1 s2.0 S0166516212002583 Main

International Journal of Coal Geology 111 (2013) 522
Contents lists available at SciVerse ScienceDirect
International Journal of Coal Geology

journal homepage: www.elsevier.com/locate/ijcoalgeo
Petrological and geochemical composition of lignite from the D eld,

Kolubara basin (Serbia)
Dragana ivoti a,, Ksenija Stojanovi b, Ivan Greti b, Branimir Jovanievi b, Olga Cvetkovi c,
Aleksandra ajnovi c, Vladimir Simi a, Rajko Stojakovi d, Georg Scheeder e
a
University of Belgrade, Faculty of Mining and Geology, Djusina 7, 11000 Belgrade, Serbia
University of Belgrade, Faculty of Chemistry, Studentski trg 12-16, 11000 Belgrade, Serbia
Center of Chemistry, IChTM, Studentski trg 12-16, 11000 Belgrade, Serbia
d
Electric Power Industry of Serbia, EACP MB Kolubara plc, OPM Baroevac, 11565 Baroevac, Serbia
e
Federal Institute for Geosciences and Natural Resources, Steveledge 2, 30655 Hannover, Germany
b
c
a r t i c l e
i n f o
Article history:
Received 3 February 2012
Received in revised form 10 October 2012
Accepted 24 October 2012
Available online 14 November 2012
Keywords:
Kolubara basin
Lignites
Macerals
Biomarkers
Paleoenvironment
a b s t r a c t
The Upper Miocene lignite from the Main coal seam in the D eld, Kolubara basin, is a typical humic coal with
huminite, liptinite and inertinite concentrations of up to 83.7 vol.%, 17.2 vol.% and 15.5 vol.%, respectively. In
the huminite group, textinite and ulminite are the most abundant macerals with variable amounts of
densinite and attrinite. Liptodetrinite and sporinite are the most common macerals of the liptinite group,
while inertodetrinite is the most abundant maceral of the inertinite group. The mineral matter consists mostly of clay minerals. The main sources of organic matter were gymnosperms (conifers) and microbial biomass,
followed by angiosperms. Based on composition of saturated and aromatic diterpenoids it has been established
that coal forming plants belonged to the gymnosperm families Taxodiaceae, Podocarpaceae, Cupressaceae,
Araucariaceae, Phyllocladaceae and Pinaceae. Peatication occurred in neutral to slightly acidic, fresh water environment. Composition and distribution of biomarkers show that diagenetic changes of the organic matter were
mainly governed by bacterial activity in a suboxic to oxic environment. Based on distribution of aromatic
diterpenoids a novel diagenetic pathway for transformation of abietane-type precursors under suboxic to oxic conditions is proposed. Variations in compositions of macerals and biomarkers are in concordance with pronounced
seasonality during Pontian, which caused changes in the water level, redox conditions during peatication, and
to some extent vegetation differences in the paleo-plant communities.
2012 Elsevier B.V. All rights reserved.
1. Introduction
The Upper Miocene Kolubara lignite basin is economically one of
the most important coal basins in Serbia. It is located about 60 km
SSW of Belgrade, and covers an area of almost 600 km 2, extending
in the EW direction up to 55 km, and in the SN direction up to
15 km. This basin is divided into several elds (A, B, C, D, E,
F, G, Veliki Crljeni, opi-Lazarevac, Tamnava Istok, Tamnava
Zapad, Radljevo, Zvizdar and Ruklade; Fig. 1). Lignite is exploited
in the elds C, D, and Tamnava Zapad. The D eld which is the
focus of this study is situated in eastern part of the Kolubara basin. At
the beginning of exploitation it extended over an area of almost 20 km2
and the remaining surface with mineable coal seams is about 6 km2.
The northern border is represented by outcroping and erosion of the
Main coal seam. The western border of the deposit is a natural extension
to the G eld and the southern to the E eld. The eastern border is also
marked by outcroping of the Main coal seam.
Corresponding author. Tel.: +381 11 3219 251; fax: +381 11 3235 537.
E-mail address: draganar@rgf.bg.ac.rs (D. ivoti).
0166-5162/$ see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.coal.2012.10.014
Since 1896, within the Kolubara basin about 883.2 Mt lignite, in

total, has been produced, of which 866.8 Mt in open pit mines and
16.3 Mt in underground mines being active until 1974 (http://
www.rbkolubara.co.rs). Annually, the Kolubara basin produces about
30 Mt lignite, which amounts to 70% of total coal production in Serbia.
According to the Geological Survey of the Kolubara basin, the lignite resources and reserves are currently estimated at 2811 Mt. Most of the lignite produced (90%) is used for electricity generation in thermal power
plants Nikola Tesla in Obrenovac and Kolubara in Veliki Crljeni, with
total capacity of 3160 MW (http://www.eps.rs). About 17 billion kWh is
annually produced from Kolubara coal, which represents 52% of Serbia's
total electricity generation.
Geological exploration began at the eastern part of the basin since the
late 19th century. Upper Miocene (Pontian) age of the coal-bearing sediments was conrmed in studies carried out by Stevanovi (1951) and
Panti and Duli (1993).
The distribution of palynomorph assemblages in the lignite from
the D eld (Panti and Duli, 1993) suggests that trees and bushes played
an important role in lignite formation. According to this study, the presence of TaxodiaceaeNyssaceae and Cupressaceae indicates a wet forest
D. ivoti et al. / International Journal of Coal Geology 111 (2013) 522
Fig. 1. Simplied geological map of the Kolubara basin.
mire during peat accumulation. Other palynomorph assemblages indicate a wetter part of a mire, a mixed mire with Myrica, Alnus, Salix,
Graminae sp., and rare water lilies. Dryer parts of the paleomire include
spores of Polypodiaceae, Sequoia, Betula, Carya, Fagus, Tilia, Ericaceae,
Lauraceae, Luquidambar and Cedrus. Coniferous pollen (Pinus, Abies,
Pineace, and Tsuga) indicates the presence of a hilly region in the vicinity of the paleomire (Panti and Duli, 1993).
Previous petrographical investigations (Ercegovac and Pulejkovi,
1991; Ercegovac et al., 2006) done on the samples from several boreholes from the Main coal seam, showed that the lignite from the
Kolubara basin is a typical humic coal with a high huminite content
(93.5 vol.%, on a mineral-matter-free basis, mmf) and relatively low
liptinite (3.3 vol.%, mmf) and inertinite contents (3.3 vol.%, mmf).
The most abundant macerals are textinite and ulminite with variable
amounts of densinite and attrinite. Petrographical study on core samples from seven boreholes (Ercegovac and Pulejkovi, 1991) showed a
variation in maceral composition through the seam prole. The most
abundant macerals are textinite (6.587.0 vol.%, mineral-matter included) and ulminite (3.550.3 vol.%) with variable amounts of attrinite
(4.535.5 vol.%), densinite (0.516.0 vol.%), gelinite (2.522.5 vol.%) and
corpohuminite (0.57.5 vol.%). Liptinite ranges from 1.0 to 19.0 vol.%,
and inertinite from 0.5 to 13.5 vol.%. Average huminite reectance of

the coal seams from the Kolubara basin is 0.30%, thus placing the coal at
lignite stage of coalication.
During liquefaction by direct catalytic hydrogenation, lignite from
Tamnava eld displayed a high degree of conversion (>84%; Aleksi et
al., 1997; Vitorovi et al., 1996) while on the contrary, lignite from the
D eld showed a lower degree of conversion (Vitorovi et al., 1994).
In the present study, the petrographical and geochemical characteristics of the thickest and most productive D eld lignites were investigated in detail, in order to evaluate the origin of the organic matter
and the characteristics of the depositional environment. In addition, a
novel diagenetic pathway for transformation of abietane-type precursors under suboxic to oxic conditions is proposed.
2. Geological setting
2.1. Lithological setting of the Kolubara Basin
The area of the Kolubara basin consists of Paleozoic, Mesozoic,
Tertiary, and Quaternary rocks (Ercegovac and Pulejkovi, 1991; Fig. 2).
Both, the border and the basement of this basin consist of Devonian
Fig. 2. General lithostratigraphic column of the Kolubara basin (after Vukovi and Bogdanovi, 2010).
Fig. 3. Cross sections of the Kolubara lignite basin.
and Carboniferous schist, gneiss, slate and sandstone, Mesozoic carbonate

and marly sediments, Tertiary daciteandesite rocks and pyroclastics, lacustrine, brackish and marine clastic sediments.
2.1.1. Paleozoic
Paleozoic rocks consist of DevonianCarboniferous phyllite with
redeposited blocks and fragments of limestone and Carboniferous terrigenous sediments (phyllite, rarely quartz sandstone with lenses of
limestone). In the contact zone with Brajkovac and Bukulja granite
Paleozoic rocks are partly metamorphosed, forming hornfels, amphibolite, mica schist and gneiss. The Paleozoic rocks occur along the southern
border of the Kolubara basin.
2.1.2. Mesozoic
Mesozoic sedimentation begun in Lower Triassic with clastic rocks
mica-rich sandstone and shales, while during Middle and Upper Triassic
bedded to thick-bedded dolomitic limestones and massive limestones
deposited. Triassic sediments mostly occur in the central and western
part of the southern rim of the basin.
The Upper Cretaceous rock succession is comprised of ysch
(alternation of limestone, marlstone, sandstone and siltstone). These
sediments outcrop along the southern border of the Kolubara lignite
basin (Fig. 1).
2.1.3. Cenozoic
Volcanic and pyroclastic rocks of Upper Oligocene and Lower to
Middle Miocene age formed in the SE rim of the Kolubara basin and
consist of phenoandesite, phenodacite, quartz-latite, ignimbrite and
quartz-latite tuff.
The Kolubara basin was formed in the Pannonian Basin System in
shallow lacustrine, delta plain and uvial environments. During the
late Miocene it became increasingly widespread as Lake Pannon
(e.g. Magyar et al., 1999) lled with coal-bearing sediments in the
central part of Serbia. Neogene of the Kolubara basin consists of the

