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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 extraction showed that Li, Sc, Ti, Cr, Y, Zr, REEs,
and mineralogy of the barkinite liptobiolith of and Th in the coal mainly occur as silicates, while
the Late Permian age from the Jinshan Mine, Be and W are related to organic matter. Pyrite is
Guangde County, Anhui Province, China. Sam- the dominant source of S, Mo, Hg, Tl, and Pb.
ples were examined using inductively coupled Gallium only occurs in silicate, and U and V occur
plasma-mass spectroscopy, X-ray fluorescence, both in organic and silicate associations.
cold-vapor atomic absorption spectrometry, ion-
selective electrode, sequential chemical extrac- Keywords Geochemistry Æ Barkinite liptobiolith Æ
tion, scanning electron microscopy equipped with Trace elements Æ Major elements Æ Late Permian Æ
energy-dispersive X-ray, and optical microscopy. Jinshan Mine Æ China
The coal is a medium-ash and high-sulfur
resource. Minerals in the coal are composed of
kaolinite, pyrite, calcite, and quartz. Pyrite and Introduction
calcite are derived from seawater during peat
accumulation. Quartz in the coal is of authigenic Understanding the migration and enrichment of
origin. Part of the kaolinite is from a land-source the trace elements in coal is important, both
region, and part occurs as cell-fillings and is of academically in developing coal-forming theories
authigenic origin. The results also indicate that the and practically in optimizing coal utilization.
barkinite liptobiolith contains some toxic ele- These elements may serve as indicators of min-
ments in high concentrations. Elements including eralization during coal formation, and some ele-
Li, Be, Si, Sc, Ti, V, Cr, Fe, Ga, Se, Y, Zr, Mo, the ments are major contributors to environmental
rare earth elements (REEs), W, Hg, Tl, Pb, Th, pollution during coal combustion and utilization
and U in the coals are enriched in the barkinite (Dai & Ren, 2006; Seredin & Shpirt, 1995). Many
liptobiolith. Results of sequential chemical previous studies have examined the inorganic
geochemistry of Chinese coals (Dai, Hou, Ren, &
Tang, 2003a; Dai, Ren, Hou, & Shao, 2003b; Dai,
Y. Sun (&) Æ M. Lin Æ P. Qin Æ C. Zhao Æ K. Jin Ren, Zhang, & Hou, 2003c; Dai, Ren, & Ma,
Key Laboratory of Resource Exploration Research of 2004b; Dai, Chou, Yue, Luo, & Ren, 2005a, Dai,
Hebei Province, Hebei University of Engineering,
Ren, Tang, Yue, & Hao, 2005b; Finkelman et al.,
Guangmingnan Street 195, Handan, Hebei 056038,
China 2002; Luo et al., 2004) and the petrologic and
e-mail: sun_yz@hotmail.com organic geochemistry of barkinite of China (Sun

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

& Kalkreuth, 2000). However, we have found no Longtan Formation. The non-coal-bearing strata
studies concerned with the inorganic geochemis- underlying the Longtan Formation are Early
try of barkinite. Barkinite is a peculiar maceral of Permian Gufeng Formation (P1g) and Xixia
Chinese coal petrographic nomenclature, because Formation (P1x), and are Carboniferous sedi-
its morphological features suggest an origin from ments. The overlying non-coal-bearing forma-
bark tissue (Sun, 2003; Sun, Püttmann, Kalkreuth, tions include Triassic, Jurassic, Cretaceous,
& Horsfield, 2002; Zhong & Smyth, 1997). In this Tertiary, and Quaternary systems.
paper we report new data on the mineralogy and
geochemistry of this peculiar maceral.
Experimental methods

