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Anhydrous plutonium tetrafluoride is an important intermediate in the production of metallic Pu. This historically important compound is also known to exist in at least two distinct, yet understudied hydrate forms, PuF 4 · x H 2 O(s) (0.5 ≤ x ≤ 2) and PuF 4 ·2.5H 2 O(s). X-ray diffraction (XRD), thermogravimetric analysis (TGA), and scanning electron microscopy (SEM) are the most common tools used to characterize these materials, often in a context for studying structural and morphological changes that arise from aging or calcination. However, fundamental electronic and vibrational spectroscopic information is rather scarce. Here, we measured the visible and shortwave infrared (SWIR) diffuse reflectance, Fourier transform infrared (FTIR), fluorescence and Raman spectra of PuF 4 (s) and PuF 4 · x H 2 O(s) to obtain a better electronic and vibrational fingerprint. Our work provides clear indication of the polymeric structure of anhydrous PuF 4 , consistent with the Raman spectrum of UF 4 (s) and its hydrates. This is supplemented with XRD, TGA and SEM analysis. Findings in this study indicate that the spectra are modified by particle size, which in turn is influenced by synthetic technique.

Multiple bench-scale filtration campaigns of Hanford tank waste supernatant on a backpulseable dead-end filtration skid have provided greater insight into the solids that cause fouling and reduce filter performance. The solids collected during each campaign were concentrated from the backpulse solutions and examined using automated particle analysis (APA) methods with scanning electron microscopy and X-ray energy dispersive spectroscopy to categorize particle types and their morphological characteristics. We show that with APA, thousands of particles can be analyzed to provide accurate insight into the phases that may be impacting filter performance., Competing Interests: Declaration of Competing Interest All authors declare no competing financial interests., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Reported is the synthesis, crystal structure, and solid-state characterization of a new americium containing metal-organic framework (MOF), [Am(C 9 H 3 O 6 )(H 2 O)], MOF-76(Am) . This material is constructed from Am 3+ metal centers and 1,3,5-tricarboxylic acid (BTC) ligands, forming a porous three-dimensional framework that is isostructural with several known trivalent lanthanide (Ln) analogs (e.g., Ce, Nd, and Sm-Lu). The Am 3+ ions have seven coordinates and assume a distorted, capped trigonal prismatic geometry with C 1 symmetry. The Am 3+ -O bonds were studied via infrared spectroscopy and compared to several MOF-76(Ln) analogs, where Ln = Nd 3+ , Eu 3+ , Tb 3+ , and Ho 3+ . The results show that the strength of the ligand carboxylate stretching and bending modes increase with Nd 3+ < Eu 3+ < Am 3+ < Tb 3+ < Ho 3+ , suggesting the metal-oxygen bonds are predominantly ionic. Optical absorbance spectroscopy measurements reveal strong f - f transitions; some exhibit pronounced crystal field splitting. The photoluminescence spectrum contains weak Am 3+ -based emission that is achieved through direct and indirect metal center excitation. The weak emissive behavior is somewhat surprising given that ligand-to-metal resonance energy transfer is efficient in the isoelectronic Eu 3+ (4f 6 ) and related Tb 3+ (4f 8 ) analogs. The optical properties were explored further within a series of heterometallic MOF-76(Tb 1- x Am x ) ( x = 0.8, 0.2, and 0.1) samples, and the results reveal enhanced Am 3+ photoluminescence.

We report the structural, vibrational, and optical properties of americium formate (Am(CHO 2 ) 3 ) crystals synthesized via the in situ hydrolysis of dimethylformamide (DMF). The coordination polymer features Am 3+ ions linked by formate ligands into a three-dimensional network that is isomorphous to several lanthanide analogs, (e. g., Eu 3+ , Nd 3+ , Tb 3+ ). Structure determination revealed a nine-coordinate Am 3+ 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-O5 D 1' → 7 F 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., (© 2023 Battelle Memorial Institute and The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

