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At least 343 records · Page 19

Sensor Development for Liquid Water Detection in Dry Storage Casks: FY 2023 Status

Modeling efforts were undertaken in fiscal year (FY) 2023 to evaluate the feasibility and capability for sensing of liquid water inside canister-based dry cask storage systems (DCSSs). The focus was on the development of full-scale finite element models (FEMs) of ultrasound propagation through DCSS canister components. For these initial investigations, simulation of the baseplate component was targeted, envisioning water collection at the bottom of a vertically oriented canister. The effects of internal canister components (i.e., fuel basket, fuel assemblies) on ultrasound propagation in the baseplate component were evaluated in these efforts. The environment inside a DCSS confinement is intended to be inert and free of water to prevent potential corrosion of used fuel cladding or other internal hardware. Spent fuel assemblies are dried, after storage in water pools, to make sure water has been removed from assembly cavities. However, there is some uncertainty about the amount of residual water potentially left behind in a DCSS after drying processes, because water can become trapped in cavities or other small crevices in the surfaces formed by the fuel cladding, fuel assemblies, and other internal hardware components. Considering the complex space- and time-dependent temperature profiles in DCSSs, water may be in a liquid or gas phase depending on its location in the cask and how long the cask has been in storage. Evacuating most water and oxidizing agents contained within a canister is recommended by NUREG-1536 (NRC 2010), which covers DCSSs. As summarized by Salazar et al. (2020), existing guidance typically relies on achievable vacuum pumping pressures sustained over a hold period as a signal of dryness and water removal. However, time series data about water removal from full-scale commercial drying procedures are lacking (Hanson and Alsaed 2019). A review of drying specifications from several vendors led to the conclusion that if the specifications are followed correctly, the residual moisture in DCSSs should present an insignificant risk of cladding degradation (Knoll and Gilbert 1987). A more recent analysis concluded that much larger quantities of residual water could remain in DCSSs, but the amount would still not be expected to lead to significant corrosion of fuel cladding or other internal components (Jung et al. 2013). Industry drying procedures are mostly prescriptive in nature, and operational issues arising during the process could result in incomplete drying. A summary of operational issues and potential negative effects of residual water is provided by Salazar et al. (2019). Experimental efforts are ongoing to validate the extent of water removal in a DCSS based on drying procedures used at nuclear power plants through well-designed investigations of drying process efficacy and water retention (Durbin et al. 2021; Pulido et al. 2022a, Pulido et al. 2022b). This has been approached by simulating limited portions of a DCSS internal volume and fuel assemblies. So far, these efforts have focused on the effects of potential water trapping in the dashpot region of control rod guide tubes but are expected to be expanded to include the effects of other internal hardware features and failed fuel rod cladding. A method for detection and measurement of liquid water (Meyer et al. 2022; Meyer et al. 2021), in tandem with the drying information gained through experimental investigations, provides comprehensive bases for understanding the internal conditions of DCSSs and provides technical information to support licensing decisions.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Optimization of Conditions for Photoluminescence-Based Sensing of Critical Minerals: Strategies and Outlook

Economically critical minerals and metals are vital to America’s security, with application areas in energy, advanced technologies, and defense systems. The growing implementation of renewable energy sources such as electric vehicles is expected to significantly increase demand for these minerals, while the global supply is monopolistic, with most of the production occurring in a few countries outside of the US. To mitigate potential supply chain vulnerabilities, the domestic production of economically critical metals has become a bipartisan priority of the US government, and unconventional sources such as coal and its utilization byproducts such as fly ash and acid mine drainage are being actively explored as an alternative method for meeting domestic demand. Slow and expensive characterization methods for critical metals present a significant pain point for domestic production, which has led to the exploration of alternative low-cost, portable platforms capable of detecting target metals during resource prospecting and downstream process monitoring. The National Energy Technology Laboratory has developed a portable fiber optic-based luminescence spectrometer that utilizes a metal-organic framework (MOF) material to detect and distinguish parts-per-billion levels of the visible-emitting rare earth elements terbium, dysprosium, samarium, and europium, which are all economically critical metals. Although preliminary results with this system are promising, a crucial barrier to practical deployment is the ability to operate in low pH, high ionic strength environments, as acidic conditions and the presence of other metal ions can significantly reduce luminescence signal. Here, current strategies related to sample treatment, material design, and sensor configuration are discussed in the context of improving sensor performance in application-relevant conditions. Additionally, future opportunities, such as the optimization of the sensing binding environment through computational methods and specific metals to be removed for treatment will be discussed, presenting a forward-looking view for innovation in luminescent sensing of critical metals.

