Intrusion-related, carbonate rock–hosted replacement deposits are an important source of global base metal production that includes: Cu-Zn skarn, Zn-Pb-Ag carbonate replacement and Ag-base metal deposits. These deposits are located in multiple geological settings and are commonly associated with low-grade Cu-Mo calc-alkaline porphyry districts. Visible alteration halos to these deposits range from ten to hundreds of metres around high temperature skarn deposits, being small to imperceptible around the distal relatively low temperature members of this clan. Patterns of visible and cryptic alteration are described and constrained in this study particularly around paleo-fluid flow zones at different distances and elevations from the ore centre. This was done in order to identify the large-scale zonation, mechanisms, and effects of fluid infiltration especially into the distal portions of these deposits. The main alteration tracers employed included mineralogy, major and trace element geochemistry, oxygen and carbon isotopes, and the fluorescent signature of calcite veins associated with the fluids conduits. Two areas were selected for this study: the large Cu-Zn Antamina skarn and the Ag-base metal Uchucchacua vein deposits in the Peruvian Central Andes as these deposits represent the end-members of the polymetallic carbonate rock-hosted deposits and hence, provide an excellent opportunity to examine the margins and upper sections of these hydrothermal systems. Geochronological analyses of intrusive dikes were used to establish the magmatic and hydrothermal evolution associated with mineralization, as well as the genetic linkage between proximal and distal portions of the mineralizing system at Antamina. Oxygen, carbon and strontium isotope data of vein minerals is also used to constrain the temperature of the fluids proximal and distal to the magmatic centre. Chemical data of fluorescent and non-fluorescent veins were used to determine the main activators of fluorescence and to constrain its relationship with mineralizing fluids. In summary, results of this research identify a large-scale zonation of visible and cryptic alteration around paleo-fluid flow zones demonstrating the linkage between Ag-base metal veins, replacement and skarn deposits. Anomalous halos determined throughout Antamina and Uchucchacua deposits may contribute to the development of a more systematic exploration methodology for these types of deposits.

Intrusion-related, carbonate rock–hosted replacement deposits are an important source of global base metal production that includes: Cu-Zn skarn, Zn-Pb-Ag carbonate replacement and Ag-base metal deposits. These deposits are located in multiple geological settings and are commonly associated with low-grade Cu-Mo calc-alkaline porphyry districts. Visible alteration halos to these deposits range from ten to hundreds of metres around high temperature skarn deposits, being small to imperceptible around the distal relatively low temperature members of this clan. Patterns of visible and cryptic alteration are described and constrained in this study particularly around paleo-fluid flow zones at different distances and elevations from the ore centre. This was done in order to identify the large-scale zonation, mechanisms, and effects of fluid infiltration especially into the distal portions of these deposits. The main alteration tracers employed included mineralogy, major and trace element geochemistry, oxygen and carbon isotopes, and the fluorescent signature of calcite veins associated with the fluids conduits. Two areas were selected for this study: the large Cu-Zn Antamina skarn and the Ag-base metal Uchucchacua vein deposits in the Peruvian Central Andes as these deposits represent the end-members of the polymetallic carbonate rock-hosted deposits and hence, provide an excellent opportunity to examine the margins and upper sections of these hydrothermal systems. Geochronological analyses of intrusive dikes were used to establish the magmatic and hydrothermal evolution associated with mineralization, as well as the genetic linkage between proximal and distal portions of the mineralizing system at Antamina. Oxygen, carbon and strontium isotope data of vein minerals is also used to constrain the temperature of the fluids proximal and distal to the magmatic centre. Chemical data of fluorescent and non-fluorescent veins were used to determine the main activators of fluorescence and to constrain its relationship with mineralizing fluids. In summary, results of this research identify a large-scale zonation of visible and cryptic alteration around paleo-fluid flow zones demonstrating the linkage between Ag-base metal veins, replacement and skarn deposits. Anomalous halos determined throughout Antamina and Uchucchacua deposits may contribute to the development of a more systematic exploration methodology for these types of deposits.

