Bentonite clays are exposed in Paleogene strata stretching over 650 km parallel to the Texas coastline. This study focuses on a white and blue and a yellow and brown commercial Ca-montmorillonite bentonite near the city of Gonzales, Gonzales county, Texas. The deposits have stratigraphic ages of Late Eocene (~36.7 - 32.7 Ma). The bentonites in these deposits have varying colors, purities and brightness affording them diverse industrial uses. The distribution and geologic character of the high purity white and blue bentonite suggests that the deposit represents an accumulation of volcanic ash in a secondary tidal channel during the ash-fall event. A low rate of terrigenous clastic sedimentation and rapid accumulation of fresh ash were critical to the formation of high purity clay. The lower purity yellow and brown bentonites appear to have a fluvial origin marked by higher rates of detrital sedimentation and episodic accumulation of clay and ash. The bentonite and associated strata were studied using optical microscopy, SEM, XRD and REE analyses to constrain their textural, mineralogic, and chemical character. vii Eocene pyroclastic volcanism is well documented from sources in southwestern North America, specifically in the Sierra Madre Occidental (Mexico), Trans-Pecos (Texas) and Mogollan-Datil (New Mexico) volcanic fields. Projected Eocene wind patterns support this region as a potential source for the Gonzales bentonites. A comparison of the trace and REE fingerprints of the white and blue bentonites and the yellow and brown bentonites with data available for Late Eocene volcanics in the North American Volcanic Database provides a couple of potential matches. The strongest potential match for the Late Eocene bentonite protolith is described as a sample of silicic tuff with an age range of 32.2 – 30.6 Ma, located in the southern Mexican state of Oaxaca. While the trace and REE match is strong, the tuff is somewhat young compared to the Jackson Group sediments. In addition, the sample location is due almost directly south of the Gonzales deposits, rather than the western location expected for a Gonzales bentonite source. The other potential matches are located in New Mexico, and the Mexican state of Chihuahua. These potential matches only have 6 REE available for comparison, and require further investigation. Many Paleogene volcanic units in southern North America are undocumented with regard to REE data or precise absolute ages. As additional geochemical analyses become available for a more extensive suite of Paleogene volcanic units, stronger matches with Gulf of Mexico Basin bentonites are expected to emerge. / text

Financiadora de Estudos e Projetos / Agência Nacional do Petróleo / O Membro Maruim da Formação Riachuelo (Neoalbiano), na parte terrestre da Sub-bacia de Sergipe, contém fácies de água rasa compostas, principalmente, por rudstone/grainstone oncolítico oolítico, com baixo conteúdo e variedade de bioclastos. A correlação dos afloramentos e análise petrográfica detalhada, envolvendo catodoluminescência, microscopia eletrônica de varredura (MEV) e estudos isotópicos e análise química elementar, permitiram a reconstrução da história diagenética do intervalo estudado. As rochas carbonáticas do Membro Maruim estão completamente afetadas por processos diagenéticos associados aos estágios eogenético, mesogenético e telogenético. A dolomitização foi um dos principais produtos diagenéticos observados no estágio eogenético e encontra-se substituindo total ou parcialmente os calcários do Membro Maruim. A dolomitização concentra-se no topo dos ciclos deposicionais descritos na área de estudo e diminuem gradativamente para a base dos mesmos. As relações entre a porosidade e a dolomitização foram estudadas com base nas comparações da fábrica cristalina da dolomita preservada nos afloramentos estudados. Os resultados isotópicos das dolomitas indicam que o processo de dolomitização ocorreu a partir do refluxo de salmouras em um ambiente ligeiramente hipersalino (penesalino). As áreas mais próximas ao contato com a salmoura, fonte dos fluidos dolomitizantes, exibem menor desenvolvimento de porosidade, uma vez que nessas regiões ocorreriam processos de superdolomitização (Pedreira Carapeba). Nestas áreas a assinatura isotópica do carbono e do oxigênio é muito positiva (o valor do δ13C varia de 2.37 a 4.83 e o valor do δ18O oscila entre 0.61 e 3.92), indicando que os processos diagenéticos tardios não teriam alterado significativamente a assinatura isotópica original. As dolomitas geradas nas áreas afastadas da salmoura (pedreiras Massapé, Inorcal I, Inorcal II, Inhumas e Santo Antônio) exibem um maior desenvolvimento de porosidade e têm uma composição isotópica de carbono e oxigênio mais negativa (o valor do δ13C varia de -5.66 a 2.61 e o valor do δ18O oscila entre -4.25 e 0.38). A assinatura isotópica das dolomitas descritas nestas pedreiras também se encontra alterada por processos de dedolomitização. Os cimentos diagenéticos precipitados durante o estágio mesogenético foram os principais responsáveis pela obliteração da porosidade primária e secundária dos calcários do Membro Maruim. Adicionalmente, estes cimentos diagenéticos tardios calcitizaram as dolomitas, fechando parcialmente a porosidade secundária das mesmas. A porosidade das rochas carbonáticas também se encontra fortemente reduzida pela compactação mecânica e química. A dissolução foi o único processo que levou à geração de porosidade secundária no estágio telogenético, porém em porcentagens muito baixas. As fácies dolomíticas são as que apresentam maior desenvolvimento de porosidade secundária, como consequência dos processos de dissolução no ambiente telogenético. A dissolução compreende um dos últimos eventos