Hydrogeochemical contrast between brown and grey sand aquifers in shallow depth

of Bengal Basin: Consequences for sustainable drinking water supply

Ashis Biswas
a, b,
, Bibhash Nath
c
, Prosun Bhattacharya
a
, Dipti Halder
a, b
, Amit K. Kundu
b
, Ujjal Mandal
b
,
Abhijit Mukherjee
d
, Debashis Chatterjee
b
, Carl-Magnus Mrth
e
, Gunnar Jacks
a
a
KTH-International Groundwater Arsenic Research Group, Department of Land and Water Resources Engineering, KTH Royal Institute of Technology, SE-100 44 Stockholm, Sweden
b
Department of Chemistry, University of Kalyani, Kalyani, 741235, West Bengal, India
c
School of Geosciences, The University of Sydney, Sydney, NSW 2006, Australia
d
Department of Geology and Geophysics, Indian Institute of Technology-Kharagpur, Kharagpur, 721302, West Bengal, India
e
Department of Geological Sciences, Stockholm University, SE-106 91 Stockholm, Sweden
a b s t r a c t a r t i c l e i n f o
Article history:
Received 19 April 2012
Received in revised form 9 May 2012
Accepted 10 May 2012
Available online xxxx
Keywords:
Bengal Basin
Arsenic
Manganese
Redox condition
Sustainable drinking water supply
Delineation of safe aquifer(s) that can be targeted by cheap drilling technology for tubewell (TW) installation
becomes highly imperative to ensure access to safe and sustainable drinking water sources for the arsenic
(As) affected population in Bengal Basin. This study investigates the potentiality of brown sand aquifers
(BSA) as a safe drinking water source by characterizing its hydrogeochemical contrast to grey sand aquifers
(GSA) within shallow depth (b70 m) over an area of 100 km
2
in Chakdaha Block of Nadia district, West
Bengal, India. The results indicate that despite close similarity in major ion composition, the redox condition
is markedly different in groundwater of the two studied aquifers. The redox condition in the BSA is delineated
to be Mn oxy-hydroxide reducing, not sufciently lowered for As mobilization into groundwater. In contrast,
the enrichments of NH
4
+
, PO
4
3
, Fe and As along with lower Eh in groundwater of GSA reect reductive dis-
solution of Fe oxy-hydroxide coupled to microbially mediated oxidation of organic matter as the prevailing
redox process causing As mobilization into groundwater of this aquifer type. In some portions of GSA the
redox status even has reached to the stage of SO
4
2
reduction, which to some extent might sequester dis-
solved As from groundwater by co-precipitation with authigenic pyrite. Despite having low concentration
of As in groundwater of the BSA the concentration of Mn often exceeds the drinking water guidelines,
which warrants rigorous assessment of attendant health risk for Mn prior to considering mass scale exploi-
tation of the BSA for possible sustainable drinking water supply.
2012 Elsevier B.V. All rights reserved.
1. Introduction
The extent of human exposure due to naturally occurring dissolved
arsenic (As) in the Holocene sedimentary aquifers of Bengal Basin has
been recognized as world's largest mass poisoning in human history
(Smith et al., 2000). The presence of elevated As (>10 g/L) in ground-
water was rst reported from West Bengal (currently Paschim Banga),
India in early 1980s (Saha, 1984). In the subsequent years, such enrich-
ment was also accounted from the aquifers of Bangladesh (Dhar et al.,
1997; Roy Chowdhury et al., 1999). Currently about 60 million of the
people fromthese regions are at risk of chronic As toxicity due to expo-
sure from drinking water as well as other dietary components
(Chakraborti et al., 2008; Chatterjee et al., 2010; Halder et al., 2012).
Since after rst reporting of As in groundwater, signicant pro-
gresses have been made in the context of its source characterization,
identication of mobilization and immobilization processes, spatial
and vertical distributions, etc. (Bhattacharya et al., 1997; Nickson et
al., 1998; BGS and DPHE, 1999, 2001; Harvey et al., 2002; van Geen et
al., 2003; Islam et al., 2004; Ravenscroft et al., 2005; Polizzotto et al.,
2008; Nath et al., 2009; Polya and Charlet, 2009; Mukherjee et al.,
2011; Biswas et al., 2012). These developments have led to the govern-
ments of West Bengal, India and Bangladesh to introduce various miti-
gation strategies together with international aid agencies to ensure safe
drinking water supply among the affected population. The undertaken
strategies include treatment of surface water (pond as well as river
water), rain water harvesting, installation of dug wells, tubewell (TW)
switching (changing of drinking water source from high As TWs to
nearest lowAs TWs), installation of deep TWs (depth >150 m) and dis-
tribution of households and community lters (Jakariya et al., 2003,
2007). Nevertheless, the community acceptance of most of these strat-
egies is not very promising because of technical, economical and social
constraints (Jakariya et al., 2003, 2007; Ahmed et al., 2006; Nath et al.,
Science of the Total Environment 431 (2012) 402412
Corresponding author at: KTH-International Groundwater Arsenic Research Group,
Department of Land and Water Resources Engineering, KTHRoyal Institute of Technology,
SE-100 44 Stockholm, Sweden. Tel.: +46 8790 7967; fax: +46 8790 6857.
E-mail address: ashis@kth.se (A. Biswas).
0048-9697/$ see front matter 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.scitotenv.2012.05.031
Contents lists available at SciVerse ScienceDirect
Science of the Total Environment
j our nal homepage: www. el sevi er . com/ l ocat e/ sci t ot env
2008a; Johnston et al., 2010). People living in the rural villages do not
prefer alternative drinking water sources other than TW water located
within their premises. Ironically, the use of TWwater for domestic pur-
pose is deeply embedded into the daily life of the rural villagers
(Johnston et al., 2010). Thus TW switching and deep TW installation
only gained popularity and effectively reduced the number of exposed
population (Ahmed et al., 2006). However, the installation of deep
TWs requires advanced drilling technology, which increases the instal-
lation cost (5001200 USD) several times as compared to shallow TWs
installation (depth b70 m, cost 50120 USD) (Hug et al., 2011). Rural
villagers cannot afford the cost to install household deep TWs. Instead,
they need to depend on the community TWs, which are also few in
number or on the deep TWs installed by wealthier people in the com-
munity. Additionally villagers are also reluctant to collect drinking
water fromTWowned by someone else, a powerful social burden to ac-
cess safe drinking water by means of TWswitching and deep TWinstal-
lation (Johnston et al., 2010). Consequently 54% of the exposed
population in Bangladesh still have no other options except to drink
As contaminated water (Ahmed et al., 2006). Thus, to prioritize sustain-
able As mitigation management and achieve the United Nations (UN)
Millennium Development Goals (MDGs) of halving the proportion of
population having no access to sustainable safe drinking water world-
wide by 2015 (Target 7C), it becomes extremely imperative to delineate
safe aquifer(s) within shallow depth, which can be targeted by locally
available cheap drilling technology.
Fewrecent studies have investigated the ongoing indigenous drilling
practice by local drillers in the rural Bengal and attempted to correlate
aquifer sediment color with the occurrence of As in groundwater (van
Geen et al., 2002, 2003; Jakariya et al., 2007; von Brmssen et al., 2007,
2008; Pal and Mukherjee, 2008, 2009; Bundschuh et al., 2010). Based
on the studies in Bangladesh it is reported that grey sand aquifers
(GSA) are mostly contaminated with dissolved As (>10 g/L), whereas
brown sand aquifers (BSA) may be safe (b10 g/L) (e.g. von Brmssen
et al., 2007). The underlying reason for the occurrence of contrasting dis-
solved As in groundwater of these two aquifers has been hypothesized
as: being sub-aerially oxidized during temporal sea level regression peri-
od (Umitsu, 1993) the redox condition of the BSA is quite high, not
reaching the stage of Fe oxy-hydroxide reduction (von Brmssen et al.,
2007, 2008), which is prevailing at the GSAcausing high As groundwater
(Bhattacharya et al., 1997; Nickson et al., 1998). In some places the BSAis
also overlain by lowpermeable red clay layer (considered as a Palaeosol
layer by Goodbred and Kuehl, 2000), which protects the recharges of As
and/or dissolved organic matter (DOC) rich groundwater from the GSA
(Shibasaki et al., 2007; von Brmssen et al., 2008; McArthur et al.,
2011). Consequently the BSA within shallow depth has been suggested
to be targeted for safe drinking water supply in Bangladesh (von
Brmssen et al., 2007; Bundschuh et al., 2010). However, so far no at-
tempt has been made to hydrogeochemically validate the redox status
of these two aquifers, which could be extremely important for assessing
the long term sustainability of BSA for safe drinking water supply.
In order to explore the groundwater evolution and validate redox
status at BSA and GSA the present study has undertaken a detailed
hydrogeochemical investigation within shallow depth (b70 m). The
decisive factors responsible for different redox conditions within the
aquifers have been delineated by discriminant analysis. Factor analy-
sis has been performed to explain the occurrence of As and Mn in
terms of similar covariance of the hydrogeochemical parameters. Fi-
nally effort has been made to justify the potentiality of BSA for sus-
tainable drinking water supply.
2. Materials and methods
2.1. Study area settings
The study area (100 km
2
; 23.0223.14N, 88.4988.62E) is locat-
ed approximately 60 km north of Kolkata city, in the Chakdaha Block
of Nadia district, West Bengal. The area is bounded on the west by
river Hooghly (distributaries of river Ganges) and on the east by
river Ichamati. Our concurrent lithological study (Biswas et al., man-
uscript under preparation) has investigated the distribution of differ-
ent aquifers (in terms of aquifer sediment color) within shallow
depth of the study area, based on drilling of 29 boreholes by locally
available hand suction drilling technology (Fig. 1). Hydrogeologically
the aquifers of the study area represent part of the Sonar Bangla
Aquifer (Mukherjee et al., 2007a). Though local drillers are very ef-
cient to classify different colors of the sediment, there is still risk of
misidentication (von Brmssen et al., 2007). In order to minimize
this risk, aquifers within shallow depth were classied according to
two major sediment color categories: viz grey and brown. In the
eld, sediment form each 1.5 m interval was assigned either grey or
brown color by looking into the washed sediment soon after their re-
covery from the borehole, prior to atmospheric oxidation.
The BSA was distributed along central (northsouth transect) and
southwestern region, whereas the distribution of GSA was limited to
northwest (beside Hooghly river) and eastern region (parallel to
northsouth transact of BSA) of the study area (Fig. 1). In most of
the boreholes, drilling revealed the formation of either BSA or GSA.
Over the entire study area the thickness of surface aquitard, which
caps the BSA, was higher than that caps the GSA. Only at central
northern part of the study area the GSA was overlying the BSA
(Fig. 1). In most of these boreholes, the BSA was separated from the
GSA by a red clay layer (Biswas et al., manuscript under preparation).
The depth to top of the BSA was highest in southwestern part. Drilling
of two boreholes (BH-11 and 12) at the southwestern region was
stopped at 50 m even before reaching any aquifer. However, the drill-
er conrmed the presence of BSA at the base of red clay layer around
the depth of 7080 m.
2.2. Groundwater sampling and analysis
A total of 57 groundwater samples (35 fromGSA and 22 fromBSA)
were collected from the existing TWs installed in shallow depth
(b70 m, except for 3 TWs installed in BSA) close to 29 drilled bore-
hole locations (Fig. 1). Prior to groundwater sampling the TWs were
purged continuously until pH, electrical conductivity (EC) tempera-
ture (T) and oxidation reduction potential (ORP, latter corrected
with respect to standard hydrogen electrode for Eh) were stabilized.
The pH, EC, T, ORP and dissolved oxygen (DO) were measured by
HACH multimeter (HQd40) coupled to specic IntelliCAL electrode
(pH: PHC10105; EC: CDC40105; ORP: MTC10105; DO: LDO10105).
The electrodes for ORP and DO were tted with ow cell to minimize
the contact of water with atmospheric oxygen during measurement.
The alkalinity (reported as HCO
3

