THE AQUEOUS GEOCHEMISTRY OF THE RARE-EARTH ELEMENTS - CRITICAL STABILITY-CONSTANTS FOR COMPLEXES WITH SIMPLE CARBOXYLIC-ACIDS AT 25-DEGREES-C AND 1-BAR AND THEIR APPLICATION TO NUCLEAR WASTE MANAGEMENT

The mobility of the rare-earth elements (REE) is relevant to nuclear waste management in that REE are produced during radioactive decay in high-level waste and they are good chemical analogues for some of the trivalent actinides (e.g., Am3+ and Cm3+). Carboxylic acids are present naturally in many geologic fluids and also have been disposed of along with radionuclides; such complexing agents may increase the mobility of the REE (actinides) and need to be considered in geochemical models of the transport of these metals into the far-field environment. In this study, available stability constants for the formation of REE complexes with the organic ligands acetate, adipate, benzoate, citrate, ETDA, formate, fumarate, glutarate, glycolate, alpha-hydroxyisobutyrate, isobutyrate, lactate, maleate, malonate, alpha-mercaptoacetate, oxalate, m-phthalate, o-phthalate, propionate, salicylate and succinate have been critically evaluated. Those stability constants considered most reliable were, where necessary, corrected to 25-degrees-C using published enthalpy data and, where possible, corrected to infinite dilution using a model based on the Pitzer equations. These data provide the basis for future geochemical modelling of the behavior of the REE in nuclear waste disposal sites. Some simple geochemical calculations presented in this paper suggest that monodentate ligands such as acetate are unlikely to contribute significantly to REE (actinide) mobility in most nuclear waste disposal environments. However, ligands capable of chelating in a multi-dentate manner, e.g., oxalate, malonate, succinate, EDTA, etc., may increase the mobility of trivalent lanthanides and actinides significantly, even though their concentrations are lower than monodentate ligands in most natural environments. However, the effectiveness of any of these organic ligands depends on the concentrations of competing ions, such as Ca2+, Mg2+, etc., being low relative to the total ligand concentration.