Chemosphere 224 (2019) 140e150

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Chemosphere
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Multilayer arsenic mobilization and multimetal co-enrichment in the

alluvium (Brahmaputra) plains of India: A tale of redox domination
along the depth
Arbind Kumar Patel a, Nilotpal Das b, Manish Kumar c, *
a
Department of Environmental Science, Tezpur University, Assam, 784-021, India
b
Department of Civil Engineering, Indian Institute of Technology Guwahati, Assam, 781-039, India
c
Discipline of Earth Science, Indian Institute of Technology Gandhinagar, Gujarat, 382-355, India

h i g h l i g h t s g r a p h i c a l a b s t r a c t

Multilevel groundwater monitoring

in the Indian alluvium plain for
arsenic mobilization.

ORP emerged as the single most
important governing feature of
arsenic release with depth.

Secondary anthropogenic forcing
supplements reductive hydrolysis of
Fe/Mn(hydr)oxides.

Supersaturated states of hydrozincite
attributed to the elevated levels of Zn
at all depths.

Co-occurrence of Zn, Pb, Mn and As
aggravate the health and environ-
mental implication.

a r t i c l e i n f o a b s t r a c t

Article history: The study attempts to understand arsenic (As) mobilization in a shallow aquifer with depth variation
Received 26 July 2018 while focusing on the potential co-occurrence of As with priority metals (zinc and lead), using a pilot
Received in revised form scale multilevel groundwater monitoring system (MGWS). Groundwater samples (n ¼ 72) were collected
12 February 2019
bi-weekly (every 15 days) from the multilevel sampler (4.6, 9.2 and 13.8 m depths), installed at Tezpur,
Accepted 15 February 2019
Available online 18 February 2019
Sonitpur district of Brahmaputra floodplain (BFP), Assam, India, for a period of 1 year (August 2013eJuly
2014). Both geogenic and anthropogenic influences were found to affect the studied unconfined aquifer.
Handling Editor: X. Cao At 4.6 m, weathering dominated due to interaction with CO2 and infiltrating water. Prevalent high pH (7.9
e8.6) at all three depths in association with strong oxidizing condition (at 4.6 m) during the drier months
Keywords: seem to play a crucial role in desorption based As release. Multivariate analyses revealed that redox
Arsenic potential (ORP) remains the primary controller of As release at all three depths. With depth, stronger
Zinc anoxic conditions resulted in the dominance of reductive hydrolysis leading to a co-occurrence scenario
Lead of As (max 4.6 mgL1) with Zn (max 2514 mgL1) and Pb (max 740 mL1) with influences of anthropogenic
Brahmaputra flood plain
modes of activities like agriculture and dry deposition from a brick kiln. Multi-element enrichment is an
Co-occurrence
emerging concern but the bigger picture would be to understand the peculiarities of individual aquifers,
Multilayer
as a generalization can lead to missing a ton of information. In this regard, long-term multilevel

* Corresponding author. Discipline of Earth Science, Indian Institute of Technol-

ogy Gandhinagar, Gujarat, 382-355, India.
E-mail addresses: manish.kumar@iitgn.ac.in, manish.env@gmail.com
(M. Kumar).

