Les rivières sont une source importante de constituants biogéochimiques pour les océans. Jusqu’à présent, les modèles océaniques globaux représentaient de manière inadéquate ou ignoraient simplement les apports continentaux de nutriments, de carbone, d’alcalinité provenant des rivières. En particulier, les perturbations anthropiques des apports fluviaux au cours du 20 ème siècle et leurs conséquences sur l’état physique et biogéochimique des océans - notamment la zone côtière - n’ont pas encore été analysées à l’aide d’un modèle global prenant en compte la circulation tridimensionnelle de l’océan. L’objectif principal de cette thèse était donc d’intégrer les apports biogéochimiques provenant des rivières dans un modèle océanique global afin d’améliorer la compréhension du cycle du carbone de l’océan côtier et son évolution au cours du 20 ème siècle. Dans un premier temps, mon travail a visé à l’amélioration des connaissances concernant le rôle des apports biogéochimiques fluviaux sur le cycle du carbone océanique à long-terme, en se focalisant sur la période préindustrielle. Pour cela, j’ai estimé les apports des rivières en utilisant des modèles permettant d’estimer l’érosion chimique et le transfert de matière organique desécosystèmes terrestres à l’océan. Ces apports fluviaux ont ensuite été ajoutés dans le modèle biogéochimique océanique HAMOCC et leurs impacts sur la production primaire océanique et les flux de CO2 entre l’atmosphère et l’océan ont été analysés. Les résultats nous ont permis de quantifier un dégazage de CO 2 préindustriel de 0.23 Pg C yr -1 pour l’océan global, principalement localisé à proximité de l’embouchure des rivières. Le modèle a également démontré l’existence d’un transfert inter-hémisphèrique de carbone, avec un plus grand apport des rivières à l’océan dans l’hémisphère nord, et un transfert de l’hémisphère nord à l’hémisphère sud où un dégazage net se produit. Une augmentation considérable de la production primaire océanique induite par les apports des rivières a également été prédite.La modélisation biogéochimique de l’océan côtier a ensuite été améliorée, en augmentant la vitesse de minéralisation de la matière organique dans les sédiments côtiers et en incluant la dégradation de la matière organique dissoute d’origine terrestre (tDOM) dans l’océan. Par ailleurs, notre analyse suggère un temps de résidence des eaux dans la zone côtière significativement plus courte (14-16 mois en moyenne) que celui estimé jusqu’à présent (>4 ans). Ce temps de courte résidence implique un transfert efficace de matière organiquede l’océan côtier à l’océan ouvert, un état autotrophe net de l’océan côtier, ainsi qu’un puit de CO 2 (0.06-0.08 Pg C yr -1) pour la période préindustrielle, contrairement aux hypothèses précédemment proposées dans la littérature.Dans le dernier chapitre, les perturbations océaniques induites par les changements de la concentration en CO 2 dans l’atmosphère, de la physique de l’océan et des apports biogéochimiques fluviaux au cours du 20 ème siècle ont été analysées. Les résultats indiquent que la réduction de production primaire nette (NPP) observée dans les océans tropicaux et subtropicaux, pourrait être entièrement compensée par une augmentation de la NPP dans l’océan austral et dans les systèmes côtiers de type «EBUS». Les simulations montrent aussi que l’augmentation des apports fluviaux provoque une augmentation de NPP océanique à l’échelle de l’océan côtier (+15 %) et à l’échelle globale (+ 4 %). En conclusion, cette thèse a permis de démontrer l’importance d’inclure la variabilité spatio-temporelle des apports fluviaux et des processus biogéochimiques de l’océan côtier dans la description du cycle du carbone océanique global. Les améliorations apportées au modèle océanique global HAMOCC permettront d’affiner les prédictions du rôle de l’océan dans le cycle du carbone au cours du 21 ème siècle. / River deliver vast amounts of terrestrially derived compounds to the ocean. These fluxes are of particular importance for the coastal ocean, which is recognized as a region of disproportionate contribution to global oceanic biological fluxes. Until now, the riverine carbon, nutrient and alkalinity inputs have been poorly represented or omitted in global ocean biogeochemistry models. In particular, there has yet to be a model that considers the pre-industrial riverine loads of biogeochemical compounds to the ocean, and terrestrial inputs of organic matter are greatly simplified in their composition and reactivities in the ocean. Furthermore, the coastal ocean and its contribution to the globalcarbon cycle have remained enigmatic, with little attention being paid to this area of high biological productivity in global model analysis of carbon fluxes. Lastly, 20 th century perturbations in riverine fluxes as well as of the physical and biogeochemical states of the coastal ocean have remained unexplored in a 3-dimensional model. Thus, the main goals of this thesis are to integrate an improved representation of riverine supplies in a global ocean model, as well as to improve the representation of the coastal ocean in the model, in order to solve open questions with respect its global contributions to carbon cycling.In this thesis, I first aimed to close gaps of knowledge in the long-term implications of pre-industrial riverine loads for the oceanic cycling of carbon in a novel framework. I estimated pre-industrial biogeochemical riverine loads and their spatial distributions derived from Earth System Model variables while using a hierarchy of state-of-the-art weathering and organic matter land-ocean export models. I incorporated these loads into the global ocean biogeochemical