Semiempirical Model for Organic Aerosol Growth by Acid-Catalyzed Heterogeneous Reactions of Organic Carbonyls

摘要

Aerosol growth by heterogeneous reactions of diverse carbonyls in the presence and absence of acidified seed aerosols was studied in a 4 m long flow reactor (2.5 cm i.d.) and a 2-m{sup}3 indoor Teflon film chamber under darkness. The acid catalytic effects on heterogeneous aerosol production were observed for diverse carbonyls in various ranges of humidities and compositions of seed inorganic aerosols. Particle population data measured by a scanning mobility particle sizer were used to calculate organic aerosol growth. To accountforthe aerosol growth contributed by heterogeneous reactions, the increase in organic aerosol mass was normalized by the organic mass predicted by partitioning or the square of predicted organic mass. The carbonyl heterogeneous reactions were accelerated in the presence of acid catalysts (H{sub}2SO{sub}4), leading to higher aerosol yields than in their absence. The experimental data from aerosol yields in the flow reactor were semiempirically fitted to the model parameters to predict the organic aerosol growth. The model parameters consist of environmental characteristics and molecular structure information of organic carbonyls. Basicity constants of carbonyls were used to describe the proton affinity of carbonyls for the acid catalysts. Particle environmental factors, such as humidity, temperature, and inorganic seed composition, were expressed by excess acidity and the parameters obtained from an inorganic thermodynamic model. A stepwise regression analysis of the aerosol growth model for the experimental data revealed that either the chemical structure information of carbonyls or characteristic environmental parameters are statistically significant in the prediction of organic aerosol growth. It was concluded that this model approach is applicable to predict secondary organic aerosol formation by heterogeneous reaction.