To define water quality, the European Water Framework Directive (WFD) demands complex assessments through physicochemical, biological, and hydromorphological controls of water bodies. Since the biological assessment became the central focus with hydrochemistry playing a supporting role, an evaluation of the interrelationships within this approach deems necessary. This work identified and tested these relationships to help improve the quality and efficiency of related efforts. Data from the 384 km(2) Weisseritz catchment (eastern Erzgebirge, Saxony, Germany and northern Bohemia, Czech Republic) were used as a representative example for central European streams in mountainous areas. The data cover the time frame 1992 to 2003. To implement WFD demands, the analysis was based on accepted German methods and classifications, WFD quality standards, and novel German methods for the biological status assessment. Selected chemical parameters were compared with different versions of the German Saprobic Index, based on macroinvertebrate indicator taxa. Relevant dependencies applicable for integrated stream assessment were statistically tested. Correlation analysis showed significant relationships. The highest scores were found for nutrients (NO(2)(-), N(inorg), and total N), salinity (Cl(-), SO(4)(2-), conductivity), and microelements (K(+), Na(+), Ca(2+), Mg(2+)). The Saprobic Index used in the Integrated Assessment System for the Ecological Quality of Streams and Rivers throughout Europe using Benthic Macro-invertebrates program seems to be the most sensitive indicator to correlate with chemical parameters.