Interactions of peroxy radicals from monoterpene and isoprene oxidation simulated in the radical volatility basis set
Creators
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Schervish, Meredith
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Heinritzi, Martin
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Stolzenburg, Dominik
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Dada, Lubna
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Wang, Mingyi
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Ye, Qing
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Hofbauer, Victoria
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DeVivo, Jenna
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Bianchi, Federico
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Brilke, Sophia
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Duplissy, Jonathan
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El Haddad, Imad
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Finkenzeller, Henning
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He, Xu-Cheng
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Kvashnin, Aleksander
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Kim, Changhyuk
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Kirkby, Jasper
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Kulmala, Markku
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Lehtipalo, Katrianne
- Lopez, Brandon
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Makhmutov, Vladimir
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Mentler, Bernhard
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Molteni, Ugo
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Nie, Wei
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Petäjä, Tuuka
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Quéléver, Lauriane
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Volkamer, Rainer
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Wagner, Andrea C.
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Winkler, Paul
- Yan, Chao
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Donahue, Neil M.
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.
Copyright and License
This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence.
Acknowledgement
This work is dedicated to the memory of Astrid Kiendler-Scharr. It was supported by: Grant CHE2336463 from the U.S. National Science Foundation; the Vienna Science and Technology Fund (WWF) through project VRG22-003; Grant number PZ00P2_216181 from the Swiss National Science Foundation Ambizone Scheme; Grant number 200021_213071 from the Swiss National Foundation; and the European Research Council project NANODYNAMITE (ERC 616075).
Contributions
MS and NMD conceived the project and designed the overall scope. MS implemented and executed the radical VBS model. MS and NMD wrote the manuscript. FB, LD, SB, JD, IEH, HF, XCH, MH, AK, CK, JK, MK, KL, BL, VM, BM, UM, WN, TP, LQ, DS, RV, AW, MW, PW, CY and QY prepared the CLOUD facility and instruments and engaged in scientific discussion regarding the paper.
Data Availability
The data unique to this work are the rate coefficients and reaction sequence contained in the ESI.
Conflict of Interest
The authors declare no conflicts.
Files
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Additional details
Identifiers
- PMCID
- PMC11238171
Funding
- National Science Foundation
- CHE-2336463
- Vienna Science and Technology Fund
- VRG22-003
- Swiss National Science Foundation
- 200021_213071
- Swiss National Science Foundation
- PZ00P2_216181
- European Research Council
- 616075