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At least 253 records · Page 14

Summary of Uranium Solubility Studies in Concrete Waste Forms and Vadose Zone Environments

One of the methods being considered for safely disposing of Category 3 low-level radioactive wastes is to encase the waste in concrete. Concrete encasement would contain and isolate the waste packages from the hydrologic environment and act as an intrusion barrier. The current plan for waste isolation consists of stacking low-level waste packages on a trench floor, surrounding the stacks with reinforced steel, and encasing these packages in concrete. These concrete-encased waste stacks are expected to vary in size with maximum dimensions of 6.4 m long, 2.7 m wide, and 4 m high. The waste stacks are expected to have a surrounding minimum thickness of 15 cm of concrete encasement. These concrete-encased waste packages are expected to withstand environmental exposure (solar radiation, temperature variations, and precipitation) until an interim soil cover or permanent closure cover is installed and to remain largely intact thereafter. Any failure of concrete encasement may result in water intrusion and consequent mobilization of radionuclides from the waste packages. This report presents the results of investigations elucidating the uranium mineral phases controlling the long-term fate of uranium within concrete waste forms and the solubility of these phases in concrete pore waters and alkaline, circum-neutral vadose zone environments.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Immobilization of high-level waste salt in dechlorinated zeolite waste forms. Final report

This project addressed the main challenges associated with the disposal of electrorefiner salt: maximization of fission products in a final waste form and the associated processing costs. Since over half of the mass of the ER salt is chlorine in the form of non-radioactive chloride ions, our approach for achieving dechlorination is through the formation of HCl gas during the exchange of the metal ions into ultrastable H-Y (USHY) zeolite. The zeolite containing the fission products was then sintered into a chemically durable waste form.

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Preliminary Assessment of the Low-Temperature Waste Form Technology Coupled with Technetium Removal

The U.S. Department of Energy Office of Environmental Management (EM) is engaging the national laboratories to provide the scientific and technological rigor to support EM program and project planning, technology development and deployment, project execution, and assessment of program outcomes. As an early demonstration of this new responsibility, Pacific Northwest National Laboratory (PNNL) and Savannah River National Laboratory (SRNL) have been chartered to implement a science and technology program addressing low-temperature waste forms for immobilization of DOE aqueous waste streams, including technetium removal as an implementing technology. As a first step, the laboratories examined the technical risks and uncertainties associated with the Cast Stone waste immobilization projects at Hanford. Science and technology needs were identified for work associated with 1) conducting performance assessments and risk assessments of waste form and disposal system performance, and 2) technetium chemistry in tank wastes and separations of technetium from waste processing streams. Technical approaches to address the science and technology needs were identified and an initial sequencing priority was suggested. The following table summarizes the most significant science and technology needs and associated approaches to address those needs. These approaches and priorities will be further refined and developed as strong integrated teams of researchers from national laboratories, contractors, industry, and academia are brought together to provide the best science and technology solutions. Implementation of a science and technology program that addresses these needs by pursuing the identified approaches will have immediate benefits to DOE in reducing risks and uncertainties associated with near-term decisions regarding supplemental immobilization at Hanford. Longer term, the work has the potential for cost savings and for providing a strong technical foundation for future performance assessments at Hanford and across the DOE complex.

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Waste Classification based on Waste Form Heat Generation in Advanced Nuclear Fuel Cycles Using the Fuel-Cycle Integration and Tradeoffs (FIT) Model - 13413

This study explores the impact of wastes generated from potential future fuel cycles and the issues presented by classifying these under current classification criteria, and discusses the possibility of a comprehensive and consistent characteristics-based classification framework based on new waste streams created from advanced fuel cycles. A static mass flow model, Fuel-Cycle Integration and Tradeoffs (FIT), was used to calculate the composition of waste streams resulting from different nuclear fuel cycle choices. This analysis focuses on the impact of waste form heat load on waste classification practices, although classifying by metrics of radiotoxicity, mass, and volume is also possible. The value of separation of heat-generating fission products and actinides in different fuel cycles is discussed. It was shown that the benefits of reducing the short-term fission-product heat load of waste destined for geologic disposal are neglected under the current source-based radioactive waste classification system, and that it is useful to classify waste streams based on how favorable the impact of interim storage is in increasing repository capacity. (authors)

