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At least 1,531 records · Page 85

Independent amplitude approximations in coupled cluster valence bond theory: Incorporation of 3-electron-pair correlation and application to spin frustration in the low-lying excited states of a ferredoxin-type tetrametallic iron-sulfur cluster

We report that coupled cluster valence bond (CCVB) is a simple electronic structure method based on a perfect pairing (PP) reference with 2-pair recouplings for strong electron correlation problems. CCVB is spin-pure, size-consistent, and can exactly (in its active space) separate any molecule into atoms for which unrestricted Hartree-Fock (UHF) at dissociation is the sum of the ground state UHF energies of the atoms. However CCVB is far from a complete description of strong correlations. Its first failure to exactly describe spin-recouplings arises at the level of 3 electron pairs, such as the recoupling of 3 triplet oxygen atoms in the dissociation of singlet ozone. Such situations are often associated with spin frustration. To address this limitation, an extension of CCVB, termed CCVB+i3, is reported here that includes an independent (i) amplitude approximation to the 3-pair recouplings. CCVB+i3 thereby has the same basic computational requirements as those of CCVB, which has previously been shown to be an efficient method. CCVB+i3 correctly separates molecules that CCVB cannot. As a by-product, an independent 2-pair amplitude approximation to CCVB, called PP+i2, is also defined. Remarkably, PP+i2 can also correctly separate systems that CCVB cannot. CCVB+i3 is validated on the symmetric dissociation of D 3h ozone. CCVB+i3 is then used to explore the role of 3-pair recouplings in an [Fe 4 S 4 (SCH 3 ) 4 ] 2- cluster that has been used to model the iron-sulfur core of [Fe 4 S 4 ] ferredoxins. Using localized PP orbitals, such recouplings are demonstrated to be large in some low-lying singlet excited states of the cluster. Lastly, significant 3 pair recoupling amplitudes include the usual triangular motif associated with spin frustration and other geometric arrangements of the 3 entangled pairs across the 4 iron centers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Origin and Reactivity of the Martian Soil: A 2003 Micromission

The role of water in the development of the martian surface remains a fundamental scientific question. Did Mars have one or more "warm and wet" climatic episodes where liquid water was stable at the surface? If so, the mineral phases present in the soils should be consistent with a history of aqueous weathering. More generally, the formation of hydrated mineral phases on Mars is a strong indicator of past habitable surface environments. The primary purpose of this investigation is to help resolve the question of whether such aqueous indicators are present on Mars by probing the upper meter for diagnostic mineral species. According to Burns [1993], the formation of the ferric oxides responsible for the visible color of Mars are the result of dissolution of Fe (+2) phases from basalts followed by aqueous oxidation and precipitation of Fe" mineral assemblages. These precipitates likely included iron oxyhydroxides such as goethite (a-FeOOH) and lepidocrocite (g-FeOOH), but convincing evidence for these phases at the surface is still absent. The stability of these minerals is enhanced beneath the surface, and thus we propose a subsurface search for hydroxylated iron species as a test for a large-scale chemical weathering process based on interactions with liquid water. It is also possible that the ferric minerals on Mars are not aqueous alteration products of the rocks. A chemical study of the Pathfinder landing site concluded that the soils are not directly derived from the surrounding rocks and are enhanced in Mg and Fe. The additional source of these elements might be from other regions of Mars and transported by winds, or alternatively, from exogenic sources. Gibson [1970] proposed that the spectral reflectivity of Mars is consistent with oxidized meteoritic material. Yen and Murray [1998] further extend Gibson's idea and show, in the laboratory, that metallic iron can be readily oxidized to maghemite and hematite under present-day martian surface conditions (in the absence of liquid water). A test for a meteoritic component of the soil can be conducted, as described below, by searching for the presence of Ni at the martian surface. The average abundance of nickel in an Fe-Ni meteorite is about 7% and, if present at measurable levels in the soil, would be indicative of an exogenic contribution. In addition, it may be possible to directly search for mineral phases common in meteorites. An understanding of the formation and evolution of the martian soil would not be complete without addressing the unusual reactivity discovered by the Viking Landers The presence of an inorganic oxidant, possibly one produced as a results of photochemical processes, is the most widely accepted explanation of the Viking results. Are these chemical species simply adsorbed on soil grains, or have they reacted with the metal oxide substrates and altered the mineral structures? Could a completely different (non-photochemical) process be responsible for the soil reactivity? The various ideas for the nature of this putative oxidant could be constrained by a measurement of the change in reactivity with depth. Different compositions will have different lifetimes and mobilities and thus will have different vertical profiles. Because the oxidizing compounds are believed to actively destroy organic molecules, determination of the reactivity gradient also has significant implications for the search for life on Mars. A DS2-based microprobe system can be instrumented for a 2003 micromission to investigate the origin and reactivity of the martian soil. These measurements would provide invaluable information regarding the climate history and exobiological potential of the planet. The NMR, X ray and chemiresistor measurement approach described embodies a highly synergistic and general set of soil interrogation methods for elements, compounds, and crystal structures and can also be applied to other geologic questions of interest. For example, if the capability for precise targeting of the probes is available, then in-situ investigations of suspected evaporite and hydrothermal deposits would be possible with the same set of instruments. Additional information is contained in the original.

