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High-throughput ion irradiation of additively manufactured compositionally complex alloys

Several advanced nuclear reactor designs promise efficiency and safety improvements over the current reactor fleet but are limited by the current set of ASME code-qualified materials. Novel alloys including high-entropy alloys (HEAs), and more broadly compositionally complex alloys (CCAs), have shown promising irradiation-tolerance. However, the vast range of alloy compositions adds to an already time-consuming alloy development process. In this study, to accelerate the development of novel alloys for nuclear applications, a high-throughput (HTP) methodology has been employed. Additive manufacturing has been used to produce a compositional array of unary, binary, ternary, and quaternary alloys, including several CCAs, which span the Cr-Fe-Mn-Ni composition space. Additionally, the compositional array was homogenized at 1000°C for 24 hours and each sample was irradiated using 4-MeV Ni2+ ions at room temperature to a peak damage of 50 dpa, as estimated using SRIM, at the University of Wisconsin Ion Beam Laboratory. A custom XY stage was built to accommodate the large compositional array and half of each sample was masked during irradiation enabling both the irradiated and unirradiated properties of each alloy to be characterized side-by-side. Each alloy was characterized using X-ray fluorescence (XRF), X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and nanoindentation. CALPHAD simulations spanning the entire Cr-Fe-Mn-Ni composition space at 1000°C were performed to compare predicted equilibrium phases with phases identified experimentally from the unirradiated regions of each alloy. Nanoindentation measurements indicate radiation-induced hardening ranging from ~1-1.5 GPa in each of Cr-Fe-Mn-Ni CCAs, which is relatively insensitive to modest changes in alloy composition and comparable to hardening observed in neutron irradiated Cr-Fe-Mn-Ni CCAs in the literature. Overall, a substantial time savings was realized by employing HTP synthesis, irradiation, and characterization in this study compared to conventional techniques, the implications of which are discussed.

36 MATERIALS SCIENCE↗

Geochemical and Microstructural Characterization of Shale Rock: A Workflow for Site Evaluation for Energy–Fluids Storage

Shales are a central component of petroleum systems, as source, seal, and unconventional reservoir rocks. Unlike traditional unconventional shale, a newly emerging Caney Shale play is regarded as an unconventional of unconventional shales (UUS), due to its high content of fine-grained materials, lower reservoir porosity, dominance of nanopores, and a scarcity of visible natural fractures. Other developed unconventional shales such as the Woodford and Barnett have larger average pore size, higher porosity, and extensive natural fractures at core scale that contribute to reservoir quality. In this work, the Caney Shale was cored in entirety to characterize its interbedded ductile and reservoir intervals and establish criteria for their recognition. Representative ductile and reservoir intervals known as D2 and R3, respectively, were selected for detailed analysis including variations in elemental composition, mineralogy, facies, and the presence of natural fractures at well and core scales using X-ray fluorescence, X-ray diffraction, and thin section and core description. Characteristics of microstructure and microgeochemistry at nano- and microscales are compared using field emission scanning electron microscopy with energy dispersive spectroscopy and lowpressure nitrogen adsorption isotherms with fractal dimension analysis. The ductile (detrital clay-rich) member D2 is characterized by higher concentrations of Ti and Al and lower Si, while the reservoir R3 (possibly biogenic silica-accumulated) is characterized by lower Ti and Al and higher Si. Eight mixed carbonate–siliciclastic facies are recognized, and R3 shows a higher heterogeneity of facies stacking and average fracture abundance than D2. Further, R3 shows a more microscopically heterogeneous fabric/texture of matrix and a higher microporosity than D2 that has a higher pore surface heterogeneity. A fundamental understanding of the compositional and microstructural characteristics of UUS and further ductile/reservoir intervals will allow for a better assessment of reservoir quality, more effective production of hydrocarbons, and optimized selection of safe caprocks in carbon sequestration and subsurface hydrogen storage.

