Science of the Total Environment 539 (2016) 97–104
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Science of the Total Environment
journal homepage: www.elsevier.com/locate/scitotenv
Comparison of arsenic and antimony biogeochemical behavior in water,
soil and tailings from Xikuangshan, China
Zhiyou Fu a, Fengchang Wu a,⁎, Changli Mo b, Qiujing Deng c, Wei Meng a, John P. Giesy d,e
a
State Key Laboratory of Environmental Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012, China
Teaching Equipment and Laboratory Management Center, Guiyang University, Guiyang 550005, China
c
College of Resources and Environmental Engineering, Guizhou University, Guiyang 550002, China
d
Department of Veterinary Biomedical Sciences and Toxicology Centre, University of Saskatchewan, Saskatoon, SK, Canada
e
Zoology Dept. and Center for Integrative Toxicology, Michigan State University, East Lansing, MI 48824, USA
b
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
• As and Sb are generally thought to have
similar geochemical behavior.
• A multi-media field study was conducted
to compare their biogeochemical behavior.
• Different spatial and temporal variation
in tailings associated with changes in pH
• Bio-accumulation factors of As ~10-fold
greater than those of Sb.
• Sb accumulation N than As into nonfatty tissues such as gills and shells.
a r t i c l e
i n f o
Article history:
Received 25 June 2015
Received in revised form 30 August 2015
Accepted 30 August 2015
Available online xxxx
Editor: D. Barcelo
Keywords:
As
Sb
Mobility
Bioaccumulation
Mining/smelting
Metal
⁎ Corresponding author.
E-mail address: wufengchang@vip.skleg.cn (F. Wu).
http://dx.doi.org/10.1016/j.scitotenv.2015.08.146
0048-9697/Published by Elsevier B.V.
a b s t r a c t
Although similar geochemical behaviors of arsenic (As) and antimony (Sb) in the environment has been assumed
and widely reported, growing evidence suggests the two elements cannot, under some conditions, be assumed to
behave similarly. In this four-year study (samples collected in each year), comparative investigation of the biogeochemistry of As and Sb in water/fish, soil/vegetable, tailings/plant samples were carried out at the world's
largest active Sb mine area (Xikuangshan, China). Depending on duration the tailings had been stacked, significant differences in spatial distributions between As and Sb were found, and these were associated with change in
pH over time. Bio-accumulation factors (BAFs) of As were approximately 10-fold greater than those of Sb in fish/
water, plant/tailing, and vegetable/soil systems. Sb had higher BAF in non-fatty tissues such as gills of fishes and
shells of crabs. BAFs of Sb in vegetable/soil exhibited insignificantly, but different from As, positive correlation
with pH in soil.
Published by Elsevier B.V.
98
Z. Fu et al. / Science of the Total Environment 539 (2016) 97–104
1. Introduction
Both arsenic (As) and antimony (Sb) have been listed as priority
pollutants of interest by both the United States and European Union
(EU, 1976; USEPA, 1979). Potential toxicity and risks to health of
humans prompted concerns over their biogeochemical behaviors
(Abernathy et al., 1999; Ahmed et al., 2006; Amarasiriwardena and
Wu, 2011; Filella et al., 2002; Gebel, 1999; Shotyk et al., 2005). Arsenic
is mainly associated with Sb as a sulfide or oxide (Hale, 1981; Hawkes
and Webb, 1962; Li and Thornton, 1993). Arsenic has attracted wide attention due to its natural presence in high concentrations in some areas
such as in Bangladesh and West Bengal (Chowdhury et al., 2000; Frisbie
et al., 2002). In contrast, the relative abundance of Sb in most matrices is
generally small (e.g., less than 1 mg/kg in chondrite, basic rocks, carbonates, less than 10 mg/kg in soils, and less than 1 μg/L in unpolluted
water) (Filella et al., 2002; Smith and Huyck, 1999). However, world
annual production of Sb is approximately 4-fold greater than that of
As. Antimony is used in batteries, flame retardants, paints, semiconductors, low friction metals, paints, ceramics, and other things. The annual
output of Sb from mines in the past 20 years was 127,800 tonnes compared to 47,020 tonnes for As (USGS, 1995-2013). Pollution with Sb is
getting worse in certain cities. For instance, the concentration of Sb in
particles in the atmosphere of Tokyo, Japan is at least 2-fold greater
than that of As (Zheng et al., 2000).
Both As and Sb are group V elements, and have been assumed to
have comparable geochemical behavior and toxicity. Tremendous effort
has been devoted to understanding the biogeochemical behavior of As
(Abernathy et al., 1999; Dixit and Hering, 2003; Seyfferth et al., 2010),
whereas research specific to Sb is limited. Due to the absence of sufficient experimental data for Sb, it has been common practice to extend
the observed behavior of As (uptake, tolerance mechanisms, methylation) to Sb on the basis of the chemical similarities that exist between
the two elements (Filella et al., 2007). However, As and Sb have different coordination (e.g., their different atomic size), which would result
in different biogeochemical behavior. In fact, growing evidence also suggested the two metalloids cannot, under some conditions, be assumed
to behave similarly (Leuz et al., 2006b; Tschan et al., 2009; Wilson
et al., 2010). This is a challenge for interpreting behaviors of Sb based
on behavior of As. For instance, Sb was predominantly present as
Sb(V), while As was present as a mixture of As(III) and As(V) in the
water (Ritchie et al., 2013) and soil–water system (Mitsunobu et al.,
2006) in the vicinity of Sb mine.