diagenéticos identificados no intervalo estudado. / The Maruim Member of the Riachuelo Formation (Neoalbian), in the terrestrial part of the Sergipe Sub-basin, contains shallow water facies composed mainly of rudstone/grainstone with oncolites and oolites, characterized by the low content and variety of bioclasts. The correlation of the outcrops and the integration of the petrographic, cathodoluminescence, SEM and geochemical (elemental and isotopic study) analyses allowed the reconstruction of the diagenetic history of the studied interval. Carbonates of the Maruim Member are completely affected by diagenetic processes of the eogenetic, mesogenetic and telogenetic phases. The dolomitization was one of the main diagenetic products of the eogenetic phase and it replaces all or part of the limestones of the Maruim Member. The dolomitization is concentrated at the top of the depositional cycles described in the study area and it gradually decreases towards their base. The relationships between porosity and dolomitization were studied with basis on the comparisons of the crystalline dolomite fabric through the studied outcrops. The isotopic results of the dolomites indicate that the dolomitization process occurred from the reflux of brines in a slightly hypersaline environment (penesaline environment). The areas closest to the contact with the brine, source of the dolomitizing fluids, exhibit lower porosity development because there would have occurred processes of super dolomitization (Carapeba Quarry). In these areas, the carbon and oxygen isotopic signature is very positive (δ13C between 2.37 and 4.83, δ18O between 0.61 and 3.92), indicating that the late diagenetic processes would not have altered much the original isotopic signal. The dolomites generated in the areas farthest from the brine source of the dolomitizing fluids (Massapé, Inorcal I, Inorcal II, Inhumas and San Antonio Quarries), exhibit a greater development of porosity and have an isotopic composition of carbon and oxygen of more negative values (δ13C between -5.66 and 2.61, δ18O between -4.25 and 0.38). Moreover, in these quarries the isotopic signature of the dolomites is also altered by processes of dedolomitization. Diagenetic cements precipitated during the mesogenetic phase was responsible for the obliteration of the primary and secondary porosity of the Maruim Member limestones. Further, the late diagenetic cements calcitized the dolomite and partially closed its secondary porosity. The porosity of the carbonate rocks is also greatly reduced by mechanical and chemical compaction. Dissolution was the only process that led to the generation of secondary porosity in the telogenetic stage, although in very low proportions. The dolomitic facies are those that present greater development of secondary porosity as a result of the dissolution processes in the telogenetic environment. The dissolution comprises one of the last diagenetic events identified in the studied interval.

Financiadora de Estudos e Projetos / Agência Nacional do Petróleo / O Membro Maruim da Formação Riachuelo (Neoalbiano), na parte terrestre da Sub-bacia de Sergipe, contém fácies de água rasa compostas, principalmente, por rudstone/grainstone oncolítico oolítico, com baixo conteúdo e variedade de bioclastos. A correlação dos afloramentos e análise petrográfica detalhada, envolvendo catodoluminescência, microscopia eletrônica de varredura (MEV) e estudos isotópicos e análise química elementar, permitiram a reconstrução da história diagenética do intervalo estudado. As rochas carbonáticas do Membro Maruim estão completamente afetadas por processos diagenéticos associados aos estágios eogenético, mesogenético e telogenético. A dolomitização foi um dos principais produtos diagenéticos observados no estágio eogenético e encontra-se substituindo total ou parcialmente os calcários do Membro Maruim. A dolomitização concentra-se no topo dos ciclos deposicionais descritos na área de estudo e diminuem gradativamente para a base dos mesmos. As relações entre a porosidade e a dolomitização foram estudadas com base nas comparações da fábrica cristalina da dolomita preservada nos afloramentos estudados. Os resultados isotópicos das dolomitas indicam que o processo de dolomitização ocorreu a partir do refluxo de salmouras em um ambiente ligeiramente hipersalino (penesalino). As áreas mais próximas ao contato com a salmoura, fonte dos fluidos dolomitizantes, exibem menor desenvolvimento de porosidade, uma vez que nessas regiões ocorreriam processos de superdolomitização (Pedreira Carapeba). Nestas áreas a assinatura isotópica do carbono e do oxigênio é muito positiva (o valor do δ13C varia de 2.37 a 4.83 e o valor do δ18O oscila entre 0.61 e 3.92), indicando que os processos diagenéticos tardios não teriam alterado significativamente a assinatura isotópica original. As dolomitas geradas nas áreas afastadas da salmoura (pedreiras Massapé, Inorcal I, Inorcal II, Inhumas e Santo Antônio) exibem um maior desenvolvimento de porosidade e têm uma composição isotópica de carbono e oxigênio mais negativa (o valor do δ13C varia de -5.66 a 2.61 e o valor do δ18O oscila entre -4.25 e 0.38). A assinatura isotópica das dolomitas descritas nestas pedreiras também se encontra alterada por processos de dedolomitização. Os cimentos diagenéticos precipitados durante o estágio mesogenético foram os principais responsáveis pela obliteração da porosidade primária e secundária dos calcários do Membro Maruim. Adicionalmente, estes cimentos diagenéticos tardios calcitizaram as dolomitas, fechando parcialmente a porosidade secundária das mesmas. A porosidade das rochas carbonáticas também se encontra fortemente reduzida pela compactação mecânica e química. A dissolução foi o único processo