Fe-rich Compositions Research Articles

Charge-Compensation-Driven Failure Mechanism of Ni Redox in Fe-Rich Ni/Fe/Mn-Based O3-Type Layered Oxide Sodium-Ion Cathodes.

For cathode materials of sodium-ion batteries, O3-type Ni/Fe/Mn-based (Na-NFM) layered oxides have garnered extensive attention because of high economic viability, environmental friendliness, and the potential for high energy density. Among them, Fe-rich compositions exhibit higher initial charge capacity and lower bill-of-material costs, while they fade rapidly and exhibit low initial coulombic efficiency, hindering their commercialization prospects. In this work, we investigate the failure of Fe-rich Na-NFM materials through X-ray absorption spectroscopy methods. The results reveal a combined failure mechanism that encompasses not only the conventional theory of Fe migration but also an abnormal Ni-redox deterioration, which has not yet been reported. More factors related to the failure of Fe-rich Na-NFM layered oxides are discussed in detail. These findings are expected to inspire targeted research efforts toward Fe-rich Na-NFM materials, thereby accelerating the practical application of sodium-ion batteries.

Ab Initio Studies of Mechanical, Dynamical, and Thermodynamic Properties of Fe-Pt Alloys.

The density functional theory (DFT) framework in the generalized gradient approximation (GGA) was employed to study the mechanical, dynamical, and thermodynamic properties of the ordered bimetallic Fe-Pt alloys with stoichiometric structures Fe3Pt, FePt, and FePt3. These alloys exhibit remarkable magnetic properties, high coercivity, excellent chemical stability, high magnetization, and corrosion resistance, making them potential candidates for application in high-density magnetic storage devices, magnetic recording media, and spintronic devices. The calculations of elastic constants showed that all the considered Fe-Pt alloys satisfy the Born necessary conditions for mechanical stability. Calculations on macroscopic elastic moduli showed that Fe-Pt alloys are ductile and characterized by greater resistance to deformation and volume change under external shearing forces. Furthermore, Fe-Pt alloys exhibit significant anisotropy due to variations in elastic constants and deviation of the universal anisotropy index value from zero. The equiatomic FePt showed dynamical stability, while the others showed softening of soft modes along high symmetry lines in the Brillouin zone. Moreover, from the phonon densities of states, we observed that Fe atomic vibrations are dominant at higher frequencies in Fe-rich compositions, while Pt vibrations are prevalent in Pt-rich.

Tracing the Fe-enriched quartz vein-type wolframite mineralization: Wolframite U-Pb dating and compositions of wolframite and scheelite from the Anglonggangri and Jiaoxi areas, Xizang, China

Critical factors controlling Fe-enriched wolframite formation in the quartz vein-type wolframite deposit are in controversy. The Jiaoxi and Anglonggangri are typical examples of quartz vein-type wolframite mineralization found in western Lhasa terrane. The Jiaoxi wolframite comprise dominantly early hübnerite with late ferberite, whereas, the Anglonggangri wolframite are mainly ferberite. Wolframite U-Pb dating yields direct timing of 11.0 ± 0.2 Ma and 9.7 ± 0.2 Ma for Jiaoxi and Anglonggangri tungsten mineralization, respectively. Ages together with enrichment of Nb, Ta, Ti, and Sc and depletion of Sr and most Eu anomaly within Anglonggangri wolframite confirm that metals and fluids were mainly derived from the ore-forming garnet-muscovite granite. Iron and Mn mapping of garnet in the garnet-muscovite granite suggests this granite has changed from the early Mn-enriched to late Fe-rich affinity. Therefore, initial ore-forming fluids exsolved from garnet-muscovite granite have Fe-rich composition, that was significantly modified during tungsten mineralization. Positive trend between Mg and Fe/(Fe + Mn) of wolframite indicates biotite breakdown from country rock of biotite-muscovite granite to add Fe and Mg into fluid during greisenization. Meanwhile, decomposition of plagioclase and K-feldspar provided Ca, Sr, and Eu to form late scheelite. Enrichment of Sr with positive Eu anomaly and decline of REE, Nb, and Ta are typical features of the highly evolved and modified fluid. Positive and negative Eu anomalies within the same wolframite grains reveal the oxidized character and fluctuating composition of fluid during wolframite precipitation. By contrast, negative Eu anomaly and low Mo abundance of scheelite indicate the reducing fluid during scheelite crystallization. Identification of metal and fluid sources for Anglonggangri ferberite highlights the evolved granites play more crucial roles on ferberite formation than early hübnerite crystallization and Fe addition from country rocks during hydrothermal interaction.

