Magnetite Lattice Research Articles

Nanostructured spinel ferrites: A comprehensive study on the synthesis, characterization, and magnetic properties of Zn and Mn substituted magnetite nanoparticles produced through the co-precipitation method

Seven cubic spinel ferrite nanoparticles were successfully synthesized through the co-precipitation method. These nanoparticles include Fe3O4, Zn0.4Fe0.62+Fe23+O4, Mn0.4Fe0.62+Fe23+O4, Zn0.6Mn0.4Fe0.42+Fe1.63+O4, Zn0.4Mn0.6Fe0.42+Fe1.63+O4, Zn0.4Mn0.4Fe0.22+Fe23+O4, and Zn0.4Mn0.4Fe0.42+Fe1.83+O4. The Rietveld method was used to analyze X-ray diffraction data, confirming that all samples have a single-phase cubic spinel structure. The presence of zinc and manganese ions in magnetite lattice leads to changes in lattice parameters and crystallite size, resulting in a range of 7–12 nm crystallite sizes. Fourier transform infrared spectroscopy (FT-IR) analysis of nanoparticles reveals two significant adsorption peaks at 560-576 cm−1 and 437-449 cm−1, corresponding to metal ion stretching vibrations at tetrahedral and octahedral sites. The X-ray photoelectron spectroscopy (XPS) analysis revealed the presence of iron, zinc, and manganese in various oxidation states. Scanning electron microscopy (SEM) and Transmission electron microscopy (TEM) images showed spherical, agglomerated nanoparticles. The study confirmed the elemental composition and mapping images of prepared samples using energy-dispersive X-ray spectroscopy (EDS). The magnetic properties of the synthesized nanoparticles were meticulously examined utilizing a vibrating sample magnetometer (VSM) at room temperature. A direct correlation is established between the structural alterations induced by Zn2+/Mn2+ and their subsequent effects on magnetic characteristics, specifically through the reallocation of cations and the mechanisms of electron hopping occurring at the B-sites. The structural modifications result in enhanced superparamagnetic behavior, exhibiting saturation magnetization values between 46.01 and 69.38 emu/g. The sustainable characteristics of these materials render them highly viable options for applications in environmental remediation and green technology.

Insight into the influence mechanism of chloride ions towards in-situ electric-induced uranium incorporation into magnetite

The application of electrochemical methods for incorporating uranium into the magnetite lattice has demonstrated efficacy and durability in remediating radioactive contamination. However, the impact of different ions, particularly electrolyte ions, on this process remains unclear. Herein, we successfully achieved simultaneous magnetite crystallization and uranium incorporation within an electrochemical system using an iron anode. Chloride ions have been identified as having a pivotal role in the generation of ferrous ions via pitting corrosion, thereby establishing an advantageous reducing environment that promotes the transformation of γ-FeOOH to magnetite. Unlike the surface adsorption process of γ-FeOOH, magnetite predominantly eradicates uranium through an incorporation mechanism. Consequently, the existence of chloride ions markedly boosts the effectiveness of uranium elimination and the stability of the resultant substance. Specifically, under conditions of a pH of 5 and a chloride ions concentration of 18 mM, uranium removal reaches nearly 100%. Additionally, findings from uranium leaching experiments indicate that γ-FeOOH removed 25.4% stable, 63.57% metastable, and 11.03% unstable uranium, while magnetite removed 60.35% stable, 24.81% metastable, and 14.84% unstable uranium. This research offers insight into the potential role of electrolyte ions in facilitating in-situ electric-induced uranium incorporation.

