International Journal of Coal Geology 57 (2004) 49 – 61

www.elsevier.com/locate/ijcoalgeo

Mineral matter and potentially hazardous trace elements

in coals from Qianxi Fault Depression Area in
southwestern Guizhou, China
Junying Zhang a,*, Deyi Ren b, Yanming Zhu c, Chen-Lin Chou d,
Rongshu Zeng e, Baoshan Zheng f
a
National Laboratory of Coal Combustion, Huazhong University of Science and Technology, Wuhan 430074, China
b
China University of Mining and Technology (Beijing), Beijing 100083, China
c
China University of Mining and Technology (Xuzhou), Xuzhou 221008, China
d
Illinois State Geological Survey, 615 East Peabody Drive, Champaign, IL 61820, USA
e
Institute of Geology and Geophysics, Chinese Academy of Sciences, Beijing 100029, China
f
Institute of Geochemistry, Chinese Academy of Sciences, Guiyang 550002, China
Received 12 December 2002; accepted 22 July 2003

Abstract

Mineralogy, coal chemistry and 21 potentially hazardous trace elements (PHTEs) of 44 coal samples from the Qianxi Fault
Depression Area (QFDA) in southwestern Guizhou province, China have been systematically studied. The major minerals in
coals studied are quartz, kaolinite, illite, pyrite, calcite, smectite, marcasite and accessory minerals, including rutile, dolomite,
siderite, gypsum, chlorite, melanterite, apatite, collophane and florencite. The SiO2 content shows a broad variation (0.8 –
30.7%). A high SiO2 content in Late Permian coals reflects their enrichment in quartz. The Al2O3 content varies from 0.8% to
13.4%, Fe2O3 from 0.2% to 14.6%, CaO from < 0.1% to 11.9% and the contents of other oxides are relatively low. The
relationship between the major oxides and the ash content of coals from high to low is in the order of
Si>Al>K>Ti>Na>Mg>Ca>Fe>S. A comparison with World coal averages shows that the Late Permian coals in QFDA are
highly enriched in As, Hg, F and U, and are slightly enriched in Mo, Se, Th, V and Zn. The Late Triassic coals in QFDA are
highly enriched in As and Hg, and are slightly enriched in Mo, Th and U. The concentrations of As, Hg, Mo, Se, Tl and Zn in
the QFDA coal are higher than other Guizhou coal and Liupanshui coal nearby.
The QFDA is an area strongly affected by the low-temperature hydrothermal activity during its geologic history (Yanshanian
Age, about 189 Ma). The coals in QFDA are enriched in volatile PHTEs, including As, Hg, Se, Sb, Mo, among others. The
regions where the coals are enriched in As, Hg and F have been mapped. The regions of coals enriched in volatile PHTEs
overlap with the regions of noble metal ore deposits. These coals are located in the cores of anticline and anticlinorium, which
are connected with the profound faults through the normal faults. Coals are enriched in volatile PHTEs as a result of the low-
temperature hydrothermal activity associated with tectonic faulting.
D 2003 Elsevier B.V. All rights reserved.

Keywords: Potentially hazardous trace elements; Coal; Low-temperature hydrothermalism; Southwestern Guizhou

* Corresponding author. Fax: +86-27-87545526.

E-mail address: jyzhang@hust.edu.cn (J. Zhang).

