Groundwater for Sustainable Development 7 (2018) 348–358

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Groundwater for Sustainable Development

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Research paper

pH dependent leachings of some trace metals and metalloid species from T

lead smelter slag and their fate in natural geochemical environment
⁎
Nabajyoti Saikiaa, , Rashmi Rekha Boraha, Kaberijyoti Konwara, Carlo Vandecasteleeb
a
Department of Chemistry, The Assam Kaziranga University, Jorhat 785006, Assam, India
b
Department of Chemical Engineering, Katholieke Universiteit Leuven, Willem de Croylaan 46, 3001 Leuven, Belgium

A R T I C L E I N F O A B S T R A C T

Keywords: The influence of pH on the leaching behaviours of As, Cd, Cu, Mo, Ni, Pb, Se and Zn from a lead smelter slag was
Lead smelter slag assessed to understand the ground water pollution potential of slag and the toxicity in geo-environmental
Heavy metals conditions. Leaching of slag was investigated by using European EN 12457-2 and prEN 14429 leaching tests. The
pH dependent leaching results obtained from prEN 14429 leaching test were used to determine the acid neutralization capacity (ANC) of
Water pollution
slag. The pH dependent leaching results were further assessed by considering existing geo-chemical modeling
Waste management
results of similar types of wastes. Results indicate that the concentrations of some toxic metal and metalloid
species in the leachate are higher than their specified limits prescribed for safe landfill disposal as inert or non-
reactive hazardous solid waste as well as for safe disposal of effluent in inland surface water. The ANC values
obtained for slag at pH values 7, 5 and 4 are 0.75 meqv/g, 3.72 meqv/g and 37.30 meqv/g respectively. The low
ANC values as well as the high concentrations of majority of the toxic elements in leachates especially at the pH
range of 5–7 indicate hazardous nature of slag for disposal under open atmosphere. The leaching behaviours of
iron and calcium under varying pH conditions have profound effect on the pH dependent mobilities of most of
the trace elements present in the slag. The sodium, potassium and chloride leaching from slag particularly in the
pH range of 4–12 are pH independent and therefore do not have any effect on the mobilities of toxic elements.

1. Introduction treatment or use of slag as raw materials in road construction and as

Various types of solid wastes are generated from municipalities and
several industrial processes. These wastes are categorized based on
their properties such as material types, hazard potentials or based on
their origins e.g. organic, inorganic. Considering hazard potentials,
these wastes can be classified into two types: inert, e.g. glass bottles,
excavated soil, building and demolition waste, and hazardous waste
with high concentrations of heavy metals and toxic organic compounds
such as nonferrous slags, fly ash and APC residue generated in muni-
cipality solid waste incineration plants. However, regardless of the
type, hazard potential or origin, the effective managements of solid
wastes are important tasks for an environmentally sound society.
Recycling as construction materials and land filling after detoxification
are the major management options for these wastes (Mitchell et al.,
1992; Chandler et al., 1997).
Ferrous and non-ferrous industries are among the most important
producers of solid wastes such as metallurgical slag, wastes from air
pollution control technology applied in these industries, and various
sludges produced from blast furnaces. The disposal of slag after
aggregates in concrete preparations is the major management options of
these slags (Hughes and Halliburton, 1973; Vegas et al., 2008;
Penpolcharoen, 2005; Morrison et al., 2003; Atzeni et al., 1996; Saikia
et al., 2008, 2012). Despite the substantial amounts of slags are gen-
erated from non-ferrous metal (Pb, Zn, Cu, Ni and Cr) processing in-
dustries, very less numbers of studies are so far conducted to use non-
ferrous slags as raw materials in concrete production or in road
construction. On the other hand, slags and other wastes generated from
iron processing industries are widely used in cement and concrete
productions. The presence of elevated levels of toxic elements like As,
Cd, Pb and Se may be the major reason for not considering these slags
as secondary materials in various infrastructure activities.
The Pb- and Zn-slags are produced during pyro-metallurgical
treatment of sulfide ores. Most of the pyro-metallurgical wastes or
metal smelter slags are dispersed in open environment or used in road
constructions without any treatment (Barna et al., 2004; Jin et al.,
2014). The natural weathering of slag stored in slag heap can change
the mineralogy of slag (Sobanska et al., 2016). The release of toxic
elements from slags upon contact with acidic rain water can pollute the

⁎
Corresponding author.
E-mail addresses: saikianj@gmail.com, nabajyoti@kazirangauniversity.in (N. Saikia).

