A l'heure actuelle le rôle des zones côtières dans le cycle global du carbone est encore relativement mal documenté. Ceci est lié à la forte hétérogénéité et au fort dynamisme de ces zones au sein desquelles de nombreux processus physiques et biologiques interagissent sur les stocks et les flux de carbone. Le carbone organique dissous (DOC) est un élément essentiel à la compréhension du cycle du carbone océanique, notamment dans les zones côtières où il peut représenter jusqu'à 90% du carbone organique total. Compte tenu des nombreuses incertitudes qui résident encore sur la dynamique de cette matière carbonée, l'objectif général de cette thèse visait à améliorer les connaissances sur la distribution du DOC au niveau de ces interfaces "continent/océan" en s'appuyant sur les propriétés optiques de la fraction colorée de ce DOC, la matière organique dissoute (CDOM). Pour cela, des échantillonnages ont été réalisés entre 2010 et 2015 dans trois sites côtiers fortement contrastés (Manche orientale, Guyane Française, Vietnam) et ont permis de : (i) caractériser la dynamique de la CDOM et du DOC et d'identifier une forte hétérogénéité de la relation entre ces deux paramètres au sein de ces sites côtiers aux caractéristiques contrastés, (ii) de proposer une relation novatrice applicable à la télédétection "couleur de l'eau" permettant de dériver les concentrations en DOC à partir des propriétés optiques de la CDOM potentiellement généralisable dans des sites côtiers dominés par les apports terrigènes. Dans un second temps, des études en milieu contrôle (45 jours) couplées à un suivi de terrain (2012-2014) ont été effectuées afin de caractériser spécifiquement la cinétique et l'impact d'une production biologique de matière organique dissoute sur les relations entre CDOM et DOC. Elles ont permis d'identifier un marquage optique (i.e. S320-412) de cette production autochtone de MOD lors de l'efflorescence printanière de Phaeocystis.globosa caractéristique des eaux côtières de la Manche et de proposer une approche pour estimer les contenus en DOC depuis les propriétés optiques du CDOM dans de telles situations de production marine de matière organique dissoute. / The coastal ocean represents an important component of the global carbon cycle however its participation to the overall carbon flux is currently not well constrained. Information on DOC stock and its variability in the coastel ocean is however still very scarce and its represents a strong limitation to our current understanding of the exact role of these ecosystems in the oceanic carbon cycle. In this context, the general aims of this study was to get more insights on dissolved organic carbon dynamics in the coastal ocean through the optical properties of dissolved organic matter (CDOM) that present the advantage to be easily measured from in situ or satellite observations. In practice, in situ data gathered during several sampling cruises conducted in three constrasted continental margins (Eastern Channel, French Guiana, Vietnam) have allowed : (i) the characterization of the strong regional discrepancies in the CDOM-DOC relationships between the three coastal sites investigated, (ii) the possible use of a generalized parameterization to retrieve DOC concentrations from CDOM optical properties (estimated in situ or from ocean color remote sensing)over a large range of coastal sites dominated by terrestrial imput of DOM. A further objective of this work was to investigate the impact on DOM dynamics of the phytoplankton bloom event of Phaeocystis.globosa known to affect the coastal waters of the eastern English Channel during the spring period. In practice, this DOM production was investigated during a 45 days mesocom experiment coupled to field survey data (2012-1014) leading to the identification of an optical marker of this marine CDOM production (i.e. S320-412). We further demonstrated that this optical parameter provides useful information to enhance our ability to retrieve DIC 1 from CDOM optical properties in a context of an algal bloom event.

Permafrost soils in the Arctic store large quantities of organic matter, roughly twice the amount of carbon that was present in the atmosphere before the industrial revolution. This freeze-locked carbon pool is susceptible to thawing caused by amplified global warming at high latitudes. The remobilization of old permafrost carbon facilitates its degradation to carbon dioxide and methane, thereby providing a positive feedback to climate change. Accelerating coastal erosion in addition to projected rising river discharge with enhancing sediment loads are anticipated to transport increasing amounts of land-derived organic carbon (OC) to the Arctic Ocean. On its shallow continental shelves, this material may be remineralized in the water column or in the sediments, transported without being altered off shelf towards the deep sea of the Arctic Interior or buried in marine sediments and hence sequestered from the contemporary carbon cycle. The fate of terrigenous material in the marine environment, though offering potentially important mechanisms to either strengthen or attenuate the permafrost-carbon climate feedback, is so far insufficiently understood. In this doctoral thesis, sediments from the wide East Siberian Arctic Shelf, the world’s largest shelf-sea system, were used to investigate some of the key processes for OC cycling. A range of bulk sediment properties, carbon isotopes and molecular markers