We have developed a specialized microfluidic electrochemical cell that enables in situ investigation of the electrochemical corrosion of microgram quantities of redox active solids. The advantage of downscaling is the reduction of hazards, waste, expense, and greatly expanding data collection for hazardous materials, including radioactive samples. Cyclic voltammetry was used to monitor the oxidation-reduction cycle of minute quantities of micron-size uraninite (UO 2 ) particles, from the formation of hexavalent uranium (U(vi)), U 3 O 7 and reduction to UO 2+ x . Reaction progress was also studied in situ with scanning electron microscopy. The electrochemical measurements matched those obtained at the bulk-scale and were consistent with ex situ characterization of the run products by X-ray photoelectron spectroscopy, scanning transmission electron microscopy, and atomic force microscopy; thus, demonstrating the utility of the microfluidic approach for studying radioactive materials., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

We present a novel anode interface modification on the β″-alumina solid-state electrolyte that improves the wetting behavior of molten sodium in battery applications. Heat treating a simple slurry, composed only of water, acetone, carbon black, and lead acetate, formed a porous carbon network decorated with PbO x (0 ≤ x ≤ 2) nanoparticles between 10 and 50 nm. Extensive performance analysis, through impedance spectroscopy and symmetric cycling, shows a stable, low-resistance interface for close to 6000 cycles. Furthermore, an intermediate temperature Na-S cell with a modified β″-alumina solid-state electrolyte could achieve an average stable cycling capacity as high as 509 mA h/g. This modification drastically decreases the amount of Pb content to approximately 3% in the anode interface (6 wt % or 0.4 mol %) and could further eliminate the need for toxic Pb altogether by replacing it with environmentally benign Sn. Overall, in situ reduction of oxide nanoparticles created a high-performance anode interface, further enabling large-scale applications of liquid metal anodes with solid-state electrolytes.

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 (CeO 2 ) 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 (CeO 2 ) 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.

Our present understanding of surface dissolution of nuclear fuels such as uranium dioxide (UO 2 ) is limited by the use of nonlocal characterization techniques. Here we discuss the use of state-of-the-art scanning transmission electron microscopy (STEM) to reveal atomic-scale changes occurring to a UO 2 thin film subjected to anoxic dissolution in deionized water. No amorphization of the UO 2 film surface during dissolution is observed, and dissolution occurs preferentially at surface reactive sites that present as surface pits which increase in size as the dissolution proceeds. Using a combination of STEM imaging modes, energy-dispersive X-ray spectroscopy (STEM-EDS), and electron energy loss spectroscopy (STEM-EELS), we investigate structural defects and oxygen passivation of the surface that originates from the filling of the octahedral interstitial site in the center of the unit cells and its associated lattice contraction. Taken together, our results reveal complex pathways for both the dissolution and infiltration of solutions into UO 2 surfaces.

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., (© 2020. The Author(s).)

The ability to acquire high-quality spatially-resolved mass spectrometry data is sought in many fields of study, but it often comes with high cost of instrumentation and a high level of expertise required. In addition, techniques highly regarded for isotopic analysis applications such as thermal ionization mass spectrometry (TIMS) do not have the ability to acquire spatially-resolved data. Another drawback is that for radioactive materials, which are often of interest for isotopic analysis in geochemistry and nuclear forensics applications, high-end instruments often have restrictions on radioactivity and non-dispersibility requirements. We have applied the use of a traditional microanalysis tool, the focused ion beam/scanning electron microscope (FIB/SEM), for preparation of radioactive materials either for direct analysis by spatially-resolved instruments such as secondary ion mass spectrometry (SIMS) and laser ablation inductively-coupled mass spectrometry (LA-ICP-MS), or similarly to provide some level of spatial resolution to techniques that do not inherently have that ability such as TIMS or quadrupole inductively coupled plasma mass spectrometry (Q-ICP-MS). We applied this preparation technique to various uranium compounds, which was especially useful for reducing sample sizes and ensuring non-dispersibility to allow for entry into non-radiological or ultra-trace facilities. Our results show how this site-specific preparation can provide spatial context for nominally bulk techniques such as TIMS and Q-ICP-MS. In addition, the analysis of samples extracted from a uranium dioxide fuel pellet via all methods, but especially NanoSIMS and LA-ICP-MS, showed enrichment heterogeneities that are important for nuclear forensics and are of interest for fuel performance., (Copyright © 2020 The Authors. Published by Elsevier B.V. All rights reserved.)

