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增强 NO 对甲苯光氧化生成光吸收性二次有机气溶胶的作用。

Enhancing effect of NO on the formation of light-absorbing secondary organic aerosols from toluene photooxidation.

机构信息

Key Lab of Geographic Information Science of the Ministry of Education, School of Geographic Sciences, East China Normal University, Shanghai 210062, China.

Key Lab of Geographic Information Science of the Ministry of Education, School of Geographic Sciences, East China Normal University, Shanghai 210062, China; Institute of Eco-Chongming, 3663 North Zhongshan Road, Shanghai 200062, China.

出版信息

Sci Total Environ. 2021 Nov 10;794:148714. doi: 10.1016/j.scitotenv.2021.148714. Epub 2021 Jun 27.

Abstract

Aromatic hydrocarbons are one of the major precursors of atmospheric brown carbon (BrC) and both abundantly co-exist with NO in the urban atmosphere especially in winter haze period. However, the impact of NOx on the formation of BrC derived from aromatic hydrocarbons is still not fully understood. In this study, the yield and light absorption of secondary organic aerosols (SOA) from toluene photooxidation under various nitrogen oxides (NO) levels were investigated by using a 5 m photooxidation smog chamber. A trend of increase at first and then decrease in the SOA yield with an increasing NO concentration was observed. The acid-catalyzed heterogeneous reactions lead to the increase of SOA yield in the low-NO regime. The formation of low-volatility species might be suppressed at high-NO conditions is responsible for the decreased SOA yield. In contrast, light absorption and mass absorption coefficient (MAC) of the toluene-derived SOA continuously increased with the increasing NO concentrations. HR-ToF-AMS results showed that nitrogen-containing organic compounds (NOCs) are the main species that lead to the increase of the SOA light absorption. The ratio of CHN family to the total NOCs, which are derived from the nitro compounds, also increased dominantly with the increasing NO levels and accounted for more than half of the total NOCs when the NO concentration increased to 495 ppbv, indicating that nitro compounds rather than organic nitrates are the major light-absorbing species and preferably formed in the toluene oxidation process.

摘要

芳香烃是大气棕色碳 (BrC) 的主要前体之一,尤其是在冬季雾霾期间,它们与 NO 在城市大气中大量共存。然而,NOx 对源自芳香烃的 BrC 形成的影响仍未完全了解。在这项研究中,我们使用 5m 光氧化烟雾箱研究了不同氮氧化物 (NO) 水平下甲苯光氧化生成的二次有机气溶胶 (SOA) 的产率和光吸收。结果表明,SOA 产率随着 NO 浓度的增加呈现先增加后减少的趋势。在低 NO 条件下,酸催化的非均相反应导致 SOA 产率增加。在高 NO 条件下,低挥发性物种的形成可能受到抑制,这是导致 SOA 产率降低的原因。相比之下,甲苯衍生 SOA 的光吸收和质量吸收系数 (MAC) 随着 NO 浓度的增加而持续增加。高分辨时间飞行质谱 (HR-ToF-AMS) 结果表明,含氮有机化合物 (NOCs) 是导致 SOA 光吸收增加的主要物质。来自硝基化合物的 CHN 族化合物与总 NOCs 的比值也随着 NO 浓度的增加而显著增加,当 NO 浓度增加到 495 ppbv 时,其占总 NOCs 的比例超过一半,这表明硝基化合物而不是有机硝酸盐是主要的光吸收物质,并且在甲苯氧化过程中更容易形成。

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