Organic Matter Type, Maturity, Depositional Environmental

Subscriber access provided by University of Glasgow Library

Fossil Fuels

Organic Matter Type, Maturity, Depositional Environmental Characteristics and Liquid Hydrocarbon Potential of Late Carboniferous Kozlu Bituminuos Coal and Coaly Shale Beds (Zonguldak-Amasra Basin, NW Anatolia,Turkey): An Application of Biomarker Geochemistry Reyhan Kara-Gülbay, Gülten Yaylali-Abanuz, Sadettin Korkmaz, Mert Samet ERDO#AN, Fatma HO# ÇEB#, Selin ÇEV#K, and Elif A#IRMAN-AKTÜRK Energy Fuels, Just Accepted Manuscript • DOI: 10.1021/acs.energyfuels.9b01528 • Publication Date (Web): 02 Sep 2019 Downloaded from pubs.acs.org on September 2, 2019

Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.

is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.

Page 1 of 41 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

Organic Matter Type, Maturity, Depositional Environmental Characteristics and Liquid Hydrocarbon Potential of Late Carboniferous Kozlu Bituminuos Coal and Coaly Shale Beds (Zonguldak-Amasra Basin, NW Anatolia,Turkey): An Application of Biomarker Geochemistry R. Kara-Gülbaya*, G. Yaylalı-Abanuza, S. Korkmaza, M. S. Erdoğana, F. Hoş-Çebia, S. Çevika and E. Ağırman-Aktürkb a b

Department of Geological Engineering, Karadeniz Technical University, Trabzon, Turkey. Department of Geological Engineering, Oltu Earth Science Faculty, Atatürk University, Erzurum, Turkey.

ABSTRACT Upper Carboniferous (Westphalian A) Kozlu Formation consisting chiefly of sandstone, thick coal layers, shale and conglomerate levels crops out in the Zonguldak-Amasra Basin, NW Anatolia. Kozlu Formation contains a total of 20 mineable coal layers with thickness varying from 0.5 to 6 m. The lower level of formation is represented by lacustrine deposits whilst upper part is made up with thick flood plain sediments and meandering river deposits bearing laterally continuos coal levels. In this study, coal samples taken from coal layers within the Kozlu Formation at the Kozlu Underground Coal Mining site were evaluated by using the data obtained from pyrolysis/TOC, GC and GC-MS. The average TOC (total organic matter) value of Kozlu coals is 40.28%. The coals are characterized with relatively high HI (hydrogen index) value (average 262 mgHC/gTOC) and very low OI (oxygen index) value (2 mg CO2/gTOC). Pyrolysis data indicate that coals contain dominantly Type II and less amount of Type III kerogen and Tmax values range from 454 to 468ºC. In gas chromatographs, the recorded distribution consists predominantly of low-carbon numbered n-alkanes and subordinately of high-carbon numbered n-alkanes and TAR (terrigenous/aquatic ratio) value is very low (0.05-0.09). Pristane abundance is greater than phytane and Pr/Ph ratios are in the range of 1.11 to 1.60. The sterane abundances in the Kozlu coals is in the following order C29>C28>C27. Coals have high C19 and C20 tricyclic terpane concentrations and high (C19+C20)/C30 ratio, high C30* (diahopane) and C29Ts concentrations and high C30*/C29Ts ratio and low C31R/C30 and C29/C30 hopane ratios. DBT/P ratio of Kozlu coals is found to be very low (0.04-0.14). Based on the pyrolysis and biomarker data, the Kozlu coals are interpreted as being deposited in a suboxic-oxic continental environment in which there is effective input of clay and dominantly terrestrial (with significant lipid-rich components) and bacterial organic matter. High Tmax values, CPI values close to 1, low moretane/hopane (0.23-0.12), equilibrated 22S/(22S+22R) homopane (for C32), 20S/(20S+20R) C29 sterane (0.52-0.54) and TA(I)/TA(I+II) steroid ratios, high  sterane (0.51-0.55), C30*/C29Ts, C30*/(C30*+C30H), MPI-3 (1.241.41), MDR and MA(I)/MA(I+II) steroid are indicative of mature-late mature organic matter. Ro *Corresponding author E-mail: [email protected] ACS Paragon Plus Environment

Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

values between 0.9−1.25% determined from Tmax (454-468°C) values indicate "high volatile bituminous B-medium volatile bituminous" rank for Kozlu coal. Kozlu coals with HI values (up to 331 mg HC/gTOC) extremely higher than classical coals indicate that these coals have significant oil and gas generation potential and high S1 (average 6.04 mg HC/g rock) and S2 (110.08 mg HC/g rock) values imply that they generated notably high amount of liquid hydrocarbon and still have generation potential. Key words: Zonguldak-Amasra Basin, bituminous coal, n-alkane, biomarker, maturity, deposition environment, hydrocarbon potential 1. INTRODUCTION The Zonguldak-Amasra Basin hosts the most important bituminous coal deposits of Turkey. The coals in this basin were started to be exploited in 1848 and coals are currently mined at the Armutçuk, Kozlu, Üzülmez, Karadon and Amasra sites by the TTK (Turkish Hard Coal Enterprise). Exploration studies carried out in the basin revealed a total reserve of 1.5 billion tons of coal to a depth of -1200 m of which nearly 50% is proved reserve. Since 1942, for which reasonably reliable records are available, 246 million tons bituminous coal has been mined from the basin (exceeding 400 million tons since 1865) [1]. Carboniferous (Northern hemisphere-Laurasia coals) and Permian (Sothern hemisphereGondwana coals) bituminous coals are common across the world. The Laurasia coals comprise bituminous coals in North America, Europe and Asia whereas Gondwana coals comprise Permian bituminous coals in Australia, South Africa, Madagascar, and India [2]. The collision between Gondwana and Laurasia which started in Mississippian and continued through Pennsylvanian and Permian periods resulted in the closure of Rheic and Paleotethys oceans and thus, formation of super continent Pangaea by the assembling of all earlier continents [3,4]. During the Late Carboniferous, North America, Europe and China were located in the equator region which was quite suitable for the plant growth. Particularly wide coastal plains in the USA and Europe were covered with swamp forests consisting of tall trees. These forests facilitated the development of today’s paralic anthracite and bituminous coal occurrences. The Late Carboniferous paralic bituminous coal deposits in Europe are found in Great Britain, Belgium, North Germany-Ruhr, Poland and Spain whilst limnic bituminous coal basins of the same period are located in France, south Germany-Saar, Hungary and Romania [2]. During Permian, a cold and moisture climate regime was reigned in South Africa and widespread coal deposits were formed on flood plains and upper delta plains as a result of plant growth favoring cold climate conditions [5]. In Europe and North America, however, arid conditions prevailed and wide swamp areas and plant cover of Late Carboniferous disappeared.

2 ACS Paragon Plus Environment

Page 2 of 41

Page 3 of 41 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

Carboniferous rocks of the İstanbul Zone [6] have outcrops between İstanbul and Zonguldak districts. The İstanbul Zone covers a limited area in SW Black Sea region and during Middle Cretaceous-Paleocene it was separated from the Moesian platform to the north and moved southerly by western Black Sea and western Crimean transform faults. By the closure of the Intra-Pontide Ocean in the Early Eocene, the İstanbul Zone and Sakarya Zone were collided and assumed their present-day configuration [7, 8]. Sequences of the İstanbul Zone are quite different from other tectonostratigraphic units in NW Anatolia and stratigraphically resemble to the Paleozoic rocks exposing in southern margin of Laurasia and a belt between Western Europe and southern Urals [6, 9, 10, 11, 12]. Oplustil et al. [13] determined the Lower Asturian hiatus in between Karadon and Kızıllı Formations in the Zonguldak-Amasra Basin and suggested that the Lower Asturian hiatus has several equivalents in other Variscan basins of Europe (Dobrudzha, Upper Silesian, Intra-sudetic and central and western Bohemian basins). Oplustil et al. [13] also pointed out that tectono-sedimentary similarity they obtain is in good agreement with paleogeographic position of Zonguldak-Amasra Basin at the eastern continuation of the Central European basins and along the southern margins of Laurasia. Coal-bearing units of Zonguldak-Amasra Basin are found in Carboniferous Alacaağzı, Kozlu and Karadon formations [14, 15]. Kerey et al. [16] described a fourth formation, Kızıllı Formation, at the upper part of the sequence. Coals of Namurian-Westphalian A aged Alacaağzı Formation occur as lenticular layers with thickness of 10 cm to 1 m of limited lateral extansion and therefore do not have any economic value [17]. In the region, coals have been mined from Westphalian A aged [18] Kozlu and Westphalian BC aged [16] Karadon formations. The Zonguldak-Amasra Basin has attracted interest from several researchers due to its Carboniferous aged bituminous coal deposits with large reserve and economic potential. There are a lot of works done with different purpose in the area. Karayiğit et al. [19], Karayiğit et al. [20], Karayiğit et al. [21] and Taşçı [22] studied petrographical properties of Carboniferous coals, Yahşiman [23, 24], Akgün and Akyol [25], Cleal and van Waveren [26] and Cleal et al. [27] described the flora of coal bearing deposits. Hoşgörmez et al. [28], Yalçın [29], Hoşgörmez et al. [30], Karacan and Okadan [31], Özgökçe and Yalçın [32] and Yalçın et al. [33] studied the gas occurrences in the Zonguldak-Amasra coal basin and Konyalı [34], Kerey et al. [16] and Karayiğit and Orhan [35] investigated the sedimentological and stratigraphic development of the basin and Okay et al. [6] studied tectonic evolution of the region. Organic geochemical characteristics of Upper Carboniferous coals in the region have not been studied and therefore, in the present study we investigated pyrolysis/TOC, n-alkane and isoprenoid, saturated (sterane, terpane) and aromatic (MA and TA steroids, MP) hydrocarbon and MDBT components of coals from Westphalian A Kozlu Formation which comprise the significant part bituminous coal reserve in the Zonguldak-Amasra region. The biomarker data were evaluated in regard with organic matter type, maturity and depositional environment characteristics of coals and were correlated with the results of previous studies.


Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Although sapropelic boghead and cannel coals are the main source of oil, they contribute only 10% to the world reserve [36]. Methane is the major hydrocarbon released from humic coals which may form commercially significant gas accumulations and thus they are regarded as important source rock for oil [37,38,39,40]. In some cases, coals may also generate commercially feasible oil [41,36,40] and a few oil accumulations are found to be derived coals [42]. The Mahakam Delta area in Indonesia [43,44] and oil fields in Australia, China, USA, Canada and New Zealand are some of examples for coal-derived oils [42]. One of the aims of this study is to examine the Kozlu bituminous coals by means of liquid hydrocarbon (oil) generation. For this reason, oil/natural gas generation ability and current oil/natural gas generation potential of Kozlu bituminous coals were investigated. 2. GEOLOGICAL SETTING Hamzafakılı Formation consisting of Paleozoic quartzite and micro conglomerates comprise the basement rocks in the study area (Fig 1, 2a) [41,52]. The Göktepe Formation represented by metasandstone, metasiltstone and metaclaystone grades in to the Hamzafakılı Formation and the sequence continues upward with middle Devonian-Visean Yılanlı Formation [53]. The Yılanlı Formation is made up of limestone, dolomite, cherty limestone and shale alternation at the bottom and thick bedded limestone to the top. Carboniferous Alacaağzı, Kozlu and Karadon Formations are the coal-bearing units of the basin. The Alacaağzı Formation consisting of interbedded sandstone, siltstone, mudstone and coal layers overlies conformably the Yılanlı Formation. Sandstone, siltstone and mudstone within the unit form upward coarsening cycles and were interpreted as deltaic sequence by Kerey et al. [16]. The lower part of sequence comprises chiefly mudstone and wackestone bearing marine fauna. Coal levels within the unit were formed episodically in delta flat environment which resulted in the formation of ephemeral peat bog occurrences [13, 16]. The unit continues upward with alternation of marine and delta flat sediments and ends up with a dominant sandstone level. In the Paleozoic sequence around Zonguldak, the age of Namurian-Westphalian A was suggested for the unit [17]. Coal layers of Alacaağzı Formation occur between claystone and siltstone levels. These coal beds are lenticular with thickness varying from 10 cm to 1 m and do not have an economic value since lateral extansion is limited. The Kozlu Formation was deposited over the Alacaağzı Formation with a gradual transition. Kerey et al. [16] stated that the lower part of Kozlu Formation was represented by lacustrine deposits whilst the upper part is characterized by flood plain deposits that contain thick coal levels with lateral continuity and other parts of formation are comprised by meandering river deposits. The thickness of unit is 800 m around Bartın and Zonguldak and 0-300 m in the Armutçuk region [48]. Coal layers have thickness of 0.5 to 6 m and the unit contains mineable 20 coal layers [18]. Footwall and cap rocks of coal layers are composed mostly of claystone and siltstone [48]. The unit was suggested to be Westphalian-A in age [18]. In the region, the Kozlu Formation is conformably overlain by the 4 ACS Paragon Plus Environment

Page 4 of 41

Page 5 of 41 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

Karadon Formation. The unit is composed predominantly of coarse sandstone and conglomerates and subordinately of coal and less siltstone, mudstone and refractory clay (fire clay) interbeds. The units of the Karadon Formation were interpreted as braided river deposits and alluvial fan deposits. Based on plant fossils, the age of unit is Westphalian-BC [16]. Coaly units in the basin are unconformably overlain by Permo-Triassic, Jurassic, Cretaceous and Tertiary units. There are several coaly levels within the Kozlu Formation and in the present study coal levels so called Çay, Acılık, Domuzcu, Büyük and Kesmeli of the Kozlu Underground Coal Management were studied (Fig. 2b). Clay layers occur at the basement of the coal level in the upper part of Kozlu Formation, so called Çay Level (Fig 2b, 3d). In this level a coal sequence of 3 m thick was measured and the roof of coaly level could not be recognized within the gallery. At the bottom of this coaly level there is a claystone interlayer with thickness of 50 cm (Fig. 3d). The Acılık coal layer was measured as about 5.1 m and claystone layer are present both the top and base of coal the layer. The coal level is homogeneous and only contains a 10 cm thick claystone interlayer (Fig. 2b, 3c). The Domuzcu coal layer has thickness of 2.9 m and contains claystone at the base (Fig 2b, 3b). The upper contact of coal layer is out of gallery and no cap rock was recognized. Towards the base, coal level hosts a claystone interlayer of 34 cm thickness (Fig 3b). A sequence of 2.4 m thickness was measured from the Büyük coal layer (Fig 2b, 3a). Top and base of the layer made up of claystone and coal is observed as a homogeneous level (Fig 3a). The Kesmeli coal layer is found at the top of Kozlu Formation (Fig 2b, 3e). A coal layer of about 1.2 m thickness was recognized and the top and base of the layer are comprised by claystone (Fig 3e). 3. SAMPLES AND METHODS Domuzcu, Acılık, Çay and Kesmeli coal layers appearing at different levels in the Kozlu Underground Coal Mining site were measured and, a total of 42 coal samples were systematically collected from these layers (6, 7, 16, 9 and 4 samples respectively). In addition, 2 random samples were taken from the Çay layer. All of these coal samples were subjected to Pyrolysis/TOC analysis. Rock-Eval pyrolysis/TOC analyses were done by using a Rock-Eval 6 instrument equipped with a TOC module on 100 mg powdered sample. The samples were heated from 300°C (hold time 3 min) to 650°C at 25°C/min. The crushed rock was heated from 400°C (hold time 3 min) to 850°C (hold time 5 min) at 25°C/min for oxidation. Following Rock-Eval/TOC analysis, gas chromatography (GC) (bulk extract), gas chromatography-mass spectrometry (GC-MS) (saturated hydrocarbons - sterane and terpane/aromatic hydrocarbons - monoaromatic and triaromatic steroids, phenantrene and methylphenantrenes, dibenzotiophene, and methyl- dibenzotiophenes) analyses were conducted on extracts obtained from five samples from different coal layers (ZKÇ-6/Çay, ZKA-6/Acılık, ZKD-4/Domuzcu, ZKB-3/Büyük and ZKK-2/Kesmeli). Rock Eval/TOC, GC and GC–MS analyses were realized at the Geochemistry Laboratories of Turkish Petroleum Corporation (TPAO). 5 ACS Paragon Plus Environment

Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

The C15+ soluble organic matter (SOM) was isolated following Soxhlet extraction (40 hr) of the powdered coal samples with dichloromethane (CH2Cl2). Whole coal extracts were analyzed using a Varian 3400 gas chromatograph equipped with flame photometric (FPD) and flame ionization detectors (FID). A fused capillary column (60 m, 0.20 mm i.d.) coated with cross-linked dimethylpolysiloxane (J&W, 0.25 μm film thickness) was used. Helium was the carrier gas. The oven temperature was programmed from 40ºC (hold time 8 min) to 270ºC (hold time 60 min) at 4ºC/min. Coal extracts were de-asphaltened using n-pentane and were fractioned by thin-layer chromatography (MK-Iatroscan). n-hexane, toluene, and methanol were used for extract separation into saturated hydrocarbons, aromatic hydrocarbons, and NSO fractions, respectively. GC-MS analyses were performed on the saturated and aromatic fractions using an Agilent 5975C quadruple mass spectrometer coupled to a 7890A gas chromatograph and a 7683B automatic liquid sampler. The gas chromatograph was equipped with an HP-1MS fused silica capillary column of 60 m length, 0.25 mm i.d., and 0.25 μm film thickness. Helium was used as the carrier gas. The oven temperature was programmed from 50ºC (hold time 10 min) to 200ºC (hold time 15 min) at 10ºC/min, to 250ºC (hold time 24 min) at 5ºC/min and then to 280ºC (hold time 24 min) at 2ºC/min. Finally, the oven temperature was increased to 290ºC (hold time 40 min) at 1ºC/min. The mass spectrometer was operated in EI mode at ionization energy of 70 eV and a source temperature of 300ºC. The biomarker contents were determined using single-ion recordingly at m/z 191 for tri-, tetra- and pentacyclic triterpanes, at m/z 217 for steranes and rearranged steranes, at m/z 253 for monoaromatic steranes, at m/z 231 for triaromatic steranes, at 178 and 192 for phenantrene and methyl-phenantrene, and at m/z 187 and 198 for dibenzotiophene and methyl-dibenzotiophenes. Compounds were identified by their retention time and elution order matching. 4. RESULTS 4.1. Rock-Eval/TOC analysis TOC values of Kozlu coal layers are quite variable (Table 1). The Büyük and Acılık layers have the highest TOC contents (with average TOC values of 44.06% and 44.16%) whereas the Kesmeli layer has the lowest TOC content. Only one sample has TOC value of 55.18% and TOC contents of other samples are very low (4.03 to 20.35%) which were classified as coaly shale (Table 1). The Kozlu coals are represented by quite high S1 and S2 values. High hydrogen index (varying from 84 to 331 mgHC/gTOC with average of 262 mgHC/gTOC) and very low oxygen index values (varying from 1 to 5 mgCO2/gTOC) were recorded. Although coal samples contain significant amount of residual carbon, they are characterized by considerable quantity of pyrolysisable carbon content (Table 1). 4.2. Molecular Composition 6 ACS Paragon Plus Environment

