Fuel 181 (2016) 859–869

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Mineralogical compositions of Late Permian coals from the Yueliangtian

mine, western Guizhou, China: Comparison to coals from eastern
Yunnan, with an emphasis on the origin of the minerals
Peipei Wang ⇑, Dongping Ji, Yongchang Yang, Lixin Zhao
State Key Laboratory of Coal Resources and Safe Mining, China University of Mining and Technology (Beijing), Beijing 100083, China
College of Geoscience and Survey Engineering, China University of Mining and Technology (Beijing), Beijing 100083, China

h i g h l i g h t s

 A mineralogical comparison has been made of the Late Permian coals in west Guizhou and east Yunnan.
 Quartz and kaolinite in the No. 19 coal are related to weathering of the Emeishan basalt.
 An altered tonstein layer derived from felsic volcanic ash has been identified in the No. 19 coal.
 The studied coals have less chamosite than the Late Permian coal in east Yunnan.
 No hydrothermal mixed-layer I/S or detrital calcite was found in the coals of this study.

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

Article history: This paper reports the mineralogical characteristics of a complete coal seam in the Late Permian Longtan
Received 14 March 2016 Formation from the Yueliangtian mine, western Guizhou, southwestern China. The minerals in the coal
Received in revised form 7 May 2016 were identified using optical microscopy, scanning electron microscopy with an energy dispersive X-
Accepted 7 May 2016
ray spectrometer (SEM–EDS), and low temperature ashing plus X-ray diffraction (LTA + XRD). The results
Available online 13 May 2016
show that quartz and kaolinite are the major components of the coal mineral matter; followed by pyrite,
marcasite, anatase, and calcite; and in some cases, mixed-layer illite/smectite, chamosite, illite, ankerite,
Keywords:
apatite, and anorthite. The highly-elevated concentration of quartz in the coal is mostly derived from
Late Permian coal
Minerals in coal
siliceous solutions produced by weathering of the Emeishan basalt. However, quartz discrete particles
Emeishan basalt with large size (>100 lm) and rounded shape probably resulted from the input of felsic rock materials.
Guizhou Province The distribution and modes of occurrence of kaolinite, mixed-layer illite/smectite, illite, and anatase
reflect a terrigenous origin. In comparison with the coals from eastern Yunnan, the Yueliangtian coals
have lower proportion of authigenic chamosite, the formation of which was probably related to the injec-
tion of seawater. Pyrite occurring as individual particles or clustered framboids was most likely influ-
enced by seawater during the stages of peat accumulation or early diagenesis, while fracture-filling
pyrite probably had an epigenetic origin. Additionally, an intra-seam volcanic ash-derived tonstein layer,
which contains sharp-edged quartz, vermicular kaolinite, and well-developed zircon crystals, has been
identified in the coal of the present study.
Ó 2016 Elsevier Ltd. All rights reserved.

1. Introduction Minerals in the Late Permian coals of southwestern China have

The formation of minerals in coal may be associated with a ser-
ies of geological processes, including peat accumulation, injection
of seawater, influx of hydrothermal fluids, deposits of synsedimen-
tary volcanic-ash, diagenetic process, and coal rank advance [1–3].
⇑ Corresponding author at: State Key Laboratory of Coal Resources and Safe
Mining, China University of Mining and Technology (Beijing), Beijing 100083, China.
E-mail address: wangpeipei1100@gmail.com (P. Wang).
attracted much attention, not only because they in some cases
are carriers of valuable elements (e.g., Nb, Ta, Zr, Hf, REE, and Ga)
that have potential for industrial utilization [1,4–6], but also
because they may reflect the depositional conditions of the original
peat swamp, the geological history of the coal-bearing sequences,
and the regional tectonics [2]. It has been suggested that the
mineralogy of the Late Permian coal and coal-bearing strata in
southwestern China might not only be used as indicators for depo-
sitional environment before, during, and after peat accumulation