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Analysis of Legacy {sup 85}Kr Waste Form Samples - 16319

In the late 1970's, the Idaho Chemical Processing Plant conducted an R and D program on krypton encapsulation. Legacy samples composed of {sup 85}Kr incorporated in solid zeolite 5A material, and five small metal tubes containing a mixture of the zeolite combined with a glass matrix resulting from hot isostatic pressing, have been preserved. These samples were shipped to Oak Ridge National Laboratory (ORNL) in mid-FY 2014. After receipt and repackaging, the samples were examined by x-ray imaging and x-ray tomography. Two of the capsules appear to contain an amorphous mass within the capsules. An image of one capsule clearly shows the saw marks on the capsule and a quantity of loose pellet or bead-like material remaining in the capsule. An image of another capsule shows similar bead-like material within the intact capsule. One of the capsules was previously opened. The end of this capsule appears to have been cut off, and there are additional saw marks on the side of the capsule. X-ray tomography allowed the capsules to be viewed along the three axes. Of most interest was determining whether there was any residual material in the closed end of this capsule. The images confirmed the presence of residual material within this capsule. The material appears to be compacted but still retains some of the bead-like morphology. Based on the initial nondestructive assay (NDA) and the fact that there are two obviously breached samples, a plan was developed for exploratory tests that would be conducted with the breached specimens before opening the three intact capsules. Preparations are being made to determine the fraction of krypton/xenon remaining in the waste form matrix and the amount of rubidium remaining in the waste form matrix. The inner surface of the breached capsules will be examined for corrosion. (authors)

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Simultaneous three-dimensional elemental mapping of Hollandite and Pyrochlore material phases in ceramic waste form materials

In this study, differential X-ray absorption contrast tomography was performed on model ceramic composite systems to image the 3D spatial distributions of Ga and Nd containing phases. The model material systems were fabricated such that they contained two constituent phases. Ga–doped Ba hollandite (Ba 1.33 Ga 2.66 Ti 5.34 O 16 ), and pyrochlore (Nd 2 Ti 2 O 7 ) which are under consideration as nuclear waste immobilization matrices. Two complementary techniques have been used to characterize the 3D distribution of phases. The analysis suggests that the 3D spatial distributions of hollandite and pyrochlore can be readily identified through the distributions Ga and Nd, respectively. These results represent a critical development towards characterizing the complex microstructure inherent to practical materials such as multiphase ceramic composite waste forms. Furthermore, these methods can be applied to elucidate microstructural features that fundamentally determine the performance and properties of complex systems, which is central to the design of durable waste forms as well as many other real materials such fuel cells, batteries, ultra-high temperature ceramics.

36 MATERIALS SCIENCE↗

Candidate Low-Temperature Glass Waste Forms for Technetium-99 Recovered from Hanford Effluent Management Facility Evaporator Concentrate

