[No abstract submitted] / Applied Science, Faculty of / Materials Engineering, Department of / Graduate

Thesis (M.S.)--Wisconsin. / Includes bibliographical references (leaves 69-71).

Multifractional analysis for scheelite (G=5.9-6.1), magnetite (G=5.2), heavies (G>3.3), mediums (3.3<G<2.9), and lights (G<2.9), in drainage sediments downstream of the Clea tungsten-bearing skarn deposit, Yukon Territory, revealed three interdependent problems that complicate interpretation of results of drainage surveys for W: (1) Scheelite concentrations in stream sediments reflect, in part, hydraulic sorting rather than source distribution. (2) Low numbers of scheelite grains in stream sediments cause high random sampling and subsampling errors and present analytical difficulties. (3) Scheelite/heavies or scheelite/mediums ratios may not be appreciably higher downstream of scheelite-bearing skarn than barren bedrock, because scheelite, heavies and mediums occur in increased amounts in skarns (i.e. they covary in source materials). Hydraulic effects result in systematic changes in mineral distributions between high and low energy environments (characterized by coarse gravel and fine gravel to sand, respectively). Scheelite, magnetite, heavies and mediums concentrations in minus 10-mesh sediments are greater in high than low energy environments, and this relative enrichment increases with grain size and density (up to one-hundredfold for scheelite). Using a regression method, developed in this study, hydraulically equivalent sizes of magnetite and heavies were empirically determined for finer (3.0-3.5 phi and 3.5-4.25 phi) scheelite sizes. Ratioing the weight of scheelite to that of a hydraulically equivalent mineral greatly reduces hydraulic variability. Resulting profiles of hydraulically equivalent scheelite concentrations more clearly delineate locations of scheelite input to the stream. The rare-grain problem can be reduced at the sampling level by sampling from high energy environments (thereby exploiting hydraulic effects) and/or by sampling for finer scheelite. Heavy mineral separation is the most effective means of reducing the rare grain problem at the subsampling and analytical levels. The problem of covariance in source materials can best be remedied by ratioing to an individual (hydraulically equivalent) heavy mineral which has a constant and ubiquitous distribution in the area of interest. In this study, magnetite shows promise, but more information on its source distribution is needed. / Science, Faculty of / Earth, Ocean and Atmospheric Sciences, Department of / Graduate

