Kinetics of oxyapatite [Ca2Nd8(SiO4)6O2] and powellite [(Ca,Sr,Ba)MoO4] dissolution in glass-ceramic nuclear waste forms in acidic, neutral, and alkaline conditions
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Neeway, James J. (ORCID:0000000170468408)↗
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2011 Annual Summary Report for the Area 3 and Area 5 Radioactive Waste Management Sites at the Nevada National Security Site, Nye County, Nevada: Review of the Performance Assessments and Composite Analyses
The Maintenance Plan for the Performance Assessments and Composite Analyses for the Area 3 and Area 5 Radioactive Waste Management Sites at the Nevada Test Site (National Security Technologies, LLC, 2007a) requires an annual review to assess the adequacy of the Performance Assessments (PAs) and Composite Analyses (CAs), with the results submitted annually to U.S. Department of Energy (DOE) Office of Environmental Management. The Disposal Authorization Statements for the Area 3 and Area 5 Radioactive Waste Management Sites (RWMSs) also require that such reviews be made and that secondary or minor unresolved issues be tracked and addressed as part of the maintenance plan (DOE, 1999a; 2000).
12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
Driving Zn-MnO2 grid-scale batteries: A roadmap to cost-effective energy storage
Highlights Zn-MnO 2 batteries promise safe, reliable energy storage, and this roadmap outlines a combination of manufacturing strategies and technical innovations that could make this goal achievable. Approaches such as improved efficiency of manufacturing and increasing active material utilization will be important to getting costs as low as $100/kWh, but key materials innovations that facilitate the full 2-electron capacity utilization of MnO 2 , the use of high energy density 3D electrodes, and the promise of a separator-free battery with greater than 2V potential offer a route to batteries at $50/kWh or less. Abstract Large-scale energy storage is certain to play a significant, enabling role in the evolution of the emerging electrical grid. Battery-based storage, while not a dominant form of storage today, has opportunity to expand its utility through safe, reliable, and cost-effective technologies. Here, secondary Zn–MnO 2 batteries are highlighted as a promising extension of ubiquitous primary alkaline batteries, offering a safe, environmentally friendly chemistry in a scalable and practical energy dense technology. Importantly, there is a very realistic pathway to also making such batteries cost-effective at price points of $50/kWh or lower. By examining manufacturing examples at the Zn–MnO 2 battery manufacturer Urban Electric Power, a roadmap has been created to realize such low-cost systems. By focusing on manufacturing optimization through reduced materials waste, scalable manufacturing, and effective materials selection, costs can be significantly reduced. Ultimately, though, coupling these approaches with emerging research and development advances to enable full capacity active materials utilization and battery voltages greater than 2V are likely needed to drive costs below a target of $50/kWh. Reaching this commercially important goal, especially with a chemistry that is safe, well-known, and reliably effective stands to inject Zn–MnO 2 batteries in the storage landscape at a critical time in energy storage development and deployment. Graphical abstract
Spoerke, Erik D. (ORCID:0000000322862560)↗
Colorimetric Detection and Surface Decontamination of Metal Ions by Using Strippable Polymers - 20024
Strippable coating is a low cost and efficient decontamination method far more compatible for the cleaning of surfaces. This method allows contaminant entrapment and removal from different types of surfaces and also characterized by low-secondary waste generation after decontamination. The present work deals with the elaboration and testing of a new composition of Polyvinyl alcohol (PVA) aqueous solutions utilize the TTA (Thenoyl trifluoroacetone) ligand, employed as a strippable coating for the removal of metal ions e.g., UO{sub 2}{sup +2}, Ni{sup +2}, Cu{sup +2}, Fe{sup +3}, V{sup +5}, Eu{sup +3} and Cs{sup +} from 'contaminated' surfaces. The study aims at developing contaminant-sensing and decontaminating coatings for the detection and removal of metal ions from non porous surfaces. This 'smart' coating is shown to exhibit a clear contaminant dependent response in the form of color variation, and a detection sensitivity less than 0.5 μg per cm{sup 2}. (authors)
12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
Stabilization of an Unprecedented Hexanuclear Secondary Building Unit in a Thorium-Based Metal–Organic Framework