) was measured on site by titrating

with 0.02 N H
2
SO
4
before groundwater sampling. From each TW
four sets of groundwater samples were preserved after ltering
through 0.45 m membrane lters (Axiva) for the measurement of
Fe(II), DOC, anions, major cations, trace elements and As(III). The
sample for Fe(II) and DOC was directly ltered into 50 mL prewashed
high density polyethylene bottles (Tarson), containing 2 mL of con-
centrated HCl (12N, Suprapur, Merck). The sample for anions was l-
tered into a rubber sealed evacuated vials (VAKU-8, Hindustan
syringe & Medical devices Ltd.) by tting a needle with the lter hold-
er and was left unacidied. The samples for Fe(II) and anions were
rapped with aluminum foil to inhibit photo oxidation of the redox
sensitive parameters. In the eld As(III) and (V) were separated by
passing 20 mL sample through a Disposable Cartridge packed with
an ion exchanger, at a ow rate of 5 mL/min (Metal Soft Centre, High-
land Park, USA, Meng et al., 2001). The samples for quantication of
As(III), major cations and trace elements were acidied with HNO
3
(14N, Suprapur, Merck). In the eld all samples were stored in ice
box and nally after return to the laboratory, samples were preserved
in a refrigerator at 4 C until analysis.
403 A. Biswas et al. / Science of the Total Environment 431 (2012) 402412
Iron(II), NH
4
+
and anions were analyzed overnight after sampling
to minimize redox alteration. From each bottle of HCl acidied sam-
ples, 2 mL was pipette out for the analysis of Fe(II) and total Fe spec-
trophotometrically by the O-phenanthroline method (APHA, 1998).
The remaining volume of sample was preserved for DOC analysis by
Shimadzu 5000 TOC analyzer. Anions and NH
4
+
were analyzed in
the same sample by Metrohm Ion Chromatography (model 761 Com-
pact IC) using Metrosep Anion 1 (No. 12007935) and Metrosep Cation
12 (No. 00300349) column respectively. The major cations and trace
elements were analyzed by inductively coupled plasma optical emis-
sion spectrometer (ICP-OES, Varian Vista-PRO). Ten percent of the
samples (n=6) were selected randomly to reanalyze to test the pre-
cision of analysis by ICP-OES. For all the elements the precision of the
analysis was >97%. Furthermore, the concentration of As in all sam-
ples [for As(III) as well as total As] were also reanalyzed by hydride
generation atomic absorption spectrometer (HG-AAS, Varian AA240,
detection limit b1 g/L) (APHA, 1998). The mutual agreement be-
tween As concentrations measured by ICP-OES and HG-AAS was
>99% (pb0.01).
2.3. Multivariate statistical analysis
2.3.1. Discriminant analysis
The software package IBM SPSS Statistics 19 was used to perform
discriminant analysis, in order to characterize the decisive
hydrogeochemical parameters responsible for redox zonation within
Table 1
Covariance among the hydrogeochemical parameters.
pH Eh EC HCO
3

Cl

Ca
2+
Mg
2+
Na
+
K
+
Si
4+
SO
4
2
PO
4
3
NH
4
+
DOC Al Fe Mn As
pH 1.00 0.06 0.47 0.56 0.24 0.37 0.39 0.60 0.04 0.44 0.09 0.22 0.42 0.45 0.13 0.20 0.09 0.08
Eh 1.00 0.35 0.19 0.36 0.27 0.26 0.10 0.61 0.01 0.22 0.65 0.52 0.19 0.04 0.70 0.53 0.56
EC 1.00 0.89 0.70 0.90 0.81 0.66 0.39 0.02 0.48 0.46 0.45 0.22 0.06 0.57 0.05 0.24
HCO
3

1.00 0.39 0.84 0.81 0.66 0.18 0.21 0.23 0.32 0.40 0.24 0.09 0.38 0.22 0.24
Cl
-
1.00 0.63 0.53 0.38 0.48 0.22 0.46 0.45 0.35 0.18 0.15 0.55 0.23 0.09
Ca
2+
1.00 0.75 0.47 0.26 0.01 0.43 0.33 0.30 0.17 0.08 0.46 0.16 0.16
Mg
2+
1.00 0.35 0.24 0.08 0.44 0.38 0.33 0.09 0.02 0.46 0.02 0.25
Na
+
1.00 0.11 0.30 0.19 0.07 0.21 0.38 0.00 0.12 0.23 0.10
K
+
1.00 0.12 0.29 0.59 0.44 0.22 0.06 0.66 0.29 0.33
Si
4+
1.00 0.40 0.09 0.06 0.32 0.11 0.18 0.22 0.04
SO
4
2
1.00 0.06 0.07 0.15 0.13 0.33 0.11 0.02
PO
4
3
1.00 0.88 0.22 0.01 0.86 0.53 0.64
NH
4
+
1.00 0.34 0.02 0.76 0.41 0.68
DOC 1.00 0.04 0.18 0.06 0.11
Al 1.00 0.10 0.04 0.05
Fe 1.00 0.51 0.74
Mn 1.00 0.41
As 1.00
Underlined Pearson correlation coefcients are signicant at pb0.001.
23.12
GSA GSA
a
c
23.10
GSA
GSA & BSA
Chakdaha
23.08
RS
GSA
b
GSA
b
23.06 BSA BSA
BSA
GSA
23.04
GSA
BSA
4.0 km
23.02

