See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/280716011

International Journal of Coal Geology

Article in International Journal of Coal Geology · August 2015

DOI: 10.1016/j.coal.2015.06.012

CITATIONS READS

8 2,392

1 author:

Reyhan Kara-Gülbay
Karadeniz Technical University
33 PUBLICATIONS 267 CITATIONS

SEE PROFILE

All content following this page was uploaded by Reyhan Kara-Gülbay on 08 October 2019.

The user has requested enhancement of the downloaded file.

 International Journal of Coal Geology 149 (2015) 93–107

Contents lists available at ScienceDirect

International Journal of Coal Geology

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

Organic geochemical and petrographical characteristics of coal bearing

Oligo-Miocene sequence in the Oltu-Narman Basin (Erzurum),
NE Turkey
Reyhan Kara-Gülbay
Karadeniz Technical University, Department of Geological Engineering, 61080 Trabzon, Turkey

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

Article history: In the Oltu-Narman (Erzurum) Tertiary Basin, coals occur in the Oligo-Miocene lacustrine sequence. In this study,
Received 20 February 2015 n-alkane, isoprenoid and saturated-aromatic biomarker distributions of coals in the Sütkans region are found in
Received in revised form 26 June 2015 association with pyrolysis and petrographic data and detailed organic geochemical characteristics, depositional
Accepted 26 June 2015
environments and hydrocarbon potential of the coals are propounded.
Available online 13 July 2015
Huminite is the dominant maceral type in coals (51–84%), telohuminite is in lesser abundance, detrohuminite
Keywords:
(especially densinite) and gelohuminite (gelinite) are in higher abundance. Groundwater Influence Index
Coal (GWI) and Gelification Index (GI) are quite high for the studied coals whilst Tissue Preservation Index (TPI)
Oltu-Narman Basin and Vegetation Index (VI) are found to be extremely low. According to the results of pyrolysis, coal, coaly
Biomarker claystone and clayey coal samples contain Type II kerogen.
Depositional environment Although Sütkans coals have high ash content (6.28–44.60%, average: 27.99%), their calorific value is quite high
Maceral ratio (3947–7583 Kcal/kg). Random huminite reflectance values of coals (Vr%) are 0.4–048 (average = 0.44) indicat-
ing sub-bituminous B rank. Tmax values of coal, coaly claystone and clayey coal samples are between 413 and
437 °C. 20S/(20R + 20S), ββ/(αα + ββ) sterane, 22S/(22R + 22S) homohopane, MA(I)/MA(I + II), TA(I)/
TA(I + II) and C28TA/(C29MA + C28TA) steroid, MPI, MPR, and MDR ratios which reflect the maturity of coals
are very low; MPI-1 is intermediate and moretane/hopane ratio is high.
According to petrographical, palynological, and geochemical data, the coal sequence was formed in an environ-
ment changing in character from lacustrine to fluvial, and coals were accumulated in a swamp area with high-
water level, high pH, and intense microbial activity represented by suboxic–anoxic conditions.
© 2015 Elsevier B.V. All rights reserved.

1. Introduction Coal occurrences in the region call attention to several investigators,

and numerous studies were carried out to propound geologic structure
Turkey with a reserve of about 15 billion tons has a great potential of the region and to determine geologic properties and their economic
for lignite deposits. In Turkey there are 126 lignite deposits with re- values as well (Akalın, 1977; Altınlı, 1969; Bayraktutan, 1982; Bozkuş,
serves of more than 1 million tons and except for a few deposits, most 1990, 1992; Çetin, 1976; Karayiğit et al., 2002; Lahn, 1939; Lange,
are located in Tertiary basins. These Tertiary lignite occurrences are 1967; Nebert, 1963; Özcanoğlu, 1960; Tercan, 1987). On the contrary
mostly found in Miocene and partly in the Pliocene deposits. Lignite de- detailed organic geochemical studies on these occurrences are very lim-
posits of Oligocene age are very less and Eocene deposits are rare ited, and thus, in the present study n-alkane, isoprenoid and biomarker
(Korkmaz et al., 2008). (saturated and aromatic) distributions of coals were determined and
In the Oltu-Narman Tertiary Basin (Erzurum), coal occurrences are using other data on coals (pyrolysis and petrographic) organic geo-
found within Oligo/Miocene and Miocene lacustrine deposits (Bozkuş, chemical properties, conditions of deposition environment, and organic
1990) (Fig. 1). Oligo/Miocene coals at different locations in this basin matter type were identified. In addition, hydrocarbon generation poten-
have an economic value and have been exploited for many years as tials of coal, coaly claystone and clayey coals of Oligo/Miocene sequence
open pits and underground operations, and the coals produced were and maturity of organic matter were also investigated.
used as fuel. Coals in the Sütkans (open pit) and Balkaya (open pit and
underground operation) regions are currently mined and used as fuel. 2. Geological setting

The Oltu-Narman Tertiary Basin was examined in detail by Bozkuş

(1990) and in this study the geology of the region was utilized from
E-mail address: [email protected]. the work of Bozkuş (1990).

http://dx.doi.org/10.1016/j.coal.2015.06.012
0166-5162/© 2015 Elsevier B.V. All rights reserved.
94 R. Kara-Gülbay / International Journal of Coal Geology 149 (2015) 93–107

Fig. 1. Geological map of the Oltu-Narman Tertiary Basin (after Bozkuş, 1990). (1) Pre-Jurassic metamorphics and intrusive rocks; (2) Sedimantary sequence; (3) Upper Cretaceous flysch;
(4) Volcano-sedimentary sequence of Upper Cretaceous age; (5) Ophiolitic melange; (6) Oltu-Narman Tertiary basin and its deposits; (7) Upper Miocene–Pliocene pyroclastic rocks;
(8) Plio-Quaternary volcanics; (9) Alluvium.

The basement in Oltu-Narman Tertiary Basin is composed of Permo- in an environment with a combination of fluvial, flood plain, swamp and
Carboniferous acidic magmatic rocks and upper Cretaceous volcano- lacustrine conditions (Bozkuş, 1990).
sedimentary sequence (Fig. 2). Deposits of the Tertiary Basin start at Coaliferous sequence of the Susuz Formation was measured and
the bottom with lower-middle Eocene conglomerate, sandstone sampled at an open pit site in the northeast of Sütkans village (Fig. 3).
and siltstone (Dağdibi Formation) which are conformably overlain by At the site base, the sequence is not seen, and the lowermost part is
the upper Eocene volcano-sedimentary/shallow marine sequence composed of coaly claystones with abundant macro fossils (gastropod).
(Karataş/Yassıkuzu Formation). The upper Eocene unit is covered un- The sequence up to 17 m is composed of coal, clayey coal, and coaly
conformably by Oligocene-aged terrestrial and lacustrine deposits claystone and contains a smaller amount sterile limestone and claystone
with volcanic interlayers. The sequence continues to the top with interlayers. In between 17 and 22 m, coals with sterile limestone, marl,
Oligo-Miocene and Miocene coaliferous units (Susuz and Kömürlü For- and limestone interlayers are dominant. Below 22 m, the sequence con-
mations). Upper Miocene–Pliocene andesite and agglomerates (Penek sists of claystone, marl and limestone with coal interlayers. Below 30 m,
Formation) conformably set above the underlying units. This unit is the sequence is completely composed of claystone, marl, and limestone
conformably overlained by a volcano-sedimentary series with coal alternation and contains no coal (Fig. 3).
interbeddings. The uppermost part of the basin is composed of Plio-
Quaternary basalts. 3. Samples and methods
Colas under investigation occur in Susuz Formation of Oligo-
Miocene age (Fig. 2). This unit is composed mostly of unbedded and lo- In order to ascertain the variation in the amount of organic matter
cally thick bedded sandstone, siltstone, and claystone alternation with content and practically examine general characteristics of organic mat-
green-gray colored coal, conglomerate, and pebbly sandstone inter- ter within coal and other units with pyrolysis analysis a total of 28 sam-
layers. In some fields, the unit appears as very thin-bedded gypsum ples were analyzed. Since TOC content might vary in a short distance in
and claystone alternation. Based on spore and pollen content, the age the sequence (that consists mainly of coal, coaly claystone, clayey coal
of unit is suggested to be Oligo-Miocene. Lithological characteristics and claystone alternation), the number of samples was taken as high
and fossil content of the Susuz Formation indicate that it was deposited as possible to statistically correctly represent the sequence. 9 coal, 3
 R. Kara-Gülbay / International Journal of Coal Geology 149 (2015) 93–107 95

