Sequential analysis of hydrochemical data for watershed characterization

A methodology for characterizing the hydrogeology of watersheds using hydrochemical data that combine statistical, geochemical, and spatial techniques is presented. Surface water and ground water base flow and spring runoff samples (180 total) from a single watershed are first classified using hierarchical cluster analysis. The statistical clusters are analyzed for spatial coherence confirming that the clusters have a geological basis corresponding to topographic flowpaths and showing that the fractured rock aquifer behaves as an equivalent porous medium on the watershed scale. Then principal component analysis (PCA) is used to determine the sources of variation between parameters. PCA analysis shows that the variations within the dataset are related to variations in calcium, magnesium, SO4, and HCO3, which are derived from natural weathering reactions, and pH, NO3, and chlorine, which indicate anthropogenic impact. PHREEQC modeling is used to quantitatively describe the natural hydrochemical evolution for the watershed and aid in discrimination of samples that have an anthropogenic component. Finally, the seasonal changes in the water chemistry of individual sites were analyzed to better characterize the spatial variability of vertical hydraulic conductivity. The integrated result provides a method to characterize the hydrogeology of the watershed that fully utilizes traditional data.