Understanding the geochemistry and contamination of rivers affected by anthropogenic activities is paramount to water resources management. The Asopos river basin in central Greece is facing environmental quality deterioration threats due to industrial, urban and agricultural activities. Here, the geochemistry of river sediments and adjacent soil in terms of major and trace elements (Al, Ca, Mg, Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn) and the geochemical composition of surface water in terms of major ions, trace elements and nutrients along the Asopos river basin were determined. In addition, this study characterized potential nitrate sources through the analysis of stable isotope composition of NO₃^- (δ¹⁵Ν-ΝΟ₃^- and δ¹⁸Ο-ΝΟ₃^-). Results indicated that specific chemical constituents including nutrients (NO₂^-, NH₄⁺, PO₄^3-) and major ions (Na⁺, Cl^-) were highest in the urban, industrialized and downstream areas. On the other hand, nitrate (NO₃^-) concentration in river water (median 7.9 mg/L) showed a decreasing trend from the upstream agricultural sites to the urban area and even more in the downstream of the urban area sites. Ionic ratios (NO₃^-/Cl^-) and δ¹⁵Ν-ΝΟ₃^- values (range from +10.2 ‰ to +15.7 ‰), complemented with a Bayesian isotope mixing model, clearly showed the influence of organic wastes from septic systems and industries operating in the urban area on river nitrate geochemistry. The interpretation of geochemical data of soil and river sediment samples demonstrated the strong influence of local geology on Cr, Fe, Mn and Ni content, with isolated samples showing elevated concentrations of Cd, Cu, Pb and Zn, mostly within the industrialized urban environment. The calculation of enrichment factors based on the national background concentrations provided limited insights into the origin of geogenic metals. Overall, this study highlighted the need for a more holistic approach to assess the impact of the geological background and anthropogenic activities on river waters and sediments.

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