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D/H ratios in terrestrially sourced petroleum systems

Schimmelmann, Arndt and Sessions, Alex L. and Boreham, Christopher J. and Edwards, Dianne S. and Logan, Graham A. and Summons, Roger E. (2004) D/H ratios in terrestrially sourced petroleum systems. Organic Geochemistry, 35 (10). pp. 1169-1195. ISSN 0146-6380. doi:10.1016/j.orggeochem.2004.05.006.

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D/H ratios of terrestrially-sourced whole oils and their respective saturated, aromatic, and polar fractions, individual n-alkanes, formation waters and non-exchangeable hydrogen in kerogen were measured in potential source rocks from seven Australian petroleum basins. Data for 75 oils and condensates, their sub-fractions and 52 kerogens indicate that oil sub-fractions have δD values comparable to δD_(oil), with a ΔδD offset (δD_(kerogen)−δD_(oil)) averaging ca. 23‰. The weighted-average δD of individual n-alkanes is usually identical to δD_(oil) and δD_(saturate). A trend of increasing δD with n-alkane chain length in most oils causes individual n-alkanes from an oil to vary in δD by 30‰ or more. A modest correlation between δD for aromatic sub-fractions and formation waters indicates that about 50% of aromatic C-bound H has exchanged with water. In contrast, δD_(oil) and δD_(saturated) show no evidence for H-exchange with formation water under reservoir conditions at temperatures up to 150 °C. Acyclic isoprenoids and n-alkanes show essentially indistinguishable δD, indicating that primary isotopic differences from biosynthesis have been erased. Overall, extensive exchange of C-bound H in petroleum with other hydrogen is apparent, but seems to have affected most hydrocarbons only during their chemical genesis from precursor molecules. Our isotopic findings from terrestrially-sourced oils should be qualitatively relevant for marine oils as well.

Item Type:Article
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URLURL TypeDescription DOIArticle
Schimmelmann, Arndt0000-0003-4648-5253
Sessions, Alex L.0000-0001-6120-2763
Summons, Roger E.0000-0002-7144-8537
Additional Information:© 2004 Elsevier Ltd. Received 23 January 2004; accepted 31 May 2004 (returned to author for revision 4 April 2004); Available online 3 August 2004. This work was supported by US Department of Energy Basic Energy Research Grant number DE-FG02-00ER15032 to AS, and by the NASA Exobiology Program grants NAG5-9422 to John M. Hayes and NAG5-12356 to RES. We gratefully acknowledge the assistance of Geoscience Australia research and support staff, Janet Hope and Natalie Crawford. CJB, DSE and GAL publish with permission of the CEO of Geoscience Australia. This manuscript greatly benefited from constructive reviews by Kliti Grice and Yongchun Tang.
Funding AgencyGrant Number
Department of Energy (DOE)DE-FG02-00ER15032
Issue or Number:10
Record Number:CaltechAUTHORS:20131106-113151972
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Official Citation:Arndt Schimmelmann, Alex L. Sessions, Christopher J. Boreham, Dianne S. Edwards, Graham A. Logan, Roger E. Summons, D/H ratios in terrestrially sourced petroleum systems, Organic Geochemistry, Volume 35, Issue 10, October 2004, Pages 1169-1195, ISSN 0146-6380, (
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:42277
Deposited By: Tony Diaz
Deposited On:06 Nov 2013 22:02
Last Modified:10 Nov 2021 16:21

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