Historical Changes in Seasonal Aerosol Acidity in the Po Valley (Italy) as Inferred from Fog Water and Aerosol Measurements

Acidity profoundly affects almost every aspect that shapes the composition of ambient particles and their environmental impact. Thermodynamic analysis of gas-particle composition datasets offers robust estimates of acidity, but they are not available for long periods of time. Fog composition datasets, however, are available for many decades; we develop a thermodynamic analysis to estimate the ammonia in equilibrium with fog water and to infer the pre-fog aerosol pH starting from fog chemical composition and pH. The acidity values from the new method agree with the results of thermodynamic analysis of the available gas-particle composition data. Applying the new method to historical (25 years) fog water composition at the rural station of San Pietro Capofiume (SPC) in the Po Valley (Italy) suggests that the aerosol has been mildly acidic, with its pH decreasing by 0.5-1.5 pH units over the last decades. The observed pH of the fog water also increased 1 unit over the same period. Analysis of the simulated aerosol pH reveals that the aerosol acidity trend is driven by a decrease in aerosol precursor concentrations, and changes in temperature and relative humidity. Currently, NO_x controls would be most effective for PM_2.5 reduction in the Po valley both during summer and winter. In the future, however, seasonal transitions to the NH₃-sensitive region may occur, meaning that the NH₃ reduction policy may become increasingly necessary.