Edgar Buck

The degradation of the internal structure of plutonium (IV) oxalate during calcination was investigated with Transmission Electron Microscopy (TEM), electron diffraction, Electron Energy-Loss Spectroscopy (EELS), and 4D Scanning TEM (STEM). TEM lift-outs were prepared from samples that had been calcined at 300°C, 450°C, 650°C and 950°C. The resulting phase at all calcination temperatures was identified as PuO₂ with electron diffraction. The grain size range was obtained with high-resolution TEM. In addition, 4D STEM images were analyzed to provide grain size distributions. In the 300°C calcined sample, the grains were <10 nm in diameter, at 650°C, the grains ranged from 10 to 20 nm, and by 950°C, the grains were 95–175 nm across. Using the Kolmogorov-Smirnov (K-S) two sample test, it was shown that morphological measurements obtained from 4D-STEM provided statistically significant distributions to distinguish samples at the different calcination conditions. Using STEM-EELS, carbon was shown to be present in the low temperature calcined samples associated with oxalate but had formed carbon (possibly graphite) deposits in the 950°C calcined sample. This work highlights the new methods of STEM-EELS and 4D-STEM for studying the internal structure of special nuclear materials (SNM).

Excellent catalytic performance of oxygen vacancy enriched, nano-porous Mn₃O₄/Ni/NiMnO₃ architecture.

We report the structural, vibrational, and optical properties of americium formate (Am(CHO₂)₃) crystals synthesized via the in situ hydrolysis of dimethylformamide (DMF). The coordination polymer features Am³⁺ ions linked by formate ligands into a three‐dimensional network that is isomorphous to several lanthanide analogs, (e. g., Eu³⁺, Nd³⁺, Tb³⁺). Structure determination revealed a nine‐coordinate Am³⁺ metal center that features a unique local C_3v symmetry. The metal–ligand bonding interactions were investigated by vibrational spectroscopy, natural localized molecular orbital calculations, and the quantum theory of atoms in molecules. The results paint a predominantly ionic bond picture and suggest the metal‐oxygen bonds increase in strength from Nd−O<Eu−O<Am−O. The optical properties were probed using diffuse reflectance and photoluminescence spectroscopies. Notably, the rarely reported ⁵D_1′→⁷F_0′ emission band is observed and dominates the emission spectrum. This behavior is unusual and is attributed to the C_3v coordination environment of the metal center.

We report the structural, vibrational, and optical properties of americium formate (Am(CHO₂)₃) crystals synthesized via the in situ hydrolysis of dimethylformamide (DMF). The coordination polymer features Am³⁺ ions linked by formate ligands into a three‐dimensional network that is isomorphous to several lanthanide analogs, (e. g., Eu³⁺, Nd³⁺, Tb³⁺). Structure determination revealed a nine‐coordinate Am³⁺ metal center that features a unique local C_3v symmetry. The metal–ligand bonding interactions were investigated by vibrational spectroscopy, natural localized molecular orbital calculations, and the quantum theory of atoms in molecules. The results paint a predominantly ionic bond picture and suggest the metal‐oxygen bonds increase in strength from Nd−O<Eu−O<Am−O. The optical properties were probed using diffuse reflectance and photoluminescence spectroscopies. Notably, the rarely reported ⁵D_1′→⁷F_0′ emission band is observed and dominates the emission spectrum. This behavior is unusual and is attributed to the C_3v coordination environment of the metal center.

Introduction: This study aims to develop a microgram-scale microfluidic electrochemical cell (E-cell) for investigating the redox behavior of uranium oxide (UO₂). The traditional bulk electrochemical methods may require shielded facilities to investigate the hazardous materials, e.g., spent nuclear fuel, due to high radiation levels. Microfluidic E-cells offer advantages such as reduced radiation exposure, control over fluid flow rates, and high-throughput capabilities.

Methods: The design of the E-cell considers electrode morphology, adhesion to a thin membrane, electrode configuration, and vacuum compatibility. Three techniques, including FIB-SEM lift-out, Au coating, and polyvinylidene fluoride (PVDF) binder, are explored for fabricating and attaching microgram quantities of UO₂ as working electrodes. The PVDF binder method proves to be the most effective, enabling the creation of a vacuum-compatible microfluidic E-cell.

Results and discussion: The PVDF binder method demonstrates successful electrochemical responses and allows for real-time monitoring of UO₂ electrode behavior at the microscale. It offers chemical imaging capabilities using in situ SEM/EDS analysis. The technique provides consistent redox outcomes similar to bulk electrochemical analysis.

Conclusion: The development of a microgram-scale microfluidic electrochemical cell using the PVDF binder technique enables the investigation of UO₂ redox behavior. It offers a low-risk approach with reduced radiation exposure and high-throughput capabilities. The technique provides real-time monitoring and chemical imaging capabilities, making it valuable for studying spent nuclear fuel systems and material characterization.

Highlight of the multimodal characterization of corrosion behaviour of microgram quantities of UO₂, enabled by a novel particle-attached microfluidic electrochemical cell.

We developed a new approach to attach particles onto a conductive layer as a working electrode (WE) in a microfluidic electrochemical cell with three electrodes. Nafion, an efficient proton transfer molecule, is used to form a thin protection layer to secure particle electrodes. Spin coating is used to develop a thin and even layer of Nafion membrane. The effects of Nafion (5 wt% 20 wt%) and spinning rates were evaluated using multiple sets of replicates. The electrochemical performance of various devices was demonstrated. Additionally, the electrochemical performance of the devices is used to select and optimize fabrication conditions. The results show that a higher spinning rate and a lower Nafion concentration (5 wt%) induce a better performance, using cerium oxide (CeO2) particles as a testing model. The WE surfaces were characterized using atomic force microscopy (AFM), scanning electron microscopy-focused ion beam (SEM-FIB), time-of-flight secondary ion mass spectrometry (ToF-SIMS), and X-ray photoelectron spectroscopy (XPS). The comparison between the pristine and corroded WE surfaces shows that Nafion is redistributed after potential is applied. Our results verify that Nafion membrane offers a reliable means to secure particles onto electrodes. Furthermore, the electrochemical performance is reliable and reproducible. Thus, this approach provides a new way to study more complex and challenging particles, such as uranium oxide, in the future.

