KNU/g - Kilo Novo Unit/g
Fermentation
75 g of dried BSG was pretreated with 750 mL of 1% (v/v) H 2SO4 at 85C for 24h and with 50 rpm
stirring, in a thermostatic bath. Enzymatic hydrolysis was then performed using an enzyme load of
100 L /g, corresponding to 7.5 mL of Viscozyme L for a resulting product volume of 880 mL.
Saccharomyces cerevisiae yeast at 4 g/L load was used for the fermentation step, at 30 C and
with 80 rpm stirring, for 48 h.
Sugar Determinations
Glucose, arabinose and xylose contents were determined by HPLC (Gilson) equipped with an ELS
detector (PLEMD 960, Polymer Laboratories). A 4.6 mm Chromsep SS 100 column, with pre-
column was used, with a 20 L sample loop. Operating conditions for the column were 0.4 mL/min
acetonitrile:water at 90:10, column temperature of 60 C and an analysis time of 20 min. Detector
conditions include an air flowrate of 5.20 L/min and 70 C.
Optimization of the Pretreatment Conditions

As stated before, it was decided to choose between an alkali and an acid pretreatment, performed
212
at the same temperature conditions. Nevertheless, the effect of the pretreatment method can only
be evaluated after the hydrolysis of the released polysaccharides. Thus the standard procedure
with one of the available enzymes was applied to the pretreated material. The results are shown in
Table 2, where it can be seen that the alkali pretreatment is only slightly effective in releasing
glucose, being more efficient at the lower temperature of 85 C, where it promoted the release of
5.49 g glucose/100 BSG. On the other hand, the acid pretreatment was much more efficient in
releasing not only cellulose but also larger amounts of xylose and some arabinose, and at 85 C a
total sugar amount of 36.92 g/100 g BSG could be released, being 26.9% glucose and 57.3%
xylose. Hence the acid pretreatment was chosen for further temperature optimization.
Under acidic conditions, at the temperatures of 55 and 70 C the total amount of sugars released
was much lower than at 85 C and, at 55 C xylose could not even be released at all but at 70 C
the amount of arabinose released was slightly higher than the one released at 85 C. Total sugar
released under the lower temperature acidic condition was about 50% higher than under alkaline
conditions. As the sugar that can be most easily converted into ethanol is glucose, the optimal
condition of acidic pretreatment at 85 C was chosen.
Table 2 Sugar concentration and production under different pretreatment conditions followed by
enzymatic hydrolysis with Viscozyme L.
Concentration (g/L)
Pretreatement Temperature Total Sugar/ 100g BSG
xylose arabinose glucose
Alkali 85C ND ND 4.58 5.49
Alkali 130C ND ND 2.47 2.97
Acid 85 C 17.63 4.87 8.27 36.92
Acid 130C 13.30 4.14 4.78 26.66
Acid 55 C ND 3.92 3.33 8.70
Acid 70 C 4.64 5.15 4.33 16.93
Screening of the best enzyme

Enzymatic activity was evaluated using the same amount of liquid enzymes Viscozyme L, Ultraflo L
and Ban 480L, at the recommended conditions of temperature and pH, over the acid pretreated
BSG (85 C) as resumed in Table 1. The results are shown in Table 3 where it can be seen that the
best enzyme is clearly Viscozyme, that was able to produce a total sugar amount of 32.27 g/ 100 g
BSG, of which 62.2% was xylose and and 23.2% was glucose. Viscozyme has also the advantage
of performing better under mild conditions of temperature (50 C). This represents lower energy
consumption in the hydrolysis step and at lower pH, which means less neutralizing agent to
perform the hydrolysis at higher pH of 5.1. Also, a solid supported enzyme was tested (Glucanex
100g) but the overall sugar released was similar (with a slightly better yield in glucose) to that
released while using Ultraflo L and about 50% less than when using Viscozyme L.
Table 3 - Sugar concentration and production applying different enzymes over the pretreated BSG
under the best conditions of acidic treatment at 85 C.
Concentration (g/L)
Enzyme Total Sugar/ 100g BSG
Viscozyme L 16.73 3.92 6.24 32.27
Ultraflo L 9.48 2.98 2.19 17.58
Ban 480L 9.19 2.91 1.58 16.41
Glucanex 100g 8.87 2.74 3.07 17.61
Enzymatic hydrolysis optimization

The optimization proceeded with the evaluation of the hydrolysis conditions and its influence on
sugar release. Thus the combination of a temperature of 40 and 50 C with reaction time of 30, 60
and 90 min were tested. Results shown in Table 4 allows one to conclude that the higher the
contact time the lower the total sugar production, either at a temperature of 40 or 50 C. For 30 min
of reaction time there is no significant difference in the total or individual sugar release.
213
Table 4 - Sugar concentration and production for enzymatic hydrolysis optimization.
Time Concentration (g/L)
Temperature (C) g Total Sugar/ kg BSG
(min) xylose arabinose glucose
30 15.74 4.01 7.48 326.8
40 60 14.48 3.70 6.62 297.6
90 14.29 3.80 5.98 288.9
30 15.72 3.86 7.77 328.1
50 60 14.75 3.77 5.68 290.4
90 13.84 3.87 5.45 277.9
The best conditions for performing enzymatic hydrolysis (with Viscozyme L) of 50 C and a 30 min
reaction time were chosen (total sugar release of 32.81 g/ 100 g BSG), although from a practical
point of view, the same reaction could have been performed at 40 C with no significant decrease
in the total sugar release.
Fermentation
In the final step, bioethanol production from sugar released in the former process was intended.
Pretreated and enzymaticaly hydrolysed BSG was fermented with Saccharomyces cerevisiae. After
18 h fermentation time all of the glucose was converted into ethanol, only a very small fraction of
xylose was converted (about 11.5%) and none of the arabinose could be converted into ethanol, as
shown in Table 5. Even after a 48 h reaction time there was no significant increase in sugar
conversion. The global efficiency in sugar conversion into ethanol was of 32.5%, corresponding to
a production of 42 g ethanol/ kg dry BSG, that is close to the 65 g ethanol/ kg dry BG reported by
Xiros and coworkers [8] using Fusarium oxysporum to ferment xylose and glucose, or a production
of 74 g ethanol/ kg dry BSG that was obtained by Xiros and collaborators [19] with Neurospora
crassa fungus. These results are quite interesting from the point of view of sugar production from
BSG material and the very small conversion of xylose and null conversion of arabinose can be
explained with the known incapability of Saccharomyces cerevisiae to metabolize other sugars
than glucose. A further step of converting the very large amount of xylose into ethanol will increase
drastically the BSG conversion yield into ethanol.
Table 5 - Sugar concentration along fermentation.

Concentration (g/L)
Time (h) g Total Sugar/ kg BSG Efficiency (%)
0 12.23 3.48 5.37 252.9
18 10.82 3.46 - 171.3
32.5
24 10.67 3.25 - 166.9
48 10.74 3.42 - 169.9
CONCLUSIONS
The results from this work show that BSG is a very interesting residual material for bioethanol
production. The sulphuric acid (1% v/v) preatement of BSG (500 mL/50 g dry weight) at 85 C and
50 rpm for 24 h, promoted the highest release of polysaccharides that could then be hydrolyzed
into simple sugars, using Viscozyme L at a load ratio of 834 L/50 mL of the pretreated product, at
50 C, pH of 5.1 and with a constant stirring of 50 rpm. These conditions allowed for a ratio of 32.8
g total sugar / 100 g BSG. Fermentation of the resulting broth into bioethanol with Saccharomyces
cerevisiae only allowed for the conversion of 32.5% of the sugars, thus rendering a total amount of
bioethanol of 42 g / kg BSG, instead of the maximum total amount of 168 g ethanol / kg BSG. To
make this process even more interesting, attention should be paid to the fermentation step, testing
other species that can convert arabinose and xylose, which is the most important fraction of sugars
released in the process.
Acknowledgements
Authors would like to thank Novozymes for their kind offer of several enzymes that allowed for the
realization of this work. Also UNICER is acknowledged for their financial support on the project. All
214
the team from the Laboratrio de Tecnologia Qumica of ISEP is acknowledged for their constant
help and suggestions in the lab.
Literature References
[1] International Energy Agency (IEA), World energy outlook 2010. IEA/OECD. Paris, 2010,
www.iea.org.
[2] European Renewable Energy Council (EREC), Renewable energy target for Europe 20% by
2020, January 2004. In http://www.wind-energie.de/fileadmin/dokumente/Themen_A-
Z/Europa/EREC_Targets_2020.pdf.
[3] T.M. Mata, A.A. Martins, S.K. Sikdar, C.A.V. Costa, N.S. Caetano, Biofuels sustainability
evaluation through the supply chain, Submitted to SDEWES2011, September 25 29, 2011.
[4] S.I. Mussatto, D. Dragone, I.C. Roberto, Brewers spent grain: generation, characteristics and
potential applications, Journal of Cereal Science, 43:1 (2006) 1-14.
[5] S.I. Mussatto, I.C. Roberto, Acid hydrolysis and fermentation of brewers spent grain to
produce xylitol, Journal of the Science of Food and Agriculture, 85(14) (2005) 2453-2460.
[6] J.S. White, B.K. Yohannan, G.M. Walker, Bioconversion of brewers spent grains to
bioethanol, FEMS Yeast Research, 8:7 (2008) 1175-1184.
[7] C. Xiros, E. Topakas, P. Katapodis, P. Christakopoulos, Evaluation of Fusarium oxysporum as
an enzyme factory for the hydrolysis of brewers spent grain with improved biodegradability for
ethanol production, Industrial Crops and Products, 28:2 (2008) 213-224.
[8] A. Gregori, M. Svagelj, B. Pahor, M. Berovic, F. Pohleven, The use of spent brewery grains for
Pleurotus ostreatus cultivation and enzyme production, New Biotechnology, 25:2/3 (2008)
157-161.
[9] I. Safarik, K. Horska, M. Safarikova, Magnetically modified spent grain for dye removal,
Journal of Cereal Science, 53:1 (2011) 78-80.
[10] S.I. Mussatto, M. Fernandes, G.J.M. Rocha, J.J.M. rfo, J.A. Teixeira, I.C. Roberto,
Production, characterization and application of activated carbon from brewers spent grain
lignin, Bioresource Technology, 101:7 (2010) 2450-2457.
[11] F.C. Ezeonu, A.N.C. Okaka, Process kinetics and digestion efficiency of anaerobic batch
fermentation of brewer's spent grains (BSG), Process Biochemistry, 31:1 (1996) 7-12.
[12] C. Xiros, M.aria Moukouli, E. Topakas, P. Christakopoulos, Factors affecting ferulic acid
release from Brewers spent grain by Fusarium oxysporum enzymatic system, Bioresource
Technology, 100 (2009) 59175921.
[13] S.I. Mussatto, G. Dragone, I.C. Roberto, Ferulic and p-coumaric acids extraction by alkaline
hydrolysis of brewer's spent grain, Industrial Crops and Products, 25:2 (2007) 231-237.
[14] S.I., Mussatto, I.C., Roberto, Acid hydrolysis and fermentation of brewer's spent grain to
produce xylitol, 85:14 (2005) 2453-2460.
[15] A.J. Jay, M.L. Parker, R. Faulks, F. Husband, P. Wilde, A.C. Smith, C.B. Faulds, K.W.
Waldron, A systematic micro-dissection of brewers spent grain, Journal of Cereal Science,
47:2 (2008) 357-364.
[16] APHA, AWAA, WPCF, Standard Methods for the Examination of Water and Wastewater. 18th
ed., 1992.
[17] NP EN ISO 6865. Animal feeding stuffs. Determination of crude fiber content. Method with
intermediate filtration (2009).
[18] ASTM D5865-10, Standard Test Method for Gross Calorific Value of Coal and Coke (2010).
[19] C. Xiros, E. Topakas, P. Katapodis, P. Christakopoulos, Hydrolysis and fermentation of
brewers spent grain by Neurospora crassa, Bioresource Technology, 99 (2008) 54275435.
215
PRODUCTION OF SINTERED -ALUMINA BY EXPLOSIVE COMPACTION

FROM LOW TEMPERATURE CALCINATED ALUMINIUMRICH SLUDGE
1 2 3
A. R. Farinha , R. Mendes and M. T. Vieira
1
CEMUC Centro de Engenharia Mecnica da Universidade de Coimbra, Department of
Mechanical Engineering, University of Coimbra, Coimbra, Portugal, rita.farinha@dem.uc.pt
2
ADAI Associao para o Desenvolvimento da Aerodinmica Industrial, Department of
Mechanical Engineering, University of Coimbra, Coimbra, Portugal, ricardo.mendes@dem.uc.pt
3
CEMUC Centro de Engenharia Mecnica da Universidade de Coimbra, Department of
Mechanical Engineering, University of Coimbra, Coimbra, Portugal, teresa.vieira@dem.uc.pt
ABSTRACT
During explosive compaction the -alumina was transformed into -alumina. At
atmospheric pressure this phase transformation starts at 1200C. Moreover, it was
detected that the sulfur content of 4.5% (w/w) registered in sludge calcinated at 800C
was reduced to 0.04% (w/w) after explosive compaction. The final real density of
3
calcinated and consolidated powders was 3930 kg/m , which is close to the density of -
alumina. The sintering after detonation leads to parts with hardness values close to those
of -alumina produced by conventional techniques. These unexpected results open a
sustainable possibility to make the recovery of Al-rich sludge and the production of -
alumina bulk by explosive compaction into a reality.
Keywords: Al-rich sludge; explosive compaction; phase transformation; -alumina
INTRODUCTION
The recycling and valorization of Al-rich sludge from aluminum anodizing industries represented a
challenge for researchers that struggle to decrease the environmental impact of these industries.
This objective is particularly relevant in countries where anodizing industries have a great
implantation, as is yet the portuguese case. Furthermore, due to its high alumina content after
calcination, several opportunities are being envisaged for its high-tech valorisation. Some studies
have shown the possibility of mullitization by using aluminium sludge mixed with silica-rich wastes
[1, 2]. Others have used sludge (as-received and previously dried or calcinated) as a single raw
material or combined with common ceramic components; using different conventional strategies of
shape forming and sintering, the maximum apparent density value of such material was 3300
3
kg/m [3].
Previous research work revealed that to produce only -alumina by calcination it was considered
necessary to calcinate it up to 1650 C. This heat treatment induces an agglomeration of the
sludge particles, a reduction of their specific surface area, and a significant reduction their
sinterability [4]. Explosive compaction was shown to substantially distort the crystal lattice, activate
the particle surface, and lead to particle fragmentation, thus promoting the sintering process [5].
After explosive compaction only after sintering it was possible to attain a density and hardness
similar to sintered from commercial -alumina [4]. These results make this strategy to recover
aluminum sludge impossible due to high energy costs. In order to decrease the environmental
impact of the heat treatments (calcination and sintering), the main objective of the present work
was to study the explosive compaction of sludge calcinated at lower temperatures, such as 800 C,
and subsequent sintering. Some anodizing industries that have heat-recovery systems furnish
sludge heat-treated at this temperature.
216
EXPERIMENTAL DETAILS
In this study Al-rich sludge heated up to 800 C and kept at that temperature for 1h, after which the
heat-treated powders were milled in an agate mortar and sieved cut at 100 m. The powders were
characterized concerning particle size and density, using laser diffraction spectrometry (LS130,
Coulter Corporation), according to the Fraunhofer model, and Helium Picnometry (Accupy 1330,
Micromeritics Instrument Corporation), respectively. The phase composition was evaluated by X-
ray diffraction (Phillips) with BraggBrentano set up and Co (K) radiation.
The explosive compaction experiments were carried out using the simplest and most well-known
direct method, cylindrical configuration (Fig. 1). The steel tube containing the powder, and closed at
both ends, was surrounded by the explosive. When detonated from upwards, a ring-shaped
detonation front developed in an axial direction, driving the container wall inward and originating a
shock wave which proceeds into the powder carrying out a compaction or consolidation of the
powder [6].
The powder container was filled by pouring small amounts of the powder into the steel tube and
then uniaxially compressing the powder. The filled tube was weighted and the density evaluated.
Ammonium nitrate based water-in-oil emulsion sensitized with hollow perlite micro spheres was
used as explosive composition.
Fig. 1. The explosive compaction process.
After explosive compaction, the tube was cross sectioned and the different surfaces of rods
polished; in some cases the steel tube was removed. Sintering of specimens after explosive
compaction was carried out for dwell times of 1h at two different temperatures (1200 and 1650 C).
The content of sulfur in the specimens before and after explosion was evaluated by elemental
analyzer (EA1108 Fisons Carlo Erba Instruments). The fracture surfaces were observed by
Scanning Electron Microscope [SEM] (JSM-5310, Jeol).
The densification of powders after explosion and sintering was estimated from microhardness
values (Micro Hardness Tester HMV-2 Shimadzu Corporation) using a Vickers indentor and a
maximum load of 2.94 N during 15 seg.
217
The sludge as-received was constituted by aluminium hydroxide and water. After heating at 800C
the main phase was -alumina (Fig. 2). In both cases the nanometric character of the crystallite
3
size is evident. The density was 2850 kg/m and the mean size of particles 31 m (Fig. 3).

o
T=800 C
Intensity [u.a.]
As reveided
20 40 60 80 100
o
2 [ ]
Fig. 2. X-ray diffractograms of the sludge as-received and after heating at 800C
(o:boehmite, :-alumina).
3
Volume [%]
0
0,1 1 10 100
Particle size [m]
Fig. 3. Particle size distribution.
The compacts produced with powder heated at 800 C using a ratio between the mass of explosive
to powder (E/M) of 6 and a detonation velocity (D) of 4900 m/s can be observed in fig. 4. In the top
of the cylinder, the compact did not present cracks. However, in the base of the cylinder spiral
cracks occurred.
218
spiral
cracks
2 mm 2 mm
(a) (b)
Fig. 4. Compacts photography (a - top, b - base).
The detonation of powder preheated at 800 C led to a phase transformation of -alumina into -
alumina (Fig. 5) in the entire compact. For the same sludge but submitted at atmospheric pressure
this transformation occurred at 1200C [4]. Once there was a phase transformation, the density of
3
the powder also changed from 2850 to 3930 kg/m ; the last value is very close to that of
commercial -alumina. This phase transformation was also reported elsewhere in nanometric -
alumina [7].

Intensity [u.a.]

After explosion

Before explosion
20 40 60 80 100
o
2[]
Fig. 5. X-ray diffractograms of the powder before and after explosion (: -alumina, : -alumina).
One of the compounds often present in this type of sludge is metal sulphates. The presence of the
group sulphates can be prejudicial to the valorisation of this type of waste, since it can lead to the
production of sulphuric acid. Given the importance of sulphur, this element was evaluated before
and after explosion. It was found that the sludge had 4.5% (w/w) of sulphur before explosion,
219
whereas after the quantity of this element was only 0.04% (w/w). The reduction of sulphates during
the explosion is an advantage, since explosion gases must be treated before being released into
the atmosphere and so the sulphur resulting from the sludge can be treated at the same time. If
sulphur release occurred during calcination or sintering, then it would be necessary to carry out
these processes in heat treatment furnaces with gas treatment. In addition, sulphur release during
sintering would cause porosity which would decrease the quality of the final product.
The fracture surface of the compact (fig. 6) showed a good compaction and its morphology was not
lamellar, which is typical of sludge calcinated at temperatures lower than 1200 C and explosively-
compacted. The compacts microstructure was nevertheless similar to that of sludge calcinated at
1650 C and compressed by explosives [4].
(a) (b)
Fig. 6. SEM images of the fracture surface of the compacts after explosion.
When the explosion compaction was not enough for the consolidation of the sludge, it was
necessary to submit the compact to a sintering process. For sintering, two different temperatures
(1200 C and 1650 C) were selected. The temperature of 1650 C is the typical temperature used
for sintering of alumina. Having in mind the nanometric character of the sludge pre-treated, the
effect of lower temperature of sintering as 1200 C [5] was studied. Given that one of the objectives
of this study was to minimize the environmental impact, it made sense to try the low temperature
sintering. The values of hardness of compacts before and after sintering were summarized in table
1.
Table 1. Hardness of compacts before and after sintering.
Explosion and sintering

Process Explosion
1 h at 1200 C 1 h at 1650 C
Hardness [GPa] 4.91.0 8.61.4 15.60.8
It was observed that the hardness values for the compacts without sintering were very low when
compared to typical values of alumina; this shows that during explosion only compression
occurred, without interparticle bonding. For hardness after 1 h at 1200 C, values were already
higher, indicating that some interparticle bonding had occurred, though still low values. The study
of the low temperature sintering should be continued, once the sintering temperature and time have
not been optimized. Hardness after 1 h at 1650 C was identical to the hardness of the compact
produced through the sludge calcinated at 1650 C, detonated and sintered at this same
temperature for 4 h. In this case hardness values are similar to the sinters of commercial alumina
produced by conventional methods of pressing.
220
CONCLUSION
From sludge calcinated at 800 C, which consists mainly of -alumina and sulphates, by explosive
compaction it is possible to produce -alumina with low sulphur content.
The sintering after explosive compaction leads to parts with hardness values close to those of
alumina produced by conventional techniques.
This study has shown the possibility of recovering this type of sludge to produce parts of -alumina,
however the study will continue with the optimization of sintering at low temperatures and the
possibility of using sludge calcinated at temperatures below 800 C to minimize the environmental
impact.
ACKNOWLEDGMENTS
The authors would like to thank the Portuguese Foundation for Science and Technology (FCT)
thought SFRH/BD/41214/2007 for financial support, and to the LEDAP Laboratory of Energetics
and Detonics where the compaction tests were realized.
References
[1] S.C. Vieira, A.S. Ramos, MT Vieira, Mullitization kinetics from silica- and alumina-rich wastes,
Ceram. Int. 33 (2007) 59-66.
[2] F.A. Costa Oliveira, V. Livramento, F. Delmas, Novel mullite-based ceramics manufactured from
inorganic wastes I. Densification behavior, J. Mat. Proc. Tech. 196 (2008) 101-108.
[3] M.J. Ribeiro, D.U. Tulyaganov, J.M. Ferreira, J.A. Labrincha, Production of Al-rich sludge-
containing ceramic bodies by different shaping techniques, J. Mat. Proc. Tech. 148. (2004) 139-
146.
[4] A.R. Farinha, J.B., Ribeiro, R. Mendes, M.T. Vieira, Sock activation of -alumina from calcinated
Al-rich sludge, Ceram. Int., 35 (2009) 1897-1904.
[5] A. A. Bukaemskii, E. N. Fedorova, Explosive Compaction and Low-Temperature Sintering of
Alumina Nanopowders, Combust., Explos. Shock Waves, 44 (2008) 717-728
[6] R.A. Prmmer, Latest Results in the Explosive Compaction of Metal & Ceramic Power and their
th
Mistures, 4 International of the Center of High Energy Forming in Estes Park/Co.(1973).
[7] R.A. Prmmer, P. Weimar, Explosive Consolidation of Nanopowders, Interceram. 51 (2002)
394-397.
221
13th September
Session 2.4
( HAZARDOUS WASTES TREATMENTS )
Chairman: Regina Monteiro
222
LIGNOCELLULOSIC WASTES TO FORMULATE BIOMIXES FOR

PESTICIDES DEGRADATION IN BIODED REACTOR
1,3 3 3 3 2
M.C. Diez , C. Urrutia , O. Rubilar , G. Tortella , F. Gallardo
1
Chemical Engineering Dept., University of La Frontera, Temuco, Chile. mcdiez@ufro.cl
2
Chemical Science Dept. University of La Frontera, Temuco, Chile. fgallar@ufro.cl
3
Scientific and Technological Bioresource Nucleus-BIOREN, University of La Frontera,
Temuco, Chile
ABSTRACT
The effect of different types of soil (Clay soil, Sandy soil and Trumao soil), different
lignocellulosic residues (wheat straw, pine sawdust and barley husk) and incubation
temperature on biological activities in the biomix of biobed system were evaluated. The
biomix was prepared with peat, soil and lignocellulosic materials in different volumetric
proportions. Biological activities (fluorescein diacetate hydrolysis (FDA) and ligninolytic
activity) were evaluated periodically. Also, the degradation of a mixture of pesticides
(atrazine, chlorpyrifos, iprodione and isoproturon) in the biomixes was evaluated.
Trumao soil has high content of organic matter compared with Clay soil and Sandy soil.
Lignin and cellulose content were high in pine sawdust compared with barley husk and
wheat straw. In the biomix FDA hydrolysis increased as temperature increases especially
when wheat straw and barley husk were present in the biomix with trumao soil. The
ligninolytic activity was high at 20 and 30C, except in the biomixes with barley husk,
where highest activities were found at 10C. The degradation of the pesticides was high
(> 70%), except for the fungicide iprodione, especially when barley husk was added in the
biomix. The dissipation of the pesticides in the biobed was associated with both
adsorption and degradation processes.
Keywords: Lignocellulosic wastes; biomixtures; biobed; pesticides
INTRODUCTION
The agriculture is a relevant sector in Chile with an increase of approximately 70% of the areas
destined for these activities in the last 10 years. Especially, the region of the Araucana
concentrates more than 60 % of the cultures of cereals of the country, with the consistent
generation of residues (> 1000000 ton/year). On the other hand, modern farming and food
production requires high quantity of pesticides. However, surface and groundwater can be
contaminated due to their inadequate management. To solve this problem, the biobed technology
originated in Sweden can be used. The biobed is an excavation in the soil sealed in the bottom and
filled with a biomix of soil, peat and lignocellulosic material that allow retention and later
degradation of pesticides in situ, minimizing the soil and water contamination [1].
An adequate biomixture promotes pesticide binding and an efficient and robust microbial flora with
a durable pesticide degradation capacity able to tolerate pesticides at high concentrations, at
repeated applications and in mixtures [1]. The straw stimulates the growth of ligninolytic
microorganisms (such as white-rot fungi) and the production of extracellular ligninolytic enzymes as
phenoloxidases (peroxidases and laccases). Ligninolytic enzymes present broad specificity makes
them suitable for degradation of mixtures of pesticides. The peat contributes to sorption capacity,
moisture control and also abiotic degradation of pesticides. In addition, peat decreases the pH of the
biomixture, which is favorable for fungi and their pesticide-degrading enzymes [2]. The soil is an
important source of microorganisms in the biobed, between them, pesticide-degrading bacteria (as
Actinomycetes) that can act synergistically with fungi, at the sometime, enhances the sorption
223
capacity in the biobed due to it humus and clay content. According with Castillo et al. [1] the high C/N
ratio and the low pH of the biomixture may restrict bacterial processes.
The straw is generally accepted as lignocellulocic material in the biobed, due to its availability on
farms and low cost. However, some other lignin-rich component should be present in the
biomixture of the various systems developed today [2,3,4]. Depending on its availability in some
places, the straw in the biomixture has been replaced by other materials, for example, chitin, citrus
peel, vine branches, coconut byproduct, and composted farmyard manure [5,6]. To choose some
material to replace straw, it is necessary to know its composition and maintain an adequate C/N
ratio and other elements (micronutrients) in order to promote the best conditions for
microorganisms growth in the biobed. The effect of soils type used for biobeds mixture was studied
by Fogg and Boxall [7]. They found that there were no significant differences in the biobed
performance. However, the soils used in their study had a low level of organic matter compared
with soil of the south of Chile (Andisol and Ultisol). Chilean Andisol could be an effective
component of biobeds due to its high organic matter content with great affinity for pollutants due to
the presence of humic and fulvic acid and reactive clays like Al and Fe hydroxide groups [8] and
has been used efficiently for chlorophenols adsorption and degradation [9]. Therefore, the goal of
this study was to evaluate the effect of different types lignocellulosic residues and types of soil on
biological activities of a biomix and in the degradation of pesticides.

Preparation of biomix: The biomix was prepared by mixing different soils (Clay soil, Sandy soil
and Trumao soil), different lignocellulosic materials (wheat straw, pine sawdust and barley husk)
and peat in the volumentric proportion described in Table 1. The top soils were sampled from 0-20
cm depth, air dried at room temperature and sieved through 2 mm mesh. The wheat straw was
chopped to obtain pieces smaller than 2 cm in length. All materials were mixture in the volumetric
proportion previously described and were incubated during 30 days at 10, 20 and 30 1 C.
Distilled water was added to maintain biomixes with 60% of water holding capacity (WHC). At the
end of incubation period, fluorescein diacetate hydrolysis (FDA), and ligninolytic activity were
measured.
Pesticides degradation in the biomixes: Samples of each pre-incubated biomix (10 g d-w) were
placed in glass jars of 500 mL and were spiked with a solution of commercial pesticides mixture of
-1
atrazine, isoproturon, iprodione and chlorpyrifos (100 mg kg each) and were incubated for 40
days at 20 1C. The moisture content was maintained at 60% of water holding capacity (WHC) by
addition of distilled water. Each experiment was carried out in triplicate under destructive sampling
mode. Biomixes without pesticides were used as control. The residual pesticides, FDA activity and
peroxidase activity were periodically measured.
Analytical methods
Ligninolytic enzyme activity: The analysis was performed using the MBTH/DMAB assay
according to the methodology described by Castillo et al. [10]. To extract the enzymes, samples of
the biomix (10 g d.w.) were weighed into Erlenmeyer flasks and 50 mL of 100 mM succinate-lactate
buffer (pH 4.5) were added to each sample. The flasks were shaken at 100 rpm for 2 h, and 10 mL
of the supernatant were collected and centrifuged at 4,000 rpm for 20 min and filtered through 0.45
m membrane (National Scientifics filter unit). The reaction mixture contained 300L of 6.6 mM
DMAB, 100L of 1.4 mM MBTH, 30L of 20 mM MnSO 4, 10L of 10 mM H2O2, and 1560L of the
sample in a 100 mM succinic/lactic acid buffer pH 4.5. The reaction was followed at 590 nm (=
-1 -1 TM
0.053 M cm ) in a spectrophotometer (Spectronic Genesis 2PC). Because no correction was
made for the possible presence of lignin peroxidase (LiP) and laccase (Lac) activity, this
measurement may represent the sum of manganese peroxidase, LiP and laccase [3].
Fluorescein diacetate hydrolysis: The total microbial activity was measured by monitoring
fluorescein diacetate hydrolysis (FDA) according to the methodology described by Schnrer and
Rosswall [11] with slight modifications. Briefly, 1g of biomix from glass flasks was incubated in a 30
mL conical flask with 9.9 mL of sterile 60 mM sodium phosphate buffer, pH 7.8. The reaction was
-1
started by adding 0.1 mL of a FDA solution (2.0 mg mL ). After 1 h of incubation at 25 1 C, 10
224
mL of acetone was added to stop the reaction. The absorbance at 490 nm was determined after
removal of the biomix by centrifugation and filtration. The concentration of the released fluorescein
was calculated by a calibration curve with standard quantities of FDA and the results were
-1 -1
expressed as g FDA g h .
RESULTS
Characterization: The characterization of the components of the biomixes showed that Trumao
soil has a high content of organic matter (11.7%) compared with Clay soil (3%) and Sandy soil
(2%). Lignin and cellulose content were high in pine sawdust (20.6 and 54.3%, respectively)
compared with barley husk (2.4 and 9.6%) and wheat straw (9.9 and 41.8%). The biomixes with
more organic matter content were composed with Clay soil and Trumao soil and these values
increased when barley husk or pine sawdust were added to the biomix (Table 1).
Table 1. Volumetric proportion of component of the biomix and its characterization

Lignocellulosic Biomix characterization
Biomix Soil Peat wastes [%]
[%] [%] OM N pH
WS PS BH
[%] [mg/kg]
A1 Clay 25 50 0 0 10.7 1.2 5.7
A2 25 25 25 0 13.5 1.9 6.0
A3 25 0 25 19.0 6.2 5.1
A4 0 0 50 22.2 13.8 5.2
A5 0 50 0 26.0 1.3 5.9
B1 Sandy 25 50 0 0 7.8 0.9 5.3
B2 25 25 25 0 12.9 0.9 5.8
B3 25 0 25 12.3 3.8 5.9
B4 0 0 50 17.3 6.1 5.6
B5 0 50 0 17.5 0.7 5.4
C1 Trumao 25 50 0 0 13.1 5.4 5.1
C2 25 25 25 0 14.2 4.6 5.8
C3 25 0 25 20.7 7.8 5.4
C4 0 0 50 27.6 17 6.1
C5 0 50 0 22.7 1.3 5.3
WS=Wheat straw; PS=Pine sawdust; BH=Barley husk
Biological activity: Biological parameters such as FDA hydrolysis (Figure 1) and ligninolytic
activity (Figure 2) were affected by the incubation temperature and the lignocellulosic residues
used to prepare the biomixes. FDA increased as the temperature increases, the highest values
were obtained at 30 C, mainly when wheat straw and barley husk were present in the biomix
(between 4 and 6 g g-1 h-1). Samples of biomix with husk barley (A3, A4, B3, B4, C3 and C4)
stimulated microbial activity (highest FDA values) probably due to the low lignin and cellulose
contents of the barley husk (2.4 and 9.6%, respectively) and the highest values of available
nitrogen in the biomixes prepared with this residue (Table 1). On the other hand, samples of biomix
with pine sawdust (A2, A5, B2, B5, C2 and C5) presented the lowest values of FDA probably due
to the high lignin content (20.6%) of the sawdust and less accessible source of carbon and
nutrients in the biomix for consumption by microorganisms.
225
10
8
ug FDA/g/h
4
a
2
0
A1 A2 A3 A4 A5 B1 B2 B3 B4 B5 C1 C2 C3 C4 C5
Biomix
10C 20C 30C
Figure 1. FDA activity in the biomixes composed with Clay soil (A1 to A5), Sandy soil (B1 to B5)
and Trumao soil (C1 to C5), incubated at 10, 20 and 30 C during 30 days.
The ligninolytic activity increased in the biomixes prepared with Clay soil as the temperature
increases. However, ligninolytic activity in some biomixes with Sandy soil (B1, B2, B4 and B5) and
Trumao soil (C3 and C4) was high at 10C. This effect might be due to the fact that the barley husk
possess a high quantity of microorganisms those that take part in the degradation of organic
compound [12]. Nevertheless, not all the microorganisms are capable of secreting ligninolytic
enzymes, which are associated principally to white-rot fungi. These fungi have a slow growth and
can growth in a wide range of temperatures. Therefore, at 10 C the growth and activity of
antagonistic microorganisms to the white-rot fungi could be diminished.
0.6
0.5
Peroxidases U/kg
0.4
0.3
0.2
0.1
0.0
A1 A2 A3 A4 A5 B1 B2 B3 B4 B5 C1 C2 C3 C4 C5
Biomix
10C 20C 30C
Figure 2. Ligninolytic activity in the biomixes with Clay soil (A1 to A5), Sandy soil (B1 to B5) and
Trumao soil (C1 to C5), incubated at 10, 20 and 30 C during 30 days
Therefore, the biological activities were highest in biomixes composed with Clay and Trumao soils
and these were affected by the temperature more than for the incubation time. Lignocellulosic
residues stimulated both ligninolytic and FDA activities, especially in the biomix composed with
wheat straw and barley husk. Similar results were found in the CO2 evolution (data non shown).
226
Degradation of pesticides: The degradation of the pesticides was high (> 70%) in the biomixes
prepared with the different lignocellulosic residues, except for iprodione (Table 2). Atrazine, was
highly removed in all biomixes tested (> 65%), mainly when wheat straw and barley husk were
used. Isoproturon and chlorpyrifos were also removed but in a lesser extent. The less percentage
of degradation of iprodione could be due to iprodione is a fungicide and the composition of the
biomixes favors the growth of fungi, especially of white-rot fungi [1].
Considering that the pesticides tested are moderately mobile or non mobile, the dissipation of the
pesticides in the biobed was associated with both adsorption and degradation processes.
Moreover, the degradation of the pesticides was associated with a high respiration activity
especially in biomixes prepared with Trumao soil (C1 C2 and C3) due to its high organic matter and
nitrogen contents.
-1
Table 2. Degradation (%) of pesticides (100 mg kg ) after 40 days of incubation at 20C.
Biomix Atrazine Ioproturon Iprodione Chlorpyrifos
A1 89.8 2.4 a 79.1 0.7 a 24.8 1.7 a 76.1 0.9 ab
A2 66.2 4.2 c 63.6 0.2 b 25.6 1.2 a 86.8 0.2 a
A3 77.0 0.2 b 53.2 0.2 c 34.3 0.2 a 57.8 0.2 b
B1 76.5 0.2 b 77.4 2.2 a 52.9 5.2 b 72.9 0.7 ab
B2 75.0 4.2 b 63.3 1.4 ab 38.1 0.3 c 77.2 1.1 a
B3 92.7 0.2 a 52.4 1.7 b 68.4 1.2 a 55.9 1.7 b
C1 73.4 0.4 b 74.4 0.4 a 32.3 1.2 a 76.1 1.2 a
C2 71.6 0.3 c 44.3 1.2 b 25.9 1.5 a 55.7 1.1 a
C3 92.7 0.5 a 65.0 0.2 a 23.6 1.1 a 63.7 0.4 a
Conclusions
Therefore, the biological activities were highest in biomixes composed with Clay and Trumao soils
and these were affected by the temperature more that for the incubation time. All lignocellulosic
material stimulated both ligninolytic and FDA activities, but the highest values were found in the
biomixes composed with barley husk.
Acknowledgements: Financed by Fondecyt 1090678 and INNOVA-CORFO Project N 09FCO2-

6021
References
[1] M.P. Castillo, L. Torstensson, J. Stenstrm, Biobeds for Environmental Protection from
Pesticide Uses A Review. J. Agric. Food Chem. 56 (2008) 62066219.
[2] L. Torstensson, M.P. Castillo, Use of biobeds in Sweden to minimize environmental spillages
from agricultural spraying equipment, Pesticide Outlook. 8 (1997) 24-27.
[3] M.P. Castillo, L. Tortensson, 2007. Effect of biobed composition, moisture, and temperature
on the degradation of pesticides, J. Agric. Food Chem. 55 (2007) 5725-5733.
[4] L. Coppola, M.P. Castillo, E. Monaci, C. Vischetti, Adaptation of the biobed composition for
chlorpyrifos degradation to southern Europe conditions, Journal of Agricultural and Food
Chemistry. 55 (2007) 396-401.
[5] P. Genot, N. Huynh, P. Debongnie, L. Pussemier, Effects of addition of straw, chitin and
manure to new or recycled biofilters on their pesticides retention and degradation properties,
MededelingensFaculteit Landbouwkundige en Toegepaste Biologische Wetenschappen 67
(2002) 117-128.
[6] C, Vischetti, L. Coppola, E. Monaci, A. Cardinali, M.P. Castillo, Microbial impact of the
pesticide chlorpyrifos in Swedish and Italian biobeds, Agronomy for Sustainable Development.
27 (2007) 267-272.
227
[7] P. Fogg, A.B.A. Boxall, Effect of different soil textures on leaching potential and degradation of
pesticides in biobeds, J.Agric. Food Chem. 52 (2004) 56435652.
[8] M. Cea, J.C. Seaman, A. Jara, B. Fuentes, M.L. Mora, M.C. Diez. 2007. Adsorption Behavior
of 2,4-Dichlorophenol and Pentachlorophenol in an Allophanic Soil, Chemosphere 67 (2007)
1354-1360.
[9] M.C. Diez, G.R. Tortella, Pentachlorophenol Degradation in Two Biological Systems: Biobed
and Fixed-Bed Column, Inoculated with the Fungus Anthracophyllum discolor, J. Soil Sci.
Plant Nutr. 8 (2008) 132-133.
[10] M.P. Castillo, J. Stenstrom, P. Ander, Determination of manganese peroxidase activity with 3-
methyl-2-benzothiazolinone hydrazone and 3-(dimethylamino)benzoic acid, Anal. Biochem
218 (1994) 399-404.
[11] J. Schnurer, T. Rosswall. Fluorescein diacetate hydrolysis as a measure of total microbial
activity insoil and litter. Appl. Environ. Microbiol. 43 (1982) 1256-1261.
[12] S.K. Winiewska, J. Nalaskowski, E. Witka-Jeewska, J. Hupka, J.D. Miller, Surface
properties of barley straw, Colloids and Surfaces B: Biointerfaces 29 (2003) 131-142.
228
TITANIUM DIOXIDE PHOTODEGRADATION OF INDIGO CARMINE DYE IN

WATER
1* 2,3 1 4 4
Enrico M. Saggioro , A.S.Oliveira , T. Pavessi , L.Vidal , A. Ferro-Filho , L.F.Vieira
2 1
Ferreira , J.C. Moreira
*saggi_br@hotmail.com
1 Fundao Oswaldo Cruz (CESTEH),Av. Leopoldo Bulhes, 1480 - 21041-210 RJ, Brasil
2- Centro de Qumica-Fsica Molecular e Instituto de Nanocincias e Nanotecnologia,
IST,UTL, Av. Rovisco Pais,1 -1049001 Lisboa, Portugal
3 Centro Interdisciplinar de Investigao e Inovao, ESTG, Instituto Politcnico de Portalegre,
Lugar da Abadessa Apartado 148 -7301901 Portalegre, Portugal
4 Fundao Oswaldo Cruz(IOC),Av. Brasil 4365 21040-360 , Rio de Janeiro, RJ, Brasil
ABSTRACT
Indigo carmine (IC) is one of the oldest dyes and still one of most important used. Its
major industry application is the dyeing of clothes (blue jeans). It is considered highly
toxic to humans, can cause skin and eye irritation. Titanium dioxide (TiO2) is the most
commonly used semiconductor to produce hydroxyl radicals. The aim of this study was to
assess dye degradation mediated by TiO2 under artificial light and sunlight and make
ecotoxicological tests to the treated effluent with Daphinia similis .The irradiation of water
samples of the dye was performed with a mercury-vapor lamp (125 W) and sunlight (Rio
de Janeiro, Brazil). Indigo carmine were irradiated for 5h in different concentrations of
-1 -3 -1
TiO2 1 gL a 1x10 gL . The decomposition followed with by UVVis absorption
observing the decrease of the IC absorption at mx=610nm of the dye. The degradation
rate increased with the concentration of TiO 2. At 15 min was observed 99% degradation
-1 -3 -1
for 1gL , and 8% to 1x10 gL . However, the degradation rate constant decreases to the
-1 -1 -3 -1
concentration 1x10 gL and the increases to 1x10 gL . Under artificial light the dye
-2 -1
decolorized 98% in 5h and sunlight 90% in 90min, both with a concentration of 10 gL of
TiO2. Tests with Daphnia similis showed a reduction of the immobility when treating a
-1 -1
solution of 1 gL dye and 0.1gL TiO2. It is possible to use solar irradiation to reduce the
reaction time and the energy cost of the treatment.
Keywords: Indigo carmine; titanium dioxide; advanced oxidative processes; photocatalysis
INTRODUCTION
Indigo carmine (IC) is one of the oldest dyes and still one of most important used. Its major industry
application is the dyeing of clothes (blue jeans). Is considered highly toxic to humans, can cause
skin and eye irritation, it interfers with neural development and had carcinogenic properties [1]. The
advanced oxidative processes (AOP) have high efficiency and can greatly simplify solid residues
management; it also shows other advantageous aspects such as simplicity and low cost [2].
Titanium dioxide (TiO2) is the most commonly used semiconductor to produce hydroxyl radicals
229
[3,4]. The aim of this study was to assess dye degradation mediated by TiO2 under artificial light
and sunlight and make ecotoxicological tests to the treated effluent with Daphinia similis .
Figure 1. Structure of indigo carmine
EXPERIMENTAL
The irradiation was with a mercury-vapor lamp (125 W) and sunlight located at S 2252`37.3`è W
-1
4315`0.9`` (Rio de Janeiro, Brazil). Amounts of 100 mL of aqueous solution (30 mgL ) of indigo
-1 -3 -1
carmine were irradiated for 5h in different concentrations of TiO 2 (1 gL a 1x10 gL ). Samples (0,
15, 30, 45, 60, 90, 120, 180 e 300 min) the dye were followed with a UVVis spectrophotometer
observing the decrease of the absorption at mx=610nm of the dye. The final treated effluent has
its toxicity tested with Daphinia similis[5].
Figure 2. Tests of photocatalytic degradation of IC. a) artificial light with a mercury-vapor lamp b) sunlight
230
RESULTS and DISCUSSION
The results of indigo carmine photodegradation are presented at Figures 3 and 4,

respectively for artificial irradiation and solar.
-1 2
Figure 3. Degradation IC 30mgL under artificial light with a mercury-vapor lamp 125 W (2,80 mW/cm ) with
-3 -1 -1
1x10 gL to 1 gL of TiO2, followed with a UVVis spectrophotometer from 200-900nm.
Both artificial and solar irradiations show to be very efficient on the degradation of indigo
carmine in water. From the reported results we can observe that the degradation rate increased
-1
with the concentration of TiO2. At 15 min of irradiation was observed 99% degradation for 1gL ,
-3 -1
and 8% to 1x10 gL . After 5h both artificial and solar irradiations degraded about 99.8% of dye.
Under artificial light the dye decolorized 98% in 5h and with sunlight 90% in 90min, both with a
-2 -1
concentration of 10 gL of TiO2.
231
-1 -3 -1 -1
Figure 4. Degradation IC 30mgL under sunligth with 1x10 gL to 1 gL of TiO2, followed with a UV-Vis
2
spectrophotometer from 200-900nm. Solar irradiation was 2,834 mW/cm .
Figure 5 presented the variation of percentage color lost under solar irradiation in a cloudy
(Figure 5a) and in a sunny day (Figure 5b) and artificial lamp (Figure 5c).
232
-1 -3 -1 -1
Figure 4. Degradation IC 30mgL under sunligth with 1x10 gL to 1 gL of TiO2, followed with a UV-Vis
2
spectrophotometer from 200-900nm. Solar irradiation in a a) cloudy (0,88428571 mW/cm ); b) sunny
2 2
day (2,83428571 mW/cm ) and c) artificial lamp (2,65 mW/cm )
This later result clearly puts in evidence that although degradations is quicker under
intense sunny days, the method is totally suitable treatment all year arround since the degradation
still occurs with reasonably high efficiency in cloudy days.
Tests of the final irradiated solutions (ie, those irradiated during 300 minutes) with Daphnia
-1
similis showed a reduction of the immobility of the Daphnias when treating a solution of 1 gL dye
-1
and 0.1gL TiO2 showing that there is no increase of toxicity of the treated model effluent. This is
an important verification that frequently is forgotten after effluent treatments.
90
Imobilizao, inibio (%)
80
70
60
50
40
30
20
10
0
0 15 30 45 60 90 120 180 300
Tempo(min)
Graphic 1. Acute test of the Daphnia similis
Toxicity increases at initial treatment stages due to formation of toxic products. By the end
of 5 hours a significant decrease on the toxicity is observed.
Graphic 2. The sun along the year in location S 2252`37.3`è W 4315`0.9`` (Rio de Janeiro,
Brazil)
233
CONCLUSION
TiO2 photocatalysis in suspension is a promising alternative for treatment of textile dyes

either with artificial or solar irradiation. It is possible to use solar irradiation to reduce the reaction
time and the energy cost of the treatment. We also confirmed that besides colour lost there isnt
increase of the toxicity of the efluents.
REFERENCES
[1] N. Barka, A. Assabbane, A. Nounah, Y. Aît Ichou, J. Harz. Mater., 152, (2008) p. 1054-59
[2] A.P.F.M, Urzedo. Rapid Commun. Mass Spectrom., 21, (2007) p. 18931899.
[3] L.M.S, Colpini. Dyes and Pigments., 76, (2008) p. 525-529
[4] A.S.Oliveira, E.Saggioro, N.Barbosa, A.Mazzei, L.F.V.Ferreira, J. Moreira. Rev. Chim., 62
(2010) 00.
[5] OECD Guideline for testing of chemicals Daphnia sp., (2004) p.
ACKNOWLEDGMENTS
The authors thanks to FCT (project PTDC\QUI\65510\2006) in Portugal and CNPq and Faperj in
Brazil.
234
St
ANODIC OXIDATION OF LEACHATES FROM SANITARY LANDFILLS
A. Fernandes1, L. Ciraco2, M.J. Pacheco3 and A. Lopes4

UMTP and Department of Chemistry, University of Beira Interior, Rua Marqus dvila e
Bolama, 6201-001 Covilh, Portugal,
1
annabelf@ubi.pt; 2lciriaco@ubi.pt; 3mjap@ubi.pt; 4analopes@ubi.pt
ABSTRACT
The electrochemical treatment of leachate samples from an intermunicipal sanitary
landfill, collected after the in-situ biological treatment, was carried out using anodic
oxidation performed with a boron-doped diamond electrode. The influence of the
current intensity on the rate of organic load and nitrogen removals was assessed.
The best results were attained for the assays run at the highest applied current density
(600 A m-2) and, after 6 h, the removals in the different parameters used to follow the
assays were the following: chemical oxygen demand - 47%; dissolved organic carbon
- 30%; total Kjeldhal nitrogen - 39%; total ammonium nitrogen - 43%; absorbance at
275 nm 66%. However, the highest average current efficiency was obtained for the
assays run at the lowest current density tested, 200 A m-2.
The average current efficiency was also calculated for the different assays and,
despite the current control, it was lower than 100%, being the highest value (68%)
presented by the assay run at the lowest current density, 200 A m-2. This assay was
also the one that presented the lowest energy cost per kg of COD removed.
Keywords: Sanitary landfill leachate; Anodic oxidation; BDD electrodes
INTRODUCTION
Although the European Union Landfill Directive (1999/31/EC) has been built on the concept of
landfill ban (progressive banning of municipal biodegradable wastes from landfill to achieve
35% of 1995 levels by 2020), landfilling is often regarded as the last resort waste management
option [1]. This type of garbage disposal leads to the formation of leachates, defined as
aqueous effluents generated as a consequence of rainwater percolation through municipal
landfills, which contain organic compounds, heavy metals, ammonium, chloride and many other
soluble compounds [2]. The poor biodegradability of landfill leachates implies that, in most
cases, a single technology is not enough to achieve acceptable levels of pollution decrease and
combined biophysical-chemical processes have to be performed [3].
An emerging technology to treat effluents containing persistent pollutants that has received
great development in the last years involves electrochemical techniques that can also be used
to treat landfill leachates [4]. Although different materials are being used as anodes in the
oxidation of persistent pollutants, the best results are obtained with boron-doped diamond
(BDD) anodes, due to their unique chemical, electrochemical and structural stabilities that allow
their use at high potentials, where most organic pollutants can be oxidized [5].
There are several reports describing the application of electrochemical oxidation using BDD
anodes as a post-treatment method in landfill leachates [6-10]. Cabeza et al. [6] study the
feasibility of removing ammonium from landfill leachates by electrochemical oxidation, using a
BDD electrode as anode. Experimental results showed very good ammonium removal. Also, it
-
was observed that when additional Cl was provided, the treatment efficiency increased. The
effect of chloride ions in the treatment of landfill leachates was also conducted by Anglada and
collaborators [7,8] at a pilot plant with BDD anodes, and they showed that the concentration of
chloride has an effect on the oxidation of ammonia and that chloride ions compete with organic
matter to be oxidized at the anode. Moreover, organic matter and ammonia oxidation are highly
influenced by the applied current density; a change in the mechanism of organic matter
oxidation is observed when high current densities are applied [7].
235
The effect of various operating conditions, such as treatment time, current intensity, initial pH
and initial concentration of chloride ions, on the electrochemical oxidation of landfill leachate
with BDD anodes were also studied [8,9].
A BDD electrode was also used in a comparative study between coagulation and activated
carbon adsorption vs. electrochemical oxidation with a landfill leachate that had previously
undergone biological treatment [10]. Experimental results have shown that 50% COD removal
was achieved by coagulation, being 80% of the remaining organic load removed by activated
carbon adsorption, when applied after coagulation treatment, while electrochemical oxidation
led to a COD removal of 90%, without the formation of solid residues.
The aim of this work was to study the influence of the current density on the anodic oxidation of
a landfill leachate pretreated by biological processes, using as anode a BDD electrode.
EXPERIMENTAL
The leachate samples used in this study were collected in March 2011, at a portuguese
intermunicipal sanitary landfill site, after being pretreated on site by biological processes.
Experiments were conducted in batch mode, with imposed current densities varying from 200 to
-2
600 A m , using 200 mL of leachate. A BDD Diachem anode, with an immersed area of 10
2
cm , and a stainless steel cathode, with identical area, were used. A GW, Lab DC, model GPS-
3030D (030V, 03A), was used as power supply. The assays were conducted at room
temperature, with stirring and without adding support electrolyte. Degradation tests were
followed by dissolved organic (DOC), inorganic (DIC) and total carbon (TC), chemical oxygen
demand (COD), total Kjeldahl (TKN) and ammonia nitrogen (AN) and UV-Visible absorption
spectrophotometry.
Dissolved organic, inorganic and total carbon were measured in a Shimadzu TOC-V CSH
analyser. Samples used in these determinations were filtrated through 0.45 m glass microfiber
filters. Chemical oxygen demand determinations were performed using closed reflux and
titrimetric method [11]. Total Kjeldahl and ammonia nitrogen were determined according to
standard procedures using a Kjeldatherm block-digestion-system and a Vapodest 20s
distillation system, both from Gerhardt [11]. UV-Visible absorbance was measured from 200 to
800 nm using a Shimatzu UV-1800 spectrophotometer.

Figure 1 presents the variations of COD and carbon (TC, DOC and DIC) with time for the
assays performed at different applied intensities, 200, 400 and 600 mA, which correspond to the
-2
current densities of 200, 400 and 600 A m , respectively. We can observe an increase in COD
Fig. 1. Variation of COD (a) and TC, DOC and DIC (b) with time for the anodic oxidation of 200
mL leachate samples run at different applied intensities. Anode: BDD, 10 cm2 geometric area.
236
removal with current intensity. This behavior is explained by the fact that, due to the high initial
COD, the process is being run under current control and an increase in current intensity
promotes an increase in the oxidation rate of the organic matter. However, the dissolved carbon
removal is almost independent of current intensity during the first 2 or 3 h assay. Only after this
initial period we can observe a dependence of the removal of the different forms of carbon with
current intensity. This means that, although the oxidation of the compounds present in the
leachate is taking place, the rate of mineralization of the organic compounds during the initial
period is lower than that of the oxidation.
Table 1 contains a summary of the initial values of the parameters used to follow the anodic
degradation of the leachate samples and their respective removals after 6 h assays. TKN and
AN removals, like those of COD and DOC, increase with current intensity, which is expected in
the case of current controlled processes. It is also possible to conclude that most of the nitrogen
removal is due to the ammonium elimination, which is one of the important features of the
anodic oxidation performed with BDD electrodes [6]. Table 1 shows also the average current
efficiency, ACE, calculated according to the following equation [12]:
CODt - COD0
ACE = 100 F V (1)
8 I t
where the parameters have the following meanings: F, Faraday constant; V, volume in m3; I,
current intensity in A; t, time in s; and COD in mg L-1. Despite the anodic oxidations performed
are under current control, the complexity of the leachate samples lead to ACE lower than the
typical value for the processes controlled by current, i.e., 100%. In fact, the highest ACE was
observed for the assay run at 200 A m-2, since the guarantee that all the species present are
under current control can only be attained for very low current densities.
Table 1. Initial values of the parameters used to follow the anodic degradation of the leachate
samples and their respective removals after 6 h assays, as well as ACE, for the different assays
performed.
Current density / [A m-2] 200 400 600
initial / [g L-1] 5.60 0.16
COD -1
/ [g L ] 1.22 1.60 2.65
removal
/ [%] 22 28 47
initial / [g L-1] 1.80 0.05
DOC / [mg L ]
-1
176 308 545
removal
/ [%] 10 17 30
initial / [g L-1] 0.90 0.02
DIC / [mg L ]
-1
483 417 596
removal
/ [%] 54 46 66
initial / [g L-1] 1.55 0.06
TKN / [mg L ]
-1
306 340 606
removal
/ [%] 20 22 39
initial / [g L-1] 1.15 0.02
AN / [mg L ]
-1
260 333 496
removal
/ [%] 23 29 43
Abs. (275 nm) removal / [%] 38 54 66
ACE / [%] 68 45 49
According to the model previously proposed in the literature for electrolysis under current
limited control [13], the trend of COD during electrochemical oxidation can be predicted by Eq.
2. Theoretical slopes, 8I/FV, can then be calculated for each of the assayed current intensities.
8I
COD(t) = COD0 - t (2)
FV
237
In Fig. 2 a), theoretical and experimental slopes of Eq. 2 are presented and it is very clear that
the difference between them increases with current intensity. Figure 2 b) also presents a
representation of DOC vs. COD for the data included in part (a) and, apart from the data
obtained during the first hour of the assays, there is a constant ratio between DOC and COD
that points to a constant mineralization efficiency [14].
Figure 2. a) Experimental (COD-COD0) vs. time data and theoretical slopes from Eq. 2 for the
assays performed at different current intensities. b) DOC vs COD experimental data obtained at
various current densities and linear fitting to the experimental data.
CONCLUSIONS
With the results obtained in this work it is possible to conclude that the application of the
electrochemical technology as a tertiary treatment of leachates from sanitary landfills is an
alternative, after a biological process, to eliminate the remaining organic load. Because of the
complexity of the leachate composition, the applicability of the theoretical models for the
electrochemical degradation is limited, since it is very difficult to find a situation where the
electrodegradation of all the compounds present in the mixture are simultaneously controlled by
current. This way, to increase the current efficiency and to decrease energy costs, it is
preferable to work with low current intensities, although this leads to an increase in the
treatment period.
ACKNOWLEDGMENTS
Financial support from Fundao para a Cincia e a Tecnologia, FCT, PTDC/AAC-
AMB/103112/2008, and ICI-Santander Totta Investigao, for the grant awarded to A.
Fernandes, are gratefully acknowledged.
REFERENCES
[1] T. Eggen, M. Moeder, A. Arukwe, Municipal landfill leachates: A significant source for new
and emerging pollutants, Sci. Total Environ. 408 (2010) 5147-5157.
[2] C.B. man, C. Junestedt, Chemical characterization of landfill leachates 400 parameters
and compounds, Waste Manage. 28 (2008) 1876-1891.
[3] A. Cabeza, O. Primo, A.M. Urtiaga, I. Ortiz, Definition of a Clean Process for the Treatment
of Landfill Leachates: Integration of Electrooxidation and Ion Exchange Technologies,
Separ. Sci. Technol. 42 (2007) 15851596.
[4] Y. Deng, J.D. Englehardt, Electrochemical oxidation for landfill leachate treatment, Waste
Manage. 27 (2007) 380388.
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[5] M. Panizza, G. Cerisola, Application of diamond electrodes to electrochemical processes,
Electrochim. Acta 51 (2004) 191-199.
[6] A. Cabeza, A. Urtiaga, M.J. Rivero, I. Ortiz, Ammonium removal from landfill leachate by
anodic oxidation, J. Hazard. Mater. 144 (2007) 715-719.
[7] A. Anglada, A. Urtiaga, I. Ortiz, Pilot Scale Performance of the Electro-Oxidation of Landfill
Leachate at Boron-Doped Diamond Anodes, Environ. Sci. Technol. 43 (2009) 2035-2040.
[8] A. Anglada, A.M. Urtiaga, I. Ortiz, Laboratory and pilot plant scale study on the
electrochemical oxidation of landfill leachate, J. Hazard. Mater. 181 (2010) 729-735.
[9] A. Anglada, A. Urtiaga, I. Ortiz, D. Mantzavinos, E. Diamadopoulos, Boron doped diamond
anodic treatment of landfill leachate: Evaluation of operating variables and formation of
oxidation by-products, Water Res. 45 (2011) 828-838.
[10] C. Papastavrou, D. Mantzavinos, E. Diamadopoulos, A comparative treatment of stabilized
landfill leachate: Coagulation and activated carbon adsorption vs. electrochemical
oxidation, Environ. Technol. 30 (2009) 1547-1553.
[11] A. Eaton, L. Clesceri, E. Rice, A. Greenberg, M.A. Franson, Standard Methods for
Examination of Water and Wastewater, twenty-first ed., American Public Health
Association, Washington, DC, 2005.
[12] C. Comninellis, C. Pulgarin, Anodic oxidation of phenol for waste water treatment, J. Appl.
Electrochem. 21 (1991) 703-708.
[13] M. Pannizza, P.A. Michaud, G. Cerisola, C. Comninellis, Anodic oxidation of 2-naphthol at
boron-doped diamond electrodes, J. Electroanal. Chem. 507 (2001) 206214.
[14] M.J. Pacheco, A. Moro, A. Lopes, L. Ciraco, I. Gonalves, Degradation of phenols using-
boron doped diamond electrodes: A method for quantifying the extent of combustion,
Electrochim. Acta 53 (2007) 629-636.
239
SOLUBLE CUTTING OIL VALORISATION BY ANAEROBIC CO-DIGESTION WITH PIG MANURE:

DISCONTINUOUS ASSAYS
1,a 1 1 1 1 2 2 2
Alvarez, J.A. , Villar, P. Pascual, A. , Pena R , Herrero, L , Rodriguez-Verde, I , Carballa, M. and Lema, J.M.
1
Dpt. Emvironment, AIMEN Technology Centre, C/ Relva, 27A, O Porrio Pontevedra , Spain.
2
Dpt. Chemical Engineering, School of Engineering, University of Santiago de Compostela, Campus Vida, Ra
Lope Gmez de Marzoa, s/n. 15782 Santiago de Compostela, Spain.
a
Phone: 986 344 000 (Ext: 304); Fax: 986 337 302; Email: jaalvarez@aimen.es
ABSTRACT
One of the main hazardous waste produced in metal industry are cutting fluids. Taking into account their organic
nature, cutting fluid management may be possible through biological treatment.
Since taladrine can contain a high concentration of heavy metals, chemicals and other toxic substances for
anaerobic microorganisms, anaerobic co-digestion with other substrate, such as pig manure, would provide a
solution to the treatment process of this oil waste. In this way, discontinuous assays have been conducted to
assess the anaerobic biodegradability (%) and methane potential (L CH 4/kg substrate) of each waste separately
and 2 blends of pig slurry:taladrine (85:15 and 95:5 in volume percentage). Substrate feed consisted of 10 mL of
pig manure, 10 mL of blend 85:15 or 95:5 or 3 mL of taladrine to the respective assays. Therefore, the substrate
concentration varied from 2.7 to 3.6 g CODtotal/L. Control assays with only inoculum were also included. Methane
production was monitored through an alkaline solution displacement system (inverted Marriotte flask system).
Despite of using no acclimatized anaerobic biomass, taladrine was biodegraded to methane in a 34% and it was
reached a methane potential of 27.2 L CH4/kg substrate. In relation to co-digestion tests, COD removal increased
from 42% to 47% when manure was mixed with 5% of taladrine. On the other hand, taladrine biodegradability
increased from 34% to 51% when it is co-digested with pig manure in a blend 95: 5 of manure:taladrine.
According to these preliminary data, aqueous cutting oils as taladrine are capable of being valorised by anaerobic
co-digestion, decreasing inhibition effect of the toxic substances that taladrine contains. Currently, continuous
assays are being carried out to optimise the best operation conditions.
Keywords: cutting fluids; taladrine; anaerobic co-digestion; pig manure, methane potential
INTRODUCTION
Metalworking fluids are widely used for cooling and lubricating during the machining process. The worldwide
9
annual usage is estimated to exceed 210 L and the waste could be more than ten times the usage, as the oil
fluids have to be diluted prior to use (Cheng et al., 2005).
Before considering the details of treatment methodology, a review of the latest legislation requirements is essential
in order to understand the standards to be met. First of all, the European Union demands that cutting fluid
manufacturers and suppliers provide products that are both safe to use and ecologically acceptable during their
production and use (BLF, 2003). Legislation regarding the regulation of cutting fluids relates not only to health and
safety but also to environmental concerns. The European Union Water Directive (2000/60/EC) has also prioritised
substances and identified actions to be taken in order to minimize the impact on the environment. Furthermore,
240
the European Union Directive (2000/76/EC) has addressed the problem of waste from incineration and provided
an even stricter framework aimed at reducing the negative effect on the environment. The key pollutants to be
reduced are nitrogen oxides (NOx), sulphur dioxide (SO 2), hydrogen chloride (HCl) and heavy metals (European
Union, 2000a, b). Consequently it limits the amount of spent metal working fluids being disposed of by means of
incineration. In other words, an alternative and cost effective option has to be identified and applied. The tightening
legislation relating to this waste disposal has forced all industries to review their effluent treatment processes or
waste disposal options to meet the targets.
Cutting oil fluids, also called metal cutting fluids or metalworking fluids, can be divided into four main types: whole
oil, oil emulsion, semi-synthetic solution and synthetic solution. The three last types of cutting oils are diluted
aqueous solutions between 2% and 15% and they are called as generic name of taladrine (Foltz, 2002).
The complexity of the composition of taladrine residue has created huge difficulties for the waste disposal
companies which deal with this type of waste, according to relevant reports and personal communications with
several waste disposal providers and manufactures (SIGAUS, 2011; Metalflow, 2011). These taladrines may
contain all or part of the following substances: mineral oils (naphthenic or paraffinic nature); animal or vegetable
oils; synthetic oil (alkylbenzene ...); emulsifiers (cationic, anionic -Na2SO4-, no anionic surfactants -triethanolamine,
polyglycol, alilfenol oxyethylene-); corrosion inhibitors (nitrite -NaNO2-, nitrite -dicyclohexylammonium - , amines -
mono-bi-triethanolamine, ciclohexilaminines-, borate bacteriostatic- and carbonates); bactericide-fungicide
(phenols, formaldehyde, pentachlorophenol); extreme pressure additives (chlorinated paraffins, sulfur-containing
additives, phosphorus additives -zinc dialkyl-); moisturizers or stabilizers (polyglycols, amine alcohols and
phosphates); defoamers (silicone as dimetilsiloxan); dyes; complexing (EDTA) and heavy metals (molybdenum,
zinc).
Cutting oil fluid treatments can be chemical, physical and biological (Sutton et al. 1985; Kim et al., 1989, 1992,
1994, Portela et al., 2001, Ji et al., 2004; Cheng et al., 2005). In early 1990, the main treatment methods were
chemical and physical processes, for example, chemical or polymers addition (lime, alum, sodium aluminate, etc.),
and the use of ultrafiltration and evaporation (Burke, 1991), while biological treatments were not used.
Although cutting fluid treatment plants have been around for a long time, many of them are not suitable for treating
water-based fluids because most treatment plants were designed to treat oil-based fluids (Sutton et al, 1985, Kim
et al., 1994). Amendments have been made to improve these facilities so they can be used for biological
treatment. However, hybrid plants that contain physical and biological processes have also been used (Thomas,
2001). Besides, genetic engineering has been used to identify certain species capable of improving overall cutting
oil waste treatment (Van der Gast et al., 2004).
Regarding cutting oil biological treatment, carbon, nitrogen, phosphorus and sulphur are critical from the point of
bacterial growth. Cutting fluids contain a reduced concentration of carbon, nitrogen and sulphur (Cheng et al.,
2005). According to Schreyer and Coughlin (1999), a phosphorus supplement improved microorganism growth
and treatment outcomes. Therefore, phosphorus and other nutrient contribution should be made as a direct
addition or through another waste which may contain them (Schreyer and Coughlin, 1999; Chen et al., 2004).
Foxall-Van Aken et al. (1986) pointed out that fatty acids as sole carbon source produce a higher positive effect on
bacterial growth than petrol naphthenic components.
241
According to Deepak et al. (1994), biological reactor temperature to treat this waste varies from 15 to 40 C. COD
was reduced when the temperature increases from 15 to 30C. On the other hand, Cheng et al. (2004) found that
COD removal was doubled when operation temperature increased from 30 to 40 C. In addition to temperature,
pH is also an important factor to consider when operating a bioreactor. The normal range of pH varies between 6
and 8.5. A high pH helps biocide activity (Rossmoor, 1981), so that, alkaline compound formation in the treatment
process should be avoided. Van der Gast and Thompson (2004) studied the effects of pH control on cutting fluid
treatment and their results showed that the optimum pH range for the biological treatment is between 6 and 7.
The idea of anaerobic co-digestion offers several possible ecological, technological and economical advantages,
so it can improve organic waste treatment through anaerobic digestion. Anaerobic co-digestion can increase CH4
production of manure digesters by 50200%, depending on the operating conditions and the co-substrates used
(Callaghan et al. 1999; Murto et al., 2004; Amon et al., 2006; Neves et al., 2008, Alvarez et al., 2010). Biogas
production by anaerobic co-digestion can be an interesting alternative to the current management technology of
this oil waste (incineration), since anaerobic co-digestion provides an energetic valorisation and also reduces the
risk of pollutant emission to the atmosphere.
Co-digestion is defined as the anaerobic treatment of a mixture of at least two different waste types with the aim of
improving the efficiency of the anaerobic digestion process. Therefore, it is very important to establish the best
blend in order to maximise methane production, avoid inhibition processes and make profitable biogas plants
(lvarez et al, 2010). The main issue for co-digestion process lies in balancing several parameters in the co-
substrate mixture: macro- and micronutrients, C:N ratio, pH, inhibitors/toxic compounds, biodegradable organic
matter and dry matter (Hartmann et al., 2003). Therefore, the mixture of pig manure and cutting oil waste is
adequate since manure provides alkalinity and nutrients that are necessary for the development of anaerobic
treatment and taladrine provides soluble organic matter which can improve methane production.
The aim of this work was to study the anaerobic biodegradability and methane potential of taladrine waste and the
effect of using this taladrine as co-substrate in pig manure anaerobic digestion. Discontinuous assays were
conducted to obtain these parameters using an alkaline solution displacement system (inverted Marriotte flask
system).
MATERIAL AND METHODS

Waste and inoculum sample
Pig manure was taken from a sewer of a 150-pig fattener and sow farm, which collects both faeces and urine. It
was stored at 4C until characterisation. Manure samples were homogenised and sieved to 2 mm. Taladrine was
sampled at AIMEN mechanical workshop and it was stored at ambient temperature until characterisation.
Granular biomass from a pilot hybrid reactor (UASB-FA) treating wine waste and pig manure was used as
inoculum in the biodegradation assays. Inoculum volatile organic matter was 30.5 g VSS/L.
Analytical methods
Standard Methods (1995) were applied for pH and conductivity measurements and for the determination of total
+
alkalinity, total and soluble COD, TSS, VSS and total Kjeldahl nitrogen and ammonium (NH 4 -N). Volatile fatty
acids (VFA acetic acid, propionic acid and butyric acid) were determined by gas chromatography (HP, 5890A)
equipped with a flame ionisation detector. Samples were previously centrifuged (5 min, 3500 rpm), and the
242
supernatant filtrated through 0.45 m cellulose filters. Total lipid content was determined using a liquid-liquid
- + -2 + + + +2
extraction method (ASTM D 4281-95). Anionic and cationic compounds (F , Na , SO4 , Li , Na , K , Ca ) were
analyzed by ionic chromatography (UNE-EN ISO 14911:2000 and UNE-EN ISO 10304-1:2009) using a HPLC
device (Shimadzu LC-10AD).
Discontinuous assays
Batch assays were carried out in 250-mL glass flasks with coiled butyl rubber stoppers. All tests were performed in
duplicate under the following operating conditions: 35C, static operation (but 1 or 2 daily manual agitations of 2
minutes were carried out) and 5 g VSS/L of inoculum. Substrate feed consisted of 10 mL of pig manure sample in
manure tests, 10 mL of manure:taladrine blend (85:15 and 95:5 in volume, respectively) in blend tests and 3 mL of
taladrine sample in taladrine tests. The substrate concentration varied from 2.7 to 3.6 g COD total/L. Control assays
with only inoculum were also conducted.
In all assays and for each feeding, 230 mL of each macro and micro nutrient stock solutions (Ruz et al., 2009)
and 1 g NaHCO3 /g CODsubstrate were added. Before adjusting pH to 7.07.2 and flushing the liquid and headspace
with N2, 0.46 mL (2 mL/L) of Na2S (50 g/L) was added to each assay as a reducing agent. An initial liquid volume
of 230 mL was used in all assays. Methane production was obtained by measuring the displaced volume of an
alkaline solution contained in Mariotte flasks. A diagram of the experimental set-up is showed in Figure 1, while a
summary of assay operation conditions is indicated in Table 1.
1 . - Water tank
2 . - 250 mL glass flask 5
3 . - Thermostat
4 . - Non-return flask
5 . - Mariotte flask
6 . - Test tube
3
4
1 6
Figure 1. Experimental set-up diagram of discontinuous assays
Calculations
The experimental specific methane potential at standard temperature and pressure conditions ( 0 C and 1 atm)
was calculated by dividing the CH4 volume produced by the substrate quantity at the beginning of the assay in wet
243
weight (L CH4/kg substrate and L CH4/kg COD). To obtain the theoretical specific methane potential, 100%
degradation of the substrate COD was assumed. Anaerobic biodegradation percentage was calculated as the ratio
between the experimental methane produced and the theoretic methane calculated. COD removal was obtained
from the initial COD value at day 0 and the final COD concentration at day 30.
Methane production of the control assay was subtracted from methane production of inoculum and substrate
assays.
Table 1. Operation conditions of discontinuous assays

Assay Inoculum Substrate Substrate volume Temperature
(g VSS/L) concentration (mL) (C)
(g COD/L)
Inoculum control 5 0 0 35
Inoculum + Pig Manure (100%) 5 2.7 10 35
Inoculum + Taladrine (100%) 5 2.7 3 35
Inoculum + Manure (85%) +
5 3.6 10 35
Taladrine (15%) (85:15 blend)
Inoculum + Manure (95%) +
5 3.0 10 35
Taladrine (5%) (95:5 blend)

Waste characterisation
Pig manure and taladrine characteristics are indicated in Table 2. Basically, pig manure contributes moisture,
buffer effect and feasible nutrients while taladrine provides soluble organic matter to the mixture.
According personal communications (Metalflow, 2011), soluble COD of taladrine comes from high concentrations
of mono-ethylene-glycol (or other alcohols and polyglycols), which are soluble in water and acts as coadjuvant to
generate an aqueous-oily fluid and also as antifreeze. Surfactants can also provide soluble COD to taladrine. The
high amount of nitrogen in taladrine is due to monoditrietanolamines, which are used to neutralize acids and for
avoiding corrosion of metal surfaces. These amines are also responsible of the high pH (around 9) of the
taladrines. Usually, taladrine contains biocides (such as fungicides, phenol and formaldehyde) and boric acid to
prevent metal oxidation. Both compounds inhibit bacteria growth, so that they will reduce taladrine biodegradability
Table 2. Physico-chemical characteristics of pig manure and taladrine (mean standard deviation).
Parameter Pig manure Taladrine

pH 7.37 0.03 9.26 0.02
Conductivity (mS/cm) 12.32 0.42 10.46 0.03
Total Alkalinity (gCaCO3/L) 9.1 0.1 19.2 0.2
TSS (g/L) 56.5 2.1 0.5 0.1
VSS (g/L) 39.4 1.0 0.4 0.1
Total COD (g/L) 62.2 1.1 208.8 0.8
Soluble COD (g/L) 4.2 0.6 197.6 1.7
Oil and grease (mg/L) 340 42 280 29
244
TKN-N (g/L) 3.3 0.3 4.8 0.5

NH4-N (g/L) 2.1 0.0 0.6 0.0
a
Fluoride (mg/L) < 0.3 ND
Chloride (mg/L) 836 2 88
Phosphate (mg/L) 42 ND
Sulphate (mg/L) 19.0 112
Lithium (mg/L) 222 ND
Sodium (mg/L) 441 5 224
Calcium (mg/L) <1 75
a
Not determined
Discontinuous assays
Figure 2 shows the accumulated methane production, while Figure 3 indicates the COD removal during
discontinuous assay performance.
300 300
Accumulated methane
Taladrine
production (mL)
250 250
200
Pig manure 200
150 150
100 100
50 50
0 0
0 5 10 15 20 25 30 0 5 10 15 20 25 30
400 300
Accumulated methane
350 250
85:15 blend
production (mL)
300
200
95:5 blend
250
200 150
150
100
100
50 50
0 0
0 5 10 15 20 25 30 0 5 10 15 20 25 30
Time (d) Time (d)
Figure 2: Methane production in discontinuous assays. Red line indicates theoretic maximum methane volume.
A summary of the results obtained in these discontinuous assays is showed in Table 3, where final pH of the tests,
anaerobic biodegradation and methane potential are indicated.
It is important to remark that there was no accumulation of VFA in any assays carried out, since a null
concentration of VFA was measured during each assay operation. These results prove that hydrolytic step was the
limiting stage of the process either in manure tests or blend tests, as consequence of the high concentration of
particulate organic matter that contains manure and blend samples. In the case of taladrine assays, which contain
a high concentration of soluble organic matter, the presence of toxic compounds reduced acetogenic bacteria
activity.
245
3.5 3.5
Pig Manure 3.0
Taladrine
3.0
2.5 2.5
COD (g/L)
2.0 2.0
1.5 1.5
1.0 1.0
0.5 0.5
0.0 0.0
0 5 10 15 20 25 30 0 5 10 15 20 25 30
4.5 4.0
4.0
85:15 blend 3.5
95:5 blend
3.5 3.0
COD (g/L)
3.0 2.5
2.5
2.0
2.0
1.5
1.5
1.0
1.0
0.5 0.5
0.0 0.0
0 5 10 15 20 25 30 0 5 10 15 20 25 30
Time (d) Time (d)
Figure 3: Total COD monitoring in discontinuous assays.
Table 3. Organic matter removal and methane production parameters of each test (according to COD monitoring).
Assay Anaerobic Methane potential (L Methane potential (L
Assay
final pH biodegradation (%) CH4lkg substrate) CH4/ kg CODadded)
Pig Manure 7.50 46.6 12.6 195
Taladrine 8.06 34.4 27.2 144
85:15 blend 7.78 39.6 14.6 165
95:5 blend 7.35 51.4 16.1 215
Despite of reaching a final pH of 8.06, taladrine was biodegraded to methane in a 34% and a methane potential of
27.2 L CH4/kg substrate was reached.
Regarding co-digestion assays, anaerobic biodegradation increased from 47% to 51% when manure was mixed
with 5% of taladrine. Besides, pig manure methane potential was increased from 12.6 to 16.1 L CH4/ kg substrate.
On the other hand, taladrine biodegradability increased from 34% to 51% when it was co-digested with pig manure
in a blend 95:5 of manure:taladrine.
On the contrary, COD removal and biodegradability percentage in 85:15 blend (manure:taladrine in volume)
assays decreased until 37% and 40%, respectively, what indicates that optimum taladrine percentage in a manure
feeding to an anaerobic co-digester could be between 15 and 5% in volume. Therefore, anaerobic co-digestion
processes improve taladrine degradation but this oil waste can act as a toxic for pig manure degradation.
Previous studies (Table 4) have confirmed a high biodegradability (70-90% of COD removal) of diluted
metalworking fluids but data of raw taladrine waste treatment has not been conducted until now. COD removal
when raw taladrine is treated is lower than cutting oil wastewater. The presence of organic compounds (phenols,
silicones, glycols, amines, etc) or inorganic (heavy metals, chlorinated paraffins, etc) could be the cause of the low
biodegradation obtained in raw taladrine treatment.
246
Table 4: Literature results about cutting oil wastewater biological treatment
Source of cutting oil Influent COD COD

System Reference
waste (mg/L) removal (%)
Aerobic processes
Aerobic fluidized bed General Motors, Sutton et al.
2101-2306 66-81
process with sand as carrier Sandusky, OH (1985)
Activated sludge John Deere Dubuque
560-1500 70-84 Polak (1986)
suspended-growth process Works, Iowa
Packed bed reactor with Wascan Technical Viraghavan y
146-715 64
peat as the packing Institute, Canada Mathavan (1990)
Deepak et al.
Aeration-suspended growth Indian oil Co. 560 26-78
(1994)
Aerobic fluidized bed
Ollin Co., Cheshire, Schreyer y
bioreactor with sand as 3000 >90
CT Coughlin (1999)
carrier
Anaerobic processes
Anaerobic fluidized bed Simulated waste

process with GAC (granular metalworking 3300 60 Kim et al. (1989)
activated carbon) as carrier fluids
Anaerobic fluidized bed Simulated waste
process with GAC (granular metalworking 1029-5324 68 Kim et al. (1992)
activated carbon) as carrier fluids
Thermophilic fluidized
Delphi Automotive
anaerobic reactor 1050-4000 67-96 Perez et al. (2007)
Systems S.A., Cadiz
Simulated waste
Anaerobic sequencing batch Carvalhinha et al.
metalworking 500-2000 80-87
biofilm reactor (2010)
fluids
Combined process
Aerobic, anaerobic, and

Simulated waste
aerobic/anaerobic with
metalworking 1029-5324 72-100 Kim et al. (1994)
fluidized bed reactor and
fluids
suspended growth
Metallurgical Muszynski and
Anoxic/Aerobic process 14000 87
process Lebkowska (2005)
CONCLUSIONS
Anaerobic co-digestion of pig manure (base substrate) with cutting oil waste as co-substrate has been conducted.
Static discontinuous assays at 35 C with granular anaerobic inoculum were carried out to assess anaerobic
biodegradability and methane potential of these residues. The following general conclusions can be drawn from
this work:
247
- Taladrine residue, an aqueous cutting oil waste, contains different toxic compounds and substances
(polyglycols, monoditrietanolamines, biocides, boric acid, etc.) which create a lot of difficulties for their
biological treatment.
- Taladrine was biodegraded to methane in a 34% and a methane potential of 27.2 LCH4/kg substrate was
reached.
- Regarding co-digestion processes, taladrine biodegradability increased from 34% to 51% when it was co-
digested with pig manure in a blend 95:5 of manure:taladrine in volume
- Pig manure methane potential increased from 12.6 to 16.1 L CH4/ kg substrate, when pig manure was
treated with a 5% of taladrine in volume.
According to these preliminary data, aqueous cutting oils as taladrine are capable of being valorised by anaerobic
co-digestion, decreasing inhibition effect of the toxic substances that taladrine contains. An optimization of
operation conditions of these co-digestion processes will be carried out with continuous assays.
ACKNOWLEDEMENTS
This work was supported by the Xunta de Galicia through the project PGDIT 09REM001CT (METALGAS) and the
postdoctoral contract to Dr. Marta Carballa (Isidro Parga Pondal, IPP-08-37).
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Carvalhinha, P, Flores, A, Rodrigues, J, Ratusznei, S, Zaiat, M and Foresti E (2010). AnSBBR applied to the
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Cheng, C., Phipps, D.A., Alkhaddar, R. (2004). Treatment of waste metalworking fluids. In: Proceedings of the
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Ji, G.D., Yang, Y.S., Zhou, Q., Sun, T., Ni, J.R. (2004). Phytodegradation of extra heavy oil-based drill cuttings
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Van der Gast, C.J., Thompson, I.P. (2004). Effects of pH amendment on metal workingfluid wastewater biological
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Viraraghavan, T., Mathavan, G. N. (1990). Treatment of oily waters using peat. Water Pollution Research Journal
of Canada, 25, 7390.
250
13th September
Keynote Lecture II
( Management of contaminated sediments: from
detailed characterization to decision making )
Javier Viguri
251
Professor Javier Viguri [Universita de Cantabria, Spain]
Biography
Javier R. Viguri is Ph.D. in Chemistry from University of Basque Country and Professor in
Chemical Engineering at the University of Cantabria, UC, Spain. He is involved (1992/Actual) in
the UC Chemical Engineering Degree and Master/Doctorate Programs Chemical Engineering
and Process Engineering as well as in the University of Cdiz (2007/Actual) Erasmus Mundus
Master and Doctorate in Water and Coastal Management.
The research activity developed is focused in subjects related with the characterisation,
control, environmental assessment and sustainable management of industrial wastes and
marine sediments. Direction and collaboration in Research and Development Projects at
International, European and National level as well as transference results projects with the
industrial sector. He has participates in more than 70 SCI papers, 1 invention patent, 150
International Congress and 10 Ph Thesis supervision, obtaining 4 research periods of 6 years
from the Education Spanish Ministry. Member of the Editorial Board of the journal Integrated
Environmental Assessment and Management from the SETAC. During 2010 develops a
research stay of 8 months at the Chemical Engineering Department of the Carnegie Mellon
University (USA).
252
St
MANAGEMENT OF CONTAMINATED SEDIMENTS: FROM DETAILED CHARACTERIZATION TO DECISION

MAKING.
Javier R. Viguri
Dpt. Chemical Engineering and Inorganic Chemistry, University of Cantabria, Santander, Spain
Email: vigurij@unican.es
ABSTRACT
Decision support tools have been applied to manage contaminated sediments and dredged material through a
range of integrative methodologies. The use of multiple Lines of Evidence (LOE), is currently one of the best ways
of assessing sediment quality and of conducting an effective scientific risk assessment. Different integrated
methods, from the classical Triad, to the new approaches that take into account more detailed characteristics can
be used. Figure 1 shows the steps in contaminated sediment management and CO2 risk assessment process.
The characterization of sediments by different LOEs has applied to different coastal areas form the Cantabria
Region, Northern Spain, with different degree of anthropic pressure. Sediments have been studied by a
multidisciplinary approach to obtain the characterization of surface sediments; additionally, the environmental
assessment of core sediments by an integrated approach provide regional geochemical baselines for studied
chemicals and pollution and toxicity chronology.
The different LOEs applied are not independent; they have complicated relationships that depend on many
variables. For this reason a chemometric approach has been used to obtain models to predict toxicity from
chemicals content of a set of 743 test samples; the obtained models allow to predict toxicity from chemical
analysis of bulk contaminant with the inherent limitations due to the bioavailability of chemicals.
To the sediment management decision-making process, an integrated interpretation of the multiple measured
variables is necessary. In this sense, a classification and integrated interpretation of sediment quality LOEs has
been made based on, i) the individual SQGs and ALs, ii) multivariate statistical techniques, and iii) mathematical
tools as Self Organizing Maps (SOM) that allows to obtain the map and component planes for the input variables.
Our results [2] show that SOM provided a more detailed classification than multivariate statistical techniques,
which was more useful for following investigations and allow easy identification of the reasons of the obtained
groupings (LOEs) that are shared by the sites grouped together in the map.
Decision-making for sediment management is a complex task that incorporates the selections of areas for
remediation and the assessment of options for any mitigation required. We develop an integral Multicriteria
Decision Analysis (MCDA)-based methodology in two steps to rank different areas to be managed and for
prioritization of sediment management alternatives, and to illustrate its implementation using a case study in the
Bay of Santander, Spain. The integration of remedial alternatives assessment using MCDA following an MCDA-
based evaluation of spatial contamination extent allows for an integrated sediment management methodology,
incorporating economic, social, technical and environmental criteria into the decision making process [3].
253
St
Figure 1. Steps used in contaminated sediment management.
Our last application of the integrative LOE approach is related to the CO2 capture and sequestration (CCS) [4].
The need of mitigating climate change has entailed the making of decisions which involve global approaches of
emissions reduction measures. One of these measures is the use of CCS technologies with CO2 geological
storage. In these technologies, there are potential scenarios, due to leakages of CO2, which can cause effects on
the marine environment and on the human health, whose extent needs to be determined under a risk assessment
and management framework. The model of risk assessment to be applied has to take into account the effect
assessment of CO2 concentrations including as the main factors the human health, the potential receptors within
the marine environment and the chemicals released from the seawater and sediments in a decreased pH
environment. The risk characterization sets relationships between stressors, effects, and ecological entities and
provides an overall assessment of the potential hazards associated with the CSS activity. The steps showed in
Figure 1 have been applied to the risk assessment and management of CO2 leakages in contact with sediments.
[1] Viguri, JR, Riba I, Reguera D, Alvarez M, Andres A (2010) Effects of the CO2 losses from storage in SSGS on
the marine sediments: an integrated approach, Environment Spanish Ministry and Rural and Marine Affairs (Ed.).
Madrid. 119 pp.
[2] lvarez-Guerra, M, Gonzalez-Pinuela, C, Andres, A, Galan, B, Viguri, JR (2008) Assessment of SOM artificial
neural networks for the classification of sediment quality, Environ Int, 34, pp 782-790.
[3] Alvarez-Guerra, M, Canis, L, Voulvoulis, N, Viguri, JR, Linkov, I (2010) Prioritization of sediment management
alternatives using stochastic multicriteria acceptability analysis, Sci Total Environ, 408, pp 4354-4367
[4] Payn, MC, Verbinnen, B, Galan, B, Coz, A, Vandecasteele, C, Viguri, JR (2011) Potential influence of CO2
release from a CCS site on release of trace metals from marine sediment, send to Environ Pollut.
Keywords: Sediments; management; characterization; decisonmaking

Presentation format: Keynote lecture
254

13thSeptember
PostersSession

255
!
!
"#$#%&!
! ! INNOVATIVE WASTE TREATMENT TECHNOLOGIES

! ! SOIL REMEDIATION
! ! WASTE MANAGEMENT: STRATEGIES, SUSTAINABILITY, MARKETS AND INITIATIVES
! ! RECYCLING OF MATERIALS
! ! WASTE-TO-ENERGY AND RDF
! ! SPECIFIC WASTE-STREAMS (AGRI-AND ANIMAL WASTES, CONSTRUCTION AND DEMOLITION, ELECTRONICS, USED TIRES, NANOWASTES.)
! ! MUNICIPAL SOLID WASTES
! ! HAZARDOUS WASTES TREATMENTS
SOCIAL FACTORS AND EDUCATION ON WASTE MANAGEMENT
!
!
!"#$%&#'#%##(")*'+,-.'#/0-'1'+2344'
'
THEME ! REF TITLE AUTHOR
Copper as a metal collector of platinum - recovery process of used auto catalytic

3 Fornalczyk, A.
converters
11 Optimization in recycling of zinc containing industrial residues Antrekowitsch, J.
Modeling phenanthrene biodegradation by Pseudomonas stutzeri CECT 930 in batch
108 Moscoso, F.
INNOVATIVE bioreactor
WASTE
TREATMENT
163 Valorization of metallurgical waste in technical road case of blast furnace slags Cherfa, H.
TECHNOLOGIES ! Recycling technology: use of lignocellulosic waste as low-cost adsorbent for anionic
172 Contreras, E.
dyes
Hybrid strategic: minimization and utilization of agricultural residues for production
173 Contreras, E.
enzyme
205 Response surface methodology for electro-fenton process optimization Rosales, E.
74 Inability of benzene- and toluene-enrichment cultures to degrade ethylene dibromide Danko, A. S.

and 1,2-dichloroethane
77 EK-Fenton for remediation of diesel fuel polluted soil Pazos, M.
Short-term influence of the addition of Cu enriched winery wastes on Cu fractionation
86 Prez-Rodrguez, P.
in a vineyard soil
Isolation of novel benzo[a]anthracene-degrading microorganims to apply to soil
96 Perez-Paz, A.
bioremediation
SOIL
Consequences of addition of solid wastes from wineries to an acid vineyard soil in a
REMEDIATION 130 Rodriguez-Salgado, I.
field-scale experiment: soil properties and nutrient contents
133 Technosols made of wastes to recover mine soils Forjna, R.
Influence of the addition of two winery wastes in copper retention by a young vineyard
147 Prez-Rodrguez, P.
soil
176 Remediation of heavy metal-contaminated soil Balkaya, M.
203 Biodegradation of PAH polluted soil by fungi grown in an agroindustrial support Rosales, E.
Biosorption of heavy metal and dyes: a promising technology leather wastewater
204 Rosales, E.
treatment
21 Life cycle assessment of wine from Ras Baixas Barrio, T.
24 Towards a sustainable lab Serra, I.
Production of biosorbents from waste olive cake and its adsorption characteristics for
54 Fernando A. L.
Cr (VI) ion
109 Advances for the environmental protection: valorization of winery residues Moldes, A. B.
WASTE Effect of different concentrations of the extract of moringa seeds as coagulant agent in
MANAGEMENT: 123 Baker, S. A. A.
the treatment of domestic sewage
STRATEGIES,
SUSTAINABILITY, Use of coal bottom ash in mortars - analysis of its influence on the properties
MARKETS AND 142 Mustelier, N. L.
characterization
INITIATIVES !
Waste management in Portugal and Europe an overview of the past, present and
199 Ribeiro, A.
future
Design and development of an equipment to separate metallic fibers obtained from the
200 Seabra, E.
recycling process of used automobile tires
OiLCA Project: enhancing competitiveness and reducing carbon footprint of olive oil
208 Busset, G.
processes through waste management optimization using life cycle assessment
256
9 Chemical characterization and valorization of hazelnuts shells Silva, P. M.
10 Use of polyurethane waste to retain hydrocarbons in aqueous media Pion Giz, E.
49 Valorization of fats from animal wastes: biodiesel production Silva, P. C.
53 Synthesis of alumina based on industrial waste material Lpez-Andrs, S.
Construction and demolition wastes as aggregate for recycled concrete under marine
72 Thomas, C.
environments
88 Enzymatic modification of a Kraft lignin Gouveia, S.
102 Development of new insulation panels based on textile recycled fibers Herrero Castilla, L.
RECYCLING OF
MATERIALS ! 127 Chromatic properties of industrial solid waste based ferrites Pular, R.
153 Mechanical behavior of recycled aggregates from concrete waste Thomas, C,
156 Phosphogypsum as alternative raw-material for Portland cement production Braz, L. F. C.
158 Steel slag valorization - Preliminary studies Vitorino, A.
Waste with sulfur from tested concrete specimens as aggregate for structural recycled
159 Thomas, C.
concrete
192 Characterisation of automotive shredder residue Margarido, F.
68 Utilization of the ornamental rocks processing waste as soil acidity corrective Ferres, G. C.
207 Alternative raw material usage in the clay ceramic industry Coronado, M.
Valorization of waste cooking oil into biodiesel over an anionic resin as catalyst: a
184 Rosa, H.
WASTE-TO- kinetic study
ENERGY AND
RDF ! 187 Bioenergy potential of forest residues in Bizkaia (Spain) Mateos, E.
196 Influence of free fatty acid content in biodiesel production on non-edible oils Ribeiro, A.
Implementation of a composting process optimization of a mixture of agro-industrial

19 Oliveira, M.
waste with an organic accelerator
44 Preparation of activated carbon from waste leather from the tanning industry Freitas, M. M. A.
Assessment of waste electrical and electronic equipment reuse: a Life Cycle

58 Silva E. J.
Assessment approach
SPECIFIC Change of the C/N ratio in the organic material of the composting pile constituted with
WASTE- 67 Lo Monaco, P. A. V.
different poultry beddings
STREAMS (AGRI-
AND ANIMAL Leachate caracterization from winemaking bentonite residues under unsaturated water
WASTES, 100 Labrador, M.
flow
CONSTRUCTION
AND Monitoring of the C/N ratio in the composting pile constituted of crushed and not
DEMOLITION, 110 Paiva, E. C. R.
crushed chicken carcasses and different beddings
ELECTRONICS,
USED TIRES, 118 Recycling TURBOT farm waste (sludge): composting and vermicomposting Marcet, P.
NANOWASTES.) !
Head loss in the air blown through different layer thickness of organic material in
121 Matos, A. T.
composting
140 Incorporation of coffees husk ash reject into ceramic tile Acchar, W.
166 Characterization and quantitation of aluminium based nanoparticles on wastes Santos, R.
193 A mult-crtera decson makng approach for fnal dsposal process of end-of-lfe tres Ulukan, Z.
35 The effect of soil on home composting Roig, M.
56 Comparative study of the evolution of waste generation in ERSUC 2005 to 2008 Paixo, S. M. M.
Evaluation of the effect of successive application of paper mill sludge to degraded soil:
MUNICIPAL 82 Gallardo, F.
SOLID WASTES ! a column study
Comparative analysis of household waste composition in the different districts of
132 Miafodzyeva S.
Stockholm
154 Use of MSWI bottom ash frit as raw material for ceramic tiles Monteiro, R. C. C.
36 Removal of iron ions from wastewaters using Turkish natural zeolite Erdl Aydn, N.
Winery wastewater treatment with entrapped activated carbon: stimation of color
139 Vecino, X.
parameters
150 Healthcare wastes materials changes under alkaline hydrolysis treatment Pinho, S. C.
Biological monitoring of arsenic in urine of workers from an hazard waste treatment

178 Pavesi, T. P.
plant in Mau, Brazil
HAZARDOUS
WASTES Biological monitoring of Hg, Be, Cd, Ni in urine and pb in blood of hazard waste
179 Pavesi, T. P.
TREATMENTS ! incinerator workers in Mau, Brazil
Biological monitoring of mercury in urine of workers from a medical waste incineration
180 Pavesi, T. P.
plant in mau, brazil
Titanium dioxide photocatalysis on the remediation of model textile azo dyes
183 Saggioro, E. M.
wastewaters
Influence of temperature on the As leaching of sediment-based ceramic bodies by
206 Alonso-Santurde, R.
means of sequential extraction
SOCIAL
FACTORS AND
Usage & attitudes on waste paper recycling of university students and its economic
EDUCATION ON 164 Zulfikar, H.
WASTE effects in Turkey
MANAGEMENT
! ! ! !
257
OPTIMIZATION IN RECYCLING OF ZINC CONTAINING RESIDUES

2 1 1
J. Antrekowitsch , T. Griessacher and St. Steinlechner
juergen.antrekowitsch@unileoben.ac.at
thomas.griessacher@unileoben.ac.at
Stefan.steinlechner@unileoben.ac.at
ABSTRACT
Metal production and recycling industries are typically characterized by a high demand on
energy. Besides this, at the reduction processes necessary in metallurgy additionally high
amounts of reducing agents are used in this field of industry. Normally this high demand
on carbon is covered by fossil carbonaceous materials, which results in high amounts of
greenhouse gas emissions, which enhance the global warming.
In this paper two options of substitution of fossil reducing agents in heavy metals
recycling processes are described. Therefore biomass is converted into metallurgical
charcoal inside a special carbonization reactor and used as carbon-neutral reductant.
Furthermore the by-product pyrolysis gas is used as reducing agent for the recycling of
heavy metal containing residues. With such a replacement of fossil materials the CO 2-
footprint of nowadays dirty industry sectors like heavy metal recycling can be dramatically
reduced.
Keywords: Dusts; optimization, zinc, heavy metals, recycling
INTRODUCTION
Especially in industrialized countries, the recycling of different materials has become a focal point
in industry and science. The field of metallurgy today is characterized by a continuous increase in
metal demand accompanied by a decrease of available primary resources. In addition to this,
restrictions concerning waste dumping based on environmental legislation as well as high metal
prices lead to an intensified effort in recycling of metal containing residues. Therefore, beside
scraps, metal bearing slags, dusts and sludges are also considered secondary raw materials
nowadays, losing the status of being simple waste.
Nevertheless, most of the existing and upcoming processes are energy intensive and need high
amounts of reductant. Both requirements are mostly covered by the use of fossil carbon and
electrical energy. High emissions of CO2 and elevated energy costs are the result, causing lower
recycling rates as possible from the view of available resources. Analyzing various recycling
processes in metallurgy, they show a high potential in optimization concerning the following items:
- product quality
- simultaneous recovery of different metals
- substitution of fossil carbon
- energy recovery
Especially heavy metal containing wastes including zinc, lead, copper and iron are characterized
by processes based on carbothermal reduction at high temperatures.
Therefore the focal points in investigating the optimization potential of complex materials recycling
can be summarized as follows:
A primary objective is to investigate the potential for a substitution of fossil carbon used as a
reducing agent by the utilization of biomass. Although these materials partly act as an energy
258
carrier too, the focus lies on its behavior as a reducing agent, which is most important for the
metallurgical process itself.
A further essential is the detailed characterization of typical metal-containing wastes concerning
morphology and phase distribution and in order to that, the reduction and melting behavior. This
builds the base for the estimation of a possible simultaneous recovery of valuable metals from the
residue, which in turn leads to a more effective process accompanied by improved energy
efficiency.
Together with the characterization, a detailed investigation in problematical impurities of the
secondary raw materials such as halogens, arsenic, cadmium and their behavior during recycling
should create basic knowledge concerning an upgrade of product qualities. Due to the fact that the
products of such processes are still used as a feed for primary metallurgy, again the whole amount
of energy for primary winning beside that of the preceding recycling process is consumed. By a
selective separation of impurities, an upgrade of the products should be possible, which enables
their direct use for various technical applications. This leads to an explicit higher value as well as a
high potential for energy conservation.
A superior task is the modeling and balancing of the concerned metallurgical processes which on
the one hand is essential to locate the potential for an optimization regarding the above described
aims and on the other hand allows considerations on how the generated knowledge could be
successfully implemented. The necessary mass and energy balances and their dependencies on
various process parameters are generated by thermochemical calculations (e.g. FactSage, HSC)
together with basic data from the industry.
Fig. 1 illustrates the specified objectives and their interaction with the metallurgical process
concerning CO2 minimization and further optimization potentials.
Fig. 1: Specified objectives and their interaction with the metallurgical process
CHARACTERIZATION OF COMPLEX MATERIALS

Today, secondary input materials for the recycling of heavy metals can be divided into three main
categories:
- scraps mainly only containing one metal
- alloyed scraps with or without additional impurities
- mostly oxidic residues like slags, dusts and sludges containing valuable metals in the form
of oxides and other compounds
While the first category does not cause many meaningful troubles in recycling, the second one is
often already based on typically more metallurgical ground operations like selective oxidation,
vaporization, alloying, etc.
Nevertheless, today and in the future, the highest potential for an increase of recycling rates lies in
the effective treatment of the third category, materials which often show a very complex character
259
and therefore a maximum metallurgical challenge. The basis for adequate recycling processes in
many times is a combination of various metallurgical operations from pyro to hydro and
electrometallurgy. Especially a detailed characterization of such residues is mandatory to reach the
proposed aims like simultaneous recovery of various valuable metals as well as an increase in
product quality and with this, high energy efficiency.
The following basic methods are used for in depht characterization of different residues, whereas
the analysis by a high temperature heating microscope as well as detailed morphological
investigations were especially developed at the department of nonferrous metallurgy at the
University of Leoben.
- Chemical analysis (AAS, ICP)
- X-ray diffraction (XRD)
- Scanning electron microscopy (SEM) incl. energy dispersive X-ray (EDX)
- Microprobe analysis (wavelength dispersive X-ray, WDX)
- High temperature heating microscope
- Static laser light scattering
- Melting and reduction trials in laboratory scale furnaces
BEHAVIOR OF TYPICAL COMPONENTS DURING METALLURGICAL RECYCLING

As mentioned, beside the basic characterization of secondary raw materials, also the behavior of
special components is important. A lot of the concerned residues have typical phases like zinc
ferrites, halogens and lead compounds in common.
Behavior of zinc ferrite

In various metallurgical residues like leaching residues, slags and dusts, zinc and iron appear in
the form of zinc ferrite. Compared to simple zinc oxide the zinc ferrite shows a low solubility in most
of the solvents. Beside this, also the reducibility in pyrometallurgical processes is clearly hindered.
Observing a zinc ferrite particle during reduction, on the surface first of all the production of zinc
and FeO at temperatures above 1000 C occur relatively quickly. But the further reaction of FeO to
Fe is comparably relatively slow. In both cases the chemical reaction determines the speed of
conversion. After the formation of a surface layer the diffusion starts to become the step which
determines the reaction speed.
As typical influencing parameters from the side of process technology, the temperature,
atmosphere and retention time can be named. Furthermore, zinc ferrite has the property to
integrate different impurities like MnO, MgO, CaO und Al2O3, which depending on compound and
amount, affect the reduction behavior [1].
Behavior of lead and lead compounds

Lead mainly occurs in residues as PbO, PbCl2 or other more complex halogens and sometimes
PbS. As seen from the vapor pressure curves, PbCl2 shows the lowest boiling point, followed by
PbS and PbO. Caused by vaporization in most pyrometallurgical processes, lead is enriched in the
formed dust. An appreciable volatilization of metallic lead can only be found at temperatures higher
than 1400 C, which are not typical for the majority of existing recycling processes.
Investigations pointed to the fact that PbCl2 and PbS have a typical higher volatilization speed in
relation to PbO and metallic lead [2]. This was verified by observations in recycling facilities where
lead from the reduction of lead oxide remains in the slag. This in turn causes problems in landfilling
of such slags because of the solubility of the metallic lead, which leads to higher costs.
Behavior of halogen compounds

Nonferrous metals like copper, lead, zinc or tin are often recovered from various scraps as well as
from different process residues such as dusts, sludges and slags. One typical difficulty in the
treatment of these materials is that the valuable metals are accompanied by respective amounts of
halogen compounds. In most cases they either cause complications in possible reutilization
processes or a contamination of the final products. That is why an economical treatment of those
secondary raw materials is very difficult, which in turn results in decreasing recycling rates of those
materials.
260
Especially zinc bearing residues suffer from this problem, since the zinc winning electrolysis is
strongly influenced by chlorine and fluorine, which cause anode corrosion and sticking of the zinc
layer respectively. Because of these problems, the content of fluorine and chlorine in the electrolyte
is strictly limited to about 30 to 100 ppm.
For the pyrometallurgical recycling of such residues a variety of developments exists, but although
they differ significantly, they all have two things in common:
- All processes use carbothermal reduction as the basic metallurgical principle.
- They all suffer from a zinc product which is contaminated with halides.
Therefore, to meet the requirements given by the electrolysis, it becomes necessary to integrate an
additional, cost-intensive halogen removal step into the processing chain.
Investigations of steel mill dust with X-ray diffractometry and scanning electron microscopy show
that chlorine mainly exists in the form of PbCl2, ZnCl2 and NaCl, while KCl, FeCl2, FeCl3 and CaCl2
are found only in smaller amounts. This observation corresponds widely with information from
literature [3-5]. The characterization and analysis of fluorides is far more difficult, which can be
ascribed to the relatively low fluorine contents in the dust, making a measuring and quantifying with
common methods hardly possible. As typical compounds, CaF 2, ZnF2 and KF were detected.
Concerning the various fluorides, also from literature, only little information is available [3].
BIOMASS/CHARCOAL AS REDUCING AGENT

The main aims in this field are a detailed characterization and description concerning the reduction
and dissolution behavior of biomass and biocoke as well as the integration of the biomass supply in
the metallurgical process chain.
At times of global warming and climate changes, effective methods for an integrative environmental
protection also from the industry are getting more and more important. Therefore it is becoming
fundamental for the future to reduce the emissions of greenhouse gases. This fact is also
publicized by environmental legislation, where tighter regimentations occur. This ambitious target
especially in the European Union is only reachable with totally new ideas and concepts in the
energy sector as well as in the manufacturing industry. Especially the usage and application of
biomass as CO2-neutral feedstock material should be mentioned, which can offer the needed
amounts for a technical implementation [6].
Carbonization or pyrolysis is an indirect, thermal conversion process at temperatures higher than
300 C in the absence of air [7]. During this process, biomass is converted into charcoal, flammable
gases as well as tar and pyrolysis oil. Further conversion processes of biomasses are gasification,
liquefaction, fermentation or anaerobic digestion and esterification. The advantages of the
carbonization of biomasses are the possibility of the usage of the produced charcoal as a CO 2
neutral reducing agent as well as the fact that such a process can be operated autothermally, if the
emitted gases are used and post-combusted.
Fig. 2: Biomass supply for a reduction step for the treatment of the investigated residues
261
To generate an adequate charcoal, a pyrolysis process is necessary that shows the following steps
(see diagram in figure 2). Some assumptions based on data from literature were necessary to
calculate the shown flow chart.
Depending on the pyrolysis process and if the used charcoal is a by-product, for example from
biofuel production, the fixed carbon in the charcoal varies from 60 to 90 % and the charcoal yield
lies between 20 and 40 %. For this, different amounts of charcoal or initial wooden biomass are
necessary to substitute the fossil carbon in the processes. Furthermore, the quality of the produced
charcoal has to be taken into consideration, which may offer a complete carbon substitution or
otherwise only a partial one.
SIMULTANEOUS RECOVERY OF VARIOUS METALS FROM RESIDUES

Today a tendency becomes obvious to recover as many valuable metals as possible from
secondary raw materials. This is important from the ecological and economical point of view, but
needs a rather complex combination of metallurgical operations which should also enable the
production of a high quality product. Nevertheless today this goal is hardly realized in any process.
For example the following metal containing residues can be taken into account for such process
concepts:
- dusts from secondary copper industry
- steel mill dusts
- neutral leaching residue (zinc industry)
- galvanizing residues
- foundry dusts
- lead-silver residues (zinc industry)
As mentioned, with such a process high amounts of energy can be saved by passing the primary
metal winning route as well as the conservation of primary resources and the minimization of
landfilling activities. The development of such a process for different Zn, Pb-containing residues is
one main aim of the Christian Doppler Laboratory. The investigated basic process concept is a
single step unit with different options concerning preceding and subsequent process steps.
Figure 3 shows the basic flow sheet for such a process based on a metal bath shown.
Fig. 3: Basic flow of the investigated one step process [8]
Beside the residue, slag forming agents to adjust the slag basicity are added, an important factor
for achieving a low melting slag, which influences the energy consumption. Moreover electrical
energy is needed to heat up the charged material. Furthermore a reducing agent, which is petrol
coke, is added to get a reducing bath and atmosphere. The typical metals to recover in such
262
residues are zinc, lead copper, iron and tin. Some examples of the most relevant reactions are
listed below. Zinc is generally recovered in the off gas due to its low boiling point while the others
are concentrated in the metal bath. Lead could be also recovered in the off gas if it appears in
volatile components.
As mentioned above zinc oxide often is the main product of such processes and therefore its
quality is most important concerning the feasibility of the process. Investigations how to increase
this quality by especially getting rid of the halogen compounds by pyro- as well as
hydrometallurgical methods is one special focus of the research work. Hereby the behavior of
these compounds but also the interaction between them especially in case of pyrometallurgical
treatments is very important and for this studied in detail. The goal is to figure out what qualities are
possible under economical considerations and if the produced zinc oxide meets the requirements,
to brake in other markets such as the galvanizing or zinc oxide industry beside its established
utilization as secondary source in primary zinc industry.
SUMMARY AND CONLUSION

The described research field at the Christian Doppler Laboratory for optimization and biomass
utilization in heavy metal recycling aims to investigate the utilization of biomass as reduction agent
as well as further potentials for optimization in the recycling of heavy metal containing wastes.
Therefore a special focus lies on the detailed characterization of secondary raw materials
containing higher amounts of zinc, lead and copper. Based on this an essential field is the basic
study of the melting and reduction behavior of such materials. Furthermore the behavior of
impurities like halogens and possible options for their removal and with this the upgrading of the
product quality can be seen as important research fields.
In the area of biomass utilization especially the reactivity and the study of its impact on the
reduction of metallurgical recycling processes are of crucial interest. The gathering of potentials for
optimization by detailed modelling of recycling processes based on thermochemical calculations as
well as available industrial data is also an essential part and more over allows a prediction of
product qualities and energy demands of possible optimization steps or developments. Based on
various similarities of the investigated materials and process solutions for a simultaneous recovery
of different valuable metals from one residue, the generation of different basic modules is done,
which also forms a basis for the development of future recycling concepts.
REFERENCES
[1] Tong, L. F.: Reduction mechanisms and behaviour of zinc ferrite-Part 2: ZnFe2O4 solid
solutions. Trans. Instn. Min. Metall., 110, September December (2001)
[2] Kozlov, P.A.: The Waelz Process. Ore and metals publishing house (2003)
[3] Gouzhu, Y.: Characterization and Removal of Halogens in the EAF Dust and Zinc Oxide
Fume obtained from Thermal Treatment of EAF Dust. Proc.: Fourth International Symposium
on Recycling of Metals and Engineered Materials, Pittsburgh (2000) 271 - 280
[4] Hagni, A.M., R.D. Hagni, C. Demars: Mineralogical Characteristics of EAF Dusts, JOM, vol.
43, no. 4 (1991) 28 - 30
[5] Ye, G., J. White, L.-Y. Wei: Association of Halogens in Electric Arc Furnace Dust and Zinc
Oxide Fume before and after Leaching. Proc.: REWAS 99: Global Symposium on Recycling,
Waste Treatment and Clean Technology, San Sebastian (1999) 1503 - 1510
[6] Strezov, V., et. al.: Fundamental aspects of biomass carbonisation. Journal of Analytical and
Applied Pyrolysis, Vol. 48, No. 79 (2006) 2203 2220
[7] Syred, C, et. al.: A clean, efficient system for producing Charcoal, Heat and Power (CHaP).
Fuel, Vol. 85, No. 10 11 (2006) 1566 1578
[8] Steinlechner, S.: Technical feasibility and economical considerations in the recycling of
complex secondary resources. Diploma thesis, University of Leoben (2009)
263
MODELING PHENANTHRENE BIODEGRADATION BY Pseudomonas

stutzeri CECT 930 IN BATCH BIOREACTOR
1
Moscoso , F., Deive, F., Longo, M.A., Sanromn, M.A.
1 Dpt. Chemical Engineering, University of Vigo, Campus As Lagoas, Marcosende 36310, Vigo,
Spain, email: fatimamoscoso@uvigo.es
ABSTRACT
Polycyclic aromatic hydrocarbons (PAHs) are among the most prevalent and persistent
pollutants accumulated in natural environments mainly as a result of anthropogenic
activities. Bioremediation is considered as an emerging strategy to remove this type of
compounds from contaminated effluents, and allowing the transformation of these toxic
chemicals to less hazardous forms. From preliminary studies, Pseudomonas stutzeri was
demonstrated to be a microorganism with potential for aerobic degradation of several
aromatic pollutants. In this work, biodegradation of phenanthrene (Phe) by the bacteria P.
stutzeri CECT 930 in flask and bench scale bioreactor has been investigated at 37C and
pH 8.0. In all experiments, degradation percentages higher 90% were reached.
Moreover, Phe degradation rates were 3 times higher at bioreactor scale than at flask
scale. Furthermore, the depletion rate of Phe was satisfactorily fitted to a first-order
kinetic model. The influence of the medium, and the contaminants concentrations on the
growth of P. stutzeri was assessed using two different medium supplemented with
different Phe concentrations. Complementary, based on GC spectra results, it was also
elucidated that P. stutzeri completely degraded Phe via protocatechuate.
Keywords: Biodegradation, Pseudomonas stutzeri, Phenanthrene, Metabolite.
INTRODUCTION
Polycyclic aromatic hydrocarbons (PAHs) are common environmental pollutants that are made up
of two or more fused aromatic rings. They represent a large group of organic pollutants and their
presence in the environment is caused by natural events such as forest and rangeland fires
through the incomplete combustion of organic material as well as anthropogenic origin, like an
industrial operation such incomplete combustion of fossil fuels and petroleum, municipal solid
waste incineration.
Among the major pollutants, PAHs are widely distributed environmental contaminants that are
known to be highly toxic, mutagenic (which varies with the number of aromatic rings), genotoxic
and carcinogenic to living organisms, so they represent considerable environmental risks. The
presents of PAHs in the environment has monitored since the 1970s by the US Environmental
Protection Agency (US EPA) where 16 PAHs have been defined as priority pollutants and form a
subset of toxic pollutants including, for example, naphthalene, phenanthrene and anthracene [1].
It has long been known that this type of compounds are persistent in the environment due to their
physicochemical properties, which include very low aqueous solubility and vapor pressure, high
hydrophobicity (high log Pow), high adsorption coefficient and high thermodynamic stability of the
aromatic ring that makes them to be weakly bioavailable [2]. With an increase in molecular weight,
their solubility in water decreases; melting and boiling point increase and vapor pressure
decreases, so they cannot degrade easily under natural conditions [3].
Taking in consideration these facts, PAHs could be removed into the environment by means of
some technologies. There are three mains processes that play an important role in environmental
cleanup: physical, chemical and biological methods like volatilization, photolysis, chemical
degradation, bioaccumulation, and adsorption. However, the principal process for successful
removal and elimination of PAHs from the environment and the most cheap and effective way to
264
decontaminate soils and effluents is bioremediation or biodegradation. Nevertheless, the efficiency
of PAHs biodegradation is limited mainly because their poor bioavailability, which declines along
with the increasing number of aromatic rings. It is well known too, that lower molecular weight
PAHs (2-4 rings), could be removed more easily than high molecular (5-6 rings) once [4].
In general terms, process of biodegradation depends on the environmental conditions, number and
type of the microorganisms (algae, bacteria, or fungi), nature and chemical structure of the
chemical compound that is degraded [3,5].
The biodegradation process involves the breakdown of organic compounds through
biotransformation into less complex metabolite and through mineralization into inorganic minerals,
H2O, CO2 (aerobic) or CH4 (anaerobic).
Moreover, several studies, like Nasseri et al 2010 have shown that bacteria Pseudomonas are the
most efficient to degrade a wide range of aromatic compounds from benzene to benzopyrene (that
it is considered to be the most carcinogenic and toxic of PAHs) [6].
In spite of the wide diverse bacteria present in the environment, most of the bioremediation
processes of PAHS are very slow due to the properties of these pollutants. Nowadays,
considerable efforts have been focused on the enhanced solubility of these hydrophobic
compounds with the addition of surfactants. Many studies have demonstrated that using
surfactants increase solubility by decreasing the interfacial surface tension between PAHs and the
soil/water interphase. Bautista et al 2009 have confirmed that Tween-80, a non ionic surfactant,
was used as carbon source by the bacteria Pseudomonas sp.[1,7].
Phe have been used as model (in biodegradation mechanism) in order to elucidate the conditions
that affect the bioavailability and microbial degradation rate of PAHs in the environment [8]
In this study biodegradation of PAHs by P. stutzeri is investigated in order to use them to clean up
contaminated water effluents.
Chemicals and medium
The minimal medium (MM) was composed of (g/L): Na2HPO42H2O 8.5, KH2PO4 3.0, NaCl 0.5,
NH4Cl 1.0, MgSO47H2O 0.5,CaCl2 0.0147. MM also contained trace elements as follows (mg/L):
CuSO4 0.4, KI 1.0, MnSO4H2O 4.0, ZnSO47H2O 4.0,H3BO3 5.0, FeCl36H2O 2.0. Solid MM plate
1
was composed of (L MM): 15 g agar. PS medium was composed of (g/L): yeast extract 1.0, meat
extract 0.5, casein peptone 2.5, NaCl 2.5.
Phe (>99 % purity) used in degradations experiments was purchased from Sigma Aldrich
(Germany). Relevant properties of this compound are shown in Table 1. Non ionic surfactant,
Tween 80, was supplied by Merck.
Table 1: Relevant properties of phenanthrene (Phe)
Boiling Melting Aqueous

Structure M.W. V.P. (at 25C)
Point Point solubility
178.23 340C 105.5C 6.8*10-4 mmHg 1.20 (mg/L)
Microorganism
Bacteria Pseudomonas stutzeri CECT 930 was obtained from the Spanish Type Culture Collection
(ATCC 17588). P. stutzeri is a gram-negative, rod-shaped and single polar flagellated bacterium
[9].
P. stutzeri was inoculated in PS medium including 15 g/L of agar and were incubated at 26C and
pH 7.2 for 5 days.
265
Biodegradation of PAHs: Flask culture
Biodegradation experiments carry out in 3 replicates. 1.5 mL of culture were inoculates in 50 mL

MM medium containing 1% w/v of the non ionic surfactant Tween 80, and 2% v/v acetone in order
to Phe solubilisation. Since the lower solubility of Phe in water (1.20 mg/L) standard solution was
prepared dissolving it in acetone.
Erlenmeyer flasks were incubated in darkness at 150 rpm, 37C, and the initial pH was adjusted to
8.0, during 15 days. Samples were withdrawn at different intervals to monitor PAHs biodegradation
and cell density.
Biodegradation of PAHs: Bioreactor culture
The stirred tank bioreactor (Biostat B, Braun, Germany) consisted of a jacketed glass column 16
cm in internal diameter and 36.5 cm high (working volume: 3L). It was filled with the basal medium
described above containing 100 M of PAHs as the sole carbon and energy source. The
temperature was maintained at 37C by circulation of thermostatic water, and the pH was adjusted
to 8. The bioreactor was inoculated with actively growing cells from flask cultures (3% v/v).
Humidified air was supplied continuously at 0.17 vvm and samples were taken regularly during the
experimental period. All fermentations were repeated to check the reproducibility of the
experimental results and samples were analyzed by triplicate.
Cell growth determination
Biomass concentration was measured by turbidimetry at 600 nm, and the obtained-values were
converted to grams of cell dry weight per litre using a calibration curve.
HPLC PAHs analysis
Phe concentrations in the culture media were performed by reversed-phase high pressure liquid
chromatography (HPLC) equipped with a reversed phase C8 column (150-x-4.6mm, 5 m-
particule-size, Zorbax Eclipse) with its corresponding guard column. The HPLC system was an
Agilent 1100 equipped with a quaternary pump and photodiode array UV/Vis and fluorescence
detector (252.4 nm). 5 L of filtered aliquot was injected and then eluted from the column at
-1
flowrate of 1 mL min using an acetonotrile:water (40:60) as a mobile phase.
GC-MS PAHs analysis
In order to identify intermediate compounds formed during the degradation process, aliquots of 5
mL were extracted twice with 5 mL of chloroform. The organic phase extractions were combined
and dried over with anhydrous sodium sulfate [10]. 1 L of this organic phase was analyzed using
a Agilent GC 6850 gas chromatograph equipped with a HP5 MS capillary column, operating with
hydrogen carrier gas, coupled to a Agilent MD 5975 mass spectrometer (MS). The GC injector (280
C) was operated in splitless mode, 1 L aliquots were injected using an autosampler; GC oven
-1
was programmed to hold 50 C for 4 min then raise the temperature by 10 C min to 270 C,
which was held for 10 min.
Adsorption test
In order to determine the adsorption of Phe over the biomass, it was performed the following
procedure: aliquots of 1.5 mL are harvested; biomass samples were washed and re-suspended in
methanol. Then the liquids are measured by HPLC and quantify using a calibration curve.
266
Effect of medium composition on bacterial growth

The influence of the medium, and the contaminants concentrations on the growth of P. stutzeri was
assessed using flask cultures with two different medium, PS and MM supplemented with different
concentrations of Phe, between 100 and 2100 M (Figure 1). It was verified that P.stutzeri needs
some source of carbon to survive, because in the experiments carry out in MM without surfactant
or another source of carbon wasnt observed any type of cell growth. Almost is known that different
concentrations of contaminants can be affected to the microorganism. From the results it can be
stated that the use of a complex medium (PS) involves the lowest levels of growth (0.35 vs 0.65)
and a rate of degradation 9 times lower than the other alternative, MM, at the same conditions.
Data obtained are also show a performance characteristically from bacteria growing with: initial
phase, exponential growth, could be based on surfactant consume as the first sole carbon and
them the Phe are consumed [11]. The growth curves were modeled through fitting the experimental
results to a logistic equation
0.8
0.7
Biomas cocentration (g/L)
0.6
0.5
0.4
0.3
0.2
0.1
0.0
0 5 10 15 20 25 30 35
Time (h) (
Figure 1 Biomass concentration and of P. stutzeri: PS Medium; MM Medium; MM 100M Phe,
x MM 200M Phe Medium, o MM 400M Phe Medium, MM 690M Phe Medium, MM 1200M
Phe Medium, MM 2100M Phe Medium. Experimental data are represented by symbols and
logistic model by solid lines
In order to solubilize the Phe, nonionic surfactant was selected over other types of surfactants,
because of their greater hydrocarbon solubilization power, weaker sorption to charged sites, and
lower toxicity to microorganisms [12] Studies concerning the positive effects of surfactants on the
biodegradation of different PAHs, however, dealt mostly with pyrene, phenanthrene, and
anthracene in wastewater samples. Some reports showed that surfactants are also able to exhibit
negative effects on biodegradations if they compete for PAHs and hence negative effects on PAHs
biodegradation [4]. Based on the data reported by Bautista et al, 2009 [1] for metabolic utilization of
Tween 80 as carbon source, it is possible to hypothesize that this compound is being used as
cosubstrate and it can be hypothesized too that the bacterial uptake of solubilized compounds are
influenced by surfactants.
Additionally, as modeling the microbial growth and degradation can be an efficient tool to have a
better understanding of the relationship between metabolites triggering Phe degradation and the
biomasss production, an approach to quantitatively ascertain the basic parameters describing the
biological process was carried out.
267
Kinetic studies
Kinetic microbial modeling possesses a particular importance and a practical significance in
predictive microbiology, since it facilitates the control of the biological process, and license to
anticipate the microbial responses to certain environmental conditions [13].
In order to describe the effect of the different concentrations of contaminant on the rate of growth
(), the Monod kinetics was used. This model described the experimental data very well, with high
2 -1
correlation coefficient (R = 0.98). The bacteria exhibited a maximal specific growth rate of 0.23 h
and a half saturation constant of 24.16 M. These results are according with the results presented
by Jegan et al 2010 [14] who studied naphthalene degradation by Micrococcus sp.
Effects of carbon source

Effects of carbon source were investigated in order to ensure that the only source of carbon will be
the contaminant. Rate of growth in medium PS, rich medium, was lower than in minimal salt
-1
medium enrichment with non ionic surfactant (MM 1%TW), 0.097 vs 0.115 h , in presence of the
same concentration of Phe, 100 M. Influence in the rate of PAHs removal was not detected since
was eliminated completely in both media at the same time.
If it analyzed the effect of the media in the rate of COD removal, it achieved greater levels in rich
medium; this result is coherent with the own composition because is a rich medium, that means
that the initial level of COD is higher that the initial level of COD in the other medium.
Bench scale bioreactor

Taking into account the results achieved in flask cultures, the efficiency of the studied strain for the
degradation of Phe at 100 M concentration was assessed in a bench scale bioreactor (all the
biomass and biodegradation data were adequately fitted to the logistic models). As can be
concluded from the data, biomass parameters (specific growth rate, ) are quite similar to those
-1 -1
obtained in flask cultures, 0.138 h vs 0.183 h , and no differences are also observed in the
Luedeking and Piret parameters, with a stronger dependence of degradation on the biomass
parameter m. However, some differences are detected in the biodegradation parameters. Thus, the
specific degradation rate is 5 times higher at bioreactor scale, possibly due to a higher
bioavailability of Phe as carbon source. The cultivation at bioreactor scale entails an increased
transfer area, which furthers the formation of small sized bubbles which are dispersed in the culture
medium, increasing their residence time on the liquid, thus improving the degree of mixing and
aeration. This fact allows an advantageous bioprocess economy, because less time is required to
reach maximum levels of biodegradation (in flask cultures 7 days are required to achieve about
90% of degradation, while at bench scale bioreactor, just 3 days are necessary to reach the same
percentage of removal). A complementary assay of biomass sorption carries out in order to
determine the percentage of Phe adsorbed on the microorganism cells; results obtained after
analyzing all samples obtained from bioreactor cultures shown that less than 15% of Phe remained
adsorbed on the biomass.
GC-MS analyses
The results of GC-MS analyses demonstrated that P. stutzeri completely degraded Phe through
protocatechuate via, that has been previously well documented [15].In this case, the precursor of
protocatechuate, diethylphtalate, confirms that the degradation route follows the protocatechuate
via, instead of the salicylate one.
CONCLUSIONS
This study confirms the suitability of using P.stutzeri for the biodegradation of Phe both at flask and
bioreactor scale and allowed concluding a high bacterial endurance for all the range of
concentrations tested.
Acknowledgements
The authors gratefully acknowledge the financial support of the Spanish Ministry of Science and
Innovation (Project CTQ2008-0359) and Xunta de Galicia (Project 08MDS034314PR).
268
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hydrocarbons in an extremely acidic environment. Appl. Environ. Microbiol. 64 (1998) 4180-4184.
6. S. Nasseri, R. Rezaei Kalantary, N. Nourieh, K. Naddafi, A.H. Mahvi, N. Baradaran,
Influence of bioaugmentation in biodegradation of PAHs contaimated soil in bioslurry phase
reactor. Iran. J. Environ. Health Sci. Eng. 7 (2010) 199-208.
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factors of PAH (Naphthalene, Phenanthrene and Anthracene) biodegradation process by a
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and Anthracene by Pseudomonas Strain, Isolated From Coastal Area. Bioremediation J. 12 (2008)
111-116.
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Pseudomonas stutzeri. Microbiol. Mol. Biol. Rev. 70 (2006) 510-547.
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Microbial consortium bioaugmentation of a polycyclic aromatic hydrocarbons contaminated soil.
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269
VALORIZATION OF METALLURGICAL WASTE IN TECHNICAL

ROAD CASE OF BLAST FURNACE SLAGS
1 1 1 2 2
H.Cherfa , K. Ait Mokhtar , N. Saoudi , M.E.MUNOZ and A. SANTAMARIA
1 Faculty of Civil Engineering / University of Science and Technology Houari Boumediene, Algeria
ha_cherfa@yahoo.fr, kaitmokhtar@yahoo.fr, saoudinacira@yahoo.fr
2 Polymer Science and technology Department and polymer institute POLYMAT, Faculty of
chemistry, University of the Basque Country UPV/EHU, P.O.Box 1072 San Sebastian, Spain.
ABSTRACT
The blast furnace slags are metallurgical wastes, since they are byproducts of cast iron,
which come in two forms: granulated and crystallized.
The main objective of this paper is to study the mechanical properties of a material
formulated in the laboratory which is a Gravel Slag(GS) based on crushed aggregates
treated with industrial waste which is the blast furnace slag. We show in particular that
this material gives the mechanical properties allowing its use in road engineering. This
work is in the context of the valorization of blast furnace slag, which is found in large
quantities as waste dumps that came to disturb the environment.
We show in particular, as a road application, the treatment of gravel slag provides
mechanical properties allowing its use in road construction. We will introduce differents
contents of slag (10%, 15%, 20%, 25% and 30%) and test the mechanical properties of
the mixtures obtained through CBR Punching tests, simple compression test and tensile
test.
Keywords: industrial waste; slag; metallurgy; CBR; simple compression.
INTRODUCTION
In road, concern for over a decade of using waste and by-products from various sources (mining
and quarrying, metallurgical, recycling of demolition materials ...) on the one hand for questions
'environmental and other to overcome the deficit recorded in the field of road aggregates of good
qualities that are becoming increasingly rare and the high price of hydrocarbon binder that is
bitumen. The blast furnace slag is an example of this waste since they are byproducts of the
manufacture of cast iron comes in two forms: crystallized and granulated. These products are
available in large quantities in the form of slag heaps that have come to change the landscape and
disturb the environment. In Algeria the annual production of slag is estimated at 500,000 tons. The
slag does itself no virtue binding, but in the presence of water and activating hydraulic as lime, it
reacts chemically to form compounds with binding values [1].
THE BLAST FURNACE SLAG

The second product obtained during the formation of cast iron in the blast furnace is the slag. The
latter results from the merging parties' inert ore (gangue) and fluxes (limestone) that is added to the
load of the furnace to facilitate the merger. At the exit, the slag is in the form of a liquid at a
temperature of about 1450 C, isolated and rejected from the cast iron by flotation. Since the
density difference between the cast iron (7) and slag (3), so they are separated by decantation [2].
270
Process of elaboration of blast furnace slag
We develop here the two main modes, processing of the slag, which are based, one on the slow
cooling, the other on the rapid cooling and we can even say brutal.
Slow cooling
The slag is separated from the cast iron, flows through a channel into a pit where it will cool and
solidify naturally crystallizing, hence the generic name of crystallized slag (Figure 1).
Fig. 1. Elaboration of the crystallized slag
Rapid cooling
The slag can be cooled brutally and pulverized into grains of several millimeters to facilitate its
handling, it is the granulation process. The granulation is done very simply by pouring the stream of
liquid slag in a basin filled with water. The product obtained is in the form of a sand-colored called
granulated slag (Figure 2), and it is generally evacuated to places of storage or shipping.
Fig. 2. Obtaining of the granulated slag by granulation process
From a chemical point of view, we can consider the slag as a mixture of the four oxides: SiO 2 silica
/ lime CaO / Al2O3 alumina / magnesia MgO, 95 to 98% of his compositions, the remainder being
made up of secondary oxides ( FeO, MnO) and sulfur compounds [3]. The Keil diagram (triangular
diagram representing the ternary system lime-silica-alumina) is used to locate the slag compared to
other binders used in road engineering (Figure 3). This diagram shows that the slag composition
relatively close to that of Portland cement clinker, even if it requires only adding water to trigger off
a hydraulicity.
271
Glass
Pozzolana
Slags
Portland clinker
Fly ash
Alumina cement
Fig .3. Keil diagram (Rankin)
EXPERIMENTAL PROGRAM AND STUDY OF THE MATERIALS

In this experimental work, we will study the formulation of a gravel slag (GS) from an untreated
gravel on which we will introduce contents of granulated slag, respectively (10%, 15%, 20%, 25%
and 30%) and test the mechanical properties of the mixtures obtained through CBR test (evolution
in the immediate bearing and after 4 days of imbibition in water, evolution in the deformation),
simple compression test and tensile test.
The gravel slag was reconstituted in the laboratory from a granular fraction 6/20mm and sand
0/6mm. The final formulation was corrected by a sand dune 0/2mm to meet the requirements of the
specification zone.
Characterization of materials
The tests performed on the three material fractions gave the results shown in Table 1.
Table.1. Assessment of physico-chemical and mechanical properties of aggregates and sand used
Material Aggregates 6/20 Sand 0/6 Sand of dune

Silica (SiO2) [%] 4,32 5,94 95.53
Carbonates (CaCO3) [%] 95,69 89,65 3.39

L.A abrasion [%] 22,28 _ _
E.S (at 10% of fines) [%] _ 63.85 73,79
V.B _ 0,4 0,5
Superficial Neatness Coefficient [%] 0.44 _ _
Coefficient daplatissement [%] 15 _ _
apparent specific gravity [g/cm] 2.55 _ _
Absolute specific gravity [g/cm] 2.71 2.75 2.62
Analyzing aggregates grading is shown in Figure 4.
272
Fig.4. Aggregates gradation curves
Characterization of The binder

Binder used in our work is a metallurgical waste which is the granulated slag of El Hadjar (Annaba,
Algeria) from a granular fraction 0/5mm activated by slaked lime, of fresh production. The gradation
curve is shown in Figure 5 [4].
Fig. 5. Granulated slag gradation curve
Analyses performed on the slag which are shown in Table 2, show that, according to the catalog
Algerian of new pavement design, this material may be used as a binder saw the value of the
reactivity coefficient which is 39 greater than 20 the minimum value specified by that catalog.
The basicity index of 1.3 shows the basic nature of our slag which is a favorable character for use
in road engineering.
Table 2. Physical and chemical characteristics of granulated slag

Absolute specific gravity [g/cm] 2.8
Friabilit [%] 19
2
specific Surface Blaine [cm /g] 2057
Coefficient of reactivity 39
Silica (SiO2) [%] 34.99
Lime (CaO) [%] 45.78
Alumina Al2O3 [%] 9.79
The product A*C 448.19
Module basicity 1.3
Note that the product A*C is a potential reactivity of the slag in which C is the content of CaO and A is the
content of Al2O3 .
FORMULATION OF THE GRAVEL SLAG

The gravel slag (0/D) purpose of this study must have a granularity still characterized by two
factors:
273
-The maximum size of D = 20 mm which provides a high degree of homogeneity in facilitating the
mixing and reducing segregation.
-The spindle -reference to the gravel slag 0/20mm that defines the area in which the zone should
be located regularity of the mixture.
The gravel untreated was reconstituted in the laboratory from three fractions namely a sand dune,
a crushed sand 0 / 6mm and aggregate 6 / 20mm. The formulation obtained is composed of 42% 6
/ 20mm, 38% 0 / 6mm and 16% sand dune. After treatment of this basic formulation with different
contents of slag (10%, 15%, 20%, 25% and 30%), activated by 1% of lime.
Study of the CBR puncture resistance of the gravel slag

After determining of the characteristics of the modified Proctor of the gravel slag for different
contents ofslag, we perfomed the CBR puncture tests (Figure 6) according to the immediate mode
and soaked mode at 4 days of immersion in water (Figure 7).
Fig. 6. CBR puncture device Fig. 7. Soaking of CBR specimens in water
If we trace the evolution of the immediate and soaked CBR index according to the content of slag
(Figure 8), we note that this index increases with increasing the slag content to reach an optimum
at 20% of granulated slag. Thereafter, its value decreases
Fig.8. Evolution of the immediate and soaked CBR index according to the content of slag
The two curves show (Figure 8) that the addition of slag at different percentages significantly
increases the values of immediate and soaked CBR index compared to those obtained in the case
of gravel untreated (0% granulated slag), and this up to a maximum value for about 20% of
granulated slag added.
The compressive strength (resistance) RC of gravel slag at 90 days

Two sets of specimens of gravel slag compacted at the optimum Proctor, are kept at a temperature
of 20 2 for 90 days and then we maked the simple compression tests and the results are given in
Table 3.
Table 3. The values of compressive resistance at 90 days
Slag [%] 0 10 15 20 25 30
RC [bars] 30.7 45.6 60.2 70.14 65.3 67.2
274
The addition of slag improves the compressive strength of specimens since changes from a value
of 0% 30.7bars of slag to a value of 70.14 for 20% of slag and then decreases.
We note that for a slag content of 20% the compressive strength of our mixture is maximal.
The tensile strength (TS) of gravel slag at one year

From the values of tensile resistance of gravel slag at 90 days, we can deduce the values of the
tensile strength at 360 days by matching coefficients given by the standard NF P 98-114-1.
For the gravel slag we have Eq.1 :
TS (360j) = TS (90j)/0.7 (1)
The curve shown in Figure 9 shows the evolution of tensile strength of gravel slag to 360 days
according to slag contents.
Fig. 9. Evolution of tensile resistance of gravel slag to 360 days according to slag contents.
According to the specifications of Directive LCPC / SETRA of June 1983, and in the case of gravel
slag, the value of the tensile strength at 360 days must be greater than 6.5bars. In our case, for a
percentage of slag by 20% which is the optimum, there is a value 8.03 bars that is widely greater
than 6.5bars.
CONCLUSION
The results show that treatment of the gravel with a hydraulic binder based on a metallurgical
waste which is granulated slag is very interesting technically for the enhancement of local materials
and construction of foundation layers of pavements.
Improving of the bearing CBR of layers treated with slag reflects an improvement in puncture
resistance which allows them to better withstand the loads induced by traffic.
These results confirm the physical role of granulated slag, which is to fill the voids between the
grains of this mixture. This filling increases the compactness of the mixture and hence its
compressive and tensile strength. This work shows that blast furnace slag pass from simple
metallurgical waste for eliminate to a natural resource for enhance.
REFERENCES
[1] L. Zeghichi. Etude des liants et btons base des alcalis et ciments au laitier. Thse de
magister, Universit de Biskra, Biskra, Algrie, (1998),120 p
[2] BEHIM, M., REDJEL. B. & JAUBERTHIE, R.. Ractivit du laitier de haut fourneau dAnnaba
en substitution partielle du ciment. Journal de Physique IV, 12 (2002), pp 223-228.
[3] J. ALEXANDRE et J.L. SEBILEAU : le laitier de haut fourneau (laborations, traitements,
proprits et emplois.(1988).
[4] H. CHERFA, K. AIT MOKHTAR, Valorisation des dchets industriels pour la stabilisation des
couches de chausses : cas des laitiers des hauts fourneaux, Sminaire International Innovation
et Valorisation dans le Gnie Civil . Les 5 7 fvrier Hammamet, Tunisie. (2009), pp 79-89.
NORME NF P 94-078, Mesure de lindice CBR.
275
RECYCLING TECHNOLOGY: USE OF LIGNOCELLULOSIC WASTE AS LOW-

COST ADSORBENT FOR ANIONIC DYES
1,a 2 2
Palma, C. , Seplveda, L. and Contreras E.
1 Dpt. Chemical Engineering , Santa Mara University, Santiago, Chile
2 Dpt. Chemical Engineering, Santiago of Chile University, Santiago, Chile
a
email: Carolyn.palma@usm.cl
ABSTRACT
The aim of this research is to evaluate the adsorption capacity of three agro-industrial
wastes, banana peel, orange peel and Brewers spent grain, of the anionic dye, Acid
Black 1. These wastes was dried until 0.3-10% of moisture and later, milled and screened
selecting the 0.25-1.00 range of particle size. The point of zero charge determinate by
titration method are 2.4, 3.2 and 4.8 for banana peel, orange peel and Brewers spent
grain respectively. This result indicates that for pH less than zero charge point the surface
is positive favouring the uptake of anionic adsorbates. The equilibrium isotherms realized
to natural pH (5-6) indicated that the maximum adsorption capacity of Brewers spent
-1
grain (19.8 mg g ) is the same order of magnitude as that obtained with banana peel
-1 -1
(27.3 mg g ) while with orange peel the highest value was obtained (66.6 mg g ).
However the monolayer capacity of AB1 onto orange peel was increased threefold when
the process was realized at pH 2, value that is less than the respective zero charge point.
In conclusion is possible added value at the agricultural wastes using as low-cost
adsorbent of the complexes organic pollutant.
Keywords: Adsorption; Agricultural wastes; Zero charge point; Langmuir isotherm
INTRODUCTION
The release of dyes into industrial wastewater causes serious environmental problems, because
their chemical structure gives them a persistent and recalcitrant nature. Specifically the anionic
dyes which represent 20-30% of the global market have a relatively low efficiency in the dyeing
process, so that, between 10 and 50% is discharged in the effluents from the textile industries that
use them. Processes such as chemical oxidation, photo-degradation and conventional biological
treatments are not effective for this sort of pollutants since is not always achieved the
mineralization of dye remaining in the effluent some potentially hazardous molecular fragments.
Physical processes as ion exchange or adsorption are alternatives which produce a better quality
of effluent and comparatively, they can become highly effectives and low-cost.
Recently has increased the interest to investigate the possible applications of a variety of residual
biomass, which have the ability to uptake some poorly biodegradable pollutants. The adsorption
capacity of these non-conventional adsorbent is due to the presence of biopolymers such as
polysaccharides, lignin, hemicellulose and cellulose [1-2]. An interesting feature of some these
carbonaceous wastes is the physical-chemical property that as a result of the functional groups
available on their surface, enables them to form coordination complex with different dye. These
groups determine their acid-base character and therefore, the reactivity and the electrostatic
behaviour.
Since a significant amount of waste lignocellulosic such as straw, stover, stalks, seeds, bagasse,
peels, among others, is generated every year during cultivation, harvesting, processing and
consumption of agricultural products as well as from agro-industy, there are opportunities for add -
value to them using as low-cost adsorbents [3]. Different adsorbent derived from agricultural solid
276
wastes have been used for dye removal from wastewater and many studies have been published
[4-5].
The aim of this research is to evaluate the adsorption capacity of the anionic dye, Acid Black 1 onto
banana peel, orange peel and Brewers spent grain.

Residual Biomass as adsorption support: The agricultural waste used as support for adsorption,
banana peel (BP), orange peel (OP) and Brewers spent grain (BSG), were dried at ambient
temperature until it reached 10 - 15% moisture, crushed and then sieved to select the particle size
ranging from 0.25 to 1.00 mm
Adsorbat: Acid Black 1 (C.I. 20470) an anionic dye with analytical grade was used (Sigma
Aldrich). The structure and properties of dye are show in the Table 1
Determination of the zero charge point of agricultural wastes: The determination of pH value
corresponding to point of zero charge of the agricultural wastes was carried out by adding in each
flask of 1 g of biomass and 5 mL of KC1 0.1 M. Then were added in each, the appropriate aliquot
10, 7.5, 5, 2.5, 1.25 mL of HC1 0.1M or equal volumes of NaOH 0.1M with purpose of pH initial
adjust. Subsequently, enough distilled water was added in each flask to make 100 mL. These
samples were shaken for period of 1 h, after which pH was measured for each sample (pH1) and
then were added 5 mL of KCl 1 M again were shaken for period of 1 h and the pH of all them was
measured (pH2) [6].
Kinetic of dye adsorption onto biomass: Dye solutions with different initial concentration (50,
-1 -1
250 and 500 mg L ) were contacted with 2 or 4 g L of biomass in an agitated system with
temperature controlled (200 rpm, 25 2C). The evolution of residual concentration of dye in the
liquid phase with the contact time was determinate until the variation between two consecutive
measurements wasnt significant.
The adsorption capacity was determined using mass balance applied to solid and liquid phases, in
accordance with equation 1.
V (Ci C )
q (1)
m
-1
Where, q is the adsorption capacity (mg g ), V is the solution volume (L), Ci is the initial dye
-1 -1
concentration (mg L ) and C is the dye concentration on time (mg L ).
Equilibrium of dye adsorption onto biomass: Solutions with different dye initial concentration in
-1 -1
the range 50 500 mg L were contacted with 2 and 4 g L of biomass in Erlenmeyer flasks (100
mL), which were kept with agitation and temperature control (200 rpm, 25 2C) until that the
equilibrium was achieved.
Analytical assays: The samples were centrifuged and the residual dye concentration in the
supernatant solution was determined by the absorbance measures at maximum wavelength of dye
in a Helios Gamma model UV-Vis spectrophotometer (Spectronic, UK).
Table 1 Characteristics of AB1 dye

Properties of AB1 dye Molecular structure of AB1 dye
-1
Molecular weight 616.49 [g mol ]
Wavelength of maximum
620 [nm] 4-Amino-5-hydroxy-3-(p-nitrophenylazo)-6-
absorption
(phenylazo)-2,7-naphthalenedisulfonic acid
disodium salt
277
RESULTS AND DICUSSION
The zero-charge points determined for the agricultural waste were 2.4, 3.3 and 4.8 for BP, OP and
BSG respectively. These results which are show in the Figure 1 indicate that if solution pH is higher
than pHzcp the surface charge of biomass is negative, due to presence of functional groups such as
hydroxyl and carboxyl groups. Since the chromophore group of AB1 is of character anionic, uptake
of this dye is disfavored in these conditions of pH. In the contrary case, when the pH of solutions is
lower than pHzcp, the capacity of adsorption is enhanced because the surface of adsorbent will be
positively charged by the presence of amine groups [7-9].
Figure 2 shown the adsorption isotherm of AB1 obtained at natural pH (un-buffered) using OP, BP
and BSG. In these conditions the adsorption capacities are relatively low because the pH of
solution was ever higher than pH zcp and therefore, there are electrostatic repulsive interactions
between anionic dye molecule and carboxyl groups which affect negatively the removal process.
The OP presented de higher adsorption capacity for Acid Black 1 than another adsorbent studied
and these values are similar that were observed for another acid dyes as Acid Violet 17, Nylosane
Blue, Erionyl Yellow, Erionyl Red, Nylomine Red [10-11]. In the way, the adsorption capacities of
Acid Black 1 in BSG are the same magnitude than Acid Yellow 17 and Acid Blue 25 [9]. In general,
the adsorption capacities of Acid Black 1 in agricultural wastes were lower than those reported in
-1
unburned carbon residue (higher than 180 mg g ) [12].
0,20 60
0,00
0,00 4,00 8,00 12,00
-0,20 40
qe (mg g-1)
pH2 - pH1
-0,40
-0,60 20
-0,80
-1,00
0
0 100 200 300 400 500
-1,20
Ce (mg L-1)
pH1
BSG BP OP Langmuir Model
OP BP BSG
Figure 1: Point of zero charge of the agricultural Figure 2: Equilibrium isotherm of AB1 dye at pH
wastes natural
The interaction between dye Acid black 1 and agricultural waste was studied using the Langmuir
isotherm. This model is based on the formation of an ideal monolayer and is used to describe the
adsorption process that occurs on one type of binding site which are energetically homogeneous.
The Langmuir isotherm equation is represented by eq. 2 [13].
qmax k L Ce
qe (2)
(1 k L Ce )
-1
Where, qe is amount of dye adsorbed at equilibrium (mg g ), Ce is equilibrium concentration of dye
-1
in the liquid phase [mg L ], qmax is the maximum monolayer adsorption capacity of the adsorbent
-1 -1
[mg g ] and kL is the Langmuir adsorption constant related to the free energy adsorption [L mg ].
The equilibrium concentrations for the liquid and solid phase, determinate for all adsorbents, were
appropriately interpreted by the Langmuir isotherm model whose parameters are shown in the
Table 2. The model presents the best fit he experimental data for the adsorption of AB1 onto OP
2 -
and BSG (R = 98%). Additionally OP has the highest maximum capacity of adsorption (66.6 mg g
1 -1
) followed by BP (27.34 mg g ).
The low values of interaction parameter (k L) that shown in Table 2 for the three adsorbents,
indicate a poor interaction between functional groups of biomass and dye molecule because
278
prevailed the repulsive electrostatic interactions. This behavior was also reported by other
researchers [10-11].
Table 2: Parameters of Langmuir model.

-1 -1 2
Agricultural wastes qmax [mg g ] kL [L mg ] R
Brewers spent grain 19.75 0.33 0.0191 0.0015 0.986
Banana peel 27.34 1.98 0.0044 0.0007 0.981
Orange peel 66.6 1.98 0.0044 0.0030 0.707
The uptake potential of OP, BP and BSG for the removal of the AB1 dye from a solution was
assessed under favors conditions of pH. Table 3 shows the removal efficiencies by biosorption of
AB1 dye onto these agricultural wastes.
-1
Tabla 3: Removal efficiency of AB1 dye by agricultural wastes (initial concentration 50 mg L )
Banana peel Orange peel Barley spent grain
un-buffered Buffered at pH 2,5 un-buffered Buffered at pH 2,0 un-buffered
20.4 93.9 29.4 64.7 42.9
The BSG had the best performance for the AB1 dye removal in the un-buffered adsorption system,
obtaining an uptake of 43%. This level of efficiency obtained by BSG without pH control is caused
because it has the highest pHzcp. The removal efficiency of AB1 in the adsorption system buffered
using OP and BP increased between two and four times, because the surface charge of adsorbent
under these conditions, is positive. In this case the interaction with the dye was favorable. Fig. 3
shows the increase of decolorization efficiency of BP when the pH was modified at 2.5. Fig. 4
shows the effect of pH and initial dye concentration in the adsorption kinetic of Acid Black 1 onto
BP.
Decolorization efficiency (%)
30,0
93,9
q (mg g-1)
20,0
50,4
32,1
10,0
20,4 9,5
6,1
0,0
50 250 500 0 100 200 300 400
Time (min)
AB1 initial concentration (mg L-1) 50 mg L-1 natural pH 500 mg L-1 natural pH
50 mg L-1 pH 2,5 500 mg L-1 pH 2,5
BP at natural pH BP at pH 2,5 Second-order kinetic model
Figure 3: Effect of AB1 initial concentration and Figure 4: Effect of AB1 initial concentration and
pH in the removal efficiency pH in the kinetic of uptake process onto BP
In order to investigate the kinetic of AB1 biosorption process on BP, the pseudo-second-order
model was used [14]. The pseudo-second-order model is given as:
dq
k 2 ( qe q ) 2 (3)
dt
279
-1 -1
Where k2 is the pseudo-second-order rate constant (g mg min ), qe is the amount of dye
-1 -1
adsorbed at equilibrium (mg g ), and q is the amount of dye adsorbed at time t (mg g ). Integrating
Eq. (3) for the boundary conditions t = 0 to t = t and q = 0 to q = q and rearranging to obtain the
linear form according to eq. (4).
t 1 t
2
(4)
q k 2 qe qe
The rate parameters k2 and qe can be directly obtained from the intercept and slope of the plot (t/ q)
2
against t. Values of parameters k2 and qe as well as, the correlation coefficient R , for adsorption
system at natural pH and pH = 2.5 are shown in Table 4. The experimental data were fairly well
interpreted by the kinetic model of pseudo second-order because the correlation coefficients
calculated, are very closer to unity. For all initial concentrations, the equilibrium adsorption capacity
increased four-fold when the pH was changed at acid conditions. However, the rate constants
decreased between two at four times.
Table 4: Parameters of Pseudo-second-order kinetic model for the removal of Acid Black 1 by BP.
Initial dye Natural pH pH=2,5
concentration k 2 qe 2 k 2 qe 2
[mg L ]
-1 -1 -1 -1 R -1 -1 -1 R
[g mg min ] [mg g ] [g mg min ] [mg g ]
50 0.01877 2.59 0.9987 0.00493 9.95 0.9998
250 0.00221 7.05 0.9921 0.00115 25.97 0.9992
500 0.00874 7.81 0.9991 0.00151 34.13 0.9989
CONCLUSIONS
AB1 adsorption capacity was favored at pH low pH zcp of the agricultural solid waste which were
used as new adsorbent. A good fitting of Acid Black 1 sorption equilibrium data was obtained with
Langmuir model in all the range of dyes concentrations studied and kinetics of sorption of dye
follows a pseudo second order rate equation. This work revealed that the agricultural solid waste
Brewers spent grain, banana and orange peels may be the promising materials for the removal of
Acid Black 1 from aqueous solutions.
ACKNOWLEDGMENTS
This project was funded by Fondecyt 1090098.
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90 (2009), 23132342.
[2] G.Y.S. Mtui, Review: Recent advances in pretreatment of lignocellulosic waste and production
of value added products, African. J. Biotechnol. 8 (2009) 13981415.
[3] G. Annadurai, R.S. Juang, D.J. Lee, Use of cellulose-based wastes for adsorption of dyes
from aqueous solutions, J. Hazard. Mater. 92 (2002) 263274.
280
[4] M.A.M. Salleh, D.K. Mahmound, W.A.W.A. Karim, A. Idris, Cationic and anionic dye
adsorption by agricultural solid wastes: A Comprensive review, Desalination, (2011) article in
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[5] A. Bhatnagar, M. Sillanpaa, Utilization of agro-industrial and municipal waste materials as
potential adsorbents for water treatmentA review, Chem. Eng. J. 157 (2010) 277296.
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adsorbent of recalcitrant synthetic dyes, R.C. Suelo Nutr. Veg. [online] 8 (2008), 31-43.
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115-124.
281
HYBRID STRATEGIC: MINIMIZATION AND UTILIZATION OF

AGRICULTURAL RESIDUES FOR PRODUCTION ENZYME
1 1 1 *2
Elsa Contreras , Leslie Garcs , Luisa Seplveda and Carolyn Palma
1
Depto. de Ingeniera Qumica, Universidad de Santiago de Chile, Santiago de Chile
2*
Depto. de Ingeniera Qumica y Ambiental, Universidad Tcnica Federico Santa Mara,
Santiago de Chile.
ABSTRACT
With new environmental regulations on hazardous wastes, it is necessary to develop

innovative methods of treating recalcitrant compounds that lead to environmental
degradation. The research goal to degrade azo-type dyes with soluble and immobilized
peroxidase enzymes produced from agricultural wastes like banana peel. This is
+2
performed by establishing the kinetic oxidation effect of different Mn and H2O2
concentrations. The research on peroxidase enzyme production by solid-state cultures
of Pleurotus eryngii was conducted employing agricultural wastes such as banana peel.
Enzyme activity was detected in broth media culture as well as laccase, aryl alcohol
oxidase and manganese-dependent peroxidase, the last of which has the highest
concentration. A semi-purification process allowed the establishment of a single peak. It
showed manganese-dependent activity as well as independent activity with Mn of 2,6
+2
DMP. The oxidation rate of Mn with different H2O2 concentrations was evaluated. The
results demonstrated dependence of the enzyme activity on H2O2 concentrations, with
the inhibition occurring at concentrations greater than 450 M of H2O2 M with the
+2
concentration of Mn at 50 M. The preliminary results for the in vitro degradation of
BB41 by soluble and immobilized enzyme are significant with 25 % decolorization with
immobilized enzyme.
Keywords: Agricultural wastes, Ligninolytic enzyme, dye, degradation and/or decolorization.
INTRODUCTION
The new environmental regulations on hazardous wastes make it necessary to develop

innovative methods of treating recalcitrant compounds in order to prevent environmental damage.
One approach is the use of enzyme-based methods, which have a minimal impact on
ecosystems and low energy requirements. Enzyme production could be accomplished using
lignocellulosic wastes as a support substrate. These methods would allow for increasing the
value of and reduce the quantity of wastes, the production metabolites of interest at a lower cost,
and the degradation of hazardous compounds.
Azo dyes are the most extensively used in textile industries and represent 65-70% of total amount
produced [1]. Consequently, they constitute the main type of dyes present in textile wastewater.
The structure of these dyes include azo groups (-N=N-) that frequently bind to benzene or
naphthalene rings, and occasionally to aromatic heterocycles or to enolizable aliphatic groups.
The presence of chromophore groups make it difficult to biodegrade, and therefore, Azo dyes are
considered recalcitrant pollutants. Furthermore, most azo dyes are considered toxic since they
can form aromatic amines [2]. Textile dyes represent a large diversity of chemical compounds and
282
there are several conventions that can be used for their classification. Considering their ionic behavior
they are classified as cationic (Basic dyes), anionic (Acid dyes and Reactive dyes) and non-ionic.
Ligninolytic enzymes produced by white rot fungus (WRF) are known for their capacity to
completely degrade lignin, in addition to many other highly polluting compounds, such as
organochlorine insecticides, petroleum products, and textiles dyes. Recently versatile peroxidase
(VP) (E.C.1.11.1.16) has been described as a new enzyme of the ligninolytic peroxidase family,
with combined properties of lignine peroxidase (LiP) and manganese peroxidase (MnP) and
extraordinarily wide substrate specificity.
The goal of this research is to grow Pluerotus eryngii in banana peel-based medium to produce
peroxidase, with which preliminary studies were conducted on the degradation of azo-type dyes
using soluble and immobilized enzyme.
Production of peroxidases by WRF:

The production of peroxidases with WRF was accomplished using banana peel-based medium
containing 6 g banana peel, 20 ml of water and 0.5 to 1 ml inoculum /g support. The inoculums of
P. eryngii were previously obtained from submerged culture in Kimura medium. The banana peel
(Chiquita brand obtained from local supermarket) was dried to 50C in an oven for 10 d, the final
humidity was of 10%, and it was then crushed and sieved with an average diameter of 1.5 mm.
Semi-purifiying of enzyme:
To verify the type of peroxidase produced by WRF, on the day of maximum peroxidase activity
(day 18), a prepurification of an extract was obtained by size exclusion chromatography using a
column with SephacrylTM S-200 High Resolution as stationary phase and sodium tartrate (10
mM, pH 5) as mobile phase operated with a flow of 0,25 mL/min. A signal of absorbance peak
was observed at 280 nm, corresponding to the wavelength of proteins. The hemo-group of the
enzyme was visualized at 410 nm. A second step of enzyme purification was realized by HPLC
using a column of ion exchange Hi TrapTM 5mL as stationary phase and sodium tartrate buffer at
pH 5 as mobile phase. The HPLC column was operated with a retention time of approximately 30
min, a flow of 5 mL/min and, and linear gradient between 17% - 40%. The result obtained
confirmed the presence of the single peak whose molecular weight was estimated to be 43 kDa
using gel chromatography.
Immobilization of enzyme:
To immobilize the peroxidase, the crude enzyme was dissolved in phosphate buffer with pH 7 at
4C (for every 1 mL of crude enzyme, 10 mL of buffer was added), obtaining as the minimum
-1
activity 1000 U L . The activity of the enzyme was allowed to stabilize for 2 h to stabilize, and
then MANA-Agarose (per 3 mL of support was added 7 mL of solution) was added for
immobilization and incubated for 30 min to produce ionic absorption. 250 L of ethylenediamine
was then added to facilitate covalent bonding. The activity of the solution with and without support
was measured every 30 min starting from the first enzyme support contact using filter tips for
micropipettes. Gentle stirring was maintained at 4C and after the immobilization, 2 g of NaBH4
(reduction of all groups in the gel did not react with the enzyme) was added and allowed to react
for 30 min. The immobilized enzyme was then vacume filtered with filter paper and washed with
the solution buffer (2 times the volume of gel) and then stored at 4 C while maintaining moisture.
Kinetic behavior of enzyme: The reaction mixture (1 mL) contained 100 mM Na-Tartrate buffer
+2
(pH 5), approximately 2.5 g of protein, and concentrations of Mn varied between 25 to 1000
M. Reactions were carried out at 28C and initiated by addition of H2O2 in ranges between 10 to
+3
2000 M. The initial rate of complex Mn -tartrate formation was determined by following the
-1 -1
increase in absorbance at 238 nm ( 238 6500 M cm ).
Assays of in vitro degradation:
283
-1
Assays were conducted in 100 mL flasks containing 100 mM Sodium Tartrate (pH 5), 200 U L of
-1
enzyme (soluble and immobilized), 600 M MnSO 4 and 100 mgL of BB41 dyes. The reaction
began with the continuous addition of H2O2 aliquots every 5 min and with discontinuous addition
-1
every 1 h, reaching a final concentration of 100 Mh for both methods.
Enzymatic activities:
+3
Manganese peroxidase activity (named as MnP) was evaluated by the formation of Mn -tartrate
1 1
complex (238 = 6.500 M cm ) during the oxidation of 0.1 mM MnSO 4 in 100 mM sodium
tartratebuffer (pH 5) in presence of 0.1 mM H2O2 [3]. Lignin peroxidase (LiP) activity was
evaluated with 2 mM veratryl alcohol in 0.1 M sodium tartrate at pH 3 and 0.1 mM H 2O2 [4].
Laccase activity was evaluated with 5 mM 2,6-dimethoxyphenol (DMP) in 100 mM sodium citrate
1 1
buffer (pH 5.0; 469 = 27,500 M cm , referred to as DMP concentration) [5]. Aryl-alcohol oxidase
(AAO) activity was determined by the formation of veratraldehyde from 5 mM veratryl alcohol 0.1
M sodium phosphate, pH 6 [6].
Analytical techniques:
Reducing sugars were calculated by dinitrosalicylic acid method, with D-glucose as a standar [7].
Protein concentration was determined by Bradford Reagent (BioRad) at 595 nm.
RESULTS AND DISCUSSIONS
Enzyme Production
Figure 1A shows that the consumption rate of reducing sugar began to increase six fold on the
th
12 day. This coincides with an increase in protein concentration in the culture medium. The peak
-1 th
production of MnP (4000 U L ) was reached on the 18 day when the soluble reducing sugar
was exhausted. The peak production of LiP and AAO reached values of 10% and 4% with
th
respect to MnP (Figure 1B). The results achieved for broth semi-purification sampled 18
fermentation day show a peak. It shows manganese activity dependent as well as independent
activity with Mn at 2,6 DMP el cual presento actividad manganeso dependiente, asi como
actividad independiente del Mn frente a 2,6 DMP (data no shown). For this reason, the
production of peroxidase with banana peel in SSF is likely to be versatile peroxidase.
Effect of hydrogen peroxide in VP activity expression
Addition of H2O2 to in vitro degradation using MnP should be evaluated, since in excess it acts as
an inhibitor of this peroxidase [8] and therefore, the supply of H2O2 is mainly responsible for the
efficiency for in vitro degradation of dye by crude MnP [9]
284
(a) Profile of consumption of reducing sugar and production of protein
(b) Production of extracellular ligninolytic enzymes profile

Figure 1 Growth of P. eryngii in the banana peel-based culture medium
The concentration and production of peroxidases is dependent on the strain type, and it has been
reported that production by Phanerochaete chrysosporium is inhibited by hydrogen peroxide at
concentrations over 100 M, while for Bjerkandera sp BOS55, the inhbiting concentration is to
two-fold lower [10]. Figure 2A shows the effect of increasing of H2O2 concentration over the
activity of enzyme production by P. eryngii in banana peel-based medium. Furthermore, the
+2
influence of different Mn concentrations (50 - 1000 M) was included. The results indicate that
+2 +2
the inhibiting concentration of H2O2 is Mn dependent. At 50 M of Mn , the inhibiting
+2
concentration of H2O2 is from 450 M of peroxide, while between 500 and 1000 M of Mn the
inhibiting concentration is at 600 M. The enzyme production with banana peel-based medium
produces an increase in the tolerance of H2O2, maintaining a maximum level of activity in a wide
range of the inhibiting concentration (Figure 2B) compared with enzyme production in standard
+2
culture media (with glucose). Moreover, the Mn ion has a protecting affect over hydrogen
+2
peroxide inhibition, and therefore the higher Mn concentrations reduce inhibition.
+2
(a) Oxidation rate of Mn before H2O2 (b) Inhibition constants for H2O2
concentration.
+2
Figure 2. Effect of H2O2 as a function of the Mn concentration and crude enzyme
285
In vitro decolorization
Crude enzymes are preferred in practical applications due to the high cost of enzyme purification.
For this reason the assays of the soluble and immobilized enzyme were conducted with crude
enzyme.
In the Figure 3, the values obtained in the first assays in vitro for soluble and immobilized enzyme
are shown. The efficiency of decolorization was fivefold higher with immobilized enzyme. The
percent global removal is lower in both cases. Continuous or discontinuous addition of H2O2 to
culture media was not a significant variable in the degradative process.
The in vitro degradative process of tetracycline and and oxytetracycline with the crude MnP
enzyme of Phanerochaete chrysosporium has been reported to be dependent and sensitive to
different hydrogen peroxide concentrations. Concentrations over 0.2 mM of H 2O2 produce a
decrease in degradative rate in both substrates [11]. The decolorization process in this case
demonstrates a stable behavior around maximum percentage of decolorization (soluble and
immobilized enzyme), and for that reason it can be assumed that then H 2O2 concentration is
appropriate, but perhaps the enzyme concentration was limiting in the degradative process.
(a) Immobilized enzyme (b) Soluble enzyme
Figure 3 BB41 in vitro degradation by VP
CONCLUSIONS
The production of peroxidase from agricultural wastes like banana peel is possible. This
represents a new way of recycling and adding value to lignocelulitic wastes. The versatile
peroxidase had the highest concentration through SSF. Furthermore, this enzyme is sensitive to
high concentrations of hydrogen peroxide, such as the other peroxidases reported in different
research. The level of decolorization obtained for the dye under the research conditions was
around 25%.
286
ACKNOWLEDGMENTS
This project was funded by Fondecyt 1090098.
REFERENCES
[1] V.K. Gupta and Suhas, Application of low-cost adsorbents for dye removal A Review, J.
Environ. Manag. 90 (2009) 2313-2342.
[2] N. Punaveswari, J. Muthukrishnan, P. Gunasekaran, Toxicity assessment and microbial

degradation of azo dyes, Indian J Exp. Biol., 44 (2006) 618-626.
[3] M.J. Martnez, F.J. Ruz-Dueas, F. Guilln. A.T. Martnez, Purification and catalytic
properties of two manganese-peroxidase isoenzymes from Pleurotus eryngii, Eur. J.
Biochem., 237 (1996) 424-432.
[4] M. Tien, T.K. Kirk, Lignin peroxidase of Phanerochaete chrysosporium., Meth. Enzymol.
161 (1998) 238-248.
[5] C. Muoz, F. Guilln, A.T. Martnez, M.J. Martnez, Induction and characterization of
laccase in the ligninolytic fungus Pleurotus eryngii, Current Microbiol. 34 (1997) 15.
[6] F. Guilln, A.T. Martnez, M.J. Martnez, Substrate specificity and properties of the aryl-
alcohol oxidase from the ligninolytic fungus Pleurotus eryngii, Eur. J. Biochem., 209
(1992) 603-611.
[7] T.K. Ghose, Measurement of cellulase activities. Pure Appl. Chem., 59 (1987) 257-268.
[8] I. Mielgo, C. Palma, J.M. Guisan, R. Fernandez-Lafuente, M.T. Moreira, G. Feijoo, J.M.
Lema, Covalent immobilisation of manganese peroxidases (MnP) from Phanerochaete
chrysosporium and Bjerkandera sp. BOS55, Enzyme and Microbial Technology 32
(2003) 769775.
[9] G. Yu, X. Wen, R. Li, Y. Quian, In vitro degradation of a reactive azo dye by crude
ligninolytic enzymes from nonimmersed liquid culture of Phanerochaete chrysosporium.
Process Biochem. 41 (2006) 1987-1993.
[10] C. Palma, MT Moreira, G. Feijoo, JM Lema, Enhanced catalytic properties of MnP by

exogenous addition of manganese and hydrogen peroxide. Biotechnol. Letters 19 (1997)
263-265.
[11] Xianghua , J.J.L. Yannan, Enzymatic degradation of tetracycline and oxytetracycline by

crude manganese peroxidase prepared from Phanerochaete chrysosporium, Journal of
Hazardous Materials, 177 (2010) 924928
287
RESPONSE SURFACE METHODOLOGY FOR ELECTRO-FENTON PROCESS

OPTIMIZATION
Rosales, E., Prez-Paz, A., Pazos, M. and Sanromn, M.A.

