Measurement report: Vertical and temporal variability in the near-surface ozone production rate and sensitivity in an urban area in the Pearl River Delta region, China

Abstract. Understanding the near-ground vertical and temporal photochemical O3 formation mechanism is important to mitigate O3 pollution. Here, we measured the vertical profiles of O3 and its precursors at six different heights, ranging from 5 to 335 m, using a newly built vertical observation system in the Pearl River Delta (PRD) region of China. The net photochemical ozone production rate (P(O3)net) and O3 formation sensitivities at various heights were diagnosed using an observation-based model coupled with the Master Chemical Mechanism (MCM v3.3.1). Moreover, to assess model performance and identify the causative factors behind O3 pollution episodes, the P(O3)net was measured at 5 m above ground level with a custom-built detection system. In total, three O3 pollution episodes and two non-episodes were captured. The identified O3 pollution episodes were found to be jointly influenced by both photochemical production and physical transport, with local photochemical reactions playing a major role. The high index of agreement (IOA) calculated by comparing the modelled and measured P(O3)net values indicated the rationality of investigating the vertical and temporal variability in O3 formation mechanisms using model results. However, the measured P(O3)net values were generally higher than the modelled P(O3)net values, particularly under high-NOx conditions, which may indicate a potential underestimation of total RO2 by the model. Throughout the measurement period, the contribution of different reaction pathways to O3 production remained consistent across various heights, with HO2 + NO as the major O3 production pathway, followed by RO2 + NO. We observed that P(O3)net decreased with an increase in measurement height, which was primarily attributed to the reduction in O3 precursors, such as oxygenated volatile organic compounds (OVOCs) and non-methane hydrocarbons (NMHCs). The O3 formation regimes were similar at different heights during both episodes and non-episodes, either being located in the VOC-sensitive regime or in the transition regime that is more sensitive to VOCs. Diurnally, photochemical O3 formation typically remained in the VOC-sensitive regime during the morning and noon, but it transitioned to the transition regime and was more sensitive to VOCs in the afternoon at around 16:00 LT (local time). Vertical and temporal photochemical O3 formation is most sensitive to OVOCs, suggesting that targeting specific VOCs for control measures is more practical and feasible at the observation site. The vertical temporal analysis of O3 formation mechanisms near the ground surface in this study provides critical foundational knowledge that can be used to formulate effective short-term emergency and long-term control strategies to combat O3 pollution in the PRD region of China.