International Journal of Coal Geology: A B B B C C A

International Journal of Coal Geology 228 (2020) 103555
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International Journal of Coal Geology

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Petrographic and organic geochemical study of the Eocene Kosd Formation T

(northern Pannonian Basin): Implications for paleoenvironment and
hydrocarbon source potential
⁎
Sándor Körmösa,b, , Achim Bechtelb, Reinhard F. Sachsenhoferb, Balázs Géza Radovicsc,
Katalin Milotac, Félix Schuberta
a
University of Szeged, Department of Mineralogy, Geochemistry and Petrology, Egyetem u. 2, H-6722 Szeged, Hungary
b
Montanuniversität Leoben, Petroleum Geology, Peter-Tunner-str. 5, A-8700 Leoben, Austria
c
MOL Plc, Október huszonharmadika u. 18, H-1117 Budapest, Hungary
A R T I C LE I N FO A B S T R A C T
Keywords: The Eocene Kosd Formation forms part of the Hungarian Palaeogene Basin. The coal measure of this formation
Eocene Kosd Formation was investigated using an 18 m drill core from borehole W–1. Petrographic and organic geochemical in-
High volatile bituminous coal vestigations (Rock-Eval pyrolysis, biomarker analysis) were performed in order to characterize the depositional
Hungarian Palaeogene Basin environment, to determine the source of the organic matter within, and to assess the hydrocarbon generative
Organic geochemistry
potential.
Organic petrology
The presence of marine fossils, high TOC/S ratios and ash yields show that the deposition of the coal measure
occurred in a marine delta with individual coal layers accumulating in low-lying, rheotrophic mires. The dis-
tribution of land plant-derived biomarkers demonstrates that the peat-forming vegetation was dominated by
angiosperms, but the relative contribution of gymnosperms varied through time. In addition to land plants, algae
and aquatic macrophytes contributed to the biomass. This dense vegetation established a CO2-limited en-
vironment forcing aquatic plants to utilise HCO3− during photosynthesis. The marine environment, as well as
the predominance of carbonate rocks in the hinterland, caused slightly alkaline conditions, which, together with
reduced oxygen availability, stimulated sulphate-reducing bacterial activity and the microbial degradation of
plant remains. Consequently, Kosd Formation coal is very rich in sulphur (up to 8.8%). Moreover, the coal
contains vitrinite with a strong orange-brown fluorescence colour and swells strongly during pyrolysis. These
features are typical for coals with marine influences.
Vitrinite reflectance, Tmax, and biomarker proxies indicate that the organic matter is thermally mature and
that the Kosd coal reached the high volatile bituminous rank in the deep borehole (~2.6 km depth). Rock-Eval
parameters imply that the coal is gas- and oil-prone and reached the maturity threshold critical for first gas
generation and the onset of oil expulsion.
1. Introduction sedimentation in this basin was characterized by a generally trans-

gressive nature, where depocenters shifted northeastwards through
During the Eocene, the Mesozoic Tethys Ocean decayed into a series time (Báldi and Báldi-Beke, 1985; Kováč et al., 2016). Hence, coal
of intercontinental seas (Rögl, 1999). This new configuration of land formation started earlier in the area of the present-day Transdanubian
and sea areas modified oceanic circulation and climate (Popov et al., Mountains (the Middle Eocene Dorog Coal Formation) than in the North
2001). In the Late Eocene, Europe formed an archipelago and was en- Hungarian Mountains (the Upper Eocene coal-bearing Kosd Formation;
closed by a subtropical sea, where variations in sea level significantly Figs. 1, 2; Báldi-Beke, 2003a, 2003b; Gidai, 1978; Hámor-Vidó and
affected the distribution of depositional environments (Sachsenhofer Hámor, 2007). The Kosd Formation includes economic coal seams
et al., 2018). (Gidai, 1978). The Kosd coalfield (location is shown in Fig. 1) is re-
The Hungarian and Slovenian Palaeogene Basin is a predecessor of gistered in the national coal cadastre of Hungary (MGSH – Mining and
the Pannonian Basin (Tari et al., 1993). During the Eocene, Geological Survey of Hungary, 2019), however, mining of this sub-
⁎
Corresponding author at: University of Szeged, Department of Mineralogy, Geochemistry and Petrology, Egyetem u. 2, H-6722 Szeged, Hungary.
E-mail address: sandor.kormos@geo.u-szeged.hu (S. Körmös).
https://doi.org/10.1016/j.coal.2020.103555
Received 2 April 2020; Received in revised form 1 July 2020; Accepted 5 July 2020
Available online 15 July 2020
0166-5162/ © 2020 The Author(s). Published by Elsevier B.V. This is an open access article under the CC BY license
(http://creativecommons.org/licenses/BY/4.0/).
S. Körmös, et al. International Journal of Coal Geology 228 (2020) 103555
Fig. 1. Location of registered Eocene sub-bituminous coalfields: Kosd–20 (K−20), Varbó–75 (V–75), Noszvaj–1 (Nv–1), and the investigated W–1 boreholes.
Modified following the digital elevation model and digital coal cadastre of Hungary (Horváth et al., 2005; MGSH – Mining and Geological Survey of Hungary, 2019).
LSBD – Left Side Blocks of Danube.
bituminous coal ended in the 1930s (Némedi Varga, 2010).