58 GEOSCIENCES↗

Self‐Assembly Methods Induce Different Individual‐Polymer‐Block Solvation Responses

An understanding of block-specific responses to stimuli in self-assembled copolymers is essential for the effective design of responsive materials. Here, materials formed from different post-reaction processing methods of the same ROMP block copolymer exhibit different block-specific solvent responses, as characterized in situ by fluorescence lifetime imaging microscopy (FLIM). FLIM data were acquired by tagging the polar or nonpolar block separately with a covalently incorporated viscosity-sensitive fluorescent molecular rotor to measure the changing tightness or looseness of assembly upon changes in solvent composition. Rapid precipitation from an insoluble solvent to form a film results in tighter assembly and less difference in tightness/looseness between the two blocks. Further, it interrupts individual block-solvent response behavior. Both results indicate an apparent disruption of the core–shell assembly. This model from FLIM is further supported by differential scanning calorimetry (DSC) and small-angle X-ray scattering (SAXS) data from isolated solids, which show tighter long-range interactions and more long-range order in these kinetically trapped states. Here, the experiments develop FLIM as a method for pinpointing stimuli-responsive behaviors from different processing methods to individual blocks. Together these outcomes provide a future handle for tailoring solvent-triggered assembly/disassembly behavior.

López, Pía A. [University of California, Irvine, C↗

Comparison of the Chemical Composition of Liquids from the Pyrolysis and Hydrothermal Liquefaction of Lignocellulosic Materials

Major differences in thermal stability and hydrotreatment behavior of HTL and pyrolysis oils have been reported in the literature. However, little is known about the variations in the chemical composition of these oils that could explain such differences. Two commercial wood pyrolysis oils (Pyrovac and BTG), and their water-soluble (WS) and water-insoluble fractions (WIS) were analyzed and compared with the aqueous (WS WD-57 ) and oily (WIS WS-57 ) fractions obtained from hydrothermal liquefaction (HTL) of Douglas-fir. The samples were characterized by GC/MS, Karl Fischer titration, carbonyl content, total acid number, elemental composition, calorific value, proximate analysis, Fourier Transform Infrared Spectroscopy (FTIR), Folin-Ciocalteu (FC), and UV fluorescence. All the fractions were also analyzed by Fourier Transform Ion Cyclotron Resonance Mass Spectroscopy (FT-ICR-MS) and by Electrospray Ionization (EI). The most prevalent class of compounds in the water insoluble phases were phenols derived from lignin. Water-soluble phases contain mostly the oxygenated compounds derived from cellulose and hemicellulose and were richer in carbonyl functional groups. The water content of the resulting aqueous phases were between: 65 (WS BTG ) and 96 (WS Pyrovac ) wt. %. The bio-oil from BTG has higher water content and lower HHV, compared to Pyrovac oil. The GC/MS results of BTG oil show the presence of a more prominent acetic acid peak and higher TAN number than the Pyrovac oil. The GC/MS of Pyrovac oil showed more obvious mono-phenol peaks. The quantification of this family by Folin-Ciocalteu method confirmed higher content of monophenolic compounds compared with the BTG oil. The lower thermal stability of pyrolysis oils compared with HTL biocrudes can be partially explained by the fact that pyrolysis oils (BTG and Pyrovac) contain carbohydrates while HTL biocrude (WIS WD-57 ) doesn’t. Thus, we decided to further investigate the chemical differences between the phenolic rich fractions insoluble in water and the holocellulose derived compounds soluble in water. Even after water extraction, the acid content of the water insoluble fraction from BTG (WISBTG) was higher than the acid content of the water insoluble fraction obtained by HTL (WISWSD-57). Likewise, the acid content of the aqueous phases derived from pyrolysis oils (WS Pyrovac , WS BTG ) was also higher than for the aqueous phase obtained by HTL (WSWSD-57). This result is in part due to the use of bases in the HTL process that neutralizes the acid formed in that process. Moreover, the starting feedstock may also influence the differences between the oils. Although, the UV-Fluorescence spectra, ICR-MS and the EI analyses showed some minor differences in the molecular weight and chemical make-up of the oligomers soluble and insoluble in water from pyrolysis and HTL; the differences observed were not large enough to justify the differences in behavior between these oils reported in the literature. Our results suggest that the differences observed between HTL biocrudes and pyrolysis oils are likely partially due to the presence of holocellulose derived products in the pyrolysis oils and higher acid contents.

