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Journal of Cleaner Production xxx (2013) 1e8

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Journal of Cleaner Production


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Study of lead (II) adsorption onto activated carbon originating from


cow bone
Maria Alice Prado Cechinel*, Selene Maria Arruda Guelli Ulson de Souza,
Antônio Augusto Ulson de Souza
Universidade Federal de Santa Catarina, Departamento de Engenharia Química e Engenharia de Alimentos, Centro Tecnológico, Campus Universitário, Caixa
Postal 476, CEP 88040-900 Florianópolis, Santa Catarina, Brazil

a r t i c l e i n f o a b s t r a c t

Article history: In this study, the adsorption of lead (Pb2þ) onto activated carbon (AC) originating from cow bone,
Received 15 February 2013 chemically modified with HNO3, was investigated. Physico-chemical carbon characterization assays and
Received in revised form the determination of the optimum pH conditions and contact time, as well as studies on the kinetic and
7 August 2013
isothermal equilibrium and adsorbent reuse, were carried out. The AC presented a greater amount of acid
Accepted 10 August 2013
Available online xxx
functional groups than basic groups at the surface, making it efficient for cationic exchange. The pHPZC
was 4.0 and the minimum contact time required for the assays to be performed was 6 h. It was observed
that the time required to reach kinetic equilibrium decreased with increasing initial metal concentration
Keywords:
Metal removal
in solution and the values found for qexp were 32.1, 50.1 and 42.3 mg g1 for concentrations of 100, 150
Environmental technology and 200 mg L1, respectively. The pseudo-second-order kinetic model best represented the experimental
Adsorption data for all initial lead concentrations studied, presenting good linear correlation coefficients. The
Lead Langmuir and Freundlich models were used to fit the experimental data and these showed good cor-
Activated carbon relations, with the Langmuir model providing a better description of the equilibrium (higher R2 value). It
was verified that the HCl desorption showed the highest efficiency; the minimum time to reach the
desorption equilibrium was 3 h and the recovery was approximately 50%. The proposed adsorption
process efficiently removes lead present in aqueous solution and can be used in industrial processes.
Ó 2013 Elsevier Ltd. All rights reserved.

1. Introduction resource is associated with shortages that are partly due to the
accumulated contamination of water resources over years of in-
The need for the use of water in virtually all human activities, dustrial exploitation. In recent years, the environmental organs
whether urban, rural or industrial in nature, is undeniable. How- concerned with the quality of the environment have established
ever, despite being of crucial important for human survival, this stricter environmental laws for the disposal of effluents, causing
the chemical industry to increase investment in research with a
focus on the treatment of its liquid effluents and solid wastes.
Abbreviations: Ce, concentration of adsorbate in solution at equilibrium Among the contaminants present in industrial waste, heavy
(mg L1); kF, Freundlich constant for adsorption capacity of the adsorbent (L g1); metals receive considerable attention from scientists and engineers
kL, constant for the Langmuir adsorption equilibrium (L mg1); k1, constant of the
pseudo-first-order kinetics model (min1); k2, constant of the pseudo-second-order
due to their toxic nature and the adverse effects of metals on the
kinetics model (g mg1 min1); m, mass of activated carbon (g); n, Freundlich receiving water bodies. Unlike most organic pollutants, heavy
constant for the adsorption intensity (adim.); qe, amount of metal ions adsorbed at metals are usually refractory and are not easily degraded (Sekar
equilibrium (mg g1); qexp, amount of ions adsorbed experimentally (mg g1); qm, et al., 2004). As heavy metals are not decomposed into non-toxic
effective adsorption capacity (mg g1); qt, amount of metal ions adsorbed at
end products, their concentrations should be reduced to accept-
different times (mg g1); q1, amount of metal ions adsorbed at equilibrium e
pseudo-first-order kinetics (mg g1); q2, amount of metal ions adsorbed at equi- able levels before disposal into the environment (Sulaymon et al.,
librium e pseudo-second-order kinetics (mg g1); RL, Langmuir equilibrium 2009).
parameter (adim.); R2, linear correlation coefficient (adim.); t, adsorption time (min The lead present in the wastewater of many industrial processes,
or h). such as the production of paint coatings, dyes, glass and batteries
* Corresponding author. Tel.: þ55 48 3721 5231.
E-mail addresses: maria.cechinel@posgrad.ufsc.br, maria.alice.cechinel@
(Li et al., 2010), is potentially toxic to humans and to the aquatic
hotmail.com (M.A.P. Cechinel), selene@enq.ufsc.br (S.M.ArrudaG. Ulson de Souza), environment. The main consequences in the environment are the
augusto@enq.ufsc.br (A.A. Ulson de Souza). poisoning of aquatic organisms and severe changes in the aquatic

0959-6526/$ e see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.jclepro.2013.08.020

