Crystal plasticity modeling of irradiation effects on flow stress in pure-iron and iron-copper alloys
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Chakraborty, Pritam (ORCID:0000000321987409)↗
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Pumping Iron: A Multi-omics Analysis of Two Extremophilic Algae Reveals Iron Economy Management
Marine algae are responsible for half of the world's primary productivity, but this critical carbonsink is often constrained by insufficient iron. One species of marine algae, Dunaliella tertiolecta, isremarkable for its ability to maintain photosynthesis and thrive in low-iron environments. A relatedspecies, Dunaliella salina Bardawil, shares this attribute but is an extremophile found in hypersaline environments. To elucidate how algae manage their iron requirements, we produced highquality genome assemblies and transcriptomes for both species to serve as a foundation for acomparative multi-omics analysis. We identified a host of iron-uptake proteins in both species,including a massive expansion of transferrins and a novel family of siderophore-iron uptakeproteins. Complementing these multiple iron-uptake routes, ferredoxin functions as a large ironreservoir that can be released by induction of flavodoxin. Proteomic analysis revealed reducedinvestment in the photosynthetic apparatus coupled with remodeling of antenna proteins bydramatic iron-deficiency induction of TIDI1, a light harvesting complex protein found also in otherchlorophytes. These combinatorial iron scavenging and sparing strategies make Dunaliellaunique among photosynthetic organisms
iron homeostasis, phytoplankton, Iron starvation i↗
Composition and Pressure Effects on Partitioning of Ferrous Iron in Iron-Rich Lower Mantle Heterogeneities
Both seismic observations of dense low shear velocity regions and models of magma ocean crystallization and mantle dynamics support enrichment of iron in Earth’s lowermost mantle. Physical properties of iron-rich lower mantle heterogeneities in the modern Earth depend on distribution of iron between coexisting lower mantle phases (Mg,Fe)O magnesiowüstite, (Mg,Fe)SiO3 bridgmanite, and (Mg,Fe)SiO3 post-perovskite. The partitioning of iron between these phases was investigated in synthetic ferrous-iron-rich olivine compositions (Mg0.55Fe0.45)2SiO4 and (Mg0.28Fe0.72)2SiO4 at lower mantle conditions ranging from 33–128 GPa and 1900–3000 K in the laser-heated diamond anvil cell. The resulting phase assemblages were characterized by a combination of in situ X-ray diffraction and ex situ transmission electron microscopy. The exchange coefficient between bridgmanite and magnesiowüstite decreases with pressure and bulk Fe# and increases with temperature. Thermodynamic modeling determines that incorporation and partitioning of iron in bridgmanite are explained well by excess volume associated with Mg-Fe exchange. Partitioning results are used to model compositions and densities of mantle phase assemblages as a function of pressure, FeO-content and SiO2-content. Unlike average mantle compositions, iron-rich compositions in the mantle exhibit negative dependence of density on SiO2-content at all mantle depths, an important finding for interpretation of deep lower mantle structures.
Dorfman, Susannah M. (ORCID:0000000239689592)↗
Iron Ion and Iron Hydroxide Adsorption to Charge-Neutral Phosphatidylcholine Templates
Abstract not provided
Wang, Wenjie↗
Sound velocities of iron-nickel (Fe90Ni10) alloy up to 8 GPa and 773 K: The effect of nickel on the elastic properties of bcc-iron at high P-T
Sound velocities of iron and iron-based alloys at high pressure and high temperature are crucial for understanding the composition and structure of Earth’s and other telluric planetary cores. In this study, we performed ultrasonic interferometric measurements of both compressional (ν P ) and shear (ν S ) velocities on a polycrystalline body-centered-cubic (bcc)-Fe 90 Ni 10 up to 8 GPa and 773 K. The elastic moduli and their pressure and temperature derivatives are derived from least-square fits to third-order finite strain equations, yielding K S0 = 154.2(8) GPa, G 0 = 73.2(2) GPa, K' S0 = 4.6(2), G' 0 = 1.5(1), ∂K S /∂T = –0.028(1) GPa/K, and ∂G/∂T = –0.023(1) GPa/K. Furthermore, a comparison with literature data on bcc-Fe suggests that nickel not only decreases both P and S wave velocities but also weakens the temperature effects on the elastic moduli of Fe-Ni alloys.