Geological setting Eight bench samples were collected from the bark-
inite coal bed in the Jinshan Mine, following the
The Jinshan Mine is located in Guangde County, Chinese Standard Method GB 482-1995 (1995). The
southeastern Anhui Province, southern China sample for each bench was 10 cm wide and 10 cm
(Fig. 1). Coal-bearing strata belong to the Long- deep. All clay partings thicker than 30 mm were
tan Formation of the Late Permian age. Regional excluded. From top to bottom, the eight bench
geology of barkinite liptobiolith has been studied samples of coal were labeled CHD-1 to CHD-8.
by many geologists (Han, Ren, & Guo, 1983; Epoxy-bound pellets were made from the coal
Mao, Zhang, & Gu, 1997; Wang, Liu, & Song, samples, crushed and ground to < 850 lm, and
1998; Yan & Li, 1958; Zhang, Tang, Zhen, & prepared to a final polish with 0.05 lm alumina.
Guo, 1998). The paleogeography of the Late Mineral analysis was performed with reflected-
Permian in southern China ranged from upland light optics at a magnification of ·500. In addition
through continental deposits and littoral facies to to optical microscopy, the minerals in the samples
shallow marine deposits (Fig. 1). were identified by X-ray powder diffraction, using
The Late Permian coal-bearing strata in the Ni-filtered Cu-Ka radiation and a scintillation
Jinshan Mine include the Longtan Formation detector. The XRD pattern was recorded over a
(P2l) and Dalong Formation (P2d). The Longtan 2h interval of 3–70, with a step size of 0.02.
Formation is the major coal-bearing formation, A scanning electron microscope equipped with
which consists of sandstone, limestone, mudstone, an energy-dispersive X-ray spectrometer was
and coal beds, with a thickness between 18 m used to determine the distribution of elements in
and 185 m. The coal bed, with a thickness of the coal. The accelerating voltage was 20 kV, and
0.8–3.2 m, is in the uppermost portion of the the beam current was 10–10 A.

