This thesis presents models applicable for aquatic ecosystems. Geographical Information Systems (GIS) form an important part of the thesis. The dynamic mass balance models focus on nutrient fluxes, biotic/abiotic interactions and operate on different temporal and spatial scales (site, local, regional and international). The relevance and role of scale in mass balance modelling is a focal point of the thesis. A mesocosm experiment was used to construct a model to estimate the nutrient load of phosphorus and nitrogen from net cage fish farming (i.e., the site scale). The model was used to estimate what feeding conditions that are required for a sustainable aquaculture scenario, i.e., a zero nutrient load situation (a linkage between the site scale and the regional scale). A dynamic model was constructed for suspended particulate matter (SPM) and sedimentation in coastal areas (i.e., the local scale) with different morphometric characteristics and distances to the Sea. The results demonstrate that the conditions in the Sea (the regional and international scale) are of fundamental importance, also for the most enclosed coastal areas. A foodweb model for lakes was transformed and recalibrated for Baltic Sea conditions (i.e., the international scale). The model also includes a mass balance model for phosphorus and accounts for key environmental factors that regulate the presuppositions for production and biomasses of key functional groups of organisms. The potential use of the new model for setting fish quotas of cod was examined. For the intermittent (i.e., regional) scale, topographically complex areas can be difficult to define and model. Therefore, an attempt was made to construct a waterscape subbasin identification program (WASUBI). The method was tested for the Finnish Archipelago Sea and the Okavango Delta in Botswana. A comparison to results from a semi-random delineation method showed that more enclosed basins was created with the WASUBI method.

This thesis presents predictive models for important variables concerning eutrophication effects in lakes. The keystone is a dynamic phosphorus model based on ordinary differential equations. By calculating mass fluxes of phosphorus into, within and out from a lake, the concentrations of different forms of phosphorus in different compartments of the lake are estimated. The dynamic phosphorus model is critically tested and several improvements are presented, including two new compartments for colloidal phosphorus, a sub-model for suspended particulate matter (SPM) and new algorithms for lake outflow, water mixing, diffusion, water content and organic content of accumulation sediments are implemented. Predictions with the new version show good agreement against empirical data in five tested lakes. The sub-model for SPM uses the same driving variables as the basic phosphorus model, so the inclusion of this model as a sub-model does not require any additional variables. The model for SPM may also be used as a separate model giving monthly predictions of suspended particulate matter in two water compartments and one compartment with SPM available for resuspension in ET-sediments. Empirical data from Lake Erken (Sweden) and Lake Balaton (Hungary) are used to evaluate the variability in settling velocity of SPM. It is found that the variability is substantial and may be accounted for by using a dimensionless moderator for SPM concentration. Empirical data from accumulation area sediments in Lake Erken are used to develop a model for the dynamics of phosphorus sedimentation, burial and diffusion in the sediments. The model is shown to provide reasonable monthly predictions of four functional forms of phosphorus at different sediment depths. Simulations with the lake phosphorus model using two different climate scenarios indicate that lakes may respond very differently to climate change depending on their physical character. Lake Erken, with a water retention time of 7 years, appears to be much more sensitive than two basins of Lake Mälaren (Sweden) with substantially shorter retention times. The implication would be that in eutrophic lakes with long water retention times, eutrophication problems may become serious if the future becomes warmer. This will be important in contexts of lake management when remedial measures against lake eutrophication have to be taken.

Made available in DSpace on 2016-06-02T20:34:59Z (GMT). No. of bitstreams: 1 6522.pdf: 11813930 bytes, checksum: 7b3b28c9003cd9b02191060694246535 (MD5) Previous issue date: 2015-01-29 / Universidade Federal de Sao Carlos / Three different classes of emerging contaminants were analyzed in surface water samples, suspended particulate matter (SPM) and sediments from the Jundiaí River Basin - SP. The hormones 17-β-estradiol and 17-α-ethinylestradiol were the only compounds that were not detected in the matrices studied. Caffeine was the compound detected with the highest concentrations for water samples, with values up to 25000 μg/L, while in sediment samples and MPS, triclosan was the compound that had the highest concentrations, with 0.90 μg/g 79.1 g/g, respectively. Other compounds more often detected included atenolol, carbamazepine, diclofenac, propranolol and triclosan, with mean concentrations up to 17 ng/L in samples from Piraí Creek and greater than 120 ng/L for samples from Jundiaí River. A seasonal effect was observed in the concentrations of the compounds and the higher values for all of these were obtained for samples from a sampling point located downstream of a sewage treatment plant. It was found a high correlation between the concentrations of detected compounds and the electrical conductivity, which allowed suggesting the use of new contamination markers by sewage. The occurrence of studied compounds was widespread among samples from Rio Jundiaí, showing the high level of environmental impact to which this water body is exposed. / Três diferentes classes de contaminantes emergentes foram analisadas em amostras de água superficial, material particulado suspenso (MPS) e sedimentos provenientes da Bacia Hidrográfica do Rio Jundiaí - SP. Os hormônios 17-β- estradiol e 17-α-etinilestradiol foram os únicos compostos não detectados nas matrizes estudadas. A cafeína foi o composto detectado com as maiores concentrações para as amostras de água, com valores de até 25000 μg/L, enquanto nas amostras de sedimento e MPS, o triclosan foi o composto que apresentou as maiores concentrações, atingindo 0,90 μg/g e 79,1 μg/g, respectivamente. Outros compostos mais frequentemente detectados incluíram o atenolol, a carbamazepina, o diclofenaco, o propranolol e o triclosan, com concentrações médias de até 17 ng/L nas amostras do Ribeirão Piraí e superiores a 120 ng/L para o Rio Jundiaí. Observou-se um efeito sazonal nas concentrações dos compostos e os valores mais elevados para todos estes foram obtidos no ponto amostral localizado a jusante de uma estação de tratamento de esgotos. Verificou-se uma alta correlação entre as concentrações dos compostos detectados e a condutividade elétrica, o que possibilitou sugerir a utilização de novos marcadores de contaminação por esgotos. A ocorrência dos compostos em estudo foi generalizada para as amostras do Rio Jundiaí, demonstrando o alto nível de impacto ambiental a que esse corpo aquático está exposto.

