Observational Constraints on Modeling Growth and Evaporation Kinetics of Isoprene SOA

Tuesday, 16 December 2014: 4:38 PM
Rahul A Zaveri1, John E Shilling1, Alla Zelenyuk1, Jiumeng Liu1, Jacqueline Mary Wilson1, Alexander Laskin1, Bingbing Wang1, Jerome D Fast1, Richard C Easter1, Jian Wang2, Chongai Kuang2, Joel A Thornton3, Ari Setyan4, Qi Zhang5, Timothy Bruce Onasch6 and Douglas R Worsnop6, (1)Pacific Northwest National Laboratory, Richland, WA, United States, (2)Brookhaven National Laboratory, Upton, NY, United States, (3)University of Washington Seattle Campus, Seattle, WA, United States, (4)EMPA - Swiss Federal Laboratories for Materials Science & Technology, Dubendorf, Switzerland, (5)University of California Davis, Davis, CA, United States, (6)Aerodyne Research, Inc., Billerica, MA, United States
Isoprene is thought to be a major contributor to the global secondary organic aerosol (SOA) budget, and therefore has the potential to exert a significant influence on earth’s climate via aerosol direct and indirect radiative effects. Both aerosol optical and cloud condensation nuclei properties are quite sensitive to aerosol number size distribution, as opposed to the total aerosol mass concentration. Recent studies suggest that SOA particles can be highly viscous, which can affect the kinetics of SOA partitioning and size distribution evolution when the condensing organic vapors are semi-volatile. In this study, we examine the growth kinetics of SOA formed from isoprene photooxidation in the presence of pre-existing Aitken and accumulation mode aerosols in: (a) the ambient atmosphere during the CARES field campaign, and (b) the environmental chamber at PNNL. Each growth episode is analyzed and interpreted with the updated MOSAIC aerosol box model, which performs kinetic gas-particle partitioning of SOA and takes into account diffusion and chemical reaction within the particle phase. The model is initialized with the observed aerosol size distribution and composition at the beginning of the experiment, and the total amount of SOA formed in the model at any given time is constrained by the observed total amount of SOA formed. The variable model parameters include the number of condensing organic species, their gas-phase formation rates, their effective volatilities, and their bulk diffusivities in the Aitken and accumulation modes. The objective of the constrained modeling exercise is then to determine which model configuration is able to best reproduce the observed size distribution evolution, thus providing valuable insights into the possible mechanism of SOA formation. We also examine the evaporation kinetics of size-selected particles formed in the environmental chamber to provide additional constraints on the effective volatility and bulk diffusivity of the organic species. Our results suggest that SOA formed from isoprene photooxidation is semi-volatile, and the resulting size distribution evolution is highly sensitive to the phase state (bulk diffusivity) of the pre-existing aerosol. Implications of these findings on further SOA model development and evaluation strategy will be discussed.