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At least 253 records · Page 14

Glass-Bonded Monazite Waste Forms for Lanthanide and Actinide Immobilization: From Theoretical Design to Scale-Up Production and Characterization

The development of nuclear waste forms for both existing and future nuclear wastes is critical to ensuring global environmental safety. This study focuses on waste management from molten salt reactors, where fuel exists in a salt form and could be processed in real time for the removal of neutron poisons such as xenon isotopes (e.g., 135 Xe) and rare earth elements (REEs, e.g., 149 Sm). To ensure safe, stable, and long-term disposal in geological repositories, REEs must be incorporated into a durable waste form. Iron-phosphate glasses are a promising candidate due to their low melting points, high chemical durability, and their ability to incorporate high concentrations of REEs. In this study, we successfully prepared iron-phosphate glass waste forms with high Nd loadings (up to 37 mass %) in batch sizes ranging from small (23 g) to large (1600 g). The resulting materials contained up to 75 mass % NdPO 4 , contributing to their mechanical resilience and exceptional chemical durability. These findings highlight the potential of iron-phosphate glasses as high-efficiency, chemically durable waste forms and demonstrate the successful transition from theoretical design to scaled-up production.

amorphous materials↗

Experimental screening of salt hydrates for thermochemical energy storage for building heating application

The selection of a suitable salt hydrate for use in a thermochemical energy storage system is challenging. In this work, the most promising salts to store intermediate heat energy were selected and tested. The criteria set are; volumetric energy density of >500 kWh m-3 with a dehydration temperature of <100 degrees C, material cost of <3.5 USD kg-1 (<15 USD kWh-1), melting does not occur during dehydration and safety. Based on that, the salt hydrates SrCl 2 , MgSO 4 , Na 3 PO 4 , MgCl 2 and SrBr 2 were selected and tested experimentally. A constant temperature and humidity chamber was used to measure moisture sorption of different salts. The hydration is investigated under the conditions of 20 degrees C and 20, 30, 40, 60 and 80% RH, while dehydration is investigated under the conditions of 70, 100 and 140 degrees C using an oven. These dehydration temperatures of <100 degrees C are suitable for solar application whereas the dehydration temperature of 140 degrees C is suitable for waste heat. Furthermore, the salts are cycled over 30 times under the hydration conditions of 20 degrees C, 60% RH with a dehydration temperature of 100 degrees C. From these results, it is concluded that SrCl 2 and SrBr 2 are the most promising salts. This study outlines both the advantages and disadvantages of each salt and states the conditions they are most suitable for.

25 ENERGY STORAGE↗

Feasibility Study for Cathodic Protection of Waste Tanks at Hanford

The Hanford Nuclear Reservation site contains approximately 211 million liters of radioactive and chemically hazardous waste arising from nuclear weapons production, beginning with World War II, and continuing through the Cold War. The waste is stored in 177 carbon-steel underground storage tanks, of which 149 are single-shell tanks (SSTs) and the remaining are double-shell tanks (DSTs). The mission of an ongoing River Protection Project is to retrieve the waste from the underground storage tanks and then treat and immobilize (i.e., vitrify) it for disposal. Waste from the older SSTs is being progressively retrieved into the newer DSTs for storage pending treatment, immobilization, and disposal. Waste chemistry controls are in place to mitigate general corrosion, pitting corrosion, and stress corrosion cracking (SCC) and minimize corrosion risks to the carbon steel tank liners of DST at the Hanford Site. The chemistry control program focuses on preserving liner integrity while balancing the need for caustic/nitrite additions that have large downstream impacts on vitrification. Some of the DSTs store salt cake or sludge waste layers contain out-of-specification interstitial liquids that contact the primary tank bottom or sidewall. Remediation of such layers through chemical additions is not practical. At the present time, the most significant leak integrity concern at Hanford is for corrosion of the tank bottoms of DSTs where the solids layer is out of specification because of hydroxide ion depletion and consequently, pH values that are less than 12. Cathodic protection (CP) has been proposed as a possible way to protect the liners of such tanks against corrosion. The objective of this project was to investigate the feasibility of applying CP to Hanford DSTs to mitigate internal corrosion of the carbon steel tank primary liners. The scope of the project included (1) a literature review on the application of CP to storage tank systems, in general, and to waste tanks at the Savannah River Site (SRS) and Hanford, (2) a review of the finite element analysis (FEA) model recently developed to evaluate potentials for a DST, and (3) the development of a boundary element analysis (BEA) model for CP for a DST. Tank AN-107, one of the Hanford DSTs, was selected for this work because (1) the bottommost waste layer in the tank is out-of-specification, and (2) electrochemical and resistivity data, based on recent waste sampling and testing, are available for this tank. The overarching conclusion of this study is that, based on the available information, it is feasible to apply CP to mitigate internal corrosion of the primary liners of the Hanford DSTs. However, significant additional information and work are required before a CP system can be designed. Recommendations for next steps in the design of the CP system will be presented.

