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Extreme deuterium enrichment in stratospheric hydrogen and the global atmospheric budget of H2

Nature volume 424, pages 918–921 (2003)Cite this article

Abstract

Molecular hydrogen (H2) is the second most abundant trace gas in the atmosphere after methane1 (CH4). In the troposphere, the D/H ratio of H2 is enriched by 120‰ relative to the world's oceans2,3,4. This cannot be explained by the sources of H2 for which the D/H ratio has been measured to date (for example, fossil fuels and biomass burning)5,6. But the isotopic composition of H2 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 H2 produced from CH4 in the stratosphere, where production is isolated from the influences of non-photochemical sources and sinks, showing that the chain of reactions producing H2 from CH4 concentrates D in the product H2. This enrichment, which we estimate is similar on a global average in the troposphere, contributes substantially to the D/H ratio of tropospheric H2.

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Figure 1: Simplified schematic diagram of the reaction pathway from methane to molecular hydrogen for both normal CH4 and isotopically substituted CH3D.
Figure 2: Methane and hydrogen mixing ratios in the stratosphere relative to nitrous oxide and mean age.
Figure 3: Plot of δDH2 (open symbols) and δDCH4 (filled circles) in the stratosphere against methane mixing ratios.

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Acknowledgements

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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  1. Thom Rahn

    Present address: Los Alamos National Laboratory, EES-6, MS-D462, Los Alamos, New Mexico, 87545, USA

Authors and Affiliations

  1. Division of Geological and Planetary Sciences, California Institute of Technology, Pasadena, California, 91125, USA

    Thom Rahn, John M. Eiler & Paul O. Wennberg

  2. Division of Engineering and Applied Sciences, California Institute of Technology, Pasadena, California, 91125, USA

    Paul O. Wennberg

  3. Department of Chemistry, University of California at Berkeley, Berkeley, California, 94720, USA

    Kristie A. Boering & Michael C. McCarthy

  4. Department of Earth and Planetary Science, University of California at Berkeley, Berkeley, California, 94720, USA

    Kristie A. Boering

  5. Earth Systems Science Department, University of California, Irvine, Irvine, California, 92697, USA

    Stanley Tyler

  6. National Center for Atmospheric Research, Boulder, Colorado, 80307-3000, USA

    Sue Schauffler, Stephen Donnelly & Elliot Atlas

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Correspondence to Thom Rahn.

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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). https://doi.org/10.1038/nature01917

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