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The application of olivine to coastal areas is a proposed method of removing carbon dioxide from the atmosphere for climate change mitigation. Olivine is abundant and dissolves relatively fast, but it contains trace amounts of nickel (Ni), chromium (Cr), and cobalt (Co) which may be toxic to marine biota in cases of widespread coastal olivine spreading. Prior studies have suggested that Ni concentrations in marine sediments and/or the overlying water column due to olivine dissolution could be a limiting factor for its carbon capture potential. Therefore, it is critical to understand and model the processes affecting trace metal bioavailability after olivine application. This research used sand and sediments collected from a natural olivine beach (Papakōlea) and a black sand control beach (Richardson) in Hawaii to measure the adsorption of Ni, Cr, and Co to suspended particulate matter (SPM) in the water column and to beach sediments in equilibrium with pore water. The experimentally derived adsorption isotherms were then used for phase distribution modeling in the water column and sediment pore water at both sites. Cr was observed to readily precipitate in seawater without suspended solids, meaning its exposure pathway for marine organisms will likely be via sediment, regardless of interactions with solid phases. Co uptake from solution may have been influenced by biological processes based on its continuous adsorption over 30 days, but more study ofcobalt adsorption to SPM is required because of conflicting results in a repeated experiment. Thus, Ni was the focus of the phase distribution modeling in this work. Ni adsorption from seawater to SPM generated from both Papakōlea and Richardson sediments followed Langmuir adsorption models. Parameters for Ni adsorption to SPM from Papakōlea at pH 7.81 were KL = 2.74 L/kg and qmax = 931 mg/kg and for Richardson SPM at pH 8.00 they were KL = 5.69 L/kg and qmax = 1446 mg/kg. Ni adsorption to SPM was strongly affected by pH with the qmax for Richardson SPM nearly eight times greater at pH 8.00 than at pH 7.77. Ni adsorption to Papakōlea SPM was five times greater than Ni adsorption to Richardson SPM at comparable pH. Ni adsorption to beach sediments from both sites was measured for five pHs between 7.27 and 8.73. Ni adsorption was observed to be strongly affected by pH and sediment type. A significant adsorption edge was observed for the Papakōlea sediment between pH 8.00 and 8.22, while a gradual increase in adsorption was observed between pH 7.27 and pH 8.15 for the Richardson sediment. Ni adsorption to the beach sediments from pore water at the typical seawater pH of 8.05 was calculated by interpolation between adsorption models at surrounding pH values. Calculated Ni adsorption to Papakōlea sediment at pH 8.05 was linear with Kd = 22.4 L/kg while Ni adsorption to Richardson sediment at pH 8.05 followed a Langmuir model with KL = 0.8 L/kg and qmax = 179 mg/kg. Phase distribution models constructed with the experimentally derived adsorption isotherms predicted that over 85% of the Ni in the water column is dissolved. This result was similar for the water columns at both beaches and was based on typical coastal total suspended solids (TSS) concentrations (5-20 mg/L). Therefore, it is predicted that transport of Ni into marine sediments by SPM settling is much smaller than bulk transport of dissolved Ni into the open ocean. In contrast, the pore water models predict that over 95% of total Ni is adsorbed to the solid phase for both sediments. In a scenario where dissolved Ni concentration in the pore water is the maximum safe level of 8.2 ppb (US EPA environmental quality standard; EQS), Ni adsorbed to the sediment at both sites is predicted to be less than 10% of safe levels, the Florida Department of Environmental Protection’s threshold exposure limit (TEL) of 15.9 mg Ni per kg of sediment. These adsorbed Ni concentrations are likely a better indicator of threshold sediment Ni concentrations because presumably Ni adsorbed to sediments is more readily bioavailable than Ni in the structure of the olivine. In this case, dissolved Ni would be of more environmental concern than Ni in seabed sediments at sites of olivine enrichment. However, it will be important to investigate the bioavailability of Ni directly from the olivine structure to confirm this conclusion. If dissolved Ni concentration in the pore water is the limiting factor for safe application of olivine, then olivine loading rates should be based on site-specific conditions (mixing regime and the residence time of seawater in the sediment pores) to maintain a dissolved Ni concentration less than the EQS. For Papakōlea Beach, with 70% olivine in thesediments, the dissolved Ni concentrations in the pore waters were measured to be at background seawater concentrations. This is likely because of the rapid mixing and high- energy wave action at this beach. Under these conditions, very little Ni would be adsorbed to the sediments. Additional site-specific studies of Ni and Co adsorption to beach sediments should be conducted to gain a more complete understanding of the fate and transport of these trace metals and the risks posed to coastal ecosystems by their release. More experiments are needed to characterize Co adsorption in seawater to SPM and beach sediment. Additionally, Ni adsorption experiments should be performed on a wider variety of beach sediments to estimate its fate and transport at specific locations of potential olivine enrichment. Also, Ni adsorption to Papakōlea SPM was measured at pH 7.81, and since adsorption is expected to be much greater at seawater pH, the Ni adsorption experiment should be repeated at a pH greater than that of seawater to allow the construction of adsorption isotherms for Papakōlea SPM at seawater pH by interpolation. Additionally, experiments need to be conducted to determine the bioavailability of trace metals in the olivine itself and adsorbed to the olivine.

