Michele A. Lewis

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.

The precision of product consistency tests conducted with a glass-bonded ceramic waste form

The product consistency test (PCT) that is used for qualification of borosilicate high-level radioactive waste (HLW) glasses for disposal can be used for the same purpose in the qualification of the glass-bonded sodalite ceramic waste form (CWF). The CWF was developed to immobilize radioactive salt wastes generated during the electrometallurgical treatment of spent sodium-bonded nuclear fuels. An interlaboratory study was conducted to measure the precision of PCTs conducted with the CWF for comparison with the precision of PCTs conducted with HLW glasses. The six independent sets of triplicate PCT results generated in the study were used to calculate the intralaboratory and interlaboratory consistency based on the concentrations of Al, B, Na, and Si in the test solutions. The results indicate that PCTs can be conducted as precisely with the CWF as with HLW glasses. For example, the values of the reproducibility standard deviation for Al, B, Na, and Si were 1.36, 0.347, 3.40, and 2.97 mg/l for PCT with CWF. These values are within the range of values measured for borosilicate glasses, including reference HLW glasses.

Effect of different glass and zeolite A compositions on the leach resistance of ceramic waste forms

A ceramic waste form is being developed for waste generated during electrometallurgical treatment of spent nuclear fuel. The waste is generated when fission products are removed from the electrolyte, LiCl-KCl eutectic. The waste form is a composite fabricated by hot isostatic pressing a mixture of glass frit and zeolite occluded with fission products and salt. Normalized release rate is less than 1 g/m{sup 2}d for all elements in MCC-1 leach test run for 28 days in deionized water at 90 C. This leach resistance is comparable to that of early Savannah River glasses. We are investigating how leach resistance is affected by changes in cationic form of zeolite and in glass composition. Composites were made with 3 forms of zeolite A and 6 glasses. We used 3-day ASTM C1220-92 (formerly MCC-1) leach tests to screen samples for development purposes only. The leach test results show that the glass composites of zeolites 5A and 4A retain fission products equally well. Loss of Cs is small (0.1-0.5 wt%), while the loss of divalent and trivalent fission products is one or more orders of magnitude smaller. Composites of 5A retain chloride ion better in these short-term screens than 4A and 3A. The more leach resistant composites were made with durable glasses rich in silica and poor in alkaline earth oxides. XRD show that a salt phase was absent in the leach resistant composites of 5A and the better glasses but was present in the other composites with poorer leach performance. Thus, absence of salt phase corresponds to improved leach resistance. Interactions between zeolite and glass depend on composition of both.

Densification of Salt-Occluded Zeolite a Powders to a Leach-Resistant Monolith

Pyrochemical processing of spent fuel from the Integral Fast Reactor (IFR) yields a salt waste of LiCl-KCl that contains approximately 6 wt% fission products, primarily as CsCl and SrCl{sub 2}. Past work has shown that zeolite A will preferentially sorb cesium and strontium and will encapsulate the salt waste in a leach-resistant, radiation-resistant aluminosilicate matrix. However, a method is sill needed to convert the salt-occluded zeolite powders into a form suitable for geologic disposal. We are thus investigating a method that forms bonded zeolite by hot pressing a mixture of glass frit and salt-occluded zeolite powders at 990 K (717{degree}C) and 28 MPa. The leach resistance of the bonded zeolite was measured in static leach tests run for 28 days in 363 K (90{degree}C) deionized water. Normalized release rates of all elements in the bonded zeolite were low, <1 g/m{sup 2} d. Thus, the bonded zeolite may be a suitable waste form for IFR salt waste.

Picosecond pulse radiolysis studies to understand the primary processes in radiolysis

Abstract The use of pulse radiolysis to learn about processes which occur before the beginning of chemical times is discussed. Two examples, the distance distribution of positive and negative ions in n -hexane and the identity of the “dry electron” are discussed in detail. It is shown that the dry electron which reacts is not quasi-free, but instead must be associated with the solvent. Thus, the name “dry electron” is somewhat of a misnomer.

The Use of Additives for Reducing Hydrogen Yield in Mortar Containing Slag and Chloride Salts

Cementitious waste forms are being considered for immobilizing nuclear waste before disposal. In earlier work, it was found that irradiation of a mortar formulation consisting of slag, portland cement, fly ash, water, and up to 10 wt% KCl{endash}LiCl salt resulted in the generation of hydrogen. Yields were relatively high and the rates of generation were constant for the irradiation period investigated. The addition of small amounts of oxygen-rich electron scavengers to the mortar was investigated as a means for reducing hydrogen yields. The addition of NaNO{sub 3} reduced the hydrogen yield; changed the radiolytic products from hydrogen to a mixture of hydrogen, nitrogen, and N{sub 2}O; and reduced the pressurization rate after exposure to 400 Mrads. The addition of NaIO{sub 4} and KMnO{sub 4} reduced hydrogen yields slightly while the addition of Ag{sub 2}O increased the yield. Moreover, the addition of FeS to a non-slag mortar changed the radiolysis mechanism but the addition of FeO did not. The results of these experiments provided an insight into the nature of the radiolytic reactions occurring in the mortar formulations and indicated that the radiolytic generation of gases might be controlled with the proper choice of additive. 14 refs., 3 figs., 2 tabs.

Accounting for EBR-II Metallic Waste Form Degradation in TSPA

A metallic waste form (MWF) will be used to immobilize cladding hulls from spent sodium-bonded nuclear fuel rods. Laboratory tests were conducted to determine if the HLW glass degradation rate model used in Total System Performance Assessment (TSPA) calculations can be used as an upper bound for the degradation rate of the MWF. Static tests were conducted with monolithic MWF samples in pH buffer solutions to measure the degradation rates at 50, 70, and 90°C. The measured degradation rates of the MWF were compared to the rates calculated with the HLW glass degradation model. The degradation rates were calculated as the product of the specific dissolution rates and the anticipated exposed surface areas of glass and MWF in a breeched canister. This comparison showed that the rate calculated using the HLW glass degradation model bounds the rates measured for the MWF at all pH values and temperatures. These results support the potential use of HLW glass as a surrogate for MWF degradation for the purpose of performance assessment.