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At least 433 records · Page 24

Monte Carlo simulation analysis for radiation damage on Glidcop Al-15 caused by 17-20 MeV/u heavy ions

The Facility for Rare Isotope Beams (FRIB) SRF linear heavy-ion accelerator is designed to accelerate all ions up to uranium to a maximum beam power of 400 kW. Several beam intercepting devices (BIDs) are essential to the successful operation of the accelerator, including a low power charge selector (LPCS) made of copper containing 0.15% precipitated aluminum oxide by weight called Glidcop Al-15. As FRIB ramps up the primary beam power beyond the current 20 kW level, the charge selector must withstand higher radiation damage rates, typically measured in displacements per atom (dpa). Significant beam induced radiation damage including significant deformation, like swelling, blistering, and cracking has been observed on a recently removed LPCS. We also observed physical features up to about 5.5 mm wide and appear to be deeper than the projected range of any ions. This paper presents the results of Monte Carlo simulations carried out using the Particle and Heavy Ion Transport code System (PHITS), quantifying the total damage dose and ion concentration, etc. Simulating an accurate irradiation history is essential to determining the scope of post irradiation examination (PIE) work.

Fletcher, Ethan [Michigan State U.]↗

Editorial for Special Issue “Environmentally Sound In Situ Recovery Mining of Uranium”

This Special Issue features seven articles that cover a range of topics pertaining to the environmentally sound in situ recovery mining of uranium (U ISR). The topics include: (1) methods for assessing the potential environmental impacts of future U ISR operations using historical operational records and available geohydrologic, geochemical and climate data in a specific regional setting; (2) laboratory column studies to parameterize a uranium surface complexation model that can be used to predict uranium fate and transport in groundwater; and (3) a field evaluation of both a chemical reductant and a biostimulant to promote reducing geochemical conditions after oxidative mining at a U ISR facility.

54 ENVIRONMENTAL SCIENCES↗

Plutonium Oxidation State Distribution under WIPP Relevant Conditions (Rev. 2)

The oxidation state of plutonium in the Waste Isolation Pilot Plant (WIPP) environment has been a topic of interest since the initial compliance certification application. Plutonium (Pu) was initially expected to be present primarily as Pu(IV), but since the presence of Pu(III) could not be ruled out, it was also included in performance assessment (PA) calculations. The redox of the other variant actinides, uranium (U) and neptunium (Np), are also coupled to the plutonium redox. This led to a position in performance assessment calculations that is commonly referred to as “50/50”. In which half of the PA realizations assume solubility is dominated by the low oxidation state [U(IV), Np(IV), Pu(III)] and the other half assume solubility is dominated by the higher oxidation state [U(VI), Np(V), Pu(IV)]. Recently, a joint group of WIPP project participants from Los Alamos National Laboratory (LANL), Sandia National Laboratories (SNL), and the Department of Energy’s Carlsbad Field Office (DOE-CBFO) agreed on a new path forward for the oxidation state model in PA which will decouple the redox active actinides and will instead consider their redox as a function of E h . This will take the current binary approach and turn it into a system with four possible redox states.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Effect of chemical environment on the radiation chemistry of N , N -di-(2-ethylhexyl)butyramide (DEHBA) and plutonium retention

