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The reaction CH3C(O)O2 + HO2  → CH3C(O)OOH + O2 (Reaction R5a), CH3C(O)OH + O3(Reaction R5b), CH3 + CO2 + OH + O2 (Reaction R5c)was studied in a series of experiments conducted at 1000 mbar and(293 ± 2) K in the HIRAC simulation chamber. For the first time,products, (CH3C(O)OOH, CH3C(O)OH, O3 and OH) from all threebranching pathways of the reaction have been detected directly andsimultaneously. Measurements of radical precursors (CH3OH, CH3CHO),HO2 and some secondary products HCHO and HCOOH further constrained thesystem. Fitting a comprehensive model to the experimental data, obtained overa range of conditions, determined the branching ratios α(R5a)  =  0.37 ± 0.10, α(R5b) =  0.12 ± 0.04 andα(R5c) =  0.51 ± 0.12 (errors at 2σ level).Improved measurement/model agreement was achieved using k(R5)  = (2.4 ± 0.4)  ×  10−11 cm3 molecule−1 s−1,which is within the large uncertainty of the current IUPAC and JPLrecommended rate coefficients for the title reaction. The rate coefficientand branching ratios are in good agreement with a recent study performed byGroß et al. (2014b); taken together, these two studies show that the rate of OHregeneration through Reaction (R5) is more rapid than previously thought.GEOS-Chem has been used to assess the implications of the revised ratecoefficients and branching ratios; the modelling shows an enhancement of upto 5 % in OH concentrations in tropical rainforest areas and increases ofup to 10 % at altitudes of 6–8 km above the equator, compared tocalculations based on the IUPAC recommended rate coefficient and yield. Theenhanced rate of acetylperoxy consumption significantly reduces PAN in remoteregions (up to 30 %) with commensurate reductions in background NOx

atmospheric chemistry and physics

Direct measurements of OH and other product yields from the HO&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt; + CH&amp;lt;sub&amp;gt;3&amp;lt;/sub&amp;gt;C(O)O&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt; reaction