Water source characterization through spatiotemporal patterns of major,minor and trace element stream concentrations in a complex,mesoscale German catchment

The link between spatiotemporal patterns of stream water chemistry and catchment characteristics for the mesoscale Dill catchment (692 km²) in Germany is explored to assess the catchment scale controls on water quality and to characterize water sources. In order to record the spatiotemporal pattern, ‘snapshot sampling’ was applied during low, mean and high flow, including 73 nested sites throughout the catchment. Water samples were analysed for the elements Li, B, Na, Mg, Al, K, Ca, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Rb, Sr, Mo, Ba, Pb and U using inductively‐coupled‐plasma mass spectrometry, and for electric conductivity and pH. Principle component analysis and hierarchical cluster analysis were used to find typical element associations and to group water samples according to their hydrochemical fingerprints. This revealed regional hydrochemical patterns of water quality which were subsequently related to catchment attributes to draw conclusions about the controls on stream chemistry. It was found that various lithologic signals and anthropogenic point source inputs controlled the base flow hydrochemistry. During increased flows, stream waters were diluted causing additional hydrochemical variability in response to heterogeneous precipitation inputs and differences in aquifer storage capacities. The hydrochemical patterns further displayed in‐stream mixing of waters. This implied, that stream waters could be apportioned to the identified water sources throughout the catchment. The basin‐wide hydrochemical variability has the potential to outrange the tracer signatures typically inferred in studies at the hillslope scale and is able to strongly influence the complexity of the catchment output. Both have to be considered for further catchment scale tracer and modelling work. Despite the likelihood of non‐conservative behaviour, the minor and trace elements enhanced the rather qualitative discrimination of the various groundwater types, as the major cations were strongly masked by point source inputs. Copyright © 2007 John Wiley & Sons, Ltd.