Production and removal of aerosol in a polluted fog layer: model evaluation and fog effect on PM

A radiation fog physics, gas- and aqueous-phase chemistry model is evaluated against measurements in three sites in the San Joaquin Valley of California (SJV) during the winter of 1995. The measurements include for the first time vertically resolved fog chemical composition measurements. Overall the model is successful in reproducing the fog dynamics as well as the temporal and spatial variability of the fog composition (pH, sulfate, nitrate, and ammonium concentrations) in the area. Sulfate production in the fog layer is relatively slow (1–4 μg m⁻³ per fog episode) compared to the episodes in the early 1980s because of the low SO₂ concentrations in the area and the lack of oxidants inside the fog layer. Sulfate production inside the fog layer is limited by the availability of oxidants in the urban areas of the valley and by SO₂ in the more remote areas. Nitrate is produced in the rural areas of the valley by the heterogeneous reaction of N₂O₅ on fog droplets, but this reaction is of secondary importance for the more polluted urban areas. The gas-phase production of HNO₃ during the daytime is sufficient to balance the nitrate removed during the nighttime fog episodes. Entrainment of air from the layer above the fog provides another source of reactants for the fog layer. Wet removal is one of most important processes inside the fog layer in SJV. We estimate based on the three episodes investigated during IMS95 that a typical fog episode removes 500–2000 μg m⁻² of sulfate, 2500–6500 μg m⁻² of nitrate, and 2000–3500 μg m⁻² of ammonium. For the winter SJV valley the net fog effect corresponds to reductions in ground ambient concentrations of 0.05–0.2 μg m⁻³ for sulfate, 3–6 μg m⁻³ for total nitrate, and 1–3 μg m⁻³ for total ammonium.