09 BIOMASS FUELS↗

Apollo 15 geochemical X-ray fluorescence experiment - Preliminary report.

Although only part of the information from the X-ray fluorescence geochemical experiment has been analyzed, it is clear that the experiment was highly successful. Significant compositional differences among and possibly within the maria and highlands have been detected. When viewed in the light of analyzed lunar rocks and soil samples, and the data from other lunar orbital experiments (in particular, the Apollo 15 gamma-ray spectroscopy experiment), the results indicate the existence of a differential lunar highland crust, probably feldspathic. This crust appears to be related to the plagioclase-rich materials previously found in the samples from Apollo 11, Apollo 12, Apollo 14, Apollo 15, and Luna 16.

Adler, I.↗

Petrology of basalt and single-mineral fragments in the soil of the Sea of Fertility

Basalt and single-mineral particles, ranging from 150 to 425 microns, from the Luna-16 sample are studied by electron microanalysis, X-ray fluorescence analysis, and petrographic techniques. Three basalt species of different structure are identified. The structure and composition of the individual minerals (in particular of pyroxenes) indicate that the basalts have crystallized under conditions similar to those established for Apollo-11 samples.

Bence, A. E.↗

CHEMIN: A Mineralogical Dust Analyzer for the Odyssey Mission to Comet Kopff

The Odyssey spacecraft will be launched in June 2006 and will rendezvous with periodic Comet Kopff in September 2009. Odyssey will initially perform slow flybys of the active Kopff nucleus at distances between 500 and 100 km, and will then be placed in orbit around the nucleus at altitudes between 200 and 50 km. Odyssey's scientific payload of seven instruments includes CHEMIN, a mineralogical dust analyzer, which will make the first direct measurements of the crystal structure and elemental composition of cometary dust. CHEMIN will simultaneously perform X-ray Diffraction and X-ray Fluorescence (XRD/XRF) of individual 1-100 micron dust particles collected passively as the spacecraft is immersed in the comet's coma. The instrument has the geometry of a microfocus X-ray camera, with a postage stamp-sized energy-discriminating CCD in place of the film, and a miniature Cu target X-ray tube as the X-ray source. The CHEMIN flight instrument will weigh less than 2 kg., will have a total volume of about 1 liter, and will operate on 3 watts of power. Individual analyses will require 1-2 hours. XRD maxima from 5 to 65 degrees two-theta will be collected, encompassing definitive peaks for all known minerals. XRF data will be simultaneously collected for elements C through U. The instrument has sufficient resolution to allow Rietveld refinement of the diffraction data. Rock types as complex as basalt have been quantitatively analyzed using a CHEMIN laboratory prototype. Selected examples of diffraction experiments performed on more than 30 minerals and rock types by the CHEMIN laboratory prototype will be discussed.

Blake, David↗

Chromium on Eros: Further Evidence of Ordinary Chondrite Composition

The surface major element composition of the near-earth asteroid 433-Eros has been determined by x-ray fluorescence spectroscopy (XRS) on the NEAR-Shoemaker spacecraft [1]. The abundances of Mg, Al, Si, Ca and Fe match those of ordinary chondrites [1]. However, the observation that Eros appears to have a sulfur abundance at least a factor of two lower than ordinary chondrites, suggests either sulfur loss from the surface of Eros by impact and/or radiation processes (space weathering) or that its surface is comprised of a somewhat more differentiated type of material than an ordinary chondrite [1]. A definitive match for an ordinary chondrite parent body has very rarely been made, despite the conundrum that ordinary chondrites are the most prevalent type of meteorite found on Earth. Furthermore, Eros is classified as an S(IV) type asteroid [2] and being an S, it is the second most prevalent type of asteroid in the asteroid belt [3].

