Applied Geochemistry 105 (2019) 114–124

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Applied Geochemistry
journal homepage: www.elsevier.com/locate/apgeochem

Effects of pH, competing ions and aging on arsenic(V) sorption and isotopic T
exchange in contaminated soils
M.S. Rahmana,b, M.W. Clarka,c,∗, L.H. Yeea,b, M.J. Comarmondd, T.E. Paynea,d, E.D. Burtonc
a
School of Environment Science and Engineering, Southern Cross University, PO Box 157, Lismore, NSW, 2480, Australia
b
Marine Ecology Research Centre, Southern Cross University, PO Box 157, Lismore, NSW, 2480, Australia
c
Southern Cross GeoScience, Southern Cross University, PO Box 157, Lismore, NSW, 2480, Australia
d
Australian Nuclear Science and Technology Organisation, Locked Bag 2001 Kirrawee DC, NSW, 2232. Australia

A B S T R A C T

Cattle tick control in Australia using arsenicals from early 1900s to 1955 has led to the existence of some 1600 contaminated sites in northern New South Wales
alone. Sorption processes play key roles in controlling arsenic (As) accessibility and subsequent mobility in these dip soils. As(V) sorption and accessibility in three
As-contaminated soils and two uncontaminated soil types (ferralitic and sandy soils) are investigated utilizing batch sorption experiments and isotopic exchange
techniques. The aged contaminated soils displayed little or no ability to sorb additional As(V), and increasing the soil pH caused a substantial reduction in As(V)-
sorption and resulting in As(V)-release. Isotope exchange experiments further supported that any further exposure of the aged-contaminated-soils to additional As(V)
increased As-mobilization potential. Amendments of phosphate greatly decreased As(V) sorption in aged-contaminated-soils where As-sorption sites were more
highly saturated, whereas phosphate had little effect on As(V) sorption in pristine soils. Similarly, sulfate reduced As(V) sorption, but these effects were less marked
than those for phosphate, hence, the application of both PO43− and SO42− in As(V)-contaminated-soils may lead to potential As(V)- mobilization. Conversely, Ca2+
increases As(V)-sorption, which is consistent with expected changes in the surface charge characteristics from Ca2+ sorption, and/or Ca-AsO4 precipitations, con-
sequently Ca2+ amendments may improve As-retention, thereby decreasing As accessibility from cattle dip soils. Therefore, the detailed knowledge presented here
provides new insights that may be useful for the assessment and management of the As-contaminated soils.

1. Introduction behaviour of soil-bound As, because mobility, toxicity and bioavail-

Arsenic is an extremely toxic and carcinogenic element, and there-
fore, As soil contamination is a major environmental threat (Smith
et al., 1998). The historical application of As-based pesticides at cattle-
dip sites across the northern region of New South Wales (NSW) in
eastern Australia has resulted in the contamination of surrounding soils
with As at concentrations of up to 14,000 mg kg−1 (Burton et al., 2014;
McLaren et al., 1998; Niazi et al., 2011; Smith et al., 1998). Many dip
sites in the region which were investigated exceed the Australian eco-
logical investigation level (EIL) of 20 mg kg−1 (NEPM, 1999).
Arsenic-contaminated-soils, therefore, pose a substantial human
health threat due to their potential to pollute surface and ground wa-
ters, or by introducing As into the food chain through plant uptake.
Consequentially, it is essential to fully understand the fate and transport
characteristics of As in long-term contaminated-soils. Estimation of the
total As-content, adsorption, and availability in the soils is imperative
to assess the extent of contamination and risks posed to the environ-
ment, and to develop and evaluate remediation strategies (Mandal and
Suzuki, 2002; Smith et al., 1998). Moreover, a thorough understanding
of the controls on As-sorption are necessary for predicting the fate and
ability of As depend largely on the soil-bound As speciation, sorption
and desorption characteristics (Goldberg and Glaubig, 1988; Smith
et al., 2002). Hence, in order to elucidate soil-bound As-behaviour, it is
important to study the sorption/desorption processes occurring (Kundu
and Gupta, 2006; Manning and Goldberg, 1997).
Previous research has shown that Fe and Al oxy-hydroxides have a
high affinity for As (Lafferty and Loeppert, 2005; Manning and
Goldberg, 1997; Rahman et al., 2017a, 2017b; Zhang and Selim, 2005).
In contrast, because of negatively charged surfaces, most clay minerals
generally have low As adsorption capacities (Goldberg, 2002; Lin and
Puls, 2000). X-ray adsorption fine structure spectroscopy (Fendorf
et al., 1997; Manning et al., 1998) and Fourier transform infrared
spectroscopy (Goldberg and Johnston, 2001; Sun and Doner, 1996)
suggest that both As(V) and As(III) form mono- or bidentate inner-
sphere surface complexes with iron-oxyhydroxides via a ligand ex-
change mechanism. Surface complexation models have been employed
to describe As-adsorption on minerals (Goldberg, 2002; Goldberg and
Johnston, 2001; Manning et al., 1998) and several soil-bound As studies
demonstrate that adsorption correlates with Al- and Fe-oxyhydroxide
contents (Manning and Goldberg, 1997; Smith et al., 1999).

∗
Corresponding author. School of Environment Science and Engineering, Southern Cross University, PO Box 157, Lismore, NSW, 2480, Australia.
E-mail address: malcolm.clark@scu.edu.au (M.W. Clark).