Yen, Albert S.↗

Pushing the heterometal doping limit while preserving long-lived charge separation in a Ti-based MOF photocatalyst

Here, this study explores the nature, dynamics, and reactivity of the photo-induced charge separated excited state in a Fe 3+ -doped titanium-based metal organic framework (MOF), xFeMIL125-NH 2 , as a function of iron concentration. The MOF is synthesized with doping levels x = 0.5, 1 and 2 Fe node sites per octameric Ti-oxo cluster and characterized by powder x-ray diffraction, UV-vis diffuse reflectance, atomic absorption, and steady state Fe K-edge X-ray absorption spectroscopy. For each doping level, time-resolved X-ray transient absorption spectroscopy studies confirm the electron trap site role of the Fe sites in the excited state. Time scan data reveal multiexponential decay kinetics for the charge recombination processes which extend into the microsecond range for all three concentrations. A series of dye photodegradation studies, based on the oxidative decomposition of Rhodamine B, demonstrates the reactivity of the charge separated excited state and the photocatalytic capacity of these MOF materials compared to traditional heterometal-doped semiconductor photocatalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Probing the Mechanism of Selective Phosphate Adsorption from Wastewater Using Aqueous and Synchrotron X-ray Characterization

Ion exchange shows promise for recovering phosphate from wastewater as value-added products, but requires high phosphate selectivity to compete with conventional treatment. Hybrid anion exchange (HAIX) resins, which contain non-selective basic functional groups and selective iron oxide nanoparticles (FeOnp), can effectively remove phosphate from wastewater. However, knowledge gaps remain regarding the mechanisms of phosphate selectivity and influence of competing ions, hindering needed efforts to model adsorption dynamics and design scalable adsorption processes for varying wastewaters. To address these gaps, we integrated aqueous-phase adsorption analysis with solid-phase, synchrotron-based X-ray characterization; this integration facilitated elucidation of the distribution and speciation of iron, phosphate, and competing anions on HAIX resins. We compared a quaternary ammonium-functionalized HAIX resin (SBA) to a tertiary amine version (WBA) to determine the role of functional groups. X-ray radiography revealed differences in FeOnp speciation (goethite vs. ferrihydrite) and distribution (peripheral vs. homogeneous) between the resins, resulting in varied phosphate affinity and intraparticle diffusion resistance. Using micro-X-ray fluorescence (μ-XRF) and micro-X-ray absorption near-edge structure (μ-XANES) spectroscopy, we identified differences in where and how phosphate binds across resin types and wastewaters. Across wastewater compositions, FeOnp sites in WBA contribute more to phosphate adsorption than in SBA, possibly due to variations in Fe distribution and speciation. Phosphate adsorption densities calculated from quantitative μ-XRF maps matched those from aqueous analysis, demonstrating the effectiveness of this integrated approach. Altogether, results demonstrate the use of synchrotron-based X-ray characterization for investigating adsorption mechanisms and advance HAIX as a phosphate recovery technology from complex wastewaters.

