Biogenic methane formation in marine and freshwater environments: CO 2 reduction vs . acetate fermentation--Isotope evidence

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Two primary methanogenic pathways can be distinguished using the carbon and hydrogen stable isotope composition of the methane as a function of the coexisting carbon dioxide and formation water precursors. Although both pathways may occur in both marine and freshwater sediments. CO 2 reduction is dominant in the sulphate-free zone of the former, while acetate fermentation is the major pathway in freshwater sediments. Methane in marine sediments can be defined isotopically by 13 C -110 to -600/%., and D -250 to -1700 . In contrast, methane from freshwater sediments ranges from 13 C -65 to -500/%. and D -400 to -2500/%.. Carbon isotope fractionations ( c CO 2 - CH 4 ) are generally between 1.05 and 1.09 for marine sediments, while lower in freshwater sediments (1.04 to 1.06). The relationship of the methane to the formation water indicates the source of the hydrogen for CO 2 reduction to be the water directly with an associated hydrogen fractionation of -180 ± 200/%.. The CH 4 -H 2 O hydrogen fractionation is larger for acetate fermentation due to the transfer of the methyl group during methanogenesis which is depleted in deuterium and accounts for 3/4 of the hydrogen in the methane. A model is presented showing that the fourth hydrogen via acetate fermentation may ultimately come from the formation water but is isotopically fractionated. Combination of the carbon and hydrogen isotope fractionations ( C , D ) from CH 4 with CO 2 and H 2 O respectively, can clearly delineate the CO 2 reduction and acetate fermentation environments. Defining the character of the methanogenic types with carbon and hydrogen isotopes not only provides information about the environment of formation, it is also most useful in distinguishing biogenic from thermogenic methane gases.

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