https://doi.org/10.1016/j.apgeochem.2019.04.016
Received 24 July 2018; Received in revised form 4 April 2019; Accepted 17 April 2019
Available online 24 April 2019
0883-2927/ © 2019 Elsevier Ltd. All rights reserved.
M.S. Rahman, et al.
Additionally, organic matter, dissolved organic carbon, and soil phos-
phate have all been shown to suppress As(V)-adsorption by displacing
adsorbed As(V) (Grafe et al., 2001; Violante and Pigna, 2002).
Radionuclides are extremely useful in understanding soil-bound
trace-element behaviour, for example, isotopic exchange techniques
have been used in agricultural and environmental contamination stu-
dies (Clark et al., 2011b; Lopez and Graham, 1970; McDowell et al.,
2001; Tye et al., 2002; Zhang et al., 2006). Radiotracer techniques are
particularly useful for estimating the mobile fraction and such techni-
ques are often superior to simple chemical extractions because of the
operationally defined nature of extraction techniques (Payne et al.,
2004). Isotope exchange studies enable the quantification of the po-
tentially mobile or ‘bio-accessible’ proportion of the element (often
referred to as the ‘labile pool’), that is weakly bound by the soil and is
available in a soil system (Lopez and Graham, 1970, 1972).
Although much work has been devoted to examining the As-sorp-
tion in pristine or uncontaminated soils, almost no studies exist on
further As-sorption to aged-As-contaminated soils; this represents a
considerable knowledge gap in understanding of As-sorption and par-
titioning in both pristine and long-term aged contaminated soils.
Moreover, understanding the sorption behaviour in historically con-
taminated soils is important as it can provide better risk assessments
and decision making regarding management, and/or remediation. In
the case of As, 73As provides a particularly useful label for facilitating
laboratory experiments and determining its availability to contacting
aqueous phases.
Rahman et al. (2017a) presented synchrotron and isotope exchange
data, which showed that the chemical forms of arsenic changed with
time after addition to soil mixtures. Newly added-As was predominantly
mineral-surface sorbed (such as Fe-oxy-hydroxides) and readily ex-
changeable. However, the decades old, environmentally aged, soil-
bound-As from field sites had partially transformed to crystalline phases
such as svenekite, weilite, mansfieldite and scorodite. Here, we further
investigate As(V)-sorption in aged As-contaminated and corresponding
pristine soils as a function of pre-existing As-loadings, reaction pH,
cation, and competing anion concentrations using laboratory batch
sorption experiments and isotope exchange techniques.
2. Materials and methods
2.1. Soil sampling
Surface (0–30 cm) soils were collected from three As-contaminated
cattle dip sites at McLeans Ridges (28°48′1.692″S and 153°23′8.734″E),
Pearces Creek (28°46′12.513″S and 153°26′40.018″E) and Cudgen
(28°15′13.944″S and 153°33′22.182″E), representing distinctive soil
types and contamination levels in the northern rivers region of NSW,
Australia. Two pristine control soils, a ferralitic and a sandy soil, were
also collected from non-contaminated sites located in Wollongbar
(28°48′36.5″S and 153°23′50.7″E) and Cudgen (28°15′11.99′S and
153°33′32.99″E), NSW, respectively. The location map of soil sampling
sites was presented in the study by Rahman et al. (2017b). A synthe-
sized standard soil was also prepared according to OECD (Organization
for Economic Cooperation and Development) guidelines (OECD, 1984)
containing 10% organic matter (air-dried and finely ground sphagnum
peat, 2-mm sieved), 20% kaolinite clay and 70% industrial quartz sand
(> 50% particles 0.05–0.2 mm). All soil samples were air-dried and
crushed to pass through a 2-mm stainless-steel sieve. Following
crushing, the soils were thoroughly homogenized and stored in airtight
containers at room temperature for analyses and experiments. The
mineralogy was determined on dry soil samples by X-ray diffraction
(XRD), using a Bruker D4 Endeavor using Cokα X-rays and Lynx-Eye fast
detector (Rahman et al., 2017a).
The soils were characterized for pH in a 1:5 soil:water extract and
for effective cation exchange capacity (ECEC) using the method de-
scribed by Rayment and Lyons (2011). Soil organic carbon content was
115
Applied Geochemistry 105 (2019) 114–124
analysed using an elemental analyzer (LECO IR analyzer) and soil ar-
ticle size distributions were determined using the hydrometer analysis
method (Klute, 1986). Total major and trace elements were analysed
via inductively coupled plasma mass spectrometry, while As-con-
centrations were determined using a PerkinElmer ELAN DRCe (dynamic
reaction cell) ICP-MS, where the DRCe receives a small bleed of He to
disrupt poly-atomic species formation (e.g., ArCl at 75 amu) from
forming, thereby avoiding As over estimations; particularly in aqua-
regia digestions. A DPTA (Diethylenetriaminepenta-acetic acid) ex-
traction method (Lindsay and Norvell, 1978) was also used for Fe and
Mn extraction in order to approximate plant availability, particularly
for food crops (e.g. wheat).
2.2. Sorption batch experiments
Sorption studies were carried out in duplicate using batch sorption
experiments. All laboratory glass- and plastic-ware were cleaned by
soaking in 5% HCl for at least 24 h, followed by repeated rinsing with
deionized water (Milli-Q). All reagents were analytical grade and all
solutions were prepared with Milli-Q water. An As(V) stock solution
(2 g.L−1) was prepared by dissolving Na2HAsO4·7H2O in 0.01 M NaNO3
solution. This solution was used to prepare separate As(V)-working
solutions at concentrations of 0.05, 0.20, 0.27, 0.66 and 1.00 mM in
0.01 M NaNO3 solution. All solutions were adjusted to the desired pH
(5, 7 and 9) using concentrated HNO3 and/or NaOH.
Samples (1.25 g) of each soil were placed in separate polyethylene
centrifuge tubes and mixed with 50 mL As(V) solution of 0.00, 0.05,
0.20, 0.27, 0.66 and 1.00 mM separately, with a mass loading of
25 g.L−1. Capped tubes were placed on a reciprocal shaker and the
mixtures kept in suspension at 23 ± 2 °C for 96 h until a near steady
state sorption equilibrium was reached. Preliminary kinetic studies
showed that a 96 h contact time was sufficient for soil and solution
equilibrium, which is consistent with earlier work (Smith et al., 1999).
The suspension pH was periodically checked and adjusted to the desired
pH 5 using small aliquots of 0.25 M NaOH or HNO3. Following equili-
bration, samples were centrifuged at 4500 rpm for 30 min and the su-
pernatant liquor was filtered through 0.45 μm filters and collected for
As(V)-analysis. Dissolved As concentrations were determined using in-
ductively coupled plasma mass spectrometry; a PerkinElmer ELAN
DRCe ICP-MS and the soil-bound-As(V) determine as the difference
between the amount initially added and amount remaining in solution,
plus the pre-exiting soil-As.
2.3. Effect of pH, competing anions and index cation
The effects of pH, competing anions and index cation on As(V)
sorption were studied using the batch sorption approach outlined
above. The effect of pH was investigated by preparing another two
separate sorption experiments of each soil at pH 7 and 9. Additional
anion competitions were investigated by the addition of either phos-
phate (0.16 mM P) or sulfate (0.16 mM S) to each soil solutions; As(V)
concentrations of 0.00, 0.05, 0.20, 0.27, 0.66 and 1.00 mM at pH 5.
Phosphate and sulfate solutions were prepared using NaH2PO4.2H2O
and Na2SO4 in 0.01 M NaNO3 background solution, respectively. The
phosphate and sulfate were chosen in the study as the As(V) shares
many physicochemical properties with these anions which are com-
monly found in agricultural soils, which will compete against tha As(V).
Similarly, the index cation effect on As(V) sorption was investigated
using 0.01M Ca(NO3)2 as background electrolyte for replicate As(V)-
sorptions (0.00, 0.05, 0.20, 0.27, 0.66 and 1.00 mM at pH 5) as a re-
placement to the 0.01 M NaNO3 (pH 5) experiment.
2.4. Isotope exchange and leaching experiment
An initial concentration of As(V) (0.20 mM) from the sorption stu-
dies (Section 2.2) was selected for As loading in the samples used in
M.S. Rahman, et al. Applied Geochemistry 105 (2019) 114–124

