Donahue Neil M, Robinson Allen L, Trump Erica R, Riipinen Ilona, Kroll Jesse H
Carnegie Mellon University Center for Atmospheric Particle Studies, Pittsburgh, PA, USA,
Top Curr Chem. 2014;339:97-143. doi: 10.1007/128_2012_355.
Organic-aerosol phase partitioning (volatility) and oxidative aging are inextricably linked in the atmosphere because partitioning largely controls the rates and mechanisms of aging reactions as well as the actual amount of organic aerosol. Here we discuss those linkages, describing the basic theory of partitioning thermodynamics as well as the dynamics that may limit the approach to equilibrium under some conditions. We then discuss oxidative aging in three forms: homogeneous gas-phase oxidation, heterogeneous oxidation via uptake of gas-phase oxidants, and aqueous-phase oxidation. We present general scaling arguments to constrain the relative importance of these processes in the atmosphere, compared to each other and compared to the characteristic residence time of particles in the atmosphere.
在大气中,有机气溶胶的相分配(挥发性)和氧化老化有着千丝万缕的联系,因为相分配在很大程度上控制着老化反应的速率和机制以及有机气溶胶的实际含量。在此,我们讨论这些联系,阐述相分配热力学的基本理论以及在某些条件下可能限制达到平衡的动力学。然后,我们讨论三种形式的氧化老化:均相气相氧化、通过气相氧化剂吸收进行的非均相氧化以及水相氧化。我们给出一般的尺度论证,以确定这些过程在大气中的相对重要性,相互比较以及与颗粒在大气中的特征停留时间相比较。