Showing papers on "Magnetite published in 2015"

Magnetite (Fe 3 O 4 )-filled carbon nanofibers as electro-conducting/superparamagnetic nanohybrids and their multifunctional polymer composites

Abstract: A mild-temperature, nonchemical technique is used to produce a nanohybrid multifunctional (electro-conducting and magnetic) powder material by intercalating iron oxide nanoparticles in large aspect ratio, open-ended, hollow-core carbon nanofibers (CNFs). Single-crystal, superparamagnetic Fe3O4 nanoparticles (10 nm average diameter) filled the CNF internal cavity (diameter <100 nm) after successive steps starting with dispersion of CNFs and magnetite nanoparticles in aqueous or organic solvents, sequencing or combining sonication-assisted capillary imbibition and concentration-driven diffusion, and finally drying at mild temperatures. The influence of several process parameters—such as sonication type and duration, concentration of solids dispersed in solvent, CNF-to-nanoparticle mass ratio, and drying temperature—on intercalation efficiency (evaluated in terms of particle packing in the CNF cavity) was studied using electron microscopy. The magnetic CNF powder was used as a low-concentration filler in poly(methyl methacrylate) to demonstrate thin free-standing polymer films with simultaneous magnetic and electro-conducting properties. Such films could be implemented in sensors, optoelectromagnetic devices, or electromagnetic interference shields.

Redox cycling of Fe(II) and Fe(III) in magnetite by Fe-metabolizing bacteria.

Abstract: Microorganisms are a primary control on the redox-induced cycling of iron in the environment. Despite the ability of bacteria to grow using both Fe(II) and Fe(III) bound in solid-phase iron minerals, it is currently unknown whether changing environmental conditions enable the sharing of electrons in mixed-valent iron oxides between bacteria with different metabolisms. We show through magnetic and spectroscopic measurements that the phototrophic Fe(II)-oxidizing bacterium Rhodopseudomonas palustris TIE-1 oxidizes magnetite (Fe3O4) nanoparticles using light energy. This process is reversible in co-cultures by the anaerobic Fe(III)-reducing bacterium Geobacter sulfurreducens. These results demonstrate that Fe ions bound in the highly crystalline mineral magnetite are bioavailable as electron sinks and electron sources under varying environmental conditions, effectively rendering magnetite a naturally occurring battery.

Activation of Persulfate by Irradiated Magnetite: Implications for the Degradation of Phenol under Heterogeneous Photo-Fenton-Like Conditions

Abstract: We show that phenol can be effectively degraded by magnetite in the presence of persulfate (S2O8(2–)) under UVA irradiation. The process involves the radical SO4(–•), formed from S2O8(2–) in the presence of Fe(II). Although magnetite naturally contains Fe(II), the air-exposed oxide surface is fully oxidized to Fe(III) and irradiation is required to produce Fe(II). The magnetite + S2O8(2–) system was superior to the corresponding magnetite + H2O2 one in the presence of radical scavengers and in a natural water matrix, but it induced phenol mineralization in ultrapure water to a lesser extent. The leaching of Fe from the oxide surface was very limited, and much below the wastewater discharge limits. The reasonable performance of the magnetite/persulfate system in a natural water matrix and the low levels of dissolved Fe are potentially important for the removal of organic contaminants in wastewater.

Iron oxides semiconductors are efficients for solar water disinfection: A comparison with photo-Fenton processes at neutral pH

Abstract: The photocatalytic activities of four different commercially available iron (hydr)oxides semiconductors, i.e. hematite (alpha-Fe2O3), goethite (alpha-FeOOH), wustite (FeO) and magnetite (Fe3O4), were evaluated for bacteria inactivation at neutral pH in the absence or presence of H2O2. Our results showed that heterogeneous photocatalysis and/or photo-Fenton processes catalyzed by low concentrations of reagents (0.6 mg/L Fe3+ and 10 mg/L H2O2) under sunlight may serve as a disinfection method for waterborne bacterial pathogens. In particular, we found that, with the exception of magnetite which need H2O2 as electron acceptor, all the other semiconductor iron (hydr)oxides were photoactive under sunlight in absence of H2O2 (using only oxygen as electron acceptor). Furthermore, for all iron (hydr)oxide studied in this work, no bacterial reactivation and/or growth was observed after photo-Fenton treatment. The same antimicrobial activity was obtained for the photocatalytic semiconducting action of hematite and goethite. Additionally, a delayed disinfection effect was observed to continue in the dark for the photo-assisted wilstite-based treatment. Electron spin resonance (ESR) in combination with spin-trapping was employed to detect reactive oxygen species (ROS) involved in heterogeneous photocatalysis and/or photo-Fenton treatments mediated by iron (hydr)oxide particles. In particular, ESR confirmed that center dot OH and O-2(center dot-) radicals were the principal ROS produced under photo-assisted action of iron (hydr)oxide particles in the absence or presence of H2O2. We also found that the components of natural water (i.e. natural organic matter (NOM) and inorganic substances) did not interfere with the photocatalytic semiconducting action of hematite to bacterial inactivation. However, these components enhance the bacterial inactivation by heterogeneous photo-Fenton action of hematite. Overall our results demonstrated, for the first time, that low concentration of iron (hydr)oxides, acting both as photocatalytic semiconductors or catalysts of the heterogeneous photo-Fenton process at neutral pH, may provide a useful strategy for efficient bacterial disinfection. (C) 2014 Elsevier B.V. All rights reserved.