Here a four-year field study (2007–2012) was conducted in
Xikuangshan (XKS), Hunan Province, China, which is the largest active
Sb mine in the world and is nicknamed the “World's Antimony Capital”.
Many studies have been carried out in this area to understand the environmental behavior of Sb (Basnet et al., 2014; Fu et al., 2010; He, 2007;
Liu et al., 2011; Liu et al., 2010; Okkenhaug et al., 2012; Qi et al., 2011;
Wang et al., 2011; Wei et al., 2011; Wu et al., 2011). However, systematic comparison research focused on behavior between As and Sb in
different environmental compartments are limited. The primary objective of this study was to compare the biogeochemical behavior of As
with that of Sb in natural waters, soils and tailings. This study is based
on the null hypothesis that As and Sb have different biogeochemical behavior under some conditions in the environmental compartments.
China is one of the largest producers of Sb in the world, producing, on
approximately 80% of global requirements (He et al., 2012; USGS, 2012).
2. Materials and methods
2.1. Site description
The studied site, the Xikuangshan mining area, covers 70 km2, is situated between 27.7°N and 111.4°E in Hunan Province, in southwest
China (Fig. 1). The XKS Sb mine is located on a large Sb deposit. The
Sb deposit, which is about 2 km wide and 9 km long, sits in the northern
part of the Xiangzhong Basin, a specific low-temperature mineralization
depression zone with rich deposits of mercury (Hg), gold (Au), zinc
(Zn), lead (Pb), As, Sb, and coal (Fan et al., 2004; Liu et al., 2010). Stibnite
(Sb2S3) is the main ore mineral. The deposit also contains trace levels of
pyrite (FeS2), pyrrhotite (Fe1 − xS), and sphalerite (ZnS) with primary
gangue minerals such as quartz and calcite, and secondary such as barite
and fluorite (Fan et al., 2004). The Sb mining history in Xikuangshan
dates back to the nineteenth century with the first Sb smelter being constructed in 1897 and mining operations continue today. Qing river, a
tributary of the Zi river, flows through the XKS mine area and receives
a component of the mining and smelting drainage. Consequently,
there are not any aquatic organisms downstream of the river. In contrast, fish and other aquatic organisms can be found in some small reservoirs (the main sampling sites of for waters and aquatic organisms)
(Fig. 1, sites A-I) with no direct mine drainage input. There is no constructed boundary between the mining and residential areas. Lands in
the mining area are extensively used for cultivation. Vegetables from
these agricultural lands (the main sampling sites of soils and vegetables) (Fig. 1, sites S1–S8) supply most of the local residents. In the ore
separation and smelting processes, huge amounts of ore-dressing residues, tailing particles, and smelter furnace clinkers are produced.
These residues still contain high levels of Sb and other heavy metal contents compared to the uncontaminated environment. The tailings
mixed with soils were either piled up untreated in the open air. Surprisingly, some plants can survive in such harsh environment (the main
sampling sites of tailings and plants) (Fig. 1, sites T1–T6). More detailed
information on the local environmental setting is available elsewhere
(Fu et al., 2010; He, 2007; Liu et al., 2010; Wu et al., 2011).
2.2. Sample collection
In the vicinity of the XKS smelter, a total of 75 water, 104 fish,
12 crab, 81 soil, 138 vegetable, 50 tailing and 135 plant samples were
collected in December 2007, July 2008, December 2008, July 2009 and
July 2012. Fish and corresponding samples of water (filtered with
0.45-μm filtration membranes in the field) were collected from 9 sites
including rivers, ponds, reservoirs and paddy field with different distances from Sb smelting site (Fig. 1, Supplementary Material (SM)
Table S1). Crabs (Portunus pelagicus) were collected in the river at site
B. Fish included local common species, such as carp (Cyprinus carpio),
grass carp (Ctenopharyngodon idellus), crucian (Carassius auratus) and
wild carp (Hemiculter leucisculus). Vegetables and corresponding samples of soil (at 0–20 cm depths of the vegetable rhizosphere) were collected from 8 local agricultural lands near Sb smelter, tailing and
residential site (Fig. 1, SM Table S2). Vegetables included leaf, tuber vegetables, and fruit. Three samples of soil were collected for comparison
from agricultural lands in the control area of Guiyang City, located in
southwest of China. Plants and corresponding samples of tailings were
collected from 6 tailing heaps with different heaped time (Fig. 1, SM
Table S3). Samples of tailings were sampled at both the top and the
bottom of each tailing heap. Samples of plants included most of the
wild plants observed to grow on tailings.
2.3. Preparation of sample and analytical methods
Samples were immediately stored in ice-packed coolers and
transported to the laboratory where they were stored at − 20 °C for
fish samples and 2 °C for water samples. Samples of soils and tailings
were air-dried at room temperature and ground to pass a 100 meshes
sieve (i.e. 0.15 mm sieve size). Individual fish (thawed), vegetable and
plant samples were rinsed individually with tap water and deionized
water to remove possible metal contaminants. Fish organs including
gill, liver, kidney, muscle, swim bladder, and skin were dissected out
with a stainless steel scalpel. Crabs were divided into crab shells and
other tissues after removal of the viscera. Vegetable and plant are divided into ground and underground parts. The separated portions of fishes,
Z. Fu et al. / Science of the Total Environment 539 (2016) 97–104
99
Fig. 1. Map of the field study area with descriptions.
vegetables, and plants samples were washed again with deionized
water, freeze-dried (fishes and crabs) or oven dried at 40 °C for
96-hour (vegetables and plants) and ground into powders.
