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DOE OSTI2023

Physical, Chemical, and Mineralogical Characterizations of MSWI Ash Product and Recommendations for Downstream Processing

The primary objectives of this project are to (1) systematically characterize MSWI ash, and (2) based on characterization findings, design preliminary flowsheets for downstream processing. To achieve these objectives, a total of ten tasks were completed, including sample collection, physical separation tests, liberation tests, synthetic MSWI ash preparation, elemental composition analysis, sequential chemical extraction, mineralogical characterization, pozzolanic activity characterization, thermal stability characterization, processing flowsheet design, TEA and T2M, and project performance reporting. Many useful findings and conclusions were obtained from the exhaustive efforts of this project from several different aspects, including: a) Valuable Metals in MSWI Ash: MSWI ash contains a diverse array of valuable metals. Based on potential recoverable values, the most valuable metals present in MSWI ash include Fe, Ti, Mn, Cu, Zn, V, Co, Ni, Sr, Sn, Ag, Mo, and Sc. Some of these metals have been identified as critical minerals by DOE and DOI, suggesting that MSWI is a promising feedstock for critical mineral recovery. Noticeable graphical and seasonable variations in the valuable metal content of MSWI ash were observed. Nevertheless, it was challenging to discern any clear, definitive patterns for conclusions from those observations. Compared with bottom ash, fly ash contains more volatile metals, such as Zn and Sn, but less nonvolatile metals, such as Fe, Mn, Cu, Zn, Co, and Ni. Mineralogical analyses showed that MSWI ash contains a substantial amount of calcium minerals, such as portlandite, lime, gypsum, and calcite. In addition, it was found that different types of valuable metals often exist in the same particles. b) Physical Separation of MSWI Ash: Both dry sieving and wet sieving were performed on MSWI ash. A notable disparity in the size distribution of the same material was observed when using the two different sieving methods. The disparity is due to the agglomeration of small particles. For the valuable metals investigated, no significant enrichment in a specific size fraction was observed, suggesting that it is challenging to preconcentrate the valuable metals through size fractionation. Due to the presence of ferromagnetic materials, such as Fe, most of the materials reported to the magnetic products obtained by dry magnetic separation. However, the enrichment effect is minimal due to the existence of particle agglomerates. Density separation at a cut-off density of 2.7 SG or higher led to noticeable enrichment of selected valuable metals, particularly Ti. The unburned carbon present in MSWI ash was effectively removed by flotation using diesel as the collector. A novel reagent scheme, Na2S plus cationic collectors, that can efficiently beneficiate nonferrous metals plus Co was developed. c) Liberation Tests: The particle size of MSWI ash was effectively reduced by grinding, and as a result, the encapsulated valuable metal particles (if any) were liberated to a certain degree. However, particle size reductions did not noticeably enhance the beneficiation performance using the physical separation methods, primarily due to the inefficiency of these methods in processing fine particles and/or a possibility that insufficient liberation is not a limiting factor for achieving satisfactory physical separation performance. Valuable metals were classified into water leachable, ion-exchangeable, acid soluble, reducible, oxidable, and insoluble forms. It was found that the distributions in the different categories, i.e., the occurrence modes of the valuable metals, were not affected by the particle size. d) Leaching Characteristics of Metals from MSWI Ash: Most of the valuable metals were extracted from the fly ash samples when using 1 M HCl or HNO3 as the lixiviant. The leaching reaction is a very fast process, which can reach equilibrium within the first 5 min. The releasing of Co, Ni and Ag are sensitive to leaching temperature, a higher recovery value could be obtained when using relatively higher leaching temperatures. The leachability of the valuable metals present in MSWI bottom ash is relatively lower than that of fly ash. Leaching recoveries increased with elevations in the acid concentration. Relatively high leaching recoveries were obtained for REEs, Mn, Co, Ni, Cu, and Zn using 1 M HCl or HNO3 as the lixiviant. Elevations in the reaction temperature noticeably increased the leachability of the valuable metals, whereas the leachability was barely influenced by oxidizing and reducing agents. Similar to fly ash, leaching valuable metals from bottom ash is a rapid process, with most of the leaching reaction completed within the first 5 minutes. e) Combusted iPhones: The original structure of iPhones was remained after treating at 400 ºC and 600 ºC, while after being treated at 800℃, the screen bent, and the back cover of iPhone melted. Increasing the combustion temperature to 1000℃, the screen scattered, and most of the components turned into ashes. Combustion enhanced the leachability of REEs, while the leachability of the other valuable metals, except for Zn, was barely affected. Most of the REEs present in the original iPhones occurred as oxidizable forms. With elevations in the combustion temperature up to 600 ºC, the oxidizable REEs were transformed to acid soluble forms. However, further elevations in temperature resulted in decreases in the acid soluble fraction and corresponding increases in the reducible and oxidizable forms. Additionally, combustion temperature also significantly altered the occurrence modes of other metals present in the iPhones. f) Synthetic MSWI Ash: It was found that in the absence of hydrogen peroxide, all the elements except for Si were leached to certain degrees. It is noteworthy that approximately 80% of Zn was leached with 1.2 M HCl. When hydrogen peroxide was added to the reaction system, noticeable increases in the leaching recovery of Fe, Mn, Co, Ni, and Cu were observed. The leaching recovery of Al and Si was barely affected by adding hydrogen peroxide. These results suggested that the majority of Zn in the synthetic MSWI ash existed as metal oxide, a portion of Fe, Mn, Co, Ni, and Cu existed as metal oxide, and Al and Si are associated with glasses which are difficult to leach. Additionally, the remaining Fe, Mn, Co, Ni, and Cu in the metallic form were efficiently oxidized in the presence of hydrogen peroxide. g) Pozzolanic Activity and Thermal Stability of MSWI Ash: MSWI fly ash has higher pozzolanic activity compared to the bottom ash sample, which indicates that the fly ash sample consumed more portlandite because of its smaller particle size as reactivity fundamentally relates to reaction surface area. However, after the recovery of valuable elements, the pozzolanic activity of both the valuable elements fraction and the less valuable elements-rich products decreased significantly, which means that the valuable elements recovery lowers the Ca(OH)2 consumption, thus leading to the low activity of SCM. h) Flowsheet Design for Metal Recovery from MSWI Ash: Based on the results of the comprehensive physical separation and acid leaching tests, circuits that enable the beneficiation of the valuable metals were developed. In these circuits, the valuable metals are recovered into nonferrous, ferrous, and other valuable metal concentrates, which are processed separately in the acid leaching step. The subsequent separation and purification steps are simplified due to the physical beneficiation step. In addition, the overall recovery cost is reduced since physical beneficiation is much cheaper compared with chemical processing. Using different technologies, such as selective precipitation and solvent extraction, a comprehensive hydrometallurgical circuit was designed, and compounds of Cu, Zn, Mn, Co, and Ni with a purity close to or even higher than 95% were successfully generated.

