Atmospheric Chemistry and Physics www.atmos-chem-phys.net 1680-7316 1680-7324 3 6 2003 10.5194/acp-3-2015-2003 http://www.atmos-chem-phys.net/3/2015/2003/ http://www.atmos-chem-phys.net/3/2015/2003/acp-3-2015-2003.html http://www.atmos-chem-phys.net/3/2015/2003/acp-3-2015-2003.pdf 2015 2023 2003-11-19 Heavy hydrogen in the stratosphere T. Röckmann T. S. Rhee A. Engel Max-Planck-Institut für Kernphysik, Bereich Atmosphärenphysik, Saupfercheckweg 1, 69117 Heidelberg, Germany Max-Planck-Institut für Chemie, Chemie der Atmosphäre, Becherweg 27, 55122 Mainz, Germany Institut für Meteorologie und Geophysik, Universität Frankfurt, Georg Voigt Str. 14, 60325 Frankfurt, Germany We report measurements of the deuterium content of molecular hydrogen (H2) obtained from a suite of air samples that were collected during a stratospheric balloon flight between 12 and 33 km at 40º N in October 2002. Strong deuterium enrichments of up to 400 permil versus Vienna Standard Mean Ocean Water (VSMOW) are observed, while the H2 mixing ratio remains virtually constant. Thus, as hydrogen is processed through the H2 reservoir in the stratosphere, deuterium is accumulated in H2 . Using box model calculations we investigated the effects of H2 sources and sinks on the stratospheric enrichments. Results show that considerable isotope enrichments in the production of H2  from CH4 must take place, i.e., deuterium is transferred preferentially to H2 during the CH4 oxidation sequence. This supports recent conclusions from tropospheric H2 isotope measurements which show that H2 produced photochemically from CH4 and non-methane hydrocarbons must be enriched in deuterium to balance the tropospheric hydrogen isotope budget. In the absence of further data on isotope fractionations in the individual reaction steps of the CH4 oxidation sequence, this effect cannot be investigated further at present. Our measurements imply that molecular hydrogen has to be taken into account when the hydrogen isotope budget in the stratosphere is investigated.