Environ Geochem Health (2007) 29:33–44
DOI 10.1007/s10653-006-9059-8
ORIGINAL PAPER
Geochemistry of the barkinite liptobiolith (Late Permian)
from the Jinshan Mine, Anhui Province, China
Yuzhuang Sun Æ Mingyue Lin Æ Peng Qin Æ
Cunliang Zhao Æ Kankun Jin
Received: 28 August 2005 / Accepted: 3 August 2006 / Published online: 4 January 2007

Springer Science+Business Media B.V. 2006
Abstract This paper discusses the geochemistry
and mineralogy of the barkinite liptobiolith of
the Late Permian age from the Jinshan Mine,
Guangde County, Anhui Province, China. Sam-
ples were examined using inductively coupled
plasma-mass spectroscopy, X-ray fluorescence,
cold-vapor atomic absorption spectrometry, ion-
selective electrode, sequential chemical extrac-
tion, scanning electron microscopy equipped with
energy-dispersive X-ray, and optical microscopy.
The coal is a medium-ash and high-sulfur
resource. Minerals in the coal are composed of
kaolinite, pyrite, calcite, and quartz. Pyrite and
calcite are derived from seawater during peat
accumulation. Quartz in the coal is of authigenic
origin. Part of the kaolinite is from a land-source
region, and part occurs as cell-fillings and is of
authigenic origin. The results also indicate that the
barkinite liptobiolith contains some toxic ele-
ments in high concentrations. Elements including
Li, Be, Si, Sc, Ti, V, Cr, Fe, Ga, Se, Y, Zr, Mo, the
rare earth elements (REEs), W, Hg, Tl, Pb, Th,
and U in the coals are enriched in the barkinite
liptobiolith. Results of sequential chemical
Y. Sun (&) Æ M. Lin Æ P. Qin Æ C. Zhao Æ K. Jin
Key Laboratory of Resource Exploration Research of
Hebei Province, Hebei University of Engineering,
Guangmingnan Street 195, Handan, Hebei 056038,
China
e-mail: sun_yz@hotmail.com
extraction showed that Li, Sc, Ti, Cr, Y, Zr, REEs,
and Th in the coal mainly occur as silicates, while
Be and W are related to organic matter. Pyrite is
the dominant source of S, Mo, Hg, Tl, and Pb.
Gallium only occurs in silicate, and U and V occur
both in organic and silicate associations.
Keywords Geochemistry Æ Barkinite liptobiolith Æ
Trace elements Æ Major elements Æ Late Permian Æ
Jinshan Mine Æ China
Introduction
Understanding the migration and enrichment of
the trace elements in coal is important, both
academically in developing coal-forming theories
and practically in optimizing coal utilization.
These elements may serve as indicators of min-
eralization during coal formation, and some ele-
ments are major contributors to environmental
pollution during coal combustion and utilization
(Dai & Ren, 2006; Seredin & Shpirt, 1995). Many
previous studies have examined the inorganic
geochemistry of Chinese coals (Dai, Hou, Ren, &
Tang, 2003a; Dai, Ren, Hou, & Shao, 2003b; Dai,
Ren, Zhang, & Hou, 2003c; Dai, Ren, & Ma,
2004b; Dai, Chou, Yue, Luo, & Ren, 2005a, Dai,
Ren, Tang, Yue, & Hao, 2005b; Finkelman et al.,
2002; Luo et al., 2004) and the petrologic and
organic geochemistry of barkinite of China (Sun
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34
& Kalkreuth, 2000). However, we have found no
studies concerned with the inorganic geochemis-
try of barkinite. Barkinite is a peculiar maceral of
Chinese coal petrographic nomenclature, because
its morphological features suggest an origin from
bark tissue (Sun, 2003; Sun, Püttmann, Kalkreuth,
& Horsfield, 2002; Zhong & Smyth, 1997). In this
paper we report new data on the mineralogy and
geochemistry of this peculiar maceral.
Geological setting
The Jinshan Mine is located in Guangde County,
southeastern Anhui Province, southern China
(Fig. 1). Coal-bearing strata belong to the Long-
tan Formation of the Late Permian age. Regional
geology of barkinite liptobiolith has been studied
by many geologists (Han, Ren, & Guo, 1983;
Mao, Zhang, & Gu, 1997; Wang, Liu, & Song,
1998; Yan & Li, 1958; Zhang, Tang, Zhen, &
Guo, 1998). The paleogeography of the Late
Permian in southern China ranged from upland
through continental deposits and littoral facies to
shallow marine deposits (Fig. 1).
The Late Permian coal-bearing strata in the
Jinshan Mine include the Longtan Formation
(P2l) and Dalong Formation (P2d). The Longtan
Formation is the major coal-bearing formation,
which consists of sandstone, limestone, mudstone,
and coal beds, with a thickness between 18 m
and 185 m. The coal bed, with a thickness of
0.8–3.2 m, is in the uppermost portion of the
Fig. 1 Location of the
Jinshan Mine and the
paleogeographic map of
the Late Permian in
southern China (modified
from Han & Yang, 1980)
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Environ Geochem Health (2007) 29:33–44
Longtan Formation. The non-coal-bearing strata
underlying the Longtan Formation are Early
Permian Gufeng Formation (P1g) and Xixia
Formation (P1x), and are Carboniferous sedi-
ments. The overlying non-coal-bearing forma-
tions include Triassic, Jurassic, Cretaceous,
Tertiary, and Quaternary systems.
Experimental methods
Eight bench samples were collected from the bark-
inite coal bed in the Jinshan Mine, following the
Chinese Standard Method GB 482-1995 (1995). The
sample for each bench was 10 cm wide and 10 cm
deep. All clay partings thicker than 30 mm were
excluded. From top to bottom, the eight bench
samples of coal were labeled CHD-1 to CHD-8.
Epoxy-bound pellets were made from the coal
samples, crushed and ground to < 850 lm, and
prepared to a final polish with 0.05 lm alumina.
Mineral analysis was performed with reflected-
light optics at a magnification of ·500. In addition
to optical microscopy, the minerals in the samples
were identified by X-ray powder diffraction, using
Ni-filtered Cu-Ka radiation and a scintillation
detector. The XRD pattern was recorded over a
2h interval of 3–70, with a step size of 0.02.
A scanning electron microscope equipped with
an energy-dispersive X-ray spectrometer was
used to determine the distribution of elements in
the coal. The accelerating voltage was 20 kV, and
the beam current was 10–10 A.
Environ Geochem Health (2007) 29:33–44 35

