Graduate School of Global Environmental Studies, Kyoto University, Kyoto 606-8501, Japan.
Regional Environment Conservation Division, National Institute for Environmental Studies, Ibaraki 305-8506, Japan.
Environ Sci Technol. 2022 Sep 20;56(18):12926-12936. doi: 10.1021/acs.est.2c03628. Epub 2022 Sep 7.
This study presents total OH reactivity, ancillary trace species, HO reactivity, and complex isoprene-derived RO reactivity due to ambient aerosols measured during the air quality study (AQUAS)-Kyoto campaign in September, 2020. Observations were conducted during the coronavirus disease (COVID-19) pandemic (associated with reduced anthropogenic emissions). The spatial distribution of missing OH reactivity highlights that the origin of volatile organic compounds (VOCs) may be from natural-emission areas. For the first time, the real-time loss rates of HO and RO onto ambient aerosols were measured continuously and alternately. Ozone production sensitivity was investigated considering unknown trace species and heterogeneous loss effects of XO (≡HO + RO) radicals. Missing OH reactivity enhanced the ozone production potential by a factor of 2.5 on average. Heterogeneous loss of radicals could markedly suppress ozone production under low NO/NO conditions with slow gas-phase reactions of radicals and change the ozone regime from VOC- to NO-sensitive conditions. This study quantifies the relationship of missing OH reactivity and aerosol uptake of radicals with ozone production in Kyoto, a low-emission suburban area. The result has implications for future NO-reduction policies. Further studies may benefit from the combination of chemical transport models and inverse modeling over a wide spatiotemporal range.
本研究展示了 2020 年 9 月空气质量研究(AQUAS)-京都期间测量的大气气溶胶导致的总 OH 反应活性、辅助痕量物种、HO 反应活性和复杂异戊二烯衍生的 RO 反应活性。观测是在冠状病毒病(COVID-19)大流行期间进行的(与人为排放减少有关)。未检出 OH 反应活性的空间分布突出表明,挥发性有机化合物(VOC)的来源可能来自自然排放区。这是首次连续和交替地实时测量 HO 和 RO 对大气气溶胶的损耗速率。考虑到未知痕量物种和 XO(≡HO + RO)自由基的非均相损耗效应,研究了臭氧生成敏感性。未检出 OH 反应活性平均使臭氧生成潜力增强了 2.5 倍。在自由基气相反应缓慢且 NO/NO 条件较低的情况下,自由基的非均相损耗可显著抑制臭氧生成,并将臭氧机制从 VOC 敏感性条件转变为 NO 敏感性条件。本研究量化了京都(一个低排放郊区)缺失 OH 反应活性和自由基对气溶胶的吸收与臭氧生成之间的关系。该结果对未来的 NO 减排政策具有启示意义。进一步的研究可能受益于化学输送模型和逆模式在广泛的时空范围内的结合。