Le travail présenté dans cette thèse, s'inscrit dans le domaine d'étude de l'interaction des rayonnements ionisants avec les liquides polaires. Bénéficiant de l'accélérateur d'électrons picoseconde ELYSE, les études ont été menées en utilisant les techniques de la radiolyse impulsionnelle associées à la spectrophotométrie d'absorption résolue en temps dans le domaine de la picoseconde. Ce travail est réparti sur deux chapitres distincts. Le premier aborde l'étude la variation temporelle du rendement radiolytique de l'électron solvaté dans l'eau et les alcools simples. Grâce au système de détection original monté sur l'accélérateur ELYSE, composé d'une lampe flash spécialement conçue pour cette détection et d'une streak-camera utilisée pour la première fois en spectroscopie d'absorption, il a été possible d'enregistrer la totalité du déclin du rendement radiolytique de l'électron solvaté d'une façon continue dans un intervalle de temps allant de la dizaine de picoseconde à quelques centaines de nanoseconde. La capture de l'électron solvaté par le méthylviologène, a été mise à profit pour réévaluer le coefficient d'extinction molaire du spectre d'absorption de l'électron solvaté dans l'eau et l'éthanol à partir des points isobestiques qui apparaissent à l'intersection des spectres d'absorption de l'électron solvaté qui disparaît et du méthylviologène qui se forme au cours de la réaction.Le deuxième chapitre est consacré à l'étude des carbonates organiques liquides, tels que le diméthyle carbonate (DMC), le diéthyle carbonate (DEC) et le propylène carbonate (PC). Cette famille de carbonate qui n'a jamais été étudiée auparavant par radiolyse pulsée, entre dans la composition des électrolytes des batteries notamment au lithium. Les études ont été focalisées sur le PC au vu de ces caractéristiques physico-chimiques, notamment sa constante diélectrique très élevée (64) et son très fort moment dipolaire de 4,9 D. Les premiers résultats ont été obtenus d'abord sur des solutions aqueuses contenant du propylène carbonate afin d'observer les réactions de réduction et d'oxydation du PC par les espèces radiolytiques de l'eau (électron solvaté et radicaux OH). Puis après l'identification (spectrale et cinétique) de l'espèce formée par interaction avec le radical OH comme étant le radical PC* résultant de l'abstraction d'un H de la molécule de PC et l'espèce formée par interaction avec l'électron aqueux comme étant l'anion PC-, d'autres mesures ont été effectuées dans le liquide pur ainsi qu'en présence de certains intercepteurs d'électrons (biphényle, anthracène, naphtalène). Elles ont permis d'accéder au rendement radiolytique de PC- ainsi qu'à l'évaluation de son potentiel redox. Les premiers résultats sur le DEC et le DMC sont aussi exposés dans cette partie, portant dans un premier lieu sur le solvant pur et puis en présence de biphényle.

