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All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

Performance Assessment of a Generic Nuclear Waste Repository in Shale - 18392

A performance assessment (PA) is an important component of a comprehensive safety analysis for a nuclear waste repository. In a PA, probabilistic simulations of the total repository system are performed, and results are evaluated against performance metrics. Uncertainty and sensitivity analyses help prioritize additional research and model development. The United States Department of Energy (DOE) has been developing a state of the art PA simulation software tool-kit, Geologic Disposal Safety Assessment (GDSA) Framework, that couples increasingly higher fidelity models of subsystem processes into total system PA simulations. Over the past several years, PAs of generic repositories in three geologic media (salt, shale, and crystalline rock) have demonstrated ongoing developments in capability. The current PA of a nuclear waste repository in a generic shale formation showcases GDSA Framework, including capabilities in domain discretization (Cubit), multi-physics simulations (PFLOTRAN), uncertainty and sensitivity analysis (Dakota), and visualization (Paraview). The generic shale reference case considers the disposal of 22,000 metric tons heavy metal of commercial spent nuclear fuel (SNF) in a generic shale formation. PA simulations account for the thermal load and radionuclide inventory of the waste form, components of the engineered barrier system including waste package and buffer, and components of the natural barrier system including the host rock shale and underlying and overlying stratigraphic units. Two repository layouts are considered, one for emplacement of waste packages containing 12 pressurized water reactor (PWR) assemblies, and one for 4-PWR waste package emplacement. Model domains are half-symmetry and contain between 7 and 22 million grid cells. Grid refinement captures the detail of individual waste packages, emplacement drifts, access drifts, and shafts. Simulations are run in a high-performance computing (HPC) environment on 512 or 2048 processes. The governing equations describing coupled heat and fluid flow and reactive transport are solved with PFLOTRAN, an open-source, massively parallel multiphase flow and reactive transport code. Additional simulated processes include waste package degradation; waste form dissolution; radioactive decay and ingrowth in aqueous, solid, and adsorbed phases; and a simple biosphere based on a pumping well. Simulations are run to 106 y; dose and radionuclide concentrations are observed within aquifers at a point approximately 5 km downgradient of the repository. Dakota is used to sample likely ranges of input parameters including waste form and waste package degradation rates and properties of engineered and natural materials to quantify uncertainty in predicted concentrations and sensitivity to input parameters. Given the assumptions of the reference case, results of 12-PWR and 4-PWR simulations are very similar. Dose at the pumping well 5-km downgradient of the repository does not exceed 10-9 Sv/y. I-129 is the largest contributor to dose. The dose due to Cl-36, the next largest contributor, is orders of magnitude smaller. At the pumping well, the concentration of I-129 5-km downgradient does not exceed 10-14 mol/L. Rank correlation coefficients indicate that the maximum concentration of I-129 within the aquifer is sensitive to shale (repository host rock) porosity and aquifer permeability. These results affirm that HPC-capable codes can be used to simulate important multi-physics couplings directly in a total system performance assessment of a geologic repository, and can be used in prioritization of future research and model development. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2016

Structure and thermodynamics of uranium-containing iron garnets

Use of crystalline garnet as a waste form phase appears to be advantageous for accommodating actinides from nuclear waste. Previous studies show that large amounts of uranium (U) and its analogues such as cerium (Ce) and thorium (Th) can be incorporated into the garnet structure. In this study, we synthesized U loaded garnet phases, Ca 3 U x Zr 2–x Fe 3 O 12 (x = 0.5–0.7), along with the endmember phase, Ca 3 (Zr 2 )SiFe 3+ 2 O 12 , for comparison. The oxidation states of U were determined by X-ray photoelectron and absorption spectroscopies, revealing the presence of mixed pentavalent and hexavalent uranium in the phases with x = 0.6 and 0.7. The oxidation states and coordination environments of Fe were measured using transmission 57 Fe-Mössbauer spectroscopy, which shows that all iron is tetrahedrally coordinated Fe 3+ . U substitution had a significant effect on local environments, the extent of U substitution within this range had a minimal effect on the structure, and unlike in the x = 0 sample, Fe exists in two different environments in the substituted garnets. The enthalpies of formation of garnet phases from constituent oxides and elements were first time determined by high temperature oxide melt solution calorimetry. The results indicate that these substituted garnets are thermodynamically stable under reducing conditions. Furthermore, our structural and thermodynamic analysis further provides explanation for the formation of natural uranium garnet, elbrusite-(Zr), and supports the potential use of Ca 3 U x Zr 2–x Fe 3 O 12 as viable waste form phases for U and other actinides.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2013