http://dx.doi.org/10.1016/j.fuel.2016.05.043
0016-2361/Ó 2016 Elsevier Ltd. All rights reserved.
860 P. Wang et al. / Fuel 181 (2016) 859–869
[7,8], but could also provide essential information for evolution of
the Emeishan mantle plume [9,10].
The Late Permian was an important coal-forming period in
southwestern China, especially in Chongqing, southern Sichuan,
eastern Yunnan, and western Guizhou. Guizhou Province, known
as ‘‘Southern Sea of Coal”, possesses the largest preserved coal
resources in southwestern China. The mineralogical and geochem-
ical characteristics of the Late Permian coals in southwestern China
have been subjected to a number of investigations [1,4,9,11–21]
which have shown that the mineral matter in these coals has a sig-
nificant relation with the Emeishan Large Igneous Province (ELIP),
the major part of which (the Kangdian Upland) is mainly located to
the west of the coal basin that is the focus of the present study [10].
Previous studies have shown that authigenic quartz [2] and
chamosite [22,23] are the dominant components of the mineral-
assemblages in the Late Permian coals from southwestern China.
The authigenic quartz is considered to be the product of kaolinite
desilication or precipitation from siliceous solutions derived from
weathering of Emeishan basalts in the Kangdian Upland
[2,18,22–24]. It is believed that the formation of chamosite was
related to the reaction of kaolinite with Fe–Mg-rich fluids, or to
precipitation of Fe–Mg-rich siliceous solutions derived from
weathering of Emeishan basalts [22,23]. In most cases, kaolinite
is the dominant clay minerals in the Late Permian coals
[18,22,23]; however, abundant mixed-layer illite/smectite induced
by mafic magmatic activity has been found in some coals (e.g.,
Changxing mine) from eastern Yunnan [25].
Previous studies have mostly focused on the Late Permian coals
in southern Sichuan, Chongqing, and eastern Yunnan, and only a
few investigations have been carried out on the mineralogy of coals
from western Guizhou [12,14,26–29]. In this paper, we describe
the lateral variation of minerals in the Late Permian coals from
the Yueliangtian mine, Panxian Coalfield, western Guizhou and
from eastern Yunnan Province (Fig. 1), with an emphasis on the
Fig. 1. Location of the Yueliangtian mine, Panxian coalfield, western Guizhou Province, China, as well as locations of the Mahe, Xinde, Xuanwei, Taoshuping, and Changxing
mines, eastern Yunnan Province, China, and the corresponding geography during the Late Permian.
origin of the minerals in these coals and the associated host rocks
(intra-seam tonstein, roof and floor strata). Such a comparison of
mineral compositions in coals from western Guizhou and its sur-
rounding areas (particularly eastern Yunnan province, which is clo-
sely located to the Kangdian Upland; Fig. 1) could provide more
information for depositional conditions of the original peat
swamps and help reveal the relationship between the ELIP and coal
formation in the region.
2. Geological setting
The Yueliangtian coal mine is located in Panjiang Town, Panx-
ian, Guizhou Province (Fig. 1). The major coal-bearing strata in
the mine are the Upper Permian Longtan Formation, with an aver-
age thickness of 234.66 m. The Longtan Formation in the Yueliang-
tian mine mainly comprises fine sandstone, siltstone, pelitic
siltstone, silty mudstone, mudstone, and coal seams, while the
lowermost portion of the Longtan Formation is characterized by
a bauxite layer with an average thickness of 5 m (Fig. 2A). The
Longtan Formation contains 12 minable coal seams, with an aver-
age total thickness of 16.27 m. The studied No. 19 coal seam, with
an average thickness of 1.32 m, is located in the middle portion of
the Longtan Formation and is one of the most important minable
seams in this area (Fig. 2B). Two partings occurring in the No. 19
coal have a thickness of 4 (YLT19-5p) and 5 cm (YLT19-8p), respec-
tively. The roof and the floor strata of the No. 19 coal are mainly
gray fine siltstone and fine sandstone, respectively.
In contrast to the Xuanwei Formation in eastern Yunnan, which
was mainly formed in a non-marine environment, the Longtan For-
mation in western Guizhou was deposited in a continental-marine
transitional environment during the Late Permian, after the
emplacement of Emeishan Large Igneous Province (260 Ma)
[30,31]. The Xuanwei and Longtan Formations are contemporane-
ous deposits but have different sedimentary environments [32].
 P. Wang et al. / Fuel 181 (2016) 859–869
Fig. 2. (A) Sedimentary sequences in the Yueliangtian mine; (B) section of the No. 19 coal seam.
The Kangdian Upland, comprising a sequence of Emeishan basalts
in the lower section and a few felsic-intermediate rocks in the
upper section, is the primary sediment-source area for the Xuan-
wei and Longtan Formations in the study areas [33–35].
3. Samples and analytical procedures
Samples from eight coal benches (nos. YLT19-2c, YLT19-3c,
YLT19-4c, YLT19-6c, YLT19-7c, YLT19-9c, YLT19-10c, and YLT19-
11c), two partings (YLT19-5p and YLT19-8p), and two host rocks
(roof YLT19-1r and floor YLT19-12f) (Fig. 2B) were collected from
the No. 19 coal at the Yueliangtian coal mine. In order to avoid con-
tamination and oxidation, all samples were stored in plastic bags
immediately after collection. All samples were crushed and milled
to pass 200 mesh for proximate and geochemical analyses.
The proximate and related analyses, including moisture, ash
yield, volatile matter, total sulfur, forms of sulfur, and gross calori-
fic values of the coals were based on ASTM Standards D3173-11,
861
D3174-11, D3175-11 [36–38], D3177-02 [39], D2492-02 [40],
and Chinese Standards GB/T 213-2008 [41], respectively. Ultimate
analysis for carbon, hydrogen, and nitrogen was conducted using a
Vario Macro elemental analyzer. A Leica DM-4500P microscope
equipped with a Craic QDI 302TM spectrophotometer was used to
determine the mean random vitrinite reflectance. All the samples
were high-temperature ashed at 815 °C, as preparation for deter-
mining the percentage of major-element oxides (SiO2, TiO2,
Al2O3, Fe2O3, MnO, MgO, CaO, Na2O, K2O, and P2O5) by X-ray fluo-
rescence spectrometry.
Eight coal bench samples were ashed at low temperature using
an EMITECH K1050X plasma asher. After low temperature ashing,
X-ray diffraction (XRD) analysis was conducted on the low temper-
ature ashes (LTAs), as well as the un-ashed roof, floor, and parting
samples, using a D/max-2500/PC powder diffractometer with Ni-
filtered Cu-Ka radiation and a scintillation detector. Each XRD pat-
tern was recorded over a 2h interval of 2.6–70°, with a step size of
0.02°. In order to obtain the quantitative mineralogical composi-
tion, X-ray diffractograms of the coal LTAs and host rock samples
862 P. Wang et al. / Fuel 181 (2016) 859–869