Bechtel et al. (2007) performed an exhaustive geochemical study on
the Middle Eocene Dorog Coal finding that the seam originates from a
topogenous mire and evolved within a peneplane coastal area covered
with eutrophic swamps. The peat-forming vegetation at the time was
predominated by angiosperms, which is characteristic of Eocene coals
throughout central Europe (Bechtel et al., 2008). In contrast, factors
controlling the depositional environment and coal facies of the Upper
Eocene Kosd coal have not previously been investigated.
Maceral composition, petrography-based facies indicators and bio-
marker analysis became essential tools during the last decades for the
reconstruction of paleoenvironments and peat-forming floral changes
(e.g. Bechtel et al., 2003, 2007; Gross et al., 2015; Sachsenhofer et al.,
2010). Additionally, the stable carbon isotope composition of in-
dividual biological markers allows the identification of specific sources
(Hayes et al., 1987). Primary producers fix inorganic carbon through
photosynthesis, which leads to specific fractionation of carbon isotopes
(Diefendorf and Freimuth, 2017; Holtvoeth et al., 2019). Ficken et al.
(1998) found that accumulating organic matter experiences rapid mi-
crobial degradation and associated diagenetic changes in the top few
centimetres of sediment. Other studies, however, have reported no
significant changes in δ13C during early diagenesis (Li et al., 2017, and
references therein). Thermal maturation of organic matter may none-
theless affect the carbon isotope composition (Bjorøy et al., 1992;
Fig. 2. Eocene lithostratigraphy across the North-Hungarian range (modified
Clayton, 1991; Rooney et al., 1998). The degree of isotope fractionation
after Kercsmár et al., 2015; Less, 2015 oral communication). NHM – North
depends on the temperature, but the effect is limited to a range of 2‰
Hungarian Mountains and LSBD – Left Side Blocks of Danube. 1 – Gánt Bauxite
Formation, 2 – Dorog Coal Formation, 3 – Szőc Limestone Formation, 4 – as maturity progresses (Clayton, 1991; Schoell, 1984). Therefore, bio-
Csolnok Formation, 5 – Padrag Marl Formation, 6 – Tokod Formation, 7 – Kosd logically controlled isotope compositions can be used to identify pre-
Formation, 8 – Szépvölgy Limestone Formation, 9 – Buda Marl Formation. cursor sources after diagenesis (e.g. Collister et al., 1994; Freeman
et al., 1990; Rieley et al., 1991).
2
The current study is based on samples from borehole W–1, located and Less (2005) noted an upward transition from a freshwater en-
about 50 km SE from the abandoned Kosd coalfield (Fig. 1), which vironment, indicated by gastropods (Melanopsis sp.) to a shallow
drilled the Eocene succession beneath potential Oligocene hydrocarbon marine, lagoonal environment marked by the presence of nanno-
source rocks. Whereas the Oligocene source rocks have been in- plankton (Isthmolithus recurves) and foraminifers (Quinqueloculina,
vestigated by several authors (e.g. Badics and Vető, 2012; Bechtel et al., Nummulites sp.). Moreover, a proximal coastal environment is sup-
2012; Milota et al., 1995; Sachsenhofer et al., 2018), the Eocene Kosd ported by mangrove vegetation, represented by Nypa palm pollens
Formation remained largely uninvestigated. (Kvaček, 2010, and references therein; Rákosi, 1978). Coaly layers were
The aims of this study are therefore to enhance understanding of the noted by Gidai (1978) and Less (2005) in boreholes K–20 and V–75, but
depositional environment and organic matter sources in this formation, were not investigated in detail.
and to estimate the hydrocarbon potential of deep Eocene Kosd coal. To The Kosd Formation grades upward into shallow marine platform
achieve this goal, organic petrological and organic geochemical ana- carbonates of the Szépvölgy Limestone Formation (Fig. 2). The presence
lyses were performed. of the corallinacean algae and the frequently-occurring monospecific
Nummulites fabianii indicate deposition on the inner shelf, while a di-
2. Geological setting verse fauna including orthophragminas in the upper part of the for-
mation, marks a transition to an outer shelf environment during the
A series of sub-bituminous coalfields of Middle Eocene Dorog Coal deposition of Szépvölgy Limestone (Less, 2005). Continuing basin
Formation occur along the Transdanubian Mountains (Hámor-Vidó and subsidence caused deposition of the shallow bathyal Buda Marl For-
Hámor, 2007; Bechtel et al., 2007). Eocene coal in the North Hungarian mation, in low-oxic environments across the Eocene-Oligocene transi-
Mountains belongs to the Upper Eocene Kosd Formation (Fig. 1; Gidai, tion (Ozsvárt et al., 2016). The Tard Clay Formation accumulated in
1978; Báldi-Beke, 2003a, 2003b). The diachronous development of oxygen-depleted conditions (Bechtel et al., 2012; Ozsvárt et al., 2016),
depocenters followed the gradual northeastward trend of the Eocene and the Kiscell Clay Formation was deposited in a more oxygenated
transgression (Báldi and Báldi-Beke, 1985). In the western part of the environment (Bechtel et al., 2012). A sequence of siliciclastic and car-
Transdanubian Mountains, the initial transgression took place during bonate platform sediments terminates the Palaeogene succession,
the early Lutetian. The next transgression flooded the entire Transda- which is followed by thick Neogene deposits (Less, 2005; Kercsmár
nubian Range during the late Lutetian (the Dorog Coal Formation; et al., 2015).
Fig. 2). In contrast, for the eastern part of the Transdanubian Mountains The coal measures of the Kosd Formation in the former Kosd coal-
and the North Hungarian Mountains, the transgression occurred during field (Fig. 1) are 5 to 32 m thick and include three seams (Kubacska,
the Bartonian and Priabonian (the Kosd Formation; Fig. 2; Báldi-Beke, 1925; Gidai, 1978; Némedi Varga, 2010). The lower seam is 0.5 to
2003a, 2003b; Kercsmár et al., 2015; Kováč et al., 2016). 2.5 m thick and was exploited between 1904 and 1931 via an under-
The Kosd Formation crops out in small areas throughout the Buda ground mine approximately 130 m below the surface. The coal reaches
Hills, the Left Side Blocks of Danube and the Bükk Mountains. In the the sub-bituminous stage in the shallow mine. Based on contemporary
subsurface, it extends towards the south into the Gödöllő Hills (Fig. 1), data (Papp, 1913), the coal includes 3–4 wt% moisture and the ash
where it was encountered by several boreholes (e.g. Bauer et al., 2016; yield varies from 6 to 20 wt%. The elemental composition of the coal is
Palotai and Csontos, 2010). 56–67 wt% carbon, 4–6 wt% hydrogen, 1 wt% nitrogen and 5–6 wt%
The Kosd Formation unconformably overlies the Mesozoic base- sulphur (Papp, 1913). According to Némedi Varga (2010), the average
ment, which belongs to different mega-units. In the Buda Hills and the calorific value is 19 MJ/kg and the potential reserves were estimated as
Left Side Blocks of Danube (Transdanubian Range Unit) the basement is 15 Mt.
represented by Ladinian to Norian platform carbonates (e.g. the
Budaörs Dolomite Formation; the Dachstein Limestone Formation), and 3. Samples and analytical methods
cherty basinal carbonates (e.g. the Mátyáshegy Formation; Haas and
Kovács, 2012). In the Bükk Mountains (Bükk Unit), in addition to La- 3.1. Samples
dinian to Norian platform carbonates (e.g. the Berva Limestone For-
mation; the Kisfennsík Limestone Formation) and basinal carbonates Borehole W–1, drilled in the early 2000s in the southern part of the
(the Felsőtárkány Limestone Formation), a deep marine Middle to Gödöllő Hills by MOL Plc. (Fig. 1), penetrated the Kosd Formation from
Upper Jurassic sedimentary succession, with debris flows and turbi- 2415 m to 2791 m. A drill core, representing the upper section of the
dites, are present (the Mónosbél Group; Pelikán, 2005). The Mesozoic coal measures in the Kosd Formation, was recovered from 2587 m to
strata were uplifted during the Late Cretaceous and as a consequence of 2605 m. In total, 35 samples (Table 1) were obtained from this drill
the subaerial exposure intense karstification occurred (Haas and core, each of them was selected based on lithological differences and is
Kovács, 2012). representative of a 20 cm interval. In order to avoid contamination,
Depending on the palaeotopography of the karst surface, the about 0.5 cm of the outer rim of each core was removed. Moreover, to
thickness of the Kosd Formation varies considerably and reaches 244 m prevent outlier readings, samples containing pyrite aggregates or no-
in borehole Noszvaj–1 (Nv–1; the location is shown in Fig. 1; Less, dules were not selected during sample collection. Pyrite crystals in the
2005). The Kosd Formation was described in detail in two wells macroscopic range were hand-picked from the samples prior to pul-
(Kosd–20 [K−20]; Varbó–75 [V–75]; Fig. 1) by Gidai (1978) and Less verization.
(2005). In both wells, the Kosd Formation is characterized by two dif-
ferent sedimentary facies. The lower facies contains fossil- and carbo- 3.2. Petrographic analysis
nate-free variegated clay with different amounts of rock debris, de-
posited in a terrestrial environment. The overlying sediments include Fifteen core samples, including all coal and coaly shale samples as
claystone, siltstone with varying carbonate content, marl and thin coal well as selected mudstone samples, were prepared as whole-rock po-
layers (Gidai, 1978; Less, 2005). The thickness of the lower and upper lished blocks for maceral analyses. Each sample was cut perpendicular
sedimentary sequences is 63 and 12 m, respectively, at V–75 well (Less, to the bedding plane, embedded in epoxy resin and polished according
2005) and 9 and 123 m, respectively, at K–20 well (Gidai, 1978). The to standard procedures (ASTM International, 2015). Organic matter
coal is intercalated into calcareous claystone and marl at V–75 and was identified by reflected white- and UV-fluorescent light microscopy
K–20 wells, respectively, whereas the direct underlying sediments are using a Leica DM4P microscope equipped with a 50× oil-immersion
characterized by varicoloured clay with carbonate debris. The overlying objective and a point counter equipped with an OptiScan fully auto-
sediments grade into Miliolina-bearing calcareous marl. Gidai (1978) mated scanning stage. Maceral analyses were performed using a single
3
Table 1
Bulk geochemical parameters of samples from the Kosd Formation.
ID Depth Lithotype TIC TOC CEq TS Ash yield TOC/TS S1 S2 HI BI QI PI Tmax
# [m; MD] [wt%, db] [mg HC/g rock] [mg HC/g TOC] [°C]
1 2587.10 siltstone 0.6 0.6 4.9 2.5 – 0.2 0.1 0.3 51 – – 0.30 441
2 2587.75 siltstone 2.5 0.5 20.5 2.1 – 0.2 0.1 0.4 75 – – 0.24 446
3 2588.00 siltstone 1.3 0.6 10.9 2.4 – 0.2 0.2 0.4 63 – – 0.31 446
4 2589.20 siltstone 1.3 0.7 10.4 2.8 – 0.3 0.3 0.5 71 – – 0.35 445
5 2590.00 coaly shale 0.8 29.5 6.8 4.0 59.4 7.3 10.0 71.9 243 34 277 0.12 441
6 2590.20 claystone – 7.2 – 1.6 – 4.6 2.5 20.9 289 – – 0.11 443
7 2591.00 siltstone 0.9 1.2 7.5 2.9 – 0.4 0.6 1.0 80 – – 0.39 443
8 2591.80 siltstone 2.8 0.5 23.6 2.3 – 0.2 0.3 0.5 102 – – 0.37 439
9 2592.20 siltstone 4.3 0.5 36.1 1.7 – 0.3 0.1 0.3 62 – – 0.32 443
10 2593.00 siltstone 0.8 0.6 6.6 1.4 – 0.4 0.2 0.3 60 – – 0.31 446
11 2593.70 siltstone 2.3 0.6 18.9 2.5 – 0.3 0.3 0.4 65 – – 0.39 446
12 2594.40 siltstone 0.9 0.4 7.3 2.5 – 0.2 0.1 0.1 36 – – 0.33 439
13 2594.55 coaly shale 0.7 12.7 5.7 3.5 77.9 3.6 3.8 31.9 251 30 280 0.11 441
14 2594.92 siltstone 0.9 1.5 7.8 2.6 – 0.6 0.7 1.0 68 – – 0.40 439
15 2596.80 siltstone 0.9 0.5 7.8 1.7 – 0.3 0.5 0.3 66 – – 0.61 446
16 2597.00 siltstone 0.9 0.5 7.6 2.4 – 0.2 0.1 0.2 40 – – 0.38 438
17 2597.40 siltstone 1.0 0.8 8.4 3.2 – 0.3 0.3 0.5 64 – – 0.36 447
18 2598.30 siltstone 0.8 0.9 6.3 2.4 – 0.4 0.6 0.6 65 – – 0.51 437
19 2598.50 siltstone 0.6 0.8 5.2 2.5 – 0.3 0.6 0.5 54 – – 0.56 432
20 2599.00 siltstone 0.1 1.0 0.5 3.2 – 0.3 0.4 0.4 39 – – 0.47 431
21 2599.90 coal 0.4 78.4 3.6 3.4 5.8 23.0 23.4 186.3 238 30 267 0.11 443
22 2600.00 claystone – 2.9 – 4.8 – 0.6 1.1 3.0 103 – – 0.27 443
23 2600.60 claystone 0.1 2.9 1.0 3.0 – 1.0 1.5 2.9 101 – – 0.34 445
24 2600.95 coal – 45.7 – 8.8 32.1 5.2 14.6 133.1 291 32 323 0.10 441
25 2601.00 siltstone – 3.8 – 4.5 – 0.9 1.8 6.6 171 – – 0.22 448
26 2601.20 coaly shale 0.3 25.0 2.7 5.9 62.0 4.2 9.3 66.1 264 37 301 0.12 440
27 2601.40 siltstone 1.1 3.0 9.3 4.7 – 0.6 1.1 4.9 165 – – 0.19 446
28 2602.00 coaly shale – 21.8 – 4.9 66.2 4.5 6.6 53.8 247 30 277 0.11 438
29 2602.40 siltstone 1.4 1.0 11.9 3.4 – 0.3 0.9 0.8 82 – – 0.52 444
30 2602.60 siltstone 1.1 1.0 8.8 3.1 – 0.3 0.9 0.7 71 – – 0.55 441
31 2603.30 siltstone 1.1 0.7 9.1 3.0 – 0.2 0.5 0.6 90 – – 0.47 441
32 2603.50 siltstone 1.8 0.7 15.4 3.1 – 0.2 0.5 0.7 97 – – 0.41 442
33 2604.10 siltstone 3.5 0.8 29.3 2.1 – 0.4 0.4 0.7 92 – – 0.38 443
34 2604.90 coal 1.1 57.2 9.0 3.4 30.5 16.6 17.2 130.8 229 30 259 0.12 444
35 2605.00 claystone 1.1 0.8 9.4 2.6 – 0.3 0.5 0.9 107 – – 0.38 444
MD – measured depth; db – dry basis; TIC – total inorganic carbon content, TOC – total organic carbon content, CEq – calcite equivalent, TS – sulphur content, TOC/
TS – ratio of total organic carbon versus total sulphur content, S1 – free hydrocarbons, S2 – hydrocarbons generated during Rock-Eval pyrolysis, HI – hydrogen index,
BI – bitumen index, QI – quality index, PI – production index, Tmax – temperature of maximum hydrocarbon generation.
scan method (Taylor et al., 1998) considering at least 1500 individual production index (PI; PI = S1/(S1 + S2) [−]; Espitalié et al., 1977),
points to assess the minimum 500 counts of macerals. The terminology bitumen index (BI; BI = S1 × 100/TOC [mg HC/g TOC]; Killops et al.,
and classification of macerals used in this study are based on the ICCP 1998) and quality index (QI; QI = (S1 + S2) × 100/TOC [mg HC/g
system (ICCP, 1998, 2001; Pickel et al., 2017). TOC]; Pepper and Corvi, 1995).
Mean random reflectance (%Rr) of telovitrinite was measured ac- Based on the results of Rock-Eval pyrolysis and the diverse lithol-
cording to the methods of Taylor et al. (1998), and was performed ogies observed, ten samples (#20 to #29) representing the depth in-
under monochromatic (546 nm) light using an Olympus BX41 micro- terval between 2599.0 and 2602.4 m were chosen for solvent extrac-
scope equipped with a 50× oil-immersion objective and optical stan- tion. The upper- and lowermost samples represent typical low-TOC
dards of Buehler Ltd. Reflectance values were processed by image intercalating lithologies, whereas the others are coaly shale and coal
analysis (Taylor et al., 1998). samples together with their adjacent sediments.
Representative portions of powdered rock samples were extracted
3.3. Organic geochemical analysis using a Dionex ASE 350 accelerated solvent extractor. A di-
chloromethane solvent was used at confined conditions of 75 °C and
Powdered rock samples were analysed in duplicate for total sulphur 110 bar (full details of this procedure are given in Gross et al., 2015).