36 MATERIALS SCIENCE↗
NASA NTRSDate not supplied

EVA Swab Kit: Tools and Techniques for Collecting Aseptic Samples from Crewed Space Missions

Introduction: When we send humans to search for life on other planets, we'll need to know what we brought with us versus what may already be there. To ensure our crewed spacecraft meet planetary protection requirements—and to protect our science from human contamination—we'll need to assess and verify whether micro-organisms may be leaking/venting from our spacesuits. This requires collecting samples under Extravehicular Activity (EVA) conditions. Detailed, systematic research on forward contamination from robotic spacecraft has been steadily progressing since the Viking missions, but systematic studies of contamination from space suits has not been conducted in many years. The modern EMU (Extravehicular Mobility Unit) suit used by NASA is designed to leak at rates as high as 100 cc/min. Before humans land on Mars there is a critical need to understand the types and quantities of microbes that could be introduced via space suits. The Human Forward Contamination Assessment team at NASA’s Johnson Space Center (JSC) has developed a prototype EVA swab tool [1,2,3,4] designed for use in space to sample cleaned and uncleaned space suits to determine the present day microbial load and eventually the rate of leakage. The ability to assess microbial leakage early in advanced space suit and life support system design cycles will help avoid costly hardware redesign later. Test Objectives: The primary objective of EMU testing was to characterize the type of micro-organisms typically found on or near selected suit pressure joints under suit differential pressure conditions. Most human-borne microbes can fit through a 0.5 to 1.0 µm gap. Knowing which joints are more likely to leak will inform hardware design decisions. Knowing which types of micro-organisms may leak from EVA suits provides a basis for subsequent studies to characterize the viability of those organisms under destination conditions, as well as how far they might spread through natural or human-influenced processes. That data, in turn, will inform exploration mission operations and hardware design. The secondary objective of testing was to evaluate the interface between a fully suited test subject and the EVA swab tool at vacuum. Bulky EVA suits can restrict movement and limit visibility through the helmet visor. Fully suited testing is important for identifying tool design issues prior to flight. At exploration destinations, such as Mars, suited crew may be required to periodically sample their suits as part of an environmental monitoring protocol. Suit Microbial Sampling Results: This report details results of microbial swabs collected from current flight suit configurations worn by crew members assigned to upcoming ISS expedition missions as well as swabs collected from prototype suits intended for use on the Orion spacecraft. These tests were intended to characterize the types of contaminants found on flight suits under current, typical handling conditions. No attempt was made to change suit handling procedures, provide additional sterilization, or to limit typical potential contaminant sources. Using culture based techniques, we cultivated 235 CFU (colony forming units) comprised of 26 bacterial species and one fungal species on the outside of the suits. The fungal species and 14 of the bacterial species were unique to the suit surfaces and were not detected in any of the background samples collected within the chambers. We sequenced 755,434 ribosomal fragments on all of the suit surfaces from swab samples. 557,016 of these sequences represent DNA that survived at least 4 hours at vacuum. These sequences formed 2,464 OTU's (Operational Taxonomic Units, 97% similarity) showing low diversity in the samples. The most abundant sequences that survived vacuum belong to the genera Staphyloccocus, Ralstona, Bacillus and Rhodobacter all of which are common to the human microbiome. [5] See Danko et al., (2021) for more complete details of these first analyses. Further analysis of EVA suit materials with respect to the efficacy of various cleaning protocols and engineered containment solutions is planned to inform suit design for NASA’s Artemis Moon to Mars program crew testing. Swab Tool Function Results: The kit was demonstrated for fit and function in suited subject vacuum tests to determine how well the tool worked as an aseptic microbial sampling device as well as to identify any design elements that could be upgraded for EVA task specific improvement. It was found that sample acquisition efficacy could be enhanced by redesign of the sample canister to end-effector interface. Several modifications of the sample caddy assemblies to optimize EVA safety and functionality were also identified. Consequently, fabrication of the redesigned sample canister to end-effector assembly interfaces and and the sample caddy assemblies are required. Fabrication of sixteen flight sample canister assemblies (8 per each of two EVA Swab Kits) and two sample caddy assemblies are in process to be followed by hardware testing and certification to produce two flight-certified EVA Swab Kits for transport to ISS no earlier than summer of 2022. Sampling Strategy: The International Space Station is an ideal testbed for systematic studies of contamination from crewed vehicles since it has been continuously occupied for 20 years and exposed to non-terrestrial conditions. We will sample the exterior of the ISS during EVA using a purpose-built swab tool capable of maintaining sterility while undergoing temperature changes from -151 to +121°C under hard vacuum. Prior to each EVA, the project team will work with ISS mission managers to identify precise sampling locations, which will vary by EVA based on the translation paths and worksites scheduled for that particular EVA. Ideally, translation path handrails and areas near ECLSS (Environmental Control and Life Support System) external vent openings on a spacecraft would be assessed. There are currently more than a dozen ECLSS external vents on the ISS. Some are connected to systems that vent waste products, while others are intended to equalize cabin pressure. As EVA opportunity allows, microbial samples from any of these external vents would provide a valuable data point, though some will be more useful than others. Four criteria have been identified to help prioritize sampling sites near vents: • EVA Accessibility: To minimize cost, it is desired to piggy-back onto a planned EVA. Therefore, the sampling location must be readily accessible by an EVA crew • Type of Vented Products: Vent products that have been in direct contact with crew, such as cabin air, are more likely to contain microorganisms than vent products associated with isolated systems, such as experiment module combustion products. • Mass of Vented Products: Higher-flow vents are more likely to contain detectible levels of microbial contaminants than lower-flow vents. • Local Environment: Sample locations with relatively benign local conditions, such as warm surfaces shielded from direct ultraviolet (UV) radiation exposure, may be more likely to support microbial growth than locations with harsher local environmental conditions. Because EVA accessibility is the most important criteria, the proposal team worked with an astronaut and flight controllers using the Dynamic Onboard Ubiquitous Graphics (DOUG) tool. The DOUG virtual environment allows an operator to “fly” around the current ISS vehicle configuration to assess EVA translation paths, attach points, and keep-out zones. While analysis on station or rapid return to Earth would be preferable, samples collected from the exterior of the ISS have already been exposed to temperature variations between -157 and +121 °C as well as hard vacuum. Therefore, they should be fairly stable and robust. We hypothesize that samples collected from the ISS exterior could be stored for up to 6 months at -80°C without degradation. Sample canisters will be returned to Earth while frozen at -80°C for analysis, and sterilized canisters can be re-flown back to ISS to support additional sampling opportunities Relevance to NASA Exploration Objectives: These data will allow us to identify new or improved methods, technologies, and procedures for spacecraft sterilization and leakage mitigation to minimize the amount of contamination introduced to the environment by human explorers. This work is funded by NASA research grant: NNH18ZDA001N-PPR References: [1] Bell, M.S. et al. (2015) LPS XLVI, Abst. #1832 [2] Rucker et al. (2018) 42nd COSPAR (PPP.3) [3] Bell, M.S. et al. (2019) Mars Extant Life Conference, Abst. #5096.[4] Bell, M.S. et al., (2020) 43rd COSPAR (BO.2).[5] Danko D, et.al.,(2021)Front.Microbiol.12:608478.

