Issue 7, 2024

Interactions of peroxy radicals from monoterpene and isoprene oxidation simulated in the radical volatility basis set

Abstract

Isoprene affects new particle formation rates in environments and experiments also containing monoterpenes. For the most part, isoprene reduces particle formation rates, but the reason is debated. It is proposed that due to its fast reaction with OH, isoprene may compete with larger monoterpenes for oxidants. However, by forming a large amount of peroxy-radicals (RO2), isoprene may also interfere with the formation of the nucleating species compared to a purely monoterpene system. We explore the RO2 cross reactions between monoterpene and isoprene oxidation products using the radical Volatility Basis Set (radical-VBS), a simplified reaction mechanism, comparing with observations from the CLOUD experiment at CERN. We find that isoprene interferes with covalently bound C20 dimers formed in the pure monoterpene system and consequently reduces the yields of the lowest volatility (Ultra Low Volatility Organic Carbon, ULVOC) VBS products. This in turn reduces nucleation rates, while having less of an effect on subsequent growth rates.

Graphical abstract: Interactions of peroxy radicals from monoterpene and isoprene oxidation simulated in the radical volatility basis set

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Article information

Article type
Paper
Submitted
02 May 2024
Accepted
19 Jun 2024
First published
24 Jun 2024
This article is Open Access
Creative Commons BY-NC license

Environ. Sci.: Atmos., 2024,4, 740-753

Interactions of peroxy radicals from monoterpene and isoprene oxidation simulated in the radical volatility basis set

M. Schervish, M. Heinritzi, D. Stolzenburg, L. Dada, M. Wang, Q. Ye, V. Hofbauer, J. DeVivo, F. Bianchi, S. Brilke, J. Duplissy, I. El Haddad, H. Finkenzeller, X. He, A. Kvashnin, C. Kim, J. Kirkby, M. Kulmala, K. Lehtipalo, B. Lopez, V. Makhmutov, B. Mentler, U. Molteni, W. Nie, T. Petäjä, L. Quéléver, R. Volkamer, A. C. Wagner, P. Winkler, C. Yan and N. M. Donahue, Environ. Sci.: Atmos., 2024, 4, 740 DOI: 10.1039/D4EA00056K

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