Constraining Wetland and Landfill Methane Emission Signatures Through Atmospheric Methane Clumped Isotopologue Measurements

Microbial methane emissions are associated with a wide range of isotopic signatures, providing information about the sources and sinks of methane. Methods of directly sampling methane from environments such as wetlands may fail to capture the temporal and spatial variations in emissions at a specific site and time. The Keeling plot method is commonly used to infer the overarching isotopic signatures of methane sources. In this study, we have expanded the application of the Keeling plot from conventional stable isotope ratios to include novel clumped isotopologue compositions of methane. This advancement aims to provide more robust constraints on regional methane emission signatures. We analyzed methane isotopologue compositions from air samples collected above wetlands and landfills across Maryland, USA, and determined the end-member compositions for background air, wetland, and landfill sources. Our findings indicate that the isotopologue compositions of methane from regional wetland emissions exhibit seasonal variations—δ¹³C and δD values become less positive as winter approaches, reflecting changes in methane oxidation and production rates. The continuous monitoring of air methane isotopologue signatures will deepen our understanding of the seasonal patterns in methane emissions and contribute to refining the global methane budget, as valuable insights can be extracted from these measurements.