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Multi-generation gas-phase oxidation, equilibrium partitioning, and the formation and evolution of secondary organic aerosol

机译:多代气相氧化,平衡分配,以及二次有机气溶胶的形成和演化

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A new model of secondary organic aerosol (SOA) formation is developed that explicitly takes into account multi-generational oxidation as well as fragmentation of gas-phase compounds, and assumes equilibrium gas-particle partitioning. The model framework requires specification of a limited number of tunable parameters to describe the kinetic evolution of SOA mass, the average oxygen-to-carbon atomic ratio and the mean particle volatility as oxidation proceeds. These parameters describe (1) the relationship between oxygen content and volatility, (2) the probability of fragmentation and (3) the amount of oxygen added per reaction. The time-evolution and absolute value of the simulated SOA mass depends sensitively on all tunable parameters. Of the tunable parameters, the mean O : C is most sensitive to the oxygen/volatility relationship, exhibiting only a weak dependence on the other relationships. The model mean particle O : C produced from a given compound is primarily controlled by the number of carbon atoms comprising the SOA precursor, with some sensitivity to the specified oxygen/volatility relationship. The model is tested against laboratory measurements of time-dependent SOA formation from the photooxidation of -pinene and n-pentadecane and performs well (after tuning). The model can also accurately simulate the carbon-number dependence of aerosol yields previously observed for oxidation of straight-chain alkanes. This model may provide a generalized framework for the interpretation of laboratory SOA formation experiments in which explicit consideration of multiple-generations of products is required, which is true for all photo-oxidation experiments.
机译:开发了一种新的二次有机气溶胶(SOA)形成模型,其明确地考虑了多代氧化以及气相化合物的碎片,并假设平衡气体颗粒分配。模型框架需要指定有限数量的可调谐参数来描述SOA质量的动力学演变,平均氧 - 碳原子比和平均颗粒挥发性作为氧化所得。这些参数描述(1)氧含量和挥发性之间的关系,(2)碎裂的概率和(3)每次反应添加的氧气量。模拟SOA质量的时间 - 演变和绝对值敏感地取决于所有可调参数。在可调参数中,平均o:c对氧气/波动关系最敏感,表现出对其他关系的弱依赖性。由给定化合物产生的模型平均粒子O:C主要由包含SOA前体的碳原子的数量来控制,其对所述氧气/挥发性关系的一些敏感性。该模型针对从 - 烯烃和正戊烷的光氧化进行时间依赖性SOA形成的实验室测量,并进行良好(调谐后)。该模型还可以准确地模拟预先观察到的气溶胶产量的碳编号依赖性,用于直链烷烃的氧化。该模型可以提供用于解释实验室SOA形成实验的广义框架,其中需要明确考虑多一代产品,这对于所有光氧化实验为真实。

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