International Journal of Coal Geology 187 (2018) 54–70

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International Journal of Coal Geology

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Coal petrography, mineralogy, elemental compositions and T

palaeoenvironmental interpretation of Late Carboniferous coal seams in
three wells from the Kozlu coalfield (Zonguldak Basin, NW Turkey)
⁎
Ali İhsan Karayiğita, , Maria Mastalerzb, Rıza Görkem Oskaya, Rod A. Gayerc,1
a
Hacettepe University, Department of Geological Engineering, 06800 Ankara, Turkey
b
Indiana Geological and Water Survey, Indiana University, 611 N. Walnut Grove Avenue, Bloomington, IN, USA
c
Department of Earth Sciences, Cardiff University, Cardiff, United Kingdom

A R T I C L E I N F O A B S T R A C T

Keywords: A number of coal seams of Late Carboniferous age in the coal-bearing Karadon, Kozlu, and Alacaağzı formations
Late Carboniferous have been mined in several deep underground mines in the Zonguldak Basin (NW Turkey). For this study, a total
Coal petrography of 154 coal core samples were collected from three research wells that were drilled in the tectonically complex
Mineralogy settings of the Kozlu coalfield. All the coal samples were studied by means of coal petrography, mineralogy, and
Geochemistry
geochemistry. Special attention was given to the compositions and origins of fracture/cleat-filling minerals that
Fracture/cleat-infilling
were identified by SEM-EDX on polished blocks. The coal seams investigated are of bituminous rank. They are
Coal facies
Zonguldak basin characterized by low total sulphur contents (≤1.0%, on dry basis) and high gross calorific values
Turkey (22.5–40.2 MJ/kg, on dry, ash-free basis), whereas ash yields and volatile matter contents are variable. X-ray
powder diffraction data indicate that the mineralogical compositions of the studied coal seams are rather similar,
and clay minerals, along with quartz and carbonate minerals, were identified in almost all seams. The statistical
evaluations and SEM data show that some elements such as Mg, Ti, Zr, Nb, and Th are generally affiliated with
silicate minerals, whereas elements like Cu, Zn, Mo, and Pb are mainly associated with sulphide minerals. The
silicate minerals are generally detrital, and the majority of carbonate minerals are of epigenetic origin. The
epigenetic carbonate and sulphide minerals suggest that circulated solutions within coal seams were mainly
derived from Ca2 +-rich solutions leached from overlying formations such as Cretaceous aged Zonguldak for-
mations and from hydrothermal solutions that likely were derived from andesitic dykes within the basin. The
regional tectonic activities during coalification seem to have deformed coal-bearing formations and, therefore,
intra-basinal solutions could have penetrated into the studied coal seams. The epigenetic mineralisation also
resulted in elemental enrichments and elevated ash yields, total sulphur, and volatile matter contents in some
coal seams. Thus, deformation during coalification controlled some coal quality parameters in the studied wells.
The coal facies diagrams suggest that palaeomires mostly accumulated under limno-telmatic conditions, whereas
a telmatic environment was more common in palaeomires of the Kozlu Formation. Coal petrography suggests
that peat-forming vegetation and water tables in palaeomires were changeable during the Late Carboniferous.

1. Introduction
The geological evolution of Turkey resulted in the development of
several coal-bearing sedimentary basins. The majority of the coal re-
serves of Turkey are located in the Neogene aged sedimentary basins
(Oskay et al., 2013). The Carboniferous coal deposits are limited and
most of them are uneconomic, except for the Zonguldak Basin (NW
Turkey, Fig. 1a), which is located in the İstanbul Zone (southern margin
of Laurasia) (Kerey, 1985; Okay et al., 1994; Okay and Nikishin, 2015;
Şengör, 1995). There are various hypotheses about the evolution of the
Zonguldak Basin and adjacent basins in the İstanbul Zone, and the
discussion continues (Tüysüz et al., 2016, and references therein). The
discussion is mostly based on the origin and location of Zonguldak
Basin and İstanbul Zone during Carboniferous and the tectonic evolu-
tion of coal-bearing sequences after Late Carboniferous. The commonly
accepted theory is that the Palaeozoic units of this zone, including coal-
bearing Late Carboniferous sequences, were affected by several regional
tectonic events, as follows: 1) Hercynian (Variscan) orogeny, which

⁎
Corresponding author.
E-mail address: aik@hacettepe.edu.tr (A.İ. Karayiğit).
1
Retired.

