Preprints
https://doi.org/10.5194/acp-2022-85
https://doi.org/10.5194/acp-2022-85
 
04 Feb 2022
04 Feb 2022
Status: this preprint is currently under review for the journal ACP.

Identification of highly oxygenated organic molecules and their role in aerosol formation in the reaction of limonene with nitrate radical

Yindong Guo1, Hongru Shen1, Iida Pullinen2,a, Hao Luo1,3, Sungah Kang2, Luc Vereecken2, Hendrik Fuchs2, Mattias Hallquist4, Ismail-Hakki Acir2,b, Ralf Tillmann2, Franz Rohrer2, Jürgen Wildt2, Astrid Kiendler-Scharr2, Andreas Wahner2, Defeng Zhao1,5,6, and Thomas F. Mentel2 Yindong Guo et al.
  • 1Department of Atmospheric and Oceanic Sciences & Institute of Atmospheric Sciences, Fudan University, 200438, Shanghai, China
  • 2Institute of Energy and Climate Research, IEK-8: Troposphere, Forschungszentrum Jülich, 52425, Jülich, Germany
  • 3IRDR ICoE on Risk Interconnectivity and Governance on Weather/Climate Extremes Impact and Public Health, Fudan University, Shanghai 200438, China
  • 4Department of Chemistry and Molecular biology, University of Gothenburg, Göteborg, 41258, Sweden
  • 5Shanghai Frontiers Science Center of Atmosphere-Ocean Interaction, Fudan University, Shanghai 200438, China
  • 6Institute of Eco-Chongming (IEC), 20 Cuiniao Rd., Chongming, Shanghai, 202162, China
  • anow at: Department of Applied Physics, University of Eastern Finland, Kuopio, 70210, Finland
  • bnow at: Institute of Nutrition and Food Sciences, University of Bonn, Bonn, 53115, Germany

Abstract. Nighttime nitrate radical(NO3)-initiated oxidation of biogenic volatile organic compounds (BVOC) such as monoterpenes is important for the formation and growth of secondary organic aerosol (SOA), which has significant impact on climate, air quality and human health. In SOA formation and growth from the oxidation of monoterpenes by NO3, highly oxygenated organic molecules (HOM) may be crucial, but their formation pathways and role in aerosol formation have yet to be clarified. Among monoterpenes, limonene is of research interest for its high emission globally and high SOA yield. In this work, HOM formation in the reaction of limonene with nitrate radical was investigated in the SAPHIR chamber (Simulation of Atmospheric PHotochemistry In a large Reaction chamber). About 280 HOM products were identified, grouped into 6 monomer series (each including 3 families) and one family, 11 dimer families and 3 trimer families. Both closed-shell products and open-shell peroxy radicals (RO2•) were observed, and many of them have not been reported previously. Monomers and dimers accounted for over 90 % of HOM concentrations. In the most abundant monomer series – C10H15–17NO6–14, carbonyl products outnumbered hydroxyl products, indicating the importance of the unimolecular RO2• termination pathway. Both RO2• autoxidation and alkoxy-peroxy pathways were found to be important processes leading to HOM. Time-dependent concentration profiles of monomer products containing nitrogen showed mainly second-generation formation patterns. Dimers were likely formed via the accretion reaction of two monomer RO2•, and HOM-trimers via the accretion reaction between monomer RO2• and dimer RO2•. Trimers are suggested to play an important role in new particle formation (NPF) observed in our experiment. A HOM yield of 1.5 % (+1.7 %/−0.7 %) was estimated considering only first-generation products. SOA mass growth could be reasonably explained by HOM condensation on particles assuming irreversible uptake of extremely low volatility organic compounds (ELVOC) and low volatility organic compounds (LVOC). This work provides evidence for the important role of HOM formed via the limonene + NO3 reaction in NPF and SOA growth.

Yindong Guo 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-2022-85', Anonymous Referee #1, 03 Mar 2022
  • RC2: 'Comment on acp-2022-85', Anonymous Referee #2, 03 May 2022

Yindong Guo et al.

Yindong Guo et al.

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Short summary
The oxidation of limonene, a common volatile emitted by trees and by chemical products, by NO3, an nighttime oxidant, forms many highly oxygenated organic molecules (HOM), including C10–30 compounds. Many HOM are second-generation organic nitrates, in which carbonyl-substituted C10 nitrates accounted a major fraction. Their formation can be explained the chemistry of peroxy radicals. HOM, especially low-volatile ones, play an important role in nighttime new particle formation and growth.
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