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DOE OSTI2023

Impacts of Lanthanide Ion Complexation on the Radiation Robustness of Diglycolamide Extractants

Nuclear power reactors represent a clean and reliable source of baseload energy. However, nuclear reactors produce used nuclear fuel (UNF), which, if not recycled/reprocessed, must be disposed of as high-level radioactive waste, necessitating long-term storage options. UNF contains approximately a third of the periodic table, including the radioactive minor actinides (MA) americium and curium. Removal of these MA from UNF would greatly reduce the radiotoxic burden, volume, and cost of a storage facility or geological repository. Thus, a significant global effort has been devoted to the design of reprocessing strategies for the clean separation of the MA from UNF. As MA separations are difficult, due to the presence of lanthanide elements in UNF and their remarkably similar chemical properties, many extractants have been studied. The diglycolamide (DGA) class of extractants are promising for this separation as they exhibit high distribution coefficients for the MAs, high metal loading capacities, and are robust in highly acidic radiation environments.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2017

The Proposed Operations Master Plan of Cigeo - 17013

The proposed operations master plan of Cigeo describes the so-called 'reference progression' of the Cigeo project as envisaged by Andra at the end of the preliminary design studies. It aims at clarifying the objectives of the industrial pilot phase and present the choices offered by the reversibility for the management of the Cigeo project. The reference progression includes the inventory of the waste to be disposed of in Cigeo used for the dimensioning (73 600 m{sup 3} of ILW-LL and 10 100 m{sup 3} of HLW). Cigeo is designed to store the waste already produced and those that will be produced in the future by the existing nuclear installations and those whose creation was authorized, until the predictable end of their operation and their dismantling. All spent fuel is assumed to be reprocessed. The reference progression also includes the duration and the projected milestones of the construction and operation phases of Cigeo until termination. Across the operating life of Cigeo, the extensions of the Cigeo repository areas proceed by successive incremental phases, from the start of the industrial pilot phase (2025) to the final closure operations planned by 2150. Reversibility is defined as the ability to offer to the next generations different choices in terms of radioactive waste long-term management. The implementation of the reversibility principle is based on both governance and technical project management tools. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2017

The Effect of Kr-85 Decay to Rb-85 on Waste Forms - 17105

Krypton-85 (Kr-85) is a volatile radionuclide released during the reprocessing of used nuclear fuel (UNF). Prior to discharge of process off-gas streams to the environment, removal of Kr-85 is required to meet emission regulations. Once removed from the off-gas streams, Kr (containing stable Kr in addition to Kr-85) must be placed in storage until the Kr-85 has decayed to levels such that its potential release would meet regulatory guidelines. The current method of storage is high-pressure metal canisters. Historically, concerns have been expressed that the decay product of Kr-85, Rubidium-85 (Rb-85), could cause corrosion and weakening in the canisters that would ultimately lead to premature failure and release of Kr-85. Alternate methods and materials, such as matrix isolation in a vapor deposited metal and immobilization in zeolites, have been investigated as storage approaches for Kr. However, even these storage methods may become compromised due to the chemical effects of Rb-85 arising from the decay of Kr-85. A review was conducted of the available literature to examine topics relevant to the effects of Rb on the long-term storage of Kr-85, examine the source terms in the context of this concern, and suggest a path forward to resolve outstanding knowledge gaps. In the course of this analysis, several knowledge gaps were identified. Examples include: o The use of solid sorbents to potentially permit more Kr-85-bearing gas to be loaded into canisters, either at the pressures used in the current method or at significantly lower pressures. o A cost-to-benefit analysis is needed to ascertain the practicality of manufacturing waste forms for Kr-85 storage with solid sorbents. o The effects of radiation and chemical transmutation in solid sorbents or matrices for this application are virtually unknown. o Fundamental data are needed on corrosion rates and mechanisms as functions of Rb concentration, storage temperature, etc., for various storage approaches (e.g., as compressed gas or encapsulated in a getter material) and storage container materials. The present analysis focused on the available information regarding storage of Kr-85 in high-pressure containers. It was judged unlikely that such containers would be compromised by corrosion from the Rb decay product, especially if the Kr recovery operations result in a gas composition with very low oxygen content. However, this conclusion should be revisited based on preliminary data gathered from analysis of legacy Kr waste forms. These legacy waste forms are a result of experiments conducted at Idaho National Laboratory over 30 y ago and have been stored for more than three Kr-85 half-lives. Evaluation of these forms indicates significant corrosion, the cause of which has not been conclusively determined. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2017

Recent Progress in the Understanding of UK Highly Active Liquor Chemistry and Properties - 17144

