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Sample records for actinide waste forms

  1. Actinide Waste Forms and Radiation Effects

    Ewing, R. C.; Weber, W. J.

    Over the past few decades, many studies of actinides in glasses and ceramics have been conducted that have contributed substantially to the increased understanding of actinide incorporation in solids and radiation effects due to actinide decay. These studies have included fundamental research on actinides in solids and applied research and development related to the immobilization of the high level wastes (HLW) from commercial nuclear power plants and processing of nuclear weapons materials, environmental restoration in the nuclear weapons complex, and the immobilization of weapons-grade plutonium as a result of disarmament activities. Thus, the immobilization of actinides has become a pressing issue for the twenty-first century (Ewing, 1999), and plutonium immobilization, in particular, has received considerable attention in the USA (Muller et al., 2002; Muller and Weber, 2001). The investigation of actinides and

  2. Pyrochlore as nuclear waste form. Actinide uptake and chemical stability

    Radioactive waste is generated by many different technical and scientific applications. For the past decades, different waste disposal strategies have been considered. Several questions on the waste disposal strategy remain unanswered, particularly regarding the long-term radiotoxicity of minor actinides (Am, Cm, Np), plutonium and uranium. These radionuclides mainly arise from high level nuclear waste (HLW), specific waste streams or dismantled nuclear weapons. Although many countries have opted for the direct disposal of spent fuel, from a scientific and technical point of view it is imperative to pursue alternative waste management strategies. Apart from the vitrification, especially for trivalent actinides and Pu, crystalline ceramic waste forms are considered. In contrast to glasses, crystalline waste forms, which are chemically and physically highly stable, allow the retention of radionuclides on well-defined lattice positions within the crystal structure. Besides polyphase ceramics such as SYNROC, single phase ceramics are considered as tailor made host phases to embed a specific radionuclide or a specific group. Among oxidic single phase ceramics pyrochlores are known to have a high potential for this application. This work examines ZrO2 based pyrochlores as potential nuclear waste forms, which are known to show a high aqueous stability and a high tolerance towards radiation damage. This work contributes to (1) understand the phase stability field of pyrochlore and consequences of non-stoichiometry which leads to pyrochlores with mixed cationic sites. Mixed cationic occupancies are likely to occur in actinide-bearing pyrochlores. (2) The structural uptake of radionuclides themselves was studied. (3) The chemical stability and the effect of phase transition from pyrochlore to defect fluorite were probed. This phase transition is important, as it is the result of radiation damage in ZrO2 based pyrochlores. ZrO2 - Nd2O3 pellets with pyrochlore and defect

  3. Pyrochlore as nuclear waste form. Actinide uptake and chemical stability

    Finkeldei, Sarah Charlotte

    2015-07-01

    Radioactive waste is generated by many different technical and scientific applications. For the past decades, different waste disposal strategies have been considered. Several questions on the waste disposal strategy remain unanswered, particularly regarding the long-term radiotoxicity of minor actinides (Am, Cm, Np), plutonium and uranium. These radionuclides mainly arise from high level nuclear waste (HLW), specific waste streams or dismantled nuclear weapons. Although many countries have opted for the direct disposal of spent fuel, from a scientific and technical point of view it is imperative to pursue alternative waste management strategies. Apart from the vitrification, especially for trivalent actinides and Pu, crystalline ceramic waste forms are considered. In contrast to glasses, crystalline waste forms, which are chemically and physically highly stable, allow the retention of radionuclides on well-defined lattice positions within the crystal structure. Besides polyphase ceramics such as SYNROC, single phase ceramics are considered as tailor made host phases to embed a specific radionuclide or a specific group. Among oxidic single phase ceramics pyrochlores are known to have a high potential for this application. This work examines ZrO{sub 2} based pyrochlores as potential nuclear waste forms, which are known to show a high aqueous stability and a high tolerance towards radiation damage. This work contributes to (1) understand the phase stability field of pyrochlore and consequences of non-stoichiometry which leads to pyrochlores with mixed cationic sites. Mixed cationic occupancies are likely to occur in actinide-bearing pyrochlores. (2) The structural uptake of radionuclides themselves was studied. (3) The chemical stability and the effect of phase transition from pyrochlore to defect fluorite were probed. This phase transition is important, as it is the result of radiation damage in ZrO{sub 2} based pyrochlores. ZrO{sub 2} - Nd{sub 2}O{sub 3} pellets

  4. Peculiarities of phase formation in synthesis of actinide waste forms

    The phase formation processes by synthesis of the materials with the zirconolite and pyrochlore structure are studied through the methods of the x-ray phase analysis and electron microscopy with the purpose of optimizing the conditions for production of the matrices, used for immobilization of the actinide-containing wastes. It is established, that 20 hours are required for achieving the equilibrium in the CaO-TiO2-ZrO2 system at 1300 deg C and 5 hours - at 1450-1550 deg C. More than 20 hours are required for achieving the equilibrium in the Gd2O3-TiO2 system at 1100 deg C, less than 20 hours at 1200 deg C, about 1 hour - at 1300 deg C and less than 1 hour - at 1400-1550 deg C. The slowest phase formation processes take place in the Gd2O3-ZrO2 system, whereby at 1550 deg C no complete synthesis was observed even during 48 hours. The products of reactions, performed at lower temperatures or durations, contained the components of the initial charge along with the target phases with the zirconolite or pyrochlore structure

  5. Alloy waste forms for metal fission products and actinides isolated by spent nuclear fuel treatment

    Waste form alloys are being developed at Argonne National Laboratory for the disposal of remnant metallic wastes from an electrometallurgical process developed to treat spent nuclear fuel. This metal waste form consists of the fuel cladding (stainless steel or Zircaloy), noble metal fission products (e.g., Ru, Pd, Mo and Tc), and other metallic wastes. The main constituents of the metal waste stream are the cladding hulls (85 to 90 wt%); using the hulls as the dominant alloying component minimizes the overall waste volume as compared to vitrification or metal encapsulation. Two nominal compositions for the waste form are being developed: (1) stainless steel-15 wt% zirconium for stainless steel-clad fuels and (2) zirconium-8 wt% stainless steel for Zircaloy-clad fuels. The noble metal fission products are the primary source of radiation in the metal waste form. However, inclusion of actinides in the metal waste form is being investigated as an option for interim or ultimate storage. Simulated waste form alloys were prepared and analyzed to determine the baseline alloy microstructures and the microstructural distribution of noble metals and actinides. Corrosion tests of the metal waste form alloys indicate that they are highly resistant to corrosion

  6. Fundamental thermodynamics of actinide-bearing mineral waste forms

    In September 2000, the US and Russia reached an agreement to jointly disposition roughly 68 metric tons of weapons usable plutonium. (Agreement 2000) In Russia, 34 metric tonnes of weapons-grade plutonium will be dispositioned by burning the plutonium as mixed oxide (MOX) fuel. In the US, 25 metric tons of plutonium recovered from pits and clean metal will likewise be dispositioned by burning as mixed oxide (MOX) fuel and about 9 metric tonnes of plutonium stored throughout the DOE complex will be dispositioned by immobilization in a ceramic which will then be encapsulated in high-level waste (HLW) glass. In all cases, the plutonium will be made equal to or less attractive for reuse in nuclear weapons than the much larger and growing inventory of plutonium in spent nuclear fuel. This threshold of unattractiveness is commonly referred to as the ''spent fuel standard.'' In the US, the final products from plutonium disposition, irradiated fuel and ceramic encapsulated HLW, will be emplaced in the Federal Waste Repository, which is assumed to be Yucca Mountain. The ceramic form selected for the disposition of plutonium is composed of a series of titanate-based phases which are generally referred to as SYNROC (short for Synthetic Rock). The particular formulation that was selected is composed of about 80 vol % pyrochlore, about 15 vol % brannerite, and about 5 vol % rutile. If impurities are present in the PuO2 feed material, about a half a dozen other phases can also form. The most common of these are zirconolite and a silicate glass. A screening process conducted in 1995, resulted in the selection of borosilicate glasses and titanate-based ceramics (e.g. SYNROCs) as the best available options for immobilization of plutonium. In 1998, a pyrochlore-rich ceramic form was selected in preference to a boro-silicate glass form. More information about the development and selection of the ceramic formulation can be found in the Plutonium Immobilization Program's Baseline

  7. Fundamental Thermodynamics of Actinide-Bearing Mineral Waste Forms - Final Report

    Williamson, Mark A.; Ebbinghaus, Bartley B.; Navrotsky, Alexandra

    2001-03-01

    The end of the Cold War raised the need for the technical community to be concerned with the disposition of excess nuclear weapon material. The plutonium will either be converted into mixed-oxide fuel for use in nuclear reactors or immobilized in glass or ceramic waste forms and placed in a repository. The stability and behavior of plutonium in the ceramic materials as well as the phase behavior and stability of the ceramic material in the environment is not well established. In order to provide technically sound solutions to these issues, thermodynamic data are essential in developing an understanding of the chemistry and phase equilibria of the actinide-bearing mineral waste form materials proposed as immobilization matrices. Mineral materials of interest include zircon, zirconolite, and pyrochlore. High temperature solution calorimetry is one of the most powerful techniques, sometimes the only technique, for providing the fundamental thermodynamic data needed to establish optimum material fabrication parameters, and more importantly understand and predict the behavior of the mineral materials in the environment. The purpose of this project is to experimentally determine the enthalpy of formation of actinide orthosilicates, the enthalpies of formation of actinide substituted zirconolite and pyrochlore, and develop an understanding of the bonding characteristics and stabilities of these materials.

  8. Fundamental thermodynamics of actinide-bearing mineral waste forms. 1998 annual progress report

    'The end of the Cold War raised the need for the technical community to be concerned with the disposition of excess nuclear weapon material. The plutonium will either be converted into mixed-oxide fuel for use in nuclear reactors or immobilized in glass or ceramic waste forms and placed in a repository. The stability and behavior of plutonium in the ceramic materials as well as the phase behavior and stability of the ceramic material in the environment is not well established. In order to provide technically sound solutions to these issues, thermodynamic data are essential in developing an understanding of the chemistry and phase equilibria of the actinide-bearing mineral waste form materials proposed as immobilization matrices. Mineral materials of interest include zircon, zirconolite, and pyrochlore. High temperature solution calorimetry is one of the most powerful techniques, sometimes the only technique, for providing the fundamental thermodynamic data needed to establish optimum material fabrication parameters, and more importantly, understand and predict the behavior of the mineral materials in the environment. The purpose of this project is to experimentally determine the enthalpy of formation of actinide orthosilicates, the enthalpy of formation of actinide substituted zircon, zirconolite and pyrochlore, and develop an understanding of the bonding characteristics and stability of these materials. This report summarizes work after eight months of a three year project.'

  9. Fundamental Thermodynamics of Actinide-Bearing Mineral Waste Forms - Final Report

    The end of the Cold War raised the need for the technical community to be concerned with the disposition of excess nuclear weapon material. The plutonium will either be converted into mixed-oxide fuel for use in nuclear reactors or immobilized in glass or ceramic waste forms and placed in a repository. The stability and behavior of plutonium in the ceramic materials as well as the phase behavior and stability of the ceramic material in the environment is not well established. In order to provide technically sound solutions to these issues, thermodynamic data are essential in developing an understanding of the chemistry and phase equilibria of the actinide-bearing mineral waste form materials proposed as immobilization matrices. Mineral materials of interest include zircon, zirconolite, and pyrochlore. High temperature solution calorimetry is one of the most powerful techniques, sometimes the only technique, for providing the fundamental thermodynamic data needed to establish optimum material fabrication parameters, and more importantly understand and predict the behavior of the mineral materials in the environment. The purpose of this project is to experimentally determine the enthalpy of formation of actinide orthosilicates, the enthalpies of formation of actinide substituted zirconolite and pyrochlore, and develop an understanding of the bonding characteristics and stabilities of these materials

  10. Stainless steel-zirconium alloy waste forms for metallic fission products and actinides during treatment of spent nuclear fuel

    Stainless steel-zirconium waste form alloys are being developed for the disposal of metallic wastes recovered from spent nuclear fuel using an electrometallurgical process developed by Argonne National Laboratory. The metal waste form comprises the fuel cladding, noble metal fission products and other metallic constituents. Two nominal waste form compositions are being developed: (1) stainless steel-15 wt% zirconium for stainless steel-clad fuels. The noble metal fission products are the primary source of radiation and their contribution to the waste form radioactivity has been calculated. The disposition of actinide metals in the waste alloys is also being explored. Simulated waste form alloys were prepared to study the baseline alloy microstructures and the microstructural distribution of noble metals and actinides, and to evaluate corrosion performance

  11. Actinides in liquid waste formed in the regeneration of nuclear fuel from a VVER-1000 reactor

    In the radiochemical reprocessing of spent fuel from nuclear reactors, a considerable amount of liquid, solid, and gaseous waste is formed; this waste is potentially dangerous to humans and requires the development of special and complex technological techniques for its localization and reliable long-term storage. The most hazardous are liquid wastes of high specific activity - water-tailings solutions obtained in the first cycle of extraction after the removal of uranium and plutonium. These solutions contain more than 99.9% of all the other transuranic elements - isotopes of neptunium, americium, and curium. Where necessary, some fission products and actinides may be removed from wastes of high specific activity for subsequent use. The quantity, composition, and activity of these wastes varies within broad limits, depending on the type and power of the reactor, the initial nuclide composition of the fuel, and its specific energy yield, the regeneration technology, and other factors. The aim of the present work is to study some radiation characteristics of the wastes of high specific activity formed in the radiochemical reprocessing of the fuel from a VVER-1000 water-cooled, water-moderated reactor

  12. Study of crystalline actinide waste forms produced by self-propagating high-temperature synthesis

    Prospective matrices for a safe immobilisation of long-lived actinide-bearing wastes were produced by self-propagating high-temperature synthesis. The samples were examined using XRD, SEM/EDS, and TEM. The data show that the ceramics consist of oxide phases with a fluorite- or pyrochlore-type structure and also metallic Mo. The structural properties of the target actinide-loaded host phase depend primarily on the composition of the immobilised waste. It is suggested that for streams enriched with tetravalent actinides having relatively small dimension of the cations: U4+ (0.10 nm), Np4+ (0.098 nm), and Pu4+ (0.096 nm), a cubic fluorite-structured ZrO2-based solid solution can be used to fix the waste, whereas titanates or zirconates with a pyrochlore-type lattice are well suited for wastes containing large amounts of the bulkier ions of trivalent actinides (Pu3+, Am3+) and lanthanides (Nd, Ce, La, Pr). Among other elements which can be located into the octahedral sites of the pyrochlore lattice, Tc4+ with a radius of 0.065 nm is worth mentioning. Long-lived 99Tc is produced during 235U fission events. Due to a high hazard associated with this isotope, it should also be fixed in highly durable matrices such as pyrochlore

  13. Gadolinium borosilicate glass-bonded Gd-silicate apatite: a glass-ceramic nuclear waste form for actinides

    A Gd-rich crystalline phase precipitated in a sodium gadolinium alumino-borosilicate glass during synthesis. The glass has a chemical composition of 45.4-31.1 wt% Gd2O3, 28.8-34.0 wt% SiO2,10.8-14.0 wt% Na2O, 4.3-5.9 wt% Al2O3, and 10.8-14.9 wt% B2O3. Backscattered electron images revealed that the crystals are hexagonal, elongated, acicular, prismatic, skeletal or dendritic, tens of μm in size, some reaching 200 μm in length. Electron microprobe analysis confirmed that the crystals are chemically homogeneous and have a formula of NaGd9(SiO4)6O2 with minor B substitution for Si. The X-ray diffraction pattern of this phase is similar to that of lithium gadolinium silicate apatite. Thus, this hexagonal phase is a rare earth silicate with the apatite structure. We suggest that this Gd-silicate apatite in a Gd-borosilicate glass is a potential glass-ceramic nuclear waste form for actinide disposition. Am, Cm and other actinides can easily occupy the Gd-sites. The potential advantages of this glass-ceramic waste form include: 1) both the glass and apatite can be used to immobilize actinides, 2) silicate apatite is thermodynamically more stable than the glass, 3) borosilicate glass-bonded Gd-silicate apatite is easily fabricated, and 4) the Gd is an effective neutron absorber.Copyright (2001) Material Research Society

  14. Actinide burning and waste disposal

    Here we review technical and economic features of a new proposal for a synergistic waste-management system involving reprocessing the spent fuel otherwise destined for a U.S. high-level waste repository and transmuting the recovered actinides in a fast reactor. The proposal would require a U.S. fuel reprocessing plant, capable of recovering and recycling all actinides, including neptunium americium, and curium, from LWR spent fuel, at recoveries of 99.9% to 99.999%. The recovered transuranics would fuel the annual introduction of 14 GWe of actinide-burning liquid-metal fast reactors (ALMRs), beginning in the period 2005 to 2012. The new ALMRs would be accompanied by pyrochemical reprocessing facilities to recover and recycle all actinides from discharged ALMR fuel. By the year 2045 all of the LWR spent fuel now destined f a geologic repository would be reprocessed. Costs of constructing and operating these new reprocessing and reactor facilities would be borne by U.S. industry, from the sale of electrical energy produced. The ALMR program expects that ALMRs that burn actinides from LWR spent fuel will be more economical power producers than LWRs as early as 2005 to 2012, so that they can be prudently selected by electric utility companies for new construction of nuclear power plants in that era. Some leaders of DOE and its contractors argue that recovering actinides from spent fuel waste and burning them in fast reactors would reduce the life of the remaining waste to about 200-300 years, instead of 00,000 years. The waste could then be stored above ground until it dies out. Some argue that no geologic repositories would be needed. The current view expressed within the ALMR program is that actinide recycle technology would not replace the need for a geologic repository, but that removing actinides from the waste for even the first repository would simplify design and licensing of that repository. A second geologic repository would not be needed. Waste now planned

  15. Actinide separation chemistry in nuclear waste streams and materials

    The separation of actinide elements from various waste materials, produced either in nuclear fuel cycles or in past nuclear weapons production, represents a significant issue facing developed countries. Improvements in the efficiencies of the separation processes can be expected to occur as a result of better knowledge of the elements in these complex matrices. The Nuclear Science Committee of the OECD/NEA has established a task force of experts in actinide separation chemistry to review current and developing separation techniques and chemical processes. The report consist of eight chapters. In Chapter 1 the importance of actinide separation chemistry in the fields of waste management and its background are summarized.In Chapter 2 the types of waste streams are classified according to their relative importance, by physical form and by source of actinides. The basic data of actinide chemical thermodynamics, such as oxidation states, hydrolysis, complexation, sorption, Gibbs energies of formation, and volatility, were collected and are presented in Chapter 3. Actinide analyses related to separation processes are also mentioned in this chapter. The state of the art of actinide separation chemistry is classified in three groups, including hydrometallurgy, pyrochemical process and process based on fields, and is described in Chapter 4 along with the relationship of kinetics to separations. In Chapter 5 basic chemistry research needs and the inherent limitation on separation processes are discussed. Prioritization of research and development is discussed in Chapter 6 in the context of several attributes of waste management problems. These attributes include: mass or volume of waste; concentration of the actinide in the waste; expected difficulty of treating the wastes; short-term hazard of the waste; long-term hazard of the waste; projected cost of treatment; amount of secondary waste. Based on the priority, recommendations were made for the direction of future research

  16. Role of actinide behavior in waste management

    For purposes of assessing the safety of repositories of radioactive wastes placed in geologic isolation, actinide behavior in the environment has been interpreted in terms of five steps of prediction: analysis of repository stability; geosphere transport; the geosphere-biosphere interface; biosphere transport; and biosphere consequences. Each step in the analysis requires models of nuclide behavior and data on the physical and chemical properties of the radioactivity. The scope of information required in order to make reliable safety assessments has been outlined. All steps in the assessment process are coupled; reliable models and data are therefore needed for each step. The prediction phase of safety assessment is also coupled to activities concerned with waste treatment, selection of the final form of the waste, and selection of repository sites and designs. Results of the predictions can impact these activities

  17. Waste disposal aspects of actinide separation

    Two recent NRPB reports are summarized (Camplin, W.C., Grimwood, P.D. and White, I.F., The effects of actinide separation on the radiological consequences of disposal of high-level radioactive waste on the ocean bed, Harwell, National Radiological Protection Board, NRPB-R94 (1980), London, HMSO; Hill, M.D., White, I.F. and Fleishman, A.B., The effects of actinide separation on the radiological consequences of geologic disposal of high-level waste. Harwell, National Radiological Protection Board, NRPB-R95 (1980), London, HMSO). They describe preliminary environmental assessments relevant to waste arising from the reprocessing of PWR fuel. Details are given of the modelling of transport of radionuclides to man, and of the methodology for calculating effective dose equivalents in man. Emphasis has been placed on the interaction between actinide separation and the disposal options rather than comparison of disposal options. The reports show that the effects of actinide separation do depend on the disposal method. Conditions are outlined where the required substantial further research and development work on actinide separation and recycle would be justified. Toxicity indices or 'toxic potentials' can be misleading and should not be used to guide research and development. (U.K.)

  18. Treatment of actinide-containing organic waste

    A method has been developed for reducing the volume of organic wastes and recovering the actinide elements. The waste, together with gaseous oxygen (air) is introduced into a molten salt, preferably an alkali metal carbonate such as sodium carbonate. The bath is kept at 7500 - 10000C and 0.5 - 10 atm to thermally decompose and partially oxidize the waste, while substantially reducing its volume. The gaseous effluent, mainly carbon dioxide and water vapour, is vented to the atmosphere through a series of filters to remove trace amounts of actinide elements or particulate alkali metal salts. The remaining combustion products are entrained in the molten salt. Part of the molten salt-combustion product mixture is withdrawn and mixed with an aqueous medium. Insoluble combustion products are then removed from the aqueous medium and are leached with a mixture of hydrofluoric and nitric acids to solubilize the actinide elements. The actinide elements are easily recovered from the acid solution using conventional techniques. (DN)

  19. The actinide waste problem in perspective

    The long lived alpha emitting actinide waste nuclides of transplutonium elements such as Np, Am, Cm etc (also called Byproduct Actinides or BPA for short) which are proposed to be disposed of as part of High Active Waste (HAW) in deep underground geological repositories has been a persistent source of concern to opponents and critics of nuclear fission energy. In this context the recent finding of the authors that each and every transuranium nuclide, without exception, can independently support a self sustaining chain reaction raises the important philosophical question: Is it justified to continue to refer to these nuclides as nuclear waste ? Our computations have revealed that the Ksub(eff) of an assembly of each of these nuclides increases linearly with the fissility parameter (Z2/A), its threshold value for Ksub(eff) to exceed unity being 34.1 for fissile (odd neutron) nuclides and 34.9 for fissible (even neutron) nuclides. In other words higher the (Z2/A) better is its performance as a fission reactor fuel. This finding suggests that the long lived actinide waste problem can be solved by separating all the actinide nuclides from the High Active Waste stream and recycling them back into any hard spectrum fission reactor. The studies strongly support the concept of partitioning-transmutation (p-t) revived with great enthusiasm in Japan under the banner of the OMEGA proposal. However it is found that there is no need to resort to any exotic devices such as proton accelerators or fusion reactor blankets for nuclear incineration. In the context of the 232Th/233U fuel cycle it is worth noting that the quantum of transuranium nuclides generated per se is smaller by several orders of magnitude as compared to that arising from 235U/238U bearing fuels. Thus on the whole it appears that in the thorium fuel cycle partitioning and recycle of byproduct nuclides would be a less cumbersome undertaking. (author). 26 refs., 6 figs., 3 tabs

  20. Actinide recycle in LMFBRs as a waste management alternative

    Beaman, S.L.

    1979-08-21

    A strategy of actinide burnup in fast reactor systems has been investigated as an approach for reducing the long term hazards and storage requirements of the actinide waste elements and their decay daughters. The actinide recycle studies also included plutonium burnup studies in the event that plutonium is no longer required as a fuel. Particular emphasis was placed upon the timing of the recycle program, the requirements for separability of the waste materials, and the impact of the actinides on the reactor operations and performance. It is concluded that actinide recycle and plutonium burnout are attractive alternative waste management concepts. 25 refs., 14 figs., 34 tabs.

  1. Actinide recycle in LMFBRs as a waste management alternative

    A strategy of actinide burnup in fast reactor systems has been investigated as an approach for reducing the long term hazards and storage requirements of the actinide waste elements and their decay daughters. The actinide recycle studies also included plutonium burnup studies in the event that plutonium is no longer required as a fuel. Particular emphasis was placed upon the timing of the recycle program, the requirements for separability of the waste materials, and the impact of the actinides on the reactor operations and performance. It is concluded that actinide recycle and plutonium burnout are attractive alternative waste management concepts. 25 refs., 14 figs., 34 tabs

  2. Actinide removal from nitric acid waste streams

    Actinide separations research at the Rocky Flats Plant (RFP) has found ways to significantly improve plutonium secondary recovery and americium removal from nitric acid waste streams generated by plutonium purification operations. Capacity and breakthrough studies show anion exchange with Dowex 1x4 (50 to 100 mesh) to be superior for secondary recovery of plutonium. Extraction chromatography with TOPO(tri-n-octyl-phosphine oxide) on XAD-4 removes the final traces of plutonium, including hydrolytic polymer. Partial neutralization and solid supported liquid membrane transfer removes americium for sorption on discardable inorganic ion exchangers, potentially allowing for non-TRU waste disposal

  3. Characterization of actinides in simulated alkaline tank waste sludges and leach solutions

    Current plans call for an alkaline scrub of actinide-bearing sludges in the Hanford Waste tanks prior to their incorporation in glass waste forms. Though it is assumed that actinides will remain in the sludge phase during this procedure, this assumption is based on insufficient supporting thermodynamic and kinetic data. In this project the authors will investigate the fundamental chemistry of actinides in strongly alkaline solution and solid phases to strengthen the foundation and identify potential limitations of this approach. They will focus on the characterization of the leaching of actinides from simulated BiPO4, REDOX, and PUREX sludges, the identification of actinide mineral phases in the sludge simulants, and the possible solubilization of actinides by complexation and radiolysis effects. This program will provide new fundamental information on the chemical behavior and speciation of uranium, neptunium, plutonium, and americium in simulated alkaline tank waste sludges and alkaline scrub liquors. Sludge simulants will be prepared from the appropriate matrix components using published data for guidance. Actinide ions will be introduced in the oxidation states pertinent to process conditions. The authors will characterize the speciation of the actinides in the sludges using a variety of techniques. In parallel studies, they will address the chemistry of actinide ions in alkaline solutions, principally those containing chelating agents. The third critical element of this research will be to assess the impact of radiolysis on actinide behavior. By correlating actinide speciation in the solid and solution phases with sludge composition, it will be possible to predict conditions favoring mobilization (or immobilization) of actinide ions during sludge washing. The new information will increase predictability of actinide behavior during tank sludge washing, and so contribute to minimization of the volume of high level waste created

  4. Sequestering agents for the removal of actinides from waste streams

    Raymond, K.N.; White, D.J.; Xu, Jide; Mohs, T.R. [Univ. of California, Berkeley, CA (United States)

    1997-10-01

    The goal of this project is to take a biomimetic approach toward developing new separation technologies for the removal of radioactive elements from contaminated DOE sites. To achieve this objective, the authors are investigating the fundamental chemistry of naturally occurring, highly specific metal ion sequestering agents and developing them into liquid/liquid and solid supported actinide extraction agents. Nature produces sideophores (e.g., Enterobactin and Desferrioxamine B) to selectivity sequester Lewis acidic metal ions, in particular Fe(III), from its surroundings. These chelating agents typically use multiple catechols or hydroxamic acids to form polydentate ligands that chelate the metal ion forming very stable complexes. The authors are investigating and developing analogous molecules into selective chelators targeting actinide(IV) ions, which display similar properties to Fe(III). By taking advantage of differences in charge, preferred coordination number, and pH stability range, the transition from nature to actinide sequestering agents has been applied to the development of new and highly selective actinide extraction technologies. Additionally, the authors have shown that these chelating ligands are versatile ligands for chelating U(VI). In particular, they have been studying their coordination chemistry and fundamental interactions with the uranyl ion [UO{sub 2}]{sup 2+}, the dominant form of uranium found in aqueous media. With an understanding of this chemistry, and results obtained from in vivo uranium sequestration studies, it should be possible to apply these actinide(IV) extraction technologies to the development of new extraction agents for the removal of uranium from waste streams.

  5. Radiochemical separation of actinides for their determination in environmental samples and waste products

    Gleisberg, B. [Nuclear Engineering and Analytics Rossendorf, Inc. (VKTA), Dresden (Germany)

    1997-03-01

    The determination of low level activities of actinides in environmental samples and waste products makes high demands on radiochemical separation methods. Artificial and natural actinides were analyzed in samples form the surrounding areas of NPP and of uranium mines, incorporation samples, solutions containing radioactive fuel, solutions and solids resutling from the process, and in wastes. The activities are measured by {alpha}-spectrometry and {gamma}-spectrometry. (DG)

  6. Magnetic form factor studies of actinide compounds

    Some results obtained at ILL on Actinide compound form factors are reviewed. In the paramagnetic NpO2 single crystal (5mg), an induced magnetic moment of 0.07μsub(B) was obtained at 4.2K (4.6T). In the ferromagnetic phase of NpAs2 single crystal (0.2mm3), the magnetic moment (1.46μsub(B)/Np atom) has been found fixed along the [001] direction. In both cases, the Np form factors fit satisfactorily the Np4+ form factor calculated with relativistic atomic wave functions. The Fermi length for Np was deduced (b(Np) = 1.015(15)10-12cm). In the paramagnetic Laves phase UNi2 compound, equally small moments are observed on U atom (0.013(1)μsub(B)) and on Ni atom (0.016(1)μsub(B)) confirming important changes in 3d band structure of Ni by hybridization with U electrons

  7. MICROBIAL TRANSFORMATIONS OF TRU AND MIXED WASTES: ACTINIDE SPECIATION AND WASTE VOLUME REDUCTION

    Francis, A.J.; Dodge, C.J.

    2006-06-01

    The overall goals of this research project are to determine the mechanism of microbial dissolution and stabilization of actinides in Department of Energy's (DOE) TRU wastes, contaminated sludges, soils, and sediments. This includes (1) investigations on the fundamental aspects of microbially catalyzed radionuclide and metal transformations (oxidation/reduction reactions, dissolution, precipitation, chelation); (2) understanding of the microbiological processes that control speciation and alter the chemical forms of complex inorganic/organic contaminant mixtures; and (3) development of new and improved microbially catalyzed processes resulting in immobilization of metals and radionuclides in the waste with concomitant waste volume reduction.

  8. MICROBIAL TRANSFORMATIONS OF TRU AND MIXED WASTES: ACTINIDE SPECIATION AND WASTE VOLUME REDUCTION

    Francis, A.J.; Dodge, C.J.

    2006-06-01

    The overall goals of this research project are to determine the mechanism of microbial dissolution and stabilization of actinides in Department of Energy’s (DOE) TRU wastes, contaminated sludges, soils, and sediments. This includes (i) investigations on the fundamental aspects of microbially catalyzed radionuclide and metal transformations (oxidation/reduction reactions, dissolution, precipitation, chelation); (ii) understanding of the microbiological processes that control speciation and alter the chemical forms of complex inorganic/organic contaminant mixtures; and (iii) development of new and improved microbially catalyzed processes resulting in immobilization of metals and radionuclides in the waste with concomitant waste volume reduction.

  9. MICROBIAL TRANSFORMATIONS OF TRU AND MIXED WASTES: ACTINIDE SPECIATION AND WASTE VOLUME REDUCTION.

    FRANCIS, A.J.; DODGE, C.J.

    2006-11-16

    The overall goals of this research project are to determine the mechanism of microbial dissolution and stabilization of actinides in Department of Energy's (DOE) TRU wastes, contaminated sludges, soils, and sediments. This includes (1) investigations on the fundamental aspects of microbially catalyzed radionuclide and metal transformations (oxidation/reduction reactions, dissolution, precipitation, chelation); (2) understanding of the microbiological processes that control speciation and alter the chemical forms of complex inorganic/organic contaminant mixtures; and (3) development of new and improved microbially catalyzed processes resulting in immobilization of metals and radionuclides in the waste with concomitant waste volume reduction.

  10. Cleanup of hydrochloric acid waste streams from actinide processes using extraction chromatography

    Extraction chromatography is under development as a method to lower actinide activity levels in hydrochloric acid (HCl) effluent steams. Successful application of this technique would allow recycle of the largest portion of HCl, while lowering the quantity and improving the form of solid waste generated. The extraction of plutonium and americium from HCl solutions was examined for several commercial and similar laboratory-produced resins coated with n-octyl(phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO) and either tributyl phosphate (TBP), or diamyl amylphosphonate (DAAP). Distribution coefficients for Pu and Am were measured by contact studies in 1-10 M HCl, while varying REDOX conditions, actinide loading levels, and contact time intervals. Significant differences in the actinide distribution coefficients, and in the kinetics of actinide removal were observed as a function of resin formulation

  11. Removal of actinides from selected nuclear fuel reprocessing wastes

    The US Department of Energy awarded Oak Ridge National Laboratory a program to develop a cost-risk-benefit analysis of partitioning long-lived nuclides from waste and transmuting them to shorter lived or stable nuclides. Two subtasks of this program were investigated at Rocky Flats. In the first subtask, methods for solubilizing actinides in incinerator ash were tested. Two methods appear to be preferable: reaction with ceric ion in nitric acid or carbonate-nitrate fusion. The ceric-nitric acid system solubilizes 95% of the actinides in ash; this can be increased by 2 to 4% by pretreating ash with sodium hydroxide to solubilize silica. The carbonate-nitrate fusion method solubilizes greater than or equal to 98% of the actinides, but requires sodium hydroxide pretreatment. Two additional disadvantages are that it is a high-temperature process, and that it generates a lot of salt waste. The second subtask comprises removing actinides from salt wastes likely to be produced during reactor fuel fabrication and reprocessing. A preliminary feasibility study of solvent extraction methods has been completed. The use of a two-step solvent extraction system - tributyl phosphate (TBP) followed by extraction with a bidentate organophosphorous extractant (DHDECMP) - appears to be the most efficient for removing actinides from salt waste. The TBP step would remove most of the plutonium and > 99.99% of the uranium. The second step using DHDECMP would remove > 99.91% of the americium and the remaining plutonium (> 99.98%) and other actinides from the acidified salt waste. 8 figures, 11 tables

  12. Burning of actinides: A complementary waste management option?

    The TRU actinide are building up at a rate of about 90 tHM per year. Approximately 45 tHM will remain occluded in the spent fuel structures, leaving about 45 tHM available; 92% as recycled plutonium and 8% as minor actinides (neptunium, americium, curium) immobilized in vitrified waste. There is renewed interest in partitioning and transmutation (P and T), largely because of difficulties encountered throughout the world in finding suitable geologic formations in locations which are acceptable to the public. In 1988, the Japanese Atomic Energy Commission launched a very important and comprehensive R and D program. The general strategy of introducing Partitioning and Transmutation (P and T) as an alternative waste management option is based on the radiological benefit which is expected from such a venture. The selection of the actinides and long-lived fission products which are beneficial to eliminate by transmutation depends upon a number of technical factors, including hazard and decontamination factors, and the effect of geological confinement. There are two ways to approach the separation of minor actinides and long-lived fission products from reprocessing streams: by modifying the current processes in order to reroute the critical nuclides into a single solution, for example high-level liquid waste, and use this as a source for partitioning processes; and by extension of the conventional PUREX process to all minor actinides and long-lived fission products in second generation reprocessing plants. Prior to the implementation of one of these schemes, it seems obvious to improve the separation yield of plutonium from HLW within the presently running plants. Actinide P and T is not an alternative long-term waste management option. Rather, it is a complementary technique to geologic disposal capable of further decreasing the radiological impact of the fuel cycle over the very long term. 1 tab

  13. Separation of actinides and lanthanides from acidic nuclear wastes by supported liquid membranes

    Supported liquid membranes, SLM, consisting of a solution of 0.25 M octyl(phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO) and 0.75 M tributylphosphate (TBP) in decalin absorbed on thin microporous polypropylene supports, have been studied for their ability to perform selective separations and concentrations of actinide and lanthanide ions from synthetic acidic nuclear wastes. The permeability coefficients of selected actinides (Am, Pu, U, Np) and of some of the other major components of the wastes have been measured using SLMs in flat-sheet and hollow-fiber configurations. The results have shown that with the thin (25 μm) flat-sheet SLMs, using Celgard 2500 as support, the membrane permeation process is mainly controlled by the rate of diffusion through the aqueous boundary layers. With the thicker (430 μm) hollow-fiber SLMs, using Accurel hollow-fibers as support, the membrane permeation process is controlled by the rate of diffusion through both the SLM and the aqueous boundary layers. Hollow-fibers SLMs exhibited lower permeability coefficients and longer life-times. The experiments have shown that the actinides can be very efficiently removed from the synthetic waste solutions to the point that the resulting solution could be considered a non-transuranic waste (less than 100 mCi/g of disposed form). The work has demonstrated that actinide removal from synthetic waste solutions is a feasible chemical process at the laboratory scale level

  14. Densified waste form and method for forming

    Garino, Terry J.; Nenoff, Tina M.; Sava Gallis, Dorina Florentina

    2015-08-25

    Materials and methods of making densified waste forms for temperature sensitive waste material, such as nuclear waste, formed with low temperature processing using metallic powder that forms the matrix that encapsulates the temperature sensitive waste material. The densified waste form includes a temperature sensitive waste material in a physically densified matrix, the matrix is a compacted metallic powder. The method for forming the densified waste form includes mixing a metallic powder and a temperature sensitive waste material to form a waste form precursor. The waste form precursor is compacted with sufficient pressure to densify the waste precursor and encapsulate the temperature sensitive waste material in a physically densified matrix.

  15. Densified waste form and method for forming

    Garino, Terry J.; Nenoff, Tina M.; Sava Gallis, Dorina Florentina

    2016-05-17

    Materials and methods of making densified waste forms for temperature sensitive waste material, such as nuclear waste, formed with low temperature processing using metallic powder that forms the matrix that encapsulates the temperature sensitive waste material. The densified waste form includes a temperature sensitive waste material in a physically densified matrix, the matrix is a compacted metallic powder. The method for forming the densified waste form includes mixing a metallic powder and a temperature sensitive waste material to form a waste form precursor. The waste form precursor is compacted with sufficient pressure to densify the waste precursor and encapsulate the temperature sensitive waste material in a physically densified matrix.

  16. Actinides in metallic waste from electrometallurgical treatment of spent nuclear fuel

    Janney, D. E.; Keiser, D. D.

    2003-09-01

    Argonne National Laboratory has developed a pyroprocessing-based technique for conditioning spent sodium-bonded nuclear-reactor fuel in preparation for long-term disposal. The technique produces a metallic waste form whose nominal composition is stainless steel with 15 wt.% Zr (SS-15Zr), up to ˜ 11 wt.% actinide elements (primarily uranium), and a few percent metallic fission products. Actual and simulated waste forms show similar eutectic microstructures with approximately equal proportions of iron solid solution phases and Fe-Zr intermetallics. This article reports on an analysis of simulated waste forms containing uranium, neptunium, and plutonium.

  17. Evaluation of actinide volatilities in mixed waste processors

    This report is an interim status report on a study of uranium, plutonium and americium volatilities in mixed waste oxidation processors. Both thermodynamic modeling methods and experimental measurements (incinerator ashes) are being used to assess the actinide volatilities. The volatile species of greatest importance is expected to be the actinide oxyhydroxide, MO2(OH)2(g). Based on early measurements, the volatility of PuO2(OH)2(g) from PuO2(s) in the presence of 0.9 atm O2 and 0.1 atm H2O at 1330 K is found to be about 4 x 10-10 atm

  18. Chromatographic separation of actinides and fission products from nuclear wastes

    Although a number of partitioning processes have been proposed and studied to separate the minor actinides (MA: Am, Cm, Np) and some fission product elements (FPs) from nuclear wastes, most of these processes essentially utilize liquid-liquid extraction technology by using a mixture of organic extractants hydrocarbon diluents. A large amount of the secondary waste, which is difficult for treatment and disposal will be generated by the extraction process. Compared to U and Pu, the MA and FPs are significantly abundant in the spent fuel, so that the scale of an efficient partitioning process for nuclear wastes reasonably small and result in less waste amount

  19. Removal of actinides from nuclear fuel reprocessing wastes using an organophosphorous extractant

    By removing actinides from nuclear fuel reprocessing wastes, long term waste storage hazards are reduced. A solvent extraction process to remove actinides has been demonstrated in miniature mixer-settlers and in simulated columns using actinide feeds. Nonradioactive pilot plant results have established the feasibility of using pulse columns for the process

  20. ANSTO's waste forms for the 31. century

    ANSTO waste form development for high-level radioactive waste is directed towards practical applications, particularly problematic niche wastes that do not readily lend themselves to direct vitrification. Integration of waste form chemistry and processing method is emphasised. Some longstanding misconceptions about titanate ceramics are dealt with. We have a range of titanate-bearing waste form products aimed at immobilisation of tank wastes and sludges, actinide-rich wastes, INEEL calcines and Na-bearing liquid wastes, Al-rich wastes arising from reprocessing of Al-clad fuels, Mo-rich wastes arising from reprocessing of U-Mo fuels, partitioned Cs-rich wastes, and 99Tc. Waste form production techniques cover hot isostatic and uniaxial pressing, sintering, and cold-crucible melting, and these are strongly integrated into waste form design. Speciation and leach resistance of Cs and alkalis in cementitious products and geo-polymers are being studied. Recently we have embarked on studies of candidate inert matrix fuels for Pu burning. We also have a considerable program directed at basic understanding of the waste forms in regard to crystal chemistry, dissolution behaviour in aqueous media, radiation damage effects and optimum processing techniques. (authors)

  1. Removal of actinides from nuclear reprocessing wastes: a pilot plant study using non-radioactive simulants

    Nuclear fuel reprocessing wastes generated at the ICPP contain small amounts of actinides, primarily Pu and Am. Removal of these actinides reduces the long term storage hazards of the waste. The development of a flowsheet to remove trivalent actinides is discussed in this paper. Pilot plant studies used actinide simulants. As a result of these studies, the Height of a Transfer Unit (HTU) was selected as the better measure of pulse column separation efficiency

  2. Method to produce bodies containing high-radioactive waste and/or actinides in granulated glass

    According to the main patent no. 2524169, a corrosion-resistant container is filled with granulated glass which contains high-activity wastes or actinides, and a liquid metal or metal alloy is then filled in which confines the radioactive granulate when cooled down. The patent claim deals with wastes whose activity is not so high that heat must be removed at once by liquid metal. The inventor proposes to fill the metal matrix in the form of rods or shredded metal and melt it afterwards, making sure that the waste material is completely covered and enclosed, if necessary by filling in additional matrix material. (orig./MM)

  3. Feasibility studies of actinide recycle in LMFBRs as a waste management alternative

    A strategy of actinide burnup in LMFBRs is being investigated as a waste management alternative to long term storage of high level nuclear waste. This strategy is being evaluated because many of the actinides in the waste from spent-fuel reprocessing have half-lives of thousands of years and an alternative to geological storage may be desired. From a radiological viewpoint, the actinides and their daughters dominate the waste hazard for decay times beyond about 400 years. Actinide burnup in LMFBRs may be an attractive alternative to geological storage because the actinides can be effectively transmuted to fission products which have significantly shorter half-lives. Actinide burnup in LMFBRs rather than LWRs is preferred because the ratio of fission reaction rate to capture reaction rate for the actinides is higher in an LMFBR, and an LMFBR is not so sensitive to the addition of the actinide isotopes. An actinide target assembly recycle scheme is evaluated to determine the effects of the actinides on the LMFBR performance, including local power peaking, breeding ratio, and fissile material requirements. Several schemes are evaluated to identify any major problems associated with reprocessing and fabrication of recycle actinide-containing assemblies. The overall efficiency of actinide burnout in LMFBRs is evaluated, and equilibrium cycle conditions are determined. It is concluded that actinide recycle in LMFBRs offers an attractive alternative to long term storage of the actinides, and does not significantly affect the performance of the host LMFBR. Assuming a 0.1 percent or less actinide loss during reprocessing, a 0.1 percent loss of less during fabrication, and proper recycle schemes, virtually all of the actinides produced by a fission reactor economy could be transmuted in fast reactors

  4. Actinides and fission products partitioning from high level liquid waste

    The presence of small amount of mixed actinides and long-lived heat generators fission products as 137Cs and 90Sr are the major problems for safety handling and disposal of high level nuclear wastes. In this work, actinides and fission products partitioning process, as an alternative process for waste treatment is proposed. First of all, ammonium phosphotungstate (PWA), a selective inorganic exchanger for cesium separation was chosen and a new procedure for synthesizing PWA into the organic resin was developed. An strong anionic resin loaded with tungstate or phosphotungstate anion enables the precipitation of PWA directly in the resinous structure by adding the ammonium nitrate in acid medium (R-PWA). Parameters as W/P ratio, pH, reactants, temperature and aging were studied. The R-PWA obtained by using phosphotungstate solution prepared with W/P=9.6, 9 hours digestion time at 94-106 deg C and 4 to 5 months aging time showed the best capacity for cesium retention. On the other hand, Sr separation was performed by technique of extraction chromatography, using DH18C6 impregnated on XAD7 resin as stationary phase. Sr is selectively extracted from acid solution and >99% was recovered from loaded column using distilled water as eluent. Concerning to actinides separations, two extraction chromatographic columns were used. In the first one, TBP(XAD7) column, U and Pu were extracted and its separations were carried-out using HNO3 and hydroxylamine nitrate + HNO3 as eluent. In the second one, CMP0-TBP(XAD7) column, the actinides were retained on the column and the separations were done by using (NH4)2C2O4 , DTPA, HNO3 and HCl as eluent. The behavior of some fission products were also verified in both columns. Based on the obtained data, actinides and fission products Cs and Sr partitioning process, using TBP(XAD7) and CMP0-TBP(XAD7) columns for actinides separation, R-PWA column for cesium retention and DH18C6(XAD7) column for Sr isolation was performed. (author)

  5. Effects of actinide burning on waste disposal at Yucca Mountain

    Partitioning the actinides in spent fuel and transmuting them in actinide-burning liquid-metal reactors (ALMRs) is a potential method of reducing public risks from the geologic disposal of nuclear waste. In this paper, the authors present a comparison of radionuclide releases from burial at Yucca Mountain of spent fuel and of ALMR wastes. Two waste disposal schemes are considered. In each, the heat generation of the wastes at emplacement is 9.88 x 107 W, the maximum for the repository. In the first scheme, the repository contains 86,700 tonnes of initial heavy metal (IHM) of light water reactor (LWR) spent fuel. In the second scheme, all current LWRs operate for a 40-yr lifetime, producing a total of 84,000 tonnes IHM of spent fuel. This spent fuel is treated using a pyrochemical process in which 98.4% of the uranium and 99.8% of the neptunium, plutonium, americium, and curium are extracted and fabricated into ALMR fuel, with the reprocessing wastes destined for the repository. The ALMR requires this fuel for its startup and first two reloads; thereafter, it is self-sufficient. Spent ALMR fuel is also pyrochemically reprocessed: 99.9% of the transuranics is recovered and recycled into ALMR fuel, and the wastes are placed in the repository. Thus, in the second scheme, the repository contains the wastes from reprocessing all of the LWR spent fuel plus the maximum amount of ALMR reprocessing wastes allowed in the repository based on its heat generation limit

  6. Waste-form development

    Contemporary solidification agents are being investigated relative to their applications to major fuel cycle and non-fuel cycle low-level waste (LLW) streams. Work is being conducted to determine the range of conditions under which these solidification agents can be applied to specific LLW streams. These studies are directed primarily towards defining operating parameters for both improved solidification of problem wastes and solidification of new LLW streams generated from advanced volume reduction technologies. Work is being conducted to measure relevant waste form properties. These data will be compiled and evaluated to demonstrate compliance with waste form performance and shallow land burial acceptance criteria and transportation requirements

  7. Effects of actinide burning on waste disposal at Yucca Mountain

    Release rates of 15 radionuclides from waste packages expected to result from partitioning and transmutation of Light-Water Reactor (LWR) and Actinide-Burning Liquid-Metal Reactor (ALMR) spent fuel are calculated and compared to release rates from standard LWR spent fuel packages. The release rates are input to a model for radionuclide transport from the proposed geologic repository at Yucca Mountain to the water table. Discharge rates at the water table are calculated and used in a model for transport to the accessible environment, defined to be five kilometers from the repository edge. Concentrations and dose rates at the accessible environment from spent fuel and wastes from reprocessing, with partitioning and transmutation, are calculated. Partitioning and transmutation of LWR and ALMR spent fuel reduces the inventories of uranium, neptunium, plutonium, americium and curium in the high-level waste by factors of 40 to 500. However, because release rates of all of the actinides except curium are limited by solubility and are independent of package inventory, they are not reduced correspondingly. Only for curium is the repository release rate much lower for reprocessing wastes

  8. Strontium and Actinide Separations from High Level Nuclear Waste Solutions using Monosodium Titanate - Actual Waste Testing

    Peters, T.B.; Barnes, M.J.; Hobbs,D.T.; Walker, D.D.; Fondeur, F.F.; Norato, M.A.; Pulmano, R.L.; Fink, S.D.

    2005-11-01

    Pretreatment processes at the Savannah River Site will separate {sup 90}Sr, alpha-emitting and radionuclides (i.e., actinides) and {sup 137}Cs prior to disposal of the high-level nuclear waste. Separation of {sup 90}Sr and alpha-emitting radionuclides occurs by ion exchange/adsorption using an inorganic material, monosodium titanate (MST). Previously reported testing with simulants indicates that the MST exhibits high selectivity for strontium and actinides in high ionic strength and strongly alkaline salt solutions. This paper provides a summary of data acquired to measure the performance of MST to remove strontium and actinides from actual waste solutions. These tests evaluated the effects of ionic strength, mixing, elevated alpha activities, and multiple contacts of the waste with MST. Tests also provided confirmation that MST performs well at much larger laboratory scales (300-700 times larger) and exhibits little affinity for desorption of strontium and plutonium during washing.

  9. Comparative waste forms study

    A number of alternative process and waste form options exist for the immobilization of nuclear wastes. Although data exists on the characterization of these alternative waste forms, a straightforward comparison of product properties is difficult, due to the lack of standardized testing procedures. The characterization study described in this report involved the application of the same volatility, mechanical strength and leach tests to ten alternative waste forms, to assess product durability. Bulk property, phase analysis and microstructural examination of the simulated products, whose waste loading varied from 5% to 100% was also conducted. The specific waste forms investigated were as follows: Cold Pressed and Sintered PW-9 Calcine; Hot Pressed PW-9 Calcine; Hot Isostatic Pressed PW-9 Calcine; Cold Pressed and Sintered SPC-5B Supercalcine; Hot Isostatic pressed SPC-5B Supercalcine; Sintered PW-9 and 50% Glass Frit; Glass 76-68; Celsian Glass Ceramic; Type II Portland Cement and 10% PW-9 Calcine; and Type II Portland Cement and 10% SPC-5B Supercalcine. Bulk property data were used to calculate and compare the relative quantities of waste form volume produced at a spent fuel processing rate of 5 metric ton uranium/day. This quantity ranged from 3173 L/day (5280 Kg/day) for 10% SPC-5B supercalcine in cement to 83 L/day (294 Kg/day) for 100% calcine. Mechanical strength, volatility, and leach resistance tests provide data related to waste form durability. Glass, glass-ceramic and supercalcine ranked high in waste form durability where as the 100% PW-9 calcine ranked low. All other materials ranked between these two groupings

  10. Removal of actinides from dilute waste waters using polymer filtration

    More stringent US Department of Energy discharge regulations for waste waters containing radionuclides (30 pCi/L total alpha) require the development of new processes to meet the new discharge limits for actinide metal ions, particularly americium and plutonium, while minimizing waste. We have been investigating a new technology, polymer filtration, that has the potential for effectively meeting these new limits. Traditional technology uses basic iron precipitation which produces large amounts of waste sludge. The new technology is based on using water-soluble chelating polymers with ultrafiltration for physical separation. The actinide metal ions are selectively bound to the polymer and can not pass through the membrane. Small molecules and nonbinding metals pass through the membrane. Advantages of polymer filtration technology compared to ion, exchange include rapid kinetics because the binding is occurring in a homogenous solution and no mechanical strength requirement on the polymer. We will present our results on the systematic development of a new class of water-soluble chelating polymers and their binding ability from dilute acid to near neutral waters

  11. The treatment and packaging of waste plutonium and waste actinides for disposal

    The objectives of this work have been to review the current state of knowledge on the treatment and packaging of unusable or surplus plutonium and other waste actinides for disposal and to identify any gaps in data essential for the development of a preferred route. The exercise was based on published data which said the quantity currently to be disposed of was 50 tonnes in oxide form. A literature review over the period 1978 to 1988 was carried out and a computerised database specific to the exercise was created. From this it is concluded that there are no insuperable problems to the formulation of a disposal route although there is none currently proven. The preferred wasteform would be a glass or synthetic rock. The major complication lies in the fissile nature of plutonium which dictates limits to the package size and places restrictions on the production and disposal routes. Additional work necessary to permit a final decision is listed. (author)

  12. Long-term results from unsaturated testing of actinide-doped DWPF and WVDP waste glasses

    Results from drip tests designed to simulate the unsaturated conditions in the proposed Yucca Mountain Repository are reported for two actinide-doped glasses used as model waste forms. These tests are being conducted with reference glass compositions doped with neptunium, plutonium, and americium from the Defense Waste Processing Facility (DWPF) and the West Valley Demonstration Project (WVDP), and have been ongoing for over 8 years. Solution compositions, including transuranics, have been periodically determined, and selected analyses of colloid formation and composition, glass corrosion layers, and solid alteration phases have been obtained by scanning and analytical transmission electron microscopies. The importance of integrated testing has been demonstrated, as complex interactions among the glass, the groundwater, and the sensitized stainless steel have been observed. The cumulative releases of both glass-forming and dopant elements are presented along with identification of reaction phases and their partitioning between solution and solid phases. Alteration phases, including smectite clay, iron silicates, uranium silicates, and calcium thorium phosphate, have been observed forming on the glass and stainless steel and have occasionally been found suspended in solution as colloids. Actinides, except neptunium, concentrate into alteration phases or sorb onto the stainless steel. The subsequent transport of the actinides is then controlled by these phases

  13. Tomography of actinides by photofission in bulky radioactive waste packages

    Quantifying actinides using non-destructive methods, in radioactive waste packages, is a great stake to turn packages towards appropriate storage facility. But the nature of radiations emitted by actinides (alpha radiations) makes the detection of those very difficult for large volume packages characterization. Indeed, the emitted radiation is too weak, either to be detected by emission tomography or to reach required sensitivities. Therefore, it is necessary to turn to an external probing source. Tomography based on detection of delayed neutrons induced by photofission, allows to probe bulky packages. We demonstrate the suitability of this method to an industrial stage. Firstly, we determine and qualify projection matrix which connects measures at reconstructed activity of tomographic picture. Thus, during measurements on a model and a real package, we carry out convincing tomographic reconstructions with real acquisition conditions. More, we prove that it is possible to take all disruptive chemical element into account, for tomographic reconstructions, in order to obtain the best image of activity. So, we propose a finalised tomographic device, integrating a shielding cell, and checking all the activity and distribution activity criterions fixed for acceptance of radioactive waste packages in superficial storage facility. (author)

  14. Waste form development

    In this program, contemporary solidification agents are being investigated relative to their applications to major fuel cycle and non-fuel cycle low-level waste (LLW) streams. Work is being conducted to determine the range of conditions under which these solidification agents can be applied to specific LLW streams. These studies are directed primarily towards defining operating parameters for both improved solidification of problem wastes and solidification of new LLW streams generated from advanced volume reduction technologies. Work is being conducted to measure relevant waste form properties. These data will be compiled and evaluated to demonstrate compliance with waste form performance and shallow land burial acceptance criteria and transportation requirements (both as they exist and as they are modified with time). 6 tables

  15. Characterization of a ceramic waste form encapsulating radioactive electrorefiner salt

    Moschetti, T. L.; Sinkler, W.; DiSanto, T.; Noy, M.; Warren, A. R.; Cummings, D. G.; Johnson, S. G.; Goff, K. M.; Bateman, K. J.; Frank, S. M.

    1999-11-11

    Argonne National Laboratory has developed a ceramic waste form to immobilize radioactive waste salt produced during the electrometallurgical treatment of spent fuel. This study presents the first results from electron microscopy and durability testing of a ceramic waste form produced from that radioactive electrorefiner salt. The waste form consists of two primary phases: sodalite and glass. The sodalite phase appears to incorporate most of the alkali and alkaline earth fission products. Other fission products (rare earths and yttrium) tend to form a separate phase and are frequently associated with the actinides, which form mixed oxides. Seven-day leach test results are also presented.

  16. Assessment of radiation effects in defense transuranic waste forms

    The actinide concentrations of the defense transuranic (TRU) wastes were analyzed and the potential effects of the radiation on the properties of the wastes after conversion to immobile forms were assessed. The study focused on the contact-handled retrievably-stored wastes. The major components of the current inventory are defense plutonium-contaminated wastes containing various amounts of 241Am. The wastes stored at Idaho National Engineering Laboratory (INEL) are typical of the wastes in this category. There is also a substantial amount of wastes contaminated with plutonium enriched in 238Pu arising from the Department of Energy's isotopic heat-source programs. Most of these wastes are stored at the Los Alamos National Laboratory (LANL) and the Savannah River Plant (SRP) sites. Four reference wastes were selected representing a credible range of actinide activities and were used for estimating radiation doses to the final waste forms based on: INEL first stage sludge, a composite of all wastes at INEL, a composite of all wastes at LANL including both defense and heat source plutonium wastes, and a composite of all heat-source plutonium wastes at SRP free from defense plutonium. From integrated alpha and beta-gamma doses over a 105y storage period, it is concluded that: accumulated beta-gamma doses of 106 to 108 rad over a 105 y storage period will not significantly change physical properties of the waste form. The alpha decay doses are 3-30 x 1016 decays/cm3 (up to 3 x 1010 rad ionizing radiation from alpha particles) accumulated over a 105 y storage period. Radiolytic gas generation can be substantial in waste forms containing water or organic materials. The effect of leachant radiolysis on the leachabilities of TRU waste forms is not sufficiently understood to rule out the need for testing with actinide-doped specimens

  17. Radiation effects in ceramic nuclear waste forms

    This paper reports on alpha-decay event damage (a particle and recoil-nucleus) that results in atomic-scale disorder which causes changes in the molar volume, corrosion rate, stored energy, mechanical properties, and macrostructure of ceramics. These changes particularly of volume and corrosion rate, have critical implications for the long-term durability of nuclear waste forms, such as the polyphase. Ti-based ceramic Synroc. This paper reviews data on actinide-bearing (U and Th) phases of great age (>100 m.y.) found in nature and compares these results to observation on actinide-doped phases (Pu and Cm) of nearly equivalent α-decay doses. Of particular interest is evidence for annealing of radiation damage effects over geologic periods of time under ambient conditions

  18. Rapid methods for determination of small amount of actinides in waste waters

    A rapid method of plutonium and actinide sum (Ac) (except uranium) determination in waste waters has been developed. For rapid isolation of 239Pu and Ac sum a method of extraction to iron hydroxide myomphate (IHM), consisting in Ac deposition on iron hydroxide, solvent extraction by monoisooctylmethylphosphinic acid and flotation of the disperse phase into solid extract of IHM, has been applied. The method permits to concentrate plutonium quantitatively from solutions in all of its forms, including colloid ones. For analysis of solid extracts α-spectroimetric instrumentation is used. The analysis sensitivity is 1 Bg/l, relative standard deviation - 0.3. 10 refs.; 1 fig.; 2 tabs

  19. Waste form product characteristics

    The Department of Energy has operated nuclear facilities at the Idaho National Engineering Laboratory (INEL) to support national interests for several decades. Since 1953, it has supported the development of technologies for the storage and reprocessing of spent nuclear fuels (SNF) and the resultant wastes. However, the 1992 decision to discontinue reprocessing of SNF has left nearly 768 MT of SNF in storage at the INEL with unspecified plans for future dispositioning. Past reprocessing of these fuels for uranium and other resource recovery has resulted in the production of 3800 M3 calcine and a total inventory of 7600 M3 of radioactive liquids (1900 M3 destined for immediate calcination and the remaining sodium-bearing waste requiring further treatment before calcination). These issues, along with increased environmental compliance within DOE and its contractors, mandate operation of current and future facilities in an environmentally responsible manner. This will require satisfactory resolution of spent fuel and waste disposal issues resulting from the past activities. A national policy which identifies requirements for the disposal of SNF and high level wastes (HLW) has been established by the Nuclear Waste Policy Act (NWPA) Sec.8,(b) para(3)) [1982]. The materials have to be conditioned or treated, then packaged for disposal while meeting US Environmental Protection Agency (EPA) and Nuclear Regulatory Commission (NRC) regulations. The spent fuel and HLW located at the INEL will have to be put into a form and package that meets these regulatory criteria. The emphasis of Idaho Chemical Processing Plant (ICPP) future operations has shifted toward investigating, testing, and selecting technologies to prepare current and future spent fuels and waste for final disposal. This preparation for disposal may include mechanical, physical and/or chemical processes, and may differ for each of the various fuels and wastes

  20. Selective extraction of actinides from high level liquid wastes. Study of the possibilities offered by the Redox properties of actinides

    Partitioning of high level liquid wastes coming from nuclear fuel reprocessing by the PUREX process, consists in the elimination of minor actinides (Np, Am, and traces of Pu and U). Among the possible processes, the selective extraction of actinides with oxidation states higher than three is studied. First part of this work deals with a preliminary step; the elimination of the ruthenium from fission products solutions using the electrovolatilization of the RuO4 compound. The second part of this work concerns the complexation and oxidation reactions of the elements U, Np, Pu and Am in presence of a compound belonging to the insaturated polyanions family: the potassium phosphotungstate. For actinide ions with oxidation state (IV) complexed with phosphotungstate anion the extraction mechanism by dioctylamine was studied and the use of a chromatographic extraction technic permitted successful separations between tetravalents actinides and trivalents actinides. Finally, in accordance with the obtained results, the basis of a separation scheme for the management of fission products solutions is proposed

  1. Study of the actinide-lanthanide separation from nuclear waste by a new pyrochemical process

    The theoretical extraction and separation of platinoids, actinides and lanthanides is allowed by thermodynamic using two adapted reducing agents: zinc and magnesium. Thereby, a pyrochemical method for the nuclear waste processing has been devised. The high temperature handling of the elements in fluoride forms and their processing by a reactive metallic phase required special precautions. The study of the behavior of matter in exploratory systems allowed the development of an experimental technology for the treatment and contacting of phases. The thermodynamical analysis of the experimental results shows the feasibility of the process. A model was developed to predict the distribution coefficients of zirconium, uranium and lanthanum as a function of the system composition. An estimation method was proposed in order to evaluate the distribution coefficients in diluted solution of all the actinides and lanthanides existing in the fission products between LiF CaF2 and Zn-Mg at 720 deg C. Coupled with the experimental results, the estimates results may be extrapolated to concentrated solutions allowing predictions of the separation of all actinides and lanthanides. The rapidity of element transfer is induced by a thermal effect caused by the high exothermicity of the reduction by magnesium. The kinetic coefficients have been linked with the reduction enthalpy of each element. Moreover, the kinetics seem limited by chemical reaction and not by mass transfer. (author)

  2. MICROBIAL TRANSFORMATIONS OF PLUTONIUM AND OTHER ACTINIDES IN TRANSURANIC AND MIXED WASTES

    The presence of the actinides Th, U, Np, Pu, and Am in transuranic (TRU) and mixed wastes is a major concern because of their potential for migration from the waste repositories and long-term contamination of the environment. The toxicity of the actinide elements and the long half-lives of their isotopes are the primary causes for concern. In addition to the radionuclides the TRU waste consists a variety of organic materials (cellulose, plastic, rubber, chelating agents) and inorganic compounds (nitrate and sulfate). Significant microbial activity is expected in the waste because of the presence of organic compounds and nitrate, which serve as carbon and nitrogen sources and in the absence of oxygen the microbes can use nitrate and sulfate as alternate electron acceptors. Biodegradation of the TRU waste can result in gas generation and pressurization of containment areas, and waste volume reduction and subsidence in the repository. Although the physical, chemical, and geochemical processes affecting dissolution, precipitation, and mobilization of actinides have been investigated, we have only limited information on the effects of microbial processes. Microbial activity could affect the chemical nature of the actinides by altering the speciation, solubility and sorption properties and thus could increase or decrease the concentrations of actinides in solution. Under appropriate conditions, dissolution or immobilization of actinides is brought about by direct enzymatic or indirect non-enzymatic actions of microorganisms. Dissolution of actinides by microorganisms is brought about by changes in the Eh and pH of the medium, by their production of organic acids, such as citric acid, siderophores and extracellular metabolites. Immobilization or precipitation of actinides is due to changes in the Eh of the environment, enzymatic reductive precipitation (reduction from higher to lower oxidation state), biosorption, bioaccumulation, biotransformation of actinides complexed

  3. Electrochemical/Pyrometallurgical Waste Stream Processing and Waste Form Fabrication

    Steven Frank; Hwan Seo Park; Yung Zun Cho; William Ebert; Brian Riley

    2015-07-01

    This report summarizes treatment and waste form options being evaluated for waste streams resulting from the electrochemical/pyrometallurgical (pyro ) processing of used oxide nuclear fuel. The technologies that are described are South Korean (Republic of Korea – ROK) and United States of America (US) ‘centric’ in the approach to treating pyroprocessing wastes and are based on the decade long collaborations between US and ROK researchers. Some of the general and advanced technologies described in this report will be demonstrated during the Integrated Recycle Test (IRT) to be conducted as a part of the Joint Fuel Cycle Study (JFCS) collaboration between US Department of Energy (DOE) and ROK national laboratories. The JFCS means to specifically address and evaluated the technological, economic, and safe guard issues associated with the treatment of used nuclear fuel by pyroprocessing. The IRT will involve the processing of commercial, used oxide fuel to recover uranium and transuranics. The recovered transuranics will then be fabricated into metallic fuel and irradiated to transmutate, or burn the transuranic elements to shorter lived radionuclides. In addition, the various process streams will be evaluated and tested for fission product removal, electrolytic salt recycle, minimization of actinide loss to waste streams and waste form fabrication and characterization. This report specifically addresses the production and testing of those waste forms to demonstrate their compatibility with treatment options and suitability for disposal.

  4. Method for the recovery of actinide elements from nuclear reactor waste

    A process is described for partitioning and recovering actinide values from acidic waste solutions resulting from reprocessing of irradiated nuclear fuels by adding hydroxylammonium nitrate and hydrazine to the waste solution to adjust the valence of the neptunium and plutonium values in the solution to the +4 oxidation state, thus forming a feed solution and contacting the feed solution with an extractant of dihexoxyethyl phosphoric acid in an organic diluent whereby the actinide values, most of the rare earth values and some fission product values are taken up by the extractant. Separation is achieved by contacting the loaded extractant with two aqueous strip solutions, a nitric acid solution to selectively strip the americium, curium and rare earth values and an oxalate and oxalic acid or trimethylammonium hydrogen oxalate to selectively strip the neptunium, plutonium and fission product values. Uranium values remain in the extractant and may be recovered with a phosphoric acid strip. The neptunium and plutonium values are recovered from the oxalate by adding sufficient nitric acid to destroy the complexing ability of the oxalate, forming a second feed, and contacting the second feed with a second extractant of tricaprylmethylammonium nitrate in an inert diluent whereby the neptunium and plutonium values are selectively extracted. The values are recovered from the extractant with formic acid

  5. CRYSTALLINE CERAMIC WASTE FORMS: REFERENCE FORMULATION REPORT

    Brinkman, K.; Fox, K.; Marra, J.

