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在连续流动室内进行单萜光氧化反应:SOA 生成及氧化剂、NO 和 VOC 前体的影响。

Monoterpene Photooxidation in a Continuous-Flow Chamber: SOA Yields and Impacts of Oxidants, NO, and VOC Precursors.

机构信息

Atmospheric Sciences and Global Change Division, Pacific Northwest National Laboratory, Richland, Washington 99352, United States.

School of Environment, Harbin Institute of Technology, Harbin, Heilongjiang 150001, China.

出版信息

Environ Sci Technol. 2022 Sep 6;56(17):12066-12076. doi: 10.1021/acs.est.2c02630. Epub 2022 Aug 17.

Abstract

Monoterpene photooxidation plays an important role in secondary organic aerosol (SOA) formation in the atmosphere. The low-volatility products can enhance new particle formation and particle growth and thus influence climate feedback. Here, we present the results of α-pinene and Δ-3-carene photooxidation experiments conducted in continuous-flow mode in an environmental chamber under several reaction conditions. The roles of oxidants, addition of NO, and VOC molecular structure in influencing SOA yield are illustrated. SOA yield from α-pinene photooxidation shows a weak dependence on HO concentration, which is a proxy for HO concentration. The high O/C ratios observed in the α-pinene photooxidation products suggest the production of highly oxygenated organic molecules (HOM). Addition of ozone to the chamber during low-NO photooxidation experiments leads to higher SOA yield. With the addition of NO, the production of N-containing HOMs is enhanced and the SOA yield shows a modest, nonlinear dependence on the input NO concentration. Carene photooxidation leads to higher SOA yield than α-pinene under similar reaction conditions, which agrees with the lower volatility retrieved from evaporation kinetics experiments. These results improve the understanding of SOA formation from monoterpene photooxidation and could be applied to refine the representation of biogenic SOA formation in models.

摘要

单萜烯的光氧化在大气中二次有机气溶胶(SOA)的形成中起着重要作用。低挥发性产物可以促进新粒子的形成和颗粒的生长,从而影响气候反馈。在这里,我们介绍了在环境室内连续流动模式下进行的α-蒎烯和Δ-3-蒈烯光氧化实验的结果,实验在几种反应条件下进行。说明了氧化剂、NO 的添加以及 VOC 分子结构在影响 SOA 产率方面的作用。α-蒎烯光氧化产生的 SOA 产率与 HO 浓度(HO 浓度的代表)的依赖性较弱。在 α-蒎烯光氧化产物中观察到的高 O/C 比表明了高度含氧有机分子(HOM)的生成。在低 NO 光氧化实验期间,向腔室中添加臭氧会导致更高的 SOA 产率。加入 NO 后,含 N 的 HOM 的生成得到增强,并且 SOA 产率对输入的 NO 浓度表现出适度的非线性依赖性。在类似的反应条件下,蒈烯光氧化产生的 SOA 产率高于α-蒎烯,这与蒸发动力学实验中得出的较低挥发性一致。这些结果提高了对单萜烯光氧化形成 SOA 的理解,并可用于改进模型中对生物源 SOA 形成的表示。

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