were analyzed using SiroquantTM software developed by Taylor
[42]. Details of this technique have been described in Ward et al.
[43,44] and Ruan and Ward [45].
Polished coal pellets were prepared for mineralogical study
(mineral morphology and distributions) using optical microscope
and Field Emission-Scanning Electron Microscope equipped with
an EDAX energy-dispersive X-ray spectrometer (SEM–EDS).
4. Results
4.1. Coal chemistry
The data on coal chemistry for the No. 19 coal samples are
shown in Table 1. The weighted average of vitrinite reflectance
(1.02%) and volatile matter yield (28.90%) suggest that the coals
are of medium volatile bituminous rank according to the ASTM
classification (ASTM D388-12, 2012) [46]. Moreover, according to
Chinese Standards GB/T 15224.1-2010 [47], the No. 19 coal has a
medium ash yield.
Total sulfur content in the No. 19 coal ranges from 0.28% to
4.76%, with a weighted average of 1.67%, indicating a medium-
sulfur coal (coal with 1–3% total sulfur is medium-sulfur coal
[48]). The percentage of total sulfur is low (<1%) in the upper
benches (YLT19-2c, YLT19-3c, and YLT19-4c) and is mainly derived
from coal-forming plants [48,49]. However, sulfur are relatively
abundant in the middle and lower benches, suggesting that the
sulfur was mainly derived from seawater [48,50]. As indicated in
Table 1, high total sulfur contents of 4.14%, 2.02%, and 4.76% were
measured in samples YLT19-6c, YLT19-7c, and YLT19-9c, respec-
tively. The forms of sulfur analyses show that pyritic sulfur is the
dominant in these three samples, with percentages of 3.51%,
1.71%, and 3.93%, respectively.
4.2. Mineralogical characteristics
4.2.1. Minerals in coal
Table 2 lists the LTA yield of the coals, together with the miner-
alogical results of each coal LTA and non-coal sample (roof, floor,
and partings) determined by XRD and Siroquant. The minerals in
the coal LTAs are dominated by quartz (7.7–82.5%) and kaolinite
(17–70.6%), followed by pyrite (1.5–23.4%), marcasite (4.1–8.4%),
calcite (0.1–17.4%), and anatase (0.1–1.7%), while the abundance
of illite, mixed-layer illite/smectite, chamosite, and ankerite is
more variable in these samples.
Kaolinite makes up a large percentage of minerals in the coal
benches, ranging from 17% to 70.6%. Observations under the opti-
cal and scanning electron microscope show that kaolinite in the
coal benches mostly occurs as lenses and thin beds (Fig. 4A), indi-
cating a terrigenous origin. Kaolinite in some cases occurs as a
matrix for pyrite, anatase, and small quartz grains
(Figs. 4A, F and 6A). A small proportion of kaolinite occurs in
structured-maceral cells (Fig. 5F), indicating an authigenic origin
[9]. Illite and chamosite are only detectable in samples YLT19-6c
and YLT19-11c, respectively. Based on investigations by Rimmer
and Davis [51], Ward [3], and Dai et al. [52], the illite most likely
resulted from detrital materials of terrigenous origin. Chamosite
is present as cell-fillings (Fig. 5F) when studied under the SEM,
suggesting an authigenic origin.
Quartz (ranging from 7.7% to 82.5%; Table 2) is generally the
dominant mineral in the coal LTAs. The proportion of quartz is
higher in the upper benches (YLT19-2c, YLT19-3c, and YLT19-4c)
near the roof than in the middle and lower benches (Fig. 3). The
optical microscopy and SEM–EDS analyses show that the quartz
in the coals occurs mostly either as scattered irregular particles
distributed in collodetrinite (Fig. 4E), or as cell-fillings of the struc-
tured macerals (Fig. 4H). In most cases the quartz particles are fine
(<10 lm); however, large grains of quartz (>100 lm) are also
observed under both the optical microscopy and the SEM.
As indicated in Table 2, pyrite and marcasite are only observed
in the LTAs of the middle and lower coal benches. Pyrite is excep-
tionally abundant in coal bench sample YLT19-9c, consistent with
the relatively high concentration of total sulfur (4.76%; Table 1).
The pyrite has various modes of occurrence, including discrete par-
ticles, framboidal assemblages (Fig. 5A), subhedral to euhedral
crystals (Fig. 5B), massive forms in the organic matrix (Fig. 5C),
fracture-fillings (Fig. 5D), and cell-fillings (Fig. 5E). The marcasite
typically coats massive pyrite as radiating crystals (Fig. 5C). Chal-
copyrite was observed to occur as cell-fillings (Fig. 5F) under the
SEM, but is below the detection limit of the XRD and Siroquant
techniques.
Calcite occurs as a minor component in all of the coal bench
samples. The proportion of calcite is higher in the LTA of coal sam-
ples YLT19-3c and YLT19-4c than in that of other coal benches,
consistent with the high proportions of CaO in those coal samples
(Table 3). Calcite shows two modes of occurrence under optical and
electron microscopy. Most of the calcite occurs as fracture- or
cleat-fillings in collodetrinite (Fig. 5G), indicating an epigenetic ori-
gin [9,20,22,23]. Some calcite coexists with quartz or chamosite as
cell-fillings (Fig. 5F), but this is a minor mode of occurrence. A
minor proportion of ankerite was observed in the upper coal
benches of No. 19 coal, directly below the roof strata.
The proportion of anatase in the coal LTAs is generally low, and
may be below the detection limit of the XRD and Siroquant
techniques. However, the LTA of sample YLT19-6c has the highest
proportion of anatase (1.7%) among the LTAs of the coal samples.

