STOTEN-21742; No of Pages 11

Science of the Total Environment xxx (2017) xxx–xxx

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Science of the Total Environment

journal homepage: www.elsevier.com/locate/scitotenv

Arsenic behavior in different biogeochemical zonations approximately

along the groundwater flow path in Datong Basin, northern China
Junwen Zhang a, Teng Ma a,⁎, Liang Feng a, Yani Yan b, Olusegun K. Abass a,c, Zhiqiang Wang a, Huawei Cai a
a
School of Environmental Studies and State Key Laboratory of Biogeology and Environmental Geology, China University of Geosciences, 430071 Wuhan, China
b
College of Environmental Science and Engineering, Guilin University of Technology, Guilin 541004, China
c
University of Chinese Academy of Sciences, Beijing 100049, China

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

• Bacterial community structures are dis-

tinctly different along groundwater
flow path.
• Bacterial activities play key roles in
groundwater redox transformation.
• NO−3 reduction process inhibits arsenic
release, while SO24 − process doesn't.
• Reductive desorption of As(V) is an im-
portant process in weakly alkaline
groundwater.

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

Article history: Studies have shown that arsenic is desorbed/released into groundwater as a result of bacterial reduction of As(V)
Received 25 October 2016 and Fe(III). However, bacterial activities like sulfate reduction process can also reduce the content of arsenic in
Received in revised form 30 December 2016 groundwater. In this study, we examined the effects of different biogeochemical processes (e.g. NO− 2−
3 and SO4
Accepted 5 January 2017
reduction) on arsenic, by investigating the chemical characteristics and bacterial community structure of ground-
Available online xxxx
water in the Datong Basin, northern China. Along the groundwater flow path, arsenic concentration increased
Editor: D. Barcelo from b1 to 947.6 μg/L with dominant bacteria change from aerobic (Fluviicola, Rhodococcus) to denitrifying bac-
teria (Thauera, Gallionella), and then to sulfate reducing bacteria (Desulfosporosinus). According to the groundwa-
Keywords: ter redox sensitive indicators (Eh, NO− 2− −
3 , SO4 /Cl and Fe
2+
) concentrations (or ratios), the sampling points were
Arsenic approximately divided into three zones (I, I′’ and II). Variation in features of these indicators suggested that the
Biogeochemistry groundwater evolved from a weakly oxidizing environment (Zone I, Eh average 93.3 mV, respectively) to strong
Hydrogeochemistry reducing environment (Zone II, Eh average −101.8 mV). In Zone I, bacteria mainly consuming O2 or NO− 3 were
Redox environment found which inhibits Fe(III) and As(V) reduction reaction, resulting in a low As zone (b 1 to 3.3 μg/L). However, in
Zone II, where O2 and NO− 3 have been depleted, SO4
2−
reduction appears to be the dominant process, and the
Fe(III) and As(V) reduction processes are also occurring and hence, enrichment of As in the groundwater (2.8
to 947.6 μg/L, average 285.6 μg/L). Besides, bacterial Fe(III) reduction process was retarded due to the weakly al-
kaline conditions (pH 7.60–8.11, average 7.83), but abiotic Fe(III) reduction by HS− may be continued. Therefore,
we conclude that the Fe(III) and As(V) reduction processes contributed to arsenic enrichment in the groundwa-
ter, and the reductive desorption of arsenate is the main occurring process especially in the weakly alkaline

⁎ Corresponding author.
E-mail address: mateng@cug.edu.cn (T. Ma).

http://dx.doi.org/10.1016/j.scitotenv.2017.01.029
0048-9697/© 2017 Published by Elsevier B.V.