que levou à geração de porosidade secundária no estágio telogenético, porém em porcentagens muito baixas. As fácies dolomíticas são as que apresentam maior desenvolvimento de porosidade secundária, como consequência dos processos de dissolução no ambiente telogenético. A dissolução compreende um dos últimos eventos diagenéticos identificados no intervalo estudado. / The Maruim Member of the Riachuelo Formation (Neoalbian), in the terrestrial part of the Sergipe Sub-basin, contains shallow water facies composed mainly of rudstone/grainstone with oncolites and oolites, characterized by the low content and variety of bioclasts. The correlation of the outcrops and the integration of the petrographic, cathodoluminescence, SEM and geochemical (elemental and isotopic study) analyses allowed the reconstruction of the diagenetic history of the studied interval. Carbonates of the Maruim Member are completely affected by diagenetic processes of the eogenetic, mesogenetic and telogenetic phases. The dolomitization was one of the main diagenetic products of the eogenetic phase and it replaces all or part of the limestones of the Maruim Member. The dolomitization is concentrated at the top of the depositional cycles described in the study area and it gradually decreases towards their base. The relationships between porosity and dolomitization were studied with basis on the comparisons of the crystalline dolomite fabric through the studied outcrops. The isotopic results of the dolomites indicate that the dolomitization process occurred from the reflux of brines in a slightly hypersaline environment (penesaline environment). The areas closest to the contact with the brine, source of the dolomitizing fluids, exhibit lower porosity development because there would have occurred processes of super dolomitization (Carapeba Quarry). In these areas, the carbon and oxygen isotopic signature is very positive (δ13C between 2.37 and 4.83, δ18O between 0.61 and 3.92), indicating that the late diagenetic processes would not have altered much the original isotopic signal. The dolomites generated in the areas farthest from the brine source of the dolomitizing fluids (Massapé, Inorcal I, Inorcal II, Inhumas and San Antonio Quarries), exhibit a greater development of porosity and have an isotopic composition of carbon and oxygen of more negative values (δ13C between -5.66 and 2.61, δ18O between -4.25 and 0.38). Moreover, in these quarries the isotopic signature of the dolomites is also altered by processes of dedolomitization. Diagenetic cements precipitated during the mesogenetic phase was responsible for the obliteration of the primary and secondary porosity of the Maruim Member limestones. Further, the late diagenetic cements calcitized the dolomite and partially closed its secondary porosity. The porosity of the carbonate rocks is also greatly reduced by mechanical and chemical compaction. Dissolution was the only process that led to the generation of secondary porosity in the telogenetic stage, although in very low proportions. The dolomitic facies are those that present greater development of secondary porosity as a result of the dissolution processes in the telogenetic environment. The dissolution comprises one of the last diagenetic events identified in the studied interval.

No description available.

Dans les réservoirs silicoclastiques, la perte de porosité avec l'enfouissement est due à la fois à la compaction mécanique lors des 2-3 premiers kilomètres d'enfouissement, à la compaction chimique, et à la précipitation minérale (quartz, argiles, carbonates). Dès lors, la compréhension des processus responsables de l'inhibition de la compaction et/ou de la cimentation représente un triple enjeu: i) contribuer à la connaissance des mécanismes d'interactions eau-hydrocarbures-solides en milieu diagénétique profond; ii) apporter de nouveaux arguments pour reconstituer les chemins de migration des fluides à l'échelle du bassin iii) développer des guides de prospection pour l'industrie pétrolière. Les techniques analytiques telles que la pétrographie quantitative, les inclusions fluides ainsi que les modélisations diagénétiques et de bassin ont été couplées afin de comprendre les processus régissant le contrôle de la qualité du réservoir du Brent (Jurassique Moyen) à travers 8 champs pétroliers (et 11 puits) dans le bloc Q3 (Viking Graben, Northern North Sea). L'étude pétrographique quantitative du réservoir du Tarbert a permis de définir des compositions minéralogiques et des paramètres pétrophysiques (porosité) relativement similaires sur les 183 échantillons étudiés. Une paragenèse diagénétique commune à tous les champs étudiés a été établie, dominée par les ciments de quartz, de deux générations de kaolinite (K1, associée à la déstabilisation des micas et K2, associée à la dissolution des feldspaths potassiques), et de précipitation d'illite. L'approche comparative des ciments d'enfouissement n'a pas permis de rendre compte des larges gammes de porosité et perméabilité mesurées allant de 8 à 27 % et de 0,2 à 5000 mD. Contrairement au modèle diagénétique souvent évoqué, l'inhibition des ciments de quartz ne joue pas un rôle majeur dans la préservation de la porosité des réservoirs du bloc Q3. Les estimations P-V-T-X-t du piégeage des inclusions fluides couplées au modèle de bassin ont permis de reconstituer trois chemins de migration des fluides aqueux et hydrocarbonés associés à la mise en place de surpressions fluides au sein des réservoirs du Tarbert. 1) La partie Nord de la kitchen du Viking Graben alimente les champs de Hild, Jura et Islay en huiles légères très précocement (65-42 Ma) et en gaz à condensat à partir de 35-15 Ma. Ces deux migrations sont associées à une montée en surpression fluide du réservoir de 100 à 200 bar. 2) la partie Est de la kitchen de l'East Shetland alimente les champs d'Alwyn, Dunbar, et Grant en huiles lourdes à légères à partir de 42-35 Ma, associée à une faible surpression fluide (30-40 bar). 