In Brazil, the grape is produced in several regions, but in the South that the culture of the vine has great economic importance because it has suitable climatic conditions for growing this species. The application continues to Bordeaux mixture as a fungicide has caused a rise in copper in vineyard soils, especially in the copper layers of soil, causing an increased bioavailability and causing greater phytotoxicity to plants. The phytotoxicity of copper depends on the relative distribution between the chemical forms of metal, which are related to physical and chemical properties of each soil, and the soluble metal in free or complexed with organic matter (OM) present, more phytotoxic to the forms in the form of insoluble salts or associated with organic matter, oxides and clays present in the soil solid phase. Copper is toxic to a wide variety of edaphic organisms, affecting growth, morphology and metabolism of microorganisms, and thus adversely affect the characteristics of soil organic matter (SOM), since these microorganisms are responsible for degradation. Also, copper has the ability to form stable complexes with the MOS, protecting it from the humification process, because the complex formation prevents these macromolecules are able to participate in other chemical reactions and undergo changes in its structure. The overall purpose of the thesis was to evaluate the relationship between MOS and copper in soil, related to the chemical characteristics of SOM and bioavailability of copper. For the development of theory, surface samples (0-10 cm) of six soils were collected in areas of vine with a history of systematic application of heavy metals and nearby areas with native plants without copper in Serra Gaucha region of Brazil. Studies of adsorption and desorption were done to verify the retention capacity of copper in the soil, and were related to studies of fractionation of copper used to quantify and qualify the ways of metal retention in different soil components. Four soils were incubated in plastic bags, with the addition of different amounts of copper (0, 200, 400, 600 and 1.200 mg kg-1), were collected periodically for chemical analysis. Some samples of these soils were selected for the creation of chemical fractionation to study the chemical characteristics of humic substances. The results showed that soils under native forest have low copper content, from 77.2 to 84.7 mg kg-1, linked mainly in fractions more stable as the residual and MOS compared to soils with a vineyard with levels total of 674.2 to 1154.6 mg kg-1, distributed in all fractions of soil, but the retention in the more stable fractions decreased of 51.0 to 78.2% of appropriations. Studies of adsorption and desorption showed that the soils have high adsorption capacity and high hysteresis occurs due to the presence of sites with high affinity for copper. The incubation studies showed that the presence of this metal in high concentration affects the process of humification of the SOM, which explains the fact that humic substances from soils of vineyards have less aromaticity with greater presence of functional groups compared to soil under native forest. The availability of this element was changed after the incubation period and may be related to the content of the fraction of humic acid (CAH) in the soil and changes in soil pH. Plant growth was affected with the increase of copper content available and was directly proportional to the fraction of fulvic acid (CAF). / No Brasil a uva é produzida em várias regiões, principalmente na pequena propriedade, porém é no sul do país que a cultura da videira tem grande importância econômica, pois seu cultivo é feito para suprir a demanda das indústrias de sucos e vinhos que foram implantadas na região pelos descendentes de italianos. A aplicação continua de calda bordalesa como fungicida tem causado uma elevação nos teores de cobre em solos de vinhedo, principalmente nas camadas superficiais de solos, provocando maior disponibilidade do elemento e causando fitotoxidade às plantas. A fitotoxidade do cobre depende da distribuição relativa entre as formas químicas desse metal, as quais são relacionadas às propriedades físico-químicas de cada solo, sendo as formas solúveis do metal, forma livre ou complexada à matéria orgânica (MO), mais fitotóxicas em relação às formas insolúveis na forma de sais ou associados à MO, óxidos e argilas presentes na fase sólida do solo. No solo, o cobre é tóxico para uma grande variedade de organismos, afetando o crescimento, a morfologia e o metabolismo de microrganismos, e dessa forma, provocando alteração nas características da matéria orgânica do solo (MOS), uma vez que esses microrganismos são responsáveis pela sua degradação. Também, o cobre possui a capacidade de formar complexos estáveis com a MOS, protegendo-a do processo de humificação, pois a formação dos complexos impede que essas macromoléculas estejam aptas a participar de outras reações químicas e sofrer modificações em sua estrutura. Os objetivos da tese foram: a) caracterizar formas e determinar adsorção/dessorção de cobre em solos com e sem histórico de aplicação de calda bordalesa; b) extrair e analisar a qualidade de substâncias húmicas de solos incubados com diferentes teores de cobre; e c) estimar a disponibilidade do cobre às plantas em solos com aplicação de diferentes teores de cobre. Para o desenvolvimento da tese, amostras superficiais (0 10 cm) de seis solos foram coletadas em áreas de vinhedos com histórico de aplicação sistemática de calda bordalesa e de áreas próximas com mata nativa sem adição de cobre na Serra Gaúcha. Estudos de adsorção e dessorção foram feitos para verificar a capacidade máxima de retenção do cobre no solo, e foram relacionados com estudos de fracionamento do cobre utilizados