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57 Fe nuclear resonance vibrational spectroscopic studies of tetranuclear iron clusters bearing terminal iron( III )–oxido/hydroxido moieties

57 Fe nuclear resonance vibrational spectroscopy (NRVS) has been applied to study a series of tetranuclear iron ([Fe 4 ]) clusters based on a multidentate ligand platform (L 3− ) anchored by a 1,3,5-triarylbenzene linker and pyrazolate or (tertbutylamino)pyrazolate ligand (PzNH t Bu − ). These clusters bear a terminal Fe(III)–O/OH moiety at the apical position and three additional iron centers forming the basal positions. The three basal irons are connected with the apical iron center via a μ 4 -oxido ligand. Detailed vibrational analysis via density functional theory calculations revealed that strong NRVS spectral features below 400 cm −1 can be used as an oxidation state marker for the overall [Fe 4 ] cluster core. The terminal Fe(III)–O/OH stretching frequencies, which were observed in the range of 500–700 cm −1 , can be strongly modulated (energy shifts of 20–40 cm −1 were observed) upon redox events at the three remote basal iron centers of the [Fe 4 ] cluster without the change of the terminal Fe(III) oxidation state and its coordination environment. Therefore, the current study provides a quantitative vibrational analysis of how the remote iron centers within the same iron cluster exert exquisite control of the chemical reactivities and thermodynamic properties of the specific iron site that is responsible for small molecule activation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Iron and alloys of iron

All lunar soil contains iron in the metallic form, mostly as an iron-nickel alloy in concentrations of a few tenths of 1 percent. Some of this free iron can be easily separated by magnetic means. It is estimated that the magnetic separation of 100,000 tons of lunar soil would yield 150-200 tons of iron. Agglutinates contain metallic iron which could be extracted by melting and made into powder metallurgy products. The characteristics and potential uses of the pure-iron and iron-alloy lunar products are discussed. Processes for working iron that might be used in a nonterrestrial facility are also addressed.

Sastri, Sankar↗

Iron nitride permanent magnet and technique for forming iron nitride permanent magnet

A permanent magnet may include a Fe 16 N 2 phase constitution. In some examples, the permanent magnet may be formed by a technique that includes straining an iron wire or sheet comprising at least one iron crystal in a direction substantially parallel to a <001> crystal axis of the iron crystal; nitridizing the iron wire or sheet to form a nitridized iron wire or sheet; annealing the nitridized iron wire or sheet to form a Fe 16 N 2 phase constitution in at least a portion of the nitridized iron wire or sheet; and pressing the nitridized iron wires and sheets to form bulk permanent magnet.

Wang, Jian-Ping↗

Removal of As(V) from wastewaters using magnetic iron oxides formed by zero-valent iron electrocoagulation

Electrocoagulation of zero-valent iron has been widely applied to the removal of dissolved arsenic, but the solid-liquid separation of arsenic-containing precipitates remains technically challenging. In this work, zero-valent iron was electrochemically oxidized to magnetic iron oxides for the removal of As(V) from simulated and actual mining wastewaters. The results indicated that lepidocrocite was formed when zero-valent iron was oxidized by dissolved oxygen, but ferrihydrite and green rust were first formed and then transformed to magnetic iron oxides (mainly magnetite and maghemite) in the electrochemical oxidation from 0 to 0.9 V (vs. SCE), which facilitates the adsorption of As(V) and subsequent solid-liquid separation under a magnetic field. In simulated As(V)-containing solution with initial pH 7.0, zero-valent iron was electrochemically oxidized to magnetite and maghemite at 0.6 V (vs. SCE) for 2 h. The As(V) concentration first decreased from 5127.5 to 26.8 μg L -1 with a removal ratio of 99.5%. In actual mining wastewaters, zero-valent iron was electrochemically oxidized to maghemite at 0.6 V (vs. SCE) for 24 h, and the As(V) concentration decreased from 5486.4 to 3.6 μg L -1 with a removal ratio of 99.9%. The removal ratio of As(V) increased slightly with increasing potential, and increased first and then decreased with increasing initial pH. Compared with that of SO 4 2- and NO 3 - , the presence of Cl - significantly enhanced the removal of As(V). This work provides a highly efficient, facile and low-cost technique for the treatment of arsenic-containing wastewaters.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High‐Pressure Phase Stability and Thermoelastic Properties of Iron Carbonitrides and Nitrogen in the Deep Earth

