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All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Permanent Criticality Termination Processes in Disposed DPCs

This report aims at answering what, how, and when spent nuclear fuel (SNF) or dual-purpose canister (DPC) characteristics could be impacted by disposal events and processes, including decay, corrosion, dissolution, and criticality, such that the potential for criticality initiation or continuation in disposed DPCs becomes permanently significantly diminished. This report uses the term "permanent termination of criticality to denote the significant diminishment of criticality potential, not absolute prevention. The occurrence of disposal processes and events is a direct function of disposal time. For fundamental processes (e.g., decay), time is absolute; however, for other processes (e.g., corrosion), time is relative because it is driven by a combination of DPC characteristics (e.g., fuel conditions, basket composition), geologic parameters (e.g., infiltration rate), engineered barrier design, and other processes and events that impact in-package chemistry.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2024

Effective Corrosion-Resistant Single-Atom Alloy Catalyst on HfO 2 -Passivated BiVO 4 Photoanode for Durable (≈800 h) Solar Water Oxidation

Green hydrogen (H 2 ) production from solar water splitting necessitates photoelectrodes with superior photoelectrochemical (PEC) activity and durability. However, surface defects and photocorrosion instability—especially at high potentials—limit PEC performance and stability. Herein, the prototypical bismuth vanadate (BiVO 4 ) photoanode is used to demonstrate a holistic approach to improve photocurrent density and long-term stability. In this approach, high surface-area nanostructuring of BiVO 4 is combined with barium (Ba) doping with semi-crystalline hafnium oxide (HfO 2 ) surface passivation and single-atom nickel platinum (NiPt) catalysts. The introduction of Ba 2+ ions into BiVO 4 increases the concentration of conductive V 4+ ions or the ratio of V 4+ ions to oxygen vacancies, avoiding V 5+ dissolution during water oxidation. The semi-crystalline HfO 2 , which serves as a passivation layer, prevents BiVO 4 photocorrosion by suppressing harmful chemical reactions when holes are transferred to the electrolyte. The synergistic use of isolated single-atom and Ni-Pt coordination improves charge transfer at the photoanode/electrolyte interface, leading to enhanced PEC kinetics and stability. As a result, a photoelectrode is demonstrated with ≈6.5 mA cm -2 at 1.23 V versus a reversible hydrogen electrode (RHE) and continuous operation for 800 h with a negligible degradation rate. This work provides a promising approach to improve photoanodes for PEC H 2 production.

08 HYDROGEN↗
DOE OSTI2023

Impact of aquifer properties on the extent and timeline of CO 2 trapping

Abstract Geologic CO 2 sequestration in porous saline aquifers is a promising approach to reducing atmospheric concentrations of CO 2 . Reactive transport simulations provide the opportunity to analyze which factors influence geochemical reactivity in the reservoir, understand those most important for promoting CO 2 trapping, and assess individual sites. Field‐scale aquifer characterization is time and resource intensive such that here, reactive transport simulations are leveraged to enhance understanding of selected aquifer properties including porosity, permeability, depth of storage, and carbonate mineralogy on the overall CO 2 trapping potential to better select sites promoting geochemical reactivity for CO 2 trapping. There are different mechanisms for sequestrating CO 2 . Once injected, CO 2 will dissolve into the brine to create an acidic environment, resulting in the dissolution of pre‐injection formation minerals. Released ions can reprecipitate as secondary minerals. The dissolved CO 2 and mineralized CO 2 are considered as a more secure form of CO 2 trapping in this study compared to the free supercritical CO 2 . Here, a framework leveraging a controlled set of field scale simulations is developed to facilitate rapid, optimized site selection. Simulations vary aquifer properties to understand the impact of each unique property on CO 2 trapping, tracking, and comparing the amount of supercritical, aqueous, and mineralized CO 2 . The rate at which the CO 2 injected into the aquifer is converted to aqueous or mineralized CO 2 is newly defined here as the sequestration efficiency and used to compare simulation results. The reservoir depth and fraction of carbonate minerals in the formation are shown to be more important factors than reservoir porosity and permeability in affecting CO 2 trapping. However, the impact of aquifer properties on the evolution of injected CO 2 depends on the stage of the sequestration project. © 2023 Society of Chemical Industry and John Wiley & Sons, Ltd.

