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Overview of reductants utilized in nuclear fuel reprocessing/recycling

Most of the aqueous processes developed, or under consideration worldwide for the recycling of used nuclear fuel (UNF) utilize the oxido-reduction properties of actinides to separate them from other radionuclides. Generally, after acid dissolution of the UNF, (essentially in nitric acid solution), actinides are separated from the raffinate by liquid-liquid extraction using specific solvents, associated along the process, with a particular reductant that will allow the separation to occur. For example, the industrial PUREX process utilizes hydroxylamine as a plutonium reductant. Hydroxylamine has numerous advantages: not only does it have the proper attributes to reduce Pu(IV) to Pu(III), but it is also a non-metallic chemical that is readily decomposed to innocuous products by heating. However, it has been observed that the presence of high nitric acid concentrations or impurities (such as metal ions) in hydroxylamine solutions increase the likelihood of the initiation of an autocatalytic reaction. Recently there has been some interest in the application of simple hydrophilic hydroxamic ligands such as acetohydroxamic acid (AHA) for the stripping of tetravalent actinides in the UREX process flowsheet. This approach is based on the high coordinating ability of hydroxamic acids with tetravalent actinides (Np and Pu) compared with hexavalent uranium. Thus, the use of AHA offers a route for controlling neptunium and plutonium in the UREX process by complexant based stripping of Np(IV) and Pu(IV) from the TBP solvent phase, while U(VI) ions are not affected by AHA and remain solvated in the TBP phase. In the European GANEX process, AHA is also used to form hydrophilic complexes with actinides and strip them from the organic phase into nitric acid. However, AHA does not decompose completely when treated with nitric acid and hampers nitric acid recycling. In lieu of using AHA in the UREX + process, formohydroxamic acid (FHA), although not commercially available, hold promises as a replacement for AHA. FHA undergoes hydrolysis to formic acid which is volatile, thus allowing the recycling of nitric acid. Unfortunately, FHA powder was not stable in the experiments we ran in our laboratory. In addition, AHA and FHA also decompose to hydroxylamine which may undergo an autocatalytic reaction. Other reductants are available and could be extremely useful for actinides separation. The review presents the current plutonium reductants used in used nuclear fuel reprocessing and will introduce innovative and novel reductants that could become reducers for future research on UNF separation.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Water O–H Stretching Raman Signature for Strong Acid Monitoring via Multivariate Analysis

Spectroscopic techniques have been applied extensively for quantification and analysis of solution compositions. In addition to static measurements, these techniques have been implemented in flow systems providing real-time solution information. A distinct need exists for information regarding acid concentration as it affects extraction efficiency and selectivity of many separation processes. Despite of the seeming simplicity of the problem, no practical solution has been offered yet particularly for the large-scale schemes involving toxic streams such as highly radioactive nuclear wastes. Classic potentiometric technique is not amiable for on-line measurements in nuclear fuel reprocessing due to requirements of frequent calibration/maintenance and poor long-term stability in the aggressive chemical and radiation environments. In this work, the potential of using Raman spectroscopic measurements for on-line monitoring of strong acid concentration in the solutions relevant to the dissolved used fuel was investigated. The Raman water signature was monitored and recorded for nitric and hydrochloric acid solution systems of systematically varied chemical composition, ionic strength, and temperature. The generated Raman spectroscopic database was used to develop predictive chemometric models for the quantification of the acid concentration (H+), neodymium concentration (Nd3+), nitrate concentration (NO3-), density, and ionic strength. This approach was validated using a flow solvent extraction system.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Annual Report on Improved Accuracy of Pu Assay of Spent Fuel Project

The objective of this work is to improve the accuracy of plutonium assay for nuclear fuel reprocessing. This work addresses such questions as: 1) How much Pu has been recovered in a reprocessing facility?; 2) Is a reprocessing operation consistent with safeguards?; and 3) How much Pu is unaccounted for in a safeguarded facility? This improved Pu accuracy will be achieved by direct measurement of Pu using monochromatic excitation and detection. These elemental measurements will not only provide direct concentration measurements of plutonium in spent fuel dissolver solution. The increased accuracy of the Pu assay addresses the heart of safeguards by providing greater accuracy and less error in the Pu measurements of these facilities. This is further achieved by using the high energy Ka line of Pu at 103.65 keV. This allows for the direct measurement of Pu through container walls such as Zircaloy tubing which is used for the cladding of nuclear fuel rods. While ultrahigh energy X-ray fluorescence (UHEXRF) has been done at synchrotron facilities, X-ray optic technology has advanced to make possible, laboratory based instrumentation to enable such high energy measurements to be done on the bench top. Such instrumentation can change the plutonium assay measurement paradigm by offering safer, more rapid and more accurate Pu measurements through container walls nondestructively.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Off-gas Adsorption Model and Simulation - OSPREY

