Judah I. Friese

Corrosion of commercial spent nuclear fuel. 1. Formation of studtite and metastudtite

Summary The contact of commercial spent nuclear fuel (CSNF) with water over a 2-year period led to an unexpected corrosion phase and morphology. At short hydration times, crystallites of metaschoepite [(UO2)8O2(OH)12](H2O)10 were observed on the hydrated CSNF particles. Over the 2-year contact period, all evidence of metaschoepite disappeared, and the fuel particles were coated by a new alteration phase. Additionally, films of the reacted fuel were observed at the sample air-water interface of each sample. The corrosion phases on fuel powders and on the suspended films were examined by scanning electron microscopy, energy-dispersive X-ray fluorescence, and X-ray diffraction and were identified as studtite [(UO2)(O2)(H2O)2](H2O)2 and metastudtite (UO4·2H2O), respectively. The reason for the partitioning of the latter phase to the sample air-water interface is unclear at this time but may be due to structural differences between the two phases. Scanning electron micrographs of the CSNF powders indicated surface corrosion along grain boundaries and fragmentation of the primary solid. The occurrence of studtite and metastudtite on CSNF could have implications for the potential attenuation of released radionuclides during oxidative corrosion of CSNF in a geologic repository.

Maximum reasonable radioxenon releases from medical isotope production facilities and their effect on monitoring nuclear explosions

Fission gases such as (133)Xe are used extensively for monitoring the world for signs of nuclear testing in systems such as the International Monitoring System (IMS). These gases are also produced by nuclear reactors and by fission production of (99)Mo for medical use. Recently, medical isotope production facilities have been identified as the major contributor to the background of radioactive xenon isotopes (radioxenon) in the atmosphere (Stocki et al., 2005; Saey, 2009). These releases pose a potential future problem for monitoring nuclear explosions if not addressed. As a starting point, a maximum acceptable daily xenon emission rate was calculated, that is both scientifically defendable as not adversely affecting the IMS, but also consistent with what is possible to achieve in an operational environment. This study concludes that an emission of 5 × 10(9) Bq/day from a medical isotope production facility would be both an acceptable upper limit from the perspective of minimal impact to monitoring stations, but also appears to be an achievable limit for large isotope producers.

Microscale characterization of uranium(VI) silicate solids and associated neptunium(V)

Summary The uranium(VI) silicate phases uranophane, Ca[(UO2)(SiO3OH)]2·5H2O, and sodium boltwoodite, Na[(UO2)(SiO3OH)]·1.5H2O, were synthesized in the presence of small, variable quantities (0.5–2.0 mol % relative to U) of pentavalent neptunium (Np(V), as NpO2+), to investigate the nature of its association with these U(VI) solid phases. Solids were characterized by X-ray powder diffraction (XRD), gamma spectrometry (GS), scanning electron microscopy (SEM) with energy-dispersive X-ray spectroscopy (EDS), and transmission electron microscopy (TEM) with electron energy-loss spectroscopy (EELS). Neptunium concentration was determined in the bulk solid phases by GS and was found to range from 780–15800 μg/g. In some cases, Np distributions between the aqueous and solid phases were monitored, and 78–97% of the initial Np was associated with the isolated solid. Characterization of individual crystallites by TEM/EELS suggests the Np is associated with the U(VI) phase. No discrete Np phases, such as Np oxides, were observed. Because the U(VI) silicates are believed to be important solubility-controlling solids on a geologic timescale, these results suggest that the partitioning of the minor actinides to these solids must be considered when assessing the performance of a waste repository for spent nuclear fuel.

Estimates of Radioxenon Released from Southern Hemisphere Medical isotope Production Facilities Using Measured Air Concentrations and Atmospheric Transport Modeling

The International Monitoring System (IMS) of the Comprehensive-Nuclear-Test-Ban-Treaty monitors the atmosphere for radioactive xenon leaking from underground nuclear explosions. Emissions from medical isotope production represent a challenging background signal when determining whether measured radioxenon in the atmosphere is associated with a nuclear explosion prohibited by the treaty. The Australian Nuclear Science and Technology Organisation (ANSTO) operates a reactor and medical isotope production facility in Lucas Heights, Australia. This study uses two years of release data from the ANSTO medical isotope production facility and (133)Xe data from three IMS sampling locations to estimate the annual releases of (133)Xe from medical isotope production facilities in Argentina, South Africa, and Indonesia. Atmospheric dilution factors derived from a global atmospheric transport model were used in an optimization scheme to estimate annual release values by facility. The annual releases of about 6.8 × 10(14) Bq from the ANSTO medical isotope production facility are in good agreement with the sampled concentrations at these three IMS sampling locations. Annual release estimates for the facility in South Africa vary from 2.2 × 10(16) to 2.4 × 10(16) Bq, estimates for the facility in Indonesia vary from 9.2 × 10(13) to 3.7 × 10(14) Bq and estimates for the facility in Argentina range from 4.5 × 10(12) to 9.5 × 10(12) Bq.

