Since the industrial revolution, CO sub 2 has increased in the atmosphere and about 40% of the increase has been taken up by the ocean. An artifact of increasing CO sub 2 in the ocean is ocean acidification; it changes the calcium carbonate saturation state, which in turn alters the calcification rate of shelled organisms. The purpose of this dissertation is to estimate the changes in the carbonate system in the oceans, and whether these changes are due to natural (biological activity, chemical transformation or mixing of water masses) or anthropogenic (human activities) perturbations. The first hypothesis states that the presence of boric acid (B(OH) sub 3) in seawater changes the thermodynamic constants of CO sub 2, pK sup * sup 1 and pKsup * sup 2. Due to experimental limitations, the solubility of B(OH) sub 3 was determined in electrolyte solutions (LiCl, NaCl, KCl, RbCl and CsCl) instead of real or artificial seawater. The results can be used to estimate the B(OH) sub 3 activity coefficients gamma sub B and solubility [B] in natural mixed electrolyte solutions. The second hypothesis states that filtering seawater sampled in the open ocean is necessary for the determination of total alkalinity (TA). Measurement of 180 samples of surface, oxygen minimum, and deep waters in the Pacific and Indian oceans revealed that the at- sea measured TA of filtered and unfiltered samples were not statistically different. Finally, a synthesis and analysis of the carbonate parameters in the Atlantic and Indian oceans is undertaken. Results from repeat hydrographic cruises in these oceans were used for this task. Parameters TA and total CO sub 2 (TCO sub 2) are predicted using hydrographic properties and a multi-linear regression method to obtain a more homogenous dataset. The results of the predicted TA prove to be successful, which is not the case for TCO sub 2 at the surface of the ocean. Finally, it is found that the increase in anthropogenic CO sub 2 signal remineralization and mixing of water masses increase the acidity of the ocean at the surface and in deep waters, respectively. This causes the aragonite saturation horizon to shoal. Recommendations for further studies are provided in the "Summary and conclusion" chapter.

Conchas do molusco Physa sp., um gastrópode (caracol) comum de aquários de água doce, serviram como modelo para o estudo de alguns aspectos envolvidos na biomineralização. A concha calcária é constituída por cristais de carbonato de cálcio depositados em associação com uma matriz orgânica. Os componentes cristalinos e a matriz, foram estudados por microscopia eletrônica de transmissão e de varredura, e caracterizados por métodos espectroscópicos e analíticos. A constituição cristalina, em geral, assemelha-se àquela existente na maioria dos moluscos, enquanto a camada nacarada, interna da concha, apresenta comparativamente maiores variações. A matriz orgânica consta de um componente insolúvel, essencialmente constituído por polissacarídeos, enxofre e fósforo; e outro componente solúvel, com predominância de serina, glicina, ácido aspártico e ácido glutâmico. A análise feita por ativação de nêutrons demonstrou maior concentração de cálcio, sódio e estrôncio; estes elementos estão geralmente relacionados à presença de aragonita, em outras conchas de moluscos. O estudo qualitativo da fase cristalina foi realizado por difração eletrônica e por espectroscopia de infravermelho. Para análise quantitativa, usou-se a difração de raios-X, sendo os dados refinados pelo método de Rietveld. Os resultados obtidos demonstram a existência de dois polimorfos do carbonato de cálcio, aragonita e calcita, na concha da Physa. A caracterização qualitativa dos componentes inorgânico e orgânico do material estudado, mostrou semelhanças com relação a outros gêneros de moluscos. Experimentos de cristalização do carbonato de cálcio in vitro produziram aragonita e vaterita em presença de ácido aspártico ou glutâmico. Sob ação de glicina, serina ou quitina, houve formação de calcita. Em presença da matriz orgânica insolúvel, houve cristalização de calcita, enquanto a matriz solúvel induziu a cristalização da aragonita. Analisou-se quantitativamente todas as fases cristalinas obtidas nestes experimentos e estudou-se a morfologia dos cristais formados através da MEV e por MO luz. O resultado comparativo das investigações usando a concha natural, e dos cristais sintetizados, permitiu confirmar o papel fundamental da matriz orgânica no processo de cristalização do carbonato de cálcio. / Shells of Physa sp., a common freshwater gastropod snail, were used as a model for mineralization studies of calcium carbonate. The shell is a