COUPLING THERMODYNAMIC THEORY WITH MEASUREMENTS TO CHARACTERIZE ACIDITY OF ATMOSPHERIC PARTICLES

The reference method currently being used in community health studies to characterize the acidity of atmospheric particles is based upon measuring the pH of aqueous extracts of atmospheric particles collected on filter media. These measurements represent total extractable acidity, i.e., hydrogen ion concentration at sufficient dilution of the sample, rather than the actual acidity of airborne particles. In contrast, models based upon chemical equilibrium theory can be used to estimate the hydrogen ion concentration and water content of atmospheric particles from the observed concentration of major solutes (sulfate, nitrate, chloride, ammonium, and sodium). Using about 100 data points from an intensive measurement study in Uniontown, Pennsylvania during 1990, we examined the nature and the causes of the deviations.between measured and estimated hydrogen ion concentrations. We found that the measured hydrogen ion concentrations were substantially higher than the estimated concentrations because dilution of the sample during extraction promoted dissociation of bisulfate ions and hence increased the hydrogen ion concentration. Because total extractable acidity as measured by the pH method only partially characterizes particles, our results demonstrate that models should be used to augment and improve the information derived from these measurements, particularly to estimate the actual acidity of airborne particles.