A ocorrência de solos sódicos é comumente relacionada a regiões de clima semiárido ou condições de drenagem fechada (endorreica), e ambientes evaporativos. No Pantanal brasileiro, conhecido como a maior área inundável continental do mundo, os solos sódicos possuem significativa expressão em termos de área e funcionalidade ambiental, pela especificidade no desenvolvimento de plantas e no consumo intencional do solo por diversos animais e servindo como refúgio durante a cheia. Estes solos estão localizados nas partes mais elevadas da paisagem (paleodiques), situação diversa da maioria dos casos. Os processos pedogenéticos em solos sódicos do Pantanal Norte foram estudados na Reserva Particular do Patrimônio Natural (RPPN) SESC-Pantanal, no município de Barão de Melgaço-MT, em paleodiques de cinco setores em diferentes estádios de dissecação. Para tanto foram utilizadas descrições morfológicas em diversas escalas, datações de 14C em precipitados de carbonato e por luminescência opticamente estimulada (LOE) em sedimentos, modelagens geoquímicas e mineralógicas, análises espaciais de atributos químicos e físicos do solo, levantamento da condutividade elétrica aparente com sensor eletromagnético (EM-38) e estatísticas multivariadas. Nos solos dos setores mais conservados, foram observadas feições típicas de ambiente sedimentar lêntico, lâminas de carbonato de cálcio e ocorrência de diatomáceas, sugerindo que a formação das feições ocorreu pela concentração de águas. Esses ambientes ocorreram em condições de drenagem distintas das atuais, em que as planícies de inundação permaneciam isoladas, com limitações de drenagem lateral e vertical, promovendo a perda d\'água por evapotranspiração e consequentemente concentrando os íons em solução. A simulação da evaporação das águas dos rios São Lourenço e Cuiabá apresentaram resultados similares, indicando que ambos poderiam resultar na precipitação de calcita e saturação do Na+ no complexo de troca. Entretanto as feições observadas na morfologia do perfil como nas lâminas delgadas sugerem que os solos sódicos atualmente estão em degradação. A argiluviação é muito intensa e se destaca como principal processo de transformação desses solos, ocorrendo desde os mais conservados até em estádio mais avançado de dissecação. A ferrólise é evidente no estádio mais avançado de transformação dos solos, na transição entre E e Bt onde se estabelece uma porosidade cavitária por depleção tanto mecânica como química. Os carbonatos associados a canais, antigos poros e sem córtex definido, sugerem que as condições atuais não favorecem a sua formação. As análises mineralógicas indicam a presença de esmectita na parte mais preservada do paleodique, que nas condições atuais sofre interestratificação esmectita-caulinita. A hidrologia atual promove a erosão gradativa dos paleodiques que, anteriormente isolavam as lagoas, passando a uma drenagem mais aberta. A análise de componentes principais (ACP) identificou o processo redox como predominante na área de estudo e, em conjunto com os eventos de inundação, são os principais responsáveis pelas transformações dos solos. A via de transformação de solos nos paleodiques da RPPN SESC Pantanal foi LUVISSOLO-PLANOSSOLO. Estes últimos são muito susceptíveis ao processo de erosão promovido pela inundação e tendem a desaparecer, estreitamento a cordilheira progressivamente. A erosão acaba deixando pequenas elevações circulares denominadas de murundus, com elevados teores de Na+. / Sodic soils are commonly associated to semi-arid climates, closed drainage systems (endorheic) and evaporative environments. In Brazilian Pantanal, knowns as the largest continental flooded area in the earth, sodic soils have significant expression in terms of area and environmental functionality, the specificity on plants development and soil intentional consumption (geophagy) by several animals, also playing as a refuge along the flooding events. These soils are located in the higher ground of the landscape (paleodiques), different from common situation. Pedogenic processes on north Pantanal sodic soils were studied in the Private Natural Heritage Reserve (PRNP) SESC Pantanal, in Barão do Melgaço-MT, performed on \"paleodiques\" from five sectors at different dissection stages. Pedogenic process was studied by means of morphologic descriptions was done in various scales, 14C dating on carbonate precipitates and optically stimulated luminescence (OSL) in sediments, geochemical and mineralogical modeling, spatial analysis of chemical and physical properties of the soil, apparent soil electrical conductivity performed by sensor electromagnetic (EM-38) and multivariate statistics. Soil profile from more conserved sectors shows typical features of lentic sedimentation environment, calcium carbonate layer and diatoms occurrence, suggesting that the formation of these features occurred by water concentration. Current condition is the opposite from earlier, wherein the flood plains remained isolated, with limited lateral and vertical drainage promoting water loss by evaporation and therefore concentrating the ions in solution. Simulation of the evaporation of water from São Lourenço and Cuiabá rivers points out similar results, suggesting that water evaporation from both could result in calcite precipitation and Na+ saturation in exchange complex. However, the features observed in both, field morphology and thin sections suggested that sodic soils are currently in degradation. The argilluviation is very intense and stands out as the main transformation process of these soils, occurring from the most preserved even in the most advanced dissection stage of. The ferrolysis is evident in the most advanced stage processing at E and Bt transition, where it establishes a cavity porosity depletion by both mechanical and chemical. Carbonates associated with channels, old pores and channels, without a cortex, suggests the current conditions do not favor sodic soil formation. Mineralogical analyzes indicates smectite presence in the paleodique of the most preserved sector, while present conditions promotes a smectite-kaolinite interestratification. Current hydrology promotes the gradual erosion of paleodiques that previously isolated the lakes from each other, becoming a slight open drainage system. The principal component analysis (PCA) identified the redox process as major process in the study area and, along the flood events, are primarily responsible for soil transformations. Pathway of sodic soil transformation in the RPPN SESC Pantanal paleodiques was Typic Natrudalf-Glossic Natraqualf. The latter are very susceptible to erosion process, promoted by flooding and tend to disappear, narrowing the paleodique progressively. Erosion process results in smalls and circulars elevations, named mounds, with high levels of Na+.

