Les microbialithes sont des dépôts organosédimentaires benthiques résultant de la minéralisation et de la lithification de tapis microbiens, et dont les plus anciennes formes, se développant il y a 3.4 Ga, constituèrent les premiers écosystèmes terrestres. Ils forment alors une archive sédimentaire unique incluant des périodes clés de l’histoire géologique. Ce travail de thèse se propose d’analyser et de comparer les processus et produits de minéralisation dans les tapis microbiens actuels de deux environnements contrastés : un exemple de lac intracontinental hypersalin, le Grand Lac salé (GSL) aux USA ; une lagune hypersaline à alimentation marine, à Cayo Coco (Cuba) (CCLN). Le devenir des minéraux au cours de la diagenèse précoce, ainsi que leur potentiel d’enregistrement de biosignatures seront particulièrement analysés. Cette thèse se focalisera spécialement sur l’influence de trois facteurs majeurs contrôlant la minéralogie et la fabrique des microbialithes : (i) le rôle de la chimie du milieu (ii) le rôle des métabolismes microbiens (le moteur de l’alcalinité) ; (iii) le rôle de la production et de la dégradation des matrices organiques extracellulaires (EOM). Les deux cas d’études démontrent un rôle prépondérant de la production d’EOM par les cyanobactéries et leur dégradation par les bactéries hétérotrophes dans la minéralisation : (1) Dans les deux systèmes, la première phase minérale a précipiter sur les EOM alvéolaires est une phase riche en magnésium et en silicium. Ce type de minéraux nécessite des pH>8.6-8.7 pour cristalliser. (2) Une autre observation commune est que les carbonates cristallisent souvent dans des zones de forte activité des bactéries sulfato-réductrices (SRB). Notre hypothèse est que les SRB dégradent les EOM, libérant des cations (Mg2+ et Ca2+) disponibles pour la cristallisation des carbonates. Dans les tapis du CCLN et contrairement au GSL, nos résultats démontrent une forte activité de photosynthèse anoxygénique par les bactéries pourpres sulfureuses (PSB). La limite entre la zone oxique et la zone anoxique est caractérisée par un pH maximum et coïncide avec la formation d’une lamine de carbonates. Deux différences majeures sont observées entre les paragenèses du GSL et du CCLN : (1) le locus initial de la précipitation des carbonates. Dans le GSL, l’aragonite précipite dans les cyanobactéries, perminéralise leur paroi et enfin la matrice organique. Pour Cuba, une calcite magnésienne péloïdale précipite sur les EOM puis rempli les bactéries ; (2) la minéralogie et l’évolution des carbonates lors de la diagenèse précoce. Les microbialithes du GSL montrent une aragonite partiellement dissoute et une dolomite venant se développer à sa périphérie. Au CCLN, de l’aragonite se développe en surcroissance des peloïdes de HMC précédemment formés. Les différences minéralogiques des carbonates entre les deux systèmes pourraient s’expliquer par un changement du rapport Mg/Ca. Les résultats pourront être utilisés afin de mieux interpréter les conditions paléoenvironnementales et les processus microbiens en jeu dans des microbialithes de registres fossiles analogues. / Microbialites are benthic organosedimentary deposits resulting of the mineralization and lithification of the microbial mats, and the most ancient forms, developing there are 3.4 Ga, are the first earthly ecosystem. They form a unique sedimentary archive including key periods of the geological history. This study proposes to analyze and compare the processes and the products of mineralization in the modern microbial mats of two different environments: an example of intracontinental modern lake, the Great Salt Lake (USA; GSL); a lagoonal marine sea fed in Cayo Coco (Cuba; CCLN). The mineral product during of the primary diagenesis, as that them potential of biosignatures recording will be particularly detailed. This work will focus on the influence of three major factors controlling the mineralogy and the fabric of the microbialites: (i) environment chemistry role, (ii) microbial metabolisms role, (iii) role of the production and degradation of the extracellular organic matrix (EOM). Both environments studied show a high role of the EOM production by cyanobacteria and them degradation by the heterotrophic bacteria in the mineralization: (1) In both systems, the first phase to precipitate on the alveolar EOM is a rich magnesium and silica phase. This type of mineral needs pH around 8.6/8.7 to precipitate. (2) An other common observation is that carbonate precipitate generally in the high sulfate-reducing activity zones. Our hypothesis is that the sulfato-reducing bacteria (SRB) degrade the EOM, releasing cations (Mg2+ and Ca2+) available for carbonate crystallization. The limit between the oxic and anoxic zones is characterized by maximum pH coinciding with the precipitation of carbonate lamina. Two mains differences have been observed between the paragenesis both systems: (1) initial locus of the carbonate precipitation. In the GSL, the aragonite precipitates in the bacteria and then permineralizes the wall of bacteria and then the EOM network. In Cuba, the peloidal magnesian calcite precipitates on the EOM then fill the bacteria; (2) the mineralogy and the evolution of the carbonate during the preliminary diagenesis. The microbialithes of GSL show the aragonite partly dissolved and a dolomite developing next to the aragonite. In the CCLN, aragonite developing around the magnesian calcite peloids. The mineralogical carbonate differences between both systems could explain by a change of the Mg/Ca. The results could be used to better understand and interpret the paleoenvironmental conditions and the microbial processes stake in ancient microbialite analogs.

