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Cs absorption capacity and selectivity of crystalline and amorphous Hf and Zr phosphates

Removal of radioactive Cs from sodium-rich solutions is a technical challenge that goes back to post World War II nuclear waste storage and treatment; and interest in this topic was reinvigorated by the Fukushima-Daiichi nuclear power plant disaster, 10 years ago. Since the 1960's there has been considerable focus on layered Zr phosphates as robust inorganic sorbents for separation of radionuclides such as Cs. Here we present synthesis and characterization, and direct comparison of Cs sorption capacity and selectivity of four related materials: 1) crystalline α-Zr phosphate and α-Hf phosphate, and 2) amorphous analogues of these. Powder X-ray diffraction, thermogravimetry, solid-state 31P magic angle spinning nuclear magnetic resonance (MAS-NMR) spectroscopy, and compositional analysis (inductively coupled plasma optical emission spectroscopy and mass spectroscopy, ICP OES and ICP MS) provided formulae; respectively M(HPO4)2∙1H2O and M(HPO4)2∙4H2O (M = Hf, Zr) for crystalline and amorphous analogues. Maximum Cs loading, competitive Cs-Na selectivity and maximum Cs-Na loading followed by the above characterizations plus 133Cs MAS-NMR spectroscopy revealed that amorphous analogues are considerably better Cs-sorbents (based on maximum Cs-loading and selectivity over Na) than the well-studied crystalline Zr-analogue. Additionally, crystalline α-Hf phosphate is better Cs-sorbent than crystalline α-Zr phosphate. All these studies consistently show that Hf phosphate is less crystallize than Zr phosphate, when obtained under similar or identical synthesis conditions. We attribute this to lower solubility of Hf phosphate compared to Zr phosphate, preventing ‘defect healing’ during the synthesis process.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Preliminary Enhanced LAW Glass Formulation Algorithm

This report summarizes the Preliminary Enhanced LAW Glass Formulation Algorithm, its background information, and the calculations it performs. The Preliminary Enhanced LAW Glass Formulation Algorithm is a tool that has been developed in MATLAB to formulate glass at a given a waste composition, while attempting to maximize waste loading. It is intended for use at the Hanford Waste Treatment and Immobilization Plant, where nuclear waste will be vitrified into glass for safe, long-term storage. The formulated glass is required to meet several processing and product quality constraints. In addition, calculations must account for associated uncertainties in constraint prediction and measurement. The algorithm also allows for the ability to hold glass compositions closer to tested regions in order to increase confidence in the output. The algorithm must also follow nuclear quality assurance procedures and submit to rigorous validation and verification testing.

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Preliminary Enhanced LAW Glass Formulation Algorithm

This report summarizes the Preliminary Enhanced Low-Activity Waste Glass Formulation Algorithm (GFA), its background information, and the calculations it performs. The Preliminary Enhanced Low-Activity Waste GFA is a tool that has been developed in MATLAB to formulate glass for a given waste composition while attempting to maximize waste loading. It is intended for use at the Hanford Tank Waste Treatment and Immobilization Plant, where nuclear waste will be vitrified into glass. The formulated glass is required to satisfy several processing and product quality constraints. In addition, calculations must account for associated uncertainties in constraint prediction and measurement. The GFA adheres to Pacific Northwest National Laboratory nuclear quality assurance procedures and has been validated and verified.

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Preliminary Enhanced LAW Glass Formulation Algorithm

This report summarizes the Preliminary Enhanced Low-Activity Waste Glass Formulation Algorithm (GFA), its background information, and the calculations it performs. The Preliminary Enhanced Low-Activity Waste GFA is a tool developed in MATLAB to formulate glass for a given waste composition while attempting to maximize waste loading. It is intended for use at the Waste Treatment and Immobilization Plant, where nuclear waste will be vitrified into glass. The formulated glass is required to satisfy several processing and product quality constraints. In addition, calculations must account for associated uncertainties in constraint prediction and measurement. The GFA adheres to Pacific Northwest National Laboratory nuclear quality assurance procedures and has been validated and verified. In this second revision to the report, two constraints: the lithium and zirconia target constraints were amended to Table 3.1 and programmed into the algorithm. Additionally, three sections were added. Section 3.2.1 includes the Enhanced LAW Correlation Rules, an addition to the glass optimality criteria. Section 4.0 discusses a stepped process approach taken to ensure the algorithm can adequately react to differences between its recommended output and the actual measurements and transfers made during plant operation, and calculation of specific radionuclide concentrations. Section 5.2 describes changes to the user interaction with the algorithm program including the addition of a graphical user interface and compilation of the software.

