International Biodeterioration & Biodegradation xxx (2016) 1e9

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Application of siderite tailings in water-supply well for As removal:

Experiments and field tests
Zhiqiang Wang a, b, Teng Ma a, b, *, Yapeng Zhu a, b, Olusegun K. Abass a, c, Lin Liu a, d,
Chunli Su a, b, Huimei Shan a, b
a
State Key Laboratory of Biogeology and Environmental Geology, China University of Geosciences, Wuhan, 430074, China
b
School of Environmental Studies, China University of Geosciences, Wuhan, 430074, China
c
University of Chinese Academy of Sciences, Beijing 100049, China
d
Nanjing Center, China Geological Survey, Nanjing, 210016, China

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

Article history: Low-grade siderite tailings are difficult to be utilized. For further exploration on the application of
Received 25 April 2016 siderite tailings for arsenic removal, a series of theoretic and practical studies were carried out. According
Received in revised form to the experiment results and technical specifications, a water supply well using composite filtration
25 September 2016
materials of siderite and river sands was designed and a pilot run was conducted in Datong basin, China,
Accepted 14 October 2016
where the groundwater notably contains high concentrations of arsenic. Particle size of 1e2 mm was
Available online xxx
selected as the optimum scheme considering the adsorption kinetic parameters and technical specifi-
cations. Langmuir isotherm yielded a better fit to experimental data with regard to the siderite with a
Keywords:
Siderite tailings
grain size range of 1e2 mm (R2 ¼ 0.983), which indicated that the process generally tends to be a
Composite filtration materials monolayer adsorption reaction with a saturation adsorption capacity of 0.5233 mg g1. Volume pro-
Water supply well for arsenic removal portion coefficients a ¼ 0.5 was selected as the optimal scheme in view of economic factors. The supply
Pilot run water well using composite filtration materials as a pilot run performed well, with average effluent
concentration of 247.57 mg L1, and arsenic removal rates of 52%e65%. The mechanism for arsenic
removal is likely due to the hydroxyl group of Fe(OH)x/FeOOH which contributed from the hydrolysis of
FeCO3, and subsequently substituted by aqueous arsenic. Moreover, the groundwater chemical envi-
ronment contains high sulfide concentrations, which enhances the sorption of arsenic.
© 2016 Elsevier Ltd. All rights reserved.

1. Introduction potential of siderite.

Siderite, one kind of the most common iron ores, is primarily
composed of FeCO3 (Tang and Martin, 2011). China has abundant in
siderite mineral resources with a proven reserve of 1.834 billion
tons of siderite which accounts for 14% of the total proven reserves
of iron ore (Yao, 1993). Because siderite is generally low grade and
occurs together with magnesium, calcium, manganese mineral, the
iron grade of its concentrate obtained by mineral flotation is
commonly below 45% (Guan et al., 2011). Hence, majority of siderite
is discharged as tailings without utilization (Sun, 2006). It is of
profound significance for researchers to study the exploration of
siderite resource in a non-traditional way to maximize the full
* Corresponding author. School of Environmental Studies, China University of
Geosciences, Wuhan, 430074, China.
E-mail address: mateng@cug.edu.cn (T. Ma).
To date there has been an increasing interest in the utilization of
natural mineral materials for adsorption of pollutant compositions
to restore contaminated water or improve water quality (Pivovarov,
2001; Altundogan et al., 2002; Jeon et al., 2003; Jonsson and
Sherman, 2008; Liu et al., 2010; Shan et al., 2013). As a kind of
natural mineral materials, siderite has been used for treatment of
water contaminated by plumbum, fluorine, chromium and other
pollution (Mehmet et al., 2004, 2005). There are several volumes of
publications describing the role of siderite in arsenic removal from
water (Wang and Reardon, 2001; Guo et al., 2007).
High arsenic groundwater is found in eight provinces and poses
great a challenge to health of over 0.6 million people (Yu et al.,
2014). Therefore, it is imperative to develop effective and robust
techniques to remove arsenic from drinking water (Liu et al., 2013).
Adsorption method represents a promising technology for arsenic
removal from drinking water, such as coal-based mesoporous
activated carbon (Gong et al., 2015). Some kinds of biosorbents,

