water research 43 (2009) 1589–1596

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Arsenic mobility and stabilization in topsoils

Konstantina Tyrovola*, Nikolaos P. Nikolaidis

Department of Environmental Engineering, Technical University of Crete, University Campus, 73100 Chania, Crete, Greece

article info abstract

Article history: Agricultural topsoil can be polluted with arsenic due to irrigation with contaminated water
Received 27 June 2008 from geothermal sources. This work evaluates the mobility of arsenic in topsoils and
Received in revised form stabilization of arsenic with zero valent iron (ZVI), in short term experiments. The
23 December 2008 objective of this study was the development of a simplified empirical model that can
Accepted 5 January 2009 predict the concentration of iron released from ZVI and the concentration of arsenic
Published online 18 January 2009 remaining in the solution during short term stabilization experiments. The empirical
model correlates the release of arsenic from soil with dissolved iron concentration during
Keywords: stabilization experiments, in different pH and ZVI/solution ratios. Reaction time and the
Arsenic ratio of ZVI/soil affect the efficiency of arsenic stabilization in topsoils with ZVI. In addi-
Soil tion, the release/desorption experiments and adsorption experiments, under different
Stabilization conditions, showed that the concentration of arsenate desorbed from soil depends on the
Zero valent iron temperature. Higher concentrations of arsenate were reported, as the temperature
Iron corrosion increased.
ª 2009 Elsevier Ltd. All rights reserved.

1. Introduction springs and geysers or beyond the boundaries of the geothermal

Arsenic (As) is a commonly occurring toxic and carcinogenic
element. Increasing amounts of arsenic are being introduced
into soil and water environments posing serious health risks
to humans. Even though arsenic occurs in various oxidation
states (þ5, þ3, 0 and 3), arsenite (As(III)) and arsenate (As(V))
are the most common species in natural environments.
Arsenic contamination in geothermal systems has been
identified in many regions all over the world. In most
geothermal systems, arsenic is discharged mainly in the
reduced form of arsenic (As(III)) (Wilkie and Hering, 1998).
Microbiological activity seems to enhance the oxidation of
As(III) to As(V) during the ascension of geothermal hot waters
and their mixing with shallow oxidized groundwaters (Wilkie
and Hering, 1998; Langner et al., 2001). Arsenic originated from
geothermal systems can be transported to surface and
groundwaters causing contamination.
Soil contamination can occur either in the vicinity of the
geothermal system due to direct arsenic discharge from hot
system due to irrigation with contaminated water originated
from geothermal systems. The fate and behavior of arsenic in
soils depends greatly on the processes of adsorption and
desorption/release (Naidu et al., 2006; Yang et al., 2005; Zhang
and Selim, 2005; Bowell, 1994; Williams et al., 2003). Redox
conditions and pH influence arsenic speciation, bioavailability
and mobility in soils. The effect of the pH, the concentration of
phosphate and the ionic strength on adsorption/desorption of
arsenic from soils has been studied by many researchers
(Bowell, 1994; Williams et al., 2003; Lumsdon et al., 2001;
Impellitteri, 2005). The presence of phosphate in solution can
decrease the amount of arsenic sorbed by soil due to the fact
that arsenic has similar chemical behavior to that of phospho-
rous (Smith et al., 2002; Williams et al., 2003; Melamed et al.,
1995). In addition, the work of Lambkin and Alloway (2003)
showed that the addition of arsenic in soils induced the mobi-
lization of phosphate in the solution.
Remediation of arsenic-contaminated soils can be achieved
by many technologies: biological treatment, phytoremediation,