The crystal structures of thorium clusters are important for understanding the formation and transformation mechanisms of actinide species in solution, which can in turns benefit nuclear waste processing and management. However, stabilizing thorium clusters in aqueous solution is quite challenging because of their fast olation and oxolation reactions. Here, we report a thorium-based meta-organic framework, NU-905, with the formula [Th 6 (μ 3 -O) 2 (HCOO) 4 (H 2 O) 6 ] [TCPP = tetrakis(4-carboxyphenyl)porphyrin], synthesized by a solvothermal reaction in N,N-dimethylformamide and water at 120 °C. NU-905 contains a hexanuclear secondary building unit (SBU), [Th 6 (μ 3 -O) 2 (HCOO) 4 (H 2 O) 6 ], which has never been reported previously. The SBUs are capped and bridged by the tetratopic linker TCPP to form a three-dimensional network with scu topology. The activated NU-905 exhibits permanent porosity and shows high catalytic activity for the selective photooxidation of a mustard gas simulant.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Performance of the Fluidized Bed Steam Reforming Product Under Hydraulically Unsaturated Conditions
Currently, several candidates for secondary waste immobilization at the Hanford site in the State of Washington, USA are being considered. To demonstrate the durability of the product in the unsaturated Integrated Disposal Facility (IDF) at the site, a series of tests have been performed one of the candidate materials using the Pressurized Unsaturated Flow (PUF) system. The material that was tested was the Fluidized Bed Steam Reformer (FBSR) granular product and the granular product encapsulated in a geopolymer matrix. The FBSR product is composed primarily of an insoluble sodium aluminosilicate matrix with the dominant phases being feldspathoid minerals mostly nepheline, sodalite, and nosean. The PUF test method allows for the accelerated weathering of materials, including radioactive waste forms, under hydraulically unsaturated conditions, thus mimicking the open-flow and transport properties that most likely will be present at the IDF. The experiments show a trend of decreasing tracer release as a function of time for several of the elements released from the material including Na, Si, Al, and Cs. However, some of the elements, notably I and Re, show a steady release throughout the yearlong test. This result suggests that the release of these minerals from the sodalite cage occurs at a different rate compared with the dissolution of the predominant nepheline phase.
Durability testing↗
Sub-pilot-scale Production of High-Value Products from U.S. Coals
Investigators from the University of Utah, University of Wyoming and Marshall University pursued a program to study the conversion of raw coal to high-value products of carbon fiber and silicon carbide. Team members also developed an initial framework for a data portal that can incorporate laboratory data on coal processing and product quality, and also work with tools for machine learning for data analysis, data visualization and economic assessment. Experimental R&D efforts focused on the conversion of raw coal to coal tar and other byproducts, and the resulting tar intermediates were upgraded to form anisotropic and isotropic pitch materials. These pitch materials were produced from coal using both thermal (pyrolysis) and chemical (mild solvolysis liquefaction) decomposition of raw coal. Four different coals were studied: Utah bituminous coal (Sufco), Wyoming PRB coal (Black Thunder), Illinois bituminous coal (Illinois #6), and West Virginia bituminous coal (Flying Eagle). Both metallurgical-grade coking coals and lower-grade steam coals were investigated, and controlled secondary gas-phase reactions were used during a two-stage pyrolysis process to induce cracking and condensation reactions among the pyrolytic tar species. This approach successfully improved the performance of the lower grade coals for yielding pitch materials, with properties more consistent with a commercial-grade pitch that had previously demonstrated success for quality carbon fiber production. The use of waste plastic materials was also studied, to help improve physical and chemical characteristics of the intermediate tars and final pitch product; in particular, for lowering the pitch softening point to an acceptable level for melt spinning carbon fiber. Mild solvolysis liquefaction was also used as a method for producing pitch for carbon fiber production. As expected, significantly higher pitch yields were obtained using this approach, and waste plastic materials were also successfully used to reduce pitch softening point to an acceptable level. The plastic materials were also utilized to create a solvent for the mild solvolysis process, and this plastic-derived solvent was shown to provide results consistent with more expensive commercial chemical solvents, and could thus avoid the need for costly recovery and recycle of a liquefaction solvent. Additional experimental R&D focused on the production of silicon carbide (β-SiC) from the residual char byproduct from pitch production, and also on the production of carbon fiber from the anisotropic