Abstract Iron‐dominant metallic phases are likely the primary hosts for nitrogen in the reduced deep Earth, hence the storage of nitrogen in the lower mantle and the core is governed by the behavior of the Fe‐N‐C system at high temperatures and pressures. In this study, phase transitions and thermoelastic properties of iron carbonitrides were investigated at high pressure‐temperature conditions by diamond anvil cell experiments and first‐principles calculations. Experimental data revealed no phase transition in ε ‐type Fe 4 (N 0.6 C 0.4 ) or Fe 7 (N 0.75 C 0.25 ) 3 up to 60 GPa at room temperature. At high temperature, Fe 7 (N 0.75 C 0.25 ) 3 transforms into the Fe 3 C‐type phase at ∼27 GPa, and then into the Fe 7 C 3 ‐type phase at ∼45 GPa, which is also corroborated by our theoretical calculations. We found that the phase stability of iron carbonitrides mainly depends on the N/C ratio, and the elastic properties of iron carbonitrides are dominantly affected by the Fe/(N+C) ratio. Iron carbonitrides with diverse structures may be the main host for nitrogen in the deep mantle. Some iron carbonitride inclusions in lower mantle diamonds could be the residue of the primordial mantle or originate from subducted nitrogen‐bearing materials, rather than iron‐enriched phases of the outer core. In addition, our experiments confirmed the existence of Fe 7 C 3 ‐type Fe 7 C 3 ‐Fe 7 N 3 solid solutions above 40 GPa. Fe 7 C 3 ‐type Fe 7 (C, N) 3 has comparable density and thermoelastic properties to its isostructural endmembers and may be a promising candidate constituent of the Earth's inner core.

Huang, Shengxuan↗

Chemical classification of iron meteorites. VIII - Groups IC, IIE, IIIF and 97 other irons

Results are reported for determinations of Ni, Ga, Ge, and Ir concentrations in 106 iron meteorites. Three new groups are defined (IC, IIE, and IIIF) which contain 10, 12, and 5 irons, respectively. It is noted that group IC is a cohenite-rich group distantly related to IA, group IIE consists of those irons previously designated as Weekeroo Station type together with five others having similar compositions but diverse structures, and group IIIF is a well-defined group of low-Ni and low-Ge irons. Several anomalous irons are discussed, including a cluster of five plessitic octahedrites and ataxites with Ge/Ga atomic ratios ranging from 10 to 16 and a meteorite that has the second highest Ni content of any iron. It is shown that the IIE irons are compositionally similar to the mesosiderites and pallasites, and it is suggested that the three groups probably formed at approximately the same heliocentric distance.

Scott, E. R. D.↗

Metagenomic Study of Iron Homeostasis in Iron Depositing Hot Spring Cyanobacterial Community

Introduction: It is not clear how an iron-rich thermal hydrosphere could be hospitable to cyanobacteria, since reduced iron appears to stimulate oxidative stress in all domains of life and particularly in oxygenic phototrophs. Therefore, metagenomic study of cyanobacterial community in iron-depositing hot springs may help elucidate how oxygenic prokaryotes can withstand the extremely high concentrations of reactive oxygen species (ROS) produced by interaction between environmental Fe2+ and O2. Method: Anchor proteins from various species of cyanobacteria and some anoxygenic phototrophs were selected on the basis of their hypothetical role in Fe homeostasis and the suppression of oxidative stress and were BLASTed against the metagenomes of iron-depositing Chocolate Pots and freshwater Mushroom hot springs. Results: BLASTing proteins hypothesized to be involved in Fe homeostasis against the microbiomes from the two springs revealed that iron-depositing hot spring has a greater abundance of defensive proteins such as bacterioferritin comigratory protein (Bcp) and DNA-binding Ferritin like protein (Dps) than a fresh-water hot spring. One may speculate that the abundance of Bcp and Dps in an iron-depositing hot spring is connected to the need to suppress oxidative stress in bacteria inhabiting environments with high Fe2+ concnetration. In both springs, Bcp and Dps are concentrated within the cyanobacterial fractions of the microbial community (regardless of abundance). Fe3+ siderophore transport (from the transport system permease protein query) may be less essential to the microbial community of CP because of the high [Fe]. Conclusion: Further research is needed to confirm that these proteins are unique to photoautotrophs such as those living in iron-depositing hot spring.

