International Journal of Coal Geology 173 (2017) 925

Contents lists available at ScienceDirect

International Journal of Coal Geology

journal homepage: www.elsevier.com/locate/ijcoalgeo

Mineralogical and geochemical characterization of the Saray and

Pnarhisar coals, Northwest Thrace Basin, Turkey
Cemile Erarslan , Yksel rgn
Istanbul Technical University, Faculty of Mines, Geological Engineering Department, Maslak, 34469 Istanbul, Turkey

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

Article history: This study investigates the mineralogical and geochemical characteristics of coals from the Saray and Pnarhisar
Received 25 August 2016 coalelds in the Northwest Thrace Basin, using optical microscopy, scanning electron microscopy, X-ray diffrac-
Received in revised form 27 January 2017 tion and inductively coupled plasma mass spectrometry. The Saray and Pnarhisar coals were deposited in a
Accepted 27 January 2017
limnic environment. The sulfur content of the coals ranges from 0.3 to 15.3% and high sulfur contents may orig-
Available online 5 February 2017
inate from both seawater and volcanism. Pyritic and organic sulfur are the dominant sulfur forms (1.2% and 2.7%
Keywords:
on average, respectively). The mineral matter of the coals consists mainly of pyrite, barite, gypsum, muscovite
Sulfur forms and kaolinite, with minor amounts of quartz, butlerite, tamarugite and rozenite. The coals are enriched in trace
Pyritic sulfur elements, including V (61 ppm on average), Co (5.85 ppm on average), Ni (79 ppm on average), As (39.2 ppm
Sulfur origin on average), Th (3.6 ppm on average) and U (6.7 ppm on average). Based on Pearson correlation coefcients,
Seawater Ti, V, Cr, Fe, Co, Ni, Cu, Se, Rb, Au, Hg, Pb and Th have mainly inorganic afnities (rash-elements N + 0.5) in the
Volcanism Pnarhisar coals; Fe, As and Au also have inorganic afnities (rash-elements +0.5) in the Saray coals. The element
Trace elements contents and correlation coefcients indicate that the Strandja Massif, the Tethyan ophiolite belt and the oldest
Strandja Massif
basement sediments were included in the sediment source region for both coalelds, while the Strandja Massif
Northwest Thrace Basin
was the prevailing sediment source region for Pnarhisar coaleld.
2017 Elsevier B.V. All rights reserved.

1. Introduction
It is known that coal utilization and coal mining can cause signicant
environmental and health problems because of its complex mineralog-
ical and chemical composition (Carlson and Adriano, 1993; Chen et al.,
2011; Dai et al., 2012a; Finkelman, 1994, 2004; Finkelman and Gross,
1999; Finkelman et al., 2002; Goodarzi, 2006; Kolovos et al., 2002;
Singh et al., 2011; Swaine and Goodarzi, 1995; Zhang et al., 2004;
Zhao et al., 2008). However, due to increasing energy demand, many in-
dustrialized and developing countries will continue to use coal for
power generation in the decades to come (International Energy
Agency, 2015).
Identication and evaluation of the problems likely to be resulted
from the utilization of coal and the possible measures to deal with
them requires an understanding of the mineralogical, petrographic
and geochemical properties of coal (e.g. Dai et al., 2008; Finkelman,
1994; Goodarzi, 2002). Also, the mineral matter and element composi-
tion of the coal are important for interpretation of the depositional en-
vironment (Moore and Esmaeili, 2012; Ren, 1996; Scott, 2002).
Corresponding author.
E-mail address: erarslanc@itu.edu.tr (C. Erarslan).
Turkey has about 15 billion tons of coal reserves; about two billion
tons of these reserves (10%) are found in the Thrace coal basin. The
coals are generally low rank sub-bituminous coal and lignite, except
for the Carboniferous bituminous coals of the Zonguldak region (on
the Black Sea coast) (Toprak et al., 2015). The low-rank coal deposits
formed during the Eocene to Pleistocene period in lacustrine environ-
ments, with their formation controlled by either faults or volcanics
(Toprak, 2009). The late Oligocene and Miocene Thrace Basin minable
coal seams are located in Edirne (Demirhanl, Meri, Kean and
Uzunkpr), Krklareli (Pnarhisar) and Tekirda (Topular, Saray and
Malkara) provinces and these coals have been mined for domestic fuel
in general.
The Saray and Pnarhisar coalelds have been exploited since the
1970s by the General Directorate of Turkish Coal Enterprises and private
corporations. The earlier studies on these coals were just presented as
raw data (MTA, 2010; Tuncal et al., 2002). Some data are available for
the Thrace region coals on the general and petrographic characteristics
(Palmer et al., 2004; Toprak, 2009), but, up to now, there have been no
detailed studies of sulfur species, mineralogical and petrographical
characteristics, and trace element contents of these coals. Therefore,
the purpose of this study is to examine the sulfur species, mineralogical
and petrographic characteristics, and the major and trace elements in

http://dx.doi.org/10.1016/j.coal.2017.01.015
0166-5162/ 2017 Elsevier B.V. All rights reserved.
10 C. Erarslan, Y. rgn International Journal of Coal Geology 173 (2017) 925
the coals from the Saray and Pnarhisar coalelds, and to understand the
sedimentary conditions in the coal basin.
2. Geological setting
The study area is situated in the Saray (Tekirda) and Pnarhisar
(Krklareli) counties, in the Thrace Region, in the northwest of Turkey
(Fig. 1A). The Thrace Region is divided into two geological provinces;
the Strandja Massif to the north and the Thrace Basin to the south
(Siyako, 2006a; Siyako and Huvaz, 2007). The Thrace Basin sediments
were deposited on the Strandja Massif, which consists of metamorphic
rocks and Permo-Carboniferous granites (Natalin et al., 2012; Okay et
al., 2001). The oldest sediments were formed in a remnant oceanic
basin, after total consumption of the Neo-Tethyan ocean oor (Ylmaz
and Polat, 1998). Sedimentation in the basin started during the Early Eo-
cene with a marine transgression (Doust and Arkan, 1974; Keskin,
1974; Perinek et al., 2015; Saner, 1985; Turgut et al., 1983). Active vol-
canism, namely the Hisarlda volcanism, started in the Middle Eocene
and continued to the Pliocene. During this period volcanism accompa-
nied the sedimentation (Ercan, 1992; Fytikas et al., 1984; Kaymak et
al., 2007; Ylmaz and Polat, 1998).
After the Eocene transgression a regression commenced in the basin
between the Middle Oligocene and the Lower Miocene (Ediger, 1982;
Ediger, 1988). There was no sedimentation during the Middle Miocene
(Perinek et al., 2015). After this the Late Miocene?-Early Pliocene
Ergene and Krcasalih Formations were deposited in the basin (Fig. 2).
The all the coals mined in the basin were deposited during the regres-
sion period and are located in the Late Oligocene to Early Miocene
Danimen Formation (Fig. 1B, C, D). This formation was deposited
Fig. 1. A: Location map of the study area (modied from Siyako, 2006a and Ylmaz and Polat, 1998; the volcanic rocks were exaggerated for visible); B: Geological map of Edirky coal mine
from Saray coaleld; C: Geological map of the Tozakl coal mine from Pnarhisar coaleld; D: Geological map of the Akren coal mine from Pnarhisar coaleld.
within a limnic-uvial environment (Siyako and Huvaz, 2007; Siyako,
2006b; engler, 2008). The Danimen Formation is composed of delta-
ic and uvial sandstone and claystone, shale, conglomerate, coal and
volcanoclastic material. The thickness of the Danimen Formation is
1600 m (Perinek et al., 2015). The coals' thickness varies laterally
from a few cm to 15 m due to facies changes and erosion.
In the study area, there are three open pit coal mines. The Edirky
mine is located in the Saray coaleld, and the Akren and Tozakl coal
mines are located in the Pnarhisar coaleld. The strata at the Edirky
mine consist of mainly of delta plain and onshore lacustrine uvial sed-
iments. The geologic units in the Edirky coaleld are the Danimen
Formation, the Ergene Formation and alluvium (Fig. 1B). The strata in
the Tozakl coal basin consist of delta plain and uvial sediments, and
the geologic units are the Danimen Formation, Krcasalih Formation
and alluvium (Fig. 1C). The strata in the Akren coal basin consist of a
metamorphic basement and shallow marine and delta plain sediments
(Siyako, 2006a). The Yrkbayr metagranites, Koyunbaba, Soucak
and Danimen Formations are the geologic units of the Akren coal
basin (Fig. 1D).
3. Samples and methods
In this study coal samples were collected from two coalelds: the
Saray coaleld (Edirky coal mine) and the Pnarhisar coaleld (Akren
ve Tozakl coal mines). Edirky and Tozakl coal mines have two coal
seams; Akren coal mine has one coal seam. A total of 30 coal samples
were collected using a channel-prole sampling strategy at three open
pit mines; 14 coal samples from Edirky coal mine (Sample from E6 to
 C. Erarslan, Y. rgn International Journal of Coal Geology 173 (2017) 925 11

Fig. 2. Generalized stratigraphic section of the Thrace Basin (modied from Siyako and Huvaz, 2007).

E25); eight coal samples from Tozakl coal mine (Samples V4, V6, V11,
V12, V13, V14, V15 and V19) and eight coal samples from Akren coal
mine (Samples V5, V8, V9, V16, V17, V18, V20 and V21). The whole
coal samples were taken from the upper coal seams, except E12 and E
25 from Edirky coal mine and sample V13 from Tozakl coal mine.
Each coal sample was collected from a channel 15-cm in depth, 30-cm
in width and 150-cm in length.
Proximate and elemental analysis was carried out at the Turkish Coal
Enterprise (TK) Coal Laboratories in Ktahya, Turkey. Proximate analy-
sis was carried out following ASTM Standard D7582-12, 2012. Total sul-
fur content of the samples was determined using ASTM Standard
D4239-13 (2013). Elemental analysis was determined according to
ASTM Standard D5373-13 (2013). Microscopic analysis and forms of
sulfur (according to TS 329 ISO 157 standard, 2000) studies were per-
formed at the General Directorate of Mineral Research & Exploration
(MTA) Analysis Laboratories in Ankara, Turkey.
The coal samples were prepared for microscopic analysis according
to ASTM Standard D2797/D2797M-11a (2011). The maceral classica-
tion and terminology used in the study are based on ICCP (1998,
2001), Pickel et al. (2017) and Sykorova et al. (2005). Maceral analysis
and huminite reectance measurements were carried out under
reected white and uorescent light using 50 and 20 oil-immersion
objectives and a Leica DM4000M microscope. An immersion-oil with a
refractive index of 1.518 and a sapphire standard with 0.589% reec-
tance were used for the reectance measurements. The maceral content
was determined by the point counting method. Pyrite was also counted
separately from the other minerals (for example, clay, carbonate,
quartz). The reectance measurements were conducted on the gelinite
macerals in the coal samples. Digital photography was conducted using
a Leica DFC 365 FX camera.
A scanning electron microscope in conjunction with an energy-dis-
persive X-ray spectrometer (SEM-EDS) was used to study the mineral
12 C. Erarslan, Y. rgn International Journal of Coal Geology 173 (2017) 925

