D.T. Reed

Stabilization of Rocky Flats Pu-contaminated ash within chemically bonded phosphate ceramics

Abstract A feasibility study was conducted on the use of chemically bonded phosphate ceramics for stabilization of combustion residue of high transuranic (TRU) wastes. Using a matrix of magnesium potassium phosphate formed by the room-temperature reaction of MgO and KH 2 PO 4 solution, we made waste forms that contained 5 wt% Pu to satisfy the requirements of the Waste Isolation Pilot Plant. The waste forms were ceramics whose compression strength was twice that of conventional cement grout and whose connected porosity was ≈50% that of cement grout. Both surrogate and actual waste forms displayed high leaching resistance for both hazardous metals and Pu. Hydrogen generation resulting from the radiolytic decomposition of water and organic compounds present in the waste form did not appear to be a significant issue. Pu was present as PuO 2 that was physically microencapsulated in the matrix. In the process, pyrophoricity was removed and leaching resistance was enhanced. The high leaching resistance was due to the very low solubility of PuO 2 coupled with superior microencapsulation. As a result, the waste forms satisfied the current Safeguard Termination Limit requirement for storage of TRU combustion residues.

Subsurface interactions of actinide species and microorganisms: Implications for the bioremediation of actinide-organic mixtures

By reviewing how microorganisms interact with actinides in subsurface environments, we assess how bioremediation controls the fate of actinides. Actinides often are co-contaminants with strong organic chelators, chlorinated solvents, and fuel hydrocarbons. Bioremediation can immobilize the actinides, biodegrade the co-contaminants, or both. Actinides at the IV oxidation state are the least soluble, and microorganisms accelerate precipitation by altering the actinides oxidation state or its speciation. We describe how microorganisms directly oxidize or reduce actinides and how microbiological reactions that biodegrade strong organic chelators, alter the pH, and consume or produce precipitating anions strongly affect actinide speciation and, therefore, mobility. We explain why inhibition caused by chemical or radiolytic toxicities uniquely affects microbial reactions. Due to the complex interactions of the microbiological and chemical phenomema, mathematical modeling is an essential tool for research on and application of bioremedation involving co-contamination with actinides. We describe the development of mathematical models that link microbiological and geochemical reactions. Throughout, we identify the key research needs.

Bio-sorption of neptunium(V) by Pseudomonas fluorescens

Summary The bio-sorption of neptunyl (NpO2+) by Pseudomonas fluorescens was investigated. The overall goals of this research are to identify key interactions between neptunium and soil bacteria and to model these effects under subsurface-related conditions. Neptunyl, which is generally thought to be non-sorptive, was significantly sorbed under all conditions studied. At initial neptunyl concentrations of 4.75 µM and pH = 7, as much as 85% of the neptunium was sorbed under aerobic conditions. Kinetic studies show that neptunyl was sorbed rapidly within the first 15 minutes. The extent of sorption also increased with pH. In all cases, the sorbed neptunium was shown to be NpO2+ by X-ray absorption near edged spectroscopy (XANES) analysis, confirming that there was no reduction to Np(IV) under the conditions of our experiment. The sorption data were modeled using Langmuir and Freundlich isotherms. A comparison of the two approaches showed a significantly better fit for the Freundlich isotherm, and the Freundlich parameter values suggest interactions between sorbed NpO2+ molecules. These data show that bio-sorption, even for neptunyl, has a significant role in defining the speciation of neptunium and, hence, its overall mobility in the subsurface.

Relativistic density functional investigation of Pu(H2O)n3+ clusters

The solvation of the Pu{sup 3+} ion in water was investigated using relativistic density functional theory including generalized gradient corrections. Binding energies and optimized geometries for different coordination numbers of water molecules [Pu(H{sub 2}O){sub n}{sup 3+}, n=6, 8, 9, 10, 12] around the ion were calculated. The results indicate that the first solvation shell of Pu{sup 3+} is likely to contain eight or possibly nine waters with a Pu-O bond length of 2.51-2.55 {angstrom}. The theoretical results are compared with two recent EXAFS experiments on the Pu{sup 3+} aqueous system.

EXAFS/XANES studies of plutonium-loaded sodalite/glass waste forms

A sodalite/glass ceramic waste form is being developed to immobilize highly radioactive nuclear wastes in chloride form, as part of an electrochemical cleanup process. Two types of simulated waste forms were studied: where the plutonium was alone in an LiCl/KCl matrix and where simulated fission-product elements were added representative of the electrometallurgical treatment process used to recover uranium from spent nuclear fuel also containing plutonium and a variety of fission products. Extended X-ray absorption fine structure spectroscopy (EXAFS) and X-ray absorption near-edge spectroscopy (XANES) studies were performed to determine the location, oxidation state, and particle size of the plutonium within these waste form samples. Plutonium was found to segregate as plutonium(IV) oxide with a crystallite size of at least 4.8 nm in the non-fission-element case and 1.3 nm with fission elements present. No plutonium was observed within the sodalite in the waste form made from the plutonium-loaded LiCl/KCl eutectic salt. Up to 35% of the plutonium in the waste form made from the plutonium-loaded simulated fission-product salt may be segregated with a heavy-element nearest neighbor other than plutonium or occluded internally within the sodalite lattice.