88.50 88.52 88.54 88.56 88.58 88.60
Longitude
Borehole Location
Groundwater
Sampling Point
L
a
t
i
t
u
d
e
Fig. 1. The study area map: a. India, b. West Bengal, white circle in the map indicates the location of Chakdaha Block in West Bengal, c. satellite image of Chakdaha Block, Nadia
District. The distribution of brown sand aquifer (BSA) and grey sand aquifer (GSA) within shallow depth of the study area has been shown by white and blue dashed line. The
area enclosed by white dashed line represents distribution of BSA, the area outside white dashed line represents distribution of GSA and area enclosed by blue dashed line repre-
sents the area, where GSA overlies the BSA. The satellite image of the study area was acquired from Google Earth 6.0.2 (for color picture see the web version of the article).
404 A. Biswas et al. / Science of the Total Environment 431 (2012) 402412
the shallow aquifers as well as to classify groundwater samples
according to different redox zones. Eighteen hydrogeochemical pa-
rameters listed in Table 1 were included in the discriminant analysis.
To eliminate the inuence of different measurement units and make
the data set dimensionless the analytical results were rst normalized
to mean value of zero and standard deviation of 1. The normalization
also increases the inuence of variable with small variance and vice
versa (Liu et al., 2003). A two group (less and strong reducing zone)
model was adopted for this analysis. Groundwater samples were ini-
tially grouped according to sediment color of the screening depth of
TWs in the aquifers. The canonical discriminant function coefcients
for each hydrogeochemical parameters were computed to calculate
the individual discriminant function (Lee et al., 2008; Hus et al.,
2010), which ultimately separated the groundwater samples into
two different redox zones.
2.3.2. Factor analysis
In order to explain the evolution of groundwater chemistry, spe-
cically the occurrence of dissolved As and Mn in terms of association
of the hydrogeochemical parameters, factor analysis was also per-
formed using software package IBM SPSS Statistics 19. The same
data set of discriminant analysis was used for factor analysis. Principal
component analysis (PCA) was adopted to construct the correlation
coefcient matrix (Table 1) based on which eigenvalues and eigen-
vectors were calculated and the data were transformed into factors.
The criterion was set to extract factors with eigenvalue only greater
than 1 (Kaiser, 1958; Davis, 1987; Reyment and Joreskog, 1993; Liu
et al., 2003). After extraction of the factors, factor axis was rotated fol-
lowing Kaiser's Varimax algorithm (Kaiser, 1958) for easier
interpretation of the factor loadings for each factor. The factor scores
(contribution of each factor) for individual well were also computed.
The spatial distribution of these factor scores may provide better in-
sight of the underlying geochemical processes responsible for
hydrogeochemical evolution in an area (Liu et al., 2003).
2.4. Groundwater speciation modeling
For individual groundwater sample speciation modeling was per-
formed with the geochemical software package of PHREEQC (version
2.8) using wateq4f database (Parkhurst and Appelo, 1999) to calculate
the value of P
CO2
and saturation indices (SI =log [IAPK
T
1
], where
IAP and K
T
are ion activity product and equilibriumsolubility constant
at ambient temperature respectively) of major mineral phases that
may regulate the groundwater chemistry in two aquifers. Further,
the values of pe (where pe=16.9Eh at 25 C) corresponding to
Fe(III)/Fe(II) and As(V)/As(III) redox couples were also calculated
from measured concentration of Fe(III), Fe(II) and As(V), As(III) re-
spectively by PHREEQC to identify the key redox process that regu-
lates redox potential in the aquifers.
3. Results
3.1. Groundwater composition
3.1.1. Major ion chemistry
The physical properties and ionic compositions of groundwater
samples collected from BSA and GSA have been summarized in sup-
plementary data (SD) Tables 1 and 2 respectively. The results indicate
that in both aquifers groundwater has circum-neutral pH (6.877.48)
with similar temperature range (26.328.2 C). The ranges of electri-
cal conductivity (BSA: 501935 S/cm, median: 663 S/cm; GSA:
3561177 S/cm, median: 715 S/cm) suggest roughly similar ex-
tents of water-sediment interactions in both aquifers. The groundwa-
ter in both aquifers is predominantly of CaMgHCO
3
type. However,
other hydrochemical facies such as CaMgHCO
3
Cl, CaMgNa
HCO
3
and CaNaMgHCO
3
are also sometimes present due to the
local enrichment of particular ions. There is no signicant difference
between major ion concentrations in groundwater of two aquifers ex-
cept for enrichment of K
+
(median: GSA4.42, BSA2.32 mg/L) and
Cl

(median: GSA18.4, BSA6.49 mg/L) in GSA. The enrichment of

Cl

in GSA is also consistent with relatively higher EC in this aquifer.

The ranges of calculated P
CO2
indicate that for both BSA (range:
Table 2
Classication results of discriminant analysis.
Aquifer redox
condition
No. of
TWs
based on
sediment
color of
the
screening
depth
No. of TWs assigned by DA %
Correct
Strong reducing Less reducing
Strong reducing 35 33 2 94.3
Less reducing 22 0 22 100
Total 57 33 24 96.5
BSA GSA
0.10
0.22
0.34
0.46
0.58
0.70
BSA GSA
-1.0
-0.4
0.2
0.8
1.4
2.0
BSA GSA
-1.0
-0.4
0.2
0.8
1.4
2.0
BSA GSA
-1.0
-0.2
0.6
1.4
2.2
3.0
BSA GSA
-1.0
-0.4
0.2
0.8
1.4
2.0
BSA GSA
-7.0
-4.8
-2.6
-0.4
1.8
4.0
a b c
f e d
S
a
t
u
r
a
t
i
o
n

I
n
d
i
c
e
s

(
S
I
)
Fig. 2. Distribution of saturation indices (SI) for mineral phases: a. calcite (CaCO
3
); b. dolomite [CaMg(CO
3
)
2
]; c. rhodochrosite (MnCO
3
); d. manganese hydrogen phosphate
(MnHPO
4
); e. siderite (FeCO
3
) and f. vivianite [Fe
3
(PO
4
)
2
:8H
2
O] for groundwater samples collected from BSA and GSA in the study area.
405 A. Biswas et al. / Science of the Total Environment 431 (2012) 402412
10
3.42
to 10
2.9
atm, median: 10
3.01
atm) and GSA (range:
10
3.63
to 10
2.61
atm, median: 10
3.05
atm) groundwater samples
(except one sample fromGSA) have higher P
CO2
than the atmospheric
P
CO2
(10
3.5
atm). The calculation of SI further reveals that ground-
water samples are nearly at equilibrium with calcite and dolomite
(Fig. 2).
3.1.2. Distribution of redox sensitive species
In all groundwater samples collected from BSA and GSA the concen-
tration of DO and NO
3

are below detection limit (BDL). The comparison

of observed pe values (calculated from measured Eh) with that corre-
spondto Fe(III)/Fe(II) andAs(V)/As(III) redox couples reveals that the ob-
served pe values for the samples of BSA and GSA fall respectively along
the upper and lower end of calculated pe range of the Fe(III)/Fe(II)
redox couple (Fig. 3). This comparison suggests that though the redox
condition in both aquifers is controlled by the Fe(III)/Fe(II) redox equilib-
rium, the groundwater inGSAis more reducing than groundwater inBSA.
The groundwater in GSA is more enriched with species such as PO
4
3
,
NH
4
+
and SO
4
2
compare to groundwater in BSA (Fig. 4). Despite enrich-
ment of SO
4
2
in GSA the concentration is not very high (range: BDL
26.2 mg/L, median: 0.30 mg/L). Strong pungent odor of hydrogen sul-
phide (H
2
S) was noted in fewwells fromGSA during sampling. How-
ever this odor does not necessarily correspond with low SO
4
2
concentration in groundwater. Moreover, the odor of H
2
S was absent
in groundwater of BSA. This indicates that SO
4
2
reduction is not en-
tirely responsible for low SO
4
2
concentration in groundwater of the
study area. The scarcity of sulphidic minerals in the aquifer sediment
might also limit initial concentration of SO
4
2
in groundwater
(Mukherjee and Fryar, 2008). Though in Bangladesh, von Brmssen
et al. (2007) have reported the enrichments of DOC and HCO
3

in
groundwater of GSA; in present study the concentrations are similar
in both aquifers (Fig. 4).
In the GSA, 32 (91%) and 19 (54%) of the 35 collected groundwater
samples have As concentration above the WHO safe drinking water
guideline value of 10 g/L and Indian national drinking water stan-
dard of 50 g/L respectively (Fig. 4). The median value (54.3 g/L) is
higher than both WHO guideline and national standard. However, in
only 1 of 22 samples collected from BSA, the dissolved As concentra-
tion exceeds 10 g/L (Fig. 4). In GSA, As is predominantly present as
As(III) [% of As(III) range: 75100, median: 95.6] (SD Table 2), where-
as for samples collected from BSA, when As concentration exceeds in-
strumental detection limit is mostly present as As(V) [% of As(V)
range: 5.41100, median: 100, excluding BDL values] (SD Table 1).
Following the same trend the groundwater of GSA is also more
enriched with dissolved Fe (range: 0.8211.3 mg/L, median:
5.31 mg/L) compare to groundwater of BSA (range: 0.242.87 mg/L,
median: 0.44 mg/L) (Fig. 4). Though, in both aquifers Fe is predomi-
nantly present as Fe(II), the extent of predominance is signicantly
higher at GSA (range: 84.1100%, median: 94.5%) compared to BSA
(range: 36.697.2%, median: 71.2%) (SD Tables 1 and 2). The aquifer
wise distribution of dissolved Mn in groundwater follows the oppo-
site trends of As and Fe. Only 6 (17%) and 7 (20%) samples out of 35
collected from GSA have Mn concentration above previous WHO
guideline value of 400 g/L and Indian national drinking water stan-
dard of 300 g/L respectively. However out of 22 samples of BSA, in
18 (82%) and 21 (95%) samples dissolved Mn concentration exceeds
400 g/L and 300 g/L respectively (Fig. 4).
The distribution of SI for the major mineral phases, which may
regulate the concentration of Fe(II) and Mn(II) in groundwater re-
veals that groundwater in BSA are mostly at equilibrium with respect
to rhodochrosite (MnCO
3
), whereas equilibriums with respect to
-10 -5 0 5 10 15
H
2
O
/
H
2
C
(
I
V
)
/
C
(
-
I
V
)
S
(
V
I
)
/
S
(
-
I
I
)
V
(
I
V
)
/
V
(
I
I
I
)
V
(
V
)
/
V
(
I
V
)
S
e
(
I
V
)
/
S
e
(
-
I
I
)
U
(
V
I
)
/
U
(
I
V
)
A
s
(
V
)
/
A
s
(
I
I
I
)
F
e
(
I
I
I
)
/
F
e
(
I
I
)
M
n
(
I
V
)
/
M
n
(
I
I
)
N
(
I
I
I
)
/
N
(
-
I
I
I
)
N
(
V
)
/
N
(
I
I
I
)
C
r
(
V
I
)
/
C
r
(
I
I
I
)
S
e
(
V
I
)
/
S
e
(
I
V
)
O
2
/
H
2
O
Calculated pe
Fe(III)/Fe(II) As(V)/As(III)
G
S
A
B
S
A
Anoxic redox zone Oxic redox zone
S
u
l
f
i
d
i
cPost-Oxic Methanic
Hematite, goethite,
Mn-oxides
Glauconite, other Fe(II) and (III)
silicates, siderite, vivianite,
rhodochrosite
Siderite, vivianite,
rhodochrosite, earlier
formed sulfidic minerals P
y
r
i
t
e
Theoritical pe of different redox couples
M
a
x
.
7
5

