L’objectif principal de ce travail de thèse est d’évaluer l'impact des activités anthropiques sur le fonctionnement des systèmes aquatiques. L’impact des rejets urbains de Fès sur le Sebou, l'une des plus grandes rivières du Maroc, a été choisi pour cette étude. Les eaux usées domestiques et industrielles de la ville de Fès (~1M hab), véhiculées par son affluent l’oued Fès, sont rejetées dans le Sebou quasiment sans traitement. Deux sites du Sebou, en amont et en aval des rejets de la ville de Fès, et un site situé sur l’oued Fès ont été étudiés. Une campagne de prélèvement de carottes de sédiments et onze campagnes mensuelles de prélèvement d’eau et de matières en suspension (MES) ont été effectuées dans le but de quantifier les apports en nutriments, éléments traces métalliques (ETM) et carbone organique afin d’étudier la dynamique de ces polluants. Les résultats obtenus ont mis en évidence une augmentation des concentrations de presque tous les éléments étudiés en aval de la ville de Fès aussi bien dans la colonne d’eau que dans les sédiments. L’étude des carottes sédimentaires a révélé une contamination modérée par les butylétains totaux (ΣBT) avec la prédominance du monobutyétain dans les trois sites d’étude et sur toutes les profondeurs. Les sédiments du Sebou, en amont de la ville de Fès se caractérisent par les teneurs les plus faibles en métaux alors que ceux de l’oued Fès présentent une forte pollution polymétallique, accentuée dans les sédiments de surface, ce qui reflète clairement la signature d'apports anthropiques récents résultant des rejets non traités de la ville de Fès. L’augmentation consécutive des teneurs des métaux dans les sédiments du Sebou en aval de la confluence Fès-Sebou traduit l'influence significative des particules polluées de l’oued Fès. Dans la colonne d’eau, les concentrations mesurées dans le Sebou en amont de la confluence Fès-Sebou sont proches des rivières naturelles, à l’exception de Cl-, Cr, Na+ et NO3- dont les concentrations traduisent des pollutions agricoles et/ou domestiques. En revanche, la signature anthropique des rejets de la ville de Fès apparait évidente dans les eaux de l’oued Fès qui montrent des concentrations très élevées en ETM dissous et particulaires. La majorité des ETM provenant des apports anthropiques subissent des changements importants de leur coefficient de distribution Kd et présentent un comportement non conservatif dans le mélange entre les eaux du Sebou et celles de l’oued Fès. Ces résultats ont été confirmés par le modèle WHAM qui permet de prédire correctement le fractionnement dissous/particulaire, du Cu, Pb et Zn. La spéciation chimique de ces éléments ainsi que leur répartition dissous/particulaire apparaissent significativement influencées par les conditions particulières (anoxie, forte contamination, teneurs importantes en matière organique) des eaux de l’oued Fès. Ces conditions sont aussi à l’origine du comportement non conservatif de la majorité des éléments lors d'un mélange Sebou/Fès, observé aussi bien dans la colonne d’eau que dans les sédiments. / The main goal of this PhD was to evaluate the impact of the anthropogenic activities (urban, industrial or agricultural activities) on aquatic systems. The Fez metropolitan area and its impacts on the Sebou River, the main Moroccan river, were chosen as a case study. The Fez agglomeration (~1M hab), is surrounded by the Fez River, receiving the wastewaters of this developing city and then flowing into the Sebou. This work was performed on two sites along the Sebou River (upstream and downstream from the confluence with Fez River), and one site in the Fez River, downstream from the Fez city. One sampling campaigns of sediment cores and eleven sampling campaigns were performed during low flow conditions to quantify nutrients, organic carbon and trace metals and to study the dynamic and the transport of trace elements in the Sebou and Fez rivers. The obtained results revealed a global increase of studied elements in the Sebou River from upstream to downstream sampling site, in both sediments and water column. A moderate level of contamination by butyltins was observed, with monobutyltin being the dominant species across all sites and depths. The lowest level of metal pollution was identified in the Sebou's sediments upstream Fez city. Whilst the Fez' sediments were heavily polluted and exhibited bottom-up accumulation trends, which clearly evidence recent inputs from the untreated wastewaters of Fez city. The increase of metal levels in Sebou downstream sediments reflects a significant contribution of polluted particles from the Fez River. Dissolved and particulate concentrations of most of the analyzed elements in the Sebou, upstream from Fez city, are close to the natural rivers, except Cl-, Cr, Na+ et NO3- probably due to untreated urban inputs from several small/medium-size towns located upstream Fez. In the opposite On the contrary, high dissolved and particulate trace metals concentrations in the Fez River clearly indicated strong anthropogenic inputs from Fez city. Most of the studied trace metals originated from anthropogenic sources, underwent significant changes of Kd and behaved non-conservatively in the Sebou/Fez waters mixing due to drastic changes of the waters quality (anoxic condition, high concentration, high organic matter content). Dissolved/particulate partitioning were correctly assessed by WHAM-VII modeling for Cu, Pb and Zn, depicting significant differences in chemical speciation in Fez River when compared to Sebou one.