Submitted by Maria Eneide de Souza Araujo (mearaujo@ipen.br) on 2017-03-10T14:39:39Z No. of bitstreams: 1 22066.pdf: 9119613 bytes, checksum: 0b28a0c36e553b4d7b70c8a8a0d8d601 (MD5) / Made available in DSpace on 2017-03-10T14:39:39Z (GMT). No. of bitstreams: 1 22066.pdf: 9119613 bytes, checksum: 0b28a0c36e553b4d7b70c8a8a0d8d601 (MD5) / O polímero Acrilonitrila Butadieno Estireno (ABS) é um dos polímeros mais versáteis disponíveis nos dias de hoje. Atualmente o Brasil não produz o ABS, o que limita a indústria brasileira de plásticos a utilizar as variações deste polímero importadas, ofertadas no mercado nacional por distribuidores locais. Este estudo avaliou os efeitos da adição das argilas Cloisite Na® e Branca de Cubati na matriz polimérica ABS e também os efeitos decorrentes do tratamento por radiação ionizante no ABS e nos compósitos ABS/Argila como formas de modificação de um ABS convencional. Visando avaliar a diferença entre uma argila organofílica e uma organofóbica, a argila Branca de Cubati foi organofilizada e a argila Cloisite Na® foi utilizada como recebida. Foram preparados, utilizando uma extrusora dupla rosca, concentrados a 30 % em massa da argila Branca de Cubati, previamente organofilizada e da Cloisite Na® em Estireno Acrilonitrila (SAN). Os concentrados foram adicionados ao ABS a 1, 3 e 5 % em massa das argilas e foram injetados corpos de prova. Parte dos corpos de prova foi submetida à irradiação por feixe de elétrons à uma dose de 600 kGy. Os compósitos irradiados e não irradiados foram caracterizados por meio de ensaios de resistência a tração, resistência a flexão, resistência ao impacto, temperatura de distorção térmica, ponto de amolecimento Vicat, análise de termogravimétrica (TG), difração de raios X e microscopia eletrônica de varredura com emissão de campo (MEVFEG) e a correlação entre os resultados foi discutida. Foram observadas melhorias nas propriedades mecânicas, exceto resistência ao impacto, nos materiais aditivados com as argilas, sendo os melhores resultados obtidos com a argila Branca de Cubati. O tratamento por radiação ionizante favoreceu o processo de reticulação do ABS. / Dissertação (Mestrado em Tecnologia Nuclear) / IPEN/D / Instituto de Pesquisas Energéticas e Nucleares - IPEN-CNEN/SP

A formação dos monoalquil carbonatos (MACs) em meio aquoso - produzidos pela reação de um álcool e bicarbonato foi investigada por eletroforese capilar (CE) com detecção condutométrica sem contato (C4D). Foram estudadas ao todo 29 substâncias, das quais 25 apresentaram formação de adutos aniônicos monocarregados e 2 delas, adutos aniônicos com dupla carga. A eletroforese capilar proporcionou a obtenção de medidas de propriedades físico-químicas. Através do tempo de migração, foram obtidos mobilidade, coeficiente de difusão e raio iônico hidratado. Para os n-álcoois de 1 a 5 átomos de carbono, os adutos apresentaram raio iônico hidratado entre 216 pm e 310 pm. Os MACs têm raio iônico proporcional ao do álcool gerador, sendo sistematicamente maiores devidos à anexação do grupo carbonato. Quando comparado a ácidos carboxílicos de cadeia carbônica similar, os MACs possuem menor raio iônico hidratado. A obtenção dos valores da cinética de formação e hidrólise foi possível pela utilização de dupla detecção condutométrica, a qual permitia determinar a concentração do MAC em dois momentos diferentes ao longo da coluna. Devido à impossibilidade de uma calibração direta - já que os sais de MACs se decompõem em água - foi introduzida uma nova técnica de calibração que dispensa o uso de uma solução padrão do analito em favor de uma com espécie de mobilidade similar. As constantes cinética e termodinâmica foram comparadas com aquelas disponíveis na literatura, mostrando boa concordância, como no caso dos adutos para o metanol e etanol (a 25 ºC em meio aquoso), cujos valores da constante termodinâmica sugeridos pela literatura são de 3,57 e 1,80, respectivamente, enquanto que os valores calculados em nosso trabalho são de 4,2 e 2,3, a 25ºC. De forma similar ao ácido carbônico, os ácidos alquilcarbônicos (ACAs) se decompõem em meio ácido, o que dificulta a determinação da verdadeira constante de dissociação. Ainda assim, estudos em pH de 3 a 9, permitiram estimar os valores de pKa dos ácidos derivados de metanol, etanol e propanol como estando algo abaixo de 4, o que estaria em acordo com o valor de 3,6 do ácido carbônico. A formação de MACs também foi observada para dióis, como o etileno glicol e polióis, como o glicerol e manitol. Foi também possível observar, por eletroforese capilar, a formação de adutos aniônicos monovalentes para açúcares, tais como a sacarose, glicose e frutose. Por fim, a pesquisa revelou a possibilidade da formação de adutos com dupla carga - os bis(carbonatos) - para alguns dióis: o 1,4-butanodiol e o 1,6-hexanodiol. Esta é a primeira vez que estas espécies foram observadas. Estes resultados sugerem a formação de adutos aniônicos para várias outras classes de compostos, as quais possuam a hidroxila na cadeia carbônica. Embora, em meio predominantemente aquoso, estas espécies não estejam em alta concentração, trata-se de um novo conjunto de espécies a serem consideradas quando se trabalha em condições