Dpt. Chemical Engineering, University of Vigo, Campus As Lagoas, Marcosende 36310, Vigo,
Spain. email: emiliorv@uvigo.es
ABSTRACT
The textile industry produces large quantities of colored wastewater that contain
high levels of organic matter and salts. Several technologies have shown to be
effective to the treatment of colored wastewater treatment, among them, Electro-
Fenton is offering significant advantages and high efficiency in pollutants removal.
The aim of this work was to improve the ability of Electro-Fenton technique for the
remediation of wastewater contaminated with synthetic dyes. For this purpose, the
central composite design based on the response surface methodology was employed to
investigate the influence of the working conditions on the Electro-Fenton decoloration of
Azure B. Four operational parameters including dye concentration, electrode surface
area, treatment time and voltage were evaluated. Individual and interactive effects of
the four main independent parameters were evaluated.
2
ANOVA analysis showed high coefficient of determination value (R =0.9835) and
reasonable prediction second-order regression. The optimized operation parameters
2
were dye concentration 4.83 mg/L, electrode surface area 15 cm , voltage 14.19 V,
and treatment time of 34.58 min. Near complete decoloration was achieved
operating in the conditions described previously. Moreover, the obtained standard
deviation was lower than 3% in relation to the model predicted values.
Keywords: Azure B; Electro-Fenton; operational parameters; response surface methodology.
INTRODUCTION
Dyes are widely used in textile, rubber, paper, plastic and cosmetic industries for coloring process.
Two percent of the dyes produced are discharged directly in aqueous effluent, with a further 10%
subsequently lost during the textile coloration process [1]. Direct discharge of dye effluents can
cause serious problems to the environment due to contribution of high organic loading, toxicity and
aesthetic pollution related to color. Contaminated dye can absorb and reflect sunlight entering the
water stream causing interference with the growth of bacteria to levels such that the biological
degradation of impurities is impeded and an ecological imbalance result [2]. It has a negative
impact on the landscape and results in major environmental problems.
Advanced oxidation processes (AOP) are a promising technology that has received a great
attention during the last years [3]. AOP offer effective and rapid alternative treatments for various
contaminants including hazardous organic pollutants from wastewaters [4]. Among them, Electro-
Fenton is offering significant advantages as well as solving problems, without requirement for
special equipment, and high efficiency in organic pollutants removal [5,6]. The process is based on
+2
the continuous production of H2O2 by reduction of oxygen gas. Fe is added to increase the
oxidizing power of the electro-generated peroxide through the production of hydroxyl radical

(OH )(Eq. 1).
+2 +3 -
Fe + H2O2 Fe + OH + OH (1)
288
Hydrogen peroxide and ferrous ions are simultaneously produced in an aqueous medium by the
reduction of molecular oxygen, Eq. 2, and ferric ions, Eq. 3
+ -
O2 + 2H + 2e H2O2 (2)
+3 - +2
Fe + e Fe (3)
The Electro-Fenton process is more environment-friendly since it does not involve the use of
2+
harmful chemical reagents due to the fact that Fe ions, H2O2 and the produced hydroxyl radicals
(OH) are non-toxic [7]; electricity as a clean energy source is used in the process, so the overall
process does not create secondary pollutants [8].
Response surface methodology (RSM) has been applied to model and optimize several
wastewater treatments: photocatalytic [9], Fenton [10], Electro-Fenton [11]. The most important
part after applying the RSM, is the selection of appropriate design of experiment, that have a large
influence on the building of the response surface and thus its precision on the prediction [9].
In the present work, the central composite face-centered design based on the RSM was employed
to investigate the influence of the working conditions on the Electro-Fenton decoloration of Azure
B. Four operational parameters including dye concentration, electrode surface area,
treatment time and voltage were evaluated. Individual and interactive effects of the four main
independent parameters were studied.
Chemicals
Azure B (CAS 531-55-5) was a Sigma-Aldrich product. The properties of the dye are shown in the
Table 1. FeSO47H2O and Na2SO4 were obtained from Merck and Panreac respectively.
Table 1.- Dye structure and characteristics

Dye Type C.I. Structure max [nm]
N
Cationic
Azure B 52010 H3C
N S N
+ CH3 648
metachromatic
H CH3
thiazine dye
Electrochemical equipment
A glass cylindrical reactor with two electrode sheets connected to a direct current (DC) power
supply was used. The electrochemical reactor had a working volume of 0.15 L and was operated in
batch mode. The graphite electrode sheets were placed 10 mm above the bottom of the reactor.
The distance between electrodes was fixed at 60 mm. A constant potential difference was applied
according the experimental design with a power supply (HP model 3662) and the process was
monitored with a multimeter (Fluke 175). Sodium sulfate 0.01 M was used as inert electrolyte. The
experimental conditions are described in Table 2.
Table 2. Experimental conditions

Parameter Value
Reactor volume [L] 0.150
Initial pH 2
Temperature [C] 25
Sodium sulphate [M] 0.01
Iron dosage [mg/L] 150
In the Electro-Fenton process H2O2 is produced electrochemically via oxygen reduction on the
cathode. For this purpose, continuous saturation of air at atmospheric pressure was ensured by
bubbling compressed air near the cathode at about 1 L/min, starting 10 minutes before electrolysis
to reach a stationary O2 concentration. Iron dosage was initially added as FeSO 47H2O at a
289
concentration of 150 mg Fe/L. The pH was adjusted to working value, pH=2, with sodium hydroxide
or sulphuric acid to promote the formation of hydroxyl radicals in the Fenton process.
Analytical procedures
The absorption spectrum showed in all cases a single peak with a strong absorption in the visible
region at the wavelength indicated in Table 1. For all experiments, the dye concentration was
determinated spectrophotometrically (Unicam Helios , Thermo Electron Corp.) following the
diminution of the absorbance at the maximum visible wavelength using a calibration curve. The
decoloration, expressed in terms of percentage, was calculated from the concentration Eq. 4:
D=100(Ci - Ct) / Ci (4)
where D, decoloration (in %); Ci and Ct, concentration values of the dye at the initial and through
time, respectively.
The assays were done according to the experimental design.
Experimental design
Under the RSM is possible to identify optimal conditions while minimizing the number of
4
experiments required for a selected response. In this study, a 2 Central Composite Face-Centered
design (CCF) was utilized for the optimization of Electro-Fenton process parameters of Azure B
treatment. A total of 30 experiments were employed in this work including six replicates at the
central point. In order to investigate the operating parameters four main variables were selected:
dye concentration (X1), electrode surface area (X2), voltage (X3) and treatment time (X4). The
values of the four factors considered are shown in Table 3.
Table 3. Coded levels and independents variables for the Electro-Fenton process
Coded level +1 0 -1
X1 Dye concentration [mg/L] 6.9 4.9 2.9
2
X2 Electrode surface area [cm ] 15 12 9
X3 Voltage [V] 16 12 8
X4 Time [min] 15 30 45
The utilized response surface (Y) can be described by a second order model for predicting the
response in all experimental regions from the following Eq. 5:
Y= b0 + b1X1 + b2X2 + b3X3 + b4X4 + b12X1X2 + b13X1X3 + b14X1X4 +

2 2 2 2 (5)
b23X2X3 + b24X2X4 + b34X3X4 + b11X1 + b22X2 + b33X3 + b44X4
where Y is response variable of decoloration degree. The bi are regression coefficients for linear
effects; bii the regression coefficients for squared effects; bij the regression coefficients for
interaction effects and Xi are coded experimental levels of the variables.
Statistical analysis of the model was performed to evaluate the analysis of variance (ANOVA) using
Design Expert 7.0.0 software (Stat-Ease Inc., Minneapolis, USA).
In this study the Electro-Fenton process parameters optimization was carried out. This optimization
involved the following steps: performing the statistically designed experiments according to the
design, factors and levels selected; estimating the coefficients of the mathematical model to predict
the response and checking its suitability.
Regression model and statistical testing
290
Data analysis of the obtained values after 30 runs allows obtaining a semi-empirical expression in
terms of coded values of factors. The empirical relationship between the responses and
independent variables for model were obtained and expressed as Eq. 6:
Y = 82.57 + 0.31 X1 + 5.66 X2 + 15.34 X3 + 15.78 X4 + 5.04 X1X2 +

1.13 X1X3 + 0.79 X1X4 3.86 X2X3 + 0.049 X2X4 6.13 X3X4 (6)
2 2 2 2
6.17 X1 + 1.47 X2 6.81 X3 6.75 X4
2
The regression equation and determination coefficient (R ) were evaluated in order to test the fit of
2 2
the model. A value of R 0.9835 and an adjusted-R 0.9681 were obtained. Results confirm that the
2
experimental data are in good agreement with the predicted values (predicted-R 0.900).
The analysis of variance (ANOVA) quadratic regression model demonstrated that the model was
highly significant with a very low probability p-value <0.0001. The Fisher F-test (F value) was found
to be 63.95 which imply that the model is significant.
The main effects for this second-order model were determinate. Voltage, electrode surface, time,
interaction dye concentration-electrode surface, interaction electrode surface-voltage, interaction
time-voltage, squared effect of dye concentration, squared effect of voltage and squared effect of
time are significant model terms (Prob > F less than 0.05). The statistical analysis of all
experimental data showed that electrode surface, voltage and time have a significant effect on
Azure B removal.
Pareto analysis gives more significant information to interpret the results. In fact, this analysis
calculates the effect of each factor on the response, according to the following Eq. 7:
2 2
Pi = (bi / bi ) (i 0) (7)
Figure 1. Pareto graphic analysis
The Pareto graphic analyses are show in Fig. 1. The results suggest that the variables, time
(34.18%), voltage (32.30%) and lesser extent electrode surface (4.40%), produce the largest effect
on the decolourisation rate and dye concentration had minimum effect for dye decolourisation
(0.01%). These results are in agreement with ANOVA analysis.
Interaction among factors influencing Azure B decoloration

Response surface plots provide a valuable tool to predict the decoloration efficiency for different
values of the tested variables and help in identification of the type of interactions between these
variables. The main effects and interactions of the investigated factors are represented in Fig. 2.
291
(a) (b)
(c)
Figure 2. Response surface plots of decoloration: (a) dye concentration 4.9 mg/L and time (30
2
min); (b) dye concentration (4.9 mg/L) and electrode surface (12 cm ); (c) dye concentration
(4.9 mg/L) and time (30 min)
Fig. 2a depicts the response surface and contour plots for decoloration (%) as a function of initial
voltage and electrode surface for an initial dye concentration and treatment time of 4.9 mg/L and 30
2
min, respectively. As it can be seen an electrode surface between 14-15 cm at the highest voltage
reached a decoloration near of 95%.The increase of decoloration can be associated with the
greatest production of oxidizing agent though electrode reactions (Eq. 2 and Eq. 3).
2
The decoloration at electrode surface of 12 cm with a dye concentracin of 4.9 mg/L is shown in
Fig. 2b. The decoloration rate is accelerated from 8-12V at the initial steps of the process. It is
proposed that this behavior is due to that the treatment efficiency is significantly enhanced with
increasing applied current up to a certain kinetically limiting value.
Fig. 2c shows the effect of initial dye concentration and electrode surface on decoloration efficiency
working with a voltage of 12 V and a treatment time of 30 minutes. High electrode surface implies a
high level of decoloration when the dye concentration is included between 4-6 mg/L. This may be

due to a limited production of OH in these working conditions which do not allow the decoloration
over a limiting concentration of dye.
Optimal working conditions and validation

The desired goal in term of the decoloration efficiency was defined as maximize which means to
achieve the highest treatment performance. The model obtained for the decoloration can employed
to make the optimization of the working conditions. The optimal values of the process variables for
the maximum decoloration efficiency obtained were: dye concentration 4.83 mg/L, electrode
2
surface area 15 cm , voltage 14.19 V, and treatment time of 34.58 min. The theoretical
decoloration that must be reached with these conditions was 99.86 %. To confirm the accuracy of
the model, a new run in the optimal conditions was assayed. The obtained value of decoloration
was 97.73%. This means a decrease of 2.2% with reference to the predicted value. It implies that
the strategy to optimize the decoloration conditions and to obtain the maximal decoloration
efficiency by RSM for the decoloration of the dye Azure B with Electro-Fenton in this study was
successful.
292
CONCLUSIONS
The experimental design methodology was used to study the influence of experimental parameters
(initial dye concentration, electrode surface, voltage, and treatment time) on the decoloration
efficiency of Azure B by Electro-Fenton. Based on the experimental results, an empirical
relationship between the response and independent variables was attained and expressed by the
second-order polynomial equation. ANOVA showed a high coefficient of determination value
2
(R =0.9835), thus, ensuring a satisfactory adjustment of the second-order regression model with
the experimental data. The model obtained for the decoloration can be employed to make the
optimization of the working conditions. The statistical model was validated with respect to all the
four variables within the design space. The optimal working conditions obtained were: dye
2
concentration 4.83 mg/L, electrode surface area 15 cm , voltage 14.19 V, and treatment time of
34.58 min.
Acknowledgements
The authors gratefully acknowledge the financial support of Xunta de Galicia (Project
08MDS034314PR).
References
[1] J. Easton, The dye maker's view: In Colour in Dyehouse Effluent, in: P. Cooper (Ed.), Society of
Dyers and Colourists, Bradford, UK, 1995, 11.
[2] V. Vimonses, S. Lei, B. Jin, C.W.K. Chow, C. Saint, Adsorption of congo red by three Australian
kaolins, Appl. Clay. Sci. 43 (2009) 465-472.
[3] F. Emami, A.R. Tehrani-Bagha, K. Gharanjig, F.M. Menger, Kinetic study of the factors
controlling Fenton-promoted destruction of a non-biodegradable dye, Desalination 257 (2010) 124-
128.
[4] S. Hammami, A. Ouejhani, N. Bellakhal, M. Dachraoui, Application of Doehlert matrix to
determine the optimal conditions of electrochemical treatment of tannery effluents, J. Hazard.
Mater. 163 (2009) 251-258.
[5] M. Faouzi, P. Caizares, A. Gadri, J. Lobato, B. Nasr, R. Paz, M.A. Rodrigo, C. Saez, Advanced
oxidation processes for the treatment of wastes polluted with azoic dyes, Electrochim. Acta. 52
(2006) 325-331.
[6] M.S. Lucas, J.A. Peres, Decolorization of the azo dye Reactive Black 5 by Fenton and photo-
Fenton oxidation, Dyes Pigm. 71 (2006) 236-244.
[7] M.M. Ghoneim, H.S. El-Desoky, N.M. Zidan, Electro-Fenton oxidation of Sunset Yellow FCF
azo-dye in aqueous solutions, Desalination 274 (2011) 22-30.
[8] K. Jttner, U. Galla, H. Schmieder, Electrochemical approaches to environmental problems in
the process industry, Electrochim.Acta. 45 (2000) 2575-2594.
[9] V.A. Sakkas, M.A. Islam, C. Stalikas, T.A. Albanis, Photocatalytic degradation using design of
experiments: A review and example of the Congo red degradation, J. Hazard. Mater. 175 (2010)
33-44.
[10] H. Zhang, H.J. Choi, P. Canazo, C.-. Huang, Multivariate approach to the Fenton process for
the treatment of landfill leachate, J. Hazard. Mater. 161 (2009) 1306-1312.
[11] A.K. Abdessalem, N. Oturan, N. Bellakhal, M. Dachraoui, M.A. Oturan, Experimental design
methodology applied to electro-Fenton treatment for degradation of herbicide chlortoluron, Appl.
Catal. B Environ. 78 (2008) 334-341.
293
EK-FENTON FOR REMEDIATION OF DIESEL FUEL POLLUTED SOIL

1 1 1 1
M. Pazos ,F. Moscoso , E. Rosales , A. Prez-Paz, and M.A. Sanromn
1 Dpt. Chemical Engineering, University of Vigo, Campus As Lagoas, Marcosende 36310, Vigo
Spain email: fatima@uvigo.es
ABSTRACT
The treatment of diesel contaminated areas by conventional decontamination techniques
is difficult due to the low water solubility of diesel fuel. Therefore, new processes to
remediate diesel fuel contaminated soil must be developed. In this work, electrokinetic
treatment of a soil contaminated with diesel fuel (5,000 ppm) was carried out. Two
different approaches were assayed in order to obtain pollutant removal. On the one hand,
the use of surfactant (Tween 80) as process fluid during the electrokinetic treatment was
assayed to increase desorption and solubility of diesel fuel. Thus, organic pollutant in
solution can be transported by the electroosmotic flow. On the other hand, a hybrid
technology as the combination of Fenton reaction and electrokinetic remediation (EK-
Fenton) was carried out in order to favour the pollutant in situ degradation. In view of the
obtained results, it can be concluded that the diesel fuel polluted soil can be effectively
decontaminated by using hybrid electrokinetic treatment EK-Fenton. It was demonstrated
that after 30 days of treatment the EK-Fenton process reached the highest diesel fuel
removal, around 87%.
Keywords: advance oxidation process, Tween 80, Fenton reagent, diesel fuel.
INTRODUCTION
Petroleum-derived diesel is composed of approximately 75% saturated hydrocarbons (primarily

paraffins including n-, iso-, and cycloparaffins) and 25% aromatic hydrocarbons (including
naphthalenes and alkylbenzenes) [1]. As a result of its composition, mainly hydrophobic organic
compounds, diesel fuel shows low water solubility. Consequently, the treatment of diesel
contaminated areas by conventional decontamination techniques is difficult. Therefore, new
processes to remediate diesel fuel contaminated soil must be developed.
Polluted soils can be treated by in situ and ex situ methods. However, from an economic and
environmental point of view the in situ decontamination is attracting high significance. In situ
technologies are non-invasive techniques where microorganisms and/or physical-chemical
processes are used to remove pollutants from soils [2]. Among them, the electrokinetic technique
has been successfully applied to the remediation of soils, wastes and sediments polluted with
inorganic and organic contaminants [3]. One of the most important advantages of this treatment is
its efficiency on the treatment of low hydraulic permeability soils, where other techniques, as
natural attenuation or traditional remediation efforts such as pump-treat are inadequate.
In the electrokinetic treatment a low electric field is applied to promote the movement of
contaminants towards the electrode chambers. The main transport mechanisms are
electromigration, migration of ions towards the opposite charged electrode, and electro-osmosis,
movement of liquid inside the pore induced by the electric field [2]. Under this technology the
pollutants should be in solution to be transported by the electric field, thus, inorganic species, as
heavy metals, are mainly transported by electromigration. However, organic compounds, usually
uncharged, are transported with the electro-osmotic flow.
In this work, electrokinetic treatment of a soil contaminated with diesel fuel (5,000 ppm) was carried
out. Two different approaches were assayed in order to obtain pollutant removal. On the one hand,
the use of surfactant (Tween 80) as process fluid during the electrokinetic treatment was assayed
294
to increase desorption and solubility of diesel fuel. On the other hand, a hybrid technology as the
combination of Fenton reaction and electrokinetic remediation (EK-Fenton) was carried out in order
to favour the pollutant in situ degradation. Under this hybrid technology, the electric field is utilized
to mobilize the Fenton reagent through the soil and provide an adequate environment to carry out
the in situ degradation of organic compounds (Fig. 1). Reagents are homogeneously coming into
the soil by the action of the electric field. Thus, iron is utilized as a catalyst to decompose H 2O2 to
generate free hydroxyl radicals that oxidize organic compounds (Fenton reaction).
SOIL SURFACE
ANODE Fe CATHODE
DEGRADATION
Fe2++H2O2 OHFenton
+OH-+ Fe3+
+ H2O2
Process Fluid Flow
reaction PRODUCTS
-
ORGANIC
POLLUTANT
Fig. 1. EK-Fenton
Soil
Soil samples were collected from the northwest of Spain (Galicia). Samples of the top 30 cm were
taken by using an Eijkelkamp sampler and were pooled in the field. The pooled samples were
transported to the laboratory in polyethylene bags. Afterward, they were sieved and the fraction
containing particles of sizes lower than 2 mm was selected.
Sample preparation
The soil was spiked with commercial diesel fuel to yield a concentration of 5,000 mg of pollutant
per kg of soil. The mixture was easily stirred and blended homogeneously. The mixture was kept at
room temperature (20 C) for two weeks in a fume hood. Afterwards the contamination procedure,
the soil sample was mixed with deionized water to achieve moisture content, similar to natural
value, of approximately 30% (w/w). Previous each experiment, a representative sample of the
mixture was taken for the initial analysis of diesel fuel concentration, pH and moisture content.
Electrokinetic cell
Electrokinetic treatments were carried out in a cylindrical glass cell Fig. 2. Soil sample was
introduced in the central tube (approx. 150 g), which was 100 mm in length and had a 32-mm
internal diameter. At each end of the sample compartment, two electrode chambers (0.3 L) were
placed and filter paper and porous stones were used to isolate them from the solid sample.
Graphite electrodes were used for both anode and cathode. The selected processing fluid was
used to fill the electrode chambers and peristaltic pumps were used to recirculate the fluid in order
to avoid concentration gradients (Table 1). The processing fluids of experiments 1-3 were
renovated periodically in order to maintain the pH around 8.5 because the buffering capacity of the
used buffer is limited under the electric field action. In all experiments, a constant potential
difference of 30 V (3 V/cm) was applied during 30 days. Periodically, readings of current intensity,
voltage drop and pH in the electrode compartments were done
295
Fig.2. Schematic diagram of experimental set-up: (1) soil sample, (2) porous stones, (3) electrodes,
(4) electrode chambers, (5) auxiliary electrodes.
Table 1. Summary of the experiments. A: anode fluid and C: cathode fluid

Experiment Processing Fluid pH Control
A: Tris-Acetate-EDTA 0.1M pH 8.5
1 Tween 80 1%
C: Tris-Acetate-EDTA 0.1M pH 8.5
2 Tween 80 3%
3 Tween 80 3%
A: without
4 10% H2O2 0.1M Na2SO4
C: 0.5 M HNO3 pH 3
Analytical methods
Initial and final samples were taken from the soil matrix and from the cathode and anode solutions
for chemical analysis. The soil sample was removed from the soil compartment (central tube) with
a spoonbill and divided in five sections with similar size (S1-S5, namely from anode to cathode)
and they were analysed for pH, moisture content and pollutant concentrations. Duplicated
analytical determinations were done and the showed results are the mean values with an
experimental margin of error below 3%.
Diesel fuel concentration was measured as total petroleum hydrocarbon (TPH) based on EPA 9074
method. Diesel fuel was extracted with methanol from soil sample. A 1-10 g sample of soil with
diesel fuel concentration 10-2,000 ppm was extracted with 10 mL dissolvent. The resulting mixture
was allowed to settle and the free liquid was decanted into the barrel of a filter-syringe assembly.
This liquid was filtered through a 0.2-m filter into a cuvette containing water. The filtered sample
was allowed to develop for 10 minutes. During the development, any hydrocarbons present
precipitate out and become suspended in solution. The developed sample was measured UV-
visible spectrophotometrically (Unicam Helios , Thermo Electron Corp.) based on the constructed
calibration curves at absorption wavelength of 585 nm. The concentration of total recoverable
petroleum hydrocarbons present was calculated relative to the standard curve realized with
commercial diesel fuel used in the spiking process.
The pH value of solid sample was measured by adding a 1 M KCl solution to dry sample in a ratio
of 2.5 mL/g. The pH was measured, after 1 h of contact time, with a pH meter IQ Scientific
Instruments (model Stainless Steel ISFET pH Probes).
Electrokinetic treatments with Tween 80

Initially, the effect of surfactant in the processing fluid during the electrokinetic treatment of diesel
fuel polluted soil was assayed. Surfactants are chemical compounds that as a result of its structure,
hydrophilic and hydrophobic groups, can increase solubility of organic compounds, as diesel fuel,
in water. Once the diesel fuel is in the liquid phase, it can be mobilized by the action of the electric
field. The electrokinetic movement of organic compounds is mainly due to the electro-osmotic flow,
thus, to obtain an effective pollutant removal, the electro-osmotic flow should be enhanced.
296
According to HelmholtzSmoluchowski theory, the electro-osmotic flow rate is mainly proportional
to zeta potential and electric-field strength. Hence, if the current intensity of the electrokinetic
process is low, the electro-osmotic flow will be negligible. Thus, the presence of ionic species
increases the electric-field strength favouring the electro-osmotic flow. Additionally, the zeta
potential depends on nature and properties of the soil, especially soil pH [4]. Several studies have
found that favouring alkaline pH in the system increased the electro-osmotic flow [5]. Therefore, it
is necessary to have a basic medium inside the soil to enhance the pollutant removal. Under these
premises and based on our previous results in the electrokinetic treatment of PAHs mixtures [6], a
solution of Tween 80 1% was selected as processing fluid and the pH control (pH=8.5) in the
electrodes chambers was performed by using Tris-Acetate-EDTA buffering solution (Fig. 3 Exp. 1).
No electrolytes were added because the presence of the buffering solution increased by itself the
ionic strength in the electrode solutions.
1,2
Exp. 1
1,0 Exp. 2
Normalized concentration (C/C 0)
Exp. 3
0,8
0,6
0,4
0,2
0,0
S1 S2 S3 S4 S5
Fig. 3 Diesel fuel distribution after 30 days of electrokinetic treatment in experiment 1, 2 and 3.
After this treatment high pollutant removal was reached in the first section near the anode (S1).
Approximately 78% of diesel fuel was removed from this first section. Despite of a basic medium
was favored inside the soil (pH around 7.5) the amount of pollutant removed from the following
sections was low. At the end of the treatment about 31% of diesel fuel was extracted from the soil.
Although the used surfactant was the same utilized in our previous research [6], to remove PAHs
from kaolin, insignificant results were obtained. It is postulated that the pollutant concentration,
tenfold more in this work, could be the reason for this low removal. Thus, the amount of employed
surfactant should be increased.
A new experiment (Fig. 3 Exp. 2) with an increase of Tween 80 concentration in the processing
fluid was carried out. Surfactant concentration was increased from 1 to 3%, highest concentrations
are considered economically unviable. It was expected that an increase of surfactant concentration
would favour the diesel fuel removal. The diesel fuel removal in the first section (S1) of the
experiment 2 was higher (90 %) than experiment 1 (Fig. 3). However, most of diesel fuel that
migrated from this first section was concentrated in the section S2. Although after 30 days, the
removal reached in this second treatment (45%) was higher than previous one, the removal rate
is not in accordance with the expected. It is assumed that the low removal was related to low
electro-osmotic flow. The coefficient of electro-osmotic conductivity for the experiments 1 and 2 (ke,
2
m /Vs) were calculated from the equation (1)
297
Q = ke ie A (1)
Where:
3
Q: electro-osmotic flow (m /s),
ie: voltage gradient (V/m)
2
A: cross-sectional area of flow (m ).
-10 2
Similar ke value was obtained for both experiments around 1.3 x 10 m /Vs. Consequently,
although the diesel fuel was solubilized in the first sections the amount of surfactant that reached
the soil by the electro-osmotic flow was not enough to carry out an effective removal.
Different studies have proposed that the presence of complexing agents favours the organic
compound removal increasing the electro-osmotic flow one order of magnitude [7] or favoring their
soil desorption, removing the metal ions in the soil, thus organic macromolecules bound to the
mineral surface via the metal ions are released into the aqueous phase [8]. Therefore, EDTA
concentration in the Tris-Acetate-EDTA buffering solution was increased from 0.1 to 0.2 M (Exp.3).
Under these conditions, diesel fuel concentration was significantly reduced in all sections (Fig. 3).
After 30 days of treatment more than 55% of diesel fuel was removed from the soil. Although the
-10 2
electro-osmotic flow was increased (k e 1.8 x 10 m /Vs), this raise was not enough to improve
considerably the diesel fuel removal.
Electrokinetic treatment with Fenton reaction

Electrokinetic treatment can be combined with the Fenton reaction (EK-Fenton) for the in situ
removal of organic compound. Based on, a new experiment was developed with the aim of
reaching total remediation of diesel fuel polluted soil (Exp. 4 Table 1). In the EK-Fenton, the electric
field is utilized to provide an adequate environment to develop the Fenton reaction inside the soil.
Reagents are homogeneously coming into the soil by the action of the electric field. Thus, iron is
utilized as a catalyst to decompose H2O2 to generate free hydroxyl radicals that oxidize organic
compounds (Fenton reaction).In this experiment no addition of iron as catalyser was necessary
because the native soil iron content was around 18,400 ppm.
In Fig. 4 are shown the soil pH and diesel fuel distribution after the EK-Fenton process G4. High
removal was obtained in all soil sections. Approximately 87% of diesel removal was achieved after
30 days of treatment. This removal was associated with the pollutant in situ degradation during the
action of Fenton reagent formed inside the soil. The pH profile was maintained at low pH between
2.1 and 3.7 thus an adequate environment was provided to develop the Fenton reaction.
1,0 8
Normalized concentration (C/C 0)
0,8 C/Co
pH 6
0,6
pH
0,4
2
0,2
0,0 0
S1 S2 S3 S4 S5
Fig. 4 Diesel fuel distribution after 30 days of electrokinetic treatment in experiment 4.
298
CONCLUSIONS
In view of the obtained results, it can be concluded that the diesel fuel polluted soil can be
effectively decontaminated by using hybrid electrokinetic treatment. Although different strategies
were performed in order to improve the pollutant decontamination, the EK-Fenton treatment
obtained the best results. It was demonstrated that the electrokinetic remediation can be effectively
used to provide an adequate environment and introduce the reagents into the soil. It was
demonstrated that after 30 days of treatment the EK-Fenton process reached the highest diesel
fuel removal, around 87%.
Acknowledgements
This work was supported by Spanish Ministry of Science and Innovation (CTQ2008-03059/PPQ).
References
[1] ATSDR Toxicological profile for fuel oils, Department of Health and Human Services, Public
Health Service, Atlanta, GA 1995.
[2] M. Pazos, E. Rosales, T. Alcntara, J. Gmez, M.A. Sanromn, Decontamination of soils
containing PAHs by electroremediation: A review, J. Hazard. Mater. 177 (2010) 1-11.
[3] M. Pazos, M.T. Alcntara, C. Cameselle, M.A. Sanromn, Evaluation of electrokinetic technique
for industrial waste decontamination, Sep. Sci. Technol. 44 (2009) 2304-2321.
[4] A. Asadi, B.B.K. Huat, M.M. Hanafi, T.A. Mohamed, N. Shariatmadari, Role of organic matter on
electroosmotic properties and ionic modification of organic soils, Geosci. J. 13 (2009) 175-181.
[5] R.E. Saichek, K.R. Reddy, Effects of system variables on surfactant enhanced electrokinetic
removal of polycyclic aromatic hydrocarbons from clayey soils, Environ. Technol. 24 (2003) 503-
515.
[6] M.T. Alcantara, J. Gomez, M. Pazos, M.A. Sanroman, Electrokinetic remediation of PAH
mixtures from kaolin, J. Hazard. Mater. 179 (2010) 1156-1160.
[7] K.I. Popov, N.A. Shabanova, A.A. Artem'eva, E.M. Urinovich, Y.V. Tulaeva, Influence of
chelating agents on the electrokinetic potential of the clay fraction of soddy podzolic soils Kolloidnyj
Zhurnal 59 (1997), 233-235.
[8] Y. Yang, D. Ratt, B.F. Smets, J.J. Pignatello, D. Grasso, Mobilization of organic matter from a
weathered manufactured gas plant soil by metal ion complexing agents and implications for
polycyclic aromatic hydrocarbon desorption. Chemosphere 43 (2001) 43, 1013-1021.
299
ISOLATION OF NOVEL BENZO[a]ANTHRACENE-DEGRADING MICRO-

ORGANISMS TO APPLY TO SOIL BIOREMEDIATION
Perez-Paz, A., Moscoso, F., Vazquez, X., Pazos, M. and Sanromn, M.A.
Dpt. Chemical Engineering, University of Vigo, Campus As Lagoas, Marcosende 36310,
Vigo, Spain. email: fatimamoscoso@uvigo.es
ABSTRACT
Polycyclic aromatic hydrocarbons (PAHs) are an important kind of xenobiotic, persistent
pollutants in soil, slurry and air. The persistence of PAHs in the environment is mainly
due to their low solubility in water and stable polycondensed aromatic structure.
The aim of this work is the improvement of the available bank of microbial resources by
the isolation of different microorganisms and the determination of their ability to degrade
a model compound, studying the biodegradation of PAHs such as benzo[a]anthracene.
After isolating and genetic identification of the potential degrading-strain, the fungi
Trichoderma longibrachiatum and Byssochlamys spectabilis and the isolated consortium
denominated B261b were selected to develop a PAH bioremediation process.
The degradation ability of these strains was determined in liquid cultures with 100M of
benzo[a]anthracene in two successive batches. The results obtained clearly showed the
superiority of isolated consortium B261b following to Trichoderma longibrachiatum and
Byssochlamys spectabilis cultures.
Keywords: benzo[a]anthracene, biodegradation, Byssochlamys spectabilis, consortium B261b,

Trichoderma longibrachiatum
INTRODUCTION
The conventional techniques used for remediation have been to dig up contaminated soil and
remove it to a landfill, or to cap and contain the contaminated areas of a site. The methods have
some drawbacks.
Bioremediation is an option that offers the possibility to destroy or render harmless various
contaminants using natural biological activity. Bioremediation is the use of living organisms,
primarily microorganisms, to degrade the environmental contaminants into less toxic forms. It uses
naturally occurring bacteria and fungi or plants to degrade or detoxify substances hazardous to
human health and/or the environment. The microorganisms may be indigenous to a contaminated
area or they may be isolated from elsewhere and brought to the contaminated site. Contaminant
compounds are transformed by living organisms through reactions that take place as a part of their
metabolic processes. Biodegradation of a compound is often a result of the actions of multiple
organisms. When microorganisms are imported to a contaminated site to enhance degradation we
have a process known as bioaugmentation. Therefore, bioremediation uses relatively low-cost, low-
technology techniques, which generally have a high public acceptance and can often be carried out
on site. It will not always be suitable, however, as the range of contaminants on which it is effective
is limited, the time scales involved are relatively long, and the residual contaminant levels
achievable may not always be appropriate. Although the methodologies employed are not
technically complex, considerable experience and expertise may be required to design and
implement a successful bioremediation program, due to the need to thoroughly assess a site for
suitability and to optimize conditions to achieve a satisfactory result [1].
Polycyclic aromatic hydrocarbons (PAHs) are a group of organic contaminants that form from the
incomplete combustion of hydrocarbons, such as coal and gasoline. PAHs are an environmental
concern because they are toxic to aquatic life and because several are suspected human
carcinogens. Due to PAHs low solubility in water and stable polycondensed aromatic structure,
300
there are persistent in the environment. 16 of these compounds have been identified by US
Environmental Protection Agency as hazardous contaminants [2-4].
Bioremediation of PAHs is considered to be the major decomposition process, and represents a
potential solution to the environmental problems. Usually, low-molecular-weight PAHs (two or three
aromatic rings) as sole carbon and energy sources are readily degradable, but high-molecular
weight PAHs, containing four or more aromatic rings, are regarded as recalcitrant,
thermodynamically stable and more difficult to degrade [5]. Benzo[a]anthracene, a tetracyclic PAH,
has been widely used as an indicator and a model compound to study biodegradation of PAHs [6].
Bacterial and fungal isolates have been reported to grow on or mineralize PAHs, such as strains of
Bacillus subtilis and Pseudomonas aeruginosa, Penicillium sp., Diaphorobacter sp. and
Pseudoxanthomonas sp., saprotrophic soil filamentous fungi and yeasts [7]. Microbial strains
indigenous to a particular habitat have been shown to outcompete other artificially introduced
strains in bioremediation investigations of oil contaminated sites. A detailed knowledge of the
indigenous microbial ecology would therefore be an important prerequisite of the design and
implementation of any bioremediation scheme [5].
Improvement of the available bank of microbial resources and information is crucial to the proper
management of PAHs-polluted sites. The aim of this study is the isolation of different
microorganisms and the determination of their ability to degrade a model compound to study
biodegradation of PAHs such as benzo[a]anthracene.
Medium
The minimal medium (MM) was composed of (g/L): Na2HPO42H2O 8.5, KH2PO4 3.0, NaCl 0.5,
NH4Cl 1.0, MgSO47H2O 0.5, CaCl2 0.0147. MM also contained trace elements as follows (mg/L):
CuSO4 0.4, KI 1.0, MnSO4H2O 4.0, ZnSO47H2O 4.0, H3BO3 5.0, H2MoO42H2O 1.6 and
FeCl36H2O 2.0 [8]. Solid agar plate was composed of (g/L): NaCl 3, peptone 10, yeast extract 5
and agar 15.
Strain isolation
The samples from wastes polluted with polycyclic aromatic hydrocarbons (PAHs) and heavy metals
were collected. The samples were stored in sterile glass tubes with screw tops. Samples were
suspended in 100 mL of MM with 100 M benzo[a]anthracene and 1% Tween 80 (purchased from
Sigma Aldrich) and were incubated with shacking at 150 rpm at 30 C in the dark. 10-mL of the
aliquot was transferred to 100 mL of a fresh MM containing the same benzo[a]anthracene as above
and incubated under the same conditions. Strain isolation was carried out by the 13-streak plate
method, which consisted of a mechanical dilution of the samples on the surface of agar plates
describe above. The plates were incubated at 30C. Benzo[a]anthracene was sterilised by filtration
through a 20-m filter and added until final concentration of 100 M to the autoclaved medium
avoiding any possible alteration to the chemical structure of the PAH. Based on the method
described by Hanson et al. [9], the microorganism with degrading potential was selected.
Genetic identification of the selected strains

PCR AmpliTaq DNA polymerase with GeneAmp GeneAmp 10X PCR Buffer II (Applied
Biosystems) and ITS1 universal fungal primers was used PCR amplification. PCR-amplified
fragments were purified, and sequenced with an ABI PRISM 310 sequencer and a BigDye
terminator cycle sequencing ready reaction kit (Applied Biosystems). Alignment of sequences was
created by BIOEDIT software package, which were subsequently compared with sequences in
public databases of GeneBank (http://www.ncbi.nlm.nih.gov/).
Flask cultures
Submerged aerobic cultures were carried out in 250-mL Erlenmeyer flasks with 50 mL of a MM
with 100 M benzo[a]anthracene and 1% Tween 80. The pH was initially adjusted to 7.5, and the
medium without benzo[a]anthracene was autoclaved at 121C for 20 min. The flasks were
inoculated (3%) with the previously obtained cell pellets, which were then incubated in an orbital
shaker at 30C and 150 rpm.
301
Benzo[a]anthracene measure
Benzo[a]anthracene concentration in supernatant was determined by HPLC (Agilent 1100)
equipped with an XDB-C8 reverse-phase column (1504.6 mm i.d., 5 m). Prior to injection, the
samples were filtered through a 0.45-m Teflon filter. The injection volume was set at 5 L, and the
isocratic eluent (60:40 acetonitrile/water) was pumped at a rate of 1 mL/min for 10 min. Detection
was performed with a diode array detector from 200 to 400 nm, and the column temperature was
maintained at 20C.
Improvement of the available bank of microbial resources and information is crucial to the proper
management of PAHs-polluted sites. In the present work, several samples from wastes polluted
with PAHs and heavy metals have been investigated as potential sources of PAH-degrading
microorganisms.
Strain isolation and genetic identification

After isolating twelve potential degrading-strains, two of them were assured to be best in the
preliminary tests. Genetic identification by 16S rRNA sequencing was carried out for these strains,
and they were identified as Trichoderma longibrachiatum CH4 and Byssochlamys spectabilis HRE.
The sequences of both exhibited the highest similarity (99%) to those of Trichoderma
longibrachiatum and Byssochlamys spectabilis, respectively. None of the isolated strains had ever
been reported as PAHs-degrading microorganisms. Carvalho et al [10] detected that surprisingly
Trichoderma longibrachiatum, was able to directly metabolise Pentachlorophenol (PCP), leading to
its complete depletion from media. Their data emphasise the significance of the fungus to have an
interesting potential to be used in PCP bioremediation processes. In relation to the ability of
Byssochlamys spectabilis to degrade any organic compounds there are few papers. Mann et al [11]
reported the ability of four isolates, species, among them Byssochlamys sp. and compared against
P. chrysosporium for their ability to bioremediate olive mill wastewater in the presence of a
competing indigenous microflora. On the other hand, Scelza et al [12], identified as fungi belonging
to the Byssochlamys fulva strain of the taxonomic group of Ascomycetes from surfaces of the PCP-
contaminated samples. They determined that cell-free extracts of soil-isolated B. fulva displayed
enzymatic activities involved in the degradation pathway of lignin [13].
In the experimental batch process developed in this work, an isolated consortium denominated
B261b was used due to the good degradation level detected in the different PAHs degradation
tests realized.
Benzo[a]anthracene biodegradation
In this study, benzo[a]anthracene as an indicator and model compound and was experimentally
ascertained through cultivation in Erlenmeyer flasks. In a second stage, the benzo[a]anthracene
was added on day 18 at the same final concentration (100 M). Fig. 1, 2 and 3 show the
benzo[a]anthracene degradation curves to T. longibrachiatum, B. spectabilis and consortium
B261b along the cultures.
302
2D Graph 2
100
Benzo[a]antrhacene degradtaion (%)

80
60
40
20
0
0 2 4 6 8 10 12 14 16 18 20
TIme (days)
Figure 1- Profiles of benzo[a]anthracene
Col 1 vs Col degradation
2 st in successive batches of Trichoderma
nd
longibrachiatum CH4 Col
cultures:
1 vs Col 31 (solid symbol) and 2 (void symbol).
100
80
60
40
20
0
0 2 4 6 8 10 12 14 16 18 20
TIme (days)
Figure 2- Profiles of benzo[a]anthracene degradation in successive batches of Byssochlamys
Col 1 vs Col 5
spectabilis HRE cultures: 1st (solid symbol) and 2nd (void symbol).
Col 1 vs Col 6
303
2D Graph 2
100

80
60
40
20
0
0 2 4 6 8 10 12 14 16
TIme (days)
Figure 3- Profiles of benzo[a]anthracene degradation in successive batches of consortium B261b

cultures: 1stCol(solid symbol)
1 vs Col 8 and 2nd (void symbol).
Col 1 vs Col 9
As can be seen in these figures, the consortium cultures gave the highest degradation levels in
both batches, showing values around 95% in four days.
Trichoderma longibrachiatum CH4 cultures presented similar high degradation values after 10
days, although in the second batch the time was reduced to 6 days.
Byssochlamys spectabilis HRE exhibited the lowest degradation level however this result was
improved in the second batch reached near complete degradation in 6 days.
CONCLUSIONS
The abovementioned results obtained in this research showed the enormous potential of the
microorganisms isolated in the degradation of high-molecular weight PAHs. Nowadays, more
studies in polluted PAHs soil are underway in our laboratory.
Acknowledgements
References
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304
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Hursthouse, C. Silva Pereira, Screening pentachlorophenol degradation ability by environmental
fungal strains belonging to the phyla Ascomycota and Zygomycota, J. Ind. Microbiol. Biotechnol. 36
(2009) 1249-1256.
[11] J. Mann, J.L. Markham, P. Peiris, N. Nair, R.N. Spooner-Hart, P. Holford, Screening and
selection of fungi for bioremediation of olive mill wastewater, World J. Microbiol. Biotechnol. 26
(2010) 567-571.
[12] R. Scelza, M.A. Rao, L. Gianfreda, Response of an agricultural soil to pentachlorophenol
(PCP) contamination and the addition of compost or dissolved organic matter, Soil Biol. Biochem.
40 (2008) 2162-2169.
[13] H. Furukawa, M. Wieser, H. Morita, T. Sugio, T. Nagasawa, Purification and characterization of
vanillyl-alcohol oxidase from Byssochlamys fulva V107, J. Biosci. Bioeng. 87 (1999) 285-290.
305
TECHNOSOLS MADE OF WASTES TO RECOVER MINE SOILS

1 1 1 1 1
R. Forjn , V. Asensio , F.A. Vega , M.L. Andrade , E.F. Covelo
1
Departamento de Bioloxa Vexetal e Ciencia do Solo, Facultade de Bioloxia, Universidade de
Vigo, Lagoas, Marcosende, 36310 Vigo, Pontevedra, Spain. Tel.: +34986812630. Fax:
+34986812556. E-mail address: rforjan@uvigo.es
ABSTRACT (mx. 200 words)

Many mine soils are chemically, physically and biologically deficient. They can turned
into a dangerous source of pollution for superficial and sub superficial waters. At
Touro mine (NW Spain) some areas in the mine tailings are being recovered by using
Technosols, amendments that are considered as a new horizon under the mine soil.
These amendments are made of wastes from different sources and they can increase
the nutrient content in degraded soils. It was studied the effect of the addition of waste
amendments one the nutrient content of soil from a bare settling pond soil. Preliminary
results from the pot experiment indicate that the use of Technosols can be beneficial
for plant growth. They significantly increased the CECe of the mine soil, mainly
because of their Ca and Mg contents. Fulvic and humic acid contents also increased
as time elapsed as well as inorganic nitrogen contents. Periodic controls of the dosage
as well as the nutrient levels in soil are advisable to reach optimal conditions for plant
growth.
Keywords: mine soil; nutrients; settling pond; Technosol; waste amendments.
INTRODUCTION
Mining is one of the more destructive industrial activities for the environment. Mining activities
produce a huge amount of waste materials causing storage problems [1]. If no restoration plan
is done during or after the mining activity, the area can turned into a dangerous source of
pollution for superficial and sub superficial waters. The pollution is due to the characteristics of
mine soils: badly structured texture, low effective depth and very low structure because as well
as strong and fast oxidation of the waste material. The oxidation produces an intense release of
protons which create a hyperacid or hiperoxidizing environment where minerals are strongly
2- 3+ 2+ 2+ 2+ 2+ 2+
altered and ions as SO4 , Al , Fe , Mn , Pb , Cu or Zn are released [2]. In addition to high
levels of acidity, spoils are deficient in plant nutrients such as N, P, K, Ca, and Mg [3]. The lack
of both organic matter and clay fraction favours the decrease of cation exchange capacity and
nutrients. Soil pH and Eh are also most of the times modified increasing the solubility of many
elements including the metallic ones [2].
The current Spanish legislation demands from the company in charge of mining activities the
restoration of the mine soils before finishing [4]. As these mine soils must be stabilized due to
their high degradation, it is necessary to prepare the soil for a good root development and to
plant vegetation.
In the depleted copper mine from Touro (NW Spain), there are still some areas with no
restoration applied since the mining activity finished in 1988. Nowadays material for road
construction is extracted. Some areas from different mine tailings have been treated at the end
of the copper extraction by means of planting trees. At the year 2000, the company Ecological
Treatments of Norwest (T.E.N.) began to vegetate and amend some areas in the mine tailing
with the aim of improving the condition of this degraded soil. These amendments are
considered as a new horizon under the mine soil, and they are called Technosols according to
the FAO (2006) [5]. T.E.N. company tried to make new soils with this kind of amendments with
the aim of (1) simultaneously solve problems associated with waste management and with
degraded or contaminated soils, in an affordable and environmentally sound manner and (2) to
eliminate or greatly reduce the impacts of waste products in the most sensitive systems (water,
air and biota) [6]. Technosols made of wastes are believed to carry out the same ecological
functions than soils.
The availability of nutrients in some places like opencast mining and waste disposal sites
306
depends on topography, site characteristics, climatic conditions, soil water interactions,
transport processes, wetdry cycles, biogeochemical cycles, microbial induced processes and
several other anthropogenic stresses [10]. Additional nutrients that could turn into fertilizer are
contained in sewage effluent, garbage, and other organic wastes [11]. Sewage sludge contains
nutrients equal to about 5% of the N, 12% of the P, and 1% of the K applied in commercial
fertilizers in the United States [12]. Significant quantities of micronutrients are also present in
the sludge, some them in chelated forms that help to protect their availability [11].
However it is also necessary to take into account before their application in soils as
amendments some problems they can cause. Wastes are susceptible to contain heavy metals
and other toxic elements, pathogens, extreme concentrations of nutrients, salinity and non-
biodegradable materials. The successful recovery of mine soils depends not only on the
appropriate selection of wastes but also on their suitable treatment [9].
The hypothesis of this work was that wastes made of sludge from a bleach plant, municipal
solid wastes (MSW), sewage sludge, biomass (wood chips) and wastes from agrifood industry
can increase the nutrient content in degraded settling pond soils. The effect of the addition of
waste amendments one the nutrient content of soil from a bare settling pond soil has been
studied.
Soil sampling
Soil sampling was located in the settling pond in Touro mine (NW Spain) (Lat/Lon (Datum
ETRS89): 820'12.06'' W 4252'46.18'' N). This settling pond was created during the decantation
of mud from the flotation of sulphurs during the extraction of copper. This process produces big
amounts of mud and acidic waters. In general, this mud is fine material that have been grinder
and floated and finally it was accumulated in the sedimentation or settling pond. Nowadays the
settling pond is emerged and dry and a thin soil is formed. There is hardly vegetation and to
promote it the company T.E.N. has added two different Technosols. They were added with
trucks and spread in the soil surface. There was not mixing with the soil. Samples from both
Technosols and from the original soil were taken:
- Soil without treatment (SB) was taken in an area without vegetation or amendment. The only
AC horizon over the C one was sampled. Five samples were taken to do a homogeneous
sample. The pooled sample was stored in a polyethylene bag. Soil profile was described
according to the FAO (2006) [5].
- T1 is an immature Technosol made of sludge from a bleach plant, municipal solid wastes
(MSW) and natural soil from the surroundings.
- T2 is a more elaborated Technosol (more maturing time) and sieved. It was made of sewage
sludge, biomass (wood chips) and wastes from agrifood industry. These wastes were mixed
with natural soil from the surroundings.
Pot experiment
A pot experiment was designed to evaluate the effect of both Technosols in the soil from the
settling pond. This experiment was carried out in a greenhouse over three months.
The original samples (SB, T1 and T2) were air dried and sieved through 2 mm. These samples
were introduced in pots in an 8:2 ratio soil:Technosol (SB+T1 or SB+T2). Technosols were put
on the topsoil but not mixed with the soil as T.E.N. company does in the field. Replicates of
each treatment were made in order to allow sampling every month without disturbing the
incubation. A Petri dish under each pot was used to collect the leachate water during the
experiment.
Pots with SB+T1 are named TR1 and those with SB+T2 are labelled as TR2. The experiment
was running during three months and three samples were taken at time 0, 1, 2 and 3 months.
Irrigation was applied three times per week. After sampling, samples were air dried and sieved
through 2 mm.
Methods
2+ 2+ +
Cation exchange capacity was determined [13] after extracting the cations (Ca , Mg , Na y
+
K ) with 0.1M BaCl2. Cations were determined in the extracts by ICP-AES (Perkin Elmer,
307
3+
Optima 4300DV). Al was extracted with 0.1M CaCl2 [14]. Effective cation exchange capacity
(CECe) was also calculated [15].
Humic and fulvic carbon (CHA and CFA) was extracted with 0.1M NaOH in a 1:20 soil:solution
ratio [16]. Carbon concentration in all the extracts was determined in a TOC equipment (TNM-1,
Shimadzu).
Nitrates, nitrites and ammonium were determined by the modified method of [17]. Nitrogen
mineralization rate was calculated following the method of [18].
All of the experiments were performed in triplicate and the data were statistically treated with
SPSS v. 19.0 for Windows. Analysis of variance (ANOVA) and test of homogeneity of variance
were carried out. In case of homogeneity, a least significant difference (LSD) test was carried
out as post-hoc. If there was no homogeneity, Dunnetts T3 test was performed.
RESULTS AND DISCUSION
Field samples: settling pond soil (SB) and Technosols (T1 and T2)
The soil sampled in the settling pond and the Technosols taken in the field have been analysed
before the pot experiment for exchangeable cations, CECe, humic and fulvic acids contents and
+ - -
N (NH4 and NO3 +NO2 ) (Table 1).
The soil from the settling pond (SB) had very low CECe compared to T1 and T2 and its
+
concentration of H was higher than the sum of its other cations (Table 1). In fact, SB had
-1
limiting factor e for plant development [20, 21] because its CECe was under 4 cmol(+) kg .
2+ + 2+ +
Concentrations of Ca , Na , Mg and K in T2 and T1 were significantly higher than in SB
(Table 1). SB had the limiting factor Ca due to its deficit in Ca for plant development [20, 21].
3+ +
Al and H were significantly higher in SB than T1 and T2. T2 was the Technosol that should
2+
supply higher amounts of base cations, especially Ca (Table 1).
According to [19] the lowest value of CEC to allow the establishment of vegetation is 8-10
-1
cmol(+) kg . CECe in SB is close to this limit (Table 1). The significantly (P < 0.05) higher values
in T1 and especially in T2 respect to SB indicate that both Technosols could help to recover this
soil.
Humic and fulvic acid contents were significantly (P < 0.05) higher in T2 (followed by T1) than in
SB (Table 1). The soil organic fraction and its dynamic properties influence a great number of
essential processes in soils: the biochemical cycles, the soil structure and the solubilisation of
nutrients [20]. The use of organic wastes as amendments could increase the organic C content
in SB. The presence of the organic fraction in the soil affects to basic soil properties such as
cationic exchange and buffer capacity [22].
Organic nitrogen compounds must turn into inorganic N to be taken up by plants. This inorganic
N comprises a low proportion of the total soil N. The main bioavailable forms of N are
+ - -
ammonium (NH4 ) and nitrate (NO3 ). Nitrites (NO2 ) are in the soil during short periods and
sometimes under specific conditions, they are as an intermediate form of N in microbiological
processes of N transformation.
T2 had the higher concentration of ammonium, nitrates and nitrites (P < 0.05) (Table 1). T1 had
more ammonium than SB (P < 0.05), but the same concentration of nitrites and nitrates (Table
1). Because of the higher amounts of inorganic N in both Technosols in comparison with SB,
these wastes could increase the low amount of this nutrient in the soil from the settling pond.
C/N ratio is considered as a good indicator to evaluate the quality of the humus in the soil. The
lower C/N, the better the quality of organic matter is. This ratio is around 10 in favourable cases
[23].
T1 and T2 had significantly (p < 0.05) higher C/N than SB (Table 1). C/N was around 10 in both
Technosols, which indicates a good proportion of both elements in these amendments [23].
Sample pots: effects of T1 and T2 on the settling pond soil (SB)
A pot experiment was carried out to evaluate the effect of both selected waste amendments (T1
and T2) in the mine soil (SB), as mentioned above.
Exchangeable cations contents changed over three months (P < 0.05) in the pots with both
+ 2+ 2+
types of wastes (TR1 and TR2) (Table 2). Na , Mg and Ca significantly (P < 0.05) increased
308
+ 2+ 2+
in TR1 after three months, but K decreased (Table 2). In the case of TR2, both Mg and Ca
+ +
significantly (P < 0.05) increased, but Na did not significantly changed and K decreased as
+
time elapsed. K contents also decreased in TR1 (Table 1). Both TR1 and TR2 increased the
+ 2+ 2+
concentration of Na , Mg and Ca in comparison with SB after three months. CECe increased
in both TR1 and TR2 after three months (Table 2) and also compared with SB sample (Tables 1
and 2). This is very important due to the extremely low CECe in SB (Table 1).
The percentage of base saturation (V) was above 50% in TR1 and TR2 over the three months
(data not shown). This could be due to the high content in basic cations in both Technosols
(Table 1). When the degree of saturation (V) is high, it is easier for plants the absorption of
cations (nutrients) than when V is low. When V is under 50% the exchangeable places are
+ 3+
occupied by H and Al .
CHA content significantly (P < 0.05) increased in TR1 after three months, but CFA content did not
significantly changed (Table 3). It can be observed an increase in C FA in the first and second
month, so it is possible that fulvic acids have been leached over experimental time. In the case
of TR2, both humic and fulvic acids significantly (P < 0.05) increased in three months (Table 3).
There was also an increase in CFA in the first and second month, as in the case of TR1 samples,
which is possibly due to the same reason. In any case, the addition of both Technosols
increased CFA and CHA in the original soil (Tables 1 and 3).
All forms of inorganic N (ammonium, nitrates and nitrites) significantly (P < 0.05) in TR1 after
three months (Table 3). Ammonium also increased in TR2, but nitrates and nitrites did not
significantly change their concentration with this treatment (Table 3). TR2 had higher
ammonium concentration after the three months than SB, but in TR1 the content was lower
(Tables 1 and 3). Nitrates and nitrites did not increase their concentration with any of the
treatments (Tables 1 and 2). This could indicate that T1 has not enough inorganic N content to
peak in the original soil and even T2 had enough ammonium it was scarce in nitrates and
nitrites.
C/N ratio significantly (P < 0.05) decreased in TR1 after three months (Table 3). This value did
not significantly change in TR2 (Table 3). This ratio was higher in both treatments than in the
untreated soil (SB) (Tables 1 and 3). Nevertheless, C/N in both TR1 and TR2 after three months
is under 10, which means deficit in carbon content [23].
CONCLUSIONS
Preliminary results from the pot experiment indicate that the use of Technosols can be
beneficial for plant growth.
They significantly increased the CECe of the mine soil, mainly because of their Ca and Mg
contents. Fulvic and humic acid contents also increased as time elapsed in both treatments as
well as inorganic nitrogen contents.
Periodic controls of the dosage as well as the nutrient levels in soil are advisable to reach
optimal conditions for plant growth.
Table 1. Properties of initial samples.

SB T1 T2
CECe 2.44 c 8.56 b 32.81 a
+
Na 0.05 c 2.92 b 4.17 a
2+
Mg 1.22 c 2.08 b 5.27 a
+ -1
K cmol(+)kg 0.21 c 0.64 b 5.67 a
Exchangeable cation 2+
Ca 0.13 c 2.92 b 17.7 a
3+
Al 0.83 u.l. u.l.
+
H 4.43 a 0.05 b 0.06 b
C in Humic Acids 55.8 c 1410 b 6464 a
C in Fulvic Acids 56.1 c 643 b 11075 a
+ -1
NH4 mg kg 41.56 c 190 b 1719 a
- -
NO3 + NO2 10.5 b 7.5 b 2646 a
C/N 0.64 c 7.55 b 11.31 a
Values of same parameter followed by different letters in each row differ significantly with P<0.05. u.l.:
undetectable level.
309
-1
Table 2. Change over time experiment (three months) of exchangeable cations cmol(+) kg and
effective cation exchange capacity in sample pots (TR1 and TR2).
+ 2+ + 2+ 3+ +
Time Na Mg K Ca Al H CECe
0 0.32 c 0.46 c 0.43 a 1.43 c 0.80 a 1.62 b 3.44 b
1 0.51 a 0.22 d 0.06 c 1.18 d 0.69 b 0.92 c 2.66 b
TR1
2 0.43 b 1.33 b 0.11 b 3.03 b 0.63 b 2.31 a 5.53 a
3 0.59 a 2.16 a 0.08 bc 3.32 a 0.78 ab 2.69 a 6.93 a
0 0.32 b 0.76 b 0.24 b 1.94 c 0.87 c 2.14 c 4.13 c
1 0.74 a 0.55 b 0.37 a 1.58 d 0.94 c 1.29 d 4.18 c
TR2
2 0.34 b 2.37 a 0.08 d 2.86 a 1.56 a 4.43 a 7.21 a
3 0.31 b 2.14 a 0.18 c 2.63 b 1.18 b 3.23 b 6.44 b
Values of same parameter followed by different letters in each column differ significantly with P<0.05
Table 3. Change over experimental time (three months) of humic and fulvic acids (CHA and CFA,
+ - - -1
respectively), ammonium (NH4 ), nitrates (NO3 ), nitrites (NO2 ) (mg kg ) and C/N ratio in
sample pots (TR1 and TR2).
+ - -
Time CFA CHA NH4 NO3 +NO2
C/N
(months) . -1
(mg kg )
0 44.2 c 36.3 c 7.71 c 3.69 b 35.17 a
1 175 a 539 a 20.54 b 8.2 ab 6.54 bc
TR1
2 135 b 265 b 57.06 a 11.12 a 14.35 b
3 118 c 286 b 23.59 b 10.07 a 1.08 c
0 766 c 1414 c 55.92 c 8.82 a 4.69 a
1 1295 a 3646 a 109 a 12.17 a 3.19 a
TR2
2 1002 ab 1771 b 106 ab 11.41 a 4.98 a
3 954 b 1953 b 84.36 b 11.91 a 4.27 a
Values of same parameter followed by different letters in each column differ significantly with P<0.05.
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311
REMEDIATION of HEAVY METAL-CONTAMINATED SOIL
N. Balkaya
Istanbul University, Faculty of Engineering, 34320 Avcilar-Istanbul, TURKEY;
e-mail: nbalkaya@istanbul.edu.tr
ABSTRACT
One of the most prominent inorganic contaminants in soils is heavy metals such as
cadmium, chromium, mercury, zinc and lead. Metals are not degradable and may
accumulate and concentrate in surface soils over time. Excess heavy metal accumulation
in soils is toxic to humans and other living things. Therefore, soils contaminated with
heavy metals must be removed and deposited in landfills, or remediated by various
techniques. Remediation technologies are many and varied. This paper provides a review
on remediation technologies of heavy metal-contaminated soil.
Keywords: Soil; heavy metals; pollution; remediation
INTRODUCTION
Nowadays, the metal pollution of soil has become a serious environmental problem all over the
world. It can arise from various human activities such as mining, metal processing and refinery
industries, and army activities. When metals are introduced into the environment, they contaminate
the surrounding environment and remain in the environment for a long time. They accumulate
because they don't biodegrade in the way many other substances do. These metals and metalloids
could pose adverse health and ecosystem impacts.
High levels of heavy metals in soil can also lead to the contamination of water supplies. Therefore,
sustainable, cost-effective, and efficient remediation strategies for treating soil are required [1, 2].
Nowadays, there is ongoing effort to remediate heavy metal polluted soil. Traditional techniques
often used to effect these remediation processes include; top soiling contaminated soil with
uncontaminated ones, stabilization of the polluting heavy metals to prevent leaching into ground
water, soil washing, and excavating top layers of polluted soil amongs others [3].
This present review focuses on the soil remediation technologies for heavy metal contamination,
including solidification/stabilization, soil washing, soil flushing, electrokinetic remediation, extraction
of metals by microbiological means, vitrification, and phytoremediation.
Remediation of heavy metal-contaminated soils

When a large area of soil is contaminated, treatment of the soil by means of traditional methods
results in a substantially high cost. Treatment of soils can be either in-situ (on site), or ex-situ
(removed and transferred off-site), either of which is extremely expensive. Some treatment
methods include high-temperature treatments (produce a vitrified, granular, non-leachable
material), solidifying agents (produce cement-like material), and washing process (leaches out
contaminants) [4].
As stated by Mulligan et al. [5], the site characteristics, concentration, types of pollutants to be
removed, and the end use of the contaminated medium should be considered while selecting the
most appropriate soil remediation method. Therefore, choosing an adequate remediation technique
in accordance with the site characteristics, types and concentration of pollutants and the further
312
use of the contaminated soil is necessary to limit the risk of polluted soils to organisms and for
reclamation of the contaminated site [6]. The basic criterion in selecting a proper remediation
strategy for a contaminated site is to choose the least expensive applicable method to comply with
the regulatory requirements for the protection of the environment and public health. The chosen
method should neither add other toxic pollutants nor leave toxic residues, which must be
subsequently removed [7].
The methods used for the remediation of heavy metal-contaminated soils include
solidification/stabilization, soil washing and soil flushing, electrokinetic remediation, extraction of
metals by microbiological means, phytoremediation, and vitrification. These methods are
disscussed below, respectively.
Solidification/stabilization
Various chemical additives (Portland cement, kiln dust and fly ash) in solidification/stabilization
technique are used to chemically bind and immobilize contaminants or to micro-encapsulate them
in a matrix that physically prevents mobility. Solidification/stabilization can be done in-situ or ex-situ
[8]. High clay and moisture contents and debris can effect the efficiency of the
solidification/stabilization processes [5]. In this method, the heavy metal combines with the added
chemical to create a less toxic compound while it remains in the soil in a less harmful form.
Therefore, this process does not disrupt the environment or generate hazardous wastes [9].
As a result of their simplicity, but high effectiveness, in-situ applicability and low cost, stabilization
and immobilization of metals in soil are very promising [10]. It can be said that in-situ immobilization
creates new chemical compounds in which heavy metals are much less available to living things.
Compared to excavating and disposing contaminated soils elsewhere, this on-site clean-up is less
disruptive to peoples lives and to the environment [9].
Soil washing and soil flushing

Soil washing is defined as a method of transferring contaminants from the soil solid phase to the
aqueous phase by dissolving or suspending them with some chelating agents or acid solutions, or
concentrating them into a small volume of soil via separating them from sand fractions [11]. The
main parameters affecting soil washing include the mode of extraction (leaching or washing),
extraction type and concentration, solution pH, electrolyte, liquid/soil ratio (mL/g), and retention
time [12]. Soil washing has demonstrated potential effectiveness in treating heavy metals in the soil
matrix. Like soil washing, soil flushing is also known to be an efficient method in removing heavy
metals from the soils. However, a shortcoming of soil washing is that, it cannot reduce the toxicity
of the heavy metals [13].
Removal efficiency of soil flushing depends on soil pH, soil type, cation exchange capacity, particle
size, permeabilities and contaminants. High clay and organic matter contents are particularly
detrimental [5]. Due to the low hydraulic conductivity of fine-grained soils, the remediation of such
soils contaminated with heavy metals by conventional methods such as in-situ flushing has been
found to be very costly and mostly ineffective [14].
The difference between the two methods is that soil washing is an ex-situ process, whereas the soil
flushing is an in-situ process in which additional force is used to make the solution penetrate
through the ground and into the trenches or collecting wells. Although soil washing (ex-situ) is the
most commonly or preferred alternative over the in-situ approach, both methods requires extensive
site preparation, equipment mobilization, soil handling, and huge volume of water to be treated
[15]. The cost of soil washing and soil flushing is 25-300 and 100-200 $US/ton, respectively [5].
Electrokinetic remediation
Electrokinetic soil processing is a new, innovative and cost-effective remediation technology
[16,17]. If heavy metal ions can be accumulated at the limited area of soil, it may become an
alternative technology [18]. In this cleanup technology, electrodes are implanted in the soil, and a
direct current is imposed between the electrodes, allowing the charged particles in the soil water to
migrate to the oppositely charged electrode [19,20]. This technology has shown considerable
313
potential for efficient and effective removal of inorganic contaminants from fine-grained soils of low
hydraulic conductivity and large specific area when conditions are favorable [20]. Electrokinetic
remediation is one of the developing techniques that has significant potential for in-situ remediation
of the fine grained soils [14].
The efficiency of removing contaminants from soils depends on chemical processes at the
electrodes, the water content of the soil, soil type and structure, saturation of the soil, pH and pH
gradients, type and concentration of chemicals in the soil, applied current density, and sample
conditioning. The removal rates of heavy metal contaminants may be influenced by different
physicochemical properties of the soil as a result of changed pH values, hydrolysis, oxidation and
reduction reaction patterns [13]. Higher currents and longer processing periods, which will require
higher energy expenditure and increased remediation costs, are necessary in order to clean-up the
soils with high sorption capacity, such as illitic soils [21].
The yield and universal application of this technology still requires improvement. However,
promising and useful results have obtained on-site specific projects, in which other methods failed
[15].
Extraction of metals by microbiological means

The main methods for the extraction of metals by microbiological means are bioleaching and
oxidation/reduction reactions. Since soils have already been exposed to oxidizing conditions, they
require lower pH values to extract the metals. Bacteria and sulfur compounds are added for both
heap leaching and reactors [5]. The bacteria commonly used in the bioleaching process are found
to be genus Acidithiobacillus or Thiobacillus, such as Acidithiobacillus ferrooxidans,
Acidithiobacillus thiooxidans and Thiobacillus thioparus [22]. Some species of heterotrophic micro-
organisms, such as Aspergillus and Penicillium, have shown potential for metal bioleaching [23].
Bioleaching is a simple [24] and effective [24,25] technology. It is considered as a low-cost and
environmentally-friendly approach for the remediation of metal-contaminated soils [25,26]. Besides,
it has operational flexibility [26]. Although bioleaching like phytoremediation offer economical
solution, both methods are climate dependent, and the process rate and yield of recovery require
significant improvement [15].
Vitrification
Vitrification is a solidification/stabilization processing that requires thermal energy, and is suitable
for contamination in shallow depths. The efficiency of the process can be affected by high clay and
moisture contents and debris [5]. It involves the conversion of contaminated soil in a stable and
homogeneous (silicate) glass through a thermal treatment of fusion [27].
In this process, the mobility of metal contaminants can be decreased by high-temperature

treatment of the contaminated area that results in the formation of vitreous material, which is
usually an oxide solid. During the vitrification process, the increased temperature may also cause
the volatilization of volatile metal species (such as Hg) that must be collected for treatment or
disposal. Although in-situ processes are preferred due to the lower energy requirements and cost,
vitrification may be performed ex-situ or in-situ [28]. Cost of vitrification is 400-870 $US/ton [5].
Phytoremediation
Phytoremediation is defined as the engineered use of plants in-situ and ex-situ for environmental
remediation [29-30]. Wetlands are often considered sinks for contaminants, and there are many
cases in which wetland plants are utilized for removal of metals. Marshes have been proposed as
sites for phytoremediation of metals [31]. Trees potentially are the lowest-cost plant type to use for
phytoremediation [32]. Plants such as Thlaspi, Urtica, Chenopodium, Polygonum sachalase and
Alyssim have the capability to accumulate cadmium, copper, lead, nickel and zinc [33]. Since crop
plants are easily cultivated, relatively fast growing and the biomass production is much greater
compared to most of the hyperaccumulators, it was revealed that the strategy of using to use crop
plants for phytoremediation is a promising approach [34].
314
The three mechanisms used to stabilize or remove metals from soil are phytoextraction,
rhizofiltration, and phytostabilization [4]. However, phytoextraction and phytostabilization are known
to be the two important techniques that may be used to remediate heavy metal contaminated soils
[35]. Phytoextraction of heavy metal contaminated soils is a promising remediation technology [36]
which refers to the use of pollutant-accumulating plants that can extract and translocate
contaminants to the harvestable parts of roots and above-ground shoots [30,37]. Plants used for
phytoextraction may accumulate high concentrations of metals. Phytoextraction allows for in-situ
treatment. It does not generate liquid wastes and keeps soil properties intact [38].
The ideal plant for use in phytoextraction should have the ability to accumulate the metal(s)
intended to be extracted, preferably in the above-ground parts; tolerance to high metal
concentrations in soils; fast growth and high-accumulating biomass; and easily grown as an
agricultural crop and fully harvestable [37]. The wide extension of the contaminated area and the
low contamination depth makes phytoextraction a valuable cost-effective alternative to traditional
disruptive technologies [39]. The efficiency of phytoextraction is determined by the soil
characteristics such as pH, organic matter content and clay content [40]. To solubilize the metals
for enhanced phytoextraction, chelating agents that enhance metal accumulation in high biomass
producing crops are added to soil [41,42]. Addition of chelates is advocated for enhancing the
clean-up of soil contaminated by heavy metals [43].
Contrary to phytoextraction, in which hyperaccumulators may be used to remove metals from the
soil and concentrate them in above ground tissues, plants are used to immobilize metals and store
them below ground in roots and/or soil in phytostabilization [31].
The potential benefits of phytoremediation are low capital costs, aesthetically pleasing techniques,
minimization of leaching of contaminants, and soil stabilization. The operational cost of
phytoremediation is also substantially less than that of conventional treatments and involves mainly
fertilization and watering for maintenance of plant growth [29,44]. This emerging technology may
offer a cost-effective, non-intrusive and safe alternative to conventional soil clean-up techniques
[45]. Furthermore, since the contaminated site is covered by plants during phytoremediation, wind
and water erosion will be reduced [44]. However, vegetation that absorbs toxic heavy metals, that
may pose a risk to wildlife, have to be harvested and managed as a waste [29,44]. Fences, or other
ways to limit access to people and animals, and the disposal of plant matter as special waste, are
sometimes necessary [9]. Drying, incineration, gasification, pyrolysis, acid extractions, anaerobic
digestion, extraction of the oil, chlorophyll fibers from the plants can be used for this purpose [46].
Phytoremediation is a time-consuming process since it can take several growing seasons, or even
years, for contaminant concentrations to reach regulatory levels. In addition, the shutdown of plant
activity during winter months and the seasonal variation of plant metabolic activity is a handicap for
application of phytoremediation in colder climates. However, that contaminants present below
rooting depth will not be treated or extracted and that the plant or tree may not be able to grow in
soils at heavily-contaminated sites due to plant toxicity may be considered as other limitations of
phytoremediation [29,44]. Besides, this method is limited to shallow depths of contamination [5].
Phytoremediation as a soil remediation technology is only feasible when the produced biomass can
be valorized [42]. The cost of phytoremedation is 50000-200000 $US/acre [5].
CONCLUSIONS
Nowadays, there are several techniques used for remediation of heavy metal contaminated soil,
some of which are attracted increased interest among scientists and industry officials. However,
none of these techniques are completely accepted as the best treatment option. New clean-up
technologies on contaminated soils are still being investigated and tested for remediation of
contaminated sites with heavy metals.
Indeed, since cleaning contaminated soils is extremely expensive and difficult, preventing heavy
metal pollution is critical [4]. Consequently, it can be said that the best method to protect the
environment from contamination by heavy metals is prevention.
315
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BIODEGRADATION OF PAH POLLUTED SOIL BY FUNGI GROWN IN AN

AGROINDUSTRIAL SUPPORT
Rosales, E. Prez-Paz, A., Pazos, M. and Sanromn, M.A.

Dpt. Chemical Engineering, University of Vigo, Campus As Lagoas, Marcosende 36310, Vigo,
Spain. email: emiliorv@uvigo.es
ABSTRACT
Soils contaminated with PAHs have risks to human and ecological health. Different in situ
techniques have been developed to treat a contaminated soil: phytoremediation,
electrokinetic remediation, solvent extraction, chemical oxidation, thermal technologies
and bioremediation. One of the more promising techniques is bioremediation.
The aim of the present work has been to investigate the potential of orange peelings as
raw material for the production of laccase by T.versicolor and P. ostreatus under solid
state fermentation. Moreover, solid state fermentation studies to screening the potential
PAHs (phenanthrene and pyrene) degradation abilities of fungi have been done. Finally,
based on the papers described above; in this study, we have sought to determine the
technical feasibility of using spent fungi substrate from solid state fermentation to degrade
pyrene polluted soil.
The results obtained clearly show the superiority of orange peeling for laccase production
over inert support. Moreover, the high biodegradation of phenanthrene and pyrene by
whole fungal cultures during solid state fermentation has been demonstrated. Finally, the
spent fungus substrate obtained in solid state fermentation has been was to the
phenanthrene soil bioremediation. These materials provide carbon source to maintain
growth and induce enzymatic complex. The pyrene decontamination achieved in soils
was around 43% after 30 days. It is demonstrated that orange peelings are appropriate
for laccase production in solid state fermentation and the spend P.ostreatus substrate
could be used on bioremediation of polluted soils.
Keywords: Phenanthrene, Pleurotus ostreatus, pyrene, solid state fermentation, Trametes

versicolor
INTRODUCTION
Due to increased industrialisation and manufacturing processes, elevated amounts of organic

pollutants are released into the environment. The permanence of organic compounds inside the
soil depends on the type and characteristics of the pollutant as well as the properties of the solid
matrix. Some organic pollutants can be degraded inside the soil by indigenous microorganisms [1].
However, hydrophobic organic contaminants (HOC) comprise a large group of toxic and persistent
contaminants that are not suitable to be treated by natural attenuation. The low solubility of these
compounds hinders their accessibility to microorganisms for biodegradation. A well-known group of
these pollutants is polycyclic aromatic hydrocarbons (PAHs), a class of organic substances
consisting of two or more fused benzene rings made up of carbon and hydrogen atoms. These
compounds are formed during the thermal decomposition and subsequent recombination of
organic molecules. They exhibit recalcitrant and strong mutagenic/carcinogenic properties to living
beings [2].
Laccases (benzenodiol:oxygen oxidoreductases; EC 1.10.3.2) are extracellular enzymes produced
mainly by the genus Trametes. Several white-rot fungus T. versicolor and P. ostreatus have been
selected to perform the present study, since they have been recently described as good producers
of laccase. Recently, the biotechnological importance of this enzyme has been underlined [3] due
318
to its ability to oxidise both phenolic and non-phenolic lignin related compounds [4], as well as
highly recalcitrant environmental pollutants [5,6]. This makes this enzyme the ideal candidate for
the treatment of PAHs.
Most studies dealing with ligninolytic enzymes have been performed in submerged conditions
despite these fungi grow in nature in solid-state conditions. Solid-state fermentation was chosen
here for the production of laccase because it mimics the natural environment of the white-rot fungi
(wood). In addition, this technique allows the utilisation of diverse agroindustrial wastes as a
support-substrate, making the process more economical and ecological [7].
The selection of a substrate for solid state fermentation process depends upon several factors
mainly related with cost and availability. Thus, recently it has been an increasing trend towards the
utilisation of agro-industrial wastes as raw materials to produce value-added products by this
technique. The wastes generated by food processing industries like fruit peelings are a good
example of this kind of materials. Thus, the production of orange and other citrus juices generates
vast quantities of processing by-products, mainly peels, cores and segment membranes. These by-
products are not very useful as cattle feed, since their content in protein is rather low. However,
they are rich in both soluble and insoluble carbohydrates, making them an attractive raw material
for the production of value-added products. In addition, the utilisation of this kind of supports helps
in solving both the economic and the environmental problems caused by their disposal [8].
Among the different existing wastes from the alimentary industry, orange-wastes, a common by-
product from the orange and other citrus juices industry, are especially suitable for the production
of laccase [8]. Moreover, these agroindustrial wastes could be used as soil nutrient. Correia
Guerrero et al. [9], Van Heerden et al. [10] and Tuttobene et al. [11] have reported the re-use of
industrial orange wastes as organic soil fertilizers and as low-cost technology for the recycling
nutrients contained in these wastes.
The aim of the present work has been to investigate the potential of orange peelings as raw
material for the production of laccase by T.versicolor and P. ostreatus under solid state
fermentation. Moreover, solid state fermentation studies to screening the potential degradation
PAHs (phenanthrene and pyrene) abilities of fungi have been done. Finally, based on the papers
described above; in this work, the utility of the spent fungi substrate from solid state fermentation to
degrade PAHs polluted soil has been evaluated
Microorganisms
Pleurotus ostreatus f. florida (CECT 20600) and Trametes versicolor (CECT 20148) were obtained
from the Spanish Type Culture Collection of the University of Valencia.
Pleurotus ostreatus f. florida was mantained at 4C on a culture medium containing 20 g/L malt
extract, 20 g/L glucose, 1 g/L mycopeptone and 15 g/L agar powder.
Trametes versicolor was maintained on potato dextrose agar (PDA) plates at 4 C and sub-cultured
every three months.
Medium
The composition of the culture medium was according to Moldes et al. [12]. The basal medium
containing per liter: 4 g glucose, 15 g yeast extract, 0.75 g NH 4Cl, 2 g KH2PO4, 0.5 g MgSO47H2O,
0.1 g CaCl22H2O, 0.5 g KCl and 20 mM acetate buffer (pH 4.5). The vitamin solution contained per
liter 0.2 g thiamine. Basal medium was sterilized at 121 C for 20 min. After cooling, the vitamin
previously sterilized by microfiltration (0.22 m), were added to the basal medium. Cultures were
supplemented with laccase-inducing compounds (Cu 5 mM) at the beginning of cultivation [8].
Support
Cubes of polyurethane foam (edge size 0.5 cm; characteristics: density, 20 Kg/m; surface area,
2 3
41410 m /m ) were used as inert supports. Prior to use, the cubes were washed once in methanol
and three times in distilled water, then they were dried at room temperature overnight.
Orange peelings were triturated and employed as support-substrates (size 5 mm). Orange peelings
are mainly composed of both soluble and insoluble carbohydrates. The soluble sugars in orange
peel are glucose, fructose and sucrose. The insoluble polysaccharides in cell walls of orange peel
are composed of pectin, cellulose and hemicellulose. They also contain minor amounts of organic
319
acids, mainly citric, malic, malonic and oxalic, proteins, mineral ions, phenolic compounds and
polyols. Orange peelings were pretreated according to [13].
Inoculation
Inoculation of solid state fermentation was carried out directly in the Erlenmeyer flasks. Three agar
plugs (diameter, 3 mm), from an actively growing fungus on plate, were used per Erlenmeyer as
inoculum. The Erlenmeyer flasks were incubated statically under an air atmosphere at 30C and
90% humidity, to avoid evaporation, in complete darkness.
Solid state cultures

The solid state cultures were performed in cotton-plugged Erlenmeyer flasks (250 ml) containing
1.5 g of crushed orange peelings or cubes of polyurethane foam depending on the experiment and
15 mL of culture medium.
In vivo degradation of phenanthrene and pyrene

Phenanthrene and pyrene were purchased from Sigma Aldrich (Table1). These PAHs were added
to ten-day-old solid-state cultures, as an aqueous solution (1% Tween 80 and 5 mM acetone), at
final concentration of 100 M. Samples in the liquid medium were taken immediately after PAHs
addition and every two or three days thereafter.
Table 1.- Properties and chemical structures of the studied PAHs

Name/Pollutant Chemical structure CAS Molecular Solubility in
Weight water
[g/mol] [mg/L]
Phenanthrene 85-01-8 178.2 1.20
Pyrene 129-00-0 202.3 0.077
Polluted soil
Soil samples were prepared by mixing real soil with pyrene solution (completely dissolved in
hexane). The resultant soil-hexane-pyrene mixture was placed in a ventilation hood for 9 days until
the hexane completely evaporated. An initial concentration around 430 mg/kg of dried soil was
obtained.
Soil biodegradation
Biodegradation studies were performed in 250-ml flasks in triplicate. Each flask contained 10 g
contaminated soil with the spent fungi and substrate from solid state culture. The flasks were
incubated in static conditions at 30 C, with a pH of 5 for up to 4 weeks. An abiotic control without
fungus was carried out in parallel.
Laccase activity measure

Laccase activity was determined in the culture medium spectrophotometrically by the method of
Niku-Paavola et al. [14] with ABTS (2, 2-azino-di-[3-ethyl-benzothiazoline-(6)-sulphonic acid],
Boehringer) as substrate. The laccase reaction mixture (in a total volume of 3 ml) contained 2.3 ml
enzyme diluted to buffer (25 mM succinic acid, pH 3.0) and 0.7 ml 20 mM ABTS. The reaction was
monitored at room temperature by measuring the change in A 436 for 2 min. One activity unit was
defined as the amount of enzyme that oxidized 1 mol of ABTS per minute and the activities were
reported as U/L.
320
PAHs extraction and measure
The PAHs was extracted from the soil samples by a pressurized solvent extraction system using an
OnePSE instrument (Applied Separations Inc.). Dry soil was thoroughly mixed with pelletized
diatomaceous earth. When a free-flowing powder was obtained, it was placed into an extraction
vessel in the instrument. The extraction solution was composed of acetone/hexane (1:1, v/v). After
four cycles of 5 minutes at 110C and 100 bar, the extraction was complete and the collected
sample was used to determine the PAHs concentration by HPLC. Pressurized solvent extraction
can be used to replace soxhlet and sonication techniques and has been approved for use,
following EPA Method 3545A.
The PAHs concentration in liquid medium was determined by HPLC (Agilent 1100) equipped with
an XDB-C8 reverse-phase column (1504.6 mm i.d., 5 m). Prior to injection, the samples were
filtered through a 0.45-m Teflon filter. The injection volume was set at 5 l, and the isocratic
eluent (60:40 acetonitrile/water) was pumped at a rate of 1 ml/min for 10 min. Detection was
performed with a diode array detector from 200 to 400 nm, and the column temperature was
maintained at 20C.
As shown in table 2, the results obtained clearly showed the superiority of orange peeling for
laccase production over polyurethane foam. Orange peeling cultures led to laccase activities 50-
fold higher than those attained by polyurethane foam ones. This is likely due to the cellulose
content of this support, which acts as an activator of laccase activity [8].
Table 2.- Laccase production in all solid state cultures tested
Fungus+support Maximun laccase Productivity

[U/L] [U/L d]
T.versicolor + Polyurethane foam 45.19 9.04

T.versicolor + Orange peelings 3136.22 261.35
P. ostreatus + Polyurethane foam 49.41 8.24
P. ostreatus + Orange peelings 2798.20 233.18
Moreover, the biodegradation of phenanthrene and pyrene by whole fungal cultures during solid
state fermentation were studied. Phenanthrene and pyrene were added to 10 days old cultures at
final concentration of 100 M. As shown in figure 1a and b, in T. versicolor cultures, the maximum
phenanthrene removal rate was observed at the initial time.
1,0
0,8
Phenanthrene degradation
0,6
0,4
0,2
P. ostreatus
T. versicolor
0,0
0 50 100 150 200 250 300
Time (hours)
Figure 1a.- T. versicolor and P. ostreatus degradation of phenanthrene.
321
This removal time coincided with the increasing of the values of enzymatic activity obtained in
these cultures, in which the laccase peaks occurred after 12 days. When pyrene was added, the
degradation rate was slower; however the initial concentration of pyrene was reduced around the
80% after 11 days of culture. On the other hand, similar profiles were obtained when phenanthrene
and pyrene was added to solid state cultures of P. ostreatus, exhibiting removals of 91% to 95%,
respectively after only 11 days of incubation.
th
In a second stage, the PAHs were added on the 12 day at the same final concentration. Similar
behaviour was detected, although in all cases the degradation rate was rather low. The best results
were obtained in P. ostreatus cultures, reaching values higher of 90% in 10 days. Therefore, this
shows the high potential of P. ostreatus to degrade these pollutants.
1,0
0,8
Pyrene degradation
0,6
0,4
0,2
P. ostreatus
T. versicolor
0,0
0 50 100 150 200 250 300
Time (hours)
Figure 1b.- T. versicolor and P. ostreatus degradation of pyrene.
Afterwards, the spent fungus substrate obtained in solid state cultures was used to the pyrene soil
bioremediation. These materials provide carbon source to maintain growth and induce enzymatic
complex. Moreover, this waste can be used as biofertilizer. The decontamination achieved in soils
was around 43% after 30 days. It is demonstrated that orange peelings are appropriate for laccase
production in solid state cultures and the spend P.ostreatus substrate could be used on
bioremediation of polluted soils.
0,6
0,5
Pyrene soil degradation (C/C 0)
0,4
0,3
0,2
0,1
0,0
0 5 10 15 20 25 30 35
Time (days)
Figure 2.- Pyrene polluted soil bioremediation
322
CONCLUSIONS
The aforementioned results obtained in this research showed the enormous potential of orange
peelings as support-substrate for the production of laccase, under solid state conditions. Moreover,
it is demonstrated the ability of both fungi to degrade several PAHs such as phenanthrene and
pyrene.
In this work the application of wastes obtained in solid state cultures to remediation of polluted soil
have been demonstrated. Nevertheless, more studies must be done in order to confirm the use of
spent fungus-substrate in several environmental applications.
Acknowledgements
References
[1] S.V. Mohan, T. Kisa, T. Ohkuma, R.A. Kanaly, Y. Shimizu, Bioremediation technologies for
treatment of PAH-contaminated soil and strategies to enhance process efficiency,
Rev.Environ.Sci.Biotechnol. 5 (2006) 347-374.
[2] K.L. White Jr., An overview of immunotoxicology and carcinogenic aromatic hydrocarbons, J.
Environ. Sci. Health Part C Environ. Carcinog. Rev. 4 (1986) 163-202.
[3] S. Ryan, W. Schnitzhofer, T. Tzanov, A. Cavaco-Paulo, G.M. Gbitz, An acid-stable laccase
from Sclerotium rolfsii with potential for wool dye decolourization, Enzyme Microb.Technol. 33
(2003) 766-774.
[4] R. Bourbonnais, M.G. Paice, Oxidation of non-phenolic substrates. An expended role for
laccase in lignin biodegradation, FEBS Lett. 267 (1990) 99-102.
[5] J.A. Field, E. De Jong, G. Feijoo-Costa, J.A.M. De Bont, Screening for ligninolytic fungi
applicable to the biodegradation of xenobiotics, Trends Biotechnol. 11 (1993) 44-49.
[6] S.B. Pointing, Feasibility of bioremediation by white-rot fungi, Appl. Microbiol. Biotechnol. 57
(2001) 20-33.
[7] S. Rodrguez Couto, M.A. Sanromn, Application of solid-state fermentation to food industry-A
review, J. Food Eng. 76 (2006) 291-302.
[8] E. Rosales, S. Rodrguez Couto, M.A. Sanromn, Increased laccase production by Trametes
hirsuta grown on ground orange peelings, Enzyme Microb. Technol. 40 (2007) 1286-1290.
[9] C. Correia Guerrero, J. Carrasco de Brito, N. Lapa, J.F. Santos Oliveira, Re-use of industrial
orange wastes as organic fertilizers, Bioresour. Technol. 53 (1995) 43-51.
[10] I. Van Heerden, C. Cronj, S.H. Swart, J.M. Kotz, Microbial, chemical and physical aspects of
citrus waste composting, Bioresour. Technol. 81 (2002) 71-76.
[11] R. Tuttobene, G. Avola, F. Gresta, V. Abbate, Industrial orange waste as organic fertilizer in
durum wheat, Agron. Sustainable Dev. 29 (2009) 557-563.
[12] D. Moldes, P.P. Gallego, S. Rodrguez Couto, A. Sanromn, Grape seeds: The best
lignocellulosic waste to produce laccase by solid state cultures of Trametes hirsuta , Biotechnol.
Lett. 25 (2003) 491-495.
[13] E. Rosales, S. Rodrguez Couto, A. Sanromn, New uses of food waste: Application to laccase
production by Trametes hirsuta , Biotechnol. Lett. 24 (2002) 701-704.
[14] M.L. Niku-Paavola, L. Raaska, M. Itvaara, Detection of white-rot fungi by a non-toxic stain,
Mycol. Res. 94 (1991) 27-31.
323
BIOSORPTION OF HEAVY METAL AND DYES: A PROMISING

TECHNOLOGY LEATHER WASTEWATER TREATMENT
1 1 1 2
E. Rosales , M. Pazos , M.A. Sanromn and T. Tavares
1 Dpt. Chemical Engineering, University of Vigo, Campus As Lagoas, Marcosende 36310, Vigo
Spain email: emiliorv@uvigo.es, mcurras@uvigo.es, sanroman@uvigo.es
2 IBB Instituto de Biotecnologia e Bioengenharia, Centro de Engenharia Biolgica, Universidade
do Minho, Campus de Gualtar, 4710-057 Braga, Portugal email: ttavares@deb.uminho.pt
ABSTRACT
The presence of dyes and heavy metals is usual in industrial processes like chrome
tanning in tannery industry and their removal may be an environmental problem. Different
techniques were developed and applied for the treatment of dyes and heavy metals in
effluents. Among them, adsorption showed to be an economic, simple operation and an
effective technique. Zeolites have a strong affinity for cations of transition metals, but only
little affinity for anions and non-polar organic molecules. The application of a zeolite to
heavy metal removal may be improved by the presence of microorganisms. The aim of
this work is the treatment of an effluent containing dyes and toxic metals. Several
operation parameters such as pH, concentration and kinetic behavior were studied. This
innovative process for treating dyes and heavy metal effluents showed that the zeolite-
biomass system is able to perform the removal of a combination of Azure B and
chromium(VI). A mixture of dye and metal solutions was treated reaching a removal
higher than 50% in the case of chromium (VI) and higher than 99% for dye, in 8 days.
Keywords: Azure B, chromium, biosorption
INTRODUCTION
Industrial processes like chrome tanning of tannery industry use dyes and heavy metals and their
removal may be an environmental problem. These industrial processes are based on chemical
processes involving several organic and inorganic compounds such as: acids, chromium salts,
dyes, auxiliaries and other chemical additives [1]. Direct discharge of dye effluents can cause
serious problems to the environment due to their high organic loading, toxicity and aesthetic
pollution related to colour. Another environmental problem is the presence of heavy metals in the
effluent. Under certain environmental conditions, they may accumulate to toxic levels and cause
ecological damage.
Different techniques were developed and applied for the treatment of dyes and/or heavy metals in
effluents. Among them, adsorption showed to be an economic, simple operation and an effective
technique. Nowadays, the use of clay materials is being investigated by their cost and potential for
ion exchange. Zeolites have a strong affinity for cations of transition metals, but only little affinity for
anions and non-polar organic molecules [2]. The application of a zeolite to heavy metal removal
may be improved by the presence of microorganisms.
The aim of this work is the treatment of an effluent which contains dyes and toxic metals such as
Azure B and chromium (VI). In previous reports, the chromium removal by an adsorption process
has been studied and prior to study the mixture pollutants, it is necessary to know the
characteristics of the adsorption process behaviour when the effluent contains a dye as pollutant.
Therefore, in this work a sequential study has been proposed. Initially, the adsorption process of
Azure B dye in zeolite has been studied. Furthermore, a low-cost system combining the biosorption
properties of a microorganism with the ion-exchange properties of a zeolite has been developed to
remove simultaneously the chromium and dye from the effluent. This innovative process combines
324
the reduction of chromium (VI) to chromium (III) by the bacterium A. viscosus with adsorption of the
dye and chromium in a zeolite.
Dye
Dye solutions were prepared with Azure B purchased from Aldrich (CAS Number 531-55-5).
Aqueous solutions were prepared according to the experiments in concentrations between 1.5-
2500 mg/L.
Metal
Chromium solutions were prepared by diluting K2Cr2O7 (Riedel-de Haen) in distillated water.
Zeolite
2
NaY zeolite (relationship Si/Al 2.83, BET area 700 m /g) was used as support. Prior to use, the
faujasite zeolite NaY (Zeolyst International) was pre-treated by calcination at 500 C during 8 h
under a dry air stream.
Microorganism
A. viscosus was obtained from the Spanish Type Culture Collection of the University of Valencia. A
medium with 10 g/L of glucose, 5 g/L of peptone, 3 g/L of malt extract and 3 g/L of yeast extract
was used for growth and maintenance of the microorganism.
Dye batch adsorption

Erlenmeyer flasks (250 mL) containing 1 g of zeolite in 150 mL of different Azure B solutions were
employed. Isotherm studies were made with concentration solutions of Azure B between 1.5-2500
mg/L. Kinetic studies were made at a concentration of 10 mg/L for 15 minutes.
To study the effect of pH on dye removal, pH values range from 2 to 7.5. The solution pH was
regularly maintained at the desired value using H 2SO4 or NaOH (0.1 M) solutions.
All the experiments were performed in a rotary shaker at 150 rpm and 28C.
Batch biosorption
A. viscosus biofilm formation was prepared according to Quintelas and Tavares [3]. Bacterium was
harvested during the exponential phase of the growth curve. The experiments were performed with
250 mL Erlenmeyer flasks containing 1 g of zeolite covered with biofilm (bacterium concentration 5
g/L) and 150 mL of the different solutions mixture of dye and chromium at concentrations: 100
mg/L chromium with 100, 150, 300, 450, 600 mg/L of dye. All biosorption experiments were
performed in a rotary shaker at 150 rpm, temperature 28C.
Samples of 1 mL were taken, centrifuged and analysed for dye and chromium determination.
These experiments were performed twice, being the experimental error margin below 3%.
Azure B determination
The dye content was measured spectrophotometrically (T60 UV Visible, PG Instruments) in the
supernatant based on the constructed calibration curves at maximum absorption wavelength (648
nm). The sample was diluted with distilled water if the absorbance exceeded the range of
calibration curve.
Chromium determination
Hexavalent chromium was quantified by measuring absorbance at 540 nm of the purple complex of
chromium (VI) with 1,5-diphenylcarbazide in acidic solution (T60 UV Visible, PG Instruments). For
total chromium determination, the chromium (III) was first oxidized to chromium (VI) at high
temperature by the addition of an excess of potassium permanganate previous to the reaction with
1,5-diphenylcarbazide. The chromium (III) concentration was calculated by the difference between
the total chromium and chromium (VI) concentration.
Azure B and chromium adsorption uptake and removal percentages
325
The amount of dye or chromium adsorbed and the percentages of removal were calculated using
the following equations:
q = (Ci - Cf)V / M (1)

D = 100(Ci - Cf) / Ci (2)
where q is the dye uptake (mg/g); Ci and Cf the initial concentration and the concentration through
time in the solution (mg/L) respectively; V is the solution volume (L); M is the mass of adsorbent (g)
and D the percentage of dye or chromium removal (%).
Azure B adsorption. Effect of pH and Azure B concentration

Initially the effect of the solution pH on the Azure B adsorption capacity of the zeolite was studied.
The work was done at the pH values of 2, 4, 6 and 7.5 in order to obtain adsorption equilibrium
data. In all cases, adsorption showed a linear rising with instantaneous uptake followed by a
stationary state and the dye uptake profiles were high with values from 1.30 to 1.42 mg dye/gzeolite.
The best results, obtained at pH 4, may be related to the surface charge density decreasing with an
increase in the solution pH. Therefore, the electrostatic repulsion between the positively charged
dye and the surface of adsorbents is lowered, which may result in an increase in the extent of
adsorption. The low uptake value obtained at pH 6 and 7.5 can be explained by a greater
-
concentration of the OH in the system which makes a competitive reaction with the zeolite.
The effect of the Azure B concentration on zeolite adsorption was investigated under the
equilibrium conditions at pH 4. As shown in Fig.1, when the dye concentration was among 10-120
mg/L the dye removal percentages were nearly constant (98.26-99.33%). The maximum removal
percentage was 99.33% obtained with 60 mg/L of Azure B. For higher concentrations the dye
removal decreased significantly. The maximum adsorption capacity attained was 140.953
mgdye/gzeolite at an Azure B initial concentration of 2500 mg/L.
160 100
140
80
120
Decolourisation (%)
qe (mgdye/gzeolite)
100
60
80
Uptake, qe
Decolourisation 40
60
40
20
20
0 0
10 30 60 90 120 500 700 1800 2500
Initial dye concentration, Ci (mgdye/L)

Fig. 1 Uptake and decolourisation values obtained from different initial Azure B concentrations in
presence of zeolite dosage 1 g and pH 4.
326
Azure B adsorption isotherms
In order to optimize the design of an adsorption system to remove pollutants from effluent, it was
required to establish the most appropriate correlation of equilibrium curves, commonly known as
adsorption isotherms. The equations of the four analysed models along with the isotherm constants
and correlation coefficients are presented in Table 1.The results of the present study indicated that
the Langmuir model did not fit the experimental data due to low correlation coefficient value which
suggested that homogeneous and monolayer mode of adsorption was not suitable in the present
case. The Freundlich model exhibited good fit to the experimental sorption data suggesting the
heterogeneous mode of adsorption since correlation coefficient value was 0.9968. Furthermore, the
nF value, which is related to the distribution of bonded ions on the adsorbent surface, was found to
be 3.011 indicating that adsorption of dye onto zeolite is favoured [4]. A suitable explanation for the
adsorption mechanism would be that the stronger binding sites were initially occupied, with the
binding strength decreasing with increasing degree of site occupation. The abilities of the three-
parameter models, Redlich-Peterson and Sips, were examined to model the equilibrium data. In
terms of correlation coefficient values, the three-parameter models were better than the two-
parameter models as expected from the number of parameters involved in the models. Thus, the
three-parameter models suggested a non-monolayer sorption. The best representation of the
experimental results of the adsorption isotherms was obtained using the Redlich-Peterson model.
The RP value indicates that the adsorption system was between the two limiting behaviours.
Table 1. Adsorption isotherms parameters for Azure B onto NaY zeolite

2
Model Equation Constants R
bL=0.0049 [L/mg]
Langmuir qL = qmaxbLCf / (1 + bLCf) 0.9723
qmax=154 [mg/g]
1-1/n 1/n
1/nF KF=12.443 [mg L /g]
Freundlich qF = KFC 0.9968
nF=3.011
KRP=100.114 [L/g]
Redlich- RP
qRP = KRPCf / (1 + aRPCf ) aRP=7.356 [L /mg ] 0.9974
Peterson
RP=0.6808
KS=12.057
S S
Sips qS = KS Cf / (1+aSCf ) aRP=0.0078 0.9969
S=0.3491
Azure B adsorption kinetics

In order to develop applications of the system, operation control and adsorption kinetic are very
important to the process design. The system was adjusted to the pseudo-second order kinetics,
described by Ho & McKay [5]
qt = qe qe/(1+qek2t ) (4)
where qt is the amount of solute sorbed at time t (mg dye/gzeolite), qe is the amount of solute sorbed at
equilibrium (mgdye/gzeolite) and k2 the second order equilibrium rate constant (g/(mgmin)).
The pseudo-second order kinetics provides an excellent fit between the predicted curves and the
experimental values, whereas the first-order kinetics did not fit well to the experimental data. This
2
fact was confirmed by a good linearization of the data with R >0.999. Pseudo-second-order
adsorption rate constant (k2) and equilibrium uptake values (qe) were determined from the slope
and the intercepts of the plots in the linearized form of the pseudo-second-order model. The
calculated qe values (qe=1.4182 mgdye /gzeolite) also agrees very well with the experimental data
(qe=1.4172 mgdye/gzeolite). The best fit of the second-order expression suggests that the
chemisorption mechanism is involved in the adsorption.
A. viscosus-zeolite system. Model effluent treatment

In this study, the biosorbent obtained by combination of zeolite and A. viscosus has been tested in
order to degrade an effluent like chrome tanning of tannery industry. Several initial dye
327
concentrations were studied and the obtained data are shown in Fig.2. In all cases, the dye was
the first pollutant to be removed with a level higher than 99% after one hour. The chromium
removal was favoured by the presence of A. viscosus which is suggested to reduce the chromium
(VI) to its oxidation state chromium (III), thus it is more easily adsorbed in zeolite. The chromium
exhibits two adsorption stages typical of biosorption kinetics: first associated with external cell
surface reaching a removal of approximately 40% in one day, followed by intracellular
accumulation/reaction.
Azure B
Cr(VI)
100 mg/L Cr(VI) 600 mg/L Azure B
0 20 40 60 80 100
Removal (%)
Fig. 2 Removal degree into zeolite-A.viscosus system for a mixture of Azure B and chromium (VI)
after 8 days.
CONCLUSIONS
The results obtained in this work demonstrated that Azure B can be effectively removed by
adsorption in zeolite NaY. Adsorption isotherms of Azure B on the zeolite were studied using
Langmuir, Freundlich, Sips and Redlich-Peterson isotherm models. Among all the tested isotherm
models for the description of adsorption equilibrium isotherms of Azure B on zeolite, the best fitting
models were RedlichPeterson and Sips. Kinetic studies on sorption of Azure B on zeolite revealed
that pseudo-second-order model showed the best fit to the experimental data suggesting that a
chemisorption mechanism is involved in the adsorption.
The innovative zeolite-biomass system showed that this process is able to perform the removal of a
combination of Azure B and chromium reaching a removal levels higher than 50% in case of
chromium (VI) and more than 99% for Azure B. The presence of the bacterium facilitates the
reduction of the chromium (VI) and the consequent adsorption to the NaY zeolite and reduction of
the toxicity of the effluent. The system appears to be a promising process to the removal of both
pollutants simultaneously (inorganic and organic pollutants) reducing the pollutant charge and
toxicity.
Acknowledgements
This work was supported by Fundao para a Cincia e Tecnologia (FCT-Portugal) and Xunta de
Galicia under programme 08MDS034314PR. The authors are grateful to University of Vigo for
financial support of the research of Emilio Rosales under a mobility grant.
328
REFERENCES
[1] S. Hammami, A. Ouejhani, N. Bellakhal, M. Dachraoui, Application of Doehlert matrix to
determine the optimal conditions of electrochemical treatment of tannery effluents J. Hazard.
Mater. 163 (2009) 251-258.
[2] M. Vaca Mier, R. Lopez Callejas, R. Gehr, B.E. Jimenez Cisneros, P.J.J. Alvarez, Heavy metal
removal with mexican clinoptilolite: Multi-component ionic exchange, Water. Res. 35 (2001) 373-
378.
[3] C. Quintelas, T. Tavares, Removal of chromium(Vi) and cadmium(II) from aqueous solution by a
bacterial biofilm supported on granular activated carbon, Biotechnol.Lett. 23 (2001) 1349-1353.
[4] A.S. zcan, B. Erdem, A. zcan, Adsorption of Acid Blue 193 from aqueous solutions onto
BTMA-bentonite, Colloids Surf.A Physicochem.Eng.Asp. 266 (2005) 73-81.
[5] Y.S. Ho, G. McKay, Pseudo-second order model for sorption processes, Process Biochem. 34
(1999) 451-465.
[6] B. Silva, H. Figueiredo, C. Quintelas, I.C. Neves, T. Tavares, Zeolites as supports for the
biorecovery of hexavalent and trivalent chromium, Microporous Mesoporous Mater. 116 (2008)
555-560.
329
LIFE CYCLE ASSESSMENT OF WINE FROM RAS BAIXAS

1 1 1 1
T. Barrio , S. Gouveia , M.A. Sanromn and D. Moldes
1 Group of Bioprocesses. Department of Chemical Engineering. University of Vigo. 36210 Vigo.
Spain. e-mail: tebarrio@uvigo.es
ABSTRACT
The study of Life Cycle Assessment has been done regarding the winery industry in the
area of Ras Baixas (Northwest Spain). The aim of this study is to analyze the
environmental impacts of the wine making process by using the Albario grape variety.
All the stages of wine production (viticulture, wine making, transport and disposal of
empty bottles) were considered to carry out the study by using the conventional LCA
methodology.
The results of this study show that wine making and transport stages present the highest
environmental impact, specially caused by fossil fuel use. The bottling during wine
making is the process with highest environmental load due to necessary glass
production. In the viticulture stage, the most important environmental events detected
were the use of fertilizers and fuel consumption for farm work.
In order to reduce the environmental impact is necessary to act on the main variables
such as the use of fertilizers, consumption of fossil fuels, bottling and transport.
The results obtained with this analysis are compared with those derived from the
simulation of alternative scenarios that would be more eco-efficient. Results are also
compared with those from a study concerning winery in La Rioja area [1, 2], in order to
carry out the identification of the differences between these two areas of Spain.
Keywords: Life Cycle Assessment (LCA); Wine; Albario; Ras Baixas
INTRODUCTION
LCA is a powerful tool to study and analyze the environmental effect of an industrial process. The
LCA studies regarding wine production are not usual and they are just centered in very specific
areas: La Rioja [1, 2] and Tuscany [3]. An important conclusion of the studies from La Rioja is the
determination of the transport as the main activity concerning environmental impact. This impact
is due to fossil fuel consumption.
The Ras Baixas area is a region from Galicia (NW Spain) where a prestigious white wine is
produced: Albario. In this work we show for the first time the main results of the LCA of wine
production in the area of Ras Baixas. The study considers all stages of wine production and the
LCA methodology has been applied to the whole process of wine production in order to detect the
most problematic points from an environmental approach. Furthermore, several simulations
considering alternative scenarios of the wine making process have been tested to reduce the
environmental burdens. Finally a comparison between La Rioja and Ras Baixas areas is shown.
METHODS
Life Cycle Assessment

The data used to perform the analysis were obtained from a project in the Integrated Training
Center for Food Industries "A Granxa" (Ponteareas) for Albario wine making in the Ras Baixas in
2008. All inputs and outputs considered, except when indicated, are representative values of this
area.
The data obtained was treated with the SimaPro software version 7.2 from Pr Consultants
(Netherlands). Several databases have been used, especially BUWAL 250, ETH-ESU 96, 2001
IDEMAT, Industry data 2.0 and Methods. The method Ecoindicator 99 (E) was selected to carry out
the impact assessment.
330
The functional unit selected was a bottle of wine. It is considered that 1 kg of grapes produces 0.75
liters of wine, after the completed process, which corresponds to a bottle.
The analysis was divided in three parts: viticulture, wine making and transport for distribution of
wine. In addition, following these steps the disposal of the bottle was also included.
Viticulture
The study was limited to the operations made every year (liming, fertilizing, phytosanitary
treatment, pruning and harvest). Operations to be carried out after longer periods of time, such as
land preparation, planting of vineyards, driving of the vineyard over trellis, were not considered.
The inputs and outputs of viticulture stage are shown in Fig. 1.
Fig. 1. Inputs and outputs in the process of viticulture
Wine making
The processes considered in this phase are: desreming, sulphite, pressing, alcoholic fermentation,
clarification, filtration and bottling. The inputs and outputs are shown in the Fig. 2.
Fig. 2. Inputs and outputs in the process of wine making
Transport
In the area studied (Ras Baixas), the wine is mainly distributed for domestic consumption (81%)
and the rest of the production is exported (19%).
End of life of the bottle

It is necessary to take into account that currently in Spain the 60% of used glass containers are
recycled in the food sector (Ecovidrio, Spain).
331
RESULTS
Inventory
For carrying out the LCA, the first step is the making of an inventory of all inputs and outputs of all
processes involved in the production of a bottle of wine from Ras Baixas. These data are shown in
Table 1, Table 2, Table 3, Table 4 and Table 5.
Table 1. Inputs: Viticulture
ELEMENT TYPE AMOUNT [g] PHASE

Diesel 86 Farm work
CaO 4
Limestones Liming
M[g]O 11.66
15 10 15
N -P -K 40
Fertilizers K2SO4 26 Fertilizing
NH4NO3 8.5
Cu 0.26
Azoxystrobin 0.06
Cimoxanilo 0.038
Phytosanitay
Phytosanitaries Maneb 0.16
treatment
Zimeb 0.2
Ciprodinil 0.0187
Fluodioxinil 0.0125
Table 2. Outputs: Viticulture
ELEMENT TYPE AMOUNT [kg] PHASE

Canes Wood 0.266 Pruning
Grapes Albario 1.030 Harvest
Table 3. Inputs: Wine making
ELEMENT TYPE AMOUNT PHASE

Albario Desteming-
Grapes 1 [kg]
crushing
Gas disolved in Aplication of
Sulphur 105 [mg]
water sulphite
Water 1.5 [L] Cleaning
Clearing agents Bentonite 0.45 [g] Clarification
Diatomaceus
Filtration earth 3 [g] Filtration
earth
Electricity 0.1507 [kWh] Winery processes
Diesel 0.0141 [L] without bottling
Transparent
Glass 550 [g]
Bordeaux
Label Paper 2 [g]
Cork Natural 3 [g]
Bottling
Cap Aluminium 5 [g]
Cardboard box 13 [g]
Pallet Pine wood 15 [g]
Film 1.7 [g]
Electricity 0.011 [kWh]
332
Table 4. Outputs: Wine making
ELEMENT TYPE AMOUNT PHASE

Transparent
Wine bottle 1.340 [kg] Bottling
Bordeaux
Stem Albario 30 [g] Desteming
Bagasse Albario 320 [g] Pressing
Lees Albario 22.5 [mL] Debourbage
Diatomaceus
Filtration earth 3 [g] Filtration
earth
Carbon dioxide 0.097 [kg] Alcoholic fermentation
Table 5. Transport
ELEMENT TYPE UNIT [tkm] LOAD (%)

Domestic distribution
Truck 16 [ ton] 0.68 50
(Spain)
International distribution
Truck 40 [ton] 2.64 50
(Europe)
International distribution
Ship 17.6 60
(Outside Europe)
Analysis
Ras Baixas
The results of the LCA in Ras Baixas show that wine making and transport stages present the
highest environmental impact (Fig. 3), with 38% of the total impact for each one. These activities
have a strong influence in the category of Fossil Fuels and Respiratory Inorganics (Fig. 4), mainly
due to the consumption of diesel fuel for the transport phase and the power needed in the
processes in winery (power consumption implies indirect consumption of natural gas and other
energy sources).
10%
1%
Farm work
Fertilizing
48% Pesticides
41% Other materials
24%
38%
17%
38% Viticulture
Wine making Wine making
83%
Distribution Bottling
29%
Domestic distribution (Spain)
71% International distribution
Fig. 3. Environmental impacts in all process
333
Fossil fuels
Minerals
Land use
Acidification/ Eutrophication
Ecotoxicity
VITICULTURE
Ozone layer WINE MAKING
TRANSPORT
Radiation
Climate change
Respiratory inorganics
Respiratory organics
Carcinogens
0 10 20 30 40 50 60 70
mPt
Fig 4. Values according to the impact categories
In the viticulture phase the greatest burden is produced by the farm work, with 48% of the total
environmental impact, mainly due to fuel use during field work done by the tractor. The next activity
in order of importance is the use of fertilizers, with 41% of the total impact on the viticulture phase
(Fig. 3).
During wine making, the bottling is the process with highest environmental load, with 83% of the
total environmental impact of this stage. This remarkable effect is due to the necessary glass
production.
For the transport stage the most noticeable result is the high environmental effect of exportation.
Although only 19% of the wine is exported, its corresponding environmental impact is 71% of the
total impact of the transport stage, mainly due to the higher distance of destination compared with
national tansport (Fig. 3).
In order to reduce the environmental impact of the whole process of wine production and
distribution, it is possible to modify the methodology of these activities by acting on the most
environmentally negative variables such as the use of fertilizers, consumption of fossil fuels,
bottling and transport. For this reason several simulations considering alternative scenarios of the
wine making process have been carried out:
1. Ecological vine growing

2. Light bottles
3. Recycled bottles 90%
4. Bottles reuse
5. Rail transport
6. Bulk transport:
7. Use of recycled materials
8. Combination of alternative scenarios 1, 2, 4, 5, 6 and 7.
334
In Fig. 6 the main results of these simulations are shown. All the alternatives allow the
improvement of the environmental behavior of the wine making process, but the combination of
several alternatives could achieve a reduction of the total environmental impact of 64%.
Conventional 119
1. Ecological vine growing 104
2. Light bottle 101
3. Recycling 90% 117
4. Reuse of bottles 94
5. Rail transport 94
6. Bulk transpot 101
7. Recycled materials 114
8. Combination 43
0 50 100 150
mPt
Fig. 6. Alternative scenarios
Comparison: Ras Baixas vs. La Rioja

This study was limited to the inventory data of La Rioja [1, 2]. The production of wine in Ras
Baixas area seems to present lower environmental impacts than the production in La Rioja.
Viticulture stage presents the main differences between these two areas (Table 6).
Table 6. Comparison: Ras Baixas vs. La Rioja
Environmental impact Ras Baixas [mPt] Rioja [mPt]

Total 99.07 117.23
Viticulture 17.78 28.86
Wine making 35.75 41.71
Transport 45.54 46.66
Acknowledgements
S. Gouveia is grateful to Fundao para a Cincia e a Tecnologia Portugal for her fellowship and
D. Moldes is grateful to Xunta de Galicia for an IPP contract. This work was funded by Xunta de
Galicia (project 09TMT012E) and Ministry of Science and Innovation (project CTQ2009-13651).
References
[1] A. Aranda. I. Zabalza. S. Scarpellini. Economic and environmental analysis of the wine bottle
production in Spain by means of life cycle assessment. Int Jl Agric Resour Governance Ecol, 4
(2005) 178191.
[2] C. Gazulla. M. Raugei. P. Fullana-i-Palmer. Taking a life cycle look at crianza wine production in
Spain: where are the bottlenecks?. Int J Life Cycle Assess, 15 (2010) 330-337.
[3] A. Pizzigallo. C. Granai. S. Borsa. The joint use of LCA and emergy evaluation for the analysis
of two Italian wine farms . J. Environ. Manage. 86 (2) (2008) 396406.
335
EFFECT OF DIFFERENT CONCENTRATIONS OF THE EXTRACT OF

MORINGA SEEDS AS COAGULANT AGENT IN THE TREATMENT OF
DOMESTIC SEWAGE
1 2 3 4 5
S.A.A Baker , P.A.V. Lo Monaco , M.D.S Pereira , A.T. Matos and V.E. Jnior
1 Undergraduate student in Agricultural and Environmental Engineering at Federal University of
Viosa, Minas Gerais, Brazil. sandy.baker@ufv.br
2 Professor at Federal Institute of Esprito Santo, Santa Teresa, Esprito Santo, Brazil.
paolalomonaco2004@yahoo.com.br
Viosa, Minas Gerais, Brazil. magno.pereira@ufv.br
4 Professor at Agricultural Engineering Department, Federal University of Viosa, Minas Gerais,
Brazil. atmatos@ufv.br
5 DS Student in Agricultural Engineering at Federal University of Viosa, Minas Gerais, Brazil.
vejunior@yahoo.com.br
ABSTRACT
Many studies have being done in the last years to evaluate the coagulant effect of the
extract of moringa (Moringa oleifera) seeds in the treatment of several wastewaters.
According to [1], the natural coagulants/flocculating have demonstrated advantages in
relation to chemicals, specifically regarding the biodegradability, low toxicity and low
production of residual sludge. In the present work the objective was to evaluate the effect
of different concentrations of the extract of moringa seeds when it is used to remove
turbidity in the domestic sewage. Tests were performed using the Jar-test apparatus, and
was evaluated the effects of the concentrations of 0,04; 0,02; 0,1; 0,2; 0,4; 0,6; 0,8; 1,2;
1,6; 2,0; 2,4; 3,0; 4,0 and 5,0 g of grinded seeds per liter of distilled water. Mathematical
equations were adjusted by regression, relating the concentration of the extract of
moringa seeds with the domestic sewage turbidity. It was found in the tests that the
-1
concentration of 5,0 g.L of moringa seeds, for a sedimentation time of 2 h, had the
highest efficiency of turbidity removal in domestic sewage, and it was obtained turbidity
removal of 73,41; 85,25 and 77,28%, respectively.
Keywords: natural coagulant, turbidity, water treatment.
INTRODUCTION
Several researches have been conducted in the last years using the seed of moringa (Moringa
oleifera), due to the physico-chemical properties that provide this natural coagulant the potential of
clarification on various types of water treatment. Moringa seeds are characterized by high levels of
protein and lipids, being the protein the major responsible in the process of water clarification. [2]
reported the presence of a dimeric cationic protein in the moringa seeds, of high molecular weight,
which destabilizes the particles in the water through a neutralizing and adsorption process.
The use of these natural coagulants, produced on site and with low financial cost, can provide
attenuation of problems related to the consumption of non-potable water and sewage dumps
without previous treatment in water bodies. Moreover, according to [4], the natural
coagulants/flocculating have demonstrated advantages in relation to chemicals, specifically
regarding the biodegradability, low toxicity and low production of residual sludge. In experiments to
assess the better combination of concentration-pH for the remotion of suspended solids, in
wastewater of coffee fruit washing/pulping and dairy wastewater, [3] and [7], respectively,
concluded that the extract of moringa seeds has great potential as natural coagulant in the
treatment of the studied wastewaters. In addition, according to [5], the use of (Al2(SO4)3) is related
to several negative externalities, such as health problems caused by residual aluminum in treated
336
waters, difficulty in the final disposal of sludge generated at the treatment plants, alkalinity
consumption and production of large volume of sludge.
The objective of this work was to assess the effect of different concentrations of extract of moringa
seeds, when used for turbidity removal of domestic sewage. Three tests were conducted using the
Jar test apparatus, being evaluated the coagulant/flocculant effect in doses of 0.04; 0.02; 0.1; 0.2;
0.4; 0.6; 0.8; 1.2; 1.6; 2.0; 2.4; 3.0; 4.0 and 5.0 grams of crushed seeds of moringa per liter of
domestic sewage to be treated. The tests on "Jar-test" and turbidity analyses were performed at
the Water Quality Laboratory in the Department of Agricultural Engineering of the Federal
University of Viosa, Minas Gerais, Brazil. Mathematical equations were fitted by regression,
relating the concentration of extract of moringa seed with domestic sewage turbidity.
METHODOLOGY
The experiment was conducted at the Laboratory of Soil and Solid Waste of the Department of
Agricultural Engineering at the Federal University of Viosa (UFV). For the tests it was used raw
sewage from the neighborhood of Acamari, located in the Municipality of Viosa, Minas Gerais,
Brazil. The sewage was collected in an elevation station of the Department of Agricultural
Engineering. The turbidity values obtained for the raw sewage, in each of the three repetitions of
the experiment, were 58.3, 56.6 and 60.3 NTU respectively.
The extract of moringa seeds was obtained after grinding in a blender, to provide concentrations of
-1
10, 20, 40 and 50 g L of seeds, in which were used 5, 10, 20 and 25 g of Moringa seeds,
respectively, in 500 mL of distilled water for each concentration. After this process, the solution was
filtered through a 1 mm mesh. Then different aliquots were taken from these seeds suspension to
-1
provide concentrations of 0,04; 0,02; 0,1; 0,2; 0,4; 0,6; 0,8; 1,2; 1,6; 2,0; 2,4; 3,0; 4,0 and 5,0 g L
of grinded seeds.
The suspensions were mixed with 500 mL of raw sewage in beakers and placed into agitation in
the apparatus "Jar-test", remaining there for 30 seconds under agitation of 160 rpm and then for 15
minutes, under agitation of 15 rpm. The suspensions were kept at rest for two hours to give enough
time for the sedimentation process of the material. After that, samples from the supernatant were
collected to measure the turbidity, measured in Turbidimeter Marconi, model TB 1000. For
comparison purposes, a sample containing only raw sewage was placed into the apparatus "Jar-
test", without the extract of moringa seeds, and the turbidity was also measured during the
experiment.
The tests on "Jar-test" and turbidity analysis were performed at the Laboratory of Water Quality in
the Department of Agricultural Engineering at Federal University of Viosa.
It was performed three repetitions, for all concentrations of moringa seeds extract (0,04; 0,02; 0,1;
-1)
0,2; 0,4; 0,6; 0,8; 1,2; 1,6; 2,0; 2,4; 3,0; 4,0 and 5,0 g L , and through regression analysis,
mathematical equations were adjusted relating the turbidity values as a function of different
concentrations of the solutions analyzed. Adjustment resulting in the coefficient of determination
greater than 70% and minimum significance of 1% probability in the coefficients was considered
satisfactory. To perform the regression analysis, SigmaPlot 9.0 was used.

In figures 1A, 1B and 1C the graphs representing the values of effluent turbidity of domestic sewage as a
function of the doses of seeds are shown, to influent with turbidity of 56.6; 58.3 and 60.3 NTU, respectively.
337
Figure 1. Effluent values of domestic sewage turbidity as a function of the doses of Moringa seeds, to influent
of 56.6 (A); 58.3 (B) and 60.3 NTU (C).
According to the figures 1A, 1B and 1C, effluent turbidity increased when added up to
approximately 1 g of crushed seeds in each liter of domestic sewage. It is believed that this initial
increase in turbidity is associated with the increment of the own organic material contained in the
moringa seeds to the domestic sewage, considering that the addition of moringa seeds had not
been sufficient to start the process of coagulation. When higher quantities of moringa seeds were
-1
added, in other words, when the dose of seeds was higher than 1,0 g L , the coagulation effect
provided by the seeds overcame the increment of the own organic material of the seeds, causing
flocculation process in the suspension and flocculation of suspended solids, consequently, the
turbidity started to decrease.
The efficiency in turbidity reduction obtained in this work is much higher compared with the work of
[6], that in a similar experiment, but with the use of extract of moringa seed with sodium chloride
solution for treatment of domestic sewage, the removal obtained was only of 22.3% of turbidity.
It is suspected that there is no efficiency as coagulant when the extract of moringa seeds is used to
treat wastewaters rich in organic material, as in swine wastewater. The high turbidity removal
efficiency obtained in this study may be related to the fact that raw sewage doesnt have high
content of organic material in comparison to swine wastewater.
CONCLUSIONS
- Apparently, the optimal dose of moringa seeds, which provided the smallest effluent turbidity, is in the range
-1
of 4 to 5 g L in the three performed tests. When these doses were applied, reductions in the range of 70.49
to 85.25% were obtained in the domestic sewage turbidity.
338
REFERENCES
[1] A. Ndabigengesere; S. K. Narasiah,. Influence of operating parameters on turbidity removal
by coagulation with Moringa oleifera seeds. Environmental Technology, v.17, p.1103-
1112. 1996.
[2] A. Ndabigengesere; S. K Narasiah; B. G. Talbot Active agents and mechanism of
coagulation of turbid waters using Moringa oleifera. Water Research, v.29, n.2, p.703-710.
1995.
[3] A.T. Matos, C.F.G. Cabanellas, P.R. Cecon, M.S. Brasil, C.S. Mudado, Efeito da
concentrao de coagulantes e do pH da soluo na turbidez da gua, em recirculao,
utilizada no processamento dos frutos do cafeeiro. Revista Engenharia Agrcola, 27
(2007) 544-551.
[4] L.C.K. Moraes. Estudo da coagulao-ultrafiltrao com o biopolmero quitosana para a
produo de gua potvel. Universidade Estadual de Maring, Maring. 2004.
[5] M.E.R. Silva; M.D. Aquino; A.B. Santos Ps-tratamento de efluentes provenientes de
reatores anaerbios tratando esgotos sanitrios por coagulantes naturais e no-naturais.
Revista Tecnologia, v.28, n.2, p.178-190. 2007.
[6] P.A.V. Lo Monaco; , A.T. Matos; I.C.A. Ribeiro; F.S. Nascimento, A. P. Sarmento,
Utilizao de extrato de sementes de moringa como agente coagulante no tratamento de
gua para abastecimento e guas residurias. Ambi-gua, 5 (2010) 222-231.
[7] R.C. Chagas; C.B. Saraiva; D.A. Moreira; D.J.P. Silva; A.T. Matos; J.A. Farage, Uso do
extrato de moringa como agente coagulante no tratamento de guas residurias de
laticnios. In: XXVI Congresso Nacional de Laticnios. Anais... Juiz de Fora: ICLT/EPAMIG,
2009.
339
USE OF COAL BOTTOM ASH IN MORTARS - ANALYSIS OF ITS INFLUENCE

ON THE PROPERTIES CHARACTERIZATION
1 2 3 4
N.L. Mustelier , J. Cavalheiro , J.C. Rocha , M. Cheriaf
1 Dpt. of Metallurgical and Materials Engineering, University of Porto, Porto, Portugal,
niubis@fe.up.pt
2 Dpt. of Metallurgical and Materials Engineering, University of Porto, Porto, Portugal,
jcavalheiro@netcabo.pt
3 Dpt. Civil Engineering, Federal University of Santa Catarina, Florianopolis, Brazil, 88040-900,
ecv1jcr@ecv.ufsc.br
4 Dpt. Civil Engineering, Federal University of Santa Catarina, Florianopolis, BRAZIL, 88040-900,
malik@ecv.ufsc.br
ABSTRACT
Recently, the use of waste in the civil construction industry has acquired a great
importance. The bottom ashes are by-products originating the combustion of coal with
beneficial effects not only reflect the technical and economic benefit, where waste is
applied to mortar or concrete, but also make a mention of the positive factor of the
reduction of environmental impacts inherent in the process of generation and,
consequently, to final deposition. The bottom ash influence many properties such: the
water demand, the natural water, the filler effect and mechanical properties, due also to
the pozzolanic effect. These effects in the properties such as mechanical strength and
the formation of pores, influencing the moisture transport behaviour within the mortars.
The development of materials with bottom ash requires an investigation of the nature of
ashes and its effect on water behaviour of multiphase materials developed. This paper
reports on the behaviour of the mortars produced with bottom ash used as a substitute for
natural sand, evaluated according to the mechanical properties compressive strength
and tensile bond strength and some properties of moisture transport porosity,
apparent wetting angle and capillarity.
Keywords: Mortar, bottom ashes, air-entraining agent, hygro-physical property.
INTRODUCTION
Research are being developed, in search of new building materials with residues incorporated,
such as: ash coal as an alternative to reducing the volume of extraction of raw materials, conserve
non-renewable raw materials, reduced energy consumption, reducing emissions of pollutants such
as CO2, improving health and safety of the population.
The coal ashes are by-products from the combustion of coal. From burning coal in power plants,
three major wastes are generated, which are fly ash, bottom ash and slag. Studies conducted
indicate the use of ashes in bases or materials with cement. [1, 2, 3] as well as propose the
utilization of bottom ash in substitution of the sand for the making mortar and concrete. [4, 5, 6, 7]
Such studies present satisfactory results related to their properties in fresh and hardened. But the
bottom ash influence many properties such: the water demand, the natural water, the filler effect [8,
9] and mechanical properties, due also to the pozzolanic effect [10, 11, 12]. These effects in the
properties such as mechanical strength and the formation of pores, influencing the moisture
transport behaviour within the mortars. Also, bottom ash has porosity with a high capacity to retain
water, a factor which should be considered in the evaluation of the mortars produced with this by-
product since bottom ash works well as a water reservoir [13].
340
This paper reports on the behaviour of the mortars produced with bottom ash used as a substitute
for natural sand, evaluated according to the mechanical properties compressive strength and
tensile bond strength and some properties of moisture transport porosity, apparent wetting
angle and capillarity, allowing to analyse the influence of different ash content (0, 50, 100%) as well
as air incorporation agent have on properties characterization.
2. EXPERIMENTAL PROCEDURE
The materials used in this study were: Portland cement with limestone filler addition, CP-II-F, Class
32, hydrated lime type-III CH, natural sand and bottom ash, air incorporation agent (IA) based on
ligno-sulfonate and water. The bottom ash (BA) is silica-alumina material. In addition to its chemical
composition presented as one of advantages for use in replacement of natural sand to its low
3 3
density (1, 80 g/cm ) in relation to specific gravity of sand (2.57 g/cm ).
The bottom ash is composed mainly of oxides of silicon, aluminium, potassium and iron, and
belongs to the class F according to the classification proposed by ASTM C618 [14]. The
pozzolanic of bottom ash was evidenced by analysis of the consumption of calcium hydroxide by
Cheriaf et al [12]. In the analysis of pozzolanic established by standard, the index obtained was
0,73, according to the procedure NBR5752 [15].
The X-ray diffraction analysis indicates that the BA is comprised mainly of quartz and mullite. In
electron micrographs performed on mean fraction of bottom ash can be observed that due to the
process of burning ashes have spherical shapes or clusters of spheres with micro porosity (Fig. 1).
X-ray diffraction analysis SEM (Average fraction)

Fig.1 Characteristics of the bottom ash
Six different mortar coatings (M) were characterized. The mix compositions selected were based
on studies developed by SANTOS et al. [16] and produced from a formulation (mix proportion
base) by volume composed of 10.91% of cement, 30.64% lime and 58.45% sand. From the base
formulation were produced mortars with the substitution of sand by volume in bottom ash in the
following percentages: 0, 50 and 100%, where the bottom ash that was incorporated was dried, the
drying taking place in a ventilated greenhouse marinated at a temperature of 105C, over 24 h. For
each of the percentages of substitution of sand by bottom ash were prepared mortars with and
without air-entraining agent. Due to the nature of the bottom ash, the water/cement ratio (w /c) was
2.29 for all mortars. For those mortars in which additives were used, the amount of additive was
0.03% compared to the total weight of dry material.
The samples used for testing were obtained from the pilot coating systems based mounting of
small panels with dry joint and locking system peripheral, each panel being mounted horizontally
and with six concrete blocks of dimensions 140mm x 190mm x 390mm; after the end of setting,
each system was wrapped in plastic waterproof and maintaining in this way, conditioned until 28
days. The mortars were characterized for the tests on mechanical properties: the compressive
strength (NBR 12118/92) and tensile bond strength (NBR 13528/95) and for test properties of
moisture transport: open porosity and bulk density were quantified by measuring water saturation
under vacuum followed the experimental procedures shown by Saffiuddin & Hearn [17]. The
apparent wetting contact angle () was determined according to the experiment described by
Merouani [18].
341
In the test for determination of the amount of capillary water absorbed for the mortars was
monitored using a graduated Mariotte bottle (hydraulic gradient of zero). In capillary absorption was
employed distilled and deionised water. The compositions of the six mortar types and of the
contents of the bottom ash as a substitute for natural sand and mechanical properties are given in
Table 1.
Table 1 - Mix proportion and mechanical properties mortars

3
Mix proportion g/dm 0% BA 50% BA 100% BA 0% BA+IA 50% BA+IA 100% BA+IA
Cement 387 425 462 312 336 403
Lime 775 851 924 625 673 805
Natural sand 2711 1489 0 2187 1177 0
Bottom ash 0 642 1396 0 508 1216
Air incorporation 0 0 0 0,09 0,08 0,07
Water 887 974 1058 716 770 922
Density *(Kg/dm3) Fresh 2,02 1,86 1,63 1,63 1,47 1,42
Flow* (mm) 218 209 183 235 214 195
Water retention *(%) 82,75 78,04 79,70 95,61 91,74 81,00
Compressive strength *(Mpa) 1,44 2,16 2,69 0,87 1,98 2,59
Tensile bond strength **(Mpa) 0,25 0,33 0,11 0,22 0,22 0,15
Note: * Each test result is the average of tests on three sample specimens (50100 mm cylinders).
** Test result is the average of tests on three tablets random of each sample obtained after pullout.
3. RESULTS AND DISCUSSION

Through the results (Table 1), verifies that for a same relation w/c, the mortars studied present
different consistencies, being that, as much as bigger the ash content, smaller is the consistency,
occurring for the mortars without or with air-entraining agent.
Regarding the water retention capacity, have that the use of the BA implies a reduction of the water
retention capacity, and this result is consistent with found by Margon (2002) [5] and Santos et al.
(2004) [16]. However, it was not found a strong relation between the content of BA and water
retention. Analysing the data obtained from compressive strength, it is observed that the mortar
without IA had a higher compressive strength that the mortars with IA, and as we increased the
concentration of BA, increased the resistance to the compression. The results of tensile bond
strength had equal values or above 0.30 MPa which is the minimum standard prescribed by (NBR
13528/95) for external coating.
For the bulk density in the hardened state the content of BA and IA significantly influence. On Fig. 2
was observed that for both mortars, as we increased the concentration of BA decreased the bulk
density. Both the BA and the IA cause a reduction in density, which is consistent with the fact that
the density of BA be about 30% smaller than the sand and the action of the IA promoting increased
levels of air incorporated. It can be observed that the bulk density varies lineally with the content of
BA.
45
2,00
Bulk Density Apparent (kg/cm3)
1,90
40
1,80
Open Porosity (%)
1,70
35
1,60
1,50
30
1,40
1,30
25
1,20
Mortars_without IA Mortars_ with IA
1,10 y = -0,5353x + 1,8654 y = -0,4006x + 1,76
Mortars without IA Mortars with IA
1,00
R = 0,9823 R = 0,9983 20
0% 50% 100% 0% 50% 100%
Ash Content (%) Teor de CZP (%)
Fig. 2 - Apparent bulk density and open porosity.
342
The results obtained for open porosity show that for the same BA content, the porosity is reduced
with the use of IA, in cases of mortar 100 %BA. It can also be observed that there was an increase
in porosity for the mortars without IA being reversed this behaviour in the case of mortars with
additive and 100%BA, which increased the porosity of mortar. There is also that the higher the
concentration of BA, the higher the porosity, can be considered that the use of bottom ash in the
composition of the mortars contributed to a greater volume of permeable pores. This can be
explained by porosimetry due to distribution of open pores in the materials according to their
dimensions where a material with higher porosity can however present a lower uptake water,
moisture content and mass of H20 as observed with prior.
From the values of the total volume of water absorbed obtained by weighing, have that, for mortar
without air incorporation agent, the total water absorption decreased with ash content. As for the
mortar with air-entraining additives, the tendency was to increase the volume of water absorbed.
These results are shown in Fig. 3.
25
20
Vw(cm3)
15
10
0
0% 50% 100% 0%+IA 50%+IA 100%+IA
Ash Content
Fig. 3 - Total volume of water absorbed.
The sorptivity coefficient of the different mortars was obtained in a time interval of 2 to 120 minutes,
for mortars having 0% BA with and without IA, and between 10 minutes and 240 minutes for the
remaining mortars. These respective intervals were adopted such that, for all the mortars the
relation between volume of liquid absorbed by the cross sectional area of the sample (X) versus
the square root of time were linear and providing the data to calculate the sorptivity. It is important
to point out, that the samples analysed had been extracted of the pilot coating systems, having a
height of 30mm, in the case of mortars 0% BA with and without AI, the top was reached in the early
hours.
Analysing the influence of ash content on sorptivity it verifies that for the same ash content, have
that, when compare the mortars with and without IA, had a same tendency of behaviour. The
mortars with IA, in general, an increase in the coefficient of sorptivity as visualized in Fig. 4.
This increase can be attributed to the presence of permeable pores in mortars with air-entraining
additives, which causes the increase of liquid fronts in porous media.
343
10
9
8
S (cm3/cm2xmin1/2)x10-2
7
6
5
4
3
2
1
0
0 50 100
Ash Content (%)
Fig. 4 - Coefficient Sorptivity
In the Fig. 5, is presented the apparent wetting angle in function of the ash content. Through this, it
is possible observe that have not been verified a clear correlation between the ash content and the
wetting angle, being possible comment that, from the mortars with 50% BA had a diminution of the
angle of wetting with the addition of IA.
100
90
Apparent wetting angle (o)
80
70
60
50
40
0 50 100
Ash content (%)
Fig. 5 - Apparent wetting angle
From the results, one can observe that there is a tendency of BA promotes the reduction of
wettability (wetting angle increased). This reduction is due to the action of bottom ash in mortar,
because the water absorption test, such mortars have a higher rise time of the capillary fringe and
less sorptivity and total amount absorbed water. The incorporation agent promotes the formation of
pores increasing the wettability of the material.
4. CONCLUSIONS
This investigation has clearly established the influences that the addition of bottom ash and air
incorporation agent provides in the mechanical and hygric properties of mortar. The sorptivity is
significantly influenced by the ash content and the use of AI. These parameters promote the
reduction of sorptivity. However, the reduction promoted by the bottom ash is more significant and
can occur due to the refinement of the pores of the mortars. Such refinement can be caused by the
BA, because of his thinness (effect filler) and its pozzolanic potential. The air incorporation agent
acts in the reduction of the capillaries accessible to water and/or becoming more heterogeneous
the circuit of the pore radius.
344
Through the wetting angle, could not find a strong relationship due to the fact that the results were
scattered and considering that this property is strongly linked to the possible presence of absorbed
layers. But one can see that there is a decrease in wettability as BA and increases with the
additive. However, for bottom ash mortars, the mechanical properties were maintained.
REFERENCES
[1] KULA, A. OLGUN, V. SEVINC AND Y. ERDOGAN An investigation on the use of tincalore
waste, fly ash, and coal bottom ash as Portland cement replacement materials. Cement and
concrete research, 32 (2002) 227-232.
[2] MALHOTRA, V. M.; VALIMBE, P. S.; WRIGHT, M. A. Effects of fly ash and bottom ash on the
frictional behaviour of composites. Fuel. 81 (2002) 235-244.
[3] HANEHARA S.; TOMOSAWA F.; KOBAYAKAWA M.; HWANG K. Effects of water/powder ratio,
mixing ratio of fly ash, and curing temperature on pozzolanic reaction of fly ash in cement paste.
Cement and concrete research. 31 (2001) 31-39.
[4] L.B. Andrade, J.C. Rocha, M. Cheriaf. Evaluation of concrete incorporating bottom ash as a
natural aggregates replacement. Waste Management 27 (2007) 11901199.
[5] MARGON, P. V. Influncia do uso das cinzas de carvo mineral de termeltricas em
argamassas de revestimento: dosagem por curvas granulomtricas. Florianpolis, SC. UFSC.
2002. 100 p. Dissertao (Mestrado em Engenharia Civil) - Universidade Federal de Santa
Catarina.
[6] Mustelier, L.N. 2008, Estimativa do Comportamento de Paredes no Ensaio de Penetrao de
gua de Chuva atravs das Propriedades de Transferncia de Umidade dos Materiais
Constituintes. Tese (Doutorado em Engenharia Civil) Universidade Federal de Santa
Catarina. Florianpolis.
[7] PIAZZA, J. L.; RUI, V. Comportamento das cinzas pesadas de carvo mineral como substituto
da areia quartzosa em argamassas. Vitria, ES. In: Simpsio Brasileiro de Tecnologia das
Argamassas, Vitria , Anais. 1999. pp. 389-401.
[8] Odler, I., Ro bler, M.,. Investigations on the relationship between porosity, structure and
strength of hydrated portland cement pastes. II Effect of pore structure and of degree of
hydration. Cement and Concrete Research 15 (1985) 401410.
[9] Pandey, S.P., Sharma, R.L. The influence of mineral additives on the strength and porosity of
OPC mortar. Cement and Concrete Research 30 (2000) 1923.
[10] Ravina, D. Properties of fresh concrete incorporating a high volume of fly ash as partial fine
sand replacement. Materials and Strutures/ Matriaux et Constructions. 30 (1997) 473479.
[11] Chengzi, Z., Aiqin, W., Mingshu, T., Xiaoyu, L. The filling role of pozzolanic material. Cement
and Concrete Research. 26 (1996) 943947.
[12] M. Cheriaf, J. Pra, J.C. Rocha, Pozzolanic properties of pulverized coal combustion bottom
ash, Cem. Concr. Res. 29 (1999) 13871391.
[13] Barbare N, Shukla A, Bose A. Uptake and loss of water in cenosphere-concrete composite
material. Cem Concr Res. 33 (2003) 16811686.
[14] ASTM C 618, Standard Specification for Coal fly ash and raw of Calcined Natural Pozzolan for
use as a Mineral Admixture in Portland Cement Concrete, 1995.
[15] NBR, 5752Materiais Pozolnicos - Determinao de Atividade Pozolnica com cimento
Portland - Indice de Atividade Pozolnica com Cimento, Rio de Janeiro, 1992.
[16] Santos, F.I.G., Lenzi, E.J., Rocha, J.C., Cheriaf, M. 2004, Avaliao de Resduos para uso em
Argamassas -Estudo com Cinza Pesada. Proceedings of 1 Latin-American Conference of
Sustainable Construction and 10 National Meeting of Technology of Environment Built, So
Paulo: ANTAC, 2004 (in Portuguese)
[17] Safiuddin, M.D., Hearn, N. 2005, Comparison of ASTM Saturation Techniques for Measuring
the Permeable Porosity of Concrete, Cement and Concrete Research. 35 (2005) 1008-1013.
[18] L. Merouani, Phnomnes de sorption et de transfert d'humidit dans des matriaux du
btiment. tude exprimentale comparative d'un mortier de ciment et d'un enduit de faade.
Thse Docteur 3o Cycle. Institut National Polytechnique de Grenoble, 1987 (in French).
345
WASTE MANAGEMENT IN PORTUGAL AND EUROPE AN OVERVIEW OF

THE PAST, PRESENT AND FUTURE
1 2 3 4
A. Ribeiro , F. Castro , M. Macedo and J. Carvalho

3 CVR Centre for Waste Valorization, mcmacedo@live.com.pt.
ABSTRACT
As world society grows exponentially more and more wastes, have been created. Each
year European Union throws away 3 billion tons of waste, and some 90 million tons of
that are hazardous. It is clear that treating and disposing of all this material - without
harming the environment - becomes a major trouble. In the early 90s, the amount of
waste generated in Europe increased by 10%. Most of that was thrown away in
incinerators, or dumped into landfill creating environmental damage. Landfill disposal not
only takes valuable land space but also causes air, water and soil pollution, discharging
carbon dioxide (CO2) and methane (CH4) into the atmosphere and chemicals and
pesticides into the earth and groundwater. This situation is harmful to human health as
well as to plants and animals. These events triggered urgency for a responsibility and
appropriate legislation for correct waste management. EU and Portuguese policy main
objectives in the waste management is to prevent and reduce waste production, and
reduce their toxicity, through reuse and modification of production processes, adopting
cleaner technologies. Waste management must also avoid or at least reduce its risk to
human health and to environment. In Portugal, wastes sector was suffered a revolution
on the last years, due to the appearance of the Strategic Plan for Solid Waste I (PERSU
I) in 1997 and by the constant pressure from the EU for their state members and waste
producers. In December 2006 it was created the PERSU II to correct all mistakes made in
the previous plan. However soon realized that PERSU II had very ambitious goals and so
unattainable that triggered the need to reformulate these objectives. The aim of this
overview in waste management was to follow the goals outlined in PERSU II, identifying
the progress of each operational system over the years. It was also a target to compare
those results to European statistics tracing possible ways to permit compliance with EU
objectives in future.
Keywords: Waste Management; PERSU I; PERSU II; Municipal Wastes (MW)
INTRODUCTION
Municipal Wastes (MW) problem in Portugal have been getting worse over time and its resolution
seems to be far away. In Portugal as well as worldwide, MW production has grown exponentially,
and the main cause of this problem is the society growth, where the world consumerism prevails
[1]. Thus, one of the most serious problems facing any urban center is the amounts of wastes
generated. Solid wastes are presented with one of most environmental problems of actual society
and the only way to solve this problem is creating an effecting management system [2]. Although
an effective policy of Integrated Management of MW has been established in Portugal, this type of
wastes is mostly sent to landfills and incinerators (end of line-treatments). Planning and Waste
Management encompasses all types of wastes from different sources and constitute the aim of this
environment polices [3]. In Portugal the legislation on MW has been amended several times in
recent years as a reflection of its outdated compared to the demands of European Union. In fact,
most of developed countries, usually more aware of these issues, built a complete legislative
structure and framework for this problem [4]. In future, solid wastes must be seen not only as a
346
problem to solve in the most cost-effectively way, but also a potential resource of raw-materials.
Final destination given to wastes presents, in a short timeframe, a great importance and therefore it
is necessary to find the most efficient management system for them [5].
In this work it was identified and overviewed the waste management in Portugal over the years. It
was analyzed the period before the implementation of PERSU I and the execution of PERSU II in
present time. These results have also been compared with European statistics.
WASTE MANAGEMENT IN PORTUGAL PAST

Portugal situation in 1995 with regard to solid waste management was characterized by total failure
of the most basic requirements for environmental preservation, because MW were dumped in open
landfills in 76% of cases and 14% in controlled landfills [1,6].
In 1996, MW management was based on the distribution in 275 systems in the municipalities which
proceeded to the deposition on more than 300 waste landfills. That situation harmed the
landscapes and soils and provided vehicles for spreading diseases in local populations. The
exception to this scenario consisted in 13 places where the deposition was carried out controlled,
and in 5 units for organic recovery, but mostly in a poor state of exploitation [1,5]. Table 1 shows
the MSW management in Portugal in 1995.
Table 1 Solid Waste Management in Portugal in 1995 (source: Russo [5])

Solid Waste Management in Portugal [1995]
Ton/year %
MW total production 3 340 000 -
Glass recycling 90 952 2.7
Paper/cardboard recycling 33 400 1
Composting 299 190 9
Other recycling - 0.3
According to Russo [5] the characterization of Portugal state in 1995 (table 1) was made with the
available data, although in some cases unreliable, particularly in MSW production. However it was
identified a growth rate of 3% per year.
In 1997, waste sector in Portugal has undergone a revolution mostly due to the appearance and
formalization of the Strategic Plan for Municipal Solid Wastes I (in Portuguese - PERSU I) and due
to the constant pressure from European Union over the states and producers of wastes in the
expectation that targets for recovery and recycling were achieved [1,7]. The main guidelines of
PERSU I appointed to:
i. Closure of all open air landfills and their environmental remediation;
ii. Construction of infrastructure for MSW treatment;
iii. Strengthening the selective collection and the multi-material recycling;
iv. Achievement of goals for 2000-2005.
However, some of the goals outlined in PERSU I have not been realized, as can be seen in table 2.
Table 2 Overview of PERSU I accomplishment between 2000 and 2004 (source: Russo [5])
Reduction Recycling Landfills Open air dumps Incineration Composting
Year
[%] [%] [%] [%] [%] [%]
Situation in 1995 0 4 14 73 0 9
PERSU I goals for
2.5 15 41.5 0 26 15
2000
Situation in 2000 0 6 55 12 22 6
Balance in 2000 -100 60 32.5 -100 -15 -60
PERSU I goals for
5 25 23 0 22 25
2005
Situation in 2004 0 6 71 0 20 8
Balance in 2004 -100 -76 >100 100 -9 -68
347
It is possible to verify that eradication of open air dumps and incineration goals established in
PERSU I for 2005 were achieved. However, on reducing waste production the objectives
established in PERSU I were not accomplished and there was none strategy for that [5,8,9]. Indeed
there was no reduction of waste production, and recycling and composting did not reached the
established levels, having been respectively -76% and -68% for targets. The elimination of waste
dumps, presents itself as the great victory of the first generation of this plan [5,10].
WASTE MANAGEMENT IN PORTUGAL PRESENT

With the beginning of a new cycle of planning associated with the National Strategic Reference
Framework (in Portuguese - QREN) it was necessary the review of PERSU I to ensure continuity
on national and community wastes policy. Some of the reasons for the revision of PERSU I are:
Observed changes at the level of EU policy on waste (Directive N 2006/12/CE);

Approval by the Decree N 178/2006, of the new General System of Waste Management,
which showed changes in the legal sector;
Commitment made by Portugal in relation to compliance with the Kyoto Protocol to reduce
emissions and greenhouse gases.
Published through Decree N 187/2007 on 12 February, PERSU II reviews the PERSU I, and its
the new benchmark for the horizon of 2007 to 2016. This plan reviews the strategy for reduction of
Biodegradable Municipal Waste (BMW) that are sent to landfills (in Portuguese -
ENRRUBDA, 2003) and the Intervention Plan for Solid Waste and Similar (in Portuguese -
PIRSUE, 2006). The strategic guidelines presented in PERSU II are:
i. Reduce, Reutilize and Recycle;

ii. Separate at source;
iii. Minimize landfill deposition;
iv. Waste to Energy politic in not recyclable fraction;
v. Valid information at useful time;
vi. Sustainability in management systems;
vii. Kyoto protocol [1, 4,5,7].
For the horizon established in PERSU II, strategy for MSW management is completely conditioned
by the fulfillment of Community objectives set for the years: 2009, 2011 and 2016. The main goals
determined by the EU directives are listed in table 3.
Table 3 Goals of MSW management in Portugal (Source: Russo [5])

Packaging Directive N 92/2006 Landfills Directive N 152/2002
2011 2006
Total packaging waste valorization: 60% Biodegradable Municipal Wastes reduction
Total packaging waste recycling: 55-80% (BMW) to landfills by 75% related to total
Glass waste recycling: 60% amount (by weight) of BMW produced in 1995
Paper and cardboard recycling: 60% 2009
Plastic recycling: 22,5% Biodegradable Municipal Wastes reduction
Metal recycling: 50% (BMW) to landfills by 50% related to total
Wood recycling: 15% amount (by weight) of BMW produced in 1995
2016
Biodegradable Municipal Wastes reduction
(BMW) to landfills by 35% related to total
amount (by weight) of BMW produced in 1995
348
Municipal Wastes Production in Portugal
Table 4 shows the variation of municipal wastes productions in Portugal between 2005 and 2009.
Table 4 Municipal Waste production in Portugal between 2005 to 2009 (souce: APA [6]).
Population Total of MW ([tons]
2009 2008 2007 2006 2005 2009 2008 2007 2006 2005
10.144 10.135 10.126.8 10.110.2 10.082.1 5.184.5 5.154.4 4.648. 4.641.1 4.470.8
Portugal
.940 .309 80 71 54 92 34 22 03 69
Annual
variation 0.10 0.08 0.16 0.28 0.38 0.59 10.89 0.15 3.81 1.75
[%]
Total municipal wastes production in Portugal in 2009 was approximately 5.184.000 tons.
Compared with calculated values for 2008, in 2009 it was observed an increase of 0.59% in MW
production, which corresponds to 30.000 tons [6]. According to INE [3], in Portugal the amount of
waste collected between 2004 and 2009 grow at an annual rate of 3%. The amount of collected
wastes per capita also increased 3%, setting an annual MW production of 511 kg/person. These
represent a daily MW production of 1.4kg per inhabitant. In terms of quantities of wastes generated
per capita, Portugal is slightly below the EU average at 27 countries because in 2009 reached 524
kg per person.
Waste production by management operation

Waste management operations are classified due their final destination. These operations are
divided into two distinct groups: waste recovery operations and waste disposal operations. In the
first type of operation are contemplated the energy recovery (incineration), organic recovery
(composting) and selective collection (recycling). In the second type of operations it is considered
the final disposal of wastes in landfills [1,7]. Table 5 presents the MW production in Portugal by
management operation.
Table 5 Municipal waste production in Portugal by management operation between 2005-2009

(source: APA [6])
Energetic Selective
Landfill Organic Valorization Total
Year Valorization Collection
Tons % Tons % Tons % Tons % Tons
2009 3.200.676 62.0 958.883 18.6 418.404 8.1 606.629 11.7 5.184.592
2008 3.372.505 65.5 869.262 16.9 377.175 7.3 535.492 10.4 5.154.434
2007 3.014.311 64.8 825.938 17.8 318.264 6.8 489.703 10.5 4.648.222
2006 3.040.953 65.5 854.578 18.4 298.600 6.4 446.973 9.6 4.641.103
2005 2.838.373 63.5 937.102 21.0 310.433 6.9 384.961 8.6 4.470.869
In the period under review, selective collection and consequent recycling of wastes constitute the
management operation that has the fastest growing verifying that more than 11% of wastes was
been collected. Indeed between 2004 and 2009, quantities of selectively collected waste were
clearly superior that total generated waste (3%) with an average growth rate of about 15% per year
[3,6].
In the universe of undifferentiated collected wastes in 2009, the main final destination was landfill
disposal (62%) followed by energy recovery (19%) and organic recovery (8%). Landfill disposal and
energy recovery achieved average growth rates of 2% per year and organic recovery achieved 6%.
In selectively collected waste (figure 1), glass was the material collected in larger amounts in 2005,
representing almost half of the quantities collected in that year. In 2009, glass collection represents
only 11% of total selectively collected waste. In that year the main collected material was paper
and cardboard with an average growth of 18% per year [3,6].
349
Figure 1 Selective collection of MW in Portugal by material between 2004 and 2009 (source: INE
[3]).
European statistics
According to released data by EUROSTAT there are some capable comparisons that can be made
between Portugal and EU 27 for 2008 (latest year information available to EU). Figure 2 shows the
amount of municipal wastes sent to landfill disposal on Europe in 2008 and figure 3 presents the
quantity of municipal wastes recycled on Europe in 2008.
Figure 2 Municipal wastes (%) sent to landfill disposal in Figure 3 Municipal wastes (%) recycled in 2008 (source: INE
2008 (source: INE [3]) [3])
Landfill disposal represents 65% of undifferentiated collection in Portugal, which is almost 8 points
above EU average at 27 countries. Although the proportion of MW sent to landfills was slightly
higher than EU average, in Portugal the growth rate is lower than the total production of wastes
which can presents a converging trajectory to EU average [6,11].
Regarding to MW recycling, between 2004 and 2008, Portugal doubles the quantities of materials
sent to this type of operation achieving 10% of total selectively collected waste. In EU average that
value is 17%. However the evolutionary trend in recent years indicates a path of convergence with
EU average [6,11].
CONCLUSIONS
In recent decades waste generation has increased significantly mainly due to the excessive growth
of world population and their changes of habits. The intensification of migration from rural to urban
areas, the increase of disposable and packaging products and the high consumerism that
350
characterizes the contemporary society contributes to the exponentially growth of generated
wastes.
The waste management in Portugal was faced significant changes through the years. Before
implementation of PERSU I, waste management was at charge of municipalities and in most
cases, wastes were dumped in open and not controlled landfills. In 1996 after creation of PERSU I,
waste management in Portugal suffered several changes. However this proposed plan was not
completed entirely. This scenario triggered the need to formalize a new plan PERSU II. This new
plan established targets for municipal solid waste management, over 2007 to 2016. However, soon
was realized that PERSU II had very ambitious goals. In this work were verified some of these
difficulties. Comparing Portuguese data with EU statistics it is possible to observe that Portuguese
targets are below European average. Nonetheless, it is also possible to conclude that some of
these goals indicate a path of convergence with EU average, as long as traced pathway is
continued.
REFERENCES
[1] J. Levy, A. Cabeas, Resduos Slidos Urbanos Princpios e Processos, AEPSA, Lisboa
(Portugal), 2006, 331 pp.
[2] R. Oliveira, Tecnologias de Controlo da Poluio, 2010.
[3] INE, Gesto de Resduos em Portugal, 2004 2009. O sector dos resduos em Portugal.
Destaque Informao Comunicao Social, 2010, 15 pp.
[4] M. Russo, Tratamento de Resduos Slidos. University of Coimbra Science and
Technology School, 2003, 196 pp.
[5] M. Russo, Avaliao dos processos de transformao de resduos slidos urbanos em
aterro sanitrio. PhD thesis in Civil Enginnering. University of Minho Enginnering School,
2005, 320 pp.
[6] APA Caracterizao da Situao dos Resduos Urbanos em Portugal Continental em 2009,
2010, 11 pp.
[7] G. Martinho, G. Gonalves, Gesto de Resduos Urbanos. Universidade Aberta. Lisboa,
2002.
[8] M. Cruz, A Caracterizao de Resduos Slidos no mbito da sua Gesto Integrada, Master
degree thesis in Environmental Science. University of Minho Science School, 2005, 223
pp.
[9] S. Teixeira, Estratgias de Gesto de Resduos Slidos Urbanos. Master degree thesis in
Environmental Enginnering, University of Porto Enginnering School, 2004. 307 pp.
[10] M. Russo, Reorganizao do sector dos Resduos Urbanos em Portugal: Uma oportunidade
de reestruturao do PERSU II. Valorizao de Resduos, n. 16 (2011), 49 pp.
[11] APA Sistemas de Gesto de Resduos Urbanos. DOGR-DRU, 2009.
351
USE OF POLYURETHANE WASTE TO RETAIN HYDROCARBONS IN

AQUEOUS MEDIA
1 2 2 1
E. Pion Giz , F. Relea Gins , E. Gonzlez Prieto and J.M.Lpez Vilario
1 Laboratory of Chemistry, Technological Research Center, University of A Corua. Campus de
Esteiro s/n, E-15403 Ferrol. Spain. iquimica@cdf.udc.es
2 CESPA, I+D Department, Avda. Catedral 6-8, 1, E-08002 Barcelona, Spain.
e.gonzalez@cespa.es
ABSTRACT
Polyurethane is one of the biggest problems in plastics waste according its volume and
weight. The Characteristics of this polymer make quite difficult their valorization because
of its chemical and thermal properties.
In this work, the possibility of using rigid polyurethane and polyurethane foam wastes to
reduce the levels of different hydrocarbons present in water samples is tested. Tests
were made in batch and continue assays to reproduce different contact possibilities. The
target compounds were different aromatic hydrocarbons, all of them concern compounds
in the European directive to control the quality of natural waters.
This possibility would allow to different companies the use of one of their residues in a
pre-filtration system to avoid the contamination of some compounds with difficult
treatment in water.
Keywords: Polyurethane; plastics valorization; plastics waste.
INTRODUCTION
Polyurethanes are one of the most versatile materials in the world today. Their many uses range
from flexible foam in upholstered furniture, to rigid foam as insulation in walls, roofs and appliances
to thermoplastic polyurethane used in medical devices and footwear, to coatings, adhesives,
sealants and elastomers used on floors and automotive interiors. Polyurethanes frequently are
utilized in durable products with long lifetimes, often more than ten years. Polyurethane products
have become a valuable part of our modern life through improving comfort and reducing energy
consumption. Chemically are a class of polymers that is produced by the polyaddition of
polyisocyanates and polyols. They are a whole family that covers a wide range of physical
properties and they are used in most applications for their durability.
Normally the valorization possibilities are based in different uses as:
Lightweight aggregate in concrete in no structurally uses and urban furniture [1,2].
Chemical processing, where different systems are used to produce the polymer chain
breakage to produce the original or some others different monomers [3].
Included in different structures to fill in them with no special treatments.
Thermal valorization, where the calorific power of this polymer is employed to produce
electric energy.
Among these possibilities the chemical processing is the most studied. Several studies have
analyzed the possibility to obtain different compounds with commercial possibilities. T. Fukaya et al
(2006) [4] and C.H. Wu et al (2002) [5] among others have studied the recycling of rigid
polyurethane with heating process (175 200 C) in extruder conditions (high pressure) and room
temperature and atmospheric pressure respectively. There are quite more studies using flexible
polyurethane with different conditions and systems [6-8]. In almost all these studies is present the
necessity of some of these parameters: temperature, pressure and catalysis. This fact produces
that in most of cases is not commercially sustainable the recycling of great volumes of
polyurethane foams by these systems. In other cases the low quality of the chemical products
352
make impossible to find a commercial possibility, although in some cases this is possible must to
the presence of a big company close to the recycler that it needs the chemical produced.
In this work the possibility of using the polyurethane wastes to eliminate hydrocarbons from water
samples was studied. Unfortunately the presence of hydrocarbon contamination is almost
ubiquitous in sea water must to oil spill (accidents and deliberates), port traffic and others,
sometimes these hydrocarbons are also present in rivers and estuaries because of several
anthropic contamination sources. When an accident or a localized hydrocarbon spill has happened
the use of anticontamination barriers is usual. The use of two different polyurethane wastes was
assayed: polyurethane foam came from mattress and sofa (PF) and rigid polyurethanes came from
the recycling of fridges and freezers (RP). The capacity of polyurethane foams to retain a great
number of families of compounds is well known [9,10]. In this work, the possibility of using rigid
polyurethane and polyurethane foam wastes to reduce the levels of different hydrocarbons present
in water samples was tested.
EXPERIMENTAL
Polyurethane samples were taken from the polyurethane recycling plant of Cespa S.A. in Cerceda
(A Corua, Spain).
Polyurethane rigid is collected from a grinding unit used in the recycling of fridges and freezers. In
this plant are separated aluminum, iron, oils, plastics and rigid polyurethane. This polyurethane is
picked in a little cylinder format (approx. 3 mm of diameter, 10 mm large). These cylinders are
crushed in a Retsch PM100 mill (2.5 min. 450 rpm) and sieved under 63 m .
Polyurethane foam is collected from a system capable of separate strings and polyurethane foam
3
from bed mattress and sofas. This system cut and presses the foams until densities of 0.25 g/cm
approximately and finally a linear foam waste is produced. Pieces of 5 cm of diameter were cut.
In the Fig. 1 are shown SEM photographs of both kinds of samples.
Fig. 1, SEM photographs of polyurethane foam (left) and rigid polyurethane (right).
0.5 g samples (polyurethane foam was compressed until 2 mL volume) were put into glass
syringes in a Visiprep (from Supelco) system. Below this syringes were placed C18 Sep-Pak
cartridges (from Waters), these cartridges were pre-aconditioned with 5 mL of dichloromethane, 5
mL of methanol and 2x5 mL of water. Samples of 50 mL of water spiked with 2 and 10 ppb of a
mixture of polycyclic aromatic hydrocarbons (PAHs) were passed through the samples and C18
cartridges.
The PAHs retained in the cartridges were eluted with 5 mL of dichloromethane. This volume was
evaporated under N2 stream until the last drop and 1 mL of methanol was added. After this, the
samples were analyzed in a 2695 HPLC Waters system with photodiode array (Waters 2998) and
fluorescence (Waters 2475) detector.
353
The hydrocarbons analyzed are shown in table 1, where the retention time, the wave length used in
the PDA detector and the excitation and emission wave lengths used in the fluorescence detector
have been included.
Table 1. Polycyclic aromatic hydrocarbons analyzed with their retention time, PDA wave length and
excitation and emission wave length used in the fluorescence determination.
t (min) PDA (nm) Fl ex. (nm) Fl em. (nm)

Naphtalene 5.63 220 260 325
Acenaphtene 7.61 250 230 383
Fluorene 8.15 250 230 383
Phenantrene 8.56 250 230 383
Fluoranthene 9.98 270 230 383
Pyrene 11.28 270 270 400
Benzo (a) anthracene 11.45 270 270 400
Crysene 12.96 300 270 370
Benzo (b) fluoranthene 13.51 300 270 370
Benzo (k) fluoranthene 14.39 300 280 400
Benzo (a) pyrene 15.15 300 280 400
According to the experimental procedure described, the retention of theses PAHs by the
polyurethane samples was determined to evaluate the possibility of use these wastes in sea anti
contamination barriers or like a containment in companies to avoid a possible accident with an
hydrocarbons spill. In Fig. 2 and Fig. 3 are shown the adsorption capacities of polyurethane foam
and rigid polyurethane against different concentrations of hydrocarbons present in water samples.
100
Polyurethane foam 2ppb
Rigid polyurethane 2ppb
90
80
Adsoption %
70
60
50
40
Fig. 2, Adsorption capacity of polyurethane wastes when a sample of water spiked with 2 ppb of
PAHs is filtered.
354
100
Polyurethane foam 10ppb
Rigid polyurethane 10ppb
90
80
70
Adsorption %
60
50
40
30
20
Fig. 3, Adsorption capacity of polyurethane wastes when a sample of water spiked with 10 ppb of
PAHs is filtered.
PAHs levels in marine water samples are usually under 1 g/L (sum of 16 PAHs) [11]. After the
Prestige oil spill in the northwest of Spain these levels were among 0.02 and 5 g/L (sum of 16
PAHs) [12]. In this study, the polyurethane samples were tested with water spiked with 2 and 10
g/L, concentrations quite higher than expected in a natural environment. The results show the
great capacity of polyurethane foam to retain the HAPs analyzed. The retention levels were around
90 % in almost all cases. Benzo (k) fluoranthene and Benzo (a) pyrene showed worst retention
levels than the other ones.
CONCLUSIONS
The PAHs adsorption of polyurethane foam is better than the offered by the rigid polyurethane.
Polyurethane foam wastes could be reused in anti contamination marine barriers or anti accidental
spills.
ACKNOWLEDGEMENTS
This work is included in the project 10MDS040E kindly supported by the Xunta de Galicia INCITE
program.
REFERENCES
[1] Fraj, A.B.; Kismi, M. and Mounanga, P., Valorization of coarse rigid polyurethane foam waste
in lightweight aggregate concrete, Construction and Building Materials, 24 (2010) 1069-1077.
[2] Mounanga, P.; Gbongbon, W.; Poullain, P. and Turcry, P., Proportioning and characterization
of lightweight concrete mixtures made with rigid polyurethane foam wastes, Cement &
Concrete Composites, 30 (2008), 806-814.
[3] Zia, K.M.; Bhatti, H.N. and Bhatti, I.A., Methods for polyurethane and polyurethane
composites, recycling and recovery: A review, Reactive & Functional Polymers, 67 (2007),
675-692.
355
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decomposition process as chemical recycling for rigid polyurethane foam, Polymer
Degradation and Stability, 91 (2006), 2549-2553.
[5] C.H. Wu, C.Y. Chang and J.K. Li, Glycolysis of rigid polyurethane from waste refrigerators,
Polymer Degradation and Stability, 75 (2002) 413-421.
[6] C. Molero, A. de Lucas, J.F. Rodrguez, Recovery of polyols from flexible polyurethane foam
by split-phase gliclisis: glycol influence, Polymer Degradation and Stability, 91 (2006),
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[7] N. Asahi, K.Sakai, N. Kumagai, T. Nakanishi, K. Hata, S. Katoh and T. Moriyoshi,
Methanolysis investigation of commercially available polyurethane foam, Polymer
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[9] E.E. Baldez, N.F. Robaina, R.J. Cassella, Employment of polyurethane foam for the
adsorption of mthylene blue in aqueous medium, Journal of Hazardous Materials, 159
(2008), 580-586.
[10] V.A. Lemos, M.S. Santos, E.S. Santos, M.J.S. Santos, W.N.L. dos Santos, A.S. Souza, D.S.
de Jess, C.F. das Virgens, M.S. Carvalho, N. Olescczuk, M.G.R. Vale, B. Welz, S.L.C.
Ferreira, Application of polyurethane foam as a sorbent for trace metal pre-concentration A
review, Spectrochimica Acta Part B: Atomic Spectroscopy, 62 (2007), 4-12.
[11] C. Guitart, N. Garca-Flor, J.M. Bayona, and J. Albaigs. Occurrence and fate of polycyclic
aromatic hydrocarbons in the coastal surface microlayer. Marine Pollution Bulletin, 54 (2007),
186-194.
[12] J.J. Gonzlez, L. Vias, M.A. Franco, J. Fumega, J.A. Soriano, G. Grueiro, S. Muniategui, P.
Lpez Maha, D. Prada, J.M. Bayona, R. Alzaga, J. Albaigs. Spatial and temporal
distribution of dissolved/dispersed aromatic hydrocarbons in seawater in the area affected by
the Prestige oil spill. Marine Pollution Bulletin, 53 (2006), 250-259.
356
VALORIZATION OF FATS FROM ANIMAL WASTES: BIODIESEL

PRODUCTION
1 2 3 4 5
P.C. Silva , A. Sampaio , N.S. Caetano , E. Ramalho and A. Crispim
1 CIETI/DEQ/ISEP Centre of Innovation on Engineering and Industrial Technology, Chemical
Engineering Department, School of Engineering (ISEP) of Polytechnic Institute of Porto, R Dr.
Antnio Bernardino de Almeida, 431, 4200-072- Porto, Portugal, pcs@isep.ipp.pt
Antnio Bernardino de Almeida, 431, 4200-072- Porto, Portugal, 1010258@isep.ipp.pt
Antnio Bernardino de Almeida, 431, 4200-072- Porto; LEPAE/DEQ/ISEP Laboratory for
Process, Environmental and Energy Engineering, Chemical Engineering Department, School of
Engineering (ISEP) of Polytechnic Institute of Porto, Portugal Portugal, nsc@isep.ipp.pt
Antnio Bernardino de Almeida, 431, 4200-072- Porto, Portugal, err@isep.ipp.pt
Antnio Bernardino de Almeida, 431, 4200-072- Porto, Portugal, aar@isep.ipp.pt
ABSTRACT
Two of the most important concerns regarding planet sustainability are energy
management and waste disposal. Renewable energy sources and waste valorization
processes are therefore very important. Among biofuels, biodiesel has very good
utilization and environmental properties that allow partial or total replacement of diesel
fuel. Biodiesel can be produced from residues like waste frying oils and animal fats. The
purpose of this work is to produce biodiesel from fat obtained from industrial animal
residues: green and lime fleshings from tanneries and slaughterhouses wastes. The fats
were previously characterized and some of the samples presented a high acid value. For
these materials, an acid esterification step prior to the transesterification reaction was
needed, in order to lower the acid value. Transesterification with methanol was performed
using sodium hydroxide or sodium methylate as catalysts, at 65C. The quality of
biodiesel products was assessed by some of EN 14214 Standard parameters. The
results show that most of the samples are within the specifications, except for high CFPP.
This is typical of biodiesel produced from animal fats that present high saturated fatty acid
content. Nevertheless, these products can be used in mixtures with biodiesel from
vegetable oils, in order to meet standard specifications.
Keywords: Biodiesel; fleshings; fat waste valorization
INTRODUCTION
Sustainable energy management is a main world concern, considering the fact that fossil fuels
supply is limited and energy demand continues to rise. Environmental protection is also a major
concern of the International Community, leading to the signature of Kyoto Protocol (1997) where a
commitment was made regarding greenhouse gas emissions reduction. Biofuels have therefore
gained fundamental importance in this context and are now widely used as alternative to fossil
fuels. In the European Union, Directive 2003/30/EC [1] imposes a 5,75% (based on energy
content) incorporation of biofuels in all transportation fuels since December 2010. Biodiesel (a fuel
357
comprised of mono-alkyl esters of long chain fatty acids derived from vegetable oils or animal fats)
has very good utilization as well as environmental properties and is commercially used as total or
partial replacement of diesel fuel. Although biodiesel can be synthesized from many types of
triglyceride containing materials, vegetable oils are the main feedstock used in industry. Presently,
the cost of the cereals used to produce these vegetable oils is increasing due to the growing
market needs, raising biodiesel costs. Also, this huge cereals demand introduces a sustainability
problem for the next coming years and an inacceptable competition with its use as food.
Significant research effort is being dedicated to the search for alternative feedstocks. Among these,
residues as waste cooking oils and animal fats present good results as raw materials for biodiesel
production [2-4]. Furthermore, this is an environmental friendly disposal option for these residues,
while adding value to problematic wastes.
Livestock and poultry related industries generate a large amount of fat containing solid wastes,
usually with high disposal costs. In particular, tanning industry generates a high quantity of solid
wastes with high pollution level. It is known that only 20% of the hide results in finished products
[5]. From an economical and environmental point of view, there is great interest in the valorization
of the generated solid wastes.
Some researchers have already studied biodiesel production from animal fat residues, namely
chicken fat [6], fleshing oil [7] and poultry meat and bone meal [8].
Traditional biodiesel production processes are based on the transesterification of triglycerides with
methanol using an alkaline homogeneous catalyst (NaOH), in batch or continuous plants. This
process requires feedstocks with low free fatty acid (FFA) and water contents. Typical animal fats
contain from 5% to 30% FFAs [9], and soap formation may occur in considerable amounts (Fig.1)
making product separation very difficult.
O O
+ -
HO C R + NaOH Na O C R + H2O
Fatty acid Sodium Sodium soap Water

hydroxide
Figure 1. Saponification reaction of free fatty acids.

To overcome this problem, a pretreatment step is usually required to convert the free fatty acids to
methyl esters, thereby reducing the FFA level. This treatment consists of an esterification with
methanol and sulfuric acid as catalyst, producing methyl esters and water (Fig.2). After this
reaction, the treated fat can be transesterified with an alkali catalyst to convert the triglycerides to
methyl esters.
O O
(H2SO4)
HO C R + CH3OH CH3 O C R + H2O
Fatty acid Methanol Methyl ester Water
Figure 2. Esterification reaction of free fatty acids.
Besides its high FFA content, another feature of animal fats is that its fatty acid composition shows
a more saturated character than vegetable oils, presenting therefore low iodine values. Biodiesel
obtained from these raw materials usually presents poor cold flow performance, which could limit
its utilization without the use of additives or blending. On the other hand, the high degree of
saturation may benefit the oxidation stability of the product [10].
The purpose of this work is to produce biodiesel from fat obtained from four different industrial
animal residues and to compare the properties of the products with the European standards. Three
types of residues from tanneries (pressure extracted fat from green fleshings and lime fleshings
and fat obtained by thermal hydrolysis of lime fleshings) and also fat obtained by thermal extraction
of slaughterhouses residue, were chosen as raw materials for this study.
358
Fat extraction and characterization

Solid green fleshings and lime fleshings received from a tannery company were heated at 65C
2
and then pressed at 41 kg/cm using a mechanical press (Mega KMG-300). A drilled stainless steel
cylinder was designed to contain the samples during the pressing process. The extracted fat was
filtered to remove solid impurities. These samples were named S1 (fat from green fleshings) and
S2 (fat from lime fleshings).
Sample S3 is obtained by thermal hydrolysis of lime fleshings. Sample S4 is fat obtained from
slaughterhouses solid residues by thermal extraction.
All samples were characterized for moisture using gravimetric methods and fat content by Soxhlet
method. Acid value was determined according to EN 14104 standard and iodine value was
determined according to EN 14111 standard.
Biodiesel production
Biodiesel was produced by transesterification with methanol and sodium hydroxide or sodium
methylate as catalysts. For samples S2 and S4 it was necessary a pretreatment step with methanol
and sulfuric acid prior to transesterification reaction, in order to lower the acid value to less than 5
mgKOH/gfat. The conditions used in this esterification treatment were: 6:1 methanol/fat molar ratio,
1,5% (w/w, based on the fat) sulfuric acid, 2 hours and 65C. Products were separated by gravity
and acid number of treated fat was evaluated.
Transesterification step was performed at 65 C for 2h under stirring, using a 6:1 methanol/fat
molar ratio and 1% (w/w, based on the fat) sodium hydroxide.
To test the effect of sodium methylate as an alternative catalyst, sample S3 was also
transesterified using 1,5% (w/w, based on the fat) of sodium methylate instead of sodium hydroxide
(sample S3-M).
The ester product was separated by gravity and washed with water to remove the catalyst, glycerol
and methanol. A final drying step with magnesium oxide was performed, prior to product
characterization.
Biodiesel characterization
Ester product quality was evaluated by some of the EN 14214 standard parameters: density by
pycnometer method, ester content by gaseous chromatography, viscosity, acid value, iodine value
and cold filter plugging point (CFPP) according to standards EN ISO3104, EN14104, EN 14111
and EN 116, respectively.
The results of the characterization of the fats are presented in table 1. Mechanical extraction of the
fat seems to be less effective than the other processes, as fat content of samples S1 and S2 are
slightly inferior to samples S3 and S4. Low iodine values show the saturated character of animal
fats, as expected. High acid values presented by samples S2 and S4 indicate the need for an
esterification treatment prior to biodiesel production step. After this treatment, both samples
presented acid values below 5 mgKOH/gfat and thus the transesterification reaction was performed.
Table 1. Fat samples characterization.

Sample Moisture Fat content Acid value Iodine value
[% w/w, [% w/w, [mgKOH/ [giodine/
wet basis] dry basis] gfat)] 100gfat]
S1 5,5 93,1 0,3 nd

S2 3,1 96,3 10,9 41,3
S3 0,5 99,6 3,7 51,5
S4 0,7 99,9 47,8 nd
nd- not determined
359
After transesterification reaction and purification, clear light yellow biodiesel sample were obtained,
as shown in fig. 3 for samples S1 and S2. Biodiesel characterization results are shown on table 2,
as well as EN 14214 standard reference values.
Figure 3. Fat and biodiesel samples. From left to right:

sample S2- fat and biodiesel ; sample S1- fat and biodiesel.
As can be seen, all samples tested produced methyl ester mixtures that are within or very close to
the specifications for its utilization as fuel. Low iodine values of raw materials, typical of animal
fats, originate high values of CFPP and therefore poor cold flow performance of biodiesel. This
limitation can however be overcome by additivation [11] or by blending with biodiesel from
vegetable oils.
Regarding the effect of using sodium methylate instead of sodium hydroxide as catalyst, the results
do not differ significantly (samples S3 and S3-M). The industrial use of sodium methylate presents
some advantages, as it makes unnecessary the mixing step of methanol and hydroxide.
Table 2. Biodiesel properties and EN 14214 standard values.

