Transuranic chemical species in groundwater. Final report

For the past several years, staff at Pacific Northwest Laboratory (PNL) have been studying the mobility of actinides, primarily plutonium, in the groundwater of a low-level disposal site. This research has provided valuable insights into the behavior of plutonium in the groundwater. Based on the analytical data and geochemical modeling, it appears that the plutonium that enters the trench, primarily in the higher oxidation states, Pu(V,VI), is rapidly reduced as the water migrates through the highly reducing sediments of the trench and is removed from the water by adsorption of the reduced plutonium, Pu(III,IV), onto the sediments. The Pu(V,VI) also appears to be reduced in the groundwater, although not as rapidly as in the trench sediments, and removed by adsorption. Because of the redox reduction that occurs during the migration of the groundwater, the system is not at redox equilibrium. Based on the discrepancies between the calculated and analytically determined redox distribution and charge-form speciation, the thermodynamic data bases for plutonium appear either to be missing or to contain incorrect thermodynamic data for several aqueous plutonium species, including the carbonate and organic complexes of plutonium. Further research is required to determine the kinetics of plutonium oxidation/reduction reactions in natural groundwater systems and to determine thermodynamic data for carbonate and organic complexes of plutonium. 52 references, 1 figure, 6 tables