https://doi.org/10.1016/j.gsd.2018.01.009
Received 31 July 2017; Received in revised form 9 January 2018; Accepted 29 January 2018
Available online 01 February 2018
2352-801X/ © 2018 Elsevier B.V. All rights reserved.
N. Saikia et al.
soil as well as surface and ground water of nearby locality (Lewis, 1992;
Sobanska et al., 2000; Reuter et al., 2004). The greatest concentrations
of contaminant metal and metalloid species generated from nonferrous
metal smelters normally observe on the nearby soil surface of slag
disposal sites (Ettler, 2016). High concentrations of some toxic elements
such as Cd, Cu, Pb and Zn in the ground water of nearby locality of slag
disposal site due to the downward migrations of toxic metal and me-
talloid species from surface soil were also reported (de Andrade Lima
and Bernardez, 2013; Ettler, 2016). Many studies indicated that the
people leaving nearby locality of non-ferrous slag dumping sites were
affected by the toxic trace metals such as As, Cd, Cu, Pb, Zn (de Andrade
Lima and Bernardez, 2013, 2017; Carvalho et al., 2003; Ettler, 2016).
The leaching behaviours of majority of toxic elements are depen-
dent on the various physico-chemical properties of waste materials.
Different types of leaching tests are normally performed to assess the
toxicities of wastes in landfill or other disposal conditions. Leaching
tests are also performed to assess the potential risks of a waste to human
health and/or ground water (Tiwari et al., 2015). These include some
regulatory tests to evaluate the materials for specific use or disposal
scenarios. All the leaching tests are classified into two classes: batch or
static and dynamic leaching tests. In batch leaching test the size re-
duced waste is mixed with definite volume of leaching solutions and
agitated the mixture for a short period of time, typically for a few hours
or for a day. Leaching test such as European EN 12457-2 or DIN test, EN
12457-3 and American toxicity characteristic leaching procedure
(TCLP) test are the examples of regulatory batch leaching tests. The
results obtained from these types of tests are compared with specified
listed values and therefore can be used to classify wastes according to
classification types i.e. hazardous or inert. The major objective of such
regulatory specification is to prevent or reduce the negative impacts on
the environment, in particular on soil, surface water, groundwater, and
on human health from the landfilling of waste by introducing stringent
technical requirements for waste and landfills. In dynamic leaching test,
the leachate solution is renewed after a period and continued for long
term. Tests such as European prEN 14429 test and lysimeter or column
tests are the examples of dynamic leaching tests. In these tests, the
leaching solution is under continuous flux and therefore represents the
field conditions.
One of the important factors influencing the releases of con-
taminants from waste materials during leaching evaluations is pH
(Eighmy et al., 1995; Kosson et al., 2002; Krol and Mizerna, 2016;
Vitkova et al., 2009). The solubility of a species from waste materials as
well as the formations and precipitations of secondary minerals having
contaminant species leached from wastes are normally pH dependent.
In other words, the stability of a species in water or liquid medium can
be directly related with the pH of aqueous medium and therefore the
leaching behaviours of contaminant species from a waste is reflected by
the pH dependence. The pH dependence leaching behaviour of a waste
thus provides information that can help to understand the fate and
behaviour of a contaminant species in geo-environmental conditions.
Such results are often more useful than the results obtained from the
analysis of total elemental composition or results obtained from simple
batch leaching tests such as TCLP test for assessing the environmental
impacts as well as for determining the suitable management options of
waste materials (Jarošíková et al., 2017).
The pH of leachates generated in leaching experiments is controlled
by a number of factors, e.g. dissolution of atmospheric CO2, dissolution
of minerals from wastes and secondary mineral formations. To evaluate
the pH effect on metal leaching, a pH dependent static leaching test is
commonly performed over a wide range of pH (Tiwari et al., 2015;
Kosson et al., 2002). This type of leaching test also provides information
related to the potential buffering capacity of a waste material. The test
can also be used to evaluate the acid neutralization capacity of a waste
(Cappuyns and Swennen, 2008). Additional information can be ob-
tained by combining the pH dependent leaching results and geochem-
ical modeling and therefore such combination is a powerful tool to
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Groundwater for Sustainable Development 7 (2018) 348–358
understand the solid phase speciations and reactivities of toxic metal or
metalloid species in soils, sediments and waste materials (Quina et al.,
2009).
Numerous studies have been done to understand the leaching be-
haviours of several types of waste materials using various types of
leaching methodologies (Astrup et al., 2006; Cappuyns et al., 2014;
Cornelis et al., 2011; Dijkstra et al., 2006, 2008; Eighmy et al., 1995;
Engstrom, 2010; Jarošíková et al., 2017; Potysz, 2016; Quina et al.,
2009; Vitkova et al., 2009; Vitkova et al., 2013). The leaching results so
far obtained for various non-ferrous slags indicate that the majority of
the trace elements leached from slags occur at low or high pH regions
and the concentrations at natural pH regions are normally low
(Cappuyns et al., 2014; Cornelis et al., 2011; Jarošíková et al., 2017;
Potysz, 2016; Yin et al., 2016). Factors such as minerals present in slag
and atmospheric oxidative conditions during pH dependence leaching
tests controls the leachings of various elements or chemical species
from lead blast furnace slag and imperial smelting furnace slag
(Cappuyns et al., 2014; Yin et al., 2016). The geo-chemical modeling of
the results obtained from pH dependence leaching test coupled with the
mineralogical compositions of wastes and their residues obtained after
pH dependence leaching tests is a powerful tool for understanding the
involved chemical processes during leaching (Schindler et al., 2000;
Meima and Comans, 1998a; Hyks et al., 2009; Astrup et al., 2006;
Dijkstra et al., 2006, 2008; Quina et al., 2009; Cornelis et al., 2011;
Cappuyns et al., 2014). Such information can be used for assessing
environmental impact of waste materials as well (Quina et al., 2009;
Potysz, 2016; Yin et al., 2016). From the analysis of pH dependence
leaching results of a MSWI ash using geo-chemical modeling software,
Hyks et al. (2009) classified elements as availability controlled, solu-
bility controlled and complexation/sorption controlled. Quina et al.
(2009) used the available geo-chemical modeling results of pH depen-
dent leaching data of similar types of waste materials to explain the pH
dependence leaching behaviour of MSWI fly ash. Cornelis et al. (2009)
observed some striking similarities of some properties among the var-
ious types of wastes such as non-ferrous slags, MSWI bottom ash, and
APC residues (Cornelis et al., 2009).
Smelting of Pb in a blast furnace located nearby area of Antwerp,
Belgium generates large amounts of slag. The dumping of this slag in
the vicinity of smelter site is an environmental threat due to presence of
very high amounts of some metal and metalloid species. The disposal or
utilizations of lead slag in construction purposes are considered as the
major sources of toxic elements such as As, Cu, Pb, Zn present in the soil
as well as the surface and groundwater of nearby locality (Carvalho
et al., 2003; Sobanska et al., 2000). Therefore a thorough environ-
mental characterization procedure is necessary before considerations of
Pb-slag for recycling or land-filling purposes. In our previous in-
vestigation, a Pb-smelter slag was considered as a partial substitution of
sand fraction in the preparation of cement mortar (Saikia et al., 2008,
2012). The slag met the required physical and mechanical properties for
application as a partial substitution of sand fraction in cement mortar
preparation. However the leaching assessments of slag containing ce-
ment mortar samples by EN12457-2 leaching test indicated that the
concentrations of Cu, Pb and Zn in the leachate were higher than the
specified limit for recycling as construction materials. Similarly, sub-