following units (Kezovi, 2011):
1. Lower Miocene comprises fresh water marlstone, tufte, and
claystone;
2. Badenian (Middle Miocene) consisting of marine sand, loosely
bounded conglomerate, freshwater sand, clay and gravel;
3. BadenianSarmatian (Middle Miocene) consists of sand, clay and
gravel;
4. Sarmatian (Middle Miocene) comprises brackish clayeymarly and
sandy sediments and limestone;
5. Pannonian (Upper Miocene) contains caspi-brackish sand, sandy
clay, marly clay, silt, rarely gravel and marlstone;
6. Pontian (Upper Miocene) consists of fresh water clastic sediments,
with three coal seams: seam III or Lower coal seam (Fig. 3), seam II
or Main coal seam, and seam I or Upper coal seam, having average
thickness of 7 m, 25 m, and 11 m, respectively (Kezovi, 2011). The
total thickness of the Pontian series is between 250 and 320 m;
7. Quaternary formed of uvial gravel, sand, clay and sandyclayey
sediments.
In the Kolubara coal basin all the three coal seams are hosted
(Lower, Main and Upper; Fig. 3). They formed in the southern part
of the basin, while towards the north the Upper coal seam outcrops
and the Lower coal seam either outcrops or merges coal seam together
with the Main coal seam. The southern and northern parts of the
Kolubara coal basin are separated by the Medoevac fault zone (Fig. 4).
The Lower coal seam formed locally in the southern part of the
basin, mostly in F and opi-Lazarevac elds, although the extent of
this seam is not completely explored. The seam thickness is variable
up to 20 m.
The Main coal seam occurs across the entire Kolubara coal basin. In
the southern part of the basin it is more or less a uniform coal seam,
but towards the north it splits into several coal layers. Thickness varies
generally from a few to 50 m (including interbedded waste rock), but is
Fig. 4. Block-diagram of contemporary relief of the Kolubara basin with position of major fault zones, intra-basin and surrounding neotectonic units (after okovi et al., 1988, modied by Kezovi, 2010); 1. Petan fault; 2. Bari-ljivovica fault; 3. Radljevo fault; 4. Dren fault; 5. Obrenovac fault; 6. Dubrava fault; 7. elije fault; 8. Vrelo fault; and 9. Medoevac
fault.
10
locally up to 110 m (in the Zeoke area). Some parts of that coal seam are
eroded. The Main coal seam still hosts the majority of coal resources and
reserves within the Kolubara basin.
The Upper coal seam has been explored in the entire southern part of
the Kolubara basin, from the A eld in the SE, to the opi-Lazarevac eld
in the central southern part. It is a relatively homogenous coal seam, not
much disturbed by subsequent faulting, but occasionally eroded by
Kolubara and Petan rivers. The thickness is variable, up to 25 m. In the
B and C elds, as well as in a very small part of the D eld, one or two
diatomite layers formed between Main and Upper seams. The majority
of the reserves are already exploited.
The area of the D eld is comprised of Paleozoic schist, Tertiary
dacite and Pannonian sandyclayey sediments. The base of the Main
coal seam consists of clay, quartz sand and clayey sand. Usual thickness
of the Main coal seam varies from a few to 50 m (including interbedded
waste rock), locally up to 75 m. The overburden consists of Miocene
sandy clay, sand and Quaternary gravel and sand.
2.2. Paleoclimate and paleontological characteristics
Recent paleoclimate investigations based on analysis of 14 megaoras
comprise 14 to 42 different fossil taxa from 12 locations indicate relatively uniform, warm and humid climate at the territory of Serbia during
whole Miocene (Ivanov et al., 2011; Utescher et al., 2007). Major vegetation changes occurred in the Upper Miocene. This period is characterized
by relatively diverse climatic conditions, which were directed by global
climatic changes and probably complicated by regional paleogeographic
reorganizations and tectonic processes. The vegetation shows a decreasing trend in abundance of paleotropic and thermophilous elements,
reduction of macrothermic elements, and disappearance of evergreen
laurel forests. Together with these changes is a corresponding increase
in the role of arctotertiary species in plant communities, and they became
dominants in mesophytic forests. Slight cooling and some drying during
Upper Miocene, followed by uctuations of paleoclimate parameters
which display cycling changes of humid/dryer and warmer/cooler conditions were observed.
The coal-bearing strata cover almost complete by the Kolubara basin.
It is of Upper Pontian age (uppermost Miocene according to Paratethys
subdivision of the Miocene; Rgl, 1996), based on the following paleontological material (Panti and Duli, 1993):
Paleoora: Taxodium, Nyssa, Polypodiaceae, Larix, Pinus silvestris,
P. haploxylon, Picea, Abies, Fagus, Corylus, Salix, Sequoia, Myrica,
Magnoliae, Glyptostrobus;
Mollusca: Budmania sp., B. histiophora Brus., Limnocardium penslii
Fuchs., L. Zagrabiensis; Congeria rhomboidea Hoern.;
Ostracodae: Candona alta (Zal.), C. labiata Sok, C. hastata Krst., Cyproides
triangulata Krst.
2.3. Tectonic setting of the Kolubara basin
The most important fault is (okovi et al., 1988; Kezovi, 2010):
Radljevo fault (WSWNNE direction; Fig. 4), separating the central from
the southern parts of the basin.
Tectonic features of Neogene sediments are relatively uniform in
the major part of the basin; coal seams dip at low angles to the northern
and central parts of the basin. Only along the southern border of the SE
part of the basin, coal seams are characterized by a synform, due to intense post-sedimentary faulting, causing occasional coal erosion in the
SE part of the basin.
3. Samples and analytical methods
Fourteen lignite samples were collected from core Dg-29/03 from
the D eld, Kolubara basin (Fig. 1), representing different parts of the
Main coal seam. The sampling interval was determined on the basis of
lithological changes. The reconstructed column, with relative sampling

positions, is given in Fig. 5. The maceral and geochemical analyses were
performed on all fourteen lignite samples.
The macroscopic description of the coal lithotypes followed the nomenclature adopted by the ICCP (1993 in Taylor et al., 1998).
3.1. Petrographic analysis
For maceral analyses, the lignite samples were crushed to a maximum
particle size of 1 mm, mounted in epoxy resin and polished. The maceral
analyses were performed on a Leitz DMLP microscope in monochromatic
and UV light illumination on 500 points. The maceral description used in
this study follows the terminology developed by the International
Committee for Coal and Organic Petrology for huminite (Sykorova
et al., 2005), liptinite (Taylor et al., 1998) and inertinite (ICCP, 2001)
nomenclature.
The reectance measurements were performed under a monochromatic light of 546 nm using a Leitz DMRX microscope and an optical
standards having a reectance of 0.899% and 1.699% in oil, following
the procedures outlined by Taylor et al. (1998). The rank was determined by measuring the random reectance on ulminite B.
3.2. Organic geochemical analysis
Part of the samples was ground to b 150 m and analyzed on a Vario
EL III CHNS/O Elemental Analyzer, Elementar Analysensysteme GmbH.
Elemental analysis was carried out to determine the contents of sulfur
and organic carbon (Corg). Organic carbon content was determined
after removal of carbonates with diluted hydrochloric acid (1:3, v/v). Analytical moisture determination followed SRPS B.H8.390/1987 standard
(1987) and total moisture determination followed SRPS B.H8.338/1986
standard (1986). Ash yield determination followed ISO 1171 (1997).
Caloric value measurements were performed on IKA-Calorimeter adiabatic C400, followed standard procedure SRPS B.H8.318/1972 (1972).
The soluble organic matter (bitumen) was extracted from pulverized
lignite samples (b150 m) using a Dionex ASE apparatus with a mixture
of isohexane and acetone (1:1, v:v) at a temperature of 80 C and a pressure of 8 MPa. The asphaltenes were precipitated with petroleum-ether
and the remainder (maltenes) was separated into three fractions using
column chromatography over silica gel and aluminum oxide. The saturated hydrocarbon fraction was eluted with isohexane, the aromatic hydrocarbons with dichloromethane and the NSO fractions (polar fraction,
which contains nitrogen, sulfur, and oxygen compounds) with mixture
of dichloromethane and methanol (1:1, v:v).
Saturated and aromatic fractions isolated from the bitumen were analyzed by gas chromatographymass spectrometry (GCMS). A gas chromatograph Agilent 7890A GC (H5-MS capillary column, 30 m0.25 mm,
He carrier gas 1.5 cm3/min, FID) coupled to a Agilent 5975C mass selective detector (70 eV) was used. The column was heated from 80 to
310 C, at a rate of 2 C/min, and the nal temperature of 310 C was
maintained for additional 25 min. The individual peaks were identied
by comparison with literature data (Killops et al., 1995, 2003; Otto and
Simoneit, 2002; Peters et al., 2005; Philp, 1985; Stout, 1992; Tuo and Li,
2005; Wakeham et al., 1980) and on the basis of the total mass spectra
(library: NIST5a). Biomarker parameters were calculated from GCMS
chromatogram peak areas (software GCMS Data Analysis).
4. Results and discussion
4.1. Lithotypes and ash yield
The macroscopic examination of the core (Fig. 5) shows that the
oor of the Main coal seam consists of sand and clay, and the roof of
sand. Xylite-rich coal predominated in the central, upper and lower
part of the Main seam. Stratied matrix coal (Taylor et al., 1998) predominates in the bottom part of the Main seam. Small fragments of