Table 1
Bench thickness (m), proximate and ultimate analyses (%), total sulfur (%), forms of sulfur (%), gross calorific values (MJ/kg), and vitrinite random reflectance (%) of the No. 19 coal
samples.

Sample Thickness Mad Ad Vdaf Cdaf Hdaf Ndaf St,d Sp,d Ss,d So,d Qgr,d Ro,ran
YLT19-2c 0.20 1.79 36.02 26.31 88.16 5.42 1.25 0.28 23.03 nd
YLT19-3c 0.24 0.53 19.44 16.68 89.21 4.65 1.38 0.35 28.94 nd
YLT19-4c 0.26 0.96 15.32 31.50 87.03 5.27 1.43 0.53 30.57 1.05
YLT19-6c 0.20 2.48 40.37 35.67 83.84 5.54 1.31 4.14 3.51 0.13 0.50 19.90 1.03
YLT19-7c 0.20 1.92 22.74 30.43 87.09 5.20 1.36 2.02 1.71 0.04 0.27 28.16 1.03
YLT19-9c 0.20 0.63 19.58 32.34 84.68 5.23 1.41 4.76 3.93 0.09 0.74 28.96 1.01
YLT19-10c 0.20 2.05 12.87 29.38 90.56 5.01 1.52 0.85 32.52 1.04
YLT19-11c 0.20 2.42 19.38 30.55 89.14 5.74 1.76 1.00 29.56 0.96
WA 1.7a 1.55 22.85 28.90 87.49 5.24 1.43 1.67 1.08 0.03 0.18 27.84 1.02

M, moisture; A, ash yield; V, volatile matter yield; C, carbon; H, hydrogen; N, nitrogen; St, total sulfur; Sp, pyritic sulfur; Ss, sulfate sulfur; So, organic sulfur; ad, air-dry basis; d,
dry basis; daf, dry and ash-free basis; Qgr,d, gross calorific value, on a dry basis; Ro,ran, average vitrinite random reflectance; WA, weighted average for bench samples (based on
the interval thickness of each bench sample); nd, not detected.
a
Total thickness of coal benches.
 P. Wang et al. / Fuel 181 (2016) 859–869 863

Table 2
LTA yields of coal samples and mineral compositions of coal LTAs, partings, roof, and floor as determined by XRD and Siroquant (%).

Sample LTA Qu Kao Illite I/S Cha Py Mar Ana Cal Ank Ano Apa
YLT19-1r 9.1 34.9 37.3 6.2 11.4 1.0
YLT19-2c 35.91 82.5 17.0 0.3 0.3
YLT19-3c 20.25 62.5 19.2 17.4 1.0
YLT19-4c 16.69 52.4 34.9 1.5 0.5 9.8 0.9
YLT19-5p 5.3 72.1 10.3 7.2 1.9 3.2
YLT19-6c 52.76 7.7 67.1 12.9 5.8 4.7 1.7 0.1
YLT19-7c 27.40 28.3 57.0 5.4 8.4 0.5 0.4
YLT19-8p 9.2 90.8
YLT19-9c 24.14 25.5 44.4 23.4 5.5 0.2 1.1
YLT19-10c 13.67 39.2 52.0 2.5 4.4 0.1 1.9
YLT19-11c 22.13 17.7 70.6 4.2 2.0 4.1 1.4
YLT19-12f 6.3 27.9 48.9 5.8 10.3 0.8

Qu, quartz; Kao, Kaolinite; I/S, mixed-layer illite/smectite; Cha, Chamosite; Py, Pyrite; Mar, Marcasite; Ana, Anatase; Cal, Calcite; Ank, Ankerite; Ano, Anorthite; Apa, Apatite.

Fig. 3. Vertical variations of low temperature ash yield and minerals in LTA and rock samples through the No. 19 coal section in the Yueliangtian mine.

SEM analysis shows that anatase in this sample mainly occurs as
discrete particles in the kaolinite matrix (Fig. 4F), indicating a
detrital mineral of terrigenous origin.
Silicorhabdophane, identified by SEM–EDS, occurs as fracture-
or cell-fillings, coexisting with kaolinite and quartz (Fig. 5H). As
discussed by some studies (e.g., Dai et al. [53,54], Seredin and
Dai [55], and Dai et al. [56]), silicorhabdophane and rhabdophane
are the major REE carriers in some coal-hosted REY ore deposits
(REY, rare earth elements plus yttrium).
4.2.2. Minerals in partings, roof and floor strata
The two partings in the coal seam are quite different in macro-
scopical and microscopical characteristics. The parting represented
by sample YLT19-5p is a dark gray to black in color, while parting
YLT19-8p is gray-white. The mineral assemblage of sample YLT19-
5p is represented by kaolinite, illite, quartz, pyrite, marcasite, and
anatase. However, the prominent minerals in sample YLT19-8p are
made up almost entirely of kaolinite (90.8%), along with relatively
low percentage of quartz (9.2%).
The kaolinite in sample YLT19-8p occurs mainly in vermicular
form (Fig. 4B and C), indicating a process of in-situ crystallization
[11,57]. Under the SEM, the quartz in sample YLT19-8p shows
sharp edges (Fig. 4C and D). Although it is below the detection limit
of the XRD and Siroquant, a few discrete particles of anatase on the
kaolinite matrix are also observed by SEM–EDS in sample YLT19-
8p. Also under the SEM, a zircon particle in sample YLT19-8p
occurs as well-developed crystal with long prism faces and a
high-temperature eroded hole (Fig. 4C).
The kaolinite in sample YLT19-5p generally occurs as lenses and
thin beds (Fig. 6A), and to a lesser extent, as cell-fillings of struc-
tured macerals (Fig. 6B). These modes of occurrence are similar to
those in the coal bench samples. Illite is also identified in sample
YLT19-5p. Parting YLT19-5p has a very similar clay mineral associ-
ation to the LTA of coal bench sample YLT19-6c, suggesting the same
864 P. Wang et al. / Fuel 181 (2016) 859–869

