Technetium Management Using Stannous Apatite Based Waste Forms Permeable Reactive Barriers and Separtation Processes.
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These slides showcase the work done by INL in the low temperature chlorination work package during FY25.
The concept of geological disposal for high-level radioactive waste (HLW) is based on a multi-barrier system comprising the natural geological barrier that repository host rock provides and its surroundings, as well as an engineered barrier system (EBS) that includes waste form, waste canisters, buffer materials, and backfill. The multi-barrier system is expected to perform its desired functions to isolate waste from the biosphere and achieve HLW disposal. Because of the interaction processes of radionuclide decay heat with hydraulic and water-mineral reactions in the radioactive waste repository, the bentonite buffer degradation resulting from the external temperature and pressure warrants investigation. However, seldom addressed in Taiwan is the influence of thermo-hydro-chemical (T-H-C) processes on buffer material degradation in the EBS of HLW disposal repositories as related to smectite clay dehydration. Therefore, we adopted the chemical kinetic model of smectite dehydration to calculate the amount of water expelled from smectite clay minerals caused by higher temperatures of waste decay heat. We discovered that smectite clay could cause volume shrinkage because of a loss of interlayer water, which can lead to bentonite buffer compression. The results of this study may be used in advanced research on the evolution of bentonite degradation for both performance assessments and safety analyses of final HLW disposal in Taiwan. (authors)
The multi-barrier system in a nuclear waste repository typically consists of the natural barrier system (NBS), which includes the repository host rock and its surrounding subsurface environment, and the engineered barrier system (EBS). The EBS represents the man-made, engineered materials placed within a repository, including the waste form, waste canisters, buffer materials, backfill, and seals (OECD 2003).
Geological repositories for disposal of high-level nuclear waste generally rely on a multibarrier system to isolate radioactive waste from the biosphere. The multi-barrier system typically consists of the natural barrier system (NBS), which includes the repository host rock and its surrounding subsurface environment, and the engineered barrier system (EBS). The EBS represents the man-made, engineered materials placed within a repository, including the waste form, waste canisters, buffer materials, backfill, and seals (OECD, 2003). The EBS plays a significant role in the containment and long-term retardation of radionuclide release.
A generic reference case for disposal of spent nuclear fuel and high-level radioactive waste in crystalline rock is outlined. The generic cases are intended to support development of disposal system modeling capability by establishing relevant baseline conditions and parameters. Establishment of a generic reference case requires that the emplacement concept, waste inventory, waste form, waste package, backfill/buffer properties, EBS failure scenarios, host rock properties, and biosphere be specified. The focus in this report is on those elements that are unique to crystalline disposal, especially the geosphere representation. Three emplacement concepts are suggested for further analyses: a waste packages containing 4 PWR assemblies emplaced in boreholes in the floors of tunnels (KBS-3 concept), a 12-assembly waste package emplaced in tunnels, and a 32-assembly dual purpose canister emplaced in tunnels. In addition, three failure scenarios were suggested for future use: a nominal scenario involving corrosion of the waste package in the tunnel emplacement concepts, a manufacturing defect scenario applicable to the KBS-3 concept, and a disruptive glaciation scenario applicable to both emplacement concepts. The computational approaches required to analyze EBS failure and transport processes in a crystalline rock repository are similar to those of argillite/shale, with the most significant difference being that the EBS in a crystalline rock repository will likely experience highly heterogeneous flow rates, which should be represented in the model. The computational approaches required to analyze radionuclide transport in the natural system are very different because of the highly channelized nature of fracture flow. Computational workflows tailored to crystalline rock based on discrete transport pathways extracted from discrete fracture network models are recommended.