36 MATERIALS SCIENCE↗

Metallic Coating of Cerium Oxide Microspheres

The ability to remove heat is paramount to nuclear fuel performance and longevity. Retaining fission product and separating fuel from reactor coolant and the environment is also necessary to prevent radiological contamination. Conventional nuclear fuel for commercial light water reactors and radioisotope power systems (RPS) is composed of oxide powders pressed into a pellet (cm-scale) and then sealed into a metal cladding to confine the fuel. What typical fuels lack is a method to surround each particle of nuclear fuel in metal, thus providing a more intimate protection layer for accident tolerance and boosting the thermal extraction from the fuel element. In such a way, metal-coated fuel particles increase heat extraction efficiency over clad-pellet designs while increasing the accident tolerance of the fuel. Metal oxide microspheres have wide-ranging applications, including the realm of fuels for nuclear reactors and RPS. Microspheres of uranium oxide/uranium carbide, mixed uranium/plutonium oxides, transuranics, and thorium fuels have been extensively studied. Pacific Northwest National Laboratory has also demonstrated the production of 238 PuO 2 microspheres for RPS applications. Metal-coated oxide microsphere fuels may also be attractive for other applications such as nuclear thermal rockets, future nuclear reactor designs, and catalysts.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Beyond Ammonia: Nitrogen–Element Bond Forming Reactions with Coordinated Dinitrogen

The functionalization of coordinated dinitrogen to form nitrogen-element bonds en route to nitrogen-containing molecules is a long-standing challenge in chemical synthesis. The strong triple bond and the non-polarity of the N 2 molecule pose thermodynamic and kinetic challenges for promoting reactivity. Although heterogeneous, homogeneous and biological catalysts are all known for catalytic nitrogen fixation to ammonia, the catalytic synthesis of more complicated nitrogen-containing organic molecules has far less precedent. Examples of silyl radical additions to coordinated nitrogen to form silylamines stands as the lone example of a catalytic reaction involving N 2 to form a product other than ammonia. Our review surveys the field of molecular transition metal complexes, as well as recent boron examples for the formation of nitrogen-element bonds. Emphasis is placed on the coordination and activation modes of N 2 in the various metal compounds from across the transition series and how these structures can rationally inform reactivity studies. Over the past few decades, the field has evolved from the addition of carbon electrophiles in a manner similar to protonation reactions to more organometallic-inspired reactivity including insertions, 1,2-additions and cycloadditions. Various N–C, N–Si and N–B bond-forming reactions have been discovered highlighting that the challenge for catalytic chemistry is not in the reactivity of coordinated dinitrogen but rather removal of the functionalized ligand from the coordination sphere of the metal.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Validation and Parametric Investigations Using a Lumped Thermal Parameter Model of an Internal Permanent Magnet Motor

One of the key challenges for the electric vehicle industry is to develop high-power-density electric motors. Achieving higher power density requires efficient heat removal from inside the motor. In order to improve thermal management, a multi-physics modeling framework that is able to accurately predict the behavior of the motor, while being computationally efficient, is essential. This paper first presents a detailed validation of a Lumped Parameter Thermal Network (LPTN) model of an Internal Permanent Magnet (IPM) synchronous motor within the commercially available Motor-CAD® modeling environment. The IPM motor’s stator is studied at steady state, and winding losses are generated by a constant DC current. The validation is based on temperature comparison with experimental data and with more detailed Finite Element Analysis (FEA). All critical input parameters of the LPTN are considered in detail for each layer of the stator, especially the contact resistances between the impregnation, liner, laminations and housing. Finally, a sensitivity analysis for each of the critical input parameters is provided. A maximum difference of 4% — for the highest temperature in the slot windings and the end windings — was found between the LPTN and the experimental data. Comparing the results from the LPTN and the FEA model, the maximum difference was 2% for the highest temperature in the slot windings and end windings. As for the LTPN sensitivity analysis, the thermal parameter with the highest sensitivity was found to be the liner-to-lamination contact resistance. The latter is often ignored in the literature, whereas its impact on temperature rise was found to be more significant than any other contact resistance within the stator.

