Description: In serpentinised peridotite and ultramafic rock systems, methane (CH4) origin is frequently considered abiotic, but variable microbial and thermogenic components can also exist. Typically, the origin of CH4 is studied using bulk, 13C/12C and 2H/H isotopic composition, molecular gas composition, occasionally radiocarbon (14C), microbiology and geological context. Recent advances in CH4-clumped isotope methods have yielded novel insights into the formation of CH4: nonetheless, their interpretation in natural gas samples is often uncertain and requires additional research. Here, we study the origin of the gas released in hyperalkaline (pH 〉 10) springs in the Ronda Peridotite Massifs (southern Spain), combining bulk and clumped CH4 isotopes with molecular gas composition, hydrochemical (Total Organic Carbon and Platinum Group Elements in water), geothermal and geo-structural data. Five springs analysed in 2014 have been re-examined for changes in gas chemistry over time, and three newly discovered gas-bearing springs are analysed for the first time. Regardless of whether springs have microbial or abiotic isotopic fingerprints, we find that bulk CH4 isotopes are fairly stable over a seven-year period. This suggests that the CH4 source(s) or postgenetic processes (such as oxidation and diffusion) have not undergone significant temporal changes. Major variations in H2 and CH4 concentrations in certain springs may be the result of changes in gas pressure and migration intensity. Paired CH4 clumped isotopes (Δ12CH2D2 - Δ13CH3D) were analysed in two bubbling springs, where the presence of CH4 can be interpreted as non-microbial based on 13C enrichment, absence of 14C, and the presence of ethane and propane. However, these isotopes are in disequilibrium, which prevents the quantification of the gas formation temperature. Within the Δ12CH2D2 - Δ13CH3D diagram, the data lie within both the microbialgenic zone, suggested by previous authors, and the abiotic zone that results combining data from laboratory gas synthesis and other natural gas samples. Therefore, attributing a microbial origin to CH4 based only on clumped isotopes is less definite than previously assumed. The amount of Total Organic Carbon appears to be correlated with the origin of CH4, as it is higher in 13C-depleted CH4 samples and lower in 13C-enriched samples. Palladium (Pd) and Rhodium (Rh) dissolved in water (the more soluble Platinum Group Elements) can be a proxy for the chromitite ore deposits contained in plagioclase tectonite layers throughout the investigated area, which may act as catalysts for abiotic CO2 hydrogenation. Clumped isotope disequilibrium and the reported absence of diffuse CH4-bearing fluid inclusions in the peridotites appear to rule out high temperature gas genesis in post-magmatic inclusions. These observations, along with the moderate temperatures at the base of the peridotite massifs and the consistent occurrence of gas along tectonic contacts between serpentinised (H2-bearing) peridotite and carbon-bearing rocks, are compatible with the theory of low-temperature CO2 hydrogenation.

Description: Published

Description: 121799

Description: OSA5: Energia e georisorse

Description: JCR Journal

Description: Methane (CH4) emissions to the atmosphere from the oil and gas sector in Romania remain highly uncertain despite their relevance for the European Union’s goals to reduce greenhouse gas emissions. Measurements of CH4 isotopic composition can be used for source attribution, which is important in top-down studies of emissions from extended areas. We performed isotope measurements of CH4 in atmospheric air samples collected from an aircraft (24 locations) and ground vehicles (83 locations), around oil and gas production sites in Romania, with focus on the Romanian Plain. Ethane to methane ratios were derived at 412 locations of the same fossil fuel activity clusters. The resulting isotopic signals (δ13C and δ2H in CH4) covered a wide range of values, indicating mainly thermogenic gas sources (associated with oil production) in the Romanian Plain, mostly in Prahova county (δ13C from –67.8 ± 1.2 to –22.4 ± 0.04 ‰ Vienna Pee Dee Belmnite; δ2H from –255 ± 12 to –138 ± 11 ‰ Vienna Standard Mean Ocean Water) but also the presence of some natural gas reservoirs of microbial origin in Dolj, Ialomiţa, Prahova, and likely Teleorman counties. The classification based on ethane data was generally in agreement with the one based on CH4 isotopic composition and confirmed the interpretation of the gas origin. In several cases, CH4 enhancements sampled from the aircraft could directly be linked to the underlying production clusters using wind data. The combination of δ13C and δ2H signals in these samples confirms that the oil and gas production sector is the main source of CH4 emissions in the target areas. We found that average CH4 isotopic signatures in Romania are significantly lower than commonly used values for the global fossil fuel emissions. Our results emphasize the importance of regional variations in CH4 isotopes, with implications for global inversion modeling studies. Keywords:

Description: Published

Description: 6A. Geochimica per l'ambiente e geologia medica

Description: JCR Journal