https://doi.org/10.1016/j.coal.2017.12.007
Received 21 August 2017; Received in revised form 22 December 2017; Accepted 27 December 2017
Available online 28 December 2017
0166-5162/ © 2017 Elsevier B.V. All rights reserved.
A.İ. Karayiğit et al.
Fig. 1. (a) and (b) Geologic map of the study area (modified and simplified from Canca, 1994; Mann et al., 1995; Karayiğit, 2001), (c) Stratigraphic column of the Soma Basin (modified
and simplified from Canca, 1994; Karayiğit, 2001; Yalçin et al., 2002; Hoşgörmez et al., 2002).
resulted in regional uplift and eroded Late Carboniferous-Permian se-
diments, similar to the majority of late Palaeozoic coal deposits in
Eastern Europe (e.g., Dniepr-Donets Basin); 2) rifting from Eurasia and
drifting southward by transform faults during the Aptian-Albain; and 3)
collision between the İstanbul and Sakarya zones (Central Pontides)
during the Eocene (Okay et al., 1994; Okay and Tüysüz, 1999; Okay and
Nikishin, 2015; Şengör and Yılmaz, 1981; Yılmaz et al., 1997). As a
result of these tectonic movements after the Permian, coal-bearing se-
quences in the basin were deformed and buried deeper, and several
faults and folds developed within the basin (Şengör, 1995; Yalçin et al.,
2002; Yılmaz et al., 1997). Therefore, the original thickness and geo-
logical features of Carboniferous coal-bearing sequences cannot easily
be recognized, and several dissimilar models were proposed (Yalçin
et al., 2002).
The Zonguldak Basin holds about 60 coal seams in the Late
Carboniferous sequences, with thicknesses ranging between 0.5 and
5 m, and the basin contains almost all the bituminous coal reserves (c.
1.5 Gt) of Turkey (Karayiğit et al., 1998, 2000; TTK, 2017). These
seams are exploited in several underground mines in different parts of
the basin (at Armutçuk, Kozlu, Üzülmez, Karadon, Amasra), mostly for
the use in iron and steel works and to a minor extent as feed coal for the
Çatalağzı Power Plant (Fig. 1b). The Zonguldak Basin was extensively
studied in terms of regional geology, palaeopalynology, coal-bed me-
thane potential, and coal mining techniques (Ağralı, 1964, 1970; Akgün
and Akyol, 1992; Akyol, 1972; Burger et al., 2000; Can et al., 2012;
Cleal and van Waveren, 2012; Erol et al., 2013; Hoşgörmez et al., 2002;
55
International Journal of Coal Geology 187 (2018) 54–70
Hoşgörmez, 2007; Karacan and Okadan, 2000; Kerey, 1985; Nakoman,
1975; Okay et al., 1994; Şengör and Yılmaz, 1981; Tüysüz, 1999; Yalçin
et al., 2002; Yılmaz et al., 1997). However, only few studies focused on
the petrographic, mineralogical, and geochemical features of the coal
seams in the entire basin (Karayiğit, 1992, 2001, 2003; Karayiğit et al.,
1998; Mann et al., 1995). In the late 1990s, several research wells were
drilled in the tectonically complex areas of the basin to better under-
stand the geology, coal properties, and correlations of coal seams. Even
though several coal seams were cored in these wells and analyses were
conducted (e.g., pore characteristics, organic geochemistry, palynology,
coal-bed methane potential) by various researchers, only limited data
have been published from these wells (Gürdal and Yalçın, 2000, 2001;
Gürdal et al., 2004; Yalçin et al., 2002; Yürüm et al., 2001a, 2001b).
The main aim of this study is to evaluate the coal petrographic,
mineralogical, and elemental compositions of coal seams intersected in
the K20/G, K20/H, and K20/K research wells in the Zonguldak Basin
and to compare the coal properties of the studied seams among these
wells. Special objectives of this study are to investigate peat-accumu-
lation during Late Carboniferous in the Zonguldak Basin and the com-
positions and origins of fracture- and cleat-infilling minerals in these
coals.
2. Geological background
The basement rocks of the basin are mainly composed of Silurian
metasediments and Devonian marine carbonate and volcanic rocks
A.İ. Karayiğit et al.
(Dean et al., 2000; Yalçin et al., 2002; Fig. 1). The Carboniferous ba-
sinal infill commences with shallow marine carbonates, and these are
overlain by alternations of sandstone, mudstone, claystone, and thin
coal seams that were deposited in a delta-front environment. This se-
quence is known as the Yılanlı Formation and the coal-bearing Ala-
caağzı Formation. In turn, this sequence is overlain by alternations of
conglomerate, sandstone, siltstone, claystone, and coal seams that were
deposited under deltaic conditions (mainly floodplain environment),
and this section is identified as the coal-bearing Kozlu and Karadon
formations. The previous sedimentological studies were suggested that
these formations were mainly deposited in deltaic (e.g. flood-plain),
and lacustrine conditions. The upper parts of Kozlu formation also de-
posited in braided river/meandering conditions (Kerey, 1985; Yalçin
et al., 2002). Tonstein layers were also identified in the Kozlu and
Karadon formations, especially in the Amasra coalfield (Burger et al.,
2000). A previous study carried out by Canca (1994) indicated that the
thicknesses of coal-bearing formations in the Zonguldak Basin vary, and
the total thickness of the Alacaağzı Formation is 1100 m, whereas the
Kozlu and Karadon formations reach up to 925 m and 550 m, respec-
tively.
The alternations between fluvial sediments and coal seams could
reflect continuous vertical tectonic movements during the Late
Carboniferous in the Zonguldak Basin (Kerey, 1985). The palaeopaly-
nological and palaeobotanical studies from coal-bearing Carboniferous
sequences indicate Namurian age for the Alacaağız Formation, West-
phalian A age for the Kozlu Formation, and Westphalian BCD age for
the Karadon Formation (Ağralı, 1964, 1970; Akgün and Akyol, 1992;
Akyol, 1972; Nakoman, 1975; Cleal and van Waveren, 2012). Previous
studies indicate that macro- and micropalaeoflora from the Zonguldak
Basin have similarities with other Carboniferous Eastern European coal
basins (Akgün and Akyol, 1992; Cleal and van Waveren, 2012). The
regional tectonic movements (Hercynian orogeny) terminated deposi-
tion of coal-bearing sequences and caused uplift and erosion of coal-
bearing sequences during the Permian (Yalçin et al., 2002). The re-
gional extensional regime resulted in the deposition of post-Carboni-
ferous cover formations (mostly Cretaceous marine carbonates, Tertiary
sedimentary units, and some volcanics) in the basin (Tüysüz, 1999;
Tüysüz et al., 2016), and these overlie unconformably coal-bearing
formations (Fig. 2b). In addition, andesitic dykes are reported in the
cover formations and Late Carboniferous coal-bearing formations.
These dykes caused the formation of natural cokes in the Kozlu For-
mation (Karayiğit, 1992). The collision between the Sakarya and İs-
tanbul zones during the Eocene and the following period resulted in the
second deformation phase in the Zonguldak basin, which caused de-
formation of both coal-bearing and cover formations. Therefore, several
folds and faults were identified in the basin (Fig. 1).
Fig. 2. Petrographical compositions of the studied samples (a) on whole-coal basis and (b) mineral matter-free basis (V: vitrinite, L: liptinite, I: Inertinite, MM: mineral matter).
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International Journal of Coal Geology 187 (2018) 54–70
3. Material and methods
The maximum depths of the investigated K20/G, H, and K wells
drilled in the Kozlu coalfield are 1759.1 m, 2002.2 m, and 1251.6 m,
respectively. The formations identified in the three wells, in descending
order, are the members (Kapuz limestone, İnciğez clastics, Öküşne
limestone, and possible Öküşne clastics) of the Zonguldak Formation of
Barremian-Aptian age and the coal-bearing Karadon, Kozlu, and
Alacaağzı formations. The coal-bearing formations in the Kozlu 20/G,
H, and K wells were identified at the depths of 401.5 m, 424.7 m, and
468.7 m, respectively. The vertical thicknesses of coal-bearing forma-
tions are variable, and the Alacaağzı Formation was cored only in K20/
H and K20/K. The transition from the Karadon Formation to Kozlu
Formation is conformable in K20/G; however, this transition is of a
tectonic nature in K20/H and K20/K. A number of faults were also
identified in these wells. The vertical thickness of coal beds varies from
0.05 to 3.43 m, and the net total coal thickness is around 60 m in the
studied wells.
A total of 154 coal samples were collected from K20/G, H, and K.
The samples are from depths ranging from 448.8 and 1616.8 m in K20/
G, 523.9 to 1906.1 m in K20/H, and 473.8 to 1211.6 m in K20/K. The
coal is black, brittle, and contains mineral impurities (e.g., clay mineral
bands, pyrite-bands). The roof and floor rocks of the coal seams are
mainly claystone, mudstone, sandstone, and rarely conglomerate. The
intercalations are thin and composed of organic-rich mudstone and
claystone. In all three wells, coal clasts and plant fragments were
identified in coarse sandstone and conglomerate.
The standard proximate and total sulphur analyses of the coal
samples were conducted according to the American Society for Testing
and Materials (ASTM) standards at Hacettepe University (ASTM,
D3175, 2011; ASTM D3174, 2012; ASTM D5865, 2013; ASTM, 4239,
2017). The instruments were calibrated with standard materials for
bituminous coal of the LECO Co. The polished blocks for petrographic
analyses were prepared according to ASTM D2797/D2797M (2011),
and these blocks were examined under both white incident light and
blue-light excitation using a Zeiss Axioplan microscope at RWTH Aa-
chen University, a Leitz MPV-II microscope and a Leica DM4000M
microscope at Hacettepe University, and a Zeiss RS-III microscope at
Indiana University. Random reflectance of vitrinite was measured ac-
cording to ISO 7404–5 (2009), and ICCP (1998) classifications were
used for maceral identifications (ICCP, 1998, 2001; Pickel et al., 2017).
Diagrams proposed by Diessel (1992) (Tissue Preservation Index [TPI]
vs. Gelification Index [GI]), and Calder et al. (1991) (Groundwater
Influence [GWI] vs. Vegetation Index [VI] diagrams) were used for
palaeoenvironmental reconstructions. Thermal modelling was also
conducted from K20/H and K20/K using BasinMod software at Cardiff
A.İ. Karayiğit et al. International Journal of Coal Geology 187 (2018) 54–70