Page 6 of 41

Page 7 of 41 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

4.2.1. n-alkanes and isoprenoids In gas chromatographs of Kozlu (Zonguldak) coal samples, n-alkanes were recorded at C8-C35 range (Fig. 4). Also, other compounds (e.g. aromatic, resin) are present in high amounts. For all coal samples, C14 is the dominant n-alkane compound. There is a unimodal distribution in which lowcarbon numbered n-alkanes are dominant whilst high-carbon numbered n-alkanes are low in quantity. n-C17 and n-C18 are more dominant than Pr and Ph. The Pr/nC17 and Ph/nC18 ratios were calculated 0.10-0.18 and 0.10-0.20, respectively (Table 2). Pr is more dominant than Ph and, the Pr/Ph ratio is in the range of 1.11 to 1.60 (Table 2). CPI24-34 is very close to 1, varying from 0.91 to 1.08. TAR values are very low (in the range of 0.05 to 0.09). 4.2.2. Steranes and terpanes In m/z 217 mass chromatographs, there is sterane distribution represented by dominant C29 and very low C27 concentrations (Fig. 5, Table 3). Iso-steranes are in higher quantity with respect to n- and diasteranes which represent the group with the lowest abundance. 20S/(20S+20R) sterane ratio was very high (varying from 0.52 to 0.55) and sterane isomerization attained equilibrium (Table 3).  sterane ratio has not attained equilibrium and have high values (varying from 0.51 to 0.55). In m/z 191 mass chromatographs, particularly C19 and C20 tricyclic terpanes were recorded in high abundance (Fig. 6). Calculated (C19+C20)/C23 tricyclic terpane ratio was very high (Table 3). C22/C21 tricyclic terpane ratio is generally low whereas C24/C23 tricyclic terpane ratio has moderate to high values. Ts and Tm abundances are very close to each other and Tm is generally higher in abundance than Ts. The calculated moretane/hopane ratio was very low (varying between 0.12 and 0.22). C31R/C30 hopane ratio is in the range of 0.19 to 0.32, mostly greater than 0.25 (Table 3). C25 tricyclic terpane is more dominant than C26 tricyclic terpane. C29 hopane was recorded in lower amount in comparison to C30 norhopane. C29Ts and C30* have high abundance and C30* is more dominant than C29Ts. Gammacerane was recorded in low abundance. C31 is the dominant homohopane and there is a distribution represented by an abundance regularly decreasing from low-carbon numbered homohopanes to high-carbon numbered homohopanes (Fig. 7). Homohopane isomerization attained equilibrium and 22S/(22S+22R) homohopane ratio was calculated as being in the range of 0.59 to 0.62. 4.2.3. Aromatics and polar compounds On m/z 253 mass chromatographs, C27, C28 and C29 MA steroids have similar abundances and dominant steroid changes with respect to one sample to another (Fig. 7). C29/(C28+C29) MA steroid 7 ACS Paragon Plus Environment

Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ratio varying from 0.40 to 0.53 is generally high. MA(I)/MA(I+II) steroid distribution obtained from m/z 253 mass chromatographs is very high (Table 3). C26-C28 triaromatic steroids which are described as TA(II) in m/z 231 mass chromatographs were not recorded whereas C20 and C21 triaromatic steroids known as TA(I) were recorded significantly (Fig. 8). P concentrations measured in m/z 178, 192 mass chromatographs are much lower than MP concentrations. MP abundances are ordered as 2MP>1MP>3MP>9MP (Fig. 9). 2MP and 3MP are much dominant than 9MP and 1MP. MPI-3 ratio was calculated very high (varying from 1.25 to 1.42) (Table 3). On m/z 184,198 mass chromatographs, DBT abundances are generally higher than MDBT. There is a general distribution represented by dominance of 4-MDBT or 2-MDBT and low 1-MDBT content (Fig. 10). MDR and MDR' values are very high (Table 3). DBT abundances are much lower than P and the calculated DBT/P ratios are very low (Table 3). 5. DISCUSSION 5.1. Type of organic matter and depositional environment Coals are generally represented by high C24/C23 and low C22/C21 tricyclic terpane ratios. The Kozlu coals have moderate-high C24/C23 and low C22/C21 tricyclic terpane ratios (Fig. 11a). The C19 and C20 tricyclic terpane abundance is related to high terrestrial plant source and, high (C19+C20)/C23 tricyclic terpane ratios have been interpreted as an evidence of terrestrial organic matter input [49]. Very high (C19+C20)/C23 tricyclic terpane ratios of Kozlu coal samples (varying from 3.32 to 14.68) reflect high terrestrial plant content of coals. C3122R/C30 hopane ratio has been proposed to as proxy for distinguishing lacustrine and marine depositional environments and sediment having ratio less than 0.25 is interpreted as lacustrine deposits [50]. The C3122R/C30 ratios of Kozlu coal samples are generally low indicating no marine effect to the deposition of coals (Fig. 11b). High concentrations of C30* are characteristic for clay-rich sediments deposited under suboxic-oxic conditions with terrestrial and bacterial organic matter. C30*/C29Ts ratio is strongly related to depositional conditions and, it is particularly higher for sediment deposited under oxic-suboxic conditions than those deposited under anoxic conditions. C30* and C29Ts of the Kozlu coals were recorded in high concentrations. C30* is more dominant and C30*/C29Ts ratios are high. These findings indicate that clay-rich Kozlu coals were deposited under suboxic-oxic conditions and have abundant input of terrestrial and bacterial organic matter. The calculated C29/C30 hopane and (C35S/C34S) homohopane ratio which is used as a measure of carbonization was very low indicating clay-rich coals are poor in carbonate minerals (Fig.11d) . Low sterane concentrations and low sterane/hopane ratios generally point to terrestrial and/or microbial organic matter [41, 51]. Low sterane/hopane ratios of Kozlu coal samples indicate that coals mostly contain terrestrial/microbial organic matter. In coal samples, C29 is the dominant sterane and C27 steranes were recorded in low concentration (Fig. 5,11c, Table 3). Dominance of C29 sterane yields 8 ACS Paragon Plus Environment

Page 8 of 41

Page 9 of 41 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

that the Kozlu coals mainly contain terrestrial organic matter [52, 53]. Dominance of C29 over C27 and C28 monoaromatic sterane is attributed to terrestrial organic matter [51, 54]. In addition, in non-marine environments C29/(C28+C29) monoaromatic steroid ratio was found to be higher than 0.5 [51]. In three samples of Kozlu coals, C29 content is higher than other monoaromatic steroids and C29/(C28+C29) monoaromatic steroid ratio was calculated to be higher than 0.5. For other two samples, this ratio was found less than 0.5 or very close to 0.5. Available data indicate that coals were formed in a non-marine environment having abundant terrestrial organic matter input. High 9-MP concentrations have been recorded in organic matter of marine shales and high contents of 1-MPs have been preferentially found in organic matter of terrestrial source rocks [55]. In all of the Kozlu coal samples. 1-MP is more dominant than 9-MP indicating that coals contain terrestrial organic matter and were deposited in a terrestrial environment. High DBT and MDBT ratios are characteristic to marine shale and carbonates however, they have generally low concentrations in continental facies [56]. The relation between MDBT concentrations and organic facies is expressed with DBT/P ratio [56, 57]. According to Requejo [58], DBT/P ratio of 0.006 to 0.2 is typical for coals. Similarly this ratio was also determined to be very low for the Kozlu coals (Table 3). In DBT/P-Pr/Ph diagram (Fig. 11b), coal samples are plotted into the "(3) marine shale and other lacustrine" field. Based on geological data, Pr/Ph ratios less than 3 exert a great control for coals that were formed in fluvial facies (flood plain) to plot in field 3 in Fig. 11f. Even though Pr/Ph ratio generally increases with maturity, this relation is not systematic [50,59]. Albrecht et al. [60] found that Pr/Ph ratio in sediments in the Douala Basin first increased in the oil generation zone (up to 4.9) and then decreased at high maturity levels (down to 1.5). In the basis of biomarker data, Kozlu coal samples were found to be deposited in a suboxic-oxic environment (Fig. 11e) and their relatively low Pr/Ph ratios are probably associated with high maturity level. In the gas chromatographs of coal samples, C14 comprises the max n-alkane compound and an n-alkane distribution (very low TAR value varying from 0.05 to 0.09) in which low-carbon numbered n-alkanes are more dominant than high-carbon numbered n-alkanes was observed (Fig. 4, Table 2). The low-carbon numbered n-alkane abundance and very low TAR value of Kozlu coals that are represented by terrestrial organic matter may be explained with the conversion of high-carbon numbered n-alkanes to low-carbon numbered n-alkanes by thermal degradation. Pyrolysis data yield that Kozlu coals have average 262 mgHC/grTOC HI values and predominantly contain Type II and subordinately Type III kerogen (Table 1, Fig. 12). Considering the biomarker data, Kozlu coals mostly contain terrestrial organic matter and algal/bacterial organic matter to a lesser extent. Although their high terrestrial organic matter content, the composition of Type II kerogen is attributed to the mixing of lipid-rich parts (e.g. spore, pollen, resin, cutine) of terrestrial organic matter and algal/bacterial organic matter forming Type I kerogen with terrestrial organic matter forming Type III kerogen. Karayiğit et al. [20], based on petrographic data from coal samples of the Kozlu Formation, suggested that the peat deposits comprise mostly woody plants that 9 ACS Paragon Plus Environment

Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

organic matter was well preserved through the Westphalian-A and, that an herbaceous plant cover was dominant occasionally in the paleo-swamp. Vitrinite was found to be the most dominant and liptinite the least dominant maceral group (up to 13.7%) [20, 22]. Liptinite group macerals are commonly represented by sporinite, liptodetrinite and cutinite for Kozlu coal samples [20, 22]. Resinite maceral was also described by Taşçı [22]. These petrographic data support the interpretation of dominant terrestrial organic matter input that was also revealed by biomarker data. Also high HI and Type II kerogen content has been proven to be derived from liptodetrinite, sporinite, resinite and cutinite macerals that are composed of hydrogen-rich part of terrestrial organic matter (Type I). The available data indicate that Kozlu coals contain predominantly terrestrial organic matter input. In addition, the coals contain significantly lipid-rich parts (spores, pollen, resin) of terrestrial organic matter and algal/bacterial organic matter, resulting in the presence of high HI values and Type II kerogen. 5.2. Maturity of organic matter Tmax values of samples from coal layers are similar, with average Tmax value of 462ºC (Table 1). These values point to that Kozlu coals are of mature-late mature stage. Tmax values between 454 and 465 °C correspond to approximately 0.9−1.25% Ro values [61], based on this data Kozlu bituminous caol are in "high volatile bituminous B-medium volatile bituminous" rank [62]. CPI values computed from gas chromatographs are found in the range of 0.93 to 1.08 (Table 2) and these values which are very close to 1 reflect mature character of coals. As a result of homohopane isomerization in C-22, biologically existing 22R configuration transforms to 22R and 22S mixture. This makes the 22S/(22R+22S) homohopane ratio to be used in determining the maturity [49, 63]. However homohopane isomerization attains equilibrium at early maturity stage, therefore 22S/(22R+22S) homohopane ratio cannot be used to determine higher maturity stages. The homohopane ratio of coal samples varies from 0.59 to 0.62 indicating that isomerization has attained equilibrium and coals are at least at the early mature stage (Fig. 13a, Table 3). 20S/(20R+20S) and  sterane isomerization have attained equilibrium at 0.52-0.55 and 0.67-0.71, respectively and they can be successfully used to determine the immature-mature range [64]. 20S/(20R+20S) sterane ratios of th Kozlu coals ranging from 0.52 to 0.55 show that isomerization has attained equilibrium but, the  sterane ratio varying from 0.52 to 0.55 indicates that isomerization has not yet reached to equilibrium. Equilibrated 20S/(20R+20S) ratios and very high  sterane ratios show that Kozlu coals are of mature in character (Fig. 13b). With increasing thermal maturity, moretanes gradually transform to hopanes and thus the moretane/hopane ratio can be used for determining the maturity [50, 65-67]. The moretane/hopane ratios of Kozlu coal samples are low, in the range of 0.12 to 0.22, pointing the mature character of coals. C30* are more stable than C30 hopane and C29 for the maturity and, the C30* abundance increases, with increasing 10 ACS Paragon Plus Environment

Page 10 of 41

Page 11 of 41 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

maturity, much more than C30 hopane and C29Ts (particularly in late oil window) [68, 69]. The high C30* content and high C30*/C29Ts and C30*/(C30*+C30H) ratios of the Kozlu coal samples can be attributed to high maturity as well as the presence of terrestrial and bacterial organic matter depositing in a clay-rich suboxic-oxic environment. 2-MP and 3MP isomers (-isomers) are thermally more stable than 1-MP and 9- MP (-isomers) isomers and,  MP ratio (MPI-3) have been used for determining the maturity [70]. Using MPI-3 values Radke [71] categorized the oils into three maturity classes; MPI-3 value of > 1: mature, 0.8-0.1: moderately mature and < 0.8: immature level. MPI-3 values of the Kozlu coal samples are between 1.25 and 1.42 indicating high maturity. Since 4-MDBT is thermodynamically more stable than 1MDBT, with increasing maturity 4-MDBT abundance increases with respect to 1-MDBT and these alkyldibenzothiophene ratios provide insight into maturity [72, 73]. MDR and MDR' values increase with maturity and these values are found very high for the Kozlu coals (9.89-20.20 and 0.91-0.95, respectively indicating that Kozlu coals have high maturity levels. Depending on maturity increase, the MA(I)/MA(I+II) and TA(I)/TA(I+II) steroid ratios raise from 0 to 100% and they can be used to describe early mature-late mature range [50,74-76]. MA(I)/MA(I+II) steroid ratios of Kozlu coals range from 0.22 to 0.43 which point to mature character for the coal samples. On the m/z 231 mass chromatographs of samples TA(II) steroids were not recorded and TA(I)/TA(I+II) steroid ratio was computed as 1. High MA(I)/MA(I+II) and TA(I)/TA(I+II) steroid ratios reflecting 100% conversion yield that coals are of mature-late mature in character. 5.3. Potential of hydrocarbon generation Coals are important gas source rocks and may form voluminous gas accumulations [36-39]. Although limited, they are also source rocks for the liquid hydrocarbon and generate commercially feasible oil [41,42]. Liquid hydrocarbon (oil) potential of coals depends on liptinite content [40,77] and liptinite-rich coals (with abundance of %15-25) might generate significant amount of liquid hydrocarbon [78]. It was also shown that some vitrinite macerals in coals and algal and bacterial biopolymers within inertinites generate oil [79-82]. Some humic coals contain notable amount of liptinitic material that exist as hardfill, coating or invisible impregnations. Coals that contain microbial residuals, called perhydrous coal, may generate liquid hydrocarbon much more than normal coals. Liptinite content of organic material increases with increasing H content and thus H/C and HI values (direct measurement of H content by pyrolysis) become determinative for the oil generation potential of coals. It is thought that coals with H/C ratio of 0.8 or higher (HI>200) may generate oil [83,84]. The effect on H content on oil generation of coals has been experimentally shown and H content was found to be the sole parameter correlated with oil products [85].


Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Kozlu coals with liptinite content up to %13.7 [20, 22] and coaly shales have HI index values high than average coals (Table 1). Except for the Kesmeli layer (HI average is 158 mg HC/gTOC), other coal layers are represented by average HI values ranging from 261 to 284 mg HC/gTOC indicating that Kozlu bituminous coals are source rock of both gas and oil [86,87]. Very high S1 values (average 6.04 mg HC/g rock) and S1/TOC ratios (average 0.16) of Kozlu coals imply that Kozlu bituminous coals generate significant amount of liquid hydrocarbon and contain hydrocarbon in their spaces. Liquid hydrocarbons within the coal are continuingly generated and expelled from the coal. In spite of this, large amount of liquid hydrocarbon are trapped within macromolecular matrix of coal. This is attributed to low expulsion effect of coals on the heavy hydrocarbons arising from high absorption of coals [36,40,41]. The major hydrocarbon generation phase (oil window) for coals typically corresponds to semibituminous and low-volatile bituminous coal rank (vitrinite reflectance 0.5-1.6%). It was shown that before attaining at high volatile A bituminous rank coals do not generate hydrocarbon and at even high ranks (medium-volatile bituminous coal) they have high generation potential [88]. According to Tmax data, organic material of Kozlu bituminous coals are at mature-late mature stage (corresponding to "high volatile bituminous B-medium volatile bituminous" rank) and this thermal maturity level indicates that coals generate significant amount of oil and gas. Very high S2 values (average 110.08 mg HC/g rock) of Kozlu bituminous coals imply that these coals may still have high hydrocarbon (oil/gas) generation potential (Table 1). Pyrolysis data indicate that Kozlu bituminous coals might be included to the group of coals with hydrocarbon (oil) generation potential.

6. CONCLUSIONS Kozlu coal samples are classified as coaliferous clay and have TOC contents generally less than 50%. Kozlu coals are represented by relatively high HI (262 mg HC/g rock) and very low OI (2 mg CO2/g rock) values. Pyrolysis data indicate that coals predominantly contain Type II kerogen and subordinately Type III kerogen. Dominancy of C29 steranes over C27 and C28 and high (C19+C20)/C23 tricyclic terpane ratio (3.32-14.68) are evidences of terrestrial organic matter whereas low sterane/hopane ratios correspond to terrestrial and microbial organic matter. C29/(C28+C29) monoaromatic steroid ratio is between 0.44 and 0.59 and C31R/C30 hopane ratio varies from 0.21 to 0.31 indicating non-marine organic matter and deposition environment. Very high concentrations of C30*(diahopane) and C29Ts, high C30*/C29Ts ratio and Pr/Ph ratios computed in the range of 1.11 to 1.60 yield that clay-rich coals which are greatly contributed by terrestrial and bacterial organic matter were deposited under suboxic-oxic conditions. Even though the biomarker data reveal that the Kozlu coals contain high amount of terrestrial organic matter, the pyrolysis analysis gave dominantly Type II and minor Type III kerogen contents. 12 ACS Paragon Plus Environment

Page 12 of 41

Page 13 of 41 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

This has been interpreted as being resulted from mixing of lipid-rich parts (e.g. spore, pollen, resin, cutine) of terrestrial organic matter and algal/bacterial forming Type I kerogen with terrestrial organic matter forming Type III kerogen. On gas chromatographs of Kozlu coals which have high terrestrial organic matter input, low-carbon numbered n-alkanes were recorded to be dominant over high-carbon numbered n-alkanes which resulted in very low TAR value. This might be explained, depending on mature-advance mature character of the coals, by the conversion of high-carbon numbered n-alkanes to low-carbon numbered n-alkanes by thermal degradation. 22S/(22S+22R) (C32) homohopane, 20S/(20S+20R) (C29) sterane (0.52-0.55) and TA(I)/TA(I+II) steroid ratios attained saturation condition (0.60-0.62). CPI values very close to 1, low moretane/hopane

(0.12-0.22),

high

Tmax,



sterane

(0.52-0.55),

C30*/C29Ts,

C30*/(C30*+C30H), MAI/(MAI+MAII) steroid, MPI-3() ratios (1.25-1.42), MDR (9.89-20.20) and MDR’ (0.91-0.95) ratios are indicative of mature-late mature organic matter. Kozlu bituminous coals with extremely high HI values may generate oil-gas. Their mature-late mature character (corresponding to "high volatile bituminous B-medium volatile bituminous" rank) indicate that they can generate hydrocarbon (gas/oil) and high S1 and S1/TOC values show that significant amount of hydrocarbon is trapped in the voids of coals and very high S2 values yield that these coals still have high hydrocarbon (oil/gas) generation potential. Kozlu bituminous coals with these characteristics are a good example for the liquid hydrocarbon generating coals.