https://doi.org/10.1016/j.chemosphere.2019.02.097
0045-6535/© 2019 Elsevier Ltd. All rights reserved.
 A.K. Patel et al. / Chemosphere 224 (2019) 140e150
monitoring can help in the predictive understanding of the vertical stratification and co-occurrences of
multi-metals that can subsequently be applied for water production at the safer depths.
1. Introduction
Arsenic (As) release is governed by a number of different factors
like redox conditions, pH, presence of organic matter, the microbe
profile etc. (Acharyya, 2005; Bhattacharya et al., 2009; Kumar et al.,
2010; Nickson et al., 2000; Smedley and Kinniburgh, 2002; Kim
et al., 2012). Most of the initial research on As were case studies
and reports followed by a gradual shift of focus on understanding
the release mechanism, interactive behavior with other contami-
nants and health risks (Alam et al., 2002; Das et al., 1996, 2018;
Neumann et al., 2010; Radloff et al., 2011; Borah et al., 2018; Kim
et al., 2012; Kumar et al., 2017). Several studies have shown that
aquifer depth can clearly impact availability of As free water
(Warren et al., 2005; Berg et al., 2008; Becker et al., 2010; Burgess
et al., 2010; Radloff et al., 2011), as in many parts of the world, As
levels are higher in shallow unconfined aquifers, owing to favorable
conditions like recent sedimentation, higher organic matter and
interference of anthropogenic activities (Smedley and Kinniburgh,
2002). Previous studies like Smedley and Kinniburgh (2002) and
Kim et al. (2012) have proposed that with depth reducing condi-
tions become more extreme resulting into re-precipitation of As
sulphides. However, As has also been detected in some deeper
aquifers (Erban et al., 2013; Mukherjee et al., 2011; Rina et al., 2012;
Winkel et al., 2011). Overall, the literature on vertical profiling of As
concentration is much more inconspicuous than that on spatial
variation and thus need to be further explored.
It is evident that understanding the depth dependency of As
release in an aquifer and ultimately across a larger region like a
floodplain is imperative for safe drinking water production per-
spectives. However, it calls for a methodology that can enable the
access to the different aquifer strata, with a provision for simulta-
neous sampling. The multilevel groundwater monitoring system
(MGWS) can be a great tool in regards to studying the in-situ depth
variation of individual aquifers. MGWS has been used by Kim et al.
(2009) to explain for As hydrogeochemistry, but in general, such
studies are too limited, especially the one carried out in India. A
number of disadvantages associated with sampling from boreholes
and tube wells like: fixed sampling region and depth due to fixed
length of the screen as well as mixed nature of samples due to
multiple screens placed at different depths of the same tube well,
can be negated using MGWS (Guha et al., 2005). A combination
with other currently available technologies like isotope tracing
could be used to trace the pathways of vertical mobilization along
the depth, while a network of such systems in a region can generate
a flow path, recharge, discharge, and probable location of sources
and sinks in the floodplain. Other crucial factors like the involve-
ment of anthropogenic activities and environmental deposition can
also be deciphered using an integrated approach of MGWS and
isotopic studies. Applying a similar strategy to sediment samples
can even reveal microbial diversity in the different strata, and
felicitate the identification of those species which are involved in
the As release mechanism (Fan et al., 2008; Holden and Fierer,
2005; Xiong et al., 2012).
Presence of As in the BFP, India is a known fact, and previous
studies in the region have revealed the presence of a predominantly
reducing condition and the involvement of reductive hydrolysis of
Fe (hydr)oxides (Das et al., 2018, 2017; 2016; Kumar et al., 2016).
141
© 2019 Elsevier Ltd. All rights reserved.
Co-occurrences of As and fluoride (F) (Das et al., 2018, 2017, 2016;
Kumar et al., 2016a, b) as well as reports of metal pollution of
anthropogenic origin (Buragohain et al., 2010; Haloi et al., 2010;
Chakrabarty and Sarma, 2011; Haloi and Sarma, 2012) in the
groundwater of the BFP, has already been discussed in a number of
recent studies. However, both As hydrogeochemistry and co-
occurrences perspectives along with their seasonal changes need
to be discussed from the vertical variation point of view using
MGWS.
Under the light of above discussion, a pilot scale MGWS study
was conducted in an unconfined shallow aquifer of the BFP to gain a
greater understanding of the mechanism/governing factors of As
mobilization and its co-occurrences at different aquifer strata. A
brief stepwise breakdown of the methodology for realizing this
objective is as follows: I) Observation of biweekly seasonal varia-
tion in As and other dissolved ions in the groundwater at different
depth of the MGWS well; II) identification of the governing
hydrogeochemical processes that control the process of As release
at three different depths of shallow aquifer; III) Generation of a
vertical profile for As and co-occurring metals in the MGWS with
possible future scenario simulation using saturation state calcula-
tions and IV) Discussion on the environmental implications of the
MGWS studies for safe drinking water perspectives.
2. Materials and methods
2.1. Study area
The study area is a shallow unconfined aquifer located (26 410
25.9100 N 92 500 26.2700 E) about 7.5 km north of the river Brah-
maputra and 1.5 km west of river Jiya Bharali in Napaam village,
Sonitpur district, Assam, India (Fig. 1a and b). The confluence of the
Jiya Bharali River and the Brahmaputra River is quite close to the
site (Fig. 1a), and form a part of the greater BFP. The Bharali River
has significantly changed its course over time leading to a number
of dead channels formation close to our study area (Fig. 1a and b).
The aquifer under study is formed of new Alluvial sediments and
shallow in nature (30e50 mbgl) (CGWB, 2008; MWR, 2009).
Agricultural activities, mainly rice cultivation is dominant and the
aquifer itself lies in close proximity to the rice fields (Fig. 1b). A
major anthropogenic disturbance could be the location of a fully
operational brick kiln close to the study site (Fig. 1b). The climate of
the greater Sonitpur district being subtropical and humid is char-
acterized by a strong monsoon with high rainfall rates (CGWB,
2008; MWR, 2009). The average annual rainfall recorded in the
district is about 2173 mm, while the relative humidity is around 65
to 85 percent. The temperature is also quite variable, with a sum-
mer maximum of around 38 C and a winter minimum of around
7.6 C (CGWB, 2008; MWR, 2009).
2.2. Setup of multilevel groundwater sampler
MGWS was installed at the site, using polyvinyl chloride (PVC)
pipes of two different diameters. A larger pipe acting as a casing
with an internal diameter of 4 inches was used for housing three
PVC pipes each of 1 inch in diameter to sample groundwater from
three different depths (4.6, 9.2 and 13.8 m) (Fig. 1c). The depth of
142 A.K. Patel et al. / Chemosphere 224 (2019) 140e150
Fig. 1. Map of the study area a) Location in India and distance from rivers and b) presence of river meandering and brick kiln at the monitoring site, c) schematic diagram of the
multilayer sampling unit and d) lithology of the sampling area.
the well was selected on the basis of the local water table and the
thickness of the aquifer at the installation site. Side by side pre-
sentation of the lithology (Fig. 1d) reveals that the top 0.5 m con-
sists of clay followed by fine sand till 6.62 m and finally coarse and
boulders till 15.12 m. Each of the sampling pipes had a nylon mesh
fabric to prevent the mixing of the groundwater during sampling.
The slugging method consisting of raising and lowering an open
pipe in a water-filled hole was employed for digging the well. The
three pipes of different depths were attached by individual ports to
the motor for abstraction of groundwater.
2.3. Sampling and analyses
Seventy-two groundwater samples (n ¼ 72) were collected bi-
weekly on every 15th and 30th days of the month from the multi-
level sampler for a period of one year (August 2013eJuly 2014). The
groundwater samples were collected after purging for at least
5 min with an electric pump. Samples were collected from all three
depths in duplicates, one set stored in 125 ml polyethylene bottles
was filtered (0.45 mm Millipore) and acidified to pH  2 using 16 N
HNO3 for cation and trace element analyses including As. The other
set was bottled in 500 ml polyethylene bottles without filtering for
anion analyses. Headspace was avoided while sample storage to
avoid interference from air. The samples were stored at 4 C until
analyses to prevent degradation and all analyses were completed
within three months of sampling in batches.
A multi-parameter probe, HANNA HI9828 was used for onsite
measurement of pH, electrical conductivity (EC), dissolved oxygen
(DO), oxidation-reduction potential (ORP) and total dissolved solids
(TDS). Sodium (Na), potassium (K) and calcium (Ca) were analyzed
by flame photometry (Systronics Flame photometer 128, Ahme-
dabad, India). An inductively coupled plasma optical emission
spectrometer (ICP-OES, Perkin Elmer Optima DV2100, Waltham,
MA, USA) was utilized for analysis of magnesium (Mg) and the trace
elements iron (Fe), manganese (Mn), lead (Pb) and zinc (Zn).
Arsenic was analyzed using atomic absorption spectrometry (AAS,
Thermo Fisher Scientific ICE 3000, Waltham, MA, USA), the method
detection limit (MDL) for which was 0.05 mgL1. Ultra-violet
spectrophotometry (Shimadzu, UV-1700, Kyoto, Japan) was uti-
lized for analyzing sulphate (SO2 3
4 ), phosphate (PO4 ), nitrate