Tourmaline geochemical and boron isotopic compositions of the Bailongshan rare-metal pegmatite deposit: Implications for magmatic-hydrothermal evolution of the West Kunlun Orogen (NW China)

The Bailongshan in the West Kunlun Orogen (northern Tibet) is a newly-discovered super-large rare-metal (Li-Rb(-Be-Ta-Nb)) pegmatite deposit. Tourmaline occurs widely in muscovite granites and pegmatites at Bailongshan, but comprehensive study is yet to be done on the geochemical evolution of tourmaline from the magmatic to the hydrothermal stages. Here, we present a systematic study of in-situ major, trace elemental and boron isotopic variations of tourmaline from Bailongshan deposit, and discuss the tourmaline genesis and how boron isotopes change during the magmatic to hydrothermal stage. Three types of tourmaline have been identified at Bailongshan deposit, including disseminated tourmaline in the muscovite granite, medium-coarse-grained euhedral tourmaline in the barren pegmatite, and multicolored medium-coarse-grained tourmaline in the ore-bearing pegmatite. EPMA and LA-ICP-MS geochemical analyses reveal that the tourmaline samples belong mainly to alkali group, with the tourmalines from the muscovite granite and the barren pegmatite falling into the schorl solid-solution series and the ore-bearing pegmatite falling into elbaite. There is a major chemical change from Fe-rich compositions with moderate Al in the Y-sites (muscovite granite and barren pegmatite) to Li-rich compositions with high YAl and relatively high F (ore-bearing pegmatite). Most trace element contents vary over several orders of magnitude with median concentrations of 0.1–10 μg/g. High concentrations are found for Ga, Zn, Be, Sc, Sn and Li (several tens to thousands of μg/g), whereas low concentrations (<0.1 μg/g) are found for V, Rb, U, Th, W, and Hf. The tourmalines from muscovite granite and barren pegmatite yielded δ11B = -8.9 to −7.5 ‰ and −8.7 to −6.0 ‰, respectively, whilst the tourmaline in the ore-bearing pegmatite show a wider δ11B range (-8.8 to −5.2 ‰). The B isotopic values indicate a source of the continental crust in a post-collisional setting. The estimated δ11B value of parental granitic magma is −10.0 ‰. The overlap in δ11B values between muscovite granite and barren pegmatite indicates a little isotopic fractionation between tourmaline and melt. Rayleigh fractionation results in the observed δ11B decrease from zone I (-6.9 ‰) to zone V (-8.0 ‰). After the barren-pegmatite-hosted tourmaline formation, the δ11B value of boron-rich magma would have been about −11.5 ‰. The intragrain δ11B variation of tourmaline in the ore-bearing pegmatite is 2.7 ‰, much larger than that from the other zones, indicating the rim of the tourmaline crystallized from fluid exsolved. We calculated the boron-isotope fractionation (between fluid and melt) to be 4.2–5.7 ‰ at 600–450 °C. Chemical variations in tourmaline are continuous in the muscovite granite and barren pegmatite, consistent with fractional crystallization, whereas the tourmaline from the ore-bearing pegmatite may have formed during the magmatic-hydrothermal transition. The boron isotopic variations could be attributed to fractionation between melt-tourmaline, melt-fluid and tourmaline-fluid and Rayleigh fractionation.

Tin Mineralization in the Triassic Chacaltaya District (Cordillera Real, Bolivia) Traced by In Situ Chemical and δ18O-δ11B Compositions of Tourmaline

Abstract We present a petrographic and geochemical study of tourmaline from the Triassic Chacaltaya Sn-polymetallic district in the Cordillera Real of Bolivia. Tourmaline is associated with greisens, breccias, and veins, which occur around the Triassic Chacaltaya peraluminous granitic stock hosted by Silurian metasedimentary rocks. Three main petrographic types of hydrothermal tourmaline have been identified: pre-ore greisen-related (Tur-1), syn-ore breccia-related (Tur-2), and syn-ore vein-related (Tur-3). The three types of tourmaline belong to the alkali group and have Fe-rich compositions mostly close to the schorl end member. Overlapping Fe/(Fe + Mg) ratios suggest broadly similar compositions of the hydrothermal fluids during the deposition of tourmaline. The most notable differences in minor and trace element contents include relative enrichment in Zn and Li in Tur-1 and relative enrichment in Ca, Sc, V, Cr, Sr, Sn, Y, Cs, Be, and Zr in Tur-3, with Tur-2 showing intermediate compositions between those of Tur-1 and Tur-3. The progressive enrichment in Sn from Tur-1 (avg = 14 ppm) through Tur-2 (avg = 311 ppm) and Tur-3 (avg = 476 ppm) indicates an increase of Sn concentrations in the hydrothermal system coinciding with cassiterite deposition in breccias and veins. The transition from high Li and Zn contents in Tur-1 to elevated Ca, Sr, V, and Cr contents in Tur-3 is interpreted as reflecting interaction between a hydrothermal fluid of magmatic origin and the metasedimentary country rocks. Strong and relatively steady positive Eu anomalies in all tourmaline types suggest dominantly reduced hydrothermal conditions. In situ δ18O and δ11B analyses of greisen-related Tur-1 reveal crystallization in isotopic equilibrium with magmatic water derived from a peraluminous S-type granite. In contrast, higher δ18O values of breccia-related Tur-2 and vein-related Tur-3 indicate crystallization in isotopic equilibrium with a fluid of metamorphic origin or a magmatic fluid that variably interacted with the metasedimentary host rocks. Geochemical modeling reproduces interactions between a fluid of magmatic origin and the host metasedimentary rocks at moderate water/rock ratios between 0.1 and 0.5. We conclude that cassiterite mineralization in the Chacaltaya district was formed primarily through interaction between B-Sn–rich magmatic fluids and the metasedimentary country rocks.