Reduction and transformation of Cr(VI)-associated ferrihydrite by Shewanella oneidensis MR-1: Kinetics and secondary minerals

Hexavalent chromium (Cr(VI)) could be sequestrated by soils via microbial reduction to Cr(III) and association with minerals, however, quantitative understanding of metal reducing bacteria on the coupled kinetics of Cr and Fe minerals is still lacking. Here, microbial-mediated ferrihydrite transformation and reductive sequestration of Cr(VI) were investigated with Shewanella oneidensis MR-1 under varying Cr/Fe ratios. Quantitative results depicted that the contents of magnetite from ferrihydrite transformation decreased from 70 % to 22 % after 288 h as Cr/Fe ratios increased from 0 to 8 × 10−3, and reductive transformation rates increased with decreasing Cr/Fe ratio. Elemental mapping and line scan analyses at nano-scale revealed that Cr(VI) was evenly combined within fresh ferrihydrite, and a part of produced Cr(III) was doped into the crystal lattice of magnetite and goethite. Cr may be sequestrated by secondary Fe minerals via structural substitution, surface complexation, and physical encapsulation. Microscopy-based results exhibited that more Fe minerals adsorbed on the surface of cell and less cells were lysed at low Cr/Fe ratios. Confocal laser scanning microscopy depicted that less cells were alive at high Cr/Fe ratios. The amplification of extracellular electron transfer-associated genes was downregulated as Cr/Fe ratios increased. The Cr/Fe ratios could affect cell activity, the combination with Fe minerals, and Mtr gene expression, thus controlling the reductive sequestration of Cr(VI) and phase transformation of ferrihydrite. A kinetic model has been established by combining elementary reductions, and it could well describe Cr(VI) reduction and Cr(III) incorporation under various Cr/Fe ratios during dissimilatory Fe reduction process. These findings could broaden our knowledge of quantifying the migration and transport of Cr in anoxic Cr-contaminated soil environments, and could be useful for simulating Cr dynamic behaviors in the natural soil, aquatic, and sediment environments.

A threefold increase in SAR performance for magnetic hyperthermia by compositional tuning in zinc-substituted iron oxide superparamagnetic nanoparticles with superior biocompatibility

In this work, we report a ultrahigh specific absorption rate (SAR) performance in Zn-substituted magnetite superparamagnetic (SPM) nanoparticles (NPs) for potential application in magnetic hyperthermia (MHT)-based cancer treatment. Although MHT shows promise in cancer therapy, challenges such as low heating performance, agglomeration of magnetic nanoparticles (MNPs) in blood veins, cytotoxicity, and hemocompatibility have hindered clinical uses. To overcome these challenges, we adopted a reverse-micelles based coprecipitation synthesis approach to prevent MNPs agglomeration and optimized the substitution of Zn ions in magnetite to enhance heating performance. Calorimetric measurements showed SAR values of 118 W/g and 181 W/g for magnetite NPs using the initial slope method (ISM) and Box Lucas method (BLM), respectively. Through our compositional optimizations, we achieved a significant increase in SAR value by consciously substituting Zn2+ ions in the magnetite lattice. Specifically, we obtained SAR values of 325 W/g and 579 W/g (>300% increase) for Zn0.3Fe2.7O4 MNPs using ISM and BLM, respectively. This enhancement can be attributed to improved saturation magnetization (174–257 kA/m) and magneto-crystalline anisotropy (12–24 kJ/m3). The increase in saturation magnetization in the magnetite MNPs can be explained by the higher magnetic moment resulting from increased Zn concentration up to ZnxFe3-xO4(x = 0.3), strengthening the JAB interaction. However, further increases in Zn concentration lead to a decrease in saturation magnetization due to non-collinearity, as described by the Yafet-Kittle model. Our optimized MNPs exhibit improved heating performance, enabling the use of lower MNPs concentrations for cancer treatment, reducing potential toxicity effects. Biocompatibility investigations demonstrated a low hemolysis rate (<5%) in a hemolysis assay with red blood cells and high cytocompatibility (>92% cell viability) in MTT assays for all compositions, confirming their potential suitability for clinical applications. This study offers a promising approach to enhance SAR performance, addressing MHT-based cancer treatment challenges, and improving clinical suitability.

Crystal-Chemical and Biological Controls of Elemental Incorporation into Magnetite Nanocrystals.

