International Journal of Coal Geology 71 (2007) 554 – 567

www.elsevier.com/locate/ijcoalgeo

Potential source rocks, organic geochemistry and thermal

maturation in the southern depocenter (Kipourio–Grevena)
of the Mesohellenic Basin, central Greece
P. Avramidis ⁎, A. Zelilidis
Department of Geology, University of Patras, 26500 Rio-Patras Greece
Received 8 February 2006; received in revised form 1 December 2006; accepted 11 December 2006
Available online 30 December 2006

Abstract

The study area is the southern depocenter (depth N4200 m) of the Mesohellenic Basin which extends between Kipourio and
Grevena, central Greece. The Mesohellenic Basin is a Middle-Tertiary intramontane basin developed within the Hellenide orogen.
Previous studies have focused on the depositional environments, configuration and hydrocarbon potential of the basin. In this paper
we present additional geochemical and petrographic data from outcrop samples of the basin's southern depocenter, which is
considered the most promising area, in terms of hydrocarbon prospectivity. A total number of thirty six samples were analysed:
Rock-Eval pyrolysis, maceral analysis, vitrinite reflectance and thermal alteration index, bitumens extraction, liquid
chromatography, and GC-MS. The samples were collected from deltaic deposits and submarine fan sediments of Late Eocene
to Late Oligocene age. The TOC values of the analysed samples range between rich and very rich and the organic matter consists
mainly of type III kerogen and the organic matter consider to be predominately gas prone. The thermal maturity assessed from Tmax
and vitrinite reflectance shows an immature stage of the organic matter along with the presence of layers having reached the very
early mature stage. Vitrinite reflectance measurements and maturity calculations (applying the Lopatin modeling), reveal that the
lower part of the depocenter sediments falls within the ‘oil window’. The extractable organic matter (EOM) (mg bitumens/g TOC)
indicate the existence of samples (from deltaic deposits) with high ratio of transformation (EOM) (N 100 mg bitumen/g TOC). The
GC and GC-MS analyses of the biomarkers indicate mainly the occurrence of terrestrial organic matter reflecting oxidizing
conditions and both immature and very early mature stages. The results of the Rock-Eval pyrolysis and the distribution of the
isoprenoids support the assumption of the input of an organic matter mixture.
© 2006 Elsevier B.V. All rights reserved.

Keywords: Hydrocarbon potential; Depositional environment; Organic geochemistry; Mesohellenic Basin, Greece

1. Introduction (Fig. 1a). The basin formed within the Hellenide orogen
and developed from Late Eocene to Late Miocene time
The study area is the Mesohellenic Basin, a middle (Fig. 1b) as a piggy-back basin along the eastern flank of
Tertiary intramontane basin, located in central Greece. It a giant pop-up structure (Robertson, 1994).
is 130 km long, and 40 km wide and trends SSE–NNW In the Mesohellenic Basin, hydrocarbon exploration
activities have been carried out by the Public Petroleum
⁎ Corresponding author. Corporation of Greece, while studies dealing with ana-
E-mail address: p.avramidis@upatras.gr (P. Avramidis). lyses of depositional environments, basin configuration
0166-5162/$ - see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.coal.2006.12.006
 P. Avramidis, A. Zelilidis / International Journal of Coal Geology 71 (2007) 554–567 555

Fig. 1. a) Location of the study area, b) Geological map of the study area (Kipourio–Grevena); AA': the location of the cross-section (see Fig. 1d),
c) Layout of the basin with isopach map showing the two depocenters and d) Geological cross-section modified from Kontopoulos et al. (1999) and
Avramidis et al. (2002).
556 P. Avramidis, A. Zelilidis / International Journal of Coal Geology 71 (2007) 554–567