Fig. 2. The generalized columnar section of the study area (after Bozkuş, 1990).
96 R. Kara-Gülbay / International Journal of Coal Geology 149 (2015) 93–107

Fig. 3. The section of coal-bearing strata from Oltu open pit area and images of coal samples.

clayey coal, 7 coaly claystone, and 3 claystone samples were collected Petrographic and proximate analyses were conducted on 7 coal sam-
from the measured section in the Sütkans coal site, and they were sub- ples. The sample selection criteria for petrographic and proximate anal-
jected to Rock-Eval/TOC analysis (Table 1). yses was based on high TOC contents (determined by pyrolysis
 R. Kara-Gülbay / International Journal of Coal Geology 149 (2015) 93–107 97

analysis), which prove that the selected samples and number of samples was the carrier gas. The oven temperature was programmed from
were representative of the characteristics of the coal occurences in the 40 °C (hold time 8 min) to 270 °C (hold time 60 min) at 4 °C/min.
different stratigraphic levels. The thickness of coaliferous section is The coal and coaly claystone extracts were de-asphaltened using
30 m, and maturity is not a very variable parameter for a sequence hav- n-pentane and were fractioned by thin-layer chromatography (MK-
ing such low thickness (as reflected by the Tmax values). Considering the Iatroscan). n-hexane, toluene, and methanol were used for extract sep-
thickness of coaly sequence, 4 coal samples were selected to represent aration into saturated hydrocarbons, aromatic hydrocarbons, and NSO
coal formation from different parts of the section and vitrinite reflection fractions, respectively. GC–MS analyses were performed on the saturat-
analysis was performed. Two coaly claystone and one clayey coal sam- ed and aromatic fractions using an Agilent 5975C quadruple mass spec-
ples for palynological analysis were selected to represent coal trometer coupled to a 7890A gas chromatograph and a 7683B automatic
occurences from the different stratigraphic levels. liquid sampler. The gas chromatograph was equipped with an HP-1MS
Biomarker distributions are similar as long as maturity, organic mat- fused silica capillary column of 60 m length, 0.25 mm i.d., and 0.25 μm
ter type and depositional conditions of the similar facies within the film thickness. Helium was used as the carrier gas. The oven tempera-
same depositional environment are not significantly changed (Peters ture was programmed from 50 °C (hold time 10 min) to 200 °C (hold
and Moldowan, 1993). Considering the results of pyrolysis analysis, time 15 min) at 10 °C/min, to 250 °C (hold time 24 min) at 5 °C/min
the samples were selected for GC and GC–MS analysis, and GC and and then to 280 °C (hold time 24 min) at 2 °C/min. Finally, the oven
GC–MS analysis were performed on one coaly claystone and one coal temperature was increased to 290 °C (hold time 40 min) at 1 °C/min.
samples. Results of pyrolysis analysis indicate that only two of the sam- The mass spectrometer was operated in EI mode at an ionization energy
ples contain Type I kerogen with extremely high HI values (S-18, S-19) of 70 eV and a source temperature of 300 °C. The biomarker contents
and others are represented by Type II kerogen. Sample S-18, coaly were determined using single-ion recordingly at m/z 191 for terpanes
claystone, was selected for GC and GC–MS analysis because it has differ- and tricyclic triterpanes, at m/z 217 for steranes and rearranged
ent organic matter type when compared to other samples (it has the steranes, at m/z 253 for monoaromatic steranes, at m/z 231 for
highest HI value). Sample S-25, coal, was selected to represent samples triaromatic steranes, at 178 and 192 for phenantrene and methyl-
with Type II kerogen for GC and GC–MS analysis. phenantrene, and at m/z 187 and 198 for dibenzotiophene and
Rock Eval/TOC, palynological, vitrinite reflectance, GC, and GC–MS methyl-dibenzotiophenes. Compounds were identified by their reten-
analyses were at the Geochemistry Laboratories of Turkish Petroleum tion time and elution order matching.
Corporation (TPAO), proximate analyses and petrographic determina-
tions of coals were made at the Laboratories of General Directorate of 4. Results
Mineral Research and Exploration (MTA).
For petrographic determination, coal samples were prepared in ac- 4.1. Proximate analysis
cordance with ISO 7404-2, 2009; ISO 7404-3 (2009) standards and pro-
cedures outlined in Sykorova et al. (2005) and ICCP (1998, 2001). The Ash content of the coal samples is between 6.28 and 44.60%
petrographic determinations were performed with Leitz MPV-SP (Table 2). Ash content of the samples in the upper level of the sequence
reflected-light microscope and 50 × oil immersion objective. Random is higher. Volatile content value is between 30.25 and 47.32%. Total sul-
vitrinite reflectance measurements in oil immersion (Rr%) were carried fur content was measured between 1.20 and 2.51%. The gross calorific
out in reflected “white light” using the Windows-based software value of samples ranges from 7583 to −3947 kcal/kg and inversely cor-
MSP200 by Leica DM 2500P according to ICCP (1998), ISO 7404-5 related with the ash content (Table 2).
(2009). Proximate analysis was made in accordance with ASTM
D5865-04 (2004), ASTM D 4239 (2010), and ASTM D 7582 (2012) 4.2. Palynomorphs and macerals
standards.
Palynomorph contents of two coaly claystone and one clayey coal The palynomorph assemblage of samples S9, S16, and S27 consisting
sample were examined semi quantitatively. Approximately 5–20 g of of spore, pollen, fungal, dinoflagellate, and freshwater algae is given in
sample is used for the processing depending on the lithology. Standard Table 3. Samples S9 and S16 have similar palynological properties and
palynological techniques including the removal of carbonates by HCL, both samples are composed of 5% herbaceous, 80% ligneous, 5% char,
removal of silicates by HF, and heavy mineral separation by ZnCl2 and 10% amorphous organic matter. Although other index forms for Ol-
have been applied to the studied samples. Two slides have been pre- igocene are absent, fungal type spore such as Anatolinites dongyingensis,
pared for every sample for palynological examination and visual geo- which characteristic for particularly late Oligocene units in the Thrace
chemical investigations (SCI, organic matter type etc.). Analyses were region (Batı, 1996; Batı et al., 1993; Ediger and Alişan, 1989; Ediger
performed with the use of ZEISS Imager M1 biologic microscope. et al., 1990), is quite abundant. Since palynomorph assemblage deter-
Rock-Eval pyrolysis/TOC analyses of all the samples have been done mined in sample S27 is composed of various forms with wide distribu-
using a Rock-Eval 6 instrument equipped with a TOC module. The sam- tion, it can be said that the sequence was deposited in the Tertiary
ples were heated from 300 °C (hold time 3 min) to 650 °C at 25 °C/min. period. Sample S27 is composed of 5% herbaceous, 75% ligneous, and
The crushed rock was heated from 400 °C (hold time 3 min) to 850 °C 20% amorphous organic matter. Although terrestrial organic matter is
(hold time 5 min) at 25 °C/min for oxidation. Following Rock-Eval/ dominated in these three samples, aquatic organic matter content is in-
TOC analysis, gas chromatography (GC) (bulk extract) and gas creasingly found in sample S27. A terrestrial (lacustrine) environment is
chromatography–mass spectrometry (GC–MS) (saturated hydrocar- specified for these samples and no marine palinomorph was detected.
bons — sterane and terpane/aromatic hydrocarbons — monoaromatic Huminite with the abundance of 51–84% is the dominant maceral
and triaromatic steroids, phenantrene and methil-phenantrenes, type for the coal samples. Telohuminites are in low abundance whilst
dibenzotiophene, and methyl-dibenzotiophenes) analyses were con- detrohuminite (especially densinite) and gelohuminites (especially
ducted on extracts obtained from two samples (S-18, S-25). gelinite) are quite abundant. Liptinite content is 5–19% and it is in the
The C15 + soluble organic matter (SOM) was isolated following form of alginite and sporinite. Inertinite (mostly macrinite) content of
Soxhlet extraction (40 h) of the powdered rock with dichloromethane coal samples is 2–21% (Figs. 4 and 5; Table 4).
(CH2Cl2). Whole coal and coaly claystone extracts were analyzed Tissue Preservation Index (TPI), Gelification Index (GI), Groundwa-
using a Varian 3400 gas chromatograph equipped with flame ter Influence Index (GWI), and Vegetation Index (VI) which were pro-
photometric (FPD) and flame ionization detectors (FID). A fused posed by Diessel (1986) and Calder et al. (1991) and later modified by
capillary column (60 m, 0.20 mm i.d.) coated with cross-linked Kalkreuth et al. (1991) and Kalaitzidis et al. (2004) for low-rank coals
dimethylpolysiloxane (J&W, 0.25 μm film thickness) was used. Helium are used as useful indicators for lignites. Calculated GI and GWI values
98 R. Kara-Gülbay / International Journal of Coal Geology 149 (2015) 93–107

Table 1
Lithological description of the samples from Sütkans area and the analyzes carried out on the samples.

