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At least 181 records · Page 10
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

The corrosion behavior of borosilicate glass in the presence of cementitious waste forms

Borosilicate glasses are widely used for radioactive waste disposal due to their ability to incorporate a variety of contaminants and radionuclides while exhibiting high durability in various disposal scenarios. This research evaluated the dissolution of borosilicate glass using both single-pass-flow-through (ASTM C1662-18) and product consistency test (ASTM C1285-21) methods with different solutions, including a cementitious-contacted water (called grout-contacted, GC, from this point) and solutions with varying levels of dissolved cementitious species such as Si, Ca, Al. Here, the results indicated that the presence of Ca plays a crucial role in suppressing glass corrosion, as evidenced by the slower normalized dissolution rates, which were one order of magnitude lower for boron and two orders of magnitude lower for rhenium, observed in both Ca-amended and GC solutions compared to the pH 12 buffer solution. This effect is attributed to the formation of a dense, low-porosity, and strongly bonded calcium silicate hydrate (CSH) layer on the glass surface, which implies that a glass corrosion process is influenced by ion exchange involving alkali ions Na + , K + , Ca 2+ , and hydrogen-containing species. A small number of glass particles treated in the GC solution showed minor corrosion pits in the form of shallow craters with an average diameter of approximately 500 μm. This observation is correlated with a significant reduction, 2000 to 3000 times lower, in the cumulative volume of glass pores, indicating that smaller pore voids were “sealed” in the presence of Ca 2+ ions, likely attributed to the formation of CSH precipitation or other corrosion products such as calcium carbonate saturated from the grout solution. These findings suggest that the presence of dissolved Ca in the GC solution can slow down the dissolution of borosilicate glass, contrary to the expected trend of higher dissolution rates resulting from exposure to high alkaline and thus higher pH solutions.

36 MATERIALS SCIENCE↗
DOE OSTI2012

Evaluation of Fabric Membranes for Use in Saltstone Drain Water System

Saltstone Disposal Unit 2 contains a sheet drain fabric intended to separate solids from drain water to be returned to the Salt Feed Tank. A similar system installed in Vault 4 appears to be ineffective in keeping solids out of the drain water return lines. Waste Solidification Engineering is considering installation of an additional fabric membrane to supplement the existing sheet drain in SDU 2. Amerdrain 200 is the product currently installed in SDU 2. This product is no longer available, so Sitedrain 94 was used as the replacement product in this testing. Fabrics with apparent opening sizes of 10, 25, 50 and 100 microns were evaluated. These fabrics were evaluated under three separate test conditions, a water flow test, a solids retention test and a grout pour test. A flow test with water showed that installation of an additional filter layer will predictably reduce the theoretical flux through the sheet drain. The manufacturer reports the flux for Sitedrain 94 as 150 gpm/ft 2 by ASTM D-4491. This compares reasonably well with the 117 gpm/ft 2 obtained in this testing. A combination of the 10 micron fabric with Sitedrain 94 could be expected to decrease flux by about 10 times as compared to Sitedrain 94 alone. The different media were used to filter a slag and fly ash mixture from water. Slag historically has the smallest nominal particle size of the premix components. Cement was omitted from the test because of its reactivity with water would prohibit accurately particle size measurements of the filtered samples. All four media sizes were able to remove greater than 95% of particles larger than 100 microns from the slurry. The smaller opening sizes were increasingly effective in removing more particles. The 10 micron filter captured 15% of the total amount of solids used in the test. This result implies that some insoluble particles may still be able to enter the drain water collection system, although the overall solids rejection is significantly improved over the current design. Test boxes were filled with grout to evaluate the performance of the sheet drain and fabrics in a simulated vault environment. All of the tests produced a similar amount of drain water, between 8-11% of the amount of water in the mix, which is expected with the targeted formulation. All of the collected drain waters contained some amount of solids, although the 10 micron filter did not appear to allow any premix materials to pass through. The solids collected from this box are believed to consist of calcium carbonate based on one ICP-AES measurement. Any of the four candidate fabrics would be an improvement over the sheet drain alone relative to solids removal. The 10 micron fabric is the only candidate that stopped all premix material from passing. The 10 micron fabric will also cause the largest decrease in flux. This decrease in flux was not enough to inhibit the total amount of drain water removed, but may lead to increased time to remove standing water prior to subsequent pours in the facility. The acceptability of reduced liquid flux through the 10 micron fabric will depend on the amount of excess water to be removed, the time available for water removal and the total area of fabric installed at the disposal cell.

