The roles of volatile organic compound deposition and oxidation mechanisms in determining secondary organic aerosol production: A global perspective using the UKCA chemistry-climate model (vn8.4)

Abstract

The representation of volatile organic compound (VOC) deposition and oxidation mechanisms in the context of secondary organic aerosol (SOA) formation are developed in the United Kingdom Chemistry and Aerosol (UKCA) chemistry-climate model. Impacts of these developments on both the global SOA budget and model agreement with observations are quantified. Firstly, global model simulations were performed with varying VOC dry deposition and wet deposition fluxes. Including VOC dry deposition reduces the global annual-total SOA production rate by 2 %-32 %, with the range reflecting uncertainties in surface resistances. Including VOC wet deposition reduces the global annualtotal SOA production rate by 15% and is relatively insensitive to changes in effective Henry's law coefficients. Without precursor deposition, simulated SOA concentrations are lower than observed with a normalised mean bias (NMB) of -51 %. Hence, including SOA precursor deposition worsens model agreement with observations even further (NMB=-66 %). Secondly, for the anthropogenic and biomass burning VOC precursors of SOA (VOCANT=BB), model simulations were performed by (a) varying the parent hydrocarbon reactivity, (b) varying the number of reaction intermediates, and (c) accounting for differences in volatility between oxidation products from various pathways. These changes were compared to a scheme where VOCANT=BB adopts the reactivity of a monoterpene (-pinene), and is oxidised in a singlestep mechanism with a fixed SOA yield. By using the chemical reactivity of either benzene, toluene, or naphthalene for VOCANT=BB, the global annual-total VOCANT=BB oxidation rate changes by -3 %, -31 %, or -66 %, respectively, compared to when using -pinene. Increasing the number of reaction intermediates, by introducing a peroxy radical (RO2), slightly slows the rate of SOA formation, but has no impact on the global annual-total SOA production rate. However, RO2 undergoes competitive oxidation reactions, forming products with substantially different volatilities. Accounting for the differences in product volatility between RO2 oxidation pathways increases the global SOA production rate by 153% compared to using a single SOA yield. Overall, for relatively reactive compounds such as toluene and naphthalene, the reduction in reactivity for VOCANT=BB oxidation is outweighed by accounting for the difference in volatility of RO2 products, leading to a net increase in the global annual-total SOA production rate of 85% and 145 %, respectively, and improvements in model agreement (NMB of -46% and 56 %, respectively). However, for benzene, the reduction in VOCANT=BB oxidation is not outweighed by accounting for the difference in SOA yield pathways, leading to a small change in the global annual-total SOA production rate of -3 %, and a slight worsening of model agreement with observations (NMBD -77 %). These results highlight that variations in both VOC deposition and oxidation mechanisms contribute to substantial uncertainties in the global SOA budget and model agreement with observations.