characteristics in the coals. Mineralogical analysis of the powdered coal
samples was performed by X-ray powder diffraction (XRD) techniques
using a Bruker D8 Advance diffractometer with Cu K radiation and a
scan range of 470 2 at the Istanbul Technical University Geochemical
Research Laboratory. Major (SiO2, TiO2, Al2O3, Fe2O3, MnO, MgO, CaO,
Na2O, K2O, and P2O5 and Cr2O3) and trace element (Be, Sc, V, Co, Ni,
Cu, Zn, Ga, As, Se, Rb, Sr, Y, Zr, Nb, Mo, Ag, Cd, Sn, Sb, Cs, Ba, REEs (La
Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu), Hf, Ta, W, Au,
Hg, Tl, Pb, Bi, Th, and U) analyses of the coal samples were performed
at ACME Analytical Laboratory, Canada by inductively coupled plasma
mass spectrometry (ICP-MS) using LiBO2 fusion methods (The prepared
coal sample was mixed with LiBO2/Li2B4O7 ux and fused in a furnace.
The cooled bead was dissolved in ACS grade nitric acid and analyzed
by ICP-MS) and STD SO-18 standard material.
The major and trace element results were statistically treated using
the Excel and SPSS statistical programs. The correlation coefcient be-
tween the concentrations of the major oxides and trace elements and
the major oxides and the ash yields were calculated. Also, Pearson corre-
lation coefcients between the concentration of the trace elements and
the ash yield and the sulfur content and forms of sulfur were obtained.
4. Results
4.1. General characteristics and the sulfur composition of the coals
The results of the proximate and ultimate analyses, total sulfur and
forms of sulfur for the Saray and Pnarhisar coals are given in Table 1.
The moisture (as received basis), ash (dry basis), volatile matter (dry
and ash free basis) and gross caloric value (dry basis) of the samples
vary from 20.5 to 46.4%, 14.54 to 45.68%, 41.04 to 71.45%, and 1718 to
4049 kcal/kg, respectively, except for sample V15. According to the
proximate and ultimate analysis results, sample V15 from the Pnarhisar
coaleld (Tozakl coal mine), has the lowest moisture, gross caloric
value and C content (11.24%, 209 kcal/kg and 50.05%, respectively)
and the highest ash yield (79.52%). These results, especially the high
ash yield, show that sample V15 is not coal. Therefore, sample V 15
was excluded from the assessment. The huminite reectance values
vary from 0.33 to 0.37% (0.36% on mode). Based on the C content
(53.3583.68% daf), volatile matter and the caloric values, the coals
are classied as lignite according to the ASTM classication. Two values
are given in each case for the total sulfur content of the samples in Table
1. The total sulfur of the coals was determined in conjunction with the
ultimate analysis using ASTM Standard D4239-13 (2013); the forms of
sulfur, which also include the total sulfur, were determined according
to TS 329 ISO 157 standard (2000). The difference between the two
values for total sulfur in Table 1 may therefore be related the different
methods used. The total sulfur content in the coal samples displays a
signicant variation; from 1.86 to 15.3% in the Saray coals and from
2.25 to 5.9% in the Pnarhisar coals (except sample V15). The highest
sulfur percentages occur in the Edirky coals. The forms of sulfur in
the North Thrace Basin coals were determined for the rst time in this
study. As seen in Table 1, the percentages of pyritic sulfur, organic sulfur
and sulfate sulfur vary from 0.17 to 5.25%, 1.11 to 7.47%, 0.25 to 1.38%,
respectively. The total sulfur content of the Pnarhisar coals is lower
than that of the Saray coals (Table 1). The organic sulfur content of the
Pnarhisar coals is also higher than the pyritic sulfur content.

Table 1
Proximate and ultimate analysis and sulfur forms of the Saray and Pnarhisar coals.

Sample Moisture Ash V.M G.C.V. C H N O Total sulfur Total and forms of sulfur Total Rr

(wt%) (kcal/kg) (wt%) (wt%)

(a.r.b.) (d) (daf) (d) (daf) (daf) (daf) (daf) (d) Pyritic Sulfate Organic

Saray coals
E6 35.25 32.38 66.56 2448 67.08 3.82 1.24 23.75 2.78 1.56 0.54 1.11 3.21 0.37
E7 38.35 45.68 66.40 1802 65.02 8.39 1.47 6.37 10.18 3.89 1.04 3.95 8.88 0.36
E8 23.85 35.24 62.48 2847 67.88 6.22 1.67 12.25 7.76 2.56 0.83 2.13 5.52 0.36
E9 41.5 29.23 59.83 2320 70.23 5.68 1.34 15.34 5.25 1.06 1.05 2.07 4.18 nd
E10 41.05 16.55 59.17 2751 67.69 4.93 1.20 18.30 6.58 2.22 0.86 2.16 5.24 0.37
E12 44.6 18.41 58.35 2555 72.83 5.52 1.64 17.74 1.86 0.78 0.6 1.97 3.35 0.36
E16 39.3 14.54 59.47 2893 67.47 5.21 2.15 20.99 3.57 nd nd nd nd nd
E19 42.85 15.88 61.70 2708 67.94 5.46 0.68 20.63 4.46 nd nd nd nd nd
E20 33.85 29.94 65.89 2261 53.35 4.72 0.98 31.76 6.43 nd nd nd nd nd
E21 21.7 40.5 66.12 2418 53.63 3.93 0.29 16.45 15.30 5.25 1.38 7.47 14.1 0.36
E22 40.6 44.62 71.45 1718 65.35 6.72 2.22 19.22 3.60 1.23 0.42 2.06 3.71 nd
E23 46.4 18.21 57.23 2610 77.96 4.80 2.36 11.16 3.05 1.02 0.27 1.89 3.18 nd
E24 41.45 24.64 60.07 2609 76.41 4.96 1.79 11.76 3.83 1.31 0.33 2.33 3.97 0.36
E25 33.25 30.53 57.39 2866 74.51 4.74 2.27 5.18 9.24 4.42 0.68 4.03 9.13 nd

Pnarhisar coals
V4 45.25 23.72 61.06 2331 71.67 4.58 1.64 17.72 3.36 0.51 0.59 1.99 3.09 0.33
V5 45.05 21.45 61.04 2476 73.98 4.00 0.76 14.81 5.07 0.75 0.5 3.79 5.04 0.37
V6 46.1 16.11 62.88 2517 67.41 4.23 1.55 22.20 3.87 0.79 0.87 2.35 4.01 0.37
V8 35.8 25.55 65.79 2659 61.40 3.83 26.90 5.9 nd nd nd nd nd
V9 36.9 20.12 68.63 2943 64.81 3.89 23.93 5.9 0.42 0.98 4.56 5.96 nd
V11 28.45 15.87 63.31 3562 63.66 3.79 1.39 26.57 3.9 nd nd nd nd 0.35
V12 31.7 18.87 64.83 3209 65.84 3.94 1.36 25.38 2.8 nd nd nd nd nd
V13 26.69 20.89 59.56 3432 74.26 4.42 2.28 16.20 2.25 0.51 0.25 1.49 2.25 nd
V14 36.82 21.02 60.76 2912 74.65 4.57 1.91 15.61 2.57 0.49 0.33 1.64 2.46 nd
V15 11.24 79.52 91.80 209 50.05 5.47 2.00 41.19 0.27 0.11 0.19 0 0.3 nd
V16 27.64 20.18 58.51 3377 76.27 3.96 0.78 13.95 4.03 0.18 0.34 3.54 4.06 0.33
V17 21.37 15.07 49.90 4049 79.81 3.57 1.35 11.22 3.44 0.3 0.46 2.61 3.37 nd
V18 20.5 31.45 41.04 3596 83.68 3.44 1.11 8.43 2.29 0.17 0.41 1.7 2.28 nd
V19 45.43 17.62 63.12 2546 81.09 0.66 0.16 13.85 3.50 1.18 0.4 1.93 3.51 0.36
V20 45.3 15.17 63.30 2661 54.11 4.17 0.78 34.67 5.32 0.28 0.33 4.76 5.37 nd
V21 40.45 27.12 67.29 2513 nd nd nd nd 5.57 0.37 0.26 5.01 5.64 nd

a.r.b.: as received basis, d: dry basis; daf: dry and ash free basis V.M: volatile matter, G.C.V.: gross caloric value; C: carbon; H: hydrogen; N: nitrogen; O; oxygen; Rr: random reectance of
huminite; wt%: weight percent. nd: not determined.
 C. Erarslan, Y. rgn International Journal of Coal Geology 173 (2017) 925 13

4.2. Mineralogical and petrographical properties of the coals
4.2.1. Petrography
The percentages of huminite, inertinite and liptinite, pyrite and
other mineral matter for the Saray and Pnarhisar coals are given sepa-
rately in Table 2. Optical microscope data for the coal samples are pre-
sented in Fig. 3. The major maceral group in the Saray and Pnarhisar
coals is huminite (Table 2). The inertinite and liptinite contents of the
coals (3.5% and 2.5% on average, respectively) are lower than those of
the huminite maceral group. The huminite in the coals is mainly com-
posed of gelinite, densinite, corpohumunite and ulminite; sporinite,
cutunite, suberinite and resinite are the most abundant liptinite
macerals; the inertinite macerals are represented by fusinite, funginite,
macrinite and inertodetrinite (Table 2 and Fig. 3A, B, C, D, E, F). Pyrite
(9.6% on average) and other minerals (clays, calcite, quartz and musco-
vite; 7.8% on average) are associated with these macerals. As seen in Fig.
3, pyrite is intimately associated with the macerals and has a ne-grain
size. The maceral content of the coals is similar to that of other coals in
Turkey reported by Grdal (2008), Karayiit et al. (1999) and Toprak et
al. (2015). The maceral composition of the Saray and Pnarhisar coals
suggests that the coals were deposited in a limnic environment, like
that of other Turkish low-rank coals (Palmer et al., 2004).
4.2.2. Mineralogy
The results of XRD analysis for the coals are given in Table 3 and se-
lected SEM microphotographs of the coal samples are presented in Fig.
4. According to the XRD and SEM-EDS studies, sulfur-bearing minerals
are the main minerals in the coal samples (Table 3 and Fig. 4). Pyrite
is the most abundant sulfur-bearing mineral; the second most abundant
sulfur-bearing minerals are barite and gypsum. Also, minor amounts of
kaolinite, montmorillonite, muscovite, rozenite and butlerite and trace
amounts of quartz, tamarugite, gibbsite and chlorite were identied.
Pyrite is the most abundant sulfur mineral in many coal samples and
has various forms e.g. framboidal, disseminated pyrite, pyrite veins, cell
llings (Chou, 2012; Dai et al., 2002, 2007, 2015d; Moore and Esmaeili,
2012; Widodo et al., 2010). In the Saray and Pnarhisar coals pyrite oc-
curs in cleat lling, euhedral and framboidal forms (Figs. 3C, 4C, D).
These forms indicate that the pyrite in the coals is of both syngenetic
and epigenetic origin. Chou (2012) suggested that pyrite in cleats is de-
posited from migrating solutions, after the compaction of peat into coal.
Also Widodo et al. (2010) identied pyrite types in the Kutai Basin coals
and indicated that the pyrite in cleats and fractures is of epigenetic
origin. Framboidal pyrite and euhedral pyrite in coals are categorized
as syngenetic (Dai et al., 2007, 2008).
Barite and gypsum are another signicant source of the total sulfur
in the coals. These minerals may have been precipitated from marine
sulfates and Ba and Ca -rich uids in the coaleld (Chou, 2012; Grdal,
2008; Jiang et al., 2008; Edmunds, 1975; Turner and Richardson, 2004).
Rozenite and butlerite are the minor sulfate minerals in the studied
coal samples. The rozenite is generally styliform in shape (Fig. 4F) and is
visible to the naked eye in the samples taken from the Saray coaleld.
The butlerite is identied by XRD studies. It is also noted that that the
pyrite crystals are locally altered through the margins to rozenite
(FeSO4H2O) (Fig. 5). According to Kruszewski (2013) and Yossifova et
al. (2011) butlerite and rozenite are rare minerals in coals and they
are generally product of pyrite weathering. Chou et al. (2002), Ehlers
and Stiles (1965), and Hammarstrom et al. (2005) have also indicated
that rozenite is an oxidation product of iron suldes under humid con-
ditions. Tamarugite is a trace sulfate mineral in the coal samples; it is a
rare mineral which is known as a product of transformation of pyrite
(Bandy, 1938; Kruszewski, 2013).
Kaolinite, montmorillonite and muscovite are other minor minerals
in the coal samples. Kaolinite and montmorillonite in coal, especially ka-
olinite, are commonly identied as being of authigenic origin and are
very common in many coals (Dai et al., 2015a; Moore and Esmaeili,
2012; Ward, 1989, 2002). Quartz, gibbsite and chlorite are the trace
minerals in the coal samples. Quartz and gibbsite are generally intro-
duced as detrital input from the sediment source region (Dai et al.,
2015b; Dai et al., 2005b; Ward, 2002), although authigenic quartz and
in some cases, chlorite, are often observed in coal (Ward, 2016).
4.3. Geochemical composition of the coals
The major and trace element composition of the Saray and
Pnarhisar coals, together with world clark values (Dai et al., 2015a;
Ketris and Yudovich, 2009), are given in Tables 4 and 5. The correlation
coefcients were estimated for ash yield (Table 1) and the individual
major oxides (Table 4) and the relation between the ash yields and
the individual major oxides are given in Fig. 6. The ash yield is given
in Table 1. Also, the correlation coefcients were calculated between
each pair of elements, including the major oxides, and signicant rela-
tions are presented in following sections.
As seen in Table 4, the maximum major oxide values, except for
P2O5, are higher than the respective clark values for world low-rank

Table 2
Macerals in the Saray and Pnarhisar coals (%).

