The transition from the Neoproterozoic to the early Cambrian world was a critical time in the co-evolution of life and the environment, when dramatic changes in the environment, including global glaciations and rising atmospheric oxygen levels precipitated the conditions in which variety of complex life emerged, diversified, and proliferated. However, questions persist regarding the timing and duration of those environmental events, and thus the extent of their direct effect on the evolution of life. These changing environmental conditions also produced unique taphonomic conditions that preserved a wide variety of organisms, and also produced unusual early diagenetic features that can be difficult to distinguish from fossilized organisms. In order to better resolve the link between life and the environment during the Neoproterozoic to Cambrian transition I present three chapters. The first chapter of this dissertation examines the carbonate clasts from a glacial diamictite deposited at the end of the Cryogenian Period in South China. By determining the source locality of those carbonate clasts using stable carbon and oxygen isotope compositions, we can better understand the extent of the Marinoan Glaciation and the intensity of its impact on the Earth's surface. In the second chapter of this dissertation, I investigate the changing chemical conditions of ocean waters following both the Marinoan glaciation and potentially one of the most intense disruptions to the carbon cycle in Earth History, the Ediacaran Shuram carbon isotope anomaly. I use Hg concentrations and stable isotope compositions to determine changes in sediment sourcing along with changes in marine redox, such as the development of photic zone euxinia. In the third chapter, I investigate the identity of Brooksella alternata, a purportedly cnidarian fossil that was later suggested to be a hexactinellid sponge fossil. My morphological and compositional analysis reveals B. alternata to be a concretion and thus a pseudofossil. / Doctor of Philosophy / The Earth experienced major changes between 635 and ~514 million years ago; the last global scale glaciation in the history of Earth ended, early animals arose, primary producers such as algae grew larger and more complex, and the first animals that were mobile and with hard skeletal parts evolved and diversified tremendously. Concomitantly, the environment on the Earth changed dramatically: the carbon cycle experienced one of the greatest disruptions in all of Earth history and the oceans and atmosphere gradually became more oxygen-rich, though areas with low levels of dissolved molecular oxygen and high concentrations of dissolved iron or hydrogen sulfide persisted, which may have impeded the diversification of complex animals. The exact timing and intensity of these changes are not fully resolved, and by investigating this time interval in the geologic record, we can better understand how the world changed and how life at the time responded. These changing environments also produced unique conditions which led to fossils being preserved in unique ways, though these conditions also produced non-biological structures that superficially resemble fossils. The first chapter of this dissertation investigates the source of clasts made of carbonate rock from a glacial diamictite (the poorly sorted mixture of the fine-grained and coarse-grained deposits left behind as glaciers recede) in South China deposited at the end of the last global scale glaciation about 635 million years ago. By determining the source, we can evaluate how far glacial activity transported sediments. I found that the previously suggested source of these clasts does not match the geochemical fingerprint of the carbonate clasts. I propose that these carbonate clasts may have come from a source that has since become "extinct" because of glacial erosion, or they may have come from another continent (for example, India). These scenarios highlight the magnitude of the global glaciation. In the second chapter, I investigated the mercury concentrations and stable isotope compositions from organic rich shales deposited ~550 million years ago. Mercury is an emerging tool for evaluating the level of dissolved molecular oxygen in ancient oceans. In this study, I found evidence of locally complex marine oxygen levels, including evidence for photic zone euxinia, meaning waters where oxygen was absent and hydrogen sulfide was present. Such conditions are toxic to animals and may have delayed the diversification of complex animal life. In the final chapter, I analyzed the ~503 million-year-old fossil Brooksella alternata. It was first described more than 100 years ago as a jelly-fish fossil. More recently it was suggested to be a sponge fossil (though it has been ascribed many other identities). Based on morphological analysis of a large collection, I determined that Brooksella alternata is not a fossil but rather a concretion with unusual shape.