L’étude du comportement des éléments métalliques est primordiale compte tenu leur effet souvent toxique dansde nombreux écosystèmes. Ces derniers lorsqu’ils interagissent avec la Matiere Organique (MO), peuvent formerdes complexes plus ou moins stables. Ainsi, la MO joue un rôle important dans leur spéciation chimique et leurtransport. Dans ce travail, l’analyse de cette complexation est réalisée par Quenching de Fluorescence (QF).Cette technique permet de modéliser la fixation des sites de complexation à l’aide d’une constante thermodynamiquedéterminée à partir d’un modèle 1 : 1. Le quenching de fluorescence a été mesuré par spectroscopie defluorescence en mode stationnaire et en mode résolue en temps. Les mesures de fluorescence en mode stationnairefournissent des Matrices d’Excitation et d’Émission de Fluorescence (MEEFs). L’extraction des différents composantsde ces MEEFs est effectué par séparation de sources : la décomposition multilinéaire CP/PARAFAC,qui permet de caractériser spectralement les composants. Les mesures par Spectroscopie Laser Résolue en Temps(SLRT) permettent une caractérisation spectrale et temporelle des composants fluorescents. L’étude des lois dedécroissance de la fluorescence induite par impulsion laser nanoseconde en l’occurrence a permis de déterminerle type d’interaction entre la MO et les quencheurs. Pour se faire, un algorithme de déconvolution temporellea été appliqué à chaque décroissance de fluorescence mesurée. L’interprétation des données temporelles a étéaccomplie en utilisant le graphique de Stern–Volmer. Les résultats des interactions du cuivre, de l’europiumet de l’uranium avec les Acides Humiques (AH) et les Acides Fulviques (AF) montrent des décroissances defluorescences importantes et des constantes de stabilité entre 2,04 et 4,52. Le cuivre a permis de valider notremodèle d’étude et l’interaction de l’europium et l’uranium avec les AH et AF étudiés a révélé des constantesde stabilité en général en bonne corrélation avec la littérature. Les résultats de la SLRT ont souvent révélé desdécroissances bi–exponentielles et des temps de vie entre 0,40 et 14 ns et montrent que les interactions étudiéesont principalement engendrer un quenching statique et donc la formation d’un complexe moléculaire à l’étatfondamental. Cette étude a donc permis par caractérisation spectrale et temporelle, de déterminer l’interactionde la matière organique avec les métaux plus ou moins toxiques. / The study of metal elements behavior, considering their impact in various ecosystems, is of paramount importance.The latter, upon contact with Organic Matter (OM) can form weak or strong stable complexes. Therefore,OM plays an important role in their chemical speciation and transport. The analysis of these properties is carriedout by Fluorescence Quenching (QF). This technique allows introspecting ligands–metal interactions andthe 1 : 1 modeling (one ligand site, one metal) gives information about the conditional thermodynamic constant.Fluorescence quenching was measured using steady–state and time–resolved fluorescence spectroscopy.The steady–state measurements provides Excitation and Emission Matrices of fluorescence (EEMs). The extractionof the different components from these matrices is carried out by a multi–mode factor analysis such asCP/PARAFAC, which allows a spectral composition of the samples. Time-Resolved Laser Spectroscopy (TRLS)measurements allow temporal and spectral characterization of the fluorescent components. Indeed, the study ofthe fluorescence decays induced by a nanosecond pulsed laser in this case allowed to measure the interaction betweenthe OM and the quencher. For those purposes, a fluorescence lifetime deconvolution algorithm was appliedto each fluorescence decay. Analysis of the fluorescence lifetime data was accomplished using the Stern–Volmerplot which gave reliable information on the quenching process that takes place. Copper, europium and uraniuminteractions with Humic Acids (HA) and Fulvic Acids (FA) shows significant fluorescence decays and stabilityconstants between 2.04 and 4.52. Copper allowed to calibrate our model study and the interactions of europiumand uranium with the HA and FA studied reported stability constants in agreement with the literature. TRLSresults have often revealed a bi–exponential decays and fluorescence lifetimes between 0.40 and 14 ns and showsthat the studied interactions mainly lead to static quenching and thus the formation of a molecular complex inthe ground state. This study has allowed spectral and temporal characterization to determine organic matterinteraction with toxic metals.

