Ambient sulfate trends and the influence of meteorology

Data on atmospheric levels of sulfur dioxide (SO2) and sulfate were examined to quantify changes since 1989. Changes in sulfur species were adjusted to account for meteorological variability. Adjustments were made using meteorological variables expressed in terms of their principal components that were used as predictors in statistical models. Several models were tested. A generalized additive model (GAM)-based in part on nonparametric, locally smoothed predictor functions-computed the greatest association between sulfate and the meteorological predictors. Sulfate trends estimated after a GAM-based adjustment for weather-related influences were found to be primarily downward across the eastern United States by as much as 6.7% per year (average of -2.6% per year), but large spatial variability was noted. The most conspicuous characteristic in the trends was over portions of the Appalachian Mountains where very small (average = -1.6% per year) and often insignificant sulfate changes were found. The Appalachian region also experienced a tendency, after removing meteorological influences, for increases in the ratio R-S of sulfate sulfur to total sulfur. Before 1991, this ratio averaged 0.33 across all sites. Appalachian increases in RS were equivalent to 0.07 during 1989-2001 (significant for most sites at the 0.05 level), or nearly 2 times the average change at the other sites. This suggests that conditions over the Appalachians became notably more efficient at oxidizing SO2 into sulfate. Alternatively, subtle changes in local deposition patterns occurred, preferentially in and near mountainous monitoring sites, that changed the SO2-sulfate balance.