Iodine immobilization by silver-impregnated granular activated carbon in cementitious systems
Abstract not provided
Li, Dien↗
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Technetium Stabilization in Low-Solubility Sulfide Phases: A Review
We report that technetium contamination remains a major environmental problem at nuclear reprocessing sites, e.g., the Hanford Site, Washington, USA. At these sites, Tc is present in liquid waste destined for immobilization in a waste form or has been released into the subsurface environment. The high environmental risk associated with Tc is due to its long half-life (214 000 years) and the mobility of the oxidized anionic species Tc(VII)O 4 - . Under reducing conditions, TcO 4 - is readily reduced to Tc(IV), which commonly exists as a relatively insoluble and therefore immobile, hydrous Tc-oxide (TcO 2 · n H 2 O). The stability of Tc(IV) sequestered as solid phases depends on the solubility of the solid and susceptibility to reoxidation to TcO 4 - , which in turn depend on the (biogeo)chemical conditions of the environment and/or nuclear waste streams. Unfortunately, the solubility of crystalline TcO 2 or amorphous TcO 2 ·H 2 O is still above the maximum contaminant level (MCL) established by the U.S. EPA (900 pCi/L), and the kinetics of TcO 2 oxidative dissolution can be on the order of days to years. In addition to oxygen, sulfur can form complexes that significantly affect the adsorption, solubility, and reoxidation potential of Tc, especially Tc(IV). The principal technetium sulfides are TcS 2 and Tc 2 S 7 , but much less is known about the mechanisms of formation, stabilization, and reoxidation of Tc-sulfides. A common assumption is that sulfides are less soluble than their oxyhydrous counterparts. Determination of the molecular structure of Tc 2 S 7 in particular has been hampered by the propensity of this phase to precipitate as an amorphous substance. Recent work indicates that the oxidation state of Tc in Tc 2 S 7 is Tc(IV), in apparent contradiction to its nominal stoichiometry. Technetium is relatively immobile in reduced sediments and soils, but in many cases the exact sink for Tc has not been identified. Experiments and modeling have demonstrated that both abiotic and biologic mechanisms can exert strong controls on Tc mobility and that Tc binding or uptake into sulfide phases can occur. These and similar investigations also show that extended exposure to oxidizing conditions results in transformation of sulfide-stabilized Tc(IV) to a Tc(IV)O 2 -like phase without formation of measurable dissolved TcO 4 - , suggesting a solid-state transformation in which Tc(IV)-associated sulfide is preferentially oxidized before the Tc(IV) cation. This transformation of Tc(IV)-sulfides to Tc(IV)-oxides may be the main process that limits remobilization of Tc as Tc(VII)O 4 - . The efficacy of the final waste form to retain Tc also strongly depends on the ability of oxidizing species to enter the waste and convert Tc(IV) to Tc(VII). Finally, many waste form designs are reducing (e.g., cementitious waste forms such as salt stone) and, therefore, attempt to restrict access of oxidizing species such that diffusion is the rate-limiting step in remobilization of Tc.
12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
Implementing Geological Disposal of Radioactive Waste Technology Platform From the Strategic Research Agenda to its Deployment - 12015
Several European waste management organizations (WMOs) have initiated a technology platform for accelerating the implementation of deep geological disposal of radioactive waste in Europe. The most advanced waste management programmes in Europe (i.e. Finland, Sweden, and France) have already started or are prepared to start the licensing process of deep geological disposal facilities within the next decade. A technology platform called Implementing Geological Disposal of Radioactive Waste Technology Platform (IGD-TP) was launched in November 2009. A shared vision report for the platform was published stating that: 'Our vision is that by 2025, the first geological disposal facilities for spent fuel, high-level waste, and other long-lived radioactive waste will be operating safely in Europe'. In 2011, the IGD-TP had eleven WMO members and about 70 participants from academia, research, and the industry committed to its vision. The IGD-TP has started to become a tool for reducing overlapping work, to produce savings in total costs of research and implementation and to make better use of existing competence and research infrastructures. The main contributor to this is the deployment of the IGD-TP's newly published Strategic Research Agenda (SRA). The work undertaken for the SRA defined the pending research, development and demonstration (RD and D) issues and needs. The SRA document describing the identified issues that could be worked on collaboratively was published in July 2011. It is available on the project's public web site (www.igdtp.eu). The SRA was organized around 7 Key Topics covering the Safety Case, Waste forms and their behaviour, Technical feasibility and long-term performance of repository components, Development