GeolCarp_Vol52_No1_3

GEOLOGICA CARPATHICA, 52, 1, BRATISLAVA, FEBRUARY 2001

3 — 14

HYDROCARBONS MIGRATION IN TECTONIC ZONES

OF THE WESTERN TATRA MOUNTAINS CRYSTALLINE

BASEMENT (CENTRAL WESTERN CARPATHIANS)

LESZEK MARYNOWSKI

, ALEKSANDRA GAWĘDA

, STEFAN CEBULAK

and MARIUSZ JĘDRYSEK

Department of Geochemistry, Mineralogy and Petrography,

Faculty of Earth Sciences, University of Silesia,

Będzińska Street 60, 41-200 Sosnowiec, Poland; *marynows@ultra.cto.us.edu.pl

Laboratory of Isotope Geology and Biogeochemistry, Institute of Geological Sciences, University of Wrocław,

Cybulskiego Street 30, 50-205, Wrocław, Poland

(Manuscript received July 11, 2000; accepted in revised form December 12, 2000)

Abstract: In the Western Tatra Mountains crystalline basement a bituminous matter was found in tectonic zones
(faults, shatter zones). The tectonic zones run NE-SW cutting both the Variscan crystalline basement and its sedimen-
tary Mesozoic cover. Oxyreactive Thermal Analyses of whole rock samples and Gas Chromatography—Mass Spec-
troscopy analyses of extractable organic matter revealed that the bitumens in question are heavy fractions of crude
oils. The source rocks of the bitumens were marine shales and lacustrine sediments, relatively poor in organic mate-
rial, accumulated in suboxic shelf conditions. The thermal maturity of the bitumens was determined as the oil-window
stage (R

= 0.74—0.82 %). The terrestrial organic matter admixture was negligibly small, so we can suggest the age

of the source material may be older than Tertiary (by comparison with the other Carpathian oils). The comparison with
the Outer Carpathian crude oils showed that the Western Tatra bitumens resemble Jurassic oils more than Paleogene
ones. Jurassic and Upper Triassic carbonates and black shales from the overthrust Tatricum sequences seem to be a
more plausible source rocks for the investigated bitumens. The tectonic zones, rejuvenated after or during Miocene
uplift of the Tatra Block served as the paths for bitumens migration.

Key words: Tatra Mountains, crystalline basement, hydrocarbons, migration, source rocks, biomarkers, maturity.

Introduction

The  presence  of  hydrocarbons  sensu  lato  (crude  oil,  asphalt,
ozokerite etc.) in fractured crystalline rocks (especially gran-
ites)  has  been  reported  from  many  localities  in  the  world
(Great  Britain,  Venezuela,  Argentina,  China,  Egypt,  Libya,
USA). In all cases the basement reservoirs which usually form
topographic  highs  on  the  basement  paleosurface  (Parnell
1988),  are  fed  by  the  sedimentary  cover.  Hydrocarbons  can
migrate  both  downwards  –  as  a  result  of  squeezing  during
compaction,  and  laterally  –  to  the  fractured  highs.  The  re-
gional  unconformities  are  of  great  significance,  forming  the
pathways for the migration of both hydrocarbons and hydro-
thermal fluids.

There are several theories accounting for the presence of hy-

drocarbons in crystalline rocks. Most stress the role of granite
intrusions and the thermal reactivation of the basement rocks
as a source of heat and hydrothermal fluids (e.g. Parnell 1988).
The heat could cause the transformation of organic matter
while hydrothermal fluids penetrating the fractured portion of
basement could facilitate the migration of newly formed hy-
drocarbons. Other sources of heat are the radioactive elements,
although their activity tends to be connected directly or indi-
rectly with granitic plutons.

In the Tatra Mountains crystalline basement the bituminous

matter has not been described previously. The aim of this pa-
per is to as certain whether the bitumens found in the crystal-
line basement are really genetically related to the basement or
are formed by another process. The additional purpose of the

presented work was to characterize the bitumen-bearing sam-
ples and, on the basis of their characteristic features, to deter-
mine their provenance, source rocks and the environmental
conditions of hydrocarbons generation.

Geological setting and sampling

The Tatra Mountains form a rhomboidal massif, limited by

regional faults: the Subtatra fault on the south, the Choč and
Krowiarki faults on the west and north-west and the Drużbaki
(Ružbachy) fault on the east and south-east (Bac-Moszaszwili
1993, 1996). The Tatra Mountains form the northernmost crys-
talline massif among the so-called internal massifs in the Cen-
tral Western Carpathian belt, probably allochthonous and
transported to the north during the Alpine orogenesis and Car-
pathian belt formation (Lefeld & Jankowski 1985; Wieczorek
1990).