(TS) and total carbon (TC) contents using an ELTRA Helios CS-580A The saturated compounds were further separated into normal alkanes
analyser. Samples pre-treated by hot and diluted H3PO4 were used to and branched–cyclic alkanes for compound-specific isotopic analyses
determine total organic carbon (TOC) content. Total inorganic carbon using an activated molecular sieve (Merck, 500 pm pore space), cy-
(TIC = TC – TOC) was used to calculate calcite equivalent (CEq) per- clohexane, and a cyclohexane–n-pentane (12:88) solution.
centages (CEq = TIC × 8.34 [%]). Ash yields were determined ac- Saturated and aromatic hydrocarbon fractions were analysed using
cording to standard procedures (ASTM International, 2018). a gas chromatograph equipped with a 30 m DB-5MS fused silica capil-
Pyrolysis was carried out in duplicate using a Rock-Eval 6 instru- lary column (i.d. 0.25 mm; 0.25 μm film thickness) and coupled to a
ment (Lafargue et al., 1998). The S1 and S2 peaks were recorded in ThermoFisher ISQ mass spectrometer. The measuring process followed
order to determine the quantities of free (S1 [mg HC/g rock]) and is described in Gross et al. (2015).
generated hydrocarbons (S2 [mg HC/g rock]). The temperature of Stable carbon isotope measurements of n-alkanes and acyclic iso-
maximum hydrocarbon generation (Tmax [°C]) was recorded and used prenoids were performed on selected samples using a Trace GC in-
as a maturity indicator. Derived parameters were also calculated, such strument attached to a ThermoFisher DELTA-V isotope ratio mass
as the hydrogen index (HI; HI = S2 × 100/TOC [mg HC/g TOC]), spectrometer via a combustion interface (GC isolink, ThermoFisher).
4
Fig. 3. Simplified lithostratigraphy of the investigated section at the W–1 well. a) Lithologies are assigned based on well logs and drill cuttings. Drill core was
recovered from 2587 m to 2605 m. b) Preserved fossils in the siltstone, including echinoid fragment (crossed Nicols) and c) miliolid foraminifer (plane polarized
light). d) Location of organic matter rich samples in the higher resolution stratigraphy sequence selected for organic petrology and their maceral composition. Sample
depth is given as measured depth (MD).
CO2 was injected at the beginning and the end of each analysis in order 4. Results
to perform instrumental calibration. The GC column and temperature
program used were the same as above. Stable isotope ratios are re- 4.1. Lithology
ported in delta notation (δ13C; Coplen, 2011) relative to the Vienna Pee
Dee Belemnite (V-PDB) standard (δ13C = [(δ13C/δ12C)sample/(δ13C/ Based on drill cuttings and well logs (gamma ray, density, porosity)
δ12C)standard − 1]). Delta notation is expressed in parts per thousand or the Kosd Formation is 376 m thick and includes two coal horizons at
per mil (‰). The analytical error was better than 0.2‰. depths between 2594 and 2649 m (Fig. 3a). The lower and upper coal
horizons are about 9 m and 36 m thick, respectively. The sediments
5
between the coal horizons consist of grey sandstone, sandy siltstone, 22 wt%, respectively) and a lower amount of asphaltenes (avg. 13 wt%;
silty claystone, and conglomerate. Non-coal layers within the coal Table 3).
horizons comprise grey, sandy-, argillaceous-, calcareous- and coaly
siltstones. Individual coal beds are 0.1 to 2.1 m thick and include coal 4.3. Maceral composition and vitrinite reflectance
and coaly shale, and intercalations of siltstone and claystone (Fig. 3a).
The studied drill core (2587–2605 m depth) represents the upper Maceral analyses were performed on 15 samples, including coal,
portion of the coal horizon I (Fig. 3a). Its base is located in the upper coaly shale, and claystone/siltstone (Table 2). Vitrinite group macerals
part of a 2 m-thick coal bed at a depth of 2605 m. The core includes coal predominate in all samples (Figs. 3d, 5; Table 2). In coals, vitrinite
layers, which are black, consolidated and hard. Two different lithotypes macerals account for between 67 and 99 vol%. Collotelinite (37–46 vol
can be distinguished: (i) a generally bright, finely banded clarain coal, %), collodetrinite (7–48 vol%) and gelinite (10–21 vol%) are the most
which is brittle, exhibits uneven fracture and occurs as 5 to 50 cm thick abundant vitrinite macerals present. Collotelinite and collodetrinite
layers; and (ii) a stratified coaly shale, including intercalations of thin exhibit an orange-brown fluorescent colour under UV light irradiation
(< 1 cm) siltstone and claystone layers, in which the thickness varies (Fig. 5). Inertinite macerals are typically in the range of 1 to 3 vol% but
from 5 to 40 cm. The interseam sediments are dominated by sandy reach significantly higher values in banded coal samples (26 and 28 vol
siltstone, which is variably calcareous and argillaceous. Original sedi- %, in #21 and #34, respectively). In banded coal samples, funginite
mentary structures are not visible due to bioturbation, however, slumps and inertodetrinite are present in addition to fusinite. The percentages
are recognizable. Two distinct intervals with shell fragments are ob- of liptinite macerals reach 8 vol% and sporinite and alginite are present
served (2596.5–2598.0 m; 2601.5–2602.0 m). Microscopic investiga- in substantial amounts (max. 4 vol%) in some samples.
tion revealed that the siltstone is rich in fossils, including mollusc, In claystone/siltstone samples, vitrinite maceral contents vary from
brachiopod, echinoid fragments and miliolid foraminifers (Figs. 3b, c). 65 to 100 vol%. Inertinite macerals are abundant in the lowermost
sample (#35: 34 vol%; Fig. 3d; Table 2). Liptinite macerals, mainly
4.2. Bulk geochemical parameters sporinite, are generally rare and do not exceed 2 vol% (Fig. 3d;
Table 2). Framboidal pyrite occurs in substantial quantity throughout
The TOC contents of coal and coaly shale range between 45.7 and all samples, however, the highest contents are observed in the clays-
78.4 wt% (avg. 60.4 wt%) and between 12.7 and 29.5 wt% (avg. tone/siltstone samples (Table 2).
22.3 wt%), respectively, whereas the TOC contents of the interseam Vegetation- (VI) and groundwater influence indices (GWIAC) were
lithologies vary between 0.4 and 7.2 wt% (avg. 1.3 wt%). Generally, the calculated for coaly sediments based on Calder et al. (1991) and Stock
TOC contents of samples are greater than 2.9 wt% from 2599.9 m to et al. (2016; Fig. 6; Table 2). VI ranges from 0.7 to 4.8 and GWIAC varies
2602.0 m (#21 to #28), including coal beds and interseam sediments between 2.9 and 39.2 (Table 2).
(Table 1). The ash yield of coals varies between 5.8 and 77.9 wt% Mean random vitrinite reflectance was found to range from 0.67 to
(Table 1). The maximum calcite equivalent percentage in coals and 0.78 (Table 2).
intercalating sediments is 6.8 and 36.1 wt% (avg. 4.0 and 10.0 wt%),
respectively (Table 1). 4.4. Molecular composition of hydrocarbons
The sulphur content of coaly layers ranges between 3.4 and 8.8 wt%
(avg. 4.9 wt%). In the non-coaly intervals, sulphur contents vary be- 4.4.1. Straight chain alkanes and isoprenoids
tween 1.4 and 4.8 wt% (avg. 2.8 wt%). In most cases, below the depth The concentration of n-alkanes (Tables 3, 4) varies considerably
of 2599 m (#20), the sulphur contents are greater than 2.8 wt%, except across the investigated section. The compositions of identified n-alkanes
sample #35. The TOC/TS ratio varies between 3.6 and 23.0 (avg. 9.2) vary within the range of n-C13 to n-C37. Patterns of n-alkane distribution
in coaly lithotypes, whereas its value in interseam sediments ranges are characterized by a relatively uniform proportion of mid-chain n-
from 0.2 to 4.6 (avg. 0.5; Table 1). alkanes (n-C21–25; 27–38% of the total n-alkanes; Fig. 7; Table 4). Coaly
Tmax values range from 431 to 448 °C (Table 1). The HI ranges from lithologies (#21, #24, #26 and #28) and their adjacent sediments (#22
36 to 291 mg HC/g TOC (Table 1). In Tmax vs. HI plots (Figs. 4a, b), and #27) are dominated by short-chain n-alkanes (n-C15–19; 30–46%;
samples can be subdivided into two populations, reflecting those with Fig. 8). In contrast, interseam lithologies are generally dominated by
less or more than 150 mg HC/g TOC. The HI of coaly lithotypes varies long-chain n-alkanes (n-C27–31; 24–31%; Fig. 8). Furthermore, n-alkane
from 229 to 291 mg HC/g TOC (avg. 252 mg HC/g TOC). The HI in the envelopes exhibit a bimodal distribution pattern. The carbon preference
interseam sediments is from 36 to 289 mg HC/g TOC (avg. 87 mg HC/g index (CPI; Bray and Evans, 1961) is close to one (0.93–1.04, Table 4).
TOC), however, higher readings (> 150 mg HC/g TOC) were recorded The acyclic isoprenoids, including i-C13, farnesane, i-C16, norpris-
at samples #6, #25 and #27, which are adjacent to coals (Table 1). BI tane, pristane (Pr) and phytane (Ph), are present in great abundance in
and QI were calculated for coals and coaly shales, and vary from 30 to all samples (Table 3). The ratios of Pr/Ph range from 3.0 to 4.2
37 mg HC/g TOC and from 259 to 323 mg HC/g TOC, respectively (Table 4).
(Figs. 4c, d; Table 1). An important observation noted during Rock-Eval The stable carbon isotopic composition (δ13C) of n-alkanes, Pr and
pyrolysis is that coaly samples undergo stronger swelling, i.e. their Ph is similar for all studied samples (Fig. 9). With increasing chain
volume increases significantly during heating. length, δ13C values of the n-C15–19 and n-C21–25 alkanes of selected
The amount of extractable organic matter (EOM) varies between 31 samples show a decline of about 1‰, respectively. In contrast, long-
and 212 mg/g TOC and yields of EOM are usually higher in inter- chain alkanes (n-C27+) show a reversed trend and increasing δ13C with
calating sediments (Table 3). EOM is dominated by polar compounds carbon number. Pr and Ph exhibit similar isotopic compositions, but Ph
(34–50 wt%), except in samples #20 and #29, where the saturated is observed to be slightly depleted in 13C in comparison to Pr (Fig. 9).
compounds are prevalent (38 and 43 wt%, respectively). The saturated
and aromatic hydrocarbon contents ranging from 5 to 43 wt% and 14 to 4.4.2. Steroids
28 wt%, respectively. The amount of asphaltene is between 9 and 31 wt The concentration of steranes is very low in all samples (Table 3),
% (Table 3). Aside from the general dominance of polar compounds, however, in the saturated hydrocarbon fraction, 5α,14α,17α(H) ster-
coaly lithotypes are found to be characterized by similar average per- anes dominate over 5β,14α,17α(H) isomers, and are present in the
centages of aromatic hydrocarbons and asphaltenes (avg. 24 and 25 wt C27–C29 range. Normalized values of steranes were plotted on a ternary
%, respectively), and the quantity of saturated hydrocarbons is low diagram of C27, C28 and C29 regular steranes (Huang and Meinshein,
(avg. 5 wt%). In contrast, interseam lithologies are characterized by 1979), showing the relative distribution of steranes indicating organic
similar amounts of saturated and aromatic hydrocarbons (avg. 24 and matter depositional facies (Fig. 10). C29 homologues are found to
6
Fig. 4. Petroleum potential assessment. a) Plot of Tmax vs. HI, showing the maturity and type of kerogen present in the investigated samples (after Espitalié et al.,
1984). b) Plot of Tmax vs. HI, highlighting the increase in HI prior to the onset of oil expulsion (after Sykes and Snowdon, 2002). c) Rank threshold for oil- and gas
generation indicated by BI (after Sykes and Snowdon, 2002). d) Rank threshold for oil expulsion determined by QI (after Sykes and Snowdon, 2002).
Table 2
Mineral matter-free (mmf) maceral-, mineral composition, petrographic indices and random vitrinite reflectance of the investigated samples.
ID Ct Vd Cd Cg G Σ VIT S A Σ LIP F Sf Fg Ma Mi Id Σ IN Pyr DM VI GWIAC %Rr ± SD
# [vol%, mmf] [vol%]
5 44.0 4.0 33.1 – 9.8 90.9 3.5 3.9 7.4 0.5 1.2 – – – – 1.8 17.4 44.7 1.1 29.8 0.72 ± 0.03
6 – – – – – 100.0 – – – – – – – – – – 25.0 71.0 – – 0.73 ± 0.05
12 – – – – – 98.7 – – 1.3 – – – – – – – 13.2 73.8 – – 0.68 ± 0.05
13 45.9 – 32.2 – 17.4 95.5 1.1 0.5 1.6 1.0 1.8 – – – – 2.8 8.5 27.6 1.4 39.2 0.73 ± 0.04
18 – – – – – 80.4 – – – – – – – – – 19.6 17.3 79.3 – – 0.74 ± 0.06
21 59.1 – 7.4 0.6 0.2 67.4 5.7 1.3 6.9 9.1 12.7 0.3 – 1.1 2.5 25.7 0.1 0.8 4.8 2.9 0.76 ± 0.04
23 – – – – – 90.0 – – – – – – – – – 10.0 13.3 78.7 – – 0.78 ± 0.06
24 36.9 – 40.2 – 20.6 97.7 1.2 – 1.2 0.4 0.6 – – – – 1.0 8.8 24.0 0.9 16.3 0.71 ± 0.02
25 – – – – – 97.0 – – 0.8 – – – – – – 2.3 15.8 76.1 – – 0.78 ± 0.04
26 32.8 0.6 47.7 – 17.0 98.1 0.5 – 0.5 0.6 0.8 – – – – 1.4 8.2 28.9 0.7 31.2 0.68 ± 0.02
27 – – – – – 97.0 – – 1.5 – – – – – – 1.5 14.5 73.2 – – 0.75 ± 0.03
28 38.2 – 40.1 – 20.3 98.7 0.3 – 0.3 0.6 0.4 – – – – 1.0 6.1 50.2 1.0 33.4 0.67 ± 0.04
29 – – – – – 90.9 – – – – – – – – – 9.1 4.4 92.0 – – 0.73 ± 0.06
34 48.5 0.4 9.8 2.8 6.4 67.9 4.1 – 4.1 16.7 4.8 0.1 1.4 1.0 3.8 27.9 8.0 44.7 4.1 15.4 0.75 ± 0.03
35 – – – – – 64.8 – – 0.9 – – – – – – 34.3 14.8 78.2 – – 0.74 ± 0.04
Macerals that were not counted and are in very low percentages (< < 0.1 vol%) are not included in the table, however, resinite, liptodetrinite and cutinite occur in
the samples. Ct – collotelinite, Vd – vitrodetrinite, Cd – collodetrinite, Cg – corpogelinite, G – gelinite, Σ VIT – total vitrinite, S – sporinite, A – alginite, Σ LIP – total
liptinite, F – fusinite, Sf – semifusinite, Fg – funginite, Ma – macrinite, Mi – micrinite, Id – inertodetrinite, Σ IN – total inertinite, Pyr – pyrite, DM – detrital minerals,
VI – vegetation index, GWIAC – groundwater index, %Rr ± SD – mean random vitrinite reflectance ± standard deviation.
VI = (telovitrinite + fusinite + semifusinte + cutinite + sporinite + suberinite + resinite) / (detrovitrinite + inertodetrinite + alginite + liptodetrinite + ex-
sudatinite + chlorophyllinite + bituminite; Calder et al., 1991), GWIAC = (gelovitrinite + (ash yield / 2)) / (telovitrinite + vitrodetrinite); Stock et al., 2016).
prevail in the samples, followed by C28 and C27 steranes. In organic stigmastanes were identified at very low concentrations.
matter-rich samples, C29 steranes predominate in the distributions The stereoisomer ratios of S/(S + R) of ααα C29 steranes and ββ/
(Fig. 10; Table 3). The corresponding diasteranes are found in even (ββ + αα) of C29 steranes were assessed as a thermal maturity para-
lower abundance (Table 3), and exhibit similar carbon number dis- meter. Ratios of the 20S/(20S + 20R) isomers of the
tributions as the regular steranes. In the aromatic hydrocarbon frac- 5α,14α,17α(H)–C29 steranes range between 0.40 and 0.53. Moreover,
tions, monoaromatic (C29) stigmastanes and triaromatic (C28) ratios of αββ/(αββ + ααα) isomers of C29 steranes range from 0.65 to
7
Fig. 6. Chart of vegetation- (VI) and groundwater influence index (GWIAC; after
Calder et al., 1991).
The stereoisomer ratio of 22S/(22S + 22R) isomers of

