Primary Formation of Highly Oxidized Multifunctional Products in the OH-Initiated Oxidation of Isoprene : A Combined Theoretical and Experimental Study

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Wang , S , Riva , M , Yan , C , Ehn , M & Wang , L 2018 , ' Primary Formation of Highly Oxidized Multifunctional Products in the OH-Initiated Oxidation of Isoprene : A Combined Theoretical and Experimental Study ' , Environmental Science & Technology , vol. 52 , no. 21 , pp. 12255-12264 . https://doi.org/10.1021/acs.est.8b02783

Title: Primary Formation of Highly Oxidized Multifunctional Products in the OH-Initiated Oxidation of Isoprene : A Combined Theoretical and Experimental Study
Author: Wang, Sainan; Riva, Matthieu; Yan, Chao; Ehn, Mikael; Wang, Liming
Contributor organization: INAR Physics
Institute for Atmospheric and Earth System Research (INAR)
Date: 2018-11-06
Language: eng
Number of pages: 10
Belongs to series: Environmental Science & Technology
ISSN: 0013-936X
DOI: https://doi.org/10.1021/acs.est.8b02783
URI: http://hdl.handle.net/10138/322499
Abstract: It is generally assumed that isoprene-derived secondary organic aerosol (SOA) precursors are mainly formed from the secondary reactions of intermediate products with OH radicals in the gas phase and multiphase oxidation in particles. In this paper, we predicted a theoretical mechanism for the primary formation of highly oxygenated molecules (HOM) in the gas phase through successive intramolecular H-shifts and O-2 addition in the specific Z-delta isomer of hydroxyl-peroxy radicals and alkoxy radicals. The position of O-2 addition is different from that in forming hydroperoxy aldehydes. The prediction was further supported experimentally by successfully identifying a few highly oxidized peroxy radicals and closed-shell products such as C5H9O7,9, C5H10O6,7,8, and C4H8O5 in a flow reactor by chemical ionization mass spectrometry at air pressure. These HOM products could serve as important precursors to isoprene-derived SOA. Further modeling studies on the effect of NO concentration suggested that HOM formation could account for up to, similar to 11% of the branching ratio (similar to 9% from the 4-OH channel and similar to 2% from the 1-OH channel) in the reaction of isoprene with OH when the lifetimes of peroxy radicals due to bimolecular reactions are similar to 100 s, which is typical in forest regions.
Subject: SECONDARY ORGANIC AEROSOL
CHEMICAL-IONIZATION
MASS-SPECTROMETER
EPOXIDE FORMATION
RADICALS
ISOMERIZATION
OZONOLYSIS
VOLATILITY
YIELDS
NO
114 Physical sciences
116 Chemical sciences
1172 Environmental sciences
Peer reviewed: Yes
Usage restriction: openAccess
Self-archived version: acceptedVersion


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