Liu Chao, Lu Bingqing, Wang Qian, Zhang Zekun, Meng Xue, Huo Juntao, Herrmann Hartmut, Li Xiang
Department of Environmental Science & Engineering, Fudan University, Shanghai 200438, China.
Department of Environmental Science & Engineering, Fudan University, Shanghai 200438, China; Shanghai Environmental Monitoring Center, Shanghai 200235, China.
Sci Total Environ. 2024 Oct 1;945:174066. doi: 10.1016/j.scitotenv.2024.174066. Epub 2024 Jun 17.
Double high pollution (DHP) of ozone (O) and fine particulate matter (PM) has frequently been observed in China in recent years. Numerous studies have speculated that DHP might be related to nitrous acid (HONO), but the chemical mechanism involved remains unclear. Field observation results of DHP in Shanghai indicate that the high concentration of HONO produced by nitrogen dioxide (NO) heterogeneous reactions under conditions of high temperature and high humidity promotes an increase in PM and O concentrations. The box model combined with field observations to reconstruct pollution events indicates that HONO photolysis generates abundant hydroxyl (OH) radicals that rapidly oxidize volatile organic compounds (VOCs), which in turn accelerates the RO (OH, hydroperoxyl (HO), and organic peroxy (RO) radicals) cycle and causes the accumulation of O. This elevated O along with high concentrations of HONO, produces particulate nitrate (pNO) by encouraging the NO + OH reaction. This process strengthens the chemical coupling between O and PM, which can exacerbate the DHP of O and PM. Sensitivity analysis of pNO/O-NO-VOCs suggests that under nitrogen oxides (NO = NO + NO) reduction conditions, simultaneous control of pNO and O can be expected to be successfully achieved through emission reduction of alkanes and oxygenated VOCs (OVOCs). Therefore, the present research will facilitate the design of appropriate PM and O control strategies for high HONO concentration conditions, and thus alleviate the current stresses of air pollution.
近年来,中国频繁观测到臭氧(O₃)和细颗粒物(PM₂.₅)的双重高污染(DHP)现象。众多研究推测DHP可能与亚硝酸(HONO)有关,但其中涉及的化学机制仍不明确。上海DHP的实地观测结果表明,在高温高湿条件下,二氧化氮(NO₂)非均相反应产生的高浓度HONO会促使PM₂.₅和O₃浓度升高。结合实地观测结果的箱式模型对污染事件进行重建,结果表明HONO光解会产生大量的羟基(OH)自由基,这些自由基会迅速氧化挥发性有机化合物(VOCs),进而加速RO(OH、氢过氧自由基(HO₂)和有机过氧自由基(RO₂))循环并导致O₃积累。这种升高的O₃与高浓度的HONO一起,通过促进NO + OH反应生成颗粒态硝酸盐(pNO₃)。这一过程加强了O₃与PM₂.₅之间的化学耦合,可能会加剧O₃和PM₂.₅的DHP。pNO₃/O₃-NOₓ-VOCs的敏感性分析表明,在氮氧化物(NOₓ = NO + NO₂)减排条件下,通过减少烷烃和含氧挥发性有机化合物(OVOCs)的排放,有望成功实现对pNO₃和O₃的同时控制。因此,本研究将有助于设计针对高HONO浓度条件的合适的PM₂.₅和O₃控制策略,从而缓解当前的空气污染压力。