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Project Development of an Electrochemical Denitration and Caustic Generation System for HLW Pretreatment at Hanford - 26350

An engineering-scale electrochemical processing skid is proposed to perform the denitration of Hanford tank waste, which would help to mitigate a key process concern with the direct feed processing of the Hanford Tank Waste Treatment and Immobilization Plant (WTP). The reduction of nitrates and organic compounds in the waste feed will directly reduce hazardous NOx and ammonia gases generated during the vitrification process, which in turn will aid in addressing potential regulatory and safety challenges associated with processing large volumes of tank waste. This paper highlights the past legacy work, project layout, accomplishments from Phase 1 and research and development envisioned for Phase 2. An innovative electrochemical denitration and caustic generation (EDCGe) process was demonstrated for the pretreatment of tank waste at the Savannah River Site (SRS) in the early 2000s. The denitration electrolyzer, off-gas abatement system, and caustic generator electrolyzer are being developed with the intent that the denitration electrolyzer will convert nitrate and nitrite anions to nitrogen gas while also yielding other gaseous byproducts, which may include N2O, NH3, VOCs, and H2. The gaseous byproducts will be managed via a tandem off-gas catalyst-bed treatment system. The caustic generation electrolyzer will recycle NaOH from the feed to produce a clean caustic stream for use within the batching tanks at Hanford, aiding in the preparation of waste for WTP. The reduction in hazardous emissions and improved waste treatment processes provides a robust solution for nuclear waste management, contributing to environmental safety and regulatory compliance. The EDCGe technology is being adapted, modified, and updated for the preparation of the Direct Feed-High Level Waste (DF-HLW) flowsheet at Hanford. Phase 1 demonstrated a bench-scale proof-of-concept for reactions involving the denitration electrolyzer and gas phase abatement of ammonia. The electrochemical technology is drawing on the scientific outcomes that were reported in the legacy work. The results from Phase 1 demonstrated the viability of the EDCGe system in reducing the nitrogen species of simple non-radioactive waste simulants. Commercially available alloys used as electrode materials and membranes are being studied for the denitration and caustic generation electrolyzers. The continuation of this project holds promise for broader applications, such as energy-efficient ammonia production, and contributes significant advancements in nuclear waste management. Additional material discovery has been investigated into ceramic Na super ion conductive (NaSICON) materials and off-gas abatement catalyst discovery. NaSICON is of interest for selective transport of Na within the electrolyzers to make a clean caustic stream. Future integration and optimization efforts, informed by Phase 1 results and ongoing research, will continue to drive advancements in nuclear waste management technology. The technology developed for the EDCGe treatment of tank waste will also have broader potential to inform other fields, such as energy-efficient ammonia production, as well as ammonia abatement catalysis through the lessons learned in electrochemical nitrate reduction. The applications and benefits of this research extend beyond Hanford and the Savannah River Site, supported by a collaborative team of scientists and engineers from national labs, academia, and industry, ensuring a comprehensive approach to solving complex waste treatment challenges. The team is leveraging advanced electrochemical technologies, machine learning, novel catalysts tailored for gaseous nitrogen species, and cutting-edge reactor systems to enhance the process efficiency and effectiveness of the denitration process.