Dans cette thèse, nous avons décrit de nouvelles méthodes pour la préparation de polymères et de produits chimiques à partir de ressources renouvelables:Premièrement, nous avons défini une nouvelle méthode de préparation de sulfonamides, utilisant des nitro-aromatiques et des sels de sulfinate de sodium, dans une solution aqueuse de bisulfite de sodium, en tant qu’agent réducteur non toxique. Le produit a été séparé par une simple filtration. La réaction montre une chimio-sélectivité complète, seuls les substrats nitro déficitaire en électrons sont réactifs. Cependant, et contrairement à la littérature, les sels de sulfinate de sodium aromatiques et aliphatiques se sont révélés réactifs dans nos conditions. De plus, nous avons utilisé cette méthode pour préparer de manière écologique le catalyseur de zinc décrit par Karamé et al. et utilisé pour la cycloaddition du dioxyde de carbone avec des époxydes, afin d'accéder aux monomères de polycarbonates pour la préparation de polyuréthane non isocyanate.Ensuite, nous avons étudié la préparation de bis-carbonate de mannitol à partir de mannitol, en utilisant le carbonate de diméthyle comme réactif et comme solvant. Le carbonate de glycérol a été utilisé comme co-solvant en raison de ses propriétés de solubilisation intéressantes. La possibilité de synthèse des monomères diamines entièrement renouvelables a également été étudiée en utilisant des derives des sucres comme la furfurylamine et le 5-méthylfurfural. Nous avons également etudier l’aminolyse du bis-carbonate du mannitol avec la furfurylamine à la température ambiante. De plus, nous avons comparé la stabilité de ce carbonate avec les monomères carbonates commerciaux en utilisant une analyse gravimétrique thermique.Enfin, nous avons préparé le diester de 4,4'-oxydipentanoate de diéthyle à partir de lévulinate d'éthyle par éthérification réductrice sans solvant, catalysée par du triflate de cuivre, en utilisant du tétraméthydisiloxane comme agent réducteur. En outre, nous avons prouvé que ce nouveau monomère était utilisable dans la préparation des polyesters et des polyamides, dans des conditions de polycondensation classiques, en utilisant le propane diol et l’hexaméthylène diamine comme monomères modèles / In this thesis, we describe new methods for the preparation of polymers and chemicals from renewable resources: First we have defined new method for the preparation of sulfonamides, using nitro aromatics and sodium sulfinate salts, in aqueous sodium bisulfite solution as a non toxic reducing agent. The product was separated by simple filtration and the reaction show full chemoslectivity, only electron poor nitro substrates are reactive. However, in contrast with the literature, aromatic and aliphatic sodium sulfinate salts were found reactive under our conditions. In addition, we have used this method to prepare, in a green way, the active zinc catalyst reported by Karamé et al. for the cycloaddition of carbon dioxide with epoxydes, in order to access to polycarbonates monomers for non-isocyanate polyurethane preparation.Then, we have investigated the preparation of high purity mannitol bis-carbonate from mannitol using dimethyl carbonate as a reagent and as a solvent. Glycerol carbonate was used as co-solvent due to its interesting solubilization properties. The possibility of the synthesis of fully renewable diamine monomers was also investigated using furfurylamine and 5-methylfurfural derivated from sugars. We have also uncovered its high reactivity toward uncatalyzed aminolysis with furfurylamine at room temperature. Furthermore, we have compared the stability of this carbonate with existing commercial monomers using thermal gravimetric analysis.Finally, we prepared the diethyl 4,4'-oxydipentanoate diester from renewable ethyl levulinate was prepared by solventless reductive etherification, catalyzed by copper triflate, using tetramethydisiloxane as safe and low-cost reducing agent. Besides, we have proved the usability of this new monomer in the preparation of sustainable polyesters and polyamides, under classical polycondensation conditions, using propane diol and hexamethylene diamine as model monomers

Les écosystèmes côtiers sont soumis à de nombreuses perturbations entraînant la modification de leur structure et de leur fonctionnement. Afin d'estimer les parts respectives de la variabilité naturelle et de l'influence anthropique dans ce processus, et ainsi mieux prédire l'évolution de ces écosystèmes, il est nécessaire d'appréhender la variabilité de certains paramètres (température de l'océan, productivité biologique, apports de contaminants, etc.) avant toute influence anthropique majeure. Les mesures instrumentales de ces paramètres étant assez récentes, la reconstruction de la variabilité des écosystèmes côtiers avant la révolution industrielle ne peut se faire que par l'utilisation de proxies incorporés dans différents types d'archives.