propícias. / The formation of monoalkyl carbonates (MACs) in aqueous medium - resulting from an alcohol and bicarbonate - was investigated by using capillary electrophoresis with capacitively coupled contactless conductivity detection (C4D). Twenty nine substances were studied. The mono-charged anionic adducts were observed for 25 of them and double-charged species were observed for 2. Capillary electrophoresis allowed us to obtain some physical-chemical properties. The migration time was used to calculate the ionic mobility, coefficient of diffusion, and hydrodynamic radius. The radii ranged from 216 to 310 pm for the adducts formed from the n-alcohols of 1 to 5 carbon atoms, respectively. The MACs have radii proportional to the size of the alcohol, being systematically greater because of the attached carbonate group. When compared to carboxylic acids of similar carbonic chain, the MACs have smaller radii. The calculation of the kinetic constants was possible due to the double C4D detection, which allows quantitation of the MAC at two different moments along the capillary. Due to the decomposition of the MAC salt in water, a direct quantitation was not possible. Thus an indirect calibration approach was introduced, where the analyte is substituted by a stable species of similar mobility. Good agreement was obtained between the kinetic and thermodynamic constants obtained by this method and those ones available in literature. For instance, the methanol and ethanol adducts were 4.2 and 2.3 (at 25 ºC), respectively, while the literature\'s values are 3.57 and 1.80. Similarly to carbonic acid, the alkyl carbonic acids (ACAs) decompose in acid medium, which impairs the determination of the dissociation constant. Even so, studies from pH between 3 and 9 allowed us to estimate that the pKa values of the adducts for methanol, ethanol, and propanol are somewhat below 4, which is in agreement with the value 3.6 for the carbonic acid. MACs were also observed for diols and polyols as well as for sugars. Finally, double-charged species bis(carbonates) were formed with 1,4-butanediol and 1,6-hexanediol. This is the first time that these species are reported. Although the concentrations of these species are not high in an aqueous medium, they form a new set of substance to be considered in aqueous solution when the conditions are favorable.

The thesis presents observations on the CO2 concentration and carbon isotopes in air CO2 (δ13C) to constrain the inter-annual variability of carbon inventory over the Southern Ocean between the years 2011-2013. Based on the observation, the region of CO2 venting was identified over the Southern Ocean. Further, isotopic characterization allowed inferring about the possible sources of CO2 degassing and contribution from the dissolved inorganic carbon (DIC) that exsolved to generate CO2. It is concluded that the origin CO2 is mainly from the degassing of CO2 available from the dissociation of DIC or organic degradation. Live Foraminiferal samples of Globigerina bulloides from towing were captured, separated and analysed for δ18O and δ13C from various locations across the Southern Ocean between 10°N−60°S. A large similarities in the estimated values (deduced from simultaneous composition of ocean water 18O, δ13C in DIC and temperature i.e. SST under equilibrium condition) and measured δ18O and δ13C values were observed until 40°S from the equator, and hence it was concluded that the calcification depth of G. bulloides is confined to a depth of ~75-200m till 40°S latitude. However, further south (>40oS) disequilibrium from the estimates was detected. A number of possible reasons were cited for the observed disequilibrium such as (1) Deeper depth habitat (2) Partial dissolution (3) Non-equilibrium calcification (4) Oceanic Suess Effect and (5) Genetic Variability. A box model of isotopic mass balance was presented in this study to explain the pattern of enrichment in the 13C values of sea water DIC with latitude (up to about 43°S). The model shows that a steady state of the carbon isotope ratio of water is achieved in a relatively short time of ~5000 days. Rainwater isotope in the open marine condition across the latitudinal transects over Southern Ocean marking zone of precipitation and evaporation is another element of this thesis. A variation with excess lighter isotopes in rainwater was observed in high latitude rain in this study. Observed isotopic depletion is attributed to rainout process over the ocean. The average rainout fraction over the Southern Ocean in the region of zone of precipitation is ~44%, while it drops to ~25% in the zone of evaporation. Second part of the thesis presents a novel method of isotope thermometry which is called “clumped isotope (13C18O16O16O-2 in the calcite structure) thermometry”. A revision in the thermometry equation relating 47 vs T in synthetic carbonates precipitates and otoliths was proposed. The revised calibration was used on fish otoliths from the modern and past environment to estimate the temperatures. Together with the clumped isotope, conventional stable isotopes in the shell carbonates were measured to effectively reconstruct the seasonal fresh water fraction at seasonal time scales.

