Applied Geochemistry 33 (2013) 298–305

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Applied Geochemistry
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Mercury distribution in coals influenced by magmatic intrusions,

and surface waters from the Huaibei Coal Mining District, Anhui, China
Zhicao Yan a,b, Guijian Liu a,b,⇑, Ruoyu Sun a, Dun Wu a, Bin Wu a, Chuncai Zhou a
a
CAS Key Laboratory of Crust-Mantle Materials and Environment, School of Earth and Space Sciences, University of Science and Technology of China, Hefei, Anhui 230026, China
b
State Key Laboratory of Loess and Quaternary Geology, Institute of Earth Environment, The Chinese Academy of Sciences, Xi’an, Shanxi 710075, China

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

Article history: The Hg concentrations in 108 samples, comprising 81 coal samples, 1 igneous rock, 2 parting rock sam-
Received 14 June 2012 ples and 24 water samples from the Huaibei Coal Mining District, China, were determined by cold-vapor
Accepted 25 February 2013 atomic fluorescence spectrometry. The abundance and distribution of Hg in different coal mines and coal
Available online 13 March 2013
seams were studied. The weighted average Hg concentration for all coal samples in the Huaibei Coalfield
Editorial handling by A. Kolker
is 0.42 mg/kg, which is about twice that of average Chinese coals. From southwestern to northeastern
coalfield, Hg concentration shows a decreasing trend, which is presumably related to magmatic activity
and fault structures. The relatively high Hg levels are observed in coal seams Nos. 6, 7 and 10 in the
southwestern coal mines. Correlation analysis indicates that Hg in the southwestern and southernmost
coals with high Hg concentrations is associated with pyrite. The Hg concentrations in surface waters in
the Huaibei Coal Mining District range from 10 to 60 ng/L, and display a decreasing trend with distance
from a coal waste pile but are lower than the regulated levels for Hg in drinking water.
Ó 2013 Elsevier Ltd. All rights reserved.

1. Introduction
In China, coal constitutes the largest fraction (74%) in the pri-
mary energy consumption, and coal consumption in China had
reached 2.74 Gt in 2009, accounting for approximately half of the
global coal consumption (Dai et al., 2012). Mercury and its com-
pounds are among the most toxic pollutants in the environment
(USEPA, 1997). Three forms of Hg, i.e. gaseous elemental Hg,
gaseous oxidized Hg and particulate bound Hg, are emitted into
the atmosphere during coal combustion (Selin, 2009). With an
atmospheric resident lifetime of 0.5–1 a, gaseous elemental Hg
can be transported trans-boundary before deposition, whereas
the latter two Hg forms are more reactive and are readily
dry- and wet-deposited in the vicinity of emissions (Selin, 2009).
Mercury that accumulates in the aquatic environment can be
potentially transformed into hyper-toxic methyl-Hg by bacteria
and chemical species, and the most serious effect of methyl-Hg is
its bio-accumulation and bio-magnification through the food chain
in aquatic systems (USEPA, 1997; Tjerngren et al., 2012). Because
of the wide-spread uses of coal, many toxic elements including
Hg are released into the environment (Pacyna et al., 2010; Tian
et al., 2011). Moreover, the combustion of some local coals in SW
China has caused severe health problems such as endemic fluoro-
⇑ Corresponding author at: CAS Key Laboratory of Crust-Mantle Materials and
Environment, School of Earth and Space Sciences, University of Science and
Technology of China, Hefei, Anhui 230026, China. Tel.: +86 551 3603714; fax: +86
551 3621485.
E-mail address: lgj@ustc.edu.cn (G. Liu).
sis, arsenosis and selenosis which are linked to high F, As and Se
contents in coals (Ding et al., 2001; Dai et al., 2012; Zhu et al.,
2012). Although there is no direct evidence to connect Hg emis-
sions from coal combustion to health issues, the Hg emission
inventory from coal combustion (800 t) has been the largest
anthropogenic Hg source and should be taken seriously (Pacyna
et al., 2010; Streets et al., 2011).
Fluids and volatile matter derived from magmatic intrusions
can thermally upgrade coal rank and alter some geochemical
components in coals (Finkelman et al., 1998; Mastalerz et al.,
2009; Dai et al., 2012; Yang et al., 2012). However, in most cases,
coals, especially coals with no contact with magmatic rocks, are
influenced by hydrothermal fluids derived from circulating water
in coal host rocks that was heated by intrusive bodies (Dai et al.,
2012). Compared to the world average for the Hg concentration
in coal (100 ng/g) (Ketris and Yudovich, 2009), Hg enrichment,
by several fold to several orders of magnitude, has been observed
in coals influenced by magmatic intrusion and hydrothermal fluid
alteration (Finkelman et al., 1998; Dai and Ren, 2007; Zheng et al.,
2008a). The mechanism for Hg enrichment in thermally altered
coals is still under debate. For magmatic fluid altered coal, Hg
enrichment seems to relate to secondary enrichment following
volatilization of Hg (Finkelman et al., 1998; Dai et al., 2012).
Enrichment of Hg in coal altered by hydrothermal fluids involves
leaching of Hg from the coal host rocks, Hg transport by cycling
hydrothermal fluids and deposition of Hg within the coal matrix
(Diehl et al., 2004; Dai et al., 2012; Kolker, 2012). The Huaibei
Coalfield is an area that is largely affected by Mesozoic magmatic