stantial amounts of Cu, Pb, and Zn were liberated when the slag con-
taining cement mortars were subjected to NEN 7345 leaching test
(Saikia et al., 2012).
Considering the toxicity of Pb-smelter slag as well as the importance
of leaching tests in evaluating environmental impacts of wastes and
other toxic materials on the soil, surface water, and groundwater, in
this investigation, the leaching behaviours of a Pb-smelter slag was
assessed using various standard leaching tests. The toxicity of lead slag
was first evaluated by using a regulatory European short term batch
leaching test. The pH dependent leaching curves of some toxic metal
and metalloid species were eventually determined under anoxic con-
dition by using a pH static test. The interpretation of the pH dependent
N. Saikia et al.
leaching results of toxic elements were done by using existing geo-
chemical modeling results, reported for similar types of wastes. It is
envisaged that the leaching results presented in this work will be
helpful for environmental impacts assessments and risk analyses of si-
milar types of wastes too.
2. Materials and methods
2.1. Materials
The metallurgical slag used in this investigation was a residue ob-
tained from a lead blast furnace, located in the nearby area of Antwerp,
Belgium. After separation from the bullion, the slag was cooled down
and broken into finer particles. The slag used in this study was a very
hard and black-coloured granular material having diameter in the range
of 0–4 mm. All the chemicals used in this investigation were ultrapure
grade. The ultrapure, double distilled, deionized Milli-Q water with a
very low conductance value was used during the investigation.
2.2. Characterization of slag
2.2.1. Determination of chemical compositions of slag
The SiO2, SO42-, PO43- and Cl− contents in the slag were determined
by using standard gravimetric methods (Vogel, 1961). The sulfates,
chlorides and phosphates were precipitated as BaSO4, AgCl and
MgNH4PO4·6H2O respectively. The total contents of other major and
minor elements present in slag were determined by using an inductively
coupled plasma mass spectrophotometer (ICP-MS; Thermo Elemental, X
Series). Similar procedures as described in our previous communication
were used to prepare samples (Saikia et al., 2008). The liquid sample of
the slag necessary for ICP-MS analyses was generated by acid digestion
method using HNO3, HClO4 and HF acids. The concentrations obtained
(g/L) for most abundant species were converted into the weight per-
centages of the most abundant oxides. For determining pH of slag, a
solid-liquid mixture was prepared by shaking 3 g of powdered slag with
30 mL of water for 24 h using a magnetic stirrer. The results presented
in this work are the average values of three measurements.
2.2.2. Identification of minerals
To identify the major crystalline components in the slag, the X-ray
diffraction pattern of slag was recorded using a Philips PW 1830 dif-
fractometer, equipped with a graphite monochromator and a gas pro-
portional detector and using Cu Kα radiation. Minerals present in slag
were identified using the Diffract Plus software employing the ICDP
PDF-2 database.
2.3. Leaching tests
The leaching behaviour of slag was evaluated at 25 °C by using
European standard regulatory leaching test, EN 12457-2 (Saikia et al.,
2008). The EN 12457–2 leaching test is a single step batch leaching test
where water is used as a leaching solution. The leaching is done at room
temperature by using end-over-end agitation method with 24 h agita-
tion time. The liquid to solid ratio is maintained at 10. No clear defi-
nition is imposed on the particle size but the diameter of the particle
must be less than 4 mm. Accordingly, 15 g of powdered slag sample was
mixed with 150 mL distilled deionized water in 250 mL plastic bottle.
The mixture was then agitated by using an electrical shaker for 24 h.
The prEN 14429 leaching test was used to identify the leaching beha-
viour of slag under certain pH conditions. The test consists of a set of
parallel batch extractions of the sample at liquid to solid ratio of 10
(mL g−1) in closed plastic containers. In this investigation, about 15 g
samples were mixed with 150 mL aqueous solutions with increasing
quantities of HNO3 and NaOH/KOH solutions in 250 mL plastic con-
tainers and agitated for 72 h using an electrical shaker.
The agitation was done in a thermostatic chamber to keep the
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Groundwater for Sustainable Development 7 (2018) 348–358
shaking temperature at 20 °C. After completion of agitation i.e. leaching
process, the slag-aqueous solution mixtures were separated into two
portions: a portion of the solution was used for determining the pH and
conductivity and other portion was used for elemental analysis. All the
leaching experiments were done by using flat bottom horizontal shaker
with 145 rpm shaking frequency.
For analyzing elemental concentrations, about 100 mL of the lea-
chate was filtered through a 0.45 m membrane filter and separated into
two equal volume fractions. A fraction was acidified with 1 mL of 65%
HNO3 acid to bring the pH < 2 and kept to analyze the cations by ICP-
MS. The other fraction was directly used for analyzing the oxyanions of
As, Mo, Sb, Se and V by ICP-MS and sulfate and chloride by ion-chro-
matography. All the samples were kept in a refrigerator until analyses.
2.4. Analysis of elemental compositions of digested slag solution and
leachates
2.4.1. Inductively coupled plasma mass spectrophotometric analysis
The concentrations of cationic and other anionic species including
silica were determined by inductively coupled plasma mass spectro-
photometry (ICP-MS). For each elemental species, the average of total
six determinations was reported in this investigation. Moreover, to
obtain high quality data from the leaching test, several precautionary
measures were taken during whole experimental period. In all the
measurements done by ICP-MS analysis, ultrapure multi elemental
freshly prepared standard solutions with appropriate concentrations
were used for calibrations and 115In was used as an internal standard.
Adequate numbers of blank and standard solutions were used and ca-
libration was occasionally done for getting high quality data. The
flushing of rinse blank solution and nebulization of samples were done
prior to the analysis of sample until a steady state signal was achieved.
2.4.2. Ion chromatographic determinations of sulfate and chloride
The concentrations of sulfate and chloride in the leachates were
measured by a reagent-free ion-chromatography system with eluent
regeneration (RFIC-ER), model Dionex ICS 2000. The system can
measure liquid samples containing very low amounts of anions e.g.
5 ppb bromate in drinking water. Less-frequent eluent preparation re-
duces unintentional variations in the concentrations of anions, and
therefore increases the reliability and reproducibility during measure-
ments. During measurements, adequate numbers of blank and standard
solutions were used and calibration was occasionally done for getting
high quality data. For each anionic species, the average of three de-
terminations was reported.
3. Results and discussion
3.1. Chemical and mineralogical properties
The major and minor elements presents in slag are presented in
Table 1. The major oxides present in slag are the calcium oxide, iron
oxide, and silica. The combined content of these three oxides is about
90% of total oxides present in slag. The slag also contains very high
amounts of ZnO (5.01%) and PbO (2.47%), CuO (0.421%) along with
considerable amounts of As, Sb, Cr, V and Se.
The XRD pattern of slag is presented in Fig. 1. The minerals iden-
tified from the XRD patterns are presented in Table 2. The detail dis-
cussion about the mineralogical composition of slag was already pre-
sented in another publication (Saikia et al., 2008). Slag contains
calcium iron silicates (kirschstenite) and calcium zinc silicates (hard-
ystonite-akermanite) as the major minerals with substantial amounts of
sphalerite (zinc sulfide) and wuestite (FeO). The presence of consider-
able amounts of sulfide and wuestite in the slag indicates that the Pb-
slag was formed under reducing condition (Erb-Satullo et al., 2014).
The XRD analysis detects several Zn containing crystalline minerals
in slag whereas no Pb-containing crystalline minerals are present in the
N. Saikia et al. Groundwater for Sustainable Development 7 (2018) 348–358

