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ABSTRACT
Hydrothermal quartz from mineralized joints of the Carpathian 11-km-thick overburden. Prior to exhumation, thickness of the
accretionary wedge contains immiscible aqueous, oil-conden- wedge must have attained 1025 km, of which only c. 50% was
sate, methane and carbon dioxide-rich fluid inclusions. Distri- preserved until recently. Anomalously high methane densities
bution patterns of the inclusion trapping PT parameters point to (up to 0.43 g cm)3) recorded in the lowermost nappe sheets are
a crack-seal mechanism during upward and lateral migration of provisionally interpreted as a result of supralithostatic over-
hot methane-rich fluids from overpressured sediments at the pressure due to thermal cracking of oil and kerogen to methane
base of the accretionary wedge. A simple equation is proposed and pyrobitumen at temperatures above 200 C.
to calculate depths from densities and trapping pressures of the
buoyant inclusion fluids. In the Carpathian accretionary wedge, Terra Nova, 18, 440446, 2006
the paleofluid pressures of 52306 MPa correspond to a 5- to
Fluid inclusions are essential source basin of the Outer Western Carpathi-
Introduction
of information on thermal and pres- ans during crystallisation of drusy
The non-metamorphosed Tertiary sure history of non-metamorphosed quartz. The results show that the
accretionary wedge of the Carpathian accretionary complexes. Moreover, accretionary wedge must have been
orogenic system belongs to few thrust- the uid inclusions are most sensitive substantially thicker than recently
and-fold belts with economically geological barometers, from which assumed in tectonic models and
important oil and gas deposits. In also other parameters, such as depths balanced cross-sections.
such orogenic systems, knowledge on of burial and geothermal gradients,
thermal history and depth of burial is can be derived. According to recent
Geological Background
essential for identication of potential models of rock rheology (e.g. Sibson,
source rocks, uid migration paths 1990; Holbrook, 1999) and leak-o The Carpathian segment of the Euro-
and location of possible hydrocarbon data from sedimentary basins (Gaa- pean Alpine orogenic system consists
traps. Balanced modelling based on renstroom et al., 1993), pore uid of several rootless nappes composed
reection seismic proles and struc- pressure cannot exceed the lithostatic of Early CretaceousMiocene ysch
tural data provides a tool for recon- load plus cohesive (tensile) strength of sediments detached along single
struction of burial history, the rock without fracturing and reset- decollement horizon and thrust north-
quantication of erosion, shortening ting the hydrostatic pressure gradient. ward over shallow-marine Neogene
and potential trap-destruction proces- Hence, the depth of burial is com- molasse and the underlying platforms
ses. Controversial quantication of monly calculated from uid inclusion (e.g. Picha, 1996). A weakly deformed
the balanced proles in the Carpathi- trapping pressures assuming either Eocene-to-Early Miocene fore-arc y-
ans (Behrmann et al., 2000; Posp s il hydrostatic or lithostatic loads, and sch basin (Gedl, 2000; Sotak et al.,
et al., 2005b; Nemcok et al., 2006) geological constraints. However, in 2001; Kazmer et al., 2003) overlies
stems partly in the absence of data the case of trapping a buoyant hetero- Variscan crystalline basement and its
on paleothickness of the accretionary geneous uid, the inferred depths are Mesozoic cover and nappe units south
wedge, because some of the original subject to a large error margin due to of a steep suture-like zone called the
nappe units could have been removed the unknown bulk uid density and Pieniny klippen belt, which provides
during subduction (Nemcok et al., the magnitude of uid overpressure. hinterland termination of the accre-
1998) or exhumation. A crack-seal mechanism (Ramsay, tionary wedge and the boundary
1980) and uid buoyancy eect (Sa- between the outer and inner Carpa-
hagian and Proussevitch, 1992) were thians (Fig. 1).