biomineral that consists of organized crystalline deposits associated to an organic matrix, both of which were studied by transmission and scanning electron microscopy; they were further characterized by means of pectroscopic and analytical methods. As a whole, its structural organization does not differ greatly from that found in other mollusc shells, except for the innermost, nacreous layer, that lines the shell. The organic matrix in Physa was found to consist of an insoluble fraction, essentially containing a polysaccharide, sulphur and phosphor. In addition, another (soluble) fraction is present, in which serine, glycine, aspartic acid and glutamic acid residues prevail. Neutronic activation analysis demonstrates a high concentration of calcium, sodium and strontium, elements known to be related to the presence of aragonite in other molluscan shells. A qualitative study of the crystalline phase was obtained through use of electron diffraction and FTIR spectroscopy. For quantitative analysis X-ray diffraction was used, as refined by the Rietveld method. Results obtained demonstrate the existence of two calcium carbonate polymorphs, aragonite and calcite in the shell of Physa, Qualitative evaluation of both organic and inorganic material from Physa showed similarities to those found in other mollusk shells. In vitro experiments performed at similar-to-natural conditions, on crystallization of calcium carbonate, did also crystallize aragonite and vaterite, provided aspartic acid or glutamic acid were present; whereas calcite was formed in solutions containing glycine, serine or chitin. Aragonite did crystallize when the soluble organic matrix was added to the solution. All these crystalline phases obtained were quantitatively evaluated, their morphologies being studied through light and electron microscopies. A comparative study of the natural crystals from the shell, and those obtained in laboratory experiments, stresses the fundamental role of the organic matrix on calcium carbonate crystallization

Conchas do molusco Physa sp., um gastrópode (caracol) comum de aquários de água doce, serviram como modelo para o estudo de alguns aspectos envolvidos na biomineralização. A concha calcária é constituída por cristais de carbonato de cálcio depositados em associação com uma matriz orgânica. Os componentes cristalinos e a matriz, foram estudados por microscopia eletrônica de transmissão e de varredura, e caracterizados por métodos espectroscópicos e analíticos. A constituição cristalina, em geral, assemelha-se àquela existente na maioria dos moluscos, enquanto a camada nacarada, interna da concha, apresenta comparativamente maiores variações. A matriz orgânica consta de um componente insolúvel, essencialmente constituído por polissacarídeos, enxofre e fósforo; e outro componente solúvel, com predominância de serina, glicina, ácido aspártico e ácido glutâmico. A análise feita por ativação de nêutrons demonstrou maior concentração de cálcio, sódio e estrôncio; estes elementos estão geralmente relacionados à presença de aragonita, em outras conchas de moluscos. O estudo qualitativo da fase cristalina foi realizado por difração eletrônica e por espectroscopia de infravermelho. Para análise quantitativa, usou-se a difração de raios-X, sendo os dados refinados pelo método de Rietveld. Os resultados obtidos demonstram a existência de dois polimorfos do carbonato de cálcio, aragonita e calcita, na concha da Physa. A caracterização qualitativa dos componentes inorgânico e orgânico do material estudado, mostrou semelhanças com relação a outros gêneros de moluscos. Experimentos de cristalização do carbonato de cálcio in vitro produziram aragonita e vaterita em presença de ácido aspártico ou glutâmico. Sob ação de glicina, serina ou quitina, houve formação de calcita. Em presença da matriz orgânica insolúvel, houve cristalização de calcita, enquanto a matriz solúvel induziu a cristalização da aragonita. Analisou-se quantitativamente todas as fases cristalinas obtidas nestes experimentos e estudou-se a morfologia dos cristais formados através da MEV e por MO luz. O resultado comparativo das investigações usando a concha natural, e dos cristais sintetizados, permitiu confirmar o papel fundamental da matriz orgânica no processo de cristalização do carbonato de cálcio. / Shells of Physa sp., a common freshwater gastropod snail, were used as a model for mineralization studies of calcium carbonate. The shell is a biomineral that consists of organized crystalline deposits associated to an organic matrix, both of which were studied by transmission and scanning electron microscopy; they were further characterized by means of pectroscopic