Research Article

Energy Exploration & Exploitation

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Mineralogy and geochemistry ! The Author(s) 2019
DOI: 10.1177/0144598719867477
of the coal seam of journals.sagepub.com/home/eea

Shanxi Formation in
Guotun Mine, Juye
Coalfield, North China

Jingsen Zhang , Chao Jin, Lecai Xing,

Hong-Tao He, Yunyun Zhao, Yumeng Xin,
Yun Xu, Cunliang Zhao and Pengfei Sun

Abstract
This work investigated the mineralogy and geochemistry of the No. 3 coal seam in Permian
Shanxi Formation in Guotun Mine, Juye Coalfield, north China, in order to understand the
genesis of the minerals and the enrichment of trace elements. Approaches used were optical
microscopy and electron probe microanalysis for minerals, X-ray fluorescence analysis for major
elements and inductively coupled plasma mass spectrometry analysis for trace elements. The coal
is comprised of dominant kaolinite and calcite, the claystone is characteristic of major kaolinite,
montmorillonite, and proportional illite, and the sandstone contains mainly quartz and chalce-
dony, and a relative amount of feldspar and kaolinite. These minerals were derived dominantly
from the weathered source rocks with volcanic and granitic constituents in the pre-diagenetic
period, and minor from the hydrothermal deposit in the epigenetic period. The claystone is
relatively enriched in Li, Cs, Be, Nb, Mo, U, Th, V, In, Pb, Bi, and Se, which may probably be
controlled by the source rocks and the specific sedimentary environment. The enriched trace
elements are mostly associated with minerals. Li may probably occur in montmorillonite and illite,
while In, Pb, Bi, and Se occur mainly in selenio-galena.

Keywords
Kaolinite, montmorillonite, brammallite and illite, selenio-galena, mineral genesis, trace element
enrichment, volcanic and granitic rock, sedimentary environment

School of Earth Science and Engineering, Hebei University of Engineering, Handan, China
Corresponding author:
Jingsen Zhang, Hebei University of Engineering, No. 199 Guangming Nan Dajie, Handan, Hebei 056038, China.
Email: zhjsen@hebeu.edu.cn

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2 Energy Exploration & Exploitation 0(0)

Introduction
The valuable elements in coal seams, such as Li, Ga, Ge, REEs, etc., have been a hot point
in the field of coal geology recently for their high concentrations and utilization (Dai et al.,
2014; Seredin and Finkelman, 2008; Sun et al., 2012, 2013; Zhao et al., 2017; Zhuang et al.,
2006). Dai et al. (2014) reviewed the geological origin, modes of occurrence, and evaluation
methods of the coal-hosted rare metal deposits including Ge, Ga, U, Nb, and rare earth
elements; Sun et al. (2012, 2013) discovered Li deposits in the coal seams in the Inner
Mongolia Autonomous Region and Shanxi Province in north China. Mineralogical and
geochemical study is the key to clarify the distribution, origin, modes of occurrence, and
evaluation of valuable elements in coal seam (Dai et al., 2012; Singh and Singh, 1995; Sun
et al., 2010, 2012, 2013; Ward, 2002; Zhao et al., 2017). For example, Li in the
Guanbanwusu coal mainly occurs in the chlorite (an intermediate between cookeite and
chamosite), kaolinite, and possibly in illite; Ga in the same coal largely occurs in goyazite
(Dai et al., 2012). However, combustion of the coals enriched in certain elements such as As,
Cd, Hg, Be, Th, U, Tl and so on, may make potential negative effects on the environment
and humans (Finkelman and Gross, 1999; Ren et al., 2006; Swaine and Goodarzi, 1995). So,
the mineralogical and geochemical study on coals is also much significant for environmental
protection during coal utilization. Though there is an amount of coalfield in north China,
the coal seams studied in detail on mineralogy and geochemistry are still a few.
The west Shandong Province, north China, has many large coalfields formed during the
Carboniferous and Permian periods such as Yanzhou, Ji’ning, Juye, and other coalfields.
Only a few of coalfields had been studied on the coal quality, trace elements in coal and coal-
forming environment (Hu, 2009; Liu et al., 2005, 2007). Those studies mainly focused on
environmental elements and sedimentary geology, less on mineralogy and valuable elements
in coal, and they hardly concerned the Juye Coalfield developed recently. The previous
studies concerned only a few of trace elements and showed that the distribution of trace
elements in coal seams horizontally and vertically varied much in different coalfields with
the similar sedimentary environment (Hu, 2009). In addition, in the Juye Coalfield, the
mudstone near the bottom of the No. 3 coal seam was considered to be an altered volcanic
ash bed by its high natural gamma-ray (Feng and Dong, 1997); the Permian strata contained
a large amount of volcanic clast rock (Wang, 1990) and a petrological study on the No. 3
coal seam in the Yuncheng Mine indicated the existence of volcanic clast as well (Zhang,
2016). These cases are much important for the trace element enrichment in the No. 3 coal
seam but they have not been discussed in the literature. This paper will present the miner-
alogical and geochemical data of the No. 3 coal seam in the Guotun Mine, Juye Coalfield, in
order to understand the genesis of valuable and toxic elements enriched in the coal seam and
provide important information for harmless mining and utilization of coal.

Geologic setting
The Juye Coalfield is located in the Juye and Yuncheng counties, Heze city, which is at a
distance of about 200 km to Jinan city, capital of Shandong Province, to the northeast. It is
in the west Luxinan Fault Depression, Luxi Uplift, North China Craton (Figure 1). The
Luxi Uplift is bounded by Jiyang-Guangrao Fault on the north, Liaocheng-Lankao Fault
on the west, Kaifeng-Peixian Fault on the south, and Tancheng-Lujiang Fault on the east
(Figure 1, F1–F4). The Luxinan Fault Depression is bounded by Wenshang-Ningyang Fault
Zhang et al. 3

Figure 1. Sketch tectonic map of the North China Craton [modified after Liu and You (2015)] and the
location of the studied coal mine.

on the north, Yishan Fault on the east, Shanxian Fault on the south, and Liaocheng-
Lankao Fault on the west (the former three not shown in Figure 1). Abundant coal resource
occurs in this depression. There are mainly five large coalfields such as Juye, Ji’ning,
Wenshang-Ningyang, Yanzhou and Tengxian coalfields (Figure 1).
The Juye Coalfield occurs in long subsidence bounded by faults on its eastern, western,
and northern boundaries. It is 80 km long from north to south, 12 km wide from west to
east, and has a total area of about 960 km2. The coal types in Juye Coalfield include mainly
gas coal and gas-fat coal. In addition, there locally are some 1/3 coking coal, primary coking
coal, meagre coal, anthracite, and even natural coke which was formed by the Jurassic
magma intrusion. The strata in Juye Coalfield include Quaternary, Neogene, Palaeogene,
Permian, Carboniferous, Ordovician, Cambrian, and Neoarchaean units. The Neoarchaean
units consist of a series of metamorphic rocks. The Cambrian and Ordovician strata are
limestone series, and the Carboniferous and Permian strata consist of marine-terrigenous
sediments to terrigenous clasts. The Palaeogene strata occur near the southern margin of the
coalfield, and the Neogene and Quaternary strata (mainly Quaternary), with a total thick-
ness ranging from 258 m to 665 m, are the cover of the coal-bearing sequences. The coal-
bearing sequences are the Carboniferous-Permian unit including Benxi, Taiyuan, and
Shanxi Formations (Figure 2). The Juye Coalfield contains 16 coal seams, but only 4 of
them, i.e. Nos. 3, 15, 16, and 17, are mineable. The Benxi and Taiyuan Formations are
composed of grey and greyish-white quartzose sandstone, siltstone, claystone, and coal beds
interbedded with dark-grey siltstone, claystone, and limestone. The Shanxi Formation is
composed of sandstone, siltstone, claystone, and coal beds. The No. 3 coal seam occurs in
4 Energy Exploration & Exploitation 0(0)

Figure 2. Lithostratigraphic column of Guotun Mine and the sampling profile.