were employed to elucidate the relative importance of different organic matter sources, the role of cross-shelf transport and the relevance of degradation during transport and after burial. Overall, OC released from thawing permafrost constitutes a significant proportion of the sedimentary organic matter on the East Siberian Arctic Shelf. Two sediment cores from the inner and outer East Siberian Sea recorded no substantial changes in source material or clear trends in degradation status for the last century. With increasing distance from the coast, however, strong gradients were detected towards lower concentrations of increasingly reworked land-derived OC. The time spent during cross-shelf transport was consequently found to exert first-order control on degradation. Compound-specific radiocarbon dating on terrigenous biomarkers revealed a net transport time of ~4 000 years across the 600 km wide Laptev Sea shelf, yielding degradation rate constants for bulk terrigenous OC and specific biomarkers on the order of 2-4 kyr-1. From these results, the carbon flux released by degradation of terrigenous OC in surface sediments was estimated to be ~1.7 Gg yr-1, several orders of magnitude lower than what had been quantified earlier for dissolved and particulate OC in the water column. Lower oxygen availability and close associations with the mineral matrix may protect sedimentary OC from remineralization and thereby weaken the permafrost-carbon feedback to present climate change. / <p>At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 3: Submitted. Paper 4: Manuscript.</p>

O objetivo deste trabalho foi avaliar o desempenho da combinação dos processos de interozonização e sistemas pós-filtros adsorvedores na remoção de compostos orgânicos precursores e na formação de subprodutos da desinfecção, em particular os trialometanos (THM). Os ensaios foram desenvolvidos com a água filtrada proveniente da estação de tratamento de água do Alto da Boa Vista, localizada no município de São Paulo, tipo convencional, com água bruta oriunda de reservatório com elevado estado de eutrofização. O aparato experimental é constituído de um sistema de ozonização com quatro colunas em série e tempo de detenção hidráulica total de 16 minutos; e, por um sistema de quatro pós-filtros adsorvedores com diferentes tipos de carvão ativado granular, filtros F1 e F3 dotados de carvão mineral (CAG1, betuminoso) e filtros F2 e F4 compostos por carvão vegetal (CAG2, casca de coco) sendo todos operados em paralelo com valores de Tempo de Contato de Leito Vazio (TCLV) entre 15 e 20 minutos. Duas colunas receberam como afluente água filtrada pré-ozonizada (F1 e F2) e as demais colunas apenas água filtrada (F3 e F4). Os resultados indicaram que a ozonização não alterou de forma significativa os parâmetros utilizados para avaliação dos precursores, COT e UV-254 nm, e nem o THM. Inicialmente, os resultados de remoção de COT permaneceram elevados, próximos de 80% caracterizando a saturação dos leitos em torno de 240 dias para os filtros F1 e F3 (CAG1) e apenas 30 dias, com eficiências baixas para os filtros F2 e F4 (CAG2). Para THM a saturação foi próxima de 65 dias para ambos os carvões e as eficiências iniciais foram de 90% e 75%, para os filtros com CAG1 e CAG2, respectivamente. Com todos os leitos saturados, os resultados ainda indicaram boa remoção de compostos causadores de gosto e odor. Neste trabalho, os sistemas de pós-filtros adsorvedores de CAG foram efetivos para o controle das substâncias precursoras e a redução da formação de THMs, com melhores resultados para o carvão mineral CAG1 (betuminoso) independentemente do sistema de interozonização. / The main purpose of this work was to evaluate the performance of a combination of processes - inter-ozonization and post-filter GAC adsorbers systems, on the control of organic precursors and disinfection byproducts, especially trihalomethanes (THM). The experience was conducted with filtered water produced at Alto da Boa Vista conventional WTP, located at São Paulo city, where raw water comes from a high eutrofic lake. The experimental setup consists of an ozonation system with four column shaped contactors arranged in series with 16 minutes total hydraulic detention time; and, a system of four pilot scale adsorbers with different types of granular activated carbon (GAC) media, F1 and F3 filters with mineral GAC media (GAC1, bituminous) and F2 and F4 filters with vegetal GAC media (GAC2, coconut shell), all operated in parallel with empty bed contact time (EBCT) between 15 and 20 minutes. Two columns were fed with filtered and pre-ozonated water (F1 and F2) and the other two were fed with filtered water only (F3 and F4). It was observed that ozonation did not affect significantly results of precursors parameters, TOC and UV-254, and neither THM. Initially, TOC removal remained high, near 80% delineating the bed saturation around 240 days to F1 and F3 filters (GAC1) and only 30 days with low efficiency for filters F2 and F4 (GAC2). The THM bed saturation time was nearly 65 days for both media and initial efficiencies were 90% and 75% to GAC1 and GAC2, respectively. With all beds saturated, still there was a good taste and odor producing substances removal. In this work, the systems of GAC adsorbents post-filters were effective for the control of precursors and to reduce the formation of THM\'s, with better results for the CAG1 (bituminous) regardless of the use of inter-ozonization.

