Organic peroxy radical chemistry in oxidation flow reactors and environmental chambers and their atmospheric relevance


Oxidation flow reactors (OFRs) are a promising complement to environmental chambers for investigating atmospheric oxidation processes and secondary aerosol formation. However, questions have been raised about how representative the chemistry within OFRs is of that in the troposphere. We investigate the fates of organic peroxy radicals (RO2), which play a central role in atmospheric organic chemistry, in OFRs and environmental chambers by chemical kinetic modeling and compare to a variety of ambient conditions to help define a range of atmospherically relevant OFR operating conditions. For most types of RO2, their bimolecular fates in OFRs are mainly RO2 + HO2 and RO2 + NO, similar to chambers and atmospheric studies. For substituted primary RO2 and acyl RO2, RO2 + RO2 can make a significant contribution to the fate of RO2 in OFRs, chambers and the atmosphere, but RO2 + RO2 in OFRs is in general somewhat less important than in the atmosphere. At high NO, RO2 + NO dominates RO2 fate in OFRs, as in the atmosphere. At a high UV lamp setting in OFRs, RO2 + OH can be a major RO2 fate and RO2 isomerization can be negligible for common multifunctional RO2, both of which deviate from common atmospheric conditions. In the OFR254 operation mode (for which OH is generated only from the photolysis of added O3), we cannot identify any conditions that can simultaneously avoid significant organic photolysis at 254&thinsp;nm and lead to RO2 lifetimes long enough ( ∼  10&thinsp;s) to allow atmospherically relevant RO2 isomerization. In the OFR185 mode (for which OH is generated from reactions initiated by 185&thinsp;nm photons), high relative humidity, low UV intensity and low precursor concentrations are recommended for the atmospherically relevant gas-phase chemistry of both stable species and RO2. These conditions ensure minor or negligible RO2 + OH and a relative importance of RO2 isomerization in RO2 fate in OFRs within  ∼   × 2 of that in the atmosphere. Under these conditions, the photochemical age within OFR185 systems can reach a few equivalent days at most, encompassing the typical ages for maximum secondary organic aerosol (SOA) production. A small increase in OFR temperature may allow the relative importance of RO2 isomerization to approach the ambient values. To study the heterogeneous oxidation of SOA formed under atmospherically relevant OFR conditions, a different UV source with higher intensity is needed after the SOA formation stage, which can be done with another reactor in series. Finally, we recommend evaluating the atmospheric relevance of RO2 chemistry by always reporting measured and/or estimated OH, HO2, NO, NO2 and OH reactivity (or at least precursor composition and concentration) in all chamber and flow reactor experiments. An easy-to-use RO2 fate estimator program is included with this paper to facilitate the investigation of this topic in future studies.</p

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