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At least 1,135 records · Page 63

How Deep and Hot was Earth's Magma Ocean? Combined Experimental Datasets for the Metal-silicate Partitioning of 11 Siderophile Elements - Ni, Co, Mo, W, P, Mn, V, Cr, Ga, Cu and Pd

Since approximately 1990 high pressure and temperature (PT) experiments on metal-silicate systems have showed that partition coefficients (D) for siderophile (iron-loving) elements are much different than those measured at low PT conditions. The high PT data have been used to argue for a magma ocean during growth of the early Earth. Initial conclusions were based on experiments and calculations for a small number of elements such as Ni and Co. However, for many elements only a limited number of experimental data were available then, and they only hinted at values of metal-silicate D's at high PT conditions. In the ensuing decades there have been hundreds of new experiments carried out and published on a wide range of siderophile elements. At the same time several different models have been advanced to explain the siderophile elements in the earth's mantle: a) intermediate depth magma ocean; 25-30 GPa, b) deep magma ocean; up to 50 GPa, and c) early reduced and later oxidized magma ocean. Some studies have drawn conclusions based on a small subset of siderophile elements, or a set of elements that provides little leverage on the big picture (like slightly siderophile elements), and no single study has attempted to quantitatively explain more than 5 elements at a time. The purpose of this abstract is to update the predictive expressions outlined by Righter et al. (1997) with new experimental data from the last decade, test the predictive ability of these expressions against independent datasets (there are more data now to do this properly), and to apply the resulting expressions to the siderophile element patterns in Earth's upper mantle. The predictive expressions have the form: lnD = alnfO2 + b/T + cP/T + d(1Xs) + e(1Xc) + SigmafiXi + g These expressions are guided by the thermodynamics of simple metal-oxide equilibria that control each element, include terms that mimic the activity coefficients of each element in the metal and silicate, and quantify the effect of variable oxygen fugacity. Preliminary results confirm that D(Ni) and D(Co) converge at pressures near 25-30 GPa and approximately 2200 K, and show that D(Pd) and D(Cu) become too low at the PT conditions of the deepest models. Furthermore, models which force fit V and Cr mantle concentrations by metal-silicate equilibrium overlook the fact that at early Earth mantle fO2, these elements will be more compatible in Mg-perovskite and (Fe,Mg)O than in metal. Thus an intermediate depth magma ocean, at 25-30 GPa, 2200 K, and at IW-2, can explain more mantle siderophile element concentrations than other models.

Righter, Kevin↗

TOI-1235 b: A Keystone Super-Earth for Testing Radius Valley Emergence Models around Early M Dwarfs

Small planets on close-in orbits tend to exhibit envelope mass fractions of either effectively zero or up to a few percent depending on their size and orbital period. Models of thermally driven atmospheric mass loss and of terrestrial planet formation in a gas-poor environment make distinct predictions regarding the location of this rocky/nonrocky transition in period–radius space. Here we present the confirmation of TOI-1235 b (P = 3.44 days, r(p)=1.738(+0.087,-0.076)R(ꚛ)), a planet whose size and period are intermediate between the competing model predictions, thus making the system an important test case for emergence models of the rocky/nonrocky transition around early M dwarfs (R(s) = 0.630 ± 0.015 R(ꙩ), M(s) = 0.640 ± 0.016 M(ꙩ)). We confirm the TESS planet discovery using reconnaissance spectroscopy, ground-based photometry, high-resolution imaging, and a set of 38 precise radial velocities (RVs) from HARPS-N and HIRES. We measure a planet mass of 6.91(+0.75,-0.85) M(ꚛ), which implies an iron core mass fraction of 20(+15,-12)% in the absence of a gaseous envelope. The bulk composition of TOI-1235 b is therefore consistent with being Earth-like, and we constrain an H/He envelope mass fraction to be <0.5% at 90% confidence. Our results are consistent with model predictions from thermally driven atmospheric mass loss but not with gas-poor formation, suggesting that the former class of processes remains efficient at sculpting close-in planets around early M dwarfs. Our RV analysis also reveals a strong periodicity close to the first harmonic of the photometrically determined stellar rotation period that we treat as stellar activity, despite other lines of evidence favoring a planetary origin (P=21.8(+0.9,-0.8) days, m(p) sin i= 13.0(+3.8,-5.3)M(ꚛ)) that cannot be firmly ruled out by our data.