Energy & Fuels↗
DOE OSTI2022

Evaluation of subsurface transport processes of delayed gas signatures applicable to underground nuclear explosions

Radioactive gas signatures from underground nuclear explosions (UNEs) result from gas-migration processes occurring in the subsurface. The processes considered in this study either drive or retard upward migration of gases from the detonation cavity. The relative importance of these processes is evaluated by simulating subsurface transport in a dual-permeability medium for the multi-tracer Noble Gas Migration Experiment (NGME) originally intended to study some aspects of transport from a UNE. For this experiment, relevant driving processes include weak two-phase convection driven by the geothermal gradient, over pressuring of the detonation cavity, and barometric pumping while gas sorption, dissolution, radioactive decay, and usually diffusion represent retarding processes. From deterministic simulations we found that over-pressuring of the post-detonation chimney coupled with barometric pumping produced a synergistic effect amplifying the tracer-gas reaching the surface. Bounding simulations indicated that the sorption and dissolution of gases, tending to retard transport, were much smaller than anticipated by earlier laboratory studies. The NGME observations themselves show that differences in gas diffusivity have a larger effect on influencing upward transport than do the combined effects of tracer-gas sorption and dissolution, which is consistent with a Sobol’ sensitivity analysis. Both deterministic simulations and those considering parametric uncertainties of transport-related properties predict that the excess in concentration of SF 6 compared to 127 Xe as might be captured in small volumetric samples should be much smaller than the order-of-magnitude contrast found in the large-volume gas samples taken at the site. While extraction of large-volume subsurface gas samples is shown to be capable of distorting in situ gas compositions, the highly variable injection rate of SF 6 into the detonation cavity relative to that of 127 Xe at the start of the field experiment is the most likely explanation for the large difference in observed concentrations.

58 GEOSCIENCES↗
DOE OSTI2015

Optimal well placement and brine extraction for pressure management during CO 2 sequestration

Large-scale pressure increases resulting from carbon dioxide (CO 2 ) injection in the subsurface can potentially impact caprock integrity, induce reactivation of critically stressed faults, and drive CO 2 or brine through conductive features into shallow groundwater. Pressure management involving the extraction of native fluids from storage formations can be used to reduce such pressure increases. However, dealing with large volumes of extracted brine can be technically challenging and expensive. Selection of optimal well locations and pumping rates are critical for maximizing CO 2 storage and minimizing brine extraction during geologic CO 2 sequestration (GCS). Robust and efficient computerized algorithms combining reservoir models and optimization methods are needed to make proper decisions on well placement and pumping rates. This work presents a constrained differential evolution (CDE) algorithm for solving global optimization problems involving pressure management of GCS projects. Application of the CDE optimization methodology was demonstrated for a hypothetical CO 2 storage scenario in a deep sandstone reservoir in the Southern San Joaquin Basin in California, USA. Industrial-scale storage of CO 2 would generate significant pressure buildup in this formation, which in turn would raise concerns about induced seismicity due to presence of multiple faults surrounding the injection site. Through the CDE optimization algorithm coupled to a vertically-averaged reservoir simulator, we successfully estimated optimal solutions for brine extraction wells in the reservoir that would limit the local pressure along the faults to a prescribed threshold. Multiple realizations of the reservoir permeability field were created to understand the impact of reservoir heterogeneity on optimization results. Our results indicate that the reservoir slope and heterogeneity have significant impact on optimum extraction rates. Reservoir heterogeneity is also a significant factor for extraction well locations, suggesting that in practice decisions about extraction well placement through optimization should be made at later project stages when data from a few years of CO 2 injection have allowed iterative updating and refining of the reservoir forward models. Although the study focused on optimization of brine extraction, the CDE optimization methodology presented in this paper has also potential to solve other complex optimization problems related to GCS, such as increasing storage efficiency by enhancing injectivity and capillary and dissolution trapping.