A novel relationship between noble metal phase particles and fission gas bubble production in used nuclear fuel is described. The majority of Te atoms within noble metal phase undergo radioactive decay to form stable Xe within a few hours after particle formation. This results in the production of clusters of Xe atoms contained within the solid metal matrix exhibiting an equivalent gas bubble pressure approaching 1 GPa. These high pressure bubbles are stabilized by the UO 2 within the bulk of the fuel. However, when these bubbles form near the fuel/cladding interface, in combination with local and temporal damage caused by fission recoil, they are capable of overcoming the fracture strength of the UO 2 and rupturing catastrophically. The force of the resulting bubble rupture is sufficient to eject noble metal phase particles several microns into the cladding. This proposed mechanism explains the observance of noble metal phase in cladding and is consistent with a host of morphological features found near the fuel/cladding interface.

Although there have been advances in synthesizing hierarchical semiconductor materials,  few studies have investigated the fundamental nucleation mechanisms to explain the origins of such complex structures. Resolving these nucleation and growth pathways is technically challenging but  critical for developing predictive synthetic capabilities for the synthesis and application of new materials. In this Letter, we use state-of-the-art in situ liquid phase scanning electron microscopy (SEM) and high-resolution transmission electron microscopy in a combination with classical density functional theory (cDFT) to study the nucleation of highly branched wurtzite ZnO nanostructures via a facile, room-temperature aqueous synthesis route. Using a range of precursor concentrations, we systematically vary the hierarchical organization of these nanostructures. In situ liquid phase SEM demonstrates that all branches form through secondary nucleation and grow by classical processes. Neither random aggregation nor oriented attachment is observed. cDFT results imply that the morphological evolution with increasing [Zn 2+ ] arises from an interplay between a rising thermodynamic driving force, which promotes branch number and variability of orientation, and increasing barriers to interfacial transport due to ion correlation forces that alter the anisotropic kinetics of growth. These findings provide a quantitative picture of branching that sets to rest past controversies and advances efforts to decipher growth mechanisms of hierarchical structures in real solution environments.

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 [Formula: see text] 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 [Formula: see text] surface oxidation., Competing Interests: The authors declare no conflict of interest., (Copyright © 2019 the Author(s). Published by PNAS.)

We report elemental and isotopic analysis for the noble metal fission product phase found in irradiated nuclear fuel. The noble metal phase was isolated from three commercial irradiated UO 2 fuels by chemically dissolving the UO 2 fuel matrix, leaving the noble metal phase as the undissolved residue. Macro amounts of this residue were dissolved using a KOH + KNO 3 fusion and then chemically separated into individual elements for analysis by mass spectrometry. Though the composition of this phase has been previously reported, this work is the most comprehensive chemical analysis of the isolated noble metal phase to date. We report both elemental and isotopic abundances of the five major components of the noble metal phase (Mo, Tc, Ru, Rh, Pd). In addition, we report a sixth element present in high quantities in this phase, tellurium. Tellurium appears to be an integral component of noble metal particles.

Zircaloy-4 (Zr-4) based liners and getters are the principle functional components of Tritium-Producing Burnable Absorber Rods (TPBARs) in light water nuclear reactors where they reduce tritiated water into tritium gas. Upon tritium exposure, zirconium tritide is formed, which changes the chemical composition, structure and morphology of these materials. Their thermodynamic properties are affected by (i) the hydride phase identity, (ii) radial and spatial tritide/hydride (T/H) distribution, and (iii) the changes in structure and morphology of the material upon T/H-migration, and their comprehensive knowledge is needed to predict performance of these materials. This work demonstrates that controlled potential electrochemistry techniques to be highly efficient for controlled oxidative radial dissolution of Zr-4 based liners (both unloaded and loaded with hydride/deuteride as chemical surrogates for tritium). The electrodissolution is further combined with microscopic techniques to accurately determine the distribution of hydride phases. This work demonstrates a reliable technique for radially etching the liners after irradiation to provide insight into the radial and spatial distribution of tritium within the TPBAR, improving the fundamental understanding of tritium transport and providing a basis for validating predictive models., Competing Interests: The authors declare no conflicts of interest., (This journal is © The Royal Society of Chemistry.)