para quantificar e qualificar as formas de retenção do metal em diferentes componentes do solo. Quatro solos foram incubados em sacos plásticos, com adição de diferentes quantidades de cobre (0, 200, 400, 600 e 1.200 mg kg-1), sendo coletados periodicamente para análises químicas. Algumas amostras desses solos foram selecionadas para a realização do fracionamento químico para o estudo das características químicas das substâncias húmicas. Os resultados mostraram que solos sob mata nativa possuem baixo teor de cobre, entre 77,2 a 84,7 mg kg-1, ligados principalmente nas frações mais estáveis como a residual e de MOS, em comparação a solos com cultivo de videira com teores totais entre 674,2 a 1.154,6 mg kg-1, distribuídos em todas as frações do solo, porém a retenção nas frações mais estáveis diminui para 51,0 a 78,2%. Os solos possuem alta capacidade de adsorção e ocorre alta histerese devido à presença de sítios com alta afinidade com o cobre. Os estudos de incubação sugerem que a presença desse metal em alta concentração afeta a processo de humificação da MOS, que explica o fato das substâncias húmicas de solos de vinhedo ter menor aromaticidade com maior presença de grupamentos funcionais comparadas às de solos sob mata nativa. A disponibilidade desse elemento foi alterada após o período de incubação e pode estar relacionada ao teor da fração de ácidos húmicos (CAH) presentes no solo e a variação de pH do solo. O desenvolvimento das plantas foi afetado com a elevação do teor de cobre disponível e teve relação diretamente proporcional com a fração de ácidos fúlvicos (CAF).

No description available.

Les rejets urbains modifient la qualité de la matière organique dissoute (MOD) dans les milieux récepteurs et sont une source majeure de micropolluants. Il a été montré que la MOD naturelle influençait la spéciation et le devenir des micropolluants, que ce soit dans le milieu récepteur ou dans les ouvrages de traitement. L’objectif ici est d’étudier l’impact de la présence et de la qualité de la MOD sur la répartition dissous/particulaire des micropolluants dans les systèmes aquatiques, de la station d’épuration au milieu récepteur. L’originalité de notre travail est de comparer l’influence d’une MOD fulvique naturelle et d’une MOD urbaine, et de travailler à des concentrations proches des concentrations du milieu aquatique. Dans un premier temps, nous avons caractérisé l’adsorption de différents types de MOD (acides fulviques (AF) et rejets de STEP) sur différents types de particules (calcite, goethite, montmorillonite, quartz et charbon actif). Dans un second temps, nous avons caractérisé l’adsorption de certains micropolluants (éléments traces métalliques (ETM) et As (V), Hydrocarbures Aromatiques Polycycliques (HAP) et 13 produits pharmaceutiques) sur les particules en absence de MOD ou en présence de MOD ((AF) et rejets de STEP). Concernant l’influence de la MOD sur l’adsorption des ETM par les particules, les résultats obtenus montrent une diversité importante de situations selon les ETM et les particules considérées. Pour la goethite, nous avons observé une diminution de l’adsorption en présence de MOD urbaine par rapport à ce qui est observé en l’absence de MOD. Pour le charbon actif, au contraire, il y a plus d’adsorption en présence d’AF pour tous les ETM sauf pour le Cu qui est plus adsorbé en présence de MOD urbaine. Les différentes particules ont globalement présenté une capacité d’adsorption importante des HAP mais cette capacité est très fortement modulée par la MOD et ce, de manière différente selon les particules. Pour la goethite et la montmorillonite, l’adsorption des HAP a diminué en présence de MOD. Elle est plus forte en présence de MOD d’origine urbaine qu’en présence des AF dans le cas de l’adsorption des HAP légers sur la goethite et de l’adsorption de tous les HAP sur la montmorillonite. L’adsorption des HAP plus lourds sur la goethite est par contre plus faible avec la MOD urbaine qu’en présence d’AF. Concernant l’adsorption des HAP par le CAP, nous avons observé une diminution en présence de MOD particulièrement dans le cas de la MOD urbaine. Les expérimentations menées avec le sulfaméthoxazole n’ont pas permis de mettre en évidence une influence de l’origine de la MOD sur l’adsorption de cette substance. Pour les autres produits pharmaceutiques, l’adsorption sur le CAP en présence de MOD urbaine est globalement beaucoup plus faible qu’en matrice minérale et aussi plus faible qu’en matrice acides fulviques. L’abattement de ces contaminants sera donc plus faible en présence de MOD urbaine. Cela peut être relié au fractionnement de la MOD urbaine lors de son adsorption sur le CAP. Les résultats obtenus démontrent qu’il est indispensable de tenir compte du rôle de la MOD urbaine dans les milieux récepteurs anthropisés (où elle peut être majoritaire en basses-eaux) pour mieux comprendre le devenir des micropolluants dans les systèmes aquatiques et en particulier leur répartition particulaire/dissous. En outre, dans un contexte d’épuration des eaux usées, l’abattement des micropolluants est dépendant de la nature de la MOD présente, par conséquent, les résultats d’abattement des micropolluants observés en potabilisation des eaux pourraient être sensiblement différents en épuration des eaux usées / Urban discharges alter the quality of dissolved organic matter (DMO) in receiving environments and are a major source of micropollutants. Natural MOD has been shown to influence the speciation and fate of micropollutants in both the receiving and treatment media. The objective here is to study the impact of the presence and quality of MOD on the dissolved/particulate distribution of micropollutants in aquatic systems, from the treatment plant to the receiving environment. The originality of our work is to compare