24 Feb 2021

24 Feb 2021

Review status: this preprint is currently under review for the journal ACP.

Evolution of OH reactivity in low-NO volatile organic compound photooxidation investigated by the fully explicit GECKO-A model

Zhe Peng1, Julia Lee-Taylor1,2, Harald Stark1,3, John J. Orlando2, Bernard Aumont4, and Jose L. Jimenez1 Zhe Peng et al.
  • 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.

Status: final response (author comments only)

Comment types: AC – author | RC – referee | CC – community | EC – editor | CEC – chief editor | : Report abuse
  • RC1: 'Comment on acp-2021-118', Anonymous Referee #1, 19 Apr 2021
  • RC2: 'Comment on acp-2021-118', Anonymous Referee #2, 20 Apr 2021

Zhe Peng et al.


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Short summary
We use the fully explicit GECKO-A model to study the OH reactivity (OHR) evolution in the low-NO photooxidation of several volatile organic compounds. Oxidation progressively produces more saturated and functionalized species, then breaks them into small species. OHR per C atom evolution is similar for different precursors once saturated multifunctional species are formed. We also find that partitioning of these species to chamber walls leads to large deviations in chambers from the atmosphere.