Titre de l'écran-titre (visionné le 19 juin 2023) / La scheelite est un minéral de tungstène (CaWO₄) qui est présent dans plusieurs gisements magmatiques-hydrothermaux et qui est associé temporellement et spatialement à l'or dans certains gisements d'or orogéniques dans le monde. Comme la scheelite est un minéral résistant et lourd, et qu'elle est facile à identifier en raison de sa propriété luminescente, sa présence dans les sédiments a été utilisée comme outil pour cibler les gisements de tungstène et, plus récemment, les gisements d'or orogéniques dans les régions où l'exposition du substratum rocheux est rare. La scheelite contient certains éléments traces clés (Sr, Mo, REE, Na, As) dont la distribution et la concentration sont contrôlées par le contexte géologique dans lequel la scheelite s'est formée. Par conséquent, comprendre les facteurs qui contrôlent la distribution des éléments traces dans la scheelite permet d'utiliser la composition de la scheelite pour cibler les gisements minéraux. Cette thèse de doctorat étudie la composition en éléments traces de la scheelite associée aux principaux gisements magmatiques-hydrothermaux contenant de la scheelite, tels que les skarns oxydés et réduits, les veines de quartz/greisen à Sn-W, les porphyres à W-Mo et les systèmes aurifères liés à des intrusions réduites, afin d'identifier les principaux facteurs qui contrôlent la distribution des éléments mineurs et traces dans la scheelite. Ces nouvelles données sont combinées avec les données de la littérature sur les gisements d'or orogéniques contenant de la scheelite et étudiées à l'aide de l'analyse discriminante des moindres carrés partiels (PLS-DA) pour trouver les variables chimiques qui permettent de distinguer la scheelite des différents types de gisement et de les utiliser pour cibler les gisements de minerai d'or et de tungstène. Les résultats montrent que la fugacité de l'oxygène, la composition des fluides et des intrusions, les minéraux co-précipités et la salinité des fluides sont les principaux paramètres qui contrôlent l'incorporation des éléments traces dans la scheelite provenant de gisements magmatiques-hydrothermaux. Les résultats de l'analyse PLS-DA montrent que les teneurs élevées en Mo, As et V dans la scheelite sont caractéristiques des dépôts magmatiques-hydrothermaux formés sous une fugacité élevée de l'oxygène, tels que les skarns oxydés, tandis que les teneurs élevées en Nb, Mn, Y et U sont caractéristiques de la scheelite formée dans des conditions réduites, qui sont généralement associées aux skarns réduits et aux veines de quartz/greisen à Sn-W. La scheelite provenant de gisements d'or orogéniques présente une anomalie positive prédominante en Eu, une teneur élevée en Sr, et de faibles teneurs en Mo, Mn et Nb, ce qui la distingue de la scheelite liée aux gisements magmatiques-hydrothermaux. De telles différences permettent de discriminer la scheelite associée à l'or orogénique de celles des dépôts magmatiques-hydrothermaux. En plus de l'analyse PLS-DA, deux modèles de Random Forest sont proposés pour évaluer la source de la scheelite et la fertilité en or des gisements d'or orogéniques contenant de la scheelite. La grande justesse obtenue par les deux modèles renforce l'utilisation des éléments traces dans la scheelite non seulement comme un outil robuste et efficace pour cibler les gisements contenant de la scheelite, mais aussi pour évaluer la fertilité des gisements d'or orogéniques contenant de la scheelite. / Scheelite is a tungsten mineral (CaWO₄) that is present in several magmatic-hydrothermal deposits and occurs temporally and spatially associated with Au in some orogenic Au deposits worldwide. Because scheelite is a resistant, heavy mineral, and easy to identify due to luminescence propriety, its occurrence in unconsolidated sediments has been used as a tool for targeting tungsten and orogenic Au deposits in areas where the bedrock exposition is rare. Scheelite hosts some key trace elements (Sr, Mo, REE, Na, As) those distribution and concentration are controlled by the geological settings where scheelite formed. Therefore, understanding the factors that control the distribution of trace elements in scheelite provides insights for using scheelite composition to target mineral deposits. This PhD thesis investigates the trace element composition of scheelite associated with the main scheelite-bearing magmatic-hydrothermal deposits such as oxidized and reduced skarns, quartz-vein/greisen Sn-W, porphyry W-Mo and reduced intrusion-related gold systems (RIRGS) to identify the principal factors that control the distribution of minor and trace elements in scheelite. This new data is combined with literature data of scheelite-bearing orogenic Au deposits and investigated using partial least square-discriminant analysis (PLS-DA) to find the chemical variables that allow for discriminating scheelite from different deposit types and use these to target for Au and W ore deposits. The results show that oxygen fugacity, fluid and intrusion compositions, co-precipitated minerals and fluid salinity are the main parameters that control the incorporation of trace elements in scheelite from magmatic-hydrothermal deposits. The PLS-DA results show that high Mo, As and V contents in scheelite are characteristic of magmatic-hydrothermal deposits formed under high oxygen fugacity such as oxidized skarns, whereas high Nb, Mn, Y and U contents are features of scheelite formed under reduced conditions, which are commonly associated with reduced skarns and quartz-veins/greisen Sn-W deposits. Scheelite from orogenic Au deposits displays predominantly positive Eu anomaly, high Sr and low Mo, Mn and Nb contents which differ from scheelite related to magmatic-hydrothermal deposits. Such differences allow discriminate scheelite associated with orogenic gold from those of magmatic-hydrothermal deposits. In addition to PLS-DA, two Random Forest models are proposed to assess the source of scheelite and the Au endowment of scheelite-bearing orogenic Au deposits. The high accuracy obtained by the two models enhances the use of trace element in scheelite not only as a robust and efficient tool for targeting scheelite-bearing deposits, but also to assess the fertility of scheelite-bearing orogenic Au deposits.

Thesis (M.S.)--University of Missouri-Columbia, 2006. / The entire dissertation/thesis text is included in the research.pdf file; the official abstract appears in the short.pdf file (which also appears in the research.pdf); a non-technical general description, or public abstract, appears in the public.pdf file. Title from title screen of research.pdf file viewed on (February 26, 2007) Includes bibliographical references.

No description available.