Please cite this article as: Zhang, J., et al., Arsenic behavior in different biogeochemical zonations approximately along the groundwater flow path
in Datong Basin, northern Chi..., Sci Total Environ (2017), http://dx.doi.org/10.1016/j.scitotenv.2017.01.029
2 J. Zhang et al. / Science of the Total Environment xxx (2017) xxx–xxx
environment. Moreover, NO− 3 reduction process can significantly restrain the release of arsenic, but the process of
SO2−
4 reduction is insignificant for arsenic concentration decline in natural groundwater.
1. Introduction
Natural occurrence of arsenic enrichment in groundwater has been
documented worldwide, including Bangladesh, India, America, Hunga-
ry, Romania and China (Nickson et al., 2000; Nordstrom, 2002;
Smedley and Kinniburgh, 2002; Berg et al., 2007). This geogenic release
of arsenic into groundwater has resulted in sustained health related is-
sues (including skin and lung cancer), and presently poses a threat to
the livelihood of tens of millions across the globe (Chakraborti et al.,
2016). Therefore, in the past 20 years, numerous studies have been ded-
icated to probing the cause of arsenic release into groundwater and out-
comes of these studies furnish three main mechanisms which are
believed to be the culprit of this problem: First, the oxidation of arse-
nic-bearing pyrite (Chowdhury et al., 1999); second, desorption by
competitive anions (such as PO34 −, HCO− −
3 , OH ) (Acharyya et al.,
1999; Appelo et al., 2002; Jain et al., 1999); and third, is bacteria activity
(Nickson et al., 2000; Zobrist et al., 2000; Langner and Inskeep, 2000).
However, increasing research in this field have ushered in a new under-
standing that bacterially mediated dissimilatory reduction of arsenic-
bearing Fe (hydrogen) oxides minerals and reductive desorption of ar-
senate (energy-conserving respiratory) is the major cause of arsenic en-
richment in shallow aquifers (Cummings et al., 1999; Oremland and
Stolz, 2003; Islam et al., 2004; Oremland and Stolz, 2005; Campbell et
al., 2006; Kudo et al., 2013; Yadav et al., 2015; Paul et al., 2015; Das et
al., 2016).
Although copious evidences have shown that bacteria play an im-
portant role in the release of the arsenic, some others indicated that bac-
terial activities can also reduce the content of the arsenic in
groundwater. The sulfide produced during bacterial SO24 − reduction
can form minerals that remove arsenic from solution (Rittle et al.,
1995). Geochemical evidence suggests that the activity of SO2− 4 -reduc-
ing bacteria play an important role for arsenic accumulation to hazard-
ous levels (Kirk et al., 2004). In addition, the Fe (hydrogen) oxides
minerals produced by bacterial NO− 3 reduction (Fe
2+
oxidation) can
also remove arsenic. In a field test, Harvey et al. (2002) observed arsenic
content decreased coinciding with the injection of nitrate solution into
the aquifer. They concluded that this phenomenon was probably as a re-
sult of arsenic adsorption onto iron oxyhydroxides which is precipitated
by bacterial process. Moreover, laboratory experiments have demon-
strated that bacterial mediated sulfate-reducing and nitrate-reducing
processes can both remove arsenic from solution (Keimowitz et al.,
2007; Sun et al., 2009; Omoregie et al., 2013). The works described
above show that bacterial activities can promote arsenic release/de-
sorption (Fe(III) and As(V) reduction) into groundwater and also can
remove arsenic (NO− 3 and SO4
2−
reduction) from groundwater. It is
therefore worthwhile to study the different biogeochemical processes
and their effects on arsenic geochemical behavior in natural aquifers.
Typically, bacteria consume organic matter to obtain energy with
oxygen as an electron acceptor in aerobic environment. When oxygen
is depleted, other oxygen-bearing species becomes an alternative for
consumption. Chapelle (2000) indicated that bacteria in groundwater
consumed DO (dissolved oxygen), nitrate, Fe(III), sulfate and CO2 in
turn along the direction of groundwater flow, evidencing different bio-
geochemical trend with the groundwater environment evolving from
oxidative to reductive conditions. The adsorption, release and co-pre-
cipitation of arsenic in groundwater are closely related to the content
of DO, NO− 2−
3 , SO4 , Fe(III)/Fe
2+
and DOC (dissolved organic carbon)
(Fendorf et al., 2010; Sharif et al., 2008; Harvey et al., 2006). But the con-
tent of these components changes with the flow, owing to changes in
hydrological or biogeochemical process. Many studies have investigated
Please cite this article as: Zhang, J., et al., Arsenic behavior in different biogeochemical zonations approximately along the groundwater flow path
in Datong Basin, northern Chi..., Sci Total Environ (2017), http://dx.doi.org/10.1016/j.scitotenv.2017.01.029
© 2017 Published by Elsevier B.V.
the content of these components, the isotopic composition and the
change of the redox environment along the direction of groundwater
flow to explain the release mechanism of arsenic under the activity of
bacteria (Jia et al., 2014; Guo et al., 2011; Xie et al., 2009; Benner et al.,
2008; Stute et al., 2007; Postma et al., 2007). Nevertheless, only few
studies have investigated the bacterial community structure along the
groundwater flow path and examined the effects of different biogeo-
chemical processes on arsenic.
In this study, the groundwater and bacteria samples were collected
and isolated respectively along the direction of groundwater flow at a
known high-arsenic area in the Datong Basin and evaluated the follow-
ing objectives: (1) the bacteria community structure information, (2)
observed the variable characteristics of the arsenic and other redox sen-
sitive indicators contents, (3) unraveled the cause of redox environment
evolution and revealed arsenic behavior under different biogeochemical
conditions.
2. Study area
Geologically, Datong Basin is a Cenozoic Basin located in the semi-
arid region of northern China (Wang and Shpeyzer, 2000). This Basin
extends from southwest to northeast and is surrounded by the
Hengshan Mountains, the Guancen Mountains and the Hongshou
Mountains (Xie et al., 2013a). The piedmont is the main bedrock,
while the central basin consists of Quaternary unconsolidated sedi-
ments with thickness up to approximately 400 m. According to the buri-
al depths of aquifers, the Quaternary groundwater systems can be
divided into three groups: upper (5–60 m), middle (60–160 m) and
lower aquifers (N160 m) (Wang et al., 2009). The grain size of the sed-
iment generally decreases from margin to the center of the basin. The
central basin is lacustrine and alluvial-lacustrine sandy loam, silt and
silty clay with high content of organic matter. The organic matter con-
tent reaches as high as 1% in the aquifer sediments (Guo et al., 2003),
while the TOC (total organic carbon) concentration reaches up to
17.5 mg/L in groundwater (Luo et al., 2012).
The groundwater is mainly recharged by vertically infiltrating mete-
oric water and laterally penetrating fracture water from the bedrock in
the domain of the mountains (Wang et al., 2009). Discharge occurs
mainly via evapotranspiration and artificial abstraction. The Rivers are
ephemeral and emerge in July to August (monsoon), while precipitation
is the main recharge. There are two general flow regimes at Datong
Basin: (1) flow from margins mountain front areas to the central of
the basin, and (2) flow inside the basin along the direction of the river
from southwest to northeast (Xie et al., 2009). The velocity of the
groundwater movement is relatively faster in mountain front areas
than the central portion of the basin due to the aquifers characteristics,
which are mostly gravel and coarse sand with high hydraulic gradient in
mountain front areas (Wang et al., 2009). Compared to the mountain
fronts, the terrain is flat towards the basin center, while the aquifers
are mainly lacustrine and alluvial-lacustrine fine sand and silty sand
with low hydraulic gradient. The groundwater movement is relatively
slow and the velocity ranges from 0.20 m to 0.58 m per day (K = 20–
58 m per day, J b 1/100) (Xie et al., 2009). The depth of water table is
commonly b 2 to 5 m in the central portion of the basin, with an artesian
well (SHY-02) observed within the survey area.
3. Sampling and analytical methods
A total of twenty-two water samples were collected along the
groundwater flow path in August 2014 at the Datong basin. According
 J. Zhang et al. / Science of the Total Environment xxx (2017) xxx–xxx 3

to the groundwater recharge and discharge areas and the flow path dis-
tance, three groundwater bacterial samples were collected. The loca-
tions of the sampling sites are shown in Fig. 1. All sampled wells are
used for domestic supply or irrigation purposes, except a spring sample.
3.1. Groundwater sampling and analytical methods
Pumping was conducted at each groundwater sampling points for
5mins (until the Eh, pH and EC values almost stabilize) before samples
were retrieved for analysis. The spring sample was collected directly.
Samples for laboratory measurement of anions and cations were filtered
(b0.45 μm) and collected into two acid washed and pre-cleaned 50 mL
HDPE bottles. Those for cation analysis were acidified with ultra-pure
HNO3 to pH b 2, whereas the anion samples were not acidified. Samples
for total arsenic (TAs) analysis were filtered, for arsenite separated with
LC-SAX anion-exchange resin (Sigma-Aldrich) in the field (Le et al.,
2000; Sugár et al., 2013), and acidified to pH b 2 with ultra-pure HCl.
Samples for DOC analysis were also filtered, acidified to pH b 2 with
ultra-pure HCl, and stored in 20 mL amber glass bottles.
Physical and chemical parameters, including temperature (T), pH,
Eh and EC, were measured in the field using a multi-parameter portable
meter (HACH, HQ40d). Redox active water quality parameters, includ-
ing Fe2 +, HS− and NH+ 4 concentrations, were determined on site
using a portable spectrophotometer (HACH, DR2800). Alkalinity was
measured the same day using Gran titration. Major cations (K+, Na+,
Ca2 + and Mg2 +) concentrations were analyzed using inductively
coupled plasma atomic emission spectrometry (ICP-AES) (Thermo Ele-
mental IRIS Intrepid IIXSP). Anions concentrations (Cl−, NO− 2−
3 and SO4 )
were determined by ion chromatography (IC) (Metrohm 761 Compact
IC). TAs and arsenite were analyzed using hydride generation atomic
fluorescence spectrometry (HG-AFS) (AFS-820, Titan). Dissolved organ-
ic carbon (DOC) concentrations were determined using TOC analyzer
(TOC-V, Shimadzu), generating data with a standard deviation of ±
2%.The average analytical error for cations, anions and As were within