Table 1 Zn also present as metallic inclusions or in pure metallic states (Ettler

Major element (in oxide) and minor elements compositions of slag. et al., 2001).
Major Elements
3.2. Analysis using EN 12457–2 leaching test
Oxide Amount (%) Oxide Amount (%)
The concentrations of some elements in the leachate obtained from
Al2O3 5.4 BaO 0.84
slag powder after application of European standard EN 12457–2
CaO 18.9 Fe2O3 34.0
K2O 0.31 MgO 1.4 leaching test along with the limit values specified in various standards
MnO2 0.66 Na2O 0.87 are presented in Table 3. The results were already discussed in another
SiO2 25.7 SnO2 0.50 communication considering the Flemish NEN 7343 leaching limit va-
Cl¯ nd PO43- 1.2 lues for recycling as a granular construction material (Saikia et al.,
SO42- 1.2 Other 1.2
2008). Therefore the comparisons of results with such standard will not
LOD 2.5 LOI* +4.0
Minor Elements be considered in this investigation. However, the pollution potential of
Elements Amount (mg/kg) Elements Amount (mg/kg) slag is further assessed by comparing the leaching results with a na-
Pb 22,412 As 4200 tional standard specification for drinking water, standard for disposal of
Se 292 Cr 1001
effluents of municipal solid wastes in inland surface water and the
Mo 279 Cu 3236
Zn 39,169 Sb 3077 European standard specifications for landfill acceptance criteria.
Cd 5.8 Ni 416 It should be mentioned here that the tests such as lysimeter or
V 805 pH 10.6 column leaching tests are more appropriate for comparing leaching
results with the drinking water standards than the results obtained from
* + indicates weight increases due to heating.
batch leaching tests such as EN 12457–2 leaching test. This is because
of the fact that a fraction of trace elements present in leachates are
normally absorbed by the mineral surfaces during transportation of
leachates through the soil layers. Such processes can reduce the con-
centrations of trace elements in the leachates. Therefore the data ob-
tained from batch leaching tests such as EN 12457–2 leaching test may
not be appropriate to assess the toxicity of waste leachate considering
drinking water standards. The EN 12457–2 leaching test is normally
performed to classify the waste according to European landfilled di-
rective and to determine the reusability potential of a solid waste for
construction purposes. Although there are some limitations, leaching
results obtained from batch leaching tests such as synthetic precipita-
tion leaching procedure (SPLP) are occasionally compared with
drinking water standards for assessing the trace element leaching po-
tentials of waste materials (Legret et al., 2005; Townsend et al., 2003).
Izquierdo et al. (2005) obtained comparable leaching results for various
Fig. 1. XRD pattern of slag. trace elements when MSWI bottom ash to be used as an unbound
granular material for road pavements was subjected to EN 12457–2
leaching test and a column type field leaching test.
Table 2
Minerals identified in slag. Table 3 indicates that the concentrations of Al, As, Mo, Ni, Se and Pb
in the leachate generated from slag cross the standard specified limits
Mineral Name Chemical Formula Abundance Symbols prescribed for drinking water. Similarly Se and Pb concentrations in the
leachate along with the pH of leachates do not meet the specified limits
Anorthite CaAl12Si2O8 (X) An
Hardystonite-Akermanite Ca2(Mg,Zn)Si2O7 XXX Hd
set for the respective elements for safe disposal of waste effluents in
Kirschstenite CaFeSiO4 XXX K inland surface water. The concentrations of Se and Pb in the leachates
Lrrnite β-CaSiO3 (X) L do not meet the European landfilled criteria for disposal as inert as well
Quartz SiO2 (X) Q as non-reactive hazardous wastes too. Thus, the disposal of investigated
Sphalerite (ZnxCd1−x)S XX S
slag in open field will severely pollute the nearby ground as well as
Wuestite FeO X W
surface water and therefore some precautions will be necessary during
XXX: Abudant; XX: Meanly abundant; X: Lowly abundant, (X): Possibly present. handling and disposal of the Pb slag.
If we consider the total concentration, it can be inferred that the
XRD pattern although the concentrations of both metals in slag are concentrations of majority of the toxic elements in the leachates are
quite high (Table 1). Probably the amounts of Pb based crystalline quite low although their concentrations in slag are very high. This in-
minerals present in slag are below the detection limit of XRD. The same dicates that the mineralogical composition influences the leaching of
observation also indicates the difference in behaviour of these elements elements from the slag. For example, the concentration of Pb in the
during formation of slag. Because of the similarities of size of Fe2+ and leachate is quite high in comparison to the Zn concentration although
Zn2+ (ionic radii of Fe2+ and Zn2+ are 0.76 and 0.74 Å respectively), the Zn content in the slag is almost twice the amount of Pb present in
zinc can substitute the divalent Fe in several types of iron silicates slag. The leaching of low amounts of Zn despite the high Zn content in
(Ettler et al., 2001). For the similar reason, Zn can substitute Mg (ionic slag can be related with the stability of Zn containing minerals in slag:
radius: 0.72 Å) in hardystonite (Ca2(Mg,Zn)Si2O7) too. Thus because of Zn is present in some crystalline silicate minerals (hardystonite,
the similarities in size, most of the Zn are mixed with the silicates and kirchstenite) and sulfide mineral (sphalerite), which are quite stable in
oxide melts and therefore incorporated into the crystalline minerals. On applied leaching conditions (Cappuyns, 2014). On the other hand, in
the other hand, because of the larger ionic size, Pb (ionic radius: 119 Å) slag, Pb is possibly present as easily leachable metallic or intermetallic
is incompatible to the above types of silicates and oxide melts and state, and therefore substantial amounts of Pb are leached from the slag
therefore does not dissolve in melts during slag formation (Ettler et al., during leaching (Barna et al., 2004). Therefore, from the XRD study as
2001). Zn may also be present as sulfides and possibly some amounts of well as the leaching behaviour, it can be concluded that Pb in slag is

351
N. Saikia et al. Groundwater for Sustainable Development 7 (2018) 348–358

Table 3
Concentrations of elements in leachate obtained after leaching of slag according to EN12457–2 leaching test.

Parameters Amounts leached (mg/L)a Standard Specifications (mg/L) European Specification for land-filled disposald (mg/kg)

Drinking Waterb Waste Effluentc Inert Stable non-reactive hazardous Hazardous

Al 1.18 0.03
Ba 3.50 0.7 –
Ca 20.8 75 –
Fe 0.10 1.0 3.0
Mg 0.07 30 –
As 0.02 (0.11) 0.01 0.2 0.5 2.0 25
Cd 0.001 (0.02) 0.003 2.0 0.04 1.0 5.0
Cu 0.02 (0.44) 0.05 3.0 2.0 50 100
Mo 0.12 (1.0) 0.07 – 0.5 10 30
Ni 0.05 (0.08) 0.02 3.0 0.4 10 40
Pb 4.91 (49.1) 0.01 0.1 0.5 10 50
Se 0.44 (3.5) 0.01 0.05 0.1 0.5 7
Zn 0.09 (1.7) 5.0 5.0 4 50 200
pH 10.6 – 5.5–9.0 > 6.0

a
Values within brackets are in mg/kg.
b
According to Indian Standard, IS 10500 2012.
c
Schedule IV: The Environmental (Protection) Rules, 2000, Central Pollution Control Board, Govt. of India.
d
According to European Council Directive 2003/33/EC and BS EN 12457–3 limit values for landfill waste acceptance criteria.