A simple, repeatable method for determination of the degree of grain refinement in irradiated Uranium-Molybdenum fuels has been developed. This method involves mechanical potting and polishing of samples along with examination using a scanning electron microscope located outside of a hot cell. The commercially available software package Mathematica was used to determine the degree of grain refinement by way of a built-in iterative active contour method of image segmentation. Baseline methods for degree of grain refinement assessment are suggested for consideration and further development.

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. This could be useful for investigating accelerated alteration of UO 2 and can be also used to monitor radiolytic effects. Low concentrations of bromide in aqueous solutions are known to reduce the generation rate of H 2 O 2 during radiolysis and increase H 2 production. We deduced the presence of radiolytic H 2 O 2 by monitoring the formation of a uranyl peroxide solid from both solid UO 2 and a solution of ammonium uranyl carbonate at neutral pH. Additionally, the effect of bromine on water radiolysis was investigated through chemical modelling and in situ electron microscopy. By measuring the contrast in the electron microscopy images it was possible to monitor H 2 O 2 formation and diffusion from the irradiated zone in agreement with the models., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

This Critical Review reviews the origin and chemical and rheological complexity of radioactive waste at the U.S. Department of Energy Hanford Site. The waste, stored in underground tanks, was generated via three distinct processes over decades of plutonium extraction operations. Although close records were kept of original waste disposition, tank-to-tank transfers and conditions that impede equilibrium complicate our understanding of the chemistry, phase composition, and rheology of the waste. Tank waste slurries comprise particles and aggregates from nano to micro scales, with varying densities, morphologies, heterogeneous compositions, and complicated responses to flow regimes and process conditions. Further, remnant or changing radiation fields may affect the stability and rheology of the waste. These conditions pose challenges for transport through conduits or pipes to treatment plants for vitrification. Additionally, recalcitrant boehmite degrades glass quality and the high aluminum content must be reduced prior to vitrification for the manufacture of waste glass of acceptable durability. However, caustic leaching indicates that boehmite dissolves much more slowly than predicted given surface normalized rates. Existing empirical models based on ex situ experiments and observations generally only describe material balances and have not effectively predicted process performance. Recent advances in the areas of in situ microscopy, aberration-corrected transmission electron microscopy, theoretical modeling across scales, and experimental methods for probing the physics and chemistry at mineral-fluid and mineral-mineral interfaces are being implemented to build robustly predictive physics-based models.

A cementitious waste form, Cast Stone, is a possible candidate technology for the immobilization of low activity nuclear waste (LAW) at the Hanford site. This work focuses on the addition of getter materials to Cast Stone that can sequester Tc from the LAW, and in turn, lower Tc release from the Cast Stone. Two getters which produce different products upon sequestering Tc from LAW were tested: Sn(II) apatite (Sn-A) that removes Tc as a Tc(IV)-oxide and potassium metal sulfide (KMS-2) that removes Tc as a Tc(IV)-sulfide species, allowing for a comparison of stability of the form of Tc upon entering the waste form. The Cast Stone with KMS-2 getter had the best performance with addition equivalent to ∼0.08wt% of the total waste form mass. The observed diffusion (D obs ) of Tc decreased from 4.6±0.2×10 -12 cm 2 /s for Cast Stone that did not contain a getter to 5.4±0.4×10 -13 cm 2 /s for KMS-2 containing Cast Stone. It was found that Tc-sulfide species are more stable against re-oxidation within getter containing Cast Stone compared with Tc-oxide and is the origin of the decrease in Tc D obs when using the KMS-2., (Copyright © 2017 Elsevier B.V. All rights reserved.)

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.