<p> The Morrissey Formation of the Kootenay Group was mapped and sampled in three outcrops in southwestern Alberta and southeastern British Columbia; Burnt Ridge and Sparwood Ridge in British Columbia and Adanac Mine sight in Alberta. </p> <p> The lowest unit mapped was within the upper Fernie Formation (Passage beds) and consists of interbeds of sandstone and siltstone that were deposited as shallow water marine sediments. </p> <p> The Morrissey Formation conformably overlies the Fernie Formation and contains two members; the Weary Ridge Member and the Moose Mountain Member. The Weary Ridge Member consists of fine to medium grain, parallel and trough crossbedded sandstone, that was deposited as a delta-front-sand facies produced by coalescing of delta-sands from three to four delta complexes. The overlying Moose Mountain Member consists of high angle trough crossbedded, coarse grain, "salt and pepper" sandstone representing a distributary mouth bar environment. The Moose Mountain Member is unconventional in that the upper portion contains two units not seen in other sections. A marine trace fossil unit and a beach unit are both found within the upper portion of the member. These two units represent a transgression caused by channel switching and a regression and reworking of sediments into a beach respectively. </p> <p> Above the Morrissey Formation are the continental coals and fluvial systems of the Mist Mountain Formation. </p> <p> Petrographic studies on twenty five thin sections show two sedimentary sources for the Formation. The first source being chert rich Upper Paleozoic carbonates and the second source is Lower Paleozoic clastics that have previously been derived from a metamorphic complex of the Canadian Shield. The sandstones are cemented by quartz syntaxial overgrowths implying that there was a moderate degree of pressure solution, indicating a fairly high overburden pressure during diagenesis. </p> / Thesis / Bachelor of Science (BSc)

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The THEREDA model has been extended by phases and species formed within the title system. A temperature range of 0 °C to 100 °C is considered. Most of the solubility products, Pitzer parameters and association constants were adapted from the model of Königsberger et al. (Königsberger, E., Königsberger, L.-C., Gamsjäger, H.: Low-temperature thermodynamic model for the system Na2CO3−MgCO3−CaCO3−H2O. Geochim. Cosmochim. Acta, 63, (1999), pp. 3105–3119, DOI 10.1016/S0016-7037(99)00238-0). Literature on solubility data of carbonates of magnesium and calcium is critically evaluated. As far as experimental solubility data were available, they were compared with model calculations. The data comprise the minerals magnesite (MgCO3), nesquehonite (MgCO3∙3H2O), lansfordite (MgCO3∙5H2O), hydromagnesite (4MgCO3∙Mg(OH)2∙4H2O), dypingite (4MgCO3∙Mg(OH)2∙5H2O), calcite (CaCO3), aragonite (CaCO3), vaterite (CaCO3), ikaite (CaCO3∙6H2O), dolomite (MgCO3∙CaCO3), huntite (3MgCO3∙CaCO3), magnesian calcite (solid solution between CaCO3 and MgCO3), eitelite (Na2CO3·MgCO3), pirssonite (Na2CO3·CaCO3·2H2O), gaylussite (Na2CO3·CaCO3·5H2O), natrite (Na2CO3), thermonatrite (Na2CO3·H2O), Na2CO3·7H2O, natron (Na2CO3·10H2O), nahcolite (NaHCO3), wegscheiderite (Na2CO3·3NaHCO3) and trona (Na2CO3·NaHCO3·2H2O). There are minerals known as artinite (MgCO3∙Mg(OH)2∙3H2O) or barringtonite (MgCO3·2H2O), for which no solubility data exist. The literature survey also covers geochemical observations on the existence of carbonate minerals, laboratory investigations on the decomposition, formation and conversion as well as spectral and XRD characterization of carbonate phases. For important minerals, such as magnesite or hydromagnesite, the uncertainty of the solubility constants is large. The added Pitzer parameters, concern the binary cation - carbonate, cation - hydrogen carbonate and the ternary interactions, including mixing parameters of the anions HCO3-, CO32- and OH-. Mixing parameters of these anions with chloride or sulfate are not considered in this work. From the data situation and the modelling results, conclusions are drawn with respect to future experimental work to obtain more reliable equilibrium data.