Revisiting Néel 60 years on: The magnetic anisotropy of L10 FeNi (tetrataenite)

The magnetocrystalline anisotropy energy of atomically ordered L10 FeNi (the meteoritic mineral tetrataenite) is studied within a first-principles electronic structure framework. Two compositions are examined: equiatomic Fe0.5Ni0.5 and an Fe-rich composition, Fe0.56Ni0.44. It is confirmed that, for the single crystals modeled in this work, the leading-order anisotropy coefficient K1 dominates the higher-order coefficients K2 and K3. To enable comparison with experiment, the effects of both imperfect atomic long-range order and finite temperature are included. While our computational results initially appear to undershoot the measured experimental values for this system, careful scrutiny of the original analysis due to Néel et al. [J. Appl. Phys. 35, 873 (1964)] suggests that our computed value of K1 is, in fact, consistent with experimental values, and that the noted discrepancy has its origins in the nanoscale polycrystalline, multivariant nature of experimental samples, that yields much larger values of K2 and K3 than expected a priori. These results provide fresh insight into the existing discrepancies in the literature regarding the value of tetrataenite’s uniaxial magnetocrystalline anisotropy in both natural and synthetic samples.

A revised model for activity–composition relations in solid and molten FePt alloys and a preliminary model for characterization of oxygen fugacity in high-pressure experiments

Abstract. We present new models for the activity of iron (γFe) in solid face-centered cubic (fcc) and liquid FePt alloy at high temperature and pressure to facilitate their use as sliding buffer redox sensors under extreme conditions. Numerous experimental studies of γFe in FePt alloy at 100 kPa have produced a wide spread of values. By favoring high-temperature studies that are more likely to have produced equilibrium measurement and excluding experiments for compositions and temperatures that probably encountered ordered or unmixed low-temperature phases, we regress an asymmetric Margules activity–composition model with parameters WFePtfcc=-121.5±2.1 kJ mol−1 and WPtFefcc=-93.3±4.3 kJ mol−1. These values are close to the widely used model of Kessel et al. (2001), but for Pt-rich compositions they predict larger Fe activities and correspondingly more reduced oxygen fugacities. Activity–composition relations in liquid FePt are calibrated from direct measurements of activities and, most sensitively, from the trace of the Fe–Pt liquidus. Together, these yield asymmetric Margules parameters of WFePtliq=-124.5 kJ mol−1 and WPtFeliq=-94.0 kJ mol−1. The effects of pressure on both fcc and liquid FePt alloy are considered from excess-volume relations. Both solid and liquid alloy display significant positive excess volumes of mixing. Extraction of the excess volume of mixing for fcc FePt alloy requires filtering data for ordered low-temperature phases and corrections for the effects of magnetostriction on Fe-rich compositions which exhibit “Invar” behavior. Applied at high temperatures and pressures, both solid and liquid FePt alloys have strongly negative deviations from ideality at low pressure, which become closer to ideal at high pressure. These models provide a provisional basis for the calculation of aFe in high-temperature, high-pressure experiments that, when combined with estimates of aFeO, allow characterization of fO2 under conditions relevant to magma oceans, core formation, and differentiation processes in the lower mantle of Earth or on other terrestrial planets. Improvements in these models require new constraints on the equation of state of FePt fcc alloy and documentation of the high-pressure melting relations in the system Fe–Pt.

Ferric iron in chrome-bearing spinels: implications for microprobe correction procedures

AbstractWe investigated the compositions of a suite of 361 chrome-bearing spinels from spinel peridotites, ophiolitic mantle chromitites and from layered igneous intrusions in which the Fe2+/Fe3+ ratio has been determined by Mössbauer spectroscopy. We explore the crystal-chemical controls on the distribution of Fe3+ and on mineral stoichiometry with regard to electron-probe correction procedures for estimating Fe3+ in spinel. We find that chrome-bearing spinels can be subdivided into three groups: a Cr–Al-rich group; a high-Fe group; and a highly oxidised group. Spinels of the Cr–Al group are found in spinel peridotites and ophiolitic mantle chromitites. They are normal spinels with a low Fe3+ content and compositions that are close to stoichiometric. Spinels in the high-Fe group are found in layered igneous intrusions. They are also normal spinels which have higher concentrations of Fe3+ on the octahedrally coordinated site than is found for the Cr–Al group. Stoichiometric calculations tend to overestimate the Fe3+ content and their compositions do not conform to the MgO–cr# correlation found in the Cr–Al group. Spinels in the highly oxidised group are found in layered intrusions and ophiolitic mantle chromitites. They have (Fe3+/ΣFe)Möss &gt; 0.4 and high Cr (cr# &gt; 0.5), but relatively low Fe2+ (fe# 0.24–0.56). Stoichiometric calculations tend to underestimate the Fe3+ content. They represent normal spinels in which tetrahedrally coordinated Fe2+ has been oxidised to Fe3+.Our data show that spinels with greater Cr and Fe are sufficiently different in their crystal chemistry from the aluminous spinels to indicate that the EPMA correction procedures developed for Fe3+ in aluminous spinels on the basis of the Cr/Al ratio, and used in oxy-thermobarometry, are inappropriate for Cr-rich and Fe-rich compositions.