Table 1
A brief summary of arsenic content and properties of the pristine and contaminated soils from the cattle dip sites, and standard soils; full characterisation data are in
(Rahman et al., 2017a).
Soil properties Soil samples

Contaminated cattle dip sites' soils Pristine soils Standard soil

McLeans Ridges (Ferralitic soil) Pearces Creek (Ferralitic soil) Cudgen (Sandy soil) Ferralitic Sandy OECD

c
pH 5.29 4.81 5.64 5.36 5.26 4.80
Total Carbon (%) 2.52 2.90 1.47 3.43 1.16 5.85
ECEC (cmol+.kg−1)a 15.62 11.47 6.03 9.51 5.52 9.82
Total As (mg.kg−1) 4779 129.0 245.1 2.03 2.97 < 0.15
Total acid extractable (%)
Fe 6.93 9.37 0.63 8.83 0.60 0.14
Al 6.71 6.17 0.34 9.17 0.51 0.23
Mn 0.17 0.06 < 0.01 0.05 0.01 0.01
P 0.13 0.44 0.03 0.11 0.01 < 0.01
Ca 0.34 0.38 0.12 0.20 0.08 0.06
DTPA extract (mg.kg−1)b
Fe 79.07 138.1 94.06 89.92 130.0 15.01
Mn 135.1 32.07 4.02 34.85 3.95 23.04

a,b
ECEC and DTPA stand for effective cation exchange capacity and diethylenetriaminepenta acetic acid, respectively. Data represent the mean of triplicate soil
analysis (standard error of mean < ± 5%, n = 3).

isotope exchange experiments. The contaminated soils (McLeans
Ridges, Pearces Creek and Cudgen), pristine soils (ferralitic and sandy),
and standard soil (OECD) were loaded with As(V) at pH 5 in a similar
manner to sorption batch experiments (Section 2.2) where a 2.5 g
sample of each soil was mixed with 100 mL of 0.20 mM As(V) solution.
Residual solids from the As(V) loading experiment and three non-
loaded contaminated soils (McLeans Ridges, Pearces Creek and Cudgen)
were used for isotope exchange experiments.
As noted above, the isotope exchange technique was employed to
study the available or leachable portion of soils-bound-As(V). Full de-
tails of these techniques have been presented previously (Rahman et al.,
2017a). In brief, the 73As radiotracer stock solution was diluted to a 10
kBq.mL−1 working solution, which was further diluted with 10 mL of
0.10 M NaNO3 to provide an exchange solution of 5000 Bq per ex-
periment or 50 Bq.mL−1.
Each 2.50 g soil sample was suspended with 100 mL of exchange
solution under continuous stirring and a sequential stat-titration was
performed starting at pH 10 and finishing at pH 3. This method allows
for pH to be held at a constant pH for a specified period of time, but
provides a very rapid lowering of pH at the end of the holding period,
such that a plot of pH against time appears as a series of flat steps (Clark
et al., 2011b). The pH was lowered incrementally by one pH unit and
maintained for 1 h after which a 2 mL sub-sample was collected and
separated by centrifugation (0.1 μm Millipore Ultrafree®-CL mem-
brane); subsamples were subsequently diluted and acidified prior to
analysis. The 73As activities were measured by γ-ray spectrometry using
an ORTEC High-Purity Germanium (HPGe) n-type reduced background
detector (relative efficiency of 45%) coupled to an ORTEC DSPEC Pro
with MAESTRO software. Following radioisotope counting, ICP-MS and
ICP-AES analysis was conducted for determination of 75As.
distribution (L.kg−1), and N is the dimensionless reaction order (com-
monly less than one). The Langmuir equation is another widely used
equilibrium sorption model that has the form:
S= Smax(KLC)/ (1 + KLC) (2)
−1
where KL (L.mg ) is a Langmuir coefficient related to the binding
strength.
2.6. Quality assurance, quality control and statistical analysis
Soils samples were digested in duplicate for all elemental analysis
(triplicate for total-As(V) analysis) with the inclusion of reagent blanks,
analytical duplicates and one reference soil (AGAL 12). The reference
soil was used for maintaining quality and accuracy of the digestion
process. The sorption batch experiments were conducted in duplicate.
For all the As(V)-analyses from supernatant, reagent blanks, a standard
As solution of known concentration (1 mg kg−1) and a calibration check
solution for ICP-MS were utilized for quality control test. Mean total As
(V)-recoveries of 96 ± 7% (n = 2) were obtained in the reference soil,
compared to the certified value (3.39 ± 0.52 mg kg−1). The results for
As-analysis were below the detection limits for all blanks. The mean As-
concentration analysed for the standard solution was
1.02 ± 0.03 mg kg−1 (n = 12). For 73As analyses, reagent blanks and
arsenic (73As) standard solutions (12.5, 25 and 50 Bq.g−1) were in-
cluded. Gamma analyses for 73As provided are within ± 5% of true
values and corrected for radioactive decay post sampling and back-
grounds. The statistical analysis of data was performed using Genstat
and Matlab software.
3. Results and discussions