No description available.

Reconstruction studies of seasonal rainfall utilizing stable isotope based proxy approach suffer from the limitations of time resolutions. Conventional methods and archives limit the achievable resolution to annual scales. However, high resolution reconstruction (seasonal to sub-weekly scale) can be achieved in proxy records where growth rates are high enough to leave spatial signatures in an organically or inorganically deposited layer such as growth bands. In this study, aragonitic skeleton of the gastropod Lissachatina fulica (Bowdich, Giant African Land Snails) is investigated with an aim to achieve sub-weekly scale reconstruction of the Indian monsoon rainfall. These terrestrial gastropods are native of Africa and highly invasive. Their evolution in the geological time period dates back to the Pliocene and is presently distributed across the tropical belt. They exhibit a high growth rate in the presence of water and high relative humidity in the environment. As a result, they are ideally suited for the task of palaeo seasonality reconstruction. The isotopic patterns recorded in their growth bands reveal composition of environmental water at seasonal time scales. In vitro studies were carried out on L. fulica to estimate their growth rates and growth responses to changes in the physical conditions within the culture chamber. The Indian monsoon rainfall exhibits characteristic dry spells that are generally sandwiched between periods of active phases of high rainfall during the South West monsoon season. These dry spells are typically characterized by rainfall with low intensity. Isotope fingerprinting of the rain water at daily time resolution, covering the years of 2007-10 exhibited distinct isotopic ratios for the dry and wet spells. Dry spells were clearly demarcated in the record with isotopically enriched signature. In addition, the study indentified the role of three distinct moisture sources on δ18O of rain water at Bangalore, India. The variability in the oxygen isotopic composition of the Indian monsoon rainfall is predominantly controlled by this source moisture variability at inter annual time scales, while temperature and amount of rainfall tend to dominate the variability in the precipitation isotopes at seasonal and weekly scales. Simultaneous isotopic analyses of both rainwater and shell carbonates growth bands were undertaken to understand their relationship to aid in high resolution reconstruction. Carbonate found in the growth bands of the gastropods, which is precipitated under equilibrium condition from rainwater, preserves the signature of rainfall. This provides an opportunity to reconstruct rainfall parameters (i.e. amount and moisture sources) knowing the variability in shell carbonates. Stable isotopic ratios measured across the growth bands of live shell specimens collected from the southern and eastern Indian regions (Bangalore and Kolkata, respectively) were compared with the rainfall isotope ratios at these two locations; signature of dry spells were clearly identified from the study of isotopic composition in the growth bands of the gastropod specimens. The approach was also extended to older samples from historical archives from eastern Indian region (Kolkata, East India). Individual specimens belonging to the same species of gastropod, which were collected during the monsoon season of the year 1918 were used for reconstructing the seasonal pattern in monsoon rainfall over the region. The record of variation in the isotopic composition seen in the shell was compared with the rainfall data from Indian Metrological Division observatory at Kolkata station. The year 1918 was characterized as a major drought year and the signature of dry period was seen preserved in the specimen. The work under taken in this thesis will widen the scope of seasonality reconstruction using terrestrial shell fossils from palaeo records, which have been rarely investigated in paleoclimate studies from the perspective of understanding the seasonal precipitation variability.

