La carbonatation atmosphérique est un des facteurs parmi les plus importants de la durabilité du béton armé. Elle repose sur l'action du CO2 de l'atmosphère qui diffuse à travers le béton et se dissout en acide au contact de la solution interstitielle. Cette acidification du milieu induit une dissolution de la portlandite qui constitue la réserve de basicité du béton. La baisse du pH, d'une valeur de l'ordre de 13 à une valeur inférieure à 9, peut conduire à la corrosion des aciers du béton armé qui ne sont passivés et protégés qu'en milieu fortement basique. L'objectif de la thèse est de construire un modèle physico-chimique de carbonatation des matériaux cimentaires permettant de prédire la chute du pH de la solution interstitielle, variable pertinente pour appréhender la corrosion des armatures. Une riche campagne d'analyses thermogravimétriques, de gammadensimétries et de porosimétries par intrusion de mercure, réalisées sur 3 bétons différents et plusieurs pâtes de ciment à base de CEM I, permet de comprendre les mécanismes physico-chimiques, de déterminer les conséquences de la carbonatation sur la microstructure et l'état hydrique des matériaux, de calibrer et enfin de valider le modèle proposé à partir d'essais de carbonatation accélérée.

This study uses a new integrated outcrop data and airborne lidar from Slaughter Canyon, New Mexico, to quantitatively characterize the cycle-scale facies architecture within the G23-G26 high frequency sequences of the Yates Formation. High frequency cycle-scale mapping of these sequences shows sedimentological evidence for accommodation reduction associated with the Permain composite sequence (CS) 13 highstand (G23-G25). Development of the G26 HFS additionally demonstrates the isochronous balance of mixed carbonate-siliciclastic deposition across the Yates-Capitan reef-rimmed shelf during the initial CS-scale transgression following significant exposure and bypass of sand across the shelf. This sequence framework is quantitatively analyzed using progradation to aggradation (P/A) ratios, facies proportions, facies tract dip width, and facies tract bedding angles to evaluate the interplay of eustacy and syndepositional deformation as drivers of stratigraphic architecture. The sequences defined here developed in response to both eustacy and syndepositional deformation, but individual facies distributions and cycle stacking patterns were largely controlled by eustacy; while facies, cycle, and sequence thicknesses as well as facies bedding angles were locally influenced by syndepositional faulting. A reconstruction of each high frequency sequence and stepwise documentation of post-depositional fault displacement and HFS basinward rotation was generated using the lidar data. This analysis shows that the G23-G26 HFS developed basinward-dipping depositional topography from the shelf crest to the shelf margin reef. This geometry was largely unaltered by syndepositional faults during individual HFS deposition, but was rotated basinward shortly thereafter by younger fault movement. The accommodation trends recorded in this largely shelf crest to shelf margin window can be additionally projected into the middle shelf producing zones of the prolific Yates-aged reservoirs on the Northwest Shelf and Central Basin Platform. / text

Les proazaphosphatranes sont des entités phosphorées bicycliques superbasiques également connues sous le nom de superbases de Verkade et les azaphosphatranes constituent leurs acides conjugués. Les travaux de cette thèse porte sur l'étude des propriétés de ces molécules en milieu confiné. Premièrement, le confinement des superbases a été étudié au sein de structure de type hémicryptophane (molécules possédant des cavités dissymétriques formées à partir d'une unité cyclotrivératrylène et d'une seconde unité de symétrie C3). Une modulation de la basicité a pu être notamment observée dans les différentes structures étudiées possédant des tailles de cavité différentes par comparaison avec les superbases modèles dépourvues de cavité. L'activité catalytique d'une superbase encagée a pu être testée dans deux réactions de catalyse nucléophile et basique. Puis les azaphosphatranes, acides faibles aux stuctures robustes, jusque-là peu utilisés en organocatalyse ont été valorisés pour la synthèse de carbonates cycliques à partir d'époxydes et de dioxyde de carbone (CO2). Un effet sur la stabilité des catalyseurs encagés a pu être démontré. Enfin un catalyseur hétérogène a pu être mis au point par immobilisation d'un azaphosphatrane sur silice mésoporeuse de type SBA-15.