17α,21β(H)–C32 hopanes, a thermal maturity parameter, ranges from
0.55 to 0.63 (Table 4).
4.4.4. Sesquiterpenoids, diterpenoids, non-hopanoid triterpenoids

Bicyclic sesquiterpenoids are characterized by the occurrence of
8β(H)–homodrimane, 8β(H)–drimane, and 4β(H)–eudesmane.
Furthermore, rearranged drimenes and pentamethyl–trans–decalins are
also present in the studied samples. Decalins were identified as
2,2,4a,7,8–pentamethyl–trans–decalin and 1,2,2,5,5–pentamethyl–-
trans–decalin according to Nytoft et al. (2009). Diterpenoids consist of
bicyclic- (8β(H)–labdane), tricyclic- (pimarane, isopimarane and abie-
tane) and tetracyclic diterpanes (16β(H)–phyllocladane). The tetra- and
pentacyclic triterpenoids occur in the analysed samples and the fol-
lowing oleanane, ursane and lupane types were identified in non-aro-
matic hydrocarbon fractions: des–A–olean–12–ene, des–A–urs–12–ene,
10β(H)–des–A–oleanane, 10β(H)–des–A–lupane, 10β(H)–de-
s–A–ursane, lupane, urs–12–ene, and 18β(H)–oleanane, with a sub-
stantial amount of 18α(H)–oleanane.
Aromatic sesquiterpenes are represented by cadalene, calamenene
and 5,6,7,8–tetrahydrocadalene. Abietane-type aromatic diterpenoids
are present and consist of 1,2,3,4–tetrahydroretene, norsimonellite, si-
monellite, and retene. The following aromatic tetra- and pentacyclic
triterpenoids are identified in the aromatic hydrocarbon fractions: tet-
ramethyl–octahydro–chrysenes, trimethyl–tetrahydro–chrysenes, and
Fig. 5. Photomicrographs of coal samples studied. Images were taken under tri- and tetra aromatic pentacyclic triterpenoids of the oleanane- and
reflected white light (WL) and ultraviolet light (UV) using oil immersion ob- ursane-types (tetramethyl–octahydro–picenes, trimethyl–tetrahy-
jective. Samples are #5 (a, b), #21 (c, d, e, f), #26 (g, h) and #34 (i, j). A – dro–picenes).
alginite, Cd – collodetrinite, Ct – collotelinite, Cu – cutinite, F – fusinite, G –
gelinite, Id – inertodetrinite, Pyr – pyrite, Qtz – quartz, Re – resinite, S –
sporinite and Sf – semifusinite. 4.4.5. Polycyclic aromatic hydrocarbons
The total ion chromatograms of aromatic hydrocarbon fractions are
0.69 (Table 4). dominated by naphthalenes and phenanthrenes (Table 3). Naphthalene
(N) occurs at low concentrations, however, its alkylated counterparts,
methyl- (MN), dimethyl- (DMN) and trimethylnaphthalenes (TMN), are
4.4.3. Hopanoids present at a higher amount. The methylnaphthalenes (2– and 1–MN)
Hopanoids are important constituents of the non-aromatic cyclic are present in equal quantities, whereas 1,6–DMN and 1,2,5– and
triterpenoids (Table 3). The measured hopanoid patterns are char- 1,2,7–TMN predominate the dimethyl- and trimethylnaphthalenes, re-
acterized by the occurrence of 17α,21β(H)– and 17β,21β(H)–type ho- spectively.
panes from C27 to C35 with C28 hopanes being absent. The predominant Phenanthrene (P), alkylated phenanthrenes (methyl- (MP), di-
hopanoids in most samples are 17α,21β–C30 and 17β,21α–C29 hopane. methyl- (DMP) and trimethylphenanthrenes (TMP)) occur in consider-
The 17α,21β(H)–type homohopanes show a dominant pattern of ex- able concentrations in the investigated samples. The 9–, 1– and 2–MP
ponential decrease in peak height with increasing carbon number. In characterize the methylphenanthrenes. The methylphenantrene index
most samples, a series of C32– to C35–benzohopanes was identified in (MPI 1; Radke et al., 1982) varies between 0.52 and 0.59 and calculated
the aromatic hydrocarbon fractions. In all investigated samples, the vitrinite reflectance values (%Rc(MPI 1); Radke and Welte, 1983) vary
ratios of steroids to hopanoids are between 0.06 and 0.15 (Table 4). between 0.71 and 0.75%Rc (Table 4). The pattern of
8
Table 3
Rock extracts, percentage of extract fractions and concentrations of hydrocarbon species of investigated samples in the Kosd Formation.
ID a b c d e f g h i j k l m n o p q r s t u v w
# [mg/g TOC] [wt%] [μg/g TOC]
20 164 38 19 35 9 14973 2082 44 10 221 74 241 17 112 218 300 1 1336 270 1682 244 1050 216
21 31 5 26 50 19 235 78 5 1 56 21 98 2 25 21 113 12 1245 112 515 95 300 87
22 84 10 28 48 13 2018 524 11 2 59 49 321 5 100 54 373 1 3300 319 1809 321 1228 285
23 146 26 21 40 13 11588 2605 55 12 233 257 379 21 88 586 256 56 2348 220 1198 231 994 209
24 57 5 23 46 25 410 158 14 1 60 41 151 8 38 115 131 8 1277 129 630 129 452 102
25 95 13 27 42 18 2497 794 20 4 83 123 297 12 66 239 216 10 2087 190 1007 201 811 169
26 60 6 24 46 24 733 223 14 2 28 35 211 4 38 154 166 3 1451 159 703 161 475 139
27 83 12 24 47 17 2527 571 14 3 96 85 247 8 53 261 276 4 2125 236 1118 235 842 220
28 62 6 21 42 31 639 159 9 1 77 35 142 4 27 108 172 2 1334 159 691 149 497 131
29 212 43 14 34 9 28999 3485 76 21 351 151 254 21 48 908 173 1 843 262 1399 198 835 212
a – extracted organic matter, b – saturated hydrocarbons, c – aromatic hydrocarbons, d – polar compounds, e – asphaltenes, f – n-alkanes, g – isoprenoids, h – steranes,
i – diasteranes, j – hopanes, k – sesquiterpenoids, l – aromatic sesquiterpenoids, m – diterpenoids, n – aromatic diterpenoids, o – triterpenoids, p – aromatic
triterpenoids, q – naphthalenes, r – alkylated naphthalenes, s – phenanthrenes, t – alkylated phenanthrenes, u – dibenzothiophenes, v – alkylated dibenzothiophenes,
w – benzonaphthothiophenes.
dimethylphenanthrenes is predominated by 1,7–DMP, and the co-

eluting 1,3,7–, 1,3,9– and 2,7,10–TMP dominate the trimethylphenan-
threnes.
Beside the naphthalenes and phenanthrenes, polycyclic aromatic
hydrocarbons identified include chrysene, alkylated chrysenes, and
perylene.
4.4.6. Sulphur-aromatic compounds

The sulphur-containing aromatic compounds identified include di-
benzothiophenes and benzonaphthothiophenes, both of which occur in
considerable quantities in the investigated samples (Table 3). Di-
benzothiophenes are represented by dibenzothiophene (DBT), methyl-
(MDBT), dimethyl- (DMDBT) and trimethyldibenzothiophenes
(TMDBT). Methyldibenzothiophenes are characterized by 4–MDBT, co-
eluting 3– + 2–MDBT and 1–MDBT, in descending order of con-
centration. The benzonaphthothiophenes are dominated by benzo[b]
naphtho[2,1]thiophene, whereas benzo[b]naphtho[1,2]thiophene and
benzo[b]naphtho[2,3]thiophene occur in lower quantities.
The DBT/P ratios (Hughes et al., 1995) range between 0.74 and
1.04 (Fig. 11; Table 4).
Fig. 7. Normalized distribution of short- (n-C15–19), mid- (n-C21–25) and long-

5. Discussion chain (n-C27–31) n-alkanes in the studied samples.
5.1. Thermal maturity

organic matter is mature, but did not yet reach peak oil window ma-
Vitrinite reflectance (0.67–0.78%Rr; Table 2) and Tmax values turity (0.8%Rr, e.g. Peters and Cassa, 1994). Nevertheless, values of Rr
(431–448 °C; Table 1) indicate that the coals of the Kosd Formation and Tmax vary slightly and point to lower values in coaly lithotypes.
reached high volatile bituminous rank (Taylor et al., 1998) and that the The content of liptinite group macerals is limited, however, organic
Table 4
Concentration ratios of compounds in hydrocarbon fractions of samples from the Kosd Formation.
ID a b c d e f g h i j k l m n o
# [%] [%] [%]
20 22 35 25 1.00 3.30 30 24 46 0.13 0.42 0.65 0.55 0.75 0.89 0.20

21 46 27 12 1.04 4.10 14 23 63 0.06 0.50 0.67 0.57 0.71 0.83 0.17
22 39 31 15 0.97 4.22 20 23 57 0.11 0.53 0.68 0.56 0.73 0.99 0.20
23 18 29 31 0.97 3.52 26 30 44 0.10 0.43 0.66 0.59 0.74 1.03 0.11
24 35 32 17 0.96 3.76 17 17 66 0.11 0.45 0.67 0.59 0.73 0.98 0.16
25 24 33 24 0.97 3.96 26 28 45 0.10 0.44 0.67 0.57 0.72 1.04 0.15
26 34 34 16 0.93 3.63 21 27 52 0.15 0.42 0.66 0.63 0.72 1.00 0.12
27 30 35 19 1.00 3.57 25 28 46 0.06 0.46 0.66 0.59 0.73 0.98 0.10
28 37 34 13 0.96 3.30 18 20 62 0.06 0.49 0.69 0.57 0.72 0.92 0.10
29 17 38 26 1.03 3.01 38 26 36 0.09 0.40 0.66 0.57 0.73 0.74 0.06
a – n-C15–19/n-C15–35, b – n-C21–25/n-C15–35, c – n-C27–31/n-C15–35, d – CPI (Bray and Evans, 1961), e – Pr/Ph, f – C27 steranes/Σ regular steranes, g – C28 steranes/Σ
regular steranes, h – C29 steranes/Σ regular steranes, i – steranes/hopanes, j – 20S/(20S + 20R) ααα C29 steranes, k – αββ/(αββ + ααα) C29 steranes, l – 22S/
(22S + 22R) C32 hopane, m – Rc(MPI 1) (Radke and Welte, 1983), n – DBT/P (Hughes et al., 1995), o – Di- / (Di- + Triterpenoids; Bechtel et al., 2003).
9
Fig. 10. Ternary plot of regular steranes showing the normalized abundance of
C27, C28 and C29 sterane isomers and their depositional facies (after Huang and
Meinshein, 1979).
Fig. 8. Gas chromatograms (total ion current) of saturated hydrocarbon frac-

tion of (a) coal, sample #21 and (b) claystone, sample #23. n-Alkanes are la-
belled according to the carbon number. std. – standard (deuterated n-tetra-
cosane). Fig. 11. Cross-plot of pristane/phytane (Pr/Ph) vs. dibenzothiophene/phe-
nanthrene (DBT/P) ratios (after Hughes et al., 1995).
vitrinite (Wilkins and George, 2002). Hence, the vitrinite reflectance of