N,N-di-(2-ethylhexyl)butyramide (DEHBA) has been proposed as part of a hydro-reprocessing solvent extraction system for the co-extraction of uranium and plutonium from spent nuclear fuel, owing to its selectivity for hexavalent uranium and tetravalent plutonium. However, there is a critical lack of quantitative understanding regarding the impact of chemical environment on the radiation chemistry of DEHBA, and how this would affect process performance. Here we present a systematic investigation into the radiolytic degradation of DEHBA in a range of n-dodecane solvent system formulations, where we subject DEHBA to gamma irradiation, measure reaction kinetics, ligand integrity, degradation product formation, and investigate solvent system performance through uranium and plutonium extraction and strip distribution ratios. The rate of DEHBA degradation in n-dodecane was found to be slow (G = -0.31 ± 0.02 μmol J -1 ) but enhanced upon contact with the oxidizing conditions of the investigated solvent systems (organic-only, or in contact with either 0.1 or 3.0 M aqueous nitric acid). Two major degradation products were identified in the organic phase, bis-2-ethylhexylamine (b2EHA) and N-(2-ethylhexyl)butyramide (MEHBA), resulting from the cleavage of C–N bonds, and could account for the total loss of DEHBA up to ~300 kGy for organic-only conditions. Both b2EHA and MEHBA were also found to be susceptible to radiolytic degradation, having G-values of -0.12 ± 0.01 and -0.08 ± 0.01 μmol J -1 , respectively. Solvent extraction studies showed: (i) negligible change in uranium extraction and stripping with increasing absorbed dose; and (ii) plutonium extraction and retention exhibits complex dependencies on absorbed dose and chemical environment. Organic-only conditions afforded enhanced plutonium extraction and retention attributed to b2EHA, while acid contacts inhibited this effect and promoted significant plutonium retention for the highest acidity. Overall it has been demonstrated that chemical environment during irradiation has a significant influence on the extent of DEHBA degradation and plutonium retention.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Neutronic Performance of a Compact 10 MWe Nuclear Reactor with Low Enrichment (ThxU1−x)N Fuel

Abstract Recent interest in compact nuclear reactors for applications in space or in remote locations drives innovation in nuclear fuel design, especially non-oxide ceramic nuclear fuels. This work details neutronic modeling designed to support the development of a new nuclear fuel concept based on a mixture of thorium and uranium nitride. A Monte Carlo N-Particle Version 6.2 (MCNP-6) model of a compact 10 MWe reactor design which incorporates (Th x U 1− x )N fuel is presented. In this context, a “compact” reactor is a completely assembled reactor which may be emptied of coolant and transported by specialized commercial vehicle, deployed by a C130J aircraft, or launched into space. Core geometry, reflector barrels, and the heat exchange zones are designed to support reduction of overall reactor volume of core components while maintaining criticality with a fixed total fuel mass of 4500 kg. Dense mixed nitrides of thorium nitride (ThN) additions in uranium nitride (UN) in 5 wt.% increments between $$0.05 \le x \le 0.5$$ 0.05 ≤ x ≤ 0.5 have been considered for calculation of $$k_{\infty }$$ k ∞ and $$k_{{{\text{effective}}}}$$ k effective . ThN additions in UN results in a slight increase in the magnitude of the temperature coefficient of reactivity, which is negative by design. The isotopic distribution of the principal actinide inventory as a function of burnup, time, and initial fuel composition is presented and discussed within the context of the proliferation risk of this core design.

Parker, S. S. (ORCID:000000018597440X)↗

Sulfidation of magnetite with incorporated uranium

Uranium (U) is a radionuclide of key environmental interest due its abundance by mass within radioactive waste and presence in contaminated land scenarios. Ubiquitously present iron (oxyhydr)oxide mineral phases, such as (nano)magnetite, have been identified as candidates for immobilisation of U via incorporation into the mineral structure. Studies of how biogeochemicalprocesses, such as sulfidation from the presence of sulfate-reducing bacteria, may affect iron (oxyhydr)oxides and impact radionuclide mobility are important in order to underpin geological disposal of radioactive waste and manage radioactively contaminated land. Here, this study utilised a highly controlled abiotic method for sulfidation of U(V) incorporated into nanomagnetite to determine the fate and speciation of U. Upon sulfidation, transient release of U into solution occurred (~8.6 % total U) for up to 3 days, despite the highly reducing conditions. As the system evolved, lepidocrocite was observed to form over a period of days to weeks. After 10 months, XAS and geochemical data showed all U was partitioned to the solid phase, as both nanoparticulate uraninite (U(IV)O2) and a percentage of retained U(V). Further EXAFS analysis showed incorporation of the residual U(V) fraction into an iron (oxyhydr)oxide mineral phase, likely nanomagnetite or lepidocrocite. Overall, these results provide new insights into the stability of U(V) incorporated iron (oxyhydr)oxides during sulfidation, confirming the longer term retention of U in the solid phase under complex, environmentally relevant conditions.

