Wanqi Wu, Yanzhen Ge, Yan Wang, Jixin Su, Xinfeng Wang, Bin Zhou, Jianmin Chen
{"title":"中国泰山山腰氧化作用增强导致的垂直臭氧形成机制。","authors":"Wanqi Wu, Yanzhen Ge, Yan Wang, Jixin Su, Xinfeng Wang, Bin Zhou, Jianmin Chen","doi":"10.1093/pnasnexus/pgae347","DOIUrl":null,"url":null,"abstract":"<p><p>The vertical distribution of ozone (O<sub>3</sub>) 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 O<sub>3</sub> and its precursors, especially volatile organic compounds (VOCs), have led to a scarcity of research on O<sub>3</sub> formation sensitivity and mechanisms. Online measurements for O<sub>3</sub>, nitrogen oxides (NO <i><sub>x</sub></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><sub>x</sub></i> and photochemical reaction rates on the mountainside, marking it as a NO <i><sub>x</sub></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 O<sub>3</sub> peaks and higher concentrations of hydroperoxy radicals (HO<sub>2</sub>) and organic peroxy radicals (RO<sub>2</sub>). The arrival of fresh air masses rich in NO accelerated OH radical cycling, enhanced atmospheric oxidization, and significantly impacted surface O<sub>3</sub> concentrations though vertical transport. Moreover, NO <i><sub>x</sub></i> reduction scenario simulations show that when considering vertical transport, the peak O<sub>3</sub> production rate at the surface is lower due to differences in O<sub>3</sub> formation sensitivity vertically. This study highlights the significant sensitivity of O<sub>3</sub> formation to NO within the BL, underscoring the potential impact of vertical in situ O<sub>3</sub> formation above the ground on surface-level O<sub>3</sub> concentrations through vertical exchange, particularly in cities with mountainous terrain.</p>","PeriodicalId":74468,"journal":{"name":"PNAS nexus","volume":null,"pages":null},"PeriodicalIF":2.2000,"publicationDate":"2024-08-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11376371/pdf/","citationCount":"0","resultStr":"{\"title\":\"Vertical ozone formation mechanisms resulting from increased oxidation on the mountainside of Mount Tai, China.\",\"authors\":\"Wanqi Wu, Yanzhen Ge, Yan Wang, Jixin Su, Xinfeng Wang, Bin Zhou, Jianmin Chen\",\"doi\":\"10.1093/pnasnexus/pgae347\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><p>The vertical distribution of ozone (O<sub>3</sub>) 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 O<sub>3</sub> and its precursors, especially volatile organic compounds (VOCs), have led to a scarcity of research on O<sub>3</sub> formation sensitivity and mechanisms. Online measurements for O<sub>3</sub>, nitrogen oxides (NO <i><sub>x</sub></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><sub>x</sub></i> and photochemical reaction rates on the mountainside, marking it as a NO <i><sub>x</sub></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 O<sub>3</sub> peaks and higher concentrations of hydroperoxy radicals (HO<sub>2</sub>) and organic peroxy radicals (RO<sub>2</sub>). The arrival of fresh air masses rich in NO accelerated OH radical cycling, enhanced atmospheric oxidization, and significantly impacted surface O<sub>3</sub> concentrations though vertical transport. Moreover, NO <i><sub>x</sub></i> reduction scenario simulations show that when considering vertical transport, the peak O<sub>3</sub> production rate at the surface is lower due to differences in O<sub>3</sub> formation sensitivity vertically. 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引用次数: 0
摘要
臭氧(O3)在边界层(BL)内的垂直分布及其对地面的影响已被广泛研究。然而,由于在获取 O3 及其前体物质(尤其是挥发性有机化合物)的高分辨率实时数据方面存在观测限制,因此有关 O3 形成灵敏度和机制的研究十分匮乏。2022 年夏季,在中国泰山(海拔 550 米)山腰对臭氧、氮氧化物和挥发性有机化合物进行了在线测量,并与地面数据进行了比较。利用主化学机制(V3.3.1)发现,山坡上的氮氧化物与光化学反应速率之间存在正相关关系,与地面上的挥发性有机化合物限制机制不同,山坡上是氮氧化物限制机制。在山腰,较低的 NO 水平限制了羟基自由基(OH)的循环反应,导致 O3 峰值提前,氢过氧自由基(HO2)和有机过氧自由基(RO2)的浓度升高。富含 NO 的新鲜气团的到来加速了 OH 自由基循环,增强了大气氧化作用,并通过垂直传输显著影响了地表 O3 浓度。此外,NO x 减排情景模拟显示,当考虑垂直传输时,由于垂直方向上 O3 形成灵敏度的差异,地表的峰值 O3 生成率较低。这项研究凸显了基本法中 O3 的形成对 NO 的显著敏感性,强调了地面上垂直原位 O3 的形成通过垂直交换对地表 O3 浓度的潜在影响,尤其是在多山地形的城市。
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 x ), 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 x and photochemical reaction rates on the mountainside, marking it as a NO x -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 x 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.