WIERSMA, BRUCE↗

Waste Water Brine Purification through Electrodialysis Ion Exchange

Reutilizing resources onboard the International Space Station (ISS) and for future deep space missions are critical for mission longevity and sustainability. Waste water brine produced from water recovery systems contain chemical species that could be processed into a potential fertilizer for future plant systems.Fertilizer production can be achieved through a process called electrodialysis ion exchange. Waste water containing inorganic salt components are fed through a series of ion exchange membranes to produce fertilizer (a phosphate rich stream), electrolysis-grade water, and other useful commodities.A test bed was constructed to conduct controlled experiments and an experimental design procedure developed to determine the feasibility of the process. Conductivity and pH probes were utilized to determine the ion concentration in each of the product streams, along with ion chromatography (IC) to define the exact concentration of each ion in every stream throughout the experiment. This is crucial in order to convey the effectiveness of ion removal from the incoming waste water stream.The waste water and electrolyte streams were prepared in the lab prior to experimentation. Additionally, the ion exchange membrane configurations were developed and Opto 22 data analysis software incorporated to conduct measurements in real time.Ions successfully diffused across their respective membranes into the concentrate, acid, and base streams. This resulted in pure water, a phosphate rich stream, and a separate anion/hydrogen and cation/hydroxide stream.

Hancock, Matthew L.↗

An analysis of the technical status of high level radioactive waste and spent fuel management systems

The technical status of the old U.S. mailine program for high level radioactive nuclear waste management, and the newly-developing program for disposal of unreprocessed spent fuel was assessed. The method of long term containment for both of these waste forms is considered to be deep geologic isolation in bedded salt. Each major component of both waste management systems is analyzed in terms of its scientific feasibility, technical achievability and engineering achievability. The resulting matrix leads to a systematic identification of major unresolved technical or scientific questions and/or gaps in these programs.

English, T.↗

U.S. Space Station Freedom waste fluid disposal system with consideration of hydrazine waste gas injection thrusters

The results are reported of a study of various methods for propulsively disposing of waste gases. The options considered include hydrazine waste gas injection, resistojets, and eutectic salt phase change heat beds. An overview is given of the waste gas disposal system and how hydrozine waste gas injector thruster is implemented within it. Thruster performance for various gases are given and comparisons with currently available thruster models are made. The impact of disposal on station propellant requirements and electrical power usage are addressed. Contamination effects, reliability and maintainability assessments, safety issues, and operational scenarios of the waste gas thruster and disposal system are considered.