    2012-05-15

    The research conducted in this work package is aimed at taking advantage of the long term thermodynamic stability of crystalline ceramics to create more durable waste forms (as compared to high level waste glass) in order to reduce the reliance on engineered and natural barrier systems. Durable ceramic waste forms that incorporate a wide range of radionuclides have the potential to broaden the available disposal options and to lower the storage and disposal costs associated with advanced fuel cycles. Assemblages of several titanate phases have been successfully demonstrated to incorporate radioactive waste elements, and the multiphase nature of these materials allows them to accommodate variation in the waste composition. Recent work has shown that they can be successfully produced from a melting and crystallization process. The objective of this report is to explain the design of ceramic host systems culminating in a reference ceramic formulation for use in subsequent studies on process optimization and melt property data assessment in support of FY13 melter demonstration testing. The waste stream used as the basis for the development and testing is a combination of the projected Cs/Sr separated stream, the Trivalent Actinide - Lanthanide Separation by Phosphorous reagent Extraction from Aqueous Komplexes (TALSPEAK) waste stream consisting of lanthanide fission products, the transition metal fission product waste stream resulting from the transuranic extraction (TRUEX) process, and a high molybdenum concentration with relatively low noble metal concentrations. In addition to the combined CS/LN/TM High Mo waste stream, variants without Mo and without Mo and Zr were also evaluated. Based on the results of fabricating and characterizing several simulated ceramic waste forms, two reference ceramic waste form compositions are recommended in this report. The first composition targets the CS/LN/TM combined waste stream with and without Mo. The second composition targets

  6. Colloid formation during waste form reaction: implications for nuclear waste disposal

    Bates, J. K.; Bradley, J.; Teetsov, A.; Bradley, C. R.; ten Brink, Marilyn Buchholtz

    1992-01-01

    Insoluble plutonium- and americium-bearing colloidal particles formed during simulated weathering of a high-level nuclear waste glass. Nearly 100 percent of the total plutonium and americium in test ground water was concentrated in these submicrometer particles. These results indicate that models of actinide mobility and repository integrity, which assume complete solubility of actinides in ground water, underestimate the potential for radionuclide release into the environment. A colloid-trapping mechanism may be necessary for a waste repository to meet long-term performance specifications.

  7. ANSTO's waste forms for the 31. century

    Vance, E.R.; Begg, B. D.; Day, R. A.; Moricca, S.; Perera, D. S.; Stewart, M. W. A.; Carter, M. L.; McGlinn, P. J.; Smith, K. L.; Walls, P. A.; Robina, M. La

    2004-07-01

    ANSTO waste form development for high-level radioactive waste is directed towards practical applications, particularly problematic niche wastes that do not readily lend themselves to direct vitrification. Integration of waste form chemistry and processing method is emphasised. Some longstanding misconceptions about titanate ceramics are dealt with. We have a range of titanate-bearing waste form products aimed at immobilisation of tank wastes and sludges, actinide-rich wastes, INEEL calcines and Na-bearing liquid wastes, Al-rich wastes arising from reprocessing of Al-clad fuels, Mo-rich wastes arising from reprocessing of U-Mo fuels, partitioned Cs-rich wastes, and {sup 99}Tc. Waste form production techniques cover hot isostatic and uniaxial pressing, sintering, and cold-crucible melting, and these are strongly integrated into waste form design. Speciation and leach resistance of Cs and alkalis in cementitious products and geo-polymers are being studied. Recently we have embarked on studies of candidate inert matrix fuels for Pu burning. We also have a considerable program directed at basic understanding of the waste forms in regard to crystal chemistry, dissolution behaviour in aqueous media, radiation damage effects and optimum processing techniques. (authors)

  8. Microbial Transformation of TRU and Mixed Waste: Actinide Speciation and Waste Volume

    Halada, Gary P

    2008-04-10

    In order to understand the susceptibility of transuranic and mixed waste to microbial degradation (as well as any mechanism which depends upon either complexation and/or redox of metal ions), it is essential to understand the association of metal ions with organic ligands present in mixed wastes. These ligands have been found in our previous EMSP study to limit electron transfer reactions and strongly affect transport and the eventual fate of radionuclides in the environment. As transuranic waste (and especially mixed waste) will be retained in burial sites and in legacy containment for (potentially) many years while awaiting treatment and removal (or remaining in place under stewardship agreements at government subsurface waste sites), it is also essential to understand the aging of mixed wastes and its implications for remediation and fate of radionuclides. Mixed waste containing actinides and organic materials are especially complex and require extensive study. The EMSP program described in this report is part of a joint program with the Environmental Sciences Department at Brookhaven National Laboratory. The Stony Brook University portion of this award has focused on the association of uranium (U(VI)) and transuranic analogs (Ce(III) and Eu(III)) with cellulosic materials and related compounds, with development of implications for microbial transformation of mixed wastes. The elucidation of the chemical nature of mixed waste is essential for the formulation of remediation and encapsulation technologies, for understanding the fate of contaminant exposed to the environment, and for development of meaningful models for contaminant storage and recovery.

  9. Permanganate Reduction of Savannah River Site Actual Waste Samples for Strontium and Actinides Removal

    The authors investigated the performance of permanganate treatment for the removal of strontium and actinides from actual high-level waste. Researchers also conducted comparison tests with monosodium titanate (MST) as a means of evaluating the permanganate performance. Tests utilized a Tank 37H/44F composite waste solution. Personnel significantly increased the concentration of alpha emitting actinides in the waste by the addition of acidic americium/curium solution (F-Canyon Tank 17.1 solution), which contained a significant quantity of plutonium, and neptunium-237 stock solution. Tests examined three permanganate treatment options

  10. Leaching of actinides from nuclear waste glass: French experience

    The activity concentration versus time of a typical LWR glass shows that after 300 years most of the activity is attributable to three actinides (Np, Pu and Am) and to 99Tc. This activity decreases slowly, and some 50.000 years are necessary before the activity concentration drops to the level of the richest natural ores. This paper reviews the current state of knowledge concerning the kinetics of actinide release from glass subjected to aqueous leaching

  11. Limitations of actinide recycle and waste disposal consequences

    The paper emphasizes the impact of Light Water Reactor - Mixed Oxides introduction on the subsequent actinide management and fate of reprocessed and depleted uranium. The spent fuel from LWR-MOX contains in principle 75% of the initially produced plutonium. This new source term has to be considered together with the minor actinides from the conventional reprocessing. Subsequent LWR-MOX reprocessing in the first step in a very long term Pu + minor actinides management. Recycling of Pu + minor actinides in fast reactors to significantly reduce the Pu and minor actinides inventory (e.g. a factor of 10) is a very slow process which requires the development and operation of a large park of actinide burner reactors during an extended period of time. The overall feasibility of the P and T option will greatly depend on the massive introduction during the next century of fast neutron reactors as a replacement to the present LWR generation of nuclear power plants. (authors). 11 refs., 6 tabs., 2 figs

  12. Challenges in Modeling the Degradation of Ceramic Waste Forms

    Devanathan, Ramaswami; Gao, Fei; Sun, Xin

    2011-09-01

    We identify the state of the art, gaps in current understanding, and key research needs in the area of modeling the long-term degradation of ceramic waste forms for nuclear waste disposition. The directed purpose of this report is to define a roadmap for Waste IPSC needs to extend capabilities of waste degradation to ceramic waste forms, which overlaps with the needs of the subconsinuum scale of FMM interests. The key knowledge gaps are in the areas of (i) methodology for developing reliable interatomic potentials to model the complex atomic-level interactions in waste forms; (ii) characterization of water interactions at ceramic surfaces and interfaces; and (iii) extension of atomic-level insights to the long time and distance scales relevant to the problem of actinide and fission product immobilization.

  13. Technical requirements for the actinide source-term waste test program

    Phillips, M.L.F.; Molecke, M.A.

    1993-10-01

    This document defines the technical requirements for a test program designed to measure time-dependent concentrations of actinide elements from contact-handled transuranic (CH TRU) waste immersed in brines similar to those found in the underground workings of the Waste Isolation Pilot Plant (WIPP). This test program wig determine the influences of TRU waste constituents on the concentrations of dissolved and suspended actinides relevant to the performance of the WIPP. These influences (which include pH, Eh, complexing agents, sorbent phases, and colloidal particles) can affect solubilities and colloidal mobilization of actinides. The test concept involves fully inundating several TRU waste types with simulated WIPP brines in sealed containers and monitoring the concentrations of actinide species in the leachate as a function of time. The results from this program will be used to test numeric models of actinide concentrations derived from laboratory studies. The model is required for WIPP performance assessment with respect to the Environmental Protection Agency`s 40 CFR Part 191B.

  14. Technical requirements for the actinide source-term waste test program

    This document defines the technical requirements for a test program designed to measure time-dependent concentrations of actinide elements from contact-handled transuranic (CH TRU) waste immersed in brines similar to those found in the underground workings of the Waste Isolation Pilot Plant (WIPP). This test program wig determine the influences of TRU waste constituents on the concentrations of dissolved and suspended actinides relevant to the performance of the WIPP. These influences (which include pH, Eh, complexing agents, sorbent phases, and colloidal particles) can affect solubilities and colloidal mobilization of actinides. The test concept involves fully inundating several TRU waste types with simulated WIPP brines in sealed containers and monitoring the concentrations of actinide species in the leachate as a function of time. The results from this program will be used to test numeric models of actinide concentrations derived from laboratory studies. The model is required for WIPP performance assessment with respect to the Environmental Protection Agency's 40 CFR Part 191B

  15. Premises for use of fusion systems for actinide waste incineration

    The motivation for the present study is induction of a change in the attitude of fusion community and first of all of the respective decision makers with regard to the fission power. The aim is to convince them that admittance of any kinship of fusion to fission energy is not the greatest threat for its deployment. The true problems of fusion power lie in the physical and technological difficulties that are hindering the achievement of reliable operation and economical competitiveness of fusion reactors. It seems that the strong objections against any symbiosis of fusion with fission, which one could observe for over two decades, are based upon the ignorance of the public unaware of the common nuclear roots of both processes. They manifest themselves, among others, in the non-negligible activity to be induced in fusion devices, as a result of the exposition of construction materials to very strong fluxes of fusion (14 MeV) neutrons. The latter ones in addition, are the source of a very serious material damage in these materials. Meanwhile, most of the real difficulties fusion power is still facing can be effectively relaxed while shifting the heavy burden of sufficient production of energy to energy rich fission process. Seeing all this, first are reminded some important problems of existing fission power that stem from the unavoidable production of Minor Actinides, distinct by undesirable physical properties (intense radioactivity, heat release, positive reactivity coefficients). Thus, in search for solutions Fusion-Driven Incineration (FDI) subcritical systems (well remote from super prompt criticality) are proposed. Next, the problems of nuclear fusion are addressed and the use of fission energy contained in actinides of spent nuclear fuel is suggested. The main advantage of that option of fusion power, /thanks to energy release from fissions/, is the prospect of a radical reduction of necessary plasma energy gain Q to levels achievable in much smaller i.e. much

  16. Characterization Of Actinides In Simulated Alkaline Tank Waste Sludges And Leachates

    In this project, both the fundamental chemistry of actinides in alkaline solutions (relevant to those present in Hanford-style waste storage tanks), and their dissolution from sludge simulants (and interactions with supernatants) have been investigated under representative sludge leaching procedures. The leaching protocols were designed to go beyond conventional alkaline sludge leaching limits, including the application of acidic leachants, oxidants and complexing agents. The simulant leaching studies confirm in most cases the basic premise that actinides will remain in the sludge during leaching with 2-3 M NaOH caustic leach solutions. However, they also confirm significant chances for increased mobility of actinides under oxidative leaching conditions. Thermodynamic data generated improves the general level of experiemental information available to predict actinide speciation in leach solutions. Additional information indicates that improved Al removal can be achieved with even dilute acid leaching and that acidic Al(NO3)3 solutions can be decontaminated of co-mobilized actinides using conventional separations methods. Both complexing agents and acidic leaching solutions have significant potential to improve the effectiveness of conventional alkaline leaching protocols. The prime objective of this program was to provide adequate insight into actinide behavior under these conditions to enable prudent decision making as tank waste treatment protocols develop.

  17. CHARACTERIZATION OF ACTINIDES IN SIMULATED ALKALINE TANK WASTE SLUDGES AND LEACHATES

    Nash, Kenneth L.

    2008-11-20

    In this project, both the fundamental chemistry of actinides in alkaline solutions (relevant to those present in Hanford-style waste storage tanks), and their dissolution from sludge simulants (and interactions with supernatants) have been investigated under representative sludge leaching procedures. The leaching protocols were designed to go beyond conventional alkaline sludge leaching limits, including the application of acidic leachants, oxidants and complexing agents. The simulant leaching studies confirm in most cases the basic premise that actinides will remain in the sludge during leaching with 2-3 M NaOH caustic leach solutions. However, they also confirm significant chances for increased mobility of actinides under oxidative leaching conditions. Thermodynamic data generated improves the general level of experiemental information available to predict actinide speciation in leach solutions. Additional information indicates that improved Al removal can be achieved with even dilute acid leaching and that acidic Al(NO3)3 solutions can be decontaminated of co-mobilized actinides using conventional separations methods. Both complexing agents and acidic leaching solutions have significant potential to improve the effectiveness of conventional alkaline leaching protocols. The prime objective of this program was to provide adequate insight into actinide behavior under these conditions to enable prudent decision making as tank waste treatment protocols develop.

  18. Overall assessment of actinide partitioning and transmutation for waste management purposes

    A program to establish the technical feasibility and incentives for partitioning (i.e., recovering) actinides from fuel cycle wastes and then transmuting them in power reactors to shorter-lived or stable nuclides has recently been concluded at the Oak Ridge National Laboratory. The feasibility was established by experimentally investigating the reduction that can be practicably achieved in the actinide content of the wastes sent to a geologic repository, and the incentives for implementing this concept were defined by determining the incremental costs, risks, and benefits. Eight US Department of Energy laboratories and three private companies participated in the program over its 3-year duration. A reference fuel cycle was chosen based on a self-generated plutonium recycle PWR, and chemical flowsheets based on solvent extraction and ion-exchange techniques were generated that have the potential to reduce actinides in fuel fabrication and reprocessing plant wastes to less than 0.25% of those in the spent fuel. Waste treatment facilities utilizing these flowsheets were designed conceptually, and their costs were estimated. Finally, the short-term (contemporary) risks from fuel cycle operations and long-term (future) risks from deep geologic disposal of the wastes were estimated for cases with and without partitioning and transmutation. It was concluded that, while both actinide partitioning from wastes and transmutation in power reactors appear to be feasible using currently identified and studied technology, implementation of this concept cannot be justified because of the small long-term benefits and substantially increased costs of the concept

  19. Mixed Waste Focus Area - Waste form initiative

    The mission of the US Department of Energy's (DOE) Mixed Waste Focus Area (MWFA) is to provide acceptable technologies that enable implementation of mixed waste treatment systems which are developed in partnership with end-users, stakeholders, tribal governments, and regulators. To accomplish this mission, a technical baseline was established in 1996 and revised in 1997. The technical baseline forms the basis for determining which technology development activities will be supported by the MWFA. The primary attribute of the technical baseline is a set of prioritized technical deficiencies or roadblocks related to implementation of mixed waste treatment systems. The Waste Form Initiative (WFI) was established to address an identified technical deficiency related to waste form performance. The primary goal of the WFI was to ensure that the mixed low-level waste (MLLW) treatment technologies being developed, currently used, or planned for use by DOE would produce final waste forms that meet the waste acceptance criteria (WAC) of the existing and/or planned MLLW disposal facilities. The WFI was limited to an evaluation of the disposal requirements for the radioactive component of MLLW. Disposal requirements for the hazardous component are dictated by the Resource Conservation and Recovery Act (RCRA), and were not addressed. This paper summarizes the technical basis, strategy, and results of the activities performed as part of the WFI

  20. Criticality analysis of aggregations of actinides from commerical nuclear waste in geological storage

    An underground nuclear-waste terminal-storage facility for either spent fuel elements or high level waste from a reprocessing plant will contain large amounts of fissionable actinides. Such a facility must be designed to preclude the concentration of these isotopes into a critical mass. Information on the critical masses of the various isotopes present in spent fuel or high level waste is required as part of such a design effort. This study provides this information. The results of this study will be used, in conjunction with geologic transport rates of the actinide compounds, to estimate mass formation probabilities in waste repositories. A computational model was developed as part of the study to perform criticality calculations rapidly and efficiently and to produce tables and plots of actinide concentration in geologic material versus critical mass. The criticality model uses a discrete ordinates approximation to neutron transport theory and treats six energy groups and spherical geometry. Neutron cross sections were obtained from ENDF/B-IV or ENDF/B-V cross section libraries. Critical masses calculated with the computational model were checked against experimental values and against more detailed calculational values and were found to be from 30 percent less to 10 percent greater. Critical mass calculations were made for five waste types, five waste ages, five actinide elements, and four geologic compositions. Minimum critical masses were calculated for over 400 combinations of the above variables. The relative importance for criticality of the various actinides and waste types is presented in terms of the number of possible critical masses per waste container

  1. Radiation and transmutation effects relevant to solid nuclear waste forms

    Radiation effects in insulating solids are discussed in a general way as an introduction to the quite sparse published work on radiation effects in candidate nuclear waste forms other than glasses. Likely effects of transmutation in crystals and the chemical mitigation strategy are discussed. It seems probable that radiation effects in solidified HLW will not be serious if the actinides can be wholly incorporated in such radiation-resistant phases as monazite or uraninite

  2. Method of processing waste water containing actinide element by fixed tannin

    Since the waste water from a nuclear power plant is generally in an alkaline range above pH 8, in the case of processing waste water by using fixed tannin, fixed tannin is partially leached to unstable, and the adsorbing elimination rate of actinide elements contained in waste water is decreased. Accordingly, the fixed tannin is immersed and brought into contact with an aqueous solution of ammonia for pre-treatment. it is necessary that the pH value of the aqueous solution of ammonia used is higher than that of the waste water containing the actinide elements, and preferably, within a range of 10 to 12. The time of contact for ensuring the effect of the pre-treatment is at least 30 minutes for the lower limit and 60 minutes for the upper limit. In this way, the adsorbing performance itself can be improved and the processing performance for radioactive waste water can be improved. (T.M.)

  3. Strontium and Actinides Removal from Savannah River Site Actual Waste Samples by Freshly Precipitated Manganese Oxide

    The authors investigated the performance of freshly precipitated manganese oxide and monosodium titanate (MST) for the removal of strontium (Sr) and actinides from actual high-level waste. Manganese oxide precipitation occurs upon addition of a reductant such as formate (HCO2-) or peroxide (H2O2) to a waste solution containing permanganate (MnO4-). An addition of non-radioactive strontium typically precedes the MnO4- and reductant addition, which serves primarily to isotopically dilute the strontium-90 (90Sr) present in the waste. Tests utilized a Tank 37H/44F composite waste solution. Personnel significantly increased the concentration of actinides in the waste by the addition of acidic americium/curium solution (F-Canyon Tank 17.1 solution), which contained a significant quantity of plutonium (Pu), and neptunium-237 (237Np) stock solution. Initial tests examined three manganese oxide treatment options

  4. Vitreous ceramic waste form for waste immobilization

    Vitreous ceramic waste forms are being developed to complement glass waste forms in supporting DOE's environmental restoration efforts. The vitreous ceramics are composed of various metal oxide crystalline phases embedded in a silicate glass matrix. The vitreous ceramics are appropriate final waste forms for waste streams that contain large amounts of scrap metals and elements with low solubilities in glass, and have low-flux contents. Homogeneous glass waste forms are appropriate for wastes with sufficient fluxes and low metal contents. Therefore, utilization of both glass and vitreous ceramics waste forms will make vitrification technology applicable to the treatment of a much larger range of radioactive and mixed wastes. The controlled crystallization in vitreous ceramics resulted in formation of durable crystalline phases and durable residual glass matrix. The durable crystalline phases in vitreous ceramics included Ca3(PO4)2, magnetite (Fe2+Ni,Mn)Fe3+2O4, hibonite Ca(Al,Fe,Zr,Cr)12O19, baddeyelite ZrO2, zirconolite CaZrTi,O, and corundum Al2O3, which are thermodynamically more stable than normal glasses and are also less soluble in water than glasses. The durable glassy matrix in vitreous ceramics is due to the enrichment of silica and alumina during the crystallization process of vitreous ceramic formation. The vitreous ceramics showed exceptional long-term chemical durability and the processability of vitreous ceramics were also demonstrated at both bench- and pilot-scale. This paper briefly describes the use of vitreous ceramics for treating sample mixed wastes with high contents of either Cr, Fe, Zr, and Al, or alkalis

  5. Extraction of lanthanides and actinides from H. A. Waste by calix[4]arenes bearing CMPO units

    The decategorisation of radioactive liquid waste by removal of 90Sr, 137Cs and actinides (allowing the waste to be sent to a surface disposal after conditioning) or the separation of these long lived nuclides from solutions arising from the PUREX process (in order to destroy them by transmutation or to isolate them in high integrity matrixes) need very specific extractants. Carbamoylmethyl phosphine oxides are excellent extractants for actinides, especially the (N, N-di-isobutylcarbamoylmethyl) octyl phenyl phosphine oxide used in the TRUEX process. The species extracted contains three CMPO molecules per actinide cation. Thus, it seemed interesting to attach, in a suitable way and on an appropriate platform, three (or more) functional groups of the CMPO type, to better complex the trivalent cations

  6. Extraction of lanthanides and actinides from H. A. Waste by calix[4]arenes bearing CMPO units

    Dozol, J. F.; Carrera, A. Garcia; Rouquette, H.

    2000-07-01

    The decategorisation of radioactive liquid waste by removal of 90Sr, 137Cs and actinides (allowing the waste to be sent to a surface disposal after conditioning) or the separation of these long lived nuclides from solutions arising from the PUREX process (in order to destroy them by transmutation or to isolate them in high integrity matrixes) need very specific extractants. Carbamoylmethyl phosphine oxides are excellent extractants for actinides, especially the (N, N-di-isobutylcarbamoylmethyl) octyl phenyl phosphine oxide used in the TRUEX process. The species extracted contains three CMPO molecules per actinide cation. Thus, it seemed interesting to attach, in a suitable way and on an appropriate platform, three (or more) functional groups of the CMPO type, to better complex the trivalent cations.

  7. Consideration of uncertain nuclear data in the computation of the reduction of waste actinides by irradiation

    The most promising physical measure for quantity reduction of long-lived radiation sources and thus for the reduction of long-term risks at the ultimate store is further irradiation of the waste actinide nuclides in the neutron field of the reactor. In order to determine whether the nuclear data base now available on waste actinides (neptunium 237, plutonium 238, americium 241, americium 242, and americium 243) allows even now the actual design of reactors for further irradiation of such actinides, burn-up calculations must be made taking into consideration the uncertain character of nuclear data. For this purpose, an improved method for the computation of error propagation had to be elaborated. (orig./DG)

  8. Modeling of near field actinide concentrations in radioactive waste repositories in salt formations: effect of buffer materials

    Engineered barrier systems are designed to reduce the near field actinide concentrations in case of water penetration into a repository. In this paper, the influence of buffer materials, such as MgO/CaO and clays, on the solubilities of Am, Np, Pu, and U is studied. The analysis is performed for low level cemented waste forms in a rock salt formation in contact with MgCl2 saturated salt brine (Q-brine). The evolution of the geochemical milieu by cement corrosion is calculated using reaction path modeling supported by the code EQ3/6. The influence of different buffer materials is analyzed with respect to their impact on the solution chemistry and corresponding actinide concentrations. Copyright (2001) Material Research Society

  9. Waste forms for plutonium disposition

    The field of plutonium disposition is varied and of much importance, since the Department of Energy has decided on the hybrid option for disposing of the weapons materials. This consists of either placing the Pu into mixed oxide fuel for reactors or placing the material into a stable waste form such as glass. The waste form used for Pu disposition should exhibit certain qualities: (1) provide for a suitable deterrent to guard against proliferation; (2) be of minimal volume, i.e., maximize the loading; and (3) be reasonably durable under repository-like conditions. This paper will discuss several Pu waste forms that display promising characteristics

  10. Status of development of actinide blanket processing flowsheets for accelerator transmutation of nuclear waste

    An accelerator-driven subcritical nuclear system is briefly described that transmutes actinides and selected long-lived fission products. An application of this accelerator transmutation of nuclear waste (ATW) concept to spent fuel from a commercial nuclear power plant is presented as an example. The emphasis here is on a possible aqueous processing flowsheet to separate the actinides and selected long-lived fission products from the remaining fission products within the transmutation system. In the proposed system the actinides circulate through the thermal neutron flux as a slurry of oxide particles in heavy water in two loops with different average residence times: one loop for neptunium and plutonium and one for americium and curium. Material from the Np/Pu loop is processed with a short cooling time (5-10 days) because of the need to keep the total actinide inventory, low for this particular ATW application. The high radiation and thermal load from the irradiated material places severe constraints on the separation processes that can be used. The oxide particles are dissolved in nitric acid and a quarternary, ammonium anion exchanger is used to extract neptunium, plutonium, technetium, and palladium. After further cooling (about 90 days), the Am, Cm and higher actinides are extracted using a TALSPEAK-type process. The proposed operations were chosen because they have been successfully tested for processing high-level radioactive fuels or wastes in gram to kilogram quantities

  11. Materials Characterization Center. Second workshop on irradiation effects in nuclear waste forms. Summary report

    Weber, W.J.; Turcotte, R.P.

    1982-01-01

    The purpose of this second workshop on irradiations effects was to continue the discussions initiated at the first workshop and to obtain guidance for the Materials Characterization Center in developing test methods. The following major conclusions were reached: Ion or neutron irradiations are not substitutes for the actinide-doping technique, as described by the MCC-6 Method for Preparation and Characterization of Actinide-Doped Waste Forms, in the final evaluation of any waste form with respect to the radiation effects from actinide decay. Ion or neutron irradiations may be useful for screening tests or more fundamental studies. The use of these simulation techniques as screening tests for actinide decay requires that a correlation between ion or neutron irradiations and actinide decay be established. Such a correlation has not yet been established and experimental programs in this area are highly recommended. There is a need for more fundamental studies on dose-rate effects, temperature dependence, and the nature and importance of alpha-particle effects relative to the recoil nucleus in actinide decay. There are insufficient data presently available to evaluate the potential for damage from ionizing radiation in nuclear waste forms. No additional test methods were recommended for using ion or neutron irradiations to simulate actinide decay or for testing ionization damage in nuclear waste forms. It was recognized that additional test methods may be required and developed as more data become available. An American Society for Testing and Materials (ASTM) Task Group on the Simulation of Radiation Effects in Nuclear Waste Forms (E 10.08.03) was organized to act as a continuing vehicle for discussions and development of procedures, particularly with regard to ion irradiations.

  12. The nuclear waste issue: towards an assessment of the partitioning and transmutation of actinides

    First of all, this paper describes recent regulatory, scientific and technical developments in France concerning the management of high level, long-lived radioactive waste. In this context, which culminated in parliament's adoption of the radioactive waste management bill, it analyses, from an industrial viewpoint, the motivation for separating and transmuting minor actinides, as well as the technical and economic consequences for waste management. The new law underlines the need to reduce the harmfulness of radioactive waste and research into separation and transmutation is continuing with a view to 'an assessment in 2012 of the industrial perspectives for these technologies' that makes allowance for the developments made with new reactors. It is admitted that the waste will not be eradicated by transmutation and therefore that the geological disposal is inevitable. But destroying the waste, however partially, is worthy of consideration if it helps to simplify disposal and reduce costs. It may also merely reduce safety assessment uncertainty or increase calculation margins. The results of previous studies have shown that research has to focus on the minor actinides. On the one hand, they account for practically all the radiotoxicity of waste and on the other hand, with the exception of two fission products with relatively short half-lives for which suitable interim storage is to be envisaged, they are the main contributors to the thermal load. We therefore examine the possible consequences of management through actinide separation and transmutation on the fuel cycle as a whole, and the advantages to be gained for disposal or release. For example, americium makes a considerable contribution to the thermal load and transmutation would appear possible. Conversely, curium is known to be difficult to transmute and would complicate target or fuel fabrication operations. The potential savings to be made in disposal costs should also make allowance for future optimization

  13. Recovery of actinides from TBP-Na2Co3 scrub-waste solutions: the ARALEX process

    A flowsheet for the recovery of actinides from TBP-Na2CO3 scrub-waste solutions has been developed, based on batch extraction data, and tested, using laboratory-scale countercurrent extraction techniques. The process, called the ARALEX process, uses 2-ethyl-1-hexanol (2-EHOH) to extract the TBP degradation products (HDBP and H2MBP) from acidified Na2CO3 scrub waste leaving the actinides in the aqueous phase. Dibutyl and monobutyl phosphoric acids are attached to the 2-EHOH molecules through hydrogen bonds, which also diminish the ability of the HDBP and H2MBP to complex actinides. Thus all actinides remain in the aqueous raffinate. Dilute sodium hydroxide solutions can be used to back-extract the dibutyl and monobutyl phosphoric acid esters as their sodium salts. The 2-EHOH can then be recycled. After extraction of the acidified carbonate waste with 2-EHOH, the actinides may be readily extracted from the raffinate with DHDECMP or, in the case of tetra- and hexavalent actinides, with TBP. The ARALEX process can also be applied to other actinide waste streams which contain appreciable concentrations of polar organic compounds (e.g., detergents) that interfere with conventional actinide ion exchange and liquid-liquid extraction procedures. 20 figures, 6 tables

  14. Diffusion from cylindrical waste forms

    The diffusion of a single component material from a finite cylindrical waste form, initially containing a uniform concentration of the material, is investigated. Under the condition that the cylinder is maintained in a well-stirred bath, expressions for the fractional inventory leached and the leach rate are derived with allowance for the possible permanent immobilization of the diffusant through its decay to a stable product and/or its irreversible reaction with the waste form matrix. The usefulness of the reported results in nuclear waste disposal applications is emphasized. The results reported herein are related to those previously derived at Oak Ridge National Laboratory by Bell and Nestor. A numerical scheme involving the partial decoupling of nested infinite summations and the use of rapidly converging rational approximants is recommended for the efficient implementation of the expressions derived to obtain reliable estimates of the bulk diffusion constant and the rate constant describing the diffusant-waste form interaction from laboratory data

  15. STRONTIUM AND ACTINIDE SEPARATIONS FROM HIGH LEVEL NUCLEAR WASTE SOLUTIONS USING MONOSODIUM TITANATE 1. SIMULANT TESTING

    HOBBS, D. T.; BARNES, M. J.; PULMANO, R. L.; MARSHALL, K. M.; EDWARDS, T. B.; BRONIKOWSKI, M. G.; FINK, S. D.

    2005-04-14

    High-level nuclear waste produced from fuel reprocessing operations at the Savannah River Site (SRS) requires pretreatment to remove {sup 137}Cs, {sup 90}Sr and alpha-emitting radionuclides (i.e., actinides) prior to disposal. Separation processes planned at SRS include caustic side solvent extraction, for {sup 137}Cs removal, and ion exchange/sorption of {sup 90}Sr and alpha-emitting radionuclides with an inorganic material, monosodium titanate (MST). The predominant alpha-emitting radionuclides in the highly alkaline waste solutions include plutonium isotopes {sup 238}Pu, {sup 239}Pu and {sup 240}Pu. This paper provides a summary of data acquired to measure the performance of MST to remove strontium and actinides from simulated waste solutions. These tests evaluated the influence of ionic strength, temperature, solution composition and the oxidation state of plutonium.

  16. ENHANCED CHEMICAL CLEANING OF SRS WASTE TANKS TO IMPROVE ACTINIDE SOLUBILITY

    Rudisill, T.; Thompson, M.

    2011-09-20

    Processes for the removal of residual sludge from SRS waste tanks have historically used solutions containing up to 0.9 M oxalic acid to dissolve the remaining material following sludge removal. The selection of this process was based on a comparison of a number of studies performed to evaluate the dissolution of residual sludge. In contrast, the dissolution of the actinide mass, which represents a very small fraction of the waste, has not been extensively studied. The Pu, Np, and Am in the sludge is reported to be present as hydrated and crystalline oxides. To identify aqueous solutions which have the potential to increase the solubility of the actinides, the alkaline and mildly acidic test solutions shown below were selected as candidates for use in a series of solubility experiments. The efficiency of the solutions in solubilizing the actinides was evaluated using a simulated sludge prepared by neutralizing a HNO{sub 3} solution containing Pu, Np, and Am. The hydroxide concentration was adjusted to a 1.2 M excess and the solids were allowed to age for several weeks prior to starting the experiments. The sludge was washed with 0.01 M NaOH to prepare the solids for use. Following the addition of an equal portion of the solids to each test solution, the concentrations of Pu, Np, and Am were measured as a function of time over a 792 h (33 day) period to provide a direct comparison of the efficiency of each solution in solubilizing the actinide elements. Although the composition of the sludge was limited to the hydrated actinide oxides (and did not contain other components of demonstrated importance), the results of the study provides guidance for the selection of solutions which should be evaluated in subsequent tests with a more realistic surrogate sludge and actual tank waste.

  17. Waste form development/test

    The main objective of this study is to investigate new solidification agents relative to their potential application to wastes generated by advanced high volume reduction technologies, e.g., incinerator ash, dry solids, and ion exchange resins. Candidate materials selected for the solidification of these wastes include a modified sulfur cement and low-density polyethylene, neither of which are currently employed commerically for the solidification of low-level waste (LLW). As both the modified sulfur cement and the polyethylene are thermoplastic materials, a heated screw type extruder is utilized in the production of waste form samples for testing and evaluation. In this regard, work is being conducted to determine the range of conditions under which these solidification agents can be satisfactorily applied to the specific LLW streams and to provide information relevant to operating parameters and process control

  18. NNWSI waste form testing program

    A waste form testing program has been developed to ensure that the release rate of radionuclides from the engineered barrier system will meet NRC and EPA regulatory requirements. Waste form performance testing will be done under unsaturated, low water availability conditions which represent the expected repository conditions. Testing will also be done under conditions of total immersion of the waste form in repository-type water to cover the possibility that localized portions of the repository might contain standing water. Testing of reprocesses waste forms for CHLW and DHLW will use reaction vessels fabricated from Topopah Spring tuff. Chemical elements which are expected to show the highest release rates in the mildly oxidizing environment of the Topopah Spring tuff horizon at Yucca Mountain are Np and Tc. To determine the effect of residual canister material and of corrosion products from the canister/overpack, waste form testing will be done in the presence of these materials. The release rate of all radionuclides which are subject to NRC and EPA regulations will be measured, and the interactive effects of the released radionuclide and the rock reaction vessels will be determined. The testing program for spent fuel will determine the release rate from bare spent fuel pellets and from Zircaloy clad spent fuel where the cladding contains minor defects. A metal testing program for Zircaloy will establish the expected lifetime of the cladding material. Estimation of the state of cladding for fuel presently in reactor pool storage will provide baseline data for Zircaloy containment credit. 9 references, 4 figures

  19. Demonstration of innovative partitioning processes for minor actinide recycling from high active waste solutions

    The recycling of the minor actinides (MA) using the Partitioning and Transmutation strategy (P and T) could contribute significantly to reducing the volume of high level waste in a geological repository and to decreasing the waste's longterm hazards originating from the long half-life of the actinides. Several extraction processes have been developed worldwide for the separation and recovery of MA from highly active raffinates (HAR, e.g. the PUREX raffinate). A multi-cycle separation strategy has been developed within the framework of European collaborative projects. The multi-cycle processes, on the one hand, make use of different extractants for every single process. Within the recent FP7 European research project ACSEPT (Actinide reCycling by SEParation and Transmutation), the development of new innovative separation processes with a reduced number of cycles was envisaged. In the so-called 'innovative SANEX' concept, the trivalent actinides and lanthanides are co-extracted from the PUREX raffinate by a DIAMEX like process (e.g. TODGA). Then, the loaded solvent is subjected to several stripping steps. The first one concerns selectively stripping the actinides(III) with selective water-soluble ligands (SO3-Ph-BTB), followed by the subsequent stripping of trivalent lanthanides. A more challenging route studied also within our laboratories is the direct actinide(III) separation from a PUREX-type raffinate using a mixture of CyMe4BTBP and TODGA as extractants, the so-called One cycle SANEX process. A new approach, which was also studied within the ACSEPT project, is the GANEX (Grouped ActiNide EXtraction) concept addressing the simultaneous partitioning of all transuranium (TRU) elements for their homogeneous recycling in advanced generation IV reactor systems. Bulk uranium is removed in the GANEX 1st cycle, e.g. using a monoamide extractant and the GANEX 2nd cycle then separates the TRU. A solvent composed of TODGA + DMDOHEMA in kerosene has been shown to

  20. Coated particle waste form development

    Coated particle waste forms have been developed as part of the multibarrier concept at Pacific Northwest Laboratory under the Alternative Waste Forms Program for the Department of Energy. Primary efforts were to coat simulated nuclear waste glass marbles and ceramic pellets with low-temperature pyrolytic carbon (LT-PyC) coatings via the process of chemical vapor deposition (CVD). Fluidized bed (FB) coaters, screw agitated coaters (SAC), and rotating tube coaters were used. Coating temperatures were reduced by using catalysts and plasma activation. In general, the LT-PyC coatings did not provide the expected high leach resistance as previously measured for carbon alone. The coatings were friable and often spalled off the substrate. A totally different concept, thermal spray coating, was investigated at PNL as an alternative to CVD coating. Flame spray, wire gun, and plasma gun systems were evaluated using glass, ceramic, and metallic coating materials. Metal plasma spray coatings (Al, Sn, Zn, Pb) provided a two to three orders-of-magnitude increase in chemical durability. Because the aluminum coatings were porous, the superior leach resistance must be due to either a chemical interaction or to a pH buffer effect. Because they are complex, coated waste form processes rank low in process feasibility. Of all the possible coated particle processes, plasma sprayed marbles have the best rating. Carbon coating of pellets by CVD ranked ninth when compared with ten other processes. The plasma-spray-coated marble process ranked sixth out of eleven processes

  1. Coated particle waste form development

    Oma, K.H.; Buckwalter, C.Q.; Chick, L.A.

    1981-12-01

    Coated particle waste forms have been developed as part of the multibarrier concept at Pacific Northwest Laboratory under the Alternative Waste Forms Program for the Department of Energy. Primary efforts were to coat simulated nuclear waste glass marbles and ceramic pellets with low-temperature pyrolytic carbon (LT-PyC) coatings via the process of chemical vapor deposition (CVD). Fluidized bed (FB) coaters, screw agitated coaters (SAC), and rotating tube coaters were used. Coating temperatures were reduced by using catalysts and plasma activation. In general, the LT-PyC coatings did not provide the expected high leach resistance as previously measured for carbon alone. The coatings were friable and often spalled off the substrate. A totally different concept, thermal spray coating, was investigated at PNL as an alternative to CVD coating. Flame spray, wire gun, and plasma gun systems were evaluated using glass, ceramic, and metallic coating materials. Metal plasma spray coatings (Al, Sn, Zn, Pb) provided a two to three orders-of-magnitude increase in chemical durability. Because the aluminum coatings were porous, the superior leach resistance must be due to either a chemical interaction or to a pH buffer effect. Because they are complex, coated waste form processes rank low in process feasibility. Of all the possible coated particle processes, plasma sprayed marbles have the best rating. Carbon coating of pellets by CVD ranked ninth when compared with ten other processes. The plasma-spray-coated marble process ranked sixth out of eleven processes.

  2. Glass-Ceramic Waste Forms for Uranium and Plutonium Residues Wastes - 13164

    A program of work has been undertaken to treat plutonium-residues wastes at Sellafield. These have arisen from past fuel development work and are highly variable in both physical and chemical composition. The principal radiological elements present are U and Pu, with small amounts of Th. The waste packages contain Pu in amounts that are too low to be economically recycled as fuel and too high to be disposed of as lower level Pu contaminated material. NNL and ANSTO have developed full-ceramic and glass-ceramic waste forms in which hot-isostatic pressing is used as the consolidation step to safely immobilize the waste into a form suitable for long-term disposition. We discuss development work on the glass-ceramic developed for impure waste streams, in particular the effect of variations in the waste feed chemistry glass-ceramic. The waste chemistry was categorized into actinides, impurity cations, glass formers and anions. Variations of the relative amounts of these on the properties and chemistry of the waste form were investigated and the waste form was found to be largely unaffected by these changes. This work mainly discusses the initial trials with Th and U. Later trials with larger variations and work with Pu-doped samples further confirmed the flexibility of the glass-ceramic. (authors)

  3. Glass-Ceramic Waste Forms for Uranium and Plutonium Residues Wastes - 13164

    Stewart, Martin W.A.; Moricca, Sam A.; Zhang, Yingjie; Day, R. Arthur; Begg, Bruce D. [Australian Nuclear Science and Technology Organisation (ANSTO), New Illawarra Road, Lucas Heights, NSW 2234 (Australia); Scales, Charlie R.; Maddrell, Ewan R. [National Nuclear Laboratory, Sellafield, Seascale, Cumbria, UK, CA20 1PG (United Kingdom); Hobbs, Jeff [Sellafield Limited, Sellafield, Seascale, Cumbria, UK, CA20 1PG (United Kingdom)

    2013-07-01

    A program of work has been undertaken to treat plutonium-residues wastes at Sellafield. These have arisen from past fuel development work and are highly variable in both physical and chemical composition. The principal radiological elements present are U and Pu, with small amounts of Th. The waste packages contain Pu in amounts that are too low to be economically recycled as fuel and too high to be disposed of as lower level Pu contaminated material. NNL and ANSTO have developed full-ceramic and glass-ceramic waste forms in which hot-isostatic pressing is used as the consolidation step to safely immobilize the waste into a form suitable for long-term disposition. We discuss development work on the glass-ceramic developed for impure waste streams, in particular the effect of variations in the waste feed chemistry glass-ceramic. The waste chemistry was categorized into actinides, impurity cations, glass formers and anions. Variations of the relative amounts of these on the properties and chemistry of the waste form were investigated and the waste form was found to be largely unaffected by these changes. This work mainly discusses the initial trials with Th and U. Later trials with larger variations and work with Pu-doped samples further confirmed the flexibility of the glass-ceramic. (authors)

  4. Solubility and speciation of actinides in salt solutions and migration experiments of intermediate level waste in salt formations

    A comprehensive study into the solubility of the actinides americium and plutonium in concentrated salt solutions, the release of radionuclides from various forms of conditioned ILW and the migration behaviour of these nuclides through geological material specific to the Gorleben site in Lower Saxony is described. A detailed investigation into the characterization of four highly concentrated salt solutions in terms of their pH, Eh, inorganic carbon contents and their densities is given and a series of experiments investigating the solubility of standard americium(III) and plutonium(IV) hydroxides in these solutions is described. Transuranic mobility studies for solutions derived from the standard hydroxides through salt and sand have shown the presence of at least two types of species present of widely differing mobility; one migrating with approximately the same velocity as the solvent front and the other strongly retarded. Actinide mobility data are presented and discussed for leachates derived from the simulated ILW in cement and data are also presented for the migration of the fission products in leachates derived from real waste solidified in cement and bitumen. Relatively high plutonium mobilities were observed in the case of the former and in the case of the real waste leachates, cesium was found to be the least retarded. The sorption of ruthenium was found to be largely associated with the insoluble residues of the natural rock salt rather than the halite itself. (orig./RB)

  5. Applicability of molten salt oxidation to the destruction of actinide-contaminated wastes

    A 1989 ban on incineration in the state of New Mexico caused cessation of actinide-contaminated cheesecloth, paper, and wood incineration within the Plutonium Facility (TA-55) at Los Alamos National Laboratory. Subsequently, plastic wipes were substituted for cheesecloth in the cleaning of glovebox interiors. However, waste minimization is not achieved by these measures since the wipes are discarded as Waste Isolation Pilot Plant certifiable wastes. After the ban was instituted, thermal decomposition of cheesecloth under argon at elevated temperature was examined and found satisfactory although scale of operation and speed were inferior to incineration. In 1991, the ban on incineration was lifted in New Mexico but Alamos has not chosen to pursue renewal of incineration at the Plutonium Facility. This paper reports that Los Alamos is looking from alternatives to incineration and thermal decomposition which are compatible with molten salt processing technology, historically a strength in actinide research at the Laboratory. Also, the technology must significantly reduce the volume of the waste upon treatment, i.e. waste minimization. Molten salt oxidation (MSO) has the promise of such a technology

  6. Characterization of Actinides in Simulated Alkaline Tank Waste Sludges and Leachates

    During sludge washing procedures associated with tank waste remediation, actinide ions are expected to remain with the insoluble metal oxide/hydroxide residue as the sludges are scrubbed to remove Cr, P, Al, S, and thus to be transmitted conveniently to the vitrification plant. Unfortunately, in laboratory tests with actual sludge samples alkaline sludge treatment has proven less efficacious for Al and Cr removal than was hoped. To improve removal of Al and Cr, more aggressive treatments of sludges are anticipated, including contact with oxidants targeting Cr(III). In addition, our prior research on the alkaline scrubbing of sludge simulants indicated higher than expected ''solubilization'' of Np and U into concentrated alkali, and some tendency for Am to be mobilized in contact with oxidants. In this project, we are investigating the fundamental chemistry of actinides in sludge simulants under representative oxidative leaching conditions. We are also examining acidic leaching with concurrent secondary separations to enhance Al removal. Our objective is to provide adequate insight into actinide behavior under these conditions to enable prudent decision making as tank waste treatment protocols develop. We expect to identify those components of sludges that are likely to be problematic in the application of oxidative leaching protocols

  7. Secondary Waste Cast Stone Waste Form Qualification Testing Plan

    Westsik, Joseph H.; Serne, R. Jeffrey

    2012-09-26

    The Hanford Tank Waste Treatment and Immobilization Plant (WTP) is being constructed to treat the 56 million gallons of radioactive waste stored in 177 underground tanks at the Hanford Site. The WTP includes a pretreatment facility to separate the wastes into high-level waste (HLW) and low-activity waste (LAW) fractions for vitrification and disposal. The LAW will be converted to glass for final disposal at the Integrated Disposal Facility (IDF). Cast Stone – a cementitious waste form, has been selected for solidification of this secondary waste stream after treatment in the ETF. The secondary-waste Cast Stone waste form must be acceptable for disposal in the IDF. This secondary waste Cast Stone waste form qualification testing plan outlines the testing of the waste form and immobilization process to demonstrate that the Cast Stone waste form can comply with the disposal requirements. Specifications for the secondary-waste Cast Stone waste form have not been established. For this testing plan, Cast Stone specifications are derived from specifications for the immobilized LAW glass in the WTP contract, the waste acceptance criteria for the IDF, and the waste acceptance criteria in the IDF Permit issued by the State of Washington. This testing plan outlines the testing needed to demonstrate that the waste form can comply with these waste form specifications and acceptance criteria. The testing program must also demonstrate that the immobilization process can be controlled to consistently provide an acceptable waste form product. This testing plan also outlines the testing needed to provide the technical basis for understanding the long-term performance of the waste form in the disposal environment. These waste form performance data are needed to support performance assessment analyses of the long-term environmental impact of the secondary-waste Cast Stone waste form in the IDF

  8. Partitioning of actinides from high-level waste streams of Purex process using mixtures of CMPO and TBP in dodecane

    The extraction of actinides from high active aqueous raffinate waste (HAW) as well as high-level waste (HLW) solutions arising from Purex processing of thermal reactor fuels has been studied using a mixture of octyl(phenyl)-N,N-diisobutylcarbamoyl-methylphosphine oxide (CMPO) and TBP in dodecane. The results on the extraction and stripping of actinides, lanthanides, and other fission products are discussed. Optimum conditions are proposed for the efficient recovery of residual actinides from HAW and HLW streams by CMPO extraction followed by their selective stripping with suitable reagents. Experiments on the extraction and separation of actinides and lanthanides by CMPO in the presence of TBP in dodecane have also been carried out with U(VI) and Nd(III) to arrive at the limiting conditions for avoiding third-phase formation

  9. Extraction of actinides from high level waste streams of purex process using mixtures of CMPO and TBP in dodecane

    The extraction of actinides from high-active aqueous raffinate waste (HAW) as well as high level waste (HLW) solutions arising from Purex processing of thermal reactor fuels has been studied using a mixture of octyl(phenyl)-N, N-diisobutylcarbamoylmethylphosphine oxide (CMPO) and TBP in dodecane. The results on the extraction and striping of actinides, lanthanides and other fission products have been discussed in this report and optimum conditions have been proposed for the efficient recovery of residual actinides from HAW and HLW streams by CMPO extraction and for their selective stripping with suitable reagents. Experiments on the extraction and separation of actinides and lanthanides by CMPO in the presence of TBP in dodecane have also been carried out with U(VI) and Nd(III) to arrive at the limiting conditions for avoiding third phase formation. (author). 18 refs., 5 figs., 10 tabs

  10. TSA waste stream and final waste form composition

    Grandy, J.D.; Eddy, T.L.; Anderson, G.L.

    1993-01-01

    A final vitrified waste form composition, based upon the chemical compositions of the input waste streams, is recommended for the transuranic-contaminated waste stored at the Transuranic Storage Area of the Radioactive Waste Management Complex at the Idaho National Engineering Laboratory. The quantities of waste are large with a considerable uncertainty in the distribution of various waste materials. It is therefore impractical to mix the input waste streams into an ``average`` transuranic-contaminated waste. As a result, waste stream input to a melter could vary widely in composition, with the potential of affecting the composition and properties of the final waste form. This work examines the extent of the variation in the input waste streams, as well as the final waste form under conditions of adding different amounts of soil. Five prominent Rocky Flats Plant 740 waste streams are considered, as well as nonspecial metals and the ``average`` transuranic-contaminated waste streams. The metals waste stream is the most extreme variation and results indicate that if an average of approximately 60 wt% of the mixture is soil, the final waste form will be predominantly silica, alumina, alkaline earth oxides, and iron oxide. This composition will have consistent properties in the final waste form, including high leach resistance, irrespective of the variation in waste stream. For other waste streams, much less or no soil could be required to yield a leach resistant waste form but with varying properties.

  11. TSA waste stream and final waste form composition

    A final vitrified waste form composition, based upon the chemical compositions of the input waste streams, is recommended for the transuranic-contaminated waste stored at the Transuranic Storage Area of the Radioactive Waste Management Complex at the Idaho National Engineering Laboratory. The quantities of waste are large with a considerable uncertainty in the distribution of various waste materials. It is therefore impractical to mix the input waste streams into an ''average'' transuranic-contaminated waste. As a result, waste stream input to a melter could vary widely in composition, with the potential of affecting the composition and properties of the final waste form. This work examines the extent of the variation in the input waste streams, as well as the final waste form under conditions of adding different amounts of soil. Five prominent Rocky Flats Plant 740 waste streams are considered, as well as nonspecial metals and the ''average'' transuranic-contaminated waste streams. The metals waste stream is the most extreme variation and results indicate that if an average of approximately 60 wt% of the mixture is soil, the final waste form will be predominantly silica, alumina, alkaline earth oxides, and iron oxide. This composition will have consistent properties in the final waste form, including high leach resistance, irrespective of the variation in waste stream. For other waste streams, much less or no soil could be required to yield a leach resistant waste form but with varying properties

  12. Subsurface Biogeochemistry of Actinides

    Kersting, Annie B. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States). Univ. Relations and Science Education; Zavarin, Mavrik [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States). Glenn T. Seaborg Inst.

    2016-06-29

    A major scientific challenge in environmental sciences is to identify the dominant processes controlling actinide transport in the environment. It is estimated that currently, over 2200 metric tons of plutonium (Pu) have been deposited in the subsurface worldwide, a number that increases yearly with additional spent nuclear fuel (Ewing et al., 2010). Plutonium has been shown to migrate on the scale of kilometers, giving way to a critical concern that the fundamental biogeochemical processes that control its behavior in the subsurface are not well understood (Kersting et al., 1999; Novikov et al., 2006; Santschi et al., 2002). Neptunium (Np) is less prevalent in the environment; however, it is predicted to be a significant long-term dose contributor in high-level nuclear waste. Our focus on Np chemistry in this Science Plan is intended to help formulate a better understanding of Pu redox transformations in the environment and clarify the differences between the two long-lived actinides. The research approach of our Science Plan combines (1) Fundamental Mechanistic Studies that identify and quantify biogeochemical processes that control actinide behavior in solution and on solids, (2) Field Integration Studies that investigate the transport characteristics of Pu and test our conceptual understanding of actinide transport, and (3) Actinide Research Capabilities that allow us to achieve the objectives of this Scientific Focus Area (SFA and provide new opportunities for advancing actinide environmental chemistry. These three Research Thrusts form the basis of our SFA Science Program (Figure 1).

  13. R and D for actinide partitioning and recovery of valuables from high level waste using radiotracers

    In the context of growing world population with rapidly increasing energy needs and the threat of global warming due to CO2 emission (caused by fossil fuel burning), the nuclear energy may be an attractive option particularly in the developing countries. Recycling of fuel is a unique feature of nuclear power technology which makes it a favourable choice with respect to conservation of energy resources. Steady growth of global fuel reprocessing activities (6000 tHM/annum) implies a vital role of separation science in developing efficient procedures for the separation and purification of actinides and in devising safe procedures for the management of nuclear waste arising at different stages of the PUREX process. High Level Waste (HLW) comprising of the concentrate of the raffinate of the co-extraction cycle (with over 95% of the total radioactivity produced in the burn up process in reactor) need to be isolated from the biosphere. There is a consensus among the waste management technologists that the safest route to achieve this, is to deposit it in a stable geological formation after it's immobilization in suitable glass/Synroc matrix. It ensures that any risk from exposure due to accidental intervention or natural disturbance is minimized. Risk perception is essentially due to the large radiological toxicity associated with alpha emitters like 237Np, 241Am, 243Am and 245Cm. Isotopes of Pu (left unrecovered) present in HLW also contribute towards radiological toxicity. In view of the high cost involved and the need for continuous surveillance, several countries are considering modifying their reprocessing schemes to partition (isolate) long-lived actinides from HLW. Since the volume of the actinide oxides (which retain major fraction of the radio toxicity of HLW) is significantly lower as compared to the other metal oxides present in HLW, such an approach is expected to reduce the cost of immobilization as well as of disposal (in geological repository) and

  14. Actinide speciation bound to hydrous ferric oxide colloids in the near-field conditions of the waste pond at 'Mayak' facility (Russia)

    Full text of publication follows: 'Mayak' facility is a nuclear waste and spent nuclear fuel reprocessing plant located in Ural Mountains, Russia. The opened pond, Karachay Lake, was used for several decades for the discharge of low- and intermediate level waste solutions containing fission products and traces of actinides. Due to high salt concentration and high density of waste solutions, they are penetrating into the groundwater system that is represented by oxic Eh conditions. The speciation of actinides in groundwater samples collected close to Karachay Lake was studied by successive micro- and ultra-filtrations with subsequent SEM, TEM, nano-SIMS, membrane extraction and other techniques. It was established that U and Np were found in soluble fraction (pass through 10 kD ultra-filter) in the form of their bi- and tri-carbonate complexes that was supported by chemical thermodynamic calculations. In contrast, Pu and Am were bound to nano-colloids 10 kD - 50 nm in size. The SEM and TEM data indicate the presence of variety of different colloidal particles which relative concentration decrease in the row: hydrous ferric oxides (HFO) >> clays ≅ calcite > rutile ≅ hematite ≅ barite ≅ MnO2 > monazite > other phases. The SIMS with submicron resolution (Cameca nanoSIMS-50) was used to study local concentration of actinides. According to the obtained data among different colloids detected in the sample actinides were preferentially bound to HFO and MnO2 while other phases did not sorb actinides. In order to determine actinide speciation bound to HFO colloids XPS and An L3 edge XAFS measurements were done at Siberian Synchrotron Radiation Centre. The storage ring VEPP-3 with electron beam energy of 2 GeV and an average stored current of 80 mA was used as the source of radiation. Since the concentration of actinides in actual samples was too low for XAFS, the samples for measurements were prepared by contacting about 10-5 M solutions of Np(V) and Pu(V) with UFO

  15. CERAMIC WASTE FORM DATA PACKAGE

    Amoroso, J.; Marra, J.

    2014-06-13

    The purpose of this data package is to provide information about simulated crystalline waste forms that can be used to select an appropriate composition for a Cold Crucible Induction Melter (CCIM) proof of principle demonstration. Melt processing, viscosity, electrical conductivity, and thermal analysis information was collected to assess the ability of two potential candidate ceramic compositions to be processed in the Idaho National Laboratory (INL) CCIM and to guide processing parameters for the CCIM operation. Given uncertainties in the CCIM capabilities to reach certain temperatures throughout the system, one waste form designated 'Fe-MP' was designed towards enabling processing and another, designated 'CAF-5%TM-MP' was designed towards optimized microstructure. Melt processing studies confirmed both compositions could be poured from a crucible at 1600{degrees}C although the CAF-5%TM-MP composition froze before pouring was complete due to rapid crystallization (upon cooling). X-ray diffraction measurements confirmed the crystalline nature and phase assemblages of the compositions. The kinetics of melting and crystallization appeared to vary significantly between the compositions. Impedance spectroscopy results indicated the electrical conductivity is acceptable with respect to processing in the CCIM. The success of processing either ceramic composition will depend on the thermal profiles throughout the CCIM. In particular, the working temperature of the pour spout relative to the bulk melter which can approach 1700{degrees}C. The Fe-MP composition is recommended to demonstrate proof of principle for crystalline simulated waste forms considering the current configuration of INL's CCIM. If proposed modifications to the CCIM can maintain a nominal temperature of 1600{degrees}C throughout the melter, drain, and pour spout, then the CAF-5%TM-MP composition should be considered for a proof of principle demonstration.

  16. Actinide chemistry research supporting the Waste Isolation Pilot Plant (WIPP): FY94 results

    This document contains six reports on actinide chemistry research supporting the Waste Isolation Pilot Plant (WIPP). These reports, completed in FY94, are relevant to the estimation of the potential dissolved actinide concentrations in WIPP brines under repository breach scenarios. Estimates of potential dissolved actinide concentrations are necessary for WIPP performance assessment calculations. The specific topics covered within this document are: the complexation of oxalate with Th(IV) and U(VI); the stability of Pu(VI) in one WIPP-specific brine environment both with and without carbonate present; the solubility of Nd(III) in a WIPP Salado brine surrogate as a function of hydrogen ion concentration; the steady-state dissolved plutonium concentrations in a synthetic WIPP Culebra brine surrogate; the development of a model for Nd(III) solubility and speciation in dilute to concentrated sodium carbonate and sodium bicarbonate solutions; and the development of a model for Np(V) solubility and speciation in dilute to concentrated sodium Perchlorate, sodium carbonate, and sodium chloride media

  17. Actinide chemistry research supporting the Waste Isolation Pilot Plant (WIPP): FY94 results

    Novak, C.F. [ed.

    1995-08-01

    This document contains six reports on actinide chemistry research supporting the Waste Isolation Pilot Plant (WIPP). These reports, completed in FY94, are relevant to the estimation of the potential dissolved actinide concentrations in WIPP brines under repository breach scenarios. Estimates of potential dissolved actinide concentrations are necessary for WIPP performance assessment calculations. The specific topics covered within this document are: the complexation of oxalate with Th(IV) and U(VI); the stability of Pu(VI) in one WIPP-specific brine environment both with and without carbonate present; the solubility of Nd(III) in a WIPP Salado brine surrogate as a function of hydrogen ion concentration; the steady-state dissolved plutonium concentrations in a synthetic WIPP Culebra brine surrogate; the development of a model for Nd(III) solubility and speciation in dilute to concentrated sodium carbonate and sodium bicarbonate solutions; and the development of a model for Np(V) solubility and speciation in dilute to concentrated sodium Perchlorate, sodium carbonate, and sodium chloride media.

  18. Actinide separation of high-level waste using solvent extractants on magnetic microparticles

    Polymeric-coated ferromagnetic particles with an absorbed layer of octyl(phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO) diluted by tributyl phosphate (TBP) are being evaluated for application in the separation and the recovery of low concentrations of americium and plutonium from nuclear waste solutions. Due to their chemical nature, these extractants selectively complex americium and plutonium contaminants onto the particles, which can be recovered from the waste solution using a magnet. The effectiveness of the extractant-absorbed particles at removing transuranics (TRU) from simulated solutions and various nitric acid solutions was measured by gamma and liquid scintillation counting of plutonium and americium. The HNO3 concentration range was 0.01 M to 6M. The partition coefficients (Kd) for various actinides at 2M HNO3 were determined to be between 3,000 and 30,000. These values are larger than those projected for TRU recovery by traditional liquid/liquid extraction. Results from transmission electron microscopy indicated a large dependence of Kd on relative magnetite location within the polymer and the polymer surface area. Energy disperse spectroscopy demonstrated homogeneous metal complexation on the polymer surface with no metal clustering. The radiolytic stability of the particles was determined by using 60Co gamma irradiation under various conditions. The results showed that Kd more strongly depends on the nitric acid dissolution rate of the magnetite than the gamma irradiation dose. Results of actinide separation from simulated high-level waste representative of that at various DOE sites are also discussed

  19. Actinide occurrences in sediments following ground disposal of acid wastes at 216-Z-9

    Liquid acid wastes from a Pu recovery facility at Hanford were released to the ground via structures collectively termed trenches from 1955 through 1962. Data are presented from a study of the microdistribution of Am and Pu in samples from the 216-Z-9 trench. Solution sediment relationships and associated actinide removal mechanisms under acid conditions were studied. Core wells were drilled into the sediments in which this covered trench is located and in the immediate vicinity to obtain samples for quantitative mineralogical analysis and comparison of sediments from various depths of contaminated and noncontaminated areas. Analytical techniques are described and results are reported

  20. Minimization of actinide waste by multirecycling of thoriated fuels in an EPR

    2009-01-01

    This master’s thesis explores how to minimize the long-lived actinide waste that is produced in nuclear power plants by performing simulations of thoriated nuclear fuels in existing reactor designs. An European pressurized water reactor (EPR) assembly fueled with a mixture of thorium and highly enriched uranium (20% and 90% 235U) was simulated. The spent thoriated fuel is less active, and for a much shorter period of time, than uranium or uranium/plutonium fuels and less decay heat is gene...

  1. Loading Actinides in Multilayered Structures for Nuclear Waste Treatment: The First Case Study of Uranium Capture with Vanadium Carbide MXene.

    Wang, Lin; Yuan, Liyong; Chen, Ke; Zhang, Yujuan; Deng, Qihuang; Du, Shiyu; Huang, Qing; Zheng, Lirong; Zhang, Jing; Chai, Zhifang; Barsoum, Michel W; Wang, Xiangke; Shi, Weiqun

    2016-06-29

    Efficient nuclear waste treatment and environmental management are important hurdles that need to be overcome if nuclear energy is to become more widely used. Herein, we demonstrate the first case of using two-dimensional (2D) multilayered V2CTx nanosheets prepared by HF etching of V2AlC to remove actinides from aqueous solutions. The V2CTx material is found to be a highly efficient uranium (U(VI)) sorbent, evidenced by a high uptake capacity of 174 mg g(-1), fast sorption kinetics, and desirable selectivity. Fitting of the sorption isotherm indicated that the sorption followed a heterogeneous adsorption model, most probably due to the presence of heterogeneous adsorption sites. Density functional theory calculations, in combination with X-ray absorption fine structure characterizations, suggest that the uranyl ions prefer to coordinate with hydroxyl groups bonded to the V-sites of the nanosheets via forming bidentate inner-sphere complexes. PMID:27267649

  2. Study of the actinide-lanthanide separation from nuclear waste by a new pyrochemical process; Etude de la separation actinides-lanthanides des dechets nucleaires par un procede pyrochimique nouveau

    Lemort, F. [CEA Marcoule, Departement de Retraitement, des Dechets et du Demantelement, 30 - Bagnols-sur-Ceze (France)]|[Institut National Polytechnique, 38 - Grenoble (France)

    1997-01-01

    The theoretical extraction and separation of platinoids, actinides and lanthanides is allowed by thermodynamic using two adapted reducing agents: zinc and magnesium. Thereby, a pyrochemical method for the nuclear waste processing has been devised. The high temperature handling of the elements in fluoride forms and their processing by a reactive metallic phase required special precautions. The study of the behavior of matter in exploratory systems allowed the development of an experimental technology for the treatment and contacting of phases. The thermodynamical analysis of the experimental results shows the feasibility of the process. A model was developed to predict the distribution coefficients of zirconium, uranium and lanthanum as a function of the system composition. An estimation method was proposed in order to evaluate the distribution coefficients in diluted solution of all the actinides and lanthanides existing in the fission products between LiF CaF{sub 2} and Zn-Mg at 720 deg C. Coupled with the experimental results, the estimates results may be extrapolated to concentrated solutions allowing predictions of the separation of all actinides and lanthanides. The rapidity of element transfer is induced by a thermal effect caused by the high exothermicity of the reduction by magnesium. The kinetic coefficients have been linked with the reduction enthalpy of each element. Moreover, the kinetics seem limited by chemical reaction and not by mass transfer. (author) 66 refs.

  3. Recovering actinide values

    Actinide values are recovered from sodium carbonate scrub waste solutions containing these and other values along with organic compounds resulting from the radiolytic and hydrolytic degradation of neutral organophosphorus extractants such as tri-n butyl phosphate (TBP) and dihexyl-N, N-diethyl carbamylmethylene phosphonate (DHDECMP) which have been used in the reprocessing of irradiated nuclear reactor fuels. The scrub waste solution is made acidic with mineral acid, to form a feed solution which is then contacted with a water-immiscible, highly polar organic extractant which selectively extracts the degradation products from the feed solution. The feed solution can then be processed to recover the actinides for storage or recycled back into the high-level waste process stream. The extractant can be recycled after stripping the degradation products with a neutral sodium carbonate solution. (author)

  4. Production, disposal, and relative toxicity of long-lived fission products and actinides in the radioactive wastes from nuclear fuel cycles

    Chapters are devoted to the following topics: predicted future development of nuclear energy in the German Federal Republic and in Western Europe, fuel cycle variations and production of fission products and actinides in the radioactive waste from reprocessed nuclear fuels, long-lived fission products and actinides in the waste streams from the reprocessing of nuclear fuels, relative toxicity index, presently preferred waste management concepts, and alternative concepts for the elimination of high-level wastes

  5. Low temperature waste form process intensification

    Fox, K. M. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Cozzi, A. D. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Hansen, E. K. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Hill, K. A. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)

    2015-09-30

    This study successfully demonstrated process intensification of low temperature waste form production. Modifications were made to the dry blend composition to enable a 50% increase in waste concentration, thus allowing for a significant reduction in disposal volume and associated costs. Properties measurements showed that the advanced waste form can be produced using existing equipment and processes. Performance of the waste form was equivalent or better than the current baseline, with approximately double the amount of waste incorporation. The results demonstrate the feasibility of significantly accelerating low level waste immobilization missions across the DOE complex and at environmental remediation sites worldwide.