The volume values of maceral for coal sample are on a mineral free basis, and those for minerals are on
coal basis.
Zhang et al. 5

the lower Shanxi Formation. The stratum overlying the coal-bearing sequences is the non-
coal-bearing Lower Shihezi Formation. In addition, the sequences in this coalfield also
contain a few layers of Carboniferous-Permian volcanic clast rocks (Wang, 1990; Zhong
et al., 1996) and some Jurassic intrusive magmatic rocks.
The Guotun Mine, located in the middle-northern Juye Coalfield, has an area of 69.5 km2
and geological coal reserves of 780 Mt (million tonnes). The No. 3 coal seam in this mine is
separated into two subdivisions, the upper one and the lower one, by a thick sandstone bed
with a thickness ranging from 0.80 m to 27.30 m. The main mineable coal seam is the lower
No. 3 coal seam (still called the No. 3 coal seam in the following text) with the mineable
reserves of 170 Mt. The No. 3 coal seam has an average thickness of 3.84 m, with thickness
of 1.62 m on the western boundary and 7.92 m on the eastern boundary (combined with the
upper subdivision). A few of thin partings composed of claystone occur locally.

Samples and methods

There were eight samples including five coals numbered G2 to G6, one sandstone numbered
G1, and two claystone numbered G7-1 and G7-2, which were collected from the No. 3 coal
seam in Guotun Mine, Juye Coalfield. Each sample was cut over a volume of
10
10
10 cm3. The locations and characteristics of the samples are shown in Figure 2.
The coal samples are black and have a banded structure. Fine fracture is filled by white
carbonate or golden pyrite films or grains. The sandstone is grey-white, fine-grained, and has
inconspicuous bedding and negligible organic matter. The claystone is dark grey, without
bedding, and has carbonized plant clasts extensively scattered. A proportion of crack in
sandstone and claystone is filled by white carbonate film or pyrite grains. All samples were
carefully cleaned, powdered, made into blocks and thin sections, etc.
The main methods used were optical microscopy for petrography, electron probe micro-
analysis (EPMA) for mineral chemistry, X-ray fluorescence (XRF) and inductively coupled
plasma mass spectrometry (ICP-MS) for analysis of major and trace elements in rocks,
respectively. The petrographic analysis was performed on a DFC425, an optical microscope
with transmitted and reflected light manufactured by Leica Microsystems Ltd. The maceral
in coal block and mineral in the thin section were counted according to the ISO standard
(ISO 7404–3, 2009). The EPMA was quantitatively analyzed on a JEOL JXA-8100. The
XRF was analyzed on an Axiosm AX, and the ICP-MS was analyzed on an ELEMENT
XR. The EPMA, XRF, and ICP-MS were performed according to the ISO standards (ISO
22489, 2016; ISO 12677, 2011; ISO/TS 16965, 2013) in the laboratory of Beijing Research
Institute of Uranium Geology (BRIUG). The data precisions for the major and trace
elements are less than 1% and 5%, respectively.

Results
Minerals
The coal comprises maceral and mineral, and their contents range, respectively, from
81.3 vol.% to 93.6 vol.% and from 6.4 vol.% to 18.7 vol.% based on point counting
under an optical microscope (Table 1). For the maceral component, the vitrinite is dominant
with content ranging from 61.8 vol.% to 85.0 vol.% and includes mainly collodetrinite,
secondarily collotelinite and vitrodetrinite, and minor corpogelinite; the inertinite has
6 Energy Exploration & Exploitation 0(0)

Table 1. The total contents of maceral and mineral for the No. 3 coal (G2 to G6; vol. %).

Coal sample G2 G3 G4 G5 G6

Maceral 91.3 81.3 88.7 93.6 93.1

Mineral 8.7 18.7 11.3 6.4 6.9

Table 2. Maceral contents of the No. 3 coal (G2 to G6) on mineral free basis (vol. %).

Coal sample G2 G3 G4 G5 G6

Telinite 5.9 nd 4.4 3.2 4.2

Collotelinite 23.8 1.7 8.1 9.9 14.8
Collodetrinite 40.7 50.7 40.9 34.0 37.9
Gelinite 4.9 nd 1.2 0.4 6.0
Corpogelinite 0.9 0.7 0.8 0.2 13.4
Vitrodetrinite nd 14.8 10.2 14.0 8.6
Total vitrinites 76.2 67.9 65.6 61.8 85.0
Sporinite 1.5 0.9 4.2 3.4 1.4
Cutinite 0.4 nd nd nd nd
Total liptinites 1.9 0.9 4.2 3.4 1.4
Semifusinite 1.5 0.9 nd nd nd
Fusinite 7.5 2.3 4.2 7.1 5.1
Macrinite 1.2 0.6 nd 0.6 nd
Micrinite 3.7 4.2 2.6 2.0 5.4
Inertodetrinite 8.0 23.3 23.5 25.1 3.2
Total inertinites 21.9 31.2 30.2 34.8 13.6
VitriniteþInertinite 98.1 99.1 95.8 96.6 98.6
nd: not detected.

content ranging from 13.6 vol.% to 34.8 vol.%, and includes mainly inertodetrinite and
secondarily fusinite and macrinite; and the liptinite has the lowest abundance less than
4.2 vol.%, and is mainly sporinite, sometimes minor cutinite (Table 2; Figure 3(a) and
(b)). Based on the maceral component, the No. 3 coal belongs to vitrinertite in micro
lithotype. As to the mineral in coal, 14 kinds identified are kaolinite, brammallite, illite,
chamosite, quartz, pseudomorphic beta-quartz, zircon, monazite, rutile, ilmenite, calcite,
pyrite, chalcopyrite, and selenio-galena (Table 3; Figure 3). Among them, kaolinite is dom-
inant (48.6 vol.% to 81.7 vol.%, on organic matter free basis), calcite is secondarily rich
(9.2 vol.% to 45.0 vol.%), pyrite is minor (<6.2 vol.%) and occurs extensively, brammallite
(in G2, 22.9 vol.%) and quartz (in G3, 4.8 vol.%) only occur locally in the coal profile, and
the others are trace in abundance.
The claystone (G7-1 and G7-2), silty montmorillonite-kaolinite claystone, contains 11
kinds of mineral, and they are kaolinite, montmorillonite, illite, quartz, pseudomorphic
beta-quartz, rutile, monazite, zircon, apatite, pyrite, and selenio-galena (Table 4;
Figure 4). The dominantly abundant minerals are kaolinite (42.2 vol.% to 49.1 vol.%)
and montmorillonite (35.6 vol.% to 37.4 vol.%), the secondarily abundant ones are illite
(8.0 vol.% to 9.4 vol.%) and quartz (5.7 vol.% to 9.4 vol.%), and the others are minor
or trace.
Zhang et al. 7

Figure 3. Micrographs of the No. 3 coal (G2–G6) in Guotun Mine.

(a) Collotelinite, fusinite, and cutinite in sample G2, transmitted light; (b) collotelinite in G6, transmitted
light; (c) kaolinite and calcite vein in G6, BSE image; (d) kaolinite and pyrite vein in G4, BSE image; (e)
brammallite and calcite in fusinite cell cavity of G2, BSE image; (f) pseudomorph of beta-quartz in G3,
reflected light. Mineral abbreviations are after Whitney and Evans (2010) except for those not mentioned:
Brm: brammallite; b-Qz: pseudomorphic beta-quartz; Cal: calcite; Chm: chamosite; Kln: kaolinite; Py: pyrite;
Rt: rutile.
8 Energy Exploration & Exploitation 0(0)

Table 3. Mineral contents of the No. 3 coal (G2 to G6) on organic matter free basis (vol. %).

