Abiotic and biotic controls on methane formation down to 2.5Â km depth within the Precambrian Fennoscandian Shield

Despite a geological history characterised by high temperature and pressure processes and organic carbon deprived crystalline bedrock, large amounts of hydrocarbons are found in deep groundwaters within Precambrian continental shields. In many sites, methane comprises more that 80% of the dissolved gas phase reaching concentrations of tens of mmol l−1. In this study, we used isotopic methods to study the carbon isotope systematics and sources of crustal methane within the Fennoscandian Shield. The main study sites were the Outokumpu Deep Drill Hole and the Pyhäsalmi mine in Finland, both of which allow groundwater sampling down to 2.5 km depth and have been previously studied for their groundwater chemistry and microbiology. We show that the differences in the amount and isotopic composition of methane are related to the availability of carbon sources as well as processes behind the incorporation of hydrogen and carbon via abiotic and biotic pathways into hydrocarbon molecules. Supported by previously reported occurrences and isotopic data of deep groundwater methane in lithologically different locations in Finland and Sweden, we show that methane formation is controlled by microbial methanogenesis and abiotic reactions, as well as lithology with the metasedimentary environments being the most favourable for methane occurrence. Rather than a thermogenic relic, crustal methane within the Fennoscandian Shield is more likely the result of low temperature formation from ancient organic compounds or their inorganic intermediates such as graphite. Such crustal gases are characterised by the lack of major amounts of C2+ hydrocarbons and 13C-rich methane. Further, microbiological and isotopic geochemical evidence suggest that microbial methane is more common at depths shallower than 1.5 km.