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Advanced Reactors Spent Fuel & Waste Science and Technology Program

Based on the higher interest in Advanced Reactor (AR) deployment (e.g., ARDP ) for potential new fuel cycles, the Spent Fuel & Waste Science and Technology (SFWST) Program has begun to evaluate the possible implications of long-term management and final disposition of potential Advance Reactor spent nuclear fuels (SNF) that would be generated in potential advanced reactors. Safely managing and dispositioning the potential future AR SNF, and any other associated radioactive wastes, is the primary focus of this initial preliminary assessment of those. This paper summarizes three primary tasks the Spent Fuel & Waste Science and Technology (SFWST) Program is executing (or collaborating on) related to the back end of the nuclear fuel cycle (BENFC) for potential future advanced reactors: 1. Advanced Reactors Spent Fuel and Waste Streams: Strategies for the BENFC This set of activities define a high-level strategy for how to systematically approach, identify, and close research and development (R&D) gaps/potential issues associated with long-term management and final disposition of AR SNF and other possible AR waste streams. This task involves summarizing advanced reactor concepts, their likely SNF and other waste forms, and identifying previous experience with similar materials, for example from DOE-managed SNF, with closely related characteristics to the potential future AR SNF. Technical R&D gaps between the breadth of detailed understanding for safe storage, transportation and disposal of the existing light water reactor SNF fuel cycle (e.g., see NASEM, 2022) and potential future fuel cycles based on advanced reactors would then be identified. 2. Characterization and Packaging Options of Advanced Reactor SNF These activities evaluate characteristics and packaging options for advanced reactor spent fuel forms. The fuel forms are categorized into three types: (1) tri-structural isotropic (TRISO), (2) metallic, and (3) fuel salt. Emphasis is given to TRISO and metallic SNF and additional waste streams from such AR as driven by the near-term anticipated operation of the Xe-100 and the Natrium reactors as advanced-reactor demonstrations1. Preliminary information for the spent-fuel salt discharged from molten-salt reactors (MSRs) is examined to provide a baseline for future efforts. All calculations and assumptions in this work are based on publicly available information. The following characteristics are calculated or estimated for use in the preliminary assessments: SNF volume and mass, radiation/activity levels through time, thermal conditions through time, potential radionuclide source terms, chemical interactions and evolutions, disposal inventories, and waste-form lifetime. Using those characteristics, calculations to determine the applicability of existing canister designs were performed. These evaluations included geometric (e.g., dimension, volume) and mass/weight considerations, known operational approaches and loading procedures, physical and chemical considerations/conditions for storage environments, as-loaded radiation, thermal, and criticality analyses to identify constraints for storage, transportation, and disposal. 3. Back-End Management of Advanced Reactors (BEMAR) The DOE NE-8 organization has defined an Integrated Project Team to evaluate the Back End Management of Advanced Reactors (BEMAR) (includes DOE staff from a range of organizations (e.g., NE-81, NE-82, OCED) and national laboratory technical staff within the DOE NE-81 and NE-82 programs). This BEMAR group works directly with advance reactors developers to assess for the DOE the technical feasibility of storage, transportation, and disposal of AR SNF based on the characteristics provided by the developers to DOE (much of which is proprietary). The BEMAR is also tasked to develop rough-order-of-magnitude cost estimates to compare the waste management system for individual advanced reactors to existing light-water reactor management practices. To accomplish this, the BEMAR group is implementing a Systems Engineering approach.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Improbability of Nuclear Criticality in Compacted Criticality Control Overpacks after Room Closure by Salt Creep at Waste Isolation Pilot Plant

