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Preparation and evaporation of Hanford Waste treatment plant direct feed low activity waste effluent management facility simulant

The Hanford Waste Treatment and Immobilization Plant (WTP) Low Activity Waste (LAW) vitrification facility will generate an aqueous condensate recycle stream (LAW Melter Off-Gas Condensate, LMOGC) from the off-gas system. The baseline plan for disposition of this stream during full WTP operations is to send it to the WTP Pretreatment Facility, where it will be blended with LAW, concentrated by evaporation, and recycled to the LAW vitrification facility. However, during the Direct Feed LAW (DFLAW) scenario, planned disposition of this stream involves concentrating the condensate in a new evaporator at the Effluent Management Facility (EMF) and returning it to the LAW melter. The LMOGC stream will contain components, e.g. halides and sulfates, that are volatile at melter temperatures, have limited solubility in glass waste forms, and present a material corrosion concern. Because this stream will recycle within WTP, these components are expected to accumulate in the LMOGC stream, exacerbating their impact on the number of LAW glass containers that must be produced. Diverting the stream reduces the halides and sulfates in the glass and is a key objective of this program. In order to determine the disposition path, it is key to experimentally determine the fate of contaminants. To do this, testing is needed to account for the buffering chemistry of the components, determine the achievable evaporation end point, identify insoluble solids that form, determine the formation and distribution of key regulatoryimpacting constituents, and generate an aqueous stream that can be used in testing of the subsequent immobilization step. This overall program examines the potential treatment and immobilization of the LMOGC stream to enable alternative disposal. The objective of this task was to (1) prepare a simulant of the LAW Melter Off-gas Condensate expected during DFLAW operations, (2) demonstrate evaporation in order to predict the final composition of the effluents from the EMF evaporator to aid in planning for their disposition, and (3) generate concentrated evaporator bottoms for use in immobilization testing.

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Draft Experimental Plan for Commercial SNF Degradation in Repository Environments with a Focus on Fracture Matrix Degradation

This report documents work performed supporting US Department of Energy (DOE) Nuclear Energy Spent Fuel and Waste Disposition, Spent Fuel and Waste Science and Technology, under work breakdown structure element 1.08.01.03.04, “Inventory and Waste Form Characteristics and Performance.” In particular, this report fulfills the M3 milestone, M3SF-21OR010309072 "Draft Experimental Plan for Commercial SNF Degradation in Repository Environments” as described in work package SF-21OR01030907 "SNF Degradation Testing-ORNL".This experimental plan is a collaboration between ORNL, SNL, ANL, and PNNL. It is intended to support source term model development and spent fuel degradation testing in a range of generic repository conditions. Potential testing and experiments to support validation of the Fuel Matrix Dissolution Model (FMDM) and the overall development/validation of repository source term modeling are discussed.

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Ruthenium solubility and its impact on the crystallization behavior and electrical conductivity of MoO 3 -containing borosilicate-based model high-level nuclear waste glasses

The present study focuses on investigating the solubility of RuO 2 in a borosilicate-based model high-level waste glass and understanding its impact on the crystallization behavior and electrical conductivity of the resulting vitrified waste forms. The solubility limit of RuO 2 in the investigated glass composition has been determined to be 460 ppm by weight. The higher concentration of RuO 2 results in sub-micron sized Ru-rich inclusions in the glassy matrix, which eventually agglomerate to form needle-like and polyhedral RuO 2 crystals. It is observed that RuO 2 selectively promotes the crystallization of the rare-earth apatite phase over the powellite phase. The as-synthesized RuO 2 -containing glasses exhibit semiconducting behavior with a similar level of electrical conductivity below the glass transition. Here, the percolation of non-uniformly distributed RuO 2 inclusions may result in a formation of short-range low-resistive conduction pathways in the host glass matrix leading to an apparent metallic-like behavior of selected thin samples with the highest ruthenium content.