2.5. Isotherm equations 3.1. Arsenic content and properties of soils

When studying metals or metalloids sorption by soils, various
sorption-isotherm equations have been widely used to compare the
sorption by different soils; most commonly the Freundlich and
Langmuir equations (Jiang et al., 2005; Smith et al., 2002; Zhang and
Selim, 2005). The Langmuir and Freundlich equilibrium equations were
used in this study only as a means of describing the data. The Freun-
dlich equation is an empirical sorption model that can be expressed as:
S= KFCN
−1
where S represents the (total) amount of sorption (mg.kg
The McLeans Ridges soil, which has 0.48% (4779 mg kg−1) total As
(V) content, can be considered as highly contaminated, whereas the
Pearces Creek and Cudgen soils at 0.01 and 0.03% As(V) respectively
(129 and 245 mg kg−1), light to moderately contaminated (Table 1).
However, because the As-contamination in these soils occurred
some 60-years ago, their current loading can be considered to be well-
aged, and effectively oxidised to As(V) (Rahman et al., 2017a). A
dominance of As(V) is in concordance to previous studies on As-spe-
(1)
ciation in the long term As-contaminated sites (Arai et al., 2006; Burton
), KF is the et al., 2014; Cances et al., 2005; Meunier et al., 2010; Niazi et al.,

116
M.S. Rahman, et al. Applied Geochemistry 105 (2019) 114–124

Table 2
A summary of mineralogical composition of the pristine and contaminated soils from the cattle dip sites and standard soils determined by XRD.
Soil properties Soil samples

McLeans Ridges Pearces Creek Cudgen Ferralitic Sandy OECD

Minerals
SiO2 Quartz Quartz Quartz Quartz Quartz Quartz
Fe2O3 Hematite Hematite – Hematite – –
Fe3O4 Magnetite Magnetite – – – –
FeO(OH) Goethite Goethite – Goethite – –
Al4(OH)8(Si4O10) Kaolinite Kaolinite – – Kaolinite
TiO2 Anatase Anatase – Anatase – –
Na(AlSi3O8) – Feldspar – – –
Al(OH)3 – – – Gibbsite – –
FeTiO3 Ilmenite Ilmenite Ilmenite – –
Na8(AlSiO4)6(ClO4)2 – – Sodalite – Sodalite –
Na(AlSi3O8) – – Albite – – –
Na0.3(Al, Mg)2Si4O10(OH)2·8H2O – – – – Montmorillonite –

Particle size (%)a

Clay 44.96 60.08 9.03 39.10 13.92 15.02
Silt 28.01 24.02 1.06 45.86 2.01 8.91
Sand 27.03 15.90 89.91 15.04 84.07 76.07

a
Data represent the mean of triplicate soil analysis (standard error of mean < ± 5%, n = 3).

2011). The low-contaminated Pearces Creek ferralitic soil sorbed As(V) at

All contaminated soil sites recorded pH's between 4 and 6, however
total Fe concentrations varied considerably from 0.14 to 10 wt %.
Pristine sandy soil, standard (OECD) soils and contaminated sandy soil
(Cudgen) all contain < 1 wt % total (Table 1). In contrast, and as ex-
pected, the two As-contaminated ferralitic soil samples (McLeans
Ridges and Pearces Creek), and pristine ferralitic soil contained from 6
to 10 wt % total Fe. The soil mineralogy is presented in Table 2, which
shows the particle size distribution of the soils, demonstrating that the
sandy Cudgen soils, the reference sandy soil and the OECD soil form a
group of significantly lower clay content. The McLeans Ridge soil and
Pearces's Creek soil (as well as the Ferralitic reference soil) form a
second group of more clay-size-dominated soils.
3.2. Sorption of As(V) in the soils
Arsenic sorption to the soils after loading with solutions containing
As(V) and equilibrating for 96 h are presented in Fig. 1. The amount of
As(V) sorbed varied greatly between soils. However, in general, soils
containing low Fe and Al concentration (i.e., contaminated Cudgen
sandy, pristine sandy and OECD) (Table 1) sorbed much less As(V)
compared to soils with high Fe and Al concentration (i.e. contaminated
McLeans Ridges and Pearces Creek ferralitic, and pristine ferralitic
soils) (Figs. 1 and 2; Table 1). Pristine ferralitic soil sorbed As(V) up to
1250 mg kg−1 at pH 5, whereas the pristine sandy soil had 21–51% less
As(V) sorption (Fig. 1b) suggesting that As(V) sorption variability can
be attributed to the soils Fe and Al oxide content (Fig. 2; Table 2),
consistent with others findings (Manning and Goldberg, 1997; Smith
et al., 1999).
When exposed to fresh As(V) solutions, highly-contaminated
McLeans Ridges soil showed an As release to the soil solution
(45.16 mg kg−1) at lowest investigated added As(V) concentration of
0.05 mM. In contrast, at higher concentrations, further sorption of As
(V) to the soil occurred up to 523 mg kg−1 (Fig. 1a). Hence, these data
suggest that the highly contaminated soil is effectively As-saturated
(close to saturation with As or approaching over-saturation), most
likely due to limited strong binding sites as opposed to weak equili-
brium-controlled association of new As(V) to soil mineral surfaces
(Table 2) (Goldberg and Johnston, 2001; Smith et al., 2002). Hence,
further exposure of this contaminated soil to As(V) may increase As-
mobilization because of a decreased soil retention efficiency of addi-
tional As at higher concentrations.
all As addition concentrations. The amount of sorbed As(V) in the
Pearces Creek soil equated to > 92% of that sorbed by the corre-
sponding pristine ferralitic soil (Fig. 1a and b), indicating that the soil
had a substantial capacity to further bind As(V). However, there was a
significant discrepancy for the Cudgen soil where in the contaminated
soil, less than 31% As(V) was sorbed compared to the corresponding
pristine sandy soil (Fig. 1a–b). This comparison suggests that the
Cudgen soil with its low ECEC (Table 1) is much more heavily loaded
and approaching saturation with respect to its overall As(V) sorption
capacity than either the Pearces Creek sample, or the pristine ferralitic
soil (Fig. 1a and b). The OECD standard soil had relatively low As(V)
sorption capacities, displaying substantially lower As(V)-sorption than
the other non-contaminated soils (Fig. 1b); most likely due to low Fe
and Al content (Table 1). Earlier research emphasized the importance of
Fe and Al oxides as one of the main factors determining the soils’
sorption capacity for As (Fig. 2) (Manning and Goldberg, 1997; Smith
et al., 1999, 2002; Zhang and Selim, 2005). Moreover, the strong cor-
relations between Fe contents, and clay contents (Fig. 2) are not su-
prising because most Fe-containing particulates are clay sized (Rahman
et al., 2017a, b)
3.3. As(V) sorption isotherm in soils
Both Freundlich and Langmuir equations describe the As(V) sorp-
tion data well in the soils studied (Table 3), although the data were
comparatively better described by the Freundlich isotherms with
slightly more significant linear plot fitting (R2 ≈ 0.902–0.999; Table 3).
However, the highly contaminated McLeans Ridges soil showed As(V)-
releases to the equilibrium soil solution when exposed to low initial
solution concentration of As(V) (0.05 mM) (Fig. 1a, c and e), which
consequently, meant that neither Freundlich and Langmuir equations
adequately describe As(V) sorption data; McLeans Ridges soil also
showed As(V) release at initial low and higher As(V) solution con-
centrations at pH 9.
The soils showed a wide range of Freundlich KF values (Table 3),
with low values typifying soils having low As(V) sorption capacities,
and high values the reverse. For example, the Pearces Creek and pris-
tine ferralitic soils contain large amounts of extractable Fe and Al, and
the KF values for these soils are relatively large (211 and 257 L kg−1 at
pH 5, respectively; Tables 1 and 3), indicating that large proportions of
freshly added As(V) are readily sorbed by the soils. This rapid sorption