Fig. 1. Sampling sites and the spatial distribution of As concentrations in groundwater from Datong Basin.

Please cite this article as: Zhang, J., et al., Arsenic behavior in different biogeochemical zonations approximately along the groundwater flow path
in Datong Basin, northern Chi..., Sci Total Environ (2017), http://dx.doi.org/10.1016/j.scitotenv.2017.01.029
4 J. Zhang et al. / Science of the Total Environment xxx (2017) xxx–xxx
5%. Field and laboratory blanks were below the detection limits for all
the components.
3.2. Bacteria sampling and analytical methods
Approximately, 10 L of sample water was extracted from two wells
(SHY-07 and SHY-22) and a spring (SHY-12), and were filtered through
a 0.22-μm cellulose acetate membrane, respectively. The membrane fil-
ters were immediately loaded into a prepared sterile tube, and frozen at
−20 °C until DNA extraction. Prior to extraction, the membranes were
cut into pieces using sterile techniques, and transferred directly to the
prepared tubes for DNA extraction using PowerWater DNA Isolation
Kit (MoBio, Carlsbad, CA 92010, USA) and following the manufacturer's
protocol (Febria et al., 2012). The extracted DNA samples were kept at
−20 °C prior to sequencing analysis. Bacterial 16S rRNA gene sequences
were amplified using the primer pair 520F (5′-AYTGGGYDTAAAGNG-
3′) and 802R (5′-TACNVGGGTATCTAATCC-3′). PCR amplification was
carried out as follows: initial denaturation at 98 °C for 5 min, followed
by 25 cycles of 98 °C for 10 s, 50 °C for 30 s, and 72 °C for 30 s, and
then a final extension at 72 °C for 5 min. The purified amplicons were
quantified on Microplate reader (BioTek, FLx800) with Quant-iT™
PicoGreen® dsDNA Assay Kit (Invitrogen, P7589) and pooled together.
Sample libraries for sequencing were prepared according to published
protocols (Caporaso et al., 2012; Jiang et al., 2016). The samples were
further processed utilizing MiSeq Reagent Kit v3 (Illumina, MS-102-
3003) for sequencing, then analyzing the diversity and relative abun-
dance of prokaryotic communities (Wuchter et al., 2013; Degnan and
Ochman, 2012).
4. Results and discussion
4.1. Hydrochemistry
The main physical and chemical characteristics of the groundwater
samples are listed in Table 1. The total dissolved concentration of As in
the groundwater samples range from ˂1 to 947.6 μg/L. Nine out of the
22 groundwater samples contains As exceeding the 10 μg/L maximum
contamination level (MCL) (average 348.4 μg/L) (WHO, 2011), and are
mostly distributed around the center of the basin. Approximately, 59%
of the samples are below the MCL and were more dominant at the
west and east margins of the basin.
The pH of all groundwater samples were neutral to weakly alkaline
(7.22– 8.11), while Eh values are generally low at the center of the
basin (average −101.8 mV). Relatively higher Eh values were observed
near the mountain front recharge areas, which range from 60.8 to
121.4 mV (average 93.3 mV). High concentrations of NH+ 4 , Fe
2+
, and
TAs were found distributed around the center of the basin (as listed in
Table 1), however, six out of the 22 nitrate-containing groundwater
samples were below the detection limit (b0.1 mg/L). While relatively
lower concentrations of NH+ 4 near the margins of the basin (average
0.13 mg/L). Apart from sample SHY-22, the groundwater has low HS−
concentration range from b1 to 39 μg/L (average ~ 4.6 μg/L).
4.2. Variations of chemical compositions along the flow path
Xie et al. (2013b) delineated three major groundwater flow paths in
the study area: groundwater flow from two margin areas towards the
center of the basin; and that from southwest to northeast along the
Sanggan River. Accordingly, variations in chemical compositions were
observed along the described flow paths extending from the east mar-
gin to the center of the basin in this study.
Concentrations of DOC and HCO− 3 showed increasing tendency
along the groundwater flow path (Fig. 2A). The Eh value is one of the
important indexes reflecting redox environment of groundwater.
Along the flow path, the Eh values were basically stable at around
100 mV from 0 to 8.8 km. However, it drops sharply to −143.5 mV at
Please cite this article as: Zhang, J., et al., Arsenic behavior in different biogeochemical zonations approximately along the groundwater flow path
in Datong Basin, northern Chi..., Sci Total Environ (2017), http://dx.doi.org/10.1016/j.scitotenv.2017.01.029
10.8 km and then fluctuates at about − 160 to − 100 mV between
10.8 and 15.2 km (Fig. 2B). Thus, this implies the presence of redox zo-
−
nation along the groundwater flow path. Similarly, SO2− 4 /Cl ratio de-
creased steadily from 0 to 10.8 km and kept relatively constant
between 10.8 and 15.2 km (Fig. 2E). Conversely, both TAs and Fe2+ con-
centrations were generally below the detection limits (1 μg/L and
0.01 mg/L, respectively) between 0 and 8.8 km, then reveal a general
tendency of ascent between 8.8 and 15.2 km (Fig. 2C). Along the flow
path, NH+4 concentration shows a similar trend with TAs and Fe
2+
.
4.3. Bacterial community structure in groundwater
Three groundwater samples SHY-12 (0 km), SHY-07 (8.8 km) and
SHY-22 (15.2 km) were used to determine the bacterial community
structures. Results from the microbial community analysis (MCA) re-
vealed that the bacterial diversity among these three groups were sig-
nificant. This was clearly evident at the genera level, as shown in Fig. 3.
In sample SHY-12, Fluviicola, Rhodococcus, Glaciecola and Nevskia
were identified as the dominant genera in the bacterial community
structure, accounting for 16.89%, 15.46%, 7.21% and 7.23%, respectively.
Previous studies have indicated that these four kinds of dominant gen-
era are aerobic or strictly aerobic species, and their growth is usually as-
sociated with oxygen consuming (O'Sullivan et al., 2005; Conville and
Witebsky, 2007; Romanenko et al., 2003; Weon et al., 2008).
Acinetobacter, Pseudomonas, Gallionella and Thauera amounting to
15.97%, 11.67%, 10.44% and 8.74%, respectively, were the dominant gen-
era associated with sample SHY-07. Many studies have shown that
Pseudomonas can reduce As(V) to As(III) by a detoxification pathway
(Srivastava et al., 2010; Chitpirom et al., 2009), and also, Freikowski et
al. (2010) found a new Pseudomonas putida strain WB that can reduce
As(V) both by detoxification and energy-conserving respiratory path-
ways. Thauera and Gallionella typically utilize NO− 3 as an electron accep-
tor in the respiratory processes. Moreover, Gallionella can oxidize Fe2+
and reduce NO− 3 in a redox active process where Fe
2+
serves as electron
−
donor and NO3 as electron acceptor (Shinoda et al., 2004; Anderson and
Pedersen, 2003).
The MCA of sample SHY-22 revealed presence of Desulfosporosinus,
Acinetobacter, Brevundimonas and Pseudomonas as the dominant genera.
Desulfosporosinus account for more than 21.6% of SHY-22 microbial
community and this belong to Sulfate-Reducing bacteria (SRB), which
function to reduce SO24 − to HS− (Castro et al., 2000; Alazard et al.,
2010). Moreover, Desulfosporosinus also as dissimilatory arsenate-re-
spiring prokaryotes (DARPs) can utilize As(V) as an electron acceptor
(reduce As(V) to As(III)) in the respiratory processes (Oremland and
Stolz, 2005; Pérez-Jiménez et al., 2005). Acinetobacter, Pseudomonas
and Brevundimonas are other prominent bacteria that play important
roles in arsenic transformation process, most especially in high arsenic
regions (Gault et al., 2005; Li et al., 2013). Besides, laboratory experi-
ments have shown that these bacteria possess higher arsenic resistance,
with Pseudomonas demonstrating arsenic reduction ability (Chitpirom
et al., 2009; Cavalca et al., 2010). Geobacter and Desulfuromonas belong
to Geobacteraceae, a typical Fe-reducing bacteria (Fe-RB) family
(Lonergan et al., 1996), and account for 2.21% and 1.9% respectively in
SHY-22. These two genera were completely absent in samples SHY-12
and SHY-07.
However, many bacteria can use various electron acceptors for respi-
ration. For example, the genus Desulfosporosinus can use SO24 − and
As(V) as electron acceptors. Obviously, there is no sufficient evidence
to discriminate which acceptor they will choose (or use simultaneously)
through the bacterial characteristics only. Therefore, bacteria informa-
tion may be combined with groundwater chemical data to explain the
observed phenomena. For example, with the decreasing ratio of SO2− 4 /
Cl− with the dominate genus belonging to SRB, it can be rationally con-
cluded that bacterial SO2−4 reduction process is occurring in the ground-
water and that the biogeochemical analysis at genus level can reflect the
in Datong Basin, northern Chi..., Sci Total Environ (2017), http://dx.doi.org/10.1016/j.scitotenv.2017.01.029
Please cite this article as: Zhang, J., et al., Arsenic behavior in different biogeochemical zonations approximately along the groundwater flow path