Sugarcane cropping is an important component of the Brazil´s economy. As the main feedstock used to produce ethanol, the area occupied with this crop has meaningfully increased in the last years and continues to expand in order to attend to the national and international demand of this biofuel. Despite that it has been demonstrated that land-use transition into sugarcane can negatively impact the soil carbon (C) dynamics, little is known about the effect of those land use changes (LUC) processes on the distribution of soil organic carbon (SOC) within particle-size classes, and how management practices in sugarcane can contribute to the C restoration. In this sense the main objective of this study was to evaluate through a modelling application the SOC dynamics in the sugarcane crop in response to LUC and different management scenarios. For a better understanding of LUC impact on C content in both particulate organic matter and mineral-associated fraction, we performed physical soil C fractionation in 34 study areas involving the three major land-use systems affected by sugarcane expansion. Also, biometric measurements were executed in sugarcane plant and ratoon crop in order to use those data in the model parameterization as well as to recalculate the payback time of the C debt through C conversion ratio reported in the literature. Finally, we parameterized and validate the CENTURY ecosystem model for sugarcane, pastures and annual cropland by using a data-set previously collected by the Laboratório de Biogeoquímica Ambiental (CENA-USP); then different scenarios of sugarcane management were simulated: i) SC1 - Green harvesting; ii) SC2 - Green harvesting plus organic amendments and iii) Green harvesting + low N inputs. Our results showed that the C content depletion for conversion from native vegetation and pastures to sugarcane is caused by C losses in the labile fraction (37%) as wells as in the stabilized pool associated to the mineral fraction (30%). Above and belowground biomass quantification indicated a total sugarcane carbon inputs ranging from 29.6 Mg C ha-1 to 30.6 Mg C ha-1. Considering a C retention rate of 13% we estimated net carbon changes of 0.58 to 0.6 Mg C ha-1 year-1, which contribute to reduce the payback times for sugarcane biofuel carbon debts in 3.3 and 1.2 years for Cerrado wooded and pasture conversions into sugarcane respectively. The modelling study supported the Century model as a tool to access the SOC dynamics following land-use conversion and different soil management in in sugarcane. Long-term simulations suggested that changes in the sugarcane harvest from burning to green harvesting increase the soil C stock in an average of 0.21 Mg ha-1 year-1; however the potential of C accumulation is still higher when organic amendments as vinasse and filter cake are add to the soil, with mean values varying between 0.34 and 0.37 Mg ha-1 year-1 in SC2 and SC1 respectively. By analyzing the SOC dynamic at each scenario simulated, we estimated a time span of 17 and 24 years for soil C restoration in clay and sandy soils under pastures with priority suitability (SC3). The number of years was projected to be higher in clay soils with regular suitability (40 years). / A cultura da cana-de-açúcar é uma comodity importante para a economia no Brasil. Como a principal matéria prima para a produção de etanol, a área plantada com esta cultura tem incrementado significativamente nos últimos anos e a tendência é de continuar se expandindo para atender a demanda nacional e internacional deste biocombustível. Embora tenha sido demostrado que a mudança de uso da terra (MUT) para cana-de-açúcar pode afetar negativamente a dinâmica do carbono (C) no solo, há pouca informação disponível acerca do impacto dessa MUT na distribuição do C nas frações da matéria orgânica do solo, e como as praticas de manejo da cana-de-açúcar podem contribuir para o acumulo de C no solo. Nesse contexto o principal objetivo desta pesquisa foi avaliar, através da modelagem matemática, a dinâmica do carbono orgânico do solo (COS) na cultura da cana-de-açúcar em resposta a mudança de uso da terra e diferentes cenários de manejo agrícola. Fracionamento físico para separar o C associado à matéria orgânica partícula (POM) do C ligado à fração mineral do solo (<53 um) foi realizado em amostras de solo de 34 áreas de estudo envolvendo os três principais sistemas de uso da terra afetados pela expansão da cana-de-açúcar. Adicionalmente, foram realizadas avaliações biométricas da cana-de-açúcar (cana planta e soca) que objetivaram a parametrização do modelo matemático assim como recalcular o tempo de reposição do debito de C gerado. Finalmente, o modelo CENTURY foi parametrizado e devidamente validado, para posteriormente proceder à simulação de diferentes cenários futuros de manejo da cana de açúcar: i) SC1 - Colheita de cana crua (sem queima); ii) SC2 - Colheita de cana crua e adição de adubos orgânicos (vinhaça e torta de filtro); iii) Colheita de cana crua e redução da adubação nitrogenada. Os resultados indicaram que a redução do conteúdo de C devido à conversão de vegetação nativa e pastagem para cana-de-açúcar foi causada pela perda de C tanto na fração lábil (37%) quanto na fração mais estável associada a fração mineral do solo (30%). A quantificação da biomassa aérea e radicular indicou entradas de C variando de 29,6 Mg C ha-1 a 30,6 Mg C ha-1, os quais resultariam em uma taxa de acumulo liquido de 0,58 a 0,6 Mg C ha-1 ano-1, que quando considerado contribui a redução do \"payback time\" do debito de C do etanol causado pela conversão de Cerrado e pastagem em 3,3 e 2 anos respectivamente. Os resultados obtidos no estudo de modelagem matemática suportaram o uso do modelo CENTURY como uma ferramenta para avaliar a influencia da MUT e das práticas de manejo na dinâmica do COS. As simulações em longo prazo sugeriram que a supressão da queima na colheita incrementa o estoque de C em 0,21 Mg ha-1 ano-1. No entanto o potencial de acúmulo de C é ainda maior quando adubação orgânica é realizada, com valores entre 0,34 e 0,37 Mg ha-1 ano-1 respectivamente. A análise da dinâmica do COS em cada cenário de manejo simulado permitiu estimar o tempo médio de recuperação do C do solo perdido pela MUT em áreas de pastagens. Os resultados indicaram um período de 17 anos para condições de cultivo sob solos argilosos e 24 anos para solos arenosos (SC3) em áreas de alta aptidão para expansão. O modelo projetou um maior número de anos em solo argiloso sob áreas de pastagem com aptidão média (40 anos).