Phase Stability of SrTi1-XFexO3- δ Under Solid Oxide Cell Fuel-Electrode Conditions: Implications for Related Exsolution Electrode Materials

Perovskite oxides with catalytically active metal nanoparticle exsolution are receiving considerable attention as alternative Solid Oxide Cell fuel-electrode materials. For exsolution, a small amount of a cation is substituted on the B-site of the base oxide and then is reduced out of the host lattice to form nanoparticles that promote electrochemical processes. During exsolution, the host lattice generally becomes more B-site deficient. In some cases, the oxide is made initially A-site deficient to compensate for the loss of B-site cations. Thus, the stability of these oxides under a range of stoichiometries and fuel electrode conditions is of interest.Here we focus on one perovskite host material of interest, SrTi1-xFexO3- δ (STF), which has shown good fuel electrode characteristics that can be enhanced by the substitution of Ru or Ni, resulting in exsolution to form Ru-Fe or Ni-Fe alloy nanoparticles, respectively. (1, 2) Although the amounts of Ru or Ni substituted are small, typically ~ 7% of the B-site cations, the co-exsolution of a comparable amount of Fe is usually observed, resulting in substantial B-site deficiency, potentially de-stabilizing the host perovskite phase. The stability of Fe in STF is also of interest because it helps to determine the Fe content of the alloy nanoparticles. (3)This study seeks to determine the stability of STF in various reducing fuel environments. While STF has been mostly studied as SrTi0.3Fe0.7O3-δ (STF-7), it is not known if this composition provides the best combination of stability and electrochemical performance. Thus, a few additional compositions, SrTi0.5Fe0.5O3- δ (STF-5), SrTi0.4Fe0.6O3- δ (STF-6), and SrTi0.2Fe0.8O3- δ (STF-8), have been studied. In general, the Fe-rich compositions are expected to possess higher electronic and ionic conductivity, leading to good electrochemical performance, whereas the more Ti-rich compositions are expected to provide better stability. Exposure to 97% H2 – 3% H2O at 850°C for 4 h resulted in STF decomposition into BCC α-Fe and a Ruddlesden-Popper (RP) phase, but the decomposition became more limited for the more Ti-rich compositions (Figure 1a). The main Fe peak overlaps with one of the RP peaks, but the presence of α-Fe particles is clearly visible in STEM energy dispersive x-ray spectroscopy chemical mapping, shown for STF-7 in Figure 1b. Figure 1c shows that there is a critical p(O2), 1.3 x 10-20 atm, below which decomposition of perovskite STF-7 occurs. In addition to ex situ XRD as shown in Figure 1, in situ XRD results will be presented and used to confirm and quantify phase changes in combination with thermogravimetric analysis (TGA). Additionally, the conductivity and electrochemical performance of the various STF compositions will be reported and discussed relative to the phase change from perovskite to Ruddlesden Popper and the Fe exsolution. The other main materials variable to be explored is the A-to-B site stoichiometry, which will be studied over the range expected during exsolution. The implications of these results for various exsolution electrode compositions will be discussed.Figure 1: a) Reductions of STF-5 through STF-8 all yield significant decomposition as the initially pristine perovskite acquires several additional peaks. b) Using energy dispersive x-ray spectroscopy, it can be shown that significant Fe deposits appear in STF-7 after reduction at 850°C (effective pO2 1.2e-21 atm for 4 hours). c By increasing pO2 by a factor of 10, XRD patterns for STF-7 show no clear Ruddlesden-Popper or α-Fe peaks, indicating that decomposition requires significantly reducing conditions and that STF may remain stable under more oxidizing conditions.References R. Glaser, T. Zhu, H. Troiani, A. Caneiro, L. Mogni and S. Barnett, Journal of Materials Chemistry A, 6, 5193 (2018).T. Zhu, H. Troiani, L. V. Mogni, M. Santaya, M. Han and S. A. Barnett, Journal of Power Sources, 439 (2019).T. Zhu, H. E. Troiani, L. V. Mogni, M. Han and S. A. Barnett, Joule, 2, 478 (2018). Figure 1