36 MATERIALS SCIENCE↗

Summary of Calcine Disposal Development Using Hot Isostatic Pressing

Battelle Energy Alliance, LLC, has demonstrated the effectiveness of the hot isostatic press (HIP) process for treatment of hazardous high-level waste known as calcine that is stored at the Idaho Nuclear Technology and Engineering Center (INTEC) at Idaho National Laboratory. HIP trials performed with simulated calcines at Idaho National Laboratory’s Materials and Fuels Complex and an Australian Nuclear Science and Technology Organization facility from 2007 to 2010 produced a dense, monolithic waste form with increased chemical durability and effective (storage) volume reductions of ~10 to ~70% compared to granular calcine forms. In December 2009, the U.S. Department of Energy signed an amended Record of Decision selecting HIP technology as the treatment method for the 4,400 m3 of granular zirconia and alumina calcine stored at INTEC. Testing showed that HIP treatment reduces the risks associated with radioactive and hazardous constituent release, post-production handling, and long-term (repository) storage of calcines and would result in estimated storage cost savings in the billions of dollars. Battelle Energy Alliance has the ability to complete pilot-scale HIP processing of INTEC calcine, which is the next necessary step in implementing HIP processing as a calcine treatment method.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Effect of Iodide on Radiolytic Hydrogen Peroxide Generation

This report fulfills the milestone (M4SF-17PN010501041 Report on Radiolysis Modeling for the Defense Repository) to discuss continued integration of the PNNL Radiolysis Model and the ANL Mixed Potential Model. This work concerns the development of an integrated Radiolysis Model (RM) for evaluating defense waste materials (oxide and metal) degradation and radionuclide mobilization. Within an anoxic repository environment, primary oxidizing species (e.g., hydrogen peroxide (H 2 O 2 ), OH• radicals, as well as chlorate and other oxidizing species depending on the disposal environment) will be generated at the surface of the nuclear waste forms as a function of their specific activity. RM development has included expansion of chemical environments considered to encompass species for various disposal environments. PNNL has been coordinating this effort with ANL on the integration of the radiolysis work with the fuel degradation model. In this study, we demonstrate and approximate possible effects of iodide on H 2 O 2 generation. As has been shown these are conditions for which H 2 O 2 generation is reduced. We find that the presence of the iodide ion reduces the steady-state H 2 O 2 concentration, but not to the same degree as bromide at micro-molar concentrations.

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Performance of the Fluidized Bed Steam Reforming Product Under Hydraulically Unsaturated Conditions

Currently, several candidates for secondary waste immobilization at the Hanford site in the State of Washington, USA are being considered. To demonstrate the durability of the product in the unsaturated Integrated Disposal Facility (IDF) at the site, a series of tests have been performed one of the candidate materials using the Pressurized Unsaturated Flow (PUF) system. The material that was tested was the Fluidized Bed Steam Reformer (FBSR) granular product and the granular product encapsulated in a geopolymer matrix. The FBSR product is composed primarily of an insoluble sodium aluminosilicate matrix with the dominant phases being feldspathoid minerals mostly nepheline, sodalite, and nosean. The PUF test method allows for the accelerated weathering of materials, including radioactive waste forms, under hydraulically unsaturated conditions, thus mimicking the open-flow and transport properties that most likely will be present at the IDF. The experiments show a trend of decreasing tracer release as a function of time for several of the elements released from the material including Na, Si, Al, and Cs. However, some of the elements, notably I and Re, show a steady release throughout the yearlong test. This result suggests that the release of these minerals from the sodalite cage occurs at a different rate compared with the dissolution of the predominant nepheline phase.

