Seasonal variations of stable hydrogen and carbon isotope ratios of methane in subtropical freshwater sediments

Abstract

Abstract. Stable hydrogen (δD) and carbon (δ13C) isotope ratios of sedimentary methane from five subtropical Florida freshwater sites exhibited smaller, less distinct seasonal variations than previously observed in temperate sediments, apparently due to the smaller range of temperatures forcing the subtropical environments. Negative correlations observed between δD‐CH4 and δ13C‐CH4 at these sites probably resulted from mixing methane produced via acetate fermentation with methane formed from CO2 and H2. The inverse δD/δ13C trends, high sedimentary gas methane concentrations (up to 80 mole%), and visual observations imply that ebullition dominates methane transport from the sediments during at least part of the seasonal cycle. Many values deviated from the main inverse δD/δ13C trend such that bacterial oxidation was not indicated. The deviation may result from the reduction of CO2 with varying δ13C under conditions of elevated H2 concentrations or enhanced interspecies hydrogen transfer, which may cause relatively greater hydrogen isotopic fractionation. Alternatively, the deviation may result from fermentation of autotrophically formed, 13C‐depleted acetate. Differences in the δ13C of bulk organic matter from two of the sites potentially account for about half of the difference in mean δ13C‐CH4 between the two sites. In other cases, however, the immediate methanogenic precursor (e.g., acetate versus CO2/H2) appeared to be the major determinant of methane stable isotopic composition.