Nutrient recovery↗

Measurement of the Iron Spectrum in Cosmic Rays from 10 GeV/n to 2.0 TeV/n with the Calorimetric Electron Telescope on the International Space Station

The Calorimetric Electron Telescope (CALET), in operation on the International Space Station since 2015, collected a large sample of cosmic-ray iron over a wide energy interval. In this paper a measurement of the iron spectrum is presented in the range of kinetic energy per nucleon from 10GeV/n to 2.0 TeV/n allowing the inclusion of iron in the list of elements studied with unprecedented precision by space-borne instruments. The measurement is based on observations carried out from January 2016 to May 2020. The CALET instrument can identify individual nuclear species via a measurement of their electric charge with a dynamic range extending far beyond iron (up to atomic number Z = 40). The energy is measured by a homogeneous calorimeter with a total equivalent thickness of 1.2 proton interaction lengths preceded by a thin (3 radiation lengths) imaging section providing tracking and energy sampling. The analysis of the data and the detailed assessment of systematic uncertainties are described and results are compared with the findings of previous experiments. The observed differential spectrum is consistent within the errors with previous experiments. In the region from 50 GeV/n to 2 TeV/ n our present data are compatible with a single power law with spectral index−2.60±0.03.

O Adriani↗

AREVA NP MR Cladding benefits for proposed US NRC RIA and LOCA requirements

M5 is the reference alloy of AREVA NP for PWR cladding applications. It is a zirconium-based alloy containing 1% niobium, no tin, and well-controlled oxygen, iron, and sulfur contents. It has a fully recrystallized microstructure. The absence of tin in M5 results in a very low corrosion rate and hydrogen pick-up during normal operation, even at high burn-up and in high duty irradiation conditions. Due to this low hydrogen pick-up under irradiation (typically less than 100 ppm, End of Life), M5 retains a very good strength and an exceptional residual ductility during and after the accident. This allows utilities implementing M5 to simplify the safety analysis and to demonstrate significant margins regarding fuel related criteria. Simplified methods are easier for plants to implement and maintain for future plant operations and core design management. This paper specifically presents 3 examples on the safety improvement brought by M5 cladding. First, during a reactivity-induced accident (RIA), the properties of M5 are such that bounding analyses for future cycles are significantly simplified, in particular by demonstrating that fuel dispersal will not occur. The major aspects of the AREVA NP RIA methodology are presented. A second focus is made on the low hydrogen embrittlement of M5 and on its high ductility after quenching during a loss-of-coolant accident (LOCA). In a third part, the breakaway oxidation testing program currently under development in Paimboeuf (France) is described, including details about the testing devices and qualification. The tests have demonstrated that M5 cladding does not have breakaway at least up to 5000 s oxidation duration at 1000 C. degrees, which is much higher than the LOCA duration.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Global Sensitivity Analysis of a Reactive Transport Model for Mineral Scale Formation During Hydraulic Fracturing

Injection of water-based hydraulic fracturing fluid (HFF) into tight shale gas/oil formations can increase formation permeability and enhance production rates, but this process frequently causes mineral scale formation that can occlude pore space and hinder flow. To identify the most important factors that control the formation of mineral scales, we applied a novel global sensitivity analysis method—distance-based generalized sensitivity analysis (DGSA)—to a reactive transport model (RTM) that was previously built and calibrated to simulate precipitation of barite [BaSO4] and iron (hydr)oxide [Fe(OH) 3 ] in shale matrices and on fracture surfaces. Reactive transport simulations were run with model parameters randomly sampled based on assigned uncertainties. Modeling results for barite and Fe(OH)3 formation were clustered using machine-learning algorithms. A list of ranked critical input parameters was obtained after statistical quantification of cumulative distribution functions of input parameters. We found that barite formation is most sensitive to the rate of sulfate ion generation, which is determined by the pyrite dissolution rate coefficient and oxidant availability. In addition, barite formation is sensitive to the initial amounts of barite in HFF and shale, followed by barite thermodynamics/kinetics. For Fe(OH) 3 formation, the ranked factors are Fe(OH)3 precipitation rate coefficients, initial HFF pH, initial Fe(OH) 3 amount in HFF, and oxidant availability. Overall, our results provide insights into managing mineral scale formation during hydraulic fracturing to enhance production. Meanwhile, this study serves as an example of global sensitivity analysis of RTMs using the efficient, straightforward, and open-source DGSA method.