Sample Huminite Inertinite Liptinite

Gelinite Corpohuminite Densinite T.H. Fusinite Funginite Makcrinite Inertodetrinite T.I. Sporinite Cutinite Resinite T.L. Pyrite Mineral matter

Saray coals
E6 64 1 5 70 0 1 2 1 4 2 0 0 2 13 11
E7 66 3 5 74 0 1 1 0 2 2 1 0 3 11 10
E8 67 1 6 74 1 0 1 0 2 1 1 0 2 12 10
E10 67 0 6 73 1 1 1 0 3 2 1 0 3 12 9
E12 72 0 6 78 2 2 2 0 6 1 1 0 2 8 6
E21 68 1 5 74 2 0 1 0 3 2 1 0 3 11 9
E24 69 1 5 75 1 1 2 1 5 1 1 0 2 10 6

Pnarhisar coals
V4 71 0 9 80 2 1 2 0 5 2 0 0 2 7 6
V5 70 0 9 79 1 0 2 0 3 2 1 1 4 7 7
V6 71 0 8 79 1 0 1 0 2 2 0 0 2 9 8
V11 72 1 7 80 0 1 2 1 4 1 1 0 2 8 6
V16 69 1 9 79 0 1 2 0 3 1 1 0 2 9 7
V19 70 0 8 78 1 1 2 0 4 2 0 1 3 8 7
Ave. 76.4 3.5 2.5 9.6 7.8

Ave.: average; T.H.: total huminite; T.I.: total inertinite; T.L.: total liptinite.
14 C. Erarslan, Y. rgn International Journal of Coal Geology 173 (2017) 925

Fig. 3. Macerals in the Saray and Pnarhisar coals. (A), Py: pyrite, Fg: funginite, Ch: corpohuminite in sample E10; (B), Sp: sporinite in sample E6; (C), Ct: cutinite, Ul: ulminite in sample V4;
(D), Sb: suberinite, Ft: fusinite, Fl: obaphinite in sample V5, Ul: ulminite; (E), Ge: gelinite, Fg: funginite in sample E7, (F), Sp: sporinite, De: densinite in sample E6.

coals. The SiO2 percentages (whole-coal basis) vary from 1.04 to 40.12%,
Al2O3 0.87 to 19.37%, Fe2O3 0.68 to 17.88%, MgO 0.17 to 2.38%, CaO 1.23
to 5.97%, Na2O 0.01 to 0.25%, K2O 0.01 to 1.52, TiO2 0.02 to 0.53%,
P2O5 b 0.01 to 0.07%, MnO b 0.01 to 0.03%, Cr2O3 b 0.002 to 0.026%. Ac-
cording to the statistical data, there is a signicant positive correlation
coefcient (cc) between the major elements and the ash yields such
as ash-SiO2 (cc = 0.6), ash-Al2O3 (cc:0.7), ash-K2O (cc = 0.6) and
ash-TiO2(cc = 0.5) in the coals from the Pnarhisar coaleld (Fig. 6a,
b, g, h). The high percentages of SiO2, Al2O3 and K2O, along with the pos-
itive correlation coefcient between ash and these major oxides,
indicate that these elements are probably related to muscovite, quartz
and the clay minerals, in the respective coal samples. On the other
hand, the SiO2, Al2O3, K2O and TiO2 are only weakly correlated to ash
yields (cc b 0.5) in the coals from the Saray coaleld (Fig. 6a, b, g, h).
However, the SiO2, Al2O3, K2O contents of the samples are high and
these high values may also be related to quartz, muscovite and clay min-
erals determined by XRD analysis of the coal samples.
TiO2 concentrations of the coals are consistent with the clark value
for world low-rank coals (0.11% on average). The relations between
SiO2-TiO2, Al2O3-TiO2, MgO-TiO2, Na2O-TiO2, K2O-TiO2, Cr2O3-TiO2 are

Table 3
Mineral composition of Saray and Pnarhisar coals.

Sample Major minerals Minor minerals Trace minerals

Saray coaleld
Edirky Pyrite, barite, gypsum Muscovite, kaolinite, montmorillonite, butlerite, rozenite Quartz, tamarugite, chlorite, Gibbsite, corrensite (?)

Pnarhisar coaleld
Tozakl Pyrite, barite, gypsum Muscovite, kaolinite, rozenite Tamarugite, chlorite
Akren Pyrite, barite, gypsum Muscovite, kaolinite, butlerite Quartz, tamarugite
 C. Erarslan, Y. rgn International Journal of Coal Geology 173 (2017) 925 15

Fig. 4. SEM images of the minerals in the Saray and Pnarhisar coals. (A), barite in sample E10; (B), clay in sample E10; (C), alteration of sulfur from pyrite to iron sulfate in sample E7; (D),
pyrite crystals in sample V19; (E), gypsum in the sample E8; (F) styliform rozenite crystals in sample V19.

presented in Fig. 7. The statistical data show positive correlation coef-
cients between TiO2-SiO2, TiO2-Al2O3 and TiO2-K2O (Fig. 7a, b, e) in both
the Saray and Pnarhisar samples, indicating that the TiO2 content of the
coals may also be also related to the clay minerals (Fig. 8). Also TiO2-
MgO (cc 0.5) and TiO2-Cr2O3 (cc 0.7) have signicant correlations
in the coals from both of the coalelds (Fig. 7c, f). As stated by Palmer
et al. (2004), the ultrabasic remnant rocks of the Tethys ocean may
have been a source of TiO2, MgO and Cr2O3 for Turkish coals. Although
the mean Fe2O3 values of the coals are lower than the clark value for
world low-rank coals, the coals in the Saray region are enriched in
Fe2O3 (up to 17.88%). As mentioned in Sections 4.1 and 4.2, the pyrite
and pyritic sulfur contents of the coal from the Saray region are higher
than those from the Pnarhisar region. In the coals from both of the coal-
elds, it was found that there is a strong correlation coefcient between
pyritic sulfur and Fe2O3 (rps-Fe2O3 = 0.94, for the Saray coals; rps-Fe2O3 =
0.78, for the Pnarhisar coals, Table 6). Thus, relatively high content of
Fe2O3 in the coals can be related to high pyrite in the coals. Similar re-
sults were found for coals from Southwest China (Dai et al., 2006).
Compared with average values for low-rank coals reported by Ketris
and Yudovich (2009), the Northwest Thrace Basin coals are enriched in
16 C. Erarslan, Y. rgn International Journal of Coal Geology 173 (2017) 925

Fig. 5. SEM images and selected EDS data of pyrite and iron sulfate; alteration of sulfur from pyrite to iron sulfate.

Be, Sc, V, Co, Ni, Cu, Zn, As, Se, Rb, Sr, Mo, Sn, Cs, Ba, W, Pb, Th and U; on also calculated in relation to the averages for the continental crust
the other hand, the mean values for the REEs are lower than those of (Krauskopf, 1985) and results are presented in Fig. 9. As seen in Fig.
world low-rank coals (Table 5). The element enrichment factors were 9A and B, elements Hf, Lu, Nb, Zr, Rb and Ti are depleted relative to

Table 4
Major-element oxides in the Saray and Pnarhisar coals (dry basis, %).

Sample SiO2 TiO2 Al2O3 Fe2O3 MnO MgO CaO Na2O K2O P2O5 Cr2O3 LOI Sum

Saray coals
E-6 29.62 0.4 10.52 4.88 0.02 2.38 1.41 0.25 1.52 0.03 0.022 48.8 99.86
E-7 16.45 0.24 5.85 11.33 0.01 1.59 1.23 0.16 0.82 0.01 0.014 62.2 99.9
E-8 8.96 0.15 3.81 10.8 0.01 1.32 2.17 0.15 0.43 0.02 0.009 72.1 99.89
E-9 5.3 0.08 2.19 5.79 b0.01 1.2 2.01 0.12 0.24 0.01 0.005 83 99.91
E-10 6.57 0.11 2.62 8.26 b0.01 1.22 1.65 0.1 0.35 0.02 0.009 79 99.92
E-12 3.61 0.09 2.08 3.18 b0.01 1 2.15 0.15 0.05 0.02 0.005 87.6 99.92
E-16 1.1 0.03 0.87 2.35 b0.01 1 1.99 0.12 0.04 b0.01 0.005 90.4 97.94
E-19 8.01 0.13 2.96 3.66 b0.01 1.32 1.96 0.13 0.33 0.02 0.01 81.4 99.9
E-20 6.64 0.18 3.23 6.73 0.01 1.02 1.78 0.14 0.27 0.03 0.01 79.8 99.89
E-21 7.46 0.12 3.01 17.88 b0.01 1.04 1.34 0.1 0.32 0.01 0.012 68.6 99.91
E-22 4.41 0.07 1.66 3.42 b0.01 1.27 2.7 0.06 0.2 0.03 0.007 84.4 98.27
E-23 4.73 0.09 2.09 2.65 0.01 1.25 2.17 0.13 0.13 0.03 0.012 85.4 98.69
E-24 8.29 0.13 3.26 3.47 b0.01 1.34 2.01 0.13 0.35 0.01 0.011 79.6 98.64
E-25 12.38 0.21 4.52 10.95 0.03 1.35 1.24 0.08 0.36 0.03 0.026 68.7 99.89

Pnarhisar coals
V-4 7.94 0.11 3.15 2.91 b0.01 0.91 2.63 0.07 0.23 0.01 0.006 81.9 99.92
V-5 5.09 0.06 2.35 1.64 b0.01 0.21 4.03 0.08 0.19 b0.01 0.002 82.2 95.85
V-6 2.07 0.04 1.06 2.52 b0.01 0.78 2.97 0.06 0.08 b0.01 0.003 87.4 97.03
V-8 7.04 0.1 4 2.27 b0.01 0.25 4.19 0.05 0.33 b0.01 0.004 78.4 96.68
V-9 3.39 0.05 1.53 2.08 b0.01 0.17 4.86 0.04 0.11 b0.01 b0.002 82.6 94.81
V-11 2.09 0.04 1.1 2.26 b0.01 0.76 2.98 0.07 0.08 0.01 0.004 88.2 97.6
V-12 4.62 0.07 2.6 1.88 b0.01 0.78 2.66 0.05 0.1 0.01 0.003 84.9 97.69
V-13 7.21 0.1 2.8 1.86 b0.01 1.07 2.55 0.07 0.25 0.02 0.006 84 99.93
V-14 7.2 0.11 2.69 2.51 b0.01 1.07 2.33 0.09 0.34 0.02 0.011 83.5 99.91
V-15 40.12 0.53 19.37 5.29 0.01 1.83 2.54 0.11 0.95 0.03 0.021 29 99.81
V-16 5.4 0.05 1.21 0.68 b0.01 0.22 4.8 0.01 0.04 0.01 0.002 83.1 95.53
V-17 3.23 0.05 1 0.81 b0.01 0.17 3.54 0.02 0.03 0.07 b0.002 87.5 96.43
V-18 21.58 0.06 2.43 0.78 b0.01 0.53 2.52 0.06 0.14 0.07 b0.002 71.6 99.71
V-19 19.57 0.08 2.18 3.09 0.01 0.77 3.55 0.06 0.14 0.02 0.004 68.1 97.59
V-20 1.04 0.02 1.01 0.84 b0.01 0.19 5.97 0.01 0.01 b0.01 b0.002 84 93.05
V-21 6.72 0.1 3.9 1.4 b0.01 0.29 4.51 0.04 0.34 b0.01 b0.002 79.6 96.84
Min 1.04 0.02 0.87 0.68 b0.01 0.17 1.23 0.01 0.01 b0.01 b0.002 29 93.05
Max 40.12 0.53 19.37 17.88 0.03 2.38 5.97 0.25 1.52 0.07 0.026 90.4 99.93
Ave* 8.10 0.11 2.89 3.91 0.02 0.92 2.69 0.09 0.26 0.02 0.01
World** 8.47 0.33 5.98 4.85 0.015 0.22 1.23 0.16 0.19 0.092

Min: minimum; Max: maximum; Ave*: average. The average values were calculated by excluding the minimum and maximum values.
World**: world coal data from Dai et al. (2015a).
 C. Erarslan, Y. rgn International Journal of Coal Geology 173 (2017) 925 17

Table 5
Concentrations of trace elements in the Saray and Pnarhisar coals and their comparisons with world average values for low-rank coals (values in ppm, unless indicated as ppb).