Sample Density Viscosity at Acid value Iodine value CFPP Ester
3 2
[kg/m ] 40C [mm /s] [mgKOH/ [giodine/ [C] content
gfat)] 100 gfat] [%]
S1 876 5,0 0,4 nd 2 99,0
S2 878 5,7 0,1 47,9 5 90,0
S3 872 3,5 0,3 50,8 3 97,3
S3-M 872 3,7 0,5 nd 6 99,0
S4 nd nd nd nd nd 93,3
EN
14214 860-900 3,5-5,0 <0,5 <120 a) >96,5
nd- not determined ; a) Country and season specific; usually below 0C.
CONCLUSIONS
Fat obtained from different industrial animal residues was used as raw material for biodiesel
production. As expected in animal fats, some of the samples present high FFA content and a pre-
treatment step prior to the transesterification reaction is necessary. Methyl ester mixtures were
obtained under the following reaction conditions: reaction temperature: 65 C, reaction time: 2h,
methanol/fat molar ratio: 6:1, catalyst: 1% (w/w, based on the fat) sodium hydroxide. Product
360
characterization shows that these mixtures are within or close to the specifications of the most
important parameters of EN 14214 Standard. The exception is high CFPP values, as usual in
biodiesel produced from animal fat. Nevertheless, these products can be used in mixtures with
biodiesel from vegetable oils in order to meet standard specifications. This valorization route of
residual fat materials is an interesting alternative for biofuel production and also contributes to
solve the waste management problem of livestock and poultry related industries.
REFERENCES
[1] Directive 2003/30/EC of the European Parliament and Council, Official Journal of the European
Union, L 123/42, 17.5.2003.
[2] K.G.Georgogianni, M.G.Kontominas, E.Tegou, D. Avlonitis and V. Gergis, Biodiesel
Production: Reaction and Process Parameters of Alkali-Catalyzed Transesterification of Waste
Frying Oils, Energy and Fuels,21 (2007) 3023-3027.
[3] A.N. Nebel and M. Mittelbach, Biodiesel from extracted fat out of meat and bone meal, Eur. J.
Lipid Sci. Technol., 108 (2006) 398-403
[4] B. Arajo, R. Nunes, C. Moura, E. Moura, A. Cit, and J. Jnior, Synthesis and
Characterization of Beef Tallow Biodiesel, Energy Fuels, 24 (2010) 4476-4480.
[5] G.H. Burrows, Clean technology in the processing of leather, Proceedings of the XXVI
IULTCS Congress, Cape Town,(2001) 49-62.
[6] E. Alptekin, and M. Canakci, Optimization of pretreatment reaction for methyl ester production
from chicken fat, Fuel, 89 (2010) 4035-4039.
[7] A. Isler, S. Sundu, M. Tuter, and F. Karaosmanoglu, Transesterification reaction of the fat
originated from solid waste of the leather industry, Waste Management, 30 (2010) 2631-2635.
[8] M. Santos, P.C. Silva and E. Ramalho, Biodiesel production from poultry meat and bone meal,
Proceedings of the Bioenergy: Challenges and Opportunities, Universidade do Minho,
Guimares, (2008).
[9] J.V. Gerpen, Biodiesel processing and production, Fuel Processing Technology, 86
(2005)1097-1107.
[10] H. Tang, R.C de Guzman, K.Y. Simon Ng, S.O. Salley, Effect of Antioxidants on the Storage
Stability of Soybean-Oil-Based Biodiesel, Energy and Fuels,24 (2010) 2028-2033.
[11] M. Guru, B. D. Artukoglu, A. Keskin, A. Koca, Biodiesel production from waste animal fat and
improvement of its characteristics by synthesized nickel and magnesium additive, Energy
Conversion and Management, 50 (2009) 498502
361
St
SYNTHESIS OF ALUMINA BASED ON INDUSTRIAL WASTE MATERIAL
S. Lpez-Andrs1, L. Fillali2, J.A. Jimnez2, H.Tayibi2, I. Padilla2 and A. Lpez-Delgado2

1 Dpt. Cristallography and Mineralogy. Faculty of Geology, UCM. 28040 Madrid. Spain.
2 National Centre for Metallurgical Research, CSIC. Avda, Gregorio del Amo, 8. 28040 Madrid.
Spain. alopezdelgado@cenim.csic.es
ABSTRACT
A hazardous waste generated in slag milling process by the aluminium industry was used
as a raw material for the synthesis of alumina, -Al2O3. This waste is considered as
hazardous material in the European legislation due to the release of toxic gases
(hydrogen, ammonia, methane and hydrogen sulphide) in the presence of water. The
process developed in this work allows to obtaining 1 ton of alumina from 4 tons of
hazardous waste and generates an inert solid residue consisting principally of spinel,
corundum and quartz with possible uses in cements or glass industry. This process
consisted of two steps: in the first one, nearly 90% of aluminium present in the waste is
recovered as a nanocrystalline boehmite, -AlOOH by hydrothermal treatment of the
waste. In the second step, the alumina is obtained by calcination of the boehmite at
1400C in air. The chemical composition of the alumina obtained consisted of 95% Al2O3,
3.3% Fe2O3, 0.8% SiO2 and other minor oxides to balance.
Keywords: alumina; boehmite; hazardous waste; aluminium industry;
INTRODUCTION
Sustainable development strategies of industrialized countries include the adoption of
environmentally-friendly measures that affect production processes and efficient uses of the
resource, as well as the generation and management of waste. Whether in the last decades
environmental policies were aimed fundamentally to eliminate or reduce waste generation,
nowadays they seek to save natural resources through the secondary resources management.
This last strategy is promoted by the recent Directive of the European Parliament and of the
Council on Waste (European Directive 2008/98/EC) [1]. Thus a number of researches have been
focused on the use of waste for different applications and uses [2, 3].
Polymorphic aluminium oxides with the chemical formula Al2O3, and commonly referred with the
generic name of alumina, are extensively used in numerous industrial applications (ceramics,
abrasive materials, absorbents, catalysts, biomaterials, composites, pigments, etc). Commercial
alumina is obtained from bauxite ore in a process which generated one of the major residues
produced from the aluminium industry, the red mud. Two tons of bauxite are necessary to produce
1 ton of alumina. Also for specific purposes, alumina is obtained by thermal treatment of
precursors, which are generally produced by precipitation of aluminium oxy-hydroxides from
solution of reagent grade aluminium salts [4-6].
In this work, a hazardous waste obtained by the tertiary aluminium industry in the milling slag
process was used as aluminous raw material for the synthesis of alumina. From a mineralogical
point of view, this waste consisted principally of corundum, spinel, metallic aluminium, quartz,
aluminium nitride, calcite, iron oxide, aluminium sulphide and other minor oxides and salts; the total
aluminium content ranges from 25 to 40%. The waste is a heterogeneous material from the
physical-chemical point of view because it is strongly dependant on the type and quality of the
processed scrap, the classification and trapping methods used, etc. It is defined as H12 and
considered as hazardous in the European legislation due to the release of toxic gases (hydrogen,
ammonia, hydrogen sulphide, etc) in the presence of water, according to the next reactions [7]:
362
2Al + 3H2O (l) 3H2 (g) + Al2O3 G025C = -208.0kcal (1)
2AlN + 3H2O (l) 2NH3 (g) + Al2O3 G025C = -78.7kcal (2)
Al4C3 + 6H2O (l) 3CH4 (g) + 2Al2O3 G025C = -405.7kcal (3)
Al2S3 + 3H2O (l) 3H2S (g) + Al2O3 G025C = -61.4kcal (4)
The waste was subjected to a hydrothermal treatment to produce the alumina precursor, boehmite,
(-AlOOH), as describe by Gonzalo-Delgado et al. [8]. Boehmite was calcined at different
temperatures to produce -Al2O3. The thermal transformation of boehmite into alumina was
followed by simultaneous thermogravimetric/differential thermal analysis (TG/DTA). Both boehmite
and corundum were characterized by XRD, XRF and SEM/TEM. The aim of this study is the
transformation of a waste into an added-value material in an attempt to achieve the definition of
"end-of-waste" for this waste as defined in the European Directive on Waste [1].
EXPERIMENTAL
Materials and Methods

The waste product used in this work is a very fine grey coloured powder, with a characteristic odour
derived from its aluminium nitride, carbide and sulphide contents. It comes from the fine suction
system used in the slag milling operation and was supplied by a tertiary aluminium industry
(Recuperaciones y Reciclajes Roman S.L. Fuenlabrada, Madrid, Spain). The major mineralogical
composition of the waste is as follows: 31.2% Al, 20.0% Al2O3 (corundum), 15.0% MgAl2O4
(spinel), 8.4% AlN, 8.0% SiO2 (quartz), 8.2% CaCO3 (calcite), 1.8% Fe2O3 (hematite), 1.5% TiO2,
1.5% chloride (Na/K), 0.7 % Al2S3 and other minor metal oxides. From the contents of metallic
aluminium, and aluminium nitride and sulphide the calculated emission of H2, NH3 and H2S, per ton
of waste are 388.3, 45.9 and 3.1Nm3, respectively [8].
The procedure employed to produce alumina from the waste is shown in the Fig. 1.
Acid
Aluminium Alkalinization Precursor Thermal Alumina
Digestion
Waste (pH 8) (Boehmite) Treatment
(HCl, 10%)
Inert Residue Salt Solution
Step 1: hydrothermal synthesis of the precursor Step 2: calcination of the precursor
Fig.1. Scheme of the experimental procedure to obtain alumina from the aluminium waste.
The process to synthesis alumina from the aluminium waste consisted of two steps: in the first one,
the precursor (nanocrystalline boehmite, -AlOOH) was obtained by hydrothermal treatment of the
waste. In the second step, the alumina was obtained by calcination of that boehmite at 1400C in
air for 7h.
In order to obtain the precursor boehmite, 50g of the waste were heat treated and vigorously stirred
with 50mL of a solution of HCl (10% v/v) to dissolve the aluminium compounds during 150 min. The
Al3+ solution obtained, with a pH lower than 2 was separated from the solid residue by filtration in a
pressure system (Millipore YT30 142 HW with 0.2m Isopore membrane filters). Then the acid
solution was subjected to alkalinization up to pH 8 by dropwise adding a 1N NaOH solution. The
precursor is obtained as a gel which was separated by centrifugation, washed with distilled water,
dried at 150C and then it was crushed in a mortar to get a fine powder.
363
Characterization techniques
The chemical composition of the samples was determined by X-ray fluorescence (XRF, PANalytical
AXIOS wavelength-dispersive X-ray spectrometer) on compacted specimen of 37mm diameter. X-
ray diffraction (XRD) measurements for identification of crystalline phases were carried out in a
Bruker D8 advance diffractometer equipped with CuK tube. The morphological characterization of
the samples was performed by Field Emission Gun Scanning Electron Microscopy (FEG-SEM,
JEOL JSM-6500F). For those observations, the powdered sample was embedded in a polymeric
resin and sputter coated with graphite to make the sample conductive. A Transmission electron
microscopy (JEOL FEM-2100) was also used for the characterization of calcined samples.
The thermal transformation of boehmite into alumina was followed by simultaneous
thermogravimetry/differential thermal analysis (TG/DTA) in a SETARAM DTA-TG Setsys Evolution
500 at a heating rate of 20 C min-1, in air up to 1400 C. Alumina crucibles with 20 mg samples
were used. The thermal treatment of the precursor was carried out in a high alumina refractory
crucible using an electrical muffle furnace (Thermoconcept HT0417)
RESULTS AND DISCUSION

The XRD pattern of the aluminium waste is shown in Fig. 2a. The crystalline phases identified by
comparison with the powder diffraction data (JCPDS files) are metallic aluminium (1), corundum
(2), silica (3), aluminium nitride (4), calcium carbonate (5) and spinel (6). Besides, a certain amount
of amorphous phases is inferred from the background. Compared with the XRD analysis report by
Gonzalo-Delgado et al. [8], some minor differences were found, which can be attributed to the
heterogeneity of the waste. As shown in Fig. 2b, the XRD pattern of the precursor obtained by the
hydrothermal treatment of the waste consists of six broad boehmite diffraction peaks, indicating a
very small grain and low crystallinity. In this figure, reflections were indexed according to JCPDS
file 1-088-2112.
The chemical analysis of the precursor boehmite obtained by XRF and expressed as oxides wt%,
is shown in Table 1. The balanced water was 31.8%. The amount of chloride in the sample comes
from the first stage in the synthesis process. Taking into account the aluminium content in the
waste, the 90% was recovered as boehmite of relatively high purity.
Table 1. XRF results of precursor boehmite and alumina (w/w, %).
Compound Boehmite Alumina

[%] [%]
Al2O3 61.53 94.91
Fe2O3 2.05 3.31
SiO2 0.64 0.94
ZnO 0.33 0.38
CuO 0.11 0.09
Cr2O3 0.09 0.07
PbO 0.03 0.07
Cl 3.20 ----
Fig. 3a shows FEG-SEM micrographs of precursor boehmite which consists of small sized (below
100 nm) smooth round particles with certain level of agglomeration. The grain size and the low
agglomeration level indicate a low degree of crystallinity, as observed in XRD pattern (Fig. 2b).
TG/DTA studies (figure no showed in this work) revealed that the dehydration of boehmite to
transform into aluminium oxides takes place through a several overlapped endothermic reactions
characterized by a continuous mass loss up to 1028C. The total mass loss of 30.30% obtained by
TG fit well with the value obtained by XRF analysis and lets establish the stoichiometry
AlOOHnH2O, (n~0.8) [8]. The transformation of metastable alumina into corundum was observed
by an exothermic peak in the temperature range between 1062-1204C.
364
a)
1
4
3 6 4
4 1
2 4 1
2 4
3 2 ,3
3
2 2 1 4
6 5 5 3 3 1
10 20 30 40 50 60 70 80 90
2 ()
031 051
b)
120
020 002
10 20 30 40 50 60 70 80
2 (C )
104 113
c)
116
012
300
110
024
214
120 1010
036
208
211 220 131
125
20 30 40 50 60 70 80 90 100
2 (C)
Fig. 2. XRD patterns of: a) aluminium waste (1: Al, 2: Al2O3, 3: SiO2, 4: AlN, 5: CaCO3, 6: MgAl2O4); b)
boehmite obtained by hydrothermal treatment; c) -Al2O3 (corundum) obtained by calcinations at 1400C, 7h.
365
a b
Fig. 3. Scanning electron micrograph of a) the precursor boehmite obtained by hydrothermal treatment of the
waste and b) -Al2O3 (corundum) obtained by calcinations of boehmite at 1400C, 7h.
Figure 2c shows the XRD pattern of sample obtained by heating the precursor boehmite at 1400C
for 7h in air. This pattern corresponds to a highly crystalline material with narrow and well-defined
diffraction peaks, which are assignable to the hkl reflections included in the JCPDS file 1-089-7717
of -Al2O3 (corundum). The chemical composition of the alumina is collected in Table 1 and it
corresponds to 95% purity alumina. Chloride was not detected. -alumina exhibits the morphology
of coalesced round plates, some of them with a certain tendency to present a hexagonal shape as
shown in Fig. 3b. The crystals are pseudomorphs from the boehmite precursor, in agreement to
Souza et al. [9] who indicated the particle shape of the -Al2O3 varies with the nature of the
precursor. Therefore, the formation of corundum takes place through a topotactic reaction of
boehmite dehydration [10].
Fig. 4a shows a low magnification TEM image of an aggregate of small particles of corundum, and
Fig. 4b shows a high magnification of a zone of the aggregate, in which the acquisition of the high
resolution image let observe crystallographic planes. EDAX microanalysis of Fig. 4c confirmed the
composition of the particle fit well to the chemical analysis of the sample by XRF.
CONCLUSION
This study shows the possibility to recover a hazardous waste as a secondary raw material for
other industries, in an attempt to contribute to the reduction of natural resources. The process
developed in this work allows to obtaining 1 ton of nanometric sized corundum particles with an
aluminium oxide content of 95% from 4 tons of hazardous waste. The morphological and
crystallographic characteristic of this alumina (-Al2O3) would allow its use for the ceramic industry.
In this process is also generated an inert solid residue consisting principally of spinel, corundum
and quartz with possible uses in cements or glass industry.
Acknowledgments
The authors thank the MEC for financing project CTM2005-01964 and the company
Recuperaciones y Reciclajes Roman S.L. (Fuenlabrada, Madrid, Spain) for supplying the waste.
366
a b
Element Weight % Atomic % c

OK 44.42 57.87
Al K 52.87 40.84
Fe K 1.89 0.71
Si K 0.74 0.55
Cr K 0.08 0.03
Totals 100.00
Fig. 4. Transmission electron microscopy of -Al2O3 (corundum): a) low resolution image, b) high resolution of
a selected area, and c) EDAX microanalysis.
References
[1] Directive 2008/98/EC of the European Parliament and of the Council on Waste and
Repealing Certain Directives, 2008
[2] A. Lpez-Delgado, H. Tayibi. Can hazardous waste become a raw material?. The case study
of an aluminium residue: a review. Waste Manage. Res. In press (2011).
[3] G.A. Khater. Glass-ceramics in the CaOMgOAl2O3SiO2 system based on industrial waste
materials. J. non Crystal Solids 356 (2010) 3066-3070.
[4] J. Sanchez-Valente, X. Bokhimi, J.A. Toledo. Synthesis and catalytic properties of
nanostructured aluminas obtained by sol-gel method. App. Catal. A: General 264 (2) (2004)
175-181.
[5] A. Boumaza, l. Favaro, J. Ledion, G. Sattonnay, J.B. Brucbach, P. Berthet, A. M. Hunts, P.
Roy, R. Tetot. Transition alumina phases induced by heat treatment of boehmite: an X-ray
diffraction and infrared spectroscopy study. J. Sol. State Chem. 182 (2009) 1171-1176.
[6] J. Li, X. Wang, L. Wang, Y. Hao, Y. Huang, Y. Zhang, X. Sun, X. Liu. Preparation of alumina
membrane from aluminium chloride. J. Membrane. Sci. 275 (1-2) (2006) 6-11.
[7] A. Lpez-Delgado, H.Tayibi, F.J. Alguacil, F.A. Lpez. A hazardous waste from secondary
aluminium metallurgy as a new raw material for calcium aluminate glasses. J. Hazard. Mat.
A65 (1-3) (2009)180-186.
[8] L. Gonzalo-Delgado, A. Lpez-Delgado, F.A. Lpez, F.J. Alguacil and S. Lpez-Andrs.
Recycling of hazardous waste from tertiary aluminium industry in a value-added material.
Waste Management and Research. 29(2) (2011) 127-134.
[9] P. Souza Santos, H. Souza Santos, S. P. Toledo. Standard transition aluminas. Electron
microscopy studies. Materials Research, 3 (4) (2000) 104-114.
[10] S.M. Kim, Y.J. Lee, K. W. Jun, J. Y. Park, H. S. Potdar. Synthesis of thermo-stable high
surface alumina powder from sol-gel derived boehmite. Mat. Chem. Phys. 104 (2007) 56-61.
367
St
CONSTRUCTION AND DEMOLITION WASTES AS AGGREGATE FOR

RECYCLED CONCRETE UNDER MARINE ENVIRONMENTS.
C. Thomas, I .Sosa, J. Setin, J.A. Polanco, C. Medina

Dept. of Science and Engineering of Materials, University of Cantabria, College of Civil Engineering of
Santander, Spain. thomasc@unican.es
ABSTRACT
The purpose of this study is to assess the influence of the use of recycled aggregates on
some characteristics related with the durability of concrete made with them. In this paper, it is
discussed the replacement of 0% (control concrete), 20%, 50% and 100% of natural
limestone coarse aggregate, of a conventional concrete, with recycled coarse aggregate
from the concrete crushing of demolition [1-5]. The experimental technique used was based
on the study of the permeability to water and gases, also characterizing the physical and
mechanical properties of recycled concrete cured, first, in moist chamber and, secondly, in
IIIa marine environment. As for the results, it was found that the use of recycled aggregates
from concrete waste in the manufacture of recycled concrete, dosed with the same water-
cement ratio, does not generate loss of durability.
Key words: durability, waste, concrete, recycling, structures.
INTRODUCTION
The recycled concrete is one in which a partial or total replacement of aggregates, that form the
skeleton of the concrete, by recycled aggregates has been made.
The aim of this investigation is the study of the durability of recycled structural concrete. In addition, it
has been analyzed the performance of recycled control concrete comparing it with others exposed to
the marine environment. The main properties that affect the stability of concrete on the one hand,
directly exposed to the weather conditions in the city of Santander (IIIa environment) and, on the other
hand, concrete cured in moist chamber, providing ideal curing environment at a temperature of 23 C
and 99 % humidity, were compared.
100
Chamber relative humitity
Temperature [C] - Relative humidity [%]
80
60
28 days
Environmental relative humitity
40
365 days
Chamber temperature
20
Environmental temperature
0 50 100 150 200 250 300 350 400
Time [days]
Fig 1. Climatic conditions in the city of Santander (marine environment, IIIa),

Spain, for the period January 2007 - January 2008.
368
MATERIALS
Substitutions of 20%, 50% and 100% of the natural limestone aggregate (NA) (more than 2 mm of size
particles) by recycled aggregate (RA), waste composed from demolition of concrete structures, were
studied. Likewise, control concretes (CC) have been prepared, made exclusively with natural
aggregate, to compare their performances while with recycled concrete (RC). Each dose at the age of
28 and 365 days was studied and in the two mentioned environments cured: humidity chamber and
marine environment, Fig. 1.
Regarding the nature of the aggregates, the NA is crushed limestone and the RA used at this stage of
research is made from construction and demolition waste (CDW) of structural concrete, classified,
crushed, processed and removed most impurities. The components and ratios found in the RA are:
95.9% aggregate whose origin is concrete, in which 44.4% corresponds to NA (from the original
concrete) and 51.5% mortar and natural aggregate with a greater volume of adhered mortar, the 1.6%
is NA contaminated by bituminous, 1.4% ceramic aggregate (CA), 0.6% polymeric materials and,
finally, 0.4% is less than 0.063 mm size material.
The granulometry of the RA (2-20 mm) can replace a portion of gravel of 2-16 mm and 8-20 mm from
the CC in order to obtain the different dosages of RC.
Regarding the physical properties of the aggregates, the NA shows a density of 2.70 g/cm 3, a water
absorption coefficient of 1.5 % in weight and a porosity of 3.6 % in volume, typical values for natural
3
limestone aggregates. On the other hand, the RA has a density of 2.24 g/cm , a water absorption
coefficient of 5.1 % in weight and a porosity of 11 % in volume. The values obtained in the
characterization of this RA are very similar to the values of a typical structural concrete.
As can be observed, the porosity of RA is much higher than that of NA. This fact will be crucial in the
final properties of hydrated cement paste [1-7].
Two structural concrete classes have been studied, first, with 275 kg/m 3 of cement and a water-
cement ratio (w/c) of 0.65 for the H25 control concrete and, a second one, using 380 kg/m3 of cement
and a w/c of 0.5 (concrete H40), obtaining in both cases similar comparative results. In this paper are
presented the results for concrete H25.
The formulation of the dosage of the RC is determined from a substitution of aggregate in proportions
that keep the particle size invariant, replacing the same volume of recycled aggregate [1].
EXPERIMENTAL
The durability study was carried out on each of the 32 variants of concrete: 4 substitutions degrees, 2
strength classes, 2 ages and 2 curing environments. First, mechanical characterization testing: simple
compressive strength and tensile strength by the indirect method. With regard to the physical
characterization: densities, porosities and water absorption from each of the hardened concrete have
been determined.
Alongside the mechanical and physical analysis, it was determined the permeability coefficient to
gases and the maximum penetration of water under pressure, as established on standards as
indicators of the concrete durability.
In order to determine the permeability coefficient, from the Darcy equation for fluids can be obtained, in
general, the permeability coefficient of the material like:
2 P1Rl
K (1)
A( P22 P12 )
Where:
K = Permeability coefficient [m2].

= Gas viscosity [Ns/m2].
l = Sample length [m].
R = Outlet gas caudal [m3/s].
A = Cross-sectional area [m2].
369
P1 = Absolute outlet pressure [N/m2].
P2 = Absolute inlet pressure [N/m2].
The value obtained of the permeability directly using a gas, depends on the pressure and the type of
gas used. In this way, and in order to compare the permeability obtained for liquids, three different inlet
pressures for the same gas were used. In our case, the gas used is oxygen with a viscosity of 2.0210-
5
Ns/m2, under normal conditions, and the outlet pressure equals to the atmospheric pressure. The
equation (1) then becomes:
4.04 1010Rl
K (2)
A( P22 1)
Where the pressure value is expressed in bars.

With the goal of the samples optimization, with the exception of the compression samples, of each
standard concrete sample were obtained three subsamples (A, B and C) by transversal cuts. With the
sub-sample A (upper third of the standard sample) has been testing the density, porosity, absorption
and tensile properties. With the sub-sample B (central) has been determined the permeability
coefficient to gas, the maximum penetration of water under pressure and tensile strength. The
subsample C (lower third), as well as the A, have served to supplement the results of density, porosity,
absorption and tensile strength of the material.

Fig. 2 and 3 show the comparison of the mechanical properties of CC and RC cured, on one hand, in
humidity chamber and, in the other hand, under marine environment.
Compressive strength of H25; 365 days

70
60
Compressive strength [MPa]
50
40
30
Humidity Chamber
Humidity Chamber
Humidity Chamber
Humidity Chamber
IIIa Environment
IIIa Environment
IIIa Environment
IIIa Environment
20
10
0
0 20 50 100
Recycled aggregate [%]
Fig. 2. Compressive strength of H25 concrete with 365 days of age.
The compressive strength of RC is significantly higher than the CC strength, increasing in proportion to
the replacement of the NA by RA, mainly due to the reduction of the w/c of the cement matrix due to
the greater porosity and absorption of the RA [2].
370
Tensile strength H25; 365 days
5
Tensile strength [MPa]

3
Humidity Chamber
Humidity Chamber
Humidity Chamber
Humidity Chamber
IIIa Environment
IIIa Environment
IIIa Environment
IIIa Environment
1
0
0 20 50 100
Fig. 3. Tensile strength of concrete H25 with 365 days of age.
Fig. 4 and 5 show the comparison of the physical properties of CC and RC cured in humidity chamber
with those cured in marine environment.
Apparent Density - H25; 365 days

2,5
2
Apparent Density [gr/cm ]
3
1,5
1
Humidity Chamber
Humidity Chamber
Humidity Chamber
Humidity Chamber
IIIa Environment
IIIa Environment
IIIa Environment
IIIa Environment
0,5
0
0 20 50 100
Fig. 4. H25 concrete density with 365 days of age.
Porosity - H25; 365 dias

12
10
Porosity [% vol]
6
Humidity Chamber
Humidity Chamber
Humidity Chamber
Humidity Chamber
IIIa Environment
IIIa Environment
IIIa Environment
IIIa Environment
0
0 20 50 100
Fig. 5. Porosity of concrete H25 with 365 days of age.
371
Fig. 6 and 7 show the results of the durability tests of CC and RC cured in humidity chamber versus
those cured in marine environment.
Water penetration - H25; 365 days

60
50
Max. water penetration [mm]
40
30
Humidity Chamber
Humidity Chamber
Humidity Chamber
Humidity Chamber
IIIa Environment
IIIa Environment
IIIa Environment
IIIa Environment
20
10
0
0 20 50 100
Fig. 6. Maximum water penetration in concrete H25 at the age of 365 days.
Coef. of Permeab. to O - H25; 365 days

2
-18
8 10
-18
7 10
-18
6 10
Coef. Perm. [m ]
2
-18
5 10
-18
4 10
-18
3 10
Humidity Chamber
Humidity Chamber
Humidity Chamber
Humidity Chamber
IIIa Environment
IIIa Environment
IIIa Environment
IIIa Environment
-18
2 10
-18
1 10
0
0 20 50 100
Fig. 7. Permeability coefficient to oxygen of concrete H25 with 365 days of age.
ANALYSIS
Regarding the mechanical properties of concrete, it should make a distinction between compressive
strength and tensile strength. In the results for the first of the properties, there is a loss of capacity
between 20% and 5%. By contrast, in the case of indirect tensile strength, the difference found
between the cured concrete in the two different environments, it is higher than in the first case and,
moreover, is accentuated with the percentage of aggregate incorporated to the recycled concrete.
The difference found between the compressive and tensile capacity may be due to the different
resistant mechanisms acting on the two cases. In the first case, the properties of the aggregates have
not much influence in the properties of the different concretes cured under the two environments. By
contrast, the significant difference found in the indirect tensile strength between the concrete cured in
camera and outdoor, is accentuated with increasing the degree of recycling because the processes
that govern this feature is closely related to the porosity and microcracks present in the RA compared
to NA.
With regard to the density of hardened concrete, there are no great differences between the concretes
cured in two environments and the difference between them is minimal in the case of concrete with a
high degree of substitution.
It has found little difference in the apparent densities of different recycled concretes studied. The
introduction of a less dense material (RA) yields to a lower density RC. However, it is not the same
when is considered the porosity of recycled concrete because it reduces with the substitution degree.
Concrete exposed to ambient IIIa present a more open porosity between 1.5% and 0.3% in
372
comparison to the concrete cured in an ideal environment. The difference is greater when the degree
of substitution is lower.
No difference is observed due to the curing environment, in water permeability properties.
The permeability of RC depends greatly on the type of fluid to be submitted. Again, the cement paste
is responsible of this feature.
CONCLUSIONS
All properties analyzed are influenced by the best behavior of the new cement pastes obtained with
the use of recycled aggregates. These, due to the greater porosity of RA have provided an effective
minor amount of water, thereby reducing the w/c ratio; however, in order to maintain the workability by
incorporating a larger amount of superplasticizer additive should be incorporated.
As a final conclusion, can be stated that recycled concrete for structural application, made with the
same w/c ratio as the control concrete offers good protection from the penetration of external agents
than the control concrete, due to the better performance of the cement matrix. However, by reducing
the amount of the effective water, it is necessary to use superplasticizers additives that keep the flow
properties of the fresh mass.
Acknowledgements
Special thanks to the Ministry of the Environment of Spain funding the RECNHOR and CLEAM
projects and the coordination by the CEDEX.
References
[1] Comisin 2 Grupo de trabajo 2/5 "Hormign Reciclado, Utilizacin de rido reciclado para la
fabricacin de Hormign Estructural, ACHE 2006.
[2] C Thomas, J Setin, JA Polanco, Comparacin de las prestaciones mecnicas entre hormigones
reciclados con residuos de construccin y demolicin (CDWs) y hormigones convencionales,
Materiales Compuestos. 1 (2007) 221.
[3] C Thomas, J Setin, JA Polanco. Determinacin de la macroporosidad accesible y no accesible
mediante anlisis digital de imgenes en hormigones reciclados de aplicacin estructural, X
Congreso nacional de Materiales. II (2008) 923-926.
[4] C Thomas, J Setin, JA Polanco. Determinacin del lmite a fatiga en hormigones reciclados de
aplicacin estructural, Anales de Mecnica de la Fractura. 1 (2009) 283-289.
[5] C. Thomas, J. Snchez, J. Setin, J. A. Polanco, F. Ballester. Sustainable management of
construction and demolition waste: generation, recovery and applications, RECIMAT'09. 1 (2009)
156-159.
[6] M Snchez, P Alaejos, Estudio sobre las propiedades del rido reciclado. Utilizacin en hormign
estructural, 2006.
[7] SW Tabsh, AS Abdelfatah. Influence of recycled concrete aggregates on strength properties of
concrete, Constr.Build.Mater. 23 (2009) 1163-1167.
373
ENZYMATIC MODIFICATION OF A KRAFT LIGNIN

1 1 1 1
S. Gouveia , M.C. Fernndez , M.A. Sanromn and D. Moldes
1
Dpt. Chemical Engineering, University of Vigo, Campus As Lagoas, Marcosende 36310,
Vigo, Spain, gouveia@uvigo.es
ABSTRACT
Lignin is a tridimensional, amorphous, phenolic macromolecule found in the cell wall of
vascular plants, that presents a great variety of functional groups. Industrial lignins are a
by-product of the pulping process of wood in the papermaking industry and have long
been labeled as industrial waste.
In this work, the ability of a commercially available laccase from Myceliophthora
thermophila to change the chemical structure of eucalypt Kraft lignin (KL) was studied.
Furthermore, the effect of several laccase mediator systems LMSs, in the lignin
polymerization reactions was evaluated. Operating conditions such as pH, temperature,
enzyme activity and reaction time were designed to obtain larger amounts of lignin with a
high average molecular weight (Mw).
Keywords: laccase, lignin characterization, lignin polymerization
INTRODUCTION
Lignin, present in all land plants except mosses, executes three vital functions: it allows plants to
grow upright as they compete for sunlight, it enables the ascendant movement of water and
minerals through the plant's vascular tissue and it defends plants from pathogens and foraging
animals. Lignin also sequesters atmospheric carbon in its tissues and thereby plays an important
role in the carbon cycle. Around 30% of non-fossil organic carbon is kept in lignin and it is the most
abundant biological polymer on Earth after cellulose [1].
Industrial lignins are by-products of the pulping process of wood in the papermaking industry where
high-quality pulps are obtained by chemical processes that depolymerize and dissolve the lignin.
Despite its unique characteristics, only a small quantity of this largely available renewable carbon
source is isolated from spent pulping liquors and used in a wide range of products, while almost all
lignin extracted is burned to generate energy and recover chemicals [2].
However, an increase in research, has demonstrated that lignin has a high potential that goes far
beyond what has been assigned so far when used mostly as low-value fuel, feeding the boilers in
the process pulping. Its recognized that lignin is a non-toxic, potentially of high value, inexpensive
and available in large amounts raw material [3].
Among the biopolymers, the structure of lignin has been the most difficult to characterize not being
fully defined its structure or its distribution in wood [4]. Its well accepted that lignin is a molecule
based on macro phenylpropanoid monomers (Fig. 1) which differ in the degree of substitution of
the phenolic ring by methoxyl groups in positions C 3 and C5 [5]. In the case of coumaryl alcohol (H
structure) these two positions are free while in coniferyl alcohol (structure G) and sinapyl alcohol (S
structure) are mono substituted or bi substituted respectively.
374
Fig. 1 - Monomeric structures precursor of lignin. (a) p-coumaryl alcohol (4-hidroxyl phenyl, H),
(b) coniferyl alcohol (guaiacyl, G), (c) sinapyl alcohol (syringyl, S)
The lignification, ie, the polymerization process of the basic phenylpropanoid units is initiated by
oxidoreductases enzymes such as laccase or peroxidases on a reaction mechanism that involves
the oxidation of the phenolic end group to resonance-stabilized radicals that can suffer radical
coupling to form covalent bonds. The monomers are connected by different types of carbon-carbon
and ether linkages [6]. With such a wide cross-linking possibility, the result of this process is a
complex tridimensional, amorphous, phenolic macromolecule.
Although lignins heterogeneity, as far as the polymer composition, size, cross linking and functional
groups, makes this raw material remarkably interesting when concerning to chemical and
biophysical functionalities, this characteristics may also represent an handicap for some specific
applications. To overcome this fact, the modification of the structure of lignin is presented as one of
the obvious solutions, ideally producing the right lignin for each potential application.
In the quest for novel adhesion solutions and strength additives for wood composites, a common
theme is to increase bonding between the fibers. The oxidative modification of lignin stimulating the
cross-linking for improving adhesion has been described previously [6], and studies report that the
thermal stability and glass transition temperature increases with the molecular weight [7].
In this study with the aim of obtaining maximum polymerization of a kraft lignin with laccase,
several reactional conditions were studied. Furthermore, and knowing that the substrate range of
phenol-oxidizing enzymes, such as laccase, can be extended to the non-phenolic groups when
using a redox mediator [6], the introduction of several mediators in the system was tested. It is
believed that these mediators are first oxidised by laccase to an activated form that, contrary to
proteins, is small enough to penetrate the steric barriers of the lignin molecule.
To evaluate how these conditions can affect the outcome of the reaction, the products were
analyzed by size exclusion chromatography (SEC), Fourier transform infrared spectroscopy (FTIR)
and Nuclear magnetic resonance spectroscopy (NMR).
2. Materials and methods

Lignin
Kraft Lignin was isolated by acidic precipitation of the black liquor to pH 2.5 with sulfuric acid 1M
under stirring at 50C. After filtration the isolated lignin was washed twice with acidified water, pH
2.5, and dried overnight in oven at 60C. Black liquor, from Eucalyptus globulus, was donated by
ENCE (Pontevedra, Spain).
Enzyme
Laccase NS51003 from Myceliophthora thermophila was kindly donated by Novozymes
(Bagsvaerd, Denmark). The commercial enzyme was cleaned in a General Electric Sephadex G-
25M column before application.
Enzyme assay
Laccase activity was determined by oxidation of 2,2-azino-bis(3-ethylbenzthiazoline-6-sulfonate)
(ABTS) and 4-hydroxy-3,5-dimethoxybenzaldehyde azine (syringaldazine, SGZ) as substrates in a
range of pH and temperature from 4 to 8 and 30 to 70C respectively. Enzyme activity was
expressed in units (1 U=1 mol substrate oxidized per min at room temperature). The optimum pH
and temperature in ABTS were found to 5 and 70C respectively. In SGZ, The optimum pH and
temperature were 6 and 70C respectively. Enzymatic stability was tested in both substrates at
optimum conditions.
375
Enzymatic reactions
Lignin was solubilized in phosphate buffer pH 6.0 (100 mM) obtaining a solution of 1.5 M. The pH
was adjusted to pH 6. In a reaction vessel 90 mL of lignin solution was mixed with the enzyme until
-1
a final activity of 1 UmL and the reaction was held under agitation for 2h, at 70C. Control
experiment was executed, to guarantee that the products obtained are result of enzyme effect, with
a pre heat-denaturated laccase. Reaction was concluded by lowering the pH to 2.0. The reaction
product was filtered and washed twice with acidified water, pH 2.5, and dried overnight in oven at
60C.
Laccase mediator system (LMS)

Six phenolic mediators were used on the LMS oxidation reactions, namely: syringaldehyde (S),
pyrocatcehol (P), guayacol (G), vanillin (V), violuric acid (AV) and polyphenon 60 (PH60).
Enzymatic stability tests were performed for each of the mediators (final concentration 1 and 5 mM)
to ensure that the use of mediators does not lead to a rapid inactivation of the enzyme.
The LMS lignin treatment was carried out as described in enzymatic reactions and the right amount
of phenolic mediator was added to achieve a final concentration of 1mM. Experiments were carried
out with different times of addition of mediator. Mediator was added simultaneously with the
enzyme or 1h after.
Size exclusion chromatography (SEC)

SEC analyses of lignin were performed under isocratic conditions using a chromatography system
from Jasco (AS 1555 autosampler; PU 2080 plus pump, UV 975 detector). Lignin samples were
dissolved in to a final concentration of 0.5 gL-1 in NaOH 0.05 M and left in agitation for at least 24h.
Once totally dissolved the samples were filtrated in PVDF 0.2 m syringe filter and separated by
two GPC columns (Phenomenex) coupled in a series (GPC P4000 and P5000). A 100 L volume
of sample was injected in the system using NaOH 0.05 M as eluent. The running time was 26 min
at a flow rate of 1 mL min-1, at 25C and the absorbance at 254 nm was recorded. The system was
controlled and data was recorded and analyzed with ChromNAV GPC software.
Fourier transform infrared spectroscopy (FTIR)

FTIR spectra were acquired using a Jasco FT/IR 4100 spectrometer, equipped with attenuated
total reflectance (ATR). A few milligrams of solid samples of lignin, previously milled in a agate
mortar and placed to dry for 10 min under an infrared lamp, were measured between 450 and 4000
-1 -1
cm with a 4 cm resolution and 32 scans. The spectra were analyzed in the application OMNIC
32.
Nuclear magnetic resonance spectroscopy (NMR)

Acetylation
Prior to NMR analysis, samples of kraft lignin and treated lignin were subjected to acetylation.
Around 100 mg portion of dry lignin was dissolved in 1:2 pyridine/acetic anhydride. The reaction
was permitted to progress for 48 h at 37 C and was concluded by addition of methanol. The
solvents were evaporated to dryness.
1 13
The solution-state H NMR and C NMR spectrum were recorded on a Bruker Avance 400 MHz
spectrometer at 298 K using a 5 mm QNP probe with a z-gradient support and a flip angle of 30.
1 13
The lignin sample (25 mg for H, 250 mg for C) was dissolved in 1 ml DMSO-d6. Chemical shifts
1
were referenced to the residual solvent signals. H NMR experiments were recorded with 1s
13
relaxation delay, 6.3 s acquisition time, 5208.333 Hz spectral width and 16 scans. C NMR
experiments were recorded with 5s relaxation delay, 1.4 s acquisition time, 23148.148 Hz spectral
width and 50000 scans.
3 . Results and discussion

The objective of this research was to study whether NS51003 laccase is able to modify the
structure of kraft lignin and if so, under what conditions it gives a greater variation of their
functionality and increase in molecular weight distribution.
376
After the 2h laccase and laccase-mediator treatments, SEC, a widely accepted method to
determine molecular weight distribution, revealed an increase in weight average mass (Mw) of
lignins for all experiments. However, while some mediators were able to potentiate the effect of
polymerization caused by laccase alone (KL + lac), others apparently have limited this same effect.
Table 1 presents the results of Mw calculations sorted in ascending order.
Table 1 Average molecular weight of lignin

samples, before and after 2h treatment.
Sample Mw (Da)
KL 2542
KL+Lac+V 3427
KL+Lac+G 3675
KL+Lac+PH60 3698
KL+Lac 3722
KL+Lac+VA 3827
KL+Lac+S 3864
KL+Lac+P 4001
Laccase alone was capable, in experimental conditions (1 U/mL, PH 6 and T=70C), to multiply by
approximately 1.6 initial KLs Mw. When compared to the isolated effect of laccase, none of the
laccase-mediator systems tested revealed significant benefits, or losses, in the Mw obtained.
Mediator added 1h after the reaction start showed slightly better results than when added
simultaneously with the laccase.
In every case, the changes suffered by lignin are accompanied by an increase in polydispersity
index. Fig. 2, showing the chromatograms corresponding untreated KL and LMS composed by
laccase pyrocatechol (P), illustrates this effect.
Treated and untreated Kraft lignins were analyzed by FTIR spectroscopy (Fig. 3). Kraft lignin
-1
showed, as expected for a Eucalyptus lignin, predominance of S type lignin (1330 and 1125 cm ).
1654 1330 1125
KL+laccase+P
KL+laccase
Untreated KL
-1
Wavenumber (cm )
Fig. 2 Chromatogram of untreated KL and Fig. 3 FTIR spectra for untreated KL and
treated for 2h in a LMS with pyrocatechol. treated for 2h with laccase and LMS with
pyrocatechol.
377
Analyzing changes in the structure of lignin, once again it appears that the action of the mediator
did not provide further benefit, since FTIR spectra of lignin treated with laccase mediator system is
very close to the enzyme treatment alone (Fig.3). For any of the treatments carried out the major
differences are noted in the carbonyl links where, after treatment, appears a new band
-1
corresponding to conjugated C=O stretching (1654 cm ). The band corresponding to unconjugated
-1
C=O stretching (1718 cm ) existent in KL, weakens or even disappears after treatment.
The initial experimental conditions were based on previous laccase activity studies. Taking into
account that those studies were conducted in a substrate (ABTS and SGZ) different than the one
that oxidative polymerization takes place (lignin) we wondered if the initial reaction conditions were
the most appropriated. To clarify this question several experiments were planned maintaining lignin
-1
as substrate while varying pH (from 5 to 8), temperature (50 to 80) and enzyme activity (1UmL the
-1
4UmL ).
Surprisingly, as a result of a 2h treatment at optimum conditions, established as an enzymatic
-1
activity of 2 UmL , at pH=7.5 and T=70C, lignin polymerize to a blend of 3 distinct Mw, the biggest
1
of them 200 times greater than the initial KL (Fig. 4). H NMR spectra (Fig. 5), obtained after the
mentioned enzymatic treatment either with or without mediators, showed a disappearance of
protons in the lignin benzene rings.
Peak Mw (Da) Area (%)

KL
KL 2 542 100,0 Enzymatically treated lignin
1 525 230 8,8
Enzimatically
2 68 978 19,5
treated lignin
3 5 603 71,7
of protons in the lignin benzene

3
rings.
Aromatic
2 KL
1
7.0 6.0 5.0 4.0 3.0 2.0 1.0

ppm
1
Fig. 4- SEC chromatograms of kraft lignin(- - -) and Fig. 5 - H NMR spectra of polymerized lignin and
polymerized lignin ( ) at optimum conditions kraft lignin at optimum conditions
On the other hand, measures of the phenolic content indicated that there were still benzene rings
(data not showed). These results were confirmed when signals of aromatic carbons appeared in
13
the C NMR spectra (data not showed).
The degree of polymerization showed to be highly sensitive to the reaction conditions, particularly
to pH and temperature.
Probably due to steric problems, after 2 hours of treatment the lignin had reached its final weight
and there were no improvements for higher treatment times. However the reaction time, as well as
the enzyme activity used, showed major importance in relative amounts of each polymer obtained.
Conclusion
Laccase NS51003 alone, i.e., without the need of phenolic mediators, clearly was able to modify
the structure of the KL from Eucalyptus globulus studied.
Temperature and pH proved to be of crucial importance in the results of lignin polymerization. On
the contrary, the addition of mediators showed no major improvements in the results.
The functional changes perceptible in FTIR analyses led to an increase in Mw of lignin. The results
of FTIR and NMR suggests that the strong polymerization observed by SEC was due to formation
of new C-C aryl-aryl or aryl-alkyl or to new ether linkages without destruction of aromatic lignin
backbone.
This process, environmentally safe, proved to be capable of modify the molecular weight of a Kraft
lignin obtained from a byproduct of pulp industry (black liquor). In fiberboard and particleboard
industry, this method may have particular interest as the substitution of adhesive contaminants
378
such as formaldehyde, seems to pass by an improvement in self-bonding properties of its particles.
One approach is to promote the enzymatic oxidative cross-linking between the lignin on the boards.
Acknowledgements
S. Gouveia is grateful to Fundao para a Cincia e a Tecnologia Portugal for her fellowship and
D. Moldes is grateful to Xunta de Galicia for an IPP contract. This work was funded by Xunta de
Galicia (project 09TMT012E) and Ministry of Science and Innovation (project CTQ2009-13651).
ENCE (Spain) and Novozymes (Bagsvaerd, Denmark) are gratefully acknowledged for supplying
the black liquor and enzymes.
References
[1] S. Berthet et al., Disruption of LACCASE4 and 17 Results in Tissue-Specific Alterations to
Lignification of Arabidopsis thaliana Stems, Plant Cell, 23 (2011) 1124-1137.
[2] R. J. A. Gosselink, E. De Jong, B. Guran, e A. Abcherli, Co-ordination network for lignin -
Standardisation, production and applications adapted to market requirements (EUROLIGNIN), Ind.
Crop. Prod, 20 (2004) 121-129.
[3] G. Sena-Martins, E. Almeida-Vara, e J. C. Duarte, Eco-friendly new products from
enzymatically modified industrial lignins, Ind. Crop. Prod, 27 (2008) 189-195.
[4] F. S. Chakar e A. J. Ragauskas, Review of current and future softwood kraft lignin
process chemistry, Industrial Crops and Products, vol. 20, n. 2, pp. 131-141, 2004.
[5] S. Y. Lin, Methods in lignin chemistry. Springer-Verlag, 1992.
[6] P. Widsten e A. Kandelbauer, Adhesion improvement of lignocellulosic products by
enzymatic pre-treatment, Biotechnology Advances, vol. 26, n. 4, pp. 379-386, 2008.
[7] T.-Q. Yuan, J. He, F. Xu, e R.-C. Sun, Fractionation and physico-chemical analysis of
degraded lignins from the black liquor of Eucalyptus pellita KP-AQ pulping, Polymer Degradation
and Stability, vol. 94, n. 7, pp. 1142-1150, 2009.
379
DEVELOPMENT OF NEW INSULATION PANELS BASED ON TEXTIL

RECYCLED FIBERS
1 2 3 4
Herrero Castilla, L. , Rodrguez-Senn, E. , Campos Valverde I. , Fernndez Nez D. ,
5
de la Mano Ferreira, R. .
1 Environmental Area, AIMEN Technology Centre, O Porrio, Spain. Email: lherrero@aimen.es
2 Joining Tech. Plant, AIMEN Technology Centre, O Porrio, Spain. Email: erodriguez@aimen.es
3 Environmental Area, AIMEN Technology Centre, O Porrio, Spain. Email: icampos@aimen.es
4 Environmental Area, AIMEN Technology Centre, O Porrio, Spain. Email: dfnunez@aimen.es
5 Joining Tech. Plant, AIMEN Technology Centre, O Porrio, Spain. Email: rmano@aimen.es
ABSTRACT
One of the main environmental problems for clothing sub-sector is the production of
remnant waste derived from cutting processes of natural or synthetic fibers. This work is
focused on the preparation and characterization of new materials made of waste derived
from textile industry (polyester and polyurethane) by thermoforming. The final application
is the manufacturing of heat insulation panels that could be used in the building sector in
order to improve environmental protection and energy efficiency. FTIR characterization
was carried out in order to assess the composition of waste used. Thermal transitions of
waste material and degradation temperature were studied by DSC and TGA respectively.
Waste were grinding in a cutting mill with 4 mm sieve. Thermal insulation panels of 200 x
200 x 5 (L x W x T) mm of different densities were manufactured in a thermoforming hot
plate at 190C and constant pressure during 15 minutes. Thermal insulation properties
were evaluated by guarded comparative longitudinal heat flow technique. Thermal
conductivity of panels was obtained in a range between 0.053 W/mK and 0.041 W/mK,
depending on the density. The obtained values were similar to other commercial
insulation materials.
Keywords: Textile waste, insulation panel, fibre waste, thermoforming
INTRODUCTION
Textile/clothing sector plays an important role in the Spanish industry, with more than 5.500
companies and a high number of employees, representing the 6.5% of total industrial employment,
3% of manufacturing national industry and 5.3% of Spanish exports [1]. World man-made fibers
production in 2009 was more than 68.5 million tons and approximately 58% was polyester [2].
Manufacture of these fibers is based on oil-derived raw materials which have become increasingly
scarce. Therefore, researching for alternatives, both technically and economically feasible for
recovery and recycling is necessary.
One of the main environmental problems for clothing sub-sector is the production of remnant waste
derived from cutting processes of natural or synthetic fibers. The most common treatment options
for waste textiles of synthetic fibers, are based on landfill disposal (risk of soil degradation) or in
energy recovery operations using its high heat capacity for the production of electricity [3] with
environmental implications related to atmospheric emissions of pollutants like COx, NOx,
COVs[4]. The main ways of recycling are based on chemical or mechanical processes .
Chemical recycling refers to the conversion of the polymer into smaller molecules that can be used
in the manufacture of new petrochemicals and plastics products. Mechanical recycling is the
recovery of plastic waste by mechanical means for use in new products, employing techniques
such as pelletizing, pressing and temperature application [5,6].
About a third of worldwide energy consumption is used in building sector, which needs the
development of new thermal insulation materials that minimise the heat energy flow [7,8]. Insulating
380
materials are differentiated by their form of production, raw materials and their effects on human
health and the environment. All of this is reflected in the mandatory application of the new Spanish
Technical Building Code (CTE) which sets the main improvements to assure the environmental
sustainability [9]. Recycled and reused waste have been used in building sector for a wide range of
applications. For instance, rubber, paper and cardboard, wood and plastic waste have been often
applied as insulation materials in absorbent acoustic ceilings or to manufacture synthetic boards
and pipes.
Currently, textile materials begin to be used as thermal and acoustic insulators for roofs and walls
[10,11]. In order to study the applicability of a recycled material as thermal insulator is necessary to
determine two fundamental properties: thermal conductivity (its ability to transfer heat energy by a
temperature gradient) and the coefficient of heat transfer (the physical value of heat flux
transmitted by a constructive element of thickness and composition determined) [12]. In the case of
insulating foams and fibers, different models have been developed to optimise its performance
[13,14]. This work is focused on the preparation and characterization of new insulation materials
made of waste derived from textile industry (polyester and polyurethane) by thermoforming.
EXPERIMENTAL PROCEDURES
Materials
Waste derived from textile industry were obtained at SELMARK, company sited in Vigo (Galicia,
North West of Spain) and dedicated to designing and making women's underwear. The samples
were taken from the production line of foam. The material has a sandwich configuration, with a
foam core and two outer skins of textile, with areas without thermoforming (the same density and
thickness (5mm) as the raw material) and thermoformed areas with a higher densitiy (Fig. 1).
Without Thermoforming
Thermoforming
Fig. 1: Waste material
Characterization was performed on fragments from one sample of textile waste material, taking
four different zones, to study the differences between the material with and without thermoforming:
foam core without thermoforming (F1); foam core thermoformed (F2); skin of textile without
thermoforming (T1) and skin of textile thermoformed (T2). Composition was measured by FTIR
spectroscopy with a germanium ATR. Melting point was measured by differential scanning
calorimetry (DSC) from 25 C to 320 C. Degradation temperature was measured by
thermogravimetric analysis (TGA) following the next program: from 26 C to 600 C (20 C/min, N2):
from 600 C to 400 C (-50 C/min, N2); from 400 C to 900 C (20 C/min, air).
Forming process
The preconditioning of the waste was made by grinding in a cutting mill (RETSCH SM100) with a 4
mm sieve. Ground fibre waste was consolidated in a thermoforming hot plate. The device consists
in two separated parts heated by four thermal resistances (1600W, 230V AC), controlled by two T-
type thermocouples connected to two temperature controllers that allow to adjust the temperature
value separately.
Thermal insulation panels of 200 x 200 x 5 (L x W x T) mm were manufactured at 190C and
constant pressure, during 15 minutes. Different loads of waste were processed to obtain panels
2
with a density of 0.012, 0.018, 0.026, 0.033 and 0.039 g/cm .
381
Thermal insulation characterization
Thermal conductivity is the time rate of steady state heat flow (W) through a unit area of 1m thick
homogeneous material in a direction perpendicular to isothermal planes, induced by a unit
temperature difference across the sample. Thermal conductivity is a measure of the effectiveness
of a material to conduct heat.
Thermal conductivity () of the insulation panels is measured using a method based on ASTM
E1225 - 99 "Standard Test Method for Thermal conductivity of solids by the guarded heat flow
longitudinal comparative technique [15]. The value of can be determined using the following
equation (Eq. 1) where refers to the thermal conductivity, Z and T length and temperature
respectively:
Z 3 Z 2 R1 T2 T1 R 2 T4 T3 (1)
= +
m
T3 T2 2 Z 2 Z1 2 Z 4 Z 3
Fig.4 shows the system used to measure the thermal conductivity. It consists of two round
reference bars materials (alloy of aluminium and copper 2030) and the test round bar (obtained
from thermoforming panels). Diameter is 15 cm in both cases and thickness is 2.5 and 0.5 cm for
reference and test bar respectively. This whole system is covered with polyurethane. Two test
temperatures are selected for the heat source: 60 and 120 C. Temperatures are read once their
values have reached a constant value over time. The data were applied in Eq.1 to determine the
value of the thermal conductivity of materials.
Fig. 2 Scheme of cutted bars method
FTIR spectra (Fig. 3 and Fig. 4) show that samples T1 y T2 can be identified as polyurethane and
samples F1 y F2 as polyester.
T1 T2
Fig. 3: FTIR (Germaniun ATR) of samples T1 and T2
F1 F2
Fig. 4: FTIR (Germaniun ATR) of samples F1 and F2
382
FTIR spectra do not show any difference in composition in samples thermoformed or no
thermoformed. The material (foam+textile) has not suffered any change in its structure due to
thermoforming temperature (198 5C). during the manufacturing of the underwear.
DSC is a thermoanalytical technique in which the difference in the amount of heat required to
increase the temperature of a sample and a reference is measured as a function of temperature.
The result of a DSC experiment is a curve of heat flux versus temperature..
Regarding the DSC analysis, samples T1 y T2 do not show any thermal transition in the studied
range. Thus, T1 and T2 are thermo stable materials in the studied range.
Fig. 5 shows the DSC analysis of F1 y F2 with the same peak in both samples, corresponding to
the melting point at 257 C. Therefore, polyurethane does not change its melting point after
thermoforming.
F1 F2
Fig. 5: DSC of samples F1 and F2
Thermogravimetric and derivative thermogravimetric curves of samples tested are presented in Fig.
6 and Fig. 7.
T1
T2
Fig. 6: TGA of samples T1 and T2
F1 F2
Fig. 7: TGA of samples F1 and F2
TGA is one of the thermal analysis techniques used to measure the mass change, thermal
decomposition and thermal stability of composite materials. TGA curve shows the weight loss of
the analyzed material (thermal degradation) in terms of temperature. Each change in the slope
indicates the start of degradation of each species and therefore, each peak in the derivative curve
represents the average of the temperature degradation.
TGA curves of F1 and F2 are very similar. It can be observed three changes in the slope in both
curves. The derivatives of the curves represent the average of each three slopes and show clearly
383
three decomposition peaks (Table 1). Second and third changes show the same degradation
temperature, for both F1 and F2 samples. First change shows little differences, probably due to the
volatilization or stabilization of the adhesive used to join textile and foam in the raw material during
the thermoforming process.
Table 1: TGA data analysis: F1 and F2 samples

st nd rd st
1 change 2 change 3 change 1 change
Sample Ash
(N2) (N2) (N2) (Air)
Weight loss [%] 17.0 10.6 64 2.0 6.4
F1
T [C] 275.5 327.0 412.1 - -
Weight loss [%] 13.9 10.7 71.7 2.5 1.2
F2
T [C] 290.1 325.5 412.0 - -
TGA curves of T1 and T2 show an important degradation peak around 435 C (Table 2).
Table 2: TGA data analysis: T1 and T2 samples

st nd st
1 change 2 change 1 change
Sample Ash
(N2) (N2) (Air)
Weight loss [%] 15.8 71.3 10.5 2.4
T1
T [C] 296.0 441.9 - -
Weight loss [%] - 80.8 17.5 1.7
T2
T [C] - 431.3 - -
In T1, another degradation peak appears, probably due to the transfer of foam material when
separating it from textile skin (Temperature coincides with the first peak obtained in the TGA
analysis of F1 and F2) or because of the adhesive used to join textile and foam in the raw material.
Values obtained in different samples are similar to those found in literature (288C, 324C and
384C for polyurethane and 440C for polyester) [16, 17]. From the values obtained in the thermal
characterization, the thermoforming temperature was set at 190 C, to be sure to not exceed in any
case, the temperature of most unstable material, which is polyurethane.
Thermoforming temperature for manufacturing of insulation panels was set at 190 C to assure that
degradation temperature of the more unstable material (polyurethane) is not reached.
Thermal insulation characterization.

2
Density values (in g/cm ) are plotted versus the measured values of thermal conductivity (in
W/mK). Data are collected in Table 3 and plotted in Fig. 8.
0,055
0,050
[W/mK]
0,045
0,040
0,035
0,030
0,010 0,015 0,020 0,025 0,030 0,035 0,040 0,045
Density [g/cm2]
Fig. 8 Density against thermal conductivity
Table 3 Density ant thermal conductivity values
2
Density [g/cm ] 0.012 0.018 0.026 0.033 0.039
[W/mK] 0.053 0.043 0.041 0.043 0.044
384
Thermal conductivity values () vary between 0.053 W/mK and 0.041 W/mK, depending on the
2
density of the material. The minimum value is reached at a density of 0.026 g/cm . At this point,
increases slightly as the density increases due to the elimination of air, which is considered the
best thermal insulation material with a of 0.030 W/mK [18], inside the panel. The obtained values
are similar to other commercial insulation materials like: molded beads polystyrene (0,040 W/mK),
coated fibre glass (0,038 W/mK) or mineral wool granules (0,046 W/mK) [18].
Conclusion
FTIR spectra show that textile waste is formed by a polyurethane foam core and two polyester
outer skins. Thermoforming process does not affect the physical and chemical properties of waste.
Ground waste material was consolidated in panels with the conditions defined in previous
experiments (190C temperature, constant pressure). Temperature was limited by the melting point
and degradation temperature of polyurethane.
Thermal conductivity of panels was obtained in a range between 0.053 W/mK and 0.041 W/mK,
depending on the density. The obtained values were similar to other commercial insulation
materials.
REFERENCES
[1] Information on http://www.cityc.es
[2] Information on http://www.cirfs.org
[3] C.Ryu, A. N. Phan, V. N. Sharifi, J.Swithenbank, Combustion of textile residues in a packed
bed, Experimental Thermal and Fluid Science. 31 (2007) 887-895.
[4] S.M. Al-Salem, P. Lettieri, J. Baeyens, Recycling and recovery routes of plastic solid waste
(PSW): A review. Waste Management. 29 (2009) 2625-2643.
[5] W.R. Harfmann, U.S. Patent 6,130,261. (2008).
[6] G.G. Fuss, U.S Patent 5,286, 321. (1994).
[7] Information on http://www.idae.es
[8] C. Balangero, G. Jacobo, Estudio de materiales aislantes termoacsticos e higrotrmicos del
mercado de la construccin del NEA y su utilizacin en el diseo tecnolgico. Ctedra
Estructuras II - Facultad de Arquitectura y Urbanismo - Universidad Nacional del Nordeste
(2006)
[9] Information on www.codigotecnico.org
[10] J. Monjars, Evaluacin del uso de fibras textiles como aislante trmico, Invest Apl Innov
3(2), (2009).
[11] G. Barluenga, F. Hernndez, A. Aguilera, Materiales de ltima generacin y materiales
eficientes reciclaje de residuos de construccin y demolicin y su aplicacin a nuevos
materiales. Universidad de Alcal de Henares (2007).
[12] B. Mutnuri, R. Liang, H. GangaRao, Thermal conductivity characterization of FRP
composites: experimental. Thesis Submitted to the College of Engineering and Mineral
Resources at West Virginia University (2006)
[13] F. Flores Murrieta, Banco de pruebas de conductividad trmica de materiales aplicados en
edificaciones. Caos Conciencia. Divisin de Ciencias e Ingenieras. Universidad de Quintana
Roo (2006) 1870-1221. 17-28
[14]. E. Placido, M.C. Arduini-Schuster, J. Kuhn, Thermal properties predictive model for
insulating foams. Infrared Physics & Technology, 46(3) (2005) 219-231.
[15] ASTM Standard C 168-97, Terminology relating to thermal insulating materials, (1997).
[16] D. Filip, D. Macocinschi, S. Vlad, Thermogravimetric study for polyurethane materials for
biomedical applications. Composites: Part B. 42 (2011) 14741479.
[17] J. Alongui, M. Ciobanu, J. Tata, F. Carosio, J. Malucelli, Thermal Stability and Flame
Retardancy of Polyester, Cotton, and Relative Blend Textile Fabrics Subjected to SolGel
Treatments, J. App. Polymer Science. 119 (2011) 19611969.
[18] F. Incropera, D.P. Dewitt, T.L.Bergman, A.S. Lavine, Fundamentals of heat and mass
transfer, John Wiley & Sons Inc., Hoboken, (2007).
385
CHROMATIC PROPERTIES OF INDUSTRIAL SOLID WASTE BASED

FERRITES
1 2 3 4
W. Hajjaji , R.C. Pullar , M.P. Seabra and J.A. Labrincha
1 Dept. Ceramics and Glass Engineering and CICECO, University of Aveiro, Portugal.
w.hajjaji@ua.pt
rpullar@ua.pt
pseabra@ua.pt
jal@ua.pt
ABSTRACT
Hexaferrite (SrFe12O19) and monoferrite powders were prepared by the common solid
state reaction method to produce black pigments. Similar formulations have been
prepared but using chemically-pure commercial reagents, or by using a sludge generated
from a steel wiredraw ing process as source of iron oxide. The iron-rich industrial waste
used as raw material here is mainly composed of Fe2O3 (62 wt.%). Zinc and calcium are
also present in minor quantities and can form complexes such as franklinite (ZnFe 2O4)
and apatite (Ca5(PO4)3(OH,F,Cl)). Ni/Cr galvanising sludge was also used to enhance the
black coloration of monoferrite.
After calcination of the mixtures at 1000 C and 1050 C, typical x-ray diffraction patterns
of the expected SrFe12O19 and NiFe2O4 phases were obtained, together with minor peaks
of spinel-type (SrFe2O4 and ZnFe2O4) and -Fe2O3 phases. This resulted in a black
pigment with chromatic properties comparable to those of commercial formulations, such
as iron cobalt chromite (Fe,Co)(Fe,Cr) 2O4 (DCMA 13-40-9), chrome iron nickel
(Ni,Fe)(Fe,Cr)2O4 (DCMA 13-50-9), and manganese ferrite (Fe,Mn)(Fe,Mn)2O4 (DCMA
13-41-9).
Keywords: Industrial wastes; ferrites; pigments; chromatic properties.
INTRODUCTION
Trends in research for new pigment formulations are following extremely competitive market by
looking at reducing the manufacturing cost (low cost raw materials). Furthermore, environmental
friendly processes are required to lower the impact of industrial residues and wastes. In this work,
the galvanizing sludge (SG), as a source of Ni and Cr, contains a high amount of chromium [1] that
constitutes a threat to clean water, natural resources and human health. However, its use as a raw
material for ceramic pigments neutralizes the harmful environmental effects, since the thermal
treatment involved assures the desire inertness [2]. In the ferrite formulations, the iron is introduced
from another sludge (SF), that is generated from the steel wiredrawing process. The chemical
composition of these residues is reported in table 1. These by-products were used in the synthesis
of the pigments. The formulations studied were previously made from pure reagents, and these
were assessed as a standard, for comparison. Normally, commercial oxides have a high chemical
purity. However, less-pure raw materials are often used if it is demonstrated that they can have
enough stability, adequate chromatic quality and are less expensive.
In this paper, the ferrite structures; namely trevorite and hexaferrite, were studied. Belonging to the
magnetoplumbite family, strontium hexaferrite (SrM, SrFe12O19) is a hexagonal ferrite which has the
space group P63/mmc [3-5]. These compounds are usually used as permanent magnetic
materials, having a very large magnetocrystalline anisotropy, high Curie temperature, large
386
saturation magnetisation and good chemical stability [6,7]. They also have useful microwave
properties [8]. Several methods are used to prepare this black powder; sol-gel [9,10], solid state
[11], co-precipitation [12], etc.
Table 1. Chemical composition of sludges.
Component (wt. %) SG SF
Al2O3 4.73 0.14
CaO 19.5 5.31
Cl 0.23 1.40
Cr2O3 12.8 0.09
CuO 3.61 0.01
Fe2O3 1.57 62.1
K2O 0.19 --
MgO 1.02 0.21
MnO -- 0.37
Na2O 3.42 2.61
NiO 17.4 0.01
P2O5 8.75 3.09
SO3 10.6 0.11
SiO2 13.0 0.41
ZnO 2.66 2.96
Other elements* 0.28 0.01
Loss on ignition 20.7 21.2
EXPERIMENTAL
The formulations were prepared from pure reagents (P) and from industrial wastes (S, in table 2).
In order to obtain fine and homogeneous slurries, the mixtures were wet ball-milled in water for 1
hour, dried at 110C and fired at the required temperature. The subsequent firing cycle was fixed to
a 3h dwell time and a heating rate of 5C/min, reaching a maximum temperature at 1050C. The
expected phase (hexaferrite) was identified using X-ray diffraction (XRD, Rigaku Geigerflex D/max
Series). The colour measurements were obtained by a Shimadzu UV-3100 for optical
spectroscopy and a Konica Minolta Chroma Meter CR-400, using D65 illuminant and 10 standard
observer (Y:94.0, x:0.3156, y:0.3319) according to the CIE (Commission Internationale de
lEclairage) [13]. This three-dimensional representation has two basal axis consisting in a* and b*
running from positive to negative. The central vertical axis represents lightness (signified as L*)
whose values run from 0 (black) to 100 (white).
Table 2. Formulations of black of pigments (wt.%).
temperature Ni(II) acetate Cr(III) acetate Fe(III) oxide SrCO3 SG SF

PTr 1050 C 29.05 39.97 7.98 - - -
STr 1050 C - - - - 60 40
PFr 1050 C - - 90.55 9.45 - -
SFr 1050 C - - - 6.09 - 93.91
387
The XRD analysis of different powders is exposed in Fig. 1. For the Tr samples, the patterns show
the presence of trevorite (NiFe2O4) as single phase in the pure pigment (PTr). In the actual
conditions, the discrimination of the formed/expected structure (FeNi)(FeCr)2O4 and trevorite is
difficult [14,15]. Associated magnetite (Fe3O4) and chloroapatite are also present in minor
quantities due to the non-stoichiometric nature of the sludges used in the formulation.
For Fr-pigments, hexaferrite (SrFe12O19), hematite (-Fe2O3) and Sr2Fe2O5 were detected by XRD
analysis. The incomplete formation of strontium hexaferrite has been previously stated in some
2+ 3+
works. In all cases, Sr cations being larger then Fe lead to high-temperature requirement for
single-phase formation [5]. Compared to pure PFr, the sludge based SFr is less crystalline due to
the existence of contaminants that interfered with the fexaferrite formation.
Fig.1. XRD patterns of pigments.
388
The absorbance data of Tr and Fr pigments are reported in fig. 2. The hexaferrite Fr-samples show
higher absorbance compared to the Tr-samples. Between pure and sludge based powders, similar
optical behavior is observed in the visible zone. However, dissimilarities are detected in the red
light interval. According to phase composition, this is due to the variable amount of secondary
phases between the pure and sludge based powders; especially hematite. The influence of other
contaminants present in the added waste is also not excluded even if not detected in the XRD
pattern (fig. 1).
Fig 2. UV-Vis spectra.
The aspect and the colorimetric coordinates of the tested black pigments are reported in fig. 3. For
Tr-pigments, L* values are between 28 and 32. This is slightly lower than that displayed by the
commercial pigment (DCMA 13-50-9: L*a*b*=33.0/1.0/0.0) [16]. On other hand, the prepared
powders exhibited higher green (-a*) and yellow (b*) values then the commercial standard. This led
to a barely discernible brownish hue for PTr and STr pigments.
Compared to Tr-powders, the brightness of Fr ones is higher (36 to 37), as shown in the UV-Vis
spectroscopy study (Fig. 2). For the waste based product SFr, the L* and b* decreased for the
same reasons shown in the interpretation of the difference reported in the red light region in the
spectra in Fig. 2. However, this slight colour variance is hardly detected by naked eye, and should
be easily corrected and neutralized when applied in different applications.
389
Fig. 3. L* a* b* colorimetric coordinates of the tested pigments.
CONCLUSIONS
The present work resolved the use of industrial secondary materials namely; galvanizing and
wiredrawing metal-rich wastes, for the synthesis of new black pigments. The sludges were
characterized in terms of chemical composition. The pigments were based on ferrite structure
monoferrite and strontium hexaferrite.
The first pigment has the (Ni,Fe)(Fe,Cr)2O4 spinel structure, and is mainly constituted by trevorite.
In minor quantities, magnetite (Fe3O4) and chloroapatite were also detected due to the non-
stoichiometric impact of the use of sludges in the formulation. In the hexaferrite mixtures,
SrFe12O19, -Fe2O3 and Sr2Fe2O5 were identified by XRD analysis. As expected from the initial
formulations, the strontium hexaferrite was the major component of the prepared powders and the
incomplete degree of the reaction in these conditions led to the association with two minor phases.
The absorbance data of Tr and Fr pigments have shown differences between pure and waste
based formulations in the red light interval. According to the phase composition, this is due to the
variable amount of secondary phases between pure and sludge based powders; especially
hematite.
Nevertheless, in both cases, the pigments obtained from pure and secondary raw materials
exhibited a good black colour competing with commercial pigment.
ACKNOWLEDGEMENTS
The work was supported by FCT-CNR joint project 20112012 Ceramic pigments from industrial
wastes.
390
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(2011), p. 619.
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reuse, 4th ed, Editorial Boston, McGraw-Hill, 2003.
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Altaba: Journal of Solid State Chemistry Vol. 72 (1988), p. 218.
[4] R. Collongues, D. Gourier, A. Kahn-Harari, A.M. Lejus, J. Thery and D. Vivien: Annu. Rev.
Mater. Sci. Vol. 20 (1990), p. 51.
[5] S.K. Rakshit, S.C. Parida, S. Dash, Z. Singh, B.K. Sen and V. Venugopal: J. of Solid State
Chemistry Vol. 180 (2007), p. 523.
[6] Z.F. Zi, H.Y. Liu, Y.N. Liu, L. Fang, Q.C. Liu, J.M. Dai, X.B. Zhu and Y.P. Sun: J. Magn.
Magn. Mater. Vol. 322 (2010), p. 3638.
[7] J.F. Wang, C.B. Ponton and I.R. Harris, J. Magn. Magn. Mater. Vol. 234 (2001), p. 233.
[8] . zgr, Y. Alivov, and H. Morko, J. Mater. Sci. Mater. Electron. Vol. 20 (2009), p. 911.
[9] Dong-Hwang Chen and Xin-Rong He, Mater. Res. Bull. Vol. 36 (2001), p. 1369.
[10] R.C. Pullar, M.D. Taylor and A. K. Bhattacharya, J. Eur. Ceram. Soc. Vol. 22 (2002), p.
2039
[11] Xinyong Li, Gongxuan Lu and Shuben Li, J. Mater. Scie. Lett. Vol. 15 (1996), p. 397.
[12] K. Haneda, C. Miyakana and H. Kojima J. Am. Ceram. Soc. Vol. 57 (1974), p. 354.
[13] CIE, Recommendations on Uniform Colour Spaces, Colour Difference Equations,
Psychometrics Colour Terms. Suplement no. 2 of CIE Publ. No. 15 (E1-1.31) 1971, Bureau Central
de la CIE, Paris, 1978.
[14] E. Ozel, S. Turan, J. Eur. Ceram. Soc. Vol. 23 (2003), p. 97.
[15] S.E. Ziemniak, A.R. Gaddipati, P.C. Sander, Immiscibility in the NiFe2O4NiCr2O4 spinel
binary, J. Phys. Chem. Solid. Vol. 66 (2005), p. 1112.
[16] J. Calbo, S. Sorl, M. Llusar, M.A. Tena and G. Monrs: Brit. Ceram. T. Vol. 103 (2004), p.
3.
391
St
MECHANICAL BEHAVIOR OF RECYCLED AGGREGATES FROM

CONCRETE WASTE
C. Thomas, I .Sosa, J. Setin, J.A. Polanco, I. Lombillo.

Dept. of Science and Engineering of Materials, University of Cantabria, College of Civil Engineering
of Santander, Spain. thomasc@unican.es
ABSTRACT
This paper establishes the relationship between the properties of recycled aggregates
obtained from crushing and processed wastes from structural concrete versus the
properties of recycled concrete made with them. An ambitious test program has been
carried out in order to characterize completely the physical, chemical and the recycled
aggregate stability, making emphasis on its behavior to compressive strength. Regarding
the recycled concrete, mixtures have been studied with 0.65 water/cement ratio, as well
as substitution degrees of 0% (as control concrete), 20%, 50% and 100% of the
aggregate natural coarse limestone for recycled aggregates of crushed concrete obtained
from demolition, characterizing their physical and mechanical properties in order to
establish the relationship between the behavior to compressive strength of its
components and of the concrete itself.
Keywords: aggregates, concrete, recycling, compression, aggregates crushing value.
INTRODUCTION
The materials on which this work arises are recycled aggregates from crushing and processing
wastes from demolition of structural concrete, and the recycled concrete made from them. Previous
researches have been made, showing the opportunity afforded by the use of recycled aggregates
(RA) for the manufacture of concrete and in particular on the use of recycled concrete aggregates
(RCA) [1-9]. The RCA is, among all of RA, is the one which best meets the necessary requirements
for the manufacture of recycled concrete (RC). The features that they offer are suitable for these
purposes [10]. This paper deepens into the characteristics of these aggregates to finally relate
these to the characteristics of recycled concrete made from them (RC).
Necessarily, the mechanical properties of the RC have to be related to the RA. This research has
considered the recycled concrete as a composite material, on the one hand, coarse aggregate, on
the other hand, a binder matrix (MX) (hydrated cement and sand) and finally, their interfaces (IN).
Through a comprehensive test program, the RA and RC made with them have been fully
characterized. With these tests, physical properties and chemical stability of the RA were
determined, making special emphasis on the mechanical properties, and in particular their behavior
under compresive loads. In the same way, the RC has been characterized in terms of their physical
and mechanical properties, and finally the relationship between components and concrete was
analyzed in depth.
Replacements of 0% (control concrete), 20%, 50% and 100%, of natural limestone coarse
aggregate used for structural concrete, by recycled coarse aggregates from crushing demolition
concrete were studied, with a water/cement ratio (w/c) of 0.65.
392
MATERIALS
Recycled and natural aggregate

Natural aggregates (NA) used in the investigation all come from nature and from crushed
limestone. We used three distinct sizes: 0/4, 2/8 and 8/20. Results of dimensional and physical
characterization of each of the fractions of NA and RA are shown in Table 1.
Table 1. Properties of aggregates.

Aggregate Sand Gravel Gravel RA
d/D [mm] 0/4 4/8 8/20 4/20

Class: GF85 Gc85/20 Gc90/15 Gc90/15
Fines [% weight]: 7.53 0.12 0.97 0.38
Percentage of particles < 4 mm [% weight]: 100.00 71.54 1.78 25.01
3
Real density. Fractions (2-4 mm) [g/cm ]: 2.65 2.62 2.53 2.53
3
Apparent density [g/cm ]: - 2.47 2.46 2.28
Relative density [g/cm3]: - 2.58 2.53 2.51
Saturated density [g/cm3]: - 2.51 2.49 2.37
Water absorption [% weight]: - 1.86 1.20 4.02
Accessible porosity [% volume]: - 4.58 2.95 9.16
The RA used in the study was obtained from sorting and processing construction and demolition
waste (CD&W).
First, there has been a visual separation of components and it was found that the weight
percentages of components whose source is crushed concrete (natural aggregate, mortar natural
aggregate and mortar attached) was 95.55%. The remaining components found were bituminous
(1.58%), ceramics (1.39%), gypsum (0.64%) and fine material (0.43%).
Moreover, size analysis of both NA and RA used as a substitute for natural aggregates in RC
conducted according to UNE - EN 933, is shown in Figure 1.
Figure 1. Particle size distribution of the different fractions of natural and recycled aggregate.
Recycled concrete
To carry out the concrete characterization, a selection of NA and RA has been made, then standardized
cylindrical (15 x 30 cm) specimens were made with them.
The mixtures with different substitution degrees come from control mixtures designed with Fullers
method based on size distribution and w / c ratio. Once the structural control concrete is designed with a
maximum aggregate size of 20 mm, all other dosages were designed replacing the coarse fraction of the
NA by the RA percentages (20%, 50% or 100%).
393
The method of concrete fabrication was the proposed in the European standards with minor
modifications based on the special characteristics of the RA [10]. RA has significantly higher
absorption than natural aggregate, 4% by weight compared to 1.9% and 1.2% of the natural gravel.
As a consequence, a loss of mixing water occurs in fresh RC, which is proportional to the
substitution degree. For this reason it was decided to saturate previously the AR by water
immersion for 10 min, and drain for 10 min prior to its incorporation. This ensures the same
effectively water/cement ratio for all concretes.
It was produced a total of 64 samples divided into 4 doses with 3 substitution degrees, 20%
(recommended use of recycled aggregate under Spanish law), 50% and 100% of natural aggregate
limestone by RA and 0% replacement or mixture control. 10 RC specimens were used for
determining the modulus of elasticity, 3 specimens were used to determine the compressive
strength and 3 were used to determine the tensile strength by the indirect testing method.
EXPERIMENTAL PROGRAM
Los Angeles wear coefficient of the RA

The determination of this parameter is performed using the procedures described in the UNE-EN
1097-2: "Methods for the determination of resistance to fragmentation". In order to find out the
behavior of recycled aggregates with natural aggregates, it has been considered to analyze the
wear coefficient of different combinations of aggregates. It was taken the percentage related to
fraction 10/14 (required in this test) and a portion of gravel and other recycled aggregate as is
proposed in the mixtures to be analyzed. The gravel and recycled aggregate have been screened
to a size 10/14, mixed properly, and finally weighed.
Behavior of aggregates under compressive stress

In order to perform this characterization, the protocols established in the UNE 83112: Aggregates
for concrete. Determination of aggregates crushing value, were followed. The aggregates crushing
value is an indicative of its strength to compression, because unlike the test of Los Angeles,
compression is made by the action of a particle on the next one, while all of them subjected to an
external load applied gradually within a non-deformable cylinder.
According to standard, the sample selected must have particle sizes that pass through the sieve of
14 mm and are retained by the sieve of 10 mm (fraction pattern 10/14) or between opening screens
14/20, as the case. In this research, the two fractions have been considered in order to clear up
doubts about the mechanical behavior of aggregates of various sizes. Meanwhile we have
analyzed the natural aggregates crushing value and mixtures of 20%, 50% and 100% substitution
of AN by AR, as it was proceeded in Los Angeles coefficient tests. In this case fraction 14/20 was
tested in the same way as well.
As a complement to the results provided by the standard test, it was proceeded to measure the
deformation of the material and thereby to obtain the stress-strain curve of the aggregates
structure.
Mechanical properties of RC
In order to find out the compressive strength of standard concrete specimens, the premises
established in the EN 12390-3: Testing hardened concrete. Compressive strength of test
specimens have been followed. To come across the indirect tensile strength of concrete
specimens the guidelines established in the EN 12390-6:2001: Testing hardened concrete.
Indirect Tensile specimens have been followed.
In order to perform the test, an universal servo-hydraulic press of 1500 kN maximum load was
used, the load application rate was 8 kN/s for the case of tension and 10 kN/s for compression.
Modulus of elasticity of concrete

To keep on with the mechanical characterization tests, the modulus of elasticity of concrete has
been determined. To accomplished this tests, the guidelines established in the UNE 83316:1996:
Concrete tests. Determination of the modulus of elasticity in compression has been used.
Meanwhile, for the deformation record, the specimens were instrumented using strain two gauges
of 120 mm length arranged in two opposite generatrix of the cylinder.
394
RESULTS
Los Angeles wear coefficient of the RA

For high-strength concrete is recommended that the coefficient of Los Angeles does not exceed
25. The results of the analysis of soft particles of AR for the two fractions (10/12.5 and 12.5/20 mm)
considered are collected in Table 2.
Table 2. Wear coefficient of Los Angeles for NA, RA and all percentages of replacement.
Combination LA [%]
% of NA 100% NA: 21
% of RA 80% NA and 20% RA: 24
80% RA and 20% NA: 27
100% RA: 32
As it can be seen, in general, the coefficient of Los Angeles of various substitutions can be
expressed as a typical mixture rule:
LAD LAi i (1)

i
Where:
LAD : is the coefficient of Los Angeles for the corresponding mixture.
LAi: are the coefficients of Los Angeles of the i components of the mixture.
i : are the percentages of incorporation of each of the i components of the mixture.
Behavior under compressive stress of the aggregate

The results of the aggregate crushing value for the RA and all mixtures incorporating in this case
also the fraction 14/20 are presented in Table 3.
Table 3. Aggregate crushing value for the NA, RA and all percentages of replacement.
Mixture: RC-0.65
Fraction: 10/14 14/20
100% NA: 32.0 32.0
80% NA and 20% RA 31.3 31.3
80% RA and 20% NA: 30.7 30.7
100% RA: 30.0 30.0
The most interesting result of the crushing test is the stress-strain curve obtained with all different
percentages of replacement tested. Thus, an elastic behavior of the material around 15% of its
deformation it is clearly shown in Figure 2.
395
14 14
RC0.65 0% RC0.65 0%
RC0.65 20% RC0.65 20%
12 12
RC0.65 50% RC0.65 50%
RC0.65 100% RC0.65 100%
10 10
Strength [MPa]
Strength [MPa]
8 8
6 6
4 4
2 2
0 0
0 5 10 15 20 25 30 0 5 10 15 20 25 30
Strain [%] Strain [%]
Figure 2. Stress-strain curve of different mixtures of RA. Fractions 10/14 (left) and 14/20
(right).
The modulus of elasticity obtained for the fractions 10/14 and 14/20 of aggregate for all the
mixtures of RC made are presented in Table 4.
Table 4. Mechanical behavior of RA for the different mixtures.

Fraction: 10/14 14/20
Replacement: 0% 20% 50% 100% 0% 20% 50% 100%

AME [GPa]: 53.2 49.3 45.3 27.2 46.6 44.9 40.6 36.5
ALE [MPa]: 8.8 7.3 6.1 3.5 7.8 7.2 6.3 5.1
ALE Def. [%]: 15.6 13.7 13.5 12.3 16.5 15.2 15.1 14.1
Where:
AME: Modulus of elasticity of aggregate.
ALE: Limit of Elasticity of aggregate.
The results of the modulus of elasticity of RC for each percentage of replacement of NA by RA are
collected in Table 5.
Table 5. Modulus of elasticity of concrete for different mixtures of RC.

Replacement: 0% 20% 50% 100%
CME [GPa]: 32.87 32.18 30.15 23.87
Where: CME: Modulus of Elasticity of Concrete.
50
RC-0.65
Average aggregates
45
Modulus of Elasticity [MPa]
40
35
30
25
20
0 20 40 60 80 100
Substitucin percentage [%]
Figure 3. Behavior of the modulus of elasticity of recycled concrete.
396
Figure 3 shows that the behavior of concrete depends on the properties of the aggregates
contained in its skeleton. It is observed that with a higher replacement percentage of NA by RA, the
difference in the modulus of elasticity values obtained are reduced. This relationship was obtained
comparing the modulus of elasticity of concrete RC0.65 with the average values of the modulus of
elasticity obtained for the fractions of aggregates 10/14 and 14/20. In addition, it was seen that with
a higher percentage of recycled aggregate the difference between the values of RC and RA
decreases due to the characteristics of the RA.
CONCLUSIONS
In general, it is considered that is necessary to limit the coefficient of Los Angeles of the coarse
aggregate used in the manufacture of concrete, because of increasing this coefficient the
deformation under load of concrete increases and can lower the concrete strength. In general, the
recycled aggregate has a high wear coefficient value, because of along the tests, all or part of the
mortar adhered to the surface of the aggregate is detached, in addition to the loss associated to the
original aggregate.
The aggregate crushing value is reduced with the incorporation of recycled aggregate for each
fraction. Likewise, the aggregate crushing value of the fraction 10/14 is slightly higher than the
fraction 14/20. The first result is due to the adhered mortar of the RA against compressive stress.
The second result is attributable to the greater amount of mortar per volume found in the fraction
10/14 versus 14/20. In particular, it is noteworthy that among the bigger sized aggregates a small
percentage of them are made up exclusively of mortar.
There is a trend of the elastic behavior of concrete related to the properties of the aggregates
contained in it; also it is showed that increasing the percentage of recycled aggregate, the
difference between the values obtained for concrete and aggregate decreases. This suggests that
in the case that recycled concrete contains high degrees of substitution, the cement paste takes all
the responsibility than in control concretes. In addition, it has been observed how the negative
effect that involves the incorporation of RA affects less to concretes with a minor w/c ratio, resulting
therefore in more competent pastes.
References
[1] Comisin 2 Grupo de trabajo 2/5 "Hormign Reciclado". Utilizacin de rido reciclado para la
fabricacin de Hormign Estructural. : ACHE; 2006.
[2] Etxeberria M, Vazquez E, Mari A, Barra M. Influence of amount of recycled coarse aggregates
and production process on properties of recycled aggregate concrete. Cem.Concr.Res. 2007
MAY;37(5):735-42.
[3] Evangelista L, de Brito J. Mechanical behaviour of concrete made with fine recycled concrete
aggregates. Cem.Concr.Compos. 2007 MAY;29(5):397-401.
[4] Rao A, Jha KN, Misra S. Use of aggregates from recycled construction and demolition waste in
concrete. Resources Conservation and Recycling 2007 MAR;50(1):71-81.
[5] Thomas C, Setin J, Polanco JA. Determinacin del lmite a fatiga en hormigones reciclados de
aplicacin estructural. Anales de Mecnica de la Fractura 2009;1:283-289.
[6] Comparacin de las prestaciones mecnicas entre hormigones reciclados con residuos de
construccin y demolicin (RCDs) y hormigones convencionales. ; 20/09/2007; : AEMAC; 2007.
construction and demolition waste: generation, recovery and applications. RECIMAT'09
2009;1:156-9.
[8] Thomas C, Setin J, Polanco JA. Determinacin de la macroporosidad accesible y no accesible
mediante anlisis digital de imgenes en hormigones reciclados de aplicacin estructural. X
Congreso nacional de Materiales 2008;II:923-6.
[9] UNE 146121:2000. ridos para la fabricacin de hormigones. Especificaciones para los ridos
utilizados en los hormigones destinados a la fabricacin de elementos de hormign estructural.
[10] Snchez M, Alaejos P. Estudio sobre las propiedades del rido reciclado. Utilizacin en
hormign estructural. ; 2006.
397
St
WASTE WITH SULFUR FROM TESTED CONCRETE SPECIMENS AS

AGGREGATE FOR STRUCTURAL RECYCLED CONCRETE
C. Thomas1; A. Cimentada2, J. Setin1, J. A. Polanco1, J. Rico3, I. Sosa1

1 Dept. of Science and Engineering of Materials, University of Cantabria, College of Civil
Engineering of Santander. Avda. Los Castros s/n, Santander, 39005 Spain. thomasc@unican.es
2 Dpto. Investigacin y Desarrollo, Triax S.A. Faustino Cavadas 28, 39011 Peacastillo, Spain.
3 Dpto. I+D+i, Emilio Bolado S.L., 39608 Cacidedo de Camargo, Spain.
ABSTRACT
This paper presents the main results of the research carried out to analyze the technical
feasibility of using recycled aggregates obtained from crushing tested concrete
specimens in structural concrete production. In the year 2007, the total number of
standard cylindrical specimens made for quality control laboratories in Spain exceeded 5
million units. This amount is equivalent to a volume of approximately 30,000 m 3 and a
mass of 60,000 tons of concrete waste. Usually, once the specimens are tested, they are
considered waste and taken to landfills where they are mixed with other construction and
demolition wastes. Recycled aggregates obtained from test specimens of concrete have
clear advantages over concrete recycled aggregates obtained from construction and
demolition wastes. Indeed, the composition of this waste is basically concrete with small
amounts of sulfur, used in the specimen capping, unlike recycled aggregates from
construction and demolition wastes which are much more heterogeneous. Furthermore,
the characteristics of the recycled aggregate, in this case, are known with great accuracy
through the concrete specimens. Therefore, it is a material with great potential value. The
sulfur is an element that can react with most elements that contain different types of
binding, producing hazardous materials when it is taken directly to landfills. However, the
presence of sulfur in these recycled aggregates may only have negative effects on the
durability of the concrete made with them. In fact the incorporation into a cement matrix
should not be an environmental problem. In this work, an ambitious characterization
program of recycled aggregate has been obtained from testing specimens.
Keywords: aggregates, concrete, recycling, capping, sulfur.
INTRODUCTION
A great number of research has been dedicated to find different ways of using recycled aggregate
(RA) in the manufacture of concrete and, in particular, the use of recycled aggregates from
concrete (RAC) [1-9]. The properties of RAC make them the most appropriate of all RA for the
production of recycled concrete (RC) [10].
However, most studies have focused on aggregates obtained from demolitions of structural
concrete. These concretes have, in many cases, uncertain characteristics and may even have
suffered damage or degradation processes throughout their in-service lifetime.
This is not the case of recycled aggregates obtained by crushing concrete specimens (tested or
not) from control laboratories (SRA). In this case, the original concrete is well known and is usually
an early age concrete; in most cases 7 and/or 28 days. This implies a positive effect on the
characteristics of the RA and the RC made with them. First, the concrete specimens have not been
exposed to aggressive environments and therefore do not introduce hazardous agents to the new
concrete [11]. Also, the early age of the cement from the original concrete is still evolving and may
improve on the characteristics, over time, of the new concrete.
398
The number of control specimens tested in Spain during 2007 exceeded 5 million [12, 13]. This
large number becomes a waste material with a mass of approximately 60,000 tons. However, the
characteristics of this material show its great value for recycling. Hence, mixing it with other
construction and demolition wastes (CDW) generally implies a loss of properties. Due to its
characteristics, it can be best used in structural RC.
However, there is a widely assumed drawback in the use of SRA which is because of they contain
certain amounts of sulfur. The most common characterization of concrete is the compressive
strength test. Moreover, the geometry of concrete standard specimens is usually, in Europe [14]
and North America [15], cylindrical. This implies that, before testing, the specimens need to be
capped [16, 17]. Sulfur is the most widely material used in the capping process of cylindrical
specimens, whether pure or in the form of mortar. This leads to an uncertainty, whether the sulfur
found in the SRA may or may not adversely affect the durability of the RC. Incorporating sulfur into
the RC supposes a loss of mechanical properties and volumetric compatibility issues. However, in
principle, the incorporation into a cement matrix should not be an environmental problem because
under these conditions, alkaline conditions, the sulfur is a stable material [18]. Not so when the
capping sulfur is taken directly to landfill. It is an element that can react with most elements that
contain different types of binding. This sulfur in the presence of O2 and a relatively small heating is
transformed to SO2, which can turn in the presence of water, to the hazardous H2SO4. The sulfur
can also lead to H2S, even more hazardous than the H2SO4.
In order to remove the doubts, an ambitious test program has been undertaken. The aim is to
characterize the SRA and analyze the technical feasibility to produce structural concrete replacing
natural aggregates by SRA. The tests carried out on the RA have provided physical and chemical
properties as well as mechanical and stability characteristics.
MATERIALS CARACTERIZATION
Waste from concrete specimens

The RA used in this research was obtained from cylindrical test specimens (more than 5000) all
tested and broken under compressive loads. Two types of RA and two types of RC have been
analyzed. Firstly, we were able to collect a large number of specimens with presence of sulfur from
the capping and, secondly a similar number of tested specimens were gathered whose sulfur
capping layer had been removed. This made it possible to analyze two types of waste from
concrete specimens: those containing certain amounts of sulfur and other waste composed only of
concrete. Then it would be possible to define the influence of sulfur on the RA and the RC.
Once the original specimens were tested and stockpiled, approximately 30 tons of concrete waste
with sulfur (SW-I) and 30 tons of clean waste (SW-II) were obtained. The characteristics of the
original concrete from which the waste was taken are presented in Table 1.
Table 1. Characteristics of the original concrete from which the SRA is obtained.
Obtained Compression
N of crushed Specimen age average
specimens waste strength average
specimens [days]
type [MPa]
SW-I 2417 22 35.1
SW-II 2698 22 34.4
As can be seen in Table 1, the average age of the specimens is around 22 days. All the specimens
were tested under compression according to the standards specifications [14, 16]. The average of
compressive strength is around 35 MPa. These characteristics would suggest that a RA may be
obtained from them with very good features.
Sulfur from capping

In the process of capping, pure sulfur or sulfur mixed with natural dry sand (ISO 12390-2) is
normally used. Pure sulfur, below 96 C, is in the rhombohedral S8 form. When it is heated, over
118 C, the S8 crystals acquire mobility and the solid goes to the liquid state. In this liquid state, the
399
capping of the specimen is undertaken [16], and then the sulfur recrystallizes at normal conditions
to rhombohedral S8 again [18].
Recycled aggregates
Once the residue, with and without sulfur, is obtained using a mechanical crusher, each one of
these was separated into three distinct fractions: 0-6 mm (FA), 6-12 mm (FB) and 12-18 mm (FC).
These separations will greatly facilitate the mixture of the RC. The results in terms of particle size
distribution [19] are shown in Fig. 1 and the three considered fractions (FA, FB and FC) of the
crushed aggregate are presented PARTICLE
in Fig. 2. SIZE DISTRIBUTION
RECYCLED AG GREGA TES
100
80
PERCENT PA SSING [%]
60
40
20
0
8
1
125
6.3
0.5
0.063
63
20
16
14
12.5
10
0.25
0.125
40
31.5
1000 100 10 1 0,1 0,01

SIEVE SIZE, [mm] (log. s cale)
Fig. 1. Particle size distribution of the SRA before the separation.

PARTICLE SIZE DISTRIBUTION
RECYCLED AG GREGA TES
10 0
12-18
80
6-12
PERCENT PA SSING [%]
0-6
60
40
20
0
8
1
125
6.3
0.5
0.063
63
20
16
14
12.5
10
0.25
0.125
40
31.5
1000 100 10 1 0,1 0,01

SIEVE SIZE, [mm] (log. s cale)
Fig. 2. Particle size distribution of the 3 different fractions of the SRA after the separation.
The geometrical properties of the two types of aggregates considered, with sulfur (SRA-I) and
without sulfur (SRA-II) are indistinguishable. However, in terms of physical properties, as can be
seen in the results presented in Table 2, the fine fraction of the SRA-II has a greater density due to
the absence of sulfur. The crystallized free sulfur has an apparent density of 1.96 kg/m 3 (less than
the aggregate) which gives lower densities to the fractions of SRA-I.
400
Table 2. Physical properties of the SRA.
SRA
Fraction Da [kg/m3] Dsss [kg/m3] A [%]
type
FA 2.29 2.59 8.7

SRA-I FB 2.21 2.39 6.2
FC 2.16 2.32 5.8
FA 2.31 2.62 9.1
SRA-II FB 2.20 2.38 6.3
FC 2.16 2.32 5.7
Where:
Da Aparent density (kg/m 3) [20].
Dsss Saturated particles density with dry surface (kg/m3) [20].
A Water absorption (% weight) [21].
Table 3. Properties of the SRA.

SE SE4 AM LA FI MS MS* MO ClS SS
SRA type
[%] [%] [g/kg] [%] [%] [%] [%] [Y/N] [%] [%]
SRA-I 75 86 0.43 23 5 0.01 5.92 Negativ 0.03 1.51
SRA-II 74 83 0.41 25 5 0 1.2 Negativ 0.03 1.41
Where:
SE Sand Equivalent, fraction 0/2 [22].
SE4 Sand Equivalent, fraction 0/4 [22].
AM Methylene blue [23].
LA Los Angeles coef. [24].
FI Flakiness Index [25].
MS Loss with magnesium sulfate 5-cycles (%) (Fraction 10/14 mm) [26].
MS * Loss with magnesium sulfate 5-cycles (%) (Fraction out of 10/14 mm) [26].
MO Organic materials [27].
ClS Water-soluble chloride salts [27].
SS Acid-soluble sulfate salts[27].
Once the aggregates have been physically and mechanically characterized, the chemical and
mineralogical analyses of each of the fractions considered have been carried out.Three specimens
of each fraction were analyzed.Table 4 presents the results obtained.
Table 4. Quantitative analysis by EDS of the 3 fractions of the SRA-I and SRA-II.
SRA type Analysis Fraction O Mg Al Si S K Ca Fe
FA 32.8 1.1 1.1 5.1 3.6 0.9 53.9 1.5
SRA-I Weight [%] FB 34.7 0.9 1.3 5.0 1.6 0.1 56.4 0.1
FC 34.8 0.9 1.1 5.0 1.5 0.0 56.7 0.0
FA 30.3 1.3 2.0 7.8 1.0 0.7 55.7 1.2
SRA-II Weight [%] FB 32.6 1.0 1.7 6.5 0.9 0.3 56.5 0.6
FC 31.5 0.9 1.4 6.9 0.8 0.5 58.0 0.0
401
As it is shown in Table 4, the fine fraction of SRA-I have higher sulfur content. This effect may be
due to the high friability of the rhombohedral S8 sulfur crystals, whose Mohs hardness is 2. During
the process of crushing and screening of SW-I, the sulfur undergoes a greater fragmentation than
the concrete.
In order to check the crystalline state in which the sulfur is presented, and to evaluate the influence
that it may have on the characteristics of the SRA and RC, mineralogical analyses have been
performed by X-ray diffraction [28] on each fraction of the SRA-I. Fig. 3 shows the results obtained.
1600 1500 1200
C C C
+ + +
1400 T T T
+ + 1000 +
S S S
1200
1000 800
Intensity [u. a.]

1000
Intensity [u. a.]
Intensity [u. a.]
800 600
C
+
600 P
500 400
Q Q C Q DC C Q
Q
+ C + C + + C + + +
400 + C
S + P P P P
C
C
Q C C
Q C + C P S + Q
C +
+ + Q + Q
+ C + C 200
+ D S D Q D D C
200 S D Q + + + C +
D C
D CD S D C C Q D C
T P Q D QC D C S SP S D
Q T P Q D DQ C D C
Q
S SP S D D
T P Q D D Q C D CD
PQ S SP QD PQ P
0 0 0
0 10 20 30 40 50 60 70 80 0 10 20 30 40 50 60 70 80 0 10 20 30 40 50 60 70 80
2 [degree] 2 [degree] 2 [degree]
Fig. 3. X-Ray diffraction pattern of the FA (left), FB (middle) and FC (right) of SRA-I, where
C: CaCO3; Q: SiO2, P: Ca(OH) 2, T: CSH; D: CaMg(CO3)2 and S: S8.
With these tests, it has been proved that most of the sulfur detected in the rhombohedral crystalline
state is stable. The 0.9% sulfur base, observed in the SRA-II chemical analysis (Table 4) of the
cement from the original concrete, is not detected in the diffraction patterns.
CONCLUSIONS
As a final conclusion, it appears that the use of SRA, with or without sulfur, is viable for the
manufacture of recycled structural concrete for applications without exposure to high temperatures.
However, the use of the fine fraction of these aggregates means a significant loss of properties in
relation with the control concrete. Thus, for applications in which the RC is exposed to
temperatures above 100 C, those which require a high performance concrete or using the fine
fraction (0/6) of these recycled aggregates is not recommended.
Acknowledgements
We would like to thank the companies Emilio Bolado S.L. and Triax S.A. and the institution
SODERCAN, CEDTI and Spanish Ministry of Science and Technology for funding this research
project.
References
[1] VWY Tam, XF Gao, CM Tam, KM Ng. Physio-chemical reactions in recycle aggregate concrete,
J.Hazard.Mater. 163 (2009) 823-828.
[2] Comisin 2 Grupo de trabajo 2/5 "Hormign Reciclado", Utilizacin de rido reciclado para la
fabricacin de Hormign Estructural, ACHE 2006.
[3] M Etxeberria, E Vazquez, A Mari, M Barra. Influence of amount of recycled coarse aggregates
and production process on properties of recycled aggregate concrete, Cem.Concr.Res. 37 (2007)
735-742.
[4] L Evangelista, J de Brito. Mechanical behaviour of concrete made with fine recycled concrete
aggregates, Cem.Concr.Compos. 29 (2007) 397-401.
[5] A Rao, KN Jha, S Misra. Use of aggregates from recycled construction and demolition waste in
concrete, Resources Conservation and Recycling. 50 (2007) 71-81.
[6] C Thomas, J Setin, JA Polanco. Determinacin del lmite a fatiga en hormigones reciclados de
aplicacin estructural, Anales de mecnica de la fractura. 1 (2009) 283-289.
402
[7] C Thomas, J Setin, JA Polanco, Comparacin de las prestaciones mecnicas entre
hormigones reciclados con residuos de construccin y demolicin (RCDs) y hormigones
convencionales, Materiales Compuestos. 1 (2007) 221.
construction and demolition waste: generation, recovery and applications, RECIMAT'09. 1 (2009)
156-159.
[9] C Thomas, J Setin, JA Polanco. Determinacin de la macroporosidad accesible y no accesible
mediante anlisis digital de imgenes en hormigones reciclados de aplicacin estructural, X
Congreso nacional de Materiales. II (2008) 923-926.
[10] M Snchez, P Alaejos, Estudio sobre las propiedades del rido reciclado. Utilizacin en
hormign estructural, 2006.
[11] F Debieb, L Courard, S Kenai, R Degeimbre. Mechanical and durability properties of concrete
using contaminated recycled aggregates, Cement and Concrete Composites. 32 (2010) 421-426.
[12] J. E. Caadas, Experiencias de reciclaje en plantas de hormign preparado, 2010, pp. 189-
194.
[13] GERD, Gremio de Entidades del Reciclaje de Derribos, (2008).
[14] UNE-EN 12390-2. Ensayos de hormign endurecido. Parte 2: Fabricacin y curado de
probetas para ensayos de resistencia, (2009).
[15] ASTM C39. Compressive strength of cilindrical concrete specimens, ASTM Standards Book.
(1984).
[16] UNE-EN 12390-3. Ensayos de hormign endurecido. Parte 3: Determinacin de la resistencia
a compresin de probetas, (2009).
[17] ASTM C617. Capping cylindrical concrete specimens, ASTM Standards Book. (1984).
[18] SL Lin, WH Cross, ESK Chian, JS Lai, M Giabbai, CH Hung. Stabilization and solidification of
lead in contaminated soils, J.Hazard.Mater. 48 (1996) 95-110.
[19] UNE-EN 933-1. Ensayos para determinar las propiedades geomtricas de los ridos. Parte 1:
Determinacin de la granulometra de las partculas. Mtodos del tamizado, (1998).
[20] UNE-EN 1097-3. Ensayos para determinar las propiedades mecnicas y fsicas de los ridos.
Parte 3: Determinacin de la densidad aparente y la porosidad, (1999).
[21] UNE-EN 1097-6. Ensayos para determinar las propiedades mecnicas y fsicas de los ridos.
Parte 6: Determinacin de la densidad de partculas y la absorcin de agua, (2001).
Evaluacin de los finos. Ensayo del equivalente de arena, (2000).
Evaluacin de los finos. Ensayo de azul de metileno, (2010).
[24] UNE-EN 1097-2:1999/A1. Ensayos para determinar las propiedades mecnicas y fsicas de
los ridos. Parte 2: Mtodos para la determinacin de la resistencia a la fragmentacin, (2007).
[25] UNE-EN 933-3/A1. Ensayos para determinar las propiedades geomtricas de los ridos. Parte
3: Determinacin de la forma de las partculas. ndice de lajas, (2004).
[26] UNE-EN 1367-2. Ensayos para determinar las propiedades trmicas y de alteracin de los
ridos. Parte 2: Ensayo de sulfato de magnesio, (2010).
[27] UNE-EN 1744-5:2007. Ensayos para determinar las propiedades qumicas de los ridos. Parte
5: Determinacin del contenido de cloruros solubles en cido, .
[28] American Society for Testing Materials (ASTM). Powder Diffraction File Search Manual,
(1975).
403
CHARACTERISATION OF AUTOMOTIVE SHREDDER RESIDUE

1 2
F. Margarido , C.A. Nogueira
1 Dep. Engenharia Mecnica, Instituto Superior Tcnico (TU Lisbon), Av. Rovisco Pais, 1049-001
Lisboa, Portugal, fernanda.margarido@ist.utl.pt
2 Laboratrio Nacional de Energia e Geologia, I.P., UPCS, Estrada do Pao do Lumiar, 1649-038
Lisboa, Portugal, carlos.nogueira@lneg.pt
ABSTRACT
The autofluff residue of a Portuguese shredding facility was characterised aiming at
identifying the presence of heavy metals in several constituents of these residues, in
order to propose possible valorising solutions. Particle size analysis showed that average
characteristic diameter (d50) was 6.5 mm, the coarser fractions (> 11 mm, representing
40% of weight) being essentially composed of plastic pieces, rubber, foams and textiles,
particles in the range 2-11 mm being composed of mixed materials, while in particles
below 2 mm (referred as fines) the presence of glass, ceramics and other inorganic
materials became very frequent, in spite of a very fine foam was also detected in the very
fine fractions. XRD analysis of fines allowed detecting the crystalline phases quartz,
calcite, rutile and magnetite. Elemental analysis by EDXRF was carried out on several
fractions in the particle size range 0.02-2.0 mm, showing the presence of practically all
the elements detected in all fractions, namely Fe, Zn, Cu, Pb, Ba, Sn, and also traces of
Cd, Sb, Mo and Sr. Some of these metals are hazardous and can be problematic in what
concerns the possible valorisation of the residue.
Keywords: Automotive shredder residue; characterisation; heavy metals; recycling.
INTRODUCTION
End-of-life vehicles (ELVs) require adequate and efficient management due to environmental and
economic reasons [1-3]. Recycling of ELVs is usually carried out in auto-shredding facilities [4],
where vehicles are decontaminated, shredded and subsequently several fractions are obtained by
means of combined physical processes involving air classification, magnetic, eddy current and size
separation. The main material stream is a ferrous fraction (about 70-75% of total feed weight) sent
to steel manufacturers, a non-ferrous and heavy (polymer-rich) fractions, also potentially
recoverable, and a light fraction (also called fluff or autofluff) designated as automotive shredder
residue (ASR), representing 20-25% of initial weight, to be sent to disposal.
A typical diagram of an automotive shredder process is presented in Fig. 1. The ELVs transported
to an authorised facility are received and stored appropriately. After recording the vehicle data, it is
sent to a depollution process where hazardous components such as batteries, tires, mercury
switches and fluids (including remaining fuel, waste oil, shock absorbing oil, brake fluids and
cooling liquids) are removed. Other components for dumping or recycling are also removed at this
stage, including wheels, glass, plastic bumpers and catalytic converters. The depolluted vehicle is
then sent to the shredder, usually a hammer mill, where size reduction is carried out allowing
liberation of different materials. In the shredding chamber, the first separation occurs, the light
materials (foams, cloths) being drawn away by suction and the heavy fraction containing metals
and some plastics being discharged in the bottom of the shredder. The light fraction passes by a
magnetic separator to recover some remaining steel, resulting the ARS as waste stream. The
heavy fraction is processed through a series of physical separation steps to produce the main
stream of the process: the steel rich fraction. The separation starts with a magnetic operation
where the ferrous materials are selectively collected and afterwards passes by a picking shed
where some mixed materials are removed and the steel fraction is finally produced and sent to
404
melting in electric steelmaking facilities. The non-magnetic materials are sieved into homogeneous
particle size fractions and processed in an eddy current separator to extract the metals (essentially
copper and aluminium) from the non-metallic materials (mainly heavy plastic fragments). Finally
this fraction is manually picked to remove some non-ferrous pieces that inadvertently passed
through. Both streams, the non-ferrous and the heavy non-metals, are sent to other facilities for
recycling the contained materials.
ASR constitutes the most important environmental problem for all shredding facilities [5]. European
legislation imposes exigent recycling targets for the next years, which is originating high pressure
over the recyclers. ASR has great energy potential since most part of its components is
combustible (plastics, elastomers, textiles, accounting 60-70% of fluff). The remaining materials are
essentially inorganic, namely glass, ceramics, electric wire and paints (Fig. 2). However, in spite of
depolluting operation, fluff residues still contain traces of several potentially hazardous substances
such as organic fluids and heavy metals, which inhibit valorising options. So, it is actually very
difficult to reduce the landfilled materials to values less than 20%.
A research is being carried out for the characterisation of ASR samples from a Portuguese
automotive shredder plant. The main objective is to characterise several fractions of this residue
and to identify the distribution of heavy metals in order to assess possible valorising options. The
initial results of this research are here reported.
EOL Tires, Batteries,

Vehicle Reception Depollution Fluids, Others
Magnetic Ferrous
Shredding Heavy Magnetic Picking fraction
Separation
fraction (RECYCLING)
Light
fraction Non To non-ferrous
magnetic and heavy non-metal
To ferrous fractions
Magnetic metal
Separation fraction
Non
metallic
Sieving Eddy-current Picking
Separation
ASR or autofluff
(DISPOSAL)
Metallic
Heavy non-metal
Non-ferrous metals fraction
(RECYCLING) (RECYCLING)
Fig. 1 Simplified diagram of the process of an automotive shredder plant.
EXPERIMENTAL
The initial ASR sample was kindly provided by a Portuguese auto-shredder company (Ecometais,
Seixal). The sample was manually homogenised and sorted using a Jones divisor into several
samples of about 1 kg. The particle size was assessed by sieving with a magnetic stirrer (Fritsch
Analysett 3) using standard sieves of several apertures, from 50 mm to 0.020 mm. Chemical
analysis of fine fractions was carried out by a Energy Dispersive X-ray Fluorescence (EDXRF)
spectrometer (TN Spectrace Quanx) with a rhodium source. The X-ray diffraction experiments was
performed by a diffractometer (Philips PW 1830), with a Cu K source using acquisition values of
40 kV and 30 mA and a scanning speed of 1(2)/min.
405
Ceramics; 4 Electric
materials; 3
Paints; 6
Textiles; 12 Others; 2
Glass; 15
Elastomers; 18 Plastics; 40
Fig. 2 Typical composition (wt%) of main materials of ASR.

After reception and sorting/homogenising, the particle size distribution of the ASR sample was
determined by sieving. The results obtained (Fig. 3), showed that this waste is essentially
composed of large fragments. Average particle size (d50) is 6.5 mm. More than 40% of weight has
dimensions higher than 11 mm. Visual analyses combined with microscope observation allowed to
conclude that this coarse fraction is very rich in plastics, rubber, foams and textiles, but is
contaminated by small particles and powder. The intermediate fraction, between 2-11 mm,
weighting about 30%, is composed by mixed materials. Below 2 mm, the ASR is essentially rich on
inorganic materials such as glass, ceramics and small metallic and plastic particles. A very fine
foam also appears in small particle size fractions.
It seems that a sieving operation can remove substantial part of inorganic materials, such as
hazardous metals, contained in the fines (20-30% from ASR weight), allowing to increase its
potential energy content. In order to identify the presence of metals in the ASR, several fractions of
different particle sizes (from 2 mm to 0.02 mm) were analysed by EDXRF technique, which allows
a qualitative and also semi-quantitative elemental determination according with the respective peak
areas. Note that the conditions used were optimised for transition metals and not allowed detection
of light elements such as Al and Si. An example of spectra obtained is presented in Fig. 4,
revealing the presence of several metallic elements. In all fractions analysed, substantial quantities
of iron were found, and some non-ferrous metals like copper, zinc and lead also appeared as
secondary elements. These can be present as metallic phases from steel, copper, and other alloys,
or even metal oxides. These elements are used in electric/electronic equipment. Barium is another
element clearly identified in all fractions analysed of ASR, probably coming from plastic
components or from electronic devices. Minor or trace elements found were tin, antimony,
molybdenum, strontium and cadmium.
These results prove that some metallic hazardous elements are present in the fine fractions of
ASR. However, the larger fragments also contain contamination of aggregated fine powders,
essentially the textiles which have high absorption characteristics, but its content is much lower
than in fines. In order to decrease the powders content in larger pieces and to allow its energy
valorisation, these contaminants shall be removed as well as possible. Two techniques are
proposed to allow aggregated particles to liberate from gross materials: (1) wet sieving or water
washing followed by sieving; (2) Mechanical treatment by grinding. Some preliminary tests using
these two alternatives were already carried out, showing that fine powders are disaggregated from
the gross ASR fraction, thus decreasing its contamination. Research shall proceed to optimize
these operations.
406
100
Cumulative w% finer 80
60
40
20
0
0.01 0.1 1 10
Particle size (mm)
Fig. 3 Particle size cumulative distribution curve of ASR sample (average of 7 trials).
3000
Fe
2500
Ba
2000
Intensity (a.u.)
1500
Pb
1000 Zn Pb Ba
Fe Sn
Sn
Ca Pb
500 Sb
Cu Zn Sr Pb Mo
Cd
0
3 8 13 18 23 28 33 38
Energy (keV)
Fig. 4 EDXRF spectra of ASR fractions (particle size 1-2 mm).
The analysis of the particles by X-ray diffraction allowed identifying the main crystalline phases
present in the residue (Fig. 5). All the samples analysed contained SiO2 (quartz) and CaCO3
(calcite), most of them also contained TiO2 (rutile) and some of them Fe3O4 (magnetite). Glass
which is a major component of fine materials, is not detectable by this technique because is
amorphous. The same applies to plastic particles. Phases containing heavy metals (like Cu, Zn,
Pb, Sn) were not detected by XRD probably due to their low content.
407
Intensity (a.u.)
Fig. 5 X-ray diffractogram of ASR sample with particle size range 0.1-0.2 mm (Cu K source).
CONCLUSION
The characterisation of an ASR sample from an auto shredder facility was carried out aiming at
identifying the presence of heavy metals in several parts of this waste which are harmful
concerning its possible energy valorisation. ASR contains large fragments of organic materials with
energy value such as plastics, elastomers and textiles, but also fine particles essentially composed
of inorganic materials like glass, ceramics and metals. Several heavy metals were identified in fines
and powder, including Fe, Cu, Zn, Pb, Sn, among others, mainly in fractions bellow 2 mm, but large
fragments also contained these aggregated particles. In order to reduce contamination of ASR,
these fine particles must be removed by sieving, mechanical treatment or washing methods.
References
[1] G. Davies, Materials for Automotive Bodies, Elsevier, NY, 2003.

[2] P. Ferro, P. Nazareth, J. Amaral, Strategies for meeting EU end of life vehicles reuse/
recovery targets, J. Industrial Ecology 10 (2006) 77-93.
[3] A. Gesing, Assuring the continued recycling of light metals in end-of-life vehicles: a global
perspective, JOM 56 (2004) 18-27.
[4] M. Nourreddine, Recycling of auto shredder residue, J. Hazardous Materials 139 (2007) 481-
490.
[5] D. Mirabile, Thermal valorization of automobile shredder residue: injection in blast furnace,
Waste Management 22 (2002) 841-851
408
REUSE OF THE ORNAMENTAL ROCKS WASTE AS CORRECTIVE OF SOIL

ACIDITY
1 2 3 4 5
G.C. Ferres , A.T. Matos , V. Eustquio Jnior , J.C.M. Baptestini , P.A.V. Lo Monaco , I.
6 7
C.A. Ribeiro and S.A.A. Baker
1 MSc Student in Agricultural Engineering at Federal University of Viosa, Viosa, Minas
Gerais, Brazil. gheilacf@yahoo.com.br
2Professor at Agricultural Engineering Department, Federal University of Viosa, Viosa,
Minas Gerais, Brazil. atmatos@ufv.br
3 DS Student in Agricultural Engineering at Federal University of Viosa, Viosa, Minas
Gerais, Brazil. vejunior@yahoo.com.br
4 DS student in Agriculture Engineering at Federal University of Viosa, Viosa, Minas
Gerais, Brazil. jcbaptestini@yahoo.com.br
6 Undergraduate student in Agricultural and Environmental Engineering at Federal
University of Viosa, Viosa, Minas Gerais, Brazil. ivan.ribeiro@ufv.br
7 Undergraduate student in Agricultural and Environmental Engineering at Federal
University of Viosa, Viosa, Minas Gerais, Brazil. sandy.baker@ufv.br
ABSTRACT
During the processing of ornamental rocks (granite and marble), the stones blocks are
divided into plates, realized on multilaminar or mechanical looms, using a mixture of
water, lime and grit iron to optimize the cutting and to cool down the blades. Due to the
large amount of residue that is generated during the processing of ornamental rocks, it
becomes necessary a treatment and/or a better use, always considering the necessity of
a harmonic disposal in the environment. Thus, the objective of this study was to evaluate
the potentiality of the granite processing waste as a corrective of soil acidity. The study
was conducted at the Laboratory of Soils and Solid Waste of the Agricultural Engineering
Department in the Federal University of Viosa. The soil samples were taken from A and
B horizon of a Clayey Oxisol Red Yellow , located in the city of Viosa, Minas Gerais. The
residue of rocks presented a relative power of total neutralization equivalent to 5.11% of
CaCO3. Relatively high doses of granite dust provided small increase in the value of pH
of the soil. The recommended dose for pH correction of the soil, of the A and B horizon of
-1 -1
a Oxisol Red Yellow, were 30.5 t ha and 96.7 t ha , respectively.
keywords: ornamental rocks, solid residue, soil acidity
INTRODUCTION
During the processing of ornamental rocks (granite and marble), the stones blocks are divided into plates,
realized on multilaminar or mechanical looms, using a mixture of water, lime and grit iron to optimize the
cutting and to cool down the blades. According to [6], this process generates a residue like an abrasive
mud, which in most of the cases, is discarded on flocculation tanks or in courtyards around the production
facilities, from where is transported to industrial warehouses. According to [3], each loom, working at full
-1
capacity, can generate up to 5 t dia of residue.
Due to the large amount of waste that is generated during the processing of ornamental rocks, it becomes
necessary a treatment or a better use, always considering the necessity of a harmonic disposal in the
environment.
409
Several studies have been conducted in order to use the residue from the processing of ornamental
rocks, and may be cited those that proposes the ceramic production ([7], [11], [5]), the production of
cosmetics [8] and the use as alternative fertilizers ([3], [12]).
In the case of agricultural use, some industrial residues can be used to replace lime, due to the high
availability in which they are discarded in the environment, considering the possibility of providing the
correction of soil acidity [1], since most brazilian soils are acidic and poor in nutrients. Soil acidity is
usually associated with high levels of Al, and Ca and Mg deficiency, affecting the development of plants,
with reduction of the productivity [10]. A simple practice to correct these problems is the liming, usually
done with limestone [2].
The use of rock dust in agriculture has been much discussed, although little studied, needing more
research for greater scientific base. Due to the high amount of macronutrients, especially calcium [3]
present in these residues, opens up the possibility of using as a corrective of soil acidity. Thus, the
objective of this study was to evaluate the potentiality of the granite processing waste as a corrective of
soil acidity, obtaining a curve of pH neutralization, as well as the recommended doses of this residue, for
horizons A and B of an Oxisol Red Yellow.
METHODOLOGY
The study was conducted at the Laboratory of Soils and Solid Waste of the Department of Agricultural
Engineering at Federal University of Viosa. The granite powder sample was provided by Environmental
Association Mount Lebanon (AAMOL), located in the Municipality of Cachoeiro de Itapemirim, Esprito
Santo, Brazil. Soil samples were taken from A and B horizon of a Oxisol Red Yellow (ORY), clayey
texture, located in the city of Viosa, Minas Gerais, Brazil, situated at Latitude of 20 45' 37'' S and
longitude of 42 52' 33'' W.
The waste rock was oven-dried, under a temperature of 65 C for 24 h, then submitted to a temperature
of 105 C for 12 h and cooled to room temperature. After this stage, it was crumbled in a mortar to get a
fine powder used in the experiments. The relative efficiency (RE) and the neutralizing power (NP) of the
material (fine powder), were then determined, obtaining values of 90.7% and 5.68% of CaCO3,
respectively. Thus, it was possible to calculate the Relative Power of Total Neutralization (RPTN),
-1
obtaining 5.11% of CaCO3. The pH of the material, in CaCl2 solution of 0,1 mol L , was of 8.63.
According to [1], the main physical and chemical characteristics of A and B horizons of the ORY used in
-1
this experiment are, respectively, clay content of 63.0 and 72.0 dag kg ; pH in water of 5,5 and 5.0;
-1
organic matter content of 5.71 and 3.02 dag kg and effective cation exchange capacity (CECe) of 2.32
-1 -1
and 0.94 cmolc kg . The rock waste was studied in six doses: 0, 20, 40, 80, 160 and 320 t ha . For this,
the fine powder was mixed in samples of 500 g from the A and B horizons of an ORY, inside plastic bags,
totalizing twelve experimental units. The mixtures of powder and soil remained under moisture conditions
equivalent to water content at field capacity, incubated for a period of two weeks, time required for
reaction of the soil with the acidity corrective and to reach equilibrium. At the end of this period, the
material of the plastic bags was passed through a 2 mm sieve for determination of pH in water, at the
-1
proportion of 1:2.5, using a bench pH meter. To determine the delta pH (pH), a solution of KCl 1 mol L
was used (Table 1).
Table 1. Values of Delta pH for horizons A and B
Horizon pH in KCl pH in water pH*

A 6,05 6,09 -0,04
B 4,51 5,30 -0,79
*pH= pHKCl - pHH2O
For the confection of incubation graphs, the data were submitted to regression analysis, by means of
mathematical equations relating the pH values in water as a function of the applied dose of powdered
granite, adjustment resulting in the coefficient of determination greater than 70% was considered
satisfactory.
410
In figure 1, the incubation curves of soil with the granite dust are shown, in pH in water, for horizons A
and B.
(a) (b)
Figure 1. The pH in water as a function of the applied dose of granite dust on soil samples of A and B
horizons of the ORY.
Observing the graphs in Figure 1a and 1b, it may be noted that the granite dust resulted in an increase in
soil pH, due to the alkaline reaction provided by this material. The increase of pH in soil provides
innumerous benefits, such as reduction in the toxic effects of most heavy metals, and due to the high
amount of Ca present in this waste [3], the supply of this macronutrient, in addition to increasing the
availability of other nutrients such as N, P, K, S and Mo. Considering the correction of the pH up to 6.5, it
-1 -1
would be necessary to apply a dose of 30.5 t ha in the A horizon and 96.7 t ha in B horizon [1], working
-1
with vngole powder shell, and [9], studying limed sludge, obtained much smaller doses (2.92 t ha and
-1
9.4 t ha , respectively) for pH correction, of the same soils, up to 6.5. However, it should be emphasized
that they had much higher RPTN. [3], studying the agronomic feasibility of granite dust on coffee fields
grown in Oxisol Red Yellow cohesive, obtained values of pH equal to 5.0 or very close to this, when
-1
applied doses of 17.8; 18.2 and 23 t ha of this residue. The same authors concluded that the application
of increasing doses of granite processing waste increased the pH linearly, but in small magnitude,
demonstrating the low efficiency of the residue to correct soil pH. [12] related the low efficiency of granite
dust, as a corrective, to the low carbonate content existing in the mud coming from granite cutting, which
can be verified by the small value of NP found in the material under study (5.68% CaCO3). Additionally, in
soils with high organic matter and clay, because these factors are directly related to the buffer capacity of
the soil, it is expected that pH alterations will have even lower magnitude [10].
According to the values of delta pH of the material (Table 1), measured in the natural condition of the soil,
it appears that the soil materials of both ORY horizons studied are electronegative. Organic matter is
frequently the major source of negative charges in tropical soils [10], in this case, in the horizon A.
The results indicate that the granite pdust is a low efficiency residue for soil acidity correction, since it is
necessary to apply large doses in order to obtain small increases in soil pH. In the soil material of horizon
-1
A, a dose of 30.3 t ha of the residue provided an increase of 0.41 in pH.
CONCLUSIONS
- Relatively high doses of granite dust provided a small increase in the value of pH of the soil;
- The recommended dose for pH correction of the material of horizon A of a Oxisol Red Yellow is 30,5 t
-1 -1
ha , whereas for the correction of the horizon B is 96.7 t ha .
411
REFERENCES
[1] P.A.V. Lo Monaco, A.T. Matos, I.C.A. Ribeiro, D.L. Teixeira, R.P. Lopes, Utilizao de conchas
modas de vngole (Anomalocardia brasiliana) como corretivo da acidez do solo, in: Congresso
Interamericano de Ingeniera Sanitaria y Ambiental, 32, 2010. Punta Cana/Repblica Dominicana.
Anais... AIDIS, 2010. CD Rom.
[2] A.S. Lopes, M.C. Silva, L.R.G. Guilherme, Acidez do solo e calagem. Boletim Tcnico, 1. ANDA
Associao Nacional para Difuso de Adubos, So Paulo, 1991. Disponvel em:
http://www.anda.org.br.
[3] A.G. Martins, e C.J. Fanton, Resduo de beneficiamento do granito como fertilizante alternativo na
cultura do caf, Cincia Agronmica. 42 (2011) 16-26.
[4] A.T. Matos, Prticas de tratamento e aproveitamento agrcola de resduos slidos. Caderno Didtico
45. Associao dos Engenheiros Agrcolas de Minas Gerais, DEA/UFV, 2008.
[5] R.R. Menezes, H.S. Ferreira, G.A. Neves, Uso de rejeitos de granitos como matrias-primas
cermicas, Cermica. 48 (2002) 92-101.
[6] I.V.M. Moraes, Mrmore e granito: lavra, beneficiamento e tratamento de resduos. Dossi tcnico
da Rede de Tecnologia do Rio de Janeiro, 2006. Disponvel em: http://www.sbrt.ibict.br.
[7] J.M.S. Moreira, J.P.V.T. Manhaes, J.N.F. Holanda, Reaproveitamento de resduo de rocha
ornamental proveniente do Noroeste Fluminense em cermica vermelha, Cermica. 51 (2005) 180-
186.
[8] C.N. Oliveira, J.P.C. Queirz, R.C.C. Ribeiro, Aplicao de resduos oriundos do corte de rochas
ornamentais na produo de cosmticos, in: XVII Jornada de Iniciao Cientfica Centro de
Tecnologia Mineral (CETEM), 2009. Disponvel em: http://www.cetem.gov.br/publicacao.
[9] N.C.L. Silva, F.A.R. Luiz, C.A. Montebeller, N.S. Machado,A.T. Matos, Utilizao de lodo de esgoto
domstico caleado como corretivo de solo. In: Simpsio Mineiro de Engenharia Ambiental, 2, 2006.
Viosa/MG. Anais... UFV, 2006. CD Rom.
[10] D.M.G. Sousa, L.N. Miranda, S.A. Oliveira, Acidez do solo e sua correo, in: R.F. Novais, V.H.
Alvarez, N.F. Barros, R.L.F. Fontes, R.B. CantaruttI, J.C.L. Neves (Eds.), Fertilidade do solo, Viosa:
Sociedade Brasileira de Cincia de Solo, 2007, pp. 205-274.
[11] M.L.S. Souza Filho, A utilizao de co-produtos da siderurgia e da indstria de beneficiamento de
rochas ornamentais na produo de tijolos prensados. Vitria: Universidade Federal do Espirto
Santo, (Dissertao de Mestrado), 2005.
[12] A.C.F. Vasconcelos, L.H.G. Chaves, J.G. Luna, Uso agrcola da lama de serragem de blocos de
granito: efeito na fertilidade do solo, Agropecuria Tcnica, 24 (2003) 23-30.
412
ALTERNATIVE RAW MATERIAL USAGE IN THE CLAY CERAMIC INDUSTRY
Coronado, M. 1, Martn-Torre, M.C.1, Alonso-Santurde, R.1, Coz, A.1, Galn, B1., Andrs,
A. 1
1 Department of Chemical Engineering and Inorganic Chemistry. University of Cantabria,
Santander, Spain. coronadoml@unican.es
ABSTRACT
The global environmental impact of industrial production has increasing due to the
scarcity of raw materials and the large amount of waste generated. Considerable efforts
are being made to move towards a sustainable economy which uses finite and renewable
resources efficiently. Ecoinnovation promotes integrated initiatives such as closed-loop
production; this is the incorporation of waste flows on industrial processes as substitutes
of raw materials. In this sense, the clay-based ceramic industry is considered a proper
alternative for solid waste incorporation due to the immobilization in the ceramic matrix of
some potentially toxic metals contained in the waste after the firing process. This work
presents an updated review of available literature on the potential incorporation of
different solid wastes in ceramics. The industrial wastes were classified according to the
European Waste List (EWC) and the role played by the waste in the ceramic has been
also studied. The mechanical and environmental properties of the alternative ceramics
containing wastes must be taken into account in order to fulfill the European quality
standards. According to this review numerous kinds of wastes have being successfully
incorporated into clayey ceramics. Furthermore, in some cases, this incorporation has
proved to be technological acceptable and environmentally friendly.
Keywords: Eco-innovation, clayey ceramic, alternative raw materials, waste recycling, by-products
INTRODUCTION
Europe uses natural resources more rapidly than the natural system can replace them with, which
has caused their scarcity. Because of this, the European dependence on natural resources
imported from abroad is increasing. This dependence causes problems over the security of raw
materials supply. On the other hand, the extraction and processing of raw materials can involve
significant environmental effects in the exporting countries, what is creating an ecological
unbalance which could collapse unless action is taken to prevent this from happening. This
problem has acquired particular importance and this is why to move to a sustainable economy
which uses finite and renewable resources efficiently and responsibly and recycles strategically
important materials [1].
Eco-innovation which is the innovation that reduces the use of natural resources and decreases the
release of harmful substances across the whole life-cycle helps to enable this evolution through a
combination of technological and non-technological changes that can yield substantial
environmental improvements. The methods for introducing technological changes such as cleaner
production, pollutant control and eco-efficiency are focused on products and processes
modification or redesign, while non technological changes are based on life cycle analysis, closed
loop cycles and industrial ecology which implies modification or redesign of organisations and
institutions [2]. Industrial ecology conceptualizes industry as a man-made ecosystem that operates
in a similar way to natural ecosystems, where the waste or by product of one process is used as an
413
input into another process. Industrial ecology interacts with natural ecosystems and attempts to
move from a linear to cyclical or closed loop system.This work presents an updated review of
available literature over the last decade on the incorporation of different solid wastes or by-products
from other industrial processes as alternative raw material in the red clay ceramic industry. There
are a wide variety of solid wastes susceptible of become by-products. Consequently, the basis for
the overview was a classification of the wastes into twenty categories according to its origin based
on the European Waste Catalogue (EWC) [3]. The EWC is a hierarchical list of waste descriptions
established by Commission Decision 2000/532/EC which classifies waste materials and
categorizes them according to what they are and how they were produced. On the other hand, this
work proposes another more general classification based not only on the specific nature and origin
of the waste but also on the different role that the alternative raw materials can play in the brick
making process [5]. This work classifies the wastes into six categories associated with the
behaviour of the waste in the ceramic process and the main effects caused to the ceramic: (a)
fluxing agents, (b) fillers, (c) clay substitutes, (d) body fuels (e) pore formers and (f) property
affecting
METHODOLOGY
The methodology applied in this work in order to perform a rigorous literature review is based on
the guide developed by Randolph, J.J (2009) [4]. This guide summarizes different methodologies
for conducting a literature review. The methodology described in figure 1 has been applied for the
study case of the incorporation of industrial wastes or by-products into red clay ceramics. Figure 1
details the different steps in which this methodology is divided into.
Problem Data Literature Analysis Results presentation

Formulation Collection Matrix & Evaluation &Conclusions
Fig.1. The research stages in conducting a literature review, Randolph, J.J (2009) [7]
The problem under study in this literature review is the feasibility of the incorporation of industrial
waste or by-products in to red clayey ceramics (glazed ceramic, concrete and porcelain are
excluded from this review). The method of data collection was an electronic search of the academic
database Scopus. The explicit criteria to dictate the inclusion, or exclusion of the articles in the
review were (a) studies published in scientific journals with impact factor, (b) published between the
years 2000 and 2011 and (c) the keywords established were the following: alternative raw
materials/clay/ceramics/bricks/tiles/roofing tiles/ waste/by-products/clayey/recycling/ construction/
building/ reuse/ incorporation. A literature matrix which summarizes the most relevant information
taking into account all the articles which met the inclusion criteria established was created. The
literature matrix lists the authors and years of publication of the selected articles founded along the
Y-axis and along the X-axis the matrix lists the variables or categories considered in the study,
which were the followings (a) Kind of waste according to the EWC [3], (b) and the role played in the
ceramic matrix. Then, the analysis and interpretation of the information included in the literature
matrix is performed by studding what studies share in common and where studies differ. Finally,
the results are presented through different graphics.
RESULTS
In this work almost 130 papers have been included in order to study the state of the art of the
introduction of industrial solid wastes in to red clayey ceramics. The results of this review show that
several industrial wastes have being studied and successfully incorporated during the last decade
(years 2000 to 2011) as alternative raw materials with the aim of obtaining products useful for
different applications such as bricks, tiles or roofing tiles following the usual stages of the ceramic
processes. Figures 1 and 2 show two different classifications of the wastes included in the ceramic
industry. Figure 1 classifies the wastes according to the EWC [3] into twenty different codes from
code 01 to code 20. While figure 2 classifies the wastes based on the possible roles played in the
ceramic matrix with the aim of understanding its contribution to the industrial process.
414
Paper
130
130
120
120
120
110
110
110
100
100
100
90
9090
80
8080
70
7070
Paper N
60
6060
50
5050
40
4040
30
3030
20
2020
10
1010
00 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
11 22 3
3 4
4 55 66 7
7 88 9
9 10
10 11
11 12
12 13
13 14
14 15
15 16
16 17
17 18
18 19
19 20
20
EWC Code
EW C Code
1. Quijorna (2011) 23. Adylov (2010) 45. Menezes (2009) 67. El- Mahllawy (2008) 89. Monteiro (2006) 111. Toya (2004)
2. Dinh Hieu (2011a) 24. La Rubia-G. (2010) 46. Abreu (2009) 68. Monteiro, (2008b) 90. Lin long Kae (2006b) 112. Oliveira (2004)
3. Dinh Hieu (2011a) 25. Suklas (2010) 47. Acchar (2009) 69. Lafhaj (2008) 91. Baruzzo (2006) 113. Magalhes (2004)
4. Alonso-S. (2011) 26. Abdul-Kadir (2010b) 48. Loryuenyong (2009) 70. Moreira (2008) 92. Blasubramanian (2006) 114. Weng (2003)
5. Gosh (2011) 27. Furlani (2010) 49. Maschio (2009) 71. Little (2008) 93. Kavas (2006) 115 Cusid (2003)
6. Junkes (2011) 28. Tayibi (2010) 50. Shin, Dae-Y (2009) 72. Menezes (2008) 94. Acchar (2006) 116. Soza (2003)
7. Eliche-Q. (2011) 29.Ozkan (2010) 51. Pontikes (2009) 73. Sikalidis (2007) 95. Kurama (2006) 117. Demir (2003)
8. Fernandez-P (2011) 30. Romero, M. (2009) 52. Cultrone (2009) 74. Singh (2007) 96. Valanciene (2006) 118. Anderson (2002)
9. Karamanova (2011) 31. Dhanapandian (2009) 53. Torres, P. (2009) 75. Abali (2007) 97. Jonker (2005) 119. Basegio (2002)
10. Chee-Ming (2011) 32. De la Casa (2009) 54. Susan, R. (2009) 76. Monteiro (2007) 98. Jordan (2005) 120. Acosta (2002)
11. Freda-C. (2011) 33. Samara (2009) 55. Quaranta (2009) 77. Pappu (2007) 99. Blanco-Garca (2005) 121. Hammer (2002)
12. Haiying (2011) 34. Montero (2009a) 56. Romero, M. (2008) 78. Saboya (2007) 100. Olgun (2005) 122. Kute (2002)
13. Quaranta (2011) 35. Dondi (2009) 57. Monteiro (2008a) 79. Ibanga (2007) 101. Monteiro (2005) 123. Ramadan (2001)
14. Malaiskiene (2011) 36. Garca-U. (2009) 58. Mekki (2008) 80. Kurama (2007) 102. Magalhaes (2005) 124. Karius (2001)
15. Alonso-S. (2010). 37. Montero (2009b) 59. Demir (2008) 81. Merino (2007) 103. Ducman (2005) 125. Couto (2001)
16. Siddique (2010) 38. Carter (2009) 60. Bragana (2008) 82. Vieira (2007) 104. Menezes (2005) 126. Lind, D.F (2001)
17. Baspinar-S. (2010a) 39. Mahzuz (2009) 61. Teixera (2008) 83. Chidiac (2007) 105. Segadaes (2005) 127. Das (2000)
18. Baspinar-S. (2010b) 40. Christogerou (2009) 62. Xu, G:R.(2008) 84. Raupp-Pereira (2007) 106. Demir (2005) 128. Mishigaki (2000)
19. Dondi (2010) 41. Al-Zboon (2009) 63. Chiang, K.Y. (2008) 85. Torres, P. (2007) 107. Vieira (2004a) 129. Martelon (2000)
20. Prez- V (2010) 42. Pinheiro (2009) 64. Algin (2008) 86. Campos L.F.A (2007) 108. Monteiro (2004)
21. Abdul-Kadir (2010a) 43. Suctu (2009) 65. Chindaprasirt (2008) 87. Demir (2006) 109. Uslu (2004)
22. Asokan (2010) 44. Chiang (2009) 66. Erol (2008) 88. Lin long Kae (2006a) 110. Vieira (2004b)
Fig. 1: Industrial wastes classification according to the European Waste Catalogue (EWC) [3]
415
Fig. 2: Industrial wastes classification according to the role played in the ceramic matrix
According to figure 1 which presents a classification of the wastes based on the EWC [3], the
studies analyzed in this review does not use the entire codes of wastes in which the EWC divides
the wastes in the production of ceramics. For instance, in this review none of the papers include
wastes from coatings, adhesives, sealants and printing inks (EWC 8), wastes from the
photographic industry (EWC 9), wastes from the treatment of metals and plastics (EWC 12), oil
wastes and wastes of liquid fuels (EWC 13), as well as waste from organic solvents, refrigerants
and propellants (EWC 14). On the other hand based on figure 1 it can be concluded that fifty
percent of the studied papers introduce residues classified under EWC code 01 that are wastes
resulting from exploration, mining, quarrying, physical and chemical treatment of minerals, EWC
code 10 that are wastes from thermal processes and EWC code 19 that are wastes from waste
416
management facilities, off-site waste water treatment plants and the preparation of water intended
for human consumption and water for industrial use. It is important to remark that that according to
this review, until year 2004 wastes from thermal processes (EWC 10) were not widely investigated
for its recycling in the ceramic bodies, being during year 2007 when the most papers about
introducing of thermal wastes were published.
According to figure 2 the most common wastes introduced into ceramic bodies within EWC 01 were
wastes from mineral extraction and processing of non metalliferreous minerals, while the most
common wastes identified with EWC 10 were coal combustin by-products and residues from the
metallurgical industry. Finally, wastes from municipal waste incinerator and urban sewage sludge
were the most common alternative raw materials used in red clay ceramics within the EWC code
19. On the other hand, figure 2 shows seven different roles (A= fillers, B= fluxing agents, C= clay
substitutes, D= body fuels, E= pore formers, F= property affecting wastes) that the waste could
play in the ceramic matrix during the firing process. A single alternative material can play different
roles in the firing step. For instance, fly ash can comprise a fluxing agent, a body fuel, a clay
substitute or a body fuel. This is because the composition of the specific waste affects their
behaviour. Fly ash with high content of carbonaceous matter may act as a body fuel, fly ash may
contain alkaline compounds that form liquid phases at relative low temperatures contributing to the
sintering consolidation acting as a fluxing agents, while fly ash with low carbon content and
negligible content of alkaline compounds may act as clay substitute or as a filler when these ashes
are predominantly composed by quartz [6].
The role A of fluxing agents are composed by materials with a relatively high amount of alkaline
oxides, mainly KO2 and Na2O, which in reaction with silica and alumina promote liquid phase
formation that facilitates densification. Among the wastes included in this category are the sludge
wastes from ornamental rocks (i.e granite is considered a flux material due to its large amount of
alkaline oxides. These oxides derive from feldspars and micaceous minerals that are common
constituents of granite rock), glassy residues, fluxing ashes which may contains substances that
form liquid phases at relative lower firing temperatures and thus contribute to the sintering
consolidation of the ceramic structure, boron-containing residues [6], waelz slag and steel slag,
bone ash, IGCC (ash from the gasification of coal) and Mn-Fe solid waste. The role B of fillers
includes wastes which can partially substitute the effect caused by the sand in the vitrification
process; this means the dissolution of the inorganic waste material in the glassy phase which
occurs during the sintering of clay or reacts with clay minerals to form new mineral phases in the
fired clay structure. Among the wastes included in this category is possible to find incinerated
sewage sludge ash (ISSA), steel dust, sludge from water treatment plant (sewage sludge), steel
refining sludge, non-fluxing ashes, spent catalyst rejects, and foundry sand. The role C of clay
substitutes are composed by with certain amount of clay minerals that confer the plastic behaviour
to the ceramic matrix. Among the wastes included in this category could be municipal solid waste
incinerator slag, grog, fly ash and water treatment residues. The role D of body fuel agents
contains wastes including combustible carbon containing matter, which has a relative heat power,
and therefore they are desirable for save energy. Among the wastes included in this category are
oily residues, blast furnace sludge residue which still has a significant amount of coke, sludge from
paper industry, non-fluxing ashes with high carbon content, sewage sludge and saw dust. The role
E includes wastes that usually possess high content of organic matter which burn out to form
pores. It is important to observe that the inclusion of alternative materials in the ceramic process
normally change the properties of the fired product. All the wastes affect the final properties of the
final products with substances that modify the ceramic behavior and cannot be included in the
previous role categories. Therefore, an additional role (F) of property affecting wastes has been
included which contains all the already mentioned wastes and the rest of the summarized wastes.
According to figure 2 the most common role played by wastes in the ceramic matrix is role E of
pore formers. Porosity is a desirable property to obtain acoustic and thermal insulating products.
Fluxing agents and body fuels are the second role usually played by the waste in ceramics, due to
the energy savings that reports their introduction into the ceramic matrix and thus the economic
profits that can entail.The carbonaceous and fluxing properties of this wastes used in substitution of
417
traditional raw materials can reduce the firing temperature of the bricks considerably resulting in a
much lower heat requirement than the traditional process.
CONCLUSIONS
The main conclusions of this updated review whose aim is to classify the wastes that are able to be
incorporated into a ceramic matrix are the following:
- A wide variety of wastes are being successfully included into ceramic materials. This work
analyses and classifies the waste used among the last decade in red clay ceramics based on two
different criteria. On the one hand, its classification according to the EWC [3] to know the activities
which generate the waste flows to will be able in the future to establish feasible alternatives to
close the production cycles promoting the zero waste generation. On the other side, the
classification of the waste based on their behaviour in the ceramic matrix (fluxing agent, filler, clay
substitute, body fuel, pore former and property affecting wastes) aiming in the future to establish a
relationship between the introduction of the waste and the advantages or disadvantages caused by
its incorporation in the traditional process. Possible advantages could be the decrease in energy
cost during the firing step or the decrease in the needs of water in the moulding step due to the
high humidity of the alternative material, while among the disadvantages could be mentioned
certain constraints in the quantity of waste that can replace the original raw materials in order to
fulfil the European standards of quality for the ceramic products.
- The most frequently wastes included into the ceramic were wastes from exploration, mining,
quarrying, and physical and chemical treatment of minerals from EWC code 01, wastes from
municipal waste incinerator and urban sewage sludge that belong to EWC code 19 and coal
combustion by-products and residues from the metallurgical industry within the EWC code10, being
the last wastes more extensively studied since year 2004. On the other side it can be concluded
that the wastes used in ceramic bodies during the period under study affects on major scale to the
porosity of the final products which improves the insulation properties of the brick, as well as the
energy balance of the ceramic process.
- In this work almost 130 papers have been included in order to study the state of the art of the
introduction of industrial solid wastes in to red clayey ceramics. Unfortunately, the reference list can
not contain the entire references due to the limited space. Therefore, only some references have
been included.
ACKNOWLEDGES
The authors gratefully acknowledge financial support for this research under the framework of the
Spanish Education and Science Ministry, Project CTM 2009-11303. M, Coronado was funded by
the Spanish Ministry of Education and Science on an F.P.I. fellowship.
References
[1] European Commission. Towards a Resource Efficient Economy. 10th European Forum on
Ecoinnovation Towards a Resource Efficient Economy From Policy to Action (2011).
Information on http://ec.europa.eu/environment/ecoinnovation2011/1st_forum/ index_en.html
[2] Eco-innovation Observatory. The eco-innovation Challenge. Annual report 2010. Information
on http://www.eco-innovation.eu
[3] Environmental protection agency. The European Waste Catalogue (EWC) (2002). Information
on http://www.epa.ie
[4] Randolph, J.J, Disertation literature review. Practical Assessment Research & Evaluation Vol
14, N 13 (2009). ISSN 1531-7714.
[5] Petavratzi, E. and Barton, J. Characterization of mineral wastes, resources and processing
technologies. Heavy ceramic (brick). School of civil engineering. University of Leeds (2007)
[6] Vieira, CMF. And Monteiro, S.N. Incorporation of solid wastes in red ceramics- an updated
review. Revista materia v. 14, n.3 (2009) 881-905
418
REF 187
BIOENERGY POTENTIAL OF FOREST RESIDUES IN BIZKAIA (SPAIN)
1a 2 3 4 2 2
E. Mateos , J.M. Edeso , J. Gonzlez , J. Eguzkitza , A. Bastarrica and L. Torre
1 Dept Chemical and Environmental Engineering, University of the Basque Country, Spain
2 Dept Mining and Metallurgical Engineering and Materials Science, Basque Country, Spain
3 Dept English and German Philology, University of the Basque Country, Spain
4 Dept Applied Mathematics, University of the Basque Country, Spain
a
e-mail: esperanza.mateos@ehu.es
ABSTRACT
11
Vegetal residues constitute the most abundant biomass of our planet. Some 10
metric tons are produced annually in the biosphere with an energy content of more
18
than 2,42510 kJ. The methods for utilizing biomass residues have always been of
great interest, but this interest has recently grown in Europe and the USA due to the
potential value of forest residues as a source of useful energy. The aim of this
research work is the development of a methodology to quantify and yield cartography
of the prospective energy production of residual biomass from the most representative
forest species of Bizkaia (Spain), using a Geographic Information System (GIS)
computer tool. A model of indirect estimation has been used in order to estimate the
evolution of forest masses throughout in any area of Bizkaia. The availability of such
major biomass potential for energy production is strongly conditioned to the inherent
difficulties during the extraction process. After analyzing statistically the results
obtained, 52,214 metric tons of residual forest biomass per year are estimated. This
means a potential energy supply of 32,011 toe per year. The estimation of biomass
quantities that may generate forest activity will allow us to accomplish its planned
exploitation, taking into account both economic and environmental aspects, with the
aim of determining which the optimum location for setting up an energy production
plant is.
Keywords: GIS, forest residues, bioenergy potential, resources map
INTRODUCTION
Vegetal biomass, residual or not, has constituted a traditional resource of fuel for mankind.
Even nowadays, more than 1,500 million people depend upon these residues to meet their
energy needs. With the massive use of fossil fuels, the energy development of biomass started
diminishing steadily. However, during the last few years energy panorama has varied
remarkably worldwide. There is an increase of public awareness as a result of the serious
environmental and energy problems derived from excessive energy consumption in
industrialized countries. The traditional energy model based upon massive use of fossil fuels is
clearly unsustainable, both from the environmental point of view and from the viewpoint of
running out this resource. As a consequence, it is absolutely necessary to establish a new
energy model based upon sources diversification, rationalization and efficiency in consumption,
and respect for the environment. The overall energy potential of biomass the biosphere would
be able to generate annually is estimated at 68,080 Gtoe. This represents an enormous
biomass production potential worldwide [1]. In Spain, the energy potential of residual biomass is
about 26 Mtoe/year. In the Autonomous Community of the Basque Country, biomass is
currently the most widely used source of renewable energy. As an example, the contribution of
renewable energies to the final consumption of energy in the Basque Country was 6.8%. From
this amount, 85% was biomass [2].
Forest residues have low potentially-fermentative sugar contents in the form of high molecular
weight polymers. The characteristics and composition of these vegetable residues let us obtain
several products, provided that adequate separating techniques are used, such as ethanol,
sugars..., with different applications, as it is shown in figure 1.
419
Fig. 1 Obtaining different products from lignocellulosic residues
These last years, a growing interest in the study of biochemical processes has arisen, mainly
those that lead us to the obtaining of ethanol [3]. With the massive use of fossil fuels, the energy
development of biomass started diminishing steadily. However, during the last years, energy
panorama has varied remarkably worldwide. The use of biomass as a source of energy is a
possible alternative for mineral oil and, moreover, it could decrease environmental pollution.
Forest biomass is a substantial renewable resource that can be used as a fuel to generate
electric power and useful thermal output [4]. In this research work, the biomass resources
considered have been those produced in the forestry sector as a consequence of field
operations. Forest field byproducts are considered to be those vegetal materials produced in
forests which have experienced, up to the present date, little or null commercial demand.
The area studied is the province of Bizkaia (Spain). It is located in the north of Spain at latitude
2
4316N and longitude 256W. It extends over 2,217 km , and it is an abrupt and mountainous
province, crossed by deep valleys that descend quickly towards the sea from the near
mountains close to the also abrupt and cliffy coast. Due to the materials that appear in the area,
most of the surface in this district is made up of Mesozoic terrain with predominance of the
Lower Cretaceous (Aptian). The lands of Bizkaia form a very rugged set in which erosion has
produced an important dissection of the land (Fig. 2).
Fig. 2 Bizkaias landscape

2
The forest surface of Bizkaia amounts to 1,590 km -72% of its overall surface-, from which
2
1,306 km are estimated as wooded area. The annual forest growth in this region is estimated at
3
1,176,347 m . As a result, Bizkaia is the epicenter of forest activity in the Autonomous
Community of the Basque Country. Forestry activities generate significant quantities of wastes
and by-products that are suitable for diverse energy purposes.
For carrying out this project, it was decided to select those species that fulfil a double criterion:
high presence in the area of study, according to data obtained from the IFN-3 (Tercer Inventario
Forestal Nacional), and high potential for exploitable residue generation from the viewpoint of
energy.
The most widespread vegetable species present in Bizkaia are Pinus radiata (50%) (Fig. 3),
followed by Eucalyptus globules (10%) (Fig. 4), and Quercus robur (8%).
420
Fig. 3 Pinus radiata plot map in Bizkaia Fig. 4 Eucalyptus globulus plot map in Bizkaia
Scrub surfaces have not been considered in this study, since the surface they occupy in the
territory is rather average (8.6%), it presents low productivity, and it is a very scattered resource.
METHODOLOGY
A geographic data base is worked out within the initial phase of the project. This is carried out
by gathering data from several sources of information so that a Map of Energetic Resources of
forest biomass in Bizkaia is obtained (Inventario Forestal CAE 2005, IFN3, Mapa Forestal del
Pais Vasco 2004-2005) at a scale of 1:50,000 (MFE50).
Geographic Information Systems (GIS) are useful tools for understanding the geographic
context of a wide range of issues pertinent to bioenergy, especially energy demand and
biomass supplies. After analyzing and reviewing those methods used by different researchers
when evaluating forest biomass residues by means of GIS [5-9] the most adequate
methodology for estimating biomass residue in Bizkaia is defined [Project PIV0822 financed by
the University of the Basque Country]. An indirect methodology based on the use of linealized
alometric equations as logarithmic model has been selected (Eq. 1)
Ln Y = a + b Ln(Dn) (1)
Where:
Y represents the biomass for each fraction (expressed in kg dry mass)
Dn the average diameter in cm and
a and b are the two specific regression parameters.
This model allows straightforward calculations and improves the goodness of the statistical
analysis. However, the final result should be multiplied by a correction factor obtained from the
standard deviation of the estimate in order to eliminate the bias introduced by the logarithmic
transformation. Parameters a and b as well as the bias correction factor take different values
depending on the species under consideration [10]. These equations are applied to the bigger
feet (BF) (R > 7.5cm). In the smaller feet (SF) (R < 7.5cm), most of the tree is not good for wood
exploitation, this making the tree become almost 100% biomass residue. However, in this
research work a more conservative criterion has been used, and only 80% of the total weight
has been considered residue.
An appropriate method for estimating biomass stocks is the use of the concept stratum, which
is defined in the IFN3 [11]. Every stratum is formed by grouping the forest surfaces of similar
features, whose perimeter is marked out to a 1:50,000 scale. The IFN3 defines 12 scales in
Bizkaia (Table 1).
In order to determine the residue estimator generated in each sampling plot, it is only necessary
to know what stratum, from which the plot of the surface was taken, is catalogued. The
estimation of remains from Residual Forest Biomass (RFB) has been carried out in two different
ways. On the one hand, stratum per stratum, and on the other hand, all of them together. In
each situation the estimation is accomplished by means of a confidence interval at a 95% level
for the mean residue in metric tons per year.
421
Table 1 Basic features of the strata from IFN3 of Bizkaia
Occupation Covered Room
Stratum Predominant forest species Mass stage
(%) fraction (%) [Ha]
01 Pinus radiata >=70 Sawtimber, poles 70 - 100 45.210
02 Pinus radiata >=70 Sawtimber, poles 5 - 69 5,589
03 Pinus radiata >=70 Saplings.Seedlings 40 - 100 12,382
P. radiata and P. nigra with Quercus >=70;
04 Saplings.Seedlings 5 - 39 8,655
robur, Castanea sativa and River trees 30<=Esp,<70
Chamaecyparis lawsoniana,
05 >=70 All 5 - 100 4297
Pseudotsuga menziesii and Larix spp.
06 Pinus pinaster and Pinus nigra >=70 Sawtimber, poles 5 - 100 5,250
Q. robur y Q. robur with C. sativa, C. >=70;
07 All 5 - 100 17,650
avellana, Arbutus unedo or P. radiata 30<=Esp.<70
Quercus ilex y Quercus ilex with Q. >=70;
08 All 5 - 100 6,563
faginea, Arbutus unedo or Q. robur 30<=Esp.<70
>=70;
09 Eucalyptus spp. Sawtimber, poles 5 - 100 9.183
30<=Esp,<70
Eucalyptus spp, and Eucalyptus spp. >=70; Saplings.
10 5 - 100 3,804
with Pinus radiata 30<=Esp,<70 Seedlings
F. sylvatica and F. sylvatica with
>=70;
11 Betula spp., Castanea sativa or Q. All 5 - 100 5,523
30<=Esp,<70
robur
>=70;
12 River trees All 5 - 100 2,522
30<=Esp.<70
Occupation (%) represents the occupation percentage of predominant forest species, Mass stage represents the stage in the development
of the referred species, and Covered fraction (%) represents the percentage of land covered by the horizontal projection of vegetation
Strata 1, 2, 3, in which pinus radiata appears as the predominant species, are selected. As far
as eucalyptus is concerned, stratum number 9, whose mass state (Sawtimber, poles) advises a
final clearing or cut, is selected. The estate of eucalyptus masses in stratum number 10
(Saplings. Seedlings) does not currently add, in a meaningful way, any residual biomass. The
quantity of forest biomass residue (Tons/year) is determined after considering two factors: the
quantity of forest residue (Tons/ha-year) of the main forest species, and the surface (ha)
occupied by such species (Fig. 5).
Fig. 5 Potential biomass residue estimator
For estimating the amount of annual biomass (metric tons/year) that might be generated by
current forest masses in Bizkaia, the methodology applied uses a Geographic Information
System (GIS) with the help of the Arcview GIS 10 program. In order to carry it out, the forest
species distribution vectorial information is pasterized with a spatial resolution pixel of 2 meters
terms of its most characteristic specie. In this way, it has been possible to process an important
amount of data and to manage the results obtained [12, 13].
From these residue estimator values assigned to the different sampling points that belong to
strata 1, 2, 3 and 9, different alternatives for linking those specific values to the polygons of the
forest map were searched by Geographic Information Systems. Voronois diagram (Thiessens
Polygons) was selected due to its simplicity, and each polygon was linked to the residue
estimator whose Thiessens polygon takes in a bigger surface.
422
The energy potential of wooded species selected in petrol equivalent tons (pet) is obtained from
Eq. 2 [14]:
P = S(ha) . Er(t / ha . year) . LHV (Kcal / kg) .1000kg / t.1tep /107 Kcal (2)
Where S is surface in hectares, Er is forest wet residue estimator in tons/year, LHV represents
the lower heating value (toe t-1), and P is the available energy potential (toe). The potential
energy of biomass expressed in kJ/ha is calculated by using GIS tools (Ackview GISTM).
RESULTS
The estimation of remains from RFB has been carried out in two different ways. On the one
hand, stratum per stratum, and on the other hand, all of them together. In each situation the
estimation is accomplished by means of a confidence interval at a 95% level for the mean
residue in metric tons per year. Normality tests of the data were also carried out to determine if
the values of the random variable Eri (estimator of residue in metric tons/ha and year) present a
normal distribution. In order to do so, five different tests that belong to the R statistical software
pack nortest were used (Anderson-Darling; Kolmogorov-Smirnov; Cramer-von Mises; Pearson
and Shapiro-Francia) [15-16]. Results for the latter variable corresponding to the strata
considered in the present research work are listed in Table 2.
Table 2 Quantity of residue (RFB) according to the stratum and to the predominant species
Stratum Predominant forest species Room [Ha] RFB [t.year-1]
01 Pinus radiata 45,210 38109-41329

02 Pinus radiata 5,589 1220-1583
03 Pinus radiata 12,382 2806-4331
09 Eucalyptus spp. 9,183 6595-8454
Figures 6 and 7 show the values of the residue estimator (metric tons/ha year) that correspond
to stratum 1 (dominant species Pinus radiata) and stratum 9 (dominant species Eucalyptus
globulus) from Bizkaia.
Fig. 6 Residue estimator map from stratum 1 Fig. 7 Residue estimator map from stratum 9
The results obtained after the statistical analyses of the data showed that the amount of mean
forest biomass achieved within an interval of 95% is 52,214 metric tons/year, with an estimated
32,011toe/year energy potential.
ACKNOWLEDGEMENTS
We would like to acknowledge Vicerrectorado de Investigacin de la Universidad del Pas
Vasco-Euskal Herriko Unibertsitatea for financing project NUPV08/22 within which this research
has been carried out. The authors thank the technical and human support provided by SGIker
(UPV/EHU, MICINN, GV/EJ, ERDF and ESF).
423
REFERENCES
[1] J. Fernandez, Biomasa. Energias renovables, Cuaderno Energas renovables para todos:
Biomasa. In: http://www.energiasrenovables (2007)
[2] J.I. Hormaeche, La energa de la biomasa convertida en calefaccin, Jornadas sobre la
energa renovable de la biomasa, EVE, Gobierno Vasco (2011)
[3] M. Camps, F. Marcos, Los biocombustibles, Ed. Mundi-Prensa, Madrid (2002)
[4] E. Mateos, J. Gonzlez, Biomass: Potential source of useful energy, International
Conference on Renewable Energy and Power Quality (ICREPQ07), Book of Summaries
(2007) 199-200.
[5] L.S. Esteban, P. Prez, P. Ciria, J.E. Carrasco, Evaluacin de los recursos de biomasa
forestal en la provincia de Soria. Anlisis de alternativas para su aprovechamiento
energtico, Coleccin Documental CIEMAT (2004)
[6] M.T. Ter-Mikaelian, M.D. Korzukhin, (1997) Biomass equations for sixty-five North
American tree species, Forest Ecology and Management (1997) 1-24.
[7] L.S. Esteban, M. Ciria and Carrasco, J.E. (2008) An assessment of relevant
methodological elements and criteria for surveying sustainable agricultural and forestry
biomass by-products for energy purposes, Bioresources, 3 (2008) 910-928.
[8] L.S. Esteban, R. Garca, P. Ciria and J. Carrasco, Biomass Resources and Costs in Spain
and Southern EU Countries, Clean Hydrogen-rich Synthesis Gas Report, Chrisgras fuels
from biomass, 1 Deliverable 36 CIEMAT (2009)
[9] A. Merino, C. Rey, J. Braas and R. Rodrguez-Soalleiro, (2003) Biomasa arbrea y
acumulacin de nutrientes en plantaciones de Pinus radiata D. Don en Galicia, Invest.
Agraria, Sist. Recur. For. 12 (2) (2003) 85-98.
[10] F. Lpez-Rodrguez, C. Prez Atanet, F. Cuadros Blzquez, A. Ruiz Celma, Spatial
assessment of the bioenergy potential of forest residues in the western province of Spain,
Caceres, Biomass and Bioenergy, 33 (2009) 358-366.
[11] Tercer Inventario Forestal Nacional en versin digital para la provincia de Vizcaya (IFN3)
Ministerio de Medio Ambiente, (2006)
[12] O. Masera, A. Ghilardi, R. Drigo, A. Trossero and M. WISDOM, M (2006) A GIS-based
supply demand mapping tool for woodfuel management, Biomass and Bioenergy, 30
(2006) 618-637.
[13] Ciemat, Desarrollo de una Aplicacin en base de Sistema de Informacin Geogrfica
(SIG) para la Evaluacin de Recursos de Biomasa a travs de Internet. Especificaciones
tcnicas, Centro de Desarrollo de Energas Renovables, Soria (2009)
[14] J. Domnguez Bravo, P. Ciria, L.S. Esteban, D. Snchez and P. Lasry, Evaluacin de la
biomasa potencial como recurso energtico en la regin de Navarra, Geofocus, Rev. Int.
Ciencia y Tecnologa de la Inf. Geogrfica, 3 (2003) 1-10.
[15] S. Wolfram, The Mathematica Book, Champaign (Illinois), Wolfram Media, Inc.(2003)
[16] P. Spector, Data Manipulation with R, New York, Springer (2008)
424
INFLUENCE OF FREE FATTY ACID CONTENT IN BIODIESEL PRODUCTION

ON NON-EDIBLE OILS
1 2 3
A. Ribeiro , F. Castro and J. Carvalho
ABSTRACT
The use of alternative feedstock as waste cooking oils (WCO) and bovine tallow for
biodiesel production has some advantages. It is cheaper than edible vegetable oils and it
is a way to valorize a sub-product. Nevertheless, these oils possess some contaminants,
specially free fatty acid (FFA) content, which can reduce the quality and yield of biodiesel
production. This problem was solved by testing different operating conditions and
different transesterification procedure and equipments for each stage of processing.
Technological assessment of process was carried out to evaluate their technical benefits,
limitations and quality of final product. In this work biodiesel was produced by an alkali-
catalyzed transesterification and by a two step esterification/alkali-catalysed
transesterification in cases which FFA content has above 3%. Evaluation of quality from
raw materials and final biodiesel was performed according to standard EN 14214. Results
show that all parameters analyzed meet the standard and legislation requirements. This
evidence proves that in those operational conditions the biodiesel produced from WCO
and bovine tallow can substitute petroleum-based diesel.
Keywords: Biodiesel; Free Fatty acid (FFA); Waste Cooking Oil (WCO); Bovine tallow
INTRODUCTION
Energy is the most fundamental requirement for human existence and activities. As an effective
fuel, petroleum has been serving the world to meet its need of energy consumption. But the
dependence of mankind entirely on the fossil fuels could cause a major deficit in future.
Furthermore, the threat of supply instabilities and the increased public awareness on the impacts of
fossil fuel emissions on the environment and their potential health hazards triggered governments
around the world to impose restrictions on fossil fuel combustion emissions. Hence, the discovery
of an alternative source of energy was of immense importance to meet its energy requirements.
The application of biodiesel to our diesel engines for daily activities is advantageous for its
environmental friendliness over petro-diesel [1,2].
Biodiesel (Fatty Acid Methyl Esters) have become one of the most promising alternative biofuels in
the world [2]. Biodiesel has a higher cetane number, no aromatics, and contains 10%11% oxygen
by weight [3,4] These properties reduce the emissions of carbon monoxide (CO), hydrocarbons
(HC), and particulate matter (PM) in the exhaust gas [5, 6, 7]. According to Utlu and Kokac [8],
there was an average decrease of 14% for CO2, 17.1% for CO and 22.5% for smoke density when
using biodiesel. Puppan [9] have discussed the advantages of biofuels over fossil fuels to be: (a)
availability of renewable sources; (b) representing CO2 cycle in combustion; (c) environmentally
friendly; and (d) biodegradable and sustainable. Biodiesel, which is considered as a possible
substitute of conventional diesel fuel is commonly, composed of fatty acid methyl esters that can be
prepared from triglycerides in vegetable oils by transesterification with methanol [10]. The resulting
biodiesel is quite similar to conventional diesel fuel in its main characteristics [11].
Transesterification (fig. 1) is the process by which the glycerides present in fats or oils react with an
alcohol in the presence of a catalyst to form esters and glycerol [12,13,14]. Catalyst increases the
425
rate of the reaction and also the yield. This reaction proceeds well in the presence of some
homogeneous catalysts such as potassium hydroxide (KOH)/sodium hydroxide (NaOH) and
sulfuric acid, or heterogeneous catalysts such as metal oxides or carbonates [15]. Depending on
the undesirable compounds (especially FFA and water), each catalyst has its advantages and
disadvantages. Sodium hydroxide is very well accepted and widely used because of its low cost
and high product yield [1]. The most common alcohols widely used are methyl alcohol and ethyl
alcohol. Among these two, methanol found frequent application in the commercial uses because of
its low cost [13].
Figure 1 - Transesterication of triglycerides with alcohols.
Vegetable oils are promising feedstocks for biodiesel production since they are renewable in
nature, and can be produced on a large scale [16]. However, it may cause some problems such as
the competition with the edible oil market, which increases both the cost of edible oils and biodiesel
[17,18,19]. For instance, the mass plantation of monoculture plants could benefit the economy of
rural population while negatively affecting the water resources and the biodiversity [8]. In order to
overcome these disadvantages, many researchers are interested in others feedstocks as waste
cooking oils [13,20] and grease and animal fats [21,22], which are not suitable for human
consumption and world economy [23]. Currently, chemical methanolysis using alkali-catalyst is the
most popular commercialized process that gives high yield in short reaction time. According to
many previous studies, a large percentage of biodiesel production cost was accounted for by the
feedstock price [24]. However, cheap low grade feedstock often contains large amount of FFA. The
interference of free fatty acid (FFA) and water to the alkali-catalyzed process for producing
biodiesel has limited the use of those recycled, inexpensive, retrograde feedstock, or whatever may
significantly reduce the costs of biodiesel. It was suggested that an acid catalyst be necessarily
used to perform transesterification while feeding the low grade oil components [25]. However, the
reaction rate of transesterification catalyzed by the acid catalysis is much slower than that
catalyzed by alkali catalysis and more methanol is required [26]. Canakci and Gerpen [27]
developed a two-stage process where the level of FFA could immediately be reduced to less than
1% using an acid catalyst (H2SO4) at the first stage.
The aim of this study was evaluate the influence of FFA in biodiesel production on waste cooking
oils (WCO) and bovine tallow and analyze the best operational conditions for each feedstock. It
was tested different processes for biodiesel production by a one step alkali-catalyzed
transesterification and by an acid and alkali-catalyzed two-step transesterification. The final
products of each process were analyzed according to standard EN 14214:2003 related to biodiesel
quality.
BIODIESEL PRODUCTION WITH CATALYZED TRANSESTERIFICATION
Alkali-catalyzed transesterification
The use of alkali catalysts in transesterification reaction of waste cooking oil and animal fats is
somewhat limited, because FFA content in this feedstock oil reacts with the most common alkaline
catalysts (NaOH, KOH, and CH3ONa) to forms soaps [12]. This reaction is undesirable because
soap lowers the yield of the biodiesel and inhibits the separation of the esters from the glycerol.
Feedstocks with high free fatty acid will react undesirably with the alkali catalyst thereby forming
soap. The maximum amount of free fatty acids acceptable in an alkali- catalyzed system is below 3
wt.% of FFA. If the oil or fat feedstock has a FFA content over 3 wt. %, a pretreatment step is
necessary before the transesterification process [18].
426
Acid- and alkali-catalyzed two-step transesterification
Alkaline and acidic catalysts have their own advantages and disadvantages in transesterification of
waste cooking oil or animal fats. Hence, to avoid the problems associated with the use of these
catalysts separately, especially the problems of saponification and slow reaction time, many
researchers have developed the two-stage acid-and- alkali-catalyzed transesterification. In the first
stage, esterification of FFA present in feedstocks is carried out using acid to decrease the FFA
level to less than 1%. In the second stage, transesterification of the neutral feedstocks is performed
using an alkaline catalyst [12, 13].
Process design
Fig. 2 shows a simplified flow chart of the alkali-catalyst process tested in this study for the
transesterification of WCO and bovine tallow.
Figure 2 - Simplified process flow chart of alkali-catalyzed biodiesel production
EXPERIMENTAL PROCEDURE
Bovine tallow
Fatty acid methyl ester of bovine tallow as biodiesel fuel was prepared by base-catalyzed
transesterification of tallow with methanol in the presence of NaOH as catalyst and a process
combining acid esterification and alkali-based transesterification. Before transesterification, tallow
was heated among 105110 C for 4 h and then strained the sediment out of the tallow with filter.
After this process, the yield of oil recovery from bovine tallow was 43%. Tallow was heated to 63 C
slowly. In another flask, methanol (9:1 molar ratio methanol/tallow) was mixed with sodium
hydroxide (0.5% w/w), until all of the NaOH was dissolved in methanol. This mixture was then
added to the melted tallow, and further heated to 63 C, for 2 h. Ester was purified by washing with
distilled water and citric acid and drying to room temperature.
In the two steps esterification/transesterification tallow was heated to 63 C slowly. Methanol (6:1
molar ratio) was mixed with acid sulfuric (0.08% w/w). This mixture was then added to the melted
tallow, and further heated to 63 C, for 2 h. Ester was purified by washing with distilled water and
drying to room temperature. Transesterification reaction was realized by adding a sodium
hydroxide solution (0.01 w/w) and methanol (6:1 molar ratio methanol/tallow) to the esters from
esterification reaction at 63 C for 2 h. Ester was purified by washing with distilled water and citric
acid and drying to room temperature.
Waste cooking oils (WCO)

Fatty acid methyl ester WCO as biodiesel fuel was prepared by base-catalyzed transesterification
of WCO with methanol in the presence of NaOH as catalyst. Before transesterification, WCO was
filtered and heated among 65 - 70 C for 30 min. Methanol (5:1 molar ratio methanol/WCO) was
mixed with sodium hydroxide (0.01% w/w), until all of the NaOH was dissolved in methanol. This
mixture was then added to the WCO, stirred rigorously, and further heated to 60 C, for 2 h. Ester
427
was purified by washing with distilled water and citric acid and drying at 100 C for 4 h. The final
polishing process was realized by filtering the methyl ester in a filtering unit system.
Influence of FFA content

The non edible oils used in biodiesel production have very contaminants, which can increase the
FFA content and reduce the efficiency of the process. To determine the proportion and the
maximum FFA concentration allowable to alkali-catalyzed transesterification experiments were
realized with bovine tallow, varying the initial FFA content and the sodium hydroxide concentration
(table 1). These experiments were performed on bovine tallow because WCO has FFA content less
than 1%.
Table 1 Effect of initial FFA content in biodiesel production

Sodium Hydroxide
Initial FFA content Methanol molar ratio
concentration Mass conversion (%)
(%) (methanol/tallow)
(w/w)
2,2 0,5 89
3,5 0,75 74
9:1
5,1 1 56 (and soap formation)
7,5 1,25 (Soap formation)
These results shows that initial FFA content have a preponderant influence in alkali
transesterification because when its concentration was higher, biodiesel production expressed by
mass conversion was reduced and formed soaps. Maximum mass conversion was taken with a
lower FFA content of 2,2%. This evidence confirmed that alkali-catalyzed transesterification only
can be performed when FFA content was less than 3%.
Mass conversion
One of the most important dependent variables in this experiment is the mass conversion, which is
given by the mass ratio of biodiesel (product) to the total initial mass of the raw material and the
additives [1].
Figure 2 Mass conversion (%) of biodiesel from the different feedstocks tested
Results demonstrated that WCO biodiesel was the maximum mass conversion of 92%, alkali-
based tallow biodiesel was 89% and esterification/transesterification tallow biodiesel was 85% of
conversion (Fig.2). Mass conversion depends on several parameters like, reaction temperature and
pressure, reaction time, rate of agitation, type of alcohol used and molar ratio of alcohol to oil, type
and concentration of catalyst used and principle concentration of free fatty acids (FFA) in the feed
oil [12,13,23]. Through these results it is possible to verify that FFA was high influence in the mass
conversion because the less FFA content feedstock achieves the highest conversion.
428
Quality of Biodiesel
The major focal point for biodiesel high quality is the adherence to biodiesel standard
specifications. These standard specifications in European Union are established by EN 14214 for
biodiesel fuel [1,12,28]. The results of the analyses in the different types of biodiesel produced
(Table 2) showed that in generally the quality parameters of standard EN 14214 was
accomplished.
Table 2 Results of biodiesel produced from the different feedstocks tested according to standard
EN 14214
Alkali-based Esterification/ Limits
WCO
biodiesel from transesterification
Property Unit biodiesel Test Method
bovine tallow biodiesel from Minimum Maximum
result
result bovine tallow result
Ester content % (m/m) 96,8 0,1 94,5 0,2 92,0 0,5 96,5 EN 14103
3
Density at 15 C kg/m 881 5 883 0,85 875 1 860 900 EN ISO 3675
Viscosity at 40 C mm2/s 4,75 0,01 5,07 0,02 5,01 0,02 3,00 5,00 EN ISO 3104
Flash point C 174 2 164,0 0,5 150 2 120 - EN ISO 3679
EN ISO
Carbon residue % (m/m) 0,20 0,05 - - - 0,30
10370
Water content mg/kg 142 2 492 1 420 2 - 500 EN ISO 3679
Acid value mg KOH/g 0,25 0,05 0,46 0,02 0,48 0,02 - 0,50 EN 14104
g iodine100
Iodine value 62,82 1,50 81,22 0,02 78,22 0,01 - 120 EN 14111
g
Linolenic acid
% (m/m) 8,4 0,5 - - - 12,0 EN 14103
methyl ester
Methanol content % (m/m) 0,12 0,01 0,1 0,01 0,1 0,01 - 0,20 EN 14110
Group I metals EN14108
mg/kg 4,71 0,03 - - - 5
(Na + K) EN 14109
CONCLUSIONS
Biodiesel is gradually gaining acceptance in the market as an environmentally friendly alternative
diesel fuel. However, for biodiesel to establish and continue to mature in the market, various
aspects must be examined and overcome. Some of the key issues such as improving efficiency of
the production process, using low cost feedstock have been reviewed and analyzed. As with any
new technology or products, biodiesel will require continuous improvement especially in producing
cleaner emissions and having less impact on the environment.
On this study it was used different feedstock oils to produce biodiesel, and it was demonstrated
that the effect of various operating and processing parameters on transesterification depends on
quality and source of the feedstock oil. According to FFA content, different technological
approaches can be used. It was used the alkali-catalyzed process because FFA content in collect
frying oil was less than 1%, but when FFA content as a higher value, like on bovine tallow, it was
necessary doing a two step process: esterification and transesterification. From the technical
assessment in laboratory and a pilot plant, all of these processes proved to be feasible for
producing a high quality biodiesel product. Process using waste cooking oils and bovine tallow oil
had a high yield of conversion and the analyses on the final biodiesel showed that all quality
parameters of the standard 14214 have been respected for witch feedstock oil.
According to these results, it is possible to conclude that the biodiesel produced with tested
feedstock was liable to be used in diesel car engines, in a unique way (B100) or blending with fuel
diesel (B20, B30 and B50), without decrease of engine efficiency.
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430
PREPARATION OF ACTIVATED CARBON FROM WASTE LEATHER FROM

THE TANNING INDUSTRY
1,2 3 4
M.M.A. Freitas , M.J. Magalhes and A.A. Crispim
1 CIETI/ DEQ, Instituto Superior de Engenharia, Instituto Politcnico do Porto, R. Dr. Antnio
Bernardino de Almeida, 4200-072 Porto, Portugal, mmd@isep.ipp.pt
2 Laboratrio de Catlise e Materiais (LCM), Laboratrio Associado LSRE/LCM, Departamento de
Engenharia Qumica, Faculdade de Engenharia, Universidade do Porto, R. Dr. Roberto Frias,
4200-465 Porto, Portugal, mmd@isep.ipp.pt
Bernardino de Almeida, 4200-072 Porto, Portugal,1040845@isep.ipp.pt
Bernardino de Almeida, 4200-072 Porto, Portugal, aar@isep.ipp.pt
ABSTRACT
The main objective of the present study is to investigate the production of activated
carbons from two different types of leather waste: wet blue waste, a waste from the
tanning process with chromium and wet white waste, a waste from the tanning process
with vegetables. The methods used for the preparation of activated carbons were
physical activation with carbon dioxide and chemical activation with potassium hydroxide.
The activated carbon obtained by physical activation with higher specific surface area
was the carbon prepared from the residue of wet blue with a burn-off of 23 % (SBET= 152
2
m /g). KOH chemical activation of wet blue and wet white wastes produces activated
carbons with high adsorption capacity. Activated carbons obtained by this methodology
2
are microporous, with high specific surface area (SBET= 1696 m /g).
Keywords: Leather wastes; active carbon; physical activation; chemical activation
INTRODUCTION
The leather making process generates substantial quantities of solid and liquid wastes (hides and
skins, fats, shaving and trimming, process effluents, sludge). The most common way to manage
these solid wastes is by disposing of them on land sites.
Shavings of wet blue and wet white are solid wastes of the tanning industry with high carbon
content, making their use relevant to the preparation of materials of technological interest [1-3]. The
objective of this work was the valorization of these solids wastes by its use on the preparation of
activated carbons.
Activated carbons are commonly prepared by the well-known methods of physical activation and
chemical activation [4].
Physical activation consists of the carbonization of the precursor material and activation of the
resulting char in steam or carbon dioxide. Chemical activation is a single step process and is held
in presence of chemical reagents, such as KOH, NaOH, K2CO3, ZnCl2, and H3PO4.
Chemical activation is one of the most common techniques used to increase the microporosity of
carbon materials [4]. Many variables are involved in the activation process including the nature of
the carbon precursor, the type and amount of activating agent, the gas flow rate, the heating rate,
the operating temperature, etc. By varying the activation conditions, namely the amount of
activating agent, it should be possible to develop activated carbons with large surface areas. The
use of KOH as activating agent has been reported by different authors to obtain activated carbons
with high surface area and a well developed microporous structure [5-7].
431
The aim of this work was to evaluate the potentialities of two leather tanning wastes for the
production of low cost activated carbons by physical activation with carbon dioxide and chemical
activation with KOH. Special attention was paid to activation with KOH, and it was studied the
influence of the weight ratio KOH:waste on the surface area development of the obtained activated
carbons.
EXPERIMENTAL
Wastes of leather used in this study for the production of activated carbon, namely wet blue waste
and wet white waste, were provided by companies Dias Ruivo, Tanning and Leather Products and
Tanning Aveneda, respectively. Given the moisture content of samples of wet blue and wet white
wastes be ~ 50%, the samples were previously dried at 105 C before use.
Carbonization of wet blue and wet white wastes was studied in the temperature range of 500 C to
3
800 C under inert atmosphere (200 cm /min of N2).
In physical activation, the precursors were first carbonized at 800 C and subsequently activated at
940 C, with a heating rate of 5 C/min, using CO2 as activating agent (series wwCO2 and wbCO2).
The activation times used were 20, 40 and 60 minutes.
For chemical activation, the precursors were impregnated with KOH using hydroxide:precursor
weight ratios of 0.5:1, 1:1 and 3:1. The impregnation was carried out directly on the wastes of wet
blue and wet white (series wwKOH and wbKOH) and on carbonized wastes of wet blue (series
wbcKOH). The activation was performed in a vertical furnace under an inert atmosphere at 940 C,
with a heating rate of 5 C/min and an activation time of 1 hour. After activation the materials were
washed with HCl 0.1 M and then with water until pH=6, and then dried over night.
The precursors were characterized by elemental and proximate analysis with a CARLO ERBA EA
1108 Elemental Analyser and a TG/DSC Netzsch STA 409 PC Luxx1 System, respectively.
The textural characterization of the carbon materials, including the determination of surface areas
(SBET), was based on the N2 adsorption isotherms at 77 K using a Quantachrome Instruments Nova
4200e. The microporous volumes and mesoporous surface areas were determined by t-method,
using a standard isotherm for carbon materials.
The materials were also characterized by the determination of methylene blue index.

