Europium redox equilibria in aqueous solution

Thermochemical data and recent advances in theoretical aqueous solution chemistry enable prediction of the relative stabilities of aqueous Eu²⁺ and Eu³⁺ over a wide range of temperatures and pressures. At low temperatures, near earth surface conditions, the aqueous geochemistry of europium should be dominated by the trivalent state, except possibly in the most reducing, alkaline pore waters of anoxic marine sediments. However, at temperatures greater than about 250°C and elevated pressures, divalent europium should predominate. Even with significant amounts of complexing, trivalent europium is not stable at elevated temperatures and pressures. Consequently, under most hydrothermal and metamorphic conditions, europium in aqueous solution should be divalent. At intermediate temperatures, around 100°C, significant activities of both Eu²⁺ and Eu³⁺, and related complexes, can occur in aqueous solutions, depending on the oxidation state and the pH of the solutions, and the activities of potential ligands such as sulfate, carbonate and chloride. The predicted stability of divalent europium in aqueous solution at elevated temperatures is consistent with the large positive europium anomalies in rare earth element patterns of high-temperature barites of hydrothermal and metamorphic origin reported by Guichard et al. 5] and with the observed depletion of europium as a result of high-temperature sericitization of feldspar-bearing assemblages discovered by Alderton et al. 1]. It is suggested that significant fractionation of europium relative to the other rare earth elements may take place during high-temperature hydrothermal alteration processes, such as in the mid-oceanic ridge systems, because of the expected stability of divalent europium during these processes.