Electrochemical analysis is an efficient way to study various materials. However, nanoparticles are challenging due to the difficulty in fabricating a uniform electrode containing nanoparticles. We developed novel approaches to incorporate nanoparticles as a working electrode (WE) in a three-electrode microfluidic electrochemical cell. Specifically, conductive epoxy was used as a medium for direct application of nanoparticles onto the electrode surface. Three approaches in this work were illustrated, including sequence stamping, mix stamping, and droplet stamping. Shadow masking was used to form the conductive structure in the WE surface on a thin silicon nitride (SiN) membrane. Two types of nanomaterials, namely cerium oxide (CeO2) and graphite, were chosen as representative nanoparticles. The as-fabricated electrodes with attached particles were characterized using atomic force microscopy (AFM) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). Electrochemical analysis was performed to verify the feasibility of these nanoparticles as electrodes. Nanomaterials can be quickly assessed for their electrochemical properties using these new electrode fabrication methods in a microfluidic cell, offering a passport for rapid nanomaterial electrochemical analysis in the future.

The sequestration of metal ions into the crystal structure of minerals is common in nature. To date, the incorporation of technetium(IV) into iron minerals has been studied predominantly for systems under carefully controlled anaerobic conditions. Mechanisms of the transformation of iron phases leading to incorporation of technetium(IV) under aerobic conditions remain poorly understood. Here we investigate granular metallic iron for reductive sequestration of technetium(VII) at elevated concentrations under ambient conditions. We report the retarded transformation of ferrihydrite to magnetite in the presence of technetium. We observe that quantitative reduction of pertechnetate with a fraction of technetium(IV) structurally incorporated into non-stoichiometric magnetite benefits from concomitant zero valent iron oxidative transformation. An in-depth profile of iron oxide reveals clusters of the incorporated technetium(IV), which account for 32% of the total retained technetium estimated via X-ray absorption and X-ray photoelectron spectroscopies. This corresponds to 1.86 wt.% technetium in magnetite, providing the experimental evidence to theoretical postulations on thermodynamically stable technetium(IV) being incorporated into magnetite under spontaneous aerobic redox conditions.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

We have made observations of noble metal phase fission-product agglomerates and gaseous xenon within the fuel-cladding interaction (FCI) zone of a high-burnup UO₂ fuel. The FCI is the boundary between the UO₂ pellet outer surface and the inner wall of the oxidized Zr-liner/cladding of the fuel rod. These fission-product agglomerates are well known to occur within the spent fuel matrix, and although radionuclides have been reported by others, we reveal aspects of their speciation and morphology. That they occur as discrete particles in the oxidized Zr liner, suggests the occurrence of hitherto unknown processes in the FCI zone during reactor operation, and this may have implications for the long-term storage and disposal of these types of materials. As expected, the particle agglomerates, which ranged in size from the nanometer scale to the micrometer scale, contained mainly Mo, Ru, Tc, Rh, and Pd; however, we also found significant quantities of Te associated with Pd. Indeed, we found nanometer scale separation of the distinct Pd/Te phase from the other fission products within the particles. Often associated with the particles was concentrations of uranium, sometimes appearing as a “cloud” with a tail emanating from the fuel into the oxidized cladding liner. Many of the noble metal phase particles appeared as fractured clusters separated by Xe-gas-filled voids. Possible mechanisms of formation or transport in the cladding liner are presented.

“Phase” map showing Noble metal phase particle (orange) and U fuel fragments (green and yellow) ejected into Zr cladding (red and blue) as a result of Xe bubble rupture.

Trace analysis of nuclear materials in solid particles collected in the environment or particles in liquid slurry generated in nuclear material manufacturing processes can pinpoint elemental, organic, and isotopic signatures of nuclear fuel cycle activities and processes. Such information can support nuclear safeguards programs by increasing our ability to detect undeclared nuclear materials, routine activities for safeguarding at declared facilities, and illicit activities. However, trace radioactive material analysis in liquids and slurries is challenging using bulk approaches. For example, one drawback of sensitive analysis such as inductively coupled plasma mass spectrometry (ICP‐MS) is that sample is consumed or destroyed as a result of the technical approach. We developed a vacuum compatible microfluidic interface to enable surface analysis of liquids and solid–liquid interactions using time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS). In this work, we illustrate the initial results from the analysis of liquid uranium oxide standard solutions using in situ liquid SIMS. Because the liquid SIMS analysis is almost nondestructive, the same sample can then be analyzed by other analytical techniques or saved for future reference. Consequently, multimodal analysis is possible. Our results demonstrate that in situ liquid SIMS can be used as a new approach to analyze radioactive materials in liquid and slurry forms of relevance to diverse applications.

Oxygen defects govern the behavior of a range of materials spanning catalysis, quantum computing, and nuclear energy. Understanding and controlling these defects is particularly important for the safe use, storage, and disposal of actinide oxides in the nuclear fuel cycle, since their oxidation state influences fuel lifetimes, stability, and the contamination of groundwater. However, poorly understood nanoscale fluctuations in these systems can lead to significant deviations from bulk oxidation behavior. Here we describe the use of aberration-corrected scanning transmission electron microscopy and electron energy loss spectroscopy to resolve changes in the local oxygen defect environment in U O 2 + x surfaces. We observe large image contrast and spectral changes that reflect the presence of sizable gradients in interstitial oxygen content at the nanoscale, which we quantify through first-principles calculations and image simulations. These findings reveal an unprecedented level of excess oxygen incorporated in a complex near-surface spatial distribution, offering additional insight into defect formation pathways and kinetics during U O 2 surface oxidation.

Oxygen defects govern the behavior of a range of materials spanning catalysis, quantum computing, and nuclear energy. Understanding and controlling these defects is particularly important for the safe use, storage, and disposal of actinide oxides in the nuclear fuel cycle, since their oxidation state influences fuel lifetimes, stability, and the contamination of groundwater. However, poorly understood nanoscale fluctuations in these systems can lead to significant deviations from bulk oxidation behavior. Here we describe the use of aberration-corrected scanning transmission electron microscopy and electron energy loss spectroscopy to resolve changes in the local oxygen defect environment in U O 2 + x surfaces. We observe large image contrast and spectral changes that reflect the presence of sizable gradients in interstitial oxygen content at the nanoscale, which we quantify through first-principles calculations and image simulations. These findings reveal an unprecedented level of excess oxygen incorporated in a complex near-surface spatial distribution, offering additional insight into defect formation pathways and kinetics during U O 2 surface oxidation.