Townsend, Luke↗

Nuclear waste reduction: Exploring new pathways one step at a time

In my home country of Venezuela, nuclear energy is not a topic that attracts much attention. The government briefly oversaw some nuclear energy programs during the 1950s, but currently there are no active nuclear power facilities in the country. In fact, the Venezuelan government signed and ratified the treaty of the prohibition of nuclear weapons in 2021, which states that Venezuela has never owned, possessed or controlled nuclear weapons or programs of any kind. When I moved to the United States, however, nuclear energy became an extremely relevant topic. In the 1940s, the U.S. government established and oversaw the Manhattan Project to build atomic bombs for use in World War II. After the war, the government encouraged scientists to use this information on nuclear reactions to develop nuclear energy for peaceful civilian purposes instead.1 During these early days of nuclear research, there were no formal regulatory standards for nuclear waste management. Policies usually were self-regulated and often created based on existing policies of disposal for non-nuclear waste.2 As a result, there were instances of nuclear waste leaching into the environment and affecting local communities. So, much research has been conducted since then to characterize and store nuclear waste safely and securely.3 I first became interested in nuclear energy during my undergraduate studies when I worked on a project involving ligand synthesis to help extract actinides from nuclear waste. I then studied electrochemistry in molten salt systems for nuclear energy applications during my Ph.D. As I approached graduation, I started looking into national laboratories that have programs involving nuclear energy and waste management. At Idaho National Laboratory (INL), the focus is more on applied processes and how nuclear energy can be innovated to realize next-generation reactor design and technologies. This focus led me to apply for a Seaborg distinguished postdoctoral position at INL, for which I was chosen based on my proposal of a way to improve nuclear waste recycling. To understand my proposal, we must familiarize ourselves with the makeup of nuclear waste. After uranium dioxide is used as nuclear fuel in a reactor, the fuel matrix is then characterized by various fission products, including rare earth elements, alkali and alkaline earths, and actinides. Some of these fission products can potentially be recovered through pyroprocessing, 4 which involves the electrochemical dissolution of the used nuclear fuel in a molten chloride salt mixture at high temperatures. Though some of the fission products can be easily recovered—for example, uranium is reduced onto an inert cathode by applied potentials—numerous other fission products such as rare earth elements are difficult to recover due to their multivalent oxidation states and side reactions.5 To improve the recovery efficiency of rare earth elements specifically, I proposed investigating the fundamental interactions between rare earth elements in the molten chloride salt and their metallic form (Figure 1). The kinetic pathways and the chemical reactions of these elements, which will be elucidated through spectro-electrochemistry at high temperatures, will give insights on how the recovery efficiency can be improved. Although my research focuses on fundamental science, it will benefit the applied process by generating new scientific knowledge and closing the gap for efficient recycling of the waste: one step at a time.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Uranium Partitioning upon Ammonia Gas Treatment on Phyllosilicate Minerals