<br />Ce travail de thèse porte sur l'utilisation de la coquille de Comptopallium radula, un mollusque bivalve tropical de la famille des Pectinidae, pour reconstruire la variabilité de l'environnement dans le lagon sud-ouest de Nouvelle-Calédonie, un écosystème sous l'influence de diverses perturbations (réchauffement climatique, urbanisation, exploitation minière). Cette étude repose sur la comparaison de données géochimiques archivées dans la coquille de ce pectinidé au cours de sa vie, avec plusieurs variables physiques, chimiques et biologiques mesurées dans le lagon (suivi environnemental hebdomadaire). L'objectif de cette approche est de calibrer et de mettre en œuvre différents proxies climatiques et environnementaux.<br />Des marquages à la calcéine, effectués in situ sur des individus juvéniles, ont tout d'abord permis de démontrer que les stries de croissance présentes à la surface externe de la coquille de C. radula se forment avec une périodicité de 2 jours.<br />Des analyses isotopiques (δ18O et δ13C) ont ensuite été effectuées à partir de micro-échantillons de calcite prélevés le long de l'axe de croissance maximale de 6 coquilles juvéniles. Connaissant la périodicité de formation des stries, une date calendaire a pu être attribuée avec précision à chacun de ces prélèvements (résolution hebdomadaire). Nos résultats démontrent que les variations ontogéniques du δ18Ocalcite permettent de reconstruire les variations de la température de l'eau avec une précision de 1 °C. Quant à la composition isotopique du carbone (δ13Ccalcite), elle ne peut pas être utilisée comme proxy de la production primaire pélagique. Ses variations sont vraisemblablement contrôlées par le métabolisme benthique (sédiment et coraux).<br />Suite à ces analyses isotopiques, des analyses élémentaires ont été effectuées sur les mêmes coquilles à l'aide d'un système d'ablation laser couplé à un spectromètre de masse à plasma induit (LA-ICP-MS). Nos résultats démontrent que C. radula, au travers des concentrations en métaux dans sa coquille, ne peut être utilisé comme outil de bio-surveillance des apports en métaux dans le lagon : les variations ontogéniques de ces concentrations reflètent probablement les variations temporelles haute-fréquence des flux de métaux à l'interface eau-sédiment. Quant au baryum et au molybdène, leurs concentrations coquillières pourraient être utilisées comme proxies des biomasses de diatomées et de diazotrophes, respectivement.<br />Cette étude démontre donc le potentiel considérable de la coquille de C. radula comme archive eulérienne haute-fréquence de la variabilité climatique et environnementale dans le lagon sud-ouest de Nouvelle-Calédonie. Elle met également en lumière l'importance des processus benthiques sur l'incorporation des signaux géochimiques dans la matrice calcitique de la coquille. Son utilisation en tant qu'outil paléocéanographique est désormais conditionnée par la découverte de gisements fossiles de l'espèce.

In the Permian Basin, strata of Leonardian age typically consist of interbedded carbonates and siliciclastics interpreted to be turbidite deposits. Happy Spraberry Field produces from a 100-foot thick carbonate section in the Lower Clear Fork Formation (Lower Leonardian) on the Eastern Shelf of the Midland Basin. Reservoir facies include oolitic- to-skeletal grainstones and packstones, rudstones and in situ Tubiphytes bindstones. Depositional environments vary from open marine reefs to shallow marine oolitic shoal mounds. Best reservoir rocks are found in the oolitic-skeletal packstones. Diagenesis occurred in several phases and includes (1) micritization, (2) stabilization of skeletal fragments, (3) recrystallization of lime mud, (4) intense and selective dissolution, (5) precipitation of four different stages of calcite cement, (6) mechanical compaction, (7) late formation of anhydrite and (8) saddle dolomite and (9) replacement by chalcedony. Oomoldic porosity is the dominant pore type in oolitic grainstones and packstones. Incomplete dissolution of some ooids left ring-shaped structures that indicate ooids were originally bi-mineralic. Bacterial sulfate reduction is suggested by the presence of (1) dissolved anhydrite, (2) saddle dolomite, (3) late-stage coarse-calcite cement and (4) small clusters of pyrite. Diagenetic overprinting on depositional porosity is clearly evident in all reservoir facies and is especially important in the less-cemented parts of the oolitic grainstones where partially-dissolved ooids were subjected to mechanical compaction resulting in "eggshell" remnants. Pore filling by late anhydrite is most extensive in zones where dissolution and compaction were intense. Finally, a porosity-permeability model was constructed to present variations in oolitic packstone- rudstone-bindstone reservoir rocks. The poroperm model could not be applied to oolitic grainstone intervals because no consistent trends in the spatial distribution of porosity and permeability were identified. Routine core analysis did not produce any reliable value of water saturation (Sw). An attempt to take advantage of wireline log data indicates that the saturation exponent (n) may be variable in this reservoir.