Please cite this article in press as: Cechinel, M.A.P., et al., Study of lead (II) adsorption onto activated carbon originating from cow bone, Journal of
Cleaner Production (2013), http://dx.doi.org/10.1016/j.jclepro.2013.08.020
2 M.A.P. Cechinel et al. / Journal of Cleaner Production xxx (2013) 1e8

fauna and flora. For humans, constant exposure to lead causes preparation requires long processing steps. Al-Asheh et al. (2003)
edema, learning disabilities in children, damage to organs such as have presented results obtained for the adsorption of metals us-
the liver, kidneys and heart, and immune system disorders ing chicken feathers.
(Sreejalekshmi et al., 2009). The maximum lead discharge into Activated carbon originating from cow bone is traditionally used
receiving bodies allowed by Brazilian legislation (CONAMA, 2005) industrially to remove color from sugar (Moreno-Piraján et al.,
is 0.5 mg L1 and the current limit according to the USEPA for 2010), but its adsorbent characteristic has stimulated its use in
drinking water is 0.015 mg L1 (Momcilovic et al., 2011). several other areas, including the removal of metals present in
According to the Brazilian Ministry of Mining and Energy wastewaters. Although the use of cow bone carbon to remove metal
(Ministério de Minas e Energia, 2009), lead produced in Brazil is a ions from wastewater is still in the research phase, the potential
byproduct of zinc mining, this country lacking economically industrial use of bone carbon systems in wastewater treatment
exploitable deposits of lead at the present time. Lead production in offers good perspectives, considering the advancements made
Brazil represents 10% of the total metallic lead consumed, supplied through research on the regeneration stage and the disposal of the
largely by recycled lead. Thus, Brazil is an importer of the semi- solid waste produced.
manufactured metal. The aim of this study was to evaluate the efficiency of the
There are various techniques available for the removal of heavy adsorption of lead onto activated carbon obtained from cow bone in
metals from aqueous effluents aimed at minimizing their impact. aqueous solutions, as an alternative to conventional processes for
Chemical precipitation is the most commonly used method in large removing heavy metals aimed at adhering to Brazilian environ-
scale and requires subsequent stages of sedimentation and filtra- mental legislation. This paper presents the kinetics and equilibrium
tion before the treated water can be reused. However, for the data, and an evaluation of the ability of isothermal and kinetic
decontamination of large volumes of effluents containing metal models to describe the process behavior. Finally, data on the
ions at low concentrations the process is unsuitable because of the desorption of the adsorbed lead from the adsorbent to enable its
low efficiency and high operating costs associated with this reuse for further adsorption are reported, aimed at obtaining a
extraction process (Nerbitt and Davis, 1994). process with a lower production of residues and greater recovery of
Other methods widely used for removing heavy metals from this heavy metal.
wastewater include ion exchange, reverse osmosis, evaporation
and membrane filtration. Many of these methods have drawbacks
2. Methods
such as high costs associated with the installation, operation and
sludge disposal, and some of them are not appropriate for small-
All reagents used were of analytical grade and the solutions
scale industries (Kobya et al., 2005). Furthermore, the identifica-
were prepared with deionized water. The lead solutions were
tion of cost-effective methods for the removal of heavy metals at
prepared with 99% lead nitrate e Pb(NO3)2 (Vetec).
low concentrations represents a difficult challenge (Cordero et al.,
2004). In this regard, the adsorption process is highly effective
and economical (Fu and Wang, 2011). For this reason, the study of 2.1. Adsorbent preparation
adsorption has grown significantly in recent years, leading to
research on the development and optimization of increasingly se- The activated carbon originating from cow bone was provided
lective adsorbents. by the company BONECHAR Activated Carbon in Brazil (Maringá-
The performance of a particular adsorbent is a function of Paraná-Brazil), and is referred to as AC in this paper. The raw ma-
several factors including the pH, temperature, metal solution con- terial is exclusively bovine and underwent a physical activation
centration and surface area of the adsorbent. It is also important to process, performed at elevated temperatures (above 800  C), under
assess the desorption capacity of the material, since through this controlled conditions, providing a high surface area, formed of
process it is possible to recover the metal, which is in a concen- uniformly distributed pores classified as micro-, medium and
trated form, and restore the adsorbent for reuse, resulting in macropores.
reduced costs and waste generation. According to data provided by the company, the AC sample has
Activated carbon is currently considered as a universal adsor- large percentages of carbonate and phosphate groups. The basic
bent for removing pollutants from contaminated water due to its character of these groups decreases the potential for the adsorption
high surface area, high adsorption capacity, fast kinetics and rela- of metal ions, since acidic pH conditions in adsorption reactions
tively easy regeneration (Sathishkumar et al., 2012). Activated enhances the release of these groups, which then interact with the
carbon is a carbonaceous material with high porosity which can be metal cation. For the removal of these interferences, the acid
applied in the treatment of various wastewaters for a variety of treatment of the carbon was performed. It is essential to under-
contaminants. It is necessary, however, to research and develop stand the factors influencing the adsorption prior to modification of
activated carbons of low cost and with alternative materials for use the adsorbent in order to adapt its specific physical and chemical
in the control of water pollution (Wang et al., 2010). The ease of properties, such as surface area, pore size and the presence of
obtaining activating carbon is also a positive factor, since any ma- different surface functional groups, and increase its affinity for the
terial with a high concentration of fixed carbon can be activated, for metals present in the water (Rivera-Utrilla et al., 2011).
instance pine knots, eucalyptus, coconut bark, palm bark, fruit pips, The preparation of the AC began with the separation of the
waste oil and animal bone. desired particle sizes (30 mesh), followed by washing in distilled
Several studies have been reported on lead adsorption with water and oven drying. The AC was subjected to acid washing in
activated carbon produced from alternative materials such as 0.2 M HNO3 at a concentration of 15 g L1 in two cycles of 3 h, then
cashew nuts (SenthilKumar et al., 2012), apricot seeds (Kobya et al., washed with distilled water at pH 3.0  0.2 (QUIMIS 400M2 pH
2005), coconut shell (Sekar et al., 2004; Song et al., 2010), hazelnut meter) and oven dried The surface of the adsorbent was modified
bark (Imamoglu and Tekir, 2008), tamarind seeds (Acharya et al., with nitric acid since the oxidizing properties can be controlled by
2009), grape seeds (Al Bahri et al., 2012), tobacco waste (Kilic the temperature and acid concentration. Furthermore, there is an
et al., 2011) and rice husks (Yalçin and Sevinç, 2000; Liu et al., increase in the removal of Pb2þ by activated carbon oxidized with
2012). Research on activated carbon of animal origin is, generally, HNO3, which may be related to the cation exchange capacity being
less common than studies on materials of plant origin, since their increased by the presence of oxygenated groups (Xu and Liu, 2008).

