Organic Geochemistry 33 (2002) 1571–1591

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Variations in organic geochemistry and lithology of a

carbonate sequence deposited in a backplatform basin
(Triassic, Hungary)
Magdolna Hetényia,*, Alice Brukner-Weinb, Csanád Sajgóc, János Haasd,
Mária Hámor-Vidób, Zsuzsanna Szántóe, Mária Tóthc
a
University of Szeged, H-6701 Szeged, PO Box 651, Hungary
b
Geological Institute of Hungary, H-1 142 Budapest, PO Box 106, Hungary
c
Laboratory for Geochemical Research, H-1502 Budapest, PO Box 132, Hungary
d
Academic Research Group, Dept of Geology, Eötvös Lóránd University, H-1088 Budapest Múzeum krt. 4/a, Hungary
e
Institute of Nuclear Research of the Hungarian Academy of Sciences, H-4001 Debrecen, PO Box 51, Hungary

Abstract
The variations in the organic matter quantity and quality were studied with respect to the mineral composition of the
carbonate sequences accumulated on a gentle slope (Zl-1 well) and at the toe of the slope (Rzt-1 well) located between a
Late Triassic carbonate platform and a backplatform basin. Parallel variations observed in mineral composition and
organic geochemical features of the successions appeared to be controlled by the change in climate and by sea-level
fluctuations. The repetitive sea-level changes resulted in a variation in the carbonate-rich basin facies and in the
mineralogically heterogenous slope and toe-of-slope ones. According to Rock Eval pyrolysis, organic petrography and
carbon isotope ratios, the immature organic matter is of predominantly marine origin and composed of mainly lipti-
nites in both of the studied boreholes. The results of the GC and GC/MS analyses of the saturated hydrocarbon frac-
tions of bitumens together with the composition of kerogen pyrolysates reveal a predominant algal input with a minor
variable bacterial and subordinate terrestrial contribution for the Rzt-1 borehole. In the Zl-1 borehole a significantly
higher proportion of the bacterial biomass contributed to the organic precursors. The d13C values and the composition
of the kerogen pyrolysates together with the results of the maceral analysis and GC data suggest a relatively higher, but
moderate, higher plant derived contribution in the slope facies and at the top of the toe-of-slope facies. The elementary
composition of kerogens and Rock Eval data display type II-S kerogen in the basin and the slope facies, and type I-II-S
one in the toe-of-slope facies. Variations in the hydrogen content of the organic matter mainly reflect variations in the
preservation conditions and in primary productivity. The presence of the 2,6,10,15,19-pentamethyleicosane and the
extremely low pristane/phytane ratios indicate a relatively high methanogenic bacterial activity and strongly anoxic
depositional conditions in the Rzt-1 well, especially in two most organic-rich toe-of-slope facies.
# 2002 Elsevier Science Ltd. All rights reserved.

1. Introduction Triassic carbonate platform of the Alps–Appenines

During the Triassic, oil-source sedimentary rocks
accumulated in shallow depressions at the southern
passive margin of the Tethys. An extensional basin sys-
tem formed in the onshore marginal belt of the late
* Corresponding author. Fax: +36-62-426479.
E-mail address: hetenyi@geo.u-szeged.hu (M. Hetényi).
0146-6380/02/$ - see front matter # 2002 Elsevier Science Ltd. All rights reserved.
PII: S0146-6380(02)00188-2
domain due to the incipient rifting of the Ligurian–
Penninic ocean, which led to the disintegration of the
previously existing large carbonate platform. The basins
were filled up by fine terrigenous siliciclastics and plat-
form-derived carbonate mud during the Late Norian to
Middle Rhaetian interval. Black shales accumulated in
the restricted backplatform basins are the source for
economic oil-accumulations in the Po Valley (Italy)
(Mattiavelli and Novelly, 1990; Stefani and Burchell,
1572 M. Hetényi et al. / Organic Geochemistry 33 (2002) 1571–1591
1993) and the shaley-calcaerous sequence in the western
part of the Kössen basin (Hungary) is considered to be
the source rock of the heavy sulfur-rich oil of the adja-
cent oil field.
The Kössen basin developed in the south-western
part of the Transdanubian Range structural unit
(Fig. 1) which was located between the South Alpine
and North Alpine realms in the Triassic. It was the
part of the northward-moving Triassic Pangea (Kli-
metz, 1983; Ziegler et al., 1983; Parrish, 1993), which
moved eastward to its present position during the
Paleogene (Kázmér and Kovács, 1985; Balla, 1988;
Haas et al., 1990). In the first stage of the basin-evolu-
tion, the sea-level rise and the drowning of the pre-
viously existing platform led to the formation of platey
dolomites (Rezi Dolomite Formation). After a platform
progradation episode, a new transgression started in the
latest Norian which resulted in deposition of clayey
limestones and marlstones (Kössen Formation). A
relatively thin transitional sequence (Rezi-Kössen
Fm.) between the Rezi Dolomite Fm. and Kössen
Fm. comprises mainly dolomite and limestone. Dur-
ing the Miocene the black shales filling in the inner part
of the 100–150 m deep basin were buried at 2500–3000
m depth and they entered the oil window, generating
heavy sulfur-rich oil (Clayton and Koncz, 1994). Ther-
mally immature sediments at shallow depth can be
found at the gentle slope between the basin and the
Fig. 1. Present-day setting of the topmost Norian-Rhaetian facies zones in the Alpine - North Pannonian realm (after Haas et al.,
1995). Legend: 1, Kössen facies; 2, Dolomite; 3, Dachstein Limestone; NKW, Northern Karawanks; SKW, Southern Karawanks.
platform. They provide suitable raw material for study-
ing the organic geochemical features of the backplat-
form basin succession.
Organic geochemistry of sediments filling in small
special basins formed by disintegration of the carbonate
platform near the end of the Hauptdolomit Formation
(Triassic, Norian) of the Northern Calcerous Alps has
been described by Köster et al. (1988). Bulk organic
characteristics of Hungarian Kössen Formation (Bru-
kner-Wein and Vetó´ , 1986; Hetényi, 1989; Vetó´ et al.,
2000), as well as an evaluation for the production and
preservation of the organic matter (Vetó´ et al., 2000)
have recently been reported. However, the organic geo-
chemistry of Rezi Dolomite Formation and of the tran-
sitional sequence, as well as detailed examination of
bitumen and kerogen from Kössen beds, have not yet
been published.
The aim of this work was to examine variations in the
mineral composition and organic matter of the Rezi
Dolomite Fm. and Kössen Fm., as well as those of
transitional sequence with respect to the change in
paleoenvironmental conditions. Core samples were col-
lected from two wells (Fig. 2): well Zl-l penetrated about
50 m of the Rezi-Kössen transitional strata underlying
the upper part of Rezi Dolomite Fm. and overlying the
latest Norian section of Kössen Fm.; well Rzt-1 pene-
trated a 240 m section of the Kössen Fm. The studied
sequences were deposited on the slope (well Zl-1) and at
 M. Hetényi et al. / Organic Geochemistry 33 (2002) 1571–1591
Fig. 2. Stratigraphic chart showing South-western units of the Triassic carbonate platform, Transdanubian Range, Hungary (a).
Sketch map of the location of the Kössen basin in Hungary (b) and that of the studied boreholes in the depositional basin (c). Legend:
CAR, Camian; NOR, Norian; RHT, Rhaetian; HET, Hettangian.
the toe (well Rzt-l) of the gentle slope located between
the carbonate platform and the basin.
2. Experimental
Based on earlier Rock Eval data from more than 100
samples from Rzt-l well (Vetó´ et al., 2000) and those
from 35 samples from Zl-1 well determined in this work,
two sets of samples were selected for further organic
petrographical, geochemical and mineralogical studies.
The two sets represent the Rezi Dolomite Fm., Rezi-
Kössen Transitional sequence and Kössen Fm.
Mineral composition of the rock samples was deter-
mined by chemical and XRD methods. Organic petro-
graphic observations were carried out on polished
sections of crushed bulk rocks with reflected light
microscopy (Leica DM-RX) in oil immersion. Both
normal and fluorescence light (UV and blue excitation,
420–490 nm, barrier fitter 515 nm) were used.
Rock Eval pyrolysis was performed on whole rock
samples with a Delsi Oil Show Analyzer using standard
pyrolysis procedures (Espitalié et al., 1986; Bordenave
et al., 1993). Soluble organic matter was extracted in a
Soxhlet extractor with chloroform; ashphaltene was
precipitated with light petroleum. The petroleum-solu-
ble fraction was fractionated by successive elution from
a chromatographic column filled with silica gel using
light petroleum (saturated HC), benzene (aromatic HC)
and 1:1 benzene:methanol mixture (NSO compounds).
The saturated HC fraction was analyzed using an HP
5890A gas chromatograph fitted with a 25 m
0.2 mm-
i.d. WCOT fused-silica capillary column coated with
OV-1, using hydrogen as carrier gas and flame ioni-
zation detection (FID). The oven was programmed
from 110 to 170  C at 25  C/min and from 170 to 320  C
at 5  C/min. Samples were injected in a 20:1 split mode.
1573
GC–MS was performed using a HP5971A Mass
Selective Detector (MSD) equipped with a 30 m
0.25
mm-i.d. fused silica capillary column coated with Rtx-
5MS (0.25 mm film thickness of crossbonded 5% diphe-
nyl–95% dimethyl polysiloxane) stationary phase, a
HP7673 Auto sampler and a split/splitless injector. The
gas chromatograph was programmed from 70 to 170  C
at 40  C/min and from 170 to 330  C at 6  C/min (car-
rier gas: helium 35 cm/s, scanning mass range: 50–550
m/z). The relative abundance of the compounds was
calculated from the total ion chromatograms or from
different extracted ion chromatograms by the HP soft-
ware.
Kerogen was concentrated with repeated HC1 and
HF treatments and then extracted with chloroform.
Kerogen concentrates from the Rzt-1 borehole were
pyrolysed in a Quantum device MSSV pyrolyzer ther-
mal analysis port interfaced to a Fisons 8000 GC
(Horsfield et al., 1989). 1-2 mg kerogen was sealed in
glass capillary tubes, after a reactor pre-cleaning cycle
the tubes were cracked open, then heated from 300 to
530  C at 25  C/min and held 2 min, and the products
were swept into a cryofocussed trap. After a ballistic
heating of the trap, GC-analyses were performed using
60 m
0.25 mm fused silica non-polar bonded phase
column and flame ionization detection. The oven was pro-
grammed from 35 to 310  C at 4  C/min and held 45 min.
Following Larter (1984) the products of such pyrolysis
(according to the heating rate) are comparable to the
products of flash pyrolysis. Elemental composition of
kerogens was determined using a NA 1500 NCS analy-
ser (Fisons Instruments) at 1010  C. Carbon isotopic
analyses of kerogens, mixed with CuO, were performed
by combustion at 850  C for 15 mm and measurement
of the CO2 in a Finnigan Mat Delta S type mass-spec-
trometer. The results are given relative to the Pee Dee
Belemnite standard.
1574 M. Hetényi et al. / Organic Geochemistry 33 (2002) 1571–1591