In the past, > 200,000 kg of U was released to the Hanford Site vadose zone from disposal and leakage of waste byproducts from plutonium production during World War II and the Cold War (Zachara et al., 2007). U is highly mobile due to the presence of carbonates and oxidizing conditions, with K{sub d} of 0.1 - 8 mL/g at the site (Zachara et al., 2007; Szecsody et al., 2013; Serne et al., 2008). NH{sub 3} (gas) injection is being investigated as a remediation technique as it is an in situ method that will not introduce additional liquid that could drive contaminants deeper into vadose zone towards groundwater. Objectives: To understand the impact of alkaline injection on geochemical processes in the Hanford Site vadose zone, including: 1)Long-term fate of uranium (U); 2)Dissolution and re-precipitation of secondary minerals. Apparent K{sub d}'s increase significantly with NH{sub 3} gas treatment, especially for six-month aging. - K{sub d} decreases after aeration, primarily due to U desorption at lower pH. U removal is still significantly greater than natural conditions (K{sub d} < 8 vs. > 100 mL/g). - Three-day aeration has higher loading than six-month after ammonia gas treatment and aeration. However, significantly greater desorption of U occurs with aeration in the six-month aged sample potentially due to transformation into different, more soluble solid phases with longer term aging. - U removal is primarily due to (1) co-precipitation of U with secondary minerals and (2) adsorption to minerals' surface, although further research is required to identify dominant mechanisms. Future experiments will focus on garnering a better understanding of the solid phase U speciation. Solids will be characterized using SEM-EDS, EMPA, XPS, XAFS, and TEM to better understand the effects of basic treatments on initial minerals and formation of secondary precipitates.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DISSOLUTION OF SURROGATE U-Zr FUEL USING ALNIFLEX CONDITIONS

Non-aluminum clad spent nuclear fuel (NASNF) stored in L Basin at the Savannah River Site (SRS) is widely varied in fuel composition, design, packaging, and physical condition. The complexity of the NASNF inventory presents significant challenges, and technology development is necessary for successful disposition. One such fuel in the inventory is metallic uranium-zirconium (U-Zr) alloy fuel, the focus of this study. Electrolytic or nitric acid only dissolution of metallic U-Zr alloy can form insoluble zirconium oxide, which results in up to 52% loss of U to insoluble solids, and can be subject to potentially uncontrolled oxidation reactions [1, 2]. The AlNiflex process was determined to be a viable dissolution flowsheet for the U-Zr alloy fuel. Under a narrow set of solution concentrations, a combination of hydrofluoric acid (HF), nitric acid (HNO3), aluminum nitrate (Al(NO3)3), and hexavalent chromium can safely dissolve U-Zr intermetallic alloys, keep Zr soluble, and not significantly corrode stainless steel (SS) vessels [3, 4.

Gogolski, Jarrod M. [Savannah River National Labor↗

Imaging and Analysis of Insoluble Electrorefiner Material

Throughout pyroprocessing efforts at the Hot Fuel Examination Facility (HFEF), insoluble material has accumulated in the Electrorefiner (ER) vessel. The objective of this effort was to analyze the accumulated material to determine its origin. Material was removed from the ER salt bath and distilled to remove excess salt prior to performing analysis. Three samples were sent for chemical and isotopic analysis and underwent an ethyl acetate-bromine dissolution to segregate the oxide fraction from the metal fraction. Actinide concentrations were determined using a quadrupole–inductively coupled plasma–mass spectrometer (Q-ICP-MS). Three additional samples were sent for morphologic and elemental analysis by scanning electron microscopy (SEM) with Energy Dispersive X-ray (EDX) analysis at the Irradiated Materials Characterization Laboratory (IMCL). Analyses suggest that the material is primarily composed of UO2. with a small fraction of metal. This study draws no single conclusion as to the origin of the insoluble material in the ER. The particle sizes and morphologies observed in SEM micrographs indicate that the larger particles observed may be a result of introducing material to the ER that has not been completely reduced in Oxide Reduction (OR) operations, which precede electrorefining. Smaller particles may be due to reactions with oxygen and moisture present in HFEF. This research suggests that microscopic analysis of fuel particles before and after OR operations (including after distillation) as well as the uranium product collected on the cathode in the ER would increase understanding about particle morphology within the pyrochemical process.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Actinide arene-metalates: ion pairing effects on the electronic structure of unsupported uranium–arenide sandwich complexes