Winters, Brian A.↗

Initial Simulations of Empty Room Collapse and Reconsolidation at the Waste Isolation Pilot Plant

The Waste Isolation Pilot Plant (WIPP) is a geologic repository for defense-related nuclear waste. If left undisturbed, the virtually impermeable rock salt surrounding the repository will isolate the nuclear waste from the biosphere. If humans accidentally intrude into the repository in the future, then the likelihood of a radionuclide release to the biosphere will depend significantly on the porosity and permeability of the repository itself. Room ceilings and walls at the WIPP tend to collapse over time, causing rubble piles to form on floors of empty rooms. The surrounding rock formation will gradually compact these rubble piles until they eventually become solid salt, but the length of time for a rubble pile to reach a certain porosity and permeability is unknown. This report details the first efforts to build models to predict the porosity and permeability evolution of an empty room as it closes. Conventional geomechanical numerical methods would struggle to model empty room collapse and rubble pile consolidation, so three different meshless methods, the Immersed Isogeometric Analysis Meshfree, Reproducing Kernel Particle Method (RKPM), and the Conformal Reproducing Kernel method, were assessed. First, the meshless methods and the finite element method each simulated gradual room closure, without ceiling or wall collapse. All three methods produced equivalent room closure predictions with comparable computational speed. Second, the Immersed Isogeometric Analysis Meshfree method and RKPM simulated two-dimensional empty room collapse and rubble pile consolidation. Both methods successfully simulated large viscoplastic deformations, fracture, and rubble pile rearrangement to produce qualitatively realistic results. In addition to geomechanical simulations, the flow channels in damaged salt and crushed salt were measured using micro-computed tomography, and input into a computational fluid dynamics simulation to predict the salt's permeability. Although room for improvement exists, the current simulation approaches appear promising.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

A Thermodynamic Model for Nd(III)–Sulfate Interaction at High Ionic Strengths and Elevated Temperatures: Applications to Rare Earth Element Extraction

Neodymium (Nd), a rare earth element (REE), is critical to numerous industries. Neodymium can be extracted from ore concentrates, waste materials, or recycled materials such as recycled Nd-Fe-B permanent magnets. In a standard process, concentrated sulfuric acid (H 2 SO 4 ) is used as an extraction/leaching agent. Therefore, knowledge of Nd(III)–sulfate interaction at high ionic strengths is important for optimization of the extraction process. In addition, sulfate is also a major species in natural surface waters and present in nuclear waste streams. Nd(III) has been used a chemical analog to trivalent actinides in nuclear waste research and development. Consequently, knowledge of Nd(III)-sulfate interactions is also impactful to the field of nuclear waste management. Here, in this study, we have developed a thermodynamic model that can describe the interaction of Nd(III) with sulfate to ionic strengths up to ~ 16.5 mol·kg –1 and to temperatures up to 100 °C. The model adopts the Pitzer formulation to describe activity coefficients of aqueous species. This model can be used to design and optimize a chemical process for REE recovery from ore concentrates, recycled materials, and acid mine drainage (AMD) and to understand the mobility of REEs and actinides in the environment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Time dependent chlorination of CeO 2 , La 2 O 3 and Nd 2 O 3 by ZrCl 4 dissolved in eutectic LiCl–KCl

Partial chlorination of CeO 2 , La 2 O 3 , and Nd 2 O 3 was achieved using ZrCl 4 dissolved in molten LiCl-KCl at 450°C over a period of 4-5 hr. ZrCl 4 was pre-volatilized into an argon stream to maintain a constant vapor pressure for equilibration with the salt. This approach was effective at maintaining the ZrCl 4 concentration at the solubility limit of 1.3 mol% in the molten salt throughout the duration of two of the chlorination experiments and within about 60% of the solubility limit in the third experiment. Based on the analysis of salt samples, fractional conversion after four hours of reaction for CeO 2 , and five hours for La 2 O 3 , and Nd 2 O 3 were calculated to be 0.97, 0.28, and 0.65 respectively. Assuming a shrinking core diffusion-limited model, the diffusivity of ZrCl 4 through the hypothesized ZrO 2 layer was calculated for the chlorination of CeO 2 , La 2 O 3 , and Nd 2 O 3 were 1.76 x 10 -10 cm 2 /sec, 7.85 x 10 -12 cm 2 /sec, and 7.42 x 10 -12 cm 2 /sec, respectively. Given the extremely low values calculated for diffusivity, it was concluded that the process is chemical reaction rate limited and that a complete reaction of each rare earth oxide could be achieved. Furthermore, a chemically controlled shrinking core model was shown to also fit the experimental data closely.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Update to the Performance Assessment for the Savannah River Site Saltstone Disposal Facility - 20124

