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At least 253 records · Page 14

Waste Form Release Calculations for the 2005 Integrated Disposal Facility Performance Assessment. Erratum

This report refers to or contains K g values for glasses LAWA44, LAWB45 and LAWC22 affected by calculations errors as identified by Papathanassiu et al. (2011). The corrected K g values are reported in an erratum included in the revised version of the original report. The revised report can be referenced as follows: Pierce E. M. et al. (2004) Waste Form Release Data Package for the 2005 Integrated Disposal Facility Performance Assessment. PNNL-14805 Rev. 0 Erratum. Pacific Northwest National Laboratory, Richland, WA, USA.

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The Consolidation of Glass-Ceramic Waste forms by Hot Isostatic Pressing: Sample Optimisation - 16581

Zirconolite based glass-ceramics were developed for the disposition of plutonium residues at the UK's Sellafield site. Glass-ceramics act as double barrier systems, separating Pu into a durable ceramic phase and retaining miscellaneous material in the amorphous phase. Here we discuss the optimisation of processing parameters and formulations of these alternative waste-forms. All samples were HIPed at 1250 deg. C, 100 MPa for 4 hrs. By investigating the effects of different pre-HIP heat treatments on sample quality and throughput, and glass phase compositions on the crystalline phase assemblage, an optimised method and wasteform composition were achieved. (authors)

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Waste Form Release Data Package for the 2005 Integrated Disposal Facility Performance Assessment. Erratum

This report refers to or contains K g values for glasses LAWA44, LAWB45 and LAWC22 affected by calculations errors as identified by Papathanassiu et al. (2011). The corrected K g values are reported in an erratum included in the revised version of the original report. The revised report can be referenced as follows: Pierce E. M. et al. (2004) Waste Form Release Data Package for the 2005 Integrated Disposal Facility Performance Assessment. PNNL-14805 Rev. 0 Erratum. Pacific Northwest National Laboratory, Richland, WA, USA.

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Materials for Tc capture to increase Tc retention in glass waste form - A review - 15553

{sup 99}Technetium is a long-lived fission product found in the tank waste at the Hanford site in Washington State. In its hepta-valent species, it is volatile at the temperatures used in Hanford Tank Waste Treatment and Immobilization Plant vitrification melters, and thus is challenging to incorporate into waste glass. In order to decrease volatility and thereby increase retention, technetium can be converted into more thermally stable species. Several mineral phases, such as spinel, are able to incorporate tetravalent technetium in a chemically durable and thermally stable lattice, and these hosts may promote the decreased volatility that is desired. In order to be usefully implemented, there must be a synthetic route to these phases that is compatible with both technetium chemistry and current Hanford Tank Waste Treatment and Immobilization Plant design. Synthetic routes for spinel and other potential host phases are examined. (authors)

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Cold crucible induction melter test for crystalline ceramic waste form fabrication: A feasibility assessment

The first scaled proof-of-principle cold crucible induction melter (CCIM) test to process a multiphase ceramic waste form from a simulated combined (Cs/Sr, lanthanide and transition metal fission products) commercial used nuclear fuel waste stream was recently conducted in the United States. X-ray diffraction, 2-D X-ray absorption near edge structure (XANES), electron microscopy, inductively coupled plasma-atomic emission spectroscopy (and inductively coupled plasma-mass spectroscopy for Cs), and product consistency tests were used to characterize the fabricated CCIM material. Characterization analyses confirmed that a crystalline ceramic with a desirable phase assemblage was produced from a melt using a CCIM. We identified primary hollandite, pyrochlore/zirconolite, and perovskite phases in addition to minor phases rich in Fe, Al, or Cs. The material produced in the CCIM was chemically homogeneous and displayed a uniform phase assemblage with acceptable aqueous chemical durability.