Measurements of the pH of water samples occurred in the field
with a portable pH meter of PHBJ-260 (Shanghai Leici, China). For
soil and tailing samples pH was measured at solid/water ratio of
1:2.5 by use of PHS-3C pH meter (Shanghai Leici, China). Dissolved organic carbon (DOC) of water samples was measured by use of a High
TOC II analyzer (Elementar, Germany). Organic matter (OM) of the
soil samples were determined using the standard method described
by Lu (Lu, 2000). The OM of tailings were not determined for all
samples due to small contents in tailings (b10 g/kg) and the results
of preliminary sampling indicated there was no statistical difference
between samples.
Total concentrations of Sb and As were determined by use of hydride
generation-atomic fluorescence spectrometry (HG-AFS) with AFS-810
(Beijing Jitian, China) and PSA-10.055 (Millennium Excalibur System,
United Kingdom). Operating conditions of AFS instrument were
optimized and all calibration curves demonstrated good linearity (r N
0.999). Briefly, approximately 0.1 g aliquots of each biological sample
were digested with 3 mL of high purity HNO3 and H2O2 (3/1, v/v) in
acid-cleaned digestion vessels and approximately 0.5 g of each sample
of soil or tailings were digested with 10 mL of HNO3 and H2SO4
(1:1, v/v) and a few drops of HF. These samples were digested by
heating (b140 °C) in acid-cleaned digestion vessels (soil and tailings
were digested in Teflon vessels) (for detail, see reference Fu et al.,
2010; Wu et al., 2011). Digested samples were made up to 10 mL volume with Milli-Q water and left for 30 min until determination. All
chemical reagents used were purchased from Sinopharm Chemical
Reagent Co., Shanghai, China, except KBH4 (Sigma Chemical Co.,
St. Louis, MO., USA) and KI (Tianjin Fuchen Chemicals Reagents Co.,
Tianjin, China). All precautions were taken in order to avoid any crosscontamination during the process.
Quality control included the analyses of method blanks, blank spikes,
matrix spikes, blind duplicates and certified materials (CRMs). The
CRMs included DOLT-3 (Dogfish liver) from National Research Council,
Canada. Other CRMs obtained from the National Research Centre
for Certified Reference Materials (China) were yellow-fin tuna
(GBW08573), bush leaves (GBW07603), tomato leaves (ESP-1) and yellow red soils (GBW07406). The recoveries (Measured value/Certified
value × 100%) for As and Sb in CRMs were in the range of 91–115%
and 87–108%, respectively. All method blanks were observed to be
below corresponding As and Sb detection limits (b10 ng/L for both As
and Sb). The percentage of recoveries on spikes samples ranged from
93 to 110% for As and from 84 to 115% for Sb in all samples. The relative
standard deviation (RSD) of duplicated samples was less than 7% for
both As and Sb in samples. All samples with outliers were analyzed
again by repeating the digestion and measurement procedure.
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2.4. Statistical analyses
The statistical package SPSS for windows 16.0 (SPSS Inc., Chicago,
Illinois, USA) was used for data analyses. Geometric means were used
to describe the level of concentration of metals. Correlation coefficients
were studied using Pearson and Spearman's correlation analysis. In detail, normality of data was confirmed by the Kolmogorov–Smirnov test.
Data on the normal distribution were analyzed by use of Pearson
correlation, while data on the non-normally distribution were analyzed
by use of Spearman's correlation (non-parametric statistics).
Independent-sample T-tests were performed to test the significance of
different environmental compartments. Statistical tests were considered statistically significant if P b 0.05.
3. Results and discussion
3.1. Distribution of As and Sb
Concentrations of As and Sb in the XKS waters with means of 2.48
(0.51–12.0) μg/L and 24.7 (5.59–163) μg/L, respectively. Approximately
18% and 95% of samples of water from the Sb mine area had concentrations of As and Sb that exceeded Chinese drinking water guidelines (As:
10 μg/L, Sb: 5 μg/L) (GB5749-2006, 2006) (Table 1). These values were
significantly higher than those in river near Sb mine in Turkey
(Sb:0.02–0.1 μg/L) (Duran et al., 2007), closed to those in river near
abandoned Sb mine in New Zealand (As: 5.5–8.6 μg/L, Sb: 14–30 μg/L)
(Wilson et al., 2004), but lower than those in stream (mine drainage
input) adjacent to a Sb mine in Australia (As:46 ± 2 μg/L, Sb: 381 ±
23 μg/L) (Telford et al., 2009) and previously reported in XKS (Liu
et al., 2010) due to no direct mine drainage input in our water sampling
sites.
Concentrations of As and Sb in the XKS soils with means of 69.8
(14.9–208) and 1315 (141–8733) mg/kg, dry mass (dm), respectively,
were close to previously reported concentrations of As (3.5–
205.1 mg/kg) and Sb (101–5045 mg/kg) in soil of XKS (He, 2007). Soil
As and Sb concentrations in this study were significantly (p b 0.01)
greater than those from the control sites with mean less than
20 mg/kg, dm (Table 1), and greater than the second grade standard
value of As (25–40 mg/kg) in China environmental quality standard
for soils (GB15618-1995,1995) (Sb is absent in this standard).
Greatest concentrations of As and Sb were found in tailings with
means of 169 (29.1–853) and 3789 (684–17196) mg/kg, dm, respectively, which were twice as great as those in soils (Table 1). This results
suggested that tailings piles are a potential important source of As and
Sb in water and soils due to fact that the tailings were piled up untreated
in the open air without constructed boundary with the soil. Another
study reported in this area (Zhu et al., 2009) also suggested that interactions between water and tailings are important process controlling release and transport of As and Sb from mining/smelting sites into the
streams.
