Iron (Fe) minerals and ferrous iron (Fe(II)) play an important role in the several natural elemental cycles, including the carbon cycle, nutrient cycles, and the cycling of metals. In this work we have characterized the reactivity structural Fe(II) in several Fe minerals and in natural soil with uranium. We have studied the reactivity of Fe(II) in solution with the Fe oxide goethite conditions relevant to many natural systems. Green rusts are widely recognized as an intermediate phase in the Fe cycle. Here we investigate the reactivity of green rusts containing different structural anions with uraniumVI (UVI). We have also investigated the effect of aqueous bicarbonate on UVI sorption and reduction by green rusts. Our findings indicate that green rusts reduce UVI to UIV, and that environmentally relevant carbonate concentrations have little effect the rate and extent on this reaction. We have also investigated UVI reduction by structural Fe(II) in magnetite. Magnetite with varying stoichiometry (x = Fe2+/Fe3+) was reacted with UVI. Results from x-ray absorption spectroscopy indicate that the redox properties of magnetite dictate whether magnetite reduces UVI. In addition, magnetite reactivity can be "recharged" by electron transfer from aqueous Fe(II). There is little evidence of the reactivity of structural Fe(II) towards UVI in natural materials. We have characterized a naturally reduced soil and found it contains structural Fe(II) in clay minerals and a possible green rust-like phase. When this soil is exposed to UVI we find that Fe(II) reduces a portion of the U added. Our work highlights the potential for abiotic reduction of UVI by Fe(II) in reduced, Fe-rich environments. We have used 57Fe Mössbauer spectroscopy to study redox reactions of Fe(II) with goethite under biogeochemical conditions relevant to natural systems. When Fe(III) in goethite is substituted with aluminum or anions such as phosphate, silicate, carbonate, and natural organic matter are sorbed onto the surface of goethite, interfacial electron transfer occurs between sorbed Fe(II) and goethite. These results indicate that electron transfer between Fe(II) and Fe oxides occurs under environmentally relevant conditions. Electron transfer was blocked by phospholipids, however, suggesting electron transfer may be inhibited under eutrophic conditions.

Magnetic photocatalysts were synthesised by coating a magnetic core with a layer of photoactive titanium dioxide. This magnetic photocatalyst is for use in slurry-type reactors in which the catalyst can be easily recovered by the application of an external magnetic field. The first attempt at producing this magnetic photocatalyst involved the direct deposition of titanium dioxide onto the surface of magnetic iron oxide particles. The photoactivity of these Fe3O4/TiO2 was lower than that of single-phase TiO2 and was found to decrease with an increase in the heat treatment. These observations were explained in terms of an unfavourable heterojunction between the titanium dioxide and the iron oxide core. Fe ion diffusion from the iron oxide core into the titanium dioxide matrix upon heat treatment, leading to a highly doped TiO2 lattice, was also contributing to the observed low activities of these samples. These Fe3O4/TiO2 particles were found to be unstable, with photodissolution of the iron oxide phase being encountered. This photodissolution was dependent on the heat treatment applied, the greater the extent of the heat treatment, the lower the incidence of photodissolution. This was explained in terms of the stability of the iron oxide phases present, as well as the lower photoactivity of the titanium dioxide matrix. In fact, the observed photodissolution was found to be induced-photodissolution. That is, the photogenerated electrons in the titanium dioxide phase were being injected into the lower lying conduction band of the iron oxide core, leading to its reduction and then dissolution. Thus, the approach of directly depositing TiO2 onto the surface of a magnetic iron oxide core proved ineffective in producing a stable magnetic photocatalyst. The introduction of an intermediate passive SiO2 layer between the titanium dioxide phase and the iron oxide phase inhibited the direct electrical contact and hence prevented the photodissolution of the iron oxide phase. Improvements in the photoactivity were seen to be due to the inhibition of both the electronic and chemical interactions between the iron oxide and titanium dioxide phases. Preliminary optimisation experiments revealed that a thin SiO2 layer is sufficient for inhibiting the photodissolution. The thickness of the TiO2 coating was found not to have a significant effect on the photocatalytic performance of the coated particles. Finally, heat treating for 20 minutes at 450??C was sufficient for converting the titanium dioxide into a photoactive phase, longer heating times had no beneficial effect on the photoactivity.