Acknowledgements The Turkish Scientific Research Council (TÜBİTAK ÇAYDAG project no: 114Y631) financially supported this study. The authors would like to thank the General Directorate of Mineral Research and Exploration (MTA) and the Geochemical Laboratory of the Turkish Petroleum Co. (TPAO) for their support in analyzing the data. We acknowledge the staff of the Kozlu Hard Coal Management (TTK) for their technical support and permission for coal sampling from underground galleries in the Kozlu region. We also thank Hükmü Orhan (Selçuk University) who revised and improved the language of the paper. The authors thank anonymous referees and associate editor Hongwei Wu who provided useful comments and improved the manuscript. References (1) TTK, 2018. Turkish Hard Coal Coorporation 2017 Coal Sector Report. T.C.E.T.K.B., 46 p. (in Turkish) (2) Ünalan, G., 2010. Coal Geology. MTA, Ankara, 556p. (in Turkish). (3) Zeigler, P.A., 1990.Geological Atlas of Western and Central Europe. 2nd edition. Shell Internationale Petroleum Maatschappij (The Hauge): 239 pp. 13 ACS Paragon Plus Environment

Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

(4) Blakey, R.C., 2003. Carboniferous-Permian Paleogeography of the Assembly of Pangea, Proceedings of the XVth International Congress on Carboniferous and Permian Stratigraphy, Utrecht, the Netherlands, 10-16 August. (5) Cadle, A.B., Cairncross, B., Christie, A.D.M., Roberts, D.L., 1993. The Karoo basin of South Africa: type basin for the coal-bearing deposits of southern Africa. International Journal of Coal Geology 23, 117–157. (6) Okay, A.I., Şengör, A.M.C., Görür, N., 1994. The Black Sea: Kinematic History of Opening and its Effect on the surrounding regions, Geology 22, 267-270. (7) Görür, N., 1998. Timing of opening of the Black Sea Basin. Tectonophysics 147, 247-262. (8) Görür, N., Tüysüz, O., 1997. Petroleum Geology of the Southern Continental Margin of the Black Sea. In: Robinson, A.G. (Ed.), Regional and Petroleum Geology of the Black Sea and Surrounding Region. American Association of Petroleum Geologists, Memoirs, vol. 68, pp. 241-254. (9) Sandulescu, M., 1978. The Moesic Platform and trhe North Dobrogean Orogene, The Balkans, In: M. Lemoine Ed., Geological atlas of Alpine Europe and Adjoining Alpine areas-Elsevier, Amsterdam, 427-460. (10) Zonenshain, L.P., Korinevsky, V.G., Kazmin, V., Pechersky, D.M., Khain, V.V., Matveenkov, V.V., 1984. Plate Tectonic Model of the South Urals Development, Tectonophysics 109, 95-135. (11) Matte, P., 1986. Tectonics and Plate Tectonic Model for the Variscan Belt of Europe., Tectonophysics 126, 329-374. (12) Görür, N., Monod, O., Okay, A.I., Şengör, A.M.C., Tüysüz, O., Yiğitbaş, E., Sakınç, M., Akkök, R., 1997. Palaeogeographic and Tectonic Position of the Carboniferous Rock of the western Pontides (Turkey) in the Frame of the Variscan Belt, Bull. Soc. Geol. France 168, 197-205. (13) Oplustil, S., Lojka, R., Psenicka, J., Yılmaz, Ç., Yılmaz, M., 2018. Srdimantology and Stratigraphy of the Amasra Coalfield (Pennsylvanian), NW Turkey-New Insight from a 1 km Thick Section, Internationan Journal of Coal Geology 195, 317-346. (14) Ralli, G., 1896. Le Bassin Houiller d’Heraclee, Ann. Soc. Geol. Bel. 23, 151-267. (15) Ralli, G., 1933. Le Bassin Houiller d’Heraclee et Flore du Culm et du Houiller Moyen, İstanbul: Zellitch Freres. (16) Kerey, I.E., Kelling. G., Wagner, R.H., 1986. An Outline Stratigraphy and Palaeo Botanical Records from the Middle Carboniferous Rocks of Northwestern Turkey. Ann. Soc. Geol. Nord, CV, 203-216. (17) Derman, A.S., Özçelik, Y. 1993. Batı Karadeniz Bölgesi'ndeki Paleozoik Birimlerinin Stratigrafisi, Sedimantolojik Özellikleri ve Yörenin Muhtemel Paleocoğrafik Evrimi. A. Suat Erk Jeoloji Sempozyumu, Bildiriler, Ankara Üniversitesi, Ankara,11-20. 14 ACS Paragon Plus Environment

Page 14 of 41

Page 15 of 41 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

(18) Özler, İ., Orhan, E., Yaver, Y., Canca, N., Kır, N., Tongaç, O., 1992. Geology and Coal Occurences Between Zonguldak Değirmenağzı and Göbü Area, MTA, Ankara, V. 1. (in Turkish) (19) Karayiğit, A.İ., Gayer, R.A., Demirel, İ.H., 1998. Coal Rank and Petrography of Upper Carboniferous Seams in Amasra Coalfield, Turkey. International Journal of Coal Geology 36, 3-4, 277-294. (20) Karayiğit, A.İ., Mastaalerz, M., Oskay, R.G., Gayer, R.A., 2018a. Coal Petrography, Minerology, Elemental Compositions and Palaeoenvironmental İnterpretation of Late Caboniferous Coal Seams in Three Wells From the Kozlu Coalfield (Zonguldak Basin, NW Turkey), International Journal of Coal Geology 187, 54-70. (21) Karayiğit, A.İ., Mastalerz, M., Oskay, R.G., Buzkan, İ., 2018b. Bituminous Coal Seams from Underground Mines in the Zonguldak Basin (NW Turkey): Insights from Mineralogy, Coal Petrography, Rock-Eval Pyrolysis, and Meso and Microporosity, International Journal of Coal Geology 199, 91-112. (22) Taşçı, R., 2007. Characteristic Research of the Coal Vein of Formation of Kozlu in Alacaağızı (Armutçuk) areas. M.Sc. Thesis, Zonguldak Karaelmas University, Zonguldak. (with English abstarct in Turkish)(unpublished) (23) Yahşiman, K., 1960. New spore flora from the Amasra Coal Basin. Bulletin of the Mineral Research and Exploration 55, 46-54. (24) Yahşiman, K., 1961. Some megaspores from the Amasra /Zonguldak) Coal Basin. Bulletin of the Mineral Research and Exploration 57, 82-88. (25) Akgün, F., Akyol, E., 1992. Palynology and paleecology of the coals in Amasra-Bartın Carboniferous Basin. Turkish Journal of Earth Sciences 11, 49-56. (26) Cleal,C.J, van Waveren, I.M., 2012. A reappraisal of the Carboniferous macrofloras of the Zonguldak-Amasra Coal Basin, north-western Turkey. Geol. Croatica 65, 283-297. (27) Cleal, C.J., Stolle, E., van Waveren, I.M., King, S., Didari, V., 2017. Carboniferous Plant Fossils from northern Turkey in the Jongmans Collection, Naturalis, Leiden, Paleontological Journal 51, 7, 770-777. (28) Hoşgörmez, H., Yalçın M., Cramer, B., Gerling, P., Faber, E., Schaefer, R., 2002. Isotopic and Molecular Composition of Coal-Bed Gas in The Amasra Region (Zonguldak Basin Western Black Sea). Organic Geochemistry 33, 429-1439. (29) Yalçın, H., Karayiğit, İ.A., Cicioğlu, E., Gümüşer, G., 1997. The Relationships of Clay Mineralogy and Whole Rock Geochemistry of Eocene Aged Sorgun (Yozgat) Coal Basin. DPÜ VIII. National Clay Semp., Kütahya. (in Turkish) (30) Hoşgörmez, H., Busch, C., Yalçın, M.N., Mann, U., Schaefer, R.G., 1997. Hydrocarbon gases in coals and adjacent strata of the Zonguldak Basin, Turkey: gas composition, Absract, European Coal Conference'97, 5-10 May, İzmir-Turkey, pp. 24. 15 ACS Paragon Plus Environment

Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

(31) Karacan, C.Ö., Okadan, E. 2000. Fracture/cleat analysis of coals from Zonguldak Basin (northwestern Turkey) relative to the potential of coalbed methane roduction. International Journal of Coal Geology 44, 109-125. (32) Özgökçe, S., Yalçın, M.N., 2001. Source rock characteristics of the Carboniferous shales of the Zonguldak Basin (NW Turkey). Abstract Book of the 20th International Meeting on Organic Geochemistry, Nancy, France, 10-14 September 2001. pp. 335-336. (33) Yalçın, M.N., İnan, S., Gürdal, G., Mann, U., Schaefer, R.G., 2002. Carboniferous Coals of the Zonguldak Basin (northwest Turkey): Implications for Coalbed Methane Potential, AAPG Bulletin 86, 7, 1305-1328. (34) Konyalı, Y., 1978. Structure du bassin Houiller d'Heraclee, VIII. In: Int. Congr. Stratigr. Geol. Carboniferous, C.R. vol. 5, pp. 42-48. (35) Karayiğit, A.İ., Orhan, M.E., 1997. Field visit to the Zonguldak Coal Basin. In: Tour three, 09-10 May 1997. European Coal Conference 1997, İzmir. pp. 1-8 (36) Hunt, J. M., 1995. Petroleum Geochemistry and Geology. W. H. Freeman and Company, New York,. (37) Karweil, J., 1969. Aktuelle Probleme der Geochemie der Kohle. In P.A. Schenk and I. Havenaar (eds.), Advances in organic geochemistry 1968. Oxford: Pergamon Press, pp. 59-84. (38) Bartenstein, H., Teichmüller, R., 1974. Inkohlungsuntersuchungen; ein Schlüssel zur Prospektierung von palaozoischen Kohlenwasserstoff-Lagerstatten? Fortschr. Geol. Rheinld. Westfalen 24, 129-160. (39) Lutz, M., Kaasschieter, J.P.H., Van Vijhe, D.H., 1975. Geological factors controlling Rotliegend gas accumulations in the mid-European Basin. Proceedings of Ninth World Petroleum Congress. London: Applied Science Publishers, Vol. 2, pp. 93-103. (40) Orem, W.H., Finkelman, R.B., 2003. Coal Formation and Geochemistry. In: Mackenzie, F.T., Ed., Sediments, Diagenesis, and Sedimentary Rocks: Treatise on Geochemistry, Volume 7, Elsevier-Pergamon, Oxford, 191-222. http://dx.doi.org/10.1016/b0-08-043751-6/07097-3 (41) Tissot, B.P., Welte, D.H., 1984. Petroleum Formation and Occurrence. Springer Verlag, Heidelberg. (42) Clayton, J.L., 1993. Composition of crude oils generated from coals and coaly organic matter in shales. In Hydrocarbons from Coal, AAPG Studies in Geology #38 (eds. B. E. Law and D. D. Rice), American Association of Petroleum Geologists, Tulsa, OK, pp. 185–201. (43) Durand, B., Oudin, J.L., 1979. Exemple de migration des hydrocarbures dans une serie deltaique: le delta de la Mahakam, Indonesie. Proc. 10th World Petrol. Congr. Bucharest 2, 3–11. (44) Durand, B., Ungerer, Ph., Chiarelli, A., Oudin, J.L., 1983. Modelisation de la migration de I’huile. Application a deux exemples de bassins sedimentaires. 11th World Petroleum Congress, london, PD 1, paper 3.


