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Atmospheric Chemistry and Physics An interactive open-access journal of the European Geosciences Union
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© Author(s) 2020. This work is distributed under
the Creative Commons Attribution 4.0 License.
© Author(s) 2020. This work is distributed under
the Creative Commons Attribution 4.0 License.

Submitted as: research article 25 Mar 2020

Submitted as: research article | 25 Mar 2020

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This preprint is currently under review for the journal ACP.

Evaluation of the Chemical Composition of Gas and Particle Phase Products of Aromatic Oxidation

Archit Mehra1, Yuwei Wang2, Jordan E. Krechmer3, Andrew Lambe3, Francesca Majluf3, Melissa A. Morris3,b, Michael Priestley1,a, Thomas J. Bannan1, Daniel J. Bryant4, Kelly L. Pereira4, Jacqueline F. Hamilton4, Andrew R. Rickard4,5, Mike J. Newland4, Harald Stark3, Philip Croteau3, John T. Jayne3, Douglas R. Worsnop3, Manjula R. Canagaratna3, Lin Wang2, and Hugh Coe2,1 Archit Mehra et al.
  • 1Centre for Atmospheric Science, School of Earth and Environmental Sciences, The University of Manchester, Manchester, M13 9PL, UK
  • 2Shanghai Key Laboratory of Atmospheric Particle Pollution and Prevention (LAP3), Department of Environmental Science & Engineering, Jiangwan Campus, Fudan University, Shanghai 200438, China
  • 3Center for Aerosol and Cloud Chemistry, Aerodyne Research Inc, Billerica, Massachusetts, USA
  • 4Wolfson Atmospheric Chemistry Laboratories, Department of Chemistry, The University of York, York, UK
  • 5National Centre for Atmospheric Science (NCAS), University of York, York, UK
  • anow at: Department of Chemistry and Molecular Biology, University of Gothenburg, Gothenburg, Sweden
  • bDepartment of Chemistry and Cooperative Institute for Research in Environmental Sciences (CIRES), University of Colorado Boulder, Boulder, CO, USA

Abstract. Aromatic volatile organic compounds (VOC) are key anthropogenic pollutants emitted to the atmosphere and are important for both ozone and secondary organic aerosol (SOA) formation in urban areas. Recent studies have indicated that aromatic hydrocarbons may follow previously unknown oxidation chemistry pathways, including autoxidation that can lead to the formation of highly oxidised products. In this study we evaluate the gas and particle phase ions formed during the hydroxyl radical oxidation of substituted C9-aromatic isomers (1,3,5-trimethyl benzene, 1,2,4-trimethyl benzene, propyl benzene and isopropyl benzene) and a substituted polyaromatic hydrocarbon (1-methyl naphthalene) under low and medium NOx conditions.

The majority of product signal in both gas and particle phases comes from ions which are common to all precursors, though signal distributions are distinct for different VOCs. Gas and particle phase composition are distinct from one another, and comparison with the near explicit gas phase Master Chemical Mechanism (MCMv3.3.1) highlights a range of missing highly oxidised products in the pathways.

In the particle phase, the bulk of product signal from all precursors comes from ring scission ions, many of which have undergone further oxidation to form HOMs. Under perturbation of OH oxidation with increased NOx, the contribution of HOM ion signals to the particle phase signal remains elevated for more substituted aromatic precursors. Up to 25 % of product signal comes from ring-retaining ions including highly oxygenated organic molecules (HOMs); this is most important for the more substituted aromatics. Unique products are a minor component in these systems, and many of the dominant ions have ion formulae concurrent with other systems, highlighting the challenges in utilising marker ions for SOA.

Archit Mehra et al.

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Archit Mehra et al.

Archit Mehra et al.


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Publications Copernicus
Short summary
Aromatic volatile organic compounds (VOCs) emitted from anthropogenic activity are important for tropospheric ozone and secondary organic aerosol (SOA) formation. Here we present a detailed chemical characterisation of the SOA from four C9-aromatic isomers and a polycyclic aromatic hydrocarbon (PAH). We identify and compare their oxidation products in the gas and particle phases, showing different relative importance of oxidation pathways and proportions of highly oxygenated organic molecules.
Aromatic volatile organic compounds (VOCs) emitted from anthropogenic activity are important for...