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bacteria, fungus were also used for arsenic removal, such as Pteris
vittata L. (Feng et al., 2014), indigenous bacteria with arsC genes
(Villegas-Torres et al., 2011), and Fusarium pathogens (Ngu et al.,
1998).
Compared with other adsorbents, siderite tailings are consid-
ered to be a kind of ideal absorbents materials because of the ad-
vantages including low cost and easy obtainment. However, studies
related to siderite in the field of treatment for high arsenic
groundwater have only focused on theoretical research or labora-
tory test, rather than field applications and its effectiveness under
actual hydrochemical conditions.
Most people affected by arsenic contamination are impecu-
nious, therefore the applicability of technology, such as pump and
treat method, or in-situ technology like PRB, aeration technology,
etc. which might result in high cost, huge amount of work, sec-
ondary pollutants, is limited in many remote rural areas. However,
it's worth noting that residents in these areas live in small com-
munities and rely on tube wells as a source of drinking water. If a
water treatment device for arsenic removal is designed on the basis
of water supply tube wells, those shortcomings of above methods
would be avoided.
In this paper, we focused on the application of siderite for
arsenic removal from groundwater under field conditions and
carried out a series of theoretic and practical research. The aims of
this paper are as following: (1)to prepare and characterize the
composite filtration materials; (2)to determine the performance
parameters of adsorption and filter medium composition through
laboratory experiments; (3)to determine the specification and craft
of the well and conduct a pilot run to evaluate the effectiveness and
economy; (4)to identify the mechanism of arsenic removal by
composite filtration materials. This paper provides a feasible
method to realize utilization of siderite tailings and has important
implications for high arsenic groundwater treatment in remote
rural areas.
2. Materials and methods
2.1. Mineral collection
The siderite was collected from Fengshan mining company at
Maanshan mine, in Huangmei County, Hubei province, China
(N30 400 56.400 , E115 460 33.100 ). The mine lies in the north of Dabie
orogenic belt, and siderite at the mine was formed by mineral
alteration of Carboniferous-Permian limestone and dolomite

Fig. 1. The surface characteristics of siderite magnified1500 times (a) and 6000 times (b) by FESEM.

Fig. 2. The adsorption equilibrium time and capacity of siderite with variable grain sizes.

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 Z. Wang et al. / International Biodeterioration & Biodegradation xxx (2016) 1e9 3

Table 1 39 22015.400 , E 112 52018.100 ). Field tests using high arsenic
Correlation coefficients and isotherm parameters of both Langmuir and Freundlich
groundwater for arsenic removal were conducted in this site.
models.

Langmuir Freundlich

R2 Qm (mg g1) 1/b R2 KF 1/n 2.3. Batch experiments

0.9826 0.5233 1.9911 0.9450 0.2819 0.4929
Adsorption kinetics tests were performed using variable grain
sizes of siderite. Siderite (0.08 g) at different grain size were mixed
with 100 ml mimic arsenic solution in 16 bottles labeled number
through thermal metamorphism. Fresh siderite without intrusive 1e16 respectively and were placed in NRY-200 constant tempera-
dyke were cracked into 3 cm  6 cm  9 cm using geological ture incubators (T ¼ 25  C). The average proportion of As(III) in
hammer, and then sealed in zip-lock bags. groundwater in most study area is as high as 75%e90% (Zhao et al.,
2007) therefore the concentrations of As(III) and As(V) in mimic
solution were set as 750 mg L1 and 250 mg L1, respectively. The
2.2. Study area stock solution of As(III) and As(V) was prepared using As2O3 and
Na3AsO4$12H2O separately (AR, Sinopharm chemical reagent
Datong Basin, located north of Shanxi, is one of the most typical Co,.Ltd).
high arsenic groundwater distribution areas in China. The climate Isothermal adsorption tests were conducted to determine the
of this area belongs to classic arid and semi-arid with strong
evaporation (Xie et al., 2012). The high arsenic groundwater is
strip-shaped from east of Shuozhou through Shanyin County to Table 2
Yingxian, which formed a district with a width of 6 km and a length The results of ordered specimen cluster analysis.
of 90 km horizontally. In vertical direction, high arsenic ground- Optimal partition Derivate square Variation coefficient
water is mainly found in a shallow semi-confined aquifer of III phase
(10e50 m) (Xie et al., 2008). The groundwater velocity is about A 26.04 V0/16 h 0.47 0.1648
0.2e0.5 m d1, and is mainly composed of loose alluvial deposits of B 32.83 V0/19 h 0.41 0.1876
the Late Pleistocene and Holocene. A test site was established in C 133.58 V0/82 h 0.28 0.1395
D 196.34 V0/110 h 0.42 0.1929
Shanyin County, which is located on the south of Datong basin (N