Table 1
Hydrochemistry composition of groundwater from Datong Basin.

Sample ID Type Location Depth Elevation T pH Eh SO2−

4 HS− NO−
3 HCO−
3 Cl− Na+ Mg2+ Ca2+ K+ NH+
4 Fe2+ DOC As(III) TAs
m M °C mV mg/L μg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L mg/L μg/L μg/L

J. Zhang et al. / Science of the Total Environment xxx (2017) xxx–xxx

Eastern margin (Zone I)
SHY-07 Groundwater N:39°19′33″ E:112°49′43″ 35 1033 15.5 7.22 96.8 499.1 2 249.7 475.8 445.6 297.9 101.0 265.2 146.1 0.74 b0.01 3.6 b1 3.3
SHY-08 Groundwater N:39°18′32″ E:112°49′34″ 45 1039 16.5 7.76 101.0 24.0 b1 2.6 231.3 12.2 10.2 13.0 73.0 2.7 0.05 b0.01 2.1 b1 b1
SHY-09 Groundwater N:39°17′25″ E:112°49′26″ 55 1040 13.2 7.67 92.5 31.3 2 2.5 243.6 12.9 11.3 13.6 76.6 2.9 0.02 b0.01 2.1 b1 b1
SHY-10 Groundwater N:39°17′10″ E:112°51′05″ 110 1063 14.0 7.69 97.6 62.4 2 20.1 253.6 7.6 9.5 14.6 90.9 3.3 0.02 b0.01 2.1 b1 b1
SHY-11 Groundwater N:39°16′14″ E:112°50′34″ 35 1059 17.3 7.78 89.9 41.4 3 27.7 302.1 14.6 28.7 28.4 63.5 5.9 0.02 b0.01 1.7 b1 b1
SHY-12 Spring N:39°15′17″ E:112°51′17″ 1117 19.9 7.88 97.5 75.3 b1 7.5 251.3 8.9 38.0 24.3 47.9 9.6 0.02 b0.01 1.8 b1 b1
SHY-13 Groundwater N:39°15′46″ E:112°50′01″ 40 1054 14.3 7.94 77.2 38.6 2 3.8 251.3 12.2 25.5 20.9 50.5 2.9 0.04 b0.01 1.5 b1 b1

Center of the basin (Zone II)