Samples for geochemical analysis were crushed
and ground to less than 200 mesh. X-ray fluores-
cence (XRF, Cu–Ka source) spectrometric anal-
ysis was used to determine the oxides of the major
elements, including Si, Al, Ca, K, Na, Fe, and Mg.
Inductively coupled-plasma mass spectrometry
(ICP-MS) was used to determine the concentra-
tions of most trace elements in the coal. Mercury
was determined by cold-vapor atomic absorption
spectrometry (CV-AAS). Fluorine and boron
were determined, respectively, by an ion-selective
electrode (ISE) method and inductively coupled-
plasma atomic emission spectrometry (ICP-
AES).
Sample CHD-8 was crushed to less than 100
mesh for a six-step sequential chemical extraction
procedure (SCEP) as outlined by Dai et al.
(2004a). Leaching methods used in coal have a
major advantage over float–sink methods in that
specific elemental forms are anticipated to be ei-
ther present or absent in different fractions,
depending on their solubility behavior in the vari-
ous reagents used for the different leaching stages
(Huggins, 2002). In this study the authors identified
six types of organic to inorganic associations of
elements in coal: water-soluble, ion-exchangeable,
carbonate, organic-bonded, silicate, and sulfide.
Results and discussion
Proximate analysis
Proximate analysis and rank (vitrinite random
reflectance, %Rr) of the coal benches from the
Jinshan Mine are given in Table 1. In terms of the
Table 1 Ultimate analysis and vitrinite reflectance of the
coal from the Jinshan Mine, Anhui Province (as
percentages) (M moisture, ad as received, VM volatile
Sample no. Mad Ashd VMdaf
Chinese Classification for Coal Quality GB/T
15224.1-2004 (2004) and GB/T 15224.2-2004
(2004), the coal is categorized as a medium-ash
(>29%) and high-sulfur (>3%) coal. Sulfur in the
eight benches is mainly pyritic (Table 1). The
highest sulfur content is 15.6%, and its average
content is about 8%. Such high sulfur contents are
harmful to environments and human health. The
high organic sulfur content (average 1.04%) in
the coal cannot be accounted for by the original
plant sulfur. Therefore, there must have been
some sulfur incorporated into the peat after burial
(Chou, 1990, 1997, 2004; Dai, Ai, Jiao, Ma, & Li,
2000a).
It is difficult to determine the organic sulfur
content of individual macerals using traditional
chemical methods, due to their small size and
their intimate relationship with one another in
most coals (Chou, 1990; Dai, Ren, Tang, Shao, &
Li, 2002b; Mastalerz & Bustin, 1993; Ward &
Gurba, 1998). Raymond (1978) determined the
organic sulfur content of individual macerals di-
rectly by using an electron microprobe. The
technique in this study used a scanning electron
microscope (SEM) in conjunction with an energy
dispersive X-ray (EDX) spectrometer. The re-
sults show that the organic sulfur content in
macerals of the same coal sample decreases in the
order: barkinite (1.14%), collodetrinite (1.01%),
corpogelinite (0.97%), collotelinite (0.94%),
semifusinite (0.91), and fusinite (0.90%). The re-
sults of the organic sulfur content of the macerals
are in accordance with those of the wet chemical
analysis as described above.
The coal has an average vitrinite reflectance of
0.71% and a high yield of volatile matter (varying
matter, d on a dry base, daf on a dry and ash-free base, St
total sulfur, Sp, sulfide sulfur, Ss sulfate sufur, So organic
sulfur, Ro,ran mean random reflectance of vitrinite)
St,d Sp,d Ss,d So,d Ro,ran