0883-2927/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.apgeochem.2013.02.024
 Z. Yan et al. / Applied Geochemistry 33 (2013) 298–305 299

intrusion, but the detailed factors controlling Hg enrichment of the
Huaibei coals has not been well characterized (Zheng et al., 2008a).
Long-term coal mining activities and utilization processes have
produced large quantities of waste rocks and combustion products,
and most of them are commonly stacked near subsidence ponds
and stream banks. This coal waste may pose a threat to the sur-
rounding environment, as Hg is thought to be enriched in the high
density fractions of coal (e.g. pyrite and other sulfide minerals),
and could be mobilized by spontaneous combustion, rainwater
and aeolian erosion (Diehl et al., 2004; Hower et al., 2010; Kolker,
2012). The surface waters from ponds and a stream creek in the
coal mining subsidence area in the Huaibei Coal Mining District
have been used as drinking water and for breeding fish by the res-
idents, and few environmental studies relating to Hg contamina-
tion to the local environment have been conducted (Yu et al.,
2006).
In this study, Permian coal samples from well-documented
coal-bearing sequences were sampled from several coal mines to
investigate the concentration and distribution of Hg in coals from
the Huaibei Coal Mining District, Anhui, China. The possible factors
controlling Hg enrichment were also analyzed in detail. Water
samples from the ponds and a stream creek in the coal mining sub-
sidence area in the Huaibei Coal Mining District were sampled to
assess the possible Hg contamination in surface waters.
2. Geological setting
The Huaibei Coalfield located in the northern Anhui province is
one of the most important coalfields in China (Fig. 1A). There are
several dozen active underground coal mines in this coalfield
(Fig. 1B). The coal rank is primarily bituminous and, to a lesser ex-
tent, anthracite and natural coke owing to the effect of magmatic
intrusion.
2.1. Coal-bearing sequences
The coal-bearing sequences of the Huaibei Coalfield comprise
the Late Carboniferous Taiyuan Formation, the Early Permian
Shanxi Formation and Lower Shihezi Formation, and the Late
Permian Upper Shihezi Formation. The stratigraphic and lithologi-
cal characteristics of the coal-bearing strata are depicted in Fig. 2.
The economically minable coal seams, with total coal thickness
varying from 1.5 to 15 m, mainly occur in the Shanxi Formation
and Lower Shihezi Formation. There are only 3–12 economically
minable coal seams, although the coal-bearing sequences contain
13–46 coal seams in the Huaibei Coalfield. The Taiyuan Formation,
with a thickness ranging from 121 to 150 m, comprises 3–11 un-
minable coal seams. The Shanxi Formation, with a thickness rang-
ing from 96 to 143 m, contains 1–2 minable coal seams with a

Fig. 1. (A) Location of the Huaibei coalfield; (B) Coal mines in the Huaibei Coalfield. Note that coal samples were collected from six sample locations: the Wolonghu Coal Mine
(WLH), Baishan Coal Mine (BS), Liuer Coal Mine (LE), Qidong Coal Mine (QD), Zhuzhuang Coal Mine (ZZ), and Mengzhuang Coal Mine (MZ), and the water samples were
collected from the Luling Coal Mining Area.
300 Z. Yan et al. / Applied Geochemistry 33 (2013) 298–305

Fig. 2. Stratigraphic column of coal-bearing sequence in the Huaibei Coalfield, Anhui, China.