Addition of [UI 2 (THF) 3 (μ-OMe)] 2 ·THF (2·THF) to THF solutions containing 6 equiv. of K[C 14 H 10 ] generates the heteroleptic dimeric complexes [K(18-crown-6)(THF) 2 ] 2 [U(η 6 -C 14 H 10 )(η 4 -C 14 H 10 )(μ-OMe)] 2 ·4THF (1 18C6 ·4THF) and {[K(THF) 3 ][U(η 6 -C 14 H 10 )(η 4 -C 14 H 10 )(μ-OMe)]} 2 (1 THF ) upon crystallization of the products in THF in the presence or absence of 18-crown-6, respectively. Both 1 18C6 ·4THF and 1 THF are thermally stable in the solid-state at room temperature; however, after crystallization, they become insoluble in THF or DME solutions and instead gradually decompose upon standing. X-ray diffraction analysis reveals 1 18C6 ·4THF and 1 THF to be structurally similar, possessing uranium centres sandwiched between bent anthracenide ligands of mixed tetrahapto and hexahapto ligation modes. Yet, the two complexes are distinguished by the close contact potassium-arenide ion pairing that is seen in 1 THF but absent in 1 18C6 ·4THF, which is observed to have a significant effect on the electronic characteristics of the two complexes. Structural analysis, SQUID magnetometry data, XANES spectral characterization, and computational analyses are generally consistent with U(IV) formal assignments for the metal centres in both 1 18C6 ·4THF and 1 THF , though noticeable differences are detected between the two species. For instance, the effective magnetic moment of 1 THF (3.74 μ B ) is significantly lower than that of 1 18C6 ·4THF (4.40 μ B ) at 300 K. Furthermore, the XANES data shows the U L III -edge absorption energy for 1 THF to be 0.9 eV higher than that of 1 18C6 ·4THF, suggestive of more oxidized metal centres in the former. Of note, CASSCF calculations on the model complex {[U(η 6 -C 14 H 10 )(η 4 -C 14 H 10 )(μ-OMe)] 2 } 2– (1*) shows highly polarized uranium–arenide interactions defined by π-type bonds where the metal contributions are primarily comprised by the 6d-orbitals (7.3 ± 0.6%) with minor participation from the 5f-orbitals (1.5 ± 0.5%). These unique complexes provide new insights into actinide–arenide bonding interactions and show the sensitivity of the electronic structures of the uranium atoms to coordination sphere effects.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

MURR LEU structural and thermal hydraulics analyses: Part II – Impacts of irradiation thermo-mechanical behavior on thermal hydraulics safety analyses

A series of structural analyses have been performed to support the conversion of the University of Missouri Research Reactor (MURR) from the use of highly enriched uranium (HEU; ≥20 wt% U-235) to low-enriched uranium (LEU; <20 wt% U-235) fuel. The irradiation thermo-mechanical analysis evaluated the effects of fuel swelling, irradiation creep, thermal expansion, as well as thermal resistance from the oxide layer growth for the MURR LEU element in prototypic thermal and irradiation conditions as presented in Part I of this article. Overall, this irradiation thermo-mechanical analysis predicts smaller gap thickness reductions in previously limiting regions, and larger reductions in the middle of the outermost end channels where power density is not typically a maximum. Due to substantial differences between the channel gap reductions assumed for the previous safety analyses and those predicted by the irradiation thermo-mechanical analysis, a need to evaluate their impact on the thermal hydraulics safety analyses arose. This article presents the results from the steady-state safety analysis for normal operation as well as the two most limiting accident scenarios. The calculation models were revised in order to account for the spatial and temporal variation of the channel gap thicknesses. The results show that sufficient safety margins are still maintained for normal operation as well as during the postulated accident transients. This work provides a methodology of incorporating the irradiation thermo-mechanical behavior of plate-type fuel into the thermal hydraulics safety analyses.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Reactions of Np(VI) and Pu(VI) with Phenanthroline Result in Bending the [NpVIO2]2+ Unit and a Reduced Pu(V) Species