Chemical stabilization of tank residual waste is part of a Hanford Site tank closure strategy to reduce overall risk levels to human health and the environment. In this study, a set of column leaching experiments using tank C-104 residual waste were conducted to evaluate the leachability of uranium (U) and technetium (Tc) where grout and hydrated lime were applied as chemical stabilizing agents. The experiments were designed to simulate future scenarios where meteoric water infiltrates through the vadose zones into the interior of the tank filled with layers of grout or hydrated lime, and then contacts the residual waste. Effluent concentrations of U and Tc were monitored and compared among three different packing columns (waste only, waste + grout, and waste + grout + hydrated lime). Geochemical modeling of the effluent compositions was conducted to determine saturation indices of uranium solid phases that could control the solubility of uranium. The results indicate that addition of hydrated lime strongly stabilized the uranium through transforming uranium to a highly insoluble calcium uranate (CaUO 4 ) or similar phase, whereas no significant stabilization effect of grout or hydrated lime was observed on Tc leachability. The result implies that hydrated lime could be a great candidate for stabilizing Hanford tank residual wastes where uranium is one of the main concerns., (Published by Elsevier Ltd.)

Uranyl nitrate is a key species in the nuclear fuel cycle. However, this species is known to exist in different states of hydration, including the hexahydrate ([UO2(NO3)2(H2O)6] often called UNH), the trihydrate [UO2(NO3)2(H2O)3 or UNT], and in very dry environments the dihydrate form [UO2(NO3)2(H2O)2]. Their relative stabilities depend on both water vapor pressure and temperature. In the 1950s and 1960s, the different phases were studied by infrared transmission spectroscopy but were limited both by instrumental resolution and by the ability to prepare the samples for transmission. We have revisited this problem using time-resolved reflectance spectroscopy, which requires no sample preparation and allows dynamic analysis while the sample is exposed to a flow of N2 gas. Samples of known hydration state were prepared and confirmed via X-ray diffraction patterns of known species. In reflectance mode the hexahydrate UO2(NO3)2(H2O)6 has a distinct uranyl asymmetric stretch band at 949.0 cm(-1) that shifts to shorter wavelengths and broadens as the sample desiccates and recrystallizes to the trihydrate, first as a shoulder growing in on the blue edge but ultimately results in a doublet band with reflectance peaks at 966 and 957 cm(-1). The data are consistent with transformation from UNH to UNT as UNT has two inequivalent UO2(2+) sites. The dehydration of UO2(NO3)2(H2O)6 to UO2(NO3)2(H2O)3 is both a structural and morphological change that has the lustrous lime green UO2(NO3)2(H2O)6 crystals changing to the matte greenish yellow of the trihydrate solid. The phase transformation and crystal structures were confirmed by density functional theory calculations and optical microscopy methods, both of which showed a transformation with two distinct sites for the uranyl cation in the trihydrate, with only one in the hexahydrate.

We report on a subtle global feature of the mass action kinetics equations for water radiolysis that results in predictions of a critical behavior in H2O2 and associated radical concentrations. While radiolysis kinetics have been studied extensively in the past, it is only in recent years that high-speed computing has allowed the rapid exploration of the solution over widely varying dose and compositional conditions. We explore the radiolytic production of H2O2 under various externally fixed conditions of molecular H2 and O2 that have been regarded as problematic in the literature-specifically, "jumps" in predicted concentrations, and inconsistencies between predictions and experiments have been reported for α radiolysis. We computationally map-out a critical concentration behavior for α radiolysis kinetics using a comprehensive set of reactions. We then show that all features of interest are accurately reproduced with 15 reactions. An analytical solution for steady-state concentrations of the 15 reactions reveals regions in [H2] and [O2] where the H2O2 concentration is not unique-both stable and unstable concentrations exist. The boundary of this region can be characterized analytically as a function of G-values and rate constants independent of dose rate. Physically, the boundary can be understood as separating a region where a steady-state H2O2 concentration exists from one where it does not exist without a direct decomposition reaction. We show that this behavior is consistent with reported α radiolysis data and that no such behavior should occur for γ radiolysis. We suggest experiments that could verify or discredit a critical concentration behavior for α radiolysis and could place more restrictive ranges on G-values from derived relationships between them.

