CSNF WASTE FORM DEGRADATION: SUMMARY ABSTRACTION

The purpose of this model report is to describe the development and validation of models that can be used to calculate the release of radionuclides from commercial spent nuclear fuel (CSNF) following a hypothetical breach of the waste package and fuel cladding in the repository. The purpose also includes describing the uncertainties associated with modeling the radionuclide release for the range of CSNF types, exposure conditions, and durations for which the radionuclide release models are to be applied. This document was developed in accordance with Technical Work Plan for: Regulatory Integration Modeling and Analysis of the Waste Form and Waste Package (BSC 2004 [DIRS 169944]). This document considers radionuclides to be released from CSNF when they are available for mobilization by gas-phase mass transport, or by dissolution or colloid formation in water that may contact the fuel. Because other reports address limitations on the dissolved and colloidal radionuclide concentrations (BSC 2004 [DIRS 169944], Table 2-1), this report does not address processes that control the extent to which the radionuclides released from CSNF are mobilized and transported away from the fuel either in the gas phase or in the aqueous phase as dissolved and colloidal species. The scope is limited to consideration of degradation of the CSNF rods following an initial breach of the cladding. It considers features of CSNF that limit the availability of individual radionuclides for release into the gaseous or aqueous phases that may contact the fuel and the processes and events expected to degrade these CSNF features. In short, the purpose is to describe the characteristics of breached fuel rods and the degradation processes expected to influence radionuclide release

The role of laboratory analog experiments in assessing the performance of waste package materials

There is an immediate need to begin to validate models that can be used for assessing the performance of waste package materials in an unsaturated repository environment. This paper examines available testing information and testing approaches that could support validation of models for engineering barrier system (EBS) radionuclide release. The content is presented in the context of the general methodology that has been proposed for validating performance assessment models. Available experimental observations are used to test some of the EBS release rate modeling premises. These observations include evidence of fluid film formation on waste glass surfaces in isothermal humid environments, accelerated waste glass reaction rates under repository service conditions of large glass surface area to water volume ratio, and mobilization of radionuclides as solutes and colloids. It is concluded that some important modeling premises may not be consistent with available experimental information. However, it is also concluded that future laboratory testing, which simulates the integrated waste package systems, is needed to evaluate the significance of these inconsistencies and to test the system level models. A small-scale apparatus which was developed and tested to examine the feasibility of laboratory analog testing for the unsaturated Yucca Mountain repository environment is described. 16 refs., 4 figs., 1 tab

The Chemistry os Spent Nuclear Fuel From X-Ray Absorption Spectroscopy

Present and future nuclear fuel cycles will require an understanding of the complex chemistry of trace fission products and transuranium actinides in spent nuclear fuel (SNF). Because of the unique analytical challenges presented by SNF to the materials scientist, many of its fundamental physical and chemical properties remain poorly understood, especially on the microscopic scale. Such an understanding of the chemical states of radionuclides in SNF would benefit development of technologies for fuel monitoring, fuel performance improvement and modeling, fuel reprocessing, and spent fuel storage and disposal. We have recently demonstrated the use of synchrotron x-ray absorption spectroscopy (XAS) to examine crystal chemical properties of actinides and fission products in extracted specimens of SNF. Information obtained includes oxidation state, chemical bond coordination, and quantitative elemental concentration and distribution. We have also used XAS in a scanning mode to obtain x-ray spectral micrographs with resolution approaching 1 micron. A brief overview of the technique will be presented, along with findings on uranium, plutonium, neptunium, technetium, and molybdenum in commercial PWR SNF specimens

