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
, 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

Carnegie Mellon University
University of California at Irvine
Goethe University Frankfurt
Vienna University of Technology
University of Vienna
Paul Scherrer Institute
The University of Chicago
National Center for Atmospheric Research
University of Helsinki
Helsinki Institute of Physics
University of Colorado Boulder
University of Cambridge
Lebedev Fisysical Institute
Pusan National University
Division of Chemistry and Chemical Engineering
CERN
RAS - P.N. Lebedev Physics Institute
Moscow Institute of Physics and Technology
University of Innsbruck
Swiss Federal Institute for Forest, Snow and Landscape Research
Nanjing University
Tampere University

Research output: Contribution to journal › Article › peer-review

7 Scopus citations

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.

Original language	English
Pages (from-to)	740-753
Number of pages	14
Journal	Environmental Science: Atmospheres
Volume	4
Issue number	7
DOIs	https://doi.org/10.1039/d4ea00056k
State	Published - Jun 24 2024
Externally published	Yes

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Schervish, M., Heinritzi, M., Stolzenburg, D., Dada, L., Wang, M., Ye, Q., Hofbauer, V., DeVivo, J., Bianchi, F., Brilke, S., Duplissy, J., El Haddad, I., Finkenzeller, H., He, X. C., Kvashnin, A., Kim, C., Kirkby, J., Kulmala, M., Lehtipalo, K., ... Donahue, N. M. (2024). Interactions of peroxy radicals from monoterpene and isoprene oxidation simulated in the radical volatility basis set. Environmental Science: Atmospheres, 4(7), 740-753. https://doi.org/10.1039/d4ea00056k

@article{2fd392137cb04310ba6f753a384abd23,

title = "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.",

author = "Meredith Schervish and Martin Heinritzi and Dominik Stolzenburg and Lubna Dada and Mingyi Wang and Qing Ye and Victoria Hofbauer and Jenna DeVivo and Federico Bianchi and Sophia Brilke and Jonathan Duplissy and \{El Haddad\}, Imad and Henning Finkenzeller and He, \{Xu Cheng\} and Aleksander Kvashnin and Changhyuk Kim and Jasper Kirkby and Markku Kulmala and Katrianne Lehtipalo and Brandon Lopez and Vladimir Makhmutov and Bernhard Mentler and Ugo Molteni and Wei Nie and Tuuka Pet{\"a}j{\"a} and Lauriane Qu{\'e}l{\'e}ver and Rainer Volkamer and Wagner, \{Andrea C.\} and Paul Winkler and Chao Yan and Donahue, \{Neil M.\}",

note = "Publisher Copyright: {\textcopyright} 2024 RSC.",

year = "2024",

month = jun,

day = "24",

doi = "10.1039/d4ea00056k",

language = "English",

volume = "4",

pages = "740--753",

journal = "Environmental Science: Atmospheres",

issn = "2634-3606",

publisher = "Royal Society of Chemistry",

number = "7",

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Schervish, M, Heinritzi, M, Stolzenburg, D, Dada, L, Wang, M, Ye, Q, Hofbauer, V, DeVivo, J, Bianchi, F, Brilke, S, Duplissy, J, El Haddad, I, Finkenzeller, H, He, XC, Kvashnin, A, Kim, C, Kirkby, J, Kulmala, M, Lehtipalo, K, Lopez, B, Makhmutov, V, Mentler, B, Molteni, U, Nie, W, Petäjä, T, Quéléver, L, Volkamer, R, Wagner, AC, Winkler, P, Yan, C & Donahue, NM 2024, 'Interactions of peroxy radicals from monoterpene and isoprene oxidation simulated in the radical volatility basis set', Environmental Science: Atmospheres, vol. 4, no. 7, pp. 740-753. https://doi.org/10.1039/d4ea00056k

TY - JOUR

T1 - Interactions of peroxy radicals from monoterpene and isoprene oxidation simulated in the radical volatility basis set

AU - Schervish, Meredith

AU - Heinritzi, Martin

AU - Stolzenburg, Dominik

AU - Dada, Lubna

AU - Wang, Mingyi

AU - Ye, Qing

AU - Hofbauer, Victoria

AU - DeVivo, Jenna

AU - Bianchi, Federico

AU - Brilke, Sophia

AU - Duplissy, Jonathan

AU - El Haddad, Imad

AU - Finkenzeller, Henning

AU - He, Xu Cheng

AU - Kvashnin, Aleksander

AU - Kim, Changhyuk

AU - Kirkby, Jasper

AU - Kulmala, Markku

AU - Lehtipalo, Katrianne

AU - Lopez, Brandon

AU - Makhmutov, Vladimir

AU - Mentler, Bernhard

AU - Molteni, Ugo

AU - Nie, Wei

AU - Petäjä, Tuuka

AU - Quéléver, Lauriane

AU - Volkamer, Rainer

AU - Wagner, Andrea C.

AU - Winkler, Paul

AU - Yan, Chao

AU - Donahue, Neil M.

PY - 2024/6/24

Y1 - 2024/6/24

N2 - 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.

AB - 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.

UR - https://www.scopus.com/pages/publications/85196955458

U2 - 10.1039/d4ea00056k

DO - 10.1039/d4ea00056k

M3 - Article

AN - SCOPUS:85196955458

SN - 2634-3606

VL - 4

SP - 740

EP - 753

JO - Environmental Science: Atmospheres

JF - Environmental Science: Atmospheres

IS - 7

ER -

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

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