The P-V̄-T-X-f O2 evolution of H2O-CO2-CH4-bearing fluid in a wolframite vein: Reconstruction from fluid inclusion studies

Aqueous-carbonaceous and later pure aqueous fluid inclusions in quartz from a ferberite (Fe_.95Mn_.05 WO₄) vein within the low-grade metamorphic aureole of the Borne granite (French Massif Central) have been studied by microthermometry and Raman spectrometry. The bulk V?-X properties of the aqueous-carbonaceous inclusions have been derived using the equation of state of Heyenet al. (1982) for the low-temperature CO₂-CH₄ system. A P-T path has been proposed for their trapping using the equations of state of Jacobs and Kerrick (1981a) for the H₂O-CO₂-CH₄ system. Two main episodes were reconstructed for the history of the aqueous-carbonaceous fluid. (1) Primary H₂O-CO₂-CH₄ vapourrich inclusions in quartz indicated the early circulation of a low-density fluid (65 mole% H₂O-34 mole% CO₂-1 mole% CH₄ and traces of N₂: d = 0.35 gcm^?3) at around 550° ± 50°C and 700 ± 100 bar. Fluid cooled approximately isobarically to 450°-400°C and was progressively diluted by H₂O with a concomitant increase in density. The fO₂ of the H₂OCO₂-CH₄ fluid, estimated from the equilibrium CO₂ + 2H₂O CH₄ + 2O₂, first ranged from 10^?22 to 10^?27 bar, close to the Q-F-M buffer. Within analytical errors, these values were consistent with the presence of graphite in equilibrium with the fluid. (2) A drop in PCO₂, and therefore a drop in fO₂, was recorded by the secondary liquid-rich inclusions in quartz. The inclusions, formed at and below 400°C, were composed of H₂O and CH₄ only, and fO₂ at that stage was below that fixed by the graphite-fluid equilibrium. This second episode in the fluid-rock system could be explained by the drop of temperature below the blocking temperature of the graphite-fluid equilibrium. According to this interpretation, the blocking of the graphite-fluid equilibrium occurred at T ≥ 370°C and probably at 400°C on account of the pressure correction. Mass spectrometric data show that ferberite contains H₂O, CO₂ and CH₄ in fluid inclusions, which lie in the gap of the V?-X properties of the aqueouscarbonaceous fluid in quartz. Deposition of ferberite probably occurred at around 400°C, the previously inferred blocking temperature, resulting from either the drop in PCO₂, the drop fO₂ and/or the related pH-increase.It is concluded that the existence of a blocking-temperature for the graphite-fluid chemical equilibrium may be a critical factor for maintaining a stable fluid pressure gradient in geothermal systems occurring under greenschist facies conditions in graphite-bearing rocks.     

Late Cretaceous porphyry Cu and epithermal Cu–Au association in the Southern Panagyurishte District,Bulgaria: the paired Vlaykov Vruh and Elshitsa deposits

