Global inventory of doubly substituted isotopologues of methane (Δ <sup>13</sup> CH <sub>3</sub> D and Δ <sup>12</sup> CH <sub>2</sub> D <sub>2</sub> )

Abstract. Measurements of methane (CH4) molecules containing two rare isotopes (13CH3D and 12CH2D2), also termed doubly substituted or “clumped” isotopologues, have the potential to provide two additional isotopic dimensions to help investigate the mechanisms underlying global atmospheric trends in CH4. In this work, we summarise the current state of research on doubly substituted CH4 isotopologues, with an emphasis on compiling results of all relevant work. The database comprises 1475 records compiled from the literature published until April 2025 (https://doi.org/10.5285/51ae627da5fb41b8a767ee6c653f83e6, Defratyka et al., 2025). For field samples, 40 % of records were sourced from natural gas reservoirs, while microbial terrestrial (e.g., agriculture, lake, wetland) samples account only for 12.5 %. Lakes samples contribute 75 % to collected microbial terrestrial samples. There is limited or no representation of samples coming from significant microbial CH4 sources to the atmosphere, like wetlands, agricultural practices and landfills. To date, laboratory experiments were mostly focused on microbial (28 % of samples from laboratory experiments) and pyrogenic (15 %) methanogenesis or anaerobic (16 %), and aerobic (8 %) CH4 oxidation, with only single study of photochemical oxidation via OH and Cl, which constitutes 5 % of the laboratory experiments entries. The distinct ranges of Δ13CH3D and Δ12CH2D2 values measured in these studies suggests their potential to improve our understanding of atmospheric CH4. This work provides an overview of the major gaps in measurements and identifies where further studies should be focussed to enable the highest impact on understanding global CH4.

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Journal
Earth system science data
Published
2025-12-08
DOI
https://doi.org/10.5194/essd-17-6889-2025
Primary Topic
Atmospheric and Environmental Gas Dynamics
Type
article
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article

Global inventory of doubly substituted isotopologues of methane (Δ 13 CH 3 D and Δ 12 CH 2 D 2 )

Tim Arnold, Josué J. Jautzy, Jabrane Labidi, Jiayang Sun et al.
Earth system science data
Atmospheric and Environmental Gas Dynamics
article

Global inventory of doubly substituted isotopologues of methane (Δ 13 CH 3 D and Δ 12 CH 2 D 2 )

Tim Arnold, Josué J. Jautzy, Jabrane Labidi, Jiayang Sun, Guannan Dong, Julianne M. Fernandez, William D. Leavitt, Thomas Giunta, Jeemin H. Rhim, Ellen Lalk, Daniel L. Eldridge, Edward Young, Peter Douglas, Li‐Hung Lin, Naizhong Zhang, Thomas Röckmann, Barbara Sherwood Lollar, Malavika Sivan, Mojhgan Haghnegahdar, Jiawen Li, Shuhei Ono, Getachew Agmuas Adnew, Iñaki Vadillo, Nicole Hultquist, David T. Wang, G. Todd Ventura, Sara Defratyka, A.N. Hristov, Giuseppe Etiope, Lucía Ojeda, Ji‐Hyun Kim, Jiarui Liu
article en

Abstract

Abstract. Measurements of methane (CH4) molecules containing two rare isotopes (13CH3D and 12CH2D2), also termed doubly substituted or “clumped” isotopologues, have the potential to provide two additional isotopic dimensions to help investigate the mechanisms underlying global atmospheric trends in CH4. In this work, we summarise the current state of research on doubly substituted CH4 isotopologues, with an emphasis on compiling results of all relevant work. The database comprises 1475 records compiled from the literature published until April 2025 (https://doi.org/10.5285/51ae627da5fb41b8a767ee6c653f83e6, Defratyka et al., 2025). For field samples, 40 % of records were sourced from natural gas reservoirs, while microbial terrestrial (e.g., agriculture, lake, wetland) samples account only for 12.5 %. Lakes samples contribute 75 % to collected microbial terrestrial samples. There is limited or no representation of samples coming from significant microbial CH4 sources to the atmosphere, like wetlands, agricultural practices and landfills. To date, laboratory experiments were mostly focused on microbial (28 % of samples from laboratory experiments) and pyrogenic (15 %) methanogenesis or anaerobic (16 %), and aerobic (8 %) CH4 oxidation, with only single study of photochemical oxidation via OH and Cl, which constitutes 5 % of the laboratory experiments entries. The distinct ranges of Δ13CH3D and Δ12CH2D2 values measured in these studies suggests their potential to improve our understanding of atmospheric CH4. This work provides an overview of the major gaps in measurements and identifies where further studies should be focussed to enable the highest impact on understanding global CH4.

Earth system science dataVol. 17(12)
Dartmouth College (US), California Institute of Technology (US), Centre National de la Recherche Scientifique (FR), Planetary Science Institute (US), Pennsylvania State University (US), National Oceanic and Atmospheric Administration (US), Woodwell Climate Research Center (US), Geological Survey of Canada (CA), United States Department of Energy (US), Los Alamos National Laboratory (US), National Physical Laboratory (GB), Institut de physique du globe de Paris (FR), Ifremer (FR), University of California, Santa Barbara (US), National Taiwan University (TW), University of Toronto (CA), Lund University (SE), National Nuclear Laboratory (GB), Utrecht University (NL), Université Paris Cité (FR), University of Utah (US), Istituto Nazionale di Geofisica e Vulcanologia (IT), Babeș-Bolyai University (RO), Korea Institute of Geoscience and Mineral Resources (KR), Geocenter Denmark (DK), Massachusetts Institute of Technology (US), Saint Mary's University (CA), University of Maryland, College Park (US), Swiss Federal Laboratories for Materials Science and Technology (CH), NOAA Air Resources Laboratory (US), Universidad de Málaga (ES), University of Edinburgh (GB)
Openalex Percentile: Top 64%
Atmospheric and Environmental Gas Dynamics
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