Foley, C. N.↗

Exploring rock-regolith interfaces in Jezero crater with Mars 2020 SHERLOC

The Perseverance rover successfully landed in Jezero crater, Mars in February 2021 at the Octavia E. Butler landing site and began its mission to explore and sample an ancient crater lake basin. Principal goals of the Mars 2020 mission include characterizing the geology of Mars and seeking signs of ancient microbial life via the spacecraft cameras and spectroscopic instruments onboard. The Scanning Habitable Environments with Raman and Luminescence for Organics and Chemicals (SHERLOC) instrument is a deep UV Raman spectrometer that utilizes a 248.6nm pulsed laser. Part of SHERLOC is a color camera known as the Wide Angle Topographic Sensor for Operations and eNgineering (WATSON). The SHERLOC suite provides coordinated, spectroscopic and imaging capabilities at high spatial resolution, to detect minerals and organic molecules in microtextural context. By pairing high spatial resolution (~100 μm) resonance Raman and native fluorescence spectroscopy with microscopic imaging in a novel spacecraft capability, SHERLOC enables texture-specific molecular composition measurements of rock and regolith targets on Mars. Coordinated rock-regolith observations illuminate unique insights into weathering processes and thereby to primary properties of rocks in Jezero crater. This work describes the potential of rock-regolith interfaces to preserve unique records of geological processes in Jezero crater and can powerfully supplement observations of the more general rock record on Mars. Linking observations of local rock texture with associated regolith reveals important lithologic information based on the interrelationship between differential weathering behavior and mineralogy, grain size, and cement chemistry. Preliminary observations indicate that the polygonally fractured lithotype common near the Octavia E. Butler landing site may weather by granular disintegration and/or surface creep, a relation that can be uniquely observed at the rock-regolith interface. SHERLOC -specific observations of microtextural and elemental composition transitions presented here trace rock-regolith boundaries at multiple indurated surfaces adjacent to regolith. At these locales, grain-scale based examinations suggest chemical weathering could be related to a variably distributed coating or rind on dark rock targets that may be mafic in composition. Granule deposits overlying widely distributed fine-grained material are also observable. Mineral identifications of each phase are presented, with cross-scale comparisons to the remote insights gained by the SuperCam instrument.

Emily L. Cardarelli↗

Mapping Organic-Mineral Associations in Jezero crater

The search for potential signs of life on Mars, a primary aim of the Mars 2020 mission, is greatly informed by the detection of organic matter1. The presence of organic matter also provides key information about the habitability and biological potential of the planet throughout its history. The Perseverance rover was designed for in situ science with the ability to collect a suite of promising samples for eventual return to Earth. One of its instruments, Scanning Habitable Environments with Raman and Luminescence for Organics and Chemicals (SHERLOC), is a deep ultraviolet (DUV) Raman and fluorescence spectrometer designed to map the distribution of organic molecules and minerals on rock surfaces at a resolution of 100 μm2. With its unique spectral mapping capabilities, SHERLOC enables a novel understanding of organic-mineral relationships on Mars to better determine their formation, deposition, and preservation mechanisms. The rover’s landing site within Jezero crater combines a high potential for past habitability as the site of an ancient lake basin with a diverse set of minerals, including carbonates and clays, that may preserve organic materials and potential biosignatures. The Jezero crater floor includes three formations (fm); two of these, Máaz and Séítah, were explored as part of the mission’s first campaign. Here, we report the detection of multiple species of aromatic organic molecules using Raman and fluorescence spectroscopy across ten targets in the two formations. This is the first evidence of organic molecules in Martian materials obtained using Raman spectroscopy, and among the first using fluorescence spectroscopy, beyond Earth3. We report specific spatial patterns and classes of organic molecules in these compositionally distinct formations, potentially indicating different fates of carbon in these environments. Our findings indicate that there is a diversity of aromatic molecules prevalent on the Martian surface and these materials persist despite exposure to surface conditions. These organic molecules are largely found within minerals linked to aqueous processes, suggesting that these processes may have had a key role in organic synthesis, transport from their point of origin, or preservation.