SHY-01 Groundwater N:39°24′26″ E:112°54′27″ 26 1017 12.8 7.78 -103.8 324.2 4 b0.1 615.6 679.9 510.5 112.5 39.2 4.6 0.72 0.13 5.0 147.8 194.6
SHY-02 Groundwater N:39°23′09″ E:112°53′53″ 150 1021 15.3 7.96 -164.3 0.7 14 b0.1 324.3 11.6 71.8 17.2 16.0 0.8 1.94 0.14 10.9 102.3 144.8
SHY-03 Groundwater N:39°22′05″ E:112°51′41″ 28 1021 15.4 7.71 -146.0 45.2 b1 b0.1 471.2 191.7 178.2 50.7 40.7 1.2 1.06 0.58 3.5 835.6 947.6
SHY-04 Groundwater N:39°21′02″ E:112°50′50″ 33 1025 12.4 7.99 -105.2 0.9 5 0.5 303.6 12.5 62.1 19.7 16.2 0.6 1.18 0.02 3.2 256.6 307.2
SHY-05 Groundwater N:39°20′23″ E:112°50′40″ 32 1032 13.9 7.73 -79.4 47.6 4 10.3 262.9 101.8 63.2 22.7 88.1 2.5 0.34 0.02 2.4 b1 3.3
SHY-06 Groundwater N:39°20′32″ E:112°49′21″ 30 1026 15.1 8.11 -143.5 1.2 39 0.5 322.8 28.7 73.0 23.9 15.8 0.8 0.84 0.04 2.6 306.6 330.7
SHY-14 Groundwater N:39°21′44″ E:112°47′35″ 16 1033 15.8 7.60 -110.8 992.3 3 b0.1 676.4 1387 780.1 250.8 86.7 8.7 1.57 1.17 5.3 195.2 222.9
SHY-15 Groundwater N:39°21′14″ E:112°47′50″ 25 1031 16.4 7.66 64.9 282.7 b1 102.3 782.4 339.5 377.8 124.7 70.9 4.5 0.45 0.02 8.5 b1 2.8
SHY-16 Groundwater N:39°22′54″ E:112°46′21″ 25 1029 17.1 7.92 -74.6 469.9 b1 b0.1 507.3 216.0 391.3 60.3 27.5 3.1 0.77 0.07 2.9 b1 16.3
SHY-21 Groundwater N:39°23′24″ E:112°50′16″ 28 1025 15.5 7.74 -99.2 1339 3 b0.1 1301 750.7 1026 179.9 51.0 8.3 2.08 0.32 10.0 90.9 124.4
SHY-22 Groundwater N:39°22′15″ E:112°52′13″ 36 1020 13.2 7.89 -157.7 2.3 945 1.1 442.7 18.2 102.8 23.9 23.5 1.0 1.51 0.17 4.1 695.6 847

Western margin (Zone I′)

SHY-17 Groundwater N:39°25′13″ E:112°42′24″ 120 1096 15.6 7.84 85.1 93.3 4 35.7 420.4 47.2 166.1 20.6 37.1 2.4 0.11 b0.01 1.3 b1 b1
SHY-18 Groundwater N:39°23′48″ E:112°42′49″ 50 1062 14.0 7.74 121.4 100.7 b1 48.8 345.9 53.1 118.0 30.6 51.9 1.5 0.01 b0.01 1.7 b1 b1
SHY-19 Groundwater N:39°24′20″ E:112°43′45″ 45 1045 12.7 7.73 106.8 107.3 2 18.9 307.4 51.7 109.5 21.3 50.2 1.8 0.10 0.09 1.7 b1 b1
SHY-20 Groundwater N:39°23′52″ E:112°44′15″ 52 1034 13.3 7.81 60.8 140.6 b1 0.9 345.1 96.0 124.5 34.2 68.4 1.3 0.34 b0.01 2.0 b1 b1

5
6 J. Zhang et al. / Science of the Total Environment xxx (2017) xxx–xxx

Fig. 2. Variations of chemical components and surface elevation approximately along the groundwater flow path.

function of the bacteria if combined with other information (chemical groundwater redox environment is dominated by major elements of C,
data or basic theories). O, N, Fe, and S at different valence states in molecules or ions. However,
bacterial activities can change the valence state of these elements, which
will affect the redox environment.
4.4. Groundwater redox zonation along the flow path
In groundwater, bacteria usually oxidize organic carbon (electron
donor), and reduced O2, NO− 2−
3 , Fe(III), SO4 sequentially (Chapelle,
The sampling points are approximately divided into three zones (I, I′’
2000). Organic carbon is oxidized to CO2, and forms HCO–3 in the
and II) (Fig. 1), according to the clustering analysis results using Eh, NO−
3 ,
− groundwater. The reactions are as follows:
SO2−
4 /Cl and Fe2+ concentrations (or ratios) through by SPSS 12.0.
Zones I and I′’ are located in east and west of the basin respectively,
close to the Piedmont recharge zones. Zone II is located at the center of CH3 COO− þ2O2 →Hþ þ2HCO3 − ð1Þ
the basin, where the groundwater discharge zone and elevation is be-
tween the 1017– 1033 m. As mentioned above, Zones I and I′’ are weak
5CH3 COO− þ8NO3 − þ3Hþ →4N2 þ 4H2 O þ 10HCO3 − ð2Þ
oxidizing environment, while Zone II belongs to the strong reducing en-
vironment. Hence, the groundwater environment showed obvious redox
zonation from the Piedmont to the center of the basin. Generally, CH3 COO− þ 8FeðOHÞ3 þ 15Hþ →8Fe2þ þ20H2 O þ 2HCO3 − ð3Þ

Fig. 3. Bacterial community structure and relatively abundance of bacterial genus based on 16S rRNA clone sequence extracted from groundwater (SHY-07, SHY-12, SHY-22) from study
area.

