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Iron and stony iron meteorites chemical classification, noting Ni, Ga, Ge and Ir concentrations and metal phases
Narrow band Ross filter measurements of the Fe 25 line flux around 0.185 nm and simultaneous broadband measurements during a solar flare were used to determine the relationship between the solar coronal abundances of iron and helium. The Fe 25 ion population was also determined as a function of time. The proportional counter and the Ross filter on OSO-7 were utilized. The data were analyzed under the separate assumptions that (1) the electron density was high enough that a single temperature could characterize the continuum spectrum and the ionization equilibrium, and that (2) the electron density was low so that the ion populations trailed the electron temperature in time. It was found that the density was at least 5x10 to the 9th power, and that the high density assumption was valid. It was also found that the iron abundance is 0.000011 for a helium abundance of 0.2, relative to hydrogen.
Speculation about the possible mechanisms for core formation in small asteroids raises more questions than answers. Petrologic evidence from iron meteorites, pallasites, and astronomical observations of M asteroids suggests that many small bodies were capable of core formation. Recent work by Taylor reviews the geochemical evidence and examines the possible physical/mechanical constraints on segregation processes. Taylor's evaluation suggests that extensive silicate partial melting (preferably 50 vol. percent or greater) is required before metal can segregate from the surrounding silicate and form a metal core. The arguments for large degrees of silicate partial melting are two-fold: (1) elemental trends in iron meteorites require that the metal was at is liquidus; and (2) experimental observations of metal/sulfide inclusions in partially molten silicate meteorites show that the metal/sulfide tends to form spherules in the liquid silicate due to surface tension effects. Taylor points out that for these metal spherules to sink through a silicate mush, high degrees of silicate partial melting are required to lower the silicate yield strength. Although some qualitative experimental data exists, little is actually known about the behavior of metals and liquid sulfides dispersed in silicate systems. In addition, we have been impressed with the ability of cumulative olivine to expel trapped liquid when placed in a thermal gradient. Consequently, we undertook to accomplish the following: (1) experimentally evaluate the potential for metal/sulfide/silicate segregation in a thermal gradient; and (2) obtain quantitative data of the wetting parameters of metal-sulfide melts among silicate grains.
An exploratory application of x ray absorption near edge structure (XANES) analysis using the synchrotron x ray microprobe was undertaken to obtain Fe XANES spectra on individual sub-millimeter grains in conventional polished sections. The experiments concentrated on determinations of Fe valence in a suite of iron oxide minerals for which independent estimates of the iron speciation could be made by electron microprobe analysis and x ray diffraction.
Iron formations are ancient, laminated chemical sediments containing at least 15 wt% Fe. We discuss possible mechanisms for their formation in aqueous environments on early Mars. Such iron oxide deposits may be detectable today.
The Mossbauer (MB) spectrometers on the Mars Exploration Rovers (MER) Spirit (Gusev crater) and Opportunity (Meridiani Planum) have detected 14 Fe-bearing phases, and mineralogical assignments have been made for all except 3. Identified Fe2+-bearing phases are olivine, pyroxene, ilmenite, and troilite. Magnetite and chromite are present as mixed Fe(2+) and Fe(3+) phases. Identified Fe(3+) phase are jarosite, hematite, goethite, and nanophase ferric oxide (npOx). Fe(sup 0) (iron metal) is present as kamacite. Nanophase ferric oxide (npOx) is a generic name for octahedrally coordinated Fe(3+) alteration products that cannot be otherwise mineralogically assigned on the basis of MER data. On the Earth, npOx would include ferrihydrite, iddingsite, schwertmannite, akaganeite, and superparamagnetic hematite and goethite. The Mars Reconnaissance Orbiter CRISM instrument, a visible, near-IR hyperspectral imager (approximately 0.35 to 4 micron) enables mineralogical examination of Mars with a tool that is sensitive to H2O and to M-OH (M = Al, Si, Fe, Mg, etc.) at spatial resolution of about 20 m/pixel. We examined a CRISM image of the MER region of Gusev crater (Columbia Hills and plains to the west), looking for spectral evidence of the aqueous process apparent from the MER analyses. We also searched for spectral constraints for the mineralogical composition of our unidentified Fe-bearing phases and the forms of npOx present on Mars. We also consider evidence from analogue samples that the precursor for the goethite detected by MB in Clovis Class rocks is an iron sulfide. We suggest that there is some indirect evidence that elemental sulfur might be present to different extents in Clovis Class rocks, the Fe3Sulfate-rich soils, and perhaps even typical (Laguna Class) surface soils.
