The natural occurrences of high (&gt;10 μg/L) dissolved arsenic (As) in groundwater of Bengal Basin has put millions of people under the threat of chronic As exposure through drinking water. Present study has examined the processes that regulate As mobilization and its distribution in shallow aquifers and the potentiality of finding safe aquifers within shallow depth (&lt;50 m) for drinking water supply. The results indicate that in terms of aquifer sediment colors and water quality two types of aquifer namely brown sand aquifer (BSA) and grey sand aquifer (GSA) can be distinguished within the depth, accessible by low-cost drilling. The redox condition in the BSA is delineated to be Mn oxyhydroxides reducing, not sufficiently lowered for As mobilization resulting in high Mn and low Fe and As in groundwater. While in GSA, currently the reductive dissolution of Fe oxyhydroxides is the prevailing redox process causing As mobilization into groundwater of this aquifer type. It is revealed that the vertical distribution of As and other aqueous redox parameters is related to the redox zonation within aquifer. The decoupling of As and Fe release into groundwater is evident in the shallowest part of aquifer because of Fe enrichment by weathering of silicate minerals especially of biotite, the precipitation of secondary mineral phases like siderite and vivianite and incomplete reduction of Fe oxyhydroxides. It is characterized that the seasonal variations of As and other aqueous solutes are limited within the upper portion of aquifer only (&lt;30 m bgl) and can be related to seasonal cycling of redox status, aggregation and dispersion of As scavenging colloids, local groundwater abstraction and monsoonal recharge. The results of surface complexation modeling indicate that PO43- is the major competitor of As(III) and As(V) adsorption onto Fe oxyhydroxides. This study concludes that the reductive dissolution of Fe oxyhydroxides followed by competitive sorption reactions with the aquifer sediment is the process conducive for As enrichment in groundwater of Bengal Basin. Present study advocates that despite low concentration of As in groundwater, a rigorous assessment of attendant health risk for Mn is necessary prior to considering mass scale exploitation of the BSA for sustainable drinking water supply. This study also validates that TW platform colors can be used as a rapid screening tool for As and Mn in drinking water wells to prioritize As mitigation management. / <p>QC 20130919</p> / EURINDIA 2009-1665

This high-resolution biogeochemical study investigated spatial and temporal variability in the mixing interface zones within a wetland-aquifer system near a municipal landfill in the city of Norman, Oklahoma. Steep biogeochemical gradients indicating zones of enhanced microbial activity (e.g. iron/sulfate reduction and fermentation) were found at centimeter-scale hydrological and lithological interfaces. The small resolution study was achieved by combining passive diffusion samplers with capillary electrophoresis for chemical analysis. The spatial and temporal variability of biogeochemical processes found at the interfaces was evaluated in a depth profile over a period of three years. Correlations between geochemical parameters were determined using Principal Component Analysis (PCA) and the principal factors obtained were interpreted as a dominant biogeochemical process. Factors scores were mapped by date and depth to determine the spatial-temporal associations of the dominant processes. Fermentation was the process controlling the greatest variability in the dataset followed by iron/sulfate reduction, and methanogenesis. The effect of seasonal and hydrologic changes on biogeochemistry was evaluated from samples collected in a wet/dry period from three locations exhibiting upward, downward, and negligent hydrologic flow between aquifer and wetland. PCA was used to identify the principal biogeochemical processes and to obtain factor scores for evaluating significant seasonal and hydrological differences via analysis of variance. Iron and sulfate reduction were dominated by changes in water table levels and water flow paths, whereas methanogenesis and bacterial barite utilization were dominated by season and associated with a site with negligible flow. A preliminary study on microbial response to changes in geochemical nutrients (e.g. electron acceptors and electron donors) was conducted using in situ microcosms with the purpose of quantifying iron and sulfate reduction rates. Problems encountered in the experiment such as leaks in the microcosms did not allow the determination of respiration rates, therefore the experiments will be repeated in the future. The results suggest that iron and sulfate reduction were stimulated with the addition of sulfate and ferrihydrite (electron acceptors) and acetate and lactate (electron donors). This research demonstrates the importance of assessing biogeochemical processes at interface zones at appropriate scales and reveals the seasonal and hydrological controls on system processes.