In 2019, Savannah River Remediation developed a revision to the performance assessment (PA) on behalf of the U.S. Department of Energy (DOE) Savannah River Operations Office (SR) for the near-surface disposal of low-level waste at the Savannah River Site (SRS) Saltstone Disposal Facility (SDF). Soluble waste from SRS Tank Farms undergoes salt processing to remove cesium and other high activity constituents. The low-activity decontaminated salt solution (DSS) is then immobilized by mixing it into a cementitious waste form known as saltstone. After mixing, the saltstone is poured into leak-tight concrete vaults, known as saltstone disposal units (SDUs), where the waste form cures. By the time of facility closure, the SDF is expected to consist of 15 SDUs with a combined capacity of 1.06 E+09 L (280 Mgal) of cured saltstone. The facility operates under a Disposal Authorization Statement (DAS) from DOE and a permit from the South Carolina Department of Health and Environmental Control (SCDHEC). Since the start of operations in 1990, the SDF has received almost 6.7 E+07 L (18 Mgal) of DSS, resulting in the safe disposal of 2.7 E+16 Bq (7.3 E+05 Ci) of activity. Due to the radioactive decay of short-lived contaminants, the total remaining activity in the disposed waste is estimated to be approximately 1.4 E+16 Bq (3.9 E+05 Ci), as of September 2018. The Disposal Authorization Statement requires a demonstration that the system of engineered and natural features of the disposal facility will limit releases from the facility and be protective of human health and the environment for at least the next 1,000 years. The long-term performance of the facility was evaluated under the requirements of the DoE's Radioactive Waste Management Manual (US DOE Manual 435.1-1). Simulations were performed to demonstrate that the disposal facility would meet performance objectives specified in the manual. The evaluation was based on numerical models that simulate the releases of contaminants from the saltstone waste form. Contaminants were transported through groundwater and air pathways to points of assessment to evaluate compliance. In addition, the potential consequences of an inadvertent human intrusion (IHI) were also evaluated. In accordance with the guidance and recommendations in US DoE's technical standard for DAS, deterministic and probabilistic analyses were performed to demonstrate the SDF system, which includes the engineered cover system, the SDUs, the waste form, and the natural features of the site, provides a reasonable expectation that saltstone disposal will meet performance objectives. Post-closure doses to future members of the public (MOP) were evaluated; dose estimates from the air pathway were well below the 1.0 E-04 Sv/yr (10 mrem/yr) performance objective within 1,000 years, and the calculated doses to the MOP from all exposure pathways, including the groundwater and air pathways, were well below the 2.5 E-04 Sv/yr (25 mrem/yr) performance objective within 1,000 years. Doses following an assumed intrusion event within the facility boundaries were well below the IHI performance objectives, where the acute IHI dose was below the acute IHI dose performance objective of 5.0 E-03 Sv (500 mrem) and the chronic IHI dose was below the chronic IHI dose performance objective of 1.0 E-03 Sv/yr (100 mrem/yr) within 1,000 years. (author)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Issue Resolution During the Development of the Performance Assessment for the Savannah River Site Saltstone Disposal Facility - 20125