strategy of the repository, Safety of construction and operations, Monitoring, and Governance and stakeholder involvement. Individual Topics were prioritized within the Key Topics. Cross-cutting activities like Education and Training or Knowledge Management as well as activities remaining specific for the WMOs were as well identified in the document. For example, each WMO has to develop their own waste acceptance rules, and plan for the economics and the funding of their waste management programmes. The challenge at hand for the IGD-TP is to deploy the SRA. This is carried out by agreeing on a Deployment Plan (DP) that guides organizing the concrete joint activities between the WMOs and the other participants of the IGD-TP. The first DP points out the coordinated RD and D projects and other activities that need to be launched to produce these results over the next four to five years (by the end of 2016). The DP also describes general principles for how the joint work can be organised and funded. (authors)
12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
Performance Assessment for the E-Area Low-Level Radioactive Waste Disposal Facility at the Savannah River Site: Appendix H
This section provides supporting material for the development of DU-specific final inventory limits for the GW pathways for every generic waste form and SWF parent radionuclide requiring an inventory limit. The final inventory limits are based on nominal PA transport simulations using PORFLOW as reported in Chapter 5. The nominal PA settings represent the compliance case where some modeling parameter settings are defined based on conservative (pessimistically leaning) arguments. In the overall computational approach employed in this PA, a multitiered radionuclide screening process is adopted as discussed in Chapter 2, Section 2.3.7. In the multitiered process, the initial list of 1,252 parent radionuclides is shortened substantially using conservative, but simple, transport models, along with a reasonably low cutoff criterion of 0.1% SOF value. Multidimensional PORFLOW flow and transport modeling is employed for every parent radionuclide that failed the GW screening. The generic waste form limits represent Tier-3 analyses, while Tier-4 analyses are employed for SWF limits, where warranted.
12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
Functionalized ultra-porous titania nanofiber membranes as nuclear waste separation and sequestration scaffolds for nuclear fuels recycle.
Advanced nuclear fuel cycle concept is interested in reducing separations to a simplified, one-step process if possible. This will benefit from the development of a one-step universal getter and sequestration material so as a simplified, universal waste form was proposed in this project. We have developed a technique combining a modified sol-gel chemistry and electrospinning for producing ultra-porous ceramic nanofiber membranes with controllable diameters and porous structures as the separation/sequestration materials. These ceramic nanofiber materials have been determined to have high porosity, permeability, loading capacity, and stability in extreme conditions. These porous fiber membranes were functionalized with silver nanoparticles and nanocrystal metal organic frameworks (MOFs) to introduce specific sites to capture gas species that are released during spent nuclear fuel reprocessing. Encapsulation into a durable waste form of ceramic composition was also demonstrated.
Liu, Haiqing↗
Screening of Additional Candidate Low-Temperature Glasses for Technetium Recovered from Hanford Effluent Management Facility Evaporator Bottoms
In this annex to a previously reported study, a series of laboratory screening tests was conducted to identify low-temperature glasses that have significant potential for use in disposition of technetium from a Hanford Tank Waste Treatment & Immobilization Plant (WTP) secondary liquid waste stream. Specifically, a glass waste form is sought that would be suitable for on-site disposition of technetium, salts, and other species in a Tc-rich stream recovered by ion exchange from the future Effluent Management Facility (EMF) evaporator concentrate. In the current study, several additional candidate glasses were identified, and testing of previous candidates was extended to include the Toxicity Characteristic Leaching Procedure (TCLP). In non-radioactive testing with rhenium surrogate, new formulations incorporated a simulated ion exchange eluate at temperatures below 750 °C to produce an amorphous, or mixed crystalline-amorphous, product. Incorporation of technetium (NaTcO 4 )-containing simulated eluate was evaluated for two of these glasses. Technetium was not retained well in these glasses, confounding the previous conclusion that Tc volatilization during vitrification can be reduced by appropriate selection of low-temperature glasses. Preliminary data for additional low-temperature glass compositions and recommendations for future work are provided. This report is a deliverable associated with requisition 55068-004-03 NFE-17-0020 "Candidate Low-T Glass Waste Forms for EMF Bottoms On-Site Disposition Alternative."
