Environ Earth Sci (2012) 65:813–821
DOI 10.1007/s12665-011-1126-5
ORIGINAL ARTICLE
Bioavailability of arsenic in the soil horizon:
a laboratory column study
Sudip Jyoti Sahu • Bibhash Nath • Sharmi Roy •
Biswapati Mandal • Debashis Chatterjee
Received: 18 December 2009 / Accepted: 13 May 2011 / Published online: 15 June 2011
Ó Springer-Verlag 2011
Abstract Groundwater contaminated with arsenic (As),
when extensively used for irrigation, causes potentially
long-term detrimental effects to surface soils. Such con-
tamination can also directly affect human health when
irrigated crops, such as rice, vegetable and fruits, are used
for human consumption. Therefore, an understanding of the
leaching behavior of As in surface soils is of high impor-
tance, because such behavior may increase the bioavail-
ability of As in the soil horizon. In this study, we have
investigated the role of phosphate ions in leaching and
bioavailability of As in the soil horizon, where drinking
groundwater contains elevated levels of As (C50 lg/L).
Soil and groundwater samples were characterized in the
laboratory and measured for physical and chemical con-
stituents. The soils are generally neutral to slightly alkaline
in character (pH range 7.5–8.1) with low to moderate levels
of free Fe2O3, Al2O3, CaCO3, organic carbon, and clay
content. The measured electrical conductivity (mean
599 lS/cm) of the soils demonstrates their non-saline
nature. The Eh values (range -37 to -151 mV) of the
groundwater indicate anoxic condition with low to moder-
ate levels of bicarbonate (range 100–630 mg/L) and phos-
phate (range 0.002–4.0 mg/L). The arsenic content (range
S. J. Sahu
S. Roy
D. Chatterjee (&)
Department of Chemistry, University of Kalyani,
Kalyani 741 235, West Bengal, India
e-mail: dbchat2001@rediffmail.com
B. Nath
School of Geosciences, University of Sydney,
Sydney, NSW 2006, Australia
B. Mandal
Department of Agricultural Chemistry and Soil Science,
Bidhan Chandra Krishi Viswavidyalaya, Kalyani 741 235,
West Bengal, India
50–690 lg/L; mean 321 lg/L) in groundwater has excee-
ded both WHO recommended guideline values (10 lg/L)
and the National safe drinking water limit (50 lg/L).
Regression analyses demonstrate that the bioavailability of
As in the soil horizon is mainly controlled by the compo-
sition of free Fe2O3 and CaCO3 content of the soils. How-
ever, application of P could increase bioavailability of As
in the soil horizon and become available to plants for
uptake.
Keywords Arsenic
Bioavailability
Bicarbonate
Iron
oxyhydroxide
Phosphate
Soil properties
Introduction
Arsenic (As) is a toxic and ubiquitous element in nature,
which poses a potential threat to human health and the
environment. Arsenic is widely distributed in nature
(especially in soils) with concentrations ranging from 1 to
40 mg/kg (Eckel and Langley 1988; Yan-Chu 1994).
Arsenic can be mobilized from the soils to groundwater
under favorable geochemical conditions (e.g., Smedley and
Kinniburgh 2002; Nath et al. 2009). Recently, naturally
occurring high As concentration was observed in ground-
water in Bengal Delta Plain (BDP). Such high As occur-
rences in groundwater had received significant
international attention due to widespread exposure to
human health and the environment (e.g., Smith et al. 2000;
Guha Mazumder et al. 2000).
The bioavailability of As in soil is strongly controlled by
the adsorption and desorption processes (Quaghebeur et al.
2005; Naidu et al. 2009a). The use of arsenical pesticides
and/or fertilizers during irrigation, farming practice
enhances As accumulation in soils (Sandberg and Allen
123
814
1975). Chemisorptions of As onto soil colloid surfaces in
particular is believed to decrease the solubility of As and
thus lead to the formation of an As solid phase (Sadiq
1997). However, As concentration in soils and its solubility
strongly depends on soil properties such as soil Fe, Al, and
clay content (Smith et al. 1999). In the agricultural land,
water loss through evaporation could also cause the accu-
mulation of As in the top-soil. However, a large fraction of
the top-soil As is likely to be washed away during flooding,
while some may oxidize and form oxides of Fe, Al, and
other minerals. As a result, a cumulative accumulation of
As in surface soils is expected (Ali et al. 2003; Naidu et al.
2009b).
The presence of bicarbonate and/or phosphate in water
significantly affects As mobility in the soil horizon (Appelo
et al. 2002; Williams et al. 2003; Anawar et al. 2004).
However, the competition between bicarbonate or phos-
phate and arsenate for sorption sites varies greatly in the
presence of different soil minerals and soil chemical
properties (Woolson 1973; Johnston and Barnard 1979;
Roy et al. 1986; Peryea 1991; Melamed et al. 1995; Ana-
war et al. 2004). Peryea and Kammereck (1997) observed
that phosphate greatly enhanced the downward leaching of
arsenate in the soil horizons. De Brouwere et al. (2004)
observed that the chemical properties of the soil and the
chemical form of As are important for such processes.
Anawar et al. (2004) observed that the degree of As
leaching by bicarbonate ions varies greatly depending on
the bicarbonate concentrations in the water, amount of As
in the soils, and pH.
In this study, we have characterized soil and ground-
water samples for their chemical and physical properties.
Soil samples (in columns) were collected from the study
areas and amended with different doses of phosphate to
understand the leaching behavior of As in the soil horizon.
It is expected that the results of this study will elucidate the
factors that may control the bioavailability of As in the soil
horizon.
Fig. 1 Map of the study area
showing sampling locations
(soil and groundwater) and the
distribution of As in tube-well
water. The map also shows
locations of two sites (areas of
high and low As concentrations
in groundwater) from where soil
samples (in column) have been
collected to test P-induced As
leaching behavior. Latitude and
longitude units are in degrees
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Environ Earth Sci (2012) 65:813–821
Materials and methods
Study area
The study area (*30 km2, 20 km south of Kolkata city)
was located in Baruipur block, South 24 Parganas district,
West Bengal (Fig. 1). It was constituted mostly of guava
orchards that were usually established with soils imported
from lowland rice fields. The imported soil were generally
laid down after rainfall events and subsequently used to
plant saplings of desired tree varieties. Due to the washing
out of clay particles during rainfall, the soils of the newly
established orchard were generally light in color and low in
organic carbon compared with the rice fields, where native
grasses, residues of rice plants and other weeds grow reg-
ularly. The annual rainfall in this region is about 1,800 mm,
restricted to the wet monsoon period. The temperature
ranges between 10 and 40°C. In the pre-monsoon time,
groundwater level ranges between 2.5 and 6.8 m above
mean sea level (msl), while during post-monsoon time, the
groundwater level ranges between 2.6 and 6.5 m above msl.
Sampling and analytical techniques
Soil samples (up to 45 cm below surface, n = 30) were
collected from the guava orchards of Baruipur block, South
24 Parganas district, West Bengal for the determination of
physical and chemical characteristics. Prior to analysis, the
soil samples (in bulk) were air-dried, ground and sieved
through \2 mm sieve, and stored in a plastic containers.
The soil samples were measured for pH, electrical con-
ductivity (EC), Al2O3, free iron oxides (henceforth Fe2O3),
CaCO3, clay, and organic carbon content (Org C). For
measurement of soil pH and EC, 10 g of soil sample was
placed in a 50 ml glass beaker and mixed with 25 ml
distilled water. The suspension was stirred for approxi-
mately 30 min until equilibrium was attained. The above
mixture was then measured for pH and EC using WTW
Environ Earth Sci (2012) 65:813–821 815