model HAMOCC and investigated the induced changes in oceanic biological production and in the air-sea carbon flux, both at the global scale and in a regional shelf analysis. Finally, I summarized the results by assessing the net land sink of atmospheric carbon prescribed by the terrestrial models, and comparing it to the long-term carbon outgassing determined in the ocean model. The study reveals a pre-industrial oceanic outgassing flux of 231 Tg C yr -1 ,which is found to a large degree in proximity to the river mouths. The model also indicates an interhemispheric transfer of carbon from dominant northern hemisphere riverine inputs to outgassing in the southern hemisphere. Furthermore, I observe substantial riverine-induced increases in biological productivity in the tropical West Atlantic (+166 %), the Bay of Bengal (+377 %) and in the East China Sea (+71 %), in comparison to a model simulation which does not consider the riverine inputs.In addition to considering supplies provided by riverine fluxes, the biogeochemical representation of the coastal ocean is improved in HAMOCC, by firstly increasing organic matter remineralization rates in the coastal sediment and by secondly explicitly representing the breakdown process of terrestrial dissolved organic matter (tDOM) in the ocean. In an analysis of the coastal fluxes, the model shows a much shorter residence time of coastal waters (14-16 months) than previously assumed, which leads to an efficient cross-shelf transport of organic matter and a net autotrophic state for both the pre-industrial timeframe and the present day. The coastal ocean is also revealed as a CO2 sink for the pre-industrial time period (0.06-0.08 Pg C yr -1 ) in contrary to to the suggested source in published literature. The sink is however not only caused by the autotrophic state of the coastal ocean, but it is likely also strongly influenced by the effects of biological alkalinity production, as well as both physical and biogeochemical characteristics of open ocean inflows.In the final chapter, 20 th century oceanic perturbations due to changes in atmospheric CO 2 concentrations and in the physical climate, and to increases in riverine nutrient supplies were investigated by using sequential model simulations. The model results show that the decrease in the net primary production (NPP) in the tropical and subtropical oceans due to temperature-induced stratification may be completely compensated by increases in the Southern Ocean and in Eastern Boundary Upwelling Systems (EBUS). The model also reveals that including increases in riverine supplies causes a global ocean NPP increase of +4 %, with the coastal ocean being a particularlystrongly affected region (+15 %).This thesis shows a strong necessity to represent spatio-temporal changes in riverine supplies and of the coastal ocean state in spatially explicit global models in order to assess changes of the global cycling of carbon in the ocean in the past and potentially in the future. / Doctorat en Sciences / info:eu-repo/semantics/nonPublished

O complexo estuarino-lagunar de Cananéia-Iguape vem sofrendo diversos impactos antrópicos desde à abertura do canal artificial Valo Grande, que alterou significativamente o setor Norte do sistema com o aumento da influência fluvial. O assoreamento da região, vem sendo um problema recorrente, impactando a pesca, o turismo e a navegação. Este trabalho visa entender a dispersão do aporte terrígeno na região a partir da modelagem numérica, com dados atualizados, para melhor reprodução da simulação no estuário. Os resultados do modelo mostraram altas concentrações dos componentes biogeoquímicos no setor Norte do sistema e baixa influência da maré, ocasionando alta retenção destes elementos na região. O setor Sul apresentou baixa influência do rio e alta influência marinha, com valores de silicato e fosfato dissolvidos e matéria inorgânica em suspensão dentro do esperado para um sistema estuarino preservado. O modelo apresentou um bom comportamento para a região, com bons resultados hidrodinâmicos e de qualidade da água. Ressalta-se a importância de um contínuo monitoramento da região e o uso de modelo para acompanhar o desenvolvimento geomorfológico e as alterações biogeoquímicas do estuário para auxiliar em medidas preventivas com o intuito de minimizar o impacto antrópico no sistema. / The estuarine-lagoon complex of Cananéia-Iguape has suffered several anthropic impacts since the opening of the Valo Grande artificial channel, which significantly altered the northern sector of the system with the increase of fluvial influence. The silting up of the region has been a recurrent problem, impacting fishing, tourism and navigation. This work aims to understand the dispersion of the terrigenous contribution in the region with numerical modeling and updated data, for better reproduction of the simulation in the estuary. The results of the model showed high concentrations of the biogeochemical components in the northern sector of the system and low tidal influence, causing high retention of these elements in the region. The southern sector showed low river influence and high marine influence, with expected values of dissolved silica and phosphate and inorganic suspended matter for a preserved estuarine system. The model showed a good behavior for the region, with good hydrodynamic and water quality results. It is emphasized the importance of continuous monitoring of the region and the use of a model to monitoring the geomorphological development and the biogeochemical alterations of the estuary to assist in preventive measures with the intention of minimizing the anthropic impact in the system.