This work demonstrates a controlled potential electrochemistry with correlative microscopy for insight into the radial H-distribution into TPBAR components of light water reactors.

The development of targeted syntheses requires a better understanding of how production pathways affect the final product, but many ex situ techniques used for studying nanoparticle growth are unsuitable as standalone methods for identifying and characterizing growth mechanisms.

During electron microscopy observations of uranium-bearing phases and solutions in a liquid cell, the electron beam induced radiolysis causes changes in the chemistry of the system.

Layered (oxy) hydroxide minerals often possess out-of-plane hydrogen atoms that form hydrogen bonding networks which stabilize the layered structure. However, less is known about how the ordering of these bonds affects the structural stability and solubility of these minerals. Here, we report a new strategy that uses the focused electron beam to probe the effect of differences in hydrogen bonding networks on mineral solubility. In this regard, the dissolution behavior of boehmite (γ-AlOOH) and gibbsite (γ-Al(OH)3) were compared and contrasted in real time via liquid cell electron microscopy. Under identical such conditions, 2D-nanosheets of boehmite (γ-AlOOH) exfoliated from the bulk and then rapidly dissolved, whereas gibbsite was stable. Further, substitution of only 1% Fe(III) for Al(III) in the structure of boehmite inhibited delamination and dissolution. Factors such as pH, radiolytic species, and knock on damage were systematically studied and eliminated as proximal causes for boehmite dissolution. Instead, the creation of electron/hole pairs was considered to be the mechanism that drove dissolution. The widely disparate behaviors of boehmite, gibbsite, and Fe-doped boehmite are discussed in the context of differences in the OH bond strengths, hydrogen bonding networks, and the presence or absence of electron/hole recombination centers.

Cr(iii) is observed to prefer (near-)surface sites in boehmite, as opposed to the bulk.

The distribution and physical form of technetium in a Hanford low‐activity waste (LAW) glass was examined with scanning electron microscopy (SEM) and X‐ray diffraction (XRD). A simulated Hanford LAW glass was spiked with varying amounts of potassium pertechnetate and melted at 1000°C. The glass was melted in a sealed quartz ampoule with the air pumped out, so that volatile material could leave the glass but would not be lost from the system. Previous studies have shown that technetium remains in the glass up to about 2000 ppm, but rises to the top of the melt as a separate salt phase above this concentration. Examination by SEM shows that crystals of technetium compounds appear to grow out of the hot glass, which implies that the hot glass was supersaturated in technetium salts. Some of the technetium compound crystals had apparently melted, but other crystals had obviously not melted and must have formed after the glass had partially cooled. The technetium compounds in the salt layer are KTcO₄ and NaTcO₄, according to SEM and XRD. No TcO₂ was found in the salt phase, even though Tc(IV) has been previously reported in the glass.

Although most of the world's uranium exists as pitchblende or uraninite, this mineral can be weathered to a great variety of secondary uranium minerals, most containing the uranyl cation. Anthropogenic uranium compounds can also react in the environment, leading to spatial–chemical alterations that could be useful for nuclear forensics analyses. Soft X‐ray absorption spectroscopy (XAS) has the advantages of being non‐destructive, element‐specific and sensitive to electronic and physical structure. The soft X‐ray probe can also be focused to a spot size on the order of tens of nanometres, providing chemical information with high spatial resolution. However, before XAS can be applied at high spatial resolution, it is necessary to find spectroscopic signatures for a variety of uranium compounds in the soft X‐ray spectral region. To that end, we collected the near edge X‐ray absorption fine structure (NEXAFS) spectra of a variety of common uranyl‐bearing minerals, including uranyl carbonates, oxyhydroxides, phosphates and silicates. We find that uranyl compounds can be distinguished by class (carbonate, oxyhydroxide, phosphate or silicate) based on their oxygen K‐edge absorption spectra. This work establishes a database of reference spectra for future spatially resolved analyses. We proceed to show scanning X‐ray transmission microscopy (STXM) data from a schoepite particle in the presence of an unknown contaminant.

The mechanical properties and stability of studtite, (UO₂)(O₂)(H₂O)₂·2H₂O, and metastudtite, (UO₂)(O₂)(H₂O)₂, were investigated using density functional perturbation theory.

The occurrence of plutonium dioxide (PuO₂) either from direct deposition or from the precipitation of plutonium-bearing solutions in contaminated soils and sediments is well described, particularly for the Hanford site in Washington State. However, past research has suggested that plutonium at the Hanford site may exist in chemical forms in addition to PuO₂. Although the majority of the plutonium is present as oxide, we present evidence for the formation of nano-sized mixed plutonium- iron phosphate hydroxide structurally related to the rhabdophane group minerals in 216-Z9 crib sediments from Hanford using both transmission electron microscopy (TEM) and X-ray absorption spectroscopy (XAS). The iron-plutonium phosphate formation may depend on the local microenvironment in the sediments, availability of phosphate, and hence the distribution of these minerals may control long-term migration of plutonium in the soil.