47 OTHER INSTRUMENTATION↗

2023 Annual Report of Available Drawdowns for Each Oil Storage Cavern in the Strategic Petroleum Reserve

DOE maintains an up-to-date documentation of the number of available full drawdowns of each of the caverns at the U.S. Strategic Petroleum Reserve (SPR). This information is important for assessing the SPR’s ability to deliver oil to domestic oil companies expeditiously if national or world events dictate a rapid sale and deployment of the oil reserves. Sandia was directed to develop and implement a process to continuously assess and report the evolution of drawdown capacity, the subject of this report. This report covers impacts on drawdown availability due to SPR operations during Calendar Year 2022. A cavern has an available drawdown if, after that drawdown, the long-term stability of the cavern, the cavern field, or the oil quality are not compromised. Thus, determining the number of available drawdowns requires the consideration of several factors regarding cavern and wellbore integrity and stability, including stress states caused by cavern geometry and operations, salt damage caused by dilatant and tensile stresses, the effect of enhanced creep on wellbore integrity, and the sympathetic stress effect of operations on neighboring caverns. Finite-element geomechanical models have been used to determine the stress states in the pillars following successive drawdowns. By computing the tensile and dilatant stresses in the salt, areas of potential structural instability can be identified that may represent red flags for additional drawdowns. These analyses have found that many caverns will maintain structural integrity even when grown via drawdowns to dimensions resulting in a pillar-to-diameter ratio of less than 1.0. The analyses have also confirmed that certain caverns should only be completely drawn down one time. As the SPR caverns are utilized and partial drawdowns are performed to remove oil from the caverns (e.g., for oil sales, purchases, or exchanges authorized by the Congress or the President), the changes to the cavern caused by these procedures must be tracked and accounted for so that an ongoing assessment of the cavern’s drawdown capacity may be continued. A methodology for assessing and tracking the available drawdowns for each cavern is reiterated. This report is the latest in a series of annual reports, and it includes the baseline available drawdowns for each cavern, and the most recent assessment of the evolution of drawdown expenditures. A total of 222 million barrels of oil were released in calendar-year 2022. A nearly-equal amount of raw water was injected, resulting in an estimated 34 million barrels of cavern leaching. Twenty caverns have now expended a full drawdown. Cavern BC 18 has expended all its baseline available drawdowns, and has no drawdowns remaining. Cavern BM 103 has expended one of its two baseline drawdowns, and is now a single-drawdown cavern. All other caverns with an expenditure went from at-least-5 to at-least-4 remaining drawdowns.

02 PETROLEUM↗

Validation and Parametric Investigations Using a Lumped Thermal Parameter Model of an Internal Permanent Magnet Motor: Preprint

One of the key challenges for the electric vehicle industry is to develop high-power-density electric motors. Achieving higher power density requires efficient heat removal from inside the motor. In order to improve thermal management, a multi-physics modeling framework that is able to accurately predict the behavior of the motor, while being computationally efficient, is essential. This paper first presents a detailed validation of a Lumped Parameter Thermal Network (LPTN) model of an Internal Permanent Magnet (IPM) synchronous motor within the commercially available Motor-CAD® modeling environment. The IPM motor’s stator is studied at steady state, and winding losses are generated by a constant DC current. The validation is based on temperature comparison with experimental data and with more detailed Finite Element Analysis (FEA). All critical input parameters of the LPTN are considered in detail for each layer of the stator, especially the contact resistances between the impregnation, liner, laminations and housing. Finally, a sensitivity analysis for each of the critical input parameters is provided. A maximum difference of 4% - for the highest temperature in the slot windings and the end windings - was found between the LPTN and the experimental data. Comparing the results from the LPTN and the FEA model, the maximum difference was 2% for the highest temperature in the slot windings and end windings. As for the LTPN sensitivity analysis, the thermal parameter with the highest sensitivity was found to be the liner-to-lamination contact resistance. The latter is often ignored in the literature, whereas its impact on temperature rise was found to be more significant than any other contact resistance within the stator.