multimeter (WTW, Germany). Free iron oxides (Fe2O3)
were extracted by citrate–bicarbonate–dithionite solution
following the method of Mehra and Jackson (1960). The
clay and organic carbon contents of the soils were mea-
sured following the method described in Jackson (1973).
CaCO3 contents were extracted with 0.5 N HCl following
the procedure described in Black (1965). The Al2O3 con-
tent was extracted with 0.5 N NaOH following the proce-
dure detailed in Jackson (1973). The soil As content (easily
labile and/or surface adsorbed fractions) was determined
by extraction with 0.1 M NaHCO3 at a pH of 8.5. The
detailed soil As extraction procedure was described in
McLaren et al. (1998). The extractant was measured for As
concentrations using a hydride generation atomic absorp-
tion spectrophotometer (HG-AAS).
Groundwater pH, Eh, and EC were measured in the field
using WTW multimeters (Germany). Alkalinity (reported
as HCO3) was also measured in the field using the titri-
metric method described by Bhattacharyya et al. (2003).
The samples were filtered on-site using Sartorious filter
paper (0.45 lm) and separated into two groups: (1) filtered
un-acidified for anion (e.g., NO3, PO4 and SO4) and (2)
filtered acidified (with a few drops of HNO3, pH *2) for
total As and Fe analysis. The anion concentrations were
measured by ion chromatography (Dionex, CA, USA)
using external calibration (accuracy ±6% and precision
±5%). Arsenic and iron concentrations were measured
using a HG-AAS (accuracy and precision ±5%).
Column experiments
Undisturbed soil cores (in a polyvinyl chloride hollow pipe,
length 60 cm, inner diameter 10 cm) were collected from
two sites (areas of low and high As concentrations in

