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Inferring Ozone Production in an Urban Atmosphere using Measurements of Peroxynitric AcidObservations of peroxynitric acid (HO2NO2) obtained simultaneously with those of NO and NO2 provide a sensitive measure of the ozone photochemical production rate. We illustrate this technique for constraining the ozone production rate with observations obtained from the NCAR C-130 aircraft platform during the Megacity Initiative: Local and Global Research Observations (MILAGRO) intensive in Mexico during the spring of 2006. Sensitive and selective measurements of HO2NO2 were made in situ using chemical ionization mass spectrometry (CIMS). Observations were compared to modeled HO2NO2 concentrations obtained from the NASA Langley highly-constrained photochemical time-dependent box model. The median observed-to-calculated ratio of HO2NO2 is 1.18. At NOx levels greater than 15 ppbv, the photochemical box model underpredicts observations with an observed-to-calculated ratio of HO2NO2 of 1.57. As a result, we find that at high NOx, the ozone production rate calculated using measured HO2NO2 is faster than predicted using accepted photochemistry. Inclusion of an additional HOx source from the reaction of excited state NO2 with H2O or reduction in the rate constant of the reaction of OH with NO2 improves the agreement.
Document ID
20090014111
Acquisition Source
Goddard Space Flight Center
Document Type
Preprint (Draft being sent to journal)
Authors
Spencer, K. M.
(California Inst. of Tech. Pasadena, CA, United States)
McCabe, D. C.
(California Inst. of Tech. Pasadena, CA, United States)
Crounse, J. D.
(California Inst. of Tech. Pasadena, CA, United States)
Olson, J. R.
(NASA Langley Research Center Hampton, VA, United States)
Crawford, J. H.
(NASA Langley Research Center Hampton, VA, United States)
Weinheimer, A. J.
(National Center for Atmospheric Research Boulder, CO, United States)
Knapp, D. J.
(National Center for Atmospheric Research Boulder, CO, United States)
Montzka, D. D.
(National Center for Atmospheric Research Boulder, CO, United States)
Cantrell, C. A.
(National Center for Atmospheric Research Boulder, CO, United States)
Anderson, R. S.
(National Center for Atmospheric Research Boulder, CO, United States)
Mauldin, R. L.
(National Center for Atmospheric Research Boulder, CO, United States)
Wennberg, P. O.
(California Inst. of Tech. Pasadena, CA, United States)
Date Acquired
August 24, 2013
Publication Date
January 1, 2009
Subject Category
Environment Pollution
Funding Number(s)
CONTRACT_GRANT: NNG06GB32G
Distribution Limits
Public
Copyright
Other

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