An improved understanding of anthropogenic impacts on ocean fertility requires knowledge of anthropogenic dust mineralogy and associated Fe speciation as a critical step toward developing Fe solubility models constrained by mineralogical composition. This study explored the utility of micro-focused X-ray absorption spectroscopy ({mu}-XAS) in characterizing the speciation of Fe in urban dust samples. A micro-focused beam of 10 x 7 {micro}m made possible the measurement of the Fe K edge XAS spectra of individual dust particles in the PM5.6 size fraction collected in Newark, New Jersey, USA. Spectral analysis indicated the presence of mixtures of Fe-containing minerals within individual dust particles; we observed significant magnetite content along with other Fe(III)-(hydr)oxide minerals which could not be conclusively identified. Our data indicate that detailed quantitative determination of Fe speciation requires extended energy scans to constrain the types and relative abundance of Fe species present. We observe heterogeneity in Fe speciation at the dust particle level, which underscores the importance of analyzing a statistically adequate number of particles within each dust sample. Where possible, {mu}-XAS measurements should be complemented with additional characterization techniques such as {mu}-XRD and bulk XAS to obtain a comprehensive picture of the Fe speciation in dust materials. X-ray microprobes should be used to complement bulk methods used to determine particle composition, methods that fail to record particle heterogeneity.
This paper discusses the effects of composition and canister centerline cooling (CCC) on the microstructures, phase distribution, and chemical durability of dehalogenated iron phosphate waste forms starting from chloride-based salt simulants including KCl (Simple-1), NdCl3 (Simple-2), SrCl2 (Simple-3), LaCl3 (Simple-4), LiCl (Simple-5), CsCl (Simple-6), as well as a complex simulant containing LiCl, KCl, NaCl, CsI, SrCl2, CeCl3, and NdCl3 called ERV2. The simulants represent salt constituents present in salt wastes from electrorefiners used for electrochemical reprocessing. These salts are reacted with ammonium dihydrogen phosphate (ADP) resulting in a NH4Cl (dechlorination) byproduct that is captured and phosphate product containing oxides of the salt cations. This product is further stabilized using Fe2O3 through vitrification at higher temperatures. The results presented herein describe the properties of CCC-treated materials following dechlorination and vitrification including phase identification and quantification, elemental distributions, and chemical durabilities. The chemical durability in the CCC-cooled samples are lower durability than quenched materials for the ERV2 samples. The phases formed upon CCC cooling are very complex compositionally and microstructurally.
By reaction between synthetic phosphosiderite FePO{sub 4}{center_dot}2H{sub 2}O, urea (NH{sub 2}){sub 2}CO, and acetone (CH{sub 3}){sub 2}CO, we report a novel solvothermal synthesis of polycrystalline NH{sub 4}FePO{sub 4}{center_dot}H{sub 2}O. The preparation of other two individual phases, NH{sub 4}Fe{sub 2}(OH)(PO{sub 4}){sub 2}{center_dot}2H{sub 2}O and NH{sub 4}Fe{sub 2}(PO{sub 4}){sub 2}, is also described. The obtained product is a function of the reaction time and the N/P molar ratio in the reagent mixture, and the existence of structural memory in the dissolution-precipitation processes is discussed. Below 25 K, NH{sub 4}FePO{sub 4}{center_dot}H{sub 2}O behaves magnetically in a complex way, because both ferromagnetic and antiferromagnetic signals are superimposed, suggesting the existence of a canting of iron(II) magnetic moments. - Graphical abstract: Solvothermal synthesis of polycrystalline NH{sub 4}FePO{sub 4}{center_dot}H{sub 2}O is presented. The preparation of other two individual phases, NH{sub 4}Fe{sub 2}(OH)(PO{sub 4}){sub 2}{center_dot}2H{sub 2}O and NH{sub 4}Fe{sub 2}(PO{sub 4}){sub 2} as a function of the N/P molar ratio in the reagent mixture and the reaction time, is also described. Highlights: Black-Right-Pointing-Pointer Solvothermal synthesis of NH{sub 4}FePO{sub 4}{center_dot}H{sub 2}O from an Fe(III) phosphate: reduction process. Black-Right-Pointing-Pointer Formation of two intermediate metastable phases: phase diagram. Black-Right-Pointing-Pointer Thermal decomposition in two steps: mass loss of both water and ammonia. Black-Right-Pointing-Pointer Magnetic behaviour: AF+constant spontaneous magnetization.