Dans les eaux naturelles ou bien dans les eaux en cours de traitement, de nombreux processus peuvent générer des espèces réactives telles que de l'oxygène singulet, des ions superoxydes,des radicaux hydroxyles, ou bien d'autres oxydants. Dans les eaux naturelles, ces processus impliquent les substances humiques ou les ions nitrates en présence de lumière et d'oxygène. Dans les eaux en cours de traitement, les procédés d'oxydation avancée sont une source de production de radicaux hydroxyle. D'autres radicaux peuvent ensuite être formés par des réactions secondaires avec la matrice inorganique des eaux. Ces réactions aboutissent à la formation de radicaux inorganiques tels que les radicaux carbonates CO3*- et les radicaux chlores Cl* (atome de chlore). La réactivité de ces derniers est mal connue. Ce travail a pour but d'étudier la réactivité des radicaux carbonates et chlores avec des pesticides de type phénylurées, utilisés comme molécules modèles, et d'identifier les produits de dégradation. Le radical carbonate a été généré par la photolyse de [Co(NH3)5CO3]+, par photosensibilisation à partir de la 4- carboxybenzophenone, de la 1-nitronaphtalène et de la duroquinone et par l'excitation UV du peroxyde d'hydrogène. Le radical chlore a été généré par l'excitation UV du peroxyde d'hydrogène. Les constantes de vitesse de réaction des radicaux carbonates et chlores avec les pesticides étudiés, ont été déterminées, après validation d'une méthode de cinétique compétitive ou par modélisation cinétique. Ces constantes sont comprises pour le radical carbonate dans l'intervalle 0,35-3,5.107 L mol-1 s-1, et dans l'intervalle 1,2-3,9.108 L mol-1 s-1 pour le radical chlore. La comparaison de la réactivité des radicaux carbonates et chlores avec celle des radicaux hydroxyles, indique un facteur de l'ordre de 1000 pour le radical carbonate et de 100 pour le radical chlore, et ceci en faveur de la réactivité des radicaux hydroxyles. Plusieurs produits de dégradation du radical carbonate ont été identifiés. Il s'agit de produits d'hydroxylation du cycle aromatique, des produits issus d'une déméthylation, un dérivé quinone imine pour le fénuron, la cassure du pont dissulfure pour le metsulfuron méthyl. La comparaison des produits de dégradation formés avec les radicaux carbonates et hydroxyles met en évidence certains produits communs aux deux processus tandis que d'autres sont plus spécifiques. Les produits issus du radical carbonate sont moins nombreux en nombre que ceux issus du radical hydroxyle.

Middle Ordovician carbonates in the Lake Simcoe area, south-central Ontario were examined to determine if: (1) The δ18O values of early-stage calcite cement in hardgrounds are useful proxies for Ordovician seawater δ18O values; (2) a regional hydrothermal event affected middle Ordovician strata in the Lake Simcoe area. Whole rock samples of middle Ordovician hardgrounds and immediately overlying limestones containing early calcite cement have δ13C values ranging from -1.7 to +2.9‰ (PDB) and δ18O values ranging from -6.9 to -2.9‰ (PDB). Hardground δ18O values and the similarity of the isotopic composition between the hardgrounds and overlying limestones are consistent with diagenetic alteration during shallow burial, which indicates the hardgrounds are not useful proxies. Late-stage calcite cements have δ13C values from -8.4 to +2.9‰ (PDB) and δ18O values from -11.4 to -6.0‰ (PDB). Late-stage microcrystalline dolomites have δ13C values from -3.9 to +0.4‰ and δ18O values from -10.7 to -7.6‰. Late-stage saddle dolomites have δ13C values from -1.7 to 1.9‰ and δ18O values from -13.8 to -8.5‰. The late-stage carbonate δ18O values are more negative than the early-stage carbonate δ18O values and are interpreted to reflect progressively deeper burial diagenesis. Four types of fluid inclusions were identified in late-stage calcite, saddle dolomite, barite, and quartz. Type 1 inclusions are aqueous liquid-rich with very consistent low to very low vapour-liquid ratios and are of primary, secondary