Cast Stone Oxidation Front Evaluation: Preliminary Results For Samples Exposed To Moist Air

The rate of oxidation is important to the long-term performance of reducing salt waste forms because the solubility of some contaminants, e.g., technetium, is a function of oxidation state. TcO 4 - in the salt solution is reduced to Tc(IV) and has been shown to react with ingredients in the waste form to precipitate low solubility sulfide and/or oxide phases. Upon exposure to oxygen, the compounds containing Tc(IV) oxidize to the pertechnetate ion, Tc(VII)O 4 - , which is very soluble. Consequently the rate of technetium oxidation front advancement into a monolith and the technetium leaching profile as a function of depth from an exposed surface are important to waste form performance and ground water concentration predictions. An approach for measuring contaminant oxidation rate (effective contaminant specific oxidation rate) based on leaching of select contaminants of concern is described in this report. In addition, the relationship between reduction capacity and contaminant oxidation is addressed. Chromate (Cr(VI) was used as a non-radioactive surrogate for pertechnetate, Tc(VII), in Cast Stone samples prepared with 5 M Simulant. Cast Stone spiked with pertechnetate was also prepared and tested. Depth discrete subsamples spiked with Cr were cut from Cast Stone exposed to Savannah River Site (SRS) outdoor ambient temperature fluctuations and moist air. Depth discrete subsamples spiked with Tc-99 were cut from Cast Stone exposed to laboratory ambient temperature fluctuations and moist air. Similar conditions are expected to be encountered in the Cast Stone curing container. The leachability of Cr and Tc-99 and the reduction capacities, measured by the Angus-Glasser method, were determined for each subsample as a function of depth from the exposed surface. The results obtained to date were focused on continued method development and are preliminary and apply to the sample composition and curing / exposure conditions described in this report. The Cr oxidation front (depth to which soluble Cr was detected) for the Cast Stone sample exposed for 68 days to ambient outdoor temperatures and humid air (total age of sample was 131 days) was determined to be about 35 mm below the top sample surface exposed. The Tc oxidation front, depth at which Tc was insoluble, was not determined. Interpretation of the results indicates that the oxidation front is at least 38 mm below the exposed surface. The sample used for this measurement was exposed to ambient laboratory conditions and humid air for 50 days. The total age of the sample was 98 days. Technetium appears to be more easily oxidized than Cr in the Cast Stone matrix. The oxidized forms of Tc and Cr are soluble and therefore leachable. Longer exposure times are required for both the Cr and Tc spiked samples to better interpret the rate of oxidation. Tc spiked subsamples need to be taken further from the exposed surface to better define and interpret the leachable Tc profile. Finally Tc(VII) reduction to Tc(IV) appears to occur relatively fast. Results demonstrated that about 95 percent of the Tc(VII) was reduced to Tc(IV) during the setting and very early stage setting for a Cast Stone sample cured 10 days. Additional testing at longer curing times is required to determine whether additional time is required to reduce 100 % of the Tc(VII) in Cast Stone or whether the Tc loading exceeded the ability of the waste form to reduce 100 % of the Tc(VII). Additional testing is required for samples cured for longer times. Depth discrete subsampling in a nitrogen glove box is also required to determine whether the 5 percent Tc extracted from the subsamples was the result of the sampling process which took place in air. Reduction capacity measurements (per the Angus-Glasser method) performed on depth discrete samples could not be correlated with the amount of chromium or technetium leached from the depth discrete subsamples or with the oxidation front inferred from soluble chromium and technetium (i.e., effective Cr and Tc oxidation fronts). Residual reduction capacity in the oxidized region of the test samples indicates that the remaining reduction capacity is not effective in re-reducing Cr(VI) or Tc(VII) in the presence of oxygen. Depth discrete sampling and leaching is a useful for evaluating Cast Stone and other chemically reducing waste forms containing ground granulated blast furnace slag (GGBFS) or other reduction / sequestration reagents to control redox sensitive contaminant chemistry and leachability in the near surface disposal environment. Based on results presented in this report, reduction capacity measured by the Angus-Glasser Ce(IV) method is not an appropriate or meaningful parameter for determining or predicting Tc and Cr oxidation / retentions, speciation, or solubilities in cementitious materials such as Cast Stone. A model for predicting Tc(IV) oxidation to soluble Tc(VII) should consider the waste form porosity (pathway for oxygen ingress), oxygen source, and the contaminant specific oxidation rates and oxidation fronts. Depth discrete sampling of materials exposed to realistic conditions in combination with short term leaching of crushed samples has potential for advancing the understanding of factors influencing performance. This information can be used to support conceptual model development.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2018