Concentrations of both As and Sb in waters and soils were inversely
proportional to distance from the Sb smelter. Concentrations of As and
Sb were approximately 10-fold greater in water from within 1.5 km of
the Sb mine than concentrations 3–8 km from the smelter (Fig. 2a, the
circled area). Concentrations of As and Sb in soils from sites S1, S2, S3
and S6, near the Sb smelter and tailings, were greater than those in
other soils in the region (Table 1). These results indicated that concentrations of Sb and As in water and soil of the vicinity of the Sb mine
Table 1
Chemical parameters and concentrations of As and Sb in XKS water, tailings and soil.
Water
Sampling site
na
As (μg/L)
A
B
C
D
E
F
G
H
I
6
15
9
6
9
6
9
9
6
1.68 (1.62–1.74)
11.1 (10.8–11.8)
8.91 (7.03–12.0)
6.60 (3.46–10.3)
1.65 (0.94–2.40)
0.69 (0.65–0.73)
0.56 (0.51–0.60)
1.16 (1.03–1.38)
4.41 (3.9–5.34)
Sampling site
n
As (mg/kg)
T1
T2
T3
T4
T5
T6
9
9
8
11
7
6
Sampling site
S1
S2
S3
S4
S5
S6
S7
S8
Control site
Sb (μg/L)
pH
DOC (mg/L)
7.30 (6.93–7.40)
7.36 (6.86–7.66)
6.21 (5.78–6.47)
7.16 (6.83–7.50)
7.43 (7.22–7.60)
6.95 (6.52–7.21)
7.25 (6.79–7.62)
7.37 (7.35–7.40)
7.40 (7.08–7.73)
2.27 (2.06–3.01)
1.23 (0.89–1.31)
1.27 (0.99–1.40)
6.15 (2.26–9.86)
1.39 (0.96–1.64)
0.95 (0.63–1.28)
2.52 (2.05–3.52)
2.66 (2.32–2.96)
2.04 (1.72–2.42)
Sb (mg/kg)
pH
OM (g/kg)b
116 (62.9–170)
161 (131–181)
103 (80.9–128)
217 (29.1–853)
226 (40.1–435)
251 (106–363)
5662 (2181–8226)
2463 (1322–4067)
1784 (1391–2167)
6495 (684–12581)
8784 (3132–17196)
2087 (1349–4438)
7.16 (6.51–7.75)
4.78 (4.01–5.65)
6.72 (6.39–7.02)
7.28 (6.27–7.93)
7.41 (7.03–7.67)
7.52 (6.98–7.74)
b10 g/kg
b10 g/kg
b10 g/kg
b10 g/kg
b10 g/kg
b10 g/kg
n
As (mg/kg)
Sb (mg/kg)
pH
OM (g/kg)
9
12
8
6
8
6
16
13
3
91.5 (83.7–113)
101 (84.9–133)
103 (66.4–152)
29.3 (28.4–30.1)
43.6 (14.9–72.3)
169 (96.7–208)
60.5 (19.9–169)
45.5 (19.1–141)
12.7 (9.00–16.82)
4544 (2548–6087)
6070 (2356–8733)
1438 (524–2303)
404 (391–425)
248 (141–355)
6946 (3978–8623)
827 (157–4237)
392 (197–547)
3.23 (2.32–4.56)
6.42 (5.62–7.08)
5.44 (5.27–6.13)
6.82 (6.60–7.01)
6.93 (6.70–7.15)
5.98 (6.94–5.02)
7.46 (6.92–7.78)
6.94 (5.38–7.41)
6.36 (5.67–6.99)
6.78 (5.19–7.64)
45.5 (29.8–69.7)
79.9 (41.1–111.5)
78.7 (51.0–139.8)
31.1 (29.5–32.5)
46.9 (20.5–73.3)
17.3 (12.6–28.5)
36.6 (19.7–65.1)
55.2 (37.6–73.2)
54.4 (36.8–74.2)
81.8 (76.6–8.7)
90.7 (65.8–140)
156 (151–163)
43.7 (10.3–80.0)
6.67 (5.59–7.93)
8.70 (7.88–9.53)
10.4 (10.3–10.4)
8.66 (7.78–9.36)
13.2 (11.6–15.0)
Tailing
Soil
a
n refers to the number of samples.
The OM of tailings were not determined for all samples due to small contents in tailings (b10 g/kg) and the results of preliminary sampling indicated there was no statistical difference
between samples.
b
Z. Fu et al. / Science of the Total Environment 539 (2016) 97–104
101
Fig. 2. Correlations between concentrations of Sb and As in XKS area.
area were seriously affected by Sb smelting and mine waste management activities. Deposition of As and Sb in dust and percolation of tailing
leachate were suggested as the primary mechanisms of transport.
Despite the similarities of spatial distributions between As and Sb in
waters and soils, differences in distributions of As and Sb in tailings were
observed as a function of time (Fig. 3). In heaps of tailings that were 5 to
10 years old, concentrations of Sb in tailings on top were always greater
than those at the bottom of heaps of tailings. In contrast, concentrations
of As in tailings on the top of the heap decreased as a function of time
while those near the bottom increased. No significant differences in
concentrations of Sb were observed in tailings between different
heaped years. In contrast, concentrations of As in tailings near the top
of heaps that were 15 years old were significantly less than those in tailings that had weathered for 5 years. The different temporal distributions
of As and Sb observed in tailings suggested that mobility of Sb was less
than that of As. Recently less mobility of Sb than As were reported in soil
of Pb–Sb mining area: Sb was found mostly (97.6 to 99.6%) in the residual fraction of soil, whereas the residual fraction of As (58.3–98.8%) was
lower (Álvarez-Ayuso et al., 2012).