3. Results Fm. consists of nearly pure dolomite (more than 90%).

The amount of dolomite displays some scatter and an
Samples taken from well Zl-1 are predominantly upward decreasing trend throughout the transitional
composed of carbonates (Table 1). The Rezi Dolomite sequence and the Kössen Fm. (Fig. 3). Vitrinite reflec-

Table 1
Mineral composition (%) of the studied samples

Formation Depth (m) Quartz Clay min. Aragonite Calcite Dolomite Pyrite Others

Rzt-1
Kössen (Rhaetian) 82.5 4 8 12 59 17 – –
95.2 15 33 – 45 3 2 2
105.2 13 48 – 32 3 2 2
113.5 15 32 2 41 8 2 –
132.3 18 54 1 21 3 3 –
139.2 9 16 10 61 3 1 3
144.3 9 16 26 29 16 1 –
151.5 18 51 7 18 3 3 –
168.0 28 20 14 34 2 2 –
170.0 15 24 3 54 2 2 –
178.8 6 14 1 68 10 1 –
185.9 12 27 10 38 11 2 –

Kössen (Norian) 207.5 11 8 2 70 8 – 1

224.9 7 11 3 75 – 2 2
236.0 11 23 3 55 4 3 1
241.0 11 22 3 58 3 3 –

Zl-1 well
Kössen (Norian) 304.9 5 1 – 71 20 2 1
307.0 7 – – 64 25 2 2
312.6 2 1 – 68 30 – –
313.3 8 1 – 51 34 3 3

Transitional 314.3 8 1 – 55 90 1 –
317.4 9 – – 53 34 2 –
318.4 12 2 2 33 23 2 –
318.7 6 – – 1 59 – –
319.0 9 – 1 – 85 1 4
319.3 5 – – 5 93 – 1
320.2 4 – – – 91 – –
321.5 32 – – 1 68 – –
340.7 25 1 – – 72 1 1
341.5 8 – – – 92 – –
347.6 11 3 – – 84 1 1
347.9 28 1 – – 70 1 –
348.7 3 – – – 96 – 1
352.0 9 – – – 89 2 –
354.8 11 2 – 1 82 3 2
360.0 6 2 – 1 89 2 –
363.0 13 1 – – 85 – 1

Rezi Dolomite 373.5 5 1 – – 94 – –

373.9 9 – – – 90 1 –
374.3 3 – – 1 96 – –
378.5 8 – – 1 90 1 –
381.4 8 – – 1 91 – –
383.0 7 – – 1 90 2 –
386.0 6 – – – 94 – –
 M. Hetényi et al. / Organic Geochemistry 33 (2002) 1571–1591
Fig. 3. Vertical profile of dolomite content, organic carbon content and hydrogen index measured on whole rock samples, as well as carbon isotope and S/C ratios measured on
kerogens in well Zl-1.

1575
1576 M. Hetényi et al. / Organic Geochemistry 33 (2002) 1571–1591

tance ranging between 0.32 and 0.35% R0 shows imma-
ture organic matter in all the studied rocks. The liptinite
content of the organic matter varies between 50 and
95% and it exceeds 70% for most of the samples. Vitri-
nite and inertinite are subordinate to liptinite through-
out the studied sequence, indicating the low
contribution of higher plant derived material. Liptinites
are composed of laminated alginite, solitary planktonic
algae and colonies of tubular algae. Preservation of the
organic matter is generally good. The amount of amor-
phinite formed by the decomposition of the observed
liptinites (solitary algae and laminated alginite) varies
between 0 and 35% (Table 2). Rock Eval pyrolysis
reveals that the entire sequence contains immature type
II kerogen; Tmax ranges from 410 to 420  C for all but
one sample (Table 3). TOC content and HI values range
from 0.23 to 4.12% and from 419 to 827 mg HC/g TOC,
respectively (Table 3, Fig. 3). The elementary composi-
tion of kerogens shows sulphur-rich organic matter and
S/C values exceed 0.04 throughout the studied sequence
(Table 4). More negative carbon isotope ratios were
measured on the samples taken from the upper and
lower parts of the sequence than on samples represent-
ing the middle section (from 352 m to 319 m depth)
(Table 4). A similar trend appears in bitumen ratios and
asphaltene contents of the extracts, the smallest values of
which are found in the middle section of the succession
(Table 5, Fig. 5). Extracts contain a high proportion of

Table 2
Maceral composition (%) of the selected samples

Formation Depth (m) Maceral classes Liptinite composition

Vitr. Inert. Lipt. Amor. Lam.a. Sol.a. Tub.a.