The polymetallic carbonate-replacement prospect at Piavitsa is part of the ore-forming system of the Stratoni Fault Zone within the Kassandra mining district in northeast Greece. This district constitutes the southern segment of the Serbo-Macedonian belt, a promising region for the exploration of precious and critical metals in Greece. This master thesis is framed within the X-MINE project under the Horizon 2020 program. Three main objectives are defined: (1) to characterize the mineralization at Piavitsa utilizing reflected light microscopy, microprobe, and laser-ablation inductively coupled mass spectrometry (LA-ICP-MS), and (2) to evaluate the contributions of the scanning GeoCore X10 (XRF-XCT) technology to the understanding of the ore, and (3) to assess potential environmental impacts. At Piavitsa, an early base-metal assemblage, composed of brecciated sphalerite and As-rich pyrite, is infilled and overprinted by an assemblage of As-poor to moderately-rich pyrite, alabandite, and Mnrich sphalerite. The latter two are corroded and replaced by Mn-rich carbonate. Fractures and interstices are infilled by a late assemblage of Ca-Mn-Mg carbonate, galena, As-poor pyrite, tetrahedrite-tennantite, and in the periphery of the orebody, seligmannite-bournonite and kesterite.  Based on absolute elemental concentrations obtained by in situ LA-ICP-MS, the mineral hosts (primary; secondary) are defined as: pyrite (Fe, Co, Ni, and Au; As), sphalerite (Zn, Ga, Ge, Cd, Sn; Mn), galena and bournonite (Pb, Se, Te, Tl, and Bi; Ag, Sb), alabandite (Mn; Cd and Sb), and tetrahedrite (Cu, As, Ag, and Sb). In cocrystallized assemblages, some differences are observed. In pyritetetrahedrite asemblages, tetrahedrite mainly hosts As and Au, instead of pyrite, whereas in sphaleritealabandite assemblages, alabandite is the host of Mn, As, Ag and Sb and sphalerite, of Cd and Sn. Three concentrates are produced from the current mining operations of Hellas Gold in the Stratoni area, e.g, Mavres Petres Zn-Pb mine. From LA-ICP-MS, it is inferred that a sphalerite concentrate from the Piavitsa ore would contain Ga (peripheral ore: 150 ppm; main ore: 10-40 ppm), Sn (peripheral ore: 800-1500 ppm; main ore: 25-230 ppm), and Cd (1600-4000 ppm). The galena concentrate would contain concentrations of Ag (1300-1700 ppm), Se (50 ppm), Sb (1200-1600 ppm), and Te (85-210 ppm). The pyrite concentrate would contain Au (0.5-24.5 ppm) but would be devoid of other economical trace elements. The values given here consider 100% purity, instead of 80-90% reported in previous studies. The GeoCore X10 technology provides a good indication of measurable elements. (>0.01 wt.%), including Mn, Fe, Cu, Zn, and Pb; As, Sb and Sn. Moreover, it helps to quickly identify the main ore and gangue minerals and their distribution in the deposit. The distinction between the ore and gangue minerals can be easily achieved based on the difference in their X-ray attenuation. It is worth highlighting that mineralogical info obtained by other analytical methods is still essential to validate the outputs of the instrument and to improve the interpretations drawn from them. Regarding the environmental impacts of mining the ore, the potential for acid generation and pollutant mobilization are low due to the carbonate-rich matrix. The mining poses low radioactivity risks due to the low concentration of radionuclides. Establishing a pollutants baseline and monitoring the surrounding water bodies and soils is highly recommended to reduce overlooked environmental impacts.