and the preliminary assessment of the hydrocarbon po- studies covering the stratigraphy and the depositional
tential, have been reported by Kontopoulos et al. (1999), environments, the basin evolution is interpreted – from
Avramidis et al. (2002) and Zelilidis et al. (2002). The the western to the eastern margin – as follows: a) Middle
basin comprises two depocentres, the first one in the Eocene fan delta deposits, up to 100 m thick adjacent to
northern part (N3200 m thick) and the second in the the Krania fault, b) Middle to Late Eocene submarine
southern part (N 4200 m thick) (Fig. 1c). The basin is fan deposits — inner fan showing a thickness of 600 m
filled with sediments of Late Eocene to Late Miocene and outer fan 300 m, c) Late Eocene 900-m thick deltaic
age. The sedimentary sequences of the Mesohellenic deposits, d) Early to Late Oligocene submarine fans,
Basin consist mainly of submarine fan (sandstone and with a cumulative thickness of 1100 m comprising the
shale) and deltaic deposits. The basin is considered to inner and outer fan, and e) Miocene shelf sediments up
constitute a high-risk area in terms of hydrocarbon ex- to 900 m thick.
ploration (Avramidis et al., 2002); this is supported by
the fact that up to now no commercial deposits have 3. Materials and methods
been discovered. A licensing round for hydrocarbon
exploration and exploitation was held in 1996 (Roussos Thirty-six samples (30 hand-picked from outcrops
and Marnelis, 1995), while a second round will soon and 6 core samples) were studied in the Stratochem
take place including areas in central and northern Laboratories using (a) Rock-Eval II pyrolysis (36 sam-
Greece, such as the Mesohellenic Basin (Mavromatidis ples), (b) bitumen extraction, liquid chromatography
et al., 2004). and GC-MS (9 samples), and (c) maceral analysis and
The objective of the present paper is to present geo- vitrinite reflectance measurements.
chemical and petrographic data from outcrop samples The basic geochemical and petrographic techniques
from the southern hydrocarbon-prone depocenter of the applied, have been described in detail by Tissot and
basin. Welte (1984), Moldowan et al. (1985), Brooks et al.
(1992), Killops and Killops (1993), Peters and Moldo-
2. Geological setting wan (1993), and Hunt (1996). In the present paper we
followed the method of Espitalié et al. (1977) on the
The evolution of the Mesohellenic Basin was con- development and application of the Rock-Eval Pyro-
trolled by the activity of the Krania, Eptachori and lyzer, and parameters such as TOC, Tmax, Hydrogen
Theotokos faults (Fig. 1b,d). During the Late Eocene, Index (HI), Oxygen Index (OI), Productivity Index (PI)
and due to the activity of the Krania thrust, fan deltas and S1, S2 and S3 were obtained.
developed in the proximal part of the basin, and Solvent extraction was carried out by soxhlet tech-
submarine fans in the distal part. Also during the Late nique using chloroform and benzene/ethanol mixture
Eocene, the Eptachori thrust was activated and fan (2:1). Asphaltenes were precipitated with hexane and the
deltas developed adjacent to the fault. Due to synchro- soluble fraction was separated into saturates, aromatics
nous activity of these faults a structural platform formed, and resins (NSO compounds) on a silica-alumina col-
on which delta-plain sediments accumulated. umn by successive elution using hexane, benzene, and
In early Oligocene times, only the Eptachori thrust benzene–methanol. The solvents were evaporated and
was active and submarine fans developed throughout the weight percent of each component was determined.
the basin. During Late Oligocene to Early Miocene, For the GC analysis, the sample of whole oil was
the subsidence of the Mesohellenic Basin varied as a injected directly into a Hewlett Packard 5890 Gas Chro-
result of differential thrust activity along the basin matograph fitted with a Quadrex 50-meter fused silica
axis (Doutsos et al., 1994; Zelilidis et al., 1997). Due capillary column. The GC was programmed from 40 to
to varying tectonic regimes the basin evolved from 340 °C at 10 °C/min with a 2-minute hold at 40 °C and a
a uniformly structured basin (Early Oligocene) to 20-minute hold at 340 °C. Analytical data were pro-
an internally partitioned basin (Late Oligocene–Early cessed with a Nelson Analytical model 3000 chroma-
Miocene). tographic data system and an IBM computer hardware.
In the study area, mapping and interpretation of the All standard calculations were made including pristine/
depositional environments are based on sedimentolog- phytane ratio and carbon preference index. Two gas
ical work by Zelilidis et al. (1997) and seismic inves- chromatograms were provided, one showing all com-
tigation by Kontopoulos et al. (1999) (Fig. 1d), while a pounds between nC2 and nC40 and the other a computer
review of the geodynamic controls of the Mesohellenic enhanced version of the chromatogram between nC2 and
Basin is given by Ferriere et al. (2004). Based on the nC10. Compounds as low as ethane, could be detected if
 P. Avramidis, A. Zelilidis / International Journal of Coal Geology 71 (2007) 554–567 557