Rzt-1 well
Kössen (Rhaetian) 95.2 1.0 10.0 84.0 5.0 47.8 32.0 0.0
105.2 1.0 6.0 88.0 5.0 52.3 34.8 0.0
113.5 1.0 6.0 84.0 9.0 8.4 75.6 0.0
132.3 1.0 2.0 87.0 10.0 34.8 52.2 0.0
139.2 3.0 4.0 78.0 15.0 66.2 11.8 0.0
144.3 0.0 2.9 97.0 0.1 3.8 90.3 0.0
151.5 45.0 5.0 40.0 10.0 2.0 18.0 20.0
168.0 3.9 1.0 95.0 0.1 85.5 9.5 0.0
170.0 0.1 1.0 97.0 1.9 90.2 6.8 0.0
178.8 2.0 1.0 85.0 12.0 34.0 51.0 0.0
185.9 0.1 1.0 97.0 1.9 1.0 96.0 0.0

Kössen (Norian) 207.5 12.0 3.0 83.0 2.0 16.6 58.1 8.3
224.9 2.0 2.0 94.0 2.0 4.7 32.9 56.4
236.0 2.0 7.0 87.0 4.0 8.7 69.6 8.7
241.0 2.0 1.0 75.0 22.0 41.2 26.3 7.5

Zl-1 well
Kössen (Norian) 307.0 1.0 2.0 89.0 8.0 82.7 6.3 0.0
313.3 15.0 10.0 67.0 8.0 40.2 26.8 0.0

Transitional 314.3 0.0 5.0 94.5 0.5 86.0 8.5 0.0

317.4 0.0 8.0 82.0 10.0 24.6 57.4 0.0
318.7 2.0 8.0 86.0 4.0 8.6 77.4 0.0
321.5 0.0 4.0 95.0 1.0 0.0 28.5 66.5
340.7 0.0 1.0 84.0 15.0 79.8 0.0 4.2
347.9 1.0 5.0 59.0 35.0 47.2 11.8 0.0
352.0 10.0 28.0 50.0 5.0 5.0 45.0 0.0
360.0 4.0 10.0 71.0 2.0 2.1 22.7 46.2
363.0 2.0 5.0 87.0 1.0 0.0 87.0 0.0

Rezi Dolomite 378.5 0.0 10.0 85.0 2.0 1.7 83.3 0.0
381.4 0.0 5.0 88.0 0.0 70.4 17.6 0.0
383.0 0.0 1.0 76.0 15.0 15.2 7.6 53.2
386.0 0.0 10.0 87.0 0.0 0.0 87.0 0.0

Samples below 352.0 m contain also 3–13% migrabitumen. Liptinites composed of laminated alginites (Lam.a.), solitary alginites
(Sol.a.) and tubular alginites (Tub.a.). Samples from 95.2, 105.2 and 144.3 contain 4.2, 0.9 and 2.9% sporinite, respectively.
 M. Hetényi et al. / Organic Geochemistry 33 (2002) 1571–1591 1577

Table 3
Some bulk Rock Eval data measured on whole rock samples

Formation Depth (m) TOC (%) Tmax ( C) SI S2 HC-pot. P1 HI

Rzt-1 well
Kössen (Rhaetian) 82.5 0.9 422 0.04 2.20 2.24 0.02 244
95.2 1.4 421 0.11 3.47 3.58 0.03 248
105.2 2.7 421 0.22 11.04 11.26 0.02 409
113.5 1.9 421 0.11 4.83 4.94 0.02 254
132.3 3.8 417 1.75 17.17 18.92 0.09 452
139.2 3.1 418 0.55 19.75 20.30 0.03 637
144.3 2.5 420 0.95 12.81 13.76 0.07 512
151.5 7.3 411 2.68 46.36 49.04 0.05 635
168.0 14.6 403 5.58 110.66 116.24 0.05 758
170.0 6.1 410 1.37 44.56 45.93 0.03 731
178.8 2.3 407 0.38 11.76 12.14 0.03 511
185.9 1.6 419 0.13 4.40 4.53 0.03 275

Kössen (Norian) 207.5 4.6 402 2.49 38.34 40.83 0.06 833
224.9 6.2 402 4.99 49.46 54.45 0.09 798
236.0 5.1 391 1.72 35.05 36.77 0.05 687
241.0 6.8 393 6.49 50.73 57.22 0.11 746

Zl-1 well
Kössen (Norian)
304.9 0.95 403 0.32 6.47 6.79 0.05 681
307.0 2.79 416 1.34 18.35 19.69 0.07 657
312.6 0.66 418 0.27 5.03 5.30 0.05 762
313.3 2.33 417 0.68 13.59 14.27 0.05 583
313.9 1.36 412 0.20 8.52 8.72 0.02 626

Transitional 314.3 0.23 410 0.14 1.10 1.24 0.11 478

317.4 2.07 415 0.91 17.12 18.03 0.05 827
318.4 4.12 416 1.62 21.79 23.41 0.07 528
318.7 0.83 412 0.20 4.48 4.68 0.04 540
319.0 2.76 419 0.83 20.26 21.09 0.04 734
319.3 1.10 420 0.29 6.38 6.67 0.04 580
320.2 1.53 420 0.39 9.64 10.03 0.04 630
321.5 0.28 416 0.23 1.53 1.76 0.13 546
340.7 1.41 418 0.24 6.88 7.12 0.03 487
341.5 0.24 412 0.20 1.58 1.78 0.11 658
347.6 2.11 410 0.41 12.59 13.00 0.03 596
347.9 2.66 418 0.50 13.59 14.09 0.04 510
348.7 0.61 414 0.11 3.11 3.22 0.03 509
352.0 2.00 410 0.43 10.04 10.47 0.04 502
354.8 2.11 411 0.45 8.86 9.31 0.05 419
360.0 1.98 417 0.65 12.63 13.28 0.05 537
363.0 2.06 418 0.50 10.83 11.33 0.04 525

Rezi Dolomite 373.5 1.56 411 0.28 8.63 8.91 0.03 553
373.9 4.01 411 0.93 24.44 25.37 0.04 609
374.3 1.07 410 0.40 6.17 6.57 0.06 577
378.5 2.09 415 0.58 10.65 11.23 0.05 510
381.4 2.98 414 0.40 15.02 15.42 0.02 504
383.0 2.45 415 0.67 11.98 12.65 0.05 489
386.0 0.72 413 0.10 3.27 3.37 0.02 454

Parameter dimensions are SI, S2 and HC-pot. (mg HC/g rock), HI (mg HC/g TOC). TOC and HI values for Rzt-1 well have been
published by Vetć´ et al. (2000).
1578 M. Hetényi et al. / Organic Geochemistry 33 (2002) 1571–1591

Table 4
H/C, S/C atomic and carbon isotope ratios of kerogens. Carbon Preference Index (CPI), pristane/phytane, n-C22/n-C23+ and pen-
tamethyleicosane/n-docosane (i-C26/n-C22) ratios calculated from GC analysis of the saturated hydrocarbon fraction of bitumen

Formation Depth (m) d13C (per mil) H/C S/C CPI Pr/Ph n-C22 i-C26
n-C23þ n-C22

Rzt-1 well
Kössen (Rhaetian) 82.5 29.32 1.20 0.06 1.58 0.18 0.81 2.24
95.2 28.88 1.18 0.08 1.75 0.16 0.76 0.45
105.2 30.29 1.22 0.02 1.94 0.21 0.53 0.77
113.5 29.63 1.28 0.10 1.98 0.24 1.10 1.12
132.3 30.10 1.29 0.09 1.34 0.41 6.00 0.41
139.2 29.82 1.25 0.11 1.96 0.31 1.48 0.35
144.3 30.89 1.32 0.05 1.44 0.46 3.82 0.21
151.5 28.35 1.35 0.05 2.87 0.20 0.53 2.19
168.0 28.97 1.37 0.05 1.91 0.22 0.20 0.87
170.0 28.86 1.36 0.06 1.93 0.23 0.33 0.79
178.8 29.38 1.32 0.07 1.88 0.17 0.38 1.09
185.9 29.18 1.27 0.07 2.06 0.30 0.56 0.71