Solidified Organics Testing

The Radiochemical Engineering Development Center currently has plutonium-containing liquid organic waste that must be solidified before final disposal as solid debris waste. The documented safety analysis for the Radiochemical Engineering Development Center limits the amount of plutonium that can be released from solid debris waste forms during a fire scenario, which is less than 10 -4 airborne release fraction. Experimental results for plutonium release fractions from burning various materials has been compiled by the Department of Energy [DOE, 1994]. Combustion of organic liquids gave an average airborne release fraction of 6 × 10 -3 and combustion of surface-contaminated solids (paper, plastic, etc.) gave an average airborne release fraction of 5 × 10 -4 . Burning of 30% tri- n -butyl phosphate (TBP) in kerosene gave cerium release fractions of 5.6–7.7 × 10 -3 [Mishima and Schwendiman, 1973]. Earlier testing had evaluated many different grout-based formulations to solidify plutonium-containing organic waste liquids, and the ones used in these tests were shown to produce monolithic, fairly homogeneous solids. Each of the waste forms tested would meet the waste acceptance criteria for disposal at the Waste Isolation Pilot Plant as transuranic waste, but there were questions about whether they would meet the plutonium release criteria during a fire. The purpose of the work described here was to quantify the airborne release fraction for cerium, as a surrogate for plutonium, in these proposed waste forms. Cerium is often used as a simulant for plutonium in bench-scale testing, and cerium nitrate hexahydrate [Ce (NO 3 ) 3 ·6H 2 O] was added to the organic solutions that were solidified to prepare the surrogate waste forms for these tests. The waste forms were subjected to the designated fire scenario of 600ºC for 1 hour, and any cerium in the off-gas was trapped using a quartz filter followed by a scrubber containing 0.1 M NaOH, which is the same as used by Mishima and Schwendiman, [1973].

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2019

Method Development for High Temperature In-Situ Neutron Diffraction Measurements of Glass Crystallization on Cooling from Melt

A glass-ceramic borosilicate waste form is being considered for immobilization of waste streams of alkali, alkaline-earth, lanthanide, and transition metals generated by transuranic extraction for reprocessing used nuclear fuel. Waste forms are created by partial crystallization on cooling, primarily of oxyapatite and powellite phases. In-situ neutron diffraction experiments were performed to obtain detailed information about crystallization upon cooling from 1200°C. The combination of high temperatures and reactivity of borosilicate glass with typical containers used in neutron experiments, such as vanadium and niobium, prevented their use here. Thus, methods using sealed thick-walled silica ampoules were developed for the in-situ studies. Unexpectedly, high neutron absorption, low crystal fraction, and high silica container background made quantification difficult for these high temperature measurements. As a follow-up, proof-of-concept measurements were performed on different potential high-temperature container materials, emphasizing crystalline materials so that residual glass in the waste form sample could be more easily analyzed. Room temperature measurements were conducted with a pre-crystallized sample in ‘ideal’ containers stable at low temperatures (i.e., vanadium and thin-wall silica capillaries) and compared to the same measurements in containers stable at high temperatures (i.e, platinum, single crystal sapphire, and thick-walled silica ampoules). Results indicated that Pt is probably the best choice if suitably sealed to prevent contamination from the sample after neutron activation.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Tank Waste LDR Organics Data Summary for Sample-and-Send (Rev.1A)