58 GEOSCIENCES↗
DOE OSTI2018

Final Report - Impact of Microstructure on the Containment and Migration of CO 2 in Fractured Basalts

The overall objective of the project was to advance the scientific and technical understanding of fracture microstructure on the flow and mineralization of CO 2 injected into fractured basalt. The project combined bench-scale CO 2 -water-rock testing, geochemical characterization of rock cores, and advanced characterization of the evolution of fracture structure and carbon trapping mechanisms. A series of natural and artificial basalts were acquired and characterized for use in experiments. High pressure and high temperature experiments were performed in both batch modes and in flow-through systems. The dissolution of silicate minerals in the basalts was tracked, and the timing, identity and location of carbonate minerals that trap that added CO 2 were determined. A reactive transport model was developed that generated simulations that were consistent with the major trends in the experimental data. Novel X-ray computed tomography and nuclear magnetic resonance tools were developed as part of the project. The project found that the formation of carbonate minerals in basalts subjected to injection of CO 2 -rich aqueous solutions can be rapid and extensive. The mineral trapping rate and capacity of porous basalt is much greater than that of sandstone reservoirs. Geochemical gradients that develop upon the exposure of basalt to CO 2 -rich aqueous solutions lead to spatial localization of carbonate minerals in confined environments (e.g., narrow fractures, dead-end fractures, and vesicles). While carbonate minerals form in dead-end fractures, they do not form in ways that inhibit subsequent carbonation of the basalt.

58 GEOSCIENCES↗
DOE OSTI2026

Topology-Informed Design Rules for Deconstructable Thermoset Copolymer Networks

Existing models of thermoset deconstruction facilitated by incorporating cleavable comonomers rely on a mean-field reverse gel point paradigm, which predicts network dissolution once cleavable bonds reach a critical stoichiometric threshold, but does not account for where those bonds reside within the network architecture. Using reactive coarse-grained molecular dynamics simulations coupled with graph-theoretic analysis, we extend this stoichiometric picture to show that deconstructability is governed by the curing-imprinted network topology rather than stoichiometry alone. This topological organization is hierarchical: at the local scale, the elastic effectiveness of cross-link junctions determines which cross-links constitute the load-bearing scaffold; at the mesoscale, the cross-linking rate kinetically templates that scaffold into topologically modular communities─densely cross-linked clusters connected by sparse bridging strands that sustain network connectivity. Using betweenness centrality to identify nodes that disproportionately lie on intercommunity shortest paths, we demonstrate that effective deconstruction of the network into macromolecular fragments requires cleavable comonomers to intercept these high-centrality bridging strands. We further find that under uniform, disassortative comonomer incorporation, this topological requirement provides a mechanistic basis for extending the reverse gel point to incorporate network topology. We also show that modularity imposes a fundamental limit on fragment uniformity that persists even when the centrality requirement is met. Finally, we demonstrate that chain stiffness provides a nearly independent lever to suppress mechanically redundant cross-links and raise the glass transition temperature without significantly altering the deconstruction outcome. Together, these findings reframe the thermoset design space around network topology and provide actionable guidelines for engineering thermoset copolymers with predictable deconstructability and targeted thermomechanical performance.

coarse-grained molecular dynamics↗
DOE OSTI2022

A Fast‐Charging and High‐Temperature All‐Organic Rechargeable Potassium Battery

Abstract Developing fast‐charging, high‐temperature, and sustainable batteries is critical for the large‐scale deployment of energy storage devices in electric vehicles, grid‐scale electrical energy storage, and high temperature regions. Here, a transition metal‐free all‐organic rechargeable potassium battery (RPB) based on abundant and sustainable organic electrode materials (OEMs) and potassium resources for fast‐charging and high‐temperature applications is demonstrated. N‐doped graphene and a 2.8 m potassium hexafluorophosphate (KPF 6 ) in diethylene glycol dimethyl ether (DEGDME) electrolyte are employed to mitigate the dissolution of OEMs, enhance the electrode conductivity, accommodate large volume change, and form stable solid electrolyte interphase in the all‐organic RPB. At room temperature, the RPB delivers a high specific capacity of 188.1 mAh g −1 at 50 mA g −1 and superior cycle life of 6000 and 50000 cycles at 1 and 5 A g −1 , respectively, demonstrating an ultra‐stable and fast‐charging all‐organic battery. The impressive performance at room temperature is extended to high temperatures, where the high‐mass‐loading (6.5 mg cm −2 ) all‐organic RPB exhibits high‐rate capability up to 2 A g −1 and a long lifetime of 500 cycles at 70–100 °C, demonstrating a superb fast‐charging and high‐temperature battery. The cell configuration demonstrated in this work shows great promise for practical applications of sustainable batteries at extreme conditions.