Kössen (Norian) 207.5 28.75 1.39 0.09 2.10 0.31 0.24 1.59
224.9 29.63 1.39 0.09 1.50 0.23 0.04 1.08
236.0 31.27 1.39 0.11 1.69 0.38 0.11 0.37
241.0 30.31 1.45 0.09 1.60 0.21 0.31 1.27

Zl-1 well
Kössen (Norian) 304.9 30.71 1.35 0.09 n.d. n.d. 0.30 n.d.
307.0 30.09 1.43 0.12 1.55 0.51 0.36 0.57
312.6 29.08 1.24 0.08 n.d. n.d. 0.33 n.d.
313.3 31.11 1.29 0.10 1.22 0.70 0.31 0.48

Transitional 314.3 28.76 1.10 0.19 1.30 0.09 0.84 0.44

317.4 30.35 1.42 0.07 1.72 0.42 0.32 0.62
318.7 29.58 1.22 0.11 1.01 0.30 0.49 0.50
319.0 29.70 1.36 0.08 n.d. n.d. n.d. n.d.
321.5 28.52 1.12 0.05 1.23 0.10 0.80 0.56
340.7 27.87 1.17 0.08 1.08 0.30 0.58 0.67
341.5 28.52 1.15 0.09 n.d. n.d. n.d. n.d.
347.9 28.96 1.10 0.07 1.14 0.65 0.50 0.54
352.0 28.05 1.21 0.08 0.96 0.23 1.32 0.23
360.0 29.17 1.30 0.08 0.97 0.25 1.25 0.35
363.0 28.83 1.14 0.07 1.34 0.22 0.98 0.45

Rezi Dolomite 373.9 29.75 1.35 0.07 n.d. n.d. n.d. n.d.
378.5 30.00 1.20 0.10 1.13 0.37 1.52 0.31
381.4 29.31 1.22 0.08 1.07 0.28 1.42 0.30
383.0 28.67 1.14 0.08 1.17 0.49 2.15 0.30
386.0 29.82 1.24 0.08 1.05 0.25 0.80 0.47

n.d.=not determined.

heteroatomic compounds;
NSO values are higher than
82.0% for all of the studied samples. The ratio of the
saturated and aromatic hydrocarbons varies in a 0.28-
2.81 range (Table 5). The gas chromatograms of the
saturated hydrocarbon fractions show an odd-over-even
predominance in n-alkane distribution. The pristane/
phytane ratios are low, ranging between 0.09 and 0.86.
The ratio of 2,6,10,15,19-pentametileicosane (an irre-
gular tail-to-tail linked acyclic C25 isoprenoid) to n-
docosane is low ( <0.7) for the entire succesion (Table 4).
Results of GC/MS analysis of saturated hydrocarbon
fractions of bitumens are summarized in Table 8.
Rocks taken from well Rzt-1 are mineralogically
more heterogenous than rocks taken from well Zl-1.
Not only dolomite but calcite and aragonite also con-
tribute to carbonate minerals. The samples contain less
than 17% dolomite and the amount of calcite and ara-
gonite ranges from 18 to 75% and from 1 to 26%,
 M. Hetényi et al. / Organic Geochemistry 33 (2002) 1571–1591 1579

Table 5
Ratio and composition of bitumen

Formation Depth (m) Bitumen (mg/gTOC) A (%) R (%)
NSO (%) HCsat (%) HCar (%) SHC
SNSO

Rzt-1 well 82.5 64 5.9 71.2 77.1 17.8 5.1 0.30

Kössen (Rhaetian) 95.2 65 7.6 72.9 80.5 13.5 6.0 0.24
105.2 45 15.7 67.8 83.5 10.7 5.8 0.20
113.5 42 11.4 63.3 74.7 18.0 7.3 0.34
132.3 131 6.2 47.9 54.1 38.2 7.7 0.85
139.2 41 14.2 49.3 63.5 27.6 8.9 0.58
144.3 74 5.8 39.6 45.4 47.6 7.0 1.20
151.5 93 6.3 54.0 60.3 27.7 12.0 0.66
168.0 132 16.7 53.3 70.0 14.1 15.9 0.43
170.0 67 9.2 57.3 66.5 20.6 12.9 0.50
178.8 73 9.7 63.3 73.0 16.4 10.6 0.37
185.9 51 14.6 60.9 75.5 17.7 6.8 0.32

Kössen (Norian) 207.5 189 29.4 53.0 82.4 8.7 8.9 0.21
224.9 214 24.5 55.0 79.5 10.1 10.4 0.26
236.0 121 18.0 54.9 72.9 8.4 18.7 0.37
241.0 205 23.9 51.9 75.8 8.2 16.0 0.32

Zl-1 well
Kössen (Norian) 304.9 140 27.2 55.5 82.7 5.9 11.4 0.21
307.0 125 27.7 61.0 88.7 6.8 4.5 0.13
312.6 121 54.6 34.6 89.2 2.4 8.4 0.12
313.3 118 41.5 49.7 91.2 3.7 5.1 0.10

Transitional 314.3 78 30.5 55.8 86.3 10.1 3.6 0.16

317.4 186 40.1 49.4 89.5 2.6 7.9 0.12
318.7 62 33.9 48.7 82.6 9.7 7.7 0.21
321.5 64 19.8 66.6 86.4 7.6 6.0 0.16
340.7 55 31.5 57.9 89.4 5.8 4.8 0.12
347.9 64 35.6 52.9 88.5 2.5 9.0 0.13
352.0 64 41.6 52.3 93.9 2.7 3.4 0.06
360.0 124 51.0 45.4 96.4 1.5 2.1 0.04
363.0 53 41.9 53.1 95.0 2.6 2.4 0.05

Rezi Dolomite 378.5 91 49.6 45.7 95.3 2.7 2.0 0.05

381.4 105 55.3 41.5 96.8 1.0 2.2 0.03
383.0 112 51.4 44.8 96.2 1.8 2.0 0.04
386.0 71 50.5 41.1 91.6 6.1 2.3 0.09

A, asphaltene; R, resin.

respectively. They also contain quartz of 4–28%. More-
over, besides carbonates and quartz, clay minerals are
also present in essential amount ranging between 8 and
54% (Table 1). Organic matter is dominated by liptinite
(Table 2). Except for one sample (151.5 m depth), lipti-
nite content ranges from 75 to 97% and it exceeds 80%
for most of the samples. The amount of vitrinite is low,
less than 4.0% in all but two samples. A small amount
of sporinite, indicating land-derived organic matter, was
observed only in some samples (185.9, 168.0, 139.2 m
depth) of the Rhaetian Kössen Fm. Vitrinite reflectance
ranging between 0.30 and 0.36% Ro indicates immature
organic matter. Tmax values, measured on whole rock
samples, varying from 391 to 422  C (Table 3) also cor-
respond to the stage of diagenesis. Rock Eval data and
the elementary composition of kerogens display more
variations in the organic matter in well Rzt-1, than in
well Zl-1. TOC and HI values range from 0.9 to 14.6%
and from 244 to 833 mg HC/g TOC, respectively
(Table 3, Fig. 4). H/C ratios vary from 1.18 to 1.45 and
S/C ratios ranging between 0.05 and 0.11 for all but
one sample (Table 4) show the presence of type I-II-S
and type II-S kerogen as defined by Orr (1986) and di
Primio and Horsfield (1996). Carbon isotope ratios of
kerogens vary between 31.27 and 28.35 per mil.
Bitumen ratios range over a wide interval between 41 and
 1580
M. Hetényi et al. / Organic Geochemistry 33 (2002) 1571–1591
Fig. 4. Vertical profile of the amount of carbonate minerals, organic carbon content and hydrogen index measured on whole rock samples, as well as carbon isotope and S/C ratios
measured on kerogens in well Rzt- 1.
 M. Hetényi et al. / Organic Geochemistry 33 (2002) 1571–1591 1581