and analytical methods. As a whole, its structural organization does not differ greatly from that found in other mollusc shells, except for the innermost, nacreous layer, that lines the shell. The organic matrix in Physa was found to consist of an insoluble fraction, essentially containing a polysaccharide, sulphur and phosphor. In addition, another (soluble) fraction is present, in which serine, glycine, aspartic acid and glutamic acid residues prevail. Neutronic activation analysis demonstrates a high concentration of calcium, sodium and strontium, elements known to be related to the presence of aragonite in other molluscan shells. A qualitative study of the crystalline phase was obtained through use of electron diffraction and FTIR spectroscopy. For quantitative analysis X-ray diffraction was used, as refined by the Rietveld method. Results obtained demonstrate the existence of two calcium carbonate polymorphs, aragonite and calcite in the shell of Physa, Qualitative evaluation of both organic and inorganic material from Physa showed similarities to those found in other mollusk shells. In vitro experiments performed at similar-to-natural conditions, on crystallization of calcium carbonate, did also crystallize aragonite and vaterite, provided aspartic acid or glutamic acid were present; whereas calcite was formed in solutions containing glycine, serine or chitin. Aragonite did crystallize when the soluble organic matrix was added to the solution. All these crystalline phases obtained were quantitatively evaluated, their morphologies being studied through light and electron microscopies. A comparative study of the natural crystals from the shell, and those obtained in laboratory experiments, stresses the fundamental role of the organic matrix on calcium carbonate crystallization

Archaias angulatus, a large symbiont-bearing foraminifer (Order Miliolida) that produces a Mg-calcite shell, is common throughout the Caribbean and warm western Atlantic region. This species lives abundantly in seagrass beds along the Springs Coast of northwest Florida (up to 4 adults per gram of sediment) where spring-fed rivers emerge from a limestone aquifer, and in Florida Bay to the southeast (25 adults/g) where the sediment is primarily biogenic carbonate. In contrast, live specimens are seldom found in the seagrass beds along the central-west coast of Florida, where barrier islands are dominated by quartz sand. My working hypothesis is that substratum and carbonate chemistry, in addition to temperature and salinity, explain differences in abundance of A. angulatus associated with the seagrass meadows along the west Florida coastline and shelf. Water chemistry measurements were taken diurnally over 1-2 day periods at four sites in winter, spring and autumn of 2015. Salinity and temperature were measured in situ, and sealed bottles of seawater were transported to the laboratory for analysis of Dissolved Inorganic Carbon (DIC) and Total Alkalinity (TA). The highest TA was found in the Springs Coast (2766 μmol/kg-seawater, three-season average), along with the lowest salinities, which reveals a strong contribution from the nearby rivers, springs and seeps. A TA end-member regression analysis predicts, and sampling confirms, TA increases with proximity to the river mouth, highlighting the atypical relationship between alkalinity and salinity in this carbonate province. A gradient in the value of TA was seen among the northern three sites, with TA decreasing from the Springs Coast site southward to Fort Desoto; additionally, the pH and calcium carbonate saturation states were higher at the northernmost sites. The highest ratio of TA to DIC among all four sites was found at the southern edge of the Springs Coast, reflecting strong primary production and DIC uptake by the dense meadows of seagrass in the area. A daytime increase in the TA to DIC ratio was seen at all sites; however, the Springs Coast site (~5km from the Weeki Wachee river mouth) exhibited stronger tidal influences on TA and DIC than diurnal influences. Plots of salinity-normalized TA and DIC indicate the Weeki Wachee coastal area is impacted by calcification and dissolution to a greater extent than by photosynthesis and respiration. The gradual relief off the Springs Coast, as well as clarity of the water column, provide ideal physical habitat, and the input from spring-fed sources enhances the water chemistry for calcifying organisms. Presence of A. angulatus in low salinity waters influenced by high alkalinity riverine discharge led to a new hypothesis that calcification in A. angulatus requires high carbonate alkalinity but not necessarily full marine salinity.

