Simulating the impact of gas-wall partitioning on SOA formation using the explicit gas mechanism integrated with aqueous reactions containing electrolytes

Sanghee Han; Myoseon Jang

doi:10.1016/j.scitotenv.2020.141360

Simulating the impact of gas-wall partitioning on SOA formation using the explicit gas mechanism integrated with aqueous reactions containing electrolytes

Sci Total Environ. 2020 Dec 15:748:141360. doi: 10.1016/j.scitotenv.2020.141360. Epub 2020 Aug 7.

Authors

Sanghee Han¹, Myoseon Jang²

Affiliations

¹ Department of Environmental Engineering Science, University of Florida, Gainesville, FL, USA.
² Department of Environmental Engineering Science, University of Florida, Gainesville, FL, USA. Electronic address: mjang@ufl.edu.

PMID: 32827892
DOI: 10.1016/j.scitotenv.2020.141360

Abstract

The impact of the Teflon reactor wall on secondary organic aerosol (SOA) formation was explicitly simulated by using the Unified Partitioning Aerosol Phase Reaction (UNIPAR) model integrated with gas-wall partitioning (GWP). The formation of oxygenated semivolatile organic compounds (SVOCs) from the photooxidation of hydrocarbons (HC) was simulated by using an explicit gas-kinetic mechanism (MCM V3.3.1). In the model, SVOC's GWP and gas-particle partitioning onto preexisting particulate matter were kinetically treated with the absorption and desorption processes. The UNIPAR model streamlined aerosol growth via the oligomerization of reactive SVOCs in the organic phase and aqueous reactions in the inorganic phase. Two important GWP parameters, GWP coefficient (K_{w, i}) and the deposition rate constant (k_on_{w, i}) of SVOCs (i) to the wall were predicted by using a quantitative structure activity relationship (QSAR) employing SVOCs' physicochemical descriptors. This GWP model was then incorporated with the UNIPAR model in the DSMACC-KPP platform and simulated SOA chamber data. The three different HCs (toluene, 1,3,5-trimethylbenzene, and α-pinene) were photochemically oxidized in the presence of NO_x and inorganic seed aerosols in an outdoor photochemical smog chamber (UF-APHOR). The impact of GWP on SOA mass varied ranging from 9% to 71% with HCs, seed conditions, NO_x, and temperature. Toluene SOA in the absence of inorganic aerosol was the most sensitive to GWP. However, in the presence of wet-inorganic seed, the impact of GWP on SOA was smaller than that of non-seed SOA owing to rapid reactions of organic species in the aqueous phase. SOA mass can be significantly underestimated in the absence of wet-inorganic seed when the aerosol model employs parameters derived using SOA data with GWP artifacts.

Keywords: Aqueous reactions; Explicit mechanisms; Gas-wall partitioning; Quantitative structure activity relationship; SOA model.