Geophysical methods are frequently applied in conjunction with exploration efforts to increase the understanding of the surveyed area. Their purpose is to determine the nature of the geophysical response of the subsurface, which can reveal the lithological and structural character. By combining geophysical measurements with the drill core data, greater clarity can be achieved about the structures and lithology of the borehole. The purpose of the project was to give the student an opportunity to discover borehole logging operations and to have a greater understanding of the local geology, in particular the iron mineralizations in the apatite iron ore intersected by the boreholes. In order to do this, the student participated in performing a geophysical borehole survey and analyzing the results. These were combined with a drill core log in order to cross plot the results and increase understanding. / Geofysiska metoder används ofta i samband med prospektering för att öka förståelsen av området. Utförda från ytan ger de en relativt god tolkning av vad som kan finnas på djupet och är även kostnadseffektiva jämfört med provborrning. Borrhålsloggning sker däremot efter att själva hålet borrats och ändamålet är ofta att utöka förståelsen om området omedelbart kring det loggade hålet. Genom att kombinera geofysisk fältdata med tolkning av borrkärnan kan man erhålla en ökad förståelse för borrhålets strukturer och litologi. Syftet med det här projektet var att utöka studentens förståelse inom borrhålsloggning, samt att avgöra hur relevant metoden är för att identifiera järnmineraliseringar i apatitjärnmalmen som kännetecknar norra Bergslagen

La magnétite, Fe3O4, est un oxyde de fer naturel à valence mixte Fe(II-III), qui sous sa forme nanométrique, a un fort potentiel d’applications technologiques dans des domaines allant de la biomédecine au traitement des eaux. Les nano-magnétites sont très efficaces pour l’adsorption ainsi que la réduction et l’oxydation de divers polluants environnementaux. Elles peuvent catalyser l’oxydation de type Fenton hétérogène induisant une dégradation efficace des polluants organiques et ceci dans un large domaine de pH. Cependant, les mécanismes impliqués restent mal connus. L’objectif principal de cette étude est d’explorer la capacité de la nano-magnétite à catalyser des réactions radicalaires de type Fenton hétérogène sans ajout d’oxydants forts, mais en utilisant uniquement l’oxygène de l’air. Ces réactions pourraient par la suite constituer la base de nouveaux procédés de remédiation efficace et éco-compatible pour l’élimination des polluants organiques dans différents compartiments de l’environnement. L’acide nalidixique, un antibiotique appartenant à la famille des quinolones, a été utilisé comme contaminant modèle, car ce composé polaire et ionisable se révèle persistant dans l’environnement et récalcitrant aux traitements classiques.Après synthèse de nano-magnétite offrant une surface spécifique élevée, la sorption de l’acide nalidixique sur ce support a été étudiée en conditions anoxiques et une adsorption supérieure à 98 % a été obtenue. En présence d’oxygène, cette sorption est suivie d’une transformation du contaminant modèle. Après désorption selon un protocole qui a été développé, un taux de dégradation d’environ 60 % a été évalué après seulement 30 minutes d’oxygénation, et 80% après 90 minutes. Cinq sous-produits de NAL ont été identifiés par chromatographie liquide couplée à la spectrométrie de masse (UHPLC-MS/MS) et un schéma de dégradation a été proposé. L’analyse de la phase solide par la diffraction des rayons X et par spectroscopie d’absorption au seuil K du fer (XANES et EXAFS) démontre une oxydation significative de la magnétite en maghémite (jusqu’à 40 %). Complétés d’une part par le suivi de la teneur en Fe(II) dissous, et des expériences réalisées en présence d’un piège à radicaux hydroxyles, et d’autres part par l’interprétation des effets du pH et de son évolution lors de la réaction, ces résultats ont permis de proposer un mécanisme réactionnel qui implique la formation des espèces réactives d’oxygène suite à l’oxydation de la magnétite.Les conclusions tirées des résultats expérimentaux prouvent les potentialités prometteuses des oxydes de fer mixte dans la remédiation des sols et eaux contaminés par des composés organiques. / Magnetite, Fe3O4, is a natural mixed iron oxide Fe(II-III), that has a wide range of applications in biomedicine as well as in water treatment. Nanosized magnetite presents high capacities to adsorb and transform a wide range of contaminants via oxidative or reductive reactions. It was shown as an active catalyst for heterogeneous Fenton reactions in the removal of organic compounds under a broad range of pH. However, the mechanisms of these reactions are not well defined.The main objective of this study was to explore the nanomagnetite capacity to catalyze heterogeneous Fenton reactions in presence of dissolved oxygen, thus avoiding the use of strong chemical oxidants. These reactions could form the basis of a new efficient and eco-friendly process for the removal of organic pollutants. Nalidixic acid (NAL), an ionizable quinolone antibiotic known for being persistent and recalcitrant to classical treatments, was used as a model contaminant.We synthesized large surface area single-cristalline nanomagnetite with high NAL sorption ability (98%) under anoxic conditions. Furthermore, a desorption protocol was developed to recover the sorbed amount of NAL in order to measure the degradation percentage.Moreover, under oxic conditions, the model contaminant was transformed, up to nearly 60% and 80 % after a 30 and 90 minutes exposure to air bubbling, respectively. Five by-products issuing from the nalidixic acid oxidative degradation were identified by liquid chromatography-mass spectrometry and a degradation pathway was suggested. X-ray powder diffraction and Iron K-edge X-ray absorption spectroscopy were used to investigate mineralogical and iron redox changes in the solid phase over the course of the reaction. Magnetite was oxidized (up to about 40%) into maghemite, -Fe2O3, as the sole product of the oxidation, and without significant change in the size of the particles. These results, in addition to the monitoring of dissolved Fe(II), and experiences conducted in the presence of ethanol as hydroxyl radicals scavenger and at static pH, lead to a better understanding of the reaction mechanism and on the role of pH in the reaction efficiency. In conclusion, this study points out the promising potentialities of mixed valence iron oxides for the treatment of contaminated soils and wastewater by organic pollutants.