12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
Final Report Start-Up and Commissioning Tests on the DuraMelter 1200 HLW Pilot Melter System Using AZ-101 HLW Simulants
This document provides the final report on data and results obtained from commissioning tests performed on the one-third scale DuraMelter{trademark} 1200 (DM 1200) HLW Pilot Melter system that has been installed at VSL with an integrated prototypical off-gas treatment system. That system has replaced the DM1000 system that was used for HLW throughput testing during Part BI [1]. Both melters have similar melt surface areas (1.2 m{sup 2}) but the DM1200 is prototypical of the present RPP-WTP HLW melter design whereas the DM1000 was not. These tests were performed under a corresponding RPP-WTP Test Specification and associated Test Plan. This report is a followup to the previously issued Preliminary Data Summary Report. The DM1200 system will be used for testing and confirmation of basic design, operability, flow sheet, and process control assumptions as well as for support of waste form qualification and permitting. This will include data on processing rates, off-gas treatment system performance, recycle stream compositions, as well as process operability and reliability. Consequently, this system is a key component of the overall HLW vitrification development strategy. The results presented in this report are from the initial series of short-duration tests that were conducted to support the start-up and commissioning of this system prior to conducting the main body of development tests that have been planned for this system. These tests were directed primarily at system 'debugging,' operator training, and procedure refinement. The AZ-101 waste simulant and glass composition that was used for previous testing was selected for these tests.
12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
Effect of decades of corrosion on the microstructure of altered glasses and their radiation stability
Understanding the microstructural evolution of glasses during their interaction with water and radiation is of fundamental importance in addressing the corrosion of nuclear waste forms under geological disposal conditions. Here we report the results of more than 21 years of corrosion of two borosilicate glasses showing the formation of mesoporous C–S–H gels in Ca-bearing glasses and a mainly microporous microstructure in Al-bearing glasses. These porous corroded glasses were then irradiated with heavy ions to simulate the effects of recoil nucleus damage and monitored in real time using transmission electron microscopy with in situ ion irradiation. The ballistic collisions remarkably healed the porous corroded glasses to a pore-free homogeneous microstructure. Besides providing new insights and predictions about how doped glasses and actual waste forms may evolve under corrosion and irradiation, the results highlight the non-universal nature of the existing corrosion models and the important role that the glass composition and radiation damage play in the evolution of the microstructure during corrosion.
36 MATERIALS SCIENCE↗
Development of pyro-processing technology at CRIEPI for carving out the future of nuclear fuel cycle
Pyro-processing has been attracting increasing attention as a promising candidate as an advanced nuclear fuel cycle technology. It provides economic advantage as well as reduction in proliferation risk and burden of long live radioactive waste, especially when it is combined with advanced fuels such as metallic or nitride fuel which gives excellent burning efficiency of minor actinides (MA). CRIEPI has been developing pyro-processing technology since late eighties with both domestic and international collaborations. In the early stage, electrochemical and thermodynamic properties in LiCl-KCl eutectic melt, and fundamental feasibility of core technology like electrorefining were chiefly investigated. Currently, stress in the process chemistry development is also placed on supporting technologies, such as treatment of anode residue and high temperature distillation for cathode product from electrorefining, and so on. Waste treatment process development, such as studies on adsorption behavior of various FP elements into zeolite and conditions for the fabrication of glass-bonded sodalite waste form, are steadily improved as well. In parallel, dedicated pyro-processing equipment such as zeolite column for treatment of spent electro-refiner salt is currently in progress. Recently, an integrated engineering-scale fuel cycle tests were performed funded by Japanese government (MEXT) as an important step before proceeding to large scale hot demonstration of pyro-processing. Oxide fuels can be readily introduced into the pyro-processing by reducing them to metals by adoption of electrochemical reduction technique. Making use of this advantage, the pyro-processing is currently under preliminary evaluation for its applicability to the treatment of the corium, mainly consisting of (U,Zr)O{sub 2}, formed in different composition during the accident of the Fukushima Daiichi nuclear power plant. (authors)
11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
Bubbling Behavior in a Waste Glass Melter
Legacy tank waste from five decades of plutonium production at the Hanford Site during the Cold War will be vitrified into a stable waste form for disposal. A Waste Treatment Plant, currently under construction, houses Joule heated ceramic-lined waste glass melters wherein radioactive waste will be combined with glass formers to produce borosilicate glass. Through testing conducted in pilot-scale melters with surrogate waste, as well as operational experience at other sites, it has been demonstrated that the use of bubblers can dramatically improve the glass production rate. However, knowledge of the bubble dynamics in the molten glass is necessary for prediction and design of improved melting processes. A computational fluid dynamics model of the melter has been developed to investigate the processes affecting feed melt rate. The model shows that the convection currents within the melt pool due to Joule heating supplied by the electrodes are enhanced by forced air bubbling. In this paper, parameters influencing the formation and rise of a bubble stream in a viscous liquid are investigated. Experimental data and observations from laboratory and pilot-scale testing are integrated with first principles to develop a set of equations that form a mechanistic bubbling model to be incorporated into the melter model.