Saray Be Sc V Co Ni Cu Zn Ga As Se Rb Sr Y Zr Nb Mo Ag Cd Sn Sb Cs Ba

E-6 b1 11 98 12.3 109.3 65.5 71 11.7 15.5 0.9 76.9 161.6 10 46.6 4.8 1.7 b0.1 0.1 1 0.3 7.4 257
E-7 2 6 67 8.1 100.5 33.1 41 7.2 121.8 1.4 49.4 169.7 6.9 28 2.7 3.7 b0.1 b0.1 1 0.5 4.6 144
E-8 2 6 69 6.2 101.2 34.5 119 4.2 137.6 1.8 23.1 239.9 9 30.8 1.7 6.7 b0.1 0.1 b1 0.7 2.4 123
E-9 b1 3 40 4.1 57.2 22 17 1.8 54.8 1 13.5 219.9 6.7 14 0.9 4.3 b0.1 b0.1 b1 0.4 1.1 98
E-10 b1 4 67 7.5 93.8 39 35 3.3 86.4 1 19.1 207 7.3 19.2 2.2 5.7 b0.1 b0.1 b1 0.7 1.9 63
E-12 4 3 40 6.5 79.9 24.6 53 1.7 30.1 1 2 220.8 10.4 30.5 0.9 5.1 b0.1 b0.1 b1 0.6 0.2 94
E-16 2 2 22 3.4 52.2 9 8 b0.5 24.8 0.6 2.5 240.6 6.9 9.9 0.3 4.8 b0.1 b0.1 b1 0.4 0.2 64
E-19 b1 6 85 11.4 133.3 26.1 30 3.2 45 1.6 28.1 264.1 8.9 23.6 2.1 8.2 b0.1 b0.1 b1 1.2 2.3 81
E-20 1 7 139 11.9 891.8 30.8 31 3.8 72.5 1.7 13.7 231.2 15.6 60.4 3.2 17.8 b0.1 0.1 b1 1.6 1.3 94
E-21 b1 7 112 10.7 173.9 29.7 26 3.3 166.9 2 18.5 191.3 11.8 36.3 2.3 8.8 b0.1 b0.1 b1 1 2 75
E-22 2 5 37 3.5 71.5 9.9 17 2 37.2 0.8 13.5 224.9 7.4 18.5 1.2 23.2 b0.1 b0.1 b1 0.3 1.1 78
E-23 b1 5 35 7.7 146.1 16.1 48 2.1 23.8 0.8 8.3 275.9 10.8 30.5 1.7 4.3 b0.1 b0.1 b1 0.7 0.9 101
E-24 b1 6 62 6.9 95.2 25.2 40 1.5 24.6 0.7 25.9 247 7.7 24.7 1.8 3 b0.1 b0.1 b1 0.5 2.5 103
E-25 b1 6 75 17.8 348.1 31.8 60 3.3 131.1 1.2 22.1 150 7.8 71.1 4.6 7.5 b0.1 0.1 b1 0.7 3.5 100

Pnarhisar
V-4 1 4 43 5.3 55.1 24.3 16 2.4 21.1 1.1 22.8 152.9 8.7 16.1 1.3 5.6 b0.1 b0.1 b1 0.5 2.8 198
V-5 b1 1 11 2.4 11.1 17.9 23 b0.5 28.1 1.2 8.8 69.3 3.4 13.6 0.3 6.3 b0.1 b0.1 b1 0.1 0.3 146
V-6 2 2 21 1.5 45.8 9.7 10 b0.5 23.7 1.2 7.2 143.4 6.5 10.9 b0.1 5.8 b0.1 b0.1 b1 0.5 1.7 36
V-8 b1 2 20 3.1 5.4 7.2 35 2.4 18.7 2.4 17.9 80 4.7 16.1 1.4 10.6 b0.1 b0.1 b1 0.1 0.6 293
V-9 b1 1 b8 5.5 7.7 4.6 47 b0.5 40 3.3 4.6 87.5 3.6 11.2 b0.1 9.6 b0.1 b0.1 b1 b0.1 b0.1 370
V-11 1 2 27 3.5 69.9 15.1 11 b0.5 28.9 1.4 6.1 141 11.6 10.4 b0.1 8.9 b0.1 b0.1 b1 0.7 1.1 20
V-12 3 2 32 3.7 36.6 17 34 b0.5 19.9 1.1 9.2 131 6.9 18.2 0.8 5.4 b0.1 b0.1 1 0.5 1.1 24
V-13 b1 3 46 4.4 38.9 20.5 20 2.3 14.3 0.8 22.4 159.6 4.8 15.1 1.6 4.4 b0.1 b0.1 b1 0.5 2.3 69
V-14 1 6 108 11.5 82.4 28.1 41 3.2 24.2 0.9 18.4 146 11.8 54.2 4 5.9 b0.1 0.1 b1 1 2.4 79
V-15 7 28 97 9.5 214.4 177.8 38 20.4 b0.5 20.8 76.3 179.1 91.2 122 10 0.6 0.2 0.3 4 0.2 11.5 264
V-16 b1 2 29 0.9 3.7 4.5 11 b0.5 7.2 2.4 0.8 133.7 5 20.4 0.8 3.1 b0.1 b0.1 b1 b0.1 b0.1 740
V-17 b1 1 28 1 3.3 4.7 13 b0.5 16.2 2.6 0.3 113.7 5.2 13.1 0.6 1.3 b0.1 b0.1 b1 b0.1 b0.1 1034
V-18 1 1 16 2.2 6.1 9.2 14 0.6 10.8 2.6 3 540.9 3 17.1 0.6 1.8 b0.1 b0.1 b1 b0.1 b0.1 1787
V-19 4 5 56 4.3 69.6 21 45 b0.5 27.8 0.9 10.6 124.5 12.6 17.4 0.7 6.3 b0.1 b0.1 b1 0.8 1.8 58
V-20 b1 b1 15 1.2 4.7 7.3 36 b0.5 3.8 2.9 0.3 81.3 5.4 6.8 b0.1 0.8 b0.1 b0.1 b1 b0.1 b0.1 192
V-21 b1 2 39 4.6 6.7 14.9 74 2.4 6.8 5.7 18.9 82.1 4.6 15.8 1.3 1.4 b0.1 0.3 b1 b0.1 0.5 333
Min b1 b1 b8 0.9 3.3 4.5 8 b0.5 b0.5 0.6 0.3 69.3 3 6.8 b0.1 0.6 b0.1 b0.1 b1 b0.1 b0.1 20
Max 7 28 139 17.8 891.8 177.8 119 20.4 166.9 20.8 76.9 540.9 91.2 122 10 23.2 0.2 0.3 4 1.6 11.5 1787
Mode 2 2 67 3.5 41 3.3 0.9 13.5 6.9 30.5 1.7 4.3 0.1 1 0.5 1.1 94
Ave* 2.63 3.96 61.00 5.85 79.30 21.39 33.46 3.28 39.17 1.66 16.68 171.42 7.93 24.78 1.75 5.67 0.10 1.00 0.56 1.92 189.68
Clark 1.2 4.1 22 4.2 9 15 0.24 5.5 7.6 1 10 120 8.6 35 3.3 2.2 0.09 0.24 0.79 0.84 0.98 150

Saray La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu Hf Ta W Au (ppb) Hg Tl Pb Bi Th U

E-6 18.3 37.3 4.12 15.1 2.84 0.59 2.63 0.35 1.85 0.39 1.07 0.15 1 0.16 1.4 0.3 2 3.9 0.05 0.3 12.7 0.5 7.4 4.4
E-7 10.5 21 2.47 9.3 1.79 0.37 1.59 0.22 1.12 0.23 0.72 0.1 0.74 0.11 0.9 0.2 1.3 2.3 0.07 0.2 8.7 0.2 4.4 4.2
E-8 7.9 14.5 1.75 7.3 1.45 0.31 1.6 0.22 1.43 0.3 0.84 0.14 0.88 0.14 0.8 0.2 8.4 2.2 0.11 0.2 7.2 0.2 4.4 7.7
E-9 5.1 8.4 1.01 4.3 0.91 0.23 0.94 0.17 0.92 0.26 0.59 0.1 0.61 0.1 0.4 b0.1 1.9 0.9 0.04 0.1 4 0.2 2 3.6
E-10 4.9 11.6 1.38 5.2 1.09 0.27 1.22 0.19 1.11 0.26 0.72 0.11 0.67 0.11 0.5 0.1 3.4 1 0.07 0.2 6.2 0.1 2.5 4.3
E-12 5.8 11.4 1.26 5.6 1.05 0.32 1.32 0.21 1.37 0.33 1.04 0.16 0.99 0.17 0.6 b0.1 4.1 0.7 0.08 0.3 5.7 0.1 3.5 3.2
E-16 2.6 4.4 0.54 3 0.6 0.17 0.96 0.16 1.03 0.23 0.76 0.1 0.6 0.1 0.2 b0.1 1.3 b0.5 0.03 0.1 2.6 0.1 1 3.2
E-19 6.5 12.6 1.53 5.9 1.13 0.3 1.35 0.23 1.48 0.31 0.93 0.14 0.97 0.15 0.6 0.2 1.2 2.1 0.07 0.2 5.7 0.1 3.1 9
E-20 10.8 23.3 2.7 10.7 2.39 0.55 2.47 0.41 2.66 0.56 1.92 0.27 1.87 0.3 1.7 0.2 2.3 1.9 0.1 0.4 10.5 0.2 6.1 12.8
E-21 6.9 12.3 1.51 6.2 1.22 0.31 1.61 0.27 2 0.44 1.42 0.21 1.53 0.25 1 0.1 1.1 2.1 0.05 0.2 6.7 0.1 3.2 8.4
E-22 5.3 9.9 1.3 4.8 0.95 0.23 1.06 0.51 1.33 0.26 0.74 0.13 0.81 0.13 0.3 0.1 2.3 b0.5 0.08 0.4 3.7 0.1 1.4 2.5
E-23 5.5 12.1 1.25 5.4 1.04 0.35 1.37 0.24 1.63 0.39 1.16 0.18 1.19 0.19 0.6 0.2 2.5 b0.5 0.07 0.2 5.3 0.1 3.2 3.6
E-24 7.5 14.4 1.67 6.3 1.18 0.32 1.41 0.2 1.22 0.27 0.94 0.14 0.74 0.12 0.6 b0.1 1.4 0.9 0.06 0.1 6.9 0.2 3.3 5.1
E-25 11.6 25.8 2.79 10 1.69 0.47 1.67 0.27 1.6 0.29 0.98 0.15 0.92 0.12 1.3 0.2 1.4 b0.5 0.14 0.2 11.8 0.2 7.6 7