Raw materials characterization
The proximate and elemental analyses of the wet blue and wet white leather residues are shown in
table 1. Both residues have high carbon content and the chromium containing leather, wet blue
residue, presented a higher content in ash than wet white residue due to the presence of
chromium.
Table 1. Proximate and elemental analysis of wet-blue and wet-white leather wastes.
Wet blue Wet white

Chromium (Cr2O3) [wt%] 2,6 -
Proximate Analysis [wt%]
Volatiles 74,7 77,1
C fixed 11,5 18,8
Ash 13,8 4,1
Elemental Analysis [wt%]
C 38,9 46,0
O 39,7 31,7
H 6,2 6,5
N 13,1 13,5
S 2,2 2,2
432
Carbonization of wet blue and wet white wastes was studied in the temperature range of 500 C to
800 C, and it was verified that carbonization of both residues is complete at 800 C. At this
temperature it was obtained a char yield of ~30% for both residues.
CO2 activation
The char obtained from the carbonization of wet blue and wet white wastes was activated with
carbon dioxide at 940C. The activation time was varied (20, 40 and 60 minutes) in order to study
the influence of burn-off on the textural properties of activated carbons. The results of textural
characterization of the obtained activated carbons are shown in table 2. As can be seen in Table 2,
the activated carbons of both series have low values of specific surface area.
Table 2. Textural characterization of the activated carbons obtained by CO2 activation at 940C
from wet blue and wet white char obtained at 800C.
Methylene
B.O. S BET Vmicro Sext.
Sample blue index 2 3 2
[%] [m /g] [cm /g] [m /g]
[g/100g]
wbCO2 _20 19 6 148 0,061 32
wbCO2 _40 23 10 152 0,060 32
wbCO2 _60 50 25 59 0,002 53
wwCO2 _20 26 2 51 0,017 19

wwCO2 _40 45 5 118 0,044 21
wwCO2 _60 65 6 96 0,034 21
In both series, for the activated carbons with higher burn-off it is observed a decrease in surface
area. This decrease is due to excessive gasification, which results in the destruction of
microporous and mesoporous structures.
Comparing the results obtained on the two series, the series of activated carbons prepared from
the wet blue char exhibits best textural properties, and the activated carbon with higher specific
surface area is the carbon prepared from the residue of wet blue with a burn-off of 23 % (SBET=
2
152 m /g).
Chemical activation with KOH

The agent used for chemical activation was potassium hydroxide, and the study was focused on
the variation of weight ratio of KOH:waste. First it was used a ratio 1:1 of KOH:waste for both
residues and the impregnation was made directly on the dried wastes. Figure 1 shows the N2
adsorption isotherms at 77 K on activated carbons obtained by KOH activation of wet blue and wet
white leather wastes. It is verified that the isotherms obtained for the activated carbons are of type
I, characteristic of microporous materials.
The curvature of the isotherm at low relative pressures gives us an indication of the average size of
the microporous structure. If the curvature is farthest from the axis, we have a microporous
structure with a high average micropore size. So, we can expect that activated carbon wbKOH_1:1
has a microporous structure with a wide pore size distribution.
It is also observed that the volume of N2 adsorbed by activated carbon prepared from wet-blue
(wbKOH_1:1) is higher, meaning a higher adsorption capacity and a larger specific surface area.
Thus, wet blue waste was used to study the effect of KOH:waste ratio impregnation in textural
properties of the activated carbons. For this study it was used the wet blue char obtained at 800C,
because for the higher ratio of KOH:waste it was verified a chemical degradation of the wet blue
residue. The wet blue char was impregnated with KOH using hydroxide:char ratios of 0.5:1, 1:1 and
3:1 and activated at 940C.
Figure 2 shows the nitrogen adsorption isotherms at 77 K on activated carbons obtained by KOH
activation of wet blue char impregnated with different ratios. Activated carbons wbcKOH_3:1 and
wbcKOH_0,5:1 have similar textural properties.
433
It should be noted that the direct impregnation of the precursors originate activated carbons with
higher adsorption capacity when compared with activated carbons prepared by impregnation of the
carbonized precursor (samples wbKOH_1:1 and wbcKOH_1:1).
Figure 1. Nitrogen adsorption isotherms at 77 K on activated carbons obtained by KOH activation

of wet blue and wet white leather wastes.
Figure 2. Nitrogen adsorption isotherms at 77 K on activated carbons obtained by KOH activation

of wet blue char impregnated with different ratios.
The results of carbon yield in the activation process before and after activating agent removal are
shown in table 3. It is verified that an increase of the impregnation ratio leads to a decrease in the
yield on activated carbon. In chemical activation the activating agent is incorporated in the particles
of precursor and reacts with the products resulting from its thermal decomposition, reducing the
evolution of volatile matter and inhibiting shrinkage of the particles. However, for high
concentrations of activating agent the destruction of the carbonaceous matrix may occur, resulting
in a reduction in carbon yield.
The results of textural characterization of the obtained activated carbons are shown in table 3. All
the activated carbons prepared by chemical activation have high specific surface areas if compared
with those prepared by physical activation. Chemical activated carbons prepared with the ratio of
434
1:1 are essentially microporous materials, given the contribution of micropores to the specific
surface area to be about ~ 95% for wbKOH_1: 1 and ~ 96% for wbcKOH_1: 1.
Increasing the ratio of activating agent in the precursor and in the carbonized precursors, there is
an increase in specific surface area of the activated carbons.
After preparation of activated carbons by both methods (physical and chemical activation), it was
found that the chemical activation of wet blue and wet white wastes originates activated carbons
essentially microporous with some degree of mesoporosity, as we can observe by the values of
Vmicro and Sext and values of methylene blue index in table 3.
Table Erro! No existe nenhum texto com o estilo especificado no documento.. Textural
characterization of the activated carbons obtained by KOH activation at 940C of wet blue and wet-
white wastes and wet blue char obtained at 800C.
Methylene
KOH S BET Vmicro Sext
Sample blue index 2 3 2
[%] [%] [m /g] [cm /g] [m /g]
[g/100g]
wbKOH_0,5:1 29 12 - 894 0,182 580
wbKOH_1:1 25 10 29 1696 0,776 78
wwKOH_1:1 18 3 29 1665 0,663 106
wbcKOH_0,5:1 72 52 26 1504 0,598 375
wbcKOH_1:1 64 36 20 1145 0,507 51
wbcKOH_3:1 41 28 - 1507 0,596 377
Due to its textural characteristics, these carbons materials were tested in the color removal of a
tannery effluent. Activated carbon wbKOH_1: 1 was placed in contact with the effluent for 64 hours,
and it was obtained a color removal of 96%. It was also observed a reduction of 33% in the effluent
COD.
CONCLUSIONS
We can conclude that KOH chemical activation of wet blue and wet white wastes produces
activated carbons with high adsorption capacity. Activated carbons obtained by this methodology
are microporous, with high specific surface area.
Preliminary adsorption tests show that these activated carbons have a good performance for color
removal from effluent of tanneries.
It was concluded that both residues are good precursors for activated carbon production,
specifically using chemical activation, thereby reducing the volume of waste from tanneries sent to
the landfill.
References
[1] O. Ylmaz, I. C. Kantarli, M. Yuksel, M. Saglam, J. Yanik, Conversion of leather wastes to
useful products, Resources, Conservation and Recycling 49 (2007) 436448.
[2] R.R.Gil, R.P.Girn, B.Ruiz, M.S.Lozano, M.J.Martn and E.Fuente, Valorization of solid wastes
from the leather industry: Preparation of activated carbon by thermochemical processes, in
Proceedings of 1st Spanish National Conference on Advances in Materials Recycling and Eco
-Energy, 2009.
[3] L. C. A. Oliveira, M.C. Guerreiro, M. Gonalves, D.Q.L. Oliveira, L.C.M. Costa, 2008.
Preparation of activated carbon from leather waste: A new material containing small particle of
chromium oxide. Materials Letters, 62 (2008) 3710-3712.
[4] R . C. Bansal, F. Stoeckli, J-B. Donnet, Active carbon, Ed. Marcel Dekker, New York, 1988.
435
[5] M. M.A. Freitas, J. L. Figueiredo, Preparation of activated carbons with controlled pore size, in:
F. Rodriguez-Reinoso, B. McEnaney, J. Rouquerol and K. Unger (Eds.), Studies in Surface
Science and Catalysis 144 (2002) 261-265.
[6] H. Marsh, D. Crawford, T. M. OGrady, A. Wennerberg, Formation of active carbons from
cokes using potassium hydroxide, Carbon 22 (1984) 603-611.
[7] S. Yang, H. Hu, G. Chen, Preparation of carbon adsorbents with high surface area and a
model for calculating surface area, Carbon 40 (2002) 277-284.
436
ASSESSMENT OF WASTE ELECTRICAL AND ELECTRONIC EQUIPMENT

REUSE: A LIFE CYCLE ASSESSMENT APPROACH
1 1
E.J. Silva , M.A. Estrela
1 Environment Department, Instituto de Soldadura e Qualidade. Av. Prof. Dr. Cavaco Silva, n 33,
Taguspark Oeiras 2740-120 Porto Salvo. E-mail: ejsilva@isq.pt / maestrela@isq.pt
ABSTRACT
Background Waste Electrical and Electronic Equipment (WEEE) is considered a valuable
source for secondary raw materials if treated properly. This paper presents the results of
the Life Cycle Assessment (LCA) conducted during the ELECTROVALUE project, which
intends to improve the recycling market of electrical and electronic (EE) products through
the recovery and reuse of EE components.
Methods Two different scenarios were considered and compared. The first scenario
represents the current circumstances, where all EE components are sent to recycling.
The second scenario presents the project overview, being part of EE components, those
which confirm compliance with the quality requirements, recovered for reuse. An
assembled Printed Circuit Board (PCB) used as a control unit on a lifter, was the
functional unit selected.
Results The reuse of EE components are associated to a decrease of environmental
impacts in all analysed impact categories. The extraction of materials and EE
components manufacture are the processes which contribute mostly to the impacts.
Conclusions The EE components have large influence on an assembled PCB life cycle,
representing more than 95% of its actual environmental impacts. This influence can be
reduced to close 65% if its recovery and reuse is considered.
Keywords: Life Cycle Assessment; Waste Electrical and Electronic Equipment; Electrical and
Electronic Components; Reuse.
INTRODUCTION
In the last decade the EU has adopted several policies and regulations in order to prevent
environmental, social and economic impact associated of waste streams. The Waste Electrical and
Electronic Equipment (WEEE) were not an exception, mostly due to their production processes that
require intensive use of different materials. For this reason, these residues are considered as a
valuable source of secondary raw materials, if treated properly. However, despite many technical
solutions already available and being implemented, in most cases the environmental and social
commitments assumed by the related policies are not met.
According to the latest studies and reports, Europe produces 10.3 million tonnes of WEEE per
year, about one quarter of the world total, and this amount is expected to increase to 12.3 million
tons per year by 2020 [1]. Moreover, only 25% of medium-sized household appliances and 40% of
larger appliances collected are sent to recycling processes [1]. Considering that the use of virgin
materials in the production of this equipment is still close to 100%, these figures show not only the
extent of the WEEE stream influence on the environment, but also the potential recovery of
secondary raw materials in this type of waste .
In fact, the main drive force of the WEEE recycling market is related to the recovery of valuable
metals (e.g. gold, copper, nickel). In this regard, numerous processes for the recovery of these
metals have been developed, making the recycling of WEEE a profitable commercial alternative.
However, as mentioned in the ELFNET Roadmap [2], there is a perception that much more can be
done in this sector, namely, the recovery of some of the most expensive components, the recovery
of other materials, the evolution of existing technology, the development of standards for reuse,
437
labeling and guarantees and new design concepts through techniques of assemblies with reusable
modules.
The Electrovalue project, co-financed by the European LIFE program, comes into this direction,
aiming to improve the recycling market of electrical and electronic (EE) products through the
recovery and reuse of EE components, supporting this sector competitiveness in the adoption of
sustainable practices on waste management, materials selection and process technologies by
integrating concepts such LCA, and valorisation of end-of-life.
This article presents the results obtained by this project, particularly in regard to the LCA on
determining the environmental benefits of reusing EE components.
METHODS
Considering the results of some previous studies, that determine the environmental benefits
associated to the WEEE recycling processes [3,4,5], the main objective of this study is related to
the identification these environmental benefits in regard of EE components reuse.
Taking into account the existent amount of components in the market, and the impossibility to
cover all in a single study, a set of components were identified according to their added market
value. The identification of components was based on the design of a PCB to be incorporated as a
control unit on a lifter, specifically created for the project. For this reason, the functional unit chosen
for this study was the PCB, designed specifically for this project, containing the components types
and amounts as shown in Table 1.
Table 1 Types and amount of EE components on the PCB

Type of components Amount of components on the PCB
Fuses 2
Fuse Holders 2
Converters 1
Relays 1
Integrated Circuits 2
Connectors 6
Capacitors 6
Resistors 21
Transistors 7
Diodes 2
Digit Numeric Displays 4
Caps 1
Crystals 1
Terminal Blocks 5
The LCA methodology is widely described in many books [6] and scientific articles [7] which are
based, in most cases, on the ISO 14040 [8].
The product system was designed taking into account the availability and quality of data to each life
cycle stage. Then, the product system of this study begins with the extraction of raw materials
stage, which includes all activities related to drilling and mining processes to extract all necessary
materials from nature. Following to this extraction processes, there is a sequence of operations that
transforms these materials from a raw-material state into industrial usable materials. All these
operations are part of the material processing stage.
The next stage represents the components manufacture. This includes a several number of
processes that, generally, corresponds to the assembly of materials, already shaped and sized,
into the final product, the components. Following comes the use phase which refers to the
assembly of components to PCB by a welding processes. For this reason, and according to
functional unit defined, both solder and PCB production have been taken into account in this study.
After the assembly of EE components, the PCB is incorporated into the lifter, along with several
other types of materials. The next step is usually associated with the consumption of energy by
equipment in order to achieve the purposes for which it was created, representing the phase of EE
equipment use. Also at this stage occur equipment maintenance activities. Considering the
impossibility of predicting the energy consumed during the lifetime of the truck, the exact amounts
438
and sources of other materials that compose it, and the occurrence of these maintenance activities,
these two steps were not taken into account in this LCA.
Finally, when the holder discard the EE equipment, it begins the next stage of the life cycle called
End-of-life. Here appears the main difference between the two scenarios which are compared in
this study. Regarding scenario A, which in fact represents the current situation, the WEEE arrive
the recycler from the collection system and it is sorted accordingly with type of equipment in order
to be placed into a specific process for separation of its constituents. After these separation
processes, the recovered materials can be reused, avoiding the extraction of raw materials from
nature and its associated impacts.
In addition, in the scenario B a new stage related to the separation of components from PWB is
introduced after the separation of the WEEE constituents. This separation corresponds to a manual
process of desoldering the components from the PCB. The components, before sent for reuse
processes, passes through a certification process in order to guarantee their feasibility. Accordingly
with the results of this feasibility study, the component is sent for reuse and re-enter the life cycle at
the Application phase, if confirm in compliance, or for material recovery, if it is not in compliance,
following the actual course explained for scenario A.
In this LCA different approaches were taken into account for recycling and reuse. Due to the
impossibility on determination and tracking the recycled materials current uses, an open-loop
allocation was considered for recycling. This means that components recycled materials are used
in other product systems and were not considered. Regarding the reuse process, it was assumed
that components can be easily reintroduced in the market, mainly due to their added value and
compliance with quality requirements. Therefore, components are reintroduced in the PCB
assembly stage, making possible the application of a close-loop allocation. In addition, different
reuse percentages were given to the components in order to simulate the amount of components
that confirm in compliance and those were not in compliance with the quality requirements.
Therefore, for scenario B, three scenarios were built up with 25%, 50% and 75% reuse
percentages. In each scenario the percentage value means the components that can be sent for
reuse, due to their compliance with the quality requirements.
For both scenarios it was considered the production of two PCB. This approach is primarily related
with the fact that to consider the reuse of the EEC, they will have to go through a phase of previous
use and that, of course, somewhere in its life cycle they will have to be produced.
To perform this LCA, this study used the software SimaPro 7.2.4 [9], a commercial available
software specific for LCA. The data was obtained from the database Ecoinvent 2.2 [10], associated
also to this software. For the Life Cycle Impact Assessment (LCIA) was used Ecoindicator 99
method [11], being all considered categories accepted by the scientific community, in particular by
the UNEP / SETAC Life-Cycle Initiative.
RESULTS
According to the explained methodology, all data was calculated taking into account the functional
unit, and the environmental impacts associated with each scenario were determined. Figures 1 and
2 present the results obtained.
30
25
20
15
Pt
10
0
Scenario A Scenario B - 25% Scenario B - 50% Scenario B - 75%
Human Health Ecosystem Quality Resources
Fig. 1 Comparison of scenarios A and B environmental impacts, by damage category.
439
The figure 2 shows that the scenarios representing the reuse EE components (Scenario B) present
an overall decrease in environmental impacts when compared to the current scenario, in which all
EE components are sent for recycling (Scenario A). This decrease is also more pronounced (about
12%, 24% and 36%), as the percentage of reused EE components increases (25%, 50% and 75%
respectively).
Despite the decrease in global environmental impacts, the damage category related to the effects
on human health, still expresses considerable values even when the reuse of EE components are
assumed. According to the used impact assessment model, the procedures to determine the
impacts related to this category are based on the principle that all human beings, in present and
future, should be free from environmentally transmitted illness, disabilities or premature deaths
[11]. Thus, the impacts associated to this category are related to both human exposure to harmful
substances during one or more stages of life cycle, and the emission of these substances to the
environment, causing changes in ecosystems, biodiversity or climate that also affect the quality of
human life and prosperity.
To assess which stages of life cycle influence these results, the breakdown of damage impact
categories was made, as shown in Figure 2.
10
9
8
7
6
5
Pt
4
3
2
1
0
Carcinogens Org. Compounds Inorg. Compounds Climate Change

Radiation Ozone Layer Ecotoxicity Acidification/Eutrophication
Land Use Minerals Fossil Fuels
Fig. 2 - Comparison of scenarios A and B environmental impacts, by impact category.
According to figure 2, the impact category associated with the biggest impacts is related to human
exposure and the emission to the environment of carcinogens compounds. These values, together
with the impacts also associated with human exposure and the emission to the environment of
inorganic compounds, corroborate the results and conclusions previously mentioned. It can also be
seen in this figure the influence of impacts related to the consumption of fossil fuels, which
represents the second category with higher levels of impact. Taking into account the characteristics
of the different life cycle stages, it can be easily concluded that the stages that mostly contributes
to these results are the production of the EE components, and the extraction of its materials, which
are associated directly or indirectly to a higher energy consumption and the emission of a greater
amount of substances to the environment.
30
25
20
15
Pt
10
0
Components Production PCB Production Assembly End-of-Life
Fig. 3 Environmental impact contribution of the life cycle different stages.
440
These results also show that the influence of the end-of-life stage environmental impacts in the life
cycle of the PCB is almost zero (about 0.1% in all scenarios). For this reason, and taking into
account that the only difference between the two scenarios is the EE components reuse in the
second PCB produced, the environmental impacts associated with Scenario A are higher due to
the occurrence of the EE components production and extraction of their constituent materials.
Then, it can be concluded that the reuse of EE components leads to an indirect reduction on life
cycle environmental impacts of the PCB, once this reduction takes place due to the non-occurrence
of other stages, reducing or even avoiding associated impacts environment.
This conclusion is confirmed by the decrease registered in the consumption of raw materials
associated with the scenario B, as shown in figure 4.
2500
2000
1500
g
1000
500
0
Fig. 4 - Total consumption of raw materials in the different scenarios.
Crossing these values with those presented in figure 2, regarding the environmental impacts
associated to each scenario, the existing reduction in the consumption of raw materials is very
similar to the reduction of environmental impacts and, therefore, is the most important factor which
contributes to these results.
Finally, and in order to analyze the results from a consumer perspective, the effect of reuse of EEC
in the production of only one PCB, has been also studied. This approach was based on the
premise that the consumer of the PCB, has only influence on the environmental impacts associated
with the life cycle of the second PCB produced, particularly through the adoption of sustainable
purchasing options. Thus, in this case, the life cycle begins at a stage where environmental
impacts occurred during the life cycle of the first PCB, once they have already occurred, can not be
avoid.
Figure 5 presents the results of this approach.
16
14
12
10
8
Pt
0
Human Health Ecosystem Quality Resources
Fig. 5 - Comparison of scenarios A and B environmental impacts on the production of just one
PCB, by damage category.
441
As can be seen, the reduction of environmental impacts associated to the two scenarios is
significantly higher when compared with the previous methodology, which is solely due to the
account of EE components production stage in scenario A. Using the scenario A as a base of
comparison, scenario B presents a reduction on overall environmental impacts of 23%, 47% and
71% for rates of reuse of 25%, 50% and 75% respectively. Through these values, it can be
concluded that a consumer who purchases an EE equipment with reused EE components, can
reduce significantly the environmental impacts associated to the EE equipment life cycle.
CONCLUSIONS
The study shows that the reuse of EE components has environmental benefits when compared to
their recycling, mainly due to the avoidance of life cycle stages that present a high consumption of
raw materials. However, despite this reduction in life cycle global impacts, the category associated
with the effects of such products on human health still presents significant impact, mostly due to
the air emissions and human exposure to carcinogenic substances and inorganic compounds.
Nevertheless, and strictly by environmental point of view, a consumer that decide on an EEE
containing reused EE components, can significantly reduce the environmental impacts. This
reduction is mainly done indirectly through the encouragement of sustainable practices and
actions.
However, although not considered in this study, there are other key issues that must be taken into
account when considering the reuse of the EEC. These issues are mainly related to the reliability,
integrity, remaining lifetime, degradation, and guarantees of EE components that, due to the lack of
regulations specifying the reuse process, make difficult to achieve acceptable levels of confidence
by the consumers.
References
[1] R. Kuehr, et al., 2008 Review of Directive 2002/96 on Waste Electrical and Electronic
Equipment (WEEE), Final Report. United Nations University, Contract No:
07010401/2006/442493/ETU/G4 - ENV.G.4/ETU/2006/0032, Bonn, 2007.
[2] J. Pearce, ELFNET Roadmap European Electronic Interconnection, Version 1, European
Lead Free Soldering Network, Hertfordshire, 2007.
[3] F. Andreoli, L. Barbieri, A. Corradi, A.M. Ferrari, I. Lancellotti, P. Neri, Recycling of EOL CRT
Glass into Ceramic Glaze Formulations and Its Environmental Impact by LCA Approach, Int J
LCA. 12 (2007) 448454.
[4] R. Hischier, I. Baudin, LCA study of a plasma television device, Int J LCA. 15 (2010) 428-
438.
[5] W. Scharnhorst, Life Cycle Assessment in the Telecommunication Industry: A Review, Int J
LCA. 13 (2008) 7586.
[6] J.B. Guin, et al., Handbook of Life Cycle Assessment Operational Guide to the ISO
Standards, Kluwer Academic Publishers, New York, 2004.
[7] G. Finnveden, et al., Recent Developments in Life Cycle Assessment, Journal of
Environmental Management. 91 (2009) 1-21.
[8] ISO 14040 International Standard. In: Environmental management life cycle assessment
principles and framework, International Organisation for Standardization, Geneva, 2006.
[9] PR Consultants, SimaPro 7.2.4. Amersfoort, 2010.
[10] R. Hischier, B. Weidema, H.-J. Althaus, C. Bauer, G. Doka, R. Dones, R. Frischknecht, S.
Hellweg, S. Humbert, N. Jungbluth, T. Kllner, Y. Loerincik, M. Margni, T. Nemecek,
Implementation of Life Cycle Impact Assessment Methods, Final report ecoinvent v2.2, No.
3, Swiss Centre for Life Cycle Inventories, Dbendorf, 2010.
[11] M. Goedkoop, R.Spriensma, The Eco-indicator 99: A damage oriented method for Life Cycle
Impact Assessment, Methodology Report, Pr Consultants, Amersfoort, 2001.
.
442
EVALUATION OF THE C/N RATIO IN COMPOSTING PILES OF CARCASSES

AND DIFFERENT BEDDINGS FROM BROILER PRODUCTION FACILITIES
1 2 3 4 5
P.A.V. Lo Monaco , E.C.R. Paiva , A.T. Matos , G.C. Ferres , I.C.A. Ribeiro , S.A.A.
6
Baker
2 Professor at Civil Engineering Department, Federal University of Gois, Catalo, Gois, Brazil.
edcarlopaiva@yahoo.com.br
4 MSc Student in Agricultural and Environmental Engineering at Federal University of Viosa,
Minas Gerais, Brazil. gheilacf@yahoo.com.br
Viosa, Minas Gerais, Brazil. ivan.ribeiro@ufv.br
Viosa, Minas Gerais, Brazil. Sandy.baker@ufv.br
ABSTRACT
The objective of this work to assess the concentrations of organic carbon and total
nitrogen in composting piles of carcasses and different beddings from broiler production
facilities. The organic material was composted in static piles with forced positive aeration
(FPA) with the following treatments: FPA 01 - pile containing sugarcane bagasse, poultry
litter and ground chicken carcasses and FPA02 - coffee husks, poultry litter and ground
chicken. According to the results obtained, it may be concluded that during the entire
composting period, the values of COo of the material contained in the pile composed of
ground chicken carcasses and coffee husks were greater than those obtained in the
compost pile consisting of ground chicken carcass and sugarcane bagasse; there were
significant losses of N in both the material collected in the compost pile containing
sugarcane bagasse (65%) as well as in the material of the pile containing coffee husks
(68%). However, during the composting process, the N loss was greater in the pile
composed of sugarcane bagasse than in that with coffee husks.
Keywords: aerated static piles, poultry waste, organic fertilizers.
INTRODUCTION
World population growth has generated a proportional demand for food, materials and supplies. To
meet the demand for foods,a large quantity of residues has been produced, by-products of
agricultural and agro-industrial processes, resulting in great social, economic and environmental
problems.
Among food-producing activities in the Zona da Mata of Minas Gerais, Brazil, standing out is the
production of broiler chickens, generating large amounts of waste including poultry carcasses and
poultry litter. According to [1 ], the disposal of these carcasses in the environment, without suffering
any type of previous treatment, can lead to serious chemical and microbiological contamination
problems of soil and water, which puts the quality of life around production plants at risk.
In addition to waste generated by poultry facilities, in the same region residues are generated from
the processing of cane sugar and coffee beans, such as bagasse and husks, respectively.
According to [2], whenthese products are in abundance they can lead to the development of pests
and rodents as well as fermentation of the material, causing the formation of organic acids
443
(leachate) that produce odors and may cause contamination of soil and/or surface water and
groundwater.
Because environmental legislation, both state and federal, have established strong requirements
regarding the disposal of residues in the ground, either due to health or environmental issues, it is
important to develop techniques for final treatment/disposal of residues generated by the poultry
industry, especially carcasses of dead animals as well as those generated by the processing of
sugar cane and coffee beans.
Among the appropriate techniques for treatment and disposal of hazardous waste is composting
and subsequent incorporation into the soil, in order to utilize the product in agriculture. During the
composting process, the relationship between the concentration of carbon and nitrogen (C/N) is a
variable of paramount importance in monitoring the level of organic material degradation, since
these two nutrients are essential for decomposition by microorganisms, making it the limiting factor
in the efficiency of this process.
Due to the large availability of waste from intensive breeding of poultry and processing of coffee
beans and sugar cane in the region of Viosa, MG, Brazil, the objective of this study was to assess
the concentrations of organic carbon and total nitrogen in compost material during the composting
process in aerated static piles, containing ground carcasses and bedding of broilers mixed with
sugarcane bagasse and coffee husks.
METHODOLOGY
The compost piles were composed of chicken litter and ground carcasses and sugarcane bagasse.
The carcasses and poultry litter were obtained from farms integrated with agribusiness in the Zona
da Mata region of Minas Gerais, and sugarcane bagasse and coffee huskswere collected from
farms located in the Municipality of Paula Cndido, Minas Gerais, Brazil.
The organic material was composted in static piles with forced positive aeration (FPA) for a period
of 90 days, being 60 days with aeration and 30 days in a maturation bed. Treatments of organic
material degradation were as follows: FPA 01 - pile containing sugarcane bagasse, poultry litter
and ground chicken carcasses, at the proportion of 40% bagasse and 60% chicken litter by
volume, and FPA02 coffee husks, poultry litter and ground chicken carcasses in the same
proportion as FPA 01, i.e., 40% coffee husks and 60% chicken litter by volume.
In the two Aerated Static Piles (ASP) air distribution systems were installed, consisting of
galvanized steel modulated pipe, where the part responsible for aeration of the piles has a
triangular shape (base = 10 cm and height = 10 cm) with holes measuring 1/8"in diameter, evenly
distributed, centrifugal fan ( HP electric motor power) with operation controlled by an analog timer
(accuracy of 15 minutes) and digital thermostat (accurate to 0.1 C). The piles were mounted with
triangular cross section measuring approximately 1 m in height and 3 m in length.
Grinding of the carcasses was done by placing about 10 to 15 whole carcasses in an equipment for
this purpose, referred to as the "Cutter." After loading the carcasses, the equipment was turned on
and then by simultaneous rotation of the propeller and the basin, the carcasses were ground. The
procedure was interrupted when the material had a pasty consistency with a uniform aspect and
the appearance of ground beef.
The FPA 01 was composed of about 145 kg of ground chicken carcass, totaling about 480 kg of
material to be composted and FPA 02 was assembled with about 167 kg of chicken carcass,
totaling about 550 kg of material to be composted.
In this work, the recommendations of [3] cited by [4] were initially followed, which considered fans
3 -1 -1
of 0.5 to 2 HP with sufficient power to meet the air needs of 1200 m h t of dry organic material
into the compost. Based on these figures, it was concluded that for a mass of 0.5 tons of material,
3
fans functioning intermittently for intervals of 15 minutes would provide a volume of 150 m of air.
3 -1
According to data obtained from the fan curve, the maximum flow provided by the fan is 450 m h ,
thus, for aeration of piles of 0.5 tons of material every 15 minutes, the volume of air to be provided
3
should be 112 m .
In the piles, after the chicken carcasses were ground, samples of this material were collected and
mixed with chicken litter. Of the mass produced, samples were taken at different points in the pile,
and then mixed to obtain compost samples representative of the entire pile.
Monitoring began on the dayin which the pile was mounted, referred to as day zero, and continued
during the first phase of the process (active phase) and later stage of maturation.
444
To restore the water content of the material during composting, water was added whenever its
-1
concentration fell below 55 dag kg . Temperature was monitored daily at three points situated at
the base, center and top of the piles, by type thermocouple probes containing sensors and a digital
thermometer.
Actuation of the fan for aeration of the material was done in two ways:
- the controlled temperature was gradually increased, i.e., day 1 30 C, day 2 40 C, day 3 50
C, day 4 60 C and from day 5 on, 65 C. These values were defined based on the experiences
of [5];
- after correction of water content in the material, when the temperature of the pile reached 65 C.
This method, along with the air moistening system implanted, prevented the drying of the pile and
permitted that the thermophilic temperature range was maintained for a longer period.
After 30 days of composting, organic material samples were collected every 15 days (active phase)
and 30 days (ripening stage), for 90 days. In these samples the pH was measured (in water at a
1:5 ratio) and the C/N ratio quantified, where the organic carbon easily oxidized (OC o) was
obtained using a methodology adapted from the Walkley-Black process [6], and nitrogen by the
Kjeldahl method [7]. All tests were performed at the Laboratory of Soil and Solid Waste,
Department of Agricultural Engineering, Universidade Federal de Viosa, Brazil.
By means of regression, mathematical equations were adjusted using the program SIGMA PLOT
to relate the concentrations of organic carbon and total nitrogen, and the C/N ratio as a function of
composting time. Adjustment resulting in the coefficient of determination greater than 60% was
considered satisfactory.

Tables 1 and 2 present the concentrations of carbon easily oxidized (OCo) and total N, as well as
pH and C/N ratio of the material during the composting period. Figures 1 and 2 present graphs
containing regression curves obtained for carbon and nitrogen in function of composting time in
piles 1 and 2, respectively.
Table 1.Concentration of OCo, total N, as well as pH and the C/N ratio of material during the
composting period in the pile consisting of chicken bedding, ground chicken carcasses and
sugarcane bagasse (FPA 1)
OCo Total N
Day -1 pH C/N
-------dag kg ------
0 67.74 4.91 - 13.80
30 27.71 3.07 9.15 9.02
45 26.59 3.15 9.01 8.44
60 23.53 1.61 8.57 14.61
90 25.40 1.68 9.25 15.11
Table 2.Concentration of OCo,, total N, as well as pH and the C/N ratio of material during the
composting period in the pile consisting of chicken bedding, ground chicken carcasses and coffee
husks (FPA 2)
OCo Total N
Day -1 pH C/N
-------dag kg ------
0 68.30 5.04 - 13.55
30 28.09 3.75 9.04 7.49
45 28.59 3.57 9.27 8.00
60 30.36 1.72 9.14 17.65
90 27.80 1.60 8.94 17.37
445
Figure 1. Concentration of Organic Carbon easily oxidized OCo-(a) and Total Nitrogen NTotal -
(b) in material collected from the compost pile consisting of sugarcane bagasse, poultry bedding
and ground chicken carcasses (FPA 1).
Figure 2. Concentration of Organic Carbon easily oxidized COo- (a) and Total Nitrogen NTotal -
(b) in material collected from the compost pile consisting of coffee husks, poultry bedding and
ground chicken carcasses (FPA 1).
According to the data shown in Figures 1a and 2a, there was an exponential decrease in the
concentration of COo in the material of both piles. The large decrease in carbon in the compost is
inherent to this process, mainly resulting from the release of CO 2 due to the respiration of
microorganisms responsible for converting organic matter into humus [8].
Similar to what occurred with the concentration of CO o, there was an exponential decrease in the
concentration of NTotal with time in both compost piles (Figures 1b and 2b). Although the
accumulation of N is common in the material, due mainly to the loss of carbon as CO 2, its reduction
has been observed in the composting of organic waste, in which the initial C/N is low, as is the
case of the animal carcasses. The large concentration of this nutrient at the beginning of the
process, the relatively high temperatures observed in the process, and especially the high pH
values of the medium (Table 1), resulted in greater N loss in the form of ammonia gas.
The pH may be considered one of the principal factors for N material losses, since value above
neutrality favors the formation of ammonia, resulting in greater reductions in N content [9]. Thus, it
th
is observed that after the 30 day of composting of the poultry litter and carcasses, the formation of
ammonia was favored since the pH was always above 8.5.
There was no significant difference in NTotal losses when comparing the results obtained in samples
taken from the compost pile consisting of ground chicken carcasses and sugarcane bagasse, and
446
that consisting of ground chicken carcasses and coffee husks, obtaining values of 65 and 68%,
respectively. However, as can be observed in Table 1, throughout the composting process (except
on day 90), concentrations of NTotal were always lower in material of the compost pile consisting of
ground chicken carcasses and sugarcane bagasse (FPA1), which is possibly associated with
reduced availability of this nutrient in the material.
Losses of N occurring in the organic material analyzed in this study were quite similar to those
observed by [1], who verified N losses of 71.6% during composting of poultry waste (poultry litter
and carcasses of dead birds). According to the authors, losses begin with the hydrolysis of nitrogen
+
compounds by microorganisms that degrade Norganic, leading to the formation of N-NH4
+
(ammonification). The N-NH4 formed is used for microbial growth or for the nitrification process;
however, when presented in quantities greater than those assimilated by microorganisms, it is lost
to the atmosphere in the forms of nitrogen oxides and ammonia, the latter represents the largest
fraction of losses.
CONCLUSIONS
According to the results obtained, it may be concluded that:
- During the entire composting period, the values of CO o of the material contained in the pile
composed of ground chicken carcasses and coffee husks were greater than those obtained in the
compost pile consisting of ground chicken carcass and sugarcane bagasse;
- There were significant losses of N in both the material collected in the compost pile containing
sugarcane bagasse (65%) as well as in the material of the pile containing coffee husks (68%).
However, during the composting process, the N loss was greater in the pile composed of
sugarcane bagasse than in that with coffee husks.
REFERENCES
[1] M.A.P Orrico Jr, A.C.A Orrico, J. Lucas Jnior, Compostagem dos resduos da produo
avcola: cama de frangos e carcaas de aves, Engenharia Agrcola, 30 (2010) 538-545.
[2] A.T. Matos, Tratamento e disposio final de guas residurias e resduos slidos. AEAGRI-
MG, DEA-UFV, Viosa, 2011.
[3] M.T. Pinto, Higienizao de lodos. in: Andreoli et al. (eds). Lodo de esgotos: tratamento e
disposio final, DESA-UFMG/SANEPAR, Belo Horizonte, 2001, pp.261-317.
[4] D.M Astoni, A.T. Matos, M.A. Sartori, N.C.L. Silva, R.T.P. Barros, F.A.R Luiz, Perda de carga
em ar forado em colunas de material orgnico com diferentes profundidades e estgios de
degradao bioqumica, Engenharia na Agricultura, 16 (2008) 238-247.
[5] M.A. Azevedo, Estudo e avaliao de quatro modos de aerao para sistemas de
compostagem em leiras. Belo Horizonte: Escola de Engenharia da UFMG. (Dissertao de
Mestrado) Universidade Federal de Minas Gerais, 1993.
[6] A.T. Matos, Prticas de tratamento e aproveitamento agrcola de resduos slidos. Associao
de Engenheiros Agrcolas de Minas Gerais. Departamento de Engenharia Agrcola da UFV. (Srie
Caderno Didtico n 45), Viosa, 2008.
[7] American Public Health Association; American Water Works Association; Water Environment
Federation (APHA; AWWA; WEF). Standard methods for examination of water and wastewater.
21th ed. Washington: American Water Works Association, 2005. 1368 p.
[8] E.J. Kiehl, Manual de compostagem: Maturao e qualidade do composto. E. J. Kiehl,
Piracicaba, 2002.
[9] S,M. Tiquia, N.F.Y Tam, Fate of nitrogen during composting of chicken litter. Environmental
Pollution, 110 (2000) 535-541.
447
MONITORING OF C/N RATIO ON COMPOSTING PILES OF CHICKEN CARCASSES,

GROUND AND NOT GROUND, AND OTHER WASTE GENERATED IN THEIR
PRODUCTION
1 2 3 4 5
E.C.R. Paiva , A.T. Matos , P.A.V. Lo Monaco , G.C. Ferres , D. L. Teixeira , S.A.A.
6
Baker
1 Professor at Civil Engineering Department, Federal University of Gois, Catalo, Gois,
Brazil.edcarlopaiva@yahoo.com.br
4 MSc. Student in Agricultural Engineering at Federal University of Viosa, Minas Gerais, Brazil.
gheilacf@yahoo.com.br
Viosa, Minas Gerais, Brazil. denisleocadioufv@yahoo.com.br
Viosa, Minas Gerais, Brazil. sandy.baker@ufv.br
ABSTRACT
The objective of this work is assess the influence of carcasses conditions (ground or not
ground) incorporated into piles of different beddings from broiler production facilities in
the C/N ratio of material in the composting process. The organic material was composted
in static piles with forced positive aeration (FPA) for a period of 90, being 60 days with
aeration and 30 days in a maturation bed. The treatments were: FPA 01 pile containing
of whole chicken carcasses, sugarcane bagasse and poultry litter, FPA 02 - pile
containing ground chicken carcasses, sugarcane bagasse and poultry litter. By means of
regression, mathematical equations were adjusted relating the concentrations of OCeo
and NTotal as a function of the composting time, and adjustment resulting in the coefficient
of determination greater than 70% was considered satisfactory. According to the results
obtained, it may be concluded that during the whole composting process, the OCeo
remained lower in the pile material composed with ground chicken carcass; there were
significant losses of nitrogen in both the organic material in which chicken carcasses was
incorporated into the compost pile in the ground form (65%) as well as in that in which the
carcass was incorporated in a non-ground form (70%).
Keywords: aerated static piles, ground chicken carcass, sugarcane bagasse, poultry litter.
INTRODUCTION
Together with the growth of production index, the concern about the effects of intensive breeding of
poultry on the environment is growing as well, especially regarding the generation and disposal of
waste produced (poultry litter and chicken carcasses).
According to [1], the disposal of these carcasses in the environment, without suffering any type of
previous treatment, can lead to serious chemical and microbiological contamination problems of
soil and water, which puts the quality of life around production plants at risk.
Because environmental legislation, both state and federal, have established strong requirements
regarding the handling and disposal of waste generated, either due to health or environmental
issues, it is important to develop techniques for final treatment/disposal of residues generated by
the poultry industry, especially carcasses of dead animals.
To minimize health and environmental risks of organic waste, especially those not contaminated
with chemicals, heavy metals or other toxic substances, the usual solution is composting and its
subsequent incorporation into the soil, in order to utilize the product in agriculture. Composting of
448
dead animals carcasses is presented as technical and environmentally appropriate in the handling
of these wastes. According to [2], composting of poultry carcasses is not only a low-cost
technology, but above all, has proven efficiency as a proper way to dispose waste, in the
environment, dead animals during the growth period in broiler chicken sheds, providing the
recycling of nutrients.
The relationship between the concentration of carbon and the nitrogen (C/N) is a variable of
paramount importance in monitoring the composting process, since the proportion in which they
are found can be used to estimate the level of material degradation. Among the factors that affect
composting, can highlight the particle size, whereas according to [3], influences the aeration of the
mass, as well as being directly associated with the degradation rate and shorter time of organic
material composting.
There is little information available on the rate of decomposition of organic material composted in
various forms, especially in tropical conditions. This information is necessary for optimization of the
composting process. Therefore, the objective of this study was to evaluate the influence of
carcasses conditions (ground or not ground) incorporated in piles of beddings from broiler
production facilities in the C/N ratio of the material in the composting process.
METHODOLOGY
The compost piles were composed of chicken carcasses, chicken litter and sugarcane bagasse.
The carcasses and poultry litter were obtained from farms integrated with agribusiness in the Zona
da Mata region of Minas Gerais, and sugarcane bagasse collected from farms located in the
Municipality of Paula Cndido, Minas Gerais, Brazil.
The organic material was composted in static piles with forced positive aeration (FPA), for a period
of 90 days, being 60 days with aeration and 30 days in maturation bed. The treatments were as
follows: FPA 01 pile containing of whole chicken carcasses, sugarcane bagasse and poultry litter;
FPA 02 - pile containing ground chicken carcasses, sugarcane bagasse and poultry litter, at the
proportion of 40% bagasse and 60% chicken litter by volume. The FPA 01 was composed of about
193 kg of chicken carcass, totaling about 635 kg of material to be composted and FPA 02 was
assembled with about 145 kg of ground chicken carcass, totaling about 480 kg of material to be
composted.
Grinding of the carcasses was done by placing about 10 to 15 whole carcasses in an appropriate
equipment for this purpose, referred to as the "Cutter." After loading the carcasses, the equipment
was turned on and then by simultaneous rotation of the propeller and the basin, the carcasses
were ground. The procedure was interrupted when the material had a pasty consistency with a
uniform aspect and the appearance of ground beef.
In the two Aerated Static Piles (ASP) air distribution systems were installed, consisting of
galvanized steel modulated pipe, where the part responsible for aeration of the piles has a
triangular shape (base = 10 cm and height = 10 cm) with holes measuring 1/8"in diameter, evenly
distributed, centrifugal fan ( HP electric motor power) with operation controlled by an analog timer
(accuracy of 15 minutes) and digital thermostat (accurate to 0.1 C)
The compost piles were built with approximately 2 m base, 1 m in height and 3 m in length. The
C/N ratio and pH were monitored every 15 days, during 60 days, and then in the last 30 days, on
the stage of maturation.
Monitoring began on the day in which the pile was mounted, referred to as day zero, and continued
during the first phase of the process (active phase) and later in the stage of maturation.
To restore the water content of the material during composting, water was added whenever its
-1
concentration fell below 55 dag kg . Temperature was monitored daily at three points situated at
the base, center and top of the piles, by type thermocouple probes containing sensors and a digital
thermometer.
The organic materials samples were taken from different points of the pile and then mixed together
to obtain a representative samples of the entire material. They were then sent to the Laboratory of
Soil and Solid Waste. It was quantified the concentrations of total nitrogen (NTotal) and organic
carbon easily oxidized (OCeo), and also in these samples the pH was measured (in water at a 1:5
ratio). The organic carbon easily oxidized (OCeo) was obtained using a methodology adapted from
the Walkley-Black process [4], and nitrogen by the Kjeldahl method [5]; and the pH measured using
a bench pH meter.
449
By means of regression, mathematical equations were adjusted using the program SIGMA PLOT
9.0 to relate the concentrations of OCeo and NTotal, as a function of composting time. Adjustment
resulting in the coefficient of determination greater than 70% was considered satisfactory.

Table 1 present the concentrations of Total-N, OCeo and pH in water, during composting period and
in Figures 1 and 2 are presented the graphs containing the regression equations that relate these
variables with the number of days of composting material in piles 1 and 2, respectively.
Table 1. Concentration values of NTotal and OCeo during composting period for the pile containing
sugarcane bagasse, poultry litter and whole chicken carcass (FPA 1) and ground (FPA 2)
FPA 1 FPA 2
Dias OCeo. NTotal OCeo NTotal
-1 pH C/N -1 pH C/N
---------dag kg ------- --------dag kg --------
0 67,74 4,91 - 13,79 67,74 4,91 - 13,79

15 29,26 5,08 6,32 5,75 16,47 1,84 7,45 8,95
30 30,59 3,46 8,59 8,84 27,71 3,07 9,15 9,02
45 29,00 3,11 9,31 9,32 26,59 3,15 9,01 8,44
60 26,87 1,5 8,59 17,91 23,53 1,61 8,57 14,61
90 25,44 1,4 9,15 18,17 25,40 1,68 9,25 15,11
A B
Figure 1. Values of concentration of Organic Carbon easily oxidized - OCeo - (A) and Total
Nitrogen - NTotal - (B) for the pile containing sugarcane bagasse, poultry litter and whole chicken
carcass (FPA 1).
450
A B
Figure 2. Values of concentration of Organic Carbon easily oxidized - OCeo - (A) and Total
Nitrogen - NTotal - (B) for the pile containing sugarcane bagasse, poultry litter and ground chicken
carcass (FPA 2).
According to what is presented in Figures 1A and 2A, the OCeo tended to decrease exponentially
with time of composting. The variation in the concentration of C in the composting process occurs
due to the action of microorganisms. In aerobic respiration, microorganisms use molecular oxygen
(O2) to obtain the most part of the energy from carbon sources, producing carbon dioxide (CO 2)
and water. It is noted, especially, that the OCeo in the organic material obtained when the whole
carcass was utilized (FPA 1) remained greater than the material obtained when ground carcass
was utilized (FPA 2), during the composting process (Table 1). This occurred because of the
chicken carcass, after grinding become more susceptible to decomposing microorganisms attack,
as well as to acquiring structure that facilitates handling, allowing greater homogenization of
moisture and aeration.
Similar to what occurred with the OCeo, there was an exponential decrease in the concentration of
NTotal in organic material with time in both compost piles (Figures 1B and 2B). This decrease is
common in composting with this type of waste, due to the low initial C/N ratio of the mixture and,
therefore, because the high concentration of NTotal at the beginning of the process. This fact,
associated to high temperatures and, especially, high pH values (Table 1), resulted in greater N
loss in the form of ammonia gas. The loss in the compost pile composed of whole ground chicken
carcass was of about 70% and in the compost pile consisting of chicken carcass was, of
approximately 65%. The pH may be considered one of the principal factors in determining losses of
N, since value above neutrality favors the formation of ammonia, resulting in greater reductions in
th
N content [6]. Thus, it is observed that from the 30 day of composting of the poultry litter mixed
with poultry carcass, the formation of ammonia was favored because the pH remained above 8.5.
[1] also observed significant losses of nitrogen (71.6%) during composting of poultry waste.
According to [7], losses begin with the hydrolysis of nitrogen compounds by microorganisms that
+ +
degrade Norganic, leading to the formation of O N-NH4 (ammonification). The N-NH4 formed is used
for microbial growth or the nitrification process, however, when presented in quantities greater than
those assimilated by microorganisms, it is lost to the atmosphere in the forms of nitrogen oxides
and ammonia, and the latter represents the largest fraction of the losses.
th
As can be observed in Table 1 the compost pile 2 presents larger losses of N-NTotal in the 15 and
th
30 days, when compared with the concentrations observed in the organic material collected in
compost pile 1. This fact can be explained according to two aspects, first, in compost pile 1, having
been assembled in the form of layers, the most abundant carbon sources (from the chicken litter
material) was further from the carcasses, thus remaining during the first 15 days, being
homogenized only after this period. The second aspect is that in compost pile 2, the increase in
specific surface of the material, provided by the grinding of chicken carcass, led to greater
microbial activity, favoring nitrogen availability and therefore the loss of that not assimilated by
volatilization.
451
CONCLUSIONS
According to the results, it may be concluded that:
- During the entire composting process, the OCeo remained lower in the material of compost piles
composed of ground chicken carcass;
- There were significant losses of nitrogen in both organic material in which the chicken carcass
was incorporated into the compost pile in the ground form (65%) as well as that in which the
carcass was incorporated in a non-ground form (70%).
REFERENCES
[1] M.A.P. Orrico Jr, A.C.A. Orrico, J. Lucas Jnior, Compostagem dos resduos da produo
avcola: cama de frangos e carcaas de aves, Engenharia Agrcola, 30 (2010) 538-545.
[2] M.S.S.M. Costa, L.A.M. Costa, A. Pel, A.C.J Silva, L.D. Decarli, U.F. Matter, Desempenho de
quatro sistemas para compostagem de carcaa de aves. Revista Brasileira de Engenharia Agrcola
Ambiental, 10 (2006) 692-698.
[3] J.T.Pereira Neto, J. T. Manual de compostagem processo de baixo custo. Viosa: UFV, 2007.
[4] A.T. Matos, Prticas de tratamento e aproveitamento agrcola de resduos slidos. Associao
de Engenheiros Agrcolas de Minas Gerais. Departamento de Engenharia Agrcola da UFV. (Srie
Caderno Didtico n 45), Viosa, 2008.
[5] American Public Health Association; American Water Works Association; Water Environment
Federation (APHA; AWWA; WEF). Standard methods for examination of water and wastewater.
21th ed. Washington: American Water Works Association, 2005. 1368 p.
[6] S,M. Tiquia, N.F.Y Tam, Fate of nitrogen during composting of chicken litter. Environmental
Pollution, 110 (2000) 535-541.
[7] M.A.P. Orrico Jr, A.C. Amorim, J. Lucas Jr, Perda de nitrognio e reduo de carbono orgnico
durante o processo de compostagem dos resduos gerados na avicultura de corte. In: Reunio
Anual da Sociedade Brasileira de Zootecnia, 41, 2004, Campo Grande. Anais... Campo Grande:
SBZ, 2004. 1 CD-Rom.
452
RECYCLING TURBOT FARM WASTE (SLUDGE) : COMPOSTING AND

VERMICOMPOSTING
1 1
Marcet P., Guerra A.2, Gonzlez S. ,Eiroa J.
1
rea de Edafologa. Escuela de Ingeniera Tcnica Forestal. Universidad de Vigo. Pontevedra ,
Espaa. marcet@uvigo.es.
2
Centro de Investigacins Marias (CIMA).
ABSTRACT
The aim of this work was to evaluate the feasibility of composting and vermicomposting
solid fish waste (manure) from commercial turbot farm with differents bulking agents and
the influence on the seed germination and vegetation (Eucalyptus nitens).
Selected waste mixtures pine sawdust + sludge (3:1) (compost 1), pine sawdust + fruit
waste + sludge (1:2:1) (compost 2), poultry litter+ sludge (1:3) compost 3), and wood
shaving + sea algae + sludge (2.5: 1.5: 1)(compost 4), were composted during four
months . At the end of this process, worms of type, Eisenia andrei and Eisenia fetida,
were added to compost, to initiate vermicomposting during a further two months (VC).
The produced vermicompost had a good nutrient value, low heavy metal content, low
soluble salts and high stability. The seed germination ability was the highest in presence
of VC1, CV2 (> 85%), however with VC3 and VC4 was very low (< 10%). Eucaliptus
nitens plants did not present stress for the application of the vermicompost.
The results obtained suggest that the addition of fish manure vermicompost may be
considered a good strategy to fertilize degraded soils, which could reduce the direct
risks of water pollution for the fish farming industry.
Keywords: turbot manure, composting, fish farming sludge
INTRODUCTION
In Spain, Galicia is the number one producer in aquaculture because of its quality and quantity,
leads in turbot production, as it produces practically 95 per cent of the almost 8,000 tonnes that
comprise the total volume. Galician producers contribute 95 per cent of the national turbot
production and 85 per cent of the European production. Aquaculture waste consists primarily of
soluble metabolic products as well as solids present in the form of faeces and uneaten feed. Waste
management strategy must consider several issues, including requirements for the storage and
disposal of wastes in an environmentally safe manner.
It is well known that the fish waste have been used as organic fertilizer and nutrients for both
agricultural purposes and for rehabilitation of degraded areas. Fish sludge contains macro and
micro nutrients, especially high levels of nitrogen and phosphorus. Sewage sludge mixed with
different organic waste materials is now usual in composting experiments [1,2,3]. Composting is a
generally accepted and high beneficial method of stabilizing the organic matter container in these
wastes. The composting kill the pathogens due to the heat generated during the thermophilic
phase; and the organic compositions in waste will be converted into stabilized humic substances
through mineralization and humification with a significant reduction in volume. An odorless,
innocuous and stable organic amendment can be obtained by composting, and its use for
improving soil structure and soil organic matter has been reported worldwide [4].
Compost and vermicompost made from fish manure or sludge from biofilter could provide an
effective source of nutrient-rich organic matter. Instead of creating a disposal problem, composting
these organic materials with a suitable carbon source creates a useful and potentially marketable
product [5].Considerable information is available about composting of biosolids, animal manures,
453
and municipal solid wastes, but it is limited in the case of highly decomposable materials such as
fish wastes.
The aim of this work was to evaluate the feasibility of composting and vermicomposting solid fish
waste (manure) from commercial turbot farm with pine sawdust, wood shavings, algae and poultry
manure as bulking agents and the influence on the seed germination and vegetation.

Sludge sampling was carried from commercial turbot farm located in O Grove, Ria of Arousa
(Insuia S.L.), which is the oldest one that produces this specie in Galicia. It generates 150t per
year and a effluent volume between 1,000 and 1,500 m/h, of which around 60 m/h are prefiltered
(with a rotary filter <200 microns). Sampling was carried out with the sludge which was sown in the
pool and others were collected from the rotary filter. Six samples of sludge were taken during two
years. The samples were stored in plastic containers and refrigerated until they reached the
laboratory (<4C) Sludge was analyzer for pH, OM, macronutrients, micronutrients, heavy metals,
pathogens, and electrical conductivity. Outside composting experiments were conducted at
Ponteareas (Pontevedra). The local climate is humid oceanic type, mean annual maximum
temperature is 19,7C and minimum 9,1C, precipitation concentrated mainly in winter, with dry
summers. Two different processes were employed composting and vermicomposting. The turning
3
pile system was used for the composting process, using piles of 1m and were placed in an open
site to facilitate turnings. Temperatures were measured twice a day, at 0.50 m depth with a
compost thermometer . The plastic box systems (30L) were used for vermicomposting. The boxs
were placed in an open site. Composting requires bulking agents in order to facilitate aeration and
provide carbon sources for microorganisms. Pine sawdust, wood shavings, algae and poultry
manure were used as bulking.
Selected waste mixtures pine sawdust + sludge (3:1) (C1, compost 1), pine sawdust + fruit waste
+ sludge (1:2:1) (C2, compost 2), poultry litter+ sludge (1:3) (C3, compost 3), and wood shaving +
sea algae + sludge (2.5: 1.5: 1)(C4, compost 4)- were composted during four months . The
temperature variations during this process followed the typical three-phase pattern. At the end of
this process, worms of type, Eisenia andrei and Eisenia fetida, were added to C1,C2, C3 and C4 to
initiate vermicomposting during a further two months (VC1, VC2, VC3, VC4). Vermicompost
samples was passed through a 2mm sieve and analyzed in triplicate for: pH, electrical conductivity
+4 3- -3
(EC), ammonium (NH ), nitrate (NO ), phosphate (PO4 ), total organic carbon (TOC), total N
(TN).
Compost pH and EC was measured in water extract, TOC and TN by elemental analysis (Leco CN-
2000), heavy metal total content by acid digestion and analyzing with ICP-OES (Perkin Elmer
Optima 4300 DV) for Cd, Cr, Ni, Pb y Zn and with AAS-CV (Varian SpectrAA-250 Plus) for Hg. The
+4 3- -3
NH , NO and PO4 were extracted using acidified calcium chloride solution (0.1 M), according
to the method developed by [6], and analyzing with a segmented-flow auto analyzer (Bran Luebbe-
AA3). Echerichia Coli was determined by membrane filtration (PNT/001) and immunoenzimtico
test (PNT/007) for determined Salmonella sp.
Lollium seeds germination were tested with five vermicompost: C1, C2, C3, C4, and C5
(commercial vermicompost).
Other experiment was installed using young plant of Eucalyptus nitens, grown in pots (degraded
forest soil +vermiculite+ VC1; degraded forest soil+vermiculite + VC2; degraded soil + vermiculite).
Degradated forest soil was sampling from Pontevedra (Spain), and collected from the top 30 cm.
Biomass, water transpired by the leaves, chlorophyll, chlorophyll fluorescence, leaves number were
evaluated.The plant material was sampled from Norton tree nursery (Pontevedra), plants in early
phase of growth (10-15 cm). The plants were placed in circular pots (15 x 15cm) with soil-
vermiculite (1Kg:50g) substrate and 50g of vermicompost (VC1 or VC2). Twuelve pots (one plant
per pot) for each vermicompost (soil+ vermiculite + VC) and twelve for control (soil + vermiculite),
were submitted to concrete conditions of lighting (120 photon mol/ms), temperature (20C),
humidity and aeration. The plants were previously conditioned in the laboratory (15 days). At each
sampling date (15, 30, 45, 60, 74 days), height, biomass, water transpired by the leaves,
chlorophyll, chlorophyll fluorescence, leaves number were evaluated.
454
Manure sampling was carried from commercial turbot farm in O Grove (Pontevedra) during two
years. Manure was analyzer for pH, OM, macronutrients, micronutrients, heavy metals, pathogens,
and electrical conductivity. Characteristics of fish manure are given in Table 1.
Results showed a very high water content in fresh fish manure, a organic matter content with
values around 33,8 %, and a neutral pH (7,5), total N content with values around 3% of which
>90% was in the organic form. Heavy metal content was much lower than upper pollutant limits
regulated by the European legislation. Electrical conductivity was very high (50, 55 mS/cm), the salt
concentration about 3,25%. The C:N ratio was very low (6,3).
Two different processes were employed composting and vermicomposting. The turning pile system
was used to composting process and vertical system in plastic box for vermicomposting.
The direct vermicomposting, with selected waste mixtures pine sawdust + fish manure (C1,
compost 1), pine sawdust + fruit waste + fish manure (C2, compost 2), poultry manure + fish
manure (C3, compost 3), and wood shaving + sea algae + fish manure (C4, compost 4), was not
feasible, Eisenia andrei and Eisenia fetida were added and after 24 hours, the mortality was 100%
due to high salt content. Therefore, an initial composting process was developed, with selected
waste mixtures (C1, C2, C3 and C4) during four months. Then, after composting process, a
vermicomposting process was conducted in C1,C2, C3 and C4, were inoculated with Eisenia
andrei and Eisenia fetida for two months.
Table 1. Characteristics of fish manure (dry weight basin)
-1 -1
Parameters Heavy metals [mg.kg ] Limit [mg.kg ]
water content [%] 85,7 0.7 Hg 0,093 0.01 16
pH (H2O) 7,56 0.04 Cd 1,21 0.1 20
%C 16,94 0.5 Cr 53,26 10 1000
% TN 2,59 0.08 Ni 29,67 0.6 300
% TOM 33,8 1 Pb 34,95 0.8 750
C/N 6,38 1 Zn 718,8 43,3 2500
3- -1
PO4 [mg.kg ] 550,0 27,4 Cu 68,67 3,24 1000
+ -1
NH4 [mg.kg ] 5,28 0.7
- -1
NO3 [mg.kg ] 2,51 0.3
EC [ms/cm] 50,55 1.6
% salts 3,25 0.03
Pathogens Salmonella absence
[ufc/100ml] E. coli absence
During composting process, physical changes were observed; volume, weight, odour and water
content. The thermophilic composting period lasted for approximately 20d in all cases; the time
which passed with temperatures over 55C was 48-54 h., time enough to satisfy requirements for
processes to further reduce pathogens. Characteristics of vermicompost (C1, C2) and compost
(C3, C4) are given en Table 2.
The results showed a important electrical conductivity decrease after composting and
vermicomposting process, C1 and C2 showed the lowest EC values (4,5 and 5,6 mS/cm), and C3
presents a slightly high value (8,06 mS/cm).
At the end of the compost and vermicompost processes, C2 an C4 had a similar neutral pH (7,13
and 7,27). However, C1 presents a pH value slightly low (6, 62), it could be caused by nitrogen
-
mineralization process; C1 had the highest NO3 content.
C/N ratio was higher than fish manure in composts, C1 had C/N slightly high (34,4), however C3
and C4 showed a C/N ratio of about 13-14.
The virtual absence of ammonium nitrogen in the final compost is a good indicator of their maturity
+
[3]. In this study the NH4 content, in the finals vermicompost and compost, was around 101, 186,
-1
703 and 285 mg.kg in C1, C2, C3 and C4, respectively. These facts were consistent with other
-1
reports; thus, [7] established that an ammonium nitrogen value below 400 mg.kg indicates mature
compost; this may indicate that the composting process of C3 was slower.
455
+
The concentration of NH4 was greater in the compost in comparison with fish manure. With
respect to nitrate, C1 and C4 are the vermicompost and compost which has a higher concentration.
Table 2. Chemical characteristics of vermicompost (C1 and C2) and compost (C3 and C4) (dry
weight basin). Mean (standard deviation). (EC: electrical conductivity; n.d.: not detected)
C1 C2 C3 C4
pH 6,62 (0,03) 7,13 (0) 8,065(0,07) 7,27(0,05)
-1
EC [mS.cm ] 4,78 (0,02) 5,06 (0,03) 12 (0,05) 7,04 (0,04)
N [%] 0,87(0,03) 1,54(0,06) 1,90(0,01) 1,04(0,32)
C [%] 29,9 (2,4) 37,22(0,2) 27,76 (0,25) 13,88(2,9)
OM [%] 59,8 (4,9) 74,4(0,4) 55,52 (0,5) 27,76 (5,8)

C/N 34,4 (2,6) 24,17(1,16) 14,61 (0,06) 13,58 (1,22)
+ -1
NH4 [mg.kg ] 342,6(38,89) 644,24(40,65) 703,04(19,7) 244,44(2,46)
- -1
NO3 [mg.kg ] 562,13(139,95) 212,07 (2,5) 21,12(3,37) 519,81(52,22)
- -1
NO2 [mg.kg ] n.d. n.d. 15,17(1,64) n.d.
3- -1
PO4 [mg.kg ] 110,42(1,23) 108,41 (3,63) 46,2(3,37) 109,98(2,74)
The seed germination ability was the highest in presence of VC1, CV2, CV5 (> 85%), however with
VC3 and VC4 was very low (< 10%) (figure 1).
Figure 1. Germination seeds for Lollium with five vermicompost: C1, C2, C3, C4, and C5
(commercial vermicompost).
Percentage seed germination
10
8 VC5
VC4
Days
6 VC3
VC2
4 VC1
0 10 20 30 40 50 60 70
% germination
The results obtained in the first Eucalyptus nitens sampling (to 15 days) do not present significant
differences in any of the measured parameters. The dates obtained in the next sampling (to 30
days) reveals significant differences in the height (CV1>CV2, Control), chlorophyll (CV1>CV2) and
transpiration (control>CV1). Chlorophyll showed significant differences between CV2 and CV1 in
456
the last sampling (75 days). Biomass results were not significant with any treatment. Eucaliptus
nitens plants did not present stress for the application of the vermicompost. (Figure 2).
Figure 2. Eucalyptus nitens development along 75 days: height and leaves number.
Height (cm)
40,00
35,00
30,00
25,00
control
cm
20,00 vermicompost 1
vermicompost 2
15,00
10,00
5,00
0,00
15 days 30 days 45 days 60 days 75 days
Leaves (n)
25
20
15
control
vermicompost 1
vermicompost 2
10
0
15 days 30 days 45 days 60 days 75 days
CONCLUSIONS
The material evaluated in this study was adequate for composting. The fish manure produced
compost with good nutrient value, low heavy metal content, low soluble salts and high stability. The
results obtained suggest that the addition of fish manure compost and vermicompost may be
considered a good strategy to fertilize degraded and forest soils, which could reduce the direct
risks of water pollution for the fish farming industry. Fish manure composting is a sustainable option.
The results suggest that fish manure vermicompost have a potential use as fertilizers in soils,
which could reduce the direct risks of water pollution from the fish farming industry.
The two vermicompost used did not produce any negative effect on the development Eucaliptus
nitens. There were no significant differences between CV1 and CV2 effect on the plants.
457
References
[1] G. Li ,F. Zhang ,Y. Sun ,J. Wong, M. Fang, Chemical evaluation of sewage sludge composting
as a mature indicator for composting process, Water Air Soil Poll. 132(2001) 333-345.
[2] L. Mupondi, P. Mnkeni,M. Brutsch, The effects of goat manure, sewage sludge and EM on the
composting of pine bark, Compost Sci. Utilization 14 (2006) 201 210.
[3] L. Roca-Prez,C. Martnez, P. Marcilla, R. Boluda, Composting rice traw sewage sludge and
compost effects on the soil-plant system, Chemosphere , 75(2009) 781-787.
[4] F. Laos, M. Mazzarino, I. Walter, L. Roselli, P. Satti ,S. Moyano , Composting of fish and
biosolids in northwestern Patagonia, Bioresource Technology 81(2002), 179-186.
nd
[5] E. Shelton, J. Hinshaw, S. Thompson, An evaluation of composted fish wastes. 2 International
conference on recirculating aquaculture, 1998.
[6] V. Houba, E. Temminghoff, G. Gaikhorst, W. Van Vark. Soil analysis procedures using 0,01M
calcium chlorhide as extraction reagent. Soil Sci. Anal. 31(9/10)(2000): 1299-1396
[7] F. Zucconi , M. De Bertoldo, Specifications for solid waste compost. Biocycle (1987) :
MayJune, 5661.
458
LOSS OF PRESSURE IN AIR BLOWN THROUGH DIFFERENT

THICKNESSES OF ORGANIC MATERIAL IN COMPOSTING
1 2 3 4 5
A.T. Matos , D. L. Teixeira , I. C. Corradi , I.C.A. Ribeiro , E.C.R. Paiva
Viosa, Minas Gerais, Brazil. denisleocadioufv@yahoo.com.br
Viosa, Minas Gerais, Brazil. Isabela.corradi@ufv.br
Viosa, Minas Gerais, Brazil. ivan.ribeiro@ufv.br
5 Professor at Civil Engineering Department, Federal University of Gois, Catalo, Gois,
Brazil.edcarlopaiva@yahoo.com.br
ABSTRACT
There is little information about the loss of static pressure when air is forced into piles of
organic material in composting, notably, in regards to the influence of biochemical
degradation stadium of the material. The Purpose of this work is to adjust the curves of
decreasing static pressure of the air, when forced into piles of organic material in different
thicknesses and two stages of biochemical degradation, to permit the calculation of the
fan power demand. The waste used for measurement of loss of air pressure were coffee
husks mixed with poultry litter, in proportion to enable initial C/N ratio between 20 and
30/1. It was verified that the loss in static pressure of the air increased linearly with the
thickness of the layer of organic compost and that there was an increase in static
pressure loss with the increase in specific airflow rates, which practically was not
changed by the biochemical degradation stadium in the composting material. If the layer
has a thickness of 1 m height, the power demanded by the ventilation system of the
-1 -1
organic material is 1.2 W t , in the material before the composting, and 2.4 W t , after 60
days of composting. In the case of material layer thickness is 2 m, the power demand
-1
increases to 17.7 and 21.7 W t , respectively.
Keywords: solids residues, composting, aerated static piles, aerobic process.
INTRODUCTION
Composting is a recycling system of nutrients and a way to accelerate the decomposition of
organic matter in relation to what would occur in the environment, improving the conditions of
microorganisms activity [1]. This process is one of the most efficient ways to recycle organic waste
in order to utilize the product in agriculture [2]. In this process, the reduction in the initial volume of
waste occurs, degradation of toxic substances, or pathogens, the biodegradable organic matter is
stabilized, and this way can be handled, stored and applied as organic fertilizer, without adverse
effects to the environment, provided that the appropriate dose is used [3].
According to [4], the aeration of the compost material can be made by manual revolving (Windrow
process) or aerated static layers, therefore in the last process, fans are used, which require
-1 -1
approximately supply of 1200 m3 h t of dry organic material in composting, demanding fans of
3
370 to 1500 W. [5], to meet the oxygen demand, is recommended 0.3 to 0.6 m of O2 for each kg of
volatile solids. Considering the concentration of oxygen in the air of 22% (in volume) and that the
-1
concentration of volatile solids in the material is of 80 dag kg , would have a range of
3 -1
recommendation 71 to 142 m h of air for each ton of dry organic material.
Considering that the costs of acquisition and operation of the fan are directly related to its power,
and that this is a function of air flow, static pressure and efficiency of the ventilation system,
459
becomes important the study of the variations that influence the power demand of the equipment.
The static pressure is determined, conventionally, by means of equations or graphics relating the
loss of pressure per unit of layer thickness of the product (pressure gradient) with the specific
airflow (air flow rate per unit area).
According to [6], the pressure loss due to the passage of air through any product depends on the
specific flow, shape and characteristics of the product, the amount, size and configuration of the
voids and the thickness of the product column.
In this work, the objective was to adjust curves of static pressure loss of the air, when forced into
layers of organic material, with different thicknesses and two stadiums of biochemical degradation,
in order to enable the calculation of the power demand of the ventilation system.
METHODOLOGY
The experiment was conducted at the Experimental Area of Hydraulics, Irrigation and Drainage,
Department of Agricultural Engineering UFV, Viosa, State of Minas Gerais, Brazil. Waste used
for measurement of air pressure loss were coffee husks mixed with chicken litter, in proportion to
obtain initial C/N ratio between 20 and 30/1, and the same material, after submitted to composting
in a system of aerated static piles, during 60 days.
For measurement of pressure loss through the mass of material, it was used a prototype, as
illustrated in Figure 1, composed of the following components: (1) column of galvanized plate,
measuring 1.0 m high, with a diameter of 0.30 m; (2) plugholes for static pressure measurement,
represented by seven copper tubes (5 mm diameter), spaced 0.10 m vertically, around the column;
(3) floor drilled, consisting of plate with circular holes; (4) plenum chamber in galvanized plate,
whose dimensions are approximately: 0.52 m (length), 0.47 m (width) and 0.40 m high; (5) PVC
pipe, measuring 2.0 m in length and diameter of 0.20 m, used to inflate air from the fan to the
plenum; (6) homogenizer, for airflow standardization; (7) straight blades centrifugal fan, powered by
electric motor with power of 735 W on 3,415 rpm; (8) fixed diaphragm air inlet, to allow variation in
flow.
Figure 1. Sketch: prototype scheme used for determining the static pressure gradient in different
specific airflow rates.
The filling of the column of galvanized plate was conducted, placing successive layers of material
with a thickness of 0.20 m, followed by a period of one night to place a new layer of material to be
completed until a 1 m thickness layer was filled up, and with static pressure measurements being
made in the vertical position of 1 m.
To measure the static pressure in the plenum chamber, a digital manometer was used and to
measure air velocity, it was used an anemometer blades. The air flow was obtained by the result of
the multiplication between the average velocity of the air and cross-sectional area of the exit duct.
During the measurements of air velocity, to achieve the measurement sensitivity of the device, was
460
used a cone with a reduction in diameter for the passage of air, where the anemometer was
positioned.
Measurements of static pressure loss, in different positions in the layer of material were made with
three repetitions, in the plenum and at every 0.10 m thick in the column, in both materials analyzed.
-1 -2
The specific flow rates used ranged from 0.045 to 0.159 m3 s m .
Using linear regression, equations of pressure loss were adjusted as a function of the depth of the
layer of material, using the program Statistica.
Based on the adjusted equations, were calculated the power absorbed by the fan, using Equation 1,
in the case of aeration of material piles, before and after composting.
PxQ (1)
Pot =

where,
Pot = electrical power absorbed by the fan (W);
P = total pressure supplied by the fan (Pa);
3 -1
Q = air flow (m s );
= fan efficiency (dimensionless).

Figure 2 shows, the curves of loss of air pressure in flow, as a function of thickness of the layer of
husks of coffee mixed with poultry litter, before the start of composting process (A) and after the
material has been composted (B).
A B
Figure 2. Variation in the loss of pressure of the in the column of coffee husks mixed with poultry
litter, evaluated before the composting (A) and after composting (B), under different specific flow.
It was verified a linear increase of loss of air pressure with the thickness of the material layer through
which the air was forced to flow, both in the material that passed through the composting process
and for the material that did passed through that process. Moreover, an increase in the slope of the
curve was verified, in other words, higher pressure gradient with the increase in specific airflow.
2
Table 1 shows the adjusted curves and their respectively coefficients of determination (R ) to the
equations of pressure loss as a function of the thickness of the material layer. It is verified that the
adjusted equations were similar for the two materials, independent of biochemical degradation stage.
461
Table 1. Equations adjusted for loss in pressure (Pa) as a function of thickness (H) of the layer of
coffee husks mixed with poultry litter, before the beginning and at the end of the composting process,
for different specific flows (Qa).
3 -1 -2 2
Qa (m s m ) Equation R
before the beginning of the composting process
0,045 1,5627. H - 0,2026 0,676
0,076 4,6524. H - 0,4902 0,961
0,101 8,5087. H - 1,0719 0,959
0,129 13,720. H - 1,4574 0,993
0,144 17,219. H - 1,6079 0,994
0,159 21,016. H- 2,2157 0,996
End of the composting process
0,045 1,3726.H - 0,1176 0,823
0,076 4,0286. H + 0,1176 0,914
0,101 7,6234. H + 0,1895 0,974
0,129 13,476. H - 1,0000 0,991
0,144 17,136. H - 1,0135 0,996
0,159 21,313. H - 1,8889 0,994
3 -1 -1
Considering the application of 1200 m h t [4] and calculating the demanded power (assuming
fan efficiency of 60%) for aeration of organic material studied in this work (thickness layer of 1 m )
-1
were obtained, respectively, the values of 1.2 W t for material before it is submitted to composting
-1
and 2.4 W t to the composted material, if you use 2 m thick layer of material, the power demands
-1
become, respectively, 17.7 and 21.7 W t . Considering the specific flow rate recommended by [5],
3 -1 -1
which is 71 to 142 m h t , in other words, 8 to 17 times lower than recommended by [4], it would
-1
have a demanded power ranging from 0.001 to 0.003 W t , which would give a power of 400 to
800 times smaller. The values obtained in this work are, however, lower than those obtained by [7],
3 -1 -1
considering the flow of 1200 m h t , which obtained, for aeration of 1 m thick layer of material
-1
with 30 days of composting, demanded power of 44.2 W t . If the layer thickness was 2.0 m, the
-1
power demanded would be 63.3 t W . If the material has 90 days of composting, the authors report
-1 -1
that would be required 278 W T , to 1.0 m thick layer, and 361 W T to 2.0 m. These values are
-1 -1
lower than reported by [4], which was 820.6 W T (1.1 HP t ). The variability of the values found,
considering the different authors, suggests that, among other issues, the calculation of the power
demanded by the fan must vary with the type of waste and its characteristics (size, shape, water
content), beyond environmental factors such as room temperature, air relative humidity, among
others. In addition, one should consider if the demand of air will be to meet the oxygen demand, to
control the piles temperature or for water removal, the latter being a very common referential in
composting of sewage sludge. According to [8], the demand of air to control the temperature in the
pile is about 9 times higher than that needed to meet the demand for oxygen.
CONCLUSIONS
Based on the results obtained in this experiment, it may be concluded that:
- The loss in static air pressure increased linearly with the thickness of the layer of organic
compost;
- There was an increase in the loss of static air pressure with the increase in specific airflow rate,
and materials (compost assessed before and after the composting was performed) presented
similar behavior;
- If the layer has a thickness of 1 m in height, the power demanded by the ventilation system of the
-1 -1 -1
organic material is 1.2 W t , in material before the composting, and is 2.4 W t , after 60 days of
composting. In the case of the thickness layer of material is 2 m, the power demand increases to
-1
17.7 and 21.7 W t , respectively.
462
REFERENCES
[1] M.A.P Orrico Jr, A.C.A. Orrico, J. Lucas Jr, Compostagem da frao slida da gua residuria
de suinocultura, Engenharia Agrcola, 29 (2009), 483-491.
[2] P. Torres, A. Perez, J.C. Escobar, I.E. Uribe, R. Imery, Compostaje de bioslidos de planta de
tratamiento de guas residuals, Engenharia Agrcola, 27 (2007) 267-275.
[3] A.C.A Orrico, J. Lucas Jr, M.A.P. Orrico Jr, Caracterizao e biodigesto anaerbia dos dejetos
de caprinos, Engenharia Agrcola, 27 (2007) 639-647.
[4] M.T. Pinto, Higienizao de lodos. in: Andreoli et al. (eds). Lodo de esgotos: tratamento e
disposio final, DESA-UFMG/SANEPAR, Belo Horizonte, 2001, pp.261-317.
[5] J.T. Pereira Neto, J. Manual de compostagem, Processo de baixo custo ed. Revisada e
aumentada. Viosa, MG: Ed. UFV, 2007.
[6] N.C.L Silva, A .T.Matos, M. Sartori, D.A. Moreira, R.T.P Barros, F.A.R. LUIS, Variao na
presso esttica de ar insuflado em diferentes vazes especficas em colunas de material orgnico
com diferentes estdios de degradao bioqumica, Acta Scientiarum. Agronomy, 30 (2008),165-
170.
[7] D.A. Moreira, A.T. Matos, M. Sartori, N.C.L Silva, R.T.P , F.A.R, LUIS, Perda de carga no fluxo
de ar forado em colunas de material orgnico com diferentes profundidades e estdios de
degradao bioqumica, Engenharia na Agricultura, 16 (2008), 238-247.
[8] C.T. INCIO, P.R.M. Miller, Compostagem: cincia e prtica para gesto de resduos
orgnicos. Embrapa Solos. Rio de Janeiro, 2009.
463
THE EFFECT OF SOIL ON HOME COMPOSTING

1 2 3
M. Roig-Planasdemunt , E. Rud-Payr and R. Torres-Castillo
1 IDAEA, CSIC, Jordi Girona 18-26,08028 Barcelona, Spain. maria_rp87@hotmail.com
2 Chemical Engineering Department, University of Barcelona. Mart i Franqus, 1, 6. 08028
Barcelona, Spain. elisabet.rude@ub.edu
3 Chemical Engineering Department, University of Barcelona. Mart i Franqus, 1, 6. 08028
Barcelona, Spain. rtorres@ub.edu
ABSTRACT
This study was designed to broaden the knowledge of the latest generation of home
composters. These composters are sold with a basis, so the compost material is not in
contact with the ground. Two composters with the base and two composters on a red clay
soil, typical of the Mediterranean, were used for this purpose. The four composters were
fed daily for 116 days with organic waste materials from the University of Barcelona and
then were left to evolve without feeding. OFMSW of a bar, grass clippings and pruning
crushed of a garden were added in equal amount to four composters. The bulking agent
was added gradually from 0 % in the early days up to 5 % at the end of the feeding
period. Natural and artificial rain was combined to achieve the typical rainfall in the
working area. The weight, moisture, temperature and height of the material, the level of
odour (as nuisance), some pathogens and C/N ratio of the resulting material were
measured. The agitation was carried out once a week. No significant differences were
found between the two concepts. Significant reduction in odours was obtained when a
5 % of bulking agent was used.
Keywords: Composter, Home composting, Soil, Bulking agent, Odours.
INTRODUCTION
Traditionally, farmers have composted their organic waste in piles directly on land, in order to
obtain a useful product for enriching the soil. Nowadays, this product is known as compost. This
natural fertilizer is stable, free of pathogens and weeds seeds [1]. Moreover, it is obtained by
means of a biological process which reduces the volume and mass of solid organic waste [1,2].
The composting process can be made at industrial level or at domiciliary level. In the industrial
process conditions must be controlled whereas in home composting the process is most simple
and it does not need so much attention.
Nowadays, the Directive 1999/31/CE [3] force the population to reduce the organic fraction from
municipal solid waste (OFMSW) managed in landfills or public dumps. It has promoted different
waste treatment techniques like home composting, as a preventive action with great environmental
value for municipalities. Home composting reduces the quantity of waste that must be collected,
transported and managed at treatment facilities. In fact, it is one of the main prevention measures
for the OFMSW established by the Municipal Waste Management Program of Catalonia [4], where
the interest of the population to manage organic waste has increased [5]. In 2011 approximately
17,500 composters were handed over in 383 municipalities of Catalonia [6] with a population of
7,535,251 habitants [7]. The high demand of home composters and the scarce available
information have aroused the interest in study of the urban waste management process.
Usually it is assumed that the organic wastes must be directly in contact with soil in order that the
composting process works properly. However, in the industrial processes the organic matter is not
in touch with the ground. Thus, the main objective of this work has been the study of the influence
of the contact with soil on the composting process.
464
Materials and methods used in this work are described in this section.
Site and composter characteristics

Four units of the COMBOX 300 composter, supplied by Compostadores.com, were used in this
study. This home composter is consisting in two 150 L units that form a vertical structure.
Moreover, it can be isolated from the ground by means of a plastic basis provided by the supplier, if
its necessary. The four composters were located in the experimental area on the campus of the
University of Barcelona (UB) at the longitude 2644 E and latitude 412259 N, from October
2010 to March 2011, during 150 days of experimentation.
The soil of this campus is polygenic, resulting from the transport and sedimentation of alluvial
material from the Collserolas Range and surroundings during the quaternary [8,9]. It is the typical
Mediterranean red soil; it has a loamy sandy texture. The surface layer (20 cm) is 15 % clay, 7 %
calcium carbonate, 1.2 % of organic matter, with a pH of 7.4 and C/N ratio of 7:1. Moreover, this
soil has significant properties like high water retention, due to fine texture and moderate drainage.
Therefore, if the soil exerts some influence on the composting process, the effect will be magnified
by high soil humidity.
Experimental design
As it can be seen in Fig. 1, in order to
evaluate the effect of soil in a home
composting process, the organic waste of
two composters was in contact with soil
(S1 and S2) while the other two
composters were isolated from the soil
(P1 and P2) by means of the plastic
basis. All the composters operated at
same conditions; the only difference was
the contact or not with the soil. The
composters were fed the first 116 days of Fig. 1. Composters S and P.
a total of 150 that lasted the entire
experimental period.
From the pluviometrical data collected by the Department of Astronomy and Meteorology of the
UB, it was estimated that during rainy periods, the monthly rainfall for the zone in which
2 2
composters operate was of 80 L/m , with a peak of 40 L/m . If there was not rain during the study
2
period, then the top of the composter and the surrounding area (a total of 1 m ) was irrigated with a
sprinkler to simulate rain and keeping the soil in the same conditions as if it had rained. The
2 2
simulation included the monthly average of 80 L/m , and the peak of 40 L/m . Table 1 shows the
total water added.
Moreover, other actions were established: the addition of Organic Kitchen Waste (OKW), grass and
bulking agent and the aeration. All the composters were managed and fed in the same way and
quantities. To weight the added material a Digital Scale A&D EK-6000i was used.
Table 1. Amount of organic matter and rain (natural or simulated) added to composters and experimental periods.
Added Material [kg] Rain [L] Experimentation periods [Days]
OKW 162.0 Natural 289.2 Feeding 116

Grass 40.9 Simulated 112.0 Non-Feeding 35
Total OFMSW 203.7 Total 401.2 Total 150
Total bulking agent 10.3
Total 214.0
OKW= Organic Kitchen Waste; OFMSW= Organic Fraction from Municipal Solid Waste.
465
The composters were fed with 1-3 kg/day of OKW, provided by a canteen of the UB, which serves
300-400 menu/day. The OKW was added only in the working days and its average bulk density
3
was 620 90 kg/m . Also, occasionally, depending on the availability, grass cuttings from the
University Campus garden was added. Bulking agent was obtained from pruning of the Faculty of
Chemistry garden, at the UB. The branches were crushed with a bio-grinder Bosch Rapid 2200 to
3
sticks 3 cm long, giving a bulk density of 160 60 kg/m . It was added in a proportion of 1-5 % of
the OFMSW to produce a porous matrix that helped decomposition by facilitating the air flow along
the composting mass. Table 1 shows the amounts of OKW, grass and bulking agent added to the
composters.
Once a week, the composting material was stirred with a manual aerator in order to avoid the
anaerobic zones and the consequent production of unpleasant odours. When the composter was
fed with grass cuttings, it was also aerated to homogenize the whole material.
To evaluate the effect of soil in the composting process several operating parameters were
monitored: temperature, moisture, weight, pathogens and C:N ratio of the material, and odours and
temperature of the environment.
Temperature measurement was performed using temperature probes connected to data loggers
EJ-2E-C-16L LOGGER 2 LCD that take a measure each 30 minutes. The probes were located at
of composting mass height. In addition, a portable digital thermometer VENTIX 5989M was used
once a day to contrast the measure of the probe. The environmental temperature was provided by
the Department of Astronomy and Meteorology of the UB. Moisture was measured, once a week,
through the weight loses gravimetric technique at 105 C [10]. Odours occurred were daily
measured and classified depending on the type and intensity. Four odour types were considered:
Decomposition, Putrefaction, Ammonium and Earthy. For odour intensity, the following numerical
scale was used: 0 (absence), 1 (low), 2 (medium) and 3 (high). The odour from composters was
measured with and without cover. Once a week, all the composters were weighed using a
Dinamometer (Gram Precision S.L., model CR-200) hanged in a metallic structure and supported
in a pulley system (Polipast Hinalifting, 1,000 kg) and a rope tied to the composter which allows
raising the composter.
At the end of the experimental period, representative samples were taken to determine the C/N
ratio and the presence or not of Escherichia Coli and Salmonella. spp. The C:N ratios were
analyzed in The Centres Cientfics i Tecnolgics (CCiT) of the UB, by combustion in the standard
conditions recommended by the analyzer manufacturer. The instrument was an elemental analyzer
EA-1108 C.E. of Thermo Fisher Scientific. E. Coli and Salmonella. spp. were analyzed in The
Agroambiental Laboratory Applus Agroambiental S. A. from Lleida. The former, by the planting
method and TBX Chromogenic plate count [11] and the latter using the VIDAS immunoassay.

th
The evolution of temperature inside the composters was erratic until the day 40 . It was evolved
depending on environmental temperature. Since then the temperature rise (Fig. 2). This change
was produced because the critical mass (about 55-60 kg) had been attained in the composter.
From this mass the produced heat was lost at lower speed. This behaviour was observed in both
composting systems. Moreover, when amounts exceeding 4 kg of grass cuttings were added the
material temperature suddenly rose to values close to 50 C. If this value is maintained during
enough time, it aids to reduce or eliminate the possible agents that can constitute a health risk to
humans and animals [12]. Another observed influence was that heavy rains have affected the
temperature, which decreased due to the entry of cold water inside the composter. However, the
process was not significantly affected by the aeration actions. Along the final period, without
feeding, the temperature of the material went down approaching it to the room temperature.
As it can be seen in Fig. 2, the temperature evolution of S and P composters were very similar but
some day there were differences of about 10 degrees. These differences were caused by entries of
rain, different in each composter. The fact indicates that home composters are not yet prepared for
hard rain conditions and the user must provide it some type of protection. On the other hand, as
Table 2 shows, the mean temperatures of S and P composters were not really different. Even, the
maximum difference between replications was 3.4 C.
466
Fig. 2. Evolution of the daily mean temperature of composters S (Tdm, S) and P (Tdm, P), and of
environmental daily mean temperature (Tdm, ENV). Amount of grass added (upper graph).
Different authors [1,13,14] pointed out that moisture is the key parameter to control the efficiency of
the decomposition and that they should be around 40 - 60 % to avoid problems, especially those
related with odours. During all the experimental period the moisture was higher than 50 %, so that
no action to make it rise was required. The four composters followed the same pattern with regard
to moisture. However, on day 85, an entry of rain water was registered in P2 composter. This entry
was much higher than the respective entry at the other composters. From this day on, the moisture
in P2 composter was always the highest and was about 80 %. This is the reason why Table 2
shows a higher value in the mean moisture of P2 composter.
Table 2. Mean values of temperature and moisture for the 150 days and final values for C/N ratio and pathogens
Parameter S1 S2 S P1 P2 P
Temperature [C] 29.36 30.10 29.73 31.15 29.56 30.36
Moisture [%] 62.29 57.27 59.78 59.54 72.01 65.78
Final C:N ratio 8.9 8.4 8.7 8.7 10.6 9.7
E. Coli and Salmonella Ab Ab Ab Ab Ab Ab
Ab: absence or less than 10 cfu/g
467
The last day of operation, after 35 days without feeding, the material was not stable in any
composter yet. But, as has been shown in Table 2, this material had a good C/N ratio and was free
of investigated pathogens (E. Coli and Salmonella. spp.). Excluding the composter P2, which has
suffered the water input, Table 2 shows that there were no significant differences in the
characteristics of the material after 150 days of operation.
As it can be seen in Fig. 3 (a) when composters were fed, the mass was increasing. In the last 40
days of feeding period, the mass in the composters remained relatively constant, so that the
composting process was freeing a total matter amount similar to the added food. Afterwards, when
feeding was stopped (from day 116th), a slow fall in composters matter was produced by the
microorganisms action. The major part of the weighty loss was due to the loss of water [2]. But at
the end of the experimental period, mass reduction was very similar in both systems: 72 % at S
composters and 73 % at P composters; both measured at moisture of 60 %. The weighty difference
observed in Fig. 3 (a) was due to the rain entry in the composter P2 that was mentioned before.
The same figure shows that both weight curves were being slowly approaching due the
evaporation of this excess of water of the composter P2. Again, these results indicated that the soil
has no significant influence on the operation of the process.
(a) (b)
Fig. 3. (a) Total OFMSW added to the composter and the evolution of composters remaining mass. (b) Relation between
the added bulking agent and the liberated odours. The real points of odour intensity (integers) have been slightly
displaced to avoid their overlapping.
As one of the major complaints received by waste agencies is the production of odours in the
composting process [5], attention has been paid to such problem. Fig. 3 (b) shows the estimated
odour intensity for both types of system and the bulking agent added to all composters as
percentage of the OFMSW (discontinuous line). In general, decomposition was the predominant
odour as is usual in a composting process. Occasionally, other unpleasant odours such as
ammonia or putrefaction were smelt. It can be seen that when bulking agent was lower than 1 %
approximately, the odour was higher at the composters S. Very unpleasant odours were generated
by both types of composter while providing scarce bulking agent. By increasing the bulking agent
fraction the level of odour remained relatively constant, until bulking agent reached about 5 % by
weight. From this data, the odour level began to decrease in all composters and the operation was
more comfortable. Thus, 5 % of bulking agent was the most efficient solution to control the odours
among all the tested values. As were appointed by previous authors [1,2] the bulking agent gives
structure and porosity to the mixture and this fact aided to correct the moisture excess. In this field
of odours the contact with soil was not shown decisive again.
CONCLUSIONS
The objective of this work was to test if contact with soil affects home composting process of the
OFMSW. This effect was not identified with the different operation parameters monitored. So, it can
be concluded that, in typical Mediterranean red soils, the home composters has no need the soil
contact to operate properly. Moreover, the results showed that it was necessary to reach a
minimum mass (about 55-60 kg in this work) to ensure a suitable bio-reaction rate and to increase
the temperature. The addition of significant amounts of grass cuttings (4 kg in this study) also has
468
proved quite effective in increasing temperature. The entry of rainwater inside the composter
should be avoided. A minimum addition of 5% of bulking agent, by weight of the OFMSW, has
been required to properly control moisture and to observe a significant reduction in unpleasant
odours.
ACKNOWLEDGEMENTS
The authors appreciate the assistance of Jordi Polonio of the University of Barcelona and the
financing of the Entitat Metropolitana dels Serveis Hidrulics i del Tractament de Residus
(EMSHTR) of Barcelona, Spain.
REFERENCES
[1] R.T. Haug, The practical handbook of compost engineering. Boca Raton, Florida: CRC-
Press (1993) pp.717. ISBN 0-87371-373-7.
[2] B.K. Adhikari, S. Barrington, J. Martinez, S. King, Effectiveness of three bulking agents for
food waste composting. Waste Management, (2009), 29, pp.197-203.
[3] EU Directive 1999/31/EC. Official Jounal of the European Communities, L 182, 26/06/1999.
[4] Generalitat de Catalunya, Municipal waste management program of Catalonia 2007-2012
th
(PROGREMIC), approved by Decree 87/2010 of 29 June, DOGC, 5664, (2007), pp. 51,
919-951.
[5] EMSHTR, Entitat Metropolitana dels Serveis Hidrulics i del Tractament de Residus.
Personal communication of Division Head of Waste Prevention. (2010).
th
[6] ARC, Agncia de Residus de Catalunya. Information on http://www.arc.cat. [Visited on 15
ot June of 2011].
[7] IDESCAT, Institut dEstadstica de Catalunya. Information on http://www.idescat.cat.
th
[Visited on 10 ot July of 2011].
[8] L. Sol-Sabars, Ensayo de interpretacin del cuaternario barcelons. Miscelnea
Barcinonencia, II: 7-54, Barcelona (1963).
[9] T. Sauras, R. Vallejo, R. Simmonneau, and M. Berbel, Prelimary studies on a
Mediterranean soil and the site climatic conditions for the EURO-RESSAC project. Report
of contract CEC-CIEMAT SC-008-E/BI6-0122-F, (1992), pp. 1-42.
[10] APHA, AWWA and WEF, Method 2540B. Standard Methods for the Examination of Water
th
and Wastewater. 20 Edition, APHA, Washington, DC. (1999).
[11] W.D. Watkins, S.R. Rippey, C.R. Clavet, D.J. Kelley-Reitz and W. Burkhardt, Novel
compound for identifying Escherichia coli. Appl. Environ. Microbiol. 54 (7), (1988), 1874
1875.
[12] M. De Bertoldi, Evolution of composting strategies of solid waste management. In:
Proceeding of ORBIT 2006 - Biological Waste Management. From local to global,
Germany, (2006), pp 25-30.
[13] H.A.J. Hoitink, D.Y. Tseng, J.J. Chalmers and O.H. Tuovinen, Characterization of a Bench-
Scale System for Studying the Biodegradation of Organic Solid Wastes. Biotechnol.
Progress, (1995), 11(4): 443-451.
[14] F. Miyatake and K. Iwabuchi, Effect of compost temperature on oxygen uptake rate,
specific growth rate and enzymatic activity of microorganisms in dairy cattle manure.
Biores. Echnol., (2006) 97: 961-965.
469
COMPARATIVE STUDY OF THE EVOLUTION OF WASTE GENERATION IN ERSUC

2005 TO 2008
1
S.M.M. Paixo
1 College of Health Technology of Coimbra - Rua 5 de Outubro, Apartado 7006 3040-854 Coimbra,
Environmental Health Department supaixao@estescoimbra.pt
ABSTRACT
The waste is transversal to all human activities in different ways. Sooner or later, all material placed
on the market become waste; all production processes generate waste, even the enhancement of
waste eventually generates waste. Therefore, the aim of this study is to analyze the evolution of the
quantities of waste from undifferentiated collection and collection of thirty-six counties that
constitute the Multi Municipal System of Coastal Centre, treated and sent for recycling by ERSUC
during the years 2005 at 2008.
There is, throughout these four years, a slight increase in the quantity of waste from
undifferentiated collection as well as a significant increase in waste from the collection. However, in
relative terms there is a tendency to stabilize the quantities of waste from undifferentiated collection
and a continuous increase in the collection. It is noted that the average per capita of thirty-six cities
studied, never fall in one kilogram and that of all cities, only six, Aveiro, Coimbra, Figueira da Foz,
lhavo, Ovar and Oliveira de Azemis represent over 50% of total MSW landfilled.
It should be noted also that in terms of number of containers for the selective collection, this goes
far beyond, for all three rows of waste (paper, cardboard, plastic and metal and glass) is the
predetermined ratio of one container for each five hundred inhabitants. Of all ranks, the glass is the
one that stands out in terms of amounts collected and sent for recycling.
KEYWORDS: municipal solid waste; undifferentiated collection; selective collection; evolution
INTRODUCTION
A sustainable economy and environment require the protection of natural resources through
reduction, reuse, recovery and recycling of used materials, thus avoiding as much as possible
waste of raw materials. Promote appropriate management of increasingly scarce resources is,
without a doubt, prepare a better future in this.
It is assumed as the main objective of this study about the evolution of urban solid waste
management in the Multi Municipal System of Coastal Centre the period 2005 to 2008.
The study population corresponded to the universe of municipalities that make up the waste
management company ERSUC and corresponds to the 36 municipalities that are part of it,
including: gueda, Albergaria-a-Velha, Alvaizere, Anadia, Ansio, Arganil, Arouca, Aveiro,
Cantanhede, Castanheira de Pra, Coimbra, Condeixa-a-Nova, Estarreja, Figueira da Foz,
Figueir dos Vinhos, Gis, lhavo, Lous, Mealhada, Mira, Miranda do Corvo, Montemor-o-Velho,
Murtosa, Oliveira de Azemis, Oliveira do Bairro, Ovar, Pampilhosa da Serra, Pedrgo Grande,
Penacova, Penela, S. Joo da Madeira, Sever do Vouga, Soure, Vagos, Vale de Cambra e Vila
Nova de Poiares.
RESULTS
Year of 2005
During the year of 2005, approximately 358.394 tonnes of MSW was received and processed in the
ERSUC landfills. In terms of per capita number of kilograms of MSW generated per inhabitant per
day, it are produced on average 1,01 kg.
470
The municipalities of Coimbra, Aveiro, Figueira da Foz, Ovar, Oliveira de Azemis and lhavo, are
the major producers of MSW, representing, in its entirety, about 55% of the total amount of MSW
processed in the system. These municipalities, in addition to being the most populated, are also
those with values per capita above 1Kg/inhabitant per day, together with Mira and Aveiro, these
late ones due to the beach season strong contribution.
In terms of selective collection, it was verified that it were collected 21.392 tonnes. With regard to
the equipment installed, the ERSUC made available to the residents, in 2005, 7.701 selective
collection containers, of which 3.580 are for glass, 2.094 for paper and 2.027 for packaging. Thus,
during this year, it were reached ratios of 263 inhabitants per glass collection container, 480 per
paper collection container and 510 per packaging collection container, exceeding the target ratio of
500 inhabitants per eco point.
As for the per capita numbers relating to each group, it can be verified that the greater adhesion of
residents to the selective collection is no longer as strongly influenced by the size and development
of each municipality, and there may be some less populous municipalities showing numbers per
capita similar to the most populous ones, especially for the group of glass.
Year of 2006
In 2006, 376.913 tonnes of MSW was gathered and processed in the three landfills belonging to
ERSUC, which means, in relation to the previous year, an increase of 5,17%, reflecting a
significant increase in the production of MSW by the municipalities that are part of the system.
In terms of per capita numbers, the Multi-municipality System as a whole presents an average of
1,06 kg of MSW per inhabitant per day, and it is possible to distinguish, as it was in the previous
year, the urban and rural character of each municipality, as well as the seasonality of some. It is
verified that there was a general increase in the values per capita, and in some cases, these
increases are between 10 and 20% over the previous year.
With respect to selective collection, 24.525 tonnes were collected, which means, in relation to the
previous year, an overall increase of 14,65%, being 10,39% of glass, 15,34% of paper and
cardboard and 37,29% in packaging, including the amounts being collected at the eco centres.
As for the installed equipment, the ERSUC made available to the residents, 8.348 selective
collection containers, of which 3.763 are for glass, 2.333 for paper and 2.252 for packaging. Thus,
if were reached the ratios of 250 inhabitants per glass collection container, 436 per cardboard
collection container and 458 per packaging collection container, exceeding, like it had happened in
the previous year, the indicative ratio of 500 inhabitants per eco point.
It was verified, again, that the per capita numbers for each group of recyclable materials and the
consequent adhesion of residents to selective collection, is no longer as strongly influenced by the
size and development of each municipality as it happens in the case of the undifferentiated
collection.
Year of 2007
In 2007, 399.816 tonnes of waste was obtained and processed in the infrastructures of ERSUC, of
which 372.986 were deposited in landfill, and the remaining 26.830 were valued and recycled,
representing a total of 6,71% in the universe MSW of the Coastal Centre. Compared with the
previous year, the total amount of waste has remained virtually unchanged, having been registered
variations at the level of selective collection, which grew 9,40%, and the decrease of 1,06% in
MSW, meaning that this increase was the result of the diversion of materials from containers of
mixed waste for the selective collection network supported by the eco points installed.
In terms of packaging waste sent for recycling, it was achieved an increase of 13,47% over the
previous year, not only due to the increased amounts selectively collected and received in eco
centres, but also due to increased efficiency and effectiveness of separation in sorting stations
since they were upgraded.
Of the thirty-six municipalities that comprise the system, only six municipalities (Aveiro, Coimbra,
Figueira da Foz, lhavo, Oliveira de Azemis and Ovar) represent 55% of the MW deposited in the
three landfills and they get directly in their infrastructures 70% of the generated waste, and the
remaining 30% are delivered by the municipalities at the six ERSUC transfer stations.
In terms of per capita numbers, the average is 1,047 kg per inhabitant per day. This represents a
decrease of 1,05% over the previous year. The larger municipalities with greater purchasing power
decreased or maintained their per capita numbers, while some of the most rural ones continued
471
their growth trends. It is worth mentioning the remarkable decrease in per capita numbers relative
to the municipality of So Joo da Madeira. As a general rule, municipalities with higher yields
decreased the amounts of MSW between 2006 and 2007, except for Oliveira de Azemis whose
productions have been consistently increasing over the past years.
The effect of the slowdown in the production of waste is not so visible in smaller and more rural
municipalities since, on average, the quantity of MSW has increased over the period under review.
One possible explanation relates to the largest number of eco points in the most populous and
more concentrated municipalities, allowing larger deviations of waste from landfills, due to the
effect of the size of these municipalities.
In terms of selective collection of recyclables, it appears that 26.830 tonnes were collected which
means, comparatively to the previous year, an overall increase of 9,40%, of which 9,05% in glass,
8,64% in paper and in cardboard and 13,47% in plastics and metals, including the amounts
collected in ecocentres.
The increases do not reach the outstanding figures of the past, since, as the quantities grow every
year, the basis for calculation is systematically larger, and it is not possible to maintain exponential
growth.
In terms of installed equipment, the ERSUC made available to the residents, in 2007, 8.003
selective collection containers, of which 3.921 are for glass, 2.499 for paper and 2.383 for
packaging, reaching a ratio of 237 inhabitants per glass selective collection containers, 397 per
paper selective collection containers and 416 per packaging selective collection containers.
The production of glass packaging, as expected, is dominated by municipalities with larger
populations. However, when analyzing the per capita numbers, it appears that some of the smaller
municipalities reach very interesting numbers per capita, either because they have more ingrained
habits of separation, either by the type of existing trade, particularly with regard to the restaurant
services, or by the large amount of floating population present in areas of the coast during summer.
So, in this group, half of the municipalities have higher numbers per capita than the system
average.
For the group of paper and cardboard packaging, it stands out the very high production in the
municipality of Coimbra, perhaps, in addition to the high population, because it has many
companies in the areas of trade and services. In terms of per capita numbers, this is skewed by the
high production of Coimbra, and only fifteen municipalities have higher numbers per capita than the
system average.
As for the plastic and metal packaging, the analysis is similar to that of paper and cardboard, with
the municipality of Coimbra dominating the production. At the level of numbers per capita, about
half of the adherent municipalities exceed the system average.
Year of 2008
In 2008, 403.276 tonnes of waste was received and processed in the infrastructures of ERSUC, of
which 375.942 were deposited in landfill, and the remaining 30.290 were valued and recycled,
representing a total of 7,51% in the universe of MW of the Coastal Centre. Compared with the
previous year, the total quantity of managed waste increased 0,87%, representing an increase of
0,79% of waste destined for landfills and an increase of 12,90% of recyclable waste collected.
The MSW destined for landfill were distributed among the municipalities that form the system, and
it can be inferred that, as had already happened, only six municipalities of the thirty-six (Aveiro,
Coimbra, Figueira da Foz, lhavo, Oliveira de Azemis and Ovar) represent 54% of the total MSW
deposited in the three landfills, and that they receive directly on their infrastructures 69% of the
generated waste, and the remaining 31% were delivered by the municipalities in the six ERSUCs
transfer stations.
In terms of per capita numbers, the Multi Municipal System of Coastal Centre as a whole has a per
capita average of 1,054 kg of unsorted MSW per inhabitant per day. This represents an increase of
0,63% over the previous year. In 2008 there are notable variations in per capita numbers in some
municipalities. These values can be explained by a set of factors, alone or together, as the
variation in the resident population, the variation in the tourism, more or less acceptance of the
plans made to raise awareness concerning the prevention of waste production, among other.
In terms of selective collection of recyclables, it appears that 30.290 tonnes were collected which
means, comparatively to the previous year, an overall increase of 12,90%, of which 10,56% in
472
glass, 10,34% in paper/cardboard and 31,47% in plastics and metals, including the amounts
collected in ecocentres.
In terms of installed equipment, the ERSUC made available to the residents, during 2008, 9.323
selective collection containers, of which 4.102 are for glass, 2.663 for paper and 2.558 for
packaging.
Thus, as it has been happening over the past years, it was exceeded the ratio of 500 inhabitants
per eco point, since there is 226 inhabitants per glass selective collection containers, 365 per paper
selective collection containers and 380 per packaging selective collection containers.
The production of glass packaging, as expected, is dominated by municipalities with larger
populations. However, when analyzing the per capita numbers, it is clear that some of the smaller
municipalities reach very interesting numbers per capita, either because they have more ingrained
habits of separation, by the large amount of floating population, with primary emphasis on the
summer months or by the type of existing trade.
Like the previous year, the municipality of Coimbra stands out both in the group of paper and
cardboard packaging and in the group of metal and plastic packaging, the probable reason being
that there are many companies in the areas of trade and services.
DISCUSSION
Next we will examine the evolution of waste, both from the undifferentiated collection or the
selective collection, during the four studied years.
Graph 1 - MSW vs. Per capita numbers

With regard to undifferentiated collection, as
can be seen in the following graph, it appears
that there has been a slight increase in the
amount of waste.
It should be noted that in 2006 there was an
increase in the quantities produced not
matched by, in the same order of magnitude,
the number of inhabitants, as evidenced by the
rise of per capita numbers.
With respect to the selective collection, it is

possible to verify through the following graph,
that the per capita numbers accompany the
positive evolution of the quantities of waste
Graph 1 - MSW vs. Per capita numbers collected selectively.
This fact is very positive because it

reinforces that the awareness campaigns
have reached their target audience and
that, consequentially, citizens are more
aware and involved in separating their
waste.
From the analysis of the next graph, it is
possible to see that there has been a
major concern of the company to make
available to citizens the adequate means
to facilitate the collection of waste that can
be sent for recycling. Thus, both for the
group of paper and cardboard and for the
plastic, metal and glass packaging, the
number of containers has been increasing
since 2006, exceeding for all three groups
the ratio that is defined for an eco point per
Graph 2 - Selective collection vs. Per capita numbers
500 inhabitants.
473
The group of glass, being the first to be dynamized in Portugal, stands out from others also in the
ERSUC.
Graph 3 Density Inhabitant / Equipment
In the following graph it is possible to see the evolution, in relative terms, of both the total of
selective collection and the total of undifferentiated collection, and there is a tendency to stabilize
the quantity of waste from the undifferentiated collection and a continuous increase in the selective
collection.
Graph 4 - Percentage of Collection
CONCLUSION
A sustainable economy and environment require the protection of natural resources through
reduction, reuse, valuation and recycling of used materials, thus avoiding as much as possible, the
waste of raw materials. Promote appropriate management of increasingly scarce resources is,
without a doubt, to prepare a better future during the present.
It is assumed as the main objective of this study, to analyze the evolution in the quantities of waste
from the undifferentiated collection and the selective collection of thirty-six municipalities that
constitute the area of the Multi Municipal System of the Coastal Centre, processed and sent for
valuation by the ERSUC during the years 2005, 2006, 2007 and 2008.
It was found that, in relative terms, there is a tendency to stabilize the quantity of waste from
undifferentiated collection and a continuous increase in the selective collection.
However the slight increase seen in the total amounts obtained for the undifferentiated collection is
supported by the authors Carapeto C. et al. (2001), when they consider that the habits of life, the
population growth, the economic and industrial development and the high advertising, have
contributed to increase the excessive and irrational consumption that is motivated by the wide
availability of products, resulting in a increment in waste production.
474
It can be seen that of the thirty-six studied municipalities, only six, Aveiro, Coimbra, Figueira da
Foz, lhavo, Oliveira de Azemis and Ovar represent over 50% of the total MSW deposited in
landfill.
As for the selective collection there is a positive evolution of the quantities of waste collected. This
evolution is the result of providing the means to carry out the selective collection, including eco
points that, during the years studied, exceeded the reference value which corresponds to the ratio
of one eco point for every five hundred inhabitants. According to Carapeto C. et al. (2001), for the
success of the selective collection, it is of utmost importance to make available to residents the
adequate resources.
This increase in selective collection strengthen the idea that the awareness campaigns have been
reaching their target audience and, consequently, that citizens are more aware and involved in
separating their waste, however this is only possible if the investment in effective public awareness
campaigns continues. According to Martinho & Gonalves (1999) the success of the selective
collection is mainly due to environmental awareness campaigns, carried out in order to change
attitudes and behavior in citizens, trying to convey that each one of us has an important role in
selective collection.
However it should be noted that recycling should be the last resort of the citizen, given that
attitudes must first pass through the reduction of waste production, then through a behavior of
reuse of the waste we produce until it can no longer be used and only ultimately recycling, so there
must be an increasing investment in the prevention of waste production.
REFERENCES
(1) APA (2011); Avaliao Ambiental Estratgica do Plano Nacional de Gesto de Resduos
Resumo no Tcnico; Disponvel em URL:
http://www.apambiente.pt/concursos/TGR/Documents/AAE_PNGR_RNT.pdf
(2) Levy, J.; Cabeas, A.; Resduos Slidos Urbanos Princpios e Processos; Lisboa;
Associao das Empresas Portuguesas para o Sector do Ambiente; 2006;
(3) ERSUC consultado no URL:
http://ersuc.pt/web/index.php?option=com_content&view=article&id=46&Itemid=54
(4) Carapeto, C. et al (2001); Educao Ambiental. Universidade Aberta, Lisboa.
(5) Martinho, M.; Gonalves, M. (1999) - Gesto de Resduos. Universidade Aberta, Lisboa
475
EVALUATION OF THE EFFECT OF SUCCESSIVE APPLICATION OF PAPER

MILL SLUDGE TO DEGRADED SOIL: A COLUMN STUDY
1,3 1 2,3
F. Gallardo , M.J. Flores and M.C. Diez .
1
Chemical Science Dept. University of La Frontera, Temuco, Chile. fgallar@ufro.cl
2
Chemical Engineering Dept., University of La Frontera, Temuco, Chile. mcdiez@ufro.cl
3
Scientific and Technological Bioresource Nucleus-BIOREN, University of La Frontera,
Temuco, Chile
ABSTRACT
Chemical properties of pulp mill sludge nutrient content and low concentrations of heavy
metals and organic pollutants suggest that this material may represent a valuable
resource as a soil amendment, improving soil fertility. We studied the effect of four
successive application of secondary pulp mill sludge on mobility of some elements
through the soil profile in a column study. Soil columns received the sludge in the range
-1
of 0 to 30 ton ha during one year with a regime of water of 1200 mm per year.
Pulp mill sludge presented a high content of organic matter (68%), macronutrients (N and
P) and micronutrients (Mn and Zn). The four successive addition of sludge to Freire soil
column caused an accumulation of organic matter, P and total N in the first 0-20 cm of
-
the soil column. The highest NO3 -N content was found at 40-60 cm depth and increased
-1
as the sludge application increased from 0 to 30 ton ha . On the contrary, the highest
+
NH4 -N was found in the first 0-20 cm fraction. Zn was accumulated in the first 0-20 cm
-1
fraction increasing from 0.7 to 5.5 mg kg with the increment of the sludge from 0 to 30
-1
ton ha .
Keywords: Sludge; degraded soils; column study.
INTRODUCTION
The biological treatment of wastewater in pulp and paper industry generates considerable amount
of sludge. Chemical properties of pulp mill sludge (high organic matter content, pH, buffer capacity,
nitrogen (N) and phosphorous (P) level, and low concentrations of heavy metals and organic
pollutants) suggest that this material may represent a valuable resource as a soil amendment,
improving soil fertility [1,2,3]. Its use in soils facilitates nutrient transport, increases water-holding
capacity and serves as a partial replacement for the most expensive chemical fertilizers [4].
In Chile, there are approximately 3.1 million ha of soil derived from volcanic ash (Andisol and
Ultisol), whose main characteristics are their high P fixation capacity and acid pH [5]. Therefore, the
incorporation of organic residues into soil can increase the bioavailability and accumulation of
available P [2], which will depend on the capacity that the residue possesses to reduce the
adsorption of P in the soil, on the contribution of different species of P [6,7] and of the
microbiological capacity to degrade compounds of P with the subsequent release of phosphate.
Nitrogen is a soil nutrient whose shortage most frequently restricts the crop growth. Pulp mill
sludge contains high nitrogen content that may undergo transformation into plant-available N
+ -
forms, either as ammonium (NH4 ) or nitrate (NO3 ). Ammonium is tightly bound by the negatively
charged surfaces of clay complexes and organic matter (O.M) thus being immobilized. By contrast,
nitrate with a negative charge can readily be lost from negatively charged soils [8,9].
476
Despite the beneficial effects of the application of sludge in the soils, some considerations must be
taken into account. Environmental risks of pulp mill sludge may be estimated by monitoring
leaching of some elements that can contaminate groundwater depending on the condition of land
application. Therefore, the sludge dose should be recommended to avoid excessive leaching of
nitrate as well as to retain ammonium and available phosphorous. The aim of this work was to
study the mobility of some elements through the soil due to the successive application of pulp mill
sludge to Freire soil.

Sludge and Soil. The sludge used was a secondary sludge from the bleached Kraft mil
wastewater treatment plant (aerated pond) and was collected from a landfill after one year
disposal. In this condition the sludge becomes stable naturally and fulfills with the requirements
established in the Chilean Normative (NCh 2880) [10]. The soil used for this study was an Andisol
derived from volcanic ashes, belonging to the Freire Series, located in Southern Chile (3842` S,
7335`W). Twelve, 2 m x 6 m plots were established in Maquehue experimental station of La
Frontera University, which the downslope did not exceed 2% in any of the plots. Sludge was
applied to 9 of the 12 plots mixed with the top 5 cm of soil at three different loading rates (10, 20
-1
and 30 ton ha ); there were three replicates per treatment and the remaining untreated plots were
considered as controls.
Soil column experiment. A leaching experiment was carried out using undisturbed soil of the
plots mentioned above after one month of the sludge application. Twelve PVC cylinders (60 cm
length x 14 cm internal diameter) were buried into the soil plots with help of a hydraulic device
making sure to minimize disturbance to the soil structure inside, and gradually pushing the cylinder
down by small increments. Once the cylinders reach the desired depth (60 cm), the cylinders were
lifted out of the collection site and set in a greenhouse and were maintained at room temperature.
A plastic disc with an L-shaped tube ( inch diameter) was used for shutting the lower end of each
cylinder and take leaching solution. Soil columns received four applications of sludge (August,
-1
November, February and May) in the range of 0 to 30 ton ha completing one year. Distilled water
was added periodically to each column simulating rainfall condition of 1200 mm per year. At the
end of the experiment, the soil was extracted from the cylinders and was fractionated in depths
from 0-20, 20-40 and 40-60 cm. The samples were air dried and sieved through 2 mm sieve. The
samples were analyzed for determining organic matter, phosphorous and nitrogen content.
Analyses: The organic carbon content was determined by the dichromate oxidation method and
+3
colorimetric determination of the reduced chromate (Cr ). pH was measured in 1:2.5 (w/v)
+ -
soil/water mixture; available mineral nitrogen (N-NH4 + N-NO3 ) by extraction with KCl 2 M and
quantification by titration with HCl and specific electrode, respectively; and available P (Olsen) by
extraction with sodium bicarbonate (0.5 M, pH 8.5) and determined colorimetrically with the
molybdate-ascorbic acid method. Available microelements were determined by atomic absorption
spectrophotometry (Shimadzu GBC SensAA). Fe, Mn, Cu and Zn, were quantified after extraction
with a solution composed of DTPA (diethylenetriaminepentacetic acid), calcium chloride and TEA
(triethanolamine) buffered at 7.3 pH; and Al was quantified after extraction with KCl 1M (1:10
soil/solution ratio) by shaking for 24 h.
RESULTS
Chemical and physical characteristics of the pulp mill sludge and Freire soil
Pulp mill sludge presented a high content of organic matter (68%), macronutrients (N and P) and
micronutrients (Mn, Cu and Zn). Conversely, the contents of Fe and Al are lower compared with
Freire soil (Table 1). According to the sludge properties, it is expected that its addition to Freire soil
could contribute to improving the characteristics of this soil and therefore its fertility. In fact, soils
derived from volcanic ashes (Collipulli, Temuco and Gorbea) amended with pulp mill sludge
improved their physical, chemical and biological properties significantly [1,2,3,11]. However, the
high levels of Zn and Mn of the sludge must be taken account because these elements are
considered to be toxic for seeds germination and soil microorganisms [2]. Therefore it is important
477
to establish the better sludge-soil dosage to minimizing the inhibitory effect of the amendment on
seed germination, soil productivity and mobility of some elements through the soil due to the
successive application of pulp mill sludge.
Table 1. Chemical characteristics of soil and pulp mill sludge (means of three replicates)
Parameters Freire Soil Sludge
pH (H2O) 5.4 6.97

OM (%) 10 68
-1
N (mg kg ) 19.2 586.2
-1
P (mg kg ) 17.5 313
-1
Al (cmol(+) kg ) 0.07 0.03
-1
Cu (mg kg ) 3.2 5.04
-1
Mn (mg kg ) 6.4 111.15
-1
Zn (mg kg ) 0.5 376.30
-1
Fe (mg kg ) 54.5 18.47
Organic matter= Organic carbon x1.724 factor.
Soil column experiment

The four successive addition of sludge to Freire soil column during one year caused an
accumulation of organic matter, phosphorous and total nitrogen in the first 0-20 cm of the soil
column as a result of high levels of these components in the sludge. The concentration of these
components decreased as the depth in the soil column decreased (Table 2). Significant differences
(p<0.05) were found between different sludge dosage in organic matter and phosphorous levels in
the first 0-20 cm. Instead of no significant difference (<0.05) were found in these parameters in 20-
40 and 40-60 cm of soil column.
Table 2. Organic matter, pH, and P in Freire soil column after four successive application of sludge
in leaching experiment. Same letters indicate no significant difference at P<0.05.
Sludge Soil depth pH OM N total P Olsen

-1
[ton ha ] [cm] [%] [%]
-1
[mg kg ]
0 5.20 0.01 e 11.60 0.10 b 0.71 0.00 a 17.9 1.42 c
10 5.20 0.01 ef 12.40 0.77 ab 0.73 0.01 a 17.60 0.20 c
0-20
20 5.27 0.03 ef 12.68 0.32 ab 0.72 0.01 a 19.74 0.89 bc
30 5.37 0.03 f 13.15 0.06 a 0.80 0.01 a 24.62 1.09 a
0 5.57 0.09 abc 6.33 0.17 c 0.43 0.02 b 1.19 0.28 d
10 5.55 0.06 abcd 6.91 0.15 c 0.39 0.01 b 0.63 0.21 d
20-40
20 5.49 0.04 bcd 6.01 0.09 c 0.40 0.01 b 0.96 0.12 d
30 5.48 0.05 cd 5.84 0.16 c 0.40 0.02 b 0.58 0.12 d
0 5.74 0.09 ab 3.37 0.15 d 0.24 0.01 c 0.82 0.40 d
10 5.73 0.02 ab 3.11 0.07 d 0.23 0.01 c 0.72 0.28 d
40-60
20 5.72 0.06 ab 3.23 0.08 d 0.25 0.01 c 0.39 0.04 d
30 5.72 0.03 a 2.85 0.04 d 0.26 0.01 c 0.49 0.08 d
Values are mean standard error of the mean [n = 3]
478
-
Figure 1 shows the NO3 -N content at three depths in the soil column after four application of pulp
mill sludge during a year and with water addition simulating rainfall condition of 1200 mm per year.

We can observe that the highest NO3 N content was found at 40-60 cm depth and increased as
-1
the sludge application increased from 0 to 30 ton ha . In the 0-20 cm fraction NO3 N increased

from 70 to 203 mg kg-1, in the 20-40 cm fraction NO3 N increased from 108 to 170 mg kg-1 and in
-
the 40-60 cm fraction NO3 -N increased from 118 to 264 mg kg-1 as a result of the increment in the
sludge application. Nitrate was lixiviated from the columns due to its high solubility and negative
charge that avoids its adsorption by the soil exchange sites, and lixiviation was influenced by the
high water addition (1200mm per year) and by the type of soil (Andisol) [12]. Also, the structure and
-
texture of the soils influence the lixiviation of NO3 -N [13].
+
Figure 2 shows the NH4 -N content at three depths in the soil column after four application of
+
sludge for a period of one year. The NH4 -N was accumulated in the first 0 to 20 cm fraction
-1 -1
increasing from 7.9 to 12.4 mg kg with the increment of the sludge from 0 to 30 ton ha . On the
+ -1 -1
contrary in 40-60 cm fraction NH4 -N content was the lowest (2.4 mg kg with 30 ton ha ). The
+
lower NH4 -N concentration at the deeper fraction may be explained by the high affinity of this
cation by negatively charged surfaces. Typical zero point charge (ZPC) of these Chilean Andisol is
near 4.0-4.5 [14]. This cation is adsorbed in soil colloids by cationic exchange or by soil organic
matter.
300
0-20 cm
250 20-40 cm
40-60 cm
Nitrate (mg kg-1)
200
150
100
50
0
0 10 20 30
Sludge (ton ha-1)
Figure 1. Nitrate content at three depths in Freire column soil after four successive application of
sludge in leaching experiment.
0-20 cm
14 20-40 cm
Ammonium (mg kg-1)
12 40-60 cm
10
8
6
4
2
0
0 10 20 30
Sludge (ton ha-1)
Figure 2. Ammonium content at three depths in Freire column soil after four successive application
of sludge in leaching experiment.
The application of different doses of pulp mill sludge in the soil did not produce significant changes
in the levels of manganese and its content decreased with increasing depth in the soil columns. In
479
-1
the 0-20 cm fraction Mn content was around 6.1 mg kg and in the deeper fraction the Mn content
-1
was around 1.5 mg kg . On the other hand, Zn was accumulated in the first 0 to 20 cm fraction
-1 -1
increasing from 0.7 to 5.5 mg kg with the increment of the sludge from 0 to 30 ton ha . However
Zn was not found in the deeper fraction of the columns due to its positive charge, therefore no
negative effect could be associated with this element due to the application of the sludge in Freire
soil.
Acknowledgements: This study was financed by the project FONDECYT 1080427 and INNOVA-
CORFO Project N 09FCO2-6021
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[10] Instituto Nacional de Normalizacin (INN). Norma Chilena de Compost 2880-2004 (NCh 2880-
2004), Compost -Clasificacin y Requisitos, (2004). 23 pp.
[11] C. Aravena, C. Valentn, M.C. Diez, M. Mora, F. Gallardo, Aplicacin de lodos de planta de
tratamiento de celulosa: efecto en algunas propiedades fsicas y qumica de suelos
volcnicos. J. Soil Sc Nutr. 7 (1) (2007) 1-14.
- +
[12] M.L. Mora, P. Cartes, P. Nuez, M. Salazar, R. Demanet, Movement of NO3 -N and NH4 -N in
na Andisol and its influence on ryegrass production in a short term study, Journal of Soil
Science and Plant Nutrition. 7 (2007) 46-63.
[13] N.J. Jarvis, K.G. Villholth, B. Ulen, Modelling particle mobilization and leaching in
macroporous soil, European Journal of Soil Science. 50 (1999) 621-632.
[14] M.L. Mora, B. Schnettler, R. Demanet, Effect of liming and gypsum on soil chemistry, yield and
mineral composition of ryegrass grown in an acidic Andisol, Commun. Soil Sci. Plant Anal. 30
(1999) 1251-1266.
480
COMPARATIVE ANALYSIS OF HOUSEHOLD WASTE COMPOSITION IN THE

DIFFERENT DISTRICTS OF STOCKHOLM
1 2
S. Miafodzyeva ., N. Brandt
1 Department of Industrial Ecology, Royal Technical University (KTH), Teknikringen 34, Stockholm
11428 smi@kth.se
2 Department of Industrial Ecology, Royal Technical University (KTH), Teknikringen 34, Stockholm
11428 nilsb@kth.se
ABSTRACT
Separating household waste into fractions at the place where it was generated is one of
the most popular methods of collection household waste in most European countries. In
1994 a producer responsibility ordinance for packaging was introduced in Sweden. This
ordinance mandates householders to sort out packaging waste, clean the waste and sort
different package materials paper, plastic, glass and metal in assigned recycling bins.
Households participation is mandatory but in practice it is rarely controlled and enforced.
In our study we have focused our interest on seeing the composition of the trash bags,
theoretically the rest of the waste after household sorting. The aim of the study was to
identify the main fractions of household trash bags and the difference in the fraction
among 3 different districts in Stockholm, which have practically analogous facilities for
separate collection of household waste but rather different socioeconomically
characteristics. The chosen districts were located: one in the downtown and two in the
suburb districts, one of which has a big multicultural characteristic due to the big amount
of emigrants living there.
The results of the study show that the biggest fraction from the composition analyses is
organic fraction. This fraction is varying from 48% in the multicultural suburban district to
34% in the downtown. These results show the big opportunity for implementation the
separate organic waste collection spatially in the suburban areas of Stockholm. The
amount of packaging material in the trash bags still composes around 28-50%. The
composition of the packaging material differs in the 3 districts.
Keywords: Pick-analysis; household waste; composition.
INTRODUCTION
Around 4.485.600 tons of household waste are produced in Sweden each year [1]. Divided over
the population, each Swedish resident produces 480,2 kg of waste per year. 49,2 % of household
waste is recovered either by material recycling or by biological treatment, 48,4 percent treated
through incineration with energy recovery and 1,4 percent goes to landfill [1]. Environmental policy
requires that waste shall be treated in such a way that the maximal environmental and social
benefits are achieved. All parties participate in this work from producers to householders. In 1994 a
producer responsibility ordinance for packaging was introduced in Sweden [2,3,4,5]. This ordinance
requires that the producers of packaging materials provide a collection system. The producers
system includes approximately 6000 unmanned recycling stations (drop-off stations) for packaging
and paper that are located around the country [1]. The collection system is formed in consultation
with both producers and local authorities. The recycling stations have separate bins for newspaper
and various packaging material. Several municipalities have implemented curbside collection for
single-family dwelling or property close collection for apartment blocks dwelling.
In case of householders this ordinance mandates them to sort out packaging waste from other
waste, clean the waste, make use of the collection systems that producers provide, and finally sort
different packaging material in recycling bins. Households participation is mandatory but in reality it
481
is rarely controlled and enforced. Nevertheless official statistics show that households in Sweden
recycle substantial amounts of packaging materials [6].
In our study we have focused our interest on seeing the composition of the trash bags,
theoretically the rest of the waste after household sorting. The aim of the study was to identify the
main fractions of household trash bags and the difference in the fraction among 3 different
districts in Stockholm, which have practically analogous facilities for separate collection of
household waste but rather different socioeconomically characteristics.
METHOD AND MATERIAL

A general fraction analysis of trash bags was done using official data from Traffic Office in
Stockholm City Municipality. Data from three fraction analysis of trash bags in three municipalities
of Stockholm where chosen for this work:
Apartment building area downtown, Normalm
Apartment building suburban area, Hgsten
Apartment building suburban area, Rinkeby-Kista
All three areas have property close collection of packaging material and paper within 150 m. Trash
bags collection is also property close but can differ within the municipality and between the chosen
municipalities from refuse sacks in the apartment building to underground tanks or containers
within 100 m from the household. The collection of trash is weekly pickup in all three
municipalities. However, socioeconomically characteristics of the areas are rather different.
The fraction analysis of trash bags has been performed indoor by the variety of waste from the
trash bags sorted manually and divided to the predetermined fractions. The pick-analyses were
conducted in accordance with the manual RVF Development [7].
The analysis was conducted over three days in October, by Furumo Irebrand Waste Consultant
AB. The waste was collected twice a day from the refuse sacks, underground tanks and containers,
wrapped in garbage bags by householders. To obtain statistically representative results, the goal
was to sort about 300 kg per day from each area, resulting in a total of around 900 kg of trash
bags for each area.
All the collected waste was sorted manually and separately for three areas into the 15 agreed
fractions and later weighted. Weights were obtained for each fraction of material using two different
digitally calibrated scales. One scale can weigh up to 300 kg and had an accuracy of 100 g and a
smaller one with an accuracy of 1 g was used for weights below 2 kg.
Socio-economical characteristics of sampling areas

For this work three municipalities of Stockholm were chosen, one in the downtown of Stockholm
(Normalm) and two in the suburban areas (Hgsten in the south-west of Stockholm and Rinkeby-
Kista in the north-west of Stockholm).
Socio-economical characteristics of these three municipalities rather differ. There are a big number
of residents with foreign origin in the Rinkiby-Kista municipality, 77% from the all population of the
area (Figure 1). The majority of them have non European origin. While in Hgsten and Normalm
residents with faring origin account less than 20% and half of them coming from Europe.
The income parameter show that Hgsten and Normalm are high income areas, while Rinkiby-
Kista is low income one (Figure 2). The education level is high in the Hgsten and Normalm. There
is small number of people with only elementary school education and majority have high school
education, 60% of population in Hgsten and more than 60% in Normalm. While in Rinkiby-Kista
the number of people with high school education only 30% and majority have elementary and
secondary school level (Figure 3).
482
Figure 1. Residents of foreign origin (Source: Figure 2. Income (Source: USK, 2010).
USK, 2010).
Figure 3. Educational level 25-64 years old (Source: USK, 2010).

Around 900 kg of trash bags for each of the three areas was analyzed. The results from the
downtown area of Normalm are presented in the Figure 4.
Figure 4. Composition analyses of the trash bags, Normalm, Stockholm.
483
According to the figure 4 the biggest percentage account food waste, 34,2% from the all amount of
analyzed waste. We can see that all packaging material with newspaper and magazine still have
almost 50% of the trash bags. The biggest fraction from this material is newspaper and magazine
16,7%, later going paper packaging 11,4%, plastic 9,9%, glass and metal packaging finishes this
group of material.
Figure 5. Composition analyses of the trash bags, Hgsten, Stockholm.
In suburban area of Hgsten we can see similar trends in the fraction analyses (Figure 5). The
biggest fraction is food waste, which even more than in Normalm and account 40%. The packaging
material with newspaper accounted around 40% of trash bags waste. The leader here as in
Normalm is newspaper 14,3 percent, later going plastic packaging 9,7 %, paper packaging 9,1 %
and glass with metal packaging finishing this group of material. It can be noticed that amount of
glass packaging is two times less than in the downtown of Normalm.
In multicultural suburban area of Rinkiby-Kista the amount of food waste increased to 48 percent
and as in two previous areas account the biggest percentage from the all 15 fractions (Figure 6).
Figure 6. Composition analyses of the trash bags, Rinkiby-Kista, Stockholm.
484
The percent of packaging material together with newspaper is rather less than in the the two
previous area and account 28%. The biggest decrease in this group of material was found in the
fraction of newspaper and magazines, this can be explained by better recycling or just by less use
of newspapers by population in this area, due to the problems with language.
The amount of glass packaging is also decreased (3%) compare with the downtown area of
Normalm (8,3%) and have similar results as in other suburban area Hgsten (4,5%).
Fractions of hazardous, electronic waste and medicine waste in all three areas account very small
percentage, however in the area of Rinkiby-Kista this small percentage is a little bigger, that show
the necessity of more educational and informational work concerning the hazardous waste in the
areas of big population with different cultural background. However the amount of packaging
material and newspaper in this area is visually smaller compared with the other two areas. This can
be explained by better separating the waste or using products with less packaging. In the
multicultural area of Rinkiby-Kista is traditionally popular to buy food products in the street
vegetable market or in the national shops where the amount of product is rather bigger in the
package than in the supermarket.
CONCLUSIONS
The key findings of the analysis were as follow:
The biggest amount of trash bags account fraction of food waste, that show the potential
for the separate collection of organic waste and as the result reduction of waste in the
trash bags. The fraction of food waste increase in the suburban areas and in the area
with lower income and education characteristics.
The group of main recyclable materials (newspaper, packaging of metal, glass, plastick
and paper) still remains rather big amount of trash bag, from 50% in the high income
downtown to 28% in the lower income multicultural suburbun area with 40% in the middle
in the high income suburban area.
Fraction of newspaper remains the biggest amount in the group of recyclable materials in
the downtooun and high income suburban areas.
Fraction of glass packaging two times bigger in the downtown area comparing with
suburban areas.
REFERENCES
[1] Information on http://www.avfallsverige.se/fileadmin/uploads/Statistikfiler/SWM2010.pdf
[2] SFS, 1993. Frordningen om producentansvar fr glasfrpackningar och frpackningar av
wellpapp, SFS 1993:1154 (The Ordinance of Producer Responsibility for Glass Packaging
and Cardboard). Swedish Legislation.
[3] SFS, 1994a. Frordningen om producentansvar fr returpapper, SFS 1994:1205 (The
Ordinance of Producer Responsibility for Waste Paper). Swedish Legislation.
[4] SFS, 1994b. Frordningen om producentansvar fr frpackningar, SFS 1994:1235 (The
Ordinance of Producer Responsibility for Packaging Material). Swedish Legislation.
[5] SFS, 1997. Frordningen om producentansvar fr frpackningar, SFS 1997:185 (The
Ordinance of Producer Responsibility for Packaging Material). Swedish Legislation.
[6] Swedish Environmental Protection Agency (SEPA). Framtida producentansvar fr
frpackningar och tidningar. Raport 5648, Stockholm, 2006
[7] RVF Utveckling 2005:19 Manual fr plockanalys av hushllsavfall, ISSN 1103-4092
485
REMOVAL OF IRON IONS FROM WASTEWATERS USING TURKISH

NATURAL ZEOLITE
1 2
N. Erdl Aydn , G.Nasn Saygl
1 stanbul Technical University, Faculty of Chemical and Metallurgical Engineering, Chemical
Engineering Department, Maslak, stanbul, Turkey, erdol@itu.edu.tr
2 stanbul Technical University, Faculty of Chemical and Metallurgical Engineering, Chemical
Engineering Department, Maslak, stanbul, Turkey, nasun@itu.edu.tr
ABSTRACT
There has been a continuous concern about the discharge of metals and other trace
chemicals to the aquatic environment, particularly to potable water sources in recent
years. Although some of these metals are essential dietary elements, some of them are
cumulative poisons when ingested. The high concentration of metals in the wastewater in
generally caused by the discharge of industrial wastes to the sewage or by the infiltration
of water that has passed through deposits of metal-bearing minerals. Metals release in
wastewaters represents quite a serious environmental problem on account their well
known toxic effect on natural life.In this work studies have been performed which
demonstrate that iron ions may be retained by naturally occured zeolites. The
experimental work performed on the natural zeolite, which is found abundant quantities in
Turkey, showed that the ion exchange process is quite rapid and high quantities of iron
ions are removed from the aqueous in a short period of time.
The purpose of this study is to investigate the use of clinoptilolite, obtained from Yalova-
Karamrsel deposits, in the removal of iron ions from wastewaters. The experiments
were run in a column system. Besides, the effects of feed flow rate and particule size on
the ion exchange was also investigated.
Keywords: Waste water ; iron ; natural zeolite ; removal
INTRODUCTION
Industrial progress has made life more comfortable but at the same time the natural environment
had suffered from the detrimental effects of pollution. Among various pollutants, heavy metal ions
are very toxic and carcinogenic in nature [1]. Heavy metal pollution of water and soil is known to
affect the ecology adversely, thereby, causing health hazards in humans [2]. The presence of
heavy metals in the aquatic environment has been of great concern because of their toxicity at
lower concentrations. Same metal ions have cumulative effect capable of being assimilated and
+2 +2
stored in the tissues of organism, causing significant adverse physiological effect [1]. Pb , Cu ,
+3 +3
Fe and Cr are especially common metals that tend to accumulate in organisms, causing
numerous diseases and disorders [3].
The major sources of heavy metals in the environment include metal extraction, metal fabrication
and surface finishing, paint and pigments as well as the manucacturing of batteries. More
specifically, the main source of an appreciable iron entry into a municipal water supply is through
pipeline corrosion, metal finishing and galvanized pipe manufacturing. The presence of iron at a
level more than recommended may cause industrial and human health problem. For example, iron
toxicity can cause anorexia, oligura and diphasic shock. In the industry, iron ions deposit and can
build up in pressure tanks, water haters and pipelines, which reduces the quantity and pressure of
the water supply. In addition, iron ions combine with oxygen from air to form reddishbrown particle
(rust) impurities. These impurities can give a metallic taste and odor to water. Due to these
problem, a special attention should be paid to removing or decreasing iron ion content in industrial
water effluents[1,4].
486
It is known that in the electroplating industry big quantities of waste water are formed, which cause
serious environmental problems. Different physic-chemical and chemical methods can be applied
for purification of these waste waters. By using the ion exchange process and materials for
purification of heavy metals containing waste water can be obtained purified water for recycling.
Their application have a positive ecological effect [4, 5].
A number of treatment methods have been utilized in removing meals from industrial waste waters.
The most commonly applied methods are : precipication, ion exchange, solvent extraction,
evaporation, electrodialysis and reverse osmosis. Amongst these methods evaporation, reverse
osmosis and electrodialysis exhibit no selectivity whereas precipitation, solvent extraction and ion
exchange are selective for specific ions of interest. A major disadvantage of precipitation is the
huge generation of sludge that needs extra disposal. Solvent extraction also involves the use of
extraction chemicals that are often toxic organic substances. Ion exchange had several benefits
compared to other methods because it is relatively clean and energy efficient methods, which also
features selectivity for certain ions even in solutions of low concentration of the target ion.
Furthermore, it has high treatment capacity, high removal efficiency, fast kinetics and also be
utilized in metal recovery and water reuse, which are of economical importance [2, 6].
Both organic and inorganic ion exchangers have been synthesized and exploited in heavy metal
removal from waste effluents. During the last few decades inorganic ion exchangers have became
increasingly popular because of certain advantages over organic resins such as resistance towards
high ionizing radiation, stability at higher temperatures and selectivity towards certain metal ions [2,
7].
Heavy metals such as Cr, Cu, Pb, Cd, Co, Ni, Sb, etc., are toxic priority pollutants that commonly
interfere with the beneficial use of wastewaters for irrigation and industrial applications. The release
of heavy metals into the environment is a potential threat to aquatic ecosystem and soil quality as
well as to plant, animal and human health. The toxic metals, probably existing in high
concentrations must be effectively removed from wastewaters [8].
The use of alternative low-cost materials as potential sorbents for the removal of heavy metals has
been emphasized recently. In this regard, naturally occurring zeolites hold great potential for use as
packing material in subsurface reactive barriers intercepting ground water plumes, and for fixed
bed reactors designed to remove heavy metals from industrial wastewaters [9]. Natural zeolites are
the most important inorganic cation exchangers that exhibit high ion exchange capacity, selectivity
and compatibility with the natural environment [10].
Many adsorbents have been investigated for ion removal from water, for example, activated
carbon, silica, diatomine, and appetite. One potential strategy to use a low-cost natural and
synthetic adsorbent is zeolite [11]. Zeolite is an aluminum silicate that occurs both as natural and
as produced synthetic. Zeolite has a htree-dimensional structure with pores. It consist of silicon,
aluminum and oxygen ions. The silicon ions are neutrally charged in the crystal structure.
Aluminum ions create negative places. To keep the cargo in balance a counterion (Na+, K+) or a
proton (H+) is present in the pores. One types of zeolite have just as large pores through the entire
crystal structure. The crystal structure is stiulated by the ring size of the crystal structure. T change
the ratio of aluminum on silicon can also influence the pore size as well as the type of a counterion.
All natural zeolites contain aluminum and are hydrophilic in nature [11, 12, 13].
Clinoptilolite is the most abundant natural zeolite that occurs in relatively large minerable
sedimentary deposits in sufficiently high purity in many parts of the world. This mineral is reported
to have a classical alumina silicate cage-like structure and therefore exhibits significant macro-
porosity [14]. The selectivity series of clinoptilolite in the sodium form was determined as follows
2+ 2+ 2+ 2+ 2+ 3+ 2+ 2+ 2+
[15] Pb > Cd > Cs > Cu > Co > Cr > Zn > Ni > Hg . However, researches are mainly
performed in batch mode systems and few data are available for clinoptilolite columns [16, 17, 18,
19, 20, 21]. The design of full scale systems must consider shorter contact times and mass transfer
limitations. Therefore, the column systems that simulate the hydrodynamic characteristics of full
scale systems are recommended to conduct treatability studies [22].
The aim of this study is to investigate copper removal from wastewaters by using natural zeolite
supplied from Yalova-Karamrsel (Western Anatolia) region in Turkey. The examinations were
carried out on a column system. The effect of the process parameters on ion exchange process
has been examined.
487
EXPERIMENTAL
Zeolite Source and Reagent

Zeolite samples used in this study were taken from Yalova-Karamrsel, Turkey. The crushed
mineral was ground and sieved to 1-3 mm particle size and was dried in oven at 105C for 24 h to
remove moisture. In order to ensure the method is economical, the samples were used and stored
as provided, that is with no pre-treatment except drying. The compound used to prepare the
2+
reagent solution of iron was of analytical grade. The synthetic stock solution containing Fe ions
was prepared by dissolving a weighed quantity of the sulfate salt (FeSO4.7H2O) in deionized water.
It is known that the anions of sulfate and nitrate salts in the aqueous solutions do not form any
metal-anion complexes and do not hydrolyze [23]. Thus, the sulfate anion was considered to be
inert and its effect on ion exchange process was not observed.
Column Experiments
The column tests were carried out in a glass column at 25 1C with an inside diameter of 5 cm.
Since the ratio of column diameter to particle diameter is high, the effects of channeling have a
negligible effect. Iron (II) solution which was prepared using the stock solution by appropriate
dilution was pumped through the column at desired flow rate by a peristaltic pump. Samples were
collected from the exit of the column at different time intervals until the saturation of the bed
(C/C0=1) occurred and analyzed for copper concentration using a Varian atomic absorption
spectrophotometer. The experimental conditions are presented in Table 1 (C0: feed concentration,
H: bed height, Q: volumetric flow rate, d: particle size)
Table 1. Experimental work conditions

Run C0 H Q d
[M] [cm] [ml/min] [mm]
1 0.01 4 8,3 0,6 1
2 0.01 4 15,8 0,6 1
3 0.01 4 7,8 0,4 0,6
4 0.01 4 15,8 0,4 0,6
Effect of Flow Rate

The effect of flow rate was studied for solution concentration of 0.01 M and volumetric rate was
changed from 7,8 to 15,8 ml/min, while the bed height was held constant at 4 cm. Typical
experimental breakthrough curves are shown in Fig. 1. As it can be seen removal efficiency is
favored by lower volumetric flow rates and as the flow rate increased the breakthrough curve
becomes steeper. It is also seen that the breakthrough time, exhaustion time and uptake capacity
decreased as the flow rate increased. Corresponding time periods to reach saturation values were
found to be 270th minutes for the flow rates of 8, 4 and 1.6 respectively.
It is known that because of the relatively slow loading kinetics of zeolites, relatively long residence
times are needed [24].
When the flow rate increased, the residence time of the solute in the column decreased, which
causes the iron solution to leave the column before equilibrium occurs. Thus, the failure of attaining
local equilibrium results in lower uptake of cations from the incoming solution. On the other hand,
when the process is intraparticle mass transfer control, a slower flow rate favors the sorption and
when the process is subjected to external mass transfer control, a higher flow rate decreases the
film resistance [25]. Even though the volume of iron solution treated was higher at 15,8 ml/min, the
low flow rate of 8,3 ml/min showed a relatively high iron removal which is represented by the area
above the breakthrough curve.
488
Figure 1. Effect of flow rate on iron sorption
Effect of Particle Size

The dependence of the ion exchange performance on particle size (0.6 - 1 and 0,4 0,6 mm) was
studied while the bed height, feed concentration and flow rate were held at 4 cm, 0.01 M and 15,8
ml/min respectively. Fig. 2 shows the breakthrough curves for examined particle sizes. The
breakthrough curve of the smaller particle size raised a little steeply ranged from the break point to
the exhaustion point. Breakthrough (C/C0=0.05) of iron occurred after 5 min at particle size of 0.6-1
mm and 0.4 - 0,6 mm, respectively. It is well known that by decreasing the particle size, the
performance of ion exchange process is improved but it can be said that particle size effect is
minimal for iron. On the other hand, small particle size result in high flow resistance of the column
and should be avoided. Because, lower granulation attains higher compactness, which in turn
increases the hydraulic resistance, forms channels and pores in the layer [26].
CONCLUSIONS
In this study, iron removal from aqueous solution by using clinoptilolite was investigated in a
column system. The column system was operated at different flow rates, and adsorbent particle
sizes. When the flow rate increased the breakthrough time reaching saturation decreased
significantly because of shorter retention time. The change in the initial iron concentration affected
the breakthrough time and exhaustion time, in other words, with the increase of feed solution
concentration the zeolite becomes exhausted earlier. The particle size of clinoptilolite has no
significant effect on exchange process for iron.
As a summary, iron ions can be removed from wastewaters by using Yalova-Karamrsel, Turkey
clinoptilolite.
489
Figure 2. Effect of particle size on iron sorption
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[26] N.V.Medvidovic, J.Peric, M.Trgo, Column performance in lead removal from aqueous
solutions by fixed bed of natural zeolite-clinoptilolite, seperation and purification technology,
49(3) (2006) 237-244.
491
HEALTHCARE WASTE MATERIALS CHANGES UNDER ALKALINE

HYDROLYSIS TREATMENT
1 2 3
S.C. Pinho , M.F Almeida and O.C. Nunes
1 Lepae, Faculty of Engineering, University of Porto, scpinho@fe.up.pt
Rua Dr. Roberto Frias, s/n 4200-465 Porto
2 Lepae , Faculty of Engineering, University of Porto, mfa@fe.up.pt
3 Lepae, Faculty of Engineering, University of Porto, opnunes@fe.up.pt
ABSTRACT
In this work has been studied the behavior of some materials present in healthcare waste
when treated by alkaline hydrolysis. The alkaline hydrolysis was performed with 0.1 M, 1
M or 2 M NaOH at 135 C. The efficiency of treatment was assessed by changes on the
mass of the materials samples, and total organic carbon (TOC) and chemical oxygen
demand (COD) in the effluent resulting from alkaline hydrolysis. Among the ten tested
samples of materials, adhesive was the most degraded and showed the highest weight
loss of 53.8 wt%. The final effluent obtained by alkaline treatment is hazardous due to its
high pH, TOC and COD. The diaper and adhesive were the materials that released more
TOC and COD to the resulting effluent. Those values were 17.3 and 45.9 g C/l and 42.0
and 143.76 g O2/l, respectively.
Keywords: healthcare wastes; medical wastes; alkaline hydrolysis
INTRODUCTION
Waste management is a matter of concern in developed countries, namely in the European Union
where 3 billion tonnes of waste are produced annually of which 90 million tonnes are hazardous
ones [1].
Healthcare waste (HCW) represents only 0.3% of total waste generated in Europe, but requires
special attention due to the danger it represents to public health and environment. An inadequate
healthcare handling operation is a potential contamination source for all people handling this type
of waste, i.e., health professionals, patients, community and the environment [2,3]. Additionally,
HCW inadequate handling may originate infections inside hospitals and other health care facilities.
These infections, called nosocomial, have a rate of about 10 % [4]. The hands are the main route
of transmission; approximately 21 % of nosocomial infections are caused by microorganisms
present in the medical personnel hands. The infections explain around 25 % of the extra
hospitalization days [5].
In 2002, the results of a study made by the World Health Organization (WHO) in 22 developing
countries showed that the possibility of contracting an infection, promoted by improper HCW
handling and disposal methods varies from 18 % to 64 % [6].
The majority of HCW, of about 75-90 % is not infectious, therefore can be treated as municipal
waste. The remaining 10-25 % is classified as hazardous waste, of which 1 % is made of cutting
and perforating materials, 3 % are discarded chemicals and drugs and less than 1 % is radioactive
waste and cytostatics. While the amount of needles is just a small part of the total HCW generated,
they are a source of concern due to their high rate of infection.
There are a number of processes that can be used to treat hazardous HCW: chemical disinfection;
encapsulation; microwave disinfection; irradiation; gas sterilization; pyrolysis and oxidation. In
developed countries the most used treatments are autoclaving and incineration [7].
Alkaline hydrolysis is a technology to destroy animal carcasses, tissues, anatomical parts, blood,
body fluids, toxic agents and fixatives [8]. This process requires an aqueous solution with sodium
hydroxide or potassium hydroxide at temperatures around 150-300 C to convert all the organic
492
material present into a sterile solution of small protein molecules, amino acids, carbohydrate and
fatty acids salts. The operational conditions used in this process, temperature and alkalis
concentration on solution, destroy the protein layer of the virus and the prions peptide bonds?[8].
The behaviour of polyethylene terephthalate (PET) when exposed to alkaline hydrolysis was
studied, but little is known about the changes produced in other components, its interaction when
digested in mixtures of different materials and the emissions resulting from the treatment [9].
Alkaline hydrolysis seems to have significant advantages compared to others HCW treatments,
because it sterilizes and destroys at once, eliminates pathogens and prions and reduces the total
waste volume. It may have a range of application larger than autoclaving, since it can accept
organic tissues, too. The effluent resultant from the application of the method to HCW containing
organic fluids and tissues has a high organic load, and it can be acceptable in municipal collectors
after some pH adjustment [8]. However, the changes in common inorganic materials present in
HCW during the process as well as effluent final composition and treatability must be well known.
In this work the behavior of some materials present in HCW was studied when treated by alkaline
hydrolysis in conditions similar to the ones used in autoclaving. The efficiency of treatment was
assessed by determination of weight losses on the materials and characterization of TOC and COD
in the effluents produced by alkaline hydrolysis applied to each individual material.
EXPERIMENTAL
Materials and methods

The samples studied were materials normally present in HCW, such as surgical gloves, operating
gloves, transfusion tube, cotton, urine bag collector, surgical mask, serum bottle, syringe, adhesive
and diaper. Due to the clinical application of these materials they are subjected to additional
treatments during their manufacturing process such as disinfection, application of anti-allergic
materials, additives and others substances that may affect its behaviour under subsequent
treatments. Table 1 shows the HCW materials composition used in the experimental work.
Table 1. Composition of HCW materials used in the experimental work

Material Composition
Transfusion tube Polyvinyl chloride (PVC)
Serum bottle Low-density polyethylene
Bag collector for urine Polyvinyl chloride
Surgical glove >90% Natural rubber
Examination glove Polyvinyl chloride
Surgical mask Polypropylene; polyester and pressed polypropylene
Cotton 94% Cellulose
Diaper Cellulose fibre and polypropylene; polyethylene film;
thermoplastics adhesives; elastic threads; flocgel (sodium
polyacrylate)
Adhesive Non-woven polyester; synthetic adhesive from rubber
Syringe Polypropylene and high density polyethylene
The alkakine hydrolysis was performed in a Parr batch reactor with a titanium vessel of 450 ml
capacity under temperature control and with pressure reading. The operational conditions used in
hydrolysis were heating rate of 10 C/min to 135 C and holding time of 30 minutes. A 2.0 g sample
of individual material was placed into the reactor with alkaline solution and L/S=10:1. The sodium
hydroxide concentrations used were 0.1 M, 1 M and 2 M.
The resulting mixture was filtrated and the solid fraction was dried at room temperature following a
48 h stage in a desiccator and weighted. The effluents generated at the alkaline treatments were
characterized for pH, TOC, COD and chlorides, in the case of materials composed by PVC.
TOC was determined according to EN 1484 with a Shimadzu TC analyser, model TOC-VCSH. pH
was measured with a pH-meter, model 632 of Metrohm. COD was determined according the so-
called colorimetric method, closed reflux according to Standard Methods for Examination of Water
493
th
and Wastewater, 18 Edition, 1992. Chlorides determination was carried out according to Standard
th
Methods for Examination of Water and Wastewater, 18 Edition, 1992 [10].

The materials weight losses after alkaline hydrolysis treatments are shown in Fig. 1. The serum
bottle and syringe, which are composed by polyethylene and polypropylene, had no weight losses.
However, under the imposed treatment temperature of 135 C these materials have reached their
melting temperature, respectively 100-110 C for low-density polyethylene and 125-135 C for high
density polyethylene. The other tested materials had significant weight losses when treated by
alkaline hydrolysis. The NaOH concentration in solution visibly influenced the weight losses of the
materials, which were higher for the highest concentration tested (2 M). The transfusion tubes, bag
collectors for urine and examination gloves are all composed by PVC; despite of the same
composition, these materials showed different weight losses of, respectively, 0.2 wt%, 0.5 wt% and
1.6 % in 0.1 M NaOH solution to 1.1 wt%, 4.9 wt% and 9.2 wt% in 2 M NaOH solution. As known,
PVC exists with some variable compositions, which may explain these results. For the materials
from surgical glove, cotton and surgical mask, the obtained weight losses were in the range of 1.4-
2.4 wt% in 0.1 M NaOH solution to 3.6-8.1 wt% in 2 M NaOH solution. The highest mass loss of
about 53.8 wt% was obtained for the adhesive material when subjected to the 2 M NaOH solution.
The hydrolyzed adhesive sample decreased greatly in size and was aggregated by its glue.
60
tranf usion tube
collector f or urine
50 examination glove
mask
40 cotton
Weight loss %
surgical glove
30 diaper
adhesive
20
10
0
0,1 M 1M 2M
NaOH concentration
Figure 1. Weight losses in the HCW materials treated with alkaline hydrolysis
The effluents generated by alkaline hydrolysis had pH values around 12.6 and 13.9 for 0.1 M and 2
M NaOH solutions, respectively, as well as high organic load. Most materials tested produce
effluents with high values of TOC and COD, except for serum bottles and syringes, which values
were below 100 mg/l of TOC. The effluent resulting from the diaper treatment was among those
with the higher values of TOC and COD, respectively 17.3 g C/l and 42.0 g O2/l, while the effluent
from adhesive showed the highest TOC and COD values, respectively 45.9 g C/l and 143.8 g O2/l.
Fig. 2 and Fig. 3 show TOC and COD values for all the effluents. As seen in these figures, NaOH
concentration directly correlates with both parameter values. Chlorides in the effluents from
hydrolysis of materials with PVC, as transfusion tube, examination glove and bag collector for
urine, were below 10 mg/l which indicates no polyvinyl chloride decomposition under the studied
conditions.
494
50000
45000 serum bottle
syringe
40000
transf usion tube
35000 surgical glove
collector f or urine
TOC [mg/l]
30000 examination glove

25000 cotton
surgical mask
20000 diaper
15000 adhesive
10000
140000 bottle 5000 serum
0
syringe
120000 transfusion tube
surgical0,1 M
glove 1M 2M
100000 collector for urine
NaOH concentration
COD [mg/l]
examination glove
80000 cotton
Figure 2. TOC contentsurgical
(mg/l) in the effluents resultant from alkaline hydrolysis of HCW materials
mask
60000 diaper
adhesive
40000
20000
140000 serum bottle
0 syringe
120000 tranf usion tube
0,1 M 1M 2M
surgical
NaOH gloveconcentration
100000 collector f or urine
COD [mg/l]
examination glove
80000 cotton
surgical mask
60000 diaper
adhesive
40000
20000
0
0,1 M 1M 2M
NaOH concentration
Figure 3. Chemical oxygen demand (mg O2/l) in effluent resultant from alkaline hydrolysis of HCW
materials
CONCLUSIONS
With this study is possible to conclude that:
- Material degradation generally increases with increasing NaOH concentration in the
hydrolysis solution, as indicated by a greater weight loss and TOC and COD increase in
the resultant effluent;
- The serum bottle and syringe materials are resistant to the treatment as shown by the
practically nil weight loss and the low TOC and COD values in the effluent (<100 mg/l);
495
- The adhesive is the material with lower resistance to the treatement, since it looses more
than 50% of its weight and 46 % of its carbon as TOC when hydrolyzed with the 2 M NaOH
solution;
- Due to the high loads of TOC and COD, as well as high pH values, these effluents require
a pre-treatment, at least neutralization, before discharge in a municipal collector in order to
be treated with urban wastewaters.
REFERENCES
[1] Eurostat. Generation of waste by waste category (hazardous and non-harzadous), (2010).
Available from http://epp.eurostat.ec.europa.eu
[2] E. Franka, A.H. El-Zoka, A.H. Hussein, M. M. Elbakosh, A.K. Arafa, K.S. Ghenghesh, Hepatitis
B virus and hepatitis C virus in medical waste handlers in Tripoli, Libya. Journal of Hosp.
Infect, 72 (2009), 258-261.
[3] S A. Tamplin, D. Davidson, B. Powis, Z. O`Leary, Issues and options for the safe destruction
and disposal of used injection materials. Waste Management, 25 (2005), 655-665.
[4] R. T. Mayon-White, G. Ducel, T. Kereselidze, E. Tikomirov, An International survey of the
prevalence hospital acquired infection. Journal of Hosp. Infect. 11 (1988), 43-48
[5] M. F. Silva Maria, Descontaminao qumica de resduos lquidos orgnicos hospitalares
contaminados. Master thesis, Faculty of Engineering, University of Porto, Portugal (2001)
[6] World Health Organization. Safe health care waste management (2004). Policy paper.
Downloaded from, www.healthcarewaste.org
[7] B. Lee, M.J Ellenbecker., R. Moure-Ersaso, Alternatives for treatment and disposal cost
reduction of regulated medical waste. Waste Management, 24 (2004), 143-151.
[8] H. Thacker, Leon. Carcass Disposal: A Comprehensive Review, National Agricultural
BiosecurityCenter, Kansas State University (2004).
[9] C. Kao, W. Cheng, B. Wan, Investigation of Alkaline Hydrolysis of Polyethylene Terephthalate
by Differencial Scanning Calorimetry and Thermogravimetric Analysis. Journal of Applied
Polymer Science, Vol. 70 (1998), 1939-1945.
th
[10] Standard Methods for Examination of Waters and Waste-Water, 18 ed., 1992, publication
Office: APHA, Washington, DC.2000
[11] L. F. Diaz, L. L. Eggerth, Sh. Enkhtsetseg, G. M. Savage, Characteristics of healthcare wastes.
Waste Management, 28 (2008), 1219-1226.
[12] C. C. Lee, G. L. Huffman, Medical waste management/incineration. Journal of Hazardous
Materials, 48 (1996), 1-30.
[13] S. A. Tamplin, D. Davidson, B. Powis, Z. O`Leary, Issues and options for the safe destruction
and disposal of used injection materials. Waste Management, 25 (2005), 655-665.
Acknowledgments
S.C. Pinho thanks the FCT for the fellowship SFRD/BD/48956/2008
496
TITANIUM DIOXIDE PHOTOCATALYSIS ON THE REMEDIATION OF MODEL

TEXTILE AZO DYES WASTEWATERS
E. M. Saggioro1*, A. Oliveira2,3, T. Pavesi1, L.F. Vieira Ferreira2, J.C Moreira1

*saggi_br@hotmail.com
1Centro de Estudos da Sade do Trabalhador e Ecologia Humana, Fundao Oswaldo Cruz,Av.