25 ENERGY STORAGE↗
DOE OSTI2023

Microkinetic insights into the role of catalyst and water activity on the nucleation, growth, and dissolution during COF-5 synthesis

The chemical pathway for synthesizing covalent organic frameworks (COFs) involves a complex medley of reaction sequences over a rippling energy landscape that cannot be adequately described using existing theories. Even with the development of state-of-the-art experimental and computational tools, identifying primary mechanisms of nucleation and growth of COFs remains elusive. Other than empirically, little is known about how the catalyst composition and water activity affect the kinetics of the reaction pathway. In this work, for the first time, we employ time-resolved in situ Fourier transform infrared spectroscopy (FT-IR) coupled with a six-parameter microkinetic model consisting of ~10 million reactions and over 20 000 species. The integrated approach elucidates previously unrecognized roles of catalyst pK a on COF yield and water on growth rate and size distribution. COF crystalline yield increases with decreasing pK a of the catalysts, whereas the effect of water is to reduce the growth rate of COF and broaden the size distribution. The microkinetic model reproduces the experimental data and quantitatively predicts the role of synthesis conditions such as temperature, catalyst, and precursor concentration on the nucleation and growth rates. Furthermore, the model also validates the second-order reaction mechanism of COF-5 and predicts the activation barriers for classical and non-classical growth of COF-5 crystals. The microkinetic model developed here is generalizable to different COFs and other multicomponent systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

The effectiveness of TRIS and ammonium buffers in glass dissolution studies: a comparative analysis

Abstract Selecting appropriate buffers is crucial for evaluating the chemical durability of glass under controlled conditions such as in the EPA 1313 test designed to measure elemental release as a function of pH. The efficacy of two alkali-metal free buffers, TRIS (NH 2 C(CH 2 OH) 3 ) and ammonium chloride—ammonia (NH 3 /NH 4 Cl), was investigated during EPA 1313 testing of a simulated Hanford low-activity waste borosilicate glass in the alkaline regime (pH 8.5–10.5) at varying temperatures (RT, 40 °C, and 60 °C). While both buffers maintained the desired pH at room temperature, and up to 40 °C, the effectiveness of TRIS decreased at elevated temperatures, particularly at pH 10.5. Although 11 B NMR showed evidence of TRIS-B complexation, its effect on the rate of elemental release was found to be negligible under the test conditions. With ammonium buffer, the release of alkali cations was slightly elevated when compared to the same conditions with TRIS at early time points.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Forsterite [Mg 2 SiO 4 )] Carbonation in Wet Supercritical CO 2 : An in Situ High-Pressure X-ray Diffraction Study