58 GEOSCIENCES↗

The Principal Hugoniot of Iron-Bearing Olivine to 1465 GPa

Shock compression experiments on natural compositions are imperative to accurately model planetary accretion and the interior dynamics of planets. Combining shock compression experiments from the Sandia Z Machine and the OMEGA EP laser facility with density functional theory-based molecular dynamics calculations, we report the first pressure-density-temperature (P-ρ-T) relationship of natural iron (Fe)-bearing olivine ((Mg 0.91 Fe 0.09 ) 2 SiO 4 ) on the principal Hugoniot between 166 and 1,465 GPa. Additionally, we report the first reflectivities of natural olivine liquid in this pressure range. Compared to the magnesium-endmember forsterite (Mg 2 SiO 4 ), the presence of Fe in typical mantle abundance (~9 wt% FeO) alters the U S -u P relation of olivine. Furthermore, the shock temperature and reflectivity of olivine are indistinguishable from forsterite where experimental conditions overlap. Both forsterite and olivine increase in reflectivity (and hence optical conductivity) with increasing temperature, with a maximum reflectivity of ~31% at shock velocities greater than 22 km/s (~800 GPa).

58 GEOSCIENCES↗

Proteomic Analysis of Methanococcus voltae Grown in the Presence of Mineral and Nonmineral Sources of Iron and Sulfur

Iron sulfur (Fe-S) proteins are essential and ubiquitous across all domains of life, yet the mechanisms underpinning assimilation of iron (Fe) and sulfur (S) and biogenesis of Fe-S clusters are poorly understood. This is particularly true for anaerobic methanogenic archaea, which are known to employ more Fe-S proteins than other prokaryotes. Here, we utilized a deep proteomics analysis of Methanococcus voltae A3 cultured in the presence of either synthetic pyrite (FeS 2 ) or aqueous forms of ferrous iron and sulfide to elucidate physiological responses to growth on mineral or nonmineral sources of Fe and S. The liquid chromatography-mass spectrometry (LCMS) shotgun proteomics analysis included 77% of the predicted proteome. Through a comparative analysis of intra- and extracellular proteomes, candidate proteins associated with FeS 2 reductive dissolution, Fe and S acquisition, and the subsequent transport, trafficking, and storage of Fe and S were identified. The proteomic response shows a large and balanced change, suggesting that M. voltae makes physiological adjustments involving a range of biochemical processes based on the available nutrient source. Among the proteins differentially regulated were members of core methanogenesis, oxidoreductases, membrane proteins putatively involved in transport, Fe-S binding ferredoxin and radical S-adenosylmethionine proteins, ribosomal proteins, and intracellular proteins involved in Fe-S cluster assembly and storage. This work improves our understanding of ancient biogeochemical processes and can support efforts in biomining of minerals. Clusters of iron and sulfur are key components of the active sites of enzymes that facilitate microbial conversion of light or electrical energy into chemical bonds. The proteins responsible for transporting iron and sulfur into cells and assembling these elements into metal clusters are not well understood. Using a microorganism that has an unusually high demand for iron and sulfur, we conducted a global investigation of cellular proteins and how they change based on the mineral forms of iron and sulfur. Understanding this process will answer questions about life on early earth and has application in biomining and sustainable sources of energy.