O município de Viamão está localizado na região metropolitana de Porto Alegre, no estado do Rio Grande Sul. A barragem Mãe d\'Água foi construída em 1962, com o intuito de atender à demanda da Universidade Federal do Rio Grande do Sul, mais precisamente o Instituto de Pesquisas Hidráulicas, porém, devido à falta de planejamento urbano, durante os últimos quarenta anos, vem acarretando uma diversificada série de passivos ambientais, como contaminantes orgânicos e/ou inorgânicos. Neste seguimento, o presente trabalho busca avaliar as concentrações dos metais Zinco e Níquel, teores de matéria orgânica e a composição granulométrica nas diferentes profundidades amostradas em testemunhos de sedimentos produzidos nesta bacia hidrográfica que compõe a barragem Mãe d\'Água. As coletas de amostras foram realizadas em junho de 2014, sendo amostrados quatro testemunhos sedimentares distribuídos no lago da referida barragem. Para a extração dos testemunhos foi utilizado um amostrador de núcleo \"Piston Core\". Os sedimentos da fração menor que 63&#956;m foram destinados a análise química para verificação da presença e concentração dos elementos traço: Níquel (Ni) e Zinco (Zn). A metodologia de digestão ácida empregada é a EPA 3050, adotada pela U.S. Environment Protection Agency, sendo que as análises foram realizadas em duplicata e, para controle de qualidade, foram utilizados dois materiais de referência da USGS (U.S. Geological Survey): SGR-1b e SCO-1. Com os resultados obtidos, a caracterização granulométrica da sedimentação sob o barramento mostrou-se suscetível a contaminação por metais ao longo nas últimas décadas. Todas as amostras apresentaram concentrações de Zn e Ni acima do valor de background local e com padrões de crescimento, portanto, evidenciam a existência de enriquecimento dos sedimentos por estes elementos. Os teores de matéria orgânica quando correlacionados as concentrações de Zn e Ni evidenciaram o crescente enriquecimento nos testemunhos analisados, confirmando a alta afinidade destes elementos à sedimentos compostos de fração orgânica. O índice de geoacumulação para a maior parte das concentrações dos metais nas diferentes profundidades encontra-se caracterizadas como não poluída. Considerando que a área de estudo se caracteriza historicamente pela ocupação residencial, ações antropogênicas podem ser consideradas as principais provedoras dos passivos ambientais aos corpos d\'água. / The municipality of Viamão is located in the metropolitan region of Porto Alegre, state of Rio Grande do Sul. The Mãe D\'água Dam was built in 1962, so that demands from the Federal University of Rio Grande do Sul, more precisely the Institute of Hydraulic Research could be met. However, due to a lack of urban planning over the past forty years, the dam has caused several environmental liabilities, such as organic contaminants and / or inorganic contaminants. This manuscript addresses an evaluation of the concentrations of the metals zinc and nickel metals, organic matter content and particle size composition at different depths sampled in sediment cores produced in the watershed that comprises Mãe d\'Água. Four sediment core distributed in the dam lake were collected in June 2014, by \"Piston Core\" core sampler. Sediments whose fraction was lower than 63&#956;m were subjected to chemical analyses regarding the presence and concentration of nickel (Ni) and zinc (Zn). The acid digestion methodology employed was EPA 3050, adopted by the US Environment Protection Agency. The analyses were performed in duplicate and two USGS (US Geological Survey) reference materials, namely: SGR-1b and SCO-1 were used for the quality control. The particle size characterization of sedimentation under the bus has proved susceptible to metal contamination over the past decades. All samples showed concentrations of Zn and Ni higher than the local background values and growth patterns, which evidenced an enrichment of sediments. In comparison to the organic matter content, the Zn and Ni concentrations showed a growing enrichment, which confirmed the high affinity of these elements for sediments composed of organic fraction. The geoaccumulation index for most of the metal concentrations at different depths has been characterized as non polluted. As whereas the study area is historically by historically residential occupation, anthropogenic actions can be considered the main causes of environmental damage to water bodies.