Conselho Nacional de Desenvolvimento Científico e Tecnológico / Em trabalho de prospecção geoquímica regional por concentrado de bateia (PEREIRA e SANTOS, 1983) foi evidenciado na região de Cacaria, município de Piraí, ocorrências de scheelita. Com o objetivo de investigar a possível fonte litológica desta ocorrência, foram realizadas amostragens de sedimentos de corrente e concentrado de bateia além de investigações de campo para sua fonte. Elaborouse ainda um mapa geológico em escala de detalhe 1:25.000. As unidades estratigráficas base utilizadas no mapa foram definidas em trabalhos da empresa RIOFINEX (1977) durante pesquisas para mineralizações de Pb-Zn na região de Rio Claro. Ensaios laboratoriais envolvendo descrição de lâminas petrográficas, difratometria de raios X, fluorescência de raios X, espectrometria Raman, microscopia eletrônica de varredura e o auxílio do mineralight de ondas curtas. As mineralizações scheelitíferas encontradas foram classificadas segundo um modelo do tipo sedimentar exalativo, localmente com possíveis contribuições de atividades metassomáticas tardias, concentrando a mineralização, assim como proposto para algumas ocorrências já descritas no nordeste brasileiro. / In a mineral exploration panning concentrate programme PEREIRA AND SANTOS (1985) identified in the Cacaria region, near the Piraí City, occurences of scheelite. With the objective to investigate the lithological origin of this mineral a nonsystematic sampling by stream sediments and panning concentrate, was carried out to identify the tungsten mineralization source. A geological map was also executed at detailed scale of 1:25.000. The stratigraphic division applied to this map was defined in projects of RIOFINEX (1977) company during investigation of Pb-Zn mineralization in Rio Claro. Laboratorial trials involving description of petrography, Xray diffraction, X-ray fluorescence, Raman spectroscopy, electronic microscopy scanning and short wave mineralight. The scheelite-bearing mineralization was classified according to a exhalative sedimentary model with possible contributions of a late metasomatic activities concentrating the mineralization as proposed for some occurrences observed in northeast part of Brazil.

Conselho Nacional de Desenvolvimento Científico e Tecnológico / Em trabalho de prospecção geoquímica regional por concentrado de bateia (PEREIRA e SANTOS, 1983) foi evidenciado na região de Cacaria, município de Piraí, ocorrências de scheelita. Com o objetivo de investigar a possível fonte litológica desta ocorrência, foram realizadas amostragens de sedimentos de corrente e concentrado de bateia além de investigações de campo para sua fonte. Elaborouse ainda um mapa geológico em escala de detalhe 1:25.000. As unidades estratigráficas base utilizadas no mapa foram definidas em trabalhos da empresa RIOFINEX (1977) durante pesquisas para mineralizações de Pb-Zn na região de Rio Claro. Ensaios laboratoriais envolvendo descrição de lâminas petrográficas, difratometria de raios X, fluorescência de raios X, espectrometria Raman, microscopia eletrônica de varredura e o auxílio do mineralight de ondas curtas. As mineralizações scheelitíferas encontradas foram classificadas segundo um modelo do tipo sedimentar exalativo, localmente com possíveis contribuições de atividades metassomáticas tardias, concentrando a mineralização, assim como proposto para algumas ocorrências já descritas no nordeste brasileiro. / In a mineral exploration panning concentrate programme PEREIRA AND SANTOS (1985) identified in the Cacaria region, near the Piraí City, occurences of scheelite. With the objective to investigate the lithological origin of this mineral a nonsystematic sampling by stream sediments and panning concentrate, was carried out to identify the tungsten mineralization source. A geological map was also executed at detailed scale of 1:25.000. The stratigraphic division applied to this map was defined in projects of RIOFINEX (1977) company during investigation of Pb-Zn mineralization in Rio Claro. Laboratorial trials involving description of petrography, Xray diffraction, X-ray fluorescence, Raman spectroscopy, electronic microscopy scanning and short wave mineralight. The scheelite-bearing mineralization was classified according to a exhalative sedimentary model with possible contributions of a late metasomatic activities concentrating the mineralization as proposed for some occurrences observed in northeast part of Brazil.