Ökosystem-Ingenieure sind Organismen, deren Auswirkung auf die Funktion von Ökosystemen im Vergleich zu ihrer Anzahl und Biomasse überproportional groß ist. Ein klassisches Beispiel für Ökosystem-Ingenieure sind grabende Organismen, deren Aktivitäten (Bioturbation) sowohl die Sedimentmatrix als auch das Porenwasser in aquatischen Sedimenten beeinflussen. Solche Tiere wirken auf eine große Anzahl von biogeochemischen Prozessen in benthischen Ökosystemen ein, unter anderem auf die aerobe Atmung (Respiration). Die Respiration aquatischer Sedimente umfasst häufig über 50 % der gesamten Respiration von aquatischen Systemen und spielt eine große Rolle im globalen Kohlenstoffkreislauf. Die vorliegende Doktorarbeit beschäftigt sich mit den Auswirkungen der physikalischen Umwelt (Sedimenteigenschaften, am meistens hydraulischer Leitfähigkeit) auf die mikrobielle Respiration von Sedimenten, in denen Bioturbation durch Chironomidenlarven stattfindet. Um die Auswirkungen von Bioturbation auf Respiration zu messen und zu identifizieren, wurde eine neue Messmethode entwickelt (Kapitel 4.1). Kapitel 4.2 zeigt, dass der Einfluss von Bioturbation auf die Respiration des Sediments mit zunehmender Temperatur ansteigt. Kapitel 4.3 belegt, dass Resazurin auch für die Messung der Respiration in marinen Sedimenten geeignet ist. Kapitel 4.4 vergleicht und begutachtet die große Anzahl und Vielfalt hydrologischer, biogeochemischer und ökologischer Tracer einschließlich Resazurin. Die physikalische Umwelt (Sedimentmatrix) kontrolliert wie stark die Auswirkungen der Bioturbation auf die Respiration des Sedimentes sind. Dementsprechend liefert diese Doktorarbeit die Basis für das Verständnis der Auswirkungen benthischer Bioturbation auf Respiration und Kohlenstoffumsatz in limnischen und marinen Sedimenten. / Ecosystem engineers are organisms, whose impact on ecosystem functioning is disproportionally large compared to their abundance and biomass. A classic example of ecosystem engineers are burrowing organisms whose activities (bioturbation) affect the sediment matrix and pore solutes in aquatic sediments. Bioturbating animals are impacting on a number of biogeochemical processes in benthic ecosystems, including, among others, aerobic respiration. Respiration of aquatic sediments often comprises over 50% of the total respiration of aquatic systems, and plays a tremendous role in the global carbon cycle. The present thesis deals with the impacts of the physical environment (sediment characteristics, mainly hydraulic conductivity and grain fractions) on the (microbial) respiration of bioturbated sediments. In order to disentangle the effects of bioturbation on respiration, a novel measurement method has been developed (Chapter 4.1). Chapter 4.2 reveals that the impact of bioturbation on sediment respiration increases with increasing temperature. Chapter 4.3 shows that resazurin can also be used for the measurement of respiration in bioirrigated marine sediments. Chapter 4.4 reviews the large number and diversity of hydrological, biogeochemical and ecological tracers including resazurin. The present thesis shows that in sediments with low hydraulic conductivity (diffusion-dominated sediments) (Chapters 4.1,4.2) bioturbation is altering sediment respiration to a larger extent than in sediments with high hydraulic conductivity (advection-dominated sediment) (Chapter 4.3). The physical environment (sediment matrix) controls the intensity of the impacts of bioturbation on sediment respiration. Thus, this thesis provides a basis for understanding the impact of benthic bioturbators on respiration and carbon sequestering in freshwater and marine sediments.

