Long-Term Modeling of Plutonium Solubility at a Desert Disposal Site, Including CO2 Diffusion, Cellulose Decay, and Chelation

Abstract

The solubility of plutonium was estimated for waste buried at the Greater Confinement Disposal site in Nevada. The EQ3/6 thermochemical database was modified to include recent data on Pu complex formation, and the solubilities of two critical phases (probertite (CaNaB5O9·5H2O), added as a backfill material; and Ca sac-charate) were determined by experiment. Reaction path runs were used to model effects of cellulose degradation, including complexation of actinides by organic acids and carbonate, decay of the complexing agents, and the buildup and diffusive loss of CO2 through the permeable alluvium. For most waste interaction scenarios, long-term (≈103 years) concentrations of Pu in pore waters are ≤10−7 molal and are dominated by carbonate complexes, although organic complexes could dominate in the first ≈103 years. In unusual circumstances, carbonation of buried lithium could produce very high Pu solubilities; however, even in such a system, a slight lowering of the effective redox potential dramatically lowers Pu solubility. A sensitivity analysis suggests that the “base case” calculations are conservative, tending to overestimate long-term solubility, with the system redox and the identity of the organic acids the major sources of uncertainty.