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.

Le Haut-Atlas central est un bassin salifère structuré autour d’étroites rides diapiriques (i.e. salt walls) orientées ENE-OSO qui bordent de larges mini-bassins. L’impact de la compression cénozoïque étant relativement limitée, les structures diapiriques y sont particulièrement bien préservées. L’objectif de la thèse est d’analyser les relations entre la sédimentation et la croissance des rides diapiriques dans le cadre imposé par l’évolution du système sédimentaire, durant le Jurassique inférieur et moyen, dans la région d’Imilchil, au cœur du haut-Atlas central. Le Lias-Dogger enregistre le comblement du bassin atlasique à travers six séquences de transgression-régression de troisième ordre. Cette grande tendance régressive se manifeste par la succession de trois systèmes de dépôts. Un système carbonaté, du Toarcien au Bajocien supérieur, dont l’éventail de faciès oscille entre la rampe moyenne et la rampe externe distale. Au Bajocien supérieur l’apport de sédiments terrigènes dans le bassin provoque la disparition du système carbonaté qui est recouvert par une épaisse série sédimentaire mixte peu profonde. Ce système mixte perdure jusqu’au Bathonien inférieur puis il est progressivement remplacé par un système fluviatile silico-clastique. Les relations entre les mouvements diapiriques et la sédimentation peuvent être mises en évidence par une modification de la géométrie des dépôts, par des variations de faciès aux abords des diapirs, et/ou par des événements sédimentaires particuliers (surfaces d’érosion, brèches, niveau condensé). L’analyse de ces interactions en fonction des séquences de transgression-régression permet de définir une chronologie de l’activité diapirique. Elle est continue pendant le Jurassique inférieur et moyen mais connait une évolution polyphasée comprenant deux périodes d’activité majeure, du Toarcien à l’Aalénien terminal et du Bajocien supérieur jusqu’à ce que les diapirs soient scellés au Bathonien supérieur-Callovien inférieur. Ces deux périodes encadrent un épisode de plus faible intensité pendant la progradation et le développement de la rampe carbonatée bajocienne. Les interactions entre diapirisme et sédimentation sont synthétisées dans un modèle empirique à travers quatre types de prismes de dépôts, définis selon des critères géométriques et sédimentologiques, et qui rendent compte de la configuration du système sédimentaire, ainsi que de la position du diapir et de sa couverture au moment du dépôt : A plus grande échelle l’influence du développement des mini-bassins sur la sédimentation s’exprime par une distribution préférentielle des faciès sédimentaire dans les systèmes de dépôt carbonaté et mixte. Les faciès proximaux, et en particulier les faciès granulaires de haute énergie, se regroupent autour des rides diapiriques tandis que les faciès distaux de basse énergie se concentrent dans l’axe des mini-bassins. / The High-Atlas salt basin is formed by a set of ENE-WSW-trending and 15-to-80-kilometers-long narrow diapiric ridges (i.e. salt walls) bounding large mini-basins mildly deformed during Cenozoic shortening. The aim of this thesis is to analyze the relationships between sedimentation and diapiric growth during the Lower and Middle Jurassic in the Imilchil region (Central High-Atlas). In this area, the Lias and Dogger series form a large regressive trend composed by six third-order transgression-regression (T/R) sequences and characterized by the succession of three sedimentary systems. A carbonate system develop from Toarcian to Upper Bajocian, with a facies range from middle ramp to distal outer ramp. From Upper Bajocian, a terrigenous supply in the basin causes the end of the carbonate system and leads to the deposition of a thick shallow mixed unit. From Lower Bathonian, this mixed sedimentary system is gradually replaced by an alluvial silici-clastic system. Relationships between diapiric movements and sedimentation are interpreted from depositional geometries, facies variations in the vicinity of diapirs and/or particular sedimentary events (erosional surfaces, breccia, condensed levels). The analysis of these interactions, based on T/R sequences, enables to define a chronology of the diapiric activity in the Imilchil area. The activity is continuous during the Lower and Middle Jurassic but shows a non-linear development with two phases of high-intensity, one from Toarcian to Uppermost Aalenian, and one from Upper Bajocian. These two phases surround a period of low-intensity during the progradation and the development of the bajocian carbonate ramp system. Interactions between diapirism and sedimentation are summarized in an empirical model consisting of four types of depositional prisms defined by geometrical and sedimentological criteria. On a larger scale, the impact of the mini-basin on the sedimentation is characterized by a specific facies distribution in the carbonate and mixed depositional system. The high-energy granular facies are concentrated around the diapiric structures and the distal low-energy facies are deposited in the axis of the mini-basins.