Fig. 5. Macropetrographic prole of the D eld lignite and vertical distribution of the maceral groups, gelication index, tissue preservation index, ash content, total sulfur content, organic carbon content, the relative ratio of diterpenoids to
sum of di- and triterpenoids in saturated fraction, the relative ratio of diterpenoids to sum of di- and triterpenoids in aromatic fraction, relative content of alka-2-ones in aromatic fraction, relative ratio of 1-Ar ring/(1 + 2 + 3-Ar rings)
diterpenoids and 1-Ar ring/(1 + 3 + 4-Ar rings) triterpenoids, relative ratio of n-alkanes and hopanoids.
11
12
charcoal were found in the central and lower part of the seam.
Mineral-rich coal is present in thin layers near the roof, upper and
lower parts of seam.
The ash yield (on dry basis) of the coal samples from the D eld
(Kolubara basin) ranges between 6.67 wt.% in the xylite-rich coal to
40.45 wt.% in the mineral-rich coal from the upper part of the Main
seam (Table 1). Generally, the mineral-rich and matrix coal displays
higher ash yield than the xylite-rich coal. The very high ash yield
and its frequent vertical variation in the Main coal seam (Fig. 5) are
indicative of periodic ooding of the paleomire during deposition.
4.2. Maceral analysis
The results of the huminite reectance measurements show that
the coal from the Main coal seam of the D eld can be classied as lignite, with a mean random huminite reectance of 0.30 0.03 (ISO
11760, 2005; Table 2).
Results of maceral analysis are reported with mineral-matter included. Huminite is the prevailing maceral group in the Main seam
(51.983.7 vol.%; Table 2). The most abundant macerals are textinite
(5.757.0 vol.%; Fig. 6d) and ulminite (8.245.8 vol.%; Fig. 6d) with
variable amounts of densinite (6.133.7 vol.%; Fig. 6a) and attrinite
(1.524.4 vol.%). Telohuminite is strongly impregnated by resinous-like
substances, while detrohuminite occurs as groundmass surrounding liptinite or inertinite macerals. In some cases, detrohuminite
is interbedded with clay minerals. Contents of gelinite and corpohuminite
(Fig. 6b) are low (b5 vol.%). Gelinite appears in many cases interbedded
with ulminite or densinite, sometimes as thick layers. Corpohuminite is
disseminated throughout ulminite and textinite, sometimes in densinite,
mainly as phlobaphinite of globular or tabular shape.
Liptinite ranges from 3.8 to 17.2 vol.% with liptodetrinite
(1.57.2 vol.%) and sporinite (0.94.7 vol.%) being the most abundant
macerals. Suberinite (Fig. 6b), cutinite and resinite are present in variable amounts in all samples. Most of the sporinite have thin walls
(tenuisporinite), while sporinite with thick wall (crassisporinite) occurs
in traces. Resinite mostly occurs as cell lling or isolated small globular
bodies. They are associated with telohuminite as single bodies, commonly as impregnation in telohuminite and less with detrohuminite.
Liptodetrinite is usually associated with detrohuminite. Suberinite
usually appears as cell wall tissue associated with phlobaphinite.
Cutinite usually occurs as the thin walled (tenuicutinite) variety. The
thick walled (crassicutinite) variety was rarely observed. Alginite and
uorinite were observed in few samples (Table 2).
The percentages of inertinite, mainly inertodetrinite (Fig. 6a),
fusinite (Fig. 6c), funginite, semifusinite and macrinite range from
1.5 to 15.5 vol.% in the Main coal seam. Funginite is especially abundant in sample Dg-29/03_7 (3.7 vol.%). Inertodetrinite is disseminated throughout the coal samples. Funginite, including single and
multi-celled fungal spores and sclerotia, occurs as single bodies or
as colonies. The pores are usually lled with mineral matter, rarely
with resinite. Fusinite mostly occurs in thick bands. The pores are
usually empty but sometimes they are lled with mineral matter.
Macrinite appears in all samples.
The content of mineral matter varies between 4.4 and 34.1 vol.%,
which is consistent with the ash yield (Fig. 5; Table 2). Clays are
the most abundant minerals, while carbonates, pyrite and the
mineral-bituminous groundmass, impregnation of microscopic to
submicroscopic grains of minerals (clays/carbonates/quartz) with
dispersed bituminite (Teichmller, 1989) are less abundant. The increase
in mineral content is often related to more intense degradation of organic matter and/or contribution of clastic material. As expected, signicant
positive linear correlation (correlation coefcient, r=0.91; Fig. 7a)
between mineral matter content (Table 2) and ash yield (Table 1) is
observed.
The Tissue Preservation Index (TPI; Diessel, 1986 modied by
Ercegovac and Pulejkovi, 1991), taken as the ratio between structured and unstructured macerals of the huminite and inertinite
group, ranges from 0.80 to 6.30 (Table 2). As expected, coals with
well-preserved plant tissues (textinite and ulminite) display high TPI
values. Variations of TPI with depth (Fig. 5) could reect, to some extent,
differences in the type of peat-forming plant communities. The domination of structured macerals in almost all samples (TPI>1; Table 2) could
imply signicant contribution of gymnosperm species, which are more
resistant to degradation in comparison to angiosperms. On the other
hand, it was suggested that tissue preservation depends mostly on the
water level, the acidity/alkalinity and the climatic conditions during
peat accumulation, rather than on the botanical properties of the vegetation (Dehmer, 1995). According to this study, lowering the water
level, i.e. causing more oxic conditions, results in more extensive tissue
degradation.
The Gelication Index (GI; Diessel, 1986 modied by Ercegovac
and Pulejkovi, 1991), expressed as the ratio of gelied (ulminite,
densinite, gelinite and corpohuminite) to non-gelied (textinite and
attrinite) macerals, may indicate the relative humidity in the mire.
It is controlled by wet/dry conditions because gelication requires
the continuous presence of water (Dehmer, 1989; Diessel, 1986;
Kolcon and Sachsenhofer, 1999). Lignite from the D eld displays GI
values ranging between 0.3 and 4.7 (Table 2).
Slight cooling and some drying during Upper Miocene, followed by
uctuations of paleoclimate parameters which display cycling change
Table 1
Total moisture, caloric value, ash yield, sulfur and organic carbon contents, and values of group organic geochemical parameters of the D eld lignite (Kolubara basin).
Sample
Depth (m)
War
tot
(wt.%)
Wan
(wt.%)
Qmaf
g
(MJ/kg)
Qmaf
n
(MJ/kg)
Adb
(wt.%)
Sdb
tot
(wt.%)
Cdb
org
(wt.%)
Extract yield
(mg/g Corg)
Asphaltenes
(wt.%)
Alkanes
(wt.%)
Aromatics
(wt.%)
NSO compounds
(wt.%)
Dg-29/03_1
Dg-29/03_2
Dg-29/03_3
Dg-29/03_4
Dg-29/03_5
Dg-29/03_6
Dg-29/03_7
Dg-29/03_8
Dg-29/03_9
Dg-29/03_10
Dg-29/03_11
Dg-29/03_12
Dg-29/03_13
Dg-29/03_14
Minimum
Maximum
115.60115.90
116.52116.90
119.50120.75
121.00121.90
123.16123.70
123.70127.00
130.30133.10
133.10133.70
133.70136.00
138.20140.40
143.80146.40
146.40147.00
148.90149.90
153.20154.40
40.38
43.44
49.47
53.22
51.25
48.36
52.52
52.05
53.23
51.56
48.86
51.42
46.01
42.65
40.38
53.23
6.92
7.67
8.52
7.99
8.08
8.33
9.27
8.62
8.29
8.29
8.18
9.01
7.20
6.79
6.79
9.27
12.84
13.30
11.65
10.42
12.57
11.65
11.73
11.79
11.09
11.88
12.52
12.09
13.16
14.08
10.42
14.08
11.34
11.71
10.03
8.86
10.90
10.08
10.15
10.15
9.43
10.26
10.94
10.50
11.60
12.58
8.86
12.58
40.45
33.81
18.50
6.69
13.21
21.60
9.09
10.66
6.67
12.21
20.21
12.67
27.65
35.52
6.67
40.45
0.91
1.18
0.26
0.28
0.86
0.47
0.00
0.43
0.36
0.73
1.01
1.58
0.60
0.66
0.00
1.58
36.5
39.8
48.9
55.7
55.1
47.2
56.4
56.0
60.0
55.6
48.7
54.7
44.6
40.2
36.5
60.0
35.62
72.62
54.35
39.35
129.10
58.57
54.90
55.92
62.93
59.95
40.16
40.18
44.09
45.46
35.62
129.10
49.90
51.35
52.15
52.62
62.10
47.33
53.64
54.05
58.41
54.17
54.15
61.40
53.25
55.55
47.33
62.10
4.94
1.76
5.97
3.11
5.19
5.18
2.36
2.48
2.15
2.42
2.66
4.11
3.15
2.46
1.76
5.97
6.12
4.30
5.23
3.98
3.40
4.66
4.52
4.42
3.75
4.82
4.57
3.67
5.11
4.75
3.40
6.12
39.05
42.59
36.65
40.29
29.32
42.83
39.48
39.05
35.68
38.58
38.63
30.82
38.49
37.25
29.32
42.83
an
War
Analytical moisture content; Qmaf
Gross caloric value, moist, ash-free basis; Qmaf
Net caloric value, moist, ash-free basis; Adb Ash yield,
g
g
tot Total moisture content; W
db
dry basis; Sdb
tot Total sulfur content, dry basis; and Corg organic carbon content, dry basis.
Table 2
Maceral composition (vol.%), huminite reectance and petrographic indices of the D eld lignite, Kolubara basin.
Sample
Dg-29/03
1
Dg-29/03
3
Dg-29/03
4
Dg-29/03
5
Dg-29/03
6
Dg-29/03
7
Dg-29/03
8
Dg-29/03
9
Dg-29/03
10
Dg-29/03
11
Dg-29/03
12
Dg-29/03
13
Dg-29/03
14
Min
Max
AM
12.7
13.8
26.5
14.7
9.7
24.4
0.7
0.3
1.0
51.9
3.3
1.9
0.4
2.2
2.1
0.1
7.2
17.2
0.7
0.1
0.9
0.6
2.3
4.6
21.1
2.1
0.1
2.2
37.0
12.7
49.7
11.0
13.5
24.5
0.9
1.6
2.5
76.7
4.1
0.4
0.2
0.5
57.0
12.6
69.6
4.9
6.1
11.0
0.4
2.7
3.1
83.7
1.1
0.2
0.4
0.6
19.0
12.0
31.0
24.4
15.5
39.9
1.1
2.3
3.4
74.3
2.8
0.5
1.4
1.4
0.4
34.2
20.8
55.0
4.2
15.5
19.7
0.3
2.2
2.5
77.2
1.5
0.3
0.7
0.3
20.7
35.2
55.9
5.8
11.2
17.0
0.9
2.2
3.1
76.0
2.6
0.6
0.2
1.1
26.2
36.1
62.3
6.5
11.5
18.0
1.3
1.7
3.0
83.3
1.3
0.4
0.7
2.0
14.3
32.4
46.7
8.1
24.0
32.1
1.0
1.7
2.7
81.5
4.7
0.4
0.2
1.1
0.2
17.7
45.8
63.5
5.2
8.8
14.0
2.0
3.5
5.5
83.0
2.5
0.4
0.7
0.7
10.7
38.1
48.8
1.5
14.8
16.3
3.7
4.4
8.1
73.2
0.9
0.4
0.2
0.4
13.9
18.8
32.7
8.5
30.4
38.9
1.9
3.8
5.7
77.3
1.6
0.2
0.3
0.2
5.7
42.6
48.3
1.8
19.1
20.9
1.0
2.5
3.5
72.7
1.5
0.2
0.5
0.5
3.1
8.3
0.7
0.2
0.4
0.9
1.5
3.7
5.0
0.7
0.9
3.6
1.5
3.8
2.3
0.6
0.6
0.6
4.0
8.1
2.1
0.4
0.2
1.3
3.9
10.4
0.5
0.4
0.4
0.4
1.8
3.5
3.7
2.6
0.5
4.6
2.0
4.8
0.2
0.2
0.5
0.6
1.5
13.2
0.3
0.8
1.0
2.8
7.3
1.2
0.6
0.9
3.7
3.7
10.1
3.4
0.7
0.4
1.7
2.8
7.2
0.2
0.4
0.5
0.7
0.6
2.4
4.3
1.2
0.7
0.2
2.7
9.3
0.2
0.2
0.6
0.8
2.6
4.4
3.4
0.6
0.2
0.4
2.8
7.1
0.6
0.2
0.4
0.6
1.6
3.4
4.7
0.7
0.4
0.5
8.7
22.2
30.9
5.6
33.7
39.3
1.2
3.3
4.5
74.7
1.7
0.3
0.2
0.3
0.2
0.2
3.4
6.3
0.7
1.4
1.9
0.3
2.2
6.5
7.9
1.2
1.0
2.2
2.4
4.3
3.3
3.0
1.5
1.3
6.4
15.5
2.7
3.0
0.5
0.4
1.9
4.2
0.2
0.5
1.2
0.7
2.8
5.4
7.8
1.0
0.9
1.5
4.2
0.7
1.2
1.4
1.0
2.0
6.3
9.2
2.0
0.5
5.7
8.2
23.5
1.5
6.1
11.0
0.1
0.3
1.0
51.9
0.9
0.2
0.2
0.2
0.2
0.1
1.5
3.8
0.2
0.1
0.1
0.3
0.6
1.5
2.1
0.3
0.1
0.2
57.0
45.8
69.6
24.4
33.7
39.9
3.7
4.4
8.1
83.7
4.7
1.9
1.4
2.2
2.1
0.2
7.2
17.2
3.3
3.0
1.9
3.7
6.4
15.5
30.5
3.0
1.0
4.6
13.8
12.8
14.8
6.6
8.2
9.8
0.9
1.1
1.9
74.3
1.1
0.4
0.3
0.6
0.6
0.1
1.4
3.5
0.9
0.8
0.5
0.8
1.5
3.7
8.1
0.9
0.3
1.4
0.8
26.3
0.29
0.02
1.1
0.8
1.1
11.3
0.30
0.02
2.0
0.6
0.4
4.4
0.30
0.03
6.3
0.3
0.4
11.8
0.31
0.03
0.8
0.7
1.2
16.5
0.30
0.02
2.8
1.0
0.4
6.6
0.30
0.02
3.2
1.4
0.7
7.1
0.31
0.02
3.3
1.4
0.2
4.8
0.30
0.03
1.4
2.2
0.2
6.5
0.30
0.02
4.1
2.3
0.2
12.5
0.30
0.02
0.9
2.9
0.4
7.0
0.31
0.03
2.8
2.2
3.4
13.1
0.30
0.02
0.9
2.0
5.1
16.8
0.31
0.03
2.3
4.7
0.2
4.4
0.29
0.02
0.8
0.3
5.1
34.1
0.31
0.03
6.3
4.7
1.4
8.5
0.30
0.03
1.6
1.2
Maceral composition (vol.%)

