Observations and Explicit Modeling of Summer and Autumn Ozone Formation in Urban Beijing: Identification of Key Precursor Species and Sources

Due to the complexity and nonlinearity of the ozone (O3) production, it is vital to understand the detailed knowledge of ozone–precursor relationship for the formulation of effective mitigation of surface ozone pollution. In this study, continuous measurements of O3, volatile organic compounds (VOCs), and related parameters were conducted at an urban site of Beijing in the summer and autumn of 2019. The photochemical box model contained the Master Chemical Mechanism (MCMv3.3.1) was used to reveal the detailed information on the photochemical O3 formation. Results show that the average concentration of total VOCs (TVOC) was 31.2 ± 10.7 ppb and 37.8 ± 18.9 ppb during the summer and autumn campaign, respectively, with the largest contribution from alkanes in both seasons, which mainly originated from liquefied petroleum gas (LPG) usage (20.2%–22.6%), gasoline vehicular exhaust (21.0%–21.6%), diesel vehicular exhaust (18.1%–18.3%), solvent usage (20.4%–24.1%), and fuel evaporation (16.4%–17.4%) that identified by positive matrix factorization (PMF) model. Heavy ozone pollution episodes were observed and the net local O3 production rate during summer (EP1) and autumn (EP2) pollution episode was 9.87 ± 0.62 ppbv h−1, and 9.44 ± 1.18 ppbv h−1, respectively, which was both dominated by the reaction between HO2 with NO. The analysis of relative incremental reactivity (RIR) and O3-NOx-VOC isopleth shows that ozone formation was VOC-limited in urban Beijing, with alkenes and aromatics contributed the most to O3 formation in summer and autumn, respectively. In addition, modellings for various emission reduction scenarios were carried out, indicating the reduction of gasoline vehicles emissions in summer and both reduction of gasoline vehicles and solvent usage emissions in autumn is the best measures to efficiently reduce O3 pollution. These results improved our understanding of O3 precursors and their impact on ozone production and provided a more targeted reference for controlling ozone pollution in Beijing.