The absence of industrial scale nuclear fuel reprocessing in the U.S. has precluded the necessary driver for developing the advanced simulation capability now prevalent in so many other countries. Thus, it is essential to model complex series of unit operations to simulate, understand, and predict inherent transient behavior. A capability of accurately simulating the dynamic behavior of advanced fuel cycle separation processes is expected to provide substantial cost savings and many technical benefits. To support this capability, a modeling effort focused on the off-gas treatment system of a used nuclear fuel recycling facility is in progress. The off-gas separation consists of a series of scrubbers and adsorption beds to capture constituents of interest. Dynamic models are being developed to simulate each unit operation involved so each unit operation can be used as a stand-alone model and in series with multiple others. Currently, an adsorption model has been developed within Multi-physics Object Oriented Simulation Environment (MOOSE) developed at the Idaho National Laboratory (INL). Off-gas Separation and REcoverY (OSPREY) models the adsorption of offgas constituents for dispersed plug flow in a packed bed under non-isothermal and non-isobaric conditions. Inputs to the model include gas composition, sorbent and column properties, equilibrium and kinetic data, and inlet conditions. The simulation outputs component concentrations along the column length as a function of time from which breakthrough data can be obtained. The breakthrough data can be used to determine bed capacity, which in turn can be used to size columns. In addition to concentration data, the model predicts temperature along the column length as a function of time and pressure drop along the column length. A description of the OSPREY model, results from krypton adsorption modeling and plans for modeling the behavior of iodine, xenon, and tritium will be discussed.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Radiation-Induced Plutonium Redox Chemistry

Plutonium plays a key role in global actinide research and nuclear fuel cycle technologies, and yet, our fundamental understanding of its inherent radiation-induced chemical behavior is limited. These radiation-induced processes cannot simply be switched off, as they are as fundamentally inherent to plutonium as the impact of relativistic effects on its f-electrons. In less chemically complex actinide systems, such as aqueous solutions of neptunium and americium, , radiolysis products play a significant role in the redox cycling of their oxidation states. However, plutonium's multiple, coexisting, and chemically active oxidation states, which comprise of bare ions and dioxo cations, provide additional redox pathways that complicate radiation-induced processes. Oxidation state control is critical for the manipulation of plutonium, especially in used nuclear fuel reprocessing technologies, where oxidation specific states are successfully extracted, and others rejected. Consequently, mechanistically understanding the behavior of plutonium’s multiple oxidation states in the presence of intense ionizing radiation fields is essential for predicting the behavior of this element under multiple conditions that support the development and innovation of nuclear fuel cycle technologies. Here, we present recent advances in our understanding of plutonium radiation chemistry, including the first-ever multiscale model for predicting gamma radiation-induced plutonium redox chemistry, and new chemical kinetics for the reaction of plutonium and its complexes of tributyl phosphate (TBP), N,N-di-(2-ethylhexyl)butyramide (DEHBA), and N,N-di-(2-ethylhexyl)isobutyramide (DEHiBA) with transients radiolysis products, a measured using electron pulse radiolysis.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

OSPREY Model

The absence of industrial scale nuclear fuel reprocessing in the U.S. has precluded the necessary driver for developing the advanced simulation capability now prevalent in so many other countries. Thus, it is essential to model complex series of unit operations to simulate, understand, and predict inherent transient behavior and feedback loops. A capability of accurately simulating the dynamic behavior of advanced fuel cycle separation processes will provide substantial cost savings and many technical benefits. The specific fuel cycle separation process discussed in this report is the off-gas treatment system. The off-gas separation consists of a series of scrubbers and adsorption beds to capture constituents of interest. Dynamic models are being developed to simulate each unit operation involved so each unit operation can be used as a stand-alone model and in series with multiple others. Currently, an adsorption model has been developed within Multi-physics Object Oriented Simulation Environment (MOOSE) developed at the Idaho National Laboratory (INL). Off-gas Separation and REcoverY (OSPREY) models the adsorption of off-gas constituents for dispersed plug flow in a packed bed under non-isothermal and non-isobaric conditions. Inputs to the model include gas, sorbent, and column properties, equilibrium and kinetic data, and inlet conditions. The simulation outputs component concentrations along the column length as a function of time from which breakthrough data is obtained. The breakthrough data can be used to determine bed capacity, which in turn can be used to size columns. It also outputs temperature along the column length as a function of time and pressure drop along the column length. Experimental data and parameters were input into the adsorption model to develop models specific for krypton adsorption. The same can be done for iodine, xenon, and tritium. The model will be validated with experimental breakthrough curves. Customers will be given access to OSPREY to used and evaluate the model.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Performance Evaluation of the CHKED Multi-Elemental Analysis and Software