p
e
r
c
e
n
t
i
l
e
M
e
d
i
a
n
2
5

p
e
r
c
e
n
t
i
l
e
M
i
n
.
Legend
Expected mineral phases at different redox zones
O
b
s
e
r
v
e
d

p
e
Fig. 3. Schematic representation of redox zonation in the aquifer. The observed pe values (calculated from measured Eh) of groundwater samples collected from BSA and GSA are
compared with theoretical pe values (when the activities of equilibrated redox phases are same or P
H2
=P
O2
=1 atm at 25 C) of different redox couples and calculated pe values
correspond to Fe(III)/Fe(II) and As(V)/As(III) redox couples [calculated from measured concentration of Fe(III), Fe(II) and As(V), As(III) respectively]. Expected mineral phases at
different redox zones are also shown. The gure has been developed from Mukherjee et al. (2008).
406 A. Biswas et al. / Science of the Total Environment 431 (2012) 402412
siderite (FeCO
3
) and vivianite [Fe
3
(PO
4
)
2
:8H
2
O] are prevailing in
groundwater of GSA (Fig. 2). Saturation Indices values further indi-
cate that MnHPO
4
and Fe(III) mineral phases such as ferric hydroxide
[Fe(OH)
3
], goethite (FeOOH), hematite (Fe
2
O
3
) and magnetite
(Fe
3
O
4
) are stable in both aquifers of the study area.
3.2. Discrimination of groundwater samples
The canonical discriminant function coefcients for each hydrogeo-
chemical parameters have beensummarizedinSDTable 3. The canonical
correlation value of 0.91 indicates that two groups model explain 83%
variation among the hydrogeochemical parameters. The corresponding
discriminant loadings of each hydrogeochemical parameter (Fig. 5)
suggest that the concentrations of PO
4
3
, Fe and NH
4
+
together with the
value of Eh are the main discriminators to predict membership of
groundwater samples to the less or strong reducing group. The hit
ratio (overall predictive accuracy of the discriminant function) value of
96.5% (Table 2) strongly supports the successful classication of ground-
water samples as less or strong reducing, based on sediment color of the
screening depth of respective TW. All the groundwater samples of BSA
are reclassied as less reducing (100%accuracy), whereas only 2 ground-
water samples (HG14 andHG22) of GSA, whichwere initially grouped as
strong reducing are classied as less reducing (94.3% accuracy) by dis-
criminant analysis (Table 2).
3.3. Delineation of factors responsible for groundwater evolution
The mutual covariance of the hydrogeochemical parameters (Table 1)
indicates that the major ions are strongly positively correlated to each
other and also individually positively correlates to EC. Arsenic shows
strong positive correlation with NH
4
+
, Fe and PO
4
3
and negative correla-
tion with Eh, whereas the correlations of Mn to these parameters are op-
posite to that of As. Dissolved organic carbon does not show any
signicant correlation to other hydrogeochemical parameters.
Based on these correlations, factor analysis extracted 4 factors with
eigenvalue greater than 1, which cumulatively explain 74% of the
total hydrogeochemical variations (SD Table 4). Among the four fac-
tors, factor 1 (26.8% variance) has strong positive loadings of major
ions and EC (Fig. 6), which in turns is responsible for total dissolved
solids in groundwater. Factor 2 (26.1% variance) has positive loadings
of Fe, NH
4
+
, PO
4
3
and As and negative loadings of Eh and Mn (Fig. 6).
This factor can be termed as As mobilization as well as Mn immobiliza-
tion factor. The spatial distribution of factor scores of this As mobiliza-
tion and Mn immobilization factor for each well closely overlaps with
the distribution of GSA in the study area (Fig. 7a), which indicates that
this factor is mainly prevailing in GSA. Factor 3 possibly represents
two chemical processes. The positive loadings of DOC and NH
4
+
and
negative loading of SO
4
2
(Fig. 6) characterize the SO
4
2
reduction
BSA GSA
200
280
360
440
520
600
BSA GSA
0
6
12
18
24
30
BSA GSA
0.0
1.6
3.2
4.8
6.4
8.0
BSA GSA
0.0
1.4
2.8
4.2
5.6
7.0
BSA GSA
0.0
1.4
2.8
4.2
5.6
7.0
BSA GSA
0
4
8
12
16
20
BSA GSA
0
600
1200
1800
2400
3000
BSA GSA
0
80
160
240
320
400
H
C
O
3
-

(
m
g
/
L
)
S
O
4
2
-

(
m
g
/
L
)
D
O
C

(
m
g
/
L
)
N
H
4
+

(
m
g
/
L
)
P
O
4
3
-

(
m
g
/
L
)
F
e

(
m
g
/
L
)
M
n

(

g
/
L
)
A
s

(

g
/
L
)
Fig. 4. Distribution of redox species in groundwater of BSA and GSA. The legend of the box whisker plot is same as Fig. 2.
-0.6
-0.4
-0.2
0.0
0.2
0.4
0.6
D
i
s
c
r
i
m
i
n
a
n
t



L
o
a
d
i
n
g
s
E
h
p
H
E
C
C
a
2
+
N
a
+
M
g
2
+
K
+
S
i
4
+
N
H
4
+
H
C
O
3
-
C
l
-
S
O
4
2
-
P
O
4
3
-
M
n
A
s
A
l
D
O
C
F
e
Fig. 5. Discriminant loadings of different hydrogeochemical parameters. The higher ab-
solute value of a loading represents greater contribution of the corresponding param-
eter to discriminate groundwater as less reducing or strong reducing.
407 A. Biswas et al. / Science of the Total Environment 431 (2012) 402412
process, whereas the positive loadings of Si
4+
, Na
+
and HCO
3

together
with negative loading of pH (Fig. 6) suggest the weathering of plagio-
clase minerals (NaAlSi
3
O
8
). However, the spatial distribution of factor
3 scores does not indicate any prevalence to particular aquifer
(Fig. 7b), whichmight signify that two chemical processes are occurring
separately in two aquifers. Factor 4 has only positive loadings of Al and
Cl

(Fig. 6).
4. Discussion
4.1. Evolution of major ion chemistry in shallow aquifers
The geochemical evolution of groundwater is mainly regulated by
carbonate mineral dissolution, silicate weathering and ionexchange pro-
cesses with the aquifer materials (Dowling et al., 2003; Mukherjee and
E
h
p
H
E
C
C
a
2
+
N
a
+
M
g
2
+
K
+
S
i
4
+
N
H
4
+
H
C
O
3
-
C
l
-
S
O
4
2
-
P
O
4
3
-
M
n
A
s
A
l
D
O
C
F
e
E
h
p
H
E
C
C
a
2
+
N
a
+
M
g
2
+
K
+
S
i
4
+
N
H
4
+
H
C
O
3
-
C
l
-
S
O
4
2
-
P
O
4
3
-
M
n
A
s
A
l
D
O
C
F
e
E
h
p
H
E
C
C
a
2
+
N
a
+
M
g
2
+
K
+
S
i
4
+
N
H
4
+
H
C
O
3
-
C
l
-
S
O
4
2
-
P
O
4
3
-
M
n
A
s
A
l
D
O
C
F
e
E
h
p
H
E
C
C
a
2
+
N
a
+
M
g
2
+
K
+
S
i
4
+
N
H
4
+
H
C
O
3
-
C
l
-
S
O
4
2
-
P
O
4
3
-
M
n
A
s
A
l
D
O
C
F
e
-1.0
-0.5
0.0
0.5
1.0
-1.0
-0.5
0.0
0.5
1.0
-1.0
-0.5
0.0
0.5
1.0
-1.0
-0.5
0.0
0.5
1.0
F
a
c
t
o
r