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), 2010. / Cataloged from PDF version of thesis. / Includes bibliographical references. / Biological activity has shaped the surface of the earth in numerous ways, but life's most pervasive and persistent global impact has been the secular oxidation of the surface environment. Through primary production - the biochemical reduction of carbon dioxide to synthesize biomass - large amounts of oxidants such as molecular oxygen, sulfate and ferric iron have accumulated in the ocean, atmosphere and crust, fundamentally altering the chemical environment of the earth's surface. This thesis addresses aspects of the role of marine microorganisms in driving this process. In the first section of the thesis, biomarkers (hydrocarbon molecular fossils) are used to investigate the early history of microbial diversity and biogeochemistry. Molecular fossils from the Transvaal Supergroup, South Africa, document the presence in the oceans of a diverse microbiota, including eukaryotes, as well as oxygenic photosynthesis and aerobic biochemistry, by ca. 2.7Ga. Experimental study of the oxygen requirements of steroid biosynthesis suggests that sterane biomarkers in late Archean rocks are consistent with the persistence of microaerobic surface ocean environments long before the initial oxygenation of the atmosphere. In the second part, using Prochlorococcus (a marine cyanobacterium that is the most abundant primary producer on earth today) as a model system, we explored how microbes use the limited nutrient resources available in the marine environment to make the protein catalysts that enable primary production. Quantification of the Prochlorococcus proteome over the diel cell-division cycle reveals that protein abundances are distinct from transcript-level dynamics, and that small temporal shifts in enzyme levels can redirect metabolic fluxes. This thesis illustrates how molecular techniques can contribute to a systems-level understanding of biogeochemical processes, which will aid in reconstructing the past of, and predicting future change in, earth surface environment / by Jacob Richard Waldbauer. / Ph.D.

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), June 2011. / "June 2011." Cataloged from PDF version of thesis. / Includes bibliographical references. / Atmospheric nitrous oxide N₂O concentrations have been rising steadily for the past century as a result of human activities. In particular, human perturbation of the nitrogen cycle has increased the N₂O production rates of the two major sources of this greenhouse gas, soil and the ocean. Nitrification, and particularly ammonia oxidation, is one of the major processes that produces N₂O in the ocean. In this thesis, a series of stable isotopic methods have been used to characterize the biogeochemical controls on N₂O production by marine nitrification as well as the natural abundance stable isotopic signatures of N₂O produced by marine nitrifiers. This thesis shows that in addition to chemical controls on N₂O production rates such as oxygen (O₂) and nitrite (NO₂- ) concentrations, there are also biological controls such as nitrifier cell abundances and coastal phytoplankton blooms that may influence N₂O production by ammonia oxidizers as well. Ammonia oxidizers can produce N₂O through two separate biochemical mechanisms that have unique isotopic signatures. Using culture-based measurements of these signatures, we conclude that one of these pathways, nitrifier-denitrification, may be a significant source of N₂O produced in the South Atlantic Ocean and possibly the global ocean. / by Caitlin Frame. / Ph.D.