ADVANCED PROPULSION SYSTEMS↗

Area 6 Control Point: An Architectural Survey of the Area 6 Control Point, Nevada National Security Site, Nye County, Nevada

The U.S. Department of Energy (DOE), National Nuclear Security Administration Nevada Field Office (NNSA/NFO) proposes to demolish five buildings and five accessory resources in the Area 6 Control Point at the Nevada National Security Site (NNSS) in Nye County, Nevada. The demolition and removal of the buildings and accessories constitute an undertaking subject to review under Section 106 of the National Historic Preservation Act (NHPA) (54 United States Code [USC] § 306101) and its implementing regulations, 36 Code of Federal Regulations (CFR) Part 800. The buildings and accessories were recorded in Identification and Evaluation of 14 Architectural Resources Scheduled for Demolition, Area 6 Control Point and Vicinity, Nevada National Security Site, Nye County, Nevada (Menocal et al. 2020). The report found that the five buildings were not individually eligible for listing in the National Register of Historic Places (NRHP, National Register) but were potentially eligible as contributing elements to an unrecorded Area 6 Control Point district. The report also found that the five accessory resources were not individually eligible for the NRHP but they contributed to other historic properties, including the contributing elements to the unrecorded district. Finally, the report found that the undertaking would result in an adverse effect to historic properties. The State Historic Preservation Office (SHPO) concurred with the report’s findings regarding the eligibility of the buildings and structures in the Area of Potential Effect (APE) and that the undertaking would result in an adverse effect (Reed 2020). The NNSA/NFO, in consultation with the SHPO, then developed the Memorandum of Agreement DE-GM58-21NA25543 Between the U.S. Department of Energy and the Nevada State Historic Preservation Officer Regarding Demolition of Fourteen Buildings and Structures in Area 6 of the Nevada National Security Site, Nye County, hereafter referred to as the MOA. The MOA stipulates that a district boundary be delineated with an accompanying boundary report and supporting photographs (Stipulation III.A) followed by an architectural survey of the potential historic district (Stipulation III.B). The SHPO reviewed and concurred with the proposed district boundary and accompanying boundary report and photographs (O’Neill et al. 2021) on August 23, 2021, in fulfillment of Stipulation III.A (Reed 2021). This architectural survey report has been prepared in accordance with Stipulation III.B. It includes an NRHP evaluation of the district, identifies contributing and non-contributing elements, and is accompanied by Architectural Resource Assessment (ARA) forms. The NRHP evaluation concludes that the Area 6 Control Point is recommended eligible as a historic district under the Secretary of the Interior’s Significance Criterion A at the national level as the location of the command center and various support facilities directly related to timing and firing operations for nuclear testing on the NNSS from 1951 to 1992. It is also recommended eligible under Significance Criterion C for embodying the distinctive characteristics of a nuclear command center in the context of the Cold War and as a significant and distinguishable entity. There are a total of 29 primary resources within the district boundary. Of these, 28 are recommended as contributing elements to the Area 6 Control Point Historic District and one is recommended as non-contributing.