pseudosecondary and indeterminate origins. Type 2 inclusions are aqueous liquid-only and are of primary and secondary origins. Type 3 inclusions are oil-bearing, liquid-rich with low to medium vapor-liquid ratios and are of secondary origin. Type 4 inclusions are vapour-only and are of indeterminate origin. The type 4 inclusions analyzed did not yield any microthermometric data suggesting they are empty cavities that have lost all their fluid. Fluid inclusions of primary, secondary and pseudosecondary origins in calcite, dolomite and quartz have overlapping homogenization temperatures ranging from 43 to 188°C. Fluid inclusions of indeterminate origin in calcite and barite have homogenization temperatures from 80 to greater than 200°C. Petrographic and microthermometric evidence indicates that fluid inclusion homogenization temperatures greater than 150°C most likely are caused by stretching or leaking; therefore, are discounted. Fluid inclusion types 1 and 2 represent two fluid inclusion assemblages (FIA) based on final ice melting temperatures. The high salinity (10 to 30 wt%CaCl2) inclusions in FIA 1 are of primary, secondary, pseudosecondary and indeterminate origin in calcite, dolomite, barite and quartz. Fluid inclusions in FIA 1 are interpreted as reflecting saline basin brines from which the host minerals precipitated during burial diagenesis. The low salinity (0 to 2.7 wt%CaCl2) inclusions in FIA 2 are of secondary and indeterminate origin in calcite. Fluid inclusions in FIA 2 may reflect a meteoric origin such as in a vadose or phreatic environment based on inclusions containing different phases and variable vapor-liquid ratios. Alternatively the low salinity inclusions may reflect alteration from an influx of meteoric fluids that migrated through basement faults and fractures during periods of uplift and erosion. Early and late-stage carbonates from this study precipitated from 18O-depleted pore fluids and/or at progressively higher temperatures accompanying deeper burial. The FIA 1 homogenization temperatures support burial diagenesis at 66 to 80°C if it is assumed the rocks were buried 2 km, the surface temperature was 20°C and the geothermal gradient was between 23 to 30°C/km. An alternative interpretation is mineral precipitation during a regional hydrothermal event. Burial diagenesis does not explain the fluid inclusion homogenization temperatures of 90°C and greater unless geothermal gradients are higher than 35°C/km or burial depth is increased to 3 km or more. However, thermal maturity of organic matter in the Michigan Basin suggests Ordovician strata were never buried more than 2 km. Four models for regional hydrothermal fluid migration are: (1) gravity-driven flow; (2) ‘squeegee-type’ fluid flow; (3) convection cell fluid flow; and (4) structurally-controlled fluid flow. The gravity-driven model relies on continental heat flow and an influx of meteoric water from basin catchment areas. For the ‘squeegee, convection cell and structurally controlled models, hot fluids could have entered the region from several conduits concurrently during episodic reactivation of basement faults and fracture systems in response to intracratonic stresses created by the continuous interaction of tectonic plates. Determining which of the models best explains regional hydrothermal fluid flow in the Michigan Basin is difficult for several reasons; (1) surface temperatures and maximum burial temperatures at the time of mineral precipitation in the Michigan Basin during the Ordovician are unknown; (2) the timing of mineral precipitation in relation to tectonic pulses is undetermined; (3) there is as yet no known deep-seated heat sources in the Michigan Basin for convection to occur; and (4) it is unknown whether advection is a major process in the Michigan Basin. A collaborative multi-disciplinary research project covering geology, geophysics and hydrogeology would provide much more integrated data than is currently available from stable isotopes, fluid inclusions and organic matter.