L
o
a
d
i
n
g
s
F
a
c
t
o
r

L
o
a
d
i
n
g
s
Factor 1 Factor 2
Factor 3 Factor 4
Fig. 6. Factor loadings of different hydrogeochemical parameters in groundwater of the study area. The value of loading0.5 represents signicant contribution of the
corresponding parameter.
Longitude
23.02
23.04
23.06
23.08
23.10
23.12
L
a
t
i
t
u
d
e
GSA
BSA
GSA
BSA
GSA
GSA
GSA
GSA
GSA
BSA
4.0 km
88.50 88.52 88.54 88.56 88.58 88.60 88.50 88.52 88.54 88.56 88.58 88.60
Longitude
23.02
23.04
23.06
23.08
23.10
23.12
L
a
t
i
t
u
d
e
GSA
BSA
GSA
BSA
GSA
GSA
GSA
GSA
GSA
BSA
4.0 km
a b
Longitude
23.02
23.04
23.06
23.08
23.10
23.12
L
a
t
i
t
u
d
e
GSA
BSA
GSA
BSA
GSA
GSA
GSA
GSA
GSA
BSA
4.0 km
88.50 88.52 88.54 88.56 88.58 88.60 88.50 88.52 88.54 88.56 88.58 88.60
Longitude
23.02
23.04
23.06
23.08
23.10
23.12
L
a
t
i
t
u
d
e
GSA
BSA
GSA
BSA
GSA
GSA
GSA
GSA
GSA
BSA
4.0 km
a b
Fig. 7. Spatial distribution of factor scores of individual TW for: a. factor 2, responsible for As mobilization as well as Mn immobilization and b. factor 3, responsible for SO
4
2
re-
duction and weathering of plagioclase minerals (NaAlSi
3
O
8
) in groundwater of study area. The change of colors of the contour lines from red to yellow to green represents the con-
tinuous decrease in prevalence of the factors. The area enclosed by white dashed line represents distribution of BSA and the area outside white dashed line represents distribution of
GSA (for color picture see the web version of the article). The factor score of groundwater samples collected from GSA of the area, where GSA overlies BSA (n=6), was excluded
during plotting of spatial distribution to avoid superimposing of prevalence of the factor in BSA and GSA in this part of the study area.
408 A. Biswas et al. / Science of the Total Environment 431 (2012) 402412
Fryar, 2008). The relative contributionof these processes to the evolution
of major aqueous chemistry largely depends on the bulk mineralogy of
the aquifer sediment as well as kinetics of the chemical weathering pro-
cesses (Tardy, 1971; Faure, 1998). Possibly the longer groundwater res-
idence time in Bengal Basin as a consequence of low hydraulic gradient
(1.000.01 m/km from northern to southern part) and extended ow
path is responsible for silicate weathering and ion exchange despite of
slow kinetics (Mukherjee et al., 2007a, 2009 and ref. there in).
Mukherjee and Fryar (2008) and Mukherjee et al. (2009, 2011) have
documented in details about the interplay of these processes for the
deeper part of Sonar Bangla aquifer of western Bengal Basin, which en-
compasses the study area. In this study as suggested by Mukherjee et
al. (2009), solute mass-balance approaches have also been adopted to
demonstrate the extent of these chemical processes occurring in BSA
and GSA. On the bivariate plot of Na
+
-normalized Ca
2+
versus Na
+
-nor-
malized HCO
3

and Mg
2+
(Fig. 8), groundwater samples fromtwo aqui-
fers are clustered between the zone of global average silicate and
carbonate weathering, which indicates that both carbonate mineral dis-
solution and silicate weathering are concurrently occurring in the two
aquifers. However, the trend of the groundwater samples to fall along
the y=2x line on the bivariate plot of Ca
2+
+ Mg
2+
versus HCO
3

to-
gether with high ratio of HCO
3

to Na
+
+ K
+
in the groundwater of
BSA and GSA (Fig. 9) suggests that carbonate mineral dissolution is
more prevailing in the two aquifers. The relative enrichment of P
CO2
in
the aquifers compared to atmospheric P
CO2
and equilibriums of ground-
water with respect to the calcite and dolomite minerals are further con-
sistent withthe prevailing carbonate mineral dissolutioninthe aquifers.
To explore the extent of active cation-exchange in the aquifers, HCO
3

and SO
4
2
corrected Ca
2+
+ Mg
2+
(to exclude the contribution of
Ca
2+
and Mg
2+
from carbonate and silicate weathering) was plotted
against Cl

corrected Na
+
(to exclude the Na
+
input fromatmospheric
deposition) (Fig. 10). Jankowski et al. (1998) have reported that for the
aquifer with active cation exchange between Na
+
and Ca
2+
+ Mg
2+
,
the slope of this equivalent bivariate plot would be 1 (i.e. y=x).
Thus the slope of 0.65 and 0.86 respectively for BSA and GSA indi-
cates that cation-exchange is also to some extent responsible for the ob-
served groundwater compositions in both aquifers, while the extent is
more prominent in the GSA. Notwithstanding the higher extent of cat-
ion exchange in GSA, the concentration of Na
+
is relatively higher (al-
though not very signicantly) in the groundwater of BSA (median,
BSA: 27.2 mg/L and GSA: 22.4 mg/L). This small enrichment of Na
+
in
BSA might be due to the chemical weathering of NaAlSi
3
O
8
as indicated
by factor 3. The higher extent of cation-exchange inGSAmight also con-
tribute to the relative enrichment of K
+
in the groundwater (Mukherjee
et al., 2009). Totrace the originof Cl

enrichment inthe groundwater of

GSA, Cl
-
was plotted against Na
+
(Fig. 11). The previous mineralogical
0.01
0.10
1.00
10.00
100.00
0.0 0.1 1.0 10.0 100.0
0.01
0.10
1.00
10.00
Evaporite
Dissolution
Silicate
Weathering
Carbonate
Dissolution
Evaporite
Dissolution
Silicate
Weathering Carbonate
Dissolution
BSA GSA
H
C
O
3
-

/

N
a
+
M
g
2
+

/

N
a
+
Ca
2+
/ Na
+
0.0 0.1 1.0 10.0 100.0
Ca
2+
/ Na
+
Fig. 8. Bivariate plot of Na
+
normalized HCO
3

and Mg
2+
versus Na
+
normalized Ca
2+
to identify prevailing minerals weathering in groundwater of study area.
0
2000
4000
6000
8000
10000
0 1000 2000 3000 4000 5000
0
2000
4000
6000
8000
10000
12000
0 2000 4000 6000
BSA GSA
y = 2x
y = 2x
y = x
y = x
H
C
O
3
-

(

M
)
H
C
O
3
-

(

M
)
Ca
2+
+ Mg
2+
(M)
Na
+
+ K
+
(M)
Fig. 9. Bivariate plot of HCO
3

versus Ca
2+
+ Mg
2+
and Na
+
+ K
+
to compare the ex-
tents of carbonate and silicate weathering in groundwater of study area.
y = -0.86x + 1.04
-2.5
-1.5
-0.5
0.5
1.5
2.5
GSA
[
(
C
a
2
+

+

M
g
2
+
)

(
H
C
O
3
-
+

S
O
4
2
-
)
]

(
m
e
q
/
L
)
[
(
C
a
2
+

+

M
g
2
+
)

(
H
C
O
3
-
+

S
O
4
2
-
)
]

(
m
e
q
/
L
)
Na
+
- Cl
-
(meq/L)
y = -0.65x + 1.05
-2.5
-1.5
-0.5
0.5
1.5
2.5
-2.5 -1.5 -0.5 0.5 1.5 2.5
Na
+
- Cl
-
(meq/L)
-2.5 -1.5 -0.5 0.5 1.5 2.5
BSA
y = -x
y = -x
Fig. 10. Bivariate plot of HCO
3

and SO
4
2
corrected Ca
2+
+ Mg
2+
versus Cl

corrected
Na
+
to determine the extent of cation exchange in the aquifers of study area.
409 A. Biswas et al. / Science of the Total Environment 431 (2012) 402412
studies of aquifer sediment from the study area by Gault et al. (2005)
Nath et al. (2005, 2008c) and Charlet et al. (2007) did not report the
presence of Cl
-
minerals in the sediment. In absence of any potential
source of Cl

within the aquifer sediment, the Cl

content in ground-
water might be because of atmospheric deposition and mixing with
connate sea water. In Bangladesh, von Brmssen et al. (2007) have
reported the enrichment of Cl

and higher EC in the BSA due to mixing

with connate sea water. However in the present study area, the enrich-
ment of Cl

in shallow GSA compare to deeper BSA discards the possi-

bility of mixing with connate sea water. Furthermore, if Cl

content in
groundwater is entirely of meteoric origin, it should be balanced by
equivalent Na
+
. However, the bivariate plot of Na
+
versus Cl

indicates
that despite higher extent of cation-exchange in the GSA, in some
groundwater samples the ratio of Cl

to Na
+
is greater than 1 and
this ratio is always less than 1 for the groundwater of BSA. Previous
nest piezometric monitoring studies by Biswas et al. (2011) have also
reported similar enrichment of Cl

in near surface aquifer of the

study area. This might indicate that the enrichment of Cl

in groundwa-
ter of GSA is of anthropogenic origin such as agricultural return ow,
septic tank, domestic waste water etc. (Jacks et al., 1999; Rajmohan
and Elango, 2006; Nath et al., 2008a). By doing an isotopic study
Lawson et al. (2008) have already reported the recharge of evaporated
surface water, which might get an input from domestic waste water as
well as agricultural return ow (Charlet et al., 2007; Mukherjee et al.,
2007b), to the shallow aquifers of this study area.
4.2. Redox zonation and mobilization of As and Mn in shallow aquifers
The enrichment of As in the groundwater of Bengal Basin does not
coincide with high As concentration in the aquifer sediment (Harvey
et al., 2002; Swartz et al., 2004; Nath et al., 2005, 2008c), which has
led to conclude that rather than source, the enrichment of As in
groundwater is an artifact of groundwater evolution governed by in-
terplay of various biogeochemical interactions (Bhattacharya et al.,
2007). The most widely accepted mechanism of As mobilization in
the Bengal Basin aquifers is microbially mediated reductive dissolu-
tion of Fe and/or Mn oxy-hydroxide, to which As is adsorbed or co-
precipitated in the aquifer sediment (Bhattacharya et al., 1996,
1997, 2002; Nickson et al., 1998; Acharyya et al., 1999; Islam et al.,
2004; Gault et al., 2005; Nath et al., 2008b; Biswas et al., 2011). In
aquifers, as a consequence of microbial respiration by oxidation of or-
ganic matter, DO and NO
3

