Neal E. Blair Anna M. Martini Steve Larter William H. Orem Jennifer C. McIntosh David S. Vinson 2017 <p id="sp0045">Stable carbon and hydrogen isotope signatures of methane, water, and inorganic carbon are widely utilized in natural gas systems for distinguishing microbial and thermogenic methane and for delineating methanogenic pathways (acetoclastic, hydrogenotrophic, and/or methylotrophic methanogenesis). Recent studies of coal and shale gas systems have characterized in situ microbial communities and provided stable isotope data (δD-CH₄, δD-H₂O, δ¹³C-CH₄, and δ¹³C-CO₂) from a wider range of environments than available previously. Here we review the principal biogenic methane-yielding pathways in coal beds and shales and the isotope effects imparted on methane, document the uncertainties and inconsistencies in established isotopic fingerprinting techniques, and identify the knowledge gaps in understanding the subsurface processes that govern H and C isotope signatures of biogenic methane. We also compare established isotopic interpretations with recent microbial community characterization techniques, which reveal additional inconsistencies in the interpretation of microbial metabolic pathways in coal beds and shales. Collectively, the re-assessed data show that widely-utilized isotopic fingerprinting techniques neglect important complications in coal beds and shales.</p><p id="sp0050">Isotopic fingerprinting techniques that combine δ¹³C-CH₄ with δD-CH₄ and/or δ¹³C-CO₂have significant limitations: (1) The consistent ~&nbsp;160‰ offset between δD-H₂O and δD-CH₄ could imply that hydrogenotrophic methanogenesis is the dominant metabolic pathway in microbial gas systems. However, hydrogen isotopes can equilibrate between methane precursors and coexisting water, yielding a similar apparent H isotope signal as hydrogenotrophic methanogenesis, regardless of the actual methane formation pathway. (2) Non-methanogenic processes such as sulfate reduction, Fe oxide reduction, inputs of thermogenic methane, anaerobic methane oxidation, and/or formation water interaction can cause the apparent carbon isotope fractionation between δ¹³C-CH₄ and δ¹³C-CO₂(α¹³C_CO2-CH4) to differ from the true methanogenic fractionation, complicating interpretation of methanogenic pathways. (3) Where little-fractionating non-methanogenic bacterial processes compete with highly-fractionating methanogenesis, the mass balance between CH₄ and CO₂ is affected. This has implications for δ¹³C values and provides an alternative interpretation for net C isotope signatures than solely the pathways used by active methanogens. (4) While most of the reviewed values of δD-H₂O - δD-CH₄ and α¹³C_CO2-CH4 are apparently consistent with hydrogenotrophic methanogenesis as the dominant pathway in coal beds and shales, recent microbial community characterization techniques suggest a possible role for acetoclastic or methylotrophic methanogenesis in some basins.</p> application/pdf 10.1016/j.chemgeo.2017.01.027 en Elsevier Microbial methane from in situ biodegradation of coal and shale: A review and reevaluation of hydrogen and carbon isotope signatures article