L'étude des milieux hétérogènes carbonatés et karstifiés trouve aujourd'hui de nombreuses applications dans les problématiques environnementales, comme la description fine de la structure d'un réservoir côtier, support d'un aquifère affecté par une intrusion d'eau salée. Au sud de l'ile de Majorque (Baléares, Espagne), la plate-forme carbonatée de Llucmajor représente un site privilégié pour ce type d'étude.La caractérisation des hétérogénéités ne peut être réalisée sans une description préalable des propriétés des réservoirs carbonatés et des facteurs modifiant la structure du réservoir. Un des paramètres clés définissant la structure hétérogène est la porosité. Au regard de la large gamme de tailles d'hétérogénéités allant du micromètre à la centaine de mètre, l'utilisation de méthodes multi-échelles est nécessaire.Ce travail de thèse a porté sur la détermination multi-échelles de la porosité, allant de la microporosité à la porosité karstique, et l'établissement de relations entre les changements d'échelles d'observation de ces propriétés. Dans un premier temps, l'application de la microtomographie à rayons X extrait la microporosité et la connectivité des réseaux microporeux. Puis, la tomographie a été utilisée avec une résolution plus faible afin d'étudier le réseau micro- et macroporeux à l'échelle de la carotte. A l'échelle du puits, les images de paroi de puits permettent de déterminer la porosité allant des macropores centimétriques aux karsts. Enfin, la géophysique de surface a permis d'observer l'extension des karsts et hétérogénéités dans une grande partie du site.Ainsi, la structure poreuse du site étudié a été intégrée dans la géologie régionale de la plate-forme. L'observatoire installé sur le site pour surveiller la propagation de l'eau salée dans l'aquifère peut être replacé dans son contexte géologique et pétrophysique, afin d'affiner l'interprétation de ses mesures de variations de salinité. / The study of heterogeneous and karstified carbonates is important in many environmental issues, like the detailed description of a coastal reservoir structure containing an aquifer affected by saline intrusion. At the south of the island of Mallorca (Spain), the Llucmajor carbonate platform represents a typical site for such researches. Characterization of heterogeneities requires a better knowledge of the carbonate reservoir properties and the various factors affecting the structure. One of the key parameters defining the heterogeneous structure is the porosity. According to the wide range of heterogeneity sizes from micrometer to hundreds of meters, the use of multiscale methods is required.This thesis focused on the determination of multiscale porosities from the microporosity to karstic porosity, and of relationships between observation scale changes of these properties. Firstly, the application of X-ray microtomography allows to extract the microporosity and the microporous network connectivity. Then, X-ray tomography was used with a lower resolution to study the micro- and macro-porous network at the core scale. At the borehole scale, the borehole wall images are used to determinate macrostructures from centimeter pores to karsts. Finally, surface geophysics allows to observe the extension of karst and heterogeneities at the site scale.Finally, the porous structure of the study site is integrated into the regional geology of the platform. A hydrogeophysical observatory was installed on site to monitor the spreading of salt water in the aquifer. The interpretation of its salinity measurements can take into account the geological and petrophysical context.

