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Chloride-Based Volatility for Waste Reduction and/or Reuse of Metallic-, Oxide- and Salt-Based Reactor Fuels

The objective of the chloride based volatility project (CBV) was to demonstrate the ability to separate uranium from used fuel to enable process improvements resulting in 10x reduction of waste volume, while maintaining safeguards standards and global backend costs at $\$$1/MW-hr. Current industrial practices perform separations of used fuel using solvent media in the form of aqueous and molten salt processes, resulting in contaminated process waste. The CBV approach utilized solid state chemistry with no solvent media and was successful in chlorinating uranium and fission product oxides that sublimed into the gas phase and were collected in targeted condensation zones based on temperature gradients of chlorinated products. Recovery of better than 95% of initial uranium in the form of UCl4 was demonstrated when simulated used nuclear fuel was used. Laser induced breakdown spectroscopy, LIBS, and ultraviolet-visible spectroscopy, UV-Vis, were combined into a high temperature flow cell design and utilized as process monitoring techniques to observed chlorinated products leave the reaction vessel in real time.

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Physical Sciences Vistas (Issue 3 2020)

In this issue, highlights of our outstanding R&D supporting the Laboratory’s nuclear security mission include the following. 1. The essential nuclear materials science contributions of MST’s Materials Properties Team to a range of Lab missions, operations, and initiatives. 2. Work in the Sigma Complex supporting NNSA’s Advanced Manufacturing Development milestones by members of Sigma Division and colleagues across the Laboratory and other NNSA sites. 3. Greg Dale’s role in the Lab’s molybdenum program and today as a technical lead on the Scorpius project. 4. Measurements that reveal the role thermal interfaces play in dynamic compression experiments. 5. The first-ever synthesis of an actinide framework, which offers opportunities for understanding these structures as potential radioactive waste forms and provides new models of actinide species transport in the environment. This issue also showcases, as part of our commitment to simultaneous excellence in mission operations and community relations, the successful high-hazard repair of the LANSCE accelerator, which resulted in a large team Laboratory Distinguished Performance Award, and a virtual Summer Physics Camp for Young Women that brought together participants from around the world, even as COVID kept them socially distant in their homes.

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AFC Metal Fuel Workshop Presentations

Compilation of PowerPoint slide decks from presentations given at the 3rd Annual AFC Metal Fuels Workshop. The purpose of this workshop is to bring the national metallic fuel stakeholders together to discuss status and needs of metallic fuel and review the DOE AFC Metal Fuel R&D. Desired Outcomes - Advance Metallic Fuel Technology: 1. Stakeholder Community Building 2. National Program R&D Accountability, Planning Support, and Increased Stakeholder Advocation.

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Equity Considerations in Siting Consolidated Interim Storage Facilities for Commercial Spent Nuclear Fuel

Questions of equity and fairness are often raised by representatives from State, Tribal and local governments and members of the public when resolving conflicts over siting of nuclear facilities. However, the two terms are not synonymous: equity can be quantified while fairness is much more subjective. The Department of Energy's (DOE) December 2021 Request for Information sought input on how to site federal facilities for the temporary, consolidated storage of spent nuclear fuel (SNF) using a consent-based approach. It is anticipated that just such questions about equity and fairness associated with the potential emergence of more than one host site may be raised by the twelve groups of university, nonprofit and private sector partners (Consortia) working to support community engagement, inclusively involve stakeholders, build relationships, and develop innovative forms of mutual learning and public capacity to participate in the consent-based siting process for a federal consolidated interim storage facility during the current Planning & Capacity Building stage of the consent-based siting process. In terms of DOE's Integrated Waste Management System (IWMS), sociopolitical equity concepts are a factor in all aspects of IWMS development and operations and will be particularly applicable should two or more host sites become a possibility, either by the emergence of multiple volunteer hosts or by pursuit as a IWMS program strategy. This paper summarizes recent analyses that explore how four equity metrics - number of states, division of the projected SNF total by the year 2083, current population and land area - might be perceived by host communities, states and regions if two, three or four sites for hosting federal consolidated interim storage facilities were to be contemporaneously realized. Existing institutional arrangements, including Nuclear Regulatory Commission regions, Federal Energy Regulatory Commission regions and Low-Level Radioactive Waste Disposal Compacts, were selected to create hypothetically merged two, three and four-region scenarios to calculate how the four metrics balance out. Projected SNF burden was prioritized with regional contiguity of the consolidated regions a requirement for a functional scenario. The intent was not to promote or suggest any construct as a program objective; the configurations are geopolitical abstractions only to explore potential perceptions of equity. Understanding the possible issues of equity that could arise may benefit program efforts toward achieving a cooperative federalism wherein both the federal and multiple State governments share the goal of manifesting more than one federal consolidated interim storage facility. The main finding is that it is not possible to optimize for all four metrics simultaneously. The analyses demonstrate that trying to create a sense of equity by backfitting a solution to a random population and land distribution will always contain a degree of artificiality.