Textinite
15.3
Ulminite
8.2
(Total Telohuminite)
23.5
Attrinite
19.0
Densinite
10.6
(Total Detrohuminite)
29.6
Gelinite
0.1
Corpohuminite
1.4
(Total Gelohuminite)
1.5
Total Huminite
54.6
Sporinite
1.9
Cutinite
0.3
Resinite
0.6
Suberinite
0.9
Alginite
0.9
Fluorinite
Liptodetrinite
4.1
Total Liptinite
8.7
Fusinite
0.3
Semifusinite
Macrinite
0.1
Funginite
0.8
Inertodetrinite
1.4
Total Inertinite
2.6
Clay
30.5
Pyrite
1.8
Carbonates
0.5
Mineral-bituminous
groundmass
Other minerals
1.3
Total Mineral
34.1
Average huminite
0.29
reectance (%)
0.02
a
TPI
0.8
b
GI
0.6
Dg-29/03
2
Min minimum value; Max maximum value; and AM arithmetic mean value.
a
TPI = (textinite + ulminite + corpohuminite + fusinite + semifusinite) / (gelinite + macrinite + detrohuminite), by Diessel (1986) and modied by Ercegovac and Pulejkovi (1991).
b
GI = (ulminite + densinite + gelinite + corpohuminite) /(textinite + attrinite + inertinite), by Diessel (1986) and modied by Ercegovac and Pulejkovi (1991).
13
14
Fig. 6. Photomicrographs of typical macerals from the D eld lignite; a) Densinite (D), Inertodetrinite (Id); b) Corpohuminite (Ch), Su (Suberinite); c) Fusinite (F); and d) Textinite
(T) and Ulminite (U).
of humid/dryer and warmer/cooler conditions (Ivanov et al., 2011;

Utescher et al., 2007) caused at least to some extent vegetation differences in the paleo-plant communities. Pronounced seasonality also
caused the changes in the water table, which resulted in changes of
redox potential (Eh) during peatication. Based on generally higher GI
values in the lower part of the seam (depth interval 133153 m; Fig. 5;
Fig. 7. Correlations mineral matter content vs. ash yield (a) and mineral matter content
vs. organic carbon content (b).
Table 2), it could be assumed that during peatication water column

level was higher in the lower part of the seam. Moreover, higher GI
values in the lower part of the Main seam could imply pronounced microbial activity.
4.3. Group organic geochemical parameters
Total moisture content is typical for lignite and ranges from
40.38 wt.% to 53.23 wt.% (Table 1). The gross and net caloric value
(moist, ash-free basis) of the lignite samples ranges from 10.42 to
14.08 MJ/kg and from 8.86 to 12.58 MJ/kg, respectively (Table 1),
which is expected for a coal of this rank. The highest caloric value
is observed in the xylite-rich coal from the central part of the Main
seam.
db
Organic carbon contents (Corg
) vary between 36.5% and 60.0%
(Table 1). As expected signicant negative linear correlation between
db
Corg
and mineral matter content (r = 0.91) is observed (Fig. 7b).
db
This indicates that the differences in Corg
contents of the lignite samples are mainly controlled by varying amounts of mineral matter.
The total sulfur content in the D eld coal is low and ranges from
0.00 wt.% to 1.58 wt.% (Table 1). It is well known that the sulfur content is inuenced by the pH of the peat and by the sulfate content of
the peat waters (Bechtel et al., 2004; Casagrande, 1987). The vertical
variation of the sulfur content in the Main coal seam (Fig. 5) suggests a
variation of pH values in peat during the deposition of organic matter.
The yield of the soluble organic matter (bitumen) is high and ranges
from 35.62 to 129.10 mg/g Corg (Table 1). It has been attributed to the
high proportion of biogenic and diagenetic compounds. Several other
studies have also reported high bitumen yields for immature coals from
all around the world (Avramidis and Zelilidis, 2007; Bechtel et al., 2005;
Vu et al., 2009). In the studied samples, the contents of saturated
hydrocarbons (1.765.97 wt.%) and aromatics (3.406.12 wt.%) are low,

while the contents of asphaltenes (47.3362.10 wt.%) and NSO compounds (29.3242.83 wt.%) are high, as expected for immature terrestrial
organic material (Table 1).
4.4. Molecular composition of the organic matter
4.4.1. General characteristics
The main constituents of the saturated fraction in the lignite samples are diterpenoids, hopanoids and n-alkanes. Non-aromatic, nonhopanoid triterpenoids and steroids were identied in low amounts
(Fig. 8).
The main components in the aromatic fractions of D eld lignite
are diterpenoids and non-hopanoid triterpenoids. Other constituents
of the aromatic fraction are long-chain acyclic alkan-2-ones,
sesquiterpenoids, aromatized hopanoids and monoaromatic steroids
(Fig. 9). Perylene and -tocopherol were observed in most samples.
Domination of diterpenoids and hopanoids in the saturated fraction indicates that the main sources of organic matter (OM) were
gymnosperms (conifers) and microbial biomass, whereas relatively
high content of non-hopanoid triterpenoids in aromatic fraction implies the contribution of angiosperms to the lignite organic matter
(Figs. 8 and 9).
4.4.2. n-Alkanes and isoprenoids
n-Alkanes are abundant in the total ion current (TIC) of saturated
fraction (Fig. 8). On the basis of mass fragmentogram, m/z 71
(Fig. 10a), n-alkanes are identied in the range of C21 to C33. The
n-alkane patterns of the lignite samples are dominated by longchain homologues (C27C31) with a maximum at n-C29 and a marked
odd over even predominance, indicating a signicant contribution of
epicuticular waxes. The values of the CPI (carbon preference index)
and OEP (odd-to-even-predominance) 2 range between 3.339.68
and 2.936.45, respectively (Table 3) are in accordance with the low
rank of the lignite.
Mid-chain n-alkanes (n-C21C25), originated from vascular plants,
microalgae, cyanobacteria, Sphagnum spp. and aquatic macrophytes
(Ficken et al., 2000; Matsumoto et al., 1990; Nott et al., 2000), are
present in notably lower amount in comparison to long-chain homologues (Fig. 10a). The predominance of odd over even carbonnumbered n-alkanes in the mid-range n-alkanes (OEP 1; Table 3)
15
suggests a microbial origin, consistent with high content of hopanoid