117
M.S. Rahman, et al.
is also reflected in their higher Langmuir As(V) sorption maximum
(Smax) with much greater KL values (related to the binding strength;
Table 3). Whereas, pristine sandy and OECD soils containing sub-
stantially lower amounts of Fe and Al (Table 1), have low Freundlich KF
values (≤112 L kg−1 at pH 5; Table 3) indicating that a large amount of
the freshly added As(V) remains in solution. Consequently, a relatively
low Langmuir Smax and KL values for As(V) sorption are also observed in
the pristine sandy and OECD soils (Table 3).
Furthermore, and in contrast, the aged contaminated McLeans
Ridges and Cudgen soil had very low affinity for freshly added As(V)
compared with their corresponding pristine ferralitic and sandy soils, as
evident by the lower Freundlich Kf values (< 39 L kg−1) at pH 5
(Table 3). Similarly, aged contaminated McLeans Ridges and Cudgen
soil also have substantially lower Langmuir As(V) sorption Smax and KL's
are also observed in these highly contaminated soils compared to cor-
responding pristine ferralitic and sandy soils (Table 3).
3.4. The effect of pH on As(V) sorption
Fig. 1 shows a decrease in As(V) sorption with increasing pH for all
118
Applied Geochemistry 105 (2019) 114–124
Fig. 1. Sorption of As(V) by contaminated
cattle dip site soils as well as pristine and
standard soils. Symbols are experimental
data points. Solid curves depict results of
curve-fitting with the Freundlich equation.
The highly contaminated McLeans Ridge
soil released As to the equilibrium soil so-
lution when exposed to the initial lower
solution concentration of As (V) (0.05 mM)
at pH 5 and 7, therefore, curves are fitted to
the data using initial higher concentration
of As(V) (0.20, 0.27, 0.66 and 1.00 mM) at
which the sorption of As(V) occurred on
soils. Moreover, the release of As was ob-
served at both of the initial lower and
higher solution concentrations of As(V) at
pH 9 in the McLeans Ridges soil, conse-
quently, neither the Freundlich and
Langmuir equation were able to describe
the sorption data. Data represent the mean
values (standard error of mean < ± 4%,
n = 2).
soils studied here, which is in agreement with other studies (Manning
and Goldberg, 1996; Smith et al., 1999). The highly contaminated
McLeans Ridges soil showed ≈24% decline in As(V) sorption at pH 7 as
compared to pH 5 (Fig. 1a and c), and a much greater release of As(V)
to the soil solution was observed at pH 9 (Fig. 1e) suggesting that the
soils are nearly saturated with As(V). In comparison, the Pearces Creek
and pristine ferralitic soil showed less of a pH-dependent decline in As
(V) sorption (10–25%; Fig. 1a–f) with increasing pH, suggesting that
both of these ferralitic soils have significant As(V)-sorption capacity
even at higher pH's. The Cudgen sandy soil sorbed additional As(V)
under all pH conditions examined here, but the decline in relative
sorption was up to 88% at highest pH (Fig. 1a, c and e). Whereas, there
was a relatively lower decline in As(V) sorption (< 50%) in the pristine
sandy soil with increasing pH from 5 to 9 (Fig. 1b and d).
Overall, the pH-dependent adsorption results indicate a decrease in
As(V) sorption with increasing pH is less pronounced in the pristine
ferralitic and low contaminated ferralitic soils. Whereas, a more pro-
nounced pH-dependent release of As(V) at higher pH was found in the
aged contaminated soils (McLeans Ridges and Cudgen). The higher pH
will increase de-protonation of neutral H3AsO4 species, which will
M.S. Rahman, et al.
Fig. 2. Correlations between the As(V) sorption and Fe and Clay contents in
soils. Fitted data trendlines use (initial As(V) of 0.27 mM at pH 5) for con-
taminated soils (McLeans Ridge, Cudgen and Pearces Creek) and non-con-
taminated soils (Ferralitic, Sandy and OECD). Data represent the mean values
(standard error of mean < ± 4%, n = 2).
increase anionic concentrations and negative surface potentials as the
isoelectric points of soil minerals are crossed (Aharoni et al., 1991; Ho
et al., 2000; Sherman and Randall, 2003; Smith et al., 1999). Conse-
quently, these two interacting factors lead to a decrease in As(V)
sorption as pH increases through electrostatic repulsion. Moreover, a
release of As(V) to the soil solution observed at higher pH's in the
highly-contaminated McLeans Ridges soil was most likely due to sur-
face-charge changes (Clark et al., 2011a). Consequently, this suggests
that increases in soil pH from any alkalinity source in long-term As-
contaminated cattle dip sites may promote currently sorbed and im-
mobilised As(V) to release.
3.5. Sorption of As(V) on soils in the presence of competing anions and
index cation
The effect of phosphate (P) on the sorption of As(V) is shown in
Fig. 3a–b, where the greatest effect was observed in the McLeans Ridges
and Cudgen contaminated soils. With the McLeans Ridges and Cudgen
soils, the soil-sorbed As(V) decreased between 35 and 95% (Figs. 1aand
2a). In the contaminated soils, the effect of P appeared to be more
pronounced with a > 100% decrease in As(V) sorption at lower initial
fresh As loadings (0.05 mM) (Figs. 1aand 2a). This decrease is con-
sistent with the majority of the added As(V) being associated with both