Despite decades of actinyl chemistry, genuinely bent actinyl structures remain rare beyond uranium. We report the first crystallographic characterization of a bent neptunyl(VI) complex, NpO 2 Cl 2 (phen) 2, along with a linear plutonyl species that, unexpectedly, adopts the +V oxidation state. Coordination of two 1,10-phenanthroline ligands to NpO 2 2+ enforces pronounced bending of the O yl –Np–O yl unit to 162° through steric clashes with the axial phenathroline ligand, representing the sharpest angle reported for any neptunyl(VI) complex. In contrast, synthesis with PuO 2 2+ produces a reduced linear Pu(V) species, PuO 2 Cl(phen) 2, underscoring the redox lability and the reluctance of plutonium to distort. Raman and IR spectra yield the first experimental stretching and interaction force constants for plutonyl(V). Comparison with values for plutonyl(VI) and bent and linear uranyl(VI) and neptunyl(VI) compounds shows that reduction perturbs the actinyl bond more than bending within one oxidation state. Electrochemical and spectroscopic studies clarify phenanthroline binding to Pu(VI) and the system’s reactivity. Quantum chemical calculations indicate that bending is energetically favored in the U–Np–Pu series, but the stabilization energy decreases as the actinide atomic number increases. NBO and QTAIM analyses reveal systematic trends: increasing 5f occupancy and decreasing An–O yl bond covalency from U to Pu. These results demonstrate that ligand-induced bending in neptunyl(VI) species is not only electronically feasible but also synthetically achievable, though plutonyl(VI) is constrained by redox reactivity. This work expands the frontier of nonlinear actinyl chemistry and illuminates how structure, oxidation state, and electronic configuration interrelate across the actinyl series.

actinides↗

Resonant x-ray emission across the L 3 edge of uranium compounds

A narrow bandwidth x-ray beamline and a multi-crystal von Hamos spectrometer were used to record x-ray absorption and x-ray emission (XES) across the uranium L 3 edge of UO 2 , UO 3 , Cs 2 UO 2 Cl 4 , and Cs 2 UCl 6 . Measurements were made over 17150–17250 eV with an instrumental resolution of ∼2 eV. This resolution allowed the use of Lorentzian peak fits to the L 3 N 4 and L 3 N 5 characteristic x-ray fluorescence lines that have ∼12–13 eV lifetime widths. The fluorescence yields of the four compounds display strong white lines near threshold and multiple scattering features at higher energies. The XES spectra were fit with three Lorentzians, two for the L 3 N 4 and L 3 N 5 lines and one for inelastic scattering by 2p–6d excitations and 4d–6d final states. The intensities of the white lines were largely due to the inelastic scattering component. To support the measurements, relativistic equation-of-motion coupled-cluster and restricted active space configuration interaction calculations were performed for uranium core-excitation energies in Cs 2 UO 2 Cl 4 and Cs 2 UCl 6 . These calculations with rigorous treatments of relativistic effects are shown to provide accurate uranium L 3 -edge binding energies, L 3 N 5 emission energies, as well as the energy losses in the inelastic scattering process. The measured and calculated results show variations between compounds with U(IV) oxidation states that contain 6d 0 5f 2 electrons in their ground configurations (UO 2 and Cs 2 UCl 6 ) compared with U(VI) compounds (UO 3 and Cs 2 UO 2 Cl 4 ) with empty 5f and 6d configurations.

74 ATOMIC AND MOLECULAR PHYSICS↗

Antiferromagnetic ordering and possible lattice response to dynamic uranium valence in U 3 O 8

