Summary Serpentinites from the northern Vermont were examined for the distribution and abundance of As. XRD and electron microprobe showed the samples are composed of antigorite, chromite, magnetite, and carbonate minerals (magnesite, dolomite, calcite). The concentration in As when the samples were dissolved in H3PO4 was 10% of the concentration in As when the samples were dissolved in concentrated HF/HNO3, suggesting that As is mainly incorporated in the structure of antigorite. X-ray absorption near-edge structure spectra showed that the As is As(III) in the samples. Extended X-ray absorption fine structure spectra suggested that the As has a tetrahedral coordination and is located in the Si-site in serpentine.

A method of performing accurate oxygen analysis on cuprate based superconducting materials was established using electron probe micro analysis (EPMA). A range of YBa₂Cu₃O_δ ceramics with varying oxygen concentration were used to test the method. Using YBCO as a reference material, a suitable standard for oxygen analysis of Bi₂Sr₂CaCu₂O_δ (BiSCCO-2212) materials was obtained. This standard was used to perform full elemental analysis of a range of BiSCCO-2212 crystals, post annealed in pO₂'s between 10^-5-2atm. When the average Cu valence of each crystal was calculated and plotted as a function of the critical temperature (T_c) for each crystal, it was shown that BiSCCO-2212 materials conformed to the 'universal' trend illustrated by most other HTS and did not exhibit anomalous behaviour as had been previously believed. The phase assemblage and superconducting properties of BiSCCO-2212 Ag-clad multifilamental wires, prepared using the powder-in-tube (PIT) method by BICC, were studied as a function of a time/temperature profile. pO₂ of the processing atmosphere was found to be the predominant factor in determining the stoichiometry of the 2212 phase within wires. The phase assemblage is not simply a function of pO₂ as previously believed and can be controlled, in part, by the post annealing temperature. Homogenisation of the phase assemblage in BiSCCO-2212 Ag-clad wires can be achieved by prolonged heating (96hrs) at an appropriate temperature. An investigation into the 10K superconducting BiSCCO phase has shown the Sr-rich solid solution to extend towards the ideal stoichiometry of 2:2:1 (Bi:Sr:Cu) with increasing pO₂. Using a combination of high pO₂ (60atm) to achieve the appropriate Bi:Sr stoichiometry followed by post annealing in N₂ to adjust the oxygen content, it was possible to prepare single-phase ceramics of stoichiometry Bi_2.11(2)Sr_1.90(2)Cu_0.99(2)O_δ with a T_c=10.5K(5).

Summary Serpentinites from the northern Vermont were examined for the distribution and abundance of As. XRD and electron microprobe showed the samples are composed of antigorite, chromite, magnetite, and carbonate minerals (magnesite, dolomite, calcite). The concentration in As when the samples were dissolved in H3PO4 was 10% of the concentration in As when the samples were dissolved in concentrated HF/HNO3, suggesting that As is mainly incorporated in the structure of antigorite. X-ray absorption near-edge structure spectra showed that the As is As(III) in the samples. Extended X-ray absorption fine structure spectra suggested that the As has a tetrahedral coordination and is located in the Si-site in serpentine.

Summary Serpentinites from the northern Vermont were examined for the distribution and abundance of As. XRD and electron microprobe showed the samples are composed of antigorite, chromite, magnetite, and carbonate minerals (magnesite, dolomite, calcite). The concentration in As when the samples were dissolved in H3PO4 was 10% of the concentration in As when the samples were dissolved in concentrated HF/HNO3, suggesting that As is mainly incorporated in the structure of antigorite. X-ray absorption near-edge structure spectra showed that the As is As(III) in the samples. Extended X-ray absorption fine structure spectra suggested that the As has a tetrahedral coordination and is located in the Si-site in serpentine.

