Closing the peroxy acetyl (PA) radical budget: Observations of acyl peroxy nitrates (PAN, PPN and MPAN) during BEARPEX 2009. LaFranchi, 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., deGouw, J., a., McKay, M., Goldstein, a., H., Ren, X., R., Mao, J., Q., Cohen, R., C., de Gouw, J., a., Welsh-Bon, D., Chen, Z., & Brune, W., H. Abstracts of Papers of the American Chemical Society, 9(19):289, 10, 2009.
Closing the peroxy acetyl (PA) radical budget: Observations of acyl peroxy nitrates (PAN, PPN and MPAN) during BEARPEX 2009 [pdf]Paper  Closing the peroxy acetyl (PA) radical budget: Observations of acyl peroxy nitrates (PAN, PPN and MPAN) during BEARPEX 2009 [link]Website  abstract   bibtex   
Acyl peroxy nitrates (APNs, also known as PANs) are formed from the\noxidation of aldehydes and other oxygenated VOC (oVOC) in the presence\nof NO(2). There are both anthropogenic and biogenic oVOC precursors to\nAPNs, but a detailed evaluation of this chemistry against observations\nhas proven elusive. Here we describe measurements of PAN, PPN, and MPAN\nalong with the majority of chemicals that participate in their\nproduction and loss, including OH, HO(2), numerous oVOC, and NO(2).\nObservations were made during the Biosphere Effects on AeRosols and\nPhotochemistry Experiment (BEARPEX 2007) in the outflow of the\nSacramento urban plume. These observations are used to evaluate a\ndetailed chemical model of APN ratios and concentrations. We find that\nthe ratios of APNs are nearly independent of the loss mechanisms and\nthus an especially good test of our understanding of their sources. We\nshow that oxidation of methylvinyl ketone, methacrolein, methyl glyoxal,\nbiacetyl and acetaldehyde are all significant sources of the PAN+peroxy\nacetyl (PA) radical reservoir, accounting for 26%, 2%, 7%, 20%, and\n45%, of the production rate on average during the campaign,\nrespectively. At high temperatures, when upwind isoprene emissions are\nhighest, oxidation of non-acetaldehyde PA radical sources contributes\nover 60% to the total PA production rate, with methylvinyl ketone being\nthe most important of the isoprene-derived sources. An analysis of\nabsolute APN concentrations reveals a missing APN sink that can be\nresolved by increasing the PA+Sigma RO(2) rate constant by a factor of\n3.
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