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OWL and Waste Form Characteristics (Annual Status Update)

This report represents completion of milestone deliverable M2SF-21SN010309012 “Annual Status Update for OWL and Waste Form Characteristics” that provides an annual update on status of fiscal year (FY 2020) activities for the work package SF-20SN01030901 and is due on January 29, 2021. The Online Waste Library (OWL) has been designed to contain information regarding United States (U.S.) Department of Energy (DOE)-managed (as) high-level waste (DHLW), spent nuclear fuel (SNF), and other wastes that are likely candidates for deep geologic disposal, with links to the current supporting documents for the data (when possible; note that no classified or official-use-only (OUO) data are planned to be included in OWL). There may be up to several hundred different DOE-managed wastes that are likely to require deep geologic disposal. This draft report contains versions of the OWL model architecture for vessel information (Appendix A) and an excerpt from the OWL User’s Guide (Appendix B and SNL 2020), which are for the current OWL Version 2.0 on the Sandia External Collaboration Network (ECN).

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Fabrication of Large Size GCM Waste Forms Containing I 2 or CH 3 I Loaded AgI-MOR

Two large size Glass Composite Material (GCM) waste forms containing AgI-MOR were fabricated. One contained methyl iodide-loaded AgI-MOR that was received from Idaho National Laboratory (INL, Test 5, Beds 1 – 3) and the other contained iodine vapor loaded AgIMOR that was received from Oak Ridge National Laboratory (ORNL, SHB 2/9/15 ). The composition for each GCM was 20 wt% AgI-MOR and 80 wt% Ferro EG2922 low sintering temperature glass along with enough added silver flake to prevent any I2 loss during the firing process. The silver flake amounts were 1.2 wt% for the GCM with the INL AgI-MOR and 3 wt% for the GCM contained the ORNL AgI-MOR. The GCMs, nominally 100 g, were first uniaxially pressed to 6.35 cm (2.5 inch) diameter disks then cold isostatically pressed, before firing in air to 550°C for 1hr. They were cooled slowly (1°C/min) from the firing temperature to avoid any cracking due to temperature gradients. The final GCMs were ~5 cm in diameter (~2 inches) and non-porous with densities of ~4.2 g/cm³. X-ray diffraction indicated that they consisted of the amorphous glass phase with small amounts of mordenite and AgI. Furthermore, the presence of the AgI was confirmed by X-ray fluorescence. Methodology for the scaled up production of GCMs to 6 inch diameter or larger is also presented.

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Iodine Waste Form Corrosion: PNNL Summary Testing Report

A test method to correlate the laboratory corrosion behavior of iodine-containing waste forms (IWFs) to a conceptual long-term corrosion models is required. Several candidate methods have been evaluated previously, and each method presents unique challenges and limitations. Dynamic leach tests have emerged as the preferred candidate test method to evaluate IWFs and parameterize an eventual long-term corrosion model. This report was prepared in support of this effort to define the test suite to evaluate the corrosion of IWFs, with the goal of defining and parameterizing a conceptual long-term corrosion model. A review was presented highlighting the high degree of variability between the IWF corrosion data that is available in the literature and the need for a standardized test suite. The targeted test suite is composed of a single interval screening test, a dynamic leach test, and post-test solid characterization of the monolithic IWF samples. The data presented serves two purposes: to expand the range of IWFs evaluated with the test suite to assess method variability and to further understand the corrosion of IWFs to best inform conceptual long-term corrosion model development. A series of IWF types were included in the testing, including hot isostatically pressed Ag-mordenite, silver functionalized silica-based aerogels, iodosodalites (hot isostatic pressing, sintered, glass bonded ceramic), iodoapatite, tellurite glass and glass composite materials.

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Synthesis and characterization of super occluded LiCl-KCl in zeolite-4A as a chloride salt waste form intermediate

Here, this paper reports the hygroscopic properties of eutectic LiCl-KCl after absorption into zeolite-4A, up to salt loadings of 75 wt%. Samples of the salt occluded zeolite were hydrated in a humidity chamber at constant temperature and relative humidity for up to 100 h. At up to 45 wt% salt loading, the un-occluded phase of salt consisted primarily of NaCl, which forms when the Na + ions present in the zeolite framework exchange with Li + and K + ions from the eutectic LiCl-KCl. This results in minimal water absorption and corrosion of contacted stainless steel. At greater than 45 wt% salt loading, water absorption and corrosion progressively worsened. The mixture has a significant amount of excess LiCl-KCl, making it highly hygroscopic. This study reveals an option for the intermediate treatment of waste salt from spent nuclear fuel electrorefiners that could facilitate it to be stored in a non-inert atmosphere for extended periods of time before final conversion into a permanent waste form.