The Western Tatra Mountains crystalline basement compris-

es  a  polygenetic  granitoid  pluton,  of  Variscan  age  (340—370
Ma, Gawęda 1995; Janák et al. 1998; Todt et al. 1998) and its
pre-Variscan metamorphic envelope (380—405 Ma – Kohút et
al. 1998; 395 Ma – Gawęda 1997). Among the metamorphic
rocks two units could be distinguished, differing in metamor-
phic grade, petrographical features and geochemical character
(Janák  1994;  Gawęda  &  Kozłowski  1998;  Kozłowski  &
Gawęda  1999).  In  the  Lower  Structural  Unit  (LSU)  mica
schists,  interfoliated  with  minor  amphibolites  predominate,
metamorphosed under upper greenschist to lower amphibolite

4 MARYNOWSKI et al.

facies conditions, whereas the Upper Structural Unit (USU) is
composed of amphibolite facies migmatitic gneisses and am-
phibolites, graphitic quartzites and orthogneisses (Gawęda &
Cebulak 1999; Kozłowski & Gawęda 1999, Fig. 1).

The crystalline rocks are covered by the parautochthonous

Triassic succession and a series of nappes, containing Trias-
sic, Jurassic and Cretaceous variegated sedimentary rocks,
overthrust during the Alpine orogenesis. Faults and zones of
shattering, trending NE-SW with a strike-slip displacement,
discordantly cut both the crystalline basement and its sedi-
mentary cover (Fig. 1) and are thought to be connected to the
Miocene uplift of the Tatra Mountains crystalline basement
(Burchart 1972).

Analytical methods

The dark-grey or black samples of rocks from tectonic

zones, weighing 0.5—3 kg each were taken from the NE-SW
trending fault-zones in the crystalline basement of the Western
Tatra Mts (Fig. 1).

All microscopic observations were carried out in the Faculty

of Earth Sciences, University of Silesia. Three selected sam-
ples were analysed by XRF for major and selected trace ele-
ment at Keele University (GB) during the scholarship of the
second author, using both international and internal Keele
standards. For two samples detailed trace element analyses
(including REE) were carried out in the Activation Laborato-
ries Ltd (Canada) using ICP-MS method.

OTA – The thermal analyses of the whole-rock samples,

carried out as the oxyreactive variety (OTA – Cebulak &
Langer-Kuźniarova 1997) were conducted on the MOM Deri-
vatograph (Faculty of Earth Sciences, University of Silesia) in
an air atmosphere. The analytical conditions were: dynamic
conditions for the air suction of 1.9 cm

min

—1

, inflation rate 1

min

—1

, multiple sample holders (3—10 Pt plates). The total

mass of each analysed sample was within the range of 600—800
mg. The Oxyreactive Thermal Analysis assumes free access of
oxygen to the substance throughout the heating process, so the
reaction is a function of the structure and composition of the
sample. OTA has been used in many research works on organic
matter as the standard method of analysis.

Fractionations – Dry powdered samples were washed up

in distilled water, dried and crushed in a ball-mill to the frac-
tion below 0.2 mm

∅

and extracted in dichloromethane in

Soxhlet apparatus. The extractable organic matter (EOM) was
fractionated by thin-layer chromatography (TLC Merck plates
20

20 cm covered by silica gel 60 H 0.25 mm thick) and de-

veloped in n-hexane. Before separation the TLC plates were
activated for 3 hours at 105 °C.

GCMS – Gas Chromatography—Mass Spectroscopy (GC—

MS) analyses were carried out for aliphatic and aromatic hy-
drocarbon fractions separately. GC—MS analyses were per-
formed on a HP 5890 chromatograph with capillary columns
coated with diphenylpolysiloxane phase (HP-5, 0.25

m of the

film thickness), 60 m in length. The GC oven was pro-
grammed to increase the temperature from 45 °C to 300 °C at
a rate of 3 °C min

—1

. Helium (1 ml per min) was a carrier gas.