[pt] Atualmente, os lasers de alta potência estão sendo testados pela indústria de petróleo como ferramentas de perfuração. Isto ocorre visando dois objetivos fundamentais: (i) aumentar a eficiência na perfuração de poços (maior taxa de penetração) e (ii) melhorar o controle da geometria do corte de revestimento no processo de canhoneio de poço. Este trabalho tem como objetivo contribuir para a tecnologia de canhoneio a laser em rochas carbonáticas através do desenvolvimento de técnicas para aumentar o volume de rocha removida por unidade de tempo. Estudou-se o comportamento termomecânico das rochas carbonáticas quando um laser é utilizado como ferramenta de perfuração no processo de canhoneio. Este conhecimento, obtido através de experimentos e simulações, forneceu dados para a otimização dos parâmetros de perfuração. Foram investigadas as condições de perfuração estática (não há movimentação do feixe do laser) e dinâmica (o feixe do laser percorre uma trajetória espiral). Além disso, foram investigados os resultados da perfuração sob pressão atmosférica e também utilizando uma câmara de pressão projetada para emular a pressão confinante do reservatório. Foram realizados testes experimentais de perfuração a laser com corpos de prova feitos a partir da rocha Bege Bahia. O Bege Bahia é um afloramento utilizado para simular as rochas encontradas nos reservatórios do Pré-sal. A análise destes corpos de prova foi feita através de inspeção e da caracterização por microtomografia, permitindo observar e caracterizar as propriedades da rocha, além da zona termicamente afetada (ZTA), características geométricas do furo, e valores da energia específica da perfuração. Estes resultados foram comparados com resultados obtidos através de simulações. Na modelagem numérica, o processo de canhoneio foi simulado pelo método de elementos finitos através de um modelo termomecânico elástico transiente axissimétrico que verificou as condições de perfuração. O modelo numérico permitiu observar o comportamento das tensões e temperaturas nos testes que envolvem altas temperaturas e altas pressões. Estas grandezas são usualmente difíceis de serem medidas em ensaios experimentais e, portanto, não foram observadas nos ensaios experimentais discutidos nesta tese. Também foram obtidos através da modelagem numérica valores para propriedades da rocha e da zona termicamente afetada (ZTA), características geométricas do furo, e valores da energia específica da perfuração. Os resultados numéricos obtidos foram comparados com resultados dos ensaios experimentais. Os resultados obtidos mostraram que a condição de perfuração dinâmica consegue remover uma quantidade maior de material e produzir uma ZTA maior em Comparação com o teste estático, gerando uma melhor relação tempo x potência. Os testes estáticos e dinâmicos permitiram se chegar às condições de canhoneio mais eficientes para a perfuração da rocha. A análise de tensões do modelo mostrou uma correlação compatível com o perfil do dano encontrado nos ensaios experimentais. / [en] Currently, the petroleum industry is testing high power lasers as drilling tools. The use of these lasers for this application has two main reasons: (i) to increase the efficiency of well drilling (higher penetration rate) and (ii) to improve the control of the geometry of the hole in the casing during the perforation process of the well. The present thesis has the purpose of contributing to the laser perforation technology in carbonate rocks by developing techniques to increase the volume of rock removed by unit of time. The thermo-mechanical behavior of the carbonate rocks was studied when a laser is used as the drilling tool in the perforation process. This knowledge, obtained through experiments and simulations, supplied data for the optimization of the drilling parameters. Both static (the laser beam does not move) and dynamic (the laser beam moves in a spiral trajectory) drilling conditions were investigated. Also investigated were drilling conditions under atmospheric pressure and under high pressure, where a pressure chamber designed to emulate pressure conditions of reservoirs was used. Experimental tests were performed by laser drilling samples made of Bege Bahia rock. This rock is used to simulate rocks found in pre-salt reservoirs. The analysis of these samples was performed through inspection and microtomography characterization, allowing the observation of properties of the rocks and of the heat affected zone (HAZ), geometric characteristics of the hole, and values of the drilling specific energy. These results were compared to the results obtained by simulations. In the numerical modeling, the perforation process was simulated with the finite element method through a transient axisymmetric thermo-mechanical elastic model that verified the drilling conditions. The numerical model allowed the observation of the behavior of the tensions and temperatures in tests involving high temperatures and pressures. These properties are usually difficult to measure in experimental tests and, therefore, were not measured during the experimental tests discussed in this thesis. Also obtained by numeric modeling were: properties of the rock and of the HAZ, geometric characteristics of the hole, and values of the drilling specific energy. The numeric results obtained were compared to the experimental results. The results obtained showed that the dynamic drilling condition is able to remove a larger amount of material and produce a larger HAZ, compared to the static condition, thus generating a better time x power relation. The static and dynamic tests allowed reaching more efficient conditions for rock drilling. The analysis of the tension of the model showed a compatible correlation with the damage profile found in the experimental tests.

