Escolar Documentos
Profissional Documentos
Cultura Documentos
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
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.%,
Fig. 2. General lithostratigraphic column of the Kolubara basin (after Vukovi and Bogdanovi, 2010).
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
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
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).
Fig. 7. Correlations mineral matter content vs. ash yield (a) and mineral matter content
vs. organic carbon content (b).
15
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.
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
17
Fig. 11. Correlation between n-alkanes/hopanoids ratio and gelication index (GI).
18
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
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
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).
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 (%).
21
Bechtel, A., Gruber, W., Sachsenhofer, R.F., Gratzer, R., Lcke, A., Pttmann, W., 2003.
Depositional environment of the Late Miocene Hausruck lignite (Alpine Foreland
Basin): insights from petrography, organic geochemistry, and stable carbon isotopes. International Journal of Coal Geology 53, 153180.
Bechtel, A., Markic, M., Sachsenhofer, R.F., Jelen, B., Gratzer, R., Lcke, A., Pttmann, W.,
2004. Paleoenvironment of the upper Oligocene Trbovlje coal seam (Slovenia). International Journal of Coal Geology 57, 2348.
Bechtel, A., Sachsenhofer, R.F., Gratzer, R., Lcke, A., Pttmann, W., 2002. Parameters
determining the carbon isotopic composition of coal and fossil wood in the Early
Miocene Oberdorf lignite seam (Styrian Basin, Austria). Organic Geochemistry 33,
10011024.
Bechtel, A., Sachsenhofer, R.F., Zdravkov, A., Kostova, I., Gratzer, R., 2005. Inuence of
oral assemblage, facies and diagenesis on petrography and organic geochemistry
of the Eocene Bourgas coal and the Miocene Maritza-East lignite (Bulgaria). Organic
Geochemistry 36, 14981522.
Brassell, S.C., Lewis, C.A., de Leeuw, J.W., de Lange, F., Sinninghe Damst, J.S., 1986. Isoprenoid thiophenes: novel products of sediment diagenesis? Nature 320, 160162.
Bray, E.E., Evans, E.D., 1961. Distribution of n-parafns as a clue to recognition of source
beds. Geochimica et Cosmochimica Acta 22, 215.
Brooks, P.W., Maxwell, J.R., 1974. Early stage fate of phytol in a recently deposited lacustrine sediment. In: Tissot, B., Beinner, F. (Eds.), Advances in Organic Geochemistry
1973. ditions Technip, Paris, pp. 977991.
Brooks, P.W., Maxwell, J.R., Patience, R.L., 1978. Stereochemical relationships between
phytol and phytanic acid, dihydrophytol and C18 ketone in recent sediments.
Geochimica et Cosmochimica Acta 42, 11751180.
Burhan, R.Y.P., Trendel, J.M., Adam, P., Wehrung, P., Albrecht, P., Nissenbaum, A., 2002.
Fossil bacterial ecosystem at methane seeps: origin of organic matter from Be'eri
sulfur deposit, Israel. Geochimica et Cosmochimica Acta 66, 40854101.
Casagrande, D.J., 1987. Sulphur in peat and coal. In: Scott, A.C. (Ed.), Coal and Coalbearing Strata: Recent AdvancesGeological Society Special Publication 32, 87105.
Chaffee, A.L., Hoover, D.S., Johns, R.B., Schweighard, F.K., 1986. Biological markers
extractable from coal. In: Johns, R.B. (Ed.), Biological Markers in the Sedimentary
Record. Elsevier, Amsterdam, pp. 311345.
de Leeuw, J.W., Simoneit, B.R.T., Boon, J.J., Rijpstra, W.I.C., de Lange, F., Van der Leeden,
J.C.W., Correia, V.A., Burlingame, A.L., Schenck, P.A., 1977. Phytol derived compounds in the geosphere. In: Campos, R., Goi, J. (Eds.), Advances in Organic Geochemistry 1975, pp. 6166 (Enadimsa Madrid).
Dehmer, J., 1989. Petrographical and organic geochemical investigation of Obrerpfalz
brown coal deposit, West Germany. International Journal of Coal Geology 11,
273290.
Dehmer, J., 1995. Petrological and organic geochemical investigation of recent peats
with known environments of deposition. International Journal of Coal Geology
28, 111138.