biomarkers (Fig. 8). Moreover, relatively high abundance of C23 and
C25 n-alkane homologues implies input of aquatic macrophytes to
the organic matter, consistent with previous palynological investigation (Panti and Duli, 1993).
Short chain n-alkanes (bn-C20) are found mostly in algae and microorganisms. Short chain n-alkanes are identied in very low quantities only in the samples containing alginite according to the results
of the maceral analyses (Table 2).
Isoprenoids pristane (Pr) and phytane (Ph) are identied as traces
in three samples only. Therefore, Pr/Ph ratio could not be calculated.
Mature organic matter contains signicant amount of isoprenoids,
while immature organic matter is usually characterized by very low
concentrations of pristane and phytane (Dzou et al., 1995; Hughes
et al., 1995; Vu et al., 2009). This is probably related to the fact that
isoprenoid precursors were incorporated into the macromolecular
matrix either by esterication (Brooks et al., 1978) or by natural
sulfurization (Brassell et al., 1986) during the early diagenesis. The release of saturated isoprenoids from kerogen macromolecular matrix
occurs only after the organic matter increases due the thermal maturation (Vu et al., 2009). As shown previously, the total sulfur contents
in the lignite samples are generally low (b1.58%; Table 1), implying
that even if the depositional conditions for the investigated coals
were sufciently reducing for sulfate reduction to occur, natural
sulfurization of phytol and its derivatives would be somewhat limited
for the samples investigated here. Therefore, it is assumed that phytol
and its derivatives (e.g., phytenic acid, formed from phytol under oxic
depositional conditions) were incorporated into the kerogen (organic
matter insoluble in conventional organic and inorganic solvents)
structure during the earliest stages of diagenesis by esterication
(Brooks et al., 1978). The second pathway implies pristane formation
from the isoprenoidal side chain of tocopherol, which is often found
in relatively high concentrations in higher plants (Goossens et al.,
1984; ten Haven et al., 1987) and phytane formation from bacterial
lipids (Volkman and Maxwell, 1986). The presence of -tocopherol in
lignite extracts (Fig. 9) and absence or traces amounts of isoprenoids
are consistent with low degree of maturity.
4.4.3. Steroids and hopanoids
The analysis of the aliphatic fraction reveals extremely low contents of steroids (Fig. 8). Steroid biomarkers consist predominantly
Fig. 8. TIC (total ion current) of saturated fraction typical for investigated samples. Peak assignments: n-Alkanes are labeled according to their carbon number; D1 Isopimaradiene;
D2 4(H)-19-Norisopimarane; D3 Pimaradiene; D4 4(H)-18-Norisopimarane; D5 C20 Diterpane; D6 Norpimarane; D7 Isopimarane; D8 Fichtelite (norabietane);
D9 Pimarane; D10 16(H)-Phyllocladane; D11 16(H)-Phyllocladane; D12 16(H)-Kaurane; D13 Abieta-8,11,13-trien-7-one; T1 Des-A-olean-13(18)-ene;
T2 Des-A-olean-12-ene; T3 Des-A-lupane; , and designate congurations at C17 and C21 in hopanes, (R) designates conguration at C22 in hopanes.
16
Fig. 9. TIC (total ion current) of aromatic fraction typical for investigated samples. Peak assignments: 1 Dihydro-ar-curcumene; 2 Cuparene; 3 1,2,3,4-Tetrahydronaphthalene;
4 Calamenene; 5 Cadina-1(10),6,8 triene; 6 5,6,7,8 Tetrahydrocadalene; 7 Cadalene; 8 Isocadalene, 9 Norabietadiene; 10 6,10,14-Trimethylpentadecan-2-one; 11 19Norabieta-8,11,13-triene; 12 Norabietatetraene; 13 Hibane; 14 18-Norabieta-6,8,11,13-tetraene; 15 18-Norabieta-8,11,13-triene; 16 Dehydroabietane; 17 1,2,3,4Tetrahydroretene; 18 2-Methyl-1-(4-methylpentyl)-6-i-propyl-naphthalene; 19 Simonellite; 20 Totarane; 21 Sempervirane; 22 Retene; 23 Diaromatic diterpenoid;
24 Retene isomer; 25 6,7-Dehydroferruginol; 26 Ferruginol; 27 2-Methylretene; 28 3,4,7,12a-Tetramethyl-1,2,3,4,4a,11,12,12a-octahydrochrysene; 29 3,3,7Trimethyl-1,2,3,4-tetrahydrochrysene; 30 Perylene; 31 C27 Alkan-2-one; 32 24,25-Dinoroleana-1,3,5(10),12,14-pentaene; 33 24,25-Dinoroleana-1,3,5(10),12-tetraene; 34 D-ring
monoaromatic hopane; 35 -Tocopherol; 36 24,25-Dinorursa-1,3,5(10),12-tetraene; 37 24,25-Dinorlupa-1,3,5(10)-triene; 38 Norlanosta(eupha)hexaene; 39 C29 Alkan-2-one;
40 Isomer of 2,2,4a,9-Tetramethyl-1,2,3,4,4a,5,6,14b-octahydropicene; 41 1,2,4a,9-Tetramethyl-1,2,3,4,4a, 5,6,14b-octahydropicene; 42 2,2,4a,9-Tetramethyl-1,2,3,4,4a,5,6,14boctahydropicene; 43 Mixture of oleana-dien-3-one and unknown compound; 44 4-Methyl, 24-ethyl, 19-norcholesta-1,3,5(10)-triene; 45 7-Methyl, 3-ethyl, 1,2-cyclopentanochrysene;
46 C31 Alkan-2-one; 47 1,2,9-Trimethyl-1,2,3,4-tetrahydropicene; 48 2,2,9-Trimethyl-1,2,3,4-tetrahydropicene; 49 1,2,9-Trimethyl-1,2-dihydropicene; 50 C33 Alkan-2-one;
and 51 C35 Alkan-2-one.
Fig. 10. GCMS mass chromatograms of n-alkanes, m/z 71 (a), sterenes, m/z 215 (b), hopanoids, m/z 191 (c) and alkan-2-ones, m/z 58 (d) typical for investigated samples
6,10,14-TMPD-2-one6,10,14-Trimethylpentadecan-2-one; for other peak assignments, see Fig. 8 legend.

Table 3
Parameters calculated from distribution and abundance of n-alkanes.
Sample
CPItotala
CPI2531b
OEP 1c
OEP 2d
Dg-29/03_1
Dg-29/03_2
Dg-29/03_3
Dg-29/03_4
Dg-29/03_5
Dg-29/03_6
Dg-29/03_7
Dg-29/03_8
Dg-29/03_9
Dg-29/03_10
Dg-29/03_11
Dg-29/03_12
Dg-29/03_13
Dg-29/03_14
3.87
5.45
6.02
9.68
6.79
6.15
9.31
7.14
7.47
5.09
5.17
4.62
3.33
3.36
3.71
4.88
5.50
8.85
6.35
6.36
10.22
6.63
6.70
4.37
5.31
4.82
3.40
3.49
2.01
2.16
2.09
2.27
2.06
1.82
2.21
1.89
2.09
1.50
1.57
1.71
1.91
1.78
2.93
3.24
3.67
5.96
3.74
4.52
6.45
4.47
4.59
3.31
4.85
4.42
2.45
3.47
a
CPItotal carbon preference index determined for full distribution of n-alkanes C23C33,
CPItotal =1/2[odd(n-C23 n-C33)/even(n-C22 n-C32)+odd(n-C23 n-C33)/
even(n-C24 n-C34)] (Bray and Evans, 1961).
b
CPI2531 =1/2[(n-C25 +2n-C27 +2n-C29 +n-C31)/(n-C26 +n-C28 +n-C30)] (Marynowski
and Zato, 2010).
c
OEP 1=1/4[(n-C21 +6n-C23 +n-C25)/(n-C22 +n-C24)] (Scalan and Smith, 1970).
d
OEP 2=1/4[(n-C25 +6 n-C27 +n-C29)/(n-C26 +n-C28)] (Scalan and Smith, 1970).
of C29 4-, 2- and 5-sterenes. C28 4-, 2- and 5-sterenes are identied in trace amounts in few samples, whereas C27 homologues are
absent. The marked predominance of C29 sterenes (Fig. 10b; Table 4)
clearly indicates peat formation from terrigenous plants. Kolubara lignite has low steroids/hopanoids ratio (b0.23; Table 4), which implies
a bacteria-inuenced facies and suggests the role of microorganisms
in degradation of plant tissue.
Hopanoids are important constituents of the Kolubara lignite
samples, representing the most abundant compounds in TIC of the
saturated fraction in samples Dg-29/03_7, Dg-29/03_8, Dg-29/03_10,
Dg-29/06_11 and Dg-29/03_13 (Fig. 8).
The most probable biological precursors of hopanoid biomarkers are
bacteriohopanetetrol and 3-desoxyhopanes (Ourisson et al., 1979;
Table 4
Parameters calculated from distribution and abundance of steroid and hopanoid
biomarkers.
Sample
% C29a
Ster/
Hopb
C30Hop-17(21)-ene/ C30/
n-Alkanes/
C30-Hopane
C30(+)c Hopanoidsd
Dg-29/03_1
Dg-29/03_2
Dg-29/03_3
Dg-29/03_4
Dg-29/03_5
Dg-29/03_6
Dg-29/03_7
Dg-29/03_8
Dg-29/03_9
Dg-29/03_10
Dg-29/03_11
Dg-29/03_12
Dg-29/03_13
Dg-29/03_14
90.81
100.00
87.59
N.D.
100.00
100.00
N.D.e
N.D.
100.00
94.78
100.00
95.49
100.00
91.96
0.2254
0.0032
0.0052
0.0000
0.0067
0.0029
N.D.
N.D.
0.0008
0.0031
0.0028
0.0044
0.0002
0.0081
9.68
0.41
0.00
0.00
0.30
0.16
0.00
0.00
0.00
0.65
0.14
0.20
0.00
0.24
0.66
0.81
0.74
0.65
0.77
0.74
0.72
0.67
0.76
0.84
0.77
0.78
0.67
0.80
1.33
0.47
0.42
0.27
0.73
0.34
0.30
0.09
0.22
0.09
0.16
0.13
0.09
0.08
%C29 = 100 C29(2 + 4 + 5)-Sterenes / (C27C29)(2 + 4 + 5)-Sterenes.