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Conceptual Model Testing Related to SDU 6 Drainwell Observations

From its inception in the early 1950s through the end of the Cold War in the early 1990s, the Savannah River Site (SRS) produced nuclear materials for national defense in five reactors. Additionally, irradiated reactor fuel and target tubes were dissolved in nitric acid to recover plutonium and uranium using the PUREX (Plutonium Uranium Reduction EXtraction) process. Liquid waste from these chemical separations processes was then stored onsite in 51 underground tanks. Eight waste storage tanks have been operationally closed (i.e. cleaned and grouted) and the remaining tanks hold a mixture of liquids, insoluble solids, and precipitated salts (SRMC-LWP-2022-00001), the latter generated by evaporating water from the liquid waste. Waste is currently being retrieved from tanks and separated into 1) high-radioactivity, low-volume, and 2) low-radioactivity, high-volume components, principally through the Salt Waste Processing Facility (SWPF) (SRMC-LWP-2023-00001). The former waste stream is vitrified in the Defense Waste Processing Facility (DWPF), stored onsite, and destined for offsite disposal in a deep geologic repository. The latter stream is mixed with dry cementitious materials in the Saltstone Production Facility (SPF) and the wet slurry placed in onsite Saltstone Disposal Units (SDUs) within the Saltstone Disposal Facility (SDF), where it hardens into a cement waste form termed saltstone. A low-infiltration surface cover system will be placed over the SDF at closure, where SDUs will then be in the subsurface post-closure (SRR-CWDA-2019-00001).

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LAW Simulant Recipes for Evaluation of Real-Time, In-Line Monitoring Instruments

Statistically designed recipes were generated for evaluation of in-line instrumentation for the Real-Time In-Line Monitoring (RTIM) program in support of the Hanford Direct-Feed Low Activity Waste (DFLAW) program. The composition matrices were prepared based on Low Activity Waste (LAW) feed vector, melter feed, and Effluent Management Facility (EMF) feed information provided by the flowsheet integration modelling for the DFLAW portion of the Waste Treatment Plant (WTP) mission. These composition matrices were converted to recipes for the LAW feed using the approaches for LAW simulant recipes developed by Savannah River National Laboratory (SRNL). Recipes for the glass forming chemicals (GFCs) were developed based on expected mineral forms to be used to for each element to be added to the recipe. The recipe matrices are shown in the Appendix.

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Glass Crystallization Constraints for WTP LAW Operations: Assessment of Isothermal Treatments on Crystal Formation

Much work has been done to expand the glass composition region available for operation of the Hanford Tank Waste Treatment and Immobilization Plant. This includes the development of updated glass property-composition models as well as constraints. This report supports this effort by suggesting constraints for avoiding excessive, and likely detrimental, crystallization during melter operation while processing advanced low-activity glasses. The constraints target Cassiterite and ZrO 2 -containing phases (ZCP, e.g., Baddeleyite and Zircon) that can form when melter temperatures drop below 1100 °C. These types of crystals were found to be potentially detrimental during processing as they are denser than low-activity waste glass melts; with densities of 6.95 g/cm 3 for Cassiterite and 5.68 g/cm 3 for Baddeleyite (the most prevalent ZCP). Compared to melt densities of approximately 2.65 g/cm 3 . Thus, they have the potential to form during melter idling and settle to the bottom of the melter or inside the melter. If the crystals are present in appreciable amounts, they can result in blockages of the pour-spout riser, which impacts glass pouring and melter operation. Additionally, SnO 2 and ZrO 2 are added to glass formulations to improve glass durability. Their precipitation from the melt may reduce overall glass durability. Using previously acquired results and results from testing during this effort, the following constraints (Table S.1) were determined and are recommended to reduce the risk of forming crystals of the types and concentrations that are likely detrimental to melter operation.