Pnarhisar
V-4 6.2 11.7 1.35 5.5 1 0.24 1.12 0.2 1.26 0.27 0.91 0.12 0.77 0.11 0.5 0.1 3.7 1.1 0.08 0.2 6.1 0.2 3.5 5.9
V-5 3.7 7.5 0.77 3.1 0.63 0.13 0.55 0.07 0.34 0.07 0.24 0.04 0.21 0.03 0.3 b0.1 12.2 b0.5 0.07 0.5 4.8 b0.1 1.4 5
V-6 4.6 7.6 0.89 3.8 0.56 0.14 0.85 0.12 0.74 0.17 0.53 0.06 0.37 0.05 0.2 b0.1 1.7 b0.5 0.05 0.2 2.1 b0.1 1.4 7.2
V-8 7.3 12.8 1.39 5.1 0.93 0.24 0.96 0.13 0.76 0.15 0.41 0.05 0.37 0.05 0.3 0.1 1.4 b0.5 0.07 0.3 6.6 b0.1 3.7 25.8
V-9 7.6 13.9 1.36 4.6 0.77 0.19 0.74 0.1 0.57 0.1 0.25 0.04 0.25 0.06 0.3 b0.1 0.7 b0.5 0.11 1 4.7 b0.1 2.9 28.9
V-11 4.9 8.9 0.95 4.6 0.74 0.27 1.16 0.18 1.07 0.28 0.86 0.12 0.72 0.11 0.3 b0.1 1.4 0.8 0.08 0.4 2.8 0.1 1.6 22.3
V-12 5.9 10.6 1.12 4.9 0.83 0.2 0.94 0.14 0.8 0.18 0.58 0.08 0.58 0.08 0.4 0.2 1.2 0.7 0.06 0.4 6.9 0.2 3.3 7.8
V-13 4.7 9.4 1.09 4.5 0.94 0.19 0.88 0.15 0.87 0.2 0.57 0.08 0.51 0.09 0.5 0.1 2.1 0.7 0.03 0.1 5.4 0.2 2.9 6
V-14 6.8 14.4 1.68 6.7 1.55 0.4 1.75 0.29 1.75 0.4 1.15 0.18 1.16 0.2 1.1 0.2 2.1 1.3 0.08 0.5 6.5 0.1 2.7 4.9
V-15 35.3 64.7 8.26 34.8 10 2.67 12.76 2.34 15.62 3.32 9.96 1.48 9.89 1.59 3.1 1 2.6 13.1 0.28 0.3 76.6 1.3 32.9 11.9
V-16 7.1 14.5 1.61 5.9 1.33 0.24 1.15 0.17 0.82 0.19 0.53 0.07 0.44 0.08 0.4 0.1 0.7 b0.5 0.04 b0.1 6.2 0.3 4.2 2.2
V-17 5.7 13.3 1.53 6.8 1.09 0.27 1.09 0.15 0.94 0.16 0.48 0.06 0.51 0.07 0.2 b0.1 b0.5 0.7 0.04 b0.1 7 b0.1 4.1 1.3
V-18 15.3 23.7 2.06 5.8 0.85 0.13 0.78 0.1 0.52 0.1 0.29 0.05 0.29 0.05 0.6 b0.1 b0.5 b0.5 0.09 0.1 11.5 0.3 2.5 0.7
V-19 6 11 1.32 5.1 1.19 0.32 1.59 0.27 1.95 0.39 1.19 0.17 1.23 0.17 0.5 b0.1 1 1.8 0.07 0.2 5.3 0.1 3.3 6.3
V-20 8.3 17 1.85 7.3 1.33 0.3 1.19 0.16 0.81 0.16 0.45 0.07 0.39 0.05 b0.1 b0.1 b0.5 b0.5 0.07 0.3 6 b0.1 3.5 0.4
V-21 7.9 17.8 2.03 7.7 1.44 0.34 1.32 0.21 0.98 0.22 0.52 0.08 0.61 0.1 0.4 b0.1 0.8 0.7 0.1 2.9 12.3 0.2 8 1.3
Min 2.6 4.4 0.54 3 0.56 0.13 0.55 0.07 0.34 0.07 0.24 0.04 0.21 0.03 b0.1 b0.1 b0.5 b0.5 0.03 b0.1 2.1 b0.1 1 0.4
Max 35.3 64.7 8.26 34.8 10 2.67 12.76 2.34 15.62 3.32 9.96 1.48 9.89 1.59 3.1 1 12.2 13.1 0.28 2.9 76.6 1.3 32.9 28.9
Mode 7.9 14.5 1.53 7.3 1.09 0.27 1.59 0.27 0.39 0.72 0.1 0.74 0.11 0.6 0.2 1.4 0.7 0.07 0.2 6.2 0.2 3.5 3.6
Ave* 7.45 14.60 1.63 6.34 1.22 0.30 1.31 0.22 1.24 0.27 0.81 0.12 0.78 0.12 0.60 0.16 2.08 1.43 0.07 0.28 6.78 0.18 3.61 6.7
Clark 10 22 3.5 11 1.9 0.5 2.6 0.32 2 0.5 0.85 0.31 1 0.19 1.2 0.26 1.2 3 0.1 0.68 6.6 0.84 3.3 2.9
18 C. Erarslan, Y. rgn International Journal of Coal Geology 173 (2017) 925

Fig. 6. Relation between major element oxides and ash yields for Saray and Pnarhisar coals: a: SiO2 vs ash yield; b: Al2O3 vs ash yield; c: Fe2O3 vs ash yield; d: MgO vs ash yield; e: CaO vs
ash yield; f: Na2O vs ash yield; g: K2O vs ash yield; h: TiO2 vs ash yield; and i: Cr2O3 vs ash yield; cc: correlation coefcient.

the crust, whereas the other elements are enriched. The coals of the
Saray coaleld are much more enriched in As, Ni, Co, Fe, Cr and V than
those of the Pnarhisar coaleld.
The statistical data show that Ni, V and Co have strong correlations
(ccV-Co = 0.7, ccNi-V = 0.7, ccNi-Co = 0.5, for Saray coals; ccV-Co = 0.8,
ccNi-V = 0.7, ccNi-Co = 0.6, for Pnarhisar coals; Fig. 10a, b, c) with each
other, and that they are also enriched in the coals from both of the coal-
elds (Ni, up to 891 ppm; V, up to 139 ppm; Co, up to 17.8 ppm;
Table 5). As mentioned above, the ultrabasic remnant rocks of the Tethys
ocean may have been a source of Ni, V and Co as well as TiO2, MgO and
Cr2O3. It is known that ultrabasic-basic rocks such as peridotites,
serpentinite, and olivine-basalt are enriched in siderophile elements
(e.g., Ti, V, Mn, Fe, Co and Ni) and they are also considered as the main
source of the high Cr and Ni values in coals in other areas (Browneld
et al., 1995; Dai et al., 2005a; Palmer et al., 2004; Ren et al., 2004;
Ruppert et al., 1996).

Notes to Table 5
Min: minimum; Max: maximum; Ave*: average. The average values were calculated by excluding the minimum and maximum values.
Clark*: World average values for trace element in low-rank coals from Ketris and Yudovich (2009).
 C. Erarslan, Y. rgn International Journal of Coal Geology 173 (2017) 925 19

Fig. 7. Relation between major element oxides and ash yields for Saray and Pnarhisar coals: a: SiO2 vs TiO2; b: Al2O3 vs TiO2; c: MgO vs TiO2; d: Na2O vs TiO2; e: K2O vs TiO2; f: Cr2O3 vs TiO2,
cc: correlation coefcient.

The Zr concentrations of the coals are between 6.8 and 122 ppm. The
average Zr concentration of the coals are lower than the world clark
value (Table 5). Also, positive correlation between Zr-Nb, Zr-Hf, and
Zr-Th is obtained (Fig. 10d, e, f) for the coals from both coalelds. How-
ever, the mineral zircon could not be identied in the coal samples, ei-
ther by optical microscopy or by XRD studies.
The correlations between Rb-SiO2 and Cs-SiO2, Rb-Al2O3 and Cs-
Al2O3, and Rb-K2O and Cs-K2O are strong (cc 0.9) in the coals from
the Saray coaleld (Fig. 11); also Rb-Al2O3 and Rb-K2O correlations
are strong in the Pnarhisar coals. These results suggest that Rb and Cs
may be related to the clay minerals in the Saray coals. Dai et al.
(2015a) obtained similar correlations for these elements (rRbK =
0.95, rCsK = 0.97, rRb-Al = 0.50, rRb-Si = 0.63; r Cs-Al = 0.65, rCs-Si =
0.75) and suggested that the Rb and Cs may be related to clay minerals.
According to Swaine and Goodarzi (1995), elements As, Se, Cd and
Hg are classied as environmentally signicant elements. Arsenic is

EDS Spot 1

Fig. 8. SEM images and selected data of clay; Ti-bearing clay.

20 C. Erarslan, Y. rgn International Journal of Coal Geology 173 (2017) 925

Table 6
Pearson correlation coefcients (r) between trace elements, ash and forms of sulfur for the Saray and Pnarhisar coal samples.

Saray coals Pnarhisar coals

Elements Ash yields Total sulfur Pyritic S Sulfate S Organic S Ash yields Total sulfur Pyritic S Sulfate S Organic S

Ti 0.26 0.04 0.24 0.00 0.08 0.5 0.42 0.19 0.35 0.43
V 0.34 0.65 0.72 0.51 0.59 0.01 0.51 0.22 0.42 0.51
Cr 0.15 0.23 0.49 0.09 0.18 0.02 0.57 0.19 0.22 0.60
Fe 0.5 0.98 0.94 0.84 0.86 0.13 0.15 0.78 0.36 0.41
Co 0.01 0.38 0.62 0.08 0.38 0.21 0.22 0.17 0.06 0.27
Ni 0.02 0.44 0.64 0.05 0.46 0.13 0.51 0.63 0.01 0.66
Cu 0.00 0.07 0.20 0.17 0.10 0.21 0.42 0.49 0.31 0.51
Zn 0.06 0.05 0.05 0.14 0.25 0.17 0.52 0.14 0.16 0.52
As 0.5 0.94 0.91 0.77 0.77 0.19 0.13 0.58 0.71 0.13
Se 0.5 0.85 0.77 0.79 0.73 0.31 0.61 0.52 0.08 0.75
Rb 0.37 0.04 0.17 0.04 0.10 0.33 0.29 0.29 0.23 0.34
Sr 0.41 0.44 0.61 0.44 0.36 0.66 0.59 0.31 0.10 0.49
Mo 0.47 0.04 0.02 0.09 0.11 0.13 0.12 0.56 0.66 0.13
Sb 0.17 0.67 0.62 0.46 0.70 0.16 0.55 0.59 0.09 0.67
Ba 0.19 0.24 0.10 0.16 0.33 0.5 0.27 0.62 0.11 0.11
W 0.15 0.15 0.21 0.04 0.36 0.06 0.16 0.34 0.06 0.05
Au 0.40 0.22 0.25 0.31 0.07 0.10 0.36 0.62 0.23 0.48
Hg 0.02 0.12 0.31 0.19 0.02 0.51 0.44 0.05 0.28 0.39
Pb 0.13 0.19 0.43 0.00 0.09 0.75 0.06 0.52 0.54 0.15
Th 0.06 0.11 0.37 0.07 0.03 0.25 0.31 0.33 0.44 0.46
U 0.24 0.76 0.77 0.50 0.66 0.12 0.37 0.17 0.76 0.20

relatively abundant in the coals from both coalelds and reaches up to
166.9 ppm in the Saray coals. It is known that Turkish coals generally
have high As contents (Palmer et al., 2004), with a maximum observed
value of 3854 ppm (Karayiit et al., 2000). In general, As is associated
with pyrite and other sulde minerals (e.g. Coleman and Bragg, 1990;
Dai et al., 2005a, 2006; Goodarzi, 2002; Hower et al., 2008; Huggins
and Huffman, 1996; Ruppert et al., 2005; Yudovich and Ketris, 2005;
Zhang et al., 2002). At the same time arsenic in coal may have an organic
association (Finkelman, 1994; Zhang et al., 2002). The Se concentrations
of the coals are between 0.6 and 20.8 ppm, with an average of 1.66 ppm,
around the world average (1 ppm, Ketris and Yudovich, 2009) and
within the range for Turkish coals (Palmer et al., 2004). Selenium in
coals mainly occurs in sulde minerals (Hower et al., 2008; Swaine,
1990); however, Se can also have an organic afnity (Finkelman,
1994; Yang, 2006). In most of the samples from both coalelds the Cd
concentrations are below the detection limit (b 0.1 ppm). The Hg con-
centrations in the coals vary from 0.03 to 0.28 ppm. The average concen-
trations are lower than the world low-rank coal clark value (0.1 ppm,
Ketris and Yudovich, 2009).
Uranium and Th are the other environmentally important elements.
The average Th concentrations in the coals is around the world average
(3.6 ppm Th on average). Thorium is generally related to clay minerals