0166-5162/$ - see front matter D 2003 Elsevier B.V. All rights reserved.
doi:10.1016/j.coal.2003.07.001
50 J. Zhang et al. / International Journal of Coal Geology 57 (2004) 49–61
1. Introduction
The occurrence of high-arsenic coals in southwest
China, especially in eastern Yunnan province and
southwestern Guizhou province, is of great interest
to many people (Zheng, 1985; Zheng and Huang,
1989; Zhou and Ren, 1992; Zhou, 1994, 1998; Belkin
et al., 1997, 1998; Feng et al., 1998; Zhang, 1999;
Zhang et al., 1999, 2002; Finkelman et al. 2002). One
important reason for this interest in the high-arsenic
coals is the impact of its utilization on human health.
More than 3000 cases of arsenosis have been docu-
mented in several villages in southwestern Guizhou
province (Zheng, 1985; Zheng et al., 1999; Belkin et
al., 1997; Zhou et al., 1998; Du et al., 2000). Other
papers also discuss arsenic and mercury contents of
coals in Southwest China. Zhou and Ren (1992) and
Zhou (1998) investigated the distribution of arsenic in
coals of Yunnan province, China. They distinguished
two arsenic distribution types, syn-sedimentary with
peat deposits (such as As2O5, in Mining Area IV) and
secondary enrichment during coal metamorphism
(such as As2O5, in Mining Area IV). Zhou (1994)
also determined the content of mercury in coals in
Laochang Mining Area of eastern Yunnan province,
China (Hg, \0.03 – 3.8 ppm, average 0.38 ppm).
Zheng (1993) identified a range of As enrichment in
coals and its geochemical significance. Zheng (1985)
and Zheng et al. (1996) demonstrated that corn and
Fig. 1. Location of the QFDA.
chili pepper dried over open stoves using fluorine-
and arsenic-rich coals may be the principal factor for
the fluorine and arsenic poisoning. Belkin et al. (1997,
1998) indicated that arsenic content in coals reach
values as high as 35,000 ppm, on a whole coal basis,
and identified several As-bearing phases including
arsenopyrite, As-bearing pyrite, arsenic sulfide, Fe–
As oxide, As-bearing K – Fe –sulfate and As-bearing
iron phosphate. The organic matter appeared to con-
tain organically bound As, which may be the major
occurrence form of arsenic in some super high arsenic
coals (H2 sample). Zheng et al. (1999) described
endemic fluorosis, arsenism and selenosis relating to
coal use in southwest China. In Triassic coals in
southwestern Guizhou, the distribution of As and
Hg in a coal seam is rather inhomogeneous, the ranges
of As and Hg vary from 1.22 to 238 ppm and from
0.34 to 10.5 ppm, respectively, in random samples
(Zhang et al., 1999). Ruppert et al. (2001) reported
that the arsenic contents for individual benches ranged
from 0.6 to 418 ppm (whole coal basis) in a contin-
uous 4.55 ft (1.4 m) channel sample from the Fire
Clay coal zone, eastern Kentucky. Zhang et al. (2002)
found that a pyrite vein contained a mosaic of micron
and submicron pyrite crystals enriched in arsenic and
molybdenum.
This paper provides a systematic mineralogical
characterization, the content and distribution of the
potentially hazardous trace elements (PHTEs), and the
 J. Zhang et al. / International Journal of Coal Geology 57 (2004) 49–61 51

impact of low-temperature hydrothermalization on the
concentrations of the volatile PHTEs in the Qianxi
Fault Depression Area (QFDA) in southwestern Guiz-
hou province.
2. Geological setting
The QFDA is located in the southwestern Guizhou
province in southwest China (Fig. 1). The QFDA is a
triangular area surrounded by three deep faults and is
dissected by the Shizong-Guiyang fault. The Shui-
cheng-Ziyun fault is to the northeast, the Panxian fault
is to the northwest and the Nanpanjiang fault is to the
south of the area. These four syn-sedimentary faults
were active during accumulation of Late Permian coal
and Late Triassic coal. The tectonic activities were
very strong during the Yanshanian age (189 Ma), with
some faults still active (Wang, 1996).
This area has many noble metal ore deposits,
including gold, antimony, arsenic, mercury and thal-
lium, and sometimes is informally called the ‘‘golden
triangle’’ (He et al., 1993) (Fig. 2).
The coal-bearing strata of Late Permian and Late
Triassic ages are mainly in the Longtan (P2L),
Changxing (P2ch) and Huobachong Formations
(T3h). The coal studied in QFDA crops out in struc-
turally complex areas that appear as fault and /or fold
controlled windows exposed by erosion of overlying
strata.

Fig. 2. Locations of noble metal ore deposits and the coal samples studied in the QFDA.
52 J. Zhang et al. / International Journal of Coal Geology 57 (2004) 49–61