54 ENVIRONMENTAL SCIENCES↗

Probing f-orbital covalency through the fold angles of transuranium dithiolene complexes

The ability of the actinide elements to covalently bond to ligands is not well understood. A computational effort for compounds of the formula [Cp 2 AnS 2 C 2 H 2 ] -1,0,+1 where An = U, Np, or Pu has shown that the angle between the plane formed by the two sulfurs and the plane formed by the two sulfur atoms and the two carbons converges to 70 – 75° when the ligand is in the dithiolate state (-2 charge on the ligand). Upon oxidation of [Cp 2 NpS 2 C 2 H 2 ] 0 or [Cp 2 PuS 2 C 2 H 2 ] 0 the electron is removed from the dithiolate rather than the actinide and the dihedral angle is reduced to planarity. The reaction of NpCl 4 DME 2 with deprotonated benzene dithiol shows an intense color change suggestive of a charge transfer complex. The binding of the benzene dithiol as the dithiolate to the neptunium metal center is supported by visible, infrared and NMR spectroscopies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Sulfidation kinetics of titanium and Ti-6Al-4V with elemental sulfur

The sulfidation kinetics of titanium and Ti-6Al-4V (Ti64) using elemental sulfur were studied by measuring the amount of metal consumed instead of the change in mass or scale thickness. Here this metal consumption approach combines the parabolic oxidation law, Arrhenius equation, and Pilling-Bedworth ratio to determine the apparent activation energy and the pre-exponential factor of consumption of Ti64 during sulfidation. The estimations of apparent activation energy and pre-exponential factor were 110.4 kJ·mol -1 and 1.3×10 -9 m 2 s -1 for the titanium-sulfur, and 116.2 kJ·mol -1 and 1.2×10 -9 m2s -1 for the Ti64-sulfur system. Finally, a material removal predictor was developed to predict the amount of Ti64 consumed for a given sulfidation temperature and time.

36 MATERIALS SCIENCE↗

Hard disk drive dismantlement for critical material recovery

A system and method for recycling rare earth materials from dissimilar hard disk drives are provided. The system and method generally include scanning each hard disk drive, sorting and aligning each hard disk drive, rapid fastener removal or diversion to a metrology station, and the collection of separated value streams, optionally for formation into new magnetic stock. For each scanned hard disk drive having a match in an inventory database, the method includes the separation of an internal magnet from residual components. For each scanned hard disk drive lacking a match in the inventory database, the method includes generating a metrology data collection record containing the location of each fastener on multiple surfaces of the corresponding hard disk drive. The system and method are commercially scalable with the potential to generate between 600 and 700 metric tons of rare earth elements from a single processing facility annually, including neodymium for example.

McIntyre, Timothy J.↗

Beaver dams overshadow climate extremes in controlling riparian hydrology and water quality

Abstract Hydrologic extremes dominate chemical exports from riparian zones and dictate water quality in major river systems. Yet, changes in land use and ecosystem services alongside growing climate variability are altering hydrologic extremes and their coupled impacts on riverine water quality. In the western U.S., warming temperatures and intensified aridification are increasingly paired with the expanding range of the American beaver—and their dams, which transform hydrologic and biogeochemical cycles in riparian systems. Here, we show that beaver dams overshadow climatic hydrologic extremes in their effects on water residence time and oxygen and nitrogen fluxes in the riparian subsurface. In a mountainous watershed in Colorado, U.S.A., we find that the increase in riparian hydraulic gradients imposed by a beaver dam is 10.7–13.3 times greater than seasonal hydrologic extremes. The massive hydraulic gradient increases hyporheic nitrate removal by 44.2% relative to seasonal extremes alone. A drier, hotter climate in the western U.S. will further expand the range of beavers and magnify their impacts on watershed hydrology and biogeochemistry, illustrating that ecosystem feedbacks to climate change will alter water quality in river systems.

54 ENVIRONMENTAL SCIENCES↗

The compositional optimization and secondary phases evaluation regarding the creep resistance in Grade 91 steel through the CALPHAD approach