cumulative coal thickness of 1.9 m. The Lower Shihezi Formation,
with a thickness ranging from 102 to 151 m, comprises 4–20 coal
seams with a cumulative coal thickness of 11.6 m. The Upper Shi-
hezi Formation contains 5–13 coal seams, and only one coal seam
(No. 3) of 1.5 m thickness is minable.
2.2. Magmatic activity
Because of multiple episodes of deformation, NNE- and EW-
trending faults developed and shaped the basic geological frame-
work of the Huaibei Coalfield (Jiang et al., 2001; Tan et al., 2011).
 Z. Yan et al. / Applied Geochemistry 33 (2013) 298–305 301

The Rb/Sr isotopic age of magmatic rocks identified in an adjacent
and geologically similar coalfield, Huainan Coalfield, is 110 Ma
(Mesozoic Era, Yanshan Period) (Yang et al., 2012), which suggests
that the intrusion events occurred about 200 Ma after coal deposi-
tion (300 Ma before present). The ‘‘Yanshan period’’ refers to the
tectonic events occurring in China and East Asia from the Late
Jurassic to Early Cretaceous, and this period was characterized by
intense lithospheric extension and widespread magmatic activity
(Fang et al., 2005; Dong et al., 2008). The thickness of magmatic
rocks is greatest in the southern part of the coalfield, decreasing
to a moderate thickness in the middle part, and is present only
as thin dikes in the northern part of the coalfield. However, most
of the intrusive bodies beneath the southern part of the coalfield
are well below the coal-bearing sequences. Multi-stage deforma-
tion of the coalfield resulted in development of abundant local
faults. Large areas of direct contact between magma and coal in
the southwestern coalfield upgraded the affected coals to anthra-
cite. In the northern coalfield, thin dikes outcrop but their effect
on the coals is thought to be weak. Most of the coals in the north-
ern part of the coalfield are a more typical medium volatiles bitu-
minous rank.
3. Samples and methods
Coal samples from seams Nos. 3, 4, 5, 6, 7 and 10 were collected
at six underground coal mines of the Huaibei Coalfield: Wolonghu
Coal Mine (WLH), Baishan Coal Mine (BS), Liuer Coal Mine (LE), Qi-
dong Coal Mine (QD), Zhuzhuang Coal Mine (ZZ) and Mengzhuang
Coal Mine (MZ) (Fig. 1). These samples comprise 81 coal benches, 1
igneous rock (taken from cross-cutting diorite dike, ZZ 5-5) and 2
coal partings (ZZ 4-8 and ZZ 5-7) (detailed information is given
in the Supplementary material). Samples from coal seams Nos. 6,
7, and 10 in southwestern coal mines (i.e. WLH, BS and LE) were
collected near intrusive sills.
The numbers of the collected coal samples from the WLH, BS,
LE, ZZ, MZ, and QD are 6, 15, 12, 15, 14, and 19, respectively, and
the numbers of coal samples from coal seams 3, 4, 5, 6, 7, and 10
are 12, 14, 6, 25, 12, and 12, respectively. The bench coal samples
of uniform thickness (10 cm) were collected from working chan-
nels by cutting downward in each coal seam. All the collected sam-
ples were stored in sealed plastic bags to prevent contamination
and oxidation. Each collected sample was approximately 2 kg.
Samples were split into 200 g aliquots and ground by hand in a
quartz mortar. The ground coal samples were passed through a
120-mesh sieve, and then dried 12 h in a desicator before storage
in sealed bottles.
Water samples were collected from 3 subsidence ponds in the
Luling Coal Mining Area (LL) in the Huaibei Coal Mining District.
The ponds labeled S, X and F in Table 1 represent the water sample
locations at distances of 70, 200 and 1000 m from a coal waste pile,
respectively. Additionally, water samples from one flowing creek
labeled H, 1800 m away from the coal waste pile, were also col-
lected. Two sampling sites were selected for each coal mining sub-
sidence pond and the flowing creek (Table 1). At each sampling
site, an approximately 1 L water sample was collected respectively
from a vertical water profile of 20, 40 and 60 cm below the water
surface (Table 1). All water samples were filtered through a
0.45 lm pore-size membrane, and collected into acid-cleaned
polyethylene bottles that were rinsed three times using the sam-
pled water. The collected water samples were then acidified to
pH < 2 using high-purity HNO3, and stored at 4 °C until analysis.
The solid samples (0.1 g) were digested with 15 mL oxidizing
acid mixture (HF:HCl:HClO4:HNO3 = 1:1:3:6) in a Teflon vessel
placed in a Multiwave-3000 microwave digestion unit (150 °C,
13 atm for 6 min; 170 °C, 17 atm for 6 min; 190 °C, 22 atm for
6 min; and 210 °C, 28 atm for 9 min). After cooling, the samples
were adjusted to 50 mL with deionized water. The Hg concentra-
tions in the resulting solutions and water samples were deter-
mined by cold-vapor atomic fluorescence spectrometry (CV-AFS).
The detection limit of this method is 0.01 ng/g. The certified refer-
ence material Chinese soil standard GBW07405 was used as qual-
ity control. The procedural blanks and standards were periodically
processed with the samples. The average Hg content of GBW07405
was 0.29 ± 0.01 lg/g (n = 81), which was in excellent agreement
with the certified value of 0.29 lg/g.
The total S, pyritic S and ash yield analysis were performed in
according with Chinese Coal Analysis Standards GB/T 214, 215
and 212, respectively.
4. Results and discussion
4.1. Hg concentration and distribution
The concentrations of Hg in the coals from six coal mines in the
Huaibei Coalfield are tabulated in Table 2, along with the ash yield,
total S and pyritic S contents. The Hg concentration in the Huaibei
coals ranges from 0.01 to 1.4 mg/kg, with an arithmetic mean of
0.44 ± 0.36 mg/kg (1SD, n = 81). The arithmetic mean values of ele-
ments in coal may be biased by the uneven distribution of samples
in location and geologic time (Dai el al., 2006; Sun et al., 2010).
Therefore, the coal production amount of each coal mine was taken
as a weighting factor to estimate the mean Hg concentration of
coals from the whole Huaibei Coal Mining District. The weighted
mean Hg concentration (WM) is 0.42 mg/kg and is calculated by
the formula: WM = R(CX  PX/P) (CX: Hg mean concentration in
coals of coal mine X; PX: coal production of coal mine X; P: total