12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
Assessment of Geochemical Environment for the Proposed INL Remote-Handled Low-Level Waste Disposal Facility
Conservative sorption parameters have been estimated for the proposed Idaho National Laboratory Remote-Handled Low-Level Waste Disposal Facility. This analysis considers the influence of soils, concrete, and steel components on water chemistry and the influence of water chemistry on the relative partitioning of radionuclides over the life of the facility. A set of estimated conservative distribution coefficients for the primary media encountered by transported radionuclides has been recommended. These media include the vault system, concrete-sand-gravel mix, alluvium, and sedimentary interbeds. This analysis was prepared to support the performance assessment required by U.S. Department of Energy Order 435.1, 'Radioactive Waste Management.' The estimated distribution coefficients are provided to support release and transport calculations of radionuclides from the waste form through the vadose zone. A range of sorption parameters are provided for each key transport media, with recommended values being conservative. The range of uncertainty has been bounded through an assessment of most-likely-minimum and most-likely-maximum distribution coefficient values. The range allows for adequate assessment of mean facility performance while providing the basis for uncertainty analysis.
12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
Technetium Incorporation in Glass for the Hanford Tank Waste Treatment and Immobilization Plant
A priority of the United States Department of Energy (U.S. DOE) is to dispose of nuclear wastes accumulated in 177 underground tanks at the Hanford Nuclear Reservation in eastern Washington State. These nuclear wastes date from the Manhattan Project of World War II and from plutonium production during the Cold War. The DOE plans to separate high-level radioactive wastes from low activity wastes and to treat each of the waste streams by vitrification (immobilization of the nuclides in glass) for disposal. The immobilized low-activity waste will be disposed of here at Hanford and the immobilized high-level waste at the national geologic repository. Included in the inventory of highly radioactive wastes is large volumes of 99Tc (~9 × 10E2 TBq or ~2.5 × 104 Ci or ~1500 kg). A problem facing safe disposal of Tc-bearing wastes is the processing of waste feed into in a chemically durable waste form. Technetium incorporates poorly into silicate glass in traditional glass melting. It readily evaporates during melting of glass feeds and out of the molten glass, leading to a spectrum of high-to-low retention (ca. 20 to 80%) in the cooled glass product. DOE-ORP currently has a program at Pacific Northwest National Laboratory (PNNL), in the Department of Materials Science and Engineering at Rutgers University and in the School of Mechanical and Materials Engineering at Washington State University that seeks to understand aspects of Tc retention by means of studying Tc partitioning, molten salt formation, volatilization pathways, and cold cap chemistry. Another problem involves the stability of Tc in glass in both the national geologic repository and on-site disposal after it has been immobilized. The major environmental concern with 99Tc is its high mobility in addition to a long half-life (2.1×105 yrs). The pertechnetate ion (TcO4-) is highly soluble in water and does not adsorb well onto the surface of minerals and so migrates nearly at the same velocity as groundwater. Long-term corrosion of glass waste forms is an area of current interest to the DOE, but attention to the release of Tc from glass has been little explored. It is expected that the release of Tc from glass should be highly dependent on the local glass structure as well as the chemistry of the surrounding environment, including groundwater pH. Though the speciation of Tc in glass has been previously studied, and the Tc species present in waste glass have been previously reported, environmental Tc release mechanisms are poorly understood. The recent advances in Tc chemistry that have given rise to an understanding of incorporation in the glass giving rise to significantly higher single-pass retention during vitrification are presented. Additionally, possible changes to the baseline flowsheet that allow for relatively minor volumes of Tc reporting to secondary waste treatment will be discussed.