The mass quadrupole 5971 A, operating with an electron ener-

gy of 70 eV was a detector of separated constituents. Scanning
was carried out within the mass interval 45—550 with a cycle
time of 1 s. The solutions were prepared by diluting 1—3 mg of
each fraction in 1 ml dichloromethane. Individual compounds
were identified by mass chromatography on the basis of mass
spectra, relative retention time (Lee et al. 1979; Yawanarajah
& Kruge 1994; Radke et al. 1982, 1986, 2000; Chakhmakh-
chev et al. 1997; Peters & Moldowan 1993; Kruge 2000;
Marynowski & Czechowski 1999; Mössner et al. 1999; Möss-
ner & Wise 1999) and by co-chromatography with reference
compounds.

Isotope analysis – Isotope analyses of separated aliphatic

and aromatic fractions were performed at the Institute of Geo-
logical Sciences, Wrocław University, Laboratory of Isotope
Geology and Biochemistry. About 3 mg of hydrocarbon mate-
rial from each sample was combusted with CuO wire in a
sealed quartz tube, under vacuum at 900 °C. The CO

gas was

cryogenically purified and then introduced into a mass spec-
trometer (Finnigan Mat CH7 with a modified inlet and detec-
tion system). The carbon stable isotopes ratio (

C) was mea-

sured with a precision of 0.05 ‰. Values are quoted relative to
the PDB international standard.

Results

Microscopic and geochemical data

Strongly tectonized rocks from the NE-SW trending fault-

zones represent the predominant brittle deformation (crushing
and displacing called here shattering). In some cases the older
ductile shear-zones (probably early Variscan in age – Gawę-
da et al. 1998) were reactivated by younger brittle fault struc-
tures and there the remnants of metamorphic S-C fabric were
preserved. The tectonic zones are located mainly in the meta-
morphic rocks, usually mechanically weaker than massive gra-
nitic  intrusions.  The  metamorphic  complex  in  question  con-
sists  of  metapelitic-metapsamitic  gneisses  and  migmatites
(Burda & Gawęda 1997), interleaved with amphibolites (meta-
morphosed  tholeiitic  basalts  –  Gawęda  et  al.  2000a).  The
metapelitic-metapsamitic gneisses and migmatites are charac-
terized  by  the  typical  mineral  assemblage  Qtz+Pl±Kfs+Bt±
Grt±Sil±Ky+Ap+Ms±Gph, while amphibolites are composed
of the Hbl+Pl+Qtz+Ilm±Grt+Ap. Chondrite normalized REE
diagrams for the metamorphic rocks show typical negative Eu
anomaly and fall into one field presented in the Fig. 2 (shaded
area).  REE  patterns  of  the  selected  bitumen-bearing  rocks
show a medium fractionation trend and fall in the same field of
REE  characteristics  for  the  crystalline  rocks  of  the  Western
Tatra Mts (Table 1, Fig. 2). This fact suggests that the chemistry
of  the  original  rocks  was  not  changed  dramatically  and  REE
were not mobilized during bitumens migration. In three samples
bituminous matter is mixed with goethite (Baniste 2, Ł6, Ł20).

The cataclastic rocks are partly recrystallized and contain

quartz, sericitized feldspars, muscovite, chlorites, sometimes
remnants of biotite. Fine-grained quartz forms the mineral ce-
ment. Dark impregnations and patches concentrated along
structural planes (preserved metamorphic foliation, fractures,
etc.) were microscopically distinguishable (Figs. 3, 4).

HYDROCARBONS MIGRATION IN THE TECTONIC ZONES OF WESTERN TATRA MTS 5

The low concentration of Na

O (Table 2) is caused by the al-

kali leaching during alteration of plagioclase, while SiO

con-

tent  exceeding  75  wt.  %  is  usually  the  result  of  secondary
quartz  precipitation,  which  is  a  common  matrix  mineral  for
most of these mylonites. Reflected light microscopy shows the
presence of small quantities of sulphide minerals (tetrahedrite,
chalcopyrite) and – in some cases – barite and this is con-
firmed  by  enhanced  concentrations  of  certain  trace  elements
(Ba, Cu, Ag) in some samples from i.e. Ornak Ridge (SP2).

Mo (4—18 ppm), W (0.8—1.2 ppm), Be (3—4 ppm), U (4—9

ppm), Ni (17—31 ppm) are enriched in all analysed samples in

Fig.  1.  Geological  map  of  the  Polish  side  of  the  Western  Tatra  Mountains  with  sample  locations.  Explanations:  1  –  Lower  Structural
Complex;  2 – Upper Structural Complex; 3 – amphibolites; 4 – leucogranites (alaskites);  5 – biotitic granodiorite (Rohacze Gran-
ite);  6 – cataclastic rocks; 7 – Triassic sediments;  8 – Jurassic & Cretaceous sediments; 9 – faults; 10 – state boundary; 11 – sam-
ple locations; 12 – nappe boundary. 1—6 – Tatric basement complexes; 7—8 – Mesozoic cover and nappe complexes.