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.

<p>The results of the multivariate analyses suggest that most of the variation in the composition of the samples was of an intra-sample nature, illustrating large scale patchiness in foraminiferal distribution. There were, however, definite differences between communities around Robben Island and in St Helena Bay, and least variation was found between the control and pipeline sites, and between the stations of each site. When the trace metal concentrations and the percentage nitrogen increased, the richness, diversity and abundance of foraminifera tended to decrease. Sediment grain size positively affected abundance but negatively affected diversity and richness. In both areas mean grain size did not, however, appear to play a very large role in influencing diversity. Cadmium, copper, chromium, the percentage nitrogen and the mean grain size were identified as the most important variables influencing the community structure by the BIOENV BEST routine in PRIMER. The trace metals and percentage nitrogen only had negative effects on the diversity and abundance as well as on the abundance of the dominant genera, whereas the mean grain size had variable effects.</p>

La présente étude porte sur l’évaluation d’une méthode d’acquisition de la solution de sol présente à l’interface sol-racine, dans la rhizosphère. Cette interface constitue le lieu privilégié de prise en charge par les plantes des contaminants, tels que les métaux traces. Comme les plantes acquièrent ces éléments à partir de la phase liquide, la solution de sol de la rhizosphère est une composante clé pour déterminer la fraction de métaux traces biodisponibles. La microlysimétrie est la méthode in situ la plus appropriée pour aborder les difficultés liées à l’échelle microscopique de la rhizosphère. Ainsi, dans les études sur la biodisponibilité des métaux traces au niveau de la rhizosphère, les microlysimètres (Rhizon©) gagnent en popularité sans, toutefois, avoir fait l’objet d’études exhaustives. L’objectif de cette étude est donc d’évaluer la capacité de ces microlysimètres à préserver l’intégrité chimique de la solution, tout en optimisant leur utilisation. Pour ce faire, les microlysimètres ont été soumis à une série d’expériences en présence de solutions et de sols, où la quantité de solution prélevée et le comportement des métaux traces (Cd, Cu, Ni, Pb, Zn) ont été étudiés. Les résultats montrent que les microlysimètres fonctionnent de façon optimale lorsque le contenu en eau du sol est au-dessus de la capacité au champ et lorsqu’il y a peu de matière organique et d’argile. Les sols sableux ayant un faible contenu en C organique reproduisent mieux le volume prélevé et la solution sous la capacité au champ peut être récoltée. L’utilisation des microlysimètres dans ces sols est donc optimale. Dans les essais en solution, les microlysimètres ont atteint un équilibre avec la solution après 10 h de prélèvement. En respectant ce délai et les conditions optimales préalablement établies (pH acide et COD élevé), les microlysimètres préservent la composition chimique de la solution. Dans les essais en sol, cet équilibre n’a pas été atteint après dix jours et huit prélèvements. Le contenu en matière organique et l’activité microbienne semblent responsables de la modification des concentrations en métaux au cours de ces prélèvements, notamment, dans l’horizon FH où les microlysimètres performent très mal. En revanche, dans l’horizon B, les concentrations tendent à se stabiliser vers la fin de la série de prélèvements en se rapprochant des valeurs de référence. Bien que des valeurs plus élevées s’observent pour les microlysimètres, leurs concentrations en métaux sont comparables à celles des méthodes de référence (extrait à l’eau, lysimètres de terrain avec et sans tension). En somme, les microlysimètres se comportent généralement mieux dans l’horizon B. Même si leur utilisation est plus optimale dans un sol sableux, cet horizon est privilégié pour de futures études sur le terrain avec les microlysimètres. / This study focuses on evaluating a method of acquiring soil solution in the soil-root interface of the rhizosphere. The liquid phase of the rhizosphere constitutes the main area where plants absorb contaminants like trace metals. Thus the rhizosphere soil solution is key to determine the amount of bioavailable trace metals. Microlysimetry has been described as