Diagnosis of Photochemical Ozone Production Rates and Limiting Factors based on Observation-based Modeling Approach over East Asia: Impact of Radical Chemistry Mechanism and Ozone-Control Implications

Abstract:

Growth of tropospheric ozone, causing health and climate impacts, is concerned over East Asia, because emissions of precursors have dramatically increased. Photochemical production rates of ozone and limiting factors, primarily studied for urban locations, have been poorly assessed within a perspective of regional-scale air pollution over East Asia. We performed comprehensive observations of ozone precursors at several locations with regional representativeness and made such assessment based on the observation-based modeling approach. Here, diagnosis at Fukue Island (32.75°N, 128.68°E) remotely located in western Japan (May 2009) is highlighted, where the highest 10% of hourly ozone concentrations reached 72‒118 ppb during May influenced by Asian continental outflow. The average in-situ ozone production rate was estimated to be 6.8 ppb per day, suggesting that in-travel production was still active, while larger buildup must have occurred beforehand. Information on the chemical status of the air mass arriving in Japan is important, because it affects how further ozone production occurs after precursor addition from Japanese domestic emissions. The main limiting factor of ozone production was usually NO_x, suggesting that domestic NO_x emission control is important in reducing further ozone production and the incidence of warning issuance (>120 ppb). VOCs also increased the ozone production rate, and occasionally (14% of time) became dominant. This analysis implies that the VOC reduction legislation recently enacted should be effective. The uncertainty in the radical chemistry mechanism governing ozone production had a non-negligible impact, but the main conclusion relevant to policy was not altered. When chain termination was augmented by HO₂-H₂O + NO/NO₂ reactions and by heterogeneous loss of HO₂ on aerosol particle surfaces, the daily ozone production rate decreased by <24%, and the fraction of hours when the VOC-limited condition occurred varied from 14% to 13‒26%.