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Alkoxy Radical Bond Scissions Explain the Anomalously Low Secondary Organic Aerosol and Organonitrate Yields from α-Pinene + NO_3

Kurtén, Theo and Møller, Kristian H. and Nguyen, Tran Bao and Schwantes, Rebecca H. and Misztal, Pawel K. and Su, Luping and Wennberg, Paul O. and Fry, Juliane L. and Kjærgaard, Henrik Grum (2017) Alkoxy Radical Bond Scissions Explain the Anomalously Low Secondary Organic Aerosol and Organonitrate Yields from α-Pinene + NO_3. Journal of Physical Chemistry Letters, 2017 (8). pp. 2826-2834. ISSN 1948-7185. doi:10.1021/acs.jpclett.7b01038.

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Oxidation of monoterpenes (C_(10)H_(16)) by nitrate radicals (NO_3) constitutes an important source of atmospheric secondary organic aerosol (SOA) and organonitrates. However, knowledge of the mechanisms of their formation is incomplete and differences in yields between similar monoterpenes are poorly understood. In particular, yields of SOA and organonitrates from α-pinene + NO_3 are low, while those from Δ^3-carene + NO_3 are high. Using computational methods, we suggest that bond scission of the nitrooxy alkoxy radicals from Δ^3-carene lead to the formation of reactive keto-nitrooxy-alkyl radicals, which retain the nitrooxy moiety and can undergo further reactions to form SOA. In contrast, bond scissions of the nitrooxy alkoxy radicals from α-pinene lead almost exclusively to the formation of the relatively unreactive and volatile product pinonaldehyde (C_(10)H_(16)O_2), thereby limiting organonitrate and SOA formation. This hypothesis is supported by laboratory experiments that quantify products of the reaction of α-pinene + NO_3 under atmospherically relevant conditions.

Item Type:Article
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URLURL TypeDescription Information
Kurtén, Theo0000-0002-6416-4931
Møller, Kristian H.0000-0001-8070-8516
Schwantes, Rebecca H.0000-0002-7095-3718
Misztal, Pawel K.0000-0003-1060-1750
Wennberg, Paul O.0000-0002-6126-3854
Kjærgaard, Henrik Grum0000-0002-7275-8297
Additional Information:© 2017 American Chemical Society. This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes. Received: April 28, 2017; Accepted: June 6, 2017; Published: June 6, 2017. From the FIXCIT campaign, we thank Matthew Coggon and John Seinfeld for AMS data, Jeong-Hoo Park, Allen Goldstein, John Mak, and Alex Guenther for the PTR-MS data, John Crounse, Alex Teng and Kelvin Bates for the ToF-CIMS data and their work organizing and conducting the experiment. We also thank Alan Shusterman, Catherine Neshyba, Katie Stellmach, Rasmus V. Otkjær, Noora Hyttinen, Camilla Mia Tram, and Benjamin N. Frandsen for helpful discussions. TK thanks the Academy of Finland (266388) for funding and the CSC IT Center for Science in Espoo, Finland, for computing time. HGK and KHM thank the Center for Exploitation of Solar Energy, University of Copenhagen and the Danish Center for Scientific Computing for funding. POW thanks the NSF for funding (Grant No. CHE-1508526 and AGS-1240604). JLF gratefully acknowledges sabbatical support from the U.S. Fulbright Scholar Program and research funding from the NOAA Climate Program Office’s AC4 program (Grant No. NA13OAR4310070). The National Center for Atmospheric Research is sponsored by the National Science Foundation.
Funding AgencyGrant Number
Academy of Finland266388
University of CopenhagenUNSPECIFIED
Danish Center for Scientific ComputingUNSPECIFIED
Fulbright FoundationUNSPECIFIED
National Oceanic and Atmospheric Administration (NOAA)NA13OAR4310070
Issue or Number:8
Record Number:CaltechAUTHORS:20170608-112307794
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Official Citation:Alkoxy Radical Bond Scissions Explain the Anomalously Low Secondary Organic Aerosol and Organonitrate Yields From α-Pinene + NO3 Theo Kurtén, Kristian H. Møller, Tran B. Nguyen, Rebecca H. Schwantes, Pawel K. Misztal, Luping Su, Paul O. Wennberg, Juliane L. Fry, and Henrik G. Kjaergaard The Journal of Physical Chemistry Letters 2017 8 DOI: 10.1021/acs.jpclett.7b01038
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:78031
Deposited By: Tony Diaz
Deposited On:08 Jun 2017 21:15
Last Modified:15 Nov 2021 17:36

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