Les sols constituent le principal réservoir de carbone, avec près de deux fois plus de carbone que le pool atmosphérique. Afin de pouvoir prédire et anticiper le devenir du carbone dans le contexte actuel de changement climatique et de changement d'usage des terres, il apparaît nécessaire de mieux comprendre les processus qui régulent la décomposition des matières organiques dans les sols. Cette thèse se propose donc d'étudier deux types de régulateurs de la dynamique du carbone du sol : les propriétés de l'habitat microbien et celles des communautés microbiennes. En effet, puisque directement affectées par les changements climatiques d'une part, et les changements d'usage des terres et de pratiques culturales d'autre part, l'habitat microbien et les communautés microbiennes apparaissent comme des régulateurs clés de la dynamique du carbone du sol. Des dispositifs expérimentaux permettant de faire varier les propriétés de l'habitat microbien et celles des communautés microbiennes de façon indépendante ou simultanée ont été mis en place. Dans un premier temps, des microcosmes dont la structure du sol a été manipulée afin d'obtenir des gradients de déstructuration, ont été incubés. Dans un second temps ce sont des microcosmes mettant en jeu des gradients de diversité microbienne qui ont été incubés. Enfin, une incubation utilisant les différences naturelles de propriétés de l'habitat microbien et de communautés microbiennes a été mise en place pour tenter de hiérarchiser ces régulateurs de la décomposition des matières organiques du sol. Les résultats obtenus ont mis en évidence que l'activité microbienne de décomposition du carbone organique du sol semble plus contrôlée par les conditions environnementales (comme le pH, la texture et l'approvisionnement en substrat) que par la structure des communautés microbiennes ou leurs capacités métaboliques. En plus de cela, la fonction de minéralisation ne semble être affectée que dans le cas d'une très grande érosion de la biodiversité suggérant la présence d'un effet seuil, et que l'importance de la redondance fonctionnelle n'est pas toujours aussi grande que ce que le suggère de nombreuses études. D'autre part, dans des conditions d'aération suffisante, les mécanismes qui réguleraient la dynamique du carbone organique des sols se passeraient à des échelles très fines. / Soils represent the principal reservoir of carbon with two times as much carbon as is found in the atmospheric pool. In an effort to better predict and anticipate how soil carbon dynamics will be affected by environmental changes and by the evolution of cropping systems, it is necessary to better understand the processes that regulate soil organic matter decomposition. This study aims to investigate two regulatory mechanisms of the soil carbon dynamic: the properties of the microbial habitat and the ones of the microbial communities. Because they are directly affected by the climatic changes and by the rapid evolution of cropping systems these two mechanisms appear to have a key role in the regulation of soil carbon decomposition. Experimental designs were setup allowing the variations, independent or simultaneous, of the properties of microbial habitat and the ones of the microbial communities. First, to assess the relative importance of soil structure, microcosms with different gradient of disaggregation were incubated. Then, to assess the relative importance of diversity erosion, microcosms with microbial diversity gradient were incubated. Finally, using contrasted soils varying in their habitats and their microbial communities properties, we aimed to hierarchize these two carbon decomposition regulatory mechanisms.The obtained results indicate that microbial activity of soil organic carbon decomposition seems to be more controlled by environmental conditions (such as pH, texture and also substrate supply) than by the microbial community structure or metabolic profiles. Then we observed that organic carbon mineralisation was impacted only when the levels of diversity were very low suggesting the existence of a threshold, and that the functional redundancy is maybe not as great as numerous studies suggest. Moreover, our work showed that when conditions of aeration in the pore system are sufficient, mechanisms regulating the dynamic of soil organic carbon take place at fine spatial scales.

The Cretaceous Mowry Shale is an organic-rich, siliceous marine shale, and as such is a known source rock in the Western United States. Studies have documented that total organic carbon (TOC) in the Wind River Basin, Wyoming increases to the southeast. These studies cover large areas with limited sample sets. In this study, over 250 samples were collected near Lander, Wyoming to address spatial heterogeneity of TOC within the Mowry Shale at a much finer scale than previously examined. Samples were collected along five vertical sections at three localities, and following correlation of the vertical sections, which was strongly aided by the presence of regional bentonite horizons, samples were collected laterally from the same unit at regular 25-foot intervals. These samples were analyzed using pyrolysis and x-ray diffraction techniques. Average TOC values are fairly consistent within the study area (1.65%, with a range of 2.10% to 1.15%). Average Tmax values for vertical and lateral samples is 433 °C with a standard deviation of 7.25 °C suggesting immature to very early oil window thermal maturity. Kerogen types are determined to be dominantly type III, suggesting a dominance of terrestrial input, becoming slightly more mixed type II/III to the southeast. Redox-sensitive trace metals such as uranium, thorium, vanadium, chromium, cobalt, and molybdenum values all suggest a slightly oxygenated sediment water interface during time of deposition. These pyrolysis and trace metal data suggest that the study area was in a prograding proximal marine/prodeltaic depositional environment during Upper Mowry time with influences from higher energy bottom flows. Lateral homogeneity of strata and the low variability in geochemical character across the study area suggest that the local basin in the study area was not segmented by structural or oceanographic conditions. While efforts were made to collect unaltered outcrop samples (digging back into what appeared to be unfractured, unaltered rock), alteration or weathering of organic material is a concern for source rock evaluation of near-surface outcrops. In order to address this concern, a 5-foot-deep trench was dug back into the outcrop at the target horizon in one locality. Samples were taken at regular three-inch intervals from this trench as it was excavated to determine the effect of weathering on TOC in the study area. Based on pyrolysis results, TOC was affected by weathering only along fracture sets (several samples intersected fractures in the shallow subsurface) and did not appreciably increase from the surface to a depth of five feet. Due to the impermeable nature of shale rock, decreases of TOC due to weathering appear to be limited to the immediate surface of samples and along fracture sets.