Alternative treatment and disposition options may exist for technetium-99 (99Tc) in secondary liquid waste from the Hanford Direct-Feed Low-Activity Waste (DFLAW) process. One approach includes development of an alternate glass waste form that is suitable for on-site disposition of technetium, including salts and other species recovered by ion exchange or precipitation from the EMF evaporator concentrate. By recovering the Tc content from the stream, and not recycling the treated concentrate, the DFLAW process can potentially be operated in a more efficient manner that lowers the cost to the Department of Energy. This report provides a survey of candidate glass formulations and glass-making processes that can potentially incorporate technetium at temperatures <700 °C to avoid volatilization. Three candidate technetium feed streams are considered: (1) dilute sodium pertechnetate loaded on a non-elutable ion exchange resin; (2) dilute sodium-bearing aqueous eluent from ion exchange recovery of pertechnetate, or (3) technetium(IV) oxide precipitate containing Sn and Cr solids in an aqueous slurry. From the technical literature, promising candidate glasses are identified based on their processing temperatures and chemical durability data. The suitability and technical risk of three low-temperature glass processing routes (vitrification, encapsulation by sintering into a glass composite material, and sol-gel chemical condensation) for the three waste streams was assessed, based on available low-temperature glass data. For a subset of candidate glasses, their long-term thermodynamic behavior with exposure to water and oxygen was modeled using Geochemist’s Workbench, with and without addition of reducing stannous ion. For further evaluation and development, encapsulation of precipitated TcO2/Sn/Cr in a glass composite material based on lead-free sealing glasses is recommended as a high priority. Vitrification of pertechnetate in aqueous anion exchange eluent solution using a high lead content borate glass, or other low melting glass is also recommended for further evaluation and development. Additional laboratory studies of phase behavior and chemical durability of low-temperature glasses is also recommended to provide risk mitigation if one of the primary development paths proves infeasible. This report is a deliverable for the task “Candidate Low-T Glass Waste Forms for EMF Bottoms On-Site Disposition Alternative Option.”

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Prototype Development of Remote Operated Hot Uniaxial Press (ROHUP) to Fabricate Advanced Tc-99 Bearing Ceramic Waste Forms - 13381

The objective of this senior student project is to design and build a prototype construction of a machine that simultaneously provides the proper pressure and temperature parameters to sinter ceramic powders in-situ to create pellets of rather high densities of above 90% (theoretical). This ROHUP (Remote Operated Hot Uniaxial Press) device is designed specifically to fabricate advanced ceramic Tc-99 bearing waste forms and therefore radiological barriers have been included in the system. The HUP features electronic control and feedback systems to set and monitor pressure, load, and temperature parameters. This device operates wirelessly via portable computer using Bluetooth{sup R} technology. The HUP device is designed to fit in a standard atmosphere controlled glove box to further allow sintering under inert conditions (e.g. under Ar, He, N{sub 2}). This will further allow utilizing this HUP for other potential applications, including radioactive samples, novel ceramic waste forms, advanced oxide fuels, air-sensitive samples, metallic systems, advanced powder metallurgy, diffusion experiments and more. (authors)

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Final report: Understanding influence of thermal history and glass chemistry on kinetics of phase separation and crystallization in borosilicate glass-ceramic waste forms for aqueous reprocessed high level waste

This report provides an overview of the research activities conducted over the three-year period, October 1, 2015 to September 30, 2018. The project consisted of the US DOE component and a parallel project funded by the UK’s EPSRC. The US project is reported here, with some overview of the UK project results. The project was designed to be highly collaborative, including work in the US by Washington State University and Rutgers University, and in the UK by the University of Sheffield and the University of Warwick. Pacific Northwest National Laboratory supported the US project with some synthesis and some characterization. The overall program had two aims: (Aim 1) Understand fundamental mechanisms of the phase transitions leading to the conversion of melt to multiphase glass-ceramic as a function of composition and cooling rate; (Aim 2) Understand influence of glass chemistry on kinetics of phase separation and crystallization. This report includes the summary of the project objectives, approaches, results and deliverables.

36 MATERIALS SCIENCE↗

Three-dimensional mapping of crystalline ceramic waste form materials

Here, we demonstrate the use of synchrotron-based, transmission X-ray microscopy (TXM) and scanning electron microscopy to image the 3-D morphologies and spatial distributions of Ga-doped phases within model, single- and two-phase waste form material systems. Gallium doping levels consistent with those commonly used for nuclear waste immobilization (e.g., Ba 1.04 Cs 0.24 Ga 2.32 Ti 5.68 O 16 ) could be readily imaged. This analysis suggests that a minority phase with different stoichiometry/composition from the primary hollandite phase can be formed by the solid-state ceramic processing route with varying morphology (globular vs. cylindrical) as a function of Cs content. Our results represent a crucial step in developing the tools necessary to gain an improved understanding of the microstructural and chemical properties of waste form materials that influence their resistance to aqueous corrosion. This understanding will aid in the future design of higher durability waste form materials.

