The influence of drop size-dependent fog chemistry on aerosol processing by San Joaquin Valley fogs

Drop size-resolved measurements of fog chemistry in Californiaʹs San Joaquin Valley during the 1995 Integrated Monitoring Study reveal that fog composition varies with drop size. Small fog drops were less alkaline and typically contained higher major ion (nitrate, sulfate, ammonium) concentrations than large drops. Small drops often contained higher concentrations of Fe and Mn than large drops while H2O2 concentrations exhibited no strong drop size dependence. Simulation of an extended fog episode in Fresno, California revealed the capability of a drop size-resolved fog chemistry model to reproduce the measured (based on two drop size categories) drop size dependence of several key species. The model was also able to satisfactorily reproduce measured species-dependent deposition rates (ammonium>sulfate>nitrate) resulting from fog drop sedimentation. Both the model simulation and direct analysis of size-resolved fog composition observations and measured gas-phase oxidant concentrations indicate the importance of ozone as an aqueous-phase S(IV) oxidant in these high pH fogs. Due to the nonlinear dependence of the rate law for the ozone pathway on the hydrogen ion concentration, use of the average fog drop composition can lead to significant underprediction of aqueous phase sulfate production rates in these chemically heterogeneous fogs.