Significantly positive correlations between concentrations of As and
Sb were observed in water (r = 0.757, p b 0.01), soils (r = 0.512, p b
0.01), and tailings (r = 0.596, p b 0.01) (Fig. 2), suggesting common
sources as well as similar environmental behavior of As and Sb in XKS.
Similar broad correlations between concentrations of As and Sb in environmental compartments have been reported. For instance, similar seasonal variations in surface water (Masson et al., 2009), similar mobilized
Fig. 3. Distribution and temporal trends in concentrations of As and Sb in tailings. Independent-sample t tests: (1) top and bottom tailings: heaped 5 years, As: p = 0.023**, Sb: p =
0.001**; heaped 15 years, As: p = 0.211, Sb: p = 0.003**. (2) 5 and 15 years: top tailings,
As: p = 0.003**, Sb: p = 0.279; bottom tailings, As: p = 0.005**, Sb: p = 0.011**.
mechanism in groundwater (Willis et al., 2011), and similar little mobilization in soil leached by deionized water (Müller et al., 2007).
3.2. Biological accumulation of As and Sb
Concentrations of As in the XKS fishes, plants and vegetables with
means of 86.8 (1.0–1112) μg/kg, 13.5 (0.14–609) mg/kg and 2.32
(0.08–10.7) mg/kg, dry mass (dm), respectively. Concentrations of
Sb in the XKS fishes, plants and vegetables had means of 59.8 (1.01–
1937) μg/kg, 13.4 (1.31–91.0) mg/kg and 14.1 (0.38–84.1) mg/kg, dry
mass (dm), respectively. Sb concentrations in vegetables were closed
to the concentrations reported by He (2007) in leaves of radish plants
from the same area (1.5–121 mg/kg). But Sb concentrations in plants
were substantially lower than the concentrations reported by
Okkenhaug et al. (2011) from the same area (109–4029 mg/kg). Bioaccumulation potentials of As and Sb were clearly different. Although concentrations of As in waters, tailings and soils were approximate an order
of magnitude less than those of Sb, concentrations of As in fishes, plants
and vegetables were generally close to that of Sb (SM Table S4). The Bioaccumulation factors (BAFs, i.e. organism/exposure source concentration ratios to reflect the bioavailability of metal) calculated for As were
approximate 10-fold greater than those of Sb in fish/water, plant/tailing
and vegetable/soil systems (Fig. 4, SM Table S4), which suggests that As
and Sb might be bioaccumulated via different mechanisms. Fish, plants
and vegetables all tended to accumulate As but not Sb. Relatively low
bioavailability of Sb has been reported in soils and plants (Hammel
et al., 2000; He, 2007), in grass and small mammals (Ainsworth et al.,
1990b), in soils and human (Gebel et al., 1998), in sediments and aquatic plants (Telford et al., 2009), in waters and fishes (Fu et al., 2010). Our
observations suggested lower bioavailability of Sb than As in fish/water,
plant/tailing and vegetable/soil (Table 2).
Distributions of bioaccumulation were generally similar for As and
Sb. Both elements tended to be more accumulated by common carp
(H. leucisculus and C. carpio) than grass carp (C. idellus) (n = 31,
p b 0.05) (Fig. 4a). This suggested that the grass carp (herbivorous
fish), which mainly inhabit the surface layer of aquatic environments,
had less access to greater concentrations of Sb in sediments (Filella
et al., 2002; Fu et al., 2010). Both elements tended to be more accumulated by leafy vegetables than other vegetables (Fig. 4c). This suggested
those leaves that have been directly affected by deposition of Sb and
from the atmosphere in the region around XKS. In fact, previous studies
have reported that concentrations of Sb in leaves in XKS and other areas
with ongoing Sb smelting operations are usually greater than those in
the roots (Ainsworth et al., 1990a; He, 2007), but no significant difference in concentrations of Sb between leaves and roots was observed
in areas near an abandoned Sb mine (Baroni et al., 2000). Both As and
Sb exhibited significant accumulation in plants of the family
Pteridaceae, including Pteris vittata and Pteris henryi (Fig. 4b). This is
not surprising due to P. vittata has been demonstrated as to be a
hyper-accumulator of As (Ma et al., 2001). But our results indicated
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Table 2
Concentrations of As and Sb in XKS fish, plant and vegetables (expressed in geometric
means of concentrations in all the organism parts).