Magnetite nanoparticles possess numerous fundamental, biomedical, and industrial applications, many of which depend on tuning the magnetic properties. This is often achieved by the incorporation of trace and minor elements into the magnetite lattice. Such incorporation was shown to depend strongly on the magnetite formation pathway (i.e., abiotic vs biological), but the mechanisms controlling element partitioning between magnetite and its surrounding precipitation solution remain to be elucidated. Here, we used a combination of theoretical modeling (lattice and crystal field theories) and experimental evidence (high-resolution inductively coupled plasma-mass spectrometry and X-ray absorption spectroscopy) to demonstrate that element incorporation into abiotic magnetite nanoparticles is controlled principally by cation size and valence. Elements from the first series of transition metals (Cr to Zn) constituted exceptions to this finding, as their incorporation appeared to be also controlled by the energy levels of their unfilled 3d orbitals, in line with crystal field mechanisms. We finally show that element incorporation into biological magnetite nanoparticles produced by magnetotactic bacteria (MTB) cannot be explained by crystal-chemical parameters alone, which points to the biological control exerted by the bacteria over the element transfer between the MTB growth medium and the intracellular environment. This screening effect generates biological magnetite with a purer chemical composition in comparison to the abiotic materials formed in a solution of similar composition. Our work establishes a theoretical framework for understanding the crystal-chemical and biological controls of trace and minor cation incorporation into magnetite, thereby providing predictive methods to tailor the composition of magnetite nanoparticles for improved control over magnetic properties.

Magnetically tunable rheological properties of PVDF doped with superparamagnetic Fe3O4 nanoparticles synthesized by rapid microwave method

We report on the surfactant/additives free synthesis of single domain superparamagnetic Fe3O4 nanoparticles (FNPs) by rapid microwave synthesis method. X-Ray diffraction (XRD) and Scanning Electron Microscopy (SEM) studies reveal that FNPs were crystallized in the magnetite (Fe3O4) lattice and have granular shape with average particles size of ∼14 nm. The band gap of FNPs calculated from UV–Visible absorption spectrum is ∼2.3 eV. FNPs exhibit single domain superparamagnetic behaviour as confirmed from magnetic hysteresis loops. The nanocomposites of FNPs and β-phase of PVDF were prepared via mixed solvent approach using THF/DMF with different concentrations of FNPs. The rheological behaviour of the nanocomposites was studied with and without ageing in an applied magnetic field of 3500 Gauss for 3 h. Samples depicts shear thinning to shear thickening transition, decrease in zero shear viscosity and long frequency range viscoelastic behaviour as function of increasing FNP concentration. Increase in CST region, fluidity and complex modulus are the main consequences of magnetic aging. FNP-PVDF nanocomposites with such properties could find applications in flexible magnetic and mechanical films for soft body armor and memory storage.

In-situ production of magnetic char via rapid subcritical hydrothermal carbonisation of paunch waste

The conventional hydrothermal carbonisation (HTC) is mainly tied to the high capital investment of the reactor and low product quality. In a novel approach, the rapid subcritical HTC of paunch waste (at 240 °C for only 5 min) was proposed to enhance the quality of products and their utilisation via in-situ production of magnetic hydrochar. Magnetite nanoparticles were found on the surface of hydrochar with size of 10–20 nm and crystal lattice spacing of 0.25 nm, XRD characteristic peaks of magnetite, and strong FTIR peak at 580 cm−1 assigned to Fe-O stretching in the crystalline lattice of magnetite. Magnetic hydrochar could adsorb Congo Red at a capacity of 59.9 mg g−1. An organic-rich process water with a high COD of 43 g L−1 was co-generated along with magnetic hydrochar and assumed to be anaerobically digested. The estimated theoretical methane yield was found sufficient to run the HTC plant in an energy-neutral mode. After developing a process model in Aspen plus, the discounted cash flow analysis revealed a net present value of US$13.04 MM for 30 years of operation, which can increase to $34.79 MM if the iron precursors are sourced from locally available iron-rich sludge.