Interactions of Np(V) and U(VI) with dipicolinic acid

To complement earlier studies of the complexation kinetics of Np(V) and U(VI) by oxydiacetic acid and several diphosphonic acids, the rate of complexation of these metal ions by dipicolinic acid (pyridine-2,6-dicarboxylic acid, DPA) has been investigated by stopped-flow spectrophotometry. This ligand is distinguished from the previously studied species by the rigid planar arrangement of the ligand functional groups and the presence of a pyridine nitrogen donor atom. Reactions of DPA with UO22+ at p[H] 1 and NpO2+ at p[H] 1 and 3 adhere to the comparatively simple first-order approach to equilibrium kinetic model used to describe the earlier results. At p[H] 3, the UO22+ reaction is characterized by consecutive pseudo-first order reactions. The first is an apparent approach to equilibrium while the second process demonstrates a saturation effect, indicating the existence of a stable intermediate complex. Relative rates and activation parameters are discussed in comparison with the previous results.

Kinetic Study of the Reactions of Np(V) and U(VI) with Oxydiacetic Acid

The rate and mechanism of complexation reactions of neptunyl(V) and uranyl(VI) by oxydiacetic acid at pH 3 in 1.0 M NaC104 solutions has been investigated by stopped-flow spectrophotometry. This tridentate ligand is able to accommodate the structural requirements of the linear dioxoactinide cations, and is known to form moderately stable complexes with these metal ions. As was reported previously in a study of diphosphonate complexes of these metal ions, the rate of formation of the respective 1:1 complexes is faster for Np(V) than U(VI), despite a stronger thermodynamic driving force for the latter. This result further supports the proposition that the rate of solvent and ligand rearrangement in the precursor complex is an important parameter in determining the rate of actinyl complexation reactions. The applicability of Marcus reaction rate theory, as modified by Albery, to complexation reactions of this type is discussed.

Integrated separation scheme for measuring a suite of fission and activation products from a fresh mixed fission and activation product sample

Mixed fission and activation materials resulting from various nuclear processes and events contain a wide range of isotopes for analysis spanning almost the entire periodic table. This work describes the production of a complex synthetic sample containing fission products, activation products, and irradiated soil, and determines the percent chemical recovery of select isotopes through the integrated chemical separation scheme. Based on the results of this experiment, a complex synthetic sample can be prepared with low atom/fission ratios and isotopes of interest accurately and precisely measured following an integrated chemical separation method.

Abatement of xenon and iodine emissions from medical isotope production facilities.

The capability of the International Monitoring System (IMS) to detect xenon from underground nuclear explosions is dependent on the radioactive xenon background. Adding to the background, medical isotope production (MIP) by fission releases several important xenon isotopes including xenon-133 and iodine-133 that decays to xenon-133. The amount of xenon released from these facilities may be equivalent to or exceed that released from an underground nuclear explosion. Thus the release of gaseous fission products within days of irradiation makes it difficult to distinguish MIP emissions from a nuclear explosion. In addition, recent shortages in molybdenum-99 have created interest and investment opportunities to design and build new MIP facilities in the United States and throughout the world. Due to the potential increase in the number of MIP facilities, a discussion of abatement technologies provides insight into how the problem of emission control from MIP facilities can be tackled. A review of practices is provided to delineate methods useful for abatement of medical isotopes.

Comparison of radionuclide ratios in atmospheric nuclear explosions and nuclear releases from Chernobyl and Fukushima seen in gamma ray spectrometry

The Comprehensive Nuclear Test Ban Treaty has remote radionuclide monitoring followed by an On Site Inspection (OSI) to clarify the nature of a suspect event as part of its verification regime. An important aspect of radionuclide measurements on site is the discrimination of other potential sources of similar radionuclides such as reactor accidents or medical isotope production. The Chernobyl and Fukushima nuclear reactor disasters offer two different reactor source term environmental inputs that can be compared against historical measurements of nuclear explosions. The comparison of whole-sample gamma spectrometry measurements from these three events and the analysis of similarities and differences are presented. This analysis is a step toward confirming what is needed for measurements during an OSI under the auspices of the Comprehensive Test Ban Treaty.

Measurement of Fukushima aerosol debris in Sequim and Richland, WA and Ketchikan, AK

Aerosol collections were initiated at several locations by Pacific Northwest National Laboratory (PNNL) shortly after the Great East Japan earthquake of May 2011. Aerosol samples were transferred to laboratory high-resolution gamma spectrometers for analysis. Similar to treaty monitoring stations operating across the Northern hemisphere, iodine and other isotopes which could be volatilized at high temperature were detected. Though these locations are not far apart, they have significant variations with respect to water, mountain-range placement, and local topography. Variation in computed source terms will be shown to bound the variability of this approach to source estimation.