Division of Environmental Health & Risk Management, School of Geography, Earth & Environmental Sciences, University of Birmingham, Edgbaston, Birmingham B15 2TT, UK.
Chem Soc Rev. 2013 Dec 21;42(24):9333-91. doi: 10.1039/c3cs60147a. Epub 2013 Sep 30.
Polycyclic aromatic hydrocarbons (PAHs) are of considerable concern due to their well-recognised toxicity and especially due to the carcinogenic hazard which they present. PAHs are semi-volatile and therefore partition between vapour and condensed phases in the atmosphere and both the vapour and particulate forms undergo chemical reactions. This article briefly reviews the current understanding of vapour-particle partitioning of PAHs and the PAH deposition processes, and in greater detail, their chemical reactions. PAHs are reactive towards a number of atmospheric oxidants, most notably the hydroxyl radical, ozone, the nitrate radical (NO3) and nitrogen dioxide. Rate coefficient data are reviewed for reactions of lower molecular weight PAH vapour with these species as well as for heterogeneous reactions of higher molecular weight compounds. Whereas the data for reactions of the 2-3-ring PAH vapour are quite extensive and generally consistent, such data are mostly lacking for the 4-ring PAHs and the heterogeneous rate data (5 and more rings), which are dependent on the substrate type and reaction conditions, are less comprehensive. The atmospheric reactions of PAH lead to the formation of oxy and nitro derivatives, reviewed here, too. Finally, the capacity of PAHs for long range transport and the results of numerical model studies are described. Research needs are identified.
多环芳烃(PAHs)因其公认的毒性,特别是其致癌危害而引起了相当大的关注。PAHs 具有半挥发性,因此会在大气中的气相和凝聚相之间分配,并且气相和颗粒相都发生化学反应。本文简要回顾了当前对 PAHs 的气相-颗粒分配和 PAH 沉积过程的理解,并更详细地介绍了它们的化学反应。PAHs 对许多大气氧化剂具有反应性,最显著的是羟基自由基、臭氧、硝酸盐自由基(NO3)和二氧化氮。本文综述了低分子量 PAH 蒸气与这些物质的反应以及高分子量化合物的非均相反应的速率系数数据。尽管 2-3 环 PAH 蒸气的反应数据相当广泛且通常一致,但对于 4 环 PAHs 和非均相反应速率数据(5 环及以上),这些数据则大多缺乏,并且这些数据取决于底物类型和反应条件,因此不够全面。本文还综述了 PAH 的大气反应导致的含氧和含硝基衍生物的形成。最后,描述了 PAHs 的长距离传输能力和数值模型研究的结果。确定了研究需求。