Master of Science / Geology / Matthew W. Totten / The most common practice of typing crude oils utilizes biomarkers to gain insight on the history of the oil. This practice only considers the organic chemistry of the oil, and does not consider the trace element concentrations within the oil. Rare earth element and other trace element concentrations in crude oil might provide further insight into the oil’s source and origin. This study analyzed REE and other trace metal concentrations of crude oil in the Spivey-Grabs field of south-central Kansas through analysis by ICP-MS and ICP-AES that, coupled with visual physical characteristics of oil and FT-IR analysis, could explain the reported “compartmentalization” of the field and provide insight on the origin of the oils. Analysis of physical characteristics of the crude oils suggested the presence of two types of oil, of differing viscosities, in the field. FT-IR confirmed the presence of these two oil types based on functional groups present in the oils. The existence of a high viscosity oil could potentially explain the compartmentalization behavior in the field. PAAS-normalized REE distribution patterns showed a general LREE enrichment, a positive cerium and negative europium anomaly, and a MREE and HREE depletion, but higher viscosity oils showed additional MREE and HREE enrichment. K/Rb values ranged from 2,864 to 44,118, with oils from mixed-viscosity wells having lower ratios overall. K/Rb values of Spivey-Grabs crude oils more closely resembled those of the Lansing-Kansas City formation than the K/Rb values of the Woodford shale and Mississippian formation of the Anadarko basin. Comparing the rare earth element distribution patterns and K/Rb values from this study to those of the Woodford shale suggests the Spivey-Grabs oil originated from a local source and not from the Woodford shale.

The research work is directed towards the investigation, optimization and application of some plant-based waste materials for the removal of some toxic trace metals (Cd, Pb and Mn) as well as selected oxyhalides (CIO3-,IO3- and BrO3-) in aqueous system. Waste materials from three plants; Athrixia philicoide, an indigenous bush tea; the outer covering peels of butternut Squash (Cucurbita Moschata) and pineapple (Ananas comosus) were evaluated for their sorption efficiency of the selected metals. batch and continuous experimental processes as well as conditions that might influence the sorption of the metals were investigated. These conditions include effects of pH sorption time, amount of adsorbent, volume of the aqueous medium, amount of metals etc. Qualitative and quantitative analysis of metal ions in solution was carried out using the ion chromatograph (IC) while the functional group identification present in waste materials was established using the Fourier Transform infr-red spectroscopy (FTIR), Quantitative biosorption equilibrium of 98.99% was reached within 6h at pH 6 and 100 ppm concentration of Pb metal with Athrixiaphilicoide under 30 min contact time. Applicability of the sorption process was tested on wastewater. Results revealed that > 99.93 %; 84.5 % and 64.3 % sorption efficiency was obtained for Mn, Cd and Pb respectively at pH 7 using Ananas Comosus adsorbent. For Athrixia philicoide, sorption efficiency from spiked wastewater ranged from 99.98 % for Cd; 99.96 % for Mn and 82.5 % adsorption for Pb at pH 7. For Juglans Cinerea, wastewater sorption efficiency varied between 78.76 %, 94.50 % and 96.50 % for Cd, Mn and Pb respectively at pH6. Results from the optimized method revealed the applicability of the method to environmental water samples. Possible large scale and industrial/commercial application of developed materials and methods would be explored. ) in aqueous system. Waste materials from three plants; Athrixia philicoide, an indigenous bush tea; the outer covering peels of butternut Squash (Cucurbita Moschata) and pineapple (Ananas comosus) were evaluated for their sorption efficiency of the selected metals. Batch and continuous experimental processes as well as conditions that might influence the sorption of the metals were investigated. These conditions include effects of pH, sorption time, amount of adsorbent, volume of the aqueous medium, amount of metals etc. Qualitative and quantitative