Please cite this article as: Zhang, J., et al., Arsenic behavior in different biogeochemical zonations approximately along the groundwater flow path
in Datong Basin, northern Chi..., Sci Total Environ (2017), http://dx.doi.org/10.1016/j.scitotenv.2017.01.029
 J. Zhang et al. / Science of the Total Environment xxx (2017) xxx–xxx
CH3 COO− þSO4 2− →HS− þ 2HCO3 −
A good correlation is seen between DOC and HCO− 3 concentration
(Fig. 4). DOC and HCO− 3 content gradually increased away from the
Piedmont to the center of the basin, which may be mainly as a result
of bacterial activity. Carbonate mineral dissolution is another important
factor that might be contributing to HCO− 3 concentration increment in
groundwater: CaCO3/MgCO3 + CO2 + H2O = Ca2++ Mg2++2HCO− 3 .
However, the CO2 produced by bacterial respiration can also promote
this process, in addition, the δ13C of DIC analyzed by Xie et al. (2013a)
also confirm biological process was the most important contributor to
the DIC in the groundwater at Datong.
Zones I and I′’ are close to the Piedmont recharge zones, which main-
ly are phreatic aquifers (Wang et al., 2009). The aquifers and the head
space are made up of mostly gravel and coarse sand and have a relative-
ly large pore space. Hence, atmospheric O2 can diffuse into the ground-
water easily through the air-filled pore spaces. Additionally, the velocity
of the groundwater movement is relatively faster, generating a rapid ex-
change rate of O2. Sequencing data obtained from the bacterial commu-
nity structure of SHY-12 also confirmed the presence of aerobic bacteria
which forms the dominant genera is this region (Fig. 3). Certainly,
groundwater fluctuations (as a result of precipitation) will alter ground-
water chemical conditions and thus result in strong changes in bacteria
community structures. Near the Piedmont (Zones I and I′’), that is the
recharge area, owing to the presence of a relatively high gradient in
the area and thus preventing retention of the water in-situ, and while
some part of the flow percolates into the groundwater. Therefore,
when precipitation accompanied with dissolved O2 enters into the aqui-
fers, it results in a weakly oxidizing groundwater environment, with the
dominant genus still being aerobic. Although aerobic bacteria can con-
sume O2 partly in the groundwater, the DO is recharged constantly
and its supply is greater than consumption.
The steady rise of HCO− 3 contents indicated that the bacterial activi-
ties became stronger close to the center of the basin. Besides, the dis-
solved oxygen supply at this time is lesser than the consumption;
therefore, the dissolved oxygen concentration becomes limited or
exhausted with the increase of groundwater flow distance. Here, the
consumption of NO− 3 became the main biogeochemical process. Evi-
dence from the SHY-07 bacterial community structure also confirms
that the bacteria with nitrate reduction (denitrification) ability were
the dominant genera (Fig. 3). Therefore, the redox characteristics of
Zones I and I′’, which involves consumption of O2 and NO− 3 could be
the prevailing biogeochemical processes governing groundwater in
weak oxidation environment.
Fig. 4. The relationship between DOC and HCO−
3 concentrations in groundwater from
study area.
Please cite this article as: Zhang, J., et al., Arsenic behavior in different biogeochemical zonations approximately along the groundwater flow path
in Datong Basin, northern Chi..., Sci Total Environ (2017), http://dx.doi.org/10.1016/j.scitotenv.2017.01.029
7
ð4Þ In Zone II, the content of DOC in groundwater is relatively high due
to the prevalence of organic-rich lacustrine sediments with high con-
tent of organic matter. Additionally, the DOC content is consistent
with high content of NH+ 4 which is probably released from organic mat-
ter decomposition (Postma et al., 2007). Biogeochemical reactions
(NO− 3 , Fe(III) and SO4
2−
reductions) were highly influenced by the hy-
draulic characteristics (sluggish flow) and retention time (relatively
long) of the zone's groundwater. As a result, the nitrate content in all
the groundwater samples were lower than 1.2 mg/L except for SHY-
05 and SHY-15, and the Fe2+ content was greater than Zones I and I′’.
Moreover, an apparently high content of HS− was found rising up to
945 μg/L in SHY-22, which confirms our initial observation of a strong
H2S odor during field sampling. These observations indicate that Zone
II groundwater is in a strong reducing environment, which is consistent
with the negative Eh values.
The relatively long groundwater flow path resulted in the depletion
of O2 and NO− 3 and the thicker aquicludes above the aquifer result in
limited O2 diffusion into the groundwater, and thus rendering their sup-
ply inadequate. Additionally, the phreatic water (Zone II) table is elevat-
ed during transient monsoon (July to August), and could form
temporary wetland in the flat lands. This temporary surface water
could also prevent the diffusion of O2 into the groundwater and thus,
changing the phreatic aquifers redox conditions. As a result, the bacteri-
al community structures in the phreatic aquifers are likely to change.
However, the aquifer in this zone is confined by thick layers of
aquicludes (consisting of clay and silty clay), and thus prevents precip-
itation from its reach due to it is confinement at burial depth reaching
up 25 to 45 m. Hence, bacteria present in this zone tend to use up
Fe(III) and SO2− 4 as an electron acceptor, according to the sequence of
redox reactions reported by Borch et al., 2010. Interestingly, analysis
of SHY-22 bacterial community structure show that Desulfosporosinus
−
is the dominant genus (Fig. 3), and also, SO2− 4 /Cl ratio reduce along
the flow path (Fig. 2E), prominently reflecting SO2− 4 reduction process
in the zone. Although, the percentage of the Fe-RB is relatively small,
they are not found in SHY-12 and SHY-07. Therefore, SO2− 4 reduction
appears to be the main biogeochemical process taking place in Zone II
groundwater, as evidenced by a strong reducing environment.
4.5. Increasing arsenic content along the flow path
Similar to the groundwater environment redox zonation, the TAs
content also possess obvious zonation along the groundwater flow
path. In Zones I and II′’, TAs contents of samples are lower than 10 μg/L.
In Zone II, almost all samples have contents higher than 120 μg/L, except
for SHY-05, SHY-15 and SHY-16, and the highest reaching up to 947.6 μg/L
(SHY-03). Previous studies have indicated that the redox environment is
the principal factor controlling As content in groundwater (Nickson et al.,
2000; Smedley and Kinniburgh, 2002). In oxidizing environment, As is
generally in the form of As(V); while As(III) are commonly found in re-
ducing environment (Oremland and Stolz, 2005). Both As(V) and As(III)
species can be adsorbed to aquifer sediments (e.g. amorphous iron
oxide, hematite and goethite), however, generally As(III) is expected to
be less strongly adsorbed than As(V) at the near-neutral pH (Smedley
and Kinniburgh, 2002; Mai et al., 2014). Commonly, As(V) is absorbed
or coexist with Fe/Al (hydrogen) oxide minerals in oxidizing environ-
ment. Therefore, in the reducing environment, reductive dissolution of ar-
senic-bearing Fe (hydrogen) oxides minerals and reductive desorption of
arsenate results in increased concentration of As in groundwater. In the
study area, TAs content b 10 μg/L in Zones I and I′’ are as a result of the
weakly oxidizing condition, but Zone II is a strong reducing environment
with high TAs contents (mainly to As(III)).The groundwater TAs content
distribution pattern therefore coincides with the above views.
Although redox environment of groundwater is the main factor con-
trolling the As content, the mechanism of these changes is closely relat-
ed to bacteria activities. As mentioned above (Section 4.4), the bacteria
8 J. Zhang et al. / Science of the Total Environment xxx (2017) xxx–xxx