the most appropriate in situ method to tackle difficulties inherent to the microscopic scale of the rhizosphere. Despite the lack of an exhaustive evaluation of their performance, microlysimeters have gained popularity for in situ studies on the bioavailability of trace metals. The objective of this study was to evaluate the capacity of microlysimeter to preserve the chemical integrity of the soil solution and also to determine their optimum use conditions. To do this, microlysimeter have been submitted to a series of laboratory experiments with solutions and soils. The volume of solution extracted and trace metals (Cd, Cu, Ni, Pb, Zn) behaviour were studied. Results show that microlysimeters work optimally when soil water content is above field capacity and when the amount of clay and organic matter is low. Sandy soils with low organic carbon content have a better reproducibility for extracted volume and soil solution extraction is possible even when soil water content is below field capacity. Using microlysimeters in this soil type is thus optimal. In solution experiments, microlysimeters reached equilibrium with the control solution after ten hours of extraction. In optimal conditions (acidic pH and high DOC) and after this ten hours period, microlysimeters preserve the chemical composition of the solution. In soil experiments, this equilibrium has not been reached after eight samplings throughout ten days. Organic matter content and microbial activity could be responsible for the modification of concentrations of trace metals during sampling. This is especially true for FH horizon where microlysimeters perform poorly. In contrast, the concentrations reach the reference values toward the end of sampling serie in the B horizon and microlysimeters have a better overall performance in this horizon. Although higher values are observed for microlysimeters, trace metals concentrations are comparable to other extraction methods, specifically for the B horizon. Even if their uses are optimized in sandy soil, the B horizon should be privileged for future field studies involving microlysimeters.

<p>The results of the multivariate analyses suggest that most of the variation in the composition of the samples was of an intra-sample nature, illustrating large scale patchiness in foraminiferal distribution. There were, however, definite differences between communities around Robben Island and in St Helena Bay, and least variation was found between the control and pipeline sites, and between the stations of each site. When the trace metal concentrations and the percentage nitrogen increased, the richness, diversity and abundance of foraminifera tended to decrease. Sediment grain size positively affected abundance but negatively affected diversity and richness. In both areas mean grain size did not, however, appear to play a very large role in influencing diversity. Cadmium, copper, chromium, the percentage nitrogen and the mean grain size were identified as the most important variables influencing the community structure by the BIOENV BEST routine in PRIMER. The trace metals and percentage nitrogen only had negative effects on the diversity and abundance as well as on the abundance of the dominant genera, whereas the mean grain size had variable effects.</p>

Studies have been carried out on specific ion-exchange (Dowex 50W-X8 and Dowex 1-X8) and chelation (Chelex-100) resins, in order to determine their physical and chemical characteristics, to understand and explain their limits of function and to optimise their use as substrates in trace metal and speciation measurement by EDXRF. Structural information was obtained by scanning electron microscopy and x-ray microanalysis showing a homogeneous distribution of functional groups and retained ions on both sectioned and whole resins. Particle size experiments performed on Dowex 50W-X8 (38 - 840 µm) showed that this parameter has no effect on the relationship between intensity of fluorescence and concentration or mass of resin. Inter-element effects were not observed in the analysis of multielemental specimens prepared on ion-exchange / chelation media by EDXRF. This indicates that the proposed method has a significant advantage when compared with other methodologies. A theoretical ‘model’, based on the formation of thin films on the surface of the resin beads, has been proposed in order to link and explain the effects observed in these