Leopoldo Bulhes, 1480 - 21041-210 RJ, Rio de Janeiro, Brasil
2- Centro de Qumica-Fsica Molecular e Instituto de Nanocincias e Nanotecnologia,
IST,UTL, Av. Rovisco Pais,1 -1049001 Lisboa, Portugal
3 Centro Interdisciplinar de Investigao e Inovao, ESTG, Instituto Politcnico de Portalegre,
Lugar da Abadessa Apartado 148 -7301901 Portalegre, Portugal
ABSTRACT
Large quantities of dyes are extensively used in fundamental processing steps of textile
industries. It is estimated that from 1% to 15% of the dye is lost during dyeing processes
due incomplete fixation of the textile fiber. The class of azo dye represents 60% of the
dyes used around the world. The semiconductor titanium dioxide TiO2 produces hydroxyl
radicals that attack rapidly and non-selectively the most recalcitrant organic molecules.
The aim of this work was to assess the photodegradation of four azo dye used in textile
industry. Remazol Red RGB gran, Marine Remazol RGB 150% gran, Ultra Red Remazol
gran and Remazol Carmine Ultra RGB were the dyes used. TiO 2 P-25 Degussa was
-1 -3 -1 -1
tested in concentrations from 1 gL to 1x10 gL . And the catalyst was added to 30mgL
aqueous solutions of each dye. The samples were treated during two hours with artificial
irradiation (mercury-vapor lamp 125W). The photodegradation of the samples was
followed by UVVis spectrophotomety monitoring the decrease of the maximum
wavelenght of each dye. The photolysis is responsible for the degradation of 0 to 6% in
-1
the two hours irradiation period. The concentration of 1 gL of TiO2 promoted the highest
percentage of degradation for all dyes. By the end of two hours 75 to 95% of the dyes
-1 -1
were degraded by 0,1 gL of catalyst. However, 1gL degraded up to 93 to 99% of dyes.
Therefore, under irradiation, only the molecules adsorbed on the surface of TiO 2 can be
degraded. AOPs mediated by TiO2 are a good alternative for treatment of wastewaters
containing these azo dyes.
Keywords: Azo dyes; titanium dioxide; artificial irradiation; photocatalytic degradation
INTRODUCTION
Large quantities of dyes are extensively used in fundamental processing steps of textile industries.
It is estimated that from 1% to 15% of the dye is lost during dyeing processes due incomplete
fixation of the textile fiber and at the end of the process is released in wastewater. Hence, these
wastewaters discharged in rivers or public sewage treatment plants are highly contaminated [1].
The class of azo dye represents 60% of the dyes used around the world, fundamentally, due to the
capacity of their reactive groups to bind to textile fibers by covalent bonding [2].
497
In recent years advanced oxidation processes (AOPs) are effectively used to detoxify recalcitrant
pollutants present in industrial wastewater. The semiconductor titanium dioxide TiO2 produces
hydroxyl radicals that attack rapidly and non-selectively the most recalcitrant organic molecules [3,
4]. The aim of this work was to assess the photodegradation of four azo dyes used in textile
industry. The concentration of titanium dioxide was used as photodegradation parameter.
Figure 1. Structural of C.I Reative Black 5 and C.I Reative Red 239.
EXPERIMENTAL
Remazol Red RGB gran, Marine Remazol RGB 150% gran (5% C.I Reative Black 5) , Ultra Red
Remazol gran (35% C.I Reative Red 239) and Remazol Carmine Ultra RGB were the dyes used.
-1 -3 -1
TiO2 P-25 Degussa was tested in concentrations from 1 gL to 1x10 gL . And the catalyst was
-1
added to 30mgL aqueous solutions of each dye. The samples were treated during two hours with
artificial irradiation (mercury-vapor lamp 125W) and samples were collected at 0, 15, 30, 45, 60, 90
e 120 minutes. The photodegradation of the samples was followed by UVVis spectrophotomety
monitoring the decrease of the maximum wavelenght of each dye.
RESULTS and DISCUSSION

Figures 1 to 4 present the results of the TiO2 mediated photodegradation of the four azo dyes
studied on this work. For all of them treatment with TiO2 under artificial irradiation was un
extremely efficient photodegradation method, since after 2 hours all dyes showed substantial lost of
their colours. The photodegradation is mostlt promoted by titanium dioxide since we observed that
direct photolysis is only responsible for the degradation of 0 to 6% of these azo dyes in the two
hours irradiation period.
498
-1 -1
Figure 2. Degradation of Ultra Red Remazol gran 30mgL under mercury-vapor lamp 125W with 1 gL
-3 -1
a1x10 gL of TiO2, followed with a UVVis spectrophotometer 200-900nm.
-1 -1
Figure 3. Degradation of Remazol Red RGB gran 30mgL under mercury-vapor lamp 125W with 1 gL a
-3 -1
1x10 gL of TiO2, followed with a UVVis spectrophotometer 200-900nm.
499
-1
Figure 4. Degradation of Marine Remazol RGB 150% gran 30mgL under mercury-vapor lamp 125W with
-1 -3 -1
1gL a 1x10 gL of TiO2, followed with a UVVis spectrophotometer 200-900nm.
-1 -1
Figure 5. Degradation of Remazol Carmine Ultra RGB 30mgL under mercury-vapor lamp 125W with 1gL a
-3 -1
1x10 gL of TiO2, followed with a UVVis spectrophotometer 200-900nm.
500
Figure 6 presents the evaluation on the percentage degradation with the time of irradiation and with
the amount of the photocatalyst.
Figure 6. Degradation of azo dyes Ultra Red Remazol gran ( mx=540), Marine Remazol RGB 150% gran
-1 -1
(mx=615), Remazol Red RGB gran (mx=518), Carmine Ultra RGB (mx=515) 30mgL with 1 gL
-3 -1
to 1x10 gL TiO2.
-1
As expected the concentration of 1 gL of TiO2 promoted the highest percentage of degradation for
all dyes. This concentration degraded 90 to 93% in 45 minutes of all azo dyes. The rate constant of
degradation decreased after this time. By the end of two hours 75 to 95% of the azo dyes were
-1 -1
degraded by 0,1gL of catalyst. However, 1gL degraded up to 93 to 99% of dyes for longer
irradiation times. Therefore, under irradiation, only the molecules adsorbed on the surface of TiO 2
can be degraded. The scission of the double bond between the nitrogen atoms accounts for dyess
discoloration, when the active site becomes available and another molecule of dye occupies it.
CONCLUSION
Although other parameters must be consider, this results show that AOPs mediated by TiO 2 are a
good alternative for the treatment of wastewaters containing these azo dyes.
REFERENCES
Reference an article:
[1] Z.Zhainal, J. Harzd. Mater.,125, (2005) p. 113-120
[2] L.MS. Colpini, Dyes and Pigments., 76 (2008) p. 525-529
[3] M. Muruganandham, M. Swaminathan, Dyes and Pigments, 72 (2007) p. 137-143
[4] A.S.Oliveira, E.Saggioro, N.Barbosa, A.Mazzei, L.F.V.Ferreira, J. Moreira. Rev. Chim., 62
(2010) 00.
501
ACKNOWLEDGMENTS
The authors thanks to FCT (project PTDC\QUI\65510\2006) in Portugal and CNPq and Faperj in
Brazil.
502
INFLUENCE OF TEMPERATURE ON THE As LEACHING OF SEDIMENT-

BASED CERAMICS BODIES BY MEANS OF SEQUENTIAL EXTRACTION
1 2 3 4
R. Alonso-Santurde , A. Andrs , B. Galn and J.R. Viguri
1 Dpt. Chemical Engineering and Inorganic Chemistry. University of Cantabria. Avda. Los Castros,
s/n. 39005. Santander (Cantabria), Spain. alonsor@unican.es
s/n. 39005. Santander (Cantabria), Spain. andresa@unican.es
s/n. 39005. Santander (Cantabria), Spain. galanb@unican.es
s/n. 39005. Santander (Cantabria), Spain. vigurij@unican.es
ABSTRACT
Dredged sediments have been considered waste materials than have to be managed
properly. The sintering capacity of Santander Bay sediments has been proved, showing
that they could be used in the ceramic industry as alternative raw material. In this work a
sequential fractionation method was applied to both unfired and fired clay and sediment
samples to establish the different fractions of As and to determine the effect of the
thermal treatment on the As distribution. Leaching tests were also applied to confirm the
results. The sequential extraction results showed that As was mainly linked to
exchangeable and Fe oxides fractions in unfired samples. The high amounts of As
bounded to stable phases such as amorphous and crystalline Fe oxides indicated that the
As mobility could be considered low. Because of the thermal treatment increased the
exchangeable fraction-associated As amounts and decreased the Fe oxides-associated
ones, it could be considered that the sintering process increased the As mobility.
Leaching tests confirm these results. The As leached concentrations were higher in the
leachates from fired clay and sediment samples than in those coming from unfired ones.
Sediment showed high capacity for immobilizing As in the sintered structure.
Keywords: polluted sediment, arsenic, ceramic body, sequential extraction, leaching
INTRODUCTION
Dredging and disposal of marine and freshwater sediments often is required to maintain
navigational channels or to remediate contaminated waterways. Sediments play an important role
in maintaining water quality by removing contaminants form the water column, acting as sinks of
contaminants. However, subsequent remobilization of contaminants from the sediment can
generate high concentrations of dissolved contaminants in the aquatic environment [1].
Dredged sediments have been considered to be waste materials [2,3], and since international and
European laws have become more stringent, their management has become an environmental and
economic concern. Sediments categorized as clean material can be disposed in open-water, but
landfilling requires large spaces and long-term monitoring. On contrast, treatment processes can
reduce the toxicity and volume of dredged materials, but their costs are not yet competitive enough
[4]. The valorization of waste materials as alternative raw material in industrial systems can be
considered an interesting alternative which leads to economic profit and reduction in environmental
impact.
The incorporation of waste and by-products in the ceramic process is a good strategy because it
diminishes the amount of waste material going to landfill and saves resources and energy. The
503
thermal treatment can sinter the inorganic fraction of the waste, which acts as a fluxing agent, and
combusts the organic pollutants that are present [5]. Besides, the pollutants could be immobilized
in the clayey matrix, decreasing their releasing and reducing the environmental damage. Because
of all these reasons the incorporation of waste materials in the ceramic process has become more
and more established [6-14].
Santander Bay sediments have shown to present significant concentrations of heavy metals and
organic pollutants and thus require treatment and confined disposal for their proper management
[15-18]. In previous studies the valorisation of Santander Bay sediments in ceramic processes has
been considered. The sintering capacity of Santander Bay sediments has been proven and the
optimum sintering temperature established [19]. Pressed free-clay sediment bodies fired at this
temperature met the European standards regarding water absorption and mechanical resistance
[19,20]. Besides, the environmental behavior of both clay and sediment has been evaluated prior
and after firing by means of leaching tests [21], showing that As leaching was increased with the
thermal treatment. This highlights the necessity of understanding the influence of temperature on
the As behavior for obtaining environmentally friendly clay/sediment ceramic bodies.
Sequential extraction is a frequently used approach to evaluate metal distribution into different
chemical forms present in a solid phase and to identify the strength of metal binding to the
particulates. Despite some criticisms (potential for reagents to be non-phase specific, re-adsorption
of ions solubilized by a reagent on a different phase, results dependence on the procedure used)
the sequential extraction schemes remain widely used and are considered an essential tool in
establishing element fractionation in soils and sediments [22,23].
The aim of this work was to apply the sequential fractionation method proposed by Silveira and
cols [24] to unfired and fired samples of clay and sediment to evaluate the different fractions of As
(soluble exchangeable, surface adsorbed, organic matter, Mn oxides, poor crystalline Fe oxides,
crystalline Fe oxides, residual) and to determine the effect of the thermal treatment on the As
distribution. After that, equilibrium compliance leaching tests were applied to unfired and fired
samples to verify the capacity of the sequential extraction tests to predict the effect of firing on the
As leaching behavior.

Dredged sediments were collected in the Suances estuary (Santander Bay), while clay was
provided by a local masonry. Dredged sediments were selected because of their optimum sintering
temperature [19] was closer to the firing temperature used by the clay supplier. Both clay and
sediment were characterized for particle-size distribution by sieving. The element composition was
determined by X-ray fluorescence, XRF, using an ARL Advant XP analyzer with UNIQUANT 5.0
software. The mineralogical composition was determined by X-ray diffraction analyses (Siemens
D5000 diffractometer), using CuK radiation and operating at 30 mA and 50 kV.
Clay and sediment were thermally treated in a laboratory muffle (Hobersal, 12 PR/300) at a
maximum temperature of 1,050C, using a similar cycle to that employed in the face-brick
manufacturing. Both unfired and fired samples were submitted to the sequential fractionation
procedure (Table 1) proposed by Silveira and cols [24]. Briefly, Silveiras procedure extracts metals
associated with seven fractions: 1) soluble exchangeable, 2) surface adsorbed, (3) organic matter,
(4) Mn oxides, (5) poor crystalline Fe oxides, (6) crystalline Fe oxides, (7) residual. Sequential
extractions were carried out in triplicate, using 1 g of air-dried sediment. Sediment samples were
placed in polycarbonate centrifuge tubes, mixed in a stepwise fashion with various reagents, and
the suspensions equilibrated as describe in Table 1. According to Silveiras suggestions, after
equilibrium is reached the solution and solid phases were separated by centrifugation at 1225g for
10 min. After each successive extraction, the solid residues were suspended in 5 ml of 0.1 M NaCl,
shaken by hand, and centrifugated to displace extracting solution remaining from the previous step.
The supernatant was added to the former extractant. The solutions were filtered through a 0.45m
membrane, and the solid residues preserved. Arsenic concentrations were measured with an
inductively coupled plasma-mass spectrometry (Agilent 7500ce). Equilibrium compliance leaching
tests were developed according to UNE 12457 1-2 [25,26], and As concentrations in leachates
were analyzed by means of inductively coupled plasma-mass spectrometry (Agilent 7500ce).
504
Table 1. Sequential extraction procedure for As (1 g sample) [24]
Fraction Solution Equilibrium conditions

1. Soluble exchangeable 15 ml 0.1 M CaCl2 2h, room temperatura
2. Surface adsorbed 30 ml 1 M NaOAc (pH 5) 5 h, room temperature
3. Organic matter 5 ml NaOCl (pH 8.5) 30 min, 90-95 C
4. Mn oxides 30 ml 0.05 M NH2OH/HCl (pH 2) 30 min, room temperature
5. Poor crystalline Fe 30 ml 0.2 M oxalic acid + 0.2 M
oxides NH4 oxalate (pH3) 2 h, dark
6. Crystalline Fe oxides 40 ml 6 M HCl 24 h, room temperature
7. Residual HNO3-HCl digestion

Figure 1 shows that particles comprising clay were generally smaller than those of sediments. Both
clay and sediments were mainly composed of SiO2, Al2O3 and Fe2O3 (Table 2). Santander Bay
sediment contained also significant concentrations of CaO, MgO and K2O, which can act as fluxes
when submitted to a thermal treatment. The high sediment loss on ignition (LOI) value indicated
that high loses of organic compounds will be generated in the kiln during firing. The XRD patterns
showed that sediments were mainly composed of quartz (SiO2), calcite (CaCO3), anhydrite
(CaSO4) and dolomite (CaMg (CO3)2), while clay was composed of quartz, hematite (Fe2O3) and
different types of silicates (illite, KAl2Si3AlO10(OH)2, moscovite, KAl3Si3O10(OH)2, and orthoclase,
KAlSi2O6).
Table 1. Oxides composition of the raw

materials by means of XRF
Composition [%]
Component Clay Sediment
SiO2 63.58 53.54
Al2O3 17.16 8.43
Fe2O3 6.06 4.5
MnO 0.07 0.03
MgO 0.97 2.36
CaO 0.57 7.48
Na2O 0.63 1.51
K2O 3.08 1.85
TiO2 0.85 0.55
P2O5 0.12 0.17
LOI 6.03 19.35
The results of the sequential extraction test (Figure 2) showed that As was mainly bounded to F1
(exchangeable), F5 (amorphous Fe oxides) and F6 (crystalline Fe oxides) fractions in unfired clay
and sediment. Clay had a higher percentage of As linked to the exchangeable fraction than
sediment (47.2% vs. 17.3%), and due to the F1 fraction is related to the most easily extracted As
505
amount, As in unfired clay might have higher mobility than As in unfired sediment. However, the
amorphous and crystalline Fe oxides- associated As amounts were higher in the sediment sample
than in the clay one (79.0% vs. 42.2%), indicating than most As in sediment was bounded to
stables phases, requiring relatively extreme environments for their releasing.
The thermal treatment produced a redistribution of As in the fired matrix, increasing the As
amounts associated to the exchangeable fraction in both fired clay and sediment (72.8% in clay
and 40.1% in sediment), showing that the As quantities released should be higher after firing. This
could indicate that the liquid phase formed during the sintering process did not immobilize As in the
new structure formed. This was confirmed by the Fe oxides- associated As amounts in fired
samples (22.6 % in clay sample and 52.1% in sediment one), lower than those corresponding to
the unfired samples, excepting for sediment F6. Besides, fired sediment presented higher
percentages of As linked to both amorphous and crystalline oxides than clay, indicating that the
efficiency of the sediment sintering process to trap As was also higher than the produced in clay.
As consequence, As in sediment fired samples must have lower mobility than As in fired clay.
To verify these results equilibrium compliance leaching tests, with ultrapure water as leachant, time
of contact of 24 hours (with solution stirring) and L/S ratios of 2 and 10 were developed according
to UNE-EN 12457 1-2 [25,26]. The results (Figure 3) indicated that tests developed with L/S ratio
of 2, which simulated the equilibrium at short times and low pH values controlled by the acid
neutralization capacity of the material, produced higher As concentrations in all unfired and fired
samples than the L/S ratio of 10, which represents the exhaustion of the soluble species in the
equilibrium state.
If the effect of the thermal treatment on leaching is evaluated, it could be seen that the sintering
process increased As leaching in both clay and sediment samples. This confirmed the sequential
fractionation results, which pointed out the higher As releasing because of its bounding to less
stable fractions (F1, exchangeable fraction vs. F5 and F6, poor crystalline and crystalline Fe
oxides). Besides, leachates coming from fired clay samples presented higher As concentrations
than fired sediment ones, showing the higher capacity of sediment to immobilize As when
submitted to a thermal treatment.
Apart from the relevance of the As fractionation on leaching, anionic species releasing behavior is
highly dependent on the pH [22,27]. Thus, As leaching is favored in extreme conditions, at acidic
and alkaline pH values. The pH values obtained in the fired samples leachates (in the range 10.0-
506
10.5 pH units) were higher than those in unfired samples (in the range 7.2-7.7 oH units). This trend
may be due to the carbonates decomposition during the firing process, that generated calcium
hydroxides which increase the pH values [21]. For these reasons, in future works the relative
relevance of As fractionation and pH on the As leaching will be studied in depth by means of the
analysis of Iberian clay samples with different carbonate proportions prior and after their thermal
treatment.
CONCLUSIONS
Clay and sediment were characterized, showing that they are mainly composed of SiO2, Al2O3 and
Fe2O3. Sediments also had significant amounts of flux agents, which can contribute to the sintering
process. The XRD patterns indicated that sediments were composed of quartz, carbonates and
sulfate, while clay was constituted by quartz, hematite and silicates.
The sequential extraction test showed that As was mainly associated to exchangeable and Fe
oxides fractions in unfired samples. Because of the high As quantities bounded to stables phases
such as amorphous and crystalline Fe oxides the As mobility could be considered low, especially in
the sediment sample. The thermal treatment increased the exchangeable fraction-associated As
amounts, which could imply that As leached quantities could be higher after firing. The As quantity
bounded to the exchangeable fraction is higher in the clay sample, which seemed to indicate that
As releasing could be more significant in clay than sediment.
Equilibrium leaching tests confirmed the sequential extraction results. The As leached
concentrations were higher in fired samples of clay and sediments than in unfired ones. Leachates
coming from fired sediment samples had lower As concentrations than fired clay, showing the
higher sediment capacity to immobilize As in the sintered structure.
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in clay bricks. Constr Build Mater 22 (2008) 755-762.
[5] R. Alonso-Santurde, A. Coz, N. Quijorna, J.R. Viguri, A.Andres. Valorization of foundry sand
in clay bricks at industrial scale. J Ind Ecol 14 (2010) 217-230.
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ceramic bodies. Ceram Int 30 (2004) 99-104.
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wastes in the production of ceramic bricks and tiles. J Eur Ceram Soc 25 (2005) 1149-1158.
[8] S.N. Monteiro, C.M.F. Vieira. Effect of oily waste addition to clay ceramic. Ceram Int 31
(2005) 353-358.
[9] K.L. Lin. Feasibility study of using brick made from municipal solid waste incinerator fly ash
slag. J Hazard Mater B137 (2006) 1810-1816.
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boron wastes in the production of heavy clay ceramics. Ceram Int 35 (2009) 447-452.
[11] G. Cultrone, E. Sebastin. Fly ash addition in clayey materials to improve the quality of solid
bricks. Constr Build Mater 23 (2009) 1178-1184.
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507
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Santander, northern Spain. Environ Res 106 (2008) 304-312.
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bodies from contaminated marine sediments. Ceram Int 34 (2008) 1917-1924.
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microstructural characterization of sintered ceramic bodies from contaminated marine
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sintered contaminated marine sediments. Fresen Environ Mull 17 (2008) 1736-1743.
[22] C. Gleyzes, S. Tellier, M. Astruc. Fractionation studies of trace elements in contaminated
soils and sediment: a review of sequential extraction procedures. Trends Anal Chem 21
(2002) 451-467.
[23] N. Kreidi, G. Armiento, G. Cibin, G. Cinque, C. Crovato, E. Nardi, R. Pacifico, C. Cremisini,
A. Montana. An integrated geochemical and mineralogical approach for teh evaluation of
arsenic mobility in mining soils. J Soils Sediments 11 (2011) 37-52.
[24] M.L. Silveira, L.R.F. Alleoni, G.A. OConnor, A.C. Chang. Heavy metal sequential extraction
methods- A modification for tropical soils. Chemosphere 64 (2006) 1929-1938.
[25] UNE. UNE-EN 12457-1. Characterization of waste leaching compliance test for leaching of
granular waste material and sludges. Part 1: one stage batch test at liquid to solid ratio of 2
l/kg for materials with high solid content and with particle size below 4 mm (without or with
size reduction). 2003
[26] UNE. UNE-EN 12457-2. Characterization of waste leaching compliance test for leaching of
granular waste material and sludges. Part 2: one stage batch test at liquid to solid ratio of 10
l/kg for materials with high solid content and with particle size below 4 mm (without or with
size reduction). 2003.
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experiment. Waste Manage 22 (2002) 521-530.
ACKNOWLEDGEMENTS
This work was conducted within the framework of the Spanish Ministry of Education and science
Projects (CTM2009-11303 and CTM2008-06344-C03-01). R. Alonso-Santurde was funded by the
Spanish Ministry of Education and Science on an F.P.I. fellowship.
508
USAGE & ATTITUDES ON WASTE PAPER RECYCLING OF UNIVERSITY

STUDENTS AND ITS ECONOMIC EFFECTS IN TURKEY
1 2 3
H. Zulfikar , N. Beken and B. Engin
zulfikar@istanbul.edu.tr
nalbeken@istanbul.edu.tr
b.engin@istanbul.edu.tr
ABSTRACT
Paper, with a lot of use in industry and cultural fields, is one of the most important items
of need. Development in the paper industry is considered to be one of the decisive
elements in the country's industrial and cultural development level. Per capita paper
consumption is considered as a measure of countries' levels of development. Paper and
cardboard are mainly used in the recycling of solid wastes. Waste paper is very important
for the world economy. The main substance of the paper pulp is obtained from trees.
When used papers are recycled, the need for raw materials diminishes. Environmental
pollution is important for the use of waste as raw materials. Industrial and domestic
wastes are the sources of waste paper. When waste papers are recycled, air and water
pollution are prevented and a saving is made in water and energy consumption. Our
study was influenced by such themes and a survey was conducted among the students
from various universities representing Istanbul and Turkey. In this study, the total paper
demand of students, usage and attitudes on waste paper of students, economic
evaluation, and economic effects of paper waste recycling, as well as the level of
environmental awareness were examined.
Keywords: Waste paper recycling; statistical estimations; economic effect; environmental

awareness, environmental statistics
INTRODUCTION
Paper& board have a specific importance amongst all the recyclable solid wastes. Due to the fiber
loss at each separate use, waste paper which can at most be used only for 5 times, loses 5-30 %
in quantity while being recycled [1,2]. Industrial and domestic wastes comprise the sources for
waste paper [3]. Recycling of waste papers serve both to the prevention of air and water pollution
and economization of water and energy consumption [4.5,]. There is an explicit difference between
the treatment processes of recyclable wastes in developing and developed countries. In most
developed countries, the improvement of recycling is usually a market driven domestic market
phenomenon. The fact that the product life span hence the quantity of related wastes are both low
in developing countries leads to the low quality and quantity in the supply of secondary products.
Therefore, a raw material shortfall comes into question in the field of recycling [6]. Waste paper
constitutes the major raw material for paper manufacturing in our country. The total quantity of
waste paper collected in Turkey increased to 1.796 tonnes in 2007 and 1.840 tonnes in 2008.This
corresponds to a recycling ratio of 43 % for the year 2008 [7]. Together with the increase in the
ratio of waste paper use in paper industry, there has arised a waste paper market.. In Turkey, out
of the collected waste paper, fluting and test liner cardboards (corrugated cardboard sector
external package boxes for white appliances), chromo board and etc. are manufactured. As it can
be seen herebelow, this constitutes a significant topic which deserves to be dealt with from the
perspective of university students behaviour and attitude.
509
GOAL AND SCOPE
The importance of information gathering, informing and information management is evident in
environmental management. Studying the relationship with environmental consciousness and
current information level of young people, especially university students with high levels of
adaptation to innovation and knowledge flexibility, has a special importance in strategic decision
making processes. Therefore, throughout this study the environmental consciousness, the
information level, opinion and thoughts, behaviour and attitude of the young people pursuing higher
education, regarding solid waste, paper and cardboard wastes and recycling have been tried to be
identified. By doing this, effective environmental policy establishment and implementation together
with reaching rational outcomes at socio-economic and socio-cultural decision making processes
will be enabled. Statistics based analyses play a significant role in the formation of accurate
communication strategies and efficient and scientific environmental management strategy based
particularly on data gathered from environmental pollution, environmental consciousness and
related behaviour and attitude. To be able to make rational assessments on environment,
communication and economy, to pass beyond conventional approaches to realize the partial supply
and demand analyses at perceptional level, solid waste and paper and board wastes management,
the recycling of these wastes, and provision of scientific subsidy with environmental consciousness
for the adequacy and efficiency of the particular share to be allocated from within the national
income are all amongst the subgoals of the study. The study was realized with a total number of
447 students pursuing higher education at associate, degree and post-graduate levels in state and
foundation universities based in Istanbul. Istanbul, as a city comprising the 18 % of the total
population, 13,42 % of the total number of households, 8 % of the state universities, 4 % of the
foundation universities, It would be possible to use the outcomes of the study to come up with
nation-wide assumptions from certain perspectives. Within this scope, between April 11 May 20,
2011, a total number of 8 faculties, 2 vocational schools and 18 departments out of 3 state, 3
foundation universities and 1 foundation vocational school were selected. Eventually, the results
have been obtained through one of the quantitative research methods; face-to-face interview
technique, applied on 447 students, 419 of whom were coming from state and 28 coming from
foundation universities, 24 of whom were masters and PhD students with the rest being associate
and degree level students.
METHODS
Research Model and Sampling Method

The research has been carried out through face-to-face interview technique by employing
quantitative question form, combining both descriptive and analytical research methods. A question
form consisting of a total number of 43 questions which would also be used on the same target
audience for another subgoal and for this particular study, questions regarding environmental
consciousness, solid and paper & board wastes, recycling and expenditures have been evaluated.
Additionally the existing questions have been examined in the demographic breakdowns. Also the
data obtained by measuring different scales have been converted into percentages, to secure
efficiency in the comparison, evaluation and interpretation.
In the sampling design Multi-stage Sampling Method has been used and the method in question
has been applied with a 4 - stage process.
The sample size was determined as n=474 by tolerable error as e=0.045 with 95 % confidence
level. Nationwide and Istanbul city distributions of some of the variables taken into consideration
while determining the sample group are presented in Fig. 1 below.
510
Fig. 1. Nationwide and Istanbul City Distributions on the Basis of Certain Variables [%]
Statsitical Analyses and Tests

The statistical tests and techniques required for the results representation of the population,
internal and external validity and confidence were taken into consideration, while Cronbachs alpha
coefficient was preferred for the scales consistency and confidence tests, t test was preferred for
the comparison of two population estimates and related parametric significances.
Additionally, in group comparisons like faculties, disciplines and classes ANOVA and The Mann
Whitney U tests were used while chi-squared test was preferred for distribution conformity and
dependence tests where siginificance level was taken as 0.05 (p=0.05). Besides, in analyzing the
relation between some variables, pearson and spearman correlation analyses and regression
analyses were done and the results were evaluated at p0.05 level. For statistical tests and
analyses SPSS version 17 and PASW version 18 statistic programmes were used.
FINDINGS AND EVALUATIONS
General Evaluations
First of all, students were asked to evaluate 20 different topics/probable problems regarding
environment and its related fields under different headings. The evaluations of the students on
these different problems were measured and converted into percentages by using scales are
shown in Table 1. In Table 1, the values representing some variables are observed in percentages.
Table 1. Opinions on Environment and Other Problems Based on Certain Variables [%]
TOPICS / PROBABLE INFORMATION RISK LEVEL [%] CURRENT ANXIETY FUTURE ANXIETY
PROBLEMS LEVEL [%] LEVEL [%] LEVEL [%]
Nuclear Risks 60,08 80,81 81,65 78,75
Chemical Risks 59,82 80,03 77,9 79,41
Air Pollution 75,68 80,93 81,7 82,61
Lake, River and Sea Pollution 73.76 82,15 83,37 81,56
Solid Wastes 64,93 75,64 78,19 78,11
Soil Polllution 66,26, 77,26 77,91 76,29
Water Pollution 76,43 83,66 84,97 84,08
Unemployment 69,49 83,52 80,85 77,77
Alcohol 65,92 50,67 55,02 61,94
Drugs 61,25 77,25 72,76 71,05
Cigarette 70,12 64,21 69,19 64,25
Terror 72,62 86,41 86,31 72,77
Inflation 65,61 67,82 66,4 64,51
Traffic 75,35 73,72 71,92 72,76
Food Based Risks 67,02 77,64 75,16 74,6
Poverty 74,1 80,82 78,59 77,64
AIDS 57,53 65,26 68,13 66,47
Moral decay 68,27 74,06 73,54 76,86
Mobile Phones 74,38 66,32 66,57 73,73
Conflicts of political ineterests 73,75 79,34 78,16 82,52
As it may be seen on Table 1, amongst all the problems, the first three problems that the students
are least informed about have been identified as AIDS (57.53%), chemical risks (59.83 %) and
nuclear risks (60.08 %). Nonetheless, while the risk perception and anxiety levels of the students
for AIDS are again at low levels, risk and anxiety levels for chemical and nuclear hazards have
been identified at high and even above average levels.When the analysis was realized at lower
levels, the alcohol consumption problem was bearing rather higher risks for state university
students (55.44 %) while that particular problem was at lower risk levels (46.88 %) for foundation
university students.
511
In the next sub-title the 20 problems on which the students were asked to present their opinions,
were analyzed under the headings problems related with the environment and other
problems(economic, political and social problems) within the scope of 4 different variables.
Fig.2 Perception Levels Related to Environmental and Other Problems on the Basis of Different
Variables [%]
As it can be seen on Fig.2, the perception levels may not always be formed with information level.
When the evaluations are realized under the headings environmental problems and other
problems, significant differences have been analyzed between these two problem groups. When
the group values are lined up, it was determined that the two groups were different and that there
were no significant relations between the groups (p0.05). Thus, despite the fact that the students
information levels regarding environmental problems are lower when compared to their information
levels regarding other problems, the fact that their risk and anxiety levels have reached a
significantly high level, is observed as a natural consequence of this (p0.05). In other words, due
to intellectual consciousness and related reasons, it is probable that the students have perceived
the environmental problems with more risk and anxiety. Additionally when the topic was looked into
from the perspective of environmental problems (refer with fig.3), it was only the headings called air
pollution and water shortage where any kind of statistical difference was observed between the
students information level and risk perceptions(p0.05). The reason why there is no significant
difference despite the existence of high levels, seems probably to arise from the fact that these
problems are either more visible or appreciable. While the environmental problems that the
students are least informed about with a significant difference from the average (p0.05) are
chemical risks (59.82 %) and nuclear risks (60.08%) respectively, environmental problems that
they perceive to be the least risky with a significant difference from the average are solid wastes
2
(75.64%) and soil pollution (77.26%) respectively. (Regression Analysis, R =0.87, Adjusted
2
R =0.82, F=17.38, p=0.006<0.05 DW=1.71). Nonetheless, it was analyzed that only the risk
2
perception has an effect on the current anxiety level.( Regression Analysis, R =0.87, Adjusted
2
R =0.82 , F=17.38, p=0.006<0.05 DW=1.71, =0.82 %).
Fig. 3.Information and risk perception levels regarding environmental problems [%]
Evaluations on Solid Waste and Paper & Board Wastes
512
It was observed that the concept of solid waste does not evoke anything or does not mean
anything in one out of every six students (5.44 %) When the term solid waste is used, paper &
board was remembered by the foundation university students at a level of (71.43 %) which was
(41.29 %) higher than that of the state university students (p0.05). The concept of solid waste,
due to its importance on environmental pollution and paper&board concepts rank similarly in the
minds of the students at 82.2 % level (R=0.822). This high connection is a feature which can prove
to be effective for perceptional change in waste management. As a matter of fact, when the
importance perception of solid wastes in environmental pollution is increased by 1 point ( 1 %), this
leads to an increase of 1.82 points( 1.82 %) in the importance perception of paper&board, whereas
a 1 point increase in paper&board importance perception only leads to an increase of half point.
Fig. 4. Perception levels related to paper-board on the basis of certain variables [%]
It was observed that the students have a sense of importance above their actual information level
regarding environment or paper-board wastes (fig.4). Despite this, their anxiety level for the
particular harm caused by paper-board wastes is below their interest and importance perceptions
and seem to be in parallel with their low information levels. Thus, as a result of the relation
analyses no statistically significant relation was observed between information and interest together
with information and importance giving (p0.05). On the contrary, between information and anxiety
significant and strong relations were observed (p0.05). in a negative sense which indicates that
the anxiety will decrease when the information level increases (R=-0.749), and, between
importance giving and anxiety, when importance giving increases, anxiety will also increase.
Besides, seen that a 1 % increase in information level will decrease the anxiety level by 2.26%
2
(R =0.561, F=7.669, p=0.032<0.05). Nevertheless, a 1 % increase in importance giving level leads
2
to approximately 0.5 % (0.533 %) increase in anxiety level. (R =0.656, F=11.448, p=0.015<0.05).
Recycling
When asked for spontaneous answers as to which solid wastes can be recycled, one in every 4
university students (26 %), denoting a very high students populace, either was able to say nothing
at all or simply did not give an answer.This ratio corresponds to an approximate number of 1 million
(917,627) university students in Turkey. Amongst the respondents even statistically significant most
remembered paper&board wastes are expressed at 64.21 % which is a very low ratio
corresponding to 47,51 % within the total. The subsequent solid wastes mentioned, on the other
hand, are, plastic at very low ratios (43.4 %), glass (38,7 %), metal (21,7 %) and battery-
accumulator (15,44 %). Amongst all the solid wastes, it was observed that the kinds of waste which
are said to be recycled spontaneously and in an assisted manner are paper&board and glass, with
the former reaching above the average remembering level and the latter remaining at the limit
value (refer with fig.5). The average information level regarding recycling (43,69 %) is also at a very
low ratio. Thus the aided remembering percentage of paper & board waste to be recycled
increased to 78,46 % in comparison to the spontaneous remembering rate. This significant
increase (p<0.05) can serve as an indicator of even the concerned waste type to be recycled not to
be sufficiently present in the agenda of the students. Another piece of information is that it was
discovered that the average paper&board waste collection efforts and the level of participation in
these efforts are differentiated from battery (42,51%) and glass (29,31 %) waste collection ratios
513
Fig. 5,Spontaneous-aided remembering rates for solid wastes and their distance to mean [%]
with a significant advantage (p<0.05) and increased to 74,27 %. It was observed that the average
participation level for this particular activity was realized at a rate of 55.1 % and that one in every
two persons has taken part in it.
CONCLUSION
In this study environmental consciousness and behaviour and attitudes of the university students
from Istanbul and its environs regarding solid wastes, paper & board wastes and their recycling
have been examined. In our study, under the heading of environment and other problems, upon the
analysis of the students information and opinions, it was observed that their information level
regarding environmental problems were low whereas their risk and anxiety levels were highIn other
words, it was discovered that the anxiety level was not knowledge-based. The fact that the
students attending either state or foundation universities also led to different evaluations. When the
spontaneous remembering rate regarding the sorts of solid wastes in particular was taken into
consideration, differences were observed between state and foundation universities together with
social science and science students. Foundation university and social sciences students seem to
remember more types of waste at higher levels and instead of plastic wastes, they position
paper&board wastes at the uppermost place. Solid wastes and domestic wastes are perceived 40
% different from one another. When the field of education shifts from science to social disciplines
and further to fine arts, the importance perceptions of paper&board wastes increase in parallel.
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514
14th September
Plenary Lecture II
( Energy recovery from heavy metal contaminated
biomass using pyro-gasification processes )
Ange Nzihou
515
Professor Ange Nzihou [Ecole des Mines d Albi-Carmaux, France]
Biography
Professor Nzihou obtained his PhD degree in chemical engineering at the National Polytechnic
Institute in Toulouse, France in 1994. His research interests focus on treatment processes and
engineering new materials from waste and biomass. He has published about 120 papers in
peer-reviewed journals and confere
nce proceedings, and supervised 12PhD students and 14 post-docs. Since 2001, he has
received 24 significant grants from industry and governmental agencies.
He is currently Director of the RAPSODEE research Centre (Research on Particulate Solids,
Energy and Environment) at Ecole des Mines Albi in France, and Editor-in-Chief of Waste and
Biomass Valorization, a peer reviewed international journal edited by Springer. He is the
initiator and the Chairman of the WasteEng Conference Series dedicated to organizing
conferences and seminars on Waste and Biomass Valorization
He is currently guest professor at a number of universities in the U.S. and in China. Professor
Nzihou is an expert for several organizations (national and international) and for international
industrial groups.
516
PLENARY LECTURE
at the 1st International Conference WASTES 2001 Guimars (Portugal)
Energy Recovery from Heavy metal contaminated biomass using pyro-

gasification processes
Prof Ange Nzihou,
Universit de Toulouse; Mines Albi; CNRS; Centre RAPSODEE, Campus Jarlard, F-81013 Albi CT
cedex 09, France
Contact : ange.nzihou@mines-albi.fr
Abstract:
The paper addresses the impact of inorganic components on the pyrolysis and gasification of
waste biomass for the production of energy. Thermal treatment options have been developed
to improve biomass use in energy production. Pyrolysis and gasification are interesting
because the gases produced may be cleaned from sulphur compounds and because gases burn
more completely, with less soot and producing almost no ashes in pyrolysis in particular. An
issue to be addressed remains mineral contaminants which may interfere at different levels,
including the final emissions. Problems related to minerals present in biomass depend on the
level and nature of their presence, and how they react at high temperatures.
The decomposition of carbon or carbon compounds releases an enthalpy that can be used for
generating heat. Operators dealing with the pyrolysis and gasification of biomass in particular
are rapidly confronted with the problem of ash contents of the biomass, whether it is virgin
biomass or waste biomass. The potassium and sulphur contents pose problems related to
vaporization, condensation and melting of ash silicates. Contaminated biomass, particularly
wood impregnated with insecticides such as CCA (copper chromium arsenate) must be dealt
with separately due to the large amounts of non-combustible inorganic components which can
reach 10% by weight.
The influence minerals may have on biomass transformation into energy is examined, and the
different ways the biomass and waste biomass may be treated is reviewed. The fate and
element transfer to the atmosphere also occurs for metals with low boiling points such as Hg,
Zn and Cd. The presence of chlorides may enhance volatilization as metal chlorides. Trace
element enrichment in fly ash is related to volatilization of elements during the reaction
followed by condensation on the smaller particles with largest specific surface areas, during
the cooling step.
Two biomass streams namely residues from phytoremediation and impregnated wood wastes
are considered in this paper.
517
14th September
Session 1.5
( WASTE MANAGEMENT: STRATEGIES,
SUSTAINABILITY, MARKETS AND INITIATIVES 1 )
Chairman: Javier Viguri
518
ANALISYS OF THE PROPERTIES OF WASTE-BASED GEOPOLYMERIC

BINDERS AFTER CURING IN WATER
1 2 3
I.C. Silva , J. Castro-Gomes , A. Albuquerque
1
Castelo Branco Polytechnic Institute and Centre of Materials and Building Technologies,
University of Beira Interior, 6201-001 Covilh, Portugal, icastanheira@ipcb.pt
2
Centre of Materials and Building Technologies, University of Beira Interior, 6201-001 Covilh,
Portugal, castro.gomes@ubi.pt
3
Centre of Materials and Building Technologies, University of Beira Interior, 6201-001 Covilh,
Portugal, ajca@ubi.pt
ABSTRACT
Tungsten mud from a local mine exploration may be recycled to produce geopolymeric
binders after an alkaline activation. This procedure allows using these binders in several
applications in construction and hydraulic works avoiding the landfilling of those wastes
with several economic and environmental benefits. Preliminary tests were carried out to
study the effect of different dry curing temperatures, curing water periods and mixes of
mud and alkaline solutions on the structural stability and pH variation in water of waste-
based geopolymeric binders. The properties (bulk density, specific surface area,
chemical composition, microporosity, durability and mechanical compressive strength) of
a mix with ratios R(P/S) = 5 and R(S/H) = 4 were analyzed after curing in water. The
durability was also studied in solutions with 5% of acetic acid and sulfuric acid, revealing
good resistance of the binders to acid attack. This study also demonstrates that mining
waste mud can be used to produce geopolymeric binders for wastewater treatment
processes.
Keywords: acid conditions, compressive strength, mine waste mud, wastewater treatment
INTRODUCTION
Geopolymeric binders (or just geopolymers) may be obtained through a complex chemical reaction
in an alkaline environment (condensation and polymerization) of alumino-silicate materials, called
precursors (e.g., waste sludge, fly ash, slag and calcined clays). Due to its chemical composition, a
particularly waste mud of the Panasqueira mine, located in Portugal, one of the most important and
largest tungsten mines in the world, presents very good reactivity with alkaline activators after a
thermal calcination process and under certain mixing conditions [1] to produce waste-based
geopolymeric binders (WGB). They have potential for use in wastewater treatment processes, due
to its suitable mechanical strength [2], good durability, capacity for resistance to acids and sulfates
[3], and appropriate porosity, void ratio and specific surface. Therefore, the objective of this
investigation was to analyze several properties of WGB when in contact with water and acide
solutions in order to evaluate the suitability of the binders to be used in wastewater treatment
processes for the treatment of urban, stormwater and industrial effluents.

Characterization of the waste mud and production of alkali-activated materials
Mining waste mud obtained from Panasqueira, after submitted to calcination at 800C temperature
for 2 hours, was used as precursor (P) for the alkali-activated process. The chemical oxide and
mineral compositions of the mine waste mud, determined by energy dispersive X-ray spectroscopy
(SEM/EDS, RONTEC equipment, USA) and X-ray diffraction analysis (XRD, Rigaku - DMAX III/C
equipment, USA) showed that has 70% of Al2O3 and SiO2 and a ratio SiO2/Al2O3 between 3 and 4,
and it consists mainly of quartz and muscovite.
519
Alkali activation solution was obtained by a combination of two activators; sodium silicate (Na2SiO,
L60, defined as S) and sodium hydroxide (NaOH, defined as H) at 10M molar concentration.
Geopolymeric mixes were obtained by mixing first together both alkaline activators according to
different mass ratios and precursor was added afterwards to the mix. A small amount of water,
approximatly 10% of mass of total precursor, was added to increase its workability. Mixing was
3
kept during 10 minutes before pouring the paste into moulds of 40x40x40 mm .
Compressive strength testing

Preliminary tests have been carried out to study the effect of different dry curing temperatures,
curing water periods and mixes of mud and alkaline solutions (Na2SiO and NaOH) on the structural
stability and pH variation in water of WGB. The results showed that the mix with mud/Na2SiO ratio
(R(P/S)) and Na2SiO/NaOH ratio (R(S/H)) of 5 and 4, respectively, cured at 20C, presented good
stability in water and the pH decreased from 10 to 7 in 24 days [2]. Those results indicate that
WGB present suitable stability to be used in wastewater treatment processes by filtration and the
final effluents have a pH in agreement with the water quality European legislation.
This mix was afterwards used for testing compressive strength in dry and wet conditions. 450
3
samples with 40x40x40 mm were produced, and were first submitted to an initial dry curing period
of 7 days at 20C and approximately 40% relative humidity. Later, 210 units were kept at 20C
(Phase I) for 14, 21, 28, 35, 42, 63 and 91 days and the others 240 units were cured at 80C
(Phase II) for 7 14, 21, 28, 35, 42, 63 and 91 days. After each dry curing age, samples of each
phase were immersed in separate vessels containing approximately 1 L of water during 24 hours,
7, 14, 21, 28, 35, 42, 63, and 91 days (i.e., from 1 to 13 weeks of immersion period, as shown in
Table 1) and the water was changed every two days. To evaluate the compressive strength over
time in dry and wet conditions, three dry samples were tested for each dry curing period and each
water immersion period. Compressive strength was determined according to the ASTM C 109
standard for testing hardened concrete.
Table 1. Summary of compressive strength testing program
Phases Curing Curing Immersion Number of

Replications
temperature time (days) in water (days) samples
0, 24 hours, 7, 14,
14, 21, 28, 35, 42
I 20 C 21, 28, 35, 42, 63 3 210
63 and 91
and 91
0, 24 hours, 7, 14,
II 7, 14, 21, 28, 35, 21, 28, 35, 42, 63
80 C 3 240
42 63 and 91 and 91
Test resistance to acids

In this experiment, 18 WGB cubic samples were prepared with the aforementioned mixture and the
samples were cured at 20C for 35 days. Then, 9 samples were immersed in a 5% acetic acid
solution and 9 others in a 5% sulphuric acid solution at 20C during 1, 2 and 3 months. After those
periods, the length edges and the mass weight of all samples were observed, as well as its surface
colour, appearance and colour transparency of the water solution after samples immersion. The
compressive strength of all samples was measured.
Other properties of WGB

Properties of the mix, such as bulk density, micro porosity, weathering durability, water absorption
and void ratio were also analyzed since they are considered important for the application of WGB
as bed material for wastewater treatment process. For this experiment samples with 2 cm (similar
to natural aggregates) were produced.
In order to compare the results with other natural and artificial materials normally used in
wastewater treatment, the bulk density, micro porosity, water absorption and void ratio were
520
determined for the following materials: expanded clay LECA (Figure 1a), pozzolana and granite
(Figure 1b), and GWB (Figure 1a). The bulk density and water absorption (in % of dry mass) of the
WGB was determined in accordance with the EN1097-6 standard (used for concrete aggregates).
The void ratio was calculated in accordance to the EN1097-3 standard. The bulk density of the
expanded clay, pozzolana and granite gravel was determined using a helium pycnometer.
a) b)
Figure 1. a) Artificial aggregates: WGB (left) and LECA (right), b) Natural aggregates: pozzolana
(left) and granite (right)
Finally, the resistance of the WGB to disintegration and weathering was determined by slake
durability test, which is normally carried out in weak rocks, like shales or similar. The test consists
in estimating the resistance of equidimentional shale fragments, weighing 40g to 60g each. The
slake durability index correspond to the percentage of dry mass of the fragments retained by a
drum of 2 mm (No. 10) square-mesh after two cycles of oven drying and 10 minutes of mixing in
water under the effect of deterioration and abrasion. Test results were expressed as a slake-
durability index for each particular rock (Id1). Two groups of WGB aggregates were tested: one
comprising aggregates dried at 20C for 35 days and another with aggregates dried at 20C for 35
days after immersion in water for 63 days and dried again at 20C. Before testing, both sets were
dried in an oven at 105 C for 24 hours.
Compressive strength testing

The results presented in the Figures 2 and 3 showed that compressive strength was reduced to
approximately half of initial values (dry conditions) after 24 hours of water immersion, regardless
the curing temperature and curing age. The decrease in strength continued during the first 4 weeks
of immersion, stabilizing in most of samples after that period of time between 1 MPa and 2 MPa. In
samples cured at 20C for longer dry curing ages (91 days) the values stabilized between 2 MPa
and 3 MPa after 6 weeks of water immersion.
14 days
21 days 7 days
(MPa) room curing (20C) oven curing (80C) 14 days
(MPa)
28 days
10 35 days 21 days
42 days24 28 days
8 63 days 35 days
91 days20 42 days
6 63 days
16
4 91 days
12
2 8
0 4
0
Figure 2. Variation of the compressive strength Figure 3. Variation of the compressive strength
Immersion period over time for different water immersion periods
over time for different water immersion periods
(20C curing temperature) (80C curing temperature)Immersion period
These results show that water curing leads to a strength decrease of the WGB. This behaviour was
also observed for alkali-activated metakaolin cured in water [4]. On the other hand, the addition of
water to improve the paste workability might have affected the hydrolysis of the samples and,
521
therefore, hinders polycondensation kinetics, leading to molecular destabilization of the geopolymer
matrix. The role played by water in the whole process of geopolymer synthesis is known to be quite
important. Water in excess seems to depress the alkali activity development of calcined kaolin
before stable crystalline phases formed, which was conrmed by the compressive strength results.
A study involving calcined kaolin indicated that nonevaporable water was necessary to keep the
strength stable and the optimum content was 7.4% [5].
The compressive strength after immersion stabilized around 1 to 2 MPa, similar to the values
presented by LECA (1.7 MPa) that needs higher temperatures to be produced. As expected,
granite aggregates present higher compressive strength (up to 120 MPa).
By comparing the compressive strength of the different materials, WGB is still advantageous over
the other two materials, since are obtained from wastes (i.e., promotes the reuse of waste mud
from mine activities), may be produced at low temperature (20C), present good stability in water,
does not change significantly their characteristics, are a durable material and, therefore, may have
the same effectiveness than other materials used for pollutant removal in treatment works.
Resistance to acids
The results show that the pH of the H2SO4 and CH3COOH solutions increased to approximately 0.6
and 4.4 points, respectively, in the early days, and continued stable during the remaining time of
the experience. The samples maintained their size and colour over the 3 months of immersion in
both acid solutions (Figures 4 and 5), but a slight deposit was observed in some samples placed in
the strong acid solution.
Figure 4. WGB sample before being Figure 5. WGB sample after immersion in
immersed in sulfuric acid sulfuric acid for 3 months
Regardless the immersion period, the percentage of mass weight loss was slightly higher for
samples immersed in the H2SO4 solution, i.e. it was about 0.1% higher than in the samples
immersed in the CH3COOH solution, as show in Table 2.
Table 2. Mass weight loss for samples Table 3. Evolution of the compressive strength of WGB
exposed to 5% acid solutions over time after contact with 5% acid solutions
Immersion CH3COOH H2SO4 Immersion CH3COOH H2SO4 solution

time solution solution time (days) Water solution (5%) (5%)
(days) (5%) (5%) 28 1.948 4.201 6.465
28 0.084 0.096 56 1.852 5.222 5.303
56 0.086 0.096 84 1.664 5.087 6.452
84 0.084 0.097
These results show that the samples were quite resistant to the attack of a strong acid, presenting
mass weight loss percentages lower than the ones observed by [6] with fly ash activated by NaOH
(the mass weight losses in acetic and sulphuric acid solutions (5%) were 0.5% and 2%,
respectively). Samples activated with sodium silicate solution had 3.8% of weight gain in the
CH3COOH solution and 2.6% of weight loss in the H2SO4 solution.
Changes in the percentage of weight loss can be explained by the aluminosilicate polymer
+ +
depolymerization and liberation of silicic acid from the samples, replacement of Na and K cations
by hydrogen or hydronium ion and dealumination of the geopolymer as a result of exposure to
acidic solutions [6].
522
Initially, after immersion for 28 days, the compressive strength of the samples (Table 3) immersed
in the CH3COOH solution was similar to the one obtained for the dried samples cured at 20 C for
35 days (4 to 5 MPa) [7]. With the increase of the immersion time there was also a slight increase
in the compressive strength. After 28 days of immersion in the strong acid, the samples increased
its compressive strength up to 6.5 MPa, maintaining a stable resistance until the end of the
experiment. However, regardless the immersion time, the compressive strength of the samples
immersed in the weak acid was, generally, lower than the results obtained for the strong acid (i.e.
the CH3COOH solution - the weak acid - seems to have weakened the structure of the WGB). In
tests conducted by [6], samples activated by NaOH solution, which had a rapid strength loss after
immersion in 5% acid solutions (about 45% of losses after 2 months of immersion), slightly
recovered and presented about 40% of strength reduction after 6 months in solution. Other
samples activated by Na2SiO had about 60% of strength decline after 6 months of immersion. Very
significant fluctuations of strength were observed in these two materials that were possibly
connected to the breakdown of some geopolymer components and migration of alkalis from the
specimens into solution superimposed by the acid attack.
According to [8] the crystalline geopolymer material prepared with sodium hydroxide seems more
stable in the aggressive environment of sulphuric and acetic acid solutions than the amorphous
geopolymer prepared with a sodium silicate activator. This may happen due to the presence of
cross-linked polymer structures that successfully resist attacking. Other investigations [9] show that
alkali-activated tungsten mine waste mud mortars with aggregates such as limestone, granite and
schist present low weight loss for the curing in 5% of sulphuric, hydrochloric acid solutions during
28 days. The weight loss was assigned to the detachment of little particles from the leaching of
unreacted sodium in the matrix, leading to an increase in porosity and allowing the acid solution to
enter inside the sample and removing calcium compound.
The results show that the compressive strength remains constant for the samples immersed in the
weak acid and increases in the strong acid followed by variations that according to [5] may occur
due of alkalis migration from the geopolymeric structure to the water solution. The instability of
strength is an issue that it is unclear and it needs investigation.
Other properties of WGB

Although water curing leads to a strength decrease of WGB, the slake-durability test in wet
conditions showed that dried aggregates can be marked as medium high durable and the
material loss is more significant if the sample has already been immersed (Table 4). When sample
was already immersed and dried before the test, the proportion of retained material decreases and
the rating for durability is medium low.
Table 4. Slake durability index based on a single wet cycle, Id1 (%)
Id1 (%) retained
WGB Durability
material
Dry 81.9 medium high
Dried after soaking in
70.9 medium low
water
3
For other physical properties, the density of the WGB (1625 kg/m ) is the same order of magnitude
3
as presented by the pozzolana (2360 kg/m ), all higher than the value of the other artificial
3 3
aggregate (LECA with 320 kg/m ) and lower than the value found for crushed granite (2640 kg/m ),
all materials that are widely used in filtration systems for wastewater treatment [9]. The water
absorption of the WGB is the highest with 20%, a figure close to the absorption of pozzolana (14%)
and LECA (11%). The crushed granite has the lowest value (0.4%). The void ratio is close for the
four materials, ranging from 39% to 46%, with the pozzolana and the WGB presenting an
intermediate value of 42%. With respect to the porosity, the total area of pores is higher for LECA
2 2
(6.37 m /g) while the WGB have a lower value (2.37 m /g).
The pozzolana and the crushed granite have a very small area of total pores (0.920 and 0.053
2
m /g, respectively). In the materials studied, the highest density corresponds to the smallest total
area of pores by varying the diameter of the pores in the same way that density. The results
indicate that the physical properties of WGB are suitable to be used as material for bed media in
523
wastewater treatment processes by filtration. Aggregates with a diameter between 1 and 2 cm are
suitable for the development of biofilm [10], since the void ratio exceeds 0.40.
Thus, this study demonstrates that the use of mine waste mud to produce WGB for wastewater
treatment processes can bring the following benefits: production of recycled aggregates for water
pollution control, minimization of environmental impacts associated with waste mines and reduction
of terrestrial deposits of mineral waste.
CONCLUSIONS
The results showed that the WGB developed in this study are stable in water, do not change
significantly the characteristics of water, are durable and its compressive strength decreased with
time after immersion in water, maintaining, however, an appropriate value for use in wastewater
treatment processes with filtration.
The mass loss observed in WGB after contact with acidic solutions is mainly due to a reaction
between the geopolymer structure and the CH3COOH solution, which caused the replacement of
cations exchangeable (Na +and K+) by hydrogen ions and led the depolymerization of aluminum.
The WGB also showed adequate resistance to acid attack, which is an important property for a
material to be used in wastewater treatment.
The density, microporosity, durability, water absorption and void ratio of the WGB aggregates are
also adequate for a good adhesion and biofilm development, essential for the removal of pollutants.
References
[1] F.Pacheco-Torgal, , J.Castro-Gomes, , S.Jalali,; Investigations on mix design of tungsten mine
waste geopolymeric binder, Construction and Building Materials, 22, 9, 2008; p. 1939-1949.
[2] I.Silva, J., Castro-Gomes A. Albuquerque. Study of the structural stability, pH variation in water
and influence of the curing conditions on mechanical resistance of mineral wastes geopolymeric
artificial aggregates (WGA) as alternative materials for wastewater treatment processes. Journal of
Architecture, Civil Engineering and Environment (ACEE), V. 3, N 3, (2010) 121-128.
[3] Silva I., Castro-Gomes, J. Albuquerque A.: Effect of Acid Conditions on the Structural Stability of
Mine Waste Mud-based Geopolymeric Artificial Aggregates for Wastewater Treatment, CIIEM
Proceedings, ISBN-13: 978-84-9978-014-6, pp
[4] A.Kirschner, H.Harmuth; Investigation of geopolymer binders with respect to their application for
building materials. Ceramics Silikty., 48, 2004; p. 117-120.
[5] Z.Zuhua, , Y.Xiao, , Z.Hualun, , C.Yue,; Role of water in the synthesis of calcined kaolin-based
geopolymer, Applied Clay Science, 43, 2009; pp. 218-223.
[6] T. Bakharev, Resistance of geopolymer materials to acid attack, Cem. Concr. Res.,35, (2004)
1233-1246
[7] I. Silva, J. Castro-Gomes, A. Albuquerque, Evaluation of the stability of waste-based
geopolymeric artificial aggregates for wastewater treatment processes under different curing
conditions, CIMTEC 2010 Proceedings in Advances in Science and Technology, Vol. 69 pp 86-
91, Trans Tech Publications Switzerland), Italy.
[8] A. Fernndez- Gimnez, A.Palomo Chemical durability of geopolymers
In:Geoplolymers:structure, processing, properties and industrial applications. J.L.Provis (Ed.) WP
9:167-178, 2009.
[9] F.Pacheco-Torgal, J.Castro-Gomes, J. Said Durability and environmental performance of alkali-
activated tungsten mine waste mud mortars. Journal of Materials in Civil Engeneering, (2010) 897-
904
[10] G.Tchobanoglous, F.Burton and H.D. Stensel Wastewater Engineering, Treatment, Disposal,
and Reuse. Metcalf & Eddy, McGraw Hill, New York, USA, 2003.
524
St
ANALYSIS OF AN INTEGRATED WASTE MANAGEMENT SYSTEM: PART A

MASS AND ENERGY BALANCES
F. Vigan* and S. Consonni

Dep. of Energy, Politecnico di Milano, Via R. Lambruschini 4, 20156 Milan, Italy
LEAP Lab, Via N. Bixio 27/C, 29121 Piacenza, Italy
Phone: +39 0523 35 6882 Fax: +39 0523 62 3097
E-Mail: federico.vigano@polimi.it
ABSTRACT
This paper reports the energy results of a research project on the comprehensive
analysis of an Integrated Waste Management System (IWMS) for Municipal Solid Waste
(MSW). It is directly linked to a second paper (Part B, authored by Grosso et al.) which
reports the outcomes of a Life Cycle Assessment (LCA) for the same system.
The analysis considers the Province of Piacenza, in northern Italy, where the MSW
management is based on an integrated system approach that aims to an almost self-
sufficient condition. The Reference Scenario studied is the year 2007, when 200,000
tons circa of waste were overall collected, achieving a Source Separation Level (SSL) of
about 38.7%. Based on this scenario, a hypothetical Derived Scenario with a SSL of
50% has been considered, with a particular focus on the performances of the WtE plant.
Results show that the increase in SSL subtracts a significant amount of MSW to the WtE
plant, but such a deficit can be easily compensated by gathering all the possible
contributions from the IWMS. In this way, while the authorized treatment capacity of the
plant remains fully exploited, the thermal input increases consistently, leading to higher
utilization of the plant, higher energy efficiency and an improvement on the electricity for
sale that grows by 27.3%.
Keywords: mass and energy balances; case study; integrated waste management system.
INTRODUCTION
The management of waste in the Province of Piacenza, in northern Italy, is based on an integrated
system approach that aims to an almost self-sufficient condition. All the Municipal Solid Waste
(MSW) produced in the Province are collected by a public company that manages its delivery to
several recycling facilities (some of them inside the Province, others outside), to a Waste-to-Energy
(WtE) plant in the provincial capital, Piacenza, and to other destinations. The Reference Scenario
studied is the year 2007, when 200,000 tons circa of waste were overall collected, achieving a
Source Separation Level (SSL) of about 38.7% (calculated according to Regional regulations,
which do not include all the waste typologies collected). On the basis of this picture a Derived
scenario has been developed, in which SSL reaches 50%, the target set by the Regulation
Authority.
BACKGROUND
The Integrated Waste Management System (IWMS) of the Province of Piacenza has been studied
considering three subsystems: (i) collection, selection and delivery of waste; (ii) recycling of
recyclable fractions; (iii) energy recovery of non-recyclable fractions in the WtE plant.
In this part A paper only the main mass and energy balance aspects of subsystems (i) and (iii) are
considered, while in the part B, authored by Grosso et al. [1], all the other aspects and also the
subsystem (ii) are analyzed.
525
Collection, Selection, Delivery
In 2007, eight main Separate Collections (SC) were active in the Province: Paper, Food waste,
Aluminum bins, Wood, Other metals, Plastics, Green waste, Glass. Aside of these, other
minor collections were practiced, however the overall situation were extremely fragmented because
very different from town to town. For example, Food waste was separately collected only in few
towns on the north-east part of the Province.
Moreover, there were other six significant streams of waste:
the Unsorted Residual Waste (URW), i.e. the undifferentiated waste collected in the black
bag;
the Bulky waste;
the Road sweeping waste;
the Cemetery waste;
the Other wastes, i.e. the ensemble of what collected with the minor SC;
the Purple bag waste. This stream was the result of a particular type of collection aimed
at gathering packaging wastes: paper, plastics, etc. in a mixed form.
Bulky waste and Purple bag waste underwent heavy selection procedures to recover as much
recycling materials as possible. However the yields of these processes were quite low.
All the recyclable waste fractions were delivered to material recovery facilities, possibly after a first
selection process. Many of these facilities were outside the Province, and only few inside the
administrative boundary.
All the non-recyclable waste fractions were, instead, delivered to the WtE plant for energy recovery.
In addition to these fractions, the WtE plant received also a non-negligible amount of Industrial
Packaging Wastes (IPW), which are likened to MSW by Regional regulations, dried sewage sludge
and sanitary wastes.
Energy Recovery
The WtE plant were build between 2000 and 2002, and it is a mass-burn incinerator with energy
recovery for the sole production of electricity. It features two identical combustion lines and a
common steam cycle.
Every line comprises an air-cooled grate combustor integrated with the steam generator and a dry
flue gas treatment based on an Electrostatic Precipitator (ESP), sodium bicarbonate and active
carbon injection, and a final fabric filter stage before the stack. In the original layout the plant were
equipped with a SNCR (Selective Non-Catalytic Reduction) system for NOX control, based on the
injections of solid urea balls in the first pass of the boiler (the post-combustion chamber).
Nominal thermal input of every line is 22.67 MW on LHV (Lower Heating Value) basis, with primary
and secondary air preheating at 155C. Tertiary air is injected between the first and second flue
gas passes for fouling control and it is not preheated.
The two lines share the common bunker and feed a conventional Rankine steam cycle. Steam is
evaporated at 43 bar and superheated at 390C. The nominal steam production of every line is
28.8 t/h. The steam turbine is a single cylinder machine rotating at 6800 rpm and connected
through a gear box to a 1500 rpm electric generator. Nominal gross power output is 11 MWE. The
turbine presents three steam bleedings at 11/3/1 bar (nominal), used to feed air preheating (11 and
3 bar), sewage sludge drying (11 bar), the deareator (3 bar), and condensate preheating (1 bar).
Exhaust steam from turbine expansion is condensed in an air-cooled condenser with nominal
condensing pressure of 0.15 bar.
Fig. 1 shows a schematic representation of the plant (only one line is depicted) with some
emphasis on the combustor - boiler subsystem, and all the material streams that enter or exit such
a grouping.
SCENARIOS
The analysis carried out considered two scenarios: a Reference Scenario very similar to the
situation recorded in 2007 and a Derived Scenario. A model of the WtE plant has been developed
and calibrated on the basis of the data collected during 2007 through the DCS (Distributed Control
System) and the CEMS (Continuous Emission Monitoring System) of the plant.
Both scenarios are fully illustrated in the following.
526
TURBOGENRATOR AIR-COOLED CONDENSER
STACK
Urea
DE-NOX
INJECTION OF
DRY UREA
SODIUM ACTIVATED
Natural gas
BICARBONATE CARBON
Flue gases
ELECROSTATIC
SANITARY PRECIPITATOR (ESP)
WASTES
BOILER
SEWAGE
SLUDGE FABRIC FILTERS
URW
Waste GRATE
COMBUSTOR
BUNKER FLUE GAS FAN

Bottom ash
Fly ash
BOTTOM ASH
SELECTION
METALS
Water
TO
INERTIZATION
FLY ASH STORAGE ACIDIC GAS ABATEMENT
RESIDUES
BOTTOM ASH
Figure 1. Schematic representation of the plant layout (only one line).
Reference Scenario
The Reference Scenario is based on:
the 2007 situation for the collection of waste; it is characterized by a SSL of 38.69%
(according to Regional regulations that do not consider all the waste categories collected);
the same mix of wastes of 2007 fed to the WtE plant;
the climatic conditions of 2007, in particular the same hourly air temperature profile - an
important parameter for the prediction of air-cooled steam cycle performances;
the plant layout of 2007, inclusive of a change introduced during the year and regarding the
addition of a final heat recovery for condensate preheating before the flue gas fan, which
reduced stack temperature from 180C circa down to about 130C, increasing energy
efficiency.
Derived Scenario
The Derived Scenario is based on the Reference Scenario except for:
the waste collection that reaches 50% SSL by enhancing all the SC and suppressing the
Purple bag collection;
the delivery to the WtE plant of all the combustible residues from the selection of
separately collected waste fractions, as well as from the selection of bulky waste;
the increase of IPW sent to the WtE plant in order to saturate the authorized treatment
capacity of 120,000 tons per year;
an extended working period, from the previous 8,000 authorized hours per year, up to
8,300 hours per year (the theoretical maximum that accounts for one stop per line per year
for maintenance and one stop per year for the entire plant for steam cycle maintenance);
the introduction of a high dust SCR (Selective Catalytic Reduction) system for NOX
abatement instead of the SNCR system.
527
METHODOLOGY
Collection
Mass balance for the collection system has been drawn starting from 2007 data, adopting an
approach based on Waste fractions, and the assumption that the total amount of MSW, as well as
the amounts of the other categories considered, in the Derived Scenario are the same of those in
the Reference Scenario.
Table 1 reports 2007 data, which also characterize the Reference Scenario, as well as the picture
of the Derived Scenario, inclusive of all the variations brought by the suppression of the Purple
bag collection and the enhancement of all SC. SC effectiveness has been modulated according to
data pertaining to other Italian experiences, as described in [2].
Table 1. Figures that characterize the waste collection in the two scenarios.
Reference
Scenario Derived
(2007) Scenario Variation
[tons per year] [%]
URW 96,682 77,823 -18,859 -19.51
Cemetery wastes 76 76 0 0.00
Road sweeping waste 2,817 2,817 0 0.00
SC + selection of "Bulk y waste" and "purple bag" waste

Paper and cardboard 23,095 30,107 7,012 30.36
Food waste 4,232 11,721 7,489 176.96
Aluminium bins 273 334 61 22.34
Wood 7,884 8,628 744 9.44
Other metals 2,396 2,974 578 24.12
Plastics 3,296 4,758 1,462 44.36
Green waste 15,077 15,425 348 2.31
Glass and inerts 9,106 12,359 3,253 35.72
Others 6,553 6,616 63 0.96
Residues from "Purple bag" selection 2,151 0 -2,151 -100.00
Residues from "Bulky waste" selection 26,477 26,477 0 0.00
Total waste collected* 200,115 200,115 0 0.00
* It is different from the amount of gross MSW, because of Regional regulations that do not
consider all the waste typologies collected
Waste Fed to the WtE Plant

Table 2 shows the mass balance for the waste fed to the WtE plant in the two scenarios. In the
Reference Scenario not all the combustible residues resulting from Bulky waste selection have
been sent to the WtE plant, because MSW and other wastes already saturated the authorized plant
capacity (120,000 t/y). In the Derived Scenario, instead, due to the increase of SC which
subtracts a significant amount of MSW to the WtE plant, all these residues have been sent to
energy recovery. Moreover, to saturate the authorized treatment capacity, also all the combustible
residues from the selection of SC and some additional IPW have been assumed to be fed to the
WtE plant.
Table 2. Mass balance for the waste fed to the WtE plant in the two scenarios.
Reference
Scenario Derived
(2007) Scenario
Unsorted Residual Waste (URW) 96,682 77,823
Cemetery waste 76 76
IPW and residues from "Bulky waste" selection 14,554 32,436
Residues from "Purple bag waste" selection 2,151 0
Residues from SC waste selection 0 6,330
Dried sewage sludge and sanitary wastes 3,335 3,335
Bunker surplus 3,202 0
Total 120,000 120,000
528
A significant difference between collection mass balance and bunker mass balance in 2007 has
been fixed assuming different amounts of waste stored in the bunker at the beginning and at the
end of the year (the so-called bunker surplus). This figure appears in Table 2 for the Reference
Scenario. Instead, for the Derived Scenario this number has been set to zero.
Three waste streams have been characterized in terms of chemical composition and energy
content. The approach followed is the same explained in Consonni and Vigan [3]. These three
streams are:
the waste fed to the WtE plant in 2007 (and in the Reference Scenario);
a high LHV waste representing the IPW and the selection residues from Bulky waste and
SC processing; in fact, for simplicity, these three wastes have been considered very similar
and the same chemical / physical characterization has been assumed for all of them;
the waste fed to the WtE plant in the Derived Scenario.
Nevertheless some analysis of the bunker content were available, the mean composition of the
waste fed to the WtE plant in 2007 was not based on them, because of their statistical dispersion.
A reasonable composition has been defined in order to match the production of ashes (bottom and
fly), metals, dry and humid flue gases recorded on the plant during 2007 (a statistical analysis has
been conducted). The composition of the 2007 feedstock is reported in terms of waste fractions in
the column B of Table 3.
In the same way also a reasonable composition for IPW (hereafter including also all the selection
residues) has been set, in order to obtain a high LHV and to determine reasonable composition
and properties of the so called Base mix, reported in the column G of Table 3. The Base mix is
the mix of URW, Cemetery waste, Sanitary wastes and Dried sewage sludge fed to the WtE
plant in 2007. It does not include all the IPW that are accounted for separately. Composition and
properties of this Base mix have been determined as difference between those of the 2007 WtE
plant feedstock and those of the IPW.
This procedure has been adopted because between the Reference Scenario and the Derived
Scenario the amount of IPW changes.
Under the hypothesis that the total amount and composition of MSW produced between the two
scenarios remain constant (see Table 1), the composition of URW must change in order to meet
the variations brought by SC enhancement and the suppression of Purple bag collection (they are
evidenced in the columns H and I of Table 3).
For simplicity, Sanitary wastes and Dried sewage sludge amounts are also kept constant
between the two scenarios, thus all the variations in the composition of URW are reflected on the
composition of the Base mix. For this reason, Table 3 reports also the New base mix and the
final composition of the WtE plant feedstock for the Derived Scenario (respectively columns K and
M).
Mass and Energy Balance for the WtE Plant Boilers

The mass balance for the WtE plant has been developed considering the combustor-boiler
subsystem, as evidenced in Fig. 1. For the same subsystem also the energy balance has been
carried out, leaving the development of the energy balance for the steam cycle in a second step of
analysis.
After a statistical survey of all the data recorded by the plant DCS and CEMS, data reconciliation
has been carried out by preferring the more accurate data on flue gases with respect to, for
example, the combustion air flowrates.
The closure of the energy balance for the combustor-boiler subsystem has been possible thanks to
the data on steam production for the entire 2007. The energy balance for this subsystem in the
Reference Scenario allowed to determine the mean LHV of the waste incinerated in 2007, as well
as the corresponding boiler efficiency achieved (85.93%).
Fig. 2a shows the comparison between the mass balance of this subsystem (both lines are
considered) based on the recorded data and that based on our calibrated model. Fig. 2b, instead,
shows the energy balance for the Reference Scenario as predicted by our model.
To draw balances for the Derived Scenario, as much parameters as possible have been kept
constant. For example, the mean oxygen content in dry flue gases at the exit of boiler, which
determined the excess air with which combustion has been calculated.
The energy balance in the Derived Scenario has been used to determine the steam production,
as well as the boiler efficiency achieved in this new condition.
529
Table 3. Amounts and compositions of the waste streams fed to the WtE plant in the two scenarios.
Column A B C D E F G H I J K L M
2007 feedstock to WtE IPW Base mix Variations New base mix New feedstock to WtE
Amount in Amount in Amount in Suppr. of Amount in Amount in
"Reference Amount in "Derived "Reference Enhance- purple bag "Derived "Derived
Scenario" "Reference Scenario" Scenario" ment of SC collection Scenario" Scenario"
Waste fraction [t/y] [%] Scenario" [%] [t/y] [t/y] [%] [t/y] [t/y] [t/y] [%] [t/y] [%]
Paper and cardboard 38,251 32.75 5,312 31.80 12,328 32,939 32.91 -7,012 +684 26,611 32.76 38,939 32.45
Wood 1,752 1.50 835 5.00 1,938 917 0.92 -744 +108 281 0.35 2,219 1.85
Plastics 27,448 23.50 8,670 51.90 20,120 18,778 18.76 -1,462 +1,116 18,432 22.69 38,551 32.13
Glass and inerts 5,256 4.50 84 0.50 194 5,172 5.17 -3,253 +11 1,930 2.38 2,124 1.77
Aluminium 3,037 2.60 50 0.30 116 2,987 2.98 -61 +6 2,932 3.61 3,048 2.54
Other metals 4,205 3.60 84 0.50 194 4,121 4.12 -578 +11 3,554 4.38 3,748 3.12
Food waste 17,520 15.00 84 0.50 194 17,436 17.42 -7,490 +11 9,957 12.26 10,151 8.46
Green waste 1,810 1.55 0 0.00 0 1,810 1.81 -348 +0 1,462 1.80 1,462 1.22
Fines 11,680 10.00 84 0.50 194 11,596 11.59 0 +0 11,596 14.28 11,790 9.83
Textiles 5,840 5.00 1,503 9.00 3,489 4,336 4.33 -62 +204 4,478 5.51 7,967 6.64
Total 116,798* 100.00 16,705 100.00 38,766 100,093* 100.00 -21,010 +2,151 81,234 100.00 120,000 100.00
Ash content - 20.77 - 16.94 - - 21.39 - - - 19.60 - 18.74
Moisture content - 30.74 - 17.16 - - 32.93 - - - 32.85 - 27.78
LHV [MJ/kg] 9.80 16.83 8.66 - 9.22 11.68
* Excluding the 2007 bunk er surplus, as it results in Tab. 2.
Figure 2. (a) Mass balance for the WtE plant. Comparison between 2007 data and the outcomes of the model (Reference Scenario).
(b) Energy balance for the WtE plant as predicted by the model (Reference Scenario).
530
Fig. 3 reports mass and energy balances for the Derived Scenario in comparison with those of the
Reference Scenario.
The significantly higher LHV of the feedstock in the Derived Scenario leads to a consistent
increase in steam production, as well as in boiler efficiency, which reaches 86.91%. The
improvement in energy efficiency is due to the higher load imposed to the boilers, which reduces
the weight of fixed losses in the energy balance.
Figure 3. Comparison of mass (a) and energy (b) balances between the two scenarios.
Energy Balance for the Steam Cycle

Variables influencing the performances of the steam cycle are very numerous: turbine load,
condensing pressure, flowrates of bleedings, auxiliary consumptions, heat recovery on the
condensate and feedwater lines, other uses of steam and feedwater, etc.
Not all these variables are recorded by DCS, and many of those recorded have been measured
inaccurately. Moreover, it would be possible to carry out instantaneous data reconciliation and
record reconciled data, but on the Piacenza plant this is not done. The post-processing
reconciliation is a very challenging work, so we decided for a much simpler approach.
Our model of the steam cycle considered only two main variables that determine the specific
electric energy produced by the steam expansion. Since in our case the steam cycle is air-cooled,
the two variables considered have been the turbine load and the ambient temperature.
Turbine load has a direct effect on the turbine expansion efficiency, while ambient temperature, in
combination with turbine load, roughly determines the condensing pressure, thus the extension of
the expansion and the performances of the last expansion stage.
Also the flowrates of bleedings influence significantly the performances of the turbine expansion,
however data on them are only partially recorded and they are quite inaccurate.
Ambient temperature, in combination with turbine load, has been translated into a theoretical curve
of condensation pressure on the basis of the saturation pressure curve of water.
The electric power output of the generator (which is the gross power output of the plant) has been
converted into specific electric energy production dividing it by the steam flowrate at the admission
valve of the turbine.
A large number of data on specific electric energy production have been fitted with polynomial
forms as function of turbine load and theoretical condensing pressure. The data presented a very
high dispersion and considering several polynomial forms: the best fitting has been achieved with a
linear form (a plane). The model has been validated applying it to a number of different data sets.
The relative error on the results has always been within 1.5%.
This function, calibrated and validated on 2007 data, has then been modified to account for the
introduction of the final heat recovery on flue gases for the preheating of condensate. The
correction introduced considers on one hand the increase in power output due to the reduction of
steam bleeding for condensate preheating and, on the other hand, the reduction in power output
due to the increase in condensing pressure caused by the larger amount of steam to be
condensed. The net effect of this two phenomena is always positive (increase of power output), but
inconstant in the field of working conditions. In particular, the benefit becomes very tight at high
turbine load, when the condenser is already loaded with much exhaust steam.
531
The final curve is represented in Fig. 4a, while in Fig. 4b the statistical distribution of 2007 working
conditions is reported. Such a distribution is the same used to evaluate the performances achieved
in the Reference Scenario.
(a) (b)
Specific electric production (kJ/kg)
Yearly working hours (h/y)
Figure 4. (a) Specific gross electricity output predicted by the model as function of turbine load
and ambient temperature.
(b) Statistical distribution of working conditions recorded in 2007.
The presented procedure gives the gross electric energy production of the plant. It has been
applied also the Derived Scenario, where the steam produced by the two boilers fully loads the
steam turbine for all the 8,300 yearly working hours hypothesized. In this case, the statistical
distribution of working conditions is much simpler than those for the Reference Scenario: the only
non-full-load conditions being startup / shutdown phases and the periods of outage for
maintenance of a single line.
A procedure similar to that described above has been used to quantify auxiliary consumptions,
which are needed in order to determine the net electricity production of the plant. In this case the
same fitting attempt of recorded data has been performed and the results showed that auxiliary
consumptions correlates quite well linearly with the turbine load (which is an index of the plant
load).
The difference between gross energy production and auxiliaries consumptions yields to the net
energy production. The model applied to the 2007 situation (without the final heat recovery on flue
gases) showed a little bias, of less than 1%. This offset was corrected by means of an additional
coefficient, to match exactly the performances recorded in 2007.
The net electricity sold to the grid by the plant differs from the net production due to two factors.
The first is the purchases of electricity in the periods of outage for the maintenance of the steam
cycle. In fact the plant is connected to the electric grid only via a bidirectional high voltage line.
The second is transformation losses. For simplicity constant transformation efficiency has been
assumed for both the scenarios and for both current directions (MV to HV and HV to MV).
RESULTS
Table 4 shows the final results for the Reference Scenario compared to the data recorded in
2007. The improvement brought by the introduction of the final heat recovery on flue gases gives a
little increase in the electricity produced and then delivered to the grid. The positive sign in the
variation is very likely to be correct; however the magnitude of the variation, comparable with the
uncertainty of the model, is of scarce reliability.
532
Table 4. Final results (electrical balance) for the Reference Scenario compared with 2007
recorded data.
2007
recorded Reference
Yearly performances
data Scenario Variation
[kWh] [%]
Gross electric production 79,310,018 79,801,480 +491,462 +0.62
Auxiliary consumptions 11,049,050 11,049,050 0 +0.00
Electricity purchase from the grid 97,030 97,030 0 +0.00
Electricity from the emergency genset 50,900 50,900 0 +0.00
Gross electricity from MV to HV 68,311,868 68,803,330 +491,462 +0.72

Gross electricity from HV to MV 97,030 97,030 0 +0.00
MV/HV transformation losses 768,847 774,378 +5,531 +0.72

HV/MV transformation losses 1,092 1,092 0 +0.00
Electricity for sale 67,638,959 68,124,890 +485,931 +0.72
Much more interesting are the results of the model when applied to the Derived Scenario. They
are reported in Table 5. As it can be seen, fully loading the plant gives a consistent increase in the
gross production of electricity and only a marginal increase in auxiliary consumptions. This situation
leads to a very high gain in the net energy production and, thus, in the electricity for sale: +27.3%.
This improvement is the result of the combination of three factors:
the increase of the mean load of the plant, from 83.83% to 100% (+19.3% - be aware that
the two figures are calculated on different numbers of yearly working hours);
the increase of yearly working hours, from 8,000 to 8,300 (+3.6%);
the improvement of the net efficiency of the plant (mainly due to the increase in plant load),
from 21.96% up to 22.58%. This improvement of less than one percentage point in relative
terms is about 2.8%.
Table 5. Final results (electrical balance) for the Derived Scenario compared with those of the
Reference Scenario.
Reference Derived
Yearly performances Scenario Scenario Variation
[kWh] [%]
Gross electric production 79,801,480 99,483,778 +19,682,298 +24.66
Auxiliary consumptions 11,049,050 11,915,230 +866,180 +7.84
Electricity purchase from the grid 97,030 97,030 0 +0.00
Electricity from the emergency genset 50,900 50,900 0 +0.00
Gross electricity from MV to HV 68,803,330 87,619,448 +18,816,118 +27.35

Gross electricity from HV to MV 97,030 97,030 0 +0.00
MV/HV transformation losses 774,378 986,153 +211,775 +27.35

HV/MV transformation losses 1,092 1,092 0 +0.00
Electricity for sale 68,124,890 86,729,233 +18,604,343 +27.31
CONCLUSIONS
The evidences highlighted in this paper suggest a series of informative remarks:
The increase in SSL prospected in the Derived Scenario not only enhances recycling, but
also makes room for the energy recovery of other valuable wastes than MSW, in our case
IPW. When such wastes are not sent to energy recovery, they are likely to be disposed of
in a landfill, as it has been assumed for the Reference Scenario (see Part B).
533
Since these alternative wastes are usually characterized by higher energy content than
URW, the full exploitation of the authorized mass capacity of the WtE plant in the Derived
Scenario implies a substantial increase in the corresponding thermal input. To face this
situation, the WtE plant needs to be operated for a higher number of yearly working hours,
8,300 instead of 8,000.
The thermal input in the Derived Scenario fully saturates the thermal treatment capacity
of the plant, even assuming 8,300 hours of working time per year.
The net electric efficiency of the plant in the Derived Scenario improves significantly
thanks to the increased mean load. This, combined with the extended working time, leads
to an increase of the electricity for sale by 27.3%.
The Derived Scenario represents the extreme situation of loading for the WtE, which
casually correspond to the full exploitation of the authorized mass treatment capacity.
Were the thermal input still higher, only a reduction in the mass amount of waste treated by
the WtE plant would be possible.
AKNOWLEDGMENTS
The authors wish to thank Tecnoborgo SpA for the financial support to the study presented in this
paper, as well as for its fruitful collaboration and contribution to the understanding and the
interpretation of the plant data.
NOMENCLATURE
Table 6 reports a list of acronyms used throughout the paper with their explanations.
Table 6. List of acronyms used throughout the paper and their explanations.
CEMS Continuous Emission Monitoring LHV Lower Heating Value
System MSW Municipal Solid Waste
DCS Distributed Control System MV Medium Voltage
ESP EloctroStatic Precipitator SC Separate Collections
HV High Voltage SCR Selective Catalytic Reduction
IPW Industrial Packaging Waste SNCR Selective Non-Catalytic Reduction
IWMS Integrated Waste Management SSL Source Separation Level
System URW Unsorted Residual Waste
LCA Life Cycle Assessment WtE Waste-to-Energy
References
[1] M. Grosso, L. Rigamonti, M. Giugliano, Analysis of an integrated waste management system:
Part B Life cycle assessment, Proceedings of WASTES: Solutions, Treatments and
Opportunities, 1st International Conference, Guimares, Portugal, September 12th-14th, 2011.
[2] L. Rigamonti, M. Grosso, M. C. Sunseri, C. Dainese, F. Vigan, A. Bianchini, M. Pellegrini, S.

Consonni, S. Cernuschi, M. Giugliano, C. Saccani, Analisi comparativa di percorsi per il recupero di
materia e di energia da rifiuti urbani (In Italian), Proceedings of the SIDISA Conference, Florence,
Italy, 24th-27th June, 2008, Paper 446.
[3] S. Consonni and F. Vigan, Material and energy recovery in integrated waste management
systems: The potential for energy recovery, Waste Management. 31(2011) 2074-2084.
534
INFLUENCE OF ADDITION OF ANODIZING ALUMINIUM WASTE IN THERMAL INSULATION BRICK RED

CLAY
1,a 2 1
Marques, I. , Corker, J. and Vieira, M.T.
1
Dpt. Mechanical Engineering, University of Coimbra, Coimbra, Portugal
2
Laboratory Testing and Wear&Materials, Pedro Nunes Institute, Coimbra, Portugal
a
imarques@ipn.pt
ABSTRACT
In this study the sludge is produced from a plant of surface treatment of aluminium alloys essentially used in door and window frames,
denominated Hydrobuilding, Pombal, Portugal. The sludge results from its wastewater treatment unit. After a detailed characterization,
involving chemical composition, particle size, particle distribution, structure and crystallite size, the sludge was added in common clay used
to make bricks by Preceram, Pombal, Portugal. The final properties of the new brick, resulting from the same standard industrial treatment
were evaluated. A thermal insulation improvement of about 25% was reached. This work aims to achieve desired environmental objectives
and outcomes through a sustainable industry co-operation and produced a better product by using a waste.
Keywords: Aluminium Sludge, Red Clay, Recycling, Thermal Isolation;
INTRODUCTION
Industrial activity plays an important role in the economic development of Europe, contributing to a sustainable growth and
providing high quality jobs. However, industrial activity also has a significant impact on the environment [1]. Aluminium
anodizing and powder surface coating processes are commonly used techniques to protect metallic bodies from corrosion
eects and to achieve some aesthetic eects. These processes are highly water consuming, not only in each consecutive
chemical batch, but also to properly wash the pieces in between [2]. As a direct consequence, a huge amount of wastewater
is generated and proper treatments are required to satisfy environmental criteria of the generated euent to be sent out of
the factory, with a ecient solid content removal [3, 4 and 5]. The solid phase formed on these processes comprises a high
amount of sludge, mostly constituted by colloidal aluminium hydroxide, sodium or calcium (generated from neutralizing
solutions) and water (77 wt.%). Its physic form is agglomerated gel, but as a nanostructured material [3, 4 and 5]. Despite its
potential eco-toxicity (according to the standard DIN 38414-S4), this sludge has been often classied as non-hazardous [6].
However, the high daily-producing amounts of these sludges, along with the difficulties in reducing their volume by suitable
lter-pressing methods, makes its disposal an expensive process, specially due to its high transportation costs (40 Euros/ton
to disposal and 15 Euros/ton to transportation). In Portugal, 21 000 tons are estimated to be produced in 2015 [7] and about
100 000 metric tons per year are currently generated in EU countries [8], without being implemented any interesting
application from its re-use up to now.
The clay brick ceramic industry might constitute an interesting alternative to land disposal of sludge. In fact, actual production
levels resources (a medium-sized brickmaking produces 200 tons/day bricks) involve the consumption of huge amounts of
mineral resources. The heterogeneous character of natural raw materials, the use of several formulations and, not less
important, the firing process might ensure the desired inertness of final waste-containing products with respect to the ceramic
matrix.
This work aims to develop a thermal resistant brick by the recycling of the aluminium sludge in bricks production. For an
Industrial viability of the study it must be used the process parameters of each plant as they really operate and to have a
special attention to the costs of the recycling, particularly resulting from previous treatments and transport of sludge,
proximity is welcome. Therefore, clay and bricks production cycle of Preceram and sludge characteristics of HydroBuilding
was used in present study. Plants localization is just about 7 km between them.
535
EXPERIMENTAL
Experimental work consisted on the preparation and characterization of extruded samples of clay (C) and 3 different sets of
clay samples, adding 5 wt.% of the following additives: a micrometric Al-sludge (MS) and, a submicrometric sludge (SS).
Characterization of raw materials and formulations
Samples were prepared according to the scheme shown in Figure 1, in order to be as close
as possible to the real industry conditions.
Al-rich sludge generated from the wastewater treatment unit of an anodizing or surface
coating industrial plant (Hydrobuilding, Pombal) was used. It was previously dried at 110C
for 24h and disaggregated on an automatic mortar to micrometer and sub-micrometer
particles (particles size distribution is given on Table 1). The dried sludge is mostly
constituted by aluminium hydroxide. Aluminium, calcium and sodium sulphates are also
3
present as minor constituents and its density is 2.17 g/cm . Calcined sludge (1000C) has
3
an density about 2,8 g/cm .
Clay from production line of the brick plant (Preceram, Pombal) was used previously mixed
and homogenized in the plant, with an water content around 13%. Its density was 2.6 g/cm3
(previously dried clay).
Complete chemical characterization of the sludge and clay (by XRF for all elements
exception for sludge Sulfur content that was quantified by ICP-OES) is summarized on
Table 2.
Figure 1 scheme of steps

for samples preparation
Table 1 - Chemical compositions

Table 2- Particle size distribution of raw materials (%)
%< d10 d50 d90 Raw Al-
Clay
material sludge
SiO2 71,39 1,15
MS m 1,95 18,7 59,55
Al2O3 12,12 50,16
SS m 0,93 4,87 25,99 Fe2O3 3,59 0,1
CaO 1,04 0,17
C m 2,33 15,56 124,70
MgO 1,19
K2O 2,09 0,17
Na2O <0,20 1,69
MnO 0,05 -
MgO - 0,19
LOI 7,49 45,92
S - 1,9
According to the X-ray diffractogram (Figure 2), crystalline minerals present in clay were quartz, illite, smectite and kaolinite.
Al-sludge an amorphous boehmite, but during the firing cycle is observed an increase in intensity of the -alumina diffraction
peak (starting at 600C), (Figure 3). Large peaks also show the nanometric character of the -alumina . X-ray diffraction also
showed that -alumina was the main crystalline phase present after firing up to the clay brick maximum temperature. The
chemical analysis has shown that alumina is the main phase present on it (about 92%).
536
Figure 2 - XRD patterns of clay Figure 3 - XRD patterns of Al-sludge calcinated up to
1000C. () -alumina
The analysis of the thermal performance of the raw-materials allows the identification and understanding of the reactions that
take place during the firing cycle.
DTA/TG curves of the clay are in figure 5. On DTA curve, five endothermic steps are denoted: the first one is related to the
removal of the free water, close to 90C and, between 150 to 200C occurs the decomposition of smectite and illite.
Corresponding to these reactions, TG curve shows a weight loss of nearly 4%. Other endothermic inflection, at 490C,
shows the dehydroxylation of caulinite, corresponding to a weight loss of nearly 2%. This weight loss extends uniformly on
the TG curve, indicating late smectite and illite decompositions, also showed on the DTA curve by two smooth endothermic
peaks, between 680C and 710C. The reversible transformation of to quartz occurs approximately at 573 C
(endothermic inflection). Concerning the sludge (dried sludge), by following the DTA/TG curves (figure 6), it is visible the high
weight loss of this material during the entire firing cycle, corresponding nearly to 42% of initial weight. Removal of free water
and the decomposition of the aluminium hydroxide are identified on the extended endothermic curve inflection, between 100
to 600C. DTA curve shows another two endothermic peaks: close to 600C, one might correspond to the transformation of
Boehmite on -alumina (Al2O3)..
DTA sludge
DTA TG sludge
TG 10
0
3 1
5 -5
0
2 -1 -10
0
1 -2 -15
-5
DTA (V)
DTA (V)
-3
TG (%)
-20
TG (%)
0 -4 -10 -25
-5
-1 -6 -15 -30
-7 -35
-2 -20
-8 -40
-3 -9 -25 -45
0 100 200 300 400 500 600 700 800 900 1000 0 100 200 300 400 500 600 700 800 900 1000
Temperatura (C) Temperatura ( C)
Figure 5 Clay DTA/TG curves Figure 6 Sludge DTA/TG curves
537
Thermal expansion performance of dry sludge and
dried clay is given in figure 7. On the clay curve, its 2
shown a typical curve for this material, with an 0
expansion followed by an shrinkage stage that starts -2
dL/L0 (%)
close to the maximum sintering temperature. That -4
phenomena is related with start sintering, when is -6
initialized the closure of the structure and the -8
reduction of the porosity. On the sludge curve, its -10
possible to observe that a strong shrinkage is -12
developed right from the early stages of the heating -14
cycle until the maximum temperature is reached, 0 200 400 600 800 1000
without almost any linear dimensional variation Temperature (C)
during the cooling stage. This result highlights the
impossibility to add high contents of sludge to a clay. Figure 1 - Dilatometric curves for the Al-sludge dried at
In the present study it was limited to 5%. 110C, 24h
Results and discussion

Table 3 New Brick properties
The processability of the mixtures and morphological, physical,
mechanical and thermal properties of the new bricks were evaluated. Formulation C MS SS
The plasticity of mixtures show a slight modification, due to the addition Sludge content 0 5 5
of sludge with different particle sizes (dried at 110C, 24h) leading to (wt.%)
different contents of water. According to the values of different
characteristics of sintered specimen, (table 3), the addition of sludge
does not induce significant effects on brick processing properties. The
Plasticity [%] 22,3 31,1 24,8
presence of sludge increases the open porosity (max30%). The
addition of sludge reduces the bricks density (15%) and increases its Dry shrinkage [%] 7,9 7,7 5,6
water absorption. The values of this last property are in agreement with
the maximum values usually achieved in the bricks (max 20 wt.%). Total shrinkage [%] 7,6 7,9 5,8
The effect of decreasing particles size of aluminium sludge from
micrometric to submicrometric desagglomerated particles is mainly in Mass loss [%] 3,9 5,1 5,3
decreasing of shrinkage. Also a slight improvement in close porosity for
submicrometric particles size is observed. Bulk density [g/cm ]
3
2,0 1,7 1,7
The analysis of porositys characteristics (table 4 and figure 8) shows
differences to the clay, but the particle size of sludge does not seem to Real density [g/cm ]
3
2,5 2,6 2,6
have an important role.
The microstructures of the bricks (figure 9) show a particles distribution
Total porosity [%] 27,8 36,1 35,9
homogeneous. A reaction between the elements present on sludge and
those present on clay is not clear. Therefore, the presence of sludge on
clay matrix seems to promote porosity, but mainly decreasing the Open porosity [%] 24,0 34,7 33,0
dimension of porous with the submicrometric characteristics of the
sludge. Closed porosity [%] 3,9 1,4 3,0
Water absorption [%] 12,2 19,9 18,9
538
Figure 8 - Porosity distribution Table 4 Porosity characteristics
0,14
0,12 Formulation C MS SS
Sludge content 0 5 5
0,10 (wt.%)
dV/dlogD (ml/g)
0,08 C
MS Porosity [%] 24,29 33,93 31,92
0,06
0,04 SS Total pores [ml/g] 0,13 0,20 0,19
0,02 volume
0,00
Pores median [m] 0,77 0,71 0,58
1000 100 10 1 0,1 0,01 0,001
Dimetro (m) diameter
Sludge particles
Sludge particle
Figure 9 - Microstructure of the new brick
The influence of 5% of sludge addition on bricks is well highlighted by the compressive strength and thermal conductivity
values (tables 5 and 6). In fact, it is predictable that increasing on porosity may influence these properties.
Table 5 Samples compressive strength Table 6 - Thermal conductivity analysis
Formulation C MS SS Formulation C MS SS
Sludge content 0 5 5 Sludge content 0 5 5

(wt.%) (wt.%)
Compressive [MPa] 22 11 13 Thermal [W/mC] 0,70 0,57 0,52

strength conductivity
coefficient, k
Conclusions
Aluminium sludge can be recycled as an additive of clay. It can contribute to the thermal comfort of buildings, without
increasing the brick price. The addition of sludge causes an improvement on thermal resistance of about 25%. The others
physical-mechanical properties are reduced (water absorption and compression strength) but yet have values suitable to be
used as a conventional brick.
539
In this case, all the factors involved are based on industrial parameters and the raw materials are not selected by its best
characteristics. The clay studied was provided by the brick plant, from the production cycle and any efforts were done to
optimize its composition. Other clay from other clay pits, let to values more promising for concerning thermal insulation
leading to a about 40% with only a decreasing of mechanical resistance of about 14% [9]. The work presented must be
envisaged as a master plan study to be done with clay and sludge of different sources.
Acknowledgement
This work was developed in the framework of the scientific project QREN SeTIVERNano 13312, Produo de tijolos
trmica e estruturalmente mais resistentes por induo de nanomateriais, involving two Portuguese industries, Preceram
Industrias de construo SA and HydroBuilding Sistemas de alumnio para construo Lda.
References
[1] Toward an Improved Policy on Industrial Emissions, Communication from the Commission to the
Council, the European Parliament, the Economic and Social Committee and the Committee of the
Regions, Brussels, 21/12/2007.
[2] Guia Tcnico Sectorial. Sector dos Tratamentos de Superfcie, Elaborado no mbito do Plano
Nacional de Preveno dos Resduos Industriais (PNAPRI), INETI, Lisboa, Novembro, 2000.
[3] Folheto Tratamentos de Superfcies Anodizao, Empresa Extrusal, 2009
[4] P.F. Silva, Introduo corroso e proteco das superfcies metlicas, Belo Horizonte, Imprensa Universitria,
Universidade Federal de Minas Gerais, 1981
[5] F. Castro, C. Vilarinho, D. Soares, Gesto de resduos industriais por incorporao em materiais para construo civil
Universidade do Minho
[6] J. M. Magalhes, J. E. Silva, F. P. Castro, J. A. Labrincha, Physical and chemical characterization of metal finishing
industrial wastes, Journal Evironmental Management, 75, 157-166, 2005.
[7] INETI, Plano Nacional de Preveno de Resduos Industriais (PNAPRI), Volume I, Lisboa, 2001. INETI, Plano Nacional
de Preveno de Resduos Industriais (PNAPRI), Volume I, Lisboa, 2001.
[8] D.A. Pereira, D.M. Couto, J.A. Labrincha, Incorporation of aluminum-rich residues in refractory bricks, CFICeramic
Forum International 77 (2000) 2125.
[9] Marques, I.S.R. (2009). Estudo da influncia da adio de resduos de anodizao de alumnio no isolamento trmico de
tijolos de barro vermelho. Tese de Mestrado em Engenharia do Ambiente, Universidade de Coimbra, Coimbra.
540
ENVIRONMENTALLY FRIENDLY METHODS IN THE FOOTWEAR INDUSTRY

AS A MEANS FOR HAZARDOUS WASTE REDUCTION
J. Ferrer, M.A. Martnez, A. Zapatero, M.E. Riquelme, M. Roig, M. Bertazzo

Footwear Technological Institute (INESCOP), Elda, Spain. medioambiente@inescop.es
ABSTRACT
Traditional industrial activities have led to the generation of vast volumes of waste and
the consumption of non-renewable sources. In the leather and footwear industry, the
majority of pollutants come from the tanning phase, mainly due to the application of
chrome. The remaining processes involved in the footwear industry are also a source of
waste production. Many footwear components are based on non-renewable sources such
as TPU, used in sole making.
Therefore, there is a need to develop new productive models with a lower environmental
impact. INESCOP is running three European Projects aiming to develop greener
technologies for the footwear industry. OXATAN (Environmentally Friendly Oxazolidine-
Tanned Leather) and TiLEATHER (Titanium Tanned Leather) projects are focused on
promoting chrome free tanning methods by the use of oxazolidine and titanium
respectively. These two substances claim to be an alternative to traditional tanning
techniques in order to reduce wastewater pollution as well as diminish the environmental
impact of leather at the end of its useful life. On the other hand, the objective of ECOTPU
project is to introduce new materials obtained from renewable sources as so to produce
footwear components such as soles or stiffeners. This eco-material could be a substitute
for fuel sources, contributing thus to the production of harmless waste. This paper shows
the results obtained up to date for each of the three projects.
Keywords: Wastewater; solid waste; chrome tannage; eco-materials.
INTRODUCTION
The Footwear Technological Institute (INESCOP) is an independent service organisation that

counts on more than 600 member companies. INESCOPs main objective is the development of
scientific and technological activities such as quality control and assurance, organisation of
productive processes, studies on materials, development and incorporation of advanced
technologies, applied research, environmental issues, etc. that companies within the footwear,
leather and related sectors are incapable of carrying out individually but are, however, of great
interest to maintain and reinforce the Sector.
Amongst the environmental projects that are currently being developed by INESCOP is the
European OXATAN project, aimed at the demonstration, promotion and dissemination of
oxazolidine tanning techniques, with the partial support of the European Commission within the
framework of the LIFE+ Programme, the European TILEATHER project, the main objective of is to

introduce SANOTAN leather into the European market, and the European ECOTPU project, the

aim of which being to introduce an innovative thermoplastic material to the market (BIOTPU )
obtained from renewable resources instead of oil, with properties similar to those of products
obtained from fossil fuels currently used by footwear producers. These last two projects are
partially supported by the Executive Agency for Competitiveness and Innovation (EACI) under the
Eco-Innovation Programme.
541
OXATAN PROJECT: ENVIRONMENTALLY FRIENDLY OXAZOLIDINE-TANNED LEATHER
The transformation of an animal's skin into tanned leather involves carrying out a series of
chemical processes and mechanical operations where a putrescible material, consisting especially
of proteins, becomes a stable and resistant material that can be used in the manufacture of
footwear, leather goods, upholstery, clothing, etc. This process involves the generation of a
significant volume of wastewater and solid waste. The traditional tanning process is carried out
employing trivalent chromium salts, which interact by chemical bonding with the carboxylic groups
of collagen in the skin, giving to the leather its strength and stability properties (see figure 1).
Fig. 1 Collagen-Chrome crosslinked. Fig. 2 Collagen-Oxazolidine crosslinked.
However, in some cases, an allergy to chromium may appear. Even trivalent chromium can be
partially oxidized to hexavalent chromium, a carcinogenic agent in accordance with the
International Agency of Research on Cancer (IARC), which may be present in wastewater and
solid waste from tanneries, having a considerable impact on the environment and human health.
Within this context the LIFE OXATAN project was launched. The reviewed literature [1, 2] and
previous research studies conducted by INESCOP indicated that using oxazolidine type E, an
aldehydic tanning agent, combined with synthetic or vegetable re-tanning agents to achieve higher
shrinkage temperatures, could allow high-performance leathers to be obtained having a quality
comparable to the chrome tanned leathers. In addition, chromium content is avoided in liquid and
solid waste derived from the tanning process that can be used by footwear and upholstery
industries (see figure 2). This way, the environmental impact caused by leather tanning can be
dramatically reduced, as well as the repercussions at the end of its lifecycle, whether it be in the
form of leather trimmings in tanning, footwear and upholstery businesses or in the disposal of used
leather articles.
During the first stages of the OXATAN project execution different tanning tests have been carried
out on calf hides and sheepskins on a semi-industrial scale at INESCOPs pilot tanning plants,
using oxazolidine in combination with synthetic or vegetable re-tanning agents. In these trials the
obtained leathers tanned with oxazolidine showed an acceptable appearance and adequate
smoothness, softness, fullness and flexibility, and no significant difference between the two
combinations was detected.
Also, the determinations of physical parameters of the leathers showed to be compliant with the
limits required for footwear and upholstery articles manufactured and their chemical
characterisation proved to be compliant with the limits required for the European Eco-label for
footwear [3].
Furthermore, no differences were noted in the footwear and upholstery processing conditions of
this kind of leather or in the final appearance of the articles (see figure 3).
Fig. 3 Footwear and upholstery products made of oxazolidine tanned hides.
542
Regarding the environmental impact of this new technology, the characterization of the tanning
wastewater showed that the values of the parameters set by oxazolidine tanning are comparable in
order of magnitude to those obtained using chromium salts, but oxazolidine tanning effluents are
chrome-free; therefore, the possible trivalent chromium oxidation into hexavalent chromium is
prevented and the sludge derived from wastewater treatment is more likely to be reused, e.g. for
agriculture. Also, biodegradability tests of tanning wastewater on activated sludge showed a higher
degree of biodegradability of oxazolidine effluents than chromium effluents, thus their biological
treatment a priori seems to be more feasible.
Finally, biodegradability tests on leather showed that oxazolidine-tanned leather wastes are more
biodegradable than chrome-tanned leather wastes, so the environmental impact of waste is less
and waste management is easier (see figure 4).
Fig. 4 Leather biodegradability test equipment.
In short, oxazolidine tanning implies a significant benefit in that it is possible to considerably reduce
the environmental impact produced during the tanning process and at the end of the lifecycle of
products manufactured using this kind of leather.
TILEATHER PROJECT: TITANIUM TANNED LEATHER
Titanium is also a good candidate for leather tanning because it is a non toxic metal and gives
additional advantages since it is biocompatible, inert and avoids possible allergic reactions derived
from contact with the skin. Although titanium was considered as a possible tanning agent, the
leather industry has traditionally opted to use other agents. This was mainly due to several
difficulties in using titanium throughout the entire tanning process but the tannery Industrias del
Curtido, S.A. (INCUSA) has developed an innovate process for titanium tanning. Thus, the Eco-
Innovation TILEATHER project is being developed under INESCOPs coordination for improving
the EU market update of the titanium leather registered by INCUSA under the trade name

SANOTAN .
The titanium tanning technique uses titanium sulphate (ammonium titanyl double sulphate
Ti(NH4)2(SO4)2H2O, masked with certain organic products as a tanning agent. Titanium combines
with the skin collagen in the same way as chrome does (see figure 5).
aq aq aq
SO4
- + + -
COO Ti O Ti OOC
SO4
aq aq aq
polipptido polipptido
Fig. 5 Interaction of collagen carboxyl groups with titanium.
543
This technique makes chrome rettaning unnecessary; therefore, chrome is completely eliminated
from tanning processes and thus this technique is more environmentally friendly.

In the framework of the TiLEATHER project, SANOTAN leather is already being produced on an
industrial scale by adapting a former chromium production line. After having set up the new
production line, the first cattle hides tanned with titanium on an industrial scale were obtained, and
their mechanical properties, as well as the wastewater derived from the tanning process were
analysed according to international standards. What is more, a further step was taken with the
production of several shoe styles by the manufacturers participating in the project, with a view to
checking the suitability of said leathers.

Based on the obtained results about leather characterisation the SANOTAN leather is currently
meeting the required standards for footwear manufacture.
Upon wastewater characterisation and comparison with conventional chrome-tanning wastewater,
an improvement was noted thanks to the achievement of high exhaustion of product fixation during
titanium tanning. Table 1 shows the results of the analyses carried out.

Table1. SANOTAN leather characterisation results.
MUNICIPAL
NEW CONVENTIONAL
PARAMETER SEWAGE SYSTEM
WASTEWATER WASTEWATER
LIMITS
pH 6.9 7.1 5.5 to 9.5
Conductivity [s/cm] 4,500 6,000 2,000
Colour Imperceptible Cloudy Colourless
COD [mg/L O2] 1,450 1,900 1,500
BOD5 [mg/L O2] 560 700 1,000
Fats and oils [mg/L] 3.5 9 10
Chlorides [mg/L] 1,830 2,200 2,000
Sulphates [mg/L] 400 500 1,000
One of the objectives of the TILEATHER project is the introduction of more ecologically friendly
leathers into the European market, so it is important to test the reduction of the environmental
impact of titanium-tanned leathers at the end of their lifecycle. To check this, the study on the

biodegradability of SANOTAN leathers was set up with respect to the chrome-tanned leathers,
and tests were carried out from which an estimation of the degree of biodegradability of leathers
was obtained according to the tanning agent used. In the biodegradability tests carried out titanium-
tanned leathers showed a higher biodegradability degree than those conventionally tanned with
chrome; therefore, the environmental impact of titanium-tanned leather at the end of its lifecycle is
lower.

Finally, in order to test the suitability of SANOTAN leather for footwear production, different
footwear prototypes with different material assembly methods were manufactured. The following
trials and tests were carried out: visual inspection of footwear, weight determination, flexibility
evaluation, evaluation of perspiration management, and study on comfort. The main feedback
gathered during controlled wear trials indicated that 100% of testers considered that the upper was
soft and comfortable. Figure 6 shows different footwear styles produced by project partners using

SANOTAN leather.
The main conclusions are that titanium-tanned leathers pose an alternative already available on the
European and international market that avoids the use of chrome as well as its possible effects on
human skin, such as irritation or allergies. Also, titanium tannage implies an environmental
improvement in that leather waste does not contain chrome, chrome contamination is avoided in
tannery wastewater as well as in wastewater treatment sludge and titanium-tanned leather shows
higher biodegradability than chrome-tanned leather.
544

Fig. 6 Some footwear styles produced with SANOTAN leather.
ECOTPU PROJECT: THERMOPLASTIC POLYURETHANE (TPU) FROM RENEWABLE

SOURCES APPLIED IN FOOTWEAR
Thermoplastic polyurethanes are lineal polymers formed by the polymerization reaction of three
basic components: diisocyanate (NCORNCO), a short-chain diol (OHROH) and a long-
chain diol. This product can be used in a wide range of adhesives, injection moulding and
compounding applications.
Formerly, the chemical industry has been using old carbon taken from fossil resources, especially
oil. Since this manufacturing process does not contribute to sustainable development, it has
encouraged manufacturers to seek alternative plant-based plastics. Thus, the Eco-innovation
project ECOTPU is being developed under the coordination of INESCOP and in collaboration with

MERQUINSA to increase the EU market update of an innovative product sold under the BIOTPU

trade name which owned by MERQUINSA. The BIOTPU is a thermo plastic polyuretane partially
obtained from renewable sources (vegetable oils) that can be used in the production of footwear
components.
Moreover, but in second term, recyclability of post-consumer parts to improve the carbon footprint
of the new products as well as a very important concept to be added to the original concept of
renewability are being strongly considered.
Previous research studies proved the technical feasibility of the industrial-scale production of
BioTPUs. On a prototype-scale, BioTPUs with a bio-based content ranging from 20% to 90% were
obtained [4] (see figure 7).
Fig. 7 - Report of Biobased content analysis according to ASTM - D6866.
The mechanical properties of this family of new materials are comparable to those of conventional
TPUs and even better in some cases (see figures 8, 9, 10 and 11).

Finally, it is worth mentioning that the BIOTPU has been successfully tested in the production of
footwear components, such as soles, toe puffs and counters.
545
45 100,00
40
35 99,50
30
Elongation [%]
Tensile Strenght 99,00
[MPa]
25
Modulus 100 98,50
20
15 Modulus 300
98,00
10
97,50
5
0 97,00
ECO Polyester ECO Polyester +
96,50
D12T90 D12T90 + 168h 85C
ECO D12T90 + 168h 85C Polyester + 168h 85C
168h 85C
Fig. 8 Tensile strength. Fig. 9- Elongation.
90
80 1,2
80 1,19
Abrasion resistance [mm 3]
1,19
70
Density [g/cm3]
1,18
60
50 1,17
1,16
40 35 33
1,16
1,15
30 1,15
20 1,14
10 1,13
0 ECO D12T90 ECO D12T95 Standard polyester
ECO D12T90 SBS Standard polyester based TPU
based TPU
Fig. 10 Abrasion resistance. Fig. 11 Density.
ACKNOWLEDGMENTS
The authors thank the European Commission for the partial support to the LIFE+ Project
Environmentally friendly oxazolidine - tanned leather (OXATAN) with reference number LIFE08
ENV/E/000140 and ECO-INNOVATION Projects Titanium tanned leather (TILEATHER), with
reference number ECO/09/255727 and Thermoplastic polyurethane (TPU) from renewable
sources applied in footwear (ECOTPU), with reference number ECO/09/255887.
REFERENCES
[1] Kitty Qu, Jeff Yang, et al. Oxazolidines: the versatile leather tanning agents. Leather March
2008, p 38-40.
[2] DAquino A., Barbani N., DElia G., et al. Combined organic tanning based on mimosa and
oxazolidine: development of a semi-industrial scale process for high-quality bovine upper
leather. Journal of the Society of Leather Technologists and Chemists. Vol. 88, p 47-55.
[3] Commission Decision 2002/231/EC.
[4] ASTM-D6866 Standard test methods for determining the biobased content of solid, liquid,
and gaseous samples using radiocarbon analysis.
546
14th September
Session 2.5
( SPECIFIC WASTE-STREAMS 1 )
Chairman: Carlos Bernardo
547
USE OF BIOMASS AND/OR BIOMASS RESIDUES FOR SYNGAS

PRODUCTION BY THERMAL GASEIFICATION IN THE PORTUGUESE
NORTH ALENTEJO REGION
1 1 1
A.S. Oliveira , P.S.D. Brito and L.F.T.T. Rodrigues
1 C3i Centro Interdisciplinar de Investigao e Inovao, Instituto Politcnico de Portalegre,

Apartado 148 7300-901 Portalegre, Portugal
ABSTRACT
Bio-energy, as energy from biomass is one of the most important source of renewable
energy, and a serious alternative to fossil fuels, and a condition for an effective solution to
the environmental and energy problems to which the global society is confronted with.
This contribution describes the work that is being performed to make the characterization
of the biomass materials and some of the biomass residues resulting from agriculture
available in the Alto-Alentejo region in Portugal, and the eventual use of some of the
characterized biomasses and or residues in thermal gasification processes. In this way
we produce syngas and energy as the same time that we tread and valorize a biomass
residue.
Heat values and elemental analysis (CHNS) of the most representative biomasses and
biomass residues existents in the region are being determined in order to forecast syngas
composition resulting from the thermal gasification of the studied biomasses. Some of the
materials studied include pine wood, poplar, olive, weeping willow, willow, eucalyptus,
holm, cork, oack, broom and vine and bagasses from olive oil production.
The application of valorization technologies, including energy production will be
considered for the most promising gasification biomasses and residues. Results show
that several biomasses and residues have interesting features for use as syngas row-
material. Preliminary results of these tests are presented and discussed.
Keywords: Bioenergy; biomass; gasification; biomass wastes
INTRODUCTION
Rapid and continuous depletion of fossil fuels resources and increasing concerns with
environmental issues determines the urgent need for alternative fuels, particularly biofuels obtained
from biomasses of different origins. In fact, biomasses are among the most abundant energy
renewable sources and can be obtained in high amounts either by production of bioenergetic crops
or using forest and industrial biowastes [1-3]. Bio-energy, as energy from biomass is one of the
most important source of renewable energy, and a serious alternative to fossil fuels, and a
condition for an effective solution to the environmental and energy problems to which the global
society is confronted with. Biomass gasification appears to be a promising process for syngas
production containing methane and hydrogen to be used as energy source or row material for liquid
fuels and other chemicals. Although syngas heat value is considerably smaller than that of wood,
for example, gasification constitute a good alternative to conventional combustion technology heat
production, since the latter as to be used immediately after production. In fact, gasification is a
convenient way of transforming solid energy resources from biomass in a fuel gas that can be
easily transported or stored for latter use as fuel on internal combustion engines or even as row
material for synthesis [4]. The use of fluidized bed technology in gasification units makes possible
to use smaller gasifiers than with fixed bed. The higher efficiency of fluidized bed comes from its
higher specific reaction area when compared to fixed bed. Fluidized beds also proved to permit
548
more versatile units in terms of feeding materials of different characteristics and origins. To
produce syngas and energy as the same time that we tread and valorize biomass residues is a
challenge. For that we evaluated the potentialities of the available residues and evaluates the
quality of the syngas produced from them.
EXPERIMENTAL
Biomass gasification pilot scale plant

The experiments were performed at the gasification pilot plant (Figure 1), which is based on an up-
flow fluidized bed gasifier, that can be operated up to 850 C, under a total pressure bellow 1 bar
and at a maximum pellet feeding rate of 50 kg/h. In the present work, the results of gasification
experiments of different compositions of mixtures of vine pruning and wood pellets are presented.
Figure 1 displays also a diagram of the biomass gasification pilot scale plant used in the
experiments. Main components of the unit are the following:
Biomass feeding system with two in-line storage tanks that discharges the biomass to
the reactor at a rate of 50 kg/h, using an Arquimedes screw with variable and controllable
speed; these two storage tanks act as buffer to avoid the entrance of air trough the feeding
system.
Fluidized bed reactor is a tubular reactor with a diameter of 0,4 m and 2,5 m height,
internally coated with ceramic refractive materials; biomass enters the reactor at 0,5 m
from its base and preheated air enters the reactor from the base through a set of diffusers
that warrant a flow of about 70 m3/h; three temperature sensors are installed inside the
reactor in order to monitor and allow the control of the gasification process that occurs at a
temperatures around 800 C; syngas leaves the reactor trough his top, at about 700 C;
reactor operates at negative pressure gradient produced by a vacuum pump installed at
the end of the process line; temperature control of the reactor is a determining factor of the
gasification process and this control is achieved by the tuning the amount of air admitted to
the reactor, increasing the air flow rate to increase the reaction temperature;
Gas cooling system consists of two heat exchangers; the first heat exchanger cools the
syngas to about 300C using a air co-current flow that enters the unit, and the second heat
exchanger cools syngas down to 150C by forced flow of air coming from the exterior;
Bag Filter: the removal of carbon black and ashes particles produced during the
gasification process is performed using a cellulosic bag filter; the cleaning of the filter is
made by pressurized syngas injection; black carbon is collected at the bag filter bottom and
stored in a proper tank;
Condenser: liquid condensates removal is made by cooling syngas down to room
temperature on a third tube heat exchanger.
Tests are generally made using feeds of different ratios of the tested biomasses, at 800C.
Feedstock admission rates of 40 and 63 kg/h were tested in order to optimize the heating value of
syngas obtained.
Biomass characterization
Percentage humidity determination was performed using a heated balance (OHAHUS - MB200)
that measures the sample weight loss through the experiment time, until a constant weight is
achieved. In this work constant weight was achieved before 20 minutes heating of samples at 150
C. Elemental composition of biomass samples were determined using the Thermo Unican
Elemental Analyzer, Flash 2000, that allows the determination of the sample content in carbon,
hydrogen, nitrogen, sulfur and oxygen by gas chromatography (GC). Heat values of the sample
biomasses were calculated from elemental analysis data.
Syngas characterization
Syngas analysis was performed in a Varian 450-GC gas chromatograph with two TCD detectors
that allow the detection of H2, CO, CO2, CH4, O2, N2, C2H6, C2H4 (equipped respectively with
CP81069, CP81071, CP81072, CP81073 and CP81025 Varian GC columns), using helium the
carrier gas.
549
Figure 1 - Biomass gasification pilot scale plant at Escola Superior de Tecnologia e Gesto,
Instituto Politcnico de Portalegre, Portalegre, Portugal. The main components of the unit are
described in the text.
Syngas samples for the analysis referred above were collected in appropriate collection and
analysis bags at the condenser exit every time when the gasification of a given feedstock
composition reached its stationary state. Collected syngas samples were injected (within 1 hours
after sampling) directly from the sampling bags in the chromatograph using a peristaltic pump
operating at is maximum rate and equipped with a Marpren tube. Chromatographic peaks for the
different gases under analysis were identified based on their retention times, comparing them with
retention times of the same gases in the reference chromatogram of the custom solution, provided
by Varian. Gas mass percentage composition is calculated on the basis of peak areas.
Moisture Content
Results of moisture content of analyzed biomasses and residues are shown in Figure 3 and 4.
Figure 1: Humidity of organic wastes samples from the Alto-Alentejo region (Portugal).
Figure 4: Mass percentage humidity of biomass samples from Alto-Alentejo region (Portugal).
550
Most of the analyzed biomass samples showed moisture contents in the range of 10 to 15 %.
However samples of miscanthus, coffee grounds and sawdust have higher moisture contents of
21.67, 25.03, and 31.33 % (w/w), respectively. On the other hand, the cane and willow samples
showed the lowest moisture contents of 9.70 and 10.33 % (w/w), respectively. This homogeneity
on moisture content found for most of the samples types is probably due to the fact that biomasses
samples were kept in laboratory environment for at least one month prior to the moisture content
determination, except for the three types of biomasses with higher water content.
Moisture content of the organic residues, on the other hand, present great variability: dry olive
bagasse and ashes possess lowest moisture contents of 5.30 and 3.00 % (w/w), respectively. In
contrast bagasse paste and tars have highest moisture contents of 53.67 and 54.37 % (w/w),
respectively.
Elemental Analysis
Results of the elemental analysis of biomasses and residues are presented in Table 1 and figure 5.
Most biomass samples have similar composition, showing carbon mass percentages between 40
and 50 % and hydrogen content in the range 4 - 7 %(w/w). Nitrogen was detected only on
pelletized samples of coffea arabica L. husks, sawdust and miscanthus, although the content is as
low as 1 to 4 %. None of the analyzed biomass samples presented sulfur in their composition.
Table 1: Elemental composition of biomass samples.

Biomass %N %C %H %S %O
Pinheiro n.d. 45,59 5,37 n.d. 49,04
Choupo n.d. 45,78 5,28 n.d. 48,94
Cana n.d. 41,22 5,53 n.d. 53,26
Oliveira n.d. 46,40 6,24 n.d. 47,35
Salgueiro Choro n.d. 44,99 5,92 n.d. 49,09
Sobreiro n.d. 45,44 5,83 n.d. 48,73
Salgueiro n.d. 44,32 5,77 n.d. 49,90
Eucalipto n.d. 45,96 5,80 n.d. 48,24
Azinheira n.d. 43,55 5,40 n.d. 51,05
Carvalho n.d. 40,93 4,53 n.d. 54,53
Giesta n.d. 48,45 6,41 n.d. 45,15
Vinha n.d. 42,64 5,34 n.d. 52,02
Pellets 2,34 42,73 4,79 n.d. 50,14
Borra de Caf 4,08 40,09 4,75 n.d. 51,07
Miscanthus pellets 1,69 41,29 5,54 n.d. 51,47
Serradura 2,35 40,60 4,69 n.d. 52,35
Elemental composition of analyzed organic wastes varies quite widely, particularly in terms of C
content with values varying between 5.50 and 43.79 %. None of the samples have S and N in their
constitution. The bagasse paste sample has the lowest mass percentage of C and H, 5.51 and
1.29 %, respectively. Samples of olive stones and ash have C mass percentage lying between 20
and 30% and H content ranging between 4.26 and 1.25 %, respectively. On the other hand, olive
bagasse (?) extracts, dry bagasse and tars showed higher C and H mass percentage, varying from
41.10 to 43.79 %, and 4.62 to 6.39 %, respectively.
Figure 5: Elemental Composition of Organic Wastes.
551
Heating Values
Results of the determination of net heating value of biomasses and organic residues samples are
presented in figures 6 and 7.
All biomass samples have similar heat contents (LHV), with a small variation between 4800 and
5900 kcal. Comparison of the LHV of the various biomass samples with that of a coal sample show
an identical behavior. It seems, therefore, that biomasses collected in Alto-Alentejo region may
constitute a good option for use in thermal gasification processes.
Figure 6: Lower Heating Value of Biomass samples.
Figure 7: Lower Heating Value of Organic Wastes samples.
Organic waste, on the other hand, showed wide variations in their LHVs, particularly for the
bagasse paste samples and ash, that present lower values when compared with that of coal
samples. Dry bagasse, bagasse extracts and tars are have similar values of LHV which compares
quite well themselves with that of coal. Thus, it appears that these last three types of biomasses
are adequate for use in biomass thermal gasification processes.
Syngas characterization
Table 2 present results of Syngas composition and net heat value (NHV) from vine pruning
gasification, one of the biomasses studied above and that was found promissing.
Table 2 - Syngas composition and net heat value (NHV) of different feed compositions and admission
feedstock rates at around 800C
63,7 % wood
100 % wood
26,3 % vine pruning
3
Aparente density (kg/m ) 650 650 650 400 400
Humidity (%) 9 9 9 15 15
Admission rate (kg/h) 40 63 63 40 40
Gasification temperature
800 800 815 800 815
(C)
Syngas composition (%)
CO 21,29 23,02 24,12 16,88 16,25
H2 9,30 11,34 12,08 9,85 9,50
CH4 2,94 3,20 3,37 3,32 3,18
C2H4 0,29 0,38 0,36 0,16 0,15
C2H6 0,06 0,12 0,11 0,09 0,09
N2 53,39 49,56 47,94 51,51 53,22
CO2 11,66 11,10 10,67 17,05 16,49
Others 1,07 1,27 1,34 1,14 1,12
552
NHV (MJ/kg) 4,09 4,72 4,99 3,66 3,51
A generic analysis of the results obtained shows that the produced syngas is rich in carbon
monoxide (mass percentage between 16 % and 27 %), methane (around 3 %) and hydrogen
(about 10 %), and therefore these three gases are the main responsible for the heat content of the
syngas produced which lies between 3 and 5 MJ/kg, as can be seen in table 2. On the other hand,
it can be seen that the syngas contains high amounts of nitrogen (around 50 %) and some carbon
dioxide (between 10 % and 16 %) resulting from the partial combustion process that takes place
simultaneously with biomass gasification.
The results of wood gasification show that higher syngas NHVs increases as temperature and
biomass admission rate into the reactor increases. Indeed, the slight increase in temperature of the
reactor promotes the gasification reaction, increasing the hydrogen and carbon monoxide
production. On the other hand, considering the characteristics of a fluid bed reactor, it is seems
reasonable that increasing the amount of biomass inside the reactor will improve conditions that
leads to higher gasification yields due to an increasing of the residence time in the reactor.
Addition of vine pruning to wood pellets leads to a decrease of the NHV of the syngas produced by
biomass gasification. A further decrease was also observed when the temperature increased from
800 to 815 C. It should be noted that both decreases in NHV were accompanied by a decrease in
carbon monoxide production and consequent increase in carbon dioxide. It is also observed a
slight increase in the amount of hydrogen produced in relation to the gasification of wood pellets.
Such observations may be explained on the basis of the higher moisture content of vine pruning
relative to wood pallets. Higher moisture content may imply extra thermal energy needed for the
gasification process, and a decrease in the chemical energy that is obtained in the syngas.
Moreover, an high moisture content also increases the tendency to produce a hydrogen rich
syngas.
CONCLUSIONS
Performances of biomass used in thermal gasification process depend on several properties of
biomasses sources such as moisture content, elemental composition and calorific value. A suitable
biomass for gasification must have low moisture content, high C content and high heating value. In
terms of moisture content, all the collected biomass samples show small mass percentages, except
for miscanthus, sawdust and coffea arabica L:. Among the analyzed organic wastes, dry bagasse
and ash show the lower humidity content. Referring to the elemental analysis, all biomass analyzed
samples have relatively high levels C and H contents, when compared with some of the most
common agricultural residues used for the same effect [2,3]. Among the organic wastes extracted
and dry olive bagasses and tars present the highest mass percentage of C and H. The presence of
high C and H content could be a good indication that these biomasses could be processed by
thermal gasification to give high yields of H2 a CH4, to valuable fuels. All the collected biomasses
seem to be good options for application in biomass thermal gasification processes on the basis of
their heat content, while in the group of analyzed organic waste, dry olive bagasses, extracted olive
bagasses and tars could be considered good options for this type of uses.
The biomass gasification pilot scale plant based on fluidized bed technology installed at
Portalegres Industrial Park, Portugal, performed well during the overall period of the experiments:
the increase of gasification temperature and feedstock admission rate improves the syngas Net
Heat Value (NHV); experiments proved that mixtures of vine pruning with wood pellets can be used
to syngas production with promising composition, enabling energy valorization of this waste of wine
production.
Literature References
[1] M. Balat, Gasification of Biomass to Produce Gaseous Products, Energy Sources, A 31
(2009) 516.
[2] C. S. Chou, S. H. Lin, W. C. Lu. Preparation and characterization of solid biomass fuel
made from rice straw and rice bran. Fuel Processing Technology 90 (2009) 980-987.
[3] B. Jenkins, L. Baxter, T. Miles Jr, T. Miles. Combustion properties of biomass. Fuel
Processing Technology 54 (1998) 17-46.
Acknowledgments POCTEC Program, ALTERCEXA Project, for financial support.
553
NEW APPROACHES FOR ENVIRONMENTAL MANAGEMENT IN

EUROPEAN FOOTWEAR COMPANIES
1 1 2 2 2 3
M.J. Ferreira , F. Freitas , J. Ferrer , M.A. Martnez , L. Carbonell , M.F. Almeida
1 Centro Tecnolgico do Calado de Portugal (CTCP), So Joo da Madeira, Portugal. E-mail:
mjose.ferreira@ctcp.pt
2 Footwear Technological Institute (INESCOP), Elda, Spain. E-mail: medioambiente@inescop.es
3 LEPAE, Faculdade de Engenharia, Universidade do Porto, Porto, Portugal. E-mail: mfa@fe.up.pt
ABSTRACT
The environmental legislation is extensive, reviewed frequently and in general non-
specific for footwear industrial sector, thus requiring significant investment in technical
resources of firms within this field. European footwear companies need to have access to
updated selected legislative information that applies to the sector in terms of
environmental issues. In this regard the European project LIFE+ SHOELAW
(Environmental legislation among European footwear industries), focuses on the
development of an online tool that enables companies to recognise and improve their
legal environmental situation on waste and water management, the use of hazardous
substances and the emissions to the atmosphere, among others.
Additionally, one of the biggest issues regarding footwear environmental aspects is how
to manage solid wastes. The easiest and most implemented management option for
these wastes has been disposal in landfills. This approach discards all the resources
contained in the materials; thus, more sustainable alternatives than landfilling have been
pursued by several works with different end-of-life purposes. In this work, the potential of
using leather and rubber roughing footwear industrial waste, as such, as reinforcing
additive for shoe rubber soles is demonstrated.
Keywords: Environmental, legislation, footwear industry, leather, rubber, wastes
INTRODUCTION
Safety and sustainability in production and consumption, and health and well-being of individuals,
have been identified as two of the broad long-term societal trends, which clearly have a wide
impact on consumer behaviour and consumption patterns world-wide and create enormous
opportunities and challenges for the consumer goods industry, namely for footwear that presents
potential of growth in consumption and in production (Fig. 1) [1].
Footwear manufacturing involves the use of a large range of materials that are worked to the
appropriate size and format by appropriate technological processes (Fig. 2). For simplicity, shoe
may be divided in the upper and lower part. The first is actually made primarily of leather. The
second includes several components, the most relevant of them being the insock and insole made
of leather, cellulose fibbers or composites; and the sole made of vulcanised rubber, thermoplastic
rubber, polyurethane or others. These materials are cut, processed to adequate shape and jointed
mainly by stitching and bonding operations.
Attachment of the shoe upper and lower parts requires bottom upper materials roughing. Certain
sole materials are also rouged in the bonding margin to better prepare them for adhesion and/or in
the outer face, laterally. These operations generate leather and sole materials fibers, dusts or small
scraps, which represent 5 % to 15 % (w/w) of the solid wastes generated by shoe-making
companies. In any case, the sequential operations the materials, components and products are
subjected to, give added value to numerous resources but result also in environmental emissions.
554
15.000 Europe America
Oceania Asia (except China)
China Middle East
12.000 Africa
Million pairs
9.000
China
6.000
Asia, except China

3.000
America
Europe
0
1985 1989 1992 1995 1997 1999 2001 2003 2005 2007
Year
Figure 1 Footwear World production (1995 2008)
In general, the most significant environmental aspects relating to the footwear industry are: (1)
difficulties in gaining access to environmental legislation; and (2) management of solid wastes,
especially chromium tanned leather.
Regarding the legislation, about 42 % of footwear companies find it difficult to access to
environmental legislation and 75 % do not have a reliable system providing access to such
legislation. It is difficult to gather requirements affecting businesses at a national level, which is
even more complicated if environmental legislation concerning exportation is also to be considered.
Moreover, difficulties of small and medium sized enterprises in updating environmental regulations
are well-known, most of the time because of a lack of time or qualified personnel, and also because
information does not come in a suitable format to satisfy the companies specific needs. In fact, the
legislation is difficult to be understood and requires knowledge, time and dedication. Furthermore,
in the everyday life, this has to be carried out individually by every footwear manufacturer.
However, thanks to the SHOELAW project [2], this will be done only once and it will serve all
companies; and the language will become more straightforward.
Regarding the solid wastes, in the shoe industry, it can be estimated that an average of 0.1 kg to
0.2 kg of finished leather waste is generated by each pair produced [3]. In the EU footwear industry
9 5
about 0.94 x 10 pairs of shoes were produced in 2008 [4], consequently generating about 1 x 10
5
to 2 x 10 metric tonnes of leather waste in that year. Thus, estimating the disposal cost as 40 to
6 6
60 per metric ton, the annual cost supported by the sector was of 4 x 10 to 10 x 10 . Studies
on leather fibers and powdered rubber indicate as possible to obtain performing composite
materials [5, 6]. Most of those studies involve laborious materials pretreatments such as grinding
and chemical compatibilization.
In this work two initiatives are reported:
(1) An online tool that enables companies to know the requirements applying to them at national
level and in other countries when exporting footwear. This is the case of certain hazardous
substances such as chromium, formaldehyde or lead, whose restrictions depend on the
importing country;
(2) A comparative study on the effect of incorporating upper (leather based) and sole (rubber
based) roughing wastes, collected at an industrial site, in the range of 20 parts of additive per
hundred parts of rubber (phr) to 100 phr, on the properties of one of the elastomers more
frequently used in shoe components (acrylonitrile butadiene rubber - NBR).
555
FOOTWEAR
MANUFACTURE
CONSUMER
MATERIALS AND COMPONENTS USED
Cutting SHOES
Leather Stitching
Processing +
Plants Textiles
Trees Plastics
Rubbers Assembling EMISSIONS
Animals
Petroleum Soles
Volatile
Minerals Paper Finishing organic
Energy Composites
compounds
Adhesives
Finishing Products Packaging Liquid
Metallic parts efluents
Expedition Solid
Wastes
Retail Nuissance
ENERGY
and others
Figure 2 Simplified footwear manufacture inventory
SHOELAW PROJECT AND ONLINE TOOL

st
The SHOELAW project is scheduled for 30 months, and started on the 1 of January 2010 [2]. The
project is mainly addressed to small and medium sized footwear companies and counts on the
participation of 5 research centres and more than 50 footwear companies.
The projects main objectives are: (1) To develop an IT platform for the environmental legislative
self-diagnosis addressed to footwear companies; (2) To encourage the application and the
effective enforcement of the environmental legislation among footwear companies; (3) To improve
the environmental situation of footwear companies; and, (4) To spread out the use of the IT
platform among footwear companies.
The project started with the gathering of all the environmental legislation affecting footwear
companies at a regional, national and European level. Each research centre was in charge of
extracting all the environmental legal requirements of their respective country, all the information
being available in English as well as in the national language. Following, legal requirements were
entered in an IT platform intended for footwear companies to perform their environmental self-
diagnosis. This tool (Fig. 3) is now available at pilot testing scale for use online, and footwear
manufacturers will simply have to answer a series of questions, to learn which legal requirements
apply to them, their degree of compliance and recommendations on how they can resolve any fault
detected. Interested firms from participating countries can already pre-register (www.shoelaw.eu).
One of the targets of this project is to give to the IT platform an international dimension (initially 5
countries were part of it but it is planned to extend this tool to all interested countries). Taking into
account the extension of this tool to other countries in the world, a Microsoft Access database was
developed, which allows entering the information extracted from each countrys legislation in an
organised way, in its original language as well as in English. Information stored in this database
constitutes the basis for the environmental self-diagnosis IT platform.
The identification of the environmental legislation and corrective measures applicable to the
footwear sector requires an important effort as it is necessary to revise thoroughly all of the
environmental legislation (among hundreds of regulations) in order to compile the legislation which
affects footwear companies, to extract the applicable requirements and to define the more
adequate corrective options. Thanks to the SHOELAW project, all these regulations were gathered
in an IT platform. The main characteristics of this IT platform addressed to footwear companies are:
(1) User-friendly, in any case, if necessary, the companies can always use the help of the research
centres;
(2) Multilingual version; initially this tool will be available in 6 languages (English, Italian, Greek,
Portuguese, Slovenian and Spanish) and will be prepared to include further languages;
556
(3) Guarantee of the confidentiality of companies data, thanks to the deployment of a module that
will allow these data to be stored locally and not on the server;
(4) Possibility of self-diagnosis in interest area (waste, atmospheric emissions, wastewater, etc).
This way, users will not need to answer questions about aspects which do not affect them or
which are not of their interest;
(5) Alert service which notifies to manufacturers changes in the legislation;
(6) Statistics service to compare the environmental situation of one firm with respect to the sectors
average.
Because of their innovative nature, the alert and statistics service stand out. The alert system,
customised for each company, will allow updating environmental requirements quickly and
effectively. Each time a requirement is added or modified in the IT platform; changes will be directly
communicated by e-mails to footwear manufacturers. Furthermore, the statistics service will allow
the companies to know straight away their environmental situation, comparing it with other
companies in the same sector, not only on a regional or national scale but also with other countries
collaborating with the IT platform. Thanks to this statistics system, the compliance of each
company will be registered anonymously and will allow the selection of the desired variables
(company size, geographic area, etc.).
Figure 3 SHOELAW IT platform print screen
LEATHER AND RUBBER COMPOSITES FOR FOOTWEAR APPLICATION
Materials and Composites Preparation and Characterization

The upper roughing leather waste and roughing soles waste were collected at one industrial site,
thoroughly homogenized, and referenced, respectively, as UD and SD. Very often these two types
of wastes are mixed at the companies where they are generated. Therefore, two types of mixtures
were prepared, respectively 50 % UD + 50 % SD and 75 % UD + 25 % SD, both in w/w %. These
mixtures were referenced as MIX1 and MIX2, respectively.
NBR material was from Kumho Petrochemical, medium viscosity (45 to 50 Mooney), grade NBR
35 LM. All major other chemicals used were of rubber grade.
The NBR rubber compound was prepared according to an in-house recipe [7]. After preparation, it
was charged with the footwear wastes on a laboratory-scale open two-roll rubber mixing mill from
Roca & Guix, according to the following experimental plan: (1) 20 phr, 50 phr, and 100 phr of UD;
(2) 20 phr, 50 phr, and 100 phr of SD; (3) 20 phr, 50 phr, 75 phr and 100 phr of MIX1; and, (4) 50
phr, 75 phr and 100 phr of MIX2; to the NBR rubber compound. A control mix with no residue was
also prepared for comparison. Vulcanization was carried out in a lab hydraulic heated press at 423
K for the optimum cure times obtained by rheometric measurements. All the composites plaques
were produced in triplicate and stored at 296 K 2 K for characterization.
557
The waste materials and the composites were physically, chemically and morphologically
characterized according to the applicable standards and techniques as elsewhere reported [7].
Results and Discussion

According DL 183/2009 [8] UD and SD wastes are actually classified as granular non-hazardous
wastes. In the following paragraphs mainly the properties required for the application of
composites in footwear are reported, even thought a more extensive characterization of these
materials was carried out and presented elsewhere [7].
Selected physical properties are shown in Fig. 4. The density of all NBR composites prepared is in
3 3
the range of 1.11 Mg/m 0.05 Mg/m . Hardness increases gradually with increasing addition of
UD, SD, MIX1 and MIX2 residues from about 60 Shore A up to 85 Shore A, 80 Shore A, 85 Shore
A and 90 Shore A, respectively. These results can be attributed to the more rigid material nature of
the additives, which added higher hardness to the softer elastomer phase compared with the
vulcanizates containing no or lesser amount of additive, as has been reported for other systems [5].
Density, ISO 2781 (Method B), Mg/mm3 Hardness x 10, ISO 868, Shore A
Tear strenght, EN 12771,N/mm Tensile strenght, EN 12803, MPa
Elongation at break x 100, EN 12803, MPa Abrasion resistance x 10, EN 12770, mm3
30
25
20
15
10
0
75 1
10 I X1
1
75 X2
10 IX2
1
2
D
10 D
D
10 D
BR
SD
SD
IX
IX
IX
IX
U
I
M
M
M
M
M
M
N
20
0
0
20
50
50
20
50
0
0
50
Fig.4 - Physical properties of composites
An increment in tear resistance property is observed with the wastes addition, too: (i) UD (mainly
leather fibers granules and dusts) incorporation in 20 phr, 50 phr and 100 phr increases average
tear resistance in composites of 100 %, 122 % and 44 % relatively to the base formulation; (ii) the
same incorporation of SD (mainly rubber sole granules and dusts) promotes average tear
resistance increase of 13 %, 51 % and 42 % relatively to the base formulation; (iii) MIX1
composites with 20 phr, 50 phr, 75 phr and 100 phr incorporation increases average tear
resistance of 128 %, 83 %, 80 % and 41 % relatively to the base formulation; and, (iv) MIX2
incorporation in 50 phr, 75 phr and 100 phr produces composites with tear resistance on average
increased by 95 %, 71 % and 21 %, relatively to the base formulation. All the composites are
adequate for applications in soles for normal and demanding footwear. The considerable increase
in tear strength up to specified limits when leather containing residue additive is added is due to the
fibrous nature of leather that effectively prevents the growth of the test specimen crack.
Abrasion resistance decreases with increasing additive incorporation; nevertheless, all the
composites prepared have abrasion resistance adequate for application in soles of day-to-day use.
An increase in tensile strength relatively to the base NBR formulation is observed for the
composites: (i) 20 phr UD; (ii) 20 phr SD; and (iii) 20 phr MIX1. An increase in elongation at break
is also observed for the following composites: (i) 20 phr UD; (ii) all SD additions; (iii) 20 phr and 50
phr MIX1; and, (iv) 50 phr MIX2. Therefore, till 20 phr of UD, SD and MIX1 incorporation the
composites present tensile strength and elongation properties satisfactory for soles application.
Till 50 phr of residue additives incorporation (results not shown), the composites gave around 0.01
mm/kcycle, thus a satisfactory behaviour with respect to flexing resistance.
558
The decrease of abrasion resistance, tensile strength, elongation at break and flexing resistance
with increasing waste additives incorporation may partly be explained by the size of the additive
materials and consequent voids in the matrix. Upon abrasion, tension and stretching the voids grow
in size and interact between them, leading to material de-bonding and failure. As indicated by
Ravichandran and Natchimuthu [5, 6], a further negative contribution comes from the acidic and
hydrophilic leather nature, thus leading to poor adhesion between the leather and the matrix.
Water absorption increases with leather fibers addition due to their hydrophilic characteristics.
Nevertheless, all the composites gave water absorption below 3 % to 4 % (w/w) (results not
shown), These results indicate that even thought leather fibers have high affinity with water, when
they are consolidated in the composite, the water uptake is reduced due to the more limited
interaction of leather fibers with water and the hydrophobic nature of the rubber matrix.
CONCLUSION
The main environmental aspects affecting footwear companies are complying with the
environmental legislation and managing their solid wastes. Two approaches to face these
challenges are here presented. The use of SHOELAW online preventive tool will provide
manufacturers with the environmental legal requirements in the footwear industry, helping them to
detect and improve their weak points and boost their strong points. Additionally, the tool will give
information about environmental legislation specific to other EU countries as an instrument to
facilitate intra-community exports of footwear articles. In a different point of view, leather fibers and
powdered rubber are demonstrated as usable to obtain performing composite materials. Under the
conditions tested, the residues from footwear roughing operations, as such, with any pre-treatment,
might be recycled as day-to-day footwear rubber soles additive up to 20 phr incorporation.
BIBLIOGRAPHY
[1] APICCAPS Portuguese Footwear Manufacturers Association. Footwear, Components and
Leather Goods - Statistical Study 2009, Edition 1. Porto, Portugal, December 2010.
[2] Information on http://www.shoelaw.eu/.
th
[3] M.J. Ferreira, M.F. Almeida, Product monitoring - Towards footwear sustainability, 15
International Technical Footwear Congress, Tunis, 1 (2005) 97-107.
[4] APICCAPS Portuguese Footwear Manufacturers Association. Footwear, Components and
Leather Goods - Statistical Study 2010, Edition 1. Porto, Portugal, 2011 in Press.
[5] K. Ravichandran, N. Natchimuthu, Vulcanization characteristics and mechanical properties of
natural rubberscrap rubber compositions filled with leather particles, Polymer Int. 54 (2005)
553-559.
[6] K. Ravichandran, N. Natchimuthu, Natural Rubber - Leather Composites. Polmeros: Cincia
e Tecnologia. 15 (2005) 102-108.
[7] M.J. Ferreira, M.F Almeida, F. Freitas, Formulation and characterization of leather and
rubber wastes composites, Polymer Engineering & Science. 51 (2011) 14181427.
[8] Decreto-Lei n. 183/2009, Dirio da Repblica, 10 de Agosto de 2009 (nm. 1539), Srie I -
Ministrio do Ambiente, do Ordenamento do Territrio e do Desenvolvimento Regional.
ACKNOWLEDGEMENTS
SHOELAW project is funded by the European Union in the framework of the European
Environment programme LIFE+ (reference LIFE 08 ENV/E/000147).
The work regarding composites received the support of the Portuguese Programs POE Medida 2.2
B and PRIME Medida 3.1 A, project SHOEMAT (grant number 03/81). In this frame, the authors
acknowledge the rubber production company Procalado Produtora de Componentes para
Calado, S.A., for facilitating the use of lab, scale-up and industrial materials and equipments.
559
ESTIMATION OF HEAVY METAL TRANSFER FROM SOIL TO PLANT IN

AGRICULTURE ORGANIC WASTE REUSE SCENARIOS
1 1 2 1
C. Lopes , M. Herva , A. Franco-Ura and E. Roca
1 Sustainable Processes and Products Engineering and Management Group. Dept. of Chemical
Engineering, School of Engineering, University of Santiago de Compostela, Campus Vida, 15782
Santiago de Compostela, Spain, corresponding author: enrique.roca@usc.es
2 Process Engineering Group, Marine Research Institute IIM-CSIC, Eduardo Cabello, 6 - 36208
Vigo, Spain
ABSTRACT
The reuse of organic wastes as fertilizer represents an important outlet for wastes and
contributes to the sustainability of farming activities. However, given the presence of
several contaminants in the residues, this practice must be carried out under safety
conditions in order to avoid the pollution of soil, groundwater and vegetation, and to
protect human health. For estimating the fate and exposure of several pollutants in the
environment and predicting the probability of possible adverse effects to human health in
different exposure scenarios, the environmental risk assessment (ERA) methodology is
commonly used. In particular, when an agricultural scenario is evaluated, it is crucial to
know the concentrations of pollutants in compartments such as vegetation. The use of
simple models is preferred with that purpose.
The aim of this work was estimate heavy metal concentrations transfer from soil to plants
in pasturelands fertilized with manure. With that purpose soil-plant uptake factors (UF)
based on bioavailable metal concentrations were used. The results obtained indicated
that the use of soil-plant UF is an adequate method for estimating the metal
concentrations in plant since the relationship between the soil-plant UF and the metal
concentration in soil solution was significantly described by a power model for all metals.
Keywords: Organic waste; uptake factors; heavy metals; environmental risk assessment
INTRODUCTION
The valorization of organic wastes as a soil fertilizer offers a number of advantages over other
management alternatives. The application of organic wastes, such as manure, presents several
benefits to soil properties [1]. However, manure can be a significant source of contaminants in soil,
such as heavy metals [2]. In this sense, the application of manure in soil must be done adequately
and under appropriate conditions in order to avoid the accumulation of heavy metals in soil and
consequently the transfer to other compartments, such as soil solution and plant. This would
reduce or avoid the exposure of humans to these contaminants through different pathways [3].
Quantitative exposure to contaminants can be evaluated by employing an environmental risk
assessment (ERA) methodology [4]. This method requires an understanding of the transport of
contaminants from source to receptor. Therefore, ERA methodology may involve the estimation of
the fate of contaminants, since knowing the concentration in the different compartments involved in
a specific scenario is frequently a difficult, expensive and time-consuming task. However, the
knowledge of these variables is essential to evaluate the exposure of receptors and, consequently,
the application of simple models that only depend on concentrations of heavy metals in soil may
result very useful to carry out risk assessments.
Both mechanistic and empirical models are used to predict heavy metals uptake from soil or soil
solution to plants. Mechanistic models are based on plant and soil parameters which are difficult to
determine, e.g. diffusion coefficients of ions in the soil solution, root geometry and size and kinetic
560
parameters for the uptake of ions by the roots. In the scope of risk assessment, these approaches
may be too sophisticated and, for this reason, the use of empirical models is usually adopted [5,6].
For the prediction of metal uptake by plants, a constant soil-plant uptake factor (UF) can be used
[7]. Considering that plants uptake metals from the soil solution, environmental quality objectives
should be based on metal concentrations in soil solution rather than on total concentrations [8].
Also, since the soil-plant UF values change with the soil metal concentrations, the representative
UF value for a given plant-metal system should be estimated at a specific soil metal concentration
[9]. Otherwise, if the mean or the median are used as the representative value of a given plant and
metal system, the transfer risk will be overestimated if the plant samples values come from soils
with low metal concentrations whereas the transfer risk will be underestimated if the samples are
from soils with higher metal concentrations [9].
In this work, the estimation of heavy metal (Mn, Fe, Zn, Cu, Cr, Co, Ni, Cd and Pb) concentrations
in plant was done using soil-plant UF values. Therefore, similarly to Wang et al. [9], regression
models between the UF and the soil metal concentrations were obtained for each metal.
Furthermore, the obtained models, which show the metal transfer tendencies, are presented.

This section includes the description of the scenario, the chemical analyzes and the model used for
predict the metal concentrations transfer from soil to plants.
Characterization of the scenario

The scenario studied consisted in the reuse of cattle manure as fertilizer in pasturelands. The
investigated area, traditionally dedicated to agricultural activities, corresponds to an extension of
2250 ha of pastureland surrounding river Magdalena basin in the province of Lugo (Galicia, NW
Spain), and it was further described in other works [4,12]. 20 sampling points in different pasture
plots regularly fertilized with cattle manure were defined and 3 samples at different depths (0-5, 5-
10 and 10-20 cm) were collected from each of them. The agricultural landscape is mainly
constituted of grasslands and the measurements of plant metal concentration corresponded to the
growth form of above-ground tissue, predominantly herb and graminoid. The vegetation grown on
the selected sampling plots and 20 vegetation samples were collected (in duplicate) in May and
July months. The ERA was focused on the risk derived from heavy metals (Mn, Fe, Zn, Cu, Cr, Co,
Ni, Cd and Pb).
Description of the chemical analyses

Two extracting agents, namely DTPA (Diethylene Triamine Pentaacetic Acid) and Mehlich-3, were
employed to determine bioavailable metal concentrations in soil. DTPA and Mehlich-3 are multi-
element extraction solutions, frequently referred as universal extractants, because of its capability
for evaluating a number of elements simultaneously. DTPA is a common soil extractant for
available soil micronutrients like Zn, Fe, Cu and Mn in nearly neutral soils, worldwide accepted
after its international standardization [13]. On the other hand, Melhich-3 is an extractant developed
to measure amounts of major nutrients and micronutrients in soil, being effective in soils with a
wide range of physical and chemical properties; thus, it is proposed to be used over an extensive
range of soil pH, including not only acid but also neutral and alkaline soils [14]. Samples of plant
were subjected to digestion and heavy metals (Mn, Fe, Zn, Cu, Cr, Co, Ni, Cd and Pb) were
determined by ICP-OES with a PerkinElmer Optima 4300 DV spectrophotometer.
Model development
The application of a regression model to predict the values of concentration of heavy metals in
plant revealed to be an inappropriate option, since in most cases no significant and poor
correlations were found between metal content in soil (total and bioavailable) and soil properties
(pH, OM, P, TC and TN) with metal content in plant [15]. This is in agreement with the results
obtained by Wang et al. [9], in which no significant or poor correlations were obtained between
metal content in plant and soil properties and metal content in soil (total or bioavailable).
As an alternative, a method based on soil-plant UF was selected to estimate heavy metal
concentration in plants.
561
In this work, the estimation of heavy metal concentrations in plant was obtained using soil-plant UF.
This constant expresses the transfer of metals from soil to plant tissue under steady state
-1
conditions [16]. It can be defined as the ratio of the chemical concentration in plant Cp (mg kg ) to
-1
the chemical concentration in soil Cs (mg kg ), as it is shown in Equation 1.
Cp
UF (1)
Cs
The concentration of bioavailable metals in soil is considered to be a better parameter than total
metal concentration to predict the transfer of metals from soil to plants [8,10,11]. Then, the soil-
plant UF for a given plant-metal system should be correlated with the corresponding soil metal
concentrations (total or bioavailable) by regression models. Then, regression models between soil-
plant UF and metal concentration in soil solution were developed for each metal. The models were

performed using the software SPSS 15.0.

The soil-plant UFs on the basis of bioavailable metal concentration in soil were calculated for each
observation in the experimental data. Since the soil-plant UF is found to be dependent on the
environmental conditions (e.g., climatic regime, soil type and chemistry [17]), it is reasonable to
estimate the soil-plant UF for a specific metal concentration in soil.
Accordingly, the soil-plant UF was assessed in terms of bioavailable metal concentrations in soil
(Mehlich-3 and DTPA) and the best relationship was found. Fig. 1 presents the most significant
models obtained, showing the tendencies of bioavailable metal transfer to plant. It was observed
that soil-plant UFs decreased as the bioavailable concentrations in soil increased, for all the heavy
metals (Fig. 1). This fact was more obvious at low concentrations, where the shape of the curve
was sharper.
Fig. 1. Uptake factors calculated from bioavailable soil concentrations as a function of bioavailable
soil concentrations for the different metals.
562
It was observed that the relationship between the soil-plant UF and the bioavailable metal
concentration in soil could be significantly described by a power model for all heavy metals (Table
1). Metals like Mn, Zn, Cu and Co are nutrients and it is not surprising that their accumulation
would be regulated by plants. Baes et al. [7] also found that the UF for Cu and Zn were inversely
correlated with soil concentrations. This can be explained with the interaction of root exudates with
the surroundings solids. Excretion of root exudates, which contain organic acids, amino acids,
sugars and high molecular weight compounds, increase the solubility and bioavailability of metals
in the rhizosphere [18]. Therefore, as above mentioned, the uptake of metals is regulated by plants.
For Fe, Cu, Cr, Co and Ni, the best correlations were obtained when the bioavailable
concentrations of metals extracted with Mehlich-3 were used, while for Mn, Zn, Cd and Pb the
DTPA concentrations provided better results. The curvilinear relationships clearly indicated that the
soil-plant UF obtained from bioavailable metal concentrations in soil is not constant for a given
plant-metal system, as it varies as a function of bioavailable concentration in soil [9]. This reduction
could be attributed to a higher competition among ions at the absorption sites on roots at high
metal concentrations [19].
In the scope of ERA methodology, to evaluate the potential adverse effects on human health
resulting from the application of organic wastes containing heavy metals as fertilizer in the
production of forage, the use of soil-plant UF can result in an important method for estimate data of
metal concentration in plants, since it is a very simple and appropriate model, taking into account
the obtained results. The models obtained were significant for all the heavy metals; however, for
2
metals such as Ni and Cd, poor relationships were found, being the R values equal to 0.29 and
0.24, respectively.
Table 1. Relationship between the soil-plant UF and the metal concentration in soil solution for the
different heavy metals.
2
Metal Extractant n Model R Significance
-0.850
Mn DTPA 20 UF = 94.053Cl 0.678 0.000
-1.182
Fe Mehlich-3 16 UF = 514.893Cl 0.461 0.004
-0.976
Zn DTPA 20 UF = 29.873Cl 0.736 0.000
-0.998
Cu Mehlich-3 20 UF = 6.267Cl 0.981 0.000
-1.263
Cr Mehlich-3 13 UF = 0.472Cl 0.783 0.000
-0.904
Co Mehlich-3 20 UF = 0.752Cl 0.836 0.000
-1.286
Ni Mehlich-3 17 UF = 0.387Cl 0.288 0.026
-1.217
Cd DTPA 18 UF = 0.033Cl 0.243 0.038
-1.834
Pb DTPA 13 UF = 0.285Cl 0.644 0.001
-1
n = number of observations; UF = Uptake factor; Cl = Metal concentration in soil solution [mg kg ].
CONCLUSIONS
Reuse of manure as soil fertilizer offers a number of advantages, however this practice must be
carried out under safety conditions since metals present in manure can be released to the soil,
groundwater and plants and consequently, affected the human health. For the purpose of risk
assessment, models must be developed to estimate the concentrations of contaminants in
compartments such as soil solution and plant, in order to evaluate the risk of heavy metals to
humans through the food chain.
Significant models were obtained, for all heavy metals, when soil-plant UF based on metal
concentration in soil solution were used. Also, it was verified that with both extractants (DTPA and
Mehlich-3) good relationships can be obtained. The best models were obtained with DTPA for Mn,
Zn, Cd and Pb, and with Mehlich-3 for Fe, Cu, Cr, Co and Ni. Since the soil-plant UF changes with
the corresponding soil metal concentrations, it is recommended to estimate a representative UF
563
from the regression model between the soil-plant UF and the bioavailable metal concentration at a
given soil metal concentration.
In the context of ERA and based on the previous results obtained with correlation models for the
same area of study, it is suggested to use the soil-plant UF to obtain metal concentrations in plant,
since more reliable results would be obtained.
Acknowledgements
through the Project INDIE (CTM2010-18893) ERDF included. Marta Herva wishes to thank the
University of Santiago de Compostela for her pre-doctoral contract. Dr. Amaya Franco-Ura would
like to thank MICINN for the support provided by the Juan de la Cierva Subprogram.
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[3] A. Franco, M. Schuhmacher, E. Roca, J.L. Domingo, Application of cattle manure as fertilizer
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[12] A. Franco-Ura, C. Lpez-Mateo, E. Roca, M.L. Fernndez-Marcos, Source identification of
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(2009) 1008-1015.
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[14] A. Mehlich, Mehlich-3 soil test extractant: a modification of Mehlich-2 extractant, Commun.
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transfer from soil to vegetation in a cattle manure application scenario. In: ICCE 2009: 12th
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565
PHYTOTOXICITY ASSESSMENT THROUGH LEPIDIUM SATIVUM OF

WASTES POTENTIALLY RECYCLED BY COMPOSTING
S. Belo1, M.R Soares2, C.Matchine3, M.J. Quina3,a, J.C. Gis1, R. Quinta-Ferreira3

1 Mechanical Engineering Department, Faculty of Sciences and Technology, University of Coimbra,
Rua Lus Reis Santos - Plo II, 3030-788 Coimbra, Portugal.
2Cernas Natural Resources, Environment and Society Research Centre, Coimbra College of
Agriculture, Polytechnic Institute of Coimbra, Bencanta, 3040-316 Coimbra, Portugal
3 CIEPQPF- Research Centre on Chemical Processes Engineering and Forest Products, Chemical
Engineering Department, Faculty of Sciences and Technology, University of Coimbra, Rua Slvio
Lima - Plo II, 3030-790 Coimbra, Portugal. a email: guida@eq.uc.pt
ABSTRACT
The main goal of this study was to evaluate the phytotoxicity of several materials
potentially recycled by composting, throughout composting processes and compost in
maturation phase. For that, the effect water extracts obtained from material/compost on
seed germination and primary root growth of garden cress (Lepidium sativum) were
measured and the germination index (GI, a product of relative seed germination and root
elongation) was calculated. The results showed that some raw materials, like grass
clipping and sewage sludge can be considered free of phytotoxins (GI>80%), but other
such as chicken manure, fly ash, wheat straw and sawdust, can be very phytotoxic.
Some of these materials were valorized through composting in two sets of laboratory
experiments. The blends tested included industrial potato peels, grass clipping and
additionally sawdust or rice husk as bulking agents. The results obtained showed that
initial compositions determined the profiles of phytotoxicity and the period of maturation
as well. The phytotoxicity assessment in four experiments with sawdust revealed that
after 81 days, the GI attained the maximum level of 60%. In the experiments with rice
husk, GI profiles along time were higher, and in two cases, composts can be considered
moderately phytotoxics after 39th day, with GI of 67% and 72%. In all processes, the more
favorable GI values were obtained in composts with higher proportions of bulking agent in
their initial mixtures. The analysis of composts in maturation stage showed that the use of
sawdust as bulking agent, required more time of maturation than composts with wheat
straw. However, after 111 days, all composts showed similar levels of phytotoxicity and
can be considered mature.
Keywords: phytotoxicity; Lepidium sativum; germination index; composting.
INTRODUCTION
Composting process may be defined as the biological decomposition of organic subtracts, under
aerobic conditions that allow the production of a final stable and humus like material (compost),
free of pathogens and plant seeds [1]. In general, wastes with enough biodegradable organic
matter may be recycled through composting processes (e.g. animal manure, sawdust, straw, fruits
and vegetables). In certain cases, small amounts of inorganic materials (e.g. ashes, eggshells) can
also be valorized through this technology. The finished compost can be beneficially applied to land
as soil amendment or as a medium to grow plants. However, care must be taken in its use, and it is
required to understand the characteristics of the finished product in order to avoid any undesirable
effect [2]. In this scope, maturity is one of the most important aspects of compost quality, and
generally refers to the degree of decomposition of phytotoxic organic substances produced during
the active composting stage and to the absence of pathogens and viable weed seeds [3]. In
practice, this concept is related to the agricultural value of the compost, in what respects to its
effects on the soil and plants response to its application [4]. The phytotoxicity is an important
566
parameter that can be determined during or at end of the composting process, because it allows
assessing the degree of maturation of the compost. Various methods have been proposed in
literature for determining compost maturity, which are usually based on bioassays such as
germination index (GI) [5].
In our study, GI in aqueous extracts was calculated by using garden cress (Lepidium sativum),
since this is a well known method that gives rapid results (germination within 24 h) and reveals high
sensitivity to toxins. This bioassay evaluates if a material contains any substance that inhibit the
seed germination and root growth, and thus, GI may be referred as a lumped parameter. Some
experimental results have been shown that the negative effects on plants may occur due to
substances that induces high microbial activity that can block the existing soil-available nitrogen or
introduce phytotoxic substances in soil, such as heavy metals, phenolic compounds, ethylene and
ammonia, excess accumulation of salts or organic acids [5]. The principal objective of our study is
to assess phytotoxicity in: nine starting materials potentially recycled by composting; along with two
sets of composting experiments, each involving four experiments; and three different composts in
curing phase.

Starting material potentially recycled by composting
Nine different starting materials were evaluated in this study in what respects phytotoxicity, which
may be grouped in three categories:
i) Organic wastes: grass clipping (GC), potato peels (PP), chicken manure (CM) and sewage
sludge (SS);
ii) Inorganic wastes: eggshells (ES) and fly ashes formed in air pollution control devices from
municipal solid waste incineration (FA);
iii) Bulking agents: wheat straw (WS), sawdust (SD) and rice husk (RH).
Composting processes
In order to determine the effect of the composting on the removal of the phytotoxicity in the
mixtures of wastes, eight air-forced composting experiments were carried out. Four of the
experiments used sawdust (SD) as bulking agent (referred RSD,1 RSD,4) and in other four rice husk
(RH) was employed (referred RRH,1 RRH,4). Table 1 shows the global compositions tested, where it
can be seen that in all the cases grass clipping (GC) and potato peels (PP) were blended with a
bulking agent. Each set of composting processes were carried out in four laboratory self-heating
reactor (SHR), with a 120 L capacity, and isolated with a rubber based elastomeric material
(Aeroflex MSR). During the composting, a continuous air flow was injected in the bottom of each
reactor, and for its manual control, a minimum set point of 5% (v/v) concerning the oxygen
concentration in the exit flow rate was considered. The temperature and oxygen concentration in
reactors were monitored continuously with a data acquisition system. The thermophilic phases
lasted about 7 days and the maturation stages began on 19 to 25th day, for all composting
processes. Periodically, about 500 g of sample was collected in several random points in each
th
reactor, at days 0, 4, 11, 18, 25. Additionally, for processes with RH a sample was taken at 39
th
day, and for processes with SD at 46 and 81 day.
Table 1- Composition of the mixture for composting and operating conditions of SHR.
Experiments Mixture composting SHR operating reactor
PP [%w/w] GC [%w/w] SD [%w/w] RH [%w/w] Inlet gas temp. (C) [O2]outlet gas Span period inside SHR
[days]
RSD,1 53.0 39.8 7.2 - 22 18
RSD,2 66.0 28.0 6.0 - 22 18
RSD,3 38.7 53.0 8.3 - 22 21
RSD,4 34.3 51.6 14.1 - 22 21
>5%
RRH,1 58.7 19.4 - 21.9 22-23 25
RRH,2 50.6 32.4 - 17.0 22-23 25
RRH,3 66.0 8.1 - 25.9 22-23 25
RRH,4 74.0 8.3 - 17.7 22-23 25
567
Composts in maturation stage
In this study, the level of phytotoxicity of three composts in the final stages of maturation (C1 to C3)
was also analyzed, which were previously obtained in the same laboratory facility. These composts
were also obtained by using PP and GC. However, in the case of C1, sawdust was the bulking
agent, and for C2-C3 wheat straw was used. The collection of samples for phytotoxicity analysis of
C1-C3 composts occurred at 65 and 111th days of the maturation phases.
Preparation of aqueous extracts and seed germination assays

The aqueous extract used in germination tests was obtained by extracting 10 g of solid (dry weight)
with 100 mL of distilled water (L/S = 10). This suspension was shaken mechanically at 16 rpm
for 1 h at room temperature, and the suspension was centrifuged for 20 min to facilitate solid
liquid separation. The supernatant was filtered using a vacuum system to take about 50 mL for the
germination tests and chemical analysis. The trial run of germination tests consisted of placing a
filter paper for qualitative analysis, in a petri dish 9 cm in diameter, moistening it with 5 mL of
extract. In control tests, 5 mL of distilled water per dish were used. In each petri dish, 10 seeds
of Lepidium sativum was placed and evenly distributed. The tests took place during 48 h in closed
conditions. For each phytoxicity analysis 3 or 5 replicates were made. The incubation of samples
was carried out in an oven at 25-26 C and in dark conditions. After 48 h in the greenhouse, the
number of germinated seeds in each petri dish was counted and the roots length of the germinated
seeds was measured. The relative seed germination (RSG), relative root growth (RRG) and
germination index (GI) were calculated as follows:
(1)
(2)
(3)
If all measurements of the number seed germinated and their mean length observed in five
replicated control petri dish are combined with the five replicated extracts, then it is possible to
obtain 25 values for GI. Thus, it can be defined a mean germination index, GImean, and also a
standard error associated to it.
All data from germination tests were analyzed through box plots diagrams, for determining outliers.
One-way analysis of variance (ANOVA) was used several times to test the equality of three or
more means at one time based on variances. As null hypotheses, it was assumed that all
populations means are equal, and the alternative hypotheses is that at least one mean is different.
The level of significance considered was p=0.05.
Phytotoxicity assessment of materials with potential to be further recycled by composing

Table 2 shows some physico-chemical properties of the tested materials (moisture content, pH,
electrical conductivity, and C/N ratio), as well as phytotoxicity parameters (RSG, RRG and GI).
From GImean values calculated, it can be concluded that wastes such as GC and SS showed results
statistically similar (p = 0.357), despite the average GI of 103% and 98.6%, respectively. These
values indicate that the materials are free from phytotoxins that inhibit the germination of Lepidium
sativum, since GI attained values above 80% [6]. The extracts of RH resulted in an average GI of
74.4% and a mean standard error of 3.9%, indicating that the extract is moderately phytotoxic.
However, waste PP and ES have relatively low average GImean, 45.0% and 53.6% respectively,
showing to be phytotoxic. The high pH of ES measured in the extracts (pH = 9.66) and the low
value observed for PP (pH = 5.39), may have contributed to these values. According to Zucconi
and Bertoldi (1987), extracts characterized by GI below 60% cannot be safely applied to
agricultural soils [9].
568
Table 2- Physico-chemical properties of materials potentially usable in composting and phytotoxicity parameters.
Physico-chemical properties Phytotoxicity parameters

Materials H[%] pH EC [mS/cm] C/N RRG [%] RRG[%] GI [%] GImeanstd error
Classification
Organic wastes CM 20.14 8.89 10.5 7.48 12.0 3.48 <30* b) Very phytotoxic
PP 78.68 5.39 0.84 25.5 96.0 45.8 43.9 45.02.85 Phytotoxic
GC 70.09 8.19 0.46 11.3 100 99.5 99.5 1034.63 Non- phytotoxic
SS 9.27 7.2 1.97 5.6 100 96.0 96.0 98.67.76 Non- phytotoxic
Inorganic wastes ES 18.77 9.66 0.45 a) 100 52.0 52.0 53.63.30 Phytotoxic
FA 1.9 11.8 32.1 a) 6.0 27.1 <30* b) Very phytotoxic
Bulking agents SD 12.25 5.50 0.23 68.0 4.00 4.41 <30* b) Very phytotoxic
RH 10.61 6.75 0.87 57.5 98.0 76.4 74.9 74.43.92 Moderately
phytotoxic
WS 13.56 6.82 1.08 51.6 78.0 5.55 <30* b) Very phytotoxic
*Experimental values with low significance; a)- not quantified; b)not determined due to low significance of data.
For the other materials tested, CM, FA, WS and SD, GI values are reported as <30%, due to the
low number of germinated seeds and reduced root growth. The calculation of the GI of these
samples has limited significance and it can somehow be considered that the GI of these samples is
lower than the "limit of quantification" of the used method. Nevertheless, it can be concluded that
these materials originated extracts very phytotoxic to plants. Assessment of phytotoxicity by the
method of germination of seeds has the advantage of responding to a large number of possible
causes. However, the major disadvantage associated is the fact that it is not possible to identify the
specific causes. Indeed, phytotoxicity can result from many factors, including the presence of
substances toxic to plants, such as heavy metals or ammonium ions, fatty acids, low molecular
weight or the excessive accumulation of salts. In general, GI increases with decrease in
concentrations of NH4+-N, soluble salts and water-extractable Cu and Zn [3, 6, 8].
Thus, for example, the results obtained in the CM analysis may be related to these factors, since
the EC measured was high (10.5 mS/cm) and on the other hand, it is likely that manure may
contain high concentrations ammonium ions, since it contains urine of poultry. The result of GI in fly
ash (FA) may be a consequence of high pH (11.8) in the extract, high concentrations of heavy
metals (results not shown here) and the extremely high value of EC (32.1 mS/cm). The bulking
agents, WS and SD, also showed a high phytotoxicity, and these results were somewhat surprising
in scope of our study and not well understood so far.
Phytotoxicity assessment during composting processes

In order to monitoring phytotoxicity during these processes, the samples taken over time were used
to obtain aqueous extracts for germinating Lepidium sativum, following the methodology described.
It is noteworthy that, both in the assessment of phytotoxicity of the individual materials and during
processes with SD, five replicates were always used. In the case of processes with RH, the
number of replicates was reduced to 3, because the result of ANOVA showed that in general, the
five replicates of the control were statistically very similar (p>0.05).
The GI values determined over time in eight composting processes and its associated mean
standard errors were represented in Fig.1a-b). The evolution of GI in the processes with sawdust
(SD), Fig. 1a), revealed that germination of seeds in the initial mixtures was practically absent. This
was somewhat expected, given that SD and PP also revealed very low GI. The GI values of RSD,1,
RSD,2 and RSD,3 composts, remained very low until 18th day. The reason of these values can be
attributed to the formation of phytotoxic substances during the active phase of composting, such as
ammonium ions, fatty acids and low molecular weight phenolic acids [7-8]. On the other hand, high
values of EC were measured in the extracts of samples from 11 and 18 days (10-12 mS / cm),
which may also have contributed to these values. In RSD,4 experiment, GI exhibited a more
favorable profile, once in 11th day, GI reached 50.10%. After 46 days, the RSD,1, RSD,2 and RSD,3
showed GI below 30%, indicating that the compounds were still very phytotoxic. At this time, RSD,4
was characterized by values above 60%.
569
a) b)
Figure 1 GI profiles during composting processes with a) sawdust (RSD,1 RSD,4) and (b) rice husk (RRH,1 RRH,4).
In summary, it can be concluded that the GI values obtained for RSD,4 process stand out positively
in relation to the other experiments analyzed. Once the operating conditions were identical in all
four processes and occurred simultaneously, the differences in phytotoxicity may be related to the
proportions of the initial mixtures. Thus, the highest proportion of SD (14%) in the mixture RSD,4 led
also to the highest percentage of free air space (FAS) in the initial mixture, which facilitated the
diffusion/convection of air and thus, favoring aerobic metabolism with good efficiency for
decomposing phytotoxic substances produced during composting.
The GI profiles along with the process of composting with rice husk (RH) are shown in Fig. 1b),
where it can be seen that RRH,1 and RRH,3 follow similar trends and RRH,2 and RRH,4 as well. The
ANOVA results reinforces this idea, since by comparing the GI between extracts of different
composts in the course of composting processes, the results showed that the compounds RRH,1 and
RRH,3 should be considered equal in 0, 4, 11 and 39th day (p> 0.05) and the RRH,2 and RRH,4
th
composts on 4, 18, 25 and 39 day (p> 0.05). Globally, after an increase in GI values over time
th
until the 4 day, all processes tend to decrease GI values. Once again, this decrease can be
attributed to the formation of phytotoxic substances during the most active phase of composting. In
the last determination on RRH,2 and RRH,4 composts, at 39th day, revealed average GI values of 48.7
% and 36.5%, respectively, that are statistically equal (p=0,0786), and indicates that they are
phytotoxic and immature. In the case of RRH,1 and RRH,3, final GI of 67.1 % and 72.2 % were
observed, respectively, that are also statistically equal (p=0,403), and thus both moderately
phytotoxic, but also immature (GI<80%) [3]. For the same reasons indicated for processes with SD,
one may refer the initial compositions are determinant for phytotoxicity behavior. In fact, it should
be noted that the mixtures with lower GI are the ones with lower proportion of bulking agent RH in
its composition (approximately 17%), and the best results were obtained for the experiment with
the highest quantity of RH (25.9%).
Phytotoxicity assessment of composts in maturation stage

th
By analyzing the GI obtained for composts at 65 and 111 day of their maturation stage, Fig. 2
th
shows that with exception of compost C1 at 65 day, all measurement are higher than 60%, which
correspond to consider moderate phytotoxicity. In fact, compost C1 reveals a significant increase in
GI from 53,8 % to 82,5%, which means that 65 days were not enough to reach a high degree of
maturity. It should be noted that according to literature, the classification of non-phytotoxic and
matured requires a GI higher than 80 % [2-3]. In GI for composts C2 and C3 should be similar
considered statistically similar, since according to the ANOVA p value is equal to 0,47. Thus, for
both of the composts, 65 days could already be considered free of phytotoxins and matured.
Regarding the effects of bulking agent, sawdust in C1 and wheat straw in C2 and C3, it can be
noted that the use of SD leads to a slower composting process at the level of maturation. However,
at 111th day, composts C1-C3 have statistically equals GI (p= 0,270), and thus, similar levels of
phytotoxicity.
570
C1 C1 C2 C2 C3 C3
Figure 2 Germination index (GI) evaluated at 65 and 111th day for composts C1, C2 and C3 in maturation stage.
CONCLUSIONS
The assessment of phytotoxicity in aqueous extracts, based on germination index by using
Lepidium sativum, was performed in this study for three different contexts (raw materials,
throughout composting and in maturation phase composts). In all cases, the lumped parameter GI
revealed to be easy to calculated, rapid and statistically very significant. The results of germination
tests on materials potentially recyclable through composting showed that some of these had no
phytotoxicity, as for example, GC and SS. However, extracts from CM, FA, WS and SD proved to
be very phytotoxic without composting processing. These results are a consequence of several
factors, such as acidic or basic pH, high EC, presence of heavy metals, ammonium ions and low
molecular weight acids. The eight laboratory-scale processes followed in this study, where
composting of potato peels and grass clipping was promoted, allowed to conclude that the bulking
agent used may have a very significant effect on GI. The lowest levels of phytotoxicity
corresponded at processes with a higher proportion of bulking agent in their initial blends. In
general, higher GI was obtained in processes with rice husk than with sawdust. In the case of
composts in maturation stage, the results showed that after 65 days, the materials with wheat straw
were already matured, unlike the composts with sawdust still be considered moderately phytotoxic.
After 111 days, all composts had similar levels of phytotoxicity and could be considered mature.
References
[1] Haug, R.T., The Practical Handbook of Compost Engineering. Lewis Publishers, Boca Raton,
FL, USA, 1993.
[2] S. Tiquia, Reduction of compost phytotoxicity during the process of decomposition,
Chemocphere. 79 (2010), 506-512.
[3] M. Gao, F. Liang, A. Yu, B. Li, L. Yang, Evaluation of stability and maturity during forced-
aeration composting of chicken manure and sawdust at different C/N ratios, Chemosphere. 78
(2010),614-619.
[4] D. Cabaas-Vargas, D. Snchez-Monedero, S. Urpilainen, A. Kamilaki, E. Stentiford,
Assessing the stability and maturity of compost at large-scale plants, Ingeniera. 9 (2005), 25-
30.
[5] P. Helfrich, B. Chefetz, Y. Hadar, Y. Chen, H. Schnabl, A novel method for determining
phytotoxicity in compost, compost science & utilization. 6 (1998), 6-13.
[6] S. Tiquia, N. Tam, I. Hodgkiss, Effects of composting on phytotoxicity of spent pig-manure
sawdust litter, Environmental Pollution. 93 (1996), 249-256.
[7] M. Fang, J. Wong., Effects of lime amendment on availability of heavy metals and maturation
in sewage sludge composting, Environmental Pollution. 106 (1999), 83-89.
[8] M. M. Delgado, J. M. Imperial, C. Len-Cfreces, M. C. Garca, Phytotoxicity of uncomposted
and composted poultry manure, African Journal of plant science. 4 (2010), 154-162.
[9] M. Gmez-Brandn, C. Lazcano, J. Domnguez, J.,The evaluation of stability and maturity
during the composting of cattle manure, Chemosphere. 70 (2008), 436-444.
571
14th September
Session 3.2
( LANDFILL )
Chairman: Rosrio Oliveira
572
St
PMPHMTP: A 3D PARALLEL SOFTWARE FOR ASSESSMENT OF MUNICIPAL WASTE

LANDFILL
1 1 1 1 1 1
Pereira, B. A. , Forster, A. A. , Valado, I. P. , Ferreira, I. L. , Silva, A.J. and Castro, J. A.
1 - Federal Fluminense University Post Graduate Program on Metallurgical Engineering,
Av. Dos Trabalhadores, 420, Vila Santa Cecilia Volta Redonda RJ- Brazil, CEP: 27255-
125 Phone: +55 24 3344 3011 brunoap@metal.eeimvr.uf.br.
ABSTRACT
The urban solid waste management system has the landfill as an economical solution for the
urban waste final destination. In order to assess the environment impact into the landfill
region, it has became common the use of mathematical model for estimating the leachate
generation, gas, reaction rates, organic matter decomposition and water balance in the
landfills. This work describes a 3D parallel open code software developed in FORTRAN
90/95 language to simulate the soil contamination in municipal landfills taking in to account
the climate and landfill operational conditions. The program is able to simulate a set of
chemical species of the leachate ions considering the kinetics of mass transfer to the soil
and vice versa. The model formulation is based on transport equations for momentum and
chemical species that are solved numerically by the finite volume method and ADI solver.
The code is available in a parallel version to run on a cluster of computers, in order to attend
the demand for large amount of memory allocation and the need of fast processing. The
code has been validated for controlled experimental conditions on laboratory scale and
successfully applied to large scale simulations of landfills area
Keywords: Landfill; Waste; Mathematical model; Computational simulation.
INTRODUCTION
Studies and solutions for final treatment of solid waste indicates the landfill as one of the techniques
for management solid waste. The reason for large utilization of landfill in all parts of the world is due to
economics [1]. This way of treatment is recommended for solid wastes unrecyclable and the wastes
provided by incineration process. However is common to have information of depots of several kind of
waste in areas without any treatment technique, where the environmental impact in a long term of
these depots in the soil, underground and groundwater must be estimated [2]. The studies to
preventions and control of these areas are realized by search activities that always are investigating
new problems caused in the environmental as well as solutions of treatment for the municipal solid
wastes. The penetration of rain water in the landfill is a problem of point of view of the percolation,
since increases the leachate generation and in this way causing contamination in the soil below of the
surface and in groundwater, where then soil waterproofing ways has been used as barriers for the
contamination advance plume [3-5]. For other hand the infiltration of rainwater contribute to the
leachate stabilization [1,6]. However, a long period of dry can causing a moisture great evaporation
conducting to a delay in the organic matter biodegradation even in greats depths of the landfill [7]. As
instrument of support to the studies and evaluation of the environmental impact of the soil
contamination due to solid wastes decomposition and leachate percolation in the landfill, it has been
observed the application of mathematical models capable to estimate the leachate and gas
generation, reaction kinetics, organic matter decomposition and balance of water in landfill, among
others, in a long period [8-10]. In this context, this paper presents a parallel hybrid multi-domain
computational code (MPI-OpenMP) capable to simulate the real conditions of operation in landfills
areas. The code was constructed to run in a parallel computing environment, where each node or core
of computing executes the calculation only in one part (subdomain) of total physical domain. So, the
final solution of problem will be the joining of each physical subdomain.
573
METHODOLOGY
Mathematical model
This model considers the equations of momentum, continuity and species, Eq. (1-3):
( ) ( ) ( ) (1)
( ) ( ) (2)
( ) ( ) ( ) (3)
where is the porosity, is the density, represents the phase velocity, is the viscosity, is the
pressure, is the mass fraction of each phase component, is the diffusion coefficient and the is
the transfer of mass of the solid phase to the liquid phase and contrariwise. The index , and
represents each species, phase and direction respectively.
The term means the resistance that the solid particle offers to the fluid flow by the drag force per
volume unit and is determined through of the modified Kozeny-Carman equation [14]:
| |( )( ) (4)
where is liquid phase velocity, is solid phase velocity and is the drag coefficient and is the
hydraulic radius that are defined as:
(5)
| |
(6)
where is the viscosity in the liquid phase, is the density in the liquid phase, represents liquid
phase volumetric fraction, is the shape factor of the soil particle is the soil particle medium
diameter, and S is the particles volumetric fraction in the solid phase, that is defined as:
(7)
When the coefficient has the same value of porosity the medium porous is saturated. For a
porous medium that is not saturated has a value between to zero.
This model treats the source term associated to the kinetic of mass transfer of the species in function
of time as can be viewed in Eq. 8.
(8)
where represents the sorption rate of the chemical species by the liquid phase and represents
the sorption rate of the chemical species by the solid phase. So the source term equation can be
described in the fowling way:
[ ][ ] (9)
where is the kinetics constant, is the equation order, is the chemical specie concentration in
the liquid and solid phase and is the equilibrium concentration in the liquid and solid phase.
Some parameters is necessary to determine the equation that describe the mass transfer rate of
contaminant to the soil and contrariwise. The contact area of the solid and liquid phase is
calculated according [11], Eq. 10.
574
(10)
where s is the volumetric fraction of the solid phase, is the medium diameter of the soil particles
and is the shape factor of the soil particle.
The mass coefficient transfer, , was determined in function of the Sherwood number, , effective
diffusion coefficient of the species in the liquid phase, (LERMAN, 1979), and the medium diameter
of the soil particle, , conform presented in Eq. 11.
(11)
The Sherwood number represents the dimension of the concentration gradient in the surface [13] and
it is determined according Eq. 12.
( ) ( ) (12)
where is the modified Reynolds number and is Schmidt number.