The Hybrid K-edge Densitometer (HKED) is a high precision safeguards assay system developed by Ottmar and Eberle [1] for quantification of the U and Pu concentrations of dissolver solutions in spent nuclear fuel reprocessing. The HKED measurement supplements traditional destructive assay methods such as Isotope Dilution Mass Spectrometry (IDMS) and is an essential component of the international safeguards program implementation at these facilities. The Canberra Hybrid K-Edge Densitometry (CHKED) software was recently developed by Canberra Industries to better address the changing composition of the nuclear fuel cycle by addition of a multi-elemental analysis capability to the K-Edge transmission measurement. Our evaluation of the CHKED software was performed at the request of the International Atomic Energy Agency (IAEA) to examine the functionality and performance of the CHKED software and algorithms and identify potential areas for improvement of the software. The reader is assumed to be familiar with the HKED technique and its current implementation in safeguards assay of U and Pu in the nuclear fuel cycle. The Canberra Hybrid K-Edge Densitometry CHKED software replicates functionality of the older VMSbased Hybrid K-Edge Densitometer (HKED) software and incorporates additional analysis algorithms and tools. When the traditional HKED analyses are selected, the CHKED software appears to faithfully reproduce the measurement results as reported by the older software. The CHKED software includes a Multi-elemental K-Edge (MEKED) analysis based in part on algorithms devised at Los Alamos National Laboratory. In principle, the MEKED analysis represents a significant advancement over the traditional HKED analysis, providing a capability to analyze the actinide concentrations from complex solutions, such as low U:Pu ratios (e.g., U:Pu = 1:1) including additional minor actinide components such as Np and Am. However, this MEKED analysis is somewhat limited by reliance on a region of interest (ROI) analysis of the spectrum, the need for extensive calibration measurements and a simplistic interpretation of the KED transmission spectrum. Finally, the MEKED algorithm set associated with the CHKED software (V1.0) acquired by Oak Ridge National Laboratory (ORNL) from Canberra Industries does not seem to be “finished” (e.g., the MEKED analysis seems to only determine measurement results for two actinides with while results for the minor actinides appear to be highly dependent on declaration values).

98 NUCLEAR DISARMAMENT, SAFEGUARDS, AND PHYSICAL P↗

SRNL CRP progress report [Development of Melt Processed Ceramics for Nuclear Waste Immobilization]

A multi-phase ceramic waste form is being developed at the Savannah River National Laboratory (SRNL) for treatment of secondary waste streams generated by reprocessing commercial spent nuclear. The envisioned waste stream contains a mixture of transition, alkali, alkaline earth, and lanthanide metals. Ceramic waste forms are tailored (engineered) to incorporate waste components as part of their crystal structure based on knowledge from naturally found minerals containing radioactive and non-radioactive species similar to the radionuclides of concern in wastes from fuel reprocessing. The ability to tailor ceramics to mimic naturally occurring crystals substantiates the long term stability of such crystals (ceramics) over geologic timescales of interest for nuclear waste immobilization [1]. A durable multiphase ceramic waste form tailored to incorporate all the waste components has the potential to broaden the available disposal options and thus minimize the storage and disposal costs associated with aqueous reprocessing.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Milestone Report - Data Requirements and Test System Needs for Development of an Integrated Off-Gas Treatment System

