Atmospheric Chemistry and Physics, vol. 9 (2009) pp. 1479-1501
We describe a nearly explicit chemical mecha-nism for isoprene photooxidation guided by chamber stud-ies that include time-resolved observation of an extensive suite of volatile compounds. We provide new constraints on the chemistry of the poorly-understood isoprene δ-hydroxy channels, which account for more than one third of the to-tal isoprene carbon flux and a larger fraction of the nitrate yields. We show that the cis branch dominates the chem-istry of the δ-hydroxy channel with less than 5% of the car-bon following the trans branch. The modelled yield of iso-prene nitrates is 12±3% with a large difference between the δ and β branches. The oxidation of these nitrates releases about 50% of the NO x . Methacrolein nitrates (modelled yield from methacrolein) and methylvinylketone nitrates (modelled yield yield from methylvinylke-tone) are also observed. Propanone nitrate, produced with a yield of 1% from isoprene, appears to be the longest-lived ni-trate formed in the total oxidation of isoprene. We find a large molar yield of formic acid and suggest a novel mechanism leading to its formation from the organic nitrates. Finally, the most important features of this mechanism are summa-rized in a condensed scheme appropriate for use in global chemical transport models.
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