The Reynolds number is the ratio between the inertia force and the fluid viscous force. Schmidt
number is the ratio among the diffusivity of momentum and the diffusivity of mass [13]. These two
terms are given in the Eq. (13 14) respectively.
| |
(13)
(14)
where is the chemical species velocity in the liquid phase and is the chemical species velocity in
the soil interstitial liquid.
Numerical Solution
Momentum, mass, and species equations were discretizated by using the Finite Volume Method
(FVM), Eq. 15, applied for general coordinates system [15], where the integration is done over a
control volume. The final product of this operation is a set of algebraic equations summarized in Eq.
16. Coefficients are obtained by the power law scheme, according Patankar [16].
( ) ( ) ( ) (15)
(16)
Liquid and solid motion was obtained by applying the SIMPLE algorithm where velocity components
and pressure are iteratively determined. The numerical solution of the set of algebraic equations
demands large computational effort. A line-by-line solver based on the tri-diagonal matrix algorithm
(TDMA) was used to solve the system of algebraic equations. The ADI (Alternate Direction Implicit)
iterative procedure was applied within a common solver for all equations.
Modeling parameters
The program was validated with experimental data obtained in a column experimental test. The
experiment utilized soil and leachate of the landfill to represent its operational conditions, where in this
case the leachate is discharged into the column top with a soil layer immediately below. The
computational model considers two phases, liquid and solid, being the last considered a saturated
medium. The boundary conditions are set as inlet of leachate in the top of domain and outlet of
leachate at the bottom and extremities of the domain. Parameters such as quantity of ions simulated,
ions concentration in the liquid and solid phase, soil porosity, amount of wastes deposited, topography
of landfill, rainfall index and simulation time can be set up. The computational mesh was constructed
575
with more than 7 million of control volume, where each one has a thickness of 5 cm, covering a
2
physical domain area of approximately 350.000m .
Hybrid parallel multi-domain technique MPI/OpenMP

The hybrid scheme joins both parallel technique (MPI-message passing) and (OpenMPshared
memory) to take advantages of the parallel computing and consequently achieve better computational
performance. This process takes into account the methodology adopted in the MPI multi-domain
parallel technique where the computational load is distributed equally among the nodes or cores of
computation. However, this code considers two levels of parallelism, where the MPI is used to create
a process group in which designates one process to each subdomains and also establishes the
coupling between them by message passing. The OpenMP is used inside of each subdomain to exert
shared memory parallelism which uses computing cores of a node to execute processing threads.
RESULTS
This software is a 3D open source code that is capable of simulating the operational real conditions of
municipal landfill areas. Investigative results for contamination plume extension inside and around of
the landfill areas can be predicted in the liquid and solid phases. In the Fig. 1 and Fig. 2 are shown
examples of predictions of the software that represents the landfill surface and the ion contamination
in the liquid and solid phase, as well the growth of waste stack in the discharge area of it, the
transversal and longitudinal viewed of the landfill interior which indicate the percolation and
concentration of the ion and the concentration in function of the depth in the middle of the domain. The
Fig. 1 demonstrates an investigating of an ion concentration after one year and Fig. 2 after fifty years.
Figure 1 Computational simulation for 1 year of contamination: a) The landfill surface and the ion
contamination. b) The transversal and longitudinal viewed of the landfill interior. c) The concentration
in function of the depth in the middle of the domain.
However to attend the need for represent a physical domain of a municipal landfill and the operational
conditional of it, a great memory amount is requested and consequently the demand for computational
performance is imperative. In face of this case, some numerical techniques were employed to treat
this situation, such as the multi-domain parallel technique and the hybrid parallelism MPI/OpenMP.
576
Figure 2 Computational results for 50 years of contamination: a) The landfill surface and the ion
contamination. b) The transversal and longitudinal viewed of the landfill interior. c) The concentration
in function of the depth in the middle of the domain.
The result has shown that the computational simulation can be exerted fast and in this way answering
the wishes of scientific community. The Fig.3 shows the computational gain (speed up) of the code
when increases the number of CPU in the calculating process. As can observed the code presents a
computational progressive gain, where until a certain number of CPU some factors of performance
limitations has not been perceived, as the time spent in the communication process and the imperfect
load balancing in the subdomains.
Fig.3 Computational gain of the code
577
CONCLUSION
This paper presents a parallel 3D open software constructed in FORTRAN 90/95 language able to
simulate the contaminant transport in the liquid and solid phases in municipal landfill areas as well its
operational condition. The computational code was validated with experimental data where it was
adjusted to a column experiment. The code has been used to simulate the ions contamination in the
liquid and solid phase as well as the extension of this contamination plume. To solve the problem of
high requisition of memory due to the representation of the real physical domain and consequently the
demand for computational performance, this software uses the multi-domain simulation technique and
computing techniques such as hybrid parallelism MPI/OpenMP. Where, the code computational
performance has been a strong attractive for this kind of simulation.
REFERENCES
[1] A. A. Tatsi, and A. I. Zouboulis, A field investigation of the quantity and quality of leachate from a
municipal solid waste landfill in a Mediterranean climate, Advance in Environmental Research,
6, (2002) 207- 209.
[2] S. L., Machado, M., Karimpour-Fard, N. Shariatmadari, M. F. Carvalho, and J. C. F. do
Nascimento, Evaluation of the geotechnical properties of MSW in two Brazilian landfills, Waste
Management, 30, (2010), 25792591.
[3] A. S., Francisco, Pereira, B. A. and, J. A. Castro, 3D-Parallel Simulation of Contaminant in
Waste Disposals, Computer Technology and application, 2, (2011), 213-218.
[4] R. P. Kumar and G. R. Dodagoudar, Modeling of contaminant transport through landfill liners
using EFGM, International Journal for Numerical Analytics Methods in Geomechanics, 34,
(2010), 661688.
[5] S. A. Mirbagheri, S. A. Hashemi Monfared and H. R. Kazemi, Simulation modeling of pollutant
transport from leachate in Shiraz landfill, Environment Earth Science, 59 (2009), 287296.
[6] L. Di Palma, and R. Mecozzi, Batch and column tests of metal mobilization in soil impacted by
landfill leachate, Waste Management, 30, (2010), 15941599.
[7] J. Trnker, D. Manandhar, Q. Xiaoning, V. Sivapornpun, and W. Schll, Proceedings Sardinia,
Eighth International Waste management and Landfill Symposium, Pula, Cagliari, Italy, 2, (2001),
59-68.
[8] G. J. Farquhar, Leachate: production and characterization, Canadian Journal of Civil
Engineering, 16, (1989) 317 325.
[9] P. R. Schroeder, N. M. Aziz, C. M. Lloyd, and P. A. Zappi, The Hydrologic Evaluation of Landfill
Performance (HELP) Model: Users Guide for Version 3," EPA/600/R-94/168a, U.S.
Environmental Protection Agency Office of Research and Development, Washington, DC, (
1994).
[10] J. Fellner, and P. H. Brunner, Modeling of leachate generation from MSW landfills by a 2-
dimensional 2-domain approach, Waste Management, 30, (2010), 20842095.
[11] Yagi, J.I. Mathematical Modeling of the Flow of Four Fluids in a Packed Bed. ISIJ International,
33 (6), (1993), 619 639.
[12] A. Lerman, Geochemical process. Water and sediment environments. New York: John Wiley &
Sons, 481 p. 1979.
[13] F. P. Incropera and D. P. Witt, Fundamentals of heat and mass transfer, 4th ed., J. Wiley, New
York, 1990.
[14] J. A. Castro, A Multi-Dimensional Transient Mathematical Model of Blast Furnace Based on
Multi-Fluid Model, Ph.D. Thesis, Institute for Advanced Materials Processing, Tohoku University,
Japan. 2000.
[15] M.C. Melaaen, Calculation of Fluid Flows with Staggered and Nonstaggered Curvilinear
Nonorthogonal Grids- The Theory, Numerical Heat Transfer - Part B, 21, (1992), 1-19.
[16] S. V. Patankar, Numerical Heat Transfer and Fluid Flow, Washington, Hemisphere Publishing
Company, 197p. 1985.
[17] Rabenseifner, R., Hager, G. and Jost, G., Hybrid MPI/OpenMP Parallel Programming on
Clusters of Multi-Core SMP Nodes Parallel, Distributed and Network-based Processing, IEEE
Computer Society, (2009) 427 436.
[18] Tang, G., DAzevedo, E. F., Zhang, F., Parker, J. C., Watson, D. B. e Jardine, P., Application
of a hybrid MPI/OpenMP approach for parallel groundwater model calibration using multi-core
computers, Computers & Geosciences, 36, (2010), 14511460.
578
STUDIES ON THE IMPROVEMENT OF TREATMENT OF URBAN LANDFILL

LEACHATES BY FENTON-LIKE PROCESS USING ZVI
1 2 2 1 2
D.V. Lopes , R.C. Martins , M.J. Quina , J.C. Gis and R.M. Quinta-Ferreira
1 Department of Mechanical Engineering, Faculty of Sciences and Technology, University of
Coimbra, Rua Lus Reis Santos, 3030-790 Coimbra, Portugal
2 CIEPQPF- Research Centre on Chemical Processes Engineering and Forest Products,
Department of Chemical Engineering, Faculty of Sciences and Technology, University of Coimbra,
Rua Slvio Lima, 3030-790 Coimbra, Portugal (martins@eq.uc.pt; guida@eq.uc.pt;
rosaqf@eq.uc.pt)
ABSTRACT
The aim of the present study was to analyze the applicability of Fenton-like zero valent
iron (ZVI) process on the remediation of several landfill leachate samples coming from
different points of an existing treatment plant (ERaw, EPost-Bio and ETreat). The effects of pH
0
and Fe concentration were determined for ERaw and ETreat. It was observed that the use of
low pH values enhances the treatment efficiency. Moreover, the increase on iron load
leads to higher COD removals until a certain point after which the catalyst starts to show
radical scavenger effect. The low efficiency attained for ERaw (COD removal always below
8%) indicates that this methodology is not suitable for this effluent. However, final ETreat
within the legal limits for discharge were attained when pH=2 was used. The utilization of
iron shavings as catalyst in Fenton-like process showed to be a suitable and economical
solution on the remediation of ETreat and EPost-Bio with high COD abatements leading to
streams able to be released to the municipal sewage. According to our results, it seems
advisable to implement this technology after the existing bio-reactor substituting, this way,
the already existing physico-chemical treatment.
Keywords: Fenton-like process; ZVI; Landfill leachate; Processes integration; Environmental

protection.
INTRODUCTION
Concern regarding environmental protection has been growing over the past years due to the
increase on ecological awareness leading to stricter legislation establishing that economical growth
must consider the natural resources sustainability.
In Portugal, it is currently in force the second strategic plan for the management of MSW -
municipal solid wastes (known as PERSU II) which reinforces the definition of a waste
management hierarchy. Thus, the possibility of minimize waste production should be first
addressed, followed by the separation, reuse and recycling of materials with the main aim of
diminishing the amount of waste disposed into landfills. However, data collected in 2009 pointed
out that Portugal is generating higher loads of landfilled waste than the established limits imposed
by PERSU II.
One of the major environmental concerns associated with the disposal of MSW in landfills is related
with the large amount of leachates generated due rainwater percolation through wastes,
biochemical decomposition of the deposited materials and their inherent water [1]. These high-
strength wastewaters show a complex composition depending upon the kind of MSW disposed in
the cells, the landfill age and climatic conditions as well. In this context, the presence of toxic
and/or bio-refractory compounds allied with the high variability on the flow and type of pollutants to
be treated reduces the efficiency of the traditional activated sludge reactors. However, the social
and political concerns regarding the depletion of fresh water resources are leading to stringent
579
wastewater discharge regulations and standards worldwide imposing, this way, the development of
suitable technologies able to minimize the environmental impact of polluted streams.
2+
In the last years, Fentons process (Fe + H2O2) has arisen as an industrially interesting alternative
operating at room conditions of pressure and temperature besides involving easy to handle
reactants. This system promotes the formation of the highly reactive hydroxyl radicals, according to
Eq. 1, able to oxidize a wide range of compounds.
Fe 2+ + H 2O2 Fe3+ + HO + HO (1)
The main disadvantage associated to this technology is related with the high amount of ferrous
iron required which, at the end of the process, has to be separated from the treated effluent
(generally by precipitation) leading to considerable loads of iron containing sludge that will entail
further management [2]. Bremmer et al. [3], developed an alternative Fenton system involving the
0 2+
oxidation of iron metal sheets (Fe ) at acidic conditions generating in situ Fe (Eq. 2) in the
presence of hydrogen peroxide.
Fe0 + 2 H + Fe2 + + H 2 (2)
The main advantage of this procedure is related with the minimization of the operating costs when
compared with the use of iron salts. Moreover, a faster recycling of ferric iron at the metal sheet
surface (Eq. 3) is reported [3].
2 Fe3+ + Fe 3Fe 2+ (3)
This Fenton-like ZVI process has been applied, in the last decades, on the remediation of several
wastewaters such as olive mill effluents [2]. However, literature is scarce in what regards its
efficiency on the abatement of the pollutant character of landfill leachates. In this context, the aim
of the present paper is to test the applicability of such technology on the depuration of lechates
coming from a landfill in Portugal as a complementary process on the existing treatment plant.
Effluents Sampling
Some samples of leachate were collected in an industrial treatment plant exclusively devoted to
this wastewater generated in an urban landfill. Samples were withdrawn from three different points
as illustrated in Fig. 1, before and after the activated sludge treatment (ERaw and EPost-Bio,
respectively) and at the end of the depuration process, just before its discharge throughout the
municipal sewage (ETreat). It was our goal to analyse where the Fenton-like ZVI process would be
more suitable to be implemented.
Fig. 1. Simplified flow sheet of the landfill leachates treatment plant under study.
Oxidation Procedure
Fenton-like ZVI process was generally carried out in dark glass bottles, and in our study 40 mL of
effluent were introduced in the reactors and agitated in an orbital shaker (Heidolph Reax 20
shaker at 16 rpm). Hydrogen peroxide (industrial grade, 50 % w/w) and iron powder (-325 mesh, 97
580
%, Aldrich) were added in some experiments. When the applicability of iron shavings (obtained
from a metal turner) as catalyst in this process was studied, a reactor with 1 L (500 mL of landfill
leachate) was used. Samples were periodically withdrawn and the reaction was stopped by raising
pH to 12.
Analytical Techniques
Chemical Oxygen Demand (COD), Biochemical Oxygen Demand (BOD5), Total Suspended Solids
(TSS) and Total Dissolved Solids (TDS) were determined according to the Standard Methods [4].
pH and Oxidation Reduction Potential (ORP) were measured by CRISON micro pH 2002. Total
Phenolic Content (TPh) was quantified by Folin-Ciocalteau method while Mohr procedure was
applied for chlorides determination. The concentration of iron in the leachates composition was
determined by Atomic Absorption Spectrophometry (FAAS PerkinElmer 3000).
Characterization of Effluents
Table 1 shows the physico-chemical characterization of the collected samples and the legal limits
for discharge (LLD) throughout the local municipal sewage for each parameter.
Table 1- Physico-chemical characterization of leachate samples.
Parameter ERaw EPost-Bio ETreat LLD

pH 8.0 7.0 6.9 5.5 9.5
Redox Potential (mV) -154 120 212 *
COD (mg O2/L) 204715 154020 15736 1000
BOD5 (mg O2/L) 1253193 6558 184 800
BOD5/COD 0.61 0.042 0.011 *
Chloride (mg/L) 2049191 232620 3106120 750
Iron (mg/L) 280.1 13.80.1 850.1 20
TSS (mg/L) 20042 500168 15014 1000
TDS (mg/L) 8040424 515012 796057 *
TPh (mg GAeq/L) 2913 1065 1427 *
The results depicted in Table 1 reveal that the raw effluent presents a high load of organics with
COD and BOD5 values of 2047 mgO2/L and 1253 mgO2/L, respectively. Even if the initial
wastewater show to be biodegradable (BOD5/COD = 0.61), the stream attained after the activated
sludge reactor (EPost-Bio) still do not fulfil the legal requirements for discharge into the local municipal
sewage in what regards COD (1540 mgO2/L). The chemical post-treatment implemented
afterwards (consisting in the addition of FeCl3, H2SO4 followed by lime) is not sufficient to refine the
wastewater until the legal limits. Moreover, the biodegradability is now so low (BOD5/COD = 0.011)
that is not recommendable the application of a subsequent biological depuration. Within these
results, the applicability of Fenton-like ZVI process on the depuration of this cumbersome effluent
was tested. Moreover, in order to indentify the most suitable integration between this technology
and the already implemented processes, ERaw, EPost-Bio and ETret were studied.
Fenton-Like ZVI Process: Effect of pH

pH is a key parameter in Fenton-like processes, and thus, its impact over the depuration of ERaw
and ETreat was analysed within the range between 2 9 using 125 g/L of iron powder and 3.35 g/L
of H2O2. COD removal after 120 min is depicted for both effluents in Fig. 2a). As it can be
observed, this process reveals a negligible impact over ERaw COD removal since the higher
abatement attained was below 8 % for pH 4 and this value was kept almost unchanged for the
range of pH applied. Contrarily, this technology seems to be highly relevant if applied to ETreat with
581
COD degradation reaching 40% for pH 2. A decreased efficiency is attained when pH raises, which
is related with the diminution on HO radicals due to the formation of ferric-hydroxo complexes [2].
Moreover, hydrogen peroxide self-decomposition into oxygen and water is promoted at alkaline
conditions leading to lower amounts of oxidant available for the organics oxidation.
According to Fig. 2b), one can conclude that, while the legal limits for direct disposal into the local
municipal sewage are never reached for ERaw, an effluent suitable for discharge is attained when
ETreat is depurated by this oxidation system at pH 2.
100
ERaw
ERaw 3000 ETreat
80 a) ETreat b) Legal Limit
COD Removal (%)
COD (mg O2/L)

60 2000
40
1000
20
0 0
0 2 4 6 8 10 0 2 4 6 8 10
pH pH
Fig. 2. Effect of pH in ERaw and ETreat remediation by Fenton-like ZVI process. a) COD removal (%);
b) COD and the legal limit for discharge throughout the local municipal sewage (mg O2/L).
Fenton-Like ZVI Process: Effect of ZVI concentration

0
Effect of Fe concentration on the Fenton-process ZVI for the depuration of ERaw and ETreat was
tested within the range of 12.5 125 g/L of iron powder. In these experiments, 3.35 g/L of
hydrogen peroxide were applied and pH = 4 and pH = 2 were used for the raw and treated effluent,
respectively. According to Fig. 3, the increase on the iron load enhances to some extent the
0
process efficiency for both wastewaters. In fact, for ERaw when Fe concentration rose from 12.5 g/L
to 62.5 g/L, COD abatement was enhanced from 4.9% to 8.6%. However, the further increase on
the catalyst concentration slightly diminished the process performance. Indeed, it is reported that
the presence of an excessive iron concentration leads to a radical scavenger effect, reducing thus,
the amount of HO available to the effluents remediation. A similar behaviour was found out for
ETreat with COD removal increasing from 35.2% to 41% for iron amounts of 12.5 g/L and 25 g/L,
respectively. A slight efficiency decrease is observed when higher catalyst loads were applied.
100
ERaw COD ER
3000 COD ET
80 a) ETreat b) COD Legal Limit
COD Removal (%)
COD (mg O2/L)
60
2000
40
1000
20
0 0
0 20 40 60 80 100 120 140 0 20 40 60 80 100 120 140
Fe0 (g/L)
Fe0 (g/L)
0
Fig. 3. Effect of concentration of Fe in ERaw and ETreat degradation by Fenton-like ZVI process. a)
COD removal (%); b) COD and its legal limit of discharge throughout the local municipal sewage
(mg O2/L).
Fig. 3b) reveals that Fenton-like ZVI is able to lead to an ETreat within the legal limits for discharge
towards the local municipal sewage meaning that this process is quite interesting to refine the
stream coming from the existing treatment plant.
It is clear from these results that ERaw is not suitable to be depurated with this technology.
Therefore, further studies were performed using ETreat and also EPost-Bio, in order to verify if it is
582
possible to substitute the existing physico-chemical process by this new methodology. Moreover,
since iron powder is an expensive reagent, the following tests aimed, also, to analyse its
substitution by iron shavings. The application of this material would greatly diminish the process
operating costs since it constitutes a waste from iron processing industry that could be, therefore,
reused.
Fenton-Like ZVI Process: Application of Iron Shavings

Fig. 4a) shows COD removal for ETreat and EPost-Bio by Fenton-like ZVI process using 25 g/L of iron
shavings, 13.40 g/L of hydrogen peroxide and pH = 2. As it can be observed, COD abatement is
very fast on the first 5 min of reaction, followed by a plateau were degradation is very slight. ETreat
(2) corresponds to a duplicate experiment involving ETreat to evaluate the results reproducibility, and
in fact, both profiles are almost perfectly matched. A higher removal is observed for EPost-Bio with
48% of COD abated after 120 min of reaction, while 38% was the maximum degradation attained
for ETreat. Indeed, according to Fig. 4b), with the application of this treatment methodology, EPost-Bio
quickly met the COD and BOD5 legal limits to be disposed towards the municipal sewage.
100
COD ETreat
ETreat
3000 COD ETreat (2)
80 a) ETreat (2) COD and BOD5 (mg O2/L) b) COD EPost-Bio
EPost-Bio
BOD5 ETreat
COD Removal (%)
BOD5 ETreat (2)

60 2000 BOD5 EPost-Bio
COD Legal Limit
BOD5 Legal Limit
40
1000
20
0 0
0 10 20 30 40 50 60 70 0 10 20 30 40 50 60 70
Time (min) Time (min)
Fig. 4. Evolution of a) COD removal (%) and b) COD, BOD5 values during Fentons like process wit
iron shavings treatment of, EPosto-Bio and ETreat.
With these results, it seems that Fenton-Like process using iron shavings can be successfully
implemented after the bio-reactor existent in the leachates treatment plant in order to refine the
effluent before being released into the municipal sewage.
The metal oxidation along the process may reduce the iron shavings efficiency after some
application. Thus, to check their behaviour along reuses, several cycles were performed by adding
fresh EPost-Bio after 60 min of reaction without regenerating the catalyst. Fig. 5a) shows that the iron
shavings roughly maintained their activity during four cycles (COD removal above 60%); however,
its efficiency decreases to about 42.5% afterwards. Even so, according to Fig. 5b), the COD legal
limit for disposal into the sewage is always accomplished. Moreover, the results reproducibility was
patent when the first experiment was repeated (blank point).
100
Iron shavings reuse in cycle Iron shavings reuse in cycle
a) Iron shavings pre-test 3000 b) Iron shaving pre-test
80 COD Legal Limit
COD Removal (%)
COD (mg O2/L)
60
2000
40
1000
20
0 0
0 2 4 6 8 10 12 0 2 4 6 8 10 12
Number of repetitions Number of repetitions
Fig. 5. Evolution a) COD removal (%); b) COD values after 60 min of Fenton-Like reactions for
each cycle of the iron shavings reuse.
583
Hydrogen peroxide concentration was determined after each reuse and the results are shown in
Fig. 6. The H2O2 remain after 60 min increases along the cycles, which means that the iron
shavings are losing their capability of decomposing it into hydroxyl radicals. This is probably due to
the unavoidable loss of iron ions during the cycles, which reduces the amount of catalyst available.
Moreover, the iron shavings surface activity declines due to oxidation. This can be minimized by,
after a certain number of cycles, cleaning the catalyst surface by adding, for example, an acidic
solution.
16000
14000
12000
10000
H2O2 (ppm)
8000
6000
4000
2000
0
0 2 4 6 8 10 12
Number of repetitions
Fig. 6. Concentration of H2O2 in tests samples after each cycle of treatment.
CONCLUSIONS
One of the many environmental problems associated with landfills is the leachate production. Due
to their pollutant characteristics it is important resort to others methodologies of treatment, besides
the biological remediation, which only by itself generally shows to be inefficient.
The main goal of this study was to bring a new approach to treat landfill leachates in a low cost
point of view using Fenton-like process catalysed by ZVI.
From the analysis of the impact of pH it was concluded that acidic conditions where more efficient
regarding COD removal. Moreover, the increase on the iron powder load promoted degradation
until a certain point above which it started to act as radical scavenger minimizing, this way, the
depuration. The low remediation levels achieved for ERaw (COD removal always below 8%) indicate
that this process is not suitable to directly treat the raw effluent. However, the legal limits for
discharge were accomplished when this treatment was applied on ETreat at pH 2 (COD removal up
to 40%).
In order to minimize the treatment costs it was analysed the possibility of substituting iron powder
by iron shavings (waste from iron processing industries) as Fenton-like catalyst in the degradation
of ETreat and EPost-Bio. High COD removal was achieved for both effluents: 38% and 48%,
respectively within 60 min of reaction. Furthermore, in both cases legislation thresholds regarding
sewage disposal is complied. Iron shavings recycling revealed that efficiency decreases after 4
reuses even if COD values within the legal thresholds were attained.
Thus, our results showed that Fenton-like process over iron shavings is a suitable technology to be
implemented after the existing activated sludge reactor to refine the effluent before its disposal
towards the municipal collector.
References
[1] S. Renou, J. G. Givaudan, S. Poulain, F. Dirassousyan, P. Moulin, Landifill leachate
management: Review and opportunity, J. Hazard. Mater. 150 (2008) 468-493.
[2] M. Kallel, C. Belaid, T. Mechichi, M. Ksibi, B. Elleuch, Removal of organic load and phenolic
compounds from olive mill wastewater by Fenton oxidation with zero-valent iron, Chem. Eng.
J. 150 (2009) 391-395.
[3] D. H. Bremner, A. E. Burgess, D. Houllemare, K. Namkung, Phenol degradation using
hydroxyl radicals generated from zero-valent iron and hydrogen peroxide, Appl. Catal. B. 63
(2006) 15-19.
th
[4] Standard Methods for the Examination of Water and Wastewater, APHA, AWWA, WPCF, 18
Ed., Washington DC, 1992.
584
PARTICULARITIES OF GEOTECHNICAL INSTRUMENTATION IN SANITARY

LANDFILLS
1 2
C. Gomes and M.L. Lopes
1
COBA, S.A., R. 5 de Outubro, 323, 1649-011 Lisboa and Faculty of Engineering of Lusada
University, ccg.cristinagomes@gmail.com
2
Faculty of Engineering of Porto University, Rua Dr Roberto Frias, 4200-465 Porto, lcosta@fe.up.pt
ABSTRACT
Most monitoring programs implemented in sanitary landfills are based on the principles of
geotechnical instrumentation of earthworks, namely those of earth dams, which have to
be adapted, in particular concerning the selection of equipment and installation methods.
This paper highlights a few of the particularities associated with the instrumentation of
this type of works, with a brief description of the instrumentation plan implemented in two
sanitary landfills in northern Portugal. For each aspect of behaviour that was intended to
monitor, they outline the issues that leading to the selection of the types of equipment
and installation methods implemented and the main difficulties and adjustments
performed during the work .
Keywords: urban solid waste physical, chemical, mechanical and hydraulic properties, landfill
monitoring, instrumentation equipments, installation methods
INTRODUCTION
The geotechnical component of landfills design demands knowledge of urban solid waste physical,
chemical, mechanical and hydraulic properties and of their change during time, as well as, the use
of models representatives of the complex and evolutive behaviour of the deposited waste.
Due to the characteristics of the waste (among others, the high heterogeneity of the composition
and of the size of waste constituents; the variation during time and geographical and the
multiphase character) usually its properties are studied by performing in situ tests, by constructing
experimental landfills or by monitoring existent landfills.
The monitoring of existent landfills is based on the instrumentation principles of earthworks,
specially, earth dams, which need to be adapted, namely in what concerns the selected
equipments and installation methods. On the other hand, the bibliography is scarce and usually is
not clear in what concerns selected equipments, installation methods and difficulties aroused.
Moreover, only equipments available in the market can be selected and those are not specific for
landfills monitoring, namely to support the expected high levels of deformations and the
heterogeneity and environment physical and chemical aggressiveness.
With the objective to enhance some particularities associated to landfill monitoring, this paper
briefly describes the instrumentation plans of Lipor II (Maia) and Sto Tirso landfills putting forward
the main goal of the monitoring and some problems aroused during equipments selection and
installation methods used .
OBJECTIVES OF THE MONITORING OF STO TIRSO AND LIPOR II LANDFILLS
The instrumentation plans implemented in Lipor II and Sto Tirso landfills have, as main objective,
the study of the mechanical behaviour of the landfill, particularly, the stress-strain behaviour and its
correlation with age and decomposition phase of the waste. Generally, the following aspects,
585
during and after deposition phases, were analyzed: waste body displacements; landfill total
displacements (superficial); waste body state of stress, temperature and leachate levels; and
landfill construction story.
In StoTirso landfill the monitoring plan included three areas with waste of different age (Station A,
with recent waste, Station B, with older waste, and Station C, with ancient waste). When
equipments installation started, the deposition of waste in Stations B and C had finished, and it was
just starting in Station A 1]. In Lipor II landfill the monitoring plan included also three areas
(Stations R1, R2 and R3) and, at the beginning of the work, any waste was deposited.
During the deposition phase (1995 to 2005) of the slope landfill of Sto Tirso there was daily
incoming of waste (about 90% pre-treated). The trench landfill of Lipor II is much smaller in size
than Sto Tirso landfill, as it was designed to admit non-treated waste only when the incinerator
plant stopped for maintenance or average (2002 to 2008).
In the areas without waste (Station A of StoTirso landfill and in Lipor II landfill) the following
equipments were installed, side by side, in each waste layer to instrument: 4 total pressure cells, 1
pore pressure cell, 1 open tube piezometer, 1 magnetic plate associated to 1 inclinometer tube,
and, at the top of the layer, superficial marks to control settlements near the piezometer and the
inclinometer. In Stations B and C of Sto Tirso landfill it was installed, from the top of the landfill,
open tube piezometers, inclinometer tubes with magnetic spiders and superficial marks.
SELECTED METHODS AND EQUIPMENTS
Pressure and Temperature Monitoring

In the deposition areas, the state of stress monitoring was achieved by placing, near the top of
some waste layers, total pressure cells (EP in Fig.1) and pore pressure cells (PP in Fig. 1). In order
to measure the two-dimensional state of stress, the total pressure cells of each set were placed
with different orientation (0, 90, 45 and -45).
Fig. 1 Schematic representation of the instrumentation installed simultaneously with MSW landfill.
Concerns related with the uniform distribution of stress on total pressure cells due to the
heterogeneity of the waste and to the presence of elements with different stiffness and size
aroused. On the other hand, the high deformability of the wastes could induce significant deviation
to the cells initial location. To overcome these concerns the bigger size total pressure cells
2
available in the market were selected (vibrant wiring square cells, with 0.4x0.4 m and a reading
2
range from 0 to 700 kN/m ). To control cells levels an internal settlements control system with
magnetic plates located at the same level of the cells was installed. An electric uniaxial
inclinometer, with a reading range of +/- 10 (maximum range available), was coupled to each cell
586
oriented 90 and 45 to control rotation. Vibrant wiring temperature sensors, with a reading range
from -45C to 100, were coupled to all pressure cells.
To control pore pressures two piezometers (one open tube and the other vibrant wiring) were
placed side by side in order to measure the two components of pore pressure (due to leachate and
due to biogas). In fact, the pressures measured in the vibrant wiring piezometer are due to, both,
leachate and biogas and the pressures measured in the open tube piezometer are only due to
leachate, as the biogas would tend to escape through the top of the equipment.
The placement of the referred equipments in waste revealed to be a hard task. The main difficulty
was the preparation of the surface to install the cells, which should be as uniform as possible and
to allow proper installation of total pressure cells with different orientation. Firstly, as recommended
for soils 2], a trench with compacted and leveled bottom was opened, then, using robust metal
patterns, cavities were excavated at the bottom of the trench, spaced about 1.0 m and oriented in
accordance with the location of the cells to install (0, 90, 45 and -45). The patterns were driven in
the waste and then, manually, the waste inside the patterns and surrounding it was removed. This
method was found not feasible due to difficulties in driven the patterns in the waste and to the
change of the anticipated geometry when waste was removed.
After some other trials, it was decided to fill the bottom of the trench with a 1.0 m height compacted
layer of silty sand soils where the cavities demanded to place each cell were excavated. At one
end of the trench were installed, side by side, the two types of piezometers (open tube and vibrant
wiring) as shown in Fig. 1. In this case the installation of the equipments followed the usual
procedures for earthworks. Finally, the equipments were covered with about 0.2 to 0.3 m of soils
and the remaining volume of the trench was filled with waste. When necessary, one more layer of
waste was placed at the top of the trench to achieve 1 to 2 m height of soil and waste materials
above the cells before starting the circulation of the equipments.
From each instrumentation trench another one was excavated to accommodate the cables towards
the data acquisition system. The cables were inserted in corrugated plastic tubes, in order to
prevent their damage. Inside the cells trench the cables were placed loosen enough to avoid
pulling due to landfill deformations. Outside the landfill, until reaching the data acquisition system,
the cables were also protected in order to prevent rodents attack and UV exposure.
The maintenance of the original position of the cells and of the homogeneous surface was
confirmed visually, several months later, when accessing a damaged set of cells.
Open Tube Piezometers

The open tube piezometers were installed inside bore holes (Stations B and C of Sto Tirso landfill)
or directly in the landfill, as it rise, near each set of pressure cells (Lipor II landfill and Station A of
Sto Tirso landfill). The piezometers readings were done using a level water meter and,
simultaneously, a pore pressure cell (vibrant wiring piezometer) with temperature sensor coupled,
in order to check errors in readings and to record temperatures.
Initially, the current method for piezometers installation in soils embankments was used. This is, a
PVC vertical tube ( = 40 mm), with slots in the lower section (L = 0.5 m), wrapped with geotextile
was installed in a sand bed at the depth to collect data (PTA, Fig. 2). At the top of the sand bed,
about 0.2 m of silty sand soils was placed and over it a sealing layer of bentonite (in piezometers
placed in bore holes).
In some of these piezometers the presence of biogas was significant and leads to the impossibility
to define the level of leachate, as the rise of biogas in the piezometer dragged huge quantities of
scum, inducing the closure of the water meter circuit, as soon as the scum reached.
It was decided to change the scheme of piezometer in order to become possible the separation of
gaseous and liquid fractions. The new piezometers, named double or vectorial (PTAV), consists in
the introduction of a piezometer similar to PTA inside a larger PVC tube ( = 90 mm), with a slotted
section at a higher level than that of PTA (Fig. 2).
Leachate and biogas goes in through the slotted section at high level, the biogas rises along the
space between tubes and exits through the top, and meanwhile, the leachate goes in the thinner
tube through the slotted section at lower level. Readings of leachate level were taken in the thinner
tube.
The installation of the piezometers directly in the landfill (Station A) followed similar methodology,
but they were placed inside a cylindrical hole opened at one end of each cells pressure trench.
587
Fig. 2 Open tube piezometers scheme: a) single (PTA); b) double (PTAV).
Inclinometer Tube with Spiders or Magnetic Plates

In all the stations of the two landfills inclinometers were installed to register waste body
displacements. Where waste was deposited the inclinometers and magnetic spiders were installed
in bore holes, in the other case, first the base of the inclinometer tube was fixed, and then, as the
landfill rise, inclinometer tube sections are added and associated magnetic plates are installed.
Some of the main problems linked with the installation of these equipments are: the tube flexibility
to guarantee its integrity under the high total and differential settlements foreseen; the fixing of the
inclinometer base, which cannot move after installation; the huge settlements foreseen, which
implies the use of special telescopic connections or other system compatible with those
settlements; the connection of spiders and plates to the tubes and to the landfill in order to monitor
the real settlements of the landfill; the filling material of the space between tube and the hole lateral
surface, which should have similar stiffness as waste to guarantee the liability of data.
Plastic ABS tubes (ext = 69.85 mm) were used, as they are more flexible, even at high
temperatures, and more chemically resistant than PVC, aluminum and glass fiber. Even so, in
some cases the tubes broken (particularly, those placed at the same time as the waste), usually at
depths corresponding to layers transition. Even in the cases that tubes failure didnt occur, their
deviations relating initial position were significant and irregular along the length and, in some
cases, the cylindrical shape of the tube changes to oval due to the high temperatures of the
surrounding environment. For these, and due to the risk blockade of the reading torpedo, the
monitoring of internal horizontal displacements was disregarded. Inclinometers were only used to
control vertical settlements based on the position of magnetic plates and spiders. When the access
to the based fixed reference was lost, the location of magnetic plates and spiders was defined in
relation to the top of the inclinometer, which demanded its topographical survey at each reading.
The fixing of inclinometers base roused some difficulties, particularly where wastes were deposited.
Different installing methodologies were used (Fig. 3):
Lipor II landfill as the landfill bottom was plane and drainage and liner systems built, a concrete
foot, over the base lining system was constructed, with a HDPE (=200 mm) welded in the
center; the inclinometer was then placed and fixed inside that tube;
areas without waste in Sto Tirso landfill (Station A) as the bottom of the landfill was, in this
area, inclined and the base lining system was built, this system was cut and a hole with about 0.5
m depth was open, inside this hole a HDPE tube (=200 mm) was fixed with bentonite-cement
mortar, then the inclinometer was placed and fixed inside that tube; finally, the base lining system
was rebuilt;
588
areas with waste in Sto Tirso landfill (Stations B and C) the inclinometers were installed in bore
holes that penetrate about 1 m into the foundation; the fixation to the foundation was done by
bentonite-cement grouting; then the section just above, including the base lining system, was
isolated and fixed (by gravity grouting) with a bentonite-cement dense paste.
Fig. 3 Inclinometers base fixation: a) Lipor II; b) Stat. A (Sto Tirso); c) Sta. B e C (Sto Tirso).
At first, the connections between tubes were done using 30.5 cm length junctions (with a minimum
overlapping) and 1.5 m length tubes, in order to increase the capacity of adaptation to the waste
vertical movements. However, this methodology was disregarded, as it was found impossible to
maintain the sequence (tubes, junctions and spiders) properly fitted. Junctions riveting should be
strong enough to support the weight of all sequence, but weak enough to fail easily and allow the
tubes to follow the waste settlements. Friction between junctions and tubes was found too high,
which could imply unreal readings of settlements. To overcome these difficulties, higher length
tubes (L=3 m) with fixed junctions were used. The spiders were installed just below the junctions,
allowing their free sliding along the tube.
The installation of the inclinometers simultaneously with the landfill rise followed similar
methodology. In this case, riveting of junctions was not needed and, instead of spiders, magnetic
plates were used. To protect the plate, have a regular and horizontal surface and a good contact
overall the plate area, a layer of silty sand soils was placed at the base and at the top.
Usually the installation of inclinometer in bore holes demand the filling of the space between tubes
and the hole lateral surface with cement grouting with similar stiffness as the surrounding material
in order to spiders readings are representative. Due to waste high deformability it was considered
inappropriate the use of cement grouting, instead of it a mixture of waste (with bigger size elements
removed) with plastic spheres with small diameter was used. This mixture was introduced in small
589
quantities and compacted with a steel cylinder. This work demands great expertise and the
appropriate control of the spiders positions, to prevent the twisting of waste strips on spiders rods,
the damage or premature opening of the spiders by the steel cylinder. The opening of the magnetic
spiders was done sequentially, when the level of filling reached the position of each spider.
CONCLUDING REMARKS
Several equipments were damaged during or after installation due to:

waste deposition simultaneously with equipments installation, mainly at Lipor II landfill due to its
small size maintenance and deposition works were done very close to the instrumented areas;
high landfill deformations and the non existence in the market of specific monitoring instruments;
environmental physical and chemical aggressiveness and, once more, the non existence in the
market of specific monitoring instruments;
external causes, as rodents attack and thunderstorms;
lack of experience, in this particular type of works, of technical teams of installation and
supervision of monitoring instruments, which associated to the lack of specific bibliography leads
to the systematic use of trial and error method and to the constant adaption and improvement of
used procedures.
Table 1 resumes the total number of installed equipments, correspondent damages and most
probable causes. It can be seen that about 26% of the installed equipments in Sto Tirso landfill
were damaged (all in Station A, where installation was done as the landfill rises). The number of
equipments damaged in Lipor II landfill was much higher (about 57%), due to equipments
installation done as the landfill rises, to the small size of the landfill and to the change of
exploitation methods during the works.
Table 1- Equipments installed and correspondent damages.

Landfill Sto Tirso Lipor II
Station A B e C R1, R2, R3 Cause
Equipment Installed / damaged un]
Thunderstorm, landfill
Total pressure cells 28/11 - 22/16*
exploitation or failure
Thunderstorm, landfill
Pore pressure cells 7/4 - 6/3*
exploitation or failure
Open tube piezometers 8/2 13/0 6/6* Broken with landfill rise
Inclinometers 5/3 2/0 3/3* Broken with landfill rise
Magnetic plates 7/7 - 9/9* Access lost (6); failure (1)
Magnetic spiders 10/1 8/0 - Access lost
Superficial marks 41/1 13/0 11/1* Equipments circulation
Temperature sensors 35/12 - 28/10* Thunderstorm or failure
Pressure cells inclinometers 21/11 - 16/10* Failure or outside reading range
Total 162/52 36/0 101/58*
* Monitoring in course.
ACKNOWLEDGMENTS
The authors thanks to AMAVE and to LIPOR the support to develop this research.
REFERENCES
[1] Gomes C. G., Estudo do comportamento de aterros de resduos. Caracterizao fsica,

bioqumica e mecnica dos resduos slidos urbanos, PhD Thesis, FEUP (2008) 536p.
[2] Dunnicliff J., Geotechnical instrumentation for monitoring field performance, John Wiley &
Sons, Inc., IBN: 0-471-00546-0 (1993) 577p.
590
1st International Conference
QUALITY OF COMPOST OBTAINED FROM MUNICIPAL SOLID WASTE:

PRESENCE OF HEAVY METALS
a
C. Montejo ; C. Costa; P. Ramos; M. C. Mrquez.
Chemical Engineering Department, University of Salamanca
Address: Plaza de los Cados 1-5, 37008, Salamanca, Spain
Tel.:+34-923-294479; Fax: +34-923-294574.
a
cmontejo@usal.es
ABSTRACT
MSW compost is currently used as cover in landfills because of the bad reputation of
this product and the fear of contaminating crops with heavy metals. Concentrations of
Cr, Ni, Cu, Zn, Cd, Pb and Hg were measured in 30 samples of compost obtained
from OFMSW in 10 MBT plants. Results were compared to the Spanish legislation
which classifies compost into three categories according to their heavy metal content.
Presence of these elements in MSW compost was lower than expected and 9 of the
10 compost could be applied to soils safely. 5 of them were classified as quality B
and 4 of them as quality C. Despite the current destination as cover in landfills these
safe compost could be use as good fertilizer in soils with organic matter deficits. One
of the studied samples showed Hg content higher than allowed by the legislation
preventing its use on land. In order to assure that only high quality compost is applied
to soils, tight controls should be carried out regularly in the MBT plants.
KEYWORDS: MSW compost; soil remediation, composting, heavy metals.
INTRODUCTION
One of the most important strategies of waste management is the treatment of the organic
fraction of municipal solid waste (OFMSW). More than 215 million tonnes of municipal solid
wastes (MSW) are generated in the European Union (EU-27) every year with more than 30% of
organic matter [1]. In some of these countries, including Spain, the amount of the organic
fraction exceeds 50% [2] therefore improving the treatment of this fraction involves a
considerable increase in the efficiency of waste management. In addition, European Directive
1999/31/CE had as main target an important reduction in the amount of biodegradable waste
disposed on landfills in order to avoid negative impacts of this practice (gases emission, bad
odors, plagues proliferation, etc) and the loss of tonnes of product which could be reused. For
that reasons hundred of waste treatment plants have been installed in Europe in the last
decades. In these plants OFMSW is removed from the original stream of MSW by means of
trommels screens and stabilized mainly by means of two biological treatments, anaerobic
digestion and aerobic composting. Anaerobic digestion has the advantage of energy generation
however, composting is the most widely used biological treatment: 17% of municipal waste
treated in the EU27 in 2008 was composted [1]. Composting offers a sustainable waste
treatment strategy that combines waste stabilization and nutrients recovery where the product is
used for soil application.
591
Use on land of other stabilized organic waste such as sewage sludge is a common practice.
Use of this kind of waste, with high content of organic matter, as soil amendment become
essential considering drastic decrease of organic matter content in soils, mainly in dry regions.
Chemical fertilizers cover a significant part of soil needs however, humic substances are
essential to preserve the soil properties. Organic matter provides nutrients required for plant
growth as well as an energy source for microorganisms. Nevertheless, it should proceed
carefully when compost from organic waste is used on land. Spanish legislation bans the use of
these organic amendments in certain kind of grounds like horticultural crops during its growth
cycle. RD 824/2005 was enacted in order to regulate the use of several fertilizer products, such
as compost elaborated from OFMSW, with the aim of avoiding possible harmful effects on
water, flora, fauna and being human.
Composting should be efficient enough to assuring a minimum quality of the compost for its
application in soils. Benefits of compost uses in agriculture have been widely reported, however
excessive supply of soluble salts, phytotoxicity or high heavy metals levels appeared in the past
when MSW participated as process feedstock [3]. Chemical and physical properties of the final
product depend on several factors such as the composting facility design, the nature of
feedstock, operation conditions, length of maturation, etc [4]. Actually, in mechanical-biological
treatment plants (MBTP), compost is obtained from the OFMSW, an extremely heterogeneous
in composition, size, moisture and nutrient content feedstock; this fraction may be contaminated
with non-compostable and possibly hazardous wastes, particularly heavy metals, especially
where organic wastes are not source separated [5].
Because the fear of this kind of pollution, nowadays popularity of MSW compost has decreased
among the farmers and tonnes of this product remain stored around MBT plants. MSW compost
is not considered a safe product, raising suspicions among farmers who reject it even without
charge. Consequently, compost obtained in these facilities is only used as cover in the adjacent
landfills. However, quality of MSW compost with regard to heavy metals has not been reported
in the last years although several corrective measures were taken in this respect such as
increasing the number of batteries bins. The aim of this work was, therefore, to analyze the
presence of heavy metals in the MSW compost which is currently obtained in MBT plants in
order to investigate whether a good fertilizer product is currently being landfilled as well as to
verify the effectiveness of the corrective measures used at present.
METHODS
30 samples of 1 kg of MSW compost were taken in 10 different MBT plants. Each sample
consisted of four representative subsamples extracted from 0.5 m deep in piles of the final
product. All analyses were performed by triplicate on these 30 samples. Moisture was
measured by the weight lost after oven drying, at 105 C for 24 h. Ashes and volatile solids were
measured by weight of dry samples before and after ignition at 540C for 2h. Concentrations of
Cr, Ni, Cu, Zn, Cd, Pb and Hg were measured on the ashes by ICP-OES spectrophotometry
after digestion in a pressurized microwave.
Figure 1 shows, for each chemical substance, the average concentration obtained from the
three compost samples taken in each MBT plant (numbered 1 to 10). These results were
compared to Spanish standard requirements related to fertilizer products (RD 824/2005 [6])
whereby heavy metal concentrations in MSW compost are restricted. According to this
regulation, three kinds of compost can be established in function of threshold concentration of
592
heavy metals: the lowest level (most restrictive) corresponds to compost of quality A while the
most permissive level, which must not be exceeded, is named quality C. At the moment, there
are no unified European criteria regarding the content of heavy metals in compost although limit
values are fairly similar. Limit values of the Spanish legislation for maximum quality compost (A)
are based on the European Council Regulation (EEC) No.2092/91 as minimum requirement for
application on organic farming [7].
According to figure 1, chromium content in the compost samples is not very high in spite of the
fact that glass is the main source of Cr [8] and its presence in the OFMSW has been widely
-1
demonstrated [5]. 80 % of samples showed less than 100 g g dry compost, a value close to
level A (70 ppm), and none of them exceeded level B. Chromium in its reduced form is a
nutritional requirement for animals and has a rather low toxicity to plants, animals and humans.
However, use of compost containing Cr (VI) is forbidden because its great potential to cause
toxicity to plants, animals and microorganisms. Cr (IV) was not present in none of the compost
samples.
As figure 1 shows, nickel concentrations were generally low in all the samples with all the
values meeting the requirement of quality B, 90 ppm. Content of Ni in 90 % of the samples
was below 50 ppm. Despite the damage caused by Nickel when replace other elements in
metalloproteins, phytotoxicity has not been reported after application of MSW compost with high
content of Ni on crops [9].
Previous works have studied accumulation of copper in several crops such as corn, potato,
squash, clover and basil after application of MSW compost [9], [10]. In most of the cases metal
concentrations remained below toxic levels and species like tomato and squash fruit did not
absorb Cu from soil. For these reasons, threshold concentrations of Cu in compost are not very
low, with values of 400 and 300 ppm in qualities C and B respectively, which were not
exceed by any of the studied samples. Content of Cu in 4 of them was even lower than 70 ppm
(quality A).
The main source of zinc in waste is the batteries [8]. Despite the proved presence of these
hazardous wastes in the composting inputs [5], Zn concentration in the compost samples was
not excessive. Compost from 7 of the 10 MBT plants could be classified as quality B with
values below 500 ppm, samples from MBT plant number 2 even satisfied quality A while only
two compost samples should be classified as quality C regarding Zn content. Zn is an
essential element for plants with low potential to cause phytotoxicity consequently use of MSW
compost may be beneficial in regions deficient in Zn.
Presence of batteries in MSW can increase the concentration of cadmium and mercury in MSW
compost as well. However, levels of Cd in the compost samples were very low in 90 % of them,
with values below 0.7 ppm (quality A). Only one of them should be classified as quality C.
According to Woodbury et al. [9] most of the vegetable species can accumulate Cd and even
without MSW compost applications some plants can contain Cd over the recommended value.
Therefore, threshold limits for Cd concentration in compost are strongly limited by legislation
with 0.7, 2 and 3 ppm in qualities A, B and C respectively.
Similarly, mercury concentrations in the studied samples were really low in 90 % of them. 60%
of the samples showed values below 0.4 ppm (quality A) and less than 1.5 ppm of Hg was
found in 30 % of them. However, threshold concentration of Hg was exceeded in one of the
compost samples. Limit values for Hg content in compost are especially low due to its toxicity to
animals and humans at very low concentrations. Therefore, this high Hg content prevented the
use in land of the whole pile of compost where samples were taken.
593
ppm Cr ppm Ni
350 120
300 100
250
80
200
60
150
40
100
20
50
0 0
C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 C1 C2 C3 C4 C5 C6 C7 C8 C9 C10
ppm Cu ppm
Zn
450
1200
400
350 1000
300
800
250
200 600
150
400
100
50 200
0
0
C1 C2 C3 C4 C5 C6 C7 C8 C9 C10
C1 C2 C3 C4 C5 C6 C7 C8 C9 C10
Cd ppm Pb
ppm
250
3,5
3,0
200
2,5
150
2,0
1,5 100
1,0
50
0,5
0,0 0
C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 C1 C2 C3 C4 C5 C6 C7 C8 C9 C10
Hg
ppm
0
C1 C2 C3 C4 C5 C6 C7 C8 C9 C10
Figure 1. Concentration of heavy metals in samples of MSW compost (ppm on dry basis).
594
In the case of lead, 80 % of the samples showed concentrations below 150 ppm and were
classified as quality B. In two MBT plants Pb concentration in compost was below 200 ppm so
were included into quality C group. In general terms, levels of Pb in samples of MSW compost
were slightly higher than rest of the metals. Main source of contamination by Pb is in small
electronic devices that can be still found in MSW [2]; some pieces of these hazardous wastes
can appear in the composting inputs.
Finally, it can be asserted that in general, concentrations of heavy metals in the studied
samples of MSW compost were low. None of the ten MBT plants achieved the quality A for the
MSW compost although individual concentrations for some metals met its requirements.
According to the heavy metals content, 9 of the 10 analyzed MSW compost could be applied to
soils safely. Five of them were classified as compost of quality B whereas the other four were
classified as quality C because of a unique metal. The MSW compost obtained in one of the
MBT plants during the time when the study was carried out could not be used as organic
amendment. The Hg content was over the more permissive limit (quality C) and compost was
used as cover in the landfill.
CONCLUSIONS
Despite the suspicions aroused by compost obtained from OFMSW, the content of heavy
metals in all the analyzed samples except one met the requirements of Spanish legislation.
Once levels below the limit imposed by legislation have been proved there is no reason to use
this product only as cover in the landfills. Benefits of compost as organic amendment have been
reported and its use as cover involves a loss of a good product which can substitute some
chemical fertilizer. Certainly, application of MSW compost to soils should be done under
appropriate circumstances and following the law recommendations.
However, according to the Hg content, one of the MSW compost samples did not show quality
enough to be use on land. Consequently, it is necessary to maintain tight controls over MSW
compost in order to prevent presence of these metals in crops. Since the metals concentration
in compost is related to waste composition which is always variable and heterogeneous, these
controls should be performed periodically.
Therefore, quality of MSW compost in terms of heavy metals content can still be improved.
Their concentration can be reduced avoiding the presence of hazardous waste in raw material
i.e. in MSW. This challenge only can be achieved by two ways: improving the quality of raw
material or replacing them with better ones. Considering nowadays in this region compost is
obtained from the organic fraction mechanically removed from MSW in MBT plants, one of the
possible options could be to collect organic waste separately; better results have been always
reported with this inputs. On the other hand, improving the current inputs can only be carried out
by means of significant campaigns to raise public awareness conducted by the governments
who must also provide the appropriate resources.
ACKNOWLEDGEMENT
The authors gratefully acknowledge the financial support from the Junta de Castilla y Len
(Spain) to the experimental work described hereby.
595
REFERENCES
[1] EUROSTAT, 2010. STATISTICAL BOOKS. Environmental statistics and accounts in Europe
2010 edition. Publications office of the European Union. Luxemburg, 2010.
[2] C. Montejo, C. Costa, P. Ramos and M.C. Mrquez. Analysis and comparison of municipal
solid waste and reject fraction as fuels for incineration plants. Applied Thermal
Engineering 31 (2011) 2135-2140.
[3] Dportes, I., Benoit-Guyod, J.L., Zmirou, D., (1995). Hazard to man and the environment
posed by the use of urban waste compost: a review. The science of the total
environment. 172, 197-222.
[4] Hamoda, M.F., Abu Qdais, H.A., Newham, J., (1998). Evaluation of municipal solid waste
composting kinetics. Resources, Conservation and Recycling. 23, 209-223.
[5] Montejo C., Ramos P., Costa C. and Mrquez. M.C., (2010) Analysis of the presence of
improper materials in the composting process performed in ten MBT plants. Bioresour.
Technol. 101, 8267-8272.
[6] Ministerio de medioambiente y medio rural y marino RD 824/2005
<http://www.mapa.es/agricultura/pags/fertilizantes/documentos/RD824_2005.pdf> (Last
update 10.03.2011).
[7] Hogg D., Barth J, Favoino E, Centemero M, Caimi V, Amlinger F, Devliegher W, Brinton W
and Antler S. (2002) Comparison of compost standards within the EU, North America
and Australasia Main report. The Waste and Resources Action Programme:
<www.compostingvermont.org/pdf/WRAP_Comparison_of_Compost_Standards_2002.pd
f>
[8] Riber, C., Petersen, C. and Christensen, T.H. (2009) Chemical composition of material
fractions in Danish household waste. Waste Management.29, 1251-1257.
[9] Woodbury, P.B. (1992). Trace elements in municipal solid waste compost: A review of
potential detrimental effects on plants, soil biota and water quality. Biomass and
Bioenergy. 3, 239-259.
[10] Hargreaves, J.C., Adl, M.S., Warman, P.R., (2008). A review of the use of composted
municipal solid waste in agriculture. Agriculture, Ecosystems and Environment. 123, 1-
14.
596
VALORISATION OF SUB-PRODUCTS OF FOOD INDUSTRY FOR

ENVIRONMENTAL REMEDIATION OF PHARMACEUTICALS
1 1 1 1 2
J.G. Pacheco , A. Silva , J.T. Albergaria , H.P.A. Nouws , A. Fiza and C. Delerue-
1
Matos
1 REQUIMTE, Instituto Superior de Engenharia do Porto, Rua Dr. Antnio Bernardino de Almeida
431, 4200-072 Porto, Portugal. Email jtva@isep.ipp.pt
2 CIGAR, Faculdade de Engenharia da Universidade do Porto, Rua Dr. Roberto Frias, s/n 4200-
465 Porto, Portugal
ABSTRACT
This work reports the study of the utilization of sub-products of the food industry for the
treatment of water contaminated with the pharmaceutical product ibuprofen. The main
objectives of this work were: i) to evaluate the use of some sub-products of the food
industry as a source of polyphenols for the production of zero valent iron nanoparticles; ii)
to develop an efficient procedure for the extraction of polyphenolic compounds from the
sub-products; and iii) to study the efficiency of the iron nanoparticles to oxidize ibuprofen
in aqueous solution.
The obtained results allow the conclusion that: i) the extracts that presented the highest
polyphenol concentration were obtained after a 30-min extraction at 75C using black tea;
ii) hydrogen peroxide, one of the most widely used chemical oxidants, is unable to
degrade ibuprofen; and iii) iron nanoparticles produced using tea extracts degraded up to
55% of the initial amount of ibuprofen present in aqueous solution.
Keywords: waste valorization; zero valent iron nanoparticles; pharmaceutical products;

remediation.
INTRODUCTION
Since their identification in water, pharmaceutical compounds have been targeted as emerging
environmental contaminants, as their physico-chemical properties (e.g., log Kow, pKa and polarity)
show a tendency towards persistence in solid environmental matrices where they can accumulate
and induce adverse effects in terrestrial or aquatic organisms [1]. Pharmaceuticals are used in
large quantities for humans and livestock in industrialized countries and are continuously being
released into the environment, mainly as a result of manufacturing processes, disposal of unused
or expired products, and excreta [2]. Some of these compounds can easily move from the soil to
the groundwater, through percolation caused by rain, and subsequently to distant locations due to
their high mobility, turning the local problem into a regional issue [3].
The utilization of chemical oxidants to degrade pharmaceutical products is one possibility to solve
this kind of problem. This technology is extremely common and frequently used in the remediation
of soils contaminated with chlorinated hydrocarbons [4,5], polycyclic aromatic hydrocarbons [6,7] or
petroleum hydrocarbons [8,9]. However, its application to soils containing pharmaceutical products
is scarce and requires further work in order to evaluate its real capacity to become a valid
remediation option. Among the available oxidants, nanoscale zero-valent iron particles (nZVI) have
enormous potential to become an essential key player in this type of technology, turning it more
efficient and attractive.
Nanotechnology and nanomaterials have contributed greatly to the development of new
technologies and sustainable solutions to solve several environmental problems, particularly in the
treatment of contaminants in water and soils. In the past decade one successful application of
nanotechnology in environmental remediation was the development of nZVI [10]. The use of these
materials for the treatment of a range of hazardous and toxic wastes, and for the remediation of
597
contaminated sites, has been receiving considerable attention, mostly due to its large range of
application options and high degree of reactivity. The diminutive size of the iron nanoparticles
(below 100 nm) and their large surface area permit enhanced chemical and biological reactivity
[11].
The synthesis of the iron nanoparticles is the key point of this technology. Nanoparticles may be
produced via a top down approach, such as milling or grinding macroscale materials, or, most
commonly, via a bottom up approach, such as the chloride synthesis method, which creates
nanoparticles from component atoms or molecules.
One of the most common methods for the production of nZVI is based on the chemical reduction of
iron(III) (FeCl3 or Fe(NO3)3) with sodium borohydride (NaBH4) in aqueous solution. Recently the
development of "green" protocols for the in situ production of these nanomaterials has been
considered. These green protocols are based on the fast and single-step reduction of iron(III) using
extracts with high polyphenol contents, for example tea extracts. The polyphenols present in the
extracts act as reducing agents and stabilizing agents, preventing agglomeration by capping the
nanoparticles. Based on this green synthesis it is expectable that the use of some sub-products of
the food industry with high polyphenol contents could be the basis for a feasible and economic
method for large-scale nZVI production. With this approach it is therefore possible to valorize some
sub-products and use them in the treatment of several contaminants.
According to the Portuguese Environmental Agency about 1.5 million tones of agricultural waste
are produced every year in Portugal. Although these residues contain, in essence, many
compounds with a high commercial value, the costs of extraction and purification often impede their
usage.
The technology to obtain compounds capable of producing extracts with reducing power is often
performed using aggressive techniques [12] involving solvents with high monetary and
environmental costs.
The main objectives of this work are: i) to evaluate the use of some sub-products of the food
industry as a source of polyphenols for the production of zero valent iron nanoparticles; ii) to
develop an efficient procedure for the extraction of polyphenolic compounds from the cited sub-
products; and iii) to study the efficiency of the iron nanoparticles to oxidize ibuprofen in aqueous
solution.
Reagents and materials

Ibuprofen was purchased from Sigma-Aldrich, potassium permanganate was obtained from Merck,
sulphuric acid (98%) was obtained from Panreac, and iron (II) chloride and sodium hydroxide were
provided by Pronalab. All reagents were of analytical grade quality. Orange and lemon peels where
collected from fresh fruits and finely chopped in a blade mill before the polyphenols extraction. For
almond shell size reduction a hammer mill was used. Black tea (Lipton) was obtained from a local
store.
Extraction procedure
The production of the nanoparticles was based on the common reaction of iron (II or III) chloride
with polyphenols that were extracted from natural products through solid/liquid extractions. The
samples of the natural products were weighted and mixed with deionised water. The extractions
where carried out in a controlled-temperature water bath with orbital shaking. Different
temperatures and extraction times were tested in order to optimize the process. The extraction
efficiency was evaluated based on the total phenolic content of the extract, which was determined
by the modified Folin-Ciocalteu method [13]. The calibration curve obtained with this method was
linear in the range from 1 to 30 mg of gallic acid (GAE) and presented a correlation coefficient of
0.9987.
Remediation tests
The objectives of these tests were to verify the capacity of the studied oxidants (hydrogen peroxide
and nZVI produced from natural products) to degrade ibuprofen and to study the influence of the
-1
pH on the remediation process. To perform these tests 1.2 mg L solutions of ibuprofen were
598
prepared and the pH values of these solutions were adjusted to three levels (acid (pH 3), neutral
(pH 7) and alkaline (pH 12)) using diluted solutions of sulphuric acid and sodium hydroxide.
For the chemical oxidation tests, 250 mL of the ibuprofen solution was introduced in a glass flask
and the tests started when the oxidants were added to the stirred solution. In the tests with
hydrogen peroxide 5.0 mL of a 3% solution was added. For the tests with nZVI, equal volumes (2.5
-1
mL) of a 0.05 mol L iron(II) chloride solution and extract solution were added.
During the experiments samples were collected and analyzed using a fluorescence detector (ex:
220nm; em: 290nm) [14] according to pre-defined sampling schemes. The assay was considered
complete when the concentration of ibuprofen in the aqueous solution reached the detection limit of
the analytical method.
RESULTS AND CONCLUSIONS
Extraction tests
To identify which sub-products were suitable for the extraction of the polyphenolic compounds,
using water as the solvent, a preliminary test was performed at 75 C for 30 minutes. Due to the
different wettability of the studied materials, a fixed volume of water was used and the mass of the
different materials was adjusted. The total phenolic content of the extracts was used to evaluate
the extraction efficiency and consequently the performance of each of the studied natural sub-
products (Figure 1).
almond shell orange peel lemon peel black tea
Figure 1 - Total phenol content obtained with the studied samples (T: 75 C, extraction time: 30
min).
The results indicate that black tea provides the best results, while among the natural sub-products
lemon and orange peels presented the highest polyphenol-containing extracts.
In order to determine the best conditions for the extraction, the influence of extraction time and
-1
temperature were tested, maintaining the mass/volume ratio (0.25 g mL ) constant. The
o
temperature was maintained at 75 C during the optimization of the extraction time, and 30 minutes
was used for the optimization of the extraction temperature.
The obtained results showed that, even at relatively low temperatures, significant amounts of
polyphenols were extracted from the studied samples. The results also allowed the conclusion that
the increase of the extraction temperature using the citrus peels led to lower polyphenol
concentrations. This is due to the nature of the extracted compounds, e.g. ascorbic acid which
presents a rapid degradation rate [15].
599
Almond shells showed a different behavior: an increase of the temperature led to an increase of the
polyphenol concentration.
Although the concentration of polyphenolic compounds reached a maximum after 45 minutes for
lemon peels and almond shells, the difference when compared with the other tested extraction
times is not significant. Therefore a 30-min extraction time was chosen.
Remediation tests
In the remediation tests two oxidants were used (hydrogen peroxide and nZVI produced using
black tea extracts). Figure 2 shows the evolution of the ibuprofen concentration in the aqueous
solution during the chemical oxidation tests using hydrogen peroxide as oxidant. As can be seen in
this figure, hydrogen peroxide was not able to degrade ibuprofen at the three experimented pH
values.
1,2 Hydrogen peroxide

1
0,8
C/C0
0,6
pH=3
0,4 pH=7
pH=12
0,2
0
0 200 400 600 800 1000 1200
Time (min)
Figure 2 - Evolution of the ibuprofen concentration in the aqueous solution during the chemical
oxidation tests using hydrogen peroxide.
After these tests, the nZVIs were produced according to the results obtained in the process
optimization described above. Figure 3 shows the evolution of the concentration of ibuprofen in the
aqueous solution during the chemical oxidation tests using the nZVIs. From these results can be
concluded that the nZVIs can, at neutral pH, degrade up to 55% of the ibuprofen in the aqueous
solution. Acidic and alkaline pH values (pH 3 and 12, respectively) have a negative impact on the
nZVIs and consequently on their ability to oxidize ibuprofen. In these conditions only 25% of the
initial amount of ibuprofen was degraded.
These preliminary tests show the potential of the iron nanoparticles for environmental remediation.
However, there is still a long way ahead in order to transform this technology in a valid and efficient
option, namely the optimization of the extraction procedures and the development of an easy and
efficient in-situ application method.
600
1,2 nZVI
1
0,8
C/C0
0,6
0,4 pH=3
pH=7
0,2
pH=12
0
0 500 1000 1500 2000 2500 3000
Time (min)
Figure 3 - Evolution of the ibuprofen concentration in the aqueous solution during the chemical
oxidation tests using nZVIs.
Acknowledgements
The authors thank the Fundao para a Cincia e a Tecnologia for financial support through the
Project PTDC/ECM/103141/2008 and the pos-doc grant of J.G. Pacheco
(SFRH/BPD/73943/2010).
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occurrence and properties of principal substances, TrAC - Trends in Analytical Chemistry 23 (2004)
753-761.
[2] M.S. Daz-Cruz, M.J. Lpez De Alda, D. Barcel, Environmental behavior and analysis of
veterinary and human drugs in soils, sediments and sludge, TrAC - Trends in Analytical Chemistry
22 (2003) 340-351.
[3] J. Siemens, G. Huschek, C. Siebe, M. Kaupenjohann, Concentrations and mobility of human
pharmaceuticals in the world's largest wastewater irrigation system, Mexico City-Mezquital Valley,
Water Research 42 (2008) 2124-2134.
2
[4] G.C.C. Yang, C. Yeh, Enhanced nano-Fe3O4/S2O8 oxidation of trichloroethylene in a clayey
soil by electrokinetics, Separation and Purification Technology 79 (2011) 264271.
[5] N. Kang, I. Hua, P.S.C. Rao, Enhanced Fentons destruction of non-aqueous phase
perchloroethylene in soil systems, Chemosphere 63 (2006) 16851698.
[6] C.L. Yap, S. Gan, H.K. Ng, Fenton based remediation of polycyclic aromatic hydrocarbons-
contaminated soils, Chemosphere 83 (2011) 14141430.
[7] K.R. Reddy, K.S. Chandhuri, Fenton-Like Oxidation of Polycyclic Aromatic Hydrocarbons in
Soils Using Electrokinetics, Journal of Geotechnical and Geoenvironmental Engineering 135 (2009)
1429-1439.
[8] A. Rinaldi, M.R. Da Silva, Degradation of BTX in Contaminated Soil by Using Hydrogen
Peroxide (H2O2) and Potassium Permanganate (KMnO4), Water, Air, & Soil Pollution 217 (2011)
245254.
[9] C. Yen, K. Chen, C. Kao, S. Liang, T. Chen, Application of persulfate to remediate petroleum
hydrocarbon-contaminated soil: Feasibility and comparison with common oxidants, Journal of
Hazardous Materials 186 (2011) 20972102.
[10] K.D. Grieger, A. Fjordbge, N.B. Hartmann, E. Eriksson, P.L. Bjerg, A. Baun, Environmental
benefits and risks of zero-valent iron nanoparticles (nZVI) for in situ remediation: Risk mitigation or
trade-off?, Journal of Contaminant Hydrology 118 (2010) 165-183.
601
[11] X.Q. Li, D.W. Elliott, W.X. Zhang, Zero-Valent Iron Nanoparticles for Abatement of
Environmental Pollutants: Materials and Engineering Aspects, Critical Reviews in Solid State and
Materials Sciences 31 (2006) 111-122.
[12] M. Naczk, F. Shahidi, Phenolics in cereals, fruits and vegetables: Occurrence, extraction and
analysis, Journal of Pharmaceutical and Biomedical Analysis 41 (2006) 15231542.
[13] V.L. Singleton, J.A. Rossi, Colorimetry of total phenolics with phosphomolybdic
phosphotungstic acid reagents, American Journal of Enology and Viticulture 16 (1965) 144158.
[14] J. Sadecka, M. Cakrt, A. Hercegova, J. Polonsky, I. Skacani, Determination of ibuprofen and
naproxen in tablets, Journal of Pharmaceutical and Biomedical Analysis 25 (2001) 881891.
[15] A.N. Hiatt, L.S. Taylor, L.J. Mauer, Influence of Simultaneous Variations in Temperature and
Relative Humidity on Chemical Stability of Two Vitamin C Forms and Implications for Shelf Life
Models, Journal of Agricultural and Food Chemistry 58 (2010) 35323540.
602
14th September
Session 1.6
Chairman: Teresa Vieira
603
St
THE EFFECT OF SLATE WASTES ON RED CLAY CERAMIC PROPERTIES
Lavrador, C.M.R.1,a, Corker, J.N.C.M.2 and Vieira, M.T.3

1 Dpt. Mechanical Engineering, University of Coimbra, Rua Lus Reis Santos, 3030-788 Coimbra,
Portugal; clavrador@ipn.pt
2 Laboratory Testing and Wear & Materials, Pedro Nunes Institute, Rua Pedro Nunes 3030-199
Coimbra, Portugal; jcorker@ipn.pt
Portugal; teresa.vieira@dem.uc.pt
ABSTRACT
The industry of extraction and processing of natural stones produces enormous quantities
of waste per day. The incorporation of industrial wastes in ceramic red clay is presented
as a successful alternative that, in many cases, allows a minimization in the extraction of
raw materials, the reduction of energy consumption in the production of materials and a
decrease in environmental pollution.
The aim of this work is to study the feasibility of incorporating slate waste from the natural
stones cutting and polishing processing operations, on red clay ceramic for brick and tile
production, and if possible, maintaining the same production cycle of the building
products made from conventional raw materials.
After the chemical, mineralogical and thermal characterization of the matrix and
reinforcement, clay and slate respectively, different clay mixtures incorporating up to 20%
of slate were prepared. Laboratory scale size specimens were shaped by extrusion,
followed by conventional drying and firing procedures to test the influence of the waste
additivation on the final product properties. Whatever the reinforcement content there is a
significant improvement on water absorption resistance. An increase of mechanical
strength with the content of slate waste was observed. However, no significant
improvement of thermal resistance was achieved.
Keywords: Slate; Clay; Wastes, recovery
INTRODUCTION
Environmental issues have been gaining increasing significance and are therefore a global
concern. In the XXI century the continuous productions of wastes is a great environmental,
economic and social challenge, leading to numerous impacts on the environment [1]. All countries,
regardless of location, culture and development, produce millions of tons of wastes per day, which
leads to the necessity of creating mechanisms to promote awareness, development and
implementation of new technologies to reverse this situation. It is necessary to understand that the
inevitability of wastes creation shouldnt determine their quantity. Recycling those wastes to obtain
new materials with improved properties proves to be a successful alternative in many situations.
The traditional ceramic industry should assume its own environmental responsibilities,
incorporating in their raw materials not only their own wastes but also other by-products from
different industries. This action leads to a wide range of benefits such as the reduction of the
amount of raw materials extracted, the minimization of energy consumption in production of these
materials and a decreased on gaseous emissions. The recycling of wastes, as well as being
considered a viable way to reduce costs, can diversify and increase the supply of construction
materials with improved properties [2,3]. However, the possibility of recycling of a given material
depends on factors such as availability, quantity produced and degree of purity, market conditions,
costs and feasibility of transportation, cost associated to the process of transformation in a
reusable material, cost of waste disposal associated with the process and, finally, the
environmental damage resulting from its non-reuse.
604
One of the most disturbing factors in open pit mining is the creation of large amounts of waste piles
due to factors such as lack of planning or extraction control. The natural stone sector, which
includes the extraction of slate, generates a very high amount of wastes. That becomes a problem
to the companies responsible for their final destination [4,5]. Generally these slate wastes are
deposited at open pits near the quarries.
The aim of this work is to study the possibility of manufacturing bricks and tiles through the
incorporation of slate wastes in red clay ceramic. The choice of these wastes is based on
compositional similarities, when compared with the conventional clays used to produce the building
products. The mineral composition in slate depends on the subsequent processes of digenesis and
metamorphism on the mineralogical composition of clay. Thus, the main composition of these rocks
covers a wide variety of minerals such as quartz, illite, chlorite, muscovite, feldspar and poorly
crystallized iron oxides [6]. This work studied a form to recover the slate wastes generated by the
mining industry, resulting from cutting and polishing processes, without submitting them to any
preceding treatment and by using them as they are generally disposed in landfill. Thus, it is
assumed that the elimination of wastes depends on the limits of the incorporation, which should be
as high as possible and, not less important, on the properties and quality of the final products,
when compared with conventional ones made only from clay.
CHARACTERIZATION OF THE MATERIALS
The slate waste sample was collected from a quarry in the area of Valongo that stands out as the
largest company of ornamental slate producers in Portugal and the clay was from a Spanish clay
pit. The chemical composition of the slate waste studied was determined by Catarino [7] and the
clay composition was supplied by the Spanish company. Table 1 shows the chemical analysis of
the two materials both are mostly composed of silica, alumina and iron oxides.
Table 1: Chemical composition of slate and clay samples analyzed

Mass
SiO2 Al2O3 FeO Fe2O3 CaO MgO K2O Na2O TiO2 P2O5 MnO Other
loss
Slate 53.30 24.03 7.37 1.42 0.34 2.08 3.06 1.64 0.89 0.23 0.07 - 5.12
Clay 61.88 17.43 - 7.38 2.11 0.46 4.14 0.48 - - - 0.03 6.09
The real density was determined using a helium pycnometer, model AccuPyc 1330 from the
Micromeritcs. Slate has a density of 2.98g/cm3, slightly higher than the clay, which has a density
value of 2.74g/cm3. To determine the distribution of particle size it was used the laser diffraction
spectroscopy technique implemented in the Coulter model LS 230 from Coulter Electronics. The
powder slate exhibit a wide particle size distribution, where 10% have a diameter lower than 475.4
m, 50% smaller than 817.0 m and 90% below 1371.0 m. In case of the clay, the results indicate
the existence of 10% of particles with particle size below 1.6 m, 50% with diameter smaller than
8.6 m and 90% of the particles below 33 m. These values indicate the existence of a range of
particle size distribution of clay much smaller than the one identified for the slate.
The mineralogical composition of slate and clay powder was analyzed by X-ray diffraction, using a
Philips PW 1710 diffractometer equipment. The main mineralogical species present in the slate
powder correspond to quartz, mica and chlorite. As for the results of the clay powder, it revealed
the existence of quartz, illite, kaolinite, calcite and feldspar as the most important mineralogical
species.
The study of chemical reactions and phase transformations resulting from the increase of
temperature was performed by thermogravimetric (TG) and differential scanning calorimetry (DSC),
using a SETARAM SetSys equipment. Thermal analyses were performed at a heating rate of
-1
10C.min up to 930C in static air atmosphere.
605
Figure 1: TG and DSC curves of slate powder Figure 2: TG and DSC curves of clay powder
The DSC curve for the powder slate (figure 1) reveals three main peaks, two of which corresponds
to endothermic reactions and one to exothermic reaction. The exothermic peak displays a
maximum value for a temperature around 475C and can be related to the decomposition of
organic matter. With regard to the endothermic transformations/reactions, the first peak occurs at
maximum intensity for temperatures close to 550C. This highest peak is associated with the first
dehydroxylation of the structure of chlorite, which results in the loss of most of the OH groups
present. Around 573 C it is possible to observe a split of this peak, which can be attributed to the
allotropic transformation of the quartz to quartz . The second endothermic peak reaches the
highest value for temperatures around 700C and is related to the second stage of the chlorite
dehydroxylation. The TG curve analysis indicates two regimes of mass loss at temperatures
between 475C to 620C, and above 620C.
In case of the clay can be identified four main peaks, represented in figure 2. The first endothermic
peak shows its maximum for temperatures close to 90C and is related with the loss of adsorbed
water. The second peak observed presents a long extension ranging from 300C to 450C, and
identifies an exothermic reaction, resulted from the release of organic matter. The dehydroxylation
of kaolinite is assumed as the second endothermic peak, which presents its maximum intensity at
the temperatures around 510C. Associated with this peak is observed one split around to 573C
which, as noted above, corresponds to the cited the allotropic transformation of quartz . Finally,
there is a third endothermic peak, which results from the decomposition of calcite, with maximum
intensity at temperatures close to 800C. The TG curve shows us four different mass losses, which
corresponds to ranges of temperatures between 100C to 500C, 500C to 725C, 725C to 820C
and above 820C.
The specimens produced for this study consisted in scale models of solid bricks with dimensions of
100 mm x 60 mm x 35 mm. Four sets of specimens were produced and subsequently tested, one
with ceramic slurry having no additives and three with different slate dust additive contents: 5, 10
and 20% (%vol.).
The preparation of the feedstocks comprised several steps beginning with the water-clay mixing
and homogenization (also with the slate dust content in the case of additivated mixtures), to ensure
the necessary plasticity for molding. Ceramic green test bodies were obtained by vacuum aided
extrusion with a SHIMPO NVA-04S laboratory extruder. The samples drying stage was carried out
slowly in two different phases, first at room temperature for 24 hours to avoid the development of
fissures and cracks due to rapid water removal and later by an oven stage at 100C for 24 hours, in
order to complete the drying process. Sintering was carried out in an electric oven, COEL tunnel,
-1
with a gradual rise in temperature up to 930 C, at a rate of 3C.min , with a dwell stage of two
hours at maximum temperature followed by natural cooling. The definition of all these processes
took into account relevant aspects of industrial production, with the necessary adaptations to the
laboratory environment.
606
Processing properties
The parameters selected to evaluate the processing properties were dry shrinkage, total shrinkage,
mass loss and plasticity. When a ceramic body dries, the water evaporates and the particles of the
mixture seek to establish the best possible contact with each other. This phenomenon is
responsible for all or almost all of the shrinkage. Dry shrinkage includes the dimensional variations
that occur in specimens during the drying process up to 100C. As the data presented in table 2
shows, the larger addition of slate in the mix will lead to less shrinkage which will promote lower
dimensional variations of the samples. These results are related to the structure of the slate that,
being a compact solid rock, doesnt present great possibilities of shrinkage or capacity of water
absorption, compared with the clay. The total shrinkage (corresponding to the sum from dry and
sintering shrinkage) presents no significant variations from the values given for the dry shrinkage.
The plasticity shows a decrease on values with the increase of slate waste. Finally, it should be
noted that the mass loss, resulting from the elimination of water, organic matter and calcite during
sintering, has, as expected, a slight decrease with increasing additive content.
Table 2: Influence of slate content

Material Clay Clay with slate
Characteristics
Additive [%] 0 5 10 20
Dry shrinkage [%] 5.4 6.2 5.6 4.7
Total shrinkage [%] 5.8 6.3 5.6 4.8
Mass loss [%] 11.2 10.5 10.1 9.5
Plasticity [%] 24.3 23.7 21.6 19.8
Physical properties
Based on the standard EN 772-13: Method of test for masonry units Determination of net and
gross dry density of masonry units, the Archimedes method was used to measure bulk density,
water absorption and open porosity parameters. For this purpose sintered samples were dried in
an oven at 100C. After previous weighting in the dry state, the samples were immersed in boiling
water during 5 hours and weighted after cooling, both in a submerged and saturated state. Table 3,
shows even though the specific weight variation was not very significant, the increase level of slate
addition led to an increase of the bulk density values (due to higher specific weight of the waste
than clay material). The porosity content (including both open and close ones) (table 3) tends to
decrease with the incorporation of the slate material. This trend seems to indicate that theres a
good compatibility between the particles of clay and slate, even with the higher average particle
size, which results into a better sintering process and, consequently, a more compact structure of
the bulk body. The values referring to water absorption, being closely related to open porosity,
follows the same trend where there is a significant decrease of water absorption by the presence of
the waste material.
Table 3: Influence of slate content on physical properties

Parameters
Units Additive [%] 0 5 10 20
Bulk density [g/cm3] 1.73 1.76 1.82 1.87
Total porosity [%] 37.9 36.5 35.6 32.7
Open porosity [%] 31.3 27.8 27.6 26.7
Close porosity [%] 6.6 9.6 8.0 5.2
Water absorption [%] 18.1 15.2 15.2 14.9
In order to evaluate in more detail the pore distribution variation, complementary porosity tests
were carried out using a porosimeter from MICROMERITICS, Autopore III-9410 model, capable of
measuring pores with a diameter between 0,003 to 360 micrometers. The data shown in table 4 is
related to the porosity values that correspond to open porosity, showing that these results are
significantly higher than those calculated by Archimedes principle. This discrepancy may be the
result of increased pressure in the injection of mercury, which is able to penetrate a greater amount
607
of fluid within the specimen and reach pores unavailable with water at atmospheric pressure.
However, these values follow the trend already observed before, revealing a decrease with the
incorporation of different slate levels in the clay mixture.
Table 4: Porosimetry analysis results

Parameters
Porosity [%] 36.7 36.5 34.8 31.9
Total pore volume [mL/g] 0.22 0.21 0.19 0.17
Median pore diameter [m] 0.7 0.7 0.5 0.7
The compressive strength test was carried out after sintering the samples and was based on the
standard EN 772-1: Methods of test for masonry units Determination of mechanical strength. The
equipment used for this procedure was a SHIMADZU Autograph AG-IS model, with a 100 KN
capacity. Tests were performed at a speed of 0,1 MPa/s, after polishing the samples surfaces in
contact with the equipment in order to accurately define the samples area subjected to
compression forces during its testing. The results for compressive strength (table 5) seem to be
directly related with bulk density and porosity. The higher the bulk density and lower the porosity
(open or closed), the higher is the resistance to compression, since the structure is more compact
and therefore more resistant to forces applied externally. Although it was expected that increasing
slate content in the mix lead to higher values of mechanical resistance, this relationship was not
clear for the 20% of slate composition. The reason behind this phenomenon may be related to a
deficient mixing that didnt induced an effective homogeneity of the feedstock.
Table 5: Influence of slate content on compressive strength

Parameters
Compressive strength [MPa] 23.8 24.6 27.0 25.6
Thermal conductivity
The coefficient of thermal conductivity was calculated based on the standard EN 12667: Thermal
performance of products and building materials Determination of thermal resistance by hot plate
method protected and measurement of heat flow Products of high and medium thermal
resistance. For this calculation, the samples were placed in the form of a flat plate between a hot
and a cold plate in such conditions that the heat flux crossing the sample area is unidirectional.
Tests were carried out at a room temperature of 25C with a relative humidity of 40%. The thermal
conductivity was determined using the following formula:
(1)
K is the thermal conductivity [W/mC], Q is the rate of energy transferred [W], T is the
temperature difference between the two surfaces [C], A is the area [m2] and L is the thickness [m].
The final results correspond to an extrapolation to 10C.
Analyzing the results (table 6), it can be observed that the lower average thermal conductivity
values were registered in clays without addition (0.45 W/mC). Also tests show that although the
incorporation of 5% of slate waste has an insignificant influence on the thermal property, for
compositions reaching a 10% of slate waste, the thermal conductivity value almost duplicates
(0.85W/mC), remaining almost unchanged up to 20%.
Table 6: Thermal conductivity analysis

Parameters
Units Additive (%) 0 5 10 20
2
Thermal conductivity coefficient [W/m .C] 0.45 0.47 0.85 0.86
608
CONCLUSIONS
The study carried out concerning the incorporation of slate waste on red clay ceramic to produce
bricks and tiles allows to consider that its technical possible to produce this composite, allowing
the recycling of this industrial byproduct. The final product properties are conclusive and show an
improvement with slate content of two main properties: mechanical strength and water absorption.
Therefore, despite the feasibility of producing clay bricks and tiles from mixtures incorporating slate
wastes (without need to change the production cycle), the commercial growth of this product is
limited by the current market demand for lower thermal conductivity materials, thus its application is
only useful for specific cases (where is required a great mechanical resistance). In any case, this
study allowed demonstrating the possibility to recovery a waste, reducing its environmental impact.
References
[1] D. Eliche-Quesada, C. Martnez-Garca, M.L. Martnez-Cartas, et. al., The use of different
forms of waste in the manufacture of ceramic bricks, Applied Clay Science 52 [2011] 270-
276.
[2] R.R. Menezes, H.S. Ferreira, G.A. Neves, Use of granite sawing wastes in the production of
ceramic bricks and tiles, Journal of the European Ceramic Society 25 [2005] 1149-1158.
[3] M.T. Vieira, F.M. Barreiros, L. Catarino, Recovering inorganic wastes, Journal of Materials
Processing Technology 143-144 [2003] 454-457.
[4] J.S:M. Moreira, J.P.V.T. Magalhes, J.N.F. Holanda, Processing of red ceramic using
ornamental rock powder waste, Journal of Materials Processing Technology 196 [2008] 88-
93.
[5] M. Campos, F. Velasco, M.A. Martnez, J.M. Torralba, Recovered slate as raw material for
manufacturing sintered structural tiles, Journal of the European Ceramic Society 24 [2004]
811-819.
[6] P.J. Snchez-Soto, A. Ruiz-Conde, R.Bono, et. al., THERMAL EVOLUTION OF A SLATE,
Journal of Thermal Analysis and Calorimetry, 90 [2007] 1, 133-141.
[7] L.M.G. Catarino, Xistos ardosferos: caracterizao e recuperao de desperdcios, doctoral
thesis, University of Coimbra, Portugal,1999.
609
USE OF LIME-MUD FROM PULP MILL PLANT IN CEMENT-MORTARS

1 2 1 2 3
R. Modolo , L.Senff , V.M. Ferreira , J.A.Labrincha and L.A. Tarelho
1 Dpt. Civil Engineering/CICECO, University of Aveiro, Aveiro, Portugal, regina.modolo@ua.pt ,
victorf@ua.pt
2 Dpt. Ceramics and Glass Engineering/CICECO, University of Aveiro , Aveiro, Portugal,
lsenff@gmail.com, jal@ua.pt
3 Dpt. Environment and Arrangement, University of Aveiro, Aveiro, Portugal, ltarelho@ua.pt
ABSTRACT
Lime-mud is a solid waste generated in pulp mill plants in considerable amounts. Its
homogeneous chemical and physical characteristics allow valorization opportunities in the
construction materials sector, namely in mortars. In this paper, a potential waste
management solution was evaluated regarding the viability of this waste incorporation
with a clear benefit in terms of natural raw materials savings.
The lime-mud characterization and its incorporation in cement-based mortars were
appraised. The lime-mud effect on fresh and hardened state properties in different
mortars formulations was assessed. Workability and mechanical strength were some of
the critical features evaluated in this work.
Due to the high moisture content of this waste, the work was developed with the waste in
its natural state, saving water and energy costs, taking into account environmental and
economic factors by avoiding the waste pre-treatment.
Keywords: Lime-mud; cement-mortars; waste management.
INTRODUCTION
Large amounts of industrial wastes have been stabilized with cement or used as an additive
material in cement related manufacturing sector [1;2;3]. The pulp and paper industry is a source of
a wide range of solid residues. Both inorganic (ash, dregs and grits) and organic (sludge) solid
wastes are generated during the different stages in the production of bleached kraft pulp. The
chemical composition of the sludge, dregs and grits is dependent on the manufacturing and effluent
treatment processes and raw materials, and the composition of the ash is dependent on the fuels
and combustion technique used at individual mills [4]. Alternative ecological and economic waste
recovery techniques have been developed and implemented in pulp and paper industry due to the
increase in the amount of waste and the pressure from public opinion in the last decade. Waste
handling is a concern in pulp and paper mills as well as in all industrial plants [5]. Best available
techniques for reducing waste involve minimizing the generation of solid waste or to reuse these
materials, whenever practicable [6]. Building construction industry is a valid option to drain large
quantitative of solid wastes and, as a consequence, avoid natural resources use. Several authors
have been studying several alternatives of pulp and paper wastes valorisation replacing partially or
completely conventional raw materials. Ahmadi and Alkhaja (2001) [7] tested with success primary
sludge as a replacement of filler material in concrete mixes. Eroglu H. et al (2007) [8] studied lime
mud in composite cement manufacturing and the results suggested that the waste is practically an
additive for this application. Considering limestone one of the most used raw materials in the
construction sector, this work intends to assess a solid waste with similar characteristics of
limestone powder, namely as a standard filler. In this work, lime-mud (LM), a solid waste mainly
composed by calcium carbonate and small amount of magnesium carbonate [9] generated from
pulp and paper mill in the chemical recovery process, was studied as a replacement to a standard
limestone mineral filler (SF) in cement-mortars. Both LM and SF were chemically, mineralogical
610
and physically characterized and the results compared. Cement based mortars were produced and
tested.
In the case of mortars, workability parameters in the fresh state were measured using a flow table.
Flow table is a traditional method to determine the workability of mortars. Although it is easy to use
and widespread around the world, this technique does not discriminate the yield stress and plastic
viscosity, which are important parameters to define the rheological behavior of mortars [10,11]. For
that reason, a rheometer has been used for this purpose. In terms of the rheological behaviour,
mortars typically behave as a Bingham fluid, being characterized by a yield stress and a plastic
viscosity. The rheological behaviour was studied with a specific mortar rheometer (Viskomat PC,
Schleibinger) that is able to quantify those factors. This apparatus automatically measures torque,
up to a limit of 300 N.mm, following a preset speed-time program. The Bingham behaviour can be
expressed as the torque (T) to rotation speed (N) relation, T = g + hN, where g and h are
coefficients directly proportional to yield stress and plastic viscosity, respectively [12-15].
Additionally, the mechanical strength up to 28 days of curing, the apparent density, water
absorption and porosity were measured.
EXPERIMENTAL
Materials
The ordinary Portland cement (PC) used in this study was a CEM II 32.5 R type produced by Secil
(Portugal). The lime-mud was collected from paper pulp mill, where 420.000 t/year of this waste in
dry base is produced. It is an industrial solid waste obtained from re-causticizing process inserted
in the chemical recovery process circuit. The calibrated standard limestone mineral filler was a
commercial one. This material is conventionally used as filler in industrial mortars. PC has an
2
average particle size of 14 m and a Blaine fineness of 0.47m /g, LM has a particle size distribution
2
between 0.5 to 26 m (average 10 m) and a surface area of 5.17 m /g (BET) and the SF has a
2
particle size distribution between 0.5 to 9 m (average 2.8 m) and a surface area of 3.44 m /g
(BET). The sand particle size was below 1,2 mm (EN 933-1: 2000) [16]. The chemical composition
data (determined by X-ray fluorescence spectroscopy) of LM and SF are illustrated in Table 1.
Figure 1.Lime-mud (scanning electronic microscope photograph).
Table 1. Chemical composition of lime-mud (LM) and standard filler (SF).

CaO MgO Al2O3 SiO2 K2O Na2O Fe2O3 LOI
Sample
%
LM 51.80 0.48 0.20 0.29 0.06 1.85 0.03 43.7
SF 55.1 0.37 0.35 0.20 0.01 0.01 0.05 44.3
611
Methods
Mortars using different amounts of lime-mud and standard lime filler (0, 6, 12 and 18 %) were
produced and tested (Table 2). Lime-mud was used in its natural condition, as-received from the
paper pulp mill with 34% of moisture. This LM water was discounted from nominal water content
used to produce the mortars. The total water and the superplasticiser used in the mortars mixtures
were 62% and 0.07% in relation to cement content, respectively. The LM and SF were used as
fillers in substitution of sand by weight in dry base. The formulations were evaluated through
rheology and flow table measurements, assuring that all the samples exhibited an adequate
condition to be tested in both equipments. In this way, it was possible to obtain a complete
characterization of their fresh state behavior. A complementary study of these mortars in the
hardened state was also developed.
The procedures used to prepare the formulations included: (i) placing lime-mud and the rest of
mortar components into water; (ii) mixing for 1 min at a low rotation speed of 60 rpm; (iii) stopping
for 1 min; (iv) mixing again for 1 min at a higher rotation speed (120 rpm). The rheometer measured
the rheological behavior of fresh mortars, with a maximum speed rotation of 100 rpm during 60
minutes of total test time. The workability of mortars was measured through the slump on flow
table, according to EN 1015-3:1999 [17]. Mortars specimens with 40 40 160 mm were produced
for the mechanical test and tested after 28 curing, according to EN 1015-11:1999 [18]. Specific
density, apparent porosity and water absorption were also determined with two flexural specimen
remains by the immersion technique.
Table 2. Cement-mortars formulations.

Free LM LM SF Ratio
Cement Sand
Mortars Water Water (d.b.) (d.b.) (Filler/Cement/Sand)
(g)
0% 445 1335 276 0 0 0 0 / 25 / 75
LM6% 445 1255 232 44 80 0 4.5 / 25 / 70.5
LM12% 445 1175 189 87 160 0 9 / 25 / 66
LM18% 445 1095 145 131 240 0 13.5 / 25 / 61.5
SF6% 445 1255 276 0 0 80 4.5 / 25 / 70.5
SF12% 445 1175 276 0 0 160 9 / 25 / 66
SF18% 445 1095 276 0 0 240 13.5 / 25 / 61.5
The high content of CaCO3 in LM makes this waste an interesting material to be used as filler,
although LM and SF exhibited some significant differences like the particle size, specific surface
area and Na2O content. For that reason, such differences may be the main responsible for distinct
performance on the mortars.
Fig. 2 exhibits the torque values of mortars containing LM, SF and control (0%). In general, the
torque values of samples with LM reached the highest results if compared to the SF substitution.
When very fine particles with higher surface area are added in the mortars, they can modify the
fresh state behavior, since the free water available in the mixture tend to decrease. Thus, particle
friction in such samples is higher than those samples without additions. Moreover, in the control
sample, the superplasticiser can act exclusively on the cement particles increasing the free water,
responsible for keeping particles separate by a certain distance. In addition, describing mortars
rheological behavior as a Bingham fluid means that the material acts as a rigid body at low stresses
but flows, as a viscous fluid, at high stress having a linear relationship between shear stress and
strain rate once the threshold shear stress is exceeded [12]. The vertical lines above the torque line
of the mixtures (fig. 2) indicate intense structural formation during the test stop period (when
rotation speed goes to zero rpm). Such behavior was more evident on the samples with higher
content of LM and at the end of the test.
612
180
0% LM6% SF6% LM12% SF12% LM18% SF18%

160
140
120
Torque (N mm)
100
80
60
40
20
0
0 10 20 30 40 50 60
Time (min)
Figure 2. Torque vs. time of lime-mud and standard filler mortars.
Fig. 3 and 4 present the results concerning the effect of fine particles introduction on the plastic
viscosity and yield stress on mortars, respectively. In general, samples with LM exhibited the
highest results if compared to the LM at the beginning of the test. However, such differences
decreased along time.
1,00
0% LM6% LM12%
0,90 LM18% SF6% SF12%
0,80 SF18%
0,70
h (N mm min)
0,60
0,50
0,40
0,30
0,20
0,10
0,00
0 5 10 15 20 25 30 35 40 45 50 55 60
Time (min)
Figure 3. Plastic viscosity of mortars with lime-mud and standard filler.
This LM mortars behaviour make sense if the waste-water has not been available in the beginning
of the test as discussed before. This remaining water starts getting free of the mixture after 30
minutes of test, making the LM mixtures more fluid and keeping the registered values constant. LM
613
mortars plastic viscosity can also be confirmed through the flow table (spread diameter) results on
Table 3. The spread decreases with the LM content increase. The maximum yield stress was
observed in LM18% samples when compared to the control sample, while low constant values
were registered on samples with 12% and 18% of SF.
Table 3. Mortars flow table spread results.

Samples 0% LM6% LM12% LM18% SF6% SF12% SF18%
Spread (mm) 206 200 191 151 238 260 260
100
0% LM6% LM12%
90 LM18% SF6% SF12%
80 SF18%
70
g (N mm)
60
50
40
30
20
10
0
0 5 10 15 20 25 30 35 40 45 50 55 60
Time (min)
Figure 4. Yield stress of mortars with lime-mud and standard filler.
Table 4 presents the mortars hardened state characterization. The results show that LM does not
affects significantly mortars density and strength, as well as the porosity or water absorption when
compared to SF samples. The standard limestone filler (SF) containing mortars presents slightly
higher values of the compressive strength and lower porosity, which might be related to its particle
size distribution that might improve compaction.
Table 4. Mortars spread and hardened state characterization.

Specific Water Flexural Compressive
SD Porosity SD SD SD SD
Samples Density Absorption Strength Strength
(g/cm3) (%) (%) (Mpa) (Mpa)
0% 1.92 0.0 24 0.2 13 0.1 5.5 0.2 17 0.9
LM6% 1.90 0.0 24 0.0 13 0.1 4.9 0.4 19 1.8
LM12% 1.88 0.0 24 0.2 13 0.1 5.1 0.2 20 0.4
LM18% 1.89 0.0 25 0.1 13 0.1 5.5 0.3 21 2.4
SF6% 2.06 0.0 18 0.5 9 0.3 6.0 0.2 26 0.8
SF12% 2.04 0.0 18 0.2 9 0.1 5.8 0.3 26 0.3
SF18% 2.02 0.0 19 0.1 9 0.1 6.3 0.1 25 2.7
*SD - Standard Deviation
CONCLUSIONS
The characterization results indicate that lime-mud from pulp and paper mill represents a waste
with similar chemical and physical properties.
614
The use of this waste (lime-mud) in mortars affects significantly their rheology when compared to
SF mortars results and the control sample:
(i) The increase of LM content decreases the mortars fluidity, improving the cohesion between
the material particles in fresh state;
(ii) LM addition is equivalent to removing water from the system causing torque and yield
stress increase and plastic viscosity decrease.
The hardened properties of mortars are not hindered with LM addition when compared to control
samples. The LM waste use in cement-based materials as mortars can represent a good
alternative for thousands of tones of this waste per year. This application avoids waste landfilling
and also saves of natural resources as lime.
References
[1] B. Batchelor, Overview of waste stabilization with cement. Waste Management, 26 (2006)
689-698.
[2] M.C. Monte, E.Fuente, A. Blanco, C. Negro, Waste management from pulp and paper
production in the European Union. Waste Management & Research, 29 (2009) 293-308.
[3] B.J. Mohr, H. Nanko, K.E. Kurtis, Durability of kraft pulp fiber-cement composites to wet/dry
cycling. Cement and Concrete Composites, 27 (2005) 435-448.
[4] H. Nurmesniemi, R. Pykio, L.R. Keiski, A case study of waste management at the Northern
Finnish pulp and paper mill complex of Stora Enso Veitsiluoto Mills, Country Report, Waste
Management 27 (2007) 19391948.
[5] H. Eroglu, U. Acar, O. mamolu, O, Soil stabilization of roads sub-base using lime-mud waste
from the chemical recovery process in alkaline pulp mill. Journal of Applied Sciences 6 (5)
(2006) 1199-1203; ISSN 1812-5654.
[6] A. Hassani, H. Ganjidoust, A.A. Maghanaki, Use of plastic waste (poly-ethylene terephthalate)
in asphalt concrete mixture as aggregate replacement. Waste Management & Research; 23
(2005) 322-327.
[7] B. Ahmadi, and W. Al-Khaja, Utilization of paper waste sludge in the building construction
indusry. Resources Conservation Recovery 32 (2) (2001) 105-113.
[8] H. Eroglu, H.H. Acar Unc, O. mamolu, The effect of fry sludge addition supplied from
pulp mill on the compressive strength of cement. Journal of the University of Chemical
Technology and Metallurgy 42 (2) (2007) 169-174.
[9] J. Gaskin, Land application of pulp mill lime mud. University of Georgia, College of Agriculture
and Environmental Sciences, Cooperative Extension Service along with the Pollution
Prevention Assistance Division. Bulletin 1249, Georgia, USA, 2004.
[10] L. Senff, D. Hotza, W.L. Repette, V.M. Ferreira, J.A. Labrincha, Influence of added nanosilica
and/or silica fume on fresh and hardened properties of mortars and cement pastes Advances
in Applied Ceramics, 108 (2009).
[11] R. Modolo, V.M. Ferreira, L.M. Machado, M. Rodrigues, I. Coelho, Construction materials as a
waste management solution for cellulose sludge. Waste Management 31 (2011) 370377.
[12] H. Paiva et al., Effects of a water retaining agent on the rheological behaviour of a single-coat
render mortar. Cement Concrete Res 36 (2006) 125762.
[13] C.F. Ferraris, Measurement of rheological properties of cement past: a new approach. J Res
Natl Inst Standard Technology 104 (1999) 46178.
[14] P.G. Banfill, Rheological methods for assessing the flow properties of mortar and related
materials. Construction Building Materials 8 (1994) 4350.
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289 (1993) 149-60.
[16] EN 933-1: 2000. Tests for geometrical properties of aggregates. Part 1: Determination of
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and compressive strength of hardened mortar.
615
BIOWASTES PRODUCED AT CANTEENS OF THE UNIVERSITY OF

COIMBRA: ESTIMATION AND ECONOMICAL GAINS OF RECYCLING
1 2 1
Andreia S. D. Jesus , Margarida J. Quina , Jos C. Gis
Rua Lus Reis Santos - Plo II, 3030-788 Coimbra, Portugal; email: jose.gois@dem.uc.pt
Lima - Plo II, 3030-790 Coimbra, Portugal, email: guida@eq.uc.pt
ABSTRACT
The University of Coimbra (UC) is one the largest schools in Portugal, with eight faculties
and seventeen canteens. At present, recycling materials only includes glass, paper,
metal, plastic and vegetable oil. However, high amount of mixed wastes are disposed of
which are mostly biowastes from food preparation, and thus, may be recycled by
composting processes. The aim of this study is to estimate the global biowastes amount
produced at canteens of UC during three years (2007, 2008 and 2009), using the results
of the measurement of the mass of organic wastes associated to the preparation of
vegetables at two of the canteens during three weeks. In 2008, 1,246,764 meals were
prepared, which about 25% are prepared in Polo II and ISEC canteens, both used in this
study. Reference vegetables in our work include fruit, potato, cabbage, lettuce, garlic,
onion, carrot, sprouts, cucumber, pepper, tomato, broccoli and turnips. The
measurements were used to calculate the mass ratio of biowastes per type of vegetable
and biowastes per meal. These results were used to predict the amount of biowastes
generated at UCs canteens in 2007, 2008 and 2009. The results obtained showed that
an amount of biowastes in the range of 109.9 t to 117.2 t was produced in UC canteens
3
in 2009, which represents a volume between 379 to 404 m . During one year, this volume
may generate about 3160 reduction in waste management costs. The global analysis to
the management system used at UC canteens seems to indicate that the recycling of a
high quantity of biowaste through composting is feasible, having interesting economical
gains. On the other hand, nowadays composting is strongly recommended by the
European regulations.
Keywords: canteens biowastes; composting; recycling, economical gain
INTRODUCTION
The University of Coimbra (UC) is one of the largest high schools in the country with 17,187
students and 2,853 employees (faculty and staff), reported in 2007 and has eight faculties, grouped
into three campus. At present,17 canteens are available and an average of 6,000 meals per day
are prepared [1].
Nowadays the policy of waste management at food services of UC involves the recycling of plastic,
paper and cardboard at the warehouse and waste oil and glass bottles at canteens. Some of the
wastes with potential for recovery are included in the municipal solid waste (MSW). For disposal of
MSW 20 containers of 800 L are covering only eight canteens, considered the major producers,
according Municipal Solid Waste Regulation. In this scope, composting process may provide an
environmental sound approach to mitigate pollution by converting organic materials into a stable
humus-like product (compost) through aerobic biological oxidation.
The composting of the food preparation biowastes, in opposition to disposal in landfill, may lead to
economical and environmental gains. Indeed, nowadays recycling and conservation of natural
resources give rise to extremely important sustainability concerns in modern societies. In this
scope, composting process may provide an environmental sound approach to mitigate pollution by
616
converting organic materials into a stable humus-like product (compost) through aerobic biological
oxidation [2]. On the other hand, it is very important to note that the separate collection of biowaste
with a view to the composting is strongly recommended by the European regulations (e.g. Directive
2008/98/EC) in order to reduce the organic matter disposed of in landfills and to ensure
environmental protection.
In order to estimate the potential organic waste generated at UC canteens and snack bars that can
be sent to composting, an experimental study was conducted at CAP II and ISEC canteens in
2008. Both canteens used to serve about 25% of the total meals (170,700 at CAP II and 144,412 at
ISEC).
EXPERIMENTAL METHODOLOGY
Data base from both canteens
During three consecutive weeks (16 November to 6 December 2009) the food products and the
biowaste connected to their preparation were measured at Cap II and ISEC canteens. During the
same period was recorded the number of meals served in both canteens. The mass of food
products consumed (reference vegetables in our work include: fruit, potato, cabbage, lettuce,
garlic, onion, carrot, sprouts, cucumber, pepper, tomato, broccoli and turnips) and the biowaste
directly connected to preparation an analogical scale up to 50 kg and with 50 g of accuracy was
used in both canteens. Biowastes coked but not consumed were excluded.
Method to estimate the potential production of biowaste for composting

Using the results obtained during the three weeks of study at the two canteens the following rates
were calculated:
- Ratio of the mass of biowaste i/mass of product i consumed, T(BWi/PCi|CAP II) and T(BIi/PCi|ISEC);
- Ratio of total mass of biowastes/total mass of products consumed, T(BW/PC|CAP II) and
T(BW/PC|ISEC);
- Total mass of biowastes/number of meals T(BW/NM|CAP II) and T(BW/NM|ISEC).
Table 1 shows the symbols and terms adopted in the paper.
Table1 Symbols and terms adopted in the paper.

Variables Description Variables Description
PCi Product i consumed BW Total biowastes
BWi Biowaste i T(BWi/PCi) Rate of biowaste i/product i consumed
NM Number of meals T(BW/PC) Rate of biowastes/products consumed
PC Total products consumed T(BW/NM) Rate of biowastes/number of meals
Keys
3s 3 consecutive weeks
CAPII Canteen at Plo II
ISEC Canteen at ISEC
Using the mass ratio of biowaste for each product i consumed during the period of experimental
study, T(BWi/PCi|3s), and the annual consumption of each product i in 2008 (PCi|2008) was
calculated the annual biowaste i for each product i at both canteens in 2008 (BWi|2008-CAPII and
BWi|2008-ISEC) and the addition gives the total biowastes at each canteen in 2008 (BW|2008-CAP II and
BW|2008-ISEC). With the total mass of biowaste at each canteen in 2008 was calculated the annual
rate of biowastes per products consumed, T(BW/PC|CAP II-2008) and T(BW/PC|ISEC-2008).
With the values of biowastes estimated in 2008 at each canteen, (BW|2008-CAP II and BW|2008-ISEC)
and the number of meals (NM|2008) was calculated the ratio of waste per meal, T(BW/NM)|2008 in
CAP II and ISEC. This ratio T(BW/NM)|2008 was used to estimate the biowastes in each canteen in
2007 and 2009, using the numbers of meals.
The total of biowastes for all canteens of UC in 2008, 2007 and 2009 were calculated using the
total of products consumed (the same products as the case study) and the number of meals. The
two methods are explained:
617
Method 1 the total mass of biowaste in 2008 at UC canteens (BW|2008-UC) is calculated multiplying
the annual consumption of each product i (PCi|2008-UC) with the total ratio of biowaste i/total
consumption of product i T(BWi/PCi|3s), obtained for each canteen. Thus two different results
(BW|UC-CAP II) and (BW|UC-ISEC) were obtained.
Method 2 the total mass of biowaste in 2008, at UC canteens (BW|2008-UC) is calculated
multiplying the total number of meals in 2008 at UC canteens (NM|2008-UC) with the ratio of the total
biowaste/meal T(BW /NM|2008), obtained using CAP II and ISEC results in 2008. Method 2 was
used to estimate biowastes in 2007 and 2009 at UC canteens.

During three weeks, which corresponded to 14 consecutive days were recorded the number of
meals (NM), the consumption of each product i (PCi) and the biowaste generated by the
preparation (BWi). During this period the number of meals in both canteens was 12615 at CAP II
and 9776 at ISEC. The products consumed in 2008 and the numbers of meals in UC canteens are
shown in Table 2.
Table 2 Data from food services of UC.

2007 2008 2009
NM NM PC(kg) NM
CAP II 184122 170700 94371 166616
ISEC 154408 144412 95401 133432
UC_total 1445213 1246764 834128 1213139
Table 3 summarizes the ratio of biowaste for each product consumed at ISEC and CAP II during
the period of study. In some cases the ratios of biowaste were quite different between canteens, as
was the case of lettuce. This is explained by the difference adopted to prepare this food. The ratio
T(BW/PC) at CAP II was 18%, while at ISEC was 11%.
Table 4 shows data records obtained at each canteen during the 3 weeks and the calculated mass
ratio of biowaste per product consumed T(BWi/PCi)3s and ratio of biowaste per meal T(BW/NM)3s.
Table 3 Production rate of residue i green / green product i consumed in the CAP II and ISEC.
Product BWi/PCi|CAP II (%) BWi/PCi|ISEC (%) Product BWi/PCi|CAP II (%) BWi/PCi|ISEC (%)
Fruit 27 41 Cabbage and carrots 14 39

Potato 9 4 Sprouts 48 52
Cabbage 30 37 Cucumber 23 19
Lettuce 65 31 Pepper 28 35
French garlic 45 29 Tomato 7 18
Onion and Dry garlic 19 18 Turnip 28 -
Carrot 5 19 Broccoli 42 -
Table 4 Data records obtained during the 3 weeks of experimental work.

NM (PCi)3s (kg) (BWi)3s (kg) T(BW/PC|3s) T(BW/NM|3s)
CAP II 12615 5875 1074 18 0.085
ISEC 9776 4616 512 11 0.052
The analysis of results shows that the most representative products consumed are lettuce,
potatoes, carrots, cabbage and fruit, which together achieve 83% of the total of biowaste. Table 5
shows the (PCi) and (BWi) results of these representative products and the different ratios:
T(BWi/PCi|CAP II), T(BWi/PCi|ISEC), T(BW/NM|CAP II) and T(BW/NM|ISEC).
618
Table 5 Data records of the most representative biowastes during 3 weeks at CAP II and ISEC canteens.
Lettuce Potato Carrot Cabbage Fruit
PCi BWi PCi BW PCi BWi PCi BWi PCi BWi
CAP II (kg) 231 150 3228 288 320 17 583 177 937 255
ISEC (kg) 185 58 3620 160 70 13 296 111 203 84
T(BWi/PCi|CAP II) 65 9 5 30 27
T(BWi/PCi|ISEC) 31 4 19 37 41
T(BW/NM|CAP II) 0.019 0.023 0.0013 0.014 0.020
T(BW/NM|ISEC) 0.006 0.016 0.0013 0.011 0.006
Predication of annual biowastes at CAP II and ISEC canteenss

The annual biowastes at both canteens studied calculated for 2007, 2008 and 2009 assumed that
products consumed during the year were the same of the case study. Fig. 1 shows the predicted
mass of biowastes in 2008 (BW|2008) using as reference the ratio of biowaste per product calculated
for 3 weeks (BWi/PCi|3s). Among the products consumed in 2008 were removed from the list the
green beans and the turnips because none of them were consumed during the 3 weeks. Both
products achieve around 1% of total consumption. Potatoes and fruit are the highest consumption.
Figure 1 Products consumed and the estimated Figure 2 Products consumed and biowastes at
biowaste at CAP II in 2008. ISEC in 2008.
Fig. 2 shows the biowastes and consumption of products at ISEC in 2008. In Table 6 are compared
the ratio of biowastes per products consumed for both canteens. A difference of approximately 1%
is explained by the proximity of the meals at both canteens.
Table 6 Comparison of biowastes in both canteens in 2008 based on the ratio obtained for 3 weeks.
(PC|2008) (kg) (BW|2008) (kg) T(BW/PC|2008) (%)
CAP II 94371 15464 16
ISEC 95401 13951 15
The amount of biowastes per meal T(BW/NM) in 2008 in both canteens are : T(BW/NM) CAP II=90 g
and T(BW/NM)ISEC=100 g and was calculated for 170700 and 144412 meals respectively.
The mass of biowastes in 2007 and 2009 was predicted coupling the number of meals with the
mass of biowastes previous calculated for each canteen in 2008, Table 7.
Table 7 Biowaste in 2007 and 2009 based in the number of meals and (BW/NM) for each canteen.
2007 2009
NM BW (kg) NM BW (kg)
CAPII 184122 16680 166616 15094
ISEC 154408 14917 133432 12890
619
As the number of meals has been decreasing the mass of biowastes is decreasing too (around
1586 - 2027 kg less).
Predication of annual biowastes in UC canteenss

In order to predict the biowastes in UC canteens in 2007, 2008 and 2009 was adopted the
methodology described before:
- Method 1 to predict biowastes in 2008;
- Method 2 to predict biowastes in 2007 and 2009.
Prediction based on method 1

Based on the ratio of biowaste i/product i consumed in each of the canteens is estimated the
annual mass of waste in all canteens of UC in 2008. Fig. 3 shows the annual consumption of
products and the biowastes based on ratio achieve for CAP II and ISEC canteens. This prediction
exclude the biowastes generated by products such as water cress, spinach, green beans, turnips,
squash, mushrooms, courguetes and aromatic herbs, which globally achieve less than 1% of the
products with potential to generate biowastes.
Table 8 shows the total of products consumed and biowastes at UC canteens in 2008, according
the ratios calculated for CAP II and ISEC canteens. Using both methods to estimated biowastes in
UC canteens in 2008 - only year that the consumption of products and the number of meals was
available - the difference is 12% - 15% depending of ISEC or CAP II ratios. As several canteens
operate as snack-bar the menu not includes soup, fruit and consequently biowastes are less in
comparison. At weekend only two or three canteens operate at lunch and dinner and in August only
one canteen. Consequently the prediction for 2007 and 2009 should be higher than the values
shown in Table 8.
Figure 3 Products consumed in all canteens in 2008 and estimation of biowaste based on the ratios
T(BWi/PCi|CAP II) and T(BWi/PCi|ISEC).
Table 8 Consumption of products and biowastes generated at UC canteens in 2008.

UC canteens
PC (kg) BW(kg) T(BW/PC|2008) (%)
CAP II 834128 132236 16
ISEC 828011 137266 17
Prediction based on method 2

Based on the mass of biowaste/meal of CAP II and ISEC canteens is predicted the mass of
biowastes in 2007, 2008 and 2009 in UC canteens, Table 9.
620
Table 9 Biowastes in 2007, 2008 and 2009, in UC canteens based in T(BW/NM) in CAP II and ISEC.
2007 2008 2009
NM 1445213 1246764 1213139
BW|CAP II (kg) 130924 112946 109900
BW|ISEC (kg) 139616 120444 117196
Potential economic gains achieved with UC canteens biowastes

As previous refereed there is not an integrated management of all biowaste generated at UC
canteens and snack-bar. UC has a contract with Coimbra Municipality to supply 20 containers of
800 L for all canteens under the payment of 31,600. Using as reference 2009 year with less
biowastes the biowastes are between 109,900 and 117,196 kg. Assuming for biowaste an
3 3
average density of 290 kg/m [3] the volume is in the range 379 to 404 m . If these biowastes are
removed from the containers of 800 L used for MSW this allow an annual reduction of containers
between 474 and 505.
Table 10 Annual biowastes in UC canteens based in CAP II and ISEC reference ratios.
Ref. 2007 2008 2009
NM BW NM BW PC BW NM BW
CAP II 184122 16680 170700 94371 15464 166616 15094
ISEC 154408 14917 144412 95401 13951 133432 12890
CAP II 130924 112946 834128 132236 109900
UC 1445213 1246764 1213139
ISEC 139616 120444 828011 137266 117196
If all UC canteens are working at least 48 weeks x 5 days/week, this represents a minimum of 240
days (all weekends and August are excluded). According previous calculation two containers of
800 L per day can be eliminated. Assuming 10% of reduction in the costs of waste management
with this approach, an annual saving of 3,160 is achieved. If the company that collect and
composting the biowaste achieves a conversion factor around 30% (LIPOR reference) produces
between 32,970 and 35,159 kg of compost. Assuming that the company that collects and
processes biowaste has 20% profit/kg above the sale price, for a reference price of 0.3/kg, the
annual profit is between 1,978 and 2,110. In addition to the economical gains of recycling occurs
also the environmental benefits of non-waste disposal in landfills and the production of natural
fertilisers in contrary to the production of chemical fertilisers.
CONCLUSIONS
This study has shown that annual biowastes at UC canteens are up to 109 ton. The prediction of
annual biowastes based in the ratio of biowaste i/product i consumed is more precise than the
mass of biowaste/meal.
The results have shown that the deviation of biowaste from the MSW allow a daily reduction of at
least two containers of 800 L which can represents a reduction of at least 10% in the cost of waste
management, which provide an annual saving of around 3,160.
In addition around 32 ton of natural fertilisers can be produced substituting production of chemical
fertilisers.
References
[1] Vaz, A. L. Aco Social Escolar na Universidade de Coimbra Evoluo histrica e princpios
orientadores, Imprensa da Universidade de Coimbra, 2009.
[2] Haug, R.T., The Practical Handbook of Compost Engineering. Lewis Publishers, Boca Raton,
FL, USA, 1993.
[3] Russo, M. A. T. Tratamento de Resduos Slidos, Tese de Mestrado, FCTUC, Universidade
de Coimbra. 2003.
621
14th September
Session 2.6
( SPECIFIC WASTE-STREAMS 2 )
Chairman: Carlos Nogueira
622
St
WASTE BIODEGRADABILITY ASSESSMENT DURING HUMIFICATION

PROCESS
1 2 1 1
C.C. Matsinhe , M. R. Soares , M. J. Quina and R. Quinta-Ferreira
1
CIEPQPF- Research Centre on Chemical Processes Engineering and Forest Products, Chemical
Lima - Plo II, 3030-790 Coimbra, Portugal (E-mail: Crechula_m@hotmail.com, guida@eq.uc.pt,
rosaqf@eq.uc.pt)
2
Cernas Natural Resources, Environment and Society Research Centre, Coimbra College of
Agriculture, Polytechnic Institute of Coimbra, Bencanta, 3040-316 Coimbra, Portugal (E-mail:
msoares@esac.pt)
ABSTRACT
Amongst waste management strategies, composting is gaining interest as a suitable

method with economical and environmental profits. The mixture of wastes must be
potentially biodegradable to enhance biologically catalyzed breakdown of organic matter,
in aerobic conditions, and drive the composting process into thermophilic temperatures
required for pathogen reduction. This study aimed to predict the biodegradability of an
initial waste mixture and to investigate how this property determines the changes in
organic matter characteristics during the composting process. The initial mixtures tested
were made from potato-peel industrial waste (PP), grass clippings (GC) and sawdust
(SD) in different proportions and were composted in self heating reactors.
Biodegradability was assessed by measuring lignin content, using the Klason lignin
method. The results obtained indicated that independently of the initial mixture
composition, there is an increase in lignin content that can be related to the decrease of
the potential for biodegradation of the tested mixtures. The initial samples with the lower
and higher lignin content showed a greater and smaller mass reduction, respectively, at
the end of composting period. As expected, our results showed that higher lignin content
of an initial mixture led to lower biodegradation of the mixture.
Keywords: composting; biodegradability; biodegradable wastes.
INTRODUCTION
Composting can be defined as the aerobic microbial decomposition of organic matter of vegetable
and animal origin, under conditions that allows the development of thermophilic temperatures as a
result of the heat produced in the biological reactions, leading to a stabilized and hygienized final
product (free of pathogens and seeds), commonly known as compost [1]. Therefore the mixture of
wastes must biodegradable to occur the organic matter breakdown by microorganisms in aerobic
conditions and to force the composting process into thermophilic temperatures [2-4]. As a result,
the prediction of the biodegradable fraction of a starting composting mixture is of major importance.
623
In general, the extent to which organic matter can be degraded in composting processes is
quantified by a biodegradability index () that is defined as the fraction of the volatile solids (organic
matter) (VS) that is susceptible of being decomposed during typical composting conditions.
Several biological testing methods are available for the characterization and testing of organic
matter biodegradability which are mainly based in the biological respiration potential assessment of
the materials in aerobic conditions [5,6]. However, since these tests are time consuming and costly
it is desirable to use simpler, rapid and cheaper methods that may be a useful surrogate for
biological tests.
It is well established that lignin is the main precursor for humic substances that is mainly humified
and not mineralized, during degradation in a compost environment [7,8]. Consequently, materials
with high contents of lignin are in general poorly biodegradable [9]. In fact, the assessment of the
material lignin content may provide a non-biological test method for evaluating biodegradability [1].
During composting, since lignin loss is hardly due to extensive mineralization, one may believe that
the volatile solid fraction associated to lignin and humic like substances can be considered as a
non-biodegradable volatile solid fraction (1-) that should behave as conservative substance
throughout the process. Then, the biodegradability index () can be defined by:
where VS is the amount of biodegradable volatile solid present in the mixture (kg) quantified
according to Eq. (2):
and L represents the lignin and humic like substances content, as % of VS.
In literature few works focused in relating the biodegradability index with the lignin content.
Chandler and co-workers, in 1980, concluded that the lignin content was determinant for substrate
biodegradability in anaerobic conditions according to [1]:
However, since lignin is less inhibitory to substrate decomposition in aerobic conditions, Komilis
(2003) proposed that the correlation between VS degradation during aerobic conditions and the
initial lignin content of the composting mixture can be defined by:
The aim of the present work is to predict the biodegradability of an initial waste mixture and to
investigate how this property determines the changes in organic matter (volatile solids - VS)
characteristics during the composting process. The initial mixtures tested were made from potato
peel industrial waste (PP), grass clippings (GC) and sawdust (SD) in different proportions. These
blends were composted in self heating reactors (SHR) with 120 L of internal volume. The waste
mixtures were sampled in pre-determined times along the period of composting. Biodegradability of
each sample was assessed by measuring lignin content, using the Klason lignin method, which
involves gravimetric measurements after extracting the sample with sulphuric acid solutions to
dissolve out the other components [5].
624
EXPERIMENTAL METHODS
Experimental apparatus and monitoring of composting process

Experiments were performed in a system of four self-heating reactors (SHR) with 120 L of internal
volume (0.7 m high and 0.44 m in diameter) and isolated with a rubber based elastomeric material
(Aeroflex MSR) arranged in parallel. The reactors have a side hole that allowed the entry of
compressed air that is uniformly distributed across a perforated Perspex plate. On the top of the
reactors there are two openings for the introduction of a temperature sensor and to allow the
release of gases generated in biological reactions, as well as the feed air not consumed.
The reactors were equipped with a data acquisition system for on-line monitoring of temperature
and oxygen concentration, and the feed air flow rate was measured with rotameters. In general, the
air flow rate was controlled in order to firstly maintain the oxygen concentration of the outlet gas in
the range of 5 to 15% (v/v) and also to control the temperature of the composting material in the
reactor. The mixtures were sampled in pre-determined times (once a week). To quantify some
parameters such as lignin content, organic matter content and elemental composition,
samples were air-dried and ground to <0.22 mm.
Materials
The components used in the experiments were obtained from different sources and included
potato-peel industrial waste (PP) from a Portuguese industry of potato chips, grass clippings (GC)
from a garden centre and a football stadium, and sawdust (SD). The initial composition of each
mixture tested is shown in Table 1.
Table 1. Composting initial composition mixtures.
Mixture properties
Reactor PP (%w/w) GC (%w/w) SD (%w/w) Volatile solids (%w/w) Lignin content (% VS)
1 53.0 39.8 7.2 90.8 23.9
2 66.0 28.0 6.0 92.3 21.3
3 38.7 53.0 8.3 91.0 25.5
4 34.3 51.6 14.1 88.6 25.6
From the measurement of lignin content of the initial composting mixtures for each reactor, it
was possible to predict the conversion of organic matter that would be obtained if all biodegradable
organic matter was degraded, resulting in the maximum conversion of organic matter (xmax).
Biodegradability of each sample was calculated by Eqs. (1) and (2), and the conversion of organic
matter for each instant t is calculated by Eq. (5).
The lignin content was also monitored throughout the composting process and consequently
the conversion of organic matter in the process (xlignin) was also estimated from this determination
using the approach represented in Eq. (5). Fig. 1 shows the comparison of the conversion of
organic matter obtained experimentally with the conversion measured from the quantification of
lignin in each sampling periods prescribed. It also shows the maximum conversion of organic
matter predicted by using Eqs. (1) and (2) and by the Komilis correlation for each of the reactors.
625
The evolution of the conversion of biodegradable organic matter assessed by measurement of
lignin content, xlignin, is the same observed experimentally by assessing organic matter conversion
(xVs). In the four reactors, it is confirmed that the maximum conversion predicted by the Komilis
correlation is the better estimation of organic matter conversion for the composting period. It is also
shown in Fig.1 that independently of the initial mixture composition, there is an increase in lignin
content that can be related to the decrease of the potential for biodegradation of the tested
mixtures.
100 100
a) b)
80 80
Conversion (%)
Conversion (%)
60 60
40 40
xVS xVS
xlignin xlignin
20 20 xmax
xmax
xmax_komilis
xmax_Komilis
0 0
0 10 20 30 40 50 0 10 20 30 40 50
Time (d) Time (d)

100 100
c) d)
80 80
Conversion (%)
Conversion (%)
60
60
40
40
xVS
xlignin
xmax
xVS
20
xmax_Komilis 20 xlignin
xmax
0 xmax_Komilis
0 10 20 30 40 50 0
0 10 20 30 40 50
Time (d)
Time (d)
Fig.1. Comparison of conversion of organic matter obtained experimentally, XVS, and

by quantification of lignin content in a) reactor 1, b) reactor 2, c) reactor 3, d) in reactor 4.
The initial samples with the lower and higher lignin content showed a greater and smaller mass
reduction, respectively, at the end of composting period. Our results showed that higher lignin
content of an initial mixture led to lower biodegradation of the mixture. It is important to note
that not all biodegradable mass was degraded by the end of the composting period. However, the
remaining biodegradable mass could still be degraded if the compost period was
extended and the conditions for composting, such as moisture, C:N ratio, and aeration were
adequate. The estimation of organic matter conversion by determining lignin content seems to be a
very suitable methodology since the obtained results are consistent with those observed
experimentally. The correlation developed to estimate the potential of biodegradation for anaerobic
degradation processes indicated in Eq.(3), that is often referred in literature, it was not used in this
study, because the values of obtained were too small and even negative, since during
composting, the lignin content of tested mixtures achieves high values (more than 30 % of VS).
626
The conversion of organic matter in the reactor 4 was low, about 36%. This can be justified by the
existence of other not biodegradable materials beside lignin and by the fact that the operation
condition may not be appropriated for the microorganisms activity.
It is important to note that when the conversion of organic matter attained a plateau, the
temperature inside each SHR (results not shown here) was near the ambient temperature, which
means that the processes were in the maturation phase.
CONCLUSIONS
The assessment of biodegradability of organic matter (Eqs. (1) and (2)) by the determination of
lignin content proved to be an appropriate methodology for this purpose since the predictions for
the maximum biodegradation of organic matter were consistent with those obtained
experimentally. The estimation of the maximum biodegradation of organic matter is made
considering that all biodegradable organic matter present in the initial mixture will be degraded. In
practice, as was verified in the experiments, the degradation of biodegradable matter is not
complete, which explains the difference between the percentages of biodegradation estimated from
the determination of lignin and the percentages biodegradation verified experimentally. The great
disadvantage of this methodology is related to the time scale to determine the lignin content in
each sample (approximately 2 days). Reducing the time scale of this process, by optimizing the
time required in each step, is a challenge to be evaluated because it would allow the suitability of
this method in cases of full-scale composting.
REFERENCES
[1] R.T. Haug, The practical handbook of compost engineering, Boca Raton, Florida,1993.
[2] M. Tosin, F. Degli-Innocenti, C. Bastiol, Effect of the composting substrate on biodegradation of

solid materials under controlled composting conditions, Journal of Environmental polymer
Degradation, 4 (1996) 55-63.
[3] Ministry of Agriculture & Food, Resource Management Branch, Abbotsford BC, CANADA. 1996.
[4] N. M. Trautmann, M. E Krasny, Composting in the Classroom, Cornell Waste Management

Institute, USA, (1997).
[5] M. Lpez, O. Huerta-Pujol, F. X. Martnez-Farr, M. Soliva, Approaching compost stability from

Klason lignin modified method: Chemical stability degree for OM and N quality assessment,
Resources, Conservation and Recycling, 55 (2010)171181.
[6] R. Barrena, J. Turet, A.Busquets, M. Farrs, A. Snchez, Respirometric screening of several

types of manure and mixtures intended for composting, Bioresource Technology, (2010).
[7] R. B. Harrison, Composting and Formation of Humic Substances, University of

Washington, USA. (2007).
[8] M. Tuomela, M. Vikman, A. Hatakka, M. Itavaara, Biodegradation of lignin in a compost

environment: a review, Bioresource Technology, 72 (2000)169-183.
[9] D. P. Komilis, R. K. Ham, The effect of lignin and sugars to the aerobic decomposition
of solid wastes, Waste Management, 23 (2003) 419423.
627
DIFFERENTIAL DISTRIBUTION OF CHEMICAL AND ECOTOXICOLOGICAL

LEVELS OF BIOMASS ASHES BY SIZE FRACTIONATION
1 1 1 1
D. Dias , R. Barbosa , N. Lapa and B. Mendes
1 Universidade Nova de Lisboa, Faculdade de Cincias e Tecnologia, Departamento de Cincias
e Tecnologia da Biomassa, Campus da Caparica. 2829-516 Caparica, Portugal.
E-mail: rfb@fct.unl.pt
ABSTRACT
The main aim of this work was to study the chemical and ecotoxicological properties of
different particle size fractions of bottom and fly ashes coming from a biomass power
plant. Bottom and fly ashes were sieved in different size fractions. The size fractions with
higher mass percentages were submitted to an acidic digestion and water leaching. The
acidic samples and eluates were chemically characterized. The eluates were also
submitted to an ecotoxicological characterization. The highest concentrations of metals
and metalloids were found in the lower particle size fractions of bottom and fly ashes. It
was not observed any releasing pattern from the particle size fractions, except in the fly
ashes in which the releasing rate of some earth and alkali-earth metals seemed to
increase in the lower particle size fractions. No specific pattern on the toxicity distribution
through the different particle size fractions of bottom and fly ashes was determined,
except that the particle size fractions of bottom ashes of 4,000-10,000 m and >10,000
m have shown lower toxicity levels than the other particle size fractions.
Keywords: biomass ashes; size fractionation; chemical and ecotoxicological properties
INTRODUCTION
The combustion of forest wastes produces ashes, commonly bottom and fly ashes. The former are
collected in the bottom of the boiler, while the latter is retained in the treatment system of the
gaseous effluents. These two types of ashes have different physical and chemical properties,
depending on the biomass used and on the combustion conditions. Bottom ashes are mainly
constituted by silica, alkali and alkali-earth metals, and heavy metals. Fly ashes present an
average dimension lower than bottom ashes, while the concentration of heavy metals is generally
higher than in bottom ashes [1,2,3]. Studies focusing in both chemical and ecotoxicological
properties of size fractionated biomass ashes are scarce [4,5]. The main aim of this study was to
assess the chemical and ecotoxicological properties of size fractionated biomass ashes. The ashes
were produced during the combustion of forest wastes in a boiler of a pulp and paper industry.
Origin of biomass ashes

The biomass ashes fly and bottom ashes were from a Portuguese biomass boiler of a pulp and
paper industry that produces electricity by burning eucalyptus and pine bark in a Bubbling Fluidized
Bed Combustor (BFBC). Bottom ashes were collected in the bottom of BFBC and fly ashes were
collected in bag filters. Only sand is used in this BFBC as bed material.
Size fractionation
Bottom ashes were sieved by using meshes (Retsch) of 20, 50, 200, 500, 850, 2,000, 4,000 and
10,000 m. Fly ashes were sieved through meshes (Retsch) of 20, 50, 200, 500 and 850 m. A
628
vibratory sieve shaker AS 200 Digit (Retsch) was used (ISO 3310). Only the fractions with a mass
higher than 5% (w/w wb) were selected for further characterization.
Metals bulk content

Particle size fractions were submitted to acidic and alkaline digestions to determine the metals bulk
content. 9 ml of HNO3 and 3 ml of HCl were used to perform the acidic digestion of 0.5 g ashes.
The acidic digestion was carried out in closed vessels in a microwave digester (Milestone, Ethos
1600), for 10 min, with the following digestion cycles: 5:30 min, 500 W, 175C; 4:30 min, 400 W,
175C (USEPA Method 3051A). The digested samples were then filtered with glass fiber filters
(Schleicher & Schuell). The alkaline digestion was performed with a mixture of 20 g NaOH + 30 g
Na2CO3 in 1 L of deionized water (USEPA Method 3060A). The digested samples were then
filtered through 0.45 m membrane filters (Schleicher & Schuell) and the pH value was adjusted to
7.5. The alkaline digested samples were used for Cr VI quantification (US EPA Method 7196A).
Leaching assay, chemical and ecotoxicological characterization of the eluates

Particle size fractions were submitted to a leaching test according to the European standard EN
12457-2. The eluates were characterized for several chemical and ecotoxicological parameters.
The ecotoxicological characterization comprised the following assays: a) Luminescence inhibition
of the bacterium Vibrio fischeri (Azur Environmental Microtox system); b) Mobility inhibition of the
freshwater micro-crustacean Daphnia magna (Daphtoxkit F magna of Microbiotests); c) Mortality
of the marine micro-crustacean Artemia franciscana (Artoxkit M of Microbiotests); d) Growth
inhibition of the freshwater microalgae Selenastrum capricornutum (Algaltoxkit F of
Microbiotests); e) Growth inhibition of the marine microalgae Phaeodactylum tricornutum (Marine
Algaltoxkit of Microbiotests).
Size fractionation
Table 1 shows the particle size distribution of bottom and fly ashes.
Table 1 Particle size distribution of biomass ashes (nd: not determined)

Size fraction Bottom ashes (% w/w db) Fly ashes (% w/w db)
< 20 m 0.001 4.00
2050 m 0.329 48.0
50200 m 2.15 36.3
200500 m 9.24 10.5
500850 m 24.1 1.04
8502000 m 34.9 0.147
20004000 m 10.0 nd
400010000 m 10.8 nd
> 10000 m 8.50 nd
Being constituted by coarse particles, bottom ashes were mainly composed by ashes of 8502000
m (34.9% w/w db), 500850 m (24.1% w/w db), 400010000 m (10.8% w/w db) and 2000
4000 m (10.0% w/w db). These four size fractions comprised 79.8% of the total mass of bottom
ashes. Fly ashes are normally composed by fine particles. In this case, the majority of their mass
was constituted by particles of 2050 m (48.0% w/w db), 50200 m (36.3% w/w db) and 200
500 m (10.5% w/w db). These three particle size fractions comprised 94.8% of the total mass of
fly ashes.
Metals bulk content

Table 2 shows the metals bulk content in bottom ashes.
629
Table 2 Bulk content of metals in bottom ashes (values in mg/kg db)
Ashes 200-500 500-850 850-2000 2000-4000 4000-10,000 >10,000
Element
as-received m m m m m m
As 0.798 1.48 1.67 0.931 0.650 0.643 0.084
Sb 0.186 0.275 0.175 0.165 0.087 0.064 0.027
Se 3.10 4.27 3.41 2.87 1.65 1.54 0.771
Hg <0.470 <0.252 <0.243 <0.242 <0.229 <0.163 <0.098
Cd <12.6 <6.69 <6.44 <6.42 <5.95 <5.11 <2.15
Ni <24.7 <13.2 <12.7 <12.7 <11.7 <10.1 <4.3
Mo <38.4 <20.6 <19.8 <19.6 <18.2 <15.7 <6.58
Zn 30.3 43.3 38.1 27.0 10.1 9.82 5.92
Pb <33.5 <20.9 <20.1 <20.1 <18.6 <16.0 <6.72
Cu <16.1 <8.58 <8.26 <8.23 <7.63 <6.55 <2.75
Ba <62.6 <32.5 <32.1 <32.2 <29.8 <25.6 <10.8
Cr <19.6 <10.5 <10.1 <10.1 <9.30 <7.99 <3.36
Cr VI 0.856 0.513 0.819 0.872 0.418 0.346 0.067
Ca 14,945 17,836 17,226 10,580 6,072 2,377 1,997
Mg 4,627 4,717 4,845 3,159 2,155 914 186
Na 283 231 439 413 339 78 69
K 3,419 4,137 3,016 1,725 1,299 474 243
Fe 3,560 5,349 2,823 2,071 678 1,473 615
Al 3,737 6,815 4,102 3,145 1,837 782 152
Bottom ashes were mainly composed by alkali and alkali-earth metals and trace concentrations of
heavy metals and metalloids. Alkali (Na, K) and alkali-earth elements (Ca, Mg) were the major
components of biomass ashes due to the high concentration of these elements in the forest
biomass. Some of the metals and metalloids determined are also present in forest biomass due to
their role as minor nutrients [6,7,8]. Generally, the highest concentrations of alkali, alkali-earth
metals, heavy metals and metalloids were found in the lowest particle size fractions of 200-500 and
500-800 m.
Table 3 shows the results of bulk content of metals present in fly ashes. Once again, these ashes
were mainly composed by alkali and alkali-earth elements, and vestigial concentrations of heavy
metals and metalloids. Nevertheless, the concentrations of heavy metals were globally higher in fly
ashes than it was determined for bottom ashes. For instance, Pb was quantified in the size
fractions of 20-50 m and 50-200 m, and Cu, Ba and Cr were determined in all size fractions in
concentrations ranging from 8.96 up to 306 mg/kg db. Some trace metals are often released in
volatile forms during combustion, presenting higher concentrations in fly ashes rather than in
bottom ashes [9]. Globally, the highest concentrations of metals were once again determined in the
lowest particle size fraction (20-50 m) and the lowest concentrations were detected in the highest
particle size fraction (200-500 m).
Table 3 Bulk content of metals in fly ashes (values in mg/kg db)

Element Ashes as-received 20-50 m 50-200 m 200-500 m
As 6.27 11.2 5.59 1.99
Sb 0.514 0.967 0.578 0.329
Se 1.61 3.17 0.567 <0.170
Hg <0.503 0.408 0.598 0.477
Cd <13.4 <6.43 <6.44 <5.98
Ni <26.4 <12.7 <12.7 <11.8
Mo <41.1 <19.7 <19.7 <18.3
Zn 142 167 117 54.3
Pb <41.9 61.7 27.9 <18.7
Cu 33.1 47.0 27.5 8.96
630
Table 3 (Cont.)
Element Ashes as-received 20-50 m 50-200 m 200-500 m
Ba 248 306 141 29.9
Cr 48.6 59.0 43.9 10.2
Cr VI 0.687 0.954 0.866 0.513
Ca 43,576 58,550 37,202 7,852
Mg 22,317 28,038 9,888 5,197
Na 1,953 1,957 1,879 530
K 17,529 23,663 14,497 3,752
Fe 17,696 18,561 17,352 8,072
Al 27,913 35,861 27,604 7,890
Chemical characterization of eluates

Tables 4 and 5 show the chemical characterization of eluates of bottom and fly ashes, respectively.
The eluates of both biomass ashes were highly alkaline due to the oxides that are formed during
the combustion process in excess air. All eluates have demonstrated the high mobility of chlorides
and sulfates from bottom and fly ashes, although the mobility of these salts was inversely
proportional to the increase of particle sizes; for both ashes, chlorides have shown a decreasing
mobility with the increase of particle sizes from 200-500 up to >10,000 m, while sulfates have
shown an increasing mobility with the same increase of particle sizes. Nevertheless, due to the
higher concentrations of chlorides than sulfates in the eluates of both ashes, the TDS have shown
a variation similar to chlorides, i.e., a decrease of concentration with the increase of the particle
dimensions although this variation has been more pronounced in fly ashes.
The mobility of alkali and alkali-earth metals, namely Ca, Na and K, from both bottom and fly ashes
was the most evident characteristic of these biomass ashes. No mobility pattern of these metals
from bottom ashes was evident, since they can be highly controlled by the presence of other
chemical species, such as sulfates. In a different way, the release patterns of Ca, K, and in a lower
extent Na, seemed to follow a decreasing rate with the increase of particle sizes of fly ashes. This
is probably due to the lower concentration of controlling chemical releasing species, such as
sulfates, in fly ashes than in bottom ashes.
The eluates of both biomass ashes were characterized by low or undetectable concentrations of
heavy metals and metalloids showing the low content and low mobility of these metals in fly and
bottom ashes. No special mobility pattern from both biomass ashes was possible to define for
these groups of metals, due to the low concentrations detected.
Table 4 (Cont.) Chemical characterization of the eluates of bottom ashes

(DOC: dissolved organic carbon; TDS: total dissolved solids)
(values in mg/kg db, except pH in Sorensen scale and As, Sb and Se in g/kg db)
Ashes 200-500 500-850 850-2000 2000-4000 4000-10,000 >10,000
Parameter
pH 12.3 13.4 13.3 13.4 13.3 13.0 12.0
-
Cl 17,998 18,487 17,027 17,865 14,243 6,782 2,828
2-
SO4 105 90.3 120 101 95.4 1,128 3,040
DOC 48.3 48.7 49.0 45.9 41.2 41.0 34.8
TDS 26,263 31,311 28,238 29,189 29,255 23,301 24,749
As <3.20 <3.21 <3.20 <3.23 <3.21 <3.22 <3.19
Sb 13.3 7.34 19.1 18.4 9.19 4.42 15.8
Se <9.10 <9.13 <9.11 <9.17 <9.14 <9.17 <9.07
Hg <12.0 <12.0 <12.0 <12.1 <12.1 <12.1 <12.0
Cd <0.320 <0.321 <0.320 <0.323 <0.321 <0.322 <0.319
Ni <0.630 <0.632 <0.630 <0.635 <0.633 <0.635 <0.628
Mo 1.98 <0.981 1.55 1.35 1.95 3.03 2.36
Zn <0.130 <0.130 <0.130 <0.131 <0.131 <0.131 <0.130
Pb <1.00 <1.00 <1.00 <1.01 <1.00 <1.01 <1.00
631
Table 4 (Cont.)
Ashes 200-500 500-850 850-2000 2000-4000 4000-10,000 >10,000
Parameter
Cu <0.410 <0.411 <0.410 <0.413 <0.412 <0.413 <0.409
Ba 4.83 5.04 3.63 2.41 <1.61 <1.61 <1.59
Cr <0.500 <0.501 <0.500 <0.504 <0.502 <0.504 <0.498
Cr VI 0.248 0.243 0.220 0.243 0.235 0.259 0.059
Ca 1,303 1,505 789 928 1,429 1,531 1,517
Mg 0.495 0.098 0.064 0.321 0.163 0.452 2.67
Na 13.7 39.9 13.3 24.4 27.7 39.7 34.2
K 104 232 82.5 112 349 276 141
Fe <0.600 <0.602 <0.600 <0.605 <0.603 <0.604 <0.598
Al 3.92 3.82 4.12 4.17 3.90 4.13 13.5
Table 5 Chemical characterization of the eluates of fly ashes

(DOC: dissolved organic carbon; TDS: total dissolved solids)
(values in mg/kg db, except pH in Sorensen scale and As, Sb and Se in g/kg db)
Parameter Ashes as-received 20-50 m 50-200 m 200-500 m
pH 12.3 12.9 12.7 12.2
-
Cl 10,293 11,253 8,773 4,167
2-
SO4 80.2 75.1 80.1 201
DOC 64.6 67.9 54.8 67.0
TDS 28,658 35,385 16,689 8,154
As 8.90 3.41 22.6 9.38
Sb 6.66 6.33 10.9 14.6
Se <9.12 <9.11 <9.12 <9.14
Hg <12.0 <12.0 <12.0 <12.1
Cd <0.321 <0.320 <0.321 <0.321
Ni <0.631 <0.631 <0.631 <0.633
Mo <0.982 2.43 1.52 <0.984
Zn <0.130 <0.130 <0.130 <0.131
Pb <1.00 <1.00 <1.00 <1.00
Cu 0.990 0.992 0.987 0.980
Ba 29.8 37.7 11.3 <1.61
Cr <0.500 <0.501 <0.501 <0.502
Cr VI 0.330 0.467 0.368 0.269
Ca 7,635 9,911 6,052 2,647
Mg 0.175 <0.030 0.047 0.176
Na 338 578 285 366
K 1,132 4,253 1,030 315
Fe <0.601 <0.601 <0.601 <0.603
Al 26.5 5.12 14.6 179
Ecotoxicological characterization of eluates

Table 6 shows the ecotoxicological characterization of eluates. V. fischeri was the most sensitive
biological indicator and A. franciscana the less sensitive for all the eluates. Excluding the bacterium
V. fischeri, the biological indicators coming from marine environments (P. tricornutum and A.
franciscana) have shown lower sensitivity to the toxicity levels of all eluates than the organisms
coming from fresh water environments (S. capricornutum and D. magna). This suggests that some
degree of the toxicity level determined for fresh water organisms may be due to osmotic effect on
these organisms caused by high salt concentration present in eluates. No specific pattern on the
toxicity distribution through the different particle size fractions of bottom and fly ashes was
determined, except that the particle size fractions of bottom ashes of 4,000-10,000 m and
>10,000 m have shown lower toxicity levels than the other particle size fractions. The particle size
fraction >10,000 m was the only fraction that has not shown any toxicity level for all bio-indicators.
632
Table 6 Ecotoxicological characterization of the eluates of bottom and fly ashes (values in %)
V. fischeri S. capricornutum P. tricornutum D. magna A. franciscana
Ashes
EC50-30min EC20-72h EC50-72h EC50-48h EC50-24h
As-received <1.00 5.49 34.4 8.54 81.2
Bottom ashes
200-500 m <1.00 6.97 18.7 5.55 70.1

500-850 m <1.00 18.1 12.3 5.79 67.1
850-2,000 m <1.00 5.23 40.1 6.38 63.5
2,000-4,000 m <1.00 5.38 26.1 8.39 78.5
4,000-10,000 m 2.09 12.9 45.6 19.0 83.4
>10,000 m >99.0 >80.0 >80.0 >95.0 >90.0
As-received <1.00 2.38 25.4 11.6 >90.0
Flyashes
20-50 m <1.00 2.42 30.3 6.80 86.3

50-200 m <1.00 1.52 61.7 13.5 84.5
200-500 m <1.00 1.63 43.4 3.99 >90.0
CONCLUSIONS
The bulk characterization has shown that the ashes were mainly composed by earth and alkali-
earth metals. The concentrations of heavy metals and metalloids were vestigial or undetectable.
The highest concentrations of metals and metalloids were found in the lower particle size fractions
of bottom and fly ashes.
Chlorides, sulfates, Ca, K and, in a lower extent, Na were the main elements leached from all
fractions of bottom and fly ashes. It was not observed any releasing pattern from the particle size
fractions, except in the fly ashes in which the releasing rate of some earth and alkali-earth metals
seemed to increase in the lower particle size fractions.
No specific pattern on the toxicity distribution through the different particle size fractions of bottom
and fly ashes was determined, except that the particle size fractions of bottom ashes of 4,000-
10,000 m and >10,000 m have shown lower toxicity levels than the other particle size fractions.
References
[1] A. Sarkar, R. Rano, Water Holding Capacities of Fly Ashes: Effect of Size Fractionation, Energy
Sources Part A - Recovery Utilization and Environmental Effects, 29 (2007) 471-482.
[2] I. Obernberger, F. Biedermann, W. Widmann, R. Riedl, Concentrations of inorganic elements in
biomass fuels and recovery in the different ash fractions, Biomass and Bioenergy 12 (1997) 211-
224.
[3] M.C. Camerani, B.M. Steenari, R. Sharma, R. Beckett, Cd speciation in biomass fly ash
particles after size separation by centrifugal SPLITT, Fuel 81 (2002) 1739-1753.
[4] R. Poykio, H. Nurmesniemi, R.L. Keiski, Total and size fractionated concentrations of metals in
combustion ash from forest residues and peat, Proceedings of the Estonian Academy of Sciences
58 (2009) 247-254.
[5] O. Dahl, H. Nurmesniemi, R. Pyki, G. Watkins, Heavy metal concentrations in bottom ash and
fly ash fractions from a large-sized (246 MW) fluidized bed boiler with respect to their Finnish forest
fertilizer limit values, Fuel Proc. Technology 91 (2010) 1634-1639.
[6] O. Dahl, H. Nurmesniemi, R. Pyki, G. Watkins, Comparison of the characteristics of bottom
ash and fly ash from a medium-size (32 MW) municipal district heating plant incinerating forest
residues and peat in a fluidized-bed boiler, Fuel Proc. Technology, 90 (2009) 871-878.
[7] S. Singh, L. Ram, R. Masto, S. Verma, A comparative evaluation of minerals and trace
elements in the ashes from lignite, coal refuse, and biomass fired power plants, Intern. J. Coal
Geology, 87 (2011) 112-120.
[8] B.M. Steenari, S. Schelander, O. Lindqvist, Chemical and leaching characteristics of ash from
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ash and the influence of ash agglomeration, Biomass and Bioenergy, 16 (1999) 119-136.
633
RECYCLING PRINTERS FOR EDUCATIONAL PURPOSES

1 2 3 4
S. Shahidian , R.P.Serralheiro , J.M.Serrano and R.M.Machado
1 ICAAM, Universidade de vora, Apt.94, Ncleo de Mitra, shakib@uevora.pt
2 ICAAM, Universidade de vora, Apt.94, Ncleo de Mitra, ricardo@uevora.pt
3 ICAAM, Universidade de vora, Apt.94, Ncleo de Mitra, jmrs@uevora.pt
4 ICAAM, Universidade de vora, Apt.94, Ncleo de Mitra, rmam@uevora.pt
ABSTRACT
A large number of printers are discarded annually, most of which either end up in land-
fills, or are shredded and melted for recovery of the metallic components. At the
University of vora, Portugal, a new approach has been developed since 2007: old
printers are dismantled and the parts are used in electronics and automation classes,
protecting the environment and helping to reduce the annual cost of running the
laboratory classes. One of the most widely available printers is the HP 600 series that
was manufactured between 1994 and 2000. Each printer, once dismantled, can provide
various useful components for electronic classes, including: 2 step motors, one 12V
motor complete with gear-head and trolley, a LM35DZ precision thermometer, one
contact relay, one infra-red switch, two LDRs and one high quality LPT cable that can be
used in automation developments, using the PCs LPT port. The four years of experience
have shown that the students are more than willing to take the time to dismantle the
equipment and carefully extract the components. With the proper tools, two students can
dismantle a printer and remove the parts in less than 15 minutes. This paper presents the
individual components that can be removed and provides sample circuits and uses for the
parts in electronic and automation laboratory classes.
Keywords: Printer recycling, printer dismantling, teaching electronics
INTRODUCTION
The volume of end-of-life electronic waste is increasing rapidly. In 2010, more than 125 million
printers were shipped globally, of which over 52 million were hp brand [1]. This is a 12% increase
compared to the 2009 volume, and this number is expected to increase annually. Assuming an
average weight of 5kg per unit, this represents a total of 750 000 tons of electronic waste that need
to be recycled annually. The conventional recycling process, in use today, consists of shredding
the equipment to small parts, and using the physical and chemical properties of the individual
materials for separating them. The output of this bulk recycling process of electronics is ferrous
metals, mixed metals, glass, mixed plastics and mixed materials. Each batch is then sold for further
processing.
Metals comprise 57 percent of the total amount of electronic scrap [2], and thus many recycling
processes focus primarily on recovery of precious metals. The metals used are primarily iron, cast
iron, stainless steel and other steel alloys, aluminum and aluminum alloys, copper alloys, lead, and
zinc. Reuse of these materials can reduce the costs of constructing new systems. Some
components, such as gold and copper, are valuable enough to be reclaimed in their own right.
Plastic materials represent 19 percent of the total electronic scrap [2]. One of the problems with
plastics recycling and recovery is the difficulty in sorting the parts by type. Because of the
incompatibility of various plastics, the parts disassembled from old products must be identified and
sorted into separate different types of plastic. It is more difficult to find a market for co-mingled
plastics, than for single resin materials, and they have a lower market value. Plastic re-processors
634
pay appropriately for consistent and clean, quality recycled material which has been granulated to
a designated specification. Less than 1% of the plastics from end-of-life electronics are actually
processed for plastics-to-plastics recycling [3].
Printer recycling
HP, the worlds largest electronics company started a global Hardware Return and Recycling
Program, in 1998, as part of its Planet Partners Program, which was hailed as the most
comprehensive hardware return program worldwide [4]. In this program the equipment is ground
into small pieces and subsequently separated into its component parts (steel, aluminum, copper,
plastic, etc). Once separated, these materials are sent to specialty recyclers or used for energy
recovery. Greenpeace visited many recycling facilities in China and India where local and imported
end-of-life electronic equipment are recycled, and observed that substantial quantities of toxic
heavy metals and organic compounds were released into the workplace and the environment [5].
Dismantling vs. conventional shredding

Ideally, the goal of recycling is to generate material that is no different from virgin material,
economically. However, in the manufacturing and assembly process the virgin material is inevitably
combined with a variety of different materials, and in a sense, becomes impure. A product
composed of a single material provides the highest recycling yield, since the impurity levels are
very low.
A level of high impurity in recycled materials is one of the most common obstacles to more
widespread recycling. The level of purity determines the quality of the recycled material and its
market price. Dismantling is the ideal process for maintaining the purity of the raw material. This
process is generally perceived as uneconomical and labor intensive, but with the existing high
unemployment rate, and considering the environmental impact and hazards of the alternatives, it is
becoming more and more feasible and a means of providing employment in depressed regions.
A research conducted at the University of Massachusetts evaluated the cost of dismantling the
electronic wastes stream of the institute. It found that dismantling one ton of electronics
represented 19.1 hours of labor, plus an additional 2.4 hours, for loading and unloading the
materials. The study indicated that the University could earn an estimated $175 per ton of
processed material, assuming a labor cost of $6.25 per hour.
OBJECTIVES
With the renewed focus on automation and electronics in agricultural sciences, the curricula of the
Bachelors and Masters Programs at the University of vora now include subjects on automation,
electronics and data acquisition. In order to provide the students with the equipment and material
needed for their learning process a new approach has been successfully used: Old printers are
dismantled by the students and the parts are used in class to develop the proposed projects. This
has helped reduce the environmental footprint of the classes, and the total cost of running the
laboratory classes.
There are an estimated 2000 printers on duty at the University of vora, with a life expectancy of
five years. This translates into an annual stream of 400 decommissioned printers that are available,
free of charge. One of the most widely available and useful printers is the HP 600 series that was
manufactured between 1994 and 2000.
This study presents the results of four years of experiment with dismantling and recycling of the
printers, describes the recovered parts and some uses for them in teaching electronics.
Additionally, it describes how this dismantling program has helped the general recycling process of
the printers.
RESULTS
Each group of two students is offered a set of equipment including a microcontroller, voltmeter, 12V
battery, solar panel and miscellaneous tools and parts. Additionally, it receives an end-of-life printer
to dismantle for additional parts. The students are able to completely dismantle the printer and
635
separate the components, by material in less than 15 min. The 72 individual parts of a dismantled
printer are presented in Fig. 1. Table 1 presents the weight and material type of these components.
It should be noted that once the re-usable components are removed, practically all the remaining
components can be separated into single composition material, ready for recycling and mixture
with virgin materials. Each printer is 5000 g, of which only some 500g need further separation
before recycling.
Figure 1. Overview of the component parts of an HP 600 series printer
The main reusable components are two step motors, one 12V motor complete with gear-head and
trolley, a LM35DZ precision thermometer, one contact relay, one photo-diode/photo-sensor switch,
two LDRs, and one high quality LPT cable. A market survey of component suppliers reveals that
the total cost of purchasing these recovered components is around 70 (Table 2).
Table 1. Components of an HP 600 series printer by weight and material type.

Weight, g Material Destination
Reusable components
PM55L Motor 219.2 Ferreous metals Reuse
PM35L motor assembly 180.7 Ferreous metals Reuse
C2162-6006 Motor 221.1 Ferreous metals Reuse
Sensor Assembly 11.4 Misc. electronic Reuse
Stripe + sensor 10.9 Misc. electronic Reuse
LPT cable Copper and PE Reuse
Ferreous components
Bottom plate 1136.2 Alloy Recycle
Stainless Steel parts 415.2 Stainless steel Recycle
Back plate 174.6 Alloy Recycle
Plastic components
Misc. Black Plastic 134.7 PC 30GF Recycle
Inner beige plastic frame 411.4 PC 20GF Recycle
Beige plastic outer shell 1559.6 Policarbonate - PC Recycle
Roller Assembly 266.9 PC, rubber Shred and recycle
Electronics
PCB 146 Misc. electronic Shred and recycle
Other
Misc. Plastic and metal parts 46.5 Misc. plastic and metal Shred and recycle
Total 4934.9
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Four years of experience have shown that the students are eager and willing to take the time and
dismantle the equipment in order to recover the parts for their projects. Additionally, they make the
extra effort to dismantle and separate the remaining components, based on material and the
markings on the plastics, thus obtaining batches of pure recyclable material.
Table 2. Market value of the recovered components
Component Bulk price, (100 units) Supplier

NMB PM55L bipolar stepper motor 27.40 Digi-Key
NMB PM35L bipolar stepper motor 22.80 Digi-Key
LM35DZ thermometer 0.76 Farnell
C2162-6006 Motor 12.50 Digi-Key
Omron D2F-01FL snap switch 1.82 Mouser
Photo-diode/ photo-sensor pairs 1.75 inmotion
LPT cable 2.00 Local computer shop
Total 69.03
Reusing valuable parts and subsystems

The sensor board provides three very useful sensors for teaching electronics: a high precision
LM35 thermometer, a contact relay and a photo-diode/photo-sensor pair. The electric circuit of the
board is presented in Fig.2. The board can be either used directly or the sensors can be removed
and used individually.
Figure 2. Electric circuit of the C2162 sensor board, used in the HP 500 and 600 series.
LM35DZ
The LM35 series is an integrated circuit high precision thermometer, with a 0.4C precision. The
DZ provides linear voltage to temperature output, which makes it ideal for quick implementation in
the classroom. It provides a gain of 0.01 V per C, which facilitates temperature reading with the
ADC incorporated in the AVR microprocessors.
One of the first class projects is to make a digital thermometer using the LM35 thermometer. An
LCD and a microcontroller are the only two other components necessary for this project. Fig. 3
shows a digital thermometer that was built using the printer sensor board. It is possible to add
many functions, using the two switches, such as a function that shows the average temperature
when the switch lever is pressed.
Infra-red Switch
Another very interesting component of the sensor board is an optical switch with photo-transistor
output which is used by the printer to detect incoming paper. It is made of a LED emitter at near-
infrared (850-940nm), and a sensor. An infra-red beam crosses the opening, and if it is interrupted
by an object the output current is changed.
637
Figure 3. Digital Thermometer made with an HP 600 printer sensor board.
Omron subminiature basic switch

Hp has installed a microvoltage low-force switch to detect the opening of the printer lid. It is
assembled on the sensor board, but can be easily pulled off. In class it is used as a general-
purpose switch, as well as for control, in automation.
Step motors
The most expensive parts provided by the printer are two unipolar step-motors: The PM55L and
the PM35L permanent magnet motors made by NMB. These are precision step motors that can be
used in robotics and automation, since they can position the head with great precision. In the HP
600 series printers the PM35L is used for cleaning the printing head, and comes assembled with
an elevator that provides an up and down movement. This is very useful in visualizing and
implementing step-motor control, in real-world conditions, enhancing the learning experience of the
students. A Darlington pair array, such as the UNL2003A, can be used to easily control the step-
motors with a TTL signal from the microcontroller. The PM55L is the paper feed motor for the
printer, and is a very powerful 1A step-motor.
DC Motor
HP uses a Mabuchi motor for the carriage drive. This is a 24V DC motor with a high initial torque
(1.83 kg-cm) that rapidly moves the print cartridges during printing. In class, the whole printer
cartridge assembly is used by the students to build automatic gates. This is an excellent exercise,
as it implies implementing timing and conditional routines in the programming.
LPT Cable
The LPT cable provides an easy method for using a computer to control electric equipment. The
LPT1 port supplies a 5V current through each of the 8 wires, and this signal can be used to operate
a 5V relay, such as the Finder 40.52. A simple program, created in an appropriate language, such
as QBasic, can turn the relay on or off through the OUT &H378, 255 command. Eight different
electric devices can be controlled through this cable.
CONCLUSIONS
Four years of experience have shown that the students are more than willing to take the time and
dismantle electronic equipment for component recovery and as part of their learning process. From
each printer the students are able to retrieve useful motors, sensors and cables worth an estimated
70, at bulk price. These components provided resources for creating various automation and
robotics experiments in the classroom.
638
Figure 4. Use of the PM35L stepmotor and its elevator assembly. A UNL2003A chip is used to
interface with the microcontroller.
The students are also willing to make the extra effort to dismantle and separate the remaining
components, based on the material and the markings on the plastics. This has resulted in
separation of 4500 g of pure recycled material per printer, in addition to the useful recovered
components. The experience has also served to further awaken the environmental concern of the
students, with many of them bringing their own end-of-life equipment for dismantling to the
university. Others have asked advice on how to use end-of-life equipment to implement simple
automation systems on their own.
Analysis of the parts and the design of these printers reiterates the need for manufacturers to
develop and design clean products with longer life-spans, that are safe and easy to repair, upgrade
and recycle. In this particular case, the way the parts are intermixed, the screw types and the
difficulty in accessing the inside of the printer clearly indicate a deliberate effort at discouraging
repair and maintenance by the end user. This seems contradictory to the various environmentally
concerned programs setup by HP, to encourage end-of-life recycling. Additionally, the current
policy of most printer makers, to sell their printers at little more than the cost of the ink cartridges,
also encourages frequent renewing of the equipment and the ensuing environmental impact.
REFERENCES
[1] J. Bienvenu. U.S. and Worldwide production color printer 2011-2015 forcast and 2010 vender
shares. IDC Doc#229205. 2011.
[2] S. Klatt, Recycling personal computers, in. Computers and the environment: Understanding and
Managing their Impacts. Edited by Kuehr and Williams, pp 211-229. Kluwer Academic
Publishers. 2003.
[3] P.S. Dillon, E.N. Aqua, Recycling Market Development for Engineering Thermoplastics from
Used Electronic Equipment; Technical Report 20; Chelsea Center for Recycling and
Economic Development, University of Massachusetts: Lowell, MA, 2000.
[4] A. Degher , HPs worldwide take back and recycling programs: lessons on improving program
implementation. International Symposium on Electronics and the Environment. p.224-227.
10.1109/ISEE.2002.1003270 . 2002.
[5] K. Brigden, I. Labunska, D. Santillo, M. Allsopp, Recycling of electronic wastes in China and
India: workplace and environmental contamination. Greenpeace Research Laboratories.
Technical Note: 09/2005. 2005.
639
PHYSICO-CHEMICAL PROPERTIES AND ADSORPTION CHARACTERISTICS

OF CHARS PRODUCED IN THE CO-PYROLYSIS OF BIOMASS, PLASTIC
AND TIRE WASTES
1 1 1 1 2
M. Bernardo , N. Lapa , M. Gonalves , B. Mendes and F. Pinto
1 Universidade Nova de Lisboa, Faculdade de Cincias e Tecnologia, Departamento de Cincias e
Tecnologia da Biomassa, - 2829-516 Caparica, Portugal, maria.b@fct.unl.pt
2 Laboratrio Nacional de Energia e Geologia, Unidade de Emisses Zero, 1649-038 Lisboa,
Portugal, filomena.pinto@lneg.pt
ABSTRACT
The present work aims to perform a multistep upgrading of chars obtained during the co-
pyrolysis of plastics, biomass and tire wastes and evaluate the quality of the upgraded
chars by measuring some of their physico-chemical and textural properties.
The chars were submitted to a sequential solvent extraction with organic solvents of
increasing polarity followed by a heat treatment and finally the char samples were
subjected to an acidic demineralization procedure in order to reduce the ash content.
The quality of the upgraded char was evaluated by measuring both the iodine and
methylene blue numbers and by the estimation of the surface area, pore volume and pore
size parameters.
The results showed that the acid treatment is complementary of the solvent
decontamination in the upgrading of pyrolysis chars. The upgraded char reveals itself as
a mesoporous material having sufficient quality to be reused as adsorbent or as
precursor for high value activated carbon.
Keywords: wastes, pyrolysis chars, textural characterization, adsorption
INTRODUCTION
The interest in the recovery and upgrading of wastes such as plastics, biomass and used tyres is
growing since high amounts of these wastes are presently produced [1-3].
Pyrolysis is a thermochemical process that allows the chemical and energetic valorization of these
wastes, thus reducing the negative environmental impacts of their disposal in landfills or
incineration.
The products recovered by a typical pyrolysis process are oils rich in compounds with chemical and
energetic interest, gases with a relatively high heating value and a solid, named as pyrolytic char
that can be used as a valuable carbon material [4]. This solid char also contains almost all the
inorganic compounds present in the raw wastes and a significant amount of the condensed by-
products formed during the pyrolysis process which are distributed within the char porous structure.
Upgrading is a necessary step that converts the pyrolytic char in carbon materials with interesting
properties of porosity, surface area and pore structures. Therefore, this upgraded char becomes an
attractive by-product with industrial applications such as the production of activated carbon, a high
value product useful as a sorbent for air pollution control or wastewater treatment [5].
The main aim of this study was to perform an efficient upgrading of chars obtained during the co-
pyrolysis of plastics, biomass and tire wastes and a physico-chemical characterization of the
upgraded chars in order to evaluate their performance as adsorbents or precursors of high-quality
activated carbon.
640
EXPERIMENTAL PART
Pyrolysis experiments
The chars were obtained in the co-pyrolysis of a waste mixture composed of 30% (w/w) pine
biomass, 30% (w/w) used tires and 40% (w/w) plastic wastes (mixture of polyethylene,
polypropylene and polystyrene). Pyrolysis experiments were conducted in a batch reactor of 1 L, at
a temperature of 420 C, during 15 min, with an initial nitrogen pressure of 0.41 MPa.
More information about the pyrolysis installation can be found in previous papers [6, 7].
Upgrading of the pyrolysis chars

The chars obtained in the pyrolysis experiment were a carbonized particulate residue impregnated
with the pyrolysis oil. In order to remove and recovery these pyrolysis liquid products that were
trapped in the raw chars, a sequential solvent extraction was performed: extraction with hexane
followed by extraction with a mixture of 1:1 (v:v) hexane:acetone and a final extraction with
acetone. The solvent extractions were performed using the Soxhlet method adapted from the EPA
3540C Method [8].
The extracted chars were then heated in a muffle furnace at a temperature of 350C during 2
hours. This heat treatment aimed at an ultimate removal of semi-volatile organic matter and
pyrolytic carbon deposits that remained after the solvent extraction and that can obstruct the char
pores.
Finally, the chars were submitted to a demineralization procedure in order to decrease the ash
content: the char samples were treated with 1M HCl at 60C during 60min, with continuous stirring
in two successive washing stages. The acid to char ratio was of 100ml/g. At the end of the acidic
washing steps, the mixtures were allowed to settle and then filtrated to separate the pyrolytic char
which was washed several times with deionized water to remove residual acid and solubilize salts.
The washed samples were oven-dried at 110C, for 24h. The char submitted to the heat and
demineralization treatment is named in this work as upgraded pyrolysis char.
Physico-chemical characterization of pyrolysis chars

Proximate analysis was carried out in the char samples by measuring the progressive weight loss
associated with the combustion of samples, in a muffle furnace, from room temperature up to
750C with increments of 50C, remaining 10min at each temperature stage.
Ultimate analysis was performed with a LECO elemental analyzer. Carbon, hydrogen and nitrogen
were determined according the ASTM D5373 standard [9]. Sulfur determination followed the ASTM
D4239 standard [10].
The chars were submitted to a microwave acidic digestion with aqua regia in closed PTFE vessels
in order to determine the zinc content using a Thermo Elemental Solaar Atomic Absorption
Spectrometer (AAS).The amount of zinc leached in the two successive acidic washing steps was
also monitored by using AAS.
Textural and adsorption properties of pyrolysis chars

Iodine number was determined in the improved char according to the standard test method ASTM
D4607 [11]. Iodine number may be used as an approximation of surface area and gives an
estimation of microporosity.
To assess the removal capacity of moderate size pollutant molecules by the upgraded pyrolysis
char, the methylene blue test was performed [12]. It involves the addition of a standard methylene
blue solution to a sample of pyrolytic char until no further color reduction occurs. Like the iodine
number, it provides an indication of the adsorption potential of the carbon giving an estimation of
surface areas.
The chars obtained were also characterized by adsorption of N2 at 77K using an ASAP 2010
Micromeritics apparatus. Adsorption measurements were made after outgassing under vacuum for
at least 3h at 300C. Surface area, pore volume and pore size were some of the textural
parameters determined.