primarily present as a metallic inclusion trapped in the amorphous
glass, or in crystalline forms as a pure metal or in intermetallic state or
as sulfide compounds (Ettler et al., 2001).
3.3. Acid neutralization capacity (ANC)
The change in pH due to the additions of different volumes of acids
and bases into the slag during leaching experiments are presented in
Fig. 2. The figure indicates initial slow increase in pH from 2.5 to 4.5
with large amounts of basicity consumptions followed by a rapid
change in pH (4.5–11.8) within a very small range of acid or base
consumption zone. The changes in pH again slowdowns in the pH range
of 11.8–13.2 with increasing base additions. The slow change in pH
indicates the existence of a buffering zone at high pH region. Con-
sidering the presence of considerable amounts of Ca and Si in the slag
and in the leachates, the carbonation and associated interaction of CO2
with mineral phases like Portlandite, as well as the formations of cal-
cium silicate hydrates may be the major reason for such behaviour
(Garrabrants et al., 2004). The dissolution of acidic sulfide minerals
present in slag due to the addition of base can also increase the H+ ion
concentrations and therefore decrease the pH of leachates by introdu-
cing strong acidic environment (Cappuyns, 2014). On the other hand, at
low pH, alkali and alkaline earth metals are liberated due to the dis-
solution of silicate minerals present in slag. The emitted alkali and al-
kaline earth metals neutralize the added amounts of acids and therefore
a weak buffering zone is appeared.
The acid neutralization capacity, (ANC) of a waste (i.e. capacity of
waste to neutralize acids) is a key property to understand the long term
waste behaviour in environment as the dissolutions followed by pre-
cipitations of metals are directly related with ANC values. The results
obtained from prEN 14429 leaching test can also be used to assess the
acid neutralization capacity of a waste material too. For this purpose,
the amount of acid added in mL was converted into the equivalent of
acids per gram of dry waste and presented in Fig. 3. About 0.75 meqv/g
acid is necessary to reach the pH 7 while for reaching pH 5 this amount
increases to 3.92 meqv/g acid and for pH 4, the necessary amount of
acid is 37.25 meqv/g. This indicates the existence of a strong buffering
zone between pH 5 and 4. Moreover, in comparison to other waste
materials such as municipal incineration ash, investigated slag has very
low ANCpH7, which is in accordance with the values reported for other
non-ferrous slags (Cornelis et al., 2011).
Table 4 shows the ANC values of slag and concentrations of a few
toxic elements in leachates obtained in the pH range of 4.0–10.7. In the
same Table, the acceptable limit values for these elements according to
European directive for classifying a waste for landfilling purposes are
also presented. From the results, it can be concluded that the addition of
small amounts of acid can leached substantial amounts of toxic ele-
ments, most of which are quite higher than the standard specifications.
For example, when leaching was done by using distilled water as a
leaching solution, the concentrations of Pb and Zn in the leachate were
49.1 and 0.9 mg/kg respectively and the pH of the leachate was 10.7.
The leaching of slag by using 0.745 meqv/g acid containing water
generated a leachates having pH 7.04. The concentrations of Pb and Zn
in the leachates were 8.4 and 194 mg/kg respectively and well above

12
10.6

8
pH

4
Base Acid

0
-15 -10 -5 0 5 10 15
NaOH/HNO added (ml)
Fig. 3. Equivalents of acid added per gm of slag for determining acid neutralization ca-
Fig. 2. The pH as a function of volume of acid or base added into the leachant. pacity.

352
N. Saikia et al. Groundwater for Sustainable Development 7 (2018) 348–358

Table 4 the pH dependence leaching behaviours of most of the trace elements

Acid neutralization capacities and concentrations of elements in the leachate at different are probably dependent on the behaviours of these elements.
pH obtained after leaching of slag according to prEN 14429 test.

pH Amounts of Elements Concentration European Landfill directive 3.4. pH dependent leaching behaviour
acid added (mg/kg) (mg/kg)a
(meqv/g) In order to understand the effect of pH on the leaching behaviour of
Inert Non- Hazardous toxic metal and metalloid species, the experimental results of these
reactive
hazardous
toxic species, obtained from prEN 14429 leaching test were analyzed
and compared with the leaching behaviour of some major elements
10.7 0 Pb 49.1 0.5 10.0 50.0 present in the slag. Considering the similarities of leaching properties of
Zn 0.87 4.0 50.0 200 alkaline wastes such as MSWI bottom ash and APC residue, FFC fly ash
As 0.11 0.5 2.0 25.0
with metallurgical slags, in this investigation therefore, an attempt has
Se 3.52 0.1 0.5 7.0
9.54 0.298 Pb 1.01 been made to explain the leaching behaviours of toxic elements of slag
Zn 0.11 by using the existing geo-chemical modeling information along with the
As 0.005 surface chemistry results for related wastes (Cornelis et al., 2011; Quina
Se 2.36
et al., 2009). Table 5 shows the solubility controlling mineral phases
8.60 0.633 Pb 0.99
Zn 0.52 and physical processes those reported for various types of alkaline
As nd wastes.
Se 0.78 The higher leachabilities of elements with increasing acidity and
7.04 0.745 Pb 8.38 basicity of the leachates from neutral pH as observed from the pH de-
Zn 194.0
pendent leaching curves indicate that most of the elements are asso-
As 0.001
Se 0.45 ciated with the relatively stable silicates and oxide minerals of slag
5.07 3.72 Pb 3909.5 (Cappuyns, 2014). The pH dependent leaching of most of the major as
Zn 1451.0 well as minor metal or metalloid species exhibits a U or V-shaped
As 3.86
curves, characteristics for amphoteric nature (Vitkova et al., 2009;
Se 0.18
4.06 37.3 Pb 4376.0
Nilsson et al., 2016). The leaching amount of each element at extreme
Zn 11185.0 acidic condition is more than that observed in extreme basic condition.
As 3.27 The dissolution of minerals present in slag and consequent formations
Se 0.25 of secondary mineral phases at different pH conditions are the major
a processes which control the pH dependent behaviour of various ele-
According to European Council Directive 2003/33/EC and BS EN 12457–3 limit
values for landfill waste acceptance criteria.
ments in the leachates. Thus, at extreme high and low pH regions
(pH < 4 and pH > 13), the equilibrium concentrations of almost all
the standard specified limits for disposal as inert waste in landfill. The investigated elements are controlled by the solubilization of elements
Pb and Zn concentrations in the leachate further increased to from the slag. Considering the behaviours of various elements in the pH
3909.5 mg/kg and 1451 mg/kg respectively when leaching was done by dependence leaching curves, it can be concluded that the upward trend
using 3.72 meqv/g acid containing water. The pH of the leachate was of their concentrations observed in the leaching curve indicates the
also decreased to 5.07. The same behaviours can be observed for the dissolution of a species from minerals during leaching process. On the
majority of other trace elements. other hand, a downward trend after an upward trend indicates the
The variation of conductivity of leachate generated from slag precipitation of the species due to various physico-chemical phe-
against the variation of pH values is presented in Fig. 4. The con- nomena.
ductivities of leachates generally low in the pH range of 6–12 with a Ettringite - a hydrated calcium aluminosulfate and calcium silicate
minimum at pH about 10.9. This range also corresponds to the hydrate are the cement based minerals those can accommodate cations
minimum leaching region for most of the major and minor elements. and oxyanions of As, Mo and Se in its structure by various physico-
Fig. 4 also shows strong relationship between the pH dependent con- chemical processes (Gougar et al., 1996; Saikia et al., 2006a). These
ductivity values of leachates with the concentrations of some major and minerals are normally precipitated as secondary minerals during
trace elements present in the leachates. The dependence of conductivity leaching of high calcium and silica containing wastes such as coal fly
curve on the concentrations of Ca, Fe, Si, Pb, and Zn also indicates that ash and control the mobilities of different toxic elements at various
environmental conditions (Saikia et al., 2006a). Chemical analysis in-
dicates the presence of high amounts of CaO, SiO2 along with the
100 1000 considerable amounts of Al2O3 and SO42- in the slag. Therefore, like
Fe Ca Zn
some other wastes, these species may come into the solution due to the
Conductivity (mS/cm, log scale)

Pb Si
interaction of slag with high alkaline leaching solution and at appro-
Concentration (mg/g)

10 10 priate chemical environment they can form ettringite and calcium si-
licate hydrate type minerals (Dermatas and Meng, 2003).
The concentrations of Al, Ca, Si and sulfate in the leachate at various
1 0.1 pH are presented in Fig. 5. The more or less similar leaching curves of
calcium and silica, particularly at high pH region indicate some cor-
relation between these two species. Therefore, at high pH, there is a
0.1 0.001 strong possibility of the formation of calcium silicate hydrate type
minerals due to the reaction of calcium and silica. The formation of
such secondary mineral surfaces also controls the leaching behaviour of
0.01 0.00001
several minor elements particularly at high pH region. Engstrom (2010)
2 4 6 8 10 12 14
also observed the formation of calcium silicate hydrate during leaching
pH
of EAF slag having similar type of mineral composition. In comparison
Fig. 4. Conductivity of leachates and concentrations of some major elements in the lea- to the behaviours of other three species presented in Fig. 5, sulfate
chates as a function of pH.
concentrations in the leachate are relatively constant in the near neutral

353
N. Saikia et al. Groundwater for Sustainable Development 7 (2018) 348–358

Table 5
Solubility controlling phases.