Made available in DSpace on 2015-02-24T19:48:45Z (GMT). No. of bitstreams: 1 AdrianaBG_capa_ate_secao5.pdf: 3230514 bytes, checksum: e499db1cdb9c0ab6b161220ff77e224a (MD5) Previous issue date: 2006-10-27 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / The Curimata? estuary is located in the oriental coast of Rio Grande do Norte State in Brazil. Its importance resides in the fact that this region possesses one of the last portions of preserved mangrove in the Rio Grande do Norte State. Nevertheless, it has been severely affected by many anthropogenic activities, as sugarcane monoculture and shrimp farming. Former works demonstrated that an accumulation of heavy metals is occurring in oysters in this estuary, and perhaps it could be explained by the input of metals in this ecosystem deriving from the shrimp farming. To better understanding the origin of these metals, bottom sediment samples, cores and suspended particulate matter were collected for a characterization of metal concentrations (Al, Ba, Cd, Cu, Cr, Fe, Mn, Ni, Pb, Zn) and to determine the potentially bioavailable metals. Additionally, the enrichment ratio for each element analyzed was calculated. The mineralogical composition of sediment samples and cores were obtained by X-ray diffraction. Moreover, data of orbital remote sensing were used in order to detect and quantify suspended matter by applying a logarithmic algorithm. Geochemical data of bottom sediments and cores revealed that, excepting Ba and Pb, the elements analyzed presented concentrations characteristic of an unpolluted ecosystem (Al: 0,25 - 8,76 %; Ba: 3,03 - 870 ?g.g-1; Cd: < 0,25 ?g.g-1; Cr: 1,72 - 82,4 ?g.g-1; Cu: 0,12 -25,3 ?g.g-1; Pb: 0,38 - 23,7 ?g.g-1; Fe: 0,10 - 5,82 %; Mn: 15,1 - 815 ?g.g-1; Ni: 0,14 - 36,1 ?g.g-1; Zn: 1,37 - 113 ?g.g-1). During the dry season a distribution pattern was observed, with higher metal concentrations in the margins, decreasing toward the central portion of the channel. These metal concentrations were well correlated with mineralogical compositions, with clay minerals prevailing at the margins, and quartz and feldspar in the center. However, this pattern was not observed during the wet season, probably because of the high water flux that disturbed bottom sediments. But, as observed for the dry season, a good correlation between metal concentrations and mineralogical composition was also observed for the wet season, with high metal concentrations where there were high quantities of clay minerals. Low enrichment ratios were obtained for the majority of elements analyzed, excepting for Mn, Ba and Pb. Manganese presented the higher ratios downstream for both seasons, and it can be an evidence of anthropogenic impact by shrimp farming. As barium and lead concentrations in sediment samples presented analytical problems during the total sample digestion, one cannot be sure that the ratios obtained correspond to the reality. The highest metal concentrations in particulate matter were obtained in the portion dominated by fluvial transport for all metals analyzed, excepting for copper. Barium and zinc were the only elements that presented elevated concentrations that are not common of unpolluted ecosystems (Ba: 5730 - 8355 ?g.g-1; Zn: 3899 - 4348 ?g.g-1). However, these high concentrations could not be related to the shrimp farming and waste waters from the town of Canguaretama, once they were obtained from the fluvial particulate matter, that is upstream from the activities above mentioned. The application of the logarithmic algorithm to the processed LANDSAT image was well succeeded, although the acquired image does not correspond exactly to the field campaigns. The IKONOS image provided very detailed views of the suspended sediment concentration at the estuary, as the mixture of distinct water flows at the confluence of Cunha? and Curimata? rivers, with more turbid waters from Cunha? river, that is directly affected by effluents from shrimp farming and urban waste waters deriving from the town of Canguaretama / O estu?rio do rio Curimata? localiza-se na por??o sul do litoral oriental do Estado do Rio Grande do Norte, apresentando uma das ?ltimas por??es de manguezais no Estado. Este ecossistema tem sido fortemente afetado por diversas atividades antropog?nicas, como o cultivo de cana-de-a??car, a carcinicultura, al?m da urbaniza??o. Trabalhos anteriores neste local revelaram que ostras Crassostrea rhizophorae apresentaram concentra??es de alguns metais acima dos limites permitidos para consumo, e que talvez a entrada destes metais no estu?rio estivesse relacionada aos efluentes de carcinicultura. Para uma melhor compreens?o da origem destes metais, foram coletadas amostras de sedimento de fundo, testemunhos e material particulado em suspens?o para uma caracteriza??o das concentra??es de dez elementos maiores e tra?os (Al, Ba, Cd, Cu, Cr, Fe, Mn, Ni, Pb, Zn), bem como para a determina??o dos elementos potencialmente biodispon?veis. Al?m disso, tamb?m foi realizado o c?lculo da raz?o de enriquecimento para cada elemento analisado. A composi??o mineral?gica das amostras de sedimento de fundo e dos testemunhos foi obtida atrav?s de difratometria de raios-X. Adicionalmente, dados de sensoriamento remoto orbital foram usados a fim de se detectar e semiquantificar o material