Kruger, Albert A.↗
Fukushima Nuclear Crisis Recovery: A Modular Water Treatment System Deployed in Seven Weeks - 12489
On March 11, 2011, the magnitude 9.0 Great East Japan earthquake, Tohoku, hit off the Fukushima coast of Japan. This was one of the most powerful earthquakes in recorded history and the most powerful one known to have hit Japan. The ensuing tsunami devastated a huge area resulting in some 25,000 persons confirmed dead or missing. The perfect storm was complete when the tsunami then found the four reactor, Fukushima-Daiichi Nuclear Station directly in its destructive path. While recovery systems admirably survived the powerful earthquake, the seawater from the tsunami knocked the emergency cooling systems out and did extensive damage to the plant and site. Subsequent hydrogen generation caused explosions which extended this damage to a new level and further flooded the buildings with highly contaminated water. Some 2 million people were evacuated from a fifty mile radius of the area and evaluation and cleanup began. Teams were assembled in Tokyo the first week of April to lay out potential plans for the immediate treatment of some 63 million gallons (a number which later exceeded 110 million gallons) of highly contaminated water to avoid overflow from the buildings as well as supply the desperately needed clean cooling water for the reactors. A system had to be deployed with a very brief cold shake down and hot startup before the rainy season started in early June. Joined by team members Toshiba (oil removal system), AREVA (chemical precipitation system) and Hitachi-GE (RO system), Kurion (cesium removal system following the oil separator) proposed, designed, fabricated, delivered and started up a one of a kind treatment skid and over 100 metric tons of specially engineered and modified Ion Specific Media (ISM) customized for this very challenging seawater/oil application, all in seven weeks. After a very short cold shake down, the system went into operation on June 17, 2011 on actual waste waters far exceeding 1 million Bq/mL in cesium and many other isotopes. One must remember that, in addition to attempting to do isotope removal in the competition of seawater (as high as 18,000 ppm sodium due to concentration), some 350,000 gallons of turbine oil was dispersed into the flooded buildings as well. The proposed system consisted of a 4 guard vessel skid for the oil and debris, 4 skids containing 16 cesium towers in a lead-lag layout with removable vessels (sent to an interim storage facility), and a 4 polishing vessel skid for iodine removal and trace cesium levels. At a flow rate of at least 220 gallons per minute, the system has routinely removed over 99% of the cesium, the main component of the activity, since going on line. To date, some 50% of the original activity has been removed and stabilized and cold shutdown of the plant was announced on December 10, 2011. In March and April alone, 10 cubic feet of Engineered Herschelite was shipped to Seabrook Nuclear Power Plant, NPP, to support the April 1, 2011 outage cleanup; 400 cubic feet was shipped to Oak Ridge National Laboratory (ORNL) for strontium (Sr-90) ground water remediation; and 6000 cubic feet (100 metric tons, MT, or 220,400 pounds) was readied for the Fukushima Nuclear Power Station with an additional 100 MT on standby for replacement vessels. This experience and accelerated media production in the U.S. bore direct application to what was to soon be used in Fukushima. How such a sophisticated and totally unique system and huge amount of media could be deployable in such a challenging and changing matrix, and in only seven weeks, is outlined in this paper as well as the system and operation itself. As demonstrated herein, all ten major steps leading up to the readiness and acceptance of a modular emergency technology recovery system were met and in a very short period of time, thus utilizing three decades of experience to produce and deliver such a system literally in seven weeks: - EPRI - U.S. Testing and Experience Leading to Introduction to EPRI - Japan and Subsequently TEPCO Emergency Meetings - Three Mile Island (TMI) Media and Vitrification Experience by PNNL - Commercial Nuclear Power Plant Media Experience (including long term Cs removal) - DOE Low Active Waste (LAW) and High Level Waste (HLW) in High Salt and pH Conditions Media and Vitrification Experience - National Laboratory (e.g. Oak Ridge National Laboratory, ORNL) Ground Water Media Experience - Gulf Oil Spill Media Experience in Seawater - All Media Had to be Fully Tested at High Rad Levels in Seawater and Oil Before Arriving in Japan - Final Waste Form and Disposal Experience (e.g., vitrification) - 100 Metric Tons (6000 cubic feet or 220,400 pounds) of Media had to be Immediately Available with the same amount in production as replacement media. [To date, for 2011, 400 MT of media have been prepared for Japan alone.] - Remote Operation, Modular Water Treatment Equipment Design and Fabrication in both Commercial NPP and DOE Canyon Operations. (authors)
12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
Disposal Systems Evaluation Framework DSEF User Manual (V.3.0)
