Woodland, A. B.

Thermogenic hydrocarbons entirely deriving from the thermal degradation of organic matter usually exhibit methane to ethane plus propane ratios smaller than 100. We present hydrocarbon distribution data of continental hydrothermal gases, whose methane has been independently identifi ed to derive from the abiogenic reduction of CO2. We fi nd that excess amounts of methane with respect to thermogenic hydrocarbon distributions are characteristic for the investigated gases. A similar pattern is observed for well discharges whose temperatures are too high to support any microbially mediated methanogenesis. These findings strongly suggest that abiogenic methane production in continental-hydrothermal systems is a more widespread process than previously assumed. The maximum contribution of such emissions to the modern atmospheric CH4 budget is estimated at ~1%.

The genetic relationship between carbon-bearing species (CO, CO2, CH4, C2H6, C3H8, C2H4 and C3H6) was investigated in volcanic-hydrothermal gases emitted from Nisyros (Greece), Vesuvio, La Solfatara (Campi Flegrei) and Pantelleria (all Italy). Apparent carbon isotopic temperatures of the CH4-CO2 system are ~360°C at Nisyros, 420-460°C at Vesuvio, ~450°C at La Solfatara and ~540°C at Pantelleria. These temperatures are confirmed by measured propene/propane and H2/H2O concentration ratios. CH4 and CO2 equilibrate in the single liquid phase prior to the onset of boiling, whereas propene and propane attain equilibrium in the saturated water vapor phase. Boiling in these high-enthalpy hydrothermal systems might occur isothermally. Once vapor has been extracted from the parental liquid, CO/CO2 responds most sensitively to the temperature gradient encountered by the ascending gases. Our results imply that the CH4-CO2 isotopic geothermometer can provide reliable information about temperatures of deep hydrothermal liquids associated with volcanism. Propene/propane and H2/H2O concentration ratios should be measured along with the carbon isotopic composition of CO2 and CH4 to provide independent constraints on the geological significance of the apparent carbon isotopic temperatures.

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 theMediterranean 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

Methane (CH4) emanating from a continental volcanichydrothermal system in Nisyros, Greece, is processed through the abiogenic reduction of mantle- and marine limestonederived CO2 [1]. Evidence for the occurrence of abiogenic hydrothermal reduction of CO2 is from the chemical and carbon isotopic equilibrium patterns. We have further characterized this abiogenic methane (C1) source for the concentrations of ethane (C2) and propane (C3), as well as for the hydrogen isotopic composition of CH4, H2O, H2 and H2S. C1/C2+ ratios are significantly higher than those typically observed for purely thermogenic sources. Hydrocarbon distribution ratios for other continental-hydrothermal sources rich in CO2 are comparable to those of the Nisyros fumaroles implying that abiogenic methane might be significantly more widespread than previously assumed [2]. Relative concentrations of hydrocarbons in continental-hydrothermal discharges are even indistinguishable from those measured in ultramafic hydrothermal emissions. The fact that redox conditions do not seem to exert any control on the relative concentrations of hydrocarbons in hydrothermal emissions in general, implies that the same two sources account for hydrocarbon production in continental and ultramafic environments. One source generates methane exclusively through the selective abiogenic reduction of CO2 (Sabatierreaction). The other source produces minor amounts of methane, ethane and propane by a random process and represents either the thermal cracking of organic matter or the polymerization starting from methane. Hydrogen isotope partitioning between H2O, H2S, H2 and CH4 in Nisyros fumaroles reveals that isotopic exchange rates are highest for H2O-H2S followed by H2O-H2. In contrast to H2 and H2S, the hydrogen isotopic composition of methane exhibits almost no local variations. This is in agreement with its predominantly abiogenic hydrothermal origin and with the low temperature sensitivity of the hydrogen isotope fractionation factor between water vapor and methane.