Fig. 2. Chondrite normalized REE concentrations in the bitumen-
bearing rocks. The shaded area is the field of typical metamorphic
rocks from the Western Tatra Mountains.

Component

SP2

Czubik

16.6

26.5

32.9

55.4

3.86

6.32

15.3

24.4

3.24

4.32

1.13

0.97

3.10

3.94

0.51

0.72

2.82

4.58

0.53

0.93

1.53

2.86

0.221

0.430

1.49

2.89

0.211

0.428

(La)

/(Yb)

6.577

7.991

(La)

/(Yb)

—

fractionation index

Table 1: Rare Earth Elements (REE) concentrations in the bitumen-
bearing rocks.

relation to the other Tatra basement rocks (Mo is usually be-
low 1 ppm, sporadically 2 ppm, W – below 1 ppm, Be – be-
low 1, sporadically 1—2 ppm). The reference rock for the dis-
crimination was the so-called “mean Tatra metamorphic rock”
(MTR),  created  on  the  basis  of  the  second  author’s  whole-
rock  analyses  (Table  1;  Burda  &  Gawęda  1997;  Gawęda  &
Kozłowski 1998; Kozłowski & Gawęda 1999). For the calcu-
lation of MTR composition about a hundred chemical analy-
ses  of  metamorphic  rocks  were  used  assuming  their  volume
proportion from the field studies.

6 MARYNOWSKI et al.

Oxyreactive thermal analyses

The weight per cent of the bituminous matter, calculated

from the loss of mass at characteristic reactions in the tem-
perature range of 200—400 °C, is about 0.2—1.0 wt. %.

Oxyreactive thermal analyses of the whole-rock samples

reveal the presence of endothermic peaks in the temperature
range of 240—290 °C (after checking the mineral matrix ther-
mal characteristics), and the exothermic reactions in the tem-

Fig. 4. Microphotograph of older S-C mylonite with bituminous
impregnations on the shearing planes (Ł6). Crossed polars.

Fig. 3. Microphotograph of cataclasite with black patches of bitu-
mens (Baniste 2). 1 polar.

Sample No.

C AR

C AL

C POL

DU5

-25.87

-27.48

-27.07

DU7

-25.11

-25.17

-27.37

SP2

Nd.

-25.26

-27.13

Czubik

-26.02

-28.34

-26.82

AR – aromatic fraction; AL – aliphatic fration; POL – polar fraction

Table 3: Carbon isotope data of the extractable bituminous matter.

– Fe

as a total iron; nd – not determined concentration

Table 2: Chemical composition of the bitumen-bearing rocks and
reference mean Tatra metamorphic rock (MTR). (Major elements
given in [wt. %], selected trace elements in [ppm]).

Component

SP1

SP2

Czubik

MTR

SiO

74.47

76.46

71.16

62.06

TiO

0.58

0.31

0.71

0.97

13.11

8.96

16.87

15.64

5.08

5.84

5.11

7.43

MnO

0.05

0.07

0.11

MgO

0.85

0.56

0.45

1.76

CaO

0.06

0.04

0.09

2.86

0.27

0.10

1.44

4.39

2.92

3.08

4.16

2.66

0.14

0.11

0.15

0.47

LOI

2.8

2.94

0.25

1.38

0.003

0.10

0.004

0.001

Total

100.333

98.55

100.464

99.731

7.0

7.9

8.4

2.0

104

132

118

767

163

212

273

9230

524

556

1.89

8.9

9.13

4.65

2.3

6.2

4.33

7.06

6.4

141

168

170

3.0

2.5

4.4

16.3

27.6

3.0

2.9

1.1

1680

19.7

84.6

5.9

143

130

107.5

1.0

1.2

0.8

0.3

5.3

9.6

0.8

perature range of 280—340 °C (Fig. 5). Where goethite is
present in the analysed samples the exothermic peaks are ho-
mogenous and distinct, while in other samples the exother-
mic reactions are often non-homogenous, with subordinate
“parasitic” peaks on both slopes of the main reaction peaks.
Such thermal patterns are typical of heavy fractions of crude
oil (Cebulak et al. 1999).