Hypersaline tidal flats (HTFs) are transitional ecosystems commonly occurring in arid and semiarid coastal areas. (e.g. Australia and New Caledonia), Africa (e.g. Senegal, Gambia, and Madagascar), Central America (e.g. Nicaragua), South America (e.g. Ecuador and on the north, northeast, and southeast Brazilian coasts). Due to their location, HTFs might exert biogeochemical control over cycling of nutrients (e.g. Fe and Si) across the land to ocean transition, accelerating or retarding the nutrient export to the ocean and other adjacent ecosystems. This biogeochemical control is governed by soil physicochemical conditions (e.g. pH and salinity) and pedogenesis (e.g. redox processes). Thus, study of the soil coloidal fraction, the pedogenic processes, and the distribution of Si in the different soil components can provide a detailed characterization of HTF soils and give insights into the Si dynamics in these environments. In view of this, two HTFs on the Brazilian coast were studied on the Brazilian coast and the data are presented here. The first chapter aims to investigate the pedogenesis in HTF soils based on detailed morphological descriptions and Fe and Mn sequential extractions. The second chapter discusses silicon geochemistry in HTF soils based on sequential extractions, SEM, and XRD modeling of the fine clay fraction. And lastly, the third one reports the characteristics, distribution, and genesis of clay minerals in HTF soils on the basis of XRD modeling, TEM-EDS, FTIR, and XRF analysis. Redox reactions control the pedogenic evolution in HTF soils. These processes lead to a mobilization of Fe2+ and Mn2+ upward in the soils profiles, followed by oxidation and precipitation of Fe and Mn oxyhydroxides. These reactions, along with pyrite oxidation, lead to a transformation of the deeper soil horizons. Formation of Fe oxyhydroxides in the uppermost soil horizons exerts control on Si dynamics by co-precipitation and adsorption reactions. Together, Si associated with Fe oxyhydroxides and amorphous silicates are the main components of the readily soluble Si pool in HTF soils. The environmental conditions are conducive to clay transformations in the soils. Our data indicate that kaolinite is progressively altered to Mg-rich smectite through mixed-layering, withdrawing Si from the soil porewater. / Planícies hipersalinas costeiras (PHCs) são ecossistemas transicionais comumente encontrados em regiões áridas e semiárias. Estes ambientes são encontrados em várias regiões do mundo, tais como Oceania (e.g. Austrália e Nova Caledónia), África (e.g. Senegal, Gambia e Madagascar), América Central (e.g. Nicarágua), América do Sul (e.g. Equador e as costas norte, nordeste e sudeste do Brasil). Por estarem posicionados na transição entre os ecossistemas marinhos e de terras altas, os solos de PHCs devem exercer um controle biogeoquímico na ciclagem de nutrientes (e.g. Si e Fe), afetando o fluxo dos mesmo para o oceano e ecossitemas adjacentes. Este controle biogeoquímico é governado pelas condições fisico-químicas do meio (e.g. pH e salinidade) e pelos processos pedogenéticos atuantes nos solos (e.g. processos redox). Desta forma, o estudo da fração coloidal, da pedogênese e da distribuição do Si nos diferentes componentes do solo possibilita caracterizar detalhadamente os solos de PHCs e desvendar os processos que controlam a dinâmica de Si no ambiente. Portanto, duas PHCs localizadas na costa brasileira foram estudadas e os resultados estão apresentados em três capítulos nesta tese. O primeiro capítulo teve por objetivo investigar a pedogênese em PHCs com base em estudos morfológicos e extrações sequenciais de Fe e Mn. O segundo discute a geoquímica de silício nos solos com base em extrações sequenciais, MEV e modelagem de raios-X da fração argila fina. O terceiro capítulo discorre sobre as características, distribuição e gênese de argilominerais nos solos com base em modelagem de raios-X, MET-EDS, FTIR e FRX. As reações redox parecem controlar a evolução pedogenética nestes solos, as quais levam à mobilização ascendente de Fe2+ e Mn2+ nos perfis, oxidação da pirita e, consequentemente, transformação dos horizontes mais profundos. Estes processos também são responsáveis pela formação de oxihidróxidos de Fe e Mn nos horizontes superiores dos perfis de solo, levando à um controle do Si por reações de co-precipitação e adsorção envolvendo oxihidróxidos de Fe. O Si associado aos oxihidróxidos de Fe e silicatos amorfos são os principais componentes da fração mais solúvel de Si nos solos estudados. As condições ambientais nas PHCs são favoráveis às transformações minerais. Os dados indicam que a caulinita é alterada para esmectitas magnesianas por processos de interestratificação, removendo Si da solução do solo.

