Effect of temperature on the complexation of Uranium(VI) with fluoride in aqueous solutions

Complexation of U(VI) with fluoride at elevated temperatures in aqueous solutions was studied by spectrophotometry. Four successive complexes, UO{sub 2}F{sup +}, UO{sub 2}F{sub 2}(aq), UO{sub 2}F{sub 3}{sup -}, and UO{sub 2}F{sub 4}{sup 2-}, were identified, and the stability constants at 25, 40, 55, and 70 C were calculated. The stability of the complexes increased as the temperature was elevated. The enthalpies of complexation at 25 C were determined by microcalorimetry. Thermodynamic parameters indicate that the complexation of U(VI) with fluoride in aqueous solutions at 25 to 70 C is slightly endothermic and entropy-driven. The Specific Ion Interaction (SIT) approach was used to obtain the thermodynamic parameters of complexation at infinite dilution. Structural information on the U(VI)/fluoride complexes was obtained by extended X-ray absorption fine structure spectroscopy

Speciation, Dissolution, and Redox Reactions of Chromium Relevant to Pretreatment and Separation of High-Level Tank Wastes

Chromium, one of the problematic elements in tank sludges, is considered the most important constituent in defining the total volume of high-level radioactive waste (HLW) glass. Current sludge washing processes (e.g. caustic leaching, 3 M NaOH) are not effective in removing Cr. Such inefficient removal would result in the production of an unacceptably large volume of HLW glass and thus a tremendous increase in the cost of waste disposal. This proposed research seeks to develop fundamental data for chromium (Cr) reactions that are not currently available but are essential for developing effective methodologies for removing Cr form high-level waste (HLW). Our objectives are to study (1) the dissolution of several solid phases (e.g., CrOOH, Cr2O3(c), Cr(OH)3, and Fe and Cr, binary hydroxides, identified to be important from sludge leaching studies) in highly alkaline solutions and in the presence of other electrolytes (e.g., carbonate, phosphate, sulfate, nitrite), and (2) the effect of the nature of Cr solid phases and aqueous species on their redox reactivity with a variety of potential oxidants (H2O2, persulfate, hypochlorite, etc.). This information will provide critical support for developing enhanced pretreatment strategies for removing Cr from HLW and will achieve a major cost reduction in HLW disposal

The effect of temperature on the speciation of U(VI) in sulfate solutions

Sulfate, one of the inorganic constituents that could be present in the nuclear waste repository, forms complexes with U(VI) and affects its migration in the environment. Results show that the complexation of U(VI) with sulfate is enhanced by the increase in temperature. The effect of temperature on the complexation and speciation of U(VI) in sulfate solutions is discussed

Characterization of Actinides in Simulated Alkaline Tank Waste Sludges and Leachates

Treatment of underground tanks at Hanford with concentrated alkali to improve removal of wastelimiting components of sludges has proven less efficacious for Al and Cr removal than had been hoped. Hence, more aggressive treatments of sludges, including contact with oxidants targeting Cr(III), have been tested in a limited number of samples and found to enhance Cr removal. Unfortunately, treatments of sludge samples with oxidative alkaline leachates produce conditions under which normally insoluble actinide ions (e.g., Am3+, Pu4+, Np4+) can no longer be reliably assumed to remain in the sludge phase. Few experimental or meaningful theoretical studies of actinide chemistry in strongly alkaline, strongly oxidizing solutions have been completed. Extrapolation of acid phase thermodynamic data to these radically different conditions provides little reliable guidance for predicting actinide speciation in highly salted alkaline solutions. In this project, we are investigating the fundamental chemistry of actinides in sludge simulants and supernatants under representative oxidative leaching conditions. We are also examining the potential impact of acidic leaching with concurrent secondary separations to enhance Al removal. Our objective is to provide adequate insight into actinide behavior under these conditions to enable prudent decision making as tank waste treatment protocols develop. We expect to identify those components of sludges that are likely to be problematic in the application of oxidative leaching protocols

Effect of temperature on the hydrolysis of actinide elements in solution

Recent experimental data on the hydrolysis of U(VI), Pu(VI), Np(V), and Th(IV) at variable temperatures are summarized in this review. Data indicate that the hydrolysis reactions of U(VI), Pu(VI), Np(V), and Th (IV) are all enhanced when temperature is increased from 283 to 358 K. In general, the tendency of actinide elements in different oxidation states toward hydrolysis follows the order: An(IV) > An(VI) > An(V), which can be well described by the electrostatic model. The enhancement of hydrolysis at higher temperatures can be attributed to the increase of ionization of water with the increase of temperature. A few theoretical thermodynamic approaches for predicting the effect of temperature, including the constant enthalpy approach, the constant heat capacity approach, the DQUANT equation, and the Ryzhenko-Bryzgalin model, are tested with the experimental data

Characterization of Actinides in Simulated Alkaline Tank Waste Sludges and Leach Solutions