Mary Suzanne Bell↗
NASA NTRS2022

NASA Utilization of Space Nuclear Systems for Robotic and Human Exploration Missions: Response to EO 13972: Promoting Small Nuclear Reactors for National Defense and Space Exploration

Space Nuclear Systems (SNS) technology development offers a wide range of capabilities to support NASA’s current and future missions. Executive Order (EO) 13972, “Promoting Small Modular Reactors for National Defense and Space Exploration” [1], issued 5 January 2021, directs NASA to define requirements for NASA utilization of nuclear energy systems for human and robotic exploration missions through 2040 and analyze the costs and benefits of such requirements.” Although it is premature to define requirements and cost for future exploration missions that have not yet been formulated, this report describes planned objectives and missions by 2040 that are enabled or enhanced by nuclear systems while taking into account a number of unique considerations for nuclear energy in the space environment. Nuclear energy systems are enabling for space missions and critical capabilities where conventional forms of energy production are impractical or impossible due to mass constraints, mission duration, or distance from the Sun. Space nuclear technologies available or in development for use by 2040 utilize radioisotope decay or nuclear fission and fall into three categories: heat, power, and propulsion. Current applications utilize radioisotope power systems that provide consistent and reliable performance in the sub-kilowatt power range. More advanced SNS can enable new mission objectives where high energy density solutions are critical, or where access to solar solutions is prohibitive. Higher power radioisotope and fission systems are under development within NASA for a wide variety of human exploration and science mission applications. Planned missions designed to use radioisotope systems include Dragonfly, a rotorcraft that will explore the surface of Titan, and Persephone, a mission concept for a Pluto orbiter. Nuclear fission systems have the key advantage of providing significantly higher power, lower mass solutions from tens to even thousands of kilowatts. Fission power is enabling to a sustained human presence on the Moon and developing a robust lunar economy. Fission propulsion is enabling for missions within and beyond cis-lunar space. This report examines NASA-envisioned mission applications and associated performance needs for SNS over the next twenty years leading to 2040 along with the unique technical considerations posed by space nuclear technology development. This includes engineering and operational logistics for ground handling, thermal management, survival of the space environment, operational safety, power requirements, and service longevity. Safety to the public, the NASA work force, and agency assets remains a top priority for NASA and particular attention is given to this aspect in the design, hardware assembly, ground operation, launch, and mission operation of an SNS. NASA relies on the Department of Energy as nuclear authority and its legacy of rigorous safety procedures as standards for ground development, test, transportation, and launch site operation. The principal concern is preventing unintended radiological release to the public or environment. Radioisotope system experience has established processes, including ground operation, transportation, and launch, that are considered directly applicable to emerging fission systems; however, fission systems have unique design needs that impact the safety and performance requirements. High efficiency power conversion from both fission and radioisotope systems requires high operating temperatures necessitating both passive and active thermal management to maintain safe and nominal operating conditions. Effective cooling and waste heat rejection have special considerations for space applications, whether in zero-g or reduced gravity. Fluid and heat transfer within the reactor system is not anticipated to be impacted by reduced or zero-g environments. Cryogenic working fluids and propellant supplies utilized in some space nuclear applications will need low mass, high capacity cryocoolers to meet the long-term storage and near zero-boiloff needs. Integrated, high power density SNS capable of being packaged in a single vehicle is a key consideration for NASA. Due to concerns for complexity and reliability, in space reactor assembly and reactor refueling are not current design considerations. Expanding into a new era for space exploration depends on mass-efficient, high-energy solutions to power deep-space vehicles, operate in harsh environments, and increase mission flexibility. NASA nuclear technology investments are targeting power for surface operations and propulsion for fast-transit, deep-space missions, all with the ability to reliably operate without the need for repair or refueling. NASA’s goals, enabled by nuclear technologies, provide for exciting advances in scientific objectives and human exploration, ushering in a new space age that enables a human presence on bodies beyond our Earth.

nuclear↗
DOE OSTI2023

Testing of Microchannels and Lab-Grown Stress Corrosion Cracks for Quantification of Aerosol Transmission

