Dans le contexte de stockage des déchets radioactifs en profondeur, des interactions entre le fer métal d’une part et la roche du Callovo-Oxfordien (COx), sa fraction argileuse purifiée (SCOx) ou des phases argileuses pures (kaolinite, illite, smectites) d’autre part, sont réalisées à 90°C sous atmosphère anoxique en solution chlorurée-salée. Le rôle des minéraux non argileux du COx est également étudié. L'oxydation rapide du fer métal entraine une libération d’ions fer en solution, une augmentation du pH et une diminution du Eh (réducteur). Une dissolution partielle des phases argileuses ainsi que la précipitation de serpentines ferrifères (odinite ou berthiérine, principalement) et de magnétite en faible quantité sont alors observées. En cas d’apport d'O2 au système, les serpentines ferrifères sont déstabilisées. L'exsolution du fer permet la formation d'oxydes et d’hydroxydes de fer et des particules argileuses proches des phases initiales précipitent. Lorsque du quartz est ajouté à SCOx, la dissolution partielle de ce minéral est responsable de la modification des chemins réactionnels. La formation de magnétite est alors limitée et les serpentines ferrifères sont enrichies en silice. Dans le cas de la kaolinite, DRX, MET, XPS et analyses texturales mettent en évidence la croissance des serpentines ferrifères (berthierines majoritairement) sur la surface basale des kaolinites, formant des particules kaolinite-serpentines-Fe démixées. Les techniques spectroscopiques (Mössbauer, XAS et STXM) permettent de déterminer les rapports Fe2+/Fe3+ et AlIV/AlVI jusqu'au niveau des particules élémentaires et de proposer des formules structurales pour ces serpentines ferrifères / In the context of underground disposal of high-level radioactive waste, interactions between metallic iron and Callovo-Oxfordian rock (COx), its purified clay fraction (SCOx) or pure clay phases (kaolinite, illite, smectites) were investigated at 90°C under anoxic atmosphere in chlorine solution. Role of COx non clay minerals in these reactions was also studied. Rapid metallic iron oxidation conducts to iron cations release in solution, pH increase (8-10) and Eh decrease (reducive conditions). The partial dissolution of initial clay phases and the crystallization of Fe-serpentines (odinite or berthierine mainly) and of low amount of magnetite were observed. The introduction of O2 into the system leads to Fe-serpentines destabilisation. Iron exsolution conducts to iron oxides and hydroxides formation and clay particles with composition close to the initial ones precipitate. Addition of quartz into the system leads to the partial dissolution of this mineral and to the modification of reaction pathways. Precipitation of magnetite is reduiced and Fe-serpentines are silica enriched. In the case of kaolinite-metallic iron interaction, combinated used of XRD, MET, XPS and textural analyses evidences the growth of berthierine on the basal face of kaolinites, resulting in Fe-serpentine-kaolinite demixed particles. Through the used of spectroscopic analyses (Mössbauer, XAS and STXM), we were able to determine Fe2+/Fe3+ and AlIV/AlVI ratio in elementary particles, which allows proposing structural formulae for the Fe-serpentines

Os sistemas combinados anaeróbio/aeróbio, para tratamento de água residuária, têm sido considerados alternativas viáveis do ponto de vista técnico-econômico em relação aos sistemas tradicionais. Este trabalho consiste no desenvolvimento de nova configuração para um sistema, com dois reatores operados seqüencialmente, composto por Reator Misto Radial de Leito Fixo para tratamento e nitrificação de esgoto sanitário e Reator Anóxico Horizontal de Leito Fixo para desnitrificação da água residuária. O RMRLF mostrou ser uma configuração promissora, promoveu a remoção de matéria orgânica, favoreceu a transferência de oxigênio dissolvido devido à distribuição das espumas em seções circuncêntricas, obteve boa nitrificação e possibilitou a desnitrificação simultânea com a nitrificação. O RAHLFa obteve baixa eficiência no processo de desnitrificação. O bom desempenho do sistema é decorrente, principalmente, da operação do RMRLF e apresentou eficiências de 88%, 86% e 95% na remoção de matéria orgânica em termos de demanda química de oxigênio, retenção de sólidos suspensos voláteis e nitrificação, respectivamente. O efluente final do sistema atingiu valores de demanda química de oxigênio, sólidos suspensos voláteis, nitrito e nitrato de 41 mg.l-1, 8 mg.l-1, 0,3 mg.l-1 e 16,7 mg.l-1, respectivamente. No efluente final não foi detectada a presença de nitrogênio amoniacal. / The combined, anaerobic/aerobic systems for wastewater treatment, are considered as possible alternatives from the