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LDR Inorganic Spiked Simulants in Pozzolan-Substituted Cast Stone for Hanford Pretreated Low-Activity Tank Waste

Pretreated Low Activity Waste (PTW/LAW) at the Hanford Site, is currently projected for disposition through a cementitious waste form. The current standard formulation, Cast Stone, uses Class F fly ash, blast furnace slag, and Portland cement. However, the future availability of Class F fly ash is uncertain, as many coal-fired power plants—the source of this byproduct—are being decommissioned or converted to natural gas. This issue has prompted research into identifying and evaluating suitable alternative materials to replace fly ash in the cementitious waste forms used by the Department of Energy (DOE). The Savannah River National Laboratory (SRNL) successfully identified four natural pozzolans for the replacement of Class F fly ash in the current Savannah River Site (SRS) low-level waste (LLW) form, Saltstone.

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Oil and Natural Gas Development near and beneath Uranium Tailings Cells and Other Remediated Sites - 20358

DOE LM is responsible for maintaining remedies at more than 50 remediated sites that require active long-term surveillance and maintenance (LTS and M). Institutional controls (ICs) were established to limit human and environmental exposures to residual contamination by controlling land use, restricting access to potential hazards, and making the public aware of potential dangers from the residual contamination. ICs for each site were developed based on current and foreseeable conditions; however, these controls should evolve to mitigate potential human health and other environmental risks from unanticipated changes in activities or site conditions. Activities conducted beyond the DOE long-term care boundaries by non-DOE parties may impact the effectiveness of ICs or even the long-term stability of disposal cells and groundwater remedies. Several sites that LM manages or that will transfer to LM for LTS and M are in active oil and gas production basins. The sites are associated with uranium ore milling or nuclear test sites and have been remediated or are in the process of remediation and have no ongoing DOE mission. Particularly since 2005, hydraulic fracturing ('fracking') combined with directional drilling has dramatically increased oil and natural gas (oil/gas) production in the United States, now making it the number one hydrocarbon-producing country. Fracking has allowed production from shale and other rocks of low natural permeability that were historically not considered viable oil/gas resources. Also, because wellbores can now be drilled as many as 5 kilometers or more horizontally, hydrocarbons can be recovered from zones without having access to the surface above them. Drilling activity near Rulison, Colorado, the location of an underground nuclear detonation managed by LM, has raised public concerns that remnant radioactivity in the detonation zone could migrate to producing wells and enter the natural gas distribution system. At sites like the Falls City, Texas, Disposal site, transitioned to LM with a split estate, increased production in the region has resulted in wellbores beneath the long-term care boundary of the site. While the DOE license for Falls City was approved by the NRC in 1997 without the acquisition of the subsurface rights, NRC has raised concerns on whether this activity impacts the integrity of the cell and/or groundwater remedies. In Wyoming, LM is anticipating receiving the license for the Bear Creek site and manages the Spook site, both locations of uranium mill tailings disposal cells. These Wyoming sites are in an active region of major oil and gas development. This change in surrounding land use will require LM to work collaboratively with NRC to address these concerns. At several DOE sites radioactive waste, and often intermixed nonradioactive constituents, is permanently isolated in engineered disposal cells. At other sites, residual contamination can be present in groundwater, blast cavities, and infinite amounts within soil. Areas targeted for oil and gas development at the Texas and Wyoming sites range from depths of 2440 to 3350 meters (8000-11000 feet) below ground surface. When most site remedies were designed, oil and gas development was not considered to be an issue within the site boundary. With the more recent uses of directional drilling, fracking, and associated wastewater injections, the evaluative criteria for incoming sites and ICs for managing long-term protectiveness and regulatory compliance are changing. Although DOE surface ownership was previously thought to be a robust IC to prevent surface and subsurface development, particularly at disposal sites, that may no longer be the case. Whereas the subsurface development at Texas and Wyoming sites is currently occurring at thousands of meters beneath the surface, shallower and direct onsite development would be more of a concern for LM. The energy introduced when a well is hydraulically fractured causes microseismic events (magnitude -2 to 1.0) as the fractures propagate but does not directly cause seismic events (earthquakes) of sufficient magnitude to damage surface structures. Additionally, the extent of the hydraulic fractures is limited to the targeted depths, which are far below the surface. However, earthquakes of sufficient magnitude to damage surface structures have been attributed to the injection of wastewater into disposal wells. States that have experienced these effects have enacted regulations that limit the rate and pressures that wastewater can be injected into disposal wells. Items LM may consider are the need for monitoring the volume of water injected into nearby disposal wells and possibly installing seismic stations at sites most susceptible to damage. While the need to demonstrate that no impact from oil and gas extraction activities on a site groundwater remedy or disposal cells will vary from site to site, LM is assessing risk criteria for this activity. Though LM has not experienced an issue yet at a uranium tailings disposal site, it cannot assume that there will be none, and must address NRC concerns. LM is building on past experiences at other sites and beginning to form new processes with the hope that these concepts can be applied for other future sites. (authors)

