Isotopic signatures of CH4 and higher hydrocarbon gases from Precambrian Shield sites: A model for abiogenic polymerization of hydrocarbons

Previous studies of methane and higher hydrocarbon gases in Precambrian Shield rocks in Canada and the Witwatersrand Basin of South Africa identified two major gas types. Paleometeoric waters were dominated by hydrocarbon gases with compositional and isotopic characteristics consistent with production by methanogens utilizing the CO2 reduction pathway. In contrast the deepest, most saline fracture waters contained gases that did not resemble the products of microbial methanogenesis and were dominated by both high concentrations of H2 gas, and CH4 and higher hydrocarbon gases with isotopic signatures attributed to abiogenic processes of water–rock reaction in these high rock/water ratio, hydrogeologically-isolated fracture waters. Based on new data obtained for the higher hydrocarbon gases in particular, a model is proposed to account for carbon isotope variation between CH4 and the higher hydrocarbon gases (specifically ethane, propane, butane, and pentane) consistent with abiogenic polymerization. Values of δ13C for CH4 and the higher hydrocarbon gases predicted by the model are shown to match proposed abiogenic hydrocarbon gas end-members identified at five field sites (two in Canada and three in South Africa) suggesting that the carbon isotope patterns between the hydrocarbon homologs reflect the reaction mechanism. In addition, the δ2H isotope data for these gases are shown to be out of isotopic equilibrium, suggesting the consistent apparent fractionation observed between the hydrocarbon homologs may also reflect reaction mechanisms involved in the formation of the gases. Recent experimental and field studies of proposed abiogenic hydrocarbons such as those found at mid-ocean spreading centers and off-axis hydrothermal fields such as Lost City have begun to focus not only on the origin of CH4, but on the compositional and isotopic information contained in the higher hydrocarbon gases. The model explored in this paper suggests that while the extent of fractionation in the first step in the hydrocarbon synthesis reaction chain may vary as a function of different reaction parameters, δ13C values for the higher hydrocarbon gases may be predicted by a simple mass balance model from the δ13C values of the lower molecular weight precursors, consistent with abiogenic polymerization. Integration of isotopic data for the higher hydrocarbon gases in addition to CH4 may be critical for delineation of the origin of the hydrocarbons and investigation of formation mechanisms.