present. In addition, the concentration of C13 to C20 (nd = 1.516 at 23 °C). This calibration is linearly accurate
isoprenoids were determined and plotted. for reflectance values ranging from peat (0.20% Ro)
Computerized Gas Chromatography/Mass Spec- through anthracite (4.0% Ro). A xenon light source was
trometry (GC/MS) of saturate and aromatic fractions applied for blue-light excitation using a filter at 495 nm,
was used to evaluate various geochemical character- a barrier filter at 520 nm and a tungsten light source for
istics of oils and rock extracts, including organic facies, TAI analysis. The purpose of the analysis was to mea-
thermal maturity level and degree of alteration. The sure thermal maturation rather than exact identification
saturate and aromatic fractions were isolated by liquid of macerals.
chromatography from whole oils or source rock extracts
and injected into a HP5890 Gas Chromatograph coupled 4. Results and discussion
to a HP5971A Mass Selective Detector (MSD). The
analysis targeted two important hydrocarbon classes: The location and the depositional environment for
triterpane and sterane biomarkers and 2- and 3-ring each sample are presented in Fig. 1b, while their coor-
aromatic hydrocarbons. The Selected Ion Monitoring dinates and Rock-Eval results are showed in Table 1.
(SIM) feature of the GC/MS data acquisition system The organic geochemistry results, as well as the maceral
permits specific ions to be monitored. Ions with mass/ analysis, the vitrinite reflectance and the TAI are
charge (m/z) 191 allow characterization of specific tri- presented on Table 2.
terpenoid compounds, while ions with m/z 217 are
diagnostic for steranes. Steranes with different chemical 4.1. Rock-Eval pyrolysis
structures can be identified using different ions. Thus,
m/z 218 is characteristic of steranes with abb stereo- The TOC contents of five outer-fan (Late Oligocene)
chemistry and diasteranes exhibit a pronounced m/z 259 samples representing lignite intercalations, vary from
fragment. In addition, molecular ions characteristic of 27.58% and 56.24% (Table 1). The genetic potential
individual triterpane and sterane compounds (m/z 370, (S1 + S2) of these samples ranges from 28.43 to 66.07 kg
372, 384, 386, 398, 400, 412, 414 and 426) are acquired. HC/t rock and given the type of kerogen (Table 1), it
These molecular ions are not provided as part of the indicates a potential for gas generation. The respective
routine analytical report, but are available to confirm hydrogen index (HI = S2/TOC) vs. oxygen index
peak identifications and to identify unknown com- (OI = S3/TOC) plot on the van Krevelen diagram (van
pounds. In addition to saturated steranes, monoaromatic Krevelen, 1984; Tissot and Welte, 1984), indicates the
and triaromatic steranes were identified in the aromatic predominance of organic matter of type III (Fig. 2a).
fractions by the ions m/z 253 and 231, respectively. The Tmax values range from 410 to 432 revealing an
A Zeiss Universal microscope system was used for immature to very early mature level (Table 1; Fig. 3).
maceral analysis. Maceral analysis was performed The S2/S3 ratio (Peters, 1986), in combination with the
in 15 samples, either in whole sample or after acid types of the organic matter, indicates that the potential
treatment, using reflected and transmitted light and of these sediments is to produce mainly gas (S2/S3 b 2)
blue-light excitation. The nomenclature applied in the with exception of samples #23 and #26, where S2/
analysis was based, in general, on the classification S3 N 5, while PI values range from 0.06 to 0.1 (Table 1).
described by Stach et al. (1982). For the texture of the The eleven inner fan (Middle–Late Oligocene)
unstructured lipids the terminology proposed by samples are characterised by types III and IV kerogen
Castaòo and Sparks (1974) and Potter et al. (1998) (Fig. 2b). Although there are samples with high genetic
was followed; according to this, the various types of potential (samples #1, 35, 5, 6, 12, 22, 33), the HI being
vitrinite were grouped into one group unless it could be b 100 and the relatively low Tmax values (b 430) indicate
identified as ‘lipid-rich (or hydrogen-rich) vitrinite’ that the organic matter is thermally immature (Table 1;
(Lo, 1993). Noteworthy to mention that in this study Fig. 3). The S2/S3 ratio in relation to the kerogen type
the term ‘vitrinite’ also includes humic components of indicates basically a limited ability for gas generation
low rank (i.e. huminite). and only sample #12 (with higher HI) may has a minor
The vitrinite reflectance measurements were per- potential for liquid hydrocarbons generation. Notewor-
formed on a polished block in reflected light and TAI thy, the PI values of three samples (#2, 6 and 21) are
was performed on a strewn slide in transmitted light. relatively high (Table 1).
A halogen light source was used for vitrinite reflec- The two inner fan (Early Oligocene) samples are
tance with a digital indicator calibrated against a glass projected as kerogen types III and IV, in the HI vs. OI
standard with a reflectance of 1.02% in oil immersion diagrams (Table 1; Fig. 2c). Although the genetic
558 P. Avramidis, A. Zelilidis / International Journal of Coal Geology 71 (2007) 554–567

Table 1
Rock-Eval pyrolysis data
SAMPLE Long/Lat TOC S1 S2 S3 Tmax HI OI PI S2/S3 PP
Upper Oligocene — outer fan deposits
23 39°59′67″N 21°23′05″E 31.57 3.73 62.34 6.85 411 197 22 0.06 9.10 66.07
24 39°59′46″N 21°23′31″E 38.16 0.9 27.53 9.44 424 72 25 0.03 2.92 28.43
25 39°59′46″N 21°23′31″E 51.47 1.09 37.92 8.75 418 74 17 0.03 4.33 39.01
26 39°59′46″N 21°23′31″E 27.58 4.51 40.28 5.41 410 146 20 0.1 7.45 44.79
34 39°59′37″N 21°23′22″E 56.24 0.5 33.69 9.58 432 60 17 0.01 3.52 34.19