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Characterization and Leaching Tests of the Fluidized Bed Steam Reforming (FBSR) Waste Form for LAW Immobilization - 13400

Several supplemental technologies for treating and immobilizing Hanford low activity waste (LAW) have been evaluated. One such immobilization technology is the Fluidized Bed Steam Reforming (FBSR) granular product. The FBSR granular product is composed of insoluble sodium aluminosilicate (NAS) feldspathoid minerals. Production of the FBSR mineral product has been demonstrated both at the industrial and laboratory scale. Pacific Northwest National Laboratory (PNNL) was involved in an extensive characterization campaign. The goal of this campaign was to study the durability of the FBSR mineral product and the encapsulated FBSR product in a geo-polymer monolith. This paper gives an overview of results obtained using the ASTM C 1285 Product Consistency Test (PCT), the EPA Test Method 1311 Toxicity Characteristic Leaching Procedure (TCLP), and the ASTMC 1662 Single-Pass Flow-Through (SPFT) test. Along with these durability tests an overview of the characteristics of the waste form has been collected using Scanning Electron Microscopy (SEM), X-ray Diffraction (XRD), microwave digestions for chemical composition, and surface area from Brunauer, Emmett, and Teller (BET) theory. (authors)

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Advanced Electrochemical Waste Forms

This is a brief description of PNNL's efforts in FY2011 towards developing advanced electrochemical waste forms. This is a short section that will become part of a larger document being put together by INL.

electrochemical↗

Electrochemical corrosion of multiphase stainless steel-based alloy nuclear waste forms

Abstract The electrochemical corrosion behaviors of two multiphase alloys representing waste forms made with 316 L stainless steel and different amounts of surrogate metallic fuel wastes were measured and related to the microstructures. Potentiodynamic (PD) scans were performed in an acid brine solution and the corroded surfaces were characterized with scanning electron microscopy (SEM) to compare the electrochemical responses to the corrosion of specific phases. PD scans for the two multiphase alloys, 316 L stainless steel, and pure palladium were compared to understand the complex corrosion behavior of these multiphase alloys also recently classified as multi principle element alloys (MPEAs) and to determine the effects of alloying elements and noble metals present in constituent phases on the corrosion behavior.

Gattu, Vineeth Kumar (ORCID:0000000307265813)↗

Single Pass Flow-Through (SPFT) Test Results of Fluidized Bed Steam Reforming (FBSR) Waste Forms used for LAW Immobilization - 12252

Several supplemental technologies for treating and immobilizing Hanford low activity waste (LAW) are being evaluated. One such immobilization technology being considered is the Fluidized Bed Steam Reforming (FBSR) product, which is granular and will be monolithed into a final waste form. The granular component is composed of insoluble sodium aluminosilicate (NAS) feldspathoid minerals. Production of the FBSR mineral product has been demonstrated at the industrial, engineering, and laboratory scales. Single-Pass Flow-Through (SPFT) tests at various flow rates have been conducted with the granular products fabricated using the engineering- and laboratory-scale methods. Results show that the forward dissolution rate for the engineering-scale mineral product is 0.6 (±0.2)x10{sup -3} g/m{sup 2}d while the forward dissolution rate for the laboratory-scale mineral product is 1.3 (±0.5)x10{sup -3} g/m{sup 2}d. (authors)

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Review and Experimental Comparison of the Durability of Iodine Waste Forms in Semi-Dynamic Leach Testing

To ensure the safe disposal of radioiodine-containing nuclear wastes, a durable iodine waste form (IWF) is required. Many IWFs have been developed and evaluated for chemical durability using a wide range of test methods, making direct comparisons difficult as highlighted in this work through a review of available IWF corrosion data. To move toward a common dataset, a semi-dynamic leach test suite was experimentally demonstrated using several IWF types, providing standard comparisons. The results highlighted clear differences in corrosion resistance between various IWFs. This test suite is suggested for future studies to generate comparable data for a common dataset.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