The design of a radioactive waste repository typically involves a multi-barrier system, including the natural barrier system (NBS), i.e., the host rock and its surrounding subsurface environment, and an engineered barrier system (EBS). The EBS is to be constructed from the man-made, engineered materials placed within a repository. The repository includes the waste form, waste canisters, buffer materials, backfill, and seals. The most common buffer material for EBS is compacted bentonite, which features low permeability and high retardation of radionuclides. Extensive studies concerning the behavior of bentonite backfill in crystalline and argillite/shale geologic environments for nuclear waste disposal have been conducted by means of laboratory experiments, numerical modeling, and large-scale in situ tests in Underground Research Laboratories (URLs) in Switzerland, France, Belgium, and Japan. This report includes the results of LBNL’s research activities conducted according to the objectives and scope of the work packages “SF-20LB01030802 Engineered Barrier System R&D - LBNL” and “SF-20LB01030806 Engineered Barrier System International Collaborations - LBNL” of the Spent Fuel and Waste Science and Technology (SFWST) (formerly called Used Fuel Disposal) Campaign of the Department of Energy’s (DOE) Office of Nuclear Energy. LBNL research studies included laboratory scale tests and modeling of the evolution of the EBS bentonite and associated coupled processes, and impacts of high temperature on parameters and processes relevant to the performance of crystalline and argillite repositories, including the evaluation of the technical basis for applying the maximum allowable temperature. The results of these studies are being addressing the technical elements necessary to evaluate the EBS design concepts. Emphasis is on the study of thermal, mechanical, and chemical processes that influence the performance of EBS, and the development of modeling capability for reliable assessment of these processes, and ultimately supporting the development of the GDSA model with detailed coupled THMC process models.
Safety issues involved in the disposal of nuclear wastes in space as a complement to mined geologic repositories are examined as part of an assessment of the feasibility of nuclear waste disposal in space. General safety guidelines for space disposal developed in the areas of radiation exposure and shielding, containment, accident environments, criticality, post-accident recovery, monitoring systems and isolation are presented for a nuclear waste disposal in space mission employing conventional space technology such as the Space Shuttle. The current reference concept under consideration by NASA and DOE is then examined in detail, with attention given to the waste source and mix, the waste form, waste processing and payload fabrication, shipping casks and ground transport vehicles, launch site operations and facilities, Shuttle-derived launch vehicle, orbit transfer vehicle, orbital operations and space destination, and the system safety aspects of the concept are discussed for each component. It is pointed out that future work remains in the development of an improved basis for the safety guidelines and the determination of the possible benefits and costs of the space disposal option for nuclear wastes.
Safety guidelines are presented. Waste form, waste processing and payload fabrication facilities, shipping casks and ground transport vehicles, payload primary container/core, radiation shield, reentry systems, launch site facilities, uprooted space shuttle launch vehicle, Earth packing orbits, orbit transfer systems, and space destination are discussed. Disposed concepts and risks are then discussed.
Washington River Protection Solutions (WRPS) and its contractors at Pacific Northwest National Laboratory (PNNL) and Savannah River National Laboratory (SRNL) are conducting a development program to develop / refine the cementitious waste form for the wastes treated at the ETF and to provide the data needed to support the IDF PA. This technical approach document is intended to provide guidance to the cementitious waste form development program with respect to the waste form characterization and testing information needed to support the IDF PA. At the time of the preparation of this technical approach document, the IDF PA effort is just getting started and the approach to analyze the performance of the cementitious waste form has not been determined. Therefore, this document looks at a number of different approaches for evaluating the waste form performance and describes the testing needed to provide data for each approach. Though the approach addresses a cementitious secondary aqueous waste form, it is applicable to other waste forms such as Cast Stone for supplemental immobilization of Hanford LAW. The performance of Cast Stone as a physical and chemical barrier to the release of contaminants of concern (COCs) from solidification of Hanford liquid low activity waste (LAW) and secondary wastes processed through the Effluent Treatment Facility (ETF) is of critical importance to the Hanford Integrated Disposal Facility (IDF) total system performance assessment (TSPA). The effectiveness of cementitious waste forms as a barrier to COC release is expected to evolve with time. PA modeling must therefore anticipate and address processes, properties, and conditions that alter the physical and chemical controls on COC transport in the cementitious waste forms over time. Most organizations responsible for disposal facility operation and their