Potential impact of dispersion products of magnetite quartzites on the environment

Using XRF, TG-DTA, chemical and sedimentation analysis of the products of processing of magnetite quartzites from the N Ore Processing Plant of Krivorozhye, changes in the phase and chemical composition of samples of four stages of magnetic separation and tailings were traced compared to a sample of the raw ore, and the potential impact of the dispersion process on the environment was revealed. Thermogravimetric studies indicate phase transformations of magnetite to maghemite (250-340 ° C), polymorphic transformations of iron oxides and destruction of rock-forming minerals (430-480 ° C), conversion of alpha quartz to beta-form (564-568 ° C), dehydroxylation of iron and magnesium oxyhydroxides (385 ° C), conversion of beta-quartz to beta-cristobalite (970 ° C). In the process of enrichment, there is an increase in the loss of mass of the samples, which is %: 0.06 (I); 1.46 (II); 1.9 (III), and 2.6 (IV). According to X-ray diffraction, the main ore mineral is magnetite, the rock-forming mineral is quartz. Among the secondary minerals are sulfides, cummingtonite, actinolite, and others. It is shown that at the first stage of enrichment all primary and secondary minerals are present in the samples, at the 2nd stage sulfides disappear from the sample, at the 3rd stage secondary minerals disappear, and at the 4th stage quartz remains in the sample and it forms aggregates with magnetite. The parameter of the crystal lattice of magnetite varies between 8.397-8.403 nm, its coherent scattering region (CSR) is 31.4-35.6 nm. It is found that in the course of ore grinding the destruction of secondary minerals takes place with the removal of destruction products, as evidenced by the occurrence of disperse quartz in the tailings. According to sedimentation analysis data, in the first 20 seconds, more than half of the particles with a size of 24-28 μm were deposited from the pulp, after 3 minutes, particles with a size of 8-9 μm settled, after 6 minutes - particles with a size of 6-7 μm. Within 30 minutes, almost complete precipitation of particles with sizes of 4.5-2.7 μm was observed. Hydraulic classification of the tailings showed the deposition of mainly quartz particles in the first and second chambers of the separator, actinolite and muscovite particles were separated in the third chamber, and cummingtonite, biotite and chlorite in the fourth chamber. Analysis of the chemical composition of the dispersion products indicates that Si, Ca, and Na accumulate in the tailings, whereas Ti is removed, and could potentially enter the environment. It is shown that the tailings and separation products increase the content of Zn, and the tailings accumulate environmentally hazardous As, and Nb. At the same time, the concentrations of other elements remain stable at all stages of processing.

Characterization of the Crystallographic Preferred Orientation Relationships of the Magnetite-Hematite-Goethite Phase Transformation during Martitization

The most frequent crystallographic preferred orientations developed during the progressive phase transformation of magnetite-hematite-goethite are described and analyzed in two natural samples of banded iron formations from Carajás Mineral Province. Microtextures of martitized grains containing the three phases and the microplaty matrix were analyzed in a scanning electron microscope equipped with a detector for electron backscatter diffraction. For identifying the correlation between magnetite, hematite and goethite lattice and topotaxity during transformation, multiple orientation relationships between the three phases were tested and verified using three-dimensional misorientation analysis. The results show that basal planes of goethite coincide with basal planes of hematite, which coincide with octahedral planes of magnetite. This indicates that transformation between the three minerals happens topotactically, and the oxygen lattice framework is preserved in all members of the reaction as a form of crystallographic memory. As a result of progressive and cyclical changes in oxidation/reduction conditions, an assemblage of high-order orientation relationships is observed and assigned to a complex process of transformation twinning in-between phase transformation of magnetite, hematite and goethite. In the N4WS iron ore deposit, iron oxides/hydroxides from martitized grains work as susceptible markers of environmental changes still in solid state during the diagenetic process.