pitch. SiC was successfully synthesized using a mixture of residual char and sandstone at a ratio of 1:1. Reaction temperature and residence time were optimized and yielded a product purity of 81%. For carbon fiber production, the most successful pitch samples were obtained from the mild solvolysis liquefaction approach, combined with the use of a plastic (HDPE)-derived solvent. Fiber properties improved over time as laboratory fiber production methodologies improved, and final yields of carbon fiber were obtained with a diameter of 12.14 ± 1.10 um, Modulus of 173.73 ± 15.25 GPa, and Tensile Strength of 1.04 ± 0.10 GPa. A proof-of-concept Modern Community Research Data Portal (MCRDP) was developed and deployed for coal and coal-derived pitch characterization, with the full support of (i) remote web-based access, (ii) distributed analysis, (iii) interactive visualization and exploration, (iv) shared and long-term data access, (v) advanced query capabilities and (vi) real-time collaboration. The Coal to Products Data Portal “coaltoproducts.org” provides researchers with space to store and share data within a project, tools for analyzing and understanding data for scientific investigation, and the ability to publish data to the broader community for reproducibility. The portal leverages the Material Commons 2.0 (MC) platform developed by the Center for PRedictive Integrated Structural Materials Science (PRISMS) of the University of Michigan, to achieve long-term longevity of data collections and, more importantly, collaborative science. A number of data visualization tools were also assessed and implemented for interrogating the experimental and modeling data. The machine learning portion of this project analyzed datasets from two different coal conversion processes performed on a diverse set of coal samples from both the coal pyrolysis experiments and the solvent liquefaction experiments. The work was initiated by exploring standard regression models on the pyrolysis data, aiming to understand the impact of sample characteristics and processing conditions on key product metrics. Over the course of the project, the focus expanded to include a variety of machine learning tools, delving into both supervised and unsupervised learning methods. Models tested on the pyrolysis data included linear, ridge, lasso, elastic-net, Gaussian process, random forest regression, and AutoSklearn, and the approach was continually refined to enhance predictive accuracy and model interpretability. Similar techniques were applied to the liquefaction data with an additional focus on feature engineering. Along with mesophase content, additional outputs of interest were the pitch yield, softening point, and QI content. Insights derived from these analyses are crucial in determining the factors influencing the quality and yield of coal-derived products. As the work progressed, the research evolved from foundational model comparisons to analyses of random forests, decision paths, and feature importance scores. A thorough market analysis was performed to examine the prospects of coal-based carbon fibers. The best opportunities for coal come from its lower and more stable price relative to petroleum, particularly for subbituminous coals, which is the primary advantage that a coal refinery may have over a petroleum refinery. Before a commercial CTP production facility can be modeled, however, several things need to be understood regarding the nature of the would-be coal refinery. These include the technology to be deployed, the size of facility, the volume(s) of co-product(s), and the waste and emissions profile of the plant. The volume of co-products and waste may be substantial and will require separate market analysis to ensure viability. In the near-term, the importance of coal tar pitch, in the form of carbon pitch, to the aluminum and steel industries is likely to overshadow the alternative use of this material as an input for carbon fiber. The importance of steel and aluminum in building materials, and the need for carbon materials in their manufacturing, will ensure that demand for these products remains for the long run. In addition, carbon fiber may also be the best substitute for steel and aluminum well into the future. While society will eventually be able to shift production of much of its electricity needs to renewables, it will not be able to shift away from fossil fuels for production of high-strength construction and vehicular materials. Demand for carbon fiber is expected to increase quickly, but the volume of carbon fiber and the amount of coal that would be needed to produce even a sizeable share of this market may still be relatively small compared to current coal production. Thus, other coal-based products like graphene, graphite, carbon foams, resins, and carbon-based building products will play important roles in sustaining coal production as coal-fired power generation continues to decline.
