Ammonia and nitric acid concentrations in equilibrium with atmospheric aerosols: Experiment vs theory

The equilibrium between gaseous ammonia, nitric acid, and aerosol nitrate is discussed on the basis of a recent field experiment in southern California. Comparison is drawn between theoretical equilibrium calculations and simultaneous measurements of nitric acid, ammonia, ammonium ion, nitrate ion, sulfate ion, other ionic species, temperature and dewpoint. Particulate and gaseous pollutant concentrations at some inland sampling sites are readily explained if the aerosol is assumed to exist as an external mixture with all particulate nitrate and ammonium available to form pure NH₄NO₃. At other monitoring sites, especially near the coast, aerosol nitrate is found in the presence of NH₃ and HNO₃ concentrations that thermodynamic calculations show are too low to produce pure NH₄NO₃. This can be explained when the amount of aerosol nitrate that can be derived from reaction of nitric acid with sea salt and soil dust is taken into account. A calculation approach that accounts for the presence of mixed sulfate and nitrate salts improves the agreement between predicted and observed pollutant concentrations in the majority of cases studied. Uncertainties in these calculations arise from a number of sources including the thermodynamic quantities, and the effect of these uncertainties on the comparison between theory and experiment is discussed.