42 ENGINEERING↗
DOE OSTI2012

Analysis of the Salt Feed Tank Core Sample

The Saltstone Production Facility (SPF) immobilizes and disposes of low-level radioactive and hazardous liquid waste (salt solution) remaining from the processing of radioactive material at the Savannah River Site (SRS). Low-level waste (LLW) streams from processes at SRS are stored in Tank 50 until the LLW can be transferred to the SPF for treatment and disposal. The Salt Feed Tank (SFT) at the Saltstone Production Facility (SPF) holds approximately 6500 gallons of low level waste from Tank 50 as well as drain water returned from the Saltstone Disposal Facility (SDF) vaults. Over the past several years, Saltstone Engineering has noted the accumulation of solids in the SFT. The solids are causing issues with pump performance, agitator performance, density/level monitoring, as well as taking up volume in the tank. The tank has been sounded at the same location multiple times to determine the level of the solids. The readings have been 12, 25 and 15 inches. The SFT is 8.5 feet high and 12 feet in diameter, therefore the solids account for approximately 10 % of the tank volume. Saltstone Engineering has unsuccessfully attempted to obtain scrape samples of the solids for analysis. As a result, Savannah River National Laboratory (SRNL) was tasked with developing a soft core sampler to obtain a sample of the solids and to analyze the core sample to aid in determining a path forward for removing the solids from the SFT. The source of the material in the SFT is the drain water return system where excess liquid from the Saltstone disposal vaults is pumped back to the SFT for reprocessing. It has been shown that fresh grout from the vault enter the drain water system piping. Once these grout solids return to the SFT, they settle in the tank, set up, and can't be reprocessed, causing buildup in the tank over time. The composition of the material indicates that it is potentially toxic for chromium and mercury and the primary radionuclide is cesium-137. Qualitative measurements show that the material is not cohesive and will break apart with some force.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2015

Determining the Release of Radionuclides from Tank Waste Residual Solids: FY2015 Report

Methodology development for pore water leaching studies has been continued to support Savannah River Site High Level Waste tank closure efforts. For FY2015, the primary goal of this testing was the achievement of target pH and Eh values for pore water solutions representative of local groundwater in the presence of grout or grout-representative (CaCO 3 or FeS) solids as well as waste surrogate solids representative of residual solids expected to be present in a closed tank. For oxidizing conditions representative of a closed tank after aging, a focus was placed on using solid phases believed to be controlling pH and E h at equilibrium conditions. For three pore water conditions (shown below), the target pH values were achieved to within 0.5 pH units. Tank 18 residual surrogate solids leaching studies were conducted over an E h range of approximately 630 mV. Significantly higher Eh values were achieved for the oxidizing conditions (ORII and ORIII) than were previously observed. For the ORII condition, the target Eh value was nearly achieved (within 50 mV). However, E h values observed for the ORIII condition were approximately 160 mV less positive than the target. E h values observed for the RRII condition were approximately 370 mV less negative than the target. Achievement of more positive and more negative E h values is believed to require the addition of non-representative oxidants and reductants, respectively. Plutonium and uranium concentrations measured during Tank 18 residual surrogate solids leaching studies under these conditions (shown below) followed the general trends predicted for plutonium and uranium oxide phases, assuming equilibrium with dissolved oxygen. The highest plutonium and uranium concentrations were observed for the ORIII condition and the lowest concentrations were observed for the RRII condition. Based on these results, it is recommended that these test methodologies be used to conduct leaching studies with actual Tank 18 residual solids material. Actual waste testing will include leaching evaluations of technetium and neptunium, as well as plutonium and uranium.

