Abstract. There is growing interest in developing spatially resolved methane (CH4) isotopic source signatures to aid in geographic source attribution of CH4 emissions. CH4 hydrogen isotope measurements (δ2H–CH4) have the potential to be a powerful tool for geographic differentiation of CH4 emissions from freshwater environments, as well as other microbial sources. This is because microbial δ2H–CH4 values are partially dependent on the δ2H of environmental water (δ2H–H2O), which exhibits large and well-characterized spatial variability globally. We have refined the existing global relationship between δ2H–CH4 and δ2H–H2O by compiling a more extensive global dataset of δ2H–CH4 from freshwater environments, including wetlands, inland waters, and rice paddies, comprising a total of 129 different sites, and compared these with measurements and estimates of δ2H–H2O, as well as δ13C-CH4 and δ13C–CO2 measurements. We found that estimates of δ2H–H2O explain approximately 42 % of the observed variation in δ2H–CH4, with a flatter slope than observed in previous studies. The inferred global δ2H–CH4 vs. δ2H–H2O regression relationship is not sensitive to using either modelled precipitation δ2H or measured δ2H–H2O as the predictor variable. The slope of the global freshwater relationship between δ2H–CH4 and δ2H–H2O is similar to observations from incubation experiments but is different from pure culture experiments. This result is consistent with previous suggestions that variation in the δ2H of acetate, controlled by environmental δ2H–H2O, is important in determining variation in δ2H–CH4. The relationship between δ2H–CH4 and δ2H–H2O leads to significant differences in the distribution of freshwater δ2H–CH4 between the northern high latitudes (60–90∘ N), relative to other global regions. We estimate a flux-weighted global freshwater δ2H–CH4 of −310 ± 15 ‰, which is higher than most previous estimates. Comparison with δ13C measurements of both CH4 and CO2 implies that residual δ2H–CH4 variation is the result of complex interactions between CH4 oxidation, variation in the dominant pathway of methanogenesis, and potentially other biogeochemical variables. We observe a significantly greater distribution of δ2H–CH4 values, corrected for δ2H–H2O, in inland waters relative to wetlands, and suggest this difference is caused by more prevalent CH4 oxidation in inland waters. We used the expanded freshwater CH4 isotopic dataset to calculate a bottom-up estimate of global source δ2H–CH4 and δ13C-CH4 that includes spatially resolved isotopic signatures for freshwater CH4 sources. Our bottom-up global source δ2H–CH4 estimate (−278 ± 15 ‰) is higher than a previous estimate using a similar approach, as a result of the more enriched global freshwater δ2H–CH4 signature derived from our dataset. However, it is in agreement with top-down estimates of global source δ2H–CH4 based on atmospheric measurements and estimated atmospheric sink fractionations. In contrast our bottom-up global source δ13C-CH4 estimate is lower than top-down estimates, partly as a result of a lack of δ13C-CH4 data from C4-plant-dominated ecosystems. In general, we find there is a particular need for more data to constrain isotopic signatures for low-latitude microbial CH4 sources.

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Abstract. There is growing interest in developing spatially resolved methane (CH4) isotopic source signatures to aid in geographic source attribution of CH4 emissions. CH4 hydrogen isotope measurements (δ2H-CH4) have the potential to be a powerful tool for spatial resolution of CH4 emissions from freshwater environments, as well as other microbial sources. This is because microbial δ2H-CH4 values are partially dependent on the δ2H of environmental water (δ2H-H2O), which exhibits large and well-characterized spatial variability globally. We compiled a comprehensive global dataset of paired CH4 δ2H and δ13C measurements from freshwater environments, including wetlands, inland waters, and rice paddies, comprising a total of 131 different ecosystems, and compared these with measurements and estimates of δ2H-H2O. We found that the estimated δ2H of annual precipitation (δ2Hp) explained approximately 35 % of the observed variation in δ2H-CH4, and that the relationship between δ2H-CH4 and δ2Hp led to significant differences in the distribution of freshwater δ2H-CH4 between the northern high latitudes (60–90º N) relative to other global regions. Residual variability in δ2H-CH4 is partially explained by differences in the dominant methanogenic pathway and CH4 oxidation, as inferred from carbon isotope fractionation between CH4 and carbon dioxide (αC). Our results imply that hydrogenotrophic methanogenesis is characterized by a steeper slope of δ2H-CH4 vs. δ2Hp than acetoclastic methanogenesis, a pattern that is consistent with previous predictions. Biogeochemical sources of variability in δ2H-CH4 are reflected in apparent differences between different freshwater ecosystems, with relatively high values in rivers and bogs, and low values in fens and rice paddies, although more data is needed to verify whether these differences are significant. To estimate how changes in the spatial distribution of freshwater emissions would influence global atmospheric CH4 isotopic measurements, we developed a bottom-up mixing model of global CH4 δ2H and δ13C sources, including spatially resolved signatures for freshwater CH4 sources. This model implies that changes in high-latitude freshwater CH4 emissions would have an especially strong influence on global source δ2H-CH4. We estimate that global CH4 emissions sources have a combined δ2H value of −277±8 ‰, which is consistent with top-down estimates based on atmospheric measurements. In contrast our estimated δ13C value of −56.4±1.4 ‰ is not consistent with atmospheric measurements, suggesting possible errors in either emissions inventories or estimates of sink fluxes and isotopic fractionations. Overall our results emphasize the value of δ2H-CH4 measurements to help constrain atmospheric CH4 budgets.