Middle–upper Oligocene — inner fan deposits

1 39°59′37″ N 21°23′22″E 5.41 0.35 5.56 1.31 425 103 24 0.06 4.24 5.91
2 –//– 0.71 0.19 0.42 0.38 314 59 54 0.31 1.11 0.61
3 –//– 4.43 0.14 2.8 1.15 387 63 26 0.05 2.43 2.94
4 –//– 3.89 0.21 3.67 1.19 374 94 31 0.05 3.08 3.88
5 –//– 15.06 0.48 11.02 2.4 420 73 16 0.04 4.59 11.5
6 –//– 8.78 2.42 13.3 1.68 396 151 19 0.15 7.92 15.72
12 39°59′23″N 21°23′03″E 42.72 1.4 103.47 7.02 406 242 16 0.01 14.74 104.87
21 30°00′34″N 21°20′11″E 12.83 0.31 1.63 7.63 328 13 59 0.16 0.21 1.94
22 40°02′37″N 21°18′52″E 53.23 2.12 52.55 9.16 417 99 17 0.04 5.74 54.67
33 39°58′85″N 21°22′41″E 51.97 0.74 26.33 12.91 436 51 25 0.03 2.04 27.07
35 39°57′35″N 21°22′44″E 38.66 0.44 9.92 13.25 360 26 34 0.04 0.75 10.36

Lower Oligocene — inner fan deposits

20 39°58′31″N 21°22′12″E 8.16 0.59 2.13 5.55 439 26 68 0.22 0.38 2.72
31 40°00′12″N 21°18′61″E 48.26 1.18 54.61 9.08 428 113 19 0.02 6.01 55.79

Upper Eocene — deltaic deposits

7 39°58′20″N 21°02′10″E 54.9 15.28 137.92 13.43 409 251 24 0.1 10.27 153.2
8 39°58′20″N 21°02′10″E 14.52 0.3 11 5.98 423 76 41 0.03 1.84 11.3
9 39°58.11″N 21°22′10″E 55.6 5.47 146.28 12.51 417 263 23 0.04 11.69 151.75
10 39°58′11″N 21°22′10″E 56.12 0.72 35.95 12.45 440 64 22 0.02 2.89 36.67
11 39°58′02″N 21°22′08″E 55.01 0.35 25.65 12.11 459 47 22 0.01 2.12 26
13 39°58′02″N 21°22′08″E 57.48 2.53 36.06 13.36 427 63 23 0.07 2.70 38.59
14 39°57′77″N 21°22′05″E 65.73 43.08 163.33 3.94 391 248 6 0.21 41.45 206.41
15 39°58′72″N 21°22′44″E 64.94 40.31 172.29 3.2 387 265 5 0.19 53.84 212.6
16 39°57′24″N 21°21′25″E 67.31 44.24 213.17 3.33 385 317 5 0.17 64.02 257.41
17 39°59′24″N 21°23′25″E 5.23 0.48 10.14 0.45 422 194 9 0.05 22.53 10.62
18 39°56′89″N 21°22′23″E 35 3.82 120.98 1.62 407 346 5 0.03 74.68 124.8
27 39°56′76″N 21°21′08″E 54.56 0.45 22.31 11.35 452 41 21 0.02 1.97 22.76
28 Boreholes 45.24 3.4 111.81 13.53 416 247 30 0.03 8.26 115.21
29 –//– 44.61 0.4 22.87 11.49 435 51 26 0.02 1.99 23.27
30 –//– 59.23 5.36 159.46 12.45 417 269 21 0.03 12.81 164.82
32 –//– 61.78 12.2 136.16 9.3 411 220 15 0.08 14.64 148.36
36 –//– 56.38 0.77 30.13 12.23 438 53 22 0.02 2.46 30.9
37 –//– 44.82 0.56 23.88 11.66 433 53 26 0.02 2.05 24.44

potential seems to be moderate to high, the low HI Table 1). All analysed samples from the deltaic deposits
values (b 115) and the kerogen types, infer that the have a high genetic potential ranging from 10.62 to
results are obviously not unequivocal. 257.41 kg HC/t rock. Almost all the examined samples
The eighteen deltaic (Late Eocene) samples indicate are characterised by a S2/23 N 5 showing the existence
the presence of source rocks differing from the above of layers which could produce liquid hydrocarbons.
examined layers, by indicating kerogen type II (samples Exceptions are samples #8, 27, and 29. Moreover, based
#7, 9, 14, 14,15, 16, 17, 18, 28, 30 and 32) and type III on Tmax results, layers have been identified, which show
(#8, 10, 11, 13, 27, 29, 36 and 37). The PIs (0.17–0.21) readings (Tmax N 425) pertaining to the ‘oil window’
indicate mature levels for samples #14, 15, 16, and but the low HI shows a minor hydrocarbon potential
immature levels for the remainder samples (Fig. 1; (Fig. 3).
Table 2
Organic geochemistry — petrology results of the studied samples
EOM Vitrinite reflectance Fractionation of Extracts L.C. Isoprenoids Triterpanes Steranes Organic matter T.A.I.
Sample mg/g Min Max STDEV R0 Saturates Aromatics NSO Asphaltenes Pr/ Pr/ Ph/ OEP Ts/Tm C27 C28 C29 Lipids Humic Other Color/
Ph nC17 nC18 intense
Inertinite Vitrinite
Outer fan — Late Oligocene
24 – 0.41 0.55 0.04 0.48 – – – – – – – – – – – – 5 – – 95 (lipid Yellow/
rich vitrinite) 2
34 1.54 0.57 5.30 4.90 57.10 32.70 0.20 0.60 5.50 1.11 0.98 0.04 0.11 0.85 30 – – 70 (lipid –
rich vitrinite)