Determining the correct electronic structure of U 3 O 8 remains a formidable experimental and theoretical challenge. In the low-temperature phase, two crystallographic U sites are separated into a distinct 2U(V)+1U(VI) oxidation configuration. At low temperatures, the U(V) sites form a distorted honeycomb lattice, but the U(VI) sit on a triangular sublattice, suggesting potential for magnetic frustration effects. The spin configuration of the unpaired f electrons on the U(V) sites is likely antiferromagnetic (AFM) from susceptibility measurements, but this has not been confirmed. Here in this paper, we present a neutron scattering investigation of the structure and dynamics of U 3 O 8 from 1.7 to 600 K. We confirm static AFM ordering onset at between 22 and 25 K, which is present down to at least 1.7 K with AFM peaks corresponding to [0.5 1 1] and [0.5 2 2] in the orthorhombic phase. These measurements rule out static AFM order along the a axis of the Amm2 phase, a configuration previously suggested by theory. Above 100 K a quasielastic scattering channel opens that we speculate arises from a lattice relaxation response to thermally activated electron hopping. This term does not conform to a magnetic form factor, so it is not related to spin relaxations. If correct, this mechanism stabilizes a continuous valence transition from 2U(V)+1U(VI) in the low-temperature (T<600 K) orthorhombic phase to the hexagonal phase that contains only one degenerate U site, wherein the U valence can be dynamically stabilized between U(V)↔U(VI) by phonon-assisted electron hopping.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Using Atom Dynamics to Map the Defect Structure Around an Impurity in Nano-Hematite

The geochemical cycling of actinides such as U is strongly controlled by Fe (oxyhydr)oxides. Indeed, the strong affinity of these minerals for U has factored into the design of geologic repositories for the long-term storage of nuclear waste. Many decades of work have focused on detailing the local coordination environment U associated with hematite (a-Fe2O3), a common and stable Fe(III) oxide, in order to better predict the fate and transport of U in the sub-surface. Here, for the first time, molecular dynamic simulations and atomically resolved electron microscopy of uranium atom mobility under the beam were used to map the topology of defect clusters surrounding structurally incorporated U in hematite. The ability to observe vacancies by means of metal atom hopping can be used to directly probe defects in other materials, with promising applications in geochemistry and materials science.

Ilton, Eugene S.↗

Effects of Borate and Organics on U(VI) Solubility in WIPP Brine

The solubility of uranium (VI) in Waste Isolation Pilot Plant (WIPP)-relevant brine was determined to support ongoing WIPP recertification activities. This research was performed by the Los Alamos National Laboratory Carlsbad Operations (LANL-CO) Actinide Chemistry and Repository Science Program (ACRSP). The WIPP Actinide Source Term Program (ASTP) did not develop a model for the solubility of actinides in the VI oxidation state. The solubility of UO 2 2+ , in the absence of WIPP specific data, is presently set to be equal to a conservatively high 1 mM within the WIPP Performance Assessment (PA) for all expected WIPP conditions (SOTERM, 2019) as selected at the recommendation of the Environment Protection Agency (EPA) (EPA, 2005). According to the current WIPP chemistry model assumptions and conditions, the expected pC H+ is about 9.5 and controlled by MgO buffering CO 3 2- . The goal of this study is to perform screening experiments that account for the contributions of organics and borate on uranium solubility. In this report, the solubility of U(VI) was determined at pC H+ 9 WIPP brine in the absence or presence of borate and organics at under-saturation approach. Experiments were equilibrated for about 135 days. Organic compounds present in WIPP waste can form strong complexes with actinides and can affect the oxidation states of actinides. The organic compounds addressed in WIPP performance assessment include EDTA (Ethylenediaminetetraacetic Acid), oxalate, citrate, and acetate (SOTERM, 2019). These data quantify the effects of WIPP-relevant concentrations of borate and organics effects on the solubility of U(VI) to challenge the predictions of the WIPP actinide model and inform decisions and recommendations made in the upcoming recertification of the WIPP (CRA-2024). The experiments performed were done according to the U.S. Department of Energy (DOE) approved Test Plan entitled “Experimental Strategy to Challenge Actinide Solubility Predictions” and designated LCO-ACP-26. All data reported were obtained under the LANL-CO Quality Assurance Program, which is compliant with the DOE Carlsbad Field Office, Quality Assurance Program Document (CBFO/QAPD) (QAPD, 2017).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