In the UK Highly Active Liquor (HAL) waste is stored in stainless steel tanks prior to encapsulation in glass in one of three lines in the Waste Vitrification Plant (WVP). The chemistry and physical properties of HAL from the historic and ongoing UK reprocessing operations is well understood, following years of operations and associated research and development programmes using primarily non-active simulants. However the imminent progression to POCO of the Highly Active Storage Tanks (HASTs), where the HAL is stored, requires a more in-depth understanding of the properties of the HAL, in particular the solid phases that are known to exist. Changes in operations are expected, including the addition of new chemical wash reagents, which will result in some fundamental changes to the chemistry in the HASTs. This paper will highlight some of the key findings from recent studies into areas such as solids formation and morphology, chemical dissolution and associated re-precipitation of solids, rheology modification and chemical conversion mechanisms. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2017

Improving Decommissioning Success using the Tool of Virtual Reality; Increasing Worker Safety and Project Schedule Stability - 17193

operations, especially underwater, is essential. Equally essential is a precise game plan for disassembly which focuses attention on the skilled remote handling operators who must produce the results. Project success is based on clean, efficient cuts and take-aways, prepared paths for waste placement and containment, programmed return paths; and practice, practice, practice on the part of the operators. Recently, our Partner, WAK Ruackbau- und Entsorgungs- GmbH (Decommissioning and Waste Management Company) was tasked with dismantling and decommissioning the Karlsruhe Reprocessing Plant. The most difficult task in this project is the dismantling of the vitrification plant. Waelischmiller was selected to address this high-consequence project. Together, WAK and Waelischmiller determined that development of a virtual reality suite, where management and operators could create a virtual vitrification layout and subsequently map and rehearse their dismantling plan was essential. This approach, using Virtual Reality (VR) as a tool in streamlining operations and rehearsing difficult moves and cuts, will be a game changer for this and future projects. It will be a first-of-a-kind in Germany. The VR suite is contained in a room at the Karlsruhe facility with a large screen, control cabinet, simulation computer, a Waelischmiller Joyarm and Masterarm. To support the dismantling of the vitrification plant, WAK/HWM will conduct interactive feasibility studies for each dismantling step. All movements; cuts, take-aways and vessel segment insertion into transportation and disposal casks will be established, programed and practiced within virtual test suite. This allows savings in cost-intensive and complex construction of test rigs. Operating personnel can be trained in the VR suite, without taking the risk of damaging expensive remote handling equipment.While the operators are working on the operating element, they stand in front of a wide screen. Instead of a real TELBOT{sup R}, a virtual TELBOT{sup R} is moving on the screen in virtual reality. While practicing, the operators cannot damage the arm and the equipment, which is a big advantage. Moreover an interactive feasibility study can be realized without building a real test rig (mock-up). Consequently significant cost-expenses can be reduced. This paper will describe the virtual suite used by the WAK in Karlsruhe and the advantages of this new and innovative approach, which is unique in decommissioning of nuclear facilities. The viewpoint of each (WAK and HWM), and the decisions and benefits realized along the project path will be detailed in the paper. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2017

Self-Absorption Corrections for Plutonium Measurements With the Tomographic Gamma Scanner - 17325

The Tomographic Gamma Scanner (TGS) is a Non-Destructive Assay (NDA) instrument that combines high-resolution gamma spectroscopy with low spatial resolution three-dimensional image reconstruction in order to reduce bias and improve precision for measurements of drummed waste. The TGS technique is especially suited to measure containers with non-uniform source distributions and low-to me-dium-density heterogeneous matrices, compared with traditional NDA methods. Canberra recently built, installed, and commissioned a TGS system, intended primarily for the measurement of plutonium (Pu) bearing waste, at a European nu-clear fuel reprocessing facility. Pu assays using the TGS technique present technical challenges distinct from those typically encountered in traditional LLW applications. Among these is the need to apply corrections for self-absorption effects that occur on scales smaller than the TGS spatial resolution, and can compromise the assay result if not included in the TGS imaging methodology. We present a brief review of the Self Absorption Correction (SAC) technique, and discuss the complications involved with its application to the TGS methodology with examples from our recent experience. This work continues a Canberra history of further developing and refining a technique to solve emerging problems, having commercialized the original methodology by partnering with the research institution that pioneered it. The TGS and the SAC methodologies were originally developed by Los Alamos National Laboratory (LANL) and John Fleissner respectively, and this work illustrates how Canberra has implemented an advancement of these techniques in a new TGS system. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2017

Integrated Disposal Facility Performance Assessment: Modeling Consistency to Support Regulatory Decision Making at Hanford - 17398