Fig. 4. Minerals in the No. 19 coal. (A) Kaolinite and pyrite distributed along the bedding planes (reflected light); (B) vermicular kaolinite (reflected light); (C) vermicular
kaolinite, euhedral zircon, sharp-edged quartz, and separate anatase (SEM, back-scattered); (D) sharp-edged quartz (SEM, back-scattered); (E) quartz and calcite veins in the
collodetrinite (reflected light); (F) quartz and anatase particles (SEM, back-scattered); (G) terrigenous detrital quartz (reflected light); (H) cell-filling quartz in semifusinite
(reflected light).

input from terrigenous material [58]. The quartz in sample YLT19-
5p is mostly present as disseminated irregular particles, with a size
usually less than 20 lm (Fig. 6C). Anatase occurs as discrete parti-
cles in the kaolinite matrix (Fig. 6A), probably indicating a terrige-
nous origin. Pyrite in sample YLT19-5p occurs mainly as clustered
framboidal (Fig. 6D) and cell-filling (Fig. 6B) forms, suggesting a
syngenetic origin [3,48]. Compared with sample YLT19-8p, no
sharp-edged quartz, vermicular kaolinite, or well-developed euhe-
dral zircons were identified in sample YLT19-5p. The modes of
occurrence of the minerals in sample YLT19-5p indicate a significant
contribution from normal sediments of terrigenous origin.
As indicated in Table 2, the mineral assemblage in the roof sam-
ple is similar to that in the floor material, probably indicating the
same source of detrital input. Kaolinite and mixed-layer illite/
smectite, with a total percentage up to 70%, are the dominant min-
erals in the roof and floor, together with significant proportions of
anorthite, quartz, anatase, and apatite. The roof of the No. 19 coal
has higher quartz content (9.1%) than the floor strata. Anatase is
more abundant in the host rocks (YLT19-1r and YLT19-12f) than
in the partings, with proportions of 6.2% and 5.8%, respectively
(Table 2). Anorthite and apatite were also observed in the roof
and floor samples, which is consistent with the relatively high con-
centrations of CaO and P2O5 listed in Table 3.
4.3. Chemical composition
The percentages of major-element oxides in the No. 19 coal are
given in Table 3. Compared with the average values for Chinese
 P. Wang et al. / Fuel 181 (2016) 859–869 865

Fig. 5. Minerals in the No. 19 coal. (A) Framboidal pyrite (reflected light); (B) subhedral to euhedral pyrite crystals (reflected light); (C) marcasite growing on massive pyrite
as radiating crystals (reflected light); (D) fracture-filling pyrite (reflected light); (E) cell-filling pyrite (reflected light, oil immersion); (F) cell-filling calcite, kaolinite,
chamosite, and chalcopyrite (SEM, back-scattered); (G) calcite veins in the collodetrinite (reflected light); (H) fracture-filling silicorhabdophane (SEM, back-scattered).

coals [4], the proportions of SiO2 and TiO2 in the No. 19 coal are
higher. However, the contents of the other major-element oxides
are much lower than the averages for Chinese coals. The contents
of Fe2O3 and MgO2 are distinctly lower than those from coals of
eastern Yunnan (e.g., Xuanwei, Xinde, Taoshuping, and Mahe
mines). Silicon usually occurs in quartz and clay minerals. In the
same way, anatase is the dominant carrier of titanium in the coals.
Similarly, the low proportions of K, Na, Fe, and Mg in the coals is
consistent with the low proportions of mixed-layer illite/smectite
and chamosite. The ratio of SiO2/Al2O3 in the No. 19 coal (4.87) is
much higher not only than that in Chinese coals (1.42) but also
than the theoretical ratio for kaolinite (1.2), which is due to the
high percentage of quartz in the No. 19 coal. Sample YLT19-2c
has the highest SiO2/Al2O3 value (16.39) among the coal bench
samples, consistent with the highest quartz content (82.5%) of its
mineral matter; while sample YLT19-6c contains the lowest SiO2/
Al2O3 value (1.51), reflecting the lowest proportion of quartz
(7.7%) in the LTA material.
Table 4 shows the correlation coefficients between the ash yield
and the major-element oxides. The ash yield and CaO have a neg-
ative correlation, probably because Ca was mainly released by
macerals during coal rank evolution and precipitated in the cleats
of the low-ash coals rather than derived from terrigenous input
[3,59–62]. The strong positive correlation between the ash yield
and Na, Mg, Al, Si, K, and Ti suggests that these elements are closely
related to the mineral matter in the No. 19 coal sampled in this
study. The significant correlation of Ti with Al, Mg, Na, and K sup-
ports the coexistence of anatase and some clay minerals, which is
also consistent with the optical microscope and SEM–EDS analyses
[63].
866 P. Wang et al. / Fuel 181 (2016) 859–869

Table 3
Major element oxides and loss on ignition (LOI) of coal benches, host rocks, and partings from No. 19 coal seam (%; on whole coal/rock basis).