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

Determining the Release of Radionuclides from SRS Tank 12H Waste Residual Solids Following Tank Closure

Eight High Level Waste (HLW) tanks used to store radioactive waste slurries have been emptied and closed at the Savannah River Site (SRS). Performance Analyses (PA) modeling of the release of radionuclides from residual waste solids in these tanks into the environment over extended time periods indicated the most likely risk drivers for environmental contamination. Radionuclide leaching studies were desired to provide additional information regarding the residual waste solubility assumptions used in the models. This report serves to provide equilibrium solubility data for several radionuclides identified as risk drivers and adds to the database of solubility values reported in the previous analogous study with Tank 18F solids. Pore water leaching studies were conducted on actual SRS Tank 12H residual waste solids to support Liquid Waste tank closure efforts and closed tank Performance Analyses. Tank 12H was exposed to extensive mechanical cleaning, caustic aluminum dissolution, and oxalic acid chemical cleaning prior to closure. The methodology utilized for leach testing was developed during previous testing. Slurries of tank residual solids and grout-representative solids in simulated grout pore water solutions (based on SRS groundwater compositions) with pH and E h values expected during the aging of the closed waste tank were produced. The soluble concentrations of selected radionuclides were analyzed versus time to confirm equilibrium conditions were achieved. These are the first leach studies conducted on waste tank residuals exposed to these cleaning conditions.

Eh↗
DOE OSTI2021

Time Dependence of Methane Generation Rates from Saltstone

This report documents the tests performed to address the requirements listed in the Technical Request, which resulted in a Task Technical & Quality Assurance Plan (TTQAP) and a Run Plan to obtain the required information. The research expands previous scoping work to better understand methane generation in the Saltstone Disposal Facility (SDF). That scoping work demonstrated that methane is produced when sulfide-containing material is added to methylmercury (MeHg), which is found in the SDF Tank 50 feed waste. When Tank 50 waste is combined with grout premix solids dry feed ingredients of cement, slag cement, and fly ash, sulfides are released from the slag cement component of the premix. The prior testing results showed that while the concentration of total mercury was not affected in the pH 14 waste, the MeHg likely reacted with the sulfide contained in the slag. The scoping tests were performed in sealed reactors and thus, methane generation was not measured continuously; rather, it was measured after one hour and after 24 hours. After 24 hours, a large percentage of the MeHg was converted to methane, but after 1 hour only a small percentage of methane was released. It is noteworthy that the methane generation rate (MGR) was greater at the one-hour measurement. The data compiled from the scoping work needed to be expanded to better understand the generation of methane released from grout mixed with Tank 50 waste. This expanded study developed a more extensive knowledge of how and when methane is generated to inform the Documented Safety Analysis (DSA) of the SDF. As such, employing 8 sealed reactors, the methane generation time periods were extended to 2, 4, 6, 18, 30, 48, 72, and 96 hours (4 days). Results are documented herein to determine the capacity for MeHg, contained within Tank 50 salt solution (T50SS) simulant, to produce methane when mixed with saltstone dry feed ingredients, i.e., individual components (cement, slag, and fly ash) or a combination of those components.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2012

NEW MATERIALS DEVELOPED TO MEET REGULATORY AND TECHNICAL REQUIREMENTS ASSOCIATED WITH IN-SITU DECOMMISSIONING OF NUCLEAR REACTORS AND ASSOCIATED FACILITIES

For the 2010 ANS Embedded Topical Meeting on Decommissioning, Decontamination and Reutilization and Technology, Savannah River National Laboratory's Mike Serrato reported initial information on the newly developed specialty grout materials necessary to satisfy all requirements associated with in-situ decommissioning of P-Reactor and R-Reactor at the U.S. Department of Energy's Savannah River Site. Since that report, both projects have been successfully completed and extensive test data on both fresh properties and cured properties has been gathered and analyzed for a total of almost 191,150 m{sup 3} (250,000 yd{sup 3}) of new materials placed. The focus of this paper is to describe the (1) special grout mix for filling the P-Reactor vessel (RV) and (2) the new flowable structural fill materials used to fill the below grade portions of the facilities. With a wealth of data now in hand, this paper also captures the test results and reports on the performance of these new materials. Both reactors were constructed and entered service in the early 1950s, producing weapons grade materials for the nation's defense nuclear program. R-Reactor was shut down in 1964 and the P-Reactor in 1991. In-situ decommissioning (ISD) was selected for both facilities and performed as Comprehensive Environmental Response, Compensations and Liability Act actions (an early action for P-Reactor and a removal action for R-Reactor), beginning in October 2009. The U.S. Department of Energy concept for ISD is to physically stabilize and isolate intact, structurally robust facilities that are no longer needed for their original purpose of producing (reactor facilities), processing (isotope separation facilities), or storing radioactive materials. Funding for accelerated decommissioning was provided under the American Recovery and Reinvestment Act. Decommissioning of both facilities was completed in September 2011. ISD objectives for these CERCLA actions included: (1) Prevent industrial worker exposure to radioactive or hazardous contamination exceeding Principal Threat Source Material levels; (2) Minimize human and ecological exposure to unacceptable risk associated with radiological and hazardous constituents that are or may be present; (3) Prevent to the extent practicable the migration of radioactive or hazardous contaminants from the closed facility to the groundwater so that concentrations in groundwater do not exceed regulatory standards; (4) Eliminate or control all routes of human exposure to radiological and chemical contamination; and (5) Prevent animal intruder exposure to radioactive and hazardous contamination.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2015