technical-economical perspective, in relation to the traditional systems. The data obtained on the development and operation of a new system configuration of two reactor sequentially operated, composed of a Radial Flow Anaerobic/Aerobic Immobilized Biomass reactor (RFAAIB) for domestic sewage treatment and a Horizontal-flow Anoxic Immobilized Biomass (HAIBa) for wastewater denitrification are presented. The RFAAIB reactor was found to be a very promising configuration for promoting the organic matter removal, due to its round shape distribution of the foam matrix it favored the dissolved oxygen transfer, obtaining good nitrification and making possible to achieve simultaneous nitrification and denitrification. The HAIBa reactor obtained low efficiency in the denitrification process. The good system performance is mainly due to the RFAAIB reactor it achieved efficiency of 88%, 86% and 95% in the biochemical oxygen demand reduction process, volatile suspended solids retention and nitrification, respectively. The system final effluent achieved chemical oxygen demand, volatile suspended solids, nitrite and nitrate values of 41 mg.l-1, 8 mg.l-1, 0,3 mg.l-1 and 16,7 mg.l-1, respectively. In the final effluent no ammonium nitrogen was detected.

Thesis (Ph. D.)--Joint Program in Oceanography/Applied Ocean Science and Engineering (Massachusetts Institute of Technology, Dept. of Earth, Atmospheric, and Planetary Sciences; and the Woods Hole Oceanographic Institution), 2013. / In title on title page, "[delta]" appears as lower case Greek letters. Cataloged from PDF version of thesis. / Includes bibliographical references. / The stable isotopes, [delta]¹⁵N and [delta]¹⁸O, of nitrite and nitrate can be powerful tools used to interpret nitrogen cycling in the ocean. They are particularly useful in regions of the ocean where there are multiple sources and sinks of nitrogenous nutrients, which concentration profiles alone cannot distinguish. Examples of such regions are "oxygen deficient zones" (ODZ). They are of particular interest because they are also important hot spots of fixed N loss and production of N₂O, a potent greenhouse gas. In order to interpret these isotope profiles, the isotope systematics of each process involved must be known so that we can distinguish the isotopic signature of each process. One of the important processes to consider here is nitrification, the process by which ammonium is oxidized nitrite and then to nitrate. This thesis describes numerous experiments using both cultures of nitrifying organisms as well as natural seawater samples to determine the oxygen isotope systematics of nitrification. These experimental incubations show that the accumulation of nitrite has a large effect on the resulting [delta]¹⁸ONO3. In experiments where nitrite does not accumulate, [delta]¹⁸ONO3 produced from nitrification is between -1 to l%o. These values will be applicable for the majority of the ocean, but the nitrite isotopic exchange will be important in the regions of the ocean where nitrite accumulates, such as the base of the euphotic zone and oxygen deficient zones. [delta]¹⁸ONO2 was developed as a unique tracer in this thesis because it undergoes abiotic equilibration with water [delta]¹⁸O at a predictable rate based on pH, temperature and salinity. This rate, its dependencies, and how the [delta]¹⁸ONO2 values can be used as not only biological source indicators but also indicators of age are described. This method was applied to samples from the primary nitrite maximum in the Arabian Sea, revealing that the dominant source and sinks of nitrite are ammonia oxidation and nitrite oxidation with an average age of 37 days. Finally, using the isotope systematics of nitrification as well as the properties of nitrite oxygen isotope exchange described in this thesis, the final chapter interprets multiisotope nitrate and nitrite profiles in the Costa Rica Upwelling Dome using a simple ID model. The nitrite isotopes showed that there were multiple sources of nitrite in the primary nitrite maximum including (1) decoupling of ammonia oxidation and nitrite oxidation, (2) nitrate reduction during assimilation and leakage of nitrite by phytoplankton. In the oxygen deficient zone and secondary nitrite maximum, there were equal contributions of nitrite removal from nitrite oxidation and nitrite reduction. This recycling of nitrite to nitrate through oxidation indicates that the percentage of reduced nitrate fully consumed to N2 gas is actually smaller than previous estimates. Overall, this thesis describes new nitrogen and oxygen isotopic tracers and uses them to elucidate the complicated nitrogen biogeochemistry in oxygen deficient zones. / by Carolyn Buchwald. / Ph.D.