analysis of metal ions in solution was carried out using the ion chromatograph (IC) while the functional group identification present in waste materials was established using the Fourier Transform infra-red spectroscopy (FTIR). Quantitative biosorption equilibrium of 96.99 % was reached within 6h at pH 6 and 100 ppm concentration of Pb metal with Athrixia philicoide under 30 min contact time. Cd and Mn adsorption by the same adsorbent under similar condition were less than 50 % for individual metal evaluation experiment. However, > 99 % adsorption was achieved with Cd in a mixture of the three (3) evaluated metals. Highest adsorption of 93 % of Pb was achieved with the Butternut Squash peel (Cucurbita moschata) at the optimal sorption pH of 6 followed by quantitative sorption of 99.2 % of Mn while Cd recorded a sorption level of 45 % all at 6 pH. The sorption efficiency of Pb, Cd and Mn using pineapple peels (Ananas comosus) also at the optimal sorption conditions of (pH 6, 30 min contact time and 100 ppm metal concentration) ranged from 98.7 %, 100 % and 99.90 % respectively. / Enviromental Science / M.Sc (Enviromental Science)

O processamento anaeróbio da vinhaça se apresenta como uma alternativa para a recuperação de energia (biogás), e reaproveitamento das suas características nutricionais através da disposição no solo. Com o intuito de elevar a eficiência energética, o presente trabalho teve como objetivo estimular a produção de metano em reatores anaeróbios em batelada de lodo granular adaptado, alimentados com vinhaça de usina sucroalcooleira, por meio da adição de metais traço. Foram avaliadas as suplementações da vinhaça com Co, Zn, Mo, Ni, Mn e W. Na Fase 1 foram realizados 4 ensaios, os reatores foram analisados individualmente nas concentrações 200 μg.L-1, 350 μg.L-1, 500 μg.L-1 e 800 μg.L-1. Na Fase 2 verificou-se o comportamento dos metais em conjunto, à concentração de 350 μg.L-1 de cada micronutriente (Co, Ni, Zn, Mo, Cu e Mn). Os dados de produção acumulada de CH4 foram ajustados pelo modelo modificado de Gompertz, e foram obtidas as constantes cinéticas. Na Fase 1, verificou-se que a concentração de 200 μg.L-1 de Co foi a mais adequada aos experimentos e apresentou a maior velocidade máxima de produção de CH4, 121,30 mL.d-1 (aumento de 17% na taxa de produção de metano). Nesta mesma Fase, o W apresentou indícios de inibição à concentração de 800 μg.L-1, e os demais metais exibiram os melhores resultados nesta mesma concentração, a velocidade de produção (Rm) aumentou para o Mn (26%), Ni (25%), Cu (21%) e Mo (19%), e os rendimentos mais expressivos foram para Mo (0,267 mL CH4.mg-1 DQOrem), Zn (0,240 mL CH4.mg-1 DQOrem) e Ni (0,232 mL CH4.mg-1 DQOrem). A Fase 2 não apresentou resultados satisfatórios, as verificações não indicaram variação relevante entre os reatores do ensaio e controle. / Anaerobic processing of vinasse is presented as an alternative to energy recovery (biogas), and reuse of its nutritional characteristics through the provision on the ground. In order to increase energy efficiency, this study aimed to stimulate methane production in adapted anaerobic batch reactors with granular sludge fed with vinasse from sugarcane biorefineries, through the addition of trace metals. The supplementation vinasse were evaluated with Co, Zn, Mo, Ni, Mn and W. In phase 1 four essays were realized, and micronutrient were analyzed individually in concentrations of 200 μg.L-1, 350 μg.L-1, 500 μg.L-1 and 800 μ.L-1. In phase 2 it was observed the behavior of metal together, with micronutrients concentration of 350 μg.L-1 (Co, Ni, Zn, Mo, Cu e Mn). The data of methanes production were adjusted by Gompertz modified model and kinetics constants were obtained. In phase 1 it was verified that the concentration of 200 μg.L-1 of Co was optimal for the experiments and showed the highest maximum production velocity of CH4, 121,30 mL.d-1 (increase of 17%). In this phase W showed evidence of inhibition at a concentration of 800 μg.L-1, and other metals showed the best results in the same concentration. The velocity of production (Rm) increased to Mn (26%), Ni (25%), Cu (21%) e Mo (19%), and the most significant yields were to Mo (0,267 mL CH4.mg-1 DQOrem), Zn (0,240 mL CH4.mg-1 DQOrem) and Ni (0,232 mL CH4.mg-1 DQOrem). Phase 2 did not show satisfactory results.