  6. Actinides in alkaline media: dissolution, mineral associations, and speciation in hanford waste tank sludge simulants

    We have investigated the leaching behavior of actinides from simulants of tank waste sludges derived from the BiPO4, Redox, and PUREX processes, the principal chemical separations processes that operated at the Hanford site during 40+years of plutonium production. Fundamental investigations of the speciation of uranium and neptunium in solutions representative of proposed alkaline sludge washing liquors have also been completed. Correlation of the results from sludge leaching indicate that, while Am and Pu are generally not appreciably dissolved from the sludges into alkaline solutions in the absence of oxidants, Np and U can be mobilized during alkaline sludge washing. Leaching of sludges with acidic solutions and strong complexing agents indicate considerable association of all actinide ions with Cr, Fe, and Mn oxides in the sludge simulants. Electrochemical experiments conducted in strongly alkaline solutions have defined the formal potentials of Np in strong base and reveal that mononuclear hydrolysis products dominate the speciation of neptunium (and by analogy U and Pu) in concentrated alkali. The results of these observations are discussed in the context of alkaline sludge washing procedures associated with waste tank remediation. This work supported by the Assistant Secretary for Environmental Management under U.S. Department of Energy Contract Numbers W-31-109ENG-38 at Argonne National Laboratory and DE-AC03-76SF0098 at Lawrence Berkeley National Laboratory. (author)

  7. Computational chemistry for nuclear waste characterization and processing. Relativistic quantum chemistry of actinides

    This paper describes some of the motivations and accomplishments of our grand challenge project of the same title and focuses upon the activities at Pacific Northwest National Laboratory. The United States Department of Energy (DOE) funded the project, which finishes this fiscal year. Its objectives were to develop and apply the methods of relativistic quantum chemistry to assists in the understanding and prediction of the chemistry of actinide and lanthanide compounds. This is important to the DOE because the production of nuclear weapons at DOE facilities has left a serious legacy of environmental contamination, including millions of gallons of highly radioactive waste stored in hundreds of tanks that have exceeded their life expectancy. Much of the radioactive waste involves actinides, and their large atomic number implies that relativistic effects have important chemical consequences. By using modern non-relativistic quantum chemistry techniques, it is now possible to calculate to high accuracy the structures, energetics, and properties of molecules containing light elements. Our implementation of relativistic quantum chemical methods will, for the first time on massively parallel computers, provide capabilities for modeling heavy-element compounds similar to those currently available for light-element compounds. (author)

  8. Performance Test on Polymer Waste Form - 12137

    Lee, Se Yup [Korea Nuclear Engineering Co., Ltd., C-504 Bundang Techno-Park 145, Yatap-dong, Bundang-gu, Seongnam-si, Gyeonggi-do, 463-760 (Korea, Republic of)

    2012-07-01

    Polymer solidification was attempted to produce stable waste form for the boric acid concentrates and the dewatered spent resins. The polymer mixture was directly injected into the mold or drum which was packed with the boric acid concentrates and the dewatered spent resins, respectively. The waste form was produced by entirely curing the polymer mixture. A series of performance tests was conducted including compressive strength test, water immersion test, leach test, thermal stability test, irradiation stability test and biodegradation stability test for the polymer waste forms. From the results of the performance tests for the polymer waste forms, it is believed that the polymer waste form is very stable and can satisfy the acceptance criteria for permanent disposal. At present, performance tests with full scale polymer waste forms are being carried out in order to obtain qualification certificate by the regulatory institute in Korea. Polymer waste forms were prepared with the surrogate of boric acid concentrates and the surrogate of spent ion exchange resins respectively. Waste forms were also made in lab scale and in full scale. Lab. scale waste forms were directly subjected to a series of the performance tests. In the case of full scale waste form, the test specimens for the performance test were taken from a part of waste form by coring. A series of performance tests was conducted including compressive strength test, thermal stability test, irradiation stability test and biodegradation stability test, water immersion test, leach test, and free standing water for the polymer waste forms. In addition, a fire resistance test was performed on the waste forms by the requirement of the regulatory institute in Korea. Every polymer waste forms containing the boric acid concentrates and the spent ion exchange resins had exhibited excellent structural integrity of more than 27.58 MPa (4,000 psi) of compressive strength. On thermal stability testing, biodegradation

  9. Performance Test on Polymer Waste Form - 12137

    Polymer solidification was attempted to produce stable waste form for the boric acid concentrates and the dewatered spent resins. The polymer mixture was directly injected into the mold or drum which was packed with the boric acid concentrates and the dewatered spent resins, respectively. The waste form was produced by entirely curing the polymer mixture. A series of performance tests was conducted including compressive strength test, water immersion test, leach test, thermal stability test, irradiation stability test and biodegradation stability test for the polymer waste forms. From the results of the performance tests for the polymer waste forms, it is believed that the polymer waste form is very stable and can satisfy the acceptance criteria for permanent disposal. At present, performance tests with full scale polymer waste forms are being carried out in order to obtain qualification certificate by the regulatory institute in Korea. Polymer waste forms were prepared with the surrogate of boric acid concentrates and the surrogate of spent ion exchange resins respectively. Waste forms were also made in lab scale and in full scale. Lab. scale waste forms were directly subjected to a series of the performance tests. In the case of full scale waste form, the test specimens for the performance test were taken from a part of waste form by coring. A series of performance tests was conducted including compressive strength test, thermal stability test, irradiation stability test and biodegradation stability test, water immersion test, leach test, and free standing water for the polymer waste forms. In addition, a fire resistance test was performed on the waste forms by the requirement of the regulatory institute in Korea. Every polymer waste forms containing the boric acid concentrates and the spent ion exchange resins had exhibited excellent structural integrity of more than 27.58 MPa (4,000 psi) of compressive strength. On thermal stability testing, biodegradation

  10. Radiation damage in natural materials: implications for radioactive waste forms

    The long-term effect of radiation damage on waste forms, either crystalline or glass, is a factor in the evaluation of the integrity of waste disposal mediums. Natural analogs, such as metamict minerals, provide one approach for the evaluaton of radiation damage effects that might be observed in crystalline waste forms, such as supercalcine or synroc. Metamict minerals are a special class of amorphous materials which were initially crystalline. Although the mechanism for the loss of crystallinity in these minerals (mostly actinide-containing oxides and silicates) is not clearly understood, damage caused by alpha particles and recoil nuclei is critical to the metamictization process. The study of metamict minerals allows the evaluation of long-term radiation damage effects, particularly changes in physical and chemical properties such as microfracturing, hydrothermal alteration, and solubility. In addition, structures susceptible to metamictization share some common properties: (1) complex compositions; (2) some degree of covalent bonding, instead of being ionic close-packed MO/sub x/ structures; and (3) channels or interstitial voids which may accommodate displaced atoms or absorbed water. On the basis of these empirical criteria, minerals such as pollucite, sodalite, nepheline and leucite warrant careful scrutiny as potential waste form phases. Phases with the monazite or fluorite structures are excellent candidates

  11. Polyphase ceramic and glass-ceramic forms for immobilizing ICPP high-level nuclear waste

    Polyphase ceramic and glass-ceramic forms have been consolidated from simulated Idaho Chemical Processing Plant wastes by hot isostatic pressing calcined waste and chemical additives by 10000C or less. The ceramic forms can contain over 70 wt% waste with densities ranging from 3.5 to 3.85 g/cm3, depending upon the formulation. Major phases are CaF2, CaZrTi207, CaTiO3, monoclinic ZrO2, and amorphous intergranular material. The relative fraction of the phases is a function of the chemical additives (TiO2, CaO, and SiO2) and consolidation temperature. Zirconolite, the major actinide host, makes the ceramic forms extremely leach resistant for the actinide simulant U238. The amorphous phase controls the leach performance for Sr and Cs which is improved by the addition of SiO2. Glass-ceramic forms were also consolidated by HIP at waste loadings of 30 to 70 wt% with densities of 2.73 to 3.1 g/cm3 using Exxon 127 borosilicate glass frit. The glass-ceramic forms contain crystalline CaF2, Al203, and ZrSi04 (zircon) in a glass matrix. Natural mineral zircon is a stable host for 4+ valent actinides. 17 references, 3 figures, 5 tables

  12. Determination of long-lived fission products and actinides in Savannah River Site HLW sludge and glass for waste acceptance

    Savannah River Site (SRS) is immobilizing the radioactive, high-level waste sludge in Tank 51 into a borosilicate glass for disposal in a geologic repository. A requirement for repository acceptance is that SRS report the concentrations of certain fission product and actinide radionuclides in the glass. This paper presents measurements of many of these concentrations in both Tank 51 sludge and the final glass. The radionuclides were measured by inductively coupled plasma mass spectrometry and α, β, and γ counting methods. Examples of the radionuclides are 90Sr, 137Cs, 238U and , 239Pu. Concentrations in the glass are 3.1 times lower due to dilution of the sludge with a nonradioactive glass forming frit in the vitrification process. Results also indicated that in both the sludge and glass the relative concentrations of the long lived fission products insoluble in caustic are in proportion to their yields from the fission of 235U waste in the SRS reactors. This allowed the calculation of a fission yield scaling factor. This factor in addition to the sludge dilution factor can be used to estimate concentrations of waste acceptance radionuclides that cannot be measured in the glass. Examples of these radionuclides are 79Se, 93Zr, and 107Pd. (author)

  13. Decay calculations on medium-level and actinide-containing wastes from the LWR fuel cycle. Pt. 1

    A number of basic data on medium-level and actinide-containing waste streams from the LWR fuel cycle were evaluated and the activity and thermal decay power were calculated for the nuclide inventories of cladding hulls and fuel assembly structural materials, for feed clarification sludge, medium-level aqueous process waste, low-level solid transuranium waste and for medium-level reactor operating waste. The activity as a function of decay time of the medium-level wastes decreases within 500 to 600 years by 1 to 3 orders of magnitude and is at the same time about 1 to 2 orders of magnitude lower than the activity of the high-level waste. The thermal decay power of the medium-level wastes decreases after 10 to 100 years by about 3 orders of magnitude and is about a factor of 10 to 100 less than that of high-level waste. In the very long term the residual activity (and thermal power) decreases only slowly due to the long halflives of the dominant actinides. The activity after more that 1000 years is about 1 to 2 orders of magnitude lower than that of high-level waste, the low-level transuranium waste by a factor 10 to 4, respectively. The activity per unit volume of the packaged waste of the medium-level and actinide-containing wastes because of the bigger volume of the conditioned wastes is lower by 2 to 4 orders of magnitude up to about 500 years. After more than 1000 years the activities per unit volume are lower by a factor of 20 to 200 than that of high-level waste. (orig.)

  14. Radioactive waste forms for the future

    This volume presents a compilation of important information on the full range of radioactive waste forms that have been developed, or at least suggested, for the incorporation of high-level nuclear waste. Many of the results were published in the 'gray literature' of final reports of national laboratories or in various, generally less available, proceedings volumes. This is the first publication to draw information on nuclear waste forms for high-level wastes togehter into a single volume. A detailed presentation is given on the properties and performance of non-crystalline waste forms (borosilicate glass, sintered glass, sintered glass, and lead-iron phosphate glass), and crystalline waste forms (Synroc, tailored ceramics, TiO2-ceramic matrix, glass-ceramics and concrete). A chapter on Novel waste forms reviews a number of methods that warrant further development because of their potential superior performance and unique applications. The final chapter includes a tabulated comparison of important waste form properties and an extended discussion on the corrosion process and radiation damage effects for each waste form. Of particular interest is a performance assessment of nuclear waste borosilicate glass and the crystalline ceramic Synroc. This is the first detailed attempt to compare these two important waste forms on the basis of their materials properties. The discussion emphasizes the difficulties in making such a comparison and details the types of data that are required. (author). refs.; figs.; tabs

  15. Radioactive waste forms: A review and comparison

    Borosilicate glass is, at present, the waste form of choice for most countries and for most compositions. The selection of borosilicate glass is based mainly on an anticipated ease of processing (glass frit and the waste are mixed, melted at relatively low temperatures, and poured into canisters), the fact that the technology is well demonstrated for actual (radioactive) waste, and finally the assumption that the glass as an aperiodic solid will easily accommodate wide variation in waste stream compositions which are extremely complex and varied. There are, however, alternative waste forms which may be single or polyphase crystalline ceramics. Principal ceramic nuclear waste forms include: Synroc, tailored ceramics (= supercalcine), TiO2-matrix ceramics, glass ceramics, monazite, synthetic ''basalt'', cementitious materials, and FUETAP concrete. In addition, there are a number of ''novel'' ceramic waste forms which have been developed to only the most preliminary stages (e.g., crichtonite and cesium-Titanates), and there are several multi-barrier strategies which encapsulate one ceramic waste form in another. Finally, in recent years, spent fuel has become an important waste form. Finally, in recent years, spent fuel has become an important waste form. This paper will briefly describe the importance and types of ceramic waste forms that have been developed and review their advantages and disadvantages. (author). 9 refs

  16. Establishment of uncertainty ranges and probability distributions of actinide solubilities for performance assessment in the Waste Isolation Pilot Plant (WIPP)

    The Fracture-Matrix Transport (FMT) code developed at Sandia National Laboratories solves chemical equilibrium problems using the Pitzer activity coefficient model with a database containing actinide species. The code is capable of predicting actinide solubilities at 25 C in various ionic-strength solutions from dilute groundwaters to high-ionic-strength brines. The code uses oxidation state analogies, i.e., Am(III) is used to predict solubilities of actinides in the +III oxidation state; Th(IV) is used to predict solubilities of actinides in the +IV state; Np(V) is utilized to predict solubilities of actinides in the +V state. This code has been qualified for predicting actinide solubilities for the Waste Isolation Pilot Plant (WIPP) Compliance Certification Application in 1996, and Compliance Re-Certification Applications in 2004 and 2009. We have established revised actinide-solubility uncertainty ranges and probability distributions for Performance Assessment (PA) by comparing actinide solubilities predicted by the FMT code with solubility data in various solutions from the open literature. The literature data used in this study include solubilities in simple solutions (NaCl, NaHCO3, Na2CO3, NaClO4, KCl, K2CO3, etc.), binary mixing solutions (NaCl+NaHCO3, NaCl+Na2CO3, KCl+K2CO3, etc.), ternary mixing solutions (NaCl+Na2CO3+KCl, NaHCO3+Na2CO3+NaClO4, etc.), and multi-component synthetic brines relevant to the WIPP.

  17. Crystalline Ceramic Waste Forms: Comparison Of Reference Process For Ceramic Waste Form Fabrication

    Brinkman, K. S. [Savannah River National Laboratory; Marra, J. C. [Savannah River National Laboratory; Amoroso, J. [Savannah River National Laboratory; Tang, M. [Los Alamos National Laboratory

    2013-08-22

    The research conducted in this work package is aimed at taking advantage of the long term thermodynamic stability of crystalline ceramics to create more durable waste forms (as compared to high level waste glass) in order to reduce the reliance on engineered and natural barrier systems. Durable ceramic waste forms that incorporate a wide range of radionuclides have the potential to broaden the available disposal options and to lower the storage and disposal costs associated with advanced fuel cycles. Assemblages of several titanate phases have been successfully demonstrated to incorporate radioactive waste elements, and the multiphase nature of these materials allows them to accommodate variation in the waste composition. Recent work has shown that they can be produced from a melting and crystallization process. The objective of this report is to explore the phase formation and microstructural differences between lab scale melt processing in varying gas environments with alternative densification processes such as Hot Pressing (HP) and Spark Plasma Sintering (SPS). The waste stream used as the basis for the development and testing is a simulant derived from a combination of the projected Cs/Sr separated stream, the Trivalent Actinide - Lanthanide Separation by Phosphorous reagent Extraction from Aqueous Komplexes (TALSPEAK) waste stream consisting of lanthanide fission products, the transition metal fission product waste stream resulting from the transuranic extraction (TRUEX) process, and a high molybdenum concentration with relatively low noble metal concentrations. Melt processing as well as solid state sintering routes SPS and HP demonstrated the formation of the targeted phases; however differences in microstructure and elemental partitioning were observed. In SPS and HP samples, hollandite, pervoskite/pyrochlore, zirconolite, metallic alloy and TiO{sub 2} and Al{sub 2}O{sub 3} were observed distributed in a network of fine grains with small residual pores

  18. Crystalline Ceramic Waste Forms: Comparison Of Reference Process For Ceramic Waste Form Fabrication

    The research conducted in this work package is aimed at taking advantage of the long term thermodynamic stability of crystalline ceramics to create more durable waste forms (as compared to high level waste glass) in order to reduce the reliance on engineered and natural barrier systems. Durable ceramic waste forms that incorporate a wide range of radionuclides have the potential to broaden the available disposal options and to lower the storage and disposal costs associated with advanced fuel cycles. Assemblages of several titanate phases have been successfully demonstrated to incorporate radioactive waste elements, and the multiphase nature of these materials allows them to accommodate variation in the waste composition. Recent work has shown that they can be produced from a melting and crystallization process. The objective of this report is to explore the phase formation and microstructural differences between lab scale melt processing in varying gas environments with alternative densification processes such as Hot Pressing (HP) and Spark Plasma Sintering (SPS). The waste stream used as the basis for the development and testing is a simulant derived from a combination of the projected Cs/Sr separated stream, the Trivalent Actinide - Lanthanide Separation by Phosphorous reagent Extraction from Aqueous Komplexes (TALSPEAK) waste stream consisting of lanthanide fission products, the transition metal fission product waste stream resulting from the transuranic extraction (TRUEX) process, and a high molybdenum concentration with relatively low noble metal concentrations. Melt processing as well as solid state sintering routes SPS and HP demonstrated the formation of the targeted phases; however differences in microstructure and elemental partitioning were observed. In SPS and HP samples, hollandite, pervoskite/pyrochlore, zirconolite, metallic alloy and TiO2 and Al2O3 were observed distributed in a network of fine grains with small residual pores. The titanate phases

  19. Radium institute research on actinide separation from high-level waste. Review

    Development of efficient technologies for recovery of long-lived radionuclides from high-level wastes (HLW) is urgent for implementation of the promising management methods (transmutation and disposal), as well as for existing practice of HLW management. In Russia at 'Mayak' radiochemical plant since 1996 there has been in operation the industrial facility UE-35 which provides the recovery of cesium and strontium from HLW. The next stage is aimed at development and implementation of actinide separation technology from HLW. For this purpose the following four processes are studied and tested: processes based on chlorinated cobalt dicarbollide (ChCoDiC-process), isoamyldialkyl-phosphine oxide (POR-process), diphenyldibutylcarbamoylphosphine oxide (modified TRUEX-process) and mixture of ChCoDiC, carbamoylphosphine oxide (CMPO) and polyethylene glycol (PEG) (UNEX-process). After comprehensive study of extraction, physico-chemical and operational properties of selected extraction systems, testing of processes was conducted at test facilities with the use of actual or simulated HLW. Mixer-settlers and centrifugal contactors were used as extraction equipment in these tests. The test results show that the ChCoDiC-process can afford recovery of transplutonium and rare-earth elements (TPE and REE) from HLW and separation of them into fractions. POR-process and modified TRUEX-process enable to recover from HLW uranium, neptunium, plutonium, TPE, REE and technetium with the possibility for production of individual fractions. UNEX-process permits to attain simultaneous recovery of actinides, REE, cesium and strontium from HLW. During tests the potentialities of UNEX-process for obtaining such fractions as cesium, cesium+strontium and actinides+REE at stripping stage were demonstrated as well. (author)

  20. Partitioning of actinides from acid waste solutions of the Purex process by solvent extraction and extraction chromatography

    Disposal of nuclear wastes containing long-lived alpha emitters is a matter of great environmental concern. At this Centre, solvent extraction and extraction chromatographic studies are in progress with CMPO (Octyl(phenyl)N,N-diisobutylcarbamoylmethyl phosphine oxide) as the main extractant for the removal of actinides from Purex high active aqueous raffinate waste (HAW) and high level waste concentrate (HLW) solutions. Batch extraction studies with HAW solutions reveal that after two contacts with 0.2 M CMPO + 1.2 M TBP in dodecane, its alpha activity reduces to ∼0.2% of initial value. The CMPO loaded actinides are efficiently stripped with suitable reagents. Mixer settler experiments in progress confirm these results. Extraction chromatographic studies with CMPO impregnated Chromosorb-102 (CAC) column show higher uptakes of actinides and lanthanides as compared to other metal ions and the capacity in terms of Nd(III) is 18 mg/g of CAC at 3 M HNO3 for less than 1% breakthrough. The results indicate that CMPO based extraction chromatographic techniques have great potential for application in the removal of actinides from Purex waste streams. (author). 7 refs, 3 figs, 8 tabs

  1. Hanford Waste Vitrification Plant Project Waste Form Qualification Program Plan

    Randklev, E.H.

    1993-06-01

    The US Department of Energy has created a waste acceptance process to help guide the overall program for the disposal of high-level nuclear waste in a federal repository. This Waste Form Qualification Program Plan describes the hierarchy of strategies used by the Hanford Waste Vitrification Plant Project to satisfy the waste form qualification obligations of that waste acceptance process. A description of the functional relationship of the participants contributing to completing this objective is provided. The major activities, products, providers, and associated scheduling for implementing the strategies also are presented.

  2. Hanford Waste Vitrification Plant Project Waste Form Qualification Program Plan

    The US Department of Energy has created a waste acceptance process to help guide the overall program for the disposal of high-level nuclear waste in a federal repository. This Waste Form Qualification Program Plan describes the hierarchy of strategies used by the Hanford Waste Vitrification Plant Project to satisfy the waste form qualification obligations of that waste acceptance process. A description of the functional relationship of the participants contributing to completing this objective is provided. The major activities, products, providers, and associated scheduling for implementing the strategies also are presented

  3. New Fission-Product Waste Forms: Development and Characterization

    Alexandra Navrotsky

    2010-07-30

    Research performed on the program “New Fission Product Waste Forms: Development and Characterization,” in the last three years has fulfilled the objectives of the proposal which were to 1) establish ceramic waste forms for disposing of Cs, Sr and minor actinides, 2) fully characterize the phase relationships, structures and thermodynamic and kinetic stabilities of promising waste forms, 3) establish a sound technical basis for understanding key waste form properties, such as melting temperatures and aqueous durability, based on an in-depth understanding of waste form structures and thermochemistry, and 4) establish synthesis, testing, scaleup and commercialization routes for wasteform implementation through out in-kind collaborations. In addition, since Cs and Sr form new elements by radioactive decay, the behavior and thermodynamics of waste forms containing different proportions of Cs, Sr and their decay products were discovered using non-radioactive analogues. Collaborations among researchers from three institutions, UC Davis, Sandia National Laboratories, and Shott Inc., were formed to perform the primary work on the program. The unique expertise of each of the members in the areas of waste form development, structure/property relationships, hydrothermal and high temperature synthesis, crystal/glass production, and thermochemistry was critical to program success. In addition, collaborations with the Brigham Young Univeristy, Ben Gurion University, and Los Alamos National Laboratory, were established for standard entropies of ceramic waste forms, sol-gel synthesis, and high temperature synthesis. This work has had a significant impact in a number of areas. First, the studies of the thermodynamic stability of the mineral analogues provided an important technical foundation for assessment the viability of multicomponent oxide phases for Cs and Sr removal. Moreover, the thermodynamic data discovered in this program established information on the reaction

  4. New Fission-Product Waste Forms: Development and Characterization

    Research performed on the program 'New Fission Product Waste Forms: Development and Characterization,' in the last three years has fulfilled the objectives of the proposal which were to (1) establish ceramic waste forms for disposing of Cs, Sr and minor actinides, (2) fully characterize the phase relationships, structures and thermodynamic and kinetic stabilities of promising waste forms, (3) establish a sound technical basis for understanding key waste form properties, such as melting temperatures and aqueous durability, based on an in-depth understanding of waste form structures and thermochemistry, and (4) establish synthesis, testing, scaleup and commercialization routes for wasteform implementation through out in-kind collaborations. In addition, since Cs and Sr form new elements by radioactive decay, the behavior and thermodynamics of waste forms containing different proportions of Cs, Sr and their decay products were discovered using non-radioactive analogues. Collaborations among researchers from three institutions, UC Davis, Sandia National Laboratories, and Shott Inc., were formed to perform the primary work on the program. The unique expertise of each of the members in the areas of waste form development, structure/property relationships, hydrothermal and high temperature synthesis, crystal/glass production, and thermochemistry was critical to program success. In addition, collaborations with the Brigham Young Univeristy, Ben Gurion University, and Los Alamos National Laboratory, were established for standard entropies of ceramic waste forms, sol-gel synthesis, and high temperature synthesis. This work has had a significant impact in a number of areas. First, the studies of the thermodynamic stability of the mineral analogues provided an important technical foundation for assessment the viability of multicomponent oxide phases for Cs and Sr removal. Moreover, the thermodynamic data discovered in this program established information on the reaction

  5. A generalized definition for waste form durability

    When evaluating waste form performance, the term ''durability'' often appears in casual discourse, but in the technical literature, the focus is often on waste form ''degradation'' in terms of mass lost per unit area per unit time. Waste form degradation plays a key role in developing models of the long-term performance in a repository environment, but other factors also influence waste form performance. These include waste form geometry; density, porosity, and cracking; the presence of cladding; in-package chemistry feedback; etc. The paper proposes a formal definition of waste form ''durability'' which accounts for these effects. Examples from simple systems as well as from complex models used in the Total System Performance Assessment of Yucca Mountain are provided. The application of ''durability'' in the selection of bounding models is also discussed

  6. Investigations of actinides in the context of final disposal of high-level radioactive waste - trivalent actinides in aqueous solution

    This contribution presents a small piece of research work at KIT-INE dealing with the speciation of redox sensitive trivalent actinides like Pu(III), Np(III), and U(III) in aqueous solution. The redox preparation, stabilization, and speciation of trivalent actinide in aqueous systems are discussed here. The reductants investigated were rongalite, HYA (hydroxylamine hydrochloride), and AHA (acetohydroxamic acid). The time dependence of An(III) stability at different pH values was investigated. The An(III) species in aqueous solution have been characterized by UV-Vis and XANES spectroscopy. A broader overview of the work at KIT-INE is given in the oral presentation at the NUCAR2013 conference. (author)

  7. Miscellaneous Waste-Form FEPs

    A. Schenker

    2000-12-08

    The US DOE must provide a reasonable assurance that the performance objectives for the Yucca Mountain Project (YMP) potential radioactive-waste repository can be achieved for a 10,000-year post-closure period. The guidance that mandates this direction is under the provisions of 10 CFR Part 63 and the US Department of Energy's ''Revised Interim Guidance Pending Issuance of New US Nuclear Regulatory Commission (NRC) Regulations (Revision 01, July 22, 1999), for Yucca Mountain, Nevada'' (Dyer 1999 and herein referred to as DOE's Interim Guidance). This assurance must be demonstrated in the form of a performance assessment that: (1) identifies the features, events, and processes (FEPs) that might affect the performance of the potential geologic repository; (2) examines the effects of such FEPs on the performance of the potential geologic repository; (3) estimates the expected annual dose to a specified receptor group; and (4) provides the technical basis for inclusion or exclusion of specific FEPs.

  8. Leaching of actinides and technetium from simulated high-level waste glass

    Leach tests were conducted using a modified version of the IAEA procedure to study the behavior of glass waste-solution interactions. Release rates were determined for Tc, U, Np, Pu, Am, Cm, and Si in the following solutions: WIPP B salt brine, NaCl (287 g/l), NaCl (1.76 g/1), CaCl2 (1.66 g/l), NaHCO3 (2.52 g/l), and deionized water. The leach rates for all elements decreased an order of magnitude from their initial values during the first 20 to 30 days leaching time. The sodium bicarbonate solution produced the highest elemental release rates, while the saturated salt brine and deionized water in general gave the lowest release. Technetium has the highest initial release of all elements studied. The technetium release rates, however, decreased by over four orders of magnitude in 150 days of leaching time. In the prepared glass, technetium was phase separated, concentrating on internal pore surfaces. Neptunium, in all cases except CaCl2 solution, shows the highest actinide release rate. In general, curium and uranium have the lowest release rates. The range of actinide release rates is from 10-5 to 10-8 g/cm2/day. 25 figures, 7 tables

  9. Minimization of actinide waste by multi-recycling of thoriated fuels in the EPR reactor

    Nuttin A.

    2012-02-01

    Full Text Available The multi-recycling of innovative uranium/thorium oxide fuels for use in the European Pressurized water Reactor (EPR has been investigated. If increasing quantities of 238U, the fertile isotope in standard UO2 fuel, are replaced by 232Th, then a greater yield of new fissile material (233U is produced during the cycle than would otherwise be the case. This leads to economies of natural uranium of around 45% if the uranium in the spent fuel is multi-recycled. In addition we show that minor actinide and plutonium waste inventories are reduced and hence waste radio-toxicities and decay heats are up to a factor of 20 lower after 103 years. Two innovative fuel types named S90 and S20, ThO2 mixed with 90% and 20% enriched UO2 respectively, are compared as an alternative to standard uranium oxide (UOX and uranium/plutonium mixed oxide (MOX fuels at the longest EPR fuel discharge burn-ups of 65 GWd/t. Fissile and waste inventories are examined, waste radio-toxicities and decay heats are extracted and safety feedback coefficients are calculated.

  10. Minimization of actinide waste by multi-recycling of thoriated fuels in the EPR reactor

    Rose, S. J.; Wilson, J. N.; Capellan, N.; David, S.; Guillemin, P.; Ivanov, E.; Méplan, O.; Nuttin, A.; Siem, S.

    2012-02-01

    The multi-recycling of innovative uranium/thorium oxide fuels for use in the European Pressurized water Reactor (EPR) has been investigated. If increasing quantities of 238U, the fertile isotope in standard UO2 fuel, are replaced by 232Th, then a greater yield of new fissile material (233U) is produced during the cycle than would otherwise be the case. This leads to economies of natural uranium of around 45% if the uranium in the spent fuel is multi-recycled. In addition we show that minor actinide and plutonium waste inventories are reduced and hence waste radio-toxicities and decay heats are up to a factor of 20 lower after 103 years. Two innovative fuel types named S90 and S20, ThO2 mixed with 90% and 20% enriched UO2 respectively, are compared as an alternative to standard uranium oxide (UOX) and uranium/plutonium mixed oxide (MOX) fuels at the longest EPR fuel discharge burn-ups of 65 GWd/t. Fissile and waste inventories are examined, waste radio-toxicities and decay heats are extracted and safety feedback coefficients are calculated.

  11. Investigations of actinides in the context of final disposal of high-level radioactive waste. Trivalent actinides in aqueous solution

    The speciation of redox sensitive trivalent actinides Pu(III), Np(III), and U(III) has been studied in aqueous solution. The redox preparation, stabilization, and speciation of these trivalent actinides in aqueous systems are discussed here. The reductants investigated were rongalite, hydroxylamine hydrochloride, and acetohydroxamic acid and the An(III) species have been characterized by UV-Vis and XANES spectroscopy. The results show that the effectiveness of stabilization decreases generally in the order Pu(III) > Np(III) > U(III) and that the effectiveness of each reducing agent depends on the experimental conditions. More than 80 % of Pu(III) aquo species have been stabilized up to pH 5.5, whereas the Np(III) aquo ion could be stabilized in a pH range 0-2.5, and U(III) aquo ion is sufficiently stable at pH 1.0 and below over time periods suitable for experiments. However, this study gives a basis for the characterisation of the trivalent lighter actinides involved in complexation, sorption, and solid formation reactions in the future. (author)

  12. Liquid secondary waste. Waste form formulation and qualification

    Cozzi, A. D. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Dixon, K. L. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Hill, K. A. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); King, W. D. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Nichols, R. L. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)

    2016-03-01

    The Hanford Site Effluent Treatment Facility (ETF) currently treats aqueous waste streams generated during Site cleanup activities. When the Hanford Tank Waste Treatment and Immobilization Plant (WTP) begins operations, a liquid secondary waste (LSW) stream from the WTP will need to be treated. The volume of effluent for treatment at the ETF will increase significantly. Washington River Protection Solutions is implementing a Secondary Liquid Waste Immobilization Technology Development Plan to address the technology needs for a waste form and solidification process to treat the increased volume of waste planned for disposal at the Integrated Disposal Facility IDF). Waste form testing to support this plan is composed of work in the near term to demonstrate the waste form will provide data as input to a performance assessment (PA) for Hanford’s IDF.

  13. Liquid secondary waste. Waste form formulation and qualification

    The Hanford Site Effluent Treatment Facility (ETF) currently treats aqueous waste streams generated during Site cleanup activities. When the Hanford Tank Waste Treatment and Immobilization Plant (WTP) begins operations, a liquid secondary waste (LSW) stream from the WTP will need to be treated. The volume of effluent for treatment at the ETF will increase significantly. Washington River Protection Solutions is implementing a Secondary Liquid Waste Immobilization Technology Development Plan to address the technology needs for a waste form and solidification process to treat the increased volume of waste planned for disposal at the Integrated Disposal Facility IDF). Waste form testing to support this plan is composed of work in the near term to demonstrate the waste form will provide data as input to a performance assessment (PA) for Hanford's IDF.

  14. A comparison of radioactive waste from first generation fusion reactors and fast fission reactors with actinide recycling

    Limitations of the fission fuel resources will presumably mandate the replacement of thermal fission reactors by fast fission reactors that operate on a self-sufficient closed fuel cycle. This replacement might take place within the next one hundred years, so the direct competitors of fusion reactors will be fission reactors of the latter rather than the former type. Also, fast fission reactors, in contrast to thermal fission reactors, have the potential for transmuting long-lived actinides into short-lived fission products. The associated reduction of the long-term activation of radioactive waste due to actinides makes the comparison of radioactive waste from fast fission reactors to that from fusion reactors more rewarding than the comparison of radioactive waste from thermal fission reactors to that from fusion reactors. Radioactive waste from an experimental and a commercial fast fission reactor and an experimental and a commercial fusion reactor has been characterized. The fast fission reactors chosen for this study were the Experimental Breeder Reactor 2 and the Integral Fast Reactor. The fusion reactors chosen for this study were the International Thermonuclear Experimental Reactor and a Reduced Activation Ferrite Helium Tokamak. The comparison of radioactive waste parameters shows that radioactive waste from the experimental fast fission reactor may be less hazardous than that from the experimental fusion reactor. Inclusion of the actinides would reverse this conclusion only in the long-term. Radioactive waste from the commercial fusion reactor may always be less hazardous than that from the commercial fast fission reactor, irrespective of the inclusion or exclusion of the actinides. The fusion waste would even be far less hazardous, if advanced structural materials, like silicon carbide or vanadium alloy, were employed

  15. Combined Waste Form Cost Trade Study

    Dirk Gombert; Steve Piet; Timothy Trickel; Joe Carter; John Vienna; Bill Ebert; Gretchen Matthern

    2008-11-01

    A new generation of aqueous nuclear fuel reprocessing, now in development under the auspices of the DOE Office of Nuclear Energy (NE), separates fuel into several fractions, thereby partitioning the wastes into groups of common chemistry. This technology advance enables development of waste management strategies that were not conceivable with simple PUREX reprocessing. Conventional wisdom suggests minimizing high level waste (HLW) volume is desirable, but logical extrapolation of this concept suggests that at some point the cost of reducing volume further will reach a point of diminishing return and may cease to be cost-effective. This report summarizes an evaluation considering three groupings of wastes in terms of cost-benefit for the reprocessing system. Internationally, the typical waste form for HLW from the PUREX process is borosilicate glass containing waste elements as oxides. Unfortunately several fission products (primarily Mo and the noble metals Ru, Rh, Pd) have limited solubility in glass, yielding relatively low waste loading, producing more glass, and greater disposal costs. Advanced separations allow matching the waste form to waste stream chemistry, allowing the disposal system to achieve more optimum waste loading with improved performance. Metals can be segregated from oxides and each can be stabilized in forms to minimize the HLW volume for repository disposal. Thus, a more efficient waste management system making the most effective use of advanced waste forms and disposal design for each waste is enabled by advanced separations and how the waste streams are combined. This trade-study was designed to juxtapose a combined waste form baseline waste treatment scheme with two options and to evaluate the cost-benefit using available data from the conceptual design studies supported by DOE-NE.

  16. Bulk separation of actinides and lanthanides from actual high level liquid waste of PUREX origin using tetra-(2-ethylhexyl) diglycolamide

    Partitioning and transmutation of minor actinides is emerging as one of the preferred options for the management of high level liquid waste (HLLW) generated during the reprocessing of spent nuclear fuel. Various processes viz., DIAMEX process, TRUEX process etc. have been developed and are being tested for their use in actual application. Of late, a new class of extractant, diglycolamides, with good radiation and chemical stability and complete incinerability has emerged as the front runner for partitioning. This paper deals with the testing of indigenous and bulk synthesized N,N,N',N' tetra-(2-ethylhexyl) diglycolamide (TEHDGA) for the bulk separation of actinides and lanthanides (An and Ln) from actual HLLW

  17. Waste Form Evaluation Program. Final report

    This report presents data that can be used to assess the acceptability of polyethylene and modified sulfur cement waste forms to meet the requirements of 10 CFR 61. The waste streams selected for this study include dry evaporator concentrate salts and incinerator ash as representative wastes which result from advanced volume reduction technologies and ion exchange resins which remain problematic for solidification using commercially available matrix materials. Property evaluation tests such as compressive strength, water immersion, thermal cycling, irradiation, biodegradation and leachability were conducted for polyethylene and sulfur cement waste forms over a range of waste-to-binder ratios. Based on the results of the tests, optimal waste loadings of 70 wt % sodium sulfate, 50 wt % boric acid, 40 wt % incinerator ash and 30 wt % ion exchange resins were established for polyethylene, although maximum loadings were considerably higher. For modified sulfur cement, optimal loadings of 40 wt % sodium sulfate, 40 wt % boric acid and 40 wt % incinerator ash are reported. Ion exchange resins are not recommended for incorporation into modified sulfur cement because of poor waste form performance even at very low waste concentrations. The results indicate that all waste forms tested within the range of optimal waste concentrations satisifed the requirements of the NRC Technical Position Paper on Waste Form

  18. Scenarios for Minor Actinides Transmutation in the Frame of the French Act for Waste Management

    In the frame of the French Act for waste management, options of minor actinides (MA) transmutation are studied, based on a scenario of a 60 GWe SFR fleet deployment from 2040 to 2100. The advantages and drawbacks of different transmutation options are evaluated. The transmutation of all MA or only of americium is considered, in homogeneous mode (MA bearing fuel in all the core) or in heterogeneous mode (MA bearing radial blankets). Scenarios have been optimized to limit the impacts of MA transmutation on fuel cycle, with a reduction of the initial MA content in core in homogeneous mode to mitigate the effect on reactivity coefficients and a reduction of the fuel decay heat for transportation in heterogeneous mode. The sensitivity of results to the SFR core design is evaluated by considering a homogeneous core (SFR V2B) or a new heterogeneous core with a significant gain on sodium void effect (CFV). (author)

  19. Methods of high-sensitive analysis of actinides in liquid radioactive waste

    A complex of methods has been developed to determine actinides in liquid radioactive wastes for solving the problems of radiation, nuclear and ecological safety of nuclear reactors. The main method is based on the radiochemical separation of U, Np-Pu, Am-Cm on ion-exchange and extraction columns. An identification of radionuclides and determination of their content are performed using alpha-spectrometry. The microconcentrations of the sum of the main fissile materials U-235 and Pu-239 are determined with the usage of plastic track detectors. An independent method of U-238 content determination is the neutron activation analysis. Am-241 content is possible to determine with gamma-spectrometry. (author)

  20. Special Form Testing of Sealed Source Encapsulation for High-Alpha-Activity Actinide Materials

    Martinez, Oscar A [ORNL

    2016-01-01

    In the United States all transportation of radioactive material is regulated by the U.S. Department of Transportation (DOT). Beginning in 2008 a new type of sealed-source encapsulation package was developed and tested by Oak Ridge National Laboratory (ORNL). These packages contain high-alpha-activity actinides and are regulated and transported in accordance with the requirements for DOT Class 7 hazardous material. The DOT provides specific regulations pertaining to special form encapsulation designs. The special form designation indicates that the encapsulated radioactive contents have a very low probability of dispersion even when subjected to significant structural events. The special form designs have been shown to simplify the delivery, transport, acceptance, and receipt processes. It is intended for these sealed-source encapsulations to be shipped to various facilities making it very advantageous for them to be certified as special form. To this end, DOT Certificates of Competent Authority (CoCAs) have been sought for the design suitable for containing high-alpha-activity actinide materials. This design consists of the high-alpha-activity material encapsulated within a triangular zirconia canister, referred to as a ZipCan, tile that is then enclosed by a spherical shell. The spherical shell design, with ZipCan tile inside, was tested for compliance with the special form regulations found in 49 CFR 173.469. The spherical enclosure was subjected to 9-m impact, 1 m percussion, and 10-minute thermal tests at the Packaging Evaluation Facility located at the National Transportation Research Center in Knoxville, TN USA and operated by ORNL. Before and after each test, the test units were subjected to a helium leak check and a bubble test. The ZipCan tiles and core were also subjected to the tests required for ISO 2919:2012(E), including a Class IV impact test and heat test and subsequently subjected to helium leakage rate tests [49 CFR 173.469(a)(4)(i)]. The impact

  1. Leaching of actinide-doped nuclear waste glass in a tuff-dominated system

    A laboratory leaching test has been performed as part of a project to evaluate the suitability of tuff rocks at Yucca Mountain, Nevada, as a site for a high-level nuclear waste repository. Glass samples were placed in water inside tuff vessels, and then the tuff vessels were placed in water inside Teflon containers. Glass-component leach rates and migration through the tuff were measured for samples of the ATM-8 actinide glass, which is a PNL 76-68 based glass doped with low levels of 99Tc, 237Np, 238U, and 239Pu to simulate wastes. Disc samples of this glass were leached at 900C for 30, 90, and 183 days inside tuff vessels using a natural groundwater (J-13 well-water) as the leachant. At the end of each leaching interval, the J-13 water present inside and outside the rock vessel was analyzed for glass components in solutions. Boron, molybdenum, and technetium appear to migrate through the rock at rates that depend on the porosity of each vessel and the time. The actinide elements were found only in the inner leachate. Normalized elemental mass loss values for boron, molybdenum, and technetium were calculated using concentrations of the inner and outer leachates and assuming a negligible retention on the rock. The maximum normalized release was 2.3 g/m2 for technetium. Boron, molybdenum, technetium, and neptunium were released linearly with respect to each other, with boron and molybdenum released at about 85% of the technetium rate, and neptunium at 5 to 10% of the technetium rate. Plutonium was found at low levels in the inner leachate but was strongly sorbed on the steel and Teflon supports. Neptunium was sorbed to a lesser extent. 8 refs., 6 figs., 6 tabs

  2. Decay analysis of pre-actinide and trans-actinide nuclei formed using various projectiles on a 197Au target at ECN*=60 MeV

    Grover, Neha; Kaur, Gurvinder; Sharma, Manoj K.

    2016-01-01

    The collective clusterization approach of the dynamical cluster decay model (DCM) has been applied to study the decay of odd mass nuclei 223Pa*, 215Fr*, 227Np*, and 233Am*, which are formed in heavy-ion-induced reactions. The aim of this study is to investigate the decay pattern and related behavior of these heavy mass nuclei formed in four distinct reactions involving different projectiles (with mass A =18 -36 ) induced on 197Au target nucleus. Further, in order to analyze the role of deformations, the calculations have been done by considering spherical choice of fragmentation as well as with inclusion of quadrupole (β2) deformation. For the heavy mass region, with fission being the dominant decay mode, an attempt has been made to investigate the effect of projectile mass in reference to fission decay patterns of the pre-actinide 215Fr* nucleus and the trans-actinide nuclei 227Np* 223Pa*, 223Am* and formed at common excitation energy, ECN*=60 MeV . Besides this, the shell closure effects and the role of orientation have been explored, which suggest the presence of a noncompound nucleus process such as quasifission (QF) for the odd mass nuclei under consideration. For both the compound nucleus and the noncompound nucleus processes, the results obtained using DCM are found to have nice agreement with experimental observations. The isotopic and isobaric analysis is also worked out so as to have a comprehensive idea about the dynamics involved.

  3. Determination of long-lived fission products and actinides in Savannah River site HLW sludge and glass for waste acceptance

    Savannah River Site (SRS) is currently immobilizing the radioactive, caustic, high-level waste sludge in Tank 51 into a borosilicate glass for disposal in a geologic repository. A requirement for repository acceptance is that SRS report the concentrations of certain fission product and actinide radionuclides in the glass. This paper presents measurements of many of these concentrations in both Tank 51 sludge and the final glass. The radionuclides were measured by inductively coupled plasma - mass spectrometry and α, β, and γ counting methods. Examples of the radionuclides are Sr-90, Cs-137, U-238, Pu-239, and Cm-244. Concentrations in the glass are 3.1 times lower due to dilution of the sludge with a nonradioactive glass forming frit in the vitrification process. Results also indicated that in both the sludge and glass the relative concentrations of the long lived fission products insoluble in caustic area in proportion to their yields from the fission of U-235 in the SRS reactors. This allowed the calculation of a fission yield scaling factor. This factor in addition to the sludge dilution factor can be used to estimate concentrations of waste acceptance radionuclides that cannot be measured in the glass

  4. Study of solid extractants based on malonamides, diglycolamides, and bipyridines for the partitioning of minor actinides from high active wastes

    Šul'Aková, J.; John, J.; Šebesta, F.

    2006-01-01

    In this work, the performance of the solid extractants with polyacrylonitrile (PAN) binding matrix was studied for the separation of lanthanides and actinides from nitric acid solutions. As extractants, incorporated into the PAN matrix, the N,N‧-dimethyl-N,N‧-dibutyltetradecylmalonamide (DMDBTDMA), N,N‧-dimethyl-N,N‧-dioctyl-hexy-loxyethylmalonamide (DMDOHEMA), N,N,N‧,N‧-tetraoctyldiglycolamide (TODGA), 6,6‧-bis-(5,6-dipentyl-[1,2,4]triazin-3-yl[2,2‧]bipyridinyl (C5BTBP) were used. Weight distribution coefficients Dg of europium and several actinides have been determined for all the composite materials. The kinetics of europium uptake, practical dynamic extraction capacities, and extraction isotherms were also determined. The results obtained revealed that the solid extractants studied are prospective for the partitioning of lanthanides and actinides from liquid radioactive wastes.

  5. TEM investigation of a ceramic waste form for immobilization of process salts generated during electrometallurgical treatment of spent nuclear fuel

    Transmission electron microscopy (TEM) examination is presented of the microstructure of a ceramic waste form developed at Argonne National Lab - West for immobilization of actinides and fission products present in an electrorefiner salt. The material is produced by occluding the salt in zeolite granules, followed by hot isostatic pressing of the occluded zeolite in a mixture with a borosilicate glass. The paper presents results from a cold surrogate ceramic waste form, as well as 239Pu and 238Pu loaded samples

  6. Work within the coordinated programme on environmental evaluation and hazard assessment of the separation of the actinides from the high-level waste from fuel reprocessing followed by either transmutation of separate disposal

    Reduction of plutonium losses in non-high-level wastes streams from fuel reprocessing is important in the conventional post-fission operations and would be essential in any actinide partitioning alternatives. The balance of input process streams and output waste streams in present reprocessing technology is compared to the balance after process modifications based on recent experimental developments. The results are showing that by the introduction of new electrochemical redox processes and non-salt-forming process chemicals the routinely generated intermediate-level waste streams from PUREX reprocessing can be avoided. Plutonium-bearing waste streams can be extensively recycled within the chemical processing

  7. Leaching of nuclear power reactor wastes forms

    The leaching tests for power reactor wastes carried out at IPEN/CNEN-SP are described. These waste forms consist mainly of spent resins and boric acid concentrates solidified in ordinary Portland cement. All tests were conducted according to the ISO and IAEA recommendations. 3 years leaching results are reported, determining cesium and strontium diffusivity coefficients for boric acid waste form and ion-exchange resins. (Author)

  8. Partitioning of actinides from high active waste solution of Purex origin counter-current extraction studies using TBP and CMPO

    A solvent extraction scheme has been formulated for the partitioning of actinides from Purex high level waste (HLW). The scheme is based on the results of earlier studies carried out with simulated waste solutions. In the present studies, the scheme was tested with high active waste (HAW) solution generated during the reprocessing of spent fuel from research reactors using laboratory scale mixer-settlers. The proposed process involved two-step extraction using tri-n-butyl phosphate (TBP) and octyl (phenyl)-N,N-diisobutylcarbamolylmethylphosphine oxide (CMPO). In the first step, uranium, neptunium and plutonium were removed from the waste using TBP as extractant. The minor actinides left in the raffinate were extracted using a mixture of CMPO and TBP in the second step. The results showed complete extraction of actinides from the waste solution. Plutonium and neptunium extracted in TBP, were stripped together using a mixture of hydrogen peroxide and ascorbic acid in 2 M nitric acid medium, leaving uranium in the organic phase. Uranium can later be stripped using dilute nitric acid. Actinides extracted in CMPO-TBP phase were stripped using a mixture of formic acid, hydrazine, hydrate and citric acid. The stripping was quantitative in both the stripping runs. An additional extraction step for the preferential recovery of uranium, neptunium and plutonium from the waste solution using TBP is a modification over the conventional Truex process. Selective stripping of neptunium and plutonium from large quantities of uranium. The extraction of uranium using TBP eliminates the possibility of third phase and undesired loading of CMPO-TBP in the following step. Use of citrate-containing strippant allows the recovery of actinides from loaded CMPO-TBP mixture without causing any reflux of the actinides during stripping. The process has been developed with due consideration to minimising the generation of secondary wastes. The proposed strippants are effective even in presence of

  9. Radionuclide Retention in Concrete Waste Forms

    Mattigod, Shas V.; Bovaird, Chase C.; Wellman, Dawn M.; Wood, Marcus I.

    2010-09-30

    Assessing long-term performance of Category 3 waste cement grouts for radionuclide encasement requires knowledge of the radionuclide-cement interactions and mechanisms of retention (i.e., sorption or precipitation); the mechanism of contaminant release; the significance of contaminant release pathways; how waste form performance is affected by the full range of environmental conditions within the disposal facility; the process of waste form aging under conditions that are representative of processes occurring in response to changing environmental conditions within the disposal facility; the effect of waste form aging on chemical, physical, and radiological properties; and the associated impact on contaminant release. This knowledge will enable accurate prediction of radionuclide fate when the waste forms come in contact with groundwater. The information presented in the report provides data that 1) quantify radionuclide retention within concrete waste form materials similar to those used to encapsulate waste in the Low-Level Waste Burial Grounds (LLBG); 2) measure the effect of concrete waste form properties likely to influence radionuclide migration; and 3) quantify the stability of uranium-bearing solid phases of limited solubility in concrete.

  10. Actinide recycle

    A multitude of studies and assessments of actinide partitioning and transmutation were carried out in the late 1970s and early 1980s. Probably the most comprehensive of these was a study coordinated by Oak Ridge National Laboratory. The conclusions of this study were that only rather weak economic and safety incentives existed for partitioning and transmuting the actinides for waste management purposes, due to the facts that (1) partitioning processes were complicated and expensive, and (2) the geologic repository was assumed to contain actinides for hundreds of thousands of years. Much has changed in the few years since then. A variety of developments now combine to warrant a renewed assessment of the actinide recycle. First of all, it has become increasingly difficult to provide to all parties the necessary assurance that the repository will contain essentially all radioactive materials until they have decayed. Assurance can almost certainly be provided to regulatory agencies by sound technical arguments, but it is difficult to convince the general public that the behavior of wastes stored in the ground can be modeled and predicted for even a few thousand years. From this point of view alone there would seem to be a clear benefit in reducing the long-term toxicity of the high-level wastes placed in the repository

  11. DWPF waste form compliance plan (Draft Revision)

    The Department of Energy currently has over 100 million liters of high-level radioactive waste in storage at the Savannah River Site (SRS). In the late 1970's, the Department of Energy recognized that there were significant safety and cost advantages associated with immobilizing the high-level waste in a stable solid form. Several alternative waste forms were evaluated in terms of product quality and reliability of fabrication. This evaluation led to a decision to build the Defense Waste Processing Facility (DWPF) at SRS to convert the easily dispersed liquid waste to borosilicate glass. In accordance with the NEPA (National Environmental Policy Act) process, an Environmental Impact Statement was prepared for the facility, as well as an Environmental Assessment of the alternative waste forms, and issuance of a Record of Decision (in December, 1982) on the waste form. The Department of Energy, recognizing that start-up of the DWPF would considerably precede licensing of a repository, instituted a Waste Acceptance Process to ensure that these canistered waste forms would be acceptable for eventual disposal at a federal repository. This report is a revision of the DWPF compliance plan

  12. The effects of actinide separation on the radiological consequences of geologic disposal of high-level waste

    It has often been suggested that the potential hazard to man from the disposal of high-level radioactive waste could be reduced by removing a substantial fraction of the actinide elements. In this report the effects of actinide separation on the radiological consequences of one of the disposal options currently under consideration, that of burial in deep geologic formations, are examined. The results show that the potential radiological impact of geologic disposal of high-level waste arises from both long-lived fission products and actinides (and their daughter radionuclides). Neither class of radionuclides is of overriding importance and actinide separation would therefore reduce the radiological impact to only a limited extent and over limited periods. There might be a case for attempting to reduce doses from 237Np. To achieve this it appears to be necessary to separate both neptunium and its precursor element americium. However, there are major uncertainties in the data needed to predict doses from 237Np; further research is required to resolve these uncertainties. In addition, consideration should be given to alternative methods of reducing the radiological impact of geologic disposal. The conclusions of this assessment differ considerably from those of similar studies based on the concept of toxicity indices. Use of these indices can lead to incorrect allocation of research and development effort. (author)

  13. Role of Microbes as Biocolloids in the Transport of Actinides from a Deep Underground Radioactive Waste Repository

    Dodge, C.J.; Dunn, M.; Francis, A.J.; Gillow, J.B.; Mantione, K.; Pansoy-Hjelvik, M.E.; Papenguth, H.W.; Strietelmeier, B.A.

    1998-12-17

    We investigated the interaction of dissolved actinides Th, U, Np Zgpu, and Am, with a pure and a mixed culture of halophilic bactezia isolated from the Waste Isolation H.Iot Plant repository under anaerobic conditions to evaluate their potentiaI transport as biocolloids from the waste site. The sizes of the bacterial cells studied ranged from ().54 x 0.48 pm to 7.7 x 0.67pm Using sequential mimofiltration, we determined the ~~ation of actinides with fi-ee-living (mobile) bacterial cells suspended in a fluid medium containing. NaCl or M=W12 brine, at various phaes of their growth cycIes. The number of suspended kcteria rangy-d born 106 to 109 cells ml-*. Tine amount of actinide associatd with the wspend~ cell fraction (cakzdated & mol cell-*) was very Iow: Th, 10-*2; U, 10-1s - 10-lS; - ~ Np, 1o-15- 10-19; Pu, 10-ls -10-21 ; and h, 10-1* - 10-*9 ; and it varied with the bacteihl - CUIture studied. l%e differe&es in the asswiation are amibuted to the extent of bioamxmdation and biosorption by the bacteria pH, the compo&on of the brine, and the speziation and bioavaiIability of the actinides.

  14. Ceramic and glass radioactive waste forms

    Readey, D.W.; Cooley, C.R. (comps.)

    1977-01-01

    This report contains 14 individual presentations and 6 group reports on the subject of glass and polycrystalline ceramic radioactive waste forms. It was the general consensus that the information available on glass as a waste form provided a good basis for planning on the use of glass as an initial waste form, that crystalline ceramic forms could also be good waste forms if much more development work were completed, and that prediction of the chemical and physical stability of the waste form far into the future would be much improved if the basic synergistic effects of low temperature, radiation and long times were better understood. Continuing development of the polycrystalline ceramic forms was recommended. It was concluded that the leach rate of radioactive species from the waste form is an important criterion for evaluating its suitability, particularly for the time period before solidified waste is permanently placed in the geologic isolation of a Federal repository. Separate abstracts were prepared for 12 of the individual papers; the remaining two were previously abstracted.

  15. Rietveld analysis of ceramic nuclear waste forms

    Powder X-ray diffraction patterns were collected from three titanate waste forms - a calcine powder, a prototype ceramic without waste, and a ceramic containing 10 wt% JW-A simulated waste - and interpreted quantitatively using the Rietveld method. The calcine consisted of fluorite, pyrochlore, rutile, and amorphous material. The prototype waste form contained rutile, hollandite, zirconolite and perovskite. The phase constitution of the JW-A ceramic was freudenbergite, loveringite, hollandite, zirconolite, perovskite and baddeleyite. Procedures for the collection of X-ray data are described, as are assumptions inherent in the Rietveld approach. A selection of refined crystal data are presented

  16. Leaching of nuclear power reactor waste forms

    The leaching tests for immobilized power reactor wastes carried out at IPEN are described. These wastes forms consist mainly of spent resins and boric acid concentrates solidified in ordinary Portland cement. All tests were conducted according to the ISO and IAEA recommendations. Three years leaching results are reported. The cesium diffuvity coefficients determined out of these results are about 1 x 10-8 cm2/s for boric acid waste form and 9 x 10-9 cm2/s for ion-exchange resin waste. Strontium diffusivity coefficients found are about 3 x 10-11 cm2/s and 9 x 10-11 cm2/s respectively. (Author)

  17. Rietveld analysis of ceramic nuclear waste forms

    White, T.J. [Univ. of South Australia, Ingle Farm (Australia); Mitamura, H. [Japan Atomic Energy Research Institute, Ibaraki (Japan)

    1994-12-31

    Powder X-ray diffraction patterns were collected from three titanate waste forms - a calcine powder, a prototype ceramic without waste, and a ceramic containing 10 wt% JW-A simulated waste - and interpreted quantitatively using the Rietveld method. The calcine consisted of fluorite, pyrochlore, rutile, and amorphous material. The prototype waste form contained rutile, hollandite, zirconolite and perovskite. The phase constitution of the JW-A ceramic was freudenbergite, loveringite, hollandite, zirconolite, perovskite and baddeleyite. Procedures for the collection of X-ray data are described, as are assumptions inherent in the Rietveld approach. A selection of refined crystal data are presented.

  18. Extraction chromatographic separation of minor actinides from PUREX high-level wastes using CMPO

    An extraction chromatographic technique using octyl(phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO) adsorbed on chromosorb-102 (CAC) has been tested as an alternative to the TRUEX solvent extraction process, where CMPO has been used as the extracting agent to recover minor actinides from high-activity waste (HAW) solutions of PUREX origin. The batchwise uptake behavior of U(VI), Pu(IV), Am(III), Eu(III), Zr(IV), Fe(III), Ru(III), and TcO4- from a nitric acid medium by CAC has been studied. The uptake of actinides and lanthanides are higher than those of other fission products and inert materials. The batchwise loading experiments in the presence of Nd(III)/U(VI) have shown that at lower concentrations of these metal ions, the uptake of Pu(IV), U(VI), and Am(III) are reasonably high. Studies on loading of Nd(III), U(VI), and Pu(IV) on a column containing 1.7 g of CAC have shown that Nd(III) (30 mg) and U(VI) (90 mg) could be loaded, while Pu(IV) (∼0.6) was loaded on a small column containing 100 mg of CAC without any break-through. Further, a synthetic HAW solution as such and the actual PUREX HAW solution, after depleting the uranium content by a 30% tributyl-phosphate contact, were loaded on a CAC column. The effluents did not contain any alpha activity above the background level. The activities could subsequently be eluted with 0.0.4 M HNO3 (americium and rare earths), 0.01 M oxalic acid (plutonium), and 0.25 M Na2CO3 [U(VI)]. The recoveries of these metal ions were found to be >99%

  19. Application of extraction chromatographic technique in the recovery of actinides from Purex waste solutions using CMPO

    Extraction chromatographic technique using octyl(phenyl)-N,N-diisobutylcarbomoylmethylphosphine oxide (CMPO) adsorbed on chromosorb-102 (CAC) has been developed as a potential alternative to the Truex process, where CMPO has been deployed as the extracting agent to recover minor actinides from the high active waste (HAW) solution of Purex origin. In this connection, the batch-wise uptake behaviour of U(VI), Pu(VI), Am(III), Eu(III), Zr(IV), Fe(III), Ru(III) and TcO4 from nitric acid medium by CAC has been studied. The uptake of actinides and lanthanides are higher than those of other fission products and inert materials. The batch-wise loading experiments in presence of Nd(III)/U(VI) have shown that at lower concentration of these metal ions, the uptake of Pu(IV), U(VI) and Am(III) are reasonably high. Studies on loading of Nd(III), U(VI) and Pu(IV) on a column containing 1.7 g CAC have shown that Nd(III) (30 mg) and U(VI) (90 mg) could be loaded, while Pu(IV) (∼0.6 mg) was loaded on a small column containing 100 mg CAC without any breakthrough. Further, a synthetic HAW solution and the actual Purex HAW solution were loaded on a CAC column. The effluents did not contain any alpha activity above the background level. The activities could subsequently be eluted with 0.04 M HNO3 (Am and RE), 0.01 M oxalic acid (Pu) and 0.25 MNa2CO3 solution (U(VI)). The recoveries of these metal ions were found to be > 99%. The eluted Am and rare earth fraction is an important source for 147Pm. This process is amenable for further scaling up. (author). 17 refs., 5 figs., 8 tabs

  20. Scenarios for minor actinides transmutation in the framework of the French Act on Waste Management

    In the framework of the French Act on Waste Management, options of minor actinides (MA) transmutation are studied, based on several scenarios of sodium fast reactor deployment. Basically, one of these scenarios considers the deployment of a 60 GWe SFR fleet in two steps (20 GWe from 2040 to 2050 and 40 GWe, as well as, from 2080 to 2100). For this scenario, the advantages and drawbacks of different transmutation options are evaluated: - transmutation of all minor actinides or only of americium; - transmutation in homogeneous mode (MA bearing fuel in all the core or just in the outer core) or in heterogeneous mode (MA bearing radial blankets). Scenarios have been optimised to limit the impacts of MA transmutation on the cycle: - reduction of the initial MA content in the core in the case of transmutation in homogeneous mode to reduce the impact on reactivity coefficients; - reduction of the number of rows of blankets and fuel decay heat in the case of transmutation in heterogeneous mode. The sensitivity of transmutation options to cycle parameters such as the fuel cooling time before transportation is also assessed. Thus, the transmutation of only americium in one row of radial blankets containing initially 10 pc % Am and irradiated during the same duration as the standard fuel assemblies appears to be a suitable solution to limit the transmutation impacts on fuel cycle and facilities. A comparison of results obtained with MA transmutation in dedicated systems is also presented with a symbiotic scenario considering ADS (accelerator-driven system) deployment to transmute MA together with a SFR fleet to produce energy. The MA inventory within the cycle is higher in the case of transmutation in ADS than in the case of transmutation in SFR. Considering the industrial feasibility of MA transmutation, it appears important to study 'independently' SFR deployment and MA transmutation. Consequently, scenarios of progressive introduction of MA options are assessed

  1. Performance Test on Polymer Waste Form

    Boric acid wastewater and spent ion exchange resins are generated as a low- and medium- level radioactive wastes from pressurized light water reactors. In Korea, boric acid wastewater is concentrated and dried in the form of granules, and finally solidified by using paraffin wax. In this study, polymer solidification was attempted to produce the stable waste form for the boric acid concentrates and the dewatered spent ion exchange resins. The polymer mixture which consists of epoxy resin, amine compounds and antimony trioxide was used to solidify the boric acid concentrates and the dewatered spent ion exchange resins. To evaluate the stability of polymer waste forms, a series of standardized performance tests was conducted. Also, by the requirement of the regulatory institute in Korea, an additional test was performed to estimate fire resistance and gas generation of the waste forms. A series of performance tests was conducted including compressive strength test, thermal stability test, irradiation stability test and biodegradation stability test, water immersion test, leach test, and free standing water for the polymer waste forms. In addition, a fire resistance test and an analysis of gas generation were performed on the waste forms by the requirement of the regulatory institute in Korea. From the results of the performance tests, it is believed that the polymer waste form is very stable and can satisfy the acceptance criteria for permanent disposal

  2. Performance Test on Polymer Waste Form

    Lee, Se Yup [Korea Nuclear Engineering Co., Ltd, Seongnam (Korea, Republic of)

    2012-07-01

    Boric acid wastewater and spent ion exchange resins are generated as a low- and medium- level radioactive wastes from pressurized light water reactors. In Korea, boric acid wastewater is concentrated and dried in the form of granules, and finally solidified by using paraffin wax. In this study, polymer solidification was attempted to produce the stable waste form for the boric acid concentrates and the dewatered spent ion exchange resins. The polymer mixture which consists of epoxy resin, amine compounds and antimony trioxide was used to solidify the boric acid concentrates and the dewatered spent ion exchange resins. To evaluate the stability of polymer waste forms, a series of standardized performance tests was conducted. Also, by the requirement of the regulatory institute in Korea, an additional test was performed to estimate fire resistance and gas generation of the waste forms. A series of performance tests was conducted including compressive strength test, thermal stability test, irradiation stability test and biodegradation stability test, water immersion test, leach test, and free standing water for the polymer waste forms. In addition, a fire resistance test and an analysis of gas generation were performed on the waste forms by the requirement of the regulatory institute in Korea. From the results of the performance tests, it is believed that the polymer waste form is very stable and can satisfy the acceptance criteria for permanent disposal.

  3. Effects of Ammonium Molybdophosphate (AMP) on Strontium, Actinides, and RCRA Metals in SRS Simulated Waste

    High Level Waste samples contain elevated concentrations of radioactive cesium requiring marked dilution of the waste to facilitate handling in non-shielded facilities. The authors developed a sample treatment protocol, using ammonium molybdophosphate (AMP) to remove sufficient cesium to allow handling of the samples with minimal dilution. The sample treatment protocol includes the following steps: pH adjust the sample to the range of 0.01 to 1.0 M acidity; mix 30 mL of acidified sample with 40-60 mg of AMP; cap and shake the mixture for 30-60 seconds; filter AMP from the liquid using 0.45 PTFE syringe filters; and send filtrate directly forward for analysis. To develop the method, SRTC performed a series of tests with three different salt solutions designed to determine the propensity of ammonium molybdophosphate (AMP) to bind some of the common analytes such as the actinides (Pu, Am, Np, U), strontium, or the metals (Ag, As, Ba, Cd, Cr, Hg, Pb, Se) regulated by the Resource Conservation Recovery Act (RCRA). SRTC also examined relevant literature to summarize reported interactions between AMP and other elements

  4. Thermodynamics of the volatilization of actinide metals in the high-temperature treatment of radioactive wastes. 1998 annual progress report

    'In this project, the authors perform a detailed study of the volatilization behavior of U, Pu and possibly Am and Np under conditions relevant to the thermal treatment (destruction) of actinide-containing organic-based mixed and radioactive wastes. The primary scientific goal of the proposed work is to develop a basic thermochemical understanding of actinide volatilization and partitioning/speciation behavior in the thermal processes that are central to DOE/EM''s mixed waste treatment program. This subject addresses several technical needs/problem areas recently identified by DOE/EM''s Office of Science and Technology. In the Low-Level and Mixed Low-Level Waste problem area, emission-free destruction of organic wastes is listed as the first exemplary science need. In the TRU Waste, Plutonium Materials, and Spent Nuclear Fuel problem areas, interactions between actinides and organic residues and materials stabilization are listed as exemplary science needs. Both of these needs require high-temperature thermodynamic studies of actinides and actinide-organic interactions. A sound basis for designing safe and effective thermal treatment systems and the ability to allay public concerns about radioactive fugitive emissions are the principal benefits of the project. The proposed work is a combination of experimental studies and thermodynamic modeling. Vapor pressure measurements will be made to determine U, Pu and possibly Am volatile species and the extent of their volatilization when UO2/U3O8, PuO2 and AmO2 solids are heated to temperatures of 500 to 1,500 C under pyrolyzing (reducing) conditions or under oxidizing conditions (i.e. O2 (g) + H2O(g) mixtures) in the presence of chlorine (Cl2 (g) or HCl(g)). Work on uranium volatilization under reducing conditions will be performed in a laboratory at U. C. Berkeley in a collaboration with Professor D. R. Olander. In parallel with the experimental effort, a complete thermodynamic database for expected actinide gaseous

  5. Secondary Waste Form Down-Selection Data Package - Fluidized Bed Steam Reforming Waste Form

    The Hanford Site in southeast Washington State has 56 million gallons of radioactive and chemically hazardous wastes stored in 177 underground tanks (ORP 2010). The U.S. Department of Energy (DOE), Office of River Protection (ORP), through its contractors, is constructing the Hanford Tank Waste Treatment and Immobilization Plant (WTP) to convert the radioactive and hazardous wastes into stable glass waste forms for disposal. Within the WTP, the pretreatment facility will receive the retrieved waste from the tank farms and separate it into two treated process streams. These waste streams will be vitrified, and the resulting waste canisters will be sent to offsite (high-level waste (HLW)) and onsite (immobilized low-activity waste (ILAW)) repositories. As part of the pretreatment and ILAW processing, liquid secondary wastes will be generated that will be transferred to the Effluent Treatment Facility (ETF) on the Hanford Site for further treatment. These liquid secondary wastes will be converted to stable solid waste forms that will be disposed of in the Integrated Disposal Facility (IDF). To support the selection of a waste form for the liquid secondary wastes from WTP, Washington River Protection Solutions (WRPS) has initiated secondary waste form testing work at Pacific Northwest National Laboratory (PNNL). In anticipation of a down-selection process for a waste form for the Solidification Treatment Unit to be added to the ETF, PNNL is developing data packages to support that down-selection. The objective of the data packages is to identify, evaluate, and summarize the existing information on the four waste forms being considered for stabilizing and solidifying the liquid secondary wastes. At the Hanford Site, the FBSR process is being evaluated as a supplemental technology for treating and immobilizing Hanford LAW radioactive tank waste and for treating secondary wastes from the WTP pretreatment and LAW vitrification processes.

  6. Secondary Waste Form Down-Selection Data Package—Fluidized Bed Steam Reforming Waste Form

    Qafoku, Nikolla; Westsik, Joseph H.; Strachan, Denis M.; Valenta, Michelle M.; Pires, Richard P.

    2011-09-12

    The Hanford Site in southeast Washington State has 56 million gallons of radioactive and chemically hazardous wastes stored in 177 underground tanks (ORP 2010). The U.S. Department of Energy (DOE), Office of River Protection (ORP), through its contractors, is constructing the Hanford Tank Waste Treatment and Immobilization Plant (WTP) to convert the radioactive and hazardous wastes into stable glass waste forms for disposal. Within the WTP, the pretreatment facility will receive the retrieved waste from the tank farms and separate it into two treated process streams. These waste streams will be vitrified, and the resulting waste canisters will be sent to offsite (high-level waste [HLW]) and onsite (immobilized low-activity waste [ILAW]) repositories. As part of the pretreatment and ILAW processing, liquid secondary wastes will be generated that will be transferred to the Effluent Treatment Facility (ETF) on the Hanford Site for further treatment. These liquid secondary wastes will be converted to stable solid waste forms that will be disposed of in the Integrated Disposal Facility (IDF). To support the selection of a waste form for the liquid secondary wastes from WTP, Washington River Protection Solutions (WRPS) has initiated secondary waste form testing work at Pacific Northwest National Laboratory (PNNL). In anticipation of a down-selection process for a waste form for the Solidification Treatment Unit to be added to the ETF, PNNL is developing data packages to support that down-selection. The objective of the data packages is to identify, evaluate, and summarize the existing information on the four waste forms being considered for stabilizing and solidifying the liquid secondary wastes. At the Hanford Site, the FBSR process is being evaluated as a supplemental technology for treating and immobilizing Hanford LAW radioactive tank waste and for treating secondary wastes from the WTP pretreatment and LAW vitrification processes.