Sunanda Sharma↗

Salt Stress Induces Paramylon Accumulation and Fine-Tuning of the Macro-Organization of Thylakoid Membranes in Euglena gracilis Cells

The effects of salt stress condition on the growth, morphology, photosynthetic performance, and paramylon content were examined in the mixotrophic, unicellular, flagellate Euglena gracilis. We found that salt stress negatively influenced cell growth, accompanied by a decrease in chlorophyll (Chl) content. Circular dichroism (CD) spectroscopy revealed the changes in the macro-organization of pigment-protein complexes due to salt treatment, while the small-angle neutron scattering (SANS) investigations suggested a reduction in the thylakoid stacking, an effect confirmed by the transmission electron microscopy (TEM). At the same time, the analysis of the thylakoid membrane complexes using native-polyacrylamide gel electrophoresis (PAGE) revealed no significant change in the composition of supercomplexes of the photosynthetic apparatus. Salt stress did not substantially affect the photosynthetic activity, as reflected by the fact that Chl fluorescence yield, electron transport rate (ETR), and energy transfer between the photosystems did not change considerably in the salt-grown cells. We have observed notable increases in the carotenoid-to-Chl ratio and the accumulation of paramylon in the salt-treated cells. We propose that the accumulation of storage polysaccharides and changes in the pigment composition and thylakoid membrane organization help the adaptation of E. gracilis cells to salt stress and contribute to the maintenance of cellular processes under stress conditions.

59 BASIC BIOLOGICAL SCIENCES↗

Sub-Micrometer Scale Minor Element Mapping in Interplanetary Dust Particles: A Test for Stratospheric Contamination

Combined X-ray microprobe (XRM), energy dispersive x-ray fluorescence using a Transmission Electron Microscope (TEM), and electron microprobe measurements have determined that the average bulk chemical composition of the interplanetary dust particles (IDPs) collected from the Earth s stratosphere is enriched relative to the CI meteorite composition by a factor of 2 to 4 for carbon and for the moderately volatile elements Na, K, P, Mn, Cu, Zn, Ga, Ge, and Se, and enriched to approximately 30 times CI for Br. However, Jessberger et al., who have reported similar bulk enrichments using Proton Induced X-ray Emission (PIXE), attribute the enrichments to contamination by meteor-derived atmospheric aerosols during the several weeks these IDPs reside in the Earth s atmosphere prior to collection. Using scanning Auger spectroscopy, a very sensitive surface analysis technique, Mackinnon and Mogk have observed S contamination on the surface of IDPs, presumably due to the accretion of sulfate aerosols during stratospheric residence. But the S-rich layer they detected was so thin (approximately 100 angstroms thick) that the total amount of S on the surface was too small to significantly perturb the bulk S-content of a chondritic IDP. Stephan et al. provide support for the contamination hypothesis by reporting the enrichment of Br on the edges of the IDPs using Time-of-Flight Secondary-Ion Mass-Spectrometry (TOFSIMS), but TOF-SIMS is notorious for producing false edge-effects, particularly on irregularly-shaped samples like IDPs. Sutton et al. mapped the spatial distribution of Fe, Ni, Zn, Br, and Sr, at the approximately 2 m scale, in four IDPs using element-specific x-ray fluorescence (XRF) computed microtomography. They found the moderately volatile elements Zn and Br, although spatially inhomogeneous, were not concentrated on the surface of any of the IDPs they examined, suggesting that the Zn and the Br enrichments in the IDPs are not due to contamination during stratospheric residence.

Flynn, G. J.↗

X-ray fluorescence mapping of brain tissue reveals the profound extent of trace element dysregulation in stroke pathophysiology