59 BASIC BIOLOGICAL SCIENCES↗

Metagenomic analysis reveals global-scale patterns of ocean nutrient limitation

Genomes reveal nutrient stress patterns Within the surface ocean, nitrogen, iron, and phosphorous can all be limiting nutrients for phytoplankton depending on location. Ustick et al. used the prevalence of Prochlorococcus genes involved in nutrient acquisition to develop maps of inferred nutrient stress across the global ocean (see the Perspective by Coleman). They found broad patterns of limitation consistent with an Earth system model and nutrient addition experiments. Leveraging metagenomic data in this manner is an appealing approach that will help to expand our understanding of the biogeochemistry in the vast open ocean. Science , this issue p. 287 ; see also p. 239

Science & Technology - Other Topics↗

Exploring a quantum-information-relevant magnonic material: Ultralow damping at low temperature in the organic ferrimagnet V[TCNE]x

Quantum information science and engineering require novel low-loss magnetic materials for magnon-based quantum-coherent operations. The search for low-loss magnetic materials, traditionally driven by applications in microwave electronics near room temperature, has gained additional constraints from the need to operate at cryogenic temperatures for many applications in quantum information science and technology. Whereas yttrium iron garnet (YIG) has been the material of choice for decades, the emergence of molecule-based materials with robust magnetism and ultra-low damping has opened new avenues for exploration. Specifically, thin films of vanadium tetracyanoethylene (V[TCNE]x) can be patterned into the multiple, connected structures needed for hybrid quantum elements and have shown room-temperature Gilbert damping (α = 4 × 10−5) that rivals the intrinsic (bulk) damping otherwise seen only in highly polished YIG spheres (far more challenging to integrate into arrays). Here, the authors present a comprehensive and systematic study of the low-temperature magnetization dynamics for V[TCNE]x thin films, with implications for their application in quantum systems. These studies reveal a temperature-driven, strain-dependent magnetic anisotropy that compensates the thin-film shape anisotropy and the recovery of a magnetic resonance linewidth at 5 K that is comparable to room-temperature values (roughly 2 G at 9.4 GHz). The authors can account for these variations of the V[TCNE]x linewidth within the context of scattering from very dilute paramagnetic impurities and anticipate additional linewidth narrowing as the temperature is further reduced.

Yusuf, H. (ORCID:0000000194627928)↗

Massive Chromite in the Brenham Pallasite and the Fractionation of Cr During the Crystallization of Asteroidal Cores

Large (greater than or equal to 2 mm) chromite grains are present in IIIAB iron meteorites and in the main-group a pallasites (PMG), closely related to high-Au IIIAB irons, Pallasites seem to have formed by the intrusion of a highly evolved metallic magma from a IIIAB-like core into fragmented olivine of the overlying dunite mantle. High Cr contents are commonly encountered during the analyses of metallic samples of high-Au IIIAB irons and main-group pallasites, an indication that Cr contents were high in the intruding liquid and that Cr behaved as an incompatible element during the crystallization of the IIIAB magma, contrary to expectations based on the negative IIIAB Cr-Ni and Cr-Au trends among low-Au IIIAB irons. In a region about 10 cm across in the Brenham main-group pallasite massive chromite fills the interstices between olivine grains, the site normally occupied by metal in Brenham and other pallasites. The massive chromite may have formed as a late cumulus phase; because Fe-Ni was also crystallizing, its absence in the chromite-rich region suggests a separation associated with differences in liquid buoyancy. The coexisting chromite and olivine are zoned; in the olivine FeO is highest in pallasitic (olivine-metal) regions, lowest in rims adjacent to chromite, and intermediate in the cores of these olivines. Chromite shows the opposite zoning, with the highest FeO contents at grain edges adjacent to olivine. The observed gradients are those expected to form by Fe-Mg exchange between olivine and chromite during slow cooling at subsolidus temperatures. Compared to normal Brenham, contents of phosphoran olivine and phosphates are higher in the chromitic pallasitic region. We also report data for large-to-massive chromites present in PMG Molong and in high-Au IIIAB Bear Creek that, like Brenham, formed from a highly evolved magma. The Bear Creek chromite has a much lower Mg content than that in the pallasites, implying that, in the PMG, the Mg was extracted from the olivine during high-temperature reaction with the precipitating chromite. There are other circumstantial arguments indicating that Cr was incompatible in the metal during the crystallization of the IIIAB magma, with the concentration in die residual magma rising from an initial value of about 300 micrograms/g to a value around 700 micrograms/g when Bear Creek and Brenham were formed. We consider possible explanations for these negative Cr-Au and Cr-Ni trends and find the most probable one to be that they reflect sampling artefacts resulting from analysts avoiding visible chromite (and the commonly associated phase FeS) when choosing metal samples.