A presente dissertação apresenta uma investigação sobre a evolução tectono-metamórfica da Formação São Tomé, uma das unidades metassedimentares pertencente ao Grupo Rio Doce, no Orógeno Araçuaí. Essa unidade, de origem pelítica, ocorre em uma faixa com direção geral aproximadamente N-S, com vergência para NE, contrária ao cráton São Francisco neste setor do orógeno. Possui como litotipo principal quartzo-mica xisto, com proporções variadas de granada, estaurolita, sillimanita e plagioclásio. Duas fases deformacionais estão registradas através de uma foliação continua S1 do tipo clivagem de fratura e uma foliação S2 de clivagem de crenulação. As relações texturais indicam que parte das fases minerais se cristalizaram tanto durante o evento deformacional como em condições ausentes de tensão deviatórica, e registro de condições de pico metamórfico de 6 kbar e 650 °C. Os dados geocronológicos foram obtidos em monazita por meio de datações Th-UPb em microssonda eletrônica. Foram identificadas três populações distintas: (i) A população mais antiga de 641±32 Ma, 614±39 Ma e 607±47 Ma, a qual pode representar grãos detríticos de corpos ígneos, não mais aflorantes, relacionados a um possível estagio pré-colisional ou, tratar-se de monazitas metamórficas formadas em um primeiro evento térmico; (ii) População com idades intermediárias entre 560±32 Ma e 559±29 Ma, compatíveis com as idades do ápice metamórfico regional; (iii) População mais jovem de idades entre 501±28 Ma e 491±34 Ma, condizentes com a formação concomitante à geração dos corpos ígneos tardios. Ainda que não esteja esclarecido se essas idades estão relacionadas a eventos metamórficos distintos ou são reflexo da baixa taxa de resfriamento do orógeno, os três grupos de monazita com idades distintas estão bem estabelecidos. / The present dissertation presents an investigation on the tectono-metamorphic evolution of the São Tomé Formation, one of the metasedimentary units belonging to the Rio Doce Group, in the Araçuaí Orogen. This unit, of pelitic origin, occurs in a band with general direction approximately N-S, with vergence for NE, contrary to the São Francisco craton in this sector of the orogen. It has quartz-mica schist as main lithotype, with varying proportions of grarnet, staurolite, sillimanite and plagioclase. Two deformational phases are recorded through a continuous foliation S1 of the fracture cleavage type and a foliation S2 of crenulation cleavage. The textural relations indicate that part of the mineral phases crystallized both during the deformational event and in conditions absent of deviatore voltage, and record of metamorphic peak conditions of 6 kbar and 650 ° C. The geochronological data were obtained in monazite by means of Th-U-Pb dating in electron microprobe. Three distinct populations were identified: (i) The oldest population of 641 ± 32 Ma, 614 ± 39 Ma and 607 ± 47 Ma, which may represent detrital grains of igneous bodies, no longer outcrops, related to a possible pre- collisional or, being metamorphic monazites formed in a first thermal event; (ii) Populations with intermediate ages between 560 ± 32 Ma and 559 ± 29 Ma, compatible with regional metamorphic apex ages; (iii) Younger population between 501 ± 28 Ma and 491 ± 34 Ma, consistent with the formation concomitant with the generation of late igneous bodies. Although it is unclear whether these ages are related to distinct metamorphic events or are reflective of the low orogenic cooling rate, the three monazite groups of different ages are well established.

