Cesium, strontium, europium(III) and plutonium(IV) complexes with humic acid in solution and on montmorillonite surface

Abstract

The effect of Aldrich humic acid (HA) on the mobility of¹³⁷Cs,⁸⁵Sr,¹⁵²Eu and²³⁹Pu radionuclides was studied in Ca-montmorillonite suspensions. Verified 2-sites-2-species (2s2s) models correspond to an intensive interaction of all elements with humificated surface, what is in a remarkable contrast with the weak complexation of cesium and even strontium in solutions — the neutral ligand interaction constants β (l/mol) are log β<−9.9 and 7.56±0.21 for Cs and Sr, respectively. The result for europium complexation in solution, log β=12.49±0.18 is in a good agreement with literature data. For plutonium(IV) not only a high proton competitive constant in solution was obtained, log β β=(−0.67±0.32)+3pH, but also a strong chemisorption, which at high concentrations of humic acid (above 0.05 g/l) indicates the formation of bridge humate complexes of plutonium on the humificated surface. Logarithms of heterogeneous interaction constants ($\tilde \beta$ ₂₄ l/g) of the elements with surface humic acid are 4.47±0.23, 4.39±0.08, and 6.40±0.33 for Cs, Sr, and Eu(III), respectively, and the logarithm of the proton competitive constant ($\tilde \beta$ ₂₄, l/g) for Pu(IV) −3.80±0.72. Distribution coefficients of humic acid and metal humates between 0.01 g HA/l solution and montmorillonite were derived as logK _d(AH)=−1.04±0.11, logK _d(EuA)=1.56±0.11 and logK _d(PuA)=2.25±0.04, while the values for Cs and Sr were obtained with very high uncertainty. Speciation of the elements on montmorillonite surface is illustrated as a function of equilibrium concentration of humic acid in solution and of pH.