3. Samples and analytical procedures coal was determined according to National Standard
GB212-77 and the total sulphur content was deter-
A total of 44 coal samples (28 Permian and 16 mined by wet chemical analysis. The samples were
Triassic samples) were collected from relatively small digested with H2SO4 – HNO3 –H2O2 in a microwave-
coal mines in QFDA, in the southwestern Guizhou accelerated reaction system. The chemical composition
province, China. The samples were collected and of the coal ash was studied by X-ray fluorescence
stored carefully in plastic bags to prevent contamina- spectrometry (XRFS). Inductively coupled-plasma
tion and weathering. mass spectrometry (ICP-MS) was used to determine
The minerals in the coals were examined by optical the content of PHTEs of the Late Permian coal, and
microscopy, scanning electron microscopy – energy- instrumental neutron activation analysis (INAA) and
dispersive X-ray analysis (SEM-EDX) and powder atomic absorption spectrometry (AAS) was used to
X-ray diffraction (XRD). Microscopical analyses were determine the content of PHTEs of Late Triassic coal,
carried out under reflected white light. The ash yield in except for Se, F and Hg, which were determined by
Table 1
Ash contents and chemical compositions of the coals studied
Sample Age Aad SiO2 Fe2O3 Al2O3 TiO2 MnO CaO MgO P2O5 K2 O Na2O
(%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%)
ZM06 P2 36.3 16.6 2.0 4.4 0.4 0.01 2.3 0.2 0.009 0.5 0.1
ZM05 P2 56.3 24.8 8.9 6.0 0.5 0.04 11.9 0.3 0.003 0.7 0.1
ZM04 P2 31.4 9.1 3.5 3.5 0.2 0.01 1.0 0.1 0.004 0.3 0.1
ZM031 P2 38.2 30.7 2.4 3.6 0.1 0.01 0.8 0.1 0.005 0.3 0.1
ZM02 P2 39.9 20.1 3.9 3.5 0.1 0.01 0.2 0.1 0.003 0.3 0.1
QG07 P2 28.6 9.0 14.6 1.1 0.1 0.01 0.8 0.2 0.004 0.2 0.1
QG052 P2 12.9 4.5 1.4 1.9 0.1 0.01 2.7 0.1 0.177 0.2 0.1
QG04 P2 25.2 11.2 4.0 6.8 0.8 0.01 0.3 0.4 0.019 0.7 < 0.1
QG031 P2 21.5 8.5 2.9 5.3 0.6 0.02 3.5 0.4 0.018 0.5 0.1
QG02 P2 50.0 23.8 7.8 13.4 1.9 0.03 0.3 0.7 0.1 1.3 0.4
QG01 P2 33.2 7.6 4.7 3.9 0.4 0.04 9.2 0.5 0.005 0.3 0.1
QC03 P2 13.2 6.4 3.9 2.8 0.1 0.01 < 0.1 < 0.1 0.005 0.1 0.1
QO02 P2 12.0 6.3 1.0 4.0 0.3 0.01 < 0.1 < 0.1 0.005 0.1 0.1
QX01 P2 19.9 10.2 3.1 5.5 0.6 0.01 < 0.1 0.1 0.016 0.4 < 0.1
QXZ01 P2 16.3 7.0 0.6 1.8 0.1 0.01 5.6 0.2 0.005 0.1 0.1
XD01 P2 30.4 9.9 11.5 6.9 1.3 0.01 0.1 0.3 0.027 0.7 0.1
QL01 P2 35.2 10.8 11.0 3.2 0.2 0.01 < 0.1 0.2 0.005 0.6 0.1
PN28-1 P2 54.6 24.5 5.9 17.7 2.9 0.01 < 0.1 0.2 0.052 1.0 1.7
PN28-2 P2 47.7 25.9 7.4 10.5 1.7 0.02 < 0.1 0.2 0.05 0.7 0.5
PN28-3 P2 39.6 19.4 5.3 10.8 1.8 0.01 < 0.1 0.2 0.05 0.6 0.9
D-5 P2 15.8 9.5 1.0 3.5 0.1 0.01 0.6 0.2 0.022 0.2 0.1
D-3 P2 10.8 5.5 1.0 2.1 0.1 0.02 1.1 < 0.1 0.01 0.1 0.1
PL-17 P2 21.8 9.9 2.4 6.1 0.5 0.02 0.7 0.2 0.02 0.4 0.3
LF-1 P2 17.0 8.9 1.5 5.4 0.3 < 0.01 < 0.1 0.2 0.03 0.1 0.1
LY-1 P2 25.8 13.7 6.7 4.2 0.2 < 0.01 < 0.1 0.1 0.03 0.2 0.1
XT01 T3 16.2 7.2 3.6 3.4 0.2 0.01 0.8 0.2 0.031 0.2 0.1
LT01 T3 14.3 4.3 6.5 2.2 0.1 0.01 0.6 0.1 0.007 0.1 0.1
ZT01 T3 10.1 0.8 2.9 0.9 < 0.1 0.01 2.7 0.7 0.003 < 0.1 0.1
JT01 T3 8.2 3.6 2.9 2.2 0.1 0.01 0.4 < 0.1 0.015 0.1 < 0.1
HT01 T3 14.6 5.8 4.8 3.3 0.1 0.01 0.5 < 0.1 0.005 < 0.1 < 0.1
ST01 T3 2.6 0.9 0.2 0.8 < 0.1 0.01 0.5 < 0.1 0.005 < 0.1 < 0.1
AT01 T3 13.7 3.3 7.5 2.1 0.1 0.01 0.6 < 0.1 0.019 0.1 < 0.1
PL28 T3 16.6 8.0 1.8 5.0 0.5 < 0.01 < 0.1 0.1 0.022 0.2 0.4
PL26 T3 25.8 10.1 7.4 5.8 0.7 0.02 < 0.1 0.3 0.034 0.5 0.4
PL24 T3 26.6 11.6 5.0 7.5 1.0 0.01 < 0.1 0.2 0.034 0.5 0.6
Aad: the ash yield.
 J. Zhang et al. / International Journal of Coal Geology 57 (2004) 49–61 53