Les nanoparticules de fer manufacturées (NPs-Fe) sont des matériaux de taille nanométrique dont l’utilisation s’est, depuis peu, étendue à des domaines environnementaux. Leur dispersion dans les milieux aqueux et solides, et leurs interactions avec le vivant soulèvent toutefois encore de nombreuses questions. Dans la première partie de cette étude, nous conduisons un travail approfondi de caractérisation des NPs-Fe et précisons comment ces propriétés sont impliquées dans les processus contrôlant la stabilité colloïdale puis la réactivité chimique (capacité d’adsorption du cuivre) des NPs-Fe en solution aqueuse. Des modifications à la fois surfaciques et cristallochimiques sont appliquées afin de mettre en évidence le rôle clés de la chimie de surface des NPs-Fe. Dans cette étude, il est montré que les acides humiques limitent l’agrégation des NPs-Fe et procurent des sites d’adsorption pour les métaux. Les conditions physico-chimiques du milieu s’avèrent également jouer un rôle crucial. Le pH modifie notamment la charge de surface des NPs-Fe et les forces d’interactions électrostatiques qui en résultent. Dans un deuxième temps, nous étudions les interactions entre les NPs-Fe et les végétaux, en solution puis dans un sol. Après 63 et 57 jours, les mesures de susceptibilité magnétique montrent que les NPs-Fe s’accumulent au niveau des racines avant d’être transloquées, en moindre quantité, dans les parties aériennes des plantes. La réponse des plantes à l’exposition aux NPs-Fe se traduit par une augmentation de la biomasse végétale et des teneurs en chlorophylles et une diminution de la peroxydation lipidique. / Engineered Iron Oxide Nanoparticles (IONPs) are specific nanoscale materials that have recently been used into wide environmental applications. The dispersion of IONPs into soils and waters, as well as their interactions with living organisms, raise many scientific issues. The first part of this work is intended to provide a thorough characterization of IONPs in aqueous solution, from their intrinsic physico-chemical properties to their colloidal behavior and chemical reactivity. Surface modifications are applied to evidence the key role of surface chemistry towards most interactions IONPs encounter. In particular, humic acid reduce NPs-Fe aggregation and display a high adsorption capacity for trace metals, especially copper (Cu).On the other hand, the pH of the solution play a critical role towards NPs-Fe interactions. Depending on the pH, the surface charge of the particles are modified and hence pH is involved in the electrostatic forces that drive the particles aggregation state and contribute to metal adsorption. The second part of the study is focused on the interactions occurring with IONPs in presence of plants. Several experiments are conducted in aqueous solution and in soil columns to precise the impacts of IONPs on the growth medium and to assess the effects of IONPs on plants. Results (magnetic susceptibility) show that IONPs manage to penetrate the roots of beans and sunflower plants (57 and 63 days-old) and that they are translocated to the aerial parts in low amounts. Plants respond to IONPs penetration by increasing the plant biomass and the chlorophyll contents and by decreasing the lipid peroxidation.