Fig. 3. The breakthrough curves of columns with different volume proportion ratio of siderite and river sands.

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4 Z. Wang et al. / International Biodeterioration & Biodegradation xxx (2016) 1e9

adsorption abilities of siderite using the most optimal size deter-
mined by the experiments above. Siderite (0.5 g) with optimal size
was mixed with 50 ml arsenic mimic solution at different con-
centrations (0.5 mg L1, 1 mg L1, 5 mg L1 and 10 mg L1) in a
series bottles in constant temperature incubators (T ¼ 25  C).
The adsorption amount was calculated using the following
equations:
company) was used to observe the superficial characteristics of
siderite. The mineral composition was determined by X-ray dif-
fractiometer (X'pert MPD Pro, Panalytical). The specific surface area
measuring instrument (ASAP 2020, MICROMERITICS) was applied
to analyze the surface mineral morphology. The surface composi-
tion and valence states were obtained by X-ray photoelectron
spectroscopy (VG Multilab 2000 Thermo Fisher).

ðc0  ct ÞV
qe ¼
m 3. Results and discussion
1
where c0 is initial arsenic concentration in mimic solution (mg L ); 3.1. Properties of siderite tailings
ct is the arsenic concentration at some time point (mg L1); V is the
volume of reaction solution (L); m is the mass of siderite (g); qe is The density of tailings used in the test is 3.7e4.0 g cm3 1, and
arsenic loadings on absorbents (mg g1). the hardness (HM) is about 3.5e4.0. The results of X-ray diffraction
results indicated that the granulated tailings contain 85% siderite
2.4. Dynamic leaching tests and 8% ankerite, and powdered tailings contain 65% siderite, which
indicated that the collected tailings are suitable for arsenic removal.
River sands which were common filtration materials in the The results obtained from SEM are presented in Fig. 1. It is
study area were selected as accessories of siderite filter, because: 1) apparent that the mineral structure of siderite assumes a rhom-
river sands can reduce the cost and 2) enhance the integral strength bohedral shape with grain sizes of 1 mme5 mm. The mineral surface
of composite materials. The results of pre-test revealed that river is smooth and regular with several groups of joints, and gaps are
sands had certain abilities for arsenic removal (the adsorption ca- developed which increase the specific surface area significantly.
pacity is 67 mg g1). The river sands were collected in Shanyin The specific surface area analysis (BET) showed that the specific
County, Shanxi province, China. Prior to experiments, the sands
were washed using deionized water for 3 times and sieved into
1~2 mm. Volume proportion coefficients were defined as the vol-
ume ratio of siderite and river sands. The column experiments were
performed in 4 plexiglass columns (5.5 cm diameter, 30 cm length,
labeled as A ~ D) filled with composite materials at different ratios
(a ¼ 1, 0.75, 0.5, 0.25) and compacted in layers. The porosity is
about 0.35. Five liters deionized water was sealed in a closed tank
and deoxidized by passing nitrogen gas into the tank for about
15 min, and then made into mimic arsenic solution with the same
arsenic concentrations as above. Meanwhile, 2 mg NaS2 (AR,
Sinopharm chemical reagent Co. Ltd) was added into the mimic
solution to simulate the high sulfide concentrations in the test site
(400 mg L1). The columns were saturated with deionized water
firstly, then the mimic solution was pumped through the filter bed
with a peristaltic pump at a flow rate of 5 ml min1 after flow field
become steady.
Field leaching tests using high arsenic groundwater were per-
formed at the field site in Shanyin County. The device, process and
method of tests were the same as above. High arsenic groundwater
was collected in the site and arsenic concentration is 587.50 mg L1.