University, comparing measured random vitrinite reflectance (%Rr)
with calculated %Rr to determine basal heat flow and heat transport by
solutions into the stratigraphic column. Furthermore, palaeo-
temperature (Tpeak) in the studied coal seams was assessed from mea-
sured %Rr values, according to the formula proposed by Barker and
Pawlewicz (1994).
The mineralogical compositions of coal samples were identified
using X-ray powder diffraction (XRD) with a Cu anode tube at
Hacettepe University and Cardiff University. The scanning area covered
the 2θ interval between 4° and 60°, with a scanning angle step of 0.015°
and a time step of 1 s. The clay fraction analysis was also conducted
from selected coal samples to determine clay minerals in the studied
samples according to methodology explained by Poppe et al. (2001).
The elemental compositions of coal samples were determined using an
inductively coupled plasma mass spectrometry (ICP-MS) at Cardiff
University. Samples for ICP-MS were prepared following the method
described by Gayer et al. (1999) where 200 mg of ash is sequentially
digested, using concentrated HF, aqua regia, and 5 M HCl. Five ml of
sample solution was analysed for a wide range of trace elements. The
analytical results of the coal samples were converted to a whole coal
dry basis using the ash yield (550 °C) of each coal sample. Additionally,
18 polished coal blocks from K20/G (K20/G-1, − 2, −4, − 7, −9,
− 11, − 12, −15, − 19, −20, − 21, − 24, −25, − 26, − 29, − 30,
− 31), 5 blocks from K20/H (K20/H-1, −17, − 24, − 36, − 56), and 5
blocks from K20/K (K20/K-1, −26, −50, − 56, − 61) were coated
with carbon; these blocks were investigated under a Zeiss EVO-50 EP
type SEM–EDX at Hacettepe University to better understand the frac-
ture- and cleat-infilling minerals and the elemental content of minerals.
4. Results and discussions
4.1. Coal characteristics
The studied coal samples from the three wells display slight differ-
ences in ash yield and volatile matter content (Table 1); on the other
hand, all samples generally had low total sulphur content (≤ 1.0%, on
dry basis), and moderate to high gross calorific value (22.5–47.7 MJ/
kg, on dry, ash-free basis). The coal seams within the Alacaağzı For-
mation, sampled in two wells, generally show very high ash yields
(> 40.0%, on dry basis). The coal seams from the Kozlu Formation are
characterized by variable ash yield (Table 1), and, in turn, calorific
value and volatile matter content vary throughout the studied wells.
Volatile matter contents are relatively low in coal seams from the lower
parts of the Alacaağzı Formation. Some coal seams in the Kozlu For-
mation from K20/K have higher ash yields than the other two wells,
and ash yields exceeding 50% (on dry basis). These values are recorded
from thinner coal seams that mostly contain mineral-rich bands (e.g.,
clay minerals); thus, ash yields are elevated and lower calorific values
are recorded in these seams. The relatively higher total sulphur (9.2%
in one sample and avg. 0.9%, on dry basis) and volatile matter contents
(up to 72.3 and avg. 35.1%, on dry ash-free basis) are recorded from
seams in the upper parts of the Karadon Formation; these differences
seem to be related to change in mineralogical compositions (see Section
4.3). Compared with previous studies from different parts of the basin,
the total sulphur contents of the studied coal seams are mostly within
the range reported; however, ash yields are slightly higher in this part
of the basin (Gürdal and Yalçın, 2000; Karayiğit, 2001, 2003; Karayiğit
et al., 1998, 2000).
4.2. Maceral composition
Maceral analyses of all the samples show that there is no distinct
difference in maceral groups among coal-bearing formations, and the
macerals groups display various proportions (Fig. 2a–b). Vitrinite is the
most common maceral group, in which telovitrinite and detrovitrinite
are abundant (Fig. 4a–f). Collotellinite is most common maceral in the
telovitrinite subgroup (up to 95.2%, on mineral matter-free basis
[mmf]); however, there are slight differences in the abundance of the
detrovitrinite subgroup macerals. In the Kozlu Formation, vitrodetrinite
is generally abundant, whereas collodetrinite is relatively common in
samples from the Karadon (besides samples from K20/G) and Alacaağzı
formations. Gelovitrinite is represented only by the corpogelinite
maceral and generally occurs in low proportions (≤1.0%, on mmf).
Inertinite is common and occurs in various proportions (0.2–64.3%, on
mmf). In some samples from the Karadon and Kozlu formations, in-
ertinite contents exceed 50% (Fig. 3b), and in all samples from the
Alacaağzı Formation, inertinite accounts for > 10.0% (on mmf). Fusi-
nite and inertodetrinite are common inertinite macerals and are mostly
identified within a collodetrinite and clay mineral matrix (Fig. 4c–e).
Micrinite is also common and mostly occurs around inertodetrinite that
is embedded within collodetrinite. In some cases, micrinite bands were
also observed within collotellinite (Fig. 4f). Macrinite is identified in all
the samples from the K20/G and K20/H wells. Liptinite occurs in lower
proportions than other maceral groups and is mostly represented by
sporinite and liptodetrinite (Fig. 4g–h). The lowest proportion is re-
corded mostly from the Alacaağzı Formation, whereas liptinite mac-
erals are common in the Karadon Formation (up to 22.8%, on mmf).
Thick-walled cutinite was commonly observed in this formation
(Fig. 5a–b). Similar variations on maceral groups were also reported
from the different parts of the basin (Karayiğit, 2001, 2003; Karayiğit
et al., 1998).
In the coal seams from the lower parts of the Kozlu Formation and
almost all the samples from the Alacaağzı Formation, liptinite macerals
display very low fluorescence intensity and greyish-black colour under
white incident light. This indicates in general that these seams have a
slightly higher coalification degree than seams in the Karadon
Formation and the upper parts of the Kozlu Formation. Minerals iden-
tified by incident light microscopy are mainly clay minerals, carbonate
minerals (e.g., siderite), and pyrite (Fig. 4c–f). Mineral contents as-
sessed by the coal petrography technique are generally moderate in the

Table 1
Ranges and weighted averages (in parenthesis) of the values obtained from proximate and total sulphur analyses of the coal samples from studied wells in the Zonguldak Basin (Fm.:
formation; CV: calorific value, db: dry basis; daf: dry, ash-free basis; n: the number of samples analysed).

Formation Well Ash (wt%, db) Volatile matter (wt%, daf) Gross CV (MJ/kg, daf) Total S (wt%, db)

Alacaağzı Fm. (Namurian) K20/H (n = 2) 42.0–60.9 (59.5) 20.2–33.3 (32.3) 34.3–47.7 (46.6) 0.2–0.4 (0.2)
K20/K (n = 9) 18.1–72.8 (38.9) 21.9–36.1 (35.4) 29.0–37.1 (35.4) 0.3–1.0 (0.6)
Avg. 43.8 34.6 38.0 0.5
Kozlu Fm. (Westphalian A) K20/G (n = 23) 5.6–67.7 (21.9) 20.5–36.0 (26.7) 31.5–40.2 (35.1) 0.3–2.8 (0.7)
K20/H (n = 53) 9.8–73.2 (32.0) 18.0–50.7 (27.1) 22.5–40.0 (33.7) 0.2–4.1 (0.6)
K20/K (n = 22) 11.4–84.9 (34.9) 23.5–54.9 (31.3) 23.8–36.3 (34.1) 0.1–1.6 (0.7)
Avg. 29.0 27.4 34.2 0.6
Karadon Fm. (Westphalian BCD) K20/G (n = 10) 15.5–63.5 (28.4) 33.9–43.3 (36.2) 29.9–35.8 (33.6) 0.3–5.1 (0.7)
K20/H (n = 1) 32.3 35.4 33 2.4
K20/K (n = 34) 3.7–72.0 (26.1) 27.5–72.3 (34.0) 20.1–35.9 (32.7) 0.2–9.2 (1.1)
Avg. 27.4 35.1 33.2 0.9

57
A.İ. Karayiğit et al.
Karadon and Kozlu formations and high in the Alacaağzı Formation
(Fig. 3a). The maceral cavities and cell-lumens are generally infilled
with carbonates and clay minerals, and rarely with pyrite. The clay
minerals are also associated with macerals (e.g., vitrodetrinite and in-
ertinite) and siderite nodules. Furthermore, fracture and cleat infilling
carbonate and pyrite mineralisation is observed (Fig. 4e–f).
4.3. Vitrinite reflectance and coal rank
Random reflectance values of vitrinite (%Rr) range between 0.78%
and 1.01% in the Karadon Formation (Table 2). The %Rr values in-
crease slightly toward lower parts of the Kozlu Formation, where they
vary from 0.97 to 1.49%. The coal seams in the lower parts of this
formation cored at K20/G and K20/H display higher %Rr values than
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International Journal of Coal Geology 187 (2018) 54–70
Fig. 3. Photomicrographs of the Zonguldak coals. All
photomicrographs are taken under incident white light (a,
b, c, d, e, f, g) and blue-light excitation (h), oil immersion,
500 × total magnification. Collotelinite (Ct), collodetrinite
(Cd), vitrodetrinite (Vd), cutinite (Cut), sporinite (Sp),
liptodetrinite (Ld), fusinite (Fus), semifusinite (SF), in-
ertodetrinite (Id), micrinite (Mic), clay mineral (CM), and
pyrite (Py). %Rr values of coal samples in photo-
micrographs are: 0.87% (a and g), 1.14% (b), 1.46% (c),
1.45% (d), 1.19% (e), 1.47% (f). (For interpretation of the
references to colour in this figure legend, the reader is re-
ferred to the web version of this article.)
the coal seams cored at K20/K (Table 2, Fig. 5). This difference is
presumably related to the burial depth of these coal seams and could
explain the relatively lower %Rr values (1.18–1.28%) of coal seams of
the Alacaağzı Formation in K20/K. The %Rr values show an increasing
trend toward the lower parts of all studied wells (Fig. 5). Similar trends
are also reported from other parts of the Zonguldak Basin as well as
other Carboniferous coal basins (e.g., Dniepr-Donets and Dobrudzha
basins) in Europe (Hertle and Littke, 2000; Izart et al., 2016; Karayiğit,
1992; Karayiğit et al., 1998; Sachsenhofer et al., 2002, 2012; Zdravkov
et al., 2017).
The %Rr values might be used to estimate the maximum palaeo-
temperature (Tpeak) in coal seams. The calculated Tpeak temperatures
from measured %Rr values applying Barker and Pawlewicz's (1994)
formula (Tpeak = (lnVRr% + 1.68)/0.0124) for the coals studied show
A.İ. Karayiğit et al.
that the Karadon Formation has lower temperatures (115–136 °C) than
other formations. A consequence of %Rr increase, Tpeak temperatures
increase toward the lower parts of the studied wells; the calculated
temperatures are 133–168 °C for the Kozlu Formation and 149–169 °C
for the Alacaağzı Formation. Of note, these calculated values are for
normal burial conditions. However, tectonic movements following the
Permian period and the presence of andesitic dykes in the basin might
also have led to rapid burial of Late Carboniferous coal-bearing sedi-
ments associated with hydrothermal conditions), modifying burial-re-
lated degree of coalification. Therefore, Tpeak temperatures were also
calculated according to rapid burial conditions (Tpeak = (lnVRr%
+ 1.19)/0.00782) and, again, the Karadon Formation yielded lower
palaeotemperatures (120–153 °C) than the Kozlu (148–203 °C) and
Alacaağzı (173–206 °C) formations. The measured %Rr values are also
useful to estimate heat flow conditions and the thickness of eroded
59
International Journal of Coal Geology 187 (2018) 54–70
Fig. 4. Photomicrographs of the Zonguldak coals. All
photomicrographs are taken under incident white light (a,
c, d, e, f, g, h) and blue-light excitation (b), oil immersion,
500 × total magnification. Collotelinite (Ct), collodetrinite
(Cd), vitrodetrinite (Vd), cutinite (Cut), sporinite (Sp),
liptodetrinite (Ld), fusinite (Fus), inertodetrinite (Id), clay
mineral (CM), siderite (Sid) and pyrite (Py). %Rr values of
coal samples in photomicrographs are: 0.87% (a and c),
1.19% (d), 1.46% (e), 1.47% (f and g), 1.02% (h). (For
interpretation of the references to colour in this figure le-
gend, the reader is referred to the web version of this ar-
ticle.)
sediments (Hartkopf-Fröder et al., 2015; Hertle and Littke, 2000;
Sachsenhofer et al., 2002; Senglaub et al., 2006).
A simple 1D thermal modelling from K20/H and K20/K were ap-
plied and various scenarios were undertaken in order to determine heat
flow and erosional after Carboniferous. The first scenario for K20/H
show that no eroded coal measures and a basal flow of 63 mW/m2
(normal continental heat flow); however, no match between measured
and calculated %Rr. Therefore, either additional depositional units
subsequently eroded, or higher basal heat flow required. The second
scenario for K20/H is with a basal heat flow 63 mW/m2 and 2500 m of
Late Carboniferous, subsequently eroded pre-Cretaceous. This scenario
has good match between measured and calculated %Rr, but slight mis-
match for samples from Alacaağzı Formation. The third scenario in this
well display similar basal heat flow and eroded Carboniferous coal
measures with scenario 2; on the other hand, this model displays very
A.İ. Karayiğit et al. International Journal of Coal Geology 187 (2018) 54–70