Diagenetic studies of carbonate rocks focused for a long time on photozoan carbonate assemblages deposited in tropical climates. The results of these investigations were taken as models for the diagenetic evolution of many fossil carbonates. Only in recent years the importance of heterozoan carbonates, generally formed out of the tropics or in deeper waters, was realized. Diagenetic studies focusing on this kind of rocks are still scarce, but indicate that the diagenetic evolution of these rocks might be a better model for many fossil carbonate settings ("calcite-sea" carbonates) than the photozoan model used before.<br><br> This study deals with the determination of the diagenetic pathways and environments in such shallow-water heterozoan carbonate assemblages. Special emphasis is put on the identification of early, near-seafloor diagenetic processes and on the evaluation of the amount of constructive diagenesis in form of cementation in this diagenetic environment.<br><br> As study area the Central Mediterranean, the Maltese Islands and Sicily, was chosen. Here two sections were logged in Olio-Miocene shallow-water carbonates consisting of different kinds of heterozoan assemblages. The study area is very suitable for the investigation of constructive early diagenetic processes, as the rocks were never deeply buried and burial diagenetic pressure solution and cementation as cause of lithification could be ruled out. Nevertheless, the carbonate rocks are well lithified and form steep cliffs, implying cementation/lithification in another, shallower diagenetic environment. To determine the diagenetic pathways and environments, detailed transmitted light and cathodoluminescence petrography was carried out on thin sections. Furthermore the stable isotope (δ¹⁸O and δ¹³C) composition of the bulk rock, single biota and single cement phases was determined, as well as the major and trace element composition of the single cement phases.<br><br> Petrographically three (Sicily) to four (Maltese Islands) cementation phases, two phases of fabric selective and one of non-fabric selective dissolution, one phase of neomorphism and one of chemical compaction could be distinguished. The stable isotope measurements of the single cement phases pointed to cement precipitation from marine, marine-derived and meteoric waters. The trace element analysis indicated precipitation under reducing conditions, (A) in an open system with low rock-water interaction on the Maltese Islands and (B) in a closed system with high rock-water interaction on Sicily. For the closed systems case, aragonite as cement source could be concluded because its chemical composition was preserved in the newly formed cements.<br><br> By integrating these results, diagenetic pathways and environments for the investigated locations were established, and the cement source(s) in the different environments were determined. The diagenetic evolution started in the marine environment with the precipitation of fibrous/fibrous-bladed and epitaxial cement I. These cements formed as High Mg Calcite (HMC) directly out of marine waters. The paleoenvironmentally shallowest part of the section on the Maltese Islands was also exposed to meteoric diagenetic fluids. This meteoric influence lead to the dissolution of aragonitic and HMC skeletons, which sourced the cementation by Low Mg Calcitic (LMC) epitaxial cement II in this part of the Maltese section. Entering the burial-marine environment the main part of dissolution, cementation and neomorphism started to take place. The elevated CO2 content in this environment, caused by the decay of organic matter, lead to the dissolution of aragonitic skeletons, which sourced the cementation by LMC epitaxial cement II, bladed and blocky cements. The earlier precipitated HMC cement phases were either partly dissolved (epitaxial cement I) or neomorphosed to LMC (fibrous/fibrous-bladed and epitaxial cement I). In the burial environment weak chemical compaction took place without sourcing significant amounts of cementation. In a last phase the rocks entered the meteoric realm by uplift, which caused non-fabric selective dissolution. This study shows that early diagenetic processes, taking place at or just below the sediment-water-interface, are very important for the mineralogical stabilization of heterozoan carbonate strata. The main amount of constructive diagenesis in form of cementation takes place in this environment, sourced by dissolution of aragonitic and, to a lesser degree, of HMC skeletons.