the influence of a natural fulvic MOD and an urban MOD, and to work at concentrations close to concentrations in the aquatic environment. Initially, we characterized the adsorption of different types of MOD (fulvic acids (AF) and releases of STEP) on different types of particles (calcite, goethite, montmorillonite, quartz and activated carbon). In a second step, we characterized the adsorption of certain micropollutants (metallic trace elements (ETMs) and As (V), Polycyclic Aromatic Hydrocarbons (PAHs) and 13 pharmaceutical products) on particles in the absence of MOD or in the presence of MOD (AF) and releases of STEPs. Concerning the influence of MOD on the adsorption of ETMs by particles, the results obtained show a significant diversity of situations depending on the ETMs and particles considered. For goethite, we observed a decrease in adsorption in the presence of urban MOD compared to what is observed in the absence of MOD. For activated carbon, on the other hand, there is more adsorption in the presence of AF for all VTE except for Cu, which is more adsorbed in the presence of urban MOD. The various particles have generally exhibited a high adsorption capacity of PAHs, but this capacity is strongly modulated by the MOD, and this varies according to the particles. For goethite and montmorillonite, adsorption of PAHs decreased in the presence of MOD. It is stronger in the presence of urban MOD than in the presence of AF in the case of adsorption of light PAHs on goethite and adsorption of all PAHs on montmorillonite. The adsorption of heavier PAHs on goethite is lower with urban MOD than in the presence of AF. Concerning the adsorption of PAHs by the CAP, we observed a decrease in the presence of MOD, particularly in the case of urban MOD. Experiments conducted with sulfamethoxyazole did not reveal any influence of the origin of MOD on adsorption of this substance. For other pharmaceutical products, adsorption on CAP in the presence of urban MOD is generally much lower than in the mineral matrix and also lower than in the fulvic acid matrix. The abatement of these contaminants will therefore be lower in the presence of urban MOD. This can be related to the fractionation of urban MOD when adsorbed on the CAP. The results obtained show that it is essential to take into account the role of urban MOD in anthropized receptor environments (where it can be the majority in low-water environments) in order to better understand the fate of micropollutants in aquatic systems and in particular their particle/dissolved distribution. In addition, in a wastewater treatment context, the abatement of micropollutants is dependent on the nature of the present MOD, therefore, the abatement results of micropollutants observed in water purification could be significantly different in wastewater treatment

The majority of lakes on Earth are shallow, unproductive and located at high latitudes. These lakes are experiencing big changes due to climate change, where two environmental drivers operate simultaneously, browning and warming. How they affect lake ecosystems is not well understood. Here, I addressed this issue by using a theoretical and an experimental approach. In particular, I generated model predictions and compared them with the results of a realistic large-scale experiment, where browning and warming were manipulated in a factorial design. In addition, model outcomes were compared with data from 12 unproductive lakes sampled along a gradient of browning. Another novelty of my thesis is that it integrates benthic and pelagic food web components in the model and experimental approaches. I found that browning affected the resources availability for benthic and pelagic producers in the model and in the experiment. With browning, benthic primary producers became increasingly light limited and declined, while pelagic producers became less nutrient limited and increased. Pelagic nutrient limitation was alleviated by two non-exclusive mechanisms. Browning directly enriched the water with nutrients, and browning indirectly increased the nutrient flowing from the sediment to the pelagic habitat via suppression of benthic producers. To tease apart these two mechanisms I applied structural equation modeling (SEM). The indirect evidence by SEM suggests that both mechanisms contributed equally to the pelagic nutrient concentration in the experiment. Interestingly, a model food web with only primary producers shows similar qualitative behavior as a food web with grazers and carnivores included. This happens because carnivorous fish exert strong top-down control in the more productive habitat, which relaxes grazing pressure on primary producers and increases resource limitation in the adjacent habitat. Biomass of benthic and pelagic consumers followed the same pattern as their resources. The lake data were largely congruent with model expectations and supported the findings of the experiment. Furthermore, the model also predicted a negative relationship between total phosphorus and both primary and fish production, which was observed across the 12 lakes. Warming effects were more complex. The model predicts that warming effects should depend on browning and are expected to be strongest in the more productive of the two (benthic and pelagic) habitats. For example, at low levels of browning the biomasses of benthic algae and fish are expected to decline with warming, which was observed in the experiment. In contrast, observed warming effects at high levels of browning deviated from model expectations. The mechanisms by which browning and warming interactively affect lake food webs are still poorly understood. This thesis offers a conceptual foundation for their further study through the integration of within- and between-habitat interactions.