regulators support an iterative hierarchical safety/performance assessment approach with a general philosophy that modeling provides the critical link between the short-term understanding from laboratory and field tests, and the prediction of repository performance over repository time frames and scales. One common recommendation is that experiments be designed to permit the appropriate scaling in the models. There is a large contrast in the physical and chemical properties between the Cast Stone waste package and the IDF backfill and surrounding sediments. Cast Stone exhibits low permeability, high tortuosity, low carbonate, high pH, and low Eh whereas the backfill and native sediments have high permeability, low tortuosity, high carbonate, circumneutral pH, and high Eh. These contrasts have important implications for flow, transport, and reactions across the Cast Stone – backfill interface. Over time with transport across the interface and subsequent reactions, the sharp geochemical contrast will blur and there will be a range of spatially-distributed conditions. In general, COC mobility and transport will be sensitive to these geochemical variations, which also include physical changes in porosity and permeability from mineral reactions. Therefore, PA modeling must address processes, properties, and conditions that alter the physical and chemical controls on COC transport in the cementitious waste forms over time. Section 2 of this document reviews past Hanford PAs and SRS Saltstone PAs, which to date have mostly relied on the lumped parameter COC release conceptual models for TSPA predictions, and provides some details on the chosen values for the lumped parameters. Section 3 provides more details on the hierarchical modeling strategy and processes and mechanisms that control COC release. Section 4 summarizes and lists the key parameters for which numerical values are needed to perform PAs. Section 5 provides brief summaries of the methods used to measure the needed parameters and references to get more details.
This report represents completion of milestone deliverable M2SF-18SNO10309013 "Inventory and Waste Characterization Status Report and OWL Update that reports on FY2018 activities for the work package (WP) SF-18SNO1030901. This report provides the detailed final information for completed FY2018 work activities for WP SF-18SN01030901, and a summary of priorities for FY2019. This status report on FY2018 activities includes evaluations of waste form characteristics and waste form performance models, updates to the OWL development, and descriptions of the two planned management processes for the OWL. Updates to the OWL include an updated user's guide, additions to the OWL database content for wastes and waste forms, results of the Beta testing and changes implemented from it. There are two processes being planned in FY2018, which will be implemented in FY2019. One process covers methods for interfacing with the DOE SNF DB (DOE 2007) at INL on the numerous entries for DOE managed SNF, and the other process covers the management of updates to, and version control/archiving of, the OWL database. In FY2018, we have pursued three studies to evaluate/redefine waste form characteristics and/or performance models. First characteristic isotopic ratios for various waste forms included in postclosure performance studies are being evaluated to delineate isotope ratio tags that quantitatively identify each particular waste form. This evaluation arose due to questions regarding the relative contributions of radionuclides from disparate waste forms in GDSA results, particularly, radionuclide contributions of DOE-managed SNF vs HLW glass. In our second study we are evaluating the bases of glass waste degradation rate models to the HIP calcine waste form. The HIP calcine may likely be a ceramic matrix material, with multiple ceramic phases with/without a glass phase. The ceramic phases are likely to have different degradation performance from the glass portion. The distribution of radionuclides among those various phases may also be a factor in the radionuclide release rates. Additionally, we have an ongoing investigation of the performance behavior of TRISO particle fuels and are developing a stochastic model for the degradation of those fuels that accounts for simultaneous corrosion of the silicon carbide (SiC) layer and radionuclide diffusion through it. The detailed model of the TRISO particles themselves, will be merged with models of the degradation behavior(s) of the graphite matrix (either prismatic compacts or spherical "pebbles") containing the particles and the hexagonal graphite elements holding the compacts.
This paper provides an overview of research evaluating the use of lead tellurite glass as a waste form for salt wastes from electrochemical reprocessing of used nuclear fuel. The efficacy of using lead tellurite glass to immobilize three different salt compositions was evaluated: a LiCl-Li2O oxide reduction salt containing fission products from oxide fuel, a LiCl-KCl eutectic salt containing fission products from metallic fuel, and SrCl2. Physical and chemical properties of glasses made with these salts were characterized with X-ray diffraction, bulk density measurements, differential thermal analysis, chemical durability tests, scanning and transmission electron microscopies, and energy-dispersive X-ray spectroscopy. These glasses were found to accommodate high salt concentrations and have high densities, but further development is needed to improve chemical durability. (C) 2017 Published by Elsevier B.V.