Two new barium iron pnictide–selenides, Ba{sub 2}FeSbSe{sub 5} and Ba{sub 2}FeBiSe{sub 5}, were synthesized by a high-temperature solid-state route and their crystal structures were determined using single crystal X-ray diffraction. Both compounds are isomorphic to the high pressure phase Ba{sub 3}FeS{sub 5} and crystallize in the orthorhombic space group Pnma (No. 62) with cell parameters of a=12.603(2)/12.619(2) Å, b=9.106(1)/9.183(1) Å, c=9.145(1)/9.123(1) Å and Z=4 for Ba{sub 2}FeSbSe{sub 5} and Ba{sub 2}FeBiSe{sub 5}, respectively. According to differential scanning calorimetry, Ba{sub 2}FePnSe{sub 5} compounds exhibit high thermal stability and melt congruently at 1055(5) K (Pn=Sb) and 1105(5) K (Pn=Bi). Magnetic characterizations reveal strong antiferromagnetic nearest-neighbor interactions in both compounds resulting in an antiferromagnetic ordering at 58(1) K for Ba{sub 2}FeSbSe{sub 5} and 79(2) K for Ba{sub 2}FeBiSe{sub 5}. The magnetic interactions between Fe{sup 3+} centers, which are at least 6 Å apart from each other, are mediated by superexchange interactions. - Graphical abstract: In Ba{sub 2}FeSbSe{sub 5} and Ba{sub 2}FeBiSe{sub 5} the magnetic interactions between Fe{sup 3+} centers, which are at least 6 Å apart from each other, are mediated by superexchange interactions. - Highlights: • New compounds Ba{sub 2}FeSbSe{sub 5} and Ba{sub 2}FeBiSe{sub 5} have been synthesized. • The crystal structure was determined by single crystal X-ray diffraction. • Both compounds melt congruently at temperatures above 1000 K. • Ba{sub 2}FeSbSe{sub 5} and Ba{sub 2}FeBiSe{sub 5} exhibit AFM ordering at 58 K (Sb) and 70 K (Bi). • Magnetic exchange between Fe{sup 3+} is mediated by either Se–Sb(Bi)–Se or Se–Ba–Se bridges.
Nitrous oxide (N 2 O) is the third largest contributor to anthropogenic greenhouse gas emissions and plays a detrimental role in the depletion of ozone. Despite the contribution of N 2 O as an atmospheric pollutant, there are currently only a few examples of electrochemical N 2 O remediation to N 2 . Herein we report the electrocatalytic deoxygenation of N 2 O by iron tetraphenylporphyrin (FeTPP) to form N 2 with quantitative Faradaic efficiency and an observed rate of 1.91 s –1 . No degradation was observed after controlled potential electrolysis. Mechanistic investigation of the proposed catalytic steps determined that hydrogen-bond donors are critical for accelerating N 2 O activation and that proton transfer is involved in the rate-determining step.
A relationship between local structure and methylene blue (MB) decomposing ability of nanoparticles (NPs) of metallic iron (Fe{sup 0}) and maghemite (γ‐Fe{sub 2}O{sub 3}) was investigated by {sup 57}Fe Mössbauer spectroscopy, X-ray diffractometry and UV-visible light absorption spectroscopy. γ‐Fe{sub 2}O{sub 3} NPs were successfully prepared by mixing (NH{sub 4}){sub 2}Fe(SO{sub 4}){sub 2}⋅6H{sub 2}O (Mohr's salt) and (NH{sub 4}){sub 3}Fe(C{sub 2}O{sub 4}){sub 3}⋅3H{sub 2}O aqueous solution at 30 °C for 1 h, while those of Fe{sup 0} were obtained by the reduction of Mohr's salt with NaBH{sub 4}. From the Scherrer's equation, the smallest crystallite sizes of γ‐Fe{sub 2}O{sub 3} NPs and Fe{sup 0} NPs were determined to be 9.7 and 1.5 nm, respectively. {sup 57}Fe Mössbauer spectrum of γ‐Fe{sub 2}O{sub 3} NPs consists of a relaxed sextet with isomer shift (δ) of 0.33{sub ±0.01} mm s{sup −1}, internal magnetic field (H{sub int}) of 25.8{sub ±0.5} T, and linewidth (Γ) of 0.62{sub ±0.04} mm s{sup −1}. {sup 57}Fe Mössbauer spectrum of Fe{sup 0} NP is mainly composed of a sextet having δ, Δ, and H{sub int} of 0.00{sub ±0.01} mm s{sup −1} 0.45{sub ±0.01} mm s{sup −1}, and 22.8{sub ±0.1} T, respectively. A bleaching test of the mixture of Fe{sup 0} and γ‐Fe{sub 2}O{sub 3} NPs (3:7 ratio, 100 mg) in MB aqueous solution (20 mL) for 6 h showed a remarkable decrease of MB concentration with the first-order rate constant (k{sub MB}) of 6.7 × 10{sup −1} h{sup −1}. This value is larger than that obtained for the bleaching test using bulk Fe{sup 0}+γ‐Fe{sub 2}O{sub 3} (3:7) mixture (k{sub MB} = 6.5×10{sup −3}h{sup −1}). These results prove that MB decomposing ability is enhanced by the NPs mixture of Fe{sub 0} and γ‐Fe{sub 2}O{sub 3}.
