Abstract Dissolved major and trace element concentrations were determined from November 2000 to December 2003 in the lower Rhône River (France). Subsurface water samples were collected about twice a month and more regularly during flood events. An unusual trend was observed for As, Sb, Ni and Ba concentrations which increased with river discharge at the beginning of the floods, in contrast with other elements. Variations of Sb/Na and As/Na molar ratios show that it is related to higher contributions of waters from western tributaries of the Rhône River enriched in As, Sb, Ni and Ba due to ancient mining activities. These unusual variations of dissolved element concentrations are thus interpreted as mark of a water mass origin within the watershed.