Table 1
Concentrations of Hg in water samples in the Huaibei Coal Ming District.

Depth (cm) Sample No. Hg (ng/L) Sample No. Hg (ng/L) Sample No. Hg (ng/L) Sample No. Hg (ng/L)
20 S-1(20 cm) 50 X-1(20 cm) 30 F-1(20 cm) 30 H-1(20 cm) 10
40 S-1(40 cm) 40 X-1(40 cm) 30 F-1(40 cm) 30 H-1(40 cm) 10
60 S-1(60 cm) 30 X-1(60 cm) 30 F-1(60 cm) 30 H-1(60 cm) –
20 S-2(20 cm) 60 X-2(20 cm) 40 F-2(20 cm) 30 H-2(20 cm) 10
40 S-2(40 cm) 50 X-2(40 cm) 20 F-2(40 cm) 20 H-2(40 cm) –
60 S-2(60 cm) 60 X-2(60 cm) 40 F-2(60 cm) 20 H-2(60 cm) 10
Average 48 32 27 7

‘‘–’’ Not detected.

The ponds labeled S, X and F and the flowing creek labeled H represent the water sample locations at distances of 70, 200, 1000 and 1800 m from a coal waste pile,
respectively.
‘‘S-1’’ and ‘‘S-2’’ represent two water sampling sites in the pond labeled S. ‘‘X-1’’ and ‘‘X-2’’ represent two water sampling sites in the pond labeled X. ‘‘F-1’’ and ‘‘F-2’’ represent
two water sampling sites in the pond labeled F. ‘‘H-1’’ and ‘‘H-2’’ represent two water sampling sites in the flowing creek labeled H.
Data in parentheses refer to the distances below the water surface.
302 Z. Yan et al. / Applied Geochemistry 33 (2013) 298–305

Table 2
Ranges and means of ash yield, total S, pyretic S, and Hg contents in coals from six coal mines, Huaibei Coalfield (on a dry, whole coal basis).

