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© Author(s) 2018. This work is distributed under
the Creative Commons Attribution 4.0 License.
© Author(s) 2018. This work is distributed under
the Creative Commons Attribution 4.0 License.

Research article 24 Sep 2018

Research article | 24 Sep 2018

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This discussion paper is a preprint. It is a manuscript under review for the journal Atmospheric Chemistry and Physics (ACP).

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

Zhe Peng1, Julia Lee-Taylor1,2, John J. Orlando2, Geoffrey S. Tyndall2, and Jose L. Jimenez1 Zhe Peng et al.
  • 1Cooperative Institute for Research in Environmental Sciences and Department of Chemistry, University of Colorado, Boulder, Colorado 80309, USA
  • 2Atmospheric Chemistry Observation and Modeling Laboratory, National Center for Atmospheric Research, Boulder, Colorado 80307, USA

Abstract. Oxidation flow reactors (OFR) 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 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 (where OH is generated only from photolysis of added O3), we cannot identify any conditions that can simultaneously avoid significant organic photolysis at 254nm and lead to RO2 lifetimes long enough (~10s) to allow atmospherically relevant RO2 isomerization. In the OFR185 mode (where OH is generated from reactions initiated by 185nm photons), high relative humidity, low UV intensity and low precursor concentrations are recommended for 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 ~x2 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 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 investigation of this topic in future studies.

Zhe Peng et al.
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Zhe Peng et al.
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Short summary
The use of Oxidation Flow Reactors (OFRs) has been rapidly increasing. We investigate organic peroxy radical (RO2) chemistry in OFRs by kinetic modeling. It is found that, at low NO, UV intensity should be limited to avoid high radical levels leading to significant reaction of RO2 with OH and negligible RO2 isomerization, both of which are atmospherically irrelevant. We also develop two RO2 Fate Estimators (for general use and for OFRs, respectively) to aid experiment design and interpretation.
The use of Oxidation Flow Reactors (OFRs) has been rapidly increasing. We investigate organic...