Influence of oxidation states on plutonium mobility during long-term transport through an unsaturated subsurface environment.

Lysimeter and laboratory studies were conducted to identify the controlling chemical processes influencing Pu(IV) mobility through the vadose zone. A 52-L lysimeter containing sediment from the Savannah River Site, South Carolina and solid PuIV(NO3)4 was left exposed to natural wetting and drying cycles for 11 years before the lysimeter sediment was sampled. Pu had traveled 10 cm, with >95% of the Pu remaining within 1.25 cm of the source. Laboratory studies showed that the sediment quickly reduced Pu(V) to Pu(IV) (the pseudo-first-order reduction rate constant, Kobs, was 0.11 h(-1)). Of particular interest was that this same sediment could be induced to release very low concentrations of sorbed Pu under oxidizing conditions, presumably by oxidation of sorbed Pu(IV) to the more mobile Pu(V) species. Transport modeling supported the postulation that Pu oxidation occurred in the lysimeter sediment; the inclusion of an oxidation term in the model produced simulations that capture the Pu depth profile data. By not including the oxidation process in the model, Pu mobility was grossly underestimated by a factor of 3.5. It is concluded that both oxidation and reduction mechanisms can play an important role in Pu transportthrough the vadose zone and should be considered when evaluating disposal of Pu-bearing wastes.