2.5. Analytical methods

All the samples were filtered using 0.45 m microporous mem-

brane (Millipore, USA) and collected in PE bottles. The pH,
Oxidation-Reduction Potential (ORP) and electron conductivity
(EC) in suspensions and column effluents were determined by
portable HQ40 d meter (HACH company, USA), respectively. Redox
sensitive constituents (Fe2þ, NO þ 
2 , NH4 , HS ) were tested by
DR2800 spectrophotometer (HACH company, USA). Bicarbonate
(HCO 3 ) concentrations in the aqueous samples were determined by
using a Gran titration on the same day of sampling. The concen-
trations of cation were determined by ICP-AES (IRIS Intrepid II,
Thermo Elemental) and anions constituents (F, Cl, NO 2
3 , SO4 )
were tested by Ion Chromatography (761 Compact IC, Metrohm).
The concentrations of As(III) and total As were separated using
speciation column (LC-SAXSPE, Supelco) and then quantified by Fig. 4. The structure of drinking well used composite filter material for in-situ
arsenic removal(1- protector platform, 2- concrete base, 3- red clay cover, 4- PVC
double-channel atomic fluorescence spectrometry (AFS-9800, pipe, 5- bentonite bed, 6- permeable hose, 7- bed filtration, 8- double ring positioner,
Beijing Haiguang). 9- precipitation tube, 10- sandy gravel, 11- stainless steel inner-loop, 12- steel bar, 13-
Field emission scanning electron microscopy (SU8010, Hitachi stainless steel outer-loop).

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 Z. Wang et al. / International Biodeterioration & Biodegradation xxx (2016) 1e9 5

surface area of siderite is up to 7.78 m2 g1.
3.2. Batch experiments
Adsorption equilibrium time and capacity of the variable grain
sized materials are shown in Fig. 2. The particles with size of 200
meshes have the lowest adsorption equilibrium time (5 h). There is
a significant positive correlation between sizes and adsorption
equilibrium time, however average adsorption equilibrium capacity
of all the different grain sized materials are between 0.310 and
0.325 mg g1. The low variance coefficient (1.5%) indicated that the
different sizes have no effect on adsorption equilibrium capacity.
The specific surface area can be divided into internal surface area
and exterior surface area, among them exterior surface area is only
a small proportion of the total surface area, and the main contri-
bution comes from internal surface produced by the pore structure.
Several groups, joints and gaps developed on the surface of siderite
can be observed in Fig. 1, which increase the specific surface area
significantly and provided many adsorptive sites. Different sizes
mainly affect the exterior surface area, and more exterior surface
area increases the probability that aqueous arsenic collide with the
solid surface of siderite. However, exterior surface makes a few
contributions to the amount of adsorptive sites, thus it has little
effect on adsorption equilibrium capacity. Therefore, the adsorption
abilities of siderite are not only influenced by sizes or exterior
surface area, but also are closely interrelated to surface structures.
The adsorption equilibrium capacities of size B, size G, size F are
all below 0.31 mg g1, and size F and size G takes longer time
(>100 h) to reach an adsorption equilibrium which results in a weak
applicability for practical use. Size A and size C have an impressive
performance in arsenic adsorption considering the adsorption
equilibrium time and capacity. Nonetheless, the size of filter ma-
terials in sandy layers must be 6e8 times than aquifer media ac-
cording to the technical standard for water-supply well (GB 50296-
99). The media of the target aquifer at field site is fine sand (the
particles with the size >0.075 accounted for 50% of total weight)
and grits (the particles with the size >0.45 accounted for 50% of
total weight), therefore size A and size B are not suitable for

Fig. 5. The monitoring results of the pilot run.

Table 3
The specifications of water-supply well for in-situ arsenic removal.