Cette thèse a porté sur la détermination et l’étude écodynamique d’éléments traces métalliques sur des technosols fortement contaminés en métaux et metalloïdes en contexte de revégétalisation naturelle ou de phytoremédiation. Deux schémas d'extractions séquentielles ont été utilisés conjointement à des extractions sélectives en parallèle avec la détermination de la concentration totale dans les sols, de la concentration totale dissoute dans les eaux porales, du pool labile (sondes DGT) et des tests de germination avec des haricots nains pour étudier la spéciation, la mobilité et la phytodisponibilité de métaux et métalloïdes (Zn, Pb, Cd, As et Sb) pour les technosols de deux sites post-minier (La Petite Faye) et industriel (Mortagne-du-Nord). De plus de jeunes plants de P. euramericana Dorskamp ont été cultivés en rhizobox sur les technosols de Mortagne-du-Nord pour étudier l’effet rhizosphèrique sur la mobilité des métaux. Enfin l’effet de l’addition d’azote sous forme de nitrate et d’ammonium sur le comportement de ces métaux a été également étudié pour P. euramericana Dorskamp sur ces mêmes sols. Malgré les fortes concentrations totales en métaux et métalloïdes dans les sols du site de La Petite Faye, la mobilité de ces éléments potentiellement toxiques est limitée car associés à la fraction résiduelle. La phytodisponibilité est également limitée et corrélée avec le pool labile des technosols. La culture de P. euramericana Dorskamp a généré un effet rhizosphèrique caractérisé par une augmentation de la valeur du pH et la concentration de carbone organique dissout (COD) de la solution de sol ainsi qu’une diminution des concentrations totale dissoute des métaux (Zn, Pb et Cd) dans la solution de sol. L’addition d’azote sous forme de nitrate et d’ammonium a respectivement augmenté et diminué le pH de la solution de sol et dans le cas de l’ammonium a augmenté également le COD et stabilisé les métaux dans la rhizosphère par rapport aux sols de contrôle. / This thesis dealt with the determination and study of the ecodynamics of trace metals in technosols highly contaminated in metals and metalloids in the context of natural revegetalisation or phytoremediation. Two sequential extraction schemes were used jointly with selective extractions in parallel with the determination of the total metals concentration in soils, the total dissolved metals concentration in the soil pore water, the metals labile pool (DGT) and germination tests with dwarf beans to investigate the speciation, mobility and phytoavailability of (Zn, Pb, Cd, As and Sb) for technosols of two post-mining (La Petite Faye) and industrial (Mortagne du Nord) sites. Additionally, young plants of P. euramericana Dorskamp were cultivated in rhizobox on Mortagne du Nord technosols to investigate the rhizospheric effect on the mobility of metals. Moreover, the effect of nitrogen addition under nitrate and ammonium on the behavior of these metals has been investigated for P. euramericana Dorskamp for the same soils. Despite the high total metals and metalloids concentration in the La Petite Faye soils, the mobility of these potentially toxic elements is limited because of their association with the residual fraction. The phytoavailability is also limited and correlated with the labile pool of technosols. The culture of P. euramericana Dorskamp generated a rhizospheric effect characterized by an increase of the pH and concentration of dissolved organic carbon (DOC) in the soil pore water and a decrease in the total dissolved concentration of metals (Zn, Pb et Cd) in the soil pore water. The addition of nitrogen under nitrate or ammonium respectively increased and decreased the soil pore water pH and in the case of ammonium the DOC also increased and stabilized metals in the rhizosphere in comparison to control soils.

O presente estudo analisou aspectos do ciclo de vida e níveis de metais em Atherinella brasiliensis da praia de Itamambuca, Ubatuba (SP). As coletas foram mensais, nos períodos diurno e noturno, de setembro de 2003 a fevereiro de 2005, em quatro estações na praia e uma no rio Itamambuca, utilizando-se picaré. Os indivíduos migram diariamente para dentro do rio no período noturno. O melhor ajuste ao modelo de von Bertalanffy (CT= 164,85*(1-e-2,16(t+0,0038))) e à longevidade (A0,95= 1,378 ano) foi obtido pelo método de Ford-Walford. O índice de performance de crescimento e a mortalidade variaram de 2,77 a 2,91 e 1,64 a 1,82 ano-1, respectivamente. O valor de L50 estimado para sexos agrupados foi 86,6 mm, e os de RGS, DK e a freqüência de desovantes sugerem desova durante todo o ano, com maior intensidade do final da primavera até início do outono. A desova é parcelada, com alta freqüência e em pequenos lotes. Altas concentrações de Cr, Fe e Zn foram detectadas na musculatura, sendo maiores em indivíduos jovens e na alta temporada turística. Pode-se concluir que o peixe-rei passa todo seu ciclo de vida na praia de Itamambuca, apresenta altas taxas de crescimento e mortalidade natural, e desova ao longo de todo o ano. / The present study analyzed the life history and metal levels of Atherinella brasiliensis from Itamambuca beach, Ubatuba (SP). Surveys were conducted monthly, in diurnal and nocturnal periods, between September 2003 and February 2005, in four stations at the beach and one at the Itamambuca river, using beach seine. Individuals showed daily migration into the river at nocturnal period. The better adjustment to von Bertalanffy?s model (Lt = 164.85*(1-e-2.16(t+0.0038))) and to longevity (A0.95= 1.378 year) was obtained through Ford-Walford method. The value of estimated L50 for grouped gender was 86.6 mm, and the GSR, the DK and the spawning frequency suggest spawning during all year around, with higher intensity in late spring until middle autumn. The high frequency of spawning and the low batch fecundity indicate that the species is a batch spawner. High concentrations of Cr, Fe and Zn were detected in musculature, being higher among young individuals, and during tourist high season. In conclusion, the Brazilian silverside spends its life cycle on the Itamambuca beach, shows high growth and natural mortality rates, and spawning throughout the year.