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 35

Samples for geochemical analysis were crushed Chinese Classification for Coal Quality GB/T
and ground to less than 200 mesh. X-ray fluores- 15224.1-2004 (2004) and GB/T 15224.2-2004
cence (XRF, Cu–Ka source) spectrometric anal- (2004), the coal is categorized as a medium-ash
ysis was used to determine the oxides of the major (>29%) and high-sulfur (>3%) coal. Sulfur in the
elements, including Si, Al, Ca, K, Na, Fe, and Mg. eight benches is mainly pyritic (Table 1). The
Inductively coupled-plasma mass spectrometry highest sulfur content is 15.6%, and its average
(ICP-MS) was used to determine the concentra- content is about 8%. Such high sulfur contents are
tions of most trace elements in the coal. Mercury harmful to environments and human health. The
was determined by cold-vapor atomic absorption high organic sulfur content (average 1.04%) in
spectrometry (CV-AAS). Fluorine and boron the coal cannot be accounted for by the original
were determined, respectively, by an ion-selective plant sulfur. Therefore, there must have been
electrode (ISE) method and inductively coupled- some sulfur incorporated into the peat after burial
plasma atomic emission spectrometry (ICP- (Chou, 1990, 1997, 2004; Dai, Ai, Jiao, Ma, & Li,
AES). 2000a).
Sample CHD-8 was crushed to less than 100 It is difficult to determine the organic sulfur
mesh for a six-step sequential chemical extraction content of individual macerals using traditional
procedure (SCEP) as outlined by Dai et al. chemical methods, due to their small size and
(2004a). Leaching methods used in coal have a their intimate relationship with one another in
major advantage over float–sink methods in that most coals (Chou, 1990; Dai, Ren, Tang, Shao, &
specific elemental forms are anticipated to be ei- Li, 2002b; Mastalerz & Bustin, 1993; Ward &
ther present or absent in different fractions, Gurba, 1998). Raymond (1978) determined the
depending on their solubility behavior in the vari- organic sulfur content of individual macerals di-
ous reagents used for the different leaching stages rectly by using an electron microprobe. The
(Huggins, 2002). In this study the authors identified technique in this study used a scanning electron
six types of organic to inorganic associations of microscope (SEM) in conjunction with an energy
elements in coal: water-soluble, ion-exchangeable, dispersive X-ray (EDX) spectrometer. The re-
carbonate, organic-bonded, silicate, and sulfide. sults show that the organic sulfur content in
macerals of the same coal sample decreases in the
order: barkinite (1.14%), collodetrinite (1.01%),
Results and discussion corpogelinite (0.97%), collotelinite (0.94%),
semifusinite (0.91), and fusinite (0.90%). The re-
Proximate analysis sults of the organic sulfur content of the macerals
are in accordance with those of the wet chemical
Proximate analysis and rank (vitrinite random analysis as described above.
reflectance, %Rr) of the coal benches from the The coal has an average vitrinite reflectance of
Jinshan Mine are given in Table 1. In terms of the 0.71% and a high yield of volatile matter (varying
Table 1 Ultimate analysis and vitrinite reflectance of the matter, d on a dry base, daf on a dry and ash-free base, St
coal from the Jinshan Mine, Anhui Province (as total sulfur, Sp, sulfide sulfur, Ss sulfate sufur, So organic
percentages) (M moisture, ad as received, VM volatile sulfur, Ro,ran mean random reflectance of vitrinite)
Sample no. Mad Ashd VMdaf 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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from 44.6% to 50.2%), due to the high content of Quartz occurs as very fine particles
barkinite in the coal: a highly volatile bituminous of < 5 lm. The mode of occurrence of quartz,
rank coal. such as sharp edges, particles connecting with
each other, and sometimes filling in plant cavi-
Mineralogy ties, indicates that the quartz in the coal bed is
of authigenic origin rather than the epiclastic
Minerals in the coals from the Jinshan Mine are sediments.
mainly pyrite, quartz, clay minerals, and a trace Calcite does not occur as fracture- or cleat-
amount of calcite (Table 2). The predominant fillings but as well-developed crystals in the coal.
mode of occurrence of the pyrite is as fine grains Calcite of terrigenous origin is very rare in coal
distributed in various macerals, and sometimes (Bouška, Pešek, & Sykorova, 2000; Ward, 2002),
occurring as massive pyrite or cell-fillings; how- because it can be easily decomposed under acid
ever, other forms of pyrite, including framboidal, conditions. The well-developed crystals of calcite
fracture-filling, and nodular forms, have not indicate that calcite is derived from seawater
identified in these coals. The mode of occurrence during peat accumulation. The alkaline condi-