The solubility of different forms of precipitated ²⁴²PuO₂(am) were examined in solutions containing aqueous Fe(II) over a range of pH values. The first series of ²⁴²PuO₂(am) suspensions were prepared from a ²⁴²Pu(IV) stock that had been treated with thenoyltrifluoroacetone (TTA) to remove the ²⁴¹Am originating from the decay of ²⁴¹Pu. These ²⁴²PuO₂(am) suspensions showed much higher solubilities at the same pH value and Fe(II) concentration than previous studies using ²³⁹PuO₂(am). X-ray absorption fine structure (XAFS) spectroscopy of the precipitates showed a substantially reduced Pu–Pu backscatter over that previously observed in ²³⁹PuO₂(am) precipitates, indicating that the ²⁴²PuO₂(am) precipitates purified using TTA lacked the long range order previously found in²³⁹PuO₂(am) precipitates. The Pu(IV) stock solution was subsequently repurified using an ion exchange resin and an additional series of ²⁴²PuO₂(am) precipitates prepared. These suspensions showed higher redox potentials and total aqueous Pu concentrations than the TTA purified stock solution. The higher redox potential and aqueous Pu concentrations were in general agreement with previous studies on ²⁴²PuO₂(am) precipitates, presumably due to the removal of possible organic compounds originally present in the TTA purified stock. ²⁴²PuO₂(am) suspensions prepared with both stock solutions showed almost identical solubilities in Fe(II) containing solutions even though the initial aqueous Pu concentrations before the addition of Fe(II) were orders of magnitude different. By examining the solubility of ²⁴²PuO₂(am) prepared from both stocks in this way we have essentially approached equilibrium from both the undersaturated and oversaturated conditions. The final aqueous Pu concentrations are predictable using a chemical equilibrium model which includes the formation of a nanometer sized Fe(III) reaction product, identified in the ²⁴²PuO₂(am) suspension both by use of ⁵⁷Fe Mössbauer spectroscopy and transmission electron microscopy (TEM) analysis.

The reduction of PuO₂(am) by Fe(II) in the presence and absence of hematite was studied over a range of pH values and oxidation/reduction potentials. In contrast to thermodynamic predictions, the presence of hematite did not have a major effect on the overall reduction of PuO₂(am) to aqueous Pu(III). Instead the aqueous Pu(III) concentrations at longer time frames were accurately predicted using the measured Fe(II) concentration and existing thermodynamic data for the reaction: H₂O + H⁺+ Fe²⁺+ PuO₂(am) ⇌ Pu³⁺+ Fe(OH)₃(am) with log K =− 0.6. The accuracy of this approach in all solutions containing aqueous Fe(II), coupled with the apparent lack of oxidation of Fe(II) by O₂(g), suggests that the Fe(OH)₃(am) is formed by the oxidation of Fe(II) to Fe(III) by radiolysis. The continued generation of reactive amorphous iron hydroxide by radiolysis prevents thermodynamic equilibrium from being reached with more stable ferric oxide compounds, except possibly under acidic conditions where amorphous ferric hydroxide is soluble. The use of measured pe values, instead of aqueous Fe(II) measurements, also yields reasonable predictions of the final Pu(III) concentrations although the predictions are more uncertain.

A titanate-based ceramic waste form, rich in phases structurally related to zirconolite (CaZrTi₂O₇), is being developed as a possible method for immobilizing excess plutonium from dismantled nuclear weapons. As part of this program, Lawrence Livermore National Laboratory (LLNL) produced several ceramics that were then characterized at Argonne National Laboratory (ANL). The plutonium-loaded ceramic was found to contain a Pu-Gd zirconolite phase but also contained plutonium titanates, Gd-polymignyte, and a series of other phases. In addition, much of the Pu was remained as PuO_2-x. The Pu oxidation state in the zirconolite was determined to be mainly Pu⁴⁺, although some Pu³⁺was believed to be present.

The alteration behavior of UO₂ pellets following their reaction under unsaturated drip-test conditions, at 90°C, for time periods of up to 10 years has been examined by solid phase and leachate analyses. Sample reactions were characterized by preferential dissolution of grain boundaries between the original press-sintered UO₂ granules comprising the samples, development of a polygonal network of open channels along the intergrain boundaries, and spallation of surface granules that had undergone severe grain boundary corrosion. The development of a dense mat of alteration phases after two years of reaction trapped loose granules, resulting in reduced rates of particulate uranium release. The paragenetic sequence of alteration phases that formed on the present samples was similar to that observed in surficial weathering zones of natural uraninite (UO₂) deposits, with alkali and alkaline earth uranyl silicates representing the long-term solubility-limiting phases for uranium in both systems.

Results for a radiolysis model sensitivity study of radiolytically produced H₂O₂ are presented as they relate to Spent (or Used) Light Water Reactor uranium oxide (UO₂) nuclear fuel (UNF) oxidation in a low oxygen environment. The model builds on previous reaction kinetic studies to represent the radiolytic processes occurring at the nuclear fuel surface. Hydrogen peroxide (H₂O₂) is the dominant oxidant for spent nuclear fuel in an O₂-depleted water environment. The most sensitive parameters have been identified with respect to predictions under typical conditions. As compared with the full model with about 100 reactions, it was found that only 30 to 40 of the reactions are required to determine [H₂O₂] to one part in 10^–5 and to preserve most of the predictions for major species. This allows a systematic approach for model simplification and offers guidance in designing experiments for validation.

Drip tests designed to replicate the synergistic interactions between waste glass, repository groundwater, water vapor, and sensitized 304L stainless steel in the potential Yucca Mountain Repository have been ongoing in our laboratory for over ten years. Results will be presented from three sets of these drip tests: two with actinide-doped glasses, and one with a fully-radioactive glass. Periodic sampling of these tests have revealed trends in actinide release behavior that are consistent with their entrainment in colloidal material when as-cast glass is reacted. Results from vapor hydrated glass show that initially the actinides are completely dissolved in solution, but as the reaction proceeds, the actinides become suspended in solution. Sequential filtering and alpha spectroscopy of colloid-bearing leachate solutions indicate that more than 80% of the plutonium and americium are bound to particles that are captured by a 0.1 μm filter, while less than 10% of the neptunium is stopped by a 0.1 μm filter. Analytical transmission electron microscopy has been used to examine particles from leachate solutions and to identify several actinide-bearing phases which are responsible for the majority of actinide release during glass corrosion.

We have characterized considerable amounts of the two known uranyl peroxide phases that formed under static immersion conditions on commercial spent nuclear fuel (CSNF) samples. Milligrams of corroded fuel aggregates were observed at the air-water interface in each sample. The bulk fuel and the interfacial solids were examined by SEM, EDX, and XRD and were found to contain studtite and metastudtite, respectively. The reason for the partitioning of the two phases is not clear at this time. The unique occurrence of the floating phase prompted a radiochemical analysis of these solids. The analysis indicated that ⁹⁰Sr, ¹³⁷Cs, ⁹⁹Tc, and to a lesser extent of ^238,239Pu and ²³⁷Np, had partitioned with the air-water interface aggregates. The concentration of ²⁴¹Am in the interfacial solids was two orders of magnitude lower than the inventory in the fuel prior to contact with water. The radiochemical analyses of two fuel leachate samples are compared to reported leaching data of a similar fuel which did not result in the formation of studtite.

