1National Center for Atmospheric Research, Boulder, CO, USA
2Molina Center for Energy and the Environment, La Jolla, CA, USA
3Department of Atmospheric Sciences, Texas A&M, USA
4York University, Canada
Abstract. 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, NOx, and NOy 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-NOx, O3-CO, and O3-NOz 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 NOx 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.