Time-dependent reduction of PuO(2)(am) was studied over a range of pH values in the presence of aqueous Fe(II) and magnetite (Fe(3)O(4)) nanoparticles. At early time frames (up to 56 days) very little aqueous Pu was mobilized from PuO(2)(am), even though measured pH and redox potentials, coupled to equilibrium thermodynamic modeling, indicated the potential for significant reduction of PuO(2)(am) to relatively soluble Pu(III). Introduction of Eu(III) or Nd(III) to the suspensions as competitive cations to displace possible sorbed Pu(III) resulted in the release of significant concentrations of aqueous Pu. However, the similarity of aqueous Pu concentrations that resulted from the introduction of Eu(III)/Nd(III) to suspensions with and without magnetite indicated that the Pu was solubilized from PuO(2)(am), not from magnetite.

This study measured reductive solubilization of plutonium(IV) hydrous oxide (Pu(IV)O(2)·xH(2)O((am))) with hydrogen (H(2)) as electron donor, in the presence or absence of dissimilatory metal-reducing bacteria (DMRB), anthraquinone-2,6-disulfonate (AQDS), and ethylenediaminetetraacetate (EDTA). In PIPES buffer at pH 7 with excess H(2), Shewanella oneidensis and Geobacter sulfurreducens both solubilized <0.001% of 0.5 mM Pu(IV)O(2)·xH(2)O((am)) over 8 days, with or without AQDS. However, Pu((aq)) increased by an order of magnitude in some treatments, and increases in solubility were associated with production of Pu(III)((aq)). The solid phase of these treatments contained Pu(III)(OH)(3(am)), with more in the DMRB treatments compared with abiotic controls. In the presence of EDTA and AQDS, PuO(2)·xH(2)O((am)) was completely solubilized by S. oneidensis and G. sulfurreducens in ∼24 h. Without AQDS, bioreductive solubilization was slower (∼22 days) and less extensive (∼83-94%). In the absence of DMRB, EDTA facilitated reductive solubilization of 89% (without AQDS) to 98% (with AQDS) of the added PuO(2)·xH(2)O((am)) over 418 days. An in vitro assay demonstrated electron transfer to PuO(2)·xH(2)O((am)) from the S. oneidensis outer-membrane c-type cytochrome MtrC. Our results (1) suggest that PuO(2)·xH(2)O((am)) reductive solubilization may be important in reducing environments, especially in the presence of complexing ligands and electron shuttles, (2) highlight the environmental importance of polynuclear, colloidal Pu, (3) provide additional evidence that Pu(III)-EDTA is a more likely mobile form of Pu than Pu(IV)-EDTA, and (4) provide another example of outer-membrane cytochromes and electron-shuttling compounds facilitating bioreduction of insoluble electron acceptors in geologic environments.

During the nuclear waste vitrification process volatilized (99)Tc will be trapped by melter off-gas scrubbers and then washed out into caustic solutions, and plans are currently being contemplated for the disposal of such secondary waste. Solutions containing pertechnetate [(99)Tc(VII)O(4)(-)] were mixed with precipitating goethite and dissolved Fe(II) to determine if an iron (oxy)hydroxide-based waste form can reduce Tc(VII) and isolate Tc(IV) from oxygen. The results of these experiments demonstrate that Fe(II) with goethite efficiently catalyzes the reduction of technetium in deionized water and complex solutions that mimic the chemical composition of caustic waste scrubber media. Identification of the phases, goethite + magnetite, was performed using XRD, SEM and TEM methods. Analyses of the Tc-bearing solid products by XAFS indicate that all of the Tc(VII) was reduced to Tc(IV) and that the latter is incorporated into goethite or magnetite as octahedral Tc(IV). Batch dissolution experiments, conducted under ambient oxidizing conditions for more than 180 days, demonstrated a very limited release of Tc to solution (2-7 μg Tc/g solid). Incorporation of Tc(IV) into the goethite lattice thus provides significant advantages for limiting reoxidation and curtailing release of Tc disposed in nuclear waste repositories.