Technogenic Magnetic Particles in Soils and Ecological–Geochemical Assessment of the Soil Cover of an Industrial City in the Ural, Russia

The work is devoted to the study of pollution by technogenic magnetic particles and heavy metals of soils in the city of Gubakha, Middle Ural (Russia). The aim of the work is the ecological and geochemical assessment of the elemental chemical composition of the soils of the city of Gubakha, and the establishment of the geochemical role of technogenic magnetic particles (TMPs). For the first time, the regularities of the spatial distribution of magnetic susceptibility in the soils of the city of Gubakha were revealed, and the morphology, elemental and mineralogical compositions of magnetic particles in the soils of an industrial city in the Middle Urals were characterized using the methods of the chemical extraction of iron compounds, magnetic separation, ESEM/EDS, and Mössbauer spectroscopy. The magnetic phase of soils contains magnetite/maghemite, hematite, pyrrhotite, intermetallic alloys and chromite. Spherical magnetic particles are hollow, and have a magnetite shell and a varied surface texture. The crystal lattice of magnetite is characterized by low stoichiometry. The heavy metals Zn, Cu, Ni and Cr are concentrated in magnetic particles and have a high correlation coefficient with magnetic susceptibility. The level of contamination of Cu, Ni, Zn, Cr and Mn in the soils of a residential zone of Gubakha, estimated by the value of the pollution load index (PLI), was high. The Igeo index for Fe ranges from 6.2 to 12.2, for Cu–1.1 and Ni–1.1. The combination of methods for measuring magnetic susceptibility, determining the mineralogical composition of iron compounds, and determining the elemental chemical composition by X-ray fluorescence, has shown the effectiveness of an integrated approach for carrying out an ecological–geochemical assessment of the soil cover of Gubakha.

Fate of titanium in alkaline electro-reduction of sintered titanomagnetite

Direct electrochemical reduction of iron ore in concentrated NaOH electrolyte has been proposed as a potential route to substantially reducing the global steel industry’s CO2 emissions. Here, we report the solid-state electro-reduction of sintered pellets formed from titanomagnetite ironsand. This commercial iron ore contains ∼4 wt.% Ti which is directly incorporated within the magnetite lattice. At 110 °C, these pellets are electrochemically reduced and exhibit a well-defined reaction front which moves into the pellet as the reaction progresses. The electro-reduction process selectively produces iron metal, whilst the Ti content is not reduced. Instead, Ti becomes enriched in segregated oxide inclusions, which are subsequently transformed to a sodium iron titanate phase through taking up Na+ from the electrolyte. These inclusions adopt an elongated shape and appear to exhibit locally preferential alignment. This suggests that they may nucleate from the microscopic titanohematite lamellae which naturally occur within the original ironsand particles. The expulsion of contaminant Ti-oxides from the final reduced metal matrix has implications for the potential to development of an industrial electrochemical iron-making process utilising titanomagnetite ore.

Texture and composition of magnetite in the Duotoushan deposit, NW China: implications for ore genesis of Fe–Cu deposits

AbstractThe Duotoushan deposit is an important Fe–Cu deposit in the Aqishan–Yamansu metallogenic belt of eastern Tianshan, NW China. Magnetite occurs in two main habits which are common in many Fe–Cu deposits, i.e. platy (TD1 Mag) and granular magnetite (TD2 Mag) have been identified at Duotoushan. Platy magnetite shows two different zones (bright and dark) based on the observations by scanning electron microscopy. The bright part (TD1-L) is the main part of TD1 magnetite and lacks inclusions. The dark part (TD1-D) is very porous and has abundant tiny silicate inclusions. Granular magnetite is usually anhedral with obvious oscillatory zoning in back-scattered electron images. In general, the dark zones of magnetite are characterised by greater Si, Ca, Al and lesser Fe contents than the bright zones. In situ X-ray diffraction (XRD) analysis shows that the lattice parameter of TD1 magnetite is approximately equal to that of standard magnetite and slightly higher than that of TD2 magnetite, indicating that some cations with ionic radii smaller than those of Fe2+ or Fe3+ entered the magnetite lattice by simple or coupled substitution mechanisms in TD2 magnetite.The results in the present study show that the effects of temperature and $f_{{\rm O}_ 2}$ on platy magnetite are very limited and the changing fluid composition might be the major controlling factor for the formation of Duotoushan platy magnetite. Although the possibility that mushketovite transformed from hematite cannot be excluded entirely, evidence from in situ XRD data, pore-volume ratio calculation and the growth habit of intergrown minerals indicates that platy magnetite (TD1) coexisting with amphibole was more likely to have been precipitated originally from hydrothermal fluid. This was then affected by changes in the fluid composition which consequently led to dissolution of primary magnetite (TD1-L) and re-precipitation of TD1-D magnetite (with abundant porosity and mineral inclusions). Meanwhile, granular magnetite (TD2) with oscillatory zoning, and coexisting with epidote and quartz, was precipitated from fluid with periodic variation in temperature. These oscillatory zones are characterised by bands enriched in Si, Al and Ca alternating with bands depleted in these elements. The present investigation revealed a complex evolutionary process for magnetite formation in the Duotoushan deposit. The importance of combined investigation of texture and compositional characterisation of magnetite for study of the ore genesis and evolution of Fe–Cu deposits is highlighted.

