Superdense CO2 inclusions in Cretaceous quartz–stibnite veins hosted in low-grade Variscan basement of the Western Carpathians, Slovakia

CO₂ inclusions with density up to 1,197 kg m⁻³ occur in quartz–stibnite veins hosted in the low-grade Palaeozoic basement of the Gemericum tectonic unit in the Western Carpathians. Raman microanalysis corroborated CO₂ as dominant gas species accompanied by small amounts of nitrogen (<7.3 mol%) and methane (<2.5 mol%). The superdense CO₂ phase exsolved from an aqueous bulk fluid at temperatures of 183–237°C and pressures between 1.6 and 3.5 kbar, possibly up to 4.5 kbar. Low thermal gradients (∼12–13°C km⁻¹) and the CO₂–CH₄–N₂ fluid composition rule out a genetic link with the subjacent Permian granites and indicate an external, either metamorphogenic (oxidation of siderite, dedolomitization) or lower crustal/mantle, source of the ore-forming fluids.According to microprobe U–Pb–Th dating of monazite, the stibnite-bearing veins formed during early Cretaceous thrusting of the Gemeric basement over the adjacent Veporic unit. The 15- to 18-km depth of burial estimated from the fluid inclusion trapping PT parameters indicates a 8- to 11-km-thick Upper Palaeozoic–Jurassic accretionary complex overlying the Gemeric basement and its Permo-Triassic autochthonous cover.     

Glassy orthopyroxene granodiorites of the Pannonian Basin: tracers of ultra-high-temperature deep-crustal anatexis triggered by Tertiary basaltic volcanism

Glassy orthopyroxene granodiorite-tonalite (named pincinite after type locality) was described from basaltic lapilli tuffs of the Pliocene maar near Pinciná village in the Slovakian part of the Pannonian Basin. Two pincinite types exhibit a qualitatively similar mineral composition (quartz, An_20–55 plagioclase, intergranular silicic glass with orthopyroxene and ilmenite, ±K-feldspar), but strongly different redox potential and formation PT conditions. Peraluminous pincinite is reduced (6–7% of total iron as Fe³⁺ in corundum-normative intergranular dacitic glass) and contains ilmenite with 8–10 mol% Fe₂O₃ and orthopyroxene dominated by ferrosilite. High-density (up to 0.85 g/cm³) primary CO₂ inclusions with minor H₂, CH₄, H₂S, CO and N₂ (<2 mol% total) are present in Qtz and Plg. Equilibrium PT conditions inferred from the intergranular Opx–Ilm–Glass assemblage and fluid density correspond to 1,170±50°C, 5.6±0.4 kbar, respectively. Metaluminous pincinite is more oxidised (25–27% of total iron as Fe³⁺ in diopside-normative intergranular glass of rhyolite–trachyte–dacite composition) and contains Fe₂O₃-rich ilmenite (17–29 mol%) associated with enstatite. Fluid inclusions are composed of CO₂–H₂O mixtures with up to 38 mol% H₂O. Raman spectroscopy revealed H₂S along with dominant CO₂ in the carbonic phase. Equilibrium PT parameters for the intergranular Opx–Ilm–Glass assemblage correspond to 740±15°C, 2.8±0.1 kbar, respectively. Reducing gas species (<2 mol% total) in the CO₂-inclusions of the peraluminous pincinite resulted from hydrogen diffusion due to fH₂ gradient imposed during decrease of redox potential from the log fO₂ values near QFM during Qtz + Plg growth, to QFM-2 incidental to the superimposed Opx + Ilm assemblage in the intergranular melt. The decrease in oxygen fugacity was recorded also in the metaluminous pincinite, where log fO₂ values changed from ~QFM + 2.6 to QFM + 0.4, but hydrogen diffusion did not occur. Absence of OH-bearing minerals, major and trace element abundances (e.g. REE 300–320, Nb 55–57, Th 4–31, Zr 240–300 ppm, FeO_tot/MgO up to 11), and Sr–O isotope ratios in the pincinites are diagnostic of high-temperature anorogenic magmas originated by dehydration melting of biotite in quartz-feldspathoid crust (⁸⁷Sr/⁸⁶Sr>0.705–0.706, ¹⁸O>9 V-SMOW) around alkali basalt reservoir in depths between 17 and 20 km, and around late stage derivatives of the basalt fractionation, intruding the crust up to depths of 10–11 km. Low water activity in the pincinite parental melt was caused by CO₂-flux from the Tertiary basaltic reservoirs and intrusions. The anatexis leads to generation of a melt-depleted granulitic crust beneath the Pannonian Basin, and the pincinites are interpreted as equivalents of igneous charnockites and enderbites quenched at temperatures above solidus and unaffected by sub-solidus re-equilibration and metamorphic overprint.     