Wasson, John T.↗

Impact wear of iron rich superalloys

The impact-sliding wear resistance of chill cast and aligned eutectic Fe-base superalloys against M42 and 17-4 PH steel counterface materials is examined. The aligned material tests were run with carbide fibers perpendicular to the counterface contact surface and the characterization focused on fracture processes as observed in the subsurface microstructure of the worn materials. Metallographic analyses were performed on specimens exposed to various numbers of repetitive impact load cycles, and for comparison, two other aligned composites were tested with the same fiber orientation under identical test conditions against hardened M42 tool steel. A strong improvement was found in wear resistance of an aligned eutectic structure as compared to the corresponding randomized chill cast structure. Experiments with the softer 17-4 counterface were characterized by transfer onto the Fe-base superalloy, and the cracks formed were oriented transverse to the relative sliding direction and occurred in a periodic fashion. Observations in subsurface regions of the worn materials indicated crack intergranularity with an occasional transgranular fracture of the M7C3 carbide phase.

Wayne, S. F.↗

Grain boundary scavenging through reactive sintering of strontium and iron in samarium doped ceria electrolyte for ITSOFC applications

Highlights: • Addition of iron and strontium to Samarium doped ceria by combustion method and sintered at 1000 °C, 1200 °C, 1300 °C. • Viscous phase sintering of iron at 1200 °C modified to reactive sintering of iron and strontium at 1300 °C. • Grain boundary activation energy lowered without compensating the grain activation energy. • The highest scavenging factor of 10.52 with the lowest activation energy of 1.02eV was achieved. - Abstract: Lowering the operational temperature of ceria based electrolytes is important for commercialization of solid oxide fuel cells. Here, we report the effect of iron, strontium and iron/strontium co-addition in samarium (20 mol %) doped ceria (SDC) with respect to sintering, microstructural modifications and ionic conductivity. The nanoparticle synthesized through glycine-nitrate combustion method was sintered at 1000, 1200 and 1300 °C. An increase in density was observed in iron doped SDC due to viscous flow sintering while co-addition of strontium and iron lead to the reactive sintering at 1300 °C by forming a eutectic liquid phase which resulted in the density of 99%. The presence of iron and strontium generated a compensatory tensile strain in the lattice and an enhancement in oxygen vacancy concentration which resulted in higher ionic conductivity. Co-addition of strontium and iron in SDC, not only increases the density but also reduces the activation energy for grain boundary conductivity.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Temperature-Dependent Reaction Pathways in FeS 2 : Reversibility and the Electrochemical Formation of Fe 3 S 4

The present study has used a variety of characterization techniques to determine the products and reaction pathways involved in the rechargeable Li–FeS 2 system. We revisit both the initial lithiation and subsequent cycling of FeS 2 employing an ionic liquid electrolyte to investigate the intermediate and final charge products formed under varying thermal conditions (room temperature to 100 °C). The detection of Li 2 S and hexagonal FeS as the intermediate phases in the initial lithiation and the electrochemical formation of greigite, Fe 3 S 4 , as a charge product in the rechargeable reaction differ significantly from previous reports. The conditions for Fe 3 S 4 formation are shown to be dependent on both the temperature (~60 °C) and the availability of sulfur to drive a FeS to Fe 3 S 4 transformation. Upon further cycling, Fe 3 S 4 transforms to a lower sulfur content iron sulfide phase, a process which coincides with the loss of sulfur based on the new reaction pathways established in this work. The connection between sulfur loss, capacity fade, and charge product composition highlights the critical need to retain sulfur in the active material upon cycling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Penetration depth and absorption mechanisms of spin currents in Ir{sub 20}Mn{sub 80} and Fe{sub 50}Mn{sub 50} polycrystalline films by ferromagnetic resonance and spin pumping