  7. Evaluation of solidified cement waste forms

    A part of the program of the treatment of low and intermediate-level liquid wastes, is presented. The concrete has been suggested as a encapsulation or overpack material for long-term storage of radioactive waste from the nuclear fuel cycle, particularly in conjunction with the disposal of lowand intermediate-level waste. The influence of sodium nitrates, as a possible integrating component of waste, on some properties of national Portland cement, was investigated. The waste form properties, discussed in terms of their dependency on waste type and amount, include water/cement ratio, setting times, compressive strength and homogeneity. Criteria to be applied in the assessment of the final solidified waste are proposed. (Author)

  8. Iodine waste form summary report (FY 2007).

    Krumhansl, James Lee; Nenoff, Tina Maria; McMahon, Kevin A.; Gao, Huizhen; Rajan, Ashwath Natech

    2007-11-01

    This new program at Sandia is focused on Iodine waste form development for GNEP cycle needs. Our research has a general theme of 'Waste Forms by Design' in which we are focused on silver loaded zeolite waste forms and related metal loaded zeolites that can be validated for chosen GNEP cycle designs. With that theme, we are interested in materials flexibility for iodine feed stream and sequestration material (in a sense, the ability to develop a universal material independent on the waste stream composition). We also are designing the flexibility to work in a variety of repository or storage scenarios. This is possible by studying the structure/property relationship of existing waste forms and optimizing them to our current needs. Furthermore, by understanding the properties of the waste and the storage forms we may be able to predict their long-term behavior and stability. Finally, we are working collaboratively with the Waste Form Development Campaign to ensure materials durability and stability testing.

  9. Comparison of different options for minor actinide transmutation in the frame of the French law for waste management

    In the frame of the French Act for waste management which has been passed by French Parliament on June 28th, 2006, it is requested to obtain in 2012 an assessment of industrial perspectives of partitioning and transmutation of long-lived elements. These studies must be carried out in tight connection with GENIV systems development. The expected results must include the evaluation of technical and economic scenarios taking into account the optimization options between the minor actinide transmutation processes, their interim storage and geological disposal, including an analysis of several criteria. In this perspective, the CEA has established a working group named 'GT TES' (Working Group on Technical and Economic Scenarios) involving EDF and AREVA to define scenarios, the various criteria to evaluate them, to conduct these evaluations and then to highlight the key results. The group also relied on ANDRA for the geological storage studies. The scenarios evaluations take place in the French context. The nuclear energy production is supposed to remain constant during the scenarios and equal to 430 TWhe/year in accordance with the current French nuclear power installed capacity of 60 GW(e). The deployment of the first Sodium-cooled Fast Reactor (SFR) starts in 2040, considering that at this date the SFR technology should be mature. Several management schemes of minor actinides have been studied: Plutonium recycling in SFR (minor actinides are sent to the waste). Plutonium recycling and minor actinide (or Am alone) transmutation in SFR and in homogeneous mode ('Hom.'). Plutonium recycling and minor actinide (or Am alone) transmutation in SFR and in heterogeneous mode ('Het.'). Plutonium recycling in SFR and minor actinide transmutation in Accelerator-Driven-System (ADS). The criteria used to analyze these different scenarios, should take into account the viewpoint of scientists, industrials, administrations, and the general public. They are listed below: Inventories and

  10. SEPARATIONS AND WASTE FORMS CAMPAIGN IMPLEMENTATION PLAN

    Vienna, John D.; Todd, Terry A.; Peterson, Mary E.

    2012-11-26

    This Separations and Waste Forms Campaign Implementation Plan provides summary level detail describing how the Campaign will achieve the objectives set-forth by the Fuel Cycle Reasearch and Development (FCRD) Program. This implementation plan will be maintained as a living document and will be updated as needed in response to changes or progress in separations and waste forms research and the FCRD Program priorities.

  11. Chemical compatibility of DWPF canistered waste forms

    The Waste Acceptance Preliminary Specifications (WAPS) require that the contents of the canistered waste form are compatible with one another and the stainless steel canister. The canistered waste form is a closed system comprised of a stainless steel vessel containing waste glass, air, and condensate. This system will experience a radiation field and an elevated temperature due to radionuclide decay. This report discusses possible chemical reactions, radiation interactions, and corrosive reactions within this system both under normal storage conditions and after exposure to temperatures up to the normal glass transition temperature, which for DWPF waste glass will be between 440 and 460 degrees C. Specific conclusions regarding reactions and corrosion are provided. This document is based on the assumption that the period of interim storage prior to packaging at the federal repository may be as long as 50 years

  12. Evaluation of possible physical-chemical processes that might lead to separations of actinides in ORNL waste tanks

    Del Cul, G.D.; Toth, L.M.; Bond, W.D.; Dai, S.

    1997-09-01

    The concern that there might be some physical-chemical process which would lead to a separation of the poisoning actinides ({sup 232}Th, {sup 238}U) from the fissionable ones ({sup 239}Pu, {sup 235}U) in waste storage tanks at Oak Ridge National Laboratory has led to a paper study of potential separations processes involving these elements. At the relatively high pH values (>8), the actinides are normally present as precipitated hydroxides. Mechanisms that might then selectively dissolve and reprecipitate the actinides through thermal processes or additions of reagents were addressed. Although redox reactions, pH changes, and complexation reactions were all considered, only the last type was regarded as having any significant probability. Furthermore, only carbonate accumulation, through continual unmonitored air sparging of the tank contents, could credibly account for gross transport and separation of the actinide components. From the large amount of equilibrium data in the literature, concentration differences in Th, U, and Pu due to carbonate complexation as a function of pH have been presented to demonstrate this phenomenon. While the carbonate effect does represent a potential separations process, control of long-term air sparging and solution pH, accompanied by routine determinations of soluble carbonate concentration, should ensure that this separations process does not occur.

  13. Actinides geochemical database for performance analysis of high-level radioactive waste repositories and the program to increase its confidence

    Japan Nuclear Cycle Development Institute (JNC) published a second progress report (H12 report) in 1999 to clarify the technical confidence of the concept and technical bases for site selection and safety standards for high-level radioactive waste (HLW) geological disposal and Japan. A law for HLW final disposal was legislated based on the knowledge of the H12 report and an implementing body was established in 2000 by the law. Thus the HLW disposal program in Japan has been entered into the implementation phase. The thermodynamic database (TDB) and the sorption database (SDB) for actinides have been developed in performance analysis of the H12 report. The TDB for actinides are based on reliable measurement data, a thermodynamic models and chemical analogy. The SDB for actinides was developed and selection of distribution coefficient (Kd) was carried out under consideration of repository conditions. The validity of these databases was checked through individual migration experiments. JNC has started the work program using the QUALITY' (Quantitative Assessment Radionuclide Migration Experiment Facility) since 1999, in which we have systematically obtained migration data for radionuclides including actinides under reducing conditions. This facility enables to supply the reliable migration data widely applicable in Japanese geological conditions. (author)

  14. Evaluation of possible physical-chemical processes that might lead to separations of actinides in ORNL waste tanks

    The concern that there might be some physical-chemical process which would lead to a separation of the poisoning actinides (232Th, 238U) from the fissionable ones (239Pu, 235U) in waste storage tanks at Oak Ridge National Laboratory has led to a paper study of potential separations processes involving these elements. At the relatively high pH values (>8), the actinides are normally present as precipitated hydroxides. Mechanisms that might then selectively dissolve and reprecipitate the actinides through thermal processes or additions of reagents were addressed. Although redox reactions, pH changes, and complexation reactions were all considered, only the last type was regarded as having any significant probability. Furthermore, only carbonate accumulation, through continual unmonitored air sparging of the tank contents, could credibly account for gross transport and separation of the actinide components. From the large amount of equilibrium data in the literature, concentration differences in Th, U, and Pu due to carbonate complexation as a function of pH have been presented to demonstrate this phenomenon. While the carbonate effect does represent a potential separations process, control of long-term air sparging and solution pH, accompanied by routine determinations of soluble carbonate concentration, should ensure that this separations process does not occur

  15. Position of actinide elements in the periodic table : evolution of a generalised form (Preprint no. SSC-33)

    All the actinides and lanthanides are placed in III group and are shown separately, in the most popular forms of the periodic table, including the latest version of IUPAC. This has been leading to an avoidable debate i.e. whether to place La and Ac or Lu and Lw below Sc and Y in the III-B group. Apart from this, the group characteristic nature of most of the actinides elements, demands that a more appropriate position is to be given to these f block elements. The situation is more complex in the higher periods, in which new elements belonging to g block, h block, ... are to be included. Also, there seems to be no consensus in following a uniform and acceptable subgroup notation. The author arrived at a new form of the periodic table to successfully sort out all these issues. The table is presented. (author). 10 refs., 1 fig

  16. Low-risk alternative waste forms for problematic high-level and long-lived nuclear wastes

    Full text: The highest cost component the nuclear waste clean up challenge centres on high-level waste (HLW) and consequently the greatest opportunity for cost and schedule savings lies with optimising the approach to HLW cleanup. The waste form is the key component of the immobilisation process. To achieve maximum cost savings and optimum performance the selection of the waste form should be driven by the characteristics of the specific nuclear waste to be immobilised, rather than adopting a single baseline approach. This is particularly true for problematic nuclear wastes that are often not amenable to a single baseline approach. The use of tailored, high-performance, alternative waste forms that include ceramics and glass-ceramics, coupled with mature process technologies offer significant performance improvements and efficiency savings for a nuclear waste cleanup program. It is the waste form that determines how well the waste is locked up (chemical durability), and the number of repository disposal canisters required (waste loading efficiency). The use of alternative waste forms for problematic wastes also lowers the overall risk by providing high performance HLW treatment alternatives. The benefits tailored alternative waste forms bring to the HLW cleanup program will be briefly reviewed with reference to work carried out on the following: The HLW calcines at the Idaho National Laboratory; SYNROC ANSTO has developed a process utilising a glass-ceramic combined with mature hot-isostatic pressing (HIP) technology and has demonstrated this at a waste loading of 80 % and at a 30 kg HIP scale. The use of this technology has recently been estimated to result in a 70 % reduction in waste canisters, compared to the baseline borosilicate glass technology; Actinide-rich waste streams, particularly the work being done by SYNROC ANSTO with Nexia Solutions on the Plutonium-residues wastes at Sellafield in the UK, which if implemented is forecast to result in substantial

  17. Treatment and recycling of spent nuclear fuel. Actinide partitioning - Application to waste management

    subsequent to its in-reactor dwell time, spent fuel still contains large amounts of materials that are recoverable, for value-added energy purposes (uranium, plutonium), together with fission products, and minor actinides, making up the residues from nuclear reactions. The treatment and recycling of spent nuclear fuel, as implemented in France, entail that such materials be chemically partitioned. The development of the process involved, and its deployment on an industrial scale stand as a high achievement of French science, and technology. Treatment and recycling allow both a satisfactory management of nuclear waste to be implemented, and substantial savings, in terms of fissile material. Bolstered of late as it has been, due to spectacularly skyrocketing uranium prices, this strategy is bound to become indispensable, with the advent of the next generation of fast reactors. This Monograph surveys the chemical process used for spent fuel treatment, and its variants, both current, and future. It outlines currently ongoing investigations, setting out the challenges involved, and recent results obtained by CEA. (authors)

  18. Treatment and recycling of spent nuclear fuel. Actinide partitioning - Application to waste management

    Abonneau, E.; Baron, P.; Berthon, C.; Berthon, L.; Beziat, A.; Bisel, I.; Bonin, L.; Bosse, E.; Boullis, B.; Broudic, J.C.; Charbonnel, M.C.; Chauvin, N.; Den Auwer, C.; Dinh, B.; Duhamet, J.; Escleine, J.M.; Grandjean, S.; Guilbaud, P.; Guillaneux, D.; Guillaumont, D.; Hill, C.; Lacquement, J.; Masson, M.; Miguirditchian, M.; Moisy, P.; Pelletier, M.; Ravenet, A.; Rostaing, C.; Royet, V.; Ruas, A.; Simoni, E.; Sorel, C.; Vaudano, A.; Venault, L.; Warin, D.; Zaetta, A.; Pradel, P.; Bonin, B.; Bouquin, B.; Dozol, M.; Lecomte, M.; Forestier, A.; Beauvy, M.; Berthoud, G.; Defranceschi, M.; Ducros, G.; Guerin, Y.; Latge, C.; Limoge, Y.; Madic, C.; Santarini, G.; Seiler, J.M.; Sollogoob, P.; Vernaz, E.; Bazile, F.; Parisot, J.P.; Finot, P.; Roberts, J.F

    2008-07-01

    subsequent to its in-reactor dwell time, spent fuel still contains large amounts of materials that are recoverable, for value-added energy purposes (uranium, plutonium), together with fission products, and minor actinides, making up the residues from nuclear reactions. The treatment and recycling of spent nuclear fuel, as implemented in France, entail that such materials be chemically partitioned. The development of the process involved, and its deployment on an industrial scale stand as a high achievement of French science, and technology. Treatment and recycling allow both a satisfactory management of nuclear waste to be implemented, and substantial savings, in terms of fissile material. Bolstered of late as it has been, due to spectacularly skyrocketing uranium prices, this strategy is bound to become indispensable, with the advent of the next generation of fast reactors. This Monograph surveys the chemical process used for spent fuel treatment, and its variants, both current, and future. It outlines currently ongoing investigations, setting out the challenges involved, and recent results obtained by CEA. (authors)

  19. Humic substances in performance assessment of nuclear waste disposal: Actinide and iodine migration in the far-field. Third technical progress report

    The present report describes progress within the third and final year of the EC-project 'Humic Substances in Performance Assessment of Nuclear Waste Disposal: Actinide and Iodine Migration in the Far-Field'. The work conducted within the present project builds on a number of previous activities/project supported by the Commission. It finds its continuation within different EC FP 6 instruments and also provides for additional continued cooperation through network structures resulting from the broad cooperation within the project. Without being a formal requirement of the Commission or co-funding bodies, this report documents results in great technical detail and makes the results available to a broad scientific community. The report contains an executive summary written by the coordinator. More detailed results are given as individual contributions in the form of 12 annexes. Not all results are discussed or referred to in the executive summary report and thus readers with a deeper interest also need to consult the annexes. The overall objectives were to generate knowledge about the impact of humic substances on the migration of actinides and iodine in the far-field of a nuclear waste repository. In the beginning, focus was rather on the potential enhancement due to humic colloid mediated radionuclide transport. Thereby, sources, inventory, stability and mobility of dissolved humic substances in their colloidal form formed a key topic. Other key topics were the interaction with actinides and iodine, transport studies under near-natural conditions in the laboratory, rationalization of knowledge in models and application to three migration cases for visualization of the overall outcome. Changes relative to the original objectives were given by moving emphasis of natural chemical analogue studies from the question of kinetic exchange constants for different inventories in natural and laboratory systems to the study of anthropogenic actinide contaminants in the Irish Sea

  20. Separation of actinides and long-lived fission products from high-level radioactive wastes (a review)

    The management of high-level radioactive wastes is facilitated, if long-lived and radiotoxic actinides and fission products are separated before the final disposal. Especially important is the separation of americium, curium, plutonium, neptunium, strontium, cesium and technetium. The separated nuclides can be deposited separately from the bulk of the high-level waste, but their transmutation to short-lived nuclides is a muchmore favourable option. This report reviews the chemistry of the separation of actinides and fission products from radioactive wastes. The composition, nature and conditioning of the wastes are described. The main attention is paid to the solvent extraction chemistry of the elements and to the application of solvent extraction in unit operations of potential partitioning processes. Also reviewed is the behaviour of the elements in the ion exchange chromatography, precipitation, electrolysis from aqueous solutions and melts, and the distribution between molten salts and metals. Flowsheets of selected partitioning processes are shown and general aspects of the waste partitioning are shortly discussed. (orig.)

  1. Leaching properties of solidified TRU waste forms

    Safety analysis of waste forms requires an estimate of the ability of these forms to retain activity in the disposal environment. This program of leaching tests will determine the leaching properties of TRU contaminated incinerator ash waste forms using hydraulic cement, urea--formaldehyde, bitumen, and vinyl ester--styrene as solidification agents. Three types of leaching tests will be conducted, including both static and flow rate. Five generic groundwaters will be used. Equipment and procedures are described. Experiments have been conducted to determine plate out of 239Pu, counter efficiency, and stability of counting samples

  2. Lysimeter tests of SRP waste forms

    A field study, estimated to last 10 years, has been started to define leaching and migration rates of radionuclides from typical SRP buried wastes. The study utilizes 42 lysimeters (6-ft or 10-ft diameter by 10-ft deep) which have been charged with soil and waste to simulate burial ground conditions. Eight waste forms were selected for the study, which represent the bulk of the wastes generated at SRP. This report describes the lysimeter design, the physical and radiological characteristics of the wastes, and the experimental approach. Calculations have also been made which predict the migration of various radionuclides in the lysimeter soil. The calculations should provide guidance during the course of the study, and are the basis of recommendations made for collecting and interpreting data so that important parameters of migration can be evaluated

  3. Construction of solid waste form test facility

    The Solid Waste Form Test Facility (SWFTF) is now construction at DAEDUCK in Korea. In SWFTF, the characteristics of solidified waste products as radiological homogeneity, mechanical and thermal property, water resistance and lechability will be tested and evaluated to meet conditions for long-term storage or final disposal of wastes. The construction of solid waste form test facility has been started with finishing its design of a building and equipments in Sep. 1984, and now building construction is completed. Radioactive gas treatment system, extinguishers, cooling and heating system for the facility, electrical equipments, Master/Slave manipulator, power manipulator, lead glass and C.C.T.V. has also been installed. SWFTF will be established in the beginning of 1990's. At this report, radiation shielding door, nondestructive test of the wall, instrumentation system for the utility supply system and cell lighting system are described. (Author)

  4. Alternative Waste Forms for Electro-Chemical Salt Waste

    Crum, Jarrod V.; Sundaram, S. K.; Riley, Brian J.; Matyas, Josef; Arreguin, Shelly A.; Vienna, John D.

    2009-10-28

    This study was undertaken to examine alternate crystalline (ceramic/mineral) and glass waste forms for immobilizing spent salt from the Advanced Fuel Cycle Initiative (AFCI) electrochemical separations process. The AFCI is a program sponsored by U.S. Department of Energy (DOE) to develop and demonstrate a process for recycling spent nuclear fuel (SNF). The electrochemical process is a molten salt process for the reprocessing of spent nuclear fuel in an electrorefiner and generates spent salt that is contaminated with alkali, alkaline earths, and lanthanide fission products (FP) that must either be cleaned of fission products or eventually replaced with new salt to maintain separations efficiency. Currently, these spent salts are mixed with zeolite to form sodalite in a glass-bonded waste form. The focus of this study was to investigate alternate waste forms to immobilize spent salt. On a mole basis, the spent salt is dominated by alkali and Cl with minor amounts of alkaline earth and lanthanides. In the study reported here, we made an effort to explore glass systems that are more compatible with Cl and have not been previously considered for use as waste forms. In addition, alternate methods were explored with the hope of finding a way to produce a sodalite that is more accepting of as many FP present in the spent salt as possible. This study was done to investigate two different options: (1) alternate glass families that incorporate increased concentrations of Cl; and (2) alternate methods to produce a mineral waste form.

  5. Geochemistry of actinides. Application to the storage of high level radioactive wastes. Under the supervision of Mr Michel Treuil

    This collective research report first addresses the chemistry of actinides with a description of their atomic orbitals and the study of their behaviour in solution. The author addresses several aspects: historical overview on actinides, radioactivity, chemical reactions in aqueous solution, redox chemistry, speciation in solution with respect to water characteristics in deep storage conditions. The second part gathers several studies performed on a natural laboratory (the Oklo site in which nuclear reactions occurred about 2 billions years ago) and reports the modelling of radionuclide transfer within a geological system (the model is applied to the Oklo site). The third part addresses issues related to the nuclear fuel cycle, and the storage modes and materials envisaged and involved regarding the storage of high level radioactive wastes, notably in France

  6. Preparation techniques for ceramic waste form powder

    The electrometallurgical treatment of spent nuclear fuels result in a chloride waste salt requiring geologic disposal. Argonne National Laboratory (ANL) is developing ceramic waste forms which can incorporate this waste. Currently, zeolite- or sodalite-glass composites are produced by hot isostatic pressing (HIP) techniques. Powder preparations include dehydration of the raw zeolite powders, hot blending of these zeolite powders and secondary additives. Various approaches are being pursued to achieve adequate mixing, and the resulting powders have been HIPed and characterized for leach resistance, phase equilibria, and physical integrity

  7. Recent progress in actinide borate chemistry.

    Wang, Shuao; Alekseev, Evgeny V; Depmeier, Wulf; Albrecht-Schmitt, Thomas E

    2011-10-21

    The use of molten boric acid as a reactive flux for synthesizing actinide borates has been developed in the past two years providing access to a remarkable array of exotic materials with both unusual structures and unprecedented properties. [ThB(5)O(6)(OH)(6)][BO(OH)(2)]·2.5H(2)O possesses a cationic supertetrahedral structure and displays remarkable anion exchange properties with high selectivity for TcO(4)(-). Uranyl borates form noncentrosymmetric structures with extraordinarily rich topological relationships. Neptunium borates are often mixed-valent and yield rare examples of compounds with one metal in three different oxidation states. Plutonium borates display new coordination chemistry for trivalent actinides. Finally, americium borates show a dramatic departure from plutonium borates, and there are scant examples of families of actinides compounds that extend past plutonium to examine the bonding of later actinides. There are several grand challenges that this work addresses. The foremost of these challenges is the development of structure-property relationships in transuranium materials. A deep understanding of the materials chemistry of actinides will likely lead to the development of advanced waste forms for radionuclides present in nuclear waste that prevent their transport in the environment. This work may have also uncovered the solubility-limiting phases of actinides in some repositories, and allows for measurements on the stability of these materials. PMID:21915396

  8. CMP flowsheet development for the separation of actinides from ICPP sodium-bearing waste using centrifugal contactors

    Previous results of lab-scale batch contacts with sodium-bearing waste (SBW) simulant suggested a potential flowsheet for partitioning actinides using solvent extraction with dihexyl-N,N-diethylcarbamoylmethyl phosphonate (DHDECMP or simply CMP) as the extractant. The suggested baseline flowsheet includes: an extraction section to remove actinides from liquid SBW into the CMP solvent (0.75 M CMP, 1.0 M TBP in Isopar-L reg-sign); a thermally unstable complexant (TUCS) strip section to back-extract actinides; a sodium carbonate wash section for solvent cleanup; and a dilute HNO3 rinse section to re-acidify the solvent. The purpose of these studies was to test and develop a baseline CMP flowsheet for Idaho Chemical Processing Plant (ICPP) SBW under continuous, countercurrent conditions using centrifugal contactors. This flowsheet was tested in two experiments using the Centrifugal Contactor Mockup which consists of sixteen stages of 5.5 cm diameter centrifugal contactors (procured from Oak Ridge National Laboratory). All testing was performed using non-radioactive SBW simulant. Potential flowsheets were evaluated with regard to the behavior of the non-radioactive components potentially extracted by the CMP solvent. Specifically, the behavior of the matrix components, including Fe, Hg, and Zr, was studied. In addition, Nd was added to the SBW simulant as a surrogate for 241Am. In general, the behavior of the individual components closely paralleled that anticipated from batch testing. Based on the assumption that the behavior of Am will be very similar to the behavior of the Nd surrogate, eight extraction stages are more than sufficient to reduce the actinide content in the SBW to levels well below the NRC Class A LLW criteria of 10 nCi/g. Very little Fe or Zr were extracted from the SBW simulant, resulting in only 1% of the Fe and 4% of the Zr exiting in the high-activity waste (HAW) fraction

  9. Synthesis and characterization of novel lanthanide- and actinide-containing titanates and zircono-titanates; relevance to nuclear waste disposal

    Before experiments using actinide elements are performed, synthetic routes are tested using lanthanides of comparable ionic radii as surrogates. Compound and solid solution formation in several lanthanide-containing titanate and zircono-titanate systems have been established using X-ray diffraction (XRD) analysis, which helped to define interesting and novel experiments, some of which have been performed and are discussed, for selected actinide elements. The aqueous solubilities of several lanthanide- and actinide-containing compounds, representative of the systems studied, were tested in several leachants, including the WIPP open-quotes Aclose quotes brine, following modified Materials Characterization Center procedures (MCC-3). The WIPP open-quotes Aclose quotes brine is a synthetic substitute for that found in nature at the Waste Isolation Pilot Plant (WIPP) in New Mexico. The concentrations of cerium, used as a surrogate for plutonium, leached by the WIPP open-quotes Aclose quotes brine from all the cerium-containing compounds and solid solutions tested were below the Inductively Coupled Plasma (ICP) atomic emission spectrometry limit of detection (10 ppm) established for cerium in this brine. The concentrations of plutonium leached from the two plutonium-containing solid solutions were less than 1 ppm as determined by gross alpha counting and alpha pulse height analysis. Concentrations of strontium leached by the WIPP brine from stable strontium containing titanate compounds, studied as possible immobilizers of both 90Sr and actinide elements, were also quite low. These compound and solid solution formation investigations and the aqueous solubility studies suggest that the types of titanate and zircono-titanate compounds and solid solutions studied in this work appear to be useful as host matrices for nuclear waste immobilization

  10. Transmutations of nuclear waste. Progress report RAS programme 1995: Recycling and transmutation of actinides and fission products

    This report describes the progress of the Dutch RAS programme on 'Recycling and Transmutation of Actinides and Fission Products' over the year 1995, which is the second year of the 4-year programme 1994-1997. An extensive listing of reports and publications from 1991 to 1995 is given. Highlights in 1995 were: -The completion of the European Strategy Study on Nuclear Waste Transmutation as a result of which the understanding of transmutation of plutonium, minor actinides and long-lived fission products in thermal and fast reactors has been increased significantly. Important ECN contributions were given on Am, 99Tc and 129I transmutation options. Follow-up contracts have been obtained for the study of 100% MOX cores and accelerator-based transmutation. - Important progress in the evaluation of CANDU reactors for burning very large amounts of transuranium mixtures in inert matrices. - The first RAS irradiation experiment in the HFR, in which the transmutation of technetium and iodine was examined, has been completed and post-irradiation examination has been started. - A joint proposal of the EFTTRA cooperation for the 4th Framework Programme of the EU, to demonstrate the feasibility of the transmutation of americium in an inert matrix by an irradiation in the HFR, has been granted. - A bilateral contract with CEA has been signed to participate in the CAPRA programme, and the work in this field has been started. - The thesis work on Actinide Transmutation in Nuclear Reactor Systems was succesfully defended. New PhD studies on Pu burning in HTGR, on nuclear data for accelerator-based systems, and on the SLM-technique for separation of actinides were started. - A review study of the use of the thorium cycle as a means for nuclear waste reduction, has been completed. A follow-up of this work is embedded in an international project for the 4th Framework Programme of the EU. (orig./DG)

  11. Waste management analysis for the nuclear fuel cycle: actinide recovery from combustible waste, October 1977-March 1978

    Evaluation of the Ce(IV)-NHO3 system for recovery of actinides from incinerator ash is continuing. High-fired americium-traced plutonium oxide was completely solubilized in this system and recovery of actinides from incinerator ash was greater than or equal to 95%. Recovery of solubilized plutonium was done by solvent extraction using tributyl phosphate. Tervalent actinides will be recovered by a bidentate organophosphorus solvent extractant. The Ce(IV)-HNO3 system was compared with the F--HNO3 system now in common use. Advantages of the former include less equipment corrosion, no volatilization of silica, and better recovery of actinide in the initial contact. However, additional contacts do not significantly improve recovery (because silica is not solubilized), and the system requires a large liquid/solid ratio for efficient actinide recovery

  12. Reductive capacity measurement of waste forms for secondary radioactive wastes

    Um, Wooyong; Yang, Jung-Seok; Serne, R. Jeffrey; Westsik, Joseph H.

    2015-12-01

    The reductive capacities of dry ingredients and final solid waste forms were measured using both the Cr(VI) and Ce(IV) methods and the results were compared. Blast furnace slag (BFS), sodium sulfide, SnF2, and SnCl2 used as dry ingredients to make various waste forms showed significantly higher reductive capacities compared to other ingredients regardless of which method was used. Although the BFS exhibits appreciable reductive capacity, it requires greater amounts of time to fully react. In almost all cases, the Ce(IV) method yielded larger reductive capacity values than those from the Cr(VI) method and can be used as an upper bound for the reductive capacity of the dry ingredients and waste forms, because the Ce(IV) method subjects the solids to a strong acid (low pH) condition that dissolves much more of the solids. Because the Cr(VI) method relies on a neutral pH condition, the Cr(VI) method can be used to estimate primarily the waste form surface-related and readily dissolvable reductive capacity. However, the Cr(VI) method does not measure the total reductive capacity of the waste form, the long-term reductive capacity afforded by very slowly dissolving solids, or the reductive capacity present in the interior pores and internal locations of the solids.

  13. Reductive Capacity Measurement of Waste Forms for Secondary Radioactive Wastes

    Um, Wooyong; Yang, Jungseok; Serne, R. Jeffrey; Westsik, Joseph H.

    2015-09-28

    The reductive capacities of dry ingredients and final solid waste forms were measured using both the Cr(VI) and Ce(IV) methods and the results were compared. Blast furnace slag (BFS), sodium sulfide, SnF2, and SnCl2 used as dry ingredients to make various waste forms showed significantly higher reductive capacities compared to other ingredients regardless of which method was used. Although the BFS exhibits appreciable reductive capacity, it requires greater amounts of time to fully react. In almost all cases, the Ce(IV) method yielded larger reductive capacity values than those from the Cr(VI) method and can be used as an upper bound for the reductive capacity of the dry ingredients and waste forms, because the Ce(IV) method subjects the solids to a strong acid (low pH) condition that dissolves much more of the solids. Because the Cr(VI) method relies on a neutral pH condition, the Cr(VI) method can be used to estimate primarily the waste form surface-related and readily dissolvable reductive capacity. However, the Cr(VI) method does not measure the total reductive capacity of the waste form, the long-term reductive capacity afforded by very slowly dissolving solids, or the reductive capacity present in the interior pores and internal locations of the solids.

  14. Performance of monolithic concrete waste forms

    Liquid wastes can be made into concrete or cement waste form that can be poured into a concrete vault forming a monolith. The waste isolation performance of monolithic concrete waste forms or vaults is generally dominated by the influence of cracks through the structure. In relation to water flow rate and crack spacing, monolithic concrete vaults have three general regions of performance. At extremely low flow rates, release is strictly diffusionally limited. In most situations, flow rates will not be low enough to ensure diffusional release. At slightly greater flow rates (the magnitude of which is dependent upon the diffusion coefficients and crack spacing), release is controlled by the flow rate of water through cracks in the structure with release rate approximately proportional to Darcy flow. In this region, release is not sensitive to block size and the vault behaves as an equivalent porous medium from a mass transport perspective. At higher flow rates, release rate is controlled by diffusion out of intact blocks of waste form. In this situation the release rate is very sensitive to block size (crack spacing) but independent of flow. (author)

  15. Integral migration and source-term experiments on cement and bitumen waste forms

    This is the final report of a programme of research which formed a part of the CEC joint research project into radionuclide migration in the geosphere (MIRAGE). This study addressed the aspects of integral migration and source term. The integral migration experiment simulated, in the laboratory, the intrusion of water into the repository, the leaching of radionuclides from two intermediate-level waste-forms and the subsequent migration through the geosphere. The simulation consisted of a source of natural ground water which flowed over a sample of waste-form, at a controlled redox potential, and then through backfill and geological material packed in columns. The two waste forms used here were cemented waste from the WAK plant at Karlsruhe in the Federal Republic of Germany and bitumenized intermediate concentrates from the Marcoule plant in France. The soluble fission products such as caesium were rapidly released from the cemented waste but the actinides, and technetium in the reduced state, were retained in the waste-form. The released of all nuclides from the bitumenized waste was very low

  16. Review of glass ceramic waste forms

    Glass ceramics are being considered for the immobilization of nuclear wastes to obtain a waste form with improved properties relative to glasses. Improved impact resistance, decreased thermal expansion, and increased leach resistance are possible. In addition to improved properties, the spontaneous devitrification exhibited in some waste-containing glasses can be avoided by the controlled crystallization after melting in the glass-ceramic process. The majority of the glass-ceramic development for nuclear wastes has been conducted at the Hahn-Meitner Institute (HMI) in Germany. Two of their products, a celsian-based (BaAl3Si2O8) and a fresnoite-based (Ba2TiSi2O8) glass ceramic, have been studied at Pacific Northwest Laboratory (PNL). A basalt-based glass ceramic primarily containing diopsidic augite (CaMgSi2O6) has been developed at PNL. This glass ceramic is of interest since it would be in near equilibrium with a basalt repository. Studies at the Power Reactor and Nuclear Fuel Development Corporation (PNC) in Japan have favored a glass-ceramic product based upon diopside (CaMgSi2O6). Compositions, processing conditions, and product characterization of typical commercial and nuclear waste glass ceramics are discussed. In general, glass-ceramic waste forms can offer improved strength and decreased thermal expansion. Due to typcially large residual glass phases of up to 50%, there may be little improvement in leach resistance

  17. Characterization of radioactive waste forms. Volume 2

    This document is the second yearbook for Task 3 of the European Communities 1985-89 programme of research on radioactive waste management and disposal carried out by public organizations and private firms in the Community through cost-sharing contracts with the Commission of the European Communities. The report, in two volumes, describes progress made in 1987 within the field of Task 3: Testing and evaluation of conditioned waste and engineered barriers. The first volume of the report covers Item 3.1 Characterization of low and medium level radioactive waste forms and Item 3.5. Development of test methods for quality assurance. The second volume covers Item 3.2: High-level and alpha waste characterization and Item 3.3: Other engineered barriers. Item 3.4 on the round robin study will be treated in a separate report

  18. Characterization of radioactive waste forms. Volume 1

    This document is the second yearbook for Task 3 of the European Communities 1985-89 programme of research on radioactive waste management and disposal carried out by public organizations and private firms in the Community through costsharing contracts with the Commission of the European Communities. The report, in two volumes, describes progress made in 1987 within the field of Task 3: Testing and evaluation of conditioned waste and engineered barriers. The first volume of the report covers Item 3.1 Characterization of low and medium-level radioactive waste forms and Item 3.5 Development of test methods for quality assurance. The second volume covers Item 3.2: High-level and alpha waste characterization and Item 3.3: Other engineered barriers. Item 3.4 on the round robin study will be treated in a separate report

  19. WRAP 2A Waste Form Qualification Plan

    Burbank, D.A. Jr.

    1993-12-31

    WRAP Module 2A is a facility that will serve to treat retrieved, stored, and newly generated contact-handled mixed low level waste (MLLW) at the Department of Energy`s Hanford site near Richland, Washington. The treatment processes to be used are limited to non-thermal processes, defined as processes operating at a temperature less than 500{degree}F. In addition to waste pretreatment and conditioning processes including sorting, size reduction, and homogenization, the final treatment technologies will consist of immobilization, stabilization, and encapsulation to produce final waste forms that are suitable for disposal in compliance with all applicable regulatory requirements. The wide variety of chemical and physical characteristics exhibited by the WRAP 2A feed streams will necessitate the performance of a comprehensive waste form qualification (WFQ) testing program. The WFQ program will provide the technical basis supporting the process selection and will demonstrate that the selected treatment processes produce final waste forms that will meet all applicable regulatory requirements and performance specifications. This document describes the overall WRAP 2A WFQ program.

  20. WRAP 2A Waste Form Qualification Plan

    WRAP Module 2A is a facility that will serve to treat retrieved, stored, and newly generated contact-handled mixed low level waste (MLLW) at the Department of Energy's Hanford site near Richland, Washington. The treatment processes to be used are limited to non-thermal processes, defined as processes operating at a temperature less than 500 degree F. In addition to waste pretreatment and conditioning processes including sorting, size reduction, and homogenization, the final treatment technologies will consist of immobilization, stabilization, and encapsulation to produce final waste forms that are suitable for disposal in compliance with all applicable regulatory requirements. The wide variety of chemical and physical characteristics exhibited by the WRAP 2A feed streams will necessitate the performance of a comprehensive waste form qualification (WFQ) testing program. The WFQ program will provide the technical basis supporting the process selection and will demonstrate that the selected treatment processes produce final waste forms that will meet all applicable regulatory requirements and performance specifications. This document describes the overall WRAP 2A WFQ program

  1. The effects of actinide separation on the radiological consequences of disposal of high-level radioactive waste on the ocean bed

    One option in the management of high-level radioactive wastes is to separate the actinides prior to vitrification and disposal. This option is examined in the context of disposal of high-level wastes on the deep ocean bed. The initial quantity of waste corresponds to the generation of 1000 GW(e)y of nuclear energy, and the actinide-separation process is assumed to remove 99% of all elements of atomic number greater than that of actinium. The models used to describe the dispersion of activity from a single disposal site on the bed of the Atlantic Ocean represent both local dispersion and long-term mixing. Collective doses and doses to individuals are calculated for six potential pathways: ingestion of fish, crustacea, molluscs, plankton and seaweed, and external irradiation from contaminated beach sediments. The period from 400 to 1,000,000 years after disposal is considered. The potential radiological impact from disposal of high-level waste without separation of actinides on the ocean bed arises from the actinides; isotopes of americium, neptunium and plutonium give the highest doses. Actinide separation would reduce these doses in proportion to the effectiveness of the separation process, until doses become determined by fission products rather than actinides: the achievable dose reduction would be a factor of approximately a hundred, or less for certain pathways. This reduction applies only to doses to the public from waste disposal: no account was taken of doses arising from the separation process itself or from the management of the separated actinides. The results of the assessment are contrasted with those of similar studies based on toxicity indices. Major deficiencies are identified in the use of toxicity indices as a basis for decision-making. (author)

  2. Overview of actinide chemistry in the WIPP

    Borkowski, Marian [Los Alamos National Laboratory; Lucchini, Jean - Francois [Los Alamos National Laboratory; Richmann, Michael K [Los Alamos National Laboratory; Reed, Donald T [Los Alamos National Laboratory; Khaing, Hnin [Los Alamos National Laboratory; Swanson, Juliet [Los Alamos National Laboratory

    2009-01-01

    The year 2009 celebrates 10 years of safe operations at the Waste Isolation Pilot Plant (WIPP), the only nuclear waste repository designated to dispose defense-related transuranic (TRU) waste in the United States. Many elements contributed to the success of this one-of-the-kind facility. One of the most important of these is the chemistry of the actinides under WIPP repository conditions. A reliable understanding of the potential release of actinides from the site to the accessible environment is important to the WIPP performance assessment (PA). The environmental chemistry of the major actinides disposed at the WIPP continues to be investigated as part of the ongoing recertification efforts of the WIPP project. This presentation provides an overview of the actinide chemistry for the WIPP repository conditions. The WIPP is a salt-based repository; therefore, the inflow of brine into the repository is minimized, due to the natural tendency of excavated salt to re-seal. Reducing anoxic conditions are expected in WIPP because of microbial activity and metal corrosion processes that consume the oxygen initially present. Should brine be introduced through an intrusion scenario, these same processes will re-establish reducing conditions. In the case of an intrusion scenario involving brine, the solubilization of actinides in brine is considered as a potential source of release to the accessible environment. The following key factors establish the concentrations of dissolved actinides under subsurface conditions: (1) Redox chemistry - The solubility of reduced actinides (III and IV oxidation states) is known to be significantly lower than the oxidized forms (V and/or VI oxidation states). In this context, the reducing conditions in the WIPP and the strong coupling of the chemistry for reduced metals and microbiological processes with actinides are important. (2) Complexation - For the anoxic, reducing and mildly basic brine systems in the WIPP, the most important

  3. Lysimeter study of commercial reactor waste forms: waste form acquisition characterization and full-scale leaching

    This report describes work conducted at Brookhaven National Laboratory (BNL) as part of a joint program with Savannah River Laboratory. Typical full-scale (55-gallon drum size) waste forms were acquired by BNL from a boiling water reactor (BWR) and a pressurized water reactor (PWR). Liquid waste stream activity concentrations were analyzed by gamma spectroscopy. This information was used to determine the waste from activity inventory, providing the necessary source term for lysimeter and leaching experiments. Predominant radionuclides of interest include 60Co, 137Cs, 134Cs, and 54Mn. A full-scale leaching experiment was initiated by BNL encompassing four representative waste stream-solidification agent combinations. Waste streams tested include PWR evaporator concentrate (boric acid waste), BWR evaporator concentrate (sodium sulfate waste) and BWR evaporator concentrate plus ion exchange resins. Solidification agents include masonry cement, portland type III cement, and vinyl ester-styrene (Dow polymer). Analyses of leachates indicate measurable leach rates of 137Cs, 134Cs, and 60Co from both BWR and PWR cement waste forms. The leach rates for both cesium isotopes in cement are at least two orders of magnitude greater than those for cobalt. Leachates from the BWR Dow polymer waste form include the same isotopes present in cement leachates, with the addition of 54Mn. Cesium leach rates from the Dow polymer waste form are approximately one order of magnitude lower than from an equivalent cement waste form. The 60Co cumulative fraction release, however, is approximately three times greater for the Dow polymer waste form

  4. Microbial Transformations of TRU and Mixed Wastes: Actinide Speciation and Waste Volume Reduction

    were also prepared with 5 g bentonite per sample (at the time, a potential backfill material) and labeled BU (unamended), BUI (unamended/inoculated), BAI (amended/inoculated), and BAINO3 (amended/inoculated/excess nitrate). The samples were incubated at 30C, sampled periodically for gas production and aqueous chemical characteristics to quantify the rate and extent of microbial degradation of cellulose for WIPP Performance Assessment models. The studies at UNLV will evaluate the complexation of actinides (U,Pu) with the degraded material in both the solid and solution phase. The initial step in this experiment is the determination of the proton exchange capacity. The degraded cellulose is separated from the supernate brine solution prior to preparation of both phases. The cellulose is thoroughly washed with 0.1 M hydrochloric acid, rinsed with water and dried prior to analysis, insuring protonation and the removal of salt. The titrations are performed under argon atmosphere in a 50 mL jacketed titration vessel at room temperature with a magnetic stir bar to ensure mixture. Samples are analyzed by Epson 736GP Titrino system with a base titrant, 0.1000 +/- 0.0002 N sodium hydroxide (VWR). Between 0.2 and 0.8 grams of degraded cellulose are added to the titration vessel along with 10mL of DI water. Sample is stirred for 30min. prior to titration. The titrant is added in 0.05 mL increments every 5 mins. The pH titrations were performed in order to determine the proton exchange capacities of the degraded cellulose samples using the equation: PEC=[OH-]Veq/m where PEC is in eq/g, [OH-] is the concentration of hydroxide in mol/L, equivalence volume in L and m the mass of dried degraded cellulose in g. PEC values will be used for complexation studies with europium uranium and plutonium. Proton exchange capacities for degraded cellulose samples. Sample Avg PEC (meq/g) Standard deviation AIC 2.228E-01 0.0114 AINO3C 1.710E-01 0.0246 UC 1.824E-01 0.0323 UIC 2.132E-01 0.0450

  5. Dissolution of tailored ceramic nuclear waste forms

    Dissolution experiments on polyphase, high alumina tailored ceramic nuclear waste forms developed for the chemical immobilization of Savannah River Plant nuclear waste are described. Three forms of leach tests have been adopted; bulk samples conforming to the Materials Characterization Center Static Leach Test (MCC-1), a powdered sample leach test, and a leach test performed on transmission electron microscope thin foil samples. From analysis of these tests the crystalline phases that preferentially dissolve on leaching and the product phases formed are identified and related to the tailoring and processing schemes used in forming the ceramics. The thin foil sample leaching enables the role of intergranular amorphous phases as short-circuit leaching paths in polyphase ceramics to be investigated

  6. Mechanical environmental transport of actinides and ¹³⁷Cs from an arid radioactive waste disposal site.

    Snow, Mathew S; Clark, Sue B; Morrison, Samuel S; Watrous, Matthew G; Olson, John E; Snyder, Darin C

    2015-10-01

    Aeolian and pluvial processes represent important mechanisms for the movement of actinides and fission products at the Earth's surface. Soil samples taken in the early 1970's near a Department of Energy radioactive waste disposal site (the Subsurface Disposal Area, SDA, located in southeastern Idaho) provide a case study for studying the mechanisms and characteristics of environmental actinide and (137)Cs transport in an arid environment. Multi-component mixing models suggest actinide contamination within 2.5 km of the SDA can be described by mixing between 2 distinct SDA end members and regional nuclear weapons fallout. The absence of chemical fractionation between (241)Am and (239+240)Pu with depth for samples beyond the northeastern corner and lack of (241)Am in-growth over time (due to (241)Pu decay) suggest mechanical transport and mixing of discrete contaminated particles under arid conditions. Occasional samples northeast of the SDA (the direction of the prevailing winds) contain anomalously high concentrations of Pu with (240)Pu/(239)Pu isotopic ratios statistically identical to those in the northeastern corner. Taken together, these data suggest flooding resulted in mechanical transport of contaminated particles into the area between the SDA and a flood containment dike in the northeastern corner, following which subsequent contamination spreading in the northeastern direction resulted from wind transport of discrete particles. PMID:26107287

  7. Selective separation of actinides and long lived fission products from aged liquid wastes produced by the EUREX plant at Saluggia

    The chemical process for the selective separation of actinides and long lived fission products from aged MTR liquid wastes is described. To perform this selective separation, some chemical procedures such as precipitation and ion exchange, both in acidic and alkaline media, have been investigated, mainly at the laboratory scale, using simulated and traced waste solutions. To confirm the results obtained with simulated or traced solutions, additional tests with true MTR wastes are in progress in the analytical hot cell of ENEA EUREX pilot plant in Saluggia. With all these results, it is possible to perform a preliminary selection of the reference process. Further larger scale information will be available after experimental runs on a cold pilot plant, named SERSE, designed and built at Saluggia for engineering scale demonstration of the chemical separation process. This R and D work was performed and partially funded in the frame of the research programmes of the European Communities. (author)

  8. Alternative waste forms: a comparative study

    A characterization study utilizing comparative tests has been conducted to assess product inertness of alternative waste form materials, having evaluated at this point four basic product types: sintered ceramics, glass ceramics, glass and concrete. The seven specific waste form materials studied represent simulated nuclear waste loading of 5% to 100%, processed between room temperature and 12000C and subjected to characterization tests including phase analysis, microstructure, compression testing, volatility and leach testing. Significant conclusions based upon the results obtained to date are: sintered calcine waste form PW-9 does not retain Na, Mo and Cs when leached 900C and, in fact, does not remain a solid; glass and supercalcine are alike under both hydrous and hydrothermal leach conditions with glass exhibiting a greater retention of sodium and molybdenum, supercalcine having a greater retention of cesium, and both forms approximately equal in strontium retention; volatility measurements indicate that an order of magnitude decrease in volatility occurs when a calcine waste form is incorporated in a crystalline or glassy host; glass 76-68 is superior to supercalcine SPC-5B in retention of volatiles below 11000C because of the high release of Na from SPC-5B, however, as the temperature approaches or exceeds the glass melt temperature, volatile losses of the glass equal or exceed that of SPC-5B; glass 76-68 and supercalcine SPC-5B have high compressive strengths when compared to sintered PW-9 and cement products. This is apparently due to a stronger continuum bond resulting from a glassy matrix or crystalline ingrowth over a simple mechanical agglomeration of particles

  9. Development of a glass-encapsulated calcium phosphate wasteform for the immobilization of actinide and halide containing radioactive wastes from the pyrochemical reprocessing of plutonium metal

    Chloride-containing radioactive wastes are generated during the pyrochemical reprocessing of Pu metal. Immobilization of these wastes in borosilicate glass or Synroc-type ceramics is not viable due to the very low solubility of chlorides in these hosts. Alternative wasteforms, including zeolites and direct vitrification in phosphate glasses, were therefore studied. However, the preferred option was to immobilize the waste in calcium phosphate ceramics, forming a number of stable mineral phases including chlorapatite, chloride-substituted fluorapatite and spodiosite. The immobilization process developed in this study involves a solid state process in which waste and host powders are reacted in air at temperatures in the range of 700-800 deg. C. The ceramic products obtained by this process are non-hygroscopic free-flowing powders that require encapsulation in glass to produce a monolithic wasteform suitable for storage and ultimate disposal. A suitable relatively low melting temperature phosphate-based glass was identified. Durability trials of both the ceramic powder and sintered glass-ceramic hybrid wasteform indicate that both the halides and actinide surrogate ions are satisfactorily immobilized

  10. Comparative assessment of TRU waste forms and processes. Volume I. Waste form and process evaluations

    This study provides an assesses seven waste forms and eight processes for immobilizing transuranic (TRU) wastes. The waste forms considered are cast cement, cold-pressed cement, FUETAP (formed under elevated temperature and pressure) cement, borosilicate glass, aluminosilicate glass, basalt glass-ceramic, and cold-pressed and sintered silicate ceramic. The waste-immobilization processes considered are in-can glass melting, joule-heated glass melting, glass marble forming, cement casting, cement cold-pressing, FUETAP cement processing, ceramic cold-pressing and sintering, basalt glass-ceramic processing. Properties considered included gas generation, chemical durability, mechanical strength, thermal stability, and radiation stability. The ceramic products demonstrated the best properties, except for plutonium release during leaching. The glass and ceramic products had similar properties. The cement products generally had poorer properties than the other forms, except for plutonium release during leaching. Calculations of the Pu release indicated that the waste forms met the proposed NRC release rate limit of 1 part in 105 per year in most test conditions. The cast-cement process had the lowest processing cost, followed closely by the cold-pressed and FUETAP cement processes. Joule-heated glass melting had the lower cost of the glass processes. In-can melting in a high-quality canister had the highest cost, and cold-pressed and sintered ceramic the second highest. Labor and canister costs for in-can melting were identified. The major contributor to costs of disposing of TRU wastes in a defense waste repository is waste processing costs. Repository costs could become the dominant cost for disposing of TRU wastes in a commercial repository. It is recommended that cast and FUETAP cement and borosilicate glass waste-form systems be considered. 13 figures, 16 tables

  11. Long-term stability of high-level waste forms

    The long-term stability of HLW forms is reviewed with regard to temperature, irradiation and aqueous corrosion in a geological environment. The paper focuses on borosilicate glasses, but the radiation stability results are compared with some HLW ceramics. Thermal stability: most nuclear waste glass compositions have been adjusted to ensure a low final crystallized fraction. The crystallization of highly active Pamela glass samples was similar to that of nonradioactive glass. Radiation stability: No adverse effect of irradiation damage was found in glasses doped with short-lived actinides: volume changes were small, no significant change in the leach rate was observed, and the fracture toughness increased. For most ceramics investigated, volume changes of up to 9%, amorphization and higher leach rates were observed as a consequence of high α decay doses. For the KAB 78 ceramic, however, none of these effects were detected since the matrix was not subject to α recoil damage. Chemical stability: It has been demonstrated that alteration by water depends largely on the repository conditions. Most clay act as silica sinks, and increase the glass corrosion rate. It is possible, however, to specify realistic temperature, pressure and environmental conditions to ensure glass integrity for more than 10 000 years

  12. Effects of burn-up, recovery efficiency and waste form on the environmental impact of fusion-fission transmutation systems

    The effects of fuel cycle parameters on nuclear waste environmental impact are analyzed for an advanced system that includes a Fusion-Fission Hybrid reactor. The system aims at reduction of the long-term radiotoxicity of waste by transmuting highly radiotoxic transuranics. However, the radiological risk of the system is measured by annual doses to the public, which are controlled by reactor operations, fuel cycle processes, waste treatment processes, and design of geological repositories. In this study, the waste environmental impact for a fuel cycle with a Fusion-Fission transmutation is analyzed as a function of three different parameters: burn-up, recovery efficiency and waste form durability for two different geological repositories, one with low actinide solubility and the other with high solubility. It is found that burn-up and recovery efficiency effects on environmental impact strongly depend on repository conditions, while the most influential parameter is found to be the durability of the waste form. (author)

  13. Studies of waste form performance at Japan Atomic Energy Research Institute

    The JAERI studies on the properties of the glass and ceramic waste forms, which have been done in the last several years, are described briefly. For the long-term evaluation of glass waste form performance under repository condition, leachability has been studied from the standpoints of understanding alteration layers, the effects of groundwater and the effects of redox conditions using radioactive or non-radioactive glass samples. The studies revealed that (1) the reactions in the alteration layers, such as crystal growth, continue after the apparent release of elements from the glass almost ceases, (2) under somewhat reducing conditions, Fe dissolves easily into leachates, and the hydrated silicate surface layer tends to dissolve more easily with Fe present than in deionized water, (3) precipitation of PuO2·xH2O(am) controls the leaching of soluble species of Pu under both redox conditions, and the dominant soluble species is Pu(OH)40 under reducing condition. Ceramics are considered as the most promising materials for immobilizing the actinide-rich wastes arising from partitioning and transmutation processes because of their outstanding long-term durability. In the present study, a-decay damage effects on the density and leaching behavior of perovskite (one of three main minerals forming Synroc) were investigated by an accelerated experiment using the actinide doping technique. A decrease in density of Cm-doped perovskite reaches 1.3 % at a dose of 9 x 1017 α-decays··g-1. The leach rate of perovskite increases with an increase in accumulated a-decay dose. Zirconia- and alumina-based ceramics for incorporating actinides were also investigated by inactive laboratory tests with an emphasis on crystallographic phase stability and chemical durability. The yttria-stabilized zirconia is stable crystallographically over wide ranges of Ce and/or Nd content and has excellent chemical durability. (author)

  14. Studies of high-level waste form performance at Japan Atomic Energy Research Institute

    The JAERI studies on the properties of the glass and ceramic waste forms, which have been done in the last several years, are described briefly. For the long-term evaluation of glass waste form performance under repository condition, leachability has studied from the standpoints of understanding of alteration layers, effects of groundwater and effects of redox condition using the radioactive or non-radioactive glass samples. The studies revealed that (1) the reactions in the alteration layers, such as crystal growth, continue after the apparent release of elements from the glass almost ceases, (2) under somewhat reducing conditions, Fe dissolves easily into leachates, and hydrated silicate surface layer tends to dissolve more easily with Fe in reduced synthetic groundwater than in deionized water, (3) precipitation of PuO2·xH2O(am) is controlling the leaching of soluble species of Pu under both redox conditions, and the dominant soluble species is Pu(OH)40 under reducing condition. Ceramics are considered as most promising materials for the actinide-rich wastes arising from partitioning and transmutation processes because of their outstanding durability for long term. In the present study, α-decay damage effects on the density and leaching behavior of perovskite (1 of 3 main minerals forming Synroc) were investigated by an accelerated experiment using the actinide doping technique. A decrease in density of Cm-doped perovskite reaches 1.3% at a dose of 9x1017 α-decays·g-1. The leach rate of perovskite increases with an increase in accumulated α-decay doses. Application of zirconia- and alumina-based ceramics for incorporating actinides was also investigated by inactive laboratory tests with an emphasis on crystallographic phase stability and chemical durability. The yttria-stabilized zirconia is stable crystallographically in the wide ranges of Ce and/or Nd content and have excellent chemical durability. (author)

  15. Studies of high-level waste form performance at Japan Atomic Energy Research Institute

    Banba, Tsunetaka; Mitamura, Hisayoshi; Kuramoto, Kenichi; Kamizono, Hiroshi [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment; Inagaki, Yahohiro

    1998-02-01

    The JAERI studies on the properties of the glass and ceramic waste forms, which have been done in the last several years, are described briefly. For the long-term evaluation of glass waste form performance under repository condition, leachability has studied from the standpoints of understanding of alteration layers, effects of groundwater and effects of redox condition using the radioactive or non-radioactive glass samples. The studies revealed that (1) the reactions in the alteration layers, such as crystal growth, continue after the apparent release of elements from the glass almost ceases, (2) under somewhat reducing conditions, Fe dissolves easily into leachates, and hydrated silicate surface layer tends to dissolve more easily with Fe in reduced synthetic groundwater than in deionized water, (3) precipitation of PuO{sub 2}{center_dot}xH{sub 2}O(am) is controlling the leaching of soluble species of Pu under both redox conditions, and the dominant soluble species is Pu(OH){sub 4}{sup 0} under reducing condition. Ceramics are considered as most promising materials for the actinide-rich wastes arising from partitioning and transmutation processes because of their outstanding durability for long term. In the present study, {alpha}-decay damage effects on the density and leaching behavior of perovskite (1 of 3 main minerals forming Synroc) were investigated by an accelerated experiment using the actinide doping technique. A decrease in density of Cm-doped perovskite reaches 1.3% at a dose of 9x10{sup 17} {alpha}-decays{center_dot}g{sup -1}. The leach rate of perovskite increases with an increase in accumulated {alpha}-decay doses. Application of zirconia- and alumina-based ceramics for incorporating actinides was also investigated by inactive laboratory tests with an emphasis on crystallographic phase stability and chemical durability. The yttria-stabilized zirconia is stable crystallographically in the wide ranges of Ce and/or Nd content and have excellent

  16. Actinide phosphonate complexes in aqueous solutions

    Complexes formed by actinides with carboxylic acids, polycarboxylic acids, and aminopolycarboxylic acids play a central role in both the basic and process chemistry of the actinides. Recent studies of f-element complexes with phosphonic acid ligands indicate that new ligands incorporating doubly ionizable phosphonate groups (-PO3H2) have many properties which are unique chemically, and promise more efficient separation processes for waste cleanup and environmental restoration. Simple diphosphonate ligands form much stronger complexes than isostructural carboxylates, often exhibiting higher solubility as well. In this manuscript recent studies of the thermodynamics and kinetics of f-element complexation by 1,1 and 1,2 diphosphonic acid ligands are described

  17. I-NERI-2007-004-K, DEVELOPMENT AND CHARACTERIZATION OF NEW HIGH-LEVEL WASTE FORMS FOR ACHIEVING WASTE MINIMIZATION FROM PYROPROCESSING

    S.M. Frank

    2011-09-01

    Work describe in this report represents the final year activities for the 3-year International Nuclear Energy Research Initiative (I-NERI) project: Development and Characterization of New High-Level Waste Forms for Achieving Waste Minimization from Pyroprocessing. Used electrorefiner salt that contained actinide chlorides and was highly loaded with surrogate fission products was processed into three candidate waste forms. The first waste form, a high-loaded ceramic waste form is a variant to the CWF produced during the treatment of Experimental Breeder Reactor-II used fuel at the Idaho National Laboratory (INL). The two other waste forms were developed by researchers at the Korean Atomic Energy Research Institute (KAERI). These materials are based on a silica-alumina-phosphate matrix and a zinc/titanium oxide matrix. The proposed waste forms, and the processes to fabricate them, were designed to immobilize spent electrorefiner chloride salts containing alkali, alkaline earth, lanthanide, and halide fission products that accumulate in the salt during the processing of used nuclear fuel. This aspect of the I-NERI project was to demonstrate 'hot cell' fabrication and characterization of the proposed waste forms. The outline of the report includes the processing of the spent electrorefiner salt and the fabrication of each of the three waste forms. Also described is the characterization of the waste forms, and chemical durability testing of the material. While waste form fabrication and sample preparation for characterization must be accomplished in a radiological hot cell facility due to hazardous radioactivity levels, smaller quantities of each waste form were removed from the hot cell to perform various analyses. Characterization included density measurement, elemental analysis, x-ray diffraction, scanning electron microscopy and the Product Consistency Test, which is a leaching method to measure chemical durability. Favorable results from this

  18. Waste Form Features, Events, and Processes

    The purpose of this report is to evaluate and document the inclusion or exclusion of the waste form features, events and processes (FEPs) with respect to modeling used to support the Total System Performance Assessment for License Application (TSPA-LA). A screening decision, either Included or Excluded, is given for each FEP along with the technical bases for screening decisions. This information is required by the Nuclear Regulatory Commission (NRC) in 10 CFR 63.114 (d, e, and f) [DIRS 156605]. The FEPs addressed in this report deal with the issues related to the degradation and potential failure of the waste form and the migration of the waste form colloids. For included FEPs, this analysis summarizes the implementation of the FEP in TSPA-LA, (i.e., how the FEP is included). For excluded FEPs, this analysis provides the technical bases for exclusion from TSPA-LA (i.e., why the FEP is excluded). This revision addresses the TSPA-LA FEP list (DTN: MO0407SEPFEPLA.000 [DIRS 170760]). The primary purpose of this report is to identify and document the analyses and resolution of the features, events, and processes (FEPs) associated with the waste form performance in the repository. Forty FEPs were identified that are associated with the waste form performance. This report has been prepared to document the screening methodology used in the process of FEP inclusion and exclusion. The analyses documented in this report are for the license application (LA) base case design (BSC 2004 [DIRS 168489]). In this design, a drip shield is placed over the waste package and no backfill is placed over the drip shield (BSC 2004 [DIRS 168489]). Each FEP may include one or more specific issues that are collectively described by a FEP name and a FEP description. The FEP description may encompass a single feature, process or event, or a few closely related or coupled processes if the entire FEP can be addressed by a single specific screening argument or TSPA-LA disposition. The FEPs are

  19. Waste Form Features, Events, and Processes

    R. Schreiner

    2004-10-27

    The purpose of this report is to evaluate and document the inclusion or exclusion of the waste form features, events and processes (FEPs) with respect to modeling used to support the Total System Performance Assessment for License Application (TSPA-LA). A screening decision, either Included or Excluded, is given for each FEP along with the technical bases for screening decisions. This information is required by the Nuclear Regulatory Commission (NRC) in 10 CFR 63.114 (d, e, and f) [DIRS 156605]. The FEPs addressed in this report deal with the issues related to the degradation and potential failure of the waste form and the migration of the waste form colloids. For included FEPs, this analysis summarizes the implementation of the FEP in TSPA-LA, (i.e., how the FEP is included). For excluded FEPs, this analysis provides the technical bases for exclusion from TSPA-LA (i.e., why the FEP is excluded). This revision addresses the TSPA-LA FEP list (DTN: MO0407SEPFEPLA.000 [DIRS 170760]). The primary purpose of this report is to identify and document the analyses and resolution of the features, events, and processes (FEPs) associated with the waste form performance in the repository. Forty FEPs were identified that are associated with the waste form performance. This report has been prepared to document the screening methodology used in the process of FEP inclusion and exclusion. The analyses documented in this report are for the license application (LA) base case design (BSC 2004 [DIRS 168489]). In this design, a drip shield is placed over the waste package and no backfill is placed over the drip shield (BSC 2004 [DIRS 168489]). Each FEP may include one or more specific issues that are collectively described by a FEP name and a FEP description. The FEP description may encompass a single feature, process or event, or a few closely related or coupled processes if the entire FEP can be addressed by a single specific screening argument or TSPA-LA disposition. The FEPs are

  20. Chemical aspects of incinerating highly chlorinated and actinide α contaminated organic waste: application to the Iris process

    A fraction of the waste produced by nuclear activities is combustible, and thus suitable for incineration to produce gases, ash and fines. A typical composition representative of actual organic waste mixtures was defined for the purpose of investigating possible heat treatment processes; the composition is identified according to components Table 1 and elements Table II. The high polyvinyl chloride (PVC) content is responsible for the high chlorine potential in the process equipment. The quantity and quality of the resulting solid residue depends entirely on the inorganic load of the organic waste, whose behavior is entirely conditioned by the process conditions. For example, pure polyethylene is totally converted to gases (water and carbon dioxide), while the composition shown in Table II produces a range of oxides and chlorides. The high chlorine content results in partial chlorination of the inorganic compounds, but can also lead to interactions with the process equipment. The temperature dependent variation of the chlorination equilibrium constants of various metals clearly shows that all the elements of technological alloys may be subject to active corrosion by hydrochloric acid. However, the corresponding oxides-notably alumina-are much less sensitive to corrosion; aluminum-based alloys are therefore preferred for incinerator construction and to limit corrosion by hydrochloric acid. Thermodynamic and kinetic studies led to the development of the IRIS three-step process. Gas emissions occurring during processing of solid materials are completely oxidized in the after-burning step at 1100 deg C, and are then ducted to a HERA filtration system capable of retaining all the actinide α radionuclides. Although corrosion-related problems are attenuated in the two-step process chlorine can combine with the inorganic waste material to form chlorides with potentially damaging effects on the system; this is the case for zinc chloride and for volatile chlorides in

  1. Actinide environmental chemistry

    In order to predict release and transport rates, as well as design cleanup and containment methods, it is essential to understand the chemical reactions and forms of the actinides under aqueous environmental conditions. Four important processes that can occur with the actinide cations are: precipitation, complexation, sorption and colloid formation. Precipitation of a solid phase will limit the amount of actinide in solution near the solid phase and have a retarding effect on release and transport rates. Complexation increases the amount of actinide in solution and tends to increase release and migration rates. Actinides can sorb on to mineral or rock surfaces which tends to retard migration. Actinide ions can form or become associated with colloidal sized particles which can, depending on the nature of the colloid and the solution conditions, enhance or retard migration of the actinide. The degree to which these four processes progress is strongly dependent on the oxidation state of the actinide and tends to be similar for actinides in the same oxidation state. In order to obtain information on the speciation of actinides in solution, i.e., oxidation state, complexation form, dissolved or colloidal forms, the use of absorption spectroscopy has become a method of choice. The advent of the ultrasensitive, laser induced photothermal and fluorescence spectroscopies has made possible the detection and study of actinide ions at the parts per billion level. With the availability of third generation synchrotrons and the development of new fluorescence detectors, X-ray absorption spectroscopy (XAS) is becoming a powerful technique to study the speciation of actinides in the environment, particularly for reactions at the solid/solution interfaces. (orig.)

  2. Actinide partitioning by TODGA hollow fiber supported liquid membrane: a cold test with simulated high level waste

    Transport behaviour of lanthanides from PHWR-Simulated High Level Waste (SHLW) was investigated using hollow fibre supported liquid membrane (HFSLM) containing 0.1M TODGA (N,N,N',N'-tetraoctyl diglycolamide) + 0.5M DHOA (N,N-dihexyl octanamide) as the carrier. The transport studies were conducted on 20 litres scale as a cold test with PHWR-SHLW. All the lanthanides could be quantitatively transported into the strip phase in 18hrs. None of the other elements were transported except small quantities of Sr and Mo. The system showed reasonably good stability studied up to 72 hrs of continuous operation. The results suggested the possible application of TODGA-HFSLM system for the recovery of minor actinides from high level wastes. (author)

  3. Alternative Electrochemical Salt Waste Forms, Summary of FY11-FY12 Results

    Riley, Brian J.; Mccloy, John S.; Crum, Jarrod V.; Lepry, William C.; Rodriguez, Carmen P.; Windisch, Charles F.; Matyas, Josef; Westman, Matthew P.; Rieck, Bennett T.; Lang, Jesse B.; Olszta, Matthew J.; Pierce, David A.

    2014-03-26

    The Fuel Cycle Research and Development Program, sponsored by the U.S. Department of Energy Office of Nuclear Energy, is currently investigating alternative waste forms for wastes generated from nuclear fuel processing. One such waste results from an electrochemical separations process, called the “Echem” process. The Echem process utilizes a molten KCl-LiCl salt to dissolve the fuel. This process results in a spent salt containing alkali, alkaline earth, lanthanide halides and small quantities of actinide halides, where the primary halide is chloride with a minor iodide fraction. Pacific Northwest National Laboratory (PNNL) is concurrently investigating two candidate waste forms for the Echem spent-salt: high-halide minerals (i.e., sodalite and cancrinite) and tellurite (TeO2)-based glasses. Both of these candidates showed promise in fiscal year (FY) 2009 and FY2010 with a simplified nonradioactive simulant of the Echem waste. Further testing was performed on these waste forms in FY2011 and FY2012 to assess the possibility of their use in a sustainable fuel cycle. This report summarizes the combined results from FY2011 and FY2012 efforts.

  4. DSNF and other waste form degradation abstraction

    Thornton, Thomas A.