Rodene, Dylan [Savannah River National Laboratory ↗

Follow-on Report of Analysis of Approaches to Supplemental Treatment of Low-Activity Waste at the Hanford Nuclear Reservation (Vol. I)

The Hanford Site, in southeast Washington State, is preparing to disposition approximately 56,000,000 gallons (56 Mgal) of radioactive and chemically hazardous wastes currently stored in underground tanks at the site. Tank wastes will be divided into a high-activity fraction and a low-activity fraction for subsequent treatment and disposition. A waste processing and treatment facility, the Waste Treatment and Immobilization Plant (WTP), will include the high-level waste (HLW) vitrification facility (WTP HLW Vitrification Facility) for immobilizing the high-activity fraction and a low-activity waste (LAW) vitrification facility (WTP LAW Vitrification Facility) for immobilizing the low-activity fraction. Both facilities will use vitrification technology to immobilize the Hanford tank wastes in a glass waste form. The volume of LAW to be treated and disposed of following waste retrieval and WTP operations will exceed the planned processing capacity of the WTP LAW Vitrification Facility. ORP-11242,-River Protection Project System Plan, estimates a shortfall in LAW treatment capacity of approximately 56 Mgal, approximately 50% of the projected LAW volume. To maintain the planned tank waste processing mission schedule, the U.S. Department of Energy (DOE) will require additional LAW treatment capacity (termed “supplemental LAW”) external to the WTP process. LAW must be solidified by a treatment technology before the waste can be permanently disposed of in an approved DOE on-site disposal facility or a commercial (state or U.S. Nuclear Regulatory Commission [NRC-licensed]) off-site mixed low-level waste disposal facility. A decision on the approach to supplemental LAW treatment, processing, and disposal has not yet been made

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Follow-on Report of Analysis of Approaches to Supplemental Treatment of Low–Activity Waste at the Hanford Nuclear Reservation (Volumes I & II)

The Hanford Site, in southeast Washington State, is preparing to disposition approximately 56,000,000 gallons (56 Mgal) of radioactive and chemically hazardous wastes currently stored in underground tanks at the site. Tank wastes will be divided into a high-activity fraction and a low-activity fraction for subsequent treatment and disposition. A waste processing and treatment facility, the Waste Treatment and Immobilization Plant (WTP), will include the high-level waste (HLW) vitrification facility (WTP HLW Vitrification Facility) for immobilizing the high-activity fraction and a low-activity waste (LAW) vitrification facility (WTP LAW Vitrification Facility) for immobilizing the low-activity fraction. Both facilities will use vitrification technology to immobilize the Hanford tank wastes in a glass waste form.

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Advanced Retrieval and Disposition Techniques for Remote Handled Mixed Low-Level Waste - 20319

Legacy waste generated by the sodium-cooled fast reactor, EBR-II, program at the Idaho National Laboratory (INL) (owned by the U.S. Department of Energy and managed and operated by Battelle Energy Alliance, LLC) is challenging to treat and disposition using conventional methods. As a result, Veolia Nuclear Solutions is under contract with the Idaho National Laboratory to demonstrate an integrated retrieval and disposition solution for Remote-Handled Mixed Low-Level Waste currently stored in underground liners at INL. Delivery of the integrated solution builds on the expertise and successes of Veolia Nuclear Solutions under its Problematic Waste Treatment Initiative with INL. This initiative focuses solely on the treatment of problematic (reactive metal containing) waste streams using the Veolia Nuclear Solutions GeoMelt{sup R} In-Container Vitrification (ICV{sup TM}) technology. Under the contract, Veolia Nuclear Solutions will provide a fully commissioned prototype remote retrieval system to semi-remotely retrieve and size-reduce problematic waste liners into a safe and consolidated package for transport. The consolidated package will be shipped to Richland, Washington for demonstration treatment using the robust GeoMelt Richland system at Perma-Fix Northwest. The treated waste will ultimately be disposed of as a vitrified Low-Level Waste glass monolith. Veolia Nuclear Solutions has delivered countless remotely operated systems globally to solve some of the industry's most challenging problems. To ensure risk is mitigated in the best possible manner, a methodical phased approach is being utilized to validate the integrated solution. This contract focuses on the delivery and deployment of the prototype retrieval system onsite and the treatment of a single liner. Following successful demonstration treatment using GeoMelt ICV, the project is planning to make prototype enhancements before retrieving and treating another liner. Establishing a new integrated approach for retrieval and disposition of waste offers many benefits to INL and the U.S. Department of Energy. It is anticipated that the integrated solution will provide significant cost and schedule savings by increasing the number of liners dispositioned per year. In addition, the complexity of the overall waste disposition process will be reduced. Remotely retrieving and size-reducing waste in the field will provide additional safety to operational personnel and allow critical resources, such as hot cells, to focus on the primary missions at hand. Vitrification (using the GeoMelt ICV technology) allows for the direct processing of metal clad waste thereby significantly reducing pretreatment steps while providing a robust waste form for long-term disposal. The results from this ongoing contract are presented in this paper. (authors)