Abstract The brain is a privileged organ with regard to its trace element composition and maintains a robust barrier system to sequester this specialized environment from the rest of the body and the vascular system. Stroke is caused by loss of adequate blood flow to a region of the brain. Without adequate blood flow ischaemic changes begin almost immediately, triggering an ischaemic cascade, characterized by ion dysregulation, loss of function, oxidative damage, cellular degradation, and breakdown of the barrier that helps maintain this environment. Ion dysregulation is a hallmark of stroke pathophysiology and we observe that most elements in the brain are dysregulated after stroke. X-ray fluorescence-based detection of physiological changes in the neurometallome after stroke reveals profound ion dysregulation within the lesion and surrounding tissue. Not only are most elements significantly dysregulated after stroke, but the level of dysregulation cannot be predicted from a cell-level description of dysregulation. X-ray fluorescence imaging reveals that the stroke lesion retains <25% of essential K+ after stroke, but this element is not concomitantly elevated elsewhere in the organ. Moreover, elements like Na+, Ca2+, and Cl− are vastly elevated above levels available in normal brain tissue (>400%, >200%, and >150%, respectively). We hypothesize that weakening of the blood–brain barrier after stroke allows elements to freely diffuse down their concentration gradient so that the stroke lesion is in equilibrium with blood (and the compartments containing brain interstitial fluid and cerebrospinal fluid). The change observed for the neurometallome likely has consequences for the potential to rescue infarcted tissue, but also presents specific targets for treatment.

Biochemistry & Molecular Biology↗

Chemical Aging of Environmentally Friendly Cleaners

Use of cleaners in the manufacturing area demands bottles that will hold a sufficient amount of material and allow for easy and controlled dispensing by the operator without contamination or material leaching from the bottle. The manufacturing storage conditions are also a factor that may affect cleaner chemical integrity and its potential to leave a residue on the part. A variety of squeeze bottles stored in mild (72 F, 10 % R.H., dark) and harsh (105 F, 50 % R.H., fluorescent lighting) conditions were evaluated to determine the effect of environment and bottle exposure on the chemical composition of TCA (1,1,1 trichloroethane) replacement solvents. Low Density Polyethylene (LDPE) bottles were found to be quite permeable to all the cleaners evaluated in this study indicating this bottle type should not be used in the manufacturing area. Fluorinated Polyethylene (FLPE) bottles showed little cleaner loss and change in cleaner chemical composition over time suggesting these bottles would be acceptable for use. Chemical analysis indicates limonene-containing cleaners show increased non-volatile residue (NVR) content with storage under harsh conditions. Some cleaners use BHT (butylated hydroxytoluene) as stabilizer and to protect against limonene oxidation. Under harsh conditions, BHT was quickly depleted resulting in higher NVR levels.

Evans, K.↗

Photon Luminescence of the Moon

Luminescence is typically described as light emitted by objects at low temperatures, induced by chemical reactions, electrical energy, atomic interactions, or acoustical and mechanical stress. An example is photoluminescence created when photons (electromagnetic radiation) strike a substance and are absorbed, resulting in the emission of a resonant fluorescent or phosphorescent albedo. In planetary science, there exists X-ray fluorescence induced by sunlight absorbed by a regolith a property used to measure some of the chemical composition of the Moon s surface during the Apollo program. However, there exists an equally important phenomenon in planetary science which will be designated here as photon luminescence. It is not conventional photoluminescence because the incoming radiation that strikes the planetary surface is not photons but rather cosmic rays (CRs). Nevertheless, the result is the same: the generation of a photon albedo. In particular, Galactic CRs (GCRs) and solar energetic particles (SEPs) both induce a photon albedo that radiates from the surface of the Moon. Other particle albedos are generated as well, most of which are hazardous (e.g. neutrons). The photon luminescence or albedo of the lunar surface induced by GCRs and SEPs will be derived here, demonstrating that the Moon literally glows in the dark (when there is no sunlight or Earthshine). This extends earlier work on the same subject [1-4]. A side-by-side comparison of these two albedos and related mitigation measures will also be discussed.

Wilson, T.L.↗

Diverse Organic-Mineral Associations in Jezero Crater, Mars

The presence and distribution of preserved organic matter on the surface of Mars can provide key information about the Martian carbon cycle and the potential of the planet to host life throughout its history. Several types of organic molecules have been previously detected in Martian meteorites1 and at Gale crater, Mars. Evaluating the diversity and detectability of organic matter elsewhere on Mars is important for understanding the extent and diversity of Martian surface processes and the potential availability of carbon sources1,5,6. Here we report the detection of Raman and fluorescence spectra consistent with several species of aromatic organic molecules in the Máaz and Séítah formations within the Crater Floor sequences of Jezero crater, Mars. We report specific fluorescence-mineral associations consistent with many classes of organic molecules occurring in different spatial patterns within these compositionally distinct formations, potentially indicating different fates of carbon across environments. Our findings suggest there may be a diversity of aromatic molecules prevalent on the Martian surface, and these materials persist despite exposure to surface conditions. These potential organic molecules are largely found within minerals linked to aqueous processes, indicating that these processes may have had a key role in organic synthesis, transport or preservation.