The formation of a stress corrosion crack (SCC) in the canister wall of a dry cask storage system (DCSS) has been identified as a potential issue for the long-term storage of spent nuclear fuel. The presence of an SCC in a storage system could represent a through-wall flow path from the canister interior to the environment. Modern, vertical DCSSs are of particular interest due to the commercial practice of using higher backfill pressures in the canister, up to approximately 800 kPa, compared to their horizontal counterparts. This pressure differential offers a relatively high driving potential for blowdown of any particulates that might be present in the canister. In this study, the rates of gas flow and aerosol transmission of a spent fuel surrogate through an engineered microchannel with dimensions representative of an SCC were evaluated experimentally using coupled mass flow and aerosol analyzers. The microchannel was formed by mating two gage blocks with a linearly tapering slot orifice nominally 13 μm (0.005 in.) tall on the upstream side and 25 μm (0.0010 in.) tall on the downstream side. The orifice is 12.7 mm (0.500 in.) wide by 8.86 mm (0.349 in.) long (flow length). Surrogate aerosols of cerium oxide, CeO 2 , were seeded and mixed with either helium or air inside a pressurized tank. The aerosol characteristics were measured immediately upstream and downstream of the simulated SCC at elevated and ambient pressures, respectively. These data sets are intended to add to previous testing that characterized SCCs under well-controlled boundary conditions through the inclusion of testing improvements that establish initial conditions in a more consistent way. While the engineered microchannel has dimensions similar to actual SCCs, it does not reproduce the tortuous path the aerosol laden flow would have to traverse for eventual transmission. SCCs can be rapidly grown in a laboratory setting given the right conditions, and initial characterization and clean-flow testing has begun on lab grown crack samples provided to Sandia National Laboratories (SNL). Many such samples are required to produce statistically relevant transmission results, and SNL is developing a procedure to produce samples in welded steel plates. These ongoing testing efforts are focused on understanding the evolution in both size and quantity of a hypothetical release of aerosolized spent fuel particles from failed fuel to the canister interior and ultimately through an SCC.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2022

Modeling of ATR Fuel in DOE Standard Canisters with Helium Backfill

One pathway for road-ready and final disposition packaging configurations for the aluminum-clad spent nuclear fuel (ANSF) fuel is storage within helium backfilled sealed Department of Energy (DOE) standard canisters. The typical packaging configuration for the 15-foot DOE standard canisters places 10 advance test reactor (ATR) elements a basket, and three baskets are loaded within each DOE canister. During in-reactor operations and cooling pond storage conditions, oxyhydroxide layers form on the surface of the aluminum clad fuel. These layers produce hydrogen gas over time due to the fuel’s radiation field. As part of the packing procedure, the ATR fuel should be dried to remove any residual physio-/chemi- sorbed water bound to the surface. A 50-year CFD model of the DOE canister packaged with fuel was developed to provide a temperature profile for coupled chemical modeling of the conditions within the canister. The results of this modeling include results at fully saturated and fully dried fuel cladding conditions. In the associated experimental work, radiolysis experiments tests were completed in a helium environment, and G-values for the radiolytic production of hydrogen from the oxyhydroxide layers were provided. That reaction was coupled with the thermal profiles and gas-phase reactions to develop a 50-year model of the conditions within a sealed DOE canister with ATR fuel. For a nominal scenario of stored ATR fuel, after 50 years the model results give a 1.36 atm total pressure, 7% mole percent hydrogen, for the upper decay heat, 1.51 atm total pressure, 16% mole percent hydrogen, and for upper decay heat with undried fuel 2.6 atm total pressure, 15% mole percent hydrogen. No case modeled yields significant oxygen, and for the lower decay heat case that is modeled, hydrogen concentrations are under the 4% flammability limit after 50 years of storage. The modeled pressures for all cases modeled are below the pressure limit for the DOE standard sealed canister.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2025

Dry Deactivation of Sodium Metal in a Molten LiCl-KCl-CsCl-NaCl System

An experimental study was performed with the objective of investigating and characterizing a dry technique for deactivation of sodium metal in a molten salt system. The study was performed in three parts. First, proof-of-principle testing of the technique was performed at bench scale. It involved loading and melting tens of grams of clean sodium metal atop a pool of LiCl-KCl-CsCl eutectic at ∼300°C and then adding ammonium chloride particles while mixing. The ammonium chloride reacted with sodium to form sodium chloride and nitrogen/hydrogen off-gases. The sodium chloride assimilated into the salt pool, forming a quaternary salt mixture of LiCl-KCl-CsCl-NaCl. The proof-of-principle testing repeatedly exhibited complete deactivation of the loaded sodium metal. Second, characterization of a LiCl-KCl-CsCl-NaCl system was performed using differential scanning calorimetry to produce a partial phase diagram of LiCl-KCl-CsCl eutectic versus NaCl, which identified the liquidus, solidus, and two-phase regions of the quaternary system. Third, the dry deactivation technique was demonstrated at kg-scale in an inert atmosphere radiological glovebox with sodium metal that was previously separated in the same glovebox from uranium metal in unirradiated blanket elements for the Fermi-1 nuclear reactor. The quaternary salt product at the end of the demonstration was sampled and showed complete deactivation of the sodium metal. Here, in short, this study qualified a technique to completely deactivate batches of sodium metal in the absence of air or water. While this study focused on the deactivation of sodium metal, including bond sodium from unirradiated blanket elements, the technique is applicable to other sources of sodium metal, such as sodium metal from batteries. Furthermore, the technique could also be extended to other alkali metal systems, including lithium, sodium, potassium, rubidium, cesium, and mixtures thereof.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2025

PFAS Removal by Ion Exchange Resins: Background and Knowledge Gaps with Respect to the Hanford Site