Under DOE Order 435.1, 'Radioactive Waste Management', Washington River Protection Solutions, LLC and INTERA, Inc are currently preparing a performance assessment for the Hanford Integrated Disposal Facility, a near-surface low-activity waste disposal facility located on the Hanford Site in southeast Washington State. The disposal facility is expected to receive vitrified low-activity waste produced at the Hanford Waste Treatment and Immobilization Plant, as well as other secondary solid wastes generated during the treatment process. The performance assessment performs the analyses that will be relied upon to receive the Disposal Authorization Statement, establish waste acceptance criteria, modify the RCRA permit for the facility and make a waste-incidental-to-reprocessing determination for the vitrified tank waste. In January 2006 in the case State of Washington v. Bodman (Civil No. 2:03-cv-05018-AAM), DOE, the Washington State Department of Ecology (Ecology) and the State of Washington Attorney General's office reached a settlement agreement in Ecology's claim regarding off-site waste shipments to Hanford and the adequacy of modeling in the environmental impact statement. In response to the agreement, the DOE Office of Environmental Management set a policy to establish a consistent use of commercially available and public domain software for a vadose zone and groundwater model platform to support regulatory decisions at Hanford. In October 2012, the Associate Principal Deputy Assistant Secretary for Environmental Management released a memorandum to the manager of the Richland Operation Office directing how future environmental modeling activities to support regulatory decision making on the Hanford Site would be undertaken to be consistent with the 2006 settlement agreement. The preparation of the performance assessment must meet DOE Order 435.1 requirements and the additional direction provided by DOE. This paper will identify the approach taken to comply with the requirements in the 2012 memorandum. The paper will describe how environmental modeling performed for the 2017 Integrated Disposal Facility Performance Assessment was planned in a phased approach and how the current modeling is tied to the analyses that supported the decisions made in the environmental impact statement published in 2012. Additionally, the selection and qualification of the software selected to perform modeling activities for the performance assessment will be described. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2017

Performance Assessment for the Waste Management Area C at the Hanford Site in Southeast Washington - 17515

An initial performance assessment (PA) of Single-Shell Tank (SST) Waste Management Area C (WMA C) located at the U.S. Department of Energy's (DOE) Hanford Site in southeastern Washington has been completed to satisfy the requirements of the Hanford Federal Facility Agreement and Consent Order (HFFACO), as well as other Federal requirements and State-approved closure plans and permits. The WMA C PA assesses the fate, transport, and impacts of radionuclides within residual wastes left in tanks and ancillary equipment and facilities in their assumed closed configuration, and the subsequent risks to humans into the far future. This PA focused on radiological impacts has been developed to meet the requirements for a closure authorization under DOE O 435.1 that includes a waste incidental to reprocessing determination for residual wastes remaining in tanks, ancillary equipment, and facilities. PA results indicate that the performance objectives and measures for the all-pathways dose, the air pathway dose, the radon flux, and groundwater protection are met for both the 1,000-year compliance time period (2020 to 3020) and the post-compliance period (3020 to 12020). The peak dose for the all-pathways analysis in the 1,000-year compliance period is associated with the air pathway, with the peak dose of 4 x 10{sup -5} mSv/yr dominated by tritium resulting from upward gaseous diffusive flux from the residual waste. The peak dose within the sensitivity/uncertainty analysis time period (1,000 to 10,000 years after closure) occurs at about 1,500 years after closure, and results primarily from a peak in {sup 99}Tc groundwater concentration at 100 m down-gradient of the facility. The peak total dose within the sensitivity/uncertainty analysis time period is 0.001 mSv/yr. For all of the sensitivity analyses and uncertainty analyses evaluated, the disposal system also met the performance objectives. In the uncertainty analysis performed with the system level model based on GoldSim{sup C}, the highest calculated groundwater dose in the compliance period was about 7 x 10{sup -4} mSv/yr, and the highest calculated peak dose in the sensitivity/uncertainty analysis period was 0.025 mSv/yr.Doses associated with hypothetical inadvertent human intrusion were calculated for all sources in WMA C and compared to the acute and chronic performance measures in DOE O 435.1. The calculated doses for acute and chronic exposure scenario from potential intrusion into a waste transfer pipeline remain below the DOE O 435.1 performance measure for the time period evaluated beyond 100 years after closure. Acute exposure from drilling into the waste yielded a dose of about 0.36 mSv after the assumed 100-year institutional control period, well below the 5 mSv performance measure for acute exposure. Chronic exposure to waste from drill cuttings in a rural pasture scenario resulted in a dose of about 0.08 mSv/yr after the assumed 100-year institutional control period, well below the 1 mSv/yr performance measure for chronic exposure. (authors)