Durability testing↗

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↗

Nepheline crystallization and the residual glass composition: Understanding waste glass durability

The vast majority of High-Level Waste (HLW) originating from defense nuclear programs is sequestered and immobilized in borosilicate glass. Borosilicate glass is universally accepted for immobilizing HLW, but its efficiency has limitations based on the compositional makeup of the waste stream. The chemical durability of the glass is the most important factor in determining the longevity and usefulness of the final glass waste form. The primary detriment to this durability in glasses containing high levels of aluminum is nepheline (NaAlSiO 4 ) crystallization, as it is generally accompanied by a measurable decrease in the glass's chemical durability. This work seeks to understand nepheline crystallization, within the context of thermal history, and to elucidate the influence of compositional shifts in the residual glass (after crystallization) on the measured durability. The results presented within show a distinct deviation in leaching behavior as a function of structural makeup (calculated Q units). This understanding will provide practical information required for broadening glass compositional regions needed to more efficiently vitrify HLW.

36 MATERIALS SCIENCE↗

LABORATORY OPTIMIZATION TESTS OF TECHNETIUM DECONTAMINATION OF HANFORD WASTE TREATMENT PLANT LOW ACTIVITY WASTE OFF-GAS CONDENSATE SIMULANT

The Hanford Waste Treatment and Immobilization Plant (WTP) Low Activity Waste (LAW) vitrification facility will generate an aqueous condensate recycle stream (LAW Off-Gas Condensate) from the off-gas system. The baseline plan for disposition of this stream is to send it to the WTP Pretreatment Facility, where it will be blended with LAW, concentrated by evaporation and recycled to the LAW vitrification facility again. Alternate disposition of this stream would eliminate recycling of problematic components, and would enable de-coupled operation of the LAW melter and the Pretreatment Facilities. Eliminating this stream from recycling within WTP would also decrease the LAW vitrification mission duration and quantity of glass waste. This LAW Off-Gas Condensate stream contains components that are volatile at melter temperatures and are problematic for the glass waste form. Because this stream recycles within WTP, these components accumulate in the Condensate stream, exacerbating their impact on the number of LAW glass containers that must be produced. Approximately 32% of the sodium in Supplemental LAW comes from glass formers used to make the extra glass to dilute the halides to acceptable concentrations in the LAW glass, and diverting the stream reduces the halides in the recycled Condensate and is a key outcome of this work. Additionally, under possible scenarios where the LAW vitrification facility commences operation prior to the WTP Pretreatment facility, identifying a disposition path becomes vitally important. This task examines the potential treatment of this stream to remove radionuclides and subsequently disposition the decontaminated stream elsewhere, such as the Effluent Treatment Facility (ETF), for example. The treatment process envisioned is very similar to that used for the Actinide Removal Process (ARP) that has been operating for years at the Savannah River Site (SRS), and focuses on using mature radionuclide removal technologies that are also compatible with longterm tank storage and immobilization methods. For this new application, testing is needed to demonstrate acceptable treatment sorbents and precipitating agents and measure decontamination factors for additional radionuclides in this unique waste stream. The origin of this LAW Off-Gas Condensate stream will be the liquids from the Submerged Bed Scrubber (SBS) and the Wet Electrostatic Precipitator (WESP) from the LAW melter off-gas system. The stream is expected to be a dilute salt solution with near neutral pH, and will likely contain some insoluble solids from melter carryover. The soluble components are expected to be mostly sodium and ammonium salts of nitrate, chloride, and fluoride. This stream has not been generated yet and will not be available until the WTP begins operation, but a simulant has been produced based on models, calculations, and comparison with pilot-scale tests. One of the radionuclides that is volatile