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Disposal Concepts for a High-Temperature Repository in Shale.

Disposal of large, heat-generating waste packages containing the equivalent of 21 pressurized water reactor (PWR) assemblies or more is among the disposal concepts under investigation for a future repository for spent nuclear fuel (SNF) in the United States. Without a long (>200 years) surface storage period, disposal of 21-PWR or larger waste packages (especially if they contain high-burnup fuel) would result in in-drift and near-field temperatures considerably higher than considered in previous generic reference cases that assume either 4-PWR or 12-PWR waste packages (Jové Colón et al. 2014; Mariner et al. 2015; 2017). Sevougian et al. (2019c) identified high-temperature process understanding as a key research and development (R&D) area for the Spent Fuel and Waste Science and Technology (SFWST) Campaign. A two-day workshop in February 2020 brought together campaign scientists with expertise in geology, geochemistry, geomechanics, engineered barriers, waste forms, and corrosion processes to begin integrated development of a high-temperature reference case for disposal of SNF in a mined repository in a shale host rock. Building on the progress made in the workshop, the study team further explored the concepts and processes needed to form the basis for a high-temperature shale repository reference case. The results are described in this report and summarized..

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Test Plan for Investigation of Hydrogen Generation in SNF Canisters

This report presents a test plan to investigate radiolytic hydrogen generation in spent nuclear fuel (SNF) canisters containing Zr-based cladding materials. The initial primary contributor to the generation of radiolytic hydrogen is estimated to be the residual physisorbed water on the ZrO 2 film, post-dry out. Over the longer term the primary hydrogen source is associated with the aluminum hydroxides and water vapor. The proposed testing to be conducted in FY22 would consist of lab-scale testing on non-radioactive surrogates of oxidized ZIRLO tubing and unalloyed zirconium using a miniature steel canister (“mini-canister") designed to allow intermittent, in-situ sampling of the canister gas during irradiation. The mini-canister approach for irradiation with in-situ monitoring system was used in a recent and on-going study [McNamara and Verst, 2020a & 2020b; Verst et al., 2021] to measure radiolytic hydrogen generation from aluminum SNF cladding surrogate materials. This proposed testing will form part of the overall materials performance evaluation of the commercial SNF-in-canister system and is part of the technical bases for their continued safe dry storage

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Decoding Zeolite Crystallization and Stage III in Nuclear Waste Glasses by Coupled Modeling and Experiments