01 COAL, LIGNITE, AND PEAT↗
Ediesel: Diesel Additive production from ethanol and bio-diesel coproducts
This project has focused on supporting and expanding the U.S. ethanol industry by developing new conversion routes and products from ethanol and the byproducts made in ethanol fermentation. The work is relevant to the DOE program goals of developing high-margin chemical products in the biorefinery to economically support large-scale biofuel production. The higher alcohols from condensation of ethanol, alkylated amine compounds made by electrocatalytic alkyation, and fusel alcohols produced by modified fermentation microorganisms are all existing or potentially large-scale commodity or specialty chemicals with well-defined uses in industry. The formation of higher alcohols from ethanol in the condensed phase developed several catalysts, first in stirred batch autoclave reactors and then in a continuous flow reactor system, to achieve significant yields of n-butanol and higher alcohols. The best selectivity to higher alcohols exceeded 80% of theoretical at ethanol conversions of 30-40%. From the laboratory experiments and analysis of the phase equilibria of the species involved, a process concept was generated and simulated in AspenPlus to determine the specifications of the various equipment involved in the process. Results show that for the conversion and selectivity described above, the required n-butanol selling price of ~$1.60/kg is in the range of current n-butanol selling price in the marketplace. Several additional permutations of the process, along with evaluation of higher conversion and selectivities to desired alcohol products, showed that the production of n-butanol from ethanol should be competitive in the marketplace as the science and engineering behind the process improves with continued development. A second aspect of the project focused on producing fusel alcohols in increased quantities during ethanol fermentation. Fusel alcohols, which are composed primarily of isoamyl alcohol and minor quantities of C3-C6 alcohols, have potential as higher value feed stocks for specialty chemical production. Several strains of yeast were evaluated for fusel alcohol production, and the most efficient process for separating and purifying fusel alcohols was developed from both experiments and simulation. Finally, model fusel alcohol mixtures were subjected to condensation reactions with ethanol to prepare higher alcohols that again have potential for specialty chemical or solvent applications. In this preliminary work, measurable quantities of several species were observed, including some species that were previously unknown or uncharacterized in the literature. The third aspect of the project involved the electrocatalytic alkylation of amines with alcohols to form alkyl amines. Ethanol has been demonstrated to serve as an effective ethyl group transfer agent to the nitrogen centers of amines, a reaction with only water as a byproduct. Mild reaction conditions (60 °C, aqueous solution) are enabled by the novel use of simple, undivided electrochemical cell reactors that include long-lived, low cost catalytic electrodes. Direct polyalkylation of ammonia and isolation of the resulting triethylamine product was readily achieved in high yield. Though classical high temperature and pressure industrial scale alkylations reactions will likely continue to be used for production of simple product such as triethylamine, this approach has opened the door to the low cost, low waste use of ethanol and related primary and secondary alcohols to alkylate more delicate amines that were heretofore difficult to synthesize.
02 PETROLEUM↗
Chemical Characterization and Removal of C-14 from Irradiated Graphite-12010
Quantities of irradiated graphite waste are expected to drastically increase, which indicates the need for a graphite waste management strategy. Of greatest concern for long-term disposal of irradiated graphite is carbon-14 (C-14), with a half-life of 5730 years. Study of irradiated graphite from nuclear reactors indicates C-14 is concentrated on the outer 5 mm of the graphite structure. The aim of the research described here is to identify the chemical form of C-14 in irradiated graphite and develop a practical method by which C-14 can be removed. Characterization of pre- and post-irradiation graphite was conducted to determine bond type, functional groups, location and concentration of C-14 and its precursors via the use of surface sensitive characterization techniques. Because most surface C-14 originates from neutron activation of nitrogen, an understanding of nitrogen bonding to graphite may lead to a greater understanding of the formation pathway of C-14. However, no single technique provides a complete picture. Therefore, a portfolio of techniques has been developed, with each technique providing another piece to the puzzle that is the chemical nature of the C-14. Scanning Electron Microscopy (SEM), X-Ray Diffraction (XRD), and Raman Spectroscopy were used to evaluate the morphological features of graphite samples. The concentration, chemical composition, and bonding