Coal mines Production (Mt) Average of Hg in each coal mine Coal seam No. Ad (%) St,d (%) Sp,d (%) Hg (mg/kg)
WLH 0.90 0.81 7 (26.4–28.9)/27.7 (0.65–0.70)/0.68 (0.20–0.20)/0.20 (0.61–0.74)/0.68
10 (16.7–30.4)/23.7 (0.50–0.60)/0.55 (0.14–0.17)/0.15 (0.56–1.23)/0.88
BS 1.5 0.67 6 (19.1–33.9)/26.8 (0.56–0.69)/0.62 (0.21–0.29)/0.24 (0.22–1.35)/0.67
LE 1.3 0.47 3 (16.7–21.0)/18.7 (0.35–0.67)/0.48 (0.09–0.18)/0.13 (0.05–0.24)/0.12
4 (14.5–23.5)/19.9 (0.29–0.95)/0.60 (0.08–0.29)/0.18 (0.01–1.08)/0.33
6 (28.6–34.7)/31.6 (0.56–0.70)/0.63 (0.20–0.27)/0.23 (0.57–1.37)/0.91
QD 1.8 0.40 3 (15.8–21.8)/19.1 (0.23–0.84)/0.64 (0.06–0.22)/0.17 (0.02–0.42)/0.21
6 (27.0–34.2)/29.6 (0.45–1.29)/0.67 (0.13–0.34)/0.19 (0.08–1.40)/0.37
7 (20.7–35.9)/29.4 (0.51–0.69)/0.60 (0.13–0.21)/0.17 (0.11–1.28)/0.52
ZZ 2.4 0.32 4 (8.80–27.7)/17.7 (0.23–0.85)/0.51 (0.07–0.26)/0.15 (0.06–0.27)/0.18
5 (15.0–18.4)/16.5 (0.46–0.88)/0.64 (0.12–0.22)/0.17 (0.33–0.79)/0.54
MZ 2.2 0.19 3 (10.1–14.6)/12.6 (0.22–0.81)/0.48 (0.06–0.25)/0.14 (0.07–0.21)/0.12
7 (13.5–13.9)/13.7 (0.44–0.74)/0.59 (0.12–0.23)/0.18 (0.31–0.37)/0.34
10 (1.51–23.1)/14.0 (0.32–1.24)/0.71 (0.08–0.40)/0.21 (0.11–0.29)/0.19

WLH: Wolonghu Coal Mine; BS: Baishan Coal Mine; LE: Liuer Coal Mine; QD: Qidong Coal Mine; ZZ: Zhuzhuang Coal Mine; MZ: Mengzhuang Coal Mine.
A: ash yield; d: dry basis; St,d: total S; Sp,d: pyritic S.
The ranges (min–max) are included in parentheses followed by means.
The data for Hg, ash yield, and total S in ZZ and MZ are cited from Zheng et al. (2008a).
The detailed information for ash yield, total S, pyritic S and Hg contents in all solid samples, comprising 81 coal samples, 1 igneous rock and two parting rock samples, is given
in Table S1 of the supplementary material.

coal production of all six coal mines) (Table 2). Compared to the Hg
abundance in the upper continental crust (Rudnick and Gao, 2004),
Huaibei coals are enriched in Hg by approximately 10-fold. In addi-
tion, Huaibei coals are significantly higher in Hg than other coals
from China (0.16 mg/kg) (Dai et al., 2012), the USA (0.17 mg/kg)
(Finkelman, 1993) and the world (0.10 mg/kg) (Yudovich and Ke-
tris, 2005). The range of Hg concentrations in the coals of the Huai-
bei Coalfield are somewhat wide, which is possibly due to the local
geological conditions of each coal mine and the multi-stage geo-
logic activity in this region.
As stated above, the distribution of magmatic rocks follows
both lateral and vertical trends. Magmatic activity decreases up-
wards within coal-bearing sequences and along NNE-trending
faults. Hence, coal samples collected along faults and different coal
seams were used to investigate the relationship between mag-
matic intrusion and Hg concentrations in coals.
Fig. 3 shows the average Hg concentrations in coal samples
from six coal mines. A spatial decreasing trend of Hg concentration
1.8
1.6 Southwestern
1.4
Outlier
1.2
Southernmost
Hg (mg/kg)
is observed along the coal mines from the southwestern coalfield
(i.e. WLH, BS, LE) to the northeastern coalfield (i.e. ZZ and MZ).
Average Hg concentration in coals from southernmost QD is higher
than the latter two coal mines and lower than the first three coal
mines. However, after excluding two extremely high Hg concentra-
tions in the No. 6 (1.4 mg/kg, QD 6-8) and No.7 (1.28 mg/kg, QD 7-
8) coal seams of QD, the average Hg concentration of QD cannot be
distinguished from those of ZZ and MZ (Table 2). In the southern-
most QD, the magmatic bodies underlie the coal bearing se-
quences. During field sampling in QD, although some fractures
and vein structures in coal, possibly derived from hydrothermal
fluids, were observed, no magmatic bodies were found. Vertically,
the No. 7 coal seam in QD has an approximately 2 times greater Hg
concentration than the No. 6 and No. 3 coal seams that are higher
in the section (0.52 vs. 0.21–0.37 mg/kg) (Table 2). This implies
that nearly half of the Hg in the No.7 coal seam was possibly de-
rived from hydrothermal fluids assuming that the Hg content of
these coals were originally similar. In the southwestern WLH, BS
and LE, coal samples from seams Nos. 6, 7, and 10 collected near
intrusive sills have Hg mean concentrations of 0.67–0.91 mg/kg,
Max
which is higher than other coal seams in these three coal mines
75
(0.12–0.33 mg/kg) and all coal seams in other coal mines (0.12–
50
0.54 mg/kg) (Table 2). In the northern coalfield, a large portion of
25
intrusive bodies outcrop, and less prominently developed dikes
Min
cut across the coal seams. The mean Hg concentrations in coal