Geological disposal of radioactive wastes currently stored at Earth's surface is now the favoured management pathway for these materials. Typically, intermediate level wastes (ILW) are grouted and emplaced in a geological disposal facility (GDF) which will be backfilled, possibly with cementitious materials. Post-closure leaching of the cementitious materials in a GDF is expected to create hyperalkaline conditions in and around the repository, resulting in mineral alteration and crystallisation, both within the engineered barrier and host rock; creating a persistent chemically disturbed zone (CDZ). Iron derived from within the host rock as a result of alkaline breakdown of Fe-bearing silicate minerals (e.g. biotite, chlorite); corrosion products formed within the repository; or iron contained within the waste; will form secondary iron (oxyhydr)oxide minerals. The formation and re-crystallisation of these reactive mineral phases may sequester radionuclides through a host of processes: surface-mediated reduction to less soluble forms; adsorption onto, and/or incorporation into stable secondary or tertiary iron oxide phases. Therefore iron (oxyhydr)oxides will be key to the fate of radionuclides potentially released from within radioactive wastes disposed of in a GDF.In this study, the fate of U(VI) and Tc(VII) was considered during crystallisation of ferrihydrite to more stable iron oxide phases (e.g. hematite and magnetite) and, in three synthetic cement leachates (pH 13.1, 12.5, 10.5) designed to reflect the early-, middle- and late-stage evolution of the CDZ. XRD and SEM/TEM have been used to characterise the mineralogy during crystallisation. Partitioning of U(VI) and Tc(VII) between the solid and solution has been followed throughout, with chemical extractions used to determine the distribution of the radionuclides adsorbed to, and incorporated within the solid. Synchrotron-based XAS techniques have been utilised to probe the oxidation state and molecular scale bonding environment of the radionuclides associated with the solids. The data suggest that: U(VI) is incorporated into the hematite structure in place of Fe(III), in a distorted octahedral environment with elongation of the uranyl bond; Tc(VII) is reduced to Tc(IV) and incorporated into the octahedral site within the magnetite structure in place of Fe(III), and is retained in the same environment even after extensive oxidation of the magnetite to maghemite; and that U(VI) may also be incorporated as U(V) or U(VI) into the magnetite structure, with similar recalcitrant behaviour during oxidation. These results highlight the importance of mineral reactions within the CDZ as potentially significant pathways for immobilising radionuclides released from a GDF.