Evaluation of D and D alternatives for a DOE nuclear material processing facility - 15265

Ten scenarios for SRS Building 235-F were evaluated relative to groundwater protection through use of a 235-F GoldSim{sup TM} fate and transport model. The scenarios included two extreme scenarios, a no action scenario, four D and D grouting scenarios, and three D and D inventory removal scenarios. The fate and transport model simulated contaminant release from four 235-F process areas and the 294-2F Sand Filter and fate and transport through the vadose zone, the Upper Three Runs (UTR) aquifer, and the UTR creek. The model was a stochastic model for which 1,000 realizations were run over 100,000 years for each scenario. In association with the seven D and D alternatives only three groundwater standards out of 25 were exceeded, with the combined radium standard showing the greatest exceedance. The standards were only exceeded at the edge of the building after 10,000 years. It was estimated that there was a 90% likelihood that the combined radium standard would be exceeded for all four D and D grouting scenarios and that a 95% inventory removal from process cells 1-5 would result in an essentially zero percent likelihood that any standards would be exceeded. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2015

Characterization of unsaturated hydraulic conductivity in fractured media using the multistep outflow method - 15461

The multistep outflow method is routinely used to characterize the unsaturated hydraulic conductivity of soils. The technique involves placing a soil sample in a pressure plate apparatus, subjecting the sample to multiple gas pressures in discrete steps through time, and measuring the transient volume of pore fluid extracted. Unsaturated hydraulic property values are estimated through inverse modeling of the experimental conditions. In this study the multistep outflow concept was applied to micro-cracked cementitious materials to assess the efficacy of the technique for these materials. The cementitious materials tested were salt-waste simulant grout samples artificially damaged through oven-drying. Compared to typical soils, fractured media exhibit higher saturated conductivity and lower air-entry pressure, and the volume of fluid extractable from fractures is much lower than soil porosity. To accommodate these material differences the standard test apparatus was modified to incorporate a higher conductivity ceramic pressure plate, a high-precision digital balance for logging outflow mass, a low volume (diameter) effluent line, multiple in-line high-precision gas regulators, and a high-precision low-range pressure gauge. Testing to date indicates that the modified apparatus can provide a viable means to measure the unsaturated hydraulic properties of micro-fractured cementitious materials. However the accuracy/uniqueness of inverse modeling is limited by the inherent characteristics of fractured media: high saturated conductivity, low air-entry pressure, and strong non-linearities. Hydraulic property results in the form of van Genuchten / Mualem curves are presented for three fractured grout specimens. DOE Performance Assessments often involve cementitious barriers and/or waste forms that are predicted or assumed to degrade over time due to various mechanisms such as carbonation-influenced reinforcing steel corrosion, external sulfate attack, differential settlement, and seismic activity. Physical degradation typically takes the form of small-scale cracking / fracturing, and the affected materials reside in unsaturated hydrogeologic zones. In these cases, unsaturated hydraulic properties are needed for fractured cementitious materials to simulate moisture movement and contaminant transport within and around the facility. The outflow extraction method, as implemented in the present study, provides a suitable method for estimating these material properties. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2015

