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

Meredith Schervish; Martin Heinritzi; Dominik Stolzenburg; Lubna Dada; Mingyi Wang; Qing Ye; Victoria Hofbauer; Jenna DeVivo; Federico Bianchi; Sophia Brilke; Jonathan Duplissy; Imad El Haddad; Henning Finkenzeller; Xu-Cheng He; Aleksander Kvashnin; Changhyuk Kim; Jasper Kirkby; Markku Kulmala; Katrianne Lehtipalo; Brandon Lopez; Vladimir Makhmutov; Bernhard Mentler; Ugo Molteni; Wei Nie; Tuuka Petäjä; Lauriane Quéléver; Rainer Volkamer; Andrea C. Wagner; Paul Winkler; Chao Yan; Neil M. Donahue

doi:10.1039/D4EA00056K

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

Meredith Schervish,

^ab Martin Heinritzi,

^c Dominik Stolzenburg,

^de Lubna Dada,

^f Mingyi Wang,

^ag Qing Ye,

^ah Victoria Hofbauer,^a Jenna DeVivo,

^a Federico Bianchi,

^ij Sophia Brilke,

^e Jonathan Duplissy,

^ij Imad El Haddad,

^f Henning Finkenzeller,

^k Xu-Cheng He,

^ijl Aleksander Kvashnin,^m Changhyuk Kim,

^no Jasper Kirkby,

^cp Markku Kulmala,

^ij Katrianne Lehtipalo,

^ij Brandon Lopez,^q Vladimir Makhmutov,^rs Bernhard Mentler,

^t Ugo Molteni,

^fu Wei Nie,

^ijv Tuuka Petäjä,

^ij Lauriane Quéléver,

^ij Rainer Volkamer,

^k Andrea C. Wagner,^cw Paul Winkler,

^e Chao Yan^ijv and Neil M. Donahue

*^aq

Author affiliations

* Corresponding authors

^a Carnegie Mellon University, Department of Chemistry, Pittsburgh, PA, USA
E-mail: nmd@andrew.cmu.edu
Tel: +1 412 268-4415

^b University of California, Irvine Department of Chemistry, Irvine, CA, USA

^c Institute for Atmospheric and Environmental Sciences, Goethe University Frankfurt, 60438 Frankfurt Am Main, Germany

^d Institute of Materials Chemistry, TU Wien, 1060 Vienna, Austria

^e Faculty of Physics, University of Vienna, 1090 Vienna, Austria

^f Laboratory of Atmospheric Chemistry, Paul Scherrer Institute, 5232 Villigen, Switzerland

^g University of Chicago, Department of the Geophysical Sciences, Chicago, IL, USA

^h Atmospheric Chemistry Observations and Modeling Laboratory, U.S. National Science Foundation National Center for Atmospheric Research (NSF NCAR), Boulder, Colorado 80301, USA

ⁱ Institute for Atmospheric and Earth System Research/Physics, University of Helsinki, Helsinki 00014, Finland

^j Helsinki Institute of Physics, University of Helsinki, 00014 Helsinki, Finland

^k Department of Chemistry, CIRES, University of Colorado Boulder, Boulder, CO 80309-0215, USA

^l Yusuf Hamied Department of Chemistry, University of Cambridge, Cambridge, UK

^m Lebedev Fisysical Institute, Leninsky Prospect 53, Moscow, Russia

ⁿ School of Civil and Environmental Engineering, Pusan National University, Busan, Republic of Korea

^o Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA 91125, USA

^p CERN, The European Organization for Nuclear Research, Geneve 23 CH-1211, Switzerland

^q Carnegie Mellon University Department of Chemical Engineering, Pittsburgh, PA, USA

^r Lebedev Physical Institute of the Russian Academy of Sciences, 119991 Moscow, Russia

^s Moscow Institute of Physics and Technology (National Research University), 141701 Moscow, Russia

^t Ion Molecule Reactions & Environmental Physics Group Institute of Ion Physics and Applied Physics Leopold-Franzens University, Innsbruck Technikerstraße 25, A-6020 Innsbruck, Austria

^u Swiss Federal Research Institute WSL, Plant Regeneration Ecology, Birmensdorf, Switzerland

^v Joint International Research Laboratory of Atmospheric and Earth System Research, School of Atmospheric Sciences, Nanjing University, Nanjing, China

^w Aerosol Physics Laboratory, Physics Unit, Tampere University, FI-33014 Tampere, Finland

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.

This article is part of the themed collection: Peroxy Radicals in the Atmosphere

Environmental Science: Atmospheres

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

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

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