Inner fan — middle Late Oligocene

22 55.75 0.47 0.57 0.02 0.53 2.00 6.80 22.10 69.20 2.20 1.10 1.30 1.52 0.22 0.17 0.17 0.61 – – 100 – Yellow–
orange/2
35 – 0.42 – – – – – – – – – – – – 25 – 75 – Yellow–
orange/1

Inner fan — Early Oligocene

31 – 0.48 0.55 0.02 0.52 – – – – – – – – – – – – – – 100 –

Deltaic deposits — Late Eocene

7 95.68 0.27 0.35 0.02 0.32 – – – – – – – – – – – – 70 – 30 – Orange/
1
10 – 0.43 0.54 0.03 0.48 – – – – – – – – – – – – – – 0 100 (lipid –
rich vitrinite)
11 – 0.42 0.54 0.02 0.48 – – – – – – – – – – – – – – 50 50 (lipid –
rich vitrinite)
14 156.66 0.44 0.52 0.03 0.48 0.50 1.90 33.10 64.60 0.80 0.70 0.60 – – – – – 10 – 90 – Orange–
yellow/4
15 159.04 0.43 0.52 0.02 0.48 – – – – – – – – – – – – 20 – 80 – Yellow/
4
16 – 0.44 0.50 0.02 0.48 – – – – – – – – – – – – 30 – 70 – Yellow/
4
18 62.82 0.36 0.56 0.06 0.48 1.60 9.80 42.30 46.30 1.00 1.90 2.80 1.67 0.77 0.12 0.13 0.75 – – 60 40 (lipid Yellow/
P. Avramidis, A. Zelilidis / International Journal of Coal Geology 71 (2007) 554–567

rich vitrinite) 2
27 8.47 0.48 0.58 0.03 0.52 3.90 6.00 75.80 14.30 0.60 1.00 1.80 0.70 0.40 0.08 0.14 0.76 – – – 100 (lipid Orange/
rich vitrinite) 2
29 5.60 0.44 0.51 0.02 0.48 – – – – – – – – – – – – – – – 100 (lipid –
rich vitrinite)
37 11.52 0.47 0.59 0.03 0.53 3.00 5.80 42.40 48.80 1.20 0.90 0.90 1.37 0.30 0.05 0.10 0.84 – – 10 90 (lipid Orange/
rich vitrinite) 2
559
560 P. Avramidis, A. Zelilidis / International Journal of Coal Geology 71 (2007) 554–567

Fig. 2. Plot of HI versus OI for the analysed samples from the (a) Late Oligocene-outer fan deposits, (b) Middle to Late Oligocene inner fan deposits,
(c) Early Oligocene inner fan deposits and (d) Late Eocene deltaic deposits.

4.2. Extractable organic matter — LC-GC-GCMS with the immature or the very early mature stage (Tissot
and Welte, 1984) (Fig. 4; Table 2).
The EOM (mg/g rock) calculated from bitumen The GC analysis (Fig. 5) can also be used for inter-
extraction using Soxhlet apparatus, is used as a maturity pretation of environmental conditions at the time of
indicator. The yield of the deltaic samples N 150 mg/g deposition and the source of the organic matter (Tissot
(Table 2), is higher than this obtained from the Oli- and Welte, 1984; Moldowan et al., 1985; Killops and
gocene submarine fan. This may indicate migrated Killops, 1993; Hunt, 1996). The relative abundance of
hydrocarbons (Tissot and Welte, 1984) and the respec- the isoprenoids pristane to phytane and pristane/n-C17
tive level of maturity. Although we have high ratio of to phytane/n-C18 represents different environmental
EOM mg/g rock, the extract composition reveals the conditions (Dydik et al., 1978; Leythaeuser and
dominance of NSO compounds, which is in agreement Schwarzkopf, 1986; see Fig. 6). The pr/ph ratio ranges
 P. Avramidis, A. Zelilidis / International Journal of Coal Geology 71 (2007) 554–567 561

distribution of the normal steranes and the respective

C27– C28– C29 ternary diagram (Fig. 8), show a pos-
sible source from siltstones containing lignite lenses
(samples #19, 27, 37, 34; see Table 2). Huang and
Meinschein (1978) proposed that the distribution of C27
through C29 steranes in oils and rock extracts can be
used as an indicator of biological origin and depositional
environment. They suggest that C27 steranes derive
from plankton, whereas C29 steranes derive from ter-
restrial sources such as higher land plants. The analysed
samples are characterized by the dominance of C29
sterane and thus, are interpreted to indicate a terrestrial
origin of the organic matter (Fig. 8) (MacKenzie et al.,
1982).
Fig. 3. HI versus Tmax diagram for the examined samples.
4.3. Maceral analysis — Vitrinite reflectance–TAI