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Vitrification of Hanford Tank Wastes for Condensate Recycle and Feed Composition Changeover Testing

During the vitrification of Hanford Site nuclear waste at the Waste Treatment and Immobilization Plant (WTP), which is a part of the safe and efficient retrieval, treatment, and disposal mission of the U.S. Department of Energy Office of River Protection, the offgas condensate generated from the waste-to-glass conversion is currently planned to be concentrated by evaporation in the Effluent Management Facility (EMF). This concentrated condensate can then be recycled back to the incoming waste and vitrified. To test the recycle process, an apparatus was designed and built to mimic the EMF evaporator and was then used to concentrate a volume of condensate produced during the vitrification of a sample of Hanford tank 241-AP-107 (referred to herein as AP-107) waste in a continuous laboratory-scale melter (CLSM). The concentrated condensate was added to an additional sample of AP-107 waste, to mimic one round of the recycle process, and the combined solution was vitrified, producing a second round of recycle condensate. In the current study, the EMF test apparatus was used to concentrate the second-round recycle condensate under evaporation conditions (at 45 °C and 1.4 psia) designed to emulate EMF operation. The condensate was successfully concentrated by a factor of ~10 while retaining over 95 % of the technetium-99 ( 99 Tc), Cs, and I inventories in the concentrate. Another portion of AP-107 waste was retrieved by Washington River Protection Solutions, LLC (WRPS) and transferred to Pacific Northwest National Laboratory (PNNL), where it was pretreated and then combined with the second-round recycle AP-107 condensate concentrate and glass-forming chemicals (GFCs) to form the two-time recycle AP-107 melter feed, approximating a second round to the recycling action to be performed at the WTP. A portion of AP-105 waste was also retrieved by WRPS and provided to PNNL for pretreatment and combining with GFCs to form AP-105 melter feed. The two-time recycle AP-107 and AP-105 melter feeds were processed consecutively in the CLSM. The CLSM run proceeded for 13.63 hours, producing 9.70 kg of glass for an average glass production rate of 1464 kg m 2 d -1 during the two-time recycle AP-107 feed charging and 1568 kg m 2 d -1 during the AP-105 feed charging. The rate during AP-107 charging was essentially equivalent to the rate when processing no-recycle AP-107 feed and lower than that achieved when processing one-time recycle AP-107 feed. However, all rates were within the potential range of variability when processing melter feeds with similar composition in the CLSM. Likewise, the rate during AP-105 charging was higher than the previous rate processing AP-105, but within the potential CLSM range. The cold-cap characteristics changed from the typically thin AP-107 cold cap to a foamy-edged cold cap as previously seen with AP-105 shortly after transitioning to the AP-105 melter feed. The glass produced during the CLSM run was within 10 % of its target composition for the primary glass components. The CaO and Li 2 O targets varied by more than 1 wt% between the two-time recycle AP-107 and AP-105 glass targets and it took about 2 turnovers of the CLSM glass inventory to reach a relative chemical steady state in the glass for CaO and Li 2 O after the melter feed inputs were switched. The 99 Tc and total cesium content in the melter feeds were maintained at concentrations expected to be experienced at the WTP. During the CLSM run, while processing the two-time recycle AP-107 melter feed at a relative chemical steady state, the 99 Tc/Cs ratio was 10, and 34% of 99 Tc and 74% of Cs were retained in the glass. These values were higher than those measured in the CLSM run with one-time recycle AP-107 melter feed. After the transition to processing the AP-105 melter feed, when the production reached a relative chemical steady state, the 99 Tc/Cs ratio was 77 while 44% of 99 Tc was retained in the glass. The C's retention during this time frame reached 200% due to the excess C's in the glass after the target content decreased to 15% of its initial level in the two-time recycle AP-107 melter feed to the lower target in the Ap-105 melter feed. While iodine was below inductively coupled plasma mass spectrometry analytical reporting limits in the melter feed and glass samples, it was detected in quantities above the analytical reporting limits in the liquid and filter samples collected from the CLSM offgas treatment system. The behavior of iodine in the CLSM offgas treatment system followed a similar pattern to those of 99 Tc and Cs.

