References

ACP

Atmospheric Chemistry and Physics

ACP

1680-7324

Copernicus GmbH

Göttingen, Germany

10.5194/acp-11-10779-2011

Yields of oxidized volatile organic compounds during the OH radical initiated oxidation of isoprene, methyl vinyl ketone, and methacrolein under high-NOx conditions

Galloway

M. M.

¹ ⁴ Huisman

A. J.

¹ ⁵ Yee

L. D.

² Chan

A. W. H.

³ ⁶ Loza

C. L.

³ Seinfeld

J. H.

² ³ Keutsch

F. N.

Department of Chemistry, University of Wisconsin-Madison, Madison, WI, USA

Division of Engineering and Applied Science, California Institute of Technology, Pasadena, CA, USA

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

now at: Department of Chemistry, Reed College, Portland, OR, USA

now at: Institute for Atmosphere and Climate, ETH Zurich, Zurich, Switzerland

now at: Department of Environmental Science, Policy and Management, University of California, Berkeley, CA, USA

02 11 2011

11 21 10779 10790

This is an open-access article ditributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.

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We present first-generation and total production yields of glyoxal, methylglyoxal, glycolaldehyde, and hydroxyacetone from the oxidation of isoprene, methyl vinyl ketone (MVK), and methacrolein (MACR) with OH under high NOx conditions. Several of these first-generation yields are not included in commonly used chemical mechanisms, such as the Leeds Master Chemical Mechanism (MCM) v. 3.2. The first-generation yield of glyoxal from isoprene was determined to be 2.1 (±0.6)%. Inclusion of first-generation production of glyoxal, glycolaldehyde and hydroxyacetone from isoprene greatly improves performance of an MCM based model during the initial part of the experiments. In order to further improve performance of the MCM based model, higher generation glyoxal production was reduced by lowering the first-generation yield of glyoxal from C5 hydroxycarbonyls. The results suggest that glyoxal production from reaction of OH with isoprene under high NOx conditions can be approximated by inclusion of a first-generation production term together with secondary production only via glycolaldehyde. Analogously, methylglyoxal production can be approximated by a first-generation production term from isoprene, and secondary production via MVK, MACR and hydroxyacetone. The first-generation yields reported here correspond to less than 5% of the total oxidized yield from isoprene and thus only have a small effect on the fate of isoprene. However, due to the abundance of isoprene, the combination of first-generation yields and reduced higher generation production of glyoxal from C5 hydroxycarbonyls is important for models that include the production of the small organic molecules from isoprene.

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