Table 1 Chemical characteristics of the soil samples collected from the guava orchards of the study area
Location ID Latitude Longitude As pH EC Al2O3 CaCO3 Fe2O3 Organic carbon Clay
(mg/kg) (lS/cm) (g/kg) (g/kg) (g/kg) (g/kg) (g/kg)

SJ01 22.3490 88.4600 2.5 8.0 75 45 6.6 1.7 19 54

SJ02 22.3425 88.4725 3.0 8.0 126 42 6.0 2.3 22 48
SJ03 22.3257 88.4605 3.1 8.0 172 43 6.2 1.9 21 53
SJ04 22.3167 88.4708 3.2 8.1 219 40 5.5 2.5 21 53
SJ05 22.3250 88.4617 3.6 8.0 276 39 5.4 2.1 23 48
SJ06 22.3292 88.4820 3.6 7.9 245 39 5.5 2.6 24 48
SJ07 22.3142 88.4642 3.7 7.9 198 40 5.6 2.5 24 47
SJ08 22.3350 88.4642 4.0 7.9 230 40 5.4 0.32 25 45
SJ09 22.3200 88.4533 4.0 7.9 307 39 5.7 3.1 23 46
SJ10 22.3258 88.4767 4.4 7.9 375 34 5.0 3.0 27 47
SJ11 22.3085 88.4545 4.7 7.9 363 36 4.8 3.3 26 43
SJ12 22.3092 88.4623 5.4 7.9 509 31 4.5 3.9 31 42
SJ13 22.3615 88.4783 5.4 7.9 410 29 4.1 3.8 29 39
SJ14 22.3275 88.4575 5.8 7.8 519 30 4.1 4.1 32 40
SJ15 22.3615 88.4670 6.5 7.8 582 24 3.8 4.9 33 38
SJ16 22.3400 88.5465 6.5 7.8 634 24 3.4 4.8 34 34
SJ17 22.3357 88.4683 6.6 7.8 611 24 3.9 5.1 32 35
SJ18 22.3152 88.4495 7.1 7.8 694 24 3.0 5.5 35 32
SJ19 22.3188 88.4657 7.6 7.7 722 18 2.8 6.1 37 31
SJ20 22.3358 88.4690 7.9 7.7 722 16 2.5 5.9 36 29
SJ21 22.3107 88.4607 8.1 7.7 851 19 2.3 6.3 40 25
SJ22 22.3388 88.5053 8.6 7.6 843 16 2.0 6.9 40 26
SJ23 22.3572 88.4672 8.7 7.6 840 15 2.3 6.7 42 25
SJ24 22.3083 88.4620 9.2 7.6 908 13 1.5 7.3 43 22
SJ25 22.3347 88.4487 9.6 7.5 1,010 11 1.3 7.5 45 22
SJ26 22.3333 88.4633 9.9 7.6 1,030 8.8 1.0 7.7 44 21
SJ27 22.3330 88.5167 10 7.5 1,065 3.6 0.54 8.0 47 17
SJ28 22.3452 88.5448 11 7.5 1,160 4.6 0.63 8.5 46 16
SJ29 22.3345 88.5315 11 7.5 1,090 2.2 0.45 8.3 49 17
SJ30 22.3035 88.4692 11 7.5 1,170 2.4 0.40 8.6 49 15

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816 Environ Earth Sci (2012) 65:813–821

groundwater) to examine the influence of phosphate ions
on the bioavailability of As in the soil horizon. Each soil
profile was divided into two columns. The first column was
used as a control, while 10 ppm As was applied (from the
top) to the second column. After amending with As, the
soil columns were left for aging (15 days). On the com-
pletion of the aging period, three levels of phosphorous (1)
distilled water with no phosphorous (as a control), (2)
50 mg/kg of phosphorous, and (3) 100 mg/kg of phos-
phorous solution was applied to both groups of soil and left
for aging (18 months). During the aging period, the col-
umns were kept under moist condition by adding distilled
water to maintain the site condition. After 18 months, each
soil column was cut into four equal pieces and the samples
were collected from each parts (0, 15, 30 and 60 cm). The
collected soil samples were dried, ground, and sieved
(\2 mm), and finally extracted for As (easily labile and/or
surface adsorbed fractions) with 0.1 M NaHCO3 at a pH of
8.5. The extracted As was measured with HG-AAS.
Statistical analysis
electrical conductivity of the soils ranged between 75 and
1,170 lS/cm (mean 599 lS/cm), indicating non-saline
nature (Table 1).
Alkali bicarbonate salt (0.1 M NaHCO3) was used to
extract As (easily labile and/or surface adsorbed fractions)
from different soil horizons. The extracted As content of
the soils ranged between 2.5 and 11 mg/kg, with a mean
concentration of 6.5 mg/kg. The result showed variable
amount of As extracted from different soil layers (Fig. 2).
The depth variation showed a decreasing trend in all but
one soil column, suggesting that most of the As imported
during irrigation drawdown is being adsorbed at shallow
depth in the soil profile (0–15 cm). At pH 8.5, bicar-
bonate ion was used to displace loosely bound As from
the surface sites of Fe-oxyhydroxides and thereby
increasing bioavailability of As in the soil horizon
(Anawar et al. 2004). However, downward leaching of As
may be controlled by the permeability of the soils, which
might have partly controlled the distribution of As in the
shallow groundwater and/or uptake by the plants (Nath
et al. 2008).

