Geochemical characterization of karst groundwater in the cradle of humankind world heritage site,South Africa

The karst of the Cradle of Humankind World Heritage Site plays a major role in the assimilation or carrying of acid mine drainage, sewage effluent return flow and agricultural run-off. Infiltration of contaminated water has altered the chemical composition of the natural waters of the karst system. A multivariate statistical method in combination with conventional geochemical and spatial analysis was applied on groundwater and surface water quality samples to determine the spatial extent of hydrochemical impacts from different anthropogenic sources. The application of hierarchical cluster analysis of the major ions (148 samples) recognised three distinct hydrochemical regimes. Cluster 1 is moderately mineralized, especially with regard to chloride, nitrate and sulphate, cluster 2 has a low mineralization with all elements well within the recommended drinking water limits of South Africa and cluster 3 represents highly mineralized samples taken in the vicinity of decanting mineshafts. The cluster solution is confirmed by a simple mixing model, indicating varying contributions of three identified end members (acid mine drainage, treated sewage effluents and pristine dolomitic groundwater) to the groundwater quality in the catchment. The combination of statistical, geochemical and spatial methods in conjunction with end-member mixing analysis provides a reliable method to understand the processes responsible for the groundwater quality variations and to assist in the identification of anthropogenic impacts.