Sample Lithological description Rock Eval/TOC Vitrinite reflectance Proximate Palynology Petrography GC, GC–MS

S1a Fossiliferous coaly claystone x

S1b Fossiliferous coaly claystone x
S2 Coal x x x x
S3 Fossiliferous claystone x
S4 Coal x x x
S5 Coaly claystone x
S6 Fossiliferous coaly claystone x
S7 Coal x x x
S9 Fossiliferous coaly claystone x x
S10 Coal x x x x
S11 Coal x
S14 Fossiliferous coaly claystone x
S15 Coal x x x
S16 Clayey coal x x
S17 Clayey coal x
S18 Coaly claystone x x
S19 Claystone x
S20 Fossiliferous clayey coal x x
S23 Coal x
S24 Fossiliferous coal x x x
S25 Coal x x x x x
S27 Coaly claystone x x

of coals are mostly high (with ranges of 1.60–12.33 and 3.93–15.20, aquatic ratio (TAR) are quite high and are computed as 1.62, 1.96 and
respectively), TPI and VI index are very low (with ranges of 0.03–0.52 1.63, 2.15 for coaly claystone and coal samples, respectively.
and 0.11–0.92, respectively) (Table 4; Fig. 4).

4.4.2. Steranes and terpanes

4.3. Rock Eval analysis
Diasterane and sterane distributions of coaly claystone and coal
samples are generally similar but diasterane abundance is lower than
Average TOC contents of coal, clayey coal, coaly claystone, and
that of steranes. In both samples, normal steranes dominate over iso-
claystone samples are 47.11, 28.60, 15.09, and 6.27%, respectively. HI
and diasteranes and diasterane content of coal sample is greater than
values of coal, clayey coal, coaly claystone, and claystone are represent-
that of coaly claystone (Fig. 7; Table 7). For the coal sample, C29 is the
ed by moderate-high HI (176–722 mgHC/g rock) and very low OI
dominant sterane whilst for the coaly claystone C27 and C29 are recorded
(3–36 mgCO2/g rock) values. Average HI values of coal, clayey
asdominant and C28 is in low abundance. 20S/(20R + 20S) (for C29) and
coal, coaly claystone, and claystone samples are 288, 224, 417,
ββ/(αα + ββ) sterane ratios are very low for both samples (0.10, 0.12;
and 479 mgHC/g rock, respectively (Table 5). Tmax values of coal,
0.11, and 0.16, respectively) (Table 7). Terpane distributions of coal
clayey coal, coaly claystone, and claystone samples are in the range of
coaly claystone samples are mostly similar. Tricyclic terpanes are
413–437 °C. PI values are low for all the samples (in the range of
generally recorded in low abundance and C30 tricyclic terpane is com-
0.01–0.02).
posed of the dominant component. Ts content is very low and Tm was
recorded in much more abundance in comparison to Ts. In both sam-
4.4. Molecular composition ples, C30 hopane dominates over C29 norhopane. C31 is the dominant
homohopane and its abundance decreases towards high-number
4.4.1. n-Alkanes and isoprenoids homohopanes (Fig. 7). The Ts, C29Ts, and gammacerane contents of
In total extract gas chromatographs of coals and coaly claystone coaly claystone sample are greater than those of coal samples and Tm,
samples, a unimodal n-alkane ditribution is noticed where C27 com- C30 tricyclic terpane, C29 norhopane, normoretane, moretane,
prises the dominant peak (Fig. 6). Pristane and phytane were recorded homomoretane, C30 diahopane, C30 norhopane, and C31 homohopane
in very high concentrations and Pr/Ph ratio is high (2.08 and 3.83). Pris- contents are lower for the coaly claystone. The sterane/hopane ratio
tane and phytane are much dominant than neighboring n-alkanes and for both samples is very low (0.20 and 0.34) and hopanes are much
Pr/n-C17 and Ph/n-C18 ratios are very high (Table 6). In gas chromato- more abundant than steranes (Fig. 7; Table 7).
graphs, odd-numbered n-alkanes are much more dominated when
compared to even-numbered n-alkanes. CPI24–34 and terrigenous/
Table 3
Palynological composition of identified species in coaly claystone and clayey coal samples.
Table 2
Proximate analysis results for Sütkans coal samples. S9 S16 S27

Anatolinites Anatolinites Ovoidites ligneolus

Sample Ash Volatile matter Total sulfur Gross calorific value
dongyingensis dongyingensis
(%) (%) (%) (kcal/kg)
Pityosporites spp. Pityosporites spp. Laevigatosporites haardtii
S2 6.28 47.32 1.82 7583 Tricolpopollenites sp. Tricolporopollenites sp. Triporopollenites spp.
S4 25.33 37.82 2.51 5830 Tricolporopollenites sp. Triatriopollenites sp. Pityosporites spp.
S7 36.60 33.83 1.44 4519 Triatriopollenites sp. Inaperturopollenites Subtriporopollenites simplex
S10 8.62 38.15 1.20 7144 hiatus Inaperturopollenites hiatus
S15 30.82 35.84 1.74 5308 Ovoidites parvus Cingulatisporites
S24 44.60 30.25 1.70 3947 macrospecious
S25 43.67 38.64 1.77 4496 Sucul organizma
 R. Kara-Gülbay / International Journal of Coal Geology 149 (2015) 93–107 99

Table 4
Maceral composition (vol.%) and petrographic indices of coal samples from Sütkans area.

Macerals Sample no.

S2 S4 S7 S10 S15 S24 S25

Huminite 78 81 67 75 84 76 51
Telohuminite 2 1 6 5 10 2 10
Textinite 1 – 2 2 3 1 3
Ulminite 1 1 4 3 7 1 7
Detrohuminite 39 36 28 13 26 46 20
Attrinite 3 5 9 1 t.a. 6 4
Densinite 36 31 19 12 26 40 16
Gelohuminite 37 44 33 57 48 28 21
Gelinite 36 44 32 55 46 27 19
Corpohuminite 1 – 1 2 2 1 2
Liptinite 15 5 5 12 10 5 19
Sporinite 3 2 2 1 1 1 6
Cutinite 2 – 1 t.a. – – 6
Resinite 2 1 – 1 1 1 1
Alginite 7 2 2 9 7 3 5
Liptodetrinite 1 – t.a. 1 1 – 1
Inertinite 4 2 21 12 3 6 7
Fusinite – – 4 – – 2 1
Fig. 4. Maceral distribution (%) and variation of gelification index (GI), groundwater influ- Semi-fusinite – – 3 1 – – –
ence index (GWI), vegetation index (VI), tissue preservation index (TPI) of coal samples Funginite – – 1 1 1 – 1
from Sütkans section. Macrinite 4 2 8 10 2 4 5
Inertodetrinite – – 5 – – – –
Mineral matter 3 12 7 1 3 13 23
4.4.3. Aromatic hydrocarbons and polar compounds Pyrite 2 7 2 1 3 3 7
Although monoaromatic steroid distributions of coaly claystone and Clay and silicates 1 5 5 – – 10 16
TPI 0.07 0.03 0.31 0.30 0.43 0.10 0.52
coal samples are quite alike, MA sterane concentration of coaly GI 10.50 6.80 1.60 9.00 12.33 5.11 3.75
claystone sample are higher than that of the coal samples (Fig. 8). In GWI 15.20 14.50 3.93 11.67 7.70 5.40 4.29
both samples, C29 monoaromatic steranes dominated over C27 and C28 VI 0.19 0.11 0.46 0.35 0.35 0.12 0.92
and C27 (higher abundance for the coal sample) and C28 monoaromatic TPI (Tissue preservation index) = (telohuminite + corpohuminite + fusinite)/(attrinite +
sterane abundances are very close (Table 7). C21 and C22 monoaromatic densinite + macrinite)
steranes that are represented by MA(I) were recorded in very low abun- GI (Gelification index) = (ulminite + corpohuminite + densinite + macrinite)/(textinite +
dances in comparison to C27, C28, and C29 monoaromatic steranes and attrinite + fusinite + inertodetrinite)
MA(I)/MA(I + II) ratios of coaly claystone and coal samples were com- GWI (Groundwater influence index) = (gelohuminite + densinite + mineral matter)/
(telohuminite + attrinite)
puted with very low values (0.08 and 0.06, respectively). Triaromatic
VI (Vegetation index) = (telohuminite + fusinite + semifusinite + cutinite + sporinite +
steroid distributions are similar for both samples and C20 and C21 suberinite + resinite)/ (detrohuminite + inertodetrinite + other liptinite)
which are described as TA(I) were recorded in very low abundances t.a.: trace amount
in comparison to C26, C27, and C28 triaromatic steranes that are Bold data indicate main maceral groups.

