From shale oil to biogenic shale gas: Retracing organic-inorganic interactions in the Alum Shale (Furongian-Lower Ordovician) in southern Sweden

Methane-rich gas occurs in the total organic carbon rich Alum Shale (Furongian to Lower Ordovician) in southern Sweden. The lower part of the thermally immature Alum Shale was impregnated by bitumen locally generated by heating from magmatic intrusions from the Carboniferous to the Permian. Organic geochemical data indicate that the migrated bitumen is slightly degraded. In the upper Alum Shale, where methane is the main hydrocarbon in thermovaporization experiments, centimeter-size calcite crystals occur that contain fluid inclusions filled with oil, gas, or water. The Alum Shale is thus considered a mixed shale oil biogenic shale gas play. The presented working hypothesis to explain the biogenic methane occurrence considers that water-soluble bitumen components of the Alum Shale were converted to methane. A hydrogeochemical modeling approach allows the quantitative retracing of inorganic reactions triggered by oil degradation. The modeling results reproduce the present-day gas and mineralogical composition. The conceptual model applied to explain the methane occurrence in the Alum Shale in southern Sweden resembles the formation of biogenic methane in the Antrim Shale (Michigan Basin, United States). In both models, melting water after the Pleistocene glaciation and modem meteoric water may have diluted the contents of total dissolved solids (TDS) in basinal brines. Such pore waters with low TDS contents create a subsurface aqueous environment favorable for microbes that have the potential to form biogenic methane. Today, biogenic methane production rates, with shale as the substrate using different hydrocarbon-degrading microbial enrichment cultures in incubation experiments, range from 10 to 620 nmol per gram and per day.