Giant Kiruna-type deposits form by efficient flotation of magmatic magnetite suspensions

Abstract: Kiruna-type iron oxide-apatite (IOA) deposits are an important source of Fe ore, and two radically different processes are being actively investigated for their origin. One hypothesis invokes direct crystallization of immiscible Fe-rich melt that separated from a parent silicate magma, while the other hypothesis invokes deposition of Fe-oxides from hydrothermal fluids of either magmatic or crustal origin. Here, we present a new model based on Fe and O stable isotopes and trace and major element geochemistry data of magnetite from the ~350 Mt Fe Los Colorados IOA deposit in the Chilean iron belt that merges these divergent processes into a single sequence of events that explains all characteristic features of these curious deposits. We propose that concentration of magnetite takes place by the preferred wetting of magnetite, followed by buoyant segregation of these earlyformed magmatic magnetite-bubble pairs, which become a rising magnetite suspension that deposits massive magnetite in regionalscale transcurrent faults. Our data demonstrate an unambiguous magmatic origin, consistent with the namesake IOA analogue in the Kiruna district, Sweden. Further, our model explains the observed coexisting purely magmatic and hydrothermal-magmatic features and allows a genetic connection between Kiruna-type IOA and iron oxide-copper-gold deposits, contributing to a global understanding valuable to exploration efforts.

Synthesis, Characterization and Applications of Iron Oxide Nanoparticles - a Short Review

Abstract: Iron oxide is a polymorphous crystalline mineral, including hematite, a-Fe 2 O 3 , magnetite, Fe 3 O 4 and maghemite, g-Fe 2 O 3 . In the area of solid propulsion, nanoparticulate materials such, hematite and maghemite, exhibit high performance on thermal decomposition of ammonium perchlorate (AP).The best catalytic effect of metallic iron oxide nanoparticles was attributed to its small particle size, more active sites and high surface area, which prove most gas adsorption of released products during the thermal reactions of oxidizer. Nowadays, metallic iron nanoparticles can be synthesized via many methods, by co-precipitation, sol-gel, microemulsion, or thermal decomposition. Although there are data on these synthetic methods in the literature, there is a lack of details in nanoparticulate oxides and on the characterization techniques used. In this context, this short review presents methods for obtaining nanoparticulate iron oxides and characteristics of the different characterization techniques and decomposition of these nanomaterials. The morphologies and structures can be characterized by transmission electron microscopy, scanning electron microscopy, X-ray powder diffraction, and FT- IR spectroscopy and the textural properties by physical adsorption.

Geochemistry of magnetite from porphyry Cu and skarn deposits in the southwestern United States