<p>Knowledge about the stability of phases and their relationships in the Fe-O system at high pressures and temperatures is essential in implications of the multifarious states of iron oxides for models of the evolution of the Earth. In this respect, the iron ferrite magnetite (FeFe₂O₄) plays a significant role since it participates in the control of geochemistry of ferric iron, and hence oxygen fugacity in the Earth`s deep interior.</p><p>High-pressure experiments on Fe₃O₄ were performed using the diamond anvil cell technique combined with the laser and electrical resistive heating. The approach based on the combination of the synchrotron x-ray diffraction with Raman spectroscopic measurements benefited from the complementarity of the two methods originating from the different sensitivity to a range of structural order. High-pressure transformation of magnetite to a dense polymorph of the CaTi₂O₄-type structure proceeds via an intermediate step of the decomposition into a mixture of oxides on a microscopic scale. The kinetic hindrance of the reaction of the decomposition effectively prevents a phase separation controlled by diffusion and restricts the formation of the daughter products to locally ordered structures in the strained lattice of magnetite.</p><p>Thermodynamic analysis of the observed phase transformations along with published results on the elastic properties and pressure-induced transitions of iron oxides has led to the reassessment of the phase diagram of Fe₃O₄. The pressure - temperature field of its stability with respect to the breakdown to a mixture of oxides FeO and Fe₂O₃, and to the transition to a high-pressure form, has been accordingly modified.</p>

Knowledge about the stability of phases and their relationships in the Fe-O system at high pressures and temperatures is essential in implications of the multifarious states of iron oxides for models of the evolution of the Earth. In this respect, the iron ferrite magnetite (FeFe2O4) plays a significant role since it participates in the control of geochemistry of ferric iron, and hence oxygen fugacity in the Earth`s deep interior. High-pressure experiments on Fe3O4 were performed using the diamond anvil cell technique combined with the laser and electrical resistive heating. The approach based on the combination of the synchrotron x-ray diffraction with Raman spectroscopic measurements benefited from the complementarity of the two methods originating from the different sensitivity to a range of structural order. High-pressure transformation of magnetite to a dense polymorph of the CaTi2O4-type structure proceeds via an intermediate step of the decomposition into a mixture of oxides on a microscopic scale. The kinetic hindrance of the reaction of the decomposition effectively prevents a phase separation controlled by diffusion and restricts the formation of the daughter products to locally ordered structures in the strained lattice of magnetite. Thermodynamic analysis of the observed phase transformations along with published results on the elastic properties and pressure-induced transitions of iron oxides has led to the reassessment of the phase diagram of Fe3O4. The pressure - temperature field of its stability with respect to the breakdown to a mixture of oxides FeO and Fe2O3, and to the transition to a high-pressure form, has been accordingly modified.

Magnetite (Fe3O4) thin films were prepared by a sol-gel process in which, a solution of iron (III) nitrate dissolved in ethylene glycol was applied on glass substrates by spin coating. Xerogel films were obtained by drying the coated films at 110 &deg / C. The films were sintered between 300 &deg / C and 450 &deg / C in order to observe the phases existing in the films at different temperatures. Coating solution showed Newtonian behaviour and viscosity was found as 0.0215 Pa.s. DTA analysis showed that, sintering temperature should be selected between 291 &deg / C and 350 &deg / C in order to produce magnetite thin films. Prepared magnetite thin films were characterized by XRD, SEM, AFM, TEM, VSM and UV-Vis spectrometer. In-plane grazing angle diffraction studies showed that magnetite phase was present upon sintering the films at 300 &deg / C. From the SEM studies, it was shown that films with defect free surfaces were obtained and by cross section studies, thickness of the films was found as ~10-200 nm. AFM images showed that no cracks or any other defects on the film surface were present. TEM results proved the existence of single phase magnetite in the produced films. UV-Vis spectrum results showed that transmittance of the films increases with decreasing sintering temperature and increasing spinning rate. Up to 96% transmittance was observed between the wavelengths of 900-1100 nm. Magnetic properties of magnetite thin films were also examined by VSM (Vibrating Sample Magnetometer) and ferromagnetic behaviour was shown using VSM data.