activities prompted the groundwater to evolve from weak oxidizing to
strong reducing environment from Piedmont into the center of basin.
In the Zones I and I′’, the consumption of O2 and NO− 3 is the major
biogeochemical processes, with redox and biological restriction of
Fe(III) and As(V) reduction. Analysis of samples withdrawn from
these zones also reveals that the contents of Fe2+ and TAs are almost
below detection limit. Therefore, Fe(III) reductive dissolution or As re-
ductive desorption process will not occur in this zone, leaving a low
As groundwater content.
In Zone II, bacteria mainly use Fe(III) or SO2− 4 as electron acceptor
due to partial or complete depletion of NO− 3 . This results in Fe(III) reduc-
tion, and thus initiating the release of Fe2+ and As(V) into the ground-
water at the same time. However, the results obtained in the study
show that there is no obvious correlation between them. As(III) is the
main form of arsenic in groundwater, and the Fe2+ contents are very
low (0.02– 1.17 mg/L, average ~ 0.24 mg/L) relative to other high arsenic
groundwater areas like Bangladesh (0.01– 29 mg/L; pH 5.51–7.4, aver-
age 6.63) (Nickson et al., 2000), West Bengal (0.01– 5.26 mg/L,
average ~ 1.12 mg/L; pH 6.0–8.4, average 7.2) (Mukherjee et al.,
2009), Cambodia (0.05– 16.2 mg/L, average 2.8 mg/L; pH 5.42–8.01, av-
erage 6.94) (Berg et al., 2007), Vietnam (0.05– 56 mg/L, average
2.6 mg/L; pH 5.00–8.70, average 6.83) (Berg et al., 2007), Jianghan
Plain (1– 12 mg/L; pH 6.4– 7.6, average 7.0) (Gan et al., 2014). More in-
teresting is that the TAs contents are higher than Fe2+ contents in most
of the samples (Fig. 6C). This phenomenon is very rare in high arsenic
groundwater of the world. The low Fe2+ content could be attributed
to the formation of FeCO3, amorphous FeS and re-adsorption on Fe-
oxide minerals (Xie et al., 2013a; Guo et al., 2013). Zone II groundwater
samples (except for sample SHY-19) saturation index (SI) for siderite
(FeCO3) was calculated using PHREEQC (version 3). Although the
SIsiderite increases with Fe2+ content (Fig. 5), the formation of FeCO3 is
unlikely the main factor for the low Fe2+ content. In addition, the for-
mation of amorphous FeS was also insignificant for the low Fe2+ con-
tent due to the very low HS− content in most samples (Table 1).
Similarly, there could be other reason(s) that contributed to the rel-
ative less content of Fe2+, like relatively retarded Fe(III) reduction pro-
cess. According to the redox sequence, sulfate might be outcompeted by
amorphous Fe (hydrogen) oxide minerals when bacteria select the elec-
tron acceptor under near-neutral pH conditions (Borch et al., 2010).
However, Hansel et al. (2015) observed that ferrihydrite reduction did
not precede sulfate reduction (pH 7.2). Early studies have shown that
bacteria reduced Fe(III) before sulfate base on a thermodynamic ladder
(Lovley et al., 1994;McMahon and Chapelle, 2008), but the theory seem-
ingly is not suited in alkaline environments (Bethke et al., 2011). Fur-
thermore, Flynn et al. (2014) found that Fe-RB (Shewanella oneidensis
Fig. 5. The relationship between SIsiderite and Fe2+ concentrations in groundwater from
study area.
Please cite this article as: Zhang, J., et al., Arsenic behavior in different biogeochemical zonations approximately along the groundwater flow path
in Datong Basin, northern Chi..., Sci Total Environ (2017), http://dx.doi.org/10.1016/j.scitotenv.2017.01.029
MR-1) cannot reduce goethite (α-FeOOH) directly under alkaline con-
ditions (pH 9), however, the HS− produced subsequently reduced goe-
thite abiotically. In the study area (Zone II), perhaps the ability of the Fe-
RB directly reducing Fe(III) was retarded because of the weakly alkaline
conditions (pH 7.60–8.11, average 7.83) and also partial Fe2+ co-precip-
itation with CO2− 3 ,leading to a low Fe
2+
in groundwater. As discussed
above, the SO24 − reduction process could be said to occur in Zone II
groundwater, moreover, while the Fe-RB account for a small percentage
(about 4%) in bacterial community structure of sample SHY-22, thus,
the Fe(III) reduction may not be that strong. Besides, we also found an-
other interesting phenomenon that Bangladesh, West Bengal and other
areas (as mentioned above) have a relative high Fe2+ contents and a
wider range of pH with average near 7. In these areas, probably weakly
acidic and near-neutral conditions (in majority of the wells) created a
favorable environment which prompts bacterial Fe(III) reduction pro-
cess, therefore, the reductive dissolution of arsenic-bearing Fe (hydro-
gen) oxides minerals is the main controlling factor in these areas.
In Zone II, although bacterial Fe(III) reduction may not be high, the
HS− produced by sulfate reduction can reduce Fe(III) abiotically. There-
fore, the Fe(III) reduction process (biotic or abiotic) undoubtedly is an
important factor for groundwater arsenic contamination. However,
under reducing conditions, bacterial reductive desorption of arsenate
is another significant process for arsenic enrichment in groundwater
(Oremland and Stolz, 2003; Kudo et al., 2013). Desulfosporosinus and
Pseudomonas have a relatively high percentage in SHY-22, accounting
for 21.6% and 8.85%, respectively. Desulfosporosinus belong to Sulfate-
Reducing bacteria which have ability to reduce SO24 − to HS− (Castro
et al., 2000; Alazard et al., 2010), and also can utilize As(V) as an elec-
tron acceptor (reduce As(V) to As(III)) in the respiratory processes
(Oremland and Stolz, 2005; Pérez-Jiménez et al., 2005). Pseudomonas
can reduce As(V) to As(III) by a detoxification pathway (Srivastava et
al., 2010; Chitpirom et al., 2009) or an energy-conserving respiratory
pathway (Freikowski et al., 2010). Probably, bacterially mediated
As(V) reduction led to As(III) desorption in groundwater or the bacteria
reduced As(V) which have been already released in groundwater (re-
ductive dissolution of arsenic-bearing Fe (hydrogen) oxides minerals).
Both mechanism may be responsible, however, what is obvious is that
As(III) is the main form in the groundwater zone.
In summary, we consider the biotic/abiotic reductive dissolution of
arsenic-bearing Fe (hydrogen) oxides minerals and reductive desorp-
tion of arsenate as major causes of arsenic enrichment in the study
area aquifers. Nevertheless, it is also unclear which mechanism are the
most important factor and the contribution rate of each mechanism.
Further research is needed to explicit this problem.
4.6. The effect of nitrate on arsenic
Sample site SHY-07 was close to the center of the basin, and was di-
vided into Zone I due to its positive Eh value. It has a high NO−3 content
(249.7 mg/L) and also an unusually high K+ content (146.1 mg/L). This
could mainly be as a result of pollution. Similarly, SHY-05 and SHY-15
both have a relatively high NO− 3 content in Zone II, with values of
10.3 mg/L and 102.3 mg/L, respectively, while the rest of samples all
below 1.2 mg/L (Table 1). Moreover, these two samples are the only
ones with low arsenic contents (b10 μg/L) in Zone II. Yet, the poor linear
correlation observed between NO− 3 and arsenic, and the high levels of
NO−3 corresponds to scarcely any of arsenic (b3.4 μg/L), and vice versa
(Fig. 6A). This phenomenon coincides with others investigation
(Hosono et al., 2011; Xie et al., 2009; Nickson et al., 2000). Generally,
groundwater is in weak oxidation condition, when NO− 3 contents are
relatively high, and the arsenic contents are low. SHY-07 shows that
genus Gallionella (10.44%) and Thauera (8.74%) have a relatively high
percentage bacterial community structure, and they are able to use
NO−3 as electron acceptor. Following the possibilities described above,
arsenic release into groundwater is disadvantaged, because Fe(III) and
As(V) reduction are restricted by high content of NO− 3 . Namely, the
 J. Zhang et al. / Science of the Total Environment xxx (2017) xxx–xxx 9

