Stable Hydrogen and Carbon Isotopic Compositions of Biogenic Methanes

Stable hydrogen and carbon isotopic compositions of biogenic methanes collected from the sediments of several deep-sea, nearshore marine-estuarine, and freshwater environments were determined. The isotopic compositions of methane samples from eight different DSDP Sites (mean σD-CH4 = -1850\u3e/∞, std. dev. = 70\u3e/∞, n = 75; mean σ13C-CH4 = -71.30/∞, std. dev. = 6.30/∞, n = 44) are generally typical of methane formed via C02 reduction in deep-sea sediments. Methane collected from several freshwater environments was D-depleted (mean σD-CH4 = -3000\u3e/∞ , std. dev. = 260/∞, n = 20) and 13C-enriched (mean σ13C-CH4 = -60.10/∞, std. dev. = 6.10/∞, n = 20) compared to the deep-sea methane. Normally, acetate dissimilation is thought to account for about 60 to 70% of the total methane production in freshwater sediments. Nearshore marine-estuarine methanes appear to be isotopically intermediate (mean σD-CH4 = -2580\u3e/∞ , std. dev. = 230/∞, n = 46; σ13C-CH4 = -61.80/∞, std. dev. = 3.10/∞, n = 46) between deep-sea and freshwater methanes. Variation in the relative importance of the two main methanogenic pathways, acetate dissimilation and C02 reduction, is probably the single most important factor responsible for the differences in methane isotopic compositions among these three different types of environments. Other factors that probably contribute to the methane isotopic differences are temperature, sedimentation rate, organic matter type and amount, concentration of alternate electron acceptors, rate of methane formation and possibly postgenerative isotopic equilibration. Shallow aquatic sediments are thought to be an important source of methane to the atmosphere; the methane produced in these systems, including the ones sampled in this study, is generally substantially more 13C-depleted than expected based on the σ13C of atmospheric methane and the isotopic fractionation associated with the atmospheric sink process. Too few oD data are available to allow evaluation of the role of shallow aquatic sediments in determining atmospheric σD-CH4