Fluid-assisted retrogression of garnet and P–T history of metapelites from HP/UHP metamorphic terrane (Pohorje Mountains, Eastern Alps)

Fluid inclusions in garnet combined with element X-ray mapping, phase equilibrium modelling and conventional thermobarometry have been used to constrain the metamorphic evolution of metapelitic gneiss from the HP/UHP metamorphic terrane of Pohorje Mountains in the Eastern Alps, Slovenia. Retrograde P–T trajectory from ~2.75 GPa and 780°C is constrained by the composition of matrix phengite (6.66 apfu Si) coexisting with garnet cores, kyanite and quartz. The intersection of the X _Prp = 0.25 isopleth for the garnet with the upper stability boundary for K-feldspar in the matrix indicates near-isothermal decompression to ~0.9 GPa at 720°C. Temperatures over 650°C during this stage are corroborated by the high degree of ordering of graphite inclusions associated with Zn, Mg-rich staurolite and phlogopite in the Mg-rich (X _Prp = 0.22–0.25) garnet cores. Majority of garnet porphyroblasts are depleted in Mg (down to X _Prp = 0.09) and enriched in Mn (up to X _Sps = 0.12) along cracks and at their margins. The associated retrograde mineral assemblage comprises Zn, Mg-poor staurolite, muscovite, biotite–siderophyllite, sillimanite and quartz. The onset of the retrogression and the compositional modification of the garnet porphyroblasts were accompanied by the addition of fluid-deposited graphite around older graphite inclusions, probably due to removal of water from a graphite-buffered COH fluid by dissolution in partial silicic melt. Instantaneous expulsion of water near the melt solidus (640°C, max. 0.45 GPa) caused dissolution of the graphite at redox conditions corresponding to 0.25–1.25 logfO₂ units below the QFM buffer, giving rise to a H₂O–CO₂–CH₄ fluid trapped in primary inclusions in Mn-rich, Mg-poor, almandine garnet that reprecipitated within the retrogressed domains. The absence of re-equilibration textures and consistent densities of the fluid inclusions reflect a near-isochoric cooling postdating the near-isothermal decompression. Bulk water content in the metapelite attained 2 wt% during this stage. The low-degree partial melting and extensive hydration due to the release of the internally derived, low-pressure aqueous fluids led to the reset of peak-pressure mineral assemblage.     

Origin of the fluids associated with granodiorite-hosted,Sb-As-Au-W mineralisation at Dúbrava (Nízke Tatry Mts,Western Carpathians)

Mineral parageneses of the polymetallic, Sbrich deposit at Dúbrava has been formed during five separated stages. A fluid inclusion study demonstrates that the earliest stages with scheelite, molybdenite and arsenopyrite have been associated with immiscible CO₂ (± CH₄)-rich, low-saline fluids at temperatures between 300 and 400 °C and pressures as much as 2 kbar. Deposition of the main, superimposed ores, stibnite and zinckenite, has been intimately connected with circulation of aqeuous, moderately saline fluids (15.5–23.5 wt% NaCl equiv.) upon epithermal conditions. Salinity of the aqueous fluids associated with tetrahedrite is clustered around 10 wt% NaCl equiv. Quartz from the latest, barite stage has precipitated from aqueous fluids enriched in divalent cations. These fluids are believed to be genetically linked with Triassic evaporite formations preserved in the region. Temperature-salinity diagrams constructed from microthermometry data indicate influx of diluted meteorite water in the stibnite, tetrahedrite and barite stages. Isotopic data are in accordance with model. The ¹⁸O values between –9.3 and +1.5 have been derived for water in equilibrium with quartz, coexisting with sphalerite, tetrahedrite and barite, thus confirming the participation of isotopically lighter meteoric waters in the mineral-forming solutions. The ( ¹⁸O) values between +3.3 and +8.5 estimated for the water associated with the scheelite and arsenopyrite stages, are suggestive for the majority of metamorphic and/or magmatic water in the mineral-forming, CO₂-rich solutions.     