Abstract: A combination of petrographic observations, laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), and statistical data exploration was used in this study to determine compositional variations in hydrothermal and igneous magnetite from five porphyry Cu–Mo and skarn deposits in the southwestern United States, and igneous magnetite from the unmineralized, granodioritic Inner Zone Batholith, Japan. The most important overall discriminators for the minor and trace element chemistry of magnetite from the investigated porphyry and skarn deposits are Mg, Al, Ti, V, Mn, Co, Zn, and Ga—of these the elements with the highest variance for (I) igneous magnetite are Mg, Al, Ti, V, Mn, Zn, for (II) hydrothermal porphyry magnetite are Mg, Ti, V, Mn, Co, Zn, and for (III) hydrothermal skarn magnetite are Mg, Ti, Mn, Zn, and Ga. Nickel could only be detected at levels above the limit of reporting (LOR) in two igneous magnetites. Equally, Cr could only be detected in one igneous occurrence. Copper, As, Mo, Ag, Au, and Pb have been reported in magnetite by other authors but could not be detected at levels greater than their respective LORs in our samples. Comparison with the chemical signature of igneous magnetite from the barren Inner Zone Batholith, Japan, suggests that V, Mn, Co, and Ga concentrations are relatively depleted in magnetite from the porphyry and skarn deposits. Higher formation conditions in combination with distinct differences between melt and hydrothermal fluid compositions are reflected in Al, Ti, V, and Ga concentrations that are, on average, higher in igneous magnetite than in hydrothermal magnetite (including porphyry and skarn magnetite). Low Ti and V concentrations in combination with high Mn concentrations are characteristic features of magnetite from skarn deposits. High Mg concentrations (<1,000 ppm) are characteristic for magnetite from magnesian skarn and likely reflect extensive fluid/rock interaction. In porphyry deposits, hydrothermal magnetite from different vein types can be distinguished by varying Ti, V, Mn, and Zn contents. Titanium and V concentrations are highly variable among hydrothermal and igneous magnetites, but Ti concentrations above 3,560 ppm could only be detected in igneous magnetite, and V concentrations are on average lower in hydrothermal magnetite. The highest Ti concentrations are present in igneous magnetite from gabbro and monzonite. The lowest Ti concentrations were recorded in igneous magnetite from granodiorite and granodiorite breccia and largely overlap with Ti concentrations found in hydrothermal porphyry magnetite. Magnesium and Mn concentrations vary between magnetite from different skarn deposits but are generally greater than in hydrothermal magnetite from the porphyry deposits. High Mg, and low Ti and V concentrations characterize hydrothermal magnetite from magnesian skarn deposits and follow a trend that indicates that magnetite from skarn (calcic and magnesian) commonly has low Ti and V concentrations.

Did the massive magnetite “lava flows” of El Laco (Chile) form by magmatic or hydrothermal processes? New constraints from magnetite composition by LA-ICP-MS

Abstract: The El Laco magnetite deposits consist of more than 98 % magnetite but show field textures remarkably similar to mafic lava flows. Therefore, it has long been suggested that they represent a rare example of an effusive Fe oxide liquid. Field and petrographic evidence, however, suggest that the magnetite deposits represent replacement of andesite flows and that the textures are pseudomorphs. We determined the trace element content of magnetite by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) from various settings at El Laco and compared them with magnetite from both igneous and hydrothermal environments. This new technique allows us to place constraints on the conditions under which magnetite in these supposed magnetite “lava flows” formed. The trace element content of magnetite from the massive magnetite samples is different to any known magmatic magnetite, including primary magnetite phenocrysts from the unaltered andesite host rocks at El Laco. Instead, the El Laco magnetite is most similar in composition to hydrothermal magnetite from high-temperature environments (>500 °C), such as iron oxide-copper-gold (IOCG) and porphyry-Cu deposits. The magnetite trace elements from massive magnetite are characterised by (1) depletion in elements considered relatively immobile in hydrothermal fluids (e.g. Ti, Al, Cr, Zr, Hf and Sc); (2) enrichment in elements that are highly incompatible with magmatic magnetite (rare earth elements (REE), Si, Ca, Na and P) and normally present in very low abundance in magmatic magnetite; (3) high Ni/Cr ratios which are typical of magnetite from hydrothermal environments; and (4) oscillatory zoning of Si, Ca, Mg, REE and most high field strength elements, and zoning truncations indicating dissolution, similar to that formed in hydrothermal Fe skarn deposits. In addition, secondary magnetite in altered, brecciated host rock, forming disseminations and veins, has the same composition as magnetite from the massive lenses. Euhedral magnetite lining both open-spaced veins in the brecciated host rock and along the walls of large, hollow chimneys in the massive magnetite lenses also displays oscillatory zoning and most likely formed by fluctuating composition and/or physio-chemical conditions of the fluid. Thus, the chemical fingerprint of magnetite from the supposed El Laco magnetite lava flows supports the hydrothermal model of metasomatic replacement of andesite lava flows, by dissolution and precipitation of magnetite from high-temperature fluids, rather than a magmatic origin from an effusive Fe oxide liquid.