Iron (Fe) oxides exist in a spectrum of structures in the environment, with ferrihydrite widely considered the most bioavailable phase. Yet, ferrihydrite is unstable and rapidly transforms to more crystalline Fe(III) oxides (e.g., goethite, hematite), which are poorly reduced by model dissimilatory Fe(III)-reducing microorganisms. This begs the question, what processes and microbial groups are responsible for reduction of crystalline Fe(III) oxides within sedimentary environments? Further, how do changes in Fe mineralogy shape oxide-hosted microbial populations? To address these questions, we conducted a largescale cultivation effort using various Fe(III) oxides (ferrihydrite, goethite, hematite) and carbon substrates (glucose, lactate, acetate) along a dilution gradient to enrich for microbial populations capable of reducing Fe oxides spanning a wide range of crystallinities and reduction potentials. While carbon source was the most important variable shaping community composition within Fe(III)-reducing enrichments, both Fe oxide type and sediment dilution also had a substantial influence. For instance, with acetate as the carbon source, only ferrihydrite enrichments displayed a significant amount of Fe(III) reduction and the well known dissimilatory metal reducer Geobacter sp. was the dominant organism enriched. In contrast, when glucose and lactate were provided, all three Fe oxides were reduced and reduction coincided with the presence of fermentative (e.g., Enterobacter spp.) and sulfate-reducing bacteria (e.g., Desulfovibrio spp.). Thus, changes in Fe oxide structure and resource availability may shift Fe(III)-reducing communities between dominantly metalrespiring to fermenting and/or sulfate-reducing organisms which are capable of reducing more recalcitrant Fe phases. These findings highlight the need for further targeted investigations into the composition and activity of speciation-directed metal-reducing populations within natural environments.
A synchrotron technique, differential aperture X-ray microscopy (DAXM), has been applied to characterize the microstructure and analyze the local mesoscale residual elastic strain fields around graphite nodules embedded in ferrite matrix grains in ductile cast iron. Compressive residual elastic strains are measured with a maximum strain of ~6.5–8 × 10 –4 near the graphite nodules extending into the matrix about 20 μm, where the elastic strain is near zero. The experimental data are compared with a strain gradient calculated by a finite element model, and good accord has been found but with a significant overprediction of the maximum strain. This is discussed in terms of stress relaxation during cooling or during storage by plastic deformation of the nodule, the matrix or both. Furthermore, relaxation by plastic deformation of the ferrite is demonstrated by the formation of low energy dislocation cell structure also quantified by the DAXM technique.
Highlights: • Development of a new spintronics device. • Development of quantum spin polarized filters. • Development of theory of quantum spin polarized filter. - Abstract: Presently we report spin-polarized state transport in semiconductor–dielectric–iron–semiconductor (SDIS) four-nanolayer sandwich devices. The exchange-resonance spectra in such devices are quite specific, differing also from spectra observed earlier in other three-nanolayer devices. The theoretical model developed earlier is extended and used to interpret the available experimental results. A detailed ab initio analysis of the magnetic-field dependence of the output magnetic moment is also performed. The model predicts an exchange spectrum comprising a series of peaks, with the spectral structure determined by several factors, discussed in the paper.
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