    2000-12-20

    The purpose of this analysis/model report (AMR) is to select and/or abstract conservative degradation models for DOE-(US. Department of Energy) owned spent nuclear fuel (DSNF) and the immobilized ceramic plutonium (Pu) disposition waste forms for application in the proposed monitored geologic repository (MGR) postclosure Total System Performance Assessment (TSPA). Application of the degradation models abstracted herein for purposes other than TSPA should take into consideration the fact that they are, in general, very conservative. Using these models, the forward reaction rate for the mobilization of radionuclides, as solutes or colloids, away from the waste fondwater interface by contact with repository groundwater can then be calculated. This forward reaction rate generally consists of the dissolution reaction at the surface of spent nuclear fuel (SNF) in contact with water, but the degradation models, in some cases, may also include and account for the physical disintegration of the SNF matrix. The models do not, however, account for retardation, precipitation, or inhibition of the migration of the mobilized radionuclides in the engineered barrier system (EBS). These models are based on the assumption that all components of the DSNF waste form are released congruently with the degradation of the matrix.

  5. Synthesis of Waste Form in the Gd-Fe-Al-Ni-Mn-Cr-O System

    Poly-phase waste form which was the mixture of Gd3Fe2Al3O12 and (NixMn1-x)(FeyCr1-y)2O4 was synthesized. Also, we are intended to examine phase relation and physicochemical properties of coexisted phases in the compositions and to confirm accommodation relation of elements and phases. Two types of phase series were observed: Garnet-perovskite-spinel and Garnet-spinel. The compositions of garnets and spinels were nonstoichiometric, and especially, this poly-phase ceramics may be in a good waste form. The excessive Gd in garnets indicated the immobilization of higher content of actinides. The nonstoichiometric compositions of garnet and spinel were attributed to the formation of perovskite in that perovskite contained Gd, Fe and Al from garnet and Cr from spinel. (authors)

  6. Research in actinide chemistry

    This research studies the behavior of the actinide elements in aqueous solution. The high radioactivity of the transuranium actinides limits the concentrations which can be studied and, consequently, limits the experimental techniques. However, oxidation state analogs (trivalent lanthanides, tetravalent thorium, and hexavalent uranium) do not suffer from these limitations. Behavior of actinides in the environment are a major USDOE concern, whether in connection with long-term releases from a repository, releases from stored defense wastes or accidental releases in reprocessing, etc. Principal goal of our research was expand the thermodynamic data base on complexation of actinides by natural ligands (e.g., OH-, CO32-, PO43-, humates). The research undertakes fundamental studies of actinide complexes which can increase understanding of the environmental behavior of these elements

  7. Review of radiation effects in solid-nuclear-waste forms

    Radiation effects on the stability of high-level nuclear waste (HLW) forms are an important consideration in the development of technology to immobilize high-level radioactive waste because such effects may significantly affect the containment of the radioactive waste. Since the required containment times are long (103 to 106 years), an understanding of the long-term cumulative effects of radiation damage on the waste forms is essential. Radiation damage of nuclear waste forms can result in changes in volume, leach rate, stored energy, structure/microstructure, and mechanical properties. Any one or combination of these changes might significantly affect the long-term stability of the nuclear waste forms. This report defines the general radiation damage problem in nuclear waste forms, describes the simulation techniques currently available for accelerated testing of nuclear waste forms, and reviews the available data on radiation effects in both glass and ceramic (primarily crystalline) waste forms. 76 references

  8. Review of radiation effects in solid-nuclear-waste forms

    Weber, W.J.

    1981-09-01

    Radiation effects on the stability of high-level nuclear waste (HLW) forms are an important consideration in the development of technology to immobilize high-level radioactive waste because such effects may significantly affect the containment of the radioactive waste. Since the required containment times are long (10/sup 3/ to 10/sup 6/ years), an understanding of the long-term cumulative effects of radiation damage on the waste forms is essential. Radiation damage of nuclear waste forms can result in changes in volume, leach rate, stored energy, structure/microstructure, and mechanical properties. Any one or combination of these changes might significantly affect the long-term stability of the nuclear waste forms. This report defines the general radiation damage problem in nuclear waste forms, describes the simulation techniques currently available for accelerated testing of nuclear waste forms, and reviews the available data on radiation effects in both glass and ceramic (primarily crystalline) waste forms. 76 references.

  9. Safeguards and retrievability from waste forms

    Danker, W.

    1996-05-01

    This report describes issues discussed at a session from the PLutonium Stabilization and Immobilization Workshop related to safeguards and retrievability from waste forms. Throughout the discussion, the group probed the goals of disposition efforts, particularly an understanding of the {open_quotes}spent fuel standard{close_quotes}, since the disposition material form derives from these goals. The group felt strongly that not only the disposition goals but safeguards to meet these goals could affect the material form. Accordingly, the Department was encouraged to explore and apply safeguards as early in the implementation process as possible. It was emphasized that this was particularly true for any planned use of existing facilities. It is much easier to build safeguards approaches into the development of new facilities, than to backfit existing facilities. Accordingly, special safeguards challenges are likely to be encountered, given the cost and schedule advantages offered by use of existing facilities.

  10. Evaluation of extractants and chelating resins in polishing actinide-contaminated waste streams

    At the Los Alamos National Laboratory Plutonium Facility, anion exchange is used for recovering plutonium from nitric acid solutions. Although this approach recovers >99%, the trace amounts of plutonium and other actinides remaining in the effluent require additional processing. We are doing research to develop a secondary unit operation that can directly polish the effluent so that actinide levels are reduced to below the maximum allowed for facility discharge. We selected solvent extraction, the only unit operation that can meet the stringent process requirements imposed; several carbonyl and phosphoryl extractants were evaluated and their performance characterized. We also investigated various engineering approaches for solvent extraction; the most promising was a chelating resin loaded with extractant. Our research now focuses on the synthesis of malonamides, and our goal is to bond these extractants to a resin matrix. 7 refs., 12 figs., 1 tab

  11. Evaluation and testing of sequestering agents for the removal of actinides from waste streams

    Hoffman, D.C.; Romanovski, V.V.; Veeck, A.C. [Lawrence Livermore National Lab., CA (United States)] [and others

    1997-10-01

    The purpose of this project is to evaluate and test the complexing ability of a variety of promising new complexing agents synthesized by Professor Kenneth Raymond`s group at the University of California, Berkeley (ESP-CP TTP Number SF16C311). Some of these derivatives have already shown the potential for selectivity binding Pu(IV) in a wide range of solutions in the presence of other metals. Professor Raymond`s group uses molecular modeling to design and synthesize ligands based on modification of natural siderophores, or their analogs, for chelation of actinides. The ligands are then modified for use as liquid/liquid and solid/liquid extractants. The authors` group at the Glenn T. Seaborg Institute for Transactinium Science (ITS) at Lawrence Livermore National Laboratory determines the complex formation constants between the ligands and actinide ions, the capacity and time dependence for uptake on the resins, and the effect of other metal ions and pH.

  12. DuraLith Alkali-Aluminosilicate Geopolymer Waste Form Testing for Hanford Secondary Waste

    The primary objective of the work reported here was to develop additional information regarding the DuraLith alkali aluminosilicate geopolymer as a waste form for liquid secondary waste to support selection of a final waste form for the Hanford Tank Waste Treatment and Immobilization Plant secondary liquid wastes to be disposed in the Integrated Disposal Facility on the Hanford Site. Testing focused on optimizing waste loading, improving waste form performance, and evaluating the robustness of the waste form with respect to waste variability.

  13. DuraLith Alkali-Aluminosilicate Geopolymer Waste Form Testing for Hanford Secondary Waste

    Gong, W. L.; Lutz, Werner; Pegg, Ian L.

    2011-07-21

    The primary objective of the work reported here was to develop additional information regarding the DuraLith alkali aluminosilicate geopolymer as a waste form for liquid secondary waste to support selection of a final waste form for the Hanford Tank Waste Treatment and Immobilization Plant secondary liquid wastes to be disposed in the Integrated Disposal Facility on the Hanford Site. Testing focused on optimizing waste loading, improving waste form performance, and evaluating the robustness of the waste form with respect to waste variability.

  14. Annual report Development and characterization of solidified forms for high-level wastes: 1978.

    Ross, W.A.; Mendel, J.E.

    1979-12-01

    Development and characterization of solidified high-level waste forms are directed at determining both process properties and long-term behaviors of various solidified high-level waste forms in aqueous, thermal, and radiation environments. Waste glass properties measured as a function of composition were melt viscosity, melt electrical conductivity, devitrification, and chemical durability. The alkali metals were found to have the greatest effect upon glass properties. Titanium caused a slight decrease in viscosity and a significant increase in chemical durability in acidic solutions (pH-4). Aluminum, nickel and iron were all found to increase the formation of nickel-ferrite spinel crystals in the glass. Four multibarrier advanced waste forms were produced on a one-liter scale with simulated waste and characterized. Glass marbles encapsulated in a vacuum-cast lead alloy provided improved inertness with a minimal increase in technological complexity. Supercalcine spheres exhibited excellent inertness when coated with pyrolytic carbon and alumina and put in a metal matrix, but the processing requirements are quite complex. Tests on simulated and actual high-level waste glasses continue to suggest that thermal devitrification has a relatively small effect upon mechanical and chemical durabilities. Tests on the effects radiation has upon waste forms also continue to show changes to be relatively insignificant. Effects caused by decay of actinides can be estimated to saturate at near 10/sup 19/ alpha-events/cm/sup 3/ in homogeneous solids. Actually, in solidified waste forms the effects are usually observed around certain crystals as radiation causes amorphization and swelling of th crystals.

  15. Development and characterization of solidified forms for high-level wastes: 1978. Annual report

    Development and characterization of solidified high-level waste forms are directed at determining both process properties and long-term behaviors of various solidified high-level waste forms in aqueous, thermal, and radiation environments. Waste glass properties measured as a function of composition were melt viscosity, melt electrical conductivity, devitrification, and chemical durability. The alkali metals were found to have the greatest effect upon glass properties. Titanium caused a slight decrease in viscosity and a significant increase in chemical durability in acidic solutions (pH-4). Aluminum, nickel and iron were all found to increase the formation of nickel-ferrite spinel crystals in the glass. Four multibarrier advanced waste forms were produced on a one-liter scale with simulated waste and characterized. Glass marbles encapsulated in a vacuum-cast lead alloy provided improved inertness with a minimal increase in technological complexity. Supercalcine spheres exhibited excellent inertness when coated with pyrolytic carbon and alumina and put in a metal matrix, but the processing requirements are quite complex. Tests on simulated and actual high-level waste glasses continue to suggest that thermal devitrification has a relatively small effect upon mechanical and chemical durabilities. Tests on the effects radiation has upon waste forms also continue to show changes to be relatively insignificant. Effects caused by decay of actinides can be estimated to saturate at near 1019 alpha-events/cm3 in homogeneous solids. Actually, in solidified waste forms the effects are usually observed around certain crystals as radiation causes amorphization and swelling of th crystals

  16. Evaluation of a novel solid phase extraction composite for the removal of actinides from acidic nuclear waste solutions

    Tranter, T. J.; Mann, N. R.; Todd, T. A.; Šebesta, F.

    2003-01-01

    A novel approach for preparing granular solid phase extractants (SPE) for the separation of actinides has been developed, wherein the extractant is directly immobilised in an inert matrix. This allows substantially higher extractant loading in the SPE material than for conventional extraction chromatography resins. This approach utilises polyacrylonitrile (PAN) as the inert matrix material. The well-known actinide extractant octyl (phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO) has been impregnated within PAN granules at extractant loadings from 20 to 33 wt. % CMPO. The porosity of the PAN matrix allows the active material to have rapid and complete access to the solution containing the target contaminants, resulting in improved kinetics and higher sorption capacities. The new CMPO-PAN SPE material was prepared in a batch process. Equilibrium batch contact tests were then performed with this material to determine the efficacy for removing plutonium and uranium from acid solutions as well as simulated solutions of tank waste currently stored at the Idaho National Engineering and Environmental Laboratory (INEEL). The potential interference of non-target metals was also investigated. The equilibrium behaviour of the new composite material will be discussed.

  17. Evaluation of a novel solid phase extraction composite for the removal of actinides from acidic nuclear waste solutions

    A novel approach for preparing granular solid phase extractants (SPE) for the separation of actinides has been developed, wherein the extractant is directly immobilised in an inert matrix. This allows substantially higher extractant loading in the SPE material than for conventional extraction chromatography resins. This approach utilises polyacrylonitrile (PAN) as the inert matrix material. The well-known actinide extractant octyl (phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO) has been impregnated within PAN granules at extractant loadings from 20 to 33 wt. % CMPO. The porosity of the PAN matrix allows the active material to have rapid and complete access to the solution containing the target contaminants, resulting in improved kinetics and higher sorption capacities. The new CMPO-PAN SPE material was prepared in a batch process. Equilibrium batch contact tests were then performed with this material to determine the efficacy for removing plutonium and uranium from acid solutions as well as simulated solutions of tank waste currently stored at the Idaho National Engineering and Environmental Laboratory (INEEL). The potential interference of non-target metals was also investigated. The equilibrium behaviour of the new composite material will be discussed. (author)

  18. Decay calculations on medium-level and actinide-containing wastes from the LWR fuel cycle. Pt. 2

    1. The radiotoxicity index as inherent property of the radionuclide inventory was calculated for medium-level and actinide-containing wastes. The calculations were based on the annual limits of intake of the German Radiation Protection Ordinance as well as the new values of annual limits of intake from ICRP-30. The latter imply a higher rating of the toxicity of transuranium nuclides and a lower rating of Sr-90, Tc-99, and Ra-226. Thus, the annual radiotoxicity index is controlled by the transuranics after 10 to 100 years. 2. From the comparison of the radiotoxicity index of conditional and packed wastes with the same volume of uranium ore, it was evaluated that the relative radiotoxicity of the medium-level wastes decreases below the level of pitchblende after less than 100 years and below a 3% uranium ore after less than 2000 of decay. However, based on ICRP-30, the relative radiotoxicity index decreases below the level of pitchblende after 1000 years and decays to the level of the 3% uranium ore at about 105 years. 3. The comparison of the radiotoxicity concentration of the total disposal layer with a uranium ore deposit shows that the radiotoxicity concentration based on ICRP-30 of the self-heating wastes placed in single boreholes decays within 2000 years (high level waste within 3000 years) below the level of a uranium ore deposit of 0.2% uranium. The radiotoxicity concentration of the medium-level process waste and the alpha-waste disposed off in disposal chambers decreases to the level of a uranium ore deposit with 0.4 to 6% uranium after about 104 years, and 1% after about 105 years. (orig./HP)

  19. Lessons Learned from Characterization, Performance Assessment, and EPA Regulatory Review of the 1996 Actinide Source Term for the Waste Isolation Pilot Plant

    The Waste Isolation Pilot Plant (WIPP) is a US Department of Energy (DOE) facility for the permanent disposal of transuranic waste from defense activities. In 1996, the DOE submitted the Title 40 CFR Part 191 Compliance Certification Application for the Waste Isolation Pilot Plant (CCA) to the US Environmental Protection Agency (EPA). The CCA included a probabilistic performance assessment (PA) conducted by Sandia National Laboratories to establish compliance with the quantitative release limits defined in 40 CFR 191.13. An experimental program to collect data relevant to the actinide source term began around 1989, which eventually supported the 1996 CCA PA actinide source term model. The actinide source term provided an estimate of mobile dissolved and colloidal Pu, Am, U, Th, and Np concentrations in their stable oxidation states, and accounted for effects of uncertainty in the chemistry of brines in waste disposal areas. The experimental program and the actinide source term included in the CCA PA underwent EPA review lasting more than 1 year. Experiments were initially conducted to develop data relevant to the wide range of potential future conditions in waste disposal areas. Interim, preliminary performance assessments and actinide source term models provided insight allowing refinement of experiments and models. Expert peer review provided additional feedback and confidence in the evolving experimental program. By 1995, the chemical database and PA predictions of WIPP performance were considered reliable enough to support the decision to add an MgO backfill to waste rooms to control chemical conditions and reduce uncertainty in actinide concentrations, especially for Pu and Am. Important lessons learned through the characterization, PA modeling, and regulatory review of the actinide source term are (1) experimental characterization and PA should evolve together, with neither activity completely dominating the other, (2) the understanding of physical processes

  20. Stability testing of low-level waste forms

    The NRC Technical Position on Waste Form identifies methods for thermal cycle testing and biodegradation testing of low-level waste forms. These tests were carried out on low-level waste forms to establish whether the tests are reasonable and can be achieved. The thermal-cycle test is believed adequate for demonstrating the thermal stability of solidified waste forms. The biodegradation tests are sufficient for distinguishing materials that are susceptible to biodegradation. However, failure of either of these tests should not be regarded of itself as an indication that the waste form will biodegrade to an extent that the form does not meet the stability requirements of 10 CFR Part 61

  1. NDA issues with RFETS vitrified waste forms

    Hurd, J.; Veazey, G.

    1998-12-31

    A study was conducted at Los Alamos National Laboratory (LANL) for the purpose of determining the feasibility of using a segmented gamma scanner (SGS) to accurately perform non-destructive analysis (NDA) on certain Rocky Flats Environmental Technology Site (RFETS) vitrified waste samples. This study was performed on a full-scale vitrified ash sample prepared at LANL according to a procedure similar to that anticipated to be used at RFETS. This sample was composed of a borosilicate-based glass frit, blended with ash to produce a Pu content of {approximately}1 wt %. The glass frit was taken to a degree of melting necessary to achieve a full encapsulation of the ash material. The NDA study performed on this sample showed that SGSs with either {1/2}- or 2-inch collimation can achieve an accuracy better than 6 % relative to calorimetry and {gamma}-ray isotopics. This accuracy is achievable, after application of appropriate bias corrections, for transmissions of about {1/2} % through the waste form and counting times of less than 30 minutes. These results are valid for ash material and graphite fines with the same degree of plutonium particle size, homogeneity, sample density, and sample geometry as the waste form used to obtain the results in this study. A drum-sized thermal neutron counter (TNC) was also included in the study to provide an alternative in the event the SGS failed to meet the required level of accuracy. The preliminary indications are that this method will also achieve the required accuracy with counting times of {approximately}30 minutes and appropriate application of bias corrections. The bias corrections can be avoided in all cases if the instruments are calibrated on standards matching the items.

  2. Evaluation and selection of candidate high-level waste forms

    Seven candidate waste forms being developed under the direction of the Department of Energy's National High-Level Waste (HLW) Technology Program, were evaluated as potential media for the immobilization and geologic disposal of high-level nuclear wastes. The evaluation combined preliminary waste form evaluations conducted at DOE defense waste-sites and independent laboratories, peer review assessments, a product performance evaluation, and a processability analysis. Based on the combined results of these four inputs, two of the seven forms, borosilicate glass and a titanate based ceramic, SYNROC, were selected as the reference and alternative forms for continued development and evaluation in the National HLW Program. Both the glass and ceramic forms are viable candidates for use at each of the DOE defense waste-sites; they are also potential candidates for immobilization of commercial reprocessing wastes. This report describes the waste form screening process, and discusses each of the four major inputs considered in the selection of the two forms

  3. Waste form development for a DC arc furnace

    A laboratory crucible study was conducted to develop waste forms to treat nonradioactive simulated 238Pu heterogeneous debris waste from Savannah River, metal waste from the Idaho National Engineering Laboratory (INEL), and nominal waste also from INEL using DC arc melting. The preliminary results showed that the different waste form compositions had vastly different responses for each processing effect. The reducing condition of DC arc melting had no significant effects on the durability of some waste forms while it decreased the waste form durability from 300 to 700% for other waste forms, which resulted in the failure of some TCLP tests. The right formulations of waste can benefit from devitrification and showed an increase in durability by 40%. Some formulations showed no devitrification effects while others decreased durability by 200%. Increased waste loading also affected waste form behavior, decreasing durability for one waste, increasing durability by 240% for another, and showing no effect for the third waste. All of these responses to the processing and composition variations were dictated by the fundamental glass chemistry and can be adjusted to achieve maximal waste loading, acceptable durability, and desired processing characteristics if each waste formulation is designed for the result according to the glass chemistry

  4. Review of high-level waste form properties

    This report is a review of waste form options for the immobilization of high-level-liquid wastes from the nuclear fuel cycle. This review covers the status of international research and development on waste forms as of May 1979. Although the emphasis in this report is on waste form properties, process parameters are discussed where they may affect final waste form properties. A summary table is provided listing properties of various nuclear waste form options. It is concluded that proposed waste forms have properties falling within a relatively narrow range. In regard to crystalline versus glass waste forms, the conclusion is that either glass of crystalline materials can be shown to have some advantage when a single property is considered; however, at this date no single waste form offers optimum properties over the entire range of characteristics investigated. A long-term effort has been applied to the development of glass and calcine waste forms. Several additional waste forms have enough promise to warrant continued research and development to bring their state of development up to that of glass and calcine. Synthetic minerals, the multibarrier approach with coated particles in a metal matrix, and high pressure-high temperature ceramics offer potential advantages and need further study. Although this report discusses waste form properties, the total waste management system should be considered in the final selection of a waste form option. Canister design, canister materials, overpacks, engineered barriers, and repository characteristics, as well as the waste form, affect the overall performance of a waste management system. These parameters were not considered in this comparison

  5. Review of high-level waste form properties. [146 bibliographies

    Rusin, J.M.

    1980-12-01

    This report is a review of waste form options for the immobilization of high-level-liquid wastes from the nuclear fuel cycle. This review covers the status of international research and development on waste forms as of May 1979. Although the emphasis in this report is on waste form properties, process parameters are discussed where they may affect final waste form properties. A summary table is provided listing properties of various nuclear waste form options. It is concluded that proposed waste forms have properties falling within a relatively narrow range. In regard to crystalline versus glass waste forms, the conclusion is that either glass of crystalline materials can be shown to have some advantage when a single property is considered; however, at this date no single waste form offers optimum properties over the entire range of characteristics investigated. A long-term effort has been applied to the development of glass and calcine waste forms. Several additional waste forms have enough promise to warrant continued research and development to bring their state of development up to that of glass and calcine. Synthetic minerals, the multibarrier approach with coated particles in a metal matrix, and high pressure-high temperature ceramics offer potential advantages and need further study. Although this report discusses waste form properties, the total waste management system should be considered in the final selection of a waste form option. Canister design, canister materials, overpacks, engineered barriers, and repository characteristics, as well as the waste form, affect the overall performance of a waste management system. These parameters were not considered in this comparison.

  6. In-Drift Accumulation of Fissile Material From Waste Packages Containing Plutonium Disposition Waste Forms

    The objective of this calculation is to provide estimates of the amount of fissile material flowing out of the waste package (source term) and the accumulation of fissile elements (U and Pu) in a crushed-tuff invert. These calculations provide input for the analysis of repository impacts of the Pu-ceramic waste forms. In particular, the source term results are used as input to the far-field accumulation calculation reported in Ref. 51, and the in-drift accumulation results are used as inputs for the criticality calculations reported in Ref. 2. The results are also summarized and interpreted in Ref. 52. The scope of this calculation is the waste package (WP) Viability Assessment (VA) design, which consists of an outer corrosion-allowance material (CAM) and an inner corrosion-resistant material (CRM). This design is used in this calculation in order to be consistent with earlier Pu-ceramic degradation calculations (Ref. 15). The impact of the new Enhanced Design Alternative-I1 (EDA-11) design on the results will be addressed in a subsequent report. The design of the invert (a leveling foundation, which creates a level surface of the drift floor and supports the WP mounting structure) is consistent with the EDA-I1 design. The invert will be composed of crushed stone and a steel support structure (Ref. 17). The scope of this calculation is also defined by the nominal degradation scenario, which involves the breach of the WP (Section 10.5.1.2, Ref. 48), followed by the influx of water. Water in the WP may, in time, gradually leach the fissile components and neutron absorbers out of the ceramic waste forms. Thus, the water in the WP may become laden with dissolved actinides (e.g., Pu and U), and may eventually overflow or leak from the WP. Once the water leaves the WP, it may encounter the invert, in which the actinides may reprecipitate. Several factors could induce reprecipitation; these factors include: the high surface area of the crushed stone, and the presence of

  7. In-Drift Accumulation of Fissile Material From Waste Packages Containing Plutonium Disposition Waste Form

    H.W> Stockman; S. LeStrange

    2000-09-28

    The objective of this calculation is to provide estimates of the amount of fissile material flowing out of the waste package (source term) and the accumulation of fissile elements (U and Pu) in a crushed-tuff invert. These calculations provide input for the analysis of repository impacts of the Pu-ceramic waste forms. In particular, the source term results are used as input to the far-field accumulation calculation reported in Ref. 51, and the in-drift accumulation results are used as inputs for the criticality calculations reported in Ref. 2. The results are also summarized and interpreted in Ref. 52. The scope of this calculation is the waste package (WP) Viability Assessment (VA) design, which consists of an outer corrosion-allowance material (CAM) and an inner corrosion-resistant material (CRM). This design is used in this calculation in order to be consistent with earlier Pu-ceramic degradation calculations (Ref. 15). The impact of the new Enhanced Design Alternative-I1 (EDA-11) design on the results will be addressed in a subsequent report. The design of the invert (a leveling foundation, which creates a level surface of the drift floor and supports the WP mounting structure) is consistent with the EDA-I1 design. The invert will be composed of crushed stone and a steel support structure (Ref. 17). The scope of this calculation is also defined by the nominal degradation scenario, which involves the breach of the WP (Section 10.5.1.2, Ref. 48), followed by the influx of water. Water in the WP may, in time, gradually leach the fissile components and neutron absorbers out of the ceramic waste forms. Thus, the water in the WP may become laden with dissolved actinides (e.g., Pu and U), and may eventually overflow or leak from the WP. Once the water leaves the WP, it may encounter the invert, in which the actinides may reprecipitate. Several factors could induce reprecipitation; these factors include: the high surface area of the crushed stone, and the presence of

  8. Evaluation of Cyanex 923-coated magnetic particles for the extraction and separation of lanthanides and actinides from nuclear waste streams

    Shaibu, B. S.; Reddy, M. L. P.; Bhattacharyya, A.; Manchanda, V. K.

    2006-06-01

    In the magnetically assisted chemical separation (MACS) process, tiny ferromagnetic particles coated with solvent extractant are used to selectively separate radionuclides and hazardous metals from aqueous waste streams. The contaminant-loaded particles are then recovered from the waste solutions using a magnetic field. The contaminants attached to the magnetic particles are subsequently removed using a small volume of stripping agent. In the present study, Cyanex 923 (trialkylphosphine oxide) coated magnetic particles (cross-linked polyacrylamide and acrylic acid entrapping charcoal and iron oxide, 1:1:1, particle size=1-60 μm) are being evaluated for the possible application in the extraction and separation of lanthanides and actinides from nuclear waste streams. The uptake behaviour of Th(IV), U(VI), Am(III) and Eu(III) from nitric acid solutions was investigated by batch studies. The effects of sorption kinetics, extractant and nitric acid concentrations on the uptake behaviour of metal ions were systematically studied. The influence of fission products (Cs(I), Sr(II)) and interfering ions including Fe(III), Cr(VI), Mg(II), Mn(II), and Al(III) were investigated. The recycling capacity of the extractant-coated magnetic particles was also evaluated.

  9. CSNF WASTE FORM DEGRADATION: SUMMARY ABSTRACTION

    J.C. CUNNANE

    2004-08-31

    The purpose of this model report is to describe the development and validation of models that can be used to calculate the release of radionuclides from commercial spent nuclear fuel (CSNF) following a hypothetical breach of the waste package and fuel cladding in the repository. The purpose also includes describing the uncertainties associated with modeling the radionuclide release for the range of CSNF types, exposure conditions, and durations for which the radionuclide release models are to be applied. This document was developed in accordance with Technical Work Plan for: Regulatory Integration Modeling and Analysis of the Waste Form and Waste Package (BSC 2004 [DIRS 169944]). This document considers radionuclides to be released from CSNF when they are available for mobilization by gas-phase mass transport, or by dissolution or colloid formation in water that may contact the fuel. Because other reports address limitations on the dissolved and colloidal radionuclide concentrations (BSC 2004 [DIRS 169944], Table 2-1), this report does not address processes that control the extent to which the radionuclides released from CSNF are mobilized and transported away from the fuel either in the gas phase or in the aqueous phase as dissolved and colloidal species. The scope is limited to consideration of degradation of the CSNF rods following an initial breach of the cladding. It considers features of CSNF that limit the availability of individual radionuclides for release into the gaseous or aqueous phases that may contact the fuel and the processes and events expected to degrade these CSNF features. In short, the purpose is to describe the characteristics of breached fuel rods and the degradation processes expected to influence radionuclide release.

  10. CSNF WASTE FORM DEGRADATION: SUMMARY ABSTRACTION

    The purpose of this model report is to describe the development and validation of models that can be used to calculate the release of radionuclides from commercial spent nuclear fuel (CSNF) following a hypothetical breach of the waste package and fuel cladding in the repository. The purpose also includes describing the uncertainties associated with modeling the radionuclide release for the range of CSNF types, exposure conditions, and durations for which the radionuclide release models are to be applied. This document was developed in accordance with Technical Work Plan for: Regulatory Integration Modeling and Analysis of the Waste Form and Waste Package (BSC 2004 [DIRS 169944]). This document considers radionuclides to be released from CSNF when they are available for mobilization by gas-phase mass transport, or by dissolution or colloid formation in water that may contact the fuel. Because other reports address limitations on the dissolved and colloidal radionuclide concentrations (BSC 2004 [DIRS 169944], Table 2-1), this report does not address processes that control the extent to which the radionuclides released from CSNF are mobilized and transported away from the fuel either in the gas phase or in the aqueous phase as dissolved and colloidal species. The scope is limited to consideration of degradation of the CSNF rods following an initial breach of the cladding. It considers features of CSNF that limit the availability of individual radionuclides for release into the gaseous or aqueous phases that may contact the fuel and the processes and events expected to degrade these CSNF features. In short, the purpose is to describe the characteristics of breached fuel rods and the degradation processes expected to influence radionuclide release

  11. Formulation and Analysis of Compliant Grouted Waste Forms for SHINE Waste Streams

    Ebert, William [Argonne National Lab. (ANL), Argonne, IL (United States); Pereira, Candido [Argonne National Lab. (ANL), Argonne, IL (United States); Heltemes, Thad A. [Argonne National Lab. (ANL), Argonne, IL (United States); Youker, Amanda [Argonne National Lab. (ANL), Argonne, IL (United States); Makarashvili, Vakhtang [Argonne National Lab. (ANL), Argonne, IL (United States); Vandegrift, George F. [Argonne National Lab. (ANL), Argonne, IL (United States)

    2014-01-01

    Optional grouted waste forms were formulated for waste streams generated during the production of 99Mo to be compliant with low-level radioactive waste regulations. The amounts and dose rates of the various waste form materials that would be generated annually were estimated and used to determine the effects of various waste processing options, such as the of number irradiation cycles between uranium recovery operations, different combinations of waste streams, and removal of Pu, Cs, and Sr from waste streams for separate disposition (which is not evaluated in this report). These calculations indicate that Class C-compliant grouted waste forms can be produced for all waste streams. More frequent uranium recovery results in the generation of more chemical waste, but this is balanced by the fact that waste forms for those waste streams can accommodate higher waste loadings, such that similar amounts of grouted waste forms are required regardless of the recovery schedule. Similar amounts of grouted waste form are likewise needed for the individual and combined waste streams. Removing Pu, Cs, and Sr from waste streams lowers the waste form dose significantly at times beyond about 1 year after irradiation, which may benefit handling and transport. Although these calculations should be revised after experimentally optimizing the grout formulations and waste loadings, they provide initial guidance for process development.

  12. Laboratory procedures for waste form testing

    Mast, E.S.

    1994-09-19

    The 100 and 300 areas of the Hanford Site are included on the US Environmental Protection Agencies (EPA) National Priorities List under the Comprehensive Environmental Response, Compensation, and Liability Act (CERCLA). Soil washing is a treatment process that is being considered for the remediation of the soil in these areas. Contaminated soil washing fines can be mixed or blended with cementations materials to produce stable waste forms that can be used for beneficial purposes in mixed or low-level waste landfills, burial trenches, environmental restoration sites, and other applications. This process has been termed co-disposal. The Co-Disposal Treatability Study Test Plan is designed to identify a range of cement-based formulations that could be used in disposal efforts in Hanford in co-disposal applications. The purpose of this document is to provide explicit procedural information for the testing of co-disposal formulations. This plan also provides a discussion of laboratory safety and quality assurance necessary to ensure safe, reproducible testing in the laboratory.

  13. Laboratory procedures for waste form testing

    The 100 and 300 areas of the Hanford Site are included on the US Environmental Protection Agencies (EPA) National Priorities List under the Comprehensive Environmental Response, Compensation, and Liability Act (CERCLA). Soil washing is a treatment process that is being considered for the remediation of the soil in these areas. Contaminated soil washing fines can be mixed or blended with cementations materials to produce stable waste forms that can be used for beneficial purposes in mixed or low-level waste landfills, burial trenches, environmental restoration sites, and other applications. This process has been termed co-disposal. The Co-Disposal Treatability Study Test Plan is designed to identify a range of cement-based formulations that could be used in disposal efforts in Hanford in co-disposal applications. The purpose of this document is to provide explicit procedural information for the testing of co-disposal formulations. This plan also provides a discussion of laboratory safety and quality assurance necessary to ensure safe, reproducible testing in the laboratory

  14. Transmutation of nuclear waste. Status report RAS programme 1993: Recycling and transmutation of actinides and fission products

    The term ''nuclear transmutation'' means a conversion of long-lived radioactive nuclides into short-lived or stable nuclides and ''recycling'' means re-use of fissile material to generate energy in power reactors. With these two processes a reduction of the radiotoxicity and of its duration may be achieved, thus reducing the potential hazard to future generations. Firstly, the report gives a survey of the present situation regarding nuclear waste: its components, how the waste is produced in current LWR and possible options for interim and final storage. Then the objective of the RAS programme, the working methods and the state of the art of the research are considered. Two chapters deal with preliminary results of national and international research. A rather tentative prediction for the future is formulated. Some conclusions are drawn: It seems to be in the best interests of the Netherlands to continue the established line of reprocessing nuclear waste, should new reactors be introduced. It may be advisable to make international agreements so that in the future fission products will contain as few traces of transuranic actinides and long-lived components as possible. Consequently, nuclear waste would become cleaner in terms of long-lived components. For the transmutation of products separated in foreign countries, the Netherlands could pursue an active policy, perform research and also consider the use of MOX fuel in future Dutch reactors. Further contributions towards the solution of these problems can only be made by the Netherlands on an international level. As such, the research and study performed within the framework of the RAS-programme represents a useful international contribution. The possibilities offered by the HFR are particularly of great value. Finally, the choice of a new generation of nuclear reactors should be made not based only on the safety aspects, but also on the extent of waste production and on the transmutation possibilities (application

  15. Removing actinides using a chromatographic resin from High Activity Waste Solutions containing metallic impurities

    At the Plutonium Recycling Facility of CEA Valduc, anion exchange is used for recovering plutonium from nitric acid solutions. Although this approach recovers more than 99,9 %, the trace amounts of actinides as americium remaining in the effluent require additional processing to reduce alpha activity under the maximum allowed for surface disposal. A new process has been developed to remove actinides from these effluents with a TRUspec resin. A pilot composed of an electrochemical reactor followed by a TRUSPEC column has been designed into a glove box. Laboratory scale studies and first results on the pilot have confirmed the interesting bibliography concerning this process. The reduction of iron is effective with a yield of 98-99% and no significant retention of metallic impurities has been observed during fixing time. Moreover, Pr and Ce used as surrogates for Pu and Am are totally recovered in the elution phases. Further work will be done to validate the previous results and to qualify the overall process with active solutions

  16. Studies on actinide partitioning of high level waste solutions by technical scale solid phase extraction

    The twin column concept is designed to enhance the field of application of front chromatography. Operating in that mode, we could demonstrate, that the concentration curve of the chromatographic column effluent is composed of two fractions, the wall and interior fraction, having each a breakthrough volume at CBT/Cfeed = 50 % for the interior fraction (VBT) and CBO/Cfeed = φP/φC for the wall fraction (VBO). The corresponding volume ratio amounts to π/(π+2) = 0.61. On this basis, we established a chromatographic array composed of feed tank - 1. column - detector - 2. column - product tank and loaded the 1. column, until 1.22 VBT of feed has been conveyed through the column set. Then, CBO has been reached in the 2. column effluent. We can, thus, control the process below the detection limits of commercially available monitors. We employed the concept, to investigate the long-term behaviour of extractants recommended for the HLW partitioning. We could demonstrate, that CMPO appears to be an adequate extractant for partitioning HLW solutions in an actinide/lanthanide fraction and a fission/corrosion product fraction. However, we could not confirm, that (C1-C6H4)2=PS2H is sufficiently stable to maintain the chemical properties required for an actinide/lanthanide fractionation. We used one column filling with 10 g CMPO to process in total 1001 feed, thus economizing our studies. (author)

  17. Trends in actinide processing at Hanford

    In 1989, the mission at the Hanford Site began a dramatic and sometimes painful transition. The days of production--as we used to know it--are over. Our mission officially has become waste management and environmental cleanup. This mission change didn't eliminate many jobs--in fact, budgets have grown dramatically to support the new mission. Most all of the same skilled crafts, engineers, and scientists are still required for the new mission. This change has not eliminated the need for actinide processing, but it has certainly changed the focus that our actinide chemists and process engineers have. The focus used to be on such things as increasing capacity, improving separations efficiency, and product purity. Minimizing waste had become a more important theme in recent years and it is still a very important concept in the waste management and environmental cleanup arena. However, at Hanford, a new set of words dominates the actinide process scene as we work to deal with actinides that still reside in a variety of forms at the Hanford Site. These words are repackage, stabilize, remove, store and dispose. Some key activities in each of these areas are described in this report

  18. Solidification of simulated actinides by natural zircon

    YANG Jian-Wen; LUO Shang-Geng

    2004-01-01

    Natural zircon was used as precursor material to produce a zircon waste form bearing 20wt% simulated actinides (Nd2O3 and UO2) through a solid state reaction by a typical synroc fabrication process. The fabricated zircon waste form has relatively good physical properties (density 5.09g/cm3, open porosity 4.0%, Vickers hardness 715kg/mm2). The XRD, SEM/EDS and TEM/EDS analyses indicate that there are zircon phases containing waste elements formed through the reaction. The chemical durability and radiation stability are determined by the MCC-1method and heavy ion irradiation; the results show that the zircon waste form is highly leach resistance and relatively stable under irradiation (amorphous dose 0.7dpa). From this study, the method of using a natural mineral to solidify radioactive waste has proven to be feasible.

  19. Transportation considerations related to waste forms and canisters for Defense TRU wastes

    This report identifies and discusses the considerations imposed by transportation on waste forms and canisters for contact-handled, solid transuranic wastes from the US Department of Energy (DOE) activities. The report reviews (1) the existing raw waste forms and potential immobilized waste forms, (2) the existing and potential future DOE waste canisters and shipping containers, (3) regulations and regulatory trends for transporting commercial transuranic wastes on the ISA, (4) truck and rail carrier requirements and preferences for transporting the wastes, and (5) current and proposed Type B external packagings for transporting wastes

  20. Plutonium-238 alpha-decay damage study of the ceramic waste form.

    Frank, S M [U.S. Department of Energy, Idaho National Laboratory, P.O. Box 1625, Idaho Falls, ID 83415; Barber, T L [U.S. Department of Energy, Idaho National Laboratory, P.O. Box 1625, Idaho Falls, ID 83415; Cummings, D G [U.S. Department of Energy, Idaho National Laboratory, P.O. Box 1625, Idaho Falls, ID 83415; DiSanto, T [U.S. Department of Energy, Idaho National Laboratory, P.O. Box 1625, Idaho Falls, ID 83415; Esh, D W [U.S. Nuclear Regulatory Commission, Washington, DC 20555-0001; Giglio, J J [U.S. Department of Energy, Idaho National Laboratory, P.O. Box 1625, Idaho Falls, ID 83415; Goff, K M [U.S. Department of Energy, Idaho National Laboratory, P.O. Box 1625, Idaho Falls, ID 83415; Johnson, S G [U.S. Department of Energy, Idaho National Laboratory, P.O. Box 1625, Idaho Falls, ID 83415; Kennedy, J R [U.S. Department of Energy, Idaho National Laboratory, P.O. Box 1625, Idaho Falls, ID 83415; Jue, J-F [U.S. Department of Energy, Idaho National Laboratory, P.O. Box 1625, Idaho Falls, ID 83415; Noy, M [U.S. Department of Energy, Idaho National Laboratory, P.O. Box 1625, Idaho Falls, ID 83415; O' Holleran, T P [U.S. Department of Energy, Idaho National Laboratory, P.O. Box 1625, Idaho Falls, ID 83415; Sinkler, W [UOP LLC, 25 E Algonquin Road, Des Plaines, IL 60017

    2006-03-27

    volume has expanded slightly by 0.3% again, presumably due to alpha-decay damage. (5) No bulk sample swelling was observed. (6) No amorphization of sodalite or actinide bearing phases was observed after four years of alpha-decay damage. (7) No microcracks or phase de-bonding were observed in waste form samples aged for four years. (8) In some areas of the {sup 238}Pu doped ceramic waste form material bubbles and voids were found. Bubbles and voids with similar size and density were also found in ceramic waste form samples without actinide. These bubbles and voids are interpreted as pre-existing defects. However, some contribution to these bubbles and voids from helium gas can not be ruled out. (9) Chemical durability of {sup 238}Pu CWF has not changed significantly after four years of alpha-decay exposure except for an increase in the release of salt components and Pu. Still, the plutonium release from CWF is very low at less than 0.005 g/m{sup 2}.

  1. Biodegradation testing of TMI-2 EPICOR-II waste forms

    ASTM biodegradation tests were conducted on waste forms containing high specific activity ion exchange resins from EPICOR-II prefilters. Those tests were part of a program to test waste forms in accordance with the NRC Branch Technical Position on Waste Form. Small waste forms were manufactured using two different solidification agents, Portland Type I-II cement and vinyl ester-styrene (VES). Ion exchange material was taken from two EPICOR-II prefilters; PF-7, which contained all organic material, and PF-20, which contained organic resins and a layer of inorganic zeolites. Test results showed that the VES waste forms supported microbial growth, while cement waste forms did not support that growth. Growth was also observed adjacent to some VES waste forms. Radiation levels found in the ion exchange resins used in this study were not found to inhibit microbial growth. The extent of degradation of the waste forms could not be determined using the ASTM tests specified by the NRC Branch Technical Position on Waste Form. As a result of this work, a different testing methodology is recommended, which would provide direct verification of waste form capabilities. That methodology would evaluate solidification materials without using the ASTM procedures or subsequent compression testing. The proposed tests would provide exposure to a wide range of microbial species, use appropriately sized specimens, provide for possible use of alternate carbon sources, and extend the test length. Degradation would be determined directly by measuring metabolic activity or specimen weight loss. 16 refs., 15 figs., 3 tabs

  2. Waste forms, packages, and seals working group summary

    Sridhar, N. [Center Antonio, TX (United States); McNeil, M.B. [Nuclear Regulatory Commission, Washington, DC (United States)

    1995-09-01

    This article is a summary of the proceedings of a group discussion which took place at the Workshop on the Role of Natural Analogs in Geologic Disposal of High-Level Nuclear Waste in San Antonio, Texas on July 22-25, 1991. The working group concentrated on the subject of radioactive waste forms and packaging. Also included is a description of the use of natural analogs in waste packaging, container materials and waste forms.

  3. The construction of solid waste form test and inspection facility

    The solid waste form test and inspection facility is a facility to test and inspect the characteristics of waste forms, such as homogenity, mechanical structure, thermal behaviour, water resistance and leachability. Such kinds of characteristics in waste forms are required to meet a certain conditions for long-term storage or for final disposal of wastes. The facility will be used to evaluate safety for the disposal of wastes by test and inspection. At this moment, the efforts to search the most effective management of the radioactive wastes generated from power plants and radioisotope user are being executed by the people related to this field. Therefore, the facility becomes more significant tool because of its guidance of sucessfully converting wastes into forms to give a credit to the safety of waste disposal for managing the radioactive wastes. In addition the overall technical standards for inspecting of waste forms such as the standardized equipment and processes in the facility will be estabilished in the begining of 1990's when the project of waste management will be on the stream. Some of the items of the project have been standardized for the purpose of localization. In future, this facility will be utilized not only for the inspection of waste forms but also for the periodic decontamination apparatus by remote operation techniques. (Author)

  4. Adaptation of ICP-AES in lead cell facility in Chemistry Group, IGCAR and analysis of simulated high level waste as a part of the studies on minor actinide partitioning

    The spent fuel discharged from the nuclear reactor contains unused uranium and plutonium, and Np, Am, Cm called as minor actinides and fission products. Spent fuel is dissolved in nitric acid. U and Pu are recovered by a solvent extraction process known as PUREX process using 1.1 M TBP as extractant. The raffinate rejected is known as High Level Liquid Waste which is a complex mixture of minor actinides, corrosion products, and fission products. Partitioning of minor actinides (MA) and its transmutation is a viable strategy for the safe management of high level liquid waste (HLLW)

  5. Characterization of low and medium level radioactive waste forms

    The work reported was carried out during the first year of the Commission of the European Community's programme on the characterization of low and medium level waste forms. Ten reference waste forms plus others of special national interest have been identified covering PWR, BWR, GCR and reprocessing wastes. The immobilising media include the three main matrices: cement, polymers and bitumen, and a glass. Characterization is viewed as one input to quality assurance of the waste form and covers: waste-matrix compatibility, radiation effects, leaching, microbiological attack, shrinkage and swelling, ageing processes and thermal effects. The aim is a balanced programme of comparative data, predictive modelling and an undserstanding of basic mechanisms

  6. Production and measurement of minor actinides in the commercial fuel cycle

    Stanbro, W.D. [comp.

    1997-03-01

    The minor actinide elements, particularly neptunium and americium, are produced as a normal byproduct of the operation of thermal power reactors. Because of the existence of long-lived isotopes of these elements, they constitute the major sources of the residual radiation in spent fuel or in wastes resulting from reprocessing. This has led to examinations by some countries of the possibility of separating the minor actinides from waste products. The papers found in this report address the production of minor actinides in common thermal power reactors as well as approaches to measure these materials in various media. The first paper in this volume, {open_quotes}Production of Minor Actinides in the Commercial Fuel Cycle,{close_quotes} uses calculations with the ORIGEN2 reactor and decay code to estimate the amounts of minor actinides in spent fuel and separated plutonium as a function of reactor irradiation and the time after discharge. The second paper, {open_quotes}Destructive Assay of Minor Actinides,{close_quotes} describes a number of promising approaches for the chemical analysis of minor actinides in the various forms in which they are found at reprocessing plants. The next paper, {open_quotes}Hybrid KED/XRF Measurement of Minor Actinides in Reprocessing Plants,{close_quotes} uses the results of a simulation model to examine the possible applications of the hybrid KED/XRF instrument to the determination of minor actinides in some of the solutions found in reprocessing plants. In {open_quotes}Calorimetric Assay of Minor Actinides,{close_quotes} the authors show some possible extensions of this powerful technique beyond the normal plutonium assays to include the minor actinides. Finally, the last paper in this volume, {open_quotes}Environment Measurements of Transuranic Nuclides,{close_quotes} discusses what is known about the levels of the minor actinides in the environment and ways to analyze for these materials in environmental matrices.

  7. Phosphate bonded ceramics as candidate final-waste-form materials

    Room-temperature setting phosphate-bonded ceramics were studied as candidate materials for stabilization of DOE low-level problem mixed wastes which cannot be treated by other established stabilization techniques. Phosphates of Mg, Mg-Na, Al and Zr were studied to stabilize ash surrogate waste containing RCRA metals as nitrates and RCRA organics. We show that for a typical loading of 35 wt.% of the ash waste, the phosphate ceramics pass the TCLP test. The waste forms have high compression strength exceeding ASTM recommendations for final waste forms. Detailed X-ray diffraction studies and differential thermal analyses of the waste forms show evidence of chemical reaction of the waste with phosphoric acid and the host matrix. The SEM studies show evidence of physical bonding. The excellent performance in the leaching tests is attributed to a chemical solidification and physical as well as chemical bonding of ash wastes in these phosphate ceramics

  8. Physical modeling of contaminant diffusion from a cementious waste form

    Cementitious materials can be used to immobilize waste materials for disposal. The Westinghouse Hanford Company is pursuing approval of disposal technologies by which hazardous and radioactive wastes are blended or packaged with cementitious materials for disposal. Of significant concern is the mobility of the waste contaminants both from the waste form and in the arid soils of the Hanford Site. A physical model has been developed to study the diffusion of waste contaminants from simulated cementitious waste forms in unsaturated Hanford Site soils. The model can be used to predict cementitious waste form performance in a representative environment, support design of waste management facilities and technologies, and provide data for environmental permitting of proposed treatment and disposal facilities

  9. Alternate nuclear waste forms and interactions in geologic media

    The primary purposes of the conference on Alternate Nuclear Waste Forms and Interactions in Geologic Media were: First, to provide an opportunity for a review of the status of the research on some of the candidate alternative waste forms; second, to provide an opportunity for comparing the characteristics of alternate waste forms to those of glasses; and third, to stimulate increased interactions between those research groups that were engaged in a more basic approach to characterizing waste forms and those who were concerned with more applied aspects such as the processing of these materials. The motivating philosophy behind this third purpose of the conference was based on the idea that by operating from the soundest possible fundamental base for any of the candidate waste forms, hopefully any future unpleasant surprise - such as that alluded to earlier in the case of glass waste forms - could be avoided. Separate abstracts have been prepared for individual papers for inclusion in the Energy Data Base

  10. DURABILITY TESTING OF FLUIDIZED BED STEAM REFORMER (FBSR) WASTE FORMS

    Jantzen, C

    2006-01-06

    Fluidized Bed Steam Reforming (FBSR) is being considered as a potential technology for the immobilization of a wide variety of high sodium aqueous radioactive wastes. The addition of clay and a catalyst as co-reactants converts high sodium aqueous low activity wastes (LAW) such as those existing at the Hanford and Idaho DOE sites to a granular ''mineralized'' waste form that may be made into a monolith form if necessary. Simulant Hanford and Idaho high sodium wastes were processed in a pilot scale FBSR at Science Applications International Corporation (SAIC) Science and Technology Applications Research (STAR) facility in Idaho Falls, ID. Granular mineral waste forms were made from (1) a basic Hanford Envelope A low-activity waste (LAW) simulant and (2) an acidic INL simulant commonly referred to as sodium-bearing waste (SBW). The FBSR waste forms were characterized and the durability tested via ASTM C1285 (Product Consistency Test), the Environmental Protection Agency (EPA) Toxic Characteristic Leaching Procedure (TCLP), and the Single Pass Flow Through (SPFT) test. The durability of the FBSR waste form products was tested in order to compare the measured durability to previous FBSR waste form testing on Hanford Envelope C waste forms that were made by THOR Treatment Technologies (TTT) and to compare the FBSR durability to vitreous LAW waste forms, specifically the Hanford low activity waste (LAW) glass known as the Low-activity Reference Material (LRM). The durability of the FBSR waste form is comparable to that of the LRM glass for the test responses studied.

  11. Studies on the separation of minor actinides from high-level wastes by extraction chromatography using novel silica-based extraction resins

    Wei, Y.; Kumagai, M; Takashima, Y.; Modolo, G.; R. Odoj

    2000-01-01

    To develop an advanced partitioning process by extraction chromatography using a minimal organic solvent and compact equipment to separate minor actinides such as Am and Cm from nitrate acidic high-level waste (HLW) solution, several novel silica-based extraction resins have been prepared by impregnating organic extractants into the styrene-divinylbenzene copolymer, which is immobilized in porous silica particles (SiO2-P). The extractants include octyl(phenyl)-N, N-diisobutylcarbamoylmethylph...

  12. DSNF AND OTHER WASTE FORM DEGRADATION ABSTRACTION

    Several hundred distinct types of DOE-owned spent nuclear fuel (DSNF) may potentially be disposed in the Yucca Mountain repository. These fuel types represent many more types than can be viably individually examined for their effect on the Total System Performance Assessment for the License Application (TSPA-LA). Additionally, for most of these fuel types, there is no known direct experimental test data for the degradation and dissolution of the waste form in repository groundwaters. The approach used in the TSPA-LA model is, therefore, to assess available information on each of 11 groups of DSNF, and to identify a model that can be used in the TSPA-LA model without differentiating between individual codisposal waste packages containing different DSNF types. The purpose of this report is to examine the available data and information concerning the dissolution kinetics of DSNF matrices for the purpose of abstracting a degradation model suitable for use in describing degradation of the DSNF inventory in the Total System Performance Assessment for the License Application. The data and information and associated degradation models were examined for the following types of DSNF: Group 1--Naval spent nuclear fuel; Group 2--Plutonium/uranium alloy (Fermi 1 SNF); Group 3--Plutonium/uranium carbide (Fast Flux Test Facility-Test Fuel Assembly SNF); Group 4--Mixed oxide and plutonium oxide (Fast Flux Test Facility-Demonstration Fuel Assembly/Fast Flux Test Facility-Test Demonstration Fuel Assembly SNF); Group 5--Thorium/uranium carbide (Fort St. Vrain SNF); Group 6--Thorium/uranium oxide (Shippingport light water breeder reactor SNF); Group 7--Uranium metal (N Reactor SNF); Group 8--Uranium oxide (Three Mile Island-2 core debris); Group 9--Aluminum-based SNF (Foreign Research Reactor SNF); Group 10--Miscellaneous Fuel; and Group 11--Uranium-zirconium hydride (Training Research Isotopes-General Atomics SNF). The analyses contained in this document provide an ''upper-limit'' (i

  13. Ceramic waste form qualification using results from witness tubes

    A ceramic waste form has been developed to immobilize the salt waste stream from electrometallurgical treatment of spent nuclear fuel. The ceramic waste form is prepared in a hot isostatic press (HIP). The use of small, easily fabricated HIP capsules called witness tubes has been proposed as a practical way to obtain representative samples of ceramic waste form material for process monitoring, waste form qualification, and archiving. Witness tubes are filled with the same material used to fill the corresponding HIP can, and are HIPed along with the HIP can. Relevant physical, chemical, and performance (leach test) data are analyzed and compared. Differences between witness tube and HIP can materials are shown to be statistically insignificant, demonstrating that witness tubes do provide ceramic waste form material representative of the material in the corresponding HIP can.

  14. Cerium as a surrogate in the plutonium immobilization waste form

    Marra, James Christopher

    In the aftermath of the Cold War, approximately 50 tonnes (MT) of weapons useable plutonium (Pu) has been identified as excess. The U.S. Department of Energy (DOE) has decided that at least a portion of this material will be immobilized in a titanate-based ceramic for final disposal in a geologic repository. The baseline formulation was designed to produce a ceramic consisting primarily of a highly substituted pyrochlore with minor amounts of brannerite and hafnia-substituted rutile. Since development studies with actual actinide materials is difficult, surrogates have been used to facilitate testing. Cerium has routinely been used as an actinide surrogate in actinide chemistry and processing studies. Although cerium appeared as an adequate physical surrogate for powder handling and general processing studies, cerium was found to act significantly different from a chemical perspective in the Pu ceramic form. The reduction of cerium at elevated temperatures caused different reaction paths toward densification of the respective forms resulting in different phase assemblages and microstructural features. Single-phase fabrication studies and cerium oxidation state analyses were performed to further quantify these behavioral differences. These studies indicated that the major phases in the final phase assemblages contained point defects likely leading to their stability. Additionally, thermochemical arguments predicted that the predominant pyrochlore phase in the ceramic was metastable. The apparent metastabilty associated with primary phase in the Pu ceramic form indicated that additional studies must be performed to evaluate the thermodynamic properties of these compounds. Moreover, the metastability of this predominant phase must be considered in assessment of long-term behavior (e.g. radiation stability) of this ceramic.

  15. Electrolytic extraction of fission noble metals for waste minimizing in advanced actinide separation system

    Electrochemistry for recovering fission platinum group elements (Pd. Ru) and Re (simulator of Te) from HNO3 solutions, Electrolytic Extraction (EE) method was applied as a basic technology in the new actinides separation process. The deposition yields of these elements increased by the decrease of the initial HNO3, concentration. Co-existence of Pd2+ ion accelerates the deposition of RuNO3- and ReO4- ions, and especially Ru deposition yield was over 99% when Pd2+ ion was added during the electrolysis in 2.SN HNO3 solution. Addition of reducing reagents (hydrazine nitrate and HAN) increased Pd2+ deposition rate, however, these and the other complexing reagents (e.g., oxalic acid and EDTA) decreased the Ru deposition because of preferential Pd2+ deposition as well as those complexation with RuNO3-, respectively. On the electrolytic extraction from the simulated HLLW, the elements which had nobler standard redox potential (E0) tended to show higher deposition yields; the elements which had E0 over 0.7 V (Ru, Te, Se, Rh, Pd) can be quantitatively recovered by 3 hr. electrolysis without dilution of HLLW. (author)

  16. Secondary waste form testing : ceramicrete phosphate bonded ceramics.

    Singh, D.; Ganga, R.; Gaviria, J.; Yusufoglu, Y. (Nuclear Engineering Division); ( ES)

    2011-06-21

    The cleanup activities of the Hanford tank wastes require stabilization and solidification of the secondary waste streams generated from the processing of the tank wastes. The treatment of these tank wastes to produce glass waste forms will generate secondary wastes, including routine solid wastes and liquid process effluents. Liquid wastes may include process condensates and scrubber/off-gas treatment liquids from the thermal waste treatment. The current baseline for solidification of the secondary wastes is a cement-based waste form. However, alternative secondary waste forms are being considered. In this regard, Ceramicrete technology, developed at Argonne National Laboratory, is being explored as an option to solidify and stabilize the secondary wastes. The Ceramicrete process has been demonstrated on four secondary waste formulations: baseline, cluster 1, cluster 2, and mixed waste streams. Based on the recipes provided by Pacific Northwest National Laboratory, the four waste simulants were prepared in-house. Waste forms were fabricated with three filler materials: Class C fly ash, CaSiO{sub 3}, and Class C fly ash + slag. Optimum waste loadings were as high as 20 wt.% for the fly ash and CaSiO{sub 3}, and 15 wt.% for fly ash + slag filler. Waste forms for physical characterizations were fabricated with no additives, hazardous contaminants, and radionuclide surrogates. Physical property characterizations (density, compressive strength, and 90-day water immersion test) showed that the waste forms were stable and durable. Compressive strengths were >2,500 psi, and the strengths remained high after the 90-day water immersion test. Fly ash and CaSiO{sub 3} filler waste forms appeared to be superior to the waste forms with fly ash + slag as a filler. Waste form weight loss was {approx}5-14 wt.% over the 90-day immersion test. The majority of the weight loss occurred during the initial phase of the immersion test, indicative of washing off of residual unreacted

  17. Quality control of cemented waste forms

    Slate, L.J.

    1994-12-31

    To insure that cemented radwaste remains immobilized after disposal, certain standards have been set in Europe by the Commission of the European Communities. One such standard is compressive strength. If the compressive strength can be predicted during the early curing stages, time and money can be saved and the quality of the final waste form guaranteed. It was determined that the 7- and 28-day compressive strength from radwaste cementation can be predicted during the mixing and early curing stages by at least three methods. The three that were studied were maturity, rheology, and impedance. Maturity is a temperature-to-time measurement, rheology is a shear stress-to-shear rate measurement, and impedance is the opposition offered to the flow of alternating current. These three methods were employed on five different cemented radwaste concentrations with three different water-to-cement ratios; thus, a total of 15 different mix designs were considered. The results showed that the impedance was the easiest to employ for an on-line process. The results of the impedance method showed a very good relationship between impedance and water-to-cement ratio; therefore, an accurate prediction of compressive strength of cemented radwaste can be drawn from this method. The results of the theology method were very good. The method showed that concrete conforms to the Bingham plastic rheologic model, and the theology method can be used to predict the compressive strength of cemented radwaste, but may be too cumbersome. The results of the maturity method were shown to be limited in accuracy for determining compressive strength.

  18. Far-Field Accumulation of Fissile Material From Waste Packages Containing Plutonium Disposition Waste Form

    The objective of this calculation is to estimate the quantity of fissile material that could accumulate in fractures in the rock beneath plutonium-ceramic (Pu-ceramic) and Mixed-Oxide (MOX) waste packages (WPs) as they degrade in the potential monitored geologic repository at Yucca Mountain. This calculation is to feed another calculation (Ref. 31) computing the probability of criticality in the systems described in Section 6 and then ultimately to a more general report on the impact of plutonium on the performance of the proposed repository (Ref. 32), both developed concurrently to this work. This calculation is done in accordance with the development plan TDP-DDC-MD-000001 (Ref. 9), item 5. The original document described in item 5 has been split into two documents: this calculation and Ref. 4. The scope of the calculation is limited to only very low flow rates because they lead to the most conservative cases for Pu accumulation and more generally are consistent with the way the effluent from the WP (called source term in this calculation) was calculated (Ref. 4). Ref. 4 (''In-Drift Accumulation of Fissile Material from WPs Containing Plutonium Disposition Waste Forms'') details the evolution through time (breach time is initial time) of the chemical composition of the solution inside the WP as degradation of the fuel and other materials proceed. It is the chemical solution used as a source term in this calculation. Ref. 4 takes that same source term and reacts it with the invert; this calculation reacts it with the rock. In addition to reactions with the rock minerals (that release Si and Ca), the basic mechanisms for actinide precipitation are dilution and mixing with resident water as explained in Section 2.1.4. No other potential mechanism such as flow through a reducing zone is investigated in this calculation. No attempt was made to use the effluent water from the bottom of the invert instead of using directly the effluent water from the WP. This

  19. Far-Field Accumulation of Fissile Material From Waste Packages Containing Plutonium Disposition Waste Form

    J.P. Nicot

    2000-09-29

    The objective of this calculation is to estimate the quantity of fissile material that could accumulate in fractures in the rock beneath plutonium-ceramic (Pu-ceramic) and Mixed-Oxide (MOX) waste packages (WPs) as they degrade in the potential monitored geologic repository at Yucca Mountain. This calculation is to feed another calculation (Ref. 31) computing the probability of criticality in the systems described in Section 6 and then ultimately to a more general report on the impact of plutonium on the performance of the proposed repository (Ref. 32), both developed concurrently to this work. This calculation is done in accordance with the development plan TDP-DDC-MD-000001 (Ref. 9), item 5. The original document described in item 5 has been split into two documents: this calculation and Ref. 4. The scope of the calculation is limited to only very low flow rates because they lead to the most conservative cases for Pu accumulation and more generally are consistent with the way the effluent from the WP (called source term in this calculation) was calculated (Ref. 4). Ref. 4 (''In-Drift Accumulation of Fissile Material from WPs Containing Plutonium Disposition Waste Forms'') details the evolution through time (breach time is initial time) of the chemical composition of the solution inside the WP as degradation of the fuel and other materials proceed. It is the chemical solution used as a source term in this calculation. Ref. 4 takes that same source term and reacts it with the invert; this calculation reacts it with the rock. In addition to reactions with the rock minerals (that release Si and Ca), the basic mechanisms for actinide precipitation are dilution and mixing with resident water as explained in Section 2.1.4. No other potential mechanism such as flow through a reducing zone is investigated in this calculation. No attempt was made to use the effluent water from the bottom of the invert instead of using directly the effluent water from the

  20. Characterization of composite ceramic high level waste forms

    Argonne National Laboratory has developed a composite ceramic waste form for the disposition of high level radioactive waste produced during electrometallurgical conditioning of spent nuclear fuel. The electrorefiner LiCl/KCl eutectic salt, containing fission products and transuranics in the chloride form, is contacted with a zeolite material which removes the fission products from the salt. After salt contact, the zeolite is mixed with a glass binder. The zeolite/glass mixture is then hot isostatic pressed (HIPed) to produce the composite ceramic waste form. The ceramic waste form provides a durable medium that is well suited to incorporate fission products and transuranics in the chloride form. Presented are preliminary results of the process qualification and characterization studies, which include chemical and physical measurements and product durability testing, of the ceramic waste form

  1. Leaching from solidified waste forms under saturated and unsaturated conditions

    The leaching behavior of nitrate ion from a cement based waste form containing low-level radioactive waste was shown to be identical under saturated and unsaturated soil conditions. Only in soils containing less than 2 wt %water did the leach rate decrease. The observation of identical leach rates under saturated and unsaturated conditions is explained by diffusion through the waste form being the limiting step. Diffusion through the soil decreases in very dry soil and the limiting step changes. These laboratory tests were verified by measurements on similar, Portland cement based waste form in a field lysimeter

  2. Final report on cermet high-level waste forms

    Cermets are being developed as an alternate method for the fixation of defense and commercial high level radioactive waste in a terminal disposal form. Following initial feasibility assessments of this waste form, consisting of ceramic particles dispersed in an iron-nickel base alloy, significantly improved processing methods were developed. The characterization of cermets has continued through property determinations on samples prepared by various methods from a variety of simulated and actual high-level wastes. This report describes the status of development of the cermet waste form as it has evolved since 1977. 6 tables, 18 figures

  3. Demonstration of modifier-free trivalent actinide partitioning from simulated high-level liquid waste using unsymmetrical diglycolamide

    Partitioning of trivalent lanthanides and actinides from fast-reactor (FR) simulated high-level liquid waste (SHLLW) has been demonstrated, for the first time, using a modifier-free unsymmetrical diglycolamide, N,N,-didodecyl-N',N'-dioctyl- 3-oxapentane-1,5-diamide (D3DODGA), in n-dodecane (n-DD). The extraction behavior of various metal ions present in the FR-SHLLW was studied using a solution of 0.1 M D3DODGA/n-DD. The extraction of Am(III) was accompanied by the co-extraction of all lanthanides and unwanted metal ions such as Zr(IV), Y(III), and Pd(II) from FR-SHLLW. The coextraction of unwanted metal ions was minimized by adding suitable aqueous soluble complexing agents. The stripping of Am(III) and Ln(III) from the loaded organic phase was studied using dilute nitric acid. Based on those results, a counter-current mixer-settler run was performed in a 20-stage mixer-settler. (author)

  4. Waste Classification based on Waste Form Heat Generation in Advanced Nuclear Fuel Cycles Using the Fuel-Cycle Integration and Tradeoffs (FIT) Model

    Denia Djokic; Steven J. Piet; Layne F. Pincock; Nick R. Soelberg

    2013-02-01

    This study explores the impact of wastes generated from potential future fuel cycles and the issues presented by classifying these under current classification criteria, and discusses the possibility of a comprehensive and consistent characteristics-based classification framework based on new waste streams created from advanced fuel cycles. A static mass flow model, Fuel-Cycle Integration and Tradeoffs (FIT), was used to calculate the composition of waste streams resulting from different nuclear fuel cycle choices. This analysis focuses on the impact of waste form heat load on waste classification practices, although classifying by metrics of radiotoxicity, mass, and volume is also possible. The value of separation of heat-generating fission products and actinides in different fuel cycles is discussed. It was shown that the benefits of reducing the short-term fission-product heat load of waste destined for geologic disposal are neglected under the current source-based radioactive waste classification system , and that it is useful to classify waste streams based on how favorable the impact of interim storage is in increasing repository capacity.

  5. The investigation of the neptunium complexes formed upon interaction of high level waste glass and boom clay media

    Since complexes formed between actinides released from high level waste glass and humic acids present in high concentration in boom clay porewater may control the actinide solubility in the clay formation, a research programme has been started to study the complexes formed between neptunium, the most critical actinide in the Belgian performance assessment studies, and boom clay porewater. The leaching experiments give a maximum solution concentration of Np in boom clay porewater of 10-6 M after 24 days. In the leachates, Np is mainly associated with colloidal particles of small sizes and is present as a mixture of two oxidation states, V and IV. The retention of Np in the glass increases with increasing SA/V (geometrical surface area on solution volume ratio). A high solution concentration is accompanied by a high retention of Np. The characterisation of the mobile boom clay organic matter (OM) gives a proton exchange capacity (PEC) equal to 2.9 meq g-1 OM at pH 8.5. Related to this value, the interaction constants (β) of the literature were reviewed and calculated according to their proton exchange capacity for the pH of interest. (orig.)

