Aqueous U(VI) removal by green rust and vivianite at phosphate-rich environment

Vivianite (Fe₃²⁺(PO₄)2∙8H₂O) and green rust ([Fe₄²⁺Fe₂³⁺(OH)-₁₂][SO₄²-·2H₂O]^2-), ferrous containing minerals, could remove aqueous U(VI) in 5 min. and the efficiencies of green rust were roughly 2 times higher than that of vivianite. The zeta potential measurement results implies that the better performance of green rust might be attributed to the favorable surface charge toward uranyl phosphate species. The removal behaviors of the minerals were well fitted by pseudo-second order kinetic model (R² > 0.990) indicating the dominant removal process was chemical adsorption. Effects of Ca²⁺ and CO₃^2- at pH 7 were examined in terms of removal kinetic and capacity. The kinetic constants of aqueous U(VI) were 8 and 13 times lower (0.492 x 10^-3 g/(mg∙min); 0.305 x 10^-3 g/(mg∙min)) compared to the value in the absence of the ions. The thermodynamic equilibrium calculation showed that the stable uranyl species (uranyl tri-carbonate) were newly formed at the condition. Surface investigation on the reacted mineral with uranyl phosphates species were carried out by XPS. Ferrous iron and U(VI) on the green rust surface were completely oxidized and reduced into Fe(III) and U(IV) after 7 d. It suggests that the ferrous minerals can retard U(VI) migration in phosphate-rich groundwater through the adsorption and subsequent reduction processes.