The regression analyses were performed on the dataset Groundwater characteristics

using the statistical software package SPSS Inc. In this
analysis, the mean values of the extracted soil As content Results from the chemical analysis of the groundwater
were considered as a dependent (or criterion) variable, have been tabulated in Table 2. Groundwater has a near-
while the measured soil chemical composition was con- neutral pH (6.9 and 8.1) and a high alkalinity (range
sidered as an independent (or predictor) variable. The
multiple regression analysis allowed us to quantify the
impact of independent variables on a single dependent
variable. In the stepwise regression analysis, each inde-
pendent variable was entered in a sequence and its value
was assessed. If adding the individual independent variable
contributed to the model, then it was retained, but all other
variables in the model were re-tested to see if they still
contributed to the success of the model. If they no longer
contributed significantly they were removed. This method
ensured the smallest possible set of independent variables
included in the model.

Result and discussion

Soil properties

The pH (range 7.5–8.1) of the soils demonstrated neutral to

slightly alkaline conditions. The soils also contained
moderate to high values of organic carbon (19–49 g/kg)
and clay content (15–54 g/kg). The extracted free Fe2O3,
Al2O3, and CaCO3 content of the soils varied between 0.32
and 8.6 g/kg (mean 4.8 g/kg); 2.2–45 g/kg (mean 25 g/kg) Fig. 2 Distribution of soil As contents (in mg/kg, n = 30) at
and 0.40–6.6 g/kg (mean 3.5 g/kg), respectively. The different depths of the soil horizon

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Environ Earth Sci (2012) 65:813–821 817

139–630 mg/L; mean 309 mg/L). The electrical conduc-
tivity of groundwater ranges from 600 to 3,800 lS/cm
(mean 1,250 lS/cm). Groundwater contains low to mod-
erate levels of nitrate (range 0.01–0.43 mg/L; mean
0.12 mg/L), phosphate (range 0.01–4.0 mg/L; mean
0.49 mg/L), Fe (range 1.6–25 mg/L; mean 13 mg/L) and
sulphate (range 0.28–88 mg/L; mean 14 mg/L). The Eh
values (-144 to -37 mV) of the groundwater demonstrate
reducing nature of the aquifer. The range of As content
(50–690 lg/L; mean 321 lg/L) in groundwater exceeded
both the WHO recommended guideline value (10 lg/L)
and the National safe drinking water limit (50 lg/L).
The mobilization of As in groundwater is thought to be
controlled by the geochemical processes that involve
leaching of As from the source material (e.g., As-bearing
sulfidic minerals, Fe-oxyhydroxides etc.) (Smedley and
Kinniburgh 2002). However, accumulation of As in soils
due to irrigation drawdown and subsequent increase in
bioavailability to plants is governed by the combination of
geochemical and anthropogenic processes. The correlation
of As versus Fe in groundwater (Table 3) suggests that the
release of As at this site is controlled in part by the redox
reaction involving the dissolution of Fe-oxides. This
observation is in agreement with the previous studies from
BDP (e.g., PHED 1993; BGS and DPHE 2001; McArthur
et al. 2001). Therefore, the impact of groundwater use for
irrigation will be manifold (1) accumulation of As in sur-
face soils, (2) increasing bioavailability of As for plant
uptake, and (3) downward leaching of As to the shallow
aquifer.

