Closing the peroxy acetyl nitrate budget: observations of acyl peroxy nitrates (PAN, PPN, and MPAN) during BEARPEX 2007

dc.contributor.authorLaFranchi, B. W.
dc.contributor.authorWolfe, G. M.
dc.contributor.authorThornton, J. A.
dc.contributor.authorHarrold, S. A.
dc.contributor.authorBrowne, E.C.
dc.contributor.authorMin, K.E.
dc.contributor.authorWooldridge, P. J.
dc.contributor.authorGilman, J. B.
dc.contributor.authorKuster, W. C.
dc.contributor.authorGoldan, P. D.
dc.contributor.authorGouw, J. A. de
dc.contributor.authorMcKay, M.
dc.contributor.authorGoldstein, A. H.
dc.contributor.authorRen, X.
dc.contributor.authorMao, J.
dc.contributor.authorCohen, R. C.
dc.date.accessioned2020-09-15T18:11:35Z
dc.date.available2020-09-15T18:11:35Z
dc.date.issued2009-10-12
dc.description.abstractAcyl peroxy nitrates (APNs, also known as PANs) are formed from the oxidation of aldehydes and other oxygenated VOC (oVOC) in the presence of NO₂. There are both anthropogenic and biogenic oVOC precursors to APNs, but a detailed evaluation of this chemistry against observations has proven elusive. Here we describe measurements of PAN, PPN, and MPAN along with the majority of chemicals that participate in their production and loss, including OH, HO₂, numerous oVOC, and NO₂. Observations were made during the Biosphere Effects on AeRosols and Photochemistry Experiment (BEARPEX 2007) in the outflow of the Sacramento urban plume. These observations are used to evaluate a detailed chemical model of APN ratios and concentrations. We find that the ratios of APNs are nearly independent of the loss mechanisms and thus an especially good test of our understanding of their sources. We show that oxidation of methylvinyl ketone, methacrolein, methyl glyoxal, biacetyl and acetaldehyde are all significant sources of the PAN+peroxy acetyl (PA) radical reservoir, accounting for 26%, 2%, 7%, 20%, and 45%, of the production rate on average during the campaign, respectively. At high temperatures, when upwind isoprene emissions are highest, oxidation of non-acetaldehyde PA radical sources contributes over 60% to the total PA production rate, with methylvinyl ketone being the most important of the isoprene-derived sources. An analysis of absolute APN concentrations reveals a missing APN sink that can be resolved by increasing the PA+∑RO₂ rate constant by a factor of 3.en_US
dc.description.sponsorshipThe authors thank the UC Blodgett Forest Research Station staff for logistical support and Sierra Pacific Industries for access to their land. This work was supported by the National Science Foundation (grants ATM-0639847 (Berkeley) and ATM-0633897 (UW)). B. LaFranchi acknowledges support from the Camille and Henry Dreyfus Postdoctoral Program in Environmental Chemistry. G. Wolfe acknowledges support from NASA ESSF NNG-05GP64H.en_US
dc.description.urihttps://acp.copernicus.org/articles/9/7623/2009/en_US
dc.format.extent19 pagesen_US
dc.genrejournal articlesen_US
dc.identifierdoi:10.13016/m22mg7-zjic
dc.identifier.citationLaFranchi, B. W., Wolfe, G. M., Thornton, J. A., Harrold, S. A., Browne, E. C., Min, K. E., Wooldridge, P. J., Gilman, J. B., Kuster, W. C., Goldan, P. D., de Gouw, J. A., McKay, M., Goldstein, A. H., Ren, X., Mao, J., and Cohen, R. C.: Closing the peroxy acetyl nitrate budget: observations of acyl peroxy nitrates (PAN, PPN, and MPAN) during BEARPEX 2007, Atmos. Chem. Phys., 9, 7623–7641, https://doi.org/10.5194/acp-9-7623-2009, 2009.en_US
dc.identifier.urihttps://doi.org/10.5194/acp-9-7623-2009
dc.identifier.urihttp://hdl.handle.net/11603/19656
dc.language.isoen_USen_US
dc.publisherCopernicusen_US
dc.relation.isAvailableAtThe University of Maryland, Baltimore County (UMBC)
dc.relation.ispartofUMBC Joint Center for Earth Systems Technology
dc.relation.ispartofUMBC Physics Department
dc.rightsThis item is likely protected under Title 17 of the U.S. Copyright Law. Unless on a Creative Commons license, for uses protected by Copyright Law, contact the copyright holder or the author.
dc.rightsPublic Domain Mark 1.0*
dc.rightsThis work was written as part of one of the author's official duties as an Employee of the United States Government and is therefore a work of the United States Government. In accordance with 17 U.S.C. 105, no copyright protection is available for such works under U.S. Law.
dc.rights.urihttp://creativecommons.org/publicdomain/mark/1.0/*
dc.titleClosing the peroxy acetyl nitrate budget: observations of acyl peroxy nitrates (PAN, PPN, and MPAN) during BEARPEX 2007en_US
dc.typeTexten_US

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