Fig. 9. Enrichment factors of the coals according to continental crust A: Saray coalelds; B: Pnarhisar coalelds.
 C. Erarslan, Y. rgn International Journal of Coal Geology 173 (2017) 925
Fig. 10. Relation between V-Co-Ni and Xr-Nb, Zr-Hf and Zr-Th for Saray and Pnarhisar coals: a: Co vs V; b: Ni vs V; c: Ni vs Co; d: Zr vs Nb; e: Zr vs Hf; f: Zr vs Th, cc: correlation coefcient.
(Finkelman, 1994; Van Der Flier and Fyfe, 1985) and shows an inorganic
afnity (Dai et al., 2005b, 2012a; Kortenski and Satirov, 2002; Querol et
al., 2001; Zhang et al., 2004; Zhou et al., 2010). The U concentration in
the coals varies from 0.4 to 28.9 ppm and the concentration of U is with-
in the range for Turkish coals (0.32140 ppm; Palmer et al., 2004). How-
ever, the average U concentrations exceed the world average (Ketris
and Yudovich, 2009) (Table 5). Previous studies suggest that U enrich-
ment in coal is of syngenetic and epigenetic origin (Dai et al., 2015c;
Seredin and Finkelman, 2008).
The average REEs contents in the coal samples are lower than the
world average for brown low-rank coals (Table 5, Fig. 12). The REE dis-
tribution patterns are similar, and samples from both coalelds present
a at shape without distinct fractionations between light, intermediate
and heavy REEs like that (Fig. 12). The zigzag REE distribution patterns
for world low-ranks coals (Fig. 12), as pointed out by Dai et al. (2016), is
most likely due to analytical problems for the samples collected world-
wide (e.g. incomplete dissolution). The enrichment factor shows that
the REEs in the coals are enriched in relation to the continental crust
(Fig. 9A, B). The enrichment of REEs in the Pnarhisar coals is higher
than that in the Saray coals. The REE contents of coals are related to a
number of factors such as seawater, natural water, volcanic ash and sed-
imentary environments (Dai et al., 2016).
4.4. Pearson correlation coefcients
Pearson correlation coefcients (r) were calculated for the trace ele-
ment concentrations with respect to ash yield, total sulfur, pyritic sulfur,
sulfate sulfur and organic sulfur, and some of the results are listed in
21
Table 6. The relations between trace element concentration and ash
may provide information about the modes of occurrence of particular
elements. If rash b 0.50, the element may have an organic afnity,
whereas if rash N 0.50, the element probably has an inorganic afnity
(Dai et al., 2005a; Erarslan et al., 2014; Grdal, 2008; Kortenski and
Satirov, 2002; Zhang et al., 2004). Pearson correlation coefcients for el-
ement concentrations and total sulfur can also be used to indicate the
sulfur afnities (Grdal, 2011). As indicated in Table 6, Fe, arsenic and
Se have strong positive correlation coefcients (rash + 0.5) with the
ash yield and it can be inferred that Fe, As and Se have inorganic afni-
ties in the Saray coals. Although the remaining elements (e.g., Ti, V, Cr,
Co, Ni, Cu, Au, Rb) have positive correlations, they do not display a
strong correlation with ash yield; therefore, these elements may have
a mixture of organic and inorganic afnities in the Saray coals.
On the other hand, Ti, Sr, Ba, Hg and Pb have strong positive correla-
tions with the ash yield (rash 0.5), and these elements probably have
inorganic afnities in the Pnarhisar coals. The remaining elements do
not display any signicant correlation with ash yield, so they may
have both organic and inorganic afnities (as in the case of the Saray
coals).
The Pearson correlation coefcients between the pyritic sulfur and
Fe, Ni, As and Sb are also strong (rps N 5) (Table 6 and Fig. 13a, b, c, d)
in the coals from both coalelds. It can be said that these elements
may have pyritic sulfur afnities. Table 6 also shows that V, Fe, As, Se
and U have strong positive correlations with all of the sulfur forms in
the Saray coals, although Cr, Co and Ni have afnities only with pyritic
sulfur concentrations. As for the Pnarhisar coals, Sr and Ba have nega-
tive correlations with all of the sulfur forms; As and Mo display positive
22 C. Erarslan, Y. rgn International Journal of Coal Geology 173 (2017) 925
Fig. 11. Relation between Rb-SiO2, Rb-Al2O3 and Rb-K2O and Cs-SiO2, Cs-Al2O3 and Cs-K2O for Saray and Pnarhisar coals with correlation coefcient: a: Rb-SiO2; b: Cs-SiO2; C: Rb-Al2O3; c:
Rb-Al2O3; d: Cs-Al2O3; e: Rb-K2O; f: Cs-K2O, cc: correlation coefcient.
correlations with pyritic and sulfate sulfur; U has a positive correlation
with sulfate sulfur. The other trace elements, including Ti, V, Cr, Fe, Co,
Ni, Cu, Rb, Sr and Au, exhibit negative correlations with organic sulfur.
All of these results show that these elements may have inorganic afn-
ities in the Pnarhisar coals.
Fig. 12. Distribution patterns of average values of REEs in Saray and Pnarhisar coals and
world low-rank coals (Ketris and Yudovich, 2009), normalized to average REEs
concentrations in the Continental Crust (Krauskopf, 1985).
5. Discussion
The Saray and Pnarhisar coals are characterized by high percentages
of pyrite (up to 9.6%). The sulfur contents of both coaleld coals are
high, with the highest sulfur value occurring in the Edirky coals (up
to 15.3%). According to Chou (2012), Dai et al. (2002) and Diessel
(1992), in low sulfur coals (b 1% S) sulfur is derived from the plant ma-
terials. In medium (1 to b 3% S) and high (3% S) sulfur coals, the sulfur
may have two main sources: one is the parent plant material, the other
is sulfate in seawater that ooded the peat swamps (Chou, 2012). As
mentioned by Chou (2012), coals with lower sulfur contents are related
to uvial environments and coals with higher sulfur content are related
to seawater-inuenced environments. If there is no evidence of marine
inuence, the sulfur enrichment in the coals may be a result of the peat
environment and regional volcanism. Dai et al. (2015b and 2012b) also
suggest that high-pyrite in coals may be derived from epithermal solu-
tions, which were derived from volcanic activity in a continental envi-
ronment. As seen in Fig. 1A. volcanism was active during the Eocene
to middle Miocene, particularly in the south and southwestern parts
of the Thrace Basin. Several researchers have shown that volcanism in
the Thrace Region affected deposition during the Eocene to Pliocene pe-
riod (Ercan, 1992; Fytikas et al., 1984; Kaymak et al., 2007; Ylmaz and
 C. Erarslan, Y. rgn International Journal of Coal Geology 173 (2017) 925
Fig. 13. Relation between Pyritic S and Fe, Ni, As and Sb for Saray and Pnarhisar coals with Pearson correlation coefcient: a: Fe-Pyritic S; b: Ni-Pyritic S; c: As-Pyritic S; d: Sb-Pyritic S, pcc:
Pearson correlation coefcient.
Polat, 1998); the Danimen formation, which contains the coal seams,
was also deposited in this period (Perinek et al., 2015).
According to Palmer et al. (2004), coal seams in the northwest of
Turkey are mostly intercalated with marine sediments. Bat (1996) fur-
ther suggests that the presence of marine palynomorphs (dinoagel-
lates) indicates a restricted number of paralic coal forming basins in
the northwestern part of the Thrace Basin, and hence that the coal
seams were most probably deposited in brackish waters of transitional
lower delta plains under the effect of marine inuence. As shown in
Table 1 the total sulfur is predominantly composed of organic sulfur
and pyritic sulfur; the organic sulfur in both coaleld is higher than
the pyritic sulfur in general. The high proportions of organic sulfur
may indicate the seawater affected the coal depositional environment.
In addition, the high percentages of pyrite and pyritic sulfur in the
coals may indicate both seawater and volcanism affected the coal depo-
sitional environment.
The mineralogical compositions of the Saray and Pnarhisar coals are
quite similar, and pyrite, barite, gypsum, rozenite, butlerite, kaolinite,
muscovite, quartz, tamarugite and chlorite are the common minerals
for both coalelds. The identied minerals are rich in SiO2, Al2O3, K2O
and TiO2 (Deer et al., 1992). So, the major oxide compositions of the
coals are compatible with the mineralogical composition of the coals
in both coalelds. Also, the relatively high content of Fe2O3 in the
coals can be related to high pyrite in the coals.
Although the trace element contents of both coalelds are also sim-
ilar, the Sc, V, Cr, Fe, Co, Ni, Cu, Zn, As, Mo, Sb and Tm contents of the
Saray coals are higher than those of the Pnarhisar coals (Fig. 9A). By
contrast, the Se, W, U and REE contents of the Pnarhisar coals are higher
than those of the Saray coals (Fig. 9B). The Thrace Basin was fed from
three source regions: the oldest basement rocks of the Thrace region,
the Strandja Massif and the remnant oceanic crust of the Tethys. The dif-
ferences in geochemical composition of the coals can be explained by
the dominant sediment source regions. The Pnarhisar coaleld (espe-
cially the Akren coal mine) is located on the edge of the Strandja Mas-
sif. The Strandja Massif is one of the most important sediment-source
regions for the Thrace Basin, and it can be said that Strandja Massif is
the effective sediment source for the Pnarhisar coaleld. The massif
consists mainly of meta-granites, basic-acidic granitic and volcanic
rocks, and various meta-sedimentary rocks (Natalin et al., 2012). The
rocks of the Massif are made of mainly feldspar group minerals, quartz
and biotite. Mason and Moore (1982) suggest that rocks of granitic com-
position are enriched in lithophile elements such as Se, Th, U and REEs,
and are depleted in siderophile and chalcophile elements. Several
23
mineralization zones have been identied in the Strandja Massif, and
these zones may have affected the trace element contents of the coals
(Parlak and afak, 1995). The higher V, Cr, Fe, Co, Ni and As values in
the Saray coals indicate that the Tethys ocean remnant ultrabasic
rocks, which are composed predominantly of olivine, pyroxene and
chromite, may have been a signicant sediment source for the Saray re-
gion, together with the oldest basement rocks of Thrace region and
Strandja Massif.
6. Conclusions
The coals in the Saray and Pnarhisar coalelds were deposited in a
limnic environment. The pyrite content of the coals varies from 7 to
13% and the pyrite is of both syngenetic and epigenetic origin. Total sul-
fur in the coals varies from 1.86 to 15.3%. Pyritic sulfur and organic sulfur
are the dominant sulfur forms for both coalelds. The high percentages
of pyrite and total S indicate that both volcanism and seawater affected
the coal depositional environment. The major minerals in the Saray and
Pnarhisar coals are pyrite, barite and gypsum. Minor amounts of
rozenite, butlerite, kaolinite, montmorillonite and muscovite are pres-
ent; trace amounts of quartz, tamarugite and chlorite accompany the
major minerals. Barite, rozenite, tamarugite and chlorite in the coals
are described in this study for the rst time. The coals are enriched in
Be, Sc, V, Co, Ni, Cu, Zn, As, Se, Rb, Sr, Mo, Sn, Cs, Ba, W, Pb, Th and U.
The REEs are also enriched relative to the continental crust.
Vanadium, Cr, Fe, Co, Ni and As are more enriched in the Saray coals;
Se, U, and REEs are more enriched in the Pnarhisar coals. However, the
rare earth element content of the coalelds from the northwest Thrace
basin is lower than the average for world low-rank coals. The differ-
ences in geochemical compositions of the coalelds, the correlation co-
efcients and the Pearson correlation coefcients indicate that the
Strandja Massif was the prevailing sediment source for the Pnarhisar
eld, while the Strandja Massif, the oldest (basement) rocks of the Thra-
ce region, and the Tethyan ultrabasic rocks have been collectively active
as sediment sources for both of the coalelds.
Acknowledgements
This research was supported by the Scientic Research Projects Unit
of Istanbul Technical University (project number: 37013), the Scientic
and Technological Research Council of Turkey (TBTAK) (project