* Corresponding author. Tel.: þ30 28210 37815; fax: þ30 28210 37847.
E-mail addresses: konstantina.tyrovola@enveng.tuc.gr (K. Tyrovola), nikolaos.nikolaidis@enveng.tuc.gr (N.P. Nikolaidis).
0043-1354/$ – see front matter ª 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.watres.2009.01.001
1590 water research 43 (2009) 1589–1596
solidification/stabilization, fixation, vitrification, soil flushing,
electrokinetic remediation (U.S. EPA, 2002; Mulligan et al., 2001).
Arsenic stabilization in soils can be achieved with the addition of
iron based chemicals or other treatment solutions in order to
decrease the leachability of arsenic from contaminated soils
(Artiola et al., 1990; Warren et al., 2003; Martin and Ruby, 2003;
Yang et al., 2007; Codling and Dao, 2007). Zero valent iron (ZVI)
has been used successfully as a reactive medium for permeable
reactive barriers for in situ remediation of arsenic from
contaminated soil and groundwater in the field. The addition of
ZVI (Fe0) to soils results in the formation of Fe(II) and Fe(III)
corrosion products onto the surface of iron due to oxidation and
iron oxide coatings on soils. Corrosion products are a mixture of
amorphous Fe(III) oxide/hydroxide, magnetite and/or maghe-
mite and lepidocrocite. The formation of various corrosion
products on the surface of ZVI results in the creation of
adsorption sites for arsenic. The suggested mechanism of
arsenic removal is the formation of inner-sphere bidentate
complexes on iron corrosion products or surface precipitation
on ZVI (Nikolaidis and Tyrovola, 2006; Su and Puls, 2001). Recent
projects have been conducted and evaluated the efficiency of
ZVI on the stabilization of arsenic, chromium and copper
(Kumpiene et al., 2006) and also the factors that control the
stability of arsenic in iron treated soil (Kumpiene et al., 2007).
These projects did not study the corrosion of iron under different
conditions and they did not correlate iron corrosion with arsenic
stabilization with ZVI.
The main objective of this study was the development of
a simplified empirical model that can predict the concentra-
tion of arsenic released in the solution during short term
stabilization experiments of topsoil with ZVI. The working
hypothesis was that increasing amounts of ZVI can lead i) to
an increase of dissolved iron concentration, ii) to an increase
of arsenic stabilization and iii) to a decrease of arsenic
mobility/bioavailability in the topsoil. Therefore, we wanted
to correlate the release of arsenic from soil with dissolved iron
concentration during stabilization experiments, in different
reaction times. In order to achieve our goal first we related
iron concentration with pH under different ZVI/solution ratios
in iron corrosion experiments. Then we conducted stabiliza-
tion experiments in order to study the effectiveness of ZVI in
reducing the amount of arsenic released from soil. In this way,
we created a methodology (an empirical model) of predicting
iron and arsenic concentrations during stabilization experi-
ments. Furthermore we conducted release/desorption exper-
iments and adsorption experiments in order to understand
the behavior of topsoil under different conditions. In this way
we can evaluate i) the amount of arsenic released due to rain
or due to the irrigation of soil with uncontaminated ground-
water and ii) the amount of arsenic adsorbed with soil due to
irrigation of soil with arsenic contaminated groundwater.
2. Methodology
2.1. Materials and methods
2.1.1. Soil
Topsoil sample was collected from the area of the geothermal
field of Triglia-Petralona. Triglia is a town in Western
Chalkidiki (Central Macedonia, Greece). Arsenic contamina-
tion in the irrigation and the potable water wells in the region
of Triglia is caused by the karstic geothermal water (29–41  C),
with arsenic concentration varying from 1000 to 4000 mg/L
(Tyrovola et al., 2006). In the irrigation wells arsenic ranges
from 60 to 700 mg/L, while most of the potable water wells in
Triglia have arsenic concentrations above the drinking water
standards (10 mg/L). The work of Tyrovola et al. (2006) gives
a detailed map of the study area of Triglia.
Soil sample was homogenised, air dried and sieved. Only
the fraction smaller than 2 mm was used for the experiments.
The sample was analyzed for physical and chemical proper-
ties including particle size distribution, dry bulk density,
porosity, soil moisture, pH, organic carbon (OC), inorganic
carbon (TC) (as carbonate) and total nitrogen (TN) (CHN ana-
lyser). The soil samples were digested using Microwave 3000
(method 3051 EPA) in order to measure the total concentration
of arsenic and iron. In addition, X-ray-diffraction analysis was
conducted for the solid phase characterization.
2.2. Batch experiments for the kinetics of arsenic release
from contaminated soil
The main object of these experiments is to show the effect of
rain or irrigation with uncontaminated water to the release of
arsenic from topsoils. Batch kinetic release experiments were
conducted at three different temperatures (10, 20, 40  C), in
ambient soil pH. First, a preliminary kinetic release experi-
ment was carried out using the soil sample. This experiment
was conducted by adding 5 g of soil (<2 mm fraction) in plastic
bottles filled with 100 mL Triglia synthetic groundwater. The
bottles were placed in a shaker table at 200 rpm, in an incu-
bator in order to achieve the desired constant temperature.
The synthetic groundwater, representing the geochemistry of
Triglia geothermal groundwater, was prepared in the labora-
tory as described in the work of Tyrovola et al. (2006). Samples
were taken periodically with a syringe, centrifuged in
4000 rpm for 15 min, filtered with a nylaflo membrane 0.2 mm
filter and then analyzed for arsenic, and phosphates. Due to
the fact that the concentration of arsenic released from soil
was relatively low (about 80–110 mg/L, data not shown), we
could not proceed in the calculations of the rate of desorption/
release of arsenic. In addition, we could not observe apparent
differences in the concentration between each temperature.
For this reason, we conducted kinetic desorption experiments
with arsenic contaminated soil. These experiments were
conducted in duplicates as the preliminary ones. Arsenic
contaminated soil was prepared in the laboratory by spiking
arsenate in the uncontaminated soil sample, yielding a target
concentration of arsenate in the soil 60 mg/kg. Specifically,
contaminated soil was prepared by adding 50 g of uncon-
taminated soil sample (<2 mm fraction) in plastic bottles filled
with 1000 mL Triglia synthetic groundwater containing
5000 mg/L arsenate. The bottles were placed in a shaker table at
200 rpm, in an incubator at 20  C, for 4 days. Samples were