Non-invasive and controlled release of bioactive compounds is an important goal in the development of drug delivery systems and novel biomaterials for tissue engineering. This project aims to exert spatio-temporal control over the release of bioactive compounds from phospholipid vesicle carriers by crosslinking them with superparamagnetic iron oxide nanoparticles to form a magnetic release nanostructure. The magnetic properties of the nanoparticles allow release to be triggered by an alternating magnetic field (AMF), which induces localised heating and “melts” the vesicle membranes. The aggregates can also be manipulated in space by a static magnetic field to create patterned materials. Incorporation of these aggregates into hydrogels has created novel responsive biomaterials. Controlled release of ascorbic acid-2-phosphate has been used to induce collagen production by chondrocytes, demonstrating an AMF triggered cellular response in vitro. The existing system has been redesigned after detailed characterisation and assessment of the performance of each component. Magnetic release has been extensively assessed using fluorescence techniques to quantify release, and optimised through the development of new silica-derived nanoparticle coatings and aggregate formulations informed by quantitative characterisation of nanoparticle functionalisation. The replacement of calcium alginate hydrogels as a 3D cell culture matrix with hyaluronic acid- based hydrogels was found to eliminate gel-induced leakage of vesicle contents and also improves the compatibility of the system with a greater range of cell types. Recently the effective encapsulation and AMF-triggered release of proteins including enzymes has been demonstrated and released enzymes have been demonstrated to retain their activity. Released trypsin was shown to retain proteolytic activity while hyaluronidase released into hyaluronan-derived hydrogels has been demonstrated to influence the rheological properties of the gel. A galactose-terminated lipid has been synthesised that enables specific targeting of the asialoglycoprotein (ASGPR) cell surface receptor receptor found in human hepatocytes, demonstrating the potential for customisation of the MNPV system to particular requirements.

Orientador: Marcelo Knobel / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Física Gleb Wataghin / Made available in DSpace on 2018-08-30T18:13:51Z (GMT). No. of bitstreams: 1 OrozcoHenao_JuanManuel_M.pdf: 7687296 bytes, checksum: d9aecf2d118aed0c43ab747d0dcff34c (MD5) Previous issue date: 2016 / Resumo: Nanopartículas de magnetita com diâmetros entre 5nm e 19nm sintetizadas mediante um método de decomposição térmica são apresentadas. A caracterização estrutural é feita usando diferentes técnicas experimentais como a microscopia eletrônica de transmissão (TEM), difração de raios-X e espalhamento de raios-X a baixos ângulos (SAXS) de onde são obtidos os tamanhos e a forma das nanopartículas. As propriedades magnéticas e de magneto-hipertermia das nanopartículas são estudadas para diferentes parâmetros de produção como concentração dos surfactantes, temperaturas de refluxo e atmostfera de crescimento. A dependência com a temperatura das propriedades magnéticas são analisadas dentro do marco do modelo usual do superparamagnetismo e o modelo de interação superparamagnética (ISP), de onde os parâmetros magnéticos dependentes do tamanho como anisotropia magnética (1.06x10^4 J/m^3 até 9.91x10^4 J/m^3), momento magnético por partícula (2618?B até 11500?B), temperatura de bloqueio (18K até mais de 300K) e energia de ineração dipolar magnética (0.55x10^-21 J até 5.5x10^-21 J) são inferidos. Os resultados de magneto-hipertermia foram obtidos mediante a medição da resposta térmica das nanopartículas de magnetita suspendidas em tolueno. Valores da taxa de absorção específica (SAR) são calculados experimental e teoricamente utilizando a teoria de resposta linear para um sistema superparamagnético não interagente. Valores de SAR entre 3.0W/g e 40.3W/g e a sua dependência com a frequência e o campo aplicado são apresentados. Como resultado interessante, a resposta de magneto-hipertermia para as nanopartículas de 19nm preparadas na presença de oxigênio e mais de 10 vezes maior do que nanopartículas similares mas obtidas na ausência da atmosfera de oxigênio. Também é destacada a possibilidade de prever a resposta de magneto-hipertermia num sistema de nanopartículas magnéticas mediante a obtenção dos parâmetros de caracterização magnetica e estrutural / Abstract: Magnetite nanoparticles with diameters between 5nm and 19nm synthesized by means of a thermal decomposition method are presented. Structural characterization is made by different experimental techniques such as transmission electron microscopy (TEM), X-ray diffraction and Small Angle X-ray Scattering (SAXS) from where nanoparticles size and shape are obtained. Magnetic and magneto-hyperthermia properties of the nanoparticles are studied for different production parameters, such as surfactant concentrations, refluxing temperature and growth atmosphere. Temperature dependence of the magnetic properties are analyzed in the framework of the standard superparamagnetism model and the interacting superparamagnetic model (ISP), from where size dependent magnetic parameters for each sample such as anisotropy (1.06×10^4 J/m^3 to 9.91x10^4 J/m^3) magnetic moment per particle (2618?B to 11500?B), blocking temperature (18K to above 300K) and magnetic dipolar interaction energy on dried nanoparticle samples (0.55 × 10^?21 J to 5.5 × 10^?21 J) are inferred. Magneto-hyperthermia results are obtained by measuring the thermal response of magnetite nanoparticles dissolved in toluene. Specific absorption rate (SAR) values are theoretically and experimentally calculated by means of a linear response theory approach of a non-interacting superparamagnetic system. SAR values between 5.8W/g and 40.3W/g are reported; interestingly, the magneto-hyperthermia response for 19nm nanoparticles prepared in presence of an oxygen atmosphere is more than 10 times larger than similar particles obtained in absence of oxygen atmosphere. Also it is important to highlight the possibility to obtain the magneto-hyperthermia behavior of a magnetic nanoparticles system by knowing a priori its structural and magnetic characterization parameters / Mestrado / Física / Mestre em Física / 1247647/2013 / CAPES