Leaning the tank closure process at the Savannah River Site - 15515

The Savannah River Site liquid waste system consists of multiple facilities that safely receive and store legacy radioactive waste prior to treatment and disposition. The liquid radioactive waste is stored in large underground tanks. The waste inventory currently stored in these tanks is a complex mixture of insoluble metal hydroxide solids and soluble salt supernate. The high-level (radioactive) portion of the waste is vitrified into a glass waste form, while the low-level waste is immobilized into a cementitious grout waste form called salt-stone. Once the waste is retrieved and processed, the tanks are closed. The closure process includes; waste removal, characterizing residuals, isolating the tank systems, and stabilizing the tank with tailored grout formulations. The core of Lean is to eliminate waste or non-value added steps from processes to maximize customer value. From the perspective of the customer, 'value' is defined as any action or process for which a customer would willingly pay. In this case our product is to safely and efficiently remove waste from the underground storage tanks and demonstrate operational closure to the State of South Carolina. Savannah River Remediation (SRR) initiated the use of the Lean process in late 2013 and identified the Tank Closure process as one of the targeted areas to improve. The first step in the Lean process is to 'map' out the value stream and identify areas where non-value added steps are present and then prioritize Rapid Improvement Events (RIE). Based on this mapping process, there were a number of areas that SRR determined warranted further evaluation for improvements, including; standard equipment design, characterization, standard work packages, regulatory documentation, tank characterization, structural evaluations, engineering documentation and equipment re-use. This paper focuses on the application of the Lean process at SRR and more specifically, effective application to the Tank Closure Process. This paper discusses the value stream mapping process for Tank Closures, as well as, summarizes the RIEs and demonstrate the realized benefits. Benefits can come in a variety of forms, from schedule compression to decreased costs. Through the Lean process we have been able to identify close to $10 M in savings over the life cycle of the tank closure process and a 4 year schedule compression. Cost and schedule savings are used to accomplish further risk reduction efforts. In addition to hard benefits, there are also soft benefits. These soft benefits are a result of the process itself and help drive improved efficiencies through better communication with key stakeholders, such as regulators and customers. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2015

Salt Waste Processing Facility project lessons learned: Acquisition through construction - 15518

The Salt Waste Processing Facility (SWPF), located at the Savannah River Site (SRS) in Aiken, South Carolina, is a multi-billion dollar Liquid Radioactive Waste (LRW) processing facility that represents the keystone for the U.S. Department of Energy (DOE)-EM clean-up mission at SRS. The SWPF facilitates DOE-EM clean-up at SRS by decontaminating the salt waste, which is the dominant volumetric component in the LRW tanks, thereby allowing the cleaned salt waste to be removed from the tanks and stabilized into an approved grout-based final waste form. The small volume of removed radionuclides is sent to the Defense Waste Processing Facility (DWPF) for vitrification. Emptied LRW storage tanks are then grouted into an approved configuration for final closure. The SWPF project is currently 100% complete with design, 80% complete with construction, and 10% complete with commissioning. To date there have been numerous lessons learned with regard to project acquisition, design, procurement, construction, and quality assurance (QA) approaches (both good practices and mistakes) that are considered to be of significant value in improving the state of major project execution within the DOE-EM clean-up program as well as to the wider DOE enterprise. An overview of the current SWPF project status is provided and key lessons learned in the aforementioned areas are presented relative to improving future DOE major project execution performance. Specific areas to be addressed include strategies to optimize integration of design and nuclear safety, constructability tools for design and construction synchronization, commercial grade dedication (CGD) approaches to mitigate atrophy in the nuclear supply chain, and QA perspectives to facilitate effective and efficient project execution. (authors)

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

Adaptation of Commercially Available Robots for Conditioning and Packaging ILW at Sellafield - 18282