Current plans call for an alkaline scrub of actinide-bearing sludges in the Hanford Waste tanks prior to their incorporation in glass waste forms. Though it is assumed that actinides will remain in the sludge phase during this procedure, this assumption is based on insufficient supporting thermodynamic and kinetic data. In this project we will investigate the fundamental chemistry of actinides in strongly alkaline solution and solid phases to strengthen the foundation and identify potential limitations of this approach. We will focus on the characterization of the leaching of actinides from simulated BiPO4, REDOX, and PUREX sludges, the identification of actinide mineral phases in the sludge simulants, and the possible solubilization of actinides by complexation and radiolysis effects. This program will provide new fundamental information on the chemical behavior and speciation of uranium, neptunium, plutonium, and americium in simulated alkaline tank waste sludges and alkali ne scrub liquors. Sludge simulants will be prepared from the appropriate matrix components using published data for guidance. Actinide ions will be introduced in the oxidation states pertinent to process conditions. We will characterize the speciation of the actinides in the sludges using a variety of techniques. In parallel studies, we will address the chemistry of actinide ions in alkaline solutions, principally those containing chelating agents. The third critical element of this research will be to assess the impact of radiolysis on actinide behavior. By correlating actinide speciation in the solid and solution phases with sludge composition, it will be possible to predict conditions favoring mobilization (or immobilization) of actinide ions during sludge washing. The new information will increase predictability of actinide behavior during tank sludge washing, and so contribute to minimization of the volume of high level waste created

Characterization of Actinides in Simulated Alkaline Tank Waste Sludges and Leachates

During sludge washing procedures associated with tank waste remediation, actinide ions are expected to remain with the insoluble metal oxide/hydroxide residue as the sludges are scrubbed to remove Cr, P, Al, S, and thus to be transmitted conveniently to the vitrification plant. Unfortunately, in laboratory tests with actual sludge samples alkaline sludge treatment has proven less efficacious for Al and Cr removal than was hoped. To improve removal of Al and Cr, more aggressive treatments of sludges are anticipated, including contact with oxidants targeting Cr(III). In addition, our prior research on the alkaline scrubbing of sludge simulants indicated higher than expected ''solubilization'' of Np and U into concentrated alkali, and some tendency for Am to be mobilized in contact with oxidants. In this project, we are investigating the fundamental chemistry of actinides in sludge simulants under representative oxidative leaching conditions. We are also examining acidic leaching with concurrent secondary separations to enhance Al removal. Our objective is to provide adequate insight into actinide behavior under these conditions to enable prudent decision making as tank waste treatment protocols develop. We expect to identify those components of sludges that are likely to be problematic in the application of oxidative leaching protocols

Complexation of NpO2+ with Amine-Functionalized Diacetamide Ligands in Aqueous Solution: Thermodynamic, Structural, and Computational Studies

Complexation of Np(V) with three structurally related amine-functionalized diacetamide ligands, including 2,2'-azanediylbis( N, N'-dimethylacetamide) (ABDMA), 2,2'-(methylazanediyl)bis( N, N'-dimethylacetamide) (MABDMA), and 2,2'-(benzylazanediyl)bis( N, N'-dimethylacetamide) (BnABDMA), in aqueous solutions was investigated. The stability constants of two successive complexes, namely, NpO2L+ and NpO2L2+, where L stands for the ligands, were determined by absorption spectrophotometry. The results suggest that the stability constants of corresponding Np(V) complexes follow the trend: MABDMA > ABDMA ≈ BnABDMA. The data are discussed in terms of the basicity of the ligands and compared with those for the complexation of Np(V) with an ether oxygen-linked diacetamide ligand. Extended X-ray absorption fine structure data indicate that, similar to the complexation with Nd3+ and UO22+, the ligands coordinate to NpO2+ in a tridentate mode through the amine nitrogen and two oxygen atoms of the amide groups. Computational results, in conjunction with spectrophotometric data, verify that the 1:2 complexes (NpO2(L)2+) in aqueous solutions are highly symmetric with Np at the inversion center, so that the f-f transition of Np(V) is forbidden and NpO2(L)2+ does not display significant absorption in the near-IR region

Examination of Uranium(VI) Leaching During Ligand Promoted Dissolution of Waste Tank Sludge Surrogates

The dissolution of synthetic boehmite (?-AlOOH) by 1-hydroxyethane-1,1-diphosphonic acid (HEDPA) was examined in a series of batch adsorption/dissolution experiments. Additionally, the leaching behavior of {sup 233}U(VI) from boehmite was examined as a function of pH and HEDPA concentration. The results are discussed in terms of sludge washing procedures that may be utilized during underground tank waste remediation. In the pH range 4 to 10, complexation of Al(III) by HEDPA significantly enhanced dissolution of boehmite. This phenomenon was especially pronounced in the neutral pH region where the solubility of aluminum, in the absence of complexants, is limited by the formation of sparsely soluble aluminum hydroxides. At pH higher than 10, dissolution of synthetic boehmite was inhibited by HEDPA, likely due to sorption of Al(III):HEDPA complexes. Addition of HEDPA to equilibrated U(VI)-synthetic boehmite suspensions yielded an increase in the aqueous phase uranium concentration. Partitioning of uranium between the solid and aqueous phase is described in terms of U(VI):HEDPA speciation and dissolution of the boehmite solid phase