Under specific conditions of pH and temperature, nuclear waste immobilization borosilicate glasses may exhibit a sudden acceleration in their corrosion kinetics (stage III)—a behavior that has been associated with the formation of zeolite crystals. Such accelerated dissolution may compromise the integrity of nuclear wasteforms placed in geological depositories. However, thus far, none of the available models is able to predict the thermodynamic propensity and kinetics of zeolite precipitation as a function of the solution conditions due to (i) a lack of fundamental knowledge regarding the nucleation & growth mechanisms of zeolitic phases, (ii) uncertainty regarding the compositions (types) of zeolites that may form and the rate-limiting step in their precipitation as a function of the solution conditions, and (iii) the complexities that arise due to the vast parametric space (i.e., solution chemistry, temperature, number of secondary phases, etc.) that encompass these systems under conditions of environmental exposure. To resolve these challenges, this project aimed to unambiguously identify the thermodynamic propensity for zeolite precipitation and the kinetics thereof as a function of the solution conditions (composition, pH, and temperature). To achieve this goal: 1) We identified the solution conditions and zeolite phases relevant to nuclear glass dissolution. 2) We performed a series of ab initio molecular dynamics (AIMD) simulations to compute the thermodynamic properties of a group of characteristic zeolites that features a large range of compositions, various hydration levels, a wide range of framework structures, and partial atomic site occupancies. 3) We released a first-of-a-kind self-consistent thermodynamic database that can be used to assess the kinetics and the stability fields of zeolitic phases within a Gibbs energy minimization (GEM) framework. 4) We developed a robust geochemical modeling method allowing us to predict the stability of secondary phases (including zeolites, calcium–silicate–hydrate gels, and clays) upon the dissolution of nuclear waste immobilization glasses. 5) We introduced a model that predicts the dissolution kinetics of a series of borosilicate nuclear waste immobilization glasses in terms of the topology of their atomic network. 6) We investigated the roles of the solution composition on the crystallization kinetics of phillipsite zeolites and tobermorite silicate hydrates. Via PNNL’s collaboration and engagement, this project directly supports DOE’s nuclear waste immobilization activities by offering a technical, science-based foundation that will (i) facilitate predictions of the long-term corrosion rates and extents of existing nuclear waste immobilization glasses to help ensure safe and successful vitrification operations, (ii) inform the development of advanced glass formulations with enhanced durability, and, (iii) enable cost-savings that result from making more decisive and hence less conservative predictions while offering higher levels of nuclear waste embedment in smaller, more compact glass volumes.

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Crystallization Constraints for WTP LAW Operations: Assessment of CCC Impacts on VHT and PCT

Much work has been done to expand the glass composition region available for operation of the Hanford Waste Treatment and Immobilization Plant. This includes the development of updated glass property-composition models as well as constraints. This report supports this effort by suggesting constraints for avoiding excessive, and likely detrimental, crystallization during slow cooling of the low-activity glass waste forms in their containers. The constraints target crystals in the Na-Al-silicate and Na-Ca-silicate families. These types of crystals were found to be potentially detrimental to glass durability as they remove Al and Si from the glass matrix, resulting in poor performance of the residual glass during testing such as the Product Consistency Test and the Vapor Hydration Test. Using previously acquired results and results from testing during this effort, the constraints described in the report were determined, and are suggested as options to reduce the risk of forming crystals of the types and concentrations that are likely detrimental to glass durability.

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Containers and refractory metal coating therefore for containing radioactive materials

Fabricating structural components for a spent nuclear fuel container using the steps of forming cylindrical or rectangular channels to produce a structural component for a spent nuclear fuel container and applying a coating that includes tantalum-based material to the cylindrical or rectangular channels.

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Solidification of REDC Organics and Airborne Release Fraction Measurements

The Radiochemical Engineering Development Center (REDC) generates various liquid organic wastes from processing irradiated targets to recover heavy elements. In the past, these organics were discharged to the Oak Ridge National Laboratory (ORNL) liquid low-level waste (LLLW) system, along with the aqueous waste. Because of a reduction in aqueous LLLW from other ORNL generators and an increase in the radionuclide concentration, particularly 238 Pu, in the organic waste stream, the organics can no longer be discharged to the LLLW system. The plan is to solidify the liquid organic waste for disposal as solid debris waste. The documented safety analysis for REDC uses an airborne release fraction of 5 x 10 -4 with a respirable fraction of 0.2 for plutonium and other actinides from packaged solid debris waste during a fire scenario, for an overall airborne release fraction/respirable fraction of 10 -4 . Solidifying the organic liquids, either by using PM-199 Organoclay ® or by grouting, would produce solid waste forms with no free liquid, which should qualify for disposal at the Waste Isolation Pilot Plant. The use of Organoclay would be much simpler to implement inside a hot cell. Granular Organoclay can be added to the organic waste solutions until there is a dry layer on top of the liquid and then allowed to cure for a few hours. Grouting the liquids would require using multiple ingredients and mixing steps. Both methods produced waste forms that trapped cerium, as a surrogate for plutonium, inside the waste, with airborne release fractions during fire scenario tests of well below the 10 -4 limit.

