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

oleh: J. Zhou, J. Zhou, C. Zhang, A. Liu, B. Yuan, B. Yuan, Y. Wang, Y. Wang, W. Wang, W. Wang, J.-P. Zhou, J.-P. Zhou, Y. Hao, Y. Hao, X.-B. Li, X.-B. Li, X. He, X. He, X. Song, X. Song, Y. Chen, Y. Chen, S. Yang, S. Yang, S. Yang, S. Yang, Y. Wu, Y. Wu, B. Jiang, B. Jiang, S. Huang, S. Huang, J. Liu, J. Liu, Y. Peng, Y. Peng, J. Qi, J. Qi, M. Deng, M. Deng, B. Zhong, B. Zhong, Y. Huangfu, Y. Huangfu, M. Shao, M. Shao

Format: Article
Diterbitkan: Copernicus Publications 2024-09-01

Deskripsi

<p><span id="page9806"/>Understanding the near-ground vertical and temporal photochemical O<span class="inline-formula"><sub>3</sub></span> formation mechanism is important to mitigate O<span class="inline-formula"><sub>3</sub></span> pollution. Here, we measured the vertical profiles of O<span class="inline-formula"><sub>3</sub></span> 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 (<span class="inline-formula"><i>P</i></span>(O<span class="inline-formula"><sub>3</sub></span>)<span class="inline-formula"><sub>net</sub></span>) and O<span class="inline-formula"><sub>3</sub></span> 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 O<span class="inline-formula"><sub>3</sub></span> pollution episodes, the <span class="inline-formula"><i>P</i></span>(O<span class="inline-formula"><sub>3</sub></span>)<span class="inline-formula"><sub>net</sub></span> was measured at 5 m above ground level with a custom-built detection system. In total, three O<span class="inline-formula"><sub>3</sub></span> pollution episodes and two non-episodes were captured. The identified O<span class="inline-formula"><sub>3</sub></span> 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 <span class="inline-formula"><i>P</i></span>(O<span class="inline-formula"><sub>3</sub></span>)<span class="inline-formula"><sub>net</sub></span> values indicated the rationality of investigating the vertical and temporal variability in O<span class="inline-formula"><sub>3</sub></span> formation mechanisms using model results. However, the measured <span class="inline-formula"><i>P</i></span>(O<span class="inline-formula"><sub>3</sub></span>)<span class="inline-formula"><sub>net</sub></span> values were generally higher than the modelled <span class="inline-formula"><i>P</i></span>(O<span class="inline-formula"><sub>3</sub></span>)<span class="inline-formula"><sub>net</sub></span> values, particularly under high-NO<span class="inline-formula"><sub><i>x</i></sub></span> conditions, which may indicate a potential underestimation of total RO<span class="inline-formula"><sub>2</sub></span> by the model. Throughout the measurement period, the contribution of different reaction pathways to O<span class="inline-formula"><sub>3</sub></span> production remained consistent across various heights, with HO<span class="inline-formula"><sub>2</sub></span> <span class="inline-formula">+</span> NO as the major O<span class="inline-formula"><sub>3</sub></span> production pathway, followed by RO<span class="inline-formula"><sub>2</sub></span> <span class="inline-formula">+</span> NO. We observed that <span class="inline-formula"><i>P</i></span>(O<span class="inline-formula"><sub>3</sub></span>)<span class="inline-formula"><sub>net</sub></span> decreased with an increase in measurement height, which was primarily attributed to the reduction in O<span class="inline-formula"><sub>3</sub></span> precursors, such as oxygenated volatile organic compounds (OVOCs) and non-methane hydrocarbons (NMHCs). The O<span class="inline-formula"><sub>3</sub></span> 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 O<span class="inline-formula"><sub>3</sub></span> 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 O<span class="inline-formula"><sub>3</sub></span> 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 O<span class="inline-formula"><sub>3</sub></span> 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 O<span class="inline-formula"><sub>3</sub></span> pollution in the PRD region of China.</p>