Earth-prints repository, logo   DSpace

About DSpace Software
|earth-prints home page | roma library | bologna library | catania library | milano library | napoli library | palermo library
Please use this identifier to cite or link to this item:

Authors: Etiope, G.*
Baciu, C.*
Schoell, M.*
Title: Extreme methane deuterium, nitrogen and helium enrichment in natural gas from the Homorod seep (Romania)
Title of journal: Chemical Geology
Series/Report no.: 1-2/280 (2011)
Publisher: Elsevier
Issue Date: 7-Jan-2011
DOI: 10.1016/j.chemgeo.2010.10.019
Keywords: Methane
Mud volcano
Abstract: Methane (CH4) in terrestrial environments, whether microbial, thermogenic, or abiogenic, exhibits a large variance in C and H stable isotope ratios due to primary processes of formation. Isotopic variability can be broadened through secondary, post-genetic processes, such as mixing and isotopic fractionation by oxidation. The highest and lowest 13C and 2H (or D, deuterium) concentrations in CH4 found in various geologic environments to date, are defined as “natural” terrestrial extremes. We have discovered a new extreme in a natural gas seep with values of deuterium concentrations, δDCH4, up to+124‰that far exceed those reported for any terrestrial gas. The gas, seeping from the small Homorod mud volcano in Transylvania (Romania), also has extremely high concentrations of nitrogen (N92 vol.%) and helium (up to 1.4 vol.%). Carbon isotopes in CH4, C2H6 and CO2, and nitrogen isotopes in N2 indicate a primary organic sedimentary origin for the gas (a minor mantle component is suggested by the 3He/4He ratio, R/Ra~0.39). Both thermogenic gas formation modeling and Rayleigh fractionation modeling suggest that the extreme deuterium enrichment could be explained by an oxidation process characterised by a δDCH4 and δ13CCH4 enrichment ratio (ΔH/ΔC) of about 20, and may be accounted for by abiogenic oxidation mediated by metal oxides. All favourable conditions for such a process exist in the Homorod area, where increased heat flow during Pliocene–Quaternary volcanism may have played a key role. Finally we observed rapid variations (within 1 h) in C and H isotope ratios of CH4, and in the H2S concentrations which are likely caused by mixing of the deep oxidized CH4–N2–H2S–He rich gas with a microbial methane generated in the mud pool of one of the seeps. We hypothesize that the unusual features of Homorod gas can be the result of a rare combination of factors induced by the proximity of sedimentary organic matter, mafic, metal-rich volcanic rocks and salt diapirs,leading to the following processes: a) primary thermogenic generation of gas at temperatures between 130 and 175 °C; b) secondary alteration through abiogenic oxidation, likely triggered by the Neogene–Quaternary volcanism of the eastern Transylvanian margin; and c) mixing at the surface with microbial methane that formed through fermentation in the mud volcano water pool. The Homorod gas seep is a rare example that demonstrates how post-genetic processes can produce extreme gas isotope signatures (thus far only theorized), and that extremely positive δDCH4 values cannot be used to unambiguously distinguish between biotic and abiotic origin.
Appears in Collections:04.04.12. Fluid Geochemistry
Papers Published / Papers in press

Files in This Item:

File SizeFormatVisibility
Eti-Bac-Sch-HOMOROD-ChemGeo.pdf1.57 MBAdobe PDFView/Open

Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.

Share this record




Stumble it!



Valid XHTML 1.0! ICT Support, development & maintenance are provided by CINECA. Powered on DSpace Software. CINECA