Local Atomic and Electronic Structures of Superparamagnetic Nanoparticles Based on Iron Oxides for Local Hyperthermia in Oncology

Iron oxide-based superparamagnetic nanoparticles (Fe3O4) are obtained using the solvothermal synthesis. Both the pure nanoparticles of Fe3O4 and nanoparticles doped by samarium and gadolinium are obtained to manipulate their characteristics. The materials were investigated using X-ray diffraction, X-ray fluorescence, vibrating-sample magnetometry, electron microscopy, electron diffraction, and FT-IR spectroscopy. The nanoparticles have the average size of about 22.3 nm, a crystal lattice of magnetite, and superparamagnetic characteristics at room temperature. Based on the FT-IR spectroscopy, all the synthesized nanoparticles included in their composition a polyethylene glycol coating. The hyperthermic characteristics (SAR and ILP) are determined for the obtained nanoparticles in an alternating magnetic field (AMF). The promising prospects of using the discussed superparamagnetic nanoparticles based on iron oxide particles doped by the atoms of the rare-earth elements for the local magnetic hyperthermia are shown.

Simultaneous degradation of the anticancer drugs 5-fluorouracil and cyclophosphamide using a heterogeneous photo-Fenton process based on copper-containing magnetites (Fe3-xCuxO4)

The effect of substitution of iron by copper in the magnetite lattice was investigated in terms of the catalytic activity in the heterogeneous photo-Fenton process. The physicochemical properties of the Fe3-xCuxO4 nanoparticles were characterized by X-ray diffraction (XRD), X-ray fluorescence (WD-XRF), specific surface area measurements, field emission scanning electron microscopy (FEG-SEM), and X-ray photoelectron spectroscopy (XPS). Copper-modified magnetite showed higher catalytic activity for H2O2 conversion to HO• (estimated using 7-hydroxycoumarin), compared to pristine magnetite (Fe3O4). Consequently, improved degradation of the anticancer drugs 5-fluorouracil (5-FU) and cyclophosphamide (CP) was observed, with high efficiencies achieved using Fe2.75Cu0.25O4 (0.125 g L−1) and 15 mmol L−1 H2O2, at pH 6.5, which resulted in complete degradation of 7.7 μmol L−1 5-FU and CP after 150 min. Low leaching of Cu and Fe demonstrated the stability of the catalyst in the Fenton process, with high catalytic activity (>90%) maintained after use in 4 cycles. The addition of radical scavengers such as methanol, tert-butanol and iodide ions indicated that surface-bonded hydroxyl radicals played a major role in the degradation of 5-FU and CP in the Fe3-xCuxO4/H2O2 system. The substitution of octahedral Fe(II) sites of the magnetite lattice by Cu(II) and the partial oxidation of Cu(I) to Cu(II) and Fe(II) to Fe(III) on the catalyst surface after the Fenton reaction were confirmed by analysis of the XPS spectra.