non-, and specific sorption sites that also display a high affinity for
phosphate. Phosphate may compete with As(V) oxyanions for available
sorption sites (non- or specific), and As(V) displacement by phosphate
increases As(V) soil mobility (Das et al., 2015; Goh and Lim, 2004;
Smith et al., 2002). Interestingly, phosphate had little effect on As(V)
sorption (average reduction < 15%) in the less contaminated Pearces
Creek and pristine ferralitic soils (Fig. 1a, b, 2a & 2b), most likely be-
cause of the high availability of sorption sites and the under-saturated
nature of these soils.
119
Applied Geochemistry 105 (2019) 114–124
The suppressed sorption of As(V) in the presence of P has been re-
ported by others (Das et al., 2015; Manning and Goldberg, 1996;
Nordstrom et al., 2014; Smith et al., 2002). The increased competition
for available sorption sites between As(V) and P and the variable degree
of this competitive sorption effect may be attributed to the varying
sorption capacity and saturation (by previous As(V) contamination) of
the soils studied. In soils with low sorption capacity for new As(V)-
loadings (i.e. the contaminated McLeans Ridges and Cudgen soils;
Fig. 1a and b), the competitive effect of P was more evident than in soils
with high As(V)-sorption capacity (i.e. low contaminated Pearces Creek
and pristine ferralitic soils; Fig. 3a and b) that is, that the competitive
effect of P is most apparent in soils where sorption site availability are
low (Smith et al., 2002). Conversely, in high As(V)-adsorbing soils and
low-As solution concentration, this effect is minimized from the high
availability of sorption sites for both competing oxyanions. However, at
increased P solution concentrations, strongly-binding P competes ef-
fectively for available sorption sites thereby reducing As(V)-sorption;
this hypothesis is also supported by sorption data (Fig. 1b) for soils with
a low sorption affinity for As(V). In contrast, at low As(V) and P solu-
tion concentrations show limited P control on As(V)-sorption (< 15%
reduction; Fig. 1a, b, 2a & 2b) by the soils with high As(V)-sorption
affinities (Pearces Creek and pristine ferralitic soils), suggesting that
both ions are strongly retained by soil colloids.
In general, similar trends to those observed for As(V)-P competition
were also found in case of As(V)-S (sulfate) competition. However, the
effects of S on As(V)-sorption were not as marked as those previously
discussed for P (Fig. 1a, b, 2c & 2d), most likely because sulfate is more
weakly bound to soils than phosphate. The largest effect of S on As(V)
adsorption was observed in the highly-contaminated soils of McLeans
Ridges and Cudgen (< 24% average reduction) with an average <
17% decline in the pristine sandy and OECD soils (Fig. 1a, b, 2c & 2d).
In contrast, little effect of S on As(V) sorption was observed (< 8%
average reduction) for the lower contaminated Pearces Creek and
pristine ferralitic soils (Fig. 1a, b, 2c & 2d), consistent with the high
affinity that these soils have for freshly added As(V). This is consistent
with other work where P significantly suppressed As(V) sorption
whereas Cl−, NO3−, and SO42− additions had little effect (Livesey and
Huang, 1981). Also, phosphate may compete with arsenate for all
available adsorption sites (specific or non-specific), whereas sulfate has
been reported to compete only for non-specific sorption sites (Das et al.,
2015; Goh and Lim, 2004).
Comparisons of KF values (Table 3) further illustrate the marked
competitive effect of P in low-sorbing soils. Table 3 showed that KF in
the presence of P decreased between average 39–82% in the low
sorbing contaminated soils (McLeans Ridges and Cudgen), whereas the
reduction was < 28% in the high sorbing low contaminated and pris-
tine ferralitic soils. These data support the hypothesis that the compe-
titive effect of P on As(V)-sorption depends on number of available
sorption sites and the extent of saturation of those sites by the two
anions. Phosphate and S compete with As(V) for sorption sites on the
soil-mineral surfaces, which is pronounced for soils with limited sorp-
tion sites (e.g. McLeans Ridges and Cudgen soil), but where sorption
sites are less limited (low contaminated and pristine ferralitic), both As,
and the competing P and S are strongly retained. Therefore, application
of phosphate- and sulfate-based fertilizers to highly contaminated
McLeans Ridges and Cudgen cattle dip soils will lead to increased
sorption sites competition, and potential As(V) mobilization.
The effect of cations on As(V)-sorption (Fig. 3e–f), indicate that ir-
respective of the nature of the solution, the As(V) sorption was en-
hanced by the presence of Ca2+ ions (compare Fig. 1a, b, 2e & 2f). An
average 9–15% increase in As(V) adsorption was found in the con-
taminated McLeans Ridge and Cudgen soils in the presence of Ca2+ ions
(Figs. 1aand 2e), whereas the low-contaminated Pearces Creek and
pristine ferralitic soils sorbed an average of < 6% additional As(V) (i.e.
about half of that found in the pristine sandy and OECD soils;
Figs. 1band 2f). An increase in As(V)-sorption in the presence of added
M.S. Rahman, et al. Applied Geochemistry 105 (2019) 114–124