Ster/Hop = [(C27C29)( 2 + 4 + 5)-Sterenes] / [(C29C32)17(H)21(H)- +
(C29C31)17(H)21(H)- + (C29C31)17(H)21(H)- + C2717(H)-+C2717(H)Hopanes+(C29C31)Hop-17(21)-enes + C27-Hop-17(21)-ene + C27-hop-13(18)-ene]
(Peters et al., 2005).
c
C30/C30(+) = C3017(H)21(H)-Hopane / (C3017(H)
21(H)-Hopane + C3017(H)21(H)-Hopane) (Mackenzie et al., 1981); Sterenes
were quantied from mass chromatogram m/z 215, hopenes and hopanes were quantied from mass chromatogram m/z 191.
d
n-Alkanes/Hopanoids sum of n-alkanes divided by the sum of hopanoids quantied in the TIC (Olivella et al., 2006).
e
N.D. not determined due to the absence of sterenes.
17
Rohmer et al., 1992), identied in prokaryotic organisms (i.e. bacteria)

and fungi. Chaffee et al. (1986) emphasized that for hopanes with
fewer than 30 carbon atoms additional sources, such as ferns, lichens
and mosses, are also possible.
The low n-alkanes/hopanoids ratio (Olivella et al., 2006), calculated as
the sum of n-alkanes divided by the sum of hopanoids quantied in the
TIC (Table 4), denotes a signicant contribution of bacterial input, particularly for samples from lower parts of the seam. Identication of funginite
in all samples (Table 2) and presence of ferns, conrmed by palynological
data (Panti and Duli, 1993), imply that hopanoid biomarkers in D eld
lignite could have also originated from fungi and ferns. However, on the
basis of mass chromatogram, m/z 243, fernenes were not identied in
the lignite extracts, with exception of one sample, which contained
trace amounts of these biomarkers. A negative correlation (r=0.73;
logarithmic curve; Fig. 11) was observed between the n-alkanes/
hopanoids ratio (Table 4) and the gelication index (Table 2). The results
suggest that gelication of plant tissue is related to increased microbial
activity.
Based on mass chromatogram, m/z 191 of the saturated fraction
(Fig. 10c) the hopane composition in all samples is characterized by
the presence of 17(H)21(H), 17(H)21(H) and 17(H)21(H)
compounds with 2731 carbon atoms, with exception of C28 homologues. Other hopanoid type constituents of saturated fraction
are C27hop-13(18)-ene, C27hop-17(21)-ene, C30hop-17(21)-ene and
C3217(H)21(H)22(R)-hopane. Several samples contain C31hop17(21)-ene, C27hopan-21-one and C30hop-17(21)-en-20-one. The
presence of these hopanoid ketones clearly reects the suboxic to
oxic, slightly acidic conditions prevailing during peatication (Burhan
et al., 2002; Duan and Ma, 2001).
C3117(H)21(H)22(R)-Hopane dominates by far the hopane distribution, being the most abundant compound in the saturated fraction
of the samples Dg-29/03_7Dg-29/03_11 and Dg-29/03_13 (Figs. 8 and
10c). Prominent C31(R) hopane is often reported in low rank coals
(Stefanova et al., 2005a; Vu et al., 2009). According to van Dorselaer et
al. (1975) high amount of C31(R) hopane implies complex reactions
in acidic environments under oxic conditions. Killops et al. (1998)
suggested that the decarboxylation of 31,32-bishomohopanoic acid,
which is generally abundant in peats and soils (Quirk et al., 1984;
Ries-Kautt and Albert, 1989), could result in the formation of C3117(H)
21(H)-hopane in immature coals. Thiel et al. (2003) reported the presence of 22R-bishomohopanoic acid in the geological 17(H)21(H)
conguration in living microbial mats in the Black Sea, supporting the assumption that the C31 -hopane can be derived directly from microorganisms by decarboxylation. A direct bacterial origin is also possible for
the C29- and C31 17(H)21(H)-hopanes (Vu et al., 2009).
The contents of hopanes are considered to reect the level of the
degradation of organic matter by aerobic bacteria, whereas for the
C30hop-17(21)-ene a microbial origin from anaerobic (iron-reducing)
bacteria is assumed, as suggested by Wolff et al. (1992). Extremely low
C30hop-17(21)-ene/C30 hopane ratio, with exception of sample Dg-29/
03_1 (Table 4), predominance of C31(R)-hopane and the presence
Fig. 11. Correlation between n-alkanes/hopanoids ratio and gelication index (GI).
18
of hopanoid ketones (Fig. 10c) conrm the peatication in a suboxic to

oxic environment for the lignite samples.
Domination of -isomers in range C27 to C30 over -hopanes
and the presence of unsaturated hopenes are consistent with an immature stage of the organic matter. The ratio of 17(H)21(H) to
(17(H)21(H) + 17(H)21(H)) C30-hopanes is within the limits
established for lignite (0.50.7; Mackenzie et al., 1981) or even higher
(Table 4).
The identication of D-ring monoaromatic hopane, 7-methyl,
3-ethyl, 1,2-cyclopentanochrysene and 4-methyl, 24-ethyl, 19norcholesta-1,3,5(10)-triene (Philp, 1985) in the aromatic fraction of
all samples (Fig. 9) suggest partial aromatization of hopanoids and
steroids during diagenesis, which are consistent with pronounced
microbial activity and peatication in a suboxic to oxic environment.
4.4.4. Alkan-2-ones
Acyclic alkan-2-ones are presented in all the samples, with exception
of sample Dg-29/03_14. n-Alkan-2-one homologues contain 31 and 33
C-atoms are prominent even in the TIC of aromatic fraction (Fig. 9).
Based on mass fragmentogram, m/z 58, n-alkan-2-ones are identied
in the range of C23 to C35 (Fig. 10d). Similar to the n-alkane distribution,
the n-alkan-2-one patterns of the lignite samples are dominated by odd
long-chain homologues, C29C33. Although the distributions of the
n-alkanes and the n-alkanones in the samples are generally similar, a
main difference could be seen. In almost all of the samples, n-alkanes
have maximum at C29, followed by C31, whereas the most abundant
n-alkan-2-one is C31 followed by C33 or C29 (Fig. 10a, d). The results indicate that n-alkan-2-ones probably have few sources: a) direct contribution of ketones from higher plant waxes, which consist of C23C33
homologues with a signicant odd C number predominance and
Cmax at C29 or C31; b) microbially mediated -oxidation of the corresponding n-alkanes in the sediments or prior to incorporation into
the sediments; c) oxidative decarboxylation of n-fatty acids and oxidized alcohols, as well as elongation of a suitable fatty acid precursor
and subsequent decarboxylation, yielding longer-chain alkanones with
pronounced odd C predominance and major constituents of C27, C29
and C31 (Tuo and Li, 2005 and references therein). Recent investigations
(Ortiz et al., 2011) also showed that microbial degradation can be a
major contributor to the n-alkan-2-one distribution in sediments, rather
than a direct input of ketones from plants.
In addition to n-alkan-2-ones, 6,10,14-trimethylpentadecan-2-one
(6,10,14-TMPD-2-one), an isoprenoidal ketone was also found in most
of the samples studied (Fig. 10d). 6,10,14-TMPD-2-one is quite common
in nature, occurring widely in sediments (de Leeuw et al., 1977; Ikan et
al., 1973) and in particulate organic matter collected from the water
column (Rontani et al., 1992). Since pristane and phytane were absent
in most of the samples, it could be argued that the main pathways of
6,10,14-TMPD-2-one formation imply bacterial degradation (Brooks
and Maxwell, 1974; Brooks et al., 1978) and photosensitized oxidation
(Rontani and Giral, 1990) of free phytol and/or photodegradation of
chlorophyll-a (Rontani et al., 1991).
Therefore, alkan-2-one distribution in lignite extracts from the Main
seam conrms that diagenetic changes of the organic matter were mainly
governed by bacterial activity in a suboxic to oxic environment, consistent
with conclusions derived from interpretation of hopanoid biomarkers
and pronounced aromatization of angiosperm derived triterpenoids
(see Section 4.4.5.).
4.4.5. Sesquiterpenoids, diterpenoids, and triterpenoids with non-hopanoid
skeleton
In all samples, aromatic sesquiterpenoids occur at low quantities
(Fig. 9). Cadalene predominates over isocadalene, calamenene and
5,6,7,8-tetrahydro-cadalene. Other sesquiterpenoid constituents of the
lignite extracts are cuparene, cadina-1(10),6,8-triene and 1,2,3,4tetrahydronaphthalene, whereas dihydro-ar-curcumene was identied
only in three samples. Sesquiterpenoids are used as markers for higher
land plants because they occur in their resinous material. However,

