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At least 955 records · Page 53

Mercury Speciation of Hanford 241-AP-107 Tank Waste Samples - 20384

The concentration of key mercury species in the Hanford tank waste has not been previously measured. Based on process knowledge, an estimated inventory of 2,100 kg of mercury is assumed and was distributed in varied amounts across 149 single-shell tanks (SSTs) and 28 double-shell tanks (DSTs). Limited analyses of individual SSTs and DSTs for total mercury were all below detection, yielding upper limits in concentration estimates based solely on instrument detection limits, resulting in an uncertain mercury inventory for Hanford tanks. Accurate and reliable chemical speciation and quantification is desired to anticipate, predict, and abate the mass movements of various mercury species through the Hanford waste processing flowsheet. Highly sensitive separation and quantification methods for total, elemental, and monomethyl mercury species, in tank waste, have been developed at the Pacific Northwest National Laboratory's (PNNL) Radiochemical Processing Laboratory (RPL). A non-radiological environmental method to quantify mercury species has been adapted for application to Hanford tank 241-AP-107 raw supernatant feed, filtered feed, and cesium-decontaminated samples. These samples represent feed inventory and pretreatment process effluents prior to immobilization by vitrification. This method separates and preconcentrates total, elemental, and monomethyl mercury onto selective solid substrates with little-to-no radioactive background. The solid samples can then be released from strict radiological control, allowing for analytical work to be conducted in low-level radiological facilities. Separation of mercury species was demonstrated at PNNL's RPL in Richland, Washington before transport and analytical quantification using cold vapor atomic fluorescence spectrometry (CVAFS) at PNNL's Marine Science Laboratory (MSL) in Sequim, Washington. Additional studies were conducted to assess the stability of monomethyl mercury in distilled matrices and preconcentrated onto the Carbotrap{sup R} solid substrate to assess sample degradation over time during transport. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Hanford Double Shell Waste Tank Corrosion Studies (Final Report)

For fiscal year (FY) 2022, the Savannah River National Laboratory (SRNL) focused on two experimental tasks related to Hanford Double Shell Tank (DST) chemistry and integrity. The first task focused on understanding risk of corrosion due to formation of either continuous layers or discrete patches of solids on the tanks' inner sidewalls and bottoms. The tank bottom solids contact corrosion testing focused on studying the effects of forming a dry adherent solids layer on a carbon steel substrate. Long-term exposure tests and electrochemical tests were performed to investigate the effect of drying (i.e., removing water) from the solids phase. The second task focused on corrosion of the exterior of the secondary liner. In previous years, vapor corrosion inhibitors (VCIs) were investigated as a means of mitigating corrosion of the exterior of the secondary liner. During FY22 the utilization of nitrogen was explored as a means of corrosion mitigation. The corrosion test results with nitrogen were compared with the corrosion mitigation performance of the VCIs.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Raman Spectroscopic In Situ Monitoring of Highly Turbid Media

The ability to run chemical processing more efficiently and cost effectively is a need that spans critical materials recovery and legacy nuclear waste cleanup. Sensors integrated to provide online monitoring are essential to addressing this need by providing near-real time feedback on process conditions, which can improve efficiency, aid in decision making, and reduce the need for grab sample measurements. Optical spectroscopy is well-suited for providing online chemical composition information and has been widely applied in varied chemical systems. However, applications in turbid matrices continue to represent substantial challenges to sensor performance, where absorption or scattering of excitation light can cause significant signal interference. Here, in this study, close-focus Raman probes are investigated for use in turbid media as a way to overcome the signal loss from the scattering of the Raman excitation source. This, paired with advanced data science techniques, allowed for the development of chemometric models for the accurate quantification of several analytes of interest (NO 3 – , NO 2 – , and PO 4 3– ) in highly turbid solutions with solids loadings of up to 20 wt %. This work focuses on offline sample measurement and characterization as an initial step toward the development of online monitoring capabilities. Chemical systems of interest were focused on nuclear waste at the Hanford Site, which represents highly complex matrices that could realize significant processing benefits through the integration of online monitoring.