Based on the rationale presented, nuclear criticality is improbable after salt creep causes compaction of criticality control overpacks (CCOs) disposed at the Waste Isolation Pilot Plant, an operating repository in bedded salt for the disposal of transuranic (TRU) waste from atomic energy defense activities. For most TRU waste, the possibility of post-closure criticality is exceedingly small either because the salt neutronically isolates TRU waste canisters or because closure of a disposal room from salt creep does not sufficiently compact the low mass of fissile material. The criticality potential has been updated here because of the introduction of CCOs, which may dispose up to 380 fissile gram equivalent plutonium-239 in each container. The criticality potential is evaluated through high-fidelity geomechanical modeling of a disposal room filled with CCOs during two representative conditions: (1) large salt block fall, and (2) gradual salt compaction (without brine seepage and subsequent gas generation to permit maximum room closure). Geomechanical models of rock fall demonstrate three tiers of CCOs are not greatly disrupted. Geomechanical models of gradual room closure from salt creep predict irregular arrays of closely packed CCOs after 1000 years, when room closure has asymptotically approached maximum compaction. Criticality models of spheres and cylinders of 380 fissile gram equivalent of plutonium (as oxide) at the predicted irregular spacing demonstrate that an array of CCOs is not critical when surrounded by salt and magnesium oxide, provided the amount of hydrogenous material shipped in the CCO (usually water and plastics) is controlled or boron carbide (a neutron poison) is mixed with the fissile contents.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Partitioning of Radionuclides in Various Streams of the Mo-99 Purification Process

The Universal Neutron Irradiator (UNI) was designed to irradiate a small volume of uranium solution and to achieve high fission power without creating a large radionuclide (RN) inventory. The UNI system is equipped with a fully enclosed off-gas system with online hydrogen gas monitoring to prevent the production of an explosive atmosphere, as well as storage cylinders for capturing fission gases. It also includes a catalytic recombiner in the target capsule (to immediately recombine radiolytic hydrogen and oxygen gas in the system) and access ports for sampling the target solution and capsule headspace. In UNI Phase I experiments, 50 mL of uranyl sulfate solution was irradiated at 0.3–0.5 W/mL fission power using a tantalum target assembly to produce photoneutrons via irradiation with an electron beam. The purposes of the Phase I experiments were to test the efficacy of adding 200 ppm Fe 2+ to the target solution to prevent uranyl peroxide precipitation under representative irradiation conditions, and to monitor iodine speciation in the irradiated uranyl sulfate solution. The focus of the UNI Phase II experiments was to use an irradiated uranyl sulfate solution containing a mixture of fission products and monitor their distribution in various streams during the primary recovery column (titania-based column) that separates Mo-99 from uranium. Irradiations were designed to create sufficient activity for tracking their distribution in various processing streams using a combination of gamma counting and inductively coupled plasma mass spectrometry (ICP-MS) analyses. Obtained data will be used to better understand the composition of waste streams, accumulation of RN on the titania column, and identify what RNs accumulate in the uranyl sulfate solution. Furthermore, this knowledge will allow us to determine waste classifications for various streams produced during the Mo-99 purification process and develop an appropriate waste clean-up strategy.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Understanding Biomass and Polymer Feedstock Variability Through Analytical Pyrolysis and Two Dimensional Gas Chromatography and Mass Spectrometry

Moving toward a circular carbon economy requires enabling reuse of carbon-based macromolecules like those in biomass and polymers. Meeting this goal requires increased upcycling of waste products into higher value products. For biomass waste such as corn stover, pine needles, or bark, one approach is using pyrolysis to convert these feedstocks into bio-oil that can be used for liquid fuel or transformed into other hydrocarbon based products, like bio-polymers. Waste plastics can be upcycled or recycled into new products, or alternatively converted into bio-oil by pyrolysis. Macromolecules from biomass and polymers are challenging to convert into liquid fuel or chemical feedstocks, due to large and sometimes heterogeneous networks of polymeric bonds. We work with the Idaho National Laboratory’s Biomass Feedstock National User Facility and Department of Energy’s Feedstock Conversion Interface Consortium to develop a molecular understanding of biomass variability that occurs naturally and as a result of storage or preprocessing techniques applied to feedstocks, to understand chemical reactions occurring during pyrolysis and other biomass or polymer conversion techniques. Using two dimensional gas chromatography mass spectrometry coupled to analytical pyrolysis provides insight into the molecular changes that occur during the pyrolysis event, and these insights can extend to bench or pilot scale pyrolysis conversions. Understanding pyrolysis of biomass and polymers at a molecular level contributes to development of new tools to predict and manipulate the optimum conditions and identify the best storage, preprocessing, and conversion techniques to maximize output of specific high-value chemical species in the conversion to fuels, or to characterize feedstocks for blending before pyrolysis. Identification and understanding of the molecular level changes resulting from novel preprocessing techniques that can be used to control and manipulate the chemical output of bench or pilot scale pyrolysis is another focus of investigation, including the use of gamma irradiation, acid, or enzyme pre-treatments. We also focus on the impacts of storage conditions and techniques, which can affect moisture levels, degradation, and impacts from naturally occurring microbes in the environment.

