Fractionation of atmospheric acid and base components within storm events by precipitation scavenging processes

Concentrations of ions in storm rainwater in Texas have been monitored for each 0.254 mm increment of precipitation. The changes in concentrations have been analyzed to investigate the role of differential rates of scavenging of particulate matter of differing particle size, and especially the major acid and base components. The empirical trend at the onset of rainfall is a chemical fractionation of acids and bases with correspondingly wide pH variations. These results are confirmed by model calculations, which show a significant preferential scavenging of calcium relative to sulfate in the first 10 mm of rainfall, resulting in fractionation of bases and acids from their atmospheric concentrations. Previous studies, using Target Transformation Factor Analysis of ion concentrations in storm precipitation and regional ambient aerosol data, statistically determined the average source for acidic secondary species and alkaline particulate matter. Two types of crustal sources were identified as western and eastern soil dust. In this study, an alternate physical explanation for these two soil dust factors is offered. As a storm progresses, the elements in the local soil dust are fractionated as a result of their differential rates of precipitation scavenging, enriching species predominantly in the fine particle size and depleting elements predominantly in the coarse particle size. This fractionation process results in a single source having different elemental ratios at the beginning and at the end of a rain event. For Austin, Dallas, and Tyler, Texas, the soil dust previously identified as being from eastern sources could, instead, be a fractionated form of the western soil source.