In fiscal year 2016 an Engineering Evaluation of an integrated off-gas system was conducted. This study resulted in a report entitled Engineering Evaluation of an Integrated Off-Gas Treatment System for Used Nuclear Fuel Reprocessing Facilities (Jubin et al. 2016a), from here referred to as the “Engineering Evaluation.” This study focused on the capture and retention of the volatile radionuclides ( 3 H, 14 C, 85 Kr, and 129 I), selected semi-volatile radionuclides, specifically 106 Ru, and chemical species like NO and NO 2 generated during the dissolution of the used nuclear fuel. The study examined the design of the combined head-end off-gas streams and the vessel off-gas stream. The study drew upon the available literature to conduct the equipment sizing and sorbent usage. A number of assumptions were required to complete this analysis and major gaps in the available data were identified that, if resolved, could increase the fidelity of the engineering design.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Multi-Column Kr/Xe Separation Testing at Representative Superficial Velocities with DGOSPREY Model Validation

Previous testing of AgZ-PAN and HZ-PAN for the separation and removal of xenon and krypton from air have been promising. This report details the results of multi-column testing at superficial velocities chosen to emulate probably velocities in a full-scale used nuclear fuel reprocessing facility. Additionally, results were used to validate the DG-OSPREY model under development at Georgia Institute of Technology.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Understanding Contamination; Twenty Years of Simulating Radiological Contamination

A wide variety of simulated contamination methods have been developed by researchers to reproducibly test radiological decontamination methods. Some twenty years ago a method of non-radioactive contamination simulation was proposed at the Idaho National Laboratory (INL) that mimicked the character of radioactive cesium and zirconium contamination on stainless steel. It involved baking the contamination into the surface of the stainless steel in order to 'fix' it into a tenacious, tightly bound oxide layer. This type of contamination was particularly applicable to nuclear processing facilities (and nuclear reactors) where oxide growth and exchange of radioactive materials within the oxide layer became the predominant model for material/contaminant interaction. Additional simulation methods and their empirically derived basis (from a nuclear fuel reprocessing facility) are discussed. In the last ten years the INL, working with the Defense Advanced Research Projects Agency (DARPA) and the National Homeland Security Research Center (NHSRC), has continued to develop contamination simulation methodologies. The most notable of these newer methodologies was developed to compare the efficacy of different decontamination technologies against radiological dispersal device (RDD, 'dirty bomb') type of contamination. There are many different scenarios for how RDD contamination may be spread, but the most commonly used one at the INL involves the dispersal of an aqueous solution containing radioactive Cs-137. This method was chosen during the DARPA projects and has continued through the NHSRC series of decontamination trials and also gives a tenacious 'fixed' contamination. Much has been learned about the interaction of cesium contamination with building materials, particularly concrete, throughout these tests. The effects of porosity, cation-exchange capacity of the material and the amount of dirt and debris on the surface are very important factors. The interaction of the contaminant/substrate with the particular decontamination technology is also very important. Results of decontamination testing from hundreds of contaminated coupons have lead to certain conclusions about the contamination and the type of decontamination methods being deployed. A recent addition to the DARPA initiated methodology simulates the deposition of nuclear fallout. This contamination differs from previous tests in that it has been developed and validated purely to simulate a 'loose' type of contamination. This may represent the first time that a radiologically contaminated 'fallout' stimulant has been developed to reproducibly test decontamination methods. While no contaminant/methodology may serve as a complete example of all aspects that could be seen in the field, the study of this family of simulation methods provides insight into the nature of radiological contamination.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Belgian regulatory framework for decontamination and decommissioning - lessons learned and new initiatives

Belgium can rely on significant experience in the field of decontamination and decommissioning of nuclear facilities. Several projects are ongoing and include research reactors (BR3, Thetis), uranium and MOX fuel fabrication plants (FBFC International, Belgonucleaire), fuel reprocessing facilities (Eurochemic) and radwaste processing facilities (Belgoprocess). Additional projects are expected in the coming years with the planned final shutdown of the oldest nuclear power reactor units. Two national authorities are involved in the decontamination and decommissioning process of nuclear facilities. The FANC (together with its subsidiary Bel V) is concerned for all matters related to nuclear safety and radiation protection, while NIRAS/ONDRAF is concerned for all matters related to radioactive waste and fuel management and financial provisions. These attributions ensure that all safety and material concerns are addressed and that both the licensees and the national authorities bear their own responsibilities. They rely on an existing regulatory framework covering both the procedural and the technical aspects of the decontamination and decommissioning activities. However, opportunities for regulatory improvement were raised after some recent events in Belgium, among which the bankruptcy of a nuclear company producing radioisotopes, involving numerous additional interested parties in a complex judiciary context. Amendments in the current regulations are considered to increase the prerogatives of the authorities regarding the management of radioactive waste by a licensee, the transfer of an operating license from an operator to another, and the general decommissioning strategy of a facility. Furthermore, a dedicated 'waste and decommissioning' working group within WENRA defined new reference levels applying to the decontamination and decommissioning of nuclear facilities. Belgium committed to include these requirements explicitly in its national legislation, even though most of them were already included in the existing decommissioning authorizations. Amendments will cover the safety provisions inherent to the decontamination and decommissioning phase, such as the decommissioning strategy, the qualification of techniques, the experience feedback valorization, the periodic safety reviews, the radioactive waste management, or the final characterization of the sites. Additionally, requirements regarding the authorization process will be detailed, such as the content of the licensee's application file or the structure of the safety report covering the decontamination and decommissioning phase. These changes will contribute to a more secure regulatory framework for all interested parties. (authors)