CHD-1 4.58 44.3 44.6 15.6 14.3 0.23 1.16 0.72

CHD-2 4.69 14.4 45.9 12.1 10.9 0.34 0.92 0.73
CHD-3 4.87 22.8 45.1 2.56 1.26 0.08 1.22 0.69
CHD-4 4.72 25.6 44.7 5.64 4.27 0.15 1.22 0.73
CHD-5 4.65 17.7 45.6 4.87 3.62 0.21 1.04 0.72
CHD-6 4.71 18.5 46.9 2.69 1.63 0.09 0.97 0.70
CHD-7 4.68 20.6 47.9 8.94 7.84 0.05 1.05 0.69
CHD-8 4.77 25.0 50.2 11.6 10.4 0.41 0.75 0.71
Average 4.71 23.6 46.4 8.01 6.77 0.20 1.04 0.71

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36 Environ Geochem Health (2007) 29:33–44

from 44.6% to 50.2%), due to the high content of
barkinite in the coal: a highly volatile bituminous
rank coal.
Mineralogy
Minerals in the coals from the Jinshan Mine are
mainly pyrite, quartz, clay minerals, and a trace
amount of calcite (Table 2). The predominant
mode of occurrence of the pyrite is as fine grains
distributed in various macerals, and sometimes
occurring as massive pyrite or cell-fillings; how-
ever, other forms of pyrite, including framboidal,
fracture-filling, and nodular forms, have not
identified in these coals. The mode of occurrence
of pyrite suggests that it is syngenetic rather than
epigenetic (Chou, 1997; Dai, Sun, & Zeng,
2006e). The content of the pyrite in the top and
bottom portion of the column section is much
higher than that in the middle portion, which is
in accordance with the general variation of pyr-
ite in coals that were influenced by seawater
during peat accumulation (Chou, 1997, 2004; Dai
et al., 2002b). The variation of pyrite in the
column section showed that the mire in the study
area had been seriously influenced by seawater
in the early and late stages during peat accu-
mulation.
The clay minerals occur either as lenses or as
fine grain particles in small or as fusinite cell-
fillings. The SEM-EDX results showed that the K,
Na, and Mg content in the clay minerals is
< 0.8%, indicating that the clay minerals are
mainly kaolinite. The clay mineral identity was
also confirmed by X-ray diffraction.
Quartz occurs as very fine particles
of < 5 lm. The mode of occurrence of quartz,
such as sharp edges, particles connecting with
each other, and sometimes filling in plant cavi-
ties, indicates that the quartz in the coal bed is
of authigenic origin rather than the epiclastic
sediments.
Calcite does not occur as fracture- or cleat-
fillings but as well-developed crystals in the coal.
Calcite of terrigenous origin is very rare in coal
(Bouška, Pešek, & Sykorova, 2000; Ward, 2002),
because it can be easily decomposed under acid
conditions. The well-developed crystals of calcite
indicate that calcite is derived from seawater
during peat accumulation. The alkaline condi-
tions of peat mire influenced by seawater may
favor calcite preservation.
Geochemistry
Major elements
The concentration of major and trace elements in
the coal from the Jinshan Mine are presented in
Table 3. The average concentration of Fe2O3
(5.4%) and SiO2 (12%) are much higher than
those of ordinary coals from China and the USA,
as reported by Dai, Chou, Li, Ren, and Luo
(2006a) and Finkelman (1993), respectively. The
high concentrations of Fe2O3 and SiO2 are due to
the high percentage of pyrite and quartz in the
coal. In particular, samples CHD-1 and CHD-2
are highest in Fe2O3 and SiO2, 25% and 17%,
respectively. Overall, the concentration of major