The presence of organic chemicals regulated under the Resource Conservation and Recovery Act (RCRA) Land Disposal Restrictions (LDR) adds complexity to treating and disposing of the low activity fraction of Hanford tank waste if a low temperature treatment method such as grouting is used (SRNL-STI-2020-00228). The complexity arises from the fact that the baseline vitrification method is considered by the Washington State Department of Ecology (Ecology) as providing adequate thermal treatment for organics; a status not automatically extended to a lowtemperature process, such as solidifying the waste in a cementitious waste form. In addition, the Environmental Protection Agency (EPA) LDR program is intended to ensure that wastes are properly treated prior to disposal. Proper treatment makes hazardous waste less harmful to groundwater by reducing the mobility and/or toxicity of the hazardous constituents in the waste. EPA guidance indicates that stabilization/solidification of waste for organics could be considered impermissible dilution under the LDR dilution prohibition. In addition, waste storage activities at Hanford have required transferring and blending waste within the tank system and these activities have potentially altered the concentrations of the hazardous constituents. The LDR dilution prohibition found in 40 Code of Federal Regulations (CFR) 268.3 states that “… no generator, transporter, handler, or owner or operator of a treatment, storage, or disposal facility shall in any way dilute a restricted waste or the residual from treatment of a restricted waste as a substitute for adequate treatment …”. Hence, if LAW is to be treated using low temperature stabilization (such as cementation), then it is important to demonstrate both how past storage activities have contributed to the removal (by vacuum evaporation), or destruction (by in situ decomposition) of the LDR organics and how future retrieval and waste feed preparation will contribute to their removal (by filtration and ion exchange). Demonstrating these processes helps validate that cementation without additional organic treatment does not necessarily represent impermissible dilution. To aid in implementing cementitious solidification of Low Activity Waste (LAW), WRPS has been developing a regulatory and processing LDR treatment variance strategy termed “Sampleand-Send” that relies, in part, on demonstrating that in situ decomposition reactions along with historic evaporation of tank waste has destroyed or removed most of the LDR organics possibly associated with Hanford Tank Waste (SRNL-STI-2020-00582, SRNL-STI-2021-00453, SRNL-STI-2022-00391). Under the Sample-and-Send concept, Hanford tank waste would be retrieved, processed through a Tank-Side Cesium Removal-like system, and staged as a candidate feed that would then be sampled to confirm the waste acceptance criteria is met for solidification in an LAW cementitious treatment facility. If it can be shown that LDR organics are at concentrations below the waste acceptance criteria (WAC) for cementitious stabilization and have been sufficiently removed (by historic evaporation or by filtration and ion exchange during Cs removal), destroyed (by historic in situ decomposition), or are not soluble in LAW above the WAC then additional organic treatment is not needed prior to creating a cementitious final waste form and the concept of Sample-and-Send would be proposed to establish a non-rulemaking site-specific treatment variance using the specified method of treatment “STABL” to remove sampling requirements of the waste form after treatment. Waste not meeting the WAC could either be routed to the Hanford Waste Treatment and Immobilization Plant for LAW vitrification, or further processed by evaporation or chemical oxidation before solidifying in a cementitious waste form. A key component in implementing the Sample-and-Send strategy is identifying which of the 207 LDR organic compounds associated with the RCRA Part A permit application waste codes for the Double Shell Tanks (DSTs) and Single Shell Tanks (SSTs) and any applicable Underlying Hazardous Constituents (UHCs) from 40 CFR 268.48 should be considered as potentially present and thus subject to regulation. In addition, it is also necessary to understand the solubility volatility, and reactivity of these compounds in LAW to identify which of the potentially present LDR organic compounds are not soluble above regulatory levels or are likely to have been removed by historic evaporation or destroyed by in situ decomposition reactions. If there are potentially present LDR organic compounds that have not been removed or destroyed and are soluble above regulatorily significant concentrations then a treatability variance may be needed for these species to eliminate any concerns pertaining to impermissible dilution. The spreadsheet accompanying this calculation report contains the data and logic computations needed to screen the list of 207 LDR organics associated with Hanford tank waste to identify those potentially present and to indicate which compounds may need to be included in a treatability variance.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2018

Enhanced Evaluation Criteria to Meet the WIPP Waste Acceptance Criteria - 18655

The Waste Isolation Pilot Plant (WIPP) is a deep geologic repository for the disposal of Transuranic (TRU) waste and the only such disposal facility of its kind. TRU waste is radioactive mixed waste generated by the U. S. Department of Energy in support of National Defense. In 2014, the WIPP facility was shut down when two separate accidents occurred in the repository. The two accidents were a fire on a large underground haul truck that prompted evacuation and filled the mine with smoke and soot, and a radiation release that contaminated the exhaust ventilation and disposal areas of the mine. DOE performed two accident investigations in 2014 that resulted in many corrective actions. Some of the corrective actions resulted in significant changes in the WIPP Waste Acceptance Criteria (WAC) and are required to be applied to all TRU waste upon the resumption of shipments to WIPP. WIPP re-opened and began taking shipments again in 2017 and a large backlog of over 25,000 TRU waste containers that were certified prior to the new WAC have been undergoing re-evaluation since the re-opening. This paper will focus on the new WAC criteria that TRU waste must meet above-and-beyond previous WAC criteria and the implementation of new processes for approval. The primary area for these changes is in the area of waste characterization using Acceptable Knowledge (AK) and new detailed analyses required for chemical compatibility. The accident investigation revealed that the radiation release was due to a thermal runaway and bursting of the waste container due to inadvertent mixtures of nitrates and combustibles resulting in ignitable waste forms. In other words, the TRU waste container had incompatible contents that went undiscovered and created a hazard characteristic that was prohibited at WIPP. Through detailed chemical compatibility evaluations and new oversight, the DOE should be able to prevent a similar accident (see Figure 1). The new chemical compatibility evaluations and evaluations of oxidizing chemicals combined with combustibles are complex and detailed. Chemical compatibility is not a new requirement, but a much more detailed evaluation is a new requirement. And, obtaining historical information about the generation of the final waste form for legacy packaged waste can be very challenging. Specifically, determining possible amounts of chemicals in the waste can be extremely challenging. This paper does not explore in depth, the details of oxidizing chemicals. Other papers presented will discuss oxidizing chemicals. (author)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2024

