Atmospheric Chemistry and Physics Discussions www.atmos-chem-phys-discuss.net 1680-7367 1680-7375 9 2 2009 10.5194/acpd-9-5679-2009 http://www.atmos-chem-phys-discuss.net/9/5679/2009/ http://www.atmos-chem-phys-discuss.net/9/5679/2009/acpd-9-5679-2009.html http://www.atmos-chem-phys-discuss.net/9/5679/2009/acpd-9-5679-2009.pdf 5679 5751 2009-03-03 A consistent molecular hydrogen isotope chemistry scheme based on an independent bond approximation G. Pieterse M. C. Krol T. Röckmann t.roeckmann@uu.nl Institute for Marine and Atmospheric Research Utrecht, Utrecht, The Netherlands The isotopic composition of molecular hydrogen (H₂) produced by photochemical oxidation of methane (CH₄) and Volatile Organic Compounds (VOCs) is a key quantity in the global isotope budget of (H₂). The many individual reaction steps involved complicate its investigation. Here we present a simplified structure-activity approach to assign isotope effects to the individual elementary reaction steps in the oxidation sequence of CH₄ and some other VOCs. The approach builds on and extends the work by Gerst and Quay (2001) and Feilberg et al. (2007b). The description is generalized and allows the application, in principle, also to other compounds. The idea is that the C-H and C-D bonds – seen as reactive sites – have similar relative reaction probabilities in isotopically substituted, but otherwise identical molecules. The limitations of this approach are discussed for the reaction CH₄+Cl. The same approach is applied to VOCs, which are important precursors of H₂ that need to be included into models. Unfortunately, quantitative information on VOC isotope effects and source isotope signatures is very limited and the isotope scheme at this time is limited to a strongly parameterized statistical approach, which neglects kinetic isotope effects. 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