1Pennsylvania State University, University Park, PA, USA
2Autonomous Metropolitan University, Mexico City, Mexico
3Massachusetts Institute of Technology, Cambridge, MA, USA
4Washington State University, Pullman, WA, USA
5Pacific Northwest National Laboratory, Richland, WA, USA
Abstract. The Mexico City Metropolitan Area (MCMA) study in April 2003 had measurements of many atmospheric constituents, including OH and HO2. It provided the first opportunity to examine atmospheric oxidation in a megacity in a developing country that has more pollution than typical U.S. and European cities. At midday, OH typically reached 0.35 pptv (~7×106 cm−3), comparable to amounts observed in U.S. cities, but HO2 reached 40 pptv, more than observed in most U.S. cities. The OH reactivity was also measured, even during the highly polluted morning rush hour. MCMA's OH reactivity was 25 s−1 during most of the day and 120 s−1 at morning rush hour, which was several times greater than has been measured in any U.S. city. Median measured and modeled OH and HO2 agreed to within combined uncertainties, although for OH, the model exceeded the measurement by more than 30% during midday. OH production and loss, which were calculated from measurements, were in balance to within uncertainties, although production exceeded loss during morning rush hour. This imbalance has been observed in other cities. The HO2/OH ratio from measurements and steady-state analyses have essentially the same dependence on NO, except when NO was near 100 ppbv. This agreement is unlike other urban studies, in which HO2/OH ratio decreased much less than expected as NO increased. As a result of the active photochemistry in MCMA 2003, the median calculated ozone production from measured HO2 reached 50 ppb h−1, a much higher rate than observed in U.S. cities.