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Published December 16, 2014 | Supplemental Material + Published
Journal Article Open

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


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.

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.

Attached Files

Published - Rivera_Rios_et_al-2014-Geophysical_Research_Letters.pdf

Supplemental Material - grl52356-sup-0001-documentS1.docx


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