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

Regulation of the First British Power Reactor to Enter into an Extended Period of 'Care and Maintenance' - 18028

All eleven of the British first-generation Magnox nuclear power plants have now ceased operating and are in various stages of decommissioning. The Magnox reactors were graphite moderated, using carbon dioxide as the primary coolant. The reactor cores are contained in steel reactor pressure vessels, except for the last two stations which have pre-stressed concrete pressure vessels. All but two of the Magnox reactor stations have been completely de-fueled. The spent fuel removed has been despatched for reprocessing at Sellafield in the north-west of England. On behalf of the UK government the Nuclear Decommissioning Authority (NDA) is responsible for cleaning up the majority of the civil nuclear legacy. The current NDA decommissioning strategy is to prepare the Magnox reactor sites for an extended period of Care and Maintenance (C and M), during which quiescent safe storage will take place (also known as safe enclosure), whereby the cores and associated structures will accrue the benefits of radioactive decay over a period of decades. This will reduce the radiation doses to workers during final dismantling and site clearance. The two Magnox rector units at the Bradwell licensed nuclear site in the south-east of England are the first scheduled to enter this quiescent safe-storage period. This is planned to commence in the second-half of 2018, and is scheduled to last for around 70 years. The Office for Nuclear Regulation (ONR) is the independent regulatory body, responsible for enforcing safety and security requirements at nuclear installations in Great Britain (GB). This paper outlines the national strategic context and how ONR's regulatory regime is applied to nuclear power plant decommissioning. It addresses some of the specific challenges posed at Bradwell during the preparatory works for entry to C and M and how ONR has addressed these. It describes how this will culminate in a regulatory decision on the acceptability of the safety and security of the Bradwell site to enter this new stage of its life cycle. Over the last few years ONR has assessed and inspected various safety aspects of decommissioning, radioactive waste management and other preparations for Bradwell's entry into C and M. Some of the operator's proposals have provided challenges to ONR, particularly where there have been changes to established approaches taken at other sites, as the licensee seeks to minimise its costs. These have included how far to remove redundant structures, systems and components prior to C and M; how to define interim and end-states for fuel cooling ponds and other contaminated areas; and how to treat and store Intermediate Level Waste (ILW), for which there is no geological disposal facility yet available. ONR has begun its final assessment of safety and security justifications supplied by the site licensee, Magnox Ltd (ML). ONR is using its legal powers conferred to it under the site licence conditions to authorise this first-of-a-kind transition into a 70 year period of safe storage. (authors)

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

Combined Assay Systems for the Characterisation of Historical ILW at of the Dounreay Shaft and Silo-18140

In 1955 the Dounreay nuclear power development establishment was created on the northern coast of Scotland primarily to pursue the UK Government policy of developing Fast Breeder Reactor (FBR) technology. The site operated then by the United Kingdom Atomic Energy Authority (UKAEA) saw the development, test and operation of 3 nuclear reactors, two of them FBRs, alongside fabrication and reprocessing facilities for the FBR fuel elements. From the late 1950's until 1977 Intermediate Level radioactive Waste (ILW) generated on site was disposed of into a 65 m deep, 4.6 m diameter shaft. In January 1977, an explosion thought to be caused by hydrogen generated from sodium and potassium wastes reacting with water occurred in the upper part of the shaft, thus stopping any further waste disposal. A second ILW storage facility, the ILW-Silo, started operation in 1971 to deal with the increasing volume of intermediate level waste generated on site in the mid-1960's and continued receiving waste until 1998. The decommissioning of the Shaft and Silo facilities is a challenging engineering task due to the complexity and potential hazards linked with the retrieval and handling of historical waste. Following recovery it is intended to shred the majority of the waste and load it into 200-l assay drums. Sludges would be separated and solidified within a special annulus drum to make them suitable for assay. To support the decommissioning strategies put forward by Dounreay Site Restoration Limited (DSRL), Mirion Technologies Canberra UK Ltd have designed and completed the manufacture of a pair of combined non-destructive waste assay (NDA) systems. The two identical automated ILW counters are intended to provide a means to characterise the waste materials by performing active and passive neutron measurement as well as segmented high resolution gamma spectrometry (HRGS) of 200-l sacrificial waste drums. The active neutron technique is based on the Differential Die Away (DDA) technique using a pulsed Deuterium-Tritium neutron generator to interrogate fissile material present in the waste. The active neutron measurements support, as well as the passive neutron coincidence measurements, a matrix correction capability by use of an Add-a-Source mechanism. The publication will describe in broad lines the approach proposed by DSRL in the processing of the waste retrieved from both the Shaft and Silo facilities. It will also present a description of the overall design of the NDA counters, illustrating how the measurements to be performed will allow DSRL to safely characterise the retrieved waste materials. (authors)