Please cite this article in press as: Cechinel, M.A.P., et al., Study of lead (II) adsorption onto activated carbon originating from cow bone, Journal of
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M.A.P. Cechinel et al. / Journal of Cleaner Production xxx (2013) 1e8 3

2.2. Determination of surface functional groups equation of pseudo-first-order (Eq. (1)) and the linear kinetic model
of pseudo-second-order (Eq. (2)).
The methodology for determining the nature and amount of
surface functional groups of the AC was adapted from the Boehm k1 $t
logðqe  qt Þ ¼ logðq1 Þ  (1)
titration method (Boehm, 1994). For the determination of func- 2:303
tional groups, 0.2 g of AC were placed in contact with 50 mL of 0.1 M
HCl, NaOH, Na2CO3 and NaHCO3 in an orbital shaker (MARCONI t 1 t
¼ þ (2)
MA-410) for 24 h at 25  C with stirring at 120 rpm. Aliquots (10 mL) qt k2 $ðq2 Þ2 q2
were titrated with 0.1 M NaOH or HCl in triplicate. The number of
acid groups present on the surface of the solid was determined by
assuming that NaOH neutralizes carboxyl groups, lactones and 2.7. Adsorption isotherms
phenolics, Na2CO3 neutralizes carboxylic groups and lactones and
NaHCO3 only neutralizes carboxylic groups. The number of basic A mass of 0.10 g of AC was placed in contact with 50 mL of lead
sites was calculated considering the quantity of HCl that reacted solution in concentrations ranging from 25 to 400 mg L1, in a
with the adsorbent. water bath (MARCONI MA-410) at 25  C with stirring at 120 rpm.
The pH was adjusted to 4.0  0.3 (QUIMIS 400M2 pH meter) during
2.3. Determination of pH at the point of zero charge (pHPZC) the adsorption period, as determined in the previous test. The
samples were then filtered and the liquid phase was analyzed by
The methodology for determining the point of zero charge FAAS (SHIMADZU AA-6300). The amount of lead adsorbed at
(pHPZC) was adapted from that described by Regalbuto (Regalbuto equilibrium was calculated (in mg g1) and the adsorption pa-
and Robles, 2004) known as the “eleven point PZC measure- rameters were obtained through the linearization of the Langmuir
ment”. A mass of 0.025 g of adsorbent was placed in contact with (Eq. (3)) and Freundlich (Eq. (4)) models. The Langmuir equilibrium
25 mL of aqueous solution under 11 different conditions of initial parameter, RL, expresses the essential characteristics of the
pH (2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12), adjusted with solutions of 0.1 M isotherm (Eq. (5)). For RL > 1, the isotherm is of the unfavorable
NaOH or HNO3, in a bath with stirring (MARCONI MA-410) at type; RL ¼ 1 indicates a linear isotherm; for 0 < RL < 1 the
120 rpm for 24 h at 25  C. After this step, the pH of each solution isotherm is favorable; and for RL ¼ 0 the isotherm is irreversible.
was measured (QUIMIS 400M2 pH meter) and a plot of the initial
Ce 1 Ce
pH versus the final pH was obtained. The range where the pH of the ¼ þ (3)
solution remains constant is taken as the pH at the point of zero qe kL $qm qm
charge (pHPZC).
1
lnqe ¼ lnkF þ $lnCe (4)
2.4. Metal precipitation test n

The lead precipitation assays were performed with 25 mL of 1


RL ¼ (5)
250 mg L1 metal with the pH ranging between 2.0 and 10.0 (pH 1 þ kL $qm
meter QUIMIS 400M2), using solutions of 0.1 M HNO3 and NaOH.
The sample was left to stand for 24 h at ambient temperature for
decantation. After this time the samples were filtered and the liquid 2.8. Assays of lead desorption using several desorbent solutions
phase was analyzed by flame atomic absorption spectrophotometry
e FAAS (SHIMADZU AA-6300). Assays were performed in two phases:
Phase 1 e Adsorption: 0.1 g of AC was placed in contact with
2.5. Determining the equilibrium time for adsorption 50 mL of a 100 mg L1 lead solution in a bath (MARCONI MA-410)
shaken at 120 rpm and 25  C. The pH was adjusted to 4.0  0.3
A mass of 0.10 g of AC was placed in contact with 50 mL of a (QUIMIS 400M2 pH meter) during the adsorption period. The AC
solution of 100 mg L1 lead, with orbital shaking (MARCONI MA- was then collected by filtration, washed with distilled water and
410) at 120 rpm in a bath at 25  C for periods ranging from placed in an oven for 12 h at 60  C. The liquid phase was analyzed
30 min to 24 h. The pH was adjusted to 4.0  0.3 (QUIMIS 400M2 by FAAS (SHIMADZU AA-6300).
pH meter) with solutions of 0.1 M HNO3 and NaOH. Upon Phase 2 e Desorption: the dry and saturated AC was placed in
completion of the tests the samples were filtered and the liquid contact with 50 mL of 0.1 M HNO3, HCl, NaOH, H3PO4, NaCl and
phase analyzed by FAAS (SHIMADZU AA-6300). distilled water for 6 h in an agitated bath (MARCONI MA-410) at a
temperature of 25  C with stirring at 120 rpm. The liquid phase was
2.6. Adsorption kinetics studies filtered and analyzed by FAAS (SHIMADZU AA-6300). The desorbed
percentage was determined according to Equation (6). The desor-
A mass of 0.10 g of carbon was placed in contact with 50 mL of bent solution which achieved the highest percentage of lead
Pb(II) at concentrations of 100, 150 and 200 mg L1, with orbital removal from the AC was used in the adsorbent reuse tests.
shaking (MARCONI MA-410) at 120 rpm in a bath at 25  C. The pH
Amount desorbed ions
was adjusted to 4.0  0.3 (QUIMIS 400M2 pH meter) during the %Desorbed ¼  100 (6)
Amount adsorbed ions
adsorption period. The kinetics curves were obtained until reaching
the equilibrium concentration of the adsorbent-solution, with ali-
quots being taken at regular time intervals. Upon completion of the 2.9. Desorption kinetics
tests, the samples were filtered and the liquid phase was analyzed
by flame FAAS (SHIMADZU AA-6300). Lead adsorption was performed (Phase 1) and then the satu-
The pseudo-first-order and pseudo-second-order models were rated AC was placed in contact with the desorbent solution until
tested in all kinetics experiments performed and the kinetics pa- reaching the equilibrium concentration of adsorbent-solution
rameters were obtained through the Lagergren linear velocity contact, with aliquots being taken at regular time intervals. After