The Chatham Islands are located in the SW Pacific Ocean, approximately 850 km to the east of the South Island of New Zealand. This small group of islands is situated near the eastern margin of the Chatham Rise, an elongated section of submerged continental crust that represents part of the Late Paleozoic-Mesozoic Gondwana accretionary margin. The location and much of the geology of the Chatham Islands are attributed to intra-plate basaltic volcanism, initiated during the Late Cretaceous, in association with development of a failed rifting system to the south of the Chatham Rise. Despite the volcanic nature of much of the geology, the majority of the Cenozoic sedimentary stratigraphic record on the islands comprises non-tropical skeletal carbonate deposits whose deposition was often coeval with submarine volcanics and volcaniclastic deposits. This has resulted in complex stratigraphic relationships, with the volcanic geology exerting a strong influence on the geometry and distribution of the carbonate deposits. These limestones, despite some general field descriptions, have been little studied and are especially poorly understood from a petrographic and diagenetic perspective. The carbonate geology in detail comprises eleven discrete limestone units of Late Cretaceous through to Pleistocene age which were studied during two consecutive field expeditions over the summers of 2005 and 2006. These limestone occurrences are best exposed in scattered coastal outcrops where they form prominent rugged bluffs. While many of the younger (Oligocene to Pliocene) outcrops comprise of poorly exposed, thin and eroded limestone remnants (it;5 m thick), older (Late Paleocene to Early Oligocene) exposures can be up to 100 m in thickness. The character of these limestones is highly variable. In outcrop they display a broad range of textures and skeletal compositions, often exhibit cross-bedding, display differing degrees of porosity occlusion by cementation, and may include rare silicified horizons and evidence of hardground formation. Petrographically the limestones are skeletal grainstones and packstones with a typical compositional makeup of about 70% skeletal material, 10% siliciclasts, and 20% cement/matrix. Localised increases in siliciclastics occur where the carbonates are diluted by locally-derived volcaniclastics. The spectrum of skeletal assemblages identified within the Chatham Island limestones is diverse and appears in many cases to be comparable to the bryozoan dominant types common in mainland New Zealand and mid-latitude Australian cool-water carbonates in general. However, some key departures from the expected cool-water carbonate skeletal makeup have been identified in this study. The occurrence of stromatolitic algal mats in Late Cretaceous and Early Eocene carbonate deposits indicates not cool-temperate, but certainly warm-temperate paleoclimatic conditions. A change to cool-temperate conditions is recorded in the limestone flora/fauna from the mid-Late Miocene times following the development and later northward movement of the Subtropical Front. An uncharacteristic mix of shallow-shelf (bryozoans) and deeper water fauna (planktic foraminifera), together with their highly fragmented and abraded nature, is indicative of the likely remobilisation and redistribution of carbonate, primarily during episodic storm events. The Chatham Islands limestones formed within the relative tectonic stability of an oceanic island setting, which was conducive to ongoing carbonate accumulation throughout much of the Cenozoic. This contrasts markedly with other mainland New Zealand shelf carbonates which formed over sporadic and short-lived geological periods, experiencing greater degrees of burial cementation controlled by a relatively more active tectonic setting. As a consequence of the tectonically stable setting, the Chatham Islands limestones have experienced little burial and exhibit a paucity of burial cementation effects. They remain commonly soft and friable. Detailed petrographic investigations have shown the limestones are variably cemented by rare uneven acicular spar