experiments. The use of a batch retention system has shown distinct advantages over using columns in terms of linearity, accuracy, precision, rapidity and simplicity. Parameters such as pH and ionic strength of the solution, concentration of competing ions and volume of the sample have been proven to be critical. The maximum retention capacity has been determined as 3.2, 1.1 and 0.67 mEq/g for Dowex 50W-X8, Dowex 1-X8 and Chelex-100 respectively. The optimum mass of resin for XRF analysis was found to be 0.5 g, for all resins tested. The linear range covered 4 to 5 orders of magnitude. These findings show the potential of the investigated media to overcome instrumental and sample limitations. Based on the physico-chemical information found, methodologies for three different applications of the resins to EDXRF determinations have been developed and their analytical possibilities explored. The multi-elemental determination of metals in sewage sludge digests was achieved by retaining the metals on Dowex 50W-X8 at pH 2 and Chelex-100 at pH 4. Chelex-100 allows quantitative recoveries for Cu and Zn. A wider range of elements was determined on Dowex 50W-X8, although with poorer recoveries (60 - 90%). The limits of detection were 10 - 21 µg when Dowex 50W-X8 was used and 8 - 49 µg for Chelex-100. The method was validated by the analysis of a certified material. The determination of Kβ/Kα intensity ratios for Cr and Mn species and its potential as a tool for direct elemental speciation has also been studied. A difference in Kβ/Kα between the oxidation states of the analytes was only observed during the analysis of solutions of the metal species by EDXRF at the 98% level of confidence. Finally, the speciation and preconcentration of Cr(III) and Cr(VI) in waters has been performed by retention on Dowex 50W-X8 and Dowex 1-X8 followed by EDXRF determination. Efficient recoveries and preconcentration factors of up to 500 were achieved, leading to limits of detection of 30 µg/L for Cr(VI) and 40 µg/L for Cr(III). This method is simple, fast and inexpensive, allowing quantitative recoveries in the speciation of chromium in waste waters.

Submitted by Ana Hilda Fonseca (anahilda@ufba.br) on 2016-08-30T17:05:18Z No. of bitstreams: 1 Dissertação - Darlan S Santil.pdf: 1852568 bytes, checksum: 56dd8cda0c9cfac1cef7ea49ee2facfb (MD5) / Approved for entry into archive by Vanessa Reis (vanessa.jamile@ufba.br) on 2016-09-02T15:26:24Z (GMT) No. of bitstreams: 1 Dissertação - Darlan S Santil.pdf: 1852568 bytes, checksum: 56dd8cda0c9cfac1cef7ea49ee2facfb (MD5) / Made available in DSpace on 2016-09-02T15:26:24Z (GMT). No. of bitstreams: 1 Dissertação - Darlan S Santil.pdf: 1852568 bytes, checksum: 56dd8cda0c9cfac1cef7ea49ee2facfb (MD5) / CAPES / O presente estudo propõe a determinação de elementos maiores e traço em invertebrados marinhos por Espectrometria de Emissão Óptica com Plasma Indutivamente Acoplado (ICP OES) após um procedimento assistido por radiação ultrassom e centrífuga, empregando ácidos diluídos. Um planejamento Doehlert de três fatores foi aplicado para otimizar a extração dos elementos nas amostras de bivalves (Mytella guyanensis, Anomalocardia brasiliana e Crassostrea rhizophorae). Os fatores foram: concentração da mistura ácida (HCl + HNO3 + H3CCOOH; 1-3 mol L-1), tempo de centrifugação (10-40 min.), e velocidade de rotação (6000-10000 rpm). A eficiência de extração expressa em percentual foi escolhida como resposta analítica no processo de otimização. Além disso, todos os experimentos foram realizados analisando o material de referência certificado NIST 1566b (tecido de ostra). O percentual de recuperação obtida nas amostras de material de referência certificado pela martiz Doehlert variou de 45-95, 8-52, 35-71, 67-102, 38-78, 61-92, 58-100, 39-85 e 51-91%, respectivamente, para Ca, Cd, Cu, K, Mg, Mn, Na, Sr, e Zn. Todavia, ponto de máximo não foi obtido. Portanto, a resposta múltipla foi escolhida para obtenção dos valores máximos de extração dos metais. As seguintes condições experimentais da resposta múltipla foram selecionadas: 20 min de tempo de extração, 9000 rpm de velocidade de rotação e 1,0 mol L-1 da mistura ácida. A fim de avaliar o efeito do ultrassom na extração dos elementos, uma porção de tecido de ostra certificado foi sonicada por 15 min em um banho de ultrassom à temperatura ambiente e a solução foi centrifugada nas condições otimizadas. Os resultados mostraram que