Technological advances have been significant in recent years for managing environmentally harmful emissions (mostly CO2) resulting from combustion of fossil fuels. Deep underground geologic formations are emerging as reasonable options for long term storage of CO2 but mechanisms controlling rock and mineral stability in contact with injected supercritical fluids containing water are relatively unknown. In this paper, we discuss mineral transformation reactions occurring with forsterite (Mg2SiO4) exposed to wet supercritical CO2. Forsterite was selected as it is an important olivine group mineral present in igneous and mafic rocks and has been the subject of a large number of aqueous dissolution studies that can be compared with non-aqueous fluid tests in this study. Transformation reactions were examined by in situ high pressure x-ray diffraction in the presence of supercritical carbon dioxide (scCO2) containing dissolved water at conditions relevant to carbon sequestration. Under modest pressures (90 bar) and temperatures (50°C), scCO2 saturated with water was found to convert >70 wt% forsterite to a hydrated magnesium carbonate, nesquehonite (MgCO3 •3H2O) and magnesite (MgCO3), after 72 hours of reaction. However, comparable tests with scCO2 at only partial water saturation (82%) showed a significantly slower carbonation rate with only ~30-39 wt% conversion to nesquehonite and no evidence of the anhydrous form (MgCO3). Further decreases in water content of the scCO2 continued to reduce the extent of carbonation, until a critical moisture threshold (~30%) was crossed where forsterite no longer reacted in the presence of the wet scCO2 to form crystalline carbonates. Increasing the temperature to 75°C produced anhydrous magnesium carbonate, magnesite (MgCO3), preceded by the intermediate phase, hydromagnesite [Mg(CO3)4(OH)2 •4H2O]. Measurements conducted during in situ IR experiments at 50°C and 30% saturation identified the presence of an amorphous carbonate phase as well as the formation of a thin liquid-like water layer on the forsterite surface. The presence of this water film appears to be critical for the mineral carbonation of forsterite exposed to water bearing scCO2. In contrast, our prior studies with the mineral brucite [Mg(OH)2] showed extensive carbonation in the absence of a condensed water layer on the mineral surface. The contrasts in reaction rate and products formed demonstrated by temperature and water-content dependence highlights the importance of these kinds of studies to help enable better predictions of the long term fate of geologically stored CO2.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2011

Functionalized bimodal mesoporous silicas as carriers for controlled aspirin delivery

The bimodal mesoporous silica modified with 3-aminopropyltriethoxysilane was performed as the aspirin carrier. The samples' structure, drug loading and release profiles were characterized with X-ray diffraction, scanning electron microscopy, N{sub 2} adsorption and desorption, Fourier transform infrared spectroscopy, TG analysis, elemental analysis and UV-spectrophotometer. For further exploring the effects of the bimodal mesopores on the drug delivery behavior, the unimodal mesoporous material MCM-41 was also modified as the aspirin carrier. Meantime, Korsmeyer-Peppas equation f{sub t}=kt{sup n} was employed to analyze the dissolution data in details. It is indicated that the bimodal mesopores are beneficial for unrestricted drug molecules diffusing and therefore lead to a higher loading and faster releasing than that of MCM-41. The results show that the aspirin delivery properties are influenced considerably by the mesoporous matrix, whereas the large pore of bimodal mesoporous silica is the key point for the improved controlled-release properties. - Graphical abstract: Loading (A) and release profiles (B) of aspirin in N-BMMs and N-MCM-41 indicated that BMMs have more drug loading capacity and faster release rate than that MCM-41. Highlights: > Bimodal mesoporous silicas (BMMs) and MCM-41 modified with amino group via post-treatment procedure. > Loading and release profiles of aspirin in modified BMMs and MCM-41. > Modified BMMs have more drug loading capacity and faster release rate than that modified MCM-41.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2011

SOLIDIFICATION OF THE HANFORD LAW WASTE STREAM PRODUCED AS A RESULT OF NEAR-TANK CONTINUOUS SLUDGE LEACHING AND SODIUM HYDROXIDE RECOVERY