Metal pH range Solubility controlling phase References

As 6–10 Pb3(AsO4)2 Allison et al. (1991); Cornelis et al. (2009).

> 13 Ca3(AsO4)2.xH2O Cornelis et al. (2009); Halim et al. (2005); Phenrat et al. (2005);
Vandecasteele et al. (2002).
> 12 Adsorption of As on Fe oxide surfaces Cornelis et al. (2009); Leuz et al. (2006); Meima and Comans (1998a,
1998b).
Mo At low pH CaMoO4 Cornelis et al. (2009); Felmy et al. (1992); Kersten et al. (1997); Rai and
Zachara (1984).
Se At low pH PbSeO3 Cornelis et al. (2009); Se´by et al. (2001).
At high pH CaSeO4 Cornelis et al. (2009); Essington (1988).
Pb 4–6 Pb2(CO3)Cl2 Geysen (2004); Hyks et al. (2009); Quina et al. (2009).
6–12 PbClOH
> 12 Pb4(OH)6SO4
> 11 Sorbs into reactive surfaces such hydrous iron (hydr)oxides and hydrous
aluminum (hydr)oxides
Cd > 12 Cd(OH)2 Quina et al. (2009); Van der Bruggen et al. (1998); Van Herck et al. (2000).
9–12 Cd4(OH)6SO4 Quina et al. (2009); Van Herck et al. (2000); Yan et al. (2008).
5–10 CdCO3 Quina et al. (2009); Van der Bruggen et al. (1998); Van Herck et al. (2000).
6–12 Adsorbed by hydrous Hyks et al. (2009); Quina et al. (2009); Zhang et al. (2008).
Ferric oxide (FehOCd+ and FeOCd+)
Ni 7–14 Ni(OH)2 Quina et al. (2009); Yan et al. (2008); Zhang et al. (2008).
6–9 Adsorption by FehONi+ and FeONi+ Dijkstra et al., (2008, 2006); Quina et al. (2009);
Cu > 10 Cu(OH)2 Eighmy et al. (1995); Hyks et al. (2009); Quina et al. (2009).
5–7 Cu2CO3(OH)2 Quina et al. (2009); Zhang et al. (2008).
– Surface complexation to Fe and Al (hydr)oxides Dijkstra et al. (2006); Quina et al. (2009).
Zn 3–5 ZnSiO3 Astrup et al. (2006); Eighmy et al. (1995); Van der Bruggen et al. (1998); Van
Herck et al. (2000).
5–10 ZnCO3 Eighmy et al. (1995); Van der Bruggen et al. (1998); Van Herck et al. (2000);
Zhang et al. (2008).
>8 ZnO Van der Bruggen et al. (1998); Zhang et al. (2008).

100 Al Ca et al., 2012). The precipitation of zinc hydroxide carbonate at lowly

S Si alkaline pH range (pH around 8.0) on iron ferrihydrite can also adsorb
Concentrations (mg/g)

10
1 pH dependent leaching curves of As and Fe and Zn at pH above 10.0
0.1
0.01
0.001
0.0001
2 4 6 8 10 12
pH
Fig. 5. Concentrations of Ca, Al, Si and SO42- in the leachates as a function of pH.
to alkaline pH zones. Possibly sulfate does not have any active role on
the mobility of minor elements especially at high pH region and
therefore the role of ettringite on the mobility of trace elements can be
ruled out.
3.4.1. pH dependent leaching behaviour of oxyanions
Fig. 6 shows the pH dependent leaching behaviours of As, Mo and
Se. For comparison purpose, the pH dependent leaching curves of some
major metal species are also included in the figure. The shapes of pH
dependent leaching curve of As generates a U or V shaped curve, which
is characteristic of an amphoteric element and in accordance with the
leaching curves of Pb and Fe.
The similarities of the behaviour of Pb with AsO42- in the pH range
of acidic to pH=10.8 suggest that the formation of PbAsO4 and
Pb3(AsO4)2 may be the major solubility controlling minerals for AsO42-
at this pH region (Cornelis et al., 2009; Potysz et al., 2016). The pre-
sence of iron hydroxide surfaces can also absorb substantial amounts of
arsenate particularly at near neutral pH range (Antelo et al., 2005). The
presence of cationic species such as Ca2+, Zn2+ can also increase the As
absorption capacity of ferrihydrite due to the change in the electrostatic
forces at the solid/solution interface (Antelo et al., 2015; Carabante
arsenic from the leachates (Carabante et al., 2012). The similarity of the
also indicates the role of these two elements on the behaviour of As at
alkaline pH. However, at pH above 11.0, formation of calcium arsenate
can also play an important role on the mobility of As (Saikia et al.,
2006a). The similarity of the shapes of the leaching curves of As and Ca
at pH above 12.5 and the stability of calcium arsenate at alkaline pH
also indicates the role of Ca on the mobility of As at high pH region. The
presence of considerable amounts of SO42- in the slag and also in the
14
leachate also indicate the possibilities of presence of competitive effect
of sulfate with the oxyanions during their precipitations or sorption's on
other mineral surfaces. For example, sulfate minerals such as PbSO3 and
PbSO4 controlled the solubility of Pb at acidic pH and therefore less Pb
will be available for the formation of PbAsO4 (Table 5).
The pH dependent leaching curves of Se and Mo are more or less
similar and quite different from the As. The leaching curves of Se and
Mo reveal lower solubilities of these elements at low pH region. On the
other hand, the leaching amount gradually increases with increasing
pH, particularly at pH above 8. Wang et al. (2007) also observed similar
behaviour for Se when coal fly ash was subjected to pH dependent
leaching test. Such Se leaching behaviour was related with the forma-
tion and behaviour of iron hydroxide surfaces. The leaching behaviour
of most of the cations and anions are strongly dependent on the solu-
bility behaviour of Fe and subsequent formation of surface active sec-
ondary iron minerals such as iron hydroxides (Nilsson et al., 2016;
Adegoke et al., 2013). At low pH (i.e. acidic and near neutral condi-
tions), the surfaces of iron hydroxides are positively charged, which can
sorbed the negatively charged oxyanionic species due to attractive in-
teractions (Cornwell et al., 2004). Such interactions play an important
role on the mobilities of oxyanions. On the other hand, at higher pH,
the surfaces of iron hydroxides become negatively charged. Therefore
sites available for sorption are decreased due to the repulsive interac-
tions of oxyanions with the negatively charged iron surfaces. However,
some amounts of oxyanions remains sorbed on the iron surfaces due to