o uso da sonicação antes da centrifugação promoveu um aumento na porcentagem de recuperação dos elementos estudados. A repetitividade do procedimento auxiliado por centrífuga e ultrassom foi avaliada pela determinação de elementos maiores e traço em 10 replicatas do material certificado. Os desvios padrões relativos (RSD) para o procedimento proposto variam entre 1,8 a 4,7. A exatidão do método foi confirmada pela análise de tecido de ostra certificado (NIST 1566b) e por comparação de método analítico de referência com procedimento de digestão ácida para o tratamento das amostras (microondas com cavidade). Os resultaldos da análise da exatidão de alguns elementos estudados mostraram que não havia diferenças significativas (p<0,05) entre o método proposto e o método de referência. Concomitantemente ao desenvolvimento do método analítico, as concentrações dos elementos menores e maiores em amostras dos bivalves coletados ao longo da Baía de Todos os Santos, Bahia, Brasil foram determinadas por ICP OES após o procedimento de digestão ácida em bombas Parr. Os resultados da determinação revelaram que as concentrações de As, Cu e Zn nos bivalves estavam acima dos limites máximos estabelecidos pela ANVISA e por agências especializadas em saúde internacionais. Esses valores de concentração sugerem que deve ser feita uma análise de risco a / The present study proposes the determination of major and trace elements in marine invertebrates by Inductively Coupled Plasma Optical Emission Spectroscopy (ICP OES) after a procedure assisted by ultrasound radiation and centrifugal, employing diluted acids. A three factor Doehlert design was applied to optimize the extraction of elements in bivalves (Mytella guyanensis, Anomalocardia brasiliana and Crassostrea rhizophorae). The factors were: concentration of acid mixture (HCl + HNO3 + H3CCOOH; 1-3 mol L-1), centrifugation time (10-40 min.), and rotation velocity (6000-10000 rpm). The extraction efficiency, expressed as a percentage, was chosen as the analytical response in the optimization process. In addition, all experiments were performed by analyzing the certified reference material NIST 1566b (oyster tissue). The percentage of recovery obtained in the samples of certified reference material by Doehlert varied from 45-95, 8-52, 35-71, 67-102, 38-78, 61-92, 58-100, 39-85 and 51-91%, respectively, for Ca, Cd, Cu, K, Mg, Mn, Na, Sr, and Zn. However, maximum point wasn’t obtained. So, the multiple response was chosen to obtain the maximum extraction of the metals. The following experimental conditions of multiple response were selected: 20 min of extraction time, 9000 rpm of the speed centrifuge and 1.0 mol L-1 of the acid mixture. In order to evaluate the ultrasound effect on the extraction of trace elements a portion of the certified oyster tissue sample was sonicated for 15min in an ultrasonic bath at ambient temperature, and then the solution was centrifuged at the optimized conditions. Results showed that the use of the sonication prior to the centrifugation promoted an increase in the percentage of recovery for most studied elements. The repeatability of the centrifugation and ultra- sound assisted procedure was evaluated by the determination of trace and major elements in 10 replicates of the oyster tissue certified material. The relative standard deviations (RSD) for the centrifugation and ultrasound assisted procedure varied between 1.8 and 4.7%. The accuracy of the method was confirmed by analysis of the certified oyster tissue (NIST 1566b) and by reference analytical method comparison with acid digestion procedure for the sample treatment (microwave cavity). The results of the analysis of the accuracy of some elements studied showed that there were no significant differences (p <0.05) between the proposed method and the reference method. Concurrent with the development of the acid extraction procedure, the major and trace concentrations of elements in mussel, oyster and clams samples collected from along coastal the zones of Todos os Santos Bay were determined by ICP OES after Parr acid digestion bombs. The results of determination showed that concentrations of As, Cu and Zn in the bivalves were above the limits established by ANVISA and international agencies specializing in health. These concentration values suggest that must be a health risk analysis mainly in the communities that collect the shellfish as a subsistence activity.