sesquiterpenoid biomarkers are often not useful for a precise determination of the precursor plant community (Otto and Simoneit, 2002;
Otto et al., 1997; van Aarssen et al., 1990), with exception of cuparene.
The presence of cuparene in lignite from the D eld (Fig. 9) clearly indicates contribution of conifers family Cupressaceae, and family genera
Cupressus, Thuja and Juniperus as precursors to OM (Haberer et al.,
2006; Otto and Wilde, 2001), which is consistent with palynological
data.
Diterpenoids are main constituents of both the saturated and aromatic fraction indicating signicant contribution of gymnosperms to
the precursor OM. 16(H)-Phyllocladane and pimarane are by far
dominant in the saturated fractions. Other diterpenoid type constituents
of saturated fraction are isopimarane, norpimarane, norisopimarane,
16(H)-kaurane, 16(H)-phyllocladane, norabietane, isopimaradiene,
pimaradiene and abieta-8,11,13-trien-7-one (Fig. 8). A high amount of
16(H)-phyllocladane indicates that the lignite forming plants in
part belonged to the conifer families Taxodiaceae, Podocarpaceae,
Cupressaceae, Araucariaceae, Sciadopityaceae and Phyllocladaceae,
while the high abundance of pimarane suggests Pinaceae, Taxodiaceae
and Cupressaceae (Otto and Wilde, 2001; Otto et al., 1997; Stefanova
et al., 2002, 2005b). The higher proportion of pimarane than 16(H)phyllocladane in several samples, particularly Dg-29/03_4 and Dg-29/
03_6 (Table 5) could imply higher impact of Pinaceae to the precursor
biomass, especially as their abundance was conrmed by previous palynological investigation (Panti and Duli, 1993).
The aromatic diterpenoids consist of norabieta-6,8,11,13tetraenes, norabieta-8,11,13-trienes, 2-methyl-1-(4-methylpentyl),
6-isopropylnaphthalene, dehydroabietane, simonellite, retene,
sempervirane, totarane, hibaene, ferruginol, 6,7-dehydroferruginol,
tetrahydroretene and 2-methylretene, with simonellite and
dehydroabietane predominating in all of the samples (Fig. 9).
Almost all of the aromatic diterpenoids are non-specic conifer
markers, because they are the diagenetic products of a great variety
of abietane-type precursors that are common constituents of all conifers except Phyllocladaceae (Otto and Simoneit, 2001; Otto et al.,
1997; Stefanova et al., 2005b). On the other hand, the presence of
ferruginol, totarane and hibaene in the aromatic fraction of the D eld lignite extracts (Fig. 9) clearly indicates the contribution of Cupressaceae,
Taxodiaceae, Podocarpaceae and Araucariaceae to precursor biomass
(Otto and Wilde, 2001). This is consistent with the observation derived
from analysis of saturated biomarkers.
Abietic acid and dehydroabietane are probably the biological precursors of the saturated and aromatic abietanes. These compounds,
however, are not the only source of abietane type diterpenoids in
the geosphere, as numerous other abietane products are present in
modern resins (Wakeham et al., 1980). For example, the origin of
dehydroabietane, simonellite and retene probably partly associates
with phenolic abietanes such as ferruginol, sugiol and hinokiol, widespread in modern species of the families Taxodiaceae, Cupressaceae and
Podocarpaceae (Otto and Wilde, 2001). Pimarane- and phyllocladanederivatives are also known as possible precursors for aromatic
abietane-type diterpenoids (Alexander et al., 1987; Wakeham et al.,
1980). Transformations of pimaranes and phyllocladanes, which lead
to the formation of dehydroabietane and other aromatic diterpenoids,
are favored under acidic conditions and catalyzed by clay minerals
and, therefore, could be expected to be generated during Kolubara
lignite formation.
Under alkaline anaerobic conditions reductive processes, i.e. decarboxylation and hydrogenation of resin acids are dominant. The decarboxylation of the abietic acid followed by reduction leads to the
saturated norabietane and abietane. Abietane has not been identied
in the lignite extracts, whereas norabietane is present in relatively low
quantity. Therefore, as mentioned previously (abundant telohuminite
macerals and C31(R)-hopane, and presence of hopanoid ketones
and alkan-2-ones), it is suggested that the dominant alteration pathway
was the oxidation of abietic acid to dehydroabietic acid. Its decarboxylation generates norabieta-8,11,13-triene, which is identied in all
samples. Further aromatization leads to 1,2,3,4-tetrahydroretene
and nally to retene, which is observed in all lignite extracts
(Figs. 9 and 12). The presence of abieta-8,11,13-trien-7-one (Fig. 8)
in all samples suggests another possible degradation pathway of
dehydroabietic acid under oxic conditions. It considers in the rst step,
as proposed by Otto and Simoneit (2002), oxidation of dehydroabietic
acid to 7-oxo-dehydroabietic acid, followed by decarboxylation generating abieta-8,11,13-trien-7-one or norabieta-8,11,13-trien-7-one. Further alteration of abieta-8,11,13-trien-7-one generates simonellite,
which is the most abundant aromatic diterpenoid in all samples
(Figs. 9 and 12). Possible products formed by degradation of norabieta8,11,13-trien-7-one are norabieta-8,11,13-triene, norabieta-6,8,11,13tetraene, tetrahydroretene and nally retene. Simonellite and
2-methyl, 1-(4-methylpentyl), 6-isopropylnaphthalene, could also
originate from direct natural product, dehydroabietane (Fig. 12).
These three compounds are observed in the aromatic fraction of all
samples in relatively high proportion (Fig. 9). Another possible pathway
for the formation of abieta-8,11,13-trien-7-one could be oxidation of
dehydroabietane (Fig. 12).
The nonhopanoid triterpenoids in saturated fraction consist of
olean-12-ene, des-A-olean-enes, des-A-urs-enes and des-A-lupane.
These compounds are presented in relatively low amounts (Fig. 8).
Marked domination of des-A-ring degraded compounds is observed,
and only in four samples non-degraded oleanenes are identied. Degradation of triterpenoids' A-ring implies intense microbial activity.
Although the nonhopanoid triterpenoids represent a minor component of saturated fraction, these compounds are abundant in aromatic
fraction of coal extracts (Fig. 9). This result shows that angiosperms also
contributed to the organic matter. Considerably higher abundance of
aromatized in comparison to non-aromatized angiosperm triterpenoids
indicates intense aromatization of triterpenoids during diagenesis. The
19
same observation was also reported by Kalkreuth et al. (1998) and

Nakamura et al. (2010), which showed that aliphatic angiospermderived triterpenoids are more easily altered to aromatic derivatives
than gymnosperm-derived diterpenoids, resulting in the selective
loss of analogous aliphatic compounds. Pronounced aromatization
of triterpenoids is consistent with intense microbial activity during
peatication in a suboxic to oxic environment. Moreover, aromatization
may also be mediated by clay-catalytic processes (Rubinstein et al.,
1975; Sieskind et al., 1979).
The following aromatic tetra- and pentacyclic triterpenoids
occur in the aromatic hydrocarbon fractions: ring-A-monoaromatic
triterpenoids (24,25-dinoroleana-1,3,5(10),12-tetraene, dinoroleana1,3,5(10),12,14-pentaene, 24,25-dinorursa-1,3,5(10),12-tetraene,
24,25-dinorlupa-1,3,5(10)-triene), pentamethyldecahydrochrysene,
tetramethyloctahydrochrysenes, trimethyltetrahydrochrysenes,
tetramethyloctahydropicenes, trimethyltetrahydropicenes,
dimethyltetrahydropicene and triaromatic des-A-lupane (Fig. 9). In all
samples pentacyclic triterpenoids are notably more abundant than
tetracyclic chrysene derivatives. This result shows that the main pathway of aromatization was progressive aromatization (Stout, 1992)
and explains the low abundance of pentacyclic triterpenoids in the saturated fraction. The most prominent peaks are ring-A-monoaromatic
triterpenoids, which conrms its relatively high stability observed also
in earlier investigations (Stefanova et al., 2005a; Stout, 1992).
Due to enhanced aromatization of angiosperm derived triterpenoids,
the ratio of diterpenoids to sum of di- and terprenoids in saturated fraction, Di/(Di+Tri)sat (Bechtel et al., 2002, 2003) shows extremely high
and uniform values (above 0.95) indicating that conifers nearly exclusively contributed to lignite formation (Fig. 5; Table 5). Therefore,
in order to estimate the contribution of gymnosperm and angiosperm
vegetation in the ancient peat bogs we have used the ratio of diterpenoid
and angiosperm-derived triterpenoid aromatic biomarkers (Di/(Di+Tri)
arom; Haberer et al., 2006; Nakamura et al., 2010; Fig. 5; Table 5).
Table 5
Parameters calculated from distribution and abundance of diterpenoids and triterpenoids, and relative content of alkan-2-ones in the aromatic fraction.
Sample
Pimarane/16(H)-Phyllocladane
Di/(Di + Tri) sata
Di/(Di + Tri) aromb
1-Ar ring/(1 + 2 + 3-Ar rings)

diterpenoidsc
1-Ar ring/(1 + 3 + 4-Ar rings)