O silício encontra-se no meio marinho nas formas: dissolvida e particulada (biogênica e litogênica). O ciclo biogeoquímico deste elemento está sujeito à influência sazonal e às alterações antrópicas. Este trabalho visa entender a relação entre as diferentes formas de silício como resposta a processos de origem natural e antrópica em diferentes ambientes (Estreito de Bransfield, Antártica; Complexo Estuarino-Lagunar de Cananeia-Iguape, SP; região costeira de Recife, PE). O Estreito de Bransfield pela sua localização remota é das áreas estudadas, a menos impactada pelo homem. A região nordeste do Estreito mostrou menores concentrações de silicato na superfície associadas à menor diversidade fitoplanctônica, constituída por diatomáceas do gênero Corethron que facilitam o afundamento de Si e a remineralização do C e N. Já na região sudoeste do Estreito a concentração de silicato foi maior, assim como a influência do degelo, que contribui para uma maior disponibilidade de ferro, indicada pelo traçador Si*, aumentando a diversidade fitoplanctônica. Nesta região também houve a presença de espécies que facilitam o afundamento de C e N e a remineralização de Si. O Complexo Estuarino-Lagunar de Cananeia-Iguape, apresentou sinais de impacto antrópico sobretudo no setor norte (Iguape), mostrado pelas diferentes frações do silício que foram excelentes indicadores de processos erosivos. No setor sul a influência antrópica não foi observada, assim o silício indicou processos de origem natural como a sedimentação, evidenciada pela remoção do BSi e do LSi, e a ressuspensão onde as concentrações das frações particuladas foi maior. A região costeira de Recife está sob a influência dos aportes fluviais provenientes dos rios Capibaribe e Beberibe. A distribuição da maioria dos parâmetros, incluindo o silicato e o BSi, mostraram esta influência vinda de oeste, atingindo a barreira na saída do porto e se propagando em direção a nordeste. Devido ao maior aporte de nutrientes nas estações mais próximas à costa a produção primária foi incentivada, evidenciada pelos maiores valores de clorofila-a e BSi. Nas estações mais distantes da costa os parâmetros tiveram valores característicos de áreas oligotróficas, com as frações de silício mostrando concentrações bastante baixas. O silício se mostrou um excelente indicador de aportes continentais naturais e antrópicos. São poucos os trabalhos que quantificam o BSi e o LSi no meio aquático, assim este estudo consiste em um ponto inicial para o entendimento do silício particulado em águas brasileiras. / Silicon is found in the marine environment under the forms: dissolved and particulate (biogenic and lithogenic). The biogeochemical cycle of this element is subject to seasonal influences and anthropogenic changes. This work aims to understand the relationship between different forms of silicon in response to processes of natural and anthropogenic origin in different environments (Bransfield Strait, Antarctica; Cananeia-Iguape Estuarine-Lagoon Complex, SP ; coastal region of Recife, PE) . The Bransfield Strait is, of the studied areas, the least impacted by man, because of its remote location. The northeastern Strait region showed lower silicate concentrations associated with lower phytoplankton diversity, consisting of diatoms of the genus Corethron that facilitate sinking af Si and remineralization of C and N. In the southwestern region of the Strait silicate concentration was higher, as well as the influence of thaw, which contributes to increased iron availability, indicated by Si* tracer, that increases phytoplankton diversity. In this region there was also the presence of species that facilitate the sinking of C and N and the remineralization of Si. Cananeia-Iguape Estuarine -Lagoon Complex, showed signs of anthropogenic impact especially in the northern sector (Iguape), showed by silicon different fractions, which were excellent indicators of erosion processes. In the southern sector, anthropogenic influence was not observed. Silicon indicated processes of natural origin, like sedimentation, evidenced by the removal of BSi and LSi, and resuspension where concentrations of particulate fractions was higher. The coastal region of Recife is under influence of fluvial inputs from Capibaribe and Beberibe rivers. The distribution of most parameters, including silicate and BSi, showed this influence coming from the west, reaching the barrier at the port exit and propagating toward northeast. Due to higher nutrient availability in the stations nearest to the coast, primary production was encouraged, evidenced by high values of chlorophyll-a and BSi. In the stations more distant to the coast, the parameters had values characteristic of oligotrophic areas , with the forms of silicon showing very low concentrations. Silicon proved to be an excellent indicator of continental natural and anthropogenic contributions. There are few studies that quantify the BSi and LSi in the aquatic environment, therefore this study is a starting point for understanding particulate silicon in Brazilian waters.