09 BIOMASS FUELS↗

Use of Micro-Gravity Sensors for External Fluid Level Monitoring in Waste and Nuclear Related Applications - 20315

There are a number of applications in nuclear energy and hazardous waste disposal that require monitoring of fluids under extreme environments, including high levels of temperature, pressure, toxicity and radioactivity. Many of these applications will benefit from a monitoring technique that is external and non-invasive. Currently the sensors used are invasive, must reside inside the pressurized vessels and must penetrate the vessel walls, which can create a weakness in the vessel. Additionally, instruments that are used inside such containers must be exceptionally hardened to the environment. Information Systems Laboratories (ISL) has developed an external mass (gravimetric) measuring technique for monitoring nuclear coolant in Small Modular Reactors (SMRs), which will also work for measuring fluid levels in waste tanks, that avoids the problems inherent in invasive sensors. It utilizes a COTS gravitational sensor of unprecedented accuracy, leveraged via proper sensor placement geometry, to detect fluid changes of small amplitude from an outside position, obviating the need to penetrate the vessel. The technique is called Gravisense{sup TM}. ISL has proven via simulation and experiment that this concept can be usefully applied to monitoring fluid levels in both nuclear reactors and large waste tanks. Numerical simulation algorithms were developed to calculate the gravity effect of small changes in water level, which were verified by experiments at the NIST Physical Simulator facility at the Oregon State University. The measured ultralow noise levels of the superconducting gravimeter type which utilizes a Niobium sphere suspended in a magnetic field to attain its phenomenal accuracy, demonstrated that fluid levels in SMRs can be measured at least to within 3 cm. Furthermore, the method can distinguish between a contained leak (from reactor to containment vessel) from an external leak (from reactor to outside of containment). Additionally, simulations of waste canisters that hold spent fuel rods show that the fluid level measuring accuracy can potentially do better than 1 cm accuracy by measuring from below the vessel, and judicious placement of sensors on top of large waste tanks can potentially achieve a very impressive 2 mm measurement accuracy. These encouraging results prove that the Gravisense{sup TM} technique for fluid determination can be very useful in nuclear energy generation, testing, and research, as well as in waste monitoring situations that are difficult to monitor via traditional sensing technology. We believe that the next step should be to test the technique on canisters of the type that are currently storing waste in various DOE locations. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Spectroscopic Online Monitoring: Using a Multi-Track Visible Spectrometer to Facilitate a Mass Balance Study in a Simulated TALSPEAK Process

Nuclear energy is a promising low-carbon energy candidate to meet the increased demand for green energy, where the integration of fuel recycling can have significant benefits for material usage and waste reduction. Utilizing in situ monitoring tools can provide ample opportunities to better control and safeguard nuclear material recycle processes while also offering knowledge and insight into real-time solution properties. The simultaneous measurement of analytical targets in multiple process locations can enable real-time mass balance and material accountancy calculations. This is demonstrated here with a mass balance study of Nd 3+ on countercurrent aqueous/organic metal extraction within a single centrifugal contactor. The Nd 3+ concentration was simultaneously monitored at the inlets and outlets of both aqueous and organic phases using a visible absorbance detector that allowed for the simultaneous measurement of up to six locations. The Nd 3+ concentration was calculated by using chemical data science algorithms, where model training sets were collected on a single track of the detector. The discussion includes addressing the challenges of using a model collected on a single track and applying it as a model across the other tracks on the detector. Each track of the detector corresponds to one measurement location on the contactor. The difference in the integrated moles of Nd 3+ between the inlet and outlet at the end of the experiment was near zero, indicating that the mass balance of this experiment was maintained. Overall, the online spectroscopic monitoring was able to follow changing solution conditions and accurately measure the concentration of Nd 3+ in different locations within the contactor system.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Drying Spent Magnox Fuel for Interim Dry Storage