Climate change scenarios predict that seawater temperature and precipitation will increase in the Baltic Sea region during the next century. In the northern part of the Baltic Sea, increasing inflows of the terrestrial allochthonous dissolved organic matter (ADOM) are expected to be a major consequence of elevated rainfall, which can alter light and nutrient availability for phytoplankton. The aim of my thesis was to elucidate effects of ADOM on phytoplankton production, community, size-structure and nutritional strategy along offshore south-north gradients in the Baltic Sea, as well as in estuarine systems exposed to seasonal variation in river discharge. Field studies, a mesocosm experiment and a modeling study were used to explore these issues. Results from the field studies and mesocosm experiment illustrated that the nutritional strategy, size-structure and cellular pigment content of the phytoplankton were governed by changes in ADOM, and thus in light and nutrient availability. A summer study along an offshore south-north gradient showed that the proportion of mixotrophic phytoplankton increased towards the north. In this area the concentrations humic substances (proxy for ADOM) were high, while the light availability and phosphorus concentrations were relatively low. The phytoplankton cells responded to reduced light availability by increasing their chlorophyll a: carbon ratio. Additionally, the levels of photoprotective pigments decreased from south to north, as a result of acclimation to a low-light environment and reduced exposure to ultraviolet radiation. According to ecological assumptions picophytoplankton should be favored in light- and nutrient-limited environments. However, the results did not follow that pattern, the proportion of picophytoplankton being highest in the relatively nutrient rich Baltic Proper. The study was performed during the decline of an extensive bloom of filamentous cyanobacteria, a successional phase in which picophytoplankton often dominate the phytoplankton community. The estuarine studies performed in the Bothnian Bay (Råne estuary) and in the Bothnian Sea (Öre estuary) showed different successions. In the Råne estuary no spring phytoplankton bloom occurred and highest primary production was observed during the summer. This absence of a spring bloom was explained by low phosphorus and high ADOM concentrations, while the summer maximum could be explained by higher temperature and nutrient concentrations. In the Öre estuary a marked phytoplankton spring bloom was observed as well as an ADOM sustained bacterial production phase. The later secondary peak of bacterial production observed in summer, concomitant with an extended secondary primary production peak, suggests that autochthonous dissolved organic matter supported the bacterial growth Furthermore, the photosynthetic efficiency (i.e. phytoplankton growth rates) was lower during spring, indicating that high ADOM, and thus lower light and phosphorus availability, disfavored phytoplankton growth. Our modeling study showed that climate change can impact the food web; however effects will be different between basins. In the southern Baltic Sea elevated temperature and nutrient discharge may promote nutrient recycling and oxygen consumption, potentially extending anoxic areas, sediment nutrient release and cyanobacteria blooms. In the north, increased inflow of ADOM may promote heterotrophic bacterial production and decrease primary production due to light attenuation and lower phosphorus availability. This will favor the heterotrophic microbial food web and consequently lead to lower food web efficiency of the ecosystem.