Table 2 Chemical characteristics of the groundwater samples collected from the household domestic wells of the study area
Well Latitude Longitude Depth pH Eh EC As Fe NO3 PO4 SO4 Alkalinity
ID (m) (mV) (lS/cm) (lg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L)

SJ01 22.3490 88.4600 22 8.1 -110 850 50 25 0.01 0.12 3.2 139
SJ02 22.3425 88.4725 24 8.0 -101 1,000 610 21 0.16 0.34 0.28 335
SJ03 22.3257 88.4605 17 7.4 -63 700 220 23 0.01 0.12 2.7 189
SJ04 22.3167 88.4708 37 8.1 -40 1,100 630 20 0.43 0.32 5.2 255
SJ05 22.3250 88.4617 15 7.7 -136 750 100 3.4 0.11 4.0 4.6 602
SJ06 22.3292 88.4820 30 7.4 -60 1,600 690 24 0.01 0.16 1.9 630
SJ07 22.3142 88.4642 22 7.4 -42 650 652 20 0.41 0.08 3.3 349
SJ08 22.3350 88.4642 14 7.4 -61 800 200 21 0.08 0.52 2.1 352
SJ09 22.3200 88.4533 15 7.6 -48 800 170 20 0.01 0.08 5.1 156
SJ10 22.3258 88.4767 40 7.4 -41 1,000 553 17 0.05 1.0 5.3 449
SJ11 22.3085 88.4545 14 7.4 -40 1,200 600 19 0.41 0.34 3.7 284
SJ12 22.3092 88.4623 18 7.5 -44 1,200 510 17 0.40 0.56 5.2 290
SJ13 22.3615 88.4783 61 7.3 -51 600 440 16 0.15 0.03 3.3 260
SJ14 22.3275 88.4575 21 7.6 -53 850 110 17 0.01 0.01 13 153
SJ15 22.3615 88.4670 30 7.5 -125 700 510 17 0.40 0.99 16 167
SJ16 22.3400 88.5465 74 7.4 -89 2,800 480 18 0.01 0.01 32 175
SJ17 22.3357 88.4683 18 7.3 -44 1,700 406 13 0.01 1.7 11 480
SJ18 22.3152 88.4495 20 8.0 -58 800 210 11 0.01 0.16 3.3 182
SJ19 22.3188 88.4657 55 6.9 -58 800 271 7.4 0.11 0.36 5.3 240
SJ20 22.3358 88.4690 30 7.9 -37 1,100 271 9.1 0.01 2.1 13 416
SJ21 22.3107 88.4607 40 7.1 -71 1,200 245 9.0 0.07 0.15 3.8 455
SJ22 22.3388 88.5053 243 7.4 -95 2,500 235 9.6 0.01 0.19 62 398
SJ23 22.3572 88.4672 11 7.5 -144 1,300 90 1.6 0.01 0.03 1.2 195
SJ24 22.3083 88.4620 15 7.4 -52 1,300 209 7.5 0.41 0.29 6.2 288
SJ25 22.3347 88.4487 27 7.5 -63 650 120 5.7 0.01 0.01 7.3 142
SJ26 22.3333 88.4633 14 7.4 -50 700 510 7.0 0.30 0.64 12 388
SJ27 22.3330 88.5167 243 7.8 -86 1,800 133 3.5 0.01 0.28 57 370
SJ28 22.3452 88.5448 107 7.5 -58 2,600 102 3.2 0.01 0.01 29 250
SJ29 22.3345 88.5315 259 7.4 -45 3,800 164 5.7 0.01 0.01 88 450
SJ30 22.3035 88.4692 37 7.3 -65 900 133 3.4 0.01 0.01 1.8 215

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Table 3 Correlation coefficient (Pearson r) of different chemical characteristics of the groundwater and soil samples collected from the study
area
Groundwater composition Soil composition

pH Eh EC As Fe NO3 PO4 SO4 Alkalinity As pH EC Al2O3 CaCO3 Fe2O3 Org C Clay

pH 1
Eh -0.20 1
EC -0.11 0.01 1
As -0.05 0.30 -0.10 1
Fe 0.21 0.19 -0.26 0.53 1
NO3 0.01 0.17 -0.28 0.59 0.22 1
PO4 0.15 -0.23 -0.17 -0.02 -0.20 0.04 1
SO4 -0.04 -0.03 0.83 -0.23 -0.35 -0.25 -0.13 1
Alkalinity -0.16 0.07 0.24 0.27 -0.12 -0.04 0.54 0.18 1
As -0.31 0.04 0.45 -0.43 -0.85 -0.21 -0.19 0.52 -0.04 1
pH 0.34 0.00 -0.44 0.47 0.81 0.29 0.24 -0.53 0.04 -0.97 1
EC -0.31 0.04 0.44 -0.43 -0.86 -0.22 -0.17 0.50 -0.04 1.00 -0.96 1
Al2O3 0.30 -0.04 -0.46 0.40 0.85 0.22 0.16 -0.54 0.02 -0.99 0.96 -0.99 1
CaCO3 0.28 -0.04 -0.44 0.41 0.86 0.19 0.17 -0.53 0.01 -0.99 0.96 -0.99 0.99 1
Fe2O3 -0.26 0.03 0.44 -0.38 -0.83 -0.18 -0.21 0.50 -0.07 0.98 -0.94 0.98 -0.98 -0.97 1
Org C -0.32 0.02 0.44 -0.42 -0.85 -0.20 -0.21 0.52 -0.04 0.99 -0.97 0.99 -0.99 -0.99 0.97 1
Clay 0.31 -0.02 -0.44 0.43 0.85 0.23 0.20 -0.50 0.03 -0.99 0.97 -0.99 0.99 0.99 -0.97 -0.99 1

