Large carbon isotope variability during methanogenesis under alkaline conditions

Miller, Hannah M.; Chaudhry, Nabil; Conrad, Mark E.; Bill, Markus; Kopf, Sebastian H.; Templeton, Alexis S.

doi:10.1016/j.gca.2018.06.007

Title: Large carbon isotope variability during methanogenesis under alkaline conditions

Journal Article · Wed Jun 27 00:00:00 EDT 2018 · Geochimica et Cosmochimica Acta

DOI:https://doi.org/10.1016/j.gca.2018.06.007· OSTI ID:1479443

Miller, Hannah M. ^[1]; Chaudhry, Nabil ^[1]; Conrad, Mark E. ^[2]; Bill, Markus ^[2]; Kopf, Sebastian H. ^[1]; Templeton, Alexis S. ^[1]

Univ. of Colorado, Boulder, CO (United States). Department of Geological Sciences
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Earth Sciences Division

We report that high carbon isotope values (δ¹³C_CH4 > -40‰) have widely been used as evidence that methane in alkaline rock-hosted fluids was formed abiotically, particularly in serpentinizing systems. However, isotope fractionation during microbial methanogenesis is relatively understudied at high pH. We isolated a hydrogenotrophic Methanobacterium sp. from hyperalkaline subsurface fluids in the Samail ophiolite to assess how carbon and hydrogen isotope values of CH₄ varied depending upon pH and carbonate mineral source (NaHCO₃ or CaCO₃). The hydrogen isotope fractionation α_H20/CH4(1.46–1.66) did not vary across pH. In contrast, the expressed carbon isotope fractionation, α_CO2/CH4, ranged from 1.028 to 1.089. Carbon isotope fractionation increased with pH, reaching a maximum ¹³C depletion of -85‰. However, the ¹³C depletion significantly diminished at pH ≥ 9 for CaCO₃-amended experiments, generating δ¹³C_CH4 as high as -28‰. To evaluate the large variability in δ¹³C_CH4, we developed a steady-state model to assess how the rates of carbonate dissolution, cellular uptake of CO₂ and irreversible CH₄ production can affect the net isotope fractionation during methanogenesis. Methanobacterium sp. can produce highly depleted δ¹³C_CH4 in simulated alkaline serpentinizing fluids when dissolved inorganic carbon levels are high and methanogenesis rates are slow. However, small carbon isotope fractionation occurs when rates of carbonate dissolution are slower than cellular uptake, leading to relatively high δ¹³C_CH4 values (>~-35‰) that are traditionally interpreted to be purely “abiotic”. Lastly, microbial CH₄ can be produced in carbon-limited mafic and ultramafic rock-hosted environments on Earth and potentially other planetary bodies, but it may be difficult to isotopically identify biogenic methane when mineral carbonates are the dominant carbon source.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division; National Aeronautics and Space Administration

Grant/Contract Number:: AC02-05CH11231; SC0006886

OSTI ID:: 1479443

Alternate ID(s):: OSTI ID: 1582876

Journal Information:: Geochimica et Cosmochimica Acta, Vol. 237, Issue C; ISSN 0016-7037

Publisher:: The Geochemical Society; The Meteoritical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 30 works

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Methanogenesis
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Title: Large carbon isotope variability during methanogenesis under alkaline conditions

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