L’océan côtier occupe une position clé dans le cycle du carbone et est exposé à l’acidification des océans. Une grande partie de matière organique(MO) marine et continentale est minéralisée dans les sédiments estuariens par des voies aérobies ou anaérobies. Cette minéralisation produit du carbone inorganique dissous (DIC), mais aussi de l’alcalinité totale(TA) pour la partie anoxique, ce qui tamponne les variations de pH du système et augmente la capacitéde l’eau de mer à absorber du CO2. Des mesures dans les sédiments du prodelta du Rhône ont montré que la minéralisation anoxique, surtout la sulfato-réduction, y est dominante et produit des forts flux de TA et de DIC. Proche de l’embouchure, c’est surtout la MO continentale qui est minéralisée et la fraction marine augmente vers le large. Une expérience d’acidification des sédiments de la baie de Villefranche-sur-mer a montré que l’acidification des océans cause la dissolution des carbonates ce qui tamponne le pH dans les sédiments. / Continental shelves are key regions for theglobal carbon cycle and particularly exposed to oceanacidification. A large part of organic matter (OM) ofcontinental and marine origin is mineralized in estuarinesediments following oxic and anoxic pathways.This mineralization produces dissolved inorganic carbon(DIC) leading to acidification of the bottom waters.Anoxic mineralization can produce total alkalinity(TA) that can contribute to buffer bottom water pHand increase the CO2 storage capacity of seawater. Measurementsin the sediments of the Rhˆone River prodeltashowed that anoxic mineralization, especially sulfate reduction,are the major pathways of OM mineralizationand create high DIC and TA fluxes. Land derived OMis mineralized close to the river mouth and marine OMtakes over on the shelf. An acidification experiment withsediment cores from the bay of Villefranche evidencedthat acidification causes carbonate dissolution at thesediment surface that buffers porewater pH.

Submitted by Biblioteca de Pós-Graduação em Geoquímica BGQ (bgq@ndc.uff.br) on 2017-08-16T16:46:32Z No. of bitstreams: 1 Mega, A. M..pdf: 4299230 bytes, checksum: 4ff04b898e1e7eebe891e2a5a4dfcd98 (MD5) / Made available in DSpace on 2017-08-16T16:46:32Z (GMT). No. of bitstreams: 1 Mega, A. M..pdf: 4299230 bytes, checksum: 4ff04b898e1e7eebe891e2a5a4dfcd98 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Universidade Federal Fluminense. Instituto de Química. Programa de Pós-Graduação em Geoquímica, Niterói, RJ / Os oceanos funcionam como um reservatório natural de carbono, no qual sua solubilidade na superfície dos oceanos varia de acordo com a temperatura. Antes do período industrial, as variações na concentração de CO2 atmosférico estavam fortemente associadas às transições glacial-interglacial (G-IG), onde os menores valores de CO2 na atmosfera foram registrados nos períodos glaciais, decorrente do aumento da solubilidade do CO2 nos oceanos. Nesses períodos, o aumento da solubilidade do CO2 na coluna d’água estimulou a produção de íons carbonato, beneficiando organismos que calcificam carbonato de cálcio (CaCO3) em suas conchas e esqueletos. O processo inverso, ou seja, menor solubilidade do CO2 e, consequentemente, menor disponibilidade de íons carbonatos nos oceanos marcou os períodos interglaciais. O presente estudo teve como objetivo avaliar os efeitos das variações no peso-normalizado pelo tamanho (do inglês, size-normalized weight, SNW) de foraminíferos planctônicos durante os últimos 70.000 anos no Sudoeste do Atlântico visando compreender os efeitos da calcificação e/ou dissolução do carbonato e da microestrutura das testas de foraminíferos planctônicos que viviam na porção superior da coluna d'água (G. ruber-white e G. sacculifer-sem saco). Para tanto, foi utilizado um testemunho coletado na Bacia de Santos a 2225 m de profundidade, que compreende os últimos 185 mil anos, dos quais os primeiros 70 mil anos foram estudados. Os resultados mostraram que ambas as espécies apresentaram um aumento do SNW na transição entre os períodos G-IG, associado com indícios de dissolução nas testas do período glacial, quando observada a microestrutura. Esses resultados demonstram a ação corrosiva das águas de fundo durante os glaciais e diferem dos obtidos em outros estudos realizados no Atlântico Norte que registram características menos corrosivas durante o último glacial em profundidades de até 3500 