The oleic acid-ozone heterogeneous reaction system: products, kinetics, secondary chemistry, and atmospheric implications of a model system - a review
The oleic acid-ozone heterogeneous reaction system: products, kinetics, secondary chemistry, and atmospheric implications of a model system - a review
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DOI：
10.5194/acp-7-1237-2007
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发表时间：
2006-11
影响因子：
6.3
通讯作者：
J. Zahardis;G. Petrucci
中科院分区：
文献类型：
--
作者：
J. Zahardis;G. Petrucci
微量氧化剂对有机气溶胶的非均相处理对大气化学和气候调节具有重要意义。综述了一类典型的非均相反应体系：油酸-臭氧非均相反应体系和其他以脂肪酸及其衍生物为主要特征的非均相反应体系。介绍了臭氧分解中常见的醛类和有机酸类产物（壬二酸、壬壬酸、9-氧壬壬酸、壬醛）的分析。通过对二次化学反应的观察，记录和解释了相关的产物产率。活性Criegee中间体产生的二次反应产物以过氧化物为主，特别是二次臭氧化物和α-酰基氧烷基氢过氧化物低聚物和聚合物，其形成符合溶液和液相臭氧分解。这些高氧产物具有低挥发性和亲水性，可以增强粒子作为云凝结核（CCN）的能力。本文对该HRS的动力学描述进行了评述。大多数动力学研究表明，这种氧化过程要么是受臭氧扩散限制的近表面反应，要么是基于表面的反应。内部混合颗粒和涂层代表了对流层有机气溶胶更现实的代用品进展的下一个阶段，并介绍了基于脂肪酸或其衍生物的代用品的产物和臭氧分解引起的动力学。最后，介绍了含脂肪酸颗粒氧化处理对大气的主要影响。这些影响包括对流层中固体、半固体或粘性相的存在促进了不饱和物质的寿命延长，以及与相应的气相有机物相比，颗粒不饱和物质对臭氧的吸收率提高。油酸的臭氧分解增强了其CCN活性，这意味着氧化处理的颗粒可能有助于辐射的间接强迫。
The heterogeneous processing of organic aerosols by trace oxidants has many implications to atmospheric chemistry and climate regulation. This review covers a model heterogeneous reaction system (HRS): the oleic acid-ozone HRS and other reaction systems featuring fatty acids, and their derivatives. The analysis of the commonly observed aldehyde and organic acid products of ozonolysis (azelaic acid, nonanoic acid, 9-oxononanoic acid, nonanal) is described. The relative product yields are noted and explained by the observation of secondary chemical reactions. The secondary reaction products arising from reactive Criegee intermediates are mainly peroxidic, notably secondary ozonides and α-acyloxyalkyl hydroperoxide oligomers and polymers, and their formation is in accord with solution and liquid-phase ozonolysis. These highly oxygenated products are of low volatility and hydrophilic which may enhance the ability of particles to act as cloud condensation nuclei (CCN). The kinetic description of this HRS is critically reviewed. Most kinetic studies suggest this oxidative processing is either a near surface reaction that is limited by the diffusion of ozone or a surface based reaction. Internally mixed particles and coatings represent the next stage in the progression towards more realistic proxies of tropospheric organic aerosols and a description of the products and the kinetics resulting from the ozonolysis of these proxies, which are based on fatty acids or their derivatives, is presented. Finally, the main atmospheric implications of oxidative processing of particulate containing fatty acids are presented. These implications include the extended lifetime of unsaturated species in the troposphere facilitated by the presence of solids, semi-solids or viscous phases, and an enhanced rate of ozone uptake by particulate unsaturates compared to corresponding gas-phase organics. Ozonolysis of oleic acid enhances its CCN activity, which implies that oxidatively processed particulate may contribute to indirect forcing of radiation.