36 MATERIALS SCIENCE↗
Isotopic Constraints on the Nature of Primary Precipitates in Archean–Early Paleoproterozoic Iron Formations from Determinations of the Iron Phonon Density of States of Greenalite and 2L- and 6L-Ferrihydrite
Iron formations (IFs) are chemical sedimentary rocks that were widely deposited before the Great Oxidation Event (GOE) around 2.4- 2.2 Ga. It is generally thought that IFs precipitated as hydrated Fe 3+ oxides (HFOs) such as ferrihydrite following surface oxidation of Fe 2+ -rich, anoxic deep waters. This model often implicates biological oxidation and underpins reconstructions of marine nutrient concentrations. However, nanoscale petrography indicates that an Fe 2+ silicate, greenalite, is a common primary mineral in well-preserved IFs, motivating an alternative depositional model of anoxic ferrous silicate precipitation. It is unclear, however, if Fe 2+ -rich silicates can produce the Fe isotopic variations in IFs that are well explained by Fe 2+ oxidation. To address this question, we constrain the equilibrium Fe isotopic ( 56 Fe/ 54 Fe) fractionation of greenalite and ferrihydrite by determining the iron phonon densities of states for those minerals. Here, we use ab initio density functional theory (DFT + U) calculations and nuclear resonant inelastic X-ray scattering spectroscopy to show that ferrous greenalite should be isotopically lighter than ferrihydrite by similar to 1-1.2 parts per thousand at equilibrium, and fractionation should scale linearly with increasing Fe 3+ content in greenalite. By anchoring ferrihydrite-greenalite mineral pair fractionations to published experimental Fe isotopic fractionations between HFOs and aqueous Fe 2+ , we show that ferrous greenalite may produce all but the heaviest pre-GOE Fe isotopic compositions and mixed valence greenalites can produce the entire record. Our results suggest that heavy Fe isotope enrichments alone are not diagnostic of primary IF mineralogies, and ferrihydrite and partially oxidized or even purely ferrous greenalite are all viable primary IF mineralogies.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Structure and thermodynamics of uranium-containing iron garnets
Use of crystalline garnet as a waste form phase appears to be advantageous for accommodating actinides from nuclear waste. Previous studies show that large amounts of uranium (U) and its analogues such as cerium (Ce) and thorium (Th) can be incorporated into the garnet structure. In this study, we synthesized U loaded garnet phases, Ca 3 U x Zr 2–x Fe 3 O 12 (x = 0.5–0.7), along with the endmember phase, Ca 3 (Zr 2 )SiFe 3+ 2 O 12 , for comparison. The oxidation states of U were determined by X-ray photoelectron and absorption spectroscopies, revealing the presence of mixed pentavalent and hexavalent uranium in the phases with x = 0.6 and 0.7. The oxidation states and coordination environments of Fe were measured using transmission 57 Fe-Mössbauer spectroscopy, which shows that all iron is tetrahedrally coordinated Fe 3+ . U substitution had a significant effect on local environments, the extent of U substitution within this range had a minimal effect on the structure, and unlike in the x = 0 sample, Fe exists in two different environments in the substituted garnets. The enthalpies of formation of garnet phases from constituent oxides and elements were first time determined by high temperature oxide melt solution calorimetry. The results indicate that these substituted garnets are thermodynamically stable under reducing conditions. Furthermore, our structural and thermodynamic analysis further provides explanation for the formation of natural uranium garnet, elbrusite-(Zr), and supports the potential use of Ca 3 U x Zr 2–x Fe 3 O 12 as viable waste form phases for U and other actinides.