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Performance evaluation of the ORNL multi-elemental XRF analysis algorithms

Hybrid K-Edge Densitometer (HKED) systems integrate both K-Edge Densitometry (KED) and X-Ray Fluorescence (XRF) analyses to provide accurate rapid, assay results of the uranium and plutonium content of dissolver solution samples from nuclear fuel reprocessing facilities. Introduced for international safeguards applications in the late 1980s, the XRF component of the hybrid analyses is limited to quantification of U and Pu over a narrow range of U:Pu concentration ratios in the vicinity of ≈100. The analysis was further limited regarding the presence of minor actinide components where only a single minor actinide (typically Am) is included in the analysis and then only treated as an interference. The evolving nuclear fuel cycle has created the need to assay more complex dissolver solutions where uranium may no longer be the dominant actinide in the solution and the concentrations of the so called minor actinides (e.g., Th, Np, Am, and Cm) are sufficiently high that they can no longer be treated as impurities and ignored. Extension of the traditional HKED Region of Interest (ROI) based analysis to include these additional actinides is not possible due to the increased complexity of the XRF spectra. Oak Ridge National Laboratory (ORNL) has developed a spectral fitting approach to the HKED XRF measurement with an enhanced algorithm set to accommodate these complex XRF spectra. This report provides a summary of the spectral fitting methodology and examines the performance of these algorithms using data obtained from the ORNL HKED system, as well as data provided by the International Atomic Energy Agency (IAEA) on actual dissolver solutions.

97 MATHEMATICS AND COMPUTING↗

FCRD Advanced Reactor (Transmutation) Fuels Handbook

Transmutation of minor actinides such as Np, Am, and Cm in spent nuclear fuel is of international interest because of its potential for reducing the long-term health and safety hazards caused by the radioactivity of the spent fuel. One important approach to transmutation (currently being pursued by the DOE Fuel Cycle Research & Development Advanced Fuels Campaign) involves incorporating the minor actinides into U-Pu-Zr alloys, which can be used as fuel in fast reactors. U-Pu-Zr alloys are well suited for electrolytic refining, which leads to incorporation rare-earth fission products such as La, Ce, Pr, and Nd. It is, therefore, important to understand not only the properties of U-Pu-Zr alloys but also those of U-Pu-Zr alloys with concentrations of minor actinides (Np, Am) and rare-earth elements (La, Ce, Pr, and Nd) similar to those in reprocessed fuel. In addition to requiring extensive safety precautions, alloys containing U, Pu, and minor actinides (Np and Am) are difficult to study for numerous reasons, including their complex phase transformations, characteristically sluggish phasetransformation kinetics, tendency to produce experimental results that vary depending on the histories of individual samples, rapid oxidation, and sensitivity to contaminants such as oxygen in concentrations below a hundred parts per million. Although less toxic, rare-earth elements such as La, Ce, Pr, and Nd are also difficult to study for similar reasons. Many of the experimental measurements were made before 1980, and the level of documentation for experimental methods and results varies widely. It is, therefore, not surprising that little is known with certainty about U-Pu-Zr alloys, particularly those that also contain minor actinides and rare-earth elements. General acceptance of results commonly indicates that there is only a single measurement for a particular property. This handbook summarizes currently available information about U, Pu, Zr, Np, Am, La, Ce, Pr, and Nd and alloys of two or three of these elements. It contains information about phase diagrams and related information (including phases and phase transformations); heat capacity, entropy, and enthalpy; thermal expansion; and thermal conductivity and diffusivity. In addition to presenting information about materials properties, the handbook attempts to provide information about how well the property is known and how much variation exists between measurements. Although it includes some results from models, its primary focus is experimental data. The Handbook is organized in two sections: one with information about the U-Pu-Zr ternary and one with information about other elements and binary and vi ternary alloys in the U-Np-Pu-Am-La-Ce-Pr-Nd-Zr system. Within each section, information about elements is presented first, followed by information about binary alloys, then information about ternary alloys. The order in which the elements in each alloy are mentioned follows the order in the first sentence of this paragraph. Much of the information on the U-Pu-Zr system repeats information from the FCRD Transmutation Fuels Handbook 2015. Most of the other data has been published elsewhere (although scattered throughout numerous references, some quite obscure); however, some data from Idaho National Laboratory is presented here for the first time. As the FCRD programmatic mission evolves, future editions of this handbook will begin to include other advanced reactor fuel designs and compositions. Hence, the title of the handbook will transition to the Advanced Reactor Fuels Handbook.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Treatment of Problematic Reactive Metal Wastes Using the GeoMelt{sup R} In-Container Vitrification (ICV{sup TM}) Process - 20326