Differently shaped nanocrystalline (Fe, Y)3O4 and its adsorption efficiency toward inorganic arsenic species

Herein we report effects of partial substitution of Fe3+ by Y3+ in magnetite (Fe3O4) on morphology and inorganic arsenic species adsorption efficiency of the Fe3−xYxO4 nanoparticles formed. The series of Fe3−xYxO4 (x = 0.00, 0.042 and 0.084, labeled as Y00, Y05 and Y10, respectively) was synthesized using co-precipitation followed by microwave-hydrothermal treatment (MW) at 200 °C. With increase of yttrium content (x value), both the morphological inhomogeneity of the samples and the fraction of spinel nanorods as compared to spinel pseudospherical particles increased. By both transmission electron microscopy and x-ray powder diffraction analyses, it was determined that the direction of growth of the spinel nanorods is along the [110] crystallographic direction. The Fe3−xYxO4 affinities of adsorption toward the inorganic arsenic species, As(III) (arsenite, AsO33−) and As(V) (arsenate, AsO43−), were investigated. Increased Y3+ content related to changes in sample morphology was followed by a decrease of As(III) removal efficiency and vice versa for As(V). The increase in Y3+ content, in addition to increasing the adsorption capacity for As(V), significantly expanded the optimum pH range for the maximum removal and decreased the contact time for necessary 50% removal (t1/2) of As(V) (Y00: pH 2–3, t1/2 = 3.12 min; Y05: pH 2–6, t1/2 = 2.12 min and Y10: pH 2–10, t1/2 = 1.12 min). The results point to incorporation of Y3+ in the crystal lattice of magnetite, inducing nanorod spinel structure formation with significant changes in sorption properties important for the removal of inorganic arsenic from waters.

The role of mineral nanoparticles at a fluid-magnetite interface: Implications for trace-element uptake in hydrothermal systems

Abstract The migrating fluid-mineral interface provides an opportunity for the uptake of trace elements as solid solutions in the newly formed crystal lattice during the non-equilibrium growth of the crystal. However, mineral nanoparticles could precipitate directly from the interfacial fluid when it evolves to a supersaturated situation. To better understand the role of mineral nanoparticles in this scenario, this study focuses on a well-documented magnetite with oscillatory zoning from a skarn deposit by using high-resolution transmission electron microscopy (TEM). Our results show that the Al concentration in magnetite measured on a micrometer-scale is caused by three different effects: Al solid solution, Al-rich nanometer-sized lamellae, and zinc spinel nanoparticles in the host magnetite. Here, we propose a genetic relationship among the three different phases mentioned above. At first, a continuous increase of the Al concentration in the interfacial fluid can be incorporated into the crystal lattice of magnetite forming a solid solution. During cooling in a later stage, aluminum in magnetite is oversaturated and exsolution of hercynite (Al-rich lamellae) occurs from the host magnetite. If the Al concentration at the fluid-magnetite interface still increases during further growth of magnetite, the substitution of Fe by Al has gradually reached saturation so that aluminum cannot be incorporated in the magnetite crystal structure any longer. Using the magnetite lattice as a template, nucleation of abundant zinc spinel nanoparticles occurs. This will, in turn, lead to a gradual depletion of Al concentration in the interfacial fluid until the available ions for zinc spinel nucleation and growth have been used up. As a result, the migrating fluid-magnetite interface will enrich the Al concentration in the interfacial fluid until the available ion concentration is sufficient for nucleation of zinc spinel phase again. The fluid-mineral interface in this mechanism has been repeatedly utilized during crystal growth, providing an efficient way for the uptake of trace element from a related undersaturated bulk fluid.

Quantum-Mechanical Investigation of the Structures and Energetics of Uranium and Plutonium Incorporated into the Magnetite (Fe3O4) Lattice

Understanding the behavior of radionuclides is key to designing and implementing effective waste storage and remediation schemes. Incorporation into minerals is one process that may reduce the mobility of these contaminants. This study uses quantum-mechanical modeling to evaluate the incorporation of U and Pu into magnetite (Fe3O4), a common mineral and steel corrosion product. The incorporation from solid and aqueous sources (e.g., PuO2(s) and UO22+(aq)) with various oxidation states (Pu +3; U and Pu +4, +5, +6) is explored. Charge balancing is achieved via Fe lattice vacancies. The incorporation energies (ΔEinc) depend strongly on the stability of different actinide oxide phases and the hydration energies of aqueous species (e.g., ΔEinc of 1.38 and 2.88 eV for U5+ from δ-U2O5(s) and UO2+(aq), respectively). The calculated bonding environment of incorporated U (U–Oax = 2.16–2.24 A, CN = 2; U–Oeq = 2.30–2.34 A, CN = 4) aligns with the range of experimental results. Analysis of incorporation energies as we...