A presente dissertação apresenta uma investigação sobre a evolução tectono-metamórfica da Formação São Tomé, uma das unidades metassedimentares pertencente ao Grupo Rio Doce, no Orógeno Araçuaí. Essa unidade, de origem pelítica, ocorre em uma faixa com direção geral aproximadamente N-S, com vergência para NE, contrária ao cráton São Francisco neste setor do orógeno. Possui como litotipo principal quartzo-mica xisto, com proporções variadas de granada, estaurolita, sillimanita e plagioclásio. Duas fases deformacionais estão registradas através de uma foliação continua S1 do tipo clivagem de fratura e uma foliação S2 de clivagem de crenulação. As relações texturais indicam que parte das fases minerais se cristalizaram tanto durante o evento deformacional como em condições ausentes de tensão deviatórica, e registro de condições de pico metamórfico de 6 kbar e 650 °C. Os dados geocronológicos foram obtidos em monazita por meio de datações Th-UPb em microssonda eletrônica. Foram identificadas três populações distintas: (i) A população mais antiga de 641±32 Ma, 614±39 Ma e 607±47 Ma, a qual pode representar grãos detríticos de corpos ígneos, não mais aflorantes, relacionados a um possível estagio pré-colisional ou, tratar-se de monazitas metamórficas formadas em um primeiro evento térmico; (ii) População com idades intermediárias entre 560±32 Ma e 559±29 Ma, compatíveis com as idades do ápice metamórfico regional; (iii) População mais jovem de idades entre 501±28 Ma e 491±34 Ma, condizentes com a formação concomitante à geração dos corpos ígneos tardios. Ainda que não esteja esclarecido se essas idades estão relacionadas a eventos metamórficos distintos ou são reflexo da baixa taxa de resfriamento do orógeno, os três grupos de monazita com idades distintas estão bem estabelecidos. / The present dissertation presents an investigation on the tectono-metamorphic evolution of the São Tomé Formation, one of the metasedimentary units belonging to the Rio Doce Group, in the Araçuaí Orogen. This unit, of pelitic origin, occurs in a band with general direction approximately N-S, with vergence for NE, contrary to the São Francisco craton in this sector of the orogen. It has quartz-mica schist as main lithotype, with varying proportions of grarnet, staurolite, sillimanite and plagioclase. Two deformational phases are recorded through a continuous foliation S1 of the fracture cleavage type and a foliation S2 of crenulation cleavage. The textural relations indicate that part of the mineral phases crystallized both during the deformational event and in conditions absent of deviatore voltage, and record of metamorphic peak conditions of 6 kbar and 650 ° C. The geochronological data were obtained in monazite by means of Th-U-Pb dating in electron microprobe. Three distinct populations were identified: (i) The oldest population of 641 ± 32 Ma, 614 ± 39 Ma and 607 ± 47 Ma, which may represent detrital grains of igneous bodies, no longer outcrops, related to a possible pre- collisional or, being metamorphic monazites formed in a first thermal event; (ii) Populations with intermediate ages between 560 ± 32 Ma and 559 ± 29 Ma, compatible with regional metamorphic apex ages; (iii) Younger population between 501 ± 28 Ma and 491 ± 34 Ma, consistent with the formation concomitant with the generation of late igneous bodies. Although it is unclear whether these ages are related to distinct metamorphic events or are reflective of the low orogenic cooling rate, the three monazite groups of different ages are well established.

To provide an increased breadth in the knowledge of tephra dispersal, this pilot study examines a peat core from Lakselv in Finnmark County in northern Norway. Peat samples are exposed to burning, HCl, density separation and polarized light microscopy. One sample from a depth of 37.5-40 cm was analysed using an electron microprobe analyser (EMPA). At least two tephra horizons were identified, one at a depth of 12.5-17.5 cm and one at 37.5-40 cm. The lower horizon shows a chemical composition similar to eruptives from Jan Mayen and São Miguel, Azores while the origin of the upper horizon is unknown as no geochemical analysis was performed for that depth.