Table 3
Estimated Freundlich- and Langmuir-equation parameters for As(V) sorption in soils at different equilibration pH, and presence of competing anions and index cation.
The experiments with added P, S and Ca were undertaken at pH 5.
c c
Soils Freundlich Langmuir R2

KF (L.kg−1) N R2 KL (L.mg−1) Smax (mg.kg−1)

McLeans Ridges pH 5 38.7 0.655 0.948 0.029 704.2 0.893

pH 7 35.1 0.604 0.916 0.026 662.3 0.918
pH 9a – – – – – –
P 7.14 0.893 0.998 0.033 166.7 0.920
S 24.4 0.703 0.957 0.020 694.4 0.886
Ca 60.3 0.566 0.967 0.036 832.6 0.982

Cudgen pH 5 7.91 0.780 0.951 0.019 333.3 0.871

pH 7 5.61 0.781 0.953 0.018 243.9 0.857
pH 9 0.42 1.237b 0.985 0.007 86.96 0.733
P 4.75 0.604 0.944 0.028 196.1 0.954
S 5.70 0.805 0.973 0.015 303.0 0.836
Ca 10.1 0.764 0.953 0.022 357.1 0.932

Pearces Creek pH 5 211 0.470 0.991 0.136 1391 0.977

pH 7 182 0.485 0.980 0.133 1250 0.978
pH 9 82.9 0.620 0.974 0.061 1111 0.982
P 153 0.520 0.988 0.106 1238 0.987
S 202 0.475 0.974 0.152 1294 0.989
Ca 307 0.401 0.977 0.250 1429 0.981

Ferralitic pH 5 257 0.435 0.991 0.177 1416 0.976

pH 7 220 0.445 0.990 0.171 1220 0.983
pH 9 149 0.470 0.979 0.122 998.0 0.981
P 190 0.475 0.986 0.141 1248 0.985
S 220 0.463 0.971 0.172 1294 0.991
Ca 307 0.401 0.977 0.239 1443 0.985

Sandy pH 5 112 0.420 0.997 0.099 714.3 0.983

pH 7 81.0 0.450 0.999 0.071 627.0 0.965
pH 9 41.6 0.510 0.992 0.048 454.5 0.920
P 87.6 0.365 0.966 0.141 398.4 0.985
S 97.8 0.435 0.989 0.106 621.1 0.989
Ca 154 0.380 0.983 0.168 735.3 0.992

OECD pH 5 26.2 0.411 0.952 0.076 166.7 0.975

pH 7 11.0 0.576 0.974 0.034 159.7 0.911
pH 9 3.82 0.763 0.902 0.020 116.3 0.748
P 18.4 0.362 0.972 0.102 90.91 0.993
S 23.3 0.398 0.918 0.117 123.5 0.996
Ca 31.8 0.394 0.928 0.094 178.6 0.981

a
The isotherm equations do not describe the sorption data in these cases due to the release of As to the equilibrium soil solution when exposed to both the initial
lower and higher solution concentration of As(V).
b
This unusual value exceeding 1 is attributed to the very low As sorption obtained in this experiment.
c
Data represent the mean values (standard error of mean < ± 4%, n = 2).

Ca2+ has been reported by other studies (Naidu et al., 2009; Smith mobility and potential toxicity; this could be extended to trivalent
et al., 2002), where the index cation effect was attributed, in part, to the metals (Al and Fe; Pigna et al. (2006).
effect of the divalent cation on the nature of the As(V) species present,
and the pH of the soil suspension (pH = 0.1–0.3 units lower in the
3.6. Arsenic sorption and retention in soils using isotope exchange
presence of Ca2+ than Na+). Pigna et al. (2006) explained that in-
creasing cation valency makes the potential sorption-plane more posi-
Isotope exchange experiments compare the sorption behaviour of
tive, thereby increasing anion sorption. Therefore, changing the cation
added 73As with the natural 75As isotope, which had previously re-
from Na+ to Ca2+ at constant ionic strength increases positive charging
tained in soils by the historic As-contamination and/or been freshly
of soil-particle surfaces, thereby enhancing As(V)-sorption. In high As
added to the soils (i.e. soils pre-equilibrated with 75 A at pH 5).
(V)-sorbing soils (Pearces Creek and ferralitic soils), the presence of
Differences in the behaviour of the isotopes of the same element can
Ca2+ had little additional effect on As(V)-sorption, because there is
therefore be ascribed to irreversible phenomena or incorporation in the
already an abundance of positively charged sorption sites. Hence, these
soils.
data further support the hypothesis that the effects of competing ions
The different soils have quite different arsenic retention properties
depend on the number of available sorption sites, and the concentration
(Fig. 4a–f). For the uncontaminated soils which contain only two
of competing ions. Consequently, competition is only evident in low-
sources of arsenic (i.e., stable 75As added during the pre-equilibration
adsorbing soils (McLeans Ridges, Cudgen, pristine sandy and OECD
step and tracer 73As present in the isotope exchange part of the ex-
soils), or when the sorption sites numbers are limited by high con-
periment). A key feature of the results is that for all soils and pH values,
centrations of sorbing ions. However, these data suggest that divalent
the pre-existing 75As is more strongly bound than the 73As. For the
metal applications (e.g., Ca and Mg as chlorides or nitrates) to con-
pristine ferralitic and sandy soils, containing newly sorbed 75As(V),
taminated sites may improve As(V)-retention thereby decreasing As(V)-
some 6–21% and 19–50% of the fresh-As(V) was isotopically