Ryan Cloutier↗

Investigation into Reductive Separation of Tc-99 from Low Activity Waste Off-Gas Condensate by Zero Valent Iron Materials - 20311

This study is investigating the potential for reductive separation of technetium-99 (Tc) from off-gas condensate generated from vitrification of legacy tank waste at the Hanford Tank Waste Treatment and Immobilization Plant. Management of Tc is a high-priority activity for the U.S. Department of Energy (DOE) Office of Environmental Management (EM) complex, which must be addressed based on knowledge gaps and technology development needs outlined in the DOE-EM Technetium Management Program Plan [1]. Technetium is one of the main risk drivers in the permanent disposal of low activity waste (LAW) by vitrification at the Hanford Site due to its high volatility and only fractional incorporation into borosilicate glass. Volatilized Tc will be captured by an off-gas treatment system, and the current plan is to continuously recycle generated condensate back to the LAW glass melter feed. Off-gas recycling is effective at increasing Tc loading in the LAW glass, but it also disproportionately increases concentrations of sulfate, halides, and other volatile compounds impeding overall LAW processing leading to significantly greater waste glass volume requirements. Removal of Tc from secondary liquid waste offers an alternative disposal route to continuous off-gas recycling which may result in significant reduction of the volumes of LAW waste glass and substantial cost savings. The objective of this research funded by the DOE-EM Minority Serving Institutions Partnership Program (MSIPP) is to determine the suitability of zero valent iron (ZVI) as a separation technology to remove Tc from the off-gas condensate stream to minimize its recycle. While ZVI has been proposed for various remediation applications with Tc, it has not been studied for its suitability for removing Tc from the LAW off-gas condensate. The goal is to identify the optimal conditions for which Tc{sup (VII)} will be reduced to Tc{sup (IV)} species and incorporated into an iron matrix. This paper presents a programmatic overview of our evaluation of commercial ZVI materials for their efficiency towards Tc{sup (VII)} reductive removal from simplified off-gas simulant solutions under aerobic conditions. Tc concentrations in solutions were monitored for up to 30 days to determine efficiency and kinetics of reductive removal of Tc. The best performing candidate materials were selected for further experiments evaluating the effects of (1) variable ionic strength, (2) the presence of chromium and corrosive anions, and (3) ZVI aging on Tc{sup (VII)} reductive removal in batch experiments. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Self-Consistent Field Methods for Excited States in Strong Magnetic Fields: A Comparison Between Energy - and Variance-based Approaches

An efficient implementation of geometrical derivatives at the Hartree–Fock (HF) and current-density functional theory (CDFT) levels is presented for the study of molecular structure in strong magnetic fields. The required integral derivatives are constructed using a hybrid McMurchie–Davidson and Rys quadrature approach, which combines the amenability of the former to the evaluation of derivative integrals with the efficiency of the latter for basis sets with high angular momentum. In addition to its application to evaluating derivatives of four-center integrals, this approach is also applied to gradients using the resolution-of-the-identity approximation, enabling efficient optimization of molecular structure for many-electron systems under a strong magnetic field. The CDFT contributions have been implemented for a wide range of density functionals up to and including the meta-GGA level with current-density dependent contributions and (range-separated) hybrids for the first time. Illustrative applications are presented to the OH and benzene molecules, revealing the rich and complex chemistry induced by the presence of an external magnetic field. Challenges for geometry optimization in strong fields are highlighted, along with the requirement for careful analysis of the resulting electronic structure at each stationary point. The importance of correlation effects is examined by comparison of results at the HF and CDFT levels. The present implementation of molecular gradients at the CDFT level provides a cost-effective approach to the study of molecular structure under strong magnetic fields, opening up many new possibilities for the study of chemistry in this regime.