The Disposal Systems Evaluation Framework (DSEF) has been developed at Lawrence Livermore National Laboratory (LLNL) to formalize and facilitate the development and documentation of repository conceptual design options for a range of waste forms, geologic environments, repository design concepts, and repository operating modes. DSEF is one component of the Engineered Barrier System (EBS) family of work packages at several national laboratories led by Sandia National Laboratories (SNL), in support of the DOE Office of Nuclear Energy, specifically of the Used Fuel Disposition (UFD) Campaign within the Office of Used Nuclear Fuel Disposition Research and Development (NE-53). DSEF is a knowledge management system that allows the user to intelligently access and draw data from a case library of hundreds of completed thermal analyses (currently 721 cases in the library), and draw input from databases of material properties and repository development cost data (currently the data in these databases are drawn from more than 100 references). The core functionality of DSEF is provided by a Microsoft Office Excel 2010 workbook with macros and form controls that create a structured environment and walk the user through the steps of creating the input data required to perform disposal system evaluations internally and by interfacing with external programs. The user can choose to work with built-in data from the case library of previous analysis cases, from the material property databases, or can define their own input descriptions and data. DSEF uses the Excel worksheet protection (implemented on a sheet by sheet basis) to prevent inadvertent over-writing of formulas with data. When worksheet protection is enabled, the user can see all underlying formulas, and enter data in unprotected cells (the unprotected cells generally correspond to the yellow highlighted cells). Worksheet protection also prevents restructuring the files (adding or deleting rows or columns) and changing the formatting, as well as preventing access to the Visual Basic Editor to prevent modification of the macros. If the user needs to modify the worksheet structure, formulas, or macros, they can contact LLNL to get the password to unprotect the worksheets. However, care should be taken in making any modifications, since the macros and formulas are dependent in some cases on the current structure, range names, and macro subroutines DSEF is set up to retrieve the results of external thermal analysis program runs, summarize them graphically, and provide a template for adding the new results to the Case Library. The Case Library worksheet in DSEF is set up to create a Case Library data record for each new analysis case, at the top of the list of prior cases. Therefore, a separate DSEF file (with unique name) should be saved for each run that is to be archived. Users should submit a copy of their DSEF files to LLNL so that their results can be added to the overall Case Library and made available to other laboratories and stakeholders. LLNL will maintain the DSEF Case Library and make the most current files available on the SNL SharePoint site. The Revision History sheet documents the file evolution. One of the key objectives of DSEF is to allow the user to compare the results of thermal analyses to the thermal constraints of the design components. These comparisons can then be used to consider design, layout, and operating mode modifications to find combinations that can meet the thermal constraints for a given combination of waste form, geologic medium, surface storage time, and system concept of operation.
12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
Synthesis, Structure Elucidation, and Redox Properties of [superscript 99]Tc Complexes of Lacunary Wells-Dawson Polyoxometalates: Insights into Molecular [superscript 99]Tc-Metal Oxide Interactions
The isotope {sup 99}Tc ({beta}{sub max}, 293.7; half-life, 2.1 x 10{sup 5} years) is an abundant product of uranium-235 fission in nuclear reactors and is present throughout the radioactive waste stored in underground tanks at the Hanford and Savannah River sites. Understanding and controlling the extensive redox chemistry of {sup 99}Tc is important in identifying tunable strategies to separate {sup 99}Tc from spent fuel and from waste tanks and, once separated, to identify and develop an appropriately stable waste form for {sup 99}Tc. Polyoxometalates (POMs), nanometer-sized models for metal oxide solid-state materials, are used in this study to provide a molecular level understanding of the speciation and redox chemistry of incorporated {sup 99}Tc. In this study, {sup 99}Tc complexes of the ({alpha}{sub 2}-P{sub 2}W{sub 17}O{sub 61}){sup 10-} and ({alpha}{sub 1}-P{sub 2}W{sub 17}O{sub 61}){sup 10-} isomers were prepared. Ethylene glycol was used as a 'transfer ligand' to minimize the formation of TcO{sub 2} {center_dot} xH{sub 2}O. The solution structures, formulations, and purity of TcVO({alpha}{sub 1}/{alpha}{sub 2}-P{sub 2}W{sub 17}O{sub 61}){sup 7-} were determined by multinuclear NMR. X-ray absorption spectroscopy of the complexes is in agreement with the formulation and structures determined from {sup 31}P and {sup 183}W NMR. Preliminary electrochemistry results are consistent with the EXAFS results, showing a facile reduction of the TcVO({alpha}{sub 1}-P{sub 2}W{sub 17}O{sub 61}){sup 7-} species compared to the TcVO({alpha}{sub 2}-P{sub 2}W{sub 17}O{sub 61}){sup 7-} analog. The {alpha}{sub 1} defect is unique in that a basic oxygen atom is positioned toward the {alpha}{sub 1} site, and the Tc{sup V}O center appears to form a dative metal-metal bond with a framework W site. These attributes may lead to the assistance of protonation events that facilitate reduction. Electrochemistry comparison shows that the ReV analogs are about 200 mV more difficult to reduce in accordance with periodic trends.
