Atmospheric chemistry of small organic peroxy radicals

Abstract

Global atmospheric models play a key role in international assessments of the human impact on global climate and air pollution. To increase the accuracy and facilitate comparison of results from such models, it is essential they contain up‐to‐date chemical mechanisms. To this end, we present an evaluation of the atmospheric chemistry of the four most abundant organic peroxy radicals: CH 3 O 2, C 2 H 5 O 2, CH 3 C(O)O 2, and CH 3 C(O)CH 2 O 2. The literature data for the atmospheric reactions of these radicals are evaluated. In addition, the ultraviolet absorption cross sections for the above radicals and for HO 2 have been evaluated. The absorption spectra were fitted to an analytical formula, which enabled published spectra to be screened objectively. Published kinetic and product data were reinterpreted, or in some case reanalyzed, using the new cross sections, leading to a self‐consistent set of kinetic, mechanistic, and spectroscopic data. Product studies were also evaluated. A set of peroxy radical reaction rate coefficients and products are recommended for use in atmospheric modeling. A three‐dimensional global chemical transport model (the Intermediate Model for the Global Evolution of Species, IMAGES) was run using both previously recommended rate coefficients and the current set to highlight the sensitivity of key atmospheric trace species to the peroxy radical chemistry used in the model.