Page 16 of 41

Page 17 of 41 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

(45) MTA, 1994. Report of Carboniferous Basin in Western Black Sea, General Directorate of Mineral Research and Exploration, Zonguldak. (in Turkish)(unpublished) (46) TTK, 2016. Kozlu Hard Coal Coorporation. Measured Stratigraphic Section and Described Coal Layers. (in Turkish)(unpublished) (47) Saner, S., Taner, İ., Aksoy, Z., Siyako, M., Burkan, K.A., 1979. Geology of Karabük, Safranbolu. Turkish Petroleum Corporation, Report No: 1322, Ankara (unpublished) (48) Orhan, E., 1995. General geology of Zonguldak hard coal basin and stratigraphy of the Kozlu K20/G Well, in Zonguldak Basin Research Wells 1, Kozlu K20/G. Special publication of TUBITAK, Marmara Research Center, 217 p. (49) Peters, K.E., Moldowan, J.M., 1993. The Biomarker guide: Interpreting molecular fossils in Petroleum and Ancient Sediments; Prentice-Hall: Englewood Cliffs, NJ. (50) Peters, K.E., Walters, C.C., Moldowan, J.M., 2005. The Biomarker Guide.in: Biomarkers and Isotopes in Petroleum Exploration and Earth History, Second Ed., Vol. 2. Cambridge University Press, Cambridge, pp. 475-1155. (51) Moldowan, J.M., Seifert, W.K., Gallegos, E.J., 1985. Relationship Between Petroleum Composition and Depositional Environment of Petroleum Source Rocks. AAPG Bulletin 69, 1255–1268. (52) Huang, W.Y., Meinschein, W.G., 1979. Sterols as Ecological Indicators. Geochimica et Cosmochimica Acta 43, 739-745. (53) Czochanska, Z., Gilbert, T.D., Philp, R.P., Sheppard, C.M., Weston, R.J., Wood, T.A., Woolhouse, A.D., 1988. Geochemical Application of Sterane and Triterpane Biomarkers to a Description of Oils from the Taranaki Basin in New Zealand. Org. Geochem. 12,123−135. (54) Volkman, J.K., 1986. A Review of Sterol Markers for Marine and Terrigenous Organic Matter. Organic Geochemistry 9, 83-99. (55) Budzinski, H, Garrigues, P., Connan, J., Devillers, J., Domine, D., Radke, M., Oudin, J.L., 1995. Alkylated phenanthrene distributions as maturity and origin indicators in crude oils and rock exracts. Geochimica et Cosmochimica Acta 59, 2043-2056. (56) Radke, M., Welte, D.H., Willsch, H., 1991. Distribution of Alkylated Aromatic Hydrocarbons and dibenzothiophenes in rock of the Upper Rhine Graben. Chem. Geol. 93, 325–341. (57) Hughes, W.B, Holbaa, G., Dzou, L. I. P., 1995. The Ratio of Dibenzothiophene to Phenanthrene and Pristane to Phytane as Indicators of Depositional Environment and Litology of Petroleum in Source Rocks. Geochimica et Cosmochimica Acta 59, 3581-3598. (58) Requejo, A.G., 1994. Maturation of petroleum source rocks-II Quantitative changes in extractable hydrocarbon content and composition associated with hydrocarbon generation. Organic Geochemistry 21, 91-105.


Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

(59) Connan, J., 1974. Diagenese Naturelle et Diagenese Artificielle de la Matiere Organique a Element Vegetaux Predominants, In: Advances in Organic Geochemistry (B.P. Tissot and F. Bienner, eds.), Editipns Technip, Paris, pp. 73-95. (60) Albrecht, P., Vandenbroucke, M., Mandengue, M., 1976. Geochemical Studies on the Organic Matter from the Douala Basin (Cameroon), 1. Evolution of the Extractable Organic Matter and the Formation of Petroleum. Geochimica et Cosmochimica Acta 40, 791-9. (61) Waples, D.W., 1985. Geochemistry in Petroleum Exploration. International Human Resources Development Corporation, Boston, 232 pp. (62) Stach, E., Mackowsky, M. Th., Teichmüller, M., Taylor, G.H., Chandra, D., Teichmüller, R., 1982. Stach's Textbook of Coal Petrology. 3rd edi. Gebrüder Bortraeger, Berlin and Stuttgart, 535p. (63) Waples, D.W., Machihara, T., 1991. Biomarkers for Geologists: A Pratical Guide to the Application of Steranes and Triterpanes in Petroleum Geology. – AAPG Methods in Exploration, 9. (64) Seifert, W.K., Moldowan, J.M., 1986. Use of biological markers in petroleum exploration. In: Johns, R.B. (Ed.), Methods in Geochemistry and Geophysics 24, pp. 261-290. (65) Mackenzie, A.S., Patience, R.L., Maxwell, J.R., Vandenbroucke, M., Durand, B., 1980. Molecular Parameters of Maturation in the Toarcian Shales, Paris Basin, France-I Changes in the configuration of acyclic Isoprenoid Alkanes, Steranes, and Triterpanes, Geochimica et Cosmochimica Acta 44, 1709-21. (66) Grantham, P.J., 1986. Sterane Isomerisation and Moretane/Hopane Ratios in Crude Oils Derived from Tertiary Source Rocks. Org. Geochem. 9, 293−304. (67) Seifert, W.K., Moldowan, J.M., 1980. The Effect of thermal Stress on Source-Rock Quality as Measured by Hopane Stereochemistry. In: Advances in Organic Ggeochemistry (Douglas, A. G., Maxwell, J. R., eds.). Pergamon Press, Oxford, 229–237. (68) Horstad, I., Larter, S.R., Dypvik, H., Aagaard, P., Bjornvik, A.M., Johansen, P.E., Eriksen, S. 1990. Degradation and maturity controls on oil field petroleum column heterogeneity in the Gullfaks field, Norwegian North Sea. Organic Geochemistry 16, 497-510. (69) Moldowan, J.M., Fago, F.J., Carlson, R.M.K., Young, D.C., Van Dwyne, G., Clardy, J., Schoel, M., Pillinger, C.T., Watt, D.S., 1991. Rearranged hopanes in sediments and petroleum. Geochimica et Cosmochimica Acta 43, 3333- 3353. (70) Radke, M., Willsch, H., Leythaeuser, D., Teichmüller, M., 1982. Aromatic components of coal: Relation of distribution pattern to rank. Geochimica et Cosmochimica Acta 46, 1831-1848. (71) Radke, M., 1987. Organic geochemistry of aromatic hydrocarbons. In: Brooks. J., Welte, D. (Eds.), Advances in Petroleum Geochemistry, vol. 2. Academic Press. London, pp. 141205. (72) Radke, M., Welte, D.H., Willsch, H., 1986. Maturity parameters based on aromatic hydrocarbons: Influnce of the organic matter type. Organic Geochemistry 10, 51-63.


Page 18 of 41

Page 19 of 41 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

(73) Radke, M., Willsch, H., 1994. Exractable alklydibenzothiophenes in Posidonia Shale (Toarcian) source rocks: Relationship of yields to petroleum formation and expulsion. Geochimica et Cosmochimica Acta 23, 5223-5244. (74) Seifert, W.K., Moldowan, J.M., 1978. Applications of Steranes, Terpanesa Monoaromatics to The Maturation, Migration and Source of Crude Oils. Geochimica et Cosmochimica Acta 42, 77-95. (75) Mackenzie, A.S., Hoffmann, C.F. and Maxwell, J.R., 1981. Molecular Parameters of Maturation in the Toarcian Shales, Paris Basin, France-III. Changes in Aromatic Steroid Hydrocarbons. Geochimica et Cosmochimica Acta 45, 1345- 1355. (76) Beach, F., Peakman, T.M., Abbott, G.D., Sleeman, R., Maxwell, J.R., 1989. Laboratory Thermal Alteration of Triaromatic Steroid Hydrocarbons. Org. Geochem. 14, 109−11. (77) Snowdon L.R., 1991. Oil from Type III organic matter: resinite revisited. Org. Geochem. 17, 743–747. (78) Pearson, D.L., Moore, T.R., 2000. Coal as a thermal insulator and oil source rock. Am. Assoc. Petrol. Geol., Annu. Meet. Exp. Abstr. 113 pp. (79) Khorasani, G.K., 1987. Oil-prone coals of the Walloon coal measures, Surat basin, Australia. In Coal and Coal-bearing Strata: Recent Advances, Society Special Publication No. 32 (ed. A. C. Scott). Blackwell, London, pp. 303–310. (80) Taylor, G.H., Teichmuller, M., Davis, A., Diessel, C.F.K., Littke, R., Robert, P., 1988. Organic Petrology. Gebruder Borntraeger, Berlin. (81) Boreham, C.J., Powell, T.G., 1991. Variation in pyrolysate composition of sediments from the Jurassic Walloon coal measures, eastern Australia as a function of thermal maturation. Org. Geochem. 17, 723–733. (82) Powell, T.G., Boreham, C.J., Smyth, M., Russel, N., Cook, A.C., 1991. Petroleum source rock assessment in nonmarine sequences: pyrolysis and petrographic analysis of Australian coals and carbonaceous shales. Org. Geochem. 17, 375–394. (83) Powell, T.G., 1988. Developments in concepts of hydrocarbon generation from terrestrial organic matter. In Petroleum Resources of China and Related Subjects, Circum-Pacific Council for Energy and Mineral Resources, Earth Science Series (eds. H. C. Wagner, L. C. Wagner, F. F. H. Wang, and F. L. Wong), vol. 10, pp. 807–824. (84) Hunt, J.M., 1991. Generation of gas and oil from coal and other terrestrial organic matter. Org. Geochem. 17, 673–680. (85) Lewan, M.D., 1990. Variabilty of oil generation from coals of the BlackhawkFormation as determined by hydrous pyrolysis. Abstract, American Chemical Society National Meeting, Boston, June.


Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

(86) Jones, R.W., 1984, Comparison of Carbonate and Shale Source Rocks, in AAPG Studies in Geology 18, Petroleum Geochemistry and Source Rock Potential of Carbonate Rocks, J. Palacas, ed. (87) Merrill, R.K., 1991. Source and migration processes and evaluation techniques. Tulsa: American Association of Petroleum Geologist. (88) Newman, J., Price, L., Johnston, J.H., 1994. Source potential of New Zealand coals, based on relationships between conventional coal chemistry, Rock-Eval pyrolysis, and GCMS biomarkers. 1994 New Zealand Petroleum Conference Proceedings: The Post Maui Challenge: Investment and Development Opportunities, p. 47 (abstract).


Page 20 of 41

Page 21 of 41 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

FIGURES Figure 1. Regional map of northwest Anatolia [45] and location map showing the Kozlu Coal Mining site Figure 2. Generalised stratigraphic section of the Zonguldak-Amasra Basin [45] and The section of coal-bearing Kozlu Formation showing coal layers [46] Figure 3. The section of coal-bearing strata from Kozlu Formation, sample location and images of the coal samples; (a) Büyük (x: 4589269; y: 395967; ztaban: -490 m), (b) Domuzcu (x: 4589202; y: 396014; ztaban: -460 m), (c) Acılık (x: 4588428; y: 394994; ztaban: -482 m), (d) Çay (x: 4588640; y: 396033; ztaban: -333 m) ve (e) Kesmeli (x: 4589353; y: 396059; zta ban:

-560 m) coal layers

Figure 4. Gas chromatograms of the whole extracts from Kozlu coal samples; (a) ZKK-2 from Kesmeli , (b) ZKD-4 from Domuzcu, (c) ZKA-13 from Acılık, (d) ZKB-3 from Büyük, (e) ZKÇ-6 from Çay layers and (d) n-alkane distribution diagram of Kozlu coal samples Figure 5. m/z 217 mass chromatograms showing the distribution of sterane in the coal extract; a) ZKK2 from Kesmeli , b) ZKD-4 from Domuzcu, c) ZKA-13 from Acılık, d) ZKB-3 from Büyük, e) ZKÇ-6 from Çay layers Figure 6. m/z 191 mass chromatograms showing the distribution of terpane in the coal extract; a) ZKK-2 from Kesmeli , b) ZKD-4 from Domuzcu, c) ZKA-13 from Acılık, d) ZKB-3 from Büyük, e) ZKÇ-6 from Çay layers. Figure 7. Mass chromatograms (m/z 253) showing the distribution of monoaromatic steroid hydrocarbons; a) ZKK-2 from Kesmeli , b) ZKD-4 from Domuzcu, c) ZKA-13 from Acılık, d) ZKB-3 from Büyük, e) ZKÇ-6 from Çay layers Figure 8. Mass chromatograms (m/z 231) showing the distribution of triaromatic steroid hydrocarbons; a) ZKK-2 from Kesmeli , b) ZKD-4 from Domuzcu, c) ZKA-13 from Acılık, d) ZKB-3 from Büyük, e) ZKÇ-6 from Çay layers Figure 9. Mass chromatograms (m/z 178 and 192) showing the distribution of phenanthrene and alkylphenanthrenes (P = phenanthrene; MP = methylphenanthrene); a) ZKK-2 from Kesmeli , b) ZKD-4 from Domuzcu, c) ZKA-13 from Acılık, d) ZKB-3 from Büyük, e) ZKÇ-6 from Çay layers Figure 10. Mass chromatograms (m/z 184 and 198) showing the distribution of dibenzothiophene and methyldibenzothiophene (DBT= dibenzothiophene, MDBT = methyldibenzothiophene) in extracts of coal samples; a) ZKK-2 from Kesmeli , b) ZKD-4 from Domuzcu, c) ZKA-13 from Acılık, d) ZKB-3 from Büyük, e) ZKÇ-6 from Çay layers Figure 11. Bivariate diagrams of C24/C23 versus C22/C21 tricyclic terpane (a), C31R homohopane/C30 hopane versus C26/C25 tricyclic terpane (b), ternary diagrams of C27, C28 and C29 steranes (c), bivariate diagrams of C35S/C34S homohopane versus C29/C30 hopane (d), Pr/n-C17 versus Ph/n-C18 and DBT versus Pr/Ph (f) for the coal extract samples. Figure 12. Plots of (a) S2 versus TOC, and (b) HI versus Tmax for the analysed coal samples from Kozlu Formation 21 ACS Paragon Plus Environment

Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Figure 13. Bivariate diagrams of 22S/(22S+22R) homohopane versus 20S/(20S+20R) sterane (a), and 20S/(20S+20R) sterane versus  sterane (b) for the coal extract samples from Kozlu Formation

TABLES Table 1. Results of TOC and Rock–Eval analysis and calculated parameters for the coal and coaly shale samples from Kozlu Formation. Table 2. Parameters calculated from gas chromatograms of the whole coal extracts and vitrinite reflectance (Rr%) values Tablo 3. Biomarker compositions based on m/z 217, 191, 231, 253, 178, 192, 187, 198 mass chromatograms and calculated parameters for the coal sample extracts from Kozlu Formation


Page 22 of 41

Page 23 of 41

Energy & Fuels

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46

Page 24 of 41

Table 1 S1 S2 S3 HI OI TOC Tmax (mgHC/g (mgHC/g (mgHC/g (mgHC/g (mgCO2/g (wt%) (°C) rock) rock) rock) TOC) TOC) Kozlu Formation-Büyük Katmanı ZKB-1 44.39 8.31 129.17 1.05 459 291 2 ZKB-2 46.64 9.44 136.97 1.04 461 294 2 ZKB-3 47.45 8.04 123.21 1.66 460 260 3 ZKB-4 41.91 8.32 115.75 1.30 461 276 3 ZKB-5 39.93 7.76 98.61 1.49 460 247 4 ZKB-6 44.01 9.98 129.65 1.22 458 295 3 Average 44.06 8.64 122.23 1.29 460 277 3 Kozlu Formation-Domuzcu Katmanı ZKD-1 22.66 3.16 38.52 0.42 457 170 2 ZKD-2 22.24 3.54 32.40 0.56 461 146 3 ZKD-3 44.01 6.89 137.68 0.85 458 313 2 ZKD-4 47.10 6.80 134.84 0.78 456 286 2 ZKD-5 44.61 8.78 141.72 0.80 454 318 2 ZKD-6 42.49 7.84 140.45 0.76 455 331 2 ZKD-7 60.15 10.09 156.77 0.64 460 261 1 Average 40.47 6.73 111.77 0.69 457 261 2 Kozlu Formation-Kesmeli Katmanı ZKK-1 4.03 1.26 3.38 0.28 463 84 7 ZKK-2 55.19 12.36 141.80 0.75 462 257 1 ZKK-3 20.35 3.67 32.77 0.33 457 161 2 ZKK-4 14.29 2.87 18.60 0.35 460 130 2 Average 23.47 5.04 49.14 0.43 461 158 3 Kozlu Formation-Çay Katmanı ZKÇ-5/1 41.88 3.93 90.59 2.06 459 216 5 ZKÇ-5/2 36.17 3.50 48.61 0.93 462 134 3 ZKÇ-1 50.98 5.77 140.14 0.87 462 275 2 ZKÇ-3 42.40 8.83 138.94 1.17 460 328 3 ZKÇ-4 47.28 5.43 143.77 0.62 458 304 1 ZKÇ-5 37.09 4.58 113.72 0.74 465 307 2 ZKÇ-6 56.11 5.23 137.71 0.74 459 245 1 ZKÇ-7 38.09 4.20 107.36 0.68 463 282 2 ZKÇ-8 46.08 4.48 129.27 0.75 461 281 2 ZKÇ-9 37.74 3.59 112.73 0.68 464 299 2 ZKÇ-10 51.98 4.04 134.34 0.76 461 258 1 Average 44.16 4.87 117.93 0.91 461 266 2 Kozlu Formation-Acılık Katmanı ZKA-1 41.69 6.09 110.64 0.56 466 265 1 ZKA-2 45.25 9.51 129.76 0.57 464 287 1 ZKA-3 41.06 7.84 111.90 0.69 466 273 2 ZKA-4 43.11 8.32 113.10 0.57 465 262 1 Sample No

PY (S1+S2)

PI (S1/ S1/TOC S1+S2)

S2/S3

RC (%)

PC (%)

MINC (%)