  6. Leaching studies of low-level radioactive waste forms

    A research program has been underway at the Brookhaven National Laboratory to investigate the release of radionuclides from low-level waste forms under laboratory conditions. This paper describes the leaching behavior of Cs-137 from two major low-level waste streams, that is, ion exchange bead resin and boric acid concentrate, solidified in Portland cement. The resultant leach data are employed to evaluate and predict the release behavior of Cs-137 from low-level waste forms under field burial conditions

  7. Leaching studies of low-level radioactive waste forms

    A research program has been underway at the Brookhaven National Laboratory to investigate the release of radionuclides from low-level waste forms under laboratory conditions. This paper describes the leaching behaviour of Cs-137 from two major low-level waste streams, that is, ion exchange bead resin and boric acid concentrate, solidified in Portland cement. The resultant leach data are employed to evaluate and predict the release behaviour of Cs-137 from low-level waste forms under field burial conditions

  8. DSNF AND OTHER WASTE FORM DEGRADATION ABSTRACTION

    J. CUNNANE

    2004-11-19

    Several hundred distinct types of DOE-owned spent nuclear fuel (DSNF) may potentially be disposed in the Yucca Mountain repository. These fuel types represent many more types than can be viably individually examined for their effect on the Total System Performance Assessment for the License Application (TSPA-LA). Additionally, for most of these fuel types, there is no known direct experimental test data for the degradation and dissolution of the waste form in repository groundwaters. The approach used in the TSPA-LA model is, therefore, to assess available information on each of 11 groups of DSNF, and to identify a model that can be used in the TSPA-LA model without differentiating between individual codisposal waste packages containing different DSNF types. The purpose of this report is to examine the available data and information concerning the dissolution kinetics of DSNF matrices for the purpose of abstracting a degradation model suitable for use in describing degradation of the DSNF inventory in the Total System Performance Assessment for the License Application. The data and information and associated degradation models were examined for the following types of DSNF: Group 1--Naval spent nuclear fuel; Group 2--Plutonium/uranium alloy (Fermi 1 SNF); Group 3--Plutonium/uranium carbide (Fast Flux Test Facility-Test Fuel Assembly SNF); Group 4--Mixed oxide and plutonium oxide (Fast Flux Test Facility-Demonstration Fuel Assembly/Fast Flux Test Facility-Test Demonstration Fuel Assembly SNF); Group 5--Thorium/uranium carbide (Fort St. Vrain SNF); Group 6--Thorium/uranium oxide (Shippingport light water breeder reactor SNF); Group 7--Uranium metal (N Reactor SNF); Group 8--Uranium oxide (Three Mile Island-2 core debris); Group 9--Aluminum-based SNF (Foreign Research Reactor SNF); Group 10--Miscellaneous Fuel; and Group 11--Uranium-zirconium hydride (Training Research Isotopes-General Atomics SNF). The analyses contained in this document provide an &apos

  9. Characteristics of Cast Stone cementitious waste form for immobilization of secondary wastes from vitrification process

    Chung, Chul-Woo; Um, Wooyong; Valenta, Michelle M.; Sundaram, S. K.; Chun, Jaehun; Parker, Kent E.; Kimura, Marcia L.; Westsik, Joseph H.

    2012-01-01

    The high-temperature in vitrification process of radioactive wastes could cause radioactive technetium ( 99Tc) in secondary liquid wastes to become volatile. Solidified cementitious waste forms at low temperature were developed to immobilize radioactive secondary waste. This research focuses on the characterization of a cementitious waste form called Cast Stone. Properties including compressive strength, surface area, phase composition, and technetium leaching were measured. The results indicate that technetium diffusivity is affected by simulant type. Additionally, ettringite and AFm (Al 2O 3-Fe 2O 3-mono) main crystalline phases were formed during hydration. The Cast Stone waste form passed the qualification requirements for a secondary waste form, which are compressive strength of 3.45 MPa and technetium diffusivity of 10 -9 cm 2/s. Cast Stone was found to be a good candidate for immobilizing secondary waste streams.

  10. Review of the sorption of actinides on natural minerals

    Over the past few years, a large body of data concerning sorption of actinides on geologic media has been built in connection with high-level-waste disposal. The primary aim of the work has been to allow predictions of the migration behavior of these radionuclides in the case of a breach of the repository that allowed groundwater flow through the repository. As a result of this work, some new backfill materials specifically tailored for the actinides have also been designed. Several major mechanisms of sorption that appear to dominate the sorption of actinides have emerged from these studies. These mechanisms can be divided into solution reactions dominated by hydrolysis, chemisorption reactions, and oxidation-reduction reactions. Each of these mechanisms will be discussed in detail, with experimental examples. Surprisingly, one mechanism, cation exchange, does not play an important role; why it fails to operate in any significant way in the environmental pH region will be discussed. The implications of the sorption mechanisms for waste forms and backfill materials will be discussed in detail. These discussions will center primarily around the valence state of the actinide in various waste forms and the effect of various anions on leachability from waste forms and backfill materials

  11. Secondary Waste Form Down Selection Data Package – Ceramicrete

    Cantrell, Kirk J.; Westsik, Joseph H.

    2011-08-31

    As part of high-level waste pretreatment and immobilized low activity waste processing, liquid secondary wastes will be generated that will be transferred to the Effluent Treatment Facility on the Hanford Site for further treatment. These liquid secondary wastes will be converted to stable solid waste forms that will be disposed in the Integrated Disposal Facility. Currently, four waste forms are being considered for stabilization and solidification of the liquid secondary wastes. These waste forms are Cast Stone, Ceramicrete, DuraLith, and Fluidized Bed Steam Reformer. The preferred alternative will be down selected from these four waste forms. Pacific Northwest National Laboratory is developing data packages to support the down selection process. The objective of the data packages is to identify, evaluate, and summarize the existing information on the four waste forms being considered for stabilization and solidification of the liquid secondary wastes. The information included will be based on information available in the open literature and from data obtained from testing currently underway. This data package is for the Ceramicrete waste form. Ceramicrete is a relatively new engineering material developed at Argonne National Laboratory to treat radioactive and hazardous waste streams (e.g., Wagh 2004; Wagh et al. 1999a, 2003; Singh et al. 2000). This cement-like waste form can be used to treat solids, liquids, and sludges by chemical immobilization, microencapsulation, and/or macroencapsulation. The Ceramicrete technology is based on chemical reaction between phosphate anions and metal cations to form a strong, dense, durable, low porosity matrix that immobilizes hazardous and radioactive contaminants as insoluble phosphates and microencapsulates insoluble radioactive components and other constituents that do not form phosphates. Ceramicrete is a type of phosphate-bonded ceramic, which are also known as chemically bonded phosphate ceramics. The Ceramicrete

  12. Prediction of dissolved actinide concentrations in concentrated electrolyte solutions: a conceptual model and model results for the Waste Isolation Pilot Plant (WIPP)

    The conceptual model for WIPP dissolved concentrations is a description of the complex natural and artificial chemical conditions expected to influence dissolved actinide concentrations in the repository. By a set of physical and chemical assumptions regarding chemical kinetics, sorption substrates, and waste-brine interactions, the system was simplified to be amenable to mathematical description. The analysis indicated that an equilibrium thermodynamic model for describing actinide solubilities in brines would be tractable and scientifically supportable. This paper summarizes the conceptualization and modeling approach and the computational results as used in the WIPP application for certification of compliance with relevant regulations for nuclear waste repositories. The WIPP site contains complex natural brines ranging from sea water to 10x more concentrated than sea water. Data bases for predicting solubility of Am(III) (as well as Pu(III) and Nd(III)), Th(IV), and Np(V) in these brines under potential repository conditions have been developed, focusing on chemical interactions with Na, K, Mg, Cl, SO4, and CO3 ions, and the organic acid anions acetate, citrate, EDTA, and oxalate. The laboratory and modeling effort augmented the Harvie et al. parameterization of the Pitzer activity coefficient model so that it could be applied to the actinides and oxidation states important to the WIPP system

  13. Thermal stability testing of low-level waste forms

    The NRC Technical Position (TP) on Waste Form specifies that waste forms should be resistant to thermal degradation. The thermal cycle testing procedure outlined in the TP on Waste Form was carried out and is believed adequate for demonstrating the thermal stability of solidified waste forms. The inclusion of control samples and the monitoring of sample temperature are recommended additions to the test. An outline for reporting thermal cycling test results is given. To produce a data base on the applicability of the thermal cycling test, the following simulated laboratory-scale waste forms were prepared and tested: boric acid and sodium sulfate evaporator bottoms, mixed bed bead resins, and powdered resins each solidified in asphalt, cement and vinyl ester-styrene. Thermal cycling does not significantly affect the compressive strength of the solidified wastes, except powdered resins solidified in cement which disintegrated during the test and bead resins in cement which showed a loss of compressive strength. After temperature cycling, cement solidified bead resins showed areas of spalling and solidified sodium sulfate forms had surface deterioration. Asphalt solidified wastes, except powdered resins, deformed by slumping on temperature cycling. Free liquid was released from vinyl esterstyrene solidifed waste forms as a result of thermal cycling. Dewatered bead and powdered resins were also tested and no free liquid was released on temperature cycling. 11 refs., 12 figs., 4 tabs

  14. Preparation and leaching of radioactive INEL waste forms

    Appreciable quantities of radioactive waste are in storage at the Idaho National Engineering Laboratory (INEL). Plans are being made to convert this waste into durable solid forms for final disposal in a geological repository. Part of the inventory consists of low- and intermediate-level fission, activation, and decay products and transuranic (TRU) wastes, either stored retrievably or buried at the INEL Radioactive Waste Management area. One of the TRU wastes is a sludge from the Department of Energy Rocky Flats Plant, currently stored retrievably in 55-gallon drums. Immobilizing the TRU sludge is the primary concern of the work reported here

  15. Application of the TESEO process for actinide removal from liquid alpha wastes generated during UO2-PuO2 fuel fabrication campaigns

    The relatively new bifunctional extractant Octyl (Phenyl) NN'Diisobutylcarbamoylmethylphosphineoxide (CMPO) shows a very strong extracting power for actinides, independently from the valency state, over a wide range of acidities (0.5-6M). The objective of this work is the definition of a flowsheet for the treatment of the alpha contaminated liquid wastes of the CRE Casaccia by liquid-liquid extraction using CMPO as extractant. Tests for TRU separation of these liquid wastes were carried out using CMPO extracting system both from solutions simulating their composition and from real wastes. On the basis of the results obtained in batch and continuous countercurrent flowsheet demonstrations carried out with real wastes, using laboratory scale mixer settlers, a pilot plant has been designed and built. (author)

  16. Actinides-1981

    1981-09-01

    Abstracts of 134 papers which were presented at the Actinides-1981 conference are presented. Approximately half of these papers deal with electronic structure of the actinides. Others deal with solid state chemistry, nuclear physic, thermodynamic properties, solution chemistry, and applied chemistry.

  17. Actinides-1981

    Abstracts of 134 papers which were presented at the Actinides-1981 conference are presented. Approximately half of these papers deal with electronic structure of the actinides. Others deal with solid state chemistry, nuclear physic, thermodynamic properties, solution chemistry, and applied chemistry

  18. Application of PCT to the EBR II ceramic waste form

    We are evaluating the use of the Product Consistency Test (PCT) developed to monitor the consistency of borosilicate glass waste forms for application to the multiphase ceramic waste form (CWF) that will be used to immobilize waste salts generated during the electrometallurgical conditioning of spent sodium-bonded nuclear fuel from the Experimental Breeder Reactor No. 2 (EBR II). The CWF is a multiphase waste form comprised of about 70% sodalite, 25% borosilicate glass binder, and small amounts of halite and oxide inclusions. It must be qualified for disposal as a non-standard high-level waste (HLW) form. One of the requirements in the DOE Waste Acceptance System Requirements Document (WASRD) for HLW waste forms is that the consistency of the waste forms be monitored.[1] Use of the PCT is being considered for the CWF because of the similarities of the dissolution behaviors of both the sodalite and glass binder phases in the CWF to borosilicate HLW glasses. This paper provides (1) a summary of the approach taken in selecting a consistency test for CWF production and (2) results of tests conducted to measure the precision and sensitivity of the PCT conducted with simulated CWF

  19. Supercritical fluid extraction studies on actinides

    Uranyl nitrate and plutonium in its Pu (III) as well Pu (IV) form loaded onto a tissue paper was extracted completed from paper, glass, stainless steel as well as teflon matrices using modified SC-CO2. A further investigation on recovery of actinides independent of their drying period is expected to culminate into developing an universal procedure to handle Pu bearing waste for its recovery irrespective of its drying history and oxidation states. Such endeavors ultimately lead to the potential utility of the SFE technology for efficient nuclear waste management

  20. Testing and evaluation of polyethylene and sulfur cement waste forms

    This paper discusses the results of recent studies related to the use of polyethylene and modified sulfur cement as new binder materials for the improved solidification of low-level wastes. Waste streams selected for this study include those which result from advanced volume reduction technologies (dry evaporator concentrate salts and incinerator ash) and those that remain problematic for solidification using contemporary agents (ion-exchange resins). Maximum waste loadings were determined for each waste type. Recommended waste loadings of 70 wt % sodium sulfate, 50 wt % boric acid, 40 wt % incinerator ash and 30 wt % ion exchange resins, which are based on process control and waste form performance considerations are reported for polyethylene. For sulfur cement the recommended waste loadings of 40 wt % sodium sulfate and boric acid salts and 43 wt % incinerator ash are reported. However, incorporation of ion-exchange resin waste in modified sulfur cement is not recommended due to poor waste form performance. The work presented in this paper will, in part, present data that can be used to assess the acceptability of polyethylene and modified sulfur cement waste forms to meet the requirements of 10 CFR 61. 8 refs., 10 figs., 6 tabs

  1. Testing and evaluation of polyethylene and sulfur cement waste forms

    This paper discusses the results of recent studies related to the use of polyethylene and modified sulfur cement as new binder materials for the improved solidification of low-level wastes. Waste streams selected for this study include those which result from advanced volume reduction technologies (dry evaporator concentrate salts and incinerator ash) and those that remain problematic for solidification using contemporary agents (ion exchange resins). Maximum waste loadings were determined for each waste type. Recommended waste loadings of 70 wt% sodium sulfate, 50 wt% boric acid, 40 wt% incinerator ash and 30 wt% ion exchange resins, which are based on process control and waste form performance considerations are reported for polyethylene. For sulfur cement the recommended waste loadings of 40 wt% sodium sulfate and boric acid salts and 43 wt% incinerator ash are reported. However, incorporation of ion exchange resin waste in modified sulfur cement is not recommended due to poor waste form performance. Data is presented that can be used to assess the acceptability of polyethylene and modified sulfur cement waste forms to meet the requirements of 10 CFR 61. 8 references, 10 figures, 6 tables

  2. Incineration of PWR actinide waste to launch a low waste thorium-based energy production with ADSs

    We investigate a scenario for a smooth transition from an energy production based on PWR to one relying on the Thorium cycle. The reactors used during the transition are solid-fuel fast-neutron Accelerator Driven Systems whose initial fuel incorporates the Transuranium waste produced by the PWRs. Our work relies on a realistic computation of the neutronics of these systems. The benefits of implementing this scenario (compared to exploiting PWRs) in terms of the reduction of the total radiotoxicity (interim storage, final waste, and in core material) is evaluated along and after the transition period as well as the impact on a future repository. (author)

  3. Talc-silicon glass-ceramic waste forms for immobilization of high- level calcined waste

    Talc-silicon glass-ceramic waste forms are being evaluated as candidates for immobilization of the high level calcined waste stored onsite at the Idaho Chemical Processing Plant. These glass-ceramic waste forms were prepared by hot isostatically pressing a mixture of simulated nonradioactive high level calcined waste, talc, silicon and aluminum metal additives. The waste forms were characterized for density, chemical durability, and glass and crystalline phase compositions. The results indicate improved density and chemical durability as the silicon content is increased

  4. Reference waste forms and packing material for the Nevada Nuclear Waste Storage Investigations Project

    The Lawrence Livermore National Laboratory (LLNL), Livermore, Calif., has been given the task of designing and verifying the performance of waste packages for the Nevada Nuclear Waste Storage Investigations (NNWSI) Project. NNWSI is studying the suitability of the tuffaceous rocks at Yucca Mountain, Nevada Test Site, for the potential construction of a high-level nuclear waste repository. This report gives a summary description of the three waste forms for which LLNL is designing waste packages: spent fuel, either as intact assemblies or as consolidated fuel pins, reprocessed commercial high-level waste in the form of borosilicate glass, and reprocessed defense high-level waste from the Defense Waste Processing Facility in Aiken, S.C. Reference packing material for use with the alternative waste package design for spent fuel is also described. 14 references, 8 figures, 20 tables

  5. Integral migration and source term experiments on cement and bitumen waste forms

    This is the final report of a programme of research which formed a part of the CEC joint research project into radionuclide migration in the geosphere (MIRAGE). This study addressed the aspects of integral migration and source term. The integral migration experiment simulated, in the laboratory, the intrusion of water into the repository, the leaching of radionuclides from two intermediate level wasteforms and the subsequent migration through the geosphere. The simulation consisted of a source of natural ground water which flowed over a sample of wasteform, at a controlled redox potential, and then through backfill and geological material packed in columns. The two wasteforms used here were cemented waste from the WAK plant at Karlsruhe, W. Germany and bitumenised intermediate concentrates from the Marcoule plant in France. The soluble fission products such as caesium wire rapidly released from the cemented waste but the actinides, and technetium in the reduced state, were retained in the wasteform. The release of all nuclides from the bitumenised waste was very low. (author)

  6. Recovery of actinides from spent nuclear fuel by pyrochemical reprocessing

    The Partitioning and Transmutation (P and T) strategy is based on reduction of the long-term radiotoxicity of spent nuclear fuel by recovery and recycling of plutonium and minor actinides, i.e. Np, Am and Cm. Regardless if transmutation of actinides is conceived by a heterogeneous accelerator driven system, fast reactor concept or as integrated waste burning with a homogenous recycling of all actinides, the reprocessed fuels used are likely to be significantly different from the commercial fuels of today. Because of the fuel type and the high burn-up reached, traditional hydrometallurgical reprocessing such as used today might not be the most adequate method. The main reasons are the low solubility of some fuel materials in acidic aqueous solutions and the limited radiation stability of the organic solvents used in extraction processes. Therefore, pyrochemical separation techniques are under development worldwide, usually based on electrochemical methods, reductive extraction in a high temperature molten salt solvent or fluoride volatility techniques. The pyrochemical reprocessing developed in ITU is based on electrorefining of metallic fuel in molten LiCl-KCl using solid aluminium cathodes. This is followed by a chlorination process for the recovery of actinides from formed actinide-aluminium alloys, and exhaustive electrolysis is proposed for the clean-up of salt from the remaining actinides. In this paper, the main achievements in the electrorefining process are summarised together with results of the most recent experimental studies on characterisation of actinides-aluminium intermetallic compounds. U, Np and Pu alloys were investigated by electrochemical techniques using solid aluminium electrodes and the alloys formed by electrodeposition of the individual actinides were analysed by XRD and SEM-EDX. Some thermodynamic properties were determined from the measurements (standard electrode potentials, Gibbs energy, enthalpy and entropy of formation) as well as

  7. Effects of waste content of glass waste forms on Savannah River high-level waste disposal costs

    Effects of the waste content of glass waste forms of Savannah River high-level waste disposal costs are evaluated by their impact on the number of waste canisters produced. Changes in waste content affect onsite Defense Waste Processing Facility (DWPF) costs as well as offsite shipping and repository emplacement charges. A nominal 1% increase over the 28 wt % waste loading of DWPF glass would reduce disposal costs by about $50 million for Savannah River wastes generated to the year 2000. Waste form modifications under current study include adjustments of glass frit content to compensate for added salt decontamination residues and increased sludge loadings in the DWPF glass. Projected cost reductions demonstrate significant incentives for continued optimization of the glass waste loadings. 13 refs., 3 figs., 3 tabs

  8. Comparison of glass and crystalline nuclear waste forms

    Nuclear waste forms may be divided into two broad categories: single phase glasses with minor crystalline components (e.g., borosilicate glasses) and crystalline waste forms, either single phase (e.g., monazite) or polyphase (e.g., SYNROC). This paper reviews the materials properties data that are available for each of these two types of waste forms. The principal data include: physical, thermal and mechanical properties, chemical durability; and radiation damage effects. Complete data are only available for borosilicate glasses and SYNROC; therefore, this comparison focuses on the performance assessment of borosilicate glass and SYNROC

  9. Enhancement of cemented waste forms by supercritical CO{sub 2} carbonation of standard portland cements

    Rubin, J.B.; Carey, J.; Taylor, C.M.V.

    1997-08-01

    We are conducting experiments on an innovative transformation concept, using a traditional immobilization technique, that may significantly reduce the volume of hazardous or radioactive waste requiring transport and long-term storage. The standard practice for the stabilization of radioactive salts and residues is to mix them with cements, which may include additives to enhance immobilization. Many of these wastes do not qualify for underground disposition, however, because they do not meet disposal requirements for free liquids, decay heat, head-space gas analysis, and/or leachability. The treatment method alters the bulk properties of a cemented waste form by greatly accelerating the natural cement-aging reactions, producing a chemically stable form having reduced free liquids, as well as reduced porosity, permeability and pH. These structural and chemical changes should allow for greater actinide loading, as well as the reduced mobility of the anions, cations, and radionuclides in aboveground and underground repositories. Simultaneously, the treatment process removes a majority of the hydrogenous material from the cement. The treatment method allows for on-line process monitoring of leachates and can be transported into the field. We will describe the general features of supercritical fluids, as well as the application of these fluids to the treatment of solid and semi-solid waste forms. some of the issues concerning the economic feasibility of industrial scale-up will be addressed, with particular attention to the engineering requirements for the establishment of on-site processing facilities. Finally, the initial results of physical property measurements made on portland cements before and after supercritical fluid processing will be presented.

  10. Enhancement of cemented waste forms by supercritical CO2 carbonation of standard portland cements

    We are conducting experiments on an innovative transformation concept, using a traditional immobilization technique, that may significantly reduce the volume of hazardous or radioactive waste requiring transport and long-term storage. The standard practice for the stabilization of radioactive salts and residues is to mix them with cements, which may include additives to enhance immobilization. Many of these wastes do not qualify for underground disposition, however, because they do not meet disposal requirements for free liquids, decay heat, head-space gas analysis, and/or leachability. The treatment method alters the bulk properties of a cemented waste form by greatly accelerating the natural cement-aging reactions, producing a chemically stable form having reduced free liquids, as well as reduced porosity, permeability and pH. These structural and chemical changes should allow for greater actinide loading, as well as the reduced mobility of the anions, cations, and radionuclides in aboveground and underground repositories. Simultaneously, the treatment process removes a majority of the hydrogenous material from the cement. The treatment method allows for on-line process monitoring of leachates and can be transported into the field. We will describe the general features of supercritical fluids, as well as the application of these fluids to the treatment of solid and semi-solid waste forms. some of the issues concerning the economic feasibility of industrial scale-up will be addressed, with particular attention to the engineering requirements for the establishment of on-site processing facilities. Finally, the initial results of physical property measurements made on portland cements before and after supercritical fluid processing will be presented

  11. A study on the acceptance criteria of radioactive waste form

    It is essential to accept well solidified and packaged waste forms for the safety during the operational and post operational phase in the repository, and for this, waste the acceptance criterion is necessary for the distinction of the well solidified and packaged waste form. The objective of this report is to provide the preliminary acceptance criteria to help the later establishment of final acceptance criteria. The following factors were considered for establishing the preliminary waste acceptance criteria. 1) Matrix and waste form characteristics 2) the type of repository and its characteristics 3) establishment procedure of acceptance criteria and its technical background From this study, a qualitative preliminary criterion including the radionuclide contents, surface dose, surface contamination and so on was established. (Author)

  12. Waste Acceptance Testing of Secondary Waste Forms: Cast Stone, Ceramicrete and DuraLith

    Mattigod, Shas V.; Westsik, Joseph H.; Chung, Chul-Woo; Lindberg, Michael J.; Parker, Kent E.

    2011-08-12

    To support the selection of a waste form for the liquid secondary wastes from WTP, Washington River Protection Solutions has initiated secondary-waste-form testing work at Pacific Northwest National Laboratory (PNNL). In anticipation of a down-selection process for a waste form for the Solidification Treatment Unit to be added to the ETF, PNNL is conducting tests on four candidate waste forms to evaluate their ability to meet potential waste acceptance criteria for immobilized secondary wastes that would be placed in the IDF. All three waste forms demonstrated compressive strengths above the minimum 3.45 MPa (500 psi) set as a target for cement-based waste forms. Further, none of the waste forms showed any significant degradation in compressive strength after undergoing thermal cycling (30 cycles in a 10 day period) between -40 C and 60 C or water immersion for 90 days. The three leach test methods are intended to measure the diffusion rates of contaminants from the waste forms. Results are reported in terms of diffusion coefficients and a leachability index (LI) calculated based on the diffusion coefficients. A smaller diffusion coefficient and a larger LI are desired. The NRC, in its Waste Form Technical Position (NRC 1991), provides recommendations and guidance regarding methods to demonstrate waste stability for land disposal of radioactive waste. Included is a recommendation to conduct leach tests using the ANS 16.1 method. The resulting leachability index (LI) should be greater than 6.0. For Hanford secondary wastes, the LI > 6.0 criterion applies to sodium leached from the waste form. For technetium and iodine, higher targets of LI > 9 for Tc and LI > 11 for iodine have been set based on early waste-disposal risk and performance assessment analyses. The results of these three leach tests conducted for a total time between 11days (ASTM C1308) to 90 days (ANS 16.1) showed: (1) Technetium diffusivity: ANSI/ANS 16.1, ASTM C1308, and EPA 1315 tests indicated that

  13. Waste Acceptance Testing of Secondary Waste Forms: Cast Stone, Ceramicrete and DuraLith

    To support the selection of a waste form for the liquid secondary wastes from WTP, Washington River Protection Solutions has initiated secondary-waste-form testing work at Pacific Northwest National Laboratory (PNNL). In anticipation of a down-selection process for a waste form for the Solidification Treatment Unit to be added to the ETF, PNNL is conducting tests on four candidate waste forms to evaluate their ability to meet potential waste acceptance criteria for immobilized secondary wastes that would be placed in the IDF. All three waste forms demonstrated compressive strengths above the minimum 3.45 MPa (500 psi) set as a target for cement-based waste forms. Further, none of the waste forms showed any significant degradation in compressive strength after undergoing thermal cycling (30 cycles in a 10 day period) between -40 C and 60 C or water immersion for 90 days. The three leach test methods are intended to measure the diffusion rates of contaminants from the waste forms. Results are reported in terms of diffusion coefficients and a leachability index (LI) calculated based on the diffusion coefficients. A smaller diffusion coefficient and a larger LI are desired. The NRC, in its Waste Form Technical Position (NRC 1991), provides recommendations and guidance regarding methods to demonstrate waste stability for land disposal of radioactive waste. Included is a recommendation to conduct leach tests using the ANS 16.1 method. The resulting leachability index (LI) should be greater than 6.0. For Hanford secondary wastes, the LI > 6.0 criterion applies to sodium leached from the waste form. For technetium and iodine, higher targets of LI > 9 for Tc and LI > 11 for iodine have been set based on early waste-disposal risk and performance assessment analyses. The results of these three leach tests conducted for a total time between 11days (ASTM C1308) to 90 days (ANS 16.1) showed: (1) Technetium diffusivity: ANSI/ANS 16.1, ASTM C1308, and EPA 1315 tests indicated that

  14. Viscosity-based high temperature waste form compositions

    Reimann, G.A.

    1994-12-31

    High-temperature waste forms such as iron-enriched basalt are proposed to immobilize and stabilize a variety of low-level wastes stored at the Idaho National Engineering Laboratory. The combination of waste and soil anticipated for the waste form results in high SiO{sub 2} + Al{sub 2}O{sub 3} producing a viscous melt in an arc furnace. Adding a flux such as CaO to adjust the basicity ratio (the molar ratio of basic to acid oxides) enables tapping the furnace without resorting to extreme temperatures, but adds to the waste volume. Improved characterization of wastes will permit adjusting the basicity ratio to between 0.7 and 1.0 by blending of wastes and/or changing the waste-soil ratio. This minimizes waste form volume. Also, lower pouring temperatures will decrease electrode and refractory attrition, reduce vaporization from the melt, and, with suitable flux, facilitate crystallization. Results of laboratory tests were favorable and pilot-scale melts are planned; however, samples have not yet been subjected to leach testing.

  15. The 'granite encapsulation' route to the safe disposal of Pu and other actinide

    Gibb, F.G.F.; Taylor, K. J.; Burakov, B.E.

    2008-01-01

    Waste actinides, including plutonium, present a long-term management problem and a serious security issue. Immobilisation in mineral or ceramic waste forms for interim storage is a widely proposed first step. The safest, most secure geological disposal for Pu is in very deep boreholes and we propose that the key step to combination of these immobilisation and disposal concepts is encapsulation of the waste form in cylinders of recrystallized granite. We discuss the underpinning science, focus...

  16. The characterization of cement waste form for final disposal of decommissioning concrete wastes

    Highlights: • Decommissioning concrete waste recycling and disposal. • Compressive strength of cement waste form. • Characteristic of thermal resistance and leaching of cement waste form. - Abstract: In Korea, the decontamination and decommissioning of KRR-1, 2 at KAERI have been under way. The decommissioning of the KRR-2 was finished completely by 2011, whereas the decommissioning of KRR-1 is currently underway. A large quantity of slightly contaminated concrete waste has been generated from the decommissioning projects. The concrete wastes, 83ea of 200 L drums, and 41ea of 4 m3 containers, were generated in the decommissioning projects. The conditioning of concrete waste is needed for final disposal. Concrete waste is conditioned as follows: mortar using coarse and fine aggregates is filled with a void space after concrete rubble pre-placement into 200 L drums. Thus, this research developed an optimizing mixing ratio of concrete waste, water, and cement, and evaluated the characteristics of a cement waste form to meet the requirements specified in the disposal site specific waste acceptance criteria. The results obtained from a compressive strength test, leaching test, and thermal cycling test of cement waste forms conclude that the concrete waste, water, and cement have been suggested as an optimized mixing ratio of 75:15:10. In addition, the compressive strength of the cement waste form was satisfied, including a fine powder up to a maximum of 40 wt% in concrete debris waste of about 75%. According to the scale-up test, the mixing ratio of concrete waste, water, and cement is 75:10:15, which meets the satisfied compressive strength because of an increase in the particle size in the waste

  17. Waste form development program. Annual report, October 1982-September 1983

    This report provides a summary of the work conducted for the Waste Form Development/Test Program at Brookhaven National Laboratory in FY 1983 under the sponsorship of the US Department of Energy's Low-Level Waste Management Program. The primary focus of this work is the investigation of new solidification agents which will provide improved immobilization of low-level radioactive wastes in an efficient, cost-effective manner. A working set of preliminary waste form evaluation criteria which could impact upon the movement of radionuclides in the disposal environment was developed. The selection of potential solidification agents for further investigation is described. Two thermoplastic materials, low-density polyethylene and a modified sulfur cement were chosen as primary candidates for further study. Three waste types were selected for solidification process development and waste form property evaluation studies which represent both new volume reduction wastes (dried evaporator concentrates and incinerator ash) and current problem wastes (ion exchange resins). Preliminary process development scoping studies were conducted to verify the compatibility of selected solidification agents and waste types and the potential for improved solidification. Waste loadings of 60 wt % Na2SO4, 25 wt % H3BO3, 25 wt % incinerator ash and 50 wt % dry ion exchange resin were achieved using low density polyethylene as a matrix material. Samples incorporating 65 wt % Na2SO4, 40 wt % H3BO3, 20 wt % incinerator ash and 40 wt % dry ion exchange resin were successfully solidified in modified sulfur cement. Additional improvements are expected for both matrix materials as process parameters are optimized. Several preliminary property evaluation studies were performed to provide the basis for an initial assessment of waste form acceptability. These included a two-week water immersion test and compressive load testing

  18. INERT-MATRIX FUEL: ACTINIDE ''BURNING'' AND DIRECT DISPOSAL

    Excess actinides result from the dismantlement of nuclear weapons (Pu) and the reprocessing of commercial spent nuclear fuel (mainly 241 Am, 244 Cm and 237 Np). In Europe, Canada and Japan studies have determined much improved efficiencies for burnup of actinides using inert-matrix fuels. This innovative approach also considers the properties of the inert-matrix fuel as a nuclear waste form for direct disposal after one-cycle of burn-up. Direct disposal can considerably reduce cost, processing requirements, and radiation exposure to workers

  19. Capillary electrophoresis with laser-induced fluorescent detection method using highly emissive probes for analysis of actinides in radioactive wastes - 59092

    Actinides are important nuclides for the analysis of radioactive wastes arising from nuclear fuel cycle facilities. In order to achieve simple and rapid analysis of actinides, capillary electrophoresis-laser-induced fluorescent detection method (CE-LIF) is one of the potential candidates. In this study, new emissive probes of actinide ions suitable for CE-LIF were developed for the first time. The detection and separation of americium and neptunium ions as model nuclides were examined using several new emissive complexing probes, each of which possessed a fluoro-phore and a different chelating moiety. With a pre-capillary complexation technique without addition of the probe to separation buffer electrolyte, the highly sensitive fluorescent detection of Am and Np was successfully achieved using acyclic and macrocyclic multi-dentate probes. The results suggests that the probe with an acyclic hexa-dentate chelating moiety is suitable for detection and separation of Am and Np. The detection limit of mid-ppt levels was determined. (authors)

  20. Evaluation of solidified high-level waste forms

    One of the objectives of the IAEA waste management programme is to coordinate and promote development of improved technology for the safe management of radioactive wastes. The Agency accomplished this objective specifically through sponsoring Coordinated Research Programmes on the ''Evaluation of Solidified High Level Waste Products'' in 1977. The primary objectives of this programme are to review and disseminate information on the properties of solidified high-level waste forms, to provide a mechanism for analysis and comparison of results from different institutes, and to help coordinate future plans and actions. This report is a summary compilation of the key information disseminated at the second meeting of this programme

  1. A study of uranium and thorium migration at the Koongarra uranium deposit with application to actinide transport from nuclear waste repositories

    One way to gain confidence in modelling possible radionuclide releases is to study natural systems which are similar to components of the multibarrier waste repository. Several such analogues are currently under study and these provide useful data about radionuclide behaviour in the natural environment. One such system is the Koongarra uranium deposit in the Northern Territory. In this dissertation, the migration of actinides, primarily uranium and thorium, has been studied as an analogue for the behaviour of transuranics in the far-field of a waste repository. The major findings of this study are: 1. the main process retarding uranium migration in the dispersion fan at Koongarra is sorption, which suppresses dissolved uranium concentrations well below solubility limits, with ferrihydrite being a major sorbing phase; 2. thorium is extremely immobile, with very low dissolved concentrations and corresponding high distribution ratios for 230Th. Overall, it is estimated that colloids are relatively unimportant in Koongarra groundwater. Uranium migrates mostly as dissolved species, whereas thorium and actinium are mostly adsorbed to larger, relatively immobile particles and the stationary phase. However, of the small amount of 230Th that passes through a 1μm filter, a significant proportion is associated with colloidal particles. Actinium appears to be slightly more mobile than thorium and is associated with colloids to a greater extent, although generally present in low concentrations. These results support the possibility of colloidal transport of trivalent and tetravalent actinides in the vicinity of a nuclear waste repository. 112 refs., 23 tabs., 32 figs

  2. Applications of inductively coupled plasma-mass spectrometry to the determination of actinides and fission products in high level radioactive wastes at the Savannah River Site

    Four years of experience in applying inductively coupled plasma-mass spectrometry (ICP-MS) to the analysis of actinides and fission products in high level waste (HLW) samples at the Savannah River Site has led to the development of a number of techniques to aid in the interpretation of the mass spectral data. The goal has been to develop rapid and reliable analytical procedures that provide the necessary chemical and isotopic information to answer the process needs of the customers. Techniques that have been developed include the writing of computer software to strip the experimental data from the instrumental data files into spreadsheets or into a spectral data processing package so that the raw mass spectra can be overlain for comparison or plotted with higher output resolution. These procedures have been applied to problems ranging from the analysis of the high level waste tanks to reactor moderator water as well as environmental samples. Criticality safety analyses in some HLW waste treatment processes depend upon actinide concentration and isotopic information generated by ICP-MS, particularly in tanks with high concentrations of 137Cs and 90Sr. Experimental results for a number of these applications will be presented. These procedures represent a considerable saving in time and expense as compared to conventional chemical separation followed by radiochemical analyses, as well as decreased radiation exposure for the analysts

  3. Pelleted waste form for high-level ICPP wastes

    Simulated zirconia-type calcined waste is pelletized on a 41-cm diameter disc pelletizer using 5% bentonite, 2% metakaolin, and 2% boric acid as a solid binder and 7M phosphoric plus 4M nitric acid as a liquid binder. After heat treatment at 8000C for 2 hours the pellets are impact resistant and have a leach resistance of 10-4 g/cm2 . day, based on Soxhlet leaching for 100 hours at 950C with distilled water. An integrated pilot plant is being fabricated to verify the process. 1 figure, 4 tables

  4. Research on the chemical speciation of actinides

    A demand for the safe and effective management of spent nuclear fuel and radioactive waste generated from nuclear power plant draws increasing attention with the growth of nuclear power industry. The objective of this project is to establish the basis of research on the actinide chemistry by using advanced laser-based highly sensitive spectroscopic systems. Researches on the chemical speciation of actinides are prerequisite for the development of technologies related to nuclear fuel cycles, especially, such as the safe management of high level radioactive wastes and the chemical examination of irradiated nuclear fuels. For supporting these technologies, laser-based spectroscopies have been performed for the chemical speciation of actinide in an aqueous solutions and the quantitative analysis of actinide isotopes in spent nuclear fuels. In this report, results on the following subjects have been summarized. (1) Development of TRLFS technology for chemical speciation of actinides, (2) Development of LIBD technology for measuring solubility of actinides, (3) Chemical speciation of plutonium complexes by using a LWCC system, (4) Development of LIBS technology for the quantitative analysis of actinides, (5) Development of technology for the chemical speciation of actinides by CE, (6) Evaluation on the chemical reactions between actinides and humic substances, (7) Chemical speciation of actinides adsorbed on metal oxides surfaces, (8) Determination of actinide source terms of spent nuclear fuel

  5. Transuranic contaminated waste form characterization and data base

    McArthur, W.C.; Kniazewycz, B.G.

    1980-07-01

    This report outlines the sources, quantities, characteristics and treatment of transuranic wastes in the United States. This document serves as part of the data base necessary to complete preparation and initiate implementation of transuranic wastes, waste forms, waste container and packaging standards and criteria suitable for inclusion in the present NRC waste management program. No attempt is made to evaluate or analyze the suitability of one technology over another. Indeed, by the nature of this report, there is little critical evaluation or analysis of technologies because such analysis is only appropriate when evaluating a particular application or transuranic waste streams. Due to fiscal restriction, the data base is developed from a myriad of technical sources and does not necessarily contain operating experience and the current status of all technologies. Such an effort was beyond the scope of this report.

  6. Transuranic contaminated waste form characterization and data base

    This report outlines the sources, quantities, characteristics and treatment of transuranic wastes in the United States. This document serves as part of the data base necessary to complete preparation and initiate implementation of transuranic wastes, waste forms, waste container and packaging standards and criteria suitable for inclusion in the present NRC waste management program. No attempt is made to evaluate or analyze the suitability of one technology over another. Indeed, by the nature of this report, there is little critical evaluation or analysis of technologies because such analysis is only appropriate when evaluating a particular application or transuranic waste streams. Due to fiscal restriction, the data base is developed from a myriad of technical sources and does not necessarily contain operating experience and the current status of all technologies. Such an effort was beyond the scope of this report

  7. Radioactive Waste Minimization by Electrolytic Extraction and Destruction in a Purex-Truex Actinide Separation System

    Electrolytic extraction of noble metals from nitric acid media was investigated. The largest deposition yield was obtained for Pd, supported by its large rate constants. Rate constants of RuNO3+ and ReO4- were, however, smaller than that of Pd2+; their yield can be improved under high cathode current supply in lower nitric acid concentration. Rather high apparent activation energy was observed for the deposition of RuNO3+. Peculiar masking or synergistic effects in their electrodeposition behaviors might be due to mutual interaction of RuNO3+, Pd2+ with ReO4- in nitric acid solution. Sufficiently different redissolution potentials for deposited metals indicate their fractional recovery by anode processing.Mediatory electrochemical oxidation (MEO) was investigated for the mineralization of waste OφD[iB]CMPO (hereafter CMPO) by burning its bulky hydrocarbon moiety under the existence of various kinds of metal ions. Only Ag2+/+ offered high-current efficiency up to 75%, fairly exceeding that by direct electrooxidation. Redox coupling characterized by a simple electron transfer, Mm+ + ne- M(m-n)+ provided high E0, will act exactly as an active mediator. As for the destruction paths for CMPO by MEO, cleavage between carbonyl C and N of amide moiety was of principal importance. The coupling of Co3+/2+ is also recommended because of hydraulic advantages

  8. Analytical electron microscopy study of radioactive ceramic waste forms

    A ceramic waste form has been developed to immobilize the halide high-level waste stream from electrometallurgical treatment of spent nuclear fuel. Analytical electron microscopy studies, using both scanning and transmission instruments, have been performed to characterize the microstructure of this material. The microstructure consists primarily of sodalite granules (containing the bulk of the halides) bonded together with glass. The results of these studies are discussed in detail. Insight into the waste form fabrication process developed as a result of these studies is also discussed

  9. Evolution of 99Tc Species in Cementitious Nuclear Waste Form

    Technetium (Tc) is produced in large quantities as a fission product during the irradiation of 235U-enriched fuel for commercial power production and plutonium genesis for nuclear weapons. The most abundant isotope of Tc present in the wastes is 99Tc because of its high fission yield (∼6%) and long half-life (2.13x105 years). During the Cold War era, generation of fissile 239Pu for use in America's atomic weapons arsenal yielded nearly 1900 kg of 99Tc at the U.S. Department of Energy's (DOE) Hanford Site in southeastern Washington State. Most of this 99Tc is present in fuel reprocessing wastes temporarily stored in underground tanks awaiting retrieval and permanent disposal. After the wastes are retrieved from the storage tanks, the bulk of the high-level waste (HLW) and lowactivity waste (LAW) stream is scheduled to be converted into a borosilicate glass waste form that will be disposed of in a shallow burial facility called the Integrated Disposal Facility (IDF) at the Hanford Site. Even with careful engineering controls, volatilization of a fraction of Tc during the vitrification of both radioactive waste streams is expected. Although this volatilized Tc can be captured in melter off-gas scrubbers and returned to the melter, some of the Tc is expected to become part of the secondary waste stream from the vitrification process. The off-gas scrubbers downstream from the melters will generate a high pH, sodium-ammonium carbonate solution containing the volatilized Tc and other fugitive species. Effective and cost-efficient disposal of Tc found in the off-gas scrubber solution remains difficult. A cementitious waste form (Cast Stone) is one of the nuclear waste form candidates being considered to solidify the secondary radioactive liquid waste that will be generated by the operation of the waste treatment plant (WTP) at the Hanford Site. Because Tc leachability from the waste form is closely related with Tc speciation or oxidation state in both the simulant and

  10. Mathematical modeling of the effects of aerobic and anaerobic chelate biodegradation on actinide speciation

    Biodegradation of natural and anthropogenic chelating agents directly and indirectly affects the speciation, and, hence, the mobility of actinides in subsurface environments. We combined mathematical modeling with laboratory experimentation to investigate the effects of aerobic and anaerobic chelate biodegradation on actinide [Np(IV/V), Pu(IV)] speciation. Under aerobic conditions, nitrilotriacetic acid (NTA) biodegradation rates were strongly influenced by the actinide concentration. Actinide-chelate complexation reduced the relative abundance of available growth substrate in solution and actinide species present or released during chelate degradation were toxic to the organisms. Aerobic bio-utilization of the chelates as electron-donor substrates directly affected actinide speciation by releasing the radionuclides from complexed form into solution, where their fate was controlled by inorganic ligands in the system. Actinide speciation was also indirectly affected by pH changes caused by organic biodegradation. The two concurrent processes of organic biodegradation and actinide aqueous chemistry were accurately linked and described using CCBATCH, a computer model developed at Northwestern University to investigate the dynamics of coupled biological and chemical reactions in mixed waste subsurface environments. CCBATCH was then used to simulate the fate of Np during anaerobic citrate biodegradation. The modeling studies suggested that, under some conditions, chelate degradation can increase Np(IV) solubility due to carbonate complexation in closed aqueous systems

  11. Mathematical modelling of the effects of aerobic and anaerobic chelate biodegradation on actinide speciation

    Biodegradation of natural and anthropogenic chelating agents directly and indirectly affects the speciation, and hence, the mobility of actinides in subsurface environments. We combined mathematical modelling with laboratory experimentation to investigate the effects of aerobic and anaerobic chelate biodegradation on actinide [Np(IV/V), Pu(IV)] speciation. Under aerobic conditions, nitrilotriacetic acid (NTA) biodegradation rates were strongly influenced by the actinide concentration. Actinide-chelate complexation reduced the relative abundance of available growth substrate in solution and actinide species present or released during chelate degradation were toxic to the organisms. Aerobic bioutilization of the chelates as electron-donor substrates directly affected actinide speciation by releasing the radionuclides from complexed form into solution, where their fate was controlled by inorganic ligands in the system. Actinide speciation was also indirectly affected by pH changes caused by organic biodegradation. The two concurrent processes of organic biodegradation and actinide aqueous chemistry were accurately linked and described using CCBATCH, a computer model developed at Northwestern University to investigate the dynamics of coupled biological and chemical reactions in mixed waste subsurface environments. CCBATCH was then used to simulate the fate of Np during anaerobic citrate biodegradation. The modelling studies suggested that, under some conditions, chelate degradation can increase Np(IV) solubility due to carbonate complexation in closed aqueous systems. (orig.)

  12. Comparative assessment of TRU waste forms and processes. Volume II. Waste form data, process descriptions, and costs

    This volume contains supporting information for the comparative assessment of the transuranic waste forms and processes summarized in Volume I. Detailed data on the characterization of the waste forms selected for the assessment, process descriptions, and cost information are provided. The purpose of this volume is to provide additional information that may be useful when using the data in Volume I and to provide greater detail on particular waste forms and processes. Volume II is divided into two sections and two appendixes. The first section provides information on the preparation of the waste form specimens used in this study and additional characterization data in support of that in Volume I. The second section includes detailed process descriptions for the eight processes evaluated. Appendix A lists the results of MCC-1 leach test and Appendix B lists additional cost data. 56 figures, 12 tables

  13. Glass-ceramic waste forms for immobilizing plutonium

    Results are reported on several new glass and glass-ceramic waste formulations for plutonium disposition. The approach proposed involves employing existing calcined high level waste (HLW) present at the Idaho Chemical Processing Plant (ICPP) and an additive to: (1) aid in the formation of a durable waste form and (2) decrease the attractiveness level of the plutonium from a proliferation viewpoint. The plutonium, PuO2, loadings employed were 15 wt% (glass) and 17 wt% (glass-ceramic). Results in the form of x-ray diffraction patterns, microstructure and durability tests are presented on cerium surrogate and plutonium loaded waste forms using simulated calcined HLW and demonstrate that durable phases, zirconia and zirconolite, contain essentially all the plutonium

  14. Glass-ceramic waste forms for immobilizing plutonium

    O`Holleran, T.P.; Johnson, S.G.; Frank, S.M.; Meyer, M.K.; Noy, M.; Wood, E.L. [Argonne National Lab.-West, Idaho Falls, ID (United States); Knecht, D.A.; Vinjamuri, K.; Staples, B.A. [Lockheed Martin Idaho Technologies Co., Idaho Falls, ID (United States)

    1997-12-31

    Results are reported on several new glass and glass-ceramic waste formulations for plutonium disposition. The approach proposed involves employing existing calcined high level waste (HLW) present at the Idaho Chemical Processing Plant (ICPP) and an additive to: (1) aid in the formation of a durable waste form and (2) decrease the attractiveness level of the plutonium from a proliferation viewpoint. The plutonium, PuO{sub 2}, loadings employed were 15 wt% (glass) and 17 wt% (glass-ceramic). Results in the form of x-ray diffraction patterns, microstructure and durability tests are presented on cerium surrogate and plutonium loaded waste forms using simulated calcined HLW and demonstrate that durable phases, zirconia and zirconolite, contain essentially all the plutonium.

  15. Forming artificial soils from waste materials for mine site rehabilitation

    Yellishetty, Mohan; Wong, Vanessa; Taylor, Michael; Li, Johnson

    2014-05-01

    Surface mining activities often produce large volumes of solid wastes which invariably requires the removal of significant quantities of waste rock (overburden). As mines expand, larger volumes of waste rock need to be moved which also require extensive areas for their safe disposal and containment. The erosion of these dumps may result in landform instability, which in turn may result in exposure of contaminants such as trace metals, elevated sediment delivery in adjacent waterways, and the subsequent degradation of downstream water quality. The management of solid waste materials from industrial operations is also a key component for a sustainable economy. For example, in addition to overburden, coal mines produce large amounts of waste in the form of fly ash while sewage treatment plants require disposal of large amounts of compost. Similarly, paper mills produce large volumes of alkaline rejected wood chip waste which is usually disposed of in landfill. These materials, therefore, presents a challenge in their use, and re-use in the rehabilitation of mine sites and provides a number of opportunities for innovative waste disposal. The combination of solid wastes sourced from mines, which are frequently nutrient poor and acidic, with nutrient-rich composted material produced from sewage treatment and alkaline wood chip waste has the potential to lead to a soil suitable for mine rehabilitation and successful seed germination and plant growth. This paper presents findings from two pilot projects which investigated the potential of artificial soils to support plant growth for mine site rehabilitation. We found that pH increased in all the artificial soil mixtures and were able to support plant establishment. Plant growth was greatest in those soils with the greatest proportion of compost due to the higher nutrient content. These pot trials suggest that the use of different waste streams to form an artificial soil can potentially be used in mine site rehabilitation

  16. The analysis and handling concept of minor actinides of NPP’s waste by using Ads technology

    The contents of minor actinide elements (americium, neptunium and curium) on the spent fuel inventory from PWR operation of NPP have been calculated using Vista program. The calculation used parameters: enrichment 3.968%, power 1000 M We and burn-up is 60 M Wd/kg. The result of calculation showed that the arising of minor actinide elements on the spent fuel is 16.205 kg/year and 43.471 kg/year for PWR-UOX and PWR-MOX respectively. It is also discussed a concept of the use of ADS technology for transmuting the minor actinide elements contained in spent fuels. The result of the discussion showed that an ADS of 400 M Wth will serve 7 PWRs-UOX, and on the PWR system using UOX and MOX fuels an ADS will serve 3 PWRs. (author)

  17. Cement waste-form development for ion-exchange resins at the Rocky Flats Plant

    This report describes the development of a cement waste form to stabilize ion-exchange resins at Rocky Flats Environmental Technology Site (RFETS). These resins have an elevated potential for ignition due to inadequate wetness and contact with nitrates. The work focused on the preparation and performance evaluation of several Portland cement/resin formulations. The performance standards were chosen to address Waste Isolation Pilot Plant and Environmental Protection Agency Resource Conservation and Recovery Act requirements, compatibility with Rocky Flats equipment, and throughput efficiency. The work was performed with surrogate gel-type Dowex cation- and anion-exchange resins chosen to be representative of the resin inventory at RFETS. Work was initiated with nonactinide resins to establish formulation ranges that would meet performance standards. Results were then verified and refined with actinide-containing resins. The final recommended formulation that passed all performance standards was determined to be a cement/water/resin (C/W/R) wt % ratio of 63/27/10 at a pH of 9 to 12. The recommendations include the acceptable compositional ranges for each component of the C/W/R ratio. Also included in this report are a recommended procedure, an equipment list, and observations/suggestions for implementation at RFETS. In addition, information is included that explains why denitration of the resin is unnecessary for stabilizing its ignitability potential

  18. Actinide recovery techniques utilizing electromechanical processes

    Under certain conditions, the separation of actinides using electromechanical techniques may be an effective means of residue processing. The separation of granular mixtures of actinides and other materials discussed in this report is based on appreciable differences in the magnetic and electrical properties of the actinide elements. In addition, the high density of actinides, particularly uranium and plutonium, may render a simultaneous separation based on mutually complementary parameters. Both high intensity magnetic separation and electrostatic separation have been investigated for the concentration of an actinide waste stream. Waste stream constituents include an actinide metal alloy and broken quartz shards. The investigation of these techniques is in support of the Integral Fast Reactor (IFR) concept currently being developed at Argonne National Laboratory under the auspices of the Department of Energy

  19. Immobilization in ceramic waste forms of the residues from treatment of mixed wastes

    The Environmental Restoration and Waste Management Applied Technology Program at LLNL is developing a Mixed Waste Management Facility to demonstrate treatment technologies that provide an alternative to incineration. As part of that program, we are developing final waste forms using ceramic processing methods for the immobilization of the treatment process residues. The ceramic phase assemblages are based on using Synroc D as a starting point and varying the phase assemblage to accommodate the differences in chemistry between the treatment process residues and the defense waste for which Synroc D was developed. Two basic formulations are used, one for low ash residues resulting from treatment of organic materials contaminated with RCRA metals, and one for high ash residues generated from the treatment of plastics and paper products. Treatment process residues are mixed with ceramic precursor materials, dried, calcined, formed into pellets at room temperature, and sintered at 1150 to 1200 degrees C to produce the final waste form. This paper discusses the chemical composition of the waste streams and waste forms, the phase assemblages that serve as hosts for inorganic waste elements, and the changes in waste form characteristics as a function of variation in process parameters

  20. Study of natural zircon-xenotime assemblages for estimation of the actinide waste forms stability

    In order to estimate compositions and structural stability of YPO4-ZrSiO4-USiO4-ThSiO4 solid solution, natural specimens of (U, Th)-enriched zircon-xenotime assemblages were studied. The samples were picked from granitic pegmatites of North Karelia of about 1,850 Ma age. TEM data show that amorphization of the zircon structure is not complete. Xenotime has typical crystal structure. ASEM and EPMA results indicate that zircon and xenotime are micro-heterogeneous in there compositions. Numerous micro-inclusions (3+ vs. Zr4+ and P5+ vs. Si4+). Data on high amounts of rare earth elements and phosphorus in natural zircons are result from REE-phosphate inclusions in analyzed zircons. Content of U in the zircon allowed the estimation of the solubility of coffinite end member to be no less than 5 mol.% USiO4

  1. Glass Ceramic Waste Forms for Combined CS+LN+TM Fission Products Waste Streams

    Crum, Jarrod V.; Turo, Laura A.; Riley, Brian J.; Tang, Ming; Kossoy, Anna; Sickafus, Kurt E.

    2010-09-23

    In this study, glass ceramics were explored as an alternative waste form for glass, the current baseline, to be used for immobilizing alkaline/alkaline earth + lanthanide (CS+LN) or CS+LN+transition metal (TM) fission-product waste streams generated by a uranium extraction (UREX+) aqueous separations type process. Results from past work on a glass waste form for the combined CS+LN waste streams showed that as waste loading increased, large fractions of crystalline phases precipitated upon slow cooling.[1] The crystalline phases had no noticeable impact on the waste form performance by the 7-day product consistency test (PCT). These results point towards the development of a glass ceramic waste form for treating CS+LN or CS+LN+TM combined waste streams. Three main benefits for exploring glass ceramics are: (1) Glass ceramics offer increased solubility of troublesome components in crystalline phases as compared to glass, leading to increased waste loading; (2) The crystalline network formed in the glass ceramic results in higher heat tolerance than glass; and (3) These glass ceramics are designed to be processed by the same melter technology as the current baseline glass waste form. It will only require adding controlled canister cooling for crystallization into a glass ceramic waste form. Highly annealed waste form (essentially crack free) with up to 50X lower surface area than a typical High-Level Waste (HLW) glass canister. Lower surface area translates directly into increased durability. This was the first full year of exploring glass ceramics for the Option 1 and 2 combined waste stream options. This work has shown that dramatic increases in waste loading are achievable by designing a glass ceramic waste form as an alternative to glass. Table S1 shows the upper limits for heat, waste loading (based on solubility), and the decay time needed before treatment can occur for glass and glass ceramic waste forms. The improvements are significant for both combined waste

  2. A comparative evaluation of selected alternative nuclear waste forms

    Mechanical strength, volatility and leach resistance tests have been conducted on ten representative alternative waste form materials. Glass PNL 76-68, celsian glass ceramic, and SPC-5B supercalcine waste forms ranked the highest in overall performance while the 100% PW-9 calcine forms had the least desirable properties. Glass PNL 76-68 had the highest mechanical strength, measured by diametral compression; both glass PNL 76-68 and SPC-5B supercalcine have volatile losses less than 3 x 10-2 mg/mm2 at temperatures below 11000C. These two waste forms also provided the best overall leach resistance. Processing techniques such as hot pressing or hot isostatic pressing did not produce a significantly better product over conventional cold press and sintering techniques for SPC-5B supercalcine or PW-9 calcine. (Auth.)

  3. Technetium Waste Form Development - Progress Report

    Gelles, David S.; Ermi, Ruby M.; Buck, Edgar C.; Seffens, Rob J.; Chamberlin, Clyde E.

    2009-01-07

    Analytical electron microscopy using SEM and TEM has been used to analyze a ~5 g. ingot with composition 71.3 wt% 316SS-5.3 wt% Zr-13.2 wt% Mo-4.0 wt% Rh-6.2 wt% Re prepared at the Idaho National Laboratory. Four phase fields have been identified two of which are lamellar eutectics, with a fifth possibly present. A Zr rich phase was found distributed as fine precipitate, ~10µm in diameter, often coating large cavities. A Mo-Fe-Re-Cr lamellar eutectic phase field appears as blocky regions ~30µm in diameter, surrounded by a Fe-Mo-Cr lamellar eutectic phase field, and that in turn is surrounded by a Zr-Fe-Rh-Mo-Ni phase field. The eutectic phase separation reactions are different. The Mo-Fe-Re-Cr lamellar eutectic appears a result of austenitic steel forming at lower volume fraction within an Mo-Fe-Re intermetallic phase, whereas the Fe-Mo-Cr lamellar eutectic may be a result of the same intermetallic phase forming within a ferritic steel phase. Cavitation may have arisen either as a result of bubbles, or from loss of equiaxed particles during specimen preparation.

  4. Technetium Waste Form Development - Progress Report

    Analytical electron microscopy using SEM and TEM has been used to analyze a ∼5 g. ingot with composition 71.3 wt% 316SS-5.3 wt% Zr-13.2 wt% Mo-4.0 wt% Rh-6.2 wt% Re prepared at the Idaho National Laboratory. Four phase fields have been identified two of which are lamellar eutectics, with a fifth possibly present. A Zr rich phase was found distributed as fine precipitate, ∼10 (micro)m in diameter, often coating large cavities. A Mo-Fe-Re-Cr lamellar eutectic phase field appears as blocky regions ∼30 (micro)m in diameter, surrounded by a Fe-Mo-Cr lamellar eutectic phase field, and that in turn is surrounded by a Zr-Fe-Rh-Mo-Ni phase field. The eutectic phase separation reactions are different. The Mo-Fe-Re-Cr lamellar eutectic appears a result of austenitic steel forming at lower volume fraction within an Mo-Fe-Re intermetallic phase, whereas the Fe-Mo-Cr lamellar eutectic may be a result of the same intermetallic phase forming within a ferritic steel phase. Cavitation may have arisen either as a result of bubbles, or from loss of equiaxed particles during specimen preparation.

  5. Actinide extraction from ICPP sodium bearing waste with 0.75 M DHDECMP/TBP in Isopar L reg-sign

    Recent process development efforts at the Idaho Chemical Processing Plant include examination of solvent extraction technologies for actinide partitioning from sodium bearing waste (SBW) solutions. The use of 0.75 M dihexyl-N, N-diethylcarbamoylmethylphosphonate (DHDECMP or simply CMP) and 1.0 M tri-n-butyl phosphate (TBP) diluted in Isopar L reg-sign was explored for actinide removal from simulated SBW solutions. Experimental evaluations included batch contacts in radiotracer tests with simulated sodium bearing waste solution to measure the extraction and recovery efficiency of the organic solvent. The radioactive isotopes utilized for this study included Pu-238, Pu-239, Am-241, U-233, Np-239, Zr-95, Tc-99m, and Hg-203. Extraction contacts of the organic solvent with the traced SBW stimulant, strip (back-extraction) contacts of the loaded organic solvent with either a 1-hydroxyethane-1, 1-diphosphonic acid (HEDPA) in nitric acid solution or an oxalic acid in nitric acid solution, and solvent wash contacts with sodium carbonate were performed

  6. NNWSI [Nevada Nuclear Waste Storage Investigation] waste form testing at Argonne National Laboratory: Semiannual report, July--December 1987

    Tests are ongoing at Argonne National Laboratory to examine the reaction of glass with water under conditions that may exist in the proposed repository at Yucca Mountain, Nevada. Examination of glass reaction using the Unsaturated Test method as applied to simulated defense glass (SRL 165 black frit based) and simulated West Valley glass (ATM-10) is ongoing. The tests on SRL 165 glass have been ongoing for 104 weeks with nonstoichiometric release of Li, Na, B, and actinide elements being observed throughout the test period. The tests on ATM-10 glass have been in progress for 26 weeks and it is too early in the test cycle to assess the glass reaction. The influence of penetrating gamma radiation on the reaction of synthetic nuclear waste glasses in tuff groundwater was also investigated. Modified MCC-1 static leaching experiments were performed under radiation exposures of 1 /times/ 103 R/h and O R/h at 90/degree/C. The groundwater was acidified by nitrous and nitric acids radiolytically produced in the air. The high bicarbonate ion concentration of the groundwater prevented the pH from dropping below 6.4, however. The glass reaction, as measured by the release of glass species and the thickness of an alteration layer formed on the glass surface, was not measurably affected by radiation. 24 refs., 34 figs., 20 tabs

  7. Hot and cold pressing of (La,Ce)PO4-based nuclear waste forms

    Synthetic analogs of the mineral monazite [(Ce,La,Ca,Th,U)(P,Si)O4] are promising host phases for the isolation of actinide wastes. In the present investigation, the optimal conditions necessary to form high-density, simulated waste pellets from calcined LaPO4 and CePO4 powders have been examined. Pellets that are close to the theoretical density are necessary in order to minimize porosity and hence potential avenues along which fluid/waste interactions can take place. Calcined powders prepared by a urea precipitation process were cold pressed and hot pressed under a range of controlled conditions to form coherent, cylindrical pellets. Changes in density were examined as a function of pressure, temperature and duration of sintering. For cold-pressed pellets, a significant increase in density occurs during sintering between 10000C and 11000C. This increase is correlated with substantial grain coarsening of the pellet microstructure. A comparison of cold and hot pressing techniques suggests that, only after sintering, does the density of cold-pressed pellets approach (but not equal) that of the hot-pressed pellets. Densities >90% of the theoretical value of 5.11 g/cm3 are easily attainable by hot pressing without sintering. The significance of density differences on pellet stability will be investigated in future leaching studies. The apparent advantages of the higher densities achieved by hot pressing must be weighed against the increased technological/engineering complexities involved when working at sustained high temperatures in a remote environment. Thus the cold pressing technique may ultimately prove more practical for large-scale commercial operations

  8. Consolidated waste forms: glass marbles and ceramic pellets

    Glass marbles and ceramic pellets have been developed at Pacific Northwest Laboratory as part of the multibarrier concept for immobilizing high-level radioactive waste. These consolidated waste forms served as substrates for the application of various inert coatings and as ideal-sized particles for encapsulation in protective matrices. Marble and pellet formulations were based on existing defense wastes at Savannah River Plant and proposed commercial wastes. To produce marbles, glass is poured from a melter in a continuous stream into a marble-making device. Marbles were produced at PNL on a vibratory marble machine at rates as high as 60 kg/h. Other marble-making concepts were also investigated. The marble process, including a lead-encapsulation step, was judged as one of the more feasible processes for immobilizing high-level wastes. To produce ceramic pellets, a series of processing steps are required, which include: spray calcining - to dry liquid wastes to a powder; disc pelletizing - to convert waste powders to spherical pellets; sintering - to densify pellets and cause desired crystal formation. These processing steps are quite complex, and thereby render the ceramic pellet process as one of the least feasible processes for immobilizing high-level wastes

  9. Consolidated waste forms: glass marbles and ceramic pellets

    Treat, R.L.; Rusin, J.M.

    1982-05-01

    Glass marbles and ceramic pellets have been developed at Pacific Northwest Laboratory as part of the multibarrier concept for immobilizing high-level radioactive waste. These consolidated waste forms served as substrates for the application of various inert coatings and as ideal-sized particles for encapsulation in protective matrices. Marble and pellet formulations were based on existing defense wastes at Savannah River Plant and proposed commercial wastes. To produce marbles, glass is poured from a melter in a continuous stream into a marble-making device. Marbles were produced at PNL on a vibratory marble machine at rates as high as 60 kg/h. Other marble-making concepts were also investigated. The marble process, including a lead-encapsulation step, was judged as one of the more feasible processes for immobilizing high-level wastes. To produce ceramic pellets, a series of processing steps are required, which include: spray calcining - to dry liquid wastes to a powder; disc pelletizing - to convert waste powders to spherical pellets; sintering - to densify pellets and cause desired crystal formation. These processing steps are quite complex, and thereby render the ceramic pellet process as one of the least feasible processes for immobilizing high-level wastes.

  10. Weathering Effect on 99Tc Leachability from Cementitious Waste Form

    The mass transfer of contaminants from the solid phase to the waste form pore water, and subsequently out of the solid waste form, is directly related to the number and size distribution of pores as well as the microstructure of the waste form. Because permeability and porosity are controlled by pore aperture size, pore volume, and pore distribution, it is important to have some indication of how these characteristics change in the waste form during weathering. Knowledge of changes in these key parameters can be used to develop predictive models that estimate diffusivity or permeability of radioactive contaminants can be used to develop predictive models that estimate diffusivity or permeability of radioactive contaminants from waste forms for long-term performance assessment. It is known that dissolution or precipitation of amorphous/crystalline phases within waste forms alters their pore structure and controls the transport of contaminants our of waste forms. One very important precipitate is calcite, which is formed as a result of carbonation reactions in cement and other high-alkalinity waste forms. Enhanced oxidation can also increase Tc leachability from the waste form. To account for these changes, weathering experiments were conducted in advance to increase our understating of the long-term Tc leachability, especially out of the cementitious waste form. Pore structure analysis was characterized using both N2 absorption analysis and XMT techniques, and the results show that cementitious waste form is a relatively highly-porous material compared to other waste forms studied in this task, Detailed characterization of Cast Stone chunks and monolith specimens indicate that carbonation reactions can change the Cast Stone pore structure, which in turn may correlate with Tc leachability. Short carbonation reaction times for the Cast Stone causes pore volume and surface area increases, while the average pore diameter decreases. Based on the changes in pore volumes

  11. Solid forms for Savannah River Plant radioactive wastes

    Methods are being developed to immobilize Savannah River Plant wastes in solid forms such as cement, asphalt, or glass. 137Cs and 90Sr are the major biological hazards and heat producers in the alkaline wastes produced at SRP. In the conceptual process being studied, 137Cs removed from alkaline supernates, together with insoluble sludges that contain 90Sr, will be incorporated into solid forms of high integrity and low volume suitable for storage in a retrievable surface storage facility for about 100 years, and for eventual shipment to an off-site repository. Mineralization of 137Cs, or its fixation on zeolite prior to incorporation into solid forms, is also being studied. Economic analyses to reduce costs and fault-tree analyses to minimize risks are being conducted. Methods are being studied for removal of sludge from (and final decontamination of) waste tanks

  12. Electrochemical Corrosion Studies for Modeling Metallic Waste Form Release Rates

    Poineau, Frederic [Univ. of Nevada, Las Vegas, NV (United States); Tamalis, Dimitri [Florida Memorial Univ., Miami Gardens, FL (United States)

    2016-08-01

    The isotope 99Tc is an important fission product generated from nuclear power production. Because of its long half-life (t1/2 = 2.13.105 years) and beta-radiotoxicity (β-= 292 keV), it is a major concern in the long-term management of spent nuclear fuel.1 In the spent nuclear fuel, Tc is present as an alloy with Mo, Ru, Rh, and Pd called the epsilon-phase, the relative amount of which increases with fuel burn-up.2 In some separation schemes for spent nuclear fuel, Tc would be separated from the spent fuel and disposed of in a durable waste form.3 Technetium waste forms under consideration include metallic alloys, oxide ceramics and borosilicate glass.4, 5 In the development of a metallic waste form, after separation from the spent fuel, Tc would be converted to the metal, incorporated into an alloy and the resulting waste form stored in a repository.6 Metallic alloys under consideration include Tc-Zr alloys, Tc-stainless-steel alloys and Tc- Inconel alloys (Inconel is an alloy of Ni, Cr and iron which is resistant to corrosion). To predict the long term behavior of the metallic Tc waste form, understanding the corrosion properties of Tc metal and Tc alloys in various chemical environments is needed but efforts to model the behavior of Tc metallic alloys are limited. 7 One parameter that should also be considered in predicting the long-term behavior of the Tc waste form, is the ingrowth of stable Ru that occurs from the radioactive decay of 99Tc (99Tc "99Ru + β-). After a geological period of time, significant amount of Ru will be present in the Tc and may affect its corrosion properties. Studying the effect of Ru on the corrosion behavior of Tc is also of importance.