En période hivernale, des fondants routiers sont épandus sur les chaussées afin de préserver la sécurité des usagers. Sous l'influence de divers paramètres, ces produits se retrouvent en partie dans l'environnement, le reste étant collecté par des systèmes de rétention des eaux de ruissellement routières. Or, les bassins de rétention ne sont pas conçus pour traiter ces fondants, et jouent uniquement un rôle de régulation des flux rejetés dans l’environnement. L’effet du NaCl sur l’environnement est néfaste, en raison de sa toxicité directe envers certains organismes et, indirectement parce qu’il contribue à augmenter la mobilité des ETM (Éléments Traces Métalliques), eux-mêmes toxiques. Ceci démontre un besoin d'assainissement particulier pour ces produits. L'objectif de cette thèse est d'étudier les transferts de NaCl par un bassin de rétention, mais également d'investiguer la possibilité d'utiliser la phytoremédiation comme base d'une solution d'assainissement des eaux de ruissellement routières. Le bassin de rétention choisi comme modèle est un bassin récent situé à Chenevières (Lorraine, France), en bordure d’une route nationale. La première partie du travail a porté sur la mesure et la caractérisation des transferts de NaCl dans ce bassin. L’eau a été collectée en entrée/sortie chaque semaine pendant 3 ans, et les concentrations en NaCl et ETM mesurées. Les conditions météorologiques et les données d’épandage de sel ont été suivies pour évaluer la proportion de sel effectivement transférée vers le réseau de collecte des eaux de ruissellement routières. Les résultats montrent que 25 à 50 % du sel épandu est effectivement collecté. De plus, les résultats sur la dynamique du NaCl prouvent que le bassin joue uniquement un rôle de rétention temporaire et de dilution avant rejet vers l’environnement. Ensuite, des mesures et analyses des sédiments du bassin et des sols de bord de route ont été conduites pour caractériser la spéciation et la mobilité des ETM dans ce contexte routier particulier. Dans ce cas précis, le NaCl n’a pas eu d’effet significatif sur la mobilisation des ETM, hormis le zinc (Zn). En revanche, il a provoqué la mobilisation d’autres ions majeurs. Concernant le traitement, les procédés conventionnels de dessalement d’eau sont trop coûteux et inadaptés. C’est pourquoi les potentialités d’une solution d’assainissement par phytoremédiation ont été explorées. Trois plantes halophytes ont été sélectionnées selon des critères permettant leur utilisation en contexte routier, Armeria maritima, Atriplex halimus et Atriplex hortensis L. Des expériences de germination/croissance ont été effectuées dans différentes conditions de salinité et de concentration en Zn pour évaluer leur tolérance à la salinité, à la présence de Zn et leurs capacités d’accumulation. Ces plantes ont montré une tolérance au NaCl dans des conditions de salinité représentatives de celles mesurées dans les réseaux d’assainissement routiers à Chenevières. De plus, les trois espèces accumulent dans leurs parties aériennes des quantités significatives de NaCl, ainsi que du zinc. L'utilisation des halophytes pour la phytodésalinisation en domaine routier s'avère être une technologie prometteuse pour répondre à la problématique de l'impact environnemental des fondants routiers. / During winter, deicing salts are spread on roads in order to preserve road safety for users. Under the influence of different parameters, these compounds are partly transferred to the environment, the rest of it being collected by the road runoff retention systems. However, road runoff retention ponds have not been designed for deicing salt treatment; they only play a role in the regulation of fluxes before their rejection into the environment. Furthermore, NaCl has a harmful impact on the environment, because of its toxicity to certain aquatic organisms and because it contributes to the increase of trace metal (TM) mobility, which are toxic as well. This shows the need for a specific treatment for these compounds. The objective of this research is to bring better understanding of deicing salt dynamics in a retention pond, but also to investigate the potential use of phytoremediation as a treatment solution for road runoff. A model retention pond was selected; it is located along a highway in Chenevières (Lorraine region, France). The first part of the work focused on the monitoring and the characterization of NaCl transfers in this pond. Water was weekly sampled for 3 years at the pond input and output and NaCl and TM concentrations were measured. Meteorological conditions and salt spreading data were monitored to appraise the salt fraction actually collected by the pond. Results showed that only 25 to 50 % of the spread salt is effectively collected. Moreover, results on NaCl dynamics proved that the pond only plays a role on transient storage and salt dilution before rejection into the environment. Moreover, measurements and analyses of sampled basin sediments and roadside soils were performed to assess speciation and TM mobility in this particular context. In this case, no significant effect of NaCl was recorded except for zinc (Zn); but major ions were mobilized. When it comes to treatments, conventional desalination technologies are too expensive and inappropriate in this context. Then, potentialities of phytodesalination were explored. Three halophyte plants were selected on the basis of specific criteria, allowing their use in road runoff context: Armeria maritima, Atriplex halimus and Atriplex hortensis L. Germination and growth experiments were run in various salinity conditions and in the presence/absence of Zn, in order to assess their tolerance to salt and Zn, as well as their accumulation abilities. These plants showed a high tolerance for NaCl in salinities in the range of those encountered in road runoff existing treatment systems at Chenevières. The three species accumulated significant amounts of NaCl and zinc in their aerial parts. The use of halophytes for phytodesalination of road runoff is a promising technique to address the issue of environmental impact of deicing salts.