particulado em suspens?o atrav?s da aplica??o de um algoritmo logar?tmico. As an?lises geoqu?micas das amostras de sedimento de fundo revelaram que os elementos analisados apresentaram concentra??es caracter?sticas de um estu?rio n?o polu?do (Al: 0,25 a 8,76%; Ba: 3,03 a 870 ?g.g-1; Cd: < 0,25 ?g.g-1; Cr: 1,72 a 82,4 ?g.g-1; Cu: 0,12 a 25,3 ?g.g-1; Pb: 0,38 a 23,7 ?g.g-1; Fe: 0,10 a 5,82 %; Mn: 15,1 a 815 ?g.g-1; Ni: 0,14 a 36,1 ?g.g-1; Zn: 1,37 a 113 ?g.g-1). Um padr?o de distribui??o dos metais foi observado durante a esta??o seca, com maiores concentra??es nas margens, diminuindo em dire??o ao centro do canal. A concentra??o dos metais se mostrou bem correlacionada com as respectivas composi??es mineral?gicas das amostras de sedimento, com minerais de argila predominando nas margens, e quartzo e feldspato mais presentes no centro do canal. Contudo, este padr?o n?o foi observado durante a esta??o chuvosa, provavelmente devido ao fluxo de ?gua mais intenso que promoveu o dist?rbio dos sedimentos de fundo, com remo??o da fra??o fina das margens. Mas, da mesma forma que observado para a esta??o seca, nas amostras coletadas durante a esta??o chuvosa tamb?m se observou maiores concentra??es de metais nas amostras com predom?nio de minerais argilosos. Raz?es de enriquecimento sugestivas de aus?ncia de polui??o foram obtidas para a maioria dos elementos analisados, com exce??o de Mn. O mangan?s apresentou as maiores raz?es ? jusante da atividade de carcinicultura, as quais sugerem polui??o significativa neste trecho durante ambas as esta??es seca e chuvosa. Esta pode ser uma evid?ncia do impacto da carcinicultura no estu?rio, j? que a montante desta atividade a raz?o de enriquecimento foi baixa. No material particulado em suspens?o as maiores concentra??es de metais foram obtidas na por??o dominada pelo transporte fluvial para todos os elementos analisados, com exce??o do cobre. Os ?nicos elementos que apresentaram concentra??es elevadas, incomuns para ambientes livres de polui??o, foram b?rio (de 5730 a 8355 ?g.g-1) e zinco (de 3899 a 4348 ?g.g-1). Contudo, estas concentra??es anormais aparentam n?o estar relacionadas ? carcinicultura ou aos efluentes da cidade de Canguaretama, uma vez que foram encontrados ? montante destas atividades. A aplica??o do algoritmo logar?tmico ? imagem LANDSAT foi bem sucedida, embora a imagem adquirida n?o corresponda exatamente ?s datas de coleta do material em suspens?o. A imagem IKONOS forneceu vis?es muito detalhadas do estu?rio que permitiram observar a distribui??o do material particulado, com a mistura de fluxos de ?gua distintos na conflu?ncia dos rios Cunha? e Curimata?, sendo que o rio Cunha? apresenta ?guas mais turvas, e ? diretamente afetado pelos efluentes de carcinicultura e dejetos urbanos da cidade de Canguaretama

Fundação Carlos Chagas Filho de Amparo a Pesquisa do Estado do Rio de Janeiro / The Amazon river, located in northernBrazil, discharges between 80,000 and 250,000 m3s-1 of water onto the adjacent shelf, creating a plume of brackish water that extends hundreds of kilometers away from the river mouth. This river also carries a large amount of fine sediments to the ocean where fluid mud has been found in the topset and upper foreset layers of the subaqueous delta formed on the mid-shelf. One of the main goals of this dissertation is to describe how turbulence and suspended sediment concentration vary along the Northern Channel of the Amazon river. Water column measurements were carried out in October 2008 at six anchor stations (P1, P3, P5, P6, P8 e P9) located seaward of the river mouth; P1 and P9 were &#61566;125 km apart. Each station was occupied during &#61566;13 hours during which current speed and direction were continuously sampled with a 600 kHz Teledyne-RDI ADCP; hourly profiles of temperature, salinity, turbidity and depth were also obtained. Water samples were collected for determination of Suspended Particulate Matter (SPM) concentration and calibration of the turbidity sensor. Current speed reached values above 1.5 m s&#61485;1 in the along-channel direction (NE-SW); a remarkable ebb-flood asymmetry was observed and flows were strongly ebb-dominated. Throughout the water column, SPM concentration at stations P1 and P3 varied between 100 and 300 mg L&#61485;1 in association with the presence of freshwater. In contrast, a strong salinity gradient was observed between stations P6 and P9, coinciding with the occurrence of concentrations of SPM above 10 g L-1 (fluid mud). At stations P3, P5 and P6, interface between freshwater from the Amazon river and salt water from the continental shelf, shear stresses wereestimated through four diferents methods: Reynolds, Turbulent Kinetic Energy (TKE), modified TKE and Quadratic Law; in the nearbed region (3 mab) the computed values varied between 0 and 3 Pa. At the three stations (P3, P5 and P6) the lowest and the highest shear stress values were obtained through, respectively, the Reynolds and the TKE methods. Over the whole water column turbulence intensity was estimated through the standard deviation of the turbulent component of the along-channel current velocity (root-mean square of u); from these values, it was estimated the turbulent dissipation of energy (G), whose values at 3 mab varied between zero and 20 s&#61485;1.