The U.S. Department of Energy (DOE), Office of River Protection (ORP), is responsible for the remediation and stabilization of the Hanford Site tank farms, including 53 million gallons of highly radioactive mixed wasted waste contained in 177 underground tanks. The plan calls for all waste retrieved from the tanks to be transferred to the Waste Treatment Plant (WTP). The WTP will consist of three primary facilities including pretreatment facilities for Low Activity Waste (LAW) to remove aluminum, chromium and other solids and radioisotopes that are undesirable in the High Level Waste (HLW) stream. Removal of aluminum from HLW sludge can be accomplished through continuous sludge leaching of the aluminum from the HLW sludge as sodium aluminate; however, this process will introduce a significant amount of sodium hydroxide into the waste stream and consequently will increase the volume of waste to be dispositioned. A sodium recovery process is needed to remove the sodium hydroxide and recycle it back to the aluminum dissolution process. The resulting LAW waste stream has a high concentration of aluminum and sodium and will require alternative immobilization methods. Five waste forms were evaluated for immobilization of LAW at Hanford after the sodium recovery process. The waste forms considered for these two waste streams include low temperature processes (Saltstone/Cast stone and geopolymers), intermediate temperature processes (steam reforming and phosphate glasses) and high temperature processes (vitrification). These immobilization methods and the waste forms produced were evaluated for (1) compliance with the Performance Assessment (PA) requirements for disposal at the IDF, (2) waste form volume (waste loading), and (3) compatibility with the tank farms and systems. The iron phosphate glasses tested using the product consistency test had normalized release rates lower than the waste form requirements although the CCC glasses had higher release rates than the quenched glasses. However, the waste form failed to meet the vapor hydration test criteria listed in the WTP contract. In addition, the waste loading in the phosphate glasses were not as high as other candidate waste forms. Vitrification of HLW waste as borosilicate glass is a proven process; however the HLW and LAW streams at Hanford can vary significantly from waste currently being immobilized. The ccc glasses show lower release rates for B and Na than the quenched glasses and all glasses meet the acceptance criterion of < 4 g/L. Glass samples spiked with Re{sub 2}O{sub 7} also passed the PCT test. However, further vapor hydration testing must be performed since all the samples cracked and the test could not be performed. The waste loading of the iron phosphate and borosilicate glasses are approximately 20 and 25% respectively. The steam reforming process produced the predicted waste form for both the high and low aluminate waste streams. The predicted waste loadings for the monolithic samples is approximately 39%, which is higher than the glass waste forms; however, at the time of this report, no monolithic samples were made and therefore compliance with the PA cannot be determined. The waste loading in the geopolymer is approximately 40% but can vary with the sodium hydroxide content in the waste stream. Initial geopolymer mixes revealed compressive strengths that are greater than 500 psi for the low aluminate mixes and less than 500 psi for the high aluminate mixes. Further work testing needs to be performed to formulate a geopolymer waste form made using a high aluminate salt solution. A cementitious waste form has the advantage that the process is performed at ambient conditions and is a proven process currently in use for LAW disposal. The Saltstone/Cast Stone formulated using low and high aluminate salt solutions retained at least 97% of the Re that was added to the mix as a dopant. While this data is promising, additional leaching testing must be performed to show compliance with the PA. Compressive strength tests must also be performed on the Cast Stone monoliths to verify PA compliance. Based on testing performed for this report, the borosilicate glass and Cast Stone are the recommended waste forms for further testing. Both are proven technologies for radioactive waste disposal and the initial testing using simulated Hanford LAW waste shows compliance with the PA. Both are resistant to leaching and have greater than 25% waste loading.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2013

Improving the Estimates of Waste from the Recycling of Used Nuclear Fuel - 13410

Estimates are presented of wastes arising from the reprocessing of 50 GWD/tonne, 5 year and 50 year cooled used nuclear fuel (UNF) from Light Water Reactors (LWRs), using the 'NUEX' solvent extraction process. NUEX is a fourth generation aqueous based reprocessing system, comprising shearing and dissolution in nitric acid of the UNF, separation of uranium and mixed uranium-plutonium using solvent extraction in a development of the PUREX process using tri-n-butyl phosphate in a kerosene diluent, purification of the plutonium and uranium-plutonium products, and conversion of them to uranium trioxide and mixed uranium-plutonium dioxides respectively. These products are suitable for use as new LWR uranium oxide and mixed oxide fuel, respectively. Each unit process is described and the wastes that it produces are identified and quantified. Quantification of the process wastes was achieved by use of a detailed process model developed using the Aspen Custom Modeler suite of software and based on both first principles equilibrium and rate data, plus practical experience and data from the industrial scale Thermal Oxide Reprocessing Plant (THORP) at the Sellafield nuclear site in the United Kingdom. By feeding this model with the known concentrations of all species in the incoming UNF, the species and their concentrations in all product and waste streams were produced as the output. By using these data, along with a defined set of assumptions, including regulatory requirements, it was possible to calculate the waste forms, their radioactivities, volumes and quantities. Quantification of secondary wastes, such as plant maintenance, housekeeping and clean-up wastes, was achieved by reviewing actual operating experience from THORP during its hot operation from 1994 to the present time. This work was carried out under a contract from the United States Department of Energy (DOE) and, so as to enable DOE to make valid comparisons with other similar work, a number of assumptions were agreed. These include an assumed reprocessing capacity of 800 tonnes per year, the requirement to remove as waste forms the volatile fission products carbon-14, iodine-129, krypton-85, tritium and ruthenium-106, the restriction of discharge of any water from the facility unless it meets US Environmental Protection Agency drinking water standards, no intentional blending of wastes to lower their classification, and the requirement for the recovered uranium to be sufficiently free from fission products and neutron-absorbing species to allow it to be re-enriched and recycled as nuclear fuel. The results from this work showed that over 99.9% of the radioactivity in the UNF can be concentrated via reprocessing into a fission-product-containing vitrified product, bottles of compressed krypton storage and a cement grout containing the tritium, that together have a volume of only about one eighth the volume of the original UNF. The other waste forms have larger volumes than the original UNF but contain only the remaining 0.1% of the radioactivity. (authors)