Extensive research in recent years has failed to develop any essentially new method of large scale tungsten production. A new tungsten powder production technique from calcium tungstate (CaWO4) has recently been reported. In this thesis, this technique was further explored from the aspects of electrochemical reduction mechanism and kinetics, applicability to scheelite concentrates and industrial production. Cyclic voltammetry, constant potential and constant current electrochemical reduction tests were performed to determine the reversible cell potential. Analyses of the experimental results revealed that at least 2.2 V was required to compensate the potentials for the accompanying cell reaction and the electrode polarizations. A cell reaction was proposed by associating the experimental results and the Gibbs Energy changes of the possible reactions. An experiment (mixture) design was created to optimize the process parameters of the electrochemical reduction of CaWO4 to W in molten CaCl2-NaCl eutectic mixture. Temperature, applied voltage and the length of Kanthal wire winding of the CaWO4 pellets were selected as the process parameters and allowed to vary between the predetermined minimum and maximum values. The rates of the electrochemical reductions were interpreted from the variations of current and total charge vs. time graphs under different conditions. The analysis pointed out 640oC and 2.81 V from the created mixture design for the fastest reduction and it was seen that the effect of Kanthal wire winding on the output current was less pronounced when compared to the other two parameters. Another set of experiments was performed by full factorial design to investigate the cleaning procedure needed to remove calcium containing byproducts after electrochemical reduction experiments. Three levels were determined prior to the experiments for the selected three parameters / temperature, acid concentration and exposure time. Main effect and interaction graphs for calcium percent as a function of process parameters were plotted. Calcium contents of the samples were determined by XRF measurements. A 300 g/day capacity tungsten production line was manufactured to take the process one step closer to industrialization. Problems at larger scale were addressed as incomplete reduction, oxidation of graphite and corrosion of cathode materials. After careful research, AISI 316 Ti steel was found to impart sufficient resistance to highly corrosive environment. Oxidation of graphite anode inside the cell was lowered to acceptable levels by continuous nitrogen flow. Metallic tungsten powder was obtained from rich and flotation concentrates of Uludag Etibank Volfram Plant (closed in 1989) together with mainly iron. It was seen that tungsten and iron do not make compounds at the temperatures used for reduction (600-750oC). A basic diffusion model in the electrolyte was developed to better understand the decrease in current values and incomplete reduction encountered during large scale production. The model was used to simulate the recorded current vs. time graphs of selected experiments.

La chaine varisque ouest-européenne est une vaste province métallogénique qui abrite une large diversité de minéralisations. Une grande partie d’entre elles ont fait l'objet d'exploitations historiques, à l'instar de Salau(Pyrénées Centrales), le plus important gisement de tungstène français. Les résultats de terrain combinés aux études minéralogiques et géochimiques convergent pour montrer qu'il existe deux types de minéralisations superposées : (1) un skarn à silicates calciques, rare scheelite fine et sulfures disséminés ; (2) une brèche filonienne à sulfures massifs (pyrrhotite et chalcopyrite dominante), or et abondante scheelite grossière qui a constitué l’essentiel du minerai exploité. Cette brèche se localise dans des zones de cisaillement ductile-fragile(faille Véronique) recoupant la granodiorite. Les datations U/Pb sur zircon, apatite et scheelite situent le skarn contemporain de l'intrusion de la Fourque à 295±2 Ma alors que la brèche à sulfures massifs se forme environ6 Ma après, à 289±2 Ma. Ces minéralisations, issues de deux intrusions successives (granodiorite puis leucogranite), s’inscrivent dans l'évolution d'un modèle Intrusion Related Deposit. La mise en place de labrèche à forte teneur en or-scheelite est initiée par la focalisation progressive de la déformation régionale dans la Zone axiale des Pyrénées au sein de failles E-W dextres inverses. L'origine de l'or à l'échelle des Pyrénées pourrait s'expliquer en partie par une large répartition de ces minéralisations à forte teneur. La carte de paléotempératures RSCM a permis de localiser d’autres intrusions non affleurantes en étendant le district minéralisé sur plus de 7 km jusqu’à l’indice à W-Au d’Aurenère en Espagne. / The Western European variscan belt is a vast metallogenic district which hosts a wide diversity of mineralizations. A large part of them have been historically exploited, such as Salau (Central Pyrenees), the most important French tungsten deposit. The field results combined with the mineralogical and geochemical studies converge to show that it exists two superimposed ore types: (1) a calcic silicates skarn with rare fine grainedscheelite and disseminated sulphides; (2) a mineralized breccia with massive sulphides (pyrrhotiteand chalcopyrite dominant), gold and abundant coarse-grained scheelite which have constituted the main part of the exploited ore. This breccia is localized in ductile-fragile shear-zones (Veronique fault) which crosscut the granodiorite. U/Pb datings on zircon, apatite and scheelite place the skarn, contemporaneous of the LaFourque intrusion at 295±2 Ma while the massive sulphides breccia was formed ca. 6 Ma later at 289±2 Ma.These mineralizations, from two successive intrusions (granodiorite then leucogranite), belong to the evolution of an Intrusion Related Deposit model. The emplacement of the high grade gold and scheelite breccia was initiated by the progressive focalization of the regional deformation in the Axial Zone of the Pyrenees within EWdextral-reverse faults. The source of gold at the Pyrenees scale could be explained in part by this type of high-grade mineralizations. The RSCM paleo-temperature map has made possible to locate other undercover intrusions, extending the mineralized district over more than 7 km until the W-Au Aurenere occurrence in Spain.