Atmospheric Fate of Methyl Vinyl Ketone: Peroxy Radical Reactions with NO and HO_2
Abstract
First generation product yields from the OH-initiated oxidation of methyl vinyl ketone (3-buten-2-one, MVK) under both low and high NO conditions are reported. In the low NO chemistry, three distinct reaction channels are identified leading to the formation of (1) OH, glycolaldehyde, and acetyl peroxy R2a, (2) a hydroperoxide R2b, and (3) an α-diketone R2c. The α-diketone likely results from HO_x-neutral chemistry previously only known to occur in reactions of HO_2 with halogenated peroxy radicals. Quantum chemical calculations demonstrate that all channels are kinetically accessible at 298 K. In the high NO chemistry, glycolaldehyde is produced with a yield of 74 ± 6.0%. Two alkyl nitrates are formed with a combined yield of 4.0 ± 0.6%. We revise a three-dimensional chemical transport model to assess what impact these modifications in the MVK mechanism have on simulations of atmospheric oxidative chemistry. The calculated OH mixing ratio over the Amazon increases by 6%, suggesting that the low NO chemistry makes a non-negligible contribution toward sustaining the atmospheric radical pool.
Additional Information
© 2014 American Chemical Society. Received: October 24, 2014; Revised: December 8, 2014; Publication Date (Web): December 8, 2014. The authors thank NASA (NNX12AC06G) and NSF (AGS-1240604), the Danish Council for Independent Research-Natural Sciences, and the Danish Center for Scientific Computing (DCSC) for their support of this research. K.H.B. acknowledges support from an NSF Graduate Research Fellowship under Grant DGE-1144469. We thank Daniel Jacob and the Atmospheric Chemistry Modeling Group at Harvard University for making GEOS-Chem available for use in this study. The meteorological data used in the GEOS-Chem simulations have been provided by the Global Modeling and Assimilation Office (GMAO) at NASA Goddard Space Flight Center. Finally, we thank the reviewers for comments that improved this manuscript.Attached Files
Supplemental Material - jp5107058_si_001.pdf
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Additional details
- Eprint ID
- 53569
- DOI
- 10.1021/jp5107058
- Resolver ID
- CaltechAUTHORS:20150112-110218438
- NASA
- NNX12AC06G
- NSF
- AGS-1240604
- Danish Council for Independent Research-Natural Sciences
- Danish Center for Scientific Computing
- NSF Graduate Research Fellowship
- DGE-1144469
- Created
-
2015-01-12Created from EPrint's datestamp field
- Updated
-
2021-11-10Created from EPrint's last_modified field
- Caltech groups
- Division of Geological and Planetary Sciences