Extensive research has shown that electrochemistry is one of the factors that govern the flotation of sulfide minerals. Flotation is often adversely affected by uncontrolled oxidation, which is also an electrochemical process. The interest in pyrrhotite recovery arose after observing that there is a substantial loss of PGM due to the depression of pyrrhotite and the subsequent loss of any PGMs associated with it. The first part of this study focuses on the influence of chemical composition and crystal structure on the electrochemical behaviour of pyrrhotite in a 0.05 M Na2B4O7 solution. Rest potential and polarisation resistance measurements, as well as anodic polarisation diagrams, showed that the magnetic 4C type pyrrhotite is anodically more reactive than the non-magnetic 6C type pyrrhotite. It was also shown in cathodic polarisation diagrams that the non-magnetic 6C type pyrrhotite is a better substrate for oxygen reduction and is less susceptible to oxidation. ToF-SIMS showed the formation of an oxide layer on the pyrrhotite surface after oxidation. In the second part of this work, the influence of galvanic interactions on the electrochemical behaviour of pyrrhotite in contact with pentlandite was investigated. It was observed that, under oxygen-saturated conditions, as the amount of pentlandite increases, the reactivity towards oxidation of the mixed mineral system is reduced. Impedance measurements showed a decrease in capacitance values, indicating the formation of a continuous oxide layer on the surface and an increase in oxide layer thickness with decreasing pentlandite content. Anodic polarisation diagrams showed that under oxygen-deficient conditions and in the low potential region, pentlandite behaves as an inert material and does not have an influence on the oxidation behaviour of pyrrhotite. Hence, the anodic activities of the different magnetic 4C type pyrrhotites from Sudbury Gertrude, Phoenix and Russia were compared. It was shown that the oxidation reactivity decreased in the following order: Sudbury Gertrude magnetic 4C pyrrhotite > Phoenix magnetic 4C pyrrhotite > Russian magnetic 4C pyrrhotite; it also varied according to location. In the transpassive region, higher anodic currents were observed on the mixed samples because both pentlandite and pyrrhotite reacts. The reactivity increased in the order: pure pyrrhotite (Russia) < medium-pentlandite (Sudbury Gertrude) < high-pentlandite (Phoenix). In the presence of potassium ethyl xanthate, there was no change in the initial anodic reactivities of the different pyrrhotites. The anodic polarisation diagrams of the pure and mixed samples showed a reduction in the maximum anodic peak current, suggesting the presence of xanthate on the surface, which hinders oxidation of the mineral surface. In addition, the influence of cleaning of oxidised pyrrhotite with gaseous carbon dioxide was studied, using electrochemical and microflotation measurements. Electrochemical measurements indicated that CO2 treatment resulted in depassivation of the oxidised surfaces; this was supported by ToF-SIMS measurements that demonstrated a reduction in the oxide layer thickness after CO2 treatment. Anodic polarisation diagrams showed a higher anodic peak current, indicating that the surface is more reactive. Gaseous carbon dioxide conditioning of oxidised pyrrhotite resulted in improved flotation response of pyrrhotite with the aid of copper activation and higher air flow rate. Copyright / Dissertation (MEng)--University of Pretoria, 2010. / Materials Science and Metallurgical Engineering / unrestricted

The Arlanda area is a construction intensive area facing problems with risk of leaching of arsenic (As) from the bedrock to surface- and groundwater. Construction projects in the area have had problems with high levels of As in the bedrock and the risk of leaching increases through processing of aggregates and blasting of the bedrock. Additionally, there are high concentrations of As in potable water and elevated concentrations are correlated with occurrences of metasedimentary rock, but may also be related to other rock types. The existing geological information of the area was collected in the 1960´s and modern petrographic information as well as modelling of P-T and redox conditions are needed to understand the As mineralogy of the bedrock. Methods used in this project include field work, optical microscopy, electron microprobe analyses, geothermometry calculations, pseudosection modelling in Perple_X and geochemical modelling in PHREEQC. The results indicate that the As-rich bedrock domain include rocks of both igneous and sedimentary origin. As-bearing minerals löllingite and arsenopyrite were found in the matrix of two of the metasedimentary rock samples, while no As-minerals were found in metavolcanic samples. P-T estimates from several geothermobarometry models all suggest amphibolite facies metamorphism for the area, with pressure of 3.0-5.5 kbar and temperature of 490-640 °C. Simple modelling of equilibration of löllingite and arsenopyrite in pure water indicate that As(III) is the dominating oxidation state of As and that the molality of As increases with increasing T and decreasing pH. The results of this thesis provide new information on the petrography and P-T conditions for metamorphism of As-bearingsupracrustal rocks in the Arlanda area, but future research is needed to be able to predict the spatial occurrence of As in the bedrock. / Arlandaområdet är ett av de mest expansiva områdena i Sverige där en stor mängd infrastrukturprojekt är planerade under de närmaste 5-20 åren. Tidigare byggnadsprojekt i området har dock stött på problem med höga bakgrundshalter av arsenik (As) i berggrunden och det finns även en risk för urlakning av As från berggrunden till både yt-och grundvatten. Denna risk ökar under byggnadsarbeten i och med till exempel sprängning av berg. Ytterligare ett problem är att det i området runtomkring Arlanda ofta är höga halter av arsenik i dricksvattenbrunnar. Från data över As-halter i bergborrade brunnar har man kunnat se att höga halter av As ofta förekommer i metasedimentära bergarter, men även kan uppträda i andra bergarter. Den tillgängliga geologiska informationen över området är insamlad på 60-talet och ny petrografisk information, samt modellering av tryck- och temperaturförhållanden är nödvändig för att förstå förekomst av As i berggrunden. Målet med detta projekt är att med hjälp av fältarbete, optisk- och elektronmikroskopering, samt termodynamisk modellering få djupare kunskap kring ytbergarterna i området och utvärdera förekomsten av arsenik i dessa. Under vilka tryck- och temperaturförhållanden som de metamorfa bergarterna omvandlats studeras genom beräkningar från mineralsammansättningar samt modellering i programmet Perple_X. Resultatet från projektet visar att bergarter i As-anrikade zoner är av både magmatiskt och sedimentärt ursprung. Arsenikmineralen löllingit och arsenikkis dokumenterades endast i bergarter av sedimentärt ursprung. Bergarternas kemiska sammansättning tyder också på att de högsta As-halterna finns i de metasedimentära bergarterna. Modellering i PHREEQC visar att As(III) är den dominerande formen av As när löllingit och arsenikkis reagerar med vatten. Tryck- och temperaturberäkningar samt tryck- och termodynamisk modellering tyder på metamorfos under amfibolitfacies, med tryck omkring 3.0-5.5 kbar och temperatur omkring 490-640 °C. Resultaten från detta projekt ger ny information om de metamorfa bergarterna i Arlanda området och förekomst av As i dessa. Vidare studier är nödvändiga för att kunnaförutse i vilken form och i vilka bergarter As förekommer.

