Mechanism of Phosphorus Removal from Hanford Tank Sludge by Caustic Leaching

Two experiments were conducted to explore the mechanism by which phosphorus is removed from Hanford tank sludge by caustic leaching. In the first experiment, a series of phosphate salts were treated with 3 M NaOH under conditions prototypic of the actual leaching process to be performed in the Waste Treatment and Immobilization Plant (WTP). The phosphates used were aluminum phosphate, bismuth phosphate, chromium(III) phosphate, and -tri-calcium phosphate; all of these phases have previously been determined to exist in Hanford tank sludge. The leachate solution was sampled at selected time intervals and analyzed for the specific metal ion involved (Al, Bi, Ca, or Cr) and for P (total and as phosphate). The solids remaining after completion of the caustic leaching step were analyzed to determine the reaction product. In the second experiment, the dependence of P removal from bismuth phosphate was examined as a function of the hydroxide ion concentration. It was anticipated that a plot of log[phosphate] versus log[hydroxide] would provide insight into the phosphorus-removal mechanism. This report describes the test activities outlined in Section 6.3.2.1, Preliminary Investigation of Phosphate Dissolution, in Test Plan TP-RPP-WTP-467, Rev.1. The objectives, success criteria, and test conditions of Section 6.3.2.1 are summarized here

Separating the Minor Actinides Through Advances in Selective Coordination Chemistry

This report describes work conducted at the Pacific Northwest National Laboratory (PNNL) in Fiscal Year (FY) 2012 under the auspices of the Sigma Team for Minor Actinide Separation, funded by the U.S. Department of Energy Office of Nuclear Energy. Researchers at PNNL and Argonne National Laboratory (ANL) are investigating a simplified solvent extraction system for providing a single-step process to separate the minor actinide elements from acidic high-level liquid waste (HLW), including separating the minor actinides from the lanthanide fission products

Ion Recognition Approach to Volume Reduction of Alkaline Tank Waste by Separation of Sodium Salts

The purpose of this research involving collaboration between Oak Ridge National Laboratory (ORNL) and Pacific Northwest National Laboratory (PNNL) is to explore new approaches to the separation of sodium hydroxide, sodium nitrate, and other sodium salts from high-level alkaline tank waste. The principal potential benefit is a major reduction in disposed waste volume, obviating the building of expensive new waste tanks and reducing the costs of low-activity waste immobilization. Principles of ion recognition are being researched toward discovery of liquid-liquid extraction systems that selectively separate sodium hydroxide and sodium nitrate from other waste components. The successful concept of pseudohydroxide extraction using fluorinated alcohols and phenols is being developed at ORNL and PNNL toward a greater understanding of the controlling equilibria, role of solvation, and of synergistic effects involving crown ethers. Synthesis efforts are being directed toward enhanced sodium binding by crown ethers, both neutral and proton-ionizable. Studies with real tank waste at PNNL will provide feedback toward solvent compositions that have promising properties

Selective Media for Actinide Collection and Pre-Concentration: Results of FY 2006 Studies