L'intensification de l'effet de serre due à l'augmentation des concentrations de CO 2 dans l'atmosphère pourrait être plus élevée si ce n'est du rôle important de l'océan en tant que puits pour le CO 2 atmosphérique. Malheureusement, une conséquence de la capacité de l'océan à tamponner le CO 2 est l'acidification des eaux de surface des océans. L'océan Austral est particulièrement vulnérable à ces conséquences en raison de ses basses températures et de sa productivité primaire saisonnière élevée. La présente thèse de doctorat a comme objectif d’analyser le système des carbonates, en particulier l'état de l’acidification des océans, dans le détroit de Gerlache et dans la zone polaire de la région de la Terre Adélie. Ces deux régions présentent des hydrodynamiques différents et, par conséquent, devraient présenter des différences dans la variabilité de leur système carbonaté. À partir des données du programme brésilien NAUTILUS et du programme français MINERVE, la dynamique du système des carbonates a été évaluée dans ces régions de 2015 à 2017. Les résultats sont présentés sous la forme d'articles scientifiques qui ont été assemblés pour structurer cette thèse. Le détroit de Gerlache présentait les plus grandes variations spatiales des propriétés du système des carbonates avec des conditions potentiellement acides durant l'été austral. En comparaison, la zone polaire de Terre Adélie présente des variations interannuelles et spatiales plus importantes associées aux zones frontales. En raison de ses conditions géographiques et hydrodynamiques, le détroit de Gerlache est actuellement plus vulnérable à l'acidification des océans que la région de la Terre Adélie. / The intensification of the greenhouse effect due to increasing atmospheric CO 2 concentrations could be higher if not for the ocean’s important role as a sink for atmospheric CO 2 . A consequence of the ocean’s capacity for buffering CO 2 is the ocean acidification of sea surface waters. The Southern Ocean is particularly vulnerable to these consequences due to its low temperatures and high seasonal primary productivity. The present Ph.D. thesis focus on the analysis of the carbonate system, particularly the ocean acidification state, in the Gerlache Strait and the polar zone off the Adelie Land region. These two regions present different hydrodynamics and, consequently, are expected to present differences in their carbonate system variability. Using data sets from the Brazilian NAUTILUS programme and the French MINERVE programme, the carbonate system dynamic was assessed in these regions from 2015 to 2017. The results are presented as scientific articles, which were assembled to structure this thesis. The Gerlache Strait showed the largest spatial variations of carbonate system properties with potentially acidic conditions during austral summer. In comparison, the polar zone off Adelie Land larger inter-annual and spatial variations associated with frontal zones. Due to its geographical and hydrodynamic conditions, the Gerlache Strait is currently more vulnerable to ocean acidification than the off Adelie Landregion.

Deposition of dispersed phase from flowing dispersions onto a substrate surface is of utmost relevance for various industrial processes like fouling of sparingly soluble salts, such as CaCO3 and CaSO4 in heat exchangers and desalination evaporators which tend to form deposits on flow surfaces of tubes or pipelines conveying hard water and in water filtration and purification processes since concentration of CaCO3 in many natural water resources is equal to or greater than the saturation level. The study of deposition is also of intrinsic interest for biophysics and colloid science where vascular calcification i.e. precipitation and deposition of calcium phosphates (hydroxyapatites) in the muscular layer of the blood reduces arterial compliance and promotes congestive heart failure. Experiments were conducted on straight, circular cross section silica tubing of inner di-ameter (ranging from 0.88 mm to3.40 mm) to study the effect of electrostatic interaction and hydrodynamics on the deposition behavior of CaCO3 on silica surface when streams of aqueous solutions of Ca(NO3)2 and Na2CO3 with a concentration of 40.0 g l−1 and 25.9gl−1 respectively flowing at a volumetric flow rate of 1 l h−1 each is mixed to form CaCO3 dispersion which was then transported through silica tubing at a steady volumetric flow rate of 2lh−1. The in situ phenomenology of CaCO3 particles transport, deposition, and evolution of spatial and temporal patterns of the CaCO3 deposition on the silica surface along with the dendritic growth of CaCO3 during the flow was visually documented with the aid of a 100X optical microscope. The study discussed the deposition behavior of dispersed phase of CaCO3 from its aqueous dispersion on the silica tubing during flow and attributed charge inversion from negative to positive of silica surface, due to the adsorption of Na+ formed during precipitation reaction of CaCO3, as a plausible reason for the reversal of electrostatic interaction from attraction between initially negatively charged silica surface and positively charged CaCO3 particles which promoted deposition and subsequent evolution of patterns of CaCO3 deposition on the silica surface during the early stage of experiments to repulsion between finally net positively charged silica surface and positively charged CaCO3 particles which resulted in retarded deposition and subsequent emergence of sparsely adhered CaCO3 agglomerates as localized, limited patches of CaCO3 deposits on the silica surface during the later stage of the experiments

