L’industrialisation de l’étang de Berre au cours du 20ème siècle s’est accompagnée d’importants rejets en éléments traces métalliques (ETM) qui ont été en partie accumulés dans les sédiments et sont aujourd’hui susceptibles d’être remobilisés vers la colonne d’eau ou d’être intégrés dans le réseau trophique et d’entrainer un risque écotoxicologique.La reconstitution de l’évolution temporelle et spatiale de la contamination des sédiments montre que les niveaux de contaminations actuels des sédiments de surface sont les plus bas depuis plusieurs décennies en lien avec l’efficacité des réglementations sur les rejets industriels mises en place dans les années 1970. Ces niveaux sont faibles à modérés en surface mais de très fortes contaminations existent quelques centimètres sous la surface des sédiments.Le rôle des oxy-hydroxydes de Fe ou de Mn et des sulfures dans le contrôle de la mobilité des ETM dans le sédiment et leurs flux à l’interface eau/sédiment a pu être démontré grâce à la modélisation du transport et des réactions des composés chimiques et des ETM dans les eaux interstitielles, de leurs profils de concentrations dans la fraction réactive de la phase particulaire et d’expérimentations en conditions contrôlées au laboratoire. L’oxygénation de la colonne d’eau constitue le principal paramètre influençant cette mobilité et ces flux, et l’influence d’une réoxygénation des fonds dans le Grand Etang est discutée.Enfin, la biodisponibilité des ETM et le stress (géno)toxicologique qu’ils peuvent constituer pour un organisme benthique cible, le polychète Nereis succinea, ont été évalués par l’estimation des fractions potentiellement biodisponibles dans les sédiments (extractions chimiques et Diffusive Gradient in Thin-films), par la mesure des concentrations bioaccumulées et par l’utilisation de biomarqueurs de défense (métallothionéines) et de dommages (tests de génotoxicité). Certains ETM qui sont fortement bioaccumulés représentent un risque potentiel et pourraient être impliqués dans la dégradation de la macrofaune benthique. / The industrialization of the Berre lagoon in the 20th century was accompanied by large releases trace metals, which were partially accumulated in sediments and are now likely to be remobilized to the water column or be integrated into the food chain and cause an ecotoxicological risk.The reconstruction of the temporal and spatial trends of sediment contamination shows that current levels of contamination of surface sediments have been the lowest for decades in agreement with the effectiveness of regulations on industrial releases set up in the years 1970. These levels are low to moderate in surface but very high contamination exist a few centimeters below the sediment surface.The role of Fe and Mn oxy-hydroxides and sulfides in controlling the mobility of ETM in the sediment and fluxes at the water/sediment interface has been demonstrated through the modeling of transport and reactions of chemical compounds and trace metals in the pore waters, their concentration profiles in the reactive fraction of the particulate phase and experiments under controlled laboratory conditions. The oxygenation of the water column is the main parameter influencing the mobility and fluxes and the influence of reoxygenation of bottom water column in the Grand Etang is discussed.Finally, the bioavailability of trace metals and adverse effects they may constitute for a target benthic organism, the polychaete Nereis succinea, were evaluated by estimating the potentially bioavailable fraction in sediments (chemical extractions and Diffusive Gradient in Thin-films), by measuring bioaccumulated concentrations and by the use of biomarkers (metallothioneins and genotoxicity assays). Some highly bioaccumulated trace metals pose a potential risk and might be involved in the degradation of the benthic macrofauna.