L'apport de matière particulaire fluviale (MPF) aux eaux naturelles joue un rôle essentiel dans le cycle global des éléments et influence le cycle du carbone organique (Corg) de deux façons: 1°, les MPF comprennent une source importante d'éléments nutritifs qui peuvent augmenter la production primaire dans les océans. Par exemple, le flux global de MPF de nutriments tels que Si, P et Fe dépasse son flux dissous par des facteurs de 50, 100 et 350. 2°, l'apport de MPF des continents aux océans est un contrôle majeur de la séquestration du Corg, un processus essentiel dans la réduction du CO2 à long terme par le cycle de Corg. Pour explorer le lien entre l'apport de MPF et la production primaire dans les eaux naturelles, une série d'expériences de croissance a été réalisée impliquant deux producteurs primaires abondants: la cyanobactérie d'eau douce Synechococcus sp. (SYN), et la diatomée marine Thalassiosira weissflogii (TW). Des expériences ont été réalisées en présence et en l'absence de différentes MPF et à différents niveaux nutritifs initiaux. Les résultats démontrent que les MPF augmentent nettement la croissance de la biomasse en fonction de la concentration du MPF. Dans les expériences menées avec la cyanobactérie SYN, la présence de MPF a 1) déclenché une croissance bactérienne dans des conditions pourtant défavorables, 2) augmenté la concentration totale de biomasse et 3) déclenché une croissance bactérienne même après la consommation des nutriments initiaux. L'effet positif des MPF sur la croissance de la diatomée marine TW a été le plus évident pour les expériences n'impliquant pas de nutriments, où les diatomées se sont multipliées linéairement en présence de MPF alors que ces cultures sont mortes en absence des MPF. De plus, des études MEB ont montré un contact physique direct entre les microbes ou les substances organiques excrétées par les microbes et les MPF. Conformément aux travaux issus de la littérature, nous suggérons que les microbes peuvent acquérir des nutriments directement à partir des minéraux, ce qui augmenterait le potentiel des MPF en tant que source de nutriments. Le contact direct suggère aussi une augmentation de l'efficacité de piégeage du Corg par l'augmentation 1) du contenu de Corg absorbé sur les surfaces minérales, 2) de l'agglomération des particules organiques et inorganiques et donc la formation de neige marine ou 3) des vitesses de chute de Corg par "mineral ballasting". La fixation directe des microbes sur les surfaces minérales a également été observée dans les échantillons naturels obtenus au cours d'une étude de terrain sur la côte sud islandaise. Dans l'ensemble, cette étude fournit des preuves expérimentales de l'importance des MPF dans le cycle de Corg grâce à son impact sur la production primaire. En outre, ces travaux rassemblent des preuves que les MPF peuvent faciliter l'inhumation de Corg grâce à la fixation de microbes sur les surfaces ou à la formation des agglomérats minéraux- microbes qui chutent rapidement dans la colonne d´eau. Des études complémentaires ont été effectuées pour évaluer la qualité des compositions isotopiques du carbone, afin de préserver les estimations des taux de séquestration du Corg à travers une période géologique donnée. Les variations du degré de production primaire et du piégeage du Corg au cours des temps géologiques sont conservées dans la signature isotopique du C des carbonates. L'utilisation de ces signatures pour reconstruire les conditions environnementales passées exige cependant que ces signatures soient conservées pour des vastes échelles de temps. Les résultats expérimentaux démontrent que la composition isotopique du C de la calcite évolue continuellement vers l'équilibre isotopique entre les fluides et les minéraux. Cette observation suggère que les compositions isotopiques de C dans la calcite pourraient changer notablement si la calcite était constamment dans un déséquilibre isotopique avec son fluide coexistant. / The supply of riverine particulate material (RPM) to natural waters plays a vital role in the global cycle of the elements and is considered to influence the organic carbon cycle in two ways. First, RPM comprise a vast source of nutrients which can increase primary production in the oceans. For example, the global RPM flux of nutrients such as Si, P and Fe exceeds its corresponding dissolved flux by factors of 50, 100 and 350. Second, the supply of RPM to the oceans is a major control of organic matter (Corg) burial, an essential process in the long term CO2 drawdown via the organic pathway. To explore the link between RPM supply and primary production in natural waters, a series of microcosm growth experiments was performed with two common primary producing microbes, the freshwater cyanobacteria Synechococcus sp. and the marine diatom Thalassiosira weissflogii. Experiments were performed in the presence and absence of different RPM at different initial nutrient levels. Results demonstrate that RPM significantly increase bacterial biomass growth as a function of RPM concentration. Notably, in experiments conducted with the freshwater cyanobacteria Synechococcus sp., the presence of RPM 1) triggered bacterial growth in otherwise unfavorable conditions, 2) increased total biomass concentration, and 3) induced steady bacterial growth even after consumption of the initial nutrients. The positive effect of RPM on the growth of the marine diatom Thalassiosira weissflogii was most obvious in nutrient free experiments where cultures grew linearly with time in the presence of RPM, whereas these cultures died in RPM free controls. Furthermore, SEM investigations showed direct physical contact between microbes or microbially excreted organic substances and the particulates. In accord with reports in the literature, we suggest that microbes may acquire nutrients directly from the rock, which would again enhance the potential of RPM as source of limiting nutrients. The direct physical contact also suggests an increase in the burial efficiency of Corg through either 1) increasing Corg content absorbed on mineral surfaces, 2) increasing agglomeration and marine snow formation of organic and inorganic particles or 3) increasing organic matter settling velocities through mineral ballasting. The direct attachment of microbes on mineral surfaces was also observed in natural samples obtained from a field study at the Icelandic South coast. The positive effect of RPM on microbial growth and its effect on Corg burial are complimentary. Agglomeration is a function of suspended particle concentration, organic or inorganic. An elevated biomass concentration induced by the presence of RPM results in a high total suspended matter concentration, thus increasing the particle agglomeration rate. Taken together, this study provides experimental evidence for the importance of RPM in the organic C-cycle through its positive impact on primary production. Furthermore, it compiles evidence that particulates may facilitate organic matter burial through direct attachment of microbes on sediment surfaces or the formation of fast settling mineral/microbe agglomerations. Complimentary studies were performed to assess the quality of carbon isotope compositions to preserve estimates of Corg burial rates over geological time. Variations in the degree of primary production and Corg burial during Earths' history are recorded in the C-isotopic signature of marine carbonates. The use of carbon isotopic signatures in carbonates to reconstruct past environmental conditions, however, requires that these signatures are preserved over vast timescales. Experimental results demonstrate, that the carbon isotopic composition of calcite continuously evolves towards mineral-fluid isotopic equilibrium. This observation suggests that calcite C-isotopic compositions might change noticeably if the calcite were continuously in isotopic disequilibria with its co-existing fluid.

