Carbon and hydrogen isotopic compositions of products of open-system catalytic hydrogenation of CO2: Implications for abiogenic hydrocarbons in Earth's crust

This paper reports the isotope effects in an open-system Fischer-Tropsch type (FTT) synthesis, with implications for the origin of natural abiogenic hydrocarbons. The starting form of carbon was CO2, with carbon and hydrogen isotopic compositions measured for products of catalytic hydrogenation of CO2 on iron and cobalt catalysts (FTCO2-Fe and FTCO2-Co) at 350 and 245 degrees C, respectively, and 10 MPa. The carbon isotopic composition of the resulting saturated hydrocarbons (alkanes) as a function of carbon number shows a positive trend for both FTCO2-Fe and FTCO2-Co, with a fractionation of 2-4 parts per thousand and 3-6 parts per thousand between CH4 and C2H6 over the Fe and Co catalysts, respectively. The unsaturated hydrocarbons (alkenes) do not show any trend. A strong kinetic isotope fractionation (>40 parts per thousand) occurred between CO2 and CH4 in both experiments. The hydrogen isotope fractionation between alkanes appeared to be similar to that found in natural (thermogenic and biogenic) gases, with enrichment in deuterium of longer hydrocarbon chains; the dominant H/D fractionation occurred between CH4 and C2H6. Alkenes in the products of the FTCO2-Fe reaction are enriched in deuterium (similar to 50 parts per thousand) and do not show any trend versus carbon number. We suggest that other than FTT reactions or a simple mixing are responsible for the occurrence of the inverse isotopic trends in both delta C-13 and delta D found in light hydrocarbons in some terrestrial environments and meteorites. (C) 2010 Elsevier Ltd. All rights reserved.