coaly lithotypes may be suppressed due to the diagenetic enrichment in
hydrogen and sulphur (e.g. Peters et al., 2018 cum lit.). Considering the
relatively low content of liptinite macerals and extractable organic
matter, suppression due to sorption of generated bitumen (Carr, 2000;
Taylor et al., 1998; Wilkins and George, 2002) seems less likely.
Hopane (22S/22S + 22R C32) and sterane (20S/(20S + 20R) ααα
C29) isomerisation ratios range from 0.55 to 0.63 and from 0.40 to 0.53,
respectively (Table 4). Although this indicates that C32 hopane iso-
merisation ratios reached their equilibrium value, sterane isomerisation
ratios of C29 suggest that steranes did not. This denotes maturities
corresponding to the oil window (0.6–0.8%Rr; Mackenzie et al., 1980;
Mackenzie and Maxwell, 1981; Seifert and Moldowan, 1986; Peters
et al., 2005). This maturity assessment is supported by ratios of ββ/
(ββ + αα) isomers of the 5α,14α,17α (H)–C29 steranes (0.65–0.69;
Table 4), which are close to their equilibrium value of 0.7 (Seifert and
Fig. 9. Carbon isotopic composition of n-alkanes, pristane and phytane in coal Moldowan, 1986). CPI values close to one (0.93–1.04) further confirm
(#24), coaly shale (#26) and interseam sediments (#25, #27). this maturity assessment.
The methylphenanthrene index (MPI) is a well-established para-
matter is dominated by fluorescent vitrinite (Fig. 5; Table 2). The or- meter for classifying maturity (Radke et al., 1982) and can be used to
ange-brown fluorescence colour of the vitrinite and the strong swelling calculate vitrinite reflectance values (Radke and Welte, 1983). The
during pyrolysis both suggest the predominance of hydrogen-rich calculated vitrinite reflectance values are between 0.71 and 0.75%Rc
10
(Table 4), which fits well with the measured values. 2006; Meyers, 1997). The assimilation of HCO3− leads to 13C enrich-
ment (Aichner et al., 2010; Lamb et al., 2006; Meyers, 1997). The in-
5.2. Source of organic matter termediate-weight n-alkanes are isotopically heavier than long-chain n-
alkanes (Fig. 9), moreover, δ13C isotopic differences could be more
The Kosd coal is generally dominated by vitrinite and inertinite explicit prior to the thermal alteration. Furthermore, low-molecular
subgroup macerals (Table 2), which are derived from woody tissues of weight n-alkanes are characterized by 13C enrichment relative to mid-
herbaceous and arborescent plants (ICCP, 1998). Petrography-based chain n-alkanes (Fig. 9). However, the carbon isotopic composition of
facies indicators have been determined for the coaly lithotypes. The lake-derived organic matter is typically indistinguishable from the
vegetation index (VI; Table 2) contrasts macerals of forest affinity with surrounding watershed (Meyers, 1997). Nevertheless, the contribution
those of herbaceous and marginal aquatic affinity (Calder et al., 1991). of algae to the carbon isotope compositions measured is also suggested
All studied samples of Kosd coal, except #21 and #34, are character- by the presence of lamalginite.
ized by VI values below 3 (Fig. 6; Table 2), indicating a predominance The predominance of C29 steroids in coals is consistent with a
of herbaceous peat-forming flora. dominant origin of organic matter from vascular plants (Fig. 10;
Long-chain lipids are typically attributed to higher terrestrial plants Table 4; Huang and Meinshein, 1979), which also explains the low
(Eglinton and Hamilton, 1967), whereas mid-chain n-alkanes are re- amount of regular steranes (Doković et al., 2018; Volkman, 1986).
ported in aquatic macrophytes and Sphagnum (Bingham et al., 2010; Besides the vascular plants, the constant proportion of C28 steranes and
Dehmer, 1995; Ficken et al., 2000; Nott et al., 2000), and short-chain n- the occurrence of perylene has been suggested to indicate a contribu-
alkanes are identified predominantly in algae and other microorgan- tion from wood-degrading fungi (Marynowski et al., 2013). Hopane
isms (Cranwell, 1977; Cranwell et al., 1987). Hence, it is surprising that derivatives occur in the investigated samples, in which the bacter-
the studied coaly samples (TOC > 20 wt%) are characterized by sig- iohopanepolyols have been suggested to be the most probable biolo-
nificantly higher amounts of short-chain n-alkanes than long-chain n- gical precursors, and have been identified both in bacteria and in some
alkanes (Table 4). For example, the clean coal #21 (TOC 78.4 wt%; ash cryptogams (e.g. moss, ferns; Ourisson et al., 1979; Rohmer, 1993;
yield: 5.2 wt%) contains the highest relative percentage of short-chain Talbot et al., 2016). The occurrence of C32 to C35 benzohopanes
n-alkanes (max. 46%) and the lowest relative percentage of long-chain (Hussler et al., 1984) in the aromatic hydrocarbon fractions also sug-
n-alkanes (min. 12%; Table 4). A shift towards shorter n-alkanes may be gests that bacteriohopanetetrol was a significant constituent of the
caused by advanced maturity (e.g. Radke et al., 1980), but this effect precursor biomass. Furthermore, both the low sterane to hopane ratio
alone cannot explain the pattern observed since some low-TOC samples and the presence of drimane-type sesquiterpenoids suggest microbially
also contain high percentages of long-chain n-alkanes (e.g. #23; 31%). reworked organic matter (Alexander et al., 1983, 1984; Tissot and
The high amounts of short-chain n-alkanes in coal samples are related Welte, 1984).
to the strong fluorescence of vitrinite macerals, high S1 and BI values Sesquiterpenoids and diterpenoids are present in the analysed
(Table 1; Fig. 4c) and may be caused by either migration (Littke et al., sample sets (Table 3). The biological precursors of cadalane-type ses-
1990) or bacterial activity. Whereas relative amounts of long- and quiterpenoids are widely distributed throughout all conifer families
short-chain n-alkanes vary significantly, mid-chain n-alkanes are found (Simoneit et al., 1986; Otto et al., 1997, and references therein). Eu-
at high, relatively constant proportions (27–34%). desmane is also a non-specific indicator of higher land plants
δ13C-values of n-alkanes in the selected samples (Fig. 9) are con- (Alexander et al., 1983), hitherto missing in species of Araucariaceae
sistent with previous studies performed on coal samples (e.g. Gross and Taxaceae (Otto and Wilde, 2001). Labdane-type compounds are the
et al., 2015; Schoell et al., 1994; Simoneit et al., 1995; Schwarzbauer most common diterpenoids in conifers and have been described in all
et al., 2013; Tuo et al., 2003). Variations of carbon isotopic composi- families except in Cephalotaxaceae (Otto and Wilde, 2001). More than
tions of individual compounds are within 1‰, indicating a positive 100 pimarane- and isopimarane-type diterpenoids have been detected
correlation between sample sets (Sofer, 1984). δ13C-values also show a in species of Pinaceae, Taxodiaceae, Araucariaceae, and Cupressaceae
decreasing trend, becoming more depleted in 13C with increasing chain (Sukh Dev, 1989). Phyllocladane-type diterpenoids are widespread
length in all samples (Fig. 9), a phenomenon often observed in coals among coniferales families, except in Pinaceae (Otto and Wilde, 2001).
(e.g. Doković et al., 2018; Schoell et al., 1994; Schwarzbauer et al., Abietane-type diterpenoids can be generated by the transformation of
2013; Tuo et al., 2003). The long-chain n-alkane compounds, however, pimarane (Wakeham et al., 1980), the progressive thermal alteration of
show an opposite tendency, getting more enriched in 13C with in- phyllocladane (Alexander et al., 1987), or the dehydrogenation of
creasing chain length (Fig. 9). Both long-chain n-alkane production and abietic acids (Peters et al., 2005). Alkylated phenanthrenes have been
the biosynthetic fractionation of carbon isotopes vary among plant genetically related to abietic- and pimaric acid (Alexander et al., 1995;
types (Diefendorf et al., 2011; Lockheart et al., 1997) and studies have Laflamme and Hites, 1978; Radke et al., 1998). Based on the compo-
pointed to 13C enrichment with chain length in recent terrestrial plants sition of diterpenoids present in the studied samples, Cupressaceae
(e.g. Collister et al., 1994; Diefendorf et al., 2011; Diefendorf et al., genera presumably contributed to the arboreal vegetation.
2015; Lockheart et al., 1997; Mead et al., 2005). Nevertheless, the effect Non-hopanoid triterpenoids of oleanane-, ursane- and lupane-types
of thermal maturation on the carbon isotopic composition of organic are significant constituents of leaf waxes, wood, roots, and bark (Karrer
matter has already been considered by several authors (e.g. Bjorøy et al., 1977), and the oleanane- and ursane-types are particularly pre-
et al., 1992; Rooney et al., 1998; Schoell, 1984). Diefendorf et al. dominant in the samples investigated. These compounds are formed by
(2015) found that the catagenic stage of maturation can lead to varia- the transformation of β-amyrin, α-amyrin, and lupeol (Havelcová et al.,
tions in the magnitude and direction of the change in δ13C-values ac- 2012) and are significant biomarkers of angiosperm inputs into organic
cording to species and chain length. Therefore, the effect of thermal matter (Sukh Dev, 1989; Karrer et al., 1977). Aside from non-hopanoid
maturation on the δ13C-values measured cannot be ruled out in the triterpenoids, di- and trimethylnaphthalenes can also originate from
present study. angiosperms (van Aarssen et al., 1992; Strachan et al., 1988).
The δ13C-values correspond to common carbon isotope values of C3 The di-/(di- + triterpenoids) ratio can be used to estimate the re-
plants and freshwater algae (e.g. Close, 2019; Diefendorf and Freimuth, lative contribution of gymnosperms and angiosperms to organic matter
2017; Holtvoeth et al., 2019; Lamb et al., 2006; Meyers, 1997; O'Leary, (Bechtel et al., 2003). Very low ratios (≤0.2; Table 4) indicate that
1981). Terrestrial plants utilise atmospheric CO2 during photosynthesis, angiosperm-derived biomarkers predominate in all analysed samples of
whereas aquatic photoautotrophs use dissolved CO2[AQ] or, in the case the Kosd Formation. These results are consistent with previous ob-
of alkaline or CO2-limited conditions, can fix HCO3− as the inorganic servations on Eocene coal deposits throughout central Europe (Bechtel
carbon source for photosynthesis (Holtvoeth et al., 2019; Lamb et al., et al., 2007, 2008) and are supported by palynological data from
11
throughout the Transdanubian Mountains, which further indicates an organic matter, perylene has been related to the activity of wood-de-
angiosperm-dominated vegetation (Kvaček, 2010, and references grading fungi and indicates reducing conditions in subsurface sedi-
therein; Rákosi, 1978). Although the vegetation was dominated by ments during early diagenesis (Marynowski et al., 2013). Although the
angiosperms, a continuous upward increase in the di-/(di- + triterpe- studied coals are mature, the presence of framboidal pyrite, as well as
noids) ratio from 0.06 to 0.20 (Table 4) indicates an increasing relative perylene, indicates eogenetic origin and locally reducing conditions
contribution of gymnosperms during deposition of the studied depth (Sweeney and Kaplan, 1973).
interval (2602.4–2599.0 m). Whereas Gidai (1978) and Less (2005) have mentioned the presence
of coaly layers in wells K–20 and V–75, they did not investigate the
5.3. Depositional environment organic material. Nevertheless, the new results on well W–1 agree well
with the sedimentological and palaeontological data reported by these
GWIAC values (> 10) in the studied section suggest that the de- authors. Despite the strongly varying thickness, all three wells show a
position of the coaly lithotypes occurred in a low-lying mire with general trend from non-marine fine-grained rocks with debris flow
rheotrophic conditions (Fig. 6; Table 2; Calder et al., 1991). The pre- deposits to brackish and marine sediments. Coaly layers occur within
sence of inertinite and liptinite in the investigated Kosd coal implies the the transition zone. According to Less (2005), the upper marine part of
existence of a paleomire influenced by the fluctuation of the water table the Kosd Formation in V–75 represents a lagoonal environment domi-
(Diessel, 1992; Eble et al., 2019), allowing the accumulation of la- nated by fine-grained rocks. Based on the lithological and faunal de-
malginite during high-, and the oxidation of plant tissues during low scription provided by Gidai (1978), a similar environment can be as-
water table conditions. sumed for well K–20. In contrast, the studied interval in well W–1
The n-alkane isotope profile shows a generally declining pattern includes sandstones and conglomerates representing a delta environ-
(Fig. 9), which has previously been assigned to fluvio-deltaic origins ment. Moreover, the total thickness of the Kosd Formation in well W–1
(e.g. Bjorøy et al., 1991; Cortes et al., 2010; Dzou and Hughes, 1993; (376 m) is higher than in any other well (cf. Less, 2005).
Murray et al., 1994; Odden et al., 2002; Tuo et al., 2003; Wilhelms
et al., 1994). The Pr/Ph vs. DBT/P plot also indicates a fluvio-deltaic 5.4. Hydrocarbon generation potential
environment (Fig. 11; Hughes et al., 1995). The composition of regular