Heterogeneous activation of Oxone by substituted magnetites Fe3-xMxO4 (Cr, Mn, Co, Ni) for degradation of Acid Orange II at neutral pH

Abstract: In this study, the effect of incorporation of transition metals (i.e., Co, Mn, Cr, and Ni) into the magnetite on the reactivity towards Oxone activation was investigated at neutral pH. The magnetite samples were characterized by XRD and EXAFS. Co, Cr, and Ni were in the valences of +2, +3, and +2, respectively, while Mn was in the valences of +2 and +3. These cations occupied the octahedral sites of magnetite, but the distribution of Mn and Ni on the octahedral sites of magnetite surface increased with an increase of substitution extent. The activity of magnetites in Oxone activation was investigated through Acid Orange II (AOII) degradation at an initial pH of 7.0 with or without phosphate-buffered solution. In neutral medium, the AOII degradation by Mn, Cr, and Ni substituting magnetites followed pseudo-first-order kinetics. The incorporation of Co, Mn, and Ni improved the catalytic activity of magnetite in the order Mn tert -butyl alcohols. The different effects of studied substitutions on the reactivity of magnetite were discussed in views of reactive radical species and microstructural environment.

Reequilibration processes in magnetite from iron skarn deposits

Abstract: Textural and compositional data for magnetite from nine iron skarn deposits in Canada, Romania, and China show that most samples have reequilibrated by dissolution and reprecipitation, oxy-exsolution, and/or recrystallization. The dissolution and reprecipitation processes are most extensive and are present in most magnetite samples examined, whereas the oxy-exsolution occurs only in high-Ti magnetite, forming exsolution lamellae of Fe-Ti-Al oxides. Electron microprobe analysis indicates that the reequilibration processes have significantly modified the minor and trace element compositions of magnetite, notably Si, Mg, Ca, Al, Mn, and Ti, whereas oxy-exsolution is effective in decreasing the Ti content of high-Ti magnetite. Many analyses of magnetite grains from the skarn deposits plot variably in the banded iron formations (BIF), iron oxide–copper-gold (IOCG), or porphyry Cu fields using the Ti + V versus Ca + Al + Mn discrimination diagram. This pattern suggests that trace element data for magnetite that has unusual composition and/or reequilibrated cannot be reliably used as a petrogenetic indicator. Mixing of externally derived saline fluids with Fe-rich magmatic-hydrothermal solutions, an increase in temperature, and local decreasing pressure and f O 2 are considered the most important causes for the dissolution and reprecipitation, or recrystallization, of the magnetite; increasing f O 2 and decreasing temperature may facilitate oxy-exsolution of Fe-Ti-Al oxides in high-Ti magnetite. Results presented here highlight the importance of detailed textural characterization prior to in situ chemical analysis of magnetite grains so that mineral compositions can be properly evaluated in terms of the genesis and evolution of iron skarn deposits.

Production and transformation of mixed-valent nanoparticles generated by Fe(0) electrocoagulation.

Abstract: Mixed-valent iron nanoparticles (NP) generated electrochemically by Fe(0) electrocoagulation (EC) show promise for on-demand industrial and drinking water treatment in engineered systems. This work applies multiple characterization techniques (in situ Raman spectroscopy, XRD, SEM, and cryo-TEM) to investigate the formation and persistence of magnetite and green rust (GR) NP phases produced via the Fe(0) EC process. Current density and background electrolyte composition were examined in a controlled anaerobic system to determine the initial Fe phases generated as well as transformation products with aging. Fe phases were characterized in an aerobic EC system with both simple model electrolytes and real groundwater to investigate the formation and aging of Fe phases produced in a system representing treatment of arsenic-contaminated ground waters in South Asia. Two central pathways for magnetite production via Fe(0) EC were identified: (i) as a primary product (formation within seconds when DO absent, no intermediates detected) and (ii) as a transformation product of GR (from minutes to days depending on pH, electrolyte composition, and aging conditions). This study provides a better understanding of the formation conditions of magnetite, GR, and ferric (oxyhydr)oxides in Fe EC, which is essential for process optimization for varying source waters.

Experimental diagenesis of organo-mineral structures formed by microaerophilic Fe(II)-oxidizing bacteria

Abstract: Twisted stalks are organo-mineral structures produced by some microaerophilic Fe(II)-oxidizing bacteria at O2 concentrations as low as 3 μM. The presence of these structures in rocks having experienced a diagenetic history could indicate microbial Fe(II)-oxidizing activity as well as localized abundance of oxygen at the time of sediment deposition. Here we use spectroscopy and analytical microscopy to evaluate if--and what kind of--transformations occur in twisted stalks through experimental diagenesis. Unique mineral textures appear on stalks as temperature and pressure conditions increase. Haematite and magnetite form from ferrihydrite at 170 °C-120 MPa. Yet the twisted morphology of the stalks, and the organic matrix, mainly composed of long-chain saturated aliphatic compounds, are preserved at 250 °C-140 MPa. Our results suggest that iron minerals might play a role in maintaining the structural and chemical integrity of stalks under diagenetic conditions and provide spectroscopic signatures for the search of ancient life in the rock record.

