Atmospheric Chemistry and Physics Discussions www.atmos-chem-phys-discuss.net 1680-7367 1680-7375 8 2 2008 10.5194/acpd-8-5359-2008 http://www.atmos-chem-phys-discuss.net/8/5359/2008/ http://www.atmos-chem-phys-discuss.net/8/5359/2008/acpd-8-5359-2008.html http://www.atmos-chem-phys-discuss.net/8/5359/2008/acpd-8-5359-2008.pdf 5359 5412 2008-03-17 Oxidative capacity of the Mexico City atmosphere – Part 2: A ROx radical cycling perspective P. M. Sheehy R. Volkamer L. T. Molina M. J. Molina Massachusetts Institute of Technology, Cambridge, MA, USA Molina Center for Energy and the Environment, La Jolla, CA, USA University of California at San Diego, La Jolla, CA, USA University of Colorado at Boulder and CIRES, Boulder, CO, USA A box model using measurements from the Mexico City Metropolitan Area study in the spring of 2003 (MCMA-2003) is presented to study ROx (ROx=OH+HO2+RO2+RO) radical cycling in the troposphere. Model simulations were performed with the Master Chemical Mechanism (MCMv3.1) constrained with 10 min averaged measurements of major radical sources (i.e., HCHO, HONO, O3, CHOCHO, etc.), radical sink precursors (i.e., NO, NO2, SO2, CO, and 102 volatile organic compounds VOC), meteorological parameters (temperature, pressure, water vapor concentration, dilution), and photolysis frequencies. Modeled HOx concentrations compare favorably with measured concentrations for most of the day; however, the model under-predicts the concentrations of radicals in the early morning. This "missing reactivity" is highest during peak photochemical activity, and is least visible in a direct comparison of HOx radical concentrations. The true uncertainty due to "missing reactivity" is apparent in parameters like chain length, and ozone production (P(O3)). For example, the integral amount of ozone produced could be under-predicted by a factor of two. 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