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Criticality Analysis of FSV Spent Nuclear Fuel in the DOE Standard Canister

The U.S. Department of Energy (DOE) is responsible for managing over 300 types of spent nuclear fuel (SNF). To manage this large variety of fuel types, DOE plans to employ standardized canisters for the transportation, long-term storage, and eventual disposal of SNF. Idaho National Laboratory is currently supporting DOE’s SNF Packaging Demonstration Project, in which Fort Saint Vrain (FSV) fuel assemblies will be loaded into a DOE Standard Canister. This paper presents criticality calculations demonstrating that all four or five FSV fuel assemblies loaded into the DOE Standard Canister will remain subcritical in any expected normal or credible abnormal conditions. Previous criticality analyses were performed for one FSV fuel assembly and 12 Peach Bottom Core 2 fuel elements loaded into a DOE Standard Canister. This paper covers the criticality analysis performed for loading both four and five FSV fuel assemblies into a DOE Standard Canister. Various intact and degraded mode configurations were modeled in conducting the criticality calculations. This analysis encompassed three different configurations: (1) a single DOE Standard Canister loaded into a concrete storage overpack, (2) seven DOE Standard Canisters loaded into a concrete storage overpack, and (3) nine DOE Standard Canisters loaded into a concrete storage overpack. The overpack dimensions were varied for each of the three configurations, and transport, storage, and disposal scenarios were analyzed for each configuration. For transport scenarios, a pair of degradation cases was analyzed. In the first case, the fuel compacts became degraded and were removed from the fuel block, then deposited at the bottom of a horizontally placed canister, thereby simulating a drop event. The canister was considered to remain intact. In the second case, the spacing between horizontally placed canisters in a nine-canister overpack was reduced such that the canisters were piled on top of each other, simulating a drop event. For this case, no degradation of the canister internals or fuel was considered. For storage scenarios, the water moderator location in the system was varied to enable identification of the most reactive configurations. Dry and wet conditions were analyzed for the fuel materials, canister, and overpack. For disposal scenarios, two degradation cases were analyzed. In the first, the stainless-steel internals of the canister degraded to either hematite or goethite under both dry and wet conditions. In the second case, degraded FSV fuel formed a uranium-water slurry that filled the coolant/void holes. None of the cases presented exceeded the application specific upper subcritical limit.

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Vitrification of Hanford Tank 241-AP-105 Waste at 7 M Na and Equivalent Simulant

Hanford Site nuclear waste is to be vitrified at the Waste Treatment and Immobilization Plant (WTP), which is a part of the safe and efficient retrieval, treatment, and disposal mission of the U.S. Department of Energy Office of River Protection. Hanford tank 241-AP-105 (referred to herein as AP-105) is one of the initial Hanford radioactive tank wastes planned to be processed and vitrified. A portion of AP-105 waste was retrieved by Washington River Protection Solutions, LLC (WRPS) and transferred to Pacific Northwest National Laboratory (PNNL). The waste went through dilution by Columbia River water to reach a target sodium (Na) concentration of 7 M, solids filtration, and cesium removal by ion exchange. A glass composition was calculated from the Kim et al. glass models to satisfy the WTP baseline requirements based on the as-received sample and the target dilution to 7 M, from which a simulant was calculated and glass forming chemical (GFC) additions were determined to form a liquid/solids mixture called melter feed. To prepare for the processing of the 7 M Na AP-105 waste melter feed and learn about the production expectations, the melter feed simulant of 7 M Na AP-105 waste was processed in a non-radioactive, continuous laboratory-scale melter (CLSM) system.

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Performance Assessment for the E-Area Low-Level Radioactive Waste Disposal Facility at the Savannah River Site: Appendix D

This appendix to Chapter 5, Section 5.1 provides supplemental concentration profiles for radionuclide species in STs and ETs that contribute to at least 0.1% of the sum-of-fractions. All concentrations are reported as pCi L -1 per Ci parent buried. The following nomenclature is used for all radionuclides in all DUs: an uppercase letter suffix indicates a SWF (e.g., I-129G, C-14N, H-3F, etc.), while the absence of an uppercase letter denotes a generic waste form (e.g., I-129, C-14, H-3, etc.).

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