characteristics of C-14 and its precursors were determined through X-ray Photoelectron Spectroscopy (XPS), Time-of-Flight Secondary Ion Mass Spectrometry (SIMS), and Auger and Energy Dispersive X-ray Analysis Spectroscopy (EDX). High-surface-area graphite foam, POCOFoam{sup R}, was exposed to liquid nitrogen and irradiated. Characterization of this material has shown C-14 to C-12 ratios of 0.035. This information was used to optimize the thermal treatment of graphite. Thermal treatment of irradiated graphite as reported by Fachinger et al. (2007) uses naturally adsorbed oxygen complexes to gasify graphite, thus its effectiveness is highly dependent on the availability of adsorbed oxygen compounds. In research presented, the quantity and form of adsorbed oxygen complexes in pre- and post irradiated graphite was studied using SIMS and XPS. SIMS and XPS detected adsorbed oxygen compounds on both irradiated and unirradiated graphite. During thermal treatment graphite samples are heated in the presence of inert argon gas, which carries off gaseous products released during treatment. Experiments were performed at 900 deg. C and 1400 deg. C to evaluate the selective removal of C-14. (authors)
12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
Joint influence of γ–irradiation and high temperature shear grinding on the IR spectra and surface–energy properties of polyethylene
The optical and surface-energy properties of polyethylene (PE) subjected to γ-irradiation and post-radiation, high temperature, shear grinding are presented. Comparison of the IR spectra of the initial and γ-irradiated PE shows that oxygen-containing groups and unsaturated bonds in the polymer macromolecules are formed and accumulate during their radiolysis in air, increasing with γ-irradiation dose. A redistribution of the products of radiation-chemical conversion on the surface of the polymer granules throughout the entire volume of the powder occurs after high-temperature shear milling to a powder as observed in the IR spectrum. Polar functional groups due to oxidation reactions are observed on the surface layer of the sample after post-radiation grinding. Furthermore, the initial polymer surface is weakly basic with an acidity parameter of -0.34. The value of the acidity parameter of the sample made of ground irradiated PE has an acidic surface with an acidity parameter of 0.65. γ irradiation of the secondary processing of PE waste with high-temperature shear grinding is a promising approach to obtain a secondary PE powder with specified parameters and different degrees of functionalization.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Heat transfer from glass melt to cold cap: Computational fluid dynamics study of cavities beneath cold cap
Efficient glass production depends on the continuous supply of heat from the glass melt to the floating layer of batch, or cold cap. Computational fluid dynamics (CFD) are employed to investigate the formation and behavior of gas cavities that form beneath the batch by gases released from the collapsing primary foam bubbles, ascending secondary bubbles, and in the case of forced bubbling, from the rising bubbling gas. The gas phase fraction, temperature, and velocity distributions below the cold cap are used to calculate local and average heat transfer rates as a function of the bubbling rate. It is shown that the thickness of the cavities is nearly independent of the cold cap shape and the amount of foam evolved during batch conversion. Furthermore, it is ~7 mm and up to ~15 mm for the cases without and with forced bubbling used to promote circulation within the melt, respectively. Using computed velocity and temperature profiles, the melting rate of the simulated high-level nuclear waste glass batch was estimated to increase with the bubbling rate to the power of ~0.3 to 0.9, depending on the flow pattern. The simulation results are in good agreement with experimental data from laboratory- and pilot-scale melter tests.
12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
NJOY2016
NJOY2016 is used to convert evaluations in the Evaluated Nuclear Data Files (ENDF) format into forms useful for practical applications such as fission and fusion reactor analysis, criticality safety, radiation shielding, nuclear waste management, nuclear medicine procedures, and more. It begins with the generation of pointwise libraries, including reaction and resonance reconstruction, Doppler broadening, radiation heating and damage, thermal scattering data, unresolved resonance data, and gas production. It reviews the production of libraries for the continuous-energy Monte Carlo code MCNP, multigroup neutron, photon, and particle cross sections and matrices, and photon interaction data. Uncertainty information for ENDF data is processed, including the capability for calculating covariances of resonance data, angular distributions, energy distributions, and radioactive nuclide production. NJOY can prepare and process thermal scattering data evaluations into application libraries. It can also plot cross sections, angular distributions and secondary emission spectra.