The geological sequestration of carbon dioxide (CO2) is one of the options of controlling the greenhouse gas emissions. However, leakage of CO2 from the storage reservoir is a risk associated with geological sequestration. Over longer times, large-scale groundwater motion may cause leakage of dissolved CO2 (CO2aq). The objectives of this thesis are twofold. First, the modelling study analyzes the leakage of CO2aq along the conducting pathways. Second, a relatively safer mode of geological storage is investigated wherein CO2aq is injected in a carbonate reservoir. A reactive transport model is developed that accounts for the coupled hydrological transport and the geochemical reactions of CO2aq in the porous media. The study provides a quantitative assessment of the impact of advection, dispersion, diffusion, sorption, geochemical reactions, temperature, and heat transport on the fate of leaking CO2aq. The mass exchange between the conducting pathway and the rock matrix plays an important role in retention and reactions of leaking CO2aq. A significant retention of leaking CO2aq is caused by its mass stored in aqueous and adsorbed states and its consumption in reactions in the rock matrix along the leakage pathway. Advection causes a significant leakage of CO2aq directly from the reservoir through the matrix in comparison to the diffusion alone in the rock matrix and advection in a highly conducting, but thin fracture. Heat transport by leaking brine also plays an important role in geochemical interactions of leaking CO2aq.  Injection of CO2aq is simulated for a carbonate reservoir. Injected CO2-saturated brine being reactive causes fast dissolution of carbonate minerals in the reservoir and fast conversion of CO2aq through considered geochemical reactions. Various parameters like dispersion, sorption, temperature, and minerals reaction kinetics are found to play important role in the consumption of CO2aq in reactions. / <p>Research Funders:</p><p>(i) Higher Education Commission (HEC) of Pakistan</p><p>(ii) Lars Erik Lundberg Scholarship Foundation, Sweden</p>

タンデトロン加速器質量分析計業績報告

La capture et le stockage géologique du CO2 constituent une option importante de limitation des émissions de gaz à effet de serre au niveau des pôles industriels et des centrales de production d’énergie. Les gaz capturés à l’issu de ces chaînes de production ne sont pas constitués de CO2 pur mais contiennent une fraction (jusqu’à 10 %) de gaz annexes qui sont essentiellement Ar, N2, SOx et NOx. Ces gaz étant pour la plupart très réactifs il est essentiel de connaître leur impact sur les conditions physico-chimiques du réservoir géologique d’accueil, ainsi que sur l’environnement dans le cas d’une de contamination des aquifères voisins du stockage. Des expérimentations en laboratoire ont simulé le vieillissement de roches de réservoir et couverture en provenance d’un réservoir carbonaté du Bassin aquitain et d’assemblages minéralogiques synthétiques dans des conditions de séquestration géologique. Les roches associées à une saumure sont altérées au contact de divers composés gazeux à 100 bar et 150°C sur une durée d’un mois : CO2 pur, SO2, NO pur et un mélange contenant majoritairement du CO2 et des fractions de Ar, N2, SO2, O2. Chaque expérience est comparée à une expérience témoin où le composé gazeux est remplacé par de l’azote. Le CO2 ne montre qu’une réactivité limitée sur les minéraux des roches. Le NO et le SO2 montrent une réactivité intrinsèque passant par des dismutations en phase aqueuse ou vapeur induisant une forte altération de la roche par une attaque acide couplée à une oxydation poussée des minéraux constitutifs des roches. Le mélange de gaz montre de la même façon une réactivité double : le S02 s’oxyde en acide sulfurique s’attaquant aux carbonates et minéraux argileux et l’O2 oxyde tous les minéraux possédant du fer ou du soufre réduit. Les gaz annexes contrôlent donc la réactivité des roches en grande profondeur. Leur présence pourrait complètement changer le comportement des roches (porosité, rhéologique) lors du stockage. Leur implication devra être anticipée dans chaque cas concret de stockage en fonction de la composition du gaz d’injection, de la minéralogie et des propriétés pétrophysiques des roches. / Capture and geological storage of CO2 are an main option to limit GHEG emissions of industrial poles and power plants. The captured gases are not constituted by pure CO2 but contain a fraction (until 10 %) of other gases : Ar, N2, SOx and NOx. Most of these gases are highly reactive and could have a strong influence on physical and chemical conditions of the milieu and on the environmement if contamination of neighbour aquifers occurs by leakages. Several laboratory experiments investigated the reactivity of carbonated reservoir and cap rocks from the Aquitaine Basin as well as the reactivity of synthetic mineralogical blends in geologically relevant P-T conditions. The rocks, associated to brine, were altered in presence of various gaseous components at 100 bar and 150°C during one month : pure CO2, pure SO2, pure NO and a CO2 mixture containing fractions of Ar, N2, SO2 and O2. Each experiment was compared with a blank in which the initial gas was replaced with pure N2. Pure CO2 show a limited reactivity on the rocks. NO and SO2 show a intrinsic reactivity by disproportionations in aqueous or vapour phases implying a high alteration of rocks by compled acid – base and oxidation mechanisms. The gas mixture show also a double reactivity : SO2 is oxidized in sulphuric acid dissolving carbonates and clay minerals and O2 oxidizes all reduced mineralogical phases. These gases even in limited fractions control the reactivity of rocks. Their presence could change the behaviour of the rock toward gas and induce positive as well as negative transformations. Their implication must be checked for each geological storage as a function of gas composition, mineralogy and petrophysical.