The critical secondary phases along with critical temperatures in regard to the creep resistance of Grade 91 steel alloy were evaluated in order to optimize the composition of the alloy to improve the creep resistance. The critical temperatures which are highlighted in this paper are Ac1 (the threshold temperature in which austinite begins to form), and Ac3 (the threshold temperature at which ferrite is fully transformed into austenite). Furthermore, optimization was presented through various Cr, V, Nb, and N concentrations in Gr.91 in relation to these critical temperatures and the mole fraction of M 23 C 6 , MX, and Z-Phase as critical secondary phases. Here, the results indicate that increasing V and Nb will increase MX stability, whereas decreasing Cr and N lead to a decrease in Z-Phase and M 23 C 6 stability, which may lead to an increased creep resistance of the material. Upon further analyzing the V, Nb, and N concentrations in Gr.91, results indicate that increasing Nb content in the steel can lead to an increased stability of Nb-rich MX2 carbide which can be used to replace Z-Phase in low N steels. Simulation results indicate that elimination of N with a dramatic increase in Nb concentrations result in the stability increase of only M 23 C 6 and MX2 phases at temperature regions between 600 °C and 1370 °C and a complete removal of Z-Phase precipitation. Overall, with the elimination of N, which destabilizes Z-Phase precipitation, and an increase in Nb for NbC carbide stability, a possible solution to increasing both long-term and short-term creep resistance for Gr.91 can be achieved, though further optimization and creep experiments need to be conducted for final conclusions.

36 MATERIALS SCIENCE↗

RUScal : Software for the analysis of resonant ultrasound spectroscopy measurements

Resonant ultrasound spectroscopy is used to nondestructively measure the elastic resonances of small solids to elucidate the material's elastic properties or other qualities like size, shape, or composition. In this work, we introduce the software RUScal for the purpose of determining elastic properties by analyzing the eigenfrequencies of solid specimens with common shapes, such as rectangular parallelepipeds, cylinders (solid and hollow tube), ellipsoids, and octahedrons, as well as irregularly shaped ellipsoids that can be described analytically. All symmetry classes are supported, from isotropic to triclinic, along with the option to add or remove up to three orthogonal mirror planes as well as the ability to reorient the crystal axes with respect the sample edges via Euler angles. Additional features include tools to help find initial sets of elastic constants, including grid exploration and Monte Carlo methods, a tool to analyze frequencies as a function of sample length or crystal orientation, an error analysis tool to assess fit quality, and formatting of the input and output files for batch fitting, e.g., as a function of temperature. This software was validated with published resonant ultrasound spectroscopy data for various materials, shapes, and symmetries with noted improvements in calculation time compared to finite element methods.

47 OTHER INSTRUMENTATION↗

Evaluation of preservation protocols for oxygen-sensitive minerals within laminated aquatic sediments

Laminated sediments can record seasonal changes in sedimentation of material from anoxic waters, including minerals of the redox-sensitive elements Fe, Mn, and S that form under varying oxygen levels, mineral saturation conditions, and from microbial metabolism. However, preserving the oxygen-sensitive minerals for identification is challenging when preservation of the spatial arrangement of laminae is also required. In this study, we compare methods for embedding sedimentary materials from anoxic waters and sediments from Brownie Lake, Minnesota, USA for analysis of the speciation for Fe, Mn, and S using synchrotron-based X-ray absorption near edge spectroscopy (XANES). We found that acetone dehydration and resin replacement in a 100% N 2 glovebox successfully preserved the speciation of Fe and Mn minerals within laminated sediments. However, acetone removed some sulfur species from sediments, and epoxies contained sulfur species, which challenged identification of native sulfur species. Results from this study will aid researchers who are interested in spatial analysis of oxygen sensitive sediments, soils, or microbial mats in choosing a preservation method.

58 GEOSCIENCES↗

Process design for recovering rare-earth elements from mine tailings with low rare-earth concentrations via sequential leaching and solvent extraction