Este trabalho teve como objetivo geral a caracterização de um sistema de tratamento biológico de remoção de fenol em reator anaeróbio de leito fluidificado utilizando o nitrato como aceptor final de elétrons. O reator foi construído em acrílico transparente, com dimensões equivalentes a 190 cm de altura e 5,3 cm de diâmetro interno, totalizando um volume de 4192 cm³, dos quais cerca de 44% (1831 cm³) foram ocupados pelo meio suporte, na situação de leito fixo. Para imobilização da biomassa foram utilizadas partículas de poliestireno, que foram previamente ativadas através de ataque ácido, com o intuito de aumentar a rugosidade e a porosidade da superfície do material, facilitando a aderência da biomassa ao meio suporte. O reator foi inoculado com lodo proveniente de reator UASB, responsável pelo tratamento de despejos de suinocultura. A realização do experimento foi dividida em cinco fases, que foram alteradas de acordo com o desempenho e a estabilidade do sistema diante do aumento das concentrações de fenol e nitrato. As concentrações médias de fenol afluente estudadas foram de 52, 107, 201, 335 e 518 mg/L, de maneira que não foi detectada presença de fenol no efluente para concentrações de até 335 mg/L. A eficiência de remoção reduziu-se para aproximadamente 70%, quando foi operado com concentrações de fenol afluente superiores a 500 mg/L. A relação entre carbono (proveniente exclusivamente do fenol) e N - \'NO IND. 3\' foi aproximadamente 1, portanto, as concentrações médias afluentes de N - \'NO IND. 3\' testadas foram equivalentes a 45, 79, 157, 260 e 362 mg/L, cujas eficiências de remoção de nitrogênio foram de 94%, 89%, 86%, 79% e 51%, respectivamente. O pH efluente variou entre 7,64 e 8,35, estando de acordo com sistemas que realizam o processo de desnitrificação. Em geral, cerca de 3,8 g DQO foi consumido por grama de N - \'NO IND. 3\' removido. Não foi observado acúmulo de nitrito no sistema, considerando que o valor médio da concentração efluente foi de 1,5 mg/L de N - \'NO IND. 2\' para todo período de operação. O experimento teve duração de 162 dias, nos quais o sistema mostrou resultados satisfatórios para redução de carbono e nitrogênio, mesmo quando operado com elevadas concentrações de fenol e nitrato. / This work aimed the general characterization of a phenol removal biological treatment system in an anaerobic fluidized bed reactor using nitrate as the final electron acceptor. The reactor was built in transparent acrylic, with equivalent dimensions of 190 cm height and 5.3 cm intern diameter, resulting in 4,192 cm³ volume, which 44% were occupied by the support medium in a fix bed situation. Polystyrene particles were used to immobilize biomass, these particles were previously activated through acid attack, in order to increase materials roughness and superficial porosity, facilitating biomass adherence to the support medium. The reactor was inoculated with sludge from UASB reactor, responsible for swine culture effluent treatment. The experiment was divided in five phases, which were modified according to system performance and stability under the increase of phenol and nitrate concentrations. The mean phenol affluent concentrations studied were: 52, 107, 201, 335 and 518 mg/L, so that no phenol was detected in effluent in concentrations bellow 335 mg/L. The removal efficiency decreased to about 70% for affluent phenol concentrations over 500 mg/L. Carbon (exclusively from phenol) and N -\'NO IND. 3\' ratio was nearly 1, therefore the N \'NO IND. 3\' mean affluent concentrations tested were equivalent to 45, 79, 157, 260 e 362 mg/L, whose nitrogen removal efficiency were 94%, 89%, 86%, 79% e 51%, respectively. Effluent pH varied between 7.64 and 8.35, in agreement with denitrification process systems. In general, around 3.8 g DQO were consumed per gram of removed N \'NO IND. 3\'. No nitrite accumulation was observed in the system, considering that the mean effluent concentration was 1.5 mg/L de N - \'NO IND. 2\' to all operation period. Experiment lasted 162 days, during this time the system showed satisfactory results for carbon and nitrogen reduction, even when operated with high phenol and nitrate concentrations.