Fig. 5. Variations of the measured and calculated %Rr with depth in the studied wells.

Table 2 2012). The presence of coal clasts within coarse sandstone and con-
Ranges random reflectance (%Rr) values of vitrinite of the studied coal samples and coal glomerates in the three wells, indeed, reflects erosional periods during
seams in the Amasra area (*from Karayiğit, 1992). the Late Carboniferous. In contrast with Carboniferous Donets Basin,
Formation Kozlu area Amasra area⁎
the Zonguldak Basin was affected by Alpine Orogeny and this makes
hard to assume real thickness of Permo-Carboniferous cover of coal
Well %Rr %Rr measures. This could also explain the difference between calculated
temperature from measured %Rr and thermal models.
Alacaağzı Fm. K20/H (n = 2) 1.48–1.52 0.50–0.70
K20/K (n = 9) 1.18–1.28
Taking into account the calculated heat flow, the obtained thermal
Kozlu Fm. K20/G (n = 23) 1.00–1.49 0.66–0.98 maturation, and the regional tectonic deformation in the basin, the
K20/H (n = 53) 0.97–1.46 elevation of %Rr values in the studied wells can be expected. For
K20/K (n = 22) 0.99–1.08 comparison, %Rr values in the Amasra area (0.50–0.98%Rr) are gen-
Karadon Fm. K20/G (n = 10) 0.87–0.93 0.55–0.80
erally lower than for the Late Carboniferous coal seams examined in the
K20/H (n = 1) 0.87
K20/K (n = 34) 0.78–1.01 studied wells (Karayiğit, 1992; Karayiğit et al., 1998). The presences of
andesitic dykes and natural cokes in some Westphalian A coal seams in
the Zonguldak Basin shown by Karayiğit (1992) may suggest that the
good match between measured and calculated %Rr (Figs. 5 and 6a). In heat of potential magmatic intrusions is yet another factor to consider
total five scenarios were suggest for K20/K well. The first scenario and which may contribute, at least locally, to the elevated %Rr values of
considered no eroded coal measures and a normal continental heat flow the coal seams in the Kozlu Formation. However, volcanic rocks and/or
and, as like in K20/H well, the calculated and measured %Rr are not andesitic dykes and natural cokes are absent from the three studied
matched. The second and third scenarios calculated similar basal heat wells, and %Rr values of thermally unaffected Westphalian A coal
flow (63 mW/m2) and eroded coal measures (1700 m) pre-Cretaceous; seams in the Karadon and Üzülmez areas are also similar in range
however, the calculated and measured %Rr are matched good (Figs. 5 (0.96–1.42%Rr) with the studied coal seams (Karayiğit, 1992, 2001,
and 6a). The another scenario suggested for this well calculated 1000 m 2003). Therefore, the slightly higher %Rr values in the three studied
eroded coal measures. This scenario show that an integrated compac- wells seem to be related to different burial depths of the studied coal
tion fluid flow and heat carried by lateral fluid flow of 30 mW/m2 seams (448–1906 m) and coal seams in the Amasra area (c.
within lower parts of Karadon Formation from 145 to 129 Ma. This 120–1100 m) rather than the effect of a magmatic intrusion postdating
assumption does not match good at upper and lower parts of this well as the coalification.
like the third scenario. The final scenario calculated less eroded coal The studied coal samples from the Karadon Formation are of
measures (500 m) pre-Cretaceous. Furthermore, this scenario assume medium- to high-volatile A bituminous rank, according to ASTM D-388
an integrated compaction fluid flow and heat carried by lateral fluid (2015) classification. The coal samples from the upper parts of the
flow of 89 mW/m2 within lower parts of Karadon Formation from 145 Kozlu Formation are mostly medium-volatile bituminous coal and, in
to 129 Ma. This model is poorly match at the upper parts of Karadon parallel with the decreasing trend of volatile matter contents, coal
Formation. The higher basal heat flow calculated by this model might samples from the lower parts of this formation are generally of low-
have caused by Cretaceous andesitic dykes in the Zonguldak Basin. volatile bituminous rank. Besides one sample, coal samples from the
Overall, the calculated thickness of eroded Permo-Carboniferous cover Alacaağzı Formation are low-volatile bituminous coals. Alternatively,
might be around 2500 m at K20/H and 1700 m at K20/K. Presumably, the %Rr values along with the ash yield show that coals from the Kar-
the erosion is caused by Permian uplift in the Zonguldak Basin (Yalçin adon Formation are medium rank B, from the Kozlu are medium B to A
et al., 2002). Similar heat flows and erosion were also calculated from rank, and the Alacaağzı coal samples are medium A rank, according to
the Carboniferous Donets Basin that was affected Hercynian orogeny ECE-UN (1998) classification. The coal samples having higher than 50%
and erosion during the Permian period (Sachsenhofer et al., 2002, ash yield (on dry basis) are classified as carbonaceous rock in the

60
A.İ. Karayiğit et al.
studied wells. Similar differences among formations are also observed,
based on ISO 11760 (2005) classification. The coal samples from the
Alacaağzı Formation are of bituminous B (medium B) rank; from the
Kozlu Formation generally of bituminous (medium C-B) rank. The coal
seams in the lower parts of the Kozlu Formation in K20/G are of bitu-
minous A rank (%Rr ≥ 1.40). Finally, samples from the Karadon For-
mation are of bituminous C rank. All these indicate that coal seams in
the Alacaağzı and Kozlu formations in the three wells are of higher rank
than Namurian-Westphalian A coal seams in the Amasra area
(Karayiğit, 1992; Karayiğit et al., 1998; Yalçin et al., 2002). As men-
tioned above, this is probably a result of deeper burial depth and tec-
tonic deformation of Late Carboniferous coal seams in the study area.
61
International Journal of Coal Geology 187 (2018) 54–70
Fig. 6. Thermal and burial history curves for 1D basin
model of (a) K20/H and (b) K20/K wells (P: Pliocene, M:
Miocene, O: Oligocene, E: Eocene, Pa: Palaeocene, Carb:
Carboniferous).
4.4. Mineralogy
The XRD analyses show that raw coal samples are composed of clay
minerals (mainly kaolinite, illite, and lesser amounts of chlorite),
quartz, and carbonate minerals (Table 3). In some samples, pyrite and
feldspars were also identified as minor phases. The SEM analyses are in
agreement with the XRD results and, in addition, identified several
accessory minerals, particularly carbonate and sulphide minerals, such
as apatite, barite, biotite, cerussite, chalcopyrite, clausthalite, galena,
monazite, smithsonite, sphalerite, Fe-oxides, Ti-oxides, and zircon
(Table 3, Figs. 7–9).
Clay minerals are the dominant phases in all seams cored in K20/H
and K20/K; in contrast, in K20/G, clay minerals are dominant only in
some coal seams of the Karadon Formation (Table 3). Kaolinite is the
most common clay mineral and was detected in all studied samples. The
A.İ. Karayiğit et al. International Journal of Coal Geology 187 (2018) 54–70

Table 3
Composition of the coal samples from the Zonguldak Basin based on XRD and SEM (+++ = dominant phase > 20 wt%++ = abundant phase 20–5 wt%, + = minor phase < 5 wt
%, ± = detected in a few samples by XRD, a: accessory mineral detected by SEM-EDX).