and expected to be in greatest abundance in this LAW Off-Gas Condensate stream is Technetium-99 ({sup 99}Tc). Technetium will not be removed from the aqueous waste in the Hanford WTP, and will primarily end up immobilized in the LAW glass by repeated recycle of the off-gas condensate into the LAW melter. Other radionuclides that are low but are also expected to be in measurable concentration in the LAW Off-Gas Condensate are {sup 129}I, {sup 90}Sr, {sup 137}Cs, {sup 241}Pu, and {sup 241}Am. These are present due to their partial volatility and some entrainment in the off-gas system. This report discusses results of optimized {sup 99}Tc decontamination testing of the simulant. Testing examined use of inorganic reducing agents for {sup 99}Tc. Testing focused on minimizing the quantity of sorbents/reactants added, and minimizing mixing time to reach the decontamination targets in this simulant formulation. Stannous chloride and ferrous sulfate were tested as reducing agents to determine the minimum needed to convert soluble pertechnetate to the insoluble technetium dioxide. The reducing agents were tried with and without sorbents. The sorbents, hydroxyapatite and sodium oxalate, were expected to sorb the precipitated technetium dioxide and facilitate removal. The Phase 1 tests examined a broad range of conditions and used the initial baseline simulant. The Phase 2 tests narrowed the conditions based on Phase 1 results, and used a slightly modified simulant. Test results indicate that excellent removal of {sup 99}Tc was achieved using SnCl{sub 2} as a reductant, and was effective with or without sorption onto hydroxyapatite. This reaction worked even in the presence of air (which could oxidize the stannous ion) and at room temperature. This process was very effective at neutral pH, with a Decontamination Factor (DF) >199 in one hour with only 1 g/L of SnCl{sub 2}. Prior work had shown that it was much less effective at alkaline pH. The only deleterious effect observed was that the chromium co-precipitates with the {sup 99}c during the SnCl{sub 2} reduction. This effect was anticipated, and would have to be considered when managing disposition paths of this stream. Reduction using FeSO{sub 4} was not effective at removing {sup 99}Tc, but did remove the Cr. Chromium is present due to partial volatility and entrainment in the off-gas, and is highly oxidizing, so would be expected to react with reducing agents more quickly than pertechnetate. Testing showed that sufficient reducing agent must be added to completely reduce the chromium before the technetium is reduced and removed. Other radionuclides are also present in this off-gas condensate stream. To enable sending this stream to the Hanford ETF, and thereby divert it from the recycle where it impacts the LAW glass volume, several of these also need to be removed. Samples from optimized conditions were also measured for actinide removal in order to examine the effect of the Tc-removal process on the actinides. Plutonium was also removed by the SnCl{sub 2} precipitation process. Results of this separation testing indicate that sorption/precipitation is a viable concept and has the potential to decontaminate the {sup 99}Tc from the stream, allowing it to be diverted away from WTP and thus eliminating the impact of the recycled halides and sulfate on the LAW glass volume. Based on the results, a possible treatment scenario could involve the use of a reductive precipitation agent (SnCl{sub 2}) with or without sorbent at neutral pH to remove the Tc. Although hydroxyapatite was not necessary to effect the {sup 99}Tc removal, it may be beneficial in solid-liquid separations. Other testing will examine removal of the other radionuclides. This testing was the second phase of testing, which aimed at optimizing the process by examining the minimum amount of reductant needed and the minimum reaction time. Although results indicated that SnCl{sub 2} was effective, further work on a pH-adjusted Fe(SO{sub 4}) mixture are needed. Additional tasks are needed to examine removal of the other radionuclides, solid-liquid separation technologies, slurry rheology measurements, composition variability impacts, corrosion and erosion, and slurry storage and immobilization.

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Laboratory Scoping Tests Of Decontamination Of Hanford Waste Treatment Plant Low Activity Waste Off-Gas Condensate Simulant

