1Department of Earth, Atmospheric and Planetary Sciences, Massachusetts Institute of Technology, MA, USA
2Molina Center for Energy and the Environment, CA, USA
3Saint Louis University, MO, USA
4Department of Chemistry and Biochemistry, University of California, San Diego, CA, USA
Abstract. An episodic simulation is conducted to characterize midday (12:00–17:00 CDT) ozone (O3) photochemical production and to investigate its sensitivity to emission changes of ozone precursors in the Mexico City Metropolitan Area (MCMA) during an "O3-South" meteorological episode using the Comprehensive Air Quality Model with extensions (CAMx). High Ox (O3+NO2) photochemical production rates of 10–80 ppb/h are predicted due to the high reactivity of volatile organic compounds (VOCs) in which alkanes, alkenes, and aromatics exert comparable contributions. The predicted ozone production efficiency is between 4–10 O3 molecules per NOx molecule oxidized, and increases with VOC-to-NO2 reactivity ratio. Process apportionment analyses indicate significant outflow of pollutants such as O3 and peroxyacetyl nitrate (PAN) from the urban area to the surrounding regional environment. PAN is not in chemical-thermal equilibrium during the photochemically active periods. Sensitivity studies of O3 production suggest that O3 formation in the MCMA urban region with less chemical aging (NOz/NOy<0.3) is VOC-limited. Both the simulated behavior of O3 production and its sensitivities to precursors suggest that midday O3 formation during this episode is VOC-sensitive in the urban region on the basis of the current emissions inventory estimates, and current NOx levels depress the O3 production.