Bioavailability of arsenic in the soil horizon
Effect of soil properties
Regression analysis was performed to identify the inter-
relationships between different soil properties (e.g., pH, EC,
Al2O3, CaCO3, Fe2O3, organic carbon, and clay contents)
and the bioavailability of As in soils. The result showed
positive correlation between the extracted soil As versus
Fe2O3 (r = 0.99), and organic carbon (r = 0.99) (Table 3).
This suggests an association of As with free Fe2O3 and
organic carbon. Under moist conditions (mainly during rainy
season) As might therefore release in the root zone of the soil
layers due to microbial oxidation of organic matter, thereby
increasing the bioavailability of As in the soil horizon
and thereby increasing plant uptake. Previous studies (De
Brouwere et al. 2004; Violante and Pigna 2002) also dem-
onstrated the same, where Fe-oxides appear to be the most
important solid phase that adsorbs and retains As(V).
A stepwise regression model (soil As = 1.6 - 0.06
CaCO3** ? 0.61 Fe2O3**; R2 = 0.99; **significant at
p \ 0.01) has indicated that Fe2O3 and CaCO3 are the two
important mineral phases that control the bioavailability of
As in the soil horizon. In alkaline condition, As is less
strongly bound to Fe-oxyhydroxides than at neutral or low
pH condition (Smedley et al. 2002). Calcium carbonate
generally reacts with H? ions, causing increase in the
bicarbonate concentration and pH of the solution.
Therefore, under such conditions, bicarbonate can easily
exchange arsenate from the adsorbed phases and thereby
increasing dissolved As concentrations (Appelo et al.
2002). Appelo et al. (2002) further reported that the sorp-
tion of carbonate ions at common soil and groundwater
concentrations reduces adsorption of As onto ferrihydrite
resulting in release of As in groundwater. Moreover, the
association between Fe2O3 and As further suggests that
bioavailability of As can be controlled by the Fe-reduction
processes (e.g., breakdown of organic matter under low
redox condition) in the shallow groundwater. This issue is
currently being investigated at this site, and also supported
by the positive correlation between the dissolved As and Fe
concentrations and low Eh values (Table 3).
Effect of phosphate ion
The column tests indicated that the addition of P did not
increase the bioavailability of As in the soils collected from
the areas of low As concentrations in groundwater
(Fig. 3a). However, *70% of the adsorbed As was able to
be extracted from the soils collected from areas of high As
concentrations in groundwater (Fig. 4a). This suggests that
competitive phosphate–arsenate exchange might be an
important mechanism for increasing the bioavailability of
As in the soil horizon. Generally, phosphate enhances the
bioavailability of As in the soil environment by displacing
arsenate from the sorption sites and increasing soil P

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Environ Earth Sci (2012) 65:813–821 819

Fig. 3 Leaching of As in control and phosphate amended (50 and Fig. 4 Leaching of As in control and phosphate amended (50 and
100 mg/kg) soils collected from areas where low As concentrations in 100 mg/kg) soils collected from areas where high As concentrations
groundwater were observed: a native soil, and b As amended in groundwater were observed: a native soil, and b As amended
(10 ppm) soil (10 ppm) soil

content (Peryea and Kammereck 1997; Peryea 1998). Cao

et al. (2003) observed that phosphate amendments in the
soil significantly enhance As uptake by plants. Similar
observation is also reported by Jacobs and Keeney (1970)
and Turpeinen et al. (1999).
The addition of As (10 ppm) from the top of the soil
column to both sets of soil samples increased As adsorption
in the surface layers (Figs. 3b, 4b). This is also true for the
native soils collected from the study area, where extract-
able soil As content gradually decreases with depth
(Fig. 2). Such observation clearly suggests that the irriga-
tion drawdown at high groundwater As sites may bring As
to the top-soil and thereby increasing As content in the
surface soils. The application of different P levels to these Fig. 5 Increase in phosphorous concentration in the soil column after
soils increased the leaching of As through the soil column addition of 50 and 100 mg/kg of P in the native soils (control sample)
(Figs. 3b, 4b). This is also consistent with the increase in P
concentration in all the soil columns (Fig. 5), suggesting exchangeable fraction) is important for P-induced release
sorption of P ions in the soil/mineral surfaces. In conclu- of As in the soil environment.
sion, this study further supports that the amount of As in The mechanism of phosphate-induced As release is not
the soils and the chemical form of the sorbed As (e.g., only restricted to orchards, but also observed in agricultural