atomic fluorescence spectrometry (AFS), ion-selective
electrode (ISE) analysis and cold-vapor atomic absorp-
tion spectrometry (CV-AAS), respectively.
4. Chemistry and mineralogy of the coals
Results of optical microscope, SEM-EDX analysis,
and powder XRD analysis show that the major min-
erals in the Late Permian coals are quartz, kaolinite,
illite, pyrite, calcite, smectite and marcasite. The major
minerals in the Late Triassic coals studied are kaolin-
ite, illite, pyrite, smectite and marcasite. Late Permian
coal in Southwest China is enriched in quartz (Wang,
1996), but there is little quartz in the Late Triassic
coals studied. The accessory minerals in these coals are
rutile, dolomite, siderite, gypsum, chlorite and melan-
terite. Apatite, collophane and florencite were found in
the Late Permian coal.
The ash yield and chemical composition of 35 coal
samples are listed in Table 1. The ash yield of coals in
QFDA in southwest Guizhou, China ranges between
2.6% and 56.3%, and the Late Permian coals show
much higher ash yield than the Late Triassic coals
(29.3% and 14.9% as mean values, respectively). The
SiO2 content shows a relatively broad variation (0.8 –
30.7%), with the Late Permian coals having higher
SiO2 than the Late Triassic coals (13.4% and 5.6% as
mean values, respectively), consistent with the Late
Permian coals being enriched in quartz. The Al2O3
content varies from 0.8% to 13.4%, Fe2O3 from 0.2%
to 14.6%, TiO2 from < 0.1% to 2.9% and CaO from
< 0.1% to 11.9%. The contents of MnO, MgO, K2O
and Na2O are generally less than 1%.

Fig. 3. Variation of chemical composition of coals with ash content (Aad).

54 J. Zhang et al. / International Journal of Coal Geology 57 (2004) 49–61

A significant relationship exists between the major tion with the ash (Fig. 3). The correlation coefficient
oxides and ash content of coals. The contents of between SiO2 and ash contents (r = 0.895, n = 36) is
SiO2, Al2O3, TiO2 and K2O show a positive correla- the highest because SiO2 is contained in quartz and

Fig. 4. Distribution of PHTEs, the total S content and the ash yield (Aad) in coal seam profiles (Aad and S in %; trace elements in ppm).
 J. Zhang et al. / International Journal of Coal Geology 57 (2004) 49–61 55

aluminosilicate minerals, and these minerals consti-
tute the bulk of the ash. Relatively high correlation
coefficient for Al2O3 with ash (r = 0.714, n = 36),
indicates that most of the Al2O3 is associated with
aluminosilicate minerals. The K2O content is highly
correlated with ash content (r = 0.815, n = 36); indi-
cating that K is contained in the K-bearing clay
mineral (illite). The modes of occurrence of Ti are
mainly titanium oxides (rutile). Na is contained in
clay minerals (smectite) and NaCl; Mg in dolomite
and clay minerals; Fe in sulfides and Fe-oxide; Ca in
calcite, dolomite and apatite; and S in sulfides, sulfate
and in organic association. The relationship between
the major oxides and ash content of coals from high
to low is in the order of: Si>Al>K>Ti>Na>Mg>
Ca>Fe>S. This order is similar to that of the Kimura
(1998) results. The determination of the sulphur
content in two coal seam profiles in QFDA shows
that the total S content is highly variable in the coal
seam profiles, ranging from 2% to 6.2% in ZM coal
seam profile and from 2.2% to 5.7% in QG coal seam
profile (Fig. 4).
5. Potentially hazardous trace elements in coals
The ranges, arithmetic means and geometric means
of PHTEs in Late Permian coal and in the Late
Triassic coal in QFDA, southwestern Guizhuo, China
are listed in Tables 2 and 3.
Gluskoter et al. (1977) used a value of six times the
Clarke value to determine if an element is enriched in
the whole coal. By these criteria, As, Hg, Se, Mo and
Sb are enriched; while F, U, Zn and Tl fall between
the 1/6  and 6  range. All other PHTEs fall below
1/6  and are therefore considered depleted in the Late