In 2019, Savannah River Remediation developed a revision to the performance assessment (PA) on behalf of the U.S. Department of Energy (DOE) Savannah River Operations Office (SR) for the near-surface disposal of low-level waste at the Savannah River Site (SRS) Saltstone Disposal Facility (SDF). Soluble waste from SRS Tank Farms undergoes salt processing to remove cesium and other high-activity constituents. The low-activity decontaminated salt solution (DSS) is then immobilized by mixing it into a cementitious waste form known as saltstone. After mixing, the saltstone is poured into leak-tight concrete vaults, known as saltstone disposal units (SDUs), where the waste form cures. By the time of facility closure, the SDF is expected to consist of 15 SDUs with a combined capacity of 1.06 E+09 L (280 Mgal) of cured saltstone. The facility operates under a Disposal Authorization Statement from DOE and a permit from the South Carolina Department of Health and Environmental Control (SCDHEC). Since the start of operations in 1990, the SDF has received almost 6.7 E+07 L (18 Mgal) of DSS, resulting in the safe disposal of 2.7 E+16 Bq (7.3 E+05 Ci) of activity. Due to the radioactive decay of short-lived contaminants, the total remaining activity in the disposed waste is estimated to be approximately 1.4 E+16 Bq (3.9 E+05 Ci), as of September 2018. The Disposal Authorization Statement requires a demonstration that the system of engineered and natural features of the disposal facility will limit releases from the facility and be protective of human health and the environment for at least the next 1,000 years. The long-term performance of the facility was evaluated under the requirements of the DoE's Radioactive Waste Management Manual (US DOE Manual 435.1-1). Simulations were performed to demonstrate that the disposal facility would meet performance objectives specified in the manual. The evaluation was based on numerical models that simulate the releases of contaminants from the saltstone waste form. Contaminants were transported through groundwater and air pathways to points of assessment to evaluate compliance (i.e., 100 m from the SDUs). In addition, the potential consequences of an inadvertent human intrusion (IHI) were also evaluated. A number of issues were overcome during the development of these simulations. These issues were identified as part of internal technical reviews. Simulations are developed by people and people make mistakes, so the internal technical review process is a vital step in PA development. Specific examples of resolved issues include a unit-conversion error, an inappropriate definition for a model boundary condition, a model time-stepping issue, and an error in the calculation for the buildup of contaminants in soil. Actions taken to address these issues resulted in an improved product with a better supported technical basis and more defensible results. The identification and correction of these issues are discussed. By understanding these issues, model developers and technical reviewers working on PAs in the future may avoid repeating these types of mistakes. Transparency with respect to these mistakes builds trust between waste management sites, regulators, and stakeholders. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

A Decade of Innovative Approaches to Treating and Dispositioning Radioactive Waste at the Savannah River Site - 20620

This year marks the 70. anniversary of the U.S. Department of Energy's (DOE) Savannah River Site (SRS), located near Aiken, South Carolina. SRS is a key industrial complex responsible for environmental stewardship, environmental cleanup, waste management, and disposition of nuclear materials. SRS also continues to have a role in critical defense-related activities and the reprocessing of used reactor fuel. The SRS encompasses 803 square kilometers (310 square miles) in parts of Aiken, Barnwell, and Allendale counties. The Liquid Waste Mission starts with the safe receipt and storage of radioactive liquid waste in the waste tanks, which principally includes Cold War legacy waste, but also waste from support of National Aeronautics Space Administration missions, medical isotope production, and research activities. This 133,000 cubic meters (m{sup 3}) (35 million gallons [Mgal]) of high-level radioactive waste (HLW) is currently held in 43 large underground waste tanks. The capacity of each of these tanks range from 2,800 m{sup 3} to 5,000 m{sup 3} (0.75 to 1.33 Mgal) and were placed in operation between 1954 and 1986. In July 2009, the DOE awarded a stand-alone contract to execute the Liquid Waste Mission at SRS. The Liquid Waste Contractor selected was Savannah River Remediation LLC1 (SRR), which is responsible for receipt, storage, retrieval and treatment of all HLW, disposal of the decontaminated low-activity waste fraction, as well as operationally closing cleaned HLW tanks. Since July 2009, SRR has successfully grouted and operationally closed six large underground tanks, poured 1,476 canisters of vitrified HLW (a stable glass waste form), treated approximately 34,200 m{sup 3} (9.0 Mgal) of HLW, and dispositioned over 41,200 m{sup 3} (10.9 Mgal) of decontaminated salt solution as low-level waste (LLW) into the Saltstone Disposal Units (SDUs) being constructed by SRR on site. The innovative work performed by SRR in the LLW portion of its mission has earned it the Richard S. Hodes Award. The work conducted by SRR is the same work championed by the late Richard S. Hodes, a respected physician, statesmen, and Chairman of the Southeast Compact Commission for Low-Level Radioactive Waste Management. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Linear and Nonlinear Solvers for Simulating Multiphase Flow within Large-Scale Engineered Subsurface Systems