Brown, I.↗

Probing the lattice structure of dynamically compressed and released single crystal iron through the alpha to epsilon phase transition

In this work, experiments using broadband Laue x-ray diffraction (XRD) were used to examine the lattice structure of dynamically compressed [100]-oriented single crystal iron samples at the Dynamic Compression Sector at the Advanced Photon Source. These experiments used 1 μm thick iron single crystal samples sandwiched between a polyimide ablator and a polycarbonate window. A 100 J, 10 ns duration laser pulse incident on the polyimide ablator was used to shock compress the iron samples to initial stresses greater than 25 GPa, exceeding the ~13 GPa alpha (body-centered-cubic or bcc structure) to epsilon (hexagonal-close-packed or hcp structure) phase transition stress. XRD measurements were performed at various times relative to the shock wave entering the iron sample: early times, <~150 ps while the initial shock waves propagated through the iron; intermediate times, after the iron equilibrated with the ablator and window reaching a plateau stress state (12 or 17 GPa) lasting several nanoseconds; and late times, during uniaxial strain release. The early time measurements show that in <~150 ps, the high-pressure hcp phase is relaxed with a c/a ratio of 1.61, contrary to previous laser shock experiments where a c/a ratio of 1.7 was inferred. In the plateau stress state and partially released states, XRD measurements showed that the hcp structure retained a c/a ratio of 1.61 with no observable changes in the microstructure. Upon stress release at ~1 GPa/ns release rate, the reverse phase transition (hcp to bcc) to the original single crystal orientation (implying a transformation memory effect) was observed to reach completion somewhere between 13 and 11 GPa, indicating little stress hysteresis under rapid uniaxial strain release. A similar memory effect for the reverse hcp to bcc transformation has been previously observed under hydrostatic compression. However, the bcc/hcp orientation relationships differ somewhat between dynamic and static compression experiments, implying that the transformation pathway under uniaxial dynamic strain differs from the Burgers mechanism.

36 MATERIALS SCIENCE↗

Evaluating and Enhancing Iron Removal via Filterable Iron Precipitates Formation during Coal-Waste Bioleaching

Iron removal via jarosite precipitate formation is a commonly used technique in various hydrometallurgical processes. Excess iron removal often becomes essential to an overall metal recovery circuit. This is particularly important to processes involving iron-bearing minerals. A technique, which involved the use of pyrite to generate acid for leaching, for iron removal is critical to enabling the process. Iron removal using CaO or similar reagents is expensive and often results in lost product. In the present study, various compounds that facilitate jarosite formation, namely Na2SO4, NH4OH, KCl, and KOH, were utilized and their effect in precipitation was observed. Visual Minteq assisted simulations were run in order to evaluate favorable conditions for iron removal. Morphology and elemental composition of precipitates were analyzed using scanning electron microscopy equipped with energy-dispersive X-ray spectroscopy, and the phase purity was identified using X-ray diffraction analysis.

99 GENERAL AND MISCELLANEOUS↗

Investigation of Ionic Liquids Isolated Iron for Ductile Iron Castings

As research continues for missions beyond low-Earth orbit, in-situ resource utilization (ISRU) methods are critical. For Lunar and Martian colonization, the ability to manufacture mechanical and structural components with local resources is essential. Ionic liquids (IL) are being studied at NASA Marshall Space Flight Center (MSFC) to harvest elemental metals from meteorites and regolith oxides. In this investigation, the viability of casting ductile iron using ionic liquids sourced iron and nickel was explored given ductile iron’s range of applications and performance as an as-cast alloy. Ingots were produced using commercial elements to simulate the use of IL iron with carbon sourced from the by-products of a life support system currently tested at MSFC. Samples were cast and compared to commercial ductile iron with phase transformation diagrams,microstructures, and hardness. Results showed ionic liquids sourced elements are a viable source of elemental alloying materials for a range of ductile iron alloys.

Ionic Liquids↗

A portable and monoenergetic 24 keV neutron source based on 124Sb-9Be photoneutrons and an iron filter

A portable monoenergetic 24 keV neutron source based on the 124Sb-9Be photoneutron reaction and an iron filter has been constructed and characterized. The coincidence of the neutron energy from SbBe and the low interaction cross-section with iron (mean free path up to 29 cm) makes pure iron specially suited to shield against gamma rays from 124Sb decays while letting through the neutrons. To increase the 124Sb activity and thus the neutron flux, a >1 GBq 124Sb source was produced by irradiating a natural Sb metal pellet with a high flux of thermal neutrons in a nuclear reactor. The design of the source shielding structure makes for easy transportation and deployment. A hydrogen gas proportional counter is used to characterize the neutrons emitted by the source and a NaI detector is used for gamma background characterization. At the exit opening of the neutron beam, the characterization determined the neutron flux in the energy range 20–25 keV to be 6.00±0.30 neutrons per cm2 per second and the total gamma flux to be 245±8 gammas per cm2 per second (numbers scaled to 1 GBq activity of the 124Sb source). A liquid scintillator detector is demonstrated to be sensitive to neutrons with incident kinetic energies from 8 to 17 keV, so it can be paired with the source as a backing detector for neutron scattering calibration experiments. This photoneutron source provides a good tool for in-situ low energy nuclear recoil calibration for dark matter experiments and coherent elastic neutrino-nucleus scattering experiments.