Redox state of iron during high-pressure serpentinite dehydration

Abstract: The Cerro del Almirez massif (Spain) represents a unique fragment of serpentinized oceanic lithosphere that has been first equilibrated in the antigorite stability field (Atg-serpentinites) and then dehydrated into chlorite–olivine–orthopyroxene (Chl-harzburgites) at eclogite facies conditions during subduction. The massif preserves a dehydration front between Atg-serpentinites and Chl-harzburgites. It constitutes a suitable place to study redox changes in serpentinites and the nature of the released fluids during their dehydration. Relative to abyssal serpentinites, Atg-serpentinites display a low Fe3+/FeTotal(BR) (=0.55) and magnetite modal content (=2.8–4.3 wt%). Micro-X-ray absorption near-edge structure (μ-XANES) spectroscopy measurements of serpentines at the Fe–K edge show that antigorite has a lower Fe3+/FeTotal ratio (=0.48) than oceanic lizardite/chrysotile assemblages. The onset of Atg-serpentinites dehydration is marked by the crystallization of a Fe3+-rich antigorite (Fe3+/FeTotal = 0.6–0.75) in equilibrium with secondary olivine and by a decrease in magnetite amount (=1.6–2.2 wt%). This suggests a preferential partitioning of Fe3+ into serpentine rather than into olivine. The Atg-breakdown is marked by a decrease in Fe3+/FeTotal(BR) (=0.34–0.41), the crystallization of Fe2+-rich phases and the quasi-disappearance of magnetite (=0.6–1.4 wt.%). The observation of Fe3+-rich hematite and ilmenite intergrowths suggests that the O2 released by the crystallization of Fe2+-rich phases could promote hematite crystallization and a subsequent increase in fo2 inside the portion of the subducted mantle. Serpentinite dehydration could thus produce highly oxidized fluids in subduction zones and contribute to the oxidization of the sub-arc mantle wedge.

Growth of Iron Oxide Nanoparticles by Hydrothermal Process: Effect of Reaction Parameters on the Nanoparticle Size

Abstract: Different size of iron oxide nanoparticles were synthesized via hydrothermal process. The change of the size of nanoparticles with reaction temperatures (60, 100, 150, and 180 ℃) was investigated. To have further insight into the growth of nanoparticles, the different reaction times were also studied at the temperatures of 100, 150, and 180 ℃. The structural characterization was carried out with X-ray diffractometer and Fourier transform infrared spectroscopy. The nanoparticles were found to have high crystalline iron oxides with a mixture of magnetite and maghemite crystalline phases. With the increase of the nanoparticle size, the ratio of magnetite to maghemite phase increased and reached to a pure magnetite phase for the 123 ± 44 nm particles. When the reaction temperature increased from 100 to 180 ℃ for 12 h, the size of the nanoparticles increased from 14.5 ± 4 to 29.9 ± 9 nm according to transmission electron microscopy analysis. At 180 ℃, as the reaction time increased from 1 to 48 h, the size of nanoparticles increased from 20.6 ± 6 to 123 ± 44 nm. This means that the reaction times are more effective on the growth of the nanoparticles at high temperatures. Magnetic analysis by vibrating sample magnetometer showed that the nanoparticles are ferrimagnetic. By considering all nanoparticles, the saturation magnetization increased as the size of the nanoparticle increased. And the high size of nanoparticles reached the high saturation magnetization value at low applied magnetic fields. The structural and magnetic properties of the nanoparticles are found to be depending on the nanoparticle sizes which are substantially affected by the reaction temperature and time.

Natural Magnetite: an efficient catalyst for the degradation of organic contaminant

Abstract: Iron (hydr)oxides are ubiquitous earth materials that have high adsorption capacities for toxic elements and degradation ability towards organic contaminants. Many studies have investigated the reactivity of synthetic magnetite, while little is known about natural magnetite. Here, we first report the reactivity of natural magnetites with a variety of elemental impurities for catalyzing the decomposition of H2O2 to produce hydroxyl free radicals (•OH) and the consequent degradation of p-nitrophenol (p-NP). We observed that these natural magnetites show higher catalytic performance than that of the synthetic pure magnetite. The catalytic ability of natural magnetite with high phase purity depends on the surface site density while that for the magnetites with exsolutions relies on the mineralogical nature of the exsolved phases. The pleonaste exsolution can promote the generation of •OH and the consequent degradation of p-NP; the ilmenite exsolution has little effect on the decomposition of H2O2, but can increase the adsorption of p-NP on magnetite. Our results imply that natural magnetite is an efficient catalyst for the degradation of organic contaminants in nature.