Rare earth elements (REEs) are essential for advanced technologies and yet face significant supply chain risks due to their concentrated global production and limited domestic availability. Addressing this challenge requires efficient processes capable of upgrading low-grade secondary resources such as mine tailings. In this study, we developed a novel separation flowsheet that integrates sequential leaching and 2-stage solvent extraction (SX) processes to recover high-purity heavy REEs (HREEs) and light REEs (LREEs) from a simulated mine-tailing concentrate containing 2.4 wt% total REEs (TREEs; 0.6 wt% LREEs and 1.8 wt% HREEs). Sequential leaching with controlled pH adjustment selectively precipitated REEs while retaining the large amount of impurities in the solution, producing an REE-enriched leachate by following leaching processes with roughly twice the REE concentration and half the impurity concentration compared to that of single-step leaching. The optimized SX flowsheet employed Cyanex 572 to extract HREEs and Fe over LREEs, followed by Fe removal using tributyl phosphate (TBP), while the raffinate stream was processed by SX with di(2-ethylhexyl)phosphoric acid (D2EHPA) to recover LREEs under optimized conditions balancing both extraction efficiency and purity. Although increased extractant availability in the organic phase improved LREE recovery, it also increased co-extraction of Ca, underscoring trade-offs in process optimization. Both HREE- and LREE-rich solutions were subsequently precipitated into solid products via oxalate precipitation, resulting in high-purity REE solids containing ∼92.0 wt% HREEs (∼95.7 wt% TREEs) and ∼92.8 wt% LREEs (∼94.0 wt% TREEs). In conclusion, this proof-of-concept study using simulated mine tailings demonstrates a promising approach for upgrading low-grade REE resources, while highlighting the need for future validation with real materials.

Mine tailings↗

Disulfonamide Ligands as f-Element Extractants from Alkaline High-Level Waste

Almost 100 million gallons of high level waste (HLW) has been generated from defense reprocessing programs to support nuclear weapons production. HLW is currently stored at the Hanford and Savannah River Sites (SRS) [1]. It contains radioactive components, such as {sup 137}Cs, {sup 99}Tc and {sup 90}Sr, as well as large amounts of non-radioactive species, including solvated cations and insoluble metal hydroxides. HLW has high concentration of soluble hydroxides ([OH{sup -}] = 2 M at SRS [2]), complexing inorganic anions ([NO{sub 3}{sup -}] ∼ 0.65 - 3.7 M at SRS [2]) and a high ionic strength. Even though the majority of actinide component in alkaline HLW is precipitated, studies of An(III) and Ln(III) complexation in highly alkaline solutions in the presence of high nitrate concentrations have showed that soluble nitrate complexes can be formed [3]. The current treatment of HLW at SRS currently consists of two processes: The Actinide Removal Process (ARP) and the Next-Generation Caustic-Side Solvent Extraction process (NG-CSSX). Strontium and actinides are removed by sorption on monosodium titanate through the Actinide Removal Process (ARP) commonly referred to as the alpha-strike step [4]. Then, cesium is selectively extracted from the alkaline media via the Caustic-Side Solvent Extraction (CSSX) process [5]. The CSSX solvent consists of a calix[4]arene-crown-6 extractant dissolved in an inert hydrocarbon matrix containing i) a solvent modifier (alkylphenoxy alcohol) which increases extractant solubility and prevents third phase formation, and ii) a suppressor (trioctylamine or guanidine) - that mitigates surfactant effects. The CSSX process removes {sup 137}Cs selectively and rapidly, yet the post- CSSX aqueous stream may still contain high amounts of An, thus requiring a second ARP treatment (referred to as 'alpha-finishing') for some tanks. Despite the success of the ARP process in removing Sr and An, it often represents the kinetic bottleneck of integrated processing, as it is slower than solvent extraction. Understanding the complexation of actinides by organic ligands that are compatible with the CSSX process could eventually lead to a combined caustic-side Cs/Sr/actinide extraction process with better economics due to a reduced amount of monosodium titanate and/or a shorter required contact time with titanate during ARP. This would ensure a low-activity waste (LAW) stream with no actinides without additional ARP processing post-CSSX. Disulfonamides were studied for extraction of Sm(III) from alkaline aqueous media of pH 10-14 into dichloromethane. Up to 82% of Sm(III) was extracted from solutions of pH 12.5 -13.5 and up to 84% from solutions of pH 10.5 - 11.5. These results show some resemblance with Am extraction results by calixarene ligands previously reported [10]. Kinetic studies demonstrated that even 5 min is enough to complete stripping, whereas extraction is time-limiting process and requires up to 20 h for efficient removal of Sm(III) from alkaline aqueous media. Determination of composition of complexes in solution after extraction by the equilibrium shift method showed a 1:1 Sm(III):dsa-2 complexation ratio for the extracted species.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