Dual origin of ferropericlase inclusions within super-deep diamonds

Ferropericlase [(Mg,Fe)O] is one of the major constituents of Earth's lower mantle and the most abundant mineral inclusion in sub-lithospheric diamonds. Although a lower mantle origin for ferropericlase inclusions has often been suggested, some studies have proposed that many of these inclusions may instead form at much shallower depths, in the deep upper mantle or transition zone. No straightforward method exists to discriminate ferropericlase of lower-mantle origin without characteristic mineral associations, such as co-existing former bridgmanite. To explore ferropericlase-diamond growth relationships, we have investigated the crystallographic orientation relationships (CORs), determined by single-crystal X-ray diffraction, between 57 ferropericlase inclusions and 37 diamonds from Juina (Brazil) and Kankan (Guinea). We show that ferropericlase inclusions can develop specific (16 inclusions in 12 diamonds), rotational statistical (9 inclusions in 7 diamonds) and random (32 inclusions in 25 diamond) CORs with respect to their diamond hosts. All measured inclusions showing a specific COR were found to be Fe-rich (XFeO > 0.30). Coexistence of non-randomly and randomly oriented ferropericlase inclusions within the same diamond indicates that their CORs may be variably affected by local growth conditions. However, the occurrence of specific CORs only for Fe-rich inclusions indicates that Fe-rich ferropericlases have a distinct genesis and are syngenetic with their host diamonds. This result provides strong support for a dual origin for ferropericlase in Earth's mantle, with Fe-rich compositions likely indicating redox growth in the upper mantle, while more Mg-rich compositions with random COR mostly representing ambient lower mantle trapped as protogenetic inclusions.

Appraising the late-stage magmatic fO2 of diabasic angrites with a novel phase equilibrium approach. Implications for new and existing models of angrite petrogenesis

One of the enduring problems in angrite petrogenesis is how to reconcile the extraordinary Fe-rich compositions of many angritic liquids – which seemingly require modestly oxidized fO2 conditions that fall outside the stability field of Fe-Ni alloys during primordial melting – with the geochemical and paleomagnetic evidence that the angrite parent body contains a small metallic Fe-Ni-S-C core. One of the major impediments to resolving these contradictions stems from a distinct lack of rigorous fO2 data for the angrite meteorite clan. To begin addressing this issue, we have developed a new approach for calculating magmatic fO2 values directly from the late-stage olivine-ulvöspinel- silicate liquid assemblages that are common in the volcanic or hypabyssal angrites. The adaptation of the olivine-spinel-aSiO2liq oxybarometer for use in angrites requires a careful assessment of aSiO2liq of angritic liquids. We apply the results of metal saturated angrite crystallization experiments and an analysis of the Ca-Tschermak’s-anorthite-aSiO2liq equilibrium to obtain estimates for the aSiO2liq values of angritic magmas. We then use the aSiO2liq estimates derived from the experiments and thermodynamic analysis in conjunction with the olivine-spinel-aSiO2liq oxybarometer to calculate the magmatic fO2 of Sahara 99555, D’Orbigny, and Northwest Africa 12004. With this approach we estimate oxygen fugacity values that range from ΔIW + 0 to ΔIW + 0.25. The relatively reducing fO2 values obtained from our analysis are inconsistent with redox conditions required by the oxidized melting hypothesis. Some caution is warranted in extrapolating these late-stage magmatic fO2 values to higher temperatures; however, we stress that fractionated silicate liquids typically become more oxidized with increasing crystallization via auto-oxidation (i.e., the accumulation of incompatible ferric iron in the liquid). Therefore, we suggest that late stage magmatic fO2 values from our calculations may represent the most oxidized conditions along the angrite liquid line of descent. If this interpretation is correct, a large-scale oxidation event on the APB need not be invoked to reconcile mildly reducing conditions (ΔIW−1.35) thought to have prevailed during core formation with the magmatic fO2 record preserved in angritic meteorites. Future redox studies of compositionally primitive angrites (e.g., Northwest Africa 12774) may shed new light on the redox relationships among primitive angrite magmas, evolved angrite magmas, and core forming alloys.

Thermodynamic Modeling of Formation Enthalpies of Amorphous and Crystalline Phases in Zr, Nd, and Ce-Substituted Fe-Si Systems

The alloys that crystallize in a tetragonal ThMn12-type (space group I4/mmm) structure and are based on Fe and rare earth elements are believed to have a potential to plug the performance gap between ferrite and Nd-based magnets. Nevertheless, the progress is hindered by their poor structural stability, compared with other phases competing during the synthesis process, e.g., Th2Zn17-type. In this work, the enthalpies of the formation (and other thermodynamic parameters) of various phases in (Zr, Nd, Ce)-Fe-Si systems were calculated, with paramount focus on the Fe-rich compositions. We compared and discussed the stability range and stabilization routes for amorphous phases, solid solutions, and intermetallics. The beneficial influence of Zr and Si on the crystallization of intermetallic compounds was confirmed, simultaneously being valid for other phases. Among all of the analyzed Fe-rich phases, the lowest values for enthalpy of the formation of the amorphous phase and solid solution were determined for ZrFe10Si2 (−17.5 and −18.2 kJ/mol, respectively). Moreover, substitution by elements with a large atomic radius is indicated as a method for the introduction of topological disorder, giving possibility for the synthesis of metastable phases (even amorphous) and the utilization of more sophisticated synthesis routes in the future.