Static leach tests similar to the PCT were performed for times up to two years to assess the long-term reaction behavior of high-level nuclear waste glasses similar to those expected to be produced at the Defense Waste Processing Facility. These tests show the reaction rate to decrease with the reaction time from an initially high rate to a low rate, but then to accelerate to a higher rate after reaction times of about one year, depending on the glass surface area/leachant volume ratio (SAN) used. The solution concentrations of soluble glass components increase as the reaction is accelerated, while the release of other glass components into solution is controlled by secondary phases which form during the reaction. The net result is that the transformation of glass to stable phases is accelerated while the solution becomes enriched in soluble components that are not effectively contained in secondary phases. The rate becomes linear in time after the acceleration and may be similar to the initial forward rate. A current model of glass reaction predicts that the glass reaction will be accelerated upon the formation of secondary phases which lower the silicic acid solution concentration. These tests show the total silicon concentration to increase upon acceleration of the reaction, however, which may be due to the slightly higher pH that is attained with the acceleration. The sudden change in the reaction rate is likely due to secondary phase formation.

Titanate ceramics have been proposed as candidate materials for immobilizing excess weapons plutonium. This study focuses on the characterization of a titanate-based ceramic through X-ray diffraction (XRD), electron probe microanalysis, and electron energy-loss spectroscopy (EELS). Three distinct phases have been identified, and their volume fraction was determined from element distribution maps using Scionimage-NIH Analysis software. This analysis revealed that the pyrochlore-group phase betafite (A₂Ti₂O₇) forms the matrix of the ceramic and occupies 90.4% of the volume. Uniformly distributed in this matrix are perovskite (A₂Ti₂O₆) and Hf-enriched rutile (TiO₂), which account for 6.4 vol% and 3.1 vol%, respectively. The studied ceramic exhibits a very low porosity (0.3 vol%), which is characterized by small (<6 μm), rounded and isolated voids. In the studied ceramic, A-site cations are represented by Ca, rare earth elements, and Hf. The powder XRD pattern of the ceramic allowed refining the unit cell parameters for the cubic betafite, which is characterized by a cell edge of 10.132±0.003Å. The EELS data indicate that Ce is present as both Ce³⁺ and Ce⁴⁺ in betafite, whereas in perovskite, all Ce is trivalent.

The release of⁹⁹Tc can be used as a reliable marker for the extent of spent oxide fuel reaction under unsaturated high-drip-rate conditions at 90°C. Evidence from leachate data and from scanning and transmission electron microscopy (SEM and TEM) examination of reacted fuel samples is presented for radionuclide release, potential reaction pathways, and the formation of alteration products. In the ATM-103 fuel, 0.03 of the total inventory of⁹⁹Tc is released in 3.7 years under unsaturated and oxidizing conditions. Two reaction pathways that have been identified from SEM are 1) through-grain dissolution with subsequent formation of uranyl alteration products, and 2) grain-boundary dissolution. The major alteration product identified by X-ray diffraction (XRD) and SEM, is Na-boltwoodite, Na[(UO₂)(SiO₃OH)]H₂0, which is formed from sodium and silicon in the water leachant.

Pyrochlore-rich ceramics containing additional zirconolite, brannerite and rutile have been developed for immobilizing excess weapons plutonium. This study reports data for a ceramic containing small amounts of Al and Mo in addition to the major oxide components of Ti, U, Ca, Hf, Gd and Ce. Hafnium and Gd are added as neutron absorbers, Al and Mo represent impurities. Quantitative electron microprobe data demonstrate that UO₂ is strongly partitioned into brannerite (45 wt%), which is present as euhedral crystals with inclusions of unreacted UO₂. Pyrochlore forms the groundmass and has an average UO₂ content of 28 wt%. Zirconolite contains only 15 wt% UO₂, but is significantly more effective in accommodating Hf and Gd than both brannerite and pyrochlore. Zirconolite incorporates U together with Hf and Ce in one structural site, whereas brannerite and pyrochlore accommodate U with Gd in a site that is distinct from that occupied by Hf. Incorporation of Gd into zirconolite takes place via a coupled substitution involving Al, thus explaining the high Al₂O₃ contents (3 wt%). Molybdenum was not detected in the major oxides, and it might be present in the accessory rutile. Although the studied waste form was designed to incorporate Pu, the present dataset is also valuable because immobilization of highly fissile U (e.g., U-233) might need to be considered in the future.

This paper examines the ability of electron energy-loss spectroscopy (EELS) combined with transmission electron microscopy (TEM) to detect both low concentrations of Np in a U matrix and to provide evidence for incorporation of Np in U(VI) phases. The case for U(VI) secondary minerals acting as solubility-controlling phases for Np in repository performance assessment models has not been fully established. Direct evidence for incorporation, rather than sorption, continues to be difficult to obtain. Detection of Np with TEM-EELS is hampered by the occurrence of a plural (multiple) scattering event from the more abundant U atoms (U-M₅ + U- O_4,5), that results in severe overlap on the Np-M₅ edge at ∼3665 eV. By examining the energy âgap' between the Np-M₅ and Np-M₄ edges (184 eV), a method for observing Np independently of the plural scattering event has been established. Clear evidence of Np incorporation into synthetic studtite {(UO₂)(O₂)(H₂O)₂](H₂O)₂} and uranophane {Ca(UO₂)₂(SiO₃OH)₂(H₂O)₅} has been found with TEM-EELS. The EELS technique continues to remain an important tool for examining the potential for transuranic behavior in nuclear waste materials.

Microbe-mineral and -metal interactions represent a major intersection between the biosphere and geosphere but require high-resolution imaging and analytical tools for investigation of microscale associations. Electron microscopy has been used extensively for geomicrobial investigations, and although usedbona fide, the traditional methods of sample preparation do not preserve the native morphology of microbiological components, especially extracellular polymers. Herein, we present a direct comparative analysis of microbial interactions by conventional electron microscopy approaches with imaging at room temperature and a suite of cryogenic electron microscopy methods providing imaging in the close-to-natural hydrated state.In situ, we observed an irreversible transformation of the hydrated bacterial extracellular polymers during the traditional dehydration-based sample preparation that resulted in their collapse into filamentous structures. Dehydration-induced polymer collapse can lead to inaccurate spatial relationships and hence could subsequently affect conclusions regarding the nature of interactions between microbial extracellular polymers and their environment.

