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Abstract. OH reactivity (OHR) is an important control on the oxidative capacity in the atmosphere but remains poorly constrained in many environments, such asremote, rural, and urban atmospheres, as well as laboratory experiment setups under low-NO conditions. For an improved understanding of OHR, itsevolution during oxidation of volatile organic compounds (VOCs) is a major aspect requiring better quantification. We use the fully explicitGenerator of Explicit Chemistry and Kinetics of Organics in the Atmosphere (GECKO-A) model to study the OHR evolution in the NO-free photooxidationof several VOCs, including decane (an alkane), m-xylene (an aromatic), and isoprene (an alkene). Oxidation progressively produces more saturated and functionalized species. Total organic OHR (including precursor and products, OHRVOC) first increases for decane (as functionalization increases OH rate coefficients) and m-xylene (as much more reactive oxygenated alkenes are formed). For isoprene, C=C bond consumption leads to a rapid drop in OHRVOC before significant production of the first main saturated multifunctional product, i.e., isoprene epoxydiol. The saturated multifunctional species in the oxidation of different precursors have similar average OHRVOC per C atom. The latter oxidation follows a similar course for different precursors, involving fragmentation of multifunctional species to eventual oxidation of C1 and C2 fragments to CO2, leading tomore »a similar evolution of OHRVOC per C atom. An upper limit of the total OH consumption during complete oxidation to CO2 is roughly three per C atom. We also explore the trends in radical recycling ratios. We show that differences in the evolution of OHRVOC between the atmosphere and an environmental chamber, and between the atmosphere and an oxidation flow reactor (OFR), can be substantial, with the former being even larger, but these differences are often smaller than between precursors. The Teflon wall losses of oxygenated VOCs in chambers result in large deviations of OHRVOC from atmospheric conditions, especially for the oxidation of larger precursors, where multifunctional species may suffer substantial wall losses, resulting in significant underestimation of OHRVOC. For OFR, the deviations of OHRVOC evolution from the atmospheric case are mainly due to significant OHR contribution from RO2 and lack of efficient organic photolysis. The former can be avoided by lowering the UV lamp setting in OFR, while the latter is shown to be very difficult to avoid. However, the former may significantly offset the slowdown in fragmentation of multifunctional species due to lack of efficient organic photolysis.« less

Abstract. Oxidation flow reactors (OFRs) are a promising complement toenvironmental chambers for investigating atmospheric oxidation processes andsecondary aerosol formation. However, questions have been raised about howrepresentative the chemistry within OFRs is of that in the troposphere. Weinvestigate the fates of organic peroxy radicals (RO₂), which playa central role in atmospheric organic chemistry, in OFRs and environmentalchambers by chemical kinetic modeling and compare to a variety of ambientconditions to help define a range of atmospherically relevant OFR operatingconditions. For most types of RO₂, their bimolecular fates in OFRsare mainly RO₂+HO₂ and RO₂+NO, similar to chambers andatmospheric studies. For substituted primary RO₂ and acylRO₂, RO₂+RO₂ can make a significant contribution tothe fate of RO₂ in OFRs, chambers and the atmosphere, butRO₂+RO₂ in OFRs is in general somewhat less important than inthe atmosphere. At high NO, RO₂+NO dominates RO₂ fate inOFRs, as in the atmosphere. At a high UV lamp setting in OFRs,RO₂+OH can be a major RO₂ fate and RO₂isomerization can be negligible for common multifunctional RO₂,both of which deviate from common atmospheric conditions. In the OFR254operation mode (for which OH is generated only from the photolysismore »of addedO₃), we cannot identify any conditions that can simultaneouslyavoid significant organic photolysis at 254 nm and lead to RO₂lifetimes long enough (∼ 10 s) to allow atmospherically relevantRO₂ isomerization. In the OFR185 mode (for which OH is generatedfrom reactions initiated by 185 nm photons), high relative humidity, low UVintensity and low precursor concentrations are recommended for theatmospherically relevant gas-phase chemistry of both stable species andRO₂. These conditions ensure minor or negligible RO₂+OHand a relative importance of RO₂ isomerization in RO₂fate in OFRs within $\sim \times \mathrm{2}$ of that in the atmosphere. Under theseconditions, the photochemical age within OFR185 systems can reach a fewequivalent days at most, encompassing the typical ages for maximum secondaryorganic aerosol (SOA) production. A small increase in OFR temperature mayallow the relative importance of RO₂ isomerization to approach theambient values. To study the heterogeneous oxidation of SOA formed underatmospherically relevant OFR conditions, a different UV source with higherintensity is needed after the SOA formation stage, which can be done withanother reactor in series. Finally, we recommend evaluating the atmosphericrelevance of RO₂ chemistry by always reporting measured and/orestimated OH, HO₂, NO, NO₂ and OH reactivity (or at leastprecursor composition and concentration) in all chamber and flow reactorexperiments. An easy-to-use RO₂ fate estimator program is includedwith this paper to facilitate the investigation of this topic in futurestudies.

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