Identification of close relationship between atmospheric oxidation and ozone formation regimes in a photochemically active region

Understanding ozone (O₃) formation regime is a prerequisite in formulating an effective O₃ pollution control strategy. Photochemical indicator is a simple and direct method in identifying O₃ formation regimes. Most used indicators are derived from observations, whereas the role of atmospheric oxidation is not in consideration, which is the core driver of O₃ formation. Thus, it may impact accuracy in signaling O₃ formation regimes. In this study, an advanced three-dimensional numerical modeling system was used to investigate the relationship between atmospheric oxidation and O₃ formation regimes during a long-lasting O₃ exceedance event in September 2017 over the Pearl River Delta (PRD) of China. We discovered a clear relationship between atmospheric oxidative capacity and O₃ formation regime. Over eastern PRD, O₃ formation was mainly in a NO_x-limited regime when HO₂/OH ratio was higher than 11, while in a VOC-limited regime when the ratio was lower than 9.5. Over central and western PRD, an HO₂/OH ratio higher than 5 and lower than 2 was indicative of NO_x-limited and VOC-limited regime, respectively. Physical contribution, including horizontal transport and vertical transport, may pose uncertainties on the indication of O₃ formation regime by HO₂/OH ratio. In comparison with other commonly used photochemical indicators, HO₂/OH ratio had the best performance in differentiating O₃ formation regimes. This study highlighted the necessities in using an atmospheric oxidative capacity-based indicator to infer O₃ formation regime, and underscored the importance of characterizing behaviors of radicals to gain insight in atmospheric processes leading to O₃ pollution over a photochemically active region.