S2 den S2 S15 ul S15

50 µm 50 µm sp 50 µm 50 µm
osp
sp den
osp
ul ul
oct atr gel
pyr
sp
ul

50 µm S7 50 µm S7 50 µm S25 50 µm S25

pyr ldet cly atr

gel ul pyr res pyr
fus sp
ul

50 µm S10 50 µm S10
ul: ulminite oct :oxidised cutinite
ul atr: attrinite sp: sporinite
den: densinite osp: oxidised sporinite
pyr ct gel: gelinite res: resinite
sp fus: fusinite ldet: liptodetrinite
den mac: macrinite
mac Cly : clay minerals
pyr: framboidal pyrite

Fig. 5. Representative photomicrographs of macerals of coal samples from Sütkans section.

100 R. Kara-Gülbay / International Journal of Coal Geology 149 (2015) 93–107

Table 5
Results of TOC and Rock-Eval analysis.

Sample TOC S1 S2 S3 Tmax HI OI PI S1 + S2 S2/S3 RC PC MinC Ro

(%) (mgHC/g rock) (mgHC/g rock) (mgCO2/g rock) (°C) (mgHC/gTOC) (mgCO2/g TOC) (mgHC/g rock) (%) (%) (%) (%)

S1a 10.51 0.69 33.83 1.33 426 322 13 0.02 34.52 25 7.47 3.04 5.77
S1b 28.16 0.65 60.31 2.70 429 214 10 0.01 60.96 22 22.79 5.37 1.63
S2 54.31 1.58 197.27 3.25 422 363 6 0.01 198.85 61 37.25 17.06 11.36 0.40
S3 3.55 0.31 12.39 1.27 426 349 36 0.02 12.70 10 2.39 1.16 3.22
S4 44.59 1.11 122.64 2.81 417 275 6 0.01 123.75 44 33.86 10.73 10.74
S5 11.29 0.52 54.63 0.65 437 484 6 0.01 55.15 84 6.62 4.67 0.24
S6 4.06 0.35 17.54 0.73 421 432 18 0.02 17.89 24 2.51 1.55 4.42
S7 50.09 1.43 103.82 3.03 416 207 6 0.01 105.25 34 40.88 9.21 1.75
S9 18.48 0.82 57.17 1.63 429 309 9 0.01 57.99 35 13.44 5.04 1.03
S10 54.80 2.44 172.98 3.32 425 316 6 0.01 175.42 52 39.67 15.13 11.93 0.47
S11 38.30 0.95 101.07 2.16 416 264 6 0.01 102.02 47 29.50 8.80 3.09
S14 21.75 1.71 79.17 1.66 430 364 8 0.02 80.88 48 14.82 6.93 3.10
S15 49.02 1.27 144.54 2.54 413 295 5 0.01 145.81 57 36.48 12.54 9.94
S16 26.52 0.92 56.74 2.38 423 214 9 0.02 57.66 24 21.43 5.09 0.5
S17 33.81 1.03 79.80 2.97 419 236 9 0.01 80.83 27 26.73 7.08 0.68
S18 20.19 3.02 145.79 0.96 437 722 5 0.02 148.81 152 7.70 12.49 2.82
S19 8.99 0.77 54.74 0.47 436 609 5 0.01 55.51 116 4.31 4.68 0.32
S20 25.77 0.43 57.32 2.03 424 222 8 0.01 57.75 28 20.71 5.06 0.63 0.42
S23 35.08 0.41 61.66 2.89 423 176 8 0.01 62.07 21 29.56 5.52 1.45
S24 47.15 1.65 110.75 4.04 425 235 9 0.01 112.40 27 37.31 9.84 8.00
S25 50.64 2.82 234.97 1.61 435 464 3 0.01 237.79 146 30.56 20.08 0.92 0.48
S27 6.26 0.30 30.59 0.41 433 489 7 0.01 30.89 75 3.64 2.62 0.32

described as TA(II). TA(I)/TA(I + II) ratio for coaly claystone and coal Phenanthrene and methylphenanthrene distributions of coaly
samples are computed as 0.08 and 0.15, respectively. C28-TA/(C29- claystone and coal samples are quite similar. In both samples phenan-
MA + C28-TA) ratio for coaly claystone and coal samples is quite differ- threne was recorded in very high abundances in comparison to
ent (0.03 and 0.33, respectively) (Table 7). methylphenanthrenes and 9-methylphenanthrene dominated over
other methylphenanthrenes (Fig. 9). For the coaly claystone sample
dibenzotiophene and methyl-dibenzothiophene are in similar abun-
dance, but in the coal sample dibenzotiophene content is greater than
that of methyl-dibenzothiophene. MPR-1, MPR-2, MPR-3, and MPR-9
values that reflect the ratio of methyl-phenanthrenes to phenanthrenes
are lower for the coal samples (Table 7). In both samples methyl-
dibenzothiophenes are in similar abundance but 4MDBT is less domi-
nant than others (Fig. 9). MDR and MDR′ values which reflect the abun-
dance of 4MDBT with respect to 1MDBT are quite alike for both samples
(Table 7).

5. Discussion

5.1. Type of organic matter and depositional environment

Low TPI values (0.03–0.052; ave. 0.27) and generally high GI values
(1.6–12.33; average: 7.01) for the Sütkans coals might indicate that peat
was accumulated in a limnic, limno-telmatic environment under high
water level (Fig. 10a). GI and GWI values (15.2–529; average: 8.96)
show variations along the sequence which reveals that water level fluc-
tuated during the peat formation (Fig. 4; Table 4). Very low inertinite
maceral content and high densinite and gelinite maceral contents and
the presence of alginate show that peat was accumulated due
tounderwater conditions (Table 4). The Sütkans coals are not a homoge-
neous sequence and clayey coals contain claystone and limestone inter-
layers and are alternated with coaly claystone (Fig. 3). These levels are
indicative of a rise in the water level in the swamp and the waters
reached the lake and the peat development was restarted in swamps

Table 6
The parameters calculated from gas chromatograms for coaly claystone and coal samples
from Sütkans section.

Sample Pr/Ph Pr/nC17 Ph/nC18 CPI(24–34) TAR

S-18 2.08 5.23 3.09 1.62 1.63

Fig. 6. Gas chromatograms and n-alkane frequency distributions for coaly claystone
S-25 3.83 5.58 1.92 1.96 2.15
(a) and coal (b) samples from Sütkans section.
 R. Kara-Gülbay / International Journal of Coal Geology 149 (2015) 93–107 101

Fig. 7. m/z 217 and m/z 191mass fragmentograms for coaly claystone (a, b) and coal (c, d) samples from Sütkans section.

as a result of a drop in water level. GWI and VI values indicate that contribution from a woody plant source. Low TPI values in Sütkans
Sütkans coals were formed under high water levels at rheotrophic and coals are indicative of high-bacterial activity and high pH conditions.
mesotrophic conditions (Fig. 10b). In Pr/nC17 vs. Ph/nC18 diagram, Gelling of plant tissues by microbial activity elevates low Eh in swamp
coaly claystone sample plot into transitional depositional environment and humid and neutral-alkaline pH conditions within the high
field whilst coal sample is plotted into peat swamps area (Fig. 11). ground-water level. High GI values of coal samples show intense non-
Low VI values of Sütkans coals ranging from 0.11 to 0.92 (average acidic microbial activity during the peat formation. Well preserved cal-
0.36), low telehuminite and high detrohuminite and correspondingly cium carbonate fossil shells in both coals and coaly claystone and clayey
low TPI values indicate herbaceous/bushy plant source. Low concentra- coal levels also reflect non-acidic conditions during the peat formation.
tions of textinite, ulminite, semifusinite, and fusinite show very low In a triangular diagram developed by Mukhopadhyay (1989) based on

Table 7
Biomarker compositions based on m/z 191, 217, 231, 253, 178, 192, 187, 198 mass chromatograms and calculated parameters for coaly claystone and coal samples from the Sütkans
section.