Diessel, C.F.K., 1986. On the correlation between coal facies and depositional environments. Symposium Advance in the Study of the Sydney Basin. Proceedings, 20th,
Newcastle, pp. 1922.
Duan, Y., Ma, L., 2001. Lipid geochemistry in a sediment core from Ruoergai Marsh deposit
(Eastern Qinghai-Tibet plateau, China). Organic Geochemistry 32, 14291442.
Dzou, L.I.P., Noble, R.A., Senftle, J.T., 1995. Maturation effects on absolute biomarker
concentration in a suite of coals and associated vitrinite concentrates. Organic Geochemistry 23, 681697.
okovi, I., Marovi, M., Kneevi, V., 1988. Tectonic pattern and neotectonic activity in
KolubaraTamnava basin. Annales Gologiques de la Pninsule Balkanique 52,
201202.
Ercegovac, M., Pulejkovi, D., 1991. Petrographic composition and coalication degree
of coal in the Kolubara coal basin. Annales Gologiques de la Pninsule Balkanique
55, 223239.
Ercegovac, M., ivoti, D., Kosti, A., 2006. Geneticindustrial classication of brown
coals in Serbia. International Journal of Coal Geology 68, 3956.
Ficken, K.J., Li, B., Swain, D.L., Eglinton, G., 2000. An n-alkane proxy for the sedimentary
input of submerged/oating freshwater aquatic macrophytes. Organic Geochemistry 31, 745749.
Goossens, H., de Leeuw, J.W., Schenck, P.A., Brassell, S.C., 1984. Tocopherols as likely
precursors of pristane in ancient sediments and crude oils. Nature 312, 440442.
Haberer, M.R., Mangelsdorf, K., Wilkes, H., Horseld, B., 2006. Occurrence and
palaeoenvironmental signicance of aromatic hydrocarbon biomarkers in Oligocene
sediments from the Mallik 5L-38 Gas Hydrate Production Research Well (Canada).
Organic Geochemistry 37, 519538.
Hughes, W.B., Holba, A.G., Dzou, L.I.P., 1995. The ratios of dibenzothiophene to phenanthrene and pristane to phytane as indicators of depositional environment and lithology
of petroleum source rocks. Geochimica et Cosmochimica Acta 59, 35813598.
Ikan, R., Baedecke, M.J., Kaplan, I.R., 1973. C18-Isoprenoid ketone in recent marine sediments. Nature 244, 154155.
International Committee for Coal Petrology (ICCP), 2001. The new inertinite classication (ICCP System 1994). Fuel 80, 459471.
ISO 1171, 1997. Methods for analysis and testing of coal and coke. Determination of
Ash Content. International Organization for Standardization, Switzerland . (10 pp.).
ISO 11760, 2005. Classication of Coal. International Organization for Standardization,
Switzerland . (9 pp.).
Ivanov, D., Utescher, T., Mosbrugger, V., Djordjevi-Milutinovi, D., Molchanoff, S.,
2011. Miocene vegetation and climate dynamics in Eastern and Central Paratethys
(Southeastern Europe). Palaeogeography, Palaeoclimatology, Palaeoecology 304,
262275.
Kalkreuth, W., Keuser, C., Fowler, M., Li, M., McIntyre, D., Pttmann, W., Richardson, R.,
1998. The petrology, organic geochemistry and palynology of Tertiary age Eureka
Sound Group coals, Arctic Canada. Organic Geochemistry 29, 799809.
22
Kezovi, M., 2010. Synsedimentation development of tectonic activity coalbearing series of the KolubaraTanmnava basin. Proceedings of the 15th Congress of geologists of Serbia with International Participation, Belgrade, pp. 99102 (in Serbian
with English abstract; ISBN: 978-86-86053-08-4).
Kezovi, M., 2011. Coal bearing in Kolubara basin. The Journal of the Public Enterprise
Electric Power Industry of Serbia, Belgrade 64, 154163 (in Serbian with English
abstract; ISSN: 00135755).
Killops, S., Cook, R., Raine, J., Weston, R., Woolhouse, T., 2003. A tentative New Zealand
chemostratigraphy for the JurassicCretaceous based on terrestrial plant biomarkers. New Zealand Journal of Geology and Geophysics 46, 6377.