Please cite this article in press as: Cechinel, M.A.P., et al., Study of lead (II) adsorption onto activated carbon originating from cow bone, Journal of
Cleaner Production (2013), http://dx.doi.org/10.1016/j.jclepro.2013.08.020
4 M.A.P. Cechinel et al. / Journal of Cleaner Production xxx (2013) 1e8

the completion of the tests, the samples were filtered and the liquid
phase was analyzed by FAAS (SHIMADZU AA-6300).

2.10. Adsorbent reuse assays

The reuse assays were performed in cycles, starting with the


adsorption and ending with the desorption of the lead. After each
cycle the mass of AC was washed with distilled water and dried in
an oven at 45  C. Three cycles were conducted with the same mass
of AC.

3. Results and discussions

3.1. Determination of surface functional groups

Based on this analysis it was possible to verify the amphoteric


character of the activated carbon. This analysis is important to
verify the economic viability of using the adsorbent. If the AC has a
low amount of surface groups which promote the adsorption of
cations, a large amount of adsorbent is needed to obtain satisfac-
tory removal.
It was observed that the AC had a high acid content, notably with Fig. 1. Curve of pH at point of zero charge (pHPCZ).
the presence of carboxyl groups, which represented approximately
83% of the acid groups. The presence of carboxylic groups in large
precipitation was observed, which would modify the adsorption
quantities facilitates the adsorption process due to the cation ex-
result if such pH values were applied in the tests. This precipitation
change mechanism, where metal cations are replaced with
occurs due to Pb(II) ion association with OH-ions of the basic so-
hydrogen ions previously attacked by an acidic group. Table 1 shows
lution to form lead hydroxides. At pH < 3.0, it is possible that the
the values obtained for the surface groups. It was concluded that the
lead is present in the form of PbOHþ, even in small amounts, which
AC provided good cation exchange and therefore was a good
may explain the low precipitation in this pH range.
adsorbent for metal ions, such as lead.
Netzer and Hughes (1984) and Giraldo-Gutiérrez and Moreno-
Piraján (2008) reported an optimum pH of 4.0 for lead adsorp-
3.2. Determination of pH at the point of zero charge
tion. Kobya et al. (2005) obtained a good retention of lead in the pH
range of 3.0e6.0 and noted that at pH < 3 there was excessive
The curves in Fig. 1 show that the pHPZC is approximately 4.0. It
protonation of the carbon surface, resulting in a decrease in the
can be observed that at pH greater than 4.0 the activated carbon has
adsorption of Pb(II).
predominantly a negative charge at the surface, while below this
Considering the interference due to precipitation during the
value the surface is positively charged.
adsorption experiments with AC, the pHPZC value and the lead
In general, the pH at the point of zero charge on activated carbon
speciation diagram, the pH selected for subsequent tests in this
is close to 7.0, as shown by Babi c et al. (1999). However, this
study was 4.0  0.3. This variation is necessary as the pH control
behavior was not observed for the AC used in this study. The value
was not continuous.
obtained (4.0) can be explained by the acid treatment to which the
activated carbon was subjected prior to use, since the Hþ ions
present on the surface after treatment will be released into the
solution, lowering the pH. The adsorption of cations, such as metal
ions, is favored at pH > pHPZC, while the adsorption of anions is
favored at pH < pHPZC, due to electrostatic repulsion (Rao et al.,
2006). Thus, the lead adsorption process should be carried out at
pH equal to or greater than 4.0. To determine the optimal pH range,
the metal precipitation test was performed.

3.3. Metal precipitation test

Fig. 2 shows the lead precipitation curve obtained in the tests.


It was found that there is precipitation of the metal throughout
the pH range examined. However, at pH > 5.0 over 30%

Table 1
Concentration of surface functional groups (mEq g1).

Functional groups Concentration (mEq g1)

Basic groups 1.037  0.002


Acid groups 3.025  0.001
Carboxyl groups 2.502  0.323
Lactones 0.147  0.093
Phenolic groups 0.376  0.416 Fig. 2. Percentage of precipitated lead, after 24 h, as a function of the pH, for a Pb(II)
concentration of 250 mg L1 of Pb(II).