metros. A redução no peso das testas durante o período glacial foi atribuída à ação da dissolução dos carbonatos. A dissolução pode ocorrer abaixo da camada denominada lisoclina, porém apesar da grande mudança na profundidade da lisoclina durante os glaciais no Atlântico Sul, o testemunho, ainda assim, estaria 800 m acima da influência da lisoclina. Acima da lisoclina, a dissolução dos carbonatos pode ocorrer por diversos outros fatores, tais como pelo aumento da geração de CO2 pela atividade bentônica durante eventos de aumento de produtividade. Essa atividade bentônica tornaria a camada da interface água-sedimento corrosiva às estruturas carbonáticas. Nesse sentido, foram registrados no testemunho estudado um aumento nos teores de sílica e ferro, nutrientes que poderiam estimular um aumento da produtividade primaria, o que se refletiria nos altos níveis de carbono orgânico também registrados no testemunho durante o período glacial, estimulando, assim, a atividade bentônica. Outra possibilidade que explicaria a dissolução observada é decorrente de mudança na geometria das massas d’água durante os glaciais, o qual promoveria o contato do sedimento com massas d’água Antárticas (Águas de Fundo Antárticas-AFA), que são mais corrosivas. Entretanto, estudos anteriores realizados com o mesmo testemunho e baseados em isótopos de neodímio não corroboram a ocorrência de mudanças na geometria das massas d’água na região, pelo menos para os últimos 25 mil anos. / Oceans work as a natural reservoir of carbon, where the solubility in the surface varies with temperature. Before the industrial period, variations in the atmospheric CO2 concentration were strongly associated with the glacial-interglacial (G-IG) transitions, where the lowest atmosphere CO2 values were recorded in the glacial periods, due to the increase in the CO2 solubility. In these periods, the increase of the CO2 solubility in the water column stimulated the production of carbonate ions, benefiting organisms that calcify calcium carbonate (CaCO3) in their shells. The inverse process, that is, the lower CO2 solubility and, consequently, lower carbonate ions availability in the oceans marked the interglacial periods. The objective of this study was to evaluate the effects of size-normalized weight during the last 70.000 years in the Southwest Atlantic to understand the effects of calcification and/or dissolution of carbonate and microstructure analysis of the Planktonic foraminifera that lived in the upper portion of the water column (G. ruber-white) and G. sacculifer). For that, a core collected in the Santos Basin at 2225 m depth was used, which includes the last 185 thousand years, of which the first 70 thousand years were studied. The results showed that both species showed an increase in SNW at the transition between the G-IG periods, associated with evidence of dissolution in the glacial period, when the microstructure was observed. These results demonstrate the corrosive action of the bottom waters during the glaciers and differ from those obtained in other studies conducted in the North Atlantic that record less corrosive characteristics during the last glacial in depths of up to 3500 meters. The reduction in the weight of the shells during the glacial period was attributed to the action of the carbonate dissolution. The dissolution may occur below the lysoclin layer, but despite the large change in lysoclin depth during the glaciers in the South Atlantic, the corer would still be 800 m above the influence of lysoclin. Above lysoclin, the carbonate dissolution can occur due to several other factors, such as the increase of CO2 generation by benthic activity during productivity increase events. This benthic activity would make the water-sediment interface layer corrosive to carbonate structures. In this sense, an increase in silica and iron contents was recorded in the studied corer, nutrients which could stimulate an increase in primary productivity, which would be reflected in the high levels of organic carbon also recorded in the corer during the glacial period, stimulating benthic activity. Another possibility that would explain the observed dissolution is due to a change in the geometry of the water masses during the glaciers, which would promote the contact of the sediment with Antarctic water masses (Antarctic Bottom Water-ABW), which are more corrosive. However, previous studies carried out with the same evidence and based on neodymium isotopes do not corroborate the occurrence of changes in the geometry of water masses in the region, at least 25 ka years