1.0 Northeastern
seams from the northeastern ZZ and MZ are lower, in range of
0.12–0.54 mg/kg. Sample ZZ 5-5 from ZZ is an igneous rock with
0.8 a cross-cutting pyrite vein, postdating magmatic intrusion. The ex-
0.6 tremely high Hg concentration (8.02 mg/kg) in this rock was prob-
ably due to pyrite deposition from hydrothermal fluids (Fig. 4). As
0.4 shown in Fig. 4, Hg is also significantly enriched in the mudstone
0.2 parting sample ZZ 5-7 (4.95 mg/kg) having a cross-cutting fracture
structure. The development of the fracture structure in the parting
0.0 of the partly intruded No. 5 coal seam was due to the migration of
WLH BS LE QD ZZ MZ
hydrothermal fluids heated by intrusive bodies. The Hg carried by
hydrothermal fluids was possibly deposited in the form of sulfide
Coal Mine
minerals (e.g. pyrite) (Diehl et al., 2004; Kolker, 2012), and was
Fig. 3. Variation and ranges of Hg contents in coals from six coal mines (WLH, BS, then incorporated into the coal parting. Coal-associated epigenetic
LE, QD, ZZ, and MZ) in the Huaibei Coalfield. Numbers of samples for WLH, BS, LE, pyrite derived from hydrothermal fluids is found to contain Hg as
QD, ZZ, MZ are 6, 15, 12, 19, 15, 14, respectively. Note that WLH, BS, and LE are high as 100 mg/kg (Diehl et al., 2004; Kolker, 2012). In contrast, an-
located in the southwestern Huaibei Coalfield, QD is located in the southernmost other mudstone parting sample, ZZ4-8 coal seam No. 4, has a lower
Huaibei Coalfield, and ZZ and MZ are located in the northeastern Huaibei Coalfield,
Hg concentration of 0.33 mg/kg (Table 2). The partly altered No. 5
as also indicated in Fig. 1.
 Z. Yan et al. / Applied Geochemistry 33 (2013) 298–305 303

9 1.4
Igneous rock Total sulfur (n=81)
8 Pyritic sulfur (n=81)
1.2
7

6 1.0
Parting
5
Hg (mg/kg)

Sulfur (%)
0.8
R=0.2 (n=81)
4
0.6
0.6
0.4 R=0.5 (n=81)
0.4 Parting
0.2
0.2

0.0
0.0
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6
ZZ -1
ZZ 2
ZZ -3
ZZ -4
ZZ -5
ZZ -6
ZZ 7
ZZ 4-8
ZZ 4-9
ZZ -10
ZZ -1
ZZ -2
ZZ 3
ZZ -4
ZZ -5
ZZ -6
ZZ -7
8
4-

5-
4-

5-

Hg (mg/kg)
4

4
4
4
4

5
5

5
5
5
5
4
ZZ

Sample
Fig. 4. Variation of Hg contents in 18 samples from the Zhuzhuang Coal Mine,
Huaibei Coalfield, Anhui, China. Note that sample ZZ5-5 is an igneous rock that
contains vein pyrite, and ZZ 4-8 and ZZ 5-6 are parting samples.
Fig. 5. Relationship between Hg and S in coal samples. Note that the solid line is for
the relationship between Hg and total S in 81 coal samples with a correlation
coefficient of 0.2, and the dotted line is for the relationship between Hg and pyritic S
in 81 coal samples with a correlation coefficient of 0.5.