steranes (Fig. 10; Table 4; Huang and Meinshein, 1979) suggests a The remaining hydrocarbon generation potential of the Kosd
transition between shallow marine and deltaic paleoenvironments, Formation samples can be characterized using TOC contents and the
which provided an appropriate setting for the preservation of higher amount of free (S1) and generated hydrocarbons (S2). TOC contents of
plant triterpenoids (Strachan et al., 1988). the analysed samples are generally greater than 0.5 wt% (Table 1). The
The sulphur content of the analysed samples has a general tendency obtained HI values suggest that type III and II–III kerogen is dominant,
towards higher readings with increasing organic carbon content nevertheless, type IV kerogen also occurs (#12, #16 and #20; Fig. 4a;
(Table 3). Variations in sulphur content can be explained by an influx of Table 1). The coaly lithotypes and their adjacent intercalating sedi-
saline water towards the paleomire (Petersen and Ratanasthien, 2011) ments have excellent and fair-good petroleum potential, respectively
or by changes in pH (Markič and Sachsenhofer, 1997). Considering the (Peters, 1986; Peters and Cassa, 1994). In total, 69% of the analysed
occurrence of marine miliolid foraminifers (Fig. 3c), an influx of marine samples have HI values between 50 and 200 mg HC/g TOC and are gas-
water is obvious. In addition, the low TOC/TS ratios (Table 1) support prone, whereas 22% possess oil- and gas-prone kerogen (Peters and
marine influence (Berner, 1982, 1984). Denudation of Mesozoic car- Cassa, 1994).
bonate rocks underlying the Kosd Formation may have enhanced the Following the approach of Sykes and Snowdon (2002), coaly sam-
concentration of bicarbonate ions. Moreover, the chemical weathering ples were plotted onto diagrams of HI, BI and QI versus Tmax
in the hinterland provided nutrients to the paleovegetation. Alkaline (Figs. 4b–d). These diagrams suggest that all coaly samples are gas- and
conditions control both, bacterial decomposition of plant remnants and oil-prone (Fig. 4b) and have passed the rank threshold for oil generation
reduction of sulphates by sulphate-reducing bacteria (Markič and (BI; Fig. 4c) and expulsion (QI; Fig. 4d), furthermore, have reached the
Sachsenhofer, 1997). In the case of available reactive iron, the trans- maturity threshold for the first gas generation (BI; Fig. 4c). Fig. 4c
formation of sulphide phases into densely packed framboidal ag- emphasizes the high BI of the coal samples, which is linked to abundant
gregates of pyrite crystals is a prevalent process driven by bacterial short-chain n-alkanes and probably causes the strong fluorescence ob-
sulphate reduction (Casagrande, 1987; Hámor, 1994; Maclean et al., served in vitrinite macerals.
2008; Morad, 1998; Sweeney and Kaplan, 1973). Nevertheless, there is
a poor fit between the TS and pyrite contents, which indicates the 6. Conclusion
presence of organic sulphur. Organic sulphur-bearing compounds (e.g.
dibenzothiophenes) have been detected in considerable concentrations The investigation of the coal measure of the Eocene Kosd Formation
(Table 3). The prevalence of organic sulphur has also been described for in northern Pannonian Basin has yielded important new results re-
Eocene coals by Hámor-Vidó and Hámor (2007). The marine influence garding its depositional environment, organic matter source and hy-
and the presence of mobile Ca2+ and HCO3− ions in the continental drocarbon potential:
runoff are confirmed by the local elevation of calcite equivalent per-
centages (at #2, #8, #9, #11 and #33) in the interseam sediments (1) The coal measure evolved in a marine deltaic environment. The
(Table 1). accumulation of peat-forming vegetation in a low-lying, rheo-
In the studied samples, Pr and Ph exhibit similar carbon isotopic trophic mire was affected by fluctuations of the water table.
compositions, and are enriched in 13C relative to terrestrial plant-de- (2) Slightly alkaline conditions and the depletion in dissolved oxygen
rived n-alkanes, arguing for chlorophyll as their common source (Fig. 9; noted in the sediments promoted the reduction of sulphates by
Collister et al., 1992; Hayes et al., 1990; Hayes, 1993). Confined pyr- sulphate-reducing bacteria and bacterial decomposition of plant
olysis studies of coal samples support a maturation tendency of Pr/Ph remains. In addition to the high sulphur contents observed (max.
(Monthioux and Landais, 1989; Radke et al., 1980). Therefore, the in- 8.8%), the orange-brown fluorescence colour of vitrinite and its
terpretation of redox conditions during sedimentation based strictly on strong swelling during pyrolysis are typical indicators of marine-
Pr/Ph ratios (Didyk et al., 1978) is limited in the current study due to influenced coals.
interferences resulting from thermal maturity. Nevertheless, the oc- (3) The peat-forming flora was dominated by land plants with varying
currence of des-A-triterpenes suggests dysoxic conditions (Jacob et al., contributions of algae and aquatic macrophytes. Similar to other
2007, and references therein). Furthermore, in immature terrigenous Eocene coal seams, angiosperms predominated over gymnosperms.
12
An upward increase in the relative contribution of gymnosperms biostratigraphy and magnetostratigraphy). Bull. Hung. Geol. Soc. 133, 437–440 (in
(e.g. Cupressaceae) to the biomass is observed at depth between Hungarian with English abstract).
Bauer, M., M.Tóth, T., Raucsik, B., Garaguly, I., 2016. Petrology and paleokarst features
2599.0 and 2604.4 m. The organic matter in the paleomire was of the Gomba hydrocarbon reservoir (central Hungary). Centr. Eur. Geol. 59, 28–59.
highly reworked by microbial processing. Dense flourishing vege- https://doi.org/10.1556/24.59.2016.003.
tation established a CO2-limited environment forcing aquatic plants Bechtel, A., Sachsenhofer, R.F., Markic, M., Gratzer, R., Lücke, A., Püttmann, W., 2003.
Paleoenvironmental implications from biomarker and stable isotope investigations on
to utilise HCO3− during photosynthesis. the Pliocene Velenje lignite seam (Slovenia). Org. Geochem. 34, 1277–1298. https://
(4) Vitrinite reflectance, Tmax, and biomarker indices denote that or- doi.org/10.1016/s0146-6380(03)00114-1.
ganic matter in the Kosd Formation (as identified in deep borehole Bechtel, A., Hámor-Vidó, M., Sachsenhofer, R.F., Reischenbacher, D., Gratzer, R.,
Püttman, W., 2007. The middle Eocene Márkushegy subbituminous coal (Hungary):
W–1) is thermally mature and suggests that the Kosd coal reached Paleoenvironmental implications from petrographical and geochemical studies. Int.
high volatile bituminous rank in the research area. This is higher J. Coal Geol. 72, 33–52. https://doi.org/10.1016/j.coal.2006.12.008.
than the rank of the sub-bituminous coal in the shallow Kosd Bechtel, A., Gratzer, R., Sachsenhofer, R.F., Gusterhuber, J., Lücke, A., Püttmann, W.,
2008. Biomarker and carbon isotope variation in coal and fossil wood of Central
coalfield of the North Hungarian Mountains. This advanced ma-
Europe through the Cenozoic. Palaeogeogr. Palaeoclimatol. Palaeoecol. 262,
turity influenced the molecular and isotopic composition of hy- 166–175. https://doi.org/10.1016/j.palaeo.2008.03.005.
drocarbons. Bechtel, A., Hámor-Vidó, M., Gratzer, R., Sachsenhofer, R.F., Püttmann, W., 2012. Facies
(5) Rock-Eval pyrolysis results indicate that the coaly samples studied evolution and stratigraphic correlation in the early Oligocene Tard Clay of Hungary
as revealed by maceral, biomarker and stable isotope composition. Mar. Pet. Geol. 35,
are gas- and oil-prone and have reached the maturity threshold for 55–74. https://doi.org/10.1016/j.marpetgeo.2012.02.017.
first gas generation and the onset of oil expulsion. Berner, R.A., 1982. Burial of organic carbon and pyrite sulfur in the modern ocean: its
geochemical and environmental significance. Am. J. Sci. 282, 451–473. https://doi.
org/10.2475/ajs.282.4.451.
Declaration of Competing Interest Berner, R.A., 1984. Sedimentary pyrite formation: an update. Geochim. Cosmochim. Acta
48, 605–615. https://doi.org/10.1016/0016-7037(84)90089-9.
Bingham, E.M., McClymont, E.L., Väliranta, M., Mauquoy, D., Roberts, Z., Chambers,
The authors declare there is no conflict of interest. F.M., Evershed, R.P., 2010. Conservative composition of n-alkane biomarkers in
Sphagnum species: implications for palaeoclimate reconstruction in ombrotrophic
Acknowledgement peat bogs. Org. Geochem. 41, 214–220. https://doi.org/10.1016/j.orggeochem.
2009.06.010.
Bjorøy, M., Hall, K., Gillyon, P., Jumeau, J., 1991. Carbon isotope variations in n-alkanes
The authors gratefully acknowledge MOL Plc. for granting the and isoprenoids of whole oils. Chem. Geol. 93, 13–20. https://doi.org/10.1016/
availability of samples and the permission for submitting the manu- 0009-2541(91)90061-u.
Bjorøy, M., Hall, P.B., Hustad, E., Williams, J.A., 1992. Variation in stable carbon isotope
script. We thank IJCG's editor-in-chief Professor D. Flores and two
ratios of individual hydrocarbons as a function of artificial maturity. Org. Geochem.
anonymous reviewers for their constructive comments. The research 19, 89–105. https://doi.org/10.1016/0146-6380(92)90029-w.
was performed during the Ernst Mach scholarship period of SK, sup- Bray, E.E., Evans, E.D., 1961. Distribution of n-paraffins as a clue to recognition of source
ported by ‘Aktion Österreich-Ungarn’ (ICM-2018-12611). This work beds. Geochim. Cosmochim. Acta 22, 2–15. https://doi.org/10.1016/0016-7037(61)
90069-2.
was financially sponsored by the University of Szeged Open Access Calder, J.H., Gibling, M.R., Mukhopadhyay, P.K., 1991. Peat formation in a Westphalian
Fund (4665). B piedmont setting, Cumberland basin, Nova Scotia: implications for the maceral-
based interpretation of rheotropic and raised paleomires. B. Soc. Geol. Fr. 162,
283–298.
References Carr, A.D., 2000. Suppression and retardation of vitrinite reflectance: part 1. Formation
and significance for hydrocarbon generation. J. Petrol. Geol. 23, 313–343. https://
van Aarssen, B.G.K., Hessels, J.K.C., Abbink, O.A., de Leeuw, J.W., 1992. The occurrence doi.org/10.1111/j.1747-5457.2000.tb01022.x.
of polycyclic sesqui-, tri-, and oligoterpenoids derived from a resinous polymeric Casagrande, D.J., 1987. Sulphur in peat and coal, in: Scott, a.C. (Ed.), coal and coal-
cadinene in crude oils from Southeast Asia. Geochim. Cosmochim. Acta 56, bearing strata: recent advances. Geol. Soc. Lond. Spec. Publ. 32, 87–105. https://doi.
1231–1246. https://doi.org/10.1016/0016-7037(92)90059-r. org/10.1144/gsl.sp.1987.032.01.07.
Aichner, B., Herzschuh, U., Wilkes, H., 2010. Influence of aquatic macrophytes on the Clayton, C.J., 1991. Effect of maturity on carbon isotope ratios of oils and condensates.
stable carbon isotopic signatures of sedimentary organic matter in lakes on the Org. Geochem. 17, 887–899. https://doi.org/10.1016/0146-6380(91)90030-n.
Tibetan Plateau. Org. Geochem. 41, 706–718. https://doi.org/10.1016/j. Close, H.G., 2019. Compound-specific isotope geochemistry in the ocean. Annu. Rev. Mar.
orggeochem.2010.02.002. Sci. 11, 27–56. https://doi.org/10.1146/annurev-marine-121916-063634.
Alexander, G., Hazai, I., Grimalt, J., Albaigés, J., 1987. Occurrence and transformation of Collister, J.W., Summons, R.E., Lichtfouse, E., Hayes, J.M., 1992. An isotopic biogeo-
phyllocladanes in brown coals from Nograd Basin, Hungary. Geochim. Cosmochim. chemical study of the Green River oil shale. Org. Geochem. 19, 265–276. https://doi.
Acta 51, 2065–2073. https://doi.org/10.1016/0016-7037(87)90256-0. org/10.1016/0146-6380(92)90042-v.
Alexander, R., Kagi, R., Noble, R., 1983. Identification of the bicyclic sesquiterpenes Collister, J.W., Lichtfouse, E., Hieshima, G., Hayes, J.M., 1994. Partial resolution of
drimane and eudesmane in petroleum. J. Chem. Soc. Chem. Commun. (5), 226–228. sources of n-alkanes in the saline portion of the Parachute Creek Member, Green
https://doi.org/10.1039/c39830000226. River Formation (Piceance Creek Basin, Colorado). Org. Geochem. 21, 645–659.
Alexander, R., Kagi, R.I., Noble, R., Volkman, J.K., 1984. Identification of some bicyclic https://doi.org/10.1016/0146-6380(94)90010-8.
alkanes in petroleum. Org. Geochem. 6, 63–72. https://doi.org/10.1016/0146- Coplen, T.B., 2011. Guidelines and recommended terms for expression of stable-isotope-
6380(84)90027-5. ratio and gas-ratio measurement results. Rapid Commun. Mass Spec. 25, 2538–2560.
Alexander, R., Bastow, T.P., Fisher, S.J., Kagi, R.I., 1995. Geosynthesis of organic com- https://doi.org/10.1002/rcm.5129.
pounds: II. Methylation of phenanthrene and alkylphenanthrenes. Geochim. Cortes, J.E., Rincon, J.M., Jaramillo, J.M., Philp, R.P., Allen, J., 2010. Biomarkers and
Cosmochim. Acta 59, 4259–4266. https://doi.org/10.1016/0016-7037(95)00285-8. compound-specific stable carbon isotope of n-alkanes in crude oils from Eastern
ASTM International, 2015. ASTM D2797/D2797M-11a: Standard Practice for Preparing Llanos Basin, Colombia. J. S. Am. Earth Sci. 29, 198–213. https://doi.org/10.1016/j.
Coal Samples for Microscopical Analysis by Reflected Light. ASTM International, jsames.2009.03.010.
West Conshohocken, Pennsylvania. https://doi.org/10.1520/d2797_d2797m-11a. Cranwell, P.A., 1977. Organic Geochemistry of Cam Loch (Sutherland) sediments. Chem.