Hypersaline tidal flats (HTFs) are transitional ecosystems commonly occurring in arid and semiarid coastal areas. (e.g. Australia and New Caledonia), Africa (e.g. Senegal, Gambia, and Madagascar), Central America (e.g. Nicaragua), South America (e.g. Ecuador and on the north, northeast, and southeast Brazilian coasts). Due to their location, HTFs might exert biogeochemical control over cycling of nutrients (e.g. Fe and Si) across the land to ocean transition, accelerating or retarding the nutrient export to the ocean and other adjacent ecosystems. This biogeochemical control is governed by soil physicochemical conditions (e.g. pH and salinity) and pedogenesis (e.g. redox processes). Thus, study of the soil coloidal fraction, the pedogenic processes, and the distribution of Si in the different soil components can provide a detailed characterization of HTF soils and give insights into the Si dynamics in these environments. In view of this, two HTFs on the Brazilian coast were studied on the Brazilian coast and the data are presented here. The first chapter aims to investigate the pedogenesis in HTF soils based on detailed morphological descriptions and Fe and Mn sequential extractions. The second chapter discusses silicon geochemistry in HTF soils based on sequential extractions, SEM, and XRD modeling of the fine clay fraction. And lastly, the third one reports the characteristics, distribution, and genesis of clay minerals in HTF soils on the basis of XRD modeling, TEM-EDS, FTIR, and XRF analysis. Redox reactions control the pedogenic evolution in HTF soils. These processes lead to a mobilization of Fe2+ and Mn2+ upward in the soils profiles, followed by oxidation and precipitation of Fe and Mn oxyhydroxides. These reactions, along with pyrite oxidation, lead to a transformation of the deeper soil horizons. Formation of Fe oxyhydroxides in the uppermost soil horizons exerts control on Si dynamics by co-precipitation and adsorption reactions. Together, Si associated with Fe oxyhydroxides and amorphous silicates are the main components of the readily soluble Si pool in HTF soils. The environmental conditions are conducive to clay transformations in the soils. Our data indicate that kaolinite is progressively altered to Mg-rich smectite through mixed-layering, withdrawing Si from the soil porewater. / Planícies hipersalinas costeiras (PHCs) são ecossistemas transicionais comumente encontrados em regiões áridas e semiárias. Estes ambientes são encontrados em várias regiões do mundo, tais como Oceania (e.g. Austrália e Nova Caledónia), África (e.g. Senegal, Gambia e Madagascar), América Central (e.g. Nicarágua), América do Sul (e.g. Equador e as costas norte, nordeste e sudeste do Brasil). Por estarem posicionados na transição entre os ecossistemas marinhos e de terras altas, os solos de PHCs devem exercer um controle biogeoquímico na ciclagem de nutrientes (e.g. Si e Fe), afetando o fluxo dos mesmo para o oceano e ecossitemas adjacentes. Este controle biogeoquímico é governado pelas condições fisico-químicas do meio (e.g. pH e salinidade) e pelos processos pedogenéticos atuantes nos solos (e.g. processos redox). Desta forma, o estudo da fração coloidal, da pedogênese e da distribuição do Si nos diferentes componentes do solo possibilita caracterizar detalhadamente os solos de PHCs e desvendar os processos que controlam a dinâmica de Si no ambiente. Portanto, duas PHCs localizadas na costa brasileira foram estudadas e os resultados estão apresentados em três capítulos nesta tese. O primeiro capítulo teve por objetivo investigar a pedogênese em PHCs com base em estudos morfológicos e extrações sequenciais de Fe e Mn. O segundo discute a geoquímica de silício nos solos com base em extrações sequenciais, MEV e modelagem de raios-X da fração argila fina. O terceiro capítulo discorre sobre as características, distribuição e gênese de argilominerais nos solos com base em modelagem de raios-X, MET-EDS, FTIR e FRX. As reações redox parecem controlar a evolução pedogenética nestes solos, as quais levam à mobilização ascendente de Fe2+ e Mn2+ nos perfis, oxidação da pirita e, consequentemente, transformação dos horizontes mais profundos. Estes processos também são responsáveis pela formação de oxihidróxidos de Fe e Mn nos horizontes superiores dos perfis de solo, levando à um controle do Si por reações de co-precipitação e adsorção envolvendo oxihidróxidos de Fe. O Si associado aos oxihidróxidos de Fe e silicatos amorfos são os principais componentes da fração mais solúvel de Si nos solos estudados. As condições ambientais nas PHCs são favoráveis às transformações minerais. Os dados indicam que a caulinita é alterada para esmectitas magnesianas por processos de interestratificação, removendo Si da solução do solo.