Effect of chemical disorder on the magnetic anisotropy in L10 FeNi from first-principles calculations

We use first-principles calculations to investigate how deviations from perfect chemical order affect the magnetocrystalline anisotropy energy (MAE) in $L{1}_{0}$ FeNi. We first analyze the local chemical environment of the Fe atoms in various partially ordered configurations, using the orbital magnetic moment anisotropy (OMA) as proxy for a local contribution to the MAE. We are able to identify a specific nearest neighbor configuration and use this ``favorable environment'' to successfully design various structures with MAE higher than the perfectly ordered system. However, a systematic analysis of the correlation between local environment and OMA using smooth overlap of atomic positions indicates only a partial correlation, which exists only if the deviation from full chemical order is not too large, whereas in general no such correlation can be identified even using up to third nearest neighbors. Guided by the observation that the identified favorable environment implies an Fe-rich composition, we investigate the effect of randomly inserting additional Fe into the nominal Ni planes of the perfectly ordered structure. We find that the MAE increases with Fe content, at least up to 62.5% Fe. Thus, our paper shows that the perfectly ordered case is not the one with highest MAE and that an increased MAE can be obtained for slightly Fe-rich compositions.

SIMS matrix effects in oxygen isotope analysis of olivine and pyroxene: Application to Acfer 094 chondrite chondrules and reconsideration of the primitive chondrule minerals (PCM) line

The instrumental bias (here expressed as bias*, the difference relative to San Carlos Olivine, SC-Ol) of oxygen isotopes in secondary ion mass spectrometry (SIMS) analyses of olivine and pyroxene were investigated. Sixteen olivine (Fo0–100), nine orthopyroxene (En70–100Wo0–3), and three clinopyroxene (En28-49Wo45–50) reference materials (RMs) were utilized. The values of bias* are nearly invariant (within 0 ± 0.5‰) among magnesian olivine (Fo ≥60) RMs but decrease systematically with increasing Fe molar fraction down to ~ −10‰ (Fo0). The session-to-session variability of bias* for Fo ≥60 olivines is ≤0.3‰ but becomes slightly larger for more Fe-rich compositions (≤1.5‰). Orthopyroxene RMs have a narrow range of bias* values (−1.7‰ to −2.6‰) that show session-to-session variability ≤0.3‰; correspondingly, the sputter rates are similarly low and resemble those of Fo ≥60 olivines. Clinopyroxene RMs bias* values (−0.2‰ to +1.2‰) are more variable and have larger session-to-session variability (≤0.8‰), which appear to be independent of sputter rates. Bias* of the same RMs change slightly from session to session with different analytical settings (≤0.6‰ for Fo ≥60 and as much as 2‰ for fayalite) so that equations of bias* as a function of Fo, En, and Wo should be determined for each SIMS session by the analyses of multiple RMs.The new suite of olivine and pyroxene RMs with expanded composition range were used to correct the instrumental biases during oxygen three-isotope analysis of olivine and low-Ca pyroxene in chondrules of the ungrouped Acfer 094 chondrite, from which the primitive chondrule minerals (PCM, δ18O vs. δ17O) line was originally derived. The PCM line is considered to be a mixing trend of two extreme primary oxygen isotope reservoirs of solids in the early solar system. However, this new dataset, with better analytical precision and instrumental bias correction, allows two oxygen isotope trends to be clearly identified. One is represented by chondrules that plot on or above the PCM line, likely linked to ordinary chondrite (OC)-like materials. A second trend is represented by the major chondrule population in this chondrite that defines a regression line of δ17O = (0.968 ± 0.022) × δ18O − (3.46 ± 0.10) (MSWD = 2.0), consistent with recent oxygen isotope data of chondrules in carbonaceous chondrites (i.e., CV, CK, CO, and CM). We propose that this regression line represents a mixing of two oxygen isotope reservoirs (possibly 16O-rich solids and 16O-poor H2O ice) in the outer solar system and likely resulting from the separate evolutions of isotope reservoirs after the “Jupiter divide” built up.

Glass colourations caused by Mn-Fe redox pair : Application to ancient glass technology

Manganese is a chemical element used as a colourizer in glass industry since antiquity. Combined with iron, manganese often plays the role of a decolourizer leading to uncoloured glasses used to represent hands and faces in medieval stained glass windows. A series of medieval-like glasses has been synthesized in order to relate the colouration of glasses with the conditions of synthesis (temperature, atmosphere, glass composition). Optical absorption spectra in the UV–Vis-NIR range have been measured to follow and characterize the changes in colouration. For a given temperature, the addition of Mn in a Fe-rich glass composition implies a decrease of the concentration in Fe2+and an increase of the concentration in Fe3+ as compared to the Mn-free glass composition. The uncoloured glass composition is obtained for different contents of Mn when melting temperature varies. These results might help deciphering the complexity of colour making in ancient times.