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Behaviour of IPG waste forms bearing BaSO{sub 4} as the dominant sludge constituent generated from the treatment of water used for cooling the stricken power reactors

The great amount of water used for cooling the stricken power reactors at Fukushima Dai-ichi following the earthquake and tsunami of 11 March 2011 has resulted in accumulation of cooling water so-called the remaining water in some buildings. As the cooling water is subsequently contaminated by fission products (FPs) and some other radioactive substances, it is necessary to decontaminate this 'cooling water' to reduce the volume of liquid radioactive waste and to reuse it again for cooling the affected reactors. Some methods are applied to remove the radioactive substances from the cooling water. However, after treatments of water, there arises a secondary radioactive waste, the sludge. Steps are now taken to immobilize this sludge. In this paper, BaSO{sub 4}, as one of main constituents of the sludge, was chosen as an immobilizing target substance. The appropriate manufacturing condition of glass waste form for loading the sludge (BaSO{sub 4}) was studied and the chemical durability was evaluated by measuring the dissolution rate. For this experiment, the iron phosphate glass (IPG), which is known to possess a large loading capacity for a variety of chemical substances, was employed as the glass medium. Based on experimental results, it is evident that BaSO{sub 4} can be loaded into the IPG medium when it possesses the appropriate composition and melting temperature. During loading, BaSO{sub 4} converted into BaO, acting as a network modifier, which leads to enhanced stability of IPG. (authors)

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Analysis of NuCycle® Process Waste Streams and Identification of Candidate Waste Forms (CRADA 719) Abstract

The objective of this project is to support collaboration between PNNL and Curio to address technical gaps in the immobilization of waste streams generated by the NuCycle® process, thereby improving the overall viability of the technology. This work will be carried out in two phases, described below. Phase 1 – Waste Management Study The first phase consists of a comprehensive waste management study focused on the waste streams produced during the NuCycle® process, including those containing long lived fission products (LLFPs, e.g., I 129) and transuranic elements (TRUs). This phase involves compiling waste compositions and characteristics based on recently completed NuCycle® testing and modeling efforts. Established waste forms and processing methods will be identified for streams where they are applicable.

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Phase field-volumetric lattice Boltzmann model of ion uptake in porous nuclear waste form materials under continuous flow

The flow field within the mesopores of sorbent particles plays a crucial role in radionuclide diffusion and ion uptake kinetics, thus, impacting the overall performance of porous nuclear waste form materials. To fundamentally understand the influence of microstructures and material properties on the radionuclide absorption and retention processes requires a coupled multi-physics model that considers the advection and diffusion within the flow field, the reaction at liquid-solid interfaces, and finally, the solid-state diffusion within a complex nanoporous medium. Here, this study employs the volumetric lattice Boltzmann method (VLBM) to accurately and efficiently calculate the steady state velocity field inside the mesopores of sorbent particles. The obtained velocity field is then utilized to calculate the advection of ions in the steady flow. A phase field (PF) model of ion uptake is used to describe the reaction occurring at the solid-liquid interface and diffusion inside the porous medium. The integrated PF-VLBM model is verified in terms of the mass conservation and numerical efficiency and validated qualitatively with experimental observation data. Then, it is applied to study the influence of thermodynamic and kinetic properties, as well as flow field conditions on the ion uptake kinetics. The numerical results demonstrate that the ion uptake kinetics in porous particles has three distinct stages, which is in agreement with the observations in continuous flow experiments. In the first stage, the kinetics is predominantly controlled by the flow field and ion diffusivity in the liquid phase. The kinetics in the second stage is primarily governed by ion diffusivity in the solid phase. In the third stage the system reaches a dynamic equilibrium with a net zero uptake flux at the interface. It is also found that porous structures significantly affect the efficiency and capacity of ion uptake. The simulation results can help to understand the physics behind the observed ion uptake kinetics in experiments and to facilitate the development of constitutive equations that can account for heterogeneous microstructures in engineering performance codes.