Spintronics relies on the spin dependent transport properties of ferromagnets (Fs). Although antiferromagnets (AFs) are used for their magnetic properties only, some fundamental F-spintronics phenomena like spin transfer torque, domain wall motion, and tunnel anisotropic magnetoresistance also occur with AFs, thus making AF-spintronics attractive. Here, room temperature critical depths and absorption mechanisms of spin currents in Ir{sub 20}Mn{sub 80} and Fe{sub 50}Mn{sub 50} are determined by F-resonance and spin pumping. In particular, we find room temperature critical depths originating from different absorption mechanisms: dephasing for Ir{sub 20}Mn{sub 80} and spin flipping for Fe{sub 50}Mn{sub 50}.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

The influence of Ga additions on electric and magnetic properties of Co{sub 47}Fe{sub 21}B{sub 21}Si{sub 5}Nb{sub 6} alloy in crystal and liquid states

The influence of small additions of gallium on electric resistivity and magnetic susceptibility of the bulk glass forming Co{sub 47}Fe{sub 20.9}B{sub 21.2}Si{sub 4.6}Nb{sub 6.3} alloy was studied in a wide temperature range up to 1830 K. Gallium atoms were found to increase resistivity but decrease susceptibility of the alloy. The suppositions about clusters surrounding Ga atoms in the melt and new GFA criterion are given.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Organic preservation of vase‐shaped microfossils from the late Tonian Chuar Group, Grand Canyon, Arizona, USA

Abstract Vase‐shaped microfossils (VSMs) are found globally in middle Neoproterozoic (800–730 Ma) marine strata and represent the earliest evidence for testate (shell‐forming) amoebozoans. VSM tests are hypothesized to have been originally organic in life but are most commonly preserved as secondary mineralized casts and molds. A few reports, however, suggest possible organic preservation. Here, we test the hypothesis that VSMs from shales of the lower Walcott Member of the Chuar Group, Grand Canyon, Arizona, contain original organic material, as reported by B. Bloeser in her pioneering studies of Chuar VSMs. We identified VSMs from two thin section samples of Walcott Member black shales in transmitted light microscopy and used scanning electron microscopy to image VSMs. Carbonaceous material is found within the internal cavity of all VSM tests from both samples and is interpreted as bitumen mobilized from Walcott shales likely during the Cretaceous. Energy dispersive X‐ray spectroscopy (EDS) and wavelength dispersive X‐ray spectroscopy (WDS) reveal that VSM test walls contain mostly carbon, iron, and sulfur, while silica is present only in the surrounding matrix. Raman spectroscopy was used to compare the thermal maturity of carbonaceous material within the samples and indicated the presence of pyrite and jarosite within fossil material. X‐ray absorption spectroscopy revealed the presence of reduced organic sulfur species within the carbonaceous test walls, the carbonaceous material found within test cavities, and in the sedimentary matrix, suggesting that organic matter sulfurization occurred within the Walcott shales. Our suite of spectroscopic analyses reveals that Walcott VSM test walls are organic and sometimes secondarily pyritized (with the pyrite variably oxidized to jarosite). Both preservation modes can occur at a millimeter spatial scale within sample material, and at times even within a single specimen. We propose that sulfurization within the Walcott Shales promoted organic preservation, and furthermore, the ratio of iron to labile VSM organic material controlled the extent of pyrite replacement. Based on our evidence, we conclude that the VSMs are preserved with original organic test material, and speculate that organic VSMs may often go unrecognized, given their light‐colored, translucent appearance in transmitted light.

58 GEOSCIENCES↗