Modelling colloid association with plutonium: The effect of pH and redox potential

An analytical expression that evaluates the effect of pH and the redox potential (E) on Pu-colloid association was studied on a model basis. It includes surface complexation with one type of surface site and its formulation leads to a distribution coefficient (Kd) as a function of the pH (hydrolysis) and E (redox sensitive species). The formulation also considers the values of the stability and hydrolysis constants for all species present in solution and associated at the surface. Correlations between hydrolysis and surface complexation constants reported in the literature have been applied systematically to evaluate sorption of all species for each colloid system. The presence of ligands in solution was also taken into account. The model was applied to study the association of Pu onto colloids coated with AlOH, FeOH or SiOH groups in the presence and in the absence of carbonates in solution. The tests performed with the model suggest that the oxidation of Pu(III) to Pu(IV) has the potential to increase sorption, as demonstrated by the increased Kd values. Under natural conditions Pu may be present at oxidation states of (III)--(VI), and the effect of redox potential is significant because of the differences in the sorption of each oxidation state. When carbonates are present in the solution, the calculated values of distribution coefficient were lower than those calculated in the absence of carbonates, particularly in the case of Pu(VI). The Kd values obtained with the developed model are compared with experimental values reported for the sorption of Pu onto colloids. This model can equally be applied to study the sorption of other redox sensitive elements.