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Impeding 99 Tc(IV) mobility in novel waste forms

Technetium ( 99 Tc) 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.

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Impact of oxidation and carbonation on the release rates of iodine, selenium, technetium, and nitrogen from a cementitious waste form

Evaluation of the long-term retention mechanisms and potential release rates for the primary constituents of potential concern (COPCs) (i.e., Tc, I, Se, and nitrate) is necessary to determine if Cast Stone, a radioactive waste form, can meet performance objectives under near-surface disposal scenarios. In this work, a mineral and parameter set accounting for the solubility of I and Se in Cast Stone was developed based on pH-dependent and monolithic diffusion leaching test results, to extend a geochemical speciation model previously developed. The impact of oxidation and carbonation as environmental aging processes on the retention properties of Cast Stone for primary COPCs was systematically estimated. Physically, the effective diffusion coefficients of 4 COPCs in Cast Stone were increased after carbonation and/or oxidation, reflecting an increase in permeability to diffusion. Chemically, i) pH & pe conditions in the original Cast Stone were favorable for the stabilization of Tc, but not for I, Se, and N; ii) oxidation (with/without carbonation) of Cast Stone changed the pe & pH conditions to be detrimental for Tc stabilization; and iii) carbonation (with/without oxidation) of Cast Stone modified the pH & pe conditions to be beneficial for the stabilization of I (in system with Ag added) and Se.

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Cement As a Waste Form for Nuclear Fission Products: The Case of 90 Sr and Its Daughters [Cement As a Container for Nuclear Fission Products: The Case of 90 Sr and Its Daughters]

One of the main challenges faced by the nuclear industry is the long-term confinement of nuclear waste. Because it is inexpensive and easy to manufacture, cement is the material of choice to store large volumes of radioactive materials, in particular the low-level medium-lived fission products. It is therefore of utmost importance to assess the chemical and structural stability of cement containing radioactive species. Here, we use ab initio calculations based on density functional theory (DFT) to study the effects of 90 Sr insertion and decay in C–S–H (calcium-silicate-hydrate) in order to test the ability of cement to trap and hold this radioactive fission product and to investigate the consequences of its β-decay on the cement paste structure. We show that 90 Sr is stable when it substitutes the Ca 2+ ions in C–S–H, and so is its daughter nucleus 90 Y after β-decay. Interestingly, 90 Zr, daughter of 90 Y and final product in the decay sequence, is found to be unstable compared to the bulk phase of the element at zero K but stable when compared to the solvated ion in water. Furthermore, cement appears as a suitable waste form for 90 Sr storage.

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Hierarchical Materials as Tailored Nuclear Waste Forms: A Perspective

This perspective focuses on the synthesis, characterization and modeling of three classes of hierarchical materials with potential for sequestering radionuclides: nanoparticles, porous frameworks and crystalline salt inclusion phases. The scientific impact of hierarchical structures and the development of the underlying crystal chemistry is discussed as laying the groundwork for the design, local structure control, and synthesis of new forms of matter with tailored properties. This requires development of the necessary scientific understanding of such complex structures through integrated synthesis, characterization, and modeling studies that can allow their purposeful creation and properties. The ultimate practical aim is to provide the means to create novel structure types that can simultaneously sequester multiple radionuclides. The result will lead to the creation of safe and efficient, long lasting waste forms for fission products and transuranic elements that are the products of nuclear materials processing waste streams. The generation of the scientific base for working toward that goal is presented.

hierarchal material, review article, nuclear waste↗

Removing Cs within a continuous flow set-up by an ionic exchanger material transformable into a final waste form

Silica monoliths loaded with hexacyanoferrate (HCF) nanoparticles were designed and synthesized to selectively remove Cs + ions from an aqueous saline solution within a continuous flow set-up. The decontamination and hydrodynamic efficiency of this smart material was compared to other granularly supported HCF. Finally, a thermal treatment was applied to transform the HCF functionalized monolith into a final waste form matrix.

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