Coal sample G2 G3 G4 G5 G6

Quartz nd 4.8 nd nd nd
b-quartz nd 0.01 nd nd nd
Rutile 0.1 0.54 0.1 nd 0.15
Zircon nd 0.05 nd nd nd
Monazite nd nd nd nd 0.15
Ilmenite nd nd nd 0.05 nd
Illite nd nd 0.1 nd nd
Brammallite 22.9 nd nd nd nd
Chamosite 0.1 nd nd nd nd
Kaolinite 59.6 81.7 48.6 70.1 59.2
Calcite 16.0 9.2 45.0 23.3 37.6
Pyrite 1.2 3.7 6.2 6.2 2.9
Chalcopyrite 0.1 nd nd 0.15 nd
Selenio-galena nd nd nd 0.2 nd
nd: not detected.

Table 4. Mineral contents in the roof (G1) and floor (G7-1 and G7-2) rocks (vol. %).

Sample Quartz b-quartz Chalcedony Sanidine Microcline Perthite Albite Garnet

G1 36.8 0.14 32.5 8.0 2.0 0.5 0.5 0.1

G7-1 9.4 0.02 nd nd nd nd nd nd
G7-2 5.7 nd nd nd nd nd nd nd

Sample Rutile Zircon Monazite Apatite Biotite Illite Mont. Wonesite

G1 1.0 0.01 0.01 2.0 0.01 nd nd 4.0

G7-1 1.0 0.01 0.01 0.01 nd 9.4 37.4 nd
G7-2 1.0 0.01 0.01 nd nd 8.0 35.6 nd

Sample Aliettite Chamosite Kaolinite Fdol. Siderite Pyrite Sphalerite SelenoGalena

G1 0.01 1.0 7.0 3.0 1.0 0.4 0.01 0.01

G7-1 nd nd 42.2 nd nd 0.54 nd 0.01
G7-2 nd nd 49.1 nd Nd 0.57 nd 0.01
nd: not detected; Mont.: Montmorillonite; Fdol: Ferroan dolomite.

The sandstone (G1), a feldspathic quartz sandstone, contains 22 kinds of mineral, and
they are quartz, pseudomorphic beta-quartz, chalcedony, sanidine, albite, microcline, per-
thite, garnet, zircon, monazite, rutile, apatite, biotite, wonesite, aliettite, kaolinite, chamo-
site, ferroan dolomite, siderite, sphalerite, pyrite and selenio-galena (Table 4; Figure 5). The
dominantly abundant minerals are quartz and chalcedony, with contents of 36.8 vol.% and
32.5 vol.%, respectively; the secondarily abundant ones are alkali feldspar (including
sanidine, microcline, perthite, and albite; 11.0 vol.%), kaolinite (7.0 vol.%), wonesite
(4.0 vol.%), and ferroan dolomite (3.0 vol.%); and the others are minor or trace in
Zhang et al. 9

Figure 4. Micrographs for the claystone (G7-1 and G7-2) of the No. 3 coal seam.
(a) Quartz, kaolinite and illite, BSE image; (b) montmorillonite and kaolinite, transmitted light; (c) mica-
shaped kaolinite, BSE image; (d) the same view of figure (c), transmitted light; (e) micro-grain quartz with
kaolinite, BSE image; (f) coarse quartz clasts with crack (in the left) and pseudomorphic beta-quartz (in the
right), reflected light for the left and cross-polarized light for the right. Mineral abbreviations are after
Whitney and Evans (2010) except for those not mentioned: b-Qz: pseudomorphic beta-quartz; Ilt: illite; Kln:
kaolinite; Mnt: montmorillonite; Qz: quartz.
10 Energy Exploration & Exploitation 0(0)

Figure 5. Micrographs for the sandstone (G1) of the No. 3 coal seam.
(a) Quartz, pseudomorphic beta-quartz, chalcedony, sanidine, and kaolinite, crossed polarized light; (b)
quartz, chalcedony, intergrown sanidine and albite, mica-shaped kaolinite, BSE image; (c) kaolinite, garnet,
aliettite, micro-particle quartz and sanidine, sphalerite, BSE image; (d) quartz, sanidine, wonesite, kaolinite,
and rutile, BSE image; (e) quartz, chalcedony, kaolinite, wonesite, ferroan dolomite, and siderite, BSE image;
(f) part of image (e) under cross-polarized light. Mineral abbreviations are after Whitney and Evans (2010)
except for those not mentioned: Ab: albite; Ali: aliettite; b-Qz: pseudomorphic beta-quartz; Ccd: chal-
cedony; Fdol: ferroan dolomite; Grt: garnet; Kln: kaolinite; Qz: quartz; Rt: rutile; Sa: sanidine; Sp:
sphalerite; Wns: wonesite.
Zhang et al. 11

Table 5. Chemical compositions (wt. %) of typical minerals in the coals (G2 to G6), sandstone (G1) and
claystone (G7-1 and G7-2).

Mineral Kln Kln Kln Kln Kln Kln Kln Mnt Ilt

Sample G1 G1 G2 G3 G4 G6 G7-2 G7-2 G7-2

SiO2 47.61 47.73 44.90 47.91 45.92 46.23 48.08 50.76 54.66
TiO2 <dl 0.08 <dl 0.08 0.05 <dl 0.13 0.78 0.81
Al2O3 38.28 36.94 40.20 35.90 37.17 38.46 35.74 31.90 21.76
FeO 0.07 0.68 0.57 1.57 1.02 0.51 1.31 1.90 5.99
MnO 0.03 <dl <dl <dl 0.03 0.04 <dl <dl 0.04
MgO 0.10 0.16 0.11 0.12 0.12 0.19 0.40 1.46 3.49
CaO 0.09 0.12 0.06 0.06 0.06 0.17 0.05 <dl <dl
Na2O <dl 0.02 0.19 0.08 0.09 0.17 0.07 0.10 0.12
K2O 0.07 0.21 0.05 0.06 0.09 0.23 0.11 4.42 8.38
P2O5 <dl <dl 0.17 <dl 0.03 0.06 <dl 0.06 <dl
F <dl <dl <dl <dl <dl 0.07 <dl <dl 0.21
Total wt.% 86.25 85.94 86.25 85.78 84.58 86.13 85.89 91.38 95.46

Onormalized 14 14 14 14 14 14 14 11 11

Si 4.08 4.12 3.88 4.16 4.03 3.99 4.15 3.35 3.60

Ti <dl 0.01 <dl 0.01 <dl <dl 0.01 0.04 0.04
Al 3.87 3.76 4.09 3.68 3.85 3.92 3.64 2.48 1.69
Fe3þ <dl 0.05 <dl <dl 0.07 0.04 0.09 0.10 0.32
Fe2þ 0.01 <dl 0.04 0.11 <dl <dl <dl <dl 0.01
Mn <dl <dl <dl <dl <dl <dl <dl <dl <dl
Mg 0.01 0.02 0.01 0.02 0.02 0.02 0.05 0.14 0.34
Ca 0.01 0.01 0.01 0.01 0.01 0.02 0.01 <dl <dl
Na <dl <dl 0.03 0.01 0.02 0.03 0.01 0.01 0.02
K 0.01 0.02 0.01 0.01 0.01 0.03 0.01 0.37 0.70
Total cation 7.99 7.99 8.07 8.01 8.01 8.05 7.98 6.49 6.72

OH 8.00 8.00 8.00 8.00 8.00 7.98 8.00 2.00 1.96
F <dl <dl <dl <dl <dl 0.02 <dl <dl 0.04
Total anion 8.00 8.00 8.00 8.00 8.00 8.00 8.00 2.00 2.00

Si/Al 1.06 1.10 0.95 1.13 1.05 1.02 1.14 1.35 2.13
Total anion ¼ numbers of OHþF; Onormalized: oxygen numbers for normalizing the molecule of mineral. Mineral
abbreviations are after Whitney and Evans (2010) except for those not mentioned: Ilt: illite; Kln: kaolinite; Mnt: mont-
morillonite. <dl – below detection limits.

abundance (Table 4). The matrix and cement (being mainly kaolinite) in the sandstone are
less than 15 vol.%.
The microphotos of typical minerals in coals (G2 to G6), claystone (G7-1 and G7-2) and
sandstone (G1) are shown in Figures 3 to 5, respectively. Their chemical compositions and
normalized molecular formulas are presented in Tables 5 to 8. The important minerals are
described as following.
Kaolinite in the coal (G2 to G6), claystone (G7-1 and G7-2), and sandstone (G1), mostly
is micro-grained with a diameter ranging from 1.5 mm to 6.0 mm (Figures 3(c) to (d), 4(a) and
12 Energy Exploration & Exploitation 0(0)

Table 6. Chemical compositions (wt. %) of typical minerals in the coals (G2 to G6), sandstone (G1) and
claystone (G7-1 and G7-2).