Os setores sul e norte do complexo estuarino lagunar de Cananéia-Iguape, sujeitos a diferentes pressões antrópicas, foram estudados quanto às características hidrológicas e hidroquímicas das águas de superfície e fundo, com ênfase às concentrações de zinco, cádmio e chumbo dissolvidos. A amostragem contou com coletas espaciais e temporais, em dois períodos sazonais (outono e primavera) de 2007. Os metais estudados foram: o zinco, devido ação tóxica ou como micronutriente, dependendo de sua concentração, o cádmio e o chumbo, considerados sem função biológica positiva conhecida e com alto grau de toxicidade para a biota. A metodologia utilizada na determinação da concentração dos metais traço foi a voltametria por redissolução anódica. No setor sul, a variação da salinidade foi característica de um sistema estuarino não impactado. Os teores dos metais traço encontrados sofreram variação entre 0,040 e 0,509 ?g L-1 para o zinco, 0,001 e 0,024 ?g L-1 para o cádmio e entre 0, 030 e 0,175 ?g L-1 para o chumbo. No setor norte, a variação salinidade mostrou forte influência de água doce. O zinco sofreu variação entre 0,097 e 0,257 ?g L-1, o cádmio entre 0,004 e 0,024 ?g L-1 e o chumbo 0,033 e 0,259 ?g L-1. Nos dois setores, as concentrações dos metais traço estiveram sempre abaixo dos limites propostos pela legislação ambiental brasileira (CONAMA) e norte-americana (EPAUSA). O presente estudo mostrou um maior do impacto antrópico na região norte, com potencial de exportação para o setor sul e plataforma. As maiores concentrações dos metais traço estudados ocorreram nas águas de fundo, mais próximas à interface com o sedimento. O setor sul, sujeito a uma variação da salinidade mais definida, mostrou maior potencial para a remobilização dos metais traço para a coluna de água com o movimento de maré. O estudo dos ciclos biogeoquímicos dos metais traço deve ser incentivado no monitoramento ambiental da região. / The south and north regions of Cananeia-Iguape estuarine-lagoon system submitted to different anthropic pressures were studied to evaluate their hydrological and hydrochemical characteristics mainly considering the concentrations of dissolved zinc, cadmium and lead. The sampling included spatial and temporal samples obtained in two seasons (autumn and spring) of 2007. The metals studied were zinc as a toxic agent and micronutrient depending on the concentration and cadmium and lead with no biological positive relevance and high toxicity to the biota. The methodology used in the trace metals determination was anodic stripping voltammetry. In the south portion the salinity variation was characteristic of non-impacted estuaries. The zinc concentrations ranged from 0,040 to 0,509 ?g L-1. The cadmium ranged from 0,001 to 0,024 ?g L-1. The lead content ranged from 0,030 to 0,175 ?g L-1. In the north portion, the salinity variation showed high influence of fresh water. The zinc concentrations ranged from 0,097 to 0,257 ?g L-1. The cadmium concentrations ranged from 0,004 to 0,024 ?g L-1. The lead values ranged from 0,033 to 0,259 ?g L-1. The concentration of trace metals on both portions were below the limits proposed by the Brazilian environmental law (CONAMA) and North American (EPAUSA) legislation. The present study revealed higher anthropic impact in the north region with exporting potential to the south and to the continental shelf. Higher trace metals concentrations were observed in the bottom waters near to the sediment interface. The south region, submitted to most defined tide movements, showed an important potential for trace metals remobilization to the water column. The trace metals biogeochemistry cycles study should be enhanced for better environmental monitoring.

The Late Cretaceous–early Paleogene is the most recent period of Earth history with a dynamic carbon cycle that experienced sustained global greenhouse warmth and can offer a valuable insight into our anthropogenically-warmer future world. Yet, knowledge of ambient climate conditions and evolution of the carbon cycle at this time, along with their relation to forcing mechanisms, are still poorly constrained. In this thesis, I examine marine sediments recovered from the South Atlantic Walvis Ridge (ODP Site 1262) and Indian Ocean Ninetyeast Ridge (IODP Site U1443 and ODP Site 758), to shed new light on the evolution of the climate and carbon cycle from the Late Maastrichtian through to the Early Eocene (~67.10–52.35 Ma). The overarching aims of this thesis are: 1) to identify the long-term trends and principle forcing mechanisms driving the climate and carbon cycle during this time period, through construction of 14.75 million-year-long, orbital-resolution (~1.5–4 kyr), stratigraphically complete, benthic stable carbon (δ13Cbenthic) and oxygen (δ18Obenthic) isotope records; 2) to investigate in more detail the climatic and carbon-cycle perturbations of the Early–Middle Paleocene (e.g., the Dan-C2 event, Latest Danian Event and the Danian/Selandian Transition Event) and place these in their proper (orbital) temporal context; 3) to investigate the Late Maastrichtian warming event and its relationship to the eruption of the Deccan Traps Large Igneous Province, as well as its role (if any) in the subsequent Cretaceous/Paleogene (K/Pg) mass extinction; 4) to provide the first orbital-resolution estimates of temperature and carbonate chemistry variability from the low latitude Indian Ocean spanning the Late Paleocene–Early Eocene, through analysis of trace element and stable isotope data from multiple foraminiferal species. Taken together, the results presented in this thesis provide a critical new insight into the dynamic evolution of the climate and carbon cycle during the greenhouse world of the early Paleogene, and shed light on the potential forcing mechanisms driving the climate and carbon cycle during this time.