Simulation of multiphase flow in the subsurface is well-known to be computationally challenging. While there have been many studies that have explored approaches to overcoming these challenges, they often utilize relatively simple case studies. In this paper, we focus on the unique numerical challenges posed by modeling large-scale engineered subsurface systems, characterized by discrete features embedded in a heterogeneous natural subsurface setting. The man-made features such as shafts, tunnels, and barriers often cause multiple challenges in modeling the domain for multiphase porous media flow. This flow scenario can have a wide range of applications such as nuclear waste repositories, enhanced recovery of a petroleum reservoir, geothermal engineering, and carbon sequestration. An example of these severe numerical challenges is the case of performance assessment (PA) for Waste Isolation Pilot Plant (WIPP), the only operating deep geological repository in the US, which simulates extreme material properties of bedded salt rock formation and extreme contrast due to open excavation next to the formation. The models have extremes not only of permeability and porosity but also of the constitutive models needed for multiphase flow; additionally, they have process models like salt creep closure reducing porosity over time, fracturing in clay and anhydrite interbeds of the bedded salt, gas generation from the waste materials, and unintentional human borehole intrusions in some scenarios. Numerical simulations require the solution of coupled systems of nonlinear PDEs; in our work, we use the open-source simulator PFLOTRAN which is based on Finite Volume discretization. The solution of the nonlinear equations requires use of the Newton-Raphson iteration at each time step, which entails the solution of the linearized Jacobian system at each iteration. The effects of all the processes (i.e., large number of unknowns, highly nonlinear constitutive relations, large contrasts in material properties in short distances) lead to an ill-conditioned Jacobian matrix that severely challenges traditional linear solver, i.e., stabilized biconjugate gradient with block Jacobi incomplete LU preconditioner (BCGS-ILU) leading to non-convergence for traditional Newton-Raphson nonlinear solver causing unacceptably long computation time for each model. This paper presents linear solvers such as constrained pressure residual (CPR) two-stage preconditioner with alternate-block-factorization (ABF) and quasi- implicit pressure and explicit saturation (QIMPES) decouplers and flexible generalized residual solver (FGMRES). The new general-purpose nonlinear solver, Newton trust-region dogleg Cauchy (NTRDC), is also introduced to resolve extreme nonlinearities in the models. We demonstrate the effectiveness of each method relative to the default BCGS-Newton solver. The two best cases had nearly 50 times speed-up and achieved completion of a simulation in 14 hours that never completed due to non-convergence with the default solver. We also investigate the strong scalability of each method and discuss some of the deficiencies found for Block Jacobi preconditioner using parallel domain decomposition, and node packing effects of modern processor architecture.

