Isoprene NO3 Oxidation Products from the RO2 + HO2 Pathway

The Journal of Physical Chemistry. a
Rebecca H SchwantesPaul O Wennberg

Abstract

We describe the products of the reaction of the hydroperoxy radical (HO(2)) with the alkylperoxy radical formed following addition of the nitrate radical (NO(3)) and O(2) to isoprene. NO(3) adds preferentially to the C(1) position of isoprene (>6 times more favorably than addition to C(4)), followed by the addition of O(2) to produce a suite of nitrooxy alkylperoxy radicals (RO(2)). At an RO(2) lifetime of ∼30 s, δ-nitrooxy and β-nitrooxy alkylperoxy radicals are present in similar amounts. Gas-phase product yields from the RO(2) + HO(2) pathway are identified as 0.75-0.78 isoprene nitrooxy hydroperoxide (INP), 0.22 methyl vinyl ketone (MVK) + formaldehyde (CH(2)O) + hydroxyl radical (OH) + nitrogen dioxide (NO(2)), and 0-0.03 methacrolein (MACR) + CH(2)O + OH + NO(2). We further examined the photochemistry of INP and identified propanone nitrate (PROPNN) and isoprene nitrooxy hydroxyepoxide (INHE) as the main products. INHE undergoes similar heterogeneous chemistry as isoprene dihydroxy epoxide (IEPOX), likely contributing to atmospheric secondary organic aerosol formation.

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Citations

Dec 16, 2016·The Journal of Physical Chemistry. a·Torsten BerndtMarkku Kulmala
Jun 7, 2017·The Journal of Physical Chemistry Letters·Theo KurténHenrik G Kjaergaard
Jul 3, 2018·Atmospheric Chemistry and Physics·Jingqiu MaoLarry W Horowitz
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Jan 8, 2021·Environmental Science & Technology·Jacqueline F HamiltonAndrew R Rickard
Nov 19, 2021·The Journal of Physical Chemistry. a·Marla P DeVault, Paul J Ziemann

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