GEOLOGICA CARPATHICA, 52, 1, BRATISLAVA, FEBRUARY 2001
3 — 14
HYDROCARBONS MIGRATION IN TECTONIC ZONES
OF THE WESTERN TATRA MOUNTAINS CRYSTALLINE
BASEMENT (CENTRAL WESTERN CARPATHIANS)
, 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; *email@example.com
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
= 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.
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-
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
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
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
, inflation rate 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 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
. 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
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
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.
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
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.
Table 1: Rare Earth Elements (REE) concentrations in the bitumen-
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.
AR – aromatic fraction; AL – aliphatic fration; POL – polar fraction
Table 3: Carbon isotope data of the extractable bituminous matter.
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]).
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).
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
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.
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.
reveal the characteristics of both extractable (migratory) and
non-extractable (unresolved in organic solvents) fractions.
Non-extractable components are enriched in so-called pyro-
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
The values of dibenzothiophene/phenanthrene (DBT/P),
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
(H)-hop parameter, Table 4) and the presence of
tetracyclic triterpanes (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
steranes and C
(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
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.
HYDROCARBONS MIGRATION IN THE TECTONIC ZONES OF WESTERN TATRA MTS 9
Fig. 7. Total ion chromatogram and fragmentograms of tricyclic, tetracyclic, pentacyclic triterpanes (m/z 191) and steranes (m/z 217)
from sample Du7. The assigned peaks are listed in appendix.
that the parental organic matter was accumulated in the ma-
rine, suboxic shelf conditions.
The thermal maturity of the investigated bitumens was de-
termined on the basis of organic compounds in aliphatic and
aromatic fractions. Parameters like Ts/(Ts + Tm),
20S/(20S + 20R), MDR DMBT, TMDBT, MPI1 or TrP1 have
almost equal values for specific samples of the Western Tatra
bitumens (Fig. 10, Table in appendix). They are typical of ma-
ture organic matter at catagenetic stage of transformation
(Horsfield & Rullkötter 1994). The MDR parameter value was
recalculated to theoretical vitrinite reflectance (R
to Radke & Willsch 1994). The R
= 0.74—0.82 % are typical
of the oil-window stage of transformation. Note that the val-
ues of the popular metylphenanthrene 1 index (MPI1) are
significantly lower than the other parameters (MPI1 = 0.19—
0.23). It is widely known that this index does not work for
the II type of kerogen (algae marine organic material – Pe-
ters 1986) that can be responsible for the lowered MPI1 in-
dex values (Radke et al. 1986).
Where are the source rocks for bitumens?
Due to high metamorphic alteration, the present host rocks
of the investigated bitumens cannot be considered as their
source rocks. Considering the above mentioned characteris-
tics the most convenient source for the bitumens are the sedi-
mentary overlying rocks. They were not metamorphosed dur-
ing the Alpine overthrusting; the conodont alteration index
(CAI) from the Triassic limestones from the Tatricum se-
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
sterane composition [5
(H) 20S + 20R and 5
(H) 20S + 20R] for bitumens
from the Western Tatra Mountains. For comparison see Picha & Peters (1998).
Pr/Ph – pristane/phytane;
Ts/(Ts + Tm) – 18
(H)-22,29,30-trisnorhopane)(Peters & Moldowan 1993);
(H)-hop. – regular steranes consist of the C
(20S + 20R), 17
(H)-hopanes consist of the C
pseudohomologue (including 22S and 22R epimers) (Peters & Mol-
Homohopane Index – C
) homohopanes (Peters & Moldowan 1993);
tri – C
tricyclic terpane (Wan Hasiah 1999);
(20R + 20S) C
sterane + 5
(H)(20R + 20S)] C
(Peters & Moldowan 1993);
20S/(20S + 20R) – C
+R)] (Peters & Moldowan 1993);
MDR – methyldibenzothiophene ratio [4-MDBT]/[1-MDBT] (Radke et al. 1986);
(%) = 0.073 MDR + 0.51 (Radke & Willsch 1994);
TA(I)/TA(I + II) – sum of C
(20S + 20R) triaromatic steroids as TA(II) and
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).
Ts/(Ts + Tm)
20S/(20S + 20R)
Polycyclic Aromatic Compounds
TA(I)/TA(I + II)
Table 4: Geochemical characteristics of the bitumens from the Tatra Mountains.
HYDROCARBONS MIGRATION IN THE TECTONIC ZONES OF WESTERN TATRA MTS 11
quence is about 1.5—2.0, which together with paleomagnetic
studies, suggests that the whole complex was heated to 50—
80 °C for about 10 Ma (Grabowski et al. 1999). The highest
possible temperature of syntectonic heating was suggested
for the lower parts of the parautochthonous and overthrust
Tatricum sequences. It is 150—200 °C (Lefeld 1997a).
Comparison with the Outer Western Carpathian crude oils
showed that the investigated bitumens resemble Jurassic rock-
oils more than Paleogene ones. Jurassic marine sedimentary
rocks in the Western Tatra Mts are present both in the Tatricum
and in the Krížna Nappe. However, the Krížna Nappe Triassic-
Jurassic carbonate series were deposited in a deep sedimentary
Fig. 10. A – Ternary diagram of C
(H) hopanes. See Table 4 for detailed designations. B – Similar chromatographic dis-
tribution of metyldibenzothiophenes (m/z 198), dimetyldibenzothiophenes (m/z 212) and tentatively identified trimetyldibenzothiophenes
(m/z 228) for bitumens from the Tatra Mountains with description of individual peaks (after Chakhmakchev et al. 1997; Mössner et al.
1999). Theoretical value of vitrinite reflectance (R
[%] = 0.073 MDR + 0.51) MDR = (4-MBT)/(1-MBT) after Radke & Willsch (1994).
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.
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-
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