Spent Magnox fuel is usually stored under water for shielding and cooling following use in-reactor, but the storage water can react with Magnox clad fuel and cause corrosion and forms a sludge which generates a secondary waste product. One option to prevent unwanted corrosion and avoid expensive waste management is to dry the wet fuel. This project aims to test a drying process which will convert wet and corroded Magnox fuel to a stable form to demonstrate viability for conversion from wet to dry storage. Samples of corroded Magnox supplied by National Nuclear Laboratory. Corrosion product retrieved by various methods including dry scraping, ultrasonic treatment to form sludge and sludge drying to isolate suspension. TGA undertaken on Sample 1 and Sample 2, with brucite and hydromagnesite for comparison. Both samples showed ∼10% mass loss up to 250 deg. C attributable to water held in sample. Mass loss from dehydroxylation which liberates further water in both samples. TGA data plotted alongside chemically pure brucite and hydromagnesite shows expected similarities/differences between Sample 1(mostly brucite) and Sample 2 (brucite/hydromagnesite mixture). Following treatment, dried samples observed to slowly gain mass in ambient conditions. Presumed to be hygroscopic absorption of air water vapour as effect is reversible, with similar effect observed for hydromagnesite and brucite. Etched Magnox vacuum dried for 3.5 h at 90 deg. C to test for reaction with residual water - some discoloration but no noticeable corrosion observed. Drying etched Magnox metal to observe surface effects/corrosion during drying process.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Molar-Mass-Dependent Partitioning of Polyethylene in Nanopores of Model Catalyst Supports from Small-Angle Neutron Scattering

Heterogeneous catalysis offers opportunities to enhance valorization of plastic waste via chemical recycling through control of the upcycled product distributions. Minimizing low-value light hydrocarbons is desired; however, fundamental insights into how to control selectivity are lacking. Here we use contrast variation with small-angle neutron scattering (SANS), model perdeuterated polyethylenes (dPEs), and a model liquid hydrocracking product (tetradecane) to quantify polymer partitioning within mesoporous silica (SBA-15). Polyethylene concentration within the mesopores is increased relative to the bulk solution, and this partitioning increases as the temperature increases. However, this polyethylene partitioning is maximized when the radius of gyration of the polymer chains is comparable to the SBA-15 pore size (10 nm). An increased partitioning at higher temperatures is attributed to entropically driven adsorption of PE within the mesopores. There is no observed preferential partitioning of hexatriacontane (a model oligomer) within the mesopores at the temperatures examined. Furthermore, these results suggest that pore size could promote the selective partitioning of polymer species into the mesopores by size. For plastic upcycling, pore-size-dependent partitioning should increase the probability for the reaction of long polymers over oligomeric and small-molecule polyolefin depolymerization products.

Adsorption↗

Preliminary IHLW Formulation Algorithm Description

This report documents the initial algorithm that could be used by the Waste Treatment and Immobilization Plant (WTP) in batching high-level waste (HLW) and glass-forming chemicals (GFCs) in the HLW melter feed preparation vessel (MFPV) (HFP-VSL-00001 and -00005). Not all Hanford tank waste can be accommodated by the models developed for this report and significant expansion of the model boundaries could be achievable to reduce the WTP mission life and total canister production count. The immobilized HLW (IHLW) must meet a series of constraints to be acceptable for disposal in the Monitored Geologic Repository, which are contained in the Specification 1 of the Contract (DOE 2000), the Waste Acceptance Product Specifications (WAPS, DOE 1996), and the Waste Acceptance System Requirements Document (WASRD, DOE 2007). The IHLW Waste Form Compliance Plan (WCP, 24590-HLW-PL-RT-07-0001, Rev 3) specifies that the formulation algorithm will be developed and used to comply with the constraints associated with glass composition and properties. This report is not an engineering calculation, does not provide design input, and is not an engineering study. Algorithm inputs include the chemical analyses of the blended HLW in the HLW blend vessel (HBV) (HLP-VSL-00028, the volume and composition of the MFPV heel, the volume and composition of the MFPV after waste addition, the volume and composition of MFPV batch after GFC addition, the compositions of individual GFCs, and the mass of glass in each canister. In addition to these inputs, uncertainties in the HLW composition and processing parameters are included in the algorithm. Using the above inputs, the algorithm calculates the following outputs: 1) the volume of HLW to be transferred from the HBV to the MFPV, 2) the mass of each GFC for addition to the MFPV, 3) the composition of the glass that will be produced along with uncertainties, and 4) the predicted properties, with associated uncertainties, of the resulting IHLW. The algorithm uses the property-composition models to calculate properties with associated uncertainties and compares them with various constraints to ensure that a processable feed is formulated and a compliant IHLW is produced. The GFC additions are determined using an optimization approach to provide high confidence that the HLW glass will meet all product quality requirements and key processing constraints. For most HLW batches there are many possible glass compositions that meet all constraints. In these cases, the glass composition is optimized for a series of target component concentrations and target property values. The algorithm also incorporates process measurement and product quality uncertainties, based on the work of Piepel et al. (2005). Estimates of the various process and measurement uncertainties that affect glass compositions and predicted glass properties have been previously reported (Piepel et al. 2005, 2006) and the impacts of these estimated uncertainties on the IHLW composition envelope that meets product quality and processing-related properties with sufficient confidence were evaluated. The details of work performed to date to develop this initial GFC addition and batching algorithm are summarized in Sections 4 and 5. An example data set is used to illustrate the calculations of the algorithm summarized in Section 6. Finally, in Section 7, there is a statement of the required work to achieve a final operational IHLW formulation control algorithm. This report is not an engineering calculation, does not provide design input, and is not an engineering study.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