Table 6  of the two formations (Rezi Dolomite Fm. and

Py-GC-indices of kerogens isolated from the samples of Rzt-1 Kössen Fm.),
well  of the two boreholes (Zl-1 and Rzt-1) located at
different positions on the slope,
Formation Depth o/x phenol tol/mthio Tpr/t17
 for basin, slope and toe-of-slope facies.
(rel%)

Kössen (Rhaetian) 82.5 1.11 30 1.48 0.57 Mineral and organic composition of the studied suc-
95.2 0.84 37 1.47 0.50 cessions are compared on the basis of data measured on
105.2 1.07 39 1.34 0.57 individual samples (Tables 1–6 and 8, Figs. 3–7) and on
113.5 1.04 27 1.51 0.31 the basis of average values of data (Table 7) calculated
132.3 1.30 25 1.27 0.44 for selected samples (see Table 5).
139.2 0.65 9 1.11 0.77
144.3 0.82 7 1.15 0.43
151.5 0.63 12 1.10 0.90
4.1. Comparison of the two formations (well Zl-1).
168.0 0.50 13 0.49 1.34
170.0 1.06 20 0.79 0.86 The high amount of carbonate minerals (more than
178.8 1.02 11 0.77 0.84 90% on average, Table 7) reveals the predominance of
185.9 1.07 9 0.96 0.70 platform-derived input in both of the Kössen Fm. and
the Rezi Dolomite Fm. penetrated by well Zl-1. The
Kössen (Norian) 207.5 0.40 29 0.46 1.63 essentially smaller proportion of dolomite (less than one
224.9 0.63 15 0.33 1.55 third of carbonate minerals) indicates an incomplete
236.0 0.78 20 0.42 1.05 dolomitization of the Kössen Fm. Based on the results
241.0 0.47 12 0.33 1.37
of previous work, the observed change in the miner-
o/x: n-octene/(m+p)xylene; phenol: normalised on the basis of alogy of the sequence is interpreted as a response to

n-octene+(meta- and para-)xylenes+phenol contents in pyr- change of climate (Schmalz, 1969; Hans, 1998; Balog et
olysate; tol/mthio: toluene/2-methylthiophene; Tpr/T17: al., 1999). The semi-arid climate existing during the for-

prist-1-ene+prist-2-ene+pristane/
n-heptadecane+n-hepta- mation of the Rezi Dolomite sequence, deposited in a
decene. deep basin environment, was favourable for early
diagenetic dolomitization of carbonate sediments.
Throughout the period of a permanent evaporation,
214 mg/g TOC. They are higher than 120 mglg TOC for chemical reactions occurring in the water column and at
the Norian Kössen sequence and lower than 93 mg/g the basin floor increase the ratio of Mg2+/Ca2+ result-
TOC for most of the Rhaetian Kössen samples. Pyr- ing in the dolomitization of carbonate minerals
olysates of kerogen concentrates are dominated by an (Schmalz, 1969; Haas, 1998). The more limited dolomi-
alkene and alkane homologous series ranging from C2 tization of the Kössen carbonate minerals reflects a
to C29 with a varying unresolved ‘‘naphtenic hump’’ in cooler and humid climate. It is supported by d18O sig-
the diterpenoid range. Pyrochromatograms show abun- natures, determined by Balog et al. (1999), which reflect
dant C1–C2 alkylated benzenes and thiophenes. A lower the influence of meteoric water and less evaporation
abundance of phenols, naphtalene and methylnaphta- during the latest Norian-Rhaetian deposition. The
lenes is also observed. Isoprenoid hydrocarbons are cooler and humid climate led to more intensive weath-
represented dominantly by prist-1-ene and a relatively ering, which increased the platform-derived input, and
lower proportion of norpristane, prist-2-ene, pristane and led to the inhibition of a pervasive dolomitization.
phytane. The ratios calculated from the relative abun- The change in the paleoenvironmental conditions can
dance of various compounds in kerogen pyrolysates be recognized not only in the mineralogical but in the
(Table 6) display cyclic variations as a function of depth. organic geochemical data, too. The low pristane/phy-
The distributions of steranes (m/z 217 mass chromato- tane ratios ( < 1, Table 7) are consistent with the con-
grams) are shown in Fig. 7. tinuous existence of anoxic conditions and/or high
salinity during the deposition of the sequence (Brooks et
al., 1969; Didyk et al., 1978; Chappe et al., 1980; Bor-
4. Discussion denave, 1993). Low values of this ratio may reflect sali-
nity-dependent growth rate of halophilic bacteria
According to Rock Eval pyrolysis, organic petrography containing phytanyl lipids, which are a source for phy-
and carbon isotope ratios, the organic matter is imma- tane (Goossens et al., 1984). Different average values of
ture and of predominantly marine origin throughout this ratio (0.34 and 0.60 for the Rezi Dolomite and the
both the Zl-1 and Rzt-1 boreholes. Variations are observed Kössen Fm., respectively) can be attributed to a slightly
in the mineral composition and in the organic geochemical more saline environment during the deposition of the
features Rezi Dolomite Fm. than during that of Kössen Fm. The
 1582
M. Hetényi et al. / Organic Geochemistry 33 (2002) 1571–1591
Fig. 5. Vertical profile of dolomite content and bitumen composition [asphaltene content, the ratio of hydrocarbons relative to heteroatomic compounds (
HC/
NSO), the ratio of
saturated hydrocarbons to aromatic hydrocarbons (HCsat/HCar) and the proportion of lighter n-alkanes to heavier ones (n-C22-/n-C23+)] in well Zl-1.
 M. Hetényi et al. / Organic Geochemistry 33 (2002) 1571–1591
Fig. 6. Vertical profile of the amount of carbonate minerals and bitumen composition [asphaltene content, the ratio of hydrocarbons relative to heteroatomic compounds (
HC/

NSO), the ratio of saturated hydrocarbons to aromatic hydrocarbons (HCsat/HCar) and the proportion of lighter n-alkanes to heavier ones (n-C22-/n-C23+)] in well Rzt-1.

1583
1584 M. Hetényi et al. / Organic Geochemistry 33 (2002) 1571–1591

Fig. 7. Partial mass chromatograms (m/z 217) of the saturated hydrocarbon fractions of bitumens from selected samples of the Rzt-1
well. A: 132.3 m, B: 178.8 m, C: 241.0 m. The carbon numbers and isomers at C-20 of 5a,14a,17a(H) steranes are denoted.

lack of vitrinite reveals that higher plant-derived organic
matter is scarce in the Rezi Dolomite Fm. The presence
of vitrinite displays a minor land-derived contribution
for samples taken from the Kössen Fm. This observa-
tion is confirmed by the composition of the extracts and
by GC and GC/MS analyses of the saturated hydro-
carbon fractions of bitumens. The smaller proportion of
the short-chain n-alkanes to the long-chain ones and a
slightly higher odd-over-even carbon predominance
(calculated according to Bray and Evans, 1961, in the
 M. Hetényi et al. / Organic Geochemistry 33 (2002) 1571–1591 1585

Table 7
Average values of mineral and organic data calculated for samples selected for detailed examination
SHC HCsat n-C22btl
Formation Depth (m)
CO3 D Q Clay TOC HI d13C H/C S/C Bit. A R
NSO SNSO HCar n-C23þ Pr/Ph CPI

Rzt-1 well
Kössen (Rhaetian) B 82.5 88 17 4 8 0.9 244 29.3 1.20 0.06 64 5.9 71.2 77.1 0.30 3.5 0.8 0.18 1.58
TS 95–139 40 4 15 42 2.5 341 29.7 1.24 0.07 71 10.2 63.0 73.2 0.41 2.9 2.1 0.26 1.75
B 139–145 73 10 9 16 2.8 575 30.4 1.29 0.08 58 10.0 44.5 55.5 0.89 5.0 2.7 0.38 1.70
TS 145–170 46 2 20 32 9.3 708 28.7 1.36 0.05 97 11.0 54.9 65.9 0.53 1.6 0.3 0.21 2.24
B 170–190 69 11 9 21 2.0 393 29.3 1.30 0.07 62 12.2 62.1 74.3 0.35 2.1 0.5 0.24 1.97