Carbon stable isotopes

Calculated values of

C for aromatic fractions of extracted

bituminous matter are within the range of —25.17 to —28.34 ‰
(Table 3). Such characteristics of unbiodegradated samples are

HYDROCARBONS MIGRATION IN THE TECTONIC ZONES OF WESTERN TATRA MTS 7

typical of marine, algal or mixed marine and terrestrial source
material (Sofer 1984), with dominant planctonic type of organ-
ic matter (Fig. 6).

GC—MS analyses

The extractable fraction forms 0.03—0.32 wt. % of the

analysed samples. In the aliphatic fraction of analysed hy-
drocarbons the bimodal distribution of selected n-alkanes
was observed with the first maximum in n-C

or n-C

and

the second (smaller) maximum in n-C

(Figs. 6, 7). Sam-

ples ”Czubik” and DU5 contain a so-called “hump” that is
unresolved compound mixture (Gough & Rowland 1990).
All bitumen samples contain relatively high amounts of di-
asteranes (m/z 217; Fig. 7). The Pr/Ph ratio is about 1. The
calculated values of vitrinite reflectance, based on the me-
thyldibenzothiophene ratio (Radke & Willsch 1994) are in
the range of R

= 0.75—0.82 %. The detailed characteristics

of the parameters calculated from the GC—MS spectra are
presented in Table 4 and the assignations of the identified
compounds are in the appendix.

Discussion

The character and origin of bitumens

OTA – The OTA patterns of the analysed samples are

typical of heavy fractions of rock-oil. The thermal analyses

Fig. 5. OTA curves of the whole-rock bitumen-bearing samples
from the tectonic zones of the Western Tatra Mountains. For loca-
tion see Fig. 1.

DU 9

W 1

W 2

DU 4

DU 10

Kam 1

Type 1

Type 2

Type 3

Baniste 2

Czubik

Ł20

Ł6

Ł10

DUQ 3

DUQ 2

DU 7

DU 2

DU 3

DU 5

DTG

OTA

DTG

OTA

DTG

OTA

DTG

OTA

DTG

OTA

DTG

OTA

DTG

OTA

DTG

OTA

DTG

OTA

DTG

OTA

DTG

OTA

DTG

OTA

DTG

OTA

DTG

OTA

DTG

OTA

DTG

OTA

DTG

OTA

100

400

300

200

100

400

300

200

100

400

300

200

reveal the characteristics of both extractable (migratory) and
non-extractable (unresolved in organic solvents) fractions.
Non-extractable components are enriched in so-called pyro-
bitumens.

The results of oxyreactive thermal analysis (both DTG and

DTA) show the diversification of the thermal reactivity of
the analysed bituminous matter. We can distinguish three
types of organic material.

Type 1. Organic matter characterized by the presence of

endothermic reaction and lacking or only trace exothermic
peaks (samples DU9, DU10, W1, W2, K1; Fig. 6). Endother-
mic reactions are observed at 240/250 °C and 280/290 °C.
This type of sample lacks non-extractable components.

Type 2. Organic matter characterized by the presence of

endothermic reactions, observed as the single peak at 290 °C
or as two peaks at 240/250 °C and 280/290 °C and distinct
exothermic reaction in the temperature range of 300—360 °C
(samples DU2, DU3, DU5, DU6, Ł6, Ł10, Ł20, Czubik –
Fig. 5). Such patterns are typical of samples enriched in the
non-extractable components, showing the coking capacity.

Type 3. Sample Baniste 2 is characterized by the endother-

mic peak at 260 °C and distinct exothermic peak at 270/280
°C. The OTA patterns could suggest the susceptibility to cat-
alytic transformations in the presence of Fe-compounds.

The differences in thermal features among the analysed bi-

tumens (and consequently three distinguished types of organ-
ic matter) resulted mainly from the biodegradation and evap-
oration processes and transformation influenced by the
Fe-rich fluids, stimulating maturation processes.

GC—MS – The distribution patterns of n-alkanes suggest

a mixed (terrestrial-marine) character of the organic material
primary  for  bitumen  generation.  It  should  be  noted  that  in
many  cases  biodegradation  processes  overprint  the  primary
n-alkanes distribution patterns, causing the removal of short-
chain n-alkanes. However, the samples Czubik and DU5 re-
veal features characteristic of small to moderate biodegrada-
tion degree (Fig. 6), manifested by the partial destruction of
n-alkanes  and  isoprenoids:  Pr/Ph  Pr/n-C

ratios are partly

affected (Peters & Moldowan 1993). The thermograms of the
samples with biodegradation show the shift in endothermic
peaks to higher temperatures (see Fig. 5, sample DU5,
Czubik), which is a direct effect of the short-chain n-alkanes
removal/consumption.