Preconditioner, Nonlinear, Porous media, Multiphas↗

Determining the Solubility Behavior of Kogarkoite in Simulated Nuclear Waste

Kogarkoite (Na 3 FSO 4 ) is a sparingly soluble fluoride–sulfate double salt that has been identified in high level nuclear waste sludge at the Hanford Site and, more recently, in sludge batch compilation samples at the Savannah River Site (SRS). Due to its complex dissolution behavior, which exhibits an inverse dependence on sodium ion activity, the presence of this mineral poses significant challenges to waste retrieval and processing. Incomplete dissolution during sludge washing can lead to the retention of fluoride and sulfate in the high-level waste feed, potentially causing the formation of corrosive, immiscible molten salt layers, known as "glass gall,” in vitrification melters. Current efforts to optimize flowsheet parameters and wash-water volumes are hindered by the absence of a commercially available, certified reference material, which prevents the accurate calibration of analytical methods and the verification of dissolution kinetics. To address this critical gap, this research focuses on the laboratory synthesis of pure Kogarkoite to serve as a standard for comprehensive solubility and washing performance testing. A coupled synthesis and simulant campaign was executed using an evaporative crystallization protocol designed to replicate the dynamic concentration effects observed in tank farm operations. Thirteen simulant matrices were prepared by dissolving systematically varied ratios of sodium fluoride (NaF) and sodium sulfate (Na 2 SO 4 ) in deionized water under three distinct caustic regimes: 0.0 g (control), 4.0 g (~1 M), and 12.0 g (~3 M) sodium hydroxide (NaOH). While thermodynamic equilibrium models suggest that high-caustic environments should favor the stability of the double salt7, results from this evaporative study at 25 0 C revealed a distinct kinetic divergence. Simulants with high hydroxide loading predominantly yielded large, blocky crystals of sodium sulfate decahydrate (Na 2 SO 4 .10H 2 O). Successful synthesis of pure Kogarkoite was achieved exclusively in specific NaOH-free compositional windows, where the precipitate manifested as fine, opaque granular aggregates. Ion chromatography (IC) analysis confirmed phase purity through the simultaneous stoichiometric depletion of both fluoride and sulfate from the supernatant. This successful synthesis establishes a reproducible route to generate bulk Kogarkoite, enabling the subsequent phase of quantitative dissolution testing using inhibited water to optimize sludge-batch assembly.

Sarker, Md Sharif [Florida International Univ. (FI↗

Field-Scale Lysimeter Studies of Glass and Cementitious Waste Forms at the Hanford Site - 20392

The Hanford site Integrated Disposal Facility (IDF) will receive waste forms from vitrification activities at the Hanford Waste Treatment and Immobilization Plant (WTP). The waste form inventory to be disposed of at the IDF will consist of vitrified low-activity waste (LAW) in glass forms and solidified (or encapsulated) secondary wastes in cementitious forms. The IDF is a near-surface burial facility located near Hanford's Waste Treatment and Immobilization Plant in the 200 East Area of the site's Central Plateau. An extensive set of laboratory experimental data has been collected to support IDF performance assessment calculations of the eventual degradation of waste forms and mobility of contaminants. This paper describes the start of a field experiment to generate waste-form performance data on a larger scale (tens of centimeters), over a longer duration (five years or more), and under field conditions representative of the IDF. Results from this study are expected to improve model descriptions of contaminant mobility, reduce uncertainties about the representativeness of laboratory results in the IDF performance assessment, improve stakeholder confidence in the safe disposal of treated waste at the IDF, and facilitate the adoption of informed facility designs with the potential to reduce operational costs. A lysimeter test facility near Hanford's 200 West Area has been repurposed to carry out long-term assessments of waste forms buried in sediments excavated from the IDF. The waste forms are buried in large drainage lysimeters, open caissons that are two meters in diameter and three meters deep. Waste forms are buried in up to six locations in each lysimeter. Samplers collect pore water and drainage water beneath the waste forms and air from the pore space adjacent to waste forms. Sensors measure temperature, soil water content, soil water tension, and drainage flux. One lysimeter containing cementitious waste forms and one containing glass waste forms have been completed, along with a control lysimeter (without waste forms). The cementitious waste forms are Cast Stone grout formulations using a liquid secondary waste simulant and a generic Hanford high-salt simulant, as well as a hydrated lime-based grout formulation using a liquid secondary waste simulant. Technetium-99 and iodine-127 were added as tracers to monitor contaminant mobility. Glass waste forms were fabricated in two formulations (LAWA44 and ORLEC28), with rhenium and molybdenum tracers to monitor waste form degradation. The predicted performance of the waste forms in the lysimeters was modeled prior to installation to determine waste form size, tracer concentration/activity, and locations of sensors and samplers. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Water Sorption/Desorption Characteristics of Eutectic LiCl-KCl Salt-Occluded Zeolites