The Hanford Waste Treatment and Immobilization Plant (WTP) Low Activity Waste (LAW) vitrification facility will generate an aqueous condensate recycle stream (LAW Off-Gas Condensate) from the off-gas system. The baseline plan for disposition of this stream is to send it to the WTP Pretreatment Facility, where it will be blended with LAW, concentrated by evaporation and recycled to the LAW vitrification facility again. Alternate disposition of this stream would eliminate recycling of problematic components, and would enable de-coupled operation of the LAW melter and the Pretreatment Facilities. Eliminating this stream from recycling within WTP would also decrease the LAW vitrification mission duration and quantity of glass waste. This LAW Off-Gas Condensate stream contains components that are volatile at melter temperatures and are problematic for the glass waste form. Because this stream recycles within WTP, these components accumulate in the Condensate stream, exacerbating their impact on the number of LAW glass containers that must be produced. Approximately 32% of the sodium in Supplemental LAW comes from glass formers used to make the extra glass to dilute the halides to acceptable concentrations in the LAW glass, and diverting the stream reduces the halides in the recycled Condensate and is a key outcome of this work. Additionally, under possible scenarios where the LAW vitrification facility commences operation prior to the WTP Pretreatment facility, identifying a disposition path becomes vitally important. This task seeks to examine the potential treatment of this stream to remove radionuclides and subsequently disposition the decontaminated stream elsewhere, such as the Effluent Treatment Facility (ETF), for example. The treatment process envisioned is very similar to that used for the Actinide Removal Process (ARP) that has been operating for years at the Savannah River Site (SRS), and focuses on using mature radionuclide removal technologies that are also compatible with longterm tank storage and immobilization methods. For this new application, testing is needed to demonstrate acceptable treatment sorbents and precipitating agents and measure decontamination factors for additional radionuclides in this unique waste stream. The origin of this LAW Off-Gas Condensate stream will be the liquids from the Submerged Bed Scrubber (SBS) and the Wet Electrostatic Precipitator (WESP) from the LAW melter off-gas system. The stream is expected to be a dilute salt solution with near neutral pH, and will likely contain some insoluble solids from melter carryover. The soluble components are expected to be mostly sodium and ammonium salts of nitrate, chloride, and fluoride. This stream has not been generated yet and will not be available until the WTP begins operation, but a simulant has been produced based on models, calculations, and comparison with pilot-scale tests. One of the radionuclides that is volatile and expected to be in high concentration in this LAW Off-Gas Condensate stream is Technetium-99 ( 99 Tc). Technetium will not be removed from the aqueous waste in the Hanford WTP, and will primarily end up immobilized in the LAW glass by repeated recycle of the off-gas condensate into the LAW melter. Other radionuclides that are also expected to be in appreciable concentration in the LAW Off-Gas Condensate are 129 I, 90 Sr, 137 Cs, and {sup 241}Am. This report discusses results of preliminary radionuclide decontamination testing of the simulant. Testing examined use of Monosodium Titanate (MST) to remove 90 Sr and actinides, inorganic reducing agents for 99 Tc, and zeolites for 137 Cs. Test results indicate that excellent removal of 99 Tc was achieved using Sn(II)Cl 2 as a reductant, coupled with sorption onto hydroxyapatite, even in the presence of air and at room temperature. This process was very effective at neutral pH, with a Decontamination Factor (DF) >577 in two hours. It was less effective at alkaline pH. Conversely, removal of the cesium was more effective at alkaline pH, with a DF of 17.9. As anticipated, ammonium ion probably interfered with the Ionsiv®a IE-95 zeolite uptake of 137 Cs. Although this DF of 137 Cs was moderate, additional testing is expected to identify more effective conditions. Similarly, Monosodium Titanate (MST) was more effective at alkaline pH at removing Sr, Pu, and U, with a DF of 319, 11.6, and 10.5, respectively, within 24 hours. Actually, the Ionsiv® IE-95, which was targeting removal of Cs, was also moderately effective for Sr, and highly effective for Pu and U at alkaline pH. The only deleterious effect observed was that the chromium co-precipitates with the {sup 99}Tc during the SnCl 2 reduction. This effect was anticipated, and would have to be considered when managing disposition paths of this stream. Results of this separation testing indicate that sorption/precipitation was a viable concept and has the potential to decontaminate the stream. All radionuclides were at least partially removed by one or more of the materials tested. Based on the results, a possible treatment scenario could involve the use of a reductive precipitation agent (SnCl 2 ) and sorbent at neutral pH to remove the Tc, followed by pH adjustment and the addition of zeolite (Ionsiv® IE-95) to remove the Cs, Sr, and actinides. Addition of MST to remove Sr and actinides may not be needed. Since this was an initial phase of testing, additional tasks to improve separation methods were expected to be identified. Primarily, further testing is needed to identify the conditions for the decontamination process. Once these conditions are established, follow-on tasks likely include evaluation and testing of applicable solid-liquid separation technologies, slurry rheology measurements, composition variability testing and evaluations, corrosion and erosion testing, slurry storage and immobilization investigations, and decontaminated LAW Off-Gas Condensate evaporation and solidification.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Results of Hg Speciation Testing on 2Q15 Tank 50 and Tank 21 TCLP Extraction Fluid Samples and Tank 49 Material