3) la partie Sud de la kitchen de l'East Shetland (longue distance de migration) alimente quant à elle les champs de Forvie Central et North très tardivement en gaz à condensat (> 15 Ma). Le timing relatif entre la mise en place de la surpression fluide et l'avancement de la compaction mécanique/chimique s'est révélé être le paramètre de premier ordre régissant la préservation de la porosité des réservoirs observée dans le bloc Q3. La présence d'inclusions hydrocarbonées atypiques HT-BP (haute température-basse pression) datées du Jurassique supérieur dans les champs proches du Viking Graben, pourrait être à l'origine d'une génération d?hydrocarbures très précoce sous un régime de pression hydrostatique. Bien que n'ayant aucun impact sur l'inhibition de la contrainte effective, cette migration fluide pourrait être attribuée aux anomalies thermiques du Nord-Ouest de l'Europe liée à l'ouverture de l'Atlantique Nord. Le couplage des outils de pétrographie quantitative, inclusions fluides et modélisation de bassin a donc permis de soulever l'importance d'intégrer une vision régionale à l'étude ponctuelle de la diagenèse dans le but de comprendre le rôle des migrations fluides sur la préservation de la qualité des réservoirs silicoclastiques / In siliciclastic reservoirs, porosity loss is mainly due to the mechanical compaction in the first 2-3 km of burial, the chemical compaction and mineral precipitation (quartz, clays, carbonates). Therefore, understanding the processes responsible of the inhibition of compaction and/or cementation permits to: i) contribute to the knowledge of the water-hydrocarbon-solid interaction mechanisms in deep diagenetic environment, ii) give new arguments for the reconstruction of fluid pathways at the basin scale iii) assist the oil industry for the intensive exploration. Analytical techniques such as quantitative petrography, fluid inclusion and basin/diagenesis modelling were coupled across 8 oil fields (and 11 wells) located in the Q3 block (Viking Graben, Northern North Sea) in order to understand the processes driving the variation of the Brent reservoir quality (Middle Jurassic). Quantitative petrographic study of Tarbert reservoir allowed to define similar depositional settings (mineralogy, porosity) among the 183 studied samples. The common diagenetic paragenesis is dominated by quartz cement, two generations of kaolinite (K1, associated with the destabilization of micas and K2, associated with the dissolution of feldspars), and precipitation of illite. The petrographic data do not explain the wide range of measured porosity and permeability on plugs from 8 to 27% and from 0.2 to 5000 mD respectively. In contrast with the conventional diagenetic model, the present study shows that inhibition of quartz cements did not play a major role in the preservation of porosity in the Q3 block. P-V-T-X-t estimates of fluid inclusion trapping coupled with basin modelling allowed reconstruction of three fluid migration pathways, associated with fluid overpressures in the Tarbert reservoir. 1) The northern part of the Viking Graben kitchen supplies Hild, Jura and Islay fields with an early migration of light oils (65-42 m.y.) and condensate from 35-15 m.y. Both migrations are associated with a great fluid overpressure from 100 to 200 bar. 2) The eastern part of the East Shetland kitchen supplies Alwyn, Dunbar, Grant fields, with heavy to light oils from 42-35 m.y., associated with a low fluid overpressure (30-40 bar). 3) The southern part of the East Shetland kitchen (long distance migration) supplies Forvie North and Central fields with a very late gas condensate migration (> 15 Ma). The relative timing of the fluid overpressure build-up with the degree of mechanical and chemical compaction appears to be the first order parameter governing the preservation of reservoir porosity across the Q3 block. The presence of unusual HT-LP (high temperature-low pressure) hydrocarbon inclusions in the fields near the graben could indicate an early heavy oil generation under hydrostatic pressure conditions. Although having no impact on the inhibition of effective stress, this high-temperature fluid migration could be attributed to thermal anomalies in the Northwest of Europe related to the North Atlantic opening. The combination of quantitative petrography, fluid inclusion and basin modelling allowed to point out the impact of regional fluid migrations on the well scale diagenesis and on the siliciclastic reservoir quality preservation

Submitted by Biblioteca de Pós-Graduação em Geoquímica BGQ (bgq@ndc.uff.br) on 2016-03-28T17:23:27Z No. of bitstreams: 1 Dissertação_Christiene_FINAL_.pdf: 2691556 bytes, checksum: 6c071c6fc087c647c3aae5c59f4526d4 (MD5) / Made available in DSpace on 2016-03-28T17:23:27Z (GMT). No. of bitstreams: 1 Dissertação_Christiene_FINAL_.pdf: 2691556 bytes, checksum: 6c071c6fc087c647c3aae5c59f4526d4 (MD5) / Conselho Nacional de Desenvolvimento Científico e Tecnológico / Universidade Federal Fluminense. Instituto de Química. Programa de Pós-Graduação em Geociências-Geoquímica. Niterói, RJ / A diagênese recente de metais-traço redox-sensitivos, nutrientes e produtos metabólicos (Mn, Fe, ΣNO3-, NH4+, PO43-, SO42-, ΣH2S, sílica dissolvida (SiD), e alcalinidade) nas águas intersticiais e os fluxos de ΣNO3-, NH4+, PO43- e SiD na interface água-sedimento (IAS) foram estudados em três ambientes que representam cenários diferentes de aportes antrópicos da zona costeira do estado do Rio de Janeiro, incluindo a Baía de Cabo Frio (CF), a