Mineral Ilt Brm Chm Chm Wns Wns Bt Ali

Sample G4 G2 G1 G2 G1 G1 G1 G1

SiO2 46.15 47.99 29.18 25.53 30.63 39.91 35.05 45.85

TiO2 0.34 0.11 <dl <dl 3.33 1.51 2.83 <dl
Al2O3 30.07 37.87 23.39 24.23 14.73 15.47 19.99 4.03
FeO 4.67 0.19 23.34 31.50 27.80 10.99 19.27 22.51
MnO 0.32 <dl 0.26 <dl 0.21 0.18 0.18 0.29
MgO 1.09 0.27 9.32 5.36 10.15 15.71 7.99 12.89
CaO <dl 0.57 0.16 0.16 <dl <dl <dl 0.88
Na2O 0.38 4.35 0.04 0.09 0.17 0.15 0.09 <dl
K2O 7.31 1.27 0.36 0.05 3.01 7.69 10.43 0.10
P2O5 0.02 <dl 0.04 <dl <dl <dl <dl 0.12
F 2.72 <dl <dl <dl 0.24 3.21 0.25 0.11
Cl <dl 0.01 <dl 0.02 0.16 0.21 0.02 <dl
Total wt.% 93.07 92.62 86.09 86.94 90.43 95.03 96.10 86.78

Onormalized 11 11 14 14 11 11 11 11

Si 3.20 3.12 3.05 2.78 2.41 2.98 2.67 3.61

Ti 0.02 0.01 <dl <dl 0.20 0.08 0.16 <dl
Al 2.45 2.90 2.88 3.11 1.36 1.36 1.79 0.37
Fe3þ 0.27 <dl <dl <dl 1.09 <dl <dl 0.22
Fe2þ <dl 0.01 2.04 2.87 0.74 0.69 1.23 1.26
Mn 0.02 <dl 0.02 <dl 0.01 0.01 0.01 0.02
Mg 0.11 0.03 1.45 0.87 1.19 1.75 0.91 1.51
Ca <dl 0.04 0.02 0.02 <dl <dl <dl 0.07
Na 0.05 0.55 0.01 0.02 0.03 0.02 0.01 <dl
K 0.65 0.11 0.05 0.01 0.30 0.73 1.01 0.01
Total cation 6.77 6.77 9.52 9.68 7.33 7.62 7.79 7.07

OH 1.40 2.00 8.00 8.00 1.92 1.21 1.94 1.97

F 0.60 <dl <dl <dl 0.06 0.76 0.06 0.03
Cl <dl <dl <dl <dl 0.02 0.03 <dl <dl
Total anion 2.00 2.00 8.00 8.00 2.00 2.00 2.00 2.00

Si/Al 1.30 1.08 1.06 0.89 1.76 2.19 1.49 9.65

  
Total anion ¼ numbers of OH þF þCl ; Onormalized: oxygen numbers for normalizing the molecule of mineral. Mineral
abbreviations are after Whitney and Evans (2010) except for those not mentioned: Ali: aliettite; Brm: brammallite; Bt:
biotite; Chm: chamosite; Ilt: illite; Wns: wonesite. <dl – below detection limits.

(c) to (e), and 5(c) to (e)), but it is usually accumulated as a stripe or clump in the coal
(Figure 3(c) and (d)), or as a sheet in the claystone (Figure 4(c) and (d)) and sandstone
(Figure 5(a) and (b)), or as an intergrain filling in the sandstone (Figure 5(c) to (e)); occa-
sionally, it occurs in worm-shaped coarse crystal in the coal. The wavy stripe and some
orientating rhomboid of kaolinite mass in the coal (Figure 3(c)) indicate that they had been
reformed by flowing water. Usually, mica-sheeted kaolinite mass may be observed in the
Zhang et al. 13

Table 7. Chemical compositions (wt. %) of typical minerals in the coals (G2 to G6), sandstone (G1) and
claystone (G7-1 and G7-2).

Mineral Grt Sa Fdol Sd Sd Cal Cal Cal

Sample G1 G1 G1 G1 G1 G2 G5 G6

SiO2 38.83 62.55 <dl <dl <dl <dl <dl <dl

TiO2 0.08 <dl <dl <dl 0.10 0.06 <dl <dl
Al2O3 21.56 17.30 <dl <dl <dl 0.02 0.02 <dl
FeO 27.80 <dl 12.13 52.79 53.14 <dl 0.04 0.51
MnO 0.33 <dl 0.27 1.13 0.96 0.31 1.70 1.53
MgO 9.74 <dl 10.66 1.43 1.76 0.11 1.14 0.65
CaO 0.95 <dl 28.37 1.30 1.13 51.61 54.31 51.46
Na2O <dl 1.01 <dl <dl <dl <dl <dl 0.02
K2O <dl 16.04 <dl <dl <dl <dl <dl <dl
P2O5 0.07 <dl <dl <dl <dl 0.03 0.10 0.06
Total wt.% 99.36 96.90 51.43 56.65 57.09 52.15 57.31 54.23

Onormalized 12 8 1 1 1 1 1 1

Si 3.00 3.00 <dl <dl <dl <dl <dl <dl

Ti 0.01 <dl <dl <dl <dl <dl <dl <dl
Al 1.97 0.98 <dl <dl <dl <dl <dl <dl
Fe3þ 0.02 <dl <dl <dl <dl <dl <dl <dl
Fe2þ 1.78 <dl 0.18 0.91 0.90 <dl <dl 0.01
Mn 0.02 <dl <dl 0.02 0.02 0.01 0.02 0.02
Mg 1.12 <dl 0.28 0.04 0.05 <dl 0.03 0.02
Ca 0.08 <dl 0.54 0.03 0.03 0.99 0.94 0.95
Na <dl 0.09 <dl <dl <dl <dl <dl <dl
K <dl 0.98 <dl <dl <dl <dl <dl <dl
Total cation 8.00 5.05 1.00 1.00 1.00 1.00 0.99 1.00
Onormalized: oxygen numbers for normalizing the molecule of mineral; Mineral abbreviations are after Whitney and Evans
(2010) except for those not mentioned: Cal: calcite; Fdol: ferroan dolomite; Grt: garnet; Sa: sanidine; Sd: siderite. <dl –
below detection limits.

coal, claystone, and sandstone, especially in the claystone (Figure 4(c) and (d)) and sand-
stone (Figure 5(a) and (b)), which indicates that it was transformed in situ from a mica by
weathering. No matter what mode of occurrence it is, the kaolinite has a similar composi-
tion with a Si/Al molar ratio ranging from 0.95 to 1.13 (Tables 5), close to ideal kaolinite
(Si/Al ¼ 1.00).
Montmorillonite only observed in the claystone (G7-1 and G7-2) is mostly granular and
short-rod-shaped with a size ranging from 4 mm to 13 mm and a sheeted mass is morpho-
logically similar to a mica (Figure 4(b)). The montmorillonite is a potassium variety (mont-
morillonite-K), and its molecular formula was calculated based on the EPMA data as
(K0.37Na0.01)0.38(Mg0.14Fe3þ0.10Al1.83Ti0.04)2.11(Al0.65Si3.35)4O10(OH)2 (Table 5).
Illite and brammallite both belong to the dioctahedral interlayer-deficient mica, the former
is a potassium member, and the latter is a sodium one. The illite in the coal (G2 to G6) is
mica-sheeted and coexists with kaolinite aggregate, and that in the claystone (G7-1 and G7-2)
is granular less than 4 mm in size or short stripe-shaped with a size about 2
6 mm2 (Figure 4
14 Energy Exploration & Exploitation 0(0)

Table 8. Elemental compositions (wt. %) of sulfides in the No. 3 coal (G2, G4 and G6) and sandstone (G1).