  13. PF-4 actinide disposition strategy

    The dwindling amount of Security Category I processing and storage space across the DOE Complex has driven the need for more effective storage of nuclear materials at LANL's Plutonium Facility's (PF-4's) vault. An effort was begun in 2009 to create a strategy, a roadmap, to identify all accountable nuclear material and determine their disposition paths, the PF-4 Actinide Disposition Strategy (PADS). Approximately seventy bins of nuclear materials with similar characteristics - in terms of isotope, chemical form, impurities, disposition location, etc. - were established in a database. The ultimate disposition paths include the material to remain at LANL, disposition to other DOE sites, and disposition to waste. If all the actions described in the document were taken, over half of the containers currently in the PF-4 vault would been eliminated. The actual amount of projected vault space will depend on budget and competing mission requirements, however, clearly a significant portion of the current LANL inventory can be either dispositioned or consolidated.

  14. Proposed waste form performance criteria and testing methods for low-level mixed waste

    Proposed waste form performance criteria and testing methods were developed as guidance in judging the suitability of solidified waste as a physico-chemical barrier to releases of radionuclides and RCRA regulated hazardous components. The criteria follow from the assumption that release of contaminants by leaching is the single most important property for judging the effectiveness of a waste form. A two-tier regimen is proposed. The first tier consists of a leach test designed to determine the net, forward leach rate of the solidified waste and a leach test required by the Environmental Protection Agency (EPA). The second tier of tests is to determine if a set of stresses (i.e., radiation, freeze-thaw, wet-dry cycling) on the waste form adversely impacts its ability to retain contaminants and remain physically intact. In the absence of site-specific performance assessments (PA), two generic modeling exercises are described which were used to calculate proposed acceptable leachates

  15. Plan for spent fuel waste form testing for NNWSI [Nevada Nuclear Waste Storage Investigations

    The purpose of spent fuel waste form testing is to determine the rate of release of radionuclides from failed disposal containers holding spent fuel, under conditions appropriate to the Nevada Nuclear Waste Storage Investigations (NNWSI) Project tuff repository. The information gathered in the activities discussed in this document will be used: to assess the performance of the waste package and engineered barrier system (EBS) with respect to the containment and release rate requirements of the Nuclear Regulatory Commission, as the basis for the spent fuel waste form source term in repository-scale performance assessment modeling to calculate the cumulative releases to the accessible environment over 10,000 years to determine compliance with the Environmental Protection Agency, and as the basis for the spent fuel waste form source term in repository-scale performance assessment modeling to calculate cumulative releases over 100,000 years as required by the site evaluation process specified in the DOE siting guidelines. 34 refs

  16. Advanced waste forms research and development. Annual report

    Research and development activities on advanced (alternatives to glass) nuclear waste forms are reported. The emphasis is on two phases of the work to give essential background information on supercalcine development. The first is a report of the data obtained in the study of cesium aluminosilicate for Cs and Ru fixation. Research on the compatibility of the phases formed in the complex oxide system made up of waste and additive cations is reported. The phase stability in a number of proposed formulations was determined

  17. ACTINET: a European Network for Actinide Sciences

    Full text of publication follows: The research in Actinide sciences appear as a strategic issue for the future of nuclear systems. Sustainability issues are clearly in connection with the way actinide elements are managed (either addressing saving natural resource, or decreasing the radiotoxicity of the waste). The recent developments in the field of minor actinide P and T offer convincing indications of what could be possible options, possible future processes for the selective recovery of minor actinides. But they point out, too, some lacks in the basic understanding of key-issues (such as for instance the control An versus Ln selectivity, or solvation phenomena in organic phases). Such lacks could be real obstacles for an optimization of future processes, with new fuel compounds and facing new recycling strategies. This is why a large and sustainable work appears necessary, here in the field of basic actinide separative chemistry. And similar examples could be taken from other aspects of An science, for various applications (nuclear fuel or transmutation targets design, or migration issues,): future developments need a strong, enlarged, scientific basis. The Network ACTINET, established with the support of the European Commission, has the following objectives: - significantly improve the accessibility of the major actinide facilities to the European scientific community, and form a set of pooled facilities, as the corner-stone of a progressive integration process, - improve mobility between the member organisations, in particular between Academic Institutions and National Laboratories holding the pooled facilities, - merge part of the research programs conducted by the member institutions, and optimise the research programs and infrastructure policy via joint management procedures, - strengthen European excellence through a selection process of joint proposals, and reduce the fragmentation of the community by putting critical mass of resources and expertise on

  18. Performance testing of waste forms in a tuff environment

    This paper describes experimental work conducted to establish the chemical composition of water which will have reacted with Topopah Spring Member tuff prior to contact with waste packages. The experimental program to determine the behavior of spent fuel and borosilicate glass in the presence of this water is then described. Preliminary results of experiments using spent fuel segments with defects in the Zircaloy cladding are presented. Some results from parametric testing of a borosilicate glass with tuff and 304L stainless steel are also discussed. Experiments conducted using Topopah Spring tuff and J-13 well water have been conducted to provide an estimate of the post-emplacement environment for waste packages in a repository at Yucca Mountain. The results show that emplacement of waste packages should cause only small changes in the water chemistry and rock mineralogy. The changes in environment should not have any detrimental effects on the performance of metal barriers or waste forms. The NNWSI waste form testing program has provided preliminary results related to the release rate of radionuclides from the waste package. Those results indicate that release rates from both spent fuel and borosilicate glass should be below 1 part in 105 per year. Future testing will be directed toward making release rate testing more closely relevant to site specific conditions. 17 references, 7 figures

  19. The Ceramic Waste Form Process at Idaho National Laboratory

    Stephen Priebe

    2007-05-01

    The treatment of spent nuclear fuel for disposition using an electrometallurgical technique results in two high-level waste forms: a ceramic waste form (CWF) and a metal waste form. Reactive metal fuel constituents, including all the transuranic metals and the majority of the fission products remain in the salt as chlorides and are processed into the CWF. The solidified salt is containerized and transferred to the CWF process where it is ground in an argon atmosphere. Zeolite 4A is ground and then dried in a mechanically-fluidized dryer. The salt and zeolite are mixed in a V-mixer and heated to 500°C to occlude the salt into the structure of the zeolite. The salt-loaded zeolite is cooled, mixed with borosilicate glass frit, and transferred to a crucible, which is placed in a furnace and heated to 925°C. During this process, known as pressureless consolidation, the zeolite is converted to the final sodalite form and the glass thoroughly encapsulates the sodalite, producing a dense, leach-resistant final waste form.

  20. Transuranic waste form characterization and data base. Executive summary

    The Transuranic Waste Form Characterization and Data Base (Volume 1) provides a wide range of information from which a comprehensive data base can be established and from which standards and criteria can be developed for the present NRC waste management program. Supplementary information on each of the areas discussed in Volume 1 is presented in Appendices A through K (Volumes 2 and 3). The structure of the study (Volume 1) is outlined and appendices of Volumes 2 and 3 correlate with each main section of the report. The Executive Summary reviews the sources, quantities, characteristics and treatment of transuranic wastes in the United States. Due to the variety of potential treatment processes for transuranic wastes, the end products for long-term storage may have corresponding variations in quantities and characteristics

  1. Environmental chemistry of the actinide elements

    The environmental chemistry of the actinide elements is a new branch of science developing with the application of nuclear energy on a larger and larger scale. Various aspects of the environmental chemistry of the actinide elements are briefly reviewed in this paper, such as its significance in the nuclear waste disposal, its coverage of research fields and possible directions for future study

  2. Fire testing of fully active medium-level waste forms

    The effect of heat on packaged intermediate level waste (ILW) has been studied. This was done in order to be able to predict the behaviour of the ILW under accident conditions involving fire during transport or at the repository. In the study, experimental data were obtained and used in the development and validation of theoretical models to describe aspects of the behaviour of the waste form when subjected to heat. The prime objective was to be able to predict the amounts of radioactive materials released from a given incident. Four ILW streams were selected for experimental study. These four were chosen as the minimum that could be studied to provide a set of data that could be used in the prediction of the behaviour of the majority of ILW produced in the UK. Heating experiments were carried out on a small scale using packaged ILW samples made from active wastes or inactive simulants. Data were obtained on temperatures in the waste form, production of volatile materials, carry-forward of solid particulate materials and carry-forward of radionuclides. The results were used, together with data from full-scale experiments with inactive simulant ILW carried out at Winfrith, to develop and validate a theoretical model. This model calculates the temperature profiles within a package of immobilized ILW as a function of the applied heating conditions. The temperature of the waste form is used to predict the release of radioactive materials from the package. 4 refs., 65 figs., 13 tabs

  3. SALTSTONE VAULT CLASSIFICATION SAMPLES MODULAR CAUSTIC SIDE SOLVENT EXTRACTION UNIT/ACTINIDE REMOVAL PROCESS WASTE STREAM APRIL 2011

    Eibling, R.

    2011-09-28

    Savannah River National Laboratory (SRNL) was asked to prepare saltstone from samples of Tank 50H obtained by SRNL on April 5, 2011 (Tank 50H sampling occurred on April 4, 2011) during 2QCY11 to determine the non-hazardous nature of the grout and for additional vault classification analyses. The samples were cured and shipped to Babcock & Wilcox Technical Services Group-Radioisotope and Analytical Chemistry Laboratory (B&W TSG-RACL) to perform the Toxic Characteristic Leaching Procedure (TCLP) and subsequent extract analysis on saltstone samples for the analytes required for the quarterly analysis saltstone sample. In addition to the eight toxic metals - arsenic, barium, cadmium, chromium, mercury, lead, selenium and silver - analytes included the underlying hazardous constituents (UHC) antimony, beryllium, nickel, and thallium which could not be eliminated from analysis by process knowledge. Additional inorganic species determined by B&W TSG-RACL include aluminum, boron, chloride, cobalt, copper, fluoride, iron, lithium, manganese, molybdenum, nitrate/nitrite as Nitrogen, strontium, sulfate, uranium, and zinc and the following radionuclides: gross alpha, gross beta/gamma, 3H, 60Co, 90Sr, 99Tc, 106Ru, 106Rh, 125Sb, 137Cs, 137mBa, 154Eu, 238Pu, 239/240Pu, 241Pu, 241Am, 242Cm, and 243/244Cm. B&W TSG-RACL provided subsamples to GEL Laboratories, LLC for analysis for the VOCs benzene, toluene, and 1-butanol. GEL also determines phenol (total) and the following radionuclides: 147Pm, 226Ra and 228Ra. Preparation of the 2QCY11 saltstone samples for the quarterly analysis and for vault classification purposes and the subsequent TCLP analyses of these samples showed that: (1) The saltstone waste form disposed of in the Saltstone Disposal Facility in 2QCY11 was not characteristically hazardous for toxicity. (2) The concentrations of the eight RCRA metals and UHCs identified as possible in the saltstone waste form were present at levels below the UTS. (3) Most of the

  4. Saltstone Vault Classification Samples Modular Caustic Side Solvent Extraction Unit/Actinide Removal Process Waste Stream April 2011

    Savannah River National Laboratory (SRNL) was asked to prepare saltstone from samples of Tank 50H obtained by SRNL on April 5, 2011 (Tank 50H sampling occurred on April 4, 2011) during 2QCY11 to determine the non-hazardous nature of the grout and for additional vault classification analyses. The samples were cured and shipped to Babcock and Wilcox Technical Services Group-Radioisotope and Analytical Chemistry Laboratory (B and W TSG-RACL) to perform the Toxic Characteristic Leaching Procedure (TCLP) and subsequent extract analysis on saltstone samples for the analytes required for the quarterly analysis saltstone sample. In addition to the eight toxic metals - arsenic, barium, cadmium, chromium, mercury, lead, selenium and silver - analytes included the underlying hazardous constituents (UHC) antimony, beryllium, nickel, and thallium which could not be eliminated from analysis by process knowledge. Additional inorganic species determined by B and W TSG-RACL include aluminum, boron, chloride, cobalt, copper, fluoride, iron, lithium, manganese, molybdenum, nitrate/nitrite as Nitrogen, strontium, sulfate, uranium, and zinc and the following radionuclides: gross alpha, gross beta/gamma, 3H, 60Co, 90Sr, 99Tc, 106Ru, 106Rh, 125Sb, 137Cs, 137mBa, 154Eu, 238Pu, 239/240Pu, 241Pu, 241Am, 242Cm, and 243/244Cm. B and W TSG-RACL provided subsamples to GEL Laboratories, LLC for analysis for the VOCs benzene, toluene, and 1-butanol. GEL also determines phenol (total) and the following radionuclides: 147Pm, 226Ra and 228Ra. Preparation of the 2QCY11 saltstone samples for the quarterly analysis and for vault classification purposes and the subsequent TCLP analyses of these samples showed that: (1) The saltstone waste form disposed of in the Saltstone Disposal Facility in 2QCY11 was not characteristically hazardous for toxicity. (2) The concentrations of the eight RCRA metals and UHCs identified as possible in the saltstone waste form were present at levels below the UTS. (3) Most

  5. Managing Inventories of Heavy Actinides

    The Department of Energy (DOE) has stored a limited inventory of heavy actinides contained in irradiated targets, some partially processed, at the Savannah River Site (SRS) and Oak Ridge National Laboratory (ORNL). The 'heavy actinides' of interest include plutonium, americium, and curium isotopes; specifically 242Pu and 244Pu, 243Am, and 244/246/248Cm. No alternate supplies of these heavy actinides and no other capabilities for producing them are currently available. Some of these heavy actinide materials are important for use as feedstock for producing heavy isotopes and elements needed for research and commercial application. The rare isotope 244Pu is valuable for research, environmental safeguards, and nuclear forensics. Because the production of these heavy actinides was made possible only by the enormous investment of time and money associated with defense production efforts, the remaining inventories of these rare nuclear materials are an important part of the legacy of the Nuclear Weapons Program. Significant unique heavy actinide inventories reside in irradiated Mark-18A and Mark-42 targets at SRS and ORNL, with no plans to separate and store the isotopes for future use. Although the costs of preserving these heavy actinide materials would be considerable, for all practical purposes they are irreplaceable. The effort required to reproduce these heavy actinides today would likely cost billions of dollars and encompass a series of irradiation and chemical separation cycles for at least 50 years; thus, reproduction is virtually impossible. DOE has a limited window of opportunity to recover and preserve these heavy actinides before they are disposed of as waste. A path forward is presented to recover and manage these irreplaceable National Asset materials for future use in research, nuclear forensics, and other potential applications.

  6. The effects of radiation on intermediate-level waste forms. Task 3 characterization of radioactive waste forms a series of final reports (1985-89) no. 10

    The purpose of this programme was to determine the effects of radiation on the properties of intermediate-level waste forms relevant to their storage and disposal. It had two overall aims: to provide immediate data on the effect of radiation on important European ILW waste forms through accelerated laboratory tests; and to develop an understanding of the degradation processes so that long-term, low dose rate effects can be predicted with confidence from short-term, high dose rate experiments. The programme included cement waste forms containing inorganic wastes, organic matrix waste forms, and cement waste forms containing a substantial component of organic waste. Irradiations were carried out by external gamma sources and by the incorporation of alpha emitters, such as 238Pu. Irradiated materials included matrix materials, simulated waste forms and real waste forms. 2 figs.; 3 tabs.; 8 refs

  7. State of the art report on bituminized waste forms of radioactive wastes

    In this report, research and development results on the bituminization of radioactive wastes are closely reviewed, especially those regarding waste treatment technologies, waste solidifying procedures and the characteristics of asphalt and solidified forms. A new concept of the bituminization method is suggested in this report which can improve the characteristics of solidified forms. Stable solid forms with high leach resistance, high thermal resistance and good compression strength were produced by the suggested bituminization method, in which spent polyethylene from agricultural farms was added. This report can help further research and development of improved bituminized forms of radioactive wastes that will maintain long term stabilities in disposal sites. (author). 59 refs., 19 tabs., 18 figs

  8. State of the art report on bituminized waste forms of radioactive wastes

    Kim, Tae Kook; Shon, Jong Sik; Kim, Kil Jeong; Lee, Kang Moo; Jung, In Ha

    1998-03-01

    In this report, research and development results on the bituminization of radioactive wastes are closely reviewed, especially those regarding waste treatment technologies, waste solidifying procedures and the characteristics of asphalt and solidified forms. A new concept of the bituminization method is suggested in this report which can improve the characteristics of solidified forms. Stable solid forms with high leach resistance, high thermal resistance and good compression strength were produced by the suggested bituminization method, in which spent polyethylene from agricultural farms was added. This report can help further research and development of improved bituminized forms of radioactive wastes that will maintain long term stabilities in disposal sites. (author). 59 refs., 19 tabs., 18 figs

  9. Actinide separative chemistry

    Actinide separative chemistry has focused very heavy work during the last decades. The main was nuclear spent fuel reprocessing: solvent extraction processes appeared quickly a suitable, an efficient way to recover major actinides (uranium and plutonium), and an extensive research, concerning both process chemistry and chemical engineering technologies, allowed the industrial development in this field. We can observe for about half a century a succession of Purex plants which, if based on the same initial discovery (i.e. the outstanding properties of a molecule, the famous TBP), present huge improvements at each step, for a large part due to an increased mastery of the mechanisms involved. And actinide separation should still focus R and D in the near future: there is a real, an important need for this, even if reprocessing may appear as a mature industry. We can present three main reasons for this. First, actinide recycling appear as a key-issue for future nuclear fuel cycles, both for waste management optimization and for conservation of natural resource; and the need concerns not only major actinide but also so-called minor ones, thus enlarging the scope of the investigation. Second, extraction processes are not well mastered at microscopic scale: there is a real, great lack in fundamental knowledge, useful or even necessary for process optimization (for instance, how to design the best extracting molecule, taken into account the several notifications and constraints, from selectivity to radiolytic resistivity?); and such a need for a real optimization is to be more accurate with the search of always cheaper, cleaner processes. And then, there is room too for exploratory research, on new concepts-perhaps for processing quite new fuels- which could appear attractive and justify further developments to be properly assessed: pyro-processes first, but also others, like chemistry in 'extreme' or 'unusual' conditions (supercritical solvents, sono-chemistry, could be

  10. Degradation modeling of the ANL ceramic waste form

    A ceramic waste form composed of glass-bonded sodalite is being developed at Argonne National Laboratory (ANL) for immobilization and disposition of the molten salt waste stream from the electrometallurgical treatment process for metallic DOE spent nuclear fuel. As part of the spent fuel treatment program at ANL, a model is being developed to predict the long-term release of radionuclides under repository conditions. Dissolution tests using dilute, pH-buffered solutions have been conducted at 40, 70, and 90 C to determine the temperature and pH dependence of the dissolution rate. Parameter values measured in these tests have been incorporated into the model, and preliminary repository performance assessment modeling has been completed. Results indicate that the ceramic waste form should be acceptable in a repository environment

  11. Method of integrally forming radioactive wastes and its vessel

    Object: To introduce pellet-like radioactive waste into a concrete vessel and add a polymeric monomer into said vessel to thereby integrally form the waste and vessel. Structure: The radioactive waste is treated by a dryer to produce dried powder, which is then filled into a concrete vessel in its own state or in the form of pellet. Further, a mixture of unsaturated acid ester such as methyl methacrylate, acrylic ethyl and acrylic methyl, and one or more radical polymeric monomer such as styrene, vinyl acetate, etc., is poured into the concrete vessel together with a polymerization initiator and a polymerization promoter and the vessel is closed. The thus obtained concrete vessel is extremely safe in strength. (Yoshihara, H.)

  12. Mixture for solidification of liquid radioactive wastes into stable forms

    A mixture is proposed for cementing liquid radioactive wastes into chemically stable, mechanically strong, transportable and storable forms. The mixture consists of 60-80 wt.% Portland cement, 5-15 wt.% flue silica dust and 15-25 wt.% zeolitic tuffite. (Z.S.)

  13. Microstructural characterization of glass and ceramic simulated waste forms

    The microstructures of three nonradioactive glass samples simulating three Hanford process waste forms were characterized. Two samples of iodine sodalite which simulate the fixation of radioactive iodine were also characterized. X-ray diffraction, electron microscopy + x-ray energy dispersive spectrometry, and electron microprobe analysis were used in the characterization

  14. Characterization of cement and bitumen waste forms containing simulated low-level waste incinerator ash

    Incinerator ash from the combustion of general trash and ion exchange resins was immobilized in cement and bitumen. Tests were conducted on the resulting waste forms to provide a data base for the acceptability of actual low-level waste forms. The testing was done in accordance with the US Nuclear Regulatory Commission Technical Position on Waste Form. Bitumen had a measured compressive strength of 130 psi and a leachability index of 13 as measured with the ANS 16.1 leach test procedure. Cement demonstrated a compressive strength of 1400 psi and a leachability index of 7. Both waste forms easily exceed the minimum compressive strength of 50 psi and leachability index of 6 specified in the Technical Position. Irradiation to 108 Rad and exposure to 31 thermal cycles ranging from +600) to -300C did not significantly impact these properties. Neither waste form supported bacterial or fungal growth as measured with ASTM G21 and G22 procedures. However, there is some indication of biodegradation due to co-metabolic processes. Concentration of organic complexants in leachates of the ash, cement and bitumen were too low to significantly affect the release of radionuclides from the waste forms. Neither bitumen nor cement containing incinerator ash caused any corrosion or degradation of potential container materials including steel, polyethylene and fiberglass. However, moist ash did cause corrosion of the steel

  15. Technical area status report for low-level mixed waste final waste forms. Volume 2, Appendices

    Mayberry, J.L.; Huebner, T.L. [Science Applications International Corp., Idaho Falls, ID (United States); Ross, W. [Pacific Northwest Lab., Richland, WA (United States); Nakaoka, R. [Los Alamos National Lab., NM (United States); Schumacher, R. [Westinghouse Savannah River Co., Aiken, SC (United States); Cunnane, J.; Singh, D. [Argonne National Lab., IL (United States); Darnell, R. [EG and G Idaho, Inc., Idaho Falls, ID (United States); Greenhalgh, W. [Westinghouse Hanford Co., Richland, WA (United States)

    1993-08-01

    This report presents information on low-level mixed waste forms.The descriptions of the low-level mixed waste (LLMW) streams that are considered by the Mixed Waste Integrated Program (MWIP) are given in Appendix A. This information was taken from descriptions generated by the Mixed Waste Treatment Program (MWTP). Appendix B provides a list of characteristic properties initially considered by the Final Waste Form (FWF) Working Group (WG). A description of facilities available to test the various FWFs discussed in Volume I of DOE/MWIP-3 are given in Appendix C. Appendix D provides a summary of numerous articles that were reviewed on testing of FWFS. Information that was collected by the tests on the characteristic properties considered in this report are documented in Appendix D. The articles reviewed are not a comprehensive list, but are provided to give an indication of the data that are available.

  16. Technical area status report for low-level mixed waste final waste forms

    This report presents information on low-level mixed waste forms.The descriptions of the low-level mixed waste (LLMW) streams that are considered by the Mixed Waste Integrated Program (MWIP) are given in Appendix A. This information was taken from descriptions generated by the Mixed Waste Treatment Program (MWTP). Appendix B provides a list of characteristic properties initially considered by the Final Waste Form (FWF) Working Group (WG). A description of facilities available to test the various FWFs discussed in Volume I of DOE/MWIP-3 are given in Appendix C. Appendix D provides a summary of numerous articles that were reviewed on testing of FWFS. Information that was collected by the tests on the characteristic properties considered in this report are documented in Appendix D. The articles reviewed are not a comprehensive list, but are provided to give an indication of the data that are available

  17. Waste form development for use with ORNL waste treatment facility sludge

    A sludge that simulates Water Softening Sludge number 5 (WSS number 5 filtercake) at Oak Ridge National Laboratory was prepared and evaluated for its thermal behavior, volume reduction, stabilization, surface area and compressive strength properties. Compaction of the surrogate waste and the calcium oxide (produced by calcination) in the presence of paraffin resulted in cylindrical molds with various degrees of stability. This work has demonstrated that surrogate WSS number 5 at ORNL can be successfully stabilized by blending it with about 35 percent paraffin and compacting the mixture at 8000 psi. This compressive strength of the waste form is sufficient for temporary storage of the waste while long-term storage waste forms are developed. Considering the remarkable similarity between the surrogate and the actual filtercake, the findings of this project should be useful for treating the sludge generated by the waste treatment facility at ORNL

  18. The energy amplifier: A solid-phase, accelerator driven, sub critical Th/233 U breeder for nuclear energy production with minimal actinide waste

    We describe a hybrid system consisting of a medium current (1-10 mA), medium energy (1 GeV) proton accelerator feeding a subcritical assembly consisting of Thorium (or another fertile element) and a moderator medium (e.g. light water). Under conditions of moderate neutron flux (1014 ncm-2), we show by a computer simulation that a stable equilibrium evolves whereby the concentration of fissile 233U which is bred from Thorium is stable at about 1.3%. The 233U produces energy by fission and is continuously regenerated in-situ without resorting to any chemical separation. It is shown that the energy produced is several times larger than the energy required to power the proton accelerator, hence the name Energy Amplifier that we have chosen for that system. We have paid particular attention to the question of toxicity and show that this system will result in very small quantities of Plutonium and higher actinide waste. We also show the composition of actinides produced makes this system particularly resistant to nuclear weapons proliferation. This safe subcritical system is based on an abundant and inexpensive resource which is natural Thorium and can be built using present day technology

  19. Study and development of a method allowing the identification of actinides inside nuclear waste packages, by active neutron or photon interrogation and delayed gamma-ray spectrometry

    An accurate estimation of the alpha-activity of a nuclear waste package is necessary to select the best mode of storage. The main purpose of this work is to develop a non-destructive active method, based on the fission process and allowing the identification of actinides (235U, 238U, 239Pu). These three elements are the main alpha emitters contained inside a package. Our technique is based on the detection of delayed gammas emitted by fission products. These latter are created by irradiation with the help of a neutron or photon beam. Performances of this method have been investigated after an Active Photon or Neutron Interrogation (INA or IPA). Three main objectives were fixed in the framework of this thesis. First, we measured many yields of photofission products to compensate the lack of data in the literature. Then, we studied experimental performances of this method to identify a given actinide (239Pu in fission, 235U in photofission) present in an irradiated mixture. Finally, we assessed the application of this technique on different mock-up packages for both types of interrogation (118 l mock-up package containing EVA in fission, 220 l mock-up package with a wall of concrete in photofission). (author)

  20. Cobalt bis(dicarbollide) ions with covalently bonded CMPO groups as selective extraction agents for lanthanide and actinide cations from highly acidic nuclear waste solutions

    A new series of boron substituted cobalt bis(dicarbollide)(1-) ion (1) derivatives of the general formula [(8-CMPO-(CH2-CH2O)2-1,2-C2B9H10)(1',2'-C2B9H11)-3,3'-Co]- (CMPO = Ph2P(O)-CH2C(O)NR, R = C4H9 (3b), -C12H25 (4b), -CH2-C6H5 (5b)) was prepared by ring cleavage of the 8-dioxane-cobalt bis(dicarbollide) (2) bi-polar compound by the respective primary amines and by subsequent reaction of the resulting amino derivatives (3a-5a) with the nitrophenyl ester of diphenyl-phosphoryl-acetic acid. The compounds were synthesized with the aim to develop a new class of more efficient extraction agents for liquid/liquid extraction of polyvalent cations, i.e. lanthanides and actinides, from high-level activity nuclear waste. All compounds were characterized by a combination of 11B NMR, 1H high field NMR, Mass Spectrometry with Electro-spray and MALDI TOF ionisation, HPLC and other techniques. The molecular structure of the supramolecular Ln3+ complex of the anion 5b was determined by single crystal X-ray diffraction analysis. Crystallographic results proved that the Ln(m) atom is bonded to three functionalized cobalt bis(dicarbollide) anions in a charge compensated complex. The cation is tightly coordinated by six oxygen atoms of the CMPO terminal groups (two of each ligand) and by three water molecules completing the metal coordination number to 9. Atoms occupying the primary coordination sphere form a tri-capped trigonal prismatic arrangement. Very high liquid-liquid extraction efficiency of all anionic species was observed. Moreover, less polar toluene can be applied as an auxiliary solvent replacing the less environmentally friendly nitro- and chlorinated solvents used in the current dicarbollide liquid-liquid extraction process. The extraction coefficients are sufficiently high for possible technological applications. (authors)

  1. Impact of actinide recycle on nuclear fuel cycle health risks

    The purpose of this background paper is to summarize what is presently known about potential impacts on the impacts on the health risk of the nuclear fuel cycle form deployment of the Advanced Liquid Metal Reactor (ALMR)1 and Integral Fast Reactor (IF)2 technology as an actinide burning system. In a companion paper the impact on waste repository risk is addressed in some detail. Therefore, this paper focuses on the remainder of the fuel cycle

  2. Europart: European Research programme for partitioning of minor actinides within high active wastes issuing from the reprocessing of spent nuclear fuels

    The radiotoxicity of the vitrified nuclear wastes issuing from the reprocessing of nuclear spent fuels is mainly due to the presence of minor actinides (MAs = Np, Am and Cm) in these wastes. To simplify the definition of a deep underground repository, the elimination of MAs from the wastes followed by their destruction by transmutation is a positive strategy (P and T strategy). The European Integrated Project (IP) EUROPART concerns the definition of partitioning methods for the elimination of MAs from the wastes. Two chemical domains were selected for the research: i) hydrometallurgy, ii) pyrometallurgy. The research work is organised into 9 Work Packages (WP): 5 for hydrometallurgy and 4 for pyrometallurgy. The partnership involved in the research comprises 23 partners from 10 European countries, 1 the EC-JRC-ITU, 1 partner from Japan and 1 partner from Australia. This paper will present: i) the WPs, ii) some recent results related to the WPs, iii) the partnership and the organisation of the IP. (authors)

  3. Investigation of microscopic radiation damage in waste forms using ODNMR and AEM techniques. (EMSP Project Final Report)

    Liu, G.; Luo, J.; Beitz, J.; Li, S.; Williams, C.; Zhorin, V.

    2000-04-21

    This project seeks to understand the microscopic effects of radiation damage in nuclear waste forms. The authors' approach to this challenge encompasses studies of ceramics and glasses containing short-lived alpha- and beta-emitting actinides with electron microscopy, laser and X-ray spectroscopic techniques, and computational modeling and simulations. In order to obtain information on long-term radiation effects on waste forms, much of the effort is to investigate {alpha}-decay induced microscopic damage in 18-year old samples of crystalline yttrium and lutetium orthophosphates that initially contained {approximately} 1(wt)% of the alpha-emitting isotope {sup 244}Cm (18.1 y half life). Studies also are conducted on borosilicate glasses that contain {sup 244}Cm, {sup 241}Am, or {sup 249}Bk, respectively. The authors attempt to gain clear insights into the properties of radiation-induced structure defects and the consequences of collective defect-environment interactions, which are critical factors in assessing the long-term performance of high-level nuclear waste forms.

  4. Investigation of microscopic radiation damage in waste forms using ODNMR and AEM techniques. (EMSP Project Final Report)

    This project seeks to understand the microscopic effects of radiation damage in nuclear waste forms. The authors' approach to this challenge encompasses studies of ceramics and glasses containing short-lived alpha- and beta-emitting actinides with electron microscopy, laser and X-ray spectroscopic techniques, and computational modeling and simulations. In order to obtain information on long-term radiation effects on waste forms, much of the effort is to investigate α-decay induced microscopic damage in 18-year old samples of crystalline yttrium and lutetium orthophosphates that initially contained ∼ 1(wt)% of the alpha-emitting isotope 244Cm (18.1 y half life). Studies also are conducted on borosilicate glasses that contain 244Cm, 241Am, or 249Bk, respectively. The authors attempt to gain clear insights into the properties of radiation-induced structure defects and the consequences of collective defect-environment interactions, which are critical factors in assessing the long-term performance of high-level nuclear waste forms

  5. Research on the chemical speciation of actinides

    A demand for the safe and effective management of spent nuclear fuel and radioactive waste generated from nuclear power plant draws increasing attention with the growth of nuclear power industry. The objective of this project is to establish the basis of research on the actinide chemistry by using highly sensitive and advanced laser-based spectroscopic systems. Researches on the chemical speciation of actinides are prerequisite for the development of technologies related to nuclear fuel cycles, especially, such as the safe management of high level radioactive wastes and the chemical examination of irradiated nuclear fuels. For supporting these technologies, laser-based spectroscopies have been applied for the chemical speciation of actinide in aqueous solutions and the quantitative analysis of actinide isotopes in spent nuclear fuels. In this report, results on the following subjects have been summarized. Development of TRLFS technology for the chemical speciation of actinides, Development of laser-induced photo-acoustic spectroscopy (LPAS) system, Application of LIBD technology to investigate dynamic behaviors of actinides dissolution reactions, Development of nanoparticle analysis technology in groundwater using LIBD, Chemical speciation of plutonium complexes by using a LWCC system, Development of LIBS technology for the quantitative analysis of actinides, Evaluation on the chemical reactions between actinides and humic substances, Spectroscopic speciation of uranium-ligand complexes in aqueous solution, Chemical speciation of actinides adsorbed on metal oxides surfaces

  6. The role of chemical reaction in waste-form performance

    The dissolution rate of waste solids in a geologic repository is a complex function of waste form geometry, chemical raction rate, exterior flow field, and chemical environment. We present here an analysis to determine the stady-state mass transfer rate, over the entire range of flow conditions relevant to geologic disposal of nuclear waste. The equations for steady-state mass transfer with a chemical-reaction-rate boundary condition are solved by three different mathematical techniques which supplement each other. This theory is illustrated with laboratory leach data for borosilicate-glass and a spherical spent-fuel waste form under typical repository conditions. For borosilicate glass waste in the temperature range of 57/degree/C to 250/degree/C, dissolution rate in a repository is determined for a wide range of chemical reaction rates and for Peclet numbers from zero to well over 100, far beyond any Peclet values expected in a repository. Spent-fuel dissolution in a repository is also investigated, based on the limited leach data now available. 10 refs., 4 figs., 1 tab

  7. Chemical compatibility of HLW borosilicate glasses with actinides

    During liquid storage of HLLW the formation of actinide enriched sludges is being expected. Also during melting of HLW glasses an increase of top-to-bottom actinide concentrations can take place. Both effects have been studied. Besides, the vitrification of plutonium enriched wastes from Pu fuel element fabrication plants has been investigated with respect to an isolated vitrification process or a combined one with the HLLW. It is shown that the solidification of actinides from HLLW and actinide waste concentrates will set no principal problems. The leaching of actinides has been measured in salt brine at 230C and 1150C. (orig.)

  8. Environmental assessment: waste-form selection for SRP high-level waste

    DOE has recently decided to construct and operate a Defense Waste Processing Facility (DWPF) at the Savannah River Plant (SRP) to immobilize the high-level radioactive waste generated and stored pending disposal in a federal geologic repository. In the immobilization process the high-activity fraction of the SRP high-level waste is mixed with glass frit to form the feed for the melter. The glass is cast from an electric-heated, ceramic-lined melter into canisters. Crystalline ceramic, the leading alternative to borosilicate glass, also appears to be an acceptable form for immobilizing the SRP high-level waste. Both are expected to meet regulations and repository acceptance criteria. The assessment also shows that the environmental effects of disposing of SRP high-level waste as a crystalline ceramic form would not differ significantly from the projected effects for disposal of the borosilicate glass form. A comprehensive evaluation program led to the recommendation of borosilicate glass as the preferred waste form. 10 figures, 19 tables

  9. Diffusion-based leaching models for glassy waste forms

    Most scenarios for the disposal of high-level nuclear wastes assume burial under conditions in which only a limited quantity of groundwater will contact the waste form. In order to model these conditions, it is necessary to describe the release of species from a waste form matrix in contact with a limited volume of leachant in which the concentration of released species is not zero and is itself a function of release rate. Eight leaching models are presented that include the cases of a dissolving and a nondissolving matrix, finite, infinite, and replenished leachant volumes, and a matrix covered by a surface layer with different properties. The equations that describe these models assume a linear concentration profile of the diffusing species within the waste form and apply Fick's first law to obtain the leach rate. In three cases a direct comparison is possible between the solutions of these equations and solutions obtained by use of the diffusion equation derived from Fick's second law. Good agreement is found. The equations given are convenient for use with programmable calculators

  10. Testing of high-level waste forms under repository conditions

    The workshop on testing of high-level waste forms under repository conditions was held on 17 to 21 October 1988 in Cadarache, France, and sponsored by the Commission of the European Communities (CEC), the Commissariat a l'energie atomique (CEA) and the Savannah River Laboratory (US DOE). Participants included representatives from Australia, Belgium, Denmark, France, Germany, Italy, Japan, the Netherlands, Sweden, Switzerland, The United Kingdom and the United States. The first part of the conference featured a workshop on in situ testing of simulated nuclear waste forms and proposed package components, with an emphasis on the materials interface interactions tests (MIIT). MIIT is a sevent-part programme that involves field testing of 15 glass and waste form systems supplied by seven countries, along with potential canister and overpack materials as well as geologic samples, in the salt geology at the Waste Isolation Pilot Plant (WIPP) in Carlsbad, New Mexico, USA. This effort is still in progress and these proceedings document studies and findings obtained thus far. The second part of the meeting emphasized multinational experimental studies and results derived from repository systems simulation tests (RSST), which were performed in granite, clay and salt environments

  11. Comparative evaluation of DHDECMP [dihexyl-N,N-diethylcarbamoyl-methylphosphonate] and CMPO [octylphenyl-N,N,-diisobutylcarbamoylmethylphosphine oxide] as extractants for recovering actinides from nitric acid waste streams

    Certain neutral, bifunctional organophosphorous compounds are of special value to the nuclear industry. Dihexyl-N,N-diethylcarbomoylmethylphosphonate (DHDECMP) and octylphenyl-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO) are highly selective extractants for removing actinide and lanthanide elements from nitric acid. We obtained these two extractants from newly available commercial sources and evaluated them for recovering Am(III), Pu(IV), and U(VI) from nitric acid waste streams of plutonium processing operations. Variables included the extractant (DHSECMP or CMPO), extractant/tributylphosphate ratio, diluent, nitrate concentration, nitrate salt/nitric acid ratio, fluoride concentration, and contact time. Based on these experimental data, we selected DHDECMP as the perferred extractant for this application. 18 refs., 30 figs

  12. Radiation damage studies related to nuclear waste forms

    Much of the previously reported work on alpha radiation effects on crystalline phases of importance to nuclear waste forms has been derived from radiation effects studies of composite waste forms. In the present work, two single-phase crystalline materials, Gd2Ti2O7 (pyrochlore) and CaZrTi2O7 (zirconolite), of relative importance to current waste forms were studied independently by doping with 244Cm at the 3 wt % level. Changes in the crystalline structure measured by x-ray diffraction as a function of dose show that damage ingrowth follows an expected exponential relationship of the form ΔV/V0 = A[1-exp(-BD)]. In both cases, the materials became x-ray amorphous before the estimated saturation value was reached. The predicted magnitudes of the unit cell volume changes at saturation are 5.4% and 3.5%, respectively, for Gd2Ti2O7 and CaZrTi2O7. The later material exhibited anisotropic behavior in which the expansion of the monoclinic cell in the c0 direction was over five times that of the a0 direction. The effects of transmutations on the properties of high-level waste solids have not been studied until now because of the long half-lives of the important fission products. This problem was circumvented in the present study by preparing materials containing natural cesium and then irradiating them with neutrons to produce 134Cs, which has only a 2y half-life. The properties monitored at about one year intervals following irradiation have been density, leach rate and microstructure. A small amount of x-ray diffraction work has also been done. Small changes in density and leach rate have been observed for some of the materials, but they were not large enough to be of any consequence for the final disposal of high level wastes

  13. Zirconium phosphate waste forms for low-temperature stabilization of cesium-137-containing waste streams

    Novel chemically bonded phosphate ceramics are being developed and fabricated for low-temperature stabilization and solidification of waste streams that are not amenable to conventional high-temperature stabilization processes because volatiles are present in the wastes. A composite of zirconium-magnesium phosphate has been developed and shown to stabilize ash waste contaminated with a radioactive surrogate of 137Cs. Excellent retainment of cesium in the phosphate matrix system was observed in Toxicity Characteristic Leaching Procedure tests. This was attributed to the capture of cesium in the layered zirconium phosphate structure by intercalation ion-exchange reaction. But because zirconium phosphate has low strength, a novel zirconium/magnesium phosphate composite waste form system was developed. The performance of these final waste forms, as indicated by compression strength and durability in aqueous environments, satisfy the regulatory criteria. Test results indicate that zirconium-magnesium-phosphate-based final waste forms present a viable technology for treatment and solidification of cesium-contaminated wastes

  14. Actinides recycling assessment in a thermal reactor

    Highlights: • Actinides recycling is assessed using BWR fuel assemblies. • Four fuel rods are substituted by minor actinides rods in a UO2 and in a MOX fuel assembly. • Performance of standard fuel assemblies and the ones with the substitution is compared. • Reduction of actinides is measured for the fuel assemblies containing minor actinides rods. • Thermal reactors can be used for actinides recycling. - Abstract: Actinides recycling have the potential to reduce the geological repository burden of the high-level radioactive waste that is produced in a nuclear power reactor. The core of a standard light water reactor is composed only by fuel assemblies and there are no specific positions to allocate any actinides blanket, in this assessment it is proposed to replace several fuel rods by actinides blankets inside some of the reactor core fuel assemblies. In the first part of this study, a single uranium standard fuel assembly is modeled and the amount of actinides generated during irradiation is quantified for use it as reference. Later, in the same fuel assembly four rods containing 6 w/o of minor actinides and using depleted uranium as matrix were replaced and depletion was simulated to obtain the net reduction of minor actinides. Other calculations were performed using MOX fuel lattices instead of uranium standard fuel to find out how much reduction is possible to obtain. Results show that a reduction of minor actinides is possible using thermal reactors and a higher reduction is obtained when the minor actinides are embedded in uranium fuel assemblies instead of MOX fuel assemblies

  15. Leaching behavior of glass ceramic nuclear waste forms

    Lokken, R. O.

    1981-11-01

    Glass ceramic waste forms were investigated as alternatives to borosilicate glasses for the immobilization of high-level radioactive waste. Three glass ceramic systems were investigated, including basalt, celsian, and fresnoite, each containing 20 wt percent simulated high-level waste calcine. Static leach tests were performed on seven glass ceramic materials and one parent glass (before recrystallization). Samples were leached at 90 C for 3 to 28 days in deionized water and silicate water. The results, expressed in normalized elemental mass loss, show comparable releases from celsian and fresnoite glass ceramics. Basalt glass ceramics demonstrated the lowest normalized elemental losses with a nominal release less than 2 grams per square meter when leached in polypropylene containers. The releases from basalt glass ceramics when leached in silicate water were nearly identical with those in deionized water. The overall leachability of celsian and fresnoite glass ceramics was improved when silicate water was used as the leachant.

  16. Microelectrochemical and corrosion behaviour of metal alloy waste forms

    Within the USDOE Fuel Cycle Research and Development Program steel-based alloys have shown promise as potential waste forms for Tc-based waste streams produced from spent fuel processing. Waste stream components are alloyed with steel to create an alloy with a complex microstructure. Surface analytical techniques (SEM, EDS) coupled with long-term corrosion studies and electrochemical techniques have been used to analyze the corrosion behaviour of this material. Due to the complex alloy structure it is difficult to determine which phases are active or passive to corrosion. A microelectrochemical cell system has been employed to isolate and study individual phases and regions to separate their corrosion behaviours. Such analyses lead to a much clearer picture of alloy corrosion processes when coupled with bulk studies. (author)

  17. Research and development of waste forms for geological disposal

    Ceramics are candidate materials for immobilizing high-level waste (HLW) stemming from the reprocessing of spent fuels. We are proceeding with R and D on two types of ceramic waste form : a polyphase titanate ceramic named Synroc and three kinds of single-phase zirconium ceramics. The effect of self-irradiation damage on the long-term integrity of Synroc due to alpha decay was studied under a cooperative program between JAERI and ANSTO. The hot-pressed polyphase titanate ceramic (10 wt% waste loading) was doped with 244Cm to accumulate a dose of 1.6 x 1018 alpha decays/g. The phase assemblage of the curium-doped titanate ceramic included freudenbergite and loveringite in addition to three main phases: hollandite, perovskite and zirconolite. Accumulation of alpha decays was accompanied by a gradual decrease in density. The change in density was -2.7 % after an equivalent age of 45000 years. The durability of three single-phase zirconium ceramics which contained the appropriate amount of simulated high-level waste elements was examined at 90degC and 150degC in hydrochloric acid or deionized water. The waste forms examined included 10 mol% Y2O3-stabilized ZrO2, La2Zr2O7 with a pyrochlore structure, and CaZrO3 with a perovskite structure. La2Zr2O7 showed excellent durability, and leach rates of all constituents were less than about 10-4 g·m-2·day-1 at 150degC in deionized water. This suggests that La2Zr2O7 is a promising candidate material for immobilization of waste elements from HLW. (J.P.N.)

  18. Measurements of Mercury Released from Solidified/Stabilized Waste Forms

    This report covers work performed during FY 1999-2000 in support of treatment demonstrations conducted for the Mercury Working Group of the U.S. Department of Energy (DOE) Mixed Waste Focus Area. In order to comply with the requirements of the Resource Conservation and Recovery Act, as implemented by the U.S. Environmental Protection Agency (EPA), DOE must use one of these procedures for wastes containing mercury at levels above 260 ppm: a retorting/roasting treatment or an incineration treatment (if the wastes also contain organics). The recovered radioactively contaminated mercury must then be treated by an amalgamation process prior to disposal. The DOE Mixed Waste Focus Area and Mercury Working Group are working with the EPA to determine if some alternative processes could treat these types of waste directly, thereby avoiding for DOE the costly recovery step. They sponsored a demonstration in which commercial vendors applied their technologies for the treatment of two contaminated waste soils from Brookhaven National Laboratory. Each soil was contaminated with ∼4500 ppm mercury; however, one soil had as a major radioelement americium-241, while the other contained mostly europium-152. The project described in this report addressed the need for data on the mercury vapor released by the solidified/stabilized mixed low-level mercury wastes generated during these demonstrations as well as the comparison between the untreated and treated soils. A related work began in FY 1998, with the measurement of the mercury released by amalgamated mercury, and the results were reported in ORNL/TM-13728. Four treatments were performed on these soils. The baseline was obtained by thermal treatment performed by SepraDyne Corp., and three forms of solidification/stabilization were employed: one using sulfur polymer cement (Brookhaven National Laboratory), one using portland cement [Allied Technology Group (ATG)], and a third using proprietary additives (Nuclear Fuel Services)

  19. Preparation of a technology development roadmap for the Accelerator Transmutation of Waste (ATW) System : report of the ATW separations technologies and waste forms technical working group.

    Collins, E.; Duguid, J.; Henry, R.; Karell, E.; Laidler, J.; McDeavitt, S.; Thompson, M.; Toth, M.; Williamson, M.; Willit, J.

    1999-08-12

    In response to a Congressional mandate to prepare a roadmap for the development of Accelerator Transmutation of Waste (ATW) technology, a Technical Working Group comprised of members from various DOE laboratories was convened in March 1999 for the purpose of preparing that part of the technology development roadmap dealing with the separation of certain radionuclides for transmutation and the disposal of residual radioactive wastes from these partitioning operations. The Technical Working Group for ATW Separations Technologies and Waste Forms completed its work in June 1999, having carefully considered the technology options available. A baseline process flowsheet and backup process were identified for initial emphasis in a future research, development and demonstration program. The baseline process combines aqueous and pyrochemical processes to permit the efficient separation of the uranium, technetium, iodine and transuranic elements from the light water reactor (LWR) fuel in the head-end step. The backup process is an all- pyrochemical system. In conjunction with the aqueous process, the baseline flowsheet includes a pyrochemical process to prepare the transuranic material for fabrication of the ATW fuel assemblies. For the internal ATW fuel cycle the baseline process specifies another pyrochemical process to extract the transuranic elements, Tc and 1 from the ATW fuel. Fission products not separated for transmutation and trace amounts of actinide elements would be directed to two high-level waste forms, one a zirconium-based alloy and the other a glass/sodalite composite. Baseline cost and schedule estimates are provided for a RD&D program that would provide a full-scale demonstration of the complete separations and waste production flowsheet within 20 years.

  20. Preparation of a technology development roadmap for the Accelerator Transmutation of Waste (ATW) System : report of the ATW separations technologies and waste forms technical working group

    In response to a Congressional mandate to prepare a roadmap for the development of Accelerator Transmutation of Waste (ATW) technology, a Technical Working Group comprised of members from various DOE laboratories was convened in March 1999 for the purpose of preparing that part of the technology development roadmap dealing with the separation of certain radionuclides for transmutation and the disposal of residual radioactive wastes from these partitioning operations. The Technical Working Group for ATW Separations Technologies and Waste Forms completed its work in June 1999, having carefully considered the technology options available. A baseline process flowsheet and backup process were identified for initial emphasis in a future research, development and demonstration program. The baseline process combines aqueous and pyrochemical processes to permit the efficient separation of the uranium, technetium, iodine and transuranic elements from the light water reactor (LWR) fuel in the head-end step. The backup process is an all- pyrochemical system. In conjunction with the aqueous process, the baseline flowsheet includes a pyrochemical process to prepare the transuranic material for fabrication of the ATW fuel assemblies. For the internal ATW fuel cycle the baseline process specifies another pyrochemical process to extract the transuranic elements, Tc and 1 from the ATW fuel. Fission products not separated for transmutation and trace amounts of actinide elements would be directed to two high-level waste forms, one a zirconium-based alloy and the other a glass/sodalite composite. Baseline cost and schedule estimates are provided for a RD and D program that would provide a full-scale demonstration of the complete separations and waste production flowsheet within 20 years

  1. Crystallization behavior during melt-processing of ceramic waste forms

    Tumurugoti, Priyatham; Sundaram, S. K.; Misture, Scott T.; Marra, James C.; Amoroso, Jake

    2016-05-01

    Multiphase ceramic waste forms based on natural mineral analogs are of great interest for their high chemical durability, radiation resistance, and thermodynamic stability. Melt-processed ceramic waste forms that leverage existing melter technologies will broaden the available disposal options for high-level nuclear waste. This work reports on the crystallization behavior in selected melt-processed ceramics for waste immobilization. The phase assemblage and evolution of hollandite, zirconolite, pyrochlore, and perovskite type structures during melt processing were studied using thermal analysis, x-ray diffraction, and electron microscopy. Samples prepared by melting followed by annealing and quenching were analyzed to determine and measure the progression of the phase assemblage. Samples were melted at 1500 °C and heat-treated at crystallization temperatures of 1285 °C and 1325 °C corresponding to exothermic events identified from differential scanning calorimetry measurements. Results indicate that the selected multiphase composition partially melts at 1500 °C with hollandite coexisting as crystalline phase. Perovskite and zirconolite phases crystallized from the residual melt at temperatures below 1350 °C. Depending on their respective thermal histories, different quenched samples were found to have different phase assemblages including phases such as perovskite, zirconolite and TiO2.

  2. Tailored ceramic consolidation forms for ICPP waste compositions

    This paper reports a polyphase tailored ceramic developed for the consolidation of simulated ICPP (Idaho Chemical Processing Plant)-type high Zr content high-level waste (HLW) calcines. The ceramic is specifically designed to provide chemically stable host phases for each species present in the HLW and to maximize waste volume reduction through high loadings and form density. The ceramic is designed for a 73 wt% waste loading with a density of 3.35 ± 0.05 (g/cm3). The major phase in the ceramic is a high-silica glass, which contains the neutron poison boron as well as the majority of the nonrefractory species in the waste. The primary crystalline phases are calcium fluoride, calcium-yttrium stabilized cubic zirconia, a hexagonal apatite type silicate containing the plutonium simulant Ce, and a Cd metal phase. Minor phases include zircon, zirconolite, and a sphene-type. Leaching testing and microscopic analysis shows the ceramic form to be chemically durable, with only the glass phase showing any detectable dissolution in deionized water at 90 degrees C

  3. Salt-occluded zeolite waste forms: Crystal structures and transformability

    Neutron diffraction studies of salt-occluded zeolite and zeolite/glass composite samples, simulating nuclear waste forms loaded with fission products, have revealed complex structures, with cations assuming the dual roles of charge compensation and occlusion (cluster formation). These clusters roughly fill the 6--8 angstrom diameter pores of the zeolites. Samples are prepared by equilibrating zeolite-A with complex molten Li, K, Cs, Sr, Ba, Y chloride salts, with compositions representative of anticipated waste systems. Samples prepared using zeolite 4A (which contains exclusively sodium cations) as starting material are observed to transform to sodalite, a denser aluminosilicate framework structure, while those prepared using zeolite 5A (sodium and calcium ions) more readily retain the zeolite-A structure. Because the sodalite framework pores are much smaller than those of zeolite-A, clusters are smaller and more rigorously confined, with a correspondingly lower capacity for waste containment. Details of the sodalite structures resulting from transformation of zeolite-A depend upon the precise composition of the original mixture. The enhanced resistance of salt-occluded zeolites prepared from zeolite 5A to sodalite transformation is thought to be related to differences in the complex chloride clusters present in these zeolite mixtures. Data relating processing conditions to resulting zeolite composition and structure can be used in the selection of processing parameters which lead to optimal waste forms

  4. Integrated AMP-PAN, TRUEX, and SREX Flowsheet Test to Remove Cesium, Surrogate Actinide Elements, and Strontium from INEEL Tank Waste Using Sorbent Columns and Centrifugal Contactors

    Herbst, Ronald Scott; Law, Jack Douglas; Todd, Terry Allen; Wood, D. J.; Garn, Troy Gerry; Wade, Earlen Lawrence

    2000-02-01

    Three unit operations for the removal of selected fission products, actinides, and RCRA metals (mercury and lead) have been successfully integrated and tested for extended run times with simulated INEEL acidic tank waste. The unit operations were ion exchange for Cs removal, followed by TRUEX solvent extraction for Eu (actinide surrogate), Hg, and Re (Tc surrogate) removal, and subsequent SREX solvent extraction for Sr and Pb removal. Approximately 45 L of simulated INTEC tank waste was first processed through three ion exchange columns in series for selective Cs removal. The columns were packed with a composite ammonium molybdophosphate-polyacrylonitrile (AMP-PAN) sorbent. The experimental breakthrough data were in excellent agreement with modeling predictions based on data obtained with much smaller columns. The third column (220 cm3) was used for polishing and Cs removal after breakthrough of the up-stream columns. The Cs removal was >99.83% in the ion exchange system without interference from other species. Most of the effluent from the ion exchange (IX) system was immediately processed through a TRUEX solvent extraction flowsheet to remove europium (americium surrogate), mercury and rhenium (technetium surrogate) from the simulated waste. The TRUEX flowsheet test was performed utilizing 23 stages of 3.3-cm centrifugal contactors. Greater than 99.999% of the Eu, 96.3% of the Hg, and 56% of the Re were extracted from the simulated feed and recovered in the strip and wash streams. Over the course of the test, there was no detectable build-up of any components in the TRUEX solvent. The raffinate from the TRUEX test was stored and subsequently processed several weeks later through a SREX solvent extraction flowsheet to remove strontium, lead, and Re (Tc surrogate) from the simulated waste. The SREX flowsheet test was performed using the same centrifugal contactors used in the TRUEX test after reconfiguration and the addition of three stages. Approximately 99.9% of

  5. Integrated AMP-PAN, TRUEX, and SREX Flowsheet Test to Remove Cesium, Surrogate Actinide Elements, and Strontium from INEEL Tank Waste Using Sorbent Columns and Centrifugal Contactors

    Three unit operations for the removal of selected fission products, actinides, and RCRA metals (mercury and lead) have been successfully integrated and tested for extended run times with simulated INEEL acidic tank waste. The unit operations were ion exchange for Cs removal, followed by TRUEX solvent extraction for Eu (actinide surrogate), Hg, and Re (Tc surrogate) removal, and subsequent SREX solvent extraction for Sr and Pb removal. Approximately 45 L of simulated INTEC tank waste was first processed through three ion exchange columns in series for selective Cs removal. The columns were packed with a composite ammonium molybdophosphate-polyacrylonitrile (AMP-PAN) sorbent. The experimental breakthrough data were in excellent agreement with modeling predictions based on data obtained with much smaller columns. The third column (220 cm3) was used for polishing and Cs removal after breakthrough of the up-stream columns. The Cs removal was >99.83% in the ion exchange system without interference from other species. Most of the effluent from the ion exchange (IX) system was immediately processed through a TRUEX solvent extraction flowsheet to remove europium (americium surrogate), mercury and rhenium (technetium surrogate) from the simulated waste. The TRUEX flowsheet test was performed utilizing 23 stages of 3.3-cm centrifugal contactors. Greater than 99.999% of the Eu, 96.3% of the Hg, and 56% of the Re were extracted from the simulated feed and recovered in the strip and wash streams. Over the course of the test, there was no detectable build-up of any components in the TRUEX solvent. The raffinate from the TRUEX test was stored and subsequently processed several weeks later through a SREX solvent extraction flowsheet to remove strontium, lead, and Re (Tc surrogate) from the simulated waste. The SREX flowsheet test was performed using the same centrifugal contactors used in the TRUEX test after reconfiguration and the addition of three stages. Approximately 99.9% of

  6. Technical viability and development needs for waste forms and facilities

    Pegg, I.; Gould, T.

    1996-05-01

    The objective of this breakout session was to provide a forum to discuss technical issues relating to plutonium-bearing waste forms and their disposal facilities. Specific topics for discussion included the technical viability and development needs associated with the waste forms and/or disposal facilities. The expected end result of the session was an in-depth (so far as the limited time would allow) discussion of key issues by the session participants. The session chairs expressed allowance for, and encouragement of, alternative points of view, as well as encouragement for discussion of any relevant topics not addressed in the paper presentations. It was not the intent of this session to recommend or advocate any one technology over another.

  7. Production and characteristics for concrete waste forms to stabilize concrete waste produced during decommissioning procedure

    Since the decommissioning of nuclear plants and facilities, large quantities of slightly contaminated concrete waste have been generated. In Korea, the decontamination and decommissioning of the KRR-1, 2 at the KAERI have been under way. Concrete waste was generated 83 drums of 200L and 41 containers of 4 M3. These concrete wastes consist of rubble, coarse, and fine aggregates. And also, 24 drums of concrete sludge were generated from the saw cutting of radioactive concrete. The conditioning of concrete waste is needed for final disposal. The concrete waste is conditioned as follows: mortar using coarse and fine aggregates is filled void space after concrete rubble pre-placement into 200 L drum. The mortar needs to be solidified using cement or other materials to protect from sufficient strength and harmful opening. Especially, cement was frequently used solidification/stabilization above all the other ones because of competitive prices, convenient method and excellent quality. Thus, this paper has developed an optimizing mixing ratio of concrete waste, water, and cement and has evaluated characteristics of a cement waste form containing radioactive concrete to meet the requirements specified in disposal site specific waste acceptance criteria

  8. Polyethylene encapsulatin of nitrate salt wastes: Waste form stability, process scale-up, and economics

    A polyethylene encapsulation system for treatment of low-level radioactive, hazardous, and mixed wastes has been developed at Brookhaven National Laboratory. Polyethylene has several advantages compared with conventional solidification/stabilization materials such as hydraulic cements. Waste can be encapsulated with greater efficiency and with better waste form performance than is possible with hydraulic cement. The properties of polyethylene relevant to its long-term durability in storage and disposal environments are reviewed. Response to specific potential failure mechanisms including biodegradation, radiation, chemical attack, flammability, environmental stress cracking, and photodegradation are examined. These data are supported by results from extensive waste form performance testing including compressive yield strength, water immersion, thermal cycling, leachability of radioactive and hazardous species, irradiation, biodegradation, and flammability. The bench-scale process has been successfully tested for application with a number of specific ''problem'' waste streams. Quality assurance and performance testing of the resulting waste form confirmed scale-up feasibility. Use of this system at Rocky Flats Plant can result in over 70% fewer drums processed and shipped for disposal, compared with optimal cement formulations. Based on the current Rocky Flats production of nitrate salt per year, polyethylene encapsulation can yield an estimated annual savings between $1.5 million and $2.7 million, compared with conventional hydraulic cement systems. 72 refs., 23 figs., 16 tabs

  9. Preliminary waste form characteristics report Version 1.0. Revision 1

    Stout, R.B.; Leider, H.R. [eds.

    1991-10-11

    This report focuses on radioactive waste form characteristics that will be used to design a waste package and an engineered barrier system (EBS) for a suitable repository as part of the Yucca Mountain Project. The term waste form refers to irradiated reactor fuel, other high-level waste (HLW) in various physical forms, and other radioactive materials (other than HLW) which are received for emplacement in a geologic repository. Any encapsulating of stabilizing matrix is also referred to as a waste form.

  10. Preliminary waste form characteristics report Version 1.0. Revision 1

    This report focuses on radioactive waste form characteristics that will be used to design a waste package and an engineered barrier system (EBS) for a suitable repository as part of the Yucca Mountain Project. The term waste form refers to irradiated reactor fuel, other high-level waste (HLW) in various physical forms, and other radioactive materials (other than HLW) which are received for emplacement in a geologic repository. Any encapsulating of stabilizing matrix is also referred to as a waste form

  11. Waste form characterization and its relationship to transportation accident analysis

    The response of potential waste forms should be determined for extreme transportation environments that must be postulated for environmental impact analysis and also for hypothetical accident conditions to which packagings and contents must be subjected for licensing purposes. The best approach may be to test materials up to and beyond their failure point; such an approach would establish failure thresholds. Specification of what denotes failure would be defined by existing or proposed regulations or dictated by requirements developed from accident analysis. Responses to physical and thermal insults are the most important for licensing or analysis and need to be thoroughly characterized. Others in need of characterization might be responses to extreme chemical environments and to intense and prolonged radiation exposure. A complete characterization of waste-form responses would be desirable for environments that are considered extreme for transportation accidents but which may be typical for processing or disposal environments. In addition, the characterizations that are performed must be completed in laboratory environments which can be readily correlated to accident environments and must be meaningfully conveyed to a transportation impact analyst. As an example, leaching data as commonly presented are not usable to the analyst and are obtained under conditions that are not directly applicable to conditions of most transportation accidents. Transportation analysts are in need of data useful for calculating environmental impacts and for licensing of packagings. Future waste form development programs and associated decisions should consider the needs of transportation analysts

  12. The Ceramic Waste Form Process at the Idaho National Laboratory

    Ken Bateman; Stephen Priebe

    2006-08-01

    The treatment of spent nuclear fuel for disposition using an electrometallurgical technique results in two high-level waste forms: a ceramic waste form (CWF) and a metal waste form (MWF). The CWF is a composite of sodalite and glass, which stabilizes the active fission products (alkali, alkaline earths, and rare earths) and transuranic (TRU) elements. Reactive metal fuel constituents, including all the TRU metals and the majority of the fission products remain in the salt as chlorides and are processed into the CWF. The solidified salt is containerized and transferred to the CWF process where it is ground in an argon atmosphere. Zeolite 4A is dried in a mechanically-fluidized dryer to about 0.1 wt% moisture and ground to a particle-size range of 45µ to 250µ. The salt and zeolite are mixed in a V-mixer and heated to 500°C for about 18 hours. During this process, the salt occludes into the structure of the zeolite. The salt-loaded zeolite (SLZ) is cooled and then mixed with borosilicate glass frit with a comparable particle-size range. The SLZ/glass mixture is transferred to a crucible, which is placed in a furnace and heated to 925°C. During this process, known as pressureless consolidation, the zeolite is converted to the final sodalite form and the glass thoroughly encapsulates the sodalite, producing a dense, leach-resistant final waste form. During the last several years, changes have occurred to the process, including: particle size of input materials and conversion from hot isostatic pressing to pressureless consolidation, This paper is intended to provide the current status of the CWF process focusing on the adaptation to pressureless consolidation. Discussions will include impacts of particle size on final waste form and the pressureless consolidation cycle. A model will be presented that shows the heating and cooling cycles and the effect of radioactive decay heat on the amount of fission products that can be incorporated into the CWF.

  13. Transmutation of nuclear waste. Status report RAS programme 1994: Recycling and transmutation of actinides and fission products

    This report describes the status and progress of the Dutch RAS programme on 'Recycling and Transmutation of Actinides and Fission Products' over the year 1994, which is the first year of the second 4-year programme. This programme is outlined and a short progress report is given over 1994, including a listing of 23 reports and publications over the year 1994. Highlights of 1994 were: The completion of long-lived fission-product transmutation studies, the initiation of small-scale demonstration experiments in the HFR on Tc and I, the issue of reports on the potential of the ALMR (Advanced Liquid Metal Reactor) for transmutation adn the participation and international cooperation on irradiation experiments with actinides in inert matrices. The remaining chapters contain more extended contributions on recent developments and selected topics, under the headings: Benefits and risks of partitioning and transmutation, Perspective of chemical partitioning, Inert matrices, Evolutionary options (MOX), Perspective of heavy water reactors, Perspective of fast burners, Perspective of accelerator-based systems, Thorium cycle, Fission-product transmutation, End scenarios, and Executive summary and recommendations. (orig.)