Microphytobenthos (MPB), a mixed community of microscopic, photosynthetic organisms, algae and cyanobacteria, inhabiting the top few millimetres of bottom sediment, is a key component of intertidal mudflats. It accounts for a significant proportion of estuarine primary production, forms the base of the food chain and influences sediment distribution and resuspension (through production of extracellular polymeric substances (EPS)). Diatoms dominate the microphytobenthos community in the mid-latitudes of the Northern Hemisphere. Estuarine sediments, are a sink for metal contaminants derived from fluvial, marine and atmospheric sources. Whilst metal releases to estuaries have declined in recent years due to increased regulation and declining industrial activity, metals previously discharged and which are now locked up in saltmarsh sediments remain a concern. For example, there are indications that saltmarshes are already being eroded, due to climate change related sea level rise, in some locations. This erosion may result in the redistribution of historically contaminated sediment to locations, such as the mudflats, where it is more available to biota, such as the MPB. In addition to causing redistribution, climate change effects, such as increasing temperatures and storminess, may also alter the bioavailability of metals to MPB. Increased concentrations of metals within the MPB could potentially increase their transfer to higher organisms through the food chain with potential impacts for biota. Whilst planktonic algae have been well studied with respect to metal uptake from the water column, there has been little research involving MPB and uptake of metals from sediment. The extent to which contaminant uptake by microphytobenthic algae occurs and under what conditions is therefore poorly understood. The research presented uses laboratory, mesocosm and field studies, to gain an understanding of processes governing metal bioavailability and mechanisms for uptake from sediment to the diatoms of the MPB under the complex and variable conditions of intertidal mudflats. A laboratory study using a single diatom species Cylindrotheca closterium found that uptake of cadmium (Cd) varied with sediment properties revealing the importance of sediment particle size and organic matter content in metal bioavailability to diatoms. Additionally, this study showed that the presence of diatoms altered Cd partitioning between sediment, overlying and pore water. Specifically there was an increase in Cd in the overlying and pore water when diatoms were present, indicating that diatoms mobilise metals from the sediment to the water column potentially increasing metal bioavailability to other biota. A study was conducted using an intertidal mesocosm to increase the realism of the study system and examine uptake to a natural MPB community. Diatoms were found to have higher concentrations of all the metals analysed (except tin) than other types of algae (filamentous and sheet macroalgae), confirming their importance as a study organism with respect to metal uptake and potential mobilisation through the food chain. Sediment disturbance was shown to increase metal uptake (iron, aluminium, vanadium and lead) from the sediment to algae. This is of concern due to predicted increases in storminess which are likely to increase sediment disturbance, with the likelihood that uptake of metals to diatoms will increase in the future. However, there were also indications of an antagonistic effect of temperature on disturbance, whilst disturbance increased bioavailability and uptake, increasing temperatures reduced uptake of some metals. This highlights the importance of considering the effects of multiple stressors in complex systems. Field studies showed that concentrations of some metals were related to their position on the mudflat whilst others were related to sampling date, indicating that there may be seasonal controls, such as to the presence of greater diatom biomass in spring and autumn, on metal uptake from the sediment. The research conducted has increased understanding of metal uptake to microphytobenthic diatoms from sediment and the influence they have in transferring metals from sediment to water, however the research also raises a number of new questions. For example, there appeared to be a link between sediment organic matter content and bioavailability of metals to diatoms, although the relative contribution of the diatoms, other algae, cyanobacteria and EPS to the sediment organic matter warrants further investigation. Furthermore, it has shown that the use of laboratory and mesocosm studies for this type of research can produce similar outcomes to those observed in the field but under more controlled and easily manipulated conditions, although field studies will continue to be vital in improving understanding of metals availability and transfer.