between 0.2 and 2.2, indicating both oxidizing (#22 and 4.3.1. Late Oligocene outer fan samples
37) and reducing conditions (samples #27, 34 and 14; Sample #24: Most vitrinite fragments are lipid-rich
see Table 2). The respective plot on the pr/n-C17 and ph/ with cell-structure remnants, which lower the reflec-
n-C18 diagram indicates mainly oxidizing conditions tance (0.48%), holes, slits, etc. There are some large
and terrestrial input of organic matter. fragments of root or bark tissue with suberinite. Both
The GC-MS analysis of the saturated fractions the woody parts and the root or bark portions of plants
(Fig. 7) and the triterpane Ts/Tm ratio show early to are present. Maturity is at the top of the oil generation
mature levels of maturity ranging from 0.30 to 0.98 zone.
(Table 2). Samples #22, 27 and 37 are at the early mature Sample #34: Organic matter consists of oxidized,
stage, while #14, 18 and 34 are at the mature stage. The lipid-rich vitrinite and unstructured material (Fig. 9d)

Fig. 4. The EOM composition of the studied samples.

562 P. Avramidis, A. Zelilidis / International Journal of Coal Geology 71 (2007) 554–567

Fig. 5. The gas chromatography diagram for the deltaic sample #18.

that may be degraded humic debris. Some reflec- 4.3.4. Late Eocene deltaic samples
tance values (0.57%) may be lowered by oxidation. Sample #7: The organic matter consists of moder-
The pyrolysis data, however, indicate that maturity ately oxidized lignite fragments, angular exsudatinite or
is at a very early mature stage. Degraded humic solid bitumen with orange fluorescence, and unstruc-
debris indicates that the unstructured material is prob- tured material in a mineral groundmass. Some coals may
ably from terrestrial sources. Humic debris means form exsudates at the lignite/sub-bituminous coal
small, low-rank terrestrial fragments that cannot be boundary during coalification. Algae, animal plankton,
identified. fats and waxes experience anaerobic saprofication
during which fatty acids and other substances form.
4.3.2. Middle-Late Oligocene inner fan samples
Sample #22: Organic matter consists of large vitrinite
fragments with some exsudatinite in fractures and some
liptodetrinite inclusions. Vitrinite may be slightly lipid-
rich. Vitrinite reflectance (0.53%) indicates that the
organic matter is immature or may be at the very top
of the oil window. Rock-Eval Tmax may be slightly
lowered by exsudatinite.
Sample #35: Coal fragments consist of compressed
vitrinite components with abundant resin bodies. Frag-
ments exhibit cell structure that is different from the
remnant cell structure of lipid-rich vitrinite. Vitrinite
reflectance (0.42%) and pyrolysis data indicate that the
organic material is immature for oil generation. Resinite
may lower the pyrolysis Tmax value.

4.3.3. Early Oligocene inner fan samples

Sample #31: Vitrinite reveals characteristics of
slightly lipid-rich vitrinite (Fig. 9c) as in sample #29,
but reflectance values do not appear to be lowered. The
vitrinite reflectance (0.52%) and the pyrolysis data Fig. 6. Plot of pristane/n-C17 versus phytane/n-C18 showing the
indicate that maturity is in the oil generation zone. origin of the organic matter (fields after Hunt, 1996).
 P. Avramidis, A. Zelilidis / International Journal of Coal Geology 71 (2007) 554–567 563

Fig. 7. Representative triterpanes (m/z of 191) and steranes (m/z 217) for fragmentation for sample #18 (deltaic deposit).

The vitrinite reflectance (0.32%) and the pyrolysis data reflectance values may be slightly lowered by the lipids
indicate that the organic matter is immature for oil contained. The reflectance (0.48%) indicates that
generation. maturity is at the top of the oil window, but pyrolysis
Sample #10: The organic matter consists of large, data indicate that maturity is in the lower oil generation
slightly lipid-rich vitrinite fragments. Vitrinite exhibits zone.
remnant cell structure, holes, characteristic fractures, Samples #14, 15, 16: The organic matter consists
and some oily (exsudanite, bituminite) spots, but it does primarily of large telinite (cell wall) fragments with
not fluoresce. The reflectance values (0.48%) may be resinite or other lipid cell filling (Fig. 9a, b). Some
slightly lowered by the lipid content and reveal that large, normal vitrinite (Type A) fragments are also
maturity is probably at the top of the oil generation zone, present. Vitrinite reflectance (0.48%) shows that
although pyrolysis data show a maturity in the mid oil maturity is approaching the top of the oil window.
generation zone. Pyrolysis Tmax may be lowered by the large amount of
Sample #11: Some vitrinite fragments appear to be resinite.
normal and some are similar to the lipid-rich vitrinite in Sample #18: Large coal fragments have been
sample #10, but without cell structure remnants. Some observed, with some yellow fluorescing exsudatinite
564 P. Avramidis, A. Zelilidis / International Journal of Coal Geology 71 (2007) 554–567

Fig. 8. Ternary diagram showing the relative abundance of C27–C28–C29 normal steranes.