Reconstruction studies of seasonal rainfall utilizing stable isotope based proxy approach suffer from the limitations of time resolutions. Conventional methods and archives limit the achievable resolution to annual scales. However, high resolution reconstruction (seasonal to sub-weekly scale) can be achieved in proxy records where growth rates are high enough to leave spatial signatures in an organically or inorganically deposited layer such as growth bands. In this study, aragonitic skeleton of the gastropod Lissachatina fulica (Bowdich, Giant African Land Snails) is investigated with an aim to achieve sub-weekly scale reconstruction of the Indian monsoon rainfall. These terrestrial gastropods are native of Africa and highly invasive. Their evolution in the geological time period dates back to the Pliocene and is presently distributed across the tropical belt. They exhibit a high growth rate in the presence of water and high relative humidity in the environment. As a result, they are ideally suited for the task of palaeo seasonality reconstruction. The isotopic patterns recorded in their growth bands reveal composition of environmental water at seasonal time scales. In vitro studies were carried out on L. fulica to estimate their growth rates and growth responses to changes in the physical conditions within the culture chamber. The Indian monsoon rainfall exhibits characteristic dry spells that are generally sandwiched between periods of active phases of high rainfall during the South West monsoon season. These dry spells are typically characterized by rainfall with low intensity. Isotope fingerprinting of the rain water at daily time resolution, covering the years of 2007-10 exhibited distinct isotopic ratios for the dry and wet spells. Dry spells were clearly demarcated in the record with isotopically enriched signature. In addition, the study indentified the role of three distinct moisture sources on δ18O of rain water at Bangalore, India. The variability in the oxygen isotopic composition of the Indian monsoon rainfall is predominantly controlled by this source moisture variability at inter annual time scales, while temperature and amount of rainfall tend to dominate the variability in the precipitation isotopes at seasonal and weekly scales. Simultaneous isotopic analyses of both rainwater and shell carbonates growth bands were undertaken to understand their relationship to aid in high resolution reconstruction. Carbonate found in the growth bands of the gastropods, which is precipitated under equilibrium condition from rainwater, preserves the signature of rainfall. This provides an opportunity to reconstruct rainfall parameters (i.e. amount and moisture sources) knowing the variability in shell carbonates. Stable isotopic ratios measured across the growth bands of live shell specimens collected from the southern and eastern Indian regions (Bangalore and Kolkata, respectively) were compared with the rainfall isotope ratios at these two locations; signature of dry spells were clearly identified from the study of isotopic composition in the growth bands of the gastropod specimens. The approach was also extended to older samples from historical archives from eastern Indian region (Kolkata, East India). Individual specimens belonging to the same species of gastropod, which were collected during the monsoon season of the year 1918 were used for reconstructing the seasonal pattern in monsoon rainfall over the region. The record of variation in the isotopic composition seen in the shell was compared with the rainfall data from Indian Metrological Division observatory at Kolkata station. The year 1918 was characterized as a major drought year and the signature of dry period was seen preserved in the specimen. The work under taken in this thesis will widen the scope of seasonality reconstruction using terrestrial shell fossils from palaeo records, which have been rarely investigated in paleoclimate studies from the perspective of understanding the seasonal precipitation variability.