Enseada de Jurujuba (JU) e a Baía de Sepetiba (SE). As razões C:N:P e as assinaturas isotópicas (13C e 15N) dos sedimentos indicaram que a MO é de origem marinha no testemunho CF e JU. Já em SE ocorre matéria orgânica (MO) de origem marinha e terrestre, havendo predominância de origem fitoplanctônica. As concentrações de COT demonstraram similaridades no acúmulo do material orgânico entre a BC e a SE, enquanto JU apresentou concentrações mais altas. Os padrões de distribuição das zonas redox dentro da coluna sedimentar, baseado nos perfis de água intersticial, nos ambientes estudados mostraram serem influenciados pela variabilidade do teor de COT e processos de bioturbação e/ou físicos. Na CF, sob condições subóxicas, as principais reações redox foram bem identificadas nos sedimentos superficiais e seguiu a sequência teórica do consumo oxidante: ΣNO3->MnO2>Fe(OH)3, a zona de redução de SO42- não foi evidenciada nesse perfil. Na JU, sob condições anóxicas, os perfis de água intersticial indicaram um zoneamento redox “comprimido”, favorecendo a contração das zonas óxica-subóxica e expansão da região sulfídrica. As altas concentrações de alcalinidade, amônio e sulfeto indicaram degradação intensiva de matéria orgânica no testemunho JU, dominado pela zona de redução de sulfato e uma influência menor pela das reduções de ΣNO3-, MnO2 e Fe(OH)3. Na SE, sob condições subóxicas e a presença de macrofauna observada no sedimento, duas sequências diagenéticas sobrepostas foram observadas. A primeira sequência envolveu a redução do NO3-, MnO2 e Fe(OH)3. A segunda sequência diagenética envolveu a redução do MnO2 e Fe(OH)3. A presença de duas sequências diagenéticas pode estar relacionada aos efeitos de bioturbação e/ou outras perturbações físicas, como eventos de dragagem em áreas adjacentes e atividades de embarcações que causam ressuspensão do sedimento. A ocorrência de variação da concentração de COT no topo do testemunho SE, ressalta a perturbação do sedimento. Foi evidenciado que os fluxos de NO3- e NH4+ em CF são influenciados pelos processos de desnitrificação, em JU pelo processo de desnitrificação e redução desassimilatória de nitrato para amônio, já em SE pelos processos de desnitrificação e nitrificação. O fluxo do PO43- foi afetado pela precipitação de mineral autigênico e bioturbação do sedimento. E o fluxo de SiD foi afetado pela gradual dissolução de sílica biogênica com o aumento da profundidade. Em JU foram observados os maiores fluxos de NO3-, NH4+ e SiD na IAS. No entanto, o fluxo de PO43- mais alto foi observado na IAS da Baía de Sepetiba, provavelmente devido às baixas concentrações de PO43- encontradas na água de fundo em relação às outras áreas de estudo / The early diagenesis of the redox-sensitive trace metals, nutrients, metabolic products (Mn, Fe, ΣNO3-, NH4+, PO43-, SiD, SO42-, H2S and alcalinity) in pore waters and the fluxes of the ΣNO3-, NH4+, PO43- and DSi at the sediment-water interface (SWI) were studied in three environments that represent different scenarios of anthropogenic inputs of the coastal zone of the state of Rio de Janeiro, including the Cabo Frio Bay (CF), Jurujuba Sound (JU) and Sepetiba Bay (SE). The C:N:P ratios and isotopic signatures (13C and 15N) of the sediments indicated that organic matter (OM) is of marine origin in CF and JU core. In SE occurs OM marine and terrestrial origin, with predominance of phytoplankton origin. The TOC concentrations have demonstrated similarities in the accumulation of organic material between BC and SE, while JU submitted higher concentrations. The distribution patterns of redox zones within the sedimentary column, based on pore water profiles, in the studied environments showed to be influenced by the variability of the TOC content and bioturbation and/or physical processes. In CF, under suboxic conditions, the main redox reactions have been identified in surface sediments and followed the theoretical result of oxidant consumption: ΣNO3-> MnO2> Fe (OH)3, the SO42- reduction zone was no evidence in this profile. In JU, under anoxic conditions, the pore water profiles indicated a redox zone ‘compressed’, favoring the contraction of the oxic-suboxic zones and expansion of sulfidic region. The high concentrations of alkalinity, ammonium and sulfide indicated intensive degradation of OM in JU core dominated by the sulfate reduction zone and a smaller influence by the ΣNO3-, MnO2 and Fe (OH)3 reductions. In SE, under suboxic conditions and with the observed presence of macrofauna in the sediment, two overlapped diagenetic sequences can be observed. The first sequence involved the reduction of ΣNO3-, MnO2 and Fe (OH)3. The second diagenetic sequence involved the reduction of MnO2 and Fe (OH)3. The presence of two diagenetic sequences may be related to effects bioturbation and/or other physical disturbances, such as dredging events in adjacent areas and craft activities that cause sediment resuspension. The occurrence of variation of TOC concentration at the top of the SE core, emphasizes the disturbance of sediment. It was evidenced that the fluxes of ΣNO3- and NH4+ in CF are influenced by denitrification processes, in the JU by process denitrification and nitrate dissimilatory reduction to ammonium, as in SE by nitrification and denitrification processes. The PO43- fluxes was affected by the precipitation of autigenic mineral and bioturbation of the sediment. And the SiD flux is affected by the gradual dissolution of biogenic silica with increasing depth. In JU were observed larger fluxes of ΣNO3-, NH4+ and DSi at the SWI were observed. However, the higher PO43- fluxes was observed at the SWI Sepetiba Bay, probably due to low concentrations of PO43- found in the overlying water in relation to other areas of study.