Kahler III, A. C. (Skip)↗
NJOY2016
NJOY2016 is used to convert evaluations in the Evaluated Nuclear Data Files (ENDF) format into forms useful for practical applications such as fission and fusion reactor analysis, criticality safety, radiation shielding, nuclear waste management, nuclear medicine procedures, and more. It begins with the generation of pointwise libraries, including reaction and resonance reconstruction, Doppler broadening, radiation heating and damage, thermal scattering data, unresolved resonance data, and gas production. It reviews the production of libraries for the continuous-energy Monte Carlo code MCNP, multigroup neutron, photon, and particle cross sections and matrices, and photon interaction data. Uncertainty information for ENDF data is processed, including the capability for calculating covariances of resonance data, angular distributions, energy distributions, and radioactive nuclide production. NJOY can prepare and process thermal scattering data evaluations into application libraries. It can also plot cross sections, angular distributions and secondary emission spectra.
Kahler III, A. C. (Skip)↗
Exploring the influence of transition metals on f-element bonding
The United States aims to triple its nuclear energy production by 2050, which will result in increased uranium usage and spent nuclear fuel generation. This highlights the need for a comprehensive understanding of actinide coordination chemistry, which is crucial for the extraction, processing, purification, and fabrication of uranium-based fuels. Moreover, it is vital for the reprocessing or safe disposal of nuclear waste and effective remediation efforts. Achieving this successfully requires an in-depth understanding of f-electron behavior, as “the role of 5f electrons in bond formation remains a fundamental topic in actinide chemistry”. Introducing a second metal into the system can increase structural dimensionality and diversify structural architecture. Heterometallic systems can also alter material properties, such as magnetic and spectroscopic characteristics, luminescence, and actinide mobility. Additionally, secondary transition metals, even when present only in the second coordination sphere and not directly coordinated, can influence the electron density at the actinyl metal center. In this study, uranium heterometallic single crystals were synthesized by incorporating transition metals such as iron(III), iron(II), nickel(II), manganese(II), copper(I), and cobalt(II). The crystals were formed using 2,6-pyridine dicarboxylic acid and other structurally similar ligands with varying functional groups. The synthesized crystals were analyzed using an extensive array of analytical and computational characterization techniques, including single crystal X-ray diffraction, Raman and infrared spectroscopy, and density functional theory calculations.
37 - INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL C↗
Catalytic Hydrogenolysis of Polyethylene Under Reactive Separation
Deconstruction of polyolefins by catalytic hydrogenolysis is typically accompanied by the generation of undesired light gases. At reaction temperatures, the desired liquid products also tend to be volatile. Secondary cleavage of these liquid products contributes to light gas formation. The latter process was mitigated by reactive separation, continuously separating the liquid products from the catalyst throughout the experiment. At equivalent conversion, the yield and selectivity for oligomeric liquid species are increased under reactive separation, even though the carbon–carbon bond cleavage rate is slower than that in sealed experiments. More light gas is formed in the sealed reactor. Under 1 atm H 2 partial pressure, alkenes accompany the typical alkane hydrogenolysis products. Further, the alkene yield is higher, with greater selectivity for valuable α-olefins under reactive separation. These results provide the mechanistic insight that terminal alkenes are primary products of carbon–carbon bond cleavage during hydrogenolysis under experimental conditions, and secondary deconstruction of these species produces light gases.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Technetium Incorporation in Glass for the Hanford Tank Waste Treatment and Immobilization Plant