Fig. 5). This suggests portions of Hg are associated with pyrite.

coal seam of ZZ has a higher mean Hg concentration than other
coal seams in these two coal mines (i.e. ZZ and MZ) (Table 2).
4.2. Hg enrichment factors and modes of occurrence
From the SW to the NE part of the coalfield, Hg abundance in
coals shows a decreasing trend (Figs. 1 and 3), which is presumably
connected to the magmatic activity.
The enhanced Hg level in southernmost QD possibly relates to
the addition of Hg from ascending hydrothermal fluids. As indi-
cated above, most of the intrusive bodies underlie coal-bearing se-
quences in the southern coalfield possibly localizing the generation
of hydrothermal fluids. The invasion pathway of hydrothermal flu-
ids into QD coals is unclear, but is possibly along faults. In the
southwestern coalfield (i.e. WLH, BS, and LE), coal seams Nos. 6,
7, and 10 were intruded by magma in the forms of dikes and sills,
which split and thinned the coal seams. The intrusion of magmatic
fluids destroyed the continuity and integrity of the coal seams. Be-
cause of the magmatic intrusion into coal-bearing strata, many
areas of the coals were up-graded to anthracite and coke. When
the heat dissipated and temperatures dropped to ambient levels,
Hg may be have been added from the solutions, which were de-
The correlations of Hg vs. pyretic-S are strong for southwestern
coals (R = 0.65, n = 33) and southernmost coals (R = 0.7, n = 19),
but are very weak for northeastern coals (R = 0.1, n = 29) (Fig. 6).
Skyllberg et al. (2000) and Liu et al. (2005) concluded that organic
S compounds can capture Hg and result in the enrichment of Hg in
coals. Both pyrite and organically associated Hg are considered to
be leading carriers of Hg in coals (Cecil et al., 1979; Ruch et al.,
1974). Therefore, Hg in coals from the northeastern coal mines
(i.e., ZZ and MZ) with lower Hg concentrations possibly have a
greater organic affinity, whereas Hg in coals from the southwestern
coal mines (i.e., WLH, BS, and LE) and the southernmost coal mine
(i.e., QD) with higher Hg concentrations are possibly associated
with pyrite. However, these conclusions are only suggestions,
and more informative methods such as sequential extraction are
needed to confirm the observations.
0.45
Southernmost (n=19)
Southwestern (n=33)
0.40
Northeastern (n=29)
0.35
Pyritic sulfur (%)