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

Vitrification Process for Idaho HLW Calcine - 18433

The majority of the liquid wastes produced from reprocessing of several types of spent nuclear fuel at the Department of energy's (DOE) Idaho site have been volume reduced by calcination. The resulting ∼155,600 ft{sup 3} of calcined waste is stored in 43 shielded stainless steel bins, which have a 500-year design life. The calcined material is both a high-level waste and a RCRA hazardous waste, which complicates treatment and disposal options. In addition to a potential direct disposal option, treatment options that have been considered include steam reforming, hot isostatic pressing (HIP), and vitrification. This paper describes testing and evaluation of a vitrification option for the calcine. Vitrification to produce a borosilicate glass has the advantage that it is the only treatment that provides a waste form that meets the current HLW repository waste acceptance criteria. It is therefore the lowest risk option in terms of regulatory and legislative concerns. The present work addressed several key questions: (i) Calcine waste loadings in glass, which determine the number of HLW canisters produced and the required glass production rate (throughput) for the system design; (ii) Melt rate per unit glass pool surface area of the melter, which determines the sizing of the vitrification system; and (iii) The ability to meet waste form acceptance requirements (PCT and TCLP) while achieving reasonable waste loadings. These are issues of fundamental importance to the sizing estimates for the unit operations and overall flow-sheet and they, therefore, directly impact the cost and schedule estimates. Fully compliant, high-waste-loading glasses were developed for two of the four Idaho calcine wastes. The results demonstrate that waste loadings of 35 wt% waste oxides are achievable for the two alumina calcines and about 30 wt% is achievable for the two zirconia calcines. Testing of these formulations in a joule-heated ceramic melter showed glass production rates of over 5000 kg/(m2/d) for the Alumina calcine and over 8500 kg/(m{sup 2}/d) for the Zirconium-Na Blend calcine. These extremely high production rates translate directly into smaller system size and shorter mission duration and, therefore, reduced costs. Based on these results, a preliminary design for the full-scale vitrification system was developed. The system consists of waste receipt, vitrification, off-gas treatment, and canister sealing and decontamination equipment. The calcine is blended with the appropriate glass forming chemicals (or glass frit) and fed to the melter as a solid stream. The melter has a glass pool surface area of about 2.5 m{sup 2} and is equipped with a bubbling system to increase processing rates. Glass production rates of about 6 metric tons per day are projected. The vitrification system would be installed into the existing Idaho Waste Treatment Unit Facility (IWTU) so that no new facilities are required to house the treatment system, thus greatly reducing overall cost, duration, and risk. The system would be designed to treat all of the calcine waste within a period of 12 years at an operating efficiency of 80%, producing a total of about 8500 canisters each weighing two metric tons. (authors)

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

Aging Management Considerations for Dry Cask Storage Canisters - 18472

Dry cask storage systems (DCSSs) are used to store used nuclear fuel (UNF) at independent spent fuel storage installations (ISFSIs) prior to final geologic storage or reprocessing. As storage durations increase beyond the twenty-year period commonly implemented for licensing the storage sites, it is important to consider aging related degradation issues for DCSS components. A large portion of the DCSS designs used throughout the world employ a ventilated concrete overpack with a welded stainless steel canister that confines the UNF. This paper explores key issues related to aging management for these canister components, including: (1) canister environment, (2) inspection limitations, and (3) aging management program guidance and requirements. While the austenitic stainless steel used for the canisters are generally resistant to most forms of environmental attack, it is possible for conditions to arise that lead to pitting and even stress corrosion cracking of the canister systems. A large number of studies related to canister degradation have been performed by industry groups and government researchers, both in the US and worldwide. These advances in the collective knowledge provide insight into risk factors for DCSS. Such information is beneficial to improve ISFSI siting decisions and ensure successful relicensing of existing ISFSIs. This paper highlights relevant research and also discusses applicability to degradation of other equipment and containers used to process and isolate UNF and other nuclear waste streams from the public and the environment. Inspection of the canister surface is an important tool to investigate and evaluate the potential for degradation. Existing DCSS designs typically do not offer ready access to the canister surface in order to perform the inspection. Further complicating inspection efforts are the surface conditions present on the sheltered canisters after extended storage times, including atmospheric debris such as dust and pollen. Given ongoing development efforts, inspection capabilities and associated limitations should be assessed at multiple points in time over the course of an aging management program to incorporate new advances in the field. This paper explores the limitations of currently available capabilities in inspection and delivery, and provides insight into the gaps remaining to be filled to permit an effective inspection program. Recommendations and requirements related to programs for aging management of canisters have been published or are in progress from a variety of groups, including industry groups, regulatory authorities, and Codes and Standards. An effective aging management program should consider the technical bases of these various inputs and maintain compliance with requirements. Given multiple sources, decisions will be required when considering conflicting guidance, and this paper will include discussion of the relative merits of the various approaches. (author)