Table 2 Maceral and mineral compositions of the coals from the Jinshan Mine (as percentages) (bdl below detection limit,
AM arithmetic mean)
Sample no. Maceral Clay minerals Pyrite Quartz Calcite

CHD-1 78.2 5.2 9.6 4.2 2.8

CHD-2 85.5 2.6 7.5 3.2 1.2
CHD-3 79.8 6.7 1.1 12.4 bdl
CHD-4 84.4 8.9 4.7 1.2 0.8
CHD-5 82.8 4.4 3.2 8.6 1.0
CHD-6 78.4 4.1 7.1 9.2 1.2
CHD-7 76.3 3.2 8.5 10.6 1.4
CHD-8 68.5 4.3 10.4 14.6 2.2
AM 79.3 4.9 6.5 8.0 1.3

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Environ Geochem Health (2007) 29:33–44 37

Table 3 Concentrations of major and trace elements in the coals from the Jinshan Mine, Anhui Province (in micrograms
per gram except for oxides of major elements, which are given as percentages)
Element CHD-1 CHD-2 CHD-3 CHD-4 CHD-5 CHD-6 CHD-7 CHD-8 AM Chinaa USAb

Al2O3 11 3 8.9 11.1 4.3 4.5 3.7 4.2 6.3 6.1 2.83
CaO 3.8 1.5 0.01 1.1 1.4 1.4 1.8 1.7 1.6 1.4 0.64
Fe2O3 25 3.4 0.72 4 1.2 0.7 4.2 4.1 5.4 5.8 1.86
K2O 0.1 0.01 0.67 0.34 0.34 0.25 0.24 0.08 0.25 0.21 0.43
MgO 0.07 0.07 0.27 0.06 0.06 0.09 0.1 0.14 0.11 0.25 0.18
Na2O 0.7 0.07 0.09 0.06 0.06 0.06 0.08 0.11 0.07 0.18 0.11
SiO2 6.2 6.9 16 11 12 14 13 17 12 8.5 5.79
Li 47 68 150 140 160 230 190 190 150 32 16
Be 5.1 3 5.8 4.9 6.4 7.7 4.5 2.9 5 2.1 2.2
B 69 51 79 54 69 110 110 96 79 53 49
F 120 90 150 97 110 110 150 86 110 130 98
P 99 38 110 45 3.9 46 59 110 64 420 430
Sc 6.5 6.2 11 5 5.8 8.7 7.2 35 11 4.7 4.2
Ti 1030 1100 2090 890 2010 1990 1390 3510 1750 2200 800
V 24 20 45 31 31 43 36 340 72 35 22
Cr 23 21 42 16 19 21 16 86 31 15 15
Mn 240 31 33 28 13 26 38 71 59 120 43
Co 6.5 1.2 4.8 6.3 6.2 8.3 7.2 27 8.5 7.1 6.1
Ni 21 8.4 24 15 13 14 18 25 17 14 14
Cu 18 9.6 12 19 11 10 11 35 16 18 16
Zn 49 21 20 15 14 22 16 28 23 42 53
Ga 12 9.2 16 7.8 7.9 14 17 40 15 6.6 5.7
Ge 1.9 1.9 2.2 1.1 1.4 1.6 2.9 2.2 1.9 3 5.7
As 13 13 9.3 10 10 10 26 15 13 3.8 24
Se 3.7 6.5 2.9 2.9 2.6 2 9.6 2.2 4.1 2.5 2.8
Rb 8.1 6.3 19 1.6 1.6 3.7 3.5 6.5 6.3 9.3 21
Sr 130 43 84 59 39 40 33 130 69 140 130
Y 28 25 53 30 37 42 29 18 33 18 8.5
Zr 53 74 160 95 140 120 110 380 140 89 27
Nb 5.6 11 15 15 23 21 14 22 16 9.5 2.9
Mo 3.7 12 6.5 11 6.2 3.3 19 3.3 8.1 3.2 3.3
Cd 0.59 0.38 0.63 0.83 1.2 1.3 0.76 0.75 0.79 0.25 0.47
Sn 3.7 2 2.3 3.2 3.2 4.8 3.2 8.7 3.9 2.1 1.3
Sb 0.36 0.36 0.3 0.3 0.23 0.16 0.86 1.1 0.45 0.84 1.2
Cs 1 0.81 1.7 0.16 0.13 0.53 0.38 0.72 0.68 1.1 1.1
Ba 88 110 120 83 79 91 69 110 92 160 170
La 17 27 87 39 55 57 41 33 44 26 12
Ce 31 50 160 71 92 100 74 44 78 49 21
Pr 4.2 6.2 18 8.2 11 12 8.5 5.7 9.2 5.5 2.4
Nd 17 23 68 30 36 42 33 20 34 22 9.5
Sm 3.5 4.5 12 5.2 6.8 8.4 6.2 3.7 6.3 4.3 1.7
Eu 0.76 0.73 2.2 0.92 1.1 1.2 0.83 0.56 1 0.87 0.4
Gd 4 4.7 12 5.6 6.5 8.1 6.3 3.1 6.3 3.7 1.8
Tb 0.63 0.65 1.7 0.83 1 1.3 0.88 0.52 0.94 0.67 0.3
Dy 4.1 3.9 9.6 4.8 5.8 8.2 5.2 3.4 5.6 3.13 1.9
Ho 0.89 0.77 1.9 0.98 1.2 1.6 0.99 0.69 1.1 0.65 0.35
Er 2.7 2.2 5.4 2.9 3.5 4.8 2.9 2.3 3.4 1.86 1
Tm 0.43 0.35 0.84 0.43 0.54 0.77 0.46 0.36 0.52 0.27 0.15
Yb 2.4 2 5.1 2.5 3.1 4.4 2.8 2.2 3.1 2.12 0.95
Lu 0.44 0.33 0.86 0.44 0.53 0.78 0.43 0.4 0.53 0.3 0.14
Hf 1.7 2.6 5.1 3 4.2 4.3 4.5 9.3 4.3 3.8 0.73
Ta 0.41 0.86 1 0.81 1.5 1.5 2.3 1.6 1.3 0.66 0.22
W 16 1.5 1.3 2.2 1.4 1.7 20 7.4 6.4 1 1
Hg 1.2 0.45 0.23 0.28 0.34 0.27 0.89 1 0.59 0.19 0.17
Tl 4.3 1.7 0.61 0.56 0.52 0.32 11 4.1 2.8 0.47 1.2