A sample of off-gas condensate produced during a demonstration test of the direct-feed low-activity waste (DFLAW) Radioactive Waste Test Platform using waste retrieved from Hanford storage tank AP-105 waste was analyzed for major cations, anions, total cyanide, Resource Conservation and Recovery Act (RCRA) metals, selected radionuclides, and selected organic compounds. The remaining off-gas condensate was concentrated through evaporation and then used to produce Cast Stone waste forms. After the solid waste forms cured for 28 days, U.S. Environmental Protection Agency (EPA) Method 1311 (EPA 1992) Toxicity Characteristic Leach Procedure (TCLP) tests were conducted on two samples. The TCLP leachates were analyzed for RCRA metals, fluoride, and total cyanide. These chemical analyses were conducted to collect data on the waste form performance and to determine if the waste form will meet the disposal requirements of the Waste Control Specialists LLC (WCS) Federal Waste Disposal Facility (FWF) in Texas (WCS 2015) and the Integrated Disposal Facility at Hanford. The radionuclide results in the off-gas condensate were used to estimate concentrations in the Cast Stone waste forms; these estimates were then compared to Class C limits (30 TAC 336.362 Appendix E). With the possible exception of U-232, all measured radionuclides were determined to be below their respective Class C limits. Inductively coupled plasma-mass spectrometry (ICP-MS) was used to measure most of the radionuclides. It is not possible to differentiate the isotope measured at mass 232 between U 232 and Th-232 by mass spectroscopy. Class C limit comparisons were made by assuming two maximum possible scenarios; one in which all the isotope at mass 232 occurred as Th-232, and another assigning the entire mass contribution to U-232. If the isotope at mass 232 is all Th-232 then the waste form is well below its Class C limit; however, if the isotope at mass 232 is all U-232, then the Class C limit would be exceeded by more than a factor of 8. A chemical procedure to separate uranium from thorium followed by reanalysis by ICP-MS would be required to resolve this issue. A similar issue occurs at mass 238, which could be U-238 or Pu-238; however, in this case Pu-238 can be ruled out as a contributor to the isotope measured at mass 238 for the following reasons. Pu-238 has a half-life of 87.7 years and its daughter product (U-234) has a half-life of 2.5 × 105 years and a measured concentration of < 0.002 µg/L. If significant concentrations of Pu-238 were present in this waste, then the amount of measurable U 234 would have increased over the decades of storage in the Hanford tanks. Because this was not observed, it is concluded that the isotope measured at mass 238 is all U-238. A total of 68 organic compounds were targeted for analysis in the off-gas condensate. Of these compounds, only nine were measured above their respective minimum reportable concentration. These compounds were acenaphthene, acetone, n-butyl alcohol, p,p’-DDT, methyl ethyl ketone, nitrobenzene, o nitrophenol, pyridine, and toluene. Of the detectable compounds, only acenaphthene, acetone, o nitrophenol, and pyridine were above wastewater standards (40 CFR 268.48 - Universal Treatment Standards). None of the organic compounds exceeded the non-wastewater standards (40 CFR 268.48 - Universal Treatment Standards). Analysis of the TCLP leachates from the Cast Stone waste forms indicated that none of the analytes exceeded the Universal Treatment Standard and, in general, all were well below the standards.
Here this paper reviews key properties, applications, and examples of ceramic-metal composites (cermets), and metal matrix composites (MMC) with emphasis on their applicability as waste forms for immobilizing nuclear waste. While the literature is mature for vitrified and cementitious radioactive waste forms, cermet materials have not received adequate attention as potential candidates for immobilizing nuclear waste. To promulgate this effort, this review connects cermet and MMC design, such as hardened tools, with the chemistry of radioactive waste streams. A discussion on certification and qualification standards for cermet waste forms, literature gaps, and “how-to” sections on cermet processing techniques. Key parameters discussed include thermal conductivity, chemical durability, and waste loading, as well as examples for metal-containing waste forms. As cermet waste forms gain momentum within the community, this review paper aims ensure the end-of-life nuclear fuel cycle is addressed from a materials and waste disposition perspective.