Mangroves are coastal ecosystems that provide many ecosystem services, for example: (i) carbon sequestration; (ii) mitigation of greenhouse gas emissions; (iii) retention and immobilization of contaminants; (iv) nursery for several marine species; so it is necessary to develop mangrove protection and recovery initiatives, which are among the most impacted and degraded ecosystems in the world. In addition, many ecosystem services are related to pedogenetic soil processes, however, few studies have carried out this approach. Therefore, this study aimed to analyze two mangrove recovery initiatives in different soil contexts, aiming at identifying the restoration of pedogenetic processes and soil quality. Therefore, two mangroves with reforestation areas were analyzed in two compartments of the Brazilian coast: a) one in the state of Ceará (CE) located in the northeast region marked by a source material rich in quartz and semiarid climate; b) another located in the state of Rio de Janeiro (RJ), in the Southeast region, which presents material rich in iron and a humid tropical climate. In both sites, it was possible to observe the reestablishment of pedogenetic processes such as paludization, gleization and sulfidization, which are related to ecosystem services such as carbon sequestration and retention and immobilization of contaminants. Our study also identified the soil quality improvement using the Soil Management Assessment Framework (SMAF) tool, it is emphasized that this approach has never been used in studies involving mangroves. In fact, mangrove revegetation initiatives were able to increase soil quality of parameters such as: bulk density, carbon content, phosphorus content and pH, and the increase in soil quality positively affected the restoration of ecosystem functions such as sequestering carbon. In addition, the SMAF tool proved to be a useful tool for studies of soil quality, however, adjustments should be considered, as well as the number of variables inserted. In general we also identify that the reestablishment of pedogenetic processes may occur in a short period of time and that this approach is fundamental to infer about the capacity of impacted mangroves to develop their ecosystem functions. / Manguezais são ecossistemas costeiros que provisionam múltiplos serviços ecossistêmicos, por exemplo: (i) sequestro de carbono; (ii) mitigação das emissões de gases de efeito estufa; (iii) retenção e imobilização de contaminante; (iv) berçário para diversas espécies marinhas. Assim é necessário desenvolver iniciativas de proteção e recuperação de manguezais, uma vez que estão entre os ecossistemas mais impactados e degradados em todo o mundo. Neste sentido, muitos serviços ecossistêmicos estão relacionados a processos pedogenéticos do solo, no entanto, poucos estudos realizaram essa abordagem. Diante disso, este estudo teve como objetivo analisar duas iniciativas de recuperação de manguezais, em diferentes contextos edáficos, visando identificar o restabelecimento de processos pedogenéticos e a restauração da qualidade do solo. Portanto, foram analisados dois manguezais com áreas de replantio em dois compartimentos da costa brasileira: a) um no estado do Ceará (CE) localizado na região nordeste marcada por um material de origem rico em quartzo e clima semiárido; b) outro localizado no estado do Rio de Janeiro (RJ), região Sudeste, que apresenta material de origem rico em ferro e clima tropical úmido. Em ambos os locais estudados foi possível observar em resposta ao desenvolvimento da vegetação, o restabelecimento de processos pedogenéticos como paludização, gleização e sulfidização que estão relacionados à serviços ecossistêmicos como sequestro de carbono e retenção e imobilização de contaminantes. Nosso estudo também identificou o aumento qualidade do solo utilizando a ferramenta Soil Management Assessment Framework (SMAF), ressalta-se que essa é uma abordagem que nunca foi utilizada em estudos envolvendo manguezais. De fato, as iniciativas de revegetação de manguezais foram capazes aumentar a qualidade do solo a partir de parâmetros como: densidade, conteúdo de carbono, conteúdo de fósforo e pH e o aumento da qualidade do solo afetou positivamente o restabelecimento de funções ecossistêmicas como sequestro de carbono. Além disso, a ferramenta SMAF mostrou-se ser uma ferramenta útil para estudos de qualidade do solo, no entanto ajustes devem ser considerados, assim como o número de variáveis inseridas. Em geral também identificamos que o restabelecimento de processos de pedogenéticos pode ocorrer em curto período de tempo e que essa abordagem é fundamental para inferir sobre a capacidade de manguezais impactados de desenvolver suas funções ecossistêmicas.