Terpanes Sample no. Steroids Sample no.

S18 S25 S18 S25

C22/C21 tricyclic terpane 0.09 0.07 C27, C28, C29 MA steroids (%) 23, 21, 56 15, 17, 68
C24/C23 tricyclic terpane 0.59 1.20 MA(I)/MA(I + II) 0.08 0.06
(C19 + C20)/C23 tt. 1.06 2.02 TA(I)/TA(I + II) 0.08 0.15
Ts/(Ts + Tm) 0.28 0.03 TA[C20/(C20 + C28,20R)] 0.20 0.38
Moretane/hopane 0.30 0.60 C28-TA/(C29-MA + C28-TA) 0.03 0.33
C31 R homohopane/C30 hopane 0.20 0.08 C29/(C28 + C29) MA 0.73 0.80
C23 tt/(C23tt + C30 hopane) 0.05 0.04 Phenanthrenes
C25/C26 Tricyclic Terpane 3.59 0.71 MPI-1 0.59 0.52
C29/C30 hopane 0.50 0.78 MPI-2 0.50 0.48
C29Ts/(C29H + C29Ts) 0.43 0.08 MPI-3 (β/α MP) 0.74 0.93
C30*/C29Ts 0.14 2.14 MPR 0.50 0.75
C30*/(C30H + C30*) 0.05 0.13 MPR1 0.71 0.34
22S/(22S + 22R) (for C32) homohopane 0.36 0.23 MPR2 0.36 0.25
Sterane/hopane 0.34 0.20 MPR3 0.48 0.29
Steranes MPR9 0.43 0.24
C27, C28, C29 steranes (%) 34, 32, 34 35, 18, 47 1-MP/9-MP 1.66 1.40
n-, iso-, diasteranes (%) 49, 32, 19 44, 28, 28 Dibenzotiophenes
Diasterane/sterane 0.55 0.84 MDR 1.11 1.17
20S/(20S + 20R) for C29 0.10 0.12 MDR′ 0.53 0.54
ββ/(ββ + αα) 0.11 0.16 DBT/P 0.15 0.17

Sterane/hopane = C27, C28, C29 αα/ββ (20S + 20R)/C29–C33 hopane; 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).
102 R. Kara-Gülbay / International Journal of Coal Geology 149 (2015) 93–107

Fig. 8. m/z 253 and m/z 231 mass fragmentograms for coaly claystone (a, b) and coal (c, d) samples from Sütkans section.

maceral distributions which yields a general information on anoxic/oxic low ratio is associated with non-marine source rock or oil (Moldowan
conditions of dominant plant type and peat deposition in Paleomire, et al., 1985). Very low sterane/hopane ratio for coaly claystone and
coal and coaly claystone samples are located at apex B reflecting reed coal samples (0.34 and 0.20, respectively) is indicative of dominantly
swamp plant cover and intensity of bacterial activity under wet condi- terrestrial and microbial organic matter input in a non-marine
tions (Fig. 12). environment.
Samples from the Sütkans coal sequence with moderate-high HI Lacustrine deposits and coals are reported to have high C24/C23 and
values contain Type II kerogen (Fig. 13 a,b). Evaluation of Type II kero- low C22/C21 tricyclic terpane ratio (Kara-Gülbay et al., 2012; Peters et al.,
gen together with maceral compositions reveals that coal, coaly 2005) and the Sütkans coaly claystone and coal samples have no excep-
claystone, and clayey coal samples contain insignificant amount of lig- tion to this. C31 22R/C30 hopane ratio is reported to be less than 0.25 for
neous organic contribution, dominant terrestrial herbaceous organic lacustrine deposits and higher for marine deposits (Kara Gülbay et al.,
matter, and significant amount of bacterial and lesser algal organic mat- 2010, 2012, 2014; Kara-Gülbay and Korkmaz, 2012; Peters et al., 2005).
ter contribution. In gas chromatographs, unimodal n-alkane distribution This ratio is less than 0.25 for Sütkans samples (0.20, 0.08) consistent
which is dominated by high-carbon numbers indicates terrestrial or- with a lacustrine environment. C19 and C20 tricyclic terpane abundance
ganic matter input. High CPI and TAR values (Table 6) in coal and is associated with high terrestrial plant source and high (C19 + C20)/C23
coaly claystone samples also reveal terrestrial organic matter input, tricyclic terpane ratio is suggested to indicate terrestrial organic matter
however, lower TAR values in coaly claystone sample is attributed input (Peters and Moldowan, 1993). High (C19 + C20)/C23 tricyclic
to the fact that terrestrial organic matter content in claystone is terpane ratios of Sütkans coal and coaly claystone samples (1.06 and
lower than that which is in coal sample. Moderate-high HI index 2.02, respectively) indicate significant terrestrial organic matter input.
(176–722 mg HC/g rock) and very low OI value (3–36 mg CO2/g rock) Ts/(Ts + Tm) ratio increases with maturity which is also affected by
of coal and coaly claystone samples indicate that deposition took place source lithology (Moldowan et al., 1986). In oils or extractions particularly
in an anoxic environment. from clay stones, Ts tends to be dominant over Tm (McKirdy et al., 1983;
C30* (diahopane) abundance is due to bacterial contribution to clay- Rullkötter et al., 1985). Ts/(Ts + Tm) ratio of Sütkans coal and coaly
rich sediments being deposited in the oxic–suboxic environment claystone samples are very low (0.03 and 0.28), and this ratio is high for
(Peters et al., 2005). Volkman et al. (1983) and Philp and Gilbert the coaly claystone. C29 sterane which reflects terrestrial organic matter
(1986) propounded that the presence of C30* is associated with terres- input (Czochanska et al., 1988; Huang and Meinschein, 1979) extremely
trial organic matter input. Relative abundances of C30* and C29 Ts are dominates over C27 and C28 for the coal sample. For the Sütkans coaly
strongly related to depositional environment and high C30*/C29Ts ratio claystone and coal samples, C29 MA steroid exceptionally dominates
is indicative of oxic–suboxic conditions whilst lower values stand for over C27 and C28, and such distribution is associated with a non-marine
anoxic conditions (Peters et al., 2005). Coaly claystone sample has low organic matter in which terrestrial organic matter is dominated
C30* content, higher C29Ts content, and low C30*/C29Ts ratio but this (Moldowan et al., 1985; Volkman, 1986). In non-marine shales, C29/
ratio is very high for the coal sample. In this respect, coal sample was de- (C28 + C29) monoaromatic steroid ratio is higher than 0.5 (Moldowan
posited in an oxic–suboxic environment with hig-bacterial activity and et al., 1985). This ratio for Sütkans coal and coaly claystone samples
terrestrial organic contribution whilst coaly claystone was deposited in is 0.80 and 0.73 reflecting a non-marine organic matter. High
anoxic conditions with significantly lower bacterial and terrestrial dibenzothiophene and alkyl benzothiophene concentrations are charac-
input. Low sterane/hopane ratio reflects terrestrial or microbial teristic to marine shale and carbonates and their abundance is generally
reworked organic matter (Tissot and Welte, 1984). In addition, this low in continental facies (Radke et al., 1991). Low concentrations
 R. Kara-Gülbay / International Journal of Coal Geology 149 (2015) 93–107 103

Fig. 9. m/z 178–m/z 192 and m/z 187–m/z 196 mass fragmentograms for coaly claystone (a, b) and coal (c, d) samples from Sütkans section.