Index Specification Design foundation Reason

filter material grain(r) 1-2 mm Section 3.2 Considering adsorption equilibrium time, equilibrated adsorption
capacity and clogging
geometrical thickness of filter material(h) aquifer thickness þ30 cm technical standard for Avoiding dislocation between filer material and aquifer due to
water-supply well sedimentation and compaction during filling process
(GB50296-99)
horizontal thickness of filter 30 cm Section 3.3 The length of column in leaching experiments
material (R)
proportional coefficient 0.5 Section 3.3 The results of leaching experiments of different proportional
coefficient
filter length aquifer thickness (30 m) technical standard for To ensure well capacity
water-supply well
(GB50296-99)
borehole diameter 67.5 cm Section 3.3 The sum of horizontal thickness of filter material and central pipe diameter

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application. The adsorption equilibrium capacity of size E is higher
than that of size D, however both of two sizes have the same
adsorption equilibrium time, therefore size E is selected as the
optimal scheme.
Langmuir isotherm yielded a better fit to experimental data with
regard to the siderite with a grain size range of 1e2 mm
(R2 ¼ 0.9826) (Table 1). Langmuir isotherm assumes that the
adsorption process is a reversible phenomenon and the coverage is
monolayer (Altundogan et al., 2000). Therefore the adsorption
processes probably tended to be a monolayer adsorption reaction
and the saturation adsorption capacity is 0.5233 mg g1. KF is the
Freundlich constant denoting the adsorption capacity of the
adsorbent, and n is the adsorption intensity parameter. Values of
0.1 < n < 1 show favorable adsorption of arsenic onto adsorbents
(Namasivayam and Senthilkumar, 1998). 1/n equals 0.5 in this
experiment, which indicated that the adsorption of aqueous arsenic
on the siderite occurs easily and siderite has a stronger capacity for
arsenic adsorption.

Fig. 6. Comparison of common(a) and trace(b) components between effluent and background (The dotted black line means 10% and 50% mass deviation, respectively).

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3.3. Column experiments

X
j
 2 1 Xj

Fig. 3 shows the experimental data on a series columns filled

with composite filtration materials at different volume proportion
ratio. C0 and Ct were defined as the initial arsenic concentrations in
mimic solution and the effluent of the column, respectively. The
pore volume of the column is represented by V0. The breakthrough
curves of all treatments present a trend of the ascent of arsenic
concentrations over time. All the breakthrough curves can be
divided into 3 stages: I- initial phase, II-penetrated phase, and III-
steady phase. The break through point is selected as demarcation
point between initial phase and penetrated phase. The break
through point can be 5%, 10%, or 50% C0 (Srivastava et al., 2008). In
this paper, 5% C0 we selected was selected as the breakthrough
point The arsenic concentrations are low in the effluent at this
phase, but the duration of each treatment show great discrepancy:
A, B, C reach the breakthrough point at 4 h (4.53 V0), 13 h(14.72 V0),
43 h(50.94 V0), respectively. However, D lasts for 98 h (85.40V0),
which shows a significant ability for arsenic removal.
The experimental data after the breakthrough point is stan-
dardized, and then ordered specimen cluster analysis was con-
ducted to determine demarcation point of penetrated phase and
steady phase (as presented in Table 2). The sum of squares of de-
viations represent similarity of classification data and the optimal
segmentation is determined by the minimal sum of squares of
deviations. {Xi, Xiþ1, …Xj} represent a phase after segmentation,
1  i  j  n; Sn (2, j) represents the sum of squares of deviations
after n samples divided into 2 phases. J is the demarcation point.
Therefore the sum of squares of deviations can be calculated using
the following equation:
8 diameter of inner casing pipe is 7.5 cm. The filter length is 1.3 m. The
>
> S ð2 : 1Þ ¼ d11 þ d2n
< n
Sn ð2 : 2Þ ¼ d12 þ d3n
>
> ……………………
: sands were mixed at a volume proportion ratio of 0.5 and then
Sn ð2 : n  1Þ ¼ d1n1 þ dnn
dij ¼ Xa  Xði; jÞ ; Xði; jÞ ¼ Xa
n¼1
j  i þ 1 a¼1
As shown in Fig. 3 and Table 2, the demarcation point between
the breakthrough phase and the penetration phase of different
columns are D (196 h) >C (134 h) >B (33 h) >A (25 h). All the co-
efficients of variation of the steady phase are below 0.2, which
indicates the concentrations vary slightly. The average arsenic
removal rates of different columns are D (90.67%) > C (71.61%) > B
(65.71%) >A (28.18%), which implies that arsenic removal rates can
be higher than 65% when volume proportion ratio a is more than 1.
Considering the efficiency of arsenic removal and economic factors,
the ratio of arsenic removing rate to a is selected as the determi-
nation coefficient to confirm the optimal scheme. The result ob-
tained was as follows: B(1.31)>A(1.13)>C(1.023)>D(0.907), which
implicit that scheme B is the most significant cost-efficient scheme
and could be determined as process scheme of water supply well
for arsenic removal.
3.4. Design of water supply well for arsenic removal and pilot run
Based on the results of above experiments and the technical
standard for water-supply well (GB50296-99), the structure and
specification are designed as shown in Fig. 4. Detailed specification
of the well design can be seen in Table 3.
The pilot run was conducted in Daying test site (N 39 22015.400 , E
112 52018.100 ) in August 2013. The depth of target aquifer is about
23.2 me24.5 m, and thickness is 1.3 m. The aquifer media is dark
grey fine sands including some silt. The depth of borehole is 25.5 m
and aperture is 67.5 cm. The length of sedimentary pipe is 1 m. The
thickness of filtration materials is 30 cm in the horizontal direction
and 1.6 m in vertical direction. 618 kg siderite and 334 kg river
filled into the filter.
After installation, continuous pumping at the flow of