Minerals Alacaağzı Fm. Kozlu Fm. Karadon Fm.

K20/H K20/K K20/G K20/H K20/K K20/G K20/H K20/K

Quartz + + ++ + + ++ + +
Clay Minerals +++ +++ ++ +++ +++ ++ +++ +++
Feldspars a a ± ± a + ±
Biotite a a a a a
Zircon a a a a a
Pyrite ± ± ± ± + + ±
Sphalerite a a a a a a a
Chalcopyrite a a a a
Galena a
Barite a a a a a a
Calcite + + ++ + ++ + + +
Dolomite/Ankerite + + ± + + ++ + ++
Siderite ± + ± ± ± ±
Cerussite a
Smithsonite a
Apatite a a a a
Monazite a a
Clausthalite a
Fe-oxides a a
Ti-oxides a a a a a

SEM data show that kaolinites are either individual bodies (vermi-
cules?) and/or aggregated with quartz, feldspars, apatite, zircon, bio-
tite, and chlorite crystals (Fig. 7a–d, f). Such associations are generally
observed within tonstein and/or altered tuff layers bearing coal seams
(Bohor and Triplehorn, 1993; Dai et al., 2003; Karayiğit et al., 2017a;
Permana et al., 2013; Zhao et al., 2012). Although tonstein layers were
not identified in the studied wells, their presence (0.5–20 cm) in coal
seams from the Kozlu and Karadon formations and minerals within
kaolonitic matrix were reported from several underground mines in the
basin (Burger et al., 2000). Well-ordered kaolinite in coals generally
correlated with tonstein layers (Ward, 2016); thus, in the studied wells,
the existence of well-ordered kaolinite in coal seams of the Karadon and
Kozlu formations seem to be related with synchronous volcanic inputs.
The Ti-traces from this kaolinitic matrix also imply that these originated
from altered volcanic inputs into palaeomires (Dai et al., 2015a;
Karayiğit et al., 2017a; Ward et al., 1999). Furthermore, zircon and
apatite crystals in a kaolinitic matrix mostly have sharp edges and/or
euhedral forms (Fig. 7d), which indicate short transport from the source
area into palaeomires (Spears, 2012). Thus, kaolinite along with asso-
ciated minerals (e.g., zircon, apatite) within the matrix presumably
originated from re-worked tuff and/or synchronous volcanic inputs into
palaeomires (Fig. 7a, b, d). Kaolinite occurs also as microfracture- and
maceral cavity/cell lumens-infilling (Fig. 8c, e, f, g). Such mineralisa-
tion of kaolinite could be related to authigenic precipitation during an
epigenetic stage (Dawson et al., 2012; Permana et al., 2013) and further
suggests that some kaolinite may have an epigenetic origin in the stu-
died coal seams. The SEM-EDX data also show that the clay mineral
matrix in the coal seams of the Alacaağzı Formation and the lower parts
of the Kozlu Formation is mostly illite and, like kaolinitic samples, such
matrices are associated with mineral matter and macerals (e.g., vi-
trodetrinite, fusinite). Such associations could indicate a higher clastic
input ratio from metamorphic and volcanic rocks from marginal areas
of the basin. Quartz occurs as abundant to minor phases in the coal
seams of K20/K and K20/H; however, it is the dominant phase in the
lower parts of the Kozlu Formation in K20/G. As mentioned above,
quartz is generally associated with a matrix of clay minerals (Fig. 7a, b,
d, e); thus, quartz has a detrital origin. Additionally, in some samples,
cleats and fractures are infilled by silica, and these infillings point to an
epigenetic origin for some quartz in the studied samples (Figs. 8g, 10e,
f). Feldspars are mainly represented by K-feldspar and plagioclase and
have a detrital origin. The dominance of silicate minerals in all the
studied samples could indicate the continuous clastic inputs into pa-
laeomires during Late Carboniferous. On the other hand, the presence
of fracture/cleat-infilling silicate minerals (kaolinite and silica) may be
evidence of the circulation of Si- and/or Al-rich solutions.
Calcite, dolomite, and ankerite/ferroan dolomite are generally
abundant phases, and siderite is identified as a minor phase in some
samples by XRD (Table 3). Siderite nodules are mostly observed within
a clay-mineral matrix and macerals and, in some cases, around pyrite
crystals and ankerite/ferroan dolomite infillings (Figs. 4d, 7d, 9a, b, h).
The SEM-EDX data show that there are two types of siderite nodules in
the examined samples: 1) siderite with Ca and Mn traces, and 2) Mg-
siderites with Ca traces. The low total-sulphur contents of the studied
samples suggest that siderite nodules could have been authigenically
precipitated within palaeomires during the Late Carboniferous, whereas
siderite overgrowth around pyrite crystals imply that the chemistry of
water in the palaeomires was also changeable (Dai et al., 2007, 2011;
Ward, 2016; Zhao et al., 2016). In addition, the siderite overgrowths
around ankerite/ferroan dolomite infillings may have also formed from
precipitation of Mg and Ca-rich solutions either in early diagenetic
stages or during coalification (Dawson et al., 2012; Uysal et al., 2000).
Calcite and dolomite/ankerite are commonly identified throughout the
well sections, and their distribution is irregular. These carbonate mi-
nerals are dominant phases where they occur as fracture/cleat-infillings
(Figs. 8a–c, 9a–f), particularly in the upper parts of the Karadon For-
mation in K20/H and K20/K and the upper parts of Kozlu Formation in
K20/K and K20/G. The SEM-EDX data showed that ankerite/ferroan
dolomite and calcite were the most common fracture/cleat-infillings.
Pure dolomite was detected rarely. In some cases, ankerite infillings
crosscut calcite and/or silica infillings. The common presence of car-
bonate minerals in cleats and fractures could be related to the circu-
lation of Ca-, Mg-, and Fe-rich solutions within the studied coal seams
during epigenetic stages. The source of such solutions could be leached
Cretaceous limestones in cover formations; however, this explanation
may apply in particular to the coal seams in the upper parts of the
Karadon Formation. Furthermore, the conglomerates in the Kozlu
Formation are cemented by calcareous material, and leached solutions
from these units might also be the source of Ca-rich solutions.
The deformation and brecciation of coal could allowed to penetra-
tion of hydrothermal solutions and generally resulted in variations of %
Rr values (Hower and Davis, 1981; Hower et al., 2001; Hower and
Gayer, 2002; Permana et al., 2013). Furthermore, %Rr anomalies could