Full Scale HEPA Filter Encapsulation in Ultra-High-Performance Grout - Proof of Concept

The Hanford Tank Waste Treatment and Immobilization Plant (WTP) currently being constructed to treat radioactive waste, includes vitrification facilities for both the high-level waste (HLW) and low activity waste (LAW) fractions. Operation of the WTP will produce contaminated high-efficiency particulate air filters (HEPA), as part of the solid secondary waste (SSW) stream. The HEPA filters receive off-gas from the vessel vent header and primary off-gas treatment system in LAW Facility and remove particulate contaminants including 99 Tc and 129 I salts. The current disposal method for HEPA filters is encapsulation in metal containers using cementitious material (CM) and disposal in the Integrated Disposal Facility (IDF). Results from the 2017 IDF Performance Assessment (PA) WRPS (2018) demonstrated that while compliance is maintained for the 1000 year compliance period mandated by DOE O 435.1 and its accompanying manual, release of constituents from the HEPA filters result in exceedance of the performance objective imposed as the groundwater regulatory limit at later times. For example, at about 1500 years post-closure, solid secondary waste (SSW), including HEPA filters is predicted to become a dominant contributor to 99 Tc release and over the 10,000-year sensitivity analysis period, SSW is the dominant contributor of 129 I release to the groundwater. The estimated release could potentially be reduced if the HEPA filters are not compacted and waste containers could be distributed throughout a large space, thereby diluting the contaminant release. Additionally, a better cementitious material could be used to encapsulate the HEPA filters. One alternative method for disposal of contaminated HEPA filters is encapsulation of the filters in ultra high-performance grout (UHPG). UHPG is a variation of ultra-high-performance concrete (UHPC) is commonly used in the prestressed concrete industry for large structural members. Recent studies of UHPG show it has excellent properties for containing radionuclides such as 99 Tc and 129 I Nichols and Kaplan (2021). This report presents the results of the first attempt to encapsulate a clean, full-size HEPA filter in UHPG and evaluate the effectiveness of the immobilization process and final waste form. A full-scale proof-of-concept simulated waste form was prepared by encapsulating a HEPA filter in a 110-gallon stainless steel (SS) drum using UHPG. A change from Type I/II PC to Type 1L PLC was made after American Rock Products informed the team that they would no longer be using Type I/II by the end of 2024 and the northwest was phasing out Type I/II PC overall. Type I/II PC used in previous studies of UHPG for encapsulation (Nichols and Kaplan 2021). After the UHPG was cured both the scaled mockup and the full-scale simulated waste forms were sectioned for visual examination. UHPG completely encapsulated the filters and bonded to the external surfaces of materials comprising the filters. No cracks were observed in the sectioned waste forms.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2016

Large Diameter Deep Borehole (LDDB) Disposal Design Option for Vitrified High-Level Waste (HLW) and Granular Wastes

This study considers the feasibility of large diameter deep boreholes for waste disposal. The conceptual approach considers examples of deep large diameter boreholes that have been successfully drilled, and also other deep borehole designs proposed in the literature. The objective for large diameter boreholes would be disposal of waste packages with diameters of 22 to 29 inches, which could enable disposal of waste forms such as existing vitrified high level waste. A large-diameter deep borehole design option would also be amenable to other waste forms including calcine waste, treated Na-bonded and Na-bearing waste, and Cs and Sr capsules.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2020

Stabilization/Solidification of Tritiated Water - 20135

Tritiated water was stabilized/solidified by using calcium oxide and a polymer. First, tritiated water was changed into the powder form of calcium hydroxide by addition of tritiated water into calcium oxide. Then the produced calcium hydroxide was solidified in waste form by using a polymer binder. The specimens of waste form prepared by surrogate calcium hydroxide were subjected to compressive strength testing and water immersion testing. In addition, the specimens of waste form prepared by tritiated calcium hydroxide were subjected to leach testing. The mean compressive strength of the specimens containing 40 wt % of the surrogate calcium hydroxide was about 98.5 MPa (14,300 psi). After water immersion testing, there was no distinct change in the appearance of the specimens. The mean compressive strength of the specimens after water immersion was 79.1 MPa (11,470 psi). The mean diffusion coefficient of tritium for the specimens containing 40 wt% of tritiated calcium hydroxide was 5.4 x 10-10 cm{sup 2}/s. These findings indicate that the waste form has enough mechanical integrity and durability for final disposal and releases tritium very slowly. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2013