Fig. 7. The concentrations of HCO

3 and total As in the effluent of column experiments in the filed.

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0.76 m3 h1 (average flow of tap water) was conducted to mimic
the practical situation of water use in household. The effluent from
the well was sampled every 20 min, and the whole sampling pro-
cess lasted for 240 min. The average total arsenic concentration is
247.57 mg L1 and arsenic removal rate of 52%e65% was obtained
(see Fig. 5). The variance coefficient was 7.5%, which indicated the
well run steadily. The average As(III) concentration of effluent is
25.24 mg/L, which accounted for 9%e12% total arsenic. Considering
the background value of As(III) which was as high as 262.5 mg/L, this
indicates that the well has a good effect on As(III) removal.
Comparing the major components background concentrations
(Ca2þ, Mg2þ, Naþ, Kþ, SO2  
4 , HCO3 , Cl ) with the effluent water
(Fig. 6a), there are merely no difference of Kþ, Cl, SO2 4 between
the background values and the concentrations in effluent with the
below 10% variation. However, the contents of Ca2þ, Mg2þ, HCO
Naþ increase after treatment. A possible explanation for this might
be that FeCO3 is the main constituent which is closely coexisting
with Ca(Fe,Mg,Mn)(CO3)2. During the process of arsenic removal,
FeCO3 and Ca(Fe,Mg,Mn)(CO3)2. can continuously hydrolyze with
water which results in the increases of Ca2þ, Mg2þ, HCO 3 . The
amount of quarts and feldspar in the river sands for tests exceeded
70%, which indicates that the ascent of Naþ caused by solution of
albite.
Comparing the trace components background concentrations
(Fe, Fe2þ, S2, F, As(III), total As) with the effluent water (Fig. 6b).
There are significant difference of Fe, Fe2þ, S2, F, As(III), total As
between the background values and effluent. Except for Fe, the
mass variation of all the other constituents exceed ±50%. Among
them, F, As(III), total As and S2 decrease significantly after
treatment. Both of modified natural siderite and synthetic siderite
711.1 eV (see Fig. 8), which is close to the energy range of FeCl3
(711.0eVe711.4eV)and FeOOH (711.2eVe711.9eV) (Handbook of X-
ray photoelectron Spectroscopy, 1992). It could be inferred that the
actual speciation of Fe considering its main state is Fe(III) and is
more inclined to be FeOOH. The bending energy of As is 43.84 eV,
and sulfide is the main state of arsenic (43.1 eVe44.0eV). The solid
phase contains 0.27% As and 0.34% S, which indicates that a great
quantity of As and S are fixed from the dissolved phase to the solid
phase. Former studies revealed that the diminishing of As con-
centrations may be related to the formation of As-bearing Fe sul-
fides (Rittle et al., 1995), or the precipitation of As sulfides, e.g.
orpiment (As2S3) and realgar (AsS) (O'Day and Turekian, 2004). In
conclusion, it can be deduced that the chemical environment with
abundant sulfide could improve the ability for arsenic removal of
3, siderite.
4. Conclusion
For further exploration on the application of siderite tailings for
arsenic removal, a series of theory and practice studies was carried
27000
26000
25000
Counts(s)