Microscopic Examination of a Corrosion Front in Spent Nuclear Fuel

Spent uranium oxide nuclear fuel hosts a variety of trace chemical constituents, many of which must be sequestered from the biosphere during fuel storage and disposal. In this paper we present synchrotron x-ray absorption spectroscopy and microscopy findings that illuminate the resultant local chemistry of neptunium and plutonium within spent uranium oxide nuclear fuel before and after corrosive alteration in an air-saturated aqueous environment. We find the plutonium and neptunium in unaltered spent fuel to have a +4 oxidation state and an environment consistent with solid-solution in the UO{sub 2} matrix. During corrosion in an air-saturated aqueous environment, the uranium matrix is converted to uranyl U(VI)O{sub 2}{sup 2+} mineral assemblage that is depleted in plutonium and neptunium relative to the parent fuel. At the corrosion front interface between intact fuel and the uranyl-mineral corrosion layer, we find evidence of a thin ({approx}20 micrometer) layer that is enriched in plutonium and neptunium within a predominantly U{sup 4+} environment. Available data for the standard reduction potentials for NpO{sup 2+}/Np{sup 4+} and UO{sub 2}{sup 2+}/U{sup 4+} couples indicate that Np(IV) may not be effectively oxidized to Np(V) at the corrosion potentials of uranium dioxide spent nuclear fuel in air-saturated aqueous solutions. Neptunium is an important radionuclide in dose contribution according to performance assessment models of the proposed U. S. repository at Yucca Mountain, Nevada. A scientific understanding of how the UO{sub 2} matrix of spent nuclear fuel impacts the oxidative dissolution and reductive precipitation of neptunium is needed to predict its behavior at the fuel surface during aqueous corrosion. Neptunium would most likely be transported as aqueous Np(V) species, but for this to occur it must first be oxidized from the Np(IV) state found within the parent spent nuclear fuel [1]. In the immediate vicinity of the spent fuel's surface the redox and nucleation behavior is likely to promote/enhance nucleation of NpO{sub 2} and Np{sub 2}O{sub 5}. Alternatively, Np may be incorporated into uranyl (UO{sub 2}{sup 2+}) alteration phases [2]. In some cases, less-soluble elements such as plutonium will be enriched near the surface of the corroding fuel [3]. We have used focused synchrotron x-rays from the MRCAT beam line at the Advanced Photon Source (APS) at Argonne National Lab to examine a specimen of spent nuclear fuel that had been subject to 10 years of corrosion testing in an environment of humid air and dripping groundwater at 90 C [4]. We find evidence of a region, approximately 20 microns in thickness, enriched in plutonium and neptunium at the corrosion front that exists between the uranyl silicate alteration mineral rind and the unaltered uranium oxide fuel (Figures 1 and 2). The uranyl silicate is itself found to be depleted in these transuranic elements relative to their abundance relative to uranium in the parent fuel. This suggests a low mobility of these components owing to a resistance to oxidize further in the presence of a UO{sub 2}{sup 2+}/U{sup 4+} couple [5]

Identification of colloids in nuclear waste glass reactions

Characterization data for particulates formed under a variety of laboratory leaching conditions that simulate glass reaction in a repository environment are presented. Data on the particle size distributions and filterable fractions for neptunium, plutonium, americium, and curium were obtained by filtrations through a series of filters with pore sizes ranging from 1 {mu}m to 3.8 nm. The neptunium was found to be largely nonfilterable. Americium and plutonium were associated with filterable particles. The particles with which the americium, plutonium, and curium were associated were characterized using transmission electron microscopy (TEM) examination techniques. 8 refs., 1 fig., 2 tabs

Corrosion Tests of LWR Fuels - Nuclide Release

Two BWR fuels [64 and 71 (MWd)/kgU], one of which contained 2% Gd, and two PWR fuels [30 and 45 (MWd)/kgU], are tested by dripping groundwater on the fuels under oxidizing and hydrologically unsaturated conditions for times ranging from 2.4 to 8.2 yr at 90 C. The {sup 99}Tc, {sup 129}I, {sup 137}Cs, {sup 97}Mo, and {sup 90}Sr releases are presented to show the effects of long reaction times and of gadolinium on nuclide release. This investigation showed that the five nuclides at long reaction times have similar fractional release rates and that the presence of 2% Gd reduced the {sup 99}Tc cumulative release fraction by about an order of magnitude over that of a fuel with a similar burnup

Development of acceptance specifications for low-activity waste from the Hanford tanks

Low-activity products will be in the form of soldified waste and optional matrix and filler materials enclosed in sealed metal boxes. Acceptance specifications limit the physical characteristics of the containers, the chemical and physical characteristics of the waste form and other materials that may be in the container, the waste loading, and the radionuclide leaching characteristics of the waste form. The specifications are designed to ensure that low-activity waste products will be compatible with the driving regulatory and operational requirements and with existing production technologies

Corrosion Tests of LWR Fuels - Nuclide Release

Two BWR fuels [64 and 71 (MWd)/kgU], one of which contained 2% Gd, and two PWR fuels [30 and 45 (MWd)/kgU], are tested by dripping groundwater on the fuels under oxidizing and hydrologically unsaturated conditions for times ranging from 2.4 to 8.2 yr at 90 C. The {sup 99}Tc, {sup 129}I, {sup 137}Cs, {sup 97}Mo, and {sup 90}Sr releases are presented to show the effects of long reaction times and of gadolinium on nuclide release. This investigation showed that the five nuclides at long reaction times have similar fractional release rates and that the presence of 2% Gd reduced the {sup 99}Tc cumulative release fraction by about an order of magnitude over that of a fuel with a similar burnup