Kössen (Norian) TS 190–241 71 4 10 16 5.7 766 30.0 1.40 0.10 182 24.0 53.7 77.7 0.58 0.7 0.2 0.28 1.72

Zl–1 well
Kössen (N.) S 304–314 91 27 6 1 1.7 671 30.2 1.33 0.10 126 37.8 50.2 88.0 0.14 0.8 0.3 0.60 1.39

Transitional S 314–319 91 61 7 – 1.0 615 29.6 1.25 0.12 124 34.8 51.3 86.1 0.16 1.5 0.6 0.48 1.34
B 319–348 70 70 28 1 1.5 514 28.5 1.13 0.07 61 29.0 59.1 88.1 0.14 0.8 0.6 0.35 1.15
B 348–363 88 88 9 1 2.0 521 28.7 1.22 0.08 80 44.8 50.3 95.1 0.05 0.9 1.2 0.23 1.09

Rezi Dol. B 363–386 92 91 8 – 2.5 528 29.5 1.23 0.08 95 51.7 43.3 95.0 0.05 1.4 1.5 0.34 1.10

13

CO3, D (dolomite), Q (quartz), Clay, TOC, A (asphaltene), R (resin),
NSO:%, HI: mg HC/gTOC, d C: %, Bit. (bitumen ratio): mg/g TOC. B:
carbonate-rich basin facies, S: slope facies, TS: toe-of-slope facies.

C22–C32 range) also reveal a slightly higher land-derived
contribution in the Kössen Fm. than in the Rezi Dolo-
mite Fm. (Tables 4 and 7). This is in agreement with the
distribution of steranes (calculated from their mass
spectra, m/z 217) displaying the proportion of algal to
higher plant input (Table 8). The presence of hopanoid
hydrocarbons ranging from C27 to C35, identified on the
basis of their mass spectra, is generally considered to
show bacterial contribution. However, the ratio of
hopanes to steranes may reflect the relative contribution
of higher plants and bacteria to algae (Peters and Mol-
dowan, 1993). As a consequence, the somewhat higher
values of this ratio indicate a slightly lower relative
proportion of the algal precursor material in the Kössen
Fm. The facies ratios (h27/h30 and h29/h30) calculated
on the basis of mass chromatograms (m/z 191) also
exhibit some differences between the organic facies of
these sequences (Table 8). Conversely, samples from the
Kössen Fm. display lower average TOC and higher
average HI, H/C and S/C values than samples from the
Rezi Dolomite Fm. Average HI values and H/C ratios
are 528 mg HC/gTOC and 1.23 for the Rezi Dolomite
Fm. and 671 mg HC/gTOC and 1.33 for the Kössen
Fm. (Table 7). We think that the different hydrogen
contents is a consequence of the different preservation
conditions rather than of the minor terrestrial input in
the Kössen Fm. The increased mineral supply due to the
more intensive weathering decreased the proportion of
the organic matter in the sediment. Moreover, due to
the greater abundance of minerals, the sedimentation
rate increased, promoting the better preservation of the
organic matter and resulting in higher hydrogen content
in the Kössen Fm.
The transitional nature of the sequence between 363
and 314 m depth in well Zl-1 is manifested both in its
mineral and organic compositions. The measured
organic geochemical data primarily vary as a function of
the mineralogical composition of the rocks (Figs. 3 and
5). The complete dolomitization of carbonate sediments
throughout most of the transitional sequence (from 319
to 363 m depth) indicates that no essential change of
climate occurred during their deposition. As the
appearance of calcite (Table 1) reveals, the climate
became humid probably at the times of the deposition
of the uppermost transitional section (314–319 m
depth), near the border of the Kössen Fm. The upward
decrease in the amount of dolomite in the main part of
the transitional sequence (between 319.3 and 348 m
depth), in which dolomite is the only carbonate, is
compensated by the increasing amount of quartz. Aver-
age values of H/C ratios (Table 8) for samples taken
from this sequence (H/C: 1.13) are smaller than for
samples taken from other sections of the Zl-1 well (H/
C > 1.2). GC (
HC/
NSO, n-C22-/n-C23+) and GC/
MS data (distribution of steranes and hopane/sterane
ratio) of the saturated hydrocarbon fractions of bitu-
mens suggest a relatively greater abundance of bacterial
and higher plant input in this sequence (Tables 7 and
8). In addition, the increased amount of amorphinites
(Table 2), which are regarded as derived from bacterial
decomposition of liptinites (Köster et al., 1988), reflects
an increased bacterial activity. On the basis of the
pentamethyleicosane/n-docosane ratios, the methano-
genic bacterial activity is moderate in the entire Zl-1
borehole and especially moderate in the dolomite-rich
section.
1586 M. Hetényi et al. / Organic Geochemistry 33 (2002) 1571–1591

Table 8
Ratios calculated from (m/z 217 and m/z 191) mass chromatograms of the saturated hydrocarbon fractions of the bitumen extracted
from selected samples
C27 R C29 S mor: hop30 h27 h29
Formation Depth (m) C30R C29 R C29 SþR hop: stC27 RþS h30 h30

Rzt-1 well
Kössen (Rhaetian) 132.3 6.3 1.05 28 0.26 0.23 0.44 0.18
168.0 11.6 1.52 22 0.28 0.71 0.09 0.04
178.8 11.8 1.08 25 0.19 0.51 0.10 0.08

Kössen (Norian) 207.5 10.0 1.34 25 0.19 0.71 0.16 0.12

241.0 8.4 1.66 27 0.36 0.38 0.66 0.20

Zl-1 well
Kössen (N.) 313.3 11.5 0.78 29 0.16 2.15 0.59 0.62

Transitional 318.7 8.8 0.68 33 0.13 5.03 0.53 0.56

340.7 10.3 0.72 35 0.16 3.14 0.83 1.23

Rezi Dolomite 386.0 3.9 1.24 54 0.17 1.45 0.72 0.94

Distribution and relative proportion of the C27–C30 20R 5a,14a,17a(H) steranes: C30R, C27R/C29R. The configurational isomerization
ratios: moretane/hopane (mor./hop.) and 20S 5a,14a,17a(H) C29-sterane/20S 5a,14a,17a(H) C29 sterane+20R 5a,14a,17a(H) C29
sterane (C29S/C29S+R). Hopanes/steranes (hop30/stC27R+S): C30 17a,21b(H) hopane in m/z 191 chromatograms/C2720R and 20S
5a,14a,17a(H) cholestane in m/z 217 chromatograms. Facies-ratios: C27 17a(H)22,29,30trisnorhopane/C30 17a,21b(H) hopane (h27/
h30) and C29 17a,21b(H) norhopane/C30 17a,21b(H) hopane (h29/h30) in m/z 191 chromatograms.