Felmy, Heather M. [Pacific Northwest National Labo↗

Solubility Testing to Support the Addition of Sodium Reactor Experiment Material to Sludge Batch 10

The Savannah River Site H-Canyon Facility is planning to discard dissolved Sodium Reactor Experiment (SRE) material into Tank 51 prior to Sludge Batch 10 (SB10). SB10 with the SRE material will be processed in the Defense Waste Processing Facility (DWPF) using the Nitric-Glycolic Acid (NGA) flowsheet. The DWPF Nuclear Criticality Safety Evaluation (NCSE) protects a 14:1 mass ratio of manganese to equivalent uranium-235 in both the solid and liquid phases during processing by requiring a 70:1 mass ratio in the feed. A concern was raised that freshly precipitated manganese in the SRE material will behave differently from the manganese in sludge during DWPF processing and potentially invalidate the criticality control. To mitigate risks to the DWPF criticality controls, the Savannah River National Laboratory (SRNL) performed a metals solubility test applicable to recently precipitated manganese and uranium, as would be expected with SRE transfers to SB10. The objective of this analysis is the tracking of partitioning of the primary fissile component (uranium-235) with the credited poison (manganese) between the aqueous and insoluble phases.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Distributed sustainable metals production: opportunities for intensifying separations & alternative feedstocks

Meeting the increased demand for rare earth elements and beyond primary mined ore. Secondary sources like phosphogypsum, coal fly ash, used nuclear fuel, and electronic waste are concentrated sources of critical minerals. One strategy for a resilient supply chain is to decentralize sourcing and hydrometallurgical processing of metals. Rotating packed beds (RPBs) for solid-phase extraction and liquid-liquid extraction are gaining momentum for their ability to increase process throughput by 5-10x the state of the art. In conclusion, this review discusses advances in hydrometallurgical RPB processes and opportunities for implementation in distributed metals production.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Process for purification of waste water produced by a Kraft process pulp and paper mill

The water from paper and pulp wastes obtained from a mill using the Kraft process is purified by precipitating lignins and lignin derivatives from the waste stream with quaternary ammonium compounds, removing other impurities by activated carbon produced from the cellulosic components of the water, and then separating the water from the precipitate and solids. The activated carbon also acts as an aid to the separation of the water and solids. If recovery of lignins is also desired, then the precipitate containing the lignins and quaternary ammonium compounds is dissolved in methanol. Upon acidification, the lignin is precipitated from the solution. The methanol and quaternary ammonium compound are recovered for reuse from the remainder.

Humphrey, M. F.↗

Systematic Calculation of Pu Pourbaix Diagrams: Modelling Support for the LANL ACRSP Team

The report enclosed entitled “Systematic Calculation of Pu Pourbaix Diagrams: Modelling Support of the LANL ACRSP Team” was prepared by Amphos21 under contract to the Los Alamos National Laboratory Actinide Chemistry and Repository Science Program (ACRSP) team to support an enhanced understanding of the actinide and brine chemistry in the Waste Isolation Pilot Plant (WIPP) transuranic repository. In this report, the ThermoChimie chemistry model and database, with some slight modifications, were used to calculate Pourbaix diagrams to investigate the effects of ionic strength, organic complexation, and metal competition on the predominance diagrams for aqueous and solid plutonium species under the anoxic and reducing conditions expected in the repository. These diagrams were connected to iron chemistry phase diagrams since this iron chemistry is expected to define and control redox properties in the WIPP repository concept.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Reactions of Studtite UO 4 ·4H 2 O in Alkali Hydroxides: Isolation of Single-Crystal Uranate Phases under Mild Hydrothermal Conditions

Uranyl peroxide complexes, particularly studtite (UO 4 ·4H 2 O), are important phases within the nuclear fuel cycle, forming through radiolysis-induced reactions on the surfaces of spent fuel and in waste environments. Studtite has been identified in Hanford’s irradiated fuel storage basins, Chornobyl’s corium lavas, and is anticipated on Fukushima’s fuel debris. While its formation and stability have been extensively studied, the reactivity of UO 4 ·4H 2 O in highly alkaline environments such as those encountered in high-level nuclear waste remains underexplored. These environments contain molar concentrations of [OH - ] and present a chemically dynamic and reactive environment where actinide behavior is not well understood. Reported here are investigations of uranium reactions in concentrated alkali hydroxides under mild hydrothermal conditions (<200 °C) that have resulted in the isolation of the alkali metal uranates Li 2 UO 4 , α-Na 2 UO 4 , γ-Na 2 U 2 O 7 , and K 2 U 2 O 7 . In contrast to conventional solid-state methods (>800 °C) that typically yield polycrystalline powders, our approach enables the isolation of these uranates as single crystals, allowing us to provide single-crystal structure solutions of certain uranates for the first time. Our findings match the results of high-level waste tank sampling, confirming that sodium diuranate (Na 2 U 2 O 7 ) is the most persistent uranium phase, potentially forming through reactions of uranyl peroxide intermediates with NaOH under radiolytic and highly alkaline conditions.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Electrothermal Micromirror Adaptive Illumination

As part of the Cyclotron Road program, Helux Lighting aimed to develop a highly adaptive illumination source based on microelectromechanical system (MEMS) technology and next-generation solid state lighting. Solid state lighting has caused a paradigm shift in the industry. Developing systems that put light only where it is needed can reduce energy consumption and have an impact on the well-being of the population by eliminating glare and wasted light. Full control could also reduce the disruption of sensitive ecosystems caused by light pollution. The most advanced fixtures available today are based on mechanical components that are bulky and expensive. The track light is the only inexpensive lighting system that permits redirection and, in some cases, spot size by motorized optical components. The most advanced light fixtures today are composed of a strategically arranged array of LEDs. More recent developments in the research community include dynamic liquid crystal lenses but fail to realize simultaneous dynamic steering and spot size. In this project, Helux worked on the capability development of their controllable micromirror combined with state-of-the-art solid state lighting to electronically adjusting light position, brightness, and illumination area.