Este trabalho teve como objetivo geral a caracterização de um sistema de tratamento biológico de remoção de fenol em reator anaeróbio de leito fluidificado utilizando o nitrato como aceptor final de elétrons. O reator foi construído em acrílico transparente, com dimensões equivalentes a 190 cm de altura e 5,3 cm de diâmetro interno, totalizando um volume de 4192 cm³, dos quais cerca de 44% (1831 cm³) foram ocupados pelo meio suporte, na situação de leito fixo. Para imobilização da biomassa foram utilizadas partículas de poliestireno, que foram previamente ativadas através de ataque ácido, com o intuito de aumentar a rugosidade e a porosidade da superfície do material, facilitando a aderência da biomassa ao meio suporte. O reator foi inoculado com lodo proveniente de reator UASB, responsável pelo tratamento de despejos de suinocultura. A realização do experimento foi dividida em cinco fases, que foram alteradas de acordo com o desempenho e a estabilidade do sistema diante do aumento das concentrações de fenol e nitrato. As concentrações médias de fenol afluente estudadas foram de 52, 107, 201, 335 e 518 mg/L, de maneira que não foi detectada presença de fenol no efluente para concentrações de até 335 mg/L. A eficiência de remoção reduziu-se para aproximadamente 70%, quando foi operado com concentrações de fenol afluente superiores a 500 mg/L. A relação entre carbono (proveniente exclusivamente do fenol) e N - \'NO IND. 3\' foi aproximadamente 1, portanto, as concentrações médias afluentes de N - \'NO IND. 3\' testadas foram equivalentes a 45, 79, 157, 260 e 362 mg/L, cujas eficiências de remoção de nitrogênio foram de 94%, 89%, 86%, 79% e 51%, respectivamente. O pH efluente variou entre 7,64 e 8,35, estando de acordo com sistemas que realizam o processo de desnitrificação. Em geral, cerca de 3,8 g DQO foi consumido por grama de N - \'NO IND. 3\' removido. Não foi observado acúmulo de nitrito no sistema, considerando que o valor médio da concentração efluente foi de 1,5 mg/L de N - \'NO IND. 2\' para todo período de operação. O experimento teve duração de 162 dias, nos quais o sistema mostrou resultados satisfatórios para redução de carbono e nitrogênio, mesmo quando operado com elevadas concentrações de fenol e nitrato. / This work aimed the general characterization of a phenol removal biological treatment system in an anaerobic fluidized bed reactor using nitrate as the final electron acceptor. The reactor was built in transparent acrylic, with equivalent dimensions of 190 cm height and 5.3 cm intern diameter, resulting in 4,192 cm³ volume, which 44% were occupied by the support medium in a fix bed situation. Polystyrene particles were used to immobilize biomass, these particles were previously activated through acid attack, in order to increase materials roughness and superficial porosity, facilitating biomass adherence to the support medium. The reactor was inoculated with sludge from UASB reactor, responsible for swine culture effluent treatment. The experiment was divided in five phases, which were modified according to system performance and stability under the increase of phenol and nitrate concentrations. The mean phenol affluent concentrations studied were: 52, 107, 201, 335 and 518 mg/L, so that no phenol was detected in effluent in concentrations bellow 335 mg/L. The removal efficiency decreased to about 70% for affluent phenol concentrations over 500 mg/L. Carbon (exclusively from phenol) and N -\'NO IND. 3\' ratio was nearly 1, therefore the N \'NO IND. 3\' mean affluent concentrations tested were equivalent to 45, 79, 157, 260 e 362 mg/L, whose nitrogen removal efficiency were 94%, 89%, 86%, 79% e 51%, respectively. Effluent pH varied between 7.64 and 8.35, in agreement with denitrification process systems. In general, around 3.8 g DQO were consumed per gram of removed N \'NO IND. 3\'. No nitrite accumulation was observed in the system, considering that the mean effluent concentration was 1.5 mg/L de N - \'NO IND. 2\' to all operation period. Experiment lasted 162 days, during this time the system showed satisfactory results for carbon and nitrogen reduction, even when operated with high phenol and nitrate concentrations.