Per- and polyfluoroalkyl substances (PFAS) have been a rising concern for the past two decades, with the United States Department of Defense and Environmental Protection Agency investing millions of dollars in research into remediation and clean-up technologies. Due to the environmental persistence, toxicity, biological uptake, and ongoing changes in both federal and state regulatory space, understanding the fate and transport of PFAS compounds has been of growing concern to the US Department of Energy (DOE). The DOE’s Hanford Site is investigating historical use of PFAS and will be doing site characterization for PFAS. Thus, PFAS have not yet been identified as a contaminant concern in regulatory documents. Based on historical records that mention the discharge of aqueous film-forming foam containing PFAS and having on-site fire stations (a risk factor for PFAS contamination), it seems likely that environmental releases of PFAS may have occurred. Pump and treat (P&T) remediation is the selected remedy for multiple groundwater contaminant plumes at Hanford. These P&T systems use ion exchange (IX) as a component of aboveground treatment, with the specific resins depending on the target contaminants. There is potential that these IX resins may be able to remove PFAS from groundwater, but investigation is needed to understand affinity/selectivity and removal capacity given the groundwater composition and the operating conditions. This report provides background on PFAS uses and chemistry, then provides a review of IX resin applications for PFAS, identifying knowledge gaps. Recommendations are provided regarding research needed to address knowledge gaps and acquire information needed to propose IX as a future PFAS remediation technology at the Hanford Site, as well as other U.S. Department of Energy sites. Generally, PFAS compounds are fluorinated substances that contain at least one fully fluorinated methyl or methylene carbon – with a few noted exceptions, any chemical with at least a perfluorinated methyl group (–CF3) or a perfluorinated methylene group (–CF2–) is a PFAS. These chemical compounds are characterized as non-biodegradable, non-reactive, non-photolytic, and hydrolysis resistant. This makes them highly recalcitrant within the environment, however polyfluoroalkyl materials are less recalcitrant as the carbon chains contain C–H bonds which are more easily broken than carbon – fluorine (C–F) bonds. The backbone carbon structures are commonly punctuated with a head group, the most well-known of them are perfluorooctanesulfonic acid and perfluorooctanoic acid, which possess a sulfonate and a carboxylate group, respectively. IX resins are marketed for the removal of PFAS from water systems and industrial water, however, the mechanism of removal is not as well understood as for anion or cation removal. A better understanding of the mechanism of removal would enable the development of IX resins that have improved specificity for PFAS removal. Four knowledge gaps were identified: 1) the effect of dissolved ions on the IX resin PFAS removal effectiveness, 2) the effect of additional primary contaminants of concern (PCOCs) or secondary contaminants of concern (SCOCs) on the effectiveness of PFAS via IX resin, 3) the mechanisms of PFAS removal from water, and 4) practical solutions to IX resin regeneration and waste disposal.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2023

Building Environmental Justice and Equity into the Development of Critical Mineral Industries

The global transition toward low-carbon energy not only means an increase in demand for clean electricity and renewable resources, but also an increase in demand for the critical minerals (CMs) and rare earth elements (REEs) that these technologies rely upon. Indeed, low-carbon energy technologies, such as those used for wind turbines and electric vehicle motors, require significantly more lithium, nickel, cobalt, manganese, graphite, and other CMs than fossil-based energy technologies. The growing demand for new forms of low- carbon energy will necessitate a proportional scale-up of CM and REE extraction and processing. Presently, the majority of extraction and processing activities for CMs and REEs are concentrated in very few countries, primarily in China and the Global South. CM and REE supply chain activities conducted in or controlled by these countries are commonly associated with widespread and well- documented human rights abuses and environmental degradation. As a result of concerns related to supply chain security, worker welfare, and the overall need for additional sources of CMs and REEs, governments worldwide have begun to explore policy pathways for the development of new supply chains. The development of new supply chains for CMs and REEs re s a multifold opportunity to accelerate the global deployment of low-carbon energy fleets, reduce global carbon emissions, build political resilience—and also to enhance policy objectives of environmental justice and equity in the clean energy transition. Fulfilling these policy objectives requires energy producers to navigate a maze of global supply chain policies designed to shape and accelerate the growth of new markets. In the United States, for instance, President Biden recently implemented fiscal and trade policies that incentivize both domestic and global reliance on U.S.-produced CMs and REEs, leveraging key relationships in Asia and Europe to ensure the accelerated buildout of the U.S. supply chain. The Biden Administration’s framework also emphasizes that new supply chains for CMs, REEs, and other low-carbon energy pathways must generate benefits for marginalized and disadvantaged communities, build energy equity, and contribute to the Biden Administration’s vision of environmental justice. present CM and REE supply chains include several stages, including mining, processing, transport, utilization, and disposal, each of which involves different environmental justice considerations and potential injustices. This study explores how technical innovation, paired with responsible community engagement and empowerment, can help inform the development of energy equity and environmental justice at all stages of new supply chains. The study highlights these opportunities on a broad scale. We also lend a specific focus to research at the University of Wyoming School of Energy Resources that aims to guide the development of CM and REE industries in communities with high economic dependence on coal and other fossil fuel industries, identifying pathways to grow a U.S. domestic supply chain by producing CMs from coal, coal by-products, and coal waste streams. These production pathways represent a potential new supply for CMs across the U.S. and elsewhere, thereby enhancing national security and accelerating the widespread deployment of low-carbon energy technologies, while also generating alternative applications for remaining coal reserves and aiding in a just transition for rural energy-producing communities.

Gerace, Selena↗
DOE OSTI2020

Influences of Mg Ions and Al Ions on Deposition Behavior of Supersaturated Silicic Acid - 20261

Silicic acid can change into various species such as deposit, colloidal, and soluble form under certain conditions: for example, gradual pH changes around geological disposal repositories. In particular, silicic acid deposits narrow groundwater flow paths, thereby restricting the flow of groundwater. Such effects may contribute to a delay in radionuclide migration. Previous studies have reported that silicic acid supersaturated in sodium and calcium ions can narrow the flow paths. This study examined the effect of magnesium (Mg) and aluminum (Al) ions on the deposition of supersaturated silicic acid on the solid phase. The deposition behavior of supersaturated silicic acid on the solid phase was investigated in a batch system while changing the initial supersaturation concentration, the coexisting ion concentration, and the amount of added solid phase. In the presence of Mg ions, silicic acid precipitation increased with increasing Mg ion concentration due to the influence of the electrolyte, and crosslinking reactions. The coexistence of Al ions significantly suppressed silicic acid deposition due to the formation of a covering on the solid surface during Al ion hydrolysis under conditions of high Al concentration (1.4 mM). On the basis of these experimental results, the apparent deposition rate constant of silicic acid was estimated to be in the range from 10{sup -11} to 10{sup -10} m/s. The Damkoehler number (the dimensionless number expressed by the ratio of the characteristic time of mass transfer and the chemical reaction constant) was sufficient to cause the clogging of the host rock by deposition. This suggests that supersaturated silicic acid deposition, regardless of the presence of Mg ions (and Al ions), contributes to improving barrier performance against radionuclide migration in the host rock. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2022