Este trabalho foi desenvolvido objetivando a determinação e a avaliação dos perfis temporais da concentração de alguns elementos químicos potencialmente tóxicos presentes no material particulado em suspensão (MPS) no interior de uma pequena indústria de fundição de metais bronze, ferro e alumínio que, em concentrações elevadas, podem acarretar sérios riscos à saúde do trabalhador. Para isso foi utilizado um amostrador temporal de MPS, que coleta amostras de aerossóis em intervalo de tempo pré-programados, separando-os por tamanho: (a) fração fina ou respirável (partículas com diâmetro aerodinâmico menor que 2,5 m, MP2,5) e (b) fração grossa ou inalável (entre 2,5 a 10 m, MP10-2,5), durante todo o período do processo de fundição (da fusão à moldagem). As amostras coletadas, na forma de faixas (strips) sobre um filtro (fração fina) e sobre um impactador (fração grossa), foram analisadas pela técnica de fluorescência de raios X por dispersão de energia (EDXRF), utilizando na excitação um tubo de raios X com alvo de Mo e e na detecção dos raios X característicos um detector semicondutor de Si(Li) acoplado a um analisador de pulsos multicanal, interpretando-se posteriormente os espectros de raios X obtidos pelo aplicativo AXIL. Para algumas amostras também foi feita uma análise com microscópio eletrônico de varredura (SEM/EDS) para se conhecer a morfologia dos particulados. Deste modo foi possível determinar a concentração de elementos químicos potencialmente tóxicos presentes em um ambiente de uma pequena indústria de fundição de metais, mostrando que o momento mais crítico dessa atividade foi o da moldagem e também determinar a forma do MPS. Na fundição do bronze e ferro, as concentrações dos elementos Cr, Mn, Ni e Pb, principalmente na fração fina no momento de moldagem, mostraram-se muito superior aos limites recomendados pelas agências brasileira e norte-americana. Apesar de não haver limites recomendados para o elemento Zn, foi verificada uma alta concentração principalmente na concentração na fração fina, o mesmo sucedendo para o Cu. Com respeito a fundição de alumínio, foi observado altas concentrações principalmente de Zn e Cu, somente na fração fina, não ocorrendo na fração grossa. Pelos resultados obtidos pode-se concluir que os trabalhadores estão sujeitos a condições insalubres de trabalho nesse tipo de ambiente, aconselhando-se o uso permanente de equipamentos adequados de proteção visando de preferência a fração fina, assim como um monitoramento constante desses elementos químicos durante todas as etapas do processo de fundição, principalmente na de moldagem / The aim of this work was to evaluate the chemical concentration of some potentially toxic inorganic chemical elements and the time profiles in fine (PM2.5, particles up to 2.5 m) and coarse (PM2.5-10, particles from 2.5 to 10 m) suspended particulate matter (SPM) inside a small foundry plant - bronze, iron and aluminium -, in which at high concentrations turns a healthy concern. For these purpose, a rotating streaker airparticulate sampler for sampling during all day foundry activity was utilized. Fine SPM was collected on a filter and coarse SPM in turn by an impactor. The collected samples were analyzed by energy dispersive X-ray fluorescence (EDXRF) technique employing a Mo target tube in the excitation, and the detection was carried out through Si(Li) semiconductor detector coupled to multichannel analyser, deconvolutting the X-ray spectra with AXIL software help. It was also carried out particulated morphological analysis by scanning electron microscopy with energy dispersive X-ray spectrometer coupled (SEM/EDS). In this manner, the inorganic chemicals content were determined in the small foundry allowing concluding that the moulding step is the critical one taking into account the amount of pollutant released. During bronze and iron melting, the Cr, Mn, Ni and Pb contents in SPM were higher than allowed values by Brazilian and United States legislations. It was also verified a high Zn and Cu content, mainly in the fine suspended particulate matter, although these elements are not contemplated by national nor international laws. Thus, due to this unhealthy environmental working conditions inside the small foundry plant,a proper individual protection equipment is mandatory mainly for fine suspended particulate matter, and a constant air pollutant monitoring in foundry plants is demanded, mainly during the moulding step

Les contaminants, dissouts ou adsorbés sur les particules, sont principalement délivrés au milieu marin par les fleuves. La dynamique sédimentaire constitue alors un proxy de la dynamique de ces contaminants. Cette thèse s'inscrit dans le projet ANR AMORAD, et se focalise sur la dynamique du matériel particulaire délivré par le Rhône au Golfe du Lion (Méditerranée nord-occidentale), principal contributeur d'apports solides au Golfe (80 % des sédiments). Alors que des études antérieures ont permis de bien représenter les processus au niveau du fond, les processus régissant les comportements des matières en supension (MES), majoritairement rencontrées dans le panache turbide du Rhône, sont encore mal apréhendés. En vue de mieux décrire la dynamique de ces MES et d'améliorer les modèles hydrosédimentaires existants, l'objectif est de mieux caractériser ces particules. À cette fin, un vaste jeu de données issu de capteurs déployés in situ (données collectées pour 12 campagnes en mer, réalisées de 2011 à 2016) a été exploité, permettant d’obtenir une vision 2D verticale mais seulement ponctuelle (spatialement et temporellement). De façon complémentaire, une base de données d'images satellitaires (donnée couleur de l'eau du capteur MERIS-300m acquise entre 2002 et 2012), offrant une vue plus synoptique et long terme mais uniquement en surface, a été exploitée. Le jeu de données d'images satellitaire (plus de 800 images) a été traité de façon innovante par l'application d'un traitement semi-automatique permettant l'extraction de différentes métriques du panache turbide du Rhône (e.g. aire, limites d'extension, forme, centres géométriques, concentrations). La distribution spatiale et les caractéristiques physiques des MES telles que leur concentration dans l'eau, leur diamètre médian ou encore leur vitesse de chute ont été étudiées et estimées en fonction des différents forçages hydrométéorologiques actifs sur la zone d'étude (e.g. débit du Rhône, vents dominants). Un nouveau modèle hydrosédimentaire reposant sur le couplage du modèle hydrodynamique MARS-3D et du module sédimentaire multiclasse MIXSED a été configuré et les données in situ et satellitaires ont pu être mobilisées afin de contraindre la vitesse de chute des sédiments, paramètre clef de la modélisation de la dynamique hydrosédimentaire. / Contaminants, which can be dissolved in water or adsorbed on particles, are mainly delivered to the coastal environment by rivers. Thus, sediment dynamics reperesent a relevant proxy of contaminants dynamics. ThisPhD thesis is part of the ANR AMORAD project, of which one workpackage focuses on the fate of sediments in the coastal environment. This work focuses on the dynamics of Rhône River sediments in the Gulf of Lions (north-western mediterranean), this river delivering 80 % of the sediments of the Gulf. While previous studies over the area allowed a better understanding of physical processes at the water-sediment interface, processes driving suspended particulate matter (SPM) dynamics are still poorly understood. To better describe this SPM dynamics and improve hydrosedimentary models, the aim is to better characterize these particles. To this end, a large dataset collected from in situ deployed sensors (data collected for 12 field campaigns, conducted from 2011 to 2016) was analyzed to get a 2D vertical but ponctual view (both spatially and temporally). Complementary, a satellite images dataset (MERIS-300m ocean colour archive from 2002 to 2012) was built in order to get a long term and more synoptic view (but limited to surface).This dataset (more than 800 images) was originaly studied, applying a semi-empirical process to extract various Rhône River turbid plume metrics (e.g. area of extension, south-east-westernmost points, shape, centroids, SPM concentrations). Plume metrics and physical properties of SPM such as their concentration in water, their median diameter or their settling velocity were investigated regarding the different hydrometeorological forcings (e.g. Rhône River discharge, prevailing winds). A new hydrosedimentary model, based on the coupling of the 3D hydrodynamical model MARS-3D and the sedimentary module MIXSED, was set and ocean color and in situ data were used to constrain the settling velocity of particles, key parameter of hydrosedimentary modelling.