Intrusion-related, carbonate rock–hosted replacement deposits are an important source of global base metal production that includes: Cu-Zn skarn, Zn-Pb-Ag carbonate replacement and Ag-base metal deposits. These deposits are located in multiple geological settings and are commonly associated with low-grade Cu-Mo calc-alkaline porphyry districts. Visible alteration halos to these deposits range from ten to hundreds of metres around high temperature skarn deposits, being small to imperceptible around the distal relatively low temperature members of this clan. Patterns of visible and cryptic alteration are described and constrained in this study particularly around paleo-fluid flow zones at different distances and elevations from the ore centre. This was done in order to identify the large-scale zonation, mechanisms, and effects of fluid infiltration especially into the distal portions of these deposits. The main alteration tracers employed included mineralogy, major and trace element geochemistry, oxygen and carbon isotopes, and the fluorescent signature of calcite veins associated with the fluids conduits. Two areas were selected for this study: the large Cu-Zn Antamina skarn and the Ag-base metal Uchucchacua vein deposits in the Peruvian Central Andes as these deposits represent the end-members of the polymetallic carbonate rock-hosted deposits and hence, provide an excellent opportunity to examine the margins and upper sections of these hydrothermal systems. Geochronological analyses of intrusive dikes were used to establish the magmatic and hydrothermal evolution associated with mineralization, as well as the genetic linkage between proximal and distal portions of the mineralizing system at Antamina. Oxygen, carbon and strontium isotope data of vein minerals is also used to constrain the temperature of the fluids proximal and distal to the magmatic centre. Chemical data of fluorescent and non-fluorescent veins were used to determine the main activators of fluorescence and to constrain its relationship with mineralizing fluids. In summary, results of this research identify a large-scale zonation of visible and cryptic alteration around paleo-fluid flow zones demonstrating the linkage between Ag-base metal veins, replacement and skarn deposits. Anomalous halos determined throughout Antamina and Uchucchacua deposits may contribute to the development of a more systematic exploration methodology for these types of deposits. / Science, Faculty of / Earth, Ocean and Atmospheric Sciences, Department of / Graduate

The application of surfactants and polymers in carbonate reservoirs has a high potential with emerging technology of the manufacture of these chemicals. Tertiary or enhanced oil recovery with chemicals (CEOR) will become more relevant with decreasing new exploration of oil deposits and high remaining oil saturations in huge carbonate oil reservoirs. However, in several oil deposits, high reservoir brine salinity and moderate to high reservoir temperature are encountered. Under such conditions, many chemicals will be insoluble or degrade fast. A selection of commercial and research surfactants and polymers has been investigated for their application under brine salinity of up to 18 percent by weight with significant hardness and a moderate reservoir temperature of 70 °C. Chemical systems were tested towards outcrop limestone rock samples and calcite platelets in combination with a crude oil, which was modified by different organic acids regarding its wetting potential. Wettability alteration from preferentially oil-wet core plugs was pursued with ethoxylated tertiary amines and quaternary ammonium compounds. The main mechanism of wettability alteration towards more water-wet was proposed as extraction of carboxylate anions from the oil phase and the solid samples into aqueous micelles. Thus, high surfactant concentrations would result in improved recovery. From screening of different surfactant combinations in tertiary core flooding, one promising system of an alkyl ether sulfate and hexadecyltrimethylammonium combined with a terpolymer (TP) from acrylic acid, ATBS and NVP is proposed for the examined conditions. Low to moderate adsorption of the single surfactants and their combination as well as a favorable, stabilized phase behavior when combined with the polymer emphasize the applicability of the system. However, long term stability can be an issue with respect to the sulfate surfactant degradation at 70 °C. Analysis of mixed ionic surfactant systems after adsorption testing has been successfully pursued with a combined TC/TNb-determination.