Vertical ozone formation mechanisms resulting from increased oxidation on the mountainside of Mount Tai, China

The vertical distribution of ozone (O₃) within the boundary layer (BL) and its ground-level effects have been extensively studied. However, observational limitations in obtaining high-resolution, real-time data on O₃ and its precursors, especially volatile organic compounds (VOCs), have led to a scarcity of research on O₃ formation sensitivity and mechanisms. Online measurements for O₃, nitrogen oxides (NO <i>_x</i> ), and VOCs were made on the mountainside of Mount Tai (∼550 m a.s.l.) in China during the summer of 2022 and were compared with the data from a ground-level site. The Master Chemical Mechanism (V3.3.1) was used to uncover a positive correlation between NO <i>_x</i> and photochemical reaction rates on the mountainside, marking it as a NO <i>_x</i> -limited regime in contrast to the VOC-limited regime identified at surface. On the mountainside, lower NO levels limited hydroxyl radicals (OH) recycling reactions, resulting in earlier O₃ peaks and higher concentrations of hydroperoxy radicals (HO₂) and organic peroxy radicals (RO₂). The arrival of fresh air masses rich in NO accelerated OH radical cycling, enhanced atmospheric oxidization, and significantly impacted surface O₃ concentrations though vertical transport. Moreover, NO <i>_x</i> reduction scenario simulations show that when considering vertical transport, the peak O₃ production rate at the surface is lower due to differences in O₃ formation sensitivity vertically. This study highlights the significant sensitivity of O₃ formation to NO within the BL, underscoring the potential impact of vertical in situ O₃ formation above the ground on surface-level O₃ concentrations through vertical exchange, particularly in cities with mountainous terrain.