354
N. Saikia et al. Groundwater for Sustainable Development 7 (2018) 348–358

1000 1000
As Fe Zn Pb Si S
Pb S Ca

Concentrations (mg/g)
100 Ca Fe
Concentrations (mg/g)

10
1
1

0.1
0.001 0.01

0.001

0.0001
0.000001 2 4 6 8 10 12 14
2 4 6 8 10 12 14 pH
pH
1000
Ca Fe Zn
1000 100 Si S
Se Ba

Concentration (mg/g)
Ca Fe 10
Concentration (mg/g)

10
1

0.1 0.1

0.01
0.001 0.001

0.0001
0.00001 2 4 6 8 10 12 14
2 4 6 8 10 12 14 pH
pH 1000
Cd Si
1000 S Cl-
Mo Ba Fe Ca
Concenteations (mg/g)

10
Fe Ca
Concentration (mg/g)

0.1
1

0.001

0.001 0.00001

0.000001
2 4 6 8 10 12
pH
Fig. 6. Concentrations of As, Se, Mo and some major elements in the leachate at various
pH.
the neutralizations of some of the negative surface charges on iron
surfaces by the cationic species such as Ca2+, Mg2+, Zn2+, and Pb2+
present in the leachate. Sorption/desorption of oxyanions on the iron
hydroxide surfaces is therefore a plausible mechanism for explaining
the pH dependent leaching behaviours of Se and Mo from slag.
The minerals such as Ca and Ba selenite (at low and high pH) and
powellite (CaMoO4) are the some other mineral phases which may
control the dissolution and precipitation behaviours of these elements
too (Cornelis et al., 2009; Nishimura et al., 2009). A comparison of
leaching behaviour of Se with the leaching behaviour of Fe, Ca and Ba,
it can be concluded that Fe is the major element which controls the
selenium mobility at acidic and alkaline pH region (Fig. 6). It can also
be concluded that the mobilities of Ca2+ and Ba2+ have also effect on
the pH dependent leaching behaviour of selenium. From the similarities
of pH dependence leaching curves of Ca and Mo especially at pH > 8.5,
it can be concluded that the mobility of Mo is probably controlled by
powellite (Cornelis et al., 2009).
3.4.2. pH dependent leaching behaviours of cationic species
The pH dependent leaching results of Pb, Zn and Cd are presented in
Fig. 7. In the same Fig., the concentrations of some major elements
present in the leachate are also presented. The pH dependence leaching
0.0000001
2 4 6 8 10 12 14
pH
14
Fig. 7. Concentrations of Pb, Zn, Cd and some major elements in the leachate at various
pH.
curves of Pb and Zn exhibit characteristics V shaped curves due to their
amphoteric natures. They also exhibit minimum solubility in the pH
range of 8.0–9.5, partly due to the precipitation as hydroxides. At ex-
treme high and low pH regions (pH < 4 and > 13), the dissolved
amounts of metal species embedded in different minerals present in
waste controls the equilibrium conditions. An inspection of the pH
dependent leaching curves of all three elements reveals that the dis-
solutions and precipitations are the major mechanism for their beha-
viours under varying pH conditions. The similarities of pH dependent
curve of Pb with the pH dependent curves of Fe and Si at the pH < 5.0
indicates that the dissolution of Pb embedded in the various iron sili-
cate minerals is the major mechanism for the mobility of Pb at this pH
zone. Anglesite (PbSO4) and PbSO3 under acidic condition and laur-
ionite (Pb(OH)Cl) under alkaline condition are the major solubility
controlling phases of Pb leaching from the fly ash generated in sec-
ondary Pb smelting (Vitkova et al., 2009). On the other hand, for MSWI
APC residue, Pb2(CO)3Cl2, PbClOH and Pb(OH)2SO4 are the solubility
controlling phases at pH 4–6, 6–12 and pH > 12 respectively (Quina
et al., 2009). From the similarities of the pH dependent leaching curve
of Pb obtained in this study with the similar curves for Pb leaching
reported by Quina et al. (2009) and Vitkova et al. (2009), it can be
concluded that the same types of mineral phases are the solubility
controlling phases for Pb leaching from slag in the pH range of
4.0–10.5. The weak correlations of the pH dependent leaching curve of