Made available in DSpace on 2015-04-22T22:02:12Z (GMT). No. of bitstreams: 1 Paulo Renan.pdf: 1587343 bytes, checksum: 5a08e797bff6ad2f7e370d3d94651720 (MD5) Previous issue date: 2012-08-30 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Fractionation of the metals Fe, Mn, Zn, Cu and Ni in sediments was performed for samples collected from ten locations from igarapé Educandos sub-basin, in Manaus AM, north Brazil. From air dried sediment particles was made a sequential extraction procedure proposed by the European Community Bureau of Reference (BCR). In general, the speciation study revealed that Mn, Zn, Cu and Ni have high mobility due to their high contents in the exchangeable/acid soluble fraction, while Fe is less mobile. Principal component analysis (PCA) clearly separated the metals in groups, due to different distributions of the metals in the various fractions, in sediments from different locations. The enrichment factor (EF) obtained for each metal showed the intense anthropogenic influence in the region. Based on the risk assessment code (RAC), Mn, Zn and Ni posed a very high risk to the ecosystem (RAC > 50%), Cu pose a high risk (RAC > 31%) and Fe a low risk (RAC < 10%). / O fracionamento dos metais Fe, Mn, Zn, Cu e Ni em sedimentos de fundo foi realizado para amostras coletadas de dez locais na sub-bacia do igarapé Educandos, na cidade de Manaus Brasil. Nas partículas de sedimento seco ao ar, foi feito um procedimento de extração sequencial proposto pela European Community Bureau of Reference (BCR). De maneira geral, o estudo de especiação revelou que Mn, Zn, Cu e Ni possuem alta mobilidade devido aos seus altos conteúdos na fração solúvel em ácido/trocável, enquanto que Fe é o menos móvel. A análise de componentes principais (PCA) aplicada para as diferentes frações do procedimento BCR claramente separou os metais dentro de grupos, devido as diferentes distribuições dos metais nas várias frações. O fator de enriquecimento (FE) obtido para cada metal mostrou a intensa influência antrópica na região. Baseado no código de avaliação de risco (RAC), Mn, Zn e Ni representam um risco muito alto para este ecossistema (RAC > 50%), Cu representa um risco alto (RAC > 31%) e Fe um risco baixo (RAC < 10%).