withdrawn from the supernatant solution and analyzed for
arsenate. The concentration of arsenate in soil was calculated
through the initial mass of arsenate added to the soil and the
mass of arsenate found in the supernatant solution. Then the
soil was dried to room temperature. Arsenate containing
 water research 43 (2009) 1589–1596
water was prepared, by diluting arsenate stock solution with
Triglia synthetic water. Arsenate stock solution (1000 mg/L)
was prepared from reagent grade Na2HAsO4$7H2O (Fluka) with
ultra pure water (Barnstead Easy Pure II).
2.3. Adsorption experiments
The main object of these experiments is to show the effect of
irrigation with contaminated water to the adsorption of
arsenic from topsoils. First, kinetic adsorption experiments
were conducted in duplicates at three different temperatures
(10, 20, 40  C), by adding 5 g of uncontaminated soil sample
(<2 mm fraction) in plastic bottles filled with 100 mL Triglia
synthetic groundwater containing 2000 mg/L arsenic (as As(V)).
Arsenic containing water was prepared, by diluting arsenic
stock solution with Triglia synthetic water. Arsenic stock
solution (1000 mg/L) was prepared from reagent grade
Na2HAsO4$7H2O (Fluka) with ultra pure water (Barnstead Easy
Pure II). The bottles were placed in a shaker table at 200 rpm,
in an incubator in order to achieve the desired constant
temperature. Samples were withdrawn and analyzed, as
described in the kinetic desorption experiments. We did not
conduct adsorption experiments with arsenite (As(III))
because speciation analysis in groundwaters in the area of
Triglia shows that As(V) is the predominant specie of arsenic
(Tyrovola et al., 2006).
In addition, batch adsorption equilibrium experiments
were conducted by adding 5 g of uncontaminated soil (<2 mm
fraction) in plastic bottles filled with 100 mL of Triglia synthetic
groundwater with concentrations of arsenate (As(V)): 100, 200,
500, 1000, 2000, 3000, 4000 mg/L. The experiments were carried
out in duplicate, at three different temperatures (10, 20, 40  C),
in ambient soil pH. The bottles were placed in the incubator in
a shaker table at 200 rpm for 4 days. Samples were taken with
the same way as described above.
The rate constants of arsenic desorption and adsorption
were determined with a first-order kinetic model that has the
general equation 1: C ¼ C0$ekt, where C and C0 are the
concentration of arsenic at time t and time t ¼ 0, respectively
and k (h1) is the rate constant. Specifically, the rate constants
(k) were evaluated from the slope of the plot of ln(C ) versus
time for adsorption and desorption of arsenic. The determi-
nation of the half-time t1/2 was conducted by equation 2:
t1/2 ¼ ln 2/k. The Activation Energy, Eact (kcal mol1), for each
process was determined from the Arrhenius relationship:
k ¼ AeEact =RT (equation 3), where k (h1) is the rate constant, T
is the absolute temperature in K, A is a constant and R is the
universal gas constant (1.987 cal mol1 K1). The Eact was
determined from the slope of the plot of ln k versus 1/T using
the data for three temperatures (10, 20 and 40  C). The exper-
imental data of equilibrium adsorption were fit with both
linear (Kd) and Freundlich isotherms. The equation used to
1=n
describe Freundlich isotherm was q ¼ Kf Ce (equation 4),
where q was the concentration of As(V) adsorbed in the equi-
librium (mg As/g soil), Ce was the aqueous concentration (mg/L)
of As(V) in the equilibrium, n was the adsorption intensity
parameter and Kf was the Freundlich adsorption capacity
parameter. Parameters Kf and n were determined using linear
regression with a linearized version of Freundlich isotherm
equation, which can be described as ln q ¼ ln Kf þ 1=n ln C
1591
(equation 5). In addition, the linear isotherm was described by
the equation q ¼ Kd Ce (equation 6), where Kd was the linear
capacity parameter (L/g).
2.4. ZVI corrosion as a function of solid to solution ratio
and pH, in the presence of arsenic
The main object of these experiments is to develop an
empirical equation that can predict dissolved iron concen-
tration under different ZVI/solution ratios and pH. ZVI was
obtained from Connelly-GPM, Inc. The physical properties and
the chemical composition of ZVI used were described in the
work of Tyrovola et al. (2006). These experiments were
designed using three different iron-to-solution ratios:
0.25 g/100 mL, 0.5 g/100 mL, 1 g/100 mL, and different pH
values (5.6, 6.5, 7.0, and 7.7). An appropriate mass of ZVI was
added to plastic bottles and the bottles were then filled with
Triglia synthetic water containing arsenic (2000 mg/L) either as
As(V) or as As(III). The initial pH of the solutions was adjusted
to the desired value with the addition of small amounts of
H2SO4 or NaOH. The bottles were placed in a shaker table at
200 rpm. These experiments were run in duplicates, for 4 h, at
20  C. Samples were taken with a syringe, filtered immediately
with a nylaflo membrane 0.2 mm filter and then analyzed for
total iron and arsenic.
2.5. Stabilization experiments
These experiments were conducted in order to study the
effectiveness of ZVI in reducing the amount of arsenic
released from soil. In addition, we want to create an empirical
model of predicting iron and arsenic concentrations during
stabilization experiments. The first stabilization experiment
was conducted using different iron-to-soil ratios at three
temperatures (10, 20 and 40  C). The duration of the first
stabilization experiment was 4 h. This experiment was con-
ducted in duplicates, by adding 20 g of uncontaminated soil
(<2 mm fraction) and various masses of ZVI, in plastic bottles
filled with 100 mL of Triglia synthetic groundwater. The
bottles were placed in a shaker table at 200 rpm for 4 h.
Samples were taken with the same way as described above.
The second stabilization experiment was carried out with
different mass ratios of ZVI:soil, at 20  C and two different
time intervals (4 and 24 h). Specifically, this experiment was
carried out, in duplicates, by adding 5 g of arsenic contami-
nated sample (<2 mm fraction) and various masses of ZVI, in
plastic bottles filled with 100 mL Triglia synthetic ground-
water. The bottles were placed in a shaker table at 200 rpm for
4 and 24 h. Samples were taken with a syringe, filtered
immediately with a nylaflo membrane 0.2 mm filter and then
analyzed for total iron and arsenic.
2.6. Chemical analysis
Chemical analysis of arsenic in digested samples and soil
extracts was conducted by Anodic Stripping Voltammetry
(ASV) with a Nano Band Explorer system (U.S. EPA, 1996).
This method is applicable for the determination of free dis-
solved As(III). Total arsenic analysis was conducted after the
addition of 0.5 N thiosulfate solution in the sample in order to
1592 water research 43 (2009) 1589–1596