La matière organique dissoute (MOD) est un composant important des eaux naturelles, déterminant la forme des éléments et les émissions de gaz à effet de serre (CO2, CH4), et influence la biodiversité des milieux des eaux. Les eaux boréales sont connues pour être généralement riches en fer, et cela est vrai en particulier pour les eaux de la région étudiée (Carélie du Nord, Russie). Le fer est associée aux MOD dans les complexes de bas poids moléculaire et les colloïdes organo-ferreux de haut poids moléculaire, qui agissent comme les principaux transporteurs d'éléments traces métalliques dans le continuum hydrologique typiques de cette région : sol - marais - rivière - lac. La transformation des colloïdes organo-ferreux se fait sous l'influence de deux facteurs principaux: la dégradation bactérienne et la dégradation photochimique. Cette étude est consacrée à l'analyse du comportement du carbone organique dissous (COD) et des éléments traces (ET) des eaux de surface en zone boréale sous l'influence de l'activité métabolique des bactéries hétérotrophes et de l'oxydation photolytique des MOD sous l'effet de la lumière du soleil. Dans les expériences, un lixiviat de tourbière, un échantillon d'eau de marais, un échantillons d'eau de ruisseaux, un échantillon de rivière, un échantillon d'eau de lac humique, un échantillon d'eau de lac oligotrophique et un pluvio-lessivat collecté sous un pin, échantillons dans lesquelles dominent les MOD de nature humique, ont été utilisés comme substrats. Des expériences en laboratoire utilisant des communautés monosouches de bactéries aérobies hétérotrophes Pseudomonas aureofaciens et Pseudomonas saponiphila (prélevées sur le territoire de Carélie) ont permis d'établir que la MOD allochtone des milieux aquatiques en zone boréale possède une forte résistance à l'activité des bactéries étudiées. Le taux de minéralisation bactérienne du COD était de 0 à 4.3 mgC.L-1.jour-1 selon le substrat, et la fraction de faible poids moléculaire (<1 kDa) de la MOD est plus susceptible de destruction que celle de poids moléculaire élevé (de 1 kDa à 0.22 µm). L'interaction des bactéries avec divers substrats aqueux a montré pour une large gamme d'éléments (Al, Fe, Mn, Ni, Co, Cu, Cd, REE, U) une prédominance significative d'une adsorption rapide sur la surface cellulaire observée lors de la première heure d'expérience (t < 1h) par rapport à une diminution lente observée lors de la suite de l'expérience (1h < t < 96h), diminution lente lié à l'assimilation intracellulaire des métaux et à la coprécipitation extracellulaire des éléments avec des hydroxydes de Fe et Al. L'analyse de divers substrats a montré une augmentation de l'adsorption des métaux avec le rapport DOC/Fe dans la solution initiale, ce qui peut être due à la compétition entre Fe et d'autres cations métalliques pour les sites d'adsorption anioniques des surfaces des cellules bactériennes. Le suivi des dynamiques d'élimination des métaux des solutions expérimentales pendant 96 heures n'a pas mis en évidence de lien entre l'élimination des métaux et le pH et les valeurs absolues de concentration de DOC et de Fe. Une relation a été établie entre la diminution lente (96 h) des éléments et le degré initial de sursaturation de la solution en oxydes et hydroxydes de fer et d'aluminium. Des expériences en conditions naturelles avec des échantillons d'eau de rivière et de marais a montré que la destruction photolytique de la MOD est beaucoup plus efficace pour l'eau de marais. / Dissolved organic matter (DOM) is an important component of natural waters, determining the form of elements and the emission of greenhouse gases (CO2, CH4), as well as affecting water biodiversity. A feature of boreal waters, and in particular the study area waters (North. Karelia, Russia), is high concentration of Fe (III), associated with DOM in low-molecular complexes and in high-molecular organo-ferric colloids, which act as the main carriers of metallic trace elements in the most typical hydrological continuum soil - bog - river - lake. The transformation of organo-ferric colloids occurs under the influence of two main factors: bacterial and photochemical degradation. The present study is devoted to the analysis of dissolved organic carbon (DOC) and trace elements (TE) behavior in surface waters of the boreal zone under the influence of the heterotrophic bacteria metabolic activity and photolytic oxidation of DOM under sunlight exposure. For the purpose of experiments there were used substrates with predominate allochthonous DOM of humic nature, including peat leachate, pine crown throughfall, fen, humic lake, stream, river and oligotrophic lake. An experiment carried out in laboratory conditions using monocultures of heterotrophic aerobic bacteria Pseudomonas aureofaciens and Pseudomonas saponiphila (isolated on the territory of Karelia) allowed to establish that allochthonous DOM of the boreal zone reservoirs possesses high resistance to the activity of the explored bacteria. The rate of bacterial mineralization of DOC was observed in range from 0 to 4.3 mgC L-1day-1, depending on the substrate, and the low molecular weight fraction (<1 kDa) of DOM was found to be more prone to destruction than high molecular weight (from 1 kDa to 0.22 µm). The interaction of bacteria with various aqueous substrates showed a significant predominance of short-term (< 1 h) adsorption on the cell surface for a wide range of elements (Al, Fe, Mn, Ni, Co, Cu, Cd, REE, U) over a long term (1 h - 96 h) intracellular uptake of metals and extracellular coprecipitation of elements with Fe and Al hydroxides. Among different substrates, there was an increase in the adsorption with the increase of DOC/Fe ratio in solution, which can be linked to a competition between Fe and metal cations for anionic adsorption sites on cell surface. The long-term removal of dissolved metals did not show any link to pH, DOC, and Fe concentration.