Infrared Spectroscopic Study of Magnetic Behavior of Dysprosium Doped Magnetite Nanoparticles

Dysprosium doped magnetite (Fe3−xDyxO4 with x = 0.0–0.1) nanoparticles have been synthesized using the co-precipitation method. Magnetic characterization using vibrating sample magnetometer (VSM) has revealed an enhancement in the saturation magnetization with Dy3+ doping. The occupancy of the dopant ions in magnetite lattice has been probed using Fourier transform infrared spectroscopy (FTIR). The shifting of ν2 (Fe–O) band at 452 cm− 1 for undoped samples to 443 cm− 1 for dysprosium-doped samples is indicative of occupancy of dysprosium at the octahedral site. X-ray diffraction (XRD) patterns have been used to calculate the strain and lattice constant. The strain is found to increase with doping level and attained a maximum value for the x = 0.03. This increase in the strain can be attributed to occupancy of large diameter Dy3+ ions at the octahedral site of spinel structure of the magnetite lattice.

Interface reaction between Fe3-xSnxO4 and CaO roasted under CO-CO2 atmosphere

Part of tin in the magnetite-type tin-bearing ores existed as isomorphous Sn4+ in the lattice of magnetite (Fe3-xSnxO4, X=0–1.0), which was impossible to separate and recover by physical beneficiation methods In this study, a calcified roasting process under CO-CO2 atmosphere was applied to separate tin from the magnetite-type tin-bearing tailings, and the results indicated that the isomorphous Sn4+ in the magnetite was removed effectively. Then, Fe2.6Sn0.4O4 was synthesized to investigate the interface reaction mechanisms between CaO and Fe3-xSnxO4. The results indicated that the calcified roasting process can be divided into three stages: the ionic migration of Sn4+ on the interface between CaO and Fe3-xSnxO4 and formation of calcium stannates (Ca2SnO4/CaSnO3), diffusion of Sn4+ through the product layer (CaSnO4/Ca2SnO4), the oxidation of FeO to Fe3O4 by CO2. These findings can provide theoretical support for the utilization of magnetite-type tin-bearing tailings by the calcified roasting process.

Mineralogical and physical beneficiation studies for iron extraction from Bardaskan titanomagnetite placer deposit

In this work, a bench-scale process was developed using mineral-processing methods to recover iron from a placer deposit located in Bardaskan, Khorasan-e-Razavi, Iran. The mineralogical studies were performed by X-ray Diffraction (XRD), X-ray Fluorescence (XRF), Electron Probe Micro-Analyzer (EPMA), and an optical microscope. These studies indicated that titanomagnetite, magnetite, and hematite were presented in the sample as valuable minerals. In contrast, the gangue minerals were silicates such as pyroxene, plagioclase, quartz, feldspar, calcite, and some secondary minerals. The optimum liberation degree of the iron-containing minerals was obtained to be 75 µm with average Fe and TiO2 contents of 5% and 1%, respectively. The analysis showed that magnetite was the main iron mineral, and most of the hematite was formed due to martitization. Also minor ilmenite contents were found in hematite and magnetite in a blade form. The maximum TiO2 content in the magnetite lattice was 19%, only 8% of which was recovered to the magnetic product. Eventually, an iron concentration flow sheet was developed, which included the removal of a major part of silicates and then iron minerals by a low intensity wet magnetic separator. The final product contained 55, 7.8, and 0.77% of Fe, TiO2, and V2O5, respectively, which can be used for iron production, and V2O5 extraction (as the by-product).