Les micropolluants organiques (MPO) tels que les HAPs, PCBs et NP sont sous la surveillance étroite des différentes agences de santé et de l'environnement à cause de leurs effets toxiques, cancérigènes et perturbateurs endocriniens sur les organismes vivants. Dans l'environnement, ils se retrouvent dans le sol, les aquifères, les eaux usées, et en raison de leurs propriétés hydrophobes, ces MPO sont principalement associés aux compartiments matière organique dans les boues d'épuration et les sédiments de rivières. La digestion anaérobie, procédé de stabilisation des boues, présente un potentiel pour l'abattement de ces composés. Les deux principaux mécanismes qui régissent l'abattement dans ces conditions des MPO sont le cométabolisme et la biodisponibilité. Leur double influence est évaluée dans ce travail, avec un focus fort sur l'étude des interactions MPO-matrice, la détermination de la distribution des MPO dans les compartiments physiques de la matrice (libre, sorbé à la matière dissoute et colloïdale (DCM) et sorbé aux particules) et avec une caractérisation fonctionnelle, physique et chimique détaillée de la matrice. Pour cela, des réacteurs anaérobies continus et batch ont été mis en œuvre avec des boues de caractéristiques différentes. L'abattement des MPO varie considérablement en fonction des caractéristiques des boues s'expliquant soit par des variations du niveau de cométabolisme, soit par les différents niveaux de biodisponibilité ; ceci suggère qu'une caractérisation détaillée de la matrice boue pourrait aider à prévoir les niveaux d'abattement des MPO. Par ailleurs, les cinétiques en batch montrent que l'abattement des MPO est associé aux premières étapes de la digestion anaérobie, conjointement à leur transfert du compartiment des particules vers le compartiment aqueux. L'abattement des MPO s'observe simultanément dans les trois compartiments libre, sorbé à la DCM et sorbé aux particules. Il est aussi noté l'importance du compartiment DCM sur l'abattement des MPO de haut poids moléculaire. Les coefficients de partage KDOC et Kpart ont été calculés pour étudier les interactions MPO-matrice., Ces données couplées à celles de caractérisation fonctionnelle de la matrice par fluorescence 3D ont permis de construire un modèle explicatif et prédictif des interactions MPO-matrice à l'aide de la méthode de régression partielle des moindres carrés (PLS). Il a été constaté que le compartiment type acide humique a un rôle important dans les interactions MPO-matrice, principalement dans la phase aqueuse, et dans la phase particulaire, les protéines complexes régissent les interactions. Enfin, des modèles PLS explicatifs et prédictifs d'abattement total des MPO ont été construits. Il en ressort que l'abattement des MPO est favorisé par tous les paramètres du cométabolisme (abattement des divers compartiments matière) et par la concentration des MPO en phase aqueuse ce qui tenterait à confirmer que ce compartiment correspond au compartiment biodisponible. Le modèle prédictif basé sur les caractéristiques des boues initiales a identifié les concentrations initiales de MPO (libre, sorbé à la DCM et aux particules) comme les variables les plus importantes qui permettent de prédire l'abattement total des MPO. Cette étude contribue ainsi à mieux comprendre la répartition des MPO dans les matrices boue, et son implication dans le devenir des MPO, de prévoir cette répartition par une caractérisation fonctionnelle de la matrice et de proposer des stratégies pour optimiser l'abattement des MPO au cours de la digestion anaérobie. / Organic micropollutants (OPs) such as PAHs, NP and PCBs, are nowadays looked as environmental pollutants by environmental and health agencies because of their toxic, carcinogenic and endocrine disrupting effect on living organisms. Within the environment, they can deposit to soil, water bodies and sewage system and due to their hydrophobic properties, they are mainly associated with hydrophobic compartments such as organic matter in sewage sludge. Anaerobic digestion has been shown as a potential biological process for removing these compounds. The two main mechanisms that govern their anaerobic removals are the cometabolism and the bioavailability. In this work, cometabolism and bioavailability influences were evaluated focusing mainly on the study of the OP-organic matrix interactions, the determination of the OPs distribution among the physical compartments (free, sorbed to dissolved and colloidal matter (DCM) and sorbed to particles) combined with a detailed physical, chemical and functional matrix characterization. For this, continuous and batch anaerobic reactors were fed with different sludge samples. It was found that the OPs removals varied greatly as a function of sludge characteristics and that greater or lesser removal might be explained either by variations in cometabolism or by different levels of bioavailability, suggesting that a detailed characterization of the feed may help to predict the OPs removals. Additionally, batch kinetics demonstrated that OPs removals are coupled to the first step of the anaerobic digestion, jointly to the OPs transfer from the particules to the aqueous compartment. The OPs are simultaneously removed from the three physical compartments (free, DCM and particules). Moreover, it was highlighted the importance of the DCM fraction on the removal of the high molecular weight OPs. KDOC and Kpart partition coefficients were calculated to study the OP-organic matrix interactions coupled to a functional characterization by 3D fluorescence of the matrix in order to construct an explicative and predictive model of the OP-organic matrix interactions using partial least square regression (PLS). It was found that the humic acid-like compartment has a great role in the OP-organic matrix interactions mainly in the aqueous phase, and in the particulate phase, the complex proteins govern the interactions. Finally, explanatory and predictive PLS models of total OPs removals were constructed. It was concluded that OPs removals are favored by all cometabolic parameters (substrates removals) jointly to the aqueous OPs concentration which tends to confirm that this compartment corresponds to the bioavailable one. The predictive model based on the initial sludge characteristics, identified the initial OPs concentrations (free, DCM and particulate) as the most important variables that predict the total OPs removals. This study contributes to better understand the OPs distribution among the sludge compartments and its role in the fate and removal of the compounds, to predict this distribution through matter functional characterization and to propose strategies in order to optimize the OPs removals under anaerobic conditions.