Mineral Pyrite Pyrite Pyrite Selenio-galena Selenio-galena Sphalerite

Sample G2 G4 G6 G6 G1 G1

Fe 45.82 46.16 44.90 0.06 <dl 0.72

Co 0.05 0.02 0.05 <dl <dl <dl
Cu <dl <dl 0.07 <dl <dl 0.08
Zn <dl <dl <dl 0.06 <dl 61.04
Pb 0.11 0.10 0.29 78.31 84.56 0.10
As <dl 0.04 <dl <dl <dl 0.03
Sb <dl <dl <dl <dl 0.03 0.03
Bi <dl 0.05 <dl 0.014 <dl <dl
S 53.46 49.21 52.83 5.91 10.84 34.11
Se 0.04 <dl 0.06 16.17 6.03 <dl
Te 0.04 <dl 0.02 0.05 <dl <dl
Total wt.% 99.52 95.58 98.22 100.70 101.46 96.11

ANormalized 2 2 2 1 1 1

Fe2þ 0.98 1.08 0.98 <dl <dl 0.01

Zn2þ <dl <dl <dl <dl <dl 0.88
Pb2þ <dl <dl <dl 0.97 0.99 <dl
S2- 2.00 2.00 2.00 0.47 0. 82 1.00
Se2- <dl <dl <dl 0.53 0.18 <dl
Total ions 2.98 3.08 2.98 1.97 1.99 1.89
ANormalized – anion numbers for normalizing the molecules of minerals, here is SþSeþTeþAs. <dl – below detec-
tion limits.

(a), (c), and (e)). Their molecular formulas in the coal and claystone are: (K0.65Na0.05)0.70
(Mg0.11Mn0.02Fe3þ0.27Al1.65Ti0.02)2.07(Al0.80Si3.20)4O10[(OH)1.40F0.60]2 and (K0.72Na0.02)0.74
(Fe2þ0.01Mg0.34Fe3þ0.32Al1.29Ti0.04)2(Al0.40Si3.60)4O10[(OH)1.96F0.04]2 (Tables 5 and 6),
respectively. Brammallite only occurs as a filling of fusinite cell cavity in the coal (G2) and
coexists with calcite or occasional chamosite (Figure 3(e)), and its molecular formula is given
as (Na0.55K0.11Ca0.04)0.70(Fe0.01Mg0.03Al2.02)2.06(Al0.88Si3.12)4O10(OH)2 (Table 6).
Wonesite is a trioctahedral interlayer-deficient mica. It was observed in the sandstone
(G1) with a false form of biotite (Figure 5(d) to (f)). The assemblage of wonesite, siderite,
ferroan dolomite and kaolinite (Figure 5(e) and (f)) indicates that it may be an intermediate
of weathered biotite. The biotite is only enclosed in a quartz grain. Chemically, the wonesite
is similar to the biotite. The molecular formulas are given as (K0.30Na0.03)0.33
(Fe0.74Mn0.01Mg1.19Fe3þ0.86Ti0.20)3(Fe3þ0.23Al1.36Si2.41)4(OH1.92F0.06Cl0.02)2 and (K0.73
Na0.02)0.75(Fe0.69Mn0.01Mg1.75Ti0.08Al0.34)2.87(Al1.02Si2.98)4(OH1.21F0.76 Cl0.03)2 for the wone-
site, and as (K1.01Na0.01)1.02(Fe1.23Mn0.01Mg0.91Ti0.16Al0.46)2.77(Al1.33Si2.67)4 (OH1.94F0.06)2
for the biotite (Table 6). In addition, the wonesite reported in the literature is a sodium
one, but this text gave out a potassium one.
Chamosite is rare, occurs as a filling of fusinite cell cavity with calcite or brammallite in the
coal (G2), or coexists with wonesite in the sandstone (G1). Their molecular formulas are
(Na0.02K0.01Ca0.02)0.05(Fe2.87Mg0.87Al1.89)5.63(Al1.22Si2.78)4O10(OH)8 and (Na0.01K0.05Ca0.02)0.08
(Fe2.04Mn0.02Mg1.45Al1.93)5.44(Al0.95Si3.05)4O10(OH)8 (Table 6), respectively.
Zhang et al. 15

Feldspar in the sandstone (G1) including sanidine, microcline (with grid twinning stria-
tion), albite and perthite (intergrown sanidine and albite) is granular with a size ranging
from 8 mm to 30 mm. The sanidine, microcline, and albite are almost pure endmembers
in chemistry.
Garnet clasts in the sandstone are granular, and their partial rims have transformed into
aliettite (Figure 5(c)). The composition of garnet is (Fe2þ1.78Mg1.12Ca0.08Mn0.02)3
(Fe3þ0.02Ti0.01Al1.97)2Si3O12 (Table 7). The composition of aliettite, a regularly interstratified
talc-saponite mineral, is (K0.01Ca0.07)0.08(Mn0.02Fe1.26Mg1.51Fe3þ0.20)2.99(Fe3þ0.02
Al0.37Si3.61)4O10[(OH)1.97F0.03]2.
Quartzose clasts include quartz and chalcedony. Quartz in the coal (G3) occurs locally
and is angular or granular less than 30 mm in size. That in the claystone (G7-1 and G7-2) is
mostly angular and granular less than 20 mm (Figure 4(a) and (e)), but a few coarse grains
with cracks are in size ranging from 200 mm to 320 mm (Figure 4(f)). That in the sandstone is
angular and irregularly harbor-shaped clast, and is mostly in size ranging from 100 mm to
600 mm (Figure 5(a) to (f)), partially (coexisting with kaolinite) from 2.5 mm to 8.0 mm
(Figure 5(c)). Occasionally, diamond-shaped quartz, indicating a pseudomorph of beta-
quartz, could be observed in the coal (Figure 3(f)), claystone (Figure 4(f)) and sandstone
(Figure 5(a)). The beta-quartz pseudomorph and cracked grain may indicate their volcanic
origin. Chalcedony clast occurs in the sandstone, it has angular or long oval shape with a
size ranging from 200 mm to 900 mm, which is comprised of micro quartz crystal less than
10 mm in size (Figure 5(a) and (f)).
Carbonate mineral observed includes calcite, ferroan dolomite, and siderite. Calcite
occurs as filling of fusinite cell cavity (Figure 3(a) and (e)) and in the fine vein (Figure 3
(c)) in the coal (G2). It is chemically close to pure CaCO3 (Table 7). Ferroan dolomite and
siderite occur in the sandstone (G1), the former fills in the intergrain cavity between clasts
(Figure 5(e) and (f)) and the latter occurs with wonesite and kaolinite together (Figure 5(e)).
The ferroan dolomite is comprised of CaCO3 (54.0 mol.%), MgCO3 (28.0 mol.%), and
FeCO3 (18.0 mol.%), and the siderite has FeCO3 content more than 90 mol.%, and minor
CaCO3, MgCO3, and MnCO3 (Table 7). The modes of occurrence and compositions of
carbonate mineral imply their different origins, that is, the calcite is related to post-
diagenetic hydrothermal fluid, the ferroan dolomite and siderite are derived from a biotite
weathering after it had been deposited.
Sulfide observed includes pyrite, selenio-galena, chalcopyrite, and sphalerite. Pyrite in the
coal (G2 to G6) occurs extensively and is scattered in kaolinite mass or in calcite vein
(Figure 3(c)) or forms vein itself (Figure 3(d)). That in the claystone (G7-1 and G7-2)
and sandstone (G1) mostly occurs in vein or film. The trace elements in pyrite are minor
(Table 8). Selenio-galena in the coal, claystone, and sandstone occurs in a group as grain
less than 6.0 mm in size. It contains an amount of selenium ranging from 6.03 wt.% to
16.17 wt.% (Table 8) and a trace amount of bismuth. Chalcopyrite is trace in the coal.
Sphalerite is trace in the sandstone.
In general, the coal is comprised of dominant kaolinite and calcite; the claystone is
characteristic of major kaolinite and montmorillonite, and proportional illite; and the sand-
stone contains mainly quartz and chalcedony and relative feldspar and kaolinite (Figure 2).
Those minerals show that there are two genetic periods, pre-diagenetic and epigenetic ones.
The pre-diagenetic minerals are predominant in the coal seam, which is associated with
weathering of source rock, sedimentation, and diagenesis; and the epigenetic ones including
calcite and pyrite, etc., are minor, which are derived from the hydrothermal deposit and
16 Energy Exploration & Exploitation 0(0)

influence the coal more than the claystone and sandstone for the coal has much
more microcrack.

