We have studied the surface interaction between tetravalent plutonium and two different steel corrosion products: magnetite, which is the final product of the anoxic corrosion of steel, and goethite, which exemplifies a further oxidation of the steel surface due to the presence of active oxidants in the system. The pH of the experiments has been varied from 2 to 10 and the ionic strength from 0.001 to 0.1 M NaClO4. All the sorption experiments were carried out under N2 atmosphere. No significant effect of ionic strength was observed under the conditions studied. The pHpcz of the solids (7.78 for goethite and 6.95 for magnetite) was determined by modelling potentiometric titration data. The results of the experiments show that the sorption edge of plutonium occurs between pH 3 and 4 when using goethite as a sorbing surface and between pH 4 and 5 when magnetite is used. We have modelled the sorption data by using a simple surface complexation approach with no electrostatic term. The model used involves a reduction process of Pu(IV) to Pu(III) in the presence of magnetite, which can be explained by the interaction of the actinide with the ferrous iron present in the solid. In the case of the experiments conducted with goethite, this reduction process is not possible and, therefore, in the model we have included the sorption of tetravalent Pu. |