After mineral exploitation the residual grinded and milled material, rich in sulphide minerals and heavy metals, is often left exposed to the atmospheric variables. This weathered mine waste material can lead to the formation of acid mine drainage (AMD) which has negative effects to the environment. The fractionation of stable isotope of metals such as Cu and Fe can be measured using innovative analytical techniques developed recently and could offer a detailed hindsight of the geochemical processes occurring in mine contaminated sites. Tailings profiles from Northern Sweden with high content of Cu and Fe sulphides and in different stages of weathering and/or remediation, along with plant and soil samples from a phytoremediation test site in Ronneburg, Germany were analysed using MC-ICP-MS to measure the isotope ratios of 65Cu/63Cu and 56Fe/54Fe. The analytical method used requires anion exchange chromatography to extract Cu and Fe from a complex matrix prior to the proper isotope ratio measurement. The samples from the tailings profile were useful to interpret the geochemical processes that can lead to a fractionation of Cu and Fe in the field, since redox-driven reactions such as rock oxidation and mineral precipitation are present in such environment. This study shows that precipitation of covellite in a redox-boundary zone in a mine tailings can cause a clear fractionation of Cu (Δ65Curock-covellite= -5.66±0.05‰) and a depletion of the lighter Cu isotope in the oxidised areas of the tailings due to dissolution of the remaining Cu-sulphides. Precipitation of Fe(oxy)hydroxides as a result of the oxidation process of sulphide-bearing rocks can also fractionate Fe, being the precipitated mineral slightly enriched in 56Fe.The influence of soil bacteria and plant uptake in the fractionation of Cu and Fe was investigated in pot and field experiments at the Ronneburg site, where organic amendments were used. The results showed that the plant material was enriched in the lighter Fe isotope compared to the substrate used in the pot and field experiments, in spite of the application of a bacterial consortium. Cu isotope fractionation is more susceptible to the changes in the amendments used, being those bacterial consortium, mychorriza or compost than Fe isotope fractionation. There are differences in the fractionation values in pot and field trials, regardless of the type of organic amendment applied. As an overall view, leaves are enriched in the heavier Cu isotope compared to the soils, regardless of the amendment usedThe application of the results obtained in this work would help not only to offer a view in the cycle of Fe and Cu in the surface environment, and the understanding of the (bio)geochemical processes occurring in sulphide soil surfaces. But also in the way that current remediation techniques of metal contaminated sites could be evaluated, having in mind that simplified systems show a different Cu and Fe fractionation compared to natural systems where more variables are needed to take into account.

Les mécanismes mis en jeu lors du cyclage de batteries au Lithium Li//Li1.20Mn0.54Co0.13Ni0.13O2 ont été étudiés avec l'objectif de déterminer l'origine des capacités très élevées délivrées par les oxydes lamellaires " (1-x)LiMO2.xLi2MnO3 ". La caractérisation par diffraction des RX et des neutrons montre que la structure est maintenue et l'existence de fluctuations de composition qui peuvent être assimilées à l'existence de deux phases de compositions voisines. Les résultats des tests électrochimiques et les analyses menées au cours du cyclage en spectroscopie d'absorption des rayons X ont suggéré la participation de l'oxygène aux processus redox. Celle-ci a été confirmée par la préparation et la caractérisation de matériaux désintercalés et réintercalés chimiquement en lithium. Les analyses en microscopie électronique à transmission (HAADF-STEM) et en nanodiffraction, montrent qu'une densification associée à un dégagement d'oxygène a lieu à la périphérie des particules

Les mécanismes mis en jeu lors du cyclage de batteries au Lithium Li//Li1.20Mn0.54Co0.13Ni0.13O2 ont été étudiés avec l’objectif de déterminer l’origine des capacités très élevées délivrées par les oxydes lamellaires « (1-x)LiMO2.xLi2MnO3 ». La caractérisation par diffraction des RX et des neutrons montre que la structure est maintenue et l’existence de fluctuations de composition qui peuvent être assimilées à l’existence de deux phases de compositions voisines. Les résultats des tests électrochimiques et les analyses menées au cours du cyclage en spectroscopie d’absorption des rayons X ont suggéré la participation de l’oxygène aux processus redox. Celle-ci a été confirmée par la préparation et la caractérisation de matériaux désintercalés et réintercalés chimiquement en lithium. Les analyses en microscopie électronique à transmission (HAADF-STEM) et en nanodiffraction, montrent qu’une densification associée à un dégagement d’oxygène a lieu à la périphérie des particules / The charge and discharge mechanism of Li1.20Mn0.54Co0.13Ni0.13O2 was studied using several characterization tools in order to determine the origin of the high capacity observed for the system (1-x)LiMO2.xLi2MnO3 used as positive electrode for Li-ion batteries. The electrochemical results and in operando XAS analyses performed during the 1st cycle of Li//Li1.20Mn0.54Co0.13Ni0.13O2 cells suggested the possible participation of oxygen anion to the redox processes. It was supported by the in-depth analysis of materials prepared by chemical Li deintercalation and reinsertion. The results of XRD, HAADF-STEM and nanodiffraction analyses, combined with electrochemical experiments performed in different conditions (rate, temperature …), revealed that different types of reactions occur in the particles during the 1st cycle. Within the bulk Ni, Co and O are involved in the redox processes, whereas Mn is not: oxygen ions are oxidized in charge and reduced during the next discharge reversibly. At the surface, the same oxidation processes occur during the first charge, but with the release of oxygen gaz and a densification of the lattice. During the next discharge and subsequent cycles, the redox reaction occurring near the surface after the 1st charge involves thus Co, Ni and Mn.

