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Sorption of Th(IV) onto two-line ferrihydrite and magnetite in NaClO4 solutions has been studied as a function of pH and ionic strength revealing that sorption onto both solids increases with pH while it is independent on ionic strength. Sorption capacity of both solids is high, the maximum sorption (almost 100% of Th(IV)) occurs at pH higher than 3.5 for ferrihydrite, and higher than 3.0 for magnetite. Sorption variation with pH was modeled with three different models using the FITEQL 4.0 code: non-electrostatic model, constant capacitance model, and diffuse-double layer model. In all cases, good fit to the experimental data is obtained with one-species: a corner-sharing bidentate-mononuclear surface complex, (triple bond; length of mdashFeO)2Th2+, which coincides with the surface complex postulated on these solids surface in previous spectroscopic studies; however, the monodentate species triple bond; length of mdashFeOThOH2+ also gives a satisfactory fit. Under the experimental conditions of the present study, any effect of possible thorium colloid formation is negligible.

The uranium sorbed onto commercial magnetite has been characterized by using two different spectroscopic techniques such as X-ray photoelectron spectroscopy (XPS), and extended X-ray absorption fine structure (EXAFS). Magnetite samples have been put in contact with uranium(VI) solutions in conditions in which a high uranium uptake is expected. After several days, the magnetite surface has been analysed by XPS and EXAFS. The XPS results obtained are not conclusive regarding the uranium oxidation state in the magnetite surface. On the other hand, the results obtained with the EXAFS technique show that the uranium–magnetite sample spectrum has characteristics from both the UO2 and schoepite spectra, e.g. a relatively high coordination number of equatorial oxygens and two axial oxygens, respectively. These results would indicate that the uranium sorbed onto magnetite would be a mixture of uranium(IV) and uranium(VI).