High Resolution Fission Fragment Spectroscopy with Superconducting Microcalorimeters

Sub-1 AMU mass determination is important for determining fission yields and neutron multiplicity, which are necessary inputs for fission models. Fission models can improve spent nuclear waste stream analysis and nuclear fuel burnup determination. Here, to achieve this goal, we have used superconducting microcalorimeter detectors to directly measure the energy of fission fragments from the spontaneous fission of 252 Cf. With a fiber coupled LED pulser setup we demonstrate that we can reach a relative energy resolution of 0.1% and better for photon pulses with energies above 60 MeV. This instrument, in conjunction with time-of-flight (TOF) measurement, would allow for sub-1 atomic mass unit (AMU) mass determination of fission fragments in a future beamline application.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Analysis of Tar and Oil Derived from Pyrolysis and Copyrolysis of Waste Plastics and Biomass

Pyrolysis has been proposed as a potential technology for managing the growing volume of plastic waste generated worldwide. Co-pyrolysis of plastic waste with biomass is a promising technology for generating fuel and chemical products. However, this process generates tar as a waste product. The chemical properties of this tar have yet to be thoroughly analyzed. Further, this study presents the results of gas chromatography–mass spectrometry (GC–MS), Fourier-transform infrared spectroscopy (FTIR), and thermogravimetric analysis (TGA) of oil and tar obtained from the pyrolysis of pure plastics including high-density polyethylene (HDPE), low-density polyethylene (LDPE), polyethylene (PE), polystyrene (PS), and plastic-biomass mixtures. GC–MS analysis revealed the presence of C 7 –C 37 carbon-containing hydrocarbons, which include alkanes and alkenes as the dominant products. FTIR data revealed the presence of various functional groups, including alcohols, aldehydes, ketones, and carboxylic acids, indicating the complexity of the pyrolysis and copyrolysis oil obtained from waste plastics and biomass. TGA data show that tar from all four plastics has a higher decomposition rate, suggesting the presence of heavier hydrocarbons compared with their corresponding oils. This research will be of interest to researchers looking to advance the study of plastic and biomass waste management.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Sixty days of head-down tilt bed rest with or without artificial gravity do not affect the neuromuscular secretome

Highlights: • Long-term bed rest with/without artificial gravity does not affect the neuromuscular secretome. • Serum concentrations of markers of muscle wasting are not affected by bed rest/artificial gravity. • C-terminal Agrin Fragment serum concentrations are not affected by bed rest/artificial gravity. • Human centrifugation during bed rest does not have a negative impact on the neuromuscular secretome. Artificial gravity is a potential countermeasure to attenuate effects of weightlessness during long-term spaceflight, including losses of muscle mass and function, possibly to some extent attributable to disturbed neuromuscular interaction. The 60-day AGBRESA bed-rest study was conducted with 24 participants (16 men, 8 women; 33 ± 9 years; 175 ± 9 cm; 74 ± 10 kg; 8 control group, 8 continuous (cAG) and 8 intermittent (iAG) centrifugation) to assess the impact of bed rest with or without daily 30-min continuous/intermittent centrifugation with 1G at the centre of mass. Fasting blood samples were collected before and on day 6, 20, 40 and 57 during 6° head-down tilt bed rest. Concentrations of circulating markers of muscle wasting (GDF-8/myostatin; slow skeletal muscle troponin T; prostaglandin E2), neurotrophic factors (BDNF; GDNF) and C-terminal Agrin Fragment (CAF) were determined by ELISAs. Creatine kinase activity was assessed by colorimetric enzyme assay. Repeated-measures ANOVAs were conducted with TIME as within-subject, and INTERVENTION and SEX as between-subject factors. The analyses revealed no significant effect of bed rest or sex on any of the parameters. Continuous or intermittent artificial gravity is a safe intervention that does not have a negative impact of the neuromuscular secretome.