The quantity of stormwater runoff from the city of Adelaide almost matches the demand for drinking water. It therefore becomes increasingly important as an alternative source for water supply. This research focused at the Parafield Stormwater Harvesting Facility near Adelaide in order to better understand: (1) nutrient dynamics between the water column, sediments and plant community, (2) allochthonous and autochthonous sources of nutrients and (3) nutrient retention capacity of the reed bed. A weekly monitoring programme for the physical and chemical parameters of the water column, sediment and plant community was carried out over three years for specific locations within the reed bed. Ordination and clustering of the time series data revealed distinctive seasonal and spatial nutrient patterns. The concentrations for total nitrogen (TN) showed high concentrations for the summer period (1.04 to 1.86 mg/L) and low concentration for the winter season (0.25 to 0.46 mg/L). For the other nitrogen fractions in form of nitrate (NO₃⁻) and ammonium (NH₄⁺) the seasonal patterns were different to that of TN. In NO₃⁻ the concentrations were high during the summer and winter seasons and NH₄⁺ showed high concentration during the spring. The seasonality for total phosphorus (TP) showed high concentration for the spring period (0.049 to 0.163 mg/L) and low concentration for the other seasons (0.01 to 0.019 mg/L). A similar pattern has been observed for phosphate (PO₄³ ⁻) as well. The dissolved organic carbon (DOC) concentrations showed high concentrations during the summer period (21.36 to 31.64 mg/L) and low concentration during the winter seasons (5.48 to 7.14 mg/L). The seasonal pattern for the nutrient contents of the plant community showed highest concentrations during summer (5.5 to 34.2 gTN/kg) and lowest concentrations in winter (0.2 to 7.7 gTN/kg). Nutrient concentrations in the sediments were highest during the non-growing seasons (autumn and winter). This result indicated that the function of sediments changes seasonally from being a sink during the non-growing season by accumulating both allochthonous and autochthonous nutrients in the rainy season, and becoming a source during the growing seasons due to nutrient release from anaerobic sediments supporting the growth of the macrophyte community. Overall the function of sediment in reed bed pond of the Stormwater Harvesting Facility was to be a source of nutrients and therefore no accumulation of nutrients occurred during the study period. The research has demonstrated that the reed bed currently performs as a reasonable nutrient retention system with following nutrient removal rates: 0.85 mg TN /m²/day, 0.79 mg NO₃⁻ /m²/day, 0.28 mg NH₄⁺/m²/day, 0.05 mg TP /m²/day, 0.04 mg PO₄³ ⁻ /m²/day, and 5.75 mg DOC /m²/day. Seasonal difference in the water retention time showed that the for most of the nutrients the removal performance was most effective during autumn and winter with the exception of the removal performance of P forms, which most effective during spring and summer. For TN, NO₃⁻ and DOC the RE was most efficient at a residence time > 15days, for TP and PO₄³ ⁻ it is 5-10 days and for NH₄⁺ it is <;5days. Time–series modelling of the monitoring data resulted in rule-based prediction models for the different nutrients. Sensitivity analyses of the models revealed key driving variables for the nutrient dynamics of the reed bed. The prediction results revealed that the DO was the key driving variable influencing the nutrient concentrations in the water column and therefore to improve the water quality of the treatment water DO levels have to maintained above the threshold of 4 mg/L. Beside DO other key driving variables were turbidity, ORP and the nutrient levels from the previous site. Therefore the control of these parameters would be the start to develop a management plan for best-practice management in terms of water quality at the Parafield Stormwater Harvesting Facility. / http://proxy.library.adelaide.edu.au/login?url= http://library.adelaide.edu.au/cgi-bin/Pwebrecon.cgi?BBID=1458926 / Thesis (Ph.D.) -- University of Adelaide, School of Earth and Environmental Science, 2010