recorded in Sütkans coal and coaly claystone samples might indicate that 5.2. Maturity of organic matter
the sequence was deposited within the continental environment. The re-
lation between alkyl benzothiophene and phenanthrene concentrations Tmax values of Sütkans coal, clayey coal and coaly claystone samples
and organic facies is expressed by DBT/P ratio (Hughes et al., 1995; vary between 413 and 437 °C which reflect immature-early mature
Radke et al., 1991). DBT/P ratio of 0.06–0.2 is generally typical to coals character. Mean random huminite reflectance values (Rr%) measured
(Requejo, 1994), and this ratio for Sütkans coaly claystone and coal sam- on coal samples are between 0.40 and 0.48% (average 0.44%) which
ples is computed as 0.15 and 0.17, respectively (Table 7). In the deposition stands for sub-bituminous B rank (Stach et al., 1982). CPI(24–34) values
environment diagram, DBT-Pr/Ph ratio of coaly claystone sample plots that are computed greater than 1 (1.62–1.96) indicate immature char-
into “marine shale and other lacustrine (3)” field and coal sample corre- acter of coal and coaly claystone samples.
sponds to fluvial/deltaic (4) area (Fig. 14). 22S/(22R + 22S) homohopane (for C32), 20S/(20R + 20S), and ββ/
Geologic, palynological, petrographic, and organic geochemical data (αα + ββ) sterane (for C29) ratios increase with thermal maturity
(TOC, pyrolysis, n-alkane, isoprenoid, saturated, and aromatic biomark- (Mackenzie and McKenzie, 1983; Schoell et al., 1983; Seifert and
er distributions) on the Sütkans coal sequence indicate that the se- Moldowan, 1986), and these values computed very low coal and coaly
quence was deposited in a terrestrial environment under lacustrine– claystones (Table 7). Moretane/hopane ratio decreases with maturity
fluvial conditions. These data also yield that coal and coaliferous levels (Seifert and Moldowan, 1980) and the ratios calculated for coal and
were mostly deposited under suboxic–anoxic conditions with high pH coaly claystones (0.30, 0.60) reflect an immature character. Tricyclic
and microbial decomposition. Coal and coaliferous levels are represent- terpane/hopane ratio increases with maturity (Aquino Neto et al.,
ed dominantly by terrestrial plant and microbial organic matter and 1983) and very low C23tt/(C23tt + C30 hopane) ratios of Sütkans sam-
slightly by input of algal organic matter. ples (0.05, 0.04) are in support of low maturity.
104 R. Kara-Gülbay / International Journal of Coal Geology 149 (2015) 93–107

Fig. 12. ABC ternary diagram of the Sütkans coal samples. A = Telohuminite +
corpohuminite + spor + cutinite + resinite + suberinite; B = Detrohuminite +
gelinite + lipodetrinite + alginite; C = Inertinite.

classified as immature (Radke, 1987). MPI-3 values of Sütkans coaly

claystones and coals are computed as 0.74 and 0.93, respectively.
These values reflect an immature, moderately mature character.
It is suggested that MPR (methylphenanthrene ratio), MPI-1
(methylphenanthrene index) (Radke et al., 1982), and 1-MP/9-MP
ratio (Alexander et al., 1992) was very significant in low-rank coals
(Amijaya et al., 2006). MPI and MPR increase to a certain maturity
(VRr ≈ 2.5%) but decrease in high-rank coals. For the Sütkans coals
Fig. 10. (a) GI vs. TPI (after Diessel, 1986), (b) GWI vs. VI plot (after Calder et al., 1991) of and coaly claystones, thermodynamically less stable 1-MP and 9-MP
the Sütkans coal samples. dominate over 2MP and 3-MP and MPI and MPR values are very low
(Table 7).
It is stated that relative abundance of each alkyl-dibenzotiophene
Investigations on alkyl-phenanthrenes show that they can be used depends on the maturity. Regarding methyldibenzotiophene ratios
as a maturity parameter (Radke et al., 1982). Radke (1987) using the (MDR and MDR′), they are decreased with the maturity of 1-MDBT
MPI-3 value classified oils into three maturity categories (Stojanovic and the relative increase of 4-MDBT which is thermally more stable
et al., 2001). This value is the ratio of 2-MP and 3MP (β-isomers) (Radke et al., 1986). 4-MDBT concentration of Sütkans samples is slight-
isomers, that are thermodynamically more stable, to 1-MP and 9-MP ly higher with respect to other methyldibenzotiophenes and there is no
(α-isomers) isomers, that are thermodynamically less stable. Those significant dominance (MDR = 1.11, 1.17) (Table 7).
with MPI-3 value larger than 1 are mature, MPI-3 values between 0.8 Hussler et al. (1981) showed the presence of monoaromatic steroids
and 1.0 are moderately mature and MPI-3 value less than 0.8 are in sterane-bearing immature sediments. This might indicate that
monoaromatic steroids could be survived in mil diagenetic conditions.
However, triaromatic steroid components are not significantly recorded
in recent sediments indicating that their formation is associated with
post-depositional diagenesis stage (El-Gayar, 2005). Aromaticity is
found to increase with an increasing maturity of crude oils and sedi-
ments (Mackenzie et al., 1981; Seifert and Moldowan, 1978). Therefore,
with the increasing maturity, monoaromatic steroids (MA) transform to
triaromatic steroids (TA) and thus triaromatic steroid abundance is in-
creased. This ratio [C28TA/(C29MA + C28TA) steroid] that ranges from
0 to 100% through the maturity can be used for immature–mature inter-
val (Hunt, 1995; Peters and Moldowan, 1993). For the Sütkans coaly
claystones and coals this ratio is found as 0.03 and 0.33 reflecting an im-
mature character. Thermal maturity results in an increase in MA(I) with
respect to MA(II). The reason for this is that MA(I) is more resistant to
thermal maturity than MA(II) and with increasing maturity MA(II)
loses its side chain and transforms to MA(I) (Hunt, 1995). MA(I)/
MA(I + II) ratio attains equilibrium with a complete transformation
(100%) at the end of late mature stage (Peters et al., 2005). This param-
eter that is found as 0.08 and 0.06 for the Sütkans samples reflects an
Fig. 11. Cross plot of Pr/nC17 vs. Ph/nC18 for the Belen and Naltas shale samples (after immature character. Short-chain TA-steroids (TA-I) are increased with
Shanmugam, 1985). increasing thermal maturity and the ratio at the end of late mature
 R. Kara-Gülbay / International Journal of Coal Geology 149 (2015) 93–107 105

Fig. 13. The distribution of the Sütkans coal samples on (a) HI-Tmax and (b) TOC-S2 kerogen type diagram.

stage attains equilibrium with a complete transformation. This increase Saturated and aromatic biomarker maturity parameters show that
is related to preferential degradation of TA-II homologues rather than coal and coaly claystone samples have not reached a maturity level to
transformation of TA-I to TA-II (Beach et al., 1989; Hunt, 1995). TA(I)/ generate oil.
TA(I + II) ratio of Sütkans samples are very low (0.08, 0.15) reflecting Maceral compositions of coal samples and high GI-GWI and low VI-
ans immature character. TPI values computed from these compositions reveal that coals were de-
posited in a swamp environment with high water level where microbial
5.3. Hydrocarbon potential decomposition was elevated to high pH levels (non-acidic). The fact
that coals are alternated with coaly claystone and clayey coals and con-
Moderate-high HI values (176–722 mgHC/g rock) (Tip II kerogen) tain limestone and claystone interlayers might indicate that the envi-
arising from high S2 values of Sütkans samples indicate that coals and ronment was deepened time to time and changed to lake and during
coaly claystone samples contain significant amount of organic matter the course of the deposition of the sequence, lake and swamp conditions
that are suitable for pyrolysis and oil generation. High Potential Yield were repeated several times. Palynological and saturated-aromatic bio-
(PY) values (in the range of 12.7–237.79 mgHC/g rock) might show marker data on coal and coaly claystone samples show that deposition
that these samples have quite high hydrocarbon potential (oil and took place in a non-marine environment (terrestrial) changing in
gas). According to S2-TOC data, clayey coal and coaly claystone samples
are excellent source rocks (Fig. 15). Although high hydrocarbon poten-
tial and excellent source rock character, immature-early mature charac-
ter of the Sütkans sequence indicates that hydrocarbon generation of
economic value has not been progressed.

6. Conclusion

Coal samples from the Sütkans section have very high ash content
(6.28–44.60%, average 27.99%) but calorific value of the coals is very
high (3947–7583 Kcal/kg). Random huminite reflectance (Vr%) values
of coals are btween 0.40 and 0.48 (average 0.44) indicating a sub-
bituminous B rank. Tmax values (413–437 °C) of coal, coaly claystone
and clayey coal samples reflect immature-early mature stages.