<br><br> The results of this study imply that the primary amount of aragonitic skeletons in heterozoan carbonate sediments must be carefully assessed, as they are the main early diagenetic cement source. In fossil heterozoan carbonate rocks, aragonitic skeletons might be the cement source even when no relict structures like micritic envelops or biomolds are preserved. In general, the diagenetic evolution of heterozoan carbonate rocks is a good model for the diagenesis of "calcite-sea" time carbonate rocks. / Diagenetische Untersuchungen an Karbonatgesteinen beschränkten sich lange Zeit auf photozoische Karbonatvergesellschaftungen der tropischen Breiten. Die Ergebnisse dieser Untersuchungen wurden als modellhaft für den Diageneseverlauf vieler Karbonatgesteine angesehen. Erst in den letzten Jahren wurde die Bedeutung heterozoischer Karbonatvergesellschaften, die sich im Allgemeinen außerhalb der Tropen oder in tieferem Wasser bilden, erkannt. Diagenetische Untersuchungen an dieser Art von Karbonatgesteinen sind immer noch selten, deuten aber an, dass der Diageneseverlauf in diesen Karbonaten ein besseres Model für viele fossile Karbonatgesteine ("Calcit-Meer"-Karbonate) darstellt als das bisher benutzte photozoische Diagenesemodel. Ziel dieser Studie war die Bestimmung des Diageneseverlaufs in solch flachmarinen Karbonaten mit heterozoischer Biogenvergesellschaftung. Die Milieus, in denen die diagenetischen Veränderungen stattfanden, sollten bestimmt werden. Besonderes Augenmerk lag auf der Art und Menge von Veränderungen, die frühdiagenetisch, nahe dem Meeresboden, stattfanden. Dabei war vor allem der Anteil an konstruktiver Diagenese in Form von Zementation von Interesse.<br><br> Das Arbeitsgebiet wurde im zentralen Mittelmeerraum gewählt und befindet sich auf den Maltesischen Inseln und Sizilien. Hier wurden zwei Profile in Flachwassserkarbonaten oligo-miozänen Alters aufgenommen, die sich aus unterschiedlichen heterozoischen Biogenvergesellschaftungen zusammensetzen. Dieses Arbeitsgebiet ist für die Untersuchung konstruktiver frühdiagenetischer Prozesse besonders geeignet, da die Gesteinsabfolgen niemals tief versenkt wurden und versenkungsdiagenetisch bedingte Drucklösung und Zementation als Ursache für die Lithifizierung ausgeschlossen werden können. Trotzdem sind die untersuchten Karbonatgesteine gut verfestigt und bilden steile Kliffs, was auf Zementation/Verfestigung in einem anderen, flacheren Diagenesemilieu hinweist. Zur Bestimmung der Diageneseabfolge und der diagenetischen Milieus wurden detaillierte petrographische Untersuchungen im Durchlicht und mit Kathodolumineszenz an Dünnschliffen durchgeführt. Außerdem wurden die Verhältnisse der stabilen Isotope δ¹⁸O und δ¹³C am Gesamtgestein, an einzelnen Biogenen und an einzelnen Zementphasen bestimmt. Die Haupt- und Spurenelement Zusammensetzung (Ca, Mg, Fe, Mn und Sr) wurde an den einzelnen Zementphasen ermittelt.<br><br> Petrographisch lassen sich drei (Sizilien), beziehungsweise vier (Maltesische Inseln) Zementationsphasen, zwei Phasen von materialabhängiger und eine Phase von materialunabhängiger Lösung, sowie eine Phase von Neomorphismus und eine chemische Kompaktionsphase unterscheiden. Die Messungen der stabilen Isotopenverhältnisse an den einzelnen Zementphasen deuten auf Zementausfällung aus marinen und meteorischen Wässern sowie aus Fluiden marinen Ursprungs hin. Die Spurenelementanalyse lässt außerdem auf Zementausfällung unter reduzierenden Bedingungen schließen. Diese fand einerseits, im Falle der Maltesischen Inseln, in einem offenen System mit geringer Gesteins-Wasser-Interaktion, andererseits, im Falle von Sizilien, in einem geschlossenen System mit großer Gesteins-Wasser-Interaktion statt. Bei der Zementation in einem geschlossenen System konnte Aragonit als Zementquelle bestimmt werden, da seine charakteristische chemische Zusammensetzung im neu gebildeten Zement erhalten blieb.<br><br> Durch die Integration aller Ergebnisse konnten für die beiden Lokalitäten die Diageneseabfolgen und die diagenetischen Milieus sowie die Zementquelle(n) in diesen Milieus bestimmt werden. Die diagenetische Entwicklung begann im marinen Milieu mit der Ausfällung von fibrösem bis fibrös-blättrigem und epitaxialem Zement I. Diese Zemente wurden als Hoch Magnesium Calcit (HMC) direkt aus marinem Wasser ausgefällt. Die paläogeographisch flachsten Abschnitte des Profils auf den Maltesischen Inseln gelangten dann unter den Einfluss meteorischer Wässer. Dieser meteorische Einfluss führte zur Lösung von aragonitischen und HMC Schalen, was die Zementation mit Niedrig (Low) Magnesium Calcitischem (LMC) epitaxialem Zement II in diesem Profilabschnitt speiste. Im marinen Versenkungsmilieu fand anschließend der Hauptteil an Lösung, Zementation und Neomorphismus statt. Der erhöhte CO2-Gehalt in diesem Milieu, verursacht durch den Zerfall von organischem Material, führte zur Lösung von aragonitischen Schalen, was die Zementation mit LMC epitaxialem Zement II, blättrigem und blockigem Zement speiste. Die vorher ausgefällten HMC