24000
have a good effect on fluorine removal (Shan and Guo, 2013; Liu
et al., 2010). The fluorine concentration decreases from
23000
1.327 mg L1 to 0.596 mg L1 after treatment. Groundwater
chemical environment with high sulfide concentrations can
enhance the ability of arsenic adsorption, which results in the 22000
descent of sulfide concentrations. The discussion about the mech-
anisms will be given in next section. 21000

3.5. The mechanisms of arsenic adsorption 20000

690 700 710 720 730 740 750
As shown in Fig. 7, the effluent arsenic concentration is less than Bingding Energy(eV)
5% C0 in the first 10 h as arsenic in the injected groundwater was (a)
filtered through the column. After 80 h, the effluent arsenic con-
centration reaches the breakthrough point and then remains stable 2600
at about 260 mg L1. As shown in Fig. 7, HCO 3 and total arsenic
variation have 2 features presented as follows:1) the effluent HCO 3
2400
concentration quickly increases to a stable level (410 mg L1) in
20 h; 2) The input HCO 1
3 concentration (265.54 mg L ) is less than
2200
1
stable concentrations mg L . Severe superficial damage resulted
from the hydrolysis of siderite is observed by FESEM under 2500 2000
Counts(s)

magnification. It is speculated that an interface reaction occurs

during arsenic removal as following: 1800

FeCO3 þ H2 O4≡Fe  OH þ HCO3  1600

The hydrolysis of siderite produces iron oxide hydroxide and 1400

increases the HCO 3 concentrations. Former studies have shown
that iron oxide hydroxide have a significant effect on arsenic 1200
adsorption. Most aqueous arsenic could substitute hydroxyl in the
surface of siderite and form monodentate mononuclear or biden- 1000
tate chelate complexes (Shi et al., 2007), and arsenic could be 30 35 40 45 50
affixed to the solid surface by inner globular complex (Waychunas Bingding Energy(eV)
et al., 1993; Manning and Goldberg, 1996), which leads to the (b)
decrease of arsenic concentration.
The results of XPS revealed that the binding energy of Fe is Fig. 8. The XPS results of As (a) and Fe (b) in adsorption saturation siderite.

Please cite this article in press as: Wang, Z., et al., Application of siderite tailings in water-supply well for As removal: Experiments and field tests,
International Biodeterioration & Biodegradation (2016), http://dx.doi.org/10.1016/j.ibiod.2016.10.029
 Z. Wang et al. / International Biodeterioration & Biodegradation xxx (2016) 1e9
out in this research. The following conclusions can be obtained:
 The particle size of 1~2 mm is selected as optimal scheme
considering the adsorption equilibrium time and capacity, as
well as economic factors and technical standard requirement.
The Langmuir isotherm yielded a better fit to experimental data
which indicated that the processes are generally tended towards
a monolayer adsorption reaction and the saturation adsorption
capacity is 0.5233 mg/g.
 A pilot run of water supply well for arsenic removal performed
on field site obtained a better effect, the average concentration
of effluent after treatment was 247.57 mg/L, and the rates of
arsenic removal were 52%e65%.
 The hydroxyl of Fe(OH)x/FeOOH contributed from the hydroly-
sis of FeCO3 and substituted by aqueous arsenic was likely the
mechanisms for arsenic removal. Groundwater chemical envi-
ronment with high sulfide concentrations enhances the ability
of arsenic adsorption.
Acknowledgement
This research was financially supported by the Ministry of Sci-
ence and Technology of China (2012AA062602).
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