triterpenoidsd
Alkan-2-ones
(%)e
Dg-29/03_1
Dg-29/03_2
Dg-29/03_3
Dg-29/03_4
Dg-29/03_5
Dg-29/03_6
Dg-29/03_7
Dg-29/03_8
Dg-29/03_9
Dg-29/03_10
Dg-29/03_11
Dg-29/03_12
Dg-29/03_13
Dg-29/03_14
1.51
0.13
0.14
4.44
0.03
2.67
0.44
1.05
0.78
1.05
0.08
0.03
1.23
0.14
0.9591
0.9743
0.9977
1.0000
1.0000
0.9997
1.0000
1.0000
0.9978
0.9760
0.9693
0.9970
1.0000
0.9749
0.34
0.45
0.47
0.41
0.83
0.68
N.D.
0.55
0.67
0.52
0.65
0.52
0.76
0.70
0.41
0.34
0.38
0.36
0.27
0.32
N.D.
0.43
0.31
0.31
0.46
0.38
0.66
0.26
0.90
0.59
0.33
0.41
0.45
0.41
N.D.
0.35
0.29
0.43
0.43
0.52
0.59
0.51
0.99
6.13
9.86
8.98
4.22
7.25
N.D.
1.45
4.41
4.95
4.26
6.14
0.41
0.00
a
Di/(Di + Tri)sat = Diterpenoids /(Diterpenoids +Triterpenoids), calculated from the TIC of saturated fraction (Bechtel et al., 2002, 2003), Diterpenoids = (16(H)Phyllocladane+Pimarane+Isopimarane+Norpimarane+Norisopimarane+16(H)-Kaurane+16(H)-Phyllocladane+Norabietane+Isopimaradiene+Pimaradiene), Triterpenoids=
(Olean-12-ene+Olean-13(18)-ene+Des-A-olean-12-ene+Des-A-olean-13(18)-ene+Des-A-olean-18-ene+Des-A-urs-13(18)-ene+Des-A-urs-12-ene+Des-A-lupane).
b
Di/(Di+Tri)arom=Aromatic diterpenoids/(Aromatic diterpenoids+Aromatic triterpenoids), calculated from the TIC of aromatic fraction (Haberer et al., 2006; Nakamura et al., 2010),
Aromatic diterpenoids=(18-Norabieta-6,8,11,13-tetraene+19-Norabieta-8,11,13-triene+18-Norabieta-8,11,13-triene+2-Methyl, 1-(4-methylpentyl), 6-isopropylnaphthalene+
Dehydroabietane+Simonellite+Retene+Sempervirane + Totarane + Hibaene + Ferruginol + 6,7-Dehydroferruginol + 2-Methylretene + 1,2,3,4-Tetrahydroretene), Aromatic
triterpenoids = (24,25-Dinoroleana-1,3,5(10),12-tetraene+24,25-Dinoroleana-1,3,5(10),12,14-pentaene+24,25-Dinorursa-1,3,5(10),12-tetraene+24,25-Dinorlupa-1,3,5(10)-triene+
Pentamethyldecahydrochrysene+3,4,7,12a-Tetramethyl-1,2,3,4,4a,11,12,12a-octahydrochrysene+3,3,7,12a-Tetramethyl-1,2,3,4,4a,11,12,12a-octahydrochrysene+3,4,7-Trimethyl-1,2,3,4tetrahydrochrysene+3,3,7-Trimethyl-1,2,3,4-tetrahydrochrysene+1,2,4a,9-Tetramethyl-1,2,3,4,4a,5,6,14b-octahydropicene+2,2,4a,9-Tetramethyl-1,2,3,4,4a,5,6,14b-octahydropicene +
1,2,9-Trimethyl-1,2,3,4-tetrahydropicene + 2,2,9-Trimethyl-1,2,3,4-tetrahydropicene + 1,2,9-Trimethyl-1,2-dihydropicene + Triaromatic des-A-lupane).
c
1-Ar ring diterpenoids=(18-Norabieta-6,8,11,13-tetraene+19-Norabieta-8,11,13-triene+18-Norabieta-8,11,13-triene+Dehydroabietane), calculated from the TIC of aromatic
fraction, 2-Ar ring diterpenoids=(2-Methyl, 1-(4-methylpentyl), 6-isopropylnaphthalene+Simonellite+Tetrahydroretene), calculated from the TIC of aromatic fraction, 3-Ar ring
diterpenoids=(Retene+2-Methylretene), calculated from the TIC of aromatic fraction (Haberer et al., 2006).
d
1-Ar ring triterpenoids = (24,25-Dinoroleana-1,3,5(10),12-tetraene+24,25-Dinoroleana-1,3,5(10),12,14-pentaene+24,25-Dinorursa-1,3,5(10),12-tetraene+24,25-Dinorlupa1,3,5(10)-triene), calculated from the TIC of aromatic fraction, 3-Ar ring triterpenoids=(1,2,4a,9-Tetramethyl-1,2,3,4,4a,5,6,14b-octahydropicene+2,2,4a,9-Tetramethyl-1,2,3,4,4a,5,6,14boctahydropicene), calculated from the TIC of aromatic fraction, 4-Ar ring triterpenoids=(1,2,9-Trimethyl-1,2,3,4-tetrahydropicene + 2,2,9-Trimethyl-1,2,3,4-tetrahydropicene +
1,2,9-Trimethyl-1,2-dihydropicene), calculated from the TIC of aromatic fraction.
e
Alkan-2-ones (%) relative content of alkan-2-ones in the aromatic fraction.
20
Fig. 12. Proposed schematic pathway for oxidative diagenetic transformation of abietic acid and dehydroabietane. (Few steps are adopted from Otto and Simoneit, 2001, 2002;
Stefanova et al., 2005b). Compounds with an asterisk (*) were detected in coals from the D eld, Kolubara basin; compounds in boxes represent natural product precursors.
The lower values of this ratio in upper part of the seam indicate increasing proportion of angiosperms within the peat-forming vegetation (Table 5). Variations in Di/(Di + Tri)arom with depth (Fig. 5;
Table 5) could be attributed to the pronounced seasonality, which
caused changes of water column level, redox potential (Eh) in the
paleoenvironment and differences in vegetation of the paleo-plant
communities, consistent with conclusions derived from GI ratio. Positive correlation of Di/(Di + Tri)arom ratio (Table 5) with GI (Table 1)
(r= 0.65 for linear and 0.73 for logarithmic curve; Fig. 13, sample
Dg-29/03_5 was excluded from the diagram) suggests that lowering
the water column level, i.e. more oxidative conditions were more suitable for angiosperms.
The 1-Ar ring/(1+2+3-Ar rings) diterpenoids ratio, which is used
for an assessment of the degree of aromatization (Haberer et al., 2006)
has a relatively uniform value in the lignite samples, with exception of
one sample. Here, no relationship between increasing diagenetic alteration and increasing depth is detectable (Fig. 5; Table 5); which is not
be unexpected for a sedimentary section of only 150 m. Corresponding
1-Ar ring/(1+3+4-Ar rings) triterpenoids ratio (according to pathway
of progressive aromatization), proposed in this study, show also relative
uniform values (Fig. 5; Table 5). Considering low degree of the OM
Fig. 13. Correlation between Di/(Di + Tri)arom ratio and gelication index (GI).
maturity changes of 1-Ar ring/(1+2+3-Ar rings) diterpenoids and

1-Ar ring/(1+3+4-Ar rings) triterpenoids ratios with depth probably
imply changes in Eh potential of the depositional environment and/or
bacterial activity, rather than changes due to thermal alteration. In
addition, the inuence of clay-catalytic processes on aromatization
cannot be ruled out. Negative correlation observed between 1-Ar
ring/(1+2+ 3-Ar rings) diterpenoids and 1-Ar ring/(1+ 3+4-Ar
rings) triterpenoids, and relative proportion of alkan-2-ones in aromatic
Fig. 14. Correlations between 1-Ar ring/(1 + 2 + 3-Ar rings) diterpenoids (a) and 1-Ar
ring/(1+3+4-Ar rings) triterpenoids (b) ratios with relative proportion of alkan-2-ones
in aromatic fraction (%).
fraction, suggests that aromatization processes are preferably attributed

to microbial activity under suboxic to oxic conditions (Fig. 14).
5. Conclusions
The petrographic analysis of lignite samples collected from the Main
seam, D eld of Kolubara basin shows that huminite is the prevailing
maceral group, with a relatively high content of liptinite and inertinite.
The most abundant macerals of the huminite group are: textinite,
ulminite, densinite and attrinite, and of the liptinite group: liptodetrinite
and sporinite. Inertodetrinite, fusinite, funginite and semifusinite are the
most common macerals of the inertinite group. Clay minerals predominate, while pyrite and carbonates are less abundant.
Main sources of organic matter were gymnosperms (conifers) and
microbial biomass followed by angiosperms. Based on composition of
saturated and aromatic diterpenoids it has been established that coal
forming plants belonged to the gymnosperm families Taxodiaceae,
Podocarpaceae, Cupressaceae, Araucariaceae, Phyllocladaceae and
Pinaceae.
The results of petrological and organic geochemical examinations
suggest that the lignite from the D eld of the Kolubara basin
formed in a slightly acid to neutral deposition environment. Abundant hopanoids, predominance of C31(R)-hopane with extremely
low C30hop-17(21)-ene/C30hopane ratio and the presence of hopanoid
ketones and alkan-2-ones in the lignite extracts indicate that diagenetic
changes of the organic matter were mainly governed by bacterial activity in a suboxic to oxic environment, which caused an intense progressive aromatization of angiosperm-derived triterpenoids and partial
aromatization of hopanoids and steroids during diagenesis. Based on
the distribution of aromatic diterpenoids a novel diagenetic pathway
for transformation of abietane-type precursors under suboxic to oxic
conditions is proposed.
The vertical variations of ash yield, sulfur content, maceral composition, TPI and GI ratios, as well as the ratio of diterpenoid and
angiosperm-derived triterpenoid aromatic biomarkers of lignite, point
to the changes in pH values and water level in the mire during the accumulation of organic matter. Pronounced seasonality caused the changes
in the water table, which resulted in changes of the redox potential (Eh)
during peatication as well as vegetation differentiations in the paleoplant communities.
Group organic geochemical parameters, distribution of n-alkanes,
domination of -isomers in the range of C27 to C30 over -hopanes
and the presence of unsaturated hopenes are consistent with an immature stage of the organic matter (phase of intense diagenetic processes).
Acknowledgments
This work was nanced by the Ministry of Education and Science
of the Republic of Serbia (Projects Nos. 176006 and 176016), which
is gratefully acknowledged. We are also grateful to Prof. Dr. Deolinda
Flores, Dr. Hamed Sanei, Prof. Dr. Wolfgang Kalkreuth and an anonymous
reviewer whose helpful suggestions and comments greatly beneted
this paper. Authors also gratefully acknowledge the Montanuniversitt
Leoben, Department Angewandte Geowissenschaften und Geophysik
(Austria) for the technical support.
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International Journal of Coal Geology 111 (2013) 522

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International Journal of Coal Geology

Petrological and geochemical composition of lignite from the D eld,

Since 1896, within the Kolubara basin about 883.2 Mt lignite, in

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Fig. 1. Simplied geological map of the Kolubara basin.

D. ivoti et al. / International Journal of Coal Geology 111 (2013) 522

and inertinite from 0.5 to 13.5 vol.%. Average huminite reectance of

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Fig. 3. Cross sections of the Kolubara lignite basin.

D. ivoti et al. / International Journal of Coal Geology 111 (2013) 522

and Carboniferous schist, gneiss, slate and sandstone, Mesozoic carbonate

central part of Serbia. Neogene of the Kolubara basin consists of the

D. ivoti et al. / International Journal of Coal Geology 111 (2013) 522

lithological changes. The reconstructed column, with relative sampling

D. ivoti et al. / International Journal of Coal Geology 111 (2013) 522

D. ivoti et al. / International Journal of Coal Geology 111 (2013) 522

D. ivoti et al. / International Journal of Coal Geology 111 (2013) 522

Maceral composition (vol.%)

D. ivoti et al. / International Journal of Coal Geology 111 (2013) 522

of humid/dryer and warmer/cooler conditions (Ivanov et al., 2011;

Table 2), it could be assumed that during peatication water column

D. ivoti et al. / International Journal of Coal Geology 111 (2013) 522

hydrocarbons (1.765.97 wt.%) and aromatics (3.406.12 wt.%) are low,

suggests a microbial origin, consistent with high content of hopanoid

D. ivoti et al. / International Journal of Coal Geology 111 (2013) 522

D. ivoti et al. / International Journal of Coal Geology 111 (2013) 522

%C29 = 100 C29(2 + 4 + 5)-Sterenes / (C27C29)(2 + 4 + 5)-Sterenes.

Rohmer et al., 1992), identied in prokaryotic organisms (i.e. bacteria)

D. ivoti et al. / International Journal of Coal Geology 111 (2013) 522

of hopanoid ketones (Fig. 10c) conrm the peatication in a suboxic to

land plants because they occur in their resinous material. However,

D. ivoti et al. / International Journal of Coal Geology 111 (2013) 522

same observation was also reported by Kalkreuth et al. (1998) and

Di/(Di + Tri) sata

Di/(Di + Tri) aromb

1-Ar ring/(1 + 2 + 3-Ar rings)

1-Ar ring/(1 + 3 + 4-Ar rings)

D. ivoti et al. / International Journal of Coal Geology 111 (2013) 522

maturity changes of 1-Ar ring/(1+2+3-Ar rings) diterpenoids and

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fraction, suggests that aromatization processes are preferably attributed

D. ivoti et al. / International Journal of Coal Geology 111 (2013) 522

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