Decommissioning of sodium-cooled reactors and fast reactor technologies has generated a number of reactive metal waste configurations that are problematic to treat and typically lack cost effective treatment methods and disposition options. As a result, Veolia Nuclear Solutions, under contract with Idaho National Laboratory (owned by the U.S. Department of Energy and managed and operated by Battelle Energy Alliance, LLC) demonstrated its GeoMelt{sup R} In-Container Vitrification (ICV){sup TM} technology to safely convert sodium metal to a non-reactive vitrified oxide form. The demonstration project, supported by glass formulation and crucible testing, consisted of a series of ICV{sup TM} melts that processed elemental sodium into stable non-reactive glass. INL is currently implementing GeoMelt{sup R} technology as a means to safely and reliably convert radioactive reactive metal residues that contaminate sodium cooled reactor components into waste forms that comply with existing disposition pathways. Reactive metal wastes require treatment in order to remove the Resource Conservation and Recovery Act (RCRA) reactivity and ignitability characteristics to comply with land disposal restrictions. GeoMelt{sup R}, which is an alternative to other potential treatment approaches, provides a robust approach that chemically converts the reactive metals to an inert oxide while also immobilizing radionuclides in a vitrified waste form with durability equal to or better than vitrified nuclear fuel reprocessing wastes (very robust and inert waste forms). Most other treatment approaches generate hydrogen gas which is problematic. In 2016, Veolia Nuclear Solutions first demonstrated the effectiveness of the GeoMelt{sup R} ICV{sup TM} process in deactivating reactive sodium metal. Crucible, bench-scale, and engineering-scale demonstrations were conducted on several surrogate waste configurations with various ratios of sodium metal and glass formers. Each ratio and configuration demonstrated complete deactivation of the surrogate sodium metal. Follow-on work in 2017 demonstrated the deactivation of reactive sodium by GeoMelt{sup R} ICV{sup TM} at a higher waste loading relative to previously demonstrated work performed in 2016; the higher waste loading optimized glass chemistry while enhancing the economical full-scale treatment of reactive metals. Additionally, follow-on demonstration testing in 2018 and 2019 focused on more complex shapes and other reactive-metals (mocked up Experimental Breeder Reactor II [EBR-II] subassembly, sodium filled heat exchanger, and a can containing sodium potassium alloy) which were all performed at engineering scale. Veolia Nuclear Solutions designed, installed, and commissioned in September 2018, at Perma-Fix Northwest in Richland Washington, a 10-metric ton full-scale GeoMelt unit (GeoMelt{sup R} Richland) for the treatment of reactive metal wastes. As of September 2019, over 900 55-gallon drums containing a total of around 3,500 lb of sodium with low levels of radioactivity have been treated at GeoMelt{sup R} Richland, with resulting glass monoliths disposed at the Nevada National Security Site (NNSS). A full-scale radiological demonstration melt on an actual EBR-II subassembly has also been performed using the full-scale melter in 2019. The GeoMelt{sup R} technology is a proven radioactive waste treatment technology capable of immobilizing radioactive wastes, including bulk rubble such as drums and other steel vessels usually without pretreatment. Utilizing the GeoMelt{sup R} technology to treat reactive metals eliminates pretreatment steps resulting from having to separate the reactive metal from steel containers or jackets as GeoMelt{sup R} can easily operate at temperatures sufficient to melt the steel and expose the reactive metal for treatment. Eliminating handling steps of reactive metals is a significant safety advantage since reactive metals are pyrophoric. The results generated as a part of the 2018-2019 demonstration program are presented in the paper. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Nuclear Safety [Vol. 33, No. 4, October-December 1992]

