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Conversion of hydroperoxides to carbonyls in field and laboratory instrumentation: Observational bias in diagnosing pristine versus anthropogenically controlled atmospheric chemistry

Rivera-Rios, J. C. and Nguyen, T. B. and Crounse, J. D. and Jud, W. and St. Clair, J. M. and Mikoviny, T. and Gilman, J. B. and Lerner, B. M. and Kaiser, J. B. and de Gouw, J. and Wisthaler, A. and Hansel, A. and Wennberg, P. O. and Seinfeld, J. H. and Keutsch, F. N. (2014) Conversion of hydroperoxides to carbonyls in field and laboratory instrumentation: Observational bias in diagnosing pristine versus anthropogenically controlled atmospheric chemistry. Geophysical Research Letters, 41 (23). pp. 8645-8651. ISSN 0094-8276. http://resolver.caltech.edu/CaltechAUTHORS:20150220-091742441

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Abstract

Atmospheric volatile organic compound (VOC) oxidation mechanisms under pristine (rural/remote) and urban (anthropogenically-influenced) conditions follow distinct pathways due to large differences in nitrogen oxide (NO_x) concentrations. These two pathways lead to products that have different chemical and physical properties and reactivity. Under pristine conditions, isoprene hydroxy hydroperoxides (ISOPOOHs) are the dominant first-generation isoprene oxidation products. Utilizing authentic ISOPOOH standards, we demonstrate that two of the most commonly used methods of measuring VOC oxidation products (i.e., gas chromatography and proton transfer reaction mass spectrometry) observe these hydroperoxides as their equivalent high-NO isoprene oxidation products – methyl vinyl ketone (MVK) and methacrolein (MACR). This interference has led to an observational bias affecting our understanding of global atmospheric processes. Considering these artifacts will help close the gap on discrepancies regarding the identity and fate of reactive organic carbon, revise our understanding of surface-atmosphere exchange of reactive carbon and SOA formation, and improve our understanding of atmospheric oxidative capacity.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1002/2014GL061919DOIArticle
http://onlinelibrary.wiley.com/doi/10.1002/2014GL061919/abstractPublisherArticle
http://onlinelibrary.wiley.com/doi/10.1002/2014GL061919/suppinfoRelated ItemSupporting Information
ORCID:
AuthorORCID
Crounse, J. D.0000-0001-5443-729X
Wennberg, P. O.0000-0002-6126-3854
Seinfeld, J. H.0000-0003-1344-4068
Additional Information:© 2014 American Geophysical Union. Received 18 Sep 2014. Accepted 12 Nov 2014. Accepted article online 17 Nov 2014. Published online 8 Dec 2014. J.C.R., J.B.K., and F.N.K. thank NSF-AGS (1247421) for the support. J.B.K. also acknowledges support from the National Science Foundation Graduate Research Fellowship Program under grant DGE-1256259. J.D.C., T.B.N., J.S., and P.O.W. thank NSF grant AGS-1240604 for the support. T.B.N. also acknowledges support from the National Science Foundation Fellowship grant AGS-1331360. This work was financially supported by the Austrian Science Fund (FWF) under the project I655-B16. A.W. and T.M. acknowledge support through the Austrian Space Applications Program of the Austrian Federal Ministry for Transport, Innovation, and Technology (bmvit) and through the Visiting Scientist Program at the National Institute of Aerospace. Compound characterization, additional figures, and experimental details are available online as supporting information. The Editor thanks two anonymous reviewers for their assistance in evaluating this paper.
Funders:
Funding AgencyGrant Number
NSFAGS-1247421
NSF Graduate Research FellowshipDGE-1256259
NSFAGS-1240604
NSFAGS-1331360
Austrian Science Fund (FWF)I655-B16
Austrian Space Applications Program of the Austrian Federal Ministry for Transport, Innovation, and TechnologyUNSPECIFIED
National Institute of Aerospace Visiting Scientist ProgramUNSPECIFIED
Subject Keywords:Isoprene-oxidation; hydroperoxides; anthropogenic influence; secondary pollutant formation; interference
Record Number:CaltechAUTHORS:20150220-091742441
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20150220-091742441
Official Citation:Rivera-Rios, J. C., et al. (2014), Conversion of hydroperoxides to carbonyls in field and laboratory instrumentation: Observational bias in diagnosing pristine versus anthropogenically controlled atmospheric chemistry, Geophys. Res. Lett., 41, 8645–8651, doi:10.1002/2014GL061919.
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:55043
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:20 Feb 2015 18:03
Last Modified:06 Apr 2017 20:42

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