Vlaykov Vruh–Elshitsa represents the best example of paired porphyry Cu and epithermal Cu–Au deposits within the Late Cretaceous Apuseni–Banat–Timok–Srednogorie magmatic and metallogenic belt of Eastern Europe. The two deposits are part of the NW trending Panagyurishte magmato-tectonic corridor of central Bulgaria. The deposits were formed along the SW flank of the Elshitsa volcano-intrusive complex and are spatially associated with N110-120-trending hypabyssal and subvolcanic bodies of granodioritic composition. At Elshitsa, more than ten lenticular to columnar massive ore bodies are discordant with respect to the host rock and are structurally controlled. A particular feature of the mineralization is the overprinting of an early stage high-sulfidation mineral assemblage (pyrite ± enargite ± covellite ± goldfieldite) by an intermediate-sulfidation paragenesis with a characteristic Cu–Bi–Te–Pb–Zn signature forming the main economic parts of the ore bodies. The two stages of mineralization produced two compositionally different types of ores—massive pyrite and copper–pyrite bodies. Vlaykov Vruh shares features with typical porphyry Cu systems. Their common geological and structural setting, ore-forming processes, and paragenesis, as well as the observed alteration and geochemical lateral and vertical zonation, allow us to interpret the Elshitsa and Vlaykov Vruh deposits as the deep part of a high-sulfidation epithermal system and its spatially and genetically related porphyry Cu counterpart, respectively. The magmatic–hydrothermal system at Vlaykov Vruh–Elshitsa produced much smaller deposits than similar complexes in the northern part of the Panagyurishte district (Chelopech, Elatsite, Assarel). Magma chemistry and isotopic signature are some of the main differences between the northern and southern parts of the district. Major and trace element geochemistry of the Elshitsa magmatic complex are indicative for the medium- to high-K calc-alkaline character of the magmas. ⁸⁷Sr/⁸⁶Sr_(i) ratios of igneous rocks in the range of 0.70464 to 0.70612 and ¹⁴³Nd/¹⁴⁴Nd_(i) ratios in the range of 0.51241 to 0.51255 indicate mixed crustal–mantle components of the magmas dominated by mantellic signatures. The epsilon Hf composition of magmatic zircons (+6.2 to +9.6) also suggests mixed mantellic–crustal sources of the magmas. However, Pb isotopic signatures of whole rocks (²⁰⁶Pb/²⁰⁴Pb = 18.13–18.64, ²⁰⁷Pb/²⁰⁴Pb = 15.58–15.64, and ²⁰⁸Pb/²⁰⁴Pb = 37.69–38.56) along with common inheritance component detected in magmatic zircons also imply assimilation processes of pre-Variscan and Variscan basement at various scales. U–Pb zircon and rutile dating allowed determination of the timing of porphyry ore formation at Vlaykov Vruh (85.6 ± 0.9 Ma), which immediately followed the crystallization of the subvolcanic dacitic bodies at Elshitsa (86.11 ± 0.23 Ma) and the Elshitsa granite (86.62 ± 0.02 Ma). Strontium isotope analyses of hydrothermal sulfates and carbonates (⁸⁷Sr/⁸⁶Sr = 0.70581–0.70729) suggest large-scale interaction between mineralizing fluids and basement lithologies at Elshitsa–Vlaykov Vruh. Lead isotope compositions of hydrothermal sulfides (²⁰⁶Pb/²⁰⁴Pb = 18.432–18.534, ²⁰⁷Pb/²⁰⁴Pb = 15.608–15.647, and ²⁰⁸Pb/²⁰⁴Pb = 37.497–38.630) allow attribution of ore-formation in the porphyry and epithermal deposits in the Southern Panagyurishte district to a single metallogenic event with a common source of metals.     

Mineralogical and isotopic record of biotic and abiotic diagenesis of the Callovian-Oxfordian clayey formation of Bure (France)

The Callovian-Oxfordian (COx) clayey unit is being studied in the Eastern part of the Paris Basin at depths between 400 and 500 m depth to assess of its suitability for nuclear waste disposal. The present study combines new mineralogical and isotopic data to describe the sedimentary history of the COx unit. Petrologic study provided evidence of the following diagenetic mineral sequence: (1) framboidal pyrite and micritic calcite, (2) iron-rich euhedral carbonates (ankerite, sideroplesite) and glauconite (3) limpid calcite and dolomite and celestite infilling residual porosity in bioclasts and cracks, (4) chalcedony, (5) quartz/calcite. Pyrite in bioturbations shows a wide range of δ³⁴S (−38‰ to +34.5‰), providing evidence of bacterial sulphate reduction processes in changing sedimentation conditions. The most negative values (−38‰ to −22‰), measured in the lower part of the COx unit indicate precipitation of pyrite in a marine environment with a continuous sulphate supply. The most positive pyrite δ³⁴S values (−14‰ up to +34.5‰) in the upper part of the COx unit indicate pyrite precipitation in a closed system. Celestite δ³⁴S values reflect the last evolutionary stage of the system when bacterial activity ended; however its deposition cannot be possible without sulphate supply due to carbonate bioclast dissolution. The ⁸⁷Sr/⁸⁶Sr ratio of celestite (0.706872-0.707040) is consistent with deposition from Jurassic marine-derived waters. Carbon and oxygen isotopic compositions of bulk calcite and dolomite are consistent with marine carbonates. Siderite, only present in the maximum clay zone, has chemical composition and δ¹⁸O consistent with a marine environment. Its δ¹³C is however lower than those of marine carbonates, suggesting a contribution of ¹³C-depleted carbon from degradation of organic matter. δ¹⁸O values of diagenetic chalcedony range between +27‰ and +31‰, suggesting precipitation from marine-derived pore waters. Late calcite crosscutting a vein filled with chalcedony and celestite, and late euhedral quartz in a limestone from the top of the formation have lower δ¹⁸O values (∼+19‰), suggesting that they precipitated from meteoric fluids, isotopically close to present-day pore waters of the formation. Finally, the study illustrates the transition from very active, biotic diagenesis to abiotic diagenesis. This transition appears to be driven by compaction of the sediment, which inhibited movement of bacterial cells by reduction of porosity and pore sizes, rather than a lack of inorganic carbon or sulphates.     

The high temperature reaction zone of the Oman ophiolite: new field data,microthermometry of fluid inclusions,PIXE analyses and oxygen isotopic ratios

Marine Geophysical Research - The present study is focused on the so-called High Temprature Reaction Zone of the Oman ophiolite, a thin zone located between the roots of the sheeted dyke complex...