La dynamique des Matières en Suspension (MES) dans les estuaires macrotidaux est fortement variable à la fois spatialement (du compartiment fluvial à l'embouchure de l'estuaire) et temporellement (de la seconde à plusieurs années), mais reste primordiale pour comprendre et quantifier la dynamique sédimentaire des environnements estuariens. Avec le développement croissant des réseaux de mesures haute-fréquence à l'échelle internationale, l'objectif principal de cette étude est de qualifier et de valoriser les mesures de turbidité acquises par un réseau de mesures haute fréquence (réseau SYNAPSES) implanté d'amont en aval sur l'estuaire de la Seine (France) à la fois (i) en matière de suivi de la dynamique des MES du compartiment fluvial au bouchon vaseux et (ii) en matière d'estimation des flux de MES sur différentes échelles spatio-temporelles de l'estuaire de la Seine. Les données acquises à partir du réseau SYNAPSES et des campagnes in situ (81 journées de 12 h - OBS-3+/YSI/LISST 100X-C/ADCP 600 kHz) sur quatre stations réparties de l'estuaire fluvial à la zone du bouchon vaseux, constituent un set de données extrêmement riche et unique sur les domaines estuariens. La variabilité des relations, établies entre les mesures de turbidité [NTU] et les mesures de concentrations en MES [g.L-1] sur chacune des campagnes de l'échelle tidale à annuelle, met en évidence l'effet (i) de la technologie interne du capteur et (ii) de la variabilité des propriétés optiques inhérentes des particules (diamètre médian D50), densité sèche rhô et efficacité de diffusion Qc) sur la sensibilité des différents capteurs optiques. L'analyse conjointe des données in situ et des données SYNAPSES a permis de calibrer les mesures de turbidité en concentration massique, avec une relation validée sur le cycle annuel, spécifique à chacune des stations et des incertitudes minimisées. Après une étude de la représentativité des stations du réseau vis-à-vis de la section, les flux instantanés de MES sont estimés (i) à partir des données de concentrations en MES et de débits acquis par l'ADCP sur l'intégralité de la section et (ii) à partir des concentrations ponctuelles en MES du réseau SYNAPSES couplées au modèle hydrodynamique MARS-3D. Les comparaisons des flux de MES in situ par rapport à ceux estimés par la combinaison SYNAPSES/MARS-3D permettent de proposer un coefficient spécifique à chacune des stations du réseau SYNAPSES, dans le but d'ajuster les flux instantanés de MES estimés, avec leurs incertitudes, à partir du réseau SYNAPSES à la réalité in situ. Les outils et les démarches développés dans la thèse sur l'estuaire de la Seine pauvent être appliqués à d'autres estuaires macrotidaux pour estimer les flux sédimentaires. / The dynamics of Suspended Particulate Matter (SPM) in macrotidal estuaries is highly variable both spatially (from the fluvial compartment to the estuary mouth) and temporally (from the second to several years), but it is essential to understand and quantify the sedimentary dynamics of estuarine environments. With the development of high-frequency measurement networks around the world, the main objective of this study is to qualify the turbidity measurements acquired by a high-frequency measurement network (SYNAPSES network) located on the Seine estuary (i) in terms of monitoring the SPM dynamics from the fluvial compartment to the turbidity maximal zone (TMZ) and (ii) in terms of estimation of the SPM fluxes on different spatio-temporal scales of the Seine estuary. Data acquired from the SYNAPSES network and complementary in situ campaigns (81 days of 12 h - OBS-3+/YSI/LISST 100X-C / ADCP 600 kHz) on four stations from the fluvial estuary of the Seine Estuary to the turbidity maximal zone, are an extremely rich and unique dataset on estuarine environments. The variability in the relationship between turbidity measurements [NTU] and SPM concentration measurements [g.L-1] on each campaign, reveals the effect of (i) the internal sensor technology and (ii) the variability of the particle inherent optical properties (median diameter D50, dry density rho and scattering efficiency Qc) on the sensitivity of different optical sensors. The analysis of the in situ and the SYNAPSES data allowed to calibrate the turbidity measurements in mass concentration, with a validated relationship on the annual cycle, specific to each of the stations and reduced uncertainties. After a study of the SYNAPSES station representativeness across the section, the instantaneous fluxes of SPM are estimated (i) from the SPM concentration and liquid flow data acquired by the ADCP on the global section and (ii) from the SPM concentrations of the SYNAPSES network coupled to the hydrodynamic model MARS-3D (estimation of the liquid flow). Comparisons of SPM fluxes in situ to those estimated by the combination SYNAPSES/MARS-3D allow to propose a specific coefficient for each of the SYNAPSES network stations, xith the aim of adjusting the SPM instantaneous fluxes estimated from the SYNAPSES network to the in situ reality, with reasonable uncertainties. the tools and approaches developed in the PhD thesis on the Seine estuary can be applied to other macrotidal estuaries to estimate sedimentary fluxes.