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

Applicability of HBU Fuel Cask R and D Project to Al Clad Fuel Storage - 18558

Aluminum clad spent nuclear fuel (SNF) not destined to be reprocessed at Savannah River's H Canyon will eventually be moved from existing wet and dry storage facilities into standardized dry storage systems (e.g., Universal Canisters), ideally suited for disposal. With the current lack of disposal capacity in the U.S., placement of this SNF into dry storage requires plans for demonstrating to the regulator the safety of both the extended storage and the subsequent transportation to a future disposal facility of this SNF. For commercial SNF, concerns related to extended dry storage and subsequent transportation have been, and continue to be, addressed through several demonstration projects including, but not limited to, one for the lower burnup SNF at Idaho National Laboratory (INL) and one for the higher burnup SNF at Dominion's North Anna Power Station. Lessons learned from the more recent Orano led higher burnup demonstration project (HBU Demo Project) provides relevant information for advancing the concept of a 'smart cask' system for dry interim storage, which will allow for collection of data to support the safety demonstration for extended dry storage and subsequent transportation of the aluminum clad SNF. This 'smart cask' would eliminate the need for multiple demonstration projects that may have to be performed for different types of aluminum clad SNF designs and/or for potentially age distinguishing parameters, such as burnup or initial enrichment. This 'smart cask' would be developed and deployed by leveraging the HBU Demo Project's experience associated with modifying and deploying a TN-32B bolted carbon steel vertical storage cask system to monitor key parameters related to the criticality, structural, confinement, and thermal safety of the SNF and the canister system containing this SNF. This paper will focus on how the extensive design, licensing, and fabrication experience accumulated by the HBU Demo Project's cask system can be leveraged to support the design, licensing, and fabrication of a 'smart cask' system intended to support/confirm the interim dry storage, potential extended storage, and subsequent transportation of aluminum clad SNF, such as the Advanced Test Reactor (ATR) SNF. (authors)

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

NM in HLW Borosilicate Glass: Focus on the High Performances of the IHMM Operated at La Hague Plant - 19019

Ruthenium, palladium and rhodium, which belong to Platinum-Group Metals (PGM), are part of fission products resulting from nuclear fuel reprocessing. All High Level Waste (HLW) vitrification facilities have experienced operational issues that can be related to the presence of Noble Metals (NM) in the melter. These metals have low solubility and modify glass properties such as viscosity or electrical and thermal conductivity. These dense metals also tend to settle to the bottom of the melter. Whatever the vitrification process operated, the specific properties and behavior of NM have a propensity to impact the production capacity by decreasing the glass throughput and increasing downtimes. Orano and the CEA have studied the behavior of NM in borosilicate glass for many years. It has led to several technological improvements and process operation optimizations on the Induction Heated Metallic Melter (IHMM) currently operated at La Hague plant. These enhancements, implemented since active commissioning, have headed to a high efficiency in terms glass production and NM incorporation (more than 21000 canisters produced with up to 3 % of Noble Metals in the glass). This paper sets out the continuous improvement program implemented on the La Hague vitrification lines that has led to outstanding records of operation in terms of production capacity and NM incorporation. The benefits of the close collaboration between R and D, engineering, and operation teams is particularly emphasized. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2023

Fault Detection in the Solvent Extraction Process with Non-traditional Sensors

Solvent extraction is used to separate metals or other complexes into two different immiscible liquids and is an essential component of the PUREX Process. Improvements to the solvent extraction process can directly contribute to an organization’s ability to ensure the purity and recovery of special nuclear materials from spent nuclear fuel. Such improvements can benefit nuclear reprocessing efforts, increase fuel reutilization, and limit the concentration of actinides in nuclear waste repositories.