Marine sediments are a key component of the global carbon cycle and climate system. They host one of the largest carbon reservoirs on Earth, provide the only long-term sink for atmospheric CO2, recycle nutrients and represent the most important climate archive. Early diagenetic pro- cesses in marine sediments are thus central to our understanding of past, present and future biogeochemical cycling and climate. Because all early diagenetic processes can be directly or indirectly linked back to the degradation of organic matter (OM), advancing this understand- ing requires disentangling the different factors that control the fate of OM (sedimentation, degradation and burial) on different spatial and temporal scales. In general, the heterotrophic degradation of OM in marine sediments is controlled by the quantity and, in particular, by the ap- parent reactivity of OM that settles onto marine sediments. While the potential ((micro)biological, chemical and physical) controls on OM reactivity are increasingly well understood, their relative significance remains difficult to quantify. Traditionally, integrated data-model approaches are used to quantify apparent OM reactivity (i.e. OM degradation rate constants) at well-studied drill-sites. These approaches rely on Reaction-Transport Models (RTMs) that typically account for transport (advection, molecular diffusion, bioturbation, and bioirrigation) and reaction (pro- duction, consumption, equilibrium) processes, but vary in complexity. Apparent OM reactivity (i.e. the OM degradation rate constant) is generally considered as a free parameter that is used to fit observed depth-profiles, reaction rates or benthic-pelagic exchange fluxes. Currently, no quantitative framework exists to predict apparent OM reactivity in areas where comprehensive benthic data sets are not available.To evaluate the impact of this knowledge gap, the sensitivity of benthic biogeochemical reaction rates, as well as benthic-pelagic exchange fluxes to variations in apparent OM reactivity (i.e. reactive continuum model parameters a and ν) is explored by means of a complex, numerical diagenetic model for shelf, slope and deep sea depositional environments. Model results show that apparent OM reactivity exerts a dominant control on the magnitude of biogeochemical reaction rates and benthic-pelagic exchange fluxes across different environments. The lack of a general framework to quantify OM reactivity thus complicates the parametrization of regional and global scale diagenetic models and, thus, compromises our ability to quantify global benthic-pelagic coupling in general and OM degradation dynamics in particular.To make a first step towards an improved systematic and quantitative knowledge of OM reac- tivity, apparent OM reactivity (i.e. reactive continuum model parameters a and ν) is quantified by inverse modelling of organic carbon, sulfate (and methane) sediment profiles, as well as the location of the sulfate-methane transition zone using a complex, numerical diagenetic model for 14 individual sites across different depositional environments. Model results highlight again the dominant control of OM reactivity on biogeochemical reaction rates and benthic exchange fluxes. In addition, results show that, inversely determined ν-values fall within a narrow range (0.1 < ν < 0.2). In contrast, determined a-values span ten orders of magnitude (1 · 10−3 < a < 1·107) and are, thus, the main driver of the global variability in OM reactivity. Exploring these trends in their environmental context reveals that apparent OM reactivity is determined by a dynamic set of environmental controls rather than traditionally proposed single environmental controls (e.g. water depth, sedimentation rate, OM fluxes). However, the high computational demand associated with such a multi-species inverse model approach, as well as the limited availability of comprehensive pore water data, limits the number of apparent OM reactivity estimates. Therefore, while providing important primers for a quantification of OM reactivity on the global scale, inverse model results fall short of providing a predictive framework.To overcome the computational limitations and expand the inverse modelling of apparent OM reactivity to the global scale, the analytical model OMEN-SED is extended by integrating a nG- approximation of the reactive continuum model that is fully consistent with the general structure of OMEN-SED. The new version OMEN-SED-RCM thus provides the computational efficiency required for the inverse determination of apparent OM reactivity (i.e. reactive continuum model parameters a and ν) on the global scale. The abilities of the new model OMEN-SED-RCM in capturing observed local, as well as global patterns of diagenetic dynamics are rigorously tested by model-data, as well as model-model comparison.OMEN-SED-RCM is then used to inversely determine apparent OM reactivity by inverse modelling of 394 individual dissolved oxygen utilisation (DOU) rate measurements. DOU is commonly used as a proxy for OM reactivity, it is more widely available than comprehensive porewater data sets and global/regional benthic maps of dissolved oxygen utilisation rates (DOU) have been derived based on the growing DOU data set. Sensitivity test show that, while inverse modelling of DOU rates fails to provide a robust estimate of RCM parameter ν, it is a good indicator for RCM parameter a. Based on previous findings, parameter ν was thus assumed to be globally constant. Inversely determined a-values vary over order of magnitudes from a = 0.6 years in the South Polar region to a = 5.6 · 106 in the oligotrophic, central South Pacific. Despite a high intra- as well as interregional heterogeneity in apparent benthic OM reactivity, a