The Legacy Ponds and Silos at Sellafield site contain some of the most hazardous Intermediate Level Waste (ILW) in the UK. As part of a multi-billion pound decommissioning programme, this waste will be retrieved and transported across the site for conditioning and packaging in the Box Encapsulation Plant (BEP). Current plans are to commence plant active commissioning in 2022, which will represent a major milestone in the UK nuclear decommissioning programme. Within the plant, skips of waste will be transferred from the shielded transport package into standard 3 cubic metre ILW containers. Waste from the Pile Fuel Storage Pond and First Generation Magnox Storage Pond will be immobilised in cementitious grout before being transferred to an adjacent store. Waste from the Magnox Swarf Storage Silo will not be immobilised in grout, but will be packaged, providing multi-barrier containment. During the concept design, the project team selected commercially available robots as the most viable technology for carrying out the numerous dexterous and repetitive tasks involved in characterising, conditioning and packaging the waste within the shielded 'hot' cells. Significant technical challenges had to be overcome during the design to adapt a commercially available robot for use within a high radiation / high contamination environment, where human access is not safe even for short periods of time. These challenges included: - Designing robot assemblies that could be retrofitted into the existing cell structure that was constructed as part of an earlier project but never completed; - Designing robot assemblies that could be recovered to their 'transport' position without requiring manual intervention; - Designing robot assemblies that could be remotely removed and replaced with new ones if they failed part way through the plant operational life; - Designing through-wall service and power connections that allow maintenance and recovery; - Designing control systems and human-machine interfaces that enable both manual and automated operation of the robot, whilst avoiding collisions with the in-cell cranes and other in cell furniture; - Assessing the radiation tolerance of all items. Bespoke computer simulations and full-scale development trials have been carried out, using non-active test materials, in order to demonstrate the Technology Readiness Level (TRL) required by Sellafield Limited (SL) at each stage of the project [1]. The results of these trials have been recorded in both video and written form so that they can form part of the project's Knowledge Management database. Detailed designs and specifications for the robot assemblies have been updated to incorporate the recommendations from the development trials. Procurement and manufacture of robot assemblies has already commenced to deliver two waste handling robots, two waste container lidding / swabbing robots and associated critical spares. (authors)

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

Evaluating the Chemical Resistance of Salt-stone Disposal Unit (SDU) Concrete and Polymeric Coatings - 18494

Salt-stone Disposal Units (SDUs) are multi-million liter concrete structures that are used at the Savannah River Site (SRS) for the permanent disposal of low-activity salt solution incorporated in a cementitious grout matrix, termed salt-stone. The major chemical constituents of the salt solution include sodium, aluminum, nitrate, nitrite, hydroxide, carbonate, and sulfate. The potential exists for the SDU interior to be chronically exposed to these corrosive constituents resulting in deleterious reactions and physical damage. Sulfate attack is an example of such an interaction whereby aqueous sulfates may penetrate the concrete, and react with hydration products in the cured concrete to form expansive phases that can cause excessive strains and cracking. Recently constructed SDUs have utilized sulfate-resistant Type V cement and polymeric coatings to minimize the potential impacts of SDU concrete exposure to the highly caustic (pH > 13) salt solution. Not only must the concrete and coatings exhibit high resistance to the caustic salt solution but they are also subjected to above ambient temperatures due to the exothermic nature of the grout hydration reaction. As such, both the SDU concrete and the coatings need to be tested with respect to stability in the aforementioned chemical and thermal environments. Two primary investigations were considered in this work. The first was to evaluate the resistance of two previously used epoxy coatings (Hempel Versiline TL-45 S Novolac and EC-66 elastomeric epoxies) to chemical attack from a simulated salt solution. In addition, a third coating was included in the study, a poly-urea coating (Sherwin Williams Envirolastic AR425) that may be considered as an alternative to the epoxy coatings on future SDUs. Each coating was applied to concrete cylinders (actual SDU 6 test cores) and subsequently exposed to salt-stone, or full and half strength caustic salt solution; 50% dilution was considered since salt-stone processing involves addition of flush water to the SDUs, which is expected to dilute any residual salt solution or bleed water in the SDU. Exposure testing was conducted at 68 deg. C for 1,000 hours followed by ambient exposure to provide a full exposure time of approximately 90 days. It is important to note that evaluation criteria for the coated materials were only visual in nature. Other than coating discoloration, which was limited to the surfaces, no other visual indications of reactivity between the three coatings and any of the exposure mediums were observed. Cross-sectioned samples indicated no through-thickness coating penetration or reaction, and showed no signs of delamination. The second investigation was also performed to determine if SDU concrete without a polymeric barrier would resist ingress and reaction with salt solution at the elevated temperature. Again, only slight discoloration of the concrete surfaces was observed after the 90-day exposure test irrespective of the salt solution concentration. A requirement of structural concrete in the SDUs is that it possesses a minimum compressive strength of 42 MPa (6,000 psi). The average compressive strength of samples exposed to the full-strength salt solution was recorded at 68 MPa compared to 66 MPa for the unexposed samples thus indicating that the exposure conditions considered in this study were not detrimental to the concrete strength. (authors)