are reduced at rst and subsequently

redox status passes through the stages of Mn and Fe oxy-hydroxide
reduction, SO
4
2
reduction to methanogenesis respectively (Fig. 3)
(Stumm and Morgan, 1981). Though the origin of organic matter in
the aquifers of Bengal Basin is a lively debate (Harvey et al., 2002,
2005; Rowland et al., 2006; Sengupta et al., 2008; Neumann et al.,
2010; Datta et al., 2011). The reductive dissolution of Mn oxy-
hydroxide possibly releases both Mn as well as As into groundwater.
Nevertheless, the released As is readily readsorbed onto Fe oxy-
hydroxide in the aquifer sediment (Stben et al., 2003; Hasan et al.,
2007). Only when the redox status reaches the stage of Fe oxy-
hydroxide reduction As is mobilized into groundwater together
with Fe and retained in the aqueous phase (Bhattacharya et al.,
1996, 1997; Zheng et al., 2004; Mukherjee et al., 2008). Thus often
Fe rich groundwater is enriched with As as well, whereas the concen-
tration of As is low in Mn rich groundwater (Biswas et al., 2012).
However in the aquifer in presence of high concentration of HCO
3

and PO
4
3
, Mn and Fe are often precipitated as secondary mineral
phases like MnCO
3
, MnHPO
4
and FeCO
3
, Fe
3
(PO
4
)
2
respectively (von
Brmssen et al., 2008). Furthermore, in anoxic groundwater Mn can
also be immobilized by adsorption and/or co-precipitation onto sider-
ite and calcite by forming metastable solid solutions (FeCO
3
MnCO
3
;
CaCO
3
MnCO
3
), which further recrystallizes to pure mineral phases
(Wersin et al., 1989; Saunders and Swann, 1992). The considerable
amount of Mn incorporation into the carbonate mineral phases has
already been reported for the aquifer sediments of Bengal Basin
(Bhattacharya et al., 2001; Ahmed et al., 2004; Stollenwerk et al.,
2007). The equilibriums of groundwater with respect to MnCO
3
,
MnHPO
4
, FeCO
3
and Fe
3
(PO
4
)
2
(Fig. 2) support the cycling of Mn
and Fe in the aquifers of study area also.
The close overlapping of spatial distribution of factor score of As
mobilization and Mn immobilization factor (factor 2) with the distri-
bution of GSA in the study area (Fig. 7a) and the positive loadings of
As, Fe, NH
4
+
and PO
4
3
together with negative loadings of Eh and
Mn for this factor suggest that in GSA the redox status has lowered
beyond the stage of Mn oxy-hydroxide reduction. Currently reductive
dissolution of Fe-oxyhydroxide, possibly coupled to microbially me-
diated oxidation of organic matter is the prevailing redox processes,
which causes high As groundwater in this aquifer. The high concen-
tration of NH
4
+
and PO
4
3
was produced during oxidation of organic
matter (Bhattacharyya et al., 2003; Bhattacharya et al., 2011). Howev-
er in BSA, high enrichment of Mn along with low concentration of
NH
4
+
, PO
4
3
and Fe suggests that the redox status is mostly limited
to the stage of Mn oxy-hydroxide reduction. The comparison of ob-
served pe values with calculated pe values of Fe(III)/Fe(II) redox cou-
ple (Fig. 3) further supports the distinct redox zonation in the two
aquifers. The positive loadings of DOC and NH
4
+
in combination
with negative loading of SO
4
2
for factor 3 might represent that
even in some locations of GSA redox status has reached to the stage
of SO
4
2
reduction. The notable odor of H
2
S in some samples of GSA
further supports the ongoing SO
4
2
reduction process. This SO
4
2
re-
duction may sequester dissolved As to some extent from groundwa-
ter by co-precipitation with authigenic pyrite as reported in the
aquifer sediment of the study area (Nath et al., 2008c).
4.3. Consequences of safe drinking water supply from BSA
The present study indicates that though the concentration of dis-
solved As in groundwater of BSA is very low, the concentration of dis-
solved Mn is signicantly higher than previous WHO drinking water
guideline as well as Indian national drinking water standard. Recently,
the elevated concentration of Mn in drinking water has been also identi-
ed as potential threat to human health worldwide (e.g. Buschmann et
al., 2007; Ljung and Vahter, 2007; Bundschuh et al., 2010; Nath et al.,
2011). Nevertheless the severity of Mn exposure is comparatively
lower than As exposure (Hug et al., 2011), prolonged consumption of
drinking water with elevated Mn may decrease the intellectuality (IQ)
among children and also causes neurotoxic effect (Wasserman et al.,
2006; Bouchard et al., 2011). It should be mentioned here that recently
WHO has withdrawn the drinking water guideline for Mn by reasoning
that worldwide commonly observed concentrations of Mn in drinking
water sources are well below the health based guideline value of
400 g/L (WHO, 2011). However, our results contradict with the reason
proposed by WHO and warrant re-evaluation of drinking water guide-
line for Mn in near future. The underlying health risk of Mn in drinking
0.0
0.5
1.0
1.5
2.0
2.5
3.0
0.0 0.5 1.0 1.5 2.0 2.5 3.0
BSA GSA
y = x
C
l
-

