Atmospheric Chemistry and Physics Discussions www.atmos-chem-phys-discuss.net 1680-7367 1680-7375 9 2 2009 10.5194/acpd-9-9221-2009 http://www.atmos-chem-phys-discuss.net/9/9221/2009/ http://www.atmos-chem-phys-discuss.net/9/9221/2009/acpd-9-9221-2009.html http://www.atmos-chem-phys-discuss.net/9/9221/2009/acpd-9-9221-2009.pdf 9221 9266 2009-04-08 Simulation of Mexico City plumes during the MIRAGE-Mex field campaign using the WRF-Chem model X. Tie xxtie@ucar.edu S. Madronich G. Li Z. Ying A. Weinheimer E. Apel T. Campos National Center for Atmospheric Research, Boulder, CO, USA Molina Center for Energy and the Environment, La Jolla, CA, USA Department of Atmospheric Sciences, Texas A&M, USA York University, Canada The quantification of tropospheric O₃ production in the Mexico City outflow is a major objective of the MIRAGE-Mex field campaign. We used a regional chemistry-transport model (WRF-Chem) to predict the distribution of O₃ and its precursors in Mexico City and the surrounding region during March 2006, and compared with in-situ aircraft measurement of O₃, CO, VOCs, NO_x, and NO_y concentrations. The comparison shows that the model is capable of capturing the timing/location of the measured city plumes, and the calculated variability along the flights is generally consistent with the measured results, showing a rapid enhancement of O₃ and its precursors when city plumes are detected. However, there are some notable differences between the calculated and measured values, suggesting that, during transport from the surface of the city to the outflow plume, pollution levels are underestimated by about 0–25% during different flights. The calculated O₃-NO_x, O₃-CO, and O₃-NO_z correlations generally agree with the measured values, and the analysis of these correlations suggest that photochemical O₃ production continues in the plume downwind of the city (aged plume), adding to the O₃ already produced in the city and exported with the plume. The model is also used to quantify the contributions to OH reactivity from various compounds in the aged plume. This analysis suggests that oxygenated organics (OVOCs) have the highest OH reactivity and play important roles for the O₃ production in the aging plume. Furthermore, O₃ production per NO_x molecule consumed (O₃ production efficiency) is more efficient in the aged plume than in the young plume near the city. The major contributor to the high O₃ production efficiency in the aged plume is the reaction RO₂+NO. By contrast, the reaction of HO₂+NO is rather uniformly distributed in the plume. 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