ABSTRACT PRODUCTION OF HEAVY-MEDIA-QUALITY MAGNETITE CONCENTRATE FROM KESiKK&Ouml / PR&Uuml / IRON ORE TAILINGS G&uuml / ng&ouml / r, Kazim M. Sc. Department of Mining Engineering Supervisor: Prof. Dr. M. &Uuml / mit Atalay May 2010, 91 pages The aim of this research was to investigate the possibility of the production of a magnetite concentrate which is suitable for preparation of heavy media from iron ore tailings of G&uuml / ncem Mining Company magnetic separation facility. During the study, three different tailings named as low grade, medium grade and high grade with 5.91 % Fe3O4, 19.06 % Fe3O4 and 37.06 % Fe3O4, respectively, were used. Mineralogical analyses of test samples showed that magnetite and hematite were the major ore minerals while pyrite and chalcopyrite were found in trace amounts. Actimolite, tremolite, epidote, chlorite, quartz, calcite, and dolomite were the gangue minerals. The effects of feed particle size and applied magnetic field intensity on the Fe3O4 grade and recovery of concentrate were examined throughout magnetic concentration tests. The highest grade magnetite concentrate with 79.98% Fe3O4 content was obtained with 65.42% recovery from 100% -75 micron size feed at 1000 Gauss magnetic field intensity from high grade tailing.

Magnetic nanoparticles have been used in many areas owing to their variable characteristic behaviors. Among these iron oxide nanoparticles are one of the mostly preferred type of nanoparticles. In this study Fe3O4, namely magnetite, which is one type of magnetic iron oxide nanoparticles was used. Magnetite nanoparticles with a narrow size distribution were prepared in aqueous solution using the controlled coprecipitation method. They were characterized by electron microscopic methods (SEM and TEM), crystal structure analysis (XRD), particle size analyzer, vibrating sample magnetometer (VSM) and Raman spectrometry. The nanoparticles were coated with a thin (ca 20 nm) silica shell utilizing the hydrolysis and the polycondensation of tetraethoxysilane (TEOS) under alkaline conditions in ethanol. The presence of silica coating was investigated by energy dispersive X-ray spectrometer (EDX) measurement. After surface modification with an amino silane coupling agent, (3-Aminopropyl)triethoxysilane, histidine was covalently linked to the amine group using glutaraldehyde as cross-linker. Carbonyl complexes of rhenium [Re(CO)3(H2O)3]+ was prepared through reductive carboxylation utilyzing gaseous carbon monoxide as a source of carbonyl and amine borane (BH3NH3) as the reducing agent. The complex formation was followed by HPLC- ICP-MS system and 95% conversion of perrhanete into the complex was achieved. The magnetic nanoparticles were then labeled with the Re complex with a yield of 86.8% through the replacement of labile H2O groups with imidazolyl groups. Thus prepared particles were showed good stability in vitro. Herein rhenium was selected as a surrogate of radioactive 99mTc. However radioactive isotopes of rhenium (186-Re and 188 Re) is also used for radioactive therapy.

