Sorption isotherms and apparent concentration limits for Tc(VII) and Np(V) for a variety of groundwater/basalt systems were determined using Grande Ronde basalt samples representative of the Hanford Site candidate high-level waste repository. Under oxic redox conditions (air present), little or no sorption of technetium was observed; neptunium exhibited low to moderate sorption ratios. Under anoxic redox conditions (oxygen-free), low to moderate sorption of technetium was often observed, but the extent of sorption was highly dependent upon the groundwater composition and the method of pretreatment (if any) of the basalt. Sorption isotherms for technetium under reducing redox conditions (hydrazine added) indicate an apparent concentration limit of approximately 10−6 mol/L Tc. No apparent concentration limit was found for neptunium for concentrations in groundwater up to.∼10−6 mol/L and 8 × 10−7 mol/L under oxic and reducing (hydrazine added) redox conditions, respectively.

Valence control and valence analysis experiments suggest that the sorption or precipitation of Tc and Np from groundwater in the presence of basalt may result from a heterogeneous reaction occurring on the surface of the basalt. One of the critical factors of this reduction reaction appears to be the accessibility of the reactive ferrous iron component of the basalt. The laboratory simulation of groundwater redox conditions representative of the repository environment through the use of solution phase redox reagents is of questionable validity, and information obtained by such experimental methods may not be defensible for site performance assessment calculations. Anoxic experiments conducted in an argon-filled glove box appear better suited for the laboratory simulation of in situ redox conditions.