Completion of the Operational Closure of Tank 18F and Tank 19F at the Savannah River Site by Grouting - 13236

Radioactive waste is stored in underground waste tanks at the Savannah River Site (SRS). The low-level fraction of the waste is immobilized in a grout waste form, and the high level fraction is disposed of in a glass waste form. Once the waste is removed, the tanks are prepared for closure. Operational closure of the tanks consists of filling with grout for the purpose of chemically stabilizing residual material, filling the tank void space for long-term structural stability, and discouraging future intrusion. Two of the old-style single-shell tanks at the SRS have received regulatory approval confirming waste removal had been completed, and have been stabilized with grout as part of completing operational closure and removal from service. Consistent with the regulatory framework, two types of grout were used for the filling of Tanks 18F and 19F. Reducing grout was used to fill the entire volume of Tanks 18F and 19F (bulk fill grout) and a more flowable grout was used to fill equipment that was left in the tank (equipment fill grout). The reducing grout was added to the tanks using portable grout pumps filled from concrete trucks, and delivered the grout through slick lines to the center riser of each tank. Filling of the two tanks has been completed, and all equipment has been filled. The final capping of riser penetrations brings the operation closure of Tanks 18F and 19F to completion. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2018

Unique Facilities, Innovative Treatment Processes, and a Talented Workforce Allow Fluor Idaho to Successfully Disposition Transuranic Waste - 18388

Fluor Idaho is utilizing state-of-the-art equipment, treatment technologies, and employee expertise at the Department of Energy's (DOE) Idaho Site to treat contact-handled transuranic (CH-TRU) waste, as well as extremely challenging remote-handled transuranic (RH-TRU) waste forms, to prepare the material for shipment and permanent disposal at the Department's Waste Isolation Pilot Plant (WIPP). Nowhere else in the DOE Complex - perhaps the world - will one find the compilation of tools and an experienced workforce with an unparalleled history of safely retrieving, characterizing, treating, repackaging, certifying, and shipping TRU waste. Since 2003, the Advanced Mixed Waste Treatment Project (AMWTP) has used both conventional and unique retrieval concepts, high-tech characterization equipment - including real-time radiography and radioassay - robotics, and automated treatment processes to retrieve and treat 65,000 cubic meters of above-ground CH-TRU waste. Additionally, engineered controls and specialized personal protective equipment have allowed employees to make thousands of entries into high-radiation areas without a skin or clothing contamination incident - evidence of the employees' commitment to safety. AMWTP has encountered and found solutions for many challenging waste forms, including polychlorinated biphenyl-contaminated wastes, TRU waste containers with up to 1,000 fissile gram equivalent plutonium-239, oversized TRU boxes, and partially absorbed organic sludge waste. By utilizing additional facilities and equipment at the Accelerated Retrieval Project V and VII, Fluor Idaho has developed new processing lines and capabilities to ensure worker safety and milestone completion. These two soft-sided buildings, located at a facility adjacent to AMWTP, were originally constructed to exhume Comprehensive Environmental Response, Compensation and Liability Act (CERCLA) TRU wastes from a section of a 97-acre landfill. After a total of 1,150 cubic meters of targeted waste were removed, personnel, working in collaboration with state regulators, successfully implemented a unique regulatory strategy that allowed these CERCLA facilities to be modified and permitted to treat Resource Conservation and Recovery Act (RCRA) wastes from the AMWTP - a savings of tens of millions of dollars over the cost of constructing new buildings. Adding to the AMWTP's technological uniqueness is its ability to treat wastes from other facilities in the DOE Complex. Two prior decision documents and an agreement with the state of Idaho have allowed AMWTP to treat wastes from 15 other DOE sites. It is the only project in the complex to have done so. At another project located next to AMWTP, targeted waste exhumation within the Subsurface Disposal Area is approximately two years ahead of schedule. Crews have removed more than 8,600 cubic meters of CH-TRU and hazardous wastes from eight exhumation areas that equal a combined footprint of 4.75 acres. Less than one acre remains to be exhumed to satisfy the 2008 Record of Decision waste exhumation end state between the DOE, Environmental Protection Agency, and state of Idaho. Construction of the final building where targeted waste exhumation will continue was completed during the summer of 2017. Exhumation will be completed within the next few years. Following exhumation completion, an evapotranspiration barrier (or cap) will be constructed over the entire landfill. Fluor Idaho continues to make progress on a more challenging project involving an inventory of RH-TRU waste that also contains the reactive metal sodium. Crews are utilizing hot cells, once used for spent nuclear fuel reprocessing and high-level waste treatment at the Idaho Nuclear Technology and Engineering Center, to render this challenging waste form safe for disposal in a national geologic waste repository. The treatment methods being employed on this RH-TRU waste are unique in the DOE Complex. Minute concentrations of water are sprayed onto the sodium-contaminated material in a process called 'spritzing' to chemically change the sodium from a reactive metal to a non-reactive salt. In other cases, sodium-contaminated waste is dipped in water to initiate a reaction in a process called 'immersion.' Lastly, for more challenging waste shapes that could not be successfully treated with the two prior methods, crews lower the sodium-contaminated RH-TRU waste into a one-of-a-kind distillation unit that uses high temperature and vacuum to volatilize the sodium and recapture it in a condenser unit for disposal. The RH-TRU waste treated with this technology is then safe for permanent disposal. Fluor Idaho is proud to operate DOE's CH- and RH-TRU waste treatment facilities, as well as use innovative processes and its talented workforce to complete this important work-scope. Such capabilities allow the contractor to meet the commitments made by the DOE to the state of Idaho. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2016