In biomedical applications, magnetic nanoparticles have been used as they offer attractive possibilities. First, they have controllable sizes ranging from a few nanometers up to tens of nanometers and second, the nanoparticles are magnetic and magnetic fields can penetrate into human tissue which means that they can be manipulated by an external magnetic field gradient. In this study, Fe

Magnetic oxides have become of interest source for spin transport devices due to their high spin polarization. But the real applications of these oxides remains unsatisfactory up to date, mostly due to the change of properties as a result of nano structuring. Magnetite (Fe3O4) is one such a material. High Curie temperature and the half metallicity of Fe3O4 make it a good potential candidate for spin transport devices. Studies have shown that the nano structuring Fe3O4 changes most of it's important properties. This includes high saturation magnetization and drop of conductivity by a few orders of magnitude in Fe3O4 thin films. In this study, we have successfully grown Fe3O4 by reactive sputtering and studied the effect of transition metal buffer layers on structural, transport, and magnetic properties of Fe3O4. It is shown that the lattice strain created by different buffer layers has major impacts on the properties of Fe3O4 thin films. Also for the first time the magnetic force microscopic measurements were carried out in Fe3O4 thin films through Verwey transition. MFM data with the magnetization data have confirmed that the magnetization of Fe3O4 thin films rotate slightly out of the plane below the Verwey transition. Fe3O4 thin films were also successfully used in fabricating spin valve structures with Chromium and Permalloy. Here, the Fe3O4 was used to generated the spin polarized electrons through reflection instead of direct spin injection. This is a novel method that can be used to inject spins into materials with different conductivities, where the traditional direct spin injection fails. Also the effect of growth field on Fe3O4 and Fe3O4/Cr/Py spin valves were investigated. In Fe3O4 the growth field induced an uni-axial anisotropy while it creates a well defined parallel and anti-parallel states in spin valves. Magneto thermal phenomenon including spin dependent Seebeck effect, Planar Nernst effect, and Anomalous Nernst effect were measured in ferromagnetic thin films and spin valves. Spin dependent Seebeck effect and planar Nernst effect were directly compared with the charge counterpart anisotropic magneto resistance. All the effects exhibited similar behavior indicating the same origin, namely spin dependent scattering.

The Dannemora skarn iron ore deposit is located in the northeastern part of Bergslagen. The deposit has been mined from the 1400’s and stopped in 1992, the mine was reopen in 2012 and it will close in 2015. The Dannemora deposit is hosted by 1.9 Ga old sedimentary and volcanic rocks. The deposit consists of both manganese rich and manganese poor iron ore. The purpose of this study is to investigate the controlling factors for manganese content in both magnetite and surrounding silicate minerals, especially when garnets is present. Also the mineral assemblage and association with different host rocks lithologies shall be investigated. Petrographical and chemical studies indicate the occurrence of both calcic amphibole and Mg-Fe-Mn-Li type amphibole. The calcic amphibole is found in the majority of the samples and is dominant in manganese poor samples where as Mg-Fe-Mn-Li-type amphibole is more abundant in the manganese rich samples. Generally in the manganese rich samples garnet and epidote become more abundant, particularly if the sample is taken close to a volcanic section. / Skarn-järnmalmsfyndigheten i Dannemora är belägen i den nordöstra delen av Bergslagen. Järnmalm och mindre sulfidmineraliseringar har blivit brutna sedan 1400-talet. Gruvan stängde 1992 men togs i produktion igen under 2012. Gruvan stängs återigen under 2015. Fyndigheten är omgiven av 1.9 Ga gamla sedimentära och vulkaniska bergarter. Järnmalmsfyndigheten innehåller både manganrika och manganfattiga järnmalmer. Syftet med denna studie är att undersöka varför fyndigheten har förhöjda halter av mangan. Förändringar av manganhalter och olika värdbergarter borde ge en annorlunda mineralsammansättning i de olika miljöerna. För att svara på dessa frågor skall både mikroskopiska och kemiska undersökningar göras för att bestämma och identifiera olika mineralogiska associationer. Petrografiska och kemiska studier indikerar två olika huvudtyper av amfiboler: kalciumhaltiga amfiboler och Mg-Fe-Mn-Li-amfiboler. Kalciumamfibolerna är generellt mer spridda i proverna medan Mg-Fe-Mn-Li-amfibolerna är mer koncentrerade till de mer manganrika sektionerna. När koncentrationen av mangan är högre blir granater och även epidot och olivin vanligare, speciellt närmare vulkaniska bergarter.