(NO3 ) based on the methods prescribed by the American Public
Health Association (APHA) guidelines (APHA, 2005). Chloride (Cl)
 A.K. Patel et al. / Chemosphere 224 (2019) 140e150
and bicarbonate (HCO 3 ) were analyzed by argentometric titration
and potentiometrically (APHA, 2005).
In order to ensure precise and reliable results several QA/QC
protocol has been implemented viz. use of National Institute of
Standards and Technology (NIST) certified standard reference ma-
terials (SRM 1640) for metals in natural water [recovery ranges
between ±9% to ±15% of the certified values of Cu, Pb and Zn],
quantification of instrumental detection limit (DLs) in solution
matrix [0.02, 0.05 and 0.01 mgL1 for Cu, Pb and Zn respectively],
reagent blank run with each sample batch, use of internal standards
[Y, In and Bi], triplicate analyses and use of at least seven standard
solutions for generating calibration curve for each chemical analyte.
Furthermore, HCO 3 was analyzed in-situ and in lab with both
filtered and unfiltered samples.
Statistical analyses were done using the software package SPSS
21 (IBM Corporation, New York, USA). Bivariate relationship be-
tween the parameters was observed using Pearson's correlation
coefficient. Among multivariate analyses, principal components
analysis (PCA) and hierarchical cluster analysis (HCA) were con-
ducted to observe effective hydrogeochemical processes operating
at different depths. Varimax rotation with Kaiser normalization was
used for the PCA (Tabachnick and Fidell, 2007).
2.4. Speciation calculation of aquatic phases
The saturation indices (SI) of the selected aquatic phases in the
groundwater were calculated to deduce the relative availability of
these different fractions using MINTEQA2 version 3.1. Using inbuilt
THERMO.DBS, TYPE6.DBS, REDOX.DBS, and GASES.DBS databases,
SI were calculated after grouping the whole year of data into three
groups i.e. averages of four months for each parameter at all three
depths. The scheme of the three sections were: 1) Period P1:
August-September-October-November, 2) Period P2: December-
January-February-March and 3) Period P3: April-May-June-July.
This division of the yearly period was done based on the hydro-
graph of the area as well as variations observed in data set in order
to avoid similarity in SI.
3. Results and discussions
3.1. Seasonal dynamics of vertical water quality profiling
Fig. 2 depicts a monthly variation of a) As, b) pH c) HCO
3 , d) ORP,
e) NO 2 
3 , f) SO4 , g) Fe, and h) Cl over the wet (June to September)
and dry period (October to May). At all three depths, As concen-
tration showed a marked fluctuation with two different peaks in
September and December (Fig. 2). The first peak occurs towards the
end of the wet season, coinciding with a relative rise in ORP
(220 mV) (Fig. 2a, & d). It implies the presence of a desorptive
release of As from Fe (hydr)oxides especially towards the surface
layer as the point of zero charge (PZC) which is between 8 and 8.5
for Fe (hydr)oxides is reached. The hypothesis is substantiated by a
peak in Fe concentration (17 mgL-1) in follow up months of October
and November (Fig. 2g). Desorption again appears to be the reason
behind the second peak of As and ORP in Winter (December).
During the winter months, when groundwater abstraction is
comparatively lesser, a dip in ORP and As is observed, since aquifer
remains saturated. Owing to an increase in the withdrawal from the
month of January onwards and the associated influx of air, the ORP
also increases (Fig. 2d). Due to drop in the ORP to the lowest during
January, another smaller As spike is observed to coincide with the
greatest elevation in Fe concentrations (Fig. 2a, d and g) implying
the occurrence of reductive hydrolysis of Fe (hydr)oxides. Greater
fluctuations in both As and ORP levels during the drier season
(Fig. 2a and d) is attributed to significant influence of abstraction as
143
drawdown influences the Eh (Klimas and Gregorauskas, 2002; Berg
et al., 2008; Winkel et al., 2011), while drawdown gets stabilized
during the rainy months due to recharge.
pH and HCO 3 of the groundwater remain uniformly high during
both the wet and dry seasons (Fig. 2b and c). Alkaline pH appears to
be attributed to the anthropogenic origin, mostly due to a high
influx of soaps and detergents, as the aquifer under observation is
unconfined and highly disturbed (Goel and Kaur, 2012). Washing
powder which is used exclusively in the study area has a much
higher potential for increasing water pH due to the presence of
excess filling materials (Goel and Kaur, 2012). NO 3 exhibited high
variability and increase in its concentration (Fig. 2e), during the wet
season (Supplementary Table. 1) mainly due to leaching of
anthropogenic sources viz. septic tanks, fertilizers like NH4NO3 and
Zn(NO3)2 especially at 4.6 m. With the dry season, NO 3 values went
down progressively due to a gradual decrease in leaching (Fig. 2e).
A positive correlation was observed between As and NO 3 (Fig. 2a
and e) probably due to enhanced redox potentials during June and
September lead to higher NO 3 levels in the aquifer. Thus, the high
ORP not only maintains elevated NO 3 level but also leads to the
development of a positive correlation with As. In case of SO2 4 a
sudden and very prominent peak was found in November (Fig. 2f)
owing to the assistance from the strongly oxidized condition and
dilution effect and the lowering of the existing ORP due to varia-
tions in the monthly precipitation. A positive correlation was also
observed between As and SO2 4 during the post-monsoon. Owing to
evapotranspiration, there is a gradual increase in Cl levels during
rest of the year. It seems that weathering and evapotranspiration in
the aquifer is completely governed by the seasonal disparity.
Overall, Monthly variation of arsenic seems highly dependent on
ORP change, which in turn is greatly determined by recharge
amount and recharge water quality. Anthropogenic influence and
rainfall leading to runoff affect the levels of NO 2
3 , SO4 and PO4 .
3
3.2. Depth wise variation in groundwater chemistry
Fig. 3 represents the depth-wise variation of cations a) Naþ, b)
Mg2þ, c) Kþ, d) Ca2þ; anions e) NO 2  
3 f) SO4 g) Cl , h) HCO3 and
metals i) Fe, j) Pb, k) Zn and l) As. Except for Ca2þ (Fig. 3d), the other
alkali and alkaline earth metals do not show a significant trend with
depth. Higher average values of Ca2þ at the upper most layer is
indicative of carbonate weathering and ion-exchange (Fig. 3d).
With depth, a gradual decrease in the anthropogenic influence
results in diminished levels of NO 3 and Cl