The values of dibenzothiophene/phenanthrene (DBT/P),

alkyldibenzothiophene/alkyldibezofurane

(ADBT/ADBF)

and pristane/phytane (Pr/Ph) ratios for the analysed samples
are plotted on the genetic diagrams according to Hughes et
al. (1995) and Radke et al. (2000) (Fig. 8a,b). Three samples
plot  in  the  field  3  (marine  shales  and  lacustrine  sediments)
while  two  other  samples  plot  in  the  field  2  (lacustrine,  sul-
phate  –  poor  sediments).  However,  the  recent  data  from
rocks  of  the  Devonian  carbonate  platform  and  shelf  basin
show that marine, poor in organic matter samples also plot in
field 2 (Marynowski et al. 2000). The GC—MS data are sup-
ported by the isotopic results showing the algae and terrestri-
al source (Fig. 6).

All bitumen samples are characterized by relatively high

diasterane/sterane ratios (m/z 217 – Fig. 7, Table 4). High
diasterane concentration depends on the clay minerals con-
tent relative to the organic matter content in the rock (clay/

8 MARYNOWSKI et al.

TOC ratio – van Kaam-Peters et al. 1998). High diasterane
concentrations  could  be  caused  by  the  enrichment  in  clay
minerals  in  the  source  rocks,  which  generate  hydrocarbons
(Peters  &  Moldowan  1993)  and  suggests  a  relatively  low
concentration of organic matter in the clayey source rocks, in
which bitumens were generated. High hopane concentrations
(ster/17

(H)-hop parameter, Table 4) and the presence of

tetracyclic triterpanes (C

tetra/C

tri parameter, Table 4),

described as microbial compounds (Hughes & Holba 1988;
Wan Wasiah 1999) suggests that organic matter in the source
rocks was subjected to the secondary bacterial reworking in
the sedimentary basin after deposition.

Small amounts of cadalene and retene are present in the in-

vestigated rocks. They are the biomarkers indicating the
former presence of higher plant material (van Aarsen et al.
2000). The presence of mentioned biomarkers, originated from
higher plant material, could suggest a negligible small admix-

ture of the terrestrial organic matter influence in the source, bi-
tumen-generating rocks. However, there is a lack of oleanes,
compounds typical of angiosperms and occurring commonly
in Carpathian Tertiary oils and sediments (Kruge et al. 1996;
Lafargue et al. 1994; Köster et al. 1998a,b; Picha & Peters
1998; Franců et al. 1996; ten Haven et al. 1993).

In the ternary diagrams (Fig. 9a,b) the relative concentra-

tions of C

, C

and C

steranes and C

, C

, and

(H)-hopanes are shown. The results indicate the uniform

character of the investigated bitumens. Fig. 9a presents the
difference in sterane concentrations in the presented Western
Tatra bitumens from the sterane concentrations in samples of
oils from the Outer Carpathians (Poland and Czech Repub-
lic), of Jurassic and Oligocene age.

The hopane distribution patterns (Fig. 7, m/z 191), includ-

ing low values of the Homohopane Index (0.15—0.21, Table 4)
as well as the presence of C

*—17

(H)-diahopane suggest

Fig. 6. Carbon isotope composition of saturated versus aromatic hydrocarbon fraction (after Sofer 1984) and distribution of saturated hy-
drocarbons fractions from the selected samples. UCM – unresolved compound mixture; Pr – pristane; Ph – phytane.

10 MARYNOWSKI et al.

Fig. 8. Analysed samples from the Western Tatra Mountains in 2 cross plots: A. dibenzothiophene/phenanthrene (DBT/P) versus pristane/
phytane (Pr/Ph) ratios (based on Hughes et al. 1995) B. alkyldibenzothiophene/alkyldibenzofuranes (ADBT/ADBF) versus pristane/phytane
(Pr/Ph) ratios (after Radke et al. 2000).

Fig. 9. Ternary diagram of C

, C

and C

sterane composition [5

, 14

, 17

(H) 20S + 20R and 5

, 14

, 17

(H) 20S + 20R] for bitumens

from the Western Tatra Mountains. For comparison see Picha & Peters (1998).