Correspondence: Prof. Vratislav Hurai, employed in this article to quantita- Mineralized joints of the Creta-
Department of Mineralogy and Petrology, tively interpret large pressure uctua- ceousOligocene ysch sandstones
Comenius University, Mlynska Dolina, tions of buoyant uids percolating contain several generations of brous,
Bratislava 842 15, Slovakia. Tel.: +42 through open cavities in ysch sedi- columnar, blocky and drusy calcite
12 65 31 64 60; fax: +42 12 65 31 62 93; ments of the Tertiary accretionary and quartz, having precipitated during
e-mail: huraiova@fns.uniba.sk wedge and the associated fore-arc syn-sedimentary folding, thrusting
Fig. 1 Simplied geological map of the study area redrawn from the geological map 1:500 000 (Lexa et al., 2000). Circles with
orange, blue and white sectors denote relative proportions of oil-condensate, carbon dioxide and methane, respectively, in carbonic
uid inclusions. Non-numbered circles denote outcrops, numbered circles are boreholes: 1, Zborov 1 (37145156 m); 2, Hanus ovce
1 (4469 m); 3, Zboj 1 (38964146 m); 4, Lipany 5 (1996 m); numbers in parentheses pertain to depth intervals with the
corresponding uid inclusion composition.
and counter clockwise rotation of the solution, and variable phase ratios devoid of higher hydrocarbons is the
accretionary wedge (Swierczewska indicate trapping a heterogeneous dominant carbonic species (Fig. 1).
et al., 2000). Blocky and drusy quartz methanewater mixture (Fig. 2c). Aqueous solutions accompany the
studied represent the last generation Carbon dioxide-rich inclusions consist carbonic compounds in the whole
formed in central open uid-lled mostly of single liquid phase, and are area. Their salinities range between 0
cavities (Fig. 2a) because of an exten- thus indistinguishable from the mono- and 3.2 wt% and most likely reect
sion correlated with a post-Oligocene phase methane inclusions at room mixing of meteoric and marine waters
collapse and exhumation of the accre- temperature. The presence of carbon in the fracture uids.
tionary wedge (Swierczewska et al., dioxide at room temperature is some-
2000; Tokarski et al., 2006). times indicated by a liquidliquid
Temperature and Pressure
Oil-condensate, methane and car- vapour phase assemblage diagnostic
bon dioxide are the main carbonic of a composite CO2-rich aqueous uid In majority of cases, uid inclusions in
compounds of uid inclusions hosted (Fig. 2d). quartz are quite reliable indicators of
in blocky and drusy quartz. Fluid Methane with up to 8 mol% of crystallization PT conditions, because
composition in the quartz diers carbon dioxide is typical of mineral- of retaining their original density dur-
strongly from earlier quartz and cal- ized joints of the Magura nappe and ing tectonic transport to Earths sur-
cite generations, which contain only the underlying Dukla unit, both crop- face. Inclusions of heterogeneous
low-to-moderately saline aqueous ping out in the innermost part of the uids consisting of two or more
solutions. At room temperature, the accretionary complex. Higher gaseous immiscible phases with contrasting
oil-condensate inclusions consist of hydrocarbons and crude oil accom- densities and compositions are most
one to four phases: transparent pany the methane in the proximity of useful geothermobarometers (Roed-
oil-condensate liquid, methane-con- organic-rich Oligocene shales called der and Bodnar, 1980). The hetero-
densate vapour bubble, pale green- Menilite Beds in the Dukla unit. CO2 geneous uid mixtures are identiable
to-dark brown heavy liquid oil, and CH4 mixtures passing in places into according to variable phase ratios in
dark brown-to-opaque solid hydro- almost pure carbon dioxide liquid are coeval inclusions (Fig. 2c). Methane
carbons. The oil-condensate phase typical of the Zboj unit underlying (CO2)aqueous mixtures are suit-
uoresce white-to-pale blue under both the Magura nappe and the Du- able for determination of their trap-
365 nm UV light (Fig. 2b). Methane kla unit. Oil- and methane-rich con- ping PT parameters; because their
forms mostly monophase liquid inclu- densate occurs in the Eocene composition and density can be easily