Geochemistry
Major elements. The concentration of major elements in oxide of the sandstone (G1) and
claystone (G7-1 and G7-2) is listed in Table 9. The SiO2 and Al2O3 are dominant constit-
uents. The sandstone has high SiO2 76.87 wt.% and high Al2O3 13.39 wt.%; and the clay-
stone has moderate SiO2 52.83–56.17 wt.% and high Al2O3 27.83–30.41 wt.%, which may be
utilized as a good refractory. All rocks have moderately high K2O contents (1.36–1.86 wt.%)
and low MnO, FeO, MgO, CaO, Na2O and P2O5 contents. The major elements of rocks are
dependent on their major mineral components. High SiO2 content indicates the existence of
quartz, high Al2O3 does the increase of aluminous clay minerals, high K2O means a con-
stituent of alkali feldspar or another potassium-bearing mineral, and low MnO, FeO, MgO,
and CaO imply the lack of ferromagnesian minerals. This is consistent with the observation
that the sandstone is mainly comprised of quartz and chalcedony and that the claystone is of
kaolinite and montmorillonite. Normalized to the average composition of upper continental
crust (UCC; Rudnick and Gao, 2003), the diagram (Figure 6(a)) exhibits that the sandstone
and claystone are depleted in MnO, FeO, MgO, CaO, Na2O, P2O5 and K2O, but the
sandstone has SiO2 and Al2O3 contents proximal to the UCC, whereas the claystone only
has SiO2 proximal to that and is rich in TiO2 and Al2O3. The depletion of ferromagnesian
major elements indicates that the sandstone and claystone have similar source rocks which
are dominantly comprised of felsic constituents.

Trace and rare earth elements. The 43 trace and rare earth elements of the sandstone (G1) and
claystone (G7-1 and G7-2) are presented in Table 10. The pattern diagram of trace elements
normalized to UCC composition (Rudnick and Gao, 2003) may obviously exhibit their
relative enrichment and depletion (Figure 6(b)).
Comparing with the UCC, the sandstone (G1) is slightly enriched in only Mo, and is
depleted in other else elements, especially in Be, Sr, Cs, V, Cr, Co, Ni, Cu, Bi, Sb, Tl, U, W,

Table 9. Major oxides (wt. %) and some indices for the sandstone (G1) and claystone (G7-1 and G7-2).

Sample SiO2 TiO2 Al2O3 Fe2O3 FeO MnO MgO CaO

G1 76.87 0.33 13.39 0.20 0.80 0.01 0.49 0.64

G7-1 56.17 0.93 27.83 0.34 1.05 0.01 0.71 0.18
G7-2 52.83 0.87 30.41 0.23 1.20 <dl 0.70 0.20
Sample Na2O K 2O P2O5 LOI Total CIA CIW ICV

G1 0.69 1.86 0.04 4.68 100 83.9 85.7 0.41

G7-1 0.23 1.66 0.05 10.86 100 94.6 97.7 0.23
G7-2 0.25 1.36 0.05 11.92 100 93.7 97.7 0.22
LOI: loss on ignition. CIA ¼ 100
Al2O3/(Al2O3þCaO*þNa2OþK2O) (Nesbitt and Young, 1982); CIW ¼ 100
Al2O3/
(Al2O3þCaO*þNa2O) (Harnois, 1988); ICV ¼ (TiO2þFe2O3þMnOþMgOþCaOþNa2OþK2O)/Al2O3 (Cox et al.,
1995); CaO* ¼ value eliminating the effect of apatite and calcite, and all oxides are in molar percentage; <dl – below
detection limits.
Zhang et al. 17

Figure 6. Diagrams of major and trace elements of rocks.

(a) and (b) major elements and trace elements patterns both are normalized to UCC (Rudnick and Gao,
2003), FeO - total iron oxides.

In, Y and Sc, whose concentrations are less half of those in the UCC (Figure 6(b)).
These depleted trace elements include ferromagnesian trace elements (Cr, Co and Ni),
large ion lithophile elements (LILE; Rb, Cs, Sr and Ba), high field strength elements
(HFSE; Nb, Ta, Zr, Hf, and Ti), and heavy rare earth elements (HREE; Tb– Er). The
depletion of some trace elements in the sandstone is related to the dilution of enriched
quartz. The claystone (G7-1 and G7-2) is highly enriched in Li and Bi with concentrations
of 157
106–229
106 and 0.71
106–0.97
106, respectively (Table 10), which are
five or more times higher than that of the UCC (Figure 6(b)). It is moderately enriched in
Cs, Be, U, Th, Nb, V, Mo, In and Pb with two to four times higher concentrations than the
UCC, slightly in Ta, Zr, Hf, W, Cd, Ga and Sc, even and light REE (La–Sm) with less than
two times concentrations of the UCC (Figure 6(b)). The claystone is depleted in Sr, Ba, Cr,
Co, Ni, Cu, Zn, Sb and Tl with less than about half concentrations of the UCC (Figure 6
(b)). The claystone is depleted in ferromagnesian trace elements, LILE (Sr and Ba), but
enriched in HFSE (Nb, Ta, Zr, Hf, and Ti). The depletion and enrichment of the trace
elements in sediments reflect the elemental differentiation in the surface process and the
source constituent. The ratios of Rb/Sr, Rb/Y, Nb/Ta, Zr/Hf, and Ti/Zr are close to those
of the UCC (Table 10), which indicates that the claystone and sandstone have similar source
rock being characteristic of the UCC. The Th/U ratio is higher for the sandstone (G1) and
lower for the claystone (G7-1 and G7-2) comparing with the UCC (Table 10), which indi-
cates that the sandstone had a loss of U but the claystone increased U in the weathering and
sedimentary processes. The enriched U and Th may cause the high natural gamma-ray level
of the claystone near the bottom of the No. 3 coal seam (Feng and Dong, 1997). In addition,
combining the cases that the claystone is enriched in Pb, Bi and In, and that the selenio-
galena contains much amount of Se and minor Bi (Table 8) (Indium usually occurs in galena
but was not analyzed in this study), the trace element group of In, Pb, Bi, and Se enriched
would mostly occur in the selenio-galena in the claystone.
The claystone (G7-1 and G7-2) and sandstone (G1) have high total REE (TREE) con-
tents ranging from 114
106 to 249
106 (Table 10). The ratios of LREE/HREE (light
REE to heavy REE) range from 11.9 to 14.1, and the ratios of LaN/YbN normalized to
chondrite (McDonough and Sun, 1995) range from 12.8 to 16.4 (Table 10). These ratios are
18 Energy Exploration & Exploitation 0(0)

Table 10. Trace elements (
106) and some chemical indices of the sandstone (G1) and claystone (G7-1
and G7-2).