Le phosphore (P) est un nutriment essentiel dans le contrôle de l'eutrophisation des eaux de surface. La majorité du P causant cette eutrophisation dans les pays occidentaux est aujourd'hui issu des sols agricoles, ce qui explique pourquoi les recherches actuelles sur l'eutrophisation se focalisent sur la compréhension des mécanismes par lequel le P est relargué de ces sols. Dans cette thèse, nous étudions ces mécanismes en nous focalisant sur la fraction dissoute (DP) du P, fraction la plus menaçante du point de vue de l'eutrophisation. Une double approche a été utilisée, combinant le suivi de la composition d'eaux du sol et d'eaux de ruisseau dans un petit bassin versant (BV) agricole représentatif (BV de Kervidy-Naizin, France) et des simulations expérimentales au laboratoire. Les suivis de terrain ont révélé que les zones humides ripariennes (RW) étaient les principales zones de relargage de DP dans le BV étudié, via deux mécanismes essentiellement déclenchée par les fluctuations des hauteurs de nappe, i) la réhumectation des sols (DRW) et ii) la dissolution réductrice des oxydes de fer du sol dans de périodes d'anoxie. Ces mêmes suivis ont révélé la présence de fortes variations spatiales de la nature chimique (inorganique et organique/colloïdale) du DP relargué. Les variations saisonnières et interannuelles de l'hydroclimat, combinées aux variations locales de topographie ont été démontrées être les deux facteurs principaux contrôlant i) la fréquence des épisodes DRW, et ii) la durée des périodes anoxiques, entraînant au final de fortes variations saisonnières et interannuelles de la dynamique de relargage du DP. Comme indiqué dans un modèle conceptuel général, la topographie est sans doute le facteur clé de contrôle des variations observées, en raison de son rôle sur i) le transfert de P à partir des parcelles agricoles amont, ii) le taux de minéralisation du P organique du sol P et iii), le déclenchement des deux mécanismes de relargage précités. Les expériences en laboratoire ont confirmé le rôle des événements DRW comme processus clé causant le relargage de DP dans les RWs. Les résultats ont démontré que le DP relargué consistait non seulement de "vrai" DP inorganique et organique, mais aussi de P colloïdal, le P colloïdal et le DP organique étant les plus réactifs aux événements DRW. Les données ont aussi révélées que ces différentes formes de P provenaient de différentes sources dans le sol (méso et macroporosité pour P colloïdal et le DP organique; microporosité pour DP inorganique), et que la quantité de P colloïdal relargué était positivement corrélée avec la teneur en matière organique et la taille de biomasse microbienne du sol. Ces mêmes expériences ont confirmé le rôle des conditions anoxiques comme conditions favorisant la libération de DP dans les RWs. La dissolution réductive de sol Fe-oxyhydroxydes n'est cependant pas le seul processus impliqué, un autre processus étant la hausse du pH causée par des réactions de réduction. Les résultats obtenus démontrent que l'augmentation de pH contrôle la libération de DP dans les sols riches en matière organique, alors que ce relargage est contrôlé principalement par la réduction des oxydes de fer dans les sols pauvres en matière organique. Les données expérimentales démontrent également que l'apport de sédiments issus des sols agricoles amont accroit le relargage de DP dans les RW, probablement en raison de la dissolution des oxydes de fer de ces mêmes sédiments par les bactéries ferroréductrices des Rws. Au final, cette thèse permet de mieux contraindre les mécanismes et facteurs responsables du relargage de DP dans les bassins versants agricoles. Une conséquence très pratique de ce travail est que la conception de stratégies pour limiter les fuites de DP dans ces bassins ne peut se faire sans une prise en compte des rôles de l'hydroclimat, de la topographie locale et des propriétés du sol sur ce relargage. / Phosphorus (P) is a key nutrient in controlling surface water eutrophication. Because of the decrease of urban and industrial P emissions, most of the P nowadays causing surface water eutrophication in western countries consists of P transferred from agricultural soils, explaining why current eutrophication research focused on understanding