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CH₄ isotopic ordering records ultra-slow hydrocarbon biodegradation in the deep subsurface

Jautzy, Josué J. and Douglas, Peter M. J. and Xie, Hao and Eiler, John M. and Clark, Ian D. (2021) CH₄ isotopic ordering records ultra-slow hydrocarbon biodegradation in the deep subsurface. Earth and Planetary Science Letters, 562 . Art. No. 116841. ISSN 0012-821X. doi:10.1016/j.epsl.2021.116841.

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Investigation of the biology and biochemistry of the deep subsurface provides invaluable information regarding the limit of life in extreme environments and its role in the global carbon cycle. It has been observed that subsurface microbial CH₄ can form in apparent isotopic equilibrium, both with respect to methane clumped isotopic species and D/H fractionation with respect to coexisting water. This observation fostered the suggestion that methanogenic metabolisms in energy-starved environments can operate through slow and reversible enzymatic reactions. Here we present isotopic data including a vertical profile of clumped isotopic indices of methane from Paleozoic-aged pore waters in an aquiclude system from the Michigan Basin. We show evidence of both internal isotopic equilibrium of methane and intermolecular H-isotopic equilibrium between methane and co-occurring non-gaseous n-alkanes. Various mixing and microbial metabolic models were tested and allowed us to identify the possibility of the production of methane at thermodynamic equilibrium from the syntrophic degradation of sedimentary n-alkanes at ultra-slow rates.

Item Type:Article
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URLURL TypeDescription
Jautzy, Josué J.0000-0003-3194-3143
Douglas, Peter M. J.0000-0002-4282-6615
Xie, Hao0000-0001-5656-2035
Alternate Title:CH4 isotopic ordering records ultra-slow hydrocarbon biodegradation in the deep subsurface
Additional Information:© 2021 Published by Elsevier B.V. Received 25 August 2020, Revised 14 February 2021, Accepted 16 February 2021, Available online 3 March 2021. This research was funded by the Nuclear Waste Management Organization (NWMO), Toronto, Canada and the National Sciences and Engineering Research Council (NSERC) through an NSERC/NWMO Collaborative Research and Development grant (477852-14) held by IDC. We thank Nami Kitchen for training and assistance on Δ₁₈ measurements at Caltech and Paul Middlestead for gas % concentrations measurements assistance at the Ján Veizer Stable Isotope Laboratory (uOttawa). Ende Zuo and Dylan Luhowy are acknowledged for sampling assistance at the Bruce Nuclear Site Core Archive Facility. Monique Hobbs, Laura Kennell-Morrison and Martine M. Savard are thanked for their review of this work. Tom Al and Duane Petts are acknowledged for discussions on paleo-fluid history in the Michigan Basin. We thank the editor, Louis Derry, three anonymous reviewers and Jeanine Ash for their reviews and comments that greatly contributed to improve this manuscript. This work is dedicated to the memory of Mark R. Jensen. CRediT authorship contribution statement: J.J.J. designed the study. J.J.J., collected, purified and performed the isotopic analyses. H.X. developed and performed the analyses of the ¹²CH₂D₂ isotopologue on the production MAT 253 Ultra. J.J.J., P.M.J.D analyzed the data and wrote the manuscript with substantial editing and interpretation inputs J.M.E, I.D.C, and H.X. The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
Funding AgencyGrant Number
Nuclear Waste Management Organization (NWMO)UNSPECIFIED
Natural Sciences and Engineering Research Council of Canada (NSERC)477852-14
Subject Keywords:microbial methanogenesis; clumped isotopes; Paleozoic
Record Number:CaltechAUTHORS:20210305-071759633
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Official Citation:Josué J. Jautzy, Peter M.J. Douglas, Hao Xie, John M. Eiler, Ian D. Clark, CH4 isotopic ordering records ultra-slow hydrocarbon biodegradation in the deep subsurface, Earth and Planetary Science Letters, Volume 562, 2021, 116841, ISSN 0012-821X, (
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:108319
Deposited By: Tony Diaz
Deposited On:08 Mar 2021 23:47
Last Modified:16 Nov 2021 19:10

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