(Fig. 3e and g).

Reduction in the NO3 levels also appears to be influenced by the
increasing intensity of the reducing condition with depth. This
phenomenon is also the most probable reason behind the
increasing levels of Fe with depth, likely due to the involvement of
reductive hydrolysis of Fe (hydro)xides (Fig. 3i). Pb also displays a
similar trend like Fe (Fig. 3j), therefore it is likely that reductive
hydrolysis could be responsible for the partial release of Pb, which
increase with depth. On the other hand, reductive hydrolysis also
seemed to released Zn as there was a drastic rise in the zinc level at
9.2 m (Fig. 3k). The primary contributors for Pb and Zn are however
thought to be anthropogenic sources like dry Pb deposition from
the nearby brick kiln and Zn release from the agrochemical Zn
(NO3)2. Box plot could not display any specific trend in As with
depth.
The first insights to the interactive behavior of groundwater
with the surrounding aquifer material can be observed from the
Piper trilinear plot (Supplementary Fig. 1), (Piper, 1944).
Ca2þeHCO-3 type at 4.6 m was found to be gradually changed to
mixed type at 9.2 m and then ultimately progressing towards
NaþeHCO-3 at 13.8 m HCO 3 remains dominant implying the recent
fresh infiltrated water dominance which was further confirmed by
144 A.K. Patel et al. / Chemosphere 224 (2019) 140e150
Fig. 2. Graph depicting the monthly variation of a) As, b) pH c) HCO
the Gibbs plots (Gibbs, 1970) (Supplementary Fig. 2). Gibbs plot
indicates a gradual increase in ion exchange with depth and
dominant rock-water interaction. Effect and role of weathering on
the overall hydrogeochemistry are further investigated through
saturation state calculations for all the important minerals (Fig. 4)
and scatter plot discussed in next section.
3.3. Speciation modeling
Fig. 4 depicts saturation status of different mineral phases pre-
sent in the groundwater at 4.6 m, 9.2 m and 13.8 m in different
periods (P1, P2 and P3 representing data of August to November,
December to March and April to July respectively). Throughout the
year, at all the three depth, low levels of As is reflected through
highly unsaturated state (SI) of As bearing mineral phases like
arsenolite (As4O6). Interestingly, samples were found supersatu-
rated with Zn containing mineral hydrozincite [Zn5(CO3)2(OH)6]
throughout the year and the level of saturation was observed to be
decreasing from period P1 to P3. Hydrozincite is a common mineral
found along with carbonate minerals like calcite in the aquifer
which under alkaline conditions, prevalent in the studied aquifer,
 2 
3 , d) ORP, e) NO3 , f) SO4 , g) Fe, and h) Cl .
precipitates (Paulson et al., 1989). Fluctuation in SI of hydrozincite
from P1 to P3 is primarily a function of the seasonal variability
where during wet season (P1) leaching and concentration of
anthropogenic Zn occurs. During the dry season (P2), there is a
drastic reduction in Zn influx to the aquifer which continues till the
latter half of the P3, after which the wet season starts again. A
similar change is also observed in the SIs of calcite and dolomite
(Fig. 4) which can again be explained by the dependence of car-
bonate weathering on precipitation level.
Like hydrozincite, hydroxyapatite [Ca10(PO4)6(OH)2] also re-
mains highly saturated at all depths accounting for the common
source of Ca2þ and PO3 4 . SI indicates that precipitation of hy-
droxyapatite is higher at 9.2 m depth in the drier season (Fig. 4).
Non-conservative behavior of Fe was also observed as siderite
(FeCO3) was found to be saturated at 4.6 m during P1 but remains
slightly undersaturated state at all other depths. Infiltration
appeared to play an important role in the saturation of Fe(OH)2,
which followed a pattern similar to siderite at all depths
throughout the year (Fig. 4). This could happen due to the gener-
ation of Fe(OH)2 during the precipitation of siderite. Overall, the
aquifer appears to be vulnerable from geogenic As pollution as
 A.K. Patel et al. / Chemosphere 224 (2019) 140e150 145

Fig. 3. Box plots representing the depthwise variation of cations a) Naþ, b) Mg2þ, c) Kþ, d) Ca2þ; anions e) NO 2  
3 f) SO4 g) Cl , h) HCO3 and metals i) Fe, j) Pb, k) Zn and l) As. Star (*)
sign depicts the significant difference among three depths [** 0.01 level and * 0.05 level].