Nuclear Safety is a review journal that covers significant developments in the field of nuclear safety. Its scope includes the analysis and control of hazards associated with nuclear energy, operations involving fissionable materials, and the products of nuclear fission and their effects on the environment. Primary emphasis is on safety in reactor design, construction, and operation; however, the safety aspects of the entire fuel cycle, including fuel fabrication, spent-fuel processing, nuclear waste disposal, handling of radioisotopes, and environmental effects of these operations, are also treated. Table of Contents for this issue follows. GENERAL SAFETY CONSIDERATIONS: 499 Technical Note: Nuclear Regulatory Commission’s Examination Question Bank System, C. L Jensen and N. L. Skinner; 506 Report on the Specialists’ Meeting on Passive and Active Safety Features of Liquid-Metal Fast Breeder Reactors Organized by the International Atomic Energy Agency at Oarai Engineering Centre of Power Reactor and Nuclear Development Corporation, Japan, November 5-7,1991, S. R. Paranjpe; ACCIDENT ANALYSIS: 514 A Review of Hydrogen Production During Melt/Water Interaction in LWRs, D. F. Fletcher, B. D. Turland, and S. P. A. Lawrence; 535 A Review of the U 3 0 8 -Al Reaction as a Potential Heat Source in Research and Test Reactor Accidents, J. L. Snelgrove; CONTROL AND INSTRUMENTATION: 543 Multilevel Interfaces for Power Plant Control Rooms II: A Preliminary Design Space, K. J. Vicente; DESIGN FEATURES: 549 Twenty-Second DOE/NRC Nuclear Air Cleaning and Treatment Conference, R. R. Bellamy, D. W. Moeller, and M. W. First; 562 Book Review: Safety Assessment of Unit 5 (WWER-440/W-213) of the Greifswald Nuclear Power Station, M. H. Fontana; WASTE AND SPENT FUEL MANAGEMENT: 576 Activities Related to Waste and Spent Fuel Management, M. D. Muhlheim and E. G. Silver; OPERATING EXPERIENCES: 586 Analysis of Corrective Actions Applied to Nuclear Power Plant Operations, A. E. Cross; 593 Reactor Shutdown Experience, Compiled by J. W. Cletcher; 596 Operating U.S. Power Reactors, Compiled by M. D. Muhlheim and E. G. Silver; 609 Non-Commercial Power Operating Experience; 614 World Nuclear Performance, Compiled by M. D. Muhlheim; RECENT DEVELOPMENTS: 623 General Administrative Activities, Compiled by M. D. Muhlheim and E. G. Silver; 635 Reports, Standards, and Safety Guides, D. S. Queener; 639 Proposed Rule Changes as of June 30, 1992; ANNOUNCEMENTS: 513 Fourth International Conference on Nuclear Fuel Reprocessing and Waste Management RECOD '94; 585 International Topical Meeting on Advanced Reactors Safety; 622 International Workshop on Implementation of ALARA at Nuclear Power Plants; 648 Short Course on Nuclear Criticality Safety; 648 8th Topical Meeting on Problems in Reactor Physics MEPhi-VOLGA-93; 643 The Authors; 646 Reviewers of Nuclear Safety, Vol. 33

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

CHARACTERIZATION OF MODIFIED MONOSODIUM TITANATE - AN IMPROVED SORBENT FOR STRONTIUM AND ACTINIDE SEPARATIONS

High-level nuclear waste produced from fuel reprocessing operations at the Savannah River Site (SRS) requires pretreatment to remove {sup 134,137}Cs, {sup 90}Sr, and alpha-emitting radionuclides (i.e., actinides) prior to disposal onsite as low level waste. An inorganic sorbent, monosodium titanate (MST), is currently used to remove {sup 90}Sr and alpha-emitting radionuclides, while a caustic-side solvent extraction process is used for removing {sup 134,137}Cs. A new peroxotitanate material, modified MST, or mMST, has recently been developed and has shown increased removal kinetics and capacity for {sup 90}Sr and alpha-emitting radionuclides compared to the current baseline material, MST. This paper describes recent results focused on further characterization of this material.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