rived from the cooling magma, and then incorporated into the coal
(Finkelman et al., 1998; Dai and Ren, 2007). Moreover, Finkelman 0.30 R=0.70 (n=19)
R=0.65 (n=33)
et al. (1998) reported that Hg is partially volatilized at a tempera- 0.25
ture 150 °C and completely volatilized at 550 °C, so Hg could be
driven off from the coal by magmatic heat and then re-deposited 0.20
R=0.10 (n=29)
nearby (Dai and Ren, 2007). These mechanisms possibly explain
0.15
the enhanced Hg concentrations of coals in the three southwestern
coal mines (i.e. WLH, BS, and LE). Northeastern ZZ and MZ is an 0.10
area weakly affected by magmatic activity. Only less prominently
developed cross-cutting dikes were observed in coal seam No. 5 0.05
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6
in the northeastern ZZ. The Hg concentrations in coals from the
ZZ show that the overlying samples in contact with igneous rocks Hg (mg/kg)
(i.e. ZZ-5-3, ZZ5-4) have lower Hg than in other benches in Fig. 4.
Fig. 6. Relationship between Hg and pyritic S in coal samples. Note that the solid
Some Hg was possibly driven off by intrusive heat and enriched black line is for the relationship between Hg and pyritic sulfur in 19 coal samples
in nearby coal benches. (inverted triangle) from the coal mine in the southernmost coalfield (i.e. QD) with a
The magmatic intrusion not only caused the enrichment of Hg correlation coefficient of 0.70, the dotted line is for the relationship between Hg and
in the Huaibei coals, but also possibly altered the modes of occur- pyritic S in 33 coal samples (triangle) from the coal mines in the southwestern
coalfield (i.e. WLH, BS, and LE) with a correlation coefficient of 0.65, and the solid
rence of Hg. The correlation between Hg and total S in the Huaibei gray line is for the relationship between Hg and pyritic S in 29 coal samples (star)
coals is weak (R = 0.2, n = 81, Fig. 5), whereas the correlation be- from the coal mine in the northeastern coalfield (i.e. ZZ and MZ) with A correlation
tween Hg and pyritic-S is slightly increased (R = 0.5, n = 81, coefficient of 0.10.
304 Z. Yan et al. / Applied Geochemistry 33 (2013) 298–305
In fact, other elements besides Hg are enriched in the Huaibei
coals, the average contents of some environmental sensitive ele-
ments, such as Zn (7.3), V (3.1), Cu (2.8), Cr (2.2), Mo
(1.6), Ni (1.2), and Pb (1.1) (Zheng et al., 2008b), are higher
than the averages of the corresponding trace elements in Chinese
coals reported elsewhere (Dai et al., 2012). Finkelman et al.
(1998) also stated that some trace elements, such as V and Ni,
are enriched in the coals adjacent to a dike.
4.3. Mercury contents of surface waters
The contents of Hg in all water samples and the average Hg con-
tents in different water bodies in the Huaibei Coal Mining District
are shown in Table 1. The average Hg contents in the coal mining
subsidence ponds S, X, and F, and the flowing creek H are 48, 32,
27 and 7 ng/ L, respectively (Table 1), which are significantly lower
in comparison with the drinking water upper limit of 1000 ng/L
prescribed by the Chinese Standards for Drinking Water Quality
GB 5749–2006, 2000 ng/L in the USA (USEPA, 2001; Nam et al.,
2003), and 500 ng/L in Japan (Takahashi et al., 2008), but are com-
paratively higher than the global background value of natural
water of 5 ng/L Hg (Yan et al., 2003). A decreasing trend is observed
in ponds with increasing distance from the waste pile (Table 1),
which suggests that the waste pile produced during coal mining
activities has influenced Hg contents in the subsidence pond
waters.
Compared to surface waters in proximity to mines in the Uk-
raine that contain coals with high Hg levels (Kolker et al., 2009),
Hg contents in the surface waters in the Huaibei Coal Mining Dis-
trict are relatively lower. The water bodies in ponds S and X have
been used for breeding fish, and the water in the pond F has been
used for drinking water by some residents. The low Hg levels in the
subsidence ponds contribute little Hg exposure to local people who
rely on the waters for drinking and breeding fish. Thus, at present,
there is no need to transfer the coal waste pile from pond banks to
other places that will increase the disposal cost. The Hg flux de-
rived from coal waste piles could be accumulated in sediments in
the water bodies, where it could be transformed to highly toxic
methyl-Hg by microbial activities (Díez, 2009; Lehnherr et al.,
2012). Mercury can bio-accumulate through the food chain, and
be concentrated in fish (Clarkson, 2002; Johnsson et al., 2005; Car-
los et al., 2007; Zenrihun et al., 2007). The Hg concentrations in fish
from subsidence ponds should be determined in a further study to
give an overall picture of Hg distribution in subsidence ponds.
5. Conclusions
In 81 coal samples from the Huaibei Coalfield, Anhui province,
China, the Hg concentrations range from 0.01 to 1.4 mg/kg, with
a weighted mean of 0.42 mg/kg, which is higher than that in coals
from the rest of China, USA and the world. The Hg contents in the
Huaibei Coalfield are highest in the SW and lowest in the NE. The
Hg concentrations in southernmost coal mine with magmatic rocks
underlying coal bearing sequences have an intermediate value.
Coal seam Nos. 6, 7 and 10 in the southwestern coal mines were
extensively intruded by magmatic fluid, and Hg concentration in
these coal seams are significantly higher than other coal seams
in southwestern coal mines and all coal seams from other coal
mines in the area, which possibly relates to the magmatic intru-
sions. The cross-cutting vein and fracture structure in southern-
most coals suggests that epigenetic hydrothermal fluids were an
important source for Hg enrichment in coals. Correlation analysis
shows that in coals from the southwestern and southernmost coal
mines, pyritic-associated Hg is the most likely mode of occurrence.
The Hg contents in surface waters in the Huaibei Coal Mining Dis-
trict are relatively low and contribute little direct Hg exposure to
the local environment. However, the potential uptake of Hg in local
fish should be evaluated.
Acknowledgements
This work is supported by the National Natural Science Founda-
tion of China (No. 41173032), the National Science and Technology
Support Program (1012BAC10B02), Key Program for Science and
Technology Development of Anhui Province (No. 12010402111
and 11010401015), and the Creative project of the Huainan Mining
Industry (Group) Co. Ltd. We acknowledge the editors and review-
ers for polishing the language of the paper and for in-depth
discussion.
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.apgeochem.2013.
02.024.
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