Mathematical Modelling of the Effects of Aerobic and Anaerobic Chelate Biodegradation on Actinide Speciation

Biodegradation of natural and anthropogenic chelating agents directly and indirectly affects the speciation, and hence, the mobility of actinides in subsurface environments. We combined mathematical modelling with laboratory experimentation to investigate the effects of aerobic and anaerobic chelate biodegradation on actinide [Np(IV/V), Pu(IV)] speciation. Under aerobic conditions, nitrilotriacetic acid (NTA) biodegradation rates were strongly influenced by the actinide concentration. Actinide-chelate complexation reduced the relative abundance of available growth substrate in solution and actinide species present or released during chelate degradation were toxic to the organisms. Aerobic bioutilization of the chelates as electron-donor substrates directly affected actinide speciation by releasing the radionuclides from complexed form into solution, where their fate was controlled by inorganic ligands in the system. Actinide speciation was also indirectly affected by pH changes caused by organic biodegradation. The two concurrent processes of organic biodegradation and actinide aqueous chemistry were accurately linked and described using CCB ATCH, a computer model developed at Northwestern University to investigate the dynamics of coupled biological and chemical reactions in mixed waste subsurface environments. CCBATCH was then used to simulate the fate of Np during anaerobic citrate biodegradation. The modelling studies suggested that, under some conditions, chelate degradation can increase Np(IV) solubility due to carbonate complexation in closed aqueous systems.

Speciation of Pu(VI) in Near-Neutral Solutions via Laser Photoacoustic Spectroscopy

The high sensitivity technique of laser photoacoustic spectroscopy and visible absorption spectroscopy were utilized to investigate the hydrolysis of Pu(VI) in perchlorate media. Pu(VI) absorption bands in the 600 to 700 nm were characterized as a function of pH in the pH = 1-7 regime. The formation constant of the 1:1 hydrolysis complex was determined as {beta}{sub 11} = 5.2 based on observed changes in the absorption bands noted. In the pH region investigated, four distinct species were identified and evidence for the existence of polynuclear species was obtained. 13 refs., 12 figs., 2 tabs.

Effect of Ionizing Radiation on Moist Air Systems

The radiation chemistry of nitrogen/oxygen/water systems is reviewed. General radiolytic effects in dry nitrogen/oxygen systems are relatively well characterized. Irradiation results in the formation of steady state concentrations of ozone, nitrous oxide and nitrogen dioxide. In closed systems, the concentration observed depends on the total dose, temperature and initial gas composition. Only three studies have been published that focus on the radiation chemistry of nitrogen/oxygen/water homogeneous gas systems. Mixed phase work that is relevant to the gaseous system is also summarized. The presence of water vapor results in the formation of nitric acid and significantly changes the chemistry observed in dry air systems. Mechanistic evidence from the studies reviewed are summarized and discussed in relation to characterizing the gas phase during the containment period of a repository in tuff.

XAFS study of americium sorbed onto groundwater colloids.

The sorption of americium, as Am(III), onto groundwater colloids obtained from a marl aquifer was studied in 2 x 10(-2)M sodium bicarbonate groundwater and 2 x 10(-2)M sodium chloride bicarbonate-free solutions. At the in situ groundwater pH of 8.6, the americium was strongly sorbed onto the colloids. XAFS analyses were performed on these sorbed Am species to establish the oxidation state and its near-neighbour bonding. These XAFS data, obtained at 400 mg l(-1) colloid concentrations and total Am concentration of 1.53 x 10(-5)M (dissolved and onto colloids), indicated that Am remains trivalent, and that surface complexes are formed with the colloids without surface precipitation. This conclusion is based on the absence of Am-Am interactions in the second or third shells. The surface complexes generated by the Am(III) sorbed onto active sites are described on the basis of the XAFS data. They include the presence of about seven water molecules around the ternary surface complexes of this trivalent actinide.

Corrosion product identification and relative rates of corrosion of candidate metals in an irradiated air-steam environment

The US Department of Energy, through its Office of Civilian Radioactive Waste Management, is conducting the Yucca Mountain Project. The purpose of this project is to determine the suitability of Yucca Mountain, in southern Nevada, as a location for a high level nuclear waste repository. Previously reported work by others indicates that dicopper trihydroxide nitrate, Cu{sub 2}NO{sub 3}(OH){sub 3}, forms on copper and copper alloys subjected to irradiated moist air near room temperature. The authors have performed experiments over a range of temperature and humidity, and have found that this species is formed at temperatures up to at least 150C if low to intermediate relative humidities are present. At 150C and 100% relative humidity, only Cu{sub 2}O and CuO were observed. The relative general corrosion rates of the copper materials tested in 1-month experiments at dose rates of 0.7 and 2.0 kGy/h were Cu > 70/30 Cu-Ni > Al-bronze. High-nickel alloy 825 showed no observable corrosion.