Fish
Sampling site
na
A
C
D
E
F
G
H
I
7
24
14
21
2
13
15
8
As (μg/kg)
175 (156–188)
277 (25.8–690)
43.2 (1.00–147)
84.6 (5–1112)
94.1 (18.4–202)
73.6 (16.7–179)
63.1 (14.8–151)
41.6 (10.2–79.7)
Sb (μg/kg)
339 (207–537)
602 (237–1937)
38.8 (2.21–191)
62.5 (1.80–1173)
14.1 (1.01–31.9)
31.5 (2.28–79.9)
29.3 (2.61–122)
25.3 (1.46–88.0)
Plant
Sampling site
n
T1
T2
T3
T4
T5
T6
26
22
19
27
23
18
As (mg/kg)
47.5 (1.83–609)
7.23 (1.78–14.5)
3.80 (0.23–11.8)
9.19 (0.14–78.4)
31.1 (0.69–519)
16.1 (0.78–71.5)
Sb (mg/kg)
11.2 (1.31–44.6)
9.56 (4.53–18.4)
6.58 (1.71–27.7)
18.9 (2.24–67.8)
17.2 (1.76–75.1)
25.2 (4.41–91.0)
Vegetables
Sampling sites
n
As (mg/kg)
Sb (mg/kg)
S1
S2
S3
S4
S5
S6
S7
S8
18
18
15
11
8
15
23
30
3.85 (0.34–5.59)
4.36 (0.19–8.63)
3.68 (0.43–10.7)
3.26 (0.46–8.99)
1.41 (0.14–6.74)
3.77 (0.19–10.1)
0.813 (0.33–2.30)
0.975 (0.08–7.06)
17.0 (1.59–43.1)
30.0 (1.15–55.2)
20.6 (2.11–69.3)
14.6 (1.18–31.2)
10.2 (0.400–49.8)
30.8 (1.58–84.1)
3.65 (0.55–13.0)
9.04 (0.38–30.3)
a
Fig. 4. BAFs of As and Sb in XKS area (a: fish/water at different sites; b: plant/tailings in different family of plant; c: vegetable/soil in different species of vegetables). BAFs of As and
Sb in organisms were calculated in accordance with concentrations of metal in mixed biological samples. The vegetables in this figure refer to the edible part of vegetable samples.
that P. vittata is not an hyper-accumulator for Sb due to BAFs of Sb were
less than 1 (geometric mean of 0.031).
Accumulation of As and Sb varied among biological tissue of fish and
crab samples. Arsenic was preferentially accumulated into liver and kidney of fishes (SM Figure S1), which were recognized as the excretory
and detoxification organs. In contrast, greatest accumulations of Sb
were found in non-lipid tissues such as gills of fishes (n = 27) and shells
of crab (n = 12), whereas As was not (Fig. 5). There should be receptors
biological ligands for Sb in non-lipid tissues, but the mechanism remains
unclear. Our results were consistent with previous results: Lower concentrations of Sb were reported in fat compared to brain, kidney, liver
and spleen of rats (Poon et al., 1998), whereas significant amounts of
n refers to the number of samples.
As were concentrated in the fat fraction rather than in the non-lipid
fractions in tissues of sheep (Devalla and Feldmann, 2003).
Soils exhibited a range of pH values from 5.19–7.78. BAFs for accumulation of Sb from soil to vegetables were positively correlated with
the pH of soil for both cabbage (r = 0.164, p N 0.05) and radish (r =
0.487, p N 0.05), the dominant local vegetables (Fig. 6). The statistically
insignificant correlations suggested that BAFs of Sb in vegetable/soil
were affected by other importance factors as well (e.g., genotype, soil
type, the properties of phytochelatins), that has not been addressed in
the present study. In contrast, As exhibited the opposite trend for both
cabbage (r = − 0.412, p N 0.05) and radish (r = − 0.223, p N 0.05)
(Fig. 6). Positive correlations between Sb bioavailability and pH in soil
were in agreement with the previous reported results (Hammel et al.,
2000) that the mobility of Sb decreases with decreasing acidity of the
soils. This suggested that the co-precipitation and adsorbed
Sb(V) (including easily and rapidly oxidized Sb(III)) on iron-minerals,
the main mineral composition of Sb ores in XKS (Fan et al., 2004),
would be released with increasing pH especially at pH values above
pH 7 (Leuz et al., 2006a; Leuz et al., 2006b; Ritchie et al., 2013).
Although Sb exhibited positive correlations between concentrations
of Sb in tailings and in the corresponding plants of the family
Loganiaceae (Buddleja davidii) (r = 0.645, p N 0.05), the dominant
local wild plant, significantly negative correlations were found between
concentrations of As in tailings and in family Loganiaceae (r = −0.581,
p b 0.01) (SM Figure S2). This suggested that accumulation of As into
wild plants was not dependent on total concentrations of As in tailings,
which can be attributed to the strong mobility of As and variation of pH
in tailings. Concentrations of As in surface tailings were inversely proportional to duration they had been stacked (Fig. 3) and accompanied
acidification of the tailings due to the sulfide contained in the tailings.
The pH in surficial tailings that had been heaped for only one year was
7.28. In contrast, the average pH of surface tailings that had been weathered for 15 years was 4.28 due to H2SO4 generated from oxidation of
Z. Fu et al. / Science of the Total Environment 539 (2016) 97–104
103
Fig. 5. Bio-accumulation factors (BAFs) of As and Sb in biological organs/water.
sulfide minerals in tailings. As a result, although concentrations of As in
surface tailings decreased with duration of stacking, bioavailability of As
increased due to the lower pH. Hence As exhibited a significantly negative correlation between concentrations in Loganiaceae and tailings.
This supported the higher mobility of As than Sb in tailings discussed
in the above section of “distribution of As and Sb”.
fish/water, plant/tailing and vegetable/soil systems. Sb was more accumulated than As into non-fatty tissues such as gills of fishes and shells of
crabs. BAFs of Sb and As in vegetable/soil exhibited different insignificantly positive correlation with pH in soil. Changes in pH were also
found to be a significant factor influencing different mobility of As and
Sb over time.