Fig. 6. The plots of TAs vs. NO− 2− −

3 (A), SO4 /Cl (B), Fe
2+
(C), Eh (D) in groundwater from study area.

release or desorption of arsenic, a process that can proceed until the
NO−3 is nearly exhausted, and this corresponds to the high arsenic con-
tent versus very low NO− 3 content (b 1.2 mg/L) (Fig. 6A). In addition,
genus Gallionella has ability to reduce NO− 3 and oxidize Fe
2+
simulta-
neously (Shinoda et al., 2004; Anderson and Pedersen, 2003). Another
possibility is that arsenic have already been released, and then laterally,
Fe2 + and As(III) were oxidized by bacteria due to the input of NO− 3 arsenic transformation in groundwater pathways. Nevertheless, this as-
(maybe fertilization) and result in Fe (hydrogen) oxides co-precipita-
tion with As(V) in groundwater. Field work and laboratory experiment
have demonstrated that groundwater (or solution) arsenic content de-
creased with the input of NO− 3 and both them considered the phenom-
enon cause by the bacterial activities similar to those discussed above
(Harvey et al., 2002; Omoregie et al., 2013). These proposed mecha-
nisms for arsenic reduction have important implications for arsenic re-
mediation in high arsenic groundwater.
4.7. Potential future studies on As-groundwater biogeochemistry
As discussed above, bacterial activities play key roles in groundwater
redox transformation and have significant effect on groundwater chem-
istry. Nevertheless, bacterial communities are also transformed with
groundwater conditions, especially those areas affected by groundwater
fluctuations (altered redox conditions). Therefore, collecting samples
(groundwater and bacteria) at different time (e.g. monsoon and dry
season) or long-term monitoring is important for groundwater biogeo-
chemistry studies. While it can be argued that extraction of groundwa-
ter may give access to a limited population in aquifers especially those
attached to aquifer sediments and situated in narrower pores, chemical
components like DOC, O2, NO− 3 , SO4
2 −/
HS−, Fe2 +, and As(III) mainly
dissolved in groundwater rather than in sediment hence, the corre-
sponding bacteria that utilizes these “nutrients” should be closely asso-
ciated to those suspended in groundwater. However, the effects of
bacteria attached to aquifer sediments should not be neglected because
they mainly utilize “proxy nutrients (like ferric ions)” and may provide
significant information pertinent to understanding the mechanism of
sumption requires further study. For specific group of bacteria (e.g. arse-
nate reducing bacteria or sulfate reducing bacteria), biochemical tests or
use of amplicons of functional genes (arrA for DARPs, and dsrB for SRB)
can give more specific information for these bacteria.
5. Conclusion
The effects of different biogeochemical processes on arsenic release
in groundwater flow paths were systematically and successfully inves-
tigated in this study. The study area was divided into Zones I, I′ and II ac-
cording to the Eh, NO− 2− −
3 , SO4 /Cl and Fe
2+
concentrations (or ratios).
Zones I and I′ are located near Piedmont or alluvial fans, with TAs con-
tents of b1 to 3.3 μg/L. Zone II, located at the center of the basin had
TAs contents ranging from 2.8 to 947.6 μg/L. The groundwater environ-
ment shows obvious redox zonation from the Piedmont to the center of
the basin. Moreover, the hydrogeochemical data and bacterial commu-
nity structure analysis indicated that bacteria activities are the main fac-
tors responsible for the groundwater environment evolution from
oxidation to reduction conditions. The SO2−4 reduction process occurred
at the center of the basin, with accompanying strong reducing groundwa-
ter environment. In the weakly oxidizing environment (Zones I and I′)
the TAs contents were low, but arsenic enrichment was observed in

Please cite this article as: Zhang, J., et al., Arsenic behavior in different biogeochemical zonations approximately along the groundwater flow path
in Datong Basin, northern Chi..., Sci Total Environ (2017), http://dx.doi.org/10.1016/j.scitotenv.2017.01.029
10 J. Zhang et al. / Science of the Total Environment xxx (2017) xxx–xxx
the reducing environment (Zone II). In Zone I, bacteria mainly consumes
O2 or NO− 3 which inhibits Fe(III) and As(V) reduction reaction, resulting
in a very low As content. In Zone II, although sulfate reduction represent
the main process, the Fe(III) and As(V) reduction processes are also oc-
curring, thus leading to arsenic enrichment in groundwater. The TAs con-
tents increased from Piedmont to the center of the basin, with As(III) as
the main form. Therefore, we consider the biotic/abiotic reductive disso-
lution of arsenic-bearing Fe (hydrogen) oxides minerals and reductive
desorption of arsenate as mechanisms that both contributed to arsenic
enrichment in the study area aquifers.
Acknowledgements
The authors would like to thank the three anonymous reviewers for
their constructive suggestions and comments on this manuscript.
Funding for this project were supported jointly by National Natural Sci-
ence Foundation of China (No. 41630318 and No. 41372252), 1: 50000
Hydrogeological Survey in Key Area of Jianghan Plain (DD20160255),
National High Technology Research and Development Program of China
(863 Program) (2012AA062602), the Critical Patented Projects in the
Control and Management of the National Polluted Water Bodies
(2012ZX07204-003-04).
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