Sample Li Be Sc V Cr Co Ni Cu Zn Ga

G1 12.3 0.81 2.84 29.4 16.9 4.28 4.66 4.04 47.7 12.3
G7-1 157 3.75 17.5 192 49.5 6.24 17.5 13.1 26.3 26.9
G7-2 229 4.37 13.6 234 45.7 7.96 26.0 15.6 28.7 29.8

Sample Rb Sr Y Mo Cd In Sb Cs Ba La

G1 50.9 141 9.50 1.37 0.08 0.02 0.07 0.88 438 29.0
G7-1 77.5 169 22.2 2.66 0.12 0.13 0.23 10.2 217 52.2
G7-2 65.4 175 16.8 1.56 0.14 0.17 0.23 8.93 182 45.8

Sample Ce Pr Nd Sm Eu Gd Tb Dy Ho Er

G1 48.9 5.46 19.6 3.03 0.67 2.39 0.35 1.88 0.39 1.04
G7-1 113 11.7 43.3 8.35 1.45 5.66 0.96 5.18 1.04 2.77
G7-2 86.5 8.55 30.7 5.29 0.93 3.82 0.67 3.90 0.71 2.11

Sample Tm Yb Lu W Tl Pb Bi Th U Zr

G1 0.17 1.20 0.16 0.64 0.27 16.1 0.04 6.86 1.11 145
G7-1 0.45 2.77 0.45 2.72 0.47 51.3 0.71 23.9 7.72 283
G7-2 0.39 2.34 0.36 2.72 0.48 64.4 0.97 21.9 10.4 280

Sample Hf Nb Ta TREE LREE HREE L/H LaN/YbN dCe* dEu*

G1 4.31 8.37 0.54 114 107 7.59 14.1 16.4 0.94 0.76
G7-1 8.33 22.6 1.42 249 230 19.3 11.9 12.8 1.11 0.64
G7-2 9.75 22.5 1.71 192 178 14.3 12.4 13.3 1.06 0.63

Sample Sr/Cu Sr/Ba V/Cr Ce/La V/(VþNi) Rb/Sr Rb/Y Nb/Ta Zr/Hf Th/U

G1 34.9 0.32 1.74 1.69 0.86 0.36 5.36 15.5 33.6 6.18
G7-1 12.9 0.78 3.88 2.16 0.92 0.46 3.49 15.9 34.0 3.10
G7-2 11.2 0.96 5.12 1.89 0.90 0.37 3.89 13.2 28.7 2.11
TREE ¼ LREE þ HREE; LREE ¼ La þ Ce þ Pr þ Nd þ Sm þ Eu; HREE ¼ Gd þ Tb þ Dy þ Ho þ Er þ Tm þ Yb þ Lu; L/H ¼
LREE/HREE; dEu* ¼ EuN/(SmN
GdN)0.5; dCe* ¼ CeN/(LaN
PrN)0.5; subscript N – value normalized to chondrite
(McDonough and Sun, 1995).

just slightly higher than those of the UCC (9.33 and 10.5, respectively), which indicates that
the rocks have an REE pattern with LREE enrichment compared to HREE and is relatively
approximate to that of the UCC. The rocks both have a moderately negative Eu anomaly
(0.63–0.76); the claystone has a weak positive Ce anomaly (1.06–1.11), but the sandstone has
a weak negative one (0.94) (Table 10). Comparing with the UCC, the sandstone (G1) is
slightly depleted in REE, but the claystone (G7-1 and G7-2) is weakly enriched in REE or in
the partial members of REE (Figure 6(b)).
Zhang et al. 19

Discussion
Genesis of minerals
As mentioned above, the mineral related to the No. 3 coal seam in Guotun Mine has two
genetic periods, pre-diagenetic and epigenetic ones. Mineral origins in the pre-diagenetic
period include inheriting, weathering and authigenesis; and that in the epigenetic period is a
hydrothermal deposit.
In general, minerals in a clastic sedimentary rock are almost derived from the source
region. The sedimentary system of the Shanxi Formation bearing the No. 3 coal seam was a
river-controlled shallow water delta system, including fore delta, delta front, delta plain, and
peat bog facies in the Juye Coalfield basin (Bie, 2013; Han and Wei, 2001). The source
region of the Shanxi Formation is the orogenic belt at the northern margin of the North
China Craton (Zhu and Mou, 1987) because the orogenic belt uplifting in the Early-Middle
Devonian Epochs has made the terrain of the craton high in the north and low in the south
(Figure 1) during the Carboniferous and Permian. From the Late Carboniferous to
Permian, the post-orogenic extension led to a large amount of bimodal volcanic rock and
alkali feldspar granite in the orogenic belt (Zhang et al., 2018). The erosion of these rocks
along with the pre-Carboniferous and Carboniferous sedimentary and metamorphic rocks,
and some island arc igneous rock of early Palaeozoic (Zhang et al., 2018) may transport
mineral clasts into the North China Basin in the Permian. The major minerals in the No. 3
coal seam such as quartz, chalcedony, feldspar, mica, kaolinite, montmorillonite and trace
heavy minerals may mostly be inherited from the source region. The quartz, chalcedony,
feldspar, and mica in sandstone indicate that their source rock is dominantly a felsic vol-
canic and granitic rock, which conforms to the rock constituents of the northern uplifting
region if considering the intense weathering. The major elements of the rocks may provide
important evidence of intense weathering of the source rocks by the high values of chemical
index of alteration (CIA, Nesbitt and Young, 1982) and chemical index of weathering (CIW,
Harnois, 1988) for the sandstone and claystone (Table 9), though there are only a few
samples in this study and the high CIA value may be resulted in by high rainfall (White
and Blum, 1995) and by sediment recycling (Tian et al., 2015; Yang and Du, 2017). The
values of the index of compositional variability (ICV) for both sandstone and claystone are
well below 1 (Table 9), which is suggestive of a possible sediment recycling (Cox et al., 1995)
and of a quiescent environment of a stable craton (Weaver, 1989). However, the location of
Guotun Mine in the North China Craton well matches the case of a quiescently sedimentary
environment of the Shanxi Formation and advances the weathering grade of sediments. The
kaolinite and montmorillonite may be the weathering product of feldspar or volcanic rock.
Geochemically, the trace elements of the sandstone and claystone are much different from
the carbonaceous horizons of Permian Barakar Formation of Sattupalli coal field of
Godavari Valley in India (Prachiti et al., 2011), whose source region has mafic and felsic
rocks. Therefore, the inheriting minerals derived from the source rocks with volcanic and
granitic rocks and their weathering products are the major genesis of the minerals in the
studied coal seam.
The inheriting minerals also include minor ones derived from volcanic ash fallout accord-
ing to the petrological observation. But its proportion is probably minor because the sed-
imentary area had a far distance to the volcanic source in the northern uplifting region. The
20 Energy Exploration & Exploitation 0(0)

Figure 7. The plot of minerals of the coal and rocks in MR3–2R3–3R2 coordinates (Velde, 1985).
MR3¼NaþKþ2Ca; 2R3¼(Fe3þþAlþTi-MR3)/ 2; 3R2¼(Fe2þþMnþMg)/3; ion values are in mole. The arrows
show the evolving trends of mineral alteration in the coal and rocks.

relative proportion of quartz with characteristics of volcanic clast in the sandstone (G1) is
probably derived from the volcanic rock in the source region. The chalcedony in the sand-
stone may probably be derived from the volcanic rock in the source region. So, taking the
sandstone as a primary volcanic rock for its volcanic clast is not appropriate (Zhang, 2016),
that is, the sandstone had been reworked.
The weathering minerals here means those that are weathered after depositing in the
basin but before diagenesis. Plotting the composition of kaolinite, illite, montmorillonite,
feldspar and rock samples, etc., on the MR3–2R3–3R2 coordinate (Velde, 1985), there are
two variational trends of mineral, that one is a clear evolution from phengite (including
muscovite) to illite, then to montmorillonite, and finally to kaolinite; and that another is
defined by biotite, which is degraded to wonesite, and finally to kaolinite or chamosite
(Figure 7). Both trends are associated with loss of potassium, or iron and magnesium.
Additionally, garnet has a loss of aluminium. The transformation process between different
minerals is of great interest because it reflects all the stages of degradation of minerals and
allows people to deduce their genetic processes (Fesharaki et al., 2007). The kaolinite may be
derived from the weathering of feldspar, mica, or volcanic ash. That some mass of kaolinite,
montmorillonite, illite or wonesite still keeps the mica shape in the coal, claystone, and
sandstone is just good evidence of such a process. The calcium, iron, and magnesium
released from minerals in weathering may form calcite, siderite and dolomite retaining in
Zhang et al. 21

the rocks. An acidic condition, for an example in the peat swamp environment, is in favor of
the weathering of feldspar and forming of kaolinite.
The minor authigenic minerals include mainly the worm-shaped kaolinite in the coal,
dolomite in the sandstone, and part of sulfite in the coal, claystone, and sandstone.
The hydrothermally original minerals are mainly calcite and pyrite in veins in the coal,
claystone, and sandstone. Petrologically, the calcite vein had affected the coal more intense
than the claystone and sandstone because the coal had a large amount of crack and micro-
crack, whereas the rocks did sparsely. The epigenetic hydrothermal event was probably
induced by the widespread Jurassic magmatism in east China. Except for vein, another
occurrence of calcite in the coal is filling in the fusinite cavity, coexisting with brammallite.
Such calcite and brammallite were derived from the hydrothermal deposit for their filling
occurrence. Because that clausthalite in coal may be associated with the hydrothermal activ-
ity (Hower and Robertson, 2003), and that selenio-galena is a solid solution between galena
and clausthalite, so the selenio-galena in the coal has probably a hydrothermal origin.