The migration behavior of radionuclides in a nuclear-waste repository will be influenced, in part, by their equilibrium solubilities in the presence of radionuclide-bearing solids and/or adsorption affinities as trace components onto the surfaces of solid host phases. Uranium phases that precipitate on the surface of altered spent nuclear fuel may thus influence the mobility of radionuclides released in the near-field environment, since by proximity, these will be the first phases that the radionuclides encounter following their release from the spent fuel matrix.

We have evaluated the potential for incorporating radionuclides into crystalline compounds by precipitating uranyl phases from aqueous solutions containing dissolved rare earth elements (REE; 2.1 ppm Ce⁴⁺, 4.6 ppm Ce⁴⁺, or 286 ppm Nd³⁺). Rare earth elements serve both as monitors for evaluating the potential behavior of REE radionuclides and as surrogate elements for the actinides (e.g., Ce⁴⁺ and Nd³⁺ for Pu⁴⁺ and Am³⁺, respectively). Although the crystalline compound that formed in the present set of experiments has not been positively identified, x-ray diffraction profiles suggest the presence of a uranyl hydroxide (UO₂(OH)₂) as the principal reaction product. An analysis of the crystalline products indicate a progressive decrease in concentration of cerium; from 26, to 20, and finally 11 ppm for crystals produced in 7-, 35-, and 190-day tests, respectively (K_d = 14, 11, 3, respectively). Results with neodymium display a similar trend, with concentrations in the solid decreasing from 1240 to 922 ppm between 7 and 35 days of reaction (K_d = 14 and 11, respectively). The decreasing concentration of REEs in the uranyl crystals can be correlated with both a coarsening in crystal size and a decrease in the concentration of dissolved uranium over time. Thus, REE incorporation in the crystalline solids decreases in conjunction with a decrease in the ratio of surface area/volume of the crystals, a decrease in the rate of crystal growth as uranium concentrations are lowered, or both. These data also suggest that adsorption of REE (and by analogy, actinides) onto crystal surfaces and subsequent trapping by crystal overgrowth processes may play key roles in the limiting the mobility of radionuclides in a nuclear waste repository.

Titanate-based ceramic waste forms are currently under development for the immobilization of excess weapons plutonium. Both Hf and Gd are added to the ceramic formulation as neutron absorbers in order to satisfy a defense-in-depth concept for the waste form. The introduction of significant amounts of hafnium may be responsible for the presence of zirconolite-2M crystals in pyrochlore-based ceramics and the formation of zirconolite lamellae within pyrochlore. The zirconolite grows epitaxially on { 111 }planes of pyrochlore. Although the zirconolite lamellae within pyrochlore are non-cubic, any volume expansion due to radiation damage in the pyrochlore should still be isotropic; in addition, the presence of these intergrowths may allow some stress relief in the ceramic.

We report results of experimental studies on the behavior of Np during aqueous corrosion of unirradiated Np-bearing U oxides. Np-doped U oxides were reacted in humid air at 90°C and 150°C for several weeks within sealed stainless-steel vessels. Reacted solids were examined by scanning and transmission electron microscopies (SEM and TEM), electron energy-loss spectroscopy (EELS), and X-ray powder diffraction (XRD). Dehydrated schoepite, (UO₂)O_0.25-z(OH)_1.5+2z (0 ≤z ≤0.15), is the predominant U(VI) compound formed in these experiments. Preliminary EELS analysis on crushed grains verify that dehydrated schoepite formed at 150°C contains up to approximately 2 wt.% Np, corresponding to a maximum Np:U molar ratio of approximately 1:40. These are maximum values because the degree to which surface-sorbed Np is present on the grains analyzed is not yet known. Crystalline NpO₂ also precipitated during these experiments, and the concentration of Np in dehydrated schoepite may represent the maximum amount of Np that can be incorporated into dehydrated schoepite under the experimental conditions.

We have characterized uranyl peroxide phases on commercial spent nuclear fuel (SNF) samples formed under immersion conditions. At short times, crystallites of metaschoepite were observed on the hydrated fuel particles. Over a two-year period, all evidences of metaschoepite disappeared and in many samples, the fuel particles appeared to be coated by a new alteration phase. Additionally, milligrams of corroded fuel aggregates were observed at the sample air-water interface in each sample. The corrosion phases on bulk fuel and on the suspended materials were examined by SEM, EDX, and XRD and were identified as studtite (UO₄·4H₂0) and metastudtite (UO₄·2H₂0), respectively. The reason for the partitioning of the two phases is unclear at this time. SEM micrographs of the bulk powders indicated extensive surface corrosion and fragmentation of particles.

Oxidative dissolution of spent UO₂ fuel in vapor and dripping groundwater at 90°C occurs via general corrosion at fragment surfaces. Dissolution along fuel-grain boundaries is also evident in samples contacted by the largest volumes of groundwater, and corroded grain boundaries extend at least 20 or 30 grains deep (> 200 μm), possibly throughout mm-sized fragments. Apparent dissolution of fuel along defects that intersect grain boundaries has produced 50 to 200 nm-diameter dissolution pits that penetrate 1–2 μm into each grain, giving rise to a “worm-like” texture along fuel-grain boundaries. Sub-micrometer-sized fuel shards are common between fuel grains and may contribute to the reactive surface area of fuel exposed to groundwater. Outer surfaces of reacted fuel fragments develop a fmne-grained layer of corrosion products adjacent to the fuel (5–15 μm thick). A more coarsely crystalline layer of corrosion products commonly covers the fine-grained layer, the thickness of which varies considerably among samples (from less than 5 μm to greater than 40 μm). The thickest and most porous corrosion layers develop on fuel fragments exposed to the largest volumes of groundwater. Corrosion-layer compositions depend strongly on water flux, with uranyl oxy-hydroxides predominating in vapor experiments, and alkali and alkaline earth uranyl silicates predominating in high drip-rate experiments. Low drip-rate experiments exhibit a complex assemblage of corrosion products, including phases identified in vapor and high drip-rate experiments.