355
N. Saikia et al.
Pb with the curve of Cl- at the pH range of 2.5–5.5 and the curve of
SO42- at pH > 12.0 also supports such conclusion. The surface proper-
ties of iron hydroxide and calcium silicate hydrate can have profound
effect on the mobility of Pb especially at very high pH condition too. A
close inspection of the pH dependent leaching curves of Pb with Fe, Ca
and Si, it can be inferred that the sorption/desorption of Pb on the iron
hydroxide and calcium silicate hydrate partly controls the mobility of
Pb at pH above 10.5.
The mobility of Zn from various types of alkaline residues are
mainly controlled by the solid mineral phases like ZnCO3 and ZnO.SiO2
at pH 6, Zn5(OH)8Cl2 at pH 6–8, ZnO at pH 7–13 (Van der Bruggen
et al., 1998). On the other hand, Van Herck et al. (2000) and Quina
et al. (2009) observed ZnO.SiO2, ZnCO3 and Zn(OH)2 as the solubility
controlling phases for Zn leaching from MSWI fly. Yan et al. (2008)
observed ZnSiO3 as the only precipitating species in the leachates of
MSWI fly ash at the pH range of 6–12. Liu et al. (2016) observed strong
pH dependence on the Zn sorption by ferrihydrite at pH < 6. According
to Yan et al. (2008), only dissolution/precipitation mechanism without
considering adsorption model is sufficient to explain the leaching be-
haviour of Zn from MSWI fly ash. Considering the similarities of the Zn
leaching curve obtained in this investigation with the results presented
in Van Herck et al. (2000), Quina et al. (2009) and Yan et al. (2008)
papers, it can be concluded that the Zn leaching from slag in the pH
range of 2.5–10.5 probably follows the dissolution/precipitation me-
chanism involving species reported in these investigations. The pH
dependent leaching curve of Zn is quite similar to the curves of Fe, Si
and Ca at lower pH (< 5.5) also support that the dissolution of Zn from
the mineral phases is the major mechanism for Zn behaviour at this
region. At the pH range of 5.5–10.5, Zn is probably precipitated as
ZnSiO2 and Zn(OH)2. The similarities of the behaviour of Zn with the
behaviours of Fe and Ca at the pH range of 10.5–13.0 reveals that the
surface properties of Fe and Ca containing minerals are more important
than the dissolution/precipitation mechanism for Zn mobilization at
this basic pH region. However, at pH > 13.0, dissolution of Zn minerals
from the minerals containing Zn, Si and Fe is the major solubility
controlling mechanism of Zn from lead slag. Cd mobility at pH < 9.0 is
related with the CdCl2+ and CdCO3 (Van der Bruggen et al., 1998; Yan
et al., 2008). On the other hand, CdOH+ and Cd(OH)2 are the major
phases at pH above 10.0. (Quina et al., 2009). In several investigations,
Cd4(OH)6SO4 is considered as the major solubility controlling phases
(Yan et al., 2008; Zhang et al., 2008). Similar types of mineral phases
are probably responsible for Cd mobility in slag especially at pH range
of 4–10. However, the similarities of pH dependent curves of Cd with Fe
especially at pH above 10 indicate that the Cd mobility of slag also
dependent on the sorption/desorption of Cd compounds on iron hy-
droxide surfaces; possibly surfaces of iron hydroxides adsorbed a part of
Cd at near neutral to alkaline pH (Dijkstra et al., 2006; Meima and
Comans, 1998a, b; Yan et al., 2008).
The pH dependent leaching curves of Ni and Cu along with Fe are
presented in Fig. 8. A comparison of the leaching curves of Ni and Cu
100 Cu Ni
Concentrations (mg/g)
0.1
0.0001
0.0000001
2 4 6 8 10 12
pH
Fig. 8. Concentrations of Cu, Ni and Fe in the leachates as a function of pH.
Groundwater for Sustainable Development 7 (2018) 348–358
with Fe indicates that the mobilities of Cu and Ni are partly dependent
on the pH dependent behaviour of Fe. According to Zhang et al. (2008),
the sorption/desorption of Ni on iron hydroxide surfaces is the major
solubility controlling mechanism of Ni at the pH range of 6.0–9.0 while
at pH 7.0–14.0, the Ni mobility is controlled by Ni(OH)2. According to
Dijkstra et al., (2006, 2008), Ni leaching from bottom ash at pH
10.0–14.0 is controlled by Ni(OH)2. At the pH range above 6.0, the
sorption/desorption of Ni on the iron hydroxide surfaces partly controls
the Ni mobility in slag. However, formation of Ni(OH)2 is the major
solubility controlling mechanism of Ni at basic pH region. Similarly the
dissolution/precipitation is considered as the major solubility control-
ling mechanism of Cu particularly at pH above 5.0 (Zhang et al., 2008;
Eighmy et al., 1995; Dijkstra et al., 2006). According to Dijkstra et al.
(2006), at pH < 8.0, surface complexation on aluminum hydroxide and
iron hydroxide surface might be the major solubility controlling me-
chanism of Cu. At high pH, probably, formations of compounds such as
Cu(OH)2, Cu2CO3(OH)2 are more important than the sorption/deso-
rption for explaining mobility of Cu (Dijkstra et al., 2008). From the
comparison of Cu and Fe leaching behaviours as presented in Fig. 8, it
can be concluded that Fe compounds have little effect on the solubility
of Cu especially at pH below 13.0. Thus the sorption/desorption at low
pH and formation of copper hydroxide compounds at high pH are the
mechanisms, which possibly control the pH dependent Cu leaching
from slag.
3.4.3. pH dependent leaching behaviours of alkali metals, chloride and
sulfate
Fig. 9 shows the pH dependent leaching behaviours of Na, K Cl¯ and
SO42-. The dissolutions of these chemical species are also weakly de-
pendent on the pH of the leachates. Thus some amounts of these species
are occluded in the stable mineral phases which are solubilized at ex-
treme acidic and basic conditions along with the embedding mineral
phases. However, the pH effect is minimal at the at the pH range of
5.0–12.0. The curves reveal that the dissolution/precipitation me-
chanism partly plays a rule for chloride especially at pH < 5.0 and for
sulfate in the pH range of 4.0–7.0. The striking similarities of the pH
dependence leaching curves of Na and K with the leaching curve of Cl¯
in the acidic to pH of about 12.7 indicates the existences of similar types
of solubility controlling mechanisms for the pH dependence mobiliza-
tions of these elements. However, at higher pH, chloride mobility is
possibly controlled by the precipitations and dissolutions behaviours of
some calcium based minerals such as Fridel's salt (Ca2Al(OH)6Cl·2H2O)
(Saikia et al., 2006b)
4. Conclusions
This study was undertaken to evaluate the toxicity behaviour of a
lead smelting slag by evaluating the pH dependent leaching behaviours
100
K Cl-
Na S
Concentrations (mg/g)
Fe 10
1
0.1
0.01
14 2 4 6 8 10 12 14
pH
Fig. 9. Concentrations of Na, K, and Cl− and SO42- in the leachates as a function of pH.
356
N. Saikia et al.
of some toxic metal and metalloid species. The major conclusions of this
investigation can be briefly summarized as:
(a) The concentrations of some of the toxic metal(loid) species in the
leachates generated from slag are considerably higher than their
specified limits for drinking water as well as the limit for inland
surface disposal as effluents. Moreover the concentrations of Pb and
Se in the leachate are higher than their specified limits prescribed
for disposal of a waste as inert and non-reactive hazardous waste in
landfill. About 0.745 meqv/g acid is necessary to reach the pH 7
while for pH 5 this amount increased to 3.42 meqv/g acid and for
pH 4, the required amount is 37.3 meqv/g. The conductivity of
leachate is very low at the pH range of 6.0–11.0 with a minimum at
pH about 10.9. This pH range also corresponds to the minimum
leaching region for almost all toxic elements except Se and Mo.
(b) The shapes of the pH dependent leaching curves reveal that the
elements such as Pb, Zn, Cu, and Cd present in slag are amphoteric
in nature. The pH dependent leaching behaviour of As can be re-
lated with the leaching behaviour of Pb, and to some extent with
the behaviours of Fe and Zn. The pH dependent leaching curves of
Se and Mo are more or less similar to each other and quite different
from As. The dissolution of minerals especially Ca, Fe and Si con-
taining minerals present in slag and consequent formations of sec-
ondary mineral phases at different pH regions are the major pro-
cesses, which control the pH dependent behaviour of various
elements. The leachings of sodium, potassium and chloride from
slag particularly in the pH range of 4.0–12.0 are pH independent
and therefore their behaviours do not have effect on the mobilities
of trace elements.
(c) Finally it can be concluded that the disposal of Pb smelter slag in
open field without any treatment is a big threat to nearby area since
high amounts of toxic metal and metalloid species especially Se, Pb,
and Zn are leached from slag at the pH range of 5.0–7.0 and very
less amounts of acid is necessary to reach this pH range. Thus at-
mospheric carbonation followed by acidic rain can leached more
than legal limits of these elements and severely pollute the surface
as well as ground water. Similarly the use of slag as a raw-material
in cement based product development will also create environ-
mental problems since large amounts of toxic elements will be
liberated due to the additions of small amounts of alkaline solution
into the slag. Moreover, the methodologies applied in this in-
vestigation to analyze the pH dependence leaching results can be an
effective approach for assessing the environmental impacts of si-
milar types of other waste materials.
Acknowledgement
Authors are grateful to Dr. Geert Cornelis for his help during ana-
lysis of samples by ICP-MS. NJS acknowledges the Research Fund of
K.U. Leuven (Ref: F/05/063) for the grant of a fellowship. Authors are
also grateful to anonymous reviewers for their helpful comments.
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