(5 p). Geol. 20, 205–221. https://doi.org/10.1016/0009-2541(77)90044-4.
ASTM International, 2018. ASTM D3174–12: Standard Test Method for Ash in the Cranwell, P.A., Eglinton, G., Robinson, N., 1987. Lipids of aquatic organisms as potential
Analysis Smple of Coal and Coke from Coal. ASTM International, West contributors to lacustrine sediments—II. Org. Geochem. 11, 513–527. https://doi.
Conshohocken, Pennsylvania. https://doi.org/10.1520/d3174-12r18. (6 p). org/10.1016/0146-6380(87)90007-6.
Badics, B., Vető, I., 2012. Source rocks and petroleum systems in the Hungarian part of Dehmer, J., 1995. Petrological and organic geochemical investigation of recent peats with
the Pannonian Basin: the potential for shale gas and shale oil plays. Mar. Petrol. Geol. known environments of deposition. Int. J. Coal Geol. 28, 111–138. https://doi.org/
31, 53–69. https://doi.org/10.1016/j.marpetgeo.2011.08.015. 10.1016/0166-5162(95)00016-x.
Báldi, T., Báldi-Beke, M., 1985. The evolution of the Hungarian Paleogene Basins. Acta Didyk, B.M., Simoneit, B.R.T., Brassell, S.C., Eglinton, G., 1978. Organic geochemical
Geol. Hung. 28, 5–28. indicators of palaeoenvironmental conditions of sedimentation. Nature 272,
Báldi-Beke, M., 2003a. A dunántúli eocén kőszénösszletek fedőképződményeinek 216–222. https://doi.org/10.1038/272216a0.
rétegtana és paleoökológiája nannoplankton alapján (Stratigraphy and palaeoecology Diefendorf, A.F., Freimuth, E.J., 2017. Extracting the most from terrestrial plant-derived
of the formations overlying the Middle Eocene coal sequence based on nannofossils - n-alkyl lipids and their carbon isotopes from the sedimentary record: a review. Org.
(Transdanubia, Hungary)). Bull. Hung. Geol. Soc. 133, 325–343 (in Hungarian with Geochem. 103, 1–21. https://doi.org/10.1016/j.orggeochem.2016.10.016.
English abstract). Diefendorf, A.F., Freeman, K.H., Wing, S.L., Graham, H.V., 2011. Production of n-alkyl
Báldi-Beke, M., 2003b. A magyarországi eocén transzgressziók ideje: a nannoplankton lipids in living plants and implications for the geologic past. Geochim. Cosmochim.
biosztratigráfiai és magnetosztratígráfiai eredmények együttes értékelése (Time of Acta 75, 7472–7485. https://doi.org/10.1016/j.gca.2011.09.028.
the Eocene transgressions in Hungary: evaluation of the nannoplankton Diefendorf, A.F., Sberna, D.T., Taylor, D.W., 2015. Effect of thermal maturation on plant-
13
derived terpenoids and leaf wax n-alkyl components. Org. Geochem. 89–90, 61–70. Geochem. 38, 180–197. https://doi.org/10.1016/j.orggeochem.2006.10.007.
https://doi.org/10.1016/j.orggeochem.2015.10.006. Karrer, W., Cherbuliez, E., Eugster, C.H., 1977. Konstitution und Vorkommen der orga-
Diessel, C.F.K., 1992. Coal-Bearing Depositional Systems. Springer-Verlag, Berlin. nischen Pflanzenstoffe (exclusive Alkaloide) Ergänzungsband I. Birkhäuser Verlag,
Doković, N., Mitrović, D., Životić, D., Bechtel, A., Sachsenhofer, R.F., Matić, V., Basel und Stuttgart.
Glamočanin, L., Stojanović, K., 2018. Petrographical and organic geochemical study Kercsmár, Zs, Budai, T., Csillag, G., Selmeczi, I., Sztanó, O., 2015. Surface Geology of
of the lignite from the Smederevsko Pomoravlje field (Kostolac Basin, Serbia). Int. J. Hungary. Explanatory Notes to the Geological Map of Hungary (1,500 000).
Coal Geol. 195, 139–171. https://doi.org/10.1016/j.coal.2018.06.005. Geological and Geophysical Institute of Hungary, Budapest.
Dzou, L.I.P., Hughes, W.B., 1993. Geochemistry of oils and condensates, K field, offshore Killops, S.D., Funnell, R.H., Suggate, R.P., Sykes, R., Peters, K.E., Walters, C., Woolhouse,
Taiwan: a case study in migration fractionation. Org. Geochem. 20, 437–462. https:// A.D., Boudou, J.-P., 1998. Predicting generation and expulsion of paraffinic oil from
doi.org/10.1016/0146-6380(93)90092-p. vitrinite-rich coals. Org. Geochem. 29, 1–21. https://doi.org/10.1016/s0146-
Eble, C.F., Greb, S.F., Williams, D.A., Hower, J.C., O'Keefe, J.M.K., 2019. Palynology, 6380(98)00087-4.
organic petrology and geochemistry of the Bell coal bed in Western Kentucky, Eastern Kováč, M., Plašienka, D., Soták, J., Vojtko, R., Oszczypko, N., Less, Gy., Ćosović, V.,
Interior (Illinois) Basin, USA. Int. J. Coal Geol. 213, 103264. https://doi.org/10. Fügenschuh, B., Králiková, S., 2016. Paleogene palaeogeography and basin evolution
1016/j.coal.2019.103264. of the Western Carpathians, Northern Pannonian domain and adjoining areas. Glob.
Eglinton, G., Hamilton, R.J., 1967. Leaf epicuticular waxes. Science 156, 1322–1335. Planet. Chang. 140, 9–27. https://doi.org/10.1016/j.gloplacha.2016.03.007.
https://doi.org/10.1126/science.156.3780.1322. Kubacska, A., 1925. Daten zur Geologie der Umgebung des Nagyszál. Bull. Hung. Geol.
Espitalié, J., LaPorte, J.L., Madec, M., Marquis, F., Leplat, P., Paulet, J., Boutefeu, A., Soc. 55, 327–332.
1977. Méthode rapide de charactérisation des roches metres, de leur potential Kvaček, Z., 2010. Forest flora and vegetation of the European early Palaeogene – a re-
pétrolier et de leur degé d'évolution. Revue de l'Institut Français du Pétrole 32, view. Bull. Geosci. 85, 63–76. https://doi.org/10.3140/bull.geosci.1146.
23–42. https://doi.org/10.2516/ogst:1977002. Lafargue, E., Marquis, F., Pillot, D., 1998. Rock-Eval 6 applications in hydrocarbon ex-
Espitalié, J., Marquis, F., Barsony, I., 1984. Geochemical logging. In: Voorhees, K.J. (Ed.), ploration, production, and soil contamination studies. Revue de l'Institut Français du
Analytical Pyrolysis Techniques and Applications, Butterworths, London, pp. Pétrole 53, 421–437. https://doi.org/10.2516/ogst:1998036.
276–304. Laflamme, R.E., Hites, R.A., 1978. The global distribution of polycyclic aromatic hydro-
Ficken, K.J., Barber, K.E., Eglinton, G., 1998. Lipid biomarker, δ13C and plant macrofossil carbons in recent sediments. Geochim. Cosmochim. Acta 42, 289–303. https://doi.
stratigraphy of a Scottish montane peat bog over the last two millennia. Org. org/10.1016/0016-7037(78)90182-5.
Geochem. 28, 217–237. https://doi.org/10.1016/s0146-6380(97)00126-5. Lamb, A.L., Wilson, G.P., Leng, M.J., 2006. A review of coastal palaeoclimate and relative
Ficken, K.J., Li, B., Swain, D.L., Eglinton, G., 2000. An n-alkane proxy for the sedimentary sea-level reconstructions using δ13C and C/N ratios in organic material. Earth-Sci.
input of submerged/floating freshwater aquatic macrophytes. Org. Geochem. 31, Rev. 75, 29–57. https://doi.org/10.1016/j.earscirev.2005.10.003.
745–749. https://doi.org/10.1016/s0146-6380(00)00081-4. Less, Gy, 2005. Palaeogene. In: Pelikán, P. (Ed.), Geology of the Bükk Mountains,
Freeman, K.H., Hayes, J.M., Trendel, J.M., Albrecht, P., 1990. Evidence from carbon Explanatory Book of the Geological Map of the Bükk Mountains (1:50 000).
isotope measurements for diverse origins of sedimentary hydrocarbons. Nature 343, Hungarian Geological Society, Budapest, pp. 204–210.
254–256. https://doi.org/10.1038/343254a0. Li, R., Fan, J., Xue, J., Meyers, P.A., 2017. Effects of early diagenesis on molecular dis-
Gidai, L., 1978. A kósdi eocén képződmények rétegtani viszonyai (Conditions strati- tributions and carbon isotopic compositions of leaf wax long chain biomarker n-al-
graphiques des formations éocènes de Kósd). Bull. Hung. Geol. Soc. 108, 65–86 (in kanes: Comparison of two one-year-long burial experiments. Org. Geochem. 104,
Hungarian with extended French summary). 8–18. https://doi.org/10.1016/j.orggeochem.2016.11.006.
Gross, D., Bechtel, A., Harrington, G.J., 2015. Variability in coal facies as reflected by Littke, R., Leythaeuser, D., Radke, M., Schaefer, R.G., 1990. Petroleum generation and
organic petrological and geochemical data in Cenozoic coal beds offshore Shimokita migration in coal seams of the Carboniferous Ruhr Basin, Northwest Germany. Org.
(Japan) - IODP Exp. 337. Int. J. Coal Geol. 152, 63–79. https://doi.org/10.1016/j. Geochem. 16, 247–258. https://doi.org/10.1016/0146-6380(90)90045-2.
coal.2015.10.007. Lockheart, M.J., Van Bergen, P.F., Evershed, R.P., 1997. Variations in the stable carbon
Haas, J., Kovács, S., 2012. Pelso composite unit. In: Haas, J. (Ed.), Geology of Hungary. isotope compositions of individual lipids from the leaves of modern angiosperms:
Springer-Verlag, Berlin, pp. 21–81. implications for the study of higher land plant-derived sedimentary organic matter.
Hámor, T., 1994. The occurrence and morphology of sedimentary pyrite. Acta Geol. Org. Geochem. 26, 137–153. https://doi.org/10.1016/s0146-6380(96)00135-0.
Hung. 37, 153–181. Mackenzie, A.S., Maxwell, J.R., 1981. Assessment of thermal maturation in sedimentary
Hámor-Vidó, M., Hámor, T., 2007. Sulphur and carbon isotopic composition of power rocks by molecular measurements. In: Brooks, J. (Ed.), Organic Maturation Studies
supply coals in the Pannonian Basin, Hungary. Int. J. Coal Geol. 71, 425–427. and Fossil Fuel Exploration. Academic Press, London, pp. 239–254.
https://doi.org/10.1016/j.coal.2006.11.002. Mackenzie, A.S., Patience, R.L., Maxwell, J.R., Vandenbroucke, M., Durand, B., 1980.
Havelcová, M., Sýkorová, I., Trejtnarová, H., Šulc, A., 2012. Identification of organic Molecular parameters of maturation in the Toarcian shales, Paris Basin, France–I.
matter in lignite samples from basins in the Czech Republic: Geochemical and pet- changes in the configuration of acyclic isoprenoid alkanes, steranes, and triterpanes.
rographic properties in relation to lithotype. Fuel 99, 129–142. https://doi.org/10. Geochim. Cosmochim. Acta 44, 1709–1721. https://doi.org/10.1016/0016-7037(80)
1016/j.fuel.2012.03.025. 90222-7.
Hayes, J.M., 1993. Factors controlling 13C contents of sedimentary organic compounds: Maclean, L.C.W., Tyliszczak, T., Gilbert, P.U.P.A., Zhou, D., Pray, T.J., Onstott, C.,
principles and evidence. Mar. Geol. 133, 111–126. https://doi.org/10.1016/0025- Southam, G., 2008. A high-resolution chemical and structural study of framboidal
3227(93)90153-m. pyrite formed within a low-temperature bacterial biofilm. Geobiology 6, 471–480.
Hayes, J.M., Takigiku, R., Ocampo, R., Callot, H.J., Albrecht, P., 1987. Isotopic compo- https://doi.org/10.1111/j.1472-4669.2008.00174.x.
sitions and probable origins of organic molecules in the Eocene Messel shale. Nature Markič, M., Sachsenhofer, R.F., 1997. Petrographic composition and depositional en-
329, 48–51. https://doi.org/10.1038/329048a0. vironments of the Pliocene Velenje lignite seam (Slovenia). Int. J. Coal Geol. 33,
Hayes, J.M., Freeman, K.H., Popp, B.N., Hoham, C.H., 1990. Compound-specific isotopic 229–254. https://doi.org/10.1016/s0166-5162(96)00043-2.
analyses: a novel tool for reconstruction of ancient biogeochemical processes. Org. Marynowski, L., Smolarek, J., Bechtel, A., Philippe, M., Kurkiewicz, S., Simoneit, B.R.T.,
Geochem. 16, 1115–1128. https://doi.org/10.1016/0146-6380(90)90147-r. 2013. Perylene as an indicator of conifer fossil wood degradation by wood-degrading
Holtvoeth, J., Whiteside, J.H., Engels, S., Freitas, F.S., Grice, K., Greenwood, P., Johnson, fungi. Org. Geochem. 59, 143–151. https://doi.org/10.1016/j.orggeochem.2013.04.
S., Kendall, I., Lengger, S.K., Lücke, A., Mayr, C., Naafs, B.D.A., Rohrssen, M., 006.
Sepúlveda, J., 2019. The paleolimnologist's guide to compound-specific stable isotope Mead, R., Xu, Y., Chong, J., Jaffé, R., 2005. Sediment and soil organic matter source
analysis – an introduction to principles and applications of CSIA for Quaternary lake assessment as revealed by the molecular distribution and carbon isotopic composition
sediments. Q. Sci. Rev. 207, 101–133. https://doi.org/10.1016/j.quascirev.2019.01. of n-alkanes. Org. Geochem. 36, 363–370. https://doi.org/10.1016/j.orggeochem.
001. 2004.10.003.
Horváth, F., Bada, G., Windhoffer, G., Csontos, L., Dövény, P., Fodor, L., Grenerczy, G., Meyers, P.A., 1997. Organic geochemical proxies of paleoceanographic, paleolimnologic,
Síkhegyi, F., Szafián, P., Székely, B., Tímár, G., Tóth, L., Tóth, T., 2005. Atlas of the and paleoclimatic processes. Org. Geochem. 27, 213–250. https://doi.org/10.1016/
Present-Day Geodynamics of the Pannonian Basin: Euroconform Maps with s0146-6380(97)00049-1.
Explanatory Text. http://geophysics.elte.hu/projektek/geodinamikai_atlasz_eng.htm MGSH – Mining and Geological Survey of Hungary, 2019. Digital Coal Cadastre of
(accessed on 5 August 2019). Hungary. https://map.mbfsz.gov.hu/coal_cadastre/ (accessed on 13 January 2020).
Huang, W.Y., Meinshein, W.G., 1979. Sterols as ecological indicators. Geochim. Milota, K., Kovacs, A., Galicz, Z., 1995. Petroleum potential of the North Hungarian
Cosmochim. Acta 43, 739–745. https://doi.org/10.1016/0016-7037(79)90257-6. Oligocene sediments. Pet. Geosci. 1, 81–87. https://doi.org/10.1144/petgeo.1.1.81.
Hughes, W.B., Holba, A.G., Dzou, L.I.P., 1995. The ratios of dibenzothiophene to phe- Monthioux, M., Landais, P., 1989. Natural and artificial maturation of coal: non-hopanoid
nanthrene and pristan to phytan as indicators of depositional environment and li- biomarkers. Chem. Geol. 77, 71–85. https://doi.org/10.1016/0009-2541(89)
thology of petroleum source rocks. Geochim. Cosmochim. Acta 59, 3581–3598. 90017-x.
https://doi.org/10.1016/0016-7037(95)00225-o. Morad, S., 1998. Carbonate cementation in sandstones: distribution patterns and geo-
Hussler, G., Connan, J., Albrecht, P., 1984. Novel families of tetra- and hexacyclic aro- chemical evolution. Sp. Pub. IAS 26, 1–26. https://doi.org/10.1002/
