ABSTRACT: Determination of background values in surface waters belongs to fundamental tasks in the context of Water Framework Directive. The determined values bring information on assessment of good status of surface bodies. Different approaches, specifically statistical methods are described in the paper. Utilization of the techniques is given for three selected regions represented by crystalline, carbonate and flysch geological settings. All areas represent mountainous territory with low level of human intervention to natural environment. To examine the different methods - chlorides, sulphates, nitrates. zinc, arsenic and cadmium have been chosen among the analysed parameters. Results have shown that the complex approach is preferred to characterize the geogene background. Sensitive approach to select an optimal procedure and amount and representativeness of the data set are crucial among others. Various statistical techniques result in different background concentrations. Similarly, the different rock environment has an influence on background contents of selected analysed parameters in evaluated catchments.