Molten salt consisting primarily of eutectic LiCl-KCl is currently being used in electrorefiners in the Fuel Conditioning Facility at Idaho National Laboratory. Options are currently being evaluated for storing this salt outside of the argon atmosphere hot cell. The hygroscopic nature of eutectic LiCl-KCl makes is susceptible to deliquescence in air followed by extreme corrosion of metallic cannisters. In this study, the effect of occluding the salt into a zeolite on water sorption/desorption was tested. Two zeolites were investigated: Na-Y and zeolite 4A. Na-Y was ineffective at occluding a high percentage of the salt at either 10 or 20wt% loading. Zeolite-4A was effective at occluding the salt with high efficiency at both loading levels. Weight gain in salt occluded zeolite-4A (SOZ) from water sorption at 20% relative humidity and 40°C was 17wt% for 10% SOZ and 10wt% for 20% SOZ. In both cases, neither deliquescence nor corrosion occurred over a period of 31 days. After hydration, most of the water could be driven off by heating the hydrated salt occluded zeolite to 530°C. However, some HCl forms during dehydration due to salt hydrolysis. Over a wide range of temperatures (320–700°C) and ramp rates (5, 10, and 20°C min -1 ), HCl formation was no more than 0.6% of the Cl - in the original salt.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Qualification of Processing Batches for Tank Closure Cesium Removal Through In-Tank Batch Contact Testing - 20470

The Tank Closure Cesium Removal (TCCR) process at the Savannah River Site (SRS) is currently processing waste from Tank 10H, generating decontaminated salt solution that is sent to Tank 11H. Transfers out of Tank 11H are then disposed of on site as a grout wasteform in the SRS Saltstone Processing Facility. This is a full-scale demonstration of the use of Crystalline Silicotitanate (CST) for the decontamination of aqueous nuclear waste supernate. CST primarily removes cesium from the high sodium alkaline feed, but also adsorbs strontium, actinides, and some other trace metals. The TCCR unit is an at-tank set of four ion exchange columns, with two typically being operated in series during waste processing. Tank 10H is serving a dual function as both the salt dissolution tank as well as the feed tank for the TCCR system. Prior to operation of TCCR, Tank 10H must undergo dissolution campaigns, dissolving the salt cake to form an aqueous salt solution (supernate). After each dissolution campaign, the supernate created must be qualified prior to processing through the TCCR system. Qualification includes detailed characterization of the supernate as well as in-tank batch contact tests to determine the equilibrium loading of Cs-137 on the CST ion exchange media (IONSIV{sup TM} R9120-Ba). In support of the in-tank batch contact testing, Savannah River National Laboratory (SRNL) developed a CST sample holder, also referred to as a 'tea-bag', to hold a measured amount (∼0.1 grams) of pretreated CST between stainless steel screens. The tea-bag fits within a standard stainless steel sample vial that has been modified to allow the flow of supernate to the CST. This sample holder is then immersed in the waste tank allowing free contact between the CST beads and the surrounding liquid, at an effectively infinite liquid-to-solid phase ratio. A pair of tea-bags are deployed in the tank for a period of 10 days for each batch, after which the CST is recovered, digested, and analyzed to determine the loading of cesium isotopes on the CST. This result then supports the TCCR column thermal loading limits for processing as part of the TCCR safety basis. This paper will discuss the design and testing of the CST sample holder, as well as results from the first few batches of waste qualified and subsequently processed through the TCCR system. In addition, results from analyses of Tank 11H samples, showing decontamination of the product will be included. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