ACP Atmospheric Chemistry and Physics ACP 1680-7324 Copernicus GmbH Göttingen, Germany 10.5194/acp-9-3697-2009 Inferring ozone production in an urban atmosphere using measurements of peroxynitric acid Spencer K. M. 1 McCabe D. C. 2 6 Crounse J. D. 1 Olson J. R. 3 Crawford J. H. 3 Weinheimer A. J. 4 Knapp D. J. 4 Montzka D. D. 4 Cantrell C. A. 4 Hornbrook R. S. 4 Mauldin III R. L. 4 Wennberg P. O. 2 5 Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA, USA Division of Geological and Planetary Sciences, California Institute of Technology, Pasadena, CA, USA NASA Langley Research Center, Hampton, VA, USA National Center for Atmospheric Research, Boulder, CO, USA Division of Engineering and Applied Science, California Institute of Technology, Pasadena, CA, USA current address: AAAS Science & Technology Policy Fellow, United States Environmental Protection Agency, Washington, DC, USA 08 06 2009 9 11 3697 3707 This is an open-access article ditributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited. This article is available from http://www.atmos-chem-phys.net/9/3697/2009/acp-9-3697-2009.html The full text article is available as a PDF file from http://www.atmos-chem-phys.net/9/3697/2009/acp-9-3697-2009.pdf

Observations of peroxynitric acid (HO<sub>2</sub>NO<sub>2</sub>) obtained simultaneously with those of NO and NO<sub>2</sub> 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 HO<sub>2</sub>NO<sub>2</sub> were made in situ using chemical ionization mass spectrometry (CIMS). Observations were compared to modeled HO<sub>2</sub>NO<sub>2</sub> concentrations obtained from the NASA Langley highly-constrained photochemical time-dependent box model. The median observed-to-calculated ratio of HO<sub>2</sub>NO<sub>2</sub> is 1.18. At NO<sub>x</sub> levels greater than 15 ppbv, the photochemical box model underpredicts observations with an observed-to-calculated ratio of HO<sub>2</sub>NO<sub>2</sub> of 1.57. As a result, we find that at high NO<sub>x</sub>, the ozone production rate calculated using measured HO<sub>2</sub>NO<sub>2</sub> is faster than predicted using accepted photochemistry. Inclusion of an additional HO<sub>x</sub> source from the reaction of excited state NO<sub>2</sub> with H<sub>2</sub>O or reduction in the rate constant of the reaction of OH with NO<sub>2</sub> improves the agreement.

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