Pr/Ph – pristane/phytane;
Pr/ n-C

– pristane/n-heptadecane;

Ts/(Ts + Tm) – 18

-22,29,30-trisnorneohopane/(18

-22,29,30-trisnorneohopane

+ 17

(H)-22,29,30-trisnorhopane)(Peters & Moldowan 1993);

Steranes/17

(H)-hop. – regular steranes consist of the C

, C

ααα

(20S +

20R) and

αββ

(20S + 20R), 17

(H)-hopanes consist of the C

to C

pseudohomologue (including 22S and 22R epimers) (Peters & Mol-
dowan 1993);

Homohopane Index – C

/(C

+ C

) homohopanes (Peters & Moldowan 1993);

tetra/C

tri – C

tetracyclic terpane/C

tricyclic terpane (Wan Hasiah 1999);

ββ

ββββββββββ

αα

)–[5

(H),14

(H),17

(H)(20R+20S) C

sterane]/ [5

(H),14

(H),17

(20R + 20S) C

sterane + 5

(H),14

(H),17

(H)(20R + 20S)] C

steranes

(Peters & Moldowan 1993);

20S/(20S + 20R) – C

(H),14

(H),17

(H)20S/[C

(H),14

(H),17

(H)20(S

+R)] (Peters & Moldowan 1993);

MDR – methyldibenzothiophene ratio [4-MDBT]/[1-MDBT] (Radke et al. 1986);
R

(%) = 0.073 MDR + 0.51 (Radke & Willsch 1994);

TA(I)/TA(I + II) – sum of C

-C

(20S + 20R) triaromatic steroids as TA(II) and

the C

and C

triaromatic steroids as TA(I) (Peters & Moldowan 1993);

DMDBT – dimethyldibenzothiophene ratio, DMDBT = 2,4-DMDBT/1,4-DMDBT

(Chakhmakhchev et al. 1997);

TMDBT – trimethyldibenzothiophene ratio, TMDBT = 2,4,7-TMDBT/1,4,7-TM-

DBT (Chakhmakhchev et al. 1997);

MPI1 – methylphenanthrene index 1, MPI1 = 1.5([2-MP] + [3-MP])/([P]+[1-MP]

+ [9-MP]) (Radke & Welte 1983);

TrP1 – terphenyl ratio 1, [p-TrP]/[o-TrP] (Marynowski & Czechowski 1999).

MOLECULAR

PARAMETERS

BANISTE

Du5

Du7

CZUBIK

SP2

Isoprenoids

Pr/Ph

0.71

0.95

1.09

0.91

1.10

Pr/n-C

0.40

0.74

0.63

0.97

0.61

Triterpanes

Ts/(Ts + Tm)

0.42

0.44

0.42

0.45

0.42

Homohopane Index

0.17

0.18

0.21

0.15

0.21

tetra/C

tri

1.0

1.20

0.71

1.0

tri/C

hop

0.69

1.30

0.49

0.60

0.42

Steranes/17α(H)-hop

0.50

0.48

0.46

0.50

0.57

Steranes

-Sterane [%]

331

Dia/Ster

0.50

0.62

0.50

0.55

0.53

ββ/(ββ+αα)

0.52

0.49

0.47

0.50

0.53

20S/(20S + 20R)

0.47

0.49

0.44

0.48

0.51

Polycyclic Aromatic Compounds

MDR

4.26

3.63

3.08

3.63

[%]

0.82

0.77

0.74

0.77

TA(I)/TA(I + II)

0.33

0.30

0.29

0.50

0.25

DMDBT

0.61

0.56

0.58

0.53

0.52

TMDBT

1.04

1.10

1.12

1.15

MPI1

0.21

0.22

0.19

0.21

0.23

TrP1

0.38

0.41

0.17

0.73

0.26

Table 4: Geochemical characteristics of the bitumens from the Tatra Mountains.

12 MARYNOWSKI et al.

basin (i.e. Lefeld 1997b), which does not correspond to the
suggested oxic marine shelf conditions needed for the source
rocks of the bitumen. The Upper Triassic and/or Jurassic car-
bonate series of the parautochthonous Tatric successions
Nappe seem to be more plausible source rocks.

Mechanism of migration

The NE-SW trending faults, probably active after the Al-

pine  overthrusting,  are  likely  paths  for  migration  of  bitu-
mens. Some shear-zones could be rejuvenated earlier faults,
which  acted  formerly  as  the  paths  for  fluid  circulation  and
contain  abundant  carbonate-quartz-sulphide-barite  mineral-
ization (Wątocki 1950; Paulo 1970; Gawęda et al. 2000). Mi-
croscopic observations show that the mineralization is older
than the bituminous impregnations.