In this work, we have investigated new materials for potential use in automated radiochemical separations. The work can be divided into three primary tasks: (1) synthesis of new ligands with high affinity for actinide ions, (2) evaluation of new materials for actinide ion affinity, and (3) computational design of advanced ligand architectures for highly selective binding of actinide ions. Ligand Synthesis Work was conducted on synthesizing Kl?ui ligand derivatives containing functionalized pendant groups on the cyclopentadienyl ring. The functionalized pendent groups would allow these ligands to be attached to organic and inorganic solid supports. This work focused on synthesizing the compound Na[Cp?Co(PO(OC2H5)2)3], where Cp?= C5H4C(O)OCH3. Synthesizing this compound is feasible, but the method used in FY 2006 produced an impure material. A modified synthetic scheme has been developed and will be pursued in FY 2007. Work was also initiated on synthesizing bicyclic diamides functionalized for binding to polymeric resins or other surfaces. Researchers at the University of Oregon are collaborators in this work. To date, this effort has focused on synthesizing and characterizing a symmetrically substituted bicyclic diamide ligand with the ?COOH functionality. Again, this synthetic effort will continue into FY 2007. Separations Material Evaluation Work was conducted in FY 2006 to provide a more extensive set of data on the selectivity and affinity of extraction chromatography resins prepared by sorption of Kl?ui ligand onto an inert macroreticular polymeric support. Consistent with previous observations, it was found that these materials strongly bind tetravalent actinides. These materials also adsorb trivalent actinides at low nitric acid concentrations, but the affinity for the trivalent actinides decreases with increasing nitric acid concentration. These materials have relatively low affinity for U(VI), but they do sorb U(VI) to a greater extent than Am(III) at [HNO3] > 0.3 M. Preliminary results suggest that the Kl?ui resins can separate Pu(IV) from sample solutions containing high concentrations of competing ions. Conceptual protocols for recovery of the Pu from the resin for subsequent analysis have been proposed, but further work is needed to perfect these techniques. Work on this subject will be continued in FY 2007. Automated laboratory equipment (in conjunction with Task 3 of the NA-22 Automation Project) will be used in FY 2007 to improve the efficiency of these experiments. The sorption of actinide ions on self-assembled monolayer on mesoporous supports materials containing diphosphonate groups was also investigated. These materials also showed a very high affinity for tetravalent actinides, and they also sorbed U(VI) fairly strongly. Computational Ligand Design An extended MM3 molecular mechanics model was developed for calculating the structures of Kl?ui ligand complexes. This laid the groundwork necessary to perform the computer-aided design of bis-Kl?ui architectures tailored for Pu(IV) complexation. Calculated structures of the Kl?ui ligand complexes [Pu(Kl?ui)2(OH2)2]2+ and [Fe(Kl?ui)2]+ indicate a ''bent'' sandwich arrangement of the Kl?ui ligands in the Pu(IV) complex, whereas the Fe(III) complex prefers a ''linear'' octahedral arrangement of the two Kl?ui ligands. This offers the possibility that two Kl?ui ligands can be tethered together to form a material with very high binding affinity for Pu(IV) over Fe(III). The next step in the design process is to use de novo molecule building software (HostDesigner) to identify potential candidate architectures

Ion Recognition Approach to Volume Reduction of Alkaline Tank Waste by Separation of Sodium Salts

The purpose of this research involving collaboration between Oak Ridge National Laboratory (ORNL) and Pacific Northwest National Laboratory (PNNL) is to explore new approaches to the separation of sodium hydroxide, sodium nitrate, and other sodium salts from high-level alkaline tank waste. The principal potential benefit is a major reduction in disposed waste volume, obviating the building of expensive new waste tanks and reducing the costs of vitrification. Principles of ion recognition are being researched toward discovery of liquid-liquid extraction systems that selectively separate sodium hydroxide and sodium nitrate from other waste components. The successful concept of pseudo hydroxide extraction using fluorinated alcohols and phenols is being developed at ORNL and PNNL toward a greater understanding of the controlling equilibria, role of solvation, and of synergistic effects involving crown ethers. Synthesis efforts are being directed toward enhanced sodium binding by crown ethers, both neutral and proton-ionizable. Studies with real tank waste at PNNL will provide feedback toward solvent compositions that have promising properties