98 NUCLEAR DISARMAMENT, SAFEGUARDS, AND PHYSICAL P↗
DOE OSTI2020

Disulfonamide Ligands as f-Element Extractants from Alkaline High-Level Waste

Almost 100 million gallons of high level waste (HLW) has been generated from defense reprocessing programs to support nuclear weapons production. HLW is currently stored at the Hanford and Savannah River Sites (SRS) [1]. It contains radioactive components, such as {sup 137}Cs, {sup 99}Tc and {sup 90}Sr, as well as large amounts of non-radioactive species, including solvated cations and insoluble metal hydroxides. HLW has high concentration of soluble hydroxides ([OH{sup -}] = 2 M at SRS [2]), complexing inorganic anions ([NO{sub 3}{sup -}] ∼ 0.65 - 3.7 M at SRS [2]) and a high ionic strength. Even though the majority of actinide component in alkaline HLW is precipitated, studies of An(III) and Ln(III) complexation in highly alkaline solutions in the presence of high nitrate concentrations have showed that soluble nitrate complexes can be formed [3]. The current treatment of HLW at SRS currently consists of two processes: The Actinide Removal Process (ARP) and the Next-Generation Caustic-Side Solvent Extraction process (NG-CSSX). Strontium and actinides are removed by sorption on monosodium titanate through the Actinide Removal Process (ARP) commonly referred to as the alpha-strike step [4]. Then, cesium is selectively extracted from the alkaline media via the Caustic-Side Solvent Extraction (CSSX) process [5]. The CSSX solvent consists of a calix[4]arene-crown-6 extractant dissolved in an inert hydrocarbon matrix containing i) a solvent modifier (alkylphenoxy alcohol) which increases extractant solubility and prevents third phase formation, and ii) a suppressor (trioctylamine or guanidine) - that mitigates surfactant effects. The CSSX process removes {sup 137}Cs selectively and rapidly, yet the post- CSSX aqueous stream may still contain high amounts of An, thus requiring a second ARP treatment (referred to as 'alpha-finishing') for some tanks. Despite the success of the ARP process in removing Sr and An, it often represents the kinetic bottleneck of integrated processing, as it is slower than solvent extraction. Understanding the complexation of actinides by organic ligands that are compatible with the CSSX process could eventually lead to a combined caustic-side Cs/Sr/actinide extraction process with better economics due to a reduced amount of monosodium titanate and/or a shorter required contact time with titanate during ARP. This would ensure a low-activity waste (LAW) stream with no actinides without additional ARP processing post-CSSX. Disulfonamides were studied for extraction of Sm(III) from alkaline aqueous media of pH 10-14 into dichloromethane. Up to 82% of Sm(III) was extracted from solutions of pH 12.5 -13.5 and up to 84% from solutions of pH 10.5 - 11.5. These results show some resemblance with Am extraction results by calixarene ligands previously reported [10]. Kinetic studies demonstrated that even 5 min is enough to complete stripping, whereas extraction is time-limiting process and requires up to 20 h for efficient removal of Sm(III) from alkaline aqueous media. Determination of composition of complexes in solution after extraction by the equilibrium shift method showed a 1:1 Sm(III):dsa-2 complexation ratio for the extracted species.

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

Sulfonamide and Sulfonamido-phenol Ligands for Extraction of f-Elements from Alkaline High-Level Waste

Alkaline High Level Waste (HLW) has been accumulated at Hanford and Savannah River Sites as a result of reprocessing for nuclear weapons production during the cold war. A large volume (∼100 MGal) has been accumulated in carbon steel tanks at Savannah River (SRS) and Hanford. The tank waste contains three separate phases generated when NaOH was added to previously acidic Purex raffinates: 1-2 Supernatant liquid, salt-cake, and sludge. The sludge consists mainly of insoluble hydroxides of transition metals while the supernate and salt-cake contain caustic-soluble materials, including salts of highly radioactive fission products Cs(I) and Sr(II). Current treatment of alkaline HLW in SRS includes: i) The Actinide Removal Process (ARP), which is based on sorption of {sup 90}Sr and Actinides (An) on monosodium titanate (MST), also known as 'alpha-strike' process, followed by ii) Caustic Side Solvent Extraction (CSSX),4 which is used for the extraction of {sup 137}Cs by modified calixarenes in a hydrocarbon diluent. Residual actinides in some tanks are removed after CSSX by an additional ARP process commonly referred to as 'alpha-finishing'. Despite the success of ARP for Sr and An removal, as it is a sorption process, it represents the kinetic bottleneck of integrated salt waste processing. Hence potential introduction of additional organic ligands for actinide extraction (in a modified CSSX process) could simplify the overall integrated process, making it more efficient and economical, with less titanate needed and shorter sorption time, as some of the actinide component would be removed during CSSX. In this study tri-sulfonamide and o-sulfonamido-phenol (mono-sulfonamide) ligands have been studied as extractants for Sm(III), which is being used as an Am(III) surrogate. Our prior studies in the group using a tri-sulfonamide (iPr-tsa-B) showed favorable extraction for Sm(III) nitrate salts from alkaline solutions. Mono-sulfonamides possess similar orientation of binding sites to pyrocatechols, which have been found to be good ligands for Am(III) binding and extraction from alkaline media. Tri-sulfonamide of the type iPr-tsa-B6 (1 mM in CH{sub 2}Cl{sub 2} solution) was studied for Ln{sup 3+} extraction using Sm(NO{sub 3}){sub 3}.6H{sub 2}0 (10 and 25 μM) in alkaline solution of NaOH (0.05, 0.1, 0.2, 0.3 mM) / 0.1 M NaNO{sub 3}. Stripping of the organic phase was done using 0.1 M HNO{sub 3} and quantification of Sm{sup 3+} was done using ICP-OES at 359.3 nm. The need to improve stability of the complex led to synthesis of compounds with N-donor site closer to the central benzene ring to facilitate cation-π interactions. Synthesis of tri-sulfonamide type A: a) Chloromethyl methyl ether, SnCl{sub 4}, CH{sub 2}Cl{sub 2}, 0 deg. C, N{sub 2}, 4 h, 57%; b) NaN{sub 3}, reflux in H{sub 2}O/acetone for 22 h, 80%; c) PPh{sub 3}, THF/H{sub 2}O, 22 h, 79%; d) p-toluene sulfonyl chloride, Et{sub 3}N, 1,2-DCE, 22 h. Extraction: Sm(NO{sub 3}){sub 3}.6H{sub 2}O (2 mM) in 5 ml of aqueous NaOH (pH 10.5 - 14) + 6 ml of CH{sub 2}Cl{sub 2} solution of msa (20 mole equiv.) were rotated on a wheel (60 rpm; 20 h). Stripping: 5 ml of 0.1 M HNO{sub 3} + CH{sub 2}Cl{sub 2} solution of msa (after extraction, centrifugation and filtration) was rotated on the wheel (60 rpm; 20 h). Sm{sup 3+} was quantified using UV-Visible spectrophotometry.