fringes, poorly to well-developed syntaxial rim cements about echinoderm fragments, and equant/blocky microsparite. Staining of thin sections and cathodoluminescence petrography show these spar cement generations are non-ferroan and their very dull- to non-luminescent nature supports precipitation from Mn-poor oxygenated waters, likely of an either meteoric or combined marine/shallow burial origin. Micrite is the dominant intra- and inter-particle pore fill and occurs both as a microbioclastic matrix and as precipitated homogenous and/or micropeloidal cement. The rare fringing cements often seen in association with homogenous and/or micropeloidal micrite may be indicative of true early marine (seafloor) cement precipitation and localised hardground development. An interesting feature of the geology of the Chatham Islands is the occurrence of carbonate material within sedimentary dykes. The locations of the dykes are in association with volcanic and volcaniclastic deposits. Similarities between dyke characteristics at Red Bluff on Chatham Island with mainland occurrences from East Coast and Canterbury Basins (North and South Islands, respectively) on mainland New Zealand have been recognised. They show complex structures including sidewall striations, internal flow structures as revealed by grain sorting, and extra-clast inclusions of previous fill lithologies which are characteristic of carbonate injection. This is in contrast to other dykes which are known to be of a passive fill origin. Multiple phases of carbonate sediment injection can be recognised by crosscutting relationships enabling the determination of a parasequence of events. Possible injection mechanisms are most likely associated with sediment overloading or hydrothermal pressurisation associated with emplacement of submarine volcanics. The Chatham Islands provide an exciting example of a geologically unique and complex non-tropical carbonate depositional setting. The production of carbonates is controlled by volcanic and volcaniclastic sediment input with the types of carbonate deposits and water depth variations related to thermal uplift/subsidence in association with global eustatic sealevel and temperature changes associated with development of Southern Ocean water fronts from the Late Cretaceous-Cenozoic. Carbonate deposition on the Chatham Islands is considered to relate to a rather variable and small scale oceanic, high energy, cool-water carbonate ramp setting whose geometry was continually evolving/changing as a consequence of periodic volcanic episodes.

From the Proceedings of the 1971 Meetings of the Arizona Section - American Water Resources Assn. and the Hydrology Section - Arizona Academy of Science - April 22-23, 1971, Tempe, Arizona / The 2 major environmental problems of Arizona and the southwest are the alkalinization of soil and water by irrigation and air pollution from copper smelting. It is proposed that the amelioration of both problems may be solved through a common process. This is the production of sulfuric acid from sulfur dioxide, which is the main pollutant of smelter effluent gases. The conversion process is cheap and easy, and the sulfuric acid could then be added to irrigation waters to increase the solubility of CA carbonate in the soil, thereby decreasing alkalinity. Lower alkalinity results in increased soil permeability and increased water use efficiency by plants. The potential market for sulfuric acid in irrigation was calculated, on the basis of neutralizing 90% of the bicarbonate ion concentration in Colorado River water and Arizona well water, to be about 1.6 million tons annually, representing about 1/3 of the sulfur now dissipated by smelters as air pollution. This market includes both the Imperial Valley of California and the Mexicali Valley of Mexico, both of which are currently experiencing mounting salinity problems. Salinity itself is not amenable to this treatment, but the cumulative increase in NA and bicarbonate may be slowed and reversed, leading to gradual soil stabilization.

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No description available.