number of clear regional patterns that broadly agree with previous observations emerge. High apparent OM reactivities are generally observed in regions dominated by marine OM sources and characterized by efficient sinking of OM and a limited degradation during sinking. In contrast, the lowest apparent OM reactivities are observed for regions characterized by low marine primary production rates, in combination with a great distance to the continental shelf and slope, as well as deep water columns. Yet, results also highlight the importance of lateral transport processes for apparent OM reactivity. In particular, deep sea sediments in the vicinity of dynamic continental margin environments or under the influence of strong ocean currents can receive comparably reactive OM inputs from more productive environments and, thus, reveal OM reactivities that are higher than traditionally expected. Finally, based on the observed strong link between apparent OM reactivity (i.e. RCM parameters a) and DOU rate, a transfer function that predicts the order of magnitude of RCM parameter a as a function of DOU is used to derive, to our knowledge, the first global map of apparent OM reactivity.Finally, we use the new global map of apparent OM reactivity to quantify biogeochemical dynamics and benthic-pelagic coupling across 22 benthic provinces that cover the entire global ocean. To this end, the numerical diagenetic model BRNS model is set-up for each province and forced with regionally averaged boundary conditions derived from global data sets, as well as apparent OM reactivities informed by the global OM reactivity map. The 22 regional model set-ups were then used to quantify biogeochemical process rates, as well as benthic carbon and nutrient fluxes in each province and on the global scale. Model results of regional and global fluxes and rates fall well within the range of observed values and also agree with general globally observed patterns. Results also highlight the role of the deeper ocean for benthic-pelagic cycling and indicate towards a large regional variability in benthic cycling at great depth. This is a first step towards a more refined global estimate of benthic biogeochemical cycling that accounts for the global heterogeneity of the seafloor environment. This aspect is critical to improve our understanding of benthic feedbacks on benthic-pelagic coupling and on the carbon-climate system, which can then be incorporated in benthic processes in Earth System Models. / Les sédiments marins sont un élément clé du cycle mondial du carbone et du système climatique. Ils abritent l’un des plus grands réservoirs de carbone sur Terre, fournissent le seul puits à long terme pour le CO2 atmosphérique, recyclent les nutriments et constituent les archives climatiques les plus importantes. Les processus de la diagénèse précoce dans les sédiments marins sont donc au cœur de notre compréhension des cycles et du climat biogéochimiques passés, présents et futurs. Étant donné que tous les processus diagénétiques précoces peuvent être directement ou indirectement liés à la dégradation de la matière organique (MO), faire progresser cette compréhension nécessite de démêler les différents facteurs qui contrôlent le devenir de la MO (sédimentation, dégradation et enfouissement) à différentes échelles spatiales et temporelles. En général, la dégradation hétérotrophique de la MO dans les sédiments marins est contrôlée par la quantité et, en particulier, la réactivité apparente de la MO qui se dépose sur les sédiments marins. Bien que les contrôles potentiels ((micro) biologiques, chimiques et physiques) de la réactivité de la MO soient de mieux en mieux compris, leur importance relative reste difficile à quantifier. Traditionnellement, des approches de modèle de données intégrées sont utilisées pour quantifier la réactivité apparente de la MO (c’est-à-dire les constantes de vitesse de dégradation de la MO) sur des sites de forage bien étudiés. Ces approches reposent sur des modèles de réaction-transport (RTM) qui tiennent généralement compte des processus de transport (advection, diffusion moléculaire, bioturbation et bio-irrigation) et de réaction (production, consommation, équilibre), mais leur complexité varie. La réactivité apparente de la MO est généralement considérée comme un paramètre libre qui est utilisé pour ajuster les profils de profondeur, les taux de réaction ou les flux d’échange benthique-pélagique observés. À l’heure actuelle, aucun cadre quantitatif n’existe pour prédire la réactivité apparente de la MO dans les zones où aucun ensemble complet de données benthiques n’est disponible.Pour évaluer l’impact de ce manque de connaissance, nous avons exploré la sensibilité des taux de réaction biogéochimiques benthiques, ainsi que des flux d’échange benthique-pélagique aux variations de la réactivité apparente de la MO (c.-à-d. les paramètres du modèle de con- tinuum réactif a et ν) au moyen d’un modèle diagénétique numérique complexe appliqué aux zones de dépôts sur les plateaux, les talus et en haute mer. Les résultats du modèle montrent que la réactivité apparente de la MO exerce un contrôle dominant sur l’ampleur des taux de réaction biogéochimiques et des flux d’échange benthique-pélagique dans différents environ- nements. L’absence d’un cadre général pour quantifier la réactivité de la MO complique donc la paramétrisation des modèles diagénétiques à l’échelle régionale et mondiale et, ainsi, compromet notre capacité à quantifier le couplage benthique-pélagique global en général et la dynamique de dégradation de la MO en particulier.Pour tendre à meilleure connaissance systématique et quantitative de la réactivité de la MO, la réactivité apparente OM (c.