(
m
M
)
Na
+
(mM)
Fig. 11. Bivariate plot of Cl

versus Na
+
to trace the origin of Cl

in groundwater of
study area.
410 A. Biswas et al. / Science of the Total Environment 431 (2012) 402412
water needs to be addressed more rigorously before considering for
mass scale exploitation of BSA as safe drinking water source despite of
signicantly low As concentration in groundwater. Moreover, the sus-
tainability of the BSA in terms of advective ow of groundwater in
both natural and pumping conditions is highly suspected and deserves
future study to assess the risk of cross contamination (Mukherjee et al.,
2011). However, considering the severity of As health risk in rural Bengal
due to limited availability of As safe drinking water sources, the BSA can
be targeted temporarily for As safe drinking water with regular monitor-
ing programuntil alternate As as well as Mn safe drinking water sources
are explored and made available to the affected population.
Acknowledgements
The authors are thankful to KTH International Groundwater Arsenic
Research Group coordinated by PB. PB acknowledges the nancial sup-
port from Swedish International Development Cooperation Agency
(Sida) and Swedish Research Council (VR) through the Swedish Re-
search Link grant (VR-Sida, dnr: 348-2006-6005) and the Strategic En-
vironmental Research Foundation (MISTRA) (Idea Support Grant, dnr:
2005-035-137) for targeting safe aquifers in regions with high arsenic
in groundwater and options for sustainable drinking water supply.
The authors AB and DH are thankful to the Erasmus Mundus External
Cooperation Window (EMECW-Action II) for providing them doctoral
fellowship throughEURINDIAProgram, coordinated by KTHRoyal Insti-
tute of Technology. BNwould like to acknowledge University of Sydney
for Research Support Grant. The support from the UGC-SAP program
and Department of Science and Technology (DST), Government of
India under the FIST program to Department of Chemistry, University
of Kalyani is also duly acknowledged. We are thankful to the local vil-
lagers for their hospitality during eld campaign. We also deeply ac-
knowledge the valuable suggestions of two anonymous reviewers to
improve the earlier version of this manuscript.
Appendix A. Supplementary material
Supplementary data to this article can be found online at http://
dx.doi.org/10.1016/j.scitotenv.2012.05.031.
References
Acharyya SK, Chakraborty P, Lahiri S, Raymahashay BC, Guha S, Bhowmik A. Arsenic
poisoning in the Ganges delta. Nature 1999;401:545.
Ahmed KM, Bhattacharya P, Hasan MA, Akhter SH, Alam SMM, Bhuyian MAH. Arsenic
contamination in groundwater of alluvial aquifers in Bangladesh: an overview.
Appl Geochem 2004;19:181200.
Ahmed MF, Ahuja S, Alauddin M, Hug SJ, Lloyd JR, Pfaff A, et al. Ensuring safe drinking
water in Bangladesh. Science 2006;314:16878.
APHA, AWWA, WEF. Standard Methods for the Examination of Water and Waste
Water. 20th ed. Washington DC: American Public Health Association; 1998.
BGS, DPHE. Groundwater studies for arsenic contamination in Bangladesh. Final report,
Rapid Investigation Phase. Department of Public Health, Government of Bangla-
desh, Mott MacDonald and British Geological Survey; 1999.
BGS DPHE. Arsenic Contamination of Groundwater in Bangladesh. In: Kinniburgh DG,
Smedley PL, editors. Final report. BGS Tech. Rep. WC/00/19 Keyworth. British Geo-
logical Survey; 2001.. 267 pp.
Bhattacharya P, Chatterjee D, Jacks G. Safeguarding groundwater from arseniferous
aquifers. 22nd WEDC Conference. New Delhi; 1996. p. 25861.
Bhattacharya P, Chatterjee D, Jacks G. Occurrence of arsenic-contaminated groundwa-
ter in alluvial aquifers from delta plains, Eastern India: options for safe drinking
water supply. Int J Water Res Dev 1997;13:7992.
Bhattacharya P, Jacks G, Jana J, Sracek A, Gustafsson JP, Chatterjee D. Geochemistry of
the Holocene alluvial sediments of the Bengal Delta Plain from West Bengal,
India: implications on arsenic contamination in groundwater. In: Jacks G,
Bhattacharya P, Khan AA, editors. Groundwater arsenic contamination in the ben-
gal delta plain of bangladesh. Stockholm: KTH Special Publication; 2001. p. 2140.
Bhattacharya P, Jacks G, Ahmed KM, Routh J, Khan AA. Arsenic in groundwater of the Bengal
delta plain aquifers in Bangladesh. Bull Environ Contam Toxicol 2002;69:53845.
Bhattacharya P, Welch AH, Stollenwerk KG, McLaughlin MJ, Bundschuh J, Panaullah G. Arse-
nic in the environment: biology and chemistry. Sci Total Environ 2007;379:10920.
Bhattacharya P, Mukherjee A, Mukherjee AB. Arsenic in groundwater of India. In: Nriagu JO,
editor. Encyclopedia of environmental health, 1. Burlington: Elsevier; 2011. p. 15064.
Bhattacharyya R, Jana J, Nath B, Sahu SJ, Chatterjee D, Jacks G. Groundwater As mobiliza-
tion in the Bengal Delta Plain, the use of ferralite as a possible remedial measurea
case study. Appl Geochem 2003;18:143551.
Biswas A, Majumder S, Neidhardt H, Halder D, Bhowmick S, MukherjeeGoswami A,
et al. Groundwater chemistry and redox processes: depth dependent arsenic re-
lease mechanism. Appl Geochem 2011;26:51625.
Biswas A, Nath B, Bhattacharya P, Halder D, Kundu AK, Mandal U, et al. Testing tubewell
platform color as a rapid screening tool for arsenic and manganese in drinking
water wells. Environ Sci Technol 2012;46:43440.
Bouchard MF, Sauv S, Barbeau B, Legrand M, Brodeur ME, Bouffard T, et al. Intellectual
impairment in school-age children exposed to manganese from drinking water.
Environ Health Perspect 2011;119:13843.
Bundschuh J, Litter M, Bhattacharya P. Targeting arsenic-safe aquifers for drinking
water supplies. Environ Geochem Health 2010;32:30715.
Buschmann J, Berg M, Stengel C, Sampson ML. Arsenic and manganese contamination
of drinking water resources in Cambodia: coincidence of risk areas with low relief
topography. Environ Sci Technol 2007;41:214652.
Chakraborti D, Rahman MM, Paul K, Chowdhury UK, Sengupta MK, Lodh D, et al. Arse-
nic calamity in the Indian subcontinent: what lessons have been learned? Talanta
2008;58:3-22.
Charlet L, Chakraborty S, Appelo CAJ, Roman-Ross G, Nath B, Ansari AA, et al. Chem-
odynamics of an As hotspot in a West Bengal aquifer: a eld and reactive trans-
port modeling study. Appl Geochem 2007;22:127392.
Chatterjee D, Halder D, Majumder S, Biswas A, Nath B, Bhattacharya P, et al. Assessment
of arsenic exposure from groundwater and rice in Bengal Delta Region, West Ben-
gal, India. Water Res 2010;44:580312.
Datta S, Neal AW, Mohajerin TJ, Ocheltree T, Rosenheim BE, White CD, et al. Perennial
ponds are not an important source of water or dissolved organic matter to ground-
waters with high arsenic concentrations in West Bengal, India. Geophys Res Lett
2011;38:L20404.
Davis JC. Statistics and data analysis in geology. 2nd ed. New York: John Wiley and
Sons; 1987. p. 656.
Dhar RK, Biswas BK, Samanta G, Mandal BK, Chakraborti D, Roy S, et al. Groundwater
arsenic calamity in Bangladesh. Curr Sci 1997;73:4859.
Dowling CB, Poreda RJ, Basu AR. The groundwater geochemistry of the Bengal Basin:
weathering, chemosorption, and trace metal ux to the oceans. Geochim
Cosmochim Acta 2003;67:211736.
Faure G. Principles and applications of geochemistry. 2nd ed. Upper Saddle River, New
Jersey: Prentice Hall; 1998.
Gault AG, Islam FS, Polya DA, Charnock JM, Boothman C, Lloyd JR. Microcosm depth
prole of arsenic release in an arsenic contaminated aquifer, West Bengal. Miner
Mag 2005;69:85563.
Goodbred Jr SL, Kuehl SA. The signicance of large sediment supply, active tectonism,
and eustasy on margin sequence development: Late Quaternary stratigraphy and
evolution of the GangesBrahmaputra delta. Sediment Geol 2000;133:22748.
Halder D, Bhowmick S, Biswas A, Mandal U, Nriagu J, Guha Mazumdar DN, et al. Con-
sumption of brown rice: a potential pathway for arsenic exposure in rural Bengal.
Environ Sci Technol 2012;46:41428.
Hasan MA, Ahmed KM, Sracek O, Bhattacharya P, von Brmssen M, Broms S, et al. Ar-
senic in shallow groundwater of Bangladesh: investigations from three different
physiographic settings. Hydrogeol J 2007;15:150722.
Harvey CF, Swartz CH, Badruzzaman ABM, Keon-Blute N, Yu W, Ali MA, et al. Arsenic
mobility and groundwater extraction in Bangladesh. Science 2002;298:16026.
Harvey CF, Swartz CH, Badruzzaman ABM, Keon-Blute N, Yu W, Ali MA, et al. Ground-
water arsenic contamination on the Ganges Delta: biogeochemistry, hydrology,
human perturbations, and human suffering on a large scale. Comptes Rendus
Geosci 2005;337:28596.
Hug J, Gaertner D, Roberts LC, Schirmer M, Ruettimann T, Rosenberg TM, et al. Avoiding
high concentration of arsenic, manganese and salinity in deep tubewells in
Munshiganj District, Bangladesh. Appl Geochem 2011;26:107785.
Hus CH, Han ST, Kao YH, Liu CW. Redox characteristic and zonation of arsenic-affected multi-
layers aquifers in the Choushui River alluvial fan, Taiwan. J Hydrol 2010;391:35166.
IslamFS, Gault AG, Boothman C, Polya DA, Charnock JM, Chatterjee D, et al. Role of metal re-
ducing bacteria in arsenic release in Bengal Delta sediments. Nature 2004;430:6871.
Jacks G, Sefe F, Carling M, Hammar M, Letsamao P. Tentative nitrogen budget for pit la-
trines. Environ Geol 1999;38:199203.
Jakariya M, Chowdhury AMR, Hossain Z, Rahman M, Sarker Q, Khan RI, et al. Sustain-
able community-based safe water options to mitigate the Bangladesh arsenic ca-
tastrophean experience from two upazilas. Curr Sci 2003;52(2):1416.
Jakariya M, von Brmssen M, Jacks G, Chowdhury AMR, Ahmed KM, Bhattacharya P.
Searching for sustainable arsenic mitigation strategy in Bangladesh: experiences
from two Upazilas. Int. J. Environ. Pollut. 2007;31(374):41530.