Sample SiO2 TiO2 Al2O3 Fe2O3 MnO MgO CaO Na2O K2O P2O5 LOI SiO2/Al2O3
YLT19-1r 46.47 6.53 23.94 2.99 0.012 1.06 0.95 0.572 1.384 0.499 14.58 1.94
YLT19-2c 32.64 0.17 1.99 0.13 0.001 0.05 0.12 0.036 0.026 0.017 64.62 16.39
YLT19-3c 12.70 0.13 1.94 0.38 0.009 0.08 2.51 0.028 0.021 0.016 80.67 6.56
YLT19-4c 10.38 0.23 2.14 0.43 0.006 0.05 1.05 0.043 0.022 0.010 84.82 4.85
YLT19-5p 29.90 3.39 20.02 5.87 0.019 0.38 0.19 0.230 0.463 0.048 38.23 1.49
YLT19-6c 18.54 1.96 12.27 5.27 0.008 0.21 0.28 0.137 0.155 0.056 60.63 1.51
YLT19-7c 13.45 0.26 5.55 2.44 0.002 0.06 0.19 0.049 0.028 0.012 77.69 2.42
YLT19-8p 41.56 0.53 28.40 0.88 0.001 0.16 0.09 0.230 0.126 0.039 27.84 1.46
YLT19-9c 10.05 0.13 3.99 4.89 0.001 0.06 0.10 0.030 0.010 0.015 80.54 2.52
YLT19-10c 8.33 0.21 2.88 0.62 0.002 0.03 0.23 0.030 0.009 0.011 87.39 2.89
YLT19-11c 10.06 0.76 5.58 1.78 0.003 0.16 0.21 0.051 0.064 0.017 81.08 1.80
YLT19-12f 44.81 5.37 23.54 5.90 0.004 1.40 0.40 0.623 1.434 0.115 15.65 1.90
Averagea 14.52 0.48 4.54 1.99 0.004 0.09 0.59 0.051 0.042 0.019 77.18 4.87
Chinese coalb 8.47 0.33 5.98 4.85 0.015 0.22 1.23 0.160 0.190 0.092 nd 1.42
Xuanwei coalc 18.12 0.49 2.87 6.31 0.136 0.24 4.09 0.036 0.123 0.087 nd 6.31
Xinde coald 28.15 0.58 8.80 3.51 0.019 0.39 0.81 0.023 0.219 0.050 nd 3.20
Taoshuping coale 47.43 3.04 28.29 17.49 0.027 0.53 1.35 0.263 0.770 0.113 nd 1.68
Mahe coalf 17.31 0.50 8.26 3.40 0.030 0.21 1.57 0.140 0.320 0.070 nd 2.10

nd, no data.
a
Average value for coal bench samples.
b
Chinese average coals value from Dai et al. [4].
c
Xuanwei average coals value from Dai et al. [22].
d
Xinde average coals value from Dai et al. [9].
e
Taoshuping average coals value from Wang et al. [18].
f
Mahe average coals value from Wang et al. [20].

Fig. 6. SEM back-scattered images of minerals in the No. 19 coal. (A) Quartz, kaolinite, and anatase particles; (B) cell-filling pyrite and kaolinite; (C) quartz in the
collodetrinite; (D) framboidal pyrite.

Table 4
Correlation analysis of ash yield and major element composition.