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Follow-On Report of Analysis of Approaches to Supplemental Treatment of Low-Activity Waste at the Hanford Nuclear Reservation (Volumes I & II)

The Hanford Site, in southeast Washington State, is preparing to disposition approximately 56,000,000 gallons (56 Mgal) of radioactive and chemically hazardous wastes currently stored in underground tanks at the site. Tank wastes will be divided into a high-activity fraction and a low-activity fraction for subsequent treatment and disposition. A waste processing and treatment facility, the Waste Treatment and Immobilization Plant (WTP), will include the high-level waste (HLW) vitrification facility (WTP HLW Vitrification Facility) for immobilizing the high-activity fraction and a low-activity waste (LAW) vitrification facility (WTP LAW Vitrification Facility) for immobilizing the low-activity fraction. Both facilities will use vitrification technology to immobilize the Hanford tank wastes in a glass waste form.

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Unraveling Anion-Specific Inhibition and Structural Modulation of Gibbsite Crystallization: Implications for Aluminum Mobility in Natural and Engineered Systems

Gibbsite (α-Al(OH) 3 , sometimes designated as γ-Al(OH) 3 ) plays a crucial role in the chemistry of aluminum in the environment and industry, yet its crystallization behavior under multianionic conditions is not well understood. Here, in this study, we investigate how six common anions─fluoride (F – ), chloride (Cl – ), bromide (Br – ), nitrate (NO 3 – ), sulfate (SO 4 2– ), and phosphate (PO 4 3– )─influence the mineralization, structure, and morphology of gibbsite at room temperature. The results show that PO 4 3– , SO 4 2– , and F – strongly inhibit gibbsite formation, stabilizing amorphous or alternative crystalline phases such as nordstrandite and cryolite. On the contrary, Cl – , Br – , and NO 3 – allow partial to complete crystallization of gibbsite without significant morphological changes. Solid-state 27 Al magic angle spinning nuclear magnetic resonance provides crucial insight into aluminum coordination environments in both crystalline and amorphous phases, distinguishing between octahedral, pentahedral, and tetrahedral Al species. The density functional theory calculations reveal a direct correlation between the Al–X bond strength and the inhibition of crystallization, following the order: PO 4 3– > SO 4 2– > F – > NO 3 – > Cl – > Br – . These findings offer molecular-scale insights into anion-specific effects on aluminum hydroxide nucleation and transformation, improving the understanding of gibbsite formation and aluminum cycling in soils, phosphate retention, contaminant immobilization, and waste treatment strategies in nuclear and industrial settings. These insights can also guide the controlled synthesis of aluminum hydroxide materials with tailored crystallinity and morphology via liquid-assisted methods.

Anions effect↗

Phosphate-Based Approaches for Dechlorination and Treatment of Salt Waste from Electrochemical Processing of Used Nuclear Fuel: A Perspective on Recent Work

Phosphate-based reagents are being considered by the U.S. Department of Energy (DOE) Office of Nuclear Energy to process halide salt-based nuclear wastes for stabilization prior to disposal. As evidenced by the Experimental Breeder Reactor-II (EBR-II) project, electrochemical processing (pyroprocessing) can be employed to recover uranium and other actinides for reintegration into the nuclear fuel cycle from metallic fuels. The resultant salt-based wastes generated from electrochemical processing of EBR-II fuel contains fission products within a LiCl–KCl eutectic salt that necessitate appropriate disposal. This paper provides an overview of recent efforts to support halide-based salt waste treatment for disposition, as well as a basis for comparison with other related efforts in salt waste treatment through salt partitioning initiatives. The U.S. DOE has selected a phosphate waste form reference material for further investigation and longer-term studies.