Les potentiels de nouveaux moyens d’investigation en sciences de l’environnement, tel que la géochimie des isotopes stables du Cu et du Zn et l’étude de la spéciation des éléments en trace métalliques (ETM) par titrage acidimétrique sont évalués dans le cadre de trois cas d’études, faisant intervenir des matériaux de matrices et de concentrations en ETM variables. Afin de mettre en évidence de très subtiles variations des compositions isotopiques du Cu et du Zn dans les matériaux particulaires variablement pollués, une attention particulière à été voué à la mise au point des méthodes de séparation chimique et d’analyse par MC-ICP-MS. La méthodologie analytique a été développée afin d’exploiter tout les avantages techniques offerts par le spectromètre de masse à l’ULB. Différents modes d’introduction (plasma humide vs plasma sec (Aridus/DSN), d’acquisition des mesures (mode statique ou dynamique) de correction du biais de masse (dopage au Cu, au Zn et au Ga; correction SSBM, SSBC et EEN)ont été évaluées, pour leurs effets sur la précision et la reproductibilité des mesures. D’autres travaux ont permis de quantifier les effets des interférences spectrales et non spectrales par les éléments de la matrice (Ti, Cr, Co,Fe, Ba, Si, Na, Mg et Ca) et par le rapport dopant/analyte en vue de comprendre les sources d’inexactitudes des mesures isotopiques et d’y remédier. Les données isotopiques acquises sur des minerais, sur des (plaques de) dépôts atmosphériques (usine Pb-Zn Metaleurop de Noyelles-Godault), sur des sédiments et des matières en suspension (estuaire de l’Escaut et mer du Nord), révèlent des variations significatives des compositions isotopiques du cuivre et du zinc. Dans l’estuaire de l’Escaut, les variations temporelles (carotte non perturbée, enregistrant la sédimentation sur 30 ans) et spatiales (matières en suspension échantillonnées sur 100 km, selon le profil de salinité) sont caractérisées par des signatures isotopiques en Zn anticorrélées à celle du Cu. Les données peuvent permettre de distinguer le fond géochimique naturel (le « réservoir naturel »), les pollutions diffuses (le « réservoir anthropique commun »- intégrant de multiples sources de contamination en provenance du bassin versant) et certaines pollutions ponctuelles associées à la métallurgie du Zn. Alors que les procédés utilisés en métallurgie sont eux,capable de produire des signatures isotopiques très fractionnées en Zn, ni la diagenèse précoce dans les sédiments, ni les gradients physicochimiques développés lors du mélange des eaux continentales et marines ne sont capables d’affecter significativement la signature isotopique du Cu et du Zn en phase particulaire. Dans de tels milieux, les signatures isotopiques en Cu et Zn (ainsi que celles en Pb) semblent n’être contrôlées que par le mélange conservatif entre le « réservoir naturel » et le « réservoir anthropique commun ». Les données en elles-mêmes constituent la seule base de données isotopiques en Cu, Zn, Pb dans des matériaux particulaires anthropisés estuariens et marins jamais produite à ce jour. Elles permettent de prédire que la signature isotopique en Cu du « réservoir naturel » devrait être légèrement plus enrichie en isotopes lourds que celle du réservoir « anthropique commun » (par analogie au Zn). Si la géochimie isotopique du Cu et du Zn a le potentiel de distinguer différentes sources de pollution, l’évaluation des risques liés à ces pollutions doit tenir compte des formes chimiques des ETM, typiquement mises en évidences par les méthodes d’extraction sélectives (séquentielles, dont le protocole BCR). La méthode alternative proposée pour l’étude de la spéciation, plus versatile (capable de mettre en évidence des phases non prédéfinies et applicable à une variété de matrices plus large) est capable de surmonter plusieurs limitations (dont les problèmes de sélectivité liées au mauvais contrôle de l’acidité du milieu réactionnel) caractéristiques des méthodes traditionnelles. Appliquée à des sédiments marins/estuariens et des sols, la méthode de titrage acidimétrique s’est révélée capable de quantifier les proportions relatives des phases acido-solubles (principal problème des méthodes d’extraction sélectives), ce qui permet d’établir univoquement la spéciation des éléments qui leurs sont associés, d’évaluer la réactivité des ETM vis-à-vis du pH, mais aussi d’évaluer la sélectivité des protocoles d’extraction séquentielle « BCR » et « Tessier ». La méthode de titrage acidimétrique apporte également des informations importantes sur la géochimie des éléments majeurs dans l’estuaire de l’Escaut et met en évidence les particularités minéralogiques des sols pollués en comparaison aux sédiments. Les études de cas démontrent que ces nouvelles techniques ont des applications dans le domaine de la géochimie de l’environnement, mais peuvent également être vouées, sur le moyen/long terme à une utilisation sortant du cadre des sciences exactes. En effet, l’identification/ discrimination des sources de pollutions et l’évaluation des risques de remobilisation des polluants métalliques font partie des nombreuses questions posées par la société aux scientifiques de l’environnement.