Table 2
Ranges, arithmetic means and geometric means of PHTEs in Late Permian coals in QFDA and in Liupanshui Mining Area in southwestern
Guizhuo, China (ppm)
Element QFDA Clarke valuea EFb Liupanshuic World
Range Av. Gm. Number Range Av. Ranged Av.e
As 0.2 – 181 26.1 6.1 28 1.8 14.5 3 – 19 8 0.5 – 80 5
Ba 13 – 280 108 80 28 425 0.3 13 – 437 61 20 – 1000 500
Be 0.2 – 3.0 1.3 1 24 2.8 0.5 0.6 – 2.9 1.3 0.1 – 15 3
Cd 0.02 – 0.6 0.1 0.06 28 0.2 0.6 0.2 – 1.3 0.6 0.1 – 3 0.6
Co 1.3 – 20 6.4 4.5 28 25 0.3 3 – 18 7 0.5 – 80 5
Cr 2.2 – 62 19.8 14.7 28 100 0.2 7 – 63 15 0.5 – 60 10
Cu 6.3 – 71 25.5 18.5 24 55 0.5 13 – 228 30 0.5 – 50 15
F 178 – 2259 693 565 12 625 1.1 20 – 500 80
Hg 0.04 – 5.1 1.1 0.5 32 0.08 13.7 0.02 – 1.0 0.012
Mn 10 – >242 62 41 24 950 0.07 22 – 402 128 5 – 300 50
Mo 0.34 – 78 18.9 8 28 1.5 12.6 1 – 11 3 0.1 – 10 5
Ni 2.1 – 46 19.6 14.9 20 75 0.3 6 – 54 18 0.5 – 50 15
Pb 1.1 – 11 4.4 3.8 24 12.5 0.3 7 – 27 14 2 – 80 25
Sb 0.1 – 8 1.7 0.8 28 0.2 8.7 0.3 – 1.1 0.7 0.1 – 10 3
Se 0.8 – 14.4 6.1 4.8 28 0.05 121.2 0.2 – 10 3
Sn 0.2 – 3.1 1.8 1.4 28 2 0.9 1–5 2 1 – 10 1
Th 0.6 – 10 5.1 3.8 28 7.2 0.5 2 – 20 8 0.5 – 10 2
Tl 0.01 – 1.3 0.6 0.4 24 0.45 1.4 0.4 – 1.2 0.7 0.2 – 1 0.1
U 1 – 28.8 8.3 4.1 14 1.8 3.1 1–8 4 0.5 – 10 1
V 13 – 298 103 68 28 135 0.8 15 – 514 70 2 – 100 25
Zn 6 – 1246 120 33 28 70 1.7 5 – 106 21 5 – 300 50
Av.: arithmetic mean; Gm.: geometric mean.
a
From Mason and Moore (1982).
b
Enrichment factor relative the crustal abundance according to Gluskoter et al. (1977).
c
From Zhuang et al. (2000).
d
From Swaine (1990).
e
Compiled from Valkovic (1983), after Beaton et al. (1991).
56 J. Zhang et al. / International Journal of Coal Geology 57 (2004) 49–61

Table 3 between the 1/6  and 6  range. All other PHTEs

Ranges, arithmetic means and geometric means of PHTEs in Late fall below 1/6 .
Triassic coals in QFDA, southwestern Guizhuo, China (ppm)
In a comparison with World coal averages, the Late
Element Range Av. Gm. Number Clarke EFb
Permian coals in QFDA are highly enriched in As
valuea
(more than 5 ), Hg (more than 91 ), F (more than
As 1.2 – 238 72.5 28.6 16 1.8 30.4
8 ) and U (up to 8 ). Mo, Se, Th, V and Zn are
Ba 46 – 112 78 73 6 425 0.2
Co 2.6 – 4.9 3.4 3.3 7 25 0.1 slightly enriched. The Late Triassic coals in QFDA are
Cr 8.0 – 19.2 12.7 12.0 7 100 0.1 highly enriched in As (more than 14 ) and Hg (more
F < 10 – 152 75 49 7 625 0.1 than 100 ), whereas Mo, Th and U are slightly
Hg 0.06 – 10.5 1.61 0.81 14 0.08 20.1 enriched.
Mo 4.1 – 16.6 9.8 8.7 7 1.5 6.5
The arithmetic means of As, Mo, Sb, U and Zn in
Ni 6.8 – 37 21.9 15.9 2 75 0.3
Sb 1.3 – 7.8 3.8 3.2 7 0.2 18.8 the Late Permian coals studied are higher than in Late
Se 2.0 – 5.9 3.1 2.8 6 0.05 61 Permian coals from the Liupanshui Mining District in
Th 1.0 – 4.4 2.7 2.4 7 9.6 0.3 Guizhou province (Zhuang et al., 2000).
U 1.3 – 7 4.4 3.4 6 2.7 1.6 Feng et al. (1998) reported the average contents of
Zn 5.2 – 62 19.2 13.4 6 70 0.3
some volatile trace elements in Late Permian coals
Av.: arithmetic mean; Gm.: geometric mean. from most Coal Mining Bureaus in Guizhou province:
a
From Mason and Moore (1982).
b
Enrichment factor relative the crustal abundance according to
As, 10.2 ppm; Cd, 0.20 ppm; Hg, 0.55 ppm; Pb, 15.7
Gluskoter et al. (1977). ppm; Sb, 13.8 ppm; Se, 2.4 ppm; Tl, 0.35 ppm; and
Zn, 40.4 ppm. A comparison with his reported values
shows that the Late Permian coals in QFDA are
Permian coals in QFDA, southwestern Guizhou, Chi- highly enriched in As, Hg, Se, Tl and Zn.
na. In the Late Triassic coals in the QFDA, As, Hg, Se, Based on our study and earlier reports, we con-
Mo and Sb are also enriched, while only U falls clude that the QFDA in Southwest Guizhou is a