Os sistemas combinados anaeróbio/aeróbio, para tratamento de água residuária, têm sido considerados alternativas viáveis do ponto de vista técnico-econômico em relação aos sistemas tradicionais. Este trabalho consiste no desenvolvimento de nova configuração para um sistema, com dois reatores operados seqüencialmente, composto por Reator Misto Radial de Leito Fixo para tratamento e nitrificação de esgoto sanitário e Reator Anóxico Horizontal de Leito Fixo para desnitrificação da água residuária. O RMRLF mostrou ser uma configuração promissora, promoveu a remoção de matéria orgânica, favoreceu a transferência de oxigênio dissolvido devido à distribuição das espumas em seções circuncêntricas, obteve boa nitrificação e possibilitou a desnitrificação simultânea com a nitrificação. O RAHLFa obteve baixa eficiência no processo de desnitrificação. O bom desempenho do sistema é decorrente, principalmente, da operação do RMRLF e apresentou eficiências de 88%, 86% e 95% na remoção de matéria orgânica em termos de demanda química de oxigênio, retenção de sólidos suspensos voláteis e nitrificação, respectivamente. O efluente final do sistema atingiu valores de demanda química de oxigênio, sólidos suspensos voláteis, nitrito e nitrato de 41 mg.l-1, 8 mg.l-1, 0,3 mg.l-1 e 16,7 mg.l-1, respectivamente. No efluente final não foi detectada a presença de nitrogênio amoniacal. / The combined, anaerobic/aerobic systems for wastewater treatment, are considered as possible alternatives from the technical-economical perspective, in relation to the traditional systems. The data obtained on the development and operation of a new system configuration of two reactor sequentially operated, composed of a Radial Flow Anaerobic/Aerobic Immobilized Biomass reactor (RFAAIB) for domestic sewage treatment and a Horizontal-flow Anoxic Immobilized Biomass (HAIBa) for wastewater denitrification are presented. The RFAAIB reactor was found to be a very promising configuration for promoting the organic matter removal, due to its round shape distribution of the foam matrix it favored the dissolved oxygen transfer, obtaining good nitrification and making possible to achieve simultaneous nitrification and denitrification. The HAIBa reactor obtained low efficiency in the denitrification process. The good system performance is mainly due to the RFAAIB reactor it achieved efficiency of 88%, 86% and 95% in the biochemical oxygen demand reduction process, volatile suspended solids retention and nitrification, respectively. The system final effluent achieved chemical oxygen demand, volatile suspended solids, nitrite and nitrate values of 41 mg.l-1, 8 mg.l-1, 0,3 mg.l-1 and 16,7 mg.l-1, respectively. In the final effluent no ammonium nitrogen was detected.

Rare earth elements (REEs) and their isotopes (such as Nd isotopes) can be potentially used to trace a wide range of oceanic processes in both modern and ancient oceans, but their successful application as tracers requires a comprehensive understanding of REE cycling in the modern ocean. Previous studies of REEs in seawater were largely constrained by analytical difficulties in generating accurate and precise REE data from seawater, which typically contain REE concentrations at a sub-ppt to ppt level. A new, and relatively simple, analytical method for precise and accurate determination of all dissolved REE concentrations in reasonably small (∼100 ml) seawater samples is presented in this thesis. With the application of the new method, this thesis reports the first full-depth, zonal ocean section of all dissolved REE concentrations, collected during the CoFeMUG cruise along ∼12°S in the South Atlantic. The section approach of this study places the distribution of dissolved REE concentrations in a well-constrained hydrographic context, allowing the first quantitative assessment (by an inverse model) of the relative importance of hydrographic controls resulting from advection/mixing of ocean circulation, together with non-conservative controls resulting from local particle scavenging and remineralization, in controlling the distribution of dissolved REEs in this region. A noteworthy decoupling of Ce and Mn with respect to their cycling in the water column was also observed in this study. The application of Nd isotopes as a tracer to reconstruct changes in ocean circulation in the NW European chalk shelf sea during rapid climatic events, including the mid-Cenomanian Event and oceanic anoxic event 2 (OAE 2), suggests a tight coupling between ocean circulation and transient climatic cooling during the general warm Late Cretaceous. An advected volcanic signal during OAE 2 was registered in the seawater Nd-isotope record from the English Chalk, probably suggesting a period of enhanced ocean ventilation/mixing at this time.