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Table 3 continued
Element CHD-1 CHD-2 CHD-3 CHD-4 CHD-5 CHD-6 CHD-7 CHD-8 AM Chinaa USAb

Pb 8.3 6.1 15 29 21 38 24 43 23 15 11
Bi 0.17 0.11 0.23 0.17 0.19 0.47 0.39 0.53 0.28 0.78 < 1.0
Th 4.2 9 11 5.9 7.8 13 21 26 12 5.8 3.2
U 13 8.7 20 2.6 2.2 7.9 4 6.7 8.1 2.4 2.1
a
Dai et al. (2006a)
b
Finkelman (1993)

elements is in accordance with the mineral com-
positions described above.
Trace elements
The average concentrations of Li, Be, B, Sc, Ti, V,
Cr, Ga, Y, Zr, Mo, rare earth elements (REEs),
W, Hg, Tl, Pb, Th, and U are higher than those
in ordinary Chinese and US coals (Table 3).
Particularly, the enrichment of the toxic trace
elements Be, Cr, Hg, Tl, and Pb in the coals from
the Jinshan Mine is worth noting, due to their
toxic effects.
The Be content in the Jinshan coal varies from
3 lg/g to 6.4 lg/g, with an average of 5 lg/g. This
value is not only higher than the average mean of
Be in bituminous coal (3.0±1.2 lg/g), as reported
by Eskenazy (2006), but is also higher than that in
Chinese and American coals, as reported by Dai
et al. (2006a) and Finkelman (1993), respectively.
Eskenazy (2006) showed that there was no clear-
cut ‘‘Be content-rank’’ relationship.
Although B in the Jinshan coal (average 79 lg/
g) is higher than that in coals from China (53 lg/
g) and the USA (49 lg/g), as reported by Dai
et al. (2006a) and Finkelman (1993), respectively,
its content is comparable to the B content in coals
influenced by brackish water, reported by Swaine
(1971) and Goodarzi and Swaine (1994). The B
content in the Jinshan coal is probably attribut-
able to the seawater-influenced sedimentary
environment.
The Clarke value for Hg in coal (world-wide
average Hg content) is 0.10 lg/g, regardless of
coal rank (Yudovich & Ketris, 2005). The Hg
content of the Jinshan coal (average 0.59 lg/g) is
about six-times higher than the Clarke value for
Hg in coal. There are some coals that are en-
riched in Hg by 1–2 orders of magnitude above
the Clarke value. Such coals are located in the
Donbas (Ukraine), Appalachian Basin and Texas
(USA), Russian Far East, and Southern China.
The mercury in these coals is usually accompa-
nied by other chalcophile trace elements and is
generally associated with epigenetic hydrother-
mal fluids (Dai, Ren, Chou, Li, & Jiang, 2006c).
However, no veined pyrite or other sulfide min-
erals of epigenetic hydrothermal origin were ob-
served in the Jinshan coal, either under optical
microscopy and SEM-EDX or by XRD. The high
concentration of Hg in the coal is possibly
attributable to the high content of syngenetic
pyrite and the particular maceral barkinite in the
coal, as described below.
Thallium varies considerably in the column
section of the Jinshan coal, from 0.32 lg/g to
11 lg/g, with an average of 2.8 lg/g (Table 3).
Thallium is significantly enriched in the top and