42 ENGINEERING↗

Purification of legacy Ra-226 from ingrown Pb-210 using cation exchange chromatography

With the growing interest in using radium-226 (Ra-226) as a source material to produce essential radionuclides for targeted alpha therapies, the global demand for Ra-226 has surged, rendering its acquisition difficult. The shortage necessitates the exploration of alternative pathways to obtain this isotope beyond traditional commercial vendors. Legacy radium sources remain widespread due to Ra-226’s historical use but require the removal of ingrown daughter products to obtain a pure Ra-226 product. In conclusion, a straightforward and effective purification method for legacy Ra-226 ampoules has been developed using cation exchange chromatography, enabling the reliable conversion of legacy materials into high-purity Ra-226 solutions.

and nuclear chemistry↗

Trash-to-Gas: Trash Preparation and Feed Mechanism

One method of reducing the mass and volume of astronaut waste items during future exploration missions is a process called Trash-to-Gas (TtG), which uses thermal degradation to convert various astronaut waste items into a gas that can either be repurposed onboard or safely vented overboard. This project aims to determine which methods for pre-processing waste may enhance the gasification efficiency within a microgravity TtG reactor. Preparation methods that were investigated include mixing, pre-drying, shredding, compacting, and raw unprocessed waste. Each of these preparation methods was tested within the state-of-the-art subscale TtG system, known as the Orbital Syngas/Commodity Augmentation Reactor (OSCAR), and the resulting solid-to-gas conversion and burn durations were compared. Full-scale CAD models of these various preparation methods in conjunction with a projected full-scale TtG reactor were created using Creo Parametric. An Equivalent System Mass (ESM) analysis was then performed to trade the benefits of improved solid-to-gas performance with the costs associated with implementing the additional components that would increase system mass, power, volume, and design complexity. The results of this ESM analysis will be leveraged for future full-scale TtG system development to help reduce the overall mass, power, and volume of the system while ensuring effective reactor performance.

Ray Pitts↗

Method for carbon dioxide capture and sequestration using alkaline industrial wastes

A method of sequestering gaseous carbon dioxide in which an oxide is carbonated by contacting it with a first aqueous carbonate solution to convert a portion of the oxide into a carbonate, which precipitates from solution. By converting the oxide to a solid carbonate, the CO 2 from the first carbonate solution is sequestered into the precipitate. At the same time, an aqueous hydroxide solution is formed. The aqueous hydroxide solution is contacted with gaseous carbon dioxide which sequesters the gaseous CO 2 into a second aqueous carbonate solution. The second solution so generated is then recycled back into the process and used to convert the oxide into the precipitated carbonate.

Wang, Bu↗

Characterization of Tank 15H Sample in Support of Preliminary Cease Waste Removal and Closure Mode Determination

The Savannah River National Laboratory (SRNL) was requested by Savannah River Mission Completion (SRMC) to provide sample preparation and analysis of Tank 15H characterization samples. These samples follow an interest in exploring avenues to condense the extensive sampling of the Tank Closure process. One such pathway would be to collect a sample during an earlier waste removal campaign for analysis to determine comparability to the later residual tank inventory determined through Residual Material sampling and characterization prior to grouting. Six Tank 15H samples (HTF-15-24-9, HTF- HTF-15-24-10, HTF-15-24-11, HTF-15-24-12, HTF&#x2;15-24-13, and HTF-15-24-14) were delivered to SRNL in May of 2024. These six Tank 15H samples were taken as close as possible to the solids layer of the Tank 15H. These six Tank 15H samples were combined to form one composite sample for characterization due to the lack of sufficient solids fraction.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Feedback from International Decommissioning Planning Projects - 20269

