Neptunium solution, behavior

The oxidation-reduction behaviors of neptunium, plutonium and americium in basic solution have been determined via polarographic and coulometric studies (6-9). These studies, which showed that the more soluble (V), (VI), and (VII) oxidation states of these actinides are stable in alkaline solution under certain redox conditions, helped identify possible actinide species and oxidation states in our experiments. Actual identification of radioelement oxidation states was not done in the present experiments. 

Neptunium and plutonium sorption behaviors were remarkably similar, implying that they had similar sorption reactions and solution species. Both NaOH and NaA102 decreased neptunium and plutonium sorption. Several explanations can be offered to rationalize this behavior. First, NaOH and NaAlO, may have reacted with the sediment minerals to yield solids of lower sorptive capacity. Aluminate ion, as an anionic species, also may have competed with the similar neptunate and plutonate anions for sorption sites. Finally, sodium hydroxide may have stabilized the hydrolyzed Np02(0H) and Pu02(0H)2" species in solution, as was shown in the solubility tests, and prevented sorption. Explanation of the effect of NaOH and NaA102 on neptunium and plutonium sorption will require further investigation. 

The sorption behaviors of neptunium and plutonium were similar, thus confirming their suspected similarities in solution chemistry. Both NaOH and NaA102 decreased neptunium and... 

Investigations of the solid-state chemistry of the americium oxides have shown that americium has properties typical of the preceding elements uranium, neptunium, and plutonium as well as properties to be expected of a typical actinide element (preferred stability of the valence state 3-j-). As the production of ternary oxides of trivalent plutonium entails considerable difficulties, it may be justified to speak of a discontinuity in the solid-state chemical behavior in the transition from plutonium to americium. A similar discontinuous change in the solid-state chemical behavior is certainly expected in the transition Am Cm. Americium must be attributed an intermediate position among the neighboring elements which is much more pronounced in the reactions of the oxides than in those of the halides or the behavior in aqueous solution. 

McCubbin D. and Leonard K. S. (1997) Laboratory studies to investigate short-term oxidation and sorption behavior of neptunium in artificial and natural seawater solutions. Mar. Chem. 56, 107-121. 

The sucessful experiments for the retention of plutonium onto alumina from TTN0 -HF solution gave enough confidence to recomend the proposed method to separate traces of plutonium from waste solutions in the presence of macroamounts of uranium (VI). Of course, only macroamounts of thorium, uranium (IV) and rare earths are serious interfering ions, since they precipitate with HF. The behavior expected for neptunium in the same system should be similar to plutonium, thorium and rare earths. The retention of neptunium from HNO - HF solutions is in progress. The sorption yield for Pu was around 95%. The sorption mechanism is not well established. Figure 3 shows the proposed flowsheet for recovery of Pu traces from reprocessing waste solutions. 

The differences in sorptive behavior of Th, Pu, U, and Np are evident by examining Table II. Plutonium and thorium isotopes at tracer concentrations (parts per billion, element mass/clay mass) were equilibrated for 24 hours with the < 2-pm fraction (clay) of a silt loam soil. The pH of the equilibration solutions was 6.5 and the aqueous phase contained Ca at a concentration of 5 mM. Both tetravalent actinides failed to remain 1n solution. Whether this is a direct function of sorption mechanisms or simply related to the solubility of the ions in solution is not distinguished by the results. Uranyl ion was not removed to the same extent as the tetravalent species. Neptunium(V) sorbed very poorly. It should be noted that while Np(V) is a mono-charged cation, Np02+ does not sorb like Na+. 

Neptunium. Np is in a class with Pa no efforts have been made to use it as a fuel solute, but consideration has been given to its formation in and removal from blanket solutions of [30a]. The chemistry of neptunium has been reviewed by Hindman et al. [30b], and the hydrolytic behavior has been reviewed by Kraus [30c]. Continuous separation of Np239 would provide a Pu product of high purity by radioactive decay, whereas plutonium recovered from long-term irradiation of usually contains appreciable amounts of Pu °. Spectrophotometric cells for use at elevated temperatures and pre.ssures in the study of the chemistry of neptunium (and other materials) have recently been developed by Wag-gener [30d] and have been used to measure the absorption spectra of dilute neptunium perchlorate in its six-, five-, four-, and three-valence states, using heavy w ater as the solvent. Dilute solutions of neptunyl nitrate in nitric acid have been so studied at temperatures up to 250°C the pentavalent state was found to be stable under the test conditions [30e]. 

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