number: 115Y095), and General Directorate of Turkish Coal Enterprises
(TK). We are thankful Dr. Selami Toprak for supporting the
24 C. Erarslan, Y. rgn International Journal of Coal Geology 173 (2017) 925
petrographical and mineralogical studies. The authors would like to spe-
cial thank the editor Dr. S. Dai and the reviewer Dr. C. Ward for critical
reviews and suggestions to improve the manuscript.
References
ASTM Standard D2797/D2797M-11a, 2011. Standard Practice for Preparing Coal Samples
for Microscopical Analysis by Reected Light. ASTM International, West
Conshohocken, PA.
ASTM Standard D4239-13, 2013. Test Method for Sulfur in the Analysis Sample of Coal
and Coke Using High-temperature Tube Furnace Combustion. ASTM International,
West Conshohocken, PA.
ASTM Standard D5373-13, 2013. Determination of Carbon, Hydrogen and Nitrogen in
Analysis Samples of Coal and Carbon in Analysis Samples of Coal and Coke1. ASTM In-
ternational, West Conshohocken, PA.
ASTM Standard D7582-12, 2012. Test Method for Proximate Analysis of Coal and Coke by
Macro Thermogravimetric Analysis. ASTM International, West Conshohocken, PA.
Bandy, M.C., 1938. Mineralogy of three sulphate deposits of Northern Chile. Journal of the
Mineralogical Society of America 23, 670760.
Bat, Z., 1996. Palynostratigraphy and Coal Petrography of the Upper Oligocene Lignites of
the Northern Thrace Basin, NW Turkey, Middle East Technical University PhD thesis,
Ankara, Turkey. (364pp).
Browneld, M.E., Affolter, R.H., Stricker, G.D., Hildebrand, T.H., 1995. High chromium con-
tents in Tertiary coal deposits of northwestern Washingtona key to their deposi-
tional history. Int. J. Coal Geol. 27, 153169.
Carlson, C.L., Adriano, D.C., 1993. Environmental impacts of coal combustion residues.
J. Environ. Qual. 22, 227247.
Chen, J., Liu, G., Jiang, M., Chou, C.-L., Li, H., Wu, B., Zheng, L., Jiang, D., 2011. Geochemistry
of environmentally sensitive trace elements in Permian coals from the Huainan coal-
eld, Anhui, China. Int. J. Coal Geol. 88, 4154.
Chou, C.-L., 2012. Sulfur in coals: a review of geochemistry and origins. Int. J. Coal Geol.
100, 113.
Chou, I.-M., Seal II, R.R., Hemingway, B.S., 2002. Determination of melanteriterozenite
and chalcanthitebonattite equilibria by humidity measurements at 0.1 MPa. Am.
Mineral. 87, 108114.
Coleman, S.L., Bragg, L.J., 1990. Distribution and mode of occurrence of arsenic in coal. In:
Chyi, L.L., Chou, C.-L. (Eds.), Recent Advances in Coal Geochemistry. Geol. Soc. Am.
Spec. Pap. 248, pp. 1326.
Dai, S., Ren, D., Tang, Y., Shao, L., Li, S., 2002. Distribution, isotopic variation and origin of sulfur
in coals in the Wuda coaleld, Inner Mongolia, China. Int. J. Coal Geol. 51, 237250.
Dai, S., Ren, D., Tang, Y., Yue, M., Hao, L., 2005a. Concentration and distribution of elements in
Late Permian coals from western Guizhou Province, China. Int. J. Coal Geol. 61, 119137.
Dai, S., Chou, C.-L., Yue, M., Lou, K., Ren, D., 2005b. Mineralogy and geochemistry of a Late
Permian coal in the Dafang Coaleld, Guizhou, China: inuence from siliceous and
iron-rich calcic hydrothermal uids. Int. J. Coal Geol. 61, 241258.
Dai, S., Zeng, R., Sun, Y., 2006. Enrichment of arsenic, antimony, mercury, and thallium in a
Late Permian anthracite from Xingren, Guizhou, Southwest China. Int. J. Coal Geol. 66,
217226.
Dai, S., Zhou, P., Ren, D., Wang, X., Li, D., Zhao, L., 2007. Geochemistry and mineralogy of
the Late Permian coals from the Songzao Coaleld, Chongqing, southwestern China.
Sci. China Ser. D Earth Sci. 50, 678688.
Dai, S., Ren, D., Zhou, Y., Chou, C.-L., Wang, X., Zhao, L., Zhu, X., 2008. Mineralogy and geo-
chemistry of a superhigh-organic-sulfur coal, Yanshan Coaleld, Yunnan, China: evi-
dence for a volcanic ash component and inuence by submarine exhalation. Chem.
Geol. 255, 182194.
Dai, S., Ren, D., Chou, C.-L., Finkelman, R.B., Seredin, V.V., Zhou, Y., 2012a. Geochemistry of
trace elements in Chinese coals: a review of abundances, genetic types, impacts on
human health, and industrial utilization. Int. J. Coal Geol. 94, 321.
Dai, S., Wang, X., Seredin, V.V., Hower, J.C., Ward, C.R., O'Keefe, J.M.K., Huang, W., Li, T., Li,
X., Liu, H., Xue, W., Zhao, L., 2012b. Petrology, mineralogy, and geochemistry of the
Ge-rich coal from the Wulantuga Ge ore deposit, Inner Mongolia, China: new data
and genetic implications. Int. J. Coal Geol. 9091, 7299.
Dai, S., Li, T., Jiang, Y., Ward, C.R., Hower, J.C., Sun, J., Liu, J., Song, H., Wei, J., Li, Q., Xie, P.,
Huang, Q., 2015a. Mineralogical and geochemical compositions of the Pennsylvanian
coal in the Hailiushu Mine, Daqingshan Coaleld, Inner Mongolia, China: Implications
of sediment-source region and acid hydrothermal solutions. Int. J. Coal Geol. 137,
92110.
Dai, S., Yang, J., Ward, C.R., Hower, J.C., Liu, H., Garrison, T.M., French, D., O'Keefe, J.M.K.,
2015b. Geochemical and mineralogical evidence for a coal-hosted uranium deposit
in the Yili Basin, Xinjiang, northwestern China. Ore Geol. Rev. 70, 130.
Dai, S., Seredin, V.V., Ward, C.R., Hower, J.C., Xing, Y., Zhang, W., Song, W., Wang, P., 2015c.
Enrichment of USeMoReV in coals preserved within marine carbonate succes- Krauskopf, K.B., 1985. Jeokimyaya giri (Aykol, A., nan, K. ve Suner, F.'nin evirisi). 1308.
sions: geochemical and mineralogical data from the Late Permian Guiding Coaleld,
Guizhou, China. Mineral. Deposita 50, 159186.
Dai, S., Wang, P., Ward, C.R., Tang, Y., Song, X., Jiang, J., Hower, J.C., Li, T., Seredin, V.V.,
Wagner, N.J., Jiang, Y., Wang, X., Liu, J., 2015d. Elemental and mineralogical anomalies
in the coal-hosted Ge ore deposit of Lincang, Yunnan, southwestern China: Key role
of N2CO2-mixed hydrothermal solutions. Int. J. Coal Geol. 152, 1946.
Dai, S., Graham, I.T., Ward, C.R., 2016. A review of anomalous rare earth elements and yt-
trium in coal. Int. J. Coal Geol. 159, 8295.
Deer, W.A., Howie, R.A., Zussman, J., 1992. An Introduction to the Rock-Forming Minerals.
Longman Scientic & Technical, Edinburg (696pp).
Diessel, C.F.K., 1992. Coal-bearing Depositional Systems. Springer-Verlag, Berlin, Heidel-
berg (721 pp).
Doust, H., Arkan, Y., 1974. The geology of the Thrace Basin. Trkiye kinci Petrol Kongresi
Teblileri Kitab 119136.
Ediger, V.., 1982. Kuleli Babaeski srtnn (KB Trakya) Paleo-ortamsal incelenmesi
ve KuzeyTrakya havzasnn hidrokarbon potansiyelinindeerlendirilmesinde
yeni yaklam. Trkiye Petrolleri Anonim Ortakl Rapor No: 1995 (194p, Ankara
(unpublished)).
Ediger, V. ., 1988. Biga Yarmadas'ndaki kmrl birimlerdenalnan rneklerin
palinolojik analizi, Trkiye Petrolleri Anonim Ortakl Aratrma Merkezi Grubu
Rapor No: 809, Ankara (unpublished).
Edmunds, W.M., 1975. Geochemistry of brines in the coal measures of northeast England.
Transactions of the Institute of Mining and Metallurgy, London B 84, 3952.
Ehlers, E.G., Stiles, D.V., 1965. Melanterite-rozenite equilibrium. The American Mineralo-
gist 50, 14571461.
Erarslan, C., rgn, Y., Bozkurtolu, E., 2014. Geochemistry of trace elements in the Kean
coal and its effect on the physicochemical features of ground- and surface waters in
the coal elds, Edirne, Thrace Region, Turkey. Int. J. Coal Geol. 133, 112.
Ercan, T., 1992. Cenozoic volcanism in Thrace and its regional distribution. Geological En-
gineering 41, 3750 (in Turkish).
Finkelman, R.B., 1994. Modes of occurrence of potentially hazardous elements in coal:
levels of condence. Fuel Process. Technol. 39, 2134.
Finkelman, R., 2004. Potential health impacts of burning coal beds and waste banks. Int.
J. Coal Geol. 59, 1924.
Finkelman, R.B., Gross, M.K.P., 1999. The types of data needed for assessing the environ-
mental and human health impacts of coal. Int. J. Coal Geol. 40, 91101.
Finkelman, R.B., Orem, W., Castranova, V., Tatu, C.A., Belkin, H.E., Zheng, B., Lerch, H.E.,
Maharaj, S.V., Bates, A.L., 2002. Health impacts of coal and coal use: possible solutions.
Int. J. Coal Geol. 50, 425443.
Fytikas, M., Inncenti, F., Manetti, P., Mazzuoli, R., Peccerillo, A., Villari, L., 1984. Tertiary to
Quaternary evolution of volcanism in the Aegean region. Geol. Soc. Lond. Spec. Publ.
17, 687699.
Goodarzi, F., 2002. Mineralogy, elemental composition and modes of occurrence of ele-
ments in Canadian feed-coals. Fuel 81, 11991213.
Goodarzi, F., 2006. Assessment of elemental content of milled coal, combustion residues,
and stack emitted materials: Possible environmental effects for a Canadian pulver-
ized coal-red power plant. Int. J. Coal Geol. 65, 1725.
Grdal, G., 2008. Geochemistry of trace elements in an coal (Miocene), anakkale, Tur-
key. Int. J. Coal Geol. 74, 2840.
Grdal, G., 2011. Abundances and modes of occurrence of trace elements in the an coals
(Miocene), anakkale-Turkey. Int. J. Coal Geol. 87, 157173.
Hammarstrom, J.M., Seal II, R.R., Meier, A.L., Kornfeld, J.M., 2005. Secondary sulphate min-
erals associated with acid mine drainage in the eastern US: recycling of metals and
acidity in surcial environments. Chem. Geol. 215, 407431.
Hower, J.C., Campbell, (Iain) J.L., Teesdale, W.J., Nejedly, Z., Robertson, J.D., 2008. Scanning
proton microprobe analysis of mercury and other trace elements in Fesuldes from a
Kentucky coal. Int. J. Coal Geol. 75, 8892.
Huggins, F.E., Huffman, G.P., 1996. Modes of occurrence of trace elements in coal from
XAFS spectroscopy. Int. J. Coal Geol. 32, 3153.
International Committee for Coal and Organic Petrology (ICCP), 1998C. The new vitrinite
classication (ICCP system 1994). Fuel 77, 349358.
International Committee for Coal and Organic Petrology (ICCP), 2001C. The new inertinite
classication (ICCP system 1994). Fuel 80, 459471.
International Energy Agency, 2015. World Energy Outlook, Executive Summary, France.
Jiang, Y., Elswick, E.R., Mastalerz, M., 2008. Progression in sulfur isotopic compositions
from coal to y ash: examples from single-source combustion in Indiana. Int. J. Coal
Geol. 73, 273284.
Karayiit, A.I., Akgun, F., Gayer, R.A., Temel, A., 1999. Quality, palynology, and
palaeoenvironmental interpretation of the Ilgin lignite, Turkey. Int. J. Coal Geol. 38,
219236.
Karayiit, A.., Spears, D.A., Booth, C.A., 2000. Antimony and arsenic anomalies in the coal
seams from the Gokler coaleld, Gediz, Turkey. Int. J. Coal Geol. 44, 117.
Kaymak, N., Aldanmaz, E., Langereis, C., Spell, T.L., Gurer, O.F., Zanetti, K.A., 2007. Late
Miocene transcurrent tectonics in NW Turkey: evidence from paloemagnetism and
40
Ar-39Ar dating alkaline volcanic rocks. Geol. Mag. 144, 379392.
Keskin, C., 1974. Kuzey Trakya Havzas'nn stratigrasi. Trkiye kinci Petrol Kongresi
Teblileri Kitab 137163.
Ketris, M.P., Yudovich, Ya.E., 2009. Estimations of Clarkes for Carbonaceous biolithes:
world averages for trace element contents in black shales and coals. Int. J. Coal
Geol. 78, 135148.
Kolovos, N., Georgakopoulos, A., Filippidis, A., Kavouridis, C., 2002. Environmental effects
of lignite and intermediate steriles co-excavation in southern eld mine of Ptolemais
Northern Greece. Energy Sources 24, 561573.
Kortenski, J., Satirov, A., 2002. Trace and major element content and distribution in Neo-
gene lignite from the Soa Basin, Bugaria. Int. J. Coal Geol. 52, 6382.
T yayn, stanbul (666 p).
Kruszewski, L., 2013. Supergene sulphate minerals from the burning coal mining dumps
in the Upper Silesian Coal Basin, South Poland. Int. J. Coal Geol. 105, 91109.
Mason, B., Moore, C.B., 1982. Principles of Geochemistry. fourth ed. John Wiley & Sons,
pp. 4647.
Moore, F., Esmaeili, A., 2012. Mineralogy and geochemistry of the coals from the Karmozd
and Kiasar coal mines, Mazandaran province, Iran. Int. J. Coal Geol. 96-97, 921.
MTA, 2010. Trkiye Linyit Envanteri. Directorate of Mineral Research and Exploration
(MTA Genel Mdrl) (371 pp).
Natalin, B.A., Sunal, G., Satr, M., Toraman, E., 2012. Tectonics of the Strandja Massif, NW
Turkey: history of a Long-Lived Arc at the Northern Margin of Palaeo-Tethys. Turk.
J. Earth Sci. 21, 755798.
 C. Erarslan, Y. rgn International Journal of Coal Geology 173 (2017) 925 25

