Modeling the Formation of Secondary Organic Aerosol (SOA). 2. The Predicted Effects of Relative Humidity on Aerosol Formation in the α-Pinene-, β-Pinene-, Sabinene-, Δ^(3-)Carene-, and Cyclohexene-Ozone Systems

Abstract

Atmospheric oxidation of volatile organic compounds can lead to the formation of secondary organic aerosol (SOA) through the gas/particle (G/P) partitioning of the oxidation products. Since water is ubiquitous in the atmosphere, the extent of the partitioning for any individual organic product depends not only on the amounts and properties of the partitioning organic compounds, but also on the amount of water present. Predicting the effects of water on the atmospheric G/P distributions of organic compounds is, therefore, central to understanding SOA formation. The goals of the current work are to gain understanding of how increases in RH affect (1) overall SOA yields, (2) water uptake by SOA, (3) the behaviors of individual oxidation products, and (4) the fundamental physical properties of the SOA phase that govern the G/P distribution of each of the oxidation products. Part 1 of this series considered SOA formation from five parent hydrocarbons in the absence of water. This paper predicts how adding RH to those systems uniformly increases both the amount of condensed organic mass and the amount of liquid water in the SOA phase. The presence of inorganic components is not considered. The effect of increasing RH is predicted to be stronger for SOA produced from cyclohexene as compared to SOA produced from four monoterpenes. This is likely a result of the greater general degree of oxidation (and hydrophilicity) of the cyclohexene products. Good agreement was obtained between predicted SOA yields and laboratory SOA yield data actually obtained in the presence of water. As RH increases, the compounds that play the largest roles in changing both the organic and water masses in the SOA phase are those with vapor pressures that are intermediate between those of essentially nonvolatile and highly volatile species. RH-driven changes in the compound-dependent G/P partitioning coefficient K_p result from changes in both the average molecular weight MW_(om) of the absorbing organic/water phase, and the compound-dependent activity coefficient ζ values. Adding water to the SOA phase by increasing the RH drives down MW_(om) and thereby uniformly favors SOA condensation. The effect of RH on ζ values is compound specific and depends on the hydrophilicity of the specific compound of interest; the more hydrophilic a compound, the more increasing RH will favor its condensation into the SOA phase. The results also indicate that it may be a useful first approximation to assume that ζ = 1 for many compounds making up SOA mixtures.

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