covert all inorganic arsenic to As(III). As(V) was calculated by

a 800
10C 20C 40C
subtracting the measurement of As(III) from total arsenic. The
600

As (µg/L)
Method Detection Limit was 5 mg/L. Quality Assurance/Quality
Control (QA/QC) guidelines were followed for arsenic analysis 400
with ASV. Total analysis of arsenic and phosphates was also 200
determined with a colorimetric method (Dhar et al., 2004;
0
Johnson, 1971). Total dissolved iron was analyzed with a Hach 0 10 20 30 40 50 60 70 80 90
2010 spectrophotometer. time (hours)

b 20 10C 20C 40C

3. Results and discussion

PO4 (µg/L)
15
10
3.1. Physical and chemical characteristics of soil
5

Total arsenic concentration in the uncontaminated soil 0

sample was 8 mg/kg while total iron concentration was
552 mg/kg. The pH was 8.06, the porosity was 0.46, and the dry
bulk density was 1100 kg/m3. The fraction of soil <2 mm was
53.4%. The inorganic carbon content was 2.37%, organic
carbon content was 1.02% and nitrogen content was 0.34%.
According to the USDA Soil Textural Triangle, the soil was
characterized as silt loam. X-ray-diffraction analysis showed
that the main composition of the soil was quartz (SiO2),
calcium carbonate (CaCO3) and NaAlSi3O8. In addition, illite
and kaolinite were also identified. This soil was used for the
adsorption experiments. Arsenic contaminated soil with
60 mg/kg concentration of arsenic was used for the desorption
experiments and it was contaminated in the laboratory.
3.2. Batch experiments for the kinetic study of arsenic
release from contaminated soil
Arsenic release/desorption from contaminated soil at three
different temperatures (10, 20, 40  C), versus time is pre-
sented in Fig. 1a. Equilibrium was reached within 30 h. The
equilibrium concentration of arsenic released from soil
depends on the temperature. At 40  C the equilibrium
concentration was higher, than the equilibrium concentra-
tion at 10 and 20  C. The speciation of arsenic showed that
only arsenate (As(V)) was desorbed from the soil. Phosphates
were also released from soil at the same conditions. Fig. 1b
shows phosphate concentration versus time at three
temperatures (10, 20, 40  C). Higher concentrations of phos-
phates were measured at 40  C. The concentration of arsenic
and phosphates presented in Fig. 1 is the average concen-
tration measured in duplicate experiments. There is a signif-
icant variability in the measured concentrations in the
equilibrium which may be attributed to the experimental
errors and to the measurement of the concentration of
arsenic and phosphate. Specifically in the equilibrium, the
values of the standard deviation for arsenic concentrations at
10  C ranged from 6.5 mg/L to 90 mg/L, at 20  C ranged from
3.3 mg/L to 80 mg/L and at 40  C ranged from 6.5 mg/L to 90 mg/L.
Furthermore in the equilibrium, the values of the standard
deviation for phosphate at 10  C ranged from 0.2 mg/L to
2.5 mg/L, at 20  C ranged from 0.5 mg/L to 2.0 mg/L and at 40  C
ranged from 0.2 mg/L to 1.7 mg/L. For this reason, we cannot
observe explicit differences in the concentration of arsenic
and phosphate in equilibrium at 10 and 20  C. However, the
0 10 20 30 40 50 60 70 80 90
time (hours)
Fig. 1 – a) Release of arsenate from contaminated (60 mg/kg
As(V)) soil (5 g suspended in 100 mL) versus time at pH 8.06
and three different temperatures. Shown are As(tot)
concentrations in 0.2 mm filtered samples. b) Release of
phosphate from contaminated (60 mg/kg As(V)) soil (5 g
suspended in 100 mL) versus time at pH 8.06 and three
different temperatures. Shown are phosphate (PO3L 4 )
concentrations in 0.2 mm filtered samples.
effect of temperature is more distinguishable at 40  C where
the concentrations of arsenic and phosphate are higher than
those reported at 10 and 20  C.
The rates of As(V) desorption followed a first-order reaction
kinetic. The experimental data were modeled using the line-
arized form of the first-order kinetic model (equation 1), at
each temperature. Specifically at 20  C: ln C ¼ 0.0118*t þ 5.61
(equation 7). In addition, the half-time t1/2 of As(V) desorption
from soil was calculated at each temperature. Specifically, t1/2
is 66.6 h (2.8 days) at 10  C, 58.7 h (2.4 days) at 20  C and 45.9 h
(1.9 days) at 40  C. Table 1 presents the first-order rate
constants, k (h1) for the process of arsenate release at each
temperature and the values of Eact for arsenic desorption.
Overall, the rate of arsenate desorption increased with
temperature. However, due to the experimental variability the