[pt] O sucesso da estimulação por fraturamento é dependente da geração de condutividade. No fraturamento sustentado, a condutividade é governada pelas propriedades dos agentes de sustentação os quais são caracterizados por materiais uniformes, esféricos e de elevada resistência compressiva, capazes de manter a fratura condutiva mesmo em elevado estado de tensões. No fraturamento ácido, a condutividade depende da impressão irregular na superfície da fratura e da capacidade mecânica da rocha em sustentar um fluxo contínuo após o seu fechamento. A previsão de desempenho do reservatório requer, entre outros parâmetros, informações completas do modelo de fluxo e o decréscimo de pressão nas imediações do poço, a geometria e a condutividade resultante após o fraturamento possui grande influência nesta análise. O propósito deste trabalho visa investigar experimentalmente, a partir de testemunhos de carbonatos profundos, o comportamento de fraturas ácidas e sustentadas em diferentes estágios de tensão, desenvolver uma proposta de calibração do modelo empírico desenvolvido por Nierode e Kruk a fim de estimarmos a condutividade resultante utilizando dados de perfis com base em propriedades dinâmicas e composição mineralógica, e avaliar o impacto da condutividade na produtividade de um poço. Baseado na análise dos resultados concluiu que, é possível obter fratura ácida condutiva sob as tensões confinantes esperadas em carbonatos profundos e que fraturas sustentadas apresentam maiores condutividades, determinada pela característica do agente de sustentação utilizado, não sofrendo influência significativa com o incremento de tensão, ao contrário do fraturamento ácido. A partir dos dados indiretos obtidos de perfil a poço aberto, é possível obter uma estimativa da distribuição da condutividade de fraturas ácidas sem necessidade de testemunhos. Ao simularmos os ganhos de produtividade a partir de diversas variáveis disponíveis em cada técnica estudada de estimulação é possível ratificar que, não existe solução única indicada para carbonatos e que, a permeabilidade do meio é o fator preponderante na decisão. / [en] A well-succeeded fracturing stimulation depends on conductivity creation, which is ruled by the propping agent in sustained fracturing. These agents are characterized by uniform spherical materials of high compressive resistance, besides being capable of keeping conductivity, even under high stress state. Acid fracture conductivity depends on uneven etching on the surface of the fracture wall, as well as on the mechanical capacity of the rock to support a continuous flow after the fracture is closed. Reservoir performance predictions require, among other parameters, complete information about the flow model and about the pressure decreased around the well. The resulting geometry and conductivity after fracturing have great influence on these predictions. The aim of the present study is to experimentally investigate the behavior of acid fractures supported by different stress stages according to deep carbonate samples, as well as to develop a calibration proposition to the empirical model developed by Nierode and Kruk, in order to estimate the resulting conductivity by using data logging based on dynamic properties and mineralogical compositions. Moreover, it aims at assessing the impact of conductivity on the productivity of the well. Results of the herein performed analysis allowed concluding that it is possible to get an acid fracture under the confining stress expected for deep carbonates, and that sustained fractures have higher conductivity, which is set by the characteristics of the adopted propping agent. Therefore, different from the acid fracturing, these sustained fractures are not significantly influenced by higher stress. Based on the indirect data collected from the profile of the well, it was possible estimating acid fracture conductivity distribution, without the need of samples. The simulated productivity increase based on the different variables available for each of the assessed stimulation techniques made it possible ratifying that there is no single solution recommended for carbonates, and that the medium permeability is the main factor influencing the decision making process.

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