Variable Ash SiO2 TiO2 Al2O3 Fe2O3 MnO MgO CaO Na2O K2O P2O5
Ash 1.00
SiO2 0.96 1.00
TiO2 0.84 0.73 1.00
Al2O3 0.94 0.85 0.72 1.00
Fe2O3 0.45 0.26 0.59 0.46 1.00
MnO 0.38 0.25 0.56 0.35 0.42 1.00
MgO 0.82 0.74 0.93 0.69 0.53 0.31 1.00
CaO 0.14 0.14 0.00 0.22 0.33 0.30 0.03 1.00
Na2O 0.92 0.84 0.94 0.82 0.50 0.35 0.97 0.02 1.00
K2O 0.84 0.76 0.97 0.70 0.50 0.39 0.99 0.04 0.98 1.00
P2O5 0.66 0.62 0.82 0.54 0.20 0.41 0.69 0.15 0.75 0.78 1.00
 P. Wang et al. / Fuel 181 (2016) 859–869
5. Discussion
5.1. Origin of minerals in Late Permian coals from Yueliangtian mine
Based on the abundance, distribution, and modes of occurrence
of minerals in the No. 19 coal of the present study, we have iden-
tified a number of mineral sources including the Emeishan basalt,
felsic clastic-rock, felsic volcanic ash, seawater, and hydrothermal
fluids.
5.1.1. Influence of sediment-source region
The Emeishan basalt of the Kangdian Upland, located to west of
the Panxian coalfield, is the primary sediment-source region for
the mineral matter in the No. 19 coal at the Yueliangtian mine,
as well as for the coals from most of other areas in southwestern
China [64–67]. Sediment was supplied in the following two ways:
input of terrigenous detrital materials and influx of siliceous solu-
tions from weathering [18].
The distribution and modes of occurrence of minerals in the
coal bench samples, as well as in parting sample YLT19-5p, provide
strong evidence for input from the sediment-source area, such as
the discrete illite and anatase particles, together with the sedimen-
tary layering of the clay minerals. The clay mineralogy of coal sam-
ples YLT19-6c and YLT19-11c is different to that of other coal
bench samples, which may indicate a slight change of sedimentary
environment or input from different clastic-rocks during deposi-
tion of the No. 19 coal seam.
The vertical distribution of quartz is opposite to that of kaolinite
(Fig. 3). This indicates that kaolinite and quartz in the No. 19 coal
may result from different geological controls. The presence of abun-
dant authigenic quartz is probably due to precipitation of silica-
bearing solutions derived from weathering of the Emeishan basalt
in the Kangdian Upland [2,18], while the modes of occurrence of
the kaolinite reflect derivation from the weathering residues of the
Emeishan basalt [18,23], similar to those in the Late Permian coals
of eastern Yunnan (e.g., Xuanwei, Xinde, and Mahe coals) [9,20,22].
The ratio of TiO2 to Al2O3 is regarded as an effective indicator to
identify the origin of clastic sediments and intra-seam tonstein lay-
ers based on the similarity between the TiO2/Al2O3 ratios of mud-
stones and their parent rocks [11,35,68–71]. Indicative TiO2/Al2O3
values of felsic, intermediate, and mafic tonsteins are <0.02, 0.02–
0.08, and >0.08 [9,11,24], respectively. Except for sample YLT19-
8p, the host rocks (roof and floor) as well as parting YLT19-5p have
a TiO2/Al2O3 value >0.16, supporting a suggestion that the parent
rocks were of mafic basalt composition.
However, the modes of occurrence of quartz in the coals of this
study, e.g., distributed along the bedding planes with defined edges
and angles (Fig. 4G) and occurring mainly as discrete particles, sug-
gest that this form of quartz is of terrigenous origin. Compared
with the authigenic quartz also present in the coals, the terrige-
nous detrital quartz is usually large in size (>100 lm) (Fig. 4E, F,
and H). Such quartz is similar to the terrigenous quartz observed
in coals from eastern Yunnan (e.g., Mahe mine) [17], and provides
evidence for input of sediment derived from felsic rock during peat
accumulation [10]. The terrigenous quartz is probably related to
the Emeishan felsic clastic-rocks.
5.1.2. Input of volcanic ash
The parting YLT19-8p is identified as an intra-seam tonstein
layer, and appears to have been derived from felsic volcanic ashes.
This suggestion is supported by the following factors: (1) This part-
ing is a thin layer (5 cm) having a continuous lateral extent and a
clear top and bottom boundary in the coal seam. (2) A vermicular
texture in the kaolinite of such a parting layer is often used as an
indicator of a volcanic origin [9,57,59,72,73]. As reported by Bohor
and Triplehorn [74], such vermicular kaolinite is generally
867
regarded as a typical feature of tonsteins derived from altered vol-
canic ash layers deposited in peat swamps. (3) High-temperature
quartz characterized by sharp edges is considered to be derived
from eruption of a felsic magma pocket or volcanic neck [9,60].
Such quartz has also been found in some Late Permian partings
within coals of the surrounding areas (especially eastern Yunnan)
[9,60]. (4) Although zircons of different origins vary a lot in mor-
phology and crystal habit [60,75], studies by Zhou et al. [60,75]
have shown that detrital zircons of terrigenous origin usually have
tetragonal bipyramids with relatively short prisms and length/
width ratios around 2, while pyroclastic zircon generally has long
tetragonal prisms doubly terminated by pyramids and a length to
width ratio higher than 2.5 [9,76]. The zircon particle noted in this
study occurs as a well-developed crystal with a high length/width
ratio (>10), indicating a pyroclastic origin. (5) Parting YLT19-8p has
a TiO2/Al2O3 ratio <0.02, corresponding that expected if the parent
volcanic ash was felsic in composition [9,11,24].
5.1.3. Injection of seawater and hydrothermal fluids
As described in Section 2, the coal-bearing strata of the Longtan
Formation were deposited in a marine-terrestrial transitional envi-
ronment. Seawater may have influenced the mineralogy of the No.
19 coal during the peat-accumulation process. For example, the
formation of pyrite (e.g., framboids, euhedral crystals, and massive
form) and marcasite (radiating crystals) is generally induced by
seawater during peat accumulation or early diagenesis [3,48],
and in this study the presences of pyrite and marcasite may also
suggest the influence of seawater. In addition to seawater, syn-
genetic hydrothermal fluids may invade coal measure sequences,
causing the formation of cell-filling mineral phases, such as pyrite,
chalcopyrite, calcite, and silicorhabdophane. Hence the occurrence
of fracture-filling pyrite, calcite, and silicorhabdophane may also