A boundary layer-induced immiscibility in naturally re-equilibrated H2O-CO2-NaCl inclusions from metamorphic quartz (Western Carpathians,Czechoslovakia)

Naturally re-equilibrated fluid inclusions have been found in quartz crystals from alpine fissures of the Western Carpathians. Re-equilibration textures, such as planar arrangement of the decrepitation clusters as well as the quartz c- and a-axis oriented fracturing indicate explosion of fluid inclusions. The extent of fracturing, which is dependent on inclusion diameters, suggests inclusion fluid overpressures between 0.6–1.9 kb. Microthermometry data are controversial with the textures because of indicating roughly fixed initial fluid composition and density during re-equilibration, although inclusion volumes have been sometimes substantially reduced by crystallization of newly-formed quartz. It is concluded that fluid loss from re-equilibrated inclusions must have been compensated for by replacing equivalent quartz volume from cracks into parent inclusion. Such a mechanism has operated in a closed system and the re-equilibration related cracks have not been connected with mineral surface. The compositional and density differences between aqueous inclusions in decrepitation clusters and CO₂-rich parent inclusions cannot be interpreted in terms of classical fluid immiscibility. Moreover, monophase liquid-filled aqueous inclusions and coexisting monophase CO₂ vapour-filled inclusions in the decrepitation clusters are thermodynamically unacceptable under equilibrium metamorphic conditions. The effect of disjoining pressure resulting from structural and electrostatic forces in very thin fractures is suspected to have caused density and compositional inconsistencies between parent and cluster inclusions, as well as the unusual appearance of cluster inclusions. In high-grade metamorphic conditions, the re-equilibration probably leads to boundary layer-induced immiscibility of homogeneous H₂O–CO₂–NaCl fluids and to formation of compositionally contrasting CO₂-rich and aqueous inclusions.     

Combined U/Pb and (U–Th)/He geochronometry of basalt maars in Western Carpathians: implications for age of intraplate volcanism and origin of zircon metasomatism

The age of intraplate volcanism in northern Pannonian Basin of Carpathians is revisited using a combination of zircon U/Pb, zircon (U–Th)/He and apatite (U–Th)/He dating techniques, complemented by electron microprobe (EMP) characterisation of dated minerals. A total of six maar structures and diatremes in the South-Slovakian Volcanic Field (SSVF) were dated and the obtained new ages yielded the following key findings: Two isolated maars in SE part indirectly dated by geomorphologic constraints to Late Pleistocene are actually of Pliocene (2.8 ± 0.2 Ma) and Late Miocene (5.5 ± 0.6 Ma) ages. In contrast, two maars in NW part of the study area are of Late Pliocene age (4.1 ± 0.4 and 5.2–5.4 Ma), younger than the Late Miocene age (~6.5 Ma) inferred previously from K/Ar data on the proximal basaltic lava flows. These maars therefore belong to the second volcanic phase that was previously identified only in SE part of the SSVF. In the light of the new geochronologic data, it seems likely that the Pliocene phreatomagmatic eruptions may have occurred along extension-related, NW- and NE-trending orthogonal faults. EMP analyses and imaging revealed an extensive syn- and post-growth metasomatic replacement by dissolution-reprecipitation in the majority of zircons. Abundant silicate melt inclusions in porous metasomatised parts of the zircons are diagnostic of magmatic rather than hydrothermal metasomatism. Consistent ages of the metasomatised and non-metasomatised zones do not indicate disturbance of the U–Pb system during the metasomatism. Enrichment in U and Th loss in the metasomatised zircons are diagnostic of an increasing oxygen fugacity triggered by degassing of the volatile residual melt during the final stages of alkali basalt fractionation. Rare zircon-to-baddeleyite transformation was probably connected with lowered silica activity in carbonated basaltic magmas in south-eastern part of the study area.     

Fluid inclusion evidence for deep burial of the Tertiary accretionary wedge of the Carpathians

Hydrothermal quartz from mineralized joints of the Carpathian accretionary wedge contains immiscible aqueous, oil‐condensate, methane and carbon dioxide‐rich fluid inclusions. Distribution patterns of the inclusion trapping PT parameters point to a crack‐seal mechanism during upward and lateral migration of hot methane‐rich fluids from overpressured sediments at the base of the accretionary wedge. A simple equation is proposed to calculate depths from densities and trapping pressures of the buoyant inclusion fluids. In the Carpathian accretionary wedge, the paleofluid pressures of 52–306 MPa correspond to a 5‐ to 11‐km‐thick overburden. Prior to exhumation, thickness of the wedge must have attained 10–25 km, of which only c. 50% was preserved until recently. Anomalously high methane densities (up to 0.43 g cm^?3) recorded in the lowermost nappe sheets are provisionally interpreted as a result of supralithostatic overpressure due to thermal cracking of oil and kerogen to methane and pyrobitumen at temperatures above 200 °C.     

