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Extreme deuterium enrichment in stratospheric hydrogen and the global atmospheric budget of H_2

Rahn, Thom and Eiler, John M. and Boering, Kristie A. and Wennberg, Paul O. and McCarthy, Michael C. and Tyler, Stanley and Schauffler, Sue and Donnelly, Stephen and Atlas, Elliot (2003) Extreme deuterium enrichment in stratospheric hydrogen and the global atmospheric budget of H_2. Nature, 424 (6951). pp. 918-921. ISSN 0028-0836. doi:10.1038/nature01917.

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Molecular hydrogen (H_2) is the second most abundant trace gas in the atmosphere after methane (CH_4). In the troposphere, the D/H ratio of H_2 is enriched by 120‰ relative to the world's oceans. This cannot be explained by the sources of H_2 for which the D/H ratio has been measured to date (for example, fossil fuels and biomass burning). But the isotopic composition of H_2 from its single largest source—the photochemical oxidation of methane—has yet to be determined. Here we show that the D/H ratio of stratospheric H2 develops enrichments greater than 440‰, the most extreme D/H enrichment observed in a terrestrial material. We estimate the D/H ratio of H_2 produced from CH_4 in the stratosphere, where production is isolated from the influences of non-photochemical sources and sinks, showing that the chain of reactions producing H_2 from CH_4 concentrates D in the product H_2. This enrichment, which we estimate is similar on a global average in the troposphere, contributes substantially to the D/H ratio of tropospheric H_2.

Item Type:Article
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Wennberg, Paul O.0000-0002-6126-3854
McCarthy, Michael C.0000-0002-5450-5894
Atlas, Elliot0000-0003-3847-5346
Additional Information:© 2003 Nature Publishing Group. Received 24 January; accepted 15 July 2003. We thank N. Kitchen for assistance in the laboratory. This study was supported in part by the NSF (T.A.R., K.A.B. and S.T.), the Davidow Fund and General Motors Corp. (J.M.E), the David and Lucile Packard Foundation (K.A.B.) and the NASA Upper Atmosphere Research Program (P.O.W., K.A.B, E.A, S.S. and S.D.). The National Centre for Atmospheric Research is operated by the University Corporation for Atmospheric Research under the sponsorship of the NSF. T.R. is the recipient of a Frederick Reines postdoctoral fellowship in experimental sciences awarded by Los Alamos National Laboratory.
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General Motors CorporationUNSPECIFIED
David and Lucile Packard FoundationUNSPECIFIED
Los Alamos National LaboratoryUNSPECIFIED
Issue or Number:6951
Record Number:CaltechAUTHORS:20121205-103720228
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Official Citation:Rahn, T., Eiler, J., Boering, K. et al. Extreme deuterium enrichment in stratospheric hydrogen and the global atmospheric budget of H2. Nature 424, 918–921 (2003).
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:35820
Deposited On:05 Dec 2012 19:29
Last Modified:09 Nov 2021 23:17

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