Decommissioning of Nuclear Power Plants is an increasing reality in many countries with nuclear power. Already many years before final shutdown, planning of the decommissioning work is usually started in order to understand for example the costs, waste volume capacity and licensing work needed. In many countries it is required to have a final decommissioning plan before any decommissioning work is allowed to start. Westinghouse has been involved in international decommissioning planning for more than 30 years, where the first 20 years was mostly funding and preliminary plans due to that decommissioning was many years away. However, as many more plants are now moving into decommissioning, the focus has shifted to final decommissioning plans with budgets instead of funding plans, strategic decisions instead of choices, waste volume specifications instead of estimates and a defined approach instead of what ifs. Westinghouse has developed a methodology based on the planning and execution of many decommissioning projects in Europe, America and Asia. That international experience and understanding helps the customers to adopt a systematic planning process where strategy development is done with the end state in mind, where the goals are clearly outlined and the starting point described. The process and steps to reach the desired end state need to be clearly defined and all options/alternatives evaluated from a cost/benefit point of view. This is followed by a thorough and quantitative risk analysis in order to give solid recommendations and credible conclusions. One important feedback has been that real decommissioning experience from reference projects is invaluable for an efficient and timely progress in order not to spend unnecessary time and effort on understanding the barriers and links between different activities in decommissioning. Skilled project managers or engineers can drive the project forward, but without decommissioning experience previously gained, valuable lessons learned are not used and the same mistakes can be made again. Many utilities have invested in knowledge transfer from other decommissioning projects through site visits, exchange programs and supplier meetings, which is a valuable asset and way of implementing lessons learned from performed decommissioning projects into the planning process. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

The Role of the Organic Solvent Polarity in Isolating Uranyl Peroxide Capsule Fragments

Uranyl peroxide capsules are a fascinating class of polyoxometalates (POMs), discovered only in the 21st century. Understanding the reactivity between peroxide, alkali cations, and uranyl in alkaline solutions is important in nuclear science disciplines including mineralogy, nuclear energy, and legacy nuclear wastes. In this work, we have developed a general procedure to isolate different fragments of the uranyl-peroxide POM capsules, using organic solvents to partially remove K + salts from crude solids of the monomer building block UO 2 (O 2 ) 3 4– (K–U 1 ), leading to stabilization of these reactive fragments. Higher polarity organic solvents remove more K + salts from the crude solid, owed to higher solubility, resulting in more extensive linking of uranyl peroxide building units. By this strategy we have isolated and structurally characterized a dimer K 6 [(UO 2 ) 2 (O 2 ) 4 (OH) 2 ]·7H 2 O (K–U 2 ) and a hexamer face frequently observed in the capsules, K 12 [(UO 2 ) 6 (O 2 ) 9 (OH) 6 ]$·x$H 2 O(K–U 6 ). Comparing experimental and computed Raman spectra shows that these intermediates crystallize by a solid-to-solid transformation, via polymerization of the monomer building block. By small-angle X-ray scattering (SAXS), we track the conversion of the fragments to POM capsules; the reaction rate increases from K–U 1 (days) < K–U 2 (hours) < K–U 6 (instantaneous). This study provides a general synthetic procedure to isolate metastable uranyl peroxide oligomers and control the oligomerization, which will be later applied to systems with the heavier alkalis that are even less stable.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ultrafast solid-liquid intercalation enabled by targeted microwave energy delivery

In chemical reactions, the breaking and formation of chemical bonds usually need external energy to overcome the activation barriers. Conventional energy delivery transfers energy from heating sources via various media, hence losing efficiency and inducing side reactions. In contrast, microwave (MW) heating is known to be highly energy efficient through dipole interaction with polar media, but how exactly it transmits energy to initiate chemical reactions has been unknown. Here, we report a rigorous determination of energy delivery mechanisms underlying MW-enabled rapid hydrothermal synthesis, by monitoring the structure and temperature of all the involved components as solid-liquid intercalation reaction occurs using in situ synchrotron techniques. We reveal a hitherto unknown direct energy transmission between MW irradiation source and the targeted reactants, leading to greatly reduced energy waste, and so the ultrafast kinetics at low temperature. These findings open up new horizons for designing material synthesis reactions of high efficiency and precision.

36 MATERIALS SCIENCE↗

Potential Disposition Options for a Salt Fueled Molten Salt Reactor At the INL (A White Paper)

The molten salt reactor (MSR) design concept has been the focus of significant research and development efforts, both in the U.S. and around the world. There are generally two types of MSRs, salt fueled MSRs that have the fuel dissolved within the salt and solid fueled MSRs that only use the molten salt as a coolant. The range of conceptual designs and the flexibility of operations of MSRs results in a wide range of potential waste streams from salt fueled MSRs; all of which require safe and secure storage and eventual disposition. This white paper will 1) survey the range of salt fueled MSR designs, 2) recognize the implications of design, on the resulting waste streams, and 3) identify the definitions and regulations that apply to the safe and secure management, storage, and disposal of these streams. Research in MSR waste streams is young and the focus of intense research that requires more funding and time to become mature enough to fully support design decisions. Once a specific design is selected, a more detailed management and disposition effort must be performed.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