change was statistically noticeable when the temperature
change was 20  C (from 20 to 40  C).
3.3. Adsorption experiments
Fig. 2a shows arsenate adsorption from soil at three different
temperatures, versus time. Temperature affects the rate of
arsenate adsorption and the equilibrium arsenate concen-
tration. Equilibrium was reached within 10 h. The concen-
tration of arsenate presented in Fig. 2a is the average
concentration measured in duplicate experiments. The
values of the standard deviation for arsenate concentrations
in the equilibrium at 10  C ranged from 3.3 mg/L to 114 mg/L,
at 20  C ranged from 3.4 mg/L to 47 mg/L and at 40  C ranged
from 17 mg/L to 117 mg/L. The kinetic adsorption experiment
was modeled using a first-order kinetic model. The first-
order constants, k (h1) for the adsorption process are
 water research 43 (2009) 1589–1596 1593

were applied in order to assess the effect of temperature on

Table 1 – First-order rate constants for arsenic desorption
and adsorption. the adsorption of arsenate and release of phosphates. The
statistical criteria showed that in the equilibrium the
T ( C) k (h1) Ect (kcal/mol)
concentrations of arsenate differ at each temperature, while
Desorption of As(V) the concentrations of phosphate are statistically equivalent at
10 0.0104 2.20 all temperatures. This means that the temperature does not
20 0.0118
affect phosphate release during equilibrium. Therefore, in the
40 0.0151
equilibrium regardless of the amount of arsenate adsorbed on
Adsorption of As(V) the soil, the concentration of phosphates released in the
10 0.0109 2.34 solution is the same for all temperatures. Phosphate release
20 0.0120
during arsenate adsorption is due to the process of ion
40 0.0161
exchange and it has been also reported in the work of Lambkin
and Alloway (2003).
presented in Table 1. The rate of arsenic adsorption is The results from the adsorption equilibrium experiments,
affected by the temperature increase. In addition, the values at three temperatures, under different equilibrium concen-
of the rate of arsenate adsorption are almost equal to the trations of As(V) are presented in Fig. 3. The temperature
corresponding values of desorption, at each temperature. increase affects the amount of arsenate sorbed in the soil, only
It is well known that phosphate and arsenate have similar for the higher equilibrium concentrations of As(V). Therefore,
properties and they compete for the same sorption sites. higher mass of arsenate is adsorbed for the same equilibrium
Fig. 2b shows the concentration of phosphate released from concentration, when the temperature increases. However, the
soil, versus time, during the adsorption of arsenate. The increase of temperature does not influence arsenate adsorp-
concentration of phosphate presented in Fig. 2b is the average tion for low equilibrium concentrations of arsenate. In addi-
concentration measured in duplicate experiments. The values tion, when the added concentration of arsenate was 100 mg/L,
of the standard deviation for phosphate concentrations in the there was no adsorption of arsenate, while the equilibrium
equilibrium at 10  C ranged from 3.7 mg/L to 40.5 mg/L, at 20  C concentration varied from 80 to 110 mg/L (Fig. 3). This obser-
ranged from 3.9 mg/L to 23.5 mg/L and at 40  C ranged from vation is attributed to the fact that the concentration of
0.5 mg/L to 55 mg/L. In addition, Table 2 shows the dissolved arsenate that can be released from the uncontaminated soil
arsenate and phosphate concentrations and the amount of ranges from 80 to 110 mg/L (data not shown).
arsenate adsorbed, at each temperature in the equilibrium The concentration of qe presented in Fig. 3 is the average
(after 10 h). In the equilibrium, as the temperature increased, value measured in duplicate experiments. The values of the
the concentration of arsenate in the solution decreased and standard deviation for qe at 10  C ranged from 0.2 to 2 mg As/g
the amount of arsenate adsorbed onto the soil increased. soil, at 20  C ranged from 0.07 to 2.1 mg As/g soil and at 40  C
Statistical methods (paired t-test, Chi-square test and R2 test) ranged from 0.13 to 3.9 mg As/g soil. Furthermore, the values of
Kf, n and Kd, were calculated from the fitting of Freundlich and
linear isotherms. The values of Kf, n and Kd, are the same for
a 2500 10C 20C 40C all temperatures. Specifically, Kf ¼ 0.002 L/g and n ¼ 0.7,
2000 whereas Kd ¼ 0.034 L/g. Therefore, temperature increase does
As (µg/L)