62
A.İ. Karayiğit et al.
also be observed in Brecciated vitrinite macerals are observed in some
epigenetic carbonate-bearing samples. The severe tectonic deformation
during coalification could cause development of such deformed vitinite
structures (see Fig. 4g–h). Therefore, tectonic deformation of the Late
Carboniferous sequences in the basin presumably created fractures
within the coal seams that allow leached solutions to penetrate into
these formations via fault zones. Carbonate mineral infillings are
commonly observed, and accessory selenide minerals could also be
identified within cell-lumens. This could also explain variations in %Rr
values, in which epigenetic carbonates are generally dominant phases
as well as the presence of epigenetic clausthalite within some cell-lu-
mens (Fig. 8e–f). Within this context, the presence of accessory carbo-
nate minerals such as cerussite and smithsonite might be another in-
dicator of brecciation of coal seams; however, these minerals are
63
International Journal of Coal Geology 187 (2018) 54–70
Fig. 7. SEM backscattered images of crystalline phases in
the studied coal samples. (a) apatite (Ap), pyrite (py) and
chlorite (Chl) crystals associated with kaolinite (Kln); (b)
apatite (Ap), pyrite (py), quartz (Qtz), zircon (Zr) and
chlorite (Chl) crystals associated with kaolinite (Kln); (c)
individual kaolinite (Kln) crystals; (d) siderite (Sd), quartz
(Qtz), pyrite (Py), zircon (Zr) and alkali feldspar (Afs) as-
sociated with clay matrix (kaolinite); (e) quartz (Qtz), K-
feldspar (Kfs) and chalcopyrite (Ccp) associated with illite
(Ill); (f) association of plagioclase (Plg), alkali feldspar
(Afs), calcite (Cal) and biotite (Bt); (g) smithsonite (Smt)
within cerrusite (Cer) matrix; (h) element mapping of
image g.
identified only in one sample from the Karadon Formation (K20/K-1) in
SEM-EDX studies. Smithsonite crystals in this sample occur within a
cerussite matrix (Fig. 7g–h), and this association suggests clastic inputs
from alteration zones in metamorphic rocks from the basement rather
than precipitation of metallic-rich epigenetic solutions.
Pyrite is the only sulphide mineral detected by XRD (Table 3). Pyrite
crystals mostly have framboidal morphology and occur within a clay
mineral matrix as well as fracture/cleat infillings (Figs. 9a, e–g). Mas-
sive pyrites are also identified in some samples, but these are much less
common than framboids. These two forms indicate a dual origin for
pyrite crystals in the studied seams (Chou, 2012; Diehl et al., 2012).
Other micron-sized sulphide minerals identified by SEM-EDX within a
clay matrix are chalcopyrite, galena, and sphalerite (Table 3). The latter
is also identified as cell-lumen infillings and in fracture/cleat infillings
A.İ. Karayiğit et al.
(Figs. 8e–h and 9e–h) The presence of epigenetic sulphide minerals
suggests that circulated solutions within coal seams were also metal-
and S-rich (Dawson et al., 2012; Diehl et al., 2012). Barite in fracture/
cleat infillings can be another indicator for S-rich epigenetic solutions
(Figs. 8d, 9f).
Mineralisation in fractures and cleats shows that polymineralic as-
sociations are more common than monomineralic infillings. The pre-
sence of sulphur-bearing minerals (e.g., pyrite and barite) in the poly-
mineralic infillings suggests that S-rich solutions were initial epigenetic
solutions circulated within the studied seams. The overgrowths (e.g.,
siderite, ankerite) around fracture/cleat-infilling carbonate minerals
suggest that carbonate mineralisation in fractures/cleats developed in
two stages. The paragenetic sequences in fractures and cleats in the
studied coal seams are similar to hydrothermally influenced coals
(Diehl et al., 2012; Dai et al., 2015b; Hatch et al., 1976; Karayiğit et al.,
64
International Journal of Coal Geology 187 (2018) 54–70
Fig. 8. SEM backscattered images of crystalline phases in
the studied coal samples. (a) calcite (Cal) infillings in coal
cleat and overgrowth ankerite (Ank), ferroan dolomite (Fe-
Dol) aroun calcite infilling; (b) element mapping of image
b; (c) kaoloinite (Kln) and ankerite (Ank) infillings; (d)
pyrite (Py), barite (Brt) and calcite (Cal) infillings in coal
cleat; (e) kaolinite (Kln), calcite (Cal) and clausthalite
(Chal) infillings within cell-lumen (possibly fussinite); (f)
element mapping of image e; (g) kaolinite (Kln), calcite
(Cal), quartz (Qtz) and sphalerite (Sp) infillings within cell-
lumen and pore spaces; (h) element mapping of image h.
2017b; Permana et al., 2013). Even though the impact of andesitic
dykes was not observed in the studied wells, the hydrothermal solutions
originating from these dykes might have penetrated into the studied
coal seams. The calculated maximum palaeotemperature (115–169 °C)
of the studied coal seams could support this assumption; as a result,
fracture/cleat-infilling mineralisation is common. Influence of the
dykes could also explain relatively higher ash yields, total S, and vo-
latile matter contents of some coal samples where epigenetic miner-
alisation is common.
4.5. Elementary composition and mode of occurrence
The elemental composition on a whole-coal dry basis shows that
concentrations of Mg, Ca, and Ti are generally > 1000 μg/g in the three
wells (Table 4). The concentrations of elements P, Mn, Sr, and Ba are
A.İ. Karayiğit et al.
higher than 100 μg/g in the three wells (Table 4). Furthermore, in some
samples the concentrations of trace elements such as Co, Cu, Zn, Ge, Ce,
Rb, Zr, and Pb exceed 100 μg/g (Table 4). In comparison with most
world coals (Swaine, 1990), Th is the only element enriched in all coal-
bearing formations in the three wells studied, and elements Sc and Cs
are also enriched in the Kozlu and Alacaağzı formations. Cu, Ce, Rb, Nd,
Gd, and Dy are enriched in the Alacaağzı Formation in comparison with
most world coals (Table 4). The concentrations of most minor and trace
elements in the coal studied are higher than the world hard coals (Ketris
and Yudovich, 2009). No vertical trends in element concentrations were
identified within formations; however, higher concentrations are re-
corded mostly from the Kozlu Formation (Table 4). This could be re-
lated to higher ash yields of the samples. The average elemental con-
centrations in the studied wells are relatively higher than in other parts
of the Zonguldak Basin (Karayiğit et al., 2000; Karayiğit, 2001, 2003).
65
International Journal of Coal Geology 187 (2018) 54–70
Fig. 9. SEM backscattered images of crystalline phases in
the studied coal samples. (a) siderite (Sd) nodules embed
within maceral, and cleat-infilling ferroan dolomite (Fe-
dolomite); (b) siderite (Sd) overgrowth cleat-infilling an-
kerite (Ank); (c) calcite (Cal) infillings in coal cleat; (d)
ankerite (Ank)/ferroan dolomite (Fe-Dol) infillings in coal
cleat; (e) intermixed association of pyrite (Py), calcite (Cal)
and quartz (Qtz) in coal cleat; (f) clustered framboidal
pyrite crystals within maceral and intermixed association
of calcite (Cal), ankerite (Ank), quartz (Qtz) and barite
(Brt) within coal cleat; (g) pyrite (Py) within coal cleat and
illite (Ill) aggregates; (h) siderite nodules (Sd) and quartz
(Qtz) crystals, and sphalerite (Sp) infillings in cleat.
The conditions during peat accumulation and/or the presence of cir-
culated solutions within the studied coal seams may have caused these
differences.
Statistical methods for determining the mode of occurrence of ele-
ments in coal are widely applied; however, there are some objections,
particularly related to ash-based data, for statistical approaches (Drew
et al., 2008; Geboy et al., 2013). The accuracy problem could be
overcome by using direct methods such as SEM-EDX (Eskanazy et al.,
2010; Huggins, 2002; Karayiğit et al., 2017a). The element Ti is the
only major element that shows moderate positive correlation with ash
yield and also has moderate to strong positive correlations with Mg, Zr,
Nb, Ta, Th, and most of the rare earth elements (REEs) (Table 5). These
elements, except for Mg, also show a strong correlation with ash yield.
As mentioned previously, clay minerals are dominant phases (kaolinite
and illite) in the studied samples, and Ti is also traced from clay
A.İ. Karayiğit et al. International Journal of Coal Geology 187 (2018) 54–70

Table 4
Summarized ranges and weighted averages of the elements (in μg/g, except otherwise cited) from the Zonguldak Basin and their comparison with worldwide coals (Fm.: formation).

Elements Alacaağzı Fm. Kozlu Fm. Karadon Fm. Most world coalsa Clarke values (for hard-coals)b

Range Avg. Range Avg. Range Avg.

Ca, % 0.09–2.63 0.42 0.08–40.48 10.88 0.07–17.65 6.17 – –

Mg, % 0.28–3.21 1.11 0.47–11.19 2.74 0.04–3.56 1.46 – –
Ti, % 0.09–3.99 1.19 0.05–4.64 1.52 0.02–5.29 1.08 0.1–2 0.89
Be 2.8–13.2 4.5 < 0.83–12.00 3.0 < 1.3–12 3.8 0.1–15 2.0
P 70.1–737.4 330.4 16–1819 278 8.1–4087 645 1–3000 47
Sc 10–32 17.6 1.4–24 7.0 1.8–20 6.4 1–10 3.7
Mn 46–319 141.1 10–940⁎ 187 16-494⁎ 119 5-300 71
Co 8.7–36 17.8 1.8–46 9.5 3.5–210 11 0.5–30 6
Cu 31–119 53.2 8.9–169 29 11–75 27 0.5–50 16
Zn 17–134 50.0 2.7–627 32 6.9–829 34 5–300 28
Ga 5.9–29 16.3 2.0–33 10 3.2–30 13 1–20 6.0
Ge < 0.7–2.7 2.3 < 0.13–21 0.90 < 0.41–175 2.5 1–50 2.4
Rb 18–194 73.1 2.0–249 44 0.87–141 16 2–50 18
Sr 84–308 195.2 31–1353 161 19–1335 142 15–500 100
Y 16–35 24.5 2.6–53 13 6.6–49 16 2–50 8.2
Zr 34–198⁎ 72.3 12-312⁎ 65 11-248 80 5-200 35
Nb 2.9–17 10.5 1.1–30 7.3 1.3–26 10 3–30 4.0
Mo 1.5–4.5 2.4 0.54–30 3.3 1.6–85 5.2 0.1–10 2.1
Cs 1.9–20 11.2 0.27–51 8.4 0.10–23 2.5 0.1–5 1.1
Ba 277–1274 567.3 16–2121 323 74–1201 240 20–1000 150
La 11–57 31.3 4.2–72 21 2.1–55 25 1–40 11
Ce 22–138 68.0 8.3–136⁎ 41 4.8-109 48 2–70 23
Pr 2.6–15 7.7 0.90–15 4.7 0.67–13 5.3 1–10 3.4
Nd 11–66 32.5 3.1–57 18 2.8–48 19 3–30 12
Sm 2.3–12 6.0 0.62–11 3.6 1.1–8.9 3.7 1–6 2.2
Eu 0.8–2.2 1.4 0.13–4.5 0.92 0.36–2.1 0.9 0.1–2 0.43
Gd 2.9–12 6.3 0.64–11 3.7 1.4–8.9 3.8 0–4 2.7
Tb 0.5–1.8 1.0 0.10–1.6 0.5 0.24–1.3 0.6 0.1–1 0.31
Dy 2.8–11 5.8 0.63–9.4 3.1 1.5–7.4 3.3 1–4 2.1
Ho 0.6–2.4 1.2 0.11–2.1 0.62 0.28–1.4 0.6 0.1–2 0.57
Er 1.5–5.5 3.0 0.25–6.5 1.6 0.75–4.2 1.8 1–3 1.0
Tm 0.2–0.9 0.5 0.03–1.0 0.25 0.11–0.64 0.3 0.5–3 0.3
Yb 1.2–5.7 3.0 0.16–7.1 1.6 0.66–4.4 1.7 0.3–3 1.0
Lu 0.2–0.7 0.4 0.02–1.2 0.23 0.09–0.77 0.3 0.03–1 0.2
Ta 0.2–2.7 1.1 0.08–3.6 0.77 0.06–2.5 1.0 0.1–2 0.3
W 0.8–3.9 2.3 0.47–9.4 2.9 0.70–15 3.3 0.5–5 0.99
Tl 0.2–1.1 0.6 0.05–3.6 0.69 0.07–5.4 0.7 < 0.2–1 0.58
Pb 17–61 34.0 2.6–128 34.0 14–315 38 2–80 9
Bi 0.2–0.9 0.5 0.06–1.9 0.55 < 0.10–3.0 0.9 2–20 1.1
Th 3.4–25 13.7 1.9–54 14 1.1–38 16 0.5–10 3.2
U 1.7–13 5.7 0.84–20 5.6 1.1–80 7.5 0.5–10 1.9