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

Dismantling of the Spent Resins Hot Compaction Unit at Tihange NPP, Belgium - 19139

Design, construction and commissioning of the Spent Ion Exchange Resins Hot Compaction Unit at Tihange Nuclear Power Plant took place from 2005 till 2011. In this conditioning process, batches of radioactive resin beads were first dried to less than 4% moisture by a conical vacuum dryer. Resins were then poured in compactable 200-liter drums and super-compacted. Resulting pellets were emplaced in standard 400-liter drums, the packages qualified for final disposal in Belgium, and eventually grouted. The Belgian Waste Management Agency (ONDRAF/NIRAS) was consulted before initiating the project and issued a statement of no objection. The technology turned out to be used for the first time in the particular case of bead shaped resins (unlike powdered resins) and with a grouting requirement. Finally, commissioning tests ended in a safe and reproducible waste form, compliant with prevailing Waste Acceptance Criteria. Volume Reduction Factors of about 2 were recorded after drying and compaction. New tests were carried out to support the Qualification File of the process, which was submitted to ONDRAF/NIRAS. After performing many trials using inactive resins, the Operator dried two batches of radioactive resins and super-compacted four drums: this was a planned qualification step, aiming at the validation of process parameters. In the meantime, ONDRAF/NIRAS made parallel progress in the design of the future Near Surface Repository, where conditioned resins will be disposed of, and found some incompatibility between encapsulated dried resin beads and water intrusion hazards inside the repository. Based on the risk that dried resin beads will swell if they absorb water, causing mechanical stresses likely to compromise the integrity of the disposal site, ONDRAF/NIRAS informed Tihange NPP that the Hot Compaction Unit would not be qualified as spent resins conditioning process. Further to this irrevocable decision, the Operator undertook three actions: - The first one was the qualification and purchase of waste containers to provide additional temporary storage capacity on site for its operational spent resins; - The second one is the selection of a new spent resins conditioning process and the performance of the related qualification tests to demonstrate it meets the updated Waste Acceptance Criteria; - The last one is the dismantling of the Hot Compaction Unit to clear the space and enable the installation of new equipment. This latter task was carried out in 2018, involving decontamination and free release measurements of all the materials, a very limited fraction of it having to be further processed as radioactive waste. Nevertheless, Tihange NPP wishes to keep the super-compactor and its hydraulic unit for a possible resale or reuse for the treatment of mixed waste. (authors)

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

Measurements of Hydrogen Generation Rates using a Sealed Reactor System - 19428

Sealed reactor tests were performed to measure the hydrogen generation rate (HGR) from stored radioactive waste at the Savannah River Site. HGR may be very low, on the order of 7.5 x 10{sup -13} (m{sup 3}/h)/L [that is, cubic meters of H{sub 2} generated per hour per liter of radioactive liquid waste, or 10{sup -10} (ft{sup 3}/h)/gal]. Because the estimated HGR limit of detection for an open, continuous flow, system is approximately 7.5 x 10{sup -10} (m{sup 3}/h)/L [or 10{sup -7} (ft{sup 3}/h)/gal], a more sensitive method was needed. By accumulating generated gasses in a sealed system without a continuous purge gas, the resulting concentrations can increase the sensitivity of measurement, which is based on time of heating. In 2017, Savannah River Remediation declared a Potential Inadequacy in the Safety Analysis related to the potential thermal decomposition of organics that generate hydrogen in each of three Liquid Waste facilities: Concentration, Storage and Transfer Facility, Saltstone Production Facility, and the Defense Waste Processing Facility. The research for this study concerns low activity waste of Tank 50, which feeds the Saltstone Production Facility. This study evaluated the impact of organics including formate on the generation of H{sub 2}. Samples of SRS Tank 50 waste, which is a nominal 5 molar sodium salt solution, were sealed in stainless steel reactors and held at varying temperatures, e.g., 50 deg. C, 75 deg. C, 100 deg. C, and 120 deg. C, to determine if organic compounds are decomposing into H2. The experiments included trace solids used to stabilize waste in grout, e.g., grout-premix and Blast Furnace Slag, to determine if any solid phase reactions are present, which would accelerate or inhibit the generation of H{sub 2} at these temperatures. This paper describes the sealed reactors designed and constructed at Savannah River National Laboratory and the radioactive tests that were performed to measure HGR in both oxic and anoxic atmospheres. The shakedown tests showed the sealed reactors to be leak tight and hydrogen concentrations from calibrated standards could be accurately measured. Previous simulant tests helped to perfect the test methods and better design the radioactive tests. The radioactive results showed that the rate of hydrogen generated from Tank 50 waste, over a range of temperatures from 30 deg. C up to 120 deg. C, is bounded by an empirical relation (Hu Equation) that can be used to approximate HGRs in Tank 50 radioactive waste. (authors)