Heterogeneous reduction of actinides in higher, more soluble oxidation states to lower, more insoluble oxidation states by reductants such as Fe(II) has been the subject of intensive study for more than two decades. However, Fe(II)-induced reduction of sparingly soluble Pu(IV) to the more soluble lower oxidation state Pu(III) has been much less studied, even though such reactions can potentially increase the mobility of Pu in the subsurface. Thermodynamic calculations are presented that show how differences in the free energy of various possible solid-phase Fe(III) reaction products can greatly influence aqueous Pu(III) concentrations resulting from reduction of PuO₂(am) by Fe(II). We present the first experimental evidence that reduction of PuO₂(am) to Pu(III) by Fe(II) was enhanced when the Fe(III) mineral goethite was spiked into the reaction. The effect of goethite on reduction of Pu(IV) was demonstrated by measuring the time dependence of total aqueous Pu concentration, its oxidation state, and system pe/pH. We also re-evaluated established protocols for determining Pu(III) {[Pu(III) + Pu(IV)] - Pu(IV)} by using thenoyltrifluoroacetone (TTA) in toluene extractions; the study showed that it is important to eliminate dissolved oxygen from the TTA solutions for accurate determinations. More broadly, this study highlights the importance of the Fe(III) reaction product in actinide reduction rate and extent by Fe(II).

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 used bona 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.

This paper examines the problems associated with analysis of low levels of neptunium in a uranium matrix with electron energy-loss spectroscopy (EELS) on the transmission electron microscope (TEM). The detection of neptunium in a matrix of uranium can be impeded by the occurrence of a plural scattering event from uranium (U-M(5)+U-O(4,5)) that results in severe overlap on the Np-M(5) edge at 3665 eV. Low levels of Np (1600-6300 ppm) can be detected in a uranium solid, uranophane [Ca(UO(2))(2)(SiO(3)OH)(2)(H(2)O)(5)], by confirming that the energy gap between the Np-M(5) and Np-M(4) edges is at 184 eV and showing that the M(4)/M(5) ratio for the neptunium is smaller than that for uranium. The Richardson-Lucy deconvolution method was applied to energy-loss spectral images and was shown to increase the signal to noise ratio.

The heterogeneous reduction of U(VI) to U(IV) by ferrous iron is believed to be a key process influencing the fate and transport of U in the environment. The reactivity of both sorbed and structural Fe(II) has been studied for numerous substrates, including magnetite. Published results from U(VI)-magnetite experiments have been variable, ranging from no reduction to clear evidence for the formation of U(IV). In this contribution, we used XAS and high resolution (+/-cryogenic) XPS to study the interaction of U(VI) with nanoparticulate magnetite. The results indicated that U(VI) was partially reduced to U(V) with no evidence of U(IV). However, thermodynamic calculations indicated that U phases with average oxidation states below (V) should have been stable, indicating that the system was not in redox equilibrium. A reaction pathway that involves incorporation and stabilization of U(V) and U(VI) into secondary phases is invoked to explain the observations. The results suggest an important and previously unappreciated role of U(V) in the fate and transport of uranium in the environment.

A sample of high-level radioactive tank waste was characterized to provide a basis for developing a waste simulant. The simulant is required for pilot-scale testing of pretreatment processes in a nonradiological facility. The waste material examined was derived from the bismuth phosphate process, which was the first industrial process implemented to separate plutonium from irradiated nuclear fuel. The bismuth phosphate process sludge is a complex mixture rich in bismuth, iron, sodium, phosphorus,silicon, and uranium.The form of phosphorus in this particular tank waste material is of specific importance because that is the primary component (other than water-soluble sodium salts) that must be removed from the high-level waste solids by pretreatment. This work shows unequivocally that the phosphorus in this waste material is not present as bismuth phosphate. Rather, the phosphorus appears to be incorporated mostly into an amorphous iron(III) phosphate phase. The bismuth in the sludge solids is best described as BiFeO3. The behavior of phosphorus during caustic leaching of the bismuth phosphate process sludge solids is also discussed.