Fluorescent labeling is a method used for visualization of various types of biomolecules including proteins and protein complexes. However, the effect of protein labeling on protein structure and functions has not been investigated so far. The goal of the diploma thesis was to examine an influence of NHS-fluorescein binding on structure and function of human carbonic anhydrase I (hCA-I). The particular aims of this work were to prepare recombinant 15N-hCA-I which was used for NMR structure analysis of carbonic anhydrase upon fluorescent labeling. Furthermore, enzyme activity was measured in order to find out a correlation between the concentration of NHS- fluorescein and protein function. In addition, the reaction mixtures were systematically analyzed by ESI FT-ICR mass spectrometry. The analysis revealed experimental conditions for fluorescent labeling of human carbonic anhydrase I with minimal effect on protein structure and function. The results of this study show that the calculation of molar excess of NHS-fluorescein cannot rely on a simple procedure provided by manufacturer. However, due to decrease of enzyme activity upon fluorescent labeling, it is better to take into count the influence of NHS-fluorescein concentration on the relative enzymatic activity. Moreover, the calculation of molar...

Les plateformes carbonatées sont typiquement caractérisées par une architecture sédimentaire et stratigraphique complexe qui s’exprime à une échelle qui peut dépasser le simple affleurement. Ce travail est centré sur les dépôts Barrémien (Crétacé inférieur) de la falaise de Gresse-en-Vercors (sud-est de la France) qui nous procure une fenêtre d’observation à l’échelle de la sismique à travers une bordure de plateforme – analogue des réservoirs du Moyen Orient - idéale pour étudier en continu et à grande échelle le développement des plateformes carbonatées. Cette falaise de 500 m de haut pour 25 km de long permet d’étudier la transition entre les dépôts de peu profonds de la plateforme et ceux du bassin. De nouvelles données biostratigraphiques montrent que la série de plate-forme de Gesse-en-Vercors est essentiellement Barrémien inférieur. Quatre séquences stratigraphiques ont été définies, avec deux épisodes complets de plateforme, séparés par trois « drowning ». Les nouvelles données numériques hautes résolutions (nuage de points LIDAR et photos géoréférencées hautes résolutions) acquises par hélicoptère permettent la réalisation d’un DEM 3D haute résolution pour l’ensemble de l’affleurement. L’intégration des observations stratigraphiques et du DEM dans gOcad abouti à la création d’un modèle 3D en continu de l’architecture stratigraphique et de la répartition des facies de l’affleurement qui peu être utilisé pour interprétations stratigraphiques et sédimentologiques. Le modèle géologique qui en résulte démontre que les données numériques d’affleurement et la modélisation géologique en 3D sont des outils pertinents pour tester la caractérisation des affleurements carbonatés et les modèles conceptuels de système de plateformes carbonatées. Il permet d’appréhender les variations subtiles de profils sédimentaires et d’établir une mosaïque de facies à haute résolution tout au long de la plateforme à l’échelle de la sismique. Cette approche est particulièrement critique en ce qui concerne la caractérisation 3D des clinoformes et des cortèges de dépôts sédimentaires dans un modèle non cylindrique tel que la plateforme carbonaté : par exemple, un prisme de bas niveau apparent ou des lobes distaux qui « onlappent » en 2D correspondent en réalité à des progradations en contexte de haut niveau en 3D. / Carbonate platforms are characterized by complex sedimentary and stratigraphic architectures that can be expressed at length scale exceeding single outcrops. This work focuses on the Barremian (Lower Cretaceous) deposits of the Gresse-en-Vercors cliff (southeastern France) that provide a seismic-scale slice though a platform margin - analogous to Middle East reservoirs - ideal to study large scale carbonate platform developments in continuous. The cliffs are 500 m high and extend for 25 km along depositional dip, straddling the transition from shallow water platform to deeper basin. New biostratigraphical data shows that the Vercors platform is mainly Lower Barremian. Four stratigraphic sequences were defined, with two complete platform stages, separated by three drowning events.New high-resolution numerical data (LIDAR point-set and high-resolution georeferenced photos) obtained by helicopter survey, allowed the realization of a 3D high-resolution DEM over the entire outcrops. Integrating the stratigraphic observations and the DEM in gOcad result in a continuous 3D stratigraphic architecture and facies model of the carbonate outcrop that can be used for stratigraphic and sedimentological interpretations. The resulting geological model demonstrates that outcrop numerical data and 3D geological modeling are pertinent tools for improving carbonate outcrop characterization and conceptual models of carbonate platform systems. It allows to establish subtle sedimentary profiles and high resolution facies mosaic along seismic scale platform trend. This approach is particularly critical for the 3D characterization of clinoforms and stratigraphic system tracts in non-cylindrical carbonate systems: for example, apparent low stand wedge or distal onlapping lobes in 2D are in reality prograding high stand systems in 3D.