Comparison↗

Asymmetric vanadium-based aqueous flow batteries

Vanadium redox couples (V(II)/V(III) on a negative electrode or V(IV)/V(V) on a positive electrode) can be paired with other redox couples to form novel flow batteries (FBs). As an anolyte, the V(II)/V(III) redox couple can be paired with iron, manganese, cobalt, and cerium redox couples to form novel vanadium-iron (V-Fe), vanadium-manganese (V-Mn), vanadium-cobalt (V-Co), and vanadium-cerium (V-Ce) FBs, respectively. The V(IV)/V(V) redox couple as a catholyte can be coupled with hydrogen to form a vanadium hydrogen (V-H2) FB. In those new redox chemistries, redox reactions, energy density, round-trip efficiencies, crossover issues, and cell components (i.e., separator, ion exchange membrane, and electrode) are different from an all-vanadium flow battery discussed in previous chapters, and thus warrant a detailed discussion.

Vanadium, V-Fe, V-Ce, V-Co↗

Designing Heteroatom-Codoped Iron Metal–Organic Framework for Promotional Photoreduction of Carbon Dioxide to Ethylene

Rational engineering active sites and vantage defects of catalysts are promising but grand challenging task to enhance photoreduction CO 2 to high value-added C2 products. In this study, we designed an N,S-codoped Fe-based MIL-88B catalyst with well-defined bipyramidal hexagonal prism morphology via a facile and effective process, which was synthesized by addition of appropriate 1,2-benzisothiazolin-3-one (BIT) and acetic acid to the reaction solution. Under simulated solar irradiation, the designed catalyst exhibits high C 2 H 4 evolution yield of 17.7 μmol g -1 ∙h, which has been rarely achieved in photocatalytic CO 2 reduction process. The synergistic effect of Fe-N coordinated sites and reasonable defects in the N,S-codoped photocatalyst can accelerate the migration of photogenerated carriers, resulting in high electron density, and this in turn helps to facilitate the formation and dimerization of C-C coupling intermediates for C 2 H 4 effectively.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Observations of Highly-ionized Interstellar Iron

The spectra of 24 stars, including 5 at distances d 200 pc, have been observed in the regions of the coronal Fe X lambda 6375 and Fe X lambda 5303 lines at detection limits near an equivalent width of 1 mA in the best cases. In general agreement with predictions based on a multi-phase model of the interstellar medium, no absorption which can be attributed to Fe X or Fe X4 ions in hot interstellar gas emitting the soft X-ray background is seen in any of these spectra, except for two. Toward lambda Cephei an absorption line near lambda 6375 is measured with an equivalent width of 8.1 + or - 2 mA, a width corresponding to 20 + or - 5 km/sec or a temperature T or = (0.5 + or - 0.25) x 10 to the 6th power K, and, if it is caused by Fe X ions, a radial velocity of -355 km/sec. On that hypothesis, the interstellar gas constitutes at least 63% of the column density of gas along this light path.

Hobbs, L. M.↗

An evaluation of metallized propellants based on vehicle performance

An analytical study was conducted to determine the improvements in vehicle performance possible by burning metals with conventional liquid bipropellants. These metallized propellants theoretically offer higher specific impulse, increased propellant density and improved vehicle performance compared with conventional liquid bipropellants. Metals considered were beryllium, lithium, aluminum and iron. Liquid bipropellants were H2/O2, N2H4/N2O4, RP-1/O2 and H2/F2. A mission with a delta V = 4267.2 m/sec (14,000 ft/sec) and vehicle with propellant volume fixed at 56.63 cu m (2000 cu ft) and dry mass fixed at 2761.6 kg (6000 lb) was used, roughly representing the transfer of a chemically propelled upper-stage vehicle from a low-Earth orbit to a geosynchronous orbit. The results of thermochemical calculations and mission analysis calculations for bipropellants metallized with beryllium, lithium, aluminum and iron are presented. Technology issues pertinent to metallized propellants are discussed.

Zurawski, Robert L.↗

An evaluation of metallized propellants based on vehicle performance

An analytical study was conducted to determine the improvements in vehicle performance possible by burning metals with conventional liquid bipropellants. These metallized propellants theoretically offer higher specific impulse, increased propellant density and improved vehicle performance compared with conventional liquid bipropellants. Metals considered were beryllium, lithium, aluminum and iron. Liquid bipropellants were H2/O2, N2H4/N2O4, RP-1/O2 and H2/F2. A mission with a delta V = 4267.2 m/sec (14,000 ft/sec) and vehicle with propellant volume fixed at 56.63 cu m (2000 cu ft) and dry mass fixed at 2761.6 kg (6000 lb) was used, roughly representing the transfer of a chemically propelled upper-stage vehicle from a low-Earth orbit to a geosynchronous orbit. The results of thermochemical calculations and mission analysis calculations for bipropellants metallized with beryllium, lithium, aluminum and iron are presented. Technology issues pertinent to metallized propellants are discussed.