Bernardo et al. [13] have previously demonstrated that the chars obtained in the co-pyrolysis of
plastics, biomass and tire wastes have to be submitted to an organic decontamination in order to
641
reduce their toxicity. These authors conclude that a sequential extraction with solvents of
increasing polarity can provide a better decontamination of the pyrolysis char than an individual
extraction. Therefore, a sequential extraction of hexane, mixture of 1:1 (v/v) hexane:acetone and
acetone was performed in this work with the aim of achieving a higher extraction yield. The results
concerning the organic extraction are presented in Table 1. The global extraction yield of the
sequential extraction was of 66.0%.
Table 1. Extraction yields of the sequential extractions of the pyrolysis char with different organic
solvents.
Extract yield
Extraction step Extraction solvent
(% g/g sample)
1 Hexane 58.1
2 Hexane:Acetone (1:1 v/v) 17.2
3 Acetone 1.9
The extraction yields obtained in the different extraction steps show that more than 50% of the
condensed organic products present in the char are non polar and therefore soluble in pure
hexane. Only a residual amount of 1.9% is polar enough to resist the extraction with
hexane:acetone (1:1 v/v), being recovered with pure acetone.
Physico-chemical characterization of pyrolysis chars

Table 2 presents the results concerning the proximate and ultimate analysis of the char obtained
after the solvent extractions and after the improvement treatment. It was considered that volatiles
were the compounds lost at temperatures up to 200 C; the weight loss registered between 200C
and 350C was attributed to semi-volatile compounds while the weight decrease observed from
350 C to 650 C was assigned to losses of heavy organic compounds (fixed carbon). The residue
non-combusted above 650 C presented a stable residual weight, is considered to be mainly
composed of inorganic matter and is designated by ashes.
From the results obtained, it can be observed that the char obtained after the sequential solvent
extraction still contains a significant amount of semi-volatile compounds. In fact, the authors had
demonstrated before [13] that the extraction of these types of pyrolysis chars with organic solvents
is efficient in the removal of volatile matter, but not so much in the elimination of semi-volatile
matter. Therefore, the heat treatment at 350C during 2h applied to the extracted chars allowed to
decrease the semi-volatile content from 12.4% to 4.82%. Consequently, this heat treatment leads
to a relative increase of the fixed carbon.
Results concerning the ultimate analysis are also shown in Table 2. The upgraded char presents a
sulphur content of 0.44%. Sulphur comes from the tires waste as a result of the vulcanisation
process and the presence of this element in the char indicates that some of the metals might have
formed sulphides that were then incorporated into the char [14]. The sum of C, H, N and S contents
represents approximately 82% of the total mass, indicating that the char has an oxygen content of
about 18%. This high content of oxygen was originated from the pine biomass residue and could
have some influence on the chemical surface of the char, improving the adsorption of polar
molecules.
Table 2. Proximate and ultimate analysis of the solvent extracted char and of the upgraded char.
Semi- Fixed
Volatiles Ashes C H N S
Material volatiles carbon
(% w/w) (% w/w) (% w/w) (% w/w) (% w/w) (% w/w)
(% w/w) (% w/w)
Extracted
2.62 12.4 81.3 3.66 - - - -
char
Upgraded
2.23 4.82 91.8 1.11 79.0 1.80 1.00 0.44
char
642
The most abundant metal in the ashes (>60%) from the char organically extracted is zinc. Zinc
oxide is added to tires as an activator during the vulcanizing process so the amount of zinc in the
pyrolysis char can reach values in the g/kg range [13] that are not compatible with the safe
reutilization of the pyrolysis char by-product. Therefore, the pyrolysis char previously extracted and
heat treated was submitted to a two-step sequential acid demineralization procedure in order to
reduce the ash content and in particular the zinc content. Zinc, being the major component of the
char ash, was used as control element in the char washing study.
Fig.1 shows the concentrations of zinc in the char before and after the demineralization procedure.
A removal efficiency of 88.3% was achieved showing that hydrochloric acid is capable of reducing
the inorganic components of the char in a large extent. Different inorganic species could be
removed with different efficiencies, but a reduction of the ash content from 3.66% to 1.11% was
observed which shows that the majority of the inorganic components were significantly removed
with this procedure.
Fig.1. Zinc content in the pyrolysis char before and after the two-step acidic washing.
The high heating value of the upgraded char can be estimated using the results from the proximate
and ultimate analysis according to the Eq. 1 proposed by Channiwala [15]:
HHV (in kJ/g) = 0.3491C + 1.1783H - 0.1034O - 0.0211Ashes + 0.1005S - 0.0151N (Eq.1)
The calculated high heating value of 27.8 kJ/g indicates that this material has a calorific value
comparable to other fuels [16] making its combustion an attractive alternative.
Textural and adsorption properties of pyrolysis chars

Table 3 presents the results concerning the textural characterization and adsorption properties of
the upgraded char. In addition, the N2 adsorption-desorption isotherm at 77 K is plotted in Fig.2
The results obtained clearly indicate that the upgraded char is mainly a mesoporous material given
the low BET surface area, the low micropore area and the average pore diameter (Mesopores are
in the range of 2-50 nm).
Fig. 2 shows that N2 adsorption-desorption isotherm is of type II since there is an inflection in the
region of low pressure, a certain slope at intermediate pressure and another inflection at high
pressure followed by a marked increase of the adsorption. This type of isotherm describes
adsorption in mixed situations of micropores and open surfaces.
643
Table 3. Textural characterization, iodine and methylene blue number of the upgraded char.
Micropore Total pore Micropore Average pore Iodine Methylene

SBET
Material 2 area volume volume diameter number blue number
(m /g) 2 3 3
(m /g) (cm /g) (cm /g) (nm) (mg/g) (mg/g)
Upgraded
91.4 17.9 0.363 0.009 15.9 68.2 13.8
char
Iodine number is underestimated when compared to the surface area evaluated from the N2
2
adsorption-desorption isotherm (91.4 m /g) which was somehow expected since this parameter is
commonly used as a rough estimate of the surface area of carbon adsorbents. Nevertheless, it is a
relative indicator of porosity and adsorption capacity and a valuable parameter to be used in
preliminary studies.
The methylene blue number obtained is comparable or higher than those obtained for several
types of activated carbon prepared from different precursors [17].
Fig 2. Nitrogen adsorption-desorption isotherms at 77 K of the improved char.
CONCLUSIONS
A significant amount of char by-product can be obtained from the co-pyrolysis of biomass, plastics
and tire wastes. To justify the cost and viability of the pyrolysis process, the pyrolytic char has to be
valorized as are the gaseous and liquid products. The pyrolytic char has to be upgraded in order to
gain sufficient quality to be reused for energy recovery by combustion or as raw material to develop
higher value activated carbon.
644
In this work an improvement treatment was carried out to obtain a carbon material that can be used
as precursor for the development of adsorbents. The char obtained reveals itself as a mesoporous
material, thus it can be used for several purposes (catalysis, bulky molecular wastes adsorption,
etc). Also, the aqueous adsorption of heavy metals should be tested with this carbon since the
presence of oxygen and sulphur in the char surface can give interesting adsorption properties for
inorganic contaminants.
It should be stressed that no activation treatment was performed in the char. High quality activated
carbon with higher surface areas and microporosity characteristics can surely be obtained with an
activation treatment.
References
[1] PlasticsEurope - Association of Plastic Manufacturers in Europe, Plastics the Facts 2010.
An analysis of European plastics production, demand and recovery for 2009, Available on
the internet at: http://www.plasticseurope.org, last accessed July 2011.
[2] European tyre and rubber manufacturers association (ETRMA), End of life tyres - A
valuable resource with growing potential - 2007 edition, Available at: http://www.etrma.org,
last accessed July 2011.
[3] AEBIOM European Biomass Association, Biomass statistics, Available on the internet at:
http://www.aebiom.org, last accessed July 2011.
[4] J. M. Dias, M. C.M. Alvim-Ferraz, M. F. Almeida, J. Rivera-Utrilla and M. Snchez-Polo,
Waste materials for activated carbon preparation and its use in aqueous-phase treatment: A
review, J. Environ. Manage., 85 (2007) 833846.
[5] H. Marsh and F. Rodrguez-Reinoso, Activated carbon, first ed., Elsevier Science &
Technology Books, 2006
[6] F. Pinto, P. Costa, I. Gulyurtlu and I. Cabrita, Pyrolysis of plastic wastes. 1. Effect of plastic
waste composition on product yield, J. Anal. Appl. Pyrolysis., 51 (1999) 3955.
[7] M. Bernardo, N. Lapa, M. Gonalves, R. Barbosa, B. Mendes, F. Pinto and I. Gulyurtlu,
Toxicity of char residues produced in the co-pyrolysis of different wastes, Waste Manage., 30
(2010) 628635.
[8] United States Environmental Protection Agency (USEPA), SW-846 Test Methods for
Evaluating Solid Wastes. Physical/Chemical Methods. Method 3540C Soxhlet Extraction,
USA, December 1996.
[9] Annual Book of ASTM Standards, Vol 05.06. ASTM D5373 - Standard Test Methods for
Instrumental Determination of Carbon, Hydrogen, and Nitrogen in Laboratory Samples of
Coal and Coke, USA, 2002 edition.
[10] Annual Book of ASTM Standards, Vol 05.06. ASTM D4239 - Standard Test Methods for
Sulfur in the Analysis Sample of Coal and Coke Using High-Temperature Tube Furnace
Combustion Methods, USA, 2002 edition.
[11] Annual Book of ASTM Standards, Vol 15.01. ASTM D4607 - Standard Test Method for
Determination of Iodine Number of Activated Carbon, USA, 1994 edition.
[12] CEFIC - European Council of Chemical Manufacturers' Federations, Test methods for
activated carbon, 1986.
[13] M. Bernardo, M. Gonalves, N. Lapa, R. Barbosa, B. Mendes, F. Pinto, Characterization of
chars produced in the co-pyrolysis of different wastes: decontamination study, J. Hazard.
Mater., (2011), doi: 10.1016/j.jhazmat.2011.07.115.
[14] A. Mastral, R. lvarez, M. Calln, C. Clemente and R. Murillo, Characterization of chars from
coal-tire copyrolysis, Ind. Eng. Chem. Res., 38 (1999) 2856-2860.
[15] S. A. Channiwala, On Biomass Gasification Process and Technology Development - some
Analytical and Experimental Investigations, Ph.D. thesis, IIT Bombay, Mumbai (1992)
[16] S. Gaur and T.B. Read, Thermal Data for Natural and Synthetic Fuels, Marcel Dekker Inc,
New York, 1998.
[17] M. Rafatullaha, O. Sulaimana, R. Hashima, A. Ahmadb, Adsorption of methylene blue on
low-cost adsorbents: A review, J. Hazard. Mater., 177 (2010) 7080.
645
14th September
Keynote Lecture III

( Landfill leachate treatment where lies the solution? )
Rosrio Oliveira
646
Prof. Rosrio Oliveira [IBB Institute for Biotechnology and Bioengineering, Centre of
Biological Engineering, University of Minho, Portugal]
Biography
ROSRIO OLIVEIRA is full professor at the Department of Biological Engineering of the

University of Minho. She is the head of the master degree in Environmental Management and
head of the Biofilm research group. Her main research interests are in Biofilm Science and
Engineering and Solid Waste Treatment.
647
St
LANDFILL LEACHATE TREATMENT WHERE LIES THE SOLUTION?
Oliveira R., Cortez, S., Teixeira, P. and Mota,M.

IBB Institute for Biotechnology and Bioengineering, Centre of Biological Engineering, University of Minho,
Campus de Gualtar, 4710 057 Braga, Portugal
a
email: roliveira@deb.uminho.pt
ABSTRACT
As society and technology has developed, an increasing amount of municipal solid waste (MSW) along with
industrial and agricultural waste has been generated and the management of waste became a very organized,
specialized and complex activity. The huge amounts of waste produced every day have several detrimental
impacts of great concern, where the depletion of natural resources is one of the most important. Although several
countries have been introducing more stringent laws to reduce the amount of waste to be landfilled, in an attempt
to maximize recycling and materials recovery, landfilling is still the most generalized practice for MSW treatment.
Thus, the treatment of the high polluted waters leaching from landfills constitutes an important burden in landfill
management. The selection and design of the management and treatment of a landfill leachate has to take into
consideration factors such as leachate characteristics, effluent discharge alternatives, technological options, final
discharge requirements and economical aspects.
The alteration in leachate characteristics with the increasing age of the landfill enhances the difficulty in the design
of the treatment system. Generally, a young leachate presents weak to strongly acidic pH, high COD and TOC
concentrations and high biodegradability (BOD5/COD ratio in the range 0.4-0.7). A mature leachate (<10 years) is
characterized by a high strength of ammonium nitrogen, a moderate strength in COD, low concentrations of heavy
metals and a low BOD5/COD ratio (most often close to 0.1) [1]. Typically, most of the organic materials present in
the mature leachate have a high molecular weight and are recalcitrant compounds such as humic- and fulvic-like
acids.
The leachate treatment system must be flexible enough to produce the same effluent quality despite the aging of
the leachate and sudden and large variations in the leachate strength and volume. Accordingly, several solutions
have been implemented. Constructed wetlands were an attractive alternative but the increase in land cost and
unavailability has directed the attention to other biological treatments, which have been shown to be very effective
for the treatment of easily biodegradable young leachates becoming less effective with time. Therefore, several
physico-chemical processes have been developed and, currently, the treatment systems used for leachate
treatment include biological, physico-chemical and combinations of these processes. The difficulty in removing
recalcitrant organic matter has determined the search for effective chemical oxidation processes having the
potential of converting harmful organics into innocuous substances without the production of concentrated
residues. Consequently, advanced oxidation processes (AOPs) have increasingly been studied and applied in the
treatment of mature leachate. Nevertheless, those processes also oxidize the ammonium and organic nitrogen to
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St
nitrate greatly increasing its concentration above the legal limits for discharging, which creates the need for nitrate
reduction.
After an overview of the most common processes used in landfill leachate treatment, their drawbacks and
advantages, it will be presented the results obtained in our lab with a lab-scale rotating anoxic biological contactor
to remove the excess nitrate, from an already treated landfill leachate. The results obtained so far point out this
process as a promising alternative polishing treatment.
[1] Kurniawan, T.A., Lo, W.H., Chan, G.Y., 2006. Radicals-catalyzed oxidation reactions for degradation of
recalcitrant compounds from landfill leachate. Chem. Eng. J. 125, 35-57.
Keywords: leachate, treatment systems, COD removal, nitrate removal

Suggestion for the theme concerned: Landfill: design, construction, leachate and biogas management
Presentation format: Plenary Lecture
649
14th September
Session 1.7
Chairman: Jos Cavalheiro
650
MEDICAL WASTE MANAGEMENT SYSTEM A CASE STUDY IN A

NORTHWEST PORTUGUESE CITY
2 1
Lara C. Martins, Margarida J. Quina , Jos C. Gis
Rua Lus Reis Santos - Plo II, 3030-788 Coimbra, Portugal; email: jose.gois@dem.uc.pt
Lima - Plo II, 3030-790 Coimbra, Portugal, email: guida@eq.uc.pt
ABSTRACT
The main difficulty in order to compare the management systems of different countries is
related with the fact that many classifications are used. Portuguese legislation (Despacho
n 242/96) classifies medical wastes (MW) into four classes: Group I to Group IV. The
hazardous properties of MW from Group III and IV to the human health and to the
environment, lead to a high level of concern during the management of these wastes.
Recently, the national strategic plan for MW for the period of 2010-2016 (PERH)
indicated an overview of its management system in Portugal and established the
guidelines for next five years. In this work the management system of Hospital Santa
Luzia (HSL) in Viana do Castelo, Portugal was selected as a case study. The evolution
along time reveals that the global amount of MW decreases about 29% from 2005 to
2009, mainly due to improvements in the management of Group III, which one
corresponds to highest costs. For comparison purposes with University Hospitals of
Coimbra (HUC), some specific ratios were defined, namely kg/(bed.day) and kg/(medical
consultation). For group I and II, the HSL produces less waste than HUC. On the
contrary, for Group III and IV, HSL generates more residues than HUC. Indeed, HSL
produces 1.02 kg/(medical consultation) of MW from the group I and II, 1.17 kg/(medical
consultation) for group III, 0.08 kg/(medical consultation) for group IV. In order to
calculate the amounts of MW produced by HSL in 2016 two different scenarios were
simulated: i)- BaU scenario (Business-as-Usual); ii)- PUR (Prevention and Use of
Resources). In the BaU scenario it was estimated that HSL will decrease the global
amount of MW, mainly as result of decreasing the amount of Group III. The quantities of
Group I and II will increase slightly until 2016. In the PUR scenario, several realistic
improvements were considered and consequently it is possible to estimate a decrease for
all groups (I to IV).
Keywords: medical waste, waste management; BaU scenario; PUR scenario
INTRODUCTION
At present, medical waste(MW) is one of the major problems of society due to its hazardous
nature. In fact, the exposure to hazardous MW may cause diseases and changes in the health of
individuals, particularly for those who are involved in their selection, packaging, collection,
transport, recovery/disposal and final destination. This problem is increased when certain
epidemics appear. Thus, the waste management has a great importance and relevance.
The definition MW had several changes over the years. According to Decreto Lei No. 178/2006, of
5 September, MW "means waste resulting from activities carried out in medical units to provide
health care in activities of prevention, diagnosis, treatment, rehabilitation and research related to
human beings or animals, pharmacies, medical-legal activities , teaching and other invasive
procedures involving, such as acupuncture, piercing and tattoos. The classification of MW over the
years has not been easy. However both health professionals and the general population are well
aware of the dangers that the MW can represent, especially in terms of disease carriers.
651
In order to address this discrepancy in various settings, the EU adopted the European Waste List
(LER5) and the List of hazardous waste (LRP), facilitating the classification and management of
different types of waste between countries. The current classification applicable to MW classifies it
into four groups:
Group I - urban waste, presenting no special requirements in its treatment.
Group II - non-hazardous hospital waste, not subject to specific treatments, which can be
treated as urban.
Group III - hospital biohazardous waste, contaminated or suspected of contamination, likely to
incineration or pre - effective treatment, enabling subsequent disposal as household waste.
Group IV - specific hospital waste, incineration mandatory.
It is important to note that in the context of MW, the general hierarchy established by Directive
2008/98/CE should also be applied, which states that for the best overall environmental option
should be: prevention, preparing for re-use, recycling, other recovery methods, whereas disposal
should be the last option.
Several studies have been conducted to optimize the MW management system [1-3]. In Greece, a
study indicates that for an average of 450 beds per hospital, the rate of generation of hazardous
MW varies between 0.26 and 0.89 kg/bed/day. In the two largest hospitals in Greece, with 210 and
350 beds and an occupancy rate of 82% and 60%, the ratio was 0.29 kg/bed/day to 0.77
kg/bed/day respectively [1]. Another study in Oregon in Portland (USA), to optimize MW
management passes by the simple replacing of disposable diapers for children in cloth diapers and
the replacement of towels for cloth towels [2]. In Butterworth Hospital, Michigan, USA the measures
focused on the selection of MW at source and re-use or recycling wherever possible. One of the
actions taken was the routing of worn mattresses for homes or missions of solidarity. Recycled
paper has been used for stationery, toner cartridges have to be reloaded [3].
PORTUGUESE MW MANAGEMENT
The MW in Portugal comprise about 75% to 90% similar to municipal waste, the remaining 10 to
25% are hazardous waste [4]. Considering all types of Hospitals and Health Centers in the period
2001 to 2006, MW increased about 29% due to Groups I, II and III, corresponding to 33 % and
26% respectively. For the same period, the Group IV reached 36%. Regarding to the average of
the Group III, from 2002 to 2006, the ratio changed from 1.01 to 1.17 kg/bed/day, whereas to
Group IV there was a decrease of 0.14 to 0.13 kg/bed/day (PERH 2010-2016). The number of MW
per medical consultation can also be an important indicator. PERH 2010-2016 estimates that are
produced approximately 0.06 kg/medical consultation/year for the Group I & II, group III 0.02
kg/medical consultation/year and finally 0.001 kg/medical consultation/year in Group IV.
CASE STUDY: MW MANAGEMENT IN SANTA LUZIA HOSPITAL

The Hospital Santa Luzia (HSL) is part of the Local Health Unit of the Alto Minho, EPE (ULSAM),
which is a public company incorporated in the National Health Service. The HSL has implemented
an environmental management system (EMS) that includes a policy of MW management.
A quality policy based on international guidelines inherent in the Accreditation Process King's
Fund, the ISO 9001 and Project SINAS 2009 is also implemented. The circuit of MW in HSL is
described in Fig. 1.
Figure 1. Flow chart of the circuit of MW at HSL.
652
Considering the case study under analysis, HSL, Fig.2 shows that from 2005 to 2006 the MW of
Group I & II decreased around 24%. From 2006 this decrease continued but was less pronounced.
Since 2005, Group III has also been decreasing. For Group IV, in general there has been a very
slight decrease. It is noteworthy that the total MW has been decreasing. Comparing figures of 2005
with those of 2009 the MW decreased about 29%, which is very positive in the point of view of MW
management, once this is due to an increasing of the recyclables.
Figure 2. Evolution of the quantity of MW in HSL between 2005 and 2009.
From 2005 to 2009, in general, quantitative evolution of the four groups over the month, decreased
in August, which is explained by the lower attendance at the HSL, due to vacation. For the Group
III there is an increase during the winter and a decrease during the summer. This increasing is
probably justified by flu and cold weakness during this season, which leads to higher attendance to
the hospital. Regarding Group IV no major changes were noted. In relation to MW recycling, since
2006 that it followed the trend.
The local in the HSL that produces more waste in Groups I & II is the Bar, because there are large
amounts of municipal wastes due to the consumption of food and drinks. The intensive care unit is
the service that produces more waste in Group III, which was expected because it is the local
where treatments are regularly carry out and likely to cause biohazard wastes. Obstetrics is the
service where it is produced more waste in Group IV. Regarding to recycling, most production is in
the stores and involved cardboard or plastic.
Ratios comparison with HUC

The quantitative analysis of ratios such as kg/bed/day is important to evaluate and compare MW
management. A comparison with Hospital of the University of Coimbra (HUC) for three years (2005
to 2007) is shown in Fig. 3. The HSL is composed of 473 beds, while the HUC has 1479 beds [5].
These data are for the intermediate years (2006), and calculations were made assuming that the
number of hospital beds has not changed. For Group I & II the HSL produced less wastes. For the
Group III the values at HSL are higher, about 5.5 kg/ bed/day more in relation to HUC. For the
Group IV the scenario repeats. For the four groups the ratio of MW/medical consultation is higher
at HSL and is more pronounced in the Group III and IV.
a) b) c)
Figure 3. Comparison of MW (kg)/bed/day in the HSL and HUC (a) Year 2005 (b) Year 2006 (c) Year 2007.
653
Prediction of the MW under two different scenarios
Over the years health problems are increasing and this increase will take effect on the MW. There
are several factors and trends that may affect the MW management. Trends such as urbanization,
increased life expectancy and changes in the globalized lifestyles, which when combined together
can provide very varied chronic illnesses, including depression, diabetes, cardiovascular disease
and cancer. Simultaneously, there is the issue of climate change gradually can also have an
influence on people's health. Indirect effects related to the change in quality water, the reduction of
drinking water, the increase in waterborne diseases and food sector, the increase of the
phenomenon of air pollution and consequently the increased prevalence of respiratory diseases,
not only will provide the increase in HR, as well as new waste will result dangerous. On the other
hand, there are several factors that may affect the management of HR, as is the case of
pandemics, the new infection control measures and increased home treatment.
A prediction of MW in HSL was carried out until to 2016 taking into account two different scenarios,
according PERH from 2010 to 2116:
- BaU scenario, which admits that the amount of waste is produced according to the trend that
has occurred over the past year, through an extrapolation of data.
- PUR scenario, which assumes that the amount of waste is estimated assuming that the HSL
adopts optimization measures.
BaU scenario
Fig. 4 shows the evolution of waste by 2016 in view of the BaU. These results were calculated
based on an extrapolation of the amount of waste from 2010 to 2016, taking into account the
evolution of the same until 2009. The extrapolation will be less accurate regarding the MW in
2
Group I, II and III, since correlation coefficient, R is 0.93. However regarding Group IV
2
extrapolation is a R of 0.97. In general, according to the BaU scenario the amount of MW in Group
I and II is expected to increase. In contrast the MW in Group III and IV tend to decrease, so this
scenario is quite advantageous for the management of the MW in HSL. The trend line for the
Group IV tends to zero. However, this approach would be valid only until 2013 and subsequent the
amount of waste will tend to stabilizing.
In Portuguese hospitals there is a strong culture of use and discard on the excuse that there is risk
associated with the handling of biological waste. In fact, there is a greater restraint and rationality
regarding to the material used and there are hospital studies that indicate only 20% for the amount
of hazardous waste in hospitals, in contrast to Portugal, where the values are in the order of 30-
40% [6].
PUR scenario
Since it is impossible to avoid the production of MW, measures are to be adopted in order to
optimize the MW management. Table 1 shows some actions and targets that the PUR scenario
should adopt for the future.
Figure 4. Prediction of MW in HSL according to the Figure 5. Quantity of MW in HSL under PUR
BaU scenario (from 2006 to 2009 real data, from scenario (from 2006 to 2009 real data, from 2010 to
2010 to 2016 extrapolated data). 2016 extrapolated data).
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Table 1- Examples of actions and targets to be adopted until the end of 2016, in the PUR scenario.
Objective Target Actions

Reduce paper - Decrease in 15% the amount of paper - Use mostly digital support instead paper
residues purchased - Digitalize the hospital files/archives
- Reuse paper
- Education of employees
Reduce plastic - Decrease in 15% the amount of plastic - Buy larger packages (e.g. 10-20 L)
residues packing related with 1 L and 5 L
- Decrease the amount associated with - Eliminate the machines of snacks
snack machines
Reduce specific - Reduce the quantity of ink cartridges - Purchase of laser printers
residues and tonners - Share and standardize printers
Another of the procedures that the HSL is expected to adopt is concerned the use of medical
devices (MD) reusable. The MD may be reusable or disposable. In recent decades the use of
disposable MD has had a significant increase. The possible justification for this is the benefits in
hospital infection control, convenience of disposables and their ease of use and availability.
If the HSL adopt the measures described in table 1 and proposes to meet by the year 2016, the
PUR scenario estimates that the evolution of quantitative from 2010 to 2016 will be the same as
shown in Fig. 5. This estimate adopts a constant reduction of the four groups of wastes of 15% by
2016, representing a decrease of 2% per year.
Regarding to the total MW is notorious for Fig. 6 (a) - (d) that the estimate carried out under the
BaU scenario from 2010 to 2016 leads to production a smaller amount of MW, than for PUR
scenario. The same happens with the wastes in Group III.
For Group IV, from 2014 PUR scenario would be more favorable, when compared to the BAU
scenario.
However, under the BAU scenario, it produces a larger amount of waste in Groups I and II. In this
way is recommended to the HSL to combine both scenarios, applying the BAU scenario for wastes
of Groups III and IV, and the latter group only until 2014, and for wastes of Groups I and II adopt
the PUR scenario.
a) b)
c) d)
Figure 6. Comparison of the BAU scenario with the PUR scenario. (a) Group I and II (b) Group III (c) Group IV
(d) Total amount.
655
CONCLUSIONS
Data analysis of MW at national level shows in general, an increase of the total residues in Group I
and II and III. However, the wastes in Group IV have decreased in recent years.
Regarding HSL the production of MW related to Groups I and II has increased. In opposite, the
quantity of Groups III and IV have been decreasing. This may be explained by better selection
adopted by the professionals over the past year.
HSL ratios in kg/bed/day were compared with its of HUC. In relation to Groups I and II, the figures
are lower in HSL. In Group III production in HSL is higher. The scenario repeats itself for Group IV.
In the case of the ratios analyzed in kg/medical consultation the HSL produces more waste per
consultant for all groups.
According to the BAU scenario HSL will continue to increase waste in Group I and II by 2016 and
reduce the amounts of Group III and IV. Although the PUR scenario by 2013 indicates a reduction
in Group I and II will be not favorable once the waste is higher in Group III compared with the BAU
scenario. The best solution would be the combination of the both scenarios according to the needs
of the HSL.
References
[1] G. Sanida, A. Karagiannidis, F. Mavidou, D. Vartzopoulos, N. Moussiopoulos, S. Chatzopouslos,
Assessing Generated Quantities of Infectious medical wastes: A case study for a health region
administration in Central Macedonia, Greece, Waste Management, 30 (2008) 532-538.
[2] D.J. Gilden, K.N Scissors, J.B. Reuler,Disposable Products in the Hospital Waste Stream,
The Western Journal of Medicine, 156 (1992) 269-272.
[3] State of Michigan, Departments of Commerce and Natural Resources, Case Study - Waste Reduction:
Rx for a Healthy Environment. Butterworth Hospital, Grand Rapids, Michigan, 178 (1992) 335-517.
[4] A. Prss, E. Giroult, P. Rushbrook, Safe Management of Wastes from Health-Care Activities.
Geneve: World Health Organization, 1999.
[5] C. Silva, Gesto de resduos nos hospitais da Universidade de Coimbra. Tese de Mestrado
em Engenharia do Ambiente, FCTUC, 2008.
[6] Inormation on http://www.cham.min-saude.pt/, portal oficial da ULSAM, Portugal. Access 12
May 2010.
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THE INFLUENCE OF NANOPARTICLES OF GAMMA ALUMINA IN

THERMAL CONDUCTIVITY OF CLAYS
V.C. Neto1, I.R. Marques2, J. Corker3 and M.T. Vieira4

Portugal; vneto@ipn.pt
Portugal; imarques@ipn.pt
3 Laboratory Testing and Wear & Materials, Pedro Nunes Institute, Rua Pedro Nunes 3030-199
Coimbra, Portugal; jcorker@ipn.pt
Portugal; teresa.vieira@dem.uc.pt
ABSTRACT
The possibility to add aluminium anodizing sludge in red clay used in bricks, which can
promote a significant improvement of the thermal insulation, has as sore point to
distinguish if this increase is due to the nanocrystalline character of this sludge and/or to
the porosity induced by the presence of this kind of additive. Besides, it is very important
to estimate properly the interest on the separation of sludge in nanoparticles, usually
more or less agglomerated. In the present study, mixtures of red clay with variable
quantities of synthetic gamma-alumina nanoparticles were produced, as mimesis of
aluminium anodizing sludge after disagglomeration, firstly as previous study and then as
a small brick. After sintering, the specimen with synthetic nanoalumina (5%) reveals a
significant improvement on thermal insulation. Moreover, the mechanical properties of
the consolidate mixtures are not prejudiced by the presence of nanoparticles.
Keywords: Aluminium sludge; Clays; Nanoparticles; Disagglomeration; Thermal conductivity
INTRODUCTION
The current legislation, namely the Regulation Characteristics of Thermal Behavior of Buildings
(RCCTE), began imposing limits of compliance with minimum requirements in terms of thermal
comfort associated with a minimum expenditure of energy in buildings, and set reference values of
coefficients heat transfer of the constructive elements of each building unit [1]. These new
requirements will act as driving forces for innovation of products and construction techniques. In
practical terms, the bricks as building elements have limitations such a poor thermal insulation,
thus, any contribution to enhance the performance of the bricks is welcome and should also
contribute to an improvement in the management/recovery of the future waste arising from
demolition.
Wastes from industrial activity represent complex situations (high production, high potential of
toxicity) that contribute to the environmental impact. It represents an additional cost factor for
companies that generate them, since they have to dispose it properly. In this way, the recycling of
industrial waste to obtain new materials, presented as a booster method of sustainability,
contributes to a number of benefits. Industrial sectors strongly consumers of raw materials, as in
the case of building ceramic industry, are capable of replacing natural raw materials by sub-
products, as wastes. Marques (2009) [2], proved to be possible to recycle aluminium anodizing
sludge in ceramic red clay, with a significant increase of their thermal insulation properties.
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MATERIALS AND EXPERIMENTAL PROCEDURE
Sludge versus nanoparticles of gamma-alumina

The aluminium anodizing sludge, after drying, are composed mainly of Al2O3 (49.74%). The
mineralogical composition, performed on diffractometer using the technique of X-ray diffraction,
reveals from 700C the appearance of three peaks corresponding to the formation of gamma-
alumina. Single crystalline phase identified as the full widths at half maximum (FWHM) suggests
the presence of nanocrystallinity (up to this temperature, the difractograms showed that the sludge
should be amorphous or nanocrystalline, with crystallites of a few nanometers, as when examined
no heat treated [2, 3]). The comparison of aluminium anodizing sludge difractograms with synthetic
gamma-alumina nanoparticles (99.99% purity) (Figure 1) shows that the aluminium sludge ash is
similar to synthetic nanocrystalline alumina, but with slightly higher dimension of crystallites. Thus,
for incorporation into the clay, nanosized particles of synthetic gamma-alumina are used in this
study, as mimesis substance of aluminium anodizing sludge. The synthetic alumina has the
characteristics as follow: specific
surface 150 m-2/g; real density of 3.13
g/cm3 (measured in helium pycnometer);
d50= 50 nm (measured by Transmission
Electronic Microscopy TEM); thermal
expansion coefficient ()= 5.10-6 K-1 [4]
and loss mass, carried out thermal
analysis by processes of Differencial
Thermal Analysis/ Thermogravimetric
(DTA/TG)= 10% (at 20C/min in air),
due mainly to the removal of adsorbed
water by the material.
Fig.1 - Difractograms of sludge and nanometric gamma-alumina.
Clay
The red clay under study, provided by the Preceram Indstrias de Construo, SA group, is
composed mainly by SiO2 (71.39 %), Al2O3 (12.12 %) and iron oxides (3.59 %). The X-ray
difractogram reveals as main mineralogical phases quartz, illite, kaolinite and smectite. DTA/TG up
to 1000C showed a loss of mass, mainly in three distinct stages, corresponding to different
kinetics of diverse phase evolution. Dilatometer analysis has measured an expansion coefficient of
clay of 6.10-6 K-1, in the range from 300 to 500C. Clay was used in two different forms: exactly as it
3
comes from the industry (real density of 2.6 g/cm , %humidity= 13% and d50= 15.56 m, measured
by laser diffraction) and dried and milled in a ball mill and sieved in < 1mm (d50 = 8.56 m and real
density 2.54 g/cm3).
Shaping process
In the previous phase the raw material (red clay with and without nanoparticles of gamma-alumina)
were used to make, small massive cylinders (30 mm of diameter versus 95 mm of height)
conformed by dry pressing (%humidity=1.75%). In a second phase, were evaluated the properties
in small rectangular massive blocs (100mm x 60mm x 25mm) shaped by extrusion (%humidity= 22
to 26%), approaching, as best as possible, to the conventional ceramic process. In the first case,
the pressure applied by the hydraulic press was 50 Kgf/cm2, the additive varied from 5% to 10%
(m/m) of nanoalumina and the sintering took place in an electric oven (Termolab with power 11 kW)
for three different cycles with similar rates of heating (10C/min), with a holding time of 1 hour at
maximum temperatures of 900C, 950C and 1000C. In the second case, the bricks were made
using a laboratory extrusion machine (Shimpo NVA 04S, power 400W and capacity 200kg/h, with
a row dimension of 60 x 25mm). The drying of the bricks was realized in two phases (at
environmental temperature during 24h and then in an oven during 24h, at 105C) and was used a
thermal cycle of sintering similar to the previous study (Tmax= 950C).
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For preliminary study, small or even zero retraction and loss of mass, for all additive contents and
firing temperatures, are justified by the inherent characteristics of the shaping process (uniaxial
pressing). The Archimedes Procedure led to determine in one test the total, open and closed
porosity, water absorption and bulk density of the samples. Table 1 summarizes the main results.
Table 1 Properties as function of nanoalumina content and sintering temperature

Temperature 900C 950C 1000C
Alumina content 0% 5% 10% 0% 5% 10% 0% 5% 10%
Total porosity
25.0 29.6 33.9 25.8 29.8 33.5 21.1 30.5 33.6
[%]
Open porosity
20.9 25.3 29.4 20.6 24.8 30.2 19.0 25.2 30.1
[%]
Closed porosity
4.1 4.3 4.5 5.2 5.0 3.3 2.1 5.3 3.6
[%]
Water
10.4 13.1 16.0 10.3 12.8 16.3 9.1 13.1 16.2
absorption [%]
Bulk density
3 2.0 1.9 1.9 2.0 1.9 1.9 2.1 1.9 1.9
[g/cm ]
Whatever temperature and the nanoalumina content there is an increase the total and open
porosity. These values are associated to an increase of water absorption and decrease of bulk
density. There is not a clear trend concerning the closed porosity. The porosity measured by
Mercury Intrusion Porosimetry (MIP), that measures an open porosity (Table 2), is according to the
results based on Archimedes Method. The pore size distribution in the samples reveals an increase
in the total volume of open pores, particularly of nanometer dimensions (as the results for the
average pore diameter shows), bridging the idea of a sub-micrometer and nanometer porosity
increase.
Table 2 Porosity measured by Mercury Intrusion Porosimetry

Temperature 900C 950C 1000C
Alumina content 0% 5% 10% 0% 5% 10% 0% 5% 10%
Mercury porosity
22.8 27.8 31.0 22.3 28.2 30.0 20.1 26.8 30.6
[%]
Total pore
0.12 0.15 0.17 0.12 0.15 0.17 0.10 0.14 0.18
volume [ml/g]
Average
pore diameter 0.71 0.14 0.05 0.92 0.16 0.07 1.16 0.24 0.09
(volume) (m)
The microstructure of samples was

a) b) observed by Scanning Electron Microscopy
(SEM). In Figure 2, it is possible to observe
the location of nanoparticles in the clay
matrix. The specimens corresponding to
the clay (a) and c)) have clean surfaces.
And b) and d) exhibit microstructural
differences, where it is possible to see the
presence of nanoparticles or clusters of
c) d) nanoparticles disseminated in the clay
matrix.
Fig. 2 - Microstructure (SEM) of a) clay

(3.500X), b) with 10% additive (3.500X), c) clay
(20.000X) and d) with 10% additive (20.000X).
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The compressive strength was measured by a traction machine (with a maximum capacity of 100
kN). These tests were based on the application of a uniformly distributed load on the samples
faces, previously prepared with polishing, being guaranteed a speed of 1mm/min and an increase
in the force applied up to the rupture. Whatever the sintering temperature there is a decreasing in
compressive strengths with the increasing of nanoalumina content (Table 3). The results are
consistent with the values of open porosity. However, it isnt only total porosity, but also pore size
that may influence the compressive strength. The resistance values that are presented, compared
with the low compressive strength characteristic of this material, shows the presence of the highest
porosity in sub-micrometer or even nanometer additive particles, as previously shown [5]. Note that
the values of mechanical strength result from the forming process (pressing).
Table 3 Values of compressive strength (MPa)

Alumina content
[C] [%] 0 5 10
Temperature
900 98.0 69.1 61.9

950 88.9 68.9 61.2
1000 99.1 58.4 60.3
For the thermal characterization, it was determined the thermal conductivity (k) with the equipment
Isomet 2104 (measuring ranges between 0,015 to 6 (W/ mC) and temperatures from -20 to 70C).
Given the open porosity values, the samples were sealed for the thermal test, with a thin layer of
varnish, in order to describe only the effect of internal porosity and alumina content. The thermal
conductivity values (Table 4) are decreasing with the increasing of nanoalumina content. The
sintering temperature used does not give large discrepancies in the results, but the 5% of additive
content gives rise to a significant improvement whatever the firing temperatures (max 30%).
Table 4 Values of thermal conductivity (W/mC)

Alumina content
[C] [%] 0 5 10
Temperature
900 0.54 0.38 0.33

950 0.53 0.39 0.36
1000 0.51 0.39 0.34
Figure 3 verifies shows that the decreasing of thermal conductivity has not related with closed
porosity values, the main effect may be attribute to the presence of alumina nanoparticles.
Fig.3 - Effect of closed porosity variation in thermal conductivity for each sintering temperatures as a function
of additive content.
660
This previous study highlights that 5% of gamma-alumina nanoparticles in the clay has a more
significant role in thermal properties than 10% content. The test in small bricks shaping by
extrusion process was only carried out with this additive content. The sintering temperature
selected is similar to the maximum temperature used in bricks industry - 950C. The characteristics
of mixtures to the brick extrusion are summarized in Table 5.
Table 5 Properties of extrusion conformation

Temperature 950C
Alumina content 0% 5%
Retraction after
5.2 8.9
drying[%]
Total retraction
5.0 8.9
[%]
Loss of mass
3.1 3.7
[%]
Plasticity
18.4 34.4
[%]
The results show that the material retraction occurs mainly on drying phase and the addition of
nanoalumina particles increases this parameter. This trend is similar for the loss mass and
plasticity parameters. In fact, these retractions are associated to the higher water level necessary
to mixture the clay paste with nanoalumina. The brick properties (Table 6) are similar to the ones
resulting from pressing, with a trend to higher values, once the shaping method used is the
extrusion.
Table 6 Properties as function of nanoalumina content

Temperature 950C
Total porosity
28.0 34.8
[%]
Open porosity
26.8 32.9
[%]
Closed porosity
1.2 2,0
[%]
Water absorption
13.7 18.2
[%]
Bulk density
2.0 1.8
[g/cm3]
The analysis of the pores system in brick samples, by MIP (Table 7), came to confirm the same
results present in the first case.
Table 7 Porosity measured by Mercury Intrusion Porosimetry

Temperature 950C
Mercury porosity
25.2 30.2
[%]
Total pore
0.13 0.16
volume [%]
Average
pore diameter 1.09 0.51
(volume) (m)
661
Compressive strength values (Table 8) of the brick show that the addition of nanoalumina to red
clay plays to a role whatsoever.
Table 8 Values of compressive strength (MPa)

Alumina content
[C] [%] 0 5
Temperature
950 12.72 12.52
However thermal conductivity decreases about 17% with the addition of 5% of nanoalumina (Table
9), lower than the measured in the cylinder pressed and sintered.
Table 9 Values of thermal conductivity (W/mC)

Alumina content
[C] [%] 0 5
Temperature
950 0.46 0.38
CONCLUSIONS
The incorporation of gamma-alumina nanoparticles in brick clay contribute to a decrease of thermal
conductivity and, consequently, to an improvement of thermal insulation of the brick without a
significant loss of compressive strength. When compared with to the uniaxial pressured for the
similar thermal cycle the shaping process like extrusion can decrease the thermal improvement
effect resulting from the addition of nanoalumina.
Acknowledgment
This work was developed in the framework of the scientific project QREN SeTIVERNano 13312,
Produo de tijolos trmica e estruturalmente mais resistentes por induo de nanomateriais,
involving two Portuguese industrie, Preceram Industrias de construo SA and HydroBuilding
Sistemas de alumnio para construo, Lda.
References
[1] Decreto-Lei n 80/2006 de 4 de Abril. Regulamento das Caractersticas de Comportamento
Trmico dos Edifcios (RCCTE).
[2] I.S.R. Marques, Estudo da influncia da adio de resduos de anodizao de alumnio no
isolamento trmico de tijolos de barro vermelho. Tese de Mestrado em Engenharia do Ambiente,
Universidade de Coimbra, Coimbra (2009).
[3] S.C.P. Vieira, Comportamento das lamas de alumnio com a temperatura. Relatrio
apresentado Universidade de Coimbra para obteno da Licenciatura em Engenharia de
Materiais, Coimbra (2001).
[4] Information on http://www.engineeringtoolbox/linear-expansioncoefficients-d_95.html.
[5] J.C. Le Huec, T. Schaeverbeke, D. Clement, J. Faber and A. Le Rebeller, Influence of porosity
in the mechanical resistance of hydroxyapatite ceramics under compressive stress. Biomaterials,
16 (1995) 113-118.
662
APPLICATION OF PROMETHEE TO PRIORITIZE MSW TREATMENT

ALTERNATIVES UNDER AN ENVIRONMENTAL APPROACH
M. Herva, C. Garca-Diguez, E. Roca

1 Sustainable Processes and Products Engineering Group, Dpt. Chemical Engineering, Faculty of
Engineering, University of Santiago de Compostela, Spain. Emails: marta.herva@usc.es;
carlos.garcia.diguez@usc.es; enrique.roca@usc.es.
ABSTRACT
The choice of a municipal solid waste (MSW) treatment option is a complex task in which
a widespread set of criteria must be taken into account. Additionally to economic,
geographical situation or social aspects, the decision process should consider the
environmental perspective. With the purpose of quantifying these environmental burdens,
a wide variety of environmental and sustainability indicators have been developed in the
last years. However, integrative frameworks have been signaled as the best option to
achieve more comprehensive assessments. To this respect, Multi Criteria Analysis (MCA)
provides a family of flexible analytical tools that can effectively support decision making
with regard to complex sustainability issues.
In this work, a case study extracted from the literature was analyzed to prioritize among
four different options of MSW treatment processes. First, the Ecological Footprint (EF)
was applied as single indicator; then, other material flow indicators related to water
consumption, emissions to air and water and occupied landfill volume were included and
a ranking of alternatives was established using PROMETHEE/GAIA as MCA
methodology. The ranking obtained was (from best to worst): thermal plasma gasification,
biological treatment of organic fraction with energy recovery from refuse derived fuel,
incineration with energy recovery and landfilling.
Keywords: Multi-criteria analysis; PROMETHEE; Ecological footprint; Energy and material flow
analysis
INTRODUCTION
Nowadays, one of the priorities for municipalities is to collect, recycle, treat and dispose of the
increasing quantities of municipal solid waste (MSW) [1]. Fulfilling the sustainable management of
this waste makes necessary to take into account all phases of impact from planning to design, to
operation and to decommissioning [2]. The potential impacts caused by wastes on the environment
(pollution of air, soil, surface and ground water), the use of valuable space by landfills and poor
waste management that causes risks to public health [3] are the catalyst to handle the problem;
otherwise, waste is considered as irrelevant to production [4].
The EU directives and national policies developed since the beginning of the 1990s set targets for
recycling and recovery and restrictions on waste to landfill. As a result, the percentage of municipal
waste recycled (including composting) has increased significantly. The increasing pressure on
waste managers, planners and waste regulators to deliver a sustainable approach has spanned the
spectrum of new and existing waste treatment technologies and managerial strategies from
maintaining environmental quality at present to meet sustainability goals in the future [2,5].
The waste hierarchy defined in the Directive 2008/98/EC on waste establishes the following priority
order to be considered in waste prevention and management legislation and policy: 1) prevention;
2) preparing for re-use; 3) recycling; 4) other recovery, e.g. energy recovery; and 5) disposal.
Nonetheless, this new Directive also addresses the possibility of altering the stated hierarchy in a
specific situation, if justified by a life-cycle thinking study [6]. Thus, this kind of studies can be used
to test the waste hierarchy and identify situations where it may be modified, as for exchanging
663
order between recycling and incineration, or to place biological treatments such as anaerobic
digestion and composting [7,8]. This may depend on the waste itself, on the location where the
waste arises and its timing, as well as priorities in cases of conflicting results.
Tools are needed to predict the likely overall environmental burdens of any waste management
system. From here, several criteria can be derived that should be considered to offer a complete
and meaningful analysis of alternatives. However, considering a number of criteria at a time
certainly complicates the decision making process. In this respect, Multi Criteria Analysis (MCA)
provides a family of flexible analytical tools that can effectively support decision making with regard
to complex policy and planning problems [9,10].
In this work, four different options of MSW treatment were ranked using data from the literature.
First, the Ecological Footprint (EF) was used as single indicator; then, other indicators were
included in the appraisal and were integrated using PROMETHEE/GAIA.
Case study
The alternatives of MSW treatment [11,12] evaluated from an environmental point of view were:
landfilling with energy recovery (a1), incineration with energy recovery (a2), biological treatment of
the organic fraction (OFMSW) with energy recovery from the refuse derived fuel (a 3) and thermal
plasma gasification (a4). The selected functional unit was 1 kg of MSW treated. These alternatives
were evaluated by means of the following criteria: EF (g1), water consumption (g2), air emissions of
organic compounds (g3), air emissions of dusts (g4), water emissions of suspended solids (g5) and
occupied landfill volume (g6).
Ecological Footprint
The component method was applied and the mutually exclusive use of land approach was adopted
[13]. Hence, individual EFs were calculated for each flow in the inventory data (in a yearly basis)
and were later aggregated, according to Eq. 1 and Eq. 2, respectively.
(1)
(2)
Where EFi is the area required for the component i; NPi, EVi and EPi are the natural productivity,
embodied energy and energy productivity (associated to fossil fuel) for element i; Fj is the
equivalence factor for land type j. Equivalence factors translate a specific land type (i.e. cropland,
pasture, forest, fishing ground) into a universal unit of biologically productive area, generally a
global hectare [14].
Input and output flows included in the EF estimates were those that could properly be assessed
with this methodology (materials and energy flows) and reflected the most significant environmental
burdens of the waste treatment alternatives considered, although the inventory suffered from
certain gaps (e.g. the use of chemicals or waste water treatment were not included). Energy
balances were carried out to take into account electricity generation in all the alternatives. Among
air emissions, only those with global warming and acidifying effect were accounted for by means of
assimilation factors [15]. Finally, the EF for solid waste was the area required for landfill dumping.
For those materials that were recycled (e.g. stabilized organic fraction, ferrous materials and slag)
a counter footprint (CF) was appraised by means of avoided impacts.
Multi Criteria Analysis

The PROMETHEE/GAIA methodology was selected to conduct the MCA using the software
Decision Lab 2000 [16]. PROMETHEE (Preference Ranking Organization Method for Enrichment
Evaluation) is a non-parametric outranking method for a finite set of alternatives and is based on
positive (out +) and negative (in -) preference flows for each alternative in the valued outranking
relation to rank the alternatives according to the selected preferences (weights). In this case, the
664
Analytical Hierarchy Process (AHP), combined with the Saatys scale, was employed to derive the
criteria weights [17].
For each criterion, the preference function translates the difference between the evaluations
obtained by two alternatives into a preference degree ranging from zero to one. V-shape type
functions (Fig. 1) were selected in this case and all criteria were set to be minimized. The
establishment of thresholds required for the application of PROMETHEE was based on criteria
amplitude, given that all criteria were quantitative; hence, the threshold of indifference (q) was set
at 10% and the threshold of strict preference (p) was set at 50% of the total interval of variation for
each criterion.
P
1
q p
d
Fig. 1. Preference function selected: V-shape with indifference criterion. P refers to preference
function and d represents the difference between the evaluations for two alternatives.
RESULTS
The results from EF assessments are presented. A ranking of alternatives was established based
on the EF values and was later compared to that obtained from the MCA.
EF estimates
The gross EF, CF and net EF for the four alternatives evaluated are shown in Fig. 2. The EF values
2
obtained for 1 kg of MSW treated were 13.2, 4.9, 3.3 and 3.4 gm for alternatives a1 to a4,
respectively.
14
Gross EF
12
CF
10
Net EF
8 1
EF (gm2 kg MSW-1)
-2
a1 a2 a3 a4
-4
Landfill with energy Incineration with Biological treatment of Thermal plasma
recovery energy recovery OFMSW + energy gasification
recovery from RDF
Fig. 2. EF of the analyzed MSW treatment alternatives.
665
The worst results in terms of EF were obtained for the landfilling option, with a main contribution
from the area required to dispose of the stabilized solid waste. A quite insignificant contribution to
CF of the biogas collected was observed. The net EF was around three times higher than for the
other three alternatives. For all the alternatives assessed, air emissions posed the major
environmental pressure in terms of EF. Besides, the effect of energy recovery and material
recycling had a noticeable effect on the contribution to CF, thus diminishing the net EF in a range
from 27% to 37%. Incineration with energy recovery was undoubtedly ranked in second place,
while the difference between biological treatment of OFMSW with energy recovery from RDF and
thermal plasma gasification was not so clear. A higher gross EF was appraised for thermal plasma
gasification, but CF due to high levels of energy recovery reached in this process reduced it to a
net EF quite close to that for biological treatment of OFMSW and RDF combustion.
Ranking from MCA

Once the EF was assessed, the multi-criteria decision matrix (Table 1) was completed for criteria
defined in the methodology section. The same ranking was provided by both PROMETHEE I and II
methods (Fig. 3 and Fig. 4). Therefore, the thermal plasma process was chosen as the best
alternative whereas the landfill with energy recovery was evaluated as the worst alternative.
Criteria weights were modified in the software within a reasonable interval to conduct a sensitivity
analysis and the ranking of alternatives did not change.
Table 1. Decision matrix for the selection of MSW treatment alternatives.

Criteria
g1 g2 g3 g4 g5 g6
2 3
(gm ) (g) (g) (g) (g) (m )
-1 -2 -3
a1 13.2 0 1.210 2.710 0.03 1.4310
Alternatives
-3 -2 -4
a2 4.9 175.2 2.010 4.910 6.79 2.710
-3 -2 -4
a3 3.3 70.8 1.610 3.3210 1.23 4.910
-4
a4 3.4 151.2 1.210 0 0 0
Fig. 3. Ranking of alternatives according to PROMETHEE I.
Fig. 4. Ranking of alternatives according to PROMETHEE II.
Similar conclusions could be extracted from the GAIA plane (Fig. 5), which had a = 91.57%
(parameter that measures the amount of information preserved in the GAIA plane), thus ensuring
its reliability. The pi decision axis clearly pointed at a4 as compromise solution among all criteria,
being a3 quite close and a2 and a1 in opposite direction. All criteria seemed to be in agreement with
each other as their axes had the same orientation (only water consumption g2 could be
666
considered to be moderately conflicting). Further, a 3 and a4 conveyed strong features for most of
the criteria, conversely to a1 and a2.
Fig. 5. GAIA plane for the selection of MSW alternatives problem.
The ranking of waste treatment alternatives obtained can be considered to be in agreement with
the general recommended hierarchy for waste management [6], since energy recovery and the
generation of valuable sub-products is prioritized with respect to landfilling. Besides, when
incorporating more environmental indicators than EF, a4 was more clearly identified as the best
option. In this case study the EF proved to be a good screening indicator, although the measure
provided by this indicator did not include all potential environmental burdens due to weaknesses in
its methodology [12] and to inventory gaps.
The selection of the plasma process as best alternative must be judged cautiously. This is a novel
technology for which a small number of industrial applications exist up to date. Besides, it was not
initially conceived as a process for the treatment of MSW but for industrial ones, given its ability to
decompose hazardous substances. Further, it must be remarked that only environmental criteria
were taken into account to obtain this ranking.
CONCLUSION
In this work, a case study extracted from the literature was analyzed from an environmental point of
view. The goal was to rank different alternatives for the treatment of MSW. The application of
PROMEHTEE/GAIA as MCA methodology was found to be a suitable way to integrate the
information provided by a set of environmental criteria and to aid decision making. Also, EF proved
to be a good screening indicator although it did not provide a comprehensive measure of
environmental impacts associated to the waste treatment options considered. Besides, the ranking
obtained was in agreement with the general hierarchy recommended by legislation, prioritizing
treatment techniques that allow for energy or materials recovery. It must be noticed that inventory
data suffered from certain gaps, e.g. the use of chemicals or waste water treatment was not
included. A more detailed environmental evaluation or the extension of the system boundaries
could lead to obtain a different ranking of alternatives.
Acknowledgements
through the Project INDIE (CTM2010-18893), ERDF included. Marta Herva wishes to thank the
University of Santiago de Compostela for her pre-doctoral contract.
667
References
[1] F. Cherubini, S. Bargigli, S. Ulgiati, Life cycle assessment (LCA) of waste management
strategies: landfilling, sorting plant and incineration, Energy 34 (2009) 2116-2123.
[2] A. Pires, G. Martinho, N.-B. Chang, Solid waste management in European countries: A review
of systems analysis techniques, J. Environ. Manage. 92 (2011) 1033-1050.
[3] Environmental Protection Agency, Europes environment, The fourth assessment, Copenhagen,
Denmark, 2007 (ISBN: 978-92-9167-932-4).
[4] J.K. Seadon, Sustainable waste management systems, J. Clean. Prod. 18 (2010) 1639-1651.
[5] J.R. Barton, D. Dalley, V.S. Patel, Life cycle assessment for waste management, Waste
Manage. 16 (1996) 35-50.
[6] Directive 2008/98/EC of the European Parliament and of the Council of 19 November 2008 on
waste and repealing certain Directives, Off. J. EU L 312 (2008) 3-30.
[7] G. Finnveden, J. Johansson, P. Lind, . Moberg, Life cycle assessment of energy from solid
wastepart 1: general methodology and results, J. Clean. Prod. 13 (2005) 213229.
[8] A. Moberg, G. Finnveden, J. Johansson, P. Lind, Life cycle assessment of energy from solid
waste-part 2: landfilling compared to other treatment methods, J. Clean. Prod. 13 (2005) 231
240.
[9] R. Lahdelma, P. Salminen, J. Hokkanen, J., Using Multicriteria Methods in Environmental
Planning and Management, Environ. Manage. 26 (2000) 595605.
[10] L.A. Greening, S. Bernow, Design of coordinated energy and environmental policies: use of
multi-criteria decision-making, Energy Policy 32 (2004) 721735.
[11] U. Arena, M.L. Mastellone, F. Perugini, The environmental performance of alternative solid
waste management options: a LCA study, Chem. Eng. J. 96 (2003) 207-222.
[12] M. Herva, R. Hernando, E.F. Carrasco, E. Roca, Development of a methodology to assess the
footprint of wastes, J. Hazard. Mater. 180 (2010) 264273.
[13] C. Monfreda, M. Wackernagel, D. Deumling, Establishing national natural capital accounts
based on detailed EF and biological capacity assessments, Land Use Policy 21 (2004) 231
246.
[14] J. Kitzes, A. Peller, S. Goldfinger, M. Wackernagel, Current methods for calculation National
Ecological Footprint Account, Sci. Environ. Sustain. Soc. 4 (2007) 1-9.
[15] M. Herva, C. Garca-Diguez, A. Franco-Ura, E. Roca, New insights on ecological footprinting
as environmental indicator for production processes, Ecol. Ind., in press.
[16] Visual Decision Inc., Decision Lab 2000 - Executive edition, Getting started guide, Canada,
2009.
[17] T.L. Saaty, T.L., The analytic hierarchy and analytic network processes for the measurement
of intangible criteria and for decision-making, in: J. Figueira, S. Greco, M. Ehrgott, M. (Eds.),
Multiple Criteria Decision Analysis: State of the Art Surveys, Springer, New York, 2005, pp. 345-
406.
668
Wastes: Solutions, Treatments and Opportunities
1st Internacional Conference
September 12th- 14th 2011
OLEICO+ PROJECT: OLIVE MILL WASTES AND THE SUSTAINABILITY OF

THE OLIVE OIL INDUSTRY IN EUROPE
1 2 1 1
J. Cardoso Duarte , F.Santori , B. Ribeiro , G. Augusto
1. Laboratrio Nacional de Energia e Geologia (LNEG) - Unidade de Bioenergia, Portugal,
jose.duarte@lneg.pt; belina.ribeiro@lneg.pt; augusto.gabriela@lneg.pt
2. Istituto Superior di Ricerca Formazione sui Materiali Speciali per le Tecnologia Avanzate, Italy,
f.santori@isrim.it
ABSTRACT
Every year more than 15 millions tones of olive mill wastes (OMW) are generated in the
EU. Those wastes consist in vegetation waters, effluents from olive oil, washing, leaves
and other solids coming from wet pomaces from two phase extraction systems. Each of
these residues presents different challenges, and is sometimes covered by different legal
+
frameworks at European and National level. The Oleico project (LIFE07INF/IT/438),
brought together four European Institutions from olive oil producing Countries, Greece,
Italy, Spain and Portugal, to seek and select a set of environmental friendly technologies
for the remediation or valorization of OMW, and to raise the awareness of olive oil
stakeholders for an environmental sustainable olive mill waste management. The OMW
management is becoming a critical issue for the sustainability of olive oil industry,
because of the increasing quantities generated, the public environmental awareness and
stricter environmental laws. Challenges posed by the OMW management are as diverse
as the context of olive production itself. In all cases olive mill owners are in the top of an
economic sector of major social and environmental importance in some of the more
vulnerable Mediterranean regions of Europe, in an environment of depressed olive oil
prices and a several of legal constrains and regulations. In this paper we examine the
different contexts of OMW generation and management, their respective waste-streams
and legislative frameworks. The work will also compare the situation across the four
Member States, and presents the different technologies selected for the Awareness
Raising Campaign for the Treatment and Valorization of Olive Mill Wastes now occurring
in all Member States.
Keywords: OMW, olive oil, pomaces, leaves, wastewaters,legislation
INTRODUCTION
According with the figures of International Olive Council, the worldwide consumption of olive oil
increased of 78% between 1990 and 2010 [1]. This increase in consumption fuelled an increase
on the production of 81% in the same period, for which the UE was the main contributor with 11%
increase in production in the last 20 years [2].
The increase of olive oil production implies a proportional increase in olive mill wastes (OMW),
comprising stones, pulp, olive vegetation water and depending on the extraction process other
effluents from water input in the process. On average, olive oil is less than 20% of the olive fruit
[3]. Olive oil is a natural product, extracted using mechanical and thermal processes, therefore
OMW are also natural products. But if in nature olives fell in the soil go through a natural
degradation process slowly releasing their components, the massive quantities of natural OMW
released during the olive mill season (average 100 consecutive days every year) present high
values for most pollution parameters, particularly the organic loads (up to 160 g/l COD), and
phenolic compounds that difficult its biodegradability. Several studies have proven the negative
effects of OMW on soil microbial populations, on aquatic ecosystems and even in air medium
[3,4,5,6,7]. The research to treat and valorize these wastes is still in full swing [8,9,10], to name jus
a few of the innovative research trying to recover some of the valuable compounds of OMW.
669
The OMW management is becoming a critical issue for the sustainability of olive oil industry, because of
the increasing quantities generated, the public environmental awareness and stricter environmental
laws. In this paper we examine the different contexts of OMW generation and management, their
respective waste-streams and legislative frameworks in countries involved in LIFE OLEICO+ Project.
OLIVE MILL WASTES

Types and relative quantities of OMW are first dependent upon extraction systems. Olive mill
extraction systems have been going through a large technological evolution in the last 20-30 years.
The traditional press systems that generated a dry pomaces or orujo (Spain) and olive vegetation
water or alpechin (OMW) as main byproducts, gave room to more efficient and economic
continuous extraction systems by centrifugation. These continuous systems are named 3-phase
continuous (3PC) when they separate olive oil from olive vegetation water (OVW) and pomaces,
and 2-phase continuous (2PC) when the outputs are olive oil and pomaces mixed with the
vegetation water (alperujo), here named two-phase olive mill waste (TPOMW).
In mountain regions of extensive olive groves, olive mills are generally small press to medium 3PC
extraction. In regions of intensive olive growing, new 2PC olive mills of large capacity produce enormous
quantities of TPOMW. Big 2PC olive mills are also confronted with the washing water from continuous
extraction systems (WWC2P) that is rarely accepted in the waste water treatment plants because of its
huge quantities or heavy organic contents [11]
Regions of traditional but intensive olive production typically have a mix of olive mills of different
extraction systems and processing capacities.
Table 1 displays an adaptation of the average values pointed in [2] for the different types of OMW
generated by each tone of olives milled. These values are used to estimate OMW quantities in this
work.
Table 1 Average quantities of effluents, wastes and byproducts of olive mills with different
extraction systems, by 1 ton of crushed olives. Adapted from [2]
Extraction System OVW [l] WWC2P [l] Pomaces [kg] TPOMW [kg] Leaves [kg]
500 500
Press 50
(88% water) (26% water)
1100 550
3PC 50
(94% water) (40% water)
800
2 PC 150 50
(>60% water)
Olive vegetation water (OVW)

Olive vegetation water has been the main concern of olive mill industry, law makers and public
opinion because of its heavy environment impacts: it smells and seriously disturbs fresh surface
and ground water, brings insects, disturbs plant grow and germination and disturbs soil structure
decreasing porosity.
European Legislation doesnt allow the discharge of olive vegetation water, and this effluent is the
main reason why the European IPCC Bureau considers the 2-phase continuous system as the best
technology available for olive oil production.
However the 3PC extraction systems are nearly exclusive in Greece and preponderant in Italy where it
processes 64% of the olives milled
In all countries the usual destination of OVW are evaporation pounds, and or irrigation in
agriculture soils. Both disposal methods are regulated whether specifically or in the scope of
industrial effluents.
Evaporation pounds must have the capacity to receive all the OVW produced by the olive mill more
the precipitation volume expected during de winter in those regions. For optimal evaporation
climatic condition as in Alentejo south Portugal, the Water Authority requires the impervious
evaporation lagoon to have a maximum deep of 50 cm to receive the OMW only, and extra 20 cm
to receive the season rainfall. Area requirements are not the only drawback of evaporation ponds
that also emit bad smells, attract insects and have a bad impact in landscape.
Deposition in soil is also legally regulated and implies a quantity limit of 80 cm/ha each year (in
some regions of Italy this quantity is 50 cm/ha/y). Irrigation does not only require appropriate
agriculture surface (in Portugal irrigation can only be made in tree crops outside buffer zones from
670
surface water bodies, streams, wells and inhabited areas or dwellings), but also impervious
reservoirs and most often, transportation from the olive mill to the field.
Table 2 displays the estimated areas required for evaporation pounds or crops irrigation with OVW.
The staggering sizes of evaporation lagoons around 3PC olive mill, with associated smell and
insects shows how unpleasant this solution would be is applied universally. Remark that those
estimated areas are quite conservative, both because of conservative estimation of OVW from
Table 1, but also because the required deep of lagoons is the one established as minimum in a
region of low rainfall and long and hot summers in south Portugal.
In Table 2 are also the estimates of required irrigation areas for the disposal of OVW of each 3PC
olive mills. The last column indicates the average size of holdings with olive plantations for oil. The
numbers indicate that for instance in Greece each 3PC olive mill owner would have to agree the
use of OVW for irrigation with 10 owners of olives plantations.
Table 2 Area requirements of the most used ways to dispose OVW.

OVW Area of Area of evaporation tree crops area for Average
[m3] evaporation ponds ponds around 3PC soil disposal for olive
Country
per Country [ha] mills [m2] each 3PC olive mills holding
[ha] [ha]
Spain 243676 85 2500 16 5
Italy 2556800 570 1600 10 1,3
Greece 1944217 430 2300 14 1,5
Portugal 110532 20 1300 8 2,6
(OVW- estimated OVW produced according to Table 1, and olives crushed from sources as in Figure 2; Area of evaporation
ponds per Country [ha] area required to evaporation ponds of all OVW produced in the country, where these ponds would
have a deep of 50 cm: Area of evaporation ponds around 3PC mills average area of evaporation ponds with capacity to
evaporate OVW from 3PC mills alone. Tree crops area for soil disposal for each 3PC olive mills if all the OVW generated
were for soil disposal 80 m3/ha tree crops. Average area of olive farm calculated from EUROSTAT 2007)
Dry Pomaces and stones

Remnants of crushed olives partially drained from OVW, coming from press or 3PC olive mills
are clearly a byproduct obeying cumulatively to all requirements of the Article 5.1 Directive
2008/98/EC concerning wastes: further use of this material is certain as it have always been,
traditionally in feed production and now as a valuable raw matter for pomace oil extraction
industry; also its nearly solid nature doesnt imply particular environment hazards in its transport,
storing or manipulation. The exhausted pomace, after oil extraction is still valuable for animal
feed or energy production. Stones have been a largely used byproduct of olive mills especially
for heating due to its remarkable energy content (5000 kcl/kg).
Two-phase olive mill waste TPOMW

The 2PC extraction system that was first implemented in early 90s avoids the water input in the
process and has lower operating costs. This system is largely implemented in new olive mills in
Spain and Portugal, where it processes respectively 90% and 65% of the olives for oil. The new
2PC olive mills tend to have large capacities and in Portugal as in Spain olive for oil production is
still increasing, therefore the production of TPOMW will increase in the near future.
TPOMW is a semi-liquid residue presenting environmental risks similar to OVW because it can spill
and infiltrate. This material is also used by the oil extraction industry where it is posing new
challenges for transportation, storing and drying [2]. TPOW fails therefore the strict definition of
byproduct, and the environmental problems are effectively being exported to the pomace oil
extraction industry, upon which new 2PC olive mills are completely dependent. Table 3 depicts the
+
TPOMW generated in the OLEICO countries, in tones but also in 18 000 l road tankers that must
be used to transport this material from the olive mills to its usual destination: the pomace oil
extraction industry units.
Washing Water WWC2PC

The two-phase continuous extraction system does also generate effluents coming from the water
used to wash olives going to crush, and olive oil washing. Those effluents are also to be disposed
and pose a challenge due to the dimension of 2PC olive mills. Whereas the organic load of this
671
effluent is to as high as the olive water vegetation itself, it is still too high to be treated in waste
water treatment plants [11], and tend to have high charges of pesticide used in olive crops [12]. As
for OVW, these effluents tend to be disposed in evaporation ponds or disposed in the soil, but there
is still no specific regulation for soil spreading. In Table 3 there is an estimation of the WWC2P by
country and indicatively the average area of 0,5 m deep evaporation pond necessary to dispose
this effluent, that as for OVW will certainly emit bad smells and attract insects.
Table 3 Estimated residues of 2PC olive mills per Country. (Estimations made as in Table 2)
Estimated
Estimated Estimated Estimated Estimated
evaporation area
TPOMW by TPOMW in road TPOMW by 2PC WW2PC per mill
around 2PC mills
Country [t] tanks [18000 l] olive mill [m3] [m3]
[m2]
Spain 4 047 040 224836 3230 1011760 1600
Italy 7680 427 1536 1920 770
Greece - - - - -
Portugal 165979 9221 948 41494,667 500
Leaves and other residues from olive cleaning

About 5% of olives going to crush are olive leaves and other residues removed in the olive mill.
Olive leaves are usually used for small ruminants feed, and high biodegradable, however its ever
increasing quantities are starting to disturb olive mill owners. In Spain alone some 300 000 tons of
leaves must be transported and disposed each year.
+
Olive mills waste streams and legal frameworks in OLEICO Countries
+
All Oleico Countries are European Union Member States, therefore obliged to comply with the EU
Directives concerning water, wastes, integrated pollution prevention and control and air emissions.
However the CPIP Directive applies only to olive mill producing more than 300 t of olive oil a day
+
which excludes more than 99.9% of the nearly 10 000 olive mills operating in OLEICO Countries.
Most olive mills must conform to national and local regulations that differ with geographical
location. Table 4 points to the main differences in legislation and environmental concerns of olive
+
mill wastes across OLEICO countries.
+
Table 4 - Olive mills waste streams and legal frameworks in OLEICO Countries
Principal OMW
Country Legal Framework Main OMW Main Challenges
destinations
Due to the industry
No specific legislation on TPOMW (90% of Pomace oil extraction
Spain dimension all wastes olive
OMW. processed olives) units
pose challenges.
Extensive and specific
legislation on OMW.
TPOMW and OVW from OVW (90% of More than 5000 olive
Italy Soil spread
3PC legally equivalent. processed olives) mills, scattered in territory.
Constrains in soil spread
include slope
Specific legislation OVW from 3PC
Greece Evaporation ponds 2000 olive mills.
concerning OVW (99,9%)
TPOMW to pomace
30% of OMW are oil extraction Sector still evolving at fast
Specific legislation
Portugal OVW and 50% OMW soil spread rate. OVW main concern
concerning OVW
TPOMW and evaporation of olive mill owners.
ponds
+
Oleico - Project
+
The Oleico project selected a set of technologies able to treat, and some of them valorize the olive
mill wastes. Selected technologies characteristics are summarized in Table 5, and are being
+
promoted in the Awareness Raising Campaigns now in force in OLEICO participating countries.
This selection considered: patent and publications, type of technology (input residues),
environment impact (balance of water, energy, and other products, production of waste and air
emissions), status of technology (existing plants), and economic data (associated costs and net
income value). The ranking of technologies was performed by weighting each of the parameters
above.The eco-sustainability performance of the different technologies was heavily affected by
672
energy consumption and its consequent carbon dioxide emissions. The occurrence of bad smells
and landscape impacts of facilities did also affect this parameter. Only one technology achieved the
three smiles classification the Phytoremediation [13], because of its benign impact on landscape
after construction and low energy consumption. But this technology requires large implantation
areas depending on the amount of OMW to treat.
The Biocombus technology [14], has a positive Net Present Value, but has also a heavy impact on
landscape.
Table 5. Selected technologies of olive mill wastewaters

Technology INPUT Process Output Eco-sustainability
Electro- 3
coagulation device 100 55000 m /y Electro-
Clarified water
[15] OVW chemical
Evaporation- 3
2000 36 000 m /y Clarified water
Hydrolysis- Thermal
OVW Bio fuel
Oxidation
Phytoremediation 3
[13] 50 10 000 m /y Biological Word biomasa
Aerobic biological 3
30 m /d Biological Clarified water
treatment [16]
TIRSAV [17] All OMW more than Mixed compound for
Physical
2000 t/y other industries
Co-digestion
system applied to
waste water Clarified water and
5 t/day OVW Biological
treatment plants biogas
[18]
Biocombus [14] All OMW more than

Physical Industrial pellets
2000 t/y
Composting All OMW more than Physical and
Organic fertilizers
(3 technologies) 200 t/y biological
However the main purpose of the European Awareness Raising Campaign on Olive Mill Wastes
is exactly to raise the awareness among the sector stakeholders, about the environmental
sustainability of this economic sector that is crucial in some of the most economic, social and
environmental vulnerable regions of Europe. Olive oil industry provides invaluable contribution for
the economy and employment of all producing regions, and also landscape and biodiversity
protection for most of them [19].
The valorization or the economically viable treatment of olive mill wastes may come to prove very
important for the industry, in a moment of depressed olive oil prices. And, as the olive oil production
continues to increase, problems posed by the environmental impact of those wastes may become
unbearable burdens for the sector sustainability, in regions where the maintenance of this activity is
of utmost importance [19]
References:
[1] International Olive Council, World olive Figures,
http://www.internationaloliveoil.org/estaticos/view/131-world-olive-oil-figures,
consulted in August 2011
[2] Centre dActivits Regionales Pour la Production Propre (CAR-PP), Plan dAction pour la
Mediterrane, Prvention de la pollution dans la Production dhuile dolive, Barcelona
2000
[3] Michael Niaounakis, Constatinos P. Halvadakis, Olive Processing Waste Management :
nd
Literature Review and Patent Survey. 2 Edition, Elsevier, Oxford 2006
[4] M.J. Paredes, E. Moreno, A. Ramos-Cormenzana and J. Martinez, Characteristics of soil
after pollution with wastewaters from olive oil extraction plants, Chemosphere 16 (1987)
(7), pp. 15571564.
673
[5] M. DellaGreca, P. Monaco, G. Pinto, A. Pollio, L. Previtera and F. Temussi, Phytotoxicity
of low-molecular-weight phenols from olive mill wastewaters, Bulletin of Environmental
Contamination and Toxicology 67 (2001), pp. 352359.
[6] G. Rana, M. Rinaldi and M. Introna, Volatilisation of substances alter spreading olive
oil waste water on the soil in a Mediterranean environment, Agriculture, Ecosystems and
Environment96 (2003), pp. 4958
[7] V. Kavvadiasa, M.K. Doulaa, K. Komnitsasb, N. Liakopouloua, Disposal of olive mill wastes
in evaporation ponds: Effects on soil properties, Journal of Hazardous Materials 182 (2010)
144155
[8] M.A. Snchez-Monedero, M.L. Cayuela, C. Mondini, N. Serrami, A. Roig, Potential of
olive mill wastes for soil C sequestration ,Waste Management, Volume 28, Issue
4, 2008, Pages 767-773
[9] M.L. Cayuela, P.D. Millner, S.L.F. Meyer, A. Roig Potential of olive mill waste and compost
as biobased pesticides against weeds, fungi, and nematodes Science of The Total
Environment, Volume 399, Issues 1-3, 25 July 2008, Pages 11-18
[10] Ajmia Chouchene, Mejdi Jeguirim, Alain Favre-Reguillon, Gwenaelle Trouv, Grard Le
Buzit, Besma Khiari, Fethi Zagrouba, Energetic valorization of olive mill wastewater
impregnated on low cost absorbent: Sawdust versus olive solid waste , Energy, In Press,
Corrected Proof, Available online 16 April 2011, Journal of Hazardous Materials 182 (2010)
144155
[11] Carla Amaral, Marco S, Lucas, Joo Coutinho, Antnio Crespi, Microbiological and
physicochemical characterization of olive mill waste waters from a contnuos olive mill in
Northeastern Portugal, Bioresource Technology 99 (2008) 7215-7223
a a a
[12] M. Guardia Rubio , A. Ruiz Medina , M.I. Pascual Reguera and M.L. Fernndez de
Crdova, Multiresidue analysis of three groups of pesticides in washing waters from olive
processing by solid-phase extraction-gas chromatography with electron capture and
thermionic specific detection, Microchemical Journal Volume 85, Issue 2, April 2007,
Pages 257-264
[13] Santori, F, Anna Rita Cicalini and A Zingaretti.Exploitation of an agroindustrial wastewater:
fromOMW to biofuels Venice 2006 Biomass and Waste to Energy Symposium, Venice
November 29 to December1, 2006
[14] Claro, J. C. A. R., Valente, A. R. & Rosa-Pires, A.. A Process to Produce Biomass through
the Utilization and Recovery of Residues and Effluents from Olive Oil Production Units and
Cork Industry Wastes. Proceedings of 16th European Biomass Conference & Exhibition
From Research to Industry and Markets, Valencia, Spain, 2-6 June
[15] Boye, Birame, Farnia, G.; Sandina, G., Buso, A., Giomo, M. Removal of vegetal tannins
from wastwater by electroprecipitation combined with electrogenerated Fenton oxidation,
Journal of Applied Electrochemistry 2005, 35, 369-374.
[16] Tziotzios G., Michailakis S., Vayenas D. V. Aerobic Biological Treatment of Olive Mill
Wastewater by Olive Pulp Bacteria International Biodeterioration&Biodegradation 60 (4),
209-214, 2007.
[17] Altieri R., Esposito A. Olive mill wastes management: a novel approach working at mill
level for recycling in agriculture all kinds of effluents. International conference New
Technologies for the treatment and valorization of agro by-products. (2007) ISRIM, Terni 3-
5 October
[18] Berardino, S. Implementation of Codigestion and sludge management system in Portugal.
Water Practice & Technology IWA Publishing 2007-doi10.2166/wpt.2007.017.
[19] Filomena Duarte, Ndia Jones, Luuk Fleskens, Traditional olive orchards on sloping land:
sustainability or abandonment?, Journal of Environmental Management 89 (2008) 8698
674
MUNICIPAL SOLID WASTE MANAGEMENT PLANNING IN LOMBARDIA

REGION: LCA AS A STRATEGIC DECISION SUPPORT TOOL
1 1 1 2 3 3
L. Rigamonti , V. Brambilla , R. Luglietti , P. Zerbinati , D. De Simone , M. Severgnini , L.
3 1
Tasca and M. Grosso
1 Politecnico di Milano, DIIAR Environmental section, Piazza Leonardo da Vinci, 32 20133
Milan Italy, e-mail corresponding author: lucia.rigamonti@polimi.it
2 Regione Lombardia, Piazza Citt di Lombardia, 1 20124 Milan, Italy
3 CESTEC SpA, Viale Restelli, 5/A 20124 Milan, Italy
ABSTRACT
Life cycle assessment (LCA) has been chosen by Regione Lombardia as a strategic
support decision tool in the preparation of its new waste management plan. The goal is to
use the life cycle thinking approach to assess the current regional situation and thus to
give useful strategic indications for the future waste management.
The project (called GERLA: GEstione Rifiuti in Lombardia Analisi del ciclo di vita)
started in November 2010 and will be completed by the end of 2011. The first phase of
the study consisted in the analysis of the present management of municipal waste in
Lombardia (baseline scenario reference year 2009) and in its evaluation by means of
the LCA methodology. The critical analysis of the results of the baseline scenario has
allowed the definition of some possible future scenarios for the year 2020, with the final
goal of a further improvement of the environmental performances of the regional system.
This paper summarizes the main results obtained till now.
Keywords: Life cycle assessment, Waste management plan, Lombardia Region
INTRODUCTION
Life cycle assessment (LCA) has been chosen by Regione Lombardia as a strategic support
decision tool in the preparation of its new waste management plan. The goal is to use the life cycle
thinking approach to assess the current regional situation and thus to give useful strategic
indications for the future waste management. The research project (called GERLA: GEstione Rifiuti
in Lombardia Analisi del ciclo di vita) started in November 2010 and will be completed by the end
of 2011.
By bearing in mind that a status part (i.e. the assessment of the state-of-the-art of waste
management) and a planning part (i.e. the definition of future developments in waste
management) are the key elements of a waste management plan, the first phase of the study
consisted in the analysis of the present management of municipal waste in Lombardia (baseline
scenario reference year 2009). This has implied the identification of all the fluxes of materials
(both the source-separated fractions and the unsorted residual waste RW) in terms of quantity,
composition and destination, together with the characterisation of the most important treatment
plants, in terms of their capacity, energy and materials consumption, emissions in the environment,
energy and materials recovery. After that, the LCA methodology was applied to evaluate the
energetic and environmental impacts associated with this baseline scenario.
The critical analysis of the results of the baseline scenario has allowed the definition of some
possible future scenarios for the year 2020, with the final goal of improving the environmental
performances of the regional system.
675
Methodology and assumptions
LCA methodology was applied to analyse baseline and future scenarios and to evaluate their
impacts. LCA analyses were carried out following the ISO standards 14040 and 14044 [1, 2] and
by means of the SimaPro 7 software, developed by PR Consultants [3], in which we have created
new modules describing the life cycle of the different treatments included in both baseline and
future integrated waste management systems, as much as possible accurate in representing the
actual situation of Lombardia.
CML 2001 was adopted as the characterisation method [4] to evaluate the environmental impacts
(Global warming, Human toxicity, Acidification, Photochemical ozone creation), whereas the
Cumulative Energy Demand method [5] was chosen to assess the energy consumption of the
systems.
The LCA analysis takes into account all the fluxes of pollutants released in the environment by
each process, including both direct (e.g. those released from the waste treatment plants and from
the transport of the materials) and indirect emissions (e.g. those related to the production of the
reactants utilised in the flue gas abatement system of waste-to-energy - WTE - plants). These
positive emissions are then compared with the avoided ones [6, 7], which are those associated
with energy and material conventional productions displaced by energy and materials produced in
the waste management system. In fact, beyond treating waste, some activities (e.g. packaging
materials recycling, bio-waste composting and anaerobic digestion, and incineration of the residual
waste in waste-to-energy plants) lead to the production of new materials (called secondary
materials), compost or energy. In the LCA modelling, we have thus decided to expand the system
boundaries and to assess which products are replaced on the markets by those produced from
waste, including their replacement in the model. This methodology is called substitution by system
expansion or avoided burden method [7]. In general we have substituted the average primary
route market consumption mix (i.e. following the attributional principle [6]), except for the energy
recovery from waste where we have modelled the avoided heat and electricity according to the
consequential principle [6]. In particular, the electricity produced displaces that produced by a
combined cycle power plant fed with natural gas and the heat produced displaces that generated
by household boilers fed with natural gas.
Finally, we have used the zero burden assumption [8] meaning that the waste carries none of the
upstream burdens into the waste management system.
The functional unit is the amount of waste annually produced in Lombardia region, which is
obviously different in 2009 and in 2020 due to the expected variations of the per capita production
and of the resident population.
Baseline scenario
The focus in this study was on the management of municipal waste, in particular the six packaging
materials (glass, aluminium, iron, paper, plastic and wood), collected both in mono-material and in
multi-material way, the organic waste (food and green waste) and the residual waste. In the year
2009 the total production of these fractions in Lombardia Region was equal to about 4.4 millions
tonnes, split between 51% of source separation for material recovery and 49% of residual waste.
Out of this, 70% was sent directly to energy recovery in WTE plants, 26% was sent to mechanical-
biological pre-treatment (MBT) plants and only a negligible amount was sent directly to landfill.
Figure 1 shows the mass balance for the integrated municipal waste management system
implemented in Lombardia in 2009. The displacement of conventional products and energy, taken
into account in the LCA, is indicated, too.
After the identification of all the fluxes of materials in terms of quantity, composition and
destination, the characterisation of the treatment plants, in terms of their capacity, energy and
materials consumption, emissions in the environment, energy and materials recovery was carried
out. For this purpose, we acquired primary data via direct contacts with the most important plants
for each kind of treatment (i.e. selection plants, recycling plants, MBT plants, WTE plants,
composting plants, anaerobic digestion plants), to be utilised in the implementation of the
corresponding modules in the SimaPro software.
676
Energy:
88,676 t
LANDFILLS displacement
of fossil fuels
Residues/
Dry fraction/
Process Loss 105,175 t
bio-dried/bio-
SELECTIVE Residual waste stabilised
MONO/MULTI 2,166,350 t The residues are
MSW 570,963 t MECHANICAL BIOLOGICAL 264,055 t
sent to
4,403,066 t MATERIAL TREATMENT PLANTS RDF incineration/cement
COLLECTION kiln/landfill
121,932 t 158,880 t
according to their
Separated material Secondary fuel in 36,214 t
characteristics.
2,236,716 t cement kiln:
displacement of petcoke 85,718 t
SEPARATION OF MULTI-
MATERIAL COLLECTION
AND SELECTION OF EACH 1,506,711 t Energy + recovered
WASTE-TO-ENERGY material:
MATERIAL PLANTS displacement of fossil
fuels and primary
Residues
Ferrous metals: 60,315 t
Green waste: 436,207 t Residues products
Aluminium: 2567 t
Food waste: 419,038 t Glass: 363,944 t Recycled materials (Iron 53,119 t; Aluminium 2143
Paper: 563,590 t RECYCLING
t; Glass 363,944 t; Paper 501,595 t; Wood 137,632 t;
181,549 t Wood: 144,876 t PLANTS PET 44,298 t; HDPE 13,447 t; mix of polyolefins
673,696 t
Plastic: 109,058 t 21,266 t): displacement of primary products
ANAEROBIC COMPOSTING Residues
DIGESTION+
POST-
COMPOSTING Residues/
Process loss
Residues/ Compost (235,679 t):
Process loss displacement of peat
and mineral fertilisers
Compost (14,937 t) +
energy: displacement of
peat and mineral fertilisers,
and of fossil fuels
Fig. 1: Model of the integrated municipal waste management system implemented in Lombardia in
year 2009 (baseline scenario)
Future scenarios
The critical analysis of the results of the baseline scenario has allowed the definition of some
possible waste management scenarios for the year 2020, with the final goal to improve the
environmental performances of the regional system.
Considering the trend of historical data, a waste production of 4,838,297 tonnes has been
estimated for year 2020, with a separate collection rate of about 66%. Four future scenarios have
been analysed, in which the improvements actions described in table 1 were introduced.
Table 1: Future scenarios and respective improvement actions

Fraction of
Scenario Improvement action
interest
Increase of kerbside collection of paper, glass and plastic at the
Paper, glass, expense of bring-up collection
plastic, Removal of landfill as direct destination for residual waste
0
residual Fulfilment of internal energy consumption of WTE plants with the
waste energy produced by the plant itself (instead of buying it from the
national grid)
Those in 0 + Those of scenario 0 + introduction of the collection by trucks also for
1 green waste green waste and wood (instead of the collection carried out by each
and wood citizen with his/her own car)
Those of scenario 0 + improvement of energy recovery in anaerobic
Those in 0 +
2 digestion and treatment of all food waste through this process (instead
food waste
of composting it)
Those of scenario 0 +
recovery of aluminium (in addition to that of ferrous metals) from
3 Those in 0 WTE bottom ash
improvement of energy recovery in WTE plants increasing heat
recovery
677
removal of landfill as destination of bio-dried material (which is then
sent to WTE plants)
improvement of MBT technology replacing the process of
separation in dry and wet fractions + bio-stabilisation of the wet
fraction with bio-drying of all the residual waste
4 0+1+2+3 0+1+2+3
RESULTS
Table 1 shows the impact indicators calculated for the baseline scenario expressed first per
functional unit, which is equal to 4,403,069 tonne of waste in 2009, and then per 1 tonne of waste
produced and managed. The first ones are useful to understand the magnitude of the impacts
associated with the waste management service implemented in Lombardia in 2009 and they can
be utilised to make a comparison among the different years, taking into account the changes both
in the service and in the amount of waste produced. The indicators expressed per 1 tonne of waste
are instead not affected by the production of waste and so they can be used for a comparison
among management systems in which different technical solutions are realised. Moreover, the
results are given both including and not including the avoided impacts associated with material and
energy recovery from waste. Finally, we remember that a negative value indicates that the avoided
impacts are higher than the added ones, thus meaning a benefit for the environment; vice versa for
a positive value.
Table 1: Impact indicators for the baseline scenario

Per functional unit Per 1 t of waste
With avoided Without avoided With avoided Without avoided
Potential impact indicators
impacts impacts impacts impacts
Cumulative energy demand
-2.63E10 2.03E10 -5962 4608
[MJ eq.]
Global warming [kg CO2 eq.] 2.25E7 2.52E9 5 572
Acidification [kg SO2 eq.] -9.49E5 7.20E6 -0.22 1.64
Human toxicity
-1.85E8 6.76E8 -42 154
[kg 1,4-DCB eq.]
Photochemical ozone creation
-8.22E3 9.31E5 -0.002 0.211
[kg C2H4 eq.]
When avoided impacts are included, all indicators, except global warming, are negative, thus
indicating a positive environmental performance. Global warming indicator is positive because of
the impact associated with the management of residual waste, in particular its incineration: the
avoided impacts are not so significant to compensate those added in the environment, especially
due to the choice of the kind of displaced electricity (i.e. from natural gas in a combined cycle).
The comparison between the values with and without avoided impacts allows to understand the
importance of implementing a waste management system with the function not only of disposing
waste but even of managing it as a resource to be utilised to produce energy and materials.
Figure 2 shows the global warming indicator associated with the treatment of one tonne of each
fraction. These values multiplied by the corresponding amount of fraction managed in 2009 and
then added together give the value of 2.25E7 kg CO 2 eq. reported in table 1. As we can see, the
management of all the packaging materials, except wood, gives benefits for the environment,
thanks to the avoided impacts associated with the replacement of primary materials with secondary
materials. In particular, the recycling of aluminium gives the highest benefits in all impact indicators.
On the contrary, wood and green waste show positive values mainly due to the high impacts
associated with their collection. As previously said, the positive value for the residual waste is
associated with WTE plant modelling, whereas that for food waste is due to the limited benefits
resulting from the composting phase and the impacts for the collection.
678
ferrous food green
aluminium metals paper plastic wood glass waste waste RW
600
384
400
235 205
200
21
0
kg CO2 eq/t
-200
-400 -315
-600
-654
-800 -718
-1000 -919
-1200 -6767
Fig. 2: Global warming indicator associated with the treatment of 1 tonne of each fraction in 2009
(values include the avoided impacts)
Finally, figure 3 shows the global warming indicator for baseline scenario and future scenarios. The
increase in the separate collection (and consequently in material recycling), together with the
improvement actions, allow getting benefits also in this indicator. The best result is for future
scenario 4, which includes all the improvement actions envisaged.
For the other indicators, the improving of regional system performances varies between 128%, for
the cumulative energy demand indicator, and 7400%, for the photochemical ozone creation
indicator.
200
23
0
kg CO2 eq. * 10 6 / year
-200
-253
-400 -303
-600 -502
-636
-800
-1000 -937
-1200
baseline 0 1 2 3 4
Fig. 3: Global warming indicator for baseline scenario and future scenarios, expressed per
functional unit
679
CONCLUSIONS
LCA was chosen by Regione Lombardia as a strategic support decision tool in the definition of its
new waste management plan targeted at the year 2020. For the first time in Italy the outcomes of a
detailed LCA of a current waste management system are utilised to address future policies
pursuing the improvement of the environmental performances of the system itself.
After the evaluation of the baseline scenario (reference year 2009), a number of improvement
actions were identified and individually assessed, which can lead to environmental benefits, as
shown for example for the global warming indicator, where the emission of up to 1 million tonnes of
CO2 equivalents per year can be actually saved.
Future research within the project includes the definition of different, and more challenging,
scenarios of source separation, as well as scenarios where waste prevention activities are also
included.
Acknowledgements
The GERLA project is financially supported by CESTEC-Regione Lombardia. We wish to thank all
plant operators who have supplied primary data for the LCA.
References
[1] ISO, 2006. ISO 14040 Environmental management - Life cycle assessment - Principles and
framework.
[2] ISO, 2006. ISO 14044 Environmental management - Life cycle assessment - Requirements and
guidelines.
[3] PR Consultants, 2010. SimaPro 7 software. http://www.pre.nl/content/simapro-lca-software
[4] CML, Bureau B&G, School of System Engineering, Policy Analysis and Management Delft
University of Technology (2001) Life cycle assessment: an operational guide to the ISO
standards
[5] Jungbluth, N. and Frischknecht, R. (2004) Implementation of Life Cycle Impact Assessment
Methods, Ecoinvent report n. 3, www.ecoinvent.ch
[6] EC, JRC, IES (2010) ILCD Handbook: General guide for Life Cycle Assessment Detailed
Guidance, http://lct.jrc.ec.europa.eu/assessment/data
[7] Finnveden, G., Hauschild, M.Z., Ekvall, T., Guine, J., Heijungs, R., Hellweg, S., Koehler, A.,
Pennington, D., Suh, S. (2009) Recent developments in Life Cycle assessment, Journal of
Environmental Management, 91 (1), 1-21
[8] Ekvall T., Assefa G., Bjorklund A., Erikson O., Finnveden G., 2007. What life-cycle assessment
does and does not do in assessments of waste management. Waste Management 27, 989-996.
680
14th September
Session 2.7
( WASTE-TO-ENERGY AND RDF 1 )
Chairman: Javier Escudero
681
POTENTIAL FOR ENERGY RECOVERY FROM MALTESE MSW: A

THERMODYNAMIC ANALYSIS
1 2 3
F.J.C. Pirotta , C.A. Bernardo and E.C. Ferreira
1 Institute for Polymers and Composites / I3N. Minho University, School of Engineering, 4800-058
Guimares, Portugal. pg13990@alunos.uminho.pt
2 Institute for Polymers and Composites / I3N. Minho University, School of Engineering, 4800-058
Guimares, Portugal. cbernardo@dep.uminho.pt
3 IBB, Institute for Biotechnology & Bioengineering / CEB. Minho University, School of Engineering,
4710-057 Braga, Portugal. ecferreira@deb.uminho.pt
ABSTRACT
An investigation of the Maltese Municipal Solid Waste (MSW) potential for energy
recovery is carried in this work. In a first step, MSW composition data was collected to
evaluate the waste combustion enthalpy by a weighted average of each fraction, using
the corresponding Low Heat Value (LHV). Results indicate that each kilogram of Maltese
MSW releases circa 8,726 kJ of energy when combusted. Data from 1997 to 2009
allowed the conclusion that an incinerator with a capacity of 32.5 tonnes per hour can
treat the waste expectably generated in Malta during the plant life span. In a second step,
MSW elemental analysis was used to evaluate (i) the necessary stoichiometric air
(152.4%) and (ii) the temperature of the flue gas (915.5 C), respecting the 6% ratio
(voxygen/vfluegas) imposed by EU regulations. Finally, the thermodynamics of the steam
cycle was applied to study the possible contribution of energy recovery for electrical
power generation (PG) and co-generation (CHP). The thermal energy was analyzed
assuming its use in desalination (multi effect distillation, MED), by means of the so-called
gain output ratio (GOR) index. The final results lead to a potential power of 10 MW (PG)
3
or a minimum of 7.25 and 4.85 millions m /year of desalinated water MW (CHP).
Keywords: Islands of Malta; Municipal Solid Waste, Incineration, Energy recovery; Power; Water
desalination.
INTRODUCTION
The scarcity of energy and drinkable water sources is a real problem in the sustainability strategy
of small Islands, namely those that are 100% dependent on fossil fuels. In parallel, the intensity of
the MSW generated by human and economic activity also poses difficulties, by affecting land use
and causing environmental impacts. This is particularly critical when landfilling is the only End-of-
Life practice.
This situation has made the Islands of Malta of particular interest as a case study, especially
considering that (a) 64% of total gross inland primary energy in 2008 was consumed by the
electricity sector; and (b) the water supply depends on desalination and circa 54% of the drinkable
water is obtained by reverse osmosis. Other critical facts are: (i) Malta has the highest MSW mass
2
per area landfilled in the EU (900 tonnes/km ); (ii) MSW generation increased 48% between 1998
and 2008; (iii) 87.3% of the MSW produced in that period was landfilled; and (iv) data recently
released shows a tendency of MSW stabilization for the next years. Malta is economically
dependent of tourism activity, which exacerbates the problem of electricity and water demand as
well as waste generation during summer.
Thus, incineration of MSW with energy recovery can be an important management option,
contributing to reduce the fossil fuels dependence while concomitantly reducing the volume of the
MSW landfilled and diversifying water treatment, taking advantage of the remaining thermal
energy.
682
THE MALTESE CASE STUDY
Malta is one of the smallest countries in the world, a small archipelago, constituted by three main
Islands, Malta, Gozo and Comino, located 93 km south of Sicily and 288 km north of Africa, with a
2
total area around 316 km . In 2009 there were 412.966 inhabitants in Malta, which made it the
most densely populated country in Europe: 1,307 inhabitants per square meter.
Natural resources are limited, as the Maltese archipelago has no rivers, forests or mountains. The
Mediterranean climate, characterized by mild winters and dry, hot summers, defines its weather,
with air temperature generally between 9.5C and 33C. The hottest period of the year runs from
mid-July to mid-September and the coldest months are January and February.
The main economic sectors in Malta are (i) tourism; (ii) financial services; (iii) public services; (iv)
construction and quarrying; (v) agriculture and fisheries. The public sector generated 21.4% of the
jobs. The private sector, of which the flagship is the service sub-sector (tourism; manufacture and
wholesale and retail trade; repairs) is responsible for 73.2% of the overall employment. The
remaining jobs are due to statutory bodies.
METHODOLOGY OF THE ANALYSIS

As the key-objective of the research is to evaluate the energy obtainable from the Maltese MSW,
the analysis was divided into three phases. First (1), a literature review and a data collection were
conducted to gather information on MSW composition and generation. High heat values (HHV)
from international literature and moisture from the collected data were used to estimate its LHV. In
a second phase (2) the waste combustion model (stoichiometry of C, H, S) was used to estimate
the air throughput in accordance with operational (temperature) and UE regulations (oxygen in the
flue gas). Finally, the potential for electricity generation and water treatment was assessed by the
use of steam thermodynamics, electing two different plant options and limiting the thermal
desalination technology to multi stage distillation (MED). The gain output ratio (GOR) was applied
to estimate the potential for water desalination in a CHP plant. The combination of heat and power
was studied considering a backpressure turbine and a condensing turbine with steam extraction.
Maltese MSW characteristics and generation

A household solid waste (HSW) survey carried out in Malta, Gozo and Comino in 2002 provides
weekly composition data for every quarter of the year. HSW corresponded to circa 70% of the
waste generated in that year. The composition of the hotels and restaurants waste was estimated
using data of a pilot project performed by the National Statistics Office in 2004 that identified
primary and secondary packaging, biodegradable matter and other waste fractions in hotels and
restaurants rooms and hotels swill rooms. This information must be complemented with data from
other countries, namely that of an Irish non-household waste characterization survey, which
detailed the various Hotels and Restaurants fractions and identified which of them corresponded to
packages or to non-packages. In the case of commercial and industrial waste the composition was
taken from an EU Joint Research Centre study. The relevant data is shown in Table 1
Table 1 Maltese MSW composition

Restaurants Restaurants Commercial Commercial
Household Household HHV
Fraction/Source & Hotels & Hotels Industrial Industrial
[% w/w] [ktonne/year2002] [kJ/kg]
[% w/w] [ktonne/year2002] [% w/w] [ktonne/year2002]
Plastic Containers 4,93% 6,646 4,63% 956 22,1% 5,657 -32,564
Plastic Film 4,96% 6,688 3,35% 691 0,0% 0 -32,200
Paper 9,13% 12,307 9,74% 2,011 31,6% 8,089 -15,800
Cardboard/Cartons 5,72% 7,718 10,81% 2,232 0,0% 0 -18,463
Food Remains 57,90% 7,8071 40,44% 8,349 19,7% 5,043 -5,512
Glass Bottles 3,87% 5,218 11,67% 2,408 15,2% 3,891 -140
Iron Cans 3,56% 4,799 3,38% 697 5,8% 1,485 -698
Aluminium Cans 0,25% 334 0,99% 205 0,6% 154 -698
Textiles 3,16% 4,264 2,58% 532 1,0% 256 -17,245
Hazardous 2,08% 2,799 0% 0 0,0% 0 -12,791
Others 4,45% 5,999 4,72% 975 4,0% 1,024 -6,978
Vegetable Oils 0% 0 7,69% 1,588 0,0% 0 -38,290
683
The Table summarizes the composition of the three waste streams that make up the Maltese MSW.
The commercial and industrial waste figures were calculated using reports and studies from other
municipalities/countries, some of them with similar geographical characteristics (e.g. Cyprus).
Common materials were clustered to provide complete data for the LVH estimate. In 2002, the
Household, Hotels & Restaurants and Commercial/ industrial waste streams amounted respectively
to 134,844, 20,644 and 25,597 tonnes. The last column of the Table depicts the HHV of the
different material fractions used in the estimations, obtained from the literature [1]. The contribution
of each material fraction for the final HHV of a given stream was calculated by the product of the
corresponding weight % and HHV. The sum of the contributions of all fractions, considered as-
discarded (prior to mixing with other components in the refuse), resulted in the overall HHV [2].
Eq. 1 was used to evaluate the LHV (that accounts for the energy recoverable from MSW
combustion), with the same rationale presented in the paragraph above for the HHV. In the
equation, represents the latent heat of water vaporization, %W the moisture content (w/w) and
%H the mass percentage of hydrogen (elemental composition).
LHV (kJ/kg) = HHV x [9 x (%H) + (%W)] (1)
The final LHV of the Maltese MSW was estimated as (-)8,726 kJ/kg of waste, as shown in Table 2.
Table 2 Moisture and LHV from Maltese MSW

Household, Restaurants
Moisture
Composition & Hotels and Commercial
as-fired [%, w/w]
/Industrial LHV [kJ/kg]
Plastic Containers 13.80% -2,254
Plastic Films 13.80% -1,219
Paper 24.30% -1,736
Cardboard/Cartons 24.30% -913
Food Remains 63.60% -1,400
Glass Bottles 3% -3.3
Iron Cans 6.60% -16
Aluminium Cans 6.60% -1.6
Textiles 23.80% -429
Hazardous 12.80% -177
Others 8% -273
Vegetable Oils 59.00% -304
Total 43.5% -8,726
The forecast of the maximum yearly waste to be generated during the lifespan of an incineration
plant is essential to determine its capacity. In fact, the increase in waste generation in the future
years may lead to inadequate capacity and, consequently, to the need of an expansion, which is
not economically and environmentally desirable. Three simplified scenarios were assumed for the
MSW projections, all based on an incinerator operation time of 8,000 hours per year (Table 3).
Table 3 Scenarios for waste generation

Estimated capacity
Scenario Criterion
[tonne/hour]
Last MSW data (2009) 5% excess capacity 32.5
Historical data (1997 to 2009) Trend line (plot) 31.5
Average MSW per capita (1997 to 2009) Population projection (EUROSTAT) 32.0
Then, considering that the 32.5 tonne/hour capacity obtained in scenario 1 (with 5% excess
capacity) will cover all the predictions, for 8,000 hours of operation the future incinerator would
have to treat a maximum of 259.8 ktonnes/year up to 2030 (assuming that operations will start in
2015 and a 15 years lifespan). From hereafter this value will be used in all design calculations.
MSW combustion
The analysis of the energy involved in the MSW combustion considers the complete combustion of
the three basic elements - carbon (C), hydrogen (H), and sulphur (S) -, using typical physical and
684
elemental compositions from the literature. The oxidizing atmosphere is promoted by air injection,
assuming its composition to be 21% (molar) oxygen and 79% (molar) nitrogen. To determine the
limit amount of air in the combustion it is necessary to perform an energy balance, taking into
account the requirements of pertinent European Directives. These are: (i) the volume ratio between
oxygen and the flue gas must be equal or higher than 6%; (ii) the temperature of the flue gas must
be maintained between a minimum of 850 C, to avoid dioxins formation, and a maximum of 1050
C, to avoid the degradation of the refractory material by ash fusion. The energy balance in the
incinerator enunciates that the variation of the flue gas enthalpy (H fg) is caused by the heat
released during the combustion (LHV). Eq. 2, where Hlosses is the thermal energy lost, represents
the percentage of energy lost as a function of the total energy released, and msw is the MSW
throughput (e.g., 32.5 tonnes/hour), summarizes the energy balance. The overall flue gas enthalpy
can be evaluated by the sum of the individual enthalpies (O2, N2, H2O, CO2, SO2) [2].
Hfg = LHV x msw Hlosses = Hfg = HO2+HN2+HH2O+HCO2+HSO2 =

LHV x msw x LHV x msw = LHV x msw (1 - ) (2)
Then, the overall enthalpy variation (H) is assessed by introducing the thermodynamic concept of
specific heat at constant pressure, or constant heat capacity (Cp) [3]. A third degree polynomial
relationship between Cp and temperature, described in the literature, was used to estimate the final
temperature of each gas (by solving Eq. 2), through a trial-and-error method and an iterative
process. About 52.8% excess of the theoretical air satisfies all the previously mentioned criteria
and maximizes the potential for energy recovery; thus, recirculation of the flue gas was not deemed
necessary. Concurrently, 915.5 C and 7,864 kJ/kg were taken, respectively, as the final flue gas
temperature and the overall enthalpy variation in further calculations.
Contribution of energy recovery for the Maltese electrical sector

Energy recovery arises from the need to cool the flue gas from 915.47 C to 250 C before its
treatment in the mechanical equipments that operate at lower temperatures. In the calculations, the
flue gas represents the heat source (boiler) where the sub-saturated water is evaporated and
superheated before passing through the backpressure turbine.
The electrical potential is analyzed in the light of the Rankine cycle, determined by the ideal
enthalpies of each thermodynamic state (turbine, boiler, condenser and pump), based on state
proprieties (temperature, pressure and entropy). The isentropic efficiency, from the second
thermodynamic law, is next applied to assess the actual enthalpies (turbine and pump), necessary
to estimate the real electrical power. The estimation of the net electrical power was performed for
two different steam operational conditions, 4.0 MPa / 440 C and 5.2 MPa / 440 C, both applied in
real incineration plants. In both cases, the operational pressure and temperature of the condenser
were considered to be 0.01 MPa and 45.8C [2].
The procedure starts with the evaluation of the steam mass flow rate, ST through Eq. 3, where 3
and 1 signify the enthalpy of the superheated steam in the turbine inlet and the enthalpy of the
sub-cooled steam in the condenser outlet, the difference represents the specific enthalpy
variation and BO the efficiency of the boiler.
[msw x (915.6 - 250) x BO] / (3 1) = ST (3)
Then the shaft work (turbine), Pmech, is estimated by using Equation 4, considering the mass steam
flow rate already calculated and the enthalpy at the turbine inlet (h3) and outlet (h4).
Pmech = ST x (3 4a) (4)
Both the inefficiency of the turbo-alternator that converts mechanical into electrical energy (3%),
and the consumption of electrical energy on-site (70 kW/tonne of MSW) were taken into account in
the final estimation. Table 4 presents the results. From the data in the Table, it can be concluded
that the annual potential corresponds to about 82.0 GWh/yr (for 8,000 operation hours). Depending
on the operational conditions, it is also equivalent to approximately 3.7% to 3.8% of the total energy
685
produced in 2009 (2,167 GWh/yr). Finally, it corresponds to slightly more than the total energy
consumed by the water desalination process in that year: 79.4 (GWh/yr) [4].
Table 4 Results for electrical power generation (PG)

Operation conditions
Property Symbol Units
(4 MPa) (5.2 MPa)
Net electric power PNET,EL 10.1 10.4 MW
Overall plant efficiency nNET 22.5% 23.3% -
Electric power produced PEL 12.4 12.7 MW
Electric power consumed in the plant PEL,com 2.28 2.28 MW
Turboalternator efficiency nTA 97% 97% -
Mechanical energy Pmech 12.7 13.1 MW
Steam flow rate SHS 50.6 50.9 tonne/h
Alternatively, if one considers the heating value (HV) of the fuel oil for industrial burners (fuel oil
number 4) to be between 151.0 and 156.2 MJ per US gallon, (38.9 - 41.3 MJ/litre), and an average
power plant efficiency of 32% (as in the existing Delimara and Marsa plants), it is possible to
estimate that the corresponding avoided consumption of fuel oil will be between 2,747 and 2,845
litres per hour.
Contribution of energy recovery for electrical and water treatment (CHP)

Part of the thermal energy from MSW combustion can be used for electrical power production and
the remaining used to desalinate seawater, taking advantage of the energy to evaporate the water
from brine. The distillation is initiated at 70 to 80 C, due to the low pressure that should be
maintained over the MED cells to sustain the evaporation mechanism, as the heat losses and the
boiling point elevation (brine) influence the evaporation process [4]. In a MED plant, the
performance ratio, also called Gain Output Ratio (GOR), relates the water production to the steam
consumed. The typical GOR value is 12 kg of distillate per kilogram of steam consumed; moreover,
3
the power consumption is minimized, about 2 kWh/m [5]. To satisfy MED requirements, the steam
specification after expansion in the turbine must be at 0.035 MPa and 72.68 C [6]. Two different
types of turbines were considered: (a) backpressure, in which the superheated steam is initially
expanded in the turbine, and then condensation is performed by the MED plant and (b) condensing
turbine which has a steam extraction (5a) before complete expansion (4a, 0.01 MPa and 45.8 C).
The extracted steam (additional outlet nozzle) feeds the MED plant and the remaining steam
(turbine) follows to the condenser system after expansion to 0.01 MPa.
The evaluation of the electrical power and the flow rate of water treated when the backpressure
turbine is combined with MED follows the same procedure and formulae introduced before.
However, for the condensing turbine with steam extraction, the thermal power (upstream and
downstream) and electrical power are evaluated through Equations 5, 6 and 7.
PTH,ext-ups = ST,ext x (5a 6) (5)
PTH,ext-dow = ST x (4a 1) (6)
Pmech = ST x (3 4a) + ST,ext (3 5a) (7)
In the equations above PTH,ext-ups, ST,ext, PTH,ext-dow , 5a, 6, and 1 are respectively the thermal
power and the flow rate of the extracted steam, the thermal power of the sub-cooled steam and the
enthalpies at the outlets of the turbine, the MED process and the condenser [8]. Finally, the PES
(Primary Energy Savings) index from Directive 2004/8/EC (Eq. 8) was applied to estimate the fuel
energy saved by using a CHP plant. The index compares the fuel energy required to run the
heating and the power plants, with that required if they were replaced by the co-generation facility.
Reference PES values for a new MSW incineration plant, extracted from the Directive, are 25% for
separate electricity generation and 80% for separate heat generation. Furthermore, the efficiency
reference for separated electricity generation can be further corrected for climate conditions and
avoided grid losses.
686
PES = 1 1/[(EL,CHP/Ref E) + (TH,CHP/Ref H)] (8)
In Eq. 8, EL,CHP and TH,CHP represent, respectively, the calculated electrical and thermal power
efficiencies of the CHP plant, and Ref E, Ref H the corresponding Directive reference values. The
main results obtained are presented in Table 5. An acceptable value for PES ( 10%) is only
achieved for a steam extraction equal or greater than 90% and 5.2MPa of operational pressure.
Table 5 Results for electrical power generation and water desalination (CHP)
(4 MPa) (5.2 MPa) 5.2 MPa; Condensing
Property Symbol Units
Backpressure Backpressure ST,ext = 90% x STCond.
Net electric power PNET,EL 8.46 8.85 9.01 MW
Primary energy savings index PES 13.5% 14.6% 11.1% -
Electric power produced PEL 10.7 11.1 11.3 MW
Electric power consumed in the plant PE,com 2.28 2.28 2.28 MW
Turbo-alternator efficiency nTA 97% 97% 97% -
Mechanical energy Pmech 11.1 11.5 11.6 MW
Thermal energy available PTH 31.2 30.8 27.7 MW
Gain output ratio GOR 12 12 12 Kgwter/kgsteam
Flow-rate of water desalinated per hour VWD 606.8 610.2 529.2 tonne/h
Volume of water desalinated per year VWDY 4,854,285 4,881,859 4,393,670 m3/yr
Final electrical power (after MED) nTHP 7.25 7.63 7.91 MW
For the two backpressure configurations, the PES index shows that when MED is combined with
electrical power plant, 13.5% to 14.6% savings of primary energy can be achieved, respecting the
limit established by the European Directive. The drinkable water produced is about 30% of the total
3
water desalinated in the RO plants in 2009 (16,645,743 m ). The combined capacity for electricity
production from the backpressure turbine is achieved, allowing for 2,765 and 2,948 litres of avoided
fuel oil, respectively. On the other hand, the condensing turbine has a potential for fuel oil savings
of about 2,873 litres. Despite a lower power for water desalination if compared with the
backpressure turbine for both steam operational conditions, the condensing turbine permits
modulating the water production according to the yearly energy and water demands.
CONCLUSION
Globally, the present work allows the conclusion that the incineration of the MSW generated in
Malta can help reduce deposition in landfills, therefore decreasing the pressure on land use and
the potential for water and soil contamination. Additionally, by integrating energy recovery, it can
diminish the amount of primary energy (fuel-oil) consumed in the two existing power plants
(Delimara and Marsa) and in the seawater desalination treatment. Finally, as incineration
generated electricity can be considered as deriving from a renewable source, it can help meet the
20% renewable energy target imposed by Directive 2009/28/EC.
References
[1] Meraz AD, Kornhauserb I, Rojas F. A thermochemical concept-based equation to estimate

waste combustion enthalpy from elemental composition. Fuel 2003; 82, 1449-1507.
[2] Mastro F, Mistretta, M. Cogeneration from thermal treatment of selected municipal wastes. A
stoichiometry model building for the case study of Palermo. Waste Management 2004; 24, 309-
317.
[3] Rousseau, RMF, Ronald W. Balance in reactive process. Elementary Principles of Chemical
Process. US: John Wiley & Sons, 2000, Third volume.
[4] Zsigraiova Z, Tavares G, Semiao V, Carvalho MG. Integrated waste-to-energy conversion and
waste transportation. Energy 2009; 34, 623635.
[5] Wade, N. M. Distillation plant development and cost update. Desalination 2001; 136, 3-12.
[6] IDE Thermal desalination solution. [Online] http://www.ide-tech. com/files
/990b0fa01310a9c82f841f2183e9ebcb/downloadchapter/2010/01/MED%20Brochure.pdf27.
687
SCENARIOS FOR WASTE-TO-ENERGY USE SWEDISH PERSPECTIVE
1 1 1 1 1
B. Guziana , H. Song , E. Thorin , J. Yan , E. Dotzauer
1 School of Sustainable Development of Society and Technology, Mlardalen University, SE-72123

Vsters, Sweden, bozena.guziana@mdh.se
ABSTRACT
The use of waste for energy purposes becomes increasingly interesting, both with respect to
waste management and with respect to the energy system. The decisions on alternative
uses of waste for energy are mainly influenced by different policies and technologies related
to waste management as well as energy supply and use. Two important issues, namely, a
clear priority of waste prevention in waste management within the EU, and the growing
concern for food losses and food waste at global and at national level, shall be carefully
considered and addressed. This paper proposes scenarios for waste-to-energy systems with
a focus on Sweden and with a broader EU approach applied. As baseline for the scenario
development, an inventory of relevant policies and goals at international, national, regional
and local level is made, as well as an inventory of existing scenarios and reports about future
trends. A low waste availability level is recommended for sensitivity analysis of the
scenarios.
Keywords: waste-to-energy; scenario; biofuels; bioenergy, waste prevention; recycling parks
INTRODUCTION
The use of waste for energy purposes is becoming increasingly interesting, both in relation to waste
management and in development of the energy system. The decision on alternative uses of waste for
energy are mainly influenced by different policies and goals regarding waste management and energy
supply and use, as well as the development of different waste-to-energy technologies [1]. Waste-to-
energy has developed into one of the most commonly used technologies for tackling waste in Europe.
Waste-to-energy can make a contribution to sustainability, save resources, mitigate climate change, i
improve energy efficiency, and be an alternative to landfill [2,3,4,5]. The main objective of this paper is
to propose scenarios for a regional waste-to-energy system that are in line with main policies and
goals related to waste-to-energy at international, national, regional and local level, using the County of
Vstmanland in Sweden as a case study.The current status of the waste-to-energy chain in the county
of Vstmanland is described in a report, as part of the project REMOWE Regional Mobilising of
Sustainable Waste-to-Energy Production [6].The paper presents an overview of existing scenarios and
reports about future trend development in the field of waste-to-energy. Furthermore the background for
the recommended Low Waste sensitivity analysis is given as well as an assumption of yearly changes
of waste intensities .
METHOD
In this paper, scenarios for a region in Europe of importance for the development of waste-to-energy
systems are proposed. A region in Sweden, the County of Vstmanland, is used as a case study to
illustrate the development of the scenarios. In a first step, an inventory of policies and goals at
international, national, regional and local level is made, as well as existing scenarios and reports about
future trend development related to the waste-to-energy area. From the results of the inventory, three
main scenarios, including waste intensities are proposed.
LITERATURE REVIEW
Waste-to-energy related policies and goals at international, national, regional and local level
688
An overview of policies and goals at EU, national and regional level with relevance for the waste-to-
energy is presented in Table 1.
Table 1 Overview of waste-to-energy related policies and goals at EU, national and regional level
Energy Waste
EU (international level) EU (international level)
COM (2011) 112 A roadmap for moving to a competitive low carbon COM (2011) 13 on the Thematic Strategy on the Prevention and
economy in 2050 Recycling of Waste
COM(2011) 144 Roadmap to a Single European Transport Area Framework Waste Directive (1975, 2008)
Energy Policy (2007) 20-20-20 goal Landfill Directive
Sweden (national level) Sweden(national level)
The Swedish climate and energy policy (2009) The Swedish waste policy(2005)
Biofuels strategy (2010) Environmental objectives
A Good Built Environment /Waste
Vstmanland (reional level) Vstmanland (regional level)
Climate and energy strategy for the Vstmanland County (2008) VafabMilj Waste plan for 2009-2012
Fossil free Vstmanland 2015
Energy policies
The EU Energy policy [7] consists of two binding targets for 2020: 20% Renewable Energy Sources
(RES) share in gross final energy consumption, including the subtarget to have 10% share of RES in
transport, and 20% GHG reduction, compared to the level of 1990. The current EU goals for 2020 also
involve improving energy efficiency by 20%. The Communication A Roadmap for moving to a
competitive low carbon economy in 2050 [8] set milestones of 80% domestic reduction of GHG by
2050 (40% reduction in 2030 and 60% reduction in 2040, compared to the level of 1990). This
communication stresses that electricity will play a central role in the low carbon economy. The
Swedish Parliament [9] has decided on the target of at least 50% RES in the energy use in 2020, and
at least 10% of RES in the transportation sector. Furthermore, the ambition of the Government is that
the Swedish fleet of vehicles should be independent of fossil fuel by 2030.The parliament has also
decided on the target of 20% decreased energy intensity for the energy sector between 2008 and
2020. At the regional level, The climate and energy strategy for the Vstmanland County with goals
until 2020 [10] and the vision of a fossil free Vstmanland [11], are identified. A fossil fuel free energy
system in the Mlardalen region is described by Dahlquist, Thorin and Yan [12]. Traditionally, the
municipalities have played an important role in the Swedish energy system, both as local energy
distributors and as owners of large numbers of public buildings. Nowadays there is a great variation in
the work with energy planning at local level, which also is case in the Vstmanland County [6].
Waste policies
The revised Waste Framework Directive (WFD) was adopted in 2008 [13]. Recycling and recovery of
waste are promoted by targets, separate collection and energy efficiency criteria. Waste-to-energy
incineration is re-classified in the WFD as a recovery operation provided that waste-to-energy plants
meet certain efficiency standards. The new framework is the explicit requirement for Member States to
promote reuse and recycling. Swedish waste policy [14] is based upon the EUs waste hierarchy. The
current national waste plan was published in 2005 by the Swedish Environmental Protection Agency
th
(EPA) and a new one is under work. The 15 Swedish environmental objective, a Good Built
Environment, calls for waste prevention, a high recovery of resources in waste, while minimizing the
negative impact on peoples health and the environment [15]. The available regional waste plan is
developed by the company Vafab Milj AB [16]. The main points in the plan stresses among others
that the total quantity of waste and the hazard it poses should decrease and that the resources
contained in the waste will be utilized.
Waste-to-energy related scenarios and reports about future trends

The overview of selected sources is presented in Table 3.
Table 3. Overview of waste-to-energy related scenarios and reports.
Waste/ EU
COM (2011) 13 on the Thematic Strategy on the Prevention and
Recycling of Waste. [17]
EC(2008) Final Report. Analysis of the evolution of waste reduction Two extreme scenarios: Recyclable Society : 100% recycling of
and the scope of waste prevention. [18] recycled materials and 0% Recycling: nothing is recycled.
Waste/ Sweden
Sundquist et al. (2010) Model for Future Waste Generation [19] Four Scenarios: Global Sustainability; Global markets, Regional
markets and European Sustainability, 2030.
Ambell et al.(2010) Potential for increased material recovery of Three Scenarios: Current (2006); 2030-Business as usual; 2030
household and industrial waste (in Swedish) [20] Increased material recovery.
Sjstrm and stblom (2010). [21] Baseline scenario and Decoupling scenario, 2030.
Waste/Regional level
Vafab Milj(2009) Waste Plan 2009-2012 [16] Future waste quantity in Vstmanland
689
Energy/EU
EC(2010) EU energy trends to 2030 [22] Two scenarios, the Baseline 2009 (finalised in December 2009)
and the Reference Scenario (April 2010) are presented.
Energy/Sweden
Swedish Energy Agency (2009) Long-term Forecast for 2008;(in Energy use in main scenario up to 2030, in four alternative
Swedish) [23] scenarios up to 2020.
Swedish Energy Agency (2011) Long- term Forecast for 2010 (in Main scenario and two alternative scenarios: increased economic
Swedish) [24] development and increased fossil fuels price. The proposed
scenario spans the period 2007-2030
Gode et al. (2010) Swedish long-term low carbon scenarios. Two scenarios: the main scenario ; Biofuels 2050 and an
Exploratory study on barriers and opportunities. [25] alternative scenario Fossil Fuels+ Bio CCS 2050
Profu (2010)Scenarios for development of electricity and energy

systems to 2050 (in Swedish). [26]
RESULTS
Proposed scenarios for waste-to-energy use

The overview of proposed scenarios is given in Table 4. 2030 and 2050 have been selected as the
time horizon for the scenarios. The main substitute for fossil fuels and the possibilities of renewable
energy export are basic elements that define the scenarios as well as the development of waste
amounts.
In the Swedish energy policies [9]] the goal of a vehicle stock that is independent of fossil fuels by
2030 is set, and at the regional level there is the vision of a fossil fuel free Vstmanland, developed by
the regional association of Agenda 21 [11].Therefore, in all scenarios proposed, the transport system
is assumed to be fossil fuel free. In addition to the energy efficiency of vehicles and the reduction of
transport needs, this goal can be achieved mainly through a large quantity of transport biofuels, [25],
or with a switch to electric or alternative vehicles [26]. The proposed scenario Biofuels Sweden and
scenario Electric Vehicles relate to these suggestions.
The quantities of waste have grown steadily over the past decade in close relation to the economic
growth. However, waste prevention is a clear priority in waste management within EU and a
decoupling of waste amounts from the economic growth is foreseen [17, 18]. The Low Waste
scenarios relate to decoupling of waste amount and economic growth.
Table 4. Proposed scenarios for development of regional waste-to-energy systems

Name Description
Biofuels Sweden A fossil fuel free transport system in Sweden, based on
biofuels
Biofuels Sweden, low waste A fossil fuel free transport system in Sweden, based on
biofuels, and a low amount of waste
Electric Vehicles A fossil fuel free transport system in Sweden, with a high
proportion of electrical vehicles
Bioenergy Europe A Low carbon energy system in Europe
Bioenergy Europe, low waste A Low carbon energy system in Europe and a low
amount of waste
Electricity
Electricity is assumed as important for the fossil fuel independent transport system in Sweden [26],
and for the low carbon economy in Europe [8]]. There are two main categories of electric drive
vehicles: electric vehicles (EV) and plug-in hybrid electric vehicles (PHEV). In the scenario Electrical
Vehicles both categories are included. In this scenario, the switch to electrical drive in personal cars is
assumed to be more extensive than in scenario Biofuels Sweden. The Swedish power system is
deemed to easily manage an introduction of EVs and PHEVs [27].
The future transport activity is assumed to increase [25]. However, this switch to an electric
transport system together with energy efficiency improvements will reduce the future end-use energy
demand in the transport sector. Electrical-drive makes electrical vehicles much more energy efficient
[26, 27]. In its long-term forecast for 2008 the Swedish Energy Agency expects an electricity
consumption of 0.24 kWh / km including losses [23]. The electricity consumption per km is likely to be
even lower than that [27].
There is a huge variation in EVs and PHEVs sales projections for Europe [28]. The projections of
electric vehicles for Sweden also show huge differences. The Swedish Energy Agency in its long-term
forecast for 2020 is expected 85,000 electric drive vehicles, using 0.17 TWh [23]. The Royal Swedish
Academy of Engineering Sciences, IVA and the electric branch have developed a vision of 600 000
electric drive vehicles in 2020, using 1,5 TWh, 1 % of the current electric consumption in Sweden [27].
As mentioned earlier, the Swedish Association of the Electricity Industry [26] assumed that the
690
electricity introduction to personal cars will cover 40% of the energy demand when the goal of fossil
fuels independent transport sector will be achieved in 2030. The Swedish government supports the
development of the electric drive vehicles, and a national demonstration programme for EVs and
PHEVs is established for 2011-2014 [ 29].
Biofuels
Since Sweden is a member of the EU, scenarios with a focus on Sweden, scenario Biofuels Sweden,
and with a broader EU approach, scenario Bioenergy Europe, are proposed. In the scenario
Bioenergy Europe, a low carbon energy system in Europe is assumed. The EU energy policy consists
of a binding target to 2020: 20% RES share in gross final energy consumption [7], and according to an
EU road map on transport, the Commission plans for targets on fossil fuel free cars in cities by 2050
[30]. Sweden has the highest proportion of renewable energy in the EU, and in this scenario, Sweden
exports bioenergy to other countries in Europe.
Low waste sensitivity analysis

The Low Waste sensitivity analysis for scenarios Biofuels Sweden and Bioenergy Europe is
recommended. There are two main reasons for this. First, waste prevention remains a clear priority in
waste management within the EU [15, 27], Second, the prevention of food losses and food waste has
become a subject of concern at both global and national level. In Sweden, both of these issues are of
current interest [31, 32, 33, 34]
The quantities of waste have grown steadily over the past decade in close relation to the economic
growth. Non-increasing future waste quantities require decoupling waste amounts from the economic
growth. Where the waste quantities stabilize or decrease while the Gross Domestic Product ( GDP)
still increases, absolute decoupling of waste generation from GDP occurs; relative decoupling occurs
where total waste quantities increase at a lower rate than GDP [ 18] . Waste prevention is the highest
priority in the waste hierarchy according the revised Framework Directive. The Commission is required
to set decoupling objectives by the end of 2014 and the Member States need to set out decoupling
objectives and measures in their preventions programme [15]. The absolute decoupling is the target
for waste management in Sweden. According to the 15th environmental quality objective, A Good Built
Environment, the total quantity of waste must not increase [15].
The Swedish EPA has the mission to establish a national waste prevention plan for Sweden. In its
accounting for government commission [35] the Swedish EPA states that initially strategies for the
prevention of four waste streams will be developed: food waste, construction waste, textile waste,
household waste. These waste streams give a large environmental benefit per prevented ton. Waste
in the construction sector, household waste, and resource management in the food chain will also be
three of five priority areas in a new national waste plan coming up this fall Tthe new plan should
contribute to better use of materials and resources instead of throwing them away them [36].
There is a growing concern for food losses and food waste in particular. One-third of food produced
for human consumption is lost or wasted globally, and the per capita food waste by consumers in
Europe and North-America is 95-115 kg per year [37].The Swedish avoidable food waste is likely to be
slightly above 50 percent of the total amounts of food waste, which implies that the avoidable food
waste is 56 kg per person annually [35]. In addition to food waste, textile waste is getting more
attention in Sweden. The influx of clothing and textiles to Sweden has increased by nearly 40 percent
during the period 2000 to 2009 and in 2008 was just under 15 kg / person [38].
As mentioned earlier, the absolute decoupling of waste amounts from the economic growth is a
target both at the EU level and at the national level in Sweden. However, in most Member States
waste generation seems to increase, or at best stabilize. In the EU-27 municipal solid waste
generation (7% of total waste) has stabilized around 524 kg per year and capita (2008) [17]. The
Swedish Environmental Objectives Council states that it will be very difficult to attain the target of non-
increasing waste quantities. The total quantity of waste continues to increase, especially consumption-
related waste. The amount of household waste increased between 1998 and 2008 by 24 percent [39].
Also in the future waste quantities are expected to increase within the EU, according to the European
Environmental Agency (2005), but at a lower rate than GDP from 2020. Actually, a relative decoupling
between waste generation and GPD growth can be observed between 1999 and 2007 [17]. The
scenarios Low Waste assume that the policies and initiatives for waste prevention will result in
decreased waste quantities.
The assumptions of waste intensities are presented in two previous studies [19, 21]. In both studies
different scenarios for waste intensities in 2030 are developed. The method used is the Environmental
Medium Term Economic Model (EMEC) applied as a computable general equilibrium (CGE) model of
the Swedish economy developed and maintained by the National Institute of Economic Research for
691
analysis of the interaction between the economy and the environment. Sjstrm and stblom [21]
developed two scenarios for waste intensities: the Baseline Scenario and the Decoupling Scenario,
where absolute decoupling is attained. Sundquist et al. [19] present four different scenarios where
relative decoupling is introduced in two of them.
The total quantity of waste in Sweden continues to increase and little evidence suggests that
society in the foreseeable future would be able to live up to waste prevention targets [20]. Therefore in
this paper it is assumed that waste quantities will increase until 2030 and that absolute decoupling will
not be achieved until 2050. The waste intensities assumed by Sjstrm and stblom [21]in their
Baseline Scenario are proposed in this paper as waste intensities for Low Waste Scenarios in 2030
and for not Low Waste scenarios in 2050. The waste intensities for not Low Waste scenarios in 2030
are proposed to be in line with the assumption made by Sundquist et al. [19] in scenarios with
increased household waste, i.e. without decoupling. The consistency between assumption of
economic growth to 2030 (2,2 % per year) made by Sjstrm and stblom [21] and to 2050 (2,25 %
per year) made by Gode et al. [25] is the base for the suggestions in this paper to use the waste
intensities proposed for 2030 by Sjstrm and stblom also for 2050. Of course there is uncertainty
involved in these assumptions .
Tabel 5. Waste intensities. Yearly percentage changes 2006 -2030 based on Sundquist [19] and on Sjstrm and stblom
[21.]The figures given for 2050 low is the figures presented for 2030 in the study by Sjstrm and stblom.
2030 2030 Low waste 2050 2050 Low waste
Non-hazardous waste
Material-related -1 -1 -1 -2. 16
Production-related 0 0 0 -1.35
Household-related +1 0 0 -3.36
Hazardous waste
Material-related -1 -1 -1 2.03
Production-related 0 0 0 2.09
Household-related +1 0 0 3.36
CONCLUSIONS AND DISCUSSIONS

In this paper, an inventory of policies and goals on international, national, regional and local level, as
well as existing scenarios and reports of future trend development related to the waste-to-energy area
was made. From the results of the inventory, three main scenarios are proposed. The main substitute
for fossil fuels and the possibilities for renewable energy export are basic elements that define
scenarios. As main substitutes for the fossil fuels, biofuels and electricity are identified. Furthermore,
as Sweden is a member of the EU, scenarios both with a focus on Sweden and with a broader, EU
approach, are proposed. The inventory of policies and goals, as well as other waste-to-energy reports,
shows a growing concern for waste prevention in waste management within the EU, and [space] for
food losses and food waste at global and at national level. These issues should be addressed, and a
low waste sensitivity analysis is recommended. The Low Waste scenario in 2030 assumes relative
decoupling while this paper assumes that absolute decoupling is not achieved until 2050.
The future amount of waste that can be used in the waste-to-energy field can be affected by
increased recycling and material recovery. Sweden belongs to the world leaders in waste
management [40]. Still the quantity of waste that is recycled can increase significantly [20]. Especially
the textile and food waste streams can be mentioned here. There is no recycling for textile waste from
households at the moment. The amounts of textile waste can be as much as 205 000 kg in 2030.
compd to 20 000 in 2006 [20] .There is also a big potential for increased recovery and biological
treatment of food waste from households, restaurants and shops waste. Systems for the collection of
food waste were found in only half of the municipalities in 2009 and the target By 2010 at least 35% of
food waste from households, restaurants, caterers and retail premises will be recovered by means of
biological treatment is not achieved yet [39.]. 60 municipalities planned to introduce systems for
collection of food waste.
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693
BIODIESEL PRODUCTION BY MICROALGAE AND MACROALGAE FROM

NORTH LITTORAL PORTUGUESE COAST
1 2 3 4 5
J. Carvalho , A. Ribeiro , J. Castro , C. Vilarinho and F. Castro

3 University of Minho, a50059@alunos.uminho.pt.
4 University of Minho/CT2M, candida@dem.uminho.pt.
ABSTRACT
Biodiesel, as an alternative fuel, has many benefits. It is biodegradable, non-toxic and
compared to petroleum-based diesel, has a more favorable combustion emission profile,
such as low emissions of carbon monoxide, particulate matter and unburned
hydrocarbons. In brief, these merits make biodiesel a good alternative to petroleum
based fuel. Biodiesel feedstocks derived from microalgae and macroalgae have emerged
as one of the most promising alternative sources of lipid for use in biodiesel production
because of their high photosynthetic efficiency to produce biomass and their higher
growth rates and productivity compared to conventional crops. In addition to their fast
reproduction, they are easier to cultivate than many other types of plants and can
produce a higher yield of oil for biodiesel production.
In this work biodiesel was produced using the species of microalgae Chlorella emersonii
and Botrycoccus braunii due to its high oil content. Biodiesel productions through
macroalgae oil are in preliminary phase. Therefore, results and methodology will not be
presented in this work. Technological assessment of process was carried out to evaluate
their technical benefits, limitations and quality of final product. In this work biodiesel from
microalgae oil was produced by an alkali-catalyzed transesterification and it was
achieved 93% of mass conversion. The evaluation of quality from raw materials and final
biodiesel was performed according to standard EN 14214. Results show that all
parameters analyzed meet the standard and legislation requirements. This evidence
proves that in those operational conditions the biodiesel produced from microalgae can
substitute petroleum-based diesel.
Keywords: Biodiesel, Microalgae oil, Alkali-Catalyzed Transesterification
INTRODUCTION
Energy is the most fundamental requirement for human existence and activities. As an effective
fuel, petroleum has been serving the world to meet its need of energy consumption. But the
dependence of mankind entirely on the fossil fuels could cause a major deficit in future. The
application of biodiesel to our diesel engines for daily activities is advantageous for its
environmental friendliness over petro-diesel [1, 2]. The main advantages of using biodiesel is that
it is biodegradable, can be used without modifying existing engines, and produces less harmful gas
emissions such as sulfur oxide [1, 3]. Biodiesel reduces net carbon-dioxide emissions by 78% on a
lifecycle basis when compared to conventional diesel fuel [4]. Puppan [5] have discussed the
advantages of biofuels over fossil fuels to be: (a) availability of renewable sources; (b) representing
CO2 cycle in combustion; (c) environmentally friendly; and (d) biodegradable and sustainable.
Other advantages of biodiesel are as follows: portability, ready availability, lower sulfur and
aromatic content, and high combustion characteristics. Biodiesel, which is considered as a possible
substitute of conventional diesel fuel is commonly, composed of fatty acid methyl esters that can be
694
prepared from triglycerides in vegetable oils by transesterification with methanol [6]. The resulting
biodiesel is quite similar to conventional diesel fuel in its main characteristics [7].
Transesterification is the process by which the glycerides present in fats or oils react with an
alcohol in the presence of a catalyst to form esters and glycerol [8, 9, 10]. Catalyst increases the
rate of the reaction and also the yield. This reaction proceeds well in the presence of some
homogeneous catalysts such as potassium hydroxide (KOH)/sodium hydroxide (NaOH) and
sulfuric acid, or heterogeneous catalysts such as metal oxides or carbonates [11]. Depending on
the undesirable compounds (especially FFA and water), each catalyst has its advantages and
disadvantages. Sodium hydroxide is very well accepted and widely used because of its low cost
and high product yield [12]. The most common alcohols widely used are methyl alcohol and ethyl
alcohol. Among these two, methanol found frequent application in the commercial uses because of
its low cost [9].
Figure 1 Structure of triglycerides and principles of transesterification reaction
Vegetable oils are promising feedstocks for biodiesel production since they are renewable in
nature, and can be produced on a large scale and environmentally friendly [11]. However, it may
cause some problems such as the competition with the edible oil market, which increases both the
cost of edible oils and biodiesel [13,14,15]. For instance, the mass plantation of monoculture plants
could benefit the economy of rural population while negatively affecting the water resources and
the biodiversity [14]. In order to overcome these disadvantages, many researchers are interested in
others feedstocks as Algae oil [2,12,16,17].
The aim of this study was to evaluate biodiesel production through microalgae oil, testing different
operating conditions and equipment designs for each stage of processing. Technological
assessment of this process was carried out to evaluate their technical benefits, limitations and
quality of final product.
MICROALGAE
Microalgae have high potentials in biodiesel production compared to other oil crops. First, the
cultivation of microalgae does not need much land as compared to others plants [18]. Biodiesel
produced from microalgae will not compromise the production of food and other products derived
from crops. Second, microalgae grow extremely rapidly and many algal species are rich in oils. For
instance, heterotrophic growth of Chlorella can accumulate lipids as high as 55% of the cell dry
weight after 144 h of cultivation [19]. Oil levels of 2050% are common in microalgae [18]. These
technological advances suggest that the industrial production of biodiesel from microalgal oils may
be feasible in the near future.
The advantages of culturing microalgae as a resource of biomass are:

i. Algae are considered to be a very efficient biological system for harvesting solar energy for
the production of organic compounds;
ii. Algae are non-vascular plants, lacking (usually) complex reproductive organs;
iii. Many species of algae can be induced to produce particularly high concentrations of
chosen, commercially valuable compounds, such as proteins, carbohydrates, lipids and
pigments;
iv. Algae are microorganisms that undergo a simple cell division cycle;
v. Microalgae can be grown using sea or brackish water;
vi. Algal biomass production systems can easily be adapted to various levels of operational or
technological skills [11,12,16,17,20]
695
BIODIESEL PRODUCTION WITH CATALYZED TRANSESTERIFICATION
Alkali-catalyzed transesterification
The use of alkali catalysts in transesterification reaction of microalgae oil is somewhat limited,
because FFA content presents in this feedstock oil reacts with the most common alkaline catalysts
(NaOH, KOH, and CH3ONa) and forms soap [8]. This reaction is undesirable because soap lowers
the yield of the biodiesel and inhibits the separation of esters from glycerol. In addition, it binds with
the catalyst meaning that more catalyst will be needed and hence the process will involve a higher
cost [9]. Feedstocks with high free fatty acid will react undesirably with the alkali catalyst thereby
forming soap. Maximum amount of free fatty acids acceptable in an alkali- catalyzed system is
below 3 wt. % FFA. If the oil feedstock has a FFA content over 3 wt.%, a pretreatment step is
necessary before the transesterification process [14].
Process design
Fig. 1 shows a simplified flow chart of the alkali-catalyst process tested in this study for the
transesterification of microalgae oil.
Figure 1 - Simplified process flow chart of alkali-catalyzed biodiesel production
Materials and experimental procedure
Materials
The fuel properties of microalgae methyl ester were determined at laboratory of CVR (Center for
Waste Valorization) and FEUP (Engineering Faculty of Porto University). Microalgae species
were chosen taking into account its content in oil. Therefore was selected the species of
Chlorella emersonii and Botryococcus braunii which were purchased from ACOI -
Coimbra Collection of Algae. Methanol (purity 99.7%) and sodium hydroxide with purity of 99% was
purchased from SigmaAldrich, which were employed as the alkali catalysts in the reaction.
Sulfuric acid was also purchased from SigmaAldrich, which were employed as the acid catalysts
in the esterification reaction. Citric acid was also purchased from SigmaAldrich, which were
employed in the washing process.
Microalgae oil
The microalgae cultures were development in semi-open flasks, to simulate the conditions of
photobioreactors. The medium used, designated M7 medium was prepared according to seaweed
collection provided by ACOI - Coimbra Collection of Algae. The recovery process for collecting
algae biomass was realized trough flocculation by aluminum chloride (AlCl3.6H2O), iron chloride
(FeCl.4H2O) and aluminum sulfate (Al2(SO4)3.18H2O). For the oil extraction were tested an
ultrasound rupture system. Before transesterification, microalgae oil was filtered and heated among
65 - 70 C for 30 min. Methanol (5:1 molar ratio methanol/oil) was mixed with sodium hydroxide
(0.25% w/w), until all of the NaOH was dissolved in methanol. This mixture was then added to the
696
oil, and further heated to 60 C, for 2 h. The ester was purified by washing with distilled water and
citric acid and drying at 100 C for 4 h. The final polishing process was realized by filtering the
methyl ester in a filtering unit system.
Results and Discussion
Oil extraction
For collecting algae biomass it was tested three flocculants: aluminum chloride (AlCl3.6H2O), iron
chloride (FeCl.4H2O) and aluminum sulfate (Al2(SO4)3.18H2O). The results showed a similar
behavior for the three flocculants tested. Oil extraction was accomplished by utilization of
ultrasound to promote cellular rupture during 1 hour. Table 1 shows the oil extraction yield for both
microalgae species tested.
Table 1 Oil extraction yield for Chlorella emersonii and Botryococcus braunii
Algae Extracted Oil (g/l)
Dry weight (g/l) % %
biomass (g/l) (dry weight)
Chlorella emersonii 115.2 37.4 32.2 14.8 39.7
Botryococcus braunii 86.0 36.1 42.0 18.3 50.7
Results showed that Chlorella emersonii achieved 14.8 goil/lalgae culture and Botryococcus braunii
obtained 18.3 goil/lalgae culture. Considering the culture time and total algae biomass produced it was
-1 -1
reached an extraction coefficient of 3.7 g oil d for Chlorella emersonii and 4.6 g oil d for the
Botryococcus braunii. Campbell et al. [21] realized a technical-economic study for biodiesel
production trough Chlorella microalgae. In that study, they concluded that it was necessary an
-2 -1
extraction yield of 30 g oil m d to economic ensure the process. The lower growth rate and
extraction coefficient obtained in this work can be explained by the utilization of semi-open flasks to
simulate an open batch photobioreactor. According to Brennan and Owende [16] this type of
reactor presents the lowest biomass growth rate.
Mass conversion
One of the most important dependent variables in this experiment is the mass conversion, which is
given by the mass ratio of biodiesel (product) to the total initial mass of the raw material and the
additives [1]. Table 2 shows the mass conversion from transesterification reaction on microalgae
oil.
Table 2 Mass conversion (%) of biodiesel from microalgae oil

FFA content [%] Mass conversion [%]
Microalgae oil <1 93
Mass conversion depends on several parameters like, reaction temperature and pressure, reaction
time, rate of agitation, type of alcohol used and molar ratio of alcohol to oil, type and concentration
of catalyst used and principle concentration of free fatty acids (FFA) in the feed oil [8,9,22]. In this
case previous FFA determination revealed that microalgae oil has less than 1%. Therefore it was
realized an alkali-catalyzed transesterification. The results demonstrated that microalgae biodiesel
was the maximum mass conversion of 93%.
Quality of Biodiesel
The major focal point for biodiesel high quality is the adherence to biodiesel standard
specifications. These standard specifications in European Union are established by EN 14214 for
biodiesel fuel [1,8,23]. The results of the analyses in the different types of biodiesel produced
(Table 3) showed that in generally the quality parameters of standard EN 14214 was accomplished
697
Table 3 Results of biodiesel produced from algae oil according to standard EN 14214
Microalgae
Limits
Property Unit biodiesel result Test Method
Minimum Maximum
Ester content % (m/m) 97,5 0,2 96,5 EN 14103
Density at 15 C kg/m3 862 5 860 900 EN ISO 3675
Viscosity at 40 C mm2/s 4,21 0,05 3,00 5,00 EN ISO 3104
Flash point C 160 1,5 120 - EN ISO 3679
Carbon residue % (m/m) 0,05 0,01 - 0,30 EN ISO 10370
Water content mg/kg 472 5 - 500 EN ISO 3679
Acid value mg KOH/g 0,36 0,05 - 0,50 EN 14104
Iodine value g iodine100 g 110 1,50 - 120 EN 14111
Linolenic acid methyl ester % (m/m) 4,6 0,20 - 12,0 EN 14103
Methanol content % (m/m) 0,1 0,01 - 0,20 EN 14110
EN14108
Group I metals (Na + K) mg/kg 4,02 0,15 - 5
EN 14109
Conclusions
Biodiesel is gradually gaining acceptance in the market as an environmentally friendly alternative
diesel fuel. However, for biodiesel to established and continue to mature in the market, various
aspects must be examined and overcome. Some of the key issues such as improving efficiency of
the production process and using low cost feedstock have been reviewed and analyzed in this
work. Biodiesel production from microalgae oil presents various advantages compared to other low
cost feedstocks. However in other to compete with petroleum-based fuels cost, biodiesel
production from microalgae needs to be cheaper.
On this work it was possible to conclude the technically feasibility of the process. Microalgae oil
had a high yield of conversion and analyses on final biodiesel showed that all quality
parameters of the standard 14214 have been respected. According to these results, it is possible to
conclude that the biodiesel produced with these feedstock was liable to be used in diesel car
engines, in a unique way (B100) or blending with fuel diesel (B20, B30 and B50), without decrease
of engine efficiency. Nonetheless is important to note that in this work microalgae growth rate and
extraction coefficient had low yields which increased cost-production. The solution for this problem
requires improvements in algal biology, and in photobioreactor engineering, as the usage of tubular
photobioreactors.
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for biodiesel productionA review, Resources, Conservation and Recycling 53 (2009) 490
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[19] H. Xu, X.L. Miao, Q.Y. Wu. High quality biodiesel production from a microalga Chlorella
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268.
699
BIODIESEL PRODUCTION FROM ANIMAL FAT USING HETEROGENEOUS

CATALYSTS
1, a 1, b 1, a 2
J.M. Dias , M. C. M. Alvim-Ferraz , M. F. Almeida , J. D. Mndez-Daz ,
2 2
M. Snchez-Polo and J. Rivera-Utrilla
1
LEPAE, Faculdade de Engenharia, Universidade do Porto, R. Dr. Roberto Frias, 4200-465, Porto,
Portugal, jmdias@fe.up.pt, aferraz@fe.up.pt, mfa@fe.up.pt
2
Departamento de Qumica Inorgnica, Facultad de Ciencias, Universidad de Granada, 18071
Granada, Espaa, ppmendez@ugr.es, mansanch@ugr.es, jrivera@ugr.es
a)
Departamento de Engenharia Metalrgica e de Materiais
b)
Departamento de Engenharia Qumica
ABSTRACT
Biodiesel is a renewable fuel applied as diesel substitute, which contributes for the
diversification of energy sources. Biodiesel production limitations essentially relate with
the raw materials cost but also with the technology costs, namely those of product
purification. In order to contribute for a more sustainable biodiesel production, the present
work studied its synthesis from animal fat using heterogeneous catalysis, by evaluating: i)
the use of different solid catalysts for animal fat transesterification; ii) the influence of the
reaction conditions on biodiesel purity by using Response Surface Methodology (RSM),
with the selected catalyst; and iii) the re-use of the selected catalyst. The results showed
that from the heterogeneous catalysts studied, calcium based oxides presented the best
results. From the reaction conditions studied, according to a developed model,
temperature and interaction between temperature and catalyst concentration mostly
influenced product purity obtained from animal fat using a calcium based mixed oxide. It
was possible to reuse the catalyst without loss of activity.
Keywords: Biodiesel; Heterogeneous catalysis; Pork lard; Response Surface Methodology
INTRODUCTION
Biodiesel is a renewable fuel used as an extender or in total substitution of diesel fuel [1]. At an
industrial scale, biodiesel production is made by using virgin vegetable oils such as rapeseed and
soybean oil; however, their high prices and use as food resource are great limiting factors.
The use of waste materials has a very important role aiming to reduce biodiesel production costs
and environmental impacts caused by inappropriate waste management [2]. Waste animal fats are
produced in significant amounts at several slaughter houses and other meat processing industries
and their use as animal feed strongly decreased, due to the possible transmission of severe animal
diseases [3]. Therefore, the use of waste animal fats as raw materials for biodiesel production is
extremely relevant.
In comparison with biodiesel from vegetable origin, biodiesel from animal fats has the advantage of
a higher calorific value and cetane number. Disadvantages include being less stable to oxidation,
and having a higher cold filter plugging point [3]. The obtained fuel might however be used pure in
boilers or mixed with other raw materials, even improving some fuel characteristics [2].
Biodiesel is an ester generally produced by a transesterification reaction of the triglycerides with an
alcohol; because these reagents are not miscible, a catalyst is generally used to speed up the
reaction. Sodium hydroxide, potassium hydroxide or their alkoxides are usually applied [1]. Being
homogeneous catalysts, the washing of the product is currently performed for their removal,
leading to the production of great amounts of wastewater.
700
To reduce separation costs and environmental impacts caused by the presence of the
homogeneous catalyst, heterogeneous catalysts are currently being studied. The preparation of a
highly effective heterogeneous catalyst is known to be complex and difficult to achieve [4];
however, they can be separated by simple filtration and might improve biodiesel quality and also
reduce corrosion and toxicity problems [4].
Homogeneous reaction conditions are: temperature around 60 C, catalyst concentration less than
1 wt%, molar ratio of methanol to fat around 6:1 and reaction time of 1 h [1, 2]. In comparison,
heterogeneous catalytic reactions can be performed using: i) temperature similar and lower [5, 6]
but also much higher (120 C, 200 C) [7, 8]; ii) catalyst concentration from 2 [9] to 20 wt% [10]; iii)
molar ratio of methanol to oil/fat of 6:1 [11, 12] being commonly higher, such as 12:1 [13] and 30:1
[10]; and i) reaction time from 3 h [6] to 24 h [14]. The wide range of reaction conditions used
shows the importance of optimizing biodiesel production conditions when using such catalysts.
Among the most currently studied heterogeneous catalysts, calcium oxide, both alone and
supported, seems to be a promising catalyst [5, 11]. Huaping et al. [11] achieved vegetable oil
conversions up to 93 wt% using thermally treated calcium oxide at 70 C, 2.5 h, 1.5 wt% catalyst
and 9:1 molar ratio of methanol to oil. Other catalysts that seem to have good performance
regarding the transesterification reaction are the mixed metal oxides. Kawashima et al. [15] studied
the application of such materials for rapeseed oil transesterification clearly showing that the ones
containing calcium had the best performance; product methyl ester contents varying from 79 to 92
wt% after 10 h of reaction were obtained using around 6:1 molar ratio of methanol to oil and 60 C.
Biodiesel production using animal fats is still understudied regarding homogeneous [3], but even
more considering heterogeneous synthesis. In a study by Liu et al. [10], the use of heterogeneous
base catalysts derived from MgAl hydrotalcite was evaluated for the transesterification of poultry
fat with methanol. Conversions were higher than 90 wt%, but reaction conditions were relatively
extreme: reaction occurred for 8 hours at 120 C, using 30:1 molar ratio of methanol to fat and 10
wt% catalyst. Also, Venkat Reddy et al. [16] showed 100% conversion using nanocristaline calcium
oxide for the conversion of poultry fat to biodiesel. In that study, reaction temperature was close to
ambient (25 C), around 1 wt% catalyst was used and reaction was performed during up to 7 h
using high molar ratios of methanol to fat (around 70:1). The different conditions used in the
described studies clearly show that optimization studies should be performed for each raw material
and catalyst applied.
According to the previously described issues, the present work focused on evaluating: i) the use of
different solid catalysts for animal fat transesterification; ii) the influence of the reaction conditions
on biodiesel purity by using Response Surface Methodology (RSM), using the selected catalyst;
and iii) the re-use of the catalyst.
Materials
Pork lard was supplied by Irmos Monteiro S.A, a Portuguese meat processing industry, and was
kept in the freezer at 4 C during the experimental period. Soybean oil used was from the brand
olisoja, being donated by Sovena, SA, Portugal. Methanol 99.5% (analytical grade, Fischer
Scientific) was used for biodiesel synthesis and n-Heptane (analytical grade, Merck) was used for
catalyst cleaning and chromatographic analysis. CaO and BaO were supplied by Sigma-Aldrich
and Fe2O3 and MnO2 were supplied by Riedel-de-Han. Syringe filters used (polypropylene, 25
mm diameter and 0.2 m pore size) were supplied by VWR.
Preparation of the catalysts

Calcium oxide and different mixed oxides were prepared. CaO was prepared from CaCO3 through
its calcination at 900 C during 4 h under N2 atmosphere in a tubular furnace. Calcium manganese
oxide (CaMnOx), barium manganese oxide (BaMnOx), calcium iron oxide (CaFeOx) and barium
iron oxide (BaFeOx) were prepared by conducting a solid-state reaction by mixing each oxide in
equimolar proportion in one agate mortar, and after calcining the mixture at 900 C during 4 h
under N2 atmosphere in a tubular furnace.
Calcination procedure was repeated to avoid its deactivation when catalyst was not immediately
used. When the selected catalyst was reused, it was first heated at 550 C in a tubular furnace
701
under O2 atmosphere to ensure complete removal of organics and further activated by calcination
at 750 C during 4 h under N 2 atmosphere in a tubular furnace.
Analytical methods
The following lard properties were determined: i) acid value, by volumetric titration according to the
standard NP EN ISO 660 (2002); and iii) iodine value, determined from ester content according to
annex B of EN 14214 (2003).
The evaluation of biodiesel conversion was performed by measuring the product methyl ester
content using GC according to EN 14103 (2003). The GC analysis were performed in a a Dani GC
1000 DPC gas chromatograph (DANI Instruments S.p.A.), with an AT-WAX (Heliflex capillary,
Alltech) column (30 m, 0.32 mm internal diameter and 0.25 m film thickness). The conditions were
the same as the ones used in Dias et al. [3].
Biodiesel heterogeneous synthesis

Biodiesel synthesis was performed according to a experimental planning made using JMP
software, adopting a central composite design (CCD) and using two central points. The
dimensionless variables were designated by x1, x2 and x3, corresponding to the temperature, catalyst
concentration and molar ratio of methanol to fat, respectively. The central values (zero level)
chosen for experimental design were: temperature 50 C, catalyst concentration 3 wt.% and a
methanol to fat molar ratio of 18:1. Regarding the model fitting, the parameter estimates were
considered significant when p value < 0.05, using an F test. The determination of the critical points
of the model was accessed using JMP; in order to find the maximum values of the functions a
different approach was also performed using iterative methods (Microsoft Excel Solver).
Synthesis was made by heterogeneous basic transesterification. The pork lard was dehydrated at
100 C and after cooled to near the reaction temper ature. Biodiesel synthesis was performed in a
glass reactor consisting of a 250 mL round-bottom flask with three necks immersed in a
temperature controlling bath; the reactor was equipped with a water-cooled condenser, a magnetic
stirrer, a septum for syringe sample collection, an entrance for nitrogen and a dropping funnel. For
the transesterification, 70 g of pork lard were kept at the reaction temperature (40, 50 or 60 C);
catalyst (1, 3 or 5 wt.% relative to fat weight) was placed into the reactor which was under
controlled nitrogen atmosphere; the necessary methanol (molar ratio of methanol to fat of 9:1, 18:1
or 27:1) was added to the catalyst using the dropping funnel and kept under mixing until reaching
the reaction temperature; finally, the lard was slowly added also using the dropping funnel. The
starting of the reaction was considered to be after the addition of all the lard into the reactor; at that
time, mixing of the reactants was changed from medium to vigorous.
Methyl ester content was measured at 0.25, 0.5, 1, 2, 4 and 8 h. The sampling was made through
the septum using a syringe. Each time, around 1 mL was taken and filtered through a syringe filter
to remove residual catalyst and immediately inserted in one ice bath to ensure the reaction end.
After, the reaction mixture was distilled under vacuum, in a rotary evaporator.
A sample was taken from the lighter phase and further treated according to EN 14103 (2003) for
determination of methyl ester content by chromatographic analysis.
After the 8 h sampling, the reaction mixture was filtered under vacuum and left to complete phase
separation overnight. The catalyst was washed with 40 mL of heptane using vacuum filtration and
left to dry in the oven at 100 C.
Phases were finally separated and the excess of methanol was recovered from each separately.
Selection of the heterogeneous catalyst

Table 1 presents the obtained results regarding the preliminary experiments, performed aiming to
select the heterogeneous catalyst for detailed study.
702
Table 1: Reaction conditions and results regarding the methyl ester content using different heterogeneous
catalysts for the transesterification of soybean oil
Reaction conditions
a Methyl ester
Catalyst Molar ratio , catalyst concentration [wt%]
b content [wt%]
, reaction time [h], temperature [C]
CaMnOx 20:1, 4, 6.5, 50 / 20:1, 5, 9, 60 89.5 / 98.0
BaMnOx 20:1, 5, 7, 50 0.0
CaFeOx 20:1, 5, 9, 50 4.5
BaFeOx 20:1, 5, 7, 50 0.0
CaO 20:1, 3, 9, 50 / 20:1, 5, 9, 60 51.0 / 94.6
a
Molar ratio of methanol to oil, b Relative to weight of oil.
The experiments showed that, from the materials studied, only the ones containing calcium
presented catalytic activity.
The best results were obtained using CaMnOx and CaO; between the two, the mixed oxide catalyst
led to the product with the highest purity (98.0 wt%). For that reason, the CaMnOx catalyst was
selected for the following studies. Additionally, results were quite promising for the selected catalyst
because, from the revised work, only Kawashima et al. [27] studied similar mixed oxides as catalyst
for biodiesel production and the product showed a 92 wt.% methyl ester content when CaMnO3
was used for rapeseed oil transesterification with less alcohol (around 7:1 molar ratio), but using a
reaction time of 10 h and 10 wt.% catalyst at 60 C .
Animal fat properties

The pork lard (mean molecular weight of 860.5 g/mol) presented an acid value of 0.71 mg KOH/g
fat and an iodine value of 68 g I2/100 g fat, values similar to the ones of commercial lard [2], which
shows a very low degree of oxidation.
Influence of inert conditions in biodiesel production

As described in the experimental section, biodiesel production was performed under inert
atmosphere. This was found to be critical factor, because when such conditions were not present,
a great difference was found regarding the progression of the reaction as it is shown in Fig. 1. This
fact might be related with the inactivation of the catalyst by carbonation and/or hydration [18].
Fig. 1. Influence of inert atmosphere in methyl ester content at 40 C (5 wt% catalyst and 9:1
molar ratio of methanol to fat).
Model fitting
The response variable (methyl ester content at 8 h) was fitted to a second-order model aiming to
correlate it with the independent variables: temperature ( x1 ), catalyst concentration ( x2 ) and
methanol to fat molar ratio ( x3 ). The model presented in Equation 1 was used for the preliminary
regression fits.
3 3 2 3
Y = 0 + i xi + ii xi 2 + ij xi x j (1)
i =1 i =1 i =1 j =i +1
703
The preliminary fit showed that the linear effect of the molar ratio of methanol to fat ( x3 ) was not
significant and the interaction term of the molar ratio of methanol
2
to fat and catalyst concentration
( x3 x2 ) and the quadratic term of catalyst concentration ( x2 ) showed low significance (p value <
0.10). All the other parameters were statistically significant, except for the quadratic term regarding
the molar ratio of methanol to fat which was statistically valid at a slightly lower level of confidence
2
(p value = 0.0581). The regression model showed a determination coefficient (r ) of 0.94 and the
final equation, in terms of the dimensionless variables, is given by Equation 2.
2 2
Y = 90.9 + 8.93 x1 + 5.12 x 2 + 0.370 x3 - 5.89 x1 - 7.59 x3 - 9.85 x1 x 2 + 4.95 x1 x3 (2)
Fig. 2A shows the experimental results versus the results predicted by the model. A line of unit
slope, corresponding to zero error between experimental and predicted values, is also presented.
This figure shows that the model represents a relatively good description of the experimental data
regarding methyl ester content at 8 h of reaction time. The modeling results showed that the most
significant effect was the linear effect of temperature and the interaction between temperature and
catalyst concentration. The other effects showed similar but smaller significance.
The determination of the critical points of the model function using JMP showed a saddle point (not
an extreme). Using the Microsoft Excel Solver, the maximum was found to be at x1=1 (60 C); x2 = -
1 (1 wt%) and x3 =0.32 (21:1), corresponding to a product methyl ester content of 99.6 wt%. Fig.
2B shows the representation of the model, at the conditions leading to such maximum methyl ester
content.
A) B)
Fig. 2. A) Predicted versus experimental product methyl ester content after 8 h of reaction. Line
corresponds to zero error between experimental and predicted values. B) Response surface for
product methyl ester content at 8 h considering a molar ratio of methanol to fat of 21:1.
Fig. 3A, shows that, in fact, when studied in isolation, temperature considerably influences the
product methyl ester content. The velocity of the reaction is in fact different at the 3 temperatures.
After 8 h of reaction a maximum methyl ester content of 95.8 wt.% was obtained at 60 C
compared to a content of 87.6 wt% obtained at 50 C and a content of 80.5 wt.% obtained at 40 C.
An increase in catalyst concentration also showed a positive effect in methyl ester content, but not
so demarked after 8 h of reaction at 50 C (Fig. 3B). However, at 40 C and using a 9:1 molar ratio
of methanol to fat, a great difference is found regarding the effect of the catalyst concentration after
8 h of reaction (Fig. 3B). A purity of 59.2 wt.% was obtained using 1 wt.% catalyst whereas a 85.5
wt.% was obtained using 5 wt.% catalyst.
The model indicates, however, that when both variables increase (for values higher than the central
point conditions: 50 C, 3 wt% catalyst), a decrease in product methyl ester content occurs.
This fact suggests an interaction between the temperature and the catalyst active site under such
conditions. Kansedo et al. [19] attributed similar effect in acid heterogeneous catalysis to the fact
that the equilibrium is more rapidly established at higher concentrations and that transesterification
reactions may become stagnant or start to reverse after a certain time.
704
A) B)
Fig. 3. A) Influence of temperature in product methyl ester yield, using 3 wt% catalyst and 18:1
molar ratio of methanol to fat; B) Influence of catalyst concentration in product methyl ester yield
40 C (9:1 molar ratio of methanol to fat) and 50 C (18:1 molar ratio of methanol to fat).
Effect of reusing the catalyst

In order to determine possible loss of catalyst activity by reuse, the catalyst was reused considering
the experimental conditions at the central point. Figure 4 shows the evolution of methyl ester
content with time before and after catalyst reuse.
Fig. 4. Product methyl ester content (wt%) with time (50 C, 3 wt% and 18:1 molar ratio of
methanol to fat) before and after catalyst reuse.
Results showed that, in fact, it is possible to reuse the catalyst without significant loss of its activity,
which seems to indicate that catalytic behaviour was essentially heterogeneous.
CONCLUSIONS
From the heterogeneous catalysts studied, during preliminary studies, catalytic activity was only
observed in those containing calcium: calcium manganese oxide, calcium oxide and calcium
barium oxide. Calcium manganese oxide showed the best results.
Using calcium manganese oxide, the influence of reaction conditions on methyl ester content
(purity) after 8 hours of reaction was studied and a second-order model was obtained, describing
the influence of temperature, catalyst concentration and methanol to fat molar ratio on product
purity. Temperature and the interaction between temperature and catalyst concentration were the
parameters which mostly influenced product purity.
705
The best experimental results were obtained at 60 C, using 3 wt.% catalyst and 18:1 methanol to
fat molar ratio, leading to a product methyl ester content of 95,8 wt.%. The predictive model
estimated a maximum methyl ester content of 99.6 wt% at 60 C, using 1 wt% of catalyst and a
methanol to fat molar ratio of 21:1.
As it was possible to reuse the catalyst without loss of its activity, results seem to indicate that
catalytic behaviour was essentially heterogeneous.
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homogeneous alkali catalysts during transesterification of waste and virgin oils and
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(2009) 2828-2831.
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Preparation of Biodiesel Catalyzed by Solid Super Base of Calcium Oxide and Its Refining
Process, Chinese J Catal. 27 (2006) 391-396.
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(2008) 862-870.
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biodiesel production, Bioresource Technol. 99 (2008) 3439-3443.
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706
PYROLYSIS OF AUTO SHREDDER WASTES TO PRODUCE LIQUID

BIOFUELS
1 2 1 2 1
M. Gonalves , P. Costa , D. Brs , F. Pinto , B. Mendes
1
Universidade Nova de Lisboa, Faculdade de Cincias e Tecnologia, Departamento de Cincias e
Tecnologia da Biomassa, Faculdade de Cincias e Tecnologia-Universidade Nova de Lisboa,
2829-516 Caparica, Portugal, mmpg@fct.unl.pt
2
Laboratrio Nacional de Energia e Geologia, Unidade de Emisses Zero, Laboratrio Nacional de
Energia e Geologia, 1649-038 Lisboa, Portugal, paula.costa@lneg.pt
ABSTRACT
Granulated plastics from automobile shredder wastes were subject to pyrolysis at
different temperatures (300C to 430C), different nitrogen pressures (30 psi to 150 psi)
and different residence times (1s to 120 min). The wastes were converted to pyrolysis
products with predominance of gases and liquids. The liquid phase was fractionated by
distillation to yield a light fraction (T<150C) and a heavy fraction (150C>T>300C). The
solid products were sequentially extracted with dichloromethane and tetrahydrofurane to
recover the liquid products retained in the solid pores. Liquid products and extracts were
characterized by GC-FID (gas chromatography with flame ionization detector), and the
products with boiling points lower than 270 C were further characterized by GC-MS (gas
chromatography with mass spectrometry). The light fraction is mainly composed by
aliphatic hydrocarbons with high amounts of low boiling point components such as 2-
butene. The heavier fraction contains linear alkanes and alkenes but also cyclic
hydrocarbons including cyclohexane derivatives and some alkylbenzenes.
These results indicate that these wastes can be successfully recycled to yield biogasoline
and green-diesel, contributing to a replacement of fossil fuels and simultaneously
eliminating significant amounts of hazardous wastes that necessarily increase with the
growth in the automobile production industry.
Keywords: Automobile shredder waste, pyrolysis, biogasoline, green-diesel
INTRODUCTION
Automobile shredder wastes (ASW) are all the materials used in automobile construction excluding
metals. The rate of automobile replacement leads to a growing accumulation of such wastes
resulting in a negative pressure in the environment and in the economy. Most of these materials
are plastics, that is, polymers with high carbon content produced using monomers of fossil origin.
These wastes have usually a degree of contamination, namely zinc, lead, cadmium and PCBs that
excludes their recycling to produce food packaging materials or equivalent applications. On the
other hand, the elemental composition of these wastes (high H/C ratio, low O/C ratio) is typical of
materials with high energy content, making them interesting for conversion in biofuels.
The present technologies available for recycling or valorization of ASW, including secondary
recovery and direct waste-to-energy applications are reviewed by Vermeulen et al. [1]. Pyrolysis
and gasification are referred as emerging technologies, with a large potential in waste volume
reduction and energetic valorization but with need of further optimization and scale-up studies.
The thermal or chemical valorization of complex ASW samples composed of materials such as
plastics, rubber or foams, was studied by different authors [2-4], using processes like pyrolysis,
gasification or injection in blast furnace. These works showed that using these processes it is
possible to convert ASW in gases and liquids with a high energy content.
The catalytic conversion of other polymer rich wastes or specific polymers in gaseous and liquid
biofuels has also been addressed by several authors [5-7] using pyrolysis or gasification in the
presence of different inorganic catalysts. The use of catalysts can reduce the activation energy for
707
polymer degradation and improve the yield of liquid or gaseous products as well as their specific
composition, however, it also increases the process cost.
The thermal conversion behavior of different polymers present in ASW (polystyrene, polypropylene
and polyethylene) has been studied [8,9] in order to optimize the experimental conditions adequate
for their conversion in biofuels.
In this work, it was investigated the conversion of the polypropylene fraction of a ASW in liquid and
gaseous biofuels using pyrolysis in a moderate temperature range (350C to 430C), and also
studied the influence of the experimental conditions in the composition of the pyrolysis products.

