Isotopic patterns of hydrothermal hydrocarbons emitted from Mediterranean volcanoes

We have analyzed the carbon isotopic composition of CO2, methane, ethane, propane and n-butane, the hydrogen isotopic composition of methane as well as total concentrations of gas constituents contained in the Mediterranean volcanic-hydrothermal discharges of Nisyros (Greece), Vesuvio, La Solfatara, Ischia and Pantelleria (all Italy) to determine the origin of the hydrocarbons. Isotopic criteria conventionally used for hydrocarbon classification suggest thermogenic origins, except for Pantelleria, for which an abiogenic origin is indicated. These findings would imply that thermogenic sources can provide methane/(ethane + propane) concentration ratios as high as those usually observed for microbial hydrocarbons. However, additional consideration of gas concentration data challenges the suitability of conventional criteria for the classification of hydrocarbons emanating from hydrothermal environments. Methane seems to be in close equilibrium with co-occurring CO2, whereas its higher chain homologues are not. Therefore, it cannot be excluded that methane on the one hand and ethane, propane and n-butane on the other hand have distinct origins. The carbon isotopic composition of methane might be controlled by the carbon isotopic composition of co-occurring inorganic CO2 and by hydrothermal temperatures whereas the carbon isotopic composition of the higher n-alkanes could correspond to the maturity of organic matter and/or to the residence time of the gasses in the source system.