matic hopanoids predominant in carbonate rocks and crude oils. Org. Geochem. 6, 9781444304893.ch1.
39–49. https://doi.org/10.1016/0146-6380(84)90025-1. Murray, A.P., Summons, R.E., Boreham, C.J., Dowling, L.M., 1994. Biomarker and n-
ICCP, 1998. The new vitrinite classification (ICCP System 1994). Fuel 77, 349–358. alkane isotope profiles for Tertiary oils: relationship to source rock depositional
https://doi.org/10.1016/s0016-2361(98)80024-0. setting. Org. Geochem. 22, 521–542. https://doi.org/10.1016/0146-6380(94)
ICCP, 2001. The new inertinite classification (ICCP System 1994). Fuel 80, 459–471. 90124-4.
https://doi.org/10.1016/s0016-2361(00)00102-2. Némedi Varga, Z., 2010. Kőszénföldtan. A magyarországi kőszénelőfordulások
Jacob, J., Disnar, J.-R., Boussafir, M., Spadano Albuquerque, A.L., Sifeddine, A., Turcq, B., áttekintésével és bibliográfiájával. Bíbor kiadó, Miskolc (in Hungarian).
2007. Contrasted distributions of triterpene derivatives in the sediments of Lake Caçó Nott, C.J., Xie, S., Avsejs, L.A., Maddy, D., Chambers, F.M., Evershed, R.P., 2000. N-
reflect paleoenvironmental changes during the last 20,000 yrs in NE Brazil. Org. Alkane distributions in ombrotrophic mires as indicators of vegetation change related
14
to climate variation. Org. Geochem. 31, 231–235. https://doi.org/10.1016/s0146- compounds. Nature 352, 425–427. https://doi.org/10.1038/352425a0.
6380(99)00153-9. Rögl, F., 1999. Mediterranean and Paratethys. Facts and hypotheses of an Oligocene to
Nytoft, H.P., Samuel, O.J., Kildahl-Andersen, G., Johansen, J.E., Jones, M., 2009. Novel Miocene paleogeography (short overview). Geol. Carpath. 50, 339–349.
C15 sesquiterpanes in Niger Delta oils: structural identification and potential appli- Rohmer, M., 1993. The biosynthesis of triterpenoids of the hopane series in the
cation as new markers of angiosperm input in light oils. Org. Geochem. 40, 595–603. Eubacteria: a mine of new enzymatic reactions. Pure App. Chem. 65, 1293–1298.
https://doi.org/10.1016/j.orggeochem.2009.02.003. https://doi.org/10.1351/pac199365061293.
Odden, W., Barth, T., Talbot, M.R., 2002. Compound-specific carbon isotope analysis of Rooney, M.A., Vuletich, A.K., Griffith, C.E., 1998. Compound-specific isotope analysis as a
natural and artificially generated hydrocarbons in source rocks and petroleum fluids tool for characterizing mixed oils: an example from the West of Shetlands area. Org.
from offshore Mid-Norway. Org. Geochem. 33, 47–65. https://doi.org/10.1016/ Geochem. 29, 241–254. https://doi.org/10.1016/s0146-6380(98)00136-3.
s0146-6380(01)00127-9. Sachsenhofer, R.F., Shymanovskyy, V.A., Bechtel, A., Gratzer, R., Horsfield, B.,
O'Leary, M.H., 1981. Carbon isotope fractionation in plants. Phytochemistry 20, 553–567. Reischenbacher, D., 2010. Palaeozoic source rocks in the Dniepr–Donets Basin,
https://doi.org/10.1016/0031-9422(81)85134-5. Ukraine. Pet. Geosci. 16, 377–399. https://doi.org/10.1144/1354-079309-032.
Otto, A., Wilde, V., 2001. Sesqui-, di-, and triterpenoids as chemosystematic markers in Sachsenhofer, R.F., Popov, S.V., Coric, S., Mayer, J., Misch, D., Morton, M.T., Pupp, M.,
extant conifers – a review. Bot. Rev. 67, 141–238. https://doi.org/10.1007/ Rauball, J., Tari, G., 2018. Paratethyan petroleum source rocks: an overview. J.
bf02858076. Petrol. Geol. 41, 219–245. https://doi.org/10.1111/jpg.12702.
Otto, A., Walther, H., Püttmann, W., 1997. Sesqui- and diterpenoid biomarkers preserved Schoell, M., 1984. Stable Isotopes in Petroleum Research. In: Advances in Petroleum
in Taxodium-rich Oligocene oxbow lake clays, Weisselster basin, Germany. Org. Geochemistry, pp. 215–245. https://doi.org/10.1016/b978-0-12-032001-1.50009-2.
Geochem. 26, 105–115. https://doi.org/10.1016/s0146-6380(96)00133-7. Schoell, M., Simoneit, B.R.T., Wang, T.G., 1994. Org. Geochem. and coal petrology of
Ourisson, G., Albrecht, P., Rohmer, M., 1979. The hopanoids. Pure Appl. Chem. 51, tertiary brown coal in the Zhoujing mine, Baise Basin, South China—4. Biomarker
709–729. sources inferred from stable carbon isotope compositions of individual compounds.
Ozsvárt, P., Kocsis, L., Nyerges, A., Győri, O., Pálfy, J., 2016. The Eocene-Oligocene cli- Org. Geochem. 21, 713–719. https://doi.org/10.1016/0146-6380(94)90014-0.
mate transition in the Central Paratethys. Palaeogeogr. Palaeoclimatol. Palaeoecol. Schwarzbauer, J., Littke, R., Meier, R., Strauss, H., 2013. Stable carbon isotope ratios of
459, 471–487. https://doi.org/10.1016/j.palaeo.2016.07.034. aliphatic biomarkers in late Palaeozoic coals. Int. J. Coal Geol. 107, 127–140. https://
Palotai, M., Csontos, L., 2010. Strike-slip reactivation of a Paleogene to Miocene fold and doi.org/10.1016/j.coal.2012.10.001.
thrust belt along the central part of the Mid-Hungarian Shear Zone. Geol. Carpath. 61, Seifert, W.K., Moldowan, J.M., 1986. Use of biological markers in petroleum exploration.
4833–4893. https://doi.org/10.2478/v10096-010-0030-3. In: Johns, R.B. (Ed.), Methods in Geochemistry and Geophysics 24. Elsevier,
Papp, K., 1913. Les ressources houilléres de la Hongrie. In: McInnes, W., Dowling, D.B., Amsterdam, pp. 261–290.
Leach, W.W. (Eds.), The Coal Resource of the World. Morang and CO Limited, Simoneit, B.R.T., Grimalt, J.O., Wang, T.G., Cox, R.E., Hatcher, P.G., Nissenbaum, A.,
Toronto. 1986. Cyclic terpenoids of contemporary resinous plant detritus and of fossil woods,
Pelikán, P., 2005. Mesozoic. In: Pelikán, P. (Ed.), Geology of the Bükk Mountains, amber and coal. Org. Geochem. 10, 877–889. https://doi.org/10.1016/s0146-
Explanatory Book of the Geological Map of the Bükk Mountains (1:50 000). 6380(86)80025-0.
Hungarian Geological Society, Budapest, pp. 187–204. Simoneit, B.R.T., Schoell, M., Stefanova, M., Stojanova, G., Nosyrev, I.E., Goranova, M.,
Pepper, A.S., Corvi, P.J., 1995. Simple kinetic models of petroleum formation. Part I: oil 1995. Composition of the extract from a Carboniferous bituminous coal. 2.
and gas generation from kerogen. Mar. Petrol. Geol. 12, 291–319. https://doi.org/10. Compound-specific isotope analyses. Fuel 74, 1194–1199. https://doi.org/10.1016/
1016/0264-8172(95)98381-e. 0016-2361(95)00038-7.
Peters, K.E., 1986. Guidelines for evaluating petroleum source rocks using programmed Sofer, Z., 1984. Stable carbon isotope compositions of crude oils: application to source
pyrolysis. AAPG Bull. 70, 318–329. https://doi.org/10.1306/94885688-1704-11d7- depositional environments and petroleum alteration. AAPG Bull. 68, 31–49. https://
8645000102c1865d. doi.org/10.1306/ad460963-16f7-11d7-8645000102c1865d.
Peters, K.E., Cassa, M.R., 1994. Applied source rock geochemistry. In: Magoon, L.B., Dow, Stock, A.T., Littke, R., Lücke, A., Zieger, L., Thielemann, T., 2016. Miocene depositional
G.W. (Eds.), The Petroleum System – From Source to Trap. AAPG Mem. 60pp. 93–120 environment and climate in western Europe: the lignite deposits of the lower Rhine
(Tulsa, Oklahoma). Basin, Germany. Int. J. Coal Geol. 157, 2–18. https://doi.org/10.1016/j.coal.2015.
Peters, K.E., Walters, C.C., Moldowan, J.M., 2005. The Biomarker Guide, second ed. 06.009.
Cambridge University Press, Cambridge. Strachan, M.G., Alexander, R., Kagi, R.I., 1988. Trimethylnaphthalenes in crude oils and
Peters, K.E., Hackley, P.C., Thomas, J.J., Pomerantz, A.E., 2018. Suppression of vitrinite sediments: effects of source and maturity. Geochim. Cosmochim. Acta 52,
reflectance by bitumen generated from liptinite during hydrous pyrolysis of artificial 1255–1264. https://doi.org/10.1016/0016-7037(88)90279-7.
source rock. Org. Geochem. 125, 220–228. https://doi.org/10.1016/j.orggeochem. Sukh Dev, 1989. Terpenoids. In: Rowe, J.W. (Ed.), Natural Products of Woody Plants. vol.
2018.09.010. 1. Springer, Berlin, pp. 691–807.
Petersen, H.I., Ratanasthien, B., 2011. Coal facies in a Cenozoic paralic lignite bed, Krabi Sweeney, R.E., Kaplan, I.R., 1973. Pyrite framboid formation: laboratory synthesis and
Basin, southern Thailand: changing peat-forming conditions related to relative sea- marine sediments. Econ. Geol. 68, 618–634. https://doi.org/10.2113/gsecongeo.68.
level controlled watertable variations. Int. J. Coal Geol. 87, 2–12. https://doi.org/10. 5.618.
1016/j.coal.2011.04.004. Sykes, R., Snowdon, L.R., 2002. Guidelines for assessing the petroleum potential of coaly
Pickel, W., Kus, J., Flores, D., Kalaitzidis, S., Christanis, K., Cardott, B., Misz-Kennan, M., source rocks using Rock-Eval pyrolysis. Org. Geochem. 33, 1441–1455. https://doi.
Rodrigues, S., Hentschel, A., Hamor-Vido, M., Crosdale, P., Wagner, N., ICCP, 2017. org/10.1016/s0146-6380(02)00183-3.
Classification of liptinite – ICCP System 1994. Int. J. Coal Geol. 169, 40–61. https:// Talbot, H.M., McClymont, E.L., Inglis, G.N., Evershed, R.P., Pancost, R.D., 2016. Origin
doi.org/10.1016/j.coal.2016.11.004. and preservation of bacteriohopanepolyol signatures in Sphagnum peat from
Popov, S.V., Akhmetiev, M.A., Bugrova, E.M., Lopatin, A.V., Amitrov, O.V., Andreeva- Bissendorfer Moor (Germany). Org. Geochem. 97, 95–110. https://doi.org/10.1016/
Grigorovich, A.S., Zherikhin, V.V., Zaporozhets, N.I., Nikolaeva, I.A., j.orggeochem.2016.04.011.
Krasheninnikov, V.A., Kuzmicheva, E.I., Sytchevskaya, E.K., Shcherba, I.G., 2001. Tari, G., Báldi, T., Báldi-Beke, M., 1993. Paleogene retroarc flexural basin beneath the
Biogeography of the Northern Peri-Tethys from the late Eocene to the early Miocene: Neogene Pannonian Basin: a geodynamic model. Tectonophysics 226, 433–455.
part 1. Late Eocene. Paleontol. J. 35, S1–S68 Supp. Ser. 1. https://doi.org/10.1016/0040-1951(93)90131-3.
Radke, M., Welte, D.H., 1983. The Methylphenanthrene Index (MPI): A maturity para- Taylor, G.H., Teichmüller, M., Davis, A., Diessel, C.F.K., Littke, R., Robert, P., 1998.
meter based on aromatic hydrocarbons. In: Bjoroy, M. (Ed.), Advances in Org. Organic Petrology. Gebrüder Bontraeger, Berlin.
Geochem. Wiley, Chichester, pp. 504–512. Tissot, B.T., Welte, D.H., 1984. Petroleum Formation and Occurrences. Springer, Berlin.
Radke, M., Schaefer, R.G., Leythaeuser, D., Teichmüller, M., 1980. Composition of soluble Tuo, J., Wang, X., Chen, J., Simoneit, B.R.T., 2003. Aliphatic and diterpenoid hydro-
organic matter in coals: relation to rank and liptinite fluorescence. Geochim. carbons and their individual carbon isotope compositions in coals from the Liaohe
Cosmochim. Acta 44, 1787–1800. https://doi.org/10.1016/0016-7037(80)90228-8. Basin, China. Org. Geochem. 34, 1615–1625. https://doi.org/10.1016/j.orggeochem.
Radke, M., Welte, D.H., Willsch, H., 1982. Geochemical study of a well in the Western 2003.08.004.
Canada Basin: relation of aromatic distribution pattern to maturity of organic matter. Volkman, J.K., 1986. A review of sterol markers for marine and terrigenous organic
Geochim. Cosmochim. Acta 46, 1–10. https://doi.org/10.1016/0016-7037(82) matter. Org. Geochem. 9, 83–99. https://doi.org/10.1016/0146-6380(86)90089-6.
90285-x. Wakeham, S.G., Schaffner, C., Giger, W., 1980. Polycyclic aromatic hydrocarbons in re-
Radke, M., Hilkert, A., Rullkötter, J., 1998. Molecular stable carbon isotope compositions cent lake sediments. II. Compounds derived from biological precursors during early
of alkylphenanthrenes in coals and marine shales related to source and maturity. Org. diagenesis. Geochim. Cosmochim. Acta 44, 415–429. https://doi.org/10.1016/0016-
Geochem. 28, 785–795. https://doi.org/10.1016/s0146-6380(98)00048-5. 7037(80)90041-1.
Rákosi, L., 1978. A magyarországi eocén mangrove palinológiai adatai (Données paly- Wilhelms, A., Larter, S.R., Hall, K., 1994. A comparative study of the stable carbon iso-
nologiques de la mangrove éocène de Hongrie). In: Annual Report of the Hungarian topic composition of crude oil alkanes and associated crude oil asphaltene pyrolysate
Geological Institute of 1976, pp. 357–374 (in Hungarian with extended French alkanes. Org. Geochem. 21, 751–759. https://doi.org/10.1016/0146-6380(94)
summary). 90017-5.
Rieley, G., Collier, R.J., Jones, D.M., Eglinton, G., Eakin, P.A., Fallick, A.E., 1991. Sources Wilkins, R.V.T., George, S.C., 2002. Coal as a source rock for oil: a review. Int. J. Coal
of sedimentary lipids deduced from stable carbon-isotope analyses of individual Geol. 50, 317–361. https://doi.org/10.1016/s0166-5162(02)00134-9.
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International Journal of Coal Geology

Petrographic and organic geochemical study of the Eocene Kosd Formation T

1. Introduction sedimentation in this basin was characterized by a generally trans-

bituminous coal ended in the 1930s (Némedi Varga, 2010).

# [vol%, mmf] [vol%]

The stereoisomer ratio of 22S/(22S + 22R) isomers of

4.4.4. Sesquiterpenoids, diterpenoids, non-hopanoid triterpenoids

# [mg/g TOC] [wt%] [μg/g TOC]

dimethylphenanthrenes is predominated by 1,7–DMP, and the co-

4.4.6. Sulphur-aromatic compounds

Fig. 7. Normalized distribution of short- (n-C15–19), mid- (n-C21–25) and long-

5.1. Thermal maturity

# [%] [%] [%]

20 22 35 25 1.00 3.30 30 24 46 0.13 0.42 0.65 0.55 0.75 0.89 0.20

Fig. 8. Gas chromatograms (total ion current) of saturated hydrocarbon frac-

vitrinite (Wilkins and George, 2002). Hence, the vitrinite reﬂectance of

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