A constante intercalação entre rochas siliciclásticas, carbonáticas e hibridas gerou complexos reservatórios de petróleo na seção albiana (Grupo Barra Nova) da plataforma de Regência, porção emersa da bacia do Espírito Santo. O principal objetivo do trabalho é compreender o ambiente deposicional da sucessão sedimentar mista carbonática-siliciclástica albiana do Grupo Barra Nova nesta área e os fatores que condicionam a qualidade dos seus reservatórios. As rochas que compõe a sucessão estudada foram caracterizadas como rochas siliciclásticas, compostas por mais de 2/3 de grãos siliciclásticos, rochas carbonáticas, compostas por mais de 2/3 de grãos aloquímicos, e rochas hibridas, que possuem entre 1/3 e 2/3 de grãos siliciclásticos, sendo o restante de aloquímicos. Os grãos siliciclásticos são angulosos, mal a moderadamente selecionados, ricos em feldspatos, granadas e pesados, derivados de depósitos de primeiro ciclo, indicando transporte e deposição rápidos. Os grãos carbonáticos se encontram retrabalhados, apresentando abrasão dos envelopes dos oncolitos. A presença constante de grãos carbonáticos, inclusive nas rochas siliciclásticas, indica que as fábricas carbonáticas de água rasa eram permanentemente atuantes durante toda a deposição da sucessão analisada. Fatores como a re-deposição dos grãos carbonáticos, a intercalação caótica entre rochas carbonáticas, siliciclásticas e híbridas além do domínio de rochas maciças indicam que a deposição ocorreu principalmente por fluxos gravitacionais. Apesar da alta frequência de intercalação, foi possível reconhecer sequencias através da correlação entre as fácies e os perfis elétricos. Sequencias de 4ª ordem foram definidas pelo empilhamento de siliciclásticos finos, gradando a siliciclásticos grossos, a arenitos híbridos, culminando em carbonatos no topo. Mudanças climáticas e a variação relativa do nível do mar (influenciado pela tectônica salífera) controlaram o domínio de depósitos carbonáticos ou siliciclásticos. Durante períodos secos e de mar alto, havia aumento da fábrica carbonática enquanto períodos úmidos e de nível de mar baixo o aporte de siliciclásticos era preponderante. / The constant intercalation between siliciclastic, carbonatic and hybrid rocks generated complex petroleum reservoirs in Albian section (Barra Nova Group) of Regencia platform, onshore portion of Espirito Santo Basin. The main purpose of this work is to understand the depositional environment of Albian Barra Nova Group mixed carbonate-siliciclastic sedimentary sequence and the main factors that control the quality of the reservoirs. The rocks that constitute the succession were characterized as siliciclastic rocks, composed of more of 2/3 of siliciclastic grains, carbonate rocks, composed of more of 2/3 of carbonate allochem grains, and hybrid rocks, composed of between 1/3 and 2/3 of siliciclastic, being the remaining carbonate grains. Siliciclastic grains are angular, badly to moderately sorted, rich in feldspars, garnets and other heavy minerals, derived from first-cycle deposits through fast transport and deposition. Carbonate grains are reworked, commonly showing abrasion of the envelopes of oncolites. The constant presence of carbonate grains, even in the siliciclastic rocks, shows that the shallow water carbonate factory was permanently in activity during the whole deposition of the succession. The re-deposition of carbonate grains, the chaotic interbedding between carbonate, siliciclastic and hybrid rocks, and the dominance of massive rocks indicate that gravity flows were responsible for the transportation of the sediments. Although for the high frequency of intercalation, depositional sequences were identified through the correlation between facies analysis and well logs. 4th order sequences were defined, beginning with fine siliciclastic, grading to coarse siliciclastic to the top, followed by hybrid arenites, and culminating in carbonates at the top. Climatic changes and eustatic variation (induced by salt tectonics) controlled the sedimentation of siliciclastics and carbonates. During dry periods with high sea level the domine were of carbonatic sedimentation while wet periods with low sea level the supply of siliciclastic were abundant.