Table 4
Correlation coefficients between the content of each trace element and coal ash or selected major elements
Element Aad SiO2 Al2O3 Fe2O3 CaO + MgO K2O S Number Confidence level
(a < 0.01)
As 0.12 0.04 0.16 0.13 0.02 0.09 0.10 36 0.418
Ba 0.35 0.32 0.67 0.13 0.26 0.48 0.06 36 0.418
Be 0.09 0.08 0.60 0.02 0.27 0.52 0.06 27 0.470
Cd 0.15 0.29 0.20 0.12 0.30 0.004 0.001 27 0.470
Co 0.44 0.37 0.73 0.12 0.07 0.46 0.03 36 0.418
Cr 0.45 0.40 0.80 0.15 0.17 0.53 0.005 36 0.418
Cu 0.13 0.19 0.38 0.01 0.18 0.23 0.01 27 0.470
F 0.23 0.34 0.45 0.21 0.32 0.35 0.41 19 0.549
Hg 0.05 0.004 0.26 0.09 0.23 0.006 0.09 37 0.418
Mn 0.03 0.04 0.04 0.12 0.39 0.04 0.16 15 0.606
Mo 0.34 0.23 0.54 0.13 0.10 0.44 0.05 36 0.418
Ni 0.29 0.34 0.23 0.12 0.08 0.01 0.1 27 0.470
Pb 0.25 0.33 0.006 0.12 0.05 0.19 0.17 27 0.470
Sb 0.24 0.29 0.27 0.18 0.23 0.21 0.24 36 0.418
Se 0.22 0.19 0.48 0.22 0.24 0.25 0.1 36 0.418
Sn 0.19 0.27 0.58 0.09 0.36 0.31 0.17 27 0.470
Th 0.36 0.41 0.75 0.04 0.28 0.40 0.17 36 0.418
Tl 0.31 0.32 0.71 0.05 0.27 0.34 0.03 27 0.470
U 0.66 0.67 0.85 0.23 0.31 0.81 0.09 22 0.515
V 0.23 0.23 0.69 0.001 0.19 0.35 0.06 27 0.470
Zn 0.35 0.24 0.04 0.10 0.04 0.22 0.11 32 0.449
Aad: the ash yield.
 J. Zhang et al. / International Journal of Coal Geology 57 (2004) 49–61 57

typical area, showing enrichment of volatile PHTEs in

coals, including As, Hg, Se, Sb and Mo.
Correlation analysis was performed on the PHTEs
and coal ash or selected major elements (Table 4). At a
99% confidence level, Co, Cr and U show a positive
correlation with the coal ash, and Ba, Mo, Th and Zn
show a weak correlation. The major elements selected
were Al2O3 (representing the aluminosilicate group),
Fe2 O 3 and S (representing the sulphide group),
CaO + MgO (representing the carbonate group) and
K2O (representing the illite) (Querol et al., 1996,
1997). Trace elements showing positive correlation
with Al2O3 are Ba, Be, Co, Cr, Mo, Se, Sn, Th, Ti, U
and V. Trace elements with a positive correlation to
K2O include Ba, Be, Co, Cr, Mo and U. No correlation
between the trace elements and Fe2O3 or S indicates
the various origins of iron sulphides (Zhang et al.,
2002).
The distributions of PHTEs in two Late Permian
coal seam profiles (ZM and QG) are illustrated on Fig.
4. In the ZM coal seam profile, As, Cd, Sb, Se and Zn Fig. 5. Locations of arsenic >30 ppm in coals in QDFA,
are enriched in the low part and the upper part of the southwestern Guizhou, China.
seam, Mo and Ni are higher in the middle part of the
seam. In the QG coal seam profile, As, Ba, Mo, Ni, 35,000 ppm and from Jiaoluo Township was up to
Sb, Se and Zn are enriched in the semidull coal, and 2223 ppm.
Cr, Mo, Ni and Se are relatively enriched in the dull
coal at the bottom of the seam. 6.2. The regions of high-mercury coal in QDFA