Killops, S.D., Funnell, R.H., Suggate, R.P., Sykes, R., Peters, K.E., Walters, C., Woolhouse,
A.D., Weston, R.J., Boudou, J.-P., 1998. Predicting generation and expulsion of parafnic oil from vitrinite-rich coals. Organic Geochemistry 29, 121.
Killops, S.D., Raine, J.I., Woolhouse, A.D., Weston, R.J., 1995. Chemostratigraphic evidence of higher-plant evolution in the Taranaki Basin, New Zealand. Organic Geochemistry 23, 429445.
Kolcon, I., Sachsenhofer, R.F., 1999. Petrography, palynology and depositional environment of the early Miocene Oberdorf lignite seam (Styrian Basin, Austria). International Journal of Coal Geology 41, 275308.
Mackenzie, A.S., Patience, R.L., Maxwell, J.R., 1981. Molecular changes and the maturation of sedimentary organic matter. In: Atkinson, G., Zuckermann, J.J. (Eds.), Origin
and Chemistry of Petroleum. Proc. 3rd Annual Karcher Symposium. Pergamon
Press, Oxford, pp. 131.
Magyar, I., Geary, D.H., Mller, P., 1999. Paleogeographic evolution of the Late Miocene
Lake Pannon in Central Europe. Palaeogeography, Palaeoclimatology, Palaeoecology
147, 151167.
Marynowski, L., Zato, M., 2010. Organic matter from the Callovian (Middle Jurassic)
deposits of Lithuania: compositions, sources and depositional environments. Applied
Geochemistry 25, 933946.
Matsumoto, G.I., Akiyama, M., Watanuki, K., Torii, T., 1990. Unusual distribution of longchain
n-alkanes and n-alkenes in Antarctic soil. Organic Geochemistry 15, 403412.
Nakamura, H., Sawada, K., Takahashi, M., 2010. Aliphatic and aromatic terpenoid biomarkers in Cretaceous and Paleogene angiosperm fossils from Japan. Organic Geochemistry 41, 975980.
Nott, C.J., Xie, S., Avsejs, L.A., Maddy, D., Chambers, F.M., Evershed, R.P., 2000. n-Alkane
distributions in ombrotrophic mires as indicators of vegetation change related to
climate variation. Organic Geochemistry 31, 231235.
Olivella, M.A., Gorchs, R., de las Heras, F.X.C., 2006. Origin and distribution of biomarkers in
the sulphur rich Utrillas coal basin Teruel mining district Spain. Organic Geochemistry 37, 17271735.
Ortiz, J.E., Daz-Bautista, A., Aldasoro, J.J., Torres, T., Gallego, J.L.R., Moreno, L., Estbanez,
B., 2011. n-Alkan-2-ones in peat-forming plants from the Roanzas ombrotrophic
bog (Asturias, northern Spain). Organic Geochemistry 42, 586592.
Otto, A., Simoneit, B.R.T., 2001. Chemosystematics and diagenesis of terpenoids in fossil
conifer species and sediment from the Eocene Zeitz Formation, Saxony, Germany.
Geochimica et Cosmochimica Acta 65, 35053527.
Otto, A., Simoneit, B.R.T., 2002. Biomarkers of Holocene buried conifer logs from Bella
Coola and North Vancouver, British Columbia, Canada. Organic Geochemistry 33,
12411251.
Otto, A., Walther, H., Pttmann, W., 1997. Sesqui- and diterpenoid biomarkers preserved
in Taxodium-rich Oligocene oxbow lake clays, Weisselster Basin, Germany. Organic
Geochemistry 26, 105115.
Otto, A., Wilde, V., 2001. Sesqui-, di-, and triterpenoids as chemosystematic markers in
extant conifers a review. The Botanical Review 67, 141238.
Ourisson, G., Albrecht, P., Rohmer, M., 1979. The hopanoids: palaeochemistry and biochemistry of a group of natural products. Pure and Applied Chemistry 51, 709729.
Panti, N., Duli, I., 1993. Pontian palynomorphs in Serbia. In: Planderov, E., Konzalov, M.
(Eds.), Paleooristic and Paleoclimatic Changes during Cretaceous and Tertiary:
Geologick stav Dionza tra, Bratislava, pp. 181186 (ISBN: 80-85314-26-6).