of pyrite suggests that it is syngenetic rather than tions of peat mire influenced by seawater may
epigenetic (Chou, 1997; Dai, Sun, & Zeng, favor calcite preservation.
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 Geochemistry
in accordance with the general variation of pyr-
ite in coals that were influenced by seawater Major elements
during peat accumulation (Chou, 1997, 2004; Dai
et al., 2002b). The variation of pyrite in the The concentration of major and trace elements in
column section showed that the mire in the study the coal from the Jinshan Mine are presented in
area had been seriously influenced by seawater Table 3. The average concentration of Fe2O3
in the early and late stages during peat accu- (5.4%) and SiO2 (12%) are much higher than
mulation. those of ordinary coals from China and the USA,
The clay minerals occur either as lenses or as as reported by Dai, Chou, Li, Ren, and Luo
fine grain particles in small or as fusinite cell- (2006a) and Finkelman (1993), respectively. The
fillings. The SEM-EDX results showed that the K, high concentrations of Fe2O3 and SiO2 are due to
Na, and Mg content in the clay minerals is the high percentage of pyrite and quartz in the
< 0.8%, indicating that the clay minerals are coal. In particular, samples CHD-1 and CHD-2
mainly kaolinite. The clay mineral identity was are highest in Fe2O3 and SiO2, 25% and 17%,
also confirmed by X-ray diffraction. 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- the Clarke value. Such coals are located in the
positions described above. Donbas (Ukraine), Appalachian Basin and Texas
(USA), Russian Far East, and Southern China.
Trace elements The mercury in these coals is usually accompa-
nied by other chalcophile trace elements and is
The average concentrations of Li, Be, B, Sc, Ti, V, generally associated with epigenetic hydrother-
Cr, Ga, Y, Zr, Mo, rare earth elements (REEs), mal fluids (Dai, Ren, Chou, Li, & Jiang, 2006c).
W, Hg, Tl, Pb, Th, and U are higher than those However, no veined pyrite or other sulfide min-
in ordinary Chinese and US coals (Table 3). erals of epigenetic hydrothermal origin were ob-
Particularly, the enrichment of the toxic trace served in the Jinshan coal, either under optical
elements Be, Cr, Hg, Tl, and Pb in the coals from microscopy and SEM-EDX or by XRD. The high
the Jinshan Mine is worth noting, due to their concentration of Hg in the coal is possibly
toxic effects. attributable to the high content of syngenetic
The Be content in the Jinshan coal varies from pyrite and the particular maceral barkinite in the
3 lg/g to 6.4 lg/g, with an average of 5 lg/g. This coal, as described below.
value is not only higher than the average mean of Thallium varies considerably in the column
Be in bituminous coal (3.0±1.2 lg/g), as reported section of the Jinshan coal, from 0.32 lg/g to
by Eskenazy (2006), but is also higher than that in 11 lg/g, with an average of 2.8 lg/g (Table 3).
Chinese and American coals, as reported by Dai Thallium is significantly enriched in the top and
et al. (2006a) and Finkelman (1993), respectively. bottom portions of the column section but is very
Eskenazy (2006) showed that there was no clear- low in the middle portions (CHD-3, CHD-4,
cut ‘‘Be content-rank’’ relationship. CHD-5, and CHD-6). The high content of pyrite
Although B in the Jinshan coal (average 79 lg/ in the top and bottom portions of coal seam, as a
g) is higher than that in coals from China (53 lg/ result of seawater influence, contribute the high
g) and the USA (49 lg/g), as reported by Dai Tl concentration in the coal.
et al. (2006a) and Finkelman (1993), respectively, The concentrations of Cr (31 lg/g) and Pb
its content is comparable to the B content in coals (23 lg/g) are about twice those of the Chinese
influenced by brackish water, reported by Swaine and US coal values reported by Dai et al. (2006a)
(1971) and Goodarzi and Swaine (1994). The B and Finkelman (1993). Chromium and Pb are
content in the Jinshan coal is probably attribut- highest in the downmost portion (CHD-8) of the
able to the seawater-influenced sedimentary coal bed.
environment. The average concentration of rare earth ele-
The Clarke value for Hg in coal (world-wide ments (SREE = La+Ce+Nd+Sm+Eu+Tb+Yb+
average Hg content) is 0.10 lg/g, regardless of Lu+Y) in the coal is 190 lg/g. This is much higher
coal rank (Yudovich & Ketris, 2005). The Hg than that of US coals and the ordinary Chinese
content of the Jinshan coal (average 0.59 lg/g) is coals (Tables 4 and 5). In particular, SREE in
about six-times higher than the Clarke value for samples CHD-3 was 350 lg/g, and the L/H value
Hg in coal. There are some coals that are en- (ratio of light rare earth elements to heavy rare
riched in Hg by 1–2 orders of magnitude above 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,