Sunanda Sharma↗

Effect of bisphosphonate treatment on the oim mouse middle ear ossicles' structure, composition and hearing

Hearing loss is common in people with osteogenesis imperfecta (OI or brittle bone disease). Bisphosphonates are commonly used to treat long bone fragility in children with OI. However, its impact on the bone quality of the middle ear ossicles and hearing remains unknown. This study determines whether bisphosphonates treatment itself may contribute to hearing loss in OI by evaluating its effects in the oim/oim mouse model of severe OI having normal auditory function. Specifically, this study reports the effects of alendronate (ALN), a nitrogen-containing bisphosphonate, on ossicle morphology, porosity, and elemental composition in 14-week-old oim/oim mice treated weekly, starting at 2 weeks of age. The ossicles were examined using synchrotron microtomography and X-ray fluorescence microscopy (XFM). Hearing was assessed longitudinally until 26 weeks of age by determining auditory brainstem response (ABR) thresholds in another group of mice also treated weekly starting at 2 weeks of age. ALN treatment further reduces in size the already small oim/oim ossicles, specifically in female mice. Porosity, bone composition, and hearing function, however, were generally not affected by the ALN treatment. Furthermore, ALN does not prevent joint fusions, excessive bone formations, or enlarged joint spaces in WT or oim/oim experimental groups. One ALN-treated oim/oim mouse with a bone formation in the interior of the footplate, and one ALN-treated WT mouse with a fixed footplate had frequency-specific hearing loss. Since footplate abnormalities are not observed in PBS-treated mice in this study, it remains unclear whether ALN fails to prevent these changes or contributes to their development. Future studies should investigate the mechanisms of ossicular abnormalities and bisphosphonates modulatory role in the ossicles.

60 APPLIED LIFE SCIENCES↗

Trace Impurities Identified as Forensic Signatures in CMX-5 Fuel Pellets Using X-ray Spectroscopic Techniques

We report that small-particle analysis is a highly promising emerging forensic tool for analysis of interdicted special nuclear materials. Integration of microstructural, morphological, compositional, and molecular impurity signatures could provide significant advancements in forensic capabilities. We have applied rapid, high-sensitivity, hard X-ray synchrotron chemical imaging to analyze impurity signatures in two differently fabricated fuel pellets from the 5th Collaborative Materials Exercise (CMX5) of the IAEA Nuclear Forensics International Working Group. The spatial distributions, chemical compositions, and morphological and molecular characteristics of impurities were evaluated using X-ray absorption near-edge structure (XANES) and X-ray fluorescence chemical imaging to discover principal impurities, their granularity, particle sizes, modes of occurrence (distinct grains vs incorporation in the UO 2 lattice), and sources and mechanisms of incorporation. Differences in UO 2+x stoichiometry were detected at the microscale in nominally identical UO 2 ceramics (CMX5-A and CMX5-B), implying the presence of multiple UO 2 host phases with characteristic microstructures and feedstock compositions. Al, Fe, Ni, W, and Zr impurities and integrated impurity signature analysis identified distinctly different pellet synthesis and processing methods. For example, two different Al, W, and Zr populations in the CMX5-B sample indicated a more complex processing history than the CMX5-A sample. K-edge XANES measurements reveal both metallic and oxide forms of Fe and Ni but with different proportions between each sample. Altogether, these observations suggest multiple sources of impurities, including fabrication (e.g., force-sieving) and feedstock (mineral oxides). This study demonstrates the potential of synchrotron techniques to integrate different signatures across length scales (angstrom to micrometer) to detect and differentiate between contrasting UO 2 fuel fabrication techniques.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