Zementphasen wurden entweder teilweise gelöst (epitaxialer Zement I) oder in LMC umgewandelt (fibrös/fibrös-blättriger und epitaxialer Zement I). Im versenkungsdiagenetischen Milieu fand anschließend geringe chemische Kompaktion statt, ohne aber die Ausfällung von größeren Mengen an Zement zu speisen. In einer letzten Phase gelangten die Gesteine durch Hebung wieder ins meteorische Milieu, was materialunabhängige Lösungserscheinungen verursachte. Diese Untersuchung zeigt, dass frühdiagenetische Prozesse, die an der Sediment-Wasser-Grenzfläche oder knapp darunter stattfinden, sehr wichtig für die mineralogische Stabilisierung von heterozoischen Karbonatabfolgen sind. Der Hauptteil der konstruktiven Diagenese in Form von Zementation findet in diesem Milieu statt, gespeist durch die Lösung von aragonitischen und, zu einem geringern Teil, HMC Schalen.<br><br> Die Ergebnisse dieser Studie implizieren, dass der ursprünglich vorhandene Anteil an aragonitischen Schalen in heterozoischen Karbonatsedimenten sehr sorgfältig bestimmt werden muss, da diese Schalen die wichtigste frühdiagenetische Zementquelle darstellen. In fossilen heterozoischen Karbonatgesteinen können aragonitische Schalen die wichtigste Zementquelle darstellen, auch wenn keine Reliktstrukturen wie mikritische Hüllen oder Biomolds erhalten geblieben sind. Im Allgemeinen stellt der Diageneseablauf in heterozoischen Karbonaten ein gutes Modell für die Diagenese von "Calcit-Meer"-Karbonatgesteinen dar.

La présente étude s'inscrit dans le cadre d'un projet multidisciplinaire visant à comprendre la dynamique du carbone organique et inorganique suite à la mise en eau d'un réservoir hydroélectrique. Dans un premier temps, ces travaux avaient pour objectif de décrire et de cartographier à l'échelle du 1: 50 000 les dépôts superficiels (nature, étendue, sédimentologie et stratigraphie) afin de reconstituer les principaux évènements quaternaires de la région dans le but de définir, entre-autre, le contexte de mise en place des tourbières étudiées dans le volet paléoécologique du projet. Dans un deuxième temps, ces travaux visaient à estimer la teneur en carbone inorganique (CO₃) dans les sédiments meubles, à partir de la mesure des carbonates (CaCO₃) afin d'évaluer son impact potentiel dans l'équation du bilan global du carbone du réservoir créé. Ces travaux de caractérisation des dépôts meubles ont été réalisés dans le secteur affecté par le réservoir Eastmain-I, durant les étés de 2005 et 2006. La photo-interprétation, la campagne de validation sur le terrain et la compilation cartographique ont permis d'évaluer la répartition spatiale et l'épaisseur maximale des principaux types de dépôts quaternaires dans la zone maintenant ennoyée par le réservoir: till (superficie couverte 30 %; épaisseur maximale 6 m), fluvioglaciaire de contact (< 1 %; 10 m), proglaciaire (12 %; 4 m), marin (30 %; 11 m) et organique (18 %; 5 m). Les relevés des microformes et mésoformes d'érosion glaciaire suggèrent également qu'il y a eu quatre phases d'écoulement soit de la plus ancienne à la plus récente: NNE-SSO (006°-186°) à NNO-SSE (350°-170°), NO (310°) à ONO (290°), OSO (240°; mouvement dominant responsable de l'orientation des formes fuselées) et finalement SO (220°). De plus, lors de la déglaciation, il a été établi que la Mer de Tyrrell a envahi le territoire jusqu'à une altitude d'environ 274 m (900 pi). Cette limite marine est indiquée par des deltas, des limites de délavage dans le till et quelques accumulations littorales. C'est à l'intérieur de la zone couverte initialement par la Mer de Tyrrell que les plus vastes tourbières se sont développées. Les datations au radiocarbone de la base de six de ces tourbières indiquent qu'à 6640 ± 40 ¹⁴C BP (7 510 cal BP), le niveau de la mer était situé sous l'altitude de 246 m. Enfin, les teneurs en CaCO₃ mesurées dans les sédiments superficiels sont relativement faibles, soit inférieures à 2,45 %. Ces résultats sont en accord avec la géologie du substratum rocheux, principalement formé de roches cristallines. Les valeurs moyennes les plus élevées se trouvent dans les sédiments marins (1,77 %). Les faibles valeurs en carbonates mesurées dans les tills (1,32 %) semblent démontrer que ce secteur n'a pas été affecté de façon importante par le transport glaciaire qui aurait pu provenir d'autres sources connues de roches carbonatées (régions du lac Mistassini et de la Baie James). À l'intérieur de la portion cartographiée du réservoir EM-1, la quantité approximative de moles de CaCO₃ est de 6,16 x 10¹², soit 9,25 x 10⁰⁸ tonnes. ______________________________________________________________________________ MOTS-CLÉS DE L’AUTEUR : Eastmain-l, Cartographie, Paléogéographie quaternaire, Écoulements glaciaires, Mer de Tyrrell, Teneur en carbone inorganique.