A priority of the United States Department of Energy (U.S. DOE) is to dispose of nuclear wastes accumulated in 177 underground tanks at the Hanford Nuclear Reservation in eastern Washington State. These nuclear wastes date from the Manhattan Project of World War II and from plutonium production during the Cold War. The DOE plans to separate high-level radioactive wastes from low activity wastes and to treat each of the waste streams by vitrification (immobilization of the nuclides in glass) for disposal. The immobilized low-activity waste will be disposed of here at Hanford and the immobilized high-level waste at the national geologic repository. Included in the inventory of highly radioactive wastes is large volumes of 99Tc (~9 × 10E2 TBq or ~2.5 × 104 Ci or ~1500 kg). A problem facing safe disposal of Tc-bearing wastes is the processing of waste feed into in a chemically durable waste form. Technetium incorporates poorly into silicate glass in traditional glass melting. It readily evaporates during melting of glass feeds and out of the molten glass, leading to a spectrum of high-to-low retention (ca. 20 to 80%) in the cooled glass product. DOE-ORP currently has a program at Pacific Northwest National Laboratory (PNNL), in the Department of Materials Science and Engineering at Rutgers University and in the School of Mechanical and Materials Engineering at Washington State University that seeks to understand aspects of Tc retention by means of studying Tc partitioning, molten salt formation, volatilization pathways, and cold cap chemistry. Another problem involves the stability of Tc in glass in both the national geologic repository and on-site disposal after it has been immobilized. The major environmental concern with 99Tc is its high mobility in addition to a long half-life (2.1×105 yrs). The pertechnetate ion (TcO4-) is highly soluble in water and does not adsorb well onto the surface of minerals and so migrates nearly at the same velocity as groundwater. Long-term corrosion of glass waste forms is an area of current interest to the DOE, but attention to the release of Tc from glass has been little explored. It is expected that the release of Tc from glass should be highly dependent on the local glass structure as well as the chemistry of the surrounding environment, including groundwater pH. Though the speciation of Tc in glass has been previously studied, and the Tc species present in waste glass have been previously reported, environmental Tc release mechanisms are poorly understood. The recent advances in Tc chemistry that have given rise to an understanding of incorporation in the glass giving rise to significantly higher single-pass retention during vitrification are presented. Additionally, possible changes to the baseline flowsheet that allow for relatively minor volumes of Tc reporting to secondary waste treatment will be discussed.
Kruger, Albert A.↗
Extraction, Characterization, and Stability Studies of Bistriazinyl-Derived Carboxylic Acids
Separation of An(III) and Ln(III) ions will benefit the recycling of used nuclear fuel (UNF). For this purpose, many ligands have been tested over the years, and several separation processes have been successfully demonstrated on the laboratory scale. Current research aims at the development of new ligands that are built only with carbon, hydrogen, oxygen, and nitrogen (CHON), as they can be incinerated completely without secondary waste production. Here, we tested a new class of water-soluble ligands, the bistriazinyl-octa-carboxylic acids. One member, in particular, 2,6-bis-[5,6-di(3,4-dicarboxyphenyl)-1,2,4- triazin-3-yl]-pyridine (BTPOA), was found to be suitable for the selective separation of Am(III) and Cm(III) ions from Ln(III) ions and may act as a CHON alternative to its sulfonated analogue (SO 3 -Ph-BTP). BTPOA exhibited good extraction results and a high selectivity for Am(III) over Eu(III) ions. This ligand’s complexation of metal ions was further studied using potentiometric spectroscopy, as well as time-resolved laser-induced spectroscopy with Cm(III) and Eu(III) in aqueous HClO 4 and HNO 3 media. Conditional stability constants of each formed species were determined. In the HClO 4 system, Cm(III) formed three species (1:1, 1:2, and 1:3) through the stepwise addition of a single BTPOA molecule. On the other hand, in HNO 3 , Cm(III) formed two 1:2 complexes and one 1:3 complex, while the stepwise formation of three species was observed for Eu(III). The stability constants are comparable to the values for SO 3 -Ph-BTP. The radiolytic behavior of BTPOA was also investigated using electron pulse irradiation measurements to determine absolute rate coefficients (k) under ambient temperature conditions for the reaction of BTPOA with typical UNF reprocessing radical radiolysis products the hydrated electron (e aq − , k = (1.60 ± 0.02) × 10 10 M −1 s −1 ), the hydrogen atom (H • , k = (2.17 ± 0.03) × 10 9 M −1 s −1 ), and hydroxyl ( • OH, k = (6.95 ± 0.06) × 10 9 M −1 s −1 ) and nitrate (NO 3 • , k = (0.37 ± 0.02) × 10 7 M −1 s−1) radicals. These rate coefficients indicate that the radiolytic longevity of BTPOA should increase with HNO 3 concentration, owing to the consumption of e aq − /H • , by nitrate anions, and the replacement of • OH by the less reactive NO 3 • .
Diaz Gomez, Laura [Forschungszentrum Juelich (Germ↗
Crystal Structure and Thermodynamic Stability of Ba/Ti-Substituted Pollucites for Radioactive Cs/Ba Immobilization
Abstract not provided
Xu, Hongwu↗