electrorefiner↗

Vitrification of Hanford Tank Wastes for Condensate Recycle and Feed Composition Changeover Testing (Rev. 1)

During the vitrification of Hanford Site nuclear waste at the Waste Treatment and Immobilization Plant (WTP), which is a part of the safe and efficient retrieval, treatment, and disposal mission of the U.S. Department of Energy Office of River Protection, the offgas condensate generated from the waste-to-glass conversion is currently planned to be concentrated by evaporation in the Effluent Management Facility (EMF). This concentrated condensate can then be recycled back to the incoming waste and vitrified. To test the recycle process, an apparatus was designed and built to mimic the EMF evaporator and was then used to concentrate a volume of condensate produced during the vitrification of a sample of Hanford tank 241-AP-107 (referred to herein as AP-107) waste in a continuous laboratory-scale melter (CLSM). The concentrated condensate was added to an additional sample of AP-107 waste, to mimic one round of the recycle process, and the combined solution was vitrified, producing a second round of recycle condensate. In the current study, the EMF test apparatus was used to concentrate the second-round recycle condensate under evaporation conditions (at 45 °C and 1.4 psia) designed to emulate EMF operation. The condensate was successfully concentrated by a factor of ~10 while retaining over 95 % of the technetium-99 (99Tc), Cs, and I inventories in the concentrate. Another portion of AP-107 waste was retrieved by Washington River Protection Solutions, LLC (WRPS) and transferred to Pacific Northwest National Laboratory (PNNL), where it was pretreated and then combined with the second-round recycle AP-107 condensate concentrate and glass-forming chemicals (GFCs) to form the two-time recycle AP-107 melter feed, approximating a second round to the recycling action to be performed at the WTP. A portion of AP-105 waste was also retrieved by WRPS and provided to PNNL for pretreatment and combining with GFCs to form AP-105 melter feed. The two-time recycle AP-107 and AP-105 melter feeds were processed consecutively in the CLSM. The CLSM run proceeded for 13.63 hours, producing 9.70 kg of glass for an average glass production rate of 1464 kg m 2 d -1 during the two-time recycle AP-107 feed charging and 1568 kg m 2 d -1 during the AP-105 feed charging. The rate during AP-107 charging was essentially equivalent to the rate when processing no-recycle AP-107 feed and lower than that achieved when processing one-time recycle AP-107 feed. However, all rates were within the potential range of variability when processing melter feeds with similar composition in the CLSM. Likewise, the rate during AP-105 charging was higher than the previous rate processing AP-105, but within the potential CLSM range. The cold-cap characteristics changed from the typically thin AP-107 cold cap to a foamy-edged cold cap as previously seen with AP-105 shortly after transitioning to the AP-105 melter feed. The glass produced during the CLSM run was within 10 % of its target composition for the primary glass components. The CaO and Li 2 O targets varied by more than 1 wt% between the two-time recycle AP-107 and AP-105 glass targets and it took about 2 turnovers of the CLSM glass inventory to reach a relative chemical steady state in the glass for CaO and Li 2 O after the melter feed inputs were switched.

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Panel Session 98B: Treatment of Low-Activity Tank Waste at Hanford: Considering the Alternatives

This panel focused on alternative treatment of the Hanford Low-Activity Tank Waste. Currently, Tank Waste at the Hanford Site is to be separated into low-activity (LAW) and high-level waste (HLW) fractions, and then vitrified to produce immobilized LAW glass for onsite disposal, and HLW glass for ultimate geologic disposal. This panel discussed several commissioned studies by the National Laboratories, National Academies, and General Accountability Office to evaluate the risks, costs, and benefits associated with considering options for immobilizing portions of the Hanford LAW waste forms. Panelists with presentations: Analysis of Supplemental Treatment Approaches for Low-Activity Waste at the Hanford Nuclear Reservation Overview and Conclusions (Michael Stone); Analysis of Supplemental Treatment Approaches for Low-Activity Waste at the Hanford Nuclear Reservation: Disposal Performance Evaluation (Tom Brouns); National Academies Review of the Study on Supplemental Treatment Approaches of Low-Activity Waste at the Hanford Nuclear Reservation (Charles Ferguson); GAO Observations on Immobilizing Low-Activity Waste at DoE's Hanford Site (David Trimble)