Performance Criteria for Capture and/or Immobilization Technologies

The capture and subsequent immobilization of the four volatile radionuclides ( 3 H, 14 C, 85 Kr, and 129 I) from the off-gas streams of a used nuclear fuel reprocessing facility has been a topic of substantial research interest for the US DOE and international colleagues. Regulations set forth by the US EPA direct that some or all of these radionuclides (based upon fuel burnup, fuel type, cooling time, etc.) will require removal, to some extent, from the plant effluent streams prior to discharge to the environment. Upon removal, the radionuclide, as well as any associated sorbent, is destined for waste. Research of separation and capture methodologies has included a wide range of technologies including liquid caustic scrubbing systems, solid adsorbents, and cryogenic distillation. The studies of waste forms have been correspondingly diverse. In considering the technologies available for future development and implementation of both sorbents and waste forms, it will be necessary to use benchmarked measures of performance to objectively evaluate each sorbent system or waste form. This document is intended to provide initial guidance on the types of performance criteria for capture materials and waste forms intended for use in the recycling removal and disposal of UNF and, where possible, the minimum acceptable values for those criteria.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2019

Effect of solution chemistry on the iodine release from iodoapatite in aqueous environments

To ensure the safe disposal of nuclear waste, understanding the release process of radionuclides retained in the nuclear waste forms is of vital importance. Iodoapatite Pb 9.85 (VO 4 ) 6 I 1.7 , a potential waste form for iodine-129, was selected as a model system for ceramic waste forms in this study to understand the effect of aqueous species on iodine release. Semi-dynamic leaching tests were conducted on bulk samples in cap-sealed Teflon vessels with 0.1 mol/L NaCl, Na 2 CO 3 , Na 3 PO 4 , and Na 2 SO 4 solutions under 90 °C, fixed sample surface area to solution volume ratio of 5/m, and periodic replacement of leaching solutions. The reacted solutions were then analyzed by Inductively Coupled Plasma-Mass Spectrometry and Inductively Coupled Plasma-Optical Emission Spectrometry; the leached surfaces were characterized by X-ray diffraction, scanning electron microscopy, and infrared spectroscopy. The finding shows that, compared to deionized water, the ion-rich solutions enhanced the iodine release as a result of the increased ionic strength, reduced activity coefficient of dissolved species, and increased solution pH. Surface reactions can lead to the formations of secondary phases by ion-exchange and precipitation. These findings indicate that an ion-rich environment in the geological repository can be detrimental to the disposal safety of the nuclear waste form.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Effect of Curing Environment on the Performance Properties of Saltstone - 13335