The aim of this work was to develop a solid knowledge on formulation effects controlling offset ink-paper coating adhesion and to identify key factors of the coating and printing process affecting it. Focus lay on comprehending the impact of pigment dispersant on ink-paper coating adhesion and ultimately on the print quality of offset prints. The work covers laboratory studies, a pilot coating trial designed to produce coated material with a span in surface chemistry and structure, and an industrial offset printing trial. The lab scale studies quantified ink-paper coating adhesion failure during ink setting with a developed laboratory procedure based on the Ink-Surface Interaction Tester (ISIT) and image analysis. Additional polyacrylate dispersant resulted in slower ink setting and reduced ink-paper coating adhesion, with a dependence on its state of salt neutralisation and cation exchange, mainly in the presence of moisture/liquid water. The industrial printing trial on pilot coated papers was designed to study how these laboratory findings affected full scale offset print quality. These trials confirmed the dispersant-sensitive effect on ink-paper coating adhesion, especially at high water feeds. Evaluation of prints from the printing trial resulted in two fundamentally different types of ink adhesion failure being identified. The first type being traditional ink refusal, and the second type being a novel mechanism referred to as ink-lift-off adhesion failure. Ink-lift-off adhesion failure occurs when ink is initially deposited on the paper but then lifted off in a subsequent print unit. In this work, ink adhesion failure by this ink-lift-off mechanism was observed to occur more often than failure due to ink refusal. Print quality evaluation of the industrial prints suggested that water induced mottle was caused by a combination of ink-surface adhesion failure, creating white spots on the print, together with variation in ink layer thickness due to emulsified ink. / <p>QC 20161019</p>

La mécanique des fluides numérique (CFD) est utilisée pour modéliser la précipitation du carbonate de baryum dans un réacteur à lit fluidisé. L’étude est divisée en deux parties : la modélisation de l’hydrodynamique du réacteur et la modélisation de la précipitation du carbonate de baryum. Pour ces deux parties, les modèles sont validés par l’expérience. Dans la première partie de l’étude, des réactions instantanées de neutralisation en absence et en présence de particules solides inertes sont mises en œuvre dans le réacteur à lit fluidisé. Pour représenter la réaction chimique dans la phase liquide, plusieurs modèles son testés : le modèle Eddy Dissipation (EDM), le modèle Eddy Dissipation Concept (EDC) et le modèle modifié Eddy Dissipation- Multiple Time Scale turbulent mixer (EDM-MTS). Le modèle qui donne la meilleure prédiction de la réaction chimique est choisi : il s’agit du modèle EDM-MTS, qui demande aussi le moins de temps de calcul. Dans la deuxième partie, l’équation de bilan de population est incorporée au code de calcul pour prédire la distribution de taille des particules (PSD). La méthode des classes est implémentée couplée avec le modèle des écoulements multiphasiques Eulérien-Eulérien, le modèle de turbulence k-e et le modèle EDM-MTS. Les cinétiques de précipitation de BaCO3 sont incluses dans le modèle. Des expériences de précipitation du BaCO3 en réacteur à lit fluidisé permettent de valider le modèle de CFD développé. La PSD donnée par le modèle de CFD est en bonne concordance avec les résultats expérimentaux / Computational Fluid Dynamics (CFD) techniques are used to model the precipitation of Barium Carbonate in a solid-liquid fluidized bed reactor. The study is divided in two sections: The hydrodynamic behavior and the barium carbonate precipitation. The CFD model is validated with experimental results for both cases. In the first part, a neutralization reaction in the fluidized bed column with and without solids is carried out. In order to simulate the liquid phase reaction, the Eddy Dissipation Model (EDM), the Eddy Dissipation - Multiple Time Scale turbulent mixer model (EDM-MTS) and the Eddy Dissipation Concept (EDC) reaction models are tested. The model EDM-MTS is chosen for giving the best approach and for being the less computationally expensive. In the second part, the population balance equation is added to the model in order to calculate the Particle Size Distribution (PSD) in the fluidized bed reactor. The discrete method is chosen to solve the population balance equation coupled with the multi-phase Eulerian-Eulerian model, the k-e turbulence model and the EDM-MST model. The nucleation, growth and aggregation kinetics of BaCO3 are included in the precipitation model. The experimental BaCO3 precipitations realized in a fluidized bed reactor allowed the CFD precipitation model validation. The PSD obtained by CFD are in good agreement with the experimental PSD

[pt] Neste trabalho foi estudada a formação de camadas de produtos de corrosão em dois aços, o API 5L X80 usado para transporte de óleo e gás e o API 5CT utilizado em poço de petróleo case tubing. Foram utilizadas as técnicas de perda de massa e técnicas eletroquímicas tais como resistência a polarização linear RPL, curvas tafel e espectroscopia de impedância eletroquímica EIS foram empregadas para determinar as taxas de corrosão. Os ensaios foram realizados em condições estáticas numa solução de salmoura 3 porcento wt de NaCl sob 55 bar de pressão parcial de CO2 e total de 75bar, tempos de exposição de 7, 15, 21 e 30 dias e temperaturas de 25 Graus Celsius, 50 Graus Celsius e 75 Graus Celsius. Microscopia eletrônica de varredura MEV foi usada para a análise da morfologia. DRX e EDS foram utilizadas para determinar a composição química. As camadas formadas foram avaliadas em função da espessura, morfologia e composição química. Encontrou-se que a 25 Graus Celsius só houve formação de camada de carbonato de ferro após 30 dias de imersão para ambos os aços e que para 50 Graus Celsius e 75 Graus Celsius houve formação de duas camadas para todos os tempos de imersão cuja composição química mostrou o carbonato de ferro FeCO3 como principal produto de corrosão para os dois aços. A condição de teste que apresentou menor taxa de corrosão e maior proteção da camada de carbonato de ferro FeCO3 foi para 75 Graus Celsius e 30 dias de tempo de imersão. Os resultados de RPL e EIS são semelhantes aos obtidos por perda de massa mantendo a mesma tendência de redução com o tempo e a temperatura. / [en] This study evaluated the CO2 corrosion layer formation on the surface of two different steels, the API 5L X80 used for oil and gas transportation and the API 5CT used in oil production (case tubing). Techniques such as weight loss and electrochemical techniques as linear polarization resistance (LPR), Tafel curves, electrochemical impedance spectroscopy (EIS) were employed to determine the corrosion rate. Tests were conducted under static conditions in a brine 3 percent wt solution of of NaCl under CO2 partial pressure of 55 bar and total of 75 bar, immersion times of 7, 15, 21 and 30 days and temperatures of 25 Celcius, 50 Celcius and 75 Celcius. Analysis of the scale morphology was carried out by Scanning Electron Microscopy (SEM), and X-ray Diffraction. (XRD) and Energy Dispersive Spectroscopy (EDS) were used to determine the chemical composition. The layers formed were evaluated as a function of its thickness, morphology and chemical composition. It was found out that at 25 Celcius only after 30 days of immersion there was iron carbonate layer formation for both steels and at 50 Celcius and 75 Celcius there was the growth of two layers for all immersion times, being the chemical composition of these layers identifyed as iron carbonate FeCO3 as the main corrosion product for the two steels. The lowest corrosion rate and most protective layer of iron carbonate FeCO3 was for the condition at 75 Celcius and 30 days of immersion. The results obtained of LPR and EIS were similar to those obtained by mass loss showing the same tendency, reducing with time and temperature.