| Summary: | To avoid the improper disqualification of a watershed for which the water–rock interaction (WRI) may produce trace element concentrations exceeding established guidelines, it is of the utmost importance to properly establish natural geochemical backgrounds. Using the example of the crystalline Upper Loire River Basin, we are proposing a methodology based on the selection and chemical characterization of water and sediment samples from 10 monolithologic watersheds supposedly lowly impacted by anthropogenic inputs. We collected water samples from each watershed’s spring down to its outlet and measured dissolved major, minor and selected trace elements (Al, As, Ba, Cd, Co, Cr, Cs, Cu, La, Ni, Pb, U, V and Zn) at low- and high-water stages. Results show that the chemical signature of the stream waters is controlled by mineral weatherability rather than by the available rock stock. As a result, the variability in dissolved metal concentrations between the principal lithologies is similar to that observed within each of them. While some elements mostly result from WRI, others clearly identify high inputs from topsoil leaching. Comparison with published data evidences the need to subdivide studied watersheds into distinct sectors, according to the distance from the spring, in order to define reliable natural backgrounds.
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