Enrichment in trace elements

Coal and relative mudstone are usually enriched in some trace elements. The study on the
Handan-Xingtai Coalfield (Zhao, 2008) far to the west of the Juye Coalfield (Figure 1)
showed that the coal neighboring the rock enriched in some trace elements was usually
enriched in the same trace elements (Zhao, 2008). The claystone of the No. 3 coal seam
in Guotun Mine is enriched in Li, U, Th, V, Mo, In, Pb, Bi, and even Se. This is similar in
kind and concentration of trace elements with the mudstones in the Handan-Xingtai
Coalfield (Zhao, 2008). So, the No. 3 coal in Guotun Mine is probably enriched in the
same trace elements as the claystone, though that was not analyzed, unfortunately. The
geological report of Guotun Mine shows that the average values of V, Th, and U in the No.
3 coal are slightly higher than that in North China coal (Zhao et al., 2002) or in United
States coal (Finkelman, 1993). A neighboring coalfield, the Ji’ning Coalfield, had been
studied for 10 kinds of trace elements sensitive to the environment, i.e., As, B, Cd, Hg,
Mo, Pb, Se, Ni, Cr, in coals (Hu, 2009). Among them, As, B, Cd, Cr, Ni, and Se are
relatively enriched compared to the average values of China coal, but their contents vary
much in different coal mines, different coal seams, and different parts of the same coal seam
(Hu, 2009). The richest trace elements in coal seam known well usually are Li and Ga. The
recommended minimum mining grades of Li and Ga in coal are 120
106 and 30
106,
respectively (Sun et al., 2014), but those in mudstone has not been determined yet. Li and
Ga in part of claystone in the Handan-Xingtai Coalfield reach to the minimum mining
grades mentioned above (as the case in Guotun Mine), but those in the coal equivalent to
the No. 3 coal in Guotun Mine do not. Considering the similar sedimentary environment of
the Shanxi Formation in the two coalfields, it is less likely for the No. 3 coal in Guotun Mine
to form rare metal deposits.
The factors affecting the enrichment of trace elements in sediment are an abundant
source (Wronkiewicz and Condie, 1987) and suitable depositional environment. On one
hand, taking the Li as an example, when the Shanxi Formation in the Juye Coalfield depos-
ited, there were relative proportion of volcanic and granitic rocks in the source region, and
they were weathered to supply a relative amount of Li into the basin because Li was usually
high in felsic volcanic and granitic rocks and was an easily mobile element in the surface. On
the other hand, the delta environment of No. 3 coal seam with various sub-facies was in
22 Energy Exploration & Exploitation 0(0)

favor of the sedimentary sorting and enrichment of some trace elements. In the peat bog and
bottom sediment, Li is easily bound with small organic molecules and easily released when
small molecules are polymerized (He et al., 2016); Mo, V, U, Pb, and Se are easily enriched
in reduced condition (Tribovillard et al., 2006). Some ratios of elemental pairs in sediments
are usually used as important indicators of the sedimentary environment. For examples, The
Sr/Cu ratios greater than 10 of the sandstone and claystone indicated an arid and hot
climate (McLennan, 2001); the sandstone with a Sr/Ba ratio of 0.32 less than 0.6
(Table 10) had a terrestrial environment with fresh water, while the claystone with Sr/Ba
ratios of 0.78 and 0.96 (Table 10) had a transitional facies between terrene and marine with
brackish water (Liu and Zhou, 2007; Zheng and Liu, 1999). The high ratios of V/Cr (Jones
and Manning, 1994), V/(VþNi) (Davis et al., 1999) and Ce/La (Bai et al., 1994) of the
claystone suggested a reduced condition of sedimentation (Table 10). The peat bog related
to the No. 3 coal seam containing abundant organic compound and having reduced con-
dition provided such a suitable environment to enrich in Li, V, U, Mo, In, Pb, Bi, and Se.
However, the carriers of trace elements are another important factor influencing on their
enrichment in coal. Most of the trace elements in coal are associated with minerals, mainly
including clay, carbonate and sulfide ones, and some are with organic compound (Hu, 2009;
Zhao, 2008). The mode of occurrence of Li in coal is still an unresolved topic. The coalifi-
cation seems not to be fit for much enrichment of Li (He et al., 2016). A Li-carrier mineral
discovered in coal was an intermediate between cookeite and chamosite (Dai et al., 2012).
Lithium in coal was usually considered to be associated with illite, montmorillonite, and
kaolinite (Dai et al., 2012; Sun et al., 2012, 2013), but from the point of mineral structure,
kaolinite unfits to combine Li cation. So, the major Li-carrier may probably be montmoril-
lonite and illite. Uranium or Th occurred in zircon or monazite, and was probably associated
with an organic compound; vanadium was probably associated with clay or organic com-
pound; molybdenum occurred in sulfides (Finkelman and Gross, 1999). This study shows
that In, Pb, Bi, and Se occur mainly in selenio-galena, and minor in pyrite. For the hydro-
thermal origin of selenio-galena, the enrichment of at least some trace elements in the No. 3
coal seam is to a certain extent associated with the epigenetic hydrothermal activity.

Conclusion
The No. 3 coal seam of the Permian Shanxi Formation in Guotun Mine, Juye Coalfield,
north China, is mineralogically characteristic of different mineral constituents in the coal,
claystone, and sandstone. The coal is comprised of dominant kaolinite and calcite, the
claystone is characteristic of major kaolinite, montmorillonite, and proportional illite,
and the sandstone contains mainly quartz and chalcedony and a relative amount of feldspar
and kaolinite. These minerals were derived dominantly from the weathered source rocks
with volcanic and granitic constituents in the pre-diagenetic period, and minor from the
hydrothermal deposit in the epigenetic period.
The claystone is relatively enriched in Li, Cs, Be, Nb, Mo, U, Th, V, In, Pb, Bi and Se,
and the enrichment may be controlled by the felsic source rocks and the specific sedimentary
environment. The enriched trace elements are mostly associated with minerals. Li may
probably occur in montmorillonite and illite, while In, Pb, Bi, and Se occur mainly in
selenio-galena.
Zhang et al. 23

Acknowledgements
The authors are grateful to the reviewers for their careful reviews and detailed comments. Thanks are
given to Fangyu Ma, the General Engineer in Guotun Mine, for his great help in sampling.

Declaration of conflicting interests

The author(s) declared no potential conflicts of interest with respect to the research, authorship, and/or
publication of this article.

Funding
The author(s) disclosed receipt of the following financial support for the research, authorship, and/or
publication of this article: This research was supported by the projects of the National Natural Science
Foundation of China (No. 41330317 and 41604069), the top talent project of Science and Technology
Research in Higher Education Institutions of Hebei Province (No. BJ2018010) and the plan of the
Hebei Collaborative Innovation Centre of Coal Exploitation.

ORCID iD
Jingsen Zhang https://orcid.org/0000-0001-9605-8319

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