Genetic and temporal relations between formation waters and biogenic methane: Upper Devonian Antrim Shale, Michigan Basin, USA

Controversy remains regarding how well geochemical criteria can distinguish microbial from thermogenic methane. Natural gas in most conventional deposits has migrated from a source rock to a reservoir, rarely remaining associated with the original or cogenetic formation waters. We investigated an unusual gas reservoir, the Late Devonian Antrim Shale, in which large volumes of variably saline water are coproduced with gas. The Antrim Shale is organic-rich, of relatively low thermal maturity, extensively fractured, and is both source and reservoir for methane that is generated dominantly by microbial activity. This hydrogeologic setting permits integration of chemical and isotopic compositions of coproduced water and gas, providing a unique opportunity to characterize methane generating mechanisms. The well-developed fracture network provides a conduit for gas and water mass transport within the Antrim Shale and allows invasion of meteoric water from overlying aquifers in the glacial drift. Steep regional concentration gradients in chemical and isotopic data are observed for formation waters and gases; dilute waters grade into dense brines (300,000 ppm) over lateral distances of less than 30 km. Radiogenic (C-14 and H-3) and stable isotope (O-18 and D) analyses of shallow Antrim Shale formation waters and glacial drift groundwaters indicate recharge times from modern to 20,000 yr sp. Carbon isotope compositions of methane from Antrim Shale wells are typical of the established range for thermogenic or mixed gas (delta(13)C = -47 to -56 parts per thousand). However, the unusually high delta(13)C values of CO2 coproduced with methane (similar to+22 parts per thousand) and dissolved inorganic carbon (DIC) in formation waters (similar to 28 parts per thousand) require bacterial mediation. The delta D values of methane and coproduced formation water provide the strongest evidence of bacterial methanogenesis. Methane/[ethane + propane] ratios and delta(13)C values for ethane indicate: (1) the presence of a thermogenic gas component that increases basinward and (2) progressive bacterial oxidation of ethane as the Antrim Shale subcrop is approached. Multiple episodes of Pleistocene glaciation over northern Michigan appear critical to the development of these gas deposits. Loading of thick ice sheets may have provided hydraulic head that enhanced dilation of preexisting fractures and influx of meteoric water. The physical erosion cycle of repeated glacial advances and retreats exhumed the Antrim Shale around the northern margin of the Michigan Basin, subjecting it to near-surface physiochemical and biochemical processes. The chemical and hydrologic relations demonstrated in the Antrim Shale reservoir suggest a dynamic connection between Pleistocene glacial history of the midcontinent region and development of recoverable, microbially generated natural gas reserves. Copyright (C) 1998 Elsevier Science Ltd.