Development of electrostatic precipitator (ESP) technology to remove elemental mercury vapor, HG(0)

The presence of mercury vapor or other forms of mercury presents issues with worker safety, decommissioning facilities, and environmental impacts. As such, it is desired to develop a strategy to either remove or reduce mercury levels in Oak Ridge’s Y-12 Complex facilities. A testing methodology was developed to evaluate electrostatic precipitator technology for removal of mercury vapor. This methodology involved supplying mercury vapor-containing air to the ESP device by flowing air through a column containing alternating layers of sand and liquid mercury droplets. Initial attempts at quantifying the efficacy of the ESP device in removing mercury vapor were plagued with difficulties in controlling the flow of mercury into the ESP device due to poor performance of the generator column and the contamination of these experiments with mercury from an unknown source. These issues were resolved by creating a new generator column with slower air velocity and higher surface area of liquid mercury, along with moving the air intake for the ESP device to outside of the chemical hood in which testing took place. This resulted in a steady, quantified flow of mercury vapor from the generator column and no observation of unintended mercury sources. A final test of the ESP device under these controlled conditions showed that for a certain amount of time (on the order of 20-30 minutes) mercury concentrations were reduced by approximately 33 - 67% of the inlet concentration. However, episodic releases or pulses of mercury observed only at the outlet indicated that the mercury accumulated in the ESP device is periodically expelled. As a result, it was not deemed to be an efficient strategy for the removal of elemental mercury vapor.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2020

Combined Effort to De-Inventory the New Brunswick Laboratory of Plutonium Certified Reference Materials - 20504

To de-inventory plutonium Certified Reference Materials standards (CRMs) from the New Brunswick National Laboratory (NBL), the Argonne National Laboratory (ANL) and Savannah River National Laboratory (SRNL) formed a unique team. This teaming arrangement leveraged the different capabilities and expertise of both laboratories, helping to ensure the effort would be performed both safely and cost-effectively. With the NBL then physically housed on the ANL site, ANL served as the host-site, providing the necessary facilities and support services (e.g., supplying everything from hoods, loading equipment, and scales to Health Physics supports). From a packaging perspective, ANL's responsibilities focused mainly on characterizing and preparing the contents for shipment, followed by performing the Shipper of Record activities. With SRNL being the Package Design Authority of the 9978, the Type B packaging used for this effort, SRNL's scope included developing a Safety Analysis Report in Packaging (SARP) Letter Amendment to add the CRMs as authorized contents to the 9978. Recognizing competency, ANL prodigiously tasked SRNL to perform the actual loading of the CRMs into the 9978s, while physically on the ANL site. This paper details five different aspects of this effort. They are: 1. Characterization/validation of the CRM contents. 2. Development of the 9978 SARP Letter Amendment for the content change. 3. Development of the nitrogen inerting method to address SARP identified potential flammability concerns. 4. Renewal of the SRNL 9978 loading procedure. 5. Performance of the actual work execution activities. In 2017, the first nine packages were successfully loaded and shipped from NBL, while in 2019, the last ten were successfully loaded and planned for shipment. Without ANL leveraging SRNL's strengths, the de-inventorying of NBL of its plutonium CRMs would have likely taken many years longer. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2020

Life-Cycle Baseline Customization for the Formerly Utilized Sites Remedial Action Program - 20304

One of the responsibilities of the federal government is to estimate sound and defensible life-cycle baseline costs for use in federal budget estimates and to meet federal financial reporting requirements. To accomplish this, the US Department of Energy (DOE) Office of Legacy Management (LM) and the US Army Corps of Engineers (USACE) have partnered together to ensure that the liabilities documented in each Formerly Utilized Sites Remedial Action Program (FUSRAP) site's life-cycle baseline are specifically tailored. FUSRAP was created in the mid-1970's to clean up radiological contamination resulting from the early development of nuclear weapons. DOE was responsible for FUSRAP until October 1997, when Congress transferred the administration and execution of FUSRAP site cleanups to USACE. By 1997, DOE had completed the cleanup of 25 of the 46 sites that were active within the program and had begun cleanup at 13 additional sites. USACE was assigned responsibility for the cleanup of the 21 remaining FUSRAP sites, and at 8 additional sites that had since been referred for cleanup. The LM mission for the FUSRAP sites is to perform long-term surveillance and maintenance (LTS and M). Currently, LM provides long-term stewardship for 34 completed FUSRAP sites. Another 20 sites are under active remediation by USACE. Within the last 5 years, USACE has completed the cleanup at five FUSRAP sites and the LTS and M responsibility has been transferred to LM. By 2029, USACE will compete remediation at eight additional sites and LTS and M for those sites will transfer to LM. Because responsibilities for the FUSRAP sites transfer between USACE and LM upon completion of remedial actions, both agencies maintain life-cycle baselines for different stages of the project and both must have a strong understanding of the needs and requirements for each site. This understanding ensures that the life-cycle baselines form a complete and accurate picture of what is required for the site and for the FUSRAP program. LM focuses on several things when customizing the life-cycle baseline estimates for the FUSRAP sites, including (1) Understanding the unique requirements for each site. By reviewing site-specific documents prepared by USACE, such as Feasibility Studies and Records of Decision, and partnering with USACE to gain additional insight about site conditions and requirements for stewardship, as well as potential risks, LM can better develop the life-cycle baselines. (2) Developing site-specific labor breakdowns. This ensures the required labor mix is baselined for specific activities by comparing the labor mix required to perform activities at (a) other LM-managed FUSRAP sites and (b) non-FUSRAP LM sites and (c) by USACE at active FUSRAP sites. (3) Taking a tiered approach to life-cycle baseline planning. Estimates for sites transferring to LM in the near term (5 years) are more definitive than for sites transferring in the out-year period. Remedial actions at the near-term sites are at or near completion, providing LM a strong understanding of the LTS and M requirements and remaining liabilities. This in turn allows for site-specific customization of the baseline. (4) Using a robust risk management approach to ensure that liabilities specific to each site are identified, evaluated by probability and severity, and documented in relation to the impact to cost or schedule. To ensure the most accuracy within all the baselines, the FUSRAP life-cycle baselines are updated as needed to support program, project, and contract management needs. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2025