Zurawski, Robert L.↗

Web-Based Toxic Gas Dispersion Model for Shuttle Launch Operations

During the launch of the Space Shuttle vehicle, the burning of liquid hydrogen fuel with liquid oxygen at extreme high temperatures inside the three space shuttle main engines, and the burning of the solid propellant mixture of ammonium perchlorate oxidizer, aluminum fuel, iron oxide catalyst, polymer binder, and epoxy curing agent in the two solid rocket boosters result in the formation of a large cloud of hot, buoyant toxic exhaust gases near the ground level which subsequently rises and entrains into ambient air until the temperature and density of the cloud reaches an approximate equilibrium with ambient conditions. In this paper, toxic gas dispersion for various gases are simulated over the web for varying environmental conditions which is provided by rawinsonde data. The model simulates chemical concentration at ground level up to 10 miles (1 KM grids) in downrange up to an hour after launch. The ambient concentration of the gas dispersion and the deposition of toxic particles are used as inputs for a human health risk assessment model. The advantage of the present model is the accessibility and dissemination of model results to other NASA centers over the web. The model can be remotely operated and various scenarios can be analyzed.

Bardina, Jorge↗

From Pyrolysis Oil to Advanced Biographite Anode: Unravelling Biocoke Structural Evolution and Delayed Coking Effects

Catalytic graphitization of biomass-derived carbon offers a promising route to produce biographite as a sustainable alternative to petroleum-based synthetic graphite for lithium-ion battery (LIB) anodes. This study investigates the physicochemical properties of biocokes produced from pyrolysis oil at carbonization temperatures ranging from 150 degrees C to 500 degrees C. Using an iron (Fe) catalyst, graphitization was performed at 1500 degrees C, significantly lower than the ~3000 degrees C required for conventional synthetic graphite. The effects of introducing an intermediate-temperature hold (400 degrees C-600 degrees C) prior to graphitization were evaluated, simulating a "delayed coking" process to enable the coproduction of sustainable aviation fuels (SAFs). Chemical structure evolution during biocoke formation was analyzed, and proposed mechanisms are presented. Biographites produced via the delayed coking pathway exhibited high crystallinity and excellent electrochemical performance in both half-cell and full-cell LIB configurations. The full cells exhibited an initial discharge capacity close to the theoretical capacity of the NMC622 cathode (175 mAh/g at 4.2 V), and high capacity retention (~88%) after 150 cycles. Notably, the graphitic and electrochemical properties remained stable across the range of intermediate hold temperatures. These findings provide a foundation for optimizing temperature parameters in delayed coking systems to enable scalable, integrated production of biographite and SAFs from pyrolysis oil.

09 BIOMASS FUELS↗

High voltage electron microscopy and electron diffraction of pyroxenes in type B lunar samples from Apollo 11

Lunar pyroxene 10044 specimens cleaved and sectioned by diamond knife ultramicrotomy were examined by standard (75 to 100 kV) and high voltage (200 kV) electron microscopy and diffraction. Salient findings based on evaluation of 2000 plates show uniform 300 to 600 A-wide bands, probably corresponding to single crystal domains, with lattice spacings of 2. A High resolution bright and dark field images of iron-rich and magnesium-rich crystals were compared with corresponding electron diffraction patterns. Possible relations of observed structures to magnetic domains were considered.