in fractures. Some fragments appear normal and some vitrinite suggests a terrestrial origin of the organic matter
are lipid-rich with remnant cell structure and lowered (Teichmueller, 1986). The results of the analysis are
reflectance. The reflectance (0.48%) indicates that similar and in agreement to those of Gerolymatos et al.
maturity is approaching the top of the oil generation (1988).
zone. Pyrolysis Tmax may be lowered by exsudatinite.
Sample #27: All vitrinite fragments are lipid-rich 4.4. Burial history — TTI
with cell structure remnant, slits, fractures, etc. Reflec-
tance values may be slightly lowered. The reflectance In order to estimate the theoretical maturity of the
(0.48%) shows that maturity is in the upper oil organic matter, we used the Lopatin Time–Temperature
generation zone, but pyrolysis data indicate that Index method, adapted by Waples (1980). The TTI was
maturity is in the mid oil generation zone. calculated for a location in the central and deepest part
Sample #29: Vitrinite is slightly lipid-rich with of the Basin (Fig. 1d). Concerning the lack of boreholes
remnant cell structure, slits, oily spots, etc., and vitrinite and taking into account the sedimentary records from
reflectance values (0.48%) may be slightly lowered. outcrops and seismic profile (Kontopoulos et al., 1999),
Pyrolysis data indicate that maturity is in the oil in the calculation of TTI we used a geothermal gradient
generation zone. of 25 °C/km (Fig. 10), as a conservative approach for the
Sample #37: The vitrinite reveals characteristics of study area. The burial history is based on depositional
slightly lipid-rich vitrinite — some oily spots, holes, environments and basin evolution models of Konto-
faint remnant of cell structures and some slits. Oily spots poulos et al. (1999) and Avramidis et al. (2002). The age
occur when oily components in the lipid-rich vitrinite determination based on the contained nannofossils,
leak to the surface of the vitrinite after polishing. studied by Stoykova et al. (2002). Isopachs data for the
Reflectance (0.53%) and pyrolysis data indicate that clastic sediments, overlying the ophiolitic basement,
maturity is in the oil generation zone. were obtained from the seismic interpretations after
Thermal Alteration Indices (TAI, see Table 2) based Kontopoulos et al. (1999).
on colour intensity, show a mature level (Staplin, 1969), The TTI calculation, based on the geological model
only for samples from the Late Eocene deltaic deposits and age determinations, indicates that hydrocarbon
(samples #14, 15, 16), while the presence mostly of generation could only be expected in the lower part of
 P. Avramidis, A. Zelilidis / International Journal of Coal Geology 71 (2007) 554–567 565

Fig. 9. Representative photos showing (a) telinite with resinite and cell filling in plane light and (b) in fluorescent light, from sample #14, representing
late Eocene deltaic deposits. (c) slightly lipid-rich vitrinite in plane light, from sample #31, representing Early Oligocene inner fan deposits, and
(d) lipid-rich vitrinite and unstructured debris in plane light, from sample #34, representing Late Oligocene inner fan deposits.

the late Eocene deltaic sediments, which are modeled fluctuation of the organic matter content from rich to
to be within the top oil-window (early mature level) very rich, the occurrence of different source material,
(Fig. 10). the different sedimentary environments and the early
maturation stage of organic matter. These different
5. Conclusions features across the basin are related to the clastic
sedimentation of the sub-marine fan and deltaic
Sediments sampled from outcrops and cores from deposits; their mineralogical and chemical compo-
the Mesohellenic Basin, central Greece, indicate a nents are mainly affected by the mode and the agent
of transport. From the geochemical and petrographic
analyses of the outcrop samples we can infer that the
main feature of the organic matter is the thermal
immaturity and the existence of limited potential
source rocks, having reached the very early stage of
‘oil maturity’. From the TTI model it seems that the
deepest part of the southern depocenter (deltaic
deposits) can be thermally mature. Up to now,
however, the area has to be considered as a high-
risk area for hydrocarbon exploration, and additional
geochemical work has to be performed for the
purpose of calibrating all the maturity data with
deep borehole data. The analytical geochemical work
carried out, as well as the burial history (described
Fig. 10. TTI modeling of Lopatin method, after Waples (1980). from TTI calculation) show that the only potential
Location: at the deepest part of the basin (Fig. 1d). mature source rocks are included within the Upper
566 P. Avramidis, A. Zelilidis / International Journal of Coal Geology 71 (2007) 554–567

Eocene deltaic deposits. These deposits rendered (continued)A (continued )