The hallmark of oceanic anoxic event 1a (OAE1a) (early Aptian ~125 Ma) corresponds to worldwide deposition of black shales with total organic carbon (TOC) content > 2% and a d13C positive excursion up to ~5‰. OAE1a has been related to large igneous province volcanism and dissociation of methane hydrates during the Lower Cretaceous. However, the occurrence of atypical, coeval and diachronous organic-rich deposits associated with OAE1a, which are also characterized by positive spikes of the d13C in epicontinental to restricted marine environments of the Tethys Ocean, indicates localized responses decoupled from complex global forcing factors. The present research is a high-resolution, multiproxy approach to assess the paleoenvironmental conditions that led to enhanced carbon sequestration from the late Barremian to the middle Aptian in a restricted, Tethyan marginal basin prior to and during OAE1a. I studied the lower 240 m of the El Pui section, Organyà Basin, Spanish Pyrenees. The basin developed as the result of extensional tectonism linked to the opening of the Atlantic Ocean. At the field scale the section consists of a sequence of alternating beds of cm – m-scale, medium-gray to grayish-black limestones and marlstones with TOC up to ~4%. The results indicate that the lowest 85 m of the section, from latest Barremian –earliest Aptian, characterize a deepening phase of the basin concomitant with sustained riverine flux and intensified primary productivity. These changes induced a shift in the sedimentation pattern and decreased the oxygen levels in the water column through organic matter respiration and limited ventilation of the basin. The upper 155 m comprising the earliest – late-early Aptian document the occurrence of OAE1a and its associated geochemical signatures (TOC up to 3% and a positive shift in d13C of ~5‰). However, a low enrichment of redox-sensitive trace elements indicates that the basin did not achieve anoxic conditions. The results also suggest that a shallower-phase of the basin, coeval with platform progradation, may have increased ventilation of the basin at the same time that heightened sedimentation rates and additional input of organic matter from terrestrial sources increased the burial and preservation rate of TOC in the sediment.

Ce travail de doctorat concerne le stockage des déchets radioactifs à vie longue et haute activité en site géologique profond. Dans le concept actuellement retenu par l’Andra (Agence nationale pour la gestion des déchets radioactifs), c’est une enveloppe en acier non allié, appelée « surconteneur », qui sera au contact de l’environnement. Dans les conditions anoxiques où se retrouvera l’acier après une période initiale relativement courte, des vitesses de corrosion très faibles sont attendues, ce qui garantirait l’intégrité du surconteneur pour des millénaires. Cependant, il n’est pas exclu que des bactéries sulfurogènes puissent se développer à proximité ou au contact du surconteneur et modifier localement la cinétique de la corrosion via les espèces sulfures produites par leur métabolisme. L’objectif de cette thèse consistait à améliorer notre compréhension du système de corrosion constitué de l’acier, de sa couche de rouille essentiellement composée de sidérite FeCO3 et d’un électrolyte sulfuré.Pour ce faire, il a été nécessaire dans un premier temps de caractériser par microspectroscopie Raman les sulfures de fer impliqués dans les processus de corrosion et d’étudier les mécanismes de leur formation et de leur transformation dans différentes conditions de concentration en Fe(II) et S(-II), de pH, de température et d’oxygénation. Il a pu être démontré que le spectre Raman de la mackinawite FeS, composé qui précipite à partir de Fe(II) et S(-II) dissous dans toutes les conditions considérées ici, évoluait avec la cristallinité et l’oxydation du composé. Par ailleurs, les mécanismes de l’oxydation à 80°C en milieu acide anoxique de la mackinawite en greigite Fe3S4 ont pu être décrits. Cette étude a permis de démontrer que les sulfures de fer souvent présents sur les objets archéologiques ferreuxissus de milieux anoxiques sont soit de la mackinawite, soit étroitement apparentés à la mackinawite.Dans un deuxième temps, nous avons étudié la formation de produits de corrosion carbonatés par polarisation anodique d’électrodes d’acier à température ambiante dans des électrolytes désaérés à base de NaHCO3. Les conditions expérimentales permettant d’obtenir la sidérite ont été re précisées et utilisées pour synthétiser des couches modèles de FeCO3 sur acier. Par ailleurs, il a été observé que la rouille verte carbonatée était le principal produit se formant aux faibles concentrations en espèces carbonates (0,003 et 0,1 mol L-1 par exemple),la sidérite se formant aux fortes concentrations (0,5 et 1 mol L-1). Les conditions permettant la formation de la chukanovite, l’hydroxycarbonate de Fe(II) de formule Fe2(OH)2CO3, n’ont pas pu être explicitées, même si cette phase a été obtenue dans un électrolyte contenant à la fois des ions SO42- et HCO3- à la concentration de 0,03 mol L-1.Enfin, les interactions entre sulfures et produits de