The granulated polypropylene from automobile shredder wastes (GP-ASW) was supplied by a car
dismantling company and used as received.
The elemental composition of this material was determined using ASTM standards D 4239:00 and
D 5373:93 and CEN standard 15408.
The proximate analysis of this waste was determined using the standards ASTM D 2867-70
(humidity), ASTM D 2866-70 (ashes) and ISO 562-1981 (volatile matter). Fixed carbon was
determined by the difference from the initial mass and the sum of all other components.
The pyrolysis of the GP-ASW was performed in a high pressure, high temperature reactor (Parr
Instruments), at temperatures from 350C to 430C, nitrogen pressures 30 to 150 psi and reaction
times from 1 s to 120 min. The GP-ASW (100g) was placed in the reactor, the reactor was closed
and the air was purged through cycles of depressurization and pressurization with nitrogen. After 3
to four purging cycles the reactor was brought to the pressure and temperature conditions chosen
for the pyrolysis test, and left in those conditions, under stirring, during the period of time selected
for the experiment. The reactor was then cooled to room temperature (using a water cooling coil)
and was depressurized to a circuit equipped with a gas meter. A sample of the gaseous phase was
collected in a Tedlar bag (SKC, Inc.) and used for the determination of gas phase composition
using gas chromatography. The liquid phase was decanted from the reactor and weighed. The
liquid products were fractionated by distillation and two fractions were recovered (a light fraction
with distillation temperatures from room temperature to 150 C and a heavier fraction with
distillation temperatures from 150 C to 300 C). The fractions were weighed and analyzed by gas
chromatography and mass spectrometry. The solid residue was weighed and extracted
successively with dichloromethane and tetrahydrofuran in a Soxhlet apparatus. The solvent from
the extracts was eliminated under vacuum and the residual liquids were weighed and analyzed by
gas chromatography.
The chromatographic analysis of the gas phase was performed in a gas chromatograph (HP
Agilent 6890) equipped with a gas sampling valve, two packed columns (Molecular Sieves and
Porapack Q),a thermal conductivity detector and a flame ionization detector.
The analysis of the liquid phases and extracts by gas chromatography with flame ionization
detection was performed in a Trace GC chromatograph (Thermo Instruments) equipped with a 7
meter DB-5 capillary column (film thickness of 0,25 m) and a PTV injector.
The analysis of the liquid phases by gas chromatography and mass spectrometry was performed
using a Focus GC chromatograph and a PolarisQ mass spectrometer (Thermo); the sample was
introduced with a split-splitless injector and separated in a 60 meter DB-1 capillary column with a
1,4 m film thickness.
The liquid phase light fraction was analyzed by headspace sampling (sample volume 50 L),
collected at 60 C after a 15 min period equilibration in 4 mL vial.
The heavier fraction of the liquid phase and the extracts were dissolved in hexane and an aliquot of
1 L of the resulting solutions was injected in splitless mode.
Characterization of the waste material

The residues studied in this work were segregated automobile shredder wastes, corresponding to
polypropylene components in a granulated form with diameters from 0,8 cm to 1 cm. This material
was characterized in what concerns elemental composition and proximate analysis.
708
The granulated polypropylene is composed of 85,20% carbon and 13,89% hydrogen which
corresponds to a H/C mass ratio of 0,16 analogous to an unsaturated aliphatic hydrocarbon. Sulfur,
nitrogen and chlorine were not detected, what indicates absence of contaminants such as PCBs
that are sometimes present in this kind of material and may originated very toxic polychlorinated
dioxins or furans when the material is subject to high temperatures.
Proximate analysis showed that the granulated polypropylene contains 97% (m/m) of volatile
matter and 1,25% (m/m) of fixed carbon what indicates that most of the polypropylene mass can be
converted to liquid or gaseous pyrolysis products. The material showed low humidity (0,14% m/m)
and low ashes content (1,62% m/m).
Determination of product yields

The mass yields (% m/m) of solid and liquid pyrolysis products obtained in different experimental
conditions are presented in Table 1.
Table 1 - Mass yields of liquid and solid products as a function of pyrolysis time (at a temperature
of 400C and a N2 pressure of 50 psi), temperature (at a N2 pressure of 50 psi, during 10 min) and
nitrogen pressure (at a temperature of 400 C, during 10 min).
Mass yield (% w/w)
Time (min) 0,02 10 15
Liquid Products 79,8 94,3 95,4
Solid Products 17,0 2,2 0
Temperature 350 400 430
Solid Products 43,7 2,2 0
Pressure [psi] 30 50 150
Solid Products 0 2,2 0,5
For temperatures above 400 C a good conversion of the PG-ASW in liquid products was achieved
with yields higher than 90% w/w. At 350C, the thermal energy is not sufficient to overcome the
activation energy barrier associated with polypropylene degradation. Regarding the effect of
reaction time in the product yield, the results obtained seem to indicate that that liquids production
is favored by the increase of the reaction time, since the liquid yield raised and the solid yield
decreased. After 15 min, at the same pressure and temperature conditions, all the PG-ASW mass
was converted either in liquid or gaseous products. The liquid yield presented a negative
correlation with the nitrogen pressure, for pyrolysis experiments performed in the range from 30 psi
to 150 psi. The increase in the concentration of nitrogen inside the reactor may contribute to
prevent the condensation of gaseous products during the final cooling therefore reducing the
relative amounts of liquids in the final products.
The gas phase yield was typically around 5 % (w/w) in most conditions tested. The low yields of
gas phase can indicate that the majority of the decomposed PG-ASW condenses to give liquid or
solid products. This behavior was obtained because the temperature of the experiment was kept
relatively low (<430 C). The use of higher temperatures, with reaction times higher than 5 min,
would result in a increase in gases production, which was not intended in this study.
Composition of the gas products

The yield of gaseous products was always lower than 8 % w/w, because, as it was stated above,
the experimental conditions were selected in order to maximize the conversion in liquid products
with biofuel quality. Nevertheless the gas phase composition was determined by gas
chromatography in order to evaluate its content in fuel gases. Thermal conductivity detection was
used for the analysis of the inorganic components like H2, O2, N2, nitrogen oxides and carbon
oxides while hydrocarbon gases were detected by flame ionization (Table 2). The gas
chromatographic analysis showed that the qualitative composition was maintained for all tests, with
709
minor differences in concentration for each gas compound. It was further observed that the main
gaseous hydrocarbons present in the pyrolysis gas phase were alkanes (methane, ethane,
propane and butane) and alkenes (ethylene, propylene and cis-2-butene). The compounds present
in higher concentration were methane, ethane and propene. At the lowest temperature tested, the
propene (PP monomer) was obtained in a very high concentration, what may indicate that, at this
temperature the depolimerisation of PP is favoured.
Table 2 Average composition of the gas phase (% v/v) determined by gas chromatography.
Combustible gases concentration (% v/v)
Hydrogen 0,3 - 5,2 Propene 19,4 - 47,3
Metane 18,2 - 31,3 Propane 12,9- 9,0
Ethylene 2,2 - 4,1 Butane 1,7- 7,3
Etane 15,7 - 22,1 Cis-2-butene 0,0 - 9,7
Besides containing various hydrocarbon gases with fuel quality, the gas phase also contains
hydrogen, but its low concentration may indicate the breaking of the C-H is not favored, under the
experimental conditions used in this study.
Composition of the liquid products

The liquid phase was fractionated by distillation in order to isolate a light fraction with boiling
temperature lower than 150 C (gasoline-like fraction) and a heavier fraction with boiling
temperature higher than 150C (diesel-like fraction). The simulated distillation of these two fractions
was performed by gas chromatography with flame ionization detection in the temperature range
from 80 C to 370 C, in order to establish their boiling point profile and also to define which
fractions could be analyzed by gas chromatography and mass spectrometry.
The composition of the gasoline-like fraction of the liquid phase was evaluated by gas
chromatography-mass spectrometry and the concentration of individual components was
determined from the relative chromatographic peak area.
Figure 1 Relative composition of the liquid phase lighter fraction (boiling points < 150 C).
The lighter fraction of the liquid phase had to be injected in the vapour phase using headspace
sampling at 60 C, because the dissolution in any liquid solvent, prevents the detection of the
lighter compounds, namely 2-butene and 2-methyl-2-butene that are also the major components of
this phase. A standard mixture of alkanes (C5 to C9) was injected in the same conditions in order
to allow calculation of the composition of the liquid phase in equilibrium with the headspace.
The main components of the liquid phase light fraction are alkenes from C4 to C9. This result is
coherent with the elemental composition of the PG-ASW that showed an H/C mass ratio similar to
710
alkenes. The major components of the liquid phase light fraction obtained after pyrolysis at a
temperature of 400 C (N2 pressure= 50 psi, pyrolysis time= 10 min), were 2-methyl-2-butene, 1-
hexene and 3-nonene; when the pyrolysis temperature was increased to 430 C, keeping the other
variables constant, the concentration of 2-methyl-2-butene increased while the concentration 3-
nonene decreased. This is a typical temperature effect that corresponds to a higher degree of
thermal cracking. The more volatile component detected in the liquid phase is 2-butene, a gas at
room temperature (the normal boiling point of the cis isomer is 4 C), so is not exactly condensed
but partially dissolved in the liquid phase.
The heavier fractions of the liquid phase were analyzed by gas chromatography and mass
spectrometry and compared with a standard mixture of alkanes (C9 to C17). The chromatographic
profile of the heavier fraction of the liquid phase obtained at a temperature of 400 C, with a N 2
pressure of 150 psi, and a pyrolysis time of 10 min is presented at Figure 2.
RT: 12.69 - 58.78

37.14 NL:
100 3.61E7
37.65 TIC MS
90 E10-FR2-2
13.92
80
70
21.17
29.99 43.04
Relative Abundance
60 48.17
39.38 45.04 48.76

50
22.07 42.09 50.00

40 27.24
32.61 46.93
27.41
30 23.18
36.56 53.31
26.97 51.46 55.76
20
23.49
14.22 20.05 57.25
10 14.71
17.52
0
15 20 25 30 35 40 45 50 55
Time (min)
Figure 2 Chromatographic profile of the heavier fraction of the liquid phase obtained after
pyrolysis of the PG-ASW, at a temperature of 400 C, with a N2 pressure of 150 psi, during 10 min.
The composition of the heavier fraction of the liquid phase (diesel-like fraction) is more complex
than the lighter fraction (gasoline-like fraction). Individual components of the diesel-like fraction
were tentatively identified by comparison of the corresponding mass spectra with NIST and WILEY
mass spectra libraries. Alkenes and cycloalkenes are the most abundant components of this
fraction that also contains of alkanes, cycloalkanes and alkyl benzenes. The results of simulated
distillation of the diesel-like fraction show that most of the components of this fraction present
boiling points in the range from 100 C to 250 C, that is, they have a volatility behavior comparable
to a fossil diesel.
Conclusions
Segregated automobile shredder wastes composed of granulated polypropylene were converted to
liquid biofuels analogous to fossil gasoline and fossil fuel using pyrolysis at moderate temperatures
(< 430 C) and moderate nitrogen pressures (30 psi to 150 psi).
The biofuels thus produced are composed by aliphatic saturated and monounsaturated
hydrocarbons, what makes them adequate for direct use as fuels without requiring upgrading steps
often necessary to reduce the oxygen content of pyrolysis biooils.
The segregation of these wastes prevents contamination with other components that contain
chlorine atoms (such as polyvinylchloride), that can lead to the formation of polychlorinated dioxins
or furans when subject to high temperatures.
711
Given the high amounts of automobile shredder wastes produced nowadays, the thermal
valorization of these wastes can complement their recycling, especially when they are highly
contaminated.
Pyrolysis allows the direct waste-to-fuel valorization and produces biofuels with a good energetic
quality that may become competitive with fossil fuels.
References
[1] I. Vermeulen, J. Van Caneghem, C. Block, J. Baeyens, C. Vandecasteele, Automotive shredder
residue (ASR): Reviewing its production from end-of-life vehicles (ELVs) and its recycling,
energy or chemicals valorization, Journal of Hazardous Materials 190 (2011) 827
[2] I. de Marco, B.M. Caballero, M.A. Cabrero, M.F. Laresgoiti, A. Torres, M.J. Chomn, Recycling
of automobile shredder residues by means of pyrolysis, J. Anal. Appl. Pyrolysis 79 (2007) 403
408
[3] P. Donaja, W. Yang, W. Basiak, C. Forsgren, Recycling of automobile shredder residue with a
microwave pyrolysis combined with high temperature steam gasification, Journal of Hazardous
Materials, 182 (2010) 8089
[4] D. Mirabile, M. Ilaria Pistelli, M. Marchesini, R. Falciani, L. Chiappelli, Thermal valorisation of
automobile shredder residue: injection in blast furnace, Waste Management 22 (2002) 841851
[5] Y.-H. Lin, H.-Y. Yen, Fluidised bed pyrolysis of polypropylene over cracking catalysts for
producing hydrocarbons, Polymer Degradation and Stability 89 (2005) 101-108
[6] C. Wu, P. T. Williams, Investigation of Ni-Al, Ni-Mg-Al and Ni-Cu-Al catalyst for hydrogen
production from pyrolysisgasification of polypropylene, Applied Catalysis B: Environmental 90
(2009) 147156
[7] A. Marcilla, A. Gmez, J.A. Reyes-Labarta, A. Giner, F. Hernndez, Kinetic study of
polypropylene pyrolysis using ZSM-5 and an equilibrium fluid catalytic cracking catalyst, J. Anal.
Appl. Pyrolysis 68-69 (2003) 467-480
[8] S-S.Kim, S. Kim, Pyrolysis characteristics of polystyrene and polypropylene in a stirred batch
reactor, Chemical Engineering Journal 98 (2004) 5360
[9] A. Aboulkas, K. El harfi, A. El Bouadili, Thermal degradation behaviors of polyethylene and
polypropylene. Part I: Pyrolysis kinetics and mechanisms, Energy Conversion and Management
51 (2010) 13631369
712
14th September
Session 3.3
( SOIL REMEDIATION 1 )
Chairman: Felipe Macias
713
REMEDIATION OF SOILS CONTAMINATED WITH XYLENE COMBINING

SOIL VAPOR EXTRACTION AND BIOREMEDIATION
1,2 2 2 2 2
A.A. Soares , T. Pinho , J.T. Albergaria , V.F. Domingues and C. Delerue-Matos
1 Dept. of Agroecology and Environment, Faculty of Science and Technology, Aarhus University,
Blichers All, Postbox 50, DK-8830 Tjele, Denmark. antonio.soares@agrsci.dk
2 Requimte, Instituto Superior de Engenharia do Porto, Instituto Politcnico do Porto, Rua Dr.
Antnio Bernardino de Almeida, 431, 4200-072 Porto, Portugal. cmm@isep.ipp.pt
ABSTRACT
This work aims the study of the combination of soil vapor extraction (SVE) with
bioremediation (BR) to remediate soils contaminated with xylene. Several soil water
content (SWC) (1, 2, 3 and 4%) and natural organic matter (NOM) (4, 14 and 24%)
samples were analyzed in the SVE. Several concentrations were studied (187, 209 and
-1 -1
306 mg kg for 14% NOM and (292, 328 and 477 mg kg for 24% NOM). SVE
experiments were performed both in sandy and in humic soils.
The main goals were: (i) evaluate the performance of SVE regarding the remediation time
and the process efficiency; (ii) study the combination of both technologies in order to
identify the best option capable to achieve the legal clean up goals; and (iii) evaluate the
influence of NOM on SVE and BR. The remediation experiments performed in soils
contaminated with xylene allowed concluding that: (i) BR showed to be an efficient
technology to complement SVE according to all 14% NOM samples; (ii) NOM as source
of microorganisms and nutrients enhanced BR but hindered the SVE due the limitation on
the mass transfer of xylene from the soil to the gas phase ; (iii) Levels of contamination of
-1
xylene in soil above 328 mg kg showed to be inhibitory to microbial activity.
Keywords: BTEX, Xylene, SVE, Bioremediation
INTRODUCTION
Benzene, toluene, ethylbenzene and xylenes, commonly referred as BTEX, are critical
monoaromatic environmental contaminants worldwide. These compounds can cause serious
environmental and health problems because they are frequently found, alone or together, at
hazardous waste sites, around leaking tanks or ruptured pipelines. Thus, soil and groundwater can
be massively polluted by these compounds. The studied compound, xylene, is a clear, light-colored
or colorless, flammable liquid which evaporates quickly. Its odor is strong and sweetish like other
aromatic solvents. Xylene is also called "xylol," "dimethylbenzene," or "mixed xylenes." It may be
found in solvents for gums, resins, and rubber cleaners and degreasers paints, lacquers, and
varnishes adhesives, cements, and epoxy resins inks and dyes aviation gasolines.
Xylene encompasses three isomers of dimethylbenzene. The isomers are distinguished by the
designations by the designations ortho- (o-), meta- (m-) and para- (p-), which specify to which
carbon atoms (of the benzene ring) the two methyl groups are attached. The Annual Status Report
from Treatment Technologies for Site Cleanup issued by the United States Environmental
Protection Agency (USEPA) [1] concluded that xylene, a non-chlorinated volatile organic
compound, was found in 24% of the documented remediation projects. According to the report, the
remediation technologies that were most commonly used to remediate soils contaminated with
BTEX were SVE (used in 32% of the projects), solidification & stabilization and BR, multiphase
extraction and BR (the latter with 10%). The choice of the most appropriate remediation
technology, the estimation of the respective remediation time and efficiency are key parameters for
the success of a remediation action [2].
714
SVE is an in situ technology that is extremely efficient for the remediation of soils contaminated
with volatile and semi volatile organic compounds located in the unsaturated zone of the soil. It
relies on the maximization of volatile organic compound via vapor extraction [3-6]. The advantages
of SVE systems over other remediation technologies may be attributed to its relative low cost and
relative simplicity of installation, system operation and minimal amount of required equipment
[7].The main factors controlling the performance of SVE are the chemical composition of the
contaminants, vapor flow rates through the vadose zone, and the distribution of air flow channels
through the contaminant zone [8]. Moreover, it is known that the rate and extent of removal of
volatile organic compounds from the soil by active or passive vapor extraction systems are affected
by factors such as soil permeability, applied vacuum, airflow rate, temperature, vapor pressure,
external boundary conditions, the degree of partitioning among the vapor, liquid, dissolved and
adsorbed phases, SWC and NOM [9]. Albergaria et al. [10] performed SVE experiments in soils
contaminated with cyclohexane presenting different SWC and NOM and obtained efficiencies
above 90%. Lee et al. [11] and Malina et al. [12] investigated the feasibility of using SVE
technology for a petroleum hydrocarbon-contaminated site, both reporting high initial mass
-1
removals. Malina et al. [12] observed that 4mg g soil of toluene initially present in soil was
1
reduced by 99% within 24 days of applying a constant gas flow of 40cm h . The NOM is one of the
most important parameter on the SVE process because of its impact on the adsorption phenomena
that influence the mobility and availability of contaminants in soil.
SWC is the other parameter that strongly affects the remediation time and efficiency, due to its
influence on contaminant availability and soil permeability, which is the most important factor in
volatile organic compounds migration through soil [13]. Alvim-Ferraz et al. [14] concluded that NOM
and SWC negatively influence SVE, turning it less efficient and time consuming and, consequently,
more expensive.
BR can be defined as the breakdown of organic compounds in nature by the action of
microorganisms, such as bacteria or fungi [15]. This technology offers the potential to remediate
contaminated soil and groundwater without the need for excavation, decreasing significantly the
remediation cost. The success of a BR project depends on the type of microorganisms present in
the soil, their location and on environmental factors [16]. Previous results by Soares et al., [17]
showed that in soils contaminated with benzene, SVE, just by itself, achieved the clean up goals
-1
imposed by Spanish Legislation (1.0 mg kg ) [18] in 65% of the remediation experiments
performed. In the remaining cases, BR was implemented and showed to be efficient to finalize the
remediation process. The elimination of BTEX compounds together from soil was studied by
Margesin et al. [19]. After 18 days at 20 C, 21% of the initial total BTEX contamination (400 mg kg
-1
soil) was lost due to sorption onto soil and biodegradation decreased in the order ethylbenzene >
toluene > benzene > o-xylene.
Thereby, the combination of these technologies makes use of the quickness and high efficiency of
the early stages of the SVE and the low cost of BR to achieve the clean up goals.

The sandy soil was collected at a depth of 3 m in different places of a beach and the humic soil
was collected in a forest at a depth of 1-2 cm. Both samples were obtained from the region around
Porto, Portugal, and were stored in appropriate vessels. The characterization of the prepared soils
is described in Soares et al. [17]. Relatively high pH values were observed, due to the presence of
shell debris in sandy soils.
The evaluation of the performance of the SVE process requires the determination of the level of
contamination that remained in soil. This determination was achieved using the method described
in Albergaria et al. [10]. This method consisted in the preparation of several columns containing the
different soils with different levels of contamination. After the establishment of the equilibrium inside
the column, the concentration of the contaminant in the gas phase of the soil was determined by
gas chromatography. Through data fitting, a mathematical function relating gas phase
concentration with the level of contamination in the soil was calculated. Using this function and only
gas-phase contaminant concentration, it was possible to extrapolate the level of contamination in
the soil samples at the end of each SVE and the efficiency of the process.
The SVE experiments were performed in stainless steel columns. To evaluate if equilibrium was
reached, the concentration of the contaminant in the soil gas phase was monitored over time in
four different levels of the column. The remediation process was considered finished when the
715
-1
concentration of the contaminant in the gas phase was below 1.0 mg L [17]. The time needed to
reach this level was considered as the SVE remediation time and the remaining level of
contamination was calculated.
Therefore, the BR experiments were performed in the soils that, after SVE, presented
contamination levels above the considered legal limits. The preparation of the soils for BR
-1
consisted in the addition of substrate (MinE, 10 mL kgsoil ), prepared according to Kelly et al., [20]
and water. These experiments were considered finished when the concentration of xylene in soil
reached the legal limit. Columns were prepared with sterile soils with 14% and 24% of NOM
-1
(sterilized by autoclaving) contaminated with 100 mg kg of xylene. After the establishment of the
-1
equilibrium in the column, the concentration of xylene in the gas phase of the soil was 2.0 mg L for
-1
soil with 14% NOM and 1.0 mg L for soil with 24% NOM. When these concentrations were
reached in the BR experiments with the corresponding soil, the remediation was considered
finished. The time required to reach these levels was considered the BR time.
RESULTS
The majority of the experiments were achieved only using SVE, which demonstrate the efficiency
of SVE for the soils considered. This means that the remaining level of contamination after the SVE
-1
was below the legal limit (100 mg xylene kg of soil) and the proposed goal was considered
completely achieved and the remediation complete. It can be concluded that in sandy soils, when
higher airflow rates were used, the soil water content showed a small impact on the SVE process.
The soils with higher water content have lower capacity to adsorb the xylene, increasing the
tendency of the contaminant to transfer to the gas phase of the soil, thus becoming more mobile
and easy to extract. This behavior is enhanced by the low solubility in water of xylene and could
explain the low level of contamination observed in soils with 3% and 4% of SWC after the SVE. In
sandy soils, the effect of the SWC on SVE was clearer when lower airflow rates were used, leading
to a considerable increase on the remediation time. In humic soils, slower and less efficient
remediation results were obtained. This effect was most intense in the soil with highest NOM. This
is explained by the capacity of these soils to adsorb higher amounts of contaminant, which
subsequently reduces its mobility and capability to be extracted [21]. The impact of NOM in the
remediation time was even clearer when lower airflow rates were used, resulting in longer
remediation times and higher levels of contamination remaining in soil after the SVE treatment.
As stated before, the BR column experiments were performed in those cases in which the clean up
goals had not been achieved by SVE and that required further treatment. The soils in question
-1
were the 14% NOM soils contaminated with three levels of xylene (187, 209 and 306 mg kg ) and
the 24% NOM soils contaminated with another three levels of contamination (292, 328 and 477 mg
-1
kg ). The monitoring of the BR processes in these experiments is presented in Figure 1 and 2, for
both kind of soils (14% and 24% NOM) respectively.
Fig 1. Monitoring of bioremediation for 14% NOM.
716
Figure 1 shows that for soils with 24% NOM, the BR treatment managed to achieve the defined
clean up goals for all xylene concentrations. The monitoring curves for the three experiments
showed similar shapes, with two distinct phases. A first stage, within the first 400 hours, in which
pollutant diffusion/partition effects possibly coupled with microbial activity, originated a fast
decrease in the concentration of xylene in the gas phase of the soil. The second phase was
characterized by a slower degradation of xylene but the goal was achieved.
Figure 2 presents different results. All the experiments have a high variation. This seems to
indicate that these concentrations of xylene were affecting microbial activity and inhibiting the
bioremediation process. For all the concentrations it was noticed a peak that could be due to lack
of oxygen in the soil matrix.
Fig 2. Monitoring of bioremediation for 24% NOM.
Results from a previous study from our group on identical soils but contaminated with benzene [17]
were similar to the ones we present here: the remediation times were directly proportional to the
level of contamination and inversely proportional to NOM content, showing that organic matter
hinders SVE but enhances BR. This was explained by the fact that soils with higher organic matter
contents may be more populated by indigenous microorganisms increasing their capability to
degrade contaminants. Benzene had lower bioremediation times (did not exceed 650 h) compared
-1
with xylene (600 - 1000 h). The levels of contamination in that case were lower (70 170 mg kg ),
-1 -1
but the legal limit for benzene is lower (10 mg kg ) than for xylene (100 mg kg ). Ni et al. [22] also
concluded that Pseudomonas fulva strain TY16 uses benzene as carbon source much faster than
xylene in the same conditions. Others authors too [23-25] concluded that the biodegradation times
for toluene, ethylbenzene and xylene were longer than for benzene. Our data confirm the notion
that, although more toxic to humans, benzene is easier to remediate than its substituted analogues.
CONCLUSIONS
The remediation experiments performed in soils contaminated with xylene lead to the following
conclusions:
-The majority of the experiments reached the clean up goals just with the use of SVE ;
-SVE performed in sandy soils with higher SWC and using lower airflow rates required
considerably longer remediation times ;
-In humic soils, longer and less efficient SVE processes were observed ;
-NOM as source of microorganisms and nutrients enhanced BR but hindered the SVE due the
limitation on the mass transfer of xylene from the soil to the gas phase ;
-1
-Levels of contamination of xylene in soil above 328 mg kg showed to be inhibitory to microbial
activity.
717
Summarizing, the use of BR to complement SVE seems an adequate means to reach the cleanup
of xylene below legal limits. Despite the considerable increase of remediation time, it offers the
advantage of being an inexpensive process assuming that there is no need for rapid treatment.
References
th
[1] USEPA, Treatment Technologies For Site Cleanup: Annual Status Report, 13 Ed., Retrieved
September, 2010. Information on http://clu-in.org/asr/.
[2] J.T. Albergaria, Extraco de Vapor para Remediao de Solos Controlo dos parmetros que
limitam a descontaminao, Master Thesis, Faculdade de Engenharia da Universidade do Porto,
Porto, 2003.
[3]D. Downey, R. Miller, T.Dragoo, Procedures for conducting bioventing pilot tests and long-term
monitoring of bioventing systems.U.S. Air Force, Parsons (2004).
[4] V. Kaleris, J. Crois, Estimation of cleanup time for continuous and pulsed soil vapor extraction,
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719
PYROLYSIS AS A TECHNIQUE FOR REMEDIATION OF CONTAMINATED

SOIL
1 2 3 4
C. Bulmu , A. Badea , I. Istrate and T. Apostol
1 Dpt. Energy Generation and Use, University POLITEHNICA of Bucharest, Romania, email:
cora_bulmau@yahoo.com
adrian.badea@energ.pub.ro
ia_istrate@yahoo.com
tiberiuapostol80@gmail.ro
ABSTRACT
Thermal treatments are considered the most popular and versatile techniques because
they can be applied to a wide range of organic contaminants [1]. In the last years, for the
remediation of the polluted sites, thermal decontamination technologies present a
significant scientific and practical interest because they can provide high destruction and
removal efficiencies for organic pollutants. These remediation technologies have been
also selected for cleanup of Superfund sites [2, 3]. In the present paper, pilot plant studies
were carried out in order to evaluate the feasibility of remediation of soil contaminated
with petroleum hydrocarbons. The laboratory scale system is represented by a rotary
reactor, electrical heated. The soil samples thermal treated in the experimental campaign
are natural contaminated, collected from a Romanian area polluted with petroleum
hydrocarbons. The experiments were conducted for different pyrolysis temperatures and
focused on the influence of the process temperature on the decontamination efficiency.
The soil quality as well as the quality and amount of volatile compounds generated during
the pyrolysis process were monitored. The results have showed that satisfactory level of
soil decontamination could be achieved at high treatment temperatures. The efficiency of
the decontamination by pyrolysis treatment increases significantly while the process
temperature rises.
Keywords: contaminated; soil; pyrolysis
INTRODUCTION
The European Environmental Agency has estimated that soil contamination requiring clean up is
present at approximately 250 000 sites and that more than 80 000 sites have been cleaned up
during the last 30 years in EU countries. It is also expected that number of sites needing
remediation will increase by 50% by 2025 [4]. Many industrial sites and oil refineries contain soils
contaminated with petroleum hydrocarbons, soils considered as hazardous wastes if the
concentration of those pollutants is significantly (under criteria 40 CFR 261.24 Toxicity
Characteristic (TC) Code of Federal Regulations).
For the remediation of these sites, in the last years thermal decontamination technologies present a
significant scientific and practical interest because they can provide high destruction and removal
efficiencies for organic pollutants. These remediation technologies have been also selected for
cleanup of Superfund sites [3, 5].
The petroleum hydrocarbons are a mixing of volatile and non-volatile hydrocarbons that get to soil
surface by spill or wastes storage. They can contaminate the surface of the soil, the non-saturated
area and the underground water and represent a pollution source for a long time. The evolution of
the hydrocarbon combination depends on changes of soil water regime due to levitation
phenomena that is happening [6]. Because of many simultaneous processes (retention,
volatilization, dissolution, biodegradation) during the levitation the content of petroleum
720
contaminants is changing. On the other hand the petroleum wastes existent in soil generate
polycyclic aromatic hydrocarbons with carcinogenic potential for human health. PAH were the
subject of many research studies due to their toxicity, persistency and environmental prevalence [7,
8]. These studies mentioned 16 species of PAH, designated as priority pollutants by the United
States of Environmental Protection Agency (US-EPA). Thermal degradation of PAHs represents
one of the methods to destroy the pollutants and their hazardous by-products too. During thermal
process, generation and/or degradation of PAHs is due to their chemical structure stability and rate
of degradation.
Many hydrocarbons are of high molecular weight and exhibit low volatility, recalcitrance to microbial
breakdown, and limited solubility in, and limited extractability from soil into, many liquids such as
water and surfactant-water solutions. Thus, thermal destruction may be the preferred for
remediating sites contaminated with hydrocarbons. They employ heat to either destroy or volatilize
the hydrocarbons in contaminated soils and are the most popular and versatile techniques because
they can be effectively applied to a wide range of organic contaminants [9]. Thermal treatment
provides soil decontamination efficiencies exceeding 99%. The required treatment times can range
from a few seconds, to several tens of seconds, to multiple minutes, for treatment temperatures of
approximately 7501000C, 400600C, and 150300C, respectively [10,11].
Choosing the most appropriate technology for the soil decontamination depends on the nature of
the pollutant petroleum product, on the soil structure and composition. Not in the last it depends on
the pollutant quantity from the soil and on the surface and the depth where the petroleum product
has penetrated. To establish an optimal technology for polluted soil decontamination it is
imperiously need to adopt a systematically and organised approach in order to obtain favourable
results.
The present paper has proposed to evaluate the feasibility of the pyrolysis treatment used for soil
decontamination and to study the influence of the thermal treatment operational conditions on the
pyro-products and on remediation efficiency in case of a real soil polluted with petroleum products.
EXPERIMENTAL
Material
A soil from central aria from Romania was used for the present experimental research. It was
natural contaminated due to a mining exploitation. The samples were collected from many points of
the surface area at 20 cm and 40 cm depth, then creating a mixing. The soil mass were size-
fractionated by a cutting mill.
The elemental composition of contaminated soil report 13.36% of organic carbon some of which is
believed to decompose to light gases during thermal treatment [12, 13]. The samples of
contaminated soil are characterized by properties contained by table 1. The soil moisture amount
has been experimentally measured using a laboratory oven-drying. The soil sample has been
weighted before being introduced inside the oven-drying. Here the material has been kept at a
temperature of 105C for 24 hours. Then it was weighted again and so the moisture quantity was
calculated.
Table 1
Properties of contaminated soil
Contaminated soil properties Value Unit
Humus amount 39.2 [%]
Corg 13.36 [%]
Density 1.5 [g/cm3]
Umidity 16 [%]
TPH 71 000 [mg/kgdry soil]
721
Equipment
The laboratory scale system showed in figure 1 consist in a rotary batch reactor, electrical heated.
It was built in the Laboratory of Energetic and Environmental Renewable Resources, from Power
Engineering Faculty University POLITEHNICA of Bucharest. The installation can be used for
semi-industrial testing of different thermal treatments: pyrolysis, combustion and gasification of
solid wastes. The material treated in this system is a part of solid fuel class.
Fig. 1. Semi-industrial pyro-combustion furnace
The rotary furnace works in continuously mode for a maximum flow of 50 kg/h of soil. The moisture,
density and energy content can be different from a fuel to another fuel. Three parts compose the
experimental setup: feeding system, pyro-combustion section and flue-gas treatment line.
3
The feeding with fuel is manually operated. The storage bin is of about 0.04 m and is made of
stainless steel.
The technical schema of the experimental setup is presented in figure 2.
The combustion system is divided into 2 sections: pyrolysis reactor and combustion chamber. The
thermal decomposition process occurs inside of the first section that is a horizontal cylindrical
reactor. Its length is 1500 mm and the internal diameter attends 158 mm. The reactor is made of
thermal resistant stainless steel (W4841) and it is electrically heated by 8 electric resistances.
These are circularly distributed at the reactor extremities like two belts, disposed on a fire-clay
lining and having an electrical power of about 15 kW (7.5 kW each). In order to realize the thermal
control 4 electrical resistances are put on each belt, working in tandem 2 by 2 in diagonal line. The
pyrolysis section can work in an angle by maximum 7.
The last part of the installation is represented by the flue-gas treatment system. It is composed by:
a heat exchanger, a cyclone and a scrubber. The ash is collected at the base of the cyclone within
an ash collector. After the flue gases are cooled and partially cleaned, they are introduced into a
cylindrical scrubber where they are cleaned by washing. After the cleaning procedure, the gases
flow go through a stainless steel pipe and are evacuated into the atmosphere by means of an
exhaust fan.
Operating procedure
The experiments performed on the laboratory pyrolysis equipment aim to obtained information
about the influence of the process temperature on remediation efficiency of pyrolysis treatments.
So, only the solid part obtained from the thermal process was follow up. The ash (decontaminated
soils) resulted from the non-oxidant processes have been characterized by chemical analyses.
The feeding with material was carried manually in a continuously mode. For each experiment I
have used a flow of 20 kg/h of contaminated soil. The temperature range of the experimental
campaign was between 450C and 800C. For all thermal treatments the mass of the polluted soil
was kept in the pyrolysis reactor for 2 residential times: 15 and 30 minutes.
722
In order to established the decontamination level of pyrolysis treatments the hydrocarbons content
for the initial polluted soil and for the ash samples was determined by solvent extraction using a
Soxhlet extractor.
Fig. 2. Schema ..
1 pyrolysis reactor 6 - post combustion chamber 11 - flue-gas exhauster

2 feeding system 7 - heat exchanger 12 - combustion air admission
3 bidirectional rotating device 8 - cyclone 13 - methane admission
4 - pyrolysis reactor tilting device 9 - scrubber 14 char evacuation flange
5 - inductive heating system 10 - steam generator
RESULTS AND DISCUSSIONS

The experimental research has focused on the influence of the process temperature on
decontamination efficiency.
The results of the experiments have demonstrated that process parameter like temperature has an
important influence on the ash and volatile production [14]. Figure 3 present the variation of the two
pyro-products (ash and volatile) function of temperature. Increasing this process parameter the ash
quantity decreases while the volatile mass is rising.
Fig. 3. Variation of ash and volatiles yields function of process temperature
723
Increasing of process temperature the ash yields have decreased from 81.43% in case of pyrolysis
at 350C to 73.59% for thermal treatment conducted at 800C. Alternately, rising the pyrolysis
temperature from 350C to 800C the volatile mass has increased with 7.84%
The ash samples generated from the pyrolysis treatments were analysed in order to measure the
hydrocarbons content, so to established the pyrolysis efficiency. For this extractions
using dichloromethane were realized in a Soxhlet apparatus. Table 2 contents the values for the
remediation level of thermal treatments applied to the contaminated soil.
Table 2
Decontamination level of pyrolysis treatments
DECONTAMINATION LEVEL
[%]
Time
[min] T [C]
350 500 650 800
15 65.21 69.58 96.03 97.31
30 68.17 76.62 97.04 98.17
The variation of the pyrolysis treatments efficiency function of process temperature and residential
time and obtained in the present experimental research are shown in the graph from the figure 4.
The remediation level of decontamination treatments increases by temperature and residential time
too. For example, in case of pyrolysis processes realized for a residential time equal to 30 minutes,
the level of decontamination has raised from 68.17% ( pyrolysis at 350C) to 98.17% (pyrolysis at
800C). An important observation can be done about the difference of the decontamination level
between the treatment realized at 650C and 800C: it is a very small value 0.86%. That means it
is not need that temperature of pyrolysis process to exceed 650C. A rise of temperature up to this
value doesnt justify the energy consumption. Economical studies about this subject will be done in
the future.
The graph from below shows that pyrolysis efficiency increases as the residential time of the
process is rising. The experimental results have demonstrated a rise of decontamination level by
7% in case of non-oxidant thermal treatment realized at 500C and by 1 2% for the rest of
pyrolysis process (realized at 350C, 650C and 800C).
Fig. 4. Pyrolysis efficiency function of process temperature and residential time
724
CONCLUSIONS
The experimental results of the present research have shown that the process parameters has a
main influence on the remediation of the analysed contaminated soil. The efficiency of the pyrolysis
treatment increase signifiantly with the process temperature and less with residential time. The
efficiency of the pyrolysis treatments used for decontamination of the polluted soil has raised with
almost 30% if the process temperature was majored from 350C to 800C. The values obtained
from the present experimental campaign have shown that soil decontamination by pyrolysis
treatments can exceed 99%. So we can say that pyrolysis treatment represent a good technique for
remediation of contaminated soils.
Another conclusion is that the rise of temperature pyrolysis up to 650C doesnt justify the energy
consumption. In the future economical studies about the subject will be done. An important decision
was taken: the range of the process temperature must be reduced.
Acknowledgement
The work has been co-funded by the Sectorial Operational Programme Human Resources
Development 2007-2013 of the Romanian Ministry of Labour , Family and Social protection through
the Financial Agreement POSDRU/89/1.5/S/62557.
REFERENCE
[1] J. Merino, V. Bucal, Effect of temperature on the release of hexadecane from soil by thermal
treatment, Journal of Hazardous Materials, 143 (2007), pp. 455461
[2] P.S. Daley, Cleaning up sites with on-site process plants, Environmental Science &
Technologies, 23 (1989), pp. 912916
[3] J.J. Cudahy, W.L.J. Troxler, Thermal Treatment Remediation Industry Contractor Survey,
Journal of Air & Waste Management Association, 42 (1991), pp. 844849
[4] EEA, Progress in management of contaminated sites (CSI 015) - Assessment published August
2007
[5] P.S. Daley, Cleaning up sites with on-site process plants, Environmental Science & Technology,
23 (1989), pp. 912916
[6] M.G. Tudorache, Natural sorbents used for decontamination of soils polluted with petroleum
hydrocarbons, Dissertation Thesis, Saint Ierarh Nicholae Ed. (2010), ISBN 978-606-577-147-5, 72
pages
[7] M. Blumer, Polycyclic aromatic compounds in nature, Scientific American, 234 (1976), pp. 34-44
[8] M. Donald , K.C. Ma, Illustrated Handbook of Physical-chemical Properties and Environmental
Fate for Organic Chemicals: Introduction in Hydrocarbons, Lewis Publishers (1992), ISBN
0873715136, 9780873715133
[9] J. Merin, V. Bucal, Effect of temperature on the release of hexadecane from soil by thermal
treatment, Journal of Hazardous Materials, 143 (2007), pp. 455461
[10] U.S. EPA. Superfund: Focusing on the Nation at Large, Publication #9200.5-701A, Document
PB919-212-02, U.S. Environmental Protection Agency, Washington (1991)
[11] H.H. Saito, J.B. Howard, W.A. Peters, V. Bucal, , The Encyclopedia of Environmental
Analysis and Remediation, vol. 7, John Wiley & Sons in: R.A. Meyers Ed., New York, 1998, pp.
45544589.
[12] U.S. EPA Development and Use of EPA Synthetic Soil Matrix (SSM/SARM), U.S.
Environmental Protection Agency, Edison, NJ, 1989
[13] V., H. Saito, J.B. Howard and W.A. Peters, Products Compositions and Release Rates from
Intense Thermal Treatment of Soil, Industrial & Engineering Chemistry Research 35 (8) (1996), pp.
27252734
[14] Cora Gheorghe (Bulmu), Contributions Concerning the Biomass Revaluation by Pyrolysis
Processes, PhD Thesis, University POLITEHNICA Bucharest, Engineering Power Faculty, 2009,
183 pages
725
St
WASTE AMENDMENTS AND TREE VEGETATION TO INCREASE

NUTRIENTS CONTENT IN MINE TAILING SOILS
V. Asensio1, R. Forjn1, F.A. Vega1, M.L. Andrade1 and E.F. Covelo1

1
Departamento de Bioloxa Vexetal e Ciencia do Solo, Facultade de Bioloxia, Universidade de
Vigo, Lagoas, Marcosende, 36310 Vigo, Pontevedra, Spain. Tel.: +34 986812630. Fax: +34
986812556. E-mail address: verosaf@uvigo.es
ABSTRACT
They were selected different areas at Touro mine tailings to evaluate the effect of both
waste amendments and planted trees on nutrients content in four minesoils: i) untreated
soil (M1), ii) only vegetated soil (M2), iii) waste amended soil (M3) and iv) both amended
and vegetated soil (M4). The bioavailable K and P, Olsen P, total nitrogen Kjeldahl (TN)
and both inorganic and organic N (ON and IN) were measured.
Tree vegetation significantly increased organic and inorganic N in the minesoil. The
recently added waste amendment increased inorganic N and bioavailable P and K. Both
treatments at the same time significantly increased P and K in available form, but they did
not increase inorganic N. It was observed that waste amendments made of sewage
sludges and residues from a paper mill increased the concentration in soil of the most
important nutrients for plants (N, P and K). Since these elements can be leached or taken
by plants in a short term it is advisable the use of wastes as amendments in these soils.
Their periodic application must be controlled in order to keep a suitable level of nutrients
for plant development.
Keywords: mine tailing; soil nutrients; tree vegetation; waste amendments.
INTRODUCTION
It is very difficult to establish the cover vegetation on mine soils after a mine closes if no
remediation techniques are applied on tailings since the soils developed on them use to be poor in
organic matter and nutrients. The soils formed on tailings from metal mines as copper ones also
require treatments to solve the problem of metal bioavailability and pollution. It is well known that
soil organic matter is one of the most important sorbents in soil horizons; therefore the use of
organic wastes as amendments can not only favour nutrient availability for plant growth but also
reduce the risk of metal mobility in soils. While inorganic fertilizers are used to provide nutrients,
the amendment with biosolids would also provide nutrients and organic matter as well as favor the
slowly release of nutrients including micronutrients [3].
Nitrogen (N) and phosphorus (P) are essential elements that can limit plant growth in many
ecosystems [1, 2] and especially in minesoils. The use of different kind of amendments can create
more favorable conditions for plant growth.
The tailings from the depleted copper mine at Touro (NW Spain) are being recovered since few
years ago by means of different treatments. The copper mining activity finished in 1988 and
nowadays material for road construction is being extracted in some of the tailings. As a result many
areas in this mine are covered with unstructured material, rich in sulphurs, with extremely acidic pH
in most of the cases and poor organic matter contents. Moreover the reclamation of the tailings at
the end of the copper extraction was partially made by means of only planting trees.
The company Ecological Treatments of Northwest (T.E.N.) began in the year 2000 to vegetate and
amend some areas at the mine tailings with the aim of recovering the mine soils. T.E.N. planted
Pinus pinaster Aiton and Eucalyptus globulus Labill and they added amendments mainly composed
726
by sewage sludges and ashes from a paper mill. These amendments are considered as a new
horizon over the mine tailing soil and they are called Technosols according to [4].
The hypothesis of this work was that the planting of E. globulus Labill or P. pinaster Aiton, the
addition of waste amendments or the combination of both treatments can increase the level of
nutrients in the degraded mine soils. The aim of the work was to detect if planted trees and/or
waste amendments increased the nutrients content in mine tailing soils.
Sampling area and soil samples

Sampling place is located in Touro mine, in the northwest of Spain (Lat/Lon (Datum ETRS89): 8
20' 12.06'' W 42 52' 46.18'' N) (Fig. 1). The climate of the experimental site is Atlantic (oceanic)
where precipitation reaches 1886 mm per year (with an average of 157 mm per month). Mean daily
temperature is 12.6C and the relative humidity is 77% (annual average) [5].
Fig. 1. Touro mine.
They were selected four areas in the mine tailing at Touro and the superficial horizons of the soils
were sampled. Below the superficial horizons there is an AC horizon over the C one. Only in the
case of the soil vegetated for more years (M2) there is an A horizon over the AC, and it was also
sampled. Five samples of each horizon were taken to do a homogeneous sample of each horizon.
They were taken the first 20 cm of each AC horizon and the 5 cm of depth in the case of the only
one sampled A horizon. Each pooled sample was stored in a polyethylene bag for further
treatments and analysis. Soil profiles were described according to [4] and Fig. 2 shows the five
sampled horizons on 9th March 2010, as described below:
- M1 was taken as the control sample since it was located in an untreated and bare area.
- M2 is from an area of the mine tailing vegetated with P. pinaster Aiton 21 years ago. The A
horizon of this soil was sampled (M2A) as well as its C one (M2B), as mentioned above.
- M3 comes from an area amended with wastes since six months ago.
- M4 is in an area both amended and vegetated (E. globulus Labill) 10 years ago.
The added waste amendments (in M3 and M4) were basically made of sewage sludges and ashes
from a paper mill. They were added with trucks and spread over the soil surface.
Methods
Soil samples were air dried, passed through a 2 mm sieve and homogenized in a vibratory
homogeniser for solid samples (Fritsch Laborette 27 rotary sampler divider).
727
Standard procedures were used to determine soil stoniness [6], particle size distribution [7] and
bulk density [8]. Soil reaction was determined with pH electrode in 1:2.5 soil:water and soil:1M KCl
solution. Electrical conductivity (EC) was determined according to [9]. Exchangeable cations were
extracted with 0.1M BaCl2 [10] and their concentration in the extracts was measured by ICP-AES.
Effective cation exchange capacity (CECe) was also calculated.
Soil organic carbon was determined in the solids module (SSM) from a TOC equipment (TNM-1,
Shimadzu). The bioavailable content of K and P was extracted with 0.1M CaCl 2 [11] and total
bioavailable P content was determined by the Olsen method [12]. Total Kjeldahl-N (TN) was
determined according to [13]. Inorganic N (IN), which comprises NH4+ (ammonium) and NO3- and
NO2- (nitrates and nitrites) was analyzed according to [14].
All of the experiments were performed in triplicate and the data were statistically treated using
SPSS v. 15.0 for Windows. Analysis of variance (ANOVA) and test of homogeneity of variance
were carried out. In case of homogeneity, least significant difference (LSD) test was carried out as
post-hoc. If there was no homogeneity, Dunnetts T3 test was performed. The Mann-Whitney test
was done when the data were not parametric. Correlated bivariate analysis was also carried out
with data from all soil samples. An independent t-test was done to compare the untreated mine
tailing soil with the horizon that is analogous to it (M2B).
Fig. 2. Profiles of selected soil samples, from left to right and top to bottom: M1, M2, M3 and M4.
Nutrients in the untreated mine tailing soil (M1)

Table 1 shows the results of the soil properties and contents analyzed. Even bioavailable K is the
nutrient in highest amounts detected in M1 this is the lowest K content in all studied soils. The
same happens with the content of inorganic carbon. IN can be taken by plants; nevertheless there
is no vegetation in this soil probably due to the lack of most of the nutrients and the high C/N ratio
[15]. There was not detected bioavailable P in M1 (Table 1) and the soil organic C is less than
0.7%. This is one of the most important factors influencing the lack of nutrients which is also
728
favoured by the extremely acidic pH of M1 (3.62, Table 1), the high sand proportion in its mineral
fraction (70%) and the fact that stoniness represent more than 50% (Table 1).
Effect of tree vegetation (M2)
The positive effect of the planted vegetation and the time elapsed (21 years) on soil developing is
clearly shown since there is a new soil profile (M2A) in this area. Table 1 shows M2A properties.
Stoniness was considerably reduced compared to M1, pH is almost neutral and SOC significantly
increased on this horizon (Table 1). Nevertheless M2A is still a thin horizon (5 cm depth) and it is
less involved on plant growth than M2B where most of the roots are growing. Because of this fact
we will focus more in M2B properties for comparing with M1.
M2B had significantly (P < 0.05) more bioavailable K than the original bare soil. This fact can be
explained because of the higher pH (Table 1) since plants have the optimum profit of nutrients
when pH is around 6-7.5 [16]. Olsen P increased as well in M2B compared to M1 (Table 1),
nevertheless bioavailable P is still undetectable (Table 1). Even P bioavailability on soils is still not
well understood it is known that P is the least mobile and bioavailable nutrient under several soil
conditions [17] Since Olsen P was detected and not all forms of phosphorus that can be extracted
with Olsen method can be taken for plants [17] it is possible that a P pool exists in the M2 soil
horizons.
Vegetation significantly (P < 0.05) increased both organic and inorganic nitrogen. Organic N comes
from the fresh organic matter since there is more ON in the topsoil of the vegetated soil (M2A) than
in the bare soil (M1). Nevertheless the N content is still very low in M2 horizons. Inorganic N can
come from the nitrification of ON [18]. There was significantly (P < 0.05) much more concentration
of inorganic N in the topsoil of M2 than in its subsurface horizon (Table 1), because usually there is
more microbial activity in superficial horizons. C/N ratio significantly (P < 0.05) increased in both
horizons of the vegetated soil respect to M1 (Table 1). They were not detected significant
differences between M2B and M1 according to the ANOVA performed, but it was clearly detected
with an independent t-student test. The vegetation clearly influences (P < 0.05) the C/N ratio
according to the ANOVA carried out. It is important to observe that C/N ratio in M2 is higher than
30, and it can cause a rapid increase in microbial biomass and depletion in available N for many
plants [15].
Effect of waste amendment (M3)

M3 has more bioavailable K and Olsen P than the untreated soil (P < 0.05; Table 1), and it was
detected bioavailable P. As in the vegetated soil, pH significantly increased in M3 compared to M1
(Table 1), but there was no significant statistical influence of the amendment in pH value. It is
possible that the increase of most of the nutrients concentration in soil was due to they come from
the amendment. Both sewage sludge and ashes from paper mills can have a considerable amount
of nutrients and they could be present in their bioavailable form. Some authors have reported
significant concentrations of macro and micronutrients in wastes from paper mills [19-21] and in
sewage sludges [22]. In fact, this recently amended soil was the sample with more TN, P and K
(Table 1)
C/N ratio was lesser in the amended soil sample than in M1 (Table 1). M3 had significantly (P <
0.05) more SOC and TN than M1, but total nitrogen increased in more proportion than SOC. Both
organic and inorganic nitrogen increased significantly (P < 0.05) in the amended soil compared to
M1 (Table 1). It was probably due to the N contents come from the amendment as other nutrients
previously mentioned.
Effect of both treatments: tree vegetation and waste amendment (M4)

M4 has more available K than M1 (P < 0.05, Table 1) and in addition, M4 has P in both extracted
forms (Olsen and CaCl2).
There is more organic N in M4 than in the untreated soil, but less inorganic N (Table 1). It can be
due to ON from the organic matter was added to M4 and because of plants uptake IN faster than
microorganisms metabolize the ON.
C/N is higher in M4 than in M1 (Table 1). The ratio in M4 is extremely high and it can cause a
depletion of available N for many plants [15].
729
CONCLUSIONS
Tree vegetation significantly increased organic and inorganic N in the mine soil. The recently added
waste amendment increased inorganic N and bioavailable P and K. Both treatments at the same
time significantly increased P and K in available form, but they did not increase inorganic N.
It was observed that waste amendments made of sewage sludges and residues from a paper mill
increased the concentration in soil of the most important nutrients for plants (N, P and K).
Nevertheless, these elements can be leached or taken by plants in a short term. It is advisable the
periodic use of wastes as amendments in degraded mine soils to keep a suitable level of nutrients
for plant development.
Table 1. Characteristics of the soil samples.

M1 M2A M2B M3 M4
- Old veg. Old veg. Waste amendments Veg.+waste
Stoniness [% by volume] 53.15b 22.89e 41.14d 56.26a 46.85c
-3
Bulk density [g cm ] 1.15b 1.88a 1.88a 0.93c 0.84d
pH H2O 3.62e 6.6b 5.24d 5.78c 8.21a
-1
EC [ms cm ] 0.15c 0.12c 0.15c 1.95a 0.22b
-1
CECe [cmol kg ] 10.09d 46.98b 31.09c 119a 104a
Sand [%] 70a 51e 59d 66b 61c
Silt [%] 20e 32a 26c 24d 26b
Clay [%] 11d 17a 15b 10e 13c
Texture Sandy loam Sandy loam Sandy loam Sandy loam Sandy loam
-1
SOC [g kg ] 6.89e 35.01c 8.34d 56.29a 54.84b
-1
Olsen P [mg kg ] u.l. 14.16c 3.76d 265a 125b
-1
K bioavailable [mg kg ] 29.61e 154c 59.65d 230a 184b
-1
P bioavailable [mg kg ] u.l. u.l. u.l. 29.17a 7.15b
-1
TN [g Kg ] 0.25d 0.74b 0.28d 3.69a 0.59c
-1
IN [g Kg ] 0.11b 0.55a 0.16b 0.60a 0.15b
-1
ON [g Kg ] 0.14d 0.19c 0.12e 3.08a 0.45b
C/N ratio 28.25c 47.85b 30.74c 15.30d 161a
Mean values: three replicates of each soil sample. Values followed by different letters in each row
differ significantly with P < 0.05. u.l.: undetectable level. EC: electrical conductivity, SOC: soil
organic carbon, TN: total N, IN: inorganic N, ON: organic N.
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730
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731
A NEW APPROACH TO SOIL REMEDIATION: COUPLING

NANOTECHNOLOGY WITH ELECTRICALLY INDUCED PARTICLE
TRANSPORT (ELECTROKINETICS)
1 2 1,3 4 5
H. Gomes , Celia M.D. Ferreira , A. B. Ribeiro , G. Loch , L.M. Ottosen
1 CENSE, Departamento de Cincias e Engenharia do Ambiente, Faculdade de Cincias e
Tecnologia, Universidade Nova de Lisboa, 2829-516 Caparica, Portugal, hrg@fct.unl.pt
2 CERNAS, Departamento de Ambiente, Escola Superior Agrria de Coimbra, Portugal,
celia@esac.pt
3 abr@fct.unl.pt
4 Department of Earth Sciences, Utrecht University, Utrecht, The Netherlands, jpgl@geo.uu.nl
5 Technical University of Denmark (DTU), Denmark, lo@byg.dtu.dk
ABSTRACT
Traditional remediation technologies for Persistent Organic Pollutants (POP) such as
Polychlorinated Biphenyls (PCBs) have serious limitations and high costs. Zero valent
iron nanoparticles (nZVI) represent a new generation of environmental remediation
technologies that could provide cost-effective solutions. However, the limited transport of
nZVI through soils has been identified to be a major drawback for in situ applications. The
main research objective of this study is to find out if coupling electrokinetics and reactive
iron nanoparticles can be an effective method for treating PCBs contaminated soils,
through electrically induced nanoparticle transport. To understand the fundamental
aspects of the coupled technology the authors suggest dividing the overall problem into
three submodels (transport of nanoparticles by electroosmosis and by electrophoresis
and degradation of PCB) which are then integrated into a macroscale
transport/degradation numerical model. This paper presents the experimental approach
suggested for each submodel under study. Testing this innovative solution using the
suggested approach will allow for a deeper understanding of both the electrokinetically
enhanced transport of nZVI and PCBs dechlorination.
Keywords: Electrokinetic remediation; Zero Valent Iron nanoparticles (nZVI); coupled

technologies; Persistent Organic Pollutants
INTRODUCTION
Soil contamination is a major environmental issue worldwide, as a result of mining, industrial and
urban activities over the past two centuries. Of special concern are Persistent Organic Pollutants
(POPs), namely Polychlorinated Biphenyls (PCBs). This family of synthetic organic compounds
comprises 209 congeners that differ in chlorine number and position and with unique chemical
properties. PCBs are very persistent to degradation and hazardous to the biosphere [1]. Estimates
of total PCBs production vary between 1.2 and 2 million t, with some of the most detailed data
indicating a total global production of approximately 1.3 million t over the period from 1929 to 1993
[2]. From this cumulative global production, about 440 to 92,000 t is estimated to have been
emitted into the environment [2, 3].
In the United States, 350 of the 1,290 Superfund Sites are contaminated with PCBs [4]. In Canada,
148 sites are contaminated with PCBs in the total inventoried 20,762 federal sites [5]. In European
countries, an estimate points to 242,000 contaminated sites and about 2.4% are contaminated with
chlorinated hydrocarbons [6]. An inventory on atmospheric deposition in background surface soil,
estimates a global total PCBs soil burden of 21,000 t [7].
732
The most frequent soil remediation technologies used for PCBs are dig and dump and also dig
and incinerate. It is of utmost importance to find cost-effective technologies to remove PCBs from
soils and sediments. This has been a challenging task for decades, since traditional methods like
excavation/landfilling and incineration are expensive and imply pollution transfer.
Zero valent iron nanoparticles (nZVI) are very effective in the degradation of a wide variety of
organic soil contaminants, such as chlorinated organic solvents, organochlorine pesticides and
PCBs [8, 9]. The principle behind nZVI is reductive dehalogenation, in which iron promotes the
removal of chlorine from the pollutant molecules, degrading them into harmless by-products. Zero
valent iron nanoparticles are traditionally injected under pressure and/or by gravity to the
subsurface where treatment is needed. However, transport of nZVI is normally limited by their
aggregation and settling [10] with mobility in the subsurface being normally less than a few meters.
Since the late 1980s electrokinetic (EK) remediation has been successfully used to treat different
types of soils [11-16] and waste materials [17-22]. Although electrokinetic removal of heavy metals
from soils is one of the most studied processes [23], electroremediation has also been applied to
organic contaminants, such as herbicides [24], creosote [25], chlorinated solvents [26-27],
petroleum hydrocarbons [28-29], phenol [30] and PAHs [31-33].
The method uses a low-level direct current as the cleaning agent, to remove matrix
contaminants. Several transport mechanisms (electroosmosis, electromigration and
electrophoresis) and electrochemical reactions (electrolysis and electrodeposition) are induced by
this method [11]. The contaminants are then moved towards one of the electrode compartments
where they become concentrated. The general principle of the electrokinetic process is presented
elsewhere and several authors have critically reviewed its state of knowledge [23, 34].
This work proposes the use of electrokinetics to enhance nZVI mobility and improve standard soil
nano remediation. The concept behind this research is to create electric fields to transport
nanoparticles through the soil, so that they come into contact with the pollutants.
ZERO VALENT IRON NANOPARTICLES

A nanoparticle a collection of tens to thousands of atoms measuring about 1-100 nm in
aggregate diameter and characterized by crystalline shapes and lattice structures is the most
basic structure in nanotechnology [35].
Nanoscale iron particles have large surface areas, high surface area-to-volume ratios and a large
fraction of stepped surface [36]. Such properties combine with a unique structure and zero valence
to make nano-sized metals extremely reactive [35, 36].
In general, reactions between chlorinated organic compounds (C xHyClz) and iron in aqueous
solutions can be expressed by the following reaction [37]:
+ 0 2+ -
CxHyClz + zH + zFe CxHy+z + zFe + zCl (1)
in which iron acts as a reductant (electron donor) for the removal of chlorine. This reaction is similar
to the process occurring during iron corrosion, with the beneficial effects of transforming chlorinated
pollutants. Reductive dechlorination of PCBs by nanoscale zero-valent iron was first reported by
Zhang and Wang [38].The iron nanoparticles exhibit characteristics of both iron oxides (e.g. as a
sorbent) and metallic iron (e.g. as a reductant) [39]. Table 1 presents a summary on the review of
some of the most relevant studies for the remediation of contaminated matrices with nZVI.
Nanoparticles provide more flexibility for in situ applications than granular iron and can remain
reactive towards contaminants in soil and water for extended periods of time (> 4-8 weeks) [36].
The nanoparticlewater slurry can be injected under pressure and/or by gravity to the contaminated
plume where treatment is needed and nanoparticles can be transported effectively by the flow of
groundwater.
COUPLING NANOTECHNOLOGY WITH ELECTROKINETICS

The natural tendency of nZVI to aggregate and/or bind with soil grains is currently a limitation to the
successful delivery of nZVI into porous media formations and into low permeability soils. This work
proposes the use of electrokinetics (EK) as a way to overcome this limitation. In this coupled
733
technique the role of EK would be quite the opposite of the traditional one: instead of aiming at
getting the contaminants out, the electric driving force is used to get nanoparticles into the soil.
Table 1. Summary of studies on zero valent iron nanoparticles.

Matrix Contaminant Nanoparticle % Removal Reference
Aqueous solutions Cr(VI) and Pb(II) Zero valent iron (ZVI) - [40]
Groundwater Trichloroethene and other chlorinated Bimetallic Fe/Pd nanoparticles 96% [41]
(field case) hydrocarbons
Water/Methanol PCBs ZVI nanoparticles and - [42]
Solution palladized microscale ZVI
Water TCE and PCBs Starch-stabilized bimetallic (Fe- 80% [43]
Pd) nanoparticles
Spiked water As (III) Zero valent iron (ZVI) 100% [44]
Groundwater VOC Zero valent iron (ZVI) 65-99% [45]
(field case)
Soil PCBs Zero valent iron (ZVI) 95% [46]
Liquid waste Uranium Zero valent iron (ZVI) 98,5% [47]
effluent
Spiked water Hexachlorobenzene Zero valent iron (ZVI) - [48]
Advantages of this approach are that PCBs are degraded into simpler, non-hazardous molecules
and remaining nZVI nanoparticles will eventually aggregate and settle, being incorporated in the
soil. Contaminants are therefore destroyed in situ, not extracted, avoiding the need for further
treatment. Transfer of pollution between environmental compartments is avoided, resulting in a
more sustainable approach.
Theoretically it is possible to use electric fields to move nanoparticles through the soil to where they
are wanted. Transport mechanisms expected to be relevant in this transport are electrophoresis
and electroosmosis. Some work has already been done to test this possibility such as the one
conducted by Pamukcu et al. [49], in which polymer coated nanoparticle are transported in kaolin
by electrophoresis. Jones et al. [50] also found that nZVI could be transported through fine grained
sand with rates comparable to those predicted by electrokinetic theory. More recently, Reddy et al.
[51] studied the transport and reactivity of lactate modified nanoscale iron particles in kaolin under
applied electric potential and found that electrokinetics can enhance delivery of nanoscale iron
particles in low permeability soils. This has been confirmed by yet another study [10] where the
transport of nZVI under different electric potentials in low permeable kaolin soil was found to
increase with higher voltage gradients.
These preliminary studies use model soils spiked with contaminants, and are far from the real
conditions found in the field. Additionally, although electrokinetic remediation has been used quite
extensively for different pollutants, it has never been used to extract PCBs from soils nor coupling
electrokinetics and nanoparticles to remediate PCBs contaminated soils and sediments has ever
been reported. Coupling the two technologies, EK and nZVI, is thus a promising technology but still
at a very early stage of development. In fact, basic aspects of this complex problem still remain
unknown (such as how are PCBs attached to the soil and how this influences
degradation/dechlorination rate; what are the best operational conditions; how long will the
nanoparticles be reactive; what is the influence of different soil conditions). Perhaps one of the
most relevant question is how accurately can nZVI be moved to a specific location under real soil
conditions using electric fields and how long will this take.
EXPERIMENTAL APPROACH
To investigate the fundamental aspects of nZVI coupled with EK it is necessary to describe the
behavior of the PCB-nZVI-soil system, both quantitative and qualitative. Due to its complexity the
methodological approach proposed here is to divide the problem into smaller, simpler parts, solve
each part and integrate them into a global model. It is assumed that each part of the problem is
734
independent from the remaining parts, and that the total equals the sum of its parts. The following 3
sub-models need studying:
- Transport of nZVI by electrophoresis
- Transport of nZVI by electroosmosis
- PCB degradation
The experimental approach suggested for formulating the three sub-models is presented next.
To investigate the electrophoretic transport of nanoparticles a laboratory cell similar to the one
described in Pamukcu et al. [49] can be used. Different materials should be tested, starting with
surrogate porous media, such as glass beads, then sand and pure clay (kaolinite), before using
actual soil. This way the transport of nZVI in oxidizing/reducing environments can be understood
when no interactions with the substrate occur. After establishing the performance nZVI transport
under the electric filed (with and without pH control) and determining a mobility index, the
experiments should go one step further to include mixed substrates and real soils.
For the study of the electro-osmosis transport mechanism the laboratory cell developed at
Department of Earth Sciences of Utrecht University (DES-UU) is recommended, after adapting to
allow for monitoring of input and output quantities of nZVI. This cell allows to measure the
magnitude of the electro-osmosis effect in water saturated, clayey soil samples and to study the
transport of nanoparticles through the soil by means of electroosmosis.
For the third sub-model, PCB degradation, the strategy consists in conducting batch extraction
procedures using real contaminated soils, and determine reaction kinetics under different
experimental conditions (e.g. concentration of nZVI, electrolyte, current density, duration) in order
to optimize PCB dechlorination. The use of surfactants can enhance PCB desorption from soils,
and this should also be considered at this stage.
GLOBAL MODEL
Integration of the individual processes can be accomplished by developing a macro-scale
transport/degradation numerical model which calculates the concentration of PCB and nZVI at
each location with time.
Suggested methodology is to use experimental data obtained in each sub-model to incorporate into
existing models after adaptation. Since mass transport in a porous media (without the application of
electric fields) is already extensively addressed, work should focus on transport processes related
to the electric field, namely electro-osmosis and electromigration/electrophoresis. For this effect the
numerical code developed at DES-UU and TU-Delft to simulate chemical and induced electro-
osmotic transport in clayey soils can be adapted. Currently this model includes geochemical
processes and contaminant transport during electro-remediation of Polycyclic Aromatic
Hydrocarbons (PAH) contaminated clays. It is currently being upgraded to include active electro-
osmosis, clay weathering and contaminant-mobilization. A step further is to integrate electro-kinetic
transport of nanoparticles and PCB-degradation kinetics.
This macroscale model will provide a useful tool in the prediction of future applications of
nZVI+electrokinetics to remediate other chlorinated hydrocarbons contaminated soils.
CONCLUDING REMARKS
Using electrokinetics in conjunction with nZVI is an innovative solution, since the pollutants will not
be extracted from the soil (traditional outcome in electrokinetics) but the electric fields will instead
be the driving force behind the movement of nanoparticles deep into the subsurface, where they
degrade organic contaminants into harmless by-products. This is conceptually a waste-free
technique: existing pollutants are not extracted but in-situ destroyed, and iron nanoparticles will
eventually aggregate and settle, being incorporated in the soil. This approach avoids pollution
transfer between environmental compartments and represents an integrated approach to recover
PCB contaminated soils. There is an expected higher efficiency of the coupled techniques when
compared to the individual ones, as well as a reduction in the remediation costs when incineration
and other ex situ treatments are considered.
With this new approach, remediation of low permeability soils will become possible. Even when
hydraulic transport is reduced, nanoparticles are still transported by electric fields, avoiding
common issues of agglomeration and settlement of these particles.
735
Acknowledgments
This work has been funded by the European Regional Development Fund (ERDF) through COMPETE
Operational Programme for Competitiveness Factors (OPCF), by National funds through FCT - Fundao
para a Cincia e a Tecnologia under project PTDC/AGR AAM/10643/2008 NanoDC and by FP7-PEOPLE-
IRSES-2010-269289-ELECTROACROSS.
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nanoparticles. Adv Colloid Interfac120 (2006) 4756.
[40] Ponder, S. M., J. G. Darab and T. E. Mallouk. Remediation of Cr(VI) and Pb(II) aqueous solutions using
supported, nanoscale zero-valent iron. Environ Sci Technol 34 (2000) 12 2564-2569.
[41] Elliott, D. W. and W.-X. Zhang. Field assessment of nanoscale bimetallic particles for groundwater
treatment. Environ Sci Technol 35 (2001) 4922-4926.
[42] Lowry, G. and K. Johnson. Congener-specific dechlorination of dissolved PCBs by microscale and
nanoscale zerovalent iron in a water/methanol solution. Environ Sci Technol 38 (2004) 5208-5216.
[43] He, F. and D. Zhao. Preparation and characterization of a new class of starch-stabilized bimetallic
nanoparticles for degradation of chlorinated hydrocarbons in water. Environ Sci Technol 39 (2005) 9
3314-3320.
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[49] Pamukcu, S., L. Hannum and J. K. Wittle. Delivery and activation of nano-iron by DC electric field. J
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[50] Jones, E. H., D. A. Reynolds, A. L. Wood and D. G. Thomas. Use of electrophoresis for transporting
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[51] Reddy, K. R., K. Darko-Kagy and C. Cameselle. Electrokinetic-enhanced transport of lactate-modified
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230-237.
737
14th September
Session 1.8
Chairman: Ange Nzhiou
738
INDICATORS TO ASSESS WASTE MANAGEMENT PLANNING

INSTRUMENTS
1
P. Santana
1 Officer at Entidade Reguladora dos Servios de guas e Resduos Water and Waste Services
Regulation Authority (ERSAR), Centro Empresarial Torres de Lisboa, Rua Toms da Fonseca,
Torre G 8., 1600-209 Lisboa, Portugal, Tel. +351 210 052 200, Fax +351 210 052 259,
paula.santana@ersar.pt
ABSTRACT
In Portugal, the Strategic Plan for Municipal Solid Waste 2007 2016 (PERSU II) is the
planning instrument that reflects the national policy regarding this type of waste. PERSU
II is assessed on an annual basis and, for that purpose, a set of indicators has been
developed and annual reports are prepared. The results reflect the transition taking place
in Portugal in recent years, from a model based on landfilling towards more sustainable
solutions, centred on material and organic recycling.
Waste is also associated with pressures on the environment. Taking the Driving Force
Pressure State Impact Response (DPSIR) model as a starting point, a decoupling
indicator is defined, considering the proportion of waste disposal in relation to waste
production as environmental pressure and Gross Domestic Product (GDP) as driving
force. The indicator is calculated using PERSU II as a case study and considering several
scenarios regarding the performance of the mechanical-biological treatment (MBT), which
is a relevant process in the context of this Plan. Results indicate absolute decoupling
between driving force and environmental pressure.
The indicator is relevant as a tool for the sustainable development policy, relating the
environmental and social-economic angles and considering the waste hierarchy.
Keywords: decoupling, DPSIR, indicator, PERSU II, waste
INTRODUCTION
In modern societies, waste management is regarded as a burden and also as a potential asset. On
the one hand, waste production reflects the inefficient use of resources and implies the need for
further processing in order to ensure its environmentally sound management. Waste management
options may also be associated with negative impacts on water, air and soil. On the other hand,
materials and energy can be recovered from waste, the current trend being the closure of the
resources cycle [1].
Municipal solid waste (MSW) reflects the metabolism of society, in which, namely, consuming
patterns, marketing and economic aspects play an important role. Waste prevention is the first
priority of the waste policy, which also aims to minimize end of pipe solutions such as landfilling;
additionally, preference is given to recycling instead of energy recovery. In Portugal, MSW
production amounts to approximately 5,5 million tons a year (i.e., 517 kg/inhab./year) [2].
Strategic Plan for Municipal Solid Waste 2007 2016 (PERSU II)
The Strategic Plan for Municipal Solid Waste 2007 2016 (PERSU II) is the planning instrument
that reflects the national policy regarding this type of waste and establishes targets for separate
collection, material recycling, organic recovery, incineration and landfilling. In PERSU II an
important role is given to mechanical-biological treatment (MBT) aiming at the recovery of
recyclables, compost and refuse-derived fuel (RDF) from commingled waste, thus diverting waste
from landfill and as a contribution towards the conservation of material and energy resources [3].
739
The Water and Waste Services Regulation Authority (Entidade Reguladora dos Servios de guas
e Resduos, ERSAR) and the Portuguese Environment Agency (Agncia Portuguesa do Ambiente,
APA), of the Ministry of Agriculture, Sea, Environment and Regional Planning (Ministrio da
Agricultura, Mar, Ambiente e Ordenamento do Territrio, MAMAOT), are responsible for the annual
monitoring and assessment of PERSU II. For that purpose, a set of indicators has been developed
and annual reports are prepared. These indicators are grouped according to: i) Waste
production/reduction; ii) Packaging waste and non-packaging paper waste for recycling; iii)
Biodegradable waste management; iv) Waste management (treated waste); v) Waste management
(outputs from facilities); vi) Investment. The results, as of 2009, reflect the transition taking place in
Portugal in recent years, from a model based on landfilling (i.e., 60%), towards more sustainable
solutions, centred on material and organic recycling, as several projects are being implemented. In
addition, waste production is still rising, although a decreasing pace is envisaged [2,4].
DPSIR model and decoupling indicators

Waste production is also associated with pressures on the environment focusing, upstream, on the
extraction and use of resources, and downstream, in terms of waste management. Taking the
Driving Force Pressure State Impact Response (DPSIR) model as a starting point,
decoupling, or delinking, of environmental pressures which have a cause-effect relation with
economic aspects such as economic growth have been studied, thus involving the first two
components of the DPSIR model. Decoupling indicators (DI) can be defined as in Eq. 1 [5,6].
0
1- 1
EP represents the environmental pressure and DF the driving force. There is decoupling if 0< 1.
Absolute decoupling occurs if the environmental pressure variable shows a stable/decreasing
behaviour, while the driving force increases; in relative decoupling, the environmental pressure
variable grows at a lower rate than the driving force variable.
METHODOLOGY
The work presented in this paper is detailed in [7]. The proportion of waste disposal in relation to
waste production is considered as environmental pressure, whereas GDP is assumed as driving
force. In this framework, the decoupling indicator is expressed as in Eq. 2.
( )
1 2
( )
0
e and P represent, respectively, waste disposal and waste production. Table 1 depicts the options
that are considered for both variables.
Table 1 - Options considered for the variables waste disposal and waste production.
Variable Designation Definition
e e = Direct landfill + Refuse
Waste
E E = e + Ashes + Slag
disposal
+ Compost from MBT
Waste P P = MSW production
production MSW production Bio-waste from selective collection or separation
740
Mass balance focusing on MBT units
A mass balance model is defined for MBT units in which the characterization of input waste and the
efficiency of separation are considered. The adopted timeframe is 2009 - 2016 and several
scenarios are developed in order to study the effect of the most significant parameters, i.e., waste
characterization, selective collection of bio-waste and MBT output parameters (recyclables
including the flows for material and organic recovery, RDF and refuse), as outlined in Table 2.
Table 2 Definition of scenarios.

Waste Collection of Commingled collection (MBT outputs)
Scenario
characterisation bio-waste Recyclables RDF Refuse
1 Constant No Constant - Low efficiency Constant Constant
2 Constant No Constant - High efficiency Constant Constant
3 Constant No Increasing Variable Increasing
4 Constant Yes Increasing Variable Increasing
5 Variable Yes Increasing Variable Increasing
In Scenarios 1 and 2, all parameters are constant and Scenario 2 shows a higher efficiency of
separation that corresponds to a higher recovery of recyclables, a lower production of RDF and a
higher production of refuse. In Scenarios 3 to 5, the parameters for MBT outputs evolve from those
considered, respectively, in Scenario 1 to Scenario 2. A part of bio-waste is collected separately in
Scenarios 4 and 5. Scenario 5 also studies the variation of the composition of waste, namely
decreasing the proportion of bio-waste, paper, plastics and metals.
Table 3 shows the values for GDP, including official projections as of 2010, and MSW production,
as in PERSU II, that were considered for the calculations.
Table 3 Evolution of GDP and MSW production for the period 2009 2016.
2009 2010 2011 2012 2013 2014 2015 2016
6
GDP [10 ] 128 405 129 304 130 468 132 164 134 410 135 755 137 112 138 483
3
MSW production [10 t] 5 110 5 140 5 151 5 145 5 125 5 094 5 053 5 003
Case study considering PERSU II

The indicator is also calculated using PERSU II as a case study. The options considered for the
variables waste disposal and waste production and the performance scenarios for MBT, presented
in Tables 1 and 2, respectively, are taken into account, as well as general assumptions of the Plan.
RESULTS
Mass balance focusing on MBT units
The results for the decoupling indicator, for 2016, considering the studied scenarios and options for
the variables, are presented in Fig. 1.
0.0
decoupling
0.0
Scenario 1
0.0
Scenario 2
DI
0.0 Scenario 3
Scenario 4
0.0
Scenario 5
no decoupling
0.0
e, P E, P E', P E', P'
Figure 1 Decoupling indicator for 2016 in the different scenarios and options for the variables.
741
Decoupling occurs in all scenarios, except when increasing quantities of compost are sent to
landfill and, in addition, the efficiency of separation leads to higher refuse quantities for disposal (as
in Scenarios 3, 4 and 5, using E). The maximum value for the indicator (i.e., 0,320) is reached
using E in Scenario 4 and corresponds to an optimized recovery of recyclables, includes the
selective collection of bio-waste and a lower production of RDF and, therefore, of ashes to landfill.
If all parameters are constant, DI only depends on waste production and GDP, as expected from
Eq. 2. In Scenario 5, the proportion of recyclable components in MSW decreases when compared
to Scenario 4; DI=f(e,P,GDP) decreases (due to refuse increase); DI=f(E;P,GDP) also decreases
(as refuse and RDF ashes increase); the effect is more pronounced in DI= f(E,P,GDP), since
waste production decreases.
Fig. 2 presents the trend for driving force and environmental pressure for Scenarios 1 to 5.
Scenario 1 Scenario 2
120 120
110 110
100 100
90 90
80 80
70 70
2009 2010 2011 2012 2013 2014 2015 2016 2009 2010 2011 2012 2013 2014 2015 2016
Year Year
120 120
110 110
100 100
90 90
80 80
70 70
2009 2010 2011 2012 2013 2014 2015 2016 2009 2010 2011 2012 2013 2014 2015 2016
Year Year
Scenario 5
120 150
140
2009 = 100
130
120
(e/P) / (e/P)0 110
110 (E/P) / (E/P)0 100
90
80
70
(E'/P) / (E'/P)0
100 (E'/P') / (E'/P')0 2009
PIB / PIB0
GDP/GDP0 Ano
90
(Note: In Scenarios 1 and 2, all lines corresponding
80 to environmental pressure overlap. In Scenarios 4
and 5, li s / d / almost coincide and, in
70 Scenario 3, they overlap).
2009 2010 2011 2012 2013 2014 2015 2016
Year
Figure 2 Driving force and environmental pressure in Scenarios 1 to 5 (2009=100).
Fig. 2 shows relative decoupling in all scenarios that use option e. In Scenarios 3, 4 and 5, there is
absolute decoupling with option E and, as mentioned above, no decoupling using E.
742
Case study considering PERSU II
The results considering PERSU II as a case study show that there is decoupling in all scenarios, as
the value of the indicator is always higher than zero; however, they also reflect a lower variation
between scenarios and the different options considered for the variables. This is attributed to the
fact that the global waste management system is assessed and that the model for analysis focuses
on a part of the system, i.e., MBT. To illustrate these aspects, Fig. 3 represents the variation of the
driving force and of the environmental pressure, indexed to 2009, for Scenarios 1 and 5. The
contribution of the different elimination components in PERSU II is depicted considering option E.
120 120
100 100
Direct landfill
80 80 MSW incineration
residues
Direct landfill Sorting plant-RDF
60 60
ashes
MSW incineration
residues MBT-RDF ashes
40 40 Sorting plant-RDF
ashes MBT refuse
MBT-RDF ashes
20 20
MBT refuse PIB / PIB0
0 0
2009 2010 2011 2012 2013 2014 2015 2016 2009 2010 2011 2012 2013 2014 2015 2016
Year Year
i) Scenario 1 ii) Scenario 5

Figure 3 Contribution of elimination components in PERSU II considering option E (2009=100).
Fig. 3 shows that there is absolute decoupling in both scenarios. This result is more pronounced in
Scenario 5, although there is a relatively small difference. The most significant contribution towards
the result corresponds to the decrease in the quantities that are directly landfilled. Given the
proportion that this quantity represents, the evolution of the remaining contributions is not visible at
this scale.
CONCLUSIONS
PERSU II has been annually assessed, since 2008, by a set of indicators that measure compliment
with waste management and investment targets set in the Plan. In this context, each indicator is
linked to a variable and is calculated individually.
In the present work, considering PERSU II and the different scenarios for MBT, results indicate
absolute decoupling between driving force (i.e., GDP) and environmental pressure (i.e., proportion
of waste disposal in relation to waste production). The effect is more pronounced when a portion of
bio-waste initially processed by MBT is diverted towards selective collection for organic recovery
and also when the compost produced from commingled waste is not landfilled. However, directly
landfilled MSW highly exceeds the remaining components that are disposed, and, overall, the
indicator shows a relatively meagre difference between scenarios.
Reflecting on the options that are studied for the variable for waste elimination, it is concluded that
e does not reflect total waste going to landfill, E sets a measurement closer to the quantities being
landfilled, as it also comprises residues from energy recovery, and E overestimates the total
amount of waste disposal, since it assumes that compost from MBT is landfilled.
Furthermore, it should be stressed that several criteria regarding waste management are also in
discussion and clarification at EU level, such as the status of MSW incineration (i.e., recovery/
disposal operation) and compost (i.e., product/waste). For benchmarking, the results can also
reflect different policies for, namely, energy and fertilizers - which can influence the priorities
regarding RDF and compost production and use. These aspects can be relevant for the analysis.
743
The literature on decoupling indicators is, in general, more prolific on environmental topics such as
air pollution and greenhouse gases than on the use of materials and waste management. The
proposed indicator aims to contribute to this subject and highlights the relation between waste
management variables as environmental pressure and studies different approaches for these
variables.
The indicator is used to assess a waste management plan, PERSU II, and can be applied to other
plans, types of waste and management systems, as well as to different geographical and time
frames. Given the specific and technical concepts associated with the definition of the indicator and
with the interpretation of the results, it can be of interest mainly to the Administration and other
stakeholders involved in waste management, environment and sustainable development policies.
Some limitations can also be pointed out, namely the simplification of the mass balance and the
use of projections, and the associated error. The analysis depends on the starting point and on the
evolution of parameters, which reflects the relative but not the absolute situation. Treatment
processes also exhibit technical, economic and market limitations, such as efficiency of separation,
collection/treatment costs and market demand for the outputs of the system (i.e., recyclables,
compost and RDF); these aspects can influence the results (e.g., an optimized system is likely to
be less able to further improvements).
In conclusion, this decoupling indicator can a relevant tool, mindful of its limitations and in tandem
with other instruments, for the sustainable development policy, relating the environmental and
social-economic angles and considering the waste management hierarchy.
References
[1] APA, Plano Nacional de Gesto de Resduos 2011 2020, Proposta de PNGR, 2011
(information on: http://www.apambiente.pt).
[2] Information on http://www.ine.pt.
[3] MAOTDR, Plano Estratgico para os Resduos Slidos Urbanos 2007-2016 (PERSU II),
2007 (information on: http://www.ersar.pt).
[4] ERSAR/APA, PERSU II Plano Estratgico para os Resduos Slidos Urbanos 2007-2016.
Relatrio de Acompanhamento 2009, 2011 (information on: http://www.ersar.pt).
[5] OCDE, Sustainable development. Indicators to measure decoupling of environmental
pressure from economic growth, Ref. SG/SD(2002)1/FINAL, 2002.
[6] M. Mazzanti, R. Zoboli, Waste generation, waste disposal and policy effectiveness. Evidence
on decoupling from the European Union, Resources, Conservation and Recycling, 52
(10)(2008) 1221-1234.
[7] P.C.L.Q.P. Santana, Contribuio para o desenvolvimento de um indicador de dissociao
no mbito da gesto de resduos, Dissertao apresentada na Faculdade de Cincias e
Tecnologia da Universidade Nova de Lisboa para obteno do grau de Mestre em
Engenharia Sanitria, Lisboa, 2010 (information on: http://run.unl.pt/).
744
ANALYSIS OF AN INTEGRATED WASTE MANAGEMENT SYSTEM: PART B

LIFE CYCLE ASSESSMENT
M. Grosso*, L. Rigamonti, M. Giugliano

Politecnico di Milano DIIAR, Environmental Section
P.zza Leonardo da Vinci 32, 20133 Milano Italy
*Phone: +39-02-23996415 Fax: +39-02-23996499
*E-mail: mario.grosso@polimi.it
ABSTRACT
This paper reports the environmental results of a research project on the comprehensive
analysis of waste management in the Province of Piacenza, in northern Italy, which is
based on an integrated system approach that aims to an almost self-sufficient condition.
All the MSW produced in the Province are collected by a public company that manages
its delivery to several recycling facilities (some of them inside the Province, others
outside), to a Waste-to-Energy (WtE) plant in the provincial capital, Piacenza, and to
other destinations. The reference scenario studied is the year 2007, which is compared
to an improved scenario (year 2008), where consistent modifications in the management
of waste collection have been introduced, with the aim of increasing the separate
collection up to 50%. Environmental assessment, carried out by means of Life Cycle
Assessment (LCA), clearly shows that the prospected increase of material recycling,
coupled with an higher energy recovery efficiency from the residual waste, result in an
improvement of the environmental performances of the integrated waste management
system.
Keywords: LCA; case study; integrated waste management system
INTRODUCTION
This paper reports the environmental results of a research project on the comprehensive analysis
of an Integrated Waste Management System (IWMS) for Municipal Solid Waste (MSW). It is
directly linked to a second paper [1] which reports the mass and energy balances of the same
system (Part A).
The management of waste in the Province of Piacenza, in northern Italy, is based on an integrated
system approach that aims to an almost self-sufficient condition. All the MSW produced in the
Province are collected by a public company that manages its delivery to several recycling facilities
(some of them inside the Province, others outside), to a Waste-to-Energy (WtE) plant in the
provincial capital, Piacenza, and to other destinations. The reference scenario studied is the year
2007, when 200,000 tons circa of waste were overall collected, achieving a Source Separation
Level (SSL) of about 38.7% (calculated according to Regional regulations, which do not include all
the waste typologies collected).
The separated packaging materials (paper and cardboard, glass, plastic, metals, and wood) are
sent to selection and then to recycling plants, whereas green and food wastes are sent to
composting. It has to be pointed out that the IWMS implemented in Piacenza is based on the
maximisation of packaging materials collection, while bio-waste is separated only to a lower extent.
The residues originated during the selection of recovered materials (both packaging materials and
bio-waste) are mostly sent to landfill, with the exception of those produced during plastic recycling
activities and some few others that are routed to energy recovery.
The residual waste is sent to a WTE plant whose performances are described in the Part A paper
[1]. Fig. 1 shows the integrated waste management system in the Province of Piacenza.
745
SELECTIVE Residual waste WASTE-TO-ENERGY PLANT
MW COLLECTION (PIACENZA + OTHERS)
Collected Fly
ashes Bottom ashes
material and air pollution
control residues
Residues from
SEPARATION OF separation and
MULTIMATERIAL selection
RECOVERY
LANDFILLS
COLLECTION AND
SELECTION OF
EACH MATERIAL
Residues
Selected Selected
organic packaging Residues from
material materials recycling
SELECTION
Ferrous metals, Selected
aluminium, glass, RECYCLING PLANTS materials
plastic, paper, wood
Other waste*
Food waste
COMPOSTING + bulky waste
Green waste
PLANTS
Figure 1: Integrated waste management system in the Province of Piacenza.

* Other waste includes waste not strictly municipal (i.e. not produced by households), but similar
in composition
During 2008, consistent modifications in the management of waste collection have been
introduced, with the aim of increasing the SSL up to 50%. As consequence, MSW to be fed to the
WtE plant has changed in terms of composition and calorific value.
Methodology and assumptions
LCA methodology was applied to analyse baseline and improved scenarios and to evaluate their
impacts. LCA analyses were carried out following the ISO standards 14040 and 14044 [2, 3] and
by means of the SimaPro 7 software, developed by PR Consultants [4], in which new modules
were created, describing the life cycle of the different treatments included in the waste
management system, as much as possible accurate in representing the actual situation of the
Province of Piacenza. The impacts calculated are global warming potential (according to IPCC
2007), human toxicity potential, acidification potential and photochemical ozone creation potential
(according to CML 2001 [5]).
The LCA analysis takes into account all the fluxes of pollutants released in the environment by
each process, including both direct (e.g. those released from the waste treatment plants and from
the transport of the materials) and indirect emissions (e.g. those related to the production of the
reactants utilised in the flue gas abatement system of the WtE plant). These positive emissions
are then compared with the avoided ones [6, 7], which are those associated with energy and
material conventional productions displaced by energy and materials produced in the waste
management system. In fact, beyond treating waste, some activities (e.g. packaging materials
recycling, bio-waste composting, and incineration of the residual waste in the waste-to-energy
plant) lead to the production of new materials (called secondary materials), compost or energy. In
the LCA modelling, we have thus decided to expand the system boundaries and to assess which
products are replaced on the markets by those produced from waste, including their replacement in
the model. This methodology is called substitution by system expansion or avoided burden
746
method [7].
In the modelling of the recycling of packaging materials we have used a substitution factor of 0.83,
0.6 and 0.81 respectively for paper, wood and plastic. Moreover, we have assumed that the
electricity produced by the WTE plant displaces the same amount of electricity produced by the
thermoelectric Italian mix as of the year 2007 (9% fuel oil, 18% coal, 10% gas natural, 63% gas
natural in combined cycle). Finally we have also considered the impacts of the trucks utilised for
the collection of the different fractions of waste and of those used in the transport from the
collection point to the treatment plants. The mileage for such transports were calculated by
processing primary data directly supplied by the waste collection company.
As for the data source, for each kind of treatment we acquired primary data via direct contacts with
the plants that treat waste produced in the Province of Piacenza, while for secondary processes
and secondary production we used data from the BREF documents [8] and Ecoinvent database [9].
The zero burden assumption [10] was adopted, meaning that the waste carries none of the
upstream burdens into the waste management system.
The functional unit is the amount of waste annually produced and treated in the Province of
Piacenza according to the scheme reported in Fig. 1, which is slightly different in years 2007 and
2008 due to the expected variations occurring in the system (Tab. 1).
Table 1: Amount of waste treated in the system in years 2007 and 2008.
SCENARIO SCENARIO
Variation
2007 2008
t/year t/year %
Residual waste 96682 77823 -19.5
Paper 23095 30107 +30.4
Plastic 3296 4758 +44.4
Aluminium 273 335 +22.3
Ferrous metals 2396 2974 +24.1
Glass 9106 12359 +35.7
Wood 7884 8629 +9.4
Food waste 4232 11721 +177.0
Green waste 15077 15425 +2.3
Other 6553 6616 +1.0
Residues from multi-material separation 2151 0 -100.0
Residues from other + bulky waste
14554 25153 +72.8
separation sent to Piacenza WTE plant
Residues from other + bulky waste selection
11923 1324 -88.9
sent to other destination
Sludge + hospital waste + exhumation +
6613 3335 -49.6
stored residual waste
Other waste from outside the Province 0 7360 +100.0
Total 203835 207918 +2.0
Baseline scenario (year 2007)
In the baseline scenario (year 2007), the overall separate collection accounts for 38.7% of the total
produced waste, and it is carried out with a mix of mono and multi-material collection. The residues
from the selection of other + bulky waste are sent to Piacenza WtE plant (55%), to another WtE
plant located outside the Province (12.5%), and to landfill (32.5%). Residues from material
recovery are mostly sent to landfill.
As for the Piacenza WtE plant, its capacity is 120,000 tonnes per year, and it produces only
electricity with a yearly average net electrical efficiency of 22%. The LHV of the treated waste is
9310 kJ/kg, whereas the content of fossil carbon is 140 kg per tonne of treated waste.
747
Improved scenario (year 2008)
In the improved scenario, foreseen for year 2008, the separate collection is increased to 50%,
according to the target set by the Provincial waste management plan and to the most recent
legislation (EU Directive 2008/98). To reach this target, the collection is completely shifted to a
mono-material system. Such an increase of source separation leads to a lower amount of residual
waste available to the Piacenza WtE plant, which shows a 20% decrease (Tab. 1). It is then
possible to route to the plant a significant amount (95%) of residues arising from the selection of
other + bulky waste, while only a minor fraction of them (5%) is still sent to landfill, being not
suitable for incineration. A similar approach applies to the residues from material recovery
activities, which are sent to the Piacenza WtE plant when suitable for combustion. Finally, an
higher amount of other waste is sent to the Piacenza WtE plant in order to maintain its operation
at full capacity (120,000 t/year). The LHV of the treated waste increases to 11524 kJ/kg and the
content of fossil carbon to 191 kg per tonne of treated waste.
A further improvement of the environmental performances of the Piacenza WtE plant is obtained by
replacing the current SNCR (Selective Non Catalytic Reduction) system for NO x abatement with a
better performing SCR (Selective Catalytic Reduction) one. This will affect not only NOx
concentration at the stack, which is halved, but also that of other nitrogen compounds such as NH 3
(reduced by about three quarters) and N2O (reduced by about four fifths).
RESULTS
Results are reported in Table 2, for the years 2007 and 2008. It is clear that the prospected
increase of material recycling, coupled with an higher energy recovery efficiency from the residual
waste as described in Part A of this paper [1], result in an improvement of the environmental
performances of the integrated waste management system for all the impact indicators
investigated. Improvements range from 10% for human toxicity to more than 50% for global
warming, acidification and photochemical ozone creation.
Table 2: Environmental impact indicators for the whole IWMS of the Province of Piacenza.
Impact Year 2007 Year 2008
indicator (38.7% SSL level) (50% SSL level)
Global warming t CO2 eq./year 10,362 4,350
Acidification t SO2 eq./year -198 -299
Human toxicity t 1,4 DCB eq./year -23,013 -25,377
Photochemical
t C2H4 eq./year -17 -26
ozone creation
When the different parts of the integrated waste management system are analysed (Fig. 2), one
can observe that the improved performance of the global warming indicator derives from the
prospected increase of material recovery and to the almost complete phasing-out of landfilling. On
the contrary, energy recovery from residual waste worsens its performances mainly due to the
increase of the fossil carbon content of the treated waste, mostly caused by the higher contribution
of other waste. A similar picture is observed for the human toxicity potential, where again the
improvement is driven by the enhanced material recovery activities.
748
Global warming Global warming
40000 40000
32685
30000 30000
25875
20000 20000
t CO2 eq. / year
t CO2 eq. / year

10362
10000 10000
4847 4350
737
0 0
-10000 -10000
-20000 -20000
-20359
-30000 -30000
-29073
Material recovery Landfill WTE plant Total Material recovery Landfill Piacenza WTE plant Total

Human toxicity Human toxicity
0 0
-6
-39
-5000 -5000
t 1,4 DCB eq. / year
t 1,4 DCB eq. / year
-10000 -8157
-10000
-9249
-15000 -15000
-13724
-17214
-20000 -20000
-25000 -25000
-23013 -25377
-30000 -30000
Material recovery Landfill WTE plant Total Material recovery Landfill Piacenza WTE plant Total
Figure 2: Contribution of the three major parts of the waste management system: material recovery
(including composting), landfill and WtE.
Table 3: Environmental impact indicators for the sole WtE plant of the Province of Piacenza (data
are referred to 1 tonne of incinerated waste).
materials and
treatment of production
2007 stack fuels total
residues of energy
consumptions
global warming kg CO2 eq./t 554 38 -28 -356 209
human toxicity kg 1,4 DCB eq./t 36 19 -86 -45 -75
acidification kg SO2 eq./t 0.58 0.23 -0.15 -1.37 -0.71
photochemical ozone creation kg C2H4 eq./t 0.025 0.027 -0.021 -0.102 -0.071
materials and
treatment of production
2008 stack fuels total
residues of energy
consumptions
global warming kg CO2 eq./t 711 38 -25 -453 271
human toxicity kg 1,4 DCB eq./t 43 19 -73 -57 -68
acidification kg SO2 eq./t 0.38 0.23 -0.14 -1.74 -1.27
photochemical ozone creation kg C2H4 eq./t 0.017 0.027 -0.019 -0.129 -0.105
Some final consideration can be made on the environmental performances of the Piacenza WtE
plant, by comparing its operation in year 2007 and 2008 (Tab. 3). Per 1 tonne of waste incinerated,
higher benefits are observed in 2008 for acidification (+79%) and photochemical ozone creation
(+49%) compared to 2007. This is due to the prospected decrease of NOx emissions obtained
thanks to the replacement of SNCR with a SCR system, and to the increase of electricity
production. On the contrary, it has higher impacts in terms of global warming (+30%) due to the
high content of fossil carbon in the waste, although the increase of electricity production.
Performances for all indicators could benefit of the shift to a combined heat and power (CHP)
749
operation, provided that heat customers are available. Nevertheless this is not a straightforward
option due to a number of constraints, and particularly the climatic situation of Piacenza (where
heat requirement is high only for less than half of the year) and the relatively isolated location of the
plant compared to the city centre.
CONCLUSIONS
The evaluation of the integrated waste management system of the Province of Piacenza highlights
the role of increased material recovery in improving the environmental performances of the whole
system. This might lead to a lower amount of available residual waste to feed the existing WtE
plant, which might then suffer a lower energetic performance. When dealing with this issue, waste
managers should then evaluate the possibility to route some of the residues arising from material
selection and recovery to the WtE plant, especially when those residues are suitable for
combustion. Other fluxes of waste are also generally available, even if not strictly produced by the
households, but deriving from commercial activities, whose characteristics are very similar to the
traditional municipal solid waste. Those fluxes can be routed to the WtE plant, helping to support its
full operation capacity and preventing waste shipment to other Provinces or, worse, to landfill.
Acknowledgements
The research was funded by Tecnoborgo, the society that operates the Piacenza WtE plant.
Support by recycling plant operators of the Piacenza province in providing data is sincerely
acknowledged.
References
[1] Consonni, S., Vigan, F. (2011) Analysis of an integrated waste management system: part A -
st
mass and energy balances, WASTES: Solutions, Treatments and Opportunities 1
International Conference, September 12th 14th 2011, Guimaraes (P)
[2] ISO (2006) ISO 14040 Environmental management - Life cycle assessment - Principles and
framework
[3] ISO (2006) ISO 14044 Environmental management - Life cycle assessment - Requirements
and guidelines
[4] PR Consultants (2010) SimaPro 7 software, http://www.pre.nl/content/simapro-lca-software
[5] CML, Bureau B&G, School of System Engineering, Policy Analysis and Management Delft
University of Technology (2001) Life cycle assessment: an operational guide to the ISO
standards
[6] EC, JRC, IES (2010) ILCD Handbook: General guide for Life Cycle Assessment Detailed
Guidance, http://lct.jrc.ec.europa.eu/assessment/data
[7] Finnveden, G., Hauschild, M.Z., Ekvall, T., Guine, J., Heijungs, R., Hellweg, S., Koehler, A.,
Pennington, D., Suh, S. (2009) Recent developments in Life Cycle assessment, Journal of
Environmental Management, 91 (1), 1-21
[8] European IPPC Bureau (EIPPCB), http://eippcb.jrc.es/reference/
[9] Swiss Centre for Life Cycle Inventories (2007) Ecoinvent: The life cycle inventory data,
Version 2.0.
[10] Ekvall, T., Assefa, G., Bjorklund, A., Erikson, O., Finnveden, G. (2007) What life-cycle
assessment does and does not do in assessments of waste management, Waste Management
27, 989-996.
750
September 12th-14th 2011
A STUDY ON CONSTRUCTION WASTE MANAGEMENT

1 2 3
P. Melo , A.C. Dias and V.M. Ferreira
1 Somague Engenharia, S.A, Porto, Portugal (paulajmelo@gmail.com)
2 CESAM - Centre for Environmental and Marine Studies, Department of Environment and
Planning, University of Aveiro, 3810-193 Aveiro, Portugal (acdias@ua.pt)
3 Civil Eng. Dept., University of Aveiro/CICECO, 3810-193 Aveiro, Portugal (victorf@ua.pt)
ABSTRACT
The explosion in population growth throughout the world in recent decades prompted an increase
in economic growth and construction, which in turn increased solid waste (SW) production. This
increase in SW production places a stress factor on available space for the final disposal and
points out a need for improved methods of disposing of the waste.
The current method of disposing waste in the construction industry can be improved. Efficient
management, cost optimization and the implementation of conservative measures on the
construction site would reduce the amount of waste produced.
This study addresses the problem of waste management in construction sites with the objective of
presenting valid procedures to improve the current process of construction waste management.
The data collected in one case study was analyzed using life cycle assessment (LCA) in order to
evaluate the environment impacts associated with different alternatives for the management of
construction waste (recycling, landfill and incineration). Final conclusions are that waste must be
recycled in greater quantities, and the remaining incinerated rather than sent to landfill.
Keywords: Sustainability; waste; recycling; LCA; construction
INTRODUCTION
Sustainable development implies a concern not only for the present, but also with the quality of life
of future generations, protecting resources, ensuring an environmentally friendly economic growth.
This view, integrating development, trying to harmonize the economy, society and nature,
respecting biodiversity and natural resources, is the background of international and European
Union (EU) policies for sustainable development. However, it is also true that the global trend of
environmental degradation has increased. In this world there is still a long way to go in search of its
sustainability.
The building materials sector is the third-largest carbon dioxide (CO2) emitting industrial sector
worldwide and in the European Union [1]. This sector emits 10% of the global anthropogenic CO 2
emissions [1]. Regarding waste management within the EU, more than 450 million tons per year of
construction and demolition waste is generated, this being the largest waste stream in quantitative
terms, apart from mining and farm wastes [2]. In Portugal, the estimated production of construction
waste is 7.5 million tons in 2005 [3]. Most of this construction waste was sent to landfill disposal,
occupying a considerable volume [3].
Another key factor for achieving sustainability in construction consists in minimizing the
consumption of natural resources. This can be achieved by incorporating waste generated by
industry in building materials. The construction and demolition waste has a high potential for
recovery, meaning that 80% of this waste can be recycled [2]. Recycling of waste generated by
construction industry is vital to ensure a proper waste management.
A waste hierarchy is often suggested and used in the development of a waste disposal policy.
Different versions of hierarchy exists, but in most cases, the following order is suggested [4].
Reduce the amount of waste;
Reuse;
Recycle materials;
Incinerate with heat recovery;
Landfill disposal.
751
The main objective of this paper is to evaluate the environmental impact of construction waste
management options for a case study of construction by means of Life Cycle Assessment (LCA)
Three different management options have been compared: landfilling, recycling and incineration.
METHODOLOGY
LCA methodology
The LCA methodology was created to assess the impacts on the environment and health caused
by a particular product, process, service or activity. The analysis covers the entire lifecycle of a
product / process / business utilization, for example:
Extraction of raw materials;
Processing of raw materials;
Production;
Distribution;
Use;
Reuse (when necessary);
Maintenance;
Recycling;
Elimination (disposal).
The LCA methodology accounts for the totality of interactions that occur in different processes, and
often in different spaces and periods. The environmental aspects are determined by the input and
output of materials and energy at each stage of the life cycle of the product. These aspects, once
identified, are grouped into different categories of environmental impacts.
LCA is a standardized methodology by the International Organization for Standardization (ISO).
ISO 14040 and ISO 14044 provide the requirements, structure and methodology for conducting
LCA studies.
According to Guine et al. [6], an LCA project is more than a single study. The LCA of products is
an important technique since the choice of design options more viable from an environmental
perspective requires knowledge of all phases of product life, and considers all factors and levels of
components of the production process. Indeed, without the knowledge of the life cycle is only
possible to solve partial problems. The LCA recommends that environmental assessment is carried
out without regard to the process itself, but the product, or rather the function that aims to fulfill. The
environmental concern regarding a particular product, typically existed during their production,
during the industrial processes that led to obtaining the finished product. With the new paradigm,
there has been the extent of product liability throughout the entire life cycle.
Description of case study

The case study used is located in Portugal centre region (Mira, Coimbra district). In this site a new
2
construction took place in a land area of 2,000,000 m . The facility has a total construction area of
2
445,000 m .
In this project, concerning a fish farming plant, earthworks were performed, emissaries were
executed with "pipe jacking" techniques (high density polyethylene pipes and assembly) and other
building elements such as channel reinforced concrete, reinforced concrete tanks, metal structure
in coverage were installed. Supply chain management, support for future operation sanitation, rain,
fire and oxygenation network, as well as the electricity grid were also considered. On the projects
site temporary support structures such as, concrete plant, shipyard and concrete pipes factory
were mounted. These structures were removed during the work, recovered or partially demolished.
Defining the purpose and scope

The main objective of the study is to assess the indicators that measure the environmental impacts
of waste from the construction phase.
The functional unit is defined as the total amount of waste produced in construction work. These
residues are generated by "new" buildings, repairs and demolitions during the course of work. The
reference destinations were considered landfill or recycling.
752
Life Cycle Inventory (LCI)
The voluntary environmental management system and waste management policies and
procedures of the company were implemented during the works. The construction work lasted 24
months beginning in November 2007 and completed in November 2009. During the period in which
the projects construction took place, an inventory of waste was made and the waste was classified
according to the legislation (Portaria n 209/2004).
After analyzing the data it was found that the waste could be grouped into eight major categories
including inert waste/ demolition waste, metals, wood, plastics, used oil, glass, oily water and
paper. This consolidation is due to the fact that some waste codes used in the waste inventory
correspond to the same residues and other waste codes have the same destinations. Due to lack
of evidence or the small amounts involved, some residues were not included in the study. After the
unification of the waste groups, waste amounts per group were quantified (Table 1).
Table 1 Final waste groups of the case study

Group of waste Quant [ton] Distance Destination
[km]
Inert demolition waste 261.730 20 100% landfill
Metal / Scrap 260 250 100% recycling
Wood 95 110 100% recycling
Plastics 87 210 100% recycling
Used oil 2 590 100% treatment/ landfill
Glass 0 0 100% recycling
Oily water 44 150 100% treatment/ landfill
Paper 0 0 100% recycling
During this study it was found that 99% of the amount of waste was disposed of in landfill. This is
due to the high amount generated of "inert waste/ demolition waste. This residue is used in this
case study as filling material for the recovery of an old quarry. In this case the share of inert waste /
demolition waste was actually considered as used for recovery.
However, if we analyze the destination of the waste groups in number, we can draw different
conclusions from previous ones. The destination of the waste will change to recycling.
The reduction to eight groups of residues facilitated the analysis and the collection of LCI data. For
each group of waste, treatment processes were selected from available databases. In addition to
the current processes (recycling and landfill), the alternative process of incineration was also
chosen, in order to identify the best choice of disposal for the different waste groups. The transport
of the wastes from the construction site to the disposal facilities was also considered. The
distances associated to this transport are shown in Table 1. The inventory data for the trucks used
in this transport were also collected from available databases.
The databases included in the SimaPro software (Ecoinvent, PlasticsEurope, Word Steel
Organisation, Buwal, DK and EU27 IO) were used to obtain inventory data of the processes
involved in the study. Because the databases were mainly designed to Swiss technology, the
energy mix of the processes was adapted for the Portuguese electric energy mix.
Some minor waste flows were excluded from the analysis due to the lack of data. Some waste
operators did not provide information regarding the final disposal and distances for some wastes
and, besides there were no available data for the group used oil and oily water solution to landfill.
Life Cycle Impact Assessment (LCIA)

From the collected LCI data, environmental impacts were determined using the method CML2
(2001) [6].
The environmental impact was evaluated based on the following impact categories:
Depletion of abiotic resources (kg Sb-eq)
Climate change (kg CO2-eq)
Formation of photochemical oxidants (kg C2H4-eq)
Acidification (kg SO2-eq)
3-
Eutrophication (kg PO4 -eq)
753
The calculations were elaborated in a model consisting of several spreadsheets with the inventory
data for each final disposal process, the parameters and characterization factors included in each
impact category, and the results. The model also includes a spreadsheet with input data that the
user can change consisting in the amount of wastes generated on site according to their final
disposal option along with the travelled distance to the final disposal facility.
RESULTS
Results seem to indicate that for the current waste management practices in the case study,
landfilling (of inert waste) has a contribution significantly higher than recycling (of metal, wood,
plastics, glass and paper) for the impact category "climate change" (figure 1). It is noted that the
inert material contributes more to the impact due to the quantities involved. The case study
analyzed generated a large amount of inert material.
Figure 1 Environmental impact of the waste of the case study
With this data for the waste scrap/metals, plastics, glass and paper it is possible to show that
recycling of these materials has a minimal contribution to environmental impact compared with the
recycling of inert wastes and in some cases a negative value (figure 2).
In the recycling and incineration scenarios (figures 3 and 4), the values are negative due to avoided
impacts of the recovered materials and the generated energy. In this case both the recycling
processes and incineration have a beneficial impact on the end result and this means that these
scenarios are more environmentally friendly.
Figure 2 Environmental profile for the recycling
754
Figure 3 - Environmental profile for the landfill disposal
Figure 4 - Environmental profile for the incineration
CONCLUSIONS
Throughout this work a close monitoring of the case study was made, the environmental
management system was implemented voluntarily, rules and law specifications implemented,
environmental impact statement, etc. As in all the construction sites, this case study was subject to
internal and external audits for verification. No discrepancies were detected that would put the work
and its data in question. The starting point of this project was to implement waste management
practices and monthly data was collected and confirmed by the operators. During this period of
implementation of the systems, data was measured, and continuous improvement actions were
taken as provided generally in management systems.
In the next phase of this work, the validation of inventory data, some difficulties and limitations were
noted. It was found that the classification of waste according to European Waste List can be
somewhat random, depending on the person doing the classification. In the case study there were
similar residues with different classifications.
In the phase of inventory analysis, it is emphasized that the databases still have gaps in the area of
the recycling processes and it has not been easy to link the waste generated and the processes to
databases, leaving some waste groups without information.
Waste sorting is done in proportion to the available space at the construction site. Where the area
is limited, waste can be screened in outside the site. After estimating the types and quantities of
waste being generated, the construction site is examined to determine the most suitable areas for
waste collection, placement of containers and container types. This analysis should maintain the
concept of optimizing the results of waste management.
The results of the LCIA show that due to high amounts of inert waste involved and mainly due to
CO2 emissions, the impacts of the category "climate change" are higher in the process of landfill.
755
Several analyses showed that the indicator "climate change" reflects that the process landfill is
treated less favorably with more detrimental effects on the environment. The other groups of waste
involved in the study contribute with a smaller impact than inert waste. Companies in the country
should adopt a policy of encouragement and use of strategies for waste reduction, reuse and
recycling in order to obtain "secondary" raw materials. Another conclusion is that waste must be
recycled in greater quantities, and the remaining incinerated rather than sent to landfill.
Construction companies have to recognize the new paradigm of sustainable development and
develop a proper waste management program that will bring economic, environmental and social
effects such as reduced transport costs, reducing the amount of waste to be deposited in landfills,
reducing dependence of virgin raw materials, improving the quality of recycled materials,
elimination of illegal and unauthorized landfills.
References
1. Habert, G.B., C; Rossi, P; Chen, C; Roussel, N; , Cement production technology improve-ment
compared to factor 4 objectives. Cement and Concrete Research, 2009, 40 (5), 820-826.
2. Ortiz, O.P., J C; Castells, F; , Environmental performance of construction waste: Comparing
three scenariosfrom a case study in Catalonia, Spain Journal of Waste Management, 2010, 30
(4), 646-654.
3. APA, A.P.d.A. Resduos de construo e demolio 2010; Available from:
http://www.apambiente.pt/paginas/default.aspx.
4. Finnveden, G.J., Jessica; Lind, Per; Moberg, sa; Life cycle assessment of energy from solid
wastepart 1: general methodology and results. Journal of Cleaner Production 2005. 13, p.
213229.
5. Finnveden, G.J., Jessica; Lind, Per; Moberg, sa; Life Cycle Assessments of Energy from Solid
Waste, 2000, Stockholm Universitet, Systemekologioch FOA.
6. Guine, J.B., Handbook on Life Cycle Assessment Operational Guide to the ISO Standards,
ed. T.I.O.S. Dr Arnold Tukker, Technology and Policy, Vol. 7. 2002.
756
14th September
Session 2.8
( WASTE-TO-ENERGY AND RDF 2 )
Chairman: Eduardo Ferreira
757
INSIGHT THE CHLORINE CONTENT OF WASTE BASED ALTERNATIVE

FUELS
1 2 3 4
R. B. Silva , M. Costa , J. M. Novais and S. Martins-Dias
1 Institute for Biotechnology and Bioengineering (IBB), Centre for Biological and Chemical
Engineering (CEBQ), , Instituto Superior Tcnico (IST), Av. Rovisco Pais, 1049-001 Lisboa,
Portugal, rita.silva@ist.utl.pt
2 Mechanical Engineering Department, Instituto Superior Tcnico (IST), Av. Rovisco Pais, 1049-
001 Lisboa, Portugal, mcosta@ist.utl.pt
3 IBB,CEBQ, IST, Av. Rovisco Pais, 1049-001 Lisboa, Portugal, julio.novais@ist.utl.pt
4 IBB,CEBQ, IST, Av. Rovisco Pais, 1049-001 Lisboa, Portugal, susetedias@ist.utl.pt
ABSTRACT
Biomass and refuse derived fuels (RDF) are nowadays used as alternative combustibles
due to economic and environmental opportunity costs. Whereas combustion systems
operational constraints arising from RDF, like corrosion, slagging or fouling are still under
characterization, chlorine content appears to play a key role on these phenomena. In this
work the total chlorine content and the influence of chlorine counter ion nature are
addressed aiming to contribute to a better understanding of what should be a major
concern when this sort of fuels is burned.
The present analysis suggests that for selection of RDF combustion conditions, a
specification of organic/inorganic chlorine content ratio could be more useful than the
total chlorine content. In RDF based on the refuse of Portuguese municipal solid waste it
was found that inorganic chlorine accounts for almost total chlorine content
(~200 mg Cl/MJ fuel) indicating a corrosion tendency rather than a harmful emission
potential. When RDF is produced from commercial waste, fuels can have some organic
chlorine content (~50%), which could lead to dioxins and furans formation if burned at low
temperatures. Nonetheless, given the close relation between chlorine and alkalis content
in corrosion effects perhaps chlorine per si is not enough for a complete picture of the
technological impact of alternative fuels.
Keywords: corrosion; municipal solid waste; neutral CO2 ; water soluble chlorine
INTRODUCTION
The use of waste and biomass based fuels is currently regarded as a sound option for energy and
heat production. The most encouraging features of these alternative fuels are their local availability,
supply and price robustness. Neutral CO2 emissions are also important for industrial plants that
have to comply with CO2 trading schemes. The assessment of the way this opportunity fuels
interfere with operational, combustion and emission performance of boilers is of great interest for
potential users.
Chlorine, a minor constituent of most alternative fuels, can contribute to combustion-associated
corrosion phenomena, depending not only upon its concentration but also on the chemical form.
The mechanisms of chlorine- induced corrosion on solid fuels combustion boilers are complex but
closely related to inorganic chlorine forms and to the presence of alkali metals such as potassium
or sodium [1, 2].
Chlorinated compounds found in combustion by-products comprise alkali chlorides (AlkCl), e.g.,
KCl and NaCl, HCl, dioxins and furans. Equipment corrosion has been told to be severe at low
temperature (T< 800 C) due to the aggressiveness of the molten salts liquid phase corrosion.
The main issue is that AlkCl compounds tend to deposit and corrode the metal surfaces in heat
exchangers and superheaters where they can condense. They can also form eutectic systems for
758
which the melting point can be very low inhibiting removal by usual methods like air blowing and
thereby increasing the slagging and fouling potential [1-3]. However, the presence of other
components like sulfur or aluminosilicates sharply decreases the tendency of chlorine to bind to the
deposits at high metal temperatures [4].
Corrosion by chlorine in the gas phase is especially relevant in oxygen rich environments where it
contributes to active oxidation of alloys. In reducing conditions metal chlorides form directly on
metal surfaces. Volatilization of metal chlorides is temperature dependent as well as its
condensation on metal surfaces. Thus, temperature pattern within the boiler is determinant to the
rate of corrosion [1].
With regard to chlorinated emissions it is organic chlorine that is mainly associated to the emission
of harmful pollutants such as dioxins and furans. According to the mechanisms proposed to explain
dioxin and furans formation during combustion it is expected that the molecular chlorine, Cl2, rather
than HCl control their formation. This will preferably occur at low temperature (250-450 C) in
reactions involving fly ash [5]. For the particular case of polyvinyl chloride, PVC, that is one of
organic chlorine main sources on waste alternative fuels, the de-hydroclorination occurs between
200 C - 400 C releasing hydrogen chloride gas [6] (Zevenhoven et al, 2002). However, in oxygen
rich conditions during combustion, molecular chlorine can be formed when the temperature is
around 600 C [7]. Literature also states that sulfur and nitrogen compounds can act as inhibitors,
drastically reducing dioxins and furans formation [8,9].
In biomass based fuels the major part of chlorine is in mineral and inorganic forms. Organochlorine
is part of the nutrient cycle and it is significant, for example, for field crop material. The chlorine in
biomass is readily available and reactive as well as much of the alkalinity. Typical chlorine contents
can vary from 0.01% to 0.72% in dry fuel [2].
On waste, chlorine content and forms vary widely among fractions. Data from municipal solid waste
fractions on Germany reveals that non packaging plastics are the major source of organic chlorine
(4.5% dry basis). Kitchen waste can have up to 1% Cl in dry basis, mainly in inorganic forms [10].
In this work we discuss the results of a brief assessment of chlorine content and its forms on
different biomass and waste derived fuels towards a better understanding of possible effects of its
use on boilers.
Waste alternative fuels

Two samples of biomass - sawdust (A) and rice husk (B) and three samples of waste fuels (C, D
and E) were selected and prepared.
Waste fuel C was a mixture of office wastes like plastics, papers, cardboard and toilet papers, with
little contamination by food or other putrescible wastes, shredded to a particle size of 30 mm.
Waste fuel D consisted of the high calorific fraction of mixed municipal solid waste (fraction > 120
mm separated by trommel screening in the initial stage of a mechanical and biological treatment)
after mechanical processing which comprised particle size reduction until 30 mm and metals
removal. Waste fuel E was also the high calorific fraction of mixed waste, but collected ahead in the
MBT unit. It is composed by the material, which is rejected by several trommel screens ((i) > 120
mm and (ii) > 80 mm). Both samples D and E presented similar aspect and it was possible to
detect some organic waste contamination by means of its odour and dirty aspect.
Laboratory sample preparation

All waste samples were stabilised towards the eventual presence of pathogenic organisms by
drying at 70 C for 2 hours. Then laboratory samples were prepared and about 5 kg of each sample
was milled to a particle size of 10 mm (Retsch SM 2000 cutting mill). Then, a mass reduction step
was applied by fractional shovelling or by manual increment method in order to divide the sample
using as many increments as possible, since it is considered a heterogeneous material and
segregation can often occur. Particle size was again reduced by milling down to 4 mm and then to
1 mm for further application.
Regarding rice husk, further milling using a cryogenic mill (Spex 6770) in order to increase
homogeneity of the pellet used in the calorimeter was carried out.
Portion tests were obtained using a rotary divider (Retsch PT100) with a 6 divisions head.
759
Gross calorific value
Samples were characterised in terms of gross calorific value using the standard proceeding for
solid biofuels and solid recovered fuels [11, 12]. A 1g pellet of previously dried sample at 105 C
was burned at 30 atm in a bomb calorimeter (LECO AC 600). Results are the mean of at least
three replicates.
Total chlorine content

This parameter was determined according to standard procedures for solid biofuels and solid
recovered fuels [13,14]. Previously dried samples suffered completed combustion in the bomb
calorimeter and gaseous chlorine was captured in an alkaline solution (KOH 0.2 M and/or KOH 2.0
M) which was analysed by Ion Chromatography (IC) with ionic suppression (Methrom IC 761,
column: Metrosep A Supp 150/4.0), after filtration with a 0.45 m GF filter.
Soluble chlorine content

Inorganic chlorine was solubilised using the procedure described for solid biofuels [15]. Extraction
of soluble chlorine was carried out using 1 g of dry sample mixed with 50 ml of deionised water in a
closed glass container. Suspension was cooked in an autoclave at 121 C for 1 hour. The cooled
suspension was filtered (0.45 m GF) and the filtrate was analysed by IC. The residual part was
dried at 105 C and suffered new extraction cycles until no chlorine was detected on the filtrate.
Four replicate samples were used and the filtrate of each elution step was analysed by IC.
Ash content and chemical characterization

For samples A, B and E the ash content was quantified by thermo gravimetric analysis and the
chemical composition of the ashes was determined by use of X-ray fluorescence spectroscopy.
Constraints of bomb combustion method for alternative fuels analysis

The five different materials analysed by bomb combustion for quantification of the calorific value
(followed by total chlorine determination) revealed different behaviours, which are important to
describe.
While for waste fuels (samples C, D and E) pelletization was easy using a particle size of 1 mm the
same was not verified for solid biofuels. In the particular case of rice husk the pelletization using
dry material at 1 mm was impossible (and for sawdust was difficult). In this situation the test portion
was milled to a lower particle size and yet the pellet was very fragile, tending to disaggregate.
During combustion several replicates appeared to explode spreading the sample throughout the
calorimeter bomb or causing damage to the equipment by destruction of the fuses.
Chlorine on biomass and waste derived fuels

Experimental results for the total and soluble chlorine content quantification are showed on Fig.1.
The fuels under study present chlorine contents within the expectable range for biomass published
on literature. Soluble chlorine on rice husk (sample B) revealed to be higher than the total chlorine
content that was quantified. This could be due to the difficulty on applying the bomb combustion
method to assure total combustion, formerly reported. If total combustion is not assured, the next
step of capturing Cl2 on a proper solution can be compromised.
Considering that inorganic chlorine can be determined based on its solubility on water, this type of
chlorine appears to be the most relevant source of chlorine on waste derived fuels produced from
the high calorific fraction of mixed municipal solid waste (samples D and E). The results for the
waste fuel (C) produced from other sources like office and commercial wastes revealed that
organic chlorine accounts for 50% of the total chlorine content.
760
Fig.1 Relation between total and soluble chlorine content found for the fuels under study and
comparison with data from literature.
25
Gross calorific value (MJ/kg dry basis)
Sample A
(sawdust)
23
Sample B
(rice husk)
21
Sample C
(waste fuel - office waste)
19
Sample D
(waste fuel - MSW)
17
Sample E
(waste fuel- MSW)
15
1 10 100 1000
Total chlorine content (mg/MJ dry basis)
Fig.2 Chlorine content on biomass and waste derived fuels (for biomass fuels the soluble chlorine
content was used to express total chlorine).
Chlorine content for waste derived fuels is higher than for biomass since they have comparable
energetic contents (Fig. 2). If total chlorine content is taken into account rather than its forms there
seems to be no substantial difference between total chlorine on fuels produced from municipal solid
waste and from other flows like commercial and office waste.
761
Possible effects of the use of these fuels
In order to assess further properties of the materials under study for samples A, B and E the ash
content of and its chemical composition were determined (Fig. 3). Samples C and D are expected
to have ash compositions close to that of sample E. The sawdust (sample A) presents a very low
ash content (0.23 % wt, dry basis), while both rice husk and MSW derived waste fuel E have
relatively high ash contents; 11.6 % wt and 14.8 % wt, respectively in dry basis.
Fig.3 Chemical composition of ash on samples A, B and E.
Given the experimental data on chlorine content and forms it is expectable that waste derived fuels
give rise to higher boiler corrosion propensity than biomass. In fuels produced from municipal solid
waste inorganic chlorine seems to dominate suggesting that the effects of their combustion can be
at corrosion level rather than harmful emission when compared to office and commercial waste
derived fuels, where there is some organic chlorine content.
Results suggest that for biomasses like sawdust and rice husk little or no impact on boilers is
expectable. On sawdust this is due to its low ash (and therefore alkali metals) content and for rice
husk, which has a considerable ash content, alkali metals paucity reflects on positive combustion
behaviour). For the waste derived fuel that was studied it is expected some susceptibility towards
fouling and slagging due to the non negligible content of alkaline metals (see Fig. 3), which is in
line with literature [16]. The combination of both information on chlorine and alkaline metals content
could suggest some corrosion potential by waste derived fuels. This is due not only to total chlorine
content which implies its potential as a corroding agent but also to the clarifying on its binding to
alkaline metals in inorganic forms, whose tendency to form low temperature eutectics is already
stated [16]. Thus, low temperatures should be avoided to minimize boiler corrosion phenomena.
Commercial waste fuels with similar total chlorine content to those found on MSW derived fuels
could be a better choice conveying equipment corrosion. However, in this particular case gaseous
emissions content of HCl and other chlorine derivatives would be significant. Tillman et al. [2] have
theoretically demonstrated that the availability of alkalis can reduce the amount of HCl (g) in
emission gases from combustion from 95% to 10% when particles mean temperature raises from
850 C up to 1400 C. Biomass contains alkalis readily available which could led it to be used as
combustible and alkalis source in a co-combustion process with RDF from MSW.
CONCLUSIONS
A brief study of chlorine content and forms was carried out on waste fuels derived from municipal
and commercial solid waste towards a better understanding of possible effects of their use on
industrial boilers when compared to conventional biomass fuels like sawdust and rice husk, which
762
were used as a reference. Additional information on these fuels like ash content and chemical
composition was also assessed for integrated analysis.
Waste fuels revealed higher total chlorine content (176 243 mg Cl/MJ fuel) than biomass (27 58
mg Cl/MJ fuel dry basis). Regarding ash content, waste derived fuels have a relatively high amount
of ash along with rice husk (> 10% wt, dry basis) while sawdust shows lower ash content (< 1% wt,
dry basis).
In MSW derived fuels chlorine is mostly present in inorganic or mineral form and thus low
temperatures should be avoided to minimize boiler corrosion phenomena by alkali-chlorinated
compounds, whose presence was detected on ashes. Commercial waste fuels with total chlorine
content alike could be an option for avoiding equipment corrosion since only 50% of total chlorine
content is in inorganic form. However, in this particular case gaseous emissions content of HCl and
other chlorine derivatives would be significant.
Given the main findings of this study and in light of the reported scientific knowledge on corrosion
effects, slagging and fouling on waste and biomass fired boilers, chlorine content and forms should
be combined with information on the alkalinity of fuels. However, further knowledge is still needed
on the integrated analysis of these properties.
Acknowledgements
R. Silva acknowledges FCT for PhD grant (SFRH/BD/61752/2009).
References
[1] H. P. Nielsen, F. J. Frandsen, K. Dam-Johansen, L. L. Baxter, The implications of chlorine-
associated corrosion on the operation of biomass-fired boilers, Prog. Energy Combust. Sci. 26
(2000) 283-298.
[2] D. A.Tillman, D. Duong, B. Miller, Chlorine in solid fuels pulverized in fuel boilers sources,
forms, reactions, and consequences: a literature review, Energ. Fuel 23 (2009) 3379-3391.
[3] Balampanis, DE (2009) Comparative study on the combustion and gasification of solid
recovered fuels. Emphasis on residues characterisation and chlorine partitioning, PhD thesis,
pp 52-54, Cranfield University, http://dspace.lib.cranfield.ac.uk/handle/1826/4692
[4] M. Aho, Reduction of chlorine deposition in FB boilers with aluminium-containing additives,
Fuel 80 (2001) 1943-1951.
[5] E. Wikstrom, S. Ryan, A. Touati, M. Telfer, D. Tabor, B.K. Gullett, Importance of chlorine
speciation on de novo formation of polychlorinated dibenzo-p-dioxins and polychlorinated
dibenzofurans, Environ. Sci. Technol. 37 (2003) 1108-1113.
[6] R. Zevenhoven, E. P. Axelsen, M. Hupa, Pyrolysis of waste-derived fuel mixtures containing
PVC, Fuel 81 (2002) 507-510.
[7] K. Liu, W.-P. Pan, J.T. Riley, A study of chlorine behavior in a simulated fluidized bed
combustion system, Fuel 79 (2000) 1115-1124.
[8] R. L. Lindbauer, F. Wurst, T. Prey, Combustion dioxin suppression in municipal solid waste
incineration with sulphur additives, Chemosphere 25 (1992) 1409-1414.
[9] R. Addink, R. H. Paulus, K. Olie, Prevention of polychlorinated dibenzo-p-
dioxins/dibenzofurans formation on municipal waste incinerator fly ash using nitrogen and
sulfur compounds, Env. Sci. Technol. 30 (1996) 23502354.
[10] W. Ma, G. Hoffmann, M. Schirmer, G. Chen, V. S. Rotter, Chlorine characterization and
thermal behavior in MSW and RDF, J. Hazard. Mater. 178 (2010) 489-98.
[11] EN 14918:2009 Solid biofuels Determination of calorific value, CEN.
[12] EN 15400:2011 Solid recovered fuels Determination of calorific value, CEN.
[13] EN 15289:2011 Solid biofuels Determination of total content of sulfur and chlorine, CEN.
[14] EN 15408:2011 Solid recovered fuels Methods for the determination of sulphur (S), chlorine
(Cl), fluorine (F) and bromine (Br) content, CEN.
[15] EN 15105:2011 Solid biofuels Determination of the water soluble chloride, sodium and
potassium content, CEN.
[16] G. Dunnu, J. Maier, G. Scheffknecht, Ash fusibility and compositional data of solid recovered
fuels, Fuel 89 (2010) 1534-1540.
763
PREDICTING LIQUIDS YIELDS FROM THE PYROLYSIS OF WASTE

MIXTURES USING RESPONSE SURFACE METHODOLOGY
1,2 1 2
F. Paradela , F. Pinto , A. M. Ramos
1 UEZ LNEG, Estrada do Pao do Lumiar 22, 1649-038 Lisboa, Portugal. filipe.paradela@lneg.pt
2 REQUIMTE, Departamento de Qumica, FCT-UNL, 2829-516 Caparica, Portugal.
ABSTRACT
The influence of the reaction time and temperature, initial pressure and waste mixture
composition on the slow batch pyrolysis of a mixture of three types of wastes was studied
in this work. The wastes pyrolysed were biomass (pine), used tyres and recycled plastic,
whose main components were polyethylene (PE), polypropylene (PP) and polystyrene
(PS).
The experiments were carried out in a 1L stainless steel autoclave, in which the
experimental conditions referred before were varied and optimized. Three product
fractions were obtained (liquids, solids and gases), which were subsequently collected
and analyzed.
Previous studies [1] showed that liquid products yield and composition were affected by
experimental conditions. The optimisation of these experimental parameters was done by
response surface methodology (RSM), which allowed identifying the inter-relations
between the experimental variables and optimising simultaneously the three variables
studied. Experiment Factorial Design was used and the experimental results for the yield
of liquids were fitted with a linear model by the method of least squares with good
correlation and high statistical significance. According to the model, the production of
pyrolysis liquids is maximized when the following conditions are used: reaction
temperature 350C, reaction time 30 minutes and initial pressure 0.2MPa for a waste
mixture containing 80% plastics, 10% pine and 10% tyres.
Keywords: Plastics, biomass, tyres, wastes, pyrolysis, RSM, batch.
INTRODUCTION
Modern societies face the challenges of sustainable use of resources and appropriate
management of the produced wastes. Tyres, plastics and biomass are examples of resources
widely used all over the world, resulting in an increasing amount of residues, which have become a
problem to humankind, due to their high negative environmental impact. Land filling and
incineration processes used so far to deal with these wastes present several problems. Land filling,
the most common disposal route, does not allow the recovery of the valuable organic content of
these wastes. Though incineration has the advantage of recovering some of wastes energetic
content, pollutants like light hydrocarbons, nitrous and sulphur oxides, or dusts and dioxins are
emitted, which degrades air quality and can cause population health problems.
The natural raw material for rubber tyre and plastics production is petroleum, whose reserves have
a limited lifetime and whose prices are increasing. Therefore, it is important to develop a
sustainable management of this resource. The application of pyrolysis processes to reduce wastes
load and at the same time to recover their energetic content may be a valuable part in that
management.
This technology allows the conversion of any organic waste, namely non-biodegradable, into new
organic products used either as raw materials for several industries, or for energy production as
substitutes of conventional fuels. During pyrolysis, thermal decomposition of wastes occurs in
presence of inert atmosphere under moderate conditions of temperature and pressure [2].
764
Polymeric structure is broken down, producing smaller intermediate species, which can further
react and produce a complex mixture of smaller hydrocarbon molecules, liquid or gaseous at room
temperature.
This paper reports the results obtained when mixtures of tyre rubber, plastic wastes and biomass
(pine) were pyrolysed. The main objective was to take profit of the easier decomposition of plastics
in these conditions, creating a fluid that could improve mass and heat transfer, facilitating the
pyrolysis of the other two components, which are normally decomposed at higher temperatures.
Another objective was to study possible synergisms between these three types of wastes. The
present work employed a factorial experiment design with the aim of optimizing experimental
conditions to maximize liquid production and to derive empirical equations for the process.
EXPERIMENTAL
Procedure
The pyrolysis experiments were conducted in a 1 liter stainless Hastelloy C276 alloy autoclave (by
Parr Instruments). Detailed information about the pyrolysis installation was presented in a previous
paper [2].
Typical curves of temperature and pressure evolution obtained with the apparatus used, showed
that the heating of the mixture is a slow process, as the heat transfer from the furnace to the
autoclave interior is not readily done. Average low heating rates of 5.5C/min were obtained [1]. As
waste mixture heating is a slow process for the equipment used, the residence time of the
feedstock inside the autoclave from the start of the heating process until the end of the cooling one
till room temperature is much longer than the reaction time, which is referred as the time at which
the waste mixture is maintained at the desired pyrolysis temperature.
After the predetermined reaction temperature was maintained for the desired reaction time, the
autoclave was cooled to room temperature and then opened to retrieve the products.
The gaseous products fraction was analyzed on a Gas Chromatograph (GC) to identify and
quantify the major gas components produced with the several pyrolysis reaction conditions tested.
The liquid fraction directly recovered from the reactor (decanted liquids) was distilled according to
ASTM D86 [3] to yield three fractions: the lighter hydrocarbons distilled below 150C, the second
distillate fraction with heavier hydrocarbons (150C < boiling point < 270C) and the residue (third
distillate, b. p. >270C). The first two distillates were analyzed by GC and GC/MS. The distillation
curve of the liquid fraction was also compared to the ones of gasoline and diesel. The remaining
solid fraction was weighted and extracted with dichloromethane (DCM) and tetrahydrofuran (THF)
in a soxhlet extractor (by ASTM D5369-93 [4]) to recover the liquids adsorbed in the solid
(extracted liquids). The dried solid product was weighted to give the effective pyrolysis yield of
solids. The extracted liquids were also subsequently analyzed by GC and GC/MS.
Raw material
In this work were used recycled wastes of polyethylene (PE), polystyrene (PS) and polypropylene
(PP) previously pelletized to particles with 5 mm of diameter. The biomass used was pine (pinus
pinaster) in the form of shreds derived from forestry residues with about 2 cm of length and 2 mm
of diameter, and the tyres were filaments of the same dimension provided by a scrap tyres
recycling plant after the removal of the metal and textile parts. Tyres main components were
natural rubber (NR), styrene butadiene rubber (SBR) and butadiene rubber (BR). The experiments
in this work were conducted with the following waste mixture (%w/w): 10% tyre, 10% pine and 80%
of plastics mix (56% PE, 27% PP and 17% PS, simulating their distribution in the plastics fraction of
Portuguese MSW).
Factorial experimental design

Least-squares were used in the fitting of the dependent variable, which for the present study was
the total liquids yield of the pyrolysis process. The use of response surface methodology allows a
response evaluation with the same precision as the one obtained if only a single variable was
studied in the same experimental range [5]. In the present case, all k factors (xi, i=1 to k) represent
quantitative variables of the unknown system response Y and the values of the function (mass
765
fraction of liquids) for different sets of factors are denominated system response Ym. Using this
methodology, the expected value of this response is referred as E (Y) = [6].
The response surface applied to liquid yield optimization can then be represented by Eq. (1).
(1)
In particular, the system response could be represented by a linear regression model of the
independent variables, (Eq.2), which also takes into account the interactions between variables, or
by a second order model (Eq.3) [7].
(2)
(3)
is calculated by Eq. 4.
(4)
The regression models were obtained by using a two level factorial design ) and three
factors (k = 3) plus the central point. This design is orthogonal, which means that the predicted
variance response for the region of interest is minimal and the regression coefficients can be
assessed independently. Also, to assume numerical accuracy in the estimation of regression
coefficients, factors were coded resulting in the coded variables , given by expression (4)
(4)
in which and correspond respectively to the upper and lower level of the natural variables.
The central point can then be represented by the coded coordinates
.
As variables in models are often highly correlated, it is possible to determine the relative
importance of each factor (which is accounted in the model coefficients), as well as the
simultaneous interaction of the three factors by using this methodology.

Preliminary experiments were carried out to assess the relative influence of these three factors in
the formation of liquid compounds [1]. These previous studies also allowed to determine the best
ways to operate the system, to recover the products and to perform their analysis and gave an
insight of the experimental parameters range to be used in the factorial design.
The experimental results were fitted by a linear model with a good correlation (0.983) and degree
of statistical significance.
Plotting the predicted values versus the experimental ones (Fig. 1) shows the good fitting of the
model, with the points very near the line of perfect prediction.
766
Fig. 1: Predicted versus experimental yields for total liquids production.
Fig. 2 is an example of the response surfaces obtained when fitting the linear model to the
experimental points. Several points similar to that of Fig. 2 were obtained, which allowed to identify
experimental conditions effect on liquid product yields and to determine inter relationships among
the experimental parameters studied.
Fig. 2: Response surface for the linear prediction of liquids yield. Initial Pressure: 0.21 MPa.
It was observed that temperature was the factor with more influence on liquids yield (higher
absolute coefficient), as its increase led to decrease of yield (negative coefficient). According to the
model, the maximum yield (91.3%) would be achieved using 350C, 30 minutes and 0.2 MPa. That
happened to be one of the experimental points, with a 91.6% experimental yield, which again
attests the good fitting of the model.
767
References
[1] F. Paradela, F. Pinto, I. Cabrita, I. Gulyurtlu, A. M. Ramos, Bioenergy II: Effect of Experimental
Conditions on the Slow Batch Pyrolysis of Mixtures of Plastics, Tyres and Forestry Biomass
Wastes, Int. J. of Chem. Reactor Eng., 7 (2009): A86.
[2] F. Pinto, I. Gulyurtlu, I. Cabrita and P. Costa, Pyrolysis of plastic wastes. 1: Effect of plastic
waste composition on product yield, J. Anal. Appl. Pyrolysis, 51 (1999) 39-55.
[3] ASTM D86 (2010): Standard test method for distillation of petroleum products, lubricants and
fossil fuels; Annual Book of ASTM Standards, 1994.
[4] ASTM D5369-93 (2008) Standard Practice for Extraction of Solid Waste Samples for Chemical
Analysis Using Soxhlet Extraction.
[5] A. Ko, A. Y. Bilges, A. Rafig, M. . Koak, A factorial experimental design for oxidative
thermal decomposition of low-density polyethylene waste, J. Anal. Appl. Pyrolysis 72 (2004)
309315.
[6] M. Miranda, F. Pinto, I. Gulyurtlu, I. Cabrita, C.A. Nogueira, A. Matos, Response surface
methodology optimization applied to rubber tyre and plastic wastes thermal conversion, Fuel,
89 (2010), 2217-2229.
[7] R. H. Myers, D. C. Montgomery, Response Surface methodology: process and product
optimization using designed experiments. New York: John Wiley & Sons; 1995.
768
COMPARISON OF SUGAR CONTENT OF TWO PULPING PROCESSES IN ORDER

ND
TO PRODUCE BIOETHANOL OF 2 GENERATION
1 1 1 1 2 1 1a
N. Quijorna , T. Llano , A. Portilla , C. Rueda , A.Blanco , A. Andrs and A. Coz
1
Dpt. Chemical Engineering and Inorganic Chemistry, University of Cantabria, Santander, Spain
2
Sniace, Industrial Area, Torrelavega, Spain
a
coza@unican.es
ABSTRACT
The lignocellulosic biomass, including industrial waste from pulp and paper processing, is
one of the most potential feed stocks for fuel ethanol of second generation. The use of
bioethanol as alternative automotive fuel has promoted the study of the feasibility of its
production. The main advantages using bioethanol are the lower levels of fossil fuel
inputs as well as carbon monoxide, nitrogen oxides and hydrocarbon after combustion
compared to that of gasoline.
Depending on the pulping process, lignocellulosic waste with different physico-chemical
characteristics can be obtained. In this paper, a battery of laboratory cooking trials have
been made in order to determine the conditions to transform a paper-grade pulping
process into a dissolving pulping process and to compare the characteristics of the spent
sulfite liquor towards its valorization. The results show that the dissolving process
produces a spent liquor with more reducing sugars content which are more suitable to be
transformed into bioethanol.
Keywords: bioethanol; eco-innovation; spent sulfite liquor; pulp; valorization
INTRODUCTION
New policies and frameworks in order to prevent environmental degradation and enhance quality of
life make necessary innovation. Many companies and governments have started to use the term
Eco-Innovation to describe the contributions of business to sustainable development while
improving competitiveness. Eco-Innovation can be generally defined as innovation that results in a
reduction of environmental impact, no matter whether or not that effect is intended [1].
The constant increase of oil price and its limited sources promote the search for renewable sources
of energy [2,3]. Lignocellulosic materials are one of the main sources of renewable biomass for fuel
production. Ethanol is considered one of the most potential next generation automotive fuel and
there are a lot of reserach studies for its production based on lignocellulosic biomass through both
first and more recently second generation. The use of bioethanol as alternative automotive fuel has
promoted the study of the feasibility of its production. The main advantages using bioethanol are
the lower levels of fossil fuel inputs as well as carbon monoxide, nitrogen oxides and hydrocarbon
after combustion compared to that of gasoline. The main disadvantage of the first generation
biofuels is that the use of crops for its production, increase the price of food all over the world [4].
For this reason, the efforts are centered in new biofuels from non-food crops, vegetable waste, or
industrial waste, including waste from pulp and paper processing.
One of the main lignocellulosic wastes in pulp and paper industry is the spent waste liquor.
Depending on the process, different spent liquors are obtained. In this work, Sulfite spent liquor
(SSL) is produced from acidic magnesium-based sulfite pulping of Eucalyptus globulus. Eucalypt
species is rather common raw material for the production of sulfite pulp in South Europe and South
Africa [4]. The major components of SSL are lignosulfonates and sugars, mainly pentoses of the
hydrolysis of gluguronoxylan [3-5].
769
The sulfite pulping process could be divided in two main groups: paper and dissolving grade, giving
different pulp quality. Nowadays the demand of dissolving pulp is increasing giving a more added
value pulp, therefore the expansion of the paper grade industries to the production of dissolving
pulp is growing. Furthermore, this economical strategy can give an environmental advantage: the
higher content of sugars in the spent liquor of the dissolving pulping process could favor its
valorization into bioethanol production of second generation. At paper pulp industry, the organic
fraction of the obtained liquor, brown spent liquor, is combusted to use the heat to produce process
steam and electric power; while the inorganic fraction, base content, is treated in order to be re-
used for cooking [2,6]. However, the valorization way of this waste into bioethanol is more difficult
than the spent liquor of dissolving pulp production [2,7].
The main processes to obtain dissolving pulp are the acid sulfite and pre-hydrolysis kraft
processes. Extraction methods to convert a paper grade pulp to dissolving pulp by reducing
hemicellulose content have been developed in literature [8].
In this paper, a battery of laboratory cooking, with Eucalyptus globulus and acidic magnesium-
based sulfite as raw materials, have been made in order to determine the optimal conditions to
transform a paper-grade pulping process into a dissolving pulping process and to compare the
characteristics of the obtained liquor towards its valorization. The quality parameters of pulp
product in both cases (paper and dissolving grade) have been monitored together with the physical
and chemical properties of the liquor. An increase of the reducing sugars content has been
observed in the dissolving process making its valorization into bioethanol easier.

Materials
The cooking acid employed for the wood digestion was based on magnesium hydroxide and sulfur
dioxide. The solid-liquid-gas contact was made at laboratory scale. The composition requirements
have been determined according to a titration method with iodine and sodium hydroxide based on
Tappi 604 [9]. The wood used was hardwood, Eucalyptus globulus, was supplied by Sniace group.
The chips were sieved using 15-30 cm of length fraction.
Cooking trials
Lab tests have been developed in two lab digesters of 1 litre (Fig 1). The control system simulates
the cooking cycle and the pressure of the process. The cooking cycle was based in an acid sulfite
process to produce paper grade pulp. The control system of the lab digester reproduces the
industrial process from cooking acid preheating to degasification stages. Four trials were carried
out. Trial 1 (T1) was performed with paper grade conditions and the rest of the trials were achieved
by means of the modification of the maximum temperature, the heating rate and the dwell time in
order to obtain a dissolving grade pulp. Both, maximum temperature and heating rate of the
laboratory trials, are confidential data. Dwell time was determined by means of estimation of energy
supplied and the colour of the SSL.
770
Fig1. Laboratory scale reactors
Analytical Methods
The quality grade of cellulose pulp was evaluated by means of Kappa index (Tappi 236) [9],
intrinsic viscosity (ISO 5351) [10] and -cellulose content (Tappi 203) [9].
In addition, the main physico-chemical properties of the lignocellulosic waste SSL, were evaluated,
based on specific methodologies for wood, pulp, paper and paperboard. Density and Viscosity at
ambient temperature was measured using a Gay-Lussac picnometer and viscometer Fungilab
Alpha L series. Dry matter was measured by drying at 103-105C using a Selecta stove. Ash
content was determined at 525C (organic matter) and 900C (inorganic matter), according to the
Tappi T211 and T413 [9], respectively, using a Selecta furnace. Lignosulfonates (LS), total and
reducing sugars determinations consisted of measuring the solution absorbance at 232.5, 490 and
540 nm, respectively, by an UVvisible spectrophotometer Perkin Elmer Lambda 25 [3,11,12].
Cation content of Ca, Mg, Na and K has been measured by means of Atomic Absorption
(Shimadzu, AA7000).

The main objective of paper grade production is to achieve a high-quality pulp combined with an
acceptable yield. The chemical reactions must be stopped at a residual lignin content which can be
selectively removed in a bleaching treatment. In the case of dissolving pulp production, the major
target is to adjust a certain average molecular weight of the pulp carbohydrates, measured as
intrinsic viscosity [6].
Table 1 shows the quality properties of the cellulose pulp of all of the experiments, giving the
process conditions to obtain not only paper grade pulp (T1) but also dissolving grade pulp (T2T4).
As it was expected, Kappa Index of Trial 1 (20.47) is much higher than the rest of the experiments
(5.12-6.40) because this value (20.47) is more typical in a paper grade pulp [6,8]. The higher lignin
content of the cellulose pulp corresponds with a low purity of -cellulose (76.45%) and the intrinsic
viscosity is around two times bigger than the dissolving grade pulp. The closing of paper grade
cooking is independent on the intrinsic viscosity of the pulp.
771
Table 1. Quality properties of cellulose pulp
Trial Kappa Index Intrinsic Viscosity -cellulose
[ml/g] [%]
T1 20.47 1,284.46 76.45
T2 5.12 566.27 88.25
T3 6.18 658.19 89.53
T4 6.40 752.15 88.79
The physico-chemical characterization of SSL is represented in Tables 2 and 3. SSL consists

mainly of lignosulfonates and sugars. The process modifications do not affect significantly the
density (1072-1080 g/L) and the viscosity (2.04-2.18 cP) of SSL. The ash at 525C is related to the
organic matter of the sample and the 900C with the inorganic salts [4,9]. In this sense, T2 and T4
show high ash content at 525C and is related with higher lignosulfonate and sugar content. As it
can be expected, the magnesium salts are the major inorganic components in SSL, due to the
fresh liquor is based on magnesium hydroxide. Other inorganic components determined are
calcium, potassium and sodium, in increasing concentration order.
Table 2. Physical properties of spent sulfite liquor

Trial Dry matter Density Ash at 525C Ash at 900C Viscosity
[%] [g/L] [%] [%] [cP]
T1 13.15 1,074.70 15.07 9.63 2.15
T2 15.69 1,080.60 33.12 8.67 2.17
T3 14.24 1,072.60 17.28 7.66 2.04
T4 16.11 1,078.00 37.79 9.73 2.18
Table 3. Chemical properties of spent sulfite liquor

Trial Lignosulfonates Reducing sugars Total sugars Na K Ca Mg
[%]* [%]* [%]* [g/L] [g/L] [g/L] [g/L]
T1 43.32 9.78 20.10 0.015 0.154 0.171 8.270
T2 62.47 12.55 16.16 0.016 0.149 0.229 7.219
T3 68.74 14.62 19.33 0.014 0.129 0.141 6.534
T4 64.46 13.40 20.26 0.020 0.165 0.164 6.989
*expressed as % of dried wood
Figure 2 shows the main components of SSL for each experimental trial. As it can be observed,
Trial 1, paper grade pulp, presents lower delignification grade than Trials 2-4, dissolving grade.
Total sugar and ash content at 900C are similar in overall trials varying in the range of 16.16 to
20.26 g/L and 7.66 to 9.73%, respectively. Figure 3 shows the reducing and non-reducing sugar
proportions. Dissolving grade trials (T2-T4) present higher proportion of reducing sugars monomers
(66-77%) which are suitable to be transformed into bioethanol. The process conditions of dissolving
pulp production correspond with a more intense hydrolysis due to the transformation of
hemicelluloses into monomers [6].
772
240,0
Lignosulphonates Total sugars Ash at 900C
200,0
160,0
Concentration (g/L)
120,0
80,0
40,0
0,0
T1 T2 T3 T4
Laboratory Trials
Fig 2. Results of lignosulfonates, total sugars and ash content at 900C in the experimental trials.
100%
80%
60%
40%
20%
0%
T1 T2 T3 T4
Total sugars
Lignosulphonates Laboratory Trials
Fig 3. Results of reducing and non-reducing sugars proportions in the experimental trials.
773
CONCLUSSIONS
A set of laboratory cooking experiments, with Eucalyptus globulus and acidic magnesium-based
sulfite as raw materials, has been made in order to transform a paper grade pulp into a dissolving
grade pulp. The quality parameters of pulp product in both cases (paper and dissolving grade)
have been monitored together with the physical and chemical properties of the spent sulfite liquor,
giving the best process variables in both grades: maximum temperature, heating rate and dwell
time.
It can be concluded that the modifications of the sulfite pulping process produce a higher purity of
cellulose pulp, obtaining quality parameter values of dissolving pulp. Due to the higher
delignification and hydrolysis stages, spent sulfite liquor with higher content of lignosulfonates and
reducing sugars is obtained. The higher proportions of monomer (17-29%) of spent liquor
associated with a dissolving grade pulp allow the valorization of this lignocellulosic waste material
into bioethanol.
Acknowledgments
The authors gratefully acknowledge the financial support for this research by the EUCAFUEL
23.H031.64003 research project under the framework of the Spanish Ministry of Science and
Innovation.
References
[1] OECD (2009) Eco-Innovation in industry. Enabling green growth. ISBN 978-92-64-07722-5.
[2] Mendes C.V.T., et al. (2009). Valorisation of hardwood hemicelluloses in the kraft pulping
process by using an integrated biorefinery concept. Food and Bioproducts Processing, 87, pp 197-
207.
[3] Marques A.P. et al. (2009) Chemical composition of spent liquors from acidic magnesium-based
sulphite pulping of Eucalyptus globulus. Journal of wood chemistry and technology, 29, pp 322-
336.
[4] Xavier A.M.R.B. et al. (2010) Second-generation bioethanol from eucalypt sulphite spent liquor.
Biosource Technology, 101, pp 2755-2761.
[5] Grio F.M. et al. (2010) Hemicelluloses for fuel ethanol: A review. Bioresource technology, 101,
4775-4800.
[6] Hervert Sixta (2006) Handbook of pulp. Wiley-Vch Verlag GmbH & Co. ISBN: 3-527-30999-3.
[7] Rueda C., et al. (2011) Physico-Chemical characterization of a spent sulfite liquor oriented to its
th
valorization options. 16 International Symposium on Wood Fibre and Pulping Chemistry
(ISWFPC).
[8] Ibarra D., et al. (2010) Combination of alkaline and enzymatic treatments as a process for
upgrading sisal paper-grade pulp to dissolving-grade pulp. Bioresource Technology, 101, pp 7416-
7423.
[9] TAPPI Standard Test Methods. (1993). Fibrous Materials and Pulp Testing T1-200 Series.
[10] ISO 5351. Pulps- Determination of limiting viscosity number in cupri-ethylenediamine (CED)
solution.
[11] Ko J-J., et al. (2009). Biodegradation of high molecular weight lignin under sulphate reducing
conditions: lignin degradability and degradation by-products. Bioresource Technology, 100, pp.
1622-1627.
[12] Wang H., et al. (2012). High efficient conversion of cellulose to polyols with Ru/CNTs as
catalyst. Renewable Energy, 37, pp 192-196.
774
KINETIC STUDY OF THERMAL DE-CHLORINATION OF PVC-CONTAINING

WASTE
1,2,a 1 2 2 3 3
A. Castro , C. Carneiro , C. Vilarinho , D. Soares , C. Maes , C. Sousa and F.
2
Castro
1
CVR - Centre for Waste Valorization, Guimares, Portugal
2
CT2M - Centre for Mechanical and Materials Technologies, Mechanical Engineering Department,
University of Minho, Guimares, Portugal
3
Endutex - textile coatings, SA
a
acastro@cvresiduos.pt
ABSTRACT
With the increasing of plastics content in solid waste, both municipal and industrial, also
increases the interest in its use as an energy source.
Some of these wastes are an important potential source of energy and might be valorized
using the pyrolysis or gasification processes. However, the presence of high chlorine
contents in its composition prevents its management by a thermal process, as
consequence of toxic compounds production and their release to the atmosphere.
The present work asses a possible process for treating PVC-containing wastes in an
environmentally friendly way. It is based on the effective de-chlorination of PVC-
containing wastes through a pyrolysis process at low temperature before the
carbonaceous residue from PVC-containing wastes being subject to a subsequent
thermal treatment for energetic valorization.
Keywords: Pyrolysis, thermal degradation, PVC-containing waste, energy valorization;
INTRODUCTION
The presence of organic compounds on wastes, especially plastics, is considered an important

source of energy. However, most of these plastics contain polyvinyl chloride (PVC), causing
recycling problems when it is considered a thermal valorization process for its treatment [1],
preventing the use of those residues on these processes, which main goal is the energy recovery
[2,3]. A possible solution is to remove the chlorine from PVC-containing waste through a pyrolysis
process before being subjected to a thermal treatment, for energetic valorization.
Pyrolysis is one of the applied techniques for energetic valorization and is defined as a process of
irreversible chemical modification of compounds under the action of heat and in the absence of
oxygen, causing thermal degradation [1]. The reaction involved in this process is endothermic and
the characteristics of the obtained products are function of the waste composition and of several
operating factors, such as the temperature, pressure and residence time in the pyrolysis reactor.
The pyrolysis process is considered by several authors [2 - 8] as a possible technique for the
energy recovery from PVC-containing wastes, through the thermal degradation of the chlorine
775
molecule. PVC pyrolysis involves significant cross-linked reactions with the formation of
polyaromatic structures (possibly chlorinated) and a carbonaceous residue (char) [9]. Thus, it is
possible to break down this molecule, allowing the chlorine recovery as hydrochloric acid or
chloride [10], with potential economic gains.
However, the presence of poly(vinyl chloride) in wastes composition confines their management by
thermal valorization processes as consequence of environmental problems and corrosion of the
equipment. In fact, high levels of chlorine in wastes composition are responsible for the formation
of hydrochloric acid, chlorine gas and dioxins [11]. Therefore, a preview thermal treatment by a
pyrolysis process to remove the chlorine from PVC-containing wastes will be a suitable step if done
prior to an energy recovery process to produce a synthesis gas.
Considering thermogravimetric analysis, it is assumed that the degradation of PVC occurs between
200 and 400 C [2, 12]. At 250 C, the decomposition of PVC has already been initiated, reaching a
maximum at approximately 300 C. At 350 C the amount of chlorine present in PVC waste is less
than 0.1%, which means that at this temperature, 99.5% of the whole chlorine has already been
released [2]. At the end of the process of chlorine removal, a residual amount of chlorine remains
on the waste [9].
The C-Cl bonds in the structure of PVC have a relatively lower binding energy than the C-C and C-
H bonds, which justifies that the bonds of chlorine are the first to be broken, thus starting the
thermal degradation of PVC. The de-chlorination of PVC is a free radicals chain reaction therefore
requiring low activation energy to start, occurring at low temperatures [4, 7].
De-chlorination of PVC wastes is a mandatory step for any treatment process, able to recover
energy from these wastes. In fact, from the decomposition of PVC, one polymeric fraction can be
obtained with high energetic value:
C2H3Cl HCl + C2H2 (I)
As a matter of fact, products from the decomposition will be of the type C nHn.
This work aims the contemplation of new valorization processes and use of PVC-containing
wastes. For the PVC molecule de-chlorination, tests were performed at low temperature pyrolysis
and subsequent gasification of the remaining fraction in order to produce a synthesis gas with high
energetic potential.
EXPERIMENTAL WORK
In this work, the kinetics of thermal de-chlorination has been studied, by simultaneous DTA/TGA
determinations, under inert atmosphere. With all the experimental data obtained a multivariate
regression of ln (r) has been performed in function of 1/T and ln ([HCl]). The kinetic model has
been calculated just for points where temperature was lower than 340 C, and the obtained model
is:
2
with r = 0,9912
776
This allows considering that reaction as a first order one with activation energy of 133800 J/mol
760 J/mol.
For the kinetic study, a DTA/TGA (SDT 2960 from TA Instruments) testing at different temperatures
has been carried out in order to determine the relationship between the rate of PVC de-chlorination
and the temperature of the thermal treatment, under an inert atmosphere. It was used a
commercial pure PVC powder with the chemical formula C 2H3Cl, in which 56,7% is chlorine. The
reference is VICIR S 950 and it is a vinyl chloride homopolymer produced by a suspension
polymerization process.
Experiments have conducted up to 5 different maximum temperatures: 250, 275, 300, 325 and 400
C, with a heating rate of 10 C per minute until the desired temperature is reached. After reaching
this temperature, a stage has been done during 360 minutes. Heat flux (weight corrected heat flow
in W/g) and weight of sample, has been continuously recorded.
DTA/TGA testing performed indicates that the temperature of 340 C enables the removal of 88 %
of the chlorine present in the PVC material. The resulting de-chlorinated fraction, carbonaceous
residue, has also been characterized and it is mainly constituted by carbon. This carbonaceous
residue was testing up to 500C in DTA/DTA and was verified that the combustion reaction of the
carbonaceous material is complete at 493C demonstrating potential as a fuel source to a following
gasification in order to produce a synthesis gas with high energetic potential.
To characterize the sample of PVC used and the carbonaceous residue formed, it has been used
an TruSpec Elemental Determinator, model TruSpec CHN, of Leco with a burn time of 452
seconds and an Philips Analytical sequential X-ray fluorescence (XRF) Spectrometer model
X'Unique II.
Table 1. Comparison between the chemical composition (in wt%) of PVC sample used and the carbonaceous residue
obtained from pyrolysis at 340 C.
PVC PVC
(initial sample) (Carbonaceous residue )
Carbon 38,4 89
Hydrogen 4,9 7
Chlorine 56,7 0,07
Through table 1, we are able to conclude that the de-chlorinated fraction obtained at 340C is
mainly constituted by carbon presenting residual chlorine content, 0,07 %.
Tests were performed in the laboratory and pilot scale, where the variables temperature, pressure
and residence time inside the reactor were studied, as well as its influence on the reaction products
obtained.
The pilot plant consists in a reactor where the pyrolysis occurs, with a stainless steel body heated
by electrical resistance and a column of water where the gas is bubbled, as exemplified in figure 1.
Measuring instruments such as thermocouples and pressure gauges are used to control the
conditions (temperature and pressure) inside the reactor.
777
The fixation of the released chlorine is obtained by water absorption, forming HCl (hydrochloric
acid), CaCl2 (calcium chloride) and also NaCl (sodium chloride), when the aqueous solution,
containing CaO (calcium oxide) or NaOH (sodium hydroxide), respectively.
Figure 1: Scheme of pilot scale used for the tests.
Initially, a slight vacuum is created to remove the oxygen inside the reactor, then the test is initiated
and divided into two stages. The first stage is a low-temperature pyrolysis or carbonization, where
the de-chlorination of the PVC-containing waste reaction occurs, the released chlorine is recovered
in the column in the form of hydrochloric acid, sodium chloride or calcium chloride. After the first
stage is completed, second stage, takes place, then the carbonaceous residue (without chlorine)
resulting from the first stage, is energetically valorized, at temperatures above 550 C.
The residence time in the reactor was tested by the pressure differences, viewed through the
pressure gauge in the reactor. Thus, the reaction starts in vacuum and is assumed as completed
when the pressure reaches zero, i.e. atmospheric pressure. During the reaction, when the pressure
is 0,5 bar above atmospheric pressure, it is enough for the syngas formed inside the reactor can
bubble in column. After all the gas is released, then the pressure drops to zero on the gauge, i.e.,
atmospheric pressure, thus giving the information that the reaction is complete.
All materials used in building a pilot plant must be well chosen, because of corrosion of materials
and isolation. The absence of leakage or entry of gases must also be controlled, since the
produced gases are toxic and cannot leak to the atmosphere, and also because as pyrolysis is a
process that must take place in anoxic environment, thus it should be affected by any entry of
oxidizing agents.
The main reaction product is a synthesis gas for burning to produce heat.
778
CONCLUSIONS
In this work, the kinetics of the reaction of thermal decomposition of PVC were studied, leading to
the development of a kinetic model, with the expression ln r = 31,3 - 16100/T + 1,020 ln C (HCl).
This model was obtained for the decomposition temperatures lower than 340 C, in which almost
all chlorine is removed from the pure PVC through the chemical reaction described, with an
activation energy of 133800 J/mol, value very close to the one obtained by others researchers [4].
The kinetic model was verified in laboratorial trials, and it was observed a reduction of 88 % of the
chlorine contained in PVC, making it suitable to be used in a recovery process to obtain a synthesis
gas.
During the pyrolysis treatment, released chlorine can be fixed in the form of aqueous solution of
hydrochloric acid, calcium chloride or sodium chloride. This process shall constitute an attractive
route, envisaging environmental benefits, thereby avoiding deleterious effects of toxic gas
emissions.
In this study, we propose a methodology to remove chlorine from PVC-containing wastes allowing
the valorization of the chlorine-free remaining fraction. A double benefit can thus be achieved as it
not only saves the cost of landfilling but also produces an value added syngas.
It is concluded that for PVC-containing waste, the solution can pass through a full treatment
consisting of two phases. Where the first is to remove the chlorine from the PVC molecule and the
second is to valorize the remaining fraction.
References
[1] Lewis, F.; Ablow, C. (1976) Pyrogas From Biomass. Presented to a conference on capturing
the sun through bioconversion, Washington, D.C., Shoreham Americana Hotel. Stanford
research institute.
[2] Zevenhoven, R.; Axelsen, E.; Hupa, M. (2002) Pyrolysis of waste-derived fuel mixtures
containing PVC, Fuel, 81, pp 507-510.
[3] Kim, S. (2001) Pyrolysis of waste PVC pipe, Waste Management, 21, pp 609-616
[4] Ma, S.; Lu, Gao, J. (2002) Study of the Low Temperature Pyrolysis of PVC, Energy & Fuels,
16, pp 338-342.
[5] Jaksland, C.; Rasmussen, E.; Rohde, T. (2000) A new technology for treatment of PVC waste
Waste Management, 20, pp 463-467.
[6] Qiao, W.; Song, Y.; Yoon, S.; Korai, Y.; Mochida, I.; Yoshiga, S.; Fukuda, H.; Yamazaki A.;
(2006) Carbonization of waste PVC to develop porous carbon material without further
activation, Waste Management, 26, pp 592-598.
[7] Qing-lei, S.; Xin-gang, S.; Yun-liang, L.; He, Z.; Xiao, W.; Chuan-ge, C.; Jian-hua, L. (2007)
Thermogravimetric-Mass Spectrometric Study of the Pyrolysis Behavior of PVC, Journal of
China University of Mining & Technology, Vol.17, No.2.
779
[8] Saeed, L.; Tohka, A.; Haapala, M.; Zevenhoven, R. (2004) Pyrolysis and combustion of PVC,
PVC-wood and PVC-coal mixtures in a two-stage fluidized bed process, Fuel Processing
Technology, 85, pp 1565-1583.
[9] lazevska-Gilev, J.; Spaseska, D. (2010) Formal kinetic analysis of PVC thermal degradation,
Journal of the University of Chemical Technology and Metallurgy, 45, 3, pp 251-254.
[10] Tanaka, Y.; Tsuji, T.; Shibata, T.; Uemaki, O.; Itoh, H. (2007) Dehydrochlorination Rate in
Thermal Degradation of PVC, School of Engineering, Hokkaido University, Japan 060-8628.
[11] Kamo T., Yamamoto Y., Miki K., Sato Y. Conversion of waste polyvinyl chloride (PVC) to
useful chemicals. (1996) Resources and Environment. 305, Japan.
[12] Karayildirim, T.; Yanik, J.; Yuksel, M.; Saglam, M.; Vasile, C.; Bockhorn, H. (2006) The effect
of some fillers on PVC degradation, Journal of Analytical and Applied Pyrolysis, 75, pp 112-119
780
14th September
Keynote Lecture IV
( Reuse and recycling of waste in geotechnical related
applications. National case study of steel slag)
Antnio Roque
781
Professor Antnio Roque [LNEC - Laboratrio Nacional de Engenharia Civil. Lisboa, Portugal]
Biography
Antnio Roque is Ph.D. Civil Engineering - Soils (2001)from INSA de Lyon (France). He is, from
2009 Guest Professor, Environmental Geotechnics, Geotechnical Master Science Course for
Civil Engineers. He is from 2006 to present Senior Research Officer, Geotechnique Department
of LNEC.
The research activity developed is focused in subjects related with landfills, study of
confinement systems in polluted environments, pollutant transport through natural soils and
liners, soil-poluttant chemical compatibility, waste re-use in geotechnical works as well as
aboratory and in situ tests. He participated in more than 60 LNEC Research under Contract
Processes. He is Coordinator of the Technical Committee Waste Reuse in Geotechnical Works
of the Portuguese Geotechnical Society.
782
St
REUSE AND RECYCLING OF WASTE IN GEOTECHNICAL RELATED APPLICATIONS. NATIONAL CASE

STUDY OF STEEL SLAG
1,a 2 3 2 4
Roque, A.J. , Gomes Correia, A. , Castro, F. , Reis Ferreira, S. and Fortunato, E.
1
Geotechnique Dpt., Laboratrio Nacional de Engenharia Civil, Lisbon, Portugal
2
Dpt. Civil Engineering, University of Minho, Guimares, Portugal
3
Dpt. Mechanical Engineering, University of Minho, Guimares, Portugal
4
Transportation Dpt., Laboratrio Nacional de Engenharia Civil, Lisbon, Portugal
a
aroque@lnec.pt
ABSTRACT
In Portugal, and also at international level, preventing the production of a significant number of different types of
waste is still unfeasible. Therefore, the waste management strategy should favor the exploitation of its potential,
namely through reuse and recycling solutions, for instance, in transport infrastructures and geotechnical works.
The implementation of this practice should follow the principles of sustainable development: a) reducing the
quantities of waste that is disposed of in landfill; b) creating a new and important national market; and c)
preserving natural materials.
At Portugal there are two Iron Steel Companies (ISC). These Companies are currently operating with electric arc
furnaces: one is located at Paio Pires, Seixal (Seixal ISC), and the other at S. Pedro de Fins, Maia (Maia ISC).
The two Portuguese ISC produced about 1,500 000 tons/year of steel, being 270,000 tons/year of black steel slag.
After removing the metallic component for recycling, 250,000 tons/year of non-metallic components remained. In
accordance with data provided by the Portuguese ISC, within medium term, about 400,000 tons of black steel slag
are expected to be annually produced. The management of this large volume of material, in accordance with the
applicable legal policies, represents a significant source of concern for the ISC and for the country.
According to the routine tests and criteria for natural materials, steel slag has generally been considered, in the
past, as inappropriate for use in transportation infrastructures and geotechnical works, as many other secondary
materials.
In this framework, a Research and Development Project was underway in Portugal to determine a recycling
application in transportation infrastructures and geotechnical works for the processed steel slag (actually defined
as Inert Steel Aggregates for Construction ISAC) produced by the two Portuguese ISC. The project involved the
National Laboratory for Civil Engineering (LNEC - Laboratrio Nacional de Engenharia Civil, as coordinator), the
University of Minho (UM) and the Centre for Reuse of Waste (CVR). The main purpose of the project was to
create a mechanistic and environmental approach intended to promote the recycling of waste, in general, and
processed steel slag (ISAC), in particular.
There is some common understanding that many of the engineering test methods used for natural materials may
not predict true field performance when applied to secondary materials. For this reason, this national project gave
783
St
priority to laboratory performance-based tests for engineering properties. It also examined environmental
properties, which are relevant for secondary materials, as well as field tests to check the laboratory test results.
So, this project followed the most relevant recommendations of previous European Community projects.
In this sense, to evaluate the recycling of processed steel slag (ISAC) in transportation infrastructure and
geotechnical works, a vast experimental program was implemented in the laboratory to study the mineralogical,
chemical, environmental, geometrical, physical and mechanical properties. The aim of this preliminary study was
to compare the values of these properties obtained for the processed steel slag (ISAC) with values specified in the
Portuguese standards for natural aggregates that could be applied in transportation infrastructures.
The laboratory test results were validated in a full-scale trial by means of field tests addressing the same
engineering properties (devices which measure field stiffness by spot tests and by continuous monitoring, as well
as leaching values measured with lysimeters). This experimental approach was a sound basis to evaluate the
recycling of processed steel slag (ISAC) in transportation infrastructure and geotechnical works.
Based on the index test results obtained in laboratory it was shown that processed steel slag (ISAC) meets the
specifications of the Portuguese Roads Administration. Furthermore, the laboratory performance-based test
results demonstrate that processed steel slag (ISAC) has better mechanical properties than standard road
pavement (base and sub-base layers) materials. These results emphasize that the processed Portuguese steel
slag (ISAC) could be used in geotechnical works, and particularly in transportation infrastructures.
In addition to this laboratory study, the results of field study carried out in the full-scale field trial (embankment road
section) to evaluate mechanical and environmental performances validated the properties associated to the
laboratory test results. Particularly, they demonstrated the better mechanical performance of processed steel slag
(ISAC) when compared with natural soil and natural road pavement aggregates. Moreover, in which concerns the
environmental aspects, they confirmed that processed steel slag (ISAC) is an inert waste in terms of leachability.
On the basis of the research work developed, the steel slag is, after processing in the industrial facilities of ISC,
marketed as a new construction material, named ISAC, and, consequently, could be used in competition with
natural aggregates for construction of transportation infrastructures and geotechnical works. It should be also
mentioned, as a final remark, that according data supplied by Portuguese ISC, the accumulated tons of Maia ISAC
have already sold out and at this time there is a lack of material for delivery. The same is expected to the Seixal
ISAC where the stock is decreasing continuously. This year sales of ISAC already have a significant economic
value, of a few hundred thousand Euros.
Steel slag after being Classification of steel slag Processed steel slag (ISAC)
separated from liquid steel
The authors wish to thank the Portuguese Foundation for Science and Technology for the financial support
provided to this study (File PPCDT/ECM/56952/2004), through the Operational Program for Science and
Innovation 2010 (POCI 2010) and the European Regional Development Fund (ERDF).
784

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CVR Centro para a Valorizao de Resduos

Telef.: +351 253 510 020

Fernando Castro, Universidade do Minho, CVR, Portugal (Chair)

Ana Andrs, Universidad de Cantabria, Spain

Ana Maria Segades, Universidade de Aveiro, Portugal

Ange Nzihou, Ecole de Mines de Albi, France

Antnio Brito, Universidade do Minho, Portugal

Antnio Correia, Universidade do Minho, Portugal

Antnio Jos Roque, LNEC Laboratrio Nacional de Engenharia Civil, Portugal

Antnio Roca, Universita de Barcelona, Spain

Cndida Vilarinho, Universidade do Minho, CVR, Portugal

Carlos Bernardo, Universidade do Minho, Portugal

Carlos Franco, LNEG Laboratrio Nacional de Energia e Geologia, Portugal

Carlos Nogueira, LNEG Laboratrio Nacional de Energia e Geologia, Portugal

Derek Greedy, Warwickshire County Council, United Kingdom

Eduardo Ferreira, Universidade do Minho, CEBio, Portugal

Enzo Favoino, Scuola Agraria del Parco di Monza, Italy

Felipe Macias Vasquez, Universidade de Santiago de Compostela, Spain

Fernanda Margarido, Instituto Superior Tcnico, Lisboa

Fernando Leite, LIPOR, Portugal

Ibrahim Gulyurtlu, LNEG Laboratrio Nacional de Energia e Geologia, Portugal

Javier Viguri, Universita de Cantabria, Spain

Joana Carvalho, CVR Centro para a Valorizao de Resduos, Portugal

Joo A. Labrincha, Universidade de Aveiro, Portugal

Jos Cardona, Resinorte, Portugal

Jos Carlos Teixeira, Universidade do Minho, CEBio, Portugal

Jos Cavalheiro, Universidade do Porto, Portugal

Jos Fernando Juc, CETENE, Brasil

Jos M. P. Vieira, Universidade do Minho, Ordem dos Engenheiros, Portugal

Jos Teixeira, Universidade do Minho, Portugal

Lus Marinheiro, APESB, Portugal

Madalena Alves, Universidade do Minho, Portugal

Manuel Afonso Magalhes da Fonseca Almeida, Universidade do Porto, Portugal

Mrio Russo, Instituto Politcnico de Viana do Castelo, Portugal

Montserrat Cruells, Universita de Barcelona, Spain

Pablo Kroff, Simbiente, Chile

Patrick Sharrock, IUT de Castres, France

Paulo Ramsio, Universidade do Minho, Portugal

Pedro Machado, Braval, Portugal

Regina Monteiro, Universidade Nova de Lisboa, Portugal

Rosrio Tavares de Oliveira, Universidade do Minho, Portugal

Said Jalali, Universidade do Minho, Portugal

Teresa Vieira, Universidade de Coimbra, Portugal

Wilson Acchar, UFRN - Universidade Federa do Rio Grande do Norte, Brasil

Keynote Lecture I 142

Keynote Lecture II 251

Poster Session 255

Plenary Lecture II 515

Keynote Lecture III 646

Keynote Lecture IV 781

He is currently Chair of the WG on Biological Treatment at ISWA International Solid Waste

Chairman: Fernando Castro

SORPTION STUDIES OF Zn AND Cu BY COMPOST

MATERIALS AND METHODS

RESULTS AND DISCUSSION

Table 1 Physical and chemical composts characterization.

Table 2 Maximum sorption capacity of each compost for Cu and Zn.

WASTE POLYMERS RECYCLING IN HIGH PERFORMANCE ASPHALT

Selection of Polymer Wastes

Ring & Ball temperature [C]

Definition of the Mixtures Production Conditions

PERFORMANCE OF ASPHALT MIXTURES PRODUCED WITH WASTED POLYMERS

Fig. 3 Specimens of mixtures C1 and C2 using PEX as aggregates