bottom portions of the column section but is very
low in the middle portions (CHD-3, CHD-4,
CHD-5, and CHD-6). The high content of pyrite
in the top and bottom portions of coal seam, as a
result of seawater influence, contribute the high
Tl concentration in the coal.
The concentrations of Cr (31 lg/g) and Pb
(23 lg/g) are about twice those of the Chinese
and US coal values reported by Dai et al. (2006a)
and Finkelman (1993). Chromium and Pb are
highest in the downmost portion (CHD-8) of the
coal bed.
The average concentration of rare earth ele-
ments (SREE = La+Ce+Nd+Sm+Eu+Tb+Yb+
Lu+Y) in the coal is 190 lg/g. This is much higher
than that of US coals and the ordinary Chinese
coals (Tables 4 and 5). In particular, SREE in
samples CHD-3 was 350 lg/g, and the L/H value
(ratio of light rare earth elements to heavy rare
earth elements) is up to 9.35. The distribution

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Environ Geochem Health (2007) 29:33–44 39

Table 4 Rare earth elements in coal benches from the Jinshan Mine, Anhui Province
Sample no. LREE (lg/g) HREE (lg/g) REE (lg/g) L/H dCe dEu

CHD-1 74 16 90 4.77 0.75 0.68

CHD-2 110 15 130 7.46 0.79 0.53
CHD-3 350 37 390 9.35 0.82 0.61
CHD-4 150 19 170 8.30 0.79 0.58
CHD-5 200 22 220 9.04 0.76 0.53
CHD-6 220 30 250 7.37 0.76 0.47
CHD-7 160 20 180 8.18 0.78 0.44
CHD-8 110 13 120 8.31 0.63 0.54
AM 170 21 190 7.85 0.76 0.55

Table 5 Results of sequential chemical extraction of some trace elements in sample CHD-8 (lg/g) (bdl below detection
limit)
State Li Sc Ti Cr Y Zr REE Be W B Mo Tl Pb Hg Ga U Th V

Water soluble 12 4.3 16 bdl bdl 56 bdl bdl 1.1 bdl bdl 0.26 bdl bdl bdl bdl 1.5 bdl
Ion-exchangeable 16 bdl 41 bdl 11 bdl bdl bdl bdl bdl bdl bdl bdl bdl bdl 1.4 bdl bdl
Carbonate 22 6.5 54 25 bdl 47 30 bdl 1.6 15 2.2 bdl 4.9 bdl bdl bdl bdl bdl
Organic-bonded 62 12 150 33 12 140 69 4. 11 140 1.5 0.55 2. 6 0.11 6.5 7.1 bdl 420
Silicate 710 130 9970 340 59 1560 420 2.5 1.1 11 2.3 0.43 3.7 0.06 62 13 68 27
Sulfide 12 2. 6 40 18 9.1 54 26 bdl 1.2 bdl 16 5.5 57 1. 5 bdl bdl 3. 6 bdl

patterns of rare earth elements in the eight Results of sequential chemical extraction
benches are similar, all showing a clear Eu
depletion (Fig. 2; Table 4). The main differences The results of sequential chemical extraction
in the REEs among the eight benches are their experiments showed that Li, Sc, Ti, Cr, Y, Zr, and
different overall concentrations. REEs in the sample CHD-8 occur mainly in sili-
cates (Table 4). The in-depth studies on the mode
of occurrence of Li and Sc in coal have not been
previously reported. However, based on the
1000 geochemistry of Li, Finkelman (1981) deduced
CHD-1
CHD-2 that clay minerals are probably the main carriers
CHD-3 of Li in coal; Li may also occur in mica and
CHD-4 tourmaline. Scandium in coal may be related to
CHD-5
CHD-6 clay minerals, phosphate minerals, and organic
100
Samples/Chondrite