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2021

Chemical Recycling of Mixed Plastics in Electronic Waste Using Solvent-Based Processing

Currently, less than 20% of electronic waste (E-waste) produced in the U.S. is recycled. To improve the recycling rate of E-waste, the study aimed to: (1) identify the major plastics found within electronic shredder residue (ESR), (2) design solvents and processing conditions capable of separating out 90% of the plastic in ESR, and (3) estimate the energy efficiency of the solvent-based process developed. Preliminary screening showed 25 wt.% of the ESR was composed of plastics, with two polymers dominating the sorted plastic fraction—polystyrene (PS, 40 wt.%) and acrylonitrile butadiene styrene (ABS, 25 wt.%). Subsequently, solvents and anti-solvents were screened using Hansen Solubility Parameter Theory for PS, ABS, and ESR dissolution. The pre-screening results showed dichloromethane (DCM) and tetrahydrofuran (THF) as the most effective solvents for PS and ABS, with methanol (MeOH) and ethylene glycol (EG) as the most effective anti-solvents. By optimizing the dissolution time and the solvents used, the highest polymer dissolution yield (99 wt.%) was achieved using DCM for 48 h. Both MeOH and EG precipitated 71 wt.% of the polymer fraction of ESR. EG removed more phosphorus containing flame retardants (94 wt.%) than MeOH (69 wt.%). Energy analysis indicated that the solvent-based processes could save 25–60% of the embodied energy for PS and ABS. Characterization showed that the solvent-based processing could preserve the high molecular weight fraction of the polymers while removing flame retardants at the same time. The results from this study prove the potential of solvent-based processing to produce secondary plastic materials from E-waste for cross-industry reuse.

Anderson, Lester↗
DOE OSTI2018

Impacts of Crust Properties on the Waste Feed Delivery of Hanford Tanks with Flammability Concerns - 18161

Mitigation of flammability concerns within Hanford waste tanks is essential to Safe Storage and Waste Feed Delivery sub-functions of the River Protection Project Mission. The tanks that have a higher propensity for the generation, retention, and release of flammable gas are considered Waste Group A tanks. Group A tanks include 241-SY-103, 241-AN-103, 241-AN-104, 241-AN-105, and 241-AW-101. Successful mitigation of flammability concerns in these tanks is necessary, as they are critical to the completion of the River Protection Project Mission as indicated in the Integrated Waste Feed Delivery Plan. The benchmark for examination of tank flammability issues is 241-SY-101. Studies of Tank 241-SY-101 gas release events showed that the mechanism of gas retention and release was highly dependent on the volume and configuration of a floating crust layer. Beginning in 1993, 241-SY-101 underwent water additions and mixer pump operations resulting in dissolution of the crust. These efforts mitigated the flammability concerns of the tank. A similar mitigation approach was recommended for Tank 241-SY103 and is recommended for the other Waste Group A tanks. However, this recommended mitigation will be more or less effective based on the expected thickness of the crust present in each of the Group A tanks. Considerations of flammable gas generation and release mechanisms were essential in the development of a successful mitigation strategy for Tank 241-SY-101, and will be essential in the development of future mitigation strategies. Because crust properties are difficult to measure, tank surface level trends and current temperature profiles are evaluated to understand crust properties. 241-AN-103 and 241-AW-101 are the only two tanks with a net increase in surface level, indicating a higher generation and retention of flammable gas. Additionally, these are the two tanks with the thickest crusts, which causes both a higher retention of gas and a reduced evaporation rate. Given the current temperature profile, crust thickness for 241-AW-101 was re-evaluated to be 145 cm (57 in) ± 30 cm (12 in) which is different from its historic value. This gives 241-AW-101 the thickest crust, second only to 241-SY-101 prior to mitigation. The crust thickness for 241-AN-103, however, retains its historic value of 89 cm (35 in) ± 16 cm (6 in). These crust properties suggest modifications to the mitigation strategy are needed for each tank. For example, 241-AN-103 and 241-AW-101 will require additional water to dissolve the crust layer before flammability concerns are mitigated and further operations could commence. Implementation of the modified mitigation strategies will mitigate flammability issues and help fulfill the Safe Storage and Waste Feed Delivery sub-functions of the River Protection Project Mission safely and efficiently. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2011