  14. Actinides in earth materials: the importance of natural analogues

    Predictions of the stability of waste forms designed for long-term storage of actinides require an accurate knowledge of the long-term properties of these actinides in their host matrix. One useful approach to address this issue involves comparison of structural and thermodynamic information derived from short time-scale experiments on synthetic samples with similar information from natural samples, including natural glasses and metamict minerals. These natural analogues of synthetic waste forms, although significantly different in structure, properties and composition from the synthetic samples, offer a number of examples of earth materials that have received large doses of radioactivity (mainly α events) over very long time periods (106-109 years). In this paper, we present a review of the co-ordination chemistry of actinides in natural deep-seated earth systems and their analogues (mostly glasses, melts and radiation-damaged minerals). Special emphasis is given to data analysis methods that are important in determining accurate XAFS-derived interatomic distances and co-ordination numbers for actinides in these complex materials, including anharmonicity, multi-electronic transitions, deconvolution procedures, and ab initio calculations of near-edge structure. The effects of anharmonicity and multi-electronic transitions are best studied using high-energy resolution spectrometers on third-generation synchrotron sources. Application of these methods to selected natural minerals (crystalline and radiation-damaged) is presented, together with a comprehensive list of unusual mineral structures that are known to incorporate relatively large amounts of actinides over long periods of geologic time in a stable manner. (authors)

  15. Stability of High-Level Radioactive Waste Forms

    The objective of the proposed effort was to expand the development of solution models of complex waste glass systems that are predictive with regard to composition, phase separation, chemical activity, and volatility. The effort was to yield thermodynamic values for waste components that are fundamentally required to predict the melting/crystallization behavior during processing and leaching/corrosion behavior of waste glass in repository environments. The waste glass systems consist of dozens of chemical elements present within a limited number of phases, and thus many elements will be ''dissolved'' in the host phase(s). The nature of the chemical potential of the constituent elements is determined by their solid solution behavior. And that solid solution behavior will be governed by the energetics of interactions between species, crystalline state, site occupancy, and oxidation state of the elements. Yet, unlike metallic systems, oxide solution thermodynamic relationships are not well established as they are extremely complex with no generally accepted solution models for multiple oxide species as solutes in a solvent phase, especially in the non-equilibrium glass phase. The production of nuclear materials for defense applications at several sites in the United States has resulted in the accumulation over almost six decades of a substantial quantity of radionuclides. These materials are currently stored in a variety of forms including liquids, sludges, and solids. In addition, there are similar wastes that have resulted from the reprocessing of commercial spent fuel, although this has occurred to a much smaller extent. While the composition and characteristics of the various wastes differ, their behavior is similar in many respects. The focus of current U. S. Department of Energy (DOE) efforts with regard to permanent disposal of these materials is that they will be incorporated in a stable, insoluble host solid (a glass or specific crystalline phase)

  16. Support for DOE program in mineral waste-form development

    This research investigation relates to sintered simulation ceramic waste forms of the generic SYNROC compositional type. Though they have been formulated with simulated wastes only, they serve as prototypes for potential hot, processed, crystalline waste forms whose combined thermodynamic stability and physical integrity are considered to render them capable of long-term imobilization of high-level radwastes under deep geologic disposal conditions. The problems involved are nontrivial, largely because of the very complex nature of the radwastes: a typical waste stream would contain more than 31 cation species. When the stabilizing matrix constituents are included, the final batch composition must successfully account (and find substitutional homes for some 35 different cation species. One of the important objectives of this study thus has been to develop a computer-based method for simulating these complex ion substitutions, and for calculating the resultant phase demands and batch formulations. Primary goals of the study have been (1) use of that computer simulation capability to incorporate rationally the radwaste ions from a specific waste stream (PW-7a) into the available SYNROC lattice sites and (2) utilization of existing ceramic processing and sintering methodologies to assure (and to understand) the attainment of high density, fine microstructure, full phase development and other features of the sintered product which are known to relate directly to its integrity and leach resistance. Though improved resistance to leaching has been a continuing goal, time and budget constraints have precluded initiation of any leachability studies of these new compositions during this contract period. 27 references, 15 figures, 6 tables

  17. Actinides in silicate glasses and melts and on mineral surfaces: information on local co-ordination environments from XAFS spectroscopy and bond valence theory

    The impact of actinides on the environment is mitigated by their interaction with particle surfaces and by incorporation into suitable waste forms. In both cases, a fundamental knowledge of the local co-ordination environment of actinide ions is essential for understanding their stability in various near-surface environments under a range of conditions. When actinide ions are sorbed on mineral surfaces, the extent to which the ions are immobilised depends on the type of surface complex or solid precipitate that forms. When incorporated into a glass or crystalline waste form, the stability of the actinide will depend in part on its redox state and local co-ordination environment. In both cases, XAFS spectroscopy can provide unique information on the number and types of first and, in certain cases, more distant neighbours, and their geometric arrangement (including inter-atomic distances and a measure of their disorder). When this structural information from XAFS spectroscopy is combined with Pauling bond valence theory and modem bond valences corrected for bond length variations, it is also possible to develop plausible models for their medium-range co-ordination environments (out to ≅ 4 Angstrom radial distance around the actinide) for both sorbed actinide ions and those present in a silicate glass or melt. We discuss results from several XAFS studies of the naturally occurring actinides uranium and thorium in sorption samples, silicate glasses and silicate melts at high temperature. (authors)

  18. Results of storage studies of separated minor actinides

    In the framework of the French law of 1991 about the management of radioactive wastes, studies have been carried out on the separation, conditioning and storage of minor actinides in order to dispose of a complete and thorough processing file for spent fuels: conversion of actinide nitrate liquid solutions from deep separation processes into solid compounds, conversion of these compounds into a physical form suitable for storage, conditioning of these compounds in the form of packages, and design of storage facilities compatible with the specificities (thermal, radioactive) of separated minor actinides and with storage durations of few decades. The already-tested industrial processes have been favored, the feasibility of conditioning and storage operations have been evaluated for curium, in particular concerning the thermal aspect. The studies carried out so far have permitted to define the conversion process and the conditioning solution and to evaluate different possibilities of storage facility concepts. The future studies will focus on the development of optimized versions of facilities specific to each category of separated minor actinides. (J.S.)

  19. Description of DWPF reference waste form and canister

    1981-06-01

    This document describes the reference waste form and canister for the Defense Waste Processing Facility (DWPF). The facility is planned for location at the Savannah River Plant in Aiken, SC, and is scheduled for construction authorization during FY-1983. The reference canister is fabricated of 24-in.-OD 304L stainless steel pipe with a dished bottom, domed head, and lifting and welding flanges on the head neck. The overall canister length is 9 ft 10 in., with a wall thickness of 3/8-in. (schedule 20 pipe). The canister length was selected to reduce equipment cell height in the DWPF to a practical size. The canister diameter was selected to ensure that a filled canister with its shipping cask could be accommodated on a legal-weight truck. The overall dimensions and weight appear to be generally compatible with preliminary assessments of repository requirements. The reference waste form is borosilicate glass containing approximately 28 wt % sludge oxides with the balance glass frit. Borosilicate glass was chosen because of its high resistance to leaching by water, its relatively high solubility for nuclides found in the sludge, and its reasonably low melting temperature. The glass frit contains approximately 58% SiO/sub 2/ and 15% B/sub 2/O/sub 3/. This composition results in a low average leachability in the waste form of approximately 5 x 10/sup -9/ g/cm/sup 2/-day based on /sup 137/Cs over 365 days in 25/sup 0/C water. The canister is filled with 3260 lb of glass which occupies about 85% of the free canister volume. The filled canister will generate approximately 425 watts when filled with oxides from 5-year-old sludge and 15-year-old supernate from the Stage 1 and Stage 2 processes. The radionuclide content of the canister is about 150,000 curies, with a radiation level of 2 x 10/sup 4/ rem/hour at 1 cm.

  20. Immobilization of fission products in phosphate ceramic waste forms

    Chemically bonded phosphate ceramics (CBPCs) have several advantages that make them ideal candidates for containing radioactive and hazardous wastes. In general, phosphates have high solid-solution capacities for incorporating radionuclides, as evidenced by several phosphates (e.g., monazites and apatites) that are natural analogs of radioactive and rare-earth elements. The phosphates have high radiation stability, are refractory, and will not degrade in the presence of internal heating by fission products. Dense and hard CBPCs can be fabricated inexpensively and at low temperature by acid-base reactions between an inorganic oxide/hydroxide powder and either phosphoric acid or an acid-phosphate solution. The resulting phosphates are extremely insoluble in aqueous media and have excellent long-term durability. CBPCs offer the dual stabilization mechanisms of chemical fixation and physical encapsulation, resulting in superior waste forms. The goal of this task is develop and demonstrate the feasibility of CBPCs for S/S of wastes containing fission products. The focus of this work is to develop a low-temperature CBPC immobilization system for eluted 99Tc wastes from sorption processes

  1. Immobilization of fission products in phosphate ceramic waste forms

    Singh, D.; Wagh, A. [Argonne National Lab., IL (United States)

    1997-10-01

    Chemically bonded phosphate ceramics (CBPCs) have several advantages that make them ideal candidates for containing radioactive and hazardous wastes. In general, phosphates have high solid-solution capacities for incorporating radionuclides, as evidenced by several phosphates (e.g., monazites and apatites) that are natural analogs of radioactive and rare-earth elements. The phosphates have high radiation stability, are refractory, and will not degrade in the presence of internal heating by fission products. Dense and hard CBPCs can be fabricated inexpensively and at low temperature by acid-base reactions between an inorganic oxide/hydroxide powder and either phosphoric acid or an acid-phosphate solution. The resulting phosphates are extremely insoluble in aqueous media and have excellent long-term durability. CBPCs offer the dual stabilization mechanisms of chemical fixation and physical encapsulation, resulting in superior waste forms. The goal of this task is develop and demonstrate the feasibility of CBPCs for S/S of wastes containing fission products. The focus of this work is to develop a low-temperature CBPC immobilization system for eluted {sup 99}Tc wastes from sorption processes.

  2. Transuranic contaminated waste form characterization and data base

    This volume contains 5 appendices. Title listing are: technologies for recovery of transuranics; nondestructive assay of TRU contaminated wastes; miscellaneous waste characteristics; acceptance criteria for TRU waste; and TRU waste treatment technologies

  3. Transuranic contaminated waste form characterization and data base

    Kniazewycz, B.G.; McArthur, W.C.

    1980-07-01

    This volume contains 5 appendices. Title listing are: technologies for recovery of transuranics; nondestructive assay of TRU contaminated wastes; miscellaneous waste characteristics; acceptance criteria for TRU waste; and TRU waste treatment technologies.

  4. Technical area status report for low-level mixed waste final waste forms. Volume 1

    Mayberry, J.L.; DeWitt, L.M. [Science Applications International Corp., Idaho Falls, ID (United States); Darnell, R. [EG and G Idaho, Inc., Idaho Falls, ID (United States)] [and others

    1993-08-01

    The Final Waste Forms (FWF) Technical Area Status Report (TASR) Working Group, the Vitrification Working Group (WG), and the Performance Standards Working Group were established as subgroups to the FWF Technical Support Group (TSG). The FWF TASR WG is comprised of technical representatives from most of the major DOE sites, the Nuclear Regulatory Commission (NRC), the EPA Office of Solid Waste, and the EPA`s Risk Reduction Engineering Laboratory (RREL). The primary activity of the FWF TASR Working Group was to investigate and report on the current status of FWFs for LLNM in this TASR. The FWF TASR Working Group determined the current status of the development of various waste forms described above by reviewing selected articles and technical reports, summarizing data, and establishing an initial set of FWF characteristics to be used in evaluating candidate FWFS; these characteristics are summarized in Section 2. After an initial review of available information, the FWF TASR Working Group chose to study the following groups of final waste forms: hydraulic cement, sulfur polymer cement, glass, ceramic, and organic binders. The organic binders included polyethylene, bitumen, vinyl ester styrene, epoxy, and urea formaldehyde. Section 3 provides a description of each final waste form. Based on the literature review, the gaps and deficiencies in information were summarized, and conclusions and recommendations were established. The information and data presented in this TASR are intended to assist the FWF Production and Assessment TSG in evaluating the Technical Task Plans (TTPs) submitted to DOE EM-50, and thus provide DOE with the necessary information for their FWF decision-making process. This FWF TASR will also assist the DOE and the MWIP in establishing the most acceptable final waste forms for the various LLMW streams stored at DOE facilities.

  5. Technical area status report for low-level mixed waste final waste forms

    The Final Waste Forms (FWF) Technical Area Status Report (TASR) Working Group, the Vitrification Working Group (WG), and the Performance Standards Working Group were established as subgroups to the FWF Technical Support Group (TSG). The FWF TASR WG is comprised of technical representatives from most of the major DOE sites, the Nuclear Regulatory Commission (NRC), the EPA Office of Solid Waste, and the EPA's Risk Reduction Engineering Laboratory (RREL). The primary activity of the FWF TASR Working Group was to investigate and report on the current status of FWFs for LLNM in this TASR. The FWF TASR Working Group determined the current status of the development of various waste forms described above by reviewing selected articles and technical reports, summarizing data, and establishing an initial set of FWF characteristics to be used in evaluating candidate FWFS; these characteristics are summarized in Section 2. After an initial review of available information, the FWF TASR Working Group chose to study the following groups of final waste forms: hydraulic cement, sulfur polymer cement, glass, ceramic, and organic binders. The organic binders included polyethylene, bitumen, vinyl ester styrene, epoxy, and urea formaldehyde. Section 3 provides a description of each final waste form. Based on the literature review, the gaps and deficiencies in information were summarized, and conclusions and recommendations were established. The information and data presented in this TASR are intended to assist the FWF Production and Assessment TSG in evaluating the Technical Task Plans (TTPs) submitted to DOE EM-50, and thus provide DOE with the necessary information for their FWF decision-making process. This FWF TASR will also assist the DOE and the MWIP in establishing the most acceptable final waste forms for the various LLMW streams stored at DOE facilities

  6. Preparation of plutonium waste forms with ICPP calcined high-level waste

    Glass and glass-ceramic forms developed for the immobilization of calcined high-level wastes generated by Idaho Chemical Processing Plant (ICPP) fuel reprocessing activities have been investigated for ability to immobilize plutonium and to simultaneously incorporate calcined waste as an anti-proliferation barrier. Within the forms investigated, crystallization of host phases result in an increased loading of plutonium as well as its incorporation into potentially more durable phases than the glass. The host phases were initially formed and characterized with cerium (Ce+4) as a surrogate for plutonium (Pu+4) and samarium as a neutron absorber for criticality control. Verification of the surrogate testing results were then performed replacing cerium with plutonium. All testing was performed with surrogate calcined high-level waste. The results of these tests indicated that a potentially useful host phase, based on zirconia, can be formed either by devitrification or solid state reaction in the glass studied. This phase incorporates plutonium as well as samarium and the calcined waste becomes part of the matrix. Its ease of formation makes it potentially useful in excess plutonium dispositioning. Other durable host phases for plutonium and samarium, including zirconolite and zircon have been formed from zirconia or alumina calcine through cold press-sintering techniques and hot isostatic pressing. Host phase formation experiments conducted through vitrification or by cold press-sintering techniques are described and the results discussed. Recommendations are given for future work that extends the results of this study

  7. Leaching test of the radioactive glass waste form

    As a part of the safety evaluation tests of simulated radioactive glass waste forms, the leaching experiments were carried out at 1000C by using the Soxhlet leach test apparatus in hot cell of the Waste Safety Testing Facility(WASTEF). The composition of the glass waste form used for this study is typical of the latest composition. The leach rates of 137Cs and 90Sr were 4.28 x 10-4 g/cm2 day and 1.92 x 10-4 g/cm2 day, respectively. There was little difference between these values and the results of the previous cold tests. The leach rate of 238Pu was 1.82 x 10-6 g/cm2 day. The behavior of leached radionuclides was examined on the basis of the phenomena observed during the leaching experiment. The result implied that the concentration of Pu in the leaching solution was dependent upon the solubility of Pu. (author)

  8. Evaluation of actinide partitioning and transmutation

    After a few centuries of radioactive decay the long-lived actinides, the elements of atomic numbers 89-103, may constitute the main potential radiological health hazard in nuclear wastes. This is because all but a very few fission products (principally technetium-99 and iodine-129) have by then undergone radioactive decay to insignificant levels, leaving the actinides as the principal radionuclides remaining. It was therefore at first sight an attractive concept to recycle the actinides to nuclear reactors, so as to eliminate them by nuclear fission. Thus, investigations of the feasibility and potential benefits and hazards of the concept of 'actinide partitioning and transmutation' were started in numerous countries in the mid-1970s. This final report summarizes the results and conclusions of technical studies performed in connection with a four-year IAEA Co-ordinated Research Programme, started in 1976, on the ''Environmental Evaluation and Hazard Assessment of the Separation of Actinides from Nuclear Wastes followed by either Transmutation or Separate Disposal''. Although many related studies are still continuing, e.g. on waste disposal, long-term safety assessments, and waste actinide management (particularly for low and intermediate-level wastes), some firm conclusions on the overall concept were drawn by the programme participants, which are reflected in this report

  9. Activity release from waste packages containing LL and IL waste forms under mechanical and thermal stresses

    For transport and handling of radioactive waste packages in an underground repository safety assessments are being performed to keep any unacceptable radiation hazards from the operational staff and the population in the site neighborhood. Therefore experiments were carried out to determine source terms for activity release from waste packages containing cemented waste forms in case of heavy mechanical and thermal impacts. Mechanical impact was applied by drop test with a maximum energy input of 3.105 Nm. A special cage construction around the target (reinforced concrete covered by a 80 mm steel plate) allows the collection of the airborne fines with a particle size of < 10 μm by using micro filters in a defined geometry. In addition, in two experiments the particle fraction with an aerodynamic diameter between 1 μm and 20 μm was determined using a cascade impactor. Additional laboratory experiments were performed to determine comparative values for different waste forms. In case of thermal impact, the temperature profiles in the waste forms were measured and the release of added indicators (Cs, Sr, Eu) was determined. Further laboratory experiments were performed with inactive samples to determine the temperature dependence of water release (Thermogravimetric-Analysis)

  10. Commercial high-level-waste management: options and economics. A comparative analysis of the ceramic and glass waste forms

    Results of an estimate of the waste management costs of the commercial high-level waste from a 3000 metric ton per year reprocessing plant show that the judicious use of the ceramic waste form can save about $2 billion during a 20-year operating campaign relative to the use of the glass waste form. This assumes PWR fuel is processed and the waste is encapsulated in 0.305-m-diam canisters with ultimate emplacement in a BWIP-type horizontal-borehole repository. The estimated total cost (capital and operating) of the management in the ceramic form is $2.0 billion, and that of the glass form is $4.0 billion. Waste loading and waste form density are the driving factors in that the low-waste loading (25%) and relatively low density (3.1 g/cm3) characteristic of the glass form require several times as many canisters to handle a given waste throughput than is needed for the ceramic waste form whose waste loading capability exceeds 60% and whose waste density is nominally 5.2 g/cm3) characteristic of the glass form requires several times as many canisters to handle a given waste throughput than is needed for the ceramic waste form whose waste loading capability exceeds 60% and whose waste density is nominally 5.2 g/cm3. The minimum-cost ceramic waste form has a 60 wt. % waste loading of commercial high-level waste and requires 25 years storage before emplacement in basalt with delayed backfill. Because of the process flexibility allowed by the availability of the high-waste loading of the ceramic form, the intermediate-level liquid waste stream can be mixed with the high-level liquid waste stream and economically processed and emplaced. The cost is greater by $0.3 billion than that of the best high-level liquid waste handling process sequence ($2.3 billion vs $2.0 billion), but this difference is less than the cost of the separate disposal of the intermediate-level liquid waste

  11. Commercial high-level-waste management: options and economics. A comparative analysis of the ceramic and glass waste forms

    McKisson, R.L.; Grantham, L.F.; Guon, J.; Recht, H.L.

    1983-02-25

    Results of an estimate of the waste management costs of the commercial high-level waste from a 3000 metric ton per year reprocessing plant show that the judicious use of the ceramic waste form can save about $2 billion during a 20-year operating campaign relative to the use of the glass waste form. This assumes PWR fuel is processed and the waste is encapsulated in 0.305-m-diam canisters with ultimate emplacement in a BWIP-type horizontal-borehole repository. The estimated total cost (capital and operating) of the management in the ceramic form is $2.0 billion, and that of the glass form is $4.0 billion. Waste loading and waste form density are the driving factors in that the low-waste loading (25%) and relatively low density (3.1 g/cm/sup 3/) characteristic of the glass form require several times as many canisters to handle a given waste throughput than is needed for the ceramic waste form whose waste loading capability exceeds 60% and whose waste density is nominally 5.2 g/cm/sup 3/) characteristic of the glass form requires several times as many canisters to handle a given waste throughput than is needed for the ceramic waste form whose waste loading capability exceeds 60% and whose waste density is nominally 5.2 g/cm/sup 3/. The minimum-cost ceramic waste form has a 60 wt. % waste loading of commercial high-level waste and requires 25 years storage before emplacement in basalt with delayed backfill. Because of the process flexibility allowed by the availability of the high-waste loading of the ceramic form, the intermediate-level liquid waste stream can be mixed with the high-level liquid waste stream and economically processed and emplaced. The cost is greater by $0.3 billion than that of the best high-level liquid waste handling process sequence ($2.3 billion vs $2.0 billion), but this difference is less than the cost of the separate disposal of the intermediate-level liquid waste.

  12. Crystalline ceramics: Waste forms for the disposal of weapons plutonium

    Ewing, R.C.; Lutze, W. [New Mexico Univ., Albuquerque, NM (United States); Weber, W.J. [Pacific Northwest Lab., Richland, WA (United States)

    1995-05-01

    At present, there are three seriously considered options for the disposition of excess weapons plutonium: (i) incorporation, partial burn-up and direct disposal of MOX-fuel; (ii) vitrification with defense waste and disposal as glass ``logs``; (iii) deep borehole disposal (National Academy of Sciences Report, 1994). The first two options provide a safeguard due to the high activity of fission products in the irradiated fuel and the defense waste. The latter option has only been examined in a preliminary manner, and the exact form of the plutonium has not been identified. In this paper, we review the potential for the immobilization of plutonium in highly durable crystalline ceramics apatite, pyrochlore, monazite and zircon. Based on available data, we propose zircon as the preferred crystalline ceramic for the permanent disposition of excess weapons plutonium.

  13. Leaching from cementitious waste forms in belowground vaults

    Solidification and/or stabilization with cementitious materials prior to burial is one option for disposal of liquid hazardous and radioactive wastes. A common design for disposal of cementitious waste forms is to pour the material into large belowground vaults. The leaching performance of partially degraded monolithic vaults is examined quantitatively for facilities located in humid to semiarid climates. Development of perched water on the vault roof leading to fracture flow through the structure is predicted for a wide range of climate and design conditions. Leaching controlled by diffusion in matrix blocks out to fractures is examined parametrically in relation to water flux rate and crack spacing. Depending upon the parameters examined, release rate may be controlled by water flux rate or diffusion. Under some circumstances, contaminant release rates and exit concentrations are predicted to be inversely related. In this situation, minimization of release does not result in the lowest predicted groundwater concentrations below the vault

  14. Development of Todga extraction process for high-level liquid waste preliminary evaluation of actinide separation by calculation

    Extraction process for actinide separation from HLLW with N,N,N',N'-tetra-octyl-3-oxa-pentane-diamide (TODGA) was preliminarily evaluated by calculation of Am and Sr behaviors. Results of the calculation showed that it is possible to establish an extraction process with 0.1 M or 0.2 M TODGA in n-dodecane, where Am is extracted in a very high yield of more than 99.99% and Sr is kept in the aqueous phase in a yield of more than 99.95%. The solution volume required for the treatment of an unit amount of HLLW was also evaluated using data on extraction capacity as the first step for the estimation of the process scale. (author)

  15. The kinetics of alpha-decay-induced amorphization in zircon and apatite containing weapons-grade plutonium or other actinides

    Zircon and apatite form as actinide host phases in several high-level waste forms and have been proposed as host phases for the disposition of excess weapons-grade Pu and other actinides. Additionally, closely-related structure types appear as actinide-bearing phases among the corrosion products of spent nuclear fuel and high-level waste glasses. Self-radiation damage from α-decay of the incorporated Pu or other actinides can affect the durability and performance of these actinide-bearing phases. For both zircon and apatite, these effects can be modeled as functions of storage time and repository temperature and validated by comparison with data from natural occurrences. Natural zircons and apatites, with ages up to 4 billion years, provide abundant evidence for their long-term durability because of their wide spread use in geochronology and fission-track dating. Detailed studies of natural zircons and apatites, 238Pu-containing zircon, a 244Cm-containing silicate apatite, and ion-irradiated zircon, natural apatite and synthetic silicate apatites provide a unique basis for the analysis of α-decay effects over broad time scales. Models for α-decay effects in zircon and apatite are developed that show α-decay of Pu and other actinides will lead to a crystalline-to-amorphous transformation in zircon, but not in apatite, under conditions typical of a repository, such as the Yucca Mountain site. (orig.)

  16. ALMR potential for actinide consumption

    The Advanced Liquid Metal Reactor (ALMR) is a US Department of Energy (DOE) sponsored fast reactor design based on the Power Reactor, Innovative Small Module (PRISM) concept originated by General Electric. This reactor combines a high degree of passive safety characteristics with a high level of modularity and factory fabrication to achieve attractive economics. The current reference design is a 471 MWt modular reactor fueled with ternary metal fuel. This paper discusses actinide transmutation core designs that fit the design envelope of the ALMR and utilize spent LWR fuel as startup material and for makeup. Actinide transmutation may be accomplished in the ALMR core by using either a breeding or burning configuration. Lifetime actinide mass consumption is calculated as well as changes in consumption behavior throughout the lifetime of the reactor. Impacts on system operational and safety performance are evaluated in a preliminary fashion. Waste disposal impacts are discussed. (author)

  17. Physiochemical and spectroscopic behavior of actinides and lanthanides in solution, their sorption on minerals and their compounds formed with macromolecules; Comportamiento fisicoquimico y espectroscopico de actinidos y lantanidos en solucion, su sorcion sobre minerales y sus compuestos formados con macromoleculas

    Jimenez R, M., E-mail: melania.jimenez@inin.gob.m [ININ, Departamento de Quimica, Carretera Mexico-Toluca s/n, 52750 Ocoyoacac, Estado de Mexico (Mexico)

    2010-07-01

    From the chemical view point, the light actinides has been those most studied; particularly the uranium, because is the primordial component of the nuclear reactors. The chemical behavior of these elements is not completely defined, since they can behave as transition metals or metals of internal transition, as they are the lanthanides. The actinides are radioactive; between them they are emitters of radiation alpha, highly toxic, of live half long and some very long, and artificial elements. For all this, to know them sometimes is preferable to use their chemical similarity with the lanthanides and to study these. In particular, the migration of emitters of radiation alpha to the environment has been studied taking as model the uranium. It is necessary to mention that actinides and lanthanides elements are in the radioactive wastes of the nuclear reactors. In the Chemistry Department of the Instituto Nacional de Investigaciones Nucleares (ININ) the researches about the actinides and lanthanides began in 1983 and, between that year and 1995 several works were published in this field. In 1993 the topic was proposed as a Department project and from then around of 13 institutional projects and managerial activity have been developed, besides 4 projects approved by the National Council of Science and Technology. The objective of the projects already developed and of the current they have been contributing knowledge for the understanding of the chemical behavior of the lanthanides and actinides, as much in solution as in the solid state, their behavior in the environment and the chemistry of their complexes with recurrent and lineal macromolecules. (Author)

  18. Preparation of isotopes and sources of actinide elements

    As the C.E.A. possesses no isotopic separation facility, the productions of isotopes of actinide elements are performed: a) by neutron irradiation and chemical treatment of special targets, b) by milking decay products from stocks of aged actinide elements, c) by chemical treatment of alpha active wastes. These productions concern the following isotopes: 233U, 238Pu, 242Pu, 243Cm, 242Cm, 244Cm (a); 228Th, 229Th, 234U, 237U, 239Np, 240Pu, 241Am, 248Cm (b); 237Np, 241Am (c). These isotopes are produced to satisfy French and international needs and are sent to users in various forms: solutions, metals, oxides, fluorides, or in different sources forms. The preparation of the sources represents an important field of activities divided into two parts: 1/Industrial sources: production of large series of different sources, 2/ Scientific sources: production of sources suitable for a specific scientific problem. A large overview of these activities is given

  19. Naturally occurring crystalline phases: analogues for radioactive waste forms

    Haaker, R.F.; Ewing, R.C.

    1981-01-01

    Naturally occurring mineral analogues to crystalline phases that are constituents of crystalline radioactive waste forms provide a basis for comparison by which the long-term stability of these phases may be estimated. The crystal structures and the crystal chemistry of the following natural analogues are presented: baddeleyite, hematite, nepheline; pollucite, scheelite;sodalite, spinel, apatite, monazite, uraninite, hollandite-priderite, perovskite, and zirconolite. For each phase in geochemistry, occurrence, alteration and radiation effects are described. A selected bibliography for each phase is included.

  20. Naturally occurring crystalline phases: analogues for radioactive waste forms

    Naturally occurring mineral analogues to crystalline phases that are constituents of crystalline radioactive waste forms provide a basis for comparison by which the long-term stability of these phases may be estimated. The crystal structures and the crystal chemistry of the following natural analogues are presented: baddeleyite, hematite, nepheline; pollucite, scheelite;sodalite, spinel, apatite, monazite, uraninite, hollandite-priderite, perovskite, and zirconolite. For each phase in geochemistry, occurrence, alteration and radiation effects are described. A selected bibliography for each phase is included

  1. XAFS study on electronic structure analysis of actinide complexes

    Structures and electronic states of actinide complexes in solution were reviewed in relation to chemical separation required from nuclear fuel processing and nuclear waste disposal. Actinide complexes formed from organic compounds were studied in respect of solvent extraction in a wet method for nuclear fuel reprocessing. Particular attention was paid to the experiments by XAFS using synchrotron radiation. A Fourier transformation form of EXAFS oscillation was shown for a U(VI)-amide complex in dodecane solution. The structure radial function of Uranium-DH2EHA (N, N-dihyxyl-2-ethylhexanamice) in solution was determined by EXAFS, and the contributions of two oxygens in an axial direction and of ligand atoms coordinated in an equatorial plane, which combined with a central uranium ion, were indicated in the structure radial function. Structure parameters for U-, Np- and Pu-TBP(Tributyl phosphate) complexes, and for U-amide complexes were listed in Table. A theory predicted a systematic increase of covalency for complexes formed from UO22+∼PO22+ and TEP with an increase of atomic number of actinides, but for U-amide and U∼Pu-TBP complexes the effect of covalency was not reflected in interatomic distances. Some correlations between distribution ratios and different substituents were found in the interatomic distances between uranium and ligand atoms-Distribution ratios of U(VI) depended on interatomic distances between actinide atoms and oxygen ions in carbonyl and in nitric acid. Similarity of chemical bonds in all U-amide complexes except DH2EHA was indicated from XANES spectra of U LIII absorption edge. Three structures for Np(V)-carbon complexes were shown in a ball-and-stick model, and the structure parameters determined by EXAFS were also summarized in Table. Separation of trivalent actinide from the same valent lanthanide was described in connection with soft donors, which have donors such as sulfur and nitrogen atoms. (Kazumata, Y.)

  2. Candidate waste forms for immobilisation of waste chloride salt from pyroprocessing of spent nuclear fuel

    Highlights: ► Sodalite-based ceramics are current best candidates for incorporation of used pyrochemical nuclear waste salts. ► Cs incorporation in apatite is experimentally insignificant. ► Spodiosite is not a credible candidate for incorporation of nuclear waste. - Abstract: Sodalite/glass bodies prepared by hot isostatic pressing (HIPing) at ∼850 °C/100 MPa are candidates for immobilising fission product-bearing waste KCl–LiCl pyroprocessing salts. To study the capacity of sodalite to structurally incorporate such pyroprocessing salts, K, Li, Cs, Sr, Ba and La were individually targeted for substitution in a Na site in sodalite (Na vacancies targeted as charge compensators for alkaline and rare earths) and studied by X-ray diffraction and scanning electron microscopy after sintering in the range of 800–1000 °C. K and Li appeared to enter the sodalite, but Cs, Sr and Ba formed aluminosilicate phases and La formed an oxyapatite phase. However these non-sodalite phases have reasonable resistance to water leaching. Pure chlorapatite gives superior leach resistance to sodalite, and alkalis, alkaline and rare earth ions are generally known to enter chlorapatite, but attempts to incorporate simulated waste salt formulations into HIPed chlorapatite-based preparations or to substitute Cs alone into the structure of Ca-based chlorapatite were not successful on the basis of scanning electron microscopy. The materials exhibited severe water leachability, mainly in regard to Cs release. Attempts to substitute Cs into Ba- and Sr-based chlorapatites also did not look encouraging. Consequently the use of apatite alone to retain fission product-bearing waste pyroprocessing salts from electrolytic nuclear fuel reprocessing is problematical, but chlorapatite glass–ceramics may be feasible, albeit with reduced waste loadings. Spodiosite, Ca2(PO4)Cl, does not appear to be suitable for incorporation of Cl-bearing waste containing fission products.

  3. Actinides and the environment

    The book combines in one volume the opinions of experts regarding the interaction of radionuclides with the environment and possible ways to immobilize and dispose of nuclear waste. The relevant areas span the spectrum from pure science, such as the fundamental physics and chemistry of the actinides, geology, environmental transport mechanisms, to engineering issues such as reactor operation and the design of nuclear waste repositories. The cross-fertilization between these various areas means that the material in the book will be accessible to seasoned scientists who may wish to obtain an overview of the current state of the art in the field of environmental remediation of radionuclides, as well as to beginning scientists embarking on a career in this field. refs

  4. Leaching behavior of glass ceramic nuclear waste forms

    Glass ceramic waste forms have been investigated as alternatives to borosilicate glasses for the immobilization of high-level radioactive waste at Pacific Northwest Laboratory (PNL). Three glass ceramic systems were investigated, including basalt, celsian, and fresnoite, each containing 20 wt % simulated high-level waste calcine. Static leach tests were performed on seven glass ceramic materials and one parent glass (before recrystallization). Samples were leached at 900C for 3 to 28 days in deionized water and silicate water. The results, expressed in normalized elemental mass loss, (g/m2), show comparable releases from celsian and fresnoite glass ceramics. Basalt glass ceramics demonstrated the lowest normalized elemental losses with a nominal release less than 2 g/m2 when leached in polypropylene containers. The releases from basalt glass ceramics when leached in silicate water were nearly identical with those in deionized water. The overall leachability of celsian and fresnoite glass ceramics was improved when silicate water was used as the leachant

  5. Engineering-Scale Demonstration of DuraLith and Ceramicrete Waste Forms

    Josephson, Gary B.; Westsik, Joseph H.; Pires, Richard P.; Bickford, Jody; Foote, Martin W.

    2011-09-23

    To support the selection of a waste form for the liquid secondary wastes from the Hanford Waste Immobilization and Treatment Plant, Washington River Protection Solutions (WRPS) has initiated secondary waste form testing on four candidate waste forms. Two of the candidate waste forms have not been developed to scale as the more mature waste forms. This work describes engineering-scale demonstrations conducted on Ceramicrete and DuraLith candidate waste forms. Both candidate waste forms were successfully demonstrated at an engineering scale. A preliminary conceptual design could be prepared for full-scale production of the candidate waste forms. However, both waste forms are still too immature to support a detailed design. Formulations for each candidate waste form need to be developed so that the material has a longer working time after mixing the liquid and solid constituents together. Formulations optimized based on previous lab studies did not have sufficient working time to support large-scale testing. The engineering-scale testing was successfully completed using modified formulations. Further lab development and parametric studies are needed to optimize formulations with adequate working time and assess the effects of changes in raw materials and process parameters on the final product performance. Studies on effects of mixing intensity on the initial set time of the waste forms are also needed.

  6. Corrosion behaviour of the high level waste forms borosilicate glass and spent fuel in salt brines

    The objective of the first part of this work is to describe the extent to which Np, Pu, Am and Tc are mobilized from vitrified high-level radioactive waste into the near field of an HLW repository in a salt formation, when a hot and concentrated salt solution comes into contact with the glass. Waste form corrosion studies are conducted with a salt solution representing the composition of a fluid phase encountered in drill holes in the Gorleben salt dome. Test temperatures are determined by the designed maximum surface temperature of 200 deg. C for the vitrified waste in the Gorleben salt. The following results were obtained: 1. pH changes of the radioactive leachate are the same as in inactive leachates. 2. The time and temperature dependence of the reaction for the radioactive glass are in excellent agreement with that of the inactive glass. 3. Np, Pu, Am, and Tc have not been reimmobilized in secondary minerals. Hence, mobilization of these radionuclides is governed by the kinetics of glass dissolution. Pu oxidation states were analyzed and related to Pu concentrations. The second part is focused on the corrosion behaviour of spent fuel in contact with salt solution. For characterizing the potential chemical reactions of spent UO2 fuel during direct disposal in salt formations, corrosion tests were performed at various particle sizes with both high burnup spent fuel and unirradiated UO2. Studied effects include temperature, pH, radiolysis, oxidant concentration, surface to volume ratio (S/V) and the presence of container material. Results are applicable not only to salt media but also to others: (1) 90Sr data are indicative of matrix dissolution. (2) Except at high S/V ratios, spent fuel dissolution rates are proportional to surface area and are similar in both saline media and deionized water. (3) Dissolution rates of unirradiated UO2 are much lower and are proportional to oxidant concentration but almost independent of the nature of the oxidant. (4) It is

  7. Multiple diglycolamide functionalized ligands in room temperature ionic liquids: 'green' solvents for actinide partitioning

    Multiple-diglycolamide-functionalized ligands (MDGA) in room temperature ionic liquids (RTILs) were studied for extraction of actinides and lanthanides from aqueous acidic solutions. The extraction kinetics, separation behavior, associated thermodynamics of extraction, nature of the extracted species formed were studied. Luminescence spectroscopy was used to understand the nature of bonding between metal and ligands, formation of inner sphere/outer sphere complex etc. The radiolytic stability of solvent systems was studied and attempt was made to understand the degradation products. Finally, all the systems were evaluated for 'actinide partitioning' from synthetic high level liquid waste solution (HLLW). (author)

  8. Crystalline Ceramic Waste Forms: Report Detailing Data Collection In Support Of Potential FY13 Pilot Scale Melter Test

    Brinkman, K. S.; Amoroso, J.; Marra, J. C.; Fox, K. M.

    2012-09-21

    The research conducted in this work package is aimed at taking advantage of the long term thermodynamic stability of crystalline ceramics to create more durable waste forms (as compared to high level waste glass) in order to reduce the reliance on engineered and natural barrier systems. Durable ceramic waste forms that incorporate a wide range of radionuclides have the potential to broaden the available disposal options and to lower the storage and disposal costs associated with advanced fuel cycles. Assemblages of several titanate phases have been successfully demonstrated to incorporate radioactive waste elements, and the multiphase nature of these materials allows them to accommodate variation in the waste composition. Recent work has shown that they can be successfully produced from a melting and crystallization process. The objective of this report is to summarize the data collection in support of future melter demonstration testing for crystalline ceramic waste forms. The waste stream used as the basis for the development and testing is a combination of the projected Cs/Sr separated stream, the Trivalent Actinide - Lanthanide Separation by Phosphorous reagent Extraction from Aqueous Komplexes (TALSPEAK) waste stream consisting of lanthanide fission products, the transition metal fission product waste stream resulting from the transuranic extraction (TRUEX) process, and a high molybdenum concentration with relatively low noble metal concentrations. The principal difficulties encountered during processing of the ?reference ceramic? waste form by a melt and crystallization process were the incomplete incorporation of Cs into the hollandite phase and the presence of secondary Cs-Mo non-durable phases. In the single phase hollandite system, these issues were addressed in this study by refining the compositions to include Cr as a transition metal element and the use of Ti/TiO{sub 2} buffer to maintain reducing conditions. Initial viscosity studies of ceramic waste

  9. Integrated testing of the SRL-165 glass waste form

    Integrated testing of the important components of a glass waste form waste package has been performed in order to gain a better understanding of the processes of radionuclide release and transport in the near field environment. Based upon an interpretation of the depth of penetration of hydrogen in reacted SRL-165 glass we have modeled the radionuclide release from the glass as a combined process of (1) the diffusive exchange of alkalis and boron in the glass for hydrogen species in the solution (D = 10-16 cm2/s) and (2) surface dissolution. Surface dissolution controls the release of components not exchanged by diffusion and takes place at a rate of 1.5 to 3.0 μm/yr. Subsequent to release the radionuclides may remain in the leach solution, diffuse into the tuff, or precipitate as secondary phases. Precipitation is particularly important for plutonium and americium. Diffusive transport of radionuclides through the tuff takes place at an extremely slow rate, D = 10-16 cm2/s. As such, the mass of radionuclides incorporated in the tuff by diffusion during the tests is inconsequential relative to that in the leach solution (with the exception of plutonium) and can be ignored in mass balance calculations. Mass balance calculations based upon the release of radionuclides by surface dissolution of the glass waste form are in good agreement with observed solution chemistry when allowances are made for a pulse of dissolution early in the tests. This pulse may be due to either the rapid dissolution of high-energy surface features early in the integrated tests, or an initially high surface dissolution rate that decreases with time as silica saturation is approached, or a combination of the two

  10. Description of DWPF reference waste form and canister

    This document describes the reference waste form and canister for the Defense Waste Processing Facility (DWPF). The facility is planned for location at the Savannah River Plant in Aiken, SC, and is scheduled for construction authorization during FY-1983. The reference canister is fabricated of 24-in.-OD 304L stainless steel pipe with a dished bottom, domed head, and lifting and welding flanges on the head neck. The overall canister length is 9 ft 10 in., with a wall thickness of 3/8-in. (schedule 20 pipe). The canister length was selected to reduce equipment cell height in the DWPF to a practical size. The canister diameter was selected to ensure that a filled canister with its shipping cask could be accommodated on a legal-weight truck. The overall dimensions and weight appear to be generally compatible with preliminary assessments of repository requireiajps. The rabarajca saspa bkri is bkrksilicapa class cojtaining approximately 28 wt % sludge oxides with the balance glass frit. Borosilicate glass was chosen because of its high resistance to leaching by water, its relatively high solubility for nuclides found in the sludge, and its reasonably low melting temperature. The glass frit contains approximately 58% SiO2 and 15% B2O3. This composition results in a low average leachability in the waste form of approximately 5 x 10-9 g/cm2-day based on 137Cs over 365 days in 250C water. The canister is filled with 3260 lb of glass which occupies about 85% of the free canister volume. The filled canister will generate approximately 425 watts when filled with oxides from 5-year-old sludge and 15-year-old supernate from the Stage 1 and Stage 2 processes. The radionuclide content of the canister is about 150,000 curies, with a radiation level of 2 x 104 rem/hour at 1 cm

  11. Stability of High-Level Radioactive Waste Forms

    Besmann, T.M.

    2001-06-22

    High-level waste (HLW) glass compositions, processing schemes, limits on waste content, and corrosion/dissolution release models are dependent on an accurate knowledge of melting temperatures and thermochemical values. Unfortunately, existing models for predicting these temperatures are empirically-based, depending on extrapolations of experimental information. In addition, present models of leaching behavior of glass waste forms use simplistic assumptions or experimentally measured values obtained under non-realistic conditions. There is thus a critical need for both more accurate and more widely applicable models for HLW glass behavior, which this project addressed. Significant progress was made in this project on modeling HLW glass. Borosilicate glass was accurately represented along with the additional important components that contain iron, lithium, potassium, magnesium, and calcium. The formation of crystalline inclusions in the glass, an issue in Hanford HLW formulations, was modeled and shown to be predictive. Thus the results of this work have already demonstrated practical benefits with the ability to map compositional regions where crystalline material forms, and therefore avoid that detrimental effect. With regard to a fundamental understanding, added insights on the behavior of the components of glass have been obtained, including the potential formation of molecular clusters. The EMSP project had very significant effects beyond the confines of Environmental Management. The models developed for glass have been used to solve a very costly problem in the corrosion of refractories for glass production. The effort resulted in another laboratory, Sandia National Laboratories-Livermore, to become conversant in the techniques and to apply those through a DOE Office of Industrial Technologies project joint with PPG Industries. The glass industry as a whole is now cognizant of these capabilities, and there is a Glass Manufacturer's Research Institute

  12. Proposed research and development plan for mixed low-level waste forms

    The objective of this report is to recommend a waste form program plan that addresses waste form issues for mixed low-level waste (MLLW). The report compares the suitability of proposed waste forms for immobilizing MLLW in preparation for permanent near-surface disposal and relates them to their impact on the U.S. Department of Energy's mixed waste mission. Waste forms are classified into four categories: high-temperature waste forms, hydraulic cements, encapsulants, and specialty waste forms. Waste forms are evaluated concerning their ability to immobilize MLLW under certain test conditions established by regulatory agencies and research institutions. The tests focused mainly on leach rate and compressive strength. Results indicate that all of the waste forms considered can be tailored to give satisfactory performance immobilizing large fractions of the Department's MLLW inventory. Final waste form selection will ultimately be determined by the interaction of other, often nontechnical factors, such as economics and politics. As a result of this report, three top-level programmatic needs have been identified: (1) a basic set of requirements for waste package performance and disposal; (2) standardized tests for determining waste form performance and suitability for disposal; and (3) engineering experience operating production-scale treatment and disposal systems for MLLW

  13. Proposed research and development plan for mixed low-level waste forms

    O`Holleran, T.O.; Feng, X.; Kalb, P. [and others

    1996-12-01

    The objective of this report is to recommend a waste form program plan that addresses waste form issues for mixed low-level waste (MLLW). The report compares the suitability of proposed waste forms for immobilizing MLLW in preparation for permanent near-surface disposal and relates them to their impact on the U.S. Department of Energy`s mixed waste mission. Waste forms are classified into four categories: high-temperature waste forms, hydraulic cements, encapsulants, and specialty waste forms. Waste forms are evaluated concerning their ability to immobilize MLLW under certain test conditions established by regulatory agencies and research institutions. The tests focused mainly on leach rate and compressive strength. Results indicate that all of the waste forms considered can be tailored to give satisfactory performance immobilizing large fractions of the Department`s MLLW inventory. Final waste form selection will ultimately be determined by the interaction of other, often nontechnical factors, such as economics and politics. As a result of this report, three top-level programmatic needs have been identified: (1) a basic set of requirements for waste package performance and disposal; (2) standardized tests for determining waste form performance and suitability for disposal; and (3) engineering experience operating production-scale treatment and disposal systems for MLLW.

  14. Material Recovery and Waste Form Development FY 2015 Accomplishments Report

    The Material Recovery and Waste Form Development (MRWFD) Campaign under the U.S. Department of Energy (DOE) Fuel Cycle Technologies (FCT) Program is responsible for developing advanced separation and waste form technologies to support the various fuel cycle options defined in the DOE Nuclear Energy Research and Development Roadmap, Report to Congress, April 2010. The FY 2015 Accomplishments Report provides a highlight of the results of the research and development (R&D) efforts performed within the MRWFD Campaign in FY-14. Each section contains a high-level overview of the activities, results, technical point of contact, applicable references, and documents produced during the fiscal year. This report briefly outlines campaign management and integration activities, but primarily focuses on the many technical accomplishments made during FY-15. The campaign continued to utilize an engineering driven-science-based approach to maintain relevance and focus. There was increased emphasis on development of technologies that support near-term applications that are relevant to the current once-through fuel cycle.

  15. Material Recovery and Waste Form Development FY 2015 Accomplishments Report

    Todd, Terry Allen [Idaho National Lab. (INL), Idaho Falls, ID (United States); Braase, Lori Ann [Idaho National Lab. (INL), Idaho Falls, ID (United States)

    2015-11-01

    The Material Recovery and Waste Form Development (MRWFD) Campaign under the U.S. Department of Energy (DOE) Fuel Cycle Technologies (FCT) Program is responsible for developing advanced separation and waste form technologies to support the various fuel cycle options defined in the DOE Nuclear Energy Research and Development Roadmap, Report to Congress, April 2010. The FY 2015 Accomplishments Report provides a highlight of the results of the research and development (R&D) efforts performed within the MRWFD Campaign in FY-14. Each section contains a high-level overview of the activities, results, technical point of contact, applicable references, and documents produced during the fiscal year. This report briefly outlines campaign management and integration activities, but primarily focuses on the many technical accomplishments made during FY-15. The campaign continued to utilize an engineering driven-science-based approach to maintain relevance and focus. There was increased emphasis on development of technologies that support near-term applications that are relevant to the current once-through fuel cycle.

  16. Radiation damage effects in pyrochlore and zirconolite ceramic matrices for the immobilization of actinide-rich wastes

    Actinide-doping experiments using short-lived 238Pu and 244Cm have demonstrated that pyrochlore and zirconolite become fully amorphous at a dose of 0.2-0.5 x 1016 α/mg at ambient temperature and exhibit bulk swelling of 5-7%. Detailed studies of natural samples have included determination of the critical amorphization dose, long-term annealing rate, microstructural changes as a function of dose, and the thermal histories of the host rocks. Together, the laboratory based work and studies of natural samples indicate that the critical amorphization dose will increase by about a factor of 2-4 for samples stored at temperatures of 100-200 deg. C for up to 10 million years. These studies of alpha-decay damage have been complemented by heavy ion irradiation studies over the last ten years. Most of the irradiation work has concerned the critical amorphization dose as a function of temperature in thin films; however, some work has been carried out on bulk samples. The irradiation work indicates that most pyrochlore and zirconolite compositions will have similar critical amorphization doses at low temperatures (e.g., below 300-400 deg. C). Pyrochlore with Zr as the major B-site cation transform to a defect fluorite structure with increasing ion irradiation dose, but do not become amorphous. (authors)

  17. The ‘granite encapsulation’ route to the safe disposal of Pu and other actinides

    Gibb, F. G. F.; Taylor, K. J.; Burakov, B. E.

    2008-03-01

    Waste actinides, including plutonium, present a long-term management problem and a serious security issue. Immobilisation in mineral or ceramic waste forms for interim storage is a widely proposed first step. The safest, most secure geological disposal for Pu is in very deep boreholes and we propose that the key step to combination of these immobilisation and disposal concepts is encapsulation of the waste form in cylinders of recrystallized granite. We discuss the underpinning science, focusing on experimental work, and consider implementation. Finally, we present and discuss analyses of zircon, UO 2 and Ce-doped cubic zirconia from high pressure and temperature experiments in granitic melts that demonstrate the viability of this solution and that actinides can be isolated from the environment for millions, maybe hundreds of millions, of years.

  18. Fundamental experimental determinations of thermal and radiolytic gas generation over actinide oxides

    In the areas of actinide waste disposition and storage and medium- to long-term retrievable U and Pu materials storage, the issue of water and other small molecule interactions with pure or impure actinide oxide materials and metal has become a major concern. Small molecule reactions in these systems have led to changes in materials stoichiometry, containment corrosion and breaches, dispersal of material resulting from pressurization, and the collapse of sealed containers due to the formation of partial vacuum. The exact nature of these reactions and the resulting implications for medium- to long-term storage are not well understood, although some studies have attempted to explain them from a large body of observations and experiments. The interaction of water with actinide and actinide oxide surfaces constitutes the fundamental technical basis for understanding and predicting long-term actinide material storage behavior. In this paper some of the studies that pertain to these efforts are summarized with particular emphasis on gas generation and/or consumption events relevant to actinide materials storage. These studies include fundamental surface studies of actinide and actinide oxide materials with water vapor using a wide variety of physical chemical and surface-specific techniques. In addition, radical surface chemistry arising from radiolytic decomposition of adsorbed water molecules is experimentally examined using unique gas exposure techniques. Preliminary studies are described and compared with conventional molecular gas-solid chemical model systems. Where possible, the relevant results from the surface science studies are utilized in understanding the back reaction of H2 and O2 to form H2O at relevant pressures in actual storage scenarios (described by Morales)

  19. Reevaluation of Vitrified High-Level Waste Form Criteria for Potential Cost Savings at the Defense Waste Processing Facility - 13598

    At the Savannah River Site (SRS) the Defense Waste Processing Facility (DWPF) has been immobilizing SRS's radioactive high level waste (HLW) sludge into a durable borosilicate glass since 1996. Currently the DWPF has poured over 3,500 canisters, all of which are compliant with the U. S. Department of Energy's (DOE) Waste Acceptance Product Specifications for Vitrified High-Level Waste Forms (WAPS) and therefore ready to be shipped to a federal geologic repository for permanent disposal. Due to DOE petitioning to withdraw the Yucca Mountain License Application (LA) from the Nuclear Regulatory Commission (NRC) in 2010 and thus no clear disposal path for SRS canistered waste forms, there are opportunities for cost savings with future canister production at DWPF and other DOE producer sites by reevaluating high-level waste form requirements and compliance strategies and reducing/eliminating those that will not negatively impact the quality of the canistered waste form. (authors)

  20. Reevaluation Of Vitrified High-Level Waste Form Criteria For Potential Cost Savings At The Defense Waste Processing Facility

    At the Savannah River Site (SRS) the Defense Waste Processing Facility (DWPF) has been immobilizing SRS's radioactive high level waste (HLW) sludge into a durable borosilicate glass since 1996. Currently the DWPF has poured over 3,500 canisters, all of which are compliant with the U. S. Department of Energy's (DOE) Waste Acceptance Product Specifications for Vitrified High-Level Waste Forms (WAPS) and therefore ready to be shipped to a federal geologic repository for permanent disposal. Due to DOE petitioning to withdraw the Yucca Mountain License Application (LA) from the Nuclear Regulatory Commission (NRC) in 2010 and thus no clear disposal path for SRS canistered waste forms, there are opportunities for cost savings with future canister production at DWPF and other DOE producer sites by reevaluating high-level waste form requirements and compliance strategies and reducing/eliminating those that will not negatively impact the quality of the canistered waste form

  1. Wet oxidative degradation of cellulosic wastes 5- chemical and thermal properties of the final waste forms

    In this study, the residual solution arising from the wet oxidative degradation of solid organic cellulosic materials, as one of the component of radioactive solid wastes, using hydrogen peroxide as oxidant. Were incorporated into ordinary Portland cement matrix. Leaching as well as thermal characterizations of the final solidified waste forms were evaluated to meet the final disposal requirements. Factors, such as the amount of the residual solution incorporated, types of leachant. Release of different radionuclides and freezing-thaw treatment, that may affect the leaching characterization. Were studied systematically from the data obtained, it was found that the final solid waste from containing 35% residual solution in tap water is higher than that in ground water or sea water. Based on the data obtained from thermal analysis, it could be concluded that incorporating the residual solution form the wet oxidative degradation of cellulosic materials has no negative effect on the hydration of cement materials and consequently on the thermal stability of the final solid waste from during the disposal process

  2. Study of the sorption of actinide analogues on calcite and smectite as a model to predict the evolution of radioactive waste disposal in geological sites

    In the framework of the problem of the radioactive waste disposal in deep geological sites, the purpose of this study is to predict the sorption of radionuclides on minerals within the geological barrier, after the rupture of the containers and the release of the radionuclides into underground water. Neodymium labelled by 147Nd was used as an analogue of trivalent actinides. Calcite and smectite were used as examples of altered minerals of granitic sites. In simple media, neodymium is retained with a high affinity on both minerals. Fast kinetics of fixation, high distribution coefficients and sorption capacities are favorable factors for the slowing down of radionuclide migration in underground water. Fixation on calcite is quasi irreversible. A second kinetic step was observed, leading to an increase of the retention capacity. In the first step, this is probably a superficial sorption, but with a non-homogeneous affinity for sorption sites. An exchange mechanism of Nd3+ with Na+ et Ca2+ ions of smectite occurs. The Freundlich isotherm observed for both minerals can be used for predicting the retention of radioelements as a function of their concentration and introducing these data in a migration model after comparison with the results of dynamic and field experiments. (author)

  3. Scientific basis for long-term prediction of waste-form performance under repository conditions

    This paper presents an overview of the fundamental principles involved in predicting long-term performance of waste forms by the as-low-as-reasonably-achievable approach. Repository conditions which make up the waste-form environment, the aging of the waste form, the important radionuclides in the waste form, the chemistry of repository fluids, and multicomponent interactions testing were considered in order to describe these principles. The need for confidence limits on the prediction of waste-form performance and ways of achieving a definition of the confidence limits are discussed

  4. Improved Consolidation Process for Producing Ceramic Waste forms

    Hash, Harry C.; Hash, Mark C.

    1998-07-24

    A process for the consolidation and containment of solid or semisolid hazardous waste, which process comprises closing an end of a circular hollow cylinder, filling the cylinder with the hazardous waste, and then cold working the cylinder to reduce its diameter while simultaneously compacting the waste. The open end of the cylinder can be sealed prior to or after the cold working process. The preferred method of cold working is to draw the sealed cylinder containing the hazardous waste through a plurality of dies to simultaneously reduce the diameter of the tube while compacting the waste. This process provides a quick continuous process for consolidating hazardous waste, including radioactive waste.

  5. Reference waste form, basalts, and ground water systems for waste interaction studies

    Deju, R.A.; Ledgerwood, R.K.; Long, P.E.

    1978-09-01

    This report summarizes the type of waste form, basalt, and ground water compositions to be used in theoretical and experimental models of the geochemical environment to be simulated in studying a typical basalt repository. Waste forms to be used in the experiments include, and are limited to, glass, supercalcine, and spent unreprocessed fuel. Reference basalts selected for study include the Pomona member and the Umtanum Unit, Shwana Member, of the Columbia River Basalt Group. In addition, a sample of the Basalt International Geochemical Standard (BCR-1) will be used for cross-comparison purposes. The representative water to be used is of a sodium bicarbonate composition as determined from results of analyses of deep ground waters underlying the Hanford Site. 12 figures, 13 tables.

  6. Silica based gel as a potential waste form for high level waste from fuel reprocessing

    To assess the feasibility of safe disposal of high-level radioactive waste as synthetic clay, or material that would react with ground water to form clay, experiments have been carried out to determine the hydrothermal crystallisation and leaching behaviour of silica based gels fired at 900 deg C. Crystallisation rates at a pressure of 500 bars and at temperatures below 400 deg C are negligible and this more or less precludes pre-disposal production of synthetic clay on the scale required. Leaching experiments suggest that the leach rates of Cs from gels by distilled water are higher than those of boro-silicate glasses and SYNROC at the lower temperatures that would be preferred for geological storage. However, amounts of bulk dissolution of gels may be lower than those of boro-silicate glasses. The initial leaching behaviour of gels might be considerably improved by hot compaction at 900 to 1000 deg C. Consideration of likely waste form dissolution behaviour in a repository environment suggests that gels of appropriate composition might perform as well as, or better than, boro-silicate glasses. A novel hypothetical plant is described that could produce the gel waste form on the scale required on a more or less continuous basis. (author)

  7. Modeling minor actinide multiple recycling in a lead-cooled fast reactor to demonstrate a fuel cycle without long-lived nuclear waste

    Stanisz Przemysław

    2015-09-01

    Full Text Available The concept of closed nuclear fuel cycle seems to be the most promising options for the efficient usage of the nuclear energy resources. However, it can be implemented only in fast breeder reactors of the IVth generation, which are characterized by the fast neutron spectrum. The lead-cooled fast reactor (LFR was defined and studied on the level of technical design in order to demonstrate its performance and reliability within the European collaboration on ELSY (European Lead-cooled System and LEADER (Lead-cooled European Advanced Demonstration Reactor projects. It has been demonstrated that LFR meets the requirements of the closed nuclear fuel cycle, where plutonium and minor actinides (MA are recycled for reuse, thereby producing no MA waste. In this study, the most promising option was realized when entire Pu + MA material is fully recycled to produce a new batch of fuel without partitioning. This is the concept of a fuel cycle which asymptotically tends to the adiabatic equilibrium, where the concentrations of plutonium and MA at the beginning of the cycle are restored in the subsequent cycle in the combined process of fuel transmutation and cooling, removal of fission products (FPs, and admixture of depleted uranium. In this way, generation of nuclear waste containing radioactive plutonium and MA can be eliminated. The paper shows methodology applied to the LFR equilibrium fuel cycle assessment, which was developed for the Monte Carlo continuous energy burnup (MCB code, equipped with enhanced modules for material processing and fuel handling. The numerical analysis of the reactor core concerns multiple recycling and recovery of long-lived nuclides and their influence on safety parameters. The paper also presents a general concept of the novel IVth generation breeder reactor with equilibrium fuel and its future role in the management of MA.

  8. Impeding 99Tc(IV) mobility in novel waste forms

    Lee, Mal-Soon; Um, Wooyong; Wang, Guohui; Kruger, Albert A.; Lukens, Wayne W.; Rousseau, Roger; Glezakou, Vassiliki-Alexandra

    2016-06-01

    Technetium (99Tc) is an abundant, long-lived radioactive fission product whose mobility in the subsurface is largely governed by its oxidation state. Tc immobilization is crucial for radioactive waste management and environmental remediation. Tc(IV) incorporation in spinels has been proposed as a novel method to increase Tc retention in glass waste forms during vitrification. However, experiments under high-temperature and oxic conditions show reoxidation of Tc(IV) to volatile pertechnetate, Tc(VII). Here we examine this problem with ab initio molecular dynamics simulations and propose that, at elevated temperatures, doping with first row transition metal can significantly enhance Tc retention in magnetite in the order Co>Zn>Ni. Experiments with doped spinels at 700 °C provide quantitative confirmation of the theoretical predictions in the same order. This work highlights the power of modern, state-of-the-art simulations to provide essential insights and generate theory-inspired design criteria of complex materials at elevated temperatures.

  9. Impeding (99)Tc(IV) mobility in novel waste forms.

    Lee, Mal-Soon; Um, Wooyong; Wang, Guohui; Kruger, Albert A; Lukens, Wayne W; Rousseau, Roger; Glezakou, Vassiliki-Alexandra

    2016-01-01

    Technetium ((99)Tc) is an abundant, long-lived radioactive fission product whose mobility in the subsurface is largely governed by its oxidation state. Tc immobilization is crucial for radioactive waste management and environmental remediation. Tc(IV) incorporation in spinels has been proposed as a novel method to increase Tc retention in glass waste forms during vitrification. However, experiments under high-temperature and oxic conditions show reoxidation of Tc(IV) to volatile pertechnetate, Tc(VII). Here we examine this problem with ab initio molecular dynamics simulations and propose that, at elevated temperatures, doping with first row transition metal can significantly enhance Tc retention in magnetite in the order Co>Zn>Ni. Experiments with doped spinels at 700 °C provide quantitative confirmation of the theoretical predictions in the same order. This work highlights the power of modern, state-of-the-art simulations to provide essential insights and generate theory-inspired design criteria of complex materials at elevated temperatures. PMID:27357121

  10. Impeding 99Tc(IV) mobility in novel waste forms

    Lee, Mal-Soon; Um, Wooyong; Wang, Guohui; Kruger, Albert A.; Lukens, Wayne W.; Rousseau, Roger; Glezakou, Vassiliki-Alexandra

    2016-01-01

    Technetium (99Tc) is an abundant, long-lived radioactive fission product whose mobility in the subsurface is largely governed by its oxidation state. Tc immobilization is crucial for radioactive waste management and environmental remediation. Tc(IV) incorporation in spinels has been proposed as a novel method to increase Tc retention in glass waste forms during vitrification. However, experiments under high-temperature and oxic conditions show reoxidation of Tc(IV) to volatile pertechnetate, Tc(VII). Here we examine this problem with ab initio molecular dynamics simulations and propose that, at elevated temperatures, doping with first row transition metal can significantly enhance Tc retention in magnetite in the order Co>Zn>Ni. Experiments with doped spinels at 700 °C provide quantitative confirmation of the theoretical predictions in the same order. This work highlights the power of modern, state-of-the-art simulations to provide essential insights and generate theory-inspired design criteria of complex materials at elevated temperatures. PMID:27357121

  11. Impeding 99Tc(IV) mobility in novel waste forms

    Lee, Mal Soon; Um, Wooyong; Wang, Guohui; Kruger, Albert A.; Lukens, Wayne W.; Rousseau, Roger J.; Glezakou, Vassiliki Alexandra

    2016-06-30

    Technetium (99Tc) is a long-lived radioactive fission product whose mobility in the subsurface is largely governed by its oxidation state1. Immobilization of Tc in mineral substrates is crucial for radioactive waste management and environmental remediation. Tc(IV) incorporation in spinels2, 3 has been proposed as a novel method to increase Tc retention in glass waste forms. However, experiments with Tc-magnetite under high temperature and oxic conditions showed re-oxidation of Tc(IV) to volatile pertechnetate Tc(VII)O4-.4, 5 Here we address this problem with large-scale ab initio molecular dynamics simulations and propose that elevated temperatures, 1st row transition metal dopants can significantly enhance Tc retention in the order Co > Zn > Ni. Experiments with doped spinels at T=700 ºC provided quantitative confirmation of increased Tc retention in the same order predicted by theory. This work highlights the power of modern state-of-the-art simulations to provide essential insights and generate bottom-up design criteria of complex oxide materials at elevated temperatures.

  12. Effects of aqueous environment on long-term durability of phosphate-bonded ceramic waste forms

    Over the last few years, Argonne National Laboratory has been developing room-temperature-setting chemically-bonded phosphate ceramics for solidifying and stabilizing low-level mixed wastes. This technology is crucial for stabilizing waste streams that contain volatile species and off-gas secondary waste streams generated by high-temperature treatment of such wastes. Magnesium phosphate ceramic has been developed to treat mixed wastes such as ash, salts, and cement sludges. Waste forms of surrogate waste streams were fabricated by acid-base reactions between the mixtures of magnesium oxide powders and the wastes, and phosphoric acid or acid phosphate solutions. Dense and hard ceramic waste forms are produced in this process. The principal advantage of this technology is that the contaminants are immobilized by both chemical stabilization and subsequent microencapsulation of the reaction products. This paper reports the results of durability studies conducted on waste forms made with ash waste streams spiked with hazardous and radioactive surrogates. Standard leaching tests such as ANS 16.1 and TCLP were conducted on the final waste forms. Fates of the contaminants in the final waste forms were established by electron microscopy. In addition, stability of the waste forms in aqueous environments was evaluated with long-term water-immersion tests

  13. Waste Package Related Impacts of Plutonium Disposition Waste Form Geologic Repository

    This report provides a comprehensive summary of the waste package (WP) related impacts of the Plutonium Disposition waste forms that are being developed and evaluated by the Office of Fissile Materials Disposition of the DOE. These waste forms are of two distinct types. One type is mixed oxide spent nuclear fuel (MOX SNF), which would be received from one or more commercial nuclear reactors using MOX fuel prepared from surplus weapons plutonium. The other type is plutonium immobilized in ceramic disks, which would be embedded in HLW glass in the standard HLW glass disposal canister. The ceramic disks would occupy approximately 12% of the HLW canister volume, while most of the remaining 88% of the volume would be occupied by HLW glass. The studies reported here have been ongoing for five years, and much of the work has been presented in one of four previous annual reports. This is the first of the reports to be subject to requirements of the Office of Civilian Radioactive Waste Management Quality Assurance Requirements (DOE 1998a and CRWMS M and O 1999p). This compliance is necessary in order that the results presented here be applicable to the major upcoming OCRWM project statutory and licensing documents: the Site Recommendation, and the License Application. It is, therefore, necessary to confirm some of the results from the prior year's reports. A summary distinguishing the results that are new this year is given at the end of this executive summary. The two basic WP designs used for this study are identical to those that have been used for the commercial SNF and the HLW glass; they are used here for the MOX SNF and the immobilized plutonium, respectively. These WP designs were used for the OCRWM Viability Assessment of a Repository at Yucca Mountain (VA) document, which was recently delivered to the US Congress. The improved performance expected with these new WP designs will be covered in the Waste Package Related Impacts report for next year

  14. Prediction of the long-term performance of Crystalline nuclear waste form phrases from studies of mineral analogues

    This paper describes the use of natural analogues as a mean of assessing the long term performance of actinide host phases in crystalline nuclear waste forms. Several analytical techniques were used to study the mineral zirconolite, an important actinide host phase in SYNROC and tailored ceramics. The following conclusions were reached: 1) Natural zirconolite experiences a crystalline to aperiodic transformation at doses of approximately 1015 to 1016 alpha/mg (0.08-1.0 dpa), consistent with the results of accelerated damage testing on synthetic zirconolite. 2) Damage microstructures are consistent with the accumulation and overlap of alpha-recoil collision cascades, resulting in aperiodic domains which increase in volume as a function of dose. 3) There is evidence for long term annealing of alpha-recoil damage in zirconolite at a rate 2-5 times slower than in the structurally related mineral pyrochlore. 4) Analysis of data from the only documented natural zirconolite to show hydrothermal alteration resulting from F- and P-rich aqueous fluids at T=500-600 C and P=2 kb, suggests that Th and U are released into the fluid phase. 5) The effects of low temperature alteration of radiation damaged zirconolite by a Si-rich ground water or fluid phase were identified in the oldest (2.5 x 109 yr) sample from a research collection. Alteration involved incorporation of Si along micro fractures at the expense of Ca, Ti, and Fe, but Th and U remained immobile. In this same sample, there is evidence for migration of at least 50% of the radiogenic Pb from both unaltered and altered areas of zirconolite. Most of the Pb may have been retained within the sample as fine precipitates of galena. 21 refs., 6 figs

  15. Development of Polymeric Waste Forms for the Encapsulation of Toxic Wastes Using an Emulsion-Encapsulation Based Process

    Evans, R.; Quach, A.; Birnie, D. P.; Saez, A. E.; Ela, W. P.; Zeliniski, B. J. J.; Xia, G.; Smith, H.

    2003-01-01

    Developed technologies in vitrification, cement, and polymeric materials manufactured using flammable organic solvents have been used to encapsulate solid wastes, including low-level radioactive materials, but are impractical for high salt-content waste streams (Maio, 1998). In this work, we investigate an emulsification process for producing an aqueous-based polymeric waste form as a preliminary step towards fabricating hybrid organic/inorganic polyceram matrices. The material developed incorporates epoxy resin and polystyrene-butadiene (PSB) latex to produce a waste form that is non-flammable, light weight, of relatively low cost, and that can be loaded to a relatively high weight content of waste materials. Sodium nitrate was used as a model for the salt waste. Small-scale samples were manufactured and analyzed using leach tests designed to measure the diffusion coefficient and leachability index for the fastest diffusing species in the waste form, the salt ions. The microstructure and composition of the samples were probed using SEM/EDS techniques. The results show that some portion of the salt migrates towards the exterior surfaces of the waste forms during the curing process. A portion of the salt in the interior of the sample is contained in polymer corpuscles or sacs. These sacs are embedded in a polymer matrix phase that contains fine, well-dispersed salt crystals. The diffusion behavior observed in sections of the waste forms indicates that samples prepared using this emulsion process meet or exceed the leachability criteria suggested for low level radioactivity waste forms.

  16. Waste form characteristics report, revision 1.3

    Leider, H.R.; Stout, R.B.

    1998-07-01

    This Waste Form Characteristics Report (WFCR) update, Version 1.3, incorporates substantial additions and changes to following 10 sections of the WFCR: 2.1.3.1 Cladding Degradation; 2.1.3.2 UO2 Oxidation in Fuel; 2.1.3.5 Dissolution Release from UO{sub 2}; 2.2.1.5 Fract