CHD-7 matter (Finkelman, 1981). Swaine (1990) sug-

CHD-8 gested that Sc is related not only to minerals but
also to organic matter. Titanium mainly occurs in
oxides and clay minerals (Dai, Ren, Yang, Zhang,
& Jiao, 2000b; Finkelman, 1993) but sometimes is
10
also related to organic matter in low rank coal
(Finkelman, 1993; Swaine, 1990). There are many
reports on the mode of occurrence of Cr in
coal (Brownfield, Affolter, & Stricker, 1995;
1 Finkelman, 1995; Gluskoter et al., 1977; Huggins
La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu & Huffman, 1996; Miller & Given, 1987; Ruppert
Fig. 2 Distribution patterns of rare earth elements in the et al., 1996). There are probably three carriers of
benches of Jinshan coal Cr in coal: detrital material of terrigenous origin,

123
40
clay minerals, and organic matter. Rare earth
elements and Y mainly occur in clay minerals
(Dai, Ren, & Li, 2006d) but sometimes are
related to organic matter (Dai et al., 2006c;
Eskenazy, 1978, 1987a, b; Hower, Ruppert, &
Eble, 1999).
Elements Be and W are mainly associated with
organic material. The occurrence mode of Be in
coal was only determined on the basis of the
relationship between ash yield and Be concen-
tration (Finkelman, 1995). Indirect evidence
shows that Be occurs in both organic and inor-
ganic forms (Eskenazy, 2006). Beryllium is pre-
dominantly organically bound in deposits with
enhanced Be content, whereas the inorganic form
prevails in deposits whose Be concentration
approximates Clarke values. The enrichment in
Be is attributed to subsynchronous hydrothermal
and volcanic activity (Eskenazy, 2006). Tungsten
is mainly related to organic matter in coal
(Eskenazy, 1977; Finkelman, 1995).
SCEP results show that B occurs mainly in
association with organics; minor amounts occur in
leached silicates (Table 4). Nicholls (1968) con-
cluded that B is usually associated with the
organic fraction in coals. Finkelman (1981)
regarded B as generally organically associated,
but with illite and tourmaline as minor sources.
Studies by Dai, Ren, Tang, Shao, and Hao
(2002a) and Dai et al. (2004a) indicated that B
shows an essentially organic rather than silicate
affinity in a coalbed from Guizhou, China, which
was strongly influenced by siliceous low temper-
ature fluids.
Molybdenum, Tl, and Pb mainly occur in sul-
fides and are very low or below the detection limit
in the other five leachages. The three trace ele-
ments in coals all showed a sulfide affinity
(Finkelman, 1995; Gluskoter et al., 1977; Kolker
& Finkelman, 1998; White, Smith, & Spears,
1989).
The main carrier of Hg in the coal is sulfide,
followed by organic matter. Mercury in coal is
mainly distributed in pyrite, particularly in pyrite
of epigenetic origin (Dai et al., 2006e). In addi-
tion, some other sulfide and selenide minerals
also contain a high proportion of Hg (Dai et al.,
2006c). High-sulfur coals usually contain higher
amounts of Hg, which occurs mainly in pyrite
123
Environ Geochem Health (2007) 29:33–44
(Dai, Han, & Chou, 2006b). In addition, because
of the extremely strong affinity of Hg2+ for humic
matter, it is theoretically possible for syngenetic
(or early epigenetic) Hg to accumulate in peats
and lignites (Yudovich & Ketris, 2005). The high
content of Hg in the Jinshan coal is attributed to
the high contents of pyrite and barkinite in the
coal.
The geochemical characteristics of Ga is very
similar to that of Al, so silicate association may
contain a high proportion of Ga, as a result of
Ga substitution for Al in clay minerals (Dai
et al., 2006d). Although Ga could also show a
sulfide affinity, it generally is enriched in the
pyrite of hydrothermal origin, rather than in the
syngenetic pyrite. Gallium also showed an or-
ganic affinity in some coals (Eskenazy, 1967;
Given & Miller, 1987). Gallium in the Jinshan
coal is essentially in silicate association, only
minor in organic association and below the
detection limit in sulfide association. Moreover,
the concentration of Ga in the sample CHD-8
was so high that it was up to the industrial grade
(30 lg/g). Thus, the economic value of gallium in
the coals needs further study.