La contamination en composés aromatiques polycycliques (CAP) a été suivie entre 2014 et 2015 au cours de six campagnes d’échantillonnage sur 8 sites différents entre Auboué et Richemont. Cette section du cours d’eau correspond à la partie aval de la vallée de l’Orne profondément affectée par plus d’un siècle d’activités minières et sidérurgiques qui ont cessé entre 1968 et 2009. L’Orne a donc été le réceptacle de rejets industriels et urbains et a été profondément perturbée dans son hydrodynamisme avec la construction de plusieurs barrages. Dans ce contexte, l’occurrence des 16 hydrocarbures aromatiques polycycliques réglementaires (HAP), de 11 CAP oxygénés (O-CAP) et de 5 CAP azotés (N-CAP) et leur distribution dans les fractions dissoute et particulaire des eaux de l’Orne ont été étudiées en mettant en place des protocoles d’échantillonnage et d’analyse adaptés. Le premier objectif de ce travail a été de comparer les méthodes d’échantillonnage des matières en suspension par filtration et par centrifugation à flux continu sur le terrain. Des différences significatives ont pu être identifiées entre les deux techniques, la filtration amenant à des concentrations en CAP plus élevées du fait d’une plus grande abondance des CAP de bas poids moléculaire. Nous avons pu mettre en évidence le rôle de la fraction fine (< 5µm) et/ou colloïdale plus ou moins retenue par les filtres et qui, de part sa réactivité, piège des CAP. La comparaison des deux méthodes dans différentes situations hydrologiques nous montre que cette rétention n’est pas systématique mais plutôt corrélée à des situations de fort hydrodynamisme. Les deux méthodes d’échantillonnage des matières en suspension ne sont donc pas comparables mais complémentaires. Le suivi saisonnier et multi-sites des eaux de l’Orne montre que la concentration en CAP varie entre 1.6 et 223.7 ng L-1 dans la fraction dissoute et entre 1.5 et 105.5 µg g-1 dans la fraction particulaire avec des variations spatiales de ±35% et ±45% respectivement. Les variations de concentration des CAP dans la fraction dissoute sont importantes d’un site à l’autre lorsque le débit est faible (de 0.5 à 34 m3.s-1). Les concentrations en CAP sont faibles autour de 20 ng.L-1 et spatialement homogènes en périodes de haut débit (> 50 m3.s-1) du fait de la dilution. Les concentrations en CAP dans les matières en suspension varient entre 2.8 to 36.3 µg g-1, et montrent des concentrations stables quelles que soient les situations hydrologiques lorsqu’elles sont collectées par la centrifugeuse de terrain. La fraction dissoute est enrichie en HAP de bas poids moléculaire dans les périodes d’étiage et est marquée par l’occurrence des HAP à 5 et 6 cycles aromatiques au cours des épisodes de crue. Les CAP polaires sont au moins aussi abondants que les HAP dans la fraction dissoute et évoluent de la même façon que les HAP. La part des CAP polaires dans la fraction particulaire est significativement plus basse (de 10 à 20% de l’ensemble des CAP) / The spatio-temporal variations of the concentration and distribution of dissolved and particulate polycyclic aromatic compounds (PACs), namely 16 polycyclic aromatic hydrocarbons (PAHs), 11 oxygenated PACs (O-PACs) and 5 nitrogen PACs (N-PACs), were studied in the Orne, a river impacted for more than one century by iron mining and steel-making industry. The first objective of this work was to compare the influence of two different methods of separation of suspended particulate matter (SPM), filtration (FT) and field continuous flow centrifuge (CFC). Results showed that in half of the sampling campaigns, PAC concentrations were 2 to 8 times higher for PAHs and 2 to 10 times higher for O-PAC when SPM were collected by filtration. These differences that were not observed systematically over the six sampling campaigns could be explained by the retention of colloidal matter on glass-fiber filters that appeared as a very reactive phase particularly enriched in low molecular PACs. The two methods were then considered as complementary methods to study SPM. The second objective of this work was to perform a long term monitoring of PAC concentrations and distributions in dissolved and particulate fractions. The results from the six sampling campaigns between May 2014 and September 2015 in eight different sites showed that the PAC concentrations ranged between 1.6 to 223.7 ng L-1 in the dissolved fraction (?PACTD), and between 1,55 to 105,5 µg g-1 in the total particulate fraction, with maximum spatial variation of ±35% and ±45% respectively. The dissolved PACs spatial variations were strongly influenced by the hydrological conditions and less spatial variation was observed during high flow events as the result of dilution and homogenization of pollutants. During low flow events, particulate PACSPM-CFC concentrations were more stable and equivalent in values and distribution to the corresponding PACSPM-FT samples. Overall it was in a range between 2.8 to 36.3 µg g-1. The dominance of dissolved low molecular weight PAHTD in the low flow events decreased during high flow events due to the appearance of penta- and hexa-cyclic PAHs. The dissolved polar PACs were as high as the PAHs contribution and also subjected to seasonal changes, the O-PACs ranged between 5.6 to 90.3 ng L-1 and N-PAHs from 1.0 to 42.5 ng L-1. The particulate polar PACs concentrations and contribution were significantly lower, the highest concentrations of 8,76 µg g-1 and 29,41 µg g-1 was observed during high flow event for O-PACs and during low flow event for N-PAH respectively