The Savannah River National Laboratory (SRNL) was tasked with preparing and shipping samples for Hg speciation by Eurofins Frontier Global Sciences, Inc. in Seattle, WA on behalf of the Savannah River Remediation (SRR) Mercury Task Team. The sixth shipment of samples was designated to include SRNL Toxicity Characteristic Leaching Procedure (TCLP) extraction fluids from the 2Q15 Tank 50 and Tank 21 saltstone waste forms as well as Tank 49 material (HTF-49-15-45) collected on May 7, 2015. The TCLP extraction fluid samples were collected from duplicate extractions of two crushed saltstone fractions, one designated as “large” and one designated as “normal”. Both fractions of 2Q15 Tank 50 and Tank 21 saltstones (eight samples) were collected with the minimum possible free headspace and refrigerated prior to final dilution. The Tank 49 sample was left in its stainless steel dip bottle until it was opened and an aliquot diluted 1:100 with Eurofins deionized water on May 21, 2015. Following initial dilution in the Shielded Cells, the diluted Tank 49 sample was immediately moved to refrigeration and kept in the dark until prepared for shipment to Eurofins.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Silver-iodine secondary waste stabilization: multi-scale evaluation

Iodine-129 is a key risk driver in most low-level waste cementitious waste repositories. The objectives of this study were to determine iodine speciation in cementitious materials with slag (Grout+slag) and without slag (Grout–slag) and its impact on iodine immobilization. Additional studies were conducted to determine if grout was compatibility as a waste form for the most common adsorbent used to remove aqueous and gaseous radioiodine, silver-impregnated granular activated carbon (Ag-GAC). Rankings of iodine species by their tendency to bind to grout were: iodide << organo-iodine ≤ iodate. Similarly, ranking of grout formulations by their tendency to immobilize iodine were: Grout +slag < Grout -slag . Organo-iodine comprised >40% of the leachate solution from grout samples initially hydrated (cured) with iodide. The origin of the organic ligand comprising the organo-iodine was organic carbon in the grout material (~1200 mg/kg). Iodine in the solid phase, as determined by K-edge X-ray Absorption Near-Edge Spectroscopy, and aqueous phases were not in equilibrium and essentially no iodine speciation transformations occurred within the grout after one month of curing, irrespective of which iodine species was initially added to the mix. For the first time, these studies demonstrate that multiple iodine species can co-exist simultaneously in grout porewater, the iodine species initially added to the grout can greatly affect immobilization, and that Ag-GAC can be safely disposed in grout formulation, but not in the presence of slag. These results help explain previous data and reduce uncertainty associated with the disposal of nuclear waste.