120
M.S. Rahman, et al.
exchangeable (Fig. 4d and e), respectively. Over very short time frames
(a few days between loading and the isotope exchange step), the re-
maining significant portion of newly sorbed 75As(V) in the pristine soils
became associated with irreversible forms, resulting in a greater re-
tention compared to the tracer 73As (Fig. 4d and e). This rapid accu-
mulation of irreversibly-sorbed As(V) may result from several me-
chanisms, including surface precipitation, and/or formation of
bidentate complexes, and/or diffusion controlled reactions (Fendorf
et al., 1997; Fuller et al., 1993; Raven et al., 1998; Waychunas et al.,
1993; Zhang and Selim, 2005). Another possibility is precipitation of
scorodite, or Al- and Ca-arsenates, as previously observed in the con-
taminated soils (Rahman et al., 2017a). In addition, the ferralitic soil
had more irreversible As retention capacity compared to the sandy soil
(Fig. 4d and e), which was most likely due to the higher Fe and Al
contents for precipitation reactions, and/or the high surface areas of
fine Fe, Al-oxy-hydroxides and clays to provide adsorption sites (Tables
1 and 2). Soils rich in Fe/Al oxides and oxy-hydroxides have been
shown to rapidly sorb arsenic (Girouard and Zagury, 2009; Smith et al.,
1999; Tang et al., 2007; Yang et al., 2003; Zhang and Selim, 2005) and
high clay content soils also lead to decreased arsenic accessibility
(Girouard and Zagury, 2009). In the OECD standard soil, a highest
121
Applied Geochemistry 105 (2019) 114–124
Fig. 3. Sorption of As(V) by cattle dips sites'
contaminated, pristine and standard soils in
presence of the competing anions (P, S) and
index cation (Ca) at pH 5. Symbols are for
experimental data. Solid curves depict re-
sults of curve-fitting with the Freundlich
equation. The highly contaminated
McLeans Ridges soil released As to the
equilibrium soil solution when exposed to
the initial lower solution concentration of
As(V) (0.05 mM) in presence of phosphate
(P), sulfate (S) and Ca, therefore, the curve
is fitted to the data using initial higher
concentrations of As(V) (0.20, 0.27, 0.66
and 1.00 mM) at which the sorption of As
(V) occurred on the soils. Data represent the
mean values (standard error of mean <
± 4%, n = 2).
fraction (52–85%; Fig. 4f) of sorbed As(V) was found in reversibly
bound form, which is much higher than that found for sandy soils,
suggesting that Fe and/or Al-oxy-hydroxides play a key role in in-
creasing irreversible binding where Fe and Al are two key elemental
differences between the sandy and OECD standard soil (Tables 1 and 2).
Furthermore, the high organic carbon (5.85% as plant matter; Table 1)
in the OECD soil has been shown to increase As-accessibility (Dobran
and Zagury, 2006; Girouard and Zagury, 2009; Meunier et al., 2011).
For contaminated soils (McLeans Ridge, Pearces Creek and Cudgen),
the situation is more complex, because the sources of arsenic include
both the arsenic originally on the soils as well as (in the second set of
experiments) arsenic added during the pre-equilibration step. Due to
long exposures to arsenic in the environment, these soils have much
higher percentages of non-exchangeable arsenic (75As) (> 90% sorbed
on soil; Fig. 4a–c) resulting in less release of As to solution, compared to
the analogous experiments with pristine soils. There is a higher pro-
portion of 73As in solution than 75As for all recorded pH values
(Fig. 4a–c). This is because most of the 75As from historic As-con-
tamination is irreversibly bound to the solids and not available for
isotope exchange. This may be attributed to their long-term aging and
conditioning in the environment, over a period of decades (Bauer et al.,
M.S. Rahman, et al. Applied Geochemistry 105 (2019) 114–124

Fig. 4. Sorption behaviour of pre-existing stable 75As and added tracer 73As in isotope exchange experiments. For soils, −0.20 mM stands for freshly loaded soil with
0.20 mM As(V). Solid lines in Fig. 3a–b represent isotope exchange plots for the non-loaded contaminated soils. Dashed lines in Fig. 3a–f represent isotope exchange
plots for all freshly pre-loaded soils [i.e., contaminated, pristine and OECD soils freshly loaded with 0.20 mM 75As(V) at pH 5].

2018). During the exposure of the soils to environmental arsenic, the
arsenic in the samples has become associated with the minerals
(Table 2) and stable, strongly bound forms (Rahman et al., 2017a).
Addition of fresh As(V) (0.2 mM) to the aged contaminated soils
(McLeans Ridges, Pearces Creek and Cudgen) showed increased
amounts of exchangeable-As(V) (Fig. 4a–c), because the newly added
As(V) was more likely associated with soil-mineral surfaces (Table 2)
during the sorption experiment than the more mineralised pre-existing
As(V).
4. Conclusions
Our studies using batch sorption experiments and an isotope ex-
change technique provide a novel description of the As(V) sorption
characteristics and accessibility in the aged long-term contaminated
soils as well as non-aged As(V) loaded pristine soils. This study clearly
shows that recently contaminated soils, pose a greater environmental
risk than similarly contaminated soils, with a much older contamina-
tion history. In the contaminated soils, pH had a large effect, with a
reduction in As(V)-sorption with increasing pH, suggesting that pH
increases in the long-term contaminated soils can potentially release the
As to the environment. The additional presence of P greatly decreased
As(V)-sorption by the aged contaminated soils as did the presence of S;
S effects were not as marked as those for P. Consequently, the appli-
cation of phosphate- and sulfate-based fertilizer in As(V)-contaminated
soils can lead to potential As(V)-mobilization. However, the presence of
Ca2+ increased As(V)-sorption by all soils studied, indicating that the
application of divalent cation sources (e.g., Ca2+ and Mg2+), and by

122
M.S. Rahman, et al.
extrapolation possibly trivalent cations (e.g., Al3+ and Fe3+) to As(V)-
contaminated soil may increase As(V)-retention, resulting in a decrease
in As accessibility. Isotope exchange experiments showed that the fur-
ther exposure of the historic contaminated soils to elevated arsenic le-
vels can lead to a decreased ability to incorporate As(V) within resistant
soil particles and may possibly release and mobilize already bound As
(V). This increased mobilization may lead to strongly-bound As(V)
becoming more labile in the environment. However, it is such detailed
knowledge of soil behaviour that is vital for risk assessment and man-
agement of the As(V)-contaminated soils.
Acknowledgments
The authors acknowledge the support from SCU, Australian Institute
of Nuclear Science and Engineering (AINSE grant: ALNGRA13054)) and
Australian Nuclear Science and Technology Organisation. We would
specifically like to thank SCU staff member Barbara Harrison for helpful
discussions and assistance.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.apgeochem.2019.04.016.
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