Erosion et transferts de matières (i.e. matières en suspension-MES, associées avec le carbone et les éléments traces métalliques - ETM) par les fleuves et rivières sont contrôlés par des facteurs naturels (ex. géologie, climat) et peuvent être significativement modifiés par les pressions anthropiques et/ou, le changement climatique. En se basant sur une banque de données de concentrations en MES et de débits, à hautes résolutions temporelles (journalières) sur le long terme (1960-2008) à l’exutoire du bassin versant du Fleuve Rouge (Chine/Vietnam), les taux d’érosion ont été estimés en moyenne à 600 t/km²/an avec des valeurs variant de 160 à 1330 t/km²/an selon les années. Cette large gamme de taux d’érosion est liée fortement aux conditions hydrologiques interannualles, mais aussi à la présence de réservoir de HoaBinh en 1989. En effet, à partir 1989, chaque année, 50% de matières transportées par le Fleuve Rouge sont piégées dans ce réservoir, correspondant à un taux de sédimentation dans le réservoir de 52 à 200 cm/an. La variabilité spatiale des flux de MES du bassin versant du Fleuve Rouge au Vietnam suggère que les MES du Fleuve Rouge viennent principalement de l’érosion en amont du bassin versant (~80%), contrairement à ce que l’on observe pour le flux liquide (~21%). De plus, l’échange des processus érosion-transport-sédimentation dans la partie médiane du bassin versant dépend fortement des conditions hydrologiques ; à l’inverse, une forte sédimentation a été observée à l’entrée du Fleuve Rouge dans le delta, quelle que soit la condition hydrologique. De même, dans la partie vietnamienne du Fleuve Rouge, les facteurs majeurs influant sur le taux d’érosion seraient les maximas d’élévation et la pente moyenne du bassin. Un suivi hebdomadaire à bimestriel en 2008-2009 des paramètres biogéochimiques (carbone et ETM) ont permis de caractériser la qualité des eaux et des particules sur l’ensemble du bassin versant du Fleuve Rouge. Les concentrations en carbone organique (particulaire et dissous) dans les eaux du Fleuve Rouge sont relativement faibles et majoritairement d’origine allochtone. Les concentrations en carbone inorganique dissous (CID) sont très importantes, en faisant le composé majoritaire (60-90%) des eaux du Fleuve Rouge, en relation avec la présence de roches carbonatées dans le bassin versant. En terme de concentrations en ETM, la qualité des eaux et des particules transportées dans le bassin versant du Fleuve Rouge au Vietnam peut être qualifiée de mauvaise dans la partie amont et de médiocre en aval. L’étude de la répartition entre phase dissoute et phase particulaire a montré que l’essentiel des transferts se fait sous forme particulaire pour plupart des ETM (excepté Mo), dû aux forts taux d’érosion mécanique. De plus, l’étude à haute résolution spatiale (40 points) réalisée sur l’ensemble bassin versant du Fleuve Rouge au Vietnam des concentrations en ETM et de leur spéciation (dissous et particulaire) a mis en évidence de fortes anomalies géochimiques dans la partie amont. Enfin, l’identification des signatures géochimiques des particules érodées a révélé des signatures similaires entre les particules de l’amont et de l’aval du Fleuve Rouge, démontrant une contribution quasi-exclusive de la partie chinoise aux flux de matière (80-95% au flux total). / Erosion and transfer of suspended particulate matter (SPM), and associated elements (e.g. carbon, trace metal elements-ETM) by river are attributed to a combination of natural parameters related to geology and climatic influences and affected by human disturbance. Based on an extensive dataset of daily water discharge and SPM concentrations between 1960 and 2008 at the outlet of the Red River system, the annual SPM yield of the Red River is estimated at 600 t/km²/yr (ranged between 160 and 1330 t/km²/yr). This large range of sediment yield is strongly related to the inter-annual hydrological conditions and the operation of the HoaBinh Reservoir in 1989. In fact, the HoaBinh Reservoir reduces annual SPM delivery to the delta by half after 1989, i.e. the mean sedimentation rate of 52-200 cm/yr. The spatial variability of SPM fluxes in the Red River watershed suggests that most SPM were eroded from the upstream catchment located in China (80%), contrasting the water discharge with only 21%. In addition, the complex processes of erosion/sedimentation occurring in the middle Red River basin strongly depend on hydrological conditions; in contrast, an important sedimentation was observed at the entry point to the Red River Delta whatever the hydrological conditions. The major factors controlling the spatial variation of the sediment yields of the Vietnamese Red River watershed are maximum elevation and mean surface.During 2008-2009, high resolution sampling (weekly to bimestrial) of biogeochemical parameters (carbon and ETM) were