La thèse s’inscrit dans la problématique du dépôt de couches minces en procédés de pulvérisation réactive cathodique magnétron continu basse puissance (R-DC) et pulsé haute puissance (R-HiPIMS). Le mode réactif consiste à ajouter, dans l’argon, un gaz réactif tels que l’oxygène ou l’azote. Les oxydes et les nitrures ont de très nombreuses applications industrielles. Néanmoins, les exigences des nouvelles applications nécessitent de mieux comprendre, contrôler et maîtriser les processus fondamentaux gouvernant le transport de la matière pour optimiser ces procédés plasmas. L’objectif principal de cette thèse est d’étudier le transport des atomes pulvérisés de titane (Ti) en mélange Ar/N2 et d’établir des corrélations avec les propriétés des dépôts de type TiN. La fluorescence induite par diode laser (résolue en temps dans le cas du procédé HiPIMS) a été développée pour mesurer les fonctions de distribution en vitesse des atomes neutres Ti à l’état fondamental en fonction de la pression, de la distance par rapport à la cible et du mélange gazeux. Le degré de liberté supplémentaire qu'offre la dimension temporelle du plasma HiPIMS a permis de caractériser leur cinétique de transport en ayant la possibilité de séparer les temps caractéristiques des différents processus, et de mettre en évidence trois populations d’atomes (énergétique, quasi-thermalisée et thermalisée). Les fonctions de distribution en énergie des ions Ti+ ont été mesurées par spectrométrie de masse et des hypothèses sont proposées pour pouvoir expliquer les quatre populations identifiées. Enfin, les couches minces déposées ont été analysées par MEB, DRX et microsonde de Castaing. / The growth of thin layers in reactive-direct current magnetron sputtering (R-DC) and reactive-high power impulse magnetron sputtering (R-HiPIMS) processes is the general framework of this PhD. Reactive processes consist in the addition, in argon gas, of a reactive gas such as oxygen or nitrogen, and allow the deposition of oxides and nitrides which have many industrial applications. Nevertheless, the high level of expectations regarding new applications requires a better understanding, controlling, mastering of basic processes governing atoms transport in the view of process optimization. The main goal of this PhD is to study the transport of sputtered titanium atoms (Ti) in Ar/N2 gas mixture and to establish correlations with TiN film properties. Tunable diode laser induced fluorescence technique (time resolved in the case of HiPIMS process) has been developed in order to measure velocity distribution functions of neutral Ti atoms at the ground state, function of the pressure, the distance from the target and the gas mixture. In HiPIMS, the additional degree of freedom, given by time dimension, allowed to characterize their kinetic of transport while at the same time providing the possibility to separate characteristic time scales of different processes. Three atoms populations have been highlighted (energetic, quasi-thermalized and thermalized ones). Energy distribution functions of Ti+ ions have been measured using mass spectrometry and four populations have been observed and explained. Finally, deposited thin films have been analyzed by means of SEM, XRD and electron microprobe methods.