Incorporating previously neglected excess oxygen associated with ferric iron in matrix corrections of microprobe data from cubic and rhombohedral Fe-Ti oxides

Abstract Estimates of the oxidation states of magmas are important to current investigations of the geo-chemical characteristics of their source regions and of evolved magmatic series created during differentiation. One means of achieving such estimates is to capitalize on compositions of coexisting cubic and rhombohedral Fe-Ti oxides determined by electron microprobe. A combination of experimental calibration points and thermodynamic modeling provides a basis for translating such compositions into T-fO2 values. This has been done until recently by estimating Fe3+/ΣFe on the basis of charge balance and stoichiometry by the method of Droop (1987), after matrix corrections of X-ray intensity data have been performed, as EPMA cannot be used routinely to distinguish different elemental valence states, much less accurately quantify abundances of Fe3+ and Fe2+. The traditional approach of undertaking post-data-reduction calculations falls short of attaining the best possible quantitative results. The tactical choice of not accounting for light elements that have not been explicitly analyzed prior to matrix corrections of X-ray intensity data leads to systematic errors in reported oxide abundances for measured elements. This article addresses one such issue, the oxygen associated with Fe3+ (hereafter “excess oxygen”), on the basis of coexisting Fe-Ti oxides from Andean lavas. A new software routine in probe for EPMA (PFE) uses an iterative calculation scheme to calculate amounts of excess oxygen that would not be considered if all iron were assumed to be ferrous and then applies this excess oxygen during matrix corrections. The PFE approach reveals that Fe-concentrations have been underestimated, universally, in these minerals because O atoms absorb FeKα radiation: discrepancies increase as total Fe and Fe3+/Fe2+, hence excess oxygen, increase. Analyses of the most Fe-rich cubic oxide compositions in this data set have ~6 wt% excess oxygen and ~1 wt% more FeO+Fe2O3 than would be reported without incorporating the impact of excess oxygen in matrix corrections. Minor to negligible differences in other elements are also observed. These effects are not because excess oxygen is directly attributed to these elements, although some may be present in multiple valence states, as matrix corrections are undertaken on the basis of the conventional assumptions that they occur as Cr3+, V3+, Mn2+, Mg2+, Ca2+, and Si4+. Rather, variably small increases in total Fe propagate through the matrix corrections for other elements, and these differences may be recorded as minor increases or decreases in some concentrations, depending on the particular element and the amount of change in Fe-concentration. Fe3+/ΣFe in analyses produced with the PFE routine are essentially identical to those determined in the traditional mode, as cation proportions calculated on the basis of charge balance and stoichiometry, with the method of Droop (1987), is a necessary step. The new method: (1) provides more accurate concentrations, mainly for Fe and Ti; (2) is applicable to any mineral containing ferric iron (subject to stoichiometric constraints); (3) provides more accurate analytical totals, which can be advantageous for evaluating analytical quality; and (4) does not impact estimates of oxidation state. Oxygen fugacities and temperatures determined with the model of Ghiorso and Evans (2008) are essentially unchanged.

The Fe-FeSi phase diagram at Mercury\u2019s core conditions

Mercury’s metallic core is expected to have formed under highly reducing conditions, resulting in the presence of significant quantities of silicon alloyed to iron. Here we present the phase diagram of the Fe-FeSi system, reconstructed from in situ X-ray diffraction measurements at pressure and temperature conditions spanning over those expected for Mercury’s core, and ex situ chemical analysis of recovered samples. Under high pressure, we do not observe a miscibility gap between the cubic fcc and B2 structures, but rather the formation of a re-entrant bcc phase at temperatures close to melting. Upon melting, the investigated alloys are observed to evolve towards two distinct Fe-rich and Fe-poor liquid compositions at pressures below 35-38 GPa. The evolution of the phase diagram with pressure and temperature prescribes a range of possible core crystallization regimes, with strong dependence on the Si abundance of the core.

Nanocrystalline (Fe,Co,Ni)86B14 soft magnetic alloys prepared by ultra-rapid annealing

In this study, the glass-forming range, microstructural and soft magnetic properties of (Fe1−x-yCoxNiy)86B14 alloys were investigated in the as-cast state and after ultra-rapid annealing. The glass-forming range is seen to be the greatest for Fe-rich compositions and is limited to x ≤ 0.8 and y ≤ 0.3. Within the glass-forming range, this alloy system is observed to contain nano-scale grains with bcc and fcc structures after ultra-rapid annealing and a clear bcc-fcc transition is seen for Ni-rich compositions. Both the coercivity (Hc) and saturation magnetic polarization (Js) for the nanocrystalline (Fe1−x-yCoxNiy)86B14 alloys are generally increased by Co addition and reduced by Ni addition. Js is confirmed to be the largest for (Fe0.8Co0.2)86B14 at 1.88 T in the as-cast state and 1.98 T for (Fe0.7Co0.3)86B14 in the nanocrystalline state. The minimum Hc of 2.0 A/m is obtained for nanocrystalline (Fe0.80Co0.05Ni0.15)86B14 with a Js of 1.71 T. This composition also exhibits a lower core loss compared to the nanocrystalline Fe86B14 and Fe-based amorphous alloys at frequencies up to 1 kHz.