Fig. 15. A cross plot of total organic carbon (TOC) versus S2 for Sütkans coal samples (after
Fig. 14. DBT/P vs. Pr/Ph plot of the Sütkans coal samples (Hughes et al., 1995). Dembicki, 2009).
106 R. Kara-Gülbay / International Journal of Coal Geology 149 (2015) 93–107

character from lacustrine to fluvial under predominantly suboxic–anox- Bozkuş, C., 1992. Stratigraphy of the Olur (Erzurum) region. Geol. Bull. Turk. 35,
103–119.
ic conditions. Calder, J., Gibling, M., Mukhopadhyay, P., 1991. Peat formation in a Westphalian B pied-
Based on maceral compositions, coal samples dominantly contain mont setting, Cumberland Basin, Nova Scotia: implications for the maceral-based in-
terrestrial plant and microbial organic matter as well as less amount of terpretation of rheotrophic and raised paleomires. Bull. Soc. Geol. Fr. 162 (2),
283–298.
algal organic matter. According to pyrolysis data, coal, coaly claystone, Çetin, A., 1976. The geological report of the Erzurum (Oltu) region. MTA Report no: 23,
and clayey coal samples are composed of Type II kerogen. Biomarker Van (in Turkish).
data indicate that coal and coaly claystones dominantly contain terres- Czochanska, Z., Gilbert, T.D., Philp, R.P., Shepard, C.M., Weston, R.J., Wood, T.A.,
Woolhouse, A.D., 1988. Geochemical application of sterane and triterpane biomarkers
trial and microbial organic matter.
to a description of oils from the Taranaki Basin in New Zealand. Org. Geochem. 12,
Coal, coaly claystone, and clayey coal samples are represented by 123–135.
moderate-high HI and very low OI values. Very high HI values imply Dembicki Jr., H., 2009. Three common source rock evaluation errors made by geologists
during prospect or play appraisals. Am. Assoc. Pet. Geol. Bull. 93, 341–356.
that the samples contain significant amount of pyrolysable organic mat-
Diessel, C.F.K., 1986. On the correlation between coal facies and depositional environ-
ter. Potential yield (S1 + S2) values of the samples are very high which ments. Advances in the study of the Sidney Basin. Proc. of the 20th Symp. Department
indicate noteworthy hydrocarbon generation potential. High HI and of Geology. University of Newcastle, N.S.W., pp. 19–22.
Potential Yield (PY) values and Type II kerogen character show that Ediger, V.Ş., Alişan, C., 1989. Tertiary fungal and algal palynomorph biostratigraphy of the
Northern Thrace Basin, Turkey. Rev. Palaeobot. Palynol. 58, 139–161.
samples from the Sütkans section are represented by a significant hy- Ediger, V.Ş., Batı, Z., Alişan, C., 1990. Paleopalynology and paleoecology of calamus-like
drocarbon (oil and gas) potential. Immature-early mature character of disulcate pollen grains. Rev. Palaeobot. Palynol. 62, 97–105.
the samples propounds that hydrocarbon generation of economic sig- El-Gayar, M.Sh., 2005. Aromatic steroids in Mideastern crude oils: identification and geo-
chemical application. Pet. Sci. Technol. 23, 971–990.
nificance has not been taken place. Huang, W.Y., Meinschein, W.G., 1979. Sterols as ecological indicators. Geochim.
Cosmochim. Acta 43, 739–745.
Acknowledgements Hughes, W.B., Holba, A.G., Dzou, L.I.P., 1995. The ratio of dibenzothiophene to phenan-
threne and pristane to phytane as indicators of depositional environment and litology
of petroleum in source rocks. Geochim. Cosmochim. Acta 59, 3581–3598.
The Karadeniz Technical University (KTU) Scientific Research Foun- Hunt, J.M., 1995. Petroleum Geochemistry and Geology. W.H. Freeman and Company,
dation financially supported this study (Project No: 2008.112.005.7). New York.
Hussler, G., Chappe, B., Wehrung, P., Albrecht, P., 1981. C27–C29 ring A monoaromatic ste-
Oltu coal operation supported this study in sampling. The analyses roids in Cretaceous black shale. Nature 294, 556–558.
were carried out in the TPAO (Turkish Petroleum Corp.) Organic Geo- ICCP, 1998. The new vitrinite classification (ICCP System 1994). Fuel 77, 349–358.
chemistry and General Directorate of Mineral Research and Exploration ICCP, 2001. The new inertinite classification (ICCP System 1994). Fuel 80, 459–471.
ISO 7404-2, 2009. Methods for the petrographic analysis of coals — Part 2: Methods of
(MTA) laboratories. The author thanks these organizations. The author
preparing coal samples. Standards Australia, Level 10, The Exchange Centre 20 Bridge
thanks an anonymous reviewer and editor in chief C.Ö. Karacan who Street, GPO Box 476, AU-Sydney NSW 2001 (www.standards.org.au).
provided useful comments and improved the manuscript. ISO 7404-3, 2009. Methods for the petrographic analysis of coals — Part 3: Method of de-
termining maceral group composition. Standards Australia, Level 10, The Exchange
Centre 20 Bridge Street, GPO Box 476, AU-Sydney NSW 2001 (www.standards.org.
Appendix A. Supplementary data au).
ISO 7404-5, 2009. Methods for the petrographic analysis of coals — Part 5: Method of de-
Supplementary data associated with this article can be found in the termining microscopically the reflectance of vitrinite. Standards Australia, Level 10,
The Exchange Centre 20 Bridge Street, GPO Box 476, AU-Sydney NSW 2001 (www.
online version, at http://dx.doi.org/10.1016/j.coal.2015.06.012. These standards.org.au).
data include the Google map of the most important areas described in Kalaitzidis, P., Papazisimou, S., Bouzinos, A., Christanis, K., 2004. A short-term establish-
this article. ment of forest fen habitant during Pliocene lignite formation in the Ptolemais Basin,
NW Macedonia Greece. Int. J. Coal Geol. 57, 243–263.
Kalkreuth, W., Kotis, T., Papanicaola, C., Kokkinakis, P., 1991. The geology and coal petrol-
References ogy of a Miocene lignite profile at Meliadi Mine Katerini, Greece. Int. J. Coal Geol. 17,
51–67.
Akalın, L., 1977. Studies of Balkaya and Sütkans (Erzurum) lignite areas. MTA Report no: Kara Gülbay, R., Yurtsever, T.S., Korkmaz, S., Demirel, İ.H., 2010. Source rock potential and
224 (in Turkish). organic geochemistry of Cenomanian–Turonian Black Shales, Western Taurus, SW
Alexander, R., Larcher, A.V., Kagi, R.I., Price, P.L., 1992. An oil-source correlation study Turkey. J. Pet. Geol. 33, 355–370.
using age-spesific plant-derived aromatic biomarkers. In: Moldowan, J.M., Albrecht, Kara Gülbay, R., Şen, Ö., Korkmaz, S., Demirel, İ.H., 2014. Lower Karboniferous shales in
P., Philp, R.P. (Eds.), Biological Markers in Sediments and Petroleum. Prentice Hall, the Eastern Tauride Belt, southern Turkey: source rock characteristics. J. Pet. Geol.
New Jersey, pp. 201–220. 37, 25–42.
Altınlı, L.E., 1969. The geological investigation of the Oltu-Olur-Narman area. TPAO Report Kara-Gülbay, R., Korkmaz, S., 2012. Occurrences and origin of oils and asphaltites from
No: 449, Ankara. South East Anatolia (Turkey): implications from organic geochemistry. J. Pet. Sci.
Amijaya, H., Schwarzbauer, J., Littke, R., 2006. Organic geochemistry of the Lower Suban Eng. 90–91, 145–158.
coal seam. South Sumatra Basin. Indonesia: palaeoecological and thermal metamor- Kara-Gülbay, R., Kırmacı, M.Z., Korkmaz, S., 2012. Organic geochemistry and depositional
phism implications. Org. Geochem. 37, 261–279. environment of the Aptian bituminous limestone in the Kale Gümüşhane area (NE-
Aquino Neto, F.R., Trendel, J.M., Connan, J., Albrecht, P.A., 1983. Occurrence and formation Turkey): an example for lacustrine deposits on the platform carbonate sequence.
of tricyclic and tetracyclic terpanes in sediments and petroleums. In: Bjoroy, M., Org. Geochem. 49, 6–17.
Albrecht, C., Cornford, C., et al. (Eds.), Advances in Geochemistry 1981. John Wiley Karayiğit, A.İ., Kerey, İ.E., Bozkuş, C., 2002. Depositional environments of Oligo/Miocene
& Sons, New York, pp. 659–676. Coal-Bearing strata and coal quality from the Oltu-Balkaya Basin, Northeastern
ASTM D 4239, 2010. Standard Test Method for Sulfur in the Analysis Sample of Coal and Turkey. Energy Sources 24, 653–665.
Coke Using High-Temperature Tube Furnace Combustion Methods: American Society Korkmaz, S., Kara Gülbay, R., Turan, M., 2008. Fossil fuel potential of Turkey: a statistical
for Testing and Materials (ASTM). evaluation of reserves, production and consumption. Energy Sources Part B 3,
ASTM D 7582, 2012. Standard Test Method for Poximate Analysis of Coal and Coke by 296–304.
Macro Thermogravimetric Analysis. Lahn, S., 1939. The geological investigation of the region between Karasu and Çoruh. MTA
ASTM D5865-04, 2004. Standard Test Method for Gross Calorific Value of Coal and Coke. Report no: 838. Ankara (in Turkish).
American Society for Testing and Materials (ASTM), USA. Lange, S., 1967. The geological report of Erzurum-Oltu-Balkaya lignite Basin. MTA Report
Batı, Z., 1996. Palynostratigraphy and Coal Petrography of the Upper Oligocene Lignites of No: 122, Ankara (in Turkish).
the Northern Thrace Basin, NW Turkey (PhD Dissertation) Middle East Technical Uni- Mackenzie, A.S., McKenzie, D., 1983. Isomerization and aromatization of hydrocarbons in
versity, p. 341. sedimentary basins formed by extension. Geol. Mag. 120, 417–470.
Batı, Z., Erk, S., Akça, N., 1993. The Palynomorph, Foraminifera And Nanoplankton Biostra- Mackenzie, A.S., Hoffmann, C.F., Maxwell, J.R., 1981. Molecular parameters of maturation
tigraphy of Tertiary Units in the Thrace Basin. TPAO Research Center, Report no: in the Toarcian shales, Paris Basin, France-III. Changes in aromatic steroid hydrocar-
1947, Ankara (in Turkish). bons. Geochim. Cosmochim. Acta 45, 1345–1355.
Bayraktutan, S., 1982. The Sedimentalogical Evolution of Narman (Erzurum) Basin in Mio- McKirdy, D.M., Aldridge, A.K., Ypma, P.J.M., 1983. A geological comparison of some
cene (Ph.D. thesis), Atatürk University, Faculty of Science and Literature, Erzurum (in crude oils from Pre-Ordovician carbonate rocks. In: Bjoroy, M., Albrecht, C.,
Turkish with english abstract). Cornford, C., et al. (Eds.), Advances in Organic Geochemistry 1981. John Wiley
Beach, F., Peakman, T.M., Abbott, G.D., Sleeman, R., Maxwell, J.R., 1989. Laboratory thermal & Sons, New York.
alteration of triaromatic steroid hydrocarbons. Org. Geochem. 14, 109–111. Moldowan, J.M., Seifert, W.K., Gallegos, E.J., 1985. Relationship between petroleum com-
Bozkuş, C., 1990. Stratigraphy of northeast (Kömürlü) Oltu-Narman Tertiary basin. Geol. position and depositional environment of petroleum source rocks. AAPG Bull. 69,
Bull. Turk. 33, 47–56 (in Turkish with English abstract). 1255–1268.
 R. Kara-Gülbay / International Journal of Coal Geology 149 (2015) 93–107 107