This doctoral thesis deals with the biogeochemical processes taking place in estuarine systems known as 'rias', located at the NW of the Iberian Peninsula. Its realization has been possible thanks to financial support from the JAE-Program of the Spanish Council for Scientific Research (CSIC) co-funded by the European Social Fund (ESF), and the ‘INTERESANTE' project, funded by the CICYT. Additionally, it is a contribution to the Spanish LOICZ program (Land-Ocean Interactions in the Coastal Zone). An oceanographic characterization of the Northern Galician Rias is presented in Chapter 2. This chapter also involves an extensive analysis of summer upwelling and downwelling processes, winter shelf-water upwelling, and poleward intrusion in the northern Galician shelf. Chapter 3 deals with the fluvial contributions to the Northern Galician Rias, including the quantification of major and minor chemical elements (nutrient salts, trace elements) in the dissolved and particulate matter, chlorophyll-a, DIN, PON, DOC, POC and C/N ratio. In Chapter 4 the sediment-water fluxes of nutrients in a ria coastal systems are discussed. Fluxes driven by molecular diffusion and advective transport across sediment-water interfaces during tidal flooding for the Northern Galician Rias are calculated. Chapter 5 focuses on the hydrological, chemical and biological interactions in the Northern Galician Rias, exemplified by the case of the Ria of Barqueiro, identifying their oceanographic periods in relation to nutrient availability, primary production, phytoplankton biomass, taxonomic composition and hydrographic patterns.

In South Africa, being the second largest global coal exporter, coal mining plays a pivotal role in the growth of our economy, as well as supplying our nation’s ever increasing electricity needs; while also accounting for more than 10% of the 20 x 109 m3 water used annually in the country. Coal mining may thus be classified as a large-scale water user; known to inevitably generate wastewater [acid mine drainage (AMD)] and other waste material, including fly ash (FA). Current and conventional AMD treatment technologies include precipitation–aggregation (coagulation/flocculation) – settling as hydroxides or insoluble salts. The process stream resulting from these precipitation processes is still highly saline, therefore has to undergo secondary treatment. The best available desalination techniques include reverse osmosis (RO), electro dialysis (ED), ion exchange and evaporation. All available treatment methods associated with raw AMD and its derived process stream fall prey to numerous drawbacks. The result is that treatment is just as costly as the actual coal extraction. In addition, remediation only slows the problem down, while also having a short lifespan. Research conducted into converting fly ash, an otherwise waste material, into a marketable commodity has shown that direct mixing of known ratios of FA with AMD to a pre-determined pH, erves a dual purpose: the two wastes (AMD and FA) could be neutralized and produced a much cleaner water (secondary co-disposal [FA/AMD]-process water), broadly comparable to the process water derived from precipitation-aggregation treated AMD. The collected post process solid residues on the other hand, could be used for production of high capacity ion exchange material (e.g. zeolite A, faujasite, zeolite P, etc.). The produced ion exchange material can subsequently be utilized for the attenuation of metal species in neutralized FA/AMDprocess waters. / Magister Scientiae - MSc