4.2. Variations in the mineral and organic composition
of the studied successions related to their position on the
slope
The mineral composition and the organic geochem-
ical characteristics of the two studied successions vary as
a function of their position on the slope (Fig. 2). The
two time-equivalent sections—namely the Norian Kös-
sen sequence of the well Rzt-1 (toe-of-slope facies) and
the topmost sequence (between 319 and 304 m depth) of
the well Zl-1 (slope facies)—are compared.
The four times higher organic carbon content
(Table 7, Figs. 3 and 4) in the toe-of-slope facies (well
Rzt-1) can be attributed to the higher organic input and
the better preservation of the organic matter here. The
presence of clay minerals is probably, at least in part,
responsible for the higher amount of the organic matter
in Rzt-1 well. Adsorption of the organic matter on clay-
surfaces and the formation of organo-mineral com-
pounds promoted its preservation during deposition and
in recent sediment.
Both the mineral composition and the results of
the organic geochemical and petrographic analyses
reveal a complex mixture of precursors at the toe of
the slope. The appearance of clay minerals (16% on
average, Table 7) reflects the relatively increased land-
derived contribution. According to the petrographic
observations, benthic algae (indicating by the presence
of the remnants of tubular algae) also contributed to the
organic matter (Table 2). Bitumen composition and the
gas cbromatoghraphic data of the saturated hydro-
carbon fractions supported the heterogenity of the
organic matter. The higher ratios of hydrocarbons rela-
tive to heteroatomic compounds, the slightly more aro-
matic compounds and the decreased proportion of
lighter n-alkanes to heavier ones display a higher, but
moderate, higher plant-derived contribution to sedi-
mentary rocks deposited at the lowest part of the ramp.
The slightly stronger predominance of the odd-over-
even carbon numbered n-alkanes (CPI: 1.72 and 1.36,
respectively) can reflect a slightly higher terrestrial
input, with long-chain n-alkanes derived from cuticular
waxes of higher plants (Tissot and Welte, 1984). An
algal origin for these alkanes has also been reported.
Lichtfouse et al. (1994) pointed out that such a type of
n-alkanes can be produced by the diagenetic reduction
of Botryococcus braunii alkadienes and alkatrienes.
Based on maceral composition and the composition of
kerogen pyrolysates, the terrestrial origin seems to be
more likely: the highest relative phenol content and the
lowest ratio of n-octene/(m+p)xylene in the kerogen
pyrolysates (Table 6) in agreement with the highest CPI
value were determined for that sample (207.5 m depth)
which contains the highest amount of vitrinite (Table 1)
in the Norian Kössen sequence penetrated by the Rzt-1
borehole. This observation is confirmed by the dis-
tribution of steranes calculated from the mass spectra
of the saturated hydrocarbon fractions of bitumens.
The C27R/C29R ratios are 1.34 and 1.66 for samples
whose organic matter contains 12% (207.5 m depth)
and 2% (241.0 m depth) vitrinite, respectively (Tables 2
and 8).
 M. Hetényi et al. / Organic Geochemistry 33 (2002) 1571–1591
Nevertheless, the distribution of steranes reveals a
greater abundance of algal-derived contribution in rocks
deposited at the toe of the slope than in those deposited
on the slope. It is consistent with the elementary com-
position of kerogens and HI values indicating type I-II-
S and type II-S kerogens in the toe-of-slope and slope
facies, respectively. The varying, but relatively minor,
contribution of the higher plant remnants, manifested in
bitumen composition, could not modify the HI values,
which are determined by the significantly higher pro-
portion of the well-preserved marine organic matter.
Previous geochemical studies have described a clear
correlation between the degree of the organic matter
preservation and HI values. This dependence is char-
acteristic mainly of rocks containing predominantly
sulphur-rich marine kerogen (Lallier-Verges et al.,
1993; Vetó´ et al., 1994). The sedimentation rate was
probably the major factor controlling the preservation
of the organic matter. The lowest part of the ramp is
a favourable place for the rapid deposition of plat-
form-derived and land-derived minerals in large
quantity. Clay minerals are also believed to have an
important role in the preservation and diagenesis of
organic matter. The more limited dolomitization of
carbonate minerals in the toe-of-slope facies than slope
facies can also be attributed to the higher platform-
derived input.
The strongly anoxic depositional environment is, at
least partly, due to the high amount of the organic pre-
cursors accumulated at the lowest part of the ramp. It is
shown by the extremely low pristane/phytane ratios and
by the high pentamethyleicosane to n-docosane ratios.
The significantly higher ratios of pentamethyleicosane
to n-docosane (except one sample) exhibit higher
methanogenic bacterial activity in the Norian Kössen
sequence of the Rzt-1 borehole than in that of the Zl-l
borehole. The 2,6,10,15,19-pentamethyleicosanyl skele-
ton suggests that the alkane in marine sediments may
derive from methanogens (Brassell et al., 1980; Chappé
et al., 1980). The presence of 2,6,10,15,19-pentamethy-
leicosane in immature sediments is evidence for archae-
bacterial origin (Risatti et al., 1984).
The configurational isomerization ratios (such as
moretane/hopane and C29S/C29S+R: isomerization at
C-20 in 5a,14a,17a(H) C29-steranes) are often con-
sidered to be maturity-dependent. Variability within
these rocks, containing immature organic matter, can be
related partly to phenomena such as facies control or
different rates of isomerization on mineral surfaces.
Horsfield et al. (1994) suggested that moretane/hopane
epimerisation was controlled by acidic catalytic activity
which was higher in the less saline shale section than in
that deposited under strongly alkaline conditions (dolo-
mitized section). We observed the opposite phenom-
enon, the two isomerisations being more complete in the
dolomite rich section than in the less saline section.
1587
Consequently, another factor played the controlling role
in isomerization.
4.3. Influence of sea-level changes
Significant variations were observed both in the
mineral composition and the organic geochemical data
of the Kössen Fm., penetrated by the Rzt-1 borehole.
These variations can be interpreted by fluctuations in
sea-level. The studied sequence represents the transgres-
sive part of a third order cycle. Sedimentological analy-
sis reveals that the Late Norian toe-of-slope facies is
overlain by Rhaetian deeper basin facies (Haas and
Budai, 1995). The bulk organic geochemical data show
two organically different intervals below and above
about 190 m depth, which is considered as the Norian/
Rhaetian boundary (Oravecz and Scheffer, 1987). Rock
Eval data (Table 3) together with the elemental compo-
sition of kerogens (Table 4) reveal type I-II-S and type
II-S kerogen in the Norian and Rhaetian sequence,
respectively.
However, varying mineral composition of the succes-
sion displays repeatedly varying platform-derived and
land-derived input during deposition. It is attributed to
the high-frequency fourth order cycles (100 ka) which
were superimposed on the third order cycle (Haas,
1993). A similar effect of the short-term sea-level fluc-
tuations was published for the Pliocene of the Bahamas.
The sediments at the toe-of-slope of the Bahamas have
been shown to be influenced by the differences in plat-
form productivity during glacials and intergiacials
(Droxler and Schlager, 1985; Reijmer et al., 1988;
Westphal, 1998). The platform-derived input probably
culminated during high-stand phases when a large part
of the platform was covered by shallow water and the
area of the carbonate production extended. The rela-
tively higher transport of land-derived material occurred
during lowstand phases (Schlager, 1992).
Organic matter originated mainly from marine pre-
cursors throughout the Rzt-1 borehole but geochemical
data measured indicate minor differences in the organic
source material of the basin and toe-of-slope facies.
Most of the data reveal that long-term and short-term
low-stand phases resulted in similar organic features for
two toe-of-slope facies (from 190 to 240 and from 140 to
170 m depth). The highest CPI (Table 4) and d13C
values (Fig. 4) together with the highest vitrinite content
(Table 2) reveal the highest land-derived input for the
top of these toe-of-slope facies represented by the sam-
ples taken from 207.5 and 151.5 m depth. Nevertheless,
the GC/MS analysis of the saturated hydrocarbon frac-
tion of the extracts reveals a great abundance of algal-
derived organic matter for the entire succession and
reflects its highest contribution in the toe-of-slope facies.
The distributions of steranes (m/z 217 mass chromato-
grams) for samples representing the basin facies (178.8
1588 M. Hetényi et al. / Organic Geochemistry 33 (2002) 1571–1591
m depth), as well as the lowest (241.0 m depth) and the
uppermost (132.3 m depth) toe-of-slope facies are