Moldowan, J.M., Sundararaman, P., Schoell, M., 1986. Sensitivity of biomarker properties Schoell, M., Teschner, M., Wehner, H., Durand, B., Oudin, J.L., 1983. Maturity related bio-
to depositional environment and/or source input in the Lower Toarcian of S.W. marker and stable variations and their application to oil/source rock correlation in
Germany. Org. Geochem. 10, 915–926. the Mahakam Delta, Kalimantan. In: Bjorøy, M., et al. (Eds.), Advances in Organic
Mukhopadhyay, P., 1989. Organic petrography and organic geochemistry of Tertiary coals Geochemistry 1981. J. Wiley and Sons, New York, pp. 156–163.
from Taxas in relation to depositional environment and hydrocarbon generation. Re- Seifert, W.K., Moldowan, J.M., 1978. Applications of steranes, terpanes and
port of İnvestigations. Bureau of Economic Geology, Texas. monoaromatics to the maturation, migration and source of crude oils. Geochim.
Nebert, K., 1963. The report on geological structure of the Sütkans area and the geology of Cosmochim. Acta 42, 77–95.
the coal bed. MTA report no: 3232, Ankara. Seifert, W.K., Moldowan, J.M., 1980. The effect of thermal stress on source-rock quality as
Özcanoğlu, S., 1960. The lignite occurences in the Kemerkaya (Pakih) and Sütlüce measured by hopane stereochemistry. Phys. Chem. Earth 12, 229–237.
(Sütkans) villages (Oltu). MTA Report no: 2807, Ankara. Seifert, W.K., Moldowan, J.M., 1986. Use of biological markers in petroleum exploration.
Peters, K.E., Moldowan, J.M., 1993. The Biomarker Guide: Interpreting Molecular Fossils in In: Johns, R.B. (Ed.), Methods in Geochemistry and Geophysics 24, pp. 261–290.
Petroleum and Ancient Sediments. Englewood Cliffs, N.J., Prentice-Hall, New Jersey. Shanmugam, G., 1985. Significance of coniferous rain forests and related organic matter in
Peters, K.E., Walters, C.C., Moldowan, J.M., 2005. The Biomarker Guide. 2nd ed. Biomarkers generating commercial quantities of oil. Gippsland Basin, Australia. AAPG Bull. 69,
and Isotopes in Petroleum Exploration and Earth History vol. 2. Cambridge University 1241–1254.
Press, Cambridge, pp. 475–1155. Stach, E.M., Mackowsky, M.Th., Teichmüller, M., Taylor, G.H., Chandra, D., Teichmüller, R.,
Philp, R.P., Gilbert, T.D., 1986. Biomarker distributions in Australian oils predominantly 1982. Coal Petrology. Gebruder Borntraeger, Berlin.
derived from terrigenous source material. Org. Geochem. 10, 73–84. Stojanovic, K., Jovanciecevic, B., Pevneva, G.S., Golovko, J.A., Golovko, A.K., Pfendt, P., 2001.
Radke, M., 1987. Organic geochemistry of aromatic hydrocarbons. In: Brooks, J., Welte, D. Maturity assesment of oils from the Sakhalin oil fields in Russia: phenanthrene con-
(Eds.), Advances in Petroleum Geeochemistry vol. 2. Academic Press, London, tent as a tool. Org. Geochem. 32, 721–731.
pp. 141–205. Sykorova, I., Pickel, W., Christanis, K., Wolf, M., Taylor, G.H., Flores, D., 2005. Classification
Radke, M., Willsch, H., Leythaeuser, D., Teichmüller, M., 1982. Aromatic components of of huminite-ICCP System 1994. Int. J. Coal Geol. 62, 85–106.
coal: relation of distribution pattern to rank. Geochim. Cosmochim. Acta 46, Tercan, A.E., 1987. Petrogpaphic Characteristics of oltu-Aşkale (Erzurum) coals and pre-
1831–1848. feasibility study of Balkaya (Oltu) section. M.Sc. Hacettepe University, Department
Radke, M., Welte, D.H., Willsch, H., 1986. Maturity parameters based on aromatic hydro- of Mining Engineering, Ankara (in Turkish with english abstract).
carbons: influnce of the organic matter type. Org. Geochem. 10, 51–63. Tissot, B.P., Welte, D.H., 1984. Petroleum Formation and Occurrence. Springer Verlag,
Radke, M., Welte, D.H., Willsch, H., 1991. Distribution of alkylated aromatic hydrocarbons Heidelberg.
and dibenzothiophenes in rock of the Upper Rhine Graben. Chem. Geol. 93, 325–341. Volkman, J.K., 1986. A review of sterol markers for marine and terrigenous organic matter.
Requejo, A.G., 1994. Maturation of petroleum source rocks — II Quantitative changes in Org. Geochem. 9, 83–99.
extractable hydrocarbon content and composition associated with hydrocarbon gen- Volkman, J.K., Alexander, R., Kagi, R.I., Woodhouse, G.W., 1983. A geochemical
eration. Org. Geochem. 21, 91–105. reconstructionof oil generation in the Barrow Sub-basin of Western Australia.
Rullkötter, J., Spiro, B., Nissenbaum, A., 1985. Biological marker characteristics of oil and Geochim. Cosmochim. Acta 47, 2091–2106.
asphalts from carbonate source rocks in a rapidly subsiding graben, Dead Sea,
Israel. Geochim. Cosmochim. Acta 49, 1357–1370.

View publication stats