Dark Matter detectors (WIMPs, axions, etc.)↗

Large exotic spin torques in antiferromagnetic iron rhodium.

Spin torque is a promising tool for driving magnetization dynamics for computing technologies. These torques can be easily produced by spin-orbit effects, but for most conventional spin source materials, a high degree of crystal symmetry limits the geometry of the spin torques produced. Magnetic ordering is one way to reduce the symmetry of a material and allow exotic torques, and antiferromagnets are particularly promising because they are robust against external fields. We present spin torque ferromagnetic resonance (ST-FMR) measurements and second harmonic Hall measurements characterizing the spin torques in anti -ferromagnetic iron rhodium alloy. We report extremely large, strongly temperature-dependent exotic spin torques with a geometry apparently defined by the magnetic ordering direction. We find the spin torque efficiency of iron rhodium to be (207 +/- 94)% at 170 K and (88 +/- 32)% at room temperature. We support our conclusions with theoretical calculations showing how the antiferromagnetic ordering in iron rhodium gives rise to such exotic torques.

Gibbons, Jonathan↗

Iron-tolerant Cyanobacteria as a Tool to Study Terrestrial and Extraterrestrial Iron Deposition

We are investigating biological mechanisms of terrestrial iron deposition as analogs for Martian hematite recently confirmed by. Possible terrestrial analogs include iron oxide hydrothermal deposits, rock varnish, iron-rich laterites, ferricrete soils, moki balls, and banded iron formations (BIFs). With the discovery of recent volcanic activity in the summit craters of five Martian volcanoes, renewed interest in the iron dynamics of terrestrial hydrothermal environments and associated microorganisms is warranted. In this study we describe a new genus and species of CB exhibiting elevated dissolved iron tolerance and the ability to precipitate hematite on the surface of their exopolymeric sheathes.

Brown, I. I.↗

Comparison of Carbon XANES Spectra from an Iron Sulfide from Comet Wild 2 with an Iron Sulfide Interplanetary Dust Particle

Among one of the first particles removed from the aerogel collector from the Stardust sample return mission was an approx. 5 micron sized iron sulfide. The majority of the spectra from 5 different sections of this particle suggests the presence of aliphatic compounds. Due to the heat of capture in the aerogel we initially assumed these aliphatic compounds were not cometary but after comparing these results to a heated iron sulfide interplanetary dust particle (IDP) we believe our initial interpretation of these spectra was not correct. It has been suggested that ice coating on iron sulfides leads to aqueous alteration in IDP clusters which can then lead to the formation of complex organic compounds from unprocessed organics in the IDPs similar to unprocessed organics found in comets [1]. Iron sulfides have been demonstrated to not only transform halogenated aliphatic hydrocarbons but also enhance the bonding of rubber to steel [2,3]. Bromfield and Coville (1997) demonstrated using Xray photoelectron spectroscopy that "the surface enhancement of segregated sulfur to the surface of sulfided precipitated iron catalysts facilitates the formation of a low-dimensional structure of extraordinary properties" [4]. It may be that the iron sulfide acts in some way to protect aliphatic compounds from alteration due to heat.

Wirick, S.↗

Amino Acid Abundances and Compositions in Iron and Stony-Iron Meteorites

The organic compositions of carbonaceous chondrite meteorites have been extensively studied; however, there have been fewer reports of other meteorite classes, and almost none from iron meteorites, which contain much less carbon than carbonaceous chondrites but make up ~4% of observed meteorite falls. Here, we report the bulk amino acid content of three iron meteorites (Campo del Cielo, IAB; Canyon Diablo, IAB; and Cape York, IIIAB) and both the metal and silicate portions of a pallasite (Imilac). We developed a novel method to prepare the samples for analysis, followed by hot water extraction and analysis via liquid chromatography‐mass spectrometry. Free amino acid abundances ranging from 301 to 1216 pmol/g were observed in the meteorites, with the highest abundance in the silicate portion of the pallasite. Although some of the amino acid content could be attributed to terrestrial contamination, evidence suggests that some compounds are indigenous. A suite of C(5) amino acids was observed with a distinct distribution favoring a straight chain (n‐pentanoic acid) structure; this straight chain dominance is suggestive of that observed in thermally altered stony meteorites. Amino acids were also observed in terrestrial iron granules that were milled and analyzed in the same way as the meteorites, although the distribution of detected amino acids was different. It is possible that similar formation mechanisms existed in both the meteorites and the terrestrial iron, or that observed amino acids resulted from reactions of precursors during sample preparation. This work suggests that iron meteorites should not be overlooked for contributions of amino acids and likely other soluble organic molecules to the early Earth. Future studies of iron–nickel meteorites and asteroids, such as Psyche, may provide further insights into their potential organic inventory.

Jamie E. Elsila↗