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GeoMelt{sup R} In-Container Vitrification (ICV){sup TM} for Fukushima Daiichi Water Treatment Secondary Wastes - 20212

The Japanese government is supporting development work implemented jointly by Veolia subsidiaries Kurion Japan, K.K., Veolia Nuclear Solutions (VNS), Inc., and Veolia Nuclear Solutions Federal Services, LLC for treating radioactive waste generated from Fukushima Daiichi Nuclear Power Station (NPS) water treatment using the GeoMelt{sup TM} In-Container Vitrification (ICV){sup TM} technology. The initial work consisted of glass formulation and engineering-scale testing which was completed in 2018, in the frame of an IRID (International Research Institute for Nuclear Decommissioning) program as part of a project subsidized by Japan's Ministry of Economy, Trade and Industry (METI). The Fukushima Daiichi NPS Mid- and Long-Term Road-map requires investigation of methods to stabilize solid wastes (and to immobilize radioisotopes in the wastes) generated as a result of emergency response and decommissioning activities. Cooling water treatment has resulted in a significant amount of solid and slurry secondary wastes (mostly adsorbents and ion-exchange materials) which will require processing at some point. GeoMelt{sup R} ICV{sup TM} is a joule-heated melter technology which uses a refractory-lined single-use container combining the melter and disposal container. There is no pouring required nor concerns with refractory corrosion which allows the process to accommodate a wide range of waste chemistries and high waste loadings. The testing described here consisted of three engineering-scale melts, each processing between 212 kg and 240 kg of waste simulants, glass formers, and non-radioactive cesium (Cs) and strontium (Sr) tracers. Continuous isokinetic stack sampling of off-gas emissions was performed for each test in order to calculate Cs and Sr retention in the glass wasteform. Single-pass retention of Cs in the final glass wasteform ranged from 91.46 to 99.30%, and single-pass retention of Sr ranged from 99.76 to 100%. Planned particulate recycle will increase these retention levels. Melt 1 processed a mixture of KUR-EH (a zeolite-based ion-exchange material), simulated Advanced Liquid Processing System (ALPS) Carbonate and Iron Slurries, and glass additives. Melt 2 processed a mixture of KUR-EH, KUR-TSG (a titanate-based adsorbent), and glass additives. Melt 3 processed a mixture of KUR-EH, simulated barium sulfate/iron ferrocyanide sludge (AREVA sludge), and glass additives. Waste loadings for these melts ranged from 70 weight percent (wt%) to 82 wt%. Vitrification produces a waste form much denser than the stored water treatment secondary waste wastes, resulting in significant volume reduction. Volume reductions for the three tests ranged from 74 to 79 vol%. Vitrification produces a chemically durable wasteform. Pacific Northwest National Laboratory (PNNL) tested three glass samples from each engineering-scale melt) by the Materials Characterization Center 1 (MCC-1) test, an international standard leach test of the chemical durability of nuclear waste glasses. PNNL also obtained one U.S. reference glass (EA Glass) and two Japan reference glasses P0798) and tested these under the same MCC-1 conditions (90 deg. C, 10 m-1, DIW, and 7, 14, 28-day) as the GeoMelt{sup R} ICV{sup TM} glasses. The GeoMelt{sup R} ICV{sup TM} glasses exhibited lower total normalized releases and 14- to 28-day normalized release rates than the three reference glasses. These results suggest that the GeoMelt{sup R} ICV{sup TM} glasses have durabilities on par with high-level waste glasses under standard test conditions. Post-melt process sampling and analysis indicated no Cs migration into the melter refractory materials and very little deposition of Cs or Sr onto the melter hood or off-gas piping internals. The results of the testing indicated good Cs retention in the glass, high volume reduction and waste loadings, and excellent chemical durability. These factors are important to minimize treatment costs and to protect workers and the environment. (authors)

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Requalification and Declaration of High-alpha Cemented TRU-waste from the Late 70's and Early 80's - 20499

