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Methane Clumped Isotopes: Progress and Potential for a New Isotopic Tracer

Douglas, Peter M. J. and Stolper, Daniel A. and Eiler, John M. and Sessions, Alex L. and Lawson, Michael and Shuai, Yanhua and Bishop, Andrew and Podlaha, Olaf G. and Ferreira, Alexandre A. and Santos Neto, Eugenio V. and Niemann, Martin and Steen, Arne S. and Huang, Ling and Chimiak, Laura and Valentine, David L. and Fiebig, Jens and Luhmann, Andrew J. and Seyfried, William E., Jr. and Etiope, Giuseppe and Schoell, Martin and Inskeep, William P. and Moran, James J. and Kitchen, Nami (2017) Methane Clumped Isotopes: Progress and Potential for a New Isotopic Tracer. Organic Geochemistry, 113 . pp. 262-282. ISSN 0146-6380.

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The isotopic composition of methane is of longstanding geochemical interest, with important implications for understanding petroleum systems, atmospheric greenhouse gas concentrations, the global carbon cycle, and life in extreme environments. Recent analytical developments focusing on multiply substituted isotopologues (‘clumped isotopes’) are opening a valuable new window into methane geochemistry. When methane forms in internal isotopic equilibrium, clumped isotopes can provide a direct record of formation temperature, making this property particularly valuable for identifying different methane origins. However, it has also become clear that in certain settings methane clumped isotope measurements record kinetic rather than equilibrium isotope effects. Here we present a substantially expanded dataset of methane clumped isotope analyses, and provide a synthesis of the current interpretive framework for this parameter. In general, clumped isotope measurements indicate plausible formation temperatures for abiotic, thermogenic, and microbial methane in many geological environments, which is encouraging for the further development of this measurement as a geothermometer, and as a tracer for the source of natural gas reservoirs and emissions. We also highlight, however, instances where clumped isotope derived temperatures are higher than expected, and discuss possible factors that could distort equilibrium formation temperature signals. In microbial methane from freshwater ecosystems, in particular, clumped isotope values appear to be controlled by kinetic effects, and may ultimately be useful to study methanogen metabolism.

Item Type:Article
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URLURL TypeDescription
Stolper, Daniel A.0000-0003-3299-3177
Sessions, Alex L.0000-0001-6120-2763
Additional Information:© 2017 Elsevier Ltd. Received 26 June 2017, Revised 11 July 2017, Accepted 22 July 2017, Available online 16 August 2017. The development of the Ultra was funded by NSF-EAR. PMJD was supported in part by Royal Dutch Shell. Research on the Santa Barbara Basin was supported by NSF OCE-1046144. The manuscript benefitted from constructive reviews from Andrew Murray, Kenneth Peters, and Xinyu Xia.
Funding AgencyGrant Number
Royal Dutch ShellUNSPECIFIED
Subject Keywords:Methane; Clumped Isotopes; Geothermometry; Petroleum Systems; Biogeochemistry
Record Number:CaltechAUTHORS:20170817-141906771
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Official Citation:Peter M.J. Douglas, Daniel A. Stolper, John M. Eiler, Alex L. Sessions, Michael Lawson, Yanhua Shuai, Andrew Bishop, Olaf G. Podlaha, Alexandre A. Ferreira, Eugenio V. Santos Neto, Martin Niemann, Arne S. Steen, Ling Huang, Laura Chimiak, David L. Valentine, Jens Fiebig, Andrew J. Luhmann, William E. Seyfried, Giuseppe Etiope, Martin Schoell, William P. Inskeep, James J. Moran, Nami Kitchen, Methane clumped isotopes: Progress and potential for a new isotopic tracer, In Organic Geochemistry, Volume 113, 2017, Pages 262-282, ISSN 0146-6380, (
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:80573
Deposited By: Tony Diaz
Deposited On:17 Aug 2017 21:29
Last Modified:03 Oct 2019 18:32

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