RES³T - Rossendorf Expert System for Surface and Sorption Thermodynamics

The sorption behavior of Eu(III), Sm(III), Np(V), Pu(V), and Pu(IV) in the presence of calcite and as a function of pH and carbonate alkalinity was measured by batch sorption experiments. Eu(III) and Sm(III) sorption is similar, consistent with their observed aqueous speciation and precipitation behavior. For both rare earth elements, sorption decreases at the highest and lowest measured pHs. This is likely the result of speciation changes both of the calcite surface and the sorber. An increase in the equilibrium CO₂(g) fugacity results in a shift in the sorption behavior to lower pH, consistent with a predicted aqueous speciation shift. Np(V) and Pu(V) sorption exhibited a strong pH dependence. For Np(V), K_ds range from 0 to 217 mL/g suggesting that carbonate aqueous speciation as well as changes in the calcite surface speciation greatly affect Np(V) sorption to the calcite surface. Similar behavior was found for Pu(V). Pu(IV) sorption is also strongly pH dependent. Sorption decreases significantly at high pH as a result of Pu-carbonate complexation in solution. A surface complexation model of Sm(III), Eu(III), Np(V), Pu(V), and Pu(IV) sorption to the calcite surface was developed based on the calcite surface speciation model of Pokrovsky and Schott [1]. Sorption data were fit using one or two surface species for each sorber and could account for the effect of pH and CO₂(g) fugacity on sorption. A relatively poor model fit to Pu(IV) sorption data at high pH may result from our poor understanding of Pu(IV)-carbonate aqueous speciation. While our surface complexation model may not represent a unique solution to the sorption data, it illustrates that a surface complexation modeling approach may adequately describe the sorption behavior of a number of radionuclides at the calcite surface over a range of solution conditions.