Peters, K.E., Walters, J.M., Moldowan, J.M., 2005. The Biomarker Guide Vol. 2: Biomarkers and Isotopes in the Petroleum Exploration and Earth History. Cambridge
University Press, Cambridge.
Philp, R.P., 1985. Fossil Fuel Biomarkers: Applications and Spectra. Methods in Geochemistry and Geophysics. Elsevier, Amsterdam.
Quirk, M.M., Wardroper, A.M.K., Wheatley, R.E., Maxwell, J.R., 1984. Extended
hopanoids in peat environments. Chemical Geology 42, 2543.
Ries-Kautt, M., Albert, P., 1989. Hopane-derived triterpenoids in soils. Chemical Geology
76, 143151.
Rgl, F., 1996. Stratigraphic correlation of the Paratethys Oligocene and Miocene.
Mitteilungen. Gesellschaft der Geologie und Bergbaustudenten in Wien 41, 6573.
Rohmer, M., Bisseret, P., Neunlist, S., 1992. The hopanoids, prokaryotic triterpenoids
and precursors of ubiquitous molecular fossils. In: Moldowan, J.M., Albrecht, P.,
Philp, R.P. (Eds.), Biological Markers in Sediments and Petroleum. Prentice Hall,
Englewood Cliffs, NJ, pp. 117.
Rontani, J.-F., Baillet, G., Aubert, C., 1991. Production of cyclic isoprenoid compounds
during the photodegradation of chlorophyll- in seawater. Journal of Photochemistry
and Photobiology A: Chemistry 59, 369377.
Rontani, J.-F., Giral, P.J.-P., 1990. Signicance of photosensitized oxidation of alkanes
during the photochemical degradation of petroleum hydrocarbon fractions in seawater. International Journal of Environmental Analytical Chemistry 42, 6168.
Rontani, J.-F., Giral, P.J.-P., Baillte, G., Raphel, D., 1992. Bound 6,10,14-trimethylpentadecan2-one: a useful marker for photodegradation of chlorophylls with a phytol ester group in
seawater. Organic Geochemistry 18, 139142.
Rubinstein, I., Sieskind, O., Albrecht, P., 1975. Rearranged sterenes in a shale: occurence
and simulated formation. Journal of the Chemical Society, Perkin Transactions 1
(19), 18331836.
Scalan, E.S., Smith, J.E., 1970. An improved measure of the oddeven predominance in the
normal alkanes of sediment extracts and petroleum. Geochimica et Cosmochimica
Acta 34, 611620.
Sieskind, O., Joly, G., Albrecht, P., 1979. Simulation of the geochemical transformations
of sterols; superacid effect of clay minerals. Geochimica et Cosmochimica Acta 43,
16751680.
SRPS B.H8.318/1972, 1972. Methods of Analysis of Coal and Coke Determination of
Gross Caloric Value by the Calorimetric Bomb Method, and Calculation of Net
Caloric Value. Institute for Standardization of Serbia, Belgrade, Serbia. (11 pp.
(in Serbian)).
SRPS B.H8.338/1986, 1986. Coal and Coke Determination of Total Moisture Content
Gravimetric Method. Institute for Standardization of Serbia, Belgrade, Serbia. (5 pp.
(in Serbian)).
SRPS B.H8.390/1987, 1987. Brown Coals and Lignites Determination of Moisture Content
Indirect Gravimetric Method. Institute for Standardization of Serbia, Belgrade, Serbia.
(5 pp. (in Serbian)).
Stefanova, M., Markova, K., Marinov, S., Simoneit, B.R.T., 2005a. Molecular indicators for coalforming vegetation of the Miocene Chukurovo lignite, Bulgaria. Fuel 84, 18301838.
Stefanova, M., Markova, K., Marinov, S., Simoneit, B.R.T., 2005b. Biomarkers in the fossils from the Miocene-aged Chukurovo lignite, Bulgaria: sesqui- and diterpenoids.
Bulletin of Geosciences 80, 9397.
Stefanova, M., Oros, D.R., Otto, A., Simoneit, B.R.T., 2002. Polar aromatic biomarkers in
the Miocene Maritza-East lignite, Bulgaria. Organic Geochemistry 33, 10791091.
Stevanovi, P., 1951. Pontische Stufe im Engeren Sinne-obere Congerienschichten
Serbiens und der angrenzenden Gebiete. Serbische Akademie der Wissenschaften
Bd. CLXXXVII (2), 293361 (in German).