O Carbono Orgânico Dissolvido (COD) constitui em uma das principais formas de carbono orgânico exportado em rios e em outras vias hidrológicas preferencias nas bacias de drenagem. Na Amazônia, os estudos sobre o COD nas suas águas abrangem principalmente as grandes bacias da região central, com poucas análises sobre alterações na sua dinâmica após a substituição de florestas por pastagens, uma das mudanças no uso da terra mais comum na região. Este estudo objetivou fornecer informações que auxiliem na compreensão destes processos, através da comparação entre as dinâmicas das concentrações nas vias hidrológicas preferenciais, as exportações, e os balanços de COD durante eventos de precipitação em duas bacias de primeira ordem, sendo uma com floresta e outra com pastagem. O estudo foi conduzido numa fazenda próxima à cidade de Cacaulândia, no estado de Rondônia. As amostras foram coletadas na transição do período seco para o chuvoso (Agosto a Novembro de 2004) e período chuvoso (Janeiro a Abril de 2005). Os resultados mostraram que na transição do período seco para o chuvoso, apenas as concentrações de COD nas vias de entrada para o solo, precipitação na pastagem e precipitação interna na floresta, e de saída, pelos igarapés e água subterrânea apresentaram diferenças estatisticamente significativas entre floresta e pastagem. No período chuvoso, além destas, outras vias hidrológicas, como a solução do solo a 20 e 100 cm de profundidade e o escoamento superficial, mostraram-se distintas entre estes dois sistemas. Comparando-se os períodos do ano, em ambas as bacias as concentrações de COD nas vias hidrológicas foram superiores na época de transição do período seco para o chuvoso. A única exceção a este padrão foi observada na água subterrânea da floresta, que apresentou maiores concentrações de COD no período chuvoso. Na pastagem, o aumento do escoamento superficial resultou em maiores exportações de COD do que aquelas observadas na floresta. Como conseqüência, os balanços de COD a cada evento e anualmente, tendeu a ser mais positivos (maior retenção de COD) na última. Embora neste estudo não tenha sido possível, entre outros, quantificarem os fluxos de COD na água subterrânea e, portanto, obter um balanço mais preciso para esta forma de carbono nestes sistemas, os resultados demonstraram que a conversão de florestas em pastagens acarreta em um aumento significativo das exportações de COD, via igarapé, no último local, tanto em eventos individuais de precipitação, quanto anualmente. / Dissolved Organic Carbon (DOC) is one of the main fractions of organic carbon exported in rivers and other flow paths in watersheds. In the Amazon, studies of DOC in waters focus mainly on the large basins of the central region, with few analyses of changes in its dynamics after the replacement of forests by pastures, one of the most important land use changes in the region. This objective of this study was to obtain more information about these processes, by comparing dynamics in several flowpaths, exports and budgets of DOC during rain events in two first-order watersheds, one with forest and another with pasture. The study was conducted near city of Cacaulândia in the State of Rondônia. Samples were collected in the transition from dry to wet (August to November of 2004) and in the wet seasons (January to April of 2005). The results demonstrate that during the transition from dry to wet seasons, statistically significant differences in DOC concentrations between forest and pasture occur only in the inputs from precipitation in pasture and throughfall in forest and in the outputs in streams and groundwater. During the wet season the remaining flowpaths analyzed, soil solution at 20 and 100cm depth and overland flow, also showed statistically significant differences in DOC concentrations between forest and pasture. In terms of the periods of the year, in both watersheds DOC concentrations were higher during the transition from dry to wet seasons. The only exception to this pattern was observed in forest groundwater, with higher concentrations during the wet season. In the pasture, increases in discharge resulted in higher DOC export than in forest. As a consequence of this, DOC budgets, both in individual events and annually, showed a larger retention in the latest. Although in this study it was not possible, among others, to quantify the fluxes of DOC in groundwater, the results demonstrate that the conversion of forest into pasture causes a significant increase of DOC export in streams, both in individual rain events and on an annual basis.

Le mercure (Hg) est un polluant global et ses effets écotoxicologiques sont fortement dépendants de sa forme chimique principalement sous forme de méthylmercure (MeHg). En raison de la forte bioaccumulation et bioamplification du MeHg dans les réseaux trophiques, l'exposition humaine est associée à la consommation de poissons, mais aussi du riz produit à proximité des régions minières riches en Hg (Chine). La composition isotopique du Hg est un outil potentiellement puissant qui a été récemment utilisé pour le traçage de la contamination par mercure et les processus biogéochimiques dans l'environnement et les organismes vivants. Dans ce travail, la spéciation et la composition isotopique du mercure d'échantillons bio-environnementaux ont été étudiées afin d'élucider les voies de contamination par Hg entre les milieux contaminés et certains organismes vivants cibles, tels que le système sol-riz dans une région minière (Hg) et le biote aquatique dans une rivière polluée par une usine de production chlore/soude. Une étude écotoxicologique a également démontré que la composition isotopique de Hg dans les différents organes des poissons permet de mieux comprendre les voies métaboliques du Hg et la réponse toxicologique induite. / Mercury (Hg) is a global pollutant and its ecotoxicological effects are strongly dependent on its chemical form mainly as methylmercury (MeHg). Due to the high bioaccumulation and biomagnification of MeHg in food webs, human exposure occurs through the consumption of fish, but also rice nearby Hg mining area (China). Hg isotopes composition is a potentials powerful tool and has been recently used to trace Hg contamination and biogeochemical processes in environment and living organisms. In this work, Hg speciation and isotopic composition of bio-environmental samples has been investigated in order to elucidate Hg contamination pathways between contaminated sites and target living organisms such as soil-rice plant system in a Hg mining region and aquatic biota in a river impacted by a chlor-alkali plant. An ecotoxicological study has also demonstrated how Hg isotopic composition in different fish organs allows to better understand Hg metabolic pathways and induced toxicological response.

