Modeling Speciation and Solubility in Aqueous Systems Containing U(IV, VI), Np(IV, V, VI), Pu(III, IV, V, VI), Am(III), and Cm(III)

Abstract

A comprehensive thermodynamic model, referred to as the Mixed-Solvent Electrolyte model, has been applied to calculate phase equilibria and chemical speciation in selected aqueous actinide systems. The solution chemistry of U(IV, VI), Np(IV, V, VI), Pu(III, IV, V, VI), Am(III), and Cm(III) has been analyzed to develop the parameters of the model. These parameters include the standard-state thermochemical properties of aqueous and solid actinide species as well as the ion interaction parameters that reflect the solution’s nonideality. The model reproduces the solubility behavior and accurately predicts the formation of competing solid phases as a function of pH (from 0 to 14 and higher), temperature (up to 573 K), partial pressure of CO2 (up to $$ p_{{{\text{CO}}_{2} }} $$ = 1 bar), and concentrations of acids (to 127 mol·kg−1), bases (to 18 mol·kg−1), carbonates (to 6 mol·kg−1) and other ionic components (i.e., Na+, Ca2+, Mg2+, OH−, Cl−, $$ {\text{ClO}}_{4}^{ - } $$ , and $$ {\text{NO}}_{3}^{ - } $$ ). Redox effects on solubility and speciation have been incorporated into the model, as exemplified by the reductive and oxidative dissolution of Np(VI) and Pu(IV) solids, respectively. Thus, the model can be used to elucidate the phase and chemical equilibria for radionuclides in natural aquatic systems or in nuclear waste repository environments as a function of environmental conditions. Additionally, the model has been applied to systems relevant to nuclear fuel processing, in which nitric acid and nitrate salts of plutonium and uranium are present at high concentrations. The model reproduces speciation and solubility in the U(VI) + HNO3 + H2O and Pu(IV, VI) + HNO3 + H2O systems up to very high nitric acid concentrations ( $$ x_{{{\text{HNO}}_{3} }} \approx 0.70 $$ ). Furthermore, the similarities and differences in the solubility behavior of the actinides have been analyzed in terms of aqueous speciation.