Des études pionnières ont montré que la composition isotopique de l’azote de matières organiques terrestres (δ15Norg) est corrélée à des paramètres climatiques tels que les précipitations et la température. Appliqué à la matière organique ancienne, ce concept a permis récemment de reconstituer des cycles humides/secs à la transition Paléocène-Eocène (56 Ma). Dans la continuité de ces travaux, cette thèse vise à tester le δ15Norg comme marqueur paléoclimatique sur des coupes couvrant d’autres périodes géologiques, marquées par des changements climatiques importants : la coupe de Taskomirsay (Pliensbachien-Toarcien, ~183 Ma), la coupe de Faddeevsky (Paléogène, probablement Eocène inférieur, 53-50 Ma) et une carotte du Bassin de Rennes (Eocène-Oligocène, ~34 Ma). Parallèlement une expérience de diagenèse sur des bois actuels a été menée en laboratoire pour mieux comprendre les effets de la diagenèse sur le δ15Norg. L’expérience de diagenèse suggère que la diagenèse précoce homogénéise les valeurs de δ15N pour conduire finalement à une valeur moyenne, intégrant les différentes composantes d’un environnement. Les résultats indiquent un changement non-linéaire et rapide qui suggère qu’il s’effectue quasiment de manière instantanée à l’échelle géologique. Néanmoins, les grands changements environnementaux affectant toutes les composantes d’un écosystème pourraient être potentiellement enregistrés par le δ15Norg. Les données paléoclimatiques inférées des isotopes de l’azote organiques sur les coupes étudiées ont été confrontées à d’autres caractéristiques géochimiques des sédiments étudiés (analyses élémentaires du carbone et de l’azote, Rock-Eval, biomarqueurs moléculaires, rapport des isotopes stables du carbone et la composition isotopique en hydrogène de certains biomarqueurs moléculaires), afin (i) de déterminer les sources de la matière organique et son état de préservation, et (ii) d’obtenir un éventail informations paléoenvironnementales/paléoclimatiques sur les coupes. Le réchauffement climatique documenté au Toarcien inférieur (Taskomirsay) par d’autres méthodes n’a pas eu d’impact sur le δ15Norg, qui suggère plutôt une humidité importante et quasiment constante, en accord avec la palynologie et la géochimie moléculaire. Les résultats obtenus sur la coupe principale du Paléogène (Faddeevsky) sont plus contrastés d’un point de vue paléoclimatique avec une réponse du δ15Norg différentielle entre la base et le sommet de la coupe. A la transition Eocène-Oligocène (Bassin de Rennes), le δ15Norg enregistre une baisse importante de l’humidité, en accord avec l’analyse des minéraux argileux. La baisse concomitante des températures à cette transition n’a probablement pas eu d’effet sur le δ15Norg. Le δ15Norg semble donc être principalement influencée par la disponibilité en eau. Les limites méthodologiques et analytiques du δ15Norg sont également discutées. Il apparaît notamment que les échantillons très riches en matière organique (>40%) ne sont pas adaptés au protocole préparation des échantillons qui est actuellement utilisé. Pour les matières organiques pré-quaternaires, l’analyse directe du δ15Norg sur les kérogènes pourrait constituer une alternative intéressante. A terme, le δ15Norg, associé à d’autres outils de reconstruction paléoenvironnementale, pourrait servir à préciser les modifications du cycle de l’azote – principalement via la disponibilité en eau et en nutriments – dans les paléoécosystèmes terrestres. / Nitrogen isotopes of modern and terrettrial organic matter (δ15Norg) has been related to precipitations and temperatures. These observations were recently applied to reconstruct humid/dry cycles at the Paleocene-Eocene transition (56 Ma). Following this work, this thesis aims to test the δ15Norg as a paleoclimatic marker on field sections encompassing other geological periods, characterized by contrasted climates: the Taskomirsay section (Pliensbachian-Toarcian, ~183 My), the Faddeevsky section (Paleogene, probably Early Eocene in age, 53-50 My) and a drill core from the Rennes Basin (Eocene-Oligocene, ~34 My). In addition, modern wood were incubated to evaluate the effects of early diagenesis on δ15Norg with a paleoenvironmental perspective. The incubation of modern wood suggests that early diagenesis homogenizes δ15N values leading to an average value integrating the different components of an environment. Results showed fast and non-linear effects of early diagenesis on organic matter, suggesting almost instantaneous changes at the geological scale. Thus, major environmental changes affecting all components of an ecosystem may be potentially recorded by the δ15Norg. Paleoclimatic data inferred from the organic nitrogen isotopes of the study sediments were compared