Neptunium interaction with uranium dioxide in aqueous solution

Neptunium, Np(V) and Np(IV), sorption onto uranium dioxide surface was studied at various values of pH. Sorption was studied in two sets of experiments with different redox conditions that correspond to either Np(V) (Set 1) or Np(IV) (Set 2) in solution. In Set 1 the reduction of Np(V) was established when low pH solution covered a UO2 surface. When the pH increased, the sorption of neptunium is decreased. At pH > 5.5 neptunium sequestration from solution is governed by Np(V) sorption onto UO2.25. In Set 2 (the more anoxic conditions) complete neptunium sorption is established at pH > 2: it is present in the tetravalent form over the whole pH range. The proposed mechanisms of neptunium sorption was suggested by using pH sorption edges of Th(IV) as an analog to Np(IV) onto UO2 and Np(V) onto ThO2. The UO2 surface was characterized by X-ray photoelectron spectroscopy (XPS) after equilibration with aqueous solutions at different pH values.