12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
Electrochemical chlor-iron process for iron production from iron oxide and salt water
The iron and steel industry accounts for ~8% of global greenhouse gas emissions. Electrochemical reduction of iron ore to metal for electric arc furnaces can enable sustainable steel production, but existing electrochemical processes require expensive capital or electrolytes. Here we report a low-temperature, electrochemical cell that consumes low-cost and abundant iron oxide and aqueous sodium chloride, while co-producing sodium hydroxide and chlorine. Industrially relevant current densities and Faradaic efficiencies for iron production were demonstrated, with 94% selectivity to iron metal at an applied current density of 200 mA cm –2 . Freestanding films of phase-pure iron were formed after 4h of continuous, stable electrolysis. The process can lead to levelized costs of iron that are competitive with iron produced in fossil-fuel-powered blast furnaces, and the co-produced sodium hydroxide can be used for CO 2 capture from the air or ocean, creating a net-negative-emission process.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Chemical classification of iron meteorites. XI - Multi-element studies of 38 new irons and the high abundance of ungrouped irons from Antarctica
Concentrations of 14 elements in the metal of 38 iron meteorites and a pallasite are reported. Three samples are paired with previously classified irons, raising the number of well-classified, independent iron meteorites to 598. Several of the new irons are from Antarctica. Of 24 independent irons from Antarctica, eight are ungrouped, a much higher fraction than that among all classified irons. The difference is probably related to the fact that the median mass of Antarctic irons is about two orders of magnitude smaller than that of non-Antarctic irons. Smaller meteoroids may tend to sample a larger number of asteroidal source regions, perhaps because small meteoroids tend to have higher ejection velocities or because they have random-walked a greater increment of orbital semimajor axis away from that of the parent body.
Wasson, John T.↗
Dehalogenation of electrochemical processing salt simulants with ammonium phosphates and immobilization of salt cations in an iron phosphate glass waste form
This study demonstrates the conversion of simulated pyroprocessing salt wastes [i.e., ER(SF) and ERV2] into chemically durable iron phosphate glass waste forms through reactions with ammonium hydrogen phosphate precursors [i.e., NH4H2PO4 and (NH4)2HPO4] and added Fe2O3. The reaction of the salt simulants with the phosphate precursors resulted in dehalogenation of the salt through the production of NH4Cl and NH4I (along with water), of which the NH4Cl can be used to produce UCl3 oxidant for use in the electrorefiner during pyroprocessing. These iron phosphate glasses contain a notably higher waste loading than the baseline glass-bonded sodalite ceramic waste form, which requires about 70 vol% sodalite to accommodate Cl from the salt, because they are dehalogenated prior to vitrification. The high waste loadings coupled with higher bulk densities (~3×103 kg/m3) than glass-bonded sodalite (~2.3×103 kg/m3) mean that these glasses have a higher storage volume, i.e., the volume required to immobilize a given mass of waste. The iron phosphate glass waste forms were characterized using a variety of techniques including physical property measurements and chemical durability testing. Following initial testing, a proof-of-concept demonstration was conducted to show that the NH4Cl generated from this process could be used to produce UCl3 using depleted uranium dendrites as a feedstock.
phosphate glass, pyroprocessing, waste forms, salt↗
Coupled dynamics of iron and iron-bound organic carbon in forest soils during anaerobic reduction
Not provided.
Geochemistry & Geophysics↗
The Arabidopsis MTP8 transporter determines the localization of manganese and iron in seeds
Explore the source record for details and available documents.