Fig. 4. Saturation status of mineral phases present in the groundwater at 4.6 m, 9.2 m and 13.8 m.

observed from the low SIs of As-bearing phases which imply that
these minerals are liable to get dissolved in future.
3.4. Tracing hydrogeochemical processes and associated arsenic
mobilization
Fig. 5 presents various scattered plots of a) TZþ vs (NaþþKþ), b)
TZþ vs (Ca2þþMg2þ), c) Ca2þ/Mg2þ vs sample number d) HCO
associated samples (Fig. 5c), where for both 9.2 m and 13.8 m,
carbonate weathering takes precedence (Fig. 5c). Ca2þ/Mg2þ  1 in
nearly half of the samples derived from 9.2 m to 13.8 m, exhibit
dolomite dissolution. It further gets substantiated from HCO 3
versus Ca2þ plot (Fig. 5d) as number of samples fall along the 1:1
line indicating calcite weathering, while those to the left of the line
are mostly due to dolomite weathering. Reverse ion exchange was
3 vs
found at 9.2 m and the highest concentrations of Cl, SO2 4 and NO3


Ca2þ, e) As vs pH, f) As vs HCO 

3 , g) As vs ORP, h) As vs Cl , i) As vs Fe,
j) As vs Ca2þ, k) As vs NO 2
3 and l) As vs SO4 at three depths,
depicting governing hydro-geochemical processes operating at the
monitoring site. Ratio between total cations (TZþ) versus (NaþþKþ)
(Fig. 5a) and (Ca2þþMg2þ) (Fig. 5b) reveal the dominance of car-
bonate weathering over silicate as Ca2þ and Mg2þ contributes more
to TZþ. Silicate weathering is mostly confined to the upper layer
(4.6 m) of the aquifer as the values of Ca2þ/Mg2þ > 2 for most of the
was detected at the uppermost layer of the aquifer. As the MGWS
was set up in a rice farmland, the aforementioned chemicals spe-
cies are of agricultural origin. High DO and ORP at the top strata
could also be responsible for conserving oxidized species like SO2 4
and NO 3.
Further, no correlation was found to be existing between As and
pH, yet the highest As levels, at all three depths, coincided with the
higher pH of the particular strata (Fig. 5e). It implies that As the
146 A.K. Patel et al. / Chemosphere 224 (2019) 140e150
Fig. 5. Scattered depiction of governing hydro-geochemical processes operating at the monitoring site; a) Tzþ vs (NaþþKþ), b) Tzþ vs (Ca2þþMg2þ), c) Ca2þ/Mg2þ vs sample number
d) HCO 2þ  
3 vs Ca , e) As vs pH, f) As vs HCO3 , g) As vs ORP, h) As vs Cl , i) As vs Fe, j) As vs Ca , k) As vs NO3 and l) As vs SO4 at three depths.
release is being influenced by the prevalent alkaline pH, especially
since the environment in the aquifer is oxidizing. This alternatively
means that As is probably predominantly occurring in the form of
arsenate at 4.6 m As(V) remain adsorbed on Fe (hydr)oxides at
acidic and neutral pH which gets desorbed as the pH (~8.5) in-
creases due to the low point of zero charge (PZC) for Fe (hydr)oxides
(Bundschuh et al., 2012; Kim et al., 2012). Lack of a distinct corre-
lation between As and HCO 3 (Fig. 5f) implies the absence of
competition between these two oxyanions for sorption sites on Fe/
Mn-(hydr)oxides (Anawar et al., 2003). However, observed high As
with corresponding higher HCO 3 could arise due to precipitation-
induced weathering and dissolution of carbonates, while As at
the same time could be released due to the weathering of As-
containing mica (Dowling et al., 2002). A significant correlation
was found between As and ORP (Fig. 5g) which substantiate the
ORP based explanation of As mobilization. However, evaporation or
salt enrichment due to irrigation return flow seems not to be a
significant process as evident from the lack of any relationship
between As and Cl (Fig. 5h).
The observed negative correlation in a number of samples be-
tween the As and Fe (Fig. 5i) is attributed to the non-conservation of
Fe due to re-precipitation of Fe as siderite (FeCO3) (Kumar et al.,
2010). A weak positive relationship between As and Ca2þ, espe-
cially at 4.6 m, is due to weathering and dissolution (Fig. 5j). A
positive relation between As and NO 3 (Fig. 5k) highlights the
importance of the prevalent oxic environment and dominance of
anthropogenic sources like NH4NO3 and Zn(NO3)2, especially in the
uppermost layer. Oxic condition will also be responsible for arsenic
speciation mainly in the form of As(V), the release of which from Fe
(hydr)oxides will be stimulated by the high alkaline pH of the
aquifer (Kim et al., 2012). Competitive sorption between As
2þ  2
oxyanions and SO2 4 on positively charged surfaces like Fe (hydr)
oxides could result in an inverse relationship between the two in a
few samples collected at 4.6 and 9.2 m (Fig. 5l) which during the
dry season with the development of a stronger oxic condition could
result in a positive correlation. Under a highly oxic condition, SO2 4
reduction will be effectively hampered, while the prevalent high pH
could stimulate its desorption along with As from Fe (hydr)oxides.
Correlation analysis further revealed the importance of ORP as
the primary trigger of As release (Supplementary Table. 2), the
importance of which increases with depth. Weathering is quite
dominant at 4.6 m depth as can be observed from the positive
correlation between EC, Naþ and Mg2þ. EC, TDS and Naþ also show
positive correlation with NO 3 at this depth due to the mobilization
of anthropogenic NO 3 with the influx of water during rainy season.
High cation exchange capacity (CEC) of the top soil layer is reflected
in the positive correlation observed between Zn, TDS, Kþ, Mg2þ and
Mn. The upper layer at 4.6 m is also the most likely to be exposed to
organic matter originating from dumping of domestic waste
(Helling et al., 1964). The involvement of reductive hydrolysis is
observed in the correlation between Fe and Mn.
At medium depth of 9.2 m, a negative correlation between As
and DO becomes stronger with depth. Towards the top of the
aquifer, presence of more air and higher ORP could result in a partly
desorption based As release. With the increase in depth as the
condition becomes progressively anoxic, reductive hydrolysis may
become the dominant form of As release. The influence of weath-
ering also decreases with depth, as we do not observe any corre-
lation between EC, Naþ and HCO 3 at 9.2 m. The high levels of NO3

