Abstract

Waters from springs at Vals-les-Bains result from the mixing of a CO 2-rich, highly mineralized water with dilute, shallow subsurface water. Total content of dissolved species vary from 5 mmol/1 to 100 mmol/1. For many elements, mixing of these waters is non-linear (non-conservative) and further water-rock reactions take place. The pH is controlled by CO 2 outgassing, redox conditions are controlled by both the iron hydroxide-siderite buffer and the introduction of oxygen with shallow subsurface waters. Among the major elements, concentrations of Ca, Mg, Mn, Fe, are related to mixing, CO 2 outgassing and carbonate precipitation. Uranium shows a complex behaviour controlled by carbonate complexing, redox conditions, mixing of waters and leaching from the rocks. The 234U 238U activity ratio is near secular equilibrium. In the more dilute waters, dissolved rare earth element (REE) patterns are almost flat with a slight negative Eu anomaly. In the concentrated waters, heavy rare earth elements (Gd-Yb, HREE) are strongly enriched relative to light rare earth elements (Ce-Eu, LREE). We relate the enrichment in HREE to water chemistry and to complexing with carbonate species.

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