Rates and regimes of photochemical ozone production over Central East China in June 2006: a box model analysis using comprehensive measurements of ozone precursors

An observation-based box model approach was undertaken to estimate concentrations of OH, HO2, and RO2 radicals and the net photochemical production rate of ozone at the top of Mount Tai, located in the middle of Central East China, in June 2006. The model calculation was constrained by the measurements of O-3, H2O, CO, NO, NO2, hydrocarbon, HCHO, and CH3CHO concentrations, and temperature and J values. The net production rate of ozone was estimated to be 6.4 ppb h(-1) as a 6-h average (09: 00-15: 00 CST), suggesting 58 +/- 37 ppb of ozone is produced in one day. Thus the daytime buildup of ozone recorded at the mountain top as similar to 23 ppb on average is likely affected by in situ photochemistry as well as by the upward transport of polluted air mass in the daytime. On days with high ozone concentrations (hourly values exceeding 100 ppb at least once), in situ photochemistry was more active than it was on low ozone days, suggesting that in situ photochemistry is an important factor controlling ozone concentrations. Sensitivity model runs for which different NOx and hydrocarbon concentrations were assumed suggested that the ozone production occurred normally under NOx-limited conditions, with some exceptional periods (under volatile-organic-compound-limited conditions) in which there was fresh pollution. We also examined the possible influence of the heterogeneous loss of gaseous HO2 radicals in contact with aerosol particle surfaces on the rate and regimes of ozone production.