provide evidence for hydrothermal fluids influx as part of the epi-
genetic activity [32,77,78].
5.2. Differences in mineralogy for Late Permian coals from the
Yueliangtian mine and eastern Yunnan
In contrast to the high concentration of chamosite, regarded as
the reaction product of kaolinite with Fe–Mg-rich fluids or precip-
itation of Fe–Mg-rich siliceous solutions derived from weathering
of Emeishan basalts in the Late Permian coals of eastern Yunnan
[18,22,23], chamosite is not usually observed in No. 19 coal sam-
ples from Yueliangtian mine. The low chamosite content may indi-
cate lack of an Fe–Mg component in the siliceous solutions formed
by weathering of the Emeishan basalt in western Guizhou. A pos-
sible explanation is that the parent basalt in western Guizhou
was subjected to strong leaching besides weathering. As reported
by Ma et al. [79], Si, Mg, Ca, K, and Na can be easily leached from
basalts during weathering processes, allowing Ti, Al, and Fe to be
enriched in the weathering residues. However, Fe2+ (one essential
component of chamosite) can be easily removed under the influ-
ence of aqueous solutions. Therefore we suggest that, different
from that in the Late Permian coals from eastern Yunnan, the for-
mation mechanism of chamosite in this study was probably influ-
enced by seawater.
In addition to a relatively high proportion of terrigenous mixed-
layer illite/smectite, hydrothermal mixed-layer illite/smectite
which had been precipitated from fluids associated with mafic
magmas have been identified in the Late Permian Changxing coals
of eastern Yunnan Province [25]. However, such hydrothermal
mixed-layer illite/smectite occurring as fracture-fillings or cell-
fillings has not been observed in the coal bench samples in this
study, either by optical microscope or SEM–EDS, indicating that
there was probably no subsurface mafic magma activity associated
with the western Guizhou coal deposits.
868 P. Wang et al. / Fuel 181 (2016) 859–869
Volcanic quartz has been widely reported in the Late Permian
coals from eastern Yunnan (e.g., Taoshuping, Changxing, Xuanwei,
Xinde, and Mahe coals) [9,18,20,22,25], indicating frequent felsic
volcanism during the Late Permian period. Zhou et al. [11] and
Dai et al. [24] suggested that such felsic volcanism may be related
to the waning activity of the Emeishan mantle plume. However,
such quartz was not identified in the coal bench samples of the pre-
sent study using SEM–EDS techniques. A possible explanation is
that any such felsic volcanic eruptions provided only a small contri-
bution to the mineral matter in the western Guizhou coal seams.
Calcite in the coals of this study is thought to be mainly derived
from decomposition of organic matter and epigenetic hydrother-
mal solutions. In contrast to the mineral matter in the coals from
eastern Yunnan, such as the Taoshuping coals [18], no detrital cal-
cite was observed in the No. 19 coal of the present study. The detri-
tal calcite in eastern Yunnan is commonly considered as wind-
transported material derived from the Maokou Limestone [18],
which underlies the Emeishan basalts. Moreover, the detrital cal-
cite present in those coal seams is regarded as an indicator of an
alkaline environment [25,80] since calcite can easily be dissolved
in a more acidic environment, which inversely favors the formation
of authigenic kaolinite [3,80,81]. The absence of detrital calcite,
together with the presence of terrigenous kaolinite and a small
proportion of authigenic kaolinite in the No. 19 coal appear to pro-
vide evidence for a slight difference in the coal-forming environ-
ments during the Late Permian period between eastern Yunnan
and western Guizhou.
6. Conclusions
The Late Permian No. 19 coal from the Yueliangtian coal mine is
a medium volatile bituminous coal characterized by medium-ash
and medium-sulfur contents. Quartz, kaolinite, pyrite, marcasite,
anatase, and calcite make up most of the mineral matter in the
coals, together with a variable proportion of illite, mixed-layer
illite/smectite, chamosite, ankerite, apatite, and anorthite. The coal
benches of the No. 19 coal are rich in SiO2 (14.52%, whole-coal
basis), consistent with the abundance of quartz mostly precipitated
from siliceous solutions derived from weathering of the Emeishan
basalt. Kaolinite and mixed-layer illite/smectite occurring as lenses
and thin beds are also mainly derived from the weathering prod-
ucts of the Emeishan basalt. No hydrothermal mixed-layer illite/
smectite, derived from fluids associated with mafic magma, was
observed in the No. 19 coal. In contrast to the coals from eastern
Yunnan, the No. 19 coal has a lower concentration of authigenic
chamosite, the origin of which is influenced by seawater, as well
as pyrite and marcasite. However, some minerals, including
fracture-filling pyrite, calcite, and silicorhabdophane, represent
the post-depositional influx of hydrothermal fluids. One intra-
seam tonstein was recognized in the No. 19 coal based on the min-
eral assemblage (sharp-edged quartz + vermicular kaolinite + well-
developed zircon), providing evidence for the input of felsic vol-
canic ash. Volcanic quartz was not observed in the coal benches,
indicating that the felsic volcanic ash had little effect on the overall
mineral matter in coal bench samples. In addition, the terrigenous
quartz particles (>100 lm) suggest input of sediment derived from
felsic source rocks during peat accumulation. Detrital calcite,
which would indicate an alkaline environment, was not identified
in the No. 19 coal, reflecting a contrast in peat swamp depositional
conditions during the Late Permian period between eastern Yun-
nan and western Guizhou.
Acknowledgments
This research was supported by the National Key Basic Research
Program of China (No. 2014CB238902), the National Natural
Science Foundation of China (Nos. 41420104001 and 41272182),
and the Research Fund for the Doctoral Program of Higher Educa-
tion of China (No. 20120023120019). Many thanks are given to
Prof. Shifeng Dai for his constructive comments, which greatly
improved the quality of the paper. The authors are grateful to Prof.
James C. Hower and the other three anonymous reviewers for their
careful comments.
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