in the groundwater (Supplementary Table. 1) and its positive cor-
relation with Zn (Supplementary Table. 2) indicates the use of
Zn(NO3)2 as a fertilizer for correcting Zn deficiencies in the soil. Zinc
 A.K. Patel et al. / Chemosphere 224 (2019) 140e150
also exhibits medium correlation with Mn and low correlation with
Fe indicating the release during the process of reductive hydrolysis
of Mn and Fe (hydr)oxides. Therefore, the number of pathways for
Zn contamination in the groundwater could be more than one. This
also brings out the potential co-existence of Zn with As in the
studied aquifer, even though the latter has much lower concen-
trations comparatively. At 13.8 m, the trends are similar to 9.2 m
with a few differences. The negative correlation between DO and As
is strongest at this depth, correlation of As with ORP, and Fe with
Mn remains high. It is however unknown till what depth the
strength of reductive hydrolysis will continue to increase and
mobilize arsenic; as previous studies have stated that continued
decrease of ORP with depth ultimately leads to SO2 4 reduction and
re-precipitation of soluble As (Kim et al., 2012; Smedley and
Kinniburgh, 2002). Positive correlation of Zn with Mn and to a
lower extent with Fe, still showed that reductive hydrolysis played
a role in the release of Zn. The fact that reducing condition becomes
more prominent with depth is also visible from the reduction in the
correlation between Zn and NO 3 , as the latter is favored under an
oxidized condition.
Overall, the key trigger of groundwater chemistry seems to be
the diffusion of lesser oxygen at greater depths, resulting progres-
sive development of reducing condition with depth, leading to
increased intensity of reductive hydrolysis of (hydr)oxides of Fe and
Mn with depths, which ultimately increases Fe and Mn and trace
elements concentrations like Pb and Zn (that remain adsorbed to
such complexes). pH of the groundwater remains uniformly high at
all the depths which along with the low ORP impart As release
mechanism of the aquifer (Kim et al., 2012; Smedley and
Kinniburgh, 2002). Finally, As release seems highly ORP regu-
lated, while the absence of any relationship with Fe indicates its
non-conservation. The oxic environment results in weak positive
relationship between As and NO 3 . The negative correlation be-
tween As and SO2 4 arising due to competitive sorption is reversed
due to the development of a strong oxic condition in the dry season.
3.5. Multimetal co-enrichement
It is a matter of fact that reductive hydrolysis alone is not likely
to result into higher than their permissible limits of Pb and Zn
(10 mgL1 and 5000 mgL1 respectively (WHO, 2017) as observed in
this study (Supplementary Table. 1). A brick kiln in the vicinity of
the study area (Fig. 1b), the use of substandard coal and other
combustibles like used tires, maybe the probable sources of trace
elements found in the monitored aquifer (Ishaq et al., 2010;
Kaushik et al., 2012; Sikder. et al., 2016; Zhou et al., 2015). Co-
occurrences of As, a major geogenic pollutant, with anthropo-
genic trace elements like Pb and Zn found over the permissible
limit in this study is alarming. Previously co-occurrences of As with
several other geogenic contaminates like F, U and NO 3 , as well as Fe,
Mn and Al, have been reported (Kumar et al., 2016; Das et al., 2018
Smedley and Kinniburgh, 2002), however, our study probably for
the first time exhibits high Pb and Zn with As in a rural settings. The
primary source of Pb seem to be a brick kiln in the vicinity though
owing to Pb content of coal used in the brick kiln (Oboirien et al.,
2014; Raask, 1985). Apart from the brick kiln, used tires contain-
ing Pb (San Miguel et al., 2002) is also believed to be contributed to
it. Both of these sources are also known to have Zn apart from Zn
containing agrochemicals like Zn(NO3)2. With depth, the concen-
trations of both Pb and Zn was found to increase which coincides
with the decrease in ORP of the aquifer. This implies that Fe and Mn
(hydr)oxides are likely to be involved as secondary sources of these
two elements through reductive hydrolysis. Thus the gradual
development of a reducing condition with depth results in a co-
release of Pb, Zn and As. Despite the observed co-occurrence, the
147
As levels are quite low and, higher Pb and Zn levels were observed
only in some of the samples, especially at depth of 13.8 m.
3.6. Multivariate statistical analyses
3.6.1. Principle component analyses
Principal components analysis, when performed on the data
from the three different depths, yielded four principal components
for each of them with 64.73% of total variance (Fig. 6A1). The var-
iances in some of the PCs are explained by more than a single
hydrogeochemical process viz. PC1 with high loadings from EC, TDS
and Naþ and, medium loading due to Mg2þ represents weathering.
However, NO 3 and Zn are also represented in PC1, along with
medium negative loading from PO3 4 , this is a representation of an
anthropogenic factor. After PCA the relationship between Zn and
NO 3 becomes clearer, as correlation did not reveal a close rela-
tionship between the two at 4.6 m. The second PC with positive
loadings due to As and ORP emphasizes the importance of the
redox condition on As release. Arsenic release mechanism in the
aquifer could be a mixture of desorption from Fe (hydr)oxides and
reductive hydrolysis of Fe and Mn (hydr)oxides. The fact that Zn
may be released secondarily during the reductive hydrolysis of Fe
and Mn (hydr)oxides becomes clearer from the positive loadings of
Fe, Mn and Zn in PC3. pH, Kþ and SO2 4 alone project their loadings
in PC4. The use of fertilizer potassium sulfate (K2SO4) is the most
likely cause of this observation. However, what is not clear is the
involvement of K2SO4 in influencing the pH, as it is a neutral salt
formed from a strong acid (H2SO4) and a strong base (KOH).
PCA of the variables at 9.2 m, yielded a total variance of 60.27%
(Fig. 6A2). With an increase of just 5.6 m in depth we could observe
a notable difference. First of all, the presence of weathering be-
comes relatively weaker as its representation is relegated to PC3
from a previously higher position at PC1 at 4.6 m. This happens as
with depth, the influence of diffusing CO2 and infiltrating water
becomes lower. Here PC1 has positive loadings from ORP, PO3 4 and
Ca2þ, and negative loading from Pb, signifying the gradual domi-
nance of ORP with depth. Also, the use of monocalcium phosphate
(Ca(H2PO4)2) as a phosphate fertilizer which can be masked due to
the dominance of weathering in the upper layer seems to be
another process represented in PC1. Nitrate, Fe, Mn, and Zn are the
species imparting significant positive loadings on PC2. This PC ap-
pears to be quite interesting in the fact that it could represent the
dual origin of Zn due to the application of Zn(NO3)2 as a fertilizer,