Uranium mainly occurs in organic and silicate
association. Studies by Van der Flier and Fyfe
(1985), Swaine (1990), Finkelman (1995), and Dai
et al. (2005b) showed that there are four modes of
occurrence of U in coal: (1) the predominant
mode, uranium fixed by organic matter, (2)
absorbed by clay minerals and Fe-bearing
hydrated minerals, (3) occurring as isomorphous
replacement in zircon, apatite, rutile, monazite,
carbonate minerals, and phosphate minerals, and
(4) occurring in uranium-bearing minerals.
The mode of occurrence of Th in the coal is
different from that of U. Thorium is essentially
distributed in the silicate association but is very
low in the organic association and below the
detection limit in the sulfide association of the
ICP-MS method (Table 4). All of the reported
occurrences of Th in coal indicated that it is only
distributed in oxide and silicate minerals and
rarely in organic matter and sulfide minerals (Dai
et al., 2005b; Finkelman, 1981, 1995; Palmer &
Filby, 1984; Swaine, 1990).
Taylor and McLennan (1985) suggest an aver-
age Th/U ratio of around 4.8±0.3 for Post-
Environ Geochem Health (2007) 29:33–44
Archean shales. Ratios >4.8 indicate relative
enrichment of Th, and ratios < 4.8 indicate
relative enrichment of U. Van der Flier and Fyfe
(1985) examined the Th/U systematics of two
Canadian coal-bearing sequences and found the
highest concentrations of U in the organic rich
clays. They suggest that periodic inundation of
the coal depositional environment by marine
waters, as well as contact with more saline ground
waters, would lead to elevated U (owing to sea-
water being relatively enriched in dissolved U) by
a process of reduction of soluble U complex (e.g.,
UO2+2 ) to an insoluble uranous form. The organic-
rich clays provide potential sites for U complex-
ing (with humic acids associated with organic
matter) and adsorption on clay minerals such as
kaolinite.
The Th/U ratios in the Jinshan barkinite lip-
tobiolith seam vary between 0.34 and 5.37, with
an average of 1.52. The ratios indicate that the
Jinshan coals are enriched in U, particularly in
the uppermost bench of the seam (CHD-1) with
the lowest Th/U ratio, 0.34. The enrichment of
uranium in the coals is likely attributable to sea-
water influence during peat accumulation.
A study by Dai, Ren, Sun, and Tang (2004c)
also indicated that the coals in the Shanxi For-
mation of continental sediments from the Ordos
Basin, China, have high Th/U ratios, while the
coals formed in the seawater-influenced Taiyuan
Formation have low Th/U ratios.
The mode of occurrence of V is not clear
(Finkelman, 1995), but some reports have shown
that V occurs both in clay minerals and in organic
matter (Huggins & Huffman, 1996; Palmer &
Filby, 1984). Vanadium in the Jinshan coal is
mainly distributed in organic association but is
minor in the silicate one. The organic affinity of V
in the coal may probably be due to the high
content of barkinite, which could adsorb V during
peat accumulation.
Conclusions
(1) The Jinshan barkinite liptobiolith (Late
Permian) is a medium-ash (>29%) and high-
sulfur (>3%) coal. Sulfur in the eight
benches is mainly pyritic.
41
(2) Minerals in the coal are composed of kaoli-
nite, pyrite, calcite, and quartz. Pyrite and
calcite in the coal are derived from seawater
during peat accumulation. Quartz, and part
of the kaolinite, occur as cell-fillings of au-
thigenic origin in the coal.
(3) Elements Li, Be, Si, Sc, Ti, V, Cr, Fe, Ga, Se,
Y, Zr, Mo, REEs, W, Hg, Tl, Pb, Th, and U
are enriched in the barkinite liptobiolith.
Lithium, Sc, Ti, Cr, Y, Zr, REEs, and Th in
the coal mainly occur in silicate association,
while Be and W is related to organic matter.
Pyrite is the dominant carrier of Mo, Hg, Tl,
and Pb in the coal. Gallium is only distrib-
uted in silicate association. Uranium and V
occur both in organic and silicate association.
Acknowledgments This research was supported by the
National Key Basic Research and Development Program
(no. 2003CB214607). We wish to thank Dr. Shifeng Dai for
his constructive suggestions for the manuscript.
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