Made available in DSpace on 2014-12-17T14:08:31Z (GMT). No. of bitstreams: 1 LucianaAN.pdf: 2077489 bytes, checksum: 1da1ee4e46ae44cfe82f45be75eac385 (MD5) Previous issue date: 2008-09-19 / It is located in an area of increasing oil exploration, the region of the Lower A?u is at the mercy of a possible pollution generated by this economic activity, which includes various chemical substances harmful to health, such as metals. This thesis aims to, diagnose the areas of River Piranhas-A?u, a region of the Lower A?u, which are polluted by traces factors and more. In this study, it was determined the concentration of the chemica elements Al, CD, Cr, Cu, Fe, Mn, Ni, P, Pb, V and Zn, through the technique of ICP-OES analysis and the size of sediments and their contents organic matter. Were mapped by GPS, 12 points from collections. The interpretations of the results, together associating that allowed pollution to a possible contamination by oil activity. The results showed tha some regions have low concentrations of cadmium, lead, copper, manganese and zinc unable to promote damage to human health. However, there are places where the concentrations of certain metals chromium, iron and zinc are moderately polluted compared to the results with the reference values of literature and others that are highly polluted by iron. However, due to a greater number of wells in production in those locations, those higher concentrations, it can be suggested a possible influence of oi production in some areas with concentrations of chromium and lead are higher than the rest of the points of monitoring. Moreover, it is observed that the highest levels of metals found in sediment of finer texture and more organic matter content / Por estar situada em uma ?rea de crescente explora??o petrol?fera, a regi?o do Baixo A?u encontra-se ? merc? de uma poss?vel polui??o gerada por esta atividade econ?mica, que inclui diversas subst?ncias qu?micas prejudiciais ? sa?de, tais como os metais. Esta disserta??o tem como objetivo, diagnosticar as ?reas do Rio Piranhas-A?u, regi?o do Baixo A?u, que se encontram polu?das por elementos maiores e tra?os. Neste estudo, determinou-se a concentra??o dos elementos qu?micos Al, Cd, Cr, Cu, Fe, Mn, Ni, P, Pb, V e Zn, atrav?s da t?cnica de ICP-OES e das an?lises granulom?tricas dos sedimentos e seus respectivos teores de mat?ria org?nica. Foram mapeados por GPS, 12 pontos de coletas. As interpreta??es dos resultados, em conjunto, possibilitaram associar essa polui??o a uma poss?vel contamina??o pela atividade petrol?fera. Os resultados mostraram algumas regi?es que apresentam baixas concentra??es de c?dmio, chumbo, cobre, mangan?s e zinco, incapazes de promover preju?zos ? sa?de humana. No entanto, h? localidades nas quais as concentra??es determinadas dos metais cromo, ferro e zinco s?o moderadamente polu?das, comparando-se esses resultados com valores de refer?ncia da literatura e outras que s?o altamente polu?das por ferro. No entanto, devido a uma maior quantidade de po?os em produ??o nessas localidades, essas maiores concentra??es, pode-se inferir uma poss?vel influ?ncia da produ??o de petr?leo em algumas ?reas cujas concentra??es de cromo e chumbo s?o mais elevadas que o restante dos pontos de monitoramento. Al?m disso, observa-se que os maiores teores de metais ocorrem em sedimento de textura mais fina e com maior teor de mat?ria org?nica

Le présent travail rentre dans le cadre du projet Hubert-Curien Tassili (PHC) entre l’université de Mostaganem et l’université de Perpignan, c’est une thèse de doctorat en cotutelle qui a comme objectif la contribution à l’étude de la contamination des eaux et des sédiments de l’Oued Chéliff et de ses deux affluents Oued Rhiou et Oued Mina. Cette étude a été abordée par un prélèvement saisonnier réalisé pendant deux périodes distinctes période humide et période sèche au niveau de 15 stations le long des cours d’eau. La qualité des eaux et des sédiments des cours d’eau a été déterminée par l’analyse des paramètres physico-chimiques, des métaux et des traceurs fluorescents.Les résultats obtenus ont montré une forte contamination en conductivité, DCO, DBO5 pendant la période humide et en Cl- et MES pendant la période sèche. Les résultats des métaux ont montré des concentrations importantes en Al, Fe et Ni particulièrement au niveau de l’Oued