Sourcing hydrocarbons in CO2-rich in hydrothermal systems

Abstract

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.