sions. An additional liquid discernible Oligocene strata of fore-arc basin, inferred from temperatures of phase
in the CH4-rich inclusions corres- except for segment uplifted north of transitions on cooling and heating
ponds either to oil or to aqueous the sub-Tatric fault, where methane with assistance from experimental
Fig. 2 (a) Photomicrograph of mineralized joints in ysch sandstone, illustrating early fracture lled with columnar calcite
intersected by a later composite fracture lled with columnar calcite at margins and blocky calcite and quartz in the centre. (b)
Primary inclusions of oil-condensate from quartz veins in Middle Oligocene strata of the western part of fore-arc basin, near to
Pucov village. Inset illustrates UV uorescence (365 nm) image of the same inclusions. (c) Pseudosecondary inclusions in quartz
from methane zone of the forearc basin (Middle-Upper Eocene sandstones, Zalesie, Spis ska Magura Mountains), containing
variable proportions of methane and aqueous liquids. Monophase inclusions are composed of methane liquid. Homogenization
temperature of the aqueous inclusion with the smallest bubble marked by arrow corresponds to true trapping temperature. (d)
CO2-bearing aqueous inclusions in quartz from carbon dioxide zone of the accretionary complex. Zboj unit, Upper Eocene-Lower
Oligocene, Zboj-1 borehole, 4164 m. Black bars correspond to 1 mm in (a) and 20 lm in (b)(d).
phase diagrams and equations of state ping temperatures in the fore-arc the minimal uid inclusion trapping
(e.g. Holloway, 1981; Kleinrahm and basin and the Magura nappe com- temperature of 195 C (i.e. presuma-
Wagner, 1986; Thiery et al., 1994). In pared with those in the Dukla and the ble rock temperature) exceeded the
statistically relevant number of meas- underlying Zboj units (Fig. 3). The minimum oil cracking limit of 180 C
urements, the minimal homogeniza- temperature scatter, tending to reduc- (Tissot and Welte, 1984).
tion temperature (Th) of aqueous tion with depth, is interpreted as Pressures inferred from densities of
inclusions equals that of trapping, reecting inux of hot uid into colder methane inclusions (Fig. 3) tend to
whereas trapping pressure is dened sediments. Hence, the minimal uid increase from 52180 MPa in the fore-
by the iso-density line (isochore) of the inclusion trapping temperature is arc basin, to 76200 MPa in the Ma-
coexisting methane inclusion (Vityk likely to approach that of rock, gura nappe and to 109370 MPa in
et al., 1996; Evans and Battles, 1999; whereas the maximal temperature the underlying Dukla unit. Maximum
Hurai et al., 2002). Total pressure equals that of the incoming uid. This uid pressures (450 MPa) and tem-
correction for water dissolved in the interpretation is supported by the peratures (246 C) have been recorded
methane and for expansion of the host d13C values of inclusion methane from in the Zboj unit underlying the Dukla
quartz is lower than 4 MPa in the drusy quartz of the fore-arc basin unit and the Magura nappe. The
temperature range of 160240 C and ()31& V-PDB) typical of a thermo- strongly uctuating pressures in the
the pressures up to 300 MPa (V. Hu- genic dry gas. The thermogenic individual tectonic units most likely
rai, in preparation). methane with d13C )36& was also reect cyclically changing hydrostatic
In the study area, methane-rich detected in the drusy quartz of the and lithostatic regimes caused by a
inclusions show wider scatter of trap- Dukla unit (Hurai et al., 2002), where crack-seal mechanism (Ramsay, 1980;
Fig. 4 Schematic, non-balanced cross-section of the accretionary wedge across the prole marked in Fig. 1, with the reconstructed
thickness of the removed rocks based on uid inclusion data. The cross-section was constructed using recent geological maps,
balanced cross-sections and geophysical data (Behrmann et al., 2000; Lexa et al., 2000; Oszczypko, 2004; Oszczypko-Clowes and
Oszczypko, 2004; Posp s il et al., 2005a,b; Nemcok et al., 2006). Overburden of the Silesian nappe (Si) has been reconstructed from
uid inclusion data of Jarmolowicz-Szulc and Dudok (2005).