11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
Incorporation of Technetium into Spinel Ferrites
Technetium ( 99 Tc) is a problematic fission product for the long-term disposal of nuclear waste due to its long half-life, high fission yield, and to the environmental mobility of pertechnetate, the stable species in aerobic environments. One approach to preventing 99 Tc contamination is using sufficiently durable waste forms. We report the incorporation of technetium into a family of synthetic spinel ferrites that have environmentally durable natural analogs. A combination of X-ray diffraction, X-ray absorption fine structure spectroscopy, and chemical analysis reveals that Tc(IV) replaces Fe(III) in octahedral sites and illustrates how the resulting charge mismatch is balanced. When a large excess of divalent metal ions is present, the charge is predominantly balanced by substitution of Fe(III) by M(II). When a large excess of divalent metal ions is absent, the charge is largely balanced by creation of vacancies among the Fe(III) sites (maghemitization). In most samples, Tc is present in Tc-rich regions rather than being homogeneously distributed.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Temperature-dependent void formation and growth at ion-irradiated nanocrystalline CeO 2 –Si interfaces
Ceria is a thermally stable ceramic that has numerous applications in the nuclear industry, including use in nuclear fuels and waste forms. Recently, interest has surged in nanostructured ceria due to its increased mechanical properties and electronic conductivity in comparison with bulk ceria and its ability to self-heal in response to energetic ion bombardment. Here, nanocrystalline ceria thin films grown over a silicon substrate are irradiated to fluences of up to ~4 × 10 16 ions/cm 2 under different irradiation conditions: with differing ion species (Si + and Ni + ), different ion energies (1.0–1.5 MeV), and at varying temperatures (160–600 K). Finally, while the nanocrystalline ceria is found to exhibit exceptional radiation resistance under all tested conditions, severe ion irradiation-induced mixing, void formation, and void growth are observed at the ceria/silicon interface, with the degree of damage proving to be temperature dependent.
Environmental Molecular Sciences Laboratory↗
Iodosodalite synthesis with hot isostatic pressing of precursors produced from aqueous and hydrothermal processes
Iodosodalite powders were synthesized using aqueous and hydrothermal methods, with or without sodium borosilicate glass binders, and then hot isostatically pressed (HIP) at 900 ? and 175 MPa for 3 h to convert into waste forms. After HIPing, the structures, compositions, morphologies, porosities, and leach rates of the aqueous and hydrothermally produced iodosodalite samples were compared. X-ray diffraction patterns of HIPed samples showed that iodosodalite remained as the dominant phase. However, the fraction of the iodosodalite phase decreased after HIPing, indicating decomposition of the iodosodalite structure during the HIP process. Scanning electron microscopy and chemical imaging on the cross sections of HIPed samples showed homogeneous elemental distribution for aqueous-grown iodosodalite, whereas hydrothermally grown iodosodalite samples had more heterogeneity and porosity. The densities of HIPed samples with more glass binder were generally higher than sampled HIPed without binder. The leach tests on samples containing 20 mass% glass binder showed that the iodine dissolution rate of HIPed hydrothermally grown iodosodalite was about 4 times higher than iodosodalite by aqueous method. This study provides alternative techniques for immobilizing iodine-streams in iodosodalite waste forms.
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