Clumped 13C–13C isotopologue signatures of thermogenic ethane.

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Title: Clumped 13C–13C isotopologue signatures of thermogenic ethane.
Authors: Taguchi, Koudai1 (AUTHOR) ktaguchi@jamstec.go.jp, Ueno, Yuichiro1,2,3 (AUTHOR), Gilbert, Alexis2,3 (AUTHOR), Matsui, Yohei4 (AUTHOR), Shibuya, Takazo1 (AUTHOR), Kawagucci, Shinsuke1,4 (AUTHOR)
Source: Geochimica et Cosmochimica Acta. Apr2025, Vol. 394, p258-267. 10p.
Subjects: Marine sediments, Climatology, Carbon isotopes, Dingo, Ethanes
Abstract: The origin of hydrocarbons is a central question in climate science, biogeochemistry, and astrobiology. Carbon and hydrogen isotopic ratios have been used to constrain hydrocarbon sources; however, studies based on these parameters alone are lacking. The recent development of a doubly substituted ("clumped") ethane isotopologue (13C 2 H 6) is expected to be useful in distinguishing between thermogenic and abiotic ethane owing to the specific signature of the former. However, the mechanistic determinants of clumped 13C–13C isotopologue signatures in thermogenic ethane remain insufficiently understood. In this study, we conducted pyrolysis experiments over ∼ 2 years under controlled temperatures and pressures, with lignin, docosane (C 22 H 46), and marine sediments used as reagents. All ethane samples exhibited clumped 13C–13C isotopologue signatures with similarly nearly absent or slight 13C–13C enrichment against a stochastic distribution. The 13C–13C clumping of thermally produced ethane from organic matter was similar to that of natural thermogenic ethane and different from that of putatively abiotic ethane of Kidd Creek and the Dingo gas field in the Amadeus Basin, which showed a significantly lower abundance of 13C–13C relative to stochastic distribution. The abundances of 13C–13C in ethane suggest that the signature of thermogenic ethane is inherited from a C–C bond in the precursor molecule and altered by a combinatorial effect during thermal cracking. Post-genetic ethane decomposition via heating might alter the 13C–13C signature in ethane, although the effects are difficult to observe. Thermogenic ethane should exhibit a positive clumped isotopologue signature regardless of thermal maturity; therefore, clumped isotopologue signatures may serve as key indicators to distinguish between thermogenic and abiotic ethane. [ABSTRACT FROM AUTHOR]
Copyright of Geochimica et Cosmochimica Acta is the property of Pergamon Press - An Imprint of Elsevier Science and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)
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  Data: Clumped 13C–13C isotopologue signatures of thermogenic ethane.
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  Data: <searchLink fieldCode="AR" term="%22Taguchi%2C+Koudai%22">Taguchi, Koudai</searchLink><relatesTo>1</relatesTo> (AUTHOR)<i> ktaguchi@jamstec.go.jp</i><br /><searchLink fieldCode="AR" term="%22Ueno%2C+Yuichiro%22">Ueno, Yuichiro</searchLink><relatesTo>1,2,3</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Gilbert%2C+Alexis%22">Gilbert, Alexis</searchLink><relatesTo>2,3</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Matsui%2C+Yohei%22">Matsui, Yohei</searchLink><relatesTo>4</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Shibuya%2C+Takazo%22">Shibuya, Takazo</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Kawagucci%2C+Shinsuke%22">Kawagucci, Shinsuke</searchLink><relatesTo>1,4</relatesTo> (AUTHOR)
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  Data: <searchLink fieldCode="JN" term="%22Geochimica+et+Cosmochimica+Acta%22">Geochimica et Cosmochimica Acta</searchLink>. Apr2025, Vol. 394, p258-267. 10p.
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  Data: <searchLink fieldCode="DE" term="%22Marine+sediments%22">Marine sediments</searchLink><br /><searchLink fieldCode="DE" term="%22Climatology%22">Climatology</searchLink><br /><searchLink fieldCode="DE" term="%22Carbon+isotopes%22">Carbon isotopes</searchLink><br /><searchLink fieldCode="DE" term="%22Dingo%22">Dingo</searchLink><br /><searchLink fieldCode="DE" term="%22Ethanes%22">Ethanes</searchLink>
– Name: Abstract
  Label: Abstract
  Group: Ab
  Data: The origin of hydrocarbons is a central question in climate science, biogeochemistry, and astrobiology. Carbon and hydrogen isotopic ratios have been used to constrain hydrocarbon sources; however, studies based on these parameters alone are lacking. The recent development of a doubly substituted ("clumped") ethane isotopologue (13C 2 H 6) is expected to be useful in distinguishing between thermogenic and abiotic ethane owing to the specific signature of the former. However, the mechanistic determinants of clumped 13C–13C isotopologue signatures in thermogenic ethane remain insufficiently understood. In this study, we conducted pyrolysis experiments over ∼ 2 years under controlled temperatures and pressures, with lignin, docosane (C 22 H 46), and marine sediments used as reagents. All ethane samples exhibited clumped 13C–13C isotopologue signatures with similarly nearly absent or slight 13C–13C enrichment against a stochastic distribution. The 13C–13C clumping of thermally produced ethane from organic matter was similar to that of natural thermogenic ethane and different from that of putatively abiotic ethane of Kidd Creek and the Dingo gas field in the Amadeus Basin, which showed a significantly lower abundance of 13C–13C relative to stochastic distribution. The abundances of 13C–13C in ethane suggest that the signature of thermogenic ethane is inherited from a C–C bond in the precursor molecule and altered by a combinatorial effect during thermal cracking. Post-genetic ethane decomposition via heating might alter the 13C–13C signature in ethane, although the effects are difficult to observe. Thermogenic ethane should exhibit a positive clumped isotopologue signature regardless of thermal maturity; therefore, clumped isotopologue signatures may serve as key indicators to distinguish between thermogenic and abiotic ethane. [ABSTRACT FROM AUTHOR]
– Name: AbstractSuppliedCopyright
  Label:
  Group: Ab
  Data: <i>Copyright of Geochimica et Cosmochimica Acta is the property of Pergamon Press - An Imprint of Elsevier Science and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.)
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RecordInfo BibRecord:
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      – Type: doi
        Value: 10.1016/j.gca.2025.02.017
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      – Code: eng
        Text: English
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      Pagination:
        PageCount: 10
        StartPage: 258
    Subjects:
      – SubjectFull: Marine sediments
        Type: general
      – SubjectFull: Climatology
        Type: general
      – SubjectFull: Carbon isotopes
        Type: general
      – SubjectFull: Dingo
        Type: general
      – SubjectFull: Ethanes
        Type: general
    Titles:
      – TitleFull: Clumped 13C–13C isotopologue signatures of thermogenic ethane.
        Type: main
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            NameFull: Taguchi, Koudai
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            NameFull: Ueno, Yuichiro
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            NameFull: Gilbert, Alexis
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            NameFull: Matsui, Yohei
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            NameFull: Shibuya, Takazo
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            NameFull: Kawagucci, Shinsuke
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            – D: 01
              M: 04
              Text: Apr2025
              Type: published
              Y: 2025
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              Value: 394
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