La réhabilitation des friches industrielles dans les zones urbaines est un enjeu majeur pour le développement durable des villes. La gestion et la reconversion de ces sites, imposées par la réglementation, nécessitent toutefois le développement d’outils d’évaluation des risques environnementaux et sanitaires, et de techniques de remédiation durables. Cette thèse a porté sur la mise en place d’outils multidisciplinaires pour la gestion durable des sites pollués, avec le cas particulier d’un site de recyclage de batteries au plomb caractérisé par une pollution historique en plomb principalement mais également d’autres polluants inorganiques (Cd, Sb, As, Cu et Zn), couramment définis par le terme d’Eléments Traces Métalliques (ETM). Ce travail a cherché à renseigner les mécanismes impliqués dans les systèmes polluants-sol-plantes pour renforcer la prise en compte de la qualité globale des sols dans la gestion des sites industriels, tout en essayant de répondre à des questions de la recherche appliquée. En plus des outils et procédures classiquement utilisés pour évaluer, contrôler et réduire les risques environnementaux et sanitaires causés par les sols pollués, le développement des mesures de biodisponibilité (plantes et les humains) et d’écotoxicité (différents tests biologiques: inhibition de la mobilité de daphnies, Microtox® et induction de bactéries bioluminescentes, microbiologie) permet d’affiner la classification des sols contaminés en termes de dangerosité. De plus, des plantes engrais verts (bourrache, phacélie et moutarde), communément utilisées en agriculture ou par les jardiniers (car elles améliorent les propriétés bio-physico-chimiques des sols avec un système racinaire et une grande production d’exsudats racinaires), ont été testées pour la re-fonctionnalisation des sols pollués. Enfin, les mécanismes impliqués dans le devenir des polluants dans la rhizosphère et les microorganismes associés ont été étudiés. L’ensemble des résultats fourni des éléments de réponse et des moyens d’améliorer la gestion des sols contaminés par des métaux et métalloïdes. (1) Tout d’abord, la séparation par taille des différentes fractions de sol permet une réduction significative des tonnages de matériaux contaminés et donc une économie réelle lors de la mise en décharge des sols excavés avec un gain certain en termes d’empreinte écologique. (2) Ensuite, le calcul d’écoscores pour les differents échantillons de sols pollués, sur la base des résultats des essais d’écotoxicité, ont permis d’affiner plus précisemment les risques par rapport aux paramètres physico-chimiques « classiques » requis par la réglementation. Des différences de sensibilité ont été observées en fonction de la nature de l’essai biologique, l’origine de l’échantillon, les propriétés physico-chimiques et les concentrations totales de polluants. (3) Contrairement à la phacélie, la bourrache et la moutarde ont amélioré la respiration du sol, réduit l’écotoxicité et la quantité de plomb bioaccessible et totale dans le sol, respectivement par phytostabilisation et stockage dans les racines (Pb, Sb) ou par phytoextraction et donc stockage dans les parties aériennes. En outre, ces plantes pourraient être testées sur le terrain pour une utilisation en phytoremédiation des friches industrielles et des jardins modérément pollués. Selon la nature du métal, du type de sol et des plantes, la compartimentation et la spéciation du polluant diffèrent, ainsi qu’en fonction des caractéristiques agronomiques du sol et l’activité microbienne de la rhizosphère. Un criblage moléculaire et une méta-analyse de la génomique microbienne ont permis de mettre en évidence les différences dans les communautés bactériennes étudiées en fonction du niveau de concentration métallique, des espèces végétales et des caractéristiques des sols étudiés. / Rehabilitation of brownfields in urban areas is a major challenge for the sustainable development of cities. Management and conversion of these sites, imposed by regulation, however, require the development of tools for environmental risk assessment and health and sustainable remediation techniques. This thesis focused on the establishment of multidisciplinary tools for the sustainable management of polluted site, with the particular case of rehabilitation recycling of lead batteries with a mainly historical lead pollution and other inorganic pollutants (Cd, Sb, As, Cu and Zn), currently defined as Metal Trace Elements (MTE). While trying to answer questions of applied research, this work has sought to investigate the mechanisms involved in the soil-plant pollutants to strengthen the consideration of the overall quality of soil management for industrial sites. In addition to the tools and procedures conventionally used to assess, control and reduce environmental and health risks caused by polluted