performed at five key sites along the Red River system. The organic carbon (particulate and dissolved) concentrations in the Red River are relatively low and mainly allochtonous; in contrast, the dissolved inorganic carbon are very important and is the major carbon form (60 -90%) in relation to the abundance of carbonate rocks in the Red River watershed. In terms of ETM concentrations, the quality of water and SPM transported in the Vietnamese Red River watershed can be classified as poor upstream and as mediocre downstream. The study of the partition between the dissolved and particulate phases showed that most ETM transported in the Red River are in particulate phase (except Mo), due to the high mechanical erosion rate. In addition, high spatial resolution study (40 sites) performed in the Vietnamese Red River watershed of ETM concentrations and their speciation (dissolved and particulate) has highlighted strong geochemical anomalies in the upstream Red River. Finally, the identification of geochemical signals showed a similarity in the geochemical signal of particulate metal transport between upstream and downstream of the Red River, suggesting a contribution quasi-exclusively from the upstream part (in China) in the ETM fluxes of the Red River (80 -95%). / Quá trình xói mòn và vận chuyển vật chất (chất rắn lơ lửng, các-bon và kim loại nặng) bởi các dòng sông, suối chịu ảnh hưởng tổng hợp từ các quá trình tự nhiên (địa chất, khí hậu) và các hoạt động của con người. Dựa trên các bảng số liệu ngày về hàm lượng chất rắn lơ lửng và lưu lượng nước trong giai đoạn từ năm 1960 đến năm 2008 trên trục chính của sông Hồng tại trạm Sơn Tây (hạ nguồn của hệ thông sông Hồng trước khi chảy vào vùng đồng bằng), mục tiêu đầu tiên của luận án là nghiên cứu sự biến đổi theo thời gian tải lượng trung bình chất rắn lơ lửng của sông Hồng. Các kết quả cho thấy trong giai đoạn quan trắc, hàng năm sông Hồng chuyển tải ra biển khoảng 24×106 đến 200×106 tấn/năm (trung bình các năm là 90×106 tấn /năm), tương đương với hệ số xâm thực từ 160 đến 1330 tấn/km²/năm. Chính sự phụ thuộc mạnh mẽ của hàm lượng chất rắn lơ lửng vào các điều kiện thuỷ văn khác nhau đã tạo ra sự đa dạng về tải lượng chất rắn chuyển tải hàng năm của hệ thống sông Hồng. Tuy nhiên, trong những năm 1989-1990, khi hồ chứa Hoà Bình đi vào hoạt động, tải lượng chất rắn lơ lửng chuyển tải ra biển của hệ thống sông Hồng đã giảm sút còn khoảng 50×106 tấn, tức là đã giảm khoảng 50%. Dựa trên chiều cao và thể tích của hồ Hoà Bình, hệ số lắng đọng chất rắn lơ lửng trong lòng hồ được xác định vào khoảng 52-200 cm/năm. Như vậy, sau 20 năm đi vào hoạt động, độ dầy lớp bùn đất lắng đọng trong hồ Hoà Bình khoảng 10.4-40m, làm giảm đáng kể thể tích của hồ Hoà Bình.Mục tiêu tiếp theo của luận án là thiết lập cân bằng hàm lượng chất rắn lơ lửng trong các đoạn sông từ thượng nguồn sông Hồng (trạm Lào Cai), tại các hạ nguồn của 3 nhánh sông chính (sông Hồng tại Phú Thọ, sông Đà và sông Lô tại Việt Trì) và tại Sơn Tây trong thời kỳ 2003-2008. Diễn biến của các quá trình xói mòn, chuyển tải và lắng đọng diễn ra trên các đoạn sông một cách phức tạp, đan xen lẫn nhau và phụ thuộc chặt chẽ vào các điều kiện thuỷ văn. Tuy vậy, hiện tượng lắng đọng mạnh mẽ các chất rắn lơ lửng trong vùng hạ nguồn của hệ thống sông Hồng (từ Phú Thọ đến Sơn Tây) đã được ghi nhận trong tất cả các năm quan trắc, không phụ thuộc vào điều kiện thuỷ văn. Ngoài ra, dựa vào các số liệu thu thập được, chúng tôi đã lập bản đồ xói mòn cho toàn bộ lưu vực sông Hồng tại Việt Nam. Hơn thế, các kết quả còn chỉ ra rằng độ cao và độ dốc trung bình lưu vực là hai yếu tố chính ảnh hưởng đến hệ số xâm thực của lưu vực sông Hồng.Đánh giá chất lượng nước và chất lượng chất rắn lơ lửng chuyển tải trong hệ thống sông Hồng là mục tiêu thứ 3 của luận án. Để đạt được mục tiêu trên, chúng tôi đã tiến hành lấy các mẫu nước và chất rắn lơ lủng trên trục chính cũng như trên các nhánh sông chính của sông Hồng để phân tích hàm lượng các-bon hữu cơ và vô cơ cũng như hàm lượng kim loại nặng trong hai năm 2008-2009, với chu kì lấy mẫu hàng tuần đến hàng tháng. Hàm lượng các-bon hữu cơ (dạng hoà tan và lơ lửng) trong nước sông Hồng tương đối thấp tại tất cả các điểm lấy mẫu và nguồn gốc chính của các-bon hữu cơ là allochtone. Ngược lại, hàm lượng các-bon vô cơ hoà tan rất cao, chiếm khoảng 60-90% hàm lượng các-bon tổng và được giải thích bằng sự có mặt phong phú của núi đá vôi trên toàn lưu vực. Đối với kim loại nặng, dựa trên các kết quả phân tích về hàm lượng kim loại nặng trong nước và trong chất rắn lơ lửng và các tiêu chuẩn đánh giá chất lượng nước QCVN 08, chúng tôi đã đánh giá chất lượng nước cho toàn bộ hệ thống sông Hồng từ Lào Cai đến Sơn Tây. Nếu nước sông Hồng trên vùng thượng nguồn (tại Lào Cai và Phú Thọ) không đảm bảo chất lượng để có thể sử dụng làm nguồn nước sinh hoạt thì tại các vùng hạ lưu của sông Hồng, sông Đà và sông Lô, nhìn chung nước của 3 nhánh sông có thể dùng để cung cấp nước sinh hoạt nhưng phải qua các quá trình xử lí tách cặn lơ lửng. Hơn nữa, trong năm 2008, chúng tôi đã thực hiện hai chương trình lấy mẫu nước, chất rắn lơ lửng và trầm tích trên 40 điểm phân bố đều trên toàn bộ lưu vực sông Hồng tại Việt Nam trong mùa cạn và mùa mưa.