-à-d. les paramètres du modèle de continuum réactif a et ν) est quantifiée par modélisation inverse des profils de sédiments organiques de carbone, de sulfate (et de méthane), ainsi que localisation de la zone de transition sulfate-méthane à l’aide d’un modèle diagénétique numérique complexe pour 14 sites individuels à travers différents environnements de dépôt. Les résultats du modèle mettent à nouveau en évidence le contrôle dominant de la réactivité de l’OM sur les taux de réaction biogéochimiques et les flux d’échanges benthiques. De plus, les résultats montrent que les valeurs déterminées inversement déterminées se situent dans une plage étroite (0,1 <ν<0,2). En revanche, les valeurs déterminées s’étendent sur dix ordres de grandeur (1 ·10−3 <ν< 1·107) et sont donc le principal moteur de la variabilité globale de la réactivité OM. L’exploration de ces tendances dans leur contexte environnemental révèle que la réactivité apparente de l’OM est déterminée par un ensemble dynamique de contrôles environnementaux plutôt que par des contrôles environnementaux uniques traditionnellement proposés (par exemple, la profondeur de l’eau, le taux de sédimentation, les flux OM). Cependant, la forte demande de calcul associée à une telle approche de modèle inverse multi-espèces, ainsi que la disponibilité limitée de données complètes sur l’eau interstitielle, limitent le nombre d’estimations apparentes de la réactivité OM. Par conséquent, tout en fournissant des amorces importantes pour une quantification de la réactivité de l’OM à l’échelle mondiale, les résultats du modèle inverse sont loin de fournir un cadre prédictif.Pour surmonter les limites de calcul et étendre la modélisation inverse de la réactivité apparente de l’OM à l’échelle mondiale, le modèle analytique OMEN-SED est étendu en intégrant une approximation nG du modèle de continuum réactif qui est pleinement cohérente avec la structure générale d’OMEN-SED. La nouvelle version OMEN-SED-RCM fournit ainsi l’efficacité de calcul requise pour la détermination inverse de la réactivité apparente de l’OM (c’est-à-dire les paramètres du modèle de continuum réactif a et ν) à l’échelle mondiale. Les capacités du nouveau modèle OMEN-SED-RCM à capturer les modèles locaux et globaux de dynamique diagénétique observés sont rigoureusement testés par les données du modèle, ainsi que la comparaison modèle- modèle.OMEN-SED-RCM est ensuite utilisé pour déterminer inversement la réactivité apparente de l’OM par modélisation inverse de 394 mesures individuelles du taux d’utilisation de l’oxygène dissous (DOU). Le DOU est couramment utilisé comme indicateur de la réactivité de l’OM, il est plus largement disponible que les ensembles de données exhaustifs sur l’eau interstitielle et les cartes benthiques mondiales/régionales des taux d’utilisation de l’oxygène dissous (DOU) ont été dérivées sur la base de l’ensemble de données DOU croissant. Le test de sensibilité montre que, bien que la modélisation inverse des taux de DOU ne fournisse pas une estimation robuste du paramètre RCM ν, c’est un bon indicateur pour le paramètre RCM a. Sur la base des résultats précédents, le paramètre ν a donc été supposé être globalement constant. Les valeurs a déterminées à l’inverse varient selon l’ordre de grandeur, de a = 0,6 an dans la région polaire sud à a = 5, 6 · 106 dans le Pacifique sud oligotrophique central. Malgré une forte hétérogénéité intra et interrégionale dans la réactivité apparente de la MO benthique, un certain nombre de schémas régionaux clairs qui correspondent largement aux observations précédentes émergent. Des réactivités apparentes élevées de l’OM sont généralement observées dans les régions dominées par des sources marines de MO et caractérisées par un naufrage efficace de l’OM et une dégradation limitée pendant le naufrage. En revanche, les réactivités MO apparentes les plus faibles sont observées pour les régions caractérisées par de faibles taux de production primaire marine, en combinaison avec une grande distance du plateau continental et de la pente, ainsi que des colonnes d’eau profonde. Pourtant, les résultats mettent également en évidence l’importance des processus de transport latéral pour la réactivité apparente de l’OM.En particulier, les sédiments des mers profondes au voisinage d’environnements de marge continentale dynamiques ou sous l’influence de forts courants océaniques peuvent recevoir des apports OM de réactivité comparable provenant d’environnements plus productifs et, ainsi, révéler des réactivités OM plus élevées que ce qui était traditionnellement prévu. Enfin, sur la base du lien fort observé entre la réactivité apparente de l’OM (c’est-à-dire le paramètre RCM a) et le taux DOU, une fonction de transfert qui prédit l’ordre de grandeur du paramètre RCM a en fonction de DOU est utilisée pour dériver, pour nos connaissances, la première carte mondiale de la réactivité apparente de l’OM. Les résultats du modèle des flux et des taux régionaux et mondiaux se situent bien dans la gamme des valeurs observées et également d’accord avec les tendances générales observées au niveau mondial. Les résultats mettent également en évidence le rôle de l’océan profond pour le cycle benthique-pélagique et indiquent une grande variabilité régionale du cycle benthique à grande profondeur. Il s’agit d’une première étape vers une estimation mondiale plus précise du cycle biogéochimique benthique qui tient compte de l’hétérogénéité mondiale du milieu marin. Cet aspect est essentiel pour améliorer notre compréhension des rétroactions benthiques sur le couplage benthique-pélagique et sur le système carbone-climat, qui peuvent ensuite être incorporées aux processus benthiques dans les modèles du système terrestre. / Doctorat en Sciences / info:eu-repo/semantics/nonPublished