Please cite this article in press as: Cechinel, M.A.P., et al., Study of lead (II) adsorption onto activated carbon originating from cow bone, Journal of
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M.A.P. Cechinel et al. / Journal of Cleaner Production xxx (2013) 1e8 5

3.4. Determining the equilibrium time for adsorption

Fig. 3 shows the effect of contact time on the lead adsorption by


AC for an initial Pb concentration of 100 mg L1.
It was found that approximately 60% of the lead present in the
solution, with an initial concentration of 100 mg L1, was adsorbed
by the activated carbon in 6 h, with a maximum adsorption ca-
pacity of 32.10  0.655 mg g1. At between 6 and 24 h there was a
small variation in the concentration of lead, indicating adsorption
equilibrium. Thus, a minimum contact time of 6 h was applied in
subsequent tests.

3.5. Adsorption kinetics studies

Fig. 4 shows the adsorption kinetics for the different metal


concentrations studied: 100, 150 and 200 mg L1.
It can be observed that the time in which equilibrium is reached
decreases with increasing initial concentration of metal and the
metal concentration in the solution decreases rapidly at the
beginning of the process, resulting in a high initial rate of adsorp-
tion. This behavior is explained by the fact that the adsorption Fig. 4. Effect of different lead concentrations (100, 150 and 200 mg L1) on the Pb(II)
process is faster when the number of available adsorption sites is adsorption kinetics with modified activated carbon originating from bovine bone
much greater than the amount of metal ions that can be adsorbed (T ¼ 25  C, pH 4.0  0.3, 120 rpm and m ¼ 0.1 g).
(Netzer and Hughes, 1984). Another important feature is that the
attainment of equilibrium is due to the limited mass transfer of the
obtained by the model are in line with the qexp values, confirming
liquid solution to the outer surface of the adsorbent, followed by a
the validity of this model for the adsorption of lead onto activated
slow mass transfer inside the activated carbon particles (Acharya
carbon.
et al., 2009). Lead concentrations at equilibrium for 100, 150 and
200 mg L1 were 30.99, 61.66 and 102.28 mg L1, respectively.
Table 2 shows the values obtained for the pseudo-first-order 3.6. Adsorption isotherms
and pseudo-second-order rate constants of the adsorption kinetics.
It can be observed that the adsorption of lead onto the AC fol- Table 3 shows the values obtained for the adsorption parameters
lows the pseudo-second-order kinetics, because the values ob- of the two models studied and Fig. 5 shows the isotherms for the
tained for q1 are not significant since they do not approach the Langmuir and Freundlich models, as well as the experimental
values of qexp, while the q2 values, calculated with the pseudo- values.
second-order kinetic model, are much closer to the experimental The Langmuir model provided a higher linear correlation coef-
value for the three concentrations studied, and the R2 values are ficient (R2) compared to the Freundlich model, that is, the former
much closer to 1. provided a better fit to the experimental data. The application of
The correlation coefficient R2 shows that the pseudo-second- the Langmuir model is based on the assumption that the binding of
order model best fitted the experimental data, and the q2 values the adsorbate onto the surface of the adsorbent occurs primarily
through a chemical reaction and that all sites have equal affinity for
the metal. The Freundlich isotherm model is an empirical equation
based on adsorption onto heterogenous surfaces (Li et al., 2010).
Most assumptions related to the Langmuir model (such as
adsorption onto a homogenous surface, with an identical fixed
number of adsorption sites) are invalid for the heterogenous sur-
face of activated carbon. Thus, it is appropriate to use the Langmuir
equation for qualitative and descriptive, rather than quantitative,
purposes.
However, many authors have shown that this model can be used
to describe the equilibrium behavior of various materials, including
activated. These researchers claim that the Langmuir model is more
appropriate for describing the equilibrium data than the Freundlich
model.

Table 2
Kinetics constants of pseudo-first order and pseudo-second order for adsorption
obtained with the different metal concentrations studied.

C0 (mg L1) qexp (mg g1) Pseudo-first-order Pseudo-second-order

K1 q1 R2 K2 q2 R2

100 32.10  0.66 0.446 22.741 0.939 0.044 34.483 0.992


150 50.09  0.42 0.428 25.942 0.807 0.045 52.632 0.989
Fig. 3. Effect of contact time on adsorption of Pb(II) (for T ¼ 25  C, pH ¼ 4.0  0.3, 200 42.33  1.54 0.572 22.925 0.891 0.061 45.455 0.994
120 rpm and m ¼ 0.1 g).

Please cite this article in press as: Cechinel, M.A.P., et al., Study of lead (II) adsorption onto activated carbon originating from cow bone, Journal of
Cleaner Production (2013), http://dx.doi.org/10.1016/j.jclepro.2013.08.020
6 M.A.P. Cechinel et al. / Journal of Cleaner Production xxx (2013) 1e8