Cette thèse se positionne dans le domaine des batteries lithium-ion. Elle a pourobjectif de mieux comprendre le fonctionnement de l’électrode négative de graphiteen étudiant le processus de formation du film de passivation, couramment appeléSEI (Solid Electrolyte Interface) créé à l’interface avec l’électrolyte. Ce travail nousa conduit à proposer des modèles pouvant expliquer comment se forme la SEI et àidentifier les phénomènes qui entrent en jeu dans le fonctionnement de la batterie.La SEI résulte de la réaction entre l’électrode de graphite, les ions lithium et les moléculesorganiques de l’électrolyte qui survient lors du premier processus d’insertion.Elle est principalement composée des produits de décomposition de l’électrolyte etles ions lithium consommés ne sont plus échangeables. Elle est donc responsable dela capacité irréversible observée lors du premier cycle de formation, correspondantà la différence de capacité entre le processus d’insertion et le processus de désinsertion.Il est donc essentiel de mieux comprendre les paramètres qui l’influencentpour pouvoir ainsi la contrôler et limiter la perte irréversible de capacité. Les performancesen capacité de l’élément lithium-ion sont directement liées à cette valeurde capacité irréversible, elle doit être limitée afin de maximiser la quantité d’ionslithium échangée entre l’électrode négative et l’électrode positive. La stabilité dela SEI conditionne ensuite le comportement en cyclage de l’électrode au cours dutemps.Dans ce mémoire de thèse, nous avons choisi de caractériser le comportement del’électrode de graphite en faisant varier la nature de l’électrolyte et la taille desparticules de graphite tout en restant le plus proche possible du fonctionnementd’une vraie batterie. Au travers des techniques de caractérisations électrochimiques(cyclage galvanostatique, spectroscopie d’impédance) associées à des techniques decaractérisation de surface (spectroscopie de photoélectrons X, microscopie électroniqueà balayage), les résultats obtenus ont permis de proposer un nouveau modèlede formation de la SEI.Pour l’électrolyte, nous avons choisi de ne regarder que l’effet du solvant (le carbonatede propylène) et de l’additif (le carbonate de vinylène). Ces deux composésentrent dans la composition des électrolytes utilisés dans les éléments lithium-ioncommerciaux. Pour l’électrode de graphite, le choix des particules s’avère primordialpuisque chaque type de particules possède une chimie de surface spécifique (plans223basaux ou plans prismatiques) susceptible de réagir différemment vis-à-vis de l’électrolyte.Deux particules de graphite, de taille et de morphologie différentes, ont étéétudiées. Elles sont utilisées séparément en tant que matière active dans les électrodesnégatives des batteries lithium-ion. Notre spécificité est d’avoir préparé desélectrodes constituées par un mélange de ces deux particules et de les avoir ensuitecaractérisées en formation. L’application de conditions de fonctionnement différentescomme le régime de cyclage et la température d’essai ont mis en évidence les valeursidéales conduisant à minimiser la dégradation de l’électrolyte et à optimiser laqualité du film.Nous avons abouti, au travers de l’ensemble des méthodes de caractérisations misesen oeuvre, à une meilleure compréhension des mécanismes de formation du film depassivation permettant ainsi d’améliorer cette étape essentielle à la pérennité desperformances de l’électrode dans le temps. Ce travail a donc un réel impact auniveau industriel. Le modèle de formation proposé apporte un éclairage nouveau auprocessus de formation et peut permettre également d’aider en amont à la fabricationdes particules de graphite. / This work relates to the lithium ion battery field. The purpose of this study is tobetter understand the behavior of graphite electrodes by focusing on the formationof a passive layer named Solid Electolyte Interface (SEI) which is formed at thegraphite/electrolyte interface. This work has led us to put forward models whichcan explain the SEI formation and identify the reactions which take place in alithium ion battery.The SEI results from reactions between graphite electrode, lithium ions and organicmolecules from the electrolyte during the first charge of the lithium ion battery. It ismainly composed of decomposition products from the electrolyte. Consumed lithiumions can no longer be used in the next cycle. The SEI is therefore responsible for theirreversible capacity during the first formation cycle which is the charge loss betweenthe intercalation process and the deintercalation process. It is necessary to betterunderstand the impact of the formation conditions and other parameters in orderto