This Master thesis is focused on characterization of multicompound self-compacting heavy-weight mortars resistant against long lasting influence of ionizing radiation in the underground nuclear waste storage. It examines a specific combination of properties of heavy-weight concretes and self-compacting mortars while considering the ecological and energetic impact of their production, as well as the productibility of partial substitutions that do not have negative impact on material properties. The Experimental part provides a comprehensive overview of composition and properties of self-compacting heavy-weight mortars with varying percentages of cement-to-mortar ratio. Sample properties were evaluated based on mechanical test results, thermal analysis, differential scanning calorimetry, scanning electron microscopy and X-ray diffraction.

The present work focuses on analyses of the experimental 57 Fe nuclear magnetic resonance data and the results of ab initio calculations in order to achieve deeper insight into the hyperfine and electronic structure of magnetite both below and above the Verwey phase transition. Parameters of hyperfine interactions and electronic structure data of the Cc phase of magnetite were extracted from the results of ab initio calculations based on the recently reported crystal structure. Published experimental dependences of the 57 Fe nuclear magnetic resonance frequencies on the external magnetic field direction were quantitatively reanalyzed, yielding hyperfine anisotropy data, which were compared to the analogous hyperfine field parameters from the ab initio calculations. The findings were interpreted in the context of up-to-date charge ordering models for magnetite. Attention was also paid to the impact of various cationic substitutions and defects on the electronic structure and hyperfine interactions in magnetite manifested in the 57 Fe nuclear magnetic resonance spectra: below the Verwey transition, signal intensity shifts in the spectra were analyzed; above the Verwey transition, the mean field model was adapted for an analysis of temperature dependence of satellite signal frequencies, while the anomalous...

In this thesis the influence of deposition conditions and post-deposition annealing on the structure of ultrathin iron oxide films grown on magnesium oxide (MgO) substrates is studied. The main experimental technique used is synchrotron based x-ray diffraction (XRD) but also x-ray photoelectron spectroscopy (XPS) and low energy electron diffractions (LEED) are used to characterize the samples. Studying the dependency of film structure and thickness the stoichiometry and structure is changing with increasing film thickness. For large film thickness bulk like magnetite (Fe3O4) can be observed. With decreasing thickness the oxide phase is shifting towards a wüstite (FeO) phase. When changing the deposition rate and substrate temperature a strong influence on the Fe3O4 film structure is observed. With both decreasing deposition rates and substrate temperatures the occupancy of the tetrahedral sites is strongly decreasing while the octahedral sites remain almost unaffected. By post-deposition annealing under low oxygen atmosphere it is possible to increase the ordering of the tetrahedral sites. However, this is accompanied by significant diffusion of magnesium into the iron oxide film. During post-deposition annealing of a gamma-Fe2O3 film under high vacuum a reduction of the iron oxide is observed. Increasing the temperature, first, a reduction from gamma-Fe2O3 to Fe3O4 is observed. After further increasing the temperature a reduction from Fe3O4 to FeO is observed.

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