Pulsed-neutron borehole measurements involve a physical process in which a source emits energetic neutrons that lose energy upon collisions with formation nuclei, and are eventually captured by a nucleus to form a heavier, excited state. The excited nucleus decays to its ground state by the emission of gamma rays. Both thermal-neutron and gamma-ray populations decay with time at a rate defined by Sigma, which is a nuclear property that quantifies a material’s ability to capture thermal neutrons. The large contrast in Sigma between hydrocarbon and salty connate water enables calculations of water saturation directly from pulsed-neutron measurements. Sigma logs have proven useful in the assessment of thinly bedded formations because they exhibit a small volume of investigation, and have been deemed superior to resistivity logs in the petrophysical evaluation of carbonate formations. The recognized potential of Sigma logs in formation evaluation initiated the development of multi-detector Logging-While-Drilling (LWD) Sigma measurements. These measurements are acquired using one thermal-neutron and two gamma-ray detectors at different spacings from the source. Such a design is aimed at providing distinct radial depths of investigation to detect filtrate invasion in the near-wellbore zone. Despite their formation-evaluation potential, multi-detector time-decay measurements commonly remain affected by invasion, shoulder-bed, and well-deviation effects. The purpose of this dissertation is to develop a fast-forward simulation method to reproduce multi-detector time decays and combine the method with inversion techniques to improve the petrophysical interpretation of LWD Sigma measurements. First-order perturbation theory and a library of pre-calculated Monte Carlo detector-specific sensitivity functions and time decays are used to numerically simulate borehole Sigma measurements in realistic logging environments. The new simulation method is one hundred thousand times faster than rigorous Monte Carlo calculations and remains within two capture units of disparity. Next, the fast-forward simulation method is embedded within inversion algorithms to estimate layer-by-layer radial length of invasion and formation Sigma corrected for shallow invasion, shoulder-bed, and well-deviation effects. Both fast-forward and inverse modeling algorithms are benchmarked against laboratory and synthetic time decays. The improvement of formation Sigma obtained with inversion-based interpretation leads to an improvement in the estimation of Sigma-derived water saturation. Likewise, the estimated radial length of invasion is combined with neutron and density measurements to correct the latter for invasion effects. Results indicate that the inversion-based interpretation method is well suited for the evaluation of high-porosity formations invaded by salty mud filtrate. Inversion-based interpretation of field LWD time decays enables the estimation of lower values of water saturation when compared to conventional Sigma interpretation or resistivity methods. Estimated values of water saturation are as much as fifty percent lower than predicted by conventional interpretation of Sigma logs in the case of measurements affected by shoulder-bed effects, and as much as one hundred percent lower than predicted by the conventional interpretation method for measurements additionally affected by salty filtrate invasion. The key attributes of the combined petrophysical interpretation of multi-detector Sigma, neutron, and density measurements developed in this dissertation are that it explicitly enforces the physics of all nuclear measurements, honors the pressure and temperature dependency of reservoir fluid nuclear properties, and takes into account a-priori information such as mud-filtrate salinity, connate-water salinity, and bed-boundary locations. / text

The Permian (Leonardian) aged Upper Spraberry Formation found in the Happy Field of Garza Co. TX, contains one of the best examples of a reservoir composed of resedimented carbonates in a deep-water slope-basin setting, with numerous whole core of wells with full suites of electric logs, high resolution 3D seismic coverage, and 20+ years worth of production data. Sequence stratrigraphic analysis from seismic data combined the lithologic analysis from outcrop analog, core, and well log data helps identify that the Happy Field is located within the transgressive systems tract of the fifth composite sequence in the Leonardian. The reservoir is composed of discrete allochthonous ooid and skeletal grains transported downslope via hyperconcentrated density flows sourced from a re-entrant in the shelf margin and deposited in a long-lived topographic depression at the toe-of-slope. Vertical heterogeneity due to layers of shaley silt punctuated by successive flows of oolitic and skeletal grains along with lateral heterogeneity created by younger flows of material create reservoir compartmentalization which can impede efficient development. Core-calibrated electric log correlations aids in the mapping of isolated compartments which helps with efficient development planning for the field. / text