Crystallographic Snapshots of Pre- and Post-Lanthanide Halide Hydrolysis─Reaction Products Captured by the 4-Amino-1,2,4-triazole Ligand

Reactions of lanthanide(III) chloride salts with 4-amino-1,2,4-triazole (4-NH 2 -1,2,4-Triaz) in azole melts have led to the isolation of both hydrolysis and non-hydrolysis products in the same synthesis with the inclusion of a variety of ligands, anions, and water, allowing us to capture crystallographic snapshots of different forms and intermediate hydrolysis fragments. The structural studies reported here include anhydrous and hydrated nonhydrolyzed complexes which were isolated alongside hydrolysis products giving oxide/hydroxide lanthanide(III) dimers, tetramers, and ultimately hexamers. The compounds isolated include [Nd 2 Cl 6 (μ 2 -4-NH 2 -1,2,4-Triaz) 4 (4-NH 2 -1,2,4-Triaz) 2 ], [Ce 2 Cl 4 (μ 2 -Cl) 2 (μ 2 -4-NH 2 -1,2,4-Triaz) 4 ] n , [Ce 2 (µ 2 -Cl) 4 (µ 2 -OH) 2 (µ 2 -4-NH 2 -1,2,4-Triaz) 2 ] n , [Ln 4 Cl 4 (µ 2 -Cl) 4 (µ 3 -OH) 4 (µ 2 -4-NH 2 -1,2,4-Triaz) 4 ] n •2nH 2 O (Ln = Ce, Nd), and [Ce 6 Cl 6 (µ 6 -O 0.5 )(µ 3 -Cl 0.5 ) 4 (µ 3 -Cl 0.75 ) 3 (µ 3 -OH) 0.75 (µ 2 -4-NH 2 -1,2,4-Triaz) 12 ((OH 2 ) 0.25 ) 2 ] 2 [CeCl 6 ][Cl 9 ]•xH 2 O. In all complexes all lanthanide atoms are pairwise connected via one or more 4-NH2-1,2,4-Triaz ligands and sometimes additional Cl - anions.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2020

Synthesis and Characterization of Pd-based Nanomaterials

Bimetallic nanoparticles (BNPs) consist of two different types of metals or alloys that are bonded together. Unique properties such as optical, electronic, thermal, and catalytic effects differ for each type of BNP. Important BNPs range from Au-Pd, Ag- Pt, Au-Pt, and Ag-Ni. Pd bimetallic nanoparticles are of interest due to their many applications such as catalysis and sensing. Bimetallic catalysts have increase reaction rates and have improved catalyst stability through the geometry and ligand distribution. Pd nanoparticles are considered to be a strong catalyst due to their high activity at low temperatures and high tolerance to moisture. The catalytic properties of bimetallic nanoparticles depend on the structural properties such as size and shape. Core-shell, hollow structure, and multi-shell alloy are three possible structures nanoparticles can form as bimetallic catalysts. BNPs can be synthesized through different methods to control the size, shape, and structure. To obtain different morphologies, a variety of methods can be performed. Different methods can range from the usage of the glancing angle deposition (GLAD) to the galvanic replacement reaction, but the methods all depend on the properties of the metals. The galvanic displacement reaction was the method used to obtain Pd-based nanoparticles. This reaction is best know for obtaining hollow shaped NPs. To determine what redox process was preformed, the activity series of metals was used. From the activity series of metals, silver (Ag) was selected to preform Pd-based nanoparticles. Objectives: Synthesize Ag nanoparticles and Ag-Pd nanoparticles to understand the morphology. Characterize the synthesized nanoparticles using scanning electron microscopy (SEM), phase analysis light scattering (PALS), dynamic light scattering (DLS), energy dispersive X-ray spectroscopy (EDS), and UV-Vis spectroscopy. Results: In the UV-Vis spectrum, the Ag-Pd bimetallic NP's plasmon band decreased as the volume of palladium increased. The surface charge increases as the concentration of palladium increases. The Pd{sup 2+} ions interact with the sodium citrate surface, and decrease the negative charge. Conclusion: Ag-Pd nanoparticles were successfully created and stabilized with sodium citrate. The addition of Pd decreased the prominent plasmon band of the Ag nanoparticles. The SEM analysis showed that Ag nanoparticles had a well-defined structure, while the Ag-Pd nanoparticles showed hollow and rough structure. The EDX analysis confirmed the presence of silver and palladium. This material can be used in many industrial and research fields such as organic synthesis, fuel cells, and environmental sensing and remediation.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2025

Characterization of Tank 9H Annulus Sample in Support of Residual Material Inventory Determinations

