Studying the effects of calcium and magnesium on size-distributed nitrate and ammonium with EQUISOLV II

A chemical equilibrium code was improved and used to show that calcium and magnesium have a large yet different effect on the aerosol size distribution in different regions of Los Angeles. In the code, a new technique of solving individual equilibrium equations was developed. The technique, the analytical equilibrium iteration (AEI) method, gives the same solutions (to at least 7 decimal places) as the previous technique used, the mass-flux iteration (MFI) method, but consumes 13–48 times less computer time. The model was also updated to include treatment of potassium, calcium, magnesium, and carbonate. Previously, it treated only nitrate, ammonium, chloride, sulfate, and sodium. Predictions from the updated code, EQUISOLV II, were compared with data from an eight-stage Berner impactor at Long Beach, Claremont, and Riverside during the Southern California Air Quality Study. When any equilibrium solver is applied between the gas phase and multiple aerosol size bins, unique solutions are possible only when solids (e.g., NH₄NO₃) that form from two gas-phase species are absent. For this study, unique solutions were possible only when the relative humidity exceeded 62%, and only cases in this regime are discussed. Base-case predictions of nitrate and ammonium matched observations well in most size bins of every case. When Ca and Mg were removed from calculations, coarse-mode nitrate decreased at Long Beach, as expected, to maintain charge balance. At Riverside, removing Ca and Mg had the opposite effect, increasing coarse-mode nitrate, shifting it from the accumulation mode. The reason is explained in terms of mean mixed activity coefficients. At Claremont, the charge-balance and activity-coefficient effects nearly canceled each other.