Detecting subtle hydrochemical anomalies with multivariate statistics: an example from ‘homogeneous’ groundwaters in the Great Artesian Basin,Australia

The major ion composition of Great Artesian Basin groundwater in the lower Namoi River valley is relatively homogeneous in chemical composition. Traditional graphical techniques have been combined with multivariate statistical methods to determine whether subtle differences in the chemical composition of these waters can be delineated. Hierarchical cluster analysis and principal components analysis were successful in delineating minor variations within the groundwaters of the study area that were not visually identified in the graphical techniques applied. Hydrochemical interpretation allowed geochemical processes to be identified in each statistically defined water type and illustrated how these groundwaters differ from one another. Three main geochemical processes were identified in the groundwaters: ion exchange, precipitation, and mixing between waters from different sources. Both statistical methods delineated an anomalous sample suspected of being influenced by magmatic CO₂ input. The use of statistical methods to complement traditional graphical techniques for waters appearing homogeneous is emphasized for all investigations of this type. Copyright © 2006 John Wiley & Sons, Ltd.