The regions in which the mercury in coals is

6. The regions enriched in As, Hg and F in coals in
QFDA
6.1. The regions of high-arsenic coal in QDFA
The regions in which the arsenic in coals is greater
than 30 ppm in the QFDA, southwestern Guizhou,
China have been mapped (Fig. 5). They are Xiongwu
area (A), Nibu area (B), Dayakou area (C), Getang
area (D), Longtoushan area (E), Nanmuchang area (F)
and Dachang area (G). A, B, C, D and F are the Late
Permian coal and E is the Late Triassic coal. More
than 2000 cases of arsenosis have been documented in
Jiaoluo Township in Getang area (E) (Du et al., 2000;
Zhang et al., 2000). Cases of arsenosis have been
found in 85 villages in the QFDA, southwestern
Guizhou, China (Zhou et al., 1998). Belkin et al.
(1997) reported that the arsenic concentration in coal
from Haizhi Township in Getang area was up to
greater than 0.5 ppm in the QFDA, southwestern
Guizhuo, China have been mapped (Fig. 6). They
are Nibu area (A), Getang area (B), and Longtoushan
area (C). A and B are Late Permian coal and C is Late
Triassic coal. The case of mercury poisoning from
coal burning has not been documented in the QFDA,
but the potential impact of mercury on the environ-
ment is of concern. The mercury concentration in
coals from Longtoushan area is up to 10.5 ppm, and
Belkin et al. (1997) reported that the mercury con-
centration in coals from Jiaoluo Township in Getang
area was up to 29 ppm.
6.3. The regions of high-fluorine coal in QDFA
The regions of extreme fluorine enrichment in
coals (>1000 ppm) in the QFDA, southwestern Guiz-
hou, China are only Nibu area (A) and the Liuzhi well
field (B) (Fig. 7). The fluorine concentration in coals
58 J. Zhang et al. / International Journal of Coal Geology 57 (2004) 49–61

nian Age, about 189 Ma; (c) d34S is mainly negative

Fig. 6. Locations of mercury >0.5 ppm in coals in QDFA,
southwestern Guizhou, China.
from Nibu area is up to 2259 ppm. The fluorine
concentration in coals from the Liuzhi well field is
the highest in Guizhou province. The range of fluorine
concentration is between 998.5 and 2544 ppm, and
the average is surprisingly high, 1797 ppm, in the
Liuzhi well field. The endemic fluorosis area mainly
covers northwestern Guizhou province, about 720,000
of 740,000 residents of Zhijin County in Guizhou
province have fluorosis (Zheng et al., 1999). Fluorosis
caused by coal burning in QFDA, southwestern Guiz-
hou, China is not serious as compared with north-
western Guizhou province.
and S mainly from adjoining rocks; (d) temperature of
hydrothermal solution: 150– 200 jC; (e) composition
of hydrothermal solution: high salinity, high density
hydrothermal solution mixed with organic thermal
solution; (f) origin of thermal water: crustal circulating
thermal water mixed with precipitation; (g) thermal
source: crustal magmatic body and the deep faulting;
(h) origin of the volatile PHTEs in coals: adjoining
rocks and magma; and (I) energy of migration: high
temperature and high pressure (Zhang, 1999).
The QFDA is enriched in many noble metal ore
deposits, including, gold, antimony, arsenic, mercu-
ry and thallium. These noble metal ore deposits
were formed from the low-temperature hydrother-
mal activity.
The cleat minerals in coals were mainly formed
from low-temperature hydrothermal fluids, the trace
elements are thought to have mainly derived from the
underlying rocks and hydrothermal fluids with the
temperature range of about 150 – 200 jC (Zhang,
1999). The coals enriched in the volatile PHTEs are
located in the cores of anticline and anticlinorium,
which connected with the deep faults through the
normal faults. The regions of coals enriched in volatile