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

Sorbmatech{sup R}Cs, an Innovative Highly Selective Cs Sorbent for Wastewater Decontamination - 20065

The treatment of radioactive wastewater from the operating nuclear industry (energy production, reprocessing of spent fuel, decommissioning of shut-down facilities, etc.) or in case of incidental or accidental situation (such as Fukushima Daichii NPP accident) is an important issue requiring constant improvement of the technologies and techniques used to prevent radioactive releases into the environment and/or to reduce the production of secondary waste. CEA, Orano and CTI are collaborating since 2014, with the support of the French government's program 'investments for the future', to develop Sorbmatech{sup R}Cs, an innovative and patented selective sorbent (Grandjean and Barre 2014) to deal with the removal of radioactive {sup 137}Cs, one of the most hazardous isotope to be managed in nuclear waste, highly efficient either in agitated reactor or in column process. Sorbmatech{sup R}Cs sorbent consists of mesoporous silica particles loaded with potassium-copper hexacyanoferrate nanoparticles (KCu-HCF). This peculiar structure enables much faster sorption kinetics compared to denser crystalline structures, such as Silicotitanate or Zeolite sorbents, whose drawback consists in hindering the diffusion process through the material, and whose larger sorbent particles slow down the ion exchange process. The equilibrium of Sorbmatech{sup R}Cs is reached in few minutes, even at high flow rates in a fixed-bed column process (up to 10 m.h{sup -1} Darcy velocity) with low drop pressure. Moreover, Sorbmatech{sup R}Cs can be used over a wide pH range from 2 to 10 and has a very high selectivity towards {sup 137}Cs even in brine solution (saline, mineral or sea water). This new sorbent also has a K{sub d} higher than 10{sup 5} mL.g{sup -1} depending on the salinity of the wastewater, enabling a highly efficient removal of Cs trace in radioactive wastewater compared to Cs selective sorbent such as Zeolites and Silicotitanates. Its radiological resistance enables the treatment of high, medium and low activity wastewater. The CEA-Orano-CTI/ALSYS partnership leads to the development of a simple and low-cost synthetic route, which demonstrated large-scale manufacturing of the product on a batch of 100 kg. Two products have been developed and are ready for short run market introduction so far with grain size well adapted either for column processes or agitated reactors.. Finally, the industrial implementation has been studied and largely benefits from the properties of the sorbent. Indeed, its high sorption kinetics enable high flow rates resulting in a decrease of operation times, unit sizes, and volumes of secondary waste produced. Moreover, Sorbmatech{sup R}Cs is designed to be combined into a full and integrated solution, ranging from preliminary optimization of operating conditions through numerical dimensioning model, industrial implementation and treatment of the wastewater (through cartridge or preconditioned columns systems developed thanks to Orano's extensive expertise), to long-term stabilization of generated waste (under progress). (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