Articles | Volume 9, issue 11
Atmos. Chem. Phys., 9, 3697–3707, 2009

Special issue: MILAGRO/INTEX-B 2006

Atmos. Chem. Phys., 9, 3697–3707, 2009

  08 Jun 2009

08 Jun 2009

Inferring ozone production in an urban atmosphere using measurements of peroxynitric acid

K. M. Spencer1, D. C. McCabe2,*, J. D. Crounse1, J. R. Olson3, J. H. Crawford3, A. J. Weinheimer4, D. J. Knapp4, D. D. Montzka4, C. A. Cantrell4, R. S. Hornbrook4, R. L. Mauldin III4, and P. O. Wennberg2,5 K. M. Spencer et al.
  • 1Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA, USA
  • 2Division of Geological and Planetary Sciences, California Institute of Technology, Pasadena, CA, USA
  • 3NASA Langley Research Center, Hampton, VA, USA
  • 4National Center for Atmospheric Research, Boulder, CO, USA
  • 5Division 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

Abstract. Observations 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.

Special issue
Final-revised paper