Sorption / Desorption / Reduction / Neptunium / Magnetite / HematiteSummary. Sorption and desorption experiments of Np on magnetite and hematite under aerobic and anaerobic conditions were carried out to investigate the possibility of reduction of Np(V) to Np(IV) at pH 4 to 8 within 7 days. The amount of sorbed Np on magnetite under anaerobic conditions was about 2 or 3 times greater than that under aerobic conditions. Furthermore, the results of desorption experiments indicated that the dominant sorption behavior of Np on magnetite under anaerobic conditions was quite different from that under aerobic conditions. The oxidation state of Np sorbed on the iron oxides was determined by extraction technique using 0.5 M TTA in xylene and 2.0 M HNO 3 solution from the solid phase after sorption experiment. 90% and 10% of extracted Np was Np(IV) for magnetite system under anaerobic and aerobic conditions, respectively. On the other hand, almost 100% of extracted Np was Np(V) for hematite system under both aerobic and anaerobic conditions. These results indicated that Np(V) was reduced to Np(IV) by Fe(II) in magnetite.Redox reaction between Np(V) and Fe(II) was also studied in homogeneous solution without solid to decide if Fe(II) ions released from magnetite into silution or Fe(II) on the solid cause the reduction. Only 6% of Np(V) was reduced by Fe(II) at pH = 4 and 6 even after 7 days. According to this result, it was conjectured that the reduction of Np(V) to Np(IV) takes place not in the liquid phase by Fe(II) ion but on the surface of magnetite.
Reduction rate / Sorption / Neptunium(V) / Neptunium(IV) / MagnetiteSummary. The sorption kinetics of neptunium on magnetite was investigated under both aerobic and anaerobic conditions in 0.1 mol L −1 NaNO 3 at pH = 5.7 to 5.9. It was found that the sorption of neptunium on magnetite reaches an equilibrium in 1 h under aerobic conditions, while it takes 10 h or more to reach the equilibrium under anaerobic conditions. The difference in sorption kinetics between aerobic and anaerobic conditions took place because sorption kinetics under the anaerobic condition involved the reduction of Np(V) to Np(IV), confirmed by an extraction technique using 0.5 mol L −1 TTA in xylene and 2.0 mol L −1 HNO 3 solution. The reduction rate of Np(V) by Fe(II) in magnetite was calculated in solution with magnetite. It was found that Np(V) was reduced 1000 or more times faster in solution with magnetite than the Np(V) reduction by Fe(II) ions in homogeneous solution. It was revealed that the reduction of Np(V) in solution with magnetite took place on the surface of magnetite.
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