Atmospheric Fate of Methyl Vinyl Ketone: Peroxy Radical Reactions with NO and HO2

First generation product yields from the OH-initiated oxidation of methyl vinyl ketone (3-buten-2-one, MVK) under both low and high NO conditions are reported. In the low NO chemistry, three distinct reaction channels are identified leading to the formation of (1) OH, glycolaldehyde, and acetyl peroxy R2a, (2) a hydroperoxide R2b, and (3) an alpha-diketone R2c. The alpha-diketone likely results from HOx-neutral chemistry previously only known to occur in reactions of HO2 with halogenated peroxy radicals. Quantum chemical calculations demonstrate that all channels are kinetically accessible at 298 K. In the high NO chemistry, glycolaldehyde is produced with a yield of 74 +/- 6.0%. Two alkyl nitrates are formed with a combined yield of 4.0 +/- 0.6%. We revise a three-dimensional chemical transport model to assess what impact these modifications in the MVK mechanism have on simulations of atmospheric oxidative chemistry. The calculated OH mixing ratio over the Amazon increases by 6%, suggesting that the low NO chemistry makes a non-negligible contribution toward sustaining the atmospheric radical pool.