Dehydration melting and devolatilization during exhumation of high-grade metapelites: the Tatra Mountains, Western Carpathians

Partial melting and retrogression related to Variscan tectonic exhumation have been recognized in the high-grade metapelites of the Tatra Mountains, Western Carpathians. Staurolite and kyanite relics document an early stage of the prograde metamorphism at c. 600 °C and 9–10 kbar. An increase in temperature to >730 °C at 11–12 kbar resulted in partial melting and incipient migmatization in the stability field of kyanite. Further heating at decreasing pressure during the earliest stage of exhumation led to the dehydration-melting of muscovite and biotite at >750–800 °C and 6–10 kbar, producing garnet-bearing granite as leucosomes in migmatite. Subsequent cooling is documented by garnet resorption by biotite and sillimanite (a reversal of the prograde biotite dehydration-melting reaction). This was followed by nearly isothermal decompression to c. 4–5 kbar producing cordierite and some melt due to biotite decomposition. Later nearly isobaric cooling led to cordierite pinitization and formation of orthoamphibole, chlorite and carbonates. Densities of primary, monophase CO₂–N₂ inclusions (0.69–1.06 g cm^?3) from the migmatite leucosome are consistent with the near-peak and retrograde conditions. Highly varying N₂ contents (5–30 mol%) are thought to result from the nitrogen uptake in retrograde K-bearing minerals, or dilution by CO₂ liberated during interaction of melt-derived water with metapelite graphite. The relatively high nitrogen content, not observed until now in migmatites, could have been inherited from the high-pressure metamorphism stage. It is assumed that the water-absent composition of fluid inclusions is not representative of the bulk water content (X_H2O≤0.7), which was masked by mechanical separation of the CO₂- and H₂O-dominated immiscible phases, and/or by post-entrapment modifications of the fluid inclusions. Decompression and the final stage of exhumation were accomplished by top-to-the-south thrusting as well as west–east (orogen-parallel) extension. They were most probably related to regional uplift and gravitational collapse of thermally weakened Variscan crust.     

Immiscible separation of metalliferous Fe/ Ti-oxide melts from fractionating alkali basalt: P-T-f O2 conditions and two-liquid elemental partitioning

Globules of iron-dominated (59–69 wt% FeO_tot) and titanium-dominated (43.5 wt% TiO₂) oxide melts have been detected in igneous xenoliths from Pliocene-to-Pleistocene alkali basalts of the Western Carpathians. Fluid inclusion and mineral composition data indicate immiscible separation of the high-iron-oxide melt (HIM) at magmatic temperatures. The HIM separation occurred during clinopyroxene (augite) accumulation in an alkali trachybasalt and continued during crystallization of amphibole (kaersutite) and K-feldspar (anorthoclase), the latter coexisting with trachyte and alkalic rhyolite residual melts. Some HIM was also expelled from sub-alkalic rhyolite (70–77% SiO₂), coexisting with An_27–45 plagioclase and quartz in granitic (tonalite-trondhjemite) xenoliths. Oxygen fugacities during HIM separation range from −1.4 to +0.6 log units around the QFM buffer. A close genetic relationship between HIM-hosted xenoliths and mantle-derived basaltic magma is documented by mineral ¹⁸O values ranging from 4.9 to 5.9‰ V-SMOW. δD values of gabbroic kaersutite between −61 and −86‰ V-SMOW are in agreement with a presumed primary magmatic water source. Most trace elements, except Li, Rb and Cs, have preferentially partitioned into the HIM. The HIM/Si-melt partition coefficients for transition elements (Sc, V, Cr, Co, Ni) and base metals (Zn, Cu, Mo) are between 2–160, resulting in extreme enrichment in the HIM. La and Ce also concentrate in the silicic melt, whereas Tb-Tm in the HIM. Hence, the immiscible separation causes REE fractionation and produces residual silicic melt enriched in LREE and depleted in HREE. The weak fractionation among Tb-Tm and Yb, Lu can be attributed to recurrent extraction of the HIM from the magmatic system, while flat HREE chondrite-normalized patterns are interpreted to indicate no or little loss of the HIM. Received: 30 September 1997 / Accepted: 23 March 1998