Stout, S., 1992. Aliphatic and aromatic triterpenoid hydrocarbons in a Tertiary angiospermous lignite. Organic Geochemistry 18, 5166.
Sykorova, I., Pickel, W., Christanis, K., Wolf, M., Taylor, G.H., Flores, D., 2005. Classication
of huminite ICCP system 1994. International Journal of Coal Geology 62, 85106.
Taylor, G.H., Teichmller, M., Davis, A., Diessel, C.F.K., Littke, R., Robert, P., 1998. Organic
Petrology. Gebrder Borntraeger, Berlin.
Teichmller, M., 1989. The genesis of coal from the viewpoint of coal petrology. International Journal of Coal Geology 12, 187.
ten Haven, H.L., de Leeuw, J.W., Rullktter, J., Sinninghe Damst, J.S., 1987. Restricted
utility of the pristane/phytane ratio as a palaeoenvironmental indicator. Nature
330, 641643.
Thiel, V., Blumenberg, M., Pape, T., Seifert, R., Michaelis, W., 2003. Unexpected occurrence of hopanoids at gas seeps in the Black Sea. Organic Geochemistry 34, 8187.
Tuo, J., Li, Q., 2005. Occurrence and distribution of long-chain acyclic ketones in immature coals. Applied Geochemistry 20, 553568.
Utescher, T., Djordjevic-Milutinovic, D., Bruch, A., Mosbrugger, V., 2007. Palaeoclimate and
vegetation change in Serbia during the last 30 Ma. Palaeogeography, Palaeoclimatology,
Palaeoecology 253, 141152.
van Aarssen, B.G.K., Cox, H.C., Hoogendoorn, P., de Leeuw, J.W., 1990. A cadinene biopolymer in fossil and extant dammar resins as a source for cadinanes and
bicadinanes in crude oils from South East Asia. Geochimica et Cosmochimica Acta
54, 30213031.
van Dorselaer, A., Albrecht, P., Connan, J., 1975. Changes in composition of polycyclic
alkanes by thermal maturation (Yallourn Lignite, Australia). In: Campus, R., Goi,
J. (Eds.), Advances in Organic Geochemistry. Enadimsa, Madrid, pp. 5359.
Vitorovi, D., Aleksi, B., Ercegovac, M., Markovi, B., Cvetkovi, O., Aleksi, B., 1996.
Catalytic hydrogenation of Tamnava (Yugoslavia) soft brown coal. Journal of the
Serbian Chemical Society 61, 129136.
Vitorovi, D., Aleksi, B., Ercegovac, M., Aleksi, B., Kontorovi, S., Markovi, B., Cvetkovi,
O., Mitrovski, S., 1994. Liquefaction behaviour of Kolubara soft brown coal. Fuel 73,
17571765.
Volkman, J.K., Maxwell, J.R., 1986. Acyclic isoprenoids as biological markers. In: Johns, R.B.
(Ed.), Biological Markers in the Sedimentary Record. Elsevier, Amsterdam, pp. 142.
Vu, T.T.A., Zink, K.-G., Mangelsdorf, K., Sykes, R., Wilkes, H., Horseld, B., 2009. Changes
in bulk properties and molecular compositions within New Zealand Coal Band solvent
extracts from early diagenetic to catagenetic maturity levels. Organic Geochemistry
40, 963977.
Vukovi, B., Bogdanovi, V., 2010. Possibilities and conditions of mineral resources exploitation on designed open pit Ore-eld E. Proceedings of the 15th Congress of
geologists of Serbia with International Participation, Belgrade, pp. 189194 (in Serbian
with English abstract; ISBN: 978-86-86053-08-4).
Wakeham, S.G., Schaffner, C., Giger, W., 1980. Polycyclic aromatic hydrocarbons in Recent lake sediments. II. Compounds derived from biological precursors during early
diagenesis. Geochimica et Cosmochimica Acta 44, 415429.
Wolff, G.A., Ruskin, N., Marshall, J.D., 1992. Biogeochemistry of an early diagenetic concretion from the Birchi Bed (L. Lias, W. Dorset, U.K.). Organic Geochemistry 19, 431444.
Web references
http://www.rbkolubara.co.rs (last accessed July, 13 2012).
http://www.eps.rs (last accessed July, 13 2012).