Bioreduction of Fe-bearing clay minerals and their reactivity toward pertechnetate (Tc-99)

99 Technetium ( 99 Tc) is a fission product of uranium-235 and plutonium-239 and poses a high environmental hazard due to its long half-life (t1/2 = 2.13 x 10 5 y), abundance in nuclear wastes, and environmental mobility under oxidizing conditions [i.e., Tc(VII)]. Under reducing conditions, Tc(VII) can be reduced to insoluble Tc(IV). Ferrous iron [Fe(II)], either in aqueous form or in mineral form, has been used to reduce Tc(VII) to Tc(IV). However, the reactivity of Fe(II) from clay minerals, other than nontronite, toward immobilization of Tc(VII) and its role in retention of reduced Tc(IV) have not been investigated. In this study the reactivity of a suite of clay minerals toward Tc(VII) reduction and immobilization was evaluated. The clay minerals chosen for this study included five members in the smectite-illite (S-I) series, (montmorillonite, nontronite, rectorite, mixed layered I-S, and illite), chlorite, and palygorskite. Fe-oxides were removed from these minerals with a modified dithionite-citrate-bicarbonate (DCB) procedure. The total Fe content of these clay minerals, after Fe-oxide removal, ranged from 0.7 to 30.4% by weight, and the Fe(III)/Fe(total) ratio ranged from 44.9 to 98.5%. X-ray diffraction (XRD) and Mossbauer spectroscopy results showed that after Fe oxide removal the clay minerals were free of Fe-oxides. Scanning electron microscopy (SEM) revealed that little dissolution occurred during the DCB treatment. Bioreduction experiments were performed in bicarbonate buffer (pH-7) with Fe(III) in the clay minerals as the sole electron acceptor, lactate as the sole electron donor, and Shewanella Putrifaciens CN32 cells as mediators. In select tubes, anthraquinone-2,6-disulfate (AQDS) was added as electron shuttle to facilitate electron transfer. The extent of Fe(III) bioreduction was the highest for chlorite (~43 wt%) and the lowest for palygorskite (~4.17 wt%). In the S-I series, NAu-2 was the most reducible (~31 %) and illite the least (~0.4 %). The extent and initial rate of bioreduction were positively correlated with the percent smectite in the S-I series (i.e., layer expandability). Fe(II) in the bioreduced clay minerals subsequently was used to reduce Tc(VII) to Tc(IV) in PIPES buffer. Similar to the trend of bioreduction, in the S-I series, reduced smectite showed the highest reactivity toward Tc(VII), and reduced illite exhibited the least. The initial rate of Tc(VII) reduction, after normalization to clay and Fe(II) concentrations, was positively correlated with the percent smectite in the S-I series. Fe(II) in chlorite and palygorskite was also reactive toward Tc(VII) reduction. These data demonstrate that crystal chemical parameters (layer expandability, Fe and Fe(II) contents, and surface area etc.) play important roles in controlling the extent and rate of bioreduction and the reactivity toward Tc(VII) reduction. Reduced Tc(IV) resides within clay mineral matrix, and this association could minimize any potential of reoxidation over long term.

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