Alkoxy Radical Bond Scissions Explain the Anomalously Low Secondary Organic Aerosol and Organonitrate Yields From α-Pinene + NO3

Kurtén, Theo; Møller, Kristian H.; Nguyen, Tran B.; Schwantes, Rebecca H.; Misztal, Pawel K.; Su, Luping; Wennberg, Paul O.; Fry, Juliane L.; Kjaergaard, Henrik G.

doi:10.1021/acs.jpclett.7b01038

i

Alkoxy Radical Bond Scissions Explain the Anomalously Low Secondary Organic Aerosol and Organonitrate Yields From α-Pinene + NO3

2017
By Kurtén, Theo ; Møller, Kristian H. ; Nguyen, Tran B. ; ...

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Journal Title:

The Journal of Physical Chemistry Letters
Personal Author:

Kurtén, Theo ; Møller, Kristian H. ; Nguyen, Tran B. ; Schwantes, Rebecca H. ; Misztal, Pawel K. ; Su, Luping ; Wennberg, Paul O. ; Fry, Juliane L. ; Kjaergaard, Henrik G.
NOAA Program & Office:

OAR (Oceanic and Atmospheric Research)
Description:

Oxidation of monoterpenes (C10H16) by nitrate radicals (NO3) 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 + NO3 are low, while those from Δ3-carene + NO3 are high. Using computational methods, we suggest that bond scission of the nitrooxy alkoxy radicals from Δ3-carene lead to the formation of reactive keto-nitrooxy-alkyl radicals, which retain the nitrooxy moiety and can undergo further reactions to form SOA. By 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 (C10H16O2), thereby limiting organonitrate and SOA formation. This hypothesis is supported by laboratory experiments that quantify products of the reaction of α-pinene + NO3 under atmospherically relevant conditions.
Keywords:

General Materials Science Physical And Theoretical Chemistry Physical And Theoretical Chemistry Physical And Theoretical Chemistry
Source:

The Journal of Physical Chemistry Letters, 8(13), 2826-2834
DOI:

https://doi.org/10.1021/acs.jpclett.7b01038
ISSN:

1948-7185 ; 1948-7185
Format:

PDF
Publisher:

American Chemical Society (ACS)
Document Type:

Journal Article
Funding:

Grant no. NA13OAR4310070
Rights Information:

Other
Compliance:

Library
Main Document Checksum:

urn:sha256:d9395a3e34f9a6546df2c4825a839990b4ceff62929ad710a25f95333c38a0a4
Download URL:

https://repository.library.noaa.gov/view/noaa/60552/noaa_60552_DS1.pdf
File Type:

[PDF - 1.28 MB ]

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