Evolution of OH reactivity in low-NO volatile organic compound photooxidation investigated by the fully explicit GECKO-A model
- 1Department of Chemistry and Cooperative Institute for Research in Environmental Sciences, University of Colorado, Boulder, Colorado 80309, USA
- 2Atmospheric Chemistry Observation and Modeling Laboratory, National Center for Atmospheric Research, Boulder, Colorado 80307, USA
- 3Aerodyne Research Inc., Billerica, Massachusetts 01821, USA
- 4Laboratoire Inter-Universitaire des Systèmes Atmosphériques (LISA), UMR 7583, Université Paris-Est Créteil, Université de Paris, CNRS, Institut Pierre Simon Laplace, 94010 Créteil, France
Abstract. OH reactivity (OHR) is an important control on the oxidative capacity in the atmosphere but remains poorly constrained. For an improved understanding of OHR, its evolution during oxidation of volatile organic compounds (VOCs) is a major aspect requiring better quantification. We use the fully explicit Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere (GECKO-A) model to study the OHR evolution in the low-NO photooxidation of 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 to a similar evolution of OHRVOC per C atom. An upper limit of the total OH consumption during complete oxidation to CO2 is roughly 3 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 substantial deviations of OHRVOC from atmospheric conditions, especially for the oxidation of larger precursors, where multifunctional species may suffer near-complete 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.
Zhe Peng et al.
Zhe Peng et al.
Zhe Peng et al.
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