Dans les eaux naturelles ou bien dans les eaux en cours de traitement, de nombreux processus peuvent générer des espèces réactives telles que de l´oxygène singulet, des ions superoxydes,des radicaux hydroxyles, ou bien d’autres oxydants. Dans les eaux naturelles, ces processus impliquent les substances humiques ou les ions nitrates en présence de lumière et d´oxygène. Dans les eaux en cours de traitement, les procédés d’oxydation avancée sont une source de production de radicaux hydroxyle. D’autres radicaux peuvent ensuite être formés par des réactions secondaires avec la matrice inorganique des eaux. Ces réactions aboutissent à la formation de radicaux inorganiques tels que les radicaux carbonates CO3·- et les radicaux chlores Cl· (atome de chlore). La réactivité de ces derniers est mal connue. Ce travail a pour but d’étudier la réactivité des radicaux carbonates et chlores avec des pesticides de type phénylurées, utilisés comme molécules modèles, et d’identifier les produits de dégradation. Le radical carbonate a été généré par la photolyse de [Co(NH3)5CO3]+, par photosensibilisation à partir de la 4- carboxybenzophenone, de la 1-nitronaphtalène et de la duroquinone et par l’excitation UV du peroxyde d’hydrogène. Le radical chlore a été généré par l’excitation UV du peroxyde d’hydrogène. Les constantes de vitesse de réaction des radicaux carbonates et chlores avec les pesticides étudiés, ont été déterminées, après validation d’une méthode de cinétique compétitive ou par modélisation cinétique. Ces constantes sont comprises pour le radical carbonate dans l’intervalle 0,35-3,5.107 L mol-1 s-1, et dans l’intervalle 1,2-3,9.108 L mol-1 s-1 pour le radical chlore. La comparaison de la réactivité des radicaux carbonates et chlores avec celle des radicaux hydroxyles, indique un facteur de l’ordre de 1000 pour le radical carbonate et de 100 pour le radical chlore, et ceci en faveur de la réactivité des radicaux hydroxyles. Plusieurs produits de dégradation du radical carbonate ont été identifiés. Il s’agit de produits d’hydroxylation du cycle aromatique, des produits issus d’une déméthylation, un dérivé quinone imine pour le fénuron, la cassure du pont dissulfure pour le metsulfuron méthyl. La comparaison des produits de dégradation formés avec les radicaux carbonates et hydroxyles met en évidence certains produits communs aux deux processus tandis que d’autres sont plus spécifiques. Les produits issus du radical carbonate sont moins nombreux en nombre que ceux issus du radical hydroxyle. / In natural water, humic substances are a source of reactive species production, in the presence of light and oxygen, such as singlet oxygen, superoxide, hydroxyl radicals, hydrogen peroxide but also a plurality of inorganic radicals such as the carbonate and chlorine radicals. The reactivity of these is unknown. This work aims to study the reactivity of carbonate and chorine radicals with pesticide ofphenylurea type and identify the products of degradation. The carbonate radical was generated by the photolysis of [Co(NH3)5CO3]+, by photosensitization from 4-carboxybenzophenone, from 1-nitronaphtalene and from duroquinone and by UV excitation of hydrogen peroxide. The chlorine radical was generated by UV excitation of hydrogen peroxide. The rate constants for reaction with the carbonate and chlorine radicals with the pesticides were determined after validation of competitive kinetic or kinetic modeling. These constants are included of the carbonate radical in the range 0.35-3.5x107 mol-1 L s-1, and in the range fron 1,2-3,9x108 mol-1 L s-1 for the chlorine radical. The comparison between the reactivity of the carbonate and chlorine radicals with the hydroxyl radicals, shows a factor 1000 for the carbonate radical and 100 for the chorine radical for the reactivity of hydroxyl radicals. Several degradation products were identified from the carbonate radical. These products were the hydroxylation of the aromatic ring, the products of demethylation, a derivative quionone imine for fenuron, the breaking of the bridge dissulfure for metsulfuron methyl. The comparison of the degradation products formed with carbonate and hydroxyl radicals show some common products to both processes, and others products are more specific. The products from the carbonate radical are fewer in number than those resulting from the hydroxyl radical.

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

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