The Savannah River National Laboratory (SRNL) was requested by Savannah River Mission Completion (SRMC) to provide sample preparation and characterization of the Tank 9H annulus sample in support of Residual Material Inventory Determinations. One Tank 9H sample in three vials [HTF-9-25-13, HTF-9-25-14 and HTF-9-25-15], with each vial containing approximately 200 mL of the Tank 9H annulus salt solution, were delivered to the SRNL Shielded Cells for sample preparation and characterizations in February 2025. The density of the “as-received” solution contained in each of the three Tank 9H annulus sample vials were determined followed by a solid-liquid separation on each one using 0.45-micron Nalgene® nylon filter membranes. The resulting filtrates were combined to form the Tank 9H annulus sample with a total volume of about 600 mL. The combined wet solid fractions, about a total of 4.8 grams of salt material, remaining on the filter membranes were air-dried in the Shielded Cells for 72 hours. The total weight of the air-dried solids was 2.1 grams. These air-dried solids were washed with deionized water (DI water) at a phase ratio of 60 mL DI water/gram of solids to recover insoluble solids, if any. No visible or measurable quantity of insoluble solids were recovered after DI water washing of the air-dried solids because the air-dried solids completely dissolved in the DI water. The solid fraction-wash water was not combined with the 600 mL of the filtrate solution, and the resulting solution was not screened or analyzed for radionuclides. Aliquot sample volumes of the undiluted Tank 9H annulus sample were sent to the SRNL analytical services groups for radionuclides, elementals, anions and total mercury analysis by various methods including radiochemical separations/counting methods, inductively coupled plasma-atomic emission spectroscopy (ICP-AES), and Inductively Coupled Plasma Mass Spectroscopy (ICP-MS) and special preparations. All sample analyses were performed in triplicate. This report presents the analytical characterization results for the Tank 9H annulus sample. The results are also reported where analytical methods yielded additional analytes, other than those requested by SRMC. In the characterization of the Tank 9H annulus sample, the detection limits for all the analytes, as specified in the Technical Task Request (TTR) and Task Technical and Quality Assurance Plan (TTQAP), were met.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2026

Characterization and effects of impurities on carbonate quantification in heterogenous matrices

Mineral carbonation simulates a natural weathering phenomena by breaking down silicates and oxides to form Ca & Mg carbonates. Various mineralization methods have been demonstrated as a potential technique to improve the quality of slags and tailings through neutralization and stabilization of problematic species to yield a product better suited for use in concrete. This study aims to characterize, quantify and analyze carbonates in various carbonated products such as mineralized CaCO 3 , CO 2 mineralized Steel Slags and Mine Tailings. More than 10 samples were analyzed for carbonate measurement and verification from industrial and academic partners that pioneer commercial CO 2 mineralization technologies. The samples were characterized primarily by using X-ray diffraction (XRD), Thermogravimetric Analyses (TGA), and Scanning Electron Microscopy (SEM) to gain insights into CaCO 3 content. A baseline characterization of lab-grade CaCO 3 and MgCO 3 also revealed important considerations for CaCO 3 measurement using TGA alone. The experiments using synthetic lab-grade samples also revealed that the presence of MgCO 3 /MgO can accelerate the decomposition of CaCO 3 and thus can affect measurement parameters. Lab-grade CaCO 3 samples dosed into steel slag and mine tailing also showed significant deviation in their decomposition behavior. These insights are used to inform the development of a standardized protocol for the measurement and verification of carbonate-bearing products.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2020

235-F GoldSim Fate and Transport Model: Uncertainty Quantification

Building 235-F was configured with two missions in mind: Actinide Billet Line (ABL) and the fabrication of Pu-238 oxide for space program applications. ABL produced Np-237 billets for use in SRS reactors, whereas the design process, fabrication, and examination of Pu-238 oxide powder occurred within the following areas, respectively: Plutonium Experimental Facility (PEF), Plutonium Fuel Form (PuFF), and Old Metallography Lab (OML). By 1990 production ceased and by 2006 de-inventory occurred; however, assays have shown significant holdup remains within ABL and PuFF. As a result, 235-F is a Category 2 nuclear facility, with plans to undergo deactivation and decommission (D and D) via In-Situ Disposal (ISD). The purpose of this project is to ensure United States Environmental Protection Agency (USEPA) groundwater radiation maximum contaminant level (MCL) and dosage standards are met during the D and D of 235-F by quantifying uncertainty through probabilistic modeling and evaluation of various ISD alternatives. GoldSim is a dynamic modeling software package with a graphical, object-oriented interface capable of capturing the influence of complex system input variability on probabilistic system outcomes. A GoldSim stochastic fate and transport model for 235-F was developed and matched with a PORFLOW deterministic model to simulate probabilistic release and flow of radionuclides from ABL and PuFF into the vadose zone, the Upper Three Runs (UTR) Aquifer, and UTR Creek. The GoldSim model was used to probabilistically evaluate four ISD scenarios against USEPA groundwater radiation MCLs and dosage standards. The deterministic 235-F GoldSim fate and transport model continues to be refined to match the results of the PORFLOW deterministic model to ensure the model accurately represents radionuclide movement through the groundwater system. The stochastic variables that are utilized within the GoldSim model are founded on the most current data; a conservative perspective is taken where needed. Alignment with the PORFLOW deterministic model, coupled with input stochastic variability, allows the probabilistic 235-F GoldSim model to capture the conservative breadth of possible outcomes for radionuclide fate within this particular system. This ensures that the USEPA MCLs and dosage limits hold even in the worst case scenarios.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2026

Hybrid-Energy-Powered Electrochemical Ocean Alkalinity Enhancement Model: Plant Operation, Cost, and Profitability

Electrochemical ocean alkalinity enhancement is a form of marine carbon dioxide removal, a rapidly growing industry that is powered by efficient onshore or offshore energy sources. As more and larger deployments are being planned, it is important to consider how variable energy sources like tidal energy can impact plant performance and costs. An open-source Python-based generalizable model for electrodialysis-based ocean alkalinity enhancement has been developed that can capture key system-level insights of the electrochemistry, ocean chemistry, acid disposal, and co-product creation of these plants under various conditions. The model additionally accounts for hybrid energy system performance profiles and costs via the National Laboratory of the Rockies’ H2Integrate tool. The model was used to analyze an example theoretical plant deployment in North Admiralty Inlet, including how the plant is impacted by the available energy sources in the region and the scale at which plant costs are covered by the co-products it generates, such as recycled concrete aggregates, without requiring carbon credits. The results show that the example plant could be profitable without carbon credits at commercial scales of 100,000 to 1 million tons of carbon dioxide removal per year, so long as it uses low-cost electricity sources and either sells acid or recovers recycled concrete aggregates with about 1 molar acid concentrations, though more research is needed to confirm these results.

hybrid energy↗