a
From Swaine (1990).
b
From Ketris and Yudovich (2009).
⁎
Over detection limit of ICP-MS.

Table 5
Elemental affinities deduced from the calculation of Pearson's correlation coefficients.
Correlation with ash yield (0.7 < r < 1.0)
Ce, Ga, Nd, Pr, Rb, Sc, Sm
Correlation with ash yield (0.4 < r < 0.7)
Ti, Ba, Cs, Cu, Dy, Er, Eu, Ho, La, Lu, Nb, Pb, Ta, Tb, Th, Yb, Y, Yb, Zr
Correlation with Ti content (0.4 < r < 0.7)
Mg, Ce, Dy, Eu, Ga, Gd, La, Nb, Nd, Pr, Sm, Tb, Th, Y, Zr
Correlation with total sulphur (0.5 < r < 0.1)
Co, Mo, Pb, Tl, U, Zn
Correlation with Cu content (0.5 < r < 0.7)
Ba, Ce, Cs, Dy, Eu, Ga, Gd, Ho, La, Lu, Nd, Pr, Rb, Sm, Tb, Tm, Y, Yb, Zr
minerals and biotite. All this suggests that Ti and associated elements
are derived mainly from aluminosilicate minerals. Nevertheless, ac-
cessory minerals (zircon, Ti-oxides, apatite, and monazite) within the
clay matrix (particularly a kaolinitic one) could be other sources for Ti,
Zr, and REEs in the studied samples. Clearly Ti and associated elements
have a strong inorganic affinity. Considering the presence of pyr-
oclastic/kaolinitic tonstein layers in the coal-bearing formations in
different parts of the basin and a kaolinitic matrix with other minerals
in the studied samples, these elements could have been derived from
volcanic input along with clastic inputs from metamorphic and mag-
matic rocks on the basement. This could also explain their relatively
high concentration in the Kozlu and Karadon formations (Table 4).
Similar associations are also reported from tonstein/altered tuff-bearing
coal seams as well as the Amasra area of the basin (Dai et al., 2003,
2007; Hower et al., 1999; Karayiğit, 2001, 2003; Karayiğit et al., 2017a;
Li et al., 2017; Zhao et al., 2016).
Calcium shows relatively high concentrations for the studied coals
and displays no correlation with ash yields or any other elements. The
epigenetic carbonate-mineral-bearing samples have high Ca con-
centrations; thus, Ca has a mainly inorganic affinity. Data from SEM-
EDX show that elements like Mg, P, and Mn are present in siderite and
ferroan dolomite/ankerite. Thus, Mg, P, and Mn are derived partly from
carbonate minerals in the studied samples. The circulated solutions
leached from cover units and/or conglomerates could bring additional
Ca and Mg into the studied coal seams. Their precipitation in fractures
and cleats elevated Ca and as well as Mg concentrations in certain coal
seams. The syngenetic siderite nodules imply that Ca2 +-rich water
supply into palaeomires could also be a source for Ca in the studied
samples. Furthermore, Ca is partly derived from apatite crystals within
a kaolinitic matrix; therefore, the limited proportions of Ca are likely