36 MATERIALS SCIENCE↗
Magnetic iron oxide and manganese-doped iron oxide nanoparticles for the collection of alpha-emitting radionuclides from aqueous solutions
Magnetic nanoparticles are well known to possess chemically active surfaces and high surface areas that can be employed to extract a range of ions from aqueous solutions. Additionally, their paramagnetic property provides a convenient means for bulk collection of the material from solution after the targeted ions have been adsorbed. Herein, two nanoscale amphoteric metal oxides, each possessing useful magnetic attributes, were evaluated for their ability to collect both naturally occurring radioactive isotopes (polonium (Po), radium (Ra), and uranium (U)) as well as the transuranic element americium (Am) from a suite of naturally occurring aqueous matrices. The nanomaterials include commercially available paramagnetic magnetite (Fe3O4) and magnetite that was modified to incorporate manganese (Mn) into the crystal structure. The chemical stability of these nanomaterials was evaluated in Hanford Site, WA ground water between the natural pH (~8) and pH 1 (acidified with HCl). Whereas the magnetite was observed to have good stability over the pH range, the Mn-doped material was observed to leach Mn at low pH. The materials were evaluated in parallel to characterize their uptake performance of the aforementioned alpha-emitting radionuclide spikes from Hanford Site ground water across a range of pH (from ~8 down to 2). In addition, radiotracer uptake experiments were performed on Columbia River water, seawater, and human urine at their natural pH and at pH 2. Despite the observed leaching of Mn from the Mn-doped nanomaterial in the lower pH range, it exhibited generally superior analyte extraction performance compared to the magnetite, and analyte uptake was observed across a broader pH range. The uptake behavior of the various radiotracers on these two materials at different pH levels can generally be explained by the amphoteric nature of the nanoparticle surfaces. Finally, the rate of sorption of the radiotracers on the two materials in unacidified groundwater was evaluated. The uptake curves generally indicate that equilibrium is obtained within a few minutes, which is attributed to the high surface areas of the nanomaterials and the high level of dispersion in the liquids. Overall, the results indicate that these nanomaterials may have the potential to be employed for a range of applications to extract radionuclides from aqueous solutions. These applications may include analytical chemistry, waste water treatment and remediation, mining, and in vitro radiobioassay.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Beta transmutations in apatites with ferric iron as an electron acceptor – implication for nuclear waste form development
Apatite-structured materials have been considered for immobilization of a number of fission products from reprocessing nuclear fuel because of their chemical durability as well as compositional and structural flexibility
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Closed system Fischer-Tropsch synthesis over meteoritic iron, iron ore and nickel-iron alloy
Experiments were performed in which meteoritic iron, iron ore and nickel-iron alloy were used to catalyze (in Fischer-Tropsch synthesis) the reaction of deuterium and carbon monoxide in a closed vessel. Normal alkanes and alkenes and their monomethyl substituted isomers and aromatic hydrocarbons were synthesized. Iron oxide and oxidized-reduced Canyon Diablo used as Fischer-Tropsch catalysts were found to produce aromatic hydrocarbons in distributions having many of the features of those observed in carbonaceous chondrites, but only at temperatures and reaction times well above 300 C and 6-8 h.
Nooner, D. W.↗
A Tertiary Carbon–Iron Bond as an Fe I Cl Synthon and the Reductive Alkylation of Diphosphine-Supported Iron(II) Chloride Complexes to Low-Valent Iron
We explored ligand-induced reduction of ferrous alkyl complexes via homolytic cleavage of the alkyl fragment with simple chelating diphosphines. The reactivities of the sodium salts of diphenylmethane, phenyl(trimethylsilyl)methane, or diphenyl(trimethylsilyl)methane were explored in their reactivity with (py) 4 FeCl 2 . Furthermore, we prepared a series of monoalkylated salts of the type (py) 2 FeRCl and characterized from the addition of 1 equiv of the corresponding alkyl sodium species. These complexes are isostructural and have similar magnetic properties. The double alkylation of (py) 4 FeCl 2 resulted in the formation of tetrahedral high-spin iron complexes with the sodium salts of diphenylmethane and phenyl(trimethylsilyl)methane that readily decomposed. A bis(cyclohexadienyl) sandwich complex was formed with the addition of 2 equiv of the tertiary alkyl species sodium diphenyl(trimethylsilyl)methane. The addition of chelating phosphines to (py) 2 FeRCl resulted in the overall transfer of Fe(I) chloride concurrent with loss of pyridine and alkyl radical. (dmpe) 2 FeCl was synthesized via addition of 1 equiv of sodium diphenyl(trimethylsilyl)methane, whereas the addition of 2 equiv of the sodium compound to (dmpe) 2 FeCl 2 gave the reduced Fe(0) nitrogen complex (dmpe) 2 Fe(N 2 ). Our results demonstrate that iron–alkyl homolysis can be used to afford clean, low-valent iron complexes without the use of alkali metals.
36 MATERIALS SCIENCE↗