1500 not influence the values of Kf, n and Kd.

1000
Fig. 4 shows the correlation between the adsorbed
500
concentration of arsenic and the release of phosphates (PO3 4 ),
0
0 20 40 60 80 100 120 at different temperatures. The amount of phosphate released
time (hours) from the soil increased as the amount of arsenate adsorbed
increased, at each temperature. The concentration of phos-
b 800 10C 20C 40C phate is related linearly with the amount of adsorbed arse-
nate. Statistical methods including, paired t-test, Chi-square
PO4 (µg/L)

600
test and R2 test were used to compare the three series of
400
experimental data. The results of the statistical methods
200
showed that the data did not vary with temperature. For this
0
0 20 40 60 80 100 120
time (hours)

Fig. 2 – Adsorption of arsenate by uncontaminated (8 mg/ Table 2 – Concentration of phosphate and dissolved/
kg As) soil (5 g suspended in 100 mL) versus time at pH 8.06 adsorbed arsenic during the kinetic adsorption
and three different temperatures. Shown are As(tot) experiments. Data obtained after 10 h (equilibrium).
concentrations in 0.2 mm filtered samples. b) Release of T Dissolved As Adsorbed As Dissolved PO3
4
phosphate by uncontaminated (8 mg/kg As) soil (5 g ( C) (mM) (mM) (mM)
suspended in 100 mL) versus time at pH 8.06 and three
10 12.1 (0.6) 14.6 (0.6) 5.6 (0.1)
different temperatures, during arsenate adsorption. 20 10.5 (1.1) 16.2 (1.1) 5.9 (0.5)
Shown are phosphate (PO3L 4 ) concentrations in 0.2 mm 40 9.2 (0.7) 17.5 (0.7) 5.2 (0.2)
filtered samples.
1594 water research 43 (2009) 1589–1596

60 8), whereas m is the slope of the linear relationship and b is the

10C 20C 40C
qe (µgAs/g soil)

50 intercept. The values of m and b depended linearly on the iron-to-

40
30
20
10
0
0 500 1000
Ce (µg/L)
Fig. 3 – Adsorption of arsenate by uncontaminated (8 mg/
kg As) soil (5 g suspended in 100 mL) versus equilibrium
concentration of As(V) at pH 8.06 and three different
temperatures. Shown are As(tot) concentrations in 0.2 mm
filtered samples withdrawn after 4 days (reaction time).
reason, we can conclude that temperature does not play an
important role in the slopes of Fig. 4.
The study of Lambkin and Alloway (2003) showed that for
low arsenic additions (from 0 to 100 mmol As/g soil) the
amount of phosphates released increased as the amount of
arsenic adsorbed increased. For higher amount of arsenic
adsorbed (from 100 to 550 mmol As/g soil), the amount of
phosphates released reached a plateau, indicating
a maximum (Lambkin and Alloway, 2003). In our study the
amount of phosphate released from soil did not reach
a plateau because we used low arsenic additions, at all
temperatures. Specifically, in our study the amount of arsenic
adsorbed at 40  C ranged from 55 mg/L (0.014 mmol As/g soil) to
2600 mg/L (0.694 mmol As/g soil).
3.4. ZVI corrosion and arsenic removal as a function of
solid to solution ratio and pH
solution ratio and the presence of As(III) or As(V). The linear
relations of m and b with iron-to-solution ratio were adopted by
plotting the values of m and b with the iron-to-solution ratios. In
particular, in the presence of As(V) the following equation
1500 2000 present the value of m as a function of %ZVI/solution:
m ¼ 1.4086*(%ZVI/sol)  0.335 (equation 9), (R2 ¼ 0.9956)
whereas the value of b is given by the equation: b ¼ 10.574*(%ZVI/
sol) þ 2.665 (equation 10), (R2 ¼ 0.9949). In addition, equation 11
presents the relation of dissolved iron as a function of pH and
%ZVI/solution, in the presence of As(V): [Fe] (mg/L) ¼ (%ZVI/
sol)*{1.4086*pH þ 10.574}  0.335*pH þ 2.665 (equation 11).
However the relations obtained in this work cannot esti-
mate all the processes that take place during the corrosion of
iron. In particular we cannot estimate the amounts of
Fe(III)(hydr)oxides formed at each pH.
3.5. Stabilization
The results from the first stabilization experiment at three
different temperatures are presented in Fig. 6(a). In this
experiment we used uncontaminated soil. In the absence of
ZVI, the concentration of arsenic (as As(V)) released from soil
at 10  C was 30 mg/L, at 20  C was 42 mg/L and at 40  C was
81 mg/L. In the presence of ZVI, the concentration of arsenic (as
As(V)) released from soil to the solution decreased at all
temperatures. The concentration of arsenic in the solution
greatly depends on the ratio of ZVI/soil.
The results from the second stabilization experiment are
presented in Fig. 6(b). In the absence of ZVI, the concentration
of arsenic (as As(V)) released from soil was 246 mg/L, after 4 h
and 361 mg/L after 24 h. Using the first-order kinetic model for
arsenic release (equation 7) we can predict the concentration