4. Conclusion
Acknowledgments
In this study, significant differences in mobility, bioavailability and
bioaccumulation distribution between As and Sb were observed. Different temporal distributions of As and Sb observed in tailings suggested
that mobility of Sb was less than that of As. Bio-accumulation factors
(BAFs) of As were approximately 10-fold greater than those of Sb in
This work was jointly supported by National Natural Science Foundation of China (41473109, 41003047 and 41373027) and National
Basic Research Program of China (2008CB418200). The authors wish
to thank Dr. Jianyang Guo and Dr. Yongsan Zhang for their help during
the sampling process.
Fig. 6. Correlations between soil pH and BAFs of As and Sb in cabbage and radish.
104
Z. Fu et al. / Science of the Total Environment 539 (2016) 97–104
Appendix A. Supplementary data
Supplementary data to this article can be found online at http://dx.
doi.org/10.1016/j.scitotenv.2015.08.146.
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Supplementary Material
Comparison of arsenic and antimony biogeochemical behavior in
water, soil and tailings from Xikuangshan, China
Zhiyou Fu,a Fengchang Wu, a,* Changli Mo,b Qiujing Deng,c
Wei Meng,a John P. Giesyd,e
a
State Key Laboratory of Environmental Criteria and Risk Assessment, Chinese Research
Academy of Environmental Sciences, Beijing 100012, China
b
Teaching Equipment and Laboratory Management Center, Guiyang University, Guiyang 550005,
China
c
College of Resources and Environmental Engineering, Guizhou University, Guiyang 550002,
265647 China
d
Department of Veterinary Biomedical Sciences and Toxicology Centre, University of
Saskatchewan, Saskatoon, Saskatchewan, Canada
e
Zoology Dept. and Center for Integrative Toxicology, Michigan State University, East Lansing,
MI 48824, USA
*Professor Fengchang Wu will be the corresponding author for this paper
Phone: +86-010-84915312
Fax: +86-010-84931804
E-mail: wufengchang@vip.skleg.cn
1
Table S1. Number of samples and sampling site description of water-fish system
Site
Site name
Sampling date
A
Nankuang
Jul.2008, July 2012
B
Shuichang
C
Dec.2007, Jul.2008,
July 2012
Dec.2007, Jul.2008,
Shuichang
July 2012
D
Yangjia
Dec.2007, Jul.2008
E
Shengli
Dec.2007, Jul.2008,
July 2012
F
Shengli
Jul.2008
G
Fuyuan
Jul.2008, July 2012
H
Minzhu
Dec.2007, Jul.2008,
July 2012
I
Tongxing
Jul.2008, July 2012
Site descriptions
Pond 1km from the Sb
smelting site
River 1km from the Sb
smelting site
Reservoir 1km from the
Sb smelting site
Pond 1.5km from the Sb
smelting site
Reservoir 3km from the
Sb smelting site
Paddy field 3km from the
Sb smelting site
Reservoir 4km from the
Sb smelting site
Reservoir 5km from the
Sb smelting site
Pond 8km from the Sb
smelting site
* Crab were collected in this site where no fish was sampled.
2
Water
Fish
Common name (species) of fish
6
7
15
12*
Crab (Portunus pelagicus)
9
24
Crucian,
Grass carp (Ctenopharyngodon idellus),
Wild carp (Hemiculter leucisculus）
6
14
Crucian, Grass carp
9
21
Grass carp, Crucian,
Peters)
6
2
Grass carp
9
13
Grass carp, Crucian, Carp (Cyprinus carpio)
9
15
Grass carp, Crucian, Bighead crap (Aristichthys
mobilis)
6
8
Grass carp,Herring
Crucian (Carassius auratus)
Herring (Mylopharyngodon
Table S2. Numbers of samples and sampling site description of soil-vegetable system
Site
Site name
Sampling date
Site descriptions
Soil
Vegetable
S1
Beikuang
July 2008, July
2009, July 2012
Vegetable field near abandoned ore
9
18
S2
Beikuang
July 2008, July
2009, July 2012
Vegetable field near northern
smelter of Sb (distance≤1 km)
12
18
S3
Nankuang
July 2008, July
2009, July 2012
8
15
S4
Nankuang
July 2008, July
2009, July 2012
6
11
S5
Weishaba
July 2008, July
2009, July 2012
Vegetable field near southern
smelter of Sb (distance≤1 km)
Vegetable field of residential area
near southern smelter of Sb
(distance≤1.5 km)
Vegetable field downstream of the
tailing dam (distance≤1 km)
8
8
S6
Shuichan
g
July 2008, July
2009, July 2012
Vegetable field below the tailing
and abandoned ore (distance≤0.3
km)
6
15
S7
Yangjia
July 2008, July
2009, July 2012
Vegetable field near southern
smelter of Sb (distance≤2 km)
16
23
S8
Yangjia
July 2008, July
2009, July 2012
Vegetable field downstream of the
tailing dam (distance≤2 km)
13
30
Control
Guiyang
July 2008
Vegetable field of village
3
3
Common name (species) of vegetable
Radish (Raphanus sativus L.), Chinese
Chrysanthemum(Chrysanthemum coronarium L.), Lettuce
(Lactuca sativa L.), Celery (Apium graveolens L.), Chinese
cabbage (Brassica pekinensis (Lour.) Rupr.), Pumpkin
(Cucurbita moschata)
Chinese cabbage, Pepper (Capsicum annuum L.), Radish,
Potato (Solannum tuberosum L.), Taro (Colocasia esculenta
(L.) Schoot), Pumpkin, Cowpea (Vigna unguiculata (L.)
Walp.), Eggplant (Solanum melongena L.), Corn (Zea mays
L.)