60 APPLIED LIFE SCIENCES↗

Application of On-Line Monitoring and Real-Time Characterization of Low Level Waste Samples from Hanford Tanks

Waste and treatment stream characterization is an essential part of safe, efficient, and cost-effective processing of Hanford materials. The demand for materials characterization, including chemical, radionuclide, and physical attributes during waste management, transfer, and staging operations in the Hanford tank farms, is expected to significantly increase as the U.S. Department of Energy Office of River Protection (ORP) progresses toward Hanford waste treatment and immobilization. The application of on-line monitoring can greatly improve operation timeframes and reduce costs by providing real-time data and supporting the reduction of necessary grab sample collection. Recently, our team applied Raman online monitoring and chemometric modeling to the supernate of Hanford tank 241-AP-105, and demonstrated the quantitative measurement of nine analytes within this waste. Application of this method has been expanded to additional Hanford tank wastes, AW-102 and AP-107. The performance of the process monitoring instruments and the accuracy of the chemometric models will be assessed. On-line monitoring results will be compared to anion results determined from the current standard, ion-chromatographic and inductively coupled plasma mass spectrometry methods. Comparisons of both determined values and uncertainties of results will be presented. Results will be shared with personnel working on flowsheet interfaces for the Direct-Feed Low Activity Waste mission at Hanford.

Lines, Amanda M.↗

FY24 Task 4: Studies of Phosphate and Fluoride Solubility for Dissolution of High Phosphate Tank Waste

Knowledge gaps have been identified in phosphate solubility in almost every single- and multi-component system, and particularly for aluminate in phosphate/hydroxide, where uncertainties in predicted values of aluminum solubility are greater than 50%. Solubility data of multicomponent, aqueous electrolytes containing sodium hydroxide, sodium fluoride, sodium phosphate, sodium nitrite, sodium nitrate, and dissolved gibbsite are also sparse. For example, for solutions of (i) sodium nitrate and sodium phosphate, data are only available at 30 and 50 °C, and for (ii) dissolved gibbsite in sodium hydroxide and sodium phosphate, only two data points are available at 20 and 40 °C. There is no data available on mixtures of sodium hydroxide, sodium phosphate, sodium fluoride, and dissolved gibbsite. These knowledge gaps were identified in a technical review of waste solubility data and the impact of dilution on solution stabilities and will be addressed in this work to predict aluminum hydroxide and sodium phosphate solubility in multicomponent electrolytes upon dilution, and upon variation of temperature. Results will provide the technical basis to develop accurate models for (i) gibbsite solubility and mass transfer of aluminum between solid and liquid forms following the sluicing of sludge and saltcake with water; and (ii) further blending of these suspensions with bismuth from bismuth phosphate waste, and zirconium and uranium left from the fuel decladding. This work will be essential to developing a disposition path for retrieval solutions from bismuth phosphate wastes. This effort would also support sludge washing to further reduce phosphate concentration if that process were to be added back to the flowsheet in the future.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Distribution of U, Pu and Np in a Mo-99 Recovery Process using Sachtopore NP (titania based) Absorbent Material