to other geochemical features of the latter (carbon and nitrogen elemental analyses, Rock-Eval, molecular biomarkers, carbon and nitrogen isotopes, hydrogen isotopes measured on specific-compound), in order to (i) characterize sources of the organic matter and its preservation state, and (ii) get other paleoenvironmental markers. Global warming recorded in the Early Toarcian (Taskomirsay) had no impact on the δ15Norg that suggests high and almost constant humidity. This is consistent with palynological and molecular data. Results in Faddeevsky (Paleogene) are more difficult to interpret in terms of climate changes, with a contrasted response of the δ15Norg between the base and the top of the section. At the Eocene-Oligocene transition, δ15Norg values, in agreement with clay minerals changes, recorded a significant drop in humidity. In addition, the concomitant drop in temperatures, associated with this transition, probably had no effect on the δ15Norg values. All those results highlight water availability as a first climatic control on δ15Norg values. Methodological and analytical limitations of the δ15Norg are also discussed. It is concluded that OM-rich samples (> 40%) are most probably not suitable for the protocol of preparation, which is currently used. Alternatively, direct measurements of δ15Norg values for organic pre-quaternary sediments are suggested, by analyzing kerogens of the samples. Eventually, the δ15Norg, combined with other paleoenvironmental markers, could be used to evaluate the modifications of the nitrogen cycle – mainly via water and nutrients availability – in terrestrial paleoecosystems.

Les météorites carbonées sont les objets les plus primitifs du système solaire. Ils contiennent jusqu'à 4 % de carbone, principalement présent sous forme de matière organique insoluble (MOI). Celle-ci contient des informations essentielles sur les processus d’organo-synthèse qui se déroulent dans le système solaire, qui sont jusqu'ici mal compris. Un modèle statistique a été récemment proposé pour la structure moléculaire de la MOI ainsi qu'une voie de synthèse possible pour le squelette hydrocarboné de cette macromolécule (Derenne et Robert, 2010). Le premier objectif de ce travail était de tester expérimentalement cette voie avec un plasma organique comme source de radicaux CHx. Ce dispositif a permis la formation de matière organique soluble et insoluble. La MOI a été analysée par les mêmes techniques que celles utilisées précédemment pour la MOI chondritique, révélant de nombreuses similitudes entre les deux matériaux et validant le mécanisme proposé. En outre, des analyses NanoSIMS ont révélé, à une résolution spatiale sub-micrométrique, de grandes variations isotopiques qui sont du même ordre de grandeur que celles observées dans la MOI chondritique. Ensuite, la source des hétéroatomes (N et O) dans la MOI a été expérimentalement étudiée en ajoutant des précurseurs contenant des heteroelements aux radicaux hydrocarbonés. En ce qui concerne l'azote, deux types de précurseurs ont été considérés : l’hexylamine comme source d'hydrures et l'azote moléculaire N2. Bien que les deux précurseurs conduisent à l'incorporation d'azote dans la MOI, les hydrures d'azote semblent être plus pertinents, d’après la nature des fonctions azotées formées. Deux types d'expériences ont été effectuées afin d'étudier la source potentielle d'oxygène dans la MOI chondritique. Elles ont été conçues pour tester les deux principaux scénarios proposés pour rendre compte de la présence d’oxygène dans la MOI chondritique : soit l’altération aqueuse sur le corps parent ou l’incorporation d’oxygène pendant l’organo- synthèse dans la nébuleuse solaire primitive. Lors de l’expérience simulant l'altération aqueuse, la composition chimique de la matière organique soluble et insoluble est en accord avec ce qui est observé dans la matière organique des météorites. En revanche, aucun élément en faveur de l'incorporation directe d’oxygène par des radicaux OH n’a pu être apporté. / Carbonaceous meteorites are the most primitive objects of the solar system. They contain up to 4% of carbon, mainly occurring as insoluble organic matter (IOM). This IOM contains key information about the organo-synthesis processes taking place in the Solar System, which are so far poorly understood. A statistical model was recently proposed for the IOM molecular structure along with a possible synthesis pathway for its hydrocarbon backbone (Derenne and Robert, 2010).The first aim of this work was to test experimentally this pathway using an organic plasma as a source of CHx radicals. This device allowed the formation of both soluble and insoluble OM. The IOM was analyzed through the same techniques as those previously used