KTE and Siemens launched a project to qualify a series of 391 waste drums and 115 concrete containers produced from 1979 to 1984. The waste is characterized by a high content of long-lived alpha-nuclides (TRU-waste - Pu, U, Am in the range of 1 E+11-1 E+12 Bq/ drum. This high radionuclide inventory requires a special packaging according to the waste acceptance criteria (WAC) of the repository Konrad [1] despite the fact, that the waste was treated manually. The raw waste originally was delivered in nitric acid solution and was solidified using ordinary Portland cement. The existing documentation comprises analyses, transfer documentation for the nuclear fuel nuclides and waste treatment documentation yielding information, which waste was treated together in a batch. Additionally all drums were subjected to non-destructive gamma-spectrometry assay. A small number of 7 drums were opened and sampled to support the existing declaration. For the entire series the waste products were attributed to defined batches using the accountancy data supported by the analyses and the gamma-spectrometry. Each batch was produced from a homogeneous stock of waste solution and can therefore be declared and documented together. The declaration concept is based on the gamma spectrometry results performed on the entire drums, which were corrected and extended for the uncertainty of the analyses. The declaration concept is verified by the regulator and its independent expert. The state of the project is in the documentation of the solidification campaigns followed by the planning of the container configuration. (authors)

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Vitrification of Hanford Tank 241-AP-107 with Recycled Condensate

During the vitrification of nuclear waste at the Hanford Waste Treatment and Immobilization Plant (WTP) – the primary mission of the U.S. Department of Energy Office of River Protection – the offgas condensate generated from the waste-to-glass conversion is currently planned to be concentrated by evaporation in the Effluent Management Facility (EMF). This concentrated condensate can then be recycled back to the incoming waste and vitrified. To test the recycle process, a test apparatus was designed to mimic the EMF evaporator and used to concentrate a volume of condensate that had been previously produced during the vitrification of Hanford tank 241-AP-107 (referred to herein as AP-107) waste in a continuous laboratory-scale melter (CLSM). The test apparatus successfully concentrated the AP-107 condensate by a factor of 10 while retaining over 90 % of the technetium-99 ( 99 Tc), Cs, and I inventory. A second portion of AP-107 waste was retrieved by Washington River Protection Solutions, LLC, given to Pacific Northwest National Laboratory, and combined with the AP-107 condensate concentrate after undergoing solids filtration and cesium removal by ion exchange. This combination served to approximate the recycling action to be performed at the WTP. After the addition of glass-forming chemicals (GFCs), the combined AP-107 waste and AP-107 condensate concentrate were processed in the CLSM to produce a glass, called AP-107-1R, that was designed to satisfy the WTP baseline requirements (Kim et al. 2012). During the 8.87 hours of processing, 7.27 kg of AP-107-1R glass were produced for an average glass production rate of 1739 kg m 2 d -1 . Compared to the previous run in the CLSM without recycled condensate, the run with the recycle had a greater average glass production rate, but the rate was within the potential range of variability when processing melter feeds with similar composition in the CLSM. The glass produced from the AP-107 recycle run in the CLSM was within 10 % of the target AP-107-1R glass composition with respect to the primary glass components. Analysis of the minor component impurities revealed that their content in the glass product had approached their nominal target after 2 turnovers of the glass inventory in the CLSM while the activity of the minor radionuclides was retained in the glass product. The 99 Tc and total cesium content in the combined AP-107 waste and recycled condensate were maintained at concentrations expected to be experienced at the WTP. During processing in the CLSM, at discrete sampling time periods, the target 99 Tc/Cs mass ratio in the glass formulation varied from 0.9 to 62.9. Across this range, the Cs retention in the glass ranged from 53 to 60 %, while the retention from the entire runtime totaled 68 %, values which align with Cs retention in other scaled melter systems while processing LAW melter feeds at 99 Tc/Cs mass ratios ranging from 1 to 100. The 99 Tc retention in the glass ranged from 22 to 32 %, primarily due to the cold-cap coverage on the glass melt surface, the area covered by reacting melter feed, varying from ~80 % to ~95 % during processing, demonstrating greater volatility of 99 Tc from the glass while more surface was exposed, as expected based on previous 99 Tc volatility studies.

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