Okay, A., Satr, M., Tysz, O., Akyz, S., Chen, F., 2001. The tectonics of the Strandja Mas-
sif: late-Variscan and mid-Mesozoic deformation and metamorphism in the northern
Aegean. Int. J. Earth Sci. 90, 217233.
Palmer, C.A., Tuncal, E., Dennen, Kristen O., Coburn, T.C., Finkelman, Robert B., 2004. Char-
acterization of Turkish coals: a nationwide perspective. Int. J. Coal Geol. 60, 85115.
Parlak, P., afak, ., 1995. Krklareli li-krpaa Sahas Cu-Mo Yata Deerlendirme Alpu coal basin in Turkey, its petrographical properties and depositional environ-
Raporu, MTA Raporlar Fizibilite Ettleri Dairesi Bakanl, Ankara. Rapor No: 9841
(in Turkish).
Perinek, D., Ata, N., Karatut, ., Erensoy, E., 2015. Geological Factors Controlling Potential
of Lignite Beds within the Danimen Formation in the Thrace Basin. Bull. Min. Res.
Exp. 150, 77108.
Pickel, W., Kus, J., Flores, D., Kalaitzidiz, S., Christanis, K., Cardott, B.J., Misz-Kennan, M.,
Rodrigues, S., Hentschel, A., Hamor-Vido, M., Crosdale, P., Wagner, N., ICCP, 2017.
Classication of liptinite ICCP system 1994. Int. J. Coal Geol. 169, 4061.
Querol, X., Klika, Z., Weiss, Z., Finkelman, R.B., Alastuey, A., Juan, R., Lopez-Soler, A., Plana,
F., Kolker, A., Chenery, S.R.N., 2001. Determination of element afnities by density
fractionation of bulk coal samples. Fuel 80, 8396.
Ren, D., 1996. Mineral matter in coal. In: Han, D. (Ed.), Coal Petrology of China. Publishing
House of China University of Mining and Technology, Xuzhou, pp. 6778 (in Chinese
with English abstract).
Ren, D., Xu, D., Zhao, F., 2004. A preliminary study on the enrichment mechanism and oc-
currence of hazardous trace elements in the Tertiary lignite from the Shenbei coal-
eld, China. Int. J. Coal Geol. 57, 187196.
Ruppert, L., Finkelman, R.B., Boti, E., Milosavljevic, M., Tewalt, S., Simon, N., Dulong, F.,
1996. Origin and signicance of high nickel and chromium concentrations in Pliocene
lignite of Kosovo Basin, Serbia. Int. J. Coal Geol. 29, 235258.
Ruppert, L.F., Hower, J.C., Eble, C.F., 2005. Arsenic-bearing pyrite and marcasite in the Fire
Clay coal bed, Middle Pennsylvanian Breathitt formation, eastern Kentucky. Int.J. Coal
Geol. 63, 2735.
Saner, S., 1985. Saros Krfezi dolaynn kelme istieri ve tektonik yerleimi, Kuzeydou Yang, J., 2006. Concentrations and modes of occurrence of trace elements in the Late
Ege Denizi, Trkiye. Trkiye Jeoloji Kurumu Blteni 28, 110.
Scott, C.A., 2002. Coal petrology and the origin of coal macerals: a way ahead? Int. J. Coal
Geol. 50, 119134.
engler, ., 2008. Trakya Havzas Kmr Arama Raporlar, 200520062007 yl sondaj
verileri, MTA Raporlar. 6-32. Directorate of Mineral Research and Exploration, Anka-
ra (in Turkish, unpublished).
Seredin, V.V., Finkelman, R.B., 2008. Metalliferous coals: a review of the main genetic and
geochemical types. Int. J. Coal Geol. 76, 253289.
Singh, S., Ram, L.C., Masto, E.R., Verma, S.K., 2011. A comparative evaluation of minerals
and trace elements in the ashes from lignite, coal refuse, and biomass red power
plants. Int. J. Coal Geol. 87, 112120.
Siyako, M., 2006a. Trakya blgesi litostratigra birimleri. Tersiyer Kaya Birimleri Blm,
MTA Genel Mdrl Stratigra Komitesi, pp. 4366.
Siyako, M., 2006b. Lignitic Sandstones of the Trakya Basin. Miner. Res. Explor. Bull. 123,
6372.
Siyako, M., Huvaz, O., 2007. Eocene stratigraphic evolution of the Thrace Basin, Turkey.
Sediment. Geol. 198, 7591.
Swaine, D.J., 1990. Trace Elements in Coal. Butterworths, London (290 pp).
Swaine, D.J., Goodarzi, F., 1995. Environmental Aspects of Trace Elements in Coal. Kluwer
Academic Publishers, The Netherlands (312 pp).
Sykorova, I., Pickel, W., Christanis, K., Wolf, M., Taylor, G.H., Flores, D., 2005. Classication
of huminiteICCP system 1994. Int. J. Coal Geol. 62, 85106.
Toprak, S., 2009. Petrographic properties of major coal seams in Turkey and their forma-
tion. Int. J. Coal Geol. 784, 263274.
Toprak, S., Sutcu, E.C., Senguler, I., 2015. A fault controlled, newly discovered Eskiehir
ment. Int. J. Coal Geol. 138, 127144.
TS 329 ISO 157, 2000. Coal-determination of Forms of Sulfur. Trk Standartlar (in
English).
Tuncal, E., iftci, B., Yavuz, N., Toprak, S., Kker, A., Gencer, Z., Ayk, H., ahin, N., 2002.
Chemical and Technological Properties of Turkish Tertiary Coals. MTA Maden Tetkik
ve Arama Genel Mdrl, Ankara.
Turgut, S., Siyako, M., Dilki, A., 1983. Trakya Havzasnn Jeolojisi ve Hidrokarbon
Olanaklar. Trkiye Jeoloji Kongresi Blteni 4, 3546.
Turner, B.R., Richardson, D., 2004. Geological controls on the sulphur content of coal
seams in the Northumberland Coaleld, Northeast England. Int. J. Coal Geol. 60,
169196.
Van Der Flier, E., Fyfe, W.S., 1985. Uranium-thorium systematics of two Canadian coals.
Int. J. Coal Geol. 4, 335353.
Ward, C.R., 1989. Minerals in bituminous coals of the Sydney Basin (Australia) and the Il-
linois Basin (U.S.A.). Int. J. Coal Geol. 13, 455479.
Ward, R.C., 2002. Analysis and signicance of mineral matter in coal seams. Int. J. Coal
Geol. 50, 135168.
Ward, C.R., 2016. Analysis, origin and signicance of mineral matter in coal: an updated
review. Int. J. Coal Geol. 165, 127.
Widodo, S., Oschmann, W., Bechtel, A., Sachsenhofer, R.F., Anggayana, K., Puettmann, W.,
2010. Distribution of sulfur and pyrite in coal SEAMS from Kutai Basin (East Kaliman-
tan, Indonesia): implications for paleoenvironmental conditions. Int. J. Coal Geol. 81,
151162.
Permian coals from the Puan Coaleld, southwestern Guizhou, China. Environ.
Geochem. Health 28, 567576.
Ylmaz, Y., Polat, A., 1998. Geology and evolution of the Thrace volcanism, Turkey. Acta
Vulcanol. 10, 293303.
Yossifova, M.G., Eskenazy, G.M., Valceva, S.P., 2011. Petrology, mineralogy, and geochem-
istry of submarine coals and petried forest in the Sozopol Bay, Bulgaria. Int. J. Coal
Geol. 87, 212225.
Yudovich, Ya.E., Ketris, M.P., 2005. Arsenic in coal: a review. Int. J. Coal Geol. 61, 141196.
Zhang, J.Y., Ren, D.Y., Zheng, C.G., Zeng, R.S., Chou, C.L., Liu, J., 2002. Trace element abun-
dances in major minerals of Late Permian coals from southwestern Guizhou Province,
China. Int. J. Coal Geol. 53, 5564.
Zhang, J., Ren, D., Zhu, Y., Chou, C.-L., Zeng, R., Zheng, B., 2004. Mineral matter and poten-
tially hazardous trace elements in coals from Qianxi Fault Depression Area in south-
western Guizhou, China. Int. J. Coal Geol. 57, 4961.
Zhao, Y.C., Zhang, J.Y., Huang, W.C., Wang, Z.H., Li, Y., Song, D.Y., Zhao, F.H., Zheng, C.G.,
2008. Arsenic emission during combustion of high arsenic coals from southwestern
Guizhou, China. Energy Convers. Manag. 49, 615624.
Zhou, J., Zhuang, X., Alastuey, A., Querol, X., Li, H., 2010. Geochemistry and mineralogy of
coal in the recently explored Zhundong large coal eld in the Junggar basin, Xinjiang
province, China. Int. J. Coal Geol. 82, 5167.