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820
soils, where As containing herbicides and/or insecticides
are used (Woolson 1973). Increases in As bioavailability
may induce the accumulation of As in the plants as well as
in the fruits. There are many reports available in the lit-
erature of As uptake by the fruits which might also be
detrimental to human health.
Conclusion
This study indicates that application of P to As-contami-
nated soils can appreciably increase the bioavailability of
As in the soil horizon, thereby increasing the risk associ-
ated with As uptake by plants in orchards. Bicarbonate ion
was also shown to influence As leaching at this site. The
magnitude of this behavior is varied between the soils,
which are influenced by the As loading, physical and
chemical properties of the soil, the amount of bicarbonate
present in the water.
Acknowledgments The principal author (DC) acknowledges the
support of Late Prof. Nityananda Saha (Ex-Vice Chancellor, Uni-
versity of Kalyani) to carry out this research work. The authors would
also like to acknowledge the Swedish Research Council (VR), Sida-
SAREC and Rajiv Gandhi National Drinking Water Mission
(RGNDWM), Department of Drinking Water Supply, Govt. of India
for supporting the research on high arsenic groundwater of West
Bengal, India.
References
Ali AM, Badruzzaman ABM, Jalil MA, Hossain MD, Ahmed MF,
Masud AA, Kamruzzaman M, Rahaman AM (2003) Fate of
arsenic extracted from groundwater, fate of arsenic in the
environment. Bangladesh University of Engineering and Tech-
nology (BUET), Dhaka
Anawar HM, Akai J, Sakugawa H (2004) Mobilization of arsenic
from subsurface sediments by effect of bicarbonate ions in
groundwater. Chemosphere 54:753–762
Appelo CAJ, Weiden MJJVD, Tournassat C, Charlet L (2002)
Surface complexation of ferrous iron and carbonate on ferrihy-
drite and the mobilization of arsenic. Environ Sci Technol
36:3096–3103
BGS, DPHE (2001) Arsenic contamination of groundwater in
Bangladesh, vol. 2: final report. In: Kinniburgh DG, Smedley
PL (eds) British Geological Survey (BGS) Technical Report
WC/00/19. BGS, Keyworth
Bhattacharyya R, Jana J, Nath B, Sahu SJ, Chatterjee D, Jacks G
(2003) Groundwater As mobilization in the Bengal Delta Plain,
the use of ferralite as a possible remedial measure—a case study.
Appl Geochem 18:1435–1451
Black CA (1965) Method of soil analysis, part 2, chemical and
microbiological properties. American Society of Agronomy,
Inc., Madison
Cao X, Ma LQ, Shiralipour A (2003) Effects of compost and
phosphate amendments on arsenic mobility in soils and arsenic
uptake by the hyperaccumulator, Pteris vittata L. Environ Pollut
126:157–167
123
Environ Earth Sci (2012) 65:813–821
De Brouwere K, Smolders E, Merckx R (2004) Soil properties
affecting solid–liquid distribution of As (V) in soils. Eur J Soil
Sci 55:165–173
Eckel WP, Langley WD (1988) A background-based ranking
technique for assessment of elemental enrichment in soils at
hazardous waste sites. In: Proceedings of the 9th National
Conference, Nov 28–30, Washington DC, Silver Spring, MD.
The hazardous materials control. Research Institute, 286–288
Guha Mazumder DN, Haque R, Ghosh N, De BK, Santra A,
Chakraborti D, Smith AH (2000) Arsenic in drinking water and
the prevalence of respiratory effects in West Bengal, India. Int J
Epidemiol 29:1047–1052
Jackson ML (1973) Soil Chemical analysis, 2nd edn. Prentice Hall of
India Pvt. Ltd., New Delhi, p 498
Jacobs LW, Keeney DR (1970) Arsenic phosphorous interactions on
corn. Commun Soil Sci Plant Anal 1:85–93
Johnston SE, Barnard WM (1979) Comparative effectiveness of 14
solutions for extracting arsenic from 4 western New York soils.
Soil Sci Soc Am J 43:304–308
McArthur JM, Ravencroft P, Safiullah S, Thirlwall MF (2001)
Arsenic in groundwater: testing pollution mechanism for sedi-
mentary aquifers in Bangladesh. Water Resour Res 37:109–117