Uranyl oxide hydrate phases are known to form during contact of oxide spent nuclear fuel with water under oxidizing conditions; however, less is known about the fate of fission and neutron capture products during this alteration. We describe, for the first time, evidence that neptunium can become incorporated into the uranyl secondary phase, dehydrated schoepite (UO₃•0.8H₂O). Based on the long-term durability of natural schoepite, the retention of neptunium in this alteration phase may be significant during spent fuel corrosion in an unsaturated geologic repository.

Advanced spectroscopic techniques provide new and unique tools for unraveling the nature of the electronic structure of actinide materials. Inelastic neutron scattering experiments, which address temporal aspects of lattice and magnetic fluctuations, probe electromagnetic multipole interactions and the coupling between electronic and vibrational degrees of freedom. Nuclear magnetic resonance clearly demonstrates different magnetic ground states at low temperature. Photoemission spectroscopy provides information on the occupied part of the electronic density of states and has been used to investigate the momentum-resolved electronic structure and the topology of the Fermi surface in a variety of actinide compounds. Furthermore, x-ray absorption and electron energy-loss spectroscopy have been used to probe the relativistic nature, occupation number, and degree of localization of 5f electrons across the actinide series. More recently, element- and edge-specific resonant and non-resonant inelastic x-ray scattering experiments have provided the opportunity of measuring elementary electronic excitations with higher resolution than traditional absorption techniques. Here, we will discuss results from these spectroscopic techniques and what they tell us of the electronic and magnetic properties of selected actinide materials.

The weathering of glass is reviewed by examining processes that affect the reaction of commercial, historical, natural, and nuclear waste glass under conditions of contact with humid air and slowly dripping water, which may lead to immersion in nearly static solution. Radionuclide release data from weathered glass under conditions that may exist in an unsaturated environment are presented and compared to release under standard leaching conditions. While the comparison between the release under weathering and leaching conditions is not exact, due to variability of reaction in humid air, evidence is presented of radionuclide release under a variety of conditions. These results suggest that both the amount and form of radionuclide release can be affected by the weathering of glass.

The contact of commercial spent nuclear fuel (CSNF) with water over a 2-year period led to an unexpected corrosion phase and morphology. At short hydration times, crystallites of metaschoepite [(UO₂)8O₂(OH)₁₂](H₂O)₁₀ were observed on the hydrated CSNF particles. Over the 2-year contact period, all evidence of metaschoepite disappeared, and the fuel particles were coated by a new alteration phase. Additionally, films of the reacted fuel were observed at the sample air-water interface of each sample. The corrosion phases on fuel powders and on the suspended films were examined by scanning electron microscopy, energy-dispersive X-ray fluorescence, and X-ray diffraction and were identified as studtite [(UO₂)(O₂)(H₂O)₂](H₂O)₂ and metastudtite (UO₄·2H₂O), respectively. The reason for the partitioning of the latter phase to the sample air-water interface is unclear at this time but may be due to structural differences between the two phases. Scanning electron micrographs of the CSNF powders indicated surface corrosion along grain boundaries and fragmentation of the primary solid. The occurrence of studtite and metastudtite on CSNF could have implications for the potential attenuation of released radionuclides during oxidative corrosion of CSNF in a geologic repository.

Immersing commercial spent nuclear fuel (CSNF) in deionized water produced two corrosion products after a 2-year contact period. Suspensions of aggregates were observed to form at the air–water interface for each of five samples. These suspended aggregates were characterized by X-ray diffraction (XRD) to be metastudtite (UO₄·2H₂O), while the corrosion present on the surface of the fuel itself was determined to be studtite [(UO₂)(O₂)(H₂O)₂](H₂O)₂]. The presence of unreacted UO₂matrix was below the limits of detection by XRD for the three samples examined. The result prompted a radiochemical analysis of the solids collected from the sample air–water interface. The analysis indicated that high concentrations of⁹⁰Sr,¹³⁷Cs, and⁹⁹Tc, relative to the fuel inventory, had concentrated at the air–water interface along with the aggregates of metastudtite. Concentrations of²⁴¹Am were at least two orders of magnitude lower than expected in these solids, and retention of²³⁷Np and²³⁹Pu into the corrosion product was observed. The combined radiochemical analyses of the air–water interface aggregates and leachate samples are a rare example of radionuclide partitioning to an alteration phase and may provide preliminary evidence for mechanisms that give rise to such noticeable departures from fuel-inventory values. The leachate radiochemical data are compared to existing data from hydration of the same CSNF.

The uranium(VI) silicate phases uranophane, Ca[(UO₂)(SiO₃OH)]₂·5H₂O, and sodium boltwoodite, Na[(UO₂)(SiO₃OH)]·1.5H₂O, were synthesized in the presence of small, variable quantities (0.5–2.0 mol % relative to U) of pentavalent neptunium (Np(V), as NpO₂ ⁺), to investigate the nature of its association with these U(VI) solid phases. Solids were characterized by X-ray powder diffraction (XRD), gamma spectrometry (GS), scanning electron microscopy (SEM) with energy-dispersive X-ray spectroscopy (EDS), and transmission electron microscopy (TEM) with electron energy-loss spectroscopy (EELS). Neptunium concentration was determined in the bulk solid phases by GS and was found to range from 780–15800 μg/g. In some cases, Np distributions between the aqueous and solid phases were monitored, and 78–97% of the initial Np was associated with the isolated solid. Characterization of individual crystallites by TEM/EELS suggests the Np is associated with the U(VI) phase. No discrete Np phases, such as Np oxides, were observed. Because the U(VI) silicates are believed to be important solubility-controlling solids on a geologic timescale, these results suggest that the partitioning of the minor actinides to these solids must be considered when assessing the performance of a waste repository for spent nuclear fuel.