7. Low-temperature hydrothermal activity and the

volatile PHTEs enrichment

The QFDA is a typical area in that the low-

temperature hydrothermal activity was very strong in
its geologic history (mainly during the Yanshanian
age, about 189 Ma). And the QFDA is a typical area
in terms of enrichment of volatile PHTEs in the coal,
including As, Hg, Se, Sb and Mo.
The low-temperature hydrothermal mineralization
in QFDA, southwestern Guizhou is characterized by: Fig. 7. Locations of extreme high fluorine (>1000 ppm) coals in
(a) multi-stage incursion; (b) incursion age: Yansha- QDFA, southwestern Guizhou, China.
 J. Zhang et al. / International Journal of Coal Geology 57 (2004) 49–61
Fig. 8. Relationship of arsenic content in coals and their distance to
gold ores.
PHTEs overlap with the regions of noble metal ore
deposits.
The contents of some volatile trace elements in
coals, such as, As, Se, Hg, Sb, among others, are
related to their distance to the noble metal ore depos-
its. Fig. 8 shows the relationship of the arsenic content
in coals and their distances to gold ores.
Significant epigenetic volatile PHTEs enrichment in
coals may have occurred as a result of the low-temper-
ature hydrothermal activity and tectonic movement.
During the Yanshanian age (about 189 Ma), the
deep-plutonic hydrothermal fluids carrying mineral
matter and mineralizing constituents moved up into
the upper crust through the deep faults and mixed with
precipitate water. Some of trace elements in adjoining
rocks were dissolved by the hydrothermal fluids and
the hydrothermal fluids could also dissolve part of the
organic matter. Then the hydrothermal fluids moved
into coalbeds and rock strata through the faults. The
trace elements, sulfur and mineral matter in the
hydrothermal fluids were deposited and enriched in
coalbeds (and adjacent rocks), while temperature,
pressure, pH value, fs and the activity of reduced
sulfur decreased; and the Eh value in the hydrothermal
fluids increased.
8. Summary and conclusions
The major minerals in the Late Permian coal
studied are quartz, kaolinite, illite, pyrite, calcite,
smectite and marcasite, the major minerals in the Late
Triassic coal studied are kaolinite, illite, pyrite, smec-
tite and marcasite. Late Permian coal is enriched in
quartz, but there is little quartz in the Late Triassic
59
coal studied. The other accessory minerals in coal
studied are rutile, dolomite, siderite, gypsum, chlorite
and melanterite. Apatite, collophane and florencite
were found in the Late Permian coal.
The Late Permian coals show much higher ash yield
than the Late Triassic coals, and the SiO2 content
shows a broad variation. The Al2O3 content varies
from 0.8% to 13.4%, Fe2O3 from 0.2% to 14.6%, TiO2
from < 0.1% to 2.9% and CaO from < 0.1% to 11.9%.
The contents of MnO, MgO, K2O and Na2O are
relatively low. The relationship between the major
oxides and the ash content of coal from high to low
is in the order of Si>Al>K>Ti>Na>Mg>Ca>Fe>S.
The ranges, arithmetic means and geometric means
of PHTEs in Late Permian coals and in the Late
Triassic coals in QFDA, southwestern Guizhou, China
are given. A comparison with crustal Clarke values
shows that the QFDA coals are enriched in As, Hg,
Se, Mo and Sb. A comparison with World coal
averages shows that the Late Permian coals in QFDA
are highly enriched in As, Hg, F and U, whereas Mo,
Se, Th, V and Zn are slightly enriched. The Late
Triassic coal in QFDA are highly enriched in As and
Hg, whereas Mo, Th and U are slightly enriched. The
concentrations of As, Hg, Mo, Se, Tl and Zn in the
QFDA coals are higher than other nearby Guizhou
coals and Liupanshui coals.
The QFDA is a typical area where the low-temper-
ature hydrothermal activity was very strong in its
geologic history (Yanshanian Age, about 189 Ma).
The QFDA is a typical area in the enrichment of
volatile PHTEs in coals, including As, Hg, Se, Sb,
Mo, among others. The regions of the volatile PHTEs
coals overlap with the regions of noble metal ore
deposits, including gold, antimony, arsenic, mercury
and thallium. The coals enriched in the volatile PHTEs
are located in the cores of anticline and anticlinorium,
which are connected with deep faults through the
normal faults. Significant epigenetic enrichment of
volatile PHTEs in coals occurred as a result of the
low-temperature hydrothermal activity and tectonic
movement.
Acknowledgements
This project was supported by the National Natural
Science Foundation of China (NSFC) (40133010,
60 J. Zhang et al. / International Journal of Coal Geology 57 (2004) 49–61
40272071, 49632090). The authors wish to acknowl-
edge Prof. Yang Qi of China University of Geoscience,
a member of Chinese Academy of Sciences (CAS),
Prof. Han Dexin, a member of Chinese Academy of
Engineering (CAE), and Prof. Zhang Pengfei of
CUMTB for their advice. They would also like to
thank Dr. Robert B. Finkelman of U.S. Geological
Survey (USGC) for reading an earlier version of the
manuscript and providing thoughtful comments and
constructive suggestions. Thanks are also expressed to
Dr. Jim Hower for providing constructive comments
on the manuscript and a research paper.
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