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NO 和 RH 对邻二甲苯经 OH 氧化生成二次有机气溶胶和光吸收的影响。

Effects of NO and RH on secondary organic aerosol formation and light absorption from OH oxidation of ο-xylene.

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; Institute of Eco-Chongming, 3663 North Zhongshan Road, Shanghai, 200062, China.

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

出版信息

Chemosphere. 2022 Dec;308(Pt 3):136541. doi: 10.1016/j.chemosphere.2022.136541. Epub 2022 Sep 20.

Abstract

Ο-xylene is an important aromatic volatile organic compound (VOC) in the atmosphere over urban areas. In this work, the effect of nitrogen dioxide (NO) concentration and relative humidity (RH) on the mass concentration of secondary organic aerosols (SOA) formed from ο-xylene OH oxidization was investigated in a photooxidation chamber. The ο-xylene SOA mass concentration increased from 54.2 μg m to 127.2 μg m during dry conditions, but decreased from 177.7 μg m to 146.5 μg m during high RH conditions when the initial NO concentration increased form 0 ppbv to about 900 ppbv. An increase in the ratio of [NO]/[Org] and a decrease in the oxidation state of carbon (OS) of SOA suggested that acid-catalyzed heterogeneous reaction was responsible for enhancing SOA formation with increasing NO concentrations in dry conditions. In contrast, in humid conditions, the high molecular diffusion capacity of SOA could promote the reactivity of OH towards the interior of SOA, and the enhancement of nitrous acid (HONO) formation under high NO conditions could promote the SOA aging processes and be responsible for the decreasing trend of SOA formation with NO. Light absorption by SOA was also measured, and both NO and RH enhanced the mass absorption coefficient (MAC) value for the optical properties of ο-xylene SOA. The highest MAC value of ο-xylene SOA was 0.89 m g, observed during humid conditions with an initial NO concentration of 862 ppbv, which was 3.9 times higher than in the experiment conducted in the absence of NO under dry conditions. The formation of nitrogen-containing organic compounds (NOCs) and humic-like substances (HULIS) were responsible for the increased MAC values of ο-xylene derived SOA. This study provides new insight into the effect of NO on SOA formation through the change in ο-xylene photooxidation under different RH conditions, and the complex effect of multiple environmental factors on SOA formation was also important and should not be ignored.

摘要

邻二甲苯是城市地区大气中重要的芳香挥发性有机化合物(VOC)。在这项工作中,我们在光氧化室内研究了二氧化氮(NO)浓度和相对湿度(RH)对邻二甲苯 OH 氧化生成二次有机气溶胶(SOA)的质量浓度的影响。在干燥条件下,初始 NO 浓度从 0 ppbv 增加到约 900 ppbv 时,邻二甲苯 SOA 的质量浓度从 54.2 μg/m 增加到 127.2 μg/m,但在高 RH 条件下,当初始 NO 浓度从 0 ppbv 增加到约 900 ppbv 时,邻二甲苯 SOA 的质量浓度从 177.7 μg/m 减少到 146.5 μg/m。[NO]/[Org]比值的增加和 SOA 氧化态(OS)的降低表明,在干燥条件下,随着 NO 浓度的增加,酸催化的非均相反应负责增强 SOA 的形成。相比之下,在潮湿条件下,SOA 的高分子扩散能力可以促进 OH 向 SOA 内部的反应性,而在高 NO 条件下形成的亚硝酸(HONO)可以促进 SOA 的老化过程,并导致 SOA 形成随 NO 的减少趋势。还测量了 SOA 的光吸收,NO 和 RH 都增强了邻二甲苯 SOA 的质量吸收系数(MAC)值。在初始 NO 浓度为 862 ppbv、相对湿度较高的条件下,邻二甲苯 SOA 的最高 MAC 值为 0.89 m·g,比在干燥条件下无 NO 存在的实验中观察到的最高 MAC 值 0.24 m·g 高 3.9 倍。含氮有机化合物(NOCs)和腐殖质样物质(HULIS)的形成是导致邻二甲苯衍生 SOA 的 MAC 值增加的原因。这项研究提供了新的见解,即通过不同 RH 条件下邻二甲苯光氧化的变化,NO 对 SOA 形成的影响,以及多种环境因素对 SOA 形成的复杂影响也很重要,不容忽视。

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