66
A.İ. Karayiğit et al.
derived from clastic inputs into palaeomires. Concentrations of P are
variable in the studied wells (Table 4).
The elements Ba, Cu, and Pb also show a moderate to strong cor-
relation with ash yields (Table 5). The SEM data showed the existence
of several sulphur-bearing accessory minerals in the studied samples.
Barite was commonly identified in the fracture/cleat infillings, parti-
cularly in the Alacaağzı Formation, and Sr was also traced in barite.
Like for epigenetic carbonates, circulated solutions may have brought
Sr and Ba into the studied coal seams; furthermore, these solutions
could have also caused the weathering of feldspar during the diagenetic
stage. Therefore, liberated Ba and Sr from feldspars could also pre-
cipitate within fractures and cleats. As noted previously, chalcopyrite,
sphalerite, and galena are commonly observed within cell-lumens and
fractures/cleats. These minerals are the source for Cu, Zn, and Pb in the
studied samples; thus, these elements have sulphide affinity. This affi-
nity is also supported by their positive correlations with total sulphur
contents (Table 5). Additionally, total sulphur contents show positive
correlations with Co, Mo, and U. The correlations between U and total
sulphur contents is possible related to anoxic conditions during peat
accumulation rather than geochemical affinity. The element U is gen-
erally enriched in anoxic palaeomire conditions (Siavalas et al., 2009).
The accessory Zn- and Pb -bearing carbonate minerals and clausthalite
are other minor sources for Zn and Pb in the studied coal samples (see
Figs. 7g–h and 8e–f). All these suggest that elemental enrichments in
the studied seams are mainly controlled by epigenetic factors and to a
lesser extent by syngenetic factors. The clastic input ratio from the
margins of the basin and/or re-worked tuffs probably controlled the
concentrations of aluminosilicate-affiliated elements (e.g., Ti, Zr). The
circulated solutions leached from cover formations presumably brought
additional Ca and Mg and/or re-distributed metallic elements (e.g., Cu,
Zn, Pb). These elements are enriched where epigenetic mineralisation
took place in cleats and fractures. The metallic element enrichments are
related to fracture/cleat-infilling sulphide minerals. As noted earlier,
epigenetic sulphide minerals and silica fracture/cleat infillings in the
studied seams could be related to circulated hydrothermal solutions,
and, in such cases, metallic element enrichments are commonly re-
ported (Dai et al., 2015b; Diehl et al., 2012; Karayiğit et al., 2017b;
Zhang et al., 2004). This could explain the correlations between total
sulphur content and metals-sulfophiles (e.g., Pb, Zn) in the studied
seams.
4.6. Coal facies and depositional environment
The coal facies analysis, combined with sedimentological, miner-
alogical, geochemical, and palynological data, can be a useful method
for interpreting palaeoenvironmental conditions (Bechtel et al., 2014;
Jasper et al., 2010; Karayiğit et al., 2017a; Siavalas et al., 2009; Silva
et al., 2008); however, still some criticism exists about their applic-
ability, particularly for Cenozoic coals (Crosdale, 1993; Moore and
Shearer, 2003). The Tissue Preservation Index (TPI) and Vegetation
Index (VI) values of the coal seams in the Alacaağzı Formation are
generally < 1.0 (Fig. 10). These values suggest that the preservation of
organic matter is low and herbaceous vegetation was common during
the Namurian. The previous palynological data and macrofloral data
from various parts of the Zonguldak Basin documented sporomorphs of
small ferns and herbaceous plants from coal seams in the Alacaağzı
Formation (Ağralı, 1964; Akgün and Akyol, 1992; Cleal and van
Waveren, 2012; Nakoman, 1975). Low TPI values are typical of such
small fern-dominated associations and/or low arborescent plant density
in the palaeomire surface (Izart et al., 2015; Jasper et al., 2010). Fur-
thermore, these studies reported increases in tree ferns and lycopod tree
sporomorphs in the upper parts of the Alacaağzı Formation and the
transition from Namurian to Westphalian A (Ağralı, 1964; Akgün and
Akyol, 1992; Akyol, 1972; Nakoman, 1975). Vertical distribution of VI
and TPI values of Namurian coal seams in K20/K show that higher TPI
values were recorded from the central parts and display decreasing-
67
International Journal of Coal Geology 187 (2018) 54–70
upward trends. These slight decreases at the upper parts of Alacaağzı
Formation in K20/K are likely related to the increase in clastic inputs
into the palaeomire. Thus, clastic quartz associated with clay minerals
(mostly illite) and vitrodetrinite are common, and mineral-matter
contents (as determined under reflected light microscopy) become
elevated upwards in Namurian coal seams cored in K20/K. Increased
sediment-laden water influx and/or higher energy conditions might
have terminated conditions favourable for tree-fern-dominated mire
development in the study area, and varied Gelification Index (GI) and
Groundwater Index (GWI) values were recorded within the Alacaağzı
Formation (Fig. 10).
Samples from the Kozlu Formation are generally characterized by
relatively higher TPI and VI values than from other formations. The
data placement on both diagrams indicates that the preservation of
organic matter was good and arborescent plants were common peat-
forming plants during Westphalian A in the study area (Fig. 9). The low
TPI and VI values (< 1.0) also imply that herbaceous vegetation oc-
casionally became dominant in palaeomires (Fig. 10). The palynolo-
gical data from K20/G and K20/K, and previous palynological and
macrofloral data from other parts of the basin were also in agreement
with the coal facies data (Ağralı, 1964, 1970; Akgün and Akyol, 1992;
Akyol, 1972; Cleal and van Waveren, 2012). The lycopod tree and tree
fern sporomorphs are commonly identified from the coal seams in the
Kozlu Formation, and small fern and herbs sporomorphs were docu-
mented in various proportions. High vitrinite, particularly telovitrinite,
contents in this formation is another piece of evidence of the dominance
of lycopod trees and tree ferns in palaeomires (Eble et al., 1999; Eble
and Greb, 2016; Greb et al., 1999; Mastalerz et al., 2017). The relatively
low GWI values of the studied samples from this formation (0.1–1.0) are
presumably related to the predominance of ferns, whereas GWI values
higher than 1.0 point to standing water conditions in palaeomires
(Jasper et al., 2010). The sedimentological data of this formation shows
that the palaeomires developed within a flood-plain environment
during Westphalian A (Yalçin et al., 2002). In such conditions, tree
ferns are common vegetation, and GI values > 10.0 are another in-
dicator for such vegetation (Greb et al., 2006; Jasper et al., 2010;
Phillips and Peppers, 1984). Furthermore, high GWI values (> 10.0)
are observed in clay-bearing samples that indicate flooding events into
palaeomires (Fig. 10).
No trends for coal facies indices were observed throughout the
Kozlu Formation in the studied wells, and this suggests that water tables
within palaeomires often fluctuated during Westphalian A. The TPI and
VI values of the Karadon Formation are generally around 1.0; and the
data implies that the peat-forming vegetation was composed of mix-
tures of small ferns and tree ferns. Similar vegetation associations were
also reported by palynological data from the Karadon Formation in the
studied wells and other parts of the basin (Ağralı, 1970; Akyol, 1972;
Akgün and Akyol, 1992,). The relatively high TPI and VI values (≥ 1.5)
in some samples could be an indicator for short-term increases in ar-
borescent plants within palaeomires during the deposition of the Kar-
adon Formation (Fig. 10). The medium GWI and GI values of this for-
mation are possibly related to the common existence of ferns in the
palaeomires as well as a transition between topogenous to om-
brogenous mires (Jasper et al., 2010). High inertinite contents
(≥ 20.0%, on whole coal basis, see Fig. 4b) and the existence of ma-
crinite in Kozlu and Karadon formations could imply very low water
levels in palaeomires or fire events; however, the macerals in the in-
ertinite group are mostly associated with collodetrinite and clay mi-
nerals. This suggests that inertinite macerals have a mainly allochtho-
nous origin rather than an oxidative environment in palaeomires
(O'Keefe et al., 2013).
Overall, the coal facies analysis shows that, precursor peats accu-
mulated in a limno-telmatic environment under mesotrophic condi-
tions, where ferns are a common vegetation during the Late
Carboniferous. Additionally, precursor peats of some coal seams in the
Kozlu Formation accumulated under pure telmatic conditions, and
A.İ. Karayiğit et al.
arborescent plants covered palaeomire surfaces. Considering sedi-
mentological data from coal-bearing formations in the basin, palaeo-
mires likely developed along lake shores within deltaic environments.
The water table was unstable but it continually covered the peat sur-
face. Fluctuation in the water table is probably related to flooding
periods that are common in deltaic environments; therefore, clastic
inputs were high. The syngenetic siderite nodules and framboidal pyrite
crystals are generally observed in samples having high GI values. This
implies that authigenic mineral formations seem to have occurred
during high water table conditions in palaeomires. The Ti-bearing
kaolinitic matrix and pyrite crystals point to acidic conditions within
palaeomires during the Late Carboniferous (Dai et al., 2015b; Ward
et al., 1999). However, the coexistence of syngenetic pyrite crystals and
siderite nodules in some samples implies an occasional shift toward
neutral to weak alkaline conditions in the palaeomires (Karayiğit et al.,
2017a).
5. Conclusions
The Late Carboniferous coal seams in the K20/G, K20/H, and K20/K
wells in the Zonguldak Basin are of bituminous rank and are char-
acterized by total sulphur contents. Relatively higher %Rr values in the
wells studied compared to other parts of the Zonguldak Basin and in-
creasing reflectance trends toward the lower part of the wells seem to
be a result of burial depths in this part of the basin. The coal facies data
show that a palaeomire developed mostly under limno-telmatic condi-
tions, whereas telmatic environments were more common in palaeo-
mires of the Kozlu Formation. The water table fluctuated in
68
International Journal of Coal Geology 187 (2018) 54–70
Fig. 10. GI vs. TPI plot of the coal samples from sampling
profile (after Diessel (1992; b) VI vs. GWI plot of the coal
samples from sampling profile (after Calder et al., 1991.
palaeomires, with frequent clastic inputs from the marginal areas.
Therefore, clastic minerals are generally dominant phases in the studied
seams. The presence of a kaolinitic matrix associated with accessory
minerals (e.g., apatite, zircon) suggest synchronous volcanic inputs into
palaeomires within the Kozlu and Karadon formations. In addition,
periods of relatively higher water tables allowed the formation of au-
thigenic minerals in palaeomires. The differences in elemental compo-
sitions of syngenetic siderite nodules and siderite overgrowth around
pyrite crystals imply fluctuating redox conditions in the palaeomires.
Calcite and ankerite/ferroan dolomite are the most common fracture/
cleat-infilling minerals, but epigenetic sulphide minerals, together with
kaolinite and silica, are also observed. Because tectonic evolution of the
basin resulted in the deformation of coal-bearing formations and the
development of several fault zones in the basin, basinal solutions could
penetrate into the studied coal seams. The precipitation of basinal so-
lutions caused the formation of epigenetic minerals within fracture/
cleats as well as cell-lumens of the macerals. Consequently, elemental
enrichments (e.g., Ca, Ba, Zn) in certain coal seams developed, and the
ash yields, total sulphur, and volatile matter contents of these seams are
elevated to very high. These solutions seem to have originated mainly
from leached cover formations and/or hydrothermal solutions origi-
nating from dykes within the basin. All these data suggest that the
tectonic deformations of the basin after the Carboniferous period had a
great impact on the coal characteristics of the Late Carboniferous coal
seams in the studied part of the Zonguldak Basin.
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.coal.2017.12.007.
A.İ. Karayiğit et al.
Acknowledgments
This study was partly supported by Turkish Scientific and
Technological Research Council of Turkey (TÜBİTAK) under the project
YDABCAG-70 and also by Scientific Projects Coordination Unit of
Hacettepe University under the project 014D02602003. Dr. Karayiğit
performed the petrographic, SEM, and mineralogical examinations. Dr.
Gayer performed ICP-MS and some XRD analyses and thermal model-
ling. Dr. Oskay analysed the coal facies. Dr. Karayiğit together with Drs.
Oskay and Mastalerz interpreted the data and constructed the paper.
The preliminary results of this study were presented at 67th Geological
Congress of Turkey and 67th Annual Meeting of the ICCP. The authors
would like to thank Prof. Dr. M. Namık Yalçın (İstanbul University) for
permission to use the samples from the K20/G well and to Asst. Prof.
Dr. İbrahim Buzkan (Bülent Ecevit University) for his help during
sampling. Special thanks to Prof. Dr. Ralf Littke for permission to use
the coal petrography laboratory at RWTH Aachen University. The first
author also thanks the Fulbright of Turkey Branch for funding a sci-
entific research visit to Indiana University. Finally, authors would like
to thank anonymous reviewers for their comments and suggestions.
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