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

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↗
DOE OSTI2020

Life cycle Management of 324 Project High-Activity, Mixed/Low-Level Radioactive Waste - 20506

U.S. DOE contractor CH2M Hill Plateau Remediation Company (CHPRC) manages the 324 Building and is preparing to remotely excavate and disposition the radioactive soil beneath the building to allow further deactivation of the building. The 324 Building is a non-reactor Category 2 Nuclear Facility located in the 300 Area of the Hanford Site. Records indicate that in October 1986, approximately 516 liters of a concentrated liquid waste stream containing cesium-137 ({sup 137}Cs) and strontium-90 ({sup 90}Sr) spilled onto the floor of a hot cell, B-Cell, in the 324 Building. The spill contained an estimated 1.3 million curies (Ci) of radioactivity. A breach in the sump of B-Cell was discovered in November 2009 during characterization of the soil under the building. Exposure rates in excess of 10,000 R/hr were detected through a system of access pipes installed under the hot cell, and an estimated 1.557 E+05 Ci of {sup 137}Cs and 6.842 E+04 Ci of {sup 90}Sr are in the soil beneath B-Cell. The magnitude of the soil contamination below B-Cell represents one of the most challenging remediation activities in the DOE complex. The objective of CHPRC's 324 Project is to remotely excavate and disposition the highly contaminated soil under the hot cell so building deactivation and stabilization activities can resume. Depending on the volume and radioactivity of contaminated soil under B-Cell, the material will be dispositioned either at the Hanford Site's Environmental Restoration Disposal Facility (ERDF) or in grout monoliths that will be created in the hot cells (A, C and D) next to B-Cell during future building demolition activities. The current project scope includes installing structural supports under the walls of B-Cell and using remotely operated equipment to remove debris from the hot cell, remove debris mixed with grout on the floor, saw through and remove the cell floor and liner, and excavate contaminated soil under B-Cell to a depth of up to 3.66 meters (12 feet). Addition or removal of debris in A-Cell may be required to support B-Cell cleanout and excavation activities. The base approach is to disposition debris and soil bins in the Radiochemical Engineering Cell (REC) monoliths, and subsequently disposition the monoliths during building demolition. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2021

Early age hydration and application of blended magnesium potassium phosphate cements for reduced corrosion of reactive metals

Highlights: • Magnesium potassium phosphate cements were studied for nuclear waste encapsulation. • The optimised formulation in this study was determined to be 0.24 w/s ratio. • Different reaction kinetics were discovered for the FA/MKPC and BFS/MKPC binders. • Struvite-K was the only crystalline reaction product observed via in-situ SXPD. • Uranium trials revealed MKPC corrosion was reduced compared to a UK nuclear grout. Magnesium potassium phosphate cements (MKPC) were investigated to determine their efficacy towards retardation of reactive uranium metal corrosion. Optimised low-water content, fly ash (FA) and blast furnace slag (BFS) blended MKPC formulations were developed and their fluidity, hydration behaviour, strength and phase assemblage investigated. In-situ time resolved synchrotron powder X-ray diffraction was used to detail the early age (~60 h) phase assemblage development and hydration kinetics, where the inclusion of BFS was observed to delay the formation of struvite-K by ~14 h compared to FA addition (~2 h). All samples set within this period, suggesting the possible formation of a poorly crystalline binding phase prior to struvite-K crystallisation. Long-term corrosion trials using metallic uranium indicated that MKPC systems are capable of limiting uranium corrosion rates (reduced by half), when compared to a UK nuclear industry grout, which highlights their potential application radioactive waste immobilisation.

36 MATERIALS SCIENCE↗