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

clay minerals, and organic matter. Rare earth (Dai, Han, & Chou, 2006b). In addition, because
elements and Y mainly occur in clay minerals of the extremely strong affinity of Hg2+ for humic
(Dai, Ren, & Li, 2006d) but sometimes are matter, it is theoretically possible for syngenetic
related to organic matter (Dai et al., 2006c; (or early epigenetic) Hg to accumulate in peats
Eskenazy, 1978, 1987a, b; Hower, Ruppert, & and lignites (Yudovich & Ketris, 2005). The high
Eble, 1999). content of Hg in the Jinshan coal is attributed to
Elements Be and W are mainly associated with the high contents of pyrite and barkinite in the
organic material. The occurrence mode of Be in coal.
coal was only determined on the basis of the The geochemical characteristics of Ga is very
relationship between ash yield and Be concen- similar to that of Al, so silicate association may
tration (Finkelman, 1995). Indirect evidence contain a high proportion of Ga, as a result of
shows that Be occurs in both organic and inor- Ga substitution for Al in clay minerals (Dai
ganic forms (Eskenazy, 2006). Beryllium is pre- et al., 2006d). Although Ga could also show a
dominantly organically bound in deposits with sulfide affinity, it generally is enriched in the
enhanced Be content, whereas the inorganic form pyrite of hydrothermal origin, rather than in the
prevails in deposits whose Be concentration syngenetic pyrite. Gallium also showed an or-
approximates Clarke values. The enrichment in ganic affinity in some coals (Eskenazy, 1967;
Be is attributed to subsynchronous hydrothermal Given & Miller, 1987). Gallium in the Jinshan
and volcanic activity (Eskenazy, 2006). Tungsten coal is essentially in silicate association, only
is mainly related to organic matter in coal minor in organic association and below the
(Eskenazy, 1977; Finkelman, 1995). detection limit in sulfide association. Moreover,
SCEP results show that B occurs mainly in the concentration of Ga in the sample CHD-8
association with organics; minor amounts occur in was so high that it was up to the industrial grade
leached silicates (Table 4). Nicholls (1968) con- (30 lg/g). Thus, the economic value of gallium in
cluded that B is usually associated with the the coals needs further study.
organic fraction in coals. Finkelman (1981) Uranium mainly occurs in organic and silicate
regarded B as generally organically associated, association. Studies by Van der Flier and Fyfe
but with illite and tourmaline as minor sources. (1985), Swaine (1990), Finkelman (1995), and Dai
Studies by Dai, Ren, Tang, Shao, and Hao et al. (2005b) showed that there are four modes of
(2002a) and Dai et al. (2004a) indicated that B occurrence of U in coal: (1) the predominant
shows an essentially organic rather than silicate mode, uranium fixed by organic matter, (2)
affinity in a coalbed from Guizhou, China, which absorbed by clay minerals and Fe-bearing
was strongly influenced by siliceous low temper- hydrated minerals, (3) occurring as isomorphous
ature fluids. replacement in zircon, apatite, rutile, monazite,
Molybdenum, Tl, and Pb mainly occur in sul- carbonate minerals, and phosphate minerals, and
fides and are very low or below the detection limit (4) occurring in uranium-bearing minerals.
in the other five leachages. The three trace ele- The mode of occurrence of Th in the coal is
ments in coals all showed a sulfide affinity different from that of U. Thorium is essentially
(Finkelman, 1995; Gluskoter et al., 1977; Kolker distributed in the silicate association but is very
& Finkelman, 1998; White, Smith, & Spears, low in the organic association and below the
1989). detection limit in the sulfide association of the
The main carrier of Hg in the coal is sulfide, ICP-MS method (Table 4). All of the reported
followed by organic matter. Mercury in coal is occurrences of Th in coal indicated that it is only
mainly distributed in pyrite, particularly in pyrite distributed in oxide and silicate minerals and
of epigenetic origin (Dai et al., 2006e). In addi- rarely in organic matter and sulfide minerals (Dai
tion, some other sulfide and selenide minerals et al., 2005b; Finkelman, 1981, 1995; Palmer &
also contain a high proportion of Hg (Dai et al., Filby, 1984; Swaine, 1990).
2006c). High-sulfur coals usually contain higher Taylor and McLennan (1985) suggest an aver-
amounts of Hg, which occurs mainly in pyrite age Th/U ratio of around 4.8±0.3 for Post-

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Environ Geochem Health (2007) 29:33–44 41

Archean shales. Ratios >4.8 indicate relative (2) Minerals in the coal are composed of kaoli-
enrichment of Th, and ratios < 4.8 indicate nite, pyrite, calcite, and quartz. Pyrite and
relative enrichment of U. Van der Flier and Fyfe calcite in the coal are derived from seawater
(1985) examined the Th/U systematics of two during peat accumulation. Quartz, and part
Canadian coal-bearing sequences and found the of the kaolinite, occur as cell-fillings of au-
highest concentrations of U in the organic rich thigenic origin in the coal.
clays. They suggest that periodic inundation of (3) Elements Li, Be, Si, Sc, Ti, V, Cr, Fe, Ga, Se,
the coal depositional environment by marine Y, Zr, Mo, REEs, W, Hg, Tl, Pb, Th, and U
waters, as well as contact with more saline ground are enriched in the barkinite liptobiolith.
waters, would lead to elevated U (owing to sea- Lithium, Sc, Ti, Cr, Y, Zr, REEs, and Th in
water being relatively enriched in dissolved U) by the coal mainly occur in silicate association,
a process of reduction of soluble U complex (e.g., while Be and W is related to organic matter.
UO2+2 ) to an insoluble uranous form. The organic- Pyrite is the dominant carrier of Mo, Hg, Tl,
rich clays provide potential sites for U complex- and Pb in the coal. Gallium is only distrib-
ing (with humic acids associated with organic uted in silicate association. Uranium and V
matter) and adsorption on clay minerals such as occur both in organic and silicate association.
kaolinite.
The Th/U ratios in the Jinshan barkinite lip- Acknowledgments This research was supported by the
National Key Basic Research and Development Program
tobiolith seam vary between 0.34 and 5.37, with (no. 2003CB214607). We wish to thank Dr. Shifeng Dai for
an average of 1.52. The ratios indicate that the his constructive suggestions for the manuscript.
Jinshan coals are enriched in U, particularly in
the uppermost bench of the seam (CHD-1) with
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