Integrated diagnostic framework for resolving distinct ozone formation mechanisms via observations, modeling, and machine learning

Ozone (O₃) pollution in relatively high-latitude industrial cities shows spatiotemporal patterns associated with coupled meteorological, transport, and chemical processes, yet its dominant formation mechanisms remain unresolved. This study developed an interpretable diagnostic framework integrating process-resolved Weather Research and Forecasting model coupled with Chemistry (WRF-Chem) simulations, observations, and Extreme Gradient Boosting (XGBoost) interpreted using Shapley additive explanations (SHAP) for Changchun, Northeast China (September 2023-August 2024). Surface daily maximum 8-h average O₃ exceedances occurred from April to July, peaking above 200 μg/m³. Lidar monthly means at 0.3-1.0 km peaked from April to June (108.9-111.4 μg/m³), while the 1.0-2.0 and 2.0-3.0 km layers peaked in May (97.3 and 76.4 μg/m³), indicating that lower-layer intensity and vertical extent peaked asynchronously. Across five analysis windows (E1-E5), WRF-Chem diagnosed vertical mixing as the largest positive contribution in E1 and E3 (+19.6 and +12.2 µg/m³), concurrent positive contributions in E2 led by vertical mixing (+41.3 µg/m³) and chemistry (+21.1 µg/m³), and chemistry as the largest positive contribution in E5 (+21.8 µg/m³). In E4, upper-quartile O₃ coincided with predominantly negative contributions, particularly vertical advection (-24.0 µg/m³), showing that high concentrations and hourly O₃ changes were asynchronous. XGBoost-SHAP identified 2-m temperature (T ₂) and NO₂ as the leading nonlinear predictors: T ₂-related SHAP values became positive near 18.5 °C, whereas the NO₂-related values shifted from positive at 10-20 μg/m³ to predominantly negative above 26 μg/m³. The framework integrates vertical observations, statistical attribution, and modeled tendencies to support event-scale O₃ diagnosis.