137.48 146.41 131.25 124.07 106.37 139.63 130.87

0.06 0.06 0.06 0.07 0.07 0.07 0.07

0.19 0.20 0.17 0.20 0.19 0.23 0.20

123.02 131.7 74.22 89.04 66.18 106.27 98.41

32.71 34.21 36.33 31.23 30.76 32.13 32.90

11.68 12.43 11.12 10.68 9.17 11.88 11.16

28.86 23.96 18.47 27.81 18.21 31.48 24.80

41.68 35.94 144.57 141.64 150.50 148.29 166.86 118.50

0.08 0.10 0.05 0.05 0.06 0.05 0.06 0.06

0.14 0.16 0.16 0.14 0.20 0.18 0.17 0.16

91.71 57.86 161.98 172.87 177.15 184.80 244.95 155.9

19.03 19.07 31.67 35.02 31.87 29.80 45.99 30.35

3.63 3.17 12.34 12.08 12.74 12.69 14.16 10.12

1.68 1.37 29.10 25.79 31.21 34.65 14.27 19.72

4.64 154.16 36.44 21.47 54.18

0.27 0.08 0.10 0.13 0.15

0.31 0.22 0.18 0.20 0.23

12.07 189.07 99.30 53.14 88.4

3.60 0.43 42.07 13.12 17.20 3.15 12.37 1.92 18.81 4.66

0.17 22.71 0.62 0.53 6.01

94.52 52.11 145.91 147.77 149.20 118.30 142.94 111.56 133.75 116.32 138.38 122.80

0.04 0.07 0.04 0.06 0.04 0.04 0.04 0.04 0.03 0.03 0.03 0.04

0.09 0.10 0.11 0.21 0.11 0.12 0.09 0.11 0.10 0.10 0.08 0.11

43.98 52.27 161.08 118.75 231.89 153.68 186.09 157.88 172.36 165.78 176.76 147.32

33.56 31.57 38.51 29.78 34.58 26.88 43.96 28.67 34.64 27.79 40.23 33.65

8.32 4.60 12.47 12.62 12.70 10.21 12.15 9.42 11.44 9.95 11.75 10.51

21.74 1.30 28.32 38.71 31.26 36.91 20.80 27.66 31.77 29.58 26.38 26.77

116.73 139.27 119.74 121.42

0.05 0.07 0.07 0.07

0.15 0.21 0.19 0.19

197.57 227.65 162.17 198.42

31.78 9.91 33.47 11.78 30.77 10.29 32.76 10.35

23.11 31.62 33.81 29.73


Page 25 of 41 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46

Energy & Fuels

ZKA-5 ZKA-6 ZKA-7 ZKA-8 ZKA-9 ZKA-10 ZKA-11 ZKA-12 ZKA-13 ZKA-14 ZKA-15 ZKA-16 Average General Average

35.99 37.98 42.46 40.87 40.36 43.31 43.99 44.38 45.23 36.95 40.66 38.52 41.36 40.28

7.71 9.63 9.10 10.35 8.66 6.59 4.98 3.78 5.28 2.63 3.60 2.52 6.66 6.04

112.76 109.87 127.22 120.79 113.42 123.91 123.14 124.42 126.73 91.46 118.79 121.56 117.47 110.08

0.56 0.51 0.69 0.60 0.61 0.65 0.76 0.83 0.75 0.73 0.74 0.60 0.65 0.71

463 465 462 468 466 467 467 468 462 464 463 466 465 462

313 289 300 296 281 286 280 280 280 248 292 316 284 262

2 1 2 1 2 2 2 2 2 2 2 2 2 2

120.47 119.50 136.32 131.14 122.08 130.50 128.12 128.20 132.01 94.09 122.39 124.08 124.00 116.12


0.06 0.08 0.07 0.08 0.07 0.05 0.04 0.03 0.04 0.03 0.03 0.02 0.05 0.06

0.21 0.25 0.21 0.25 0.21 0.15 0.11 0.09 0.12 0.07 0.09 0.07 0.16 0.16

201.36 215.43 184.38 201.32 185.93 190.63 162.03 149.90 168.97 125.29 160.53 202.60 183.39 158.12

25.79 27.87 30.88 29.79 29.93 32.17 32.96 33.51 33.96 28.88 30.23 27.99 30.80 30.37

10.20 10.11 11.58 11.08 10.43 11.14 11.03 10.87 11.27 8.07 10.43 10.53 10.57 9.91

35.43 33.27 32.35 35.67 34.66 32.24 34.74 30.57 33.12 35.57 37.96 37.15 33.19 26.14

Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46


Page 26 of 41

Page 27 of 41 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

Table 2 Sample No ZKB-3 ZKD-4 ZKK-2 ZKÇ-6 ZKA-13

Pr/Ph 1.60 1.11 1.43 1.25 1.25

Pr/nC17 0.18 0.14 0.10 0.13 0.18

Ph/nC18 0.16 0.20 0.10 0.18 0.19

CPI (24-34) 0.97 0.95 0.93 1.08 0.91


TAR 0.09 0.08 0.06 0.08 0.05

%Rr 0.84 0.68 0.64 0.84 0.86

Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46

Page 28 of 41

Table 3 Terpanes C22/C21 tricyclic terpane C24/C23 tricyclic terpane (C19+C20)/C23 tt. Ts/(Ts+Tm) moretane/hopane C31 R HH./C30 H. C23 tt/(C23tt+C30 hopane) C26/C25 tricyclic terpane C29/C30 hopane C29Ts/(C29H+C29Ts) C30*/C29Ts C30*/(C30H+C30*) gammacerane/ C30 hopane C35S/C34S homohopane 22S/(22S+22R)(C32) H. sterane/hopane

Büyük ZKB-3 0.27 0.39 6.07 0.48 0.12 0.19 0.16 0.67 0.49 0.36 3.47 0.49 0.02 0.36 0.61 0.42

Coal Layer-Sample No Domuzcu Kesmeli Çay ZKD-4 ZKK-2 ZKÇ-6 0.40 0.11 0.40 0.86 0.23 0.39 14.68 3.81 3.32 0.39 0.47 0.38 0.12 0.14 0.18 0.22 0.21 0.31 0.05 0.35 0.16 0.72 0.06 0.47 0.61 0.39 0.35 0.40 0.59 1.88 2.50 1.65 0.32 0.50 0.48 0.02 0.03 0.04 0.23 0.38 0.31 0.60 0.59 0.62 0.43 0.54 0.39

Acılık ZKA-13 0.37 0.49 4.97 0.58 0.22 0.24 0.40 0.47 0.52 0.68 1.25 0.58 0.06 0.60 0.60 1.84

Steroids

14, 30, 56 33, 45, 21 3.16 0.53 0.53 0.53

9, 42, 49 34, 50, 16 1.84 0.52 0.53 0.84

Dibenzothiophenes

C27,C28,C29 MA steroid (%)

MA(I)/MA(I+II) TA(I)/TA(I+II) TA[C20/(C20+C28 20R)] C28-TA/(C29-MA+C28-TA) C29/(C28+C29) MA

Büyük ZKB-3 34, 32, 35 0.22 1 0.52

Coal Layer-Sample No Domuzcu Kesmeli Çay ZKD-4 ZKK-2 ZKÇ-6 30, 34, 36 27, 34, 39 37, 38, 25 0.32 0.35 0.43 1 1 1 0.52 0.53 0.40

Acılık ZKA-13 51, 25, 24 0.31 1 0.49

Phenanthrenes MPI-1 MPI-2 MPI-3 ( MP) MPR MPR1 MPR9 MPR2 MPR3 1-MP/9-MP

0.69 0.86 1.33 1.44 0.30 0.23 0.44 0.27 1.32

0.68 0.81 1.27 1.34 0.32 0.25 0.42 0.29 1.28

0.65 0.84 1.25 1.41 0.30 0.23 0.43 0.24 1.32

0.72 0.86 1.35 1.43 0.31 0.24 0.45 0.30 1.28

0.75 0.90 1.42 1.55 0.30 0.25 0.46 0.31 1.20

13.80 0.93 0.001

9.89 0.91 0.001

12.71 0.93 0.15

14.05 0.93 0.0005

20.20 0.95 0.113

Steranes C27, C28, C29 sterane (%) n-, iso-, diasterane (%) diasterane/sterane 20S/(20S+20R) C29  C28/C29

18, 31, 51 33, 46, 21 1.83 0.55 0.55 0.59

10, 39, 51 34, 50, 16 1.61 0.53 0.53 0.76

15, 32, 53 35, 46, 18 1.92 0.52 0.51 0.62

MDR MDR' DBT/P

steran/hopan= C27. C28. C29  (20S+20R)/C29-C33 hopan; MPI-1=1.5(2MP+3MP)/(P+1MP+9MP); MPI-2=3(2MP)/(P+1MP+9MP); MPI-3= (2MP+3-MP)/(1MP+9MP); MPR=2MP/1MP; MPR1=1MP/P; MPR2=2MP/P; MPR3=3MP/P; MPR9=9MP/P; MDR=4MDBT/1MDBT; MDR'=4MDBT/(1MDBT+4MDBT); MA(I)/MA(I+II)= (C21+C22)/(C21+C22+C27+C28+C29); TA(I)/TA(I+II)= (C20+C21)/(C20+C21+C26+C27+C28)


Page 29 of 41 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

Figure 1.


Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Figure 2.


Page 30 of 41

Page 31 of 41 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

Figure 3.


Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Figure 4.


Page 32 of 41

Page 33 of 41 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

Figure 5.


Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Figure 6.


Page 34 of 41

Page 35 of 41 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

Figure 7.


Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Figure 8.


Page 36 of 41

Page 37 of 41 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

Figure 9.


Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Figure 10.


Page 38 of 41

Page 39 of 41 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

Figure 11.


Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Figure 12.


Page 40 of 41

Page 41 of 41 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

Figure 13.


Organic Matter Type, Maturity, Depositional Environmental

Recommend Documents