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Treatment of Magnesium-Thorium Alloy Used in Military Defence Equipment by Separation of Thorium and/or Thermal Oxidation - 17009

Magnesium-alloys doped with thorium (Th, 3% by weight and with a total activity content in the alloy of 120 Bq/g) to improve mechanical properties has been used in, among other applications, military equipment such as in the jet-engines in military aircraft. The material cannot, due to the presence of the radioactive Th, be handled as an ordinary scrap metal. It needs to be treated to render a more stable waste form prior to final disposal in which the amount of disposed metallic magnesium is limited due to the pyrophoric properties of such type of materials. By thermally treating the material it is possible to transform the alloy into oxide form (MgO and ThO{sub 2}) which is a much more stable form than metallic. This itself enables a form suitable for final disposal of the material. The oxidation step does however lead to an increase in volume and is therefore not an optimal treatment method. It is possible to treat the metal oxide powder in order to get a better volume reduction such as by super compaction but a better result can be obtained by separating the Th from the alloy, leaving a much smaller volume for final disposal. One way of separating the Th from the metal is by dissolution of metallic material in acid followed by directed precipitation of Th as Th-oxalate. Several parameters such as the choice of acid, metal concentration in the acid solution, pH prior to precipitation and amount of added oxalic acid have been investigated. Another method to separate Th from Mg is to perform a selective dissolution of MgO from an MgO/ThO{sub 2} mixture with HNO{sub 3} leaving only ThO{sub 2} as a residue. These tests had to be preceded with an oxidation of the alloy. The tests show that it is possible to separate Th from the metal alloy by either dissolution followed by precipitation or selective dissolution of MgO from an MgO/ThO{sub 2} mixture. This leads to very effective volume reduction of the waste. For the direct dissolution and precipitation tests typically > 95% of the magnesium can be found in the acid solution while 99.5 % of the Th is found as a solid in the filters. For the oxide dissolution tests typically 98% of the Th can be separated from the bulk material, leaving the acid solution possible to free release and dispose of in the same way as for the previous method. (authors)

36 MATERIALS SCIENCE↗

Washing Study with SRS Tank 26 Samples FTF-26-19-12 and -13

A recent analysis of Tank 26, one of the feed tanks for the Defense Waste Processing Facility (DWPF) Sludge Batch 10 (SB10), determined a higher than anticipated sulfur concentration in the supernatant and a significant amount of insoluble sulfur, which could negatively impact the DWPF glass waste form. Savannah River Remediation Engineering (SRR-E) requested that the Savannah River National Laboratory (SRNL) perform a washing study with Tank 26 material to determine amount of sulfur removed during washing tests. SRNL decanted supernate from a sample of Tank 26 until it was at 12 wt% insoluble solids. Subsequently, SRNL performed washing experiments from the 8 M sodium initial concentration to targeted endpoints of 4 M, 2 M and 1 M sodium concentration (assuming no sodium dissolution). Results show that over 80% of the sulfur was removed and nearly all the sulfur was in the aqueous phase at the end of washing, demonstrating effective removal of sulfur during washing. Additional washing is likely to decrease the sulfur concentration further since most of the sulfur was in the aqueous phase.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

M-Star ® Modeling of SME Mixing with Three Impeller Blades

Before a sample of the Slurry Mix Evaporator (SME) can be taken, the SME product sampling procedure requires that the agitator power be stable between 20 and 30 kW for at least one hour. The SME transfer to Melter Feed Tank (MFT) procedure also requires the SME agitator power be stabilized between 20 and 30 kW prior to transfer. These requirements are specified to ensure samples are homogeneous, as discussed in the Waste Form Qualification Report. During SME Batch 804, the agitator power dropped to 19 kW and struggled to achieve and maintain 20 kW. It was later discovered that the cause of the power drop was due to one of the bottom blades of the agitator breaking off. Both the sample and the transfer occurred without the power stabilizing between 20 and 30 kW. Therefore, the quality of SME Batch 804 is indeterminate, and homogeneity was questionable. To evaluate mixing in the SME with a broken agitator containing only three blades (90 degrees apart with space for a missing blade) on the bottom impeller, the Savannah River National Laboratory (SRNL) was requested to perform computer simulations of impeller mixing in the SME using M-Star ® software. The simulations will be used to determine if SME Batch 804 was well mixed and satisfies homogeneity requirements.