shown in Fig. 7. The 20R isomers (biological configur-
ation) are predominant. The rearranged- and the
14b,17b(H)-steranes are missing and the 20S isomers are
present in a moderate proportion. The dominance of
C27 regular steranes over C29 (+ C28 and C30) indicates
the highest algal input in the sample taken from 241.0 m
depth. This observation is consistent with the elemen-
tary composition of kerogens and Rock Eval data which
reveal type I-II-S kerogen in these toe-of-slope sequen-
ces. Previous work has described that the increasing
parallel rates of sedimentation and of organic matter
deposition led to the better preservation of the organic
matter during the deposition of these toe-of-slope sedi-
ments than that of basin sediments. Moreover, these
intervals, characterized by the highest preservation,
correspond to times of the highest estimated rate of
planktonic productivity in the Rzt-1 well. The estimated
rate of primary productivity is about three times higher
for the toe-of-slope facies than for the basin facies (Vetó´
et al., 2000). The extremely low Tmax values observed on
samples taken from the two toe-of-slope facies contain-
ing type I-II-S kerogen (Table 3) are not the sign of an
extremely immature organic matter but are probably
related to the type of kerogen. Tmax values allow us to
distinguish between individual zones of the maturation
and to follow the trend of thermal evolution within cat-
agenesis and metagenesis. However, it is not an entirely
reliable indicator during diagenesis. Mineral matrix
effect and high amount of NSO-compounds may modify
Rock Eval data (Larter, 1984, Espitalié et al., 1985;
Vandenbroucke et al., 1993; Hetényi, 1998). Tmax values
are also affected by the type of kerogens as the thermal
energy required to break the different type of bonds
varies. On the basis of the results of kinetic considera-
tions, di Primio and Horsfield (1996) showed that
asphaltenes and type I-S kerogens are the most labile
species present in carbonate source rocks with sulphur-
rich organic matter.
The higher relative proportion of isoprenoid hydro-
carbons in kerogen pyrolysates, considered to be chlor-
ophyll-derived compounds, was also found in the toe-
of-slope facies. Tpr/T17 ratios (
prist-1-ene+prist-2-
ene+pristane/
n-heptadecene+n-heptadecane) are
higher and smaller than 0.85 for these samples and for
basin sediments, respectively (Table 6). Curry and Sim-
pler (1988) applied a similar ratio and found that the
ratio of the abundance of the C19:1 isoprenoids prist-1-
ene and prist-2-ene to the abundance of (n-C17:1+n-
C17:0) is significantly lower in the pyrolysates of kero-
gens of similar types and levels of catagenesis from more
oxic organic facies. In addition to the anoxicity, other
factors also control this ratio. Among the precursors of
C19 isoprenoids are several candidates: chlorophyll
(Didyk et al., 1978; Ishiwatari et al., 1991), tocopherols
(Goossens et al., 1984, 1988), lipids derived from
Archaea and methanogens (Chappé et al., 1980; Row-
land, 1990), C40 isoprenoid chains (lycopane skeleton)
of algaenans (Derenne et al., 1990) and methyl-tri-
methyl-tridecyl-chromans formed from chlorophyll and
alkylphenols (Li et al., 1995). The Tpr/t17 ratio may
reflect the abundance of photosynthetic organisms
among the precursors. A lycopane origin can be ruled
out on the basis of the isoprenoid distribution in pyr-
olysates (norpristane and 2,6,10-trimethyldecane are
present among regular minor products, other C11–C20
isoprenoid alkanes are missing). The relatively great
abundance of chlorophyll in photosynthetic organism
overprints the amount of other contributors in highly
anoxic environment, where a high percentage of bio-
synthetised phytol may survive during the early (bio)-
chemical diagenesis.
The role of the short-term cycles is especially con-
spicious during the early phase of the long-term trans-
gression. When the long-term transgression culminates,
it determines the paleoenvironmental facies and prob-
ably obscures the influence of short-term episodes. Fur-
thermore, in parallel with developing of the third order
transgression, the basin continously filled up. As a result
of these processes, organic features observed in the toe-
of-slope facies up to 170 m depth can not be recognized
in the sequence above 139 m depth (Fig. 7).
The determined organic features of carbonate-rich
basin facies seem to become more pronounced with
development of the third-order transgression (Figs. 4
and 6, Table 7). The more negative d13C values mea-
sured on kerogens, the higher HCsat/HCar ratios and the
dominance of the shorter n-alkanes over the longer
ones, in accordance with the lower phenol content of
kerogen pyrolysates, reflect the increased relative
importance of the marine contribution in the upper
basin facies (139–144 m depth) compared with the lower
one (170–190 m depth). This observation is in agree-
ment with the lower clay mineral content measured for
the upper limestone sequence (Table 7). The
2,6,10,15,19-pentamethyleicosane to n-docosane ratios
(i-C26/n-C22: > 0.7 and < 0.4 for the upper and lower
basin sections, respectively) exhibit an upwardly
decreasing methanogenic bacterial activity (Table 4).
The low hopanes/steranes ratios reflect a low propor-
tion of the bacterial biomass to the algal input
throughout the succession (Table 8).
5. Conclusion
& The studied boreholes exhibit substantial varia-
tions in mineral composition, as well as in
organic matter quantity and quality as a func-
tion of their position on the slope. A higher
 M. Hetényi et al. / Organic Geochemistry 33 (2002) 1571–1591
amount of organic matter with higher hydrogen
content accumulated at the toe of the slope than
on the slope. Petrographic observations, bitu-
men compositions together with the results of
the GC and GC/MS analyses of the saturated
hydrocarbon fractions of bitumen reveal that
these variations are mainly related to different
preservation rates and partly to different com-
position of the precursor biomass. The ratios of
the 2,6,10,15,19-pentamethyleicosane to n-doc-
osane and those of pristane to phytane contents
reflect a relatively higher methanogenic bacterial
activity and a slightly more anoxic environment
in the succession deposited at the lowest part of
the ramp than in that deposited on the slope.
& Parallel variations observed in the mineralogy
and the organic geochemical features along the
successions can be attributed to the essential
changes in the paleoenvironmental conditions
occurring during the deposition of the rocks.
 Compared with the mineralogically nearly
homogenous Rezi Dolomite Fm., a greater
abundance of the significant bacterial contribu-
tion and the appearance of a minor higher plant
derived input are characteristic of the miner-
alogically more heterogenous rocks in the Rezi-
Kössen Transitional Fm. and in the Kössen Fm.
Results presented here suggest that the climate-
induced change of the preservation rate was the
major factor in controlling the nature of organic
matter rather than the minor differences
observed in the precursor material of the differ-
ent formations studied. The increased mineral
supply, due to the more intensive weathering,
decreased the organic content and promoted the
better preservation of the organic matter during
the deposition of the Kössen Fm. and the
uppermost part of the transitional sequence.
 The repeated sea-level changes exerted a major
control on the features of the Kössen Fm.,
penetrated by the Rzt-1 borehole, resulting in
variations of the basin and the toe-of-slope
facies. The deposition of the carbonate-rich
basin facies correlate with highstand phases. HI
and d13C values, results of bitumen analysis and
the composition of kerogen pyrolysates, as well
as an upwardly decreasing clay mineral content
reveal the upwardly increasing importance of
the marine contribution in these limestone sec-
tions. The results of GC and GC/MS analyses of
the saturated hydrocarbon fractions of bitumen
show the great abundance of the algal-derived
organic matter throughout the succession and
reflect its highest contribution in the toe-of-slope
facies corresponding to lowstand intervals. The
observed variations in the hydrogen-richness of
1589
the sequences with different carbonate content
are consistent with the variations of primary
productivity rates described for the Rzt-1 well
(Vetó´ et al., 2000).
& The organic matter is immature and of pre-
dominantly marine origin throughout both of
the studied boreholes. The kerogens are classi-
fied as type I-II-S for the most organic-rich toe-
of-slope facies and type II-S for basin and slope
facies.
Acknowledgements
The authors wish to thank the Hungarian Scientific
Foundation (OTKA grants No. T 34168) for funding
this work. One of us (M. Hámor-Vidó) thanks the
Bolyai János Research Fund of the Hungarian Acad-
emy of Sciences for financal support. We kindly thank
Zoltán Kárpáti for his help in GC/MS analyses. Excel-
lent rewiews and many helpful comments of the two
referees are gratefully appreciated: they significantly
improved the paper. Thanks are expressed for helpful
comments by Dr. R. Michels.
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