McLaren RG, Naidu R, Smith J, Tiller KG (1998) Fractionation and
distribution of arsenic in soils contaminated by cattle dip.
J Environ Qual 27:348–354
Mehra OP, Jackson ML (1960) Iron oxide removal from soils and
clays by a dithionite- Citrate system buffered with sodium
bicarbonate. Clay miner 7:317–327
Melamed R, Jurinak JJ, Dudley LM (1995) Effect of adsorbed
phosphate on transport of arsenate through an oxisol. Soil Sci
Am J 59:1289–1294
Naidu R, Bhattacharya P (2009) Arsenic in the environment—risks
and management strategies. Environ Geochem Health 31:1–18
Naidu R, Smith E, Imamul Huq SM, Owens G (2009) Sorption and
bioavailability of arsenic in selected Bangladesh soils. Environ
Geochem Health 31:61–68
Nath B, Sahu SJ, Jana J, Mukherjee-Goswami A, Roy S, Sarkar MJ,
Chatterjee D (2008) Hydrochemistry of arsenic-enriched aquifer
from rural West Bengal, India: a study of the arsenic exposure
and mitigation option. Water Air Soil Pollut 190:95–113
Nath B, Chakraborty S, Burnol A, Stüben D, Chatterjee D, Charlet L
(2009) Mobility of arsenic in the sub-surface environment: an
integrated hydrogeochemical study and sorption model of the
sandy aquifer materials. J Hydrol 364:236–248
Peryea FJ (1991) Phosphate induced release of arsenic from soils
contaminated with Lead arsenate. Soil Sci Soc Am J 55:
1301–1306
Peryea FJ (1998) Phosphate starter fertilizer temporarily enhances soil
arsenic uptake by apple trees grown under field conditions.
HortScience 33:826–829
Peryea FJ, Kammereck R (1997) Phosphate enhanced movement of
arsenic out of lead arsenate contaminated topsoil and through
uncontaminated subsoil. Water Air Soil Pollut 93:243–254
PHED (1993) National Drinking Water Mission project on arsenic
pollution on groundwater in West Bengal. Final report, Steering
Committee on As investigation. Govt. of West Bengal, India
Quaghebeur M, Rate A, Rengel Z, Hinz C (2005) Desorption kinetics
of arsenate from kaolinite as influenced by pH. J Environ Qual
34:479–486
Roy WR, Hassett JJ, Griffin RA (1986) Competitive interactions of
phosphate and molybdate on arsenate adsorption. Soil Sci
142:203–210
Sadiq M (1997) Arsenic chemistry in soils. An overview of
thermodynamic predictions and field observations. Water Air
Soil Pollut 93:117–136
Environ Earth Sci (2012) 65:813–821
Sandberg GR, Allen IK (1975) A proposed arsenic cycle in an
agronomic ecosystem. In: Woolson EA (ed) Arsenical pesticides.
American Chemical Society, Washington DC, pp 124–147
Smedley PL, Kinniburgh DG (2002) A review of the source, behavior
and distribution of arsenic in natural waters. Appl Geochem
17:517–568
Smedley PL, Nicolli HB, Macdonald DMJ, Barros AJ, Tullio JO
(2002) Hydrogeochemistry of arsenic and other inorganic
constituents in groundwaters from La Pampa, Argentina. Appl
Geochem 17:259–284
Smith E, Naidu R, Alston AM (1999) Chemistry of arsenic in soils I.
Sorption of arsenate and arsenite by four Australian soils.
J Environ Qual 28:1719–1726
Smith AH, Lingas EO, Rahaman M (2000) Contamination of drinking
water by arsenic in Bangladesh: a public health emergency. Bull
World Health Organ 78:1093–1103
821
Turpeinen R, Pantsar-Kallio M, Haggblom M, Kairesalo T (1999)
Influence of microbes on the mobilization, toxicity and biom-
ethylation of arsenic in soil. Sci Total Environ 236:173–180
Violante A, Pigna M (2002) Competitive sorption of arsenate and
phosphate on different clay minerals and soils. Soil Sci Soc Am J
66:1788–1796
Williams LE, Barnett MO, Kramer TA, Melville J (2003) Adsorption
and transport of arsenic (V) in experimental subsurface systems.
J Environ Qual 32:841–850
Woolson EA (1973) Arsenic phytotoxicity and uptake in six vegetable
crops. Weed Sci 21:524–527
Yan-Chu H (1994) Arsenic distribution in soils. Arsenic in the
environment, part-I: cycling and characterization. In: Nriagu JO
(eds) Wiley, New York, p 17–49
123