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Deep Borehole Disposal Safety Case

This report describes the current status of the safety case for the deep borehole disposal (DBD) concept. It builds on the safety case presented in Freeze et al. (2016), presenting new information and identifying additional information needs for specific safety case elements. At this preliminary phase of development, the DBD safety case focuses on the generic feasibility of the DBD concept. It is based on potential system designs, waste forms, engineering, and geologic conditions; however, no specific site or regulatory framework exists. Updated information is provided for the following safety case elements: (1) pre-closure basis and safety analysis, (2) post-closure basis and performance assessment, and (3) confidence enhancement. This research was performed as part of the deep borehole field test (DBFT). Based on revised U.S. Department of Energy (DOE) priorities in mid-2017, the DBFT and other research related to a DBD option was discontinued; ongoing work and documentation were closed out by the end of fiscal year (FY) 2017. This report was initiated as part of the DBFT and documented as an incomplete draft at the end of FY 2017. The report was finalized by Sandia National Laboratories in FY2018 without DOE funding, subsequent to the termination of the DBFT, and published in FY2019.

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Integrated Disposal Facility FY 2012 Glass Testing Summary Report

PNNL is conducting work to provide the technical basis for estimating radionuclide release from the engineered portion of the disposal facility for Hanford immobilized low-activity waste (ILAW). Before the ILAW can be disposed, DOE must conduct a performance assessment (PA) for the Integrated Disposal Facility (IDF) that describes the long-term impacts of the disposal facility on public health and environmental resources. As part of the ILAW glass testing program, PNNL is implementing a strategy, consisting of experimentation and modeling, to provide the technical basis for estimating radionuclide release from the glass waste form in support of future IDF PAs. Key activities in FY12 include upgrading the STOMP/eSTOMP codes to do near-field modeling, geochemical modeling of PCT tests to determine the reaction network to be used in the STOMP codes, conducting PUF tests on selected glasses to simulate and accelerate glass weathering, developing a Monte Carlo simulation tool to predict the characteristics of the weathered glass reaction layer as a function of glass composition, and characterizing glasses and soil samples exhumed from an 8-year lysimeter test. The purpose of this report is to summarize the progress made in fiscal year (FY) 2012 and the first quarter of FY 2013 toward implementing the strategy with the goal of developing an understanding of the long-term corrosion behavior of LAW glasses.

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Machine learning-enabled prediction of chemical durability of A 2 B 2 O 7 pyrochlore and fluorite

Pyrochlore-structure type and its derivative in a general formula A 2 B 2 O 7 (A = rare earth elements and actinides; B = Ti, Sn, Zr, Hf, Pb, Si, etc.) display excellent structural flexibility and rich crystal chemistry as promising nuclear waste form materials capable of immobilizing actinides and fission products. It is essential to understand these materials’ chemical durability and element release of radionuclides in order to evaluate their performance in near-field environment. However, it is a formidable grand technological challenge to experimentally perform durability testing across hundreds of thousands of possibilities resulting from their extreme compositional complexities due to cation substitutions at both A and B-sites. In this work, we demonstrate a machine learning approach to determine the key materials parameters and structural characteristics governing the leaching behaviors from a small set of selected compositions as model systems, enabling a science-based prediction of their chemical durability that can be extended to a wide range of chemical compositions. The combination of four key structural characteristics and materials parameters, including ionic radius size difference , ionic potential difference , electronegativity difference , and lattice parameter , creates features an optimized prediction of the chemical durability. Two machine learning models, linear regression and Kernel ridge regression models, are trained on the randomly-split training dataset derived from the experimentally-determined elemental release rates, and subsequently tested on the testing dataset. The predicted leaching rates from both machine learning models show an excellent agreement with the experimental data, demonstrating the feasibility of rapidly evaluating the material properties of new compositions. These results highlight the immense potential of synergizing informatics through machine learning-based models and well-controlled experiments of selected model systems to accelerate materials design and discovery with optimized compositions and performance of promising materials for effective nuclear waste management.

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