Benchmarking of clinical laboratory activities has become a tool used increasingly to enable administrators and managers to obtain an independent evaluation of the performance of the laboratory and identify opportunities for improvement. Benchmarking is particularly important because of the diversity and complexity of the various sections of the laboratory. The critical component of laboratory benchmarking is peer comparison, as solutions to shortcomings or problems can be titrated and planned through this process. The reliability of benchmarking must be supplemented and modified by the input of the manager's detailed understanding of local circumstances. At this critical moment, the changes in peer review strategies instituted by JCAHO, CAP, CLIA, and individual states create an urgent opportunity to assist medical directors and laboratory managers in maintaining an overview of the performance and quality of laboratory operations. Unannounced site visits will require prompt reports and alerts of undesirable changes in performance. The future goals of benchmarking must expand to include surveys of laboratory test utilization and patient outcomes as ultimate measures of test utility in the clinical process and important assessments of the quality of patient care.

Metaschoepite, [(UO2)8O2(OH)12] x 10H2O, and metastudtite, UO4 x 4H2O, are alteration phases anticipated in a spent nuclear fuel repository following the moist oxidation of UO2 on a geologic time scale. Dissolved concentrations and hence potential mobility of other radionuclides in the fuel, such as the neptunyl cation (NpO2+), will likely be determined by the extent of their partitioning into these U(VI) solids. 237Np is of particular interest due to its potential high mobility and long half-life (2.1 x 10(6) years.) In this study, metaschoepite has been precipitated and subsequently transformed to studtite in the presence of dissolved Np. The metaschoepite and studtite solids that formed initially contained <10 and 6500 ppm Np, respectively. Batch dissolution studies of these solids at pH 6 demonstrate release of Np that exceeds congruent dissolution of U from metastudtite; furthermore, the released Np cation remains in solution. Thus, although the Np partitions into the metastudtite solid initially, it is released to solution over time, indicating that metastudtite is not likely to serve as a host solid for Np incorporation or sorption of the neptunyl cation on long time scales.

The chemistry of underground storage tanks containing high-level waste at the Hanford Site in Washington State is an area of continued research interest. Thermodynamic models have predicted the formation of analcime and clinoptilolite in Hanford tanks, rather than cancrinite; however, these predictions were based on carbonate-cancrinite. We report the first observation of a nitrate-cancrinite [possibly Na8(K,Cs)(AlSiO4)6(NO3)2 x nH2O] extracted from a Hanford tank 241-AP-101 sample that was evaporated to 6, 8, and 10 M NaOH concentrations. The nitrate-cancrinite phase formed spherical aggregates (4 microm in diameter) that consisted of platy hexagonal crystals (approximately 0.2 microm thick). Cesium-137 was concentrated in these aluminosilicate structures. These phases possessed a morphology identical to that of nitrate-cancrinite synthesized using simulant tests of nonradioactive tank waste, supporting the contention that it is possible to develop nonradioactive artificial sludges. This investigation points to the continued importance of understanding the solubility of NO3-cancrinite and related phases. Knowledge of the detailed structure of actual phases in the tank waste helps with thermodynamic modeling of tank conditions and waste processing.

Plutonium-enriched layer has been observed in corroded spent uranium oxide fuel (CSNF). These Pu-enriched regions were examined with analytical transmission electron microscopy combined with electron energy-loss spectroscopy (EELS). The enriched region also contained U, Am, Ru, Zr, but only minor enrichment of rare earth elements. The Pu, possibly as Pu(V) according to EELS measurements, was dispersed within re-precipitated uranium oxide (identified as U3O8) nano-crystals between U(VI) secondary phases and the CSNF surface. The U, Pu, and Am enrichment was observed in the corrosion products with tests on different nuclear fuels. This may have implications for the long-term behavior of CSNF under storage in a geologic waste repository. Furthermore, there may be an increased potential for the generation of Pu-bearing colloids from this type of weathered CSNF.

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 (UO2 + x). No uranium was detected in association with phyllosilicates in the soil.