Jankowski J, Acworth RI, Shekarforoush S. Reverse ion exchange in deeply weathered por-
phyritic dacite fractured aquifer system, Yass, NewSouth Wales, Australia. In: Arehart
GB, Hulston JR, editors. 9th Internat symp waterrock interaction. Rotterdam: AA
Balkema; 1998. p. 2436.
Johnston RB, Hanchett S, Hoque Khan M. The socio-economic of arsenic removal. Nat
Geosci 2010;3:23.
Kaiser HF. The varimax criteria for analytical rotation in factor analysis. Psychometrika
1958;23(3):187200.
Lawson M, Ballentine CJ, Polya DA, Boyce AJ, Mondal D, Chatterjee D, et al. The geochemical
and isotopic composition of ground waters in West Bengal: tracing groundsurface
water interaction and its role in arsenic release. Miner Mag 2008;72:4414.
Lee JJ, Jang CS, Wang SW, Liang CP, Liu CW. Delineation of spatial redox zones using dis-
criminant analysis and geochemical modeling in arsenic affected groundwater
aquifers. Hydrol Process 2008;22:302941.
411 A. Biswas et al. / Science of the Total Environment 431 (2012) 402412
Liu CW, Lin KH, Kuo YM. Application of factor analysis in the assessment of groundwa-
ter quality in a blackfoot disease area in Taiwan. Sci Total Environ 2003;313:7789.
Ljung K, Vahter M. Time to re-evaluate the guideline value for manganese in drinking
water? Environ Health Perspect 2007;115:15338.
McArthur JM, Nath B, Banerjee DM, Purohit R, Grassineau N. Palaeosol control on
groundwater ow and pollutant distribution: the example of arsenic. Environ Sci
Technol 2011;45:137683.
Meng X, Koratis GP, Christodoulatos C, Bang S. Treatment of arsenic in Bangladesh
well water using a household co-precipitation and ltration system. Water Res
2001;35:280510.
Mukherjee A, Fryar AE, Howell PD. Regional hydrostratigraphy and groundwater ow
modeling in the arsenic-affected areas of the western Bengal basin, West Bengal,
India. Hydrogeol J 2007a;15:1397418.
Mukherjee A, Fryar AE, Rowe HD. Regional-scale stable isotopic signatures of recharge
and deep groundwater in the arsenic affected areas of West Bengal, India. J Hydrol
2007b;334:15161.
Mukherjee A, Fryar AE. Deeper groundwater chemistry and geochemical modeling of
the arsenic affected western Bengal basin, West Bengal, India. Appl Geochem
2008;23:86392.
Mukherjee A, von Brmssen M, Scanlon BR, Bhattacharya P, Fryar AE, Hasan MA, et al.
Hydrogeochemical comparison and effects of overlapping redox zones on ground-
water arsenic near the western (Bhagirathi sub-basin, India) and eastern (Meghna
sub-basin, Bangladesh) of the Bengal basin. J Contam Hydrol 2008;99:3148.
Mukherjee A, Bhattacharya P, Shi F, Fryar AE, Mukherjee AB, Xie ZM, et al. Chemical
evolution in the high arsenic groundwater of the Huhhot basin (Inner Mongolia,
PR China) and its difference from the western Bengal basin (India). Appl Geochem
2009;24:183551.
Mukherjee A, Fryar AE, Scanlon BR, Bhattacharya P, Bhattacharya A. Elevated arsenic in
deeper groundwater of the western Bengal basin, India: extent and controls from
regional to local scale. Appl Geochem 2011;26:60013.
Nath B, Berner Z, Basu Mallik S, Chatterjee D, Charlet L, Steben D. Characterization of
aquifers conducting groundwaters with low and high arsenic concentrations: a
comparative case study from West Bengal, India. Miner Mag 2005;69:84153.
Nath B, Sahu SJ, Jana J, Mukherjee-Goswami A, Roy S, Sarkar MJ, et al. Hydrochemistry
of arsenic-enriched aquifer from rural West Bengal, India: a study of the arsenic
exposure and mitigation option. Water Air Soil Pollut 2008a;190:95-113.
Nath B, Steben D, Basu Mallik S, Chatterjee D, Charlet L. Mobility of arsenic in West
Bengal aquifers conducting low and high groundwater arsenic. Part I: comparative
hydrochemical and hydrogeological characteristics. Appl Geochem 2008c;23:
97795.
Nath B, Berner Z, Chatterjee D, Basu Mallik S, Steben D. Mobility of arsenic in West
Bengal aquifer conducting low and high groundwater arsenic. Part II: comparative
geochemical prole and leaching study. Appl Geochem 2008b;23:996-1011.
Nath B, Chakraborty S, Burnol A, Stben D, Chatterjee D, Charlet L. Mobility of arsenic in
the sub-surface environment: an integrated hydrogeochemical study and sorption
model of the sandy aquifer materials. J Hydrol 2009;364:23648.
Nath B, Maity JP, Jean JS, Birch G, Kar S, Yang HJ, et al. Geochemical characterization of
arsenic-affected alluvial aquifers of the Bengal Delta (West Bengal and Bangladesh)
and Chianan Plains (SW Taiwan): implications for human health. Appl Geochem
2011;26:70511.
Neumann RB, Ashfaque KN, Badruzzaman ABM, Ashraf Ali M, Shoemaker JK, Harvey CF.
Anthropogenic inuence on groundwater arsenic concentration in Bangladesh. Nat
Geosci 2010;3:4652.
Nickson R, McArthur J, Burgess W, Ahmed KM, Ravenscroft P, Rahman M. Arsenic poi-
soning of Bangladesh groundwater. Nature 1998;395:338.
Pal T, Mukherjee PK. Orange sanda geological solution for arsenic pollution in Bengal
Delta. Curr Sci 2008;94(1):313.
Pal T, Mukherjee PK. Study of subsurface geology in locating arsenic-free groundwater
in Bengal Delta, West Bengal, India. Environ Geol 2009;56:121125.
Parkhurst DL, Appelo CAJ. User's guide to PHREEQC (version 2): a computer program
for speciation. Batchreaction, onedimensional transport, and inverse geochemi-
cal calculation. US Geol Surv Water Resour Invest Rep; 1999. p. 99-425.
Polizzotto ML, Kocar BD, Benner SG, Sampson M, Fendorf S. Near-surface wetland sed-
iments as a source of arsenic release to ground water in Asia. Nature 2008;454:
5059.
Polya D, Charlet L. Rising arsenic risk? Nat Geosci 2009;2:3834.
Rajmohan N, Elango L. Hydrogeochemistry and its relation to groundwater level uctu-
ation in the Palar and Cheyyar river basin, southern India. Hydrol Process 2006;20:
241527.
Ravenscroft P, Burgess WG, Ahmed KM, Burren M, Perrin J. Arsenic in groundwater of
the Bengal Basin, Bangladesh: distribution, eld relations, and hydrogeological set-
ting. Hydrogeol J 2005;13:72751.
Reyment RA, Joreskog KH. Applied factor analysis in the natural sciences. Cambridge,
England; New York, NY, USA: Cambridge University Press; 1993. p. 371.
Rowland HAL, Polya DA, Lloyd JR, Pancost RD. Characterization of organic matter in a
shallow, reducing, arsenic-rich aquifer, West Bengal. Org Geochem 2006;37:
110114.
Roy Chowdhury T, Basu GK, Mandal BK, Biswas BK, Chowdhury UK, Chanda CR, et al.
Arsenic poisoning in the Ganges delta. Nature 1999;401:5456.
Saha KC. Melanokeratosis from arsenical contamination of tubewell water. Indian J
Dermatol 1984;29:3746.
Saunders JA, Swann CT. Nature and origin of authigenic rhodochrosite and siderite
from the Paleozoic aquifer, northeast Mississippi, U.S.A. Appl Geochem 1992;7:
37587.
Sengupta S, McArthur JM, Sarkar A, Leng MJ, Ravenscroft P, Howarth RJ, et al. Do ponds
cause arsenic-pollution of groundwater in the Bengal Basin? An answer from West
Bengal. Environ Sci Technol 2008;42:515664.
Shibasaki N, Lei P, Kamata A. Evaluation of deep groundwater development for arsenic
mitigation in western Bangladesh. J Environ Sci Health Part A 2007;42:191932.
Smith AH, Lingas EO, Rahman M. Contamination of drinking water by arsenic in
Bangladesh: a public health emergency. Bull World Health Org 2000;78:1093103.
Stollenwerk KG, Breit GN, Welch AH, Yount JC, Whitney JW, Forster AL, et al. Arsenic
attenuation by oxidized sediments in Bangladesh. Sci Total Environ 2007;379:
13350.
Steben D, Berner Z, Chandrasekharam D, Karmakar J. Arsenic enrichment in ground-
water of West Bengal, India: geochemical evidence for mobilization of As under re-
ducing conditions. Appl Geochem 2003;18:141734.
Stumm W, Morgan JJ. Aquatic chemistry. 3rd ed. NewYork: John Wiley and Sons; 1981.
Swartz CH, Blute NK, Badruzzaman B, Ali A, Brabander D, Jay J, et al. Mobility of arsenic
in a Bangladesh aquifer: inferences from geochemical proles, leaching data, and
mineralogical characterization. Geochim Cosmochim Acta 2004;68:453957.
Tardy Y. Characterization of the principal weathering types by the geochemistry of wa-
ters from some European and African crystalline massifs. Chem Geol 1971;7:
25371.
Umitsu M. Late Quaternary sedimentary environments and landforms in the Ganges
Delta. Sediment Geol 1993;83:17786.
van Geen A, Ahasan H, Horneman AH, Dhar RK, Zheng Y, Hussain I, et al. Promotion of
well switching to mitigate the current arsenic crisis in Bangladesh. Bull World
Health Organ 2002;80(9):7327.
van Geen A, Zheng Y, Versteeg R, Stute M, Horneman A, Dhar RK, et al. Spatial variabil-
ity of arsenic in 6000 tubewells in a 25 km
2
area of Bangladesh. Water Resour Res
2003;39:1140.
von Brmssen M, Md Jakariya, Bhattacharya P, Ahmed KM, Hasan MA, Sracek O, et al.
Targeting low-arsenic aquifers in groundwater of Matlab Upazila, Southeastern
Bangladesh. Sci Total Environ 2007;379:12132.
von Brmssen M, Larsson SH, Bhattacharya P, Hasan MA, Ahmed KM, Jakariya M, et al.
Geochemical characterisation of shallow aquifer sediments of Matlab Upazila,
Southeastern Bangladeshimplications for targeting low-As aquifers. J Contam
Hydrol 2008;99(14):13749.
Wasserman GA, Liu XH, Parvez F, Ahsan H, Levy D, Factor-Litvak P, et al. Water manga-
nese exposure and children's intellectual function in Araihazar, Bangladesh. Envi-
ron Health Perspect 2006;114:1249.
Wersin P, Charlet L, Karthein R, Stumm W. From adsorption to precipitation: sorption
of Mn
2+
on FeCO
3
(s). Geochim Cosmochim Acta 1989;53:278796.
WHO. Guideline for drinking water quality. 4th ed. Geneva: World Health Organiza-
tion: Singapore; 2011.
Zheng Y, Stute M, van Geen A, Gavrieli I, Dhar RK, Simpson HJ, et al. Redox control of
arsenic mobilization in Bangladesh groundwater. Appl Geochem 2004;19:20114.
412 A. Biswas et al. / Science of the Total Environment 431 (2012) 402412