corrosion ont été étudiées. La sidérite, la lépidocrocite et la goethite sont toutes réactives vis-à-vis des sulfures. Ainsi, il apparaît clairement que les espèces sulfures produites par les BSR devraient interagir avec la couche de produits de corrosion avant d’interagir avec le métal sous-jacent. Les tests effectués sur des analogues archéologiques du 16ème siècle, immergés deux mois dans des solutions sulfurées en conditions anoxiques ont permis de le démontrer. Le principal effet de cette immersion a été la formation de sulfures de fer à l’interface entre la couche dense de produits de corrosion, essentiellement constituée de sidérite, et le milieu transformé, zone où s’entremêlent les minéraux propres au sol et ceux produits par la corrosion du fer. Les espèces sulfures n’ont pas été détectées au voisinage immédiat de la surface du métal. / This PhD work deals with the nuclear waste disposal. In France, it is envisaged byAndra (French national radioactive waste management agency) that high-level radioactivewastes will be confined in a glass matrix, stored in a stainless steel canister, it self placed in a carbon steel overpack. The wastes will then be stored at a depth of ~500 m in a deep geological repositery, drilled in a very stiff (indurated) clay (argillite) formation. The kineticsof corrosion expected for the overpack in this disposal concept are low and will stay low if the somehow protective rust layer that will develop initially on the steel surface remains undamaged. Local changes of the physico-chemical conditions may however degrade this layer and induce accelerated kinetics of corrosion. In particular, the growth of sulphate reducing bacteria (SRB) close to the steel overpack cannot be excluded and the sulphid especies these micro-organisms produce may modify the corrosion process. The aim of this work was then to achieve a better understanding of the corrosion system constituted with steel, its rust layer mainly made of siderite FeCO3, and a sulphide-containing electrolyte.First, it proved necessary to characterise the iron sulphides involved in the corrosion processes by Raman micro-spectroscopy so as to study their formation and transformation mechanisms in various conditions of Fe(II) and S(-II) concentration, pH, temperature andaeration. It could be demonstrated that the Raman spectrum of mackinawite FeS, thecompound that precipitated in any case from dissolved Fe(II) and S(-II) species with the experimental conditions considered here, depended on the crystallinity and oxidation state.Moreover, the mechanisms of the oxidation of mackinawite into greigite Fe3S4 in acidicanoxic solutions at 80°C could be described. Finally, iron sulphides, often present on archaeological artefacts, could be identified using Raman micro-spectroscopy. The compounds present were mainly mackinawite and greigite.Secondly, to investigate the nature and properties of carbonated rust layers, carbonsteel electrodes were polarised anodically in NaHCO3 electrolytes continuously de-aerated byan argon flow. The experiments were performed at room temperature. The carbonated greenrust was observed to form at 0.003 and 0.1 mol L-1 NaHCO3 whereas FeCO3 was obtained atthe largest concentrations (0.5 and 1 mol L-1). Additional experiments were performed similarly in solutions of NaHCO3 and Na2SO4. Chukanovite, the Fe(II) hydroxycarbonate with formula Fe2(OH)2CO3, could be obtained in solutions containing 0.03 mol L-1 of eachsalt.Finally, interactions between sulphide species and corrosion products were studied.Siderite, goethite and lepidocrocite proved to be reactive towards sulphide. So, it seems clear that sulphide species produced by SRB should interact with the rust layer before to reach the metal underneath. Tests were performed with ferrous archaeological artefacts immersed 2months in anoxic sulphide-containing electrolytes to demonstrate it. The main effect of theimmersion was the formation of iron sulphide at the interface between the dense corrosion products layer, mainly constitute of siderite, and the transformed medium, where minerals ofthe soil are mixed with corrosion products. Sulphide species were not detected at the vicinityof the iron surface.

Carbonate geochemistry plays an important role in understanding environmental conditions during the time of precipitation. The studies for this dissertation research were focused on carbonate precipitation and crystallization in different chemical and physical environments. The first project aimed to precipitate aragonite at low oxygen levels to identify a correlation between partitioning of trace elements and anoxic and suboxic conditions. The second study focused on the precipitation of amorphous calcium carbonate in varying magnesium concentrations to determine the identity of crystalline material after transformation of ACC. Lastly, the third project was developed to understand transformation of CaCO3 polymorphs. Specifically, whether or not geochemistry is retained from one polymorph to the next. All projects could aid in development of paleoproxies to be used for determining past environmental and climatic conditions in the past.