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Ji et al. (1) published a study examining the mechanism of the initial stages of OH-initiated oxidation of toluene. Their results challenge the mechanisms used in atmospheric chemistry models [e.g., Master Chemical Mechanism (MCM) (2)] derived from chamber experiments at atmospheric conditions, and previous experimental (3, 4) and theoretical studies (5, 6). In these mechanisms, the main product (55–65%) of the O2 reaction with the OH-adduct is a peroxy-peroxide bridged radical (cyc-RO2, Scheme 1), the subsequent chemistry of which goes on to yield dienals and the dicarbonyls: glyoxal and methylglyoxal. The present study detected a negligible yield of these dicarbonyl products. From this, the authors conclude that the cyc-RO2 pathway is insignificant under atmospheric conditions. Simplified representation of chemical mechanism of OH-initiated toluene oxidation. For clarity, …

Elucidating the fate of the OH-adduct in toluene oxidation under tropospheric boundary layer conditions