It is likely that the lighter fractions of the oils migrated (or

were flushed through by circulating water), while the heavy
fractions of crude oils were trapped in the tectonic zones.
Migration of the hydrocarbons occurred most probably dur-
ing or after overthrusting of the Mesozoic nappes.

The original chemistry of host rocks was not significantly

changed during bitumen migration, but the enhanced concen-
tration of U, W, Ni and Cr [forming the positive anomalies in
the shattered (fractured) rocks] could be connected with the
presence of bitumens. All these elements can form the metal-
organic components and are usually enriched in the bitumens
deposits. Especially uranium mobility should be considered
with care – in the Białego Valley a small uranium anomaly
was noted by the Russian IVth Prospecting Group in the tec-
tonic zone running NE-SW. In the report of 1952 the concen-
tration of U between 0.05 wt. % and 0.3 wt. % was mentioned,
correlated with the presence of strongly shattered upper Trias-
sic black shales (Wołkowicz – pers. commun.).

The original bitumen-bearing source rocks are unlikely to

be found because bitumen removal would have been induced
by the extensive tectonic movements. Nevertheless, this pa-
per is the first step in understanding of the migration process-
es within the tectonic zones in the Tatra Mountains.

Conclusions

1. Bitumens found in the NE-SW trending tectonic zones of

the Western Tatra Mountains belong to the heavy fractions of
crude oil. They were trapped in the mineral pores and locally
deposited on the tectonic planes during migration of rock-oils
and fluids along the tectonic zones, cutting both basement
rocks and the sedimentary cover rocks.

2. The source rocks of the bitumens were enriched in clay

minerals, relatively poor in organic matter and were accumu-
lated in marine, suboxic shelf conditions. The secondary bac-
terial reworking of the primary hydrocarbons took place in the
sedimentary basin after deposition.

3. Organic maturation of the investigated bitumens reached

the catagenetic stage of transformation (oil-window).

4. The source rocks of the migrated hydrocarbons could be

the Upper Triassic and/or Jurassic sedimentary series of the

Tatricum sequence. The younger (Tertiary) source was ex-
cluded on the basis of biomarkers analysis.

Acknowledgements:  The  research  was  sponsored  by  the
Polish Committee for Scientific Research (Grant No. 6PO4D
02816). Dave Emley and Margaret Aikin helped during  XRF
analyses at Keele University, Dr. J.A. Winchester is grateful-
ly acknowledged for checking the English text and for con-
structive  comments.  Dr.  St.  Wołkowicz  (PGI  Warsaw)
helped during the search for the Russian documents from the
50s and 60s.  MSc Ewa Teper is acknowledged for the help
during microphotographs preparation and S. Kurkiewicz for
the assistance during GC—MS analyses. The autors thank Dr.
Juraj Franců and three anonymous referees for helpful com-
ments on an earlier version of the paper.

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Peak number

Compound assignation

TIC

Pristane

Phytane

n-C

n-Tetradecane

n-C

n-Octadecane

n-C

n-Docosane

n-C

n-Hexacosane

n-C

n-Triacontane

m/z 191

α(H)-22,29,30-Trisnorneohopane,

α(H)-22,29,30-Trisnorhopane,

29H

- 17

α,21β(H)-30-norhopane,

29Ts

Ts - 18

α(H)-30-norneohopane,

* - 17

α(H)-diahopane,

30H

- 17

α,21β(H)-hopane,

29M

-17

β,21α(H)-hopane (moretane),

31H-S

- 17

α,21β(H)-29-homohopane 22S,

31H-R

- 17

α,21β(H)-29-homohopane 22R,

32H-S

-17

α,21β(H)-29-bishomohopane 22S,

32H-R

-17

α,21β(H)-29-bishomohopane 22R,

33H-S

-17

α,21β(H)-29-trishomohopane 22S,

33H-R

-17

α,21β(H)-29-trishomohopane 22R,

34H-S

-17

α,21β(H)-29-tetrakishomohopane 22S,

34H-R

-17

α,21β(H)-29-tetrakishomohopane 22R,

35H-S

-17

α,21β(H)-29-pentakishomohopane 22S,

35H-R

-17

α,21β(H)-29-pentakishomohopane 22R,

19T