Sonochemical Digestion of Soil and Sediment Samples

This work was performed as part of a broader effort to automate analytical methods for determination of plutonium and other radioisotopes in environmental samples. The work described here represented a screening study to determine the potential for applying ultrasonic irradiation to sample digestion. Two standard reference materials (SRMs) were used in this study: Columbia River Sediment and Rocky Flats Soil. The key experiments performed are listed below along with a summary of the results. The action of nitric acid, regardless of its concentration and liquid-to-solid ratio, did not achieve dissolution efficiency better that 20%. The major fraction of natural organic matter (NOM) remained undissolved by this treatment. Sonication did not result in improved dissolution for the SRMs tested. The action of hydrofluoric acid at concentrations of 8 M and higher achieved much more pronounced dissolution (up to 97% dissolved for the Rocky Flats soil sample and up to 78% dissolved for the Columbia River Sediment sample). Dissolution efficiency remains constant for solid-to-liquid ratios of up to 0.05 to 1 and decreases for the higher loadings of the solid phase. Sonication produced no measurable effect in improving the dissolution of the samples compared with the control digestion experiments. Combined treatment of the SRM by mixtures of HNO3 and HF showed inferior performance compared with the HF alone. An adverse effect of sonication was found for the Rocky Flats soil material, which became more noticeable at higher HF concentrations. Sonication of the Columbia River sediment samples had no positive effect in the mixed acid treatment. The results indicate that applying ultrasound in an isolated cup horn configuration does not offer any advantage over conventional ''heat and mix'' treatment for dissolution of the soil and sediment based on the SRM examined here. This conclusion, however, is based on an approach that uses gravimetric analysis to determine gross dissolution efficiency. This approach does not allow any conclusion regarding the possible advantage of sonication in selective dissolution of plutonium traces incorporated into an inorganic or organic fraction of the samples

Sonochemical Digestion of High-Fired Plutonium Dioxide Samples

This work was performed as part of a broader effort to automate analytical methods for determining plutonium and other radioisotopes in environmental samples. The work described here represented a screening study to evaluate the effect of applying ultrasonic irradiation to dissolve high-fired plutonium oxide. The major findings of this work can be summarized as follows: (1) High-fired plutonium oxide does not undergo measurable dissolution when sonicated in nitric acid solutions, even at a high concentration range of nitric acid where the calculated thermodynamic solubility of plutonium oxide exceeds the ?g/mL level. (2) Applying organic complexants (nitrilotriacetic acid) and reductants (hydroxyurea) in 1.5 M nitric acid does not significantly increase the dissolution compared with digestion in nitric acid alone. Nearly all (99.5%) of the plutonium oxide remains undissolved under these conditions. (3) The action of a strong inorganic reductant, titanium trichloride in 25 wt% HCl, results in 40% dissolution of the plutonium oxide when the titanium trichloride concentration is ?1 wt% under sonication. (4) Oxidative treatment of plutonium oxide by freshly dissolved AgO ({approx}20 mg/mL) in 1.5 M nitric acid with sonication resulted in 95% plutonium oxide dissolution. However, the same treatment of plutonium oxide mechanically mixed with 50 mg of Columbia River sediment (CRS) results in a significant decrease of dissolution yield of plutonium oxide (<20% dissolved at the same AgO loading) because of parasitic consumption of AG(II) by oxidizable components of the CRS. (5) Digesting plutonium oxide in HF resulted in dissolution yields slightly higher than 80% for HF concentration from 6 M to 14 M. Sonication did not result in any improvement in dissolution efficiency in HF. (6) Mixed nitric acid/HF solutions result in a higher dissolution yield of plutonium oxide compared with digestion in HF alone (at the same HF concentrations). Practically quantitative dissolution of PuO2 can be achieved with 6 to 8 M nitric acid + 14 M HF or 8 M nitric acid + 4 M HF mixtures. In the latter case, quantitative dissolution of plutonium oxide was demonstrated only with sonication. Overall, the results indicate that applying ultrasound in an isolated cup horn configuration to dissolve refractory plutonium oxide does not offer any substantial advantage over conventional ?heat and mix? treatment. Oxidative treatment by AgO appears to be effective only when very little or no oxidizable materials are present in the digested sample. The catalytic use of Ag(II) in the ''Catalyzed Electrolytic Plutonium Oxide Dissolution'' technology would probably be more effective than using AgO because the Ag(II) is continually regenerated electrochemically. Reductive treatment with titanium trichloride in HCl solution proves to be less efficient than the previously observed effect based on in situ generation of Ti(III) in phosphoric acid and sulfuric acid media using a dip probe sonication setup. The previous experiments, however, were performed at higher temperature and with non-steady concentration profiles of Ti(III) ion in the process of sonochemical digestion