soils; measures of bioavailability (plants and humans) and ecotoxicity (different bioassays: inhibition of the mobility of Daphnia magna, Microtox® and induction of bioluminescent bacteria and microbiology) have been developed with the aim to refine the classification of contaminated soils in terms of dangerousness. Moreover, green manure plants (borage, phacelia and mustard), commonly used in agriculture or by gardeners because they improve the bio-physico-chemical properties of soils with a root system and a large production of root exudates were tested for re-functionalization of polluted soils. Finally, the mechanisms involved in the fate of pollutants in the rhizosphere and their microorganisms in the plant were studied. The main results provide some answers and ways of improving the management of soils contaminated by metals and metalloids. (1) First, the size separation for soil fractions allows a significant reduction in tonnages of contaminated material and therefore costs for the landfill excavated soil with a gain result in terms of ecological footprint. (2) Then, calculation for the differents polluted soil samples of eco-scores based on the results of ecotoxicity tests can discriminate more accurately compared to physicochemical parameters required by the regulations. Differences in sensitivity were observed depending on the nature of the bioassay, the origin of the sample, physico-chemical properties and total concentrations of pollutants. (3) Unlike phacelia, borage and mustard improve soil respiration, ecotoxicity and reduce theamount of bioaccessible and total lead in soil, respectively by phytostabilisation and storage in roots (Pb, Sb) or phytoextraction and storage in aerial parts. Further, these plants could be field tested for use in phytoremediation of brownfields and gardens moderately polluted. Depending on the nature of the metal, the type of soil and plant, compartmentalization and speciation of the pollutant differ, and in conjunction with agronomic characteristics of soil and rhizosphere microbial activity. Molecular screening and meta-analysis of microbial genomics have enabled highlight differences in bacterial communities studied by species and growing conditions.

O complexo estuarino-lagunar de Cananéia-Iguape vem sofrendo diversos impactos antrópicos desde à abertura do canal artificial Valo Grande, que alterou significativamente o setor Norte do sistema com o aumento da influência fluvial. O assoreamento da região, vem sendo um problema recorrente, impactando a pesca, o turismo e a navegação. Este trabalho visa entender a dispersão do aporte terrígeno na região a partir da modelagem numérica, com dados atualizados, para melhor reprodução da simulação no estuário. Os resultados do modelo mostraram altas concentrações dos componentes biogeoquímicos no setor Norte do sistema e baixa influência da maré, ocasionando alta retenção destes elementos na região. O setor Sul apresentou baixa influência do rio e alta influência marinha, com valores de silicato e fosfato dissolvidos e matéria inorgânica em suspensão dentro do esperado para um sistema estuarino preservado. O modelo apresentou um bom comportamento para a região, com bons resultados hidrodinâmicos e de qualidade da água. Ressalta-se a importância de um contínuo monitoramento da região e o uso de modelo para acompanhar o desenvolvimento geomorfológico e as alterações biogeoquímicas do estuário para auxiliar em medidas preventivas com o intuito de minimizar o impacto antrópico no sistema. / The estuarine-lagoon complex of Cananéia-Iguape has suffered several anthropic impacts since the opening of the Valo Grande artificial channel, which significantly altered the northern sector of the system with the increase of fluvial influence. The silting up of the region has been a recurrent problem, impacting fishing, tourism and navigation. This work aims to understand the dispersion of the terrigenous contribution in the region with numerical modeling and updated data, for better reproduction of the simulation in the estuary. The results of the model showed high concentrations of the biogeochemical components in the northern sector of the system and low tidal influence, causing high retention of these elements in the region. The southern sector showed low river influence and high marine influence, with expected values of dissolved silica and phosphate and inorganic suspended matter for a preserved estuarine system. The model showed a good behavior for the region, with good hydrodynamic and water quality results. It is emphasized the importance of continuous monitoring of the region and the use of a model to monitoring the geomorphological development and the biogeochemical alterations of the estuary to assist in preventive measures with the intention of minimizing the anthropic impact in the system.