Radish, Onion (Allium fistulosum L.), Lettuce, Sweet potato
(Ipomoea batatas (Lam.) L.), Pepper
Chinese cabbage, Radish, Eggplant, Rapeseed (Brassica
campestris L.), Luffa (Luffa cylindrica (L.) Roem.), Garlic
(sativum L.), Corn (Zea mays L.)
Chinese cabbage, Radish, Lettuce, Cabbage (Brassica
oleracea L.), Pumpkin
Coriander (Coriandrum sativum), Radish, Pumpkin,
Rapeseed (Brassica campestris L.), Chinese Chrysanthemum,
Ipomoea (Ipomoea aquatica Forsskal), Bitter (Momordica
charantia L.), Corn (Zea mays L.)
Sweet potato, Lettuce, Chinese cabbage, Pumpkin, Radish,
Rapeseed, Garlic (sativum L.), Pepper, Cowpea, Celery, Corn
Chinese cabbage, Carrot (Daucus carota L. var. Sativa
Hoffm.), Chinese Chrysanthemum, Lettuce, Garlic,
Coriander, Lentils (Lablab purpureus (L.) Sweet), Cowpea,
Corn
Table S3. Number of samples and sampling site description of tailing-plant system
Site
Site name
Sampling date
Site descriptions
Tailing
Plant
T1
Beikuang
December 2006,
December 2007, July
2008, July 2012
Bottom taling
heaped 15 years
9
26
T2
Beikuang
December 2006,
December 2007, July
2008, July 2012
Top taling heaped
15 years
9
22
T3
Beikuang
December 2006,
December 2007, July
2008, July 2012
Old mine seam
8
19
T4
Nankuang
December 2006,
December 2007, July
2008, July 2012
Taling heaped 1
year
11
27
T5
Yangjia
December 2006,
December 2007, July
2008, July 2012
Bottom taling
heaped 5 years
7
23
T6
Yangjia
December 2006,
December 2007, July
2008, July 2012
Top taling heaped 5
years
6
18
4
Family (Species) of plant
Asteraceae (Aster ageratoides), Loganiaceae (Buddleja davidii),
Chenopodiaceae (Chenopodium album L.), Poaceae (Eriochloa villosa),
Caprifoliaceae (Lonicera japonica), Valerianaceae (Patrinia angustifoli),
Polygonaceae (Polygonum multiflorum), Pteridaceae (Pteris henryi),
Rosaceae (Pyracntha fortunei), Rubiaceae (Rubia leiocaulis), Poaceae
(Themeda villosa), Palmae (Trachycarpus fortune)
Loganiaceae (Buddleja davidii), Gleicheniaceae (Dicranopteris pedata),
Poaceae (Erigeron annuus), Dryopteridaceae (Polisticum tsus-sime),
Rosaceae (Rubus parvifoius), Poaceae (Saccharum arundinace)
Pteridaceae (Pteris vittata), Pteridaceae (Pteris henryi), Asteraceae
(Dendranthema indicum), Polygonaceae (Polygonum multifloru), Palmae
(Trachycarpus fortune)
Asteraceae (Bidens tripartita), Loganiaceae (Buddleja davidii),
Urticaceae (Debregeasia edulis), Moraceae (Ficus pumila), Asteraceae
(Inula coppa), Leguminosae (Pueratia phaseoloide), Poaceae
(Saccharum arundinace)
Asteraceae (Ainsliaea bonatii), Asteraceae (Bidens tripartita),
Chenopodiaceae (Chenopodium. Ambrosi), Urticaceae (Debregeasia
edulis), Asteraceae (Dendranthema indicum), Polygonaceae (Fagopyrum
tataricum), Moraceae (Ficus pumila), Equisetaceae (Hippochcaete
ramosi), Polygonaceae (Polygonum multiflorum), Poaceae (Saccharum
arundinace)
Loganiaceae (Buddleja davidii), Asteraceae (Ainsliaea bonatii),
Urticaceae (Debregeasia edulis), Poaceae (Themeda villosa)
Table S4. Concentratins (Geo Mean) of As and Sb in water, tailings and soil and in fish, wild plants and vegetables, and
Bio-accumulation factor (BAF) in the XKS Sb mine area.
As
Sb
Water(μg/L)
2.48
24.8
Tailings
169
3790
Concentration (mg/kg)
Soil
Fish(μg/kg)
62.9
86.8
1337
59.8
Wild plant
13.5
13.4
5
Vegetable
2.32
14.1
Bio-accumulation factor
Fish
Wild plant
Vegetable
46.1
0.066
1.50
1.99
0.0025
0.29
1000
BAFs (Fish organ / Water)
As
Sb
n=19
100
n=31
n=27
n=43
n=37
n=41
Liver Bladder Muscle
Skin
10
1
Gill Kidney
Figure S1. BAFs of As and Sb in fish organs/water
6
Buddleja (mg/kg)
Cabbage (mg/kg)
Fish liver (μg/kg)
300
300
Sb
200
As
200
r=0.645, p>0.05
100
100
0
0
0
70
140
5
Water (μg/L)0
r=0.392, p<0.05
6
12
5
Sb
4
r=0.645, p>0.05
4
As
r=0.224, p>0.05
3
3
2
2
1
0
60
2000
4000
6000
Soil (mg/kg)
60
Sb
40
r=0.645, p>0.05
30
60
90
As
r=-0.581, p<0.01
30
20
0
0
3000
6000
9000
100
200
300
400
Tailing (mg/kg)
Figure S2. Correlations of metal concentrations between in environment and in
biological compartments.
7