for the chondritic IOM, revealing numerous similarities between both materials and thus supporting the proposed pathway. Moreover, NanoSIMS analyses revealed large isotopic variations at a sub-micrometric spatial resolution that are commensurable with those observed in chondritic IOM.Then, the source of heteroatoms (N and O) into the IOM was experimentally investigated through the addition of heteroelement-containing precursors to the hydrocarbonaceous radicals. As for nitrogen, two types of precursors were considered: hexylamine as a source of nitrogen hydrides and N2. Although both precursors led to nitrogen incorporation in the IOM, nitrogen hydrides seem to be more relevant based on the nitrogen speciation. Two types of experiments were performed to investigate the potential source of oxygen in the chondritic IOM. They were designed to address the two main scenarios proposed in the literature to account for the origin of the oxygen in the chondritic IOM: either aqueous alteration on the asteroidal parent body or O incorporation during the organo-synthesis in the primitive solar nebula. When the aqueous alteration is mimicked, the chemical composition of the SOM and IOM makes this pathway a reasonable source of the chondrite oxygen moieties. In contrast, no evidence for direct incorporation of O from OH radicals could be brought.

Long term management plans for restoration of natural flow conditions through the Everglades increase the importance of understanding potential nutrient impacts of increased freshwater delivery on coastal biogeochemistry. The present study sought to increase understanding of the coastal marine system of South Florida under modern conditions and through the anthropogenic changes in the last century, on scales ranging from individual nutrient cycle processes to seasonal patterns in organic material (OM) under varying hydrodynamic regime, to century scale analysis of sedimentary records. In all applications, carbon and nitrogen stable isotopic compositions of OM were examined as natural recorders of change and nutrient cycling in the coastal system. High spatial and temporal variability in stable isotopic compositions were observed on all time scales. During a transient phytoplankton bloom, ä15N values suggested nitrogen fixation as a nutrient source supporting enhanced productivity. Seasonally, particulate organic material (POM) from ten sites along the Florida Reef Tract and in Florida Bay demonstrated variable fluctuations dependent on hydrodynamic setting. Three separate intra-annual patterns were observed, yet statistical differences were observed between groupings of Florida Bay and Atlantic Ocean sites. The POM ä15N values ranged on a quarterly basis by 7‰, while ä13C varied by 22‰. From a sediment history perspective, four cores collected from Florida Bay further demonstrated the spatial and temporal variability of the system in isotopic composition of bulk OM over time. Source inputs of OM varied with location, with terrestrial inputs dominating proximal to Everglades freshwater discharge, seagrasses dominating in open estuary cores, and a marine mixture of phytoplankton and seagrass in a core from the boundary zone between Florida Bay and the Gulf of Mexico. Significant shifts in OM geochemistry were observed coincident with anthropogenic events of the 20th century, including railroad and road construction in the Florida Keys and Everglades, and also the extensive drainage changes in Everglades hydrology. The sediment record also preserved evidence of the major hurricanes of the last century, with excursions in geochemical composition coincident with Category 4-5 storms.

Denitrification removes large amounts of reactive nitrogen (N) from ecosystems via reduction of nitrate to dinitrogen gas. In aquatic ecosystems, the influences of terrestrial and aquatic sources of organic matter (OM) on denitrification are potentially complex. Terrestrially-derived OM is often less labile than autochthonous OM; it may inhibit denitrification directly via biochemical mechanisms; and it may indirectly inhibit denitrification by reducing light availability to—and thus OM exudation by—aquatic primary producers. Using a natural dissolved OM gradient among rivers of northern Florida, I investigated these mechanisms using laboratory denitrification assays subjected to factorial amendments of NO3- and dextrose, humic acid dosing, and cross-incubations of sediments and water. Results indicated that C-limitation increased with DOC concentrations, consistent with the indirect inhibition hypothesis. Blackwater neither depressed nor stimulated denitrification rates, indicating that this DOC neither directly inhibits nor acts as a usable OM source for denitrifiers.