At the Savannah River Site (SRS), the low level radioactive waste (LLW) salt solution is immobilized as a cementitious waste form known as Saltstone. Depending on the Saltstone formulation, disposal unit size, environmental conditions and pour schedule, the waste form temperature, due to exothermic hydration reactions, can gradually increase by 30 deg. C to 50 deg. C above the starting temperature. Previous studies at Savannah River National Laboratory (SRNL) have shown that curing temperature has a negative impact on the hydraulic conductivity and other performance properties of Saltstone; specifically, these studies have shown that curing at elevated temperatures results in faster hydraulic conductivities than what is modeled in the Saltstone Performance Assessment (PA). SRNL is currently testing the performance of laboratory prepared Saltstone cured under controlled conditions (i.e. controlling relative humidity). The PA assumes that the Saltstone remains saturated; therefore, some samples are being kept completely saturated while others have a surface exposed to a high humidity environment. The formulation of these samples has been varied to continue studying the impact of processing parameters on the performance properties of Saltstone. The final water to premix (w/p) ratio of the Saltstone formulation does affect the density, porosity, and compressive strength of the cured Saltstone. The Saltstone formulations with 0.59 w/p ratios and lower had higher densities, lower porosities, and higher compressive strength than samples formulated at a higher w/p ratio. There is a general trend that the samples formulated at high w/p ratios (0.67 and higher) have the lowest density, highest porosity and lowest strength. However, for hydraulic conductivity, the curing environment had a greater effect on the results than the formulation. Therefore, the impact of elevated temperature is not as detrimental to the performance of the waste form as originally concluded, provided the curing environment is controlled and the waste form is not dried out. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2013

Management of salt waste from electrochemical processing of used nuclear fuel

Electrochemical processing of used nuclear fuel involves operation of one or more cells containing molten salt electrolyte. Processing of the fuel results in contamination of the salt via accumulation of fission products and transuranic (TRU) actinides. Upon reaching contamination limits, the salt must be removed and either disposed or treated to remove the contaminants and recycled back to the process. During development of the Experimental Breeder Reactor-II spent fuel treatment process, waste salt from the electro-refiner was to be stabilized in a ceramic waste form and disposed of in a high-level waste repository. With the cancellation of the Yucca Mountain high-level waste repository, other options are now being considered. One approach that involves direct disposal of the salt in a geologic salt formation has been evaluated. While waste forms such as the ceramic provide near-term resistance to corrosion, they may not be necessary to ensure adequate performance of the repository. To improve the feasibility of direct disposal, recycling a substantial fraction of the useful salt back to the process equipment could minimize the volume of the waste. Experiments have been run in which a cold finger is used for this purpose to crystallize LiCl from LiCl/CsCl. If it is found to be unsuitable for transportation, the salt waste could also be immobilized in zeolite without conversion to the ceramic waste form. (authors)

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2018

Experimental and modeling study of calcium carbonate precipitation and its effects on the degradation of oil well cement during carbonated brine exposure

Decalcification of cement in solutions of carbonated brine is important to a host of engineering applications, especially in subsurface service environments where cementitious materials are frequently utilized as engineered barriers for wellbore seals, as well as shaft and drift seals and waste forms for nuclear waste disposal. Analysis of leaching simulations and experiments shows that, depending on solution compositions (dissolved CO{sub 2} concentration, pH, Ca ion concentration), calcite precipitation occurring during leaching of cement in contact with carbonated brine can have a significant impact on cement reactivity, in some instances leading to complete arrest of reactivity via calcium carbonate ''pore-clogging''. We present modeling and experimental results that examine the range of solution conditions that can lead to pore-clogging. Analysis of the results shows that distinct regimes of leaching behavior, based on pH and pCO2, can be used to form a framework to better understand the occurrence of pore-clogging.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2014

Continuing the Validation of CCIM Processability for Glass Ceramic HLLW Forms: Plan for Test AFY14CCIM-GC1

This test plan covers test AFY14CCIM-GC1which is the first of two scheduled FY-2014 test runs involving glass ceramic waste forms in the Idaho National Laboratory’s Cold Crucible Induction Melter Pilot Plant. The test plan is based on the successes and challenges of previous tests performed in FY-2012 and FY-2013. The purpose of this test is to continue to collect data for validating the glass ceramic High Level Liquid Waste form processability advantages using Cold Crucible Induction Melter technology. The major objective of AFYCCIM-GC1 is to complete additional proposed crucible pouring and post tapping controlled cooling experiments not completed during previous tests due to crucible drain failure. This is necessary to qualify that no heat treatments in standard waste disposal canisters are necessary for the operational scale production of glass ceramic waste forms. Other objectives include the production and post-test analysis of surrogate waste forms made from separate pours into the same graphite mold canister, testing the robustness of an upgraded crucible bottom drain and drain heater assembly, testing the effectiveness of inductive melt initiation using a resistive starter ring with a square wave configuration, and observing the tapped molten flow behavior in pans with areas identical to standard High Level Waste disposal canisters. Testing conditions, the surrogate waste composition, key testing steps, testing parameters, and sampling and analysis requirements are defined.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