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Atmospheric Chemistry and Physics An interactive open-access journal of the European Geosciences Union
https://doi.org/10.5194/acp-2016-1126
© Author(s) 2016. This work is distributed under
the Creative Commons Attribution 3.0 License.
Research article
23 Dec 2016
Review status
This discussion paper is a preprint. A revision of the manuscript is under review for the journal Atmospheric Chemistry and Physics (ACP).
Formation of highly oxygenated organic molecules from aromatic compounds
Ugo Molteni1, Federico Bianchi1,2, Felix Klein1, Imad El Haddad1, Carla Frege1, Michel J. Rossi1, Josef Dommen1, and Urs Baltensperger1 1Laboratory of Atmospheric Chemistry, Paul Scherrer Institute, CH-5232 Villigen, Switzerland
2Department of Physics, University of Helsinki, 00014 Helsinki, Finland
Abstract. Anthropogenic volatile organic compounds (AVOC) often dominate the urban atmosphere and consist to a large degree of aromatic hydrocarbons (ArHC), such as benzene, toluene, xylenes, and trimethylbenzenes, e.g. from handling and combustion of fuels. These compounds are important precursors for the formation of secondary organic aerosol. Despite their recognized importance as atmospheric reactants, the formation of highly oxygenated molecules (HOMs) in the gas phase leading to (extremely) low volatility compounds has not been studied in the past. Here we show that oxidation of aromatics with OH leads to a subsequent autoxidation chain reaction forming HOMs with an O : C ratio of up to 1.09. This is exemplified for five single-ring ArHC (benzene, toluene, o-/m-/p-xylene, mesitylene (1,3,5-trimethylbenzene) and ethylbenzene), as well as two conjugated polycyclic ArHC (naphthalene and biphenyl). We present the identified compounds, differences in the observed oxidation patterns and discuss mechanistic pathways. We hypothesize that AVOC may contribute substantially to new particle formation events that have been detected in urban areas.

Citation: Molteni, U., Bianchi, F., Klein, F., El Haddad, I., Frege, C., Rossi, M. J., Dommen, J., and Baltensperger, U.: Formation of highly oxygenated organic molecules from aromatic compounds, Atmos. Chem. Phys. Discuss., https://doi.org/10.5194/acp-2016-1126, in review, 2016.
Ugo Molteni et al.
Ugo Molteni et al.
Ugo Molteni et al.

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Short summary
Anthropogenic volatile organic compounds often dominate the urban atmosphere and consist to a large degree of aromatics. These compounds are already known as important precursors for the formation of secondary organic aerosol. This study shows how the oxidation of aromatics with OH radical leads to subsequent autoxidation chain reactions forming highly oxygenated molecules. We hypothesize that these may contribute substantially to new particle formation events detected in urban areas.
Anthropogenic volatile organic compounds often dominate the urban atmosphere and consist to a...
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