ZVI corrosion under different pH and different iron-to-solution

ratios is presented in Fig. 5(a) and (b). Dissolved iron concentra-
tion decreased as the pH increased. This happened because iron a 4 y = -1.4879x + 11.467
R2 = 0.7546
precipitates at high pH values. However, since the samples were
3
0.25% 0.5%
0.25% 0.5% 1%
1%
Fe (mg/L)

filtered immediately and were not exposed to air, dissolved iron

was probably almost entirely in the form of Fe(II). The concen- 2
y = -1.0389x + 7.9975
2
tration of dissolved iron was linearly related to the pH in each R = 0.8886
1
iron-to-solution ratio in the presence of As(III) and As(V) (Fig. 5(a) y = -0.503x + 3.8337
R2 = 0.9205
and (b)). Specifically, the concentration of dissolved iron was 0
expressed by the generalized equation: [Fe] ¼ m*pH þ b (equation 5 6 7 8
pHactual

1200
10C 20C 40C
b 5
y = -1.7343x + 13.131
1000 4 2
R = 0.9874
PO4 (µg/L)

Fe (mg/L)

800 3 y = -1.079x + 8.2842

2 0.25% 0.5%
0.25% 0.5% 1%
1%
600 R = 0.999
2
400
200 1 y = -0.6626x + 5.0896
0 R2 = 0.9184
0
0 500 1000 1500 2000 2500 3000 5 6 7 8
Asinitial -Asfinal (µg/L) pHactual

Fig. 4 – Phosphate release by uncontaminated (8 mg/kg As)
soil (5 g suspended in 100 mL) as a function of arsenate
sorbed, at pH 8.06 and three different temperatures. Shown
are phosphate (PO3L4 ) concentrations in 0.2 mm filtered
samples, withdrawn after 4 days (reaction time).
Fig. 5 – ZVI corrosion under different zero valent iron-to-
solution ratios (ZVI/solution) and different pH at 20 8C
(reaction time 4 h): a) dissolved iron concentration in the
presence of As(III), b) dissolved iron concentration in the
presence of As(V).
 water research 43 (2009) 1589–1596 1595

a 100 40C 20C 10C

the mass ratio of ZVI/soil was 0.5 (16% reduction) and to 108 mg/L
when the mass ratio of ZVI/soil was 1 (70% reduction).
As (µg/L)

Using equation 11 and the experimental data we can

50
correlate the corrosion of iron with the removal of arsenic
released from contaminated soil at pH 7.0. Fig. 7 presents the
0
0 0,05 0,15 0,25 concentration of arsenic remaining in the solution versus the
g ZVI/g soil dissolved concentration of iron (that was determined through
the empirical equations) for 4 and 24 h. There is a linear
b Stabilization relation between the concentration of arsenic remaining in
400 4 hours 24 hours the solution and the dissolved iron concentration. In Fig. 7, the
As (µg/L)