Spent fuel from commercial nuclear reactors consists mainly of uranium oxide. However, the changes that occur during reactor operations have a profound effect on chemical and physical properties of this material. Heat build-up in the fuel pellet during reactor operations can cause redistribution of fission products. The fission products may aggregate in one of three types of precipitates; gaseous, metallic, or oxide, depending on the burn-up and in-core treatment. Radiation damage and variations in fission and neutron capture yields across the fuel pellets lead to Pu enrichment and increased porosity with increasing burn-up. A more porous surface may make the fuel more susceptible to oxidative dissolution. As the level of actinides and fission products increases, the fuel may become more resistant to oxidation. These changes may limit the usefulness of natural uraninite (UO ₂ ) analogues for predicting the geological behaviour of spent fuel disposed in a high-level waste (HLW) repository. In this Chapter, an overview of spent fuel microstructure, radiolytic effects, and alteration processes is presented. Evidence for Np incorporation into U ⁶⁺ phases, the nature of Pu surface precipitates on spent fuel, and evidence for the preferential removal of 4d-metals from ε-particles in corroded spent fuel is discussed. Understanding the potential mechanisms of radionuclide attenuation through sorption and/or incorporation requires techniques with both high spatial resolution and excellent elemental sensitivity.

Four titanate ceramics were characterized and tested. These ceramics were similar to those proposed for Pu disposition, with Ce as a surrogate for Pu. The baseline ceramic contained Ti, U, Ca, Hf, Gd, and Ce, and was made up of only four crystalline phases: pyrochlore, zirconolite, rutile, and brannerite. The three other ceramics contained different amounts of impurities that are expected in the feed. Impurities are defined as any element other than Ti, U, Ca, Hf, Gd, and Ce. The ceramics that contained impurities contained different phases than the baseline. The addition of impurities led to the absence of brannerite and the presence of amorphous silicate, Ca-Al-Ti, and perovskite phases. The results from 3 day, 90°C MCC-I tests with impurity ceramics were significantly different than the results from tests with the baseline ceramic. Overall, the addition of impurities to these titanate ceramics altered the phase assemblages, which in turn, affected the corrosion behavior.

The release fractions of the five elements in the ε-phase (⁹⁹Tc, ⁹⁷Mo, Ru, Rh, and Pd) as well as that of ²³⁸U are reported for the reaction of two oxide fuels (ATM-103 and ATM-106) in unsaturated tests under oxidizing conditions. The ⁹⁹Tc release fractions provide a lower limit for the magnitude of the spent fuel reaction. The ⁹⁹Tc release fractions indicate that a surface reaction might be the rate controlling mechanism for fuel reaction under unsaturated conditions and the oxidant is possibly H₂O₂, a product of alpha radiolysis of water.

The energy loss spectra of the rare earths are characterized by sharp M4,5 edges, the relative intensities of which are characteristic of the 4f-shell occupancy of the excited ion. For the light rare earths, the dependence of these relative peak heights on 4f-shell occupancy is quite pronounced. Thus they may be used to determine the oxidation state of the multivalent elements Ce and Pr. The second derivative of the spectrum is shown to be extremely sensitive to the chemical environment. Modern instrumentation and detection techniques allow the oxidation state of Ce and Pr to be determined even when they are present as only minor constituents.

The energy loss spectra of the rare earths are characterized by sharp M4,5 edges, the relative intensities of which are characteristic of the 4f-shell occupancy of the excited ion. For the light rare earths, the dependence of these relative peak heights on 4f-shell occupancy is quite pronounced. Thus they may be used to determine the oxidation state of the multivalent elements Ce and Pr. The second derivative of the spectrum is shown to be extremely sensitive to the chemical environment. Modern instrumentation and detection techniques allow the oxidation state of Ce and Pr to be determined even when they are present as only minor constituents.

Uranium‐contaminated soils from the U.S. Department of Energy (DOE) Fernald Site, Ohio, have been examined by a combination of backscattered electron imaging (BSE) and analytical electron microscopy with electron diffraction (AEM). The inhomogeneous distribution of particulate uranium phases in the soil required the development of a method for using ultramicrotomy to prepare transmission electron microscopy (TEM) thin sections from the SEM mounts. A water‐miscible resin was selected that allowed comparison between SEM and TEM images, permitting representative sampling of the soil. Uranium was found in iron oxides, silicates (soddyite), phosphates (autunites), and uraninite (UO_2+x). No uranium was detected in association with phyllosilicates in the soil. © 1995 Wiley‐Liss, Inc.

Electron beam techniques have been used to characterize uranium-contaminated soils at the Fernald Site, Ohio. Uranium particulates have been deposited on the soil through chemical spills and from the operation of an incinerator plant on the site. The major uranium phases have been identified by electron microscopy as uraninite, autunite, and uranium phosphite [U(PO₃)₄]. Some of the uranium has undergone weathering resulting in the redistribution of uranium within the soil.

Preliminary results for the composition of the leachate from unsaturated tests at 90°C with spent fuel for two successive periods of ~60 days each with pretreated J-13 groundwater are reported. The pH of the leachate solutions ranged from 4 to 7. The americium concentration was 10⁴ to 10⁵ greater than that reported for saturated spent fuel tests in which the leachate pH was 8. The major fraction of material in the leachate was present as colloids containing both americium and curium. The presence of actinides in a form not currently directly included in repository radionuclide transport models provides information that can be used in spent fuel reaction modeling, the performance assessment of the repository and the design of the engineering barrier system.

Static leach tests were performed in both 304L stainless steel and Teflon vessels using a synthetic high-level waste glass with either deionized water (DIW) or a tuff groundwater solution as the leachant to assess the effects of the vessel and the initial leachant composition on the extent and nature of the glass reaction. The tests were performed using monolith samples at 340 m⁻¹ and crushed samples at 2000 m⁻¹ for times up to 1 year. The results show less silicon is released from the glass into the groundwater solution than into DIW at both high and low glass surface area/leachant volume ratios (SA/V), but the alkali metal and boron releases are not affected by the leachant used. Tests performed in a stainless steel vessel resulted in slightly lower leachate pH values, but similar reaction rates to those performed in a Teflon vessel, as measured by the boron release. Blank tests with DIW or EJ-13 in the vessels showed the Teflon vessels to release small amounts of fluoride (1 to 2 ppm) and to acidify the DIW slightly (4.0 < pH < 5.6). The pH values of blank tests with EJ-13 increased from 8.2 to about 8.6 in steel and to about 9.2 in Teflon vessels. The slightly higher pH values attained in Teflon vessels are attributed to outgassing of CO₂ during the test.