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  Insights into HOx and ROx chemistry in the boreal forest via measurement of peroxyacetic acid, peroxyacetic nitric anhydride (PAN) and hydrogen peroxide

Crowley, J. N., Pouvesle, N., Phillips, G. J., Axinte, R., Fischer, H., Petajä, T., et al. (2018). Insights into HOx and ROx chemistry in the boreal forest via measurement of peroxyacetic acid, peroxyacetic nitric anhydride (PAN) and hydrogen peroxide. Atmospheric Chemistry and Physics, 18(18), 13457-13479. doi:10.5194/acp-18-13457-2018.

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 Creators:
Crowley, John N.1, Author              
Pouvesle, Nicolas1, Author              
Phillips, Gavin J.1, Author              
Axinte, Raoul1, Author              
Fischer, Horst1, Author              
Petajä, Tuukka2, Author
Nölscher, Anke1, Author              
Williams, J.1, Author              
Hens, Korbinian1, Author              
Harder, Hartwig1, Author              
Martinez-Harder, Monica1, Author              
Novelli, Anna1, Author              
Kubistin, Dagmar1, Author              
Bohn, Birger2, Author
Lelieveld, Jos1, Author              
Affiliations:
1Atmospheric Chemistry, Max Planck Institute for Chemistry, Max Planck Society, ou_1826285              
2external, ou_persistent22              

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 Abstract: Unlike many oxidised atmospheric trace gases, which have numerous production pathways, peroxyacetic acid (PAA) and PAN are formed almost exclusively in gas-phase reactions involving the hydroperoxy radical (HO2), the acetyl peroxy radical (CH3C(O)O2) and NO2 and are not believed to be directly emitted in significant amounts by vegetation. As the self-reaction of HO2 is the main photochemical route to hydrogen peroxide (H2O2), simultaneous observation of PAA, PAN and H2O2 can provide insight into the HO2 budget. We present an analysis of observations taken during a summertime campaign in a boreal forest that, in addition to natural conditions, was temporarily impacted by two biomass-burning plumes. The observations were analysed using an expression based on a steady-state assumption using relative PAA-to-PAN mixing ratios to derive HO2 concentrations. The steady-state approach generated HO2 concentrations that were generally in reasonable agreement with measurements but sometimes overestimated those observed by factors of 2 or more. We also used a chemically simple, constrained box model to analyse the formation and reaction of radicals that define the observed mixing ratios of PAA and H2O2. After nudging the simulation towards observations by adding extra, photochemical sources of HO2 and CH3C(O)O2, the box model replicated the observations of PAA, H2O2, ROOH and OH throughout the campaign, including the biomass-burning-influenced episodes during which significantly higher levels of many oxidized trace gases were observed. A dominant fraction of CH3O2 radical generation was found to arise via reactions of the CH3C(O)O2 radical. The model indicates that organic peroxy radicals were present at night in high concentrations that sometimes exceeded those predicted for daytime, and initially divergent measured and modelled HO2 concentrations and daily concentration profiles are reconciled when organic peroxy radicals are detected (as HO2) at an efficiency of 35 %. Organic peroxy radicals are found to play an important role in the recycling of OH radicals subsequent to their loss via reactions with volatile organic compounds.

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Language(s): eng - English
 Dates: 2018
 Publication Status: Published in print
 Pages: -
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 Table of Contents: -
 Rev. Type: -
 Identifiers: ISI: 000445271300003
DOI: 10.5194/acp-18-13457-2018
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Title: Atmospheric Chemistry and Physics
  Abbreviation : ACP
Source Genre: Journal
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Publ. Info: Göttingen : Copernicus Publications
Pages: - Volume / Issue: 18 (18) Sequence Number: - Start / End Page: 13457 - 13479 Identifier: ISSN: 1680-7316
CoNE: https://pure.mpg.de/cone/journals/resource/111030403014016