L’étude réalisée lors de ce travail de thèse porte sur l’évaluation de l'impact de l’agglomération Marseillaise sur le milieu côtier à travers la quantification des éléments traces métalliques (ETM) et du carbone organique. Sur le littoral méditerranéen français, Marseille représente la plus grande agglomération (~ 1.7M Ha) et possède la station d’épuration (STEP) enterrée la plus grande d’Europe (capacité de 1.62M équivalent-habitants), avec une façade directement ouverte sur la Méditerranée. L’impact de cette zone urbaine et industrialisée (flux brut) sur la zone côtière reste mal compris, de par la multiplicité des sources (apports directs(rivières/effluents) vs. apports diffus (friches industrielles côtières, aérosols, ...)) en partie contrôlée par le climat. Il en est de même des mécanismes de transfert des contaminants conditionnant leur devenir dans le milieu marin (flux nets vers le large). Dans ce contexte, différentes campagnes de prélèvements d’eau et de sédiments ont été mises en oeuvre sous des conditions climatiques contrastées (temps sec vs. pluie) dans les rivières ainsi qu'en mer, le long d’un transect allant de la côte à plus de 2 km au large des rejets. Les objectifs de cette étude visaient à déterminer les sources de contaminants au milieu côtier et à comprendre leurs mécanismes de transfert et leur devenir en mer. Par temps sec, les résultats obtenus ont montré que la dynamique du système est principalement contrôlée par les rejets de la STEP qui, par exemple, est responsable à plus de 75% des apports en Ag, Cu ou Pb au milieu côtier. Une fois en mer, les différents ETM analysés présentent un profil non conservatif, dû à un fractionnement dissous/particulaire hors équilibre dans les émissaires associé à un relargage rapide au début du gradient de salinité. Ces résultats ont été confirmés par une expérience de remobilisation réalisée au laboratoire permettant de mieux comprendre la cinétique de désorption des ETM. Dans ces conditions, il a été démontré qu'il était indispensable de filtrersur le terrain les échantillons pour ne pas sous-estimer la fraction dissoute des ETM. Par temps de pluie, le suivi des apports au cours d'une crue a montré la très grande réactivité du système, typique de rivières côtières. La majorité des ETM, transportés principalement sous forme particulaire, subissent une fois en mer des processus de désorption avec des cinétiques plus lentes et à des salinités plus importantes que par temps sec. Ces différences sont probablement liées à la nature des particules, urbaines et très organiques par temps sec, plutôt terrigène et inorganiques par temps de pluie. Enfin, une expérience de vitesse de chute des particules transitant dans le système par temps sec et de pluie a été développée au laboratoire. Elle a permis de caractériser les particules étudiées par des paramètres physico-chimiques intégrables au modèle hydro-sédimentaire de l'IFREMER, permettant de mieux évaluer le devenir des particules en zone côtière. / The aim of this PhD was to evaluate the impact from Marseille agglomeration on thecoastal area, using trace metals and organic carbon quantification. On the French Mediterraneancoast, Marseille is the largest agglomeration (~1.7M inhabitants), located directly on coast andhave the biggest European underground wastewater treatment plan (WWTP, 1.62M eq). Theimpact of this urbanized and industrialized area on the coastal zone (bulk fluxes) remainsmisunderstood, because of the multiplicity of contaminant sources (direct inputs(rivers/effluents) vs. diffusive ones (coastal industrial wasteland, aerosols, …)) partlycontrolled by climatic conditions. Similarly, the transfer mechanisms of contaminants thatcontrol their fate to the open sea (net fluxes) have to be studied. In such context, numerouswater and sediment sampling campaigns were performed during contrasted climatic conditions(baseflow vs. flood) in the tributaries and along a 2km coastal-offshore transect in front of theoutputs. The main objectives of this study were to determine contaminants sources, transfermechanisms and fate in the coastal zone. During baseflow conditions, results have shown thatthe system dynamic is mainly controlled by the WWTP inputs, that are for instance the maincontributor (>75%) of Ag, Cu or Pb inputs to the coastal area. When discharged to the sea, thestudied trace metals presented non-conservative behaviours, consecutive to adissolved/particulate fractionation out of equilibrium in the outlets associated to fastremobilization at the beginning of the salinity gradient. These results were confirmed by labremobilization experiments allowing to better understand the desorption kinetics of tracemetals. Under such conditions, it was demonstrated that on-field filtration is a prerequisite toavoid under-estimation of the dissolved fraction of trace metals. The monitoring of a flood eventduring a rainy period has shown the high reactivity of the studied system, a peculiarity ofMediterraneean coastal rivers. Most of the studied trace metals, mainly brought in theparticulate fraction, suffer desorption processes when discharged to the sea, a processcharacterized by kinetics slower and effective at higher salinity in comparison to baseflowinputs. These differences are most probably linked to the nature of particles being urban andorganic during baseflow, mostly terrigeneous and inorganic during flood. Finally, a settling rateexperiment was designed in the lab in order to evaluate the physical and chemical characteristicsof representative particles. The obtained parameters were integrated in the 3D hydrodynamicand sediment transport model of IFREMER allowing to better evaluate the fate of pollutedparticles in the coastal area.