Fernandez-Moran, H.↗

A continental rift model for the La Grande greenstone belt

Stratigraphic relationships and the geochemistry of volcanic rocks contrain the nature and timing of the tectonic and magmatic processes in the pre-deformational history of the La Grande greenstone belt in the Superior Province of north-central Quebec. The lowermost supracrustals in this belt are obscured by syntectonic granitoid intrusives. The supracrustal succession in the western part of the belt consists of a lower sequence of immature clastic sediments and mafic volcanoclastics, overlain by pillowed and massive basalts. Further east, along tectonic strike, a lower sequence of mafic volcanoclastics and immature clastic sediments is overlain by a thick sequence of pillowed and massive basalts, and resedimented coarse clastic sediments and banded iron formation. These are overlain by assive basaltic andesites, andesites and intermediate volcanoclastics intercalated with immature clastic sediments. In contrast, in the eastern part of the belt lenses of felsic volcanics and volcanoclastics occur at the base of the succession and pillowed and massive basalts are overlain by komatiites at the top. The La Grande greenstone belt can be explained as the product of continental rifting. The restricted occurence of komatiites, and eastwardly directed paleocurrents in clastic sediments in the central part of the belt are consistent with rifting commencing in the east and propagating westward with time. The increase in depth of emplacement and deposition with time of the lower three units in the central part of the belt reflects deposition in a subsiding basin. These supracrustal rocks are believed to represent the initial rift succession.

Skulski, T.↗

On the dependence of solar flare X-ray spectral line intensity ratios of highly ionized sulfur, calcium, and iron on electron temperature, differential emission measure, and atomic physics

This paper focuses on what can be learned about the emission measure distribution and certain atomic physics parameters from spectral lines of highly ionized ions of sulfur, calcium, and iron that appear in solar flare spectra. The particular lines chosen for analysis allow the electron temperature to be determined independently of the assumption of ionization equilibrium. An attempt is made to find emission measure models based on selected functional dependences of emission measure on temperature that reproduce the observed temperatures deduced from spectral line ratios as well as the relative intensities of resonance lines of different elements.

Doschek, G. A.↗

Lunar Meteorite Queen Alexandra Range 93069 and the Iron Concentration of the Lunar Highlands Surface

Lunar meteorite Queen Alexandra Range 93069 is a clast-rich, glassy-matrix regolith breccia of ferroan, highly aluminous bulk composition. It is similar in composition to other feldspathic lunar meteorites but differs in having higher concentrations of siderophile elements and incompatible trace elements. Based on electron microprobe analyses of the fusion crust, glassy matrix, and clasts, and instrumental neutron activation analysis of breccia fragments, QUE 93069 is dominated by nonmare components of ferroan, noritic- anorthosite bulk composition. Thin section QUE 93069,31 also contains a large, impact-melted, partially devitrified clast of magnesian, anorthositic-norite composition. The enrichment in Fe, Sc, and Cr and lower Mg/Fe ratio of lunar meteorites Yamato 791197 and Yamato 82192/3 compared to other feldspathic lunar meteorites can be attributed to a small proportion (5-10%) of low-Ti mare basalt. It is likely that the non- mare components of Yamato 82192/3 are similar to and occur in similar abundance to those of Yamato 86032, with which it is paired. There is a significant difference between the average FeO concentration of the lunar highlands surface as inferred from the feldspathic lunar meteorites (mean: approx. 5.0%; range: 4.3-6.1 %) and a recent estimate based on data from the Clementine mission (3.6%).

Korotev, Randy L.↗

Multihead Attention U‐Net for Magnetic Particle Imaging–Computed Tomography Image Segmentation

Magnetic particle imaging (MPI) is an emerging noninvasive molecular imaging modality with high sensitivity and specificity, exceptional linear quantitative ability, and potential for successful applications in clinical settings. Computed tomography (CT) is typically combined with the MPI image to obtain more anatomical information. Herein, a deep learning‐based approach for MPI‐CT image segmentation is presented. The dataset utilized in training the proposed deep learning model is obtained from a transgenic mouse model of breast cancer following administration of indocyanine green (ICG)‐conjugated superparamagnetic iron oxide nanoworms (NWs‐ICG) as the tracer. The NWs‐ICG particles progressively accumulate in tumors due to the enhanced permeability and retention (EPR) effect. The proposed deep learning model exploits the advantages of the multihead attention mechanism and the U‐Net model to perform segmentation on the MPI‐CT images, showing superb results. In addition, the model is characterized with a different number of attention heads to explore the optimal number for our custom MPI‐CT dataset.

Juhong, Aniwat↗