and partly from Fe and Mn (hydr)oxides. As already explained,
silicate weathering is weaker at this depth as shown by the loadings
of EC, TDS, and Naþ in PC3. The last component PC4 has maximum
variance due to DO, ORP, SO2 4 and As, and thus represent the
process of As release. Negative loading of DO along with positive
loadings of As and ORP clearly indicates the dominance of reductive
hydrolysis with depth. The decrease in ORP with depth lead to the
reduction of SO2 4 to sulfides resulting in gradually diminishing
concentrations of SO24 (Kim et al., 2012).
Reductive hydrolysis is strongly represented at 13.8 m as seen
from the positive loadings of As and ORP, and negative loading of
DO in PC1 (Fig. 6A3). Dissolution of minerals still remain important
as signified by the positive loadings of Ca2þ, Mg2þ and Cl in PC2.
Dolomite CaMg(CO3)2 dissolution could be a probable cause of Ca2þ
and Mg2þ loading. Anthropogenic influence due to the use of
Zn(NO3)2 and K2SO4 can be observed in PC3. Reductive hydrolysis of
Fe and Mn (hydr)oxides could also be responsible for the release of
adsorbed Pb to some extent as observed from the positive loadings
of Pb, Mn and As.
The overall gist of the hydrogeochemistry, irrespective of the
loading strengths of the different variables has been presented
separately in Supplementary Table. 3. We classify the combinations
148 A.K. Patel et al. / Chemosphere 224 (2019) 140e150
Fig. 6. Results of multivariate analyses at different depths i.e. A) 3-Dimensional representation of the principal components at A1) 4.6 m, A2) 9.2 m and A3) 13.8 m and B)
Dendrogram obtained from hierarchical clustering at different depths.
of these variables representing regulatory hydrogeochemical pro-
cesses into three classes, viz., most prominent, second regulatory
process and third regulatory process. At 4.6 m, ORP-AseSO4 have
been grouped together (Supplementary Table. 3) as the most
prominent regulatory set. This group represents the involvement of
ORP based mobilization of arsenic by the microbes. The second
regulatory set at 4.6 m is represented by the group CaeHCO3eP-
beNO3-TDS, which is clearly influenced by anthropogenic activities
and the seasonal rainfall recharge. Carbonate weathering is well
represented in this group, while the sources of Pb and NO 3 have
already been discussed previously. Lastly, pH-FeeMnePO4 repre-
sent the desorption of As and PO4 from Fe and Mn (hydr)oxides
under high pH.
At 9.2 m, agricultural inputs affect the grouping of FeeZneNO3
as the most prominent regulatory set (Fig. 7a, Supplementary Table.
3). Microbe-induced oxidative arsenic mobilization acts as the next
important regulatory set which is represented by Ase-
SO4eHCO3eK. The last regulatory mechanism is driven by the ORP
fluctuation of the aquifer by the chemical species of agricultural
origin like phosphates, as can be seen from the grouping of Ca-PO4-
ORP. At 13.8 m (Fig. 7a, Supplementary Table. 3), carbonate
weathering and dissolution of Fe and Mn (hydr)oxides are repre-
sented together in the most prominent set by the grouping of
CaeMg-ECeHCO3eFeeMn. Again the release of arsenic due to
desorption from Fe (hydr)oxides under the influence of high pH is
clearly seen in the grouping of pH-As-ORP. The last group consisting
of ZneNO3-DO represents another instance of anthropogenic in-
fluence in the form of agrochemical based Zn and NO3 leaching
along with the regulation of the DO by NO3.
3.6.2. Hierarchical cluster analyses
Hierarchical clustering of the data at all three depths corrobo-
rated the findings of the PCA along with some new observations. At
4.6 m (Fig. 7b), weathering and dissolution are represented by the
clustering of EC, TDS and Na, however, this cluster also contains
NO 3 . This observation which was not represented in the PCA, could
arise due to mobilization of sewage at the top layer. At the top layer
þ
clustering of SO24 , pH, DO and K represents the conservation of
SO2
4 released from anthropogenic sources like K2SO4 due to the
prevalent high oxidizing conditions. The exact nature of the rela-
tionship between Pb and Cl is not clear even though they are
clustered together. High levels of Pb in the groundwater can only
 A.K. Patel et al. / Chemosphere 224 (2019) 140e150
originate from some anthropogenic source and the most probable
mode of origin appears to be dry deposition from the nearby brick
kiln using coal high in Pb content and other combustibles like tyres.
Pairing of Fe and Mn together close to another cluster with Zn and
Mg lays the importance of Fe and Mn (hydr)oxides as the probable
sources of adsorbed species like Zn and Mg. The use of phosphate
fertilizer can be observed from the clustering of Ca2þ, HCO 3 and
PO3
4 . The grouping of Ca
2þ
and HCO 3 is representative of fresh
water towards the surface.
At 9.2 m depth, ORP still remains the primary control on the
release of As in groundwater as seen from the clustering of As and
ORP again (Fig. 7b). At this depth, Pb is clustered with Fe, Mn and
pH. The most plausible explanation could be the release of Pb due
to reductive hydrolysis of Fe and Mn (hydr)oxides, indicating a dual
release mechanism for Pb. Thus, a key discovery that came to our
attention is the co-occurrence of As with Zn and Pb. The arsenic
levels at this aquifer is low, however, a similar co-occurrence in an
aquifer with high As level could have had very high hazard impli-
cations for the local population. We also observe that Naþ and
HCO 3 and, Mg
2þ
and Cl are clustered close to each other, this
cluster could depict a transitional state depicting the change of
Ca2þeHCO-3 type water to NaþeHCO-3 water due to ion exchange.
Similar to the uppermost strata of the aquifer, EC, TDS, NO 3 and Zn;
þ
Ca and PO3 2
4 and, DO, SO4 and K are clustered together for similar
reasons at 9.2 m depth as well. The dendrogram at 13.8 m repre-
sents clustering similar to those at 9.2 m (Fig. 7b). Arsenic continues
to be influenced by the ORP, at the deepest layer reductive hydro-
lysis should be the strongest in intensity as the ORP reduces further.
One of the only differences is that Mg2þ is clustered with Cl, close
þ 
to Ca2þ and PO3þ 4 ; much further from Na and HCO3 . This repre-
sents that at greater depths, the groundwater type has a dominant
NaþeHCO-3 facie arising due to ion exchange.
Overall, within this shallow depth multivariate statistical ana-
lyses explicitly illustrated the significant difference in governing
hydrogeochemical processes at different depths at a single location
through MGWS study. Such information must be used by envi-
ronmental planners and policymakers for sustainable groundwater
management and safer water production.
4. Conclusion
The pilot scale MGWS in the BFP presented a unique insight into
the hydrogeochemistry of arsenic mobilization and potential multi-
metal co-enrichment as functions of depth in an alluvial setting. To
conclude this study, the key findings can be summarized as follows:

Among the weathering processes that govern the groundwater
chemistry, intensity of silicate weathering was predominant at
4.6 m depth, while carbonate (both calcite and dolomite)
weathering and reverse ion-exchange were more dominant
with increasing depth.

Arsenic release at all the investigated depths was found to be
highly redox dependent. At 4.6 m, the As release mechanism
was mainly desorption based owing to oxidizing nature of this
layer. With depth, a gradual shift towards a reductive hydrolysis
based mobilization was noticed.

Desorption seems to occurs as the point of zero charge (PZC) is
achieved under the alkaline conditions of the aquifer, while
primarily Fe (hydr)oxides are involved in reductive hydrolysis.
Seasonality imparts change in arsenic mobilization, with the
drier months being favorable for desorptive release due to
higher abstraction and lower rainfall resulting in a prominent
vadose zone with oxidized condition.

At all depths, multimetal co-contamination, mainly of Zn and Pb,
was noticed, owing to anthropogenic origins like brick kiln for
149
Pb enrichment and agrochemicals like Zn(NO3)2 for high Zn
levels. Reductive hydrolysis seems to be also responsible for
secondary release of these two metals implying multiple path-
ways of co-contamination.

Last but not the least, MGWS can be very insightful in under-
standing As mobilization in relation to the peculiarities of in-
dividual aquifers at different depths which can be further aided
with analyses of the microbial profile and isotopes.
Acknowledgements
We would like to thank the Department of Science and Tech-
nology (DST)- Science & Engineering Research Board (SERB) (Grant
number SR/FTP/ES-32/2012), awarded to the first author. We also
like to thank Asia Pacific Network (CRRP 2016-06MY-Kumar) for
partially funding the work in the quest of understanding similar
problem in Guwahati.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.chemosphere.2019.02.097.
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