A laboratory scale mockup of a prototypical Mo-99 recovery process has been operated in a radioactive materials hood at Savannah River National Laboratory. This equipment has been operated with realistic concentrations of uranium (U-238), plutonium (94% Pu-239), neptunium (Np-237), and non-radioisotopes of common fission products (including Mo). The goal of this work was to determine the amounts of U, Pu, and Np in the liquid waste streams created by the wash streams for the production process. The key question was how the initial acid wash volume will be handled, as this solution contains residual raffinate which amounted to ~ 3% ofthe mass ofthe feed solution in this experiment. If the initial 1.9 bed volumes (BV) of acid wash were recycled as in this experiment then the combined wash solutions can be expected to contain 0.4 g U/L, 2.7 pg Pu/L and < 14 pg Np/L. If, on the other extreme, the entire acid wash solution was discarded as waste, then the combined wash solutions can be expected to contain 11 g U/L, 3.8 pg Pu/L and ~ 80 pg Np/L. The Sachtopore NP absorbent (for Mo-99 recovery) retains a minuscule fraction ofthe U (2.3 mg U per g titania or 0.03% ofthe U in the feed). The uncertainties are too large to determine how close the absorbent is to saturation with U. Less mass but a higher fraction ofthe total Np was retained by the absorbent (0.7 pg Np per g titania or ~2% of the Np in the feed). As has been reported elsewhere, a large fraction ofthe Pu fed to the titania bed was retained by the absorbent (92% of Pu in the feed or 20 pg per g titania).

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Vitrification Testing of HLW with High Phosphate

Projections of the number of high level waste (HLW) canisters to be produced in the Hanford Tank Waste Treatment and Immobilization Plant (WTP) (e.g., [1]) are based upon the inventory of the tank wastes, the anticipated performance of the sludge treatment processes, and current understanding of the capability of the borosilicate glass waste form. The WTP HLW melter design, unlike earlier Department of Energy (DOE) melter designs, incorporates a glass bubbler system. The bubblers create active glass pool mixing and thereby improve heat and mass transfer and glass melting rate. The WTP HLW melters each have a glass surface area of 3.75 m 2 and depth of ~1.1 m. The two melters in the HLW facility together are designed to produce up to 7.5 MT of glass per day at 100% availability. Further increases in HLW waste processing rates can potentially be achieved by optimization of the feed and glass formulations, increasing the melter operating temperature above 1150⁰C, and by increasing the waste loading in the glass product. Increasing the waste loading also has the added benefit of decreasing the number of canisters for storage.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Solvent-driven aqueous separations for hypersaline brine concentration and resource recovery

Solvent-driven separation processes can extract water and high-value minerals from high salinity or contaminated brines, simultaneously reducing the environmental impact of brine disposal and enabling resource recovery. The efficient dewatering of hypersaline brines is essential for the sustainable minimal and zero liquid discharge processing of industrial wastewaters. Fractional crystallization can selectively extract ions from contaminated waste streams, allowing critical materials to be recycled, including transition and lanthanide metals required for renewable energy generation and storage. Mass transfer in solvent-driven water extraction occurs across a liquid–liquid interface, eliminating the scaling and fouling of membrane and heat exchanger surfaces and limiting the need for extensive pretreatment. Solvent-driven fractional crystallization can leverage sequential treatment and control of process conditions to rapidly recover salts without requiring evaporation of water. Despite promising applications, the principles and potential of solvent-driven aqueous separations remain poorly understood. This critical review explores the opportunities presented by solvent-based aqueous separations from the molecular to process scale, evaluating the chemistry of solvation and system design in the broader context of desalination, resource recovery, water softening, and mineral production.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Solubility Testing to Support the Addition of Sodium Reactor Experiment Material to Sludge Batch 10

The Savannah River Site H-Canyon Facility is planning to discard dissolved Sodium Reactor Experiment (SRE) material into Tank 51 prior to Sludge Batch 10 (SB10). SB10 with the SRE material will be processed in the Defense Waste Processing Facility (DWPF) using the Nitric-Glycolic Acid (NGA) flowsheet. The DWPF Nuclear Criticality Safety Evaluation (NCSE) protects a 14:1 mass ratio of manganese to equivalent uranium-235 in both the solid and liquid phases during processing by requiring a 70:1 mass ratio in the feed. A concern was raised that freshly precipitated manganese in the SRE material will behave differently from the manganese in sludge during DWPF processing and potentially invalidate the criticality control. To mitigate risks to the DWPF criticality controls, the Savannah River National Laboratory (SRNL) performed a metals solubility test applicable to recently precipitated manganese and uranium, as would be expected with SRE transfers to SB10. The objective of this analysis is the tracking of partitioning of the primary fissile component (uranium-235) with the credited poison (manganese) between the aqueous and insoluble phases.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