Fluorescence spectroscopy has become a widely used technique to characterize dissolved organic matter (DOM) and organic hazardous micro-pollutants in natural and human-influenced water bodies. Especially in rivers highly impacted by municipal and industrial wastewater treatment plants' effluents, the fluorescence signal at low-flow is mainly dominated by these discharges. At river high-flow, their influence decreases due to dilution effects, and at the same time, other compounds of DOM, stemming from diffuse inputs, can increase or even dominate. Therefore, whereas the analysis of DOM is little informative on the changing sources and pathways of emissions, fluorescence spectroscopy can enhance our understanding and our possibilities of monitoring such dynamics in river catchments. This paper analyzed samples from seven high-flow events in an Austrian river. Firstly, independent DOM components were discriminated using a parallel factor analysis (PARAFAC) to show the varying composition of DOM during different phases of high-flow events. Furthermore, partial least squares (PLS) and sparse PLS (sPLS) regression were applied to identify excitation and emission wavelengths, serving as proxy parameters for quantifying dissolved organic carbon (DOC) and chloride. The PLS models show the best prediction accuracy but use the entire excitation-emission matrix in exchange. In selecting predictors, the use of excitation and emission wavelengths adjusted via sPLS is superior to the extracted PARAFAC components. The sPLS model yields 16 wavelength combinations for DOC (RMSEsPLS = 0.41 mg L-1) and 18 wavelength combinations for chloride (RMSEsPLS = 2.21 mg L-1). In contrast to other established optical measurement methods, which require different calibrations for low- and high-flow conditions, these models based on sPLS succeed in quantifying those parameters across the entire range of flow conditions and events of various magnitudes with a relative precision of about 5 %. These results show how the application of multivariate statistical techniques enhances the exploitation of the information provided by fluorescence spectroscopy.