control and limit the irreversible charge loss. Lithium ion battery performancesdepend on this irreversible capacity, this value has to be reduced in order to maximizethe amount of exchanged lithium ions between negative and positive electrodes. TheSEI stability will determine the electrode behavior upon cycling.In this thesis, we chose to study the graphite behavior by testing several electrolytecompositions and graphite particle sizes in electrochemical cells similar to areal battery. Electrochemical techniques (galvanostatic cycling and electrochemicalimpedance spectroscopy) and surface analyses (X-ray photoelectron spectroscopy,scanning electron microscopy) will be combined. These results helped us to developa new model of the SEI formation.For the electrolyte, we chose to study the effect of the solvent (propylene carbonate)and the additive (vinylene carbonate). Both components are commonly used inthe electrolyte for commercial lithium ion batteries. For the graphite electrode, thechoice of graphite particles is essential because each graphite family has its ownsurface chemistry (basal and prismatic surfaces) which can react in many wayswith the electrolyte. Two graphite particles, with specific sizes and morphologiesare studied. They are separately used as active materials for negative electrodes inlithium ion batteries. Our unique approach is to prepare graphite electrodes basedon a mix of both particles with various compositions and then test the electrode225performances. After testing several formation conditions such as the cycling rateand the temperature, we found the ideal formation conditions for minimizing theelectrolyte decomposition and optimizing the film quality.Finally, based on all the characterization methods, we came to a better understandingof the film formation process. In this way, we have improved this essentialpreliminary step which can now lead to more durable cycling performances overtime. This study can have a major impact on the industrial level. The formationmodel cast a new light on the formation process and can therefore help to makeefficient graphite electrodes.

Le sommet du Frasnien est une époque difficile pour la biodiversité sur la Terre, en particulier pour les organismes d’eaux chaudes et peu profondes. Cette étude vise à établir un lien entre l’activité tectonique et la crise biologique. Trois coupes d’Amérique du Nord, de la marge ouest du paléocontinent Laurentia, liées au front orogénique Antler ont été étudiées pour leurs rapports isotopiques 87Sr/86Sr dans les carbonates. La coupe de Devils Gate dans le centre Nevada (USA) présente au sommet du Frasnien des faciès de turbidites carbonatées de bassin. Trois pics successifs de 87Sr/86Sr s’observent au sommet du Frasnien, entre le deux niveaux anoxiques Kellwasser. Le dernier pic est le plus élevé, il est contemporain du début du second Kellwasser et présente un rapport isotopique de 0,7094. La coupe de North Antelope Range proche de celle de Devils Gate, présente des dépôts extrêmement homogènes et réguliers de “debris-flow” carbonatés dans un bassin d’avant-pays. Un pic du 87Sr/86Sr plus modéré y est enregistré. La coupe de Mount Cinquefoil est située dans l’Alberta (Canada), dans un contexte de rampe formant une transition entre un important complexe récifal et un bassin. A nouveau un pic de 87Sr/86Sr est enregistré au début de l’événement anoxique alors que le reste de la coupe est fort homogène. Un autre pic important du 87Sr/86Sr est présent dans la partie inférieure de la coupe à la base du premier niveau Kellwasser identifié par l’étude sédimentologique. Les différents pics du 87Sr/86Sr enregistrés dans la Zone à conodontes linguiformis sur les trois coupes présentent des points communs. D’une part ils occupent la même position par rapport à la courbe de susceptibilité magnétique enregistrée dans les trois coupes, ce qui tend à montrer qu’ils sont contemporains. D’autre part ils sont systématiquement liés à des teneurs plus fortes en éléments (Al, Ti, Si, ) de la phase détritique dans les roches, ce qui permet d’établir un lien direct entre l’activité tectonique régionale, l’érosion continentale accentuée et les rapports isotopiques élevés du Sr. De plus ces pics du 87Sr/86Sr semblent liés à la mise en place des périodes d’anoxie des horizons Kellwasser par eutrophisation des eaux. La chemostratigraphie permet de reconnaître des phases bien distinctes de la sédimentologie détritique, en lien avec le contexte tectonique de chaque coupe. Enfin, la comparaison avec d’autres données de la littérature pose la question de la simultanéité des événements à la surface de la Terre. / Doctorat en Sciences / info:eu-repo/semantics/nonPublished