In the Permian Basin, strata of Leonardian age typically consist of interbedded carbonates and siliciclastics interpreted to be turbidite deposits. Happy Spraberry Field produces from a 100-foot thick carbonate section in the Lower Clear Fork Formation (Lower Leonardian) on the Eastern Shelf of the Midland Basin. Reservoir facies include oolitic- to-skeletal grainstones and packstones, rudstones and in situ Tubiphytes bindstones. Depositional environments vary from open marine reefs to shallow marine oolitic shoal mounds. Best reservoir rocks are found in the oolitic-skeletal packstones. Diagenesis occurred in several phases and includes (1) micritization, (2) stabilization of skeletal fragments, (3) recrystallization of lime mud, (4) intense and selective dissolution, (5) precipitation of four different stages of calcite cement, (6) mechanical compaction, (7) late formation of anhydrite and (8) saddle dolomite and (9) replacement by chalcedony. Oomoldic porosity is the dominant pore type in oolitic grainstones and packstones. Incomplete dissolution of some ooids left ring-shaped structures that indicate ooids were originally bi-mineralic. Bacterial sulfate reduction is suggested by the presence of (1) dissolved anhydrite, (2) saddle dolomite, (3) late-stage coarse-calcite cement and (4) small clusters of pyrite. Diagenetic overprinting on depositional porosity is clearly evident in all reservoir facies and is especially important in the less-cemented parts of the oolitic grainstones where partially-dissolved ooids were subjected to mechanical compaction resulting in "eggshell" remnants. Pore filling by late anhydrite is most extensive in zones where dissolution and compaction were intense. Finally, a porosity-permeability model was constructed to present variations in oolitic packstone- rudstone-bindstone reservoir rocks. The poroperm model could not be applied to oolitic grainstone intervals because no consistent trends in the spatial distribution of porosity and permeability were identified. Routine core analysis did not produce any reliable value of water saturation (Sw). An attempt to take advantage of wireline log data indicates that the saturation exponent (n) may be variable in this reservoir.

The production of hydrogen (H2) and methane (CH4) related to olivine hydration (i.e. serpentinization) is considered a major contributor to abiotic hydrocarbon synthesis on Earth. Recent discoveries have highlighted the importance of low temperature (<100oC) serpentinization at continental peridotite outcrops. Such sites produce substantial fluxes of abiotic CH4 from gas seeps and/or springs. A limited number of studies in the southern hemisphere offer research on low temperature abiotic hydrocarbon synthesis in natural ultramafic environments, though large areas of exposed ophiolite are prevalent. This study assesses the origin and flux of CH4 and related water-rock interactions from a previously undiscovered site in the Dun Mountain Ophiolite Belt (DMOB), located at Red Hills, New Zealand. Methane emissions from a hyper-alkaline (pH >11.6) and reduced spring of calcium hydroxide (Ca2+-OH-) type waters near the Maitlands Fault were between 730 to 17,000 mg m 2day 1. The δ13C and δD values of CH4 emitting from this spring are consistent with CH4 of abiotic origin (δ13C: 32.7 ‰ VPDB, δD: 363 ‰ V SMOW). Hyper-alkaline fluids emitting from the spring are concentrated in dissolved CH4 (2.2 mg/L) and H2 (0.7 mg/L) and display δ13CCH4 signatures consistent with other sites worldwide. Extensive and localised carbonate precipitation occurs at the hyper-alkaline Ca-rich spring. Isotopic evaluation of carbonate nodules are kinetically fractionated with 13C and 18O depletions up to 30.8 ‰ and 9.3 ‰, respectively. This disequilibrium between the mineralogy and interacting fluids and gases represents a potential habitable environment for microorganisms. Porous, layered carbonates located on the outer edges of the hyper-alkaline spring are the result of atmospheric CO2 interaction with magnesium bicarbonate (Mg2+-HCO3) and Ca2+-OH- hyper-alkaline waters. The precipitation of these carbonates offers potential insight towards low temperature CO2 sequestration. Additionally, various forms of Fe-rich amorphous material precipitate in association with Mg2+-HCO3 type waters at the Red Hills. The identification of bacteria and diatoms within this material offers supporting information regarding microbial survival in metal-rich, reduced environments. This multidisciplinary study demonstrates the interconnected nature of geological, biological and atmospheric interactions in ultramafic environments at low temperature on Earth.