Petrogenesis of coeval lamproites and kimberlites from the Wajrakarur field, Southern India: New insights from olivine compositions

Olivine is one of the most abundant phases in kimberlites and cratonic lamproites, where it occurs as mantle-derived xenocrysts and magmatic phenocrysts or rims overgrowing xenocrystic cores, indicating its prevalence throughout most of the crystallisation sequence of these magmas. Thus, olivine can provide valuable insights into kimberlite and lamproite petrogenesis. Here, we present a detailed study of olivine compositional zoning in two lamproites (P2 and P12) of the Mesoproterozoic Wajrakarur kimberlite-lamproite field in southern India and use these data to propose a genetic link between lamproites and kimberlites in the region.Olivine macrocrysts (i.e., anhedral grains >1 mm) from the P2 and P12 intrusions are strongly zoned. Comparisons with olivine from mantle xenoliths worldwide demonstrate that the cores of olivine macrocrysts are xenocrysts derived from disaggregated mantle wall-rocks. The internal zones and overgrowth rims of olivine macrocrysts and the cores of olivine phenocrysts from P2 and P12 contain magmatic Mg-chromite and Ti-magnetite inclusions and hence crystallized from the host lamproite melt. These magmatic olivine zones show increasing Mg# (molar Mg/(Mg + Fe2+)), CaO and MnO contents with decreasing NiO. This reverse differentiation trend appears to be a characteristic feature of olivine in lamproites from the Wajrakarur field.To evaluate potential petrogenetic links between coeval lamproites and kimberlites from Wajrakarur, the composition of olivine xenocrysts (i.e., macrocryst cores) was compared with that of early crystallized olivine in P2, P12 and previously studied kimberlites and lamproites. The average Mg# of olivine macrocryst cores is directly correlated with the average Mg# of magmatic olivine in lamproites and kimberlites from Wajrakarur. Coupled with their indistinguishable Sr-Nd-Hf isotope compositions, these data suggest derivation of the Wajrakarur lamproites and kimberlites from a common source, The more Fe-rich composition of liquidus olivine in the Wajrakarur lamproites compared to coeval kimberlites suggests a higher degree of assimilation of metasomatised Fe-richer lithospheric mantle by the lamproites and provides a plausible explanation for the different petrological features of the Wajrakarur lamproites and kimberlites Our results suggest that cratonic lamproites can have a remarkably similar petrogenetic history to kimberlites.

Comment on “Biogeochemical cycling of iron (hydr-)oxides and its impact on organic carbon turnover in coastal wetlands: A global synthesis and perspective” [Earth-Science Reviews (2021) 103658

Models for a xenocryst origin for kimberlite olivines emphasise the similarity between their core compositions and those in mantle peridotites. While this permits a xenocryst origin, it does not provide proof, as magmas generated in equilibrium with mantle olivines could, in principle, crystallize initial olivines matching those in the source region. Further, in several kimberlites, there is a striking disparity between the compositional range of olivine cores and that in associated mantle peridotite xenoliths from the same locality. Olivine-liquid Mg-Fe exchange coefficients and Ni partition coefficients permit equilibrium between Mg-rich mantle olivines (Mg # ~ 94–93) and magmas matching kimberlite bulk rock compositions. Glass inclusions in olivine megacrysts from the Monastery kimberlite, with compositions which overlap the range of archetypal Group I kimberlites, were interpreted to represent original liquids trapped at pressures of 4.5–6 GPa. These glass inclusions provide direct petrographic support for primitive melts matching kimberlite bulk chemistry in the lower SCLM.A majority of kimberlitic olivines show normal (decreasing Mg #) core to rim zonation. Cores of normal-zoned kimberlitic olivines are typically homogeneous, but collectively define a field with a range in Mg # and invariant or slightly decreasing Ni towards more Fe-rich compositions. The most Mg-rich cores of normal-zoned olivines typically have Mg # in the range 94–93, but there are marked differences in the Fe-rich extreme of the normal-zoned population between different kimberlite clusters. Olivine rims typically define a field characterized by steeply decreasing Ni, coupled with invariant or slightly increasing or decreasing Mg #, which invariably overlaps the Fe-extreme of core compositions of the relatively Mg-rich, normal-zoned olivines. Consequently, while there is a sharp inflection in chemical gradient between the respective fields of cores and rims, they nevertheless define a continuous compositional field. Trace element modelling demonstrates that these zonation patterns can be explained in terms of a Raleigh crystallization model.Most, if not all kimberlites are characterized by a subordinate group of olivine macrocrysts with cores that are Fe-rich relative to the field for rims, and thus show reverse zonation, which are interpreted to be linked to the Cr-poor megacryst suite. Rare Mg-rich olivines (relative to rims), have high-pressure inclusions of garnet, clinopyroxene and orthopyroxene. When present, such inclusions often show disequilibrium features such as internal chemical zonation. This points to a very short mantle residence time prior to entrainment by the host kimberlite, indicating a link to the Cr-rich megacryst suite rather than mantle peridotites. In addition to a variable, but generally subordinate proportion of olivines derived from Cr-poor and Cr-rich megacrysts, xenocrysts derived from disaggregated mantle peridotites will undoubtedly be present. While their proportions are difficult to quantify, the collective evidence points to a cognate origin for a majority of kimberlitic olivines. A kimberlite magma ascent model is proposed which provides a framework for understanding both olivine compositional variation and apparently enigmatic internal and external olivine morphology.