Appendix
indications of the presence of mature, hydrocarbon - TRITERPANE REPORT (m/z 191)
prone layers. Sample No. ST000161 Other ID: 18
The type of organic matter is related to the
No. ID Triterpane name Ret Area Area PPM
sediment charge of the Basin derived from different time %
sources. The organic material of the submarine fans
14 K C29 Tricyclic Terpane (22R) 0 0.00 b1
and the deltaic sediments derived mainly from 15 K C29 Tricyclic Terpane (22S) 0 0.00 b1
terrestrial depositional environments that were eroded 16 L C27 18aH-Trisnorhopane 57.711 4587 3.96 23
and carried towards the deeper parts of the Basin, via (Ts)
a delta system and submarine canyons. The organic 17 M C27 17aH-Trisnorhopane 59.367 5969 5.15 30
matter includes mainly kerogen type III for the (Tm)
18 N C30 Tricyclic Terpane (22R) 0 0.00 b1
submarine fan deposits and types II and III for the 19 N C30 Tricyclic Terpane (22S) 0 0.00 b1
deltaic deposits. The organic matter is predominately 20 O C28 17aH, 18aH, 21bH-28, 0 0.00 b1
gas prone; both the thermal maturity assessed from 30-Bisnorhopane
Tmax and the vitrinite reflectance indicate that the 21 P C31 Tricyclic Terpane (22R) 0 0.00 b1
22 Q C29 17aH, 21bH 25- 0 0.00 b1
organic matter is thermally immature to early mature.
Norhopane
The results of the Rock-Eval pyrolysis and the 23 P C31 Tricyclic Terpane (22S) 65.121 0 0.00 b1
biomarkers distribution support the assumption of 24 R C29 17aH, 21bH-Norhopane 65.121 19375 16.72 98
the input of an organic matter mixture. Integration of 25 S C29 18aH-Norneohopane 65.347 5390 4.65 27
all geochemical–petrographic analyses and TTI data (29Ts)
indicate that the lower part of the deltaic deposits has 26 T C30 17aH Diahopane 0 0.00 b1
27 U C29 17bH, 21aH- 67.108 3683 3.18 19
a possible hydrocarbon potential and should attract the Normoretane
main interest for further research. 28 V C30 18aH + 18bH-Oleanane 0 0.00 b1
29 W C30 17aH, 21bH-Hopane 68.573 19346 16.70 98
Acknowledgements 30 X C30 30-Nor-29-homo-17aH- 0 0.00 b1
hopane
31 Y C30 17bH, 21aH-Moretane 70.107 8667 7.48 44
This study was carried out at the Department of 32 Z C33 Tricyclic Terpane (22R) 0 0.00 b1
Geology, University of Patras, during a scholarship 33 Z C33 Tricyclic Terpane (22S) 0 0.00 b1
tenure of the first author from the Greek State Schol- 34 a C31 17aH, 21bH- 72.583 8023 6.92 40
arship's Foundation (I.K.Y.). Homohopane (22S)
35 b C31 17aH, 21bH- 73.071 11072 9.55 56
Homohopane (22R)
Appendix A 36 c C30 Gammacerane 73.577 2807 2.42 14
37 d C34 Tricyclic Terpane (22R) 0 0.00 b1
Identification of peaks for sample #18 from deltaic 38 d C34 Tricyclic Terpane (22S) 0 0.00 b1
deposits (see Fig. 7). 39 e C32 17aH,21bH- 75.791 4656 4.02 23
Bishomohopane (22S)
40 f C32 17aH, 21bH- 76.488 5859 5.06 30
TRITERPANE REPORT (m/z 191)
Bishomohopane (22R)
Sample No. ST000161 Other ID: 18 41 g C35 Tricyclic Terpane (22R) 0 0.00 b1
42 g C35 Tricyclic Terpane (22S) 0 0.00 b1
No. ID Triterpane name Ret Area Area PPM
43 h C33 17aH, 21bH- 79.505 3397 2.93 17
time %
Trishomohopane (22S)
1 A C19 Tricyclic Terpane 0 0.00 b1 44 i C33 17aH, 21bH- 80.446 3147 2.72 16
2 B C20 Tricyclic Terpane 0 0.00 b1 Trishomohopane (22R)
3 C C21 Tricyclic Terpane 0 0.00 b1 45 j C34 17aH, 21bH- 83.340 2620 2.26 13
4 D C22 Tricyclic Terpane 0 0.00 b1 Tetrahomohopane (22S)
5 E C23 Tricyclic Terpane 0 0.00 b1 46 k C34 17aH, 21bH- 84.508 3056 2.64 15
6 F C24 Tricyclic Terpane 0 0.00 b1 Tetrahomohopane (22R)
7 G C25 Tricyclic Terpane (22R) 0 0.00 b1 47 l C35 17aH, 21bH- 87.054 2378 2.05 12
8 G C25 Tricyclic Terpane (22S) 0 0.00 b1 Pentahomohopane (22S)
9 H C24 Tetracyclic Terpane 0 0.00 b1 48 m C35 17aH, 21bH- 88.362 1845 1.59 9
10 I C26 Tricyclic Terpane (22R) 0 0.00 b1 Pentahomohopane (22R)
11 I C26 Tricyclic Terpane (22S) 0 0.00 b1
12 J C28 Tricyclic Terpane (22R) 0 0.00 b1
13 J C28 Tricyclic Terpane (22S) 0 0.00 b1
 P. Avramidis, A. Zelilidis / International Journal of Coal Geology 71 (2007) 554–567 567

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