the mechanisms by which P is released from soils. In this thesis, we studied these release mechanisms for dissolved P (DP) – i.e. the most bioavailable P component for algae - using an approach combining field monitoring of soil and stream water compositions in a small, headwater catchment typical of western countries agricultural catchments (the Kervidy-Naizn catchment, France), and laboratory experimental simulations. Field monitoring data revealed that riparian wetlands (RW) are the main zones of DP release and DP production in the studied catchment, through essentially two mechanisms triggered by groundwater table fluctuations, namely i) rewetting of dry soils (DRW), and ii) reductive dissolution of soil Fe (hydr)oxides during anaerobic periods. Field monitoring data also revealed the presence of strong spatial variations in the chemical nature (inorganic vs. organic/colloidal) of the released DP, which was in relation to differences in soil properties and local topography. Seasonal and inter-annual hydroclimate variations, combined with variations in local topography were found to control the frequency of soil DRW events and duration of anaerobic periods, resulting in strong seasonal and inter-annual variations of DP release dynamics. As shown in a conceptual model, topography is likely to be the key driver of the observed spatial and temporal variations, because of its combined control on i) the transfer of P from upland fields to RW zones, ii) the mineralization rates of soil organic P and iii) the triggering of the above two release mechanisms. Laboratory leaching experiments on the same soils confirmed the role of DRW events as a major process causing DP release pulses in RWs. The data demonstrated that the released DP consisted not only of true dissolved inorganic and organic P but also of colloidal P, the latter phase being the most reactive to DRW events. The data also revealed that the different P forms came from different P sources in the soil (soil macro/mesopores for colloidal P and organic DP; soil micropores for inorganic DP) and that the amount of released colloidal P correlated positively with the organic matter contents and soil microbial biomass size of the soil. Anaerobic incubation experiments, on their hand, confirmed the role of anoxic conditions as conditions favoring the release of DP in RW. Reductive dissolution of soil Fe-oxyhydroxide was, however, not the sole process involved in that release, another process being the rise in pH caused by reduction reactions. Experimental data showed that the pH rise controlled the DP release in organic-rich soils, this release being on the contrary mainly controlled by soil Fe-oxyhydroxides reductive dissolution in organic-poor soils. Experimental data also showed that the input of soil sediments from upland fields enhanced the release of DP in RW, most likely due to the enhanced dissolution of sediment Fe-oxyhydroxides by RW Fe-reducing bacteria. Overall, this thesis allowed new constraints to be placed on the release mechanisms of DP in headwater agricultural catchments. One very practical output is that great care should be taken of hydroclimate variability, local topography, and soil property when designing and implementing management options to reduce DP release and transfer in agricultural catchments.

The thesis is focused on the electrodeposition of tantalum from ionic solution 1-butyl-1- methylpyrrolidinium bis(trifluoromethylsulfonyl) imide, ([BMP]Tf2N) at 200°C and description of related transfer and kinetic phenomena on the interface between the ionic solution and working electrode. Furthermore, the electrodeposition of tantalum layers in different ionic solutions containing tantalum salts and especially in ([BMP]Tf2N) is introduced. In the last part of the thesis, results of cyclic voltammetry, surface analysis SEM and elemental analysis EDX are discussed. MIS (metal-insulator-semiconductor) structure was determined comprising porous anodic alumina as the insulator and semiconductive TaxOy on the top of the insulator. The electric conductivity of the MIS structures was studied by using amper-volt IV and CV characteristics. The results of the cyclic voltametry, impedance spectroscopy and chronoamperometry are discussed.