300
200
100
0 verified with preliminary experiments conducted for deter-
0 0,5
g ZVI/g soil
Fig. 6 – (a) Stabilization of arsenate in uncontaminated soil
(8 mg/kg As) soil (20 g suspended in 100 mL) at three
different temperatures (10, 20, 40 8C) and different ZVI/soil
ratios. Shown are As(tot) concentrations in 0.2 mm filtered
samples, withdrawn after 4 h. (b) Stabilization of arsenic in
contaminated (60 mg/kg As(V)) soil at two different
reaction times (4 and 24 h) and different ZVI/soil ratios.
Shown are As(tot) concentrations in 0.2 mm filtered
samples.
of arsenic released from soil after 4 and 24 h. Specifically, after
4 h the concentration of arsenic released from soil was
246 mg/L while the predicted concentration of arsenic was
283 mg/L, yielding a 15% of difference. In addition after 24 h the
concentration of arsenic released from soil was 361 mg/L while
the predicted concentration of arsenic was 363 mg/L, yielding
a 0.6% of difference. The kinetic model can successfully
predict the concentration of arsenic released from soil
without the presence of ZVI.
ZVI reduced the amount of arsenic concentration released
from contaminated soil (Fig. 6(b)). The concentration of arsenic
released from soil after 4 h decreased to 170 mg/L when the mass
ratio of ZVI/soil was 0.5 (31% reduction), and to 120 mg/L when
the mass ratio of ZVI/soil was 1 (51% reduction). In addition,
arsenic released from soil after 24 h decreased to 304 mg/L when
500 4 hours 24 hours
400 y = -64.235x + 385.86
As (µg/L)
concentration of dissolved iron in 24 h was though to be equal
with the concentration of dissolved iron in 4 h. This was
1
mining iron corrosion versus time (data not shown).
Based on the results obtained from the iron corrosion
experiments, the stabilization experiments and the equations
formed we can predict the concentration of dissolved iron
exported from ZVI (equation 11) and the concentration of
arsenic remained in the solution during the stabilization
experiments (Fig. 7). Particularly, the equation that can be
used in order to predict the concentration of arsenic in the
solution after 4 h is As(V) (mg/L) ¼ 32.6*[Fe] (mg/L) þ 243.6
(equation 12) and the equation that can be used in order to
predict the concentration of arsenic in the solution after 24 h
is As(V) (mg/L) ¼ 64.2*[Fe] (mg/L) þ 385.9 (equation 13).
The root-mean-square-error (RMSE) between model and
experimental data was 4 mg/L for the stabilization experiment
conducted for 4 h and 38 mg/L for the stabilization experiment
conducted for 24 h. According to t-testing, the results are
significant at the 95% confidence level for both experiments.
In addition, according to Chi-square testing the results are
significant at the 95% confidence level for the experiment
conducted in 4 h but are not significant at the 95% confidence
level for the experiment conducted in 24 h. Finally, linear
relations were observed between the experimental data and
the model data obtained from equations, yielding good R-
square values (0.9939 and 0.9947 for the experiment con-
ducted in 4 h and 24 h, respectively).
4. Conclusions – environmental implications
This work focused on an agricultural area, which is irrigated
with geothermal water and is being cultivated extensively.
Even though we have not conducted bioavailability studies in
plants, the fact that arsenic is released from topsoil suggested
that stabilization might be necessary for future cultivation of

the land. Even though extensive surveys have not been con-
300 R2 = 0.8779
ducted for heavy metal content in topsoils, the soil European
200
Atlas suggests that there are extensive areas with arsenic
100 y = -32.582x + 243.58
R2 = 0.994 concentration higher than the typical background values of
0
10 mg/kg. This work is a first step towards reducing arsenic
0 1 2 3 4 5
mobility from topsoils and therefore its bioavailability and
Fe (mg/L)
toxicity. Specifically, in this study we developed a simplified
Fig. 7 – Correlation between the dissolved arsenic empirical model that can predict iron and arsenic concentra-
concentration released from soil with the dissolved iron tions during stabilization experiments. There was a linear
concentration leached from ZVI, at two different reaction relation between the dissolved arsenic concentration released
times (4 and 24 h), in stabilization experiments conducted from soil with the dissolved iron concentration in the stabi-
with contaminated (60 mg/kg As(V)) soil. lization experiments. The short term stabilization experi-
ments shown that the reaction time and the ratio of ZVI/soil
1596 water research 43 (2009) 1589–1596
affect the efficiency of arsenic stabilization in topsoils with
ZVI, at 20  C. Specifically, after 4 h we reported 31% reduction
in the concentration of arsenic released from soil when the
mass ratio of ZVI/soil was 0.5 and 51% reduction when the
mass ratio of ZVI/soil was 1. In addition, after 24 h we reported
16% reduction in the concentration of arsenic released from
soil when the mass ratio of ZVI/soil was 0.5 and 70% reduction
when the mass ratio of ZVI/soil was 1. Furthermore, ZVI can
effectively reduce the amount of arsenic leached from soil at
all temperatures.
In addition, the release/desorption experiments and
adsorption experiments, under different conditions, showed
that the concentration of arsenate desorbed from soil depends
on the temperature. Higher concentrations of arsenate were
reported as the temperature increased. These results should
be taken in account in the case of soil irrigation during
summer or in the case of soil irrigation with geothermal water
with high temperature.
Acknowledgments
This project was funded by the Hellenic Ministry of Education
under the contract number MIS88744 – EPEAEK II-IRAKLITOS.
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