Table 3 Table 4
Values obtained for adsorption parameters of the Langmuir and Freundlich models. Comparison between adsorption capacities of several sorbents for lead (Note: A.C.:
activated carbon).
Langmuir Freundlich
Sorbent Adsorption pH C0 Reference
qm (mg g1) 47.619 kF (L g1) 8.793
capacity (mg L1)
kL (L mg1) 0.059 1/n 0.305
(mg g1)
RL 0.263 R2 0.960
R2 0.993 Cashew nut 28.90 6.0e6.5 40 Tangjuank
shells A.C. et al., 2009.
Hazelnut husk A.C. 13.05 5.7 40 Imamoglu and
Tekir, 2008.
With respect to the Langmuir equilibrium parameter (RLÞ the Coconut shell A.C. 26.50 4.5 50 Sekar et al., 2004.
value obtained was 0.263, i.e., between 0 and 1, indicating that the Apricot stone A.C. 22.85 4.0 45 Kobya et al., 2005.
isotherm is favorable. The same favorable behavior for the 1/n ratio Van apple pulp A.C. 15.96 5.0 40 Depci et al., 2012.
Polygonum 98.39 5.0 50e75 Wang et al., 2010.
of the Freundlich isotherm was not observed. orientale A.C.
Table 4 shows a comparison between the adsorption capacities Pine cone A.C. 27.53 5.0 50e200 Mom cilovi
c
of several sorbents for lead, taken from the literature. From these et al., 2011.
results, it is possible to verify that the activated carbon obtained Cow bone A.C. 32.10 4.0 100 This study.
from cow bone has a good adsorption capacity in comparison to
other sorbents.
It can be observed that the contaminant concentration in the
3.7. Assays for lead desorption using various desorbent solutions solution increases rapidly in the first half hour, with a recovery of
approximately 60%. The concentration of the remaining lead after
Fig. 6 shows the percentages of lead removal for the six different 8 h of desorption was 45.8 mg L1.
chemical agents used in this study. Table 5 shows a comparison of the percentages of lead desorbed
HCl showed the highest efficiency, with approximately 65.5% from several different types of activated carbon using a variety of
removal in 6 h, followed in decreasing order by HNO3 (57%), H3PO4 desorbent solutions, based on data available in the literature. From
(49.9%), NaOH (14.4%), NaCl (5.8%) and distilled water (3.2%). None these results, it can be observed that the methodology used is
of the solutions used caused apparent physical changes or damage satisfactory; however, the values obtained are below those re-
to the adsorbent, enabling its reuse. ported in the literature. It should be noted that the removal effi-
Based on these findings, HCl was selected as the desorption ciency could be optimized through more detailed studies on this
agent because, besides allowing greater removal and being of low process step.
cost compared to other chemicals, the acidic medium contains After 3 h there is no change in the concentration of lead
protons which, in solution, replace the metal ions adsorbed on the recovered leading to unnecessary energy expenditure in an
carbon. The opposite effect was observed in the test performed with extended assay. Thus, 3 h was adopted as the equilibrium time for
NaOH, where there was a low recovery of Pb(II). Furthermore, the the subsequent tests.
hydrochloric acid covers the surface of the activated carbon with Hþ
ions, leaving it completely protonated for the next adsorption cycle. 3.9. Assays of adsorbent reuse

Fig. 8 shows the percentages of lead adsorption onto and


3.8. Desorption kinetics
desorption from the activated carbon originating from bovine bone
for three cycles.
Fig. 7 shows the data obtained experimentally and the kinetics
For the first cycle 82% adsorption and 52% desorption were
for the desorption of the lead adsorbed on AC using HCl as the
obtained with respect to the value of the initial concentration in the
desorbing agent.

Fig. 6. Lead desorption from activated carbon using several desorbent chemical agents
Fig. 5. Langmuir and Freundlich models for the lead adsorption isotherm. (T ¼ 25  C, 120 rpm and m ¼ 0.1 g).

Please cite this article in press as: Cechinel, M.A.P., et al., Study of lead (II) adsorption onto activated carbon originating from cow bone, Journal of
Cleaner Production (2013), http://dx.doi.org/10.1016/j.jclepro.2013.08.020
M.A.P. Cechinel et al. / Journal of Cleaner Production xxx (2013) 1e8 7

Table 5
Comparison of lead desorption percentages of several sorbents using HCl (Note: A.C.:
activated carbon).

Sorbent Desorption Reference

Coconut shell A.C. 75% Sekar et al., 2004.


Polygonum orientale A.C. 77% Wang et al., 2010.
Modified spent grain A.C. 86% Li et al., 2009.
A.C. Cloths 80e100% Kadirvelu et al., 2000.
Cow bone A.C. 60% This study.

functional groups, in particular carboxylic groups, which are facil-


itators of the adsorption and desorption processes.
It was verified that the solution pH is a highly important factor
in the lead adsorption onto AC, and at pH > 6.0 the precipitation of
metal hydroxides is the predominant process in the system, which
inhibits the quantification of the adsorption. The chemical treat-
ment promoted a decrease in the pHpcz to around 4.0, which was
determined as ideal for the experiments.
The minimum contact time for the adsorption equilibrium was
6 h and for a constant AC mass an increase in the initial concen-
Fig. 7. Desorption kinetics for lead adsorbed onto modified activated carbon origi- tration of the solution reduces the contact time required to reach
nating from bovine bone (T ¼ 25  C, 120 rpm and m ¼ 0.1 g). equilibrium. However, the time determined is valid only for this
system. On modifying, for instance, the mass, temperature and/or
agitation conditions, this time should be re-determined and,
solution (100 mg L1). For the second and third cycles 65% and 54%
therefore, this is not a good parameter for determining whether or
for adsorption and 54% and 45% for desorption, respectively, were
not the process is viable.
obtained. The decrease in the adsorption capacity of approximately
The pseudo-second-order kinetic model best represented the
27% may be the result of the cumulative effect of the incomplete
experimental kinetics data for all concentrations studied, providing
desorption process. The lead recovery remained constant, at around
good linear correlation coefficients. The kinetic study allowed it to
50%, thus it may be necessary to use an acid solution with a higher
be verified that the rate of the initial adsorption process is high.
concentration or a larger volume of desorbent solution.
The adsorption isotherms studied had a good fit to the experi-
With a view to attaining sustainable development, the lead ions
mental data and, therefore, described with good accuracy the
desorbed from the activated carbon could be recycled and returned
thermodynamic equilibrium of the studied system. The Langmuir
to factories as a raw material, rather than being deposited in san-
model showed the highest linear correlation coefficient and better
itary landfills as waste. One of the processes available for achieving
described the system equilibrium. The Langmuir isotherm for the
this recovery is electrolysis, which can be applied to transform lead
adsorption of lead was favorable, which was not observed with the
ions into elemental lead on the stainless steel electrode surface.
Freundlich isotherm.
It was found that 0.1 M HCl was the most efficient solution for
4. Conclusions the desorption of lead from the saturated AC. The minimum time
for the desorption equilibrium to be reached was 3 h, showing a
The results of this research showed that chemical modification recovery of approximately 60% in the first half hour. The initial rate
with HNO3 removed the impurities on the surface of activated of desorption is fast, and the subsequent low lead recovery rate
carbon obtained from cow bone and increased the amount of acid could be due to the saturation of the desorbent solution. The
adsorption capacity of the AC decreased by approximately 27%
between the first and third cycles of reuse. The metal recovery
remained constant at around 50% in all cycles.
In general, the AC demonstrated good lead removal efficiency,
and is potentially a new alternative for the removal and this metal
from contaminated effluents allowing its subsequent reuse.

Acknowledgments

The authors are grateful to ANP/MECPETRO for financial support


and UFSC/LABSIN-LABMASSA for the infrastructure provided for
this study.

References

Acharya, J., Sahu, J.N., Mohanty, C.R., Meikap, B.C., 2009. Removal of lead(II) from
wastewater by activated carbon developed from Tamarind wood by zinc chlo-
ride activation. Chem. Eng. J. 149 (1e3), 249e262.
Al Bahri, M., Calvo, L., Gilarranz, M.A., Rodriguez, J.J., 2012. Activated carbon from
grape seeds upon chemical activation with phosphoric acid: application to the
adsorption of diuron from water. Chem. Eng. J. 203 (1), 348e356.
Fig. 8. Percentage of lead adsorbed-desorbed per cycle (T ¼ 25  C, 120 rpm and Al-Asheh, S., Banat, F., Al-Rousan, D., 2003. Beneficial reuse of chicken feathers in
m ¼ 0.1 g). removal of heavy metals from wastewater. J. Clean. Prod. 11 (3), 321e326.

Please cite this article in press as: Cechinel, M.A.P., et al., Study of lead (II) adsorption onto activated carbon originating from cow bone, Journal of
Cleaner Production (2013), http://dx.doi.org/10.1016/j.jclepro.2013.08.020
8 M.A.P. Cechinel et al. / Journal of Cleaner Production xxx (2013) 1e8

Babi c, B.M., Milonjic, S.K., Polovina, M.J., Kaludierovi c, B.V., 1999. Point of zero Nerbitt, C.C., Davis, T.E., 1994. Removal of heavy metals from metallurgical effluents
charge and intrinsic equilibrium constants of activated carbon cloth. Carbon 37 by the simultaneous precipitation and flotation of metal sulfides using column
(3), 477e481. cells. In: Extraction and Processing for the Treatment and Minimization of
Boehm, H.P., 1994. Some aspects of the surface chemistry of carbon blacks and other Waste. The Mineral, Metals and Materials Society, Pennsylvania, USA, p. 331.
carbons. Carbon 32 (5), 759e769. Netzer, A., Hughes, D.E., 1984. Adsorption of copper, lead and cobalt by activated
CONAMA, 2005. Federal Regulation n 357. Brazil. Retrieved July 15, 2013, from carbon. Water Res. 18 (8), 927e933.
www.mma.gov.br/port/conama/res/res05/res35705.pdf. Rao, M.M., Ramesh, A., Rao, G.P.C., Seshaiah, K., 2006. Removal of copper and cad-
Cordero, B., Lodeiro, P., Herrero, R., Sastre de Vicente, M.E., 2004. Biosorption of mium from the aqueous solutions by activated carbon derived from Ceiba
Cadmium by Fucus spiralis. Environ. Chem. 1 (3), 180e187. pentandra hulls. J. Hazard. Mater. 129 (1e3), 123e129.
Depci, T., Kul, A.R., Önal, Y., 2012. Competitive adsorption of lead and zinc from Regalbuto, J.R., Robles, J.O., 2004. The Engineering of Pt/Carbon Catalyst Preparation.
aqueous solution on activated carbon prepared from Van apple pulp: study in For Application on Proton Exchange Fuel Cell Membrane (PEFCM). University of
single-and multi-solute systems. Chem. Eng. J. 200e202, 224e236. Illinois at Chicago, USA. REU 2004 Summer Program. Final Report.
Fu, F., Wang, Q., 2011. Removal of heavy metal ions from wastewaters: a review. Rivera-Utrilla, J., Sánchez-Polo, M., Gómez-Serrano, V., Álvarez, P.M., Alvim-
J. Environ. Manage. 92 (3), 407e418. Ferraz, M.C.M., Dias, J.M., 2011. Activated carbon modifications to enhance
Giraldo-Gutiérrez, L., Moreno-Piraján, J.C., 2008. Pb(II) and Cr(VI) adsorption from its water treatment applications. An overview. J. Hazard. Mater. 187 (1e3),
aqueous solution on activated carbons obtained from sugar cane husk and 1e23.
sawdust. J. Anal. Appl. Pyrolysis 81 (2), 278e284. Sathishkumar, P., Arulkumar, M., Palvannan, T., 2012. Utilization of agro-industrial
Imamoglu, M., Tekir, O., 2008. Removal of copper (II) and lead (II) ions from aqueous waste Jatropha curcas pods as an activated carbon for the adsorption of reac-
solutions by adsorption on activated carbon from a new precursor hazelnut tive dye Remazol Brilliant Blue R (RBBR). J. Clean. Prod. 22 (1), 67e75.
husks. Desalination 228 (1e3), 108e113. Sekar, M., Sakthi, V., Rengaraj, S., 2004. Kinetics and equilibrium adsorption study of
Kadirvelu, K., Faur-Brasquet, C., Le Cloirec, P., 2000. Removal of Cu(II), Pb(II), and lead(II) onto activated carbon prepared from coconut shell. J. Colloid Interface
Ni(II) by adsorption onto activated carbon cloths. Langmuir 16 (22), 8404e Sci. 279 (2), 307e313.
8409. SenthilKumar, P., Ramalingam, S., Abhinaya, R.V., Dinesh Kirupha, S., Vidhyadevi, T.,
Kilic, M., Apaydin-Varol, E., Putun, A.E., 2011. Adsorptive removal of phenol from Sivanesan, S., 2012. Adsorption equilibrium, thermodynamics, kinetics, mech-
aqueous solutions on activated carbon prepared from tobacco residues: equi- anism and process design of zinc(II) ions onto cashew nut shell. Can. J. Chem.
librium, kinetics and thermodynamics. J. Hazard. Mater. 189 (1e2), 397e403. Eng. 90 (4), 973e982.
Kobya, M., Demirbas, E., Senturk, E., Ince, M., 2005. Adsorption of heavy metal ions Song, X., Liu, H., Cheng, L., Qu, Y., 2010. Surface modification of coconut-based
from aqueous solutions by activated carbon prepared from apricot stone. Bio- activated carbon by liquid-phase oxidation and its effects on lead ion adsorp-
resour. Technol. 96 (13), 1518e1521. tion. Desalination 255 (1e3), 78e83.
Li, Q., Chai, L., Zhao, J., Yang, Z., Wang, Q., 2009. Lead desorption from modified Sreejalekshmi, K.G., Krishnan, K.A., Anirudhan, T.S., 2009. Adsorption of Pb(II) and
spent grain. Trans. Nonferrous Met. Soc. China 19 (5), 1371e1376. Pb(II)-citric acid on sawdust activated carbon: kinetic and equilibrium isotherm
Li, K., Zheng, Z., Li, Y., 2010. Characterization and lead adsorption properties of studies. J. Hazard. Mater. 161 (2e3), 1506e1513.
activated carbons prepared from cotton stalk by one-step H3PO4 activation. Sulaymon, A.H., Abid, B.A., Al-Najar, J.A., 2009. Removal of lead copper chromium
J. Hazard. Mater. 181 (1e3), 440e447. and cobalt ions onto granular activated carbon in batch and fixed-bed ad-
Liu, Y., Guo, Y., Gao, W., Wang, Z., Ma, Y., Wang, Z., 2012. Simultaneous preparation sorbers. Chem. Eng. J. 155 (3), 647e653.
of silica and activated carbon from rice husk ash. J. Clean. Prod. 32, 204e209. Tangjuank, S., Insuk, N., Tontrakoon, J., Udeye, V., 2009. Adsorption of Lead(II) and
Ministério de Minas e Energia, 2009. Brazilian Ministry of Mining and Energy. Cadmium(II) ions from aqueous solutions by adsorption on activated carbon
Technical Report 26: Profile of Lead Ore. Brazil. Retrieved July 15, 2013, from prepared from cashew nut shells. World Acad. Sci. Eng. Technol. 52 (28), 110e
www.mme.gov.br/sgm/galerias/arquivos/plano_duo_decenal/a_mineracao_ 116.
brasileira/P17_RT26_Perfil_do_Minxrio_de_Chumbo.pdf_Perfil_do_Minxrio_ Wang, L., Zhang, J., Zhao, R., Li, Y., Li, C., Zhang, C., 2010. Adsorption of Pb(II) on
de_Chumbo.pdf. activated carbon prepared from Polygonum orientale Linn.: kinetics, isotherms,
Mom cilovi
c, M., Purenovic, M., Boji
c, A., Zarubica, A., RanCelovic, M., 2011. Removal pH, and ionic strength studies. Bioresour. Technol. 101 (15), 5808e5814.
of lead(II) ions from aqueous solutions by adsorption onto pine cone activated Xu, T., Liu, X., 2008. Peanut shell activated carbon: characterization, surface
carbon. Desalination 276 (1e3), 53e59. modification and adsorption of Pb2þ from aqueous solution. Chin. J. Chem. Eng.
Moreno-Piraján, J.C., Gómez-Cruz, R., García-Cuello, V.S., Giraldo, L., 2010. Binary 16 (3), 401e406.
system Cu(II)/Pb(II) adsorption on activated carbon obtained by pyrolysis of Yalçın, N., Sevinç, V., 2000. Studies of the surface area and porosity of activated
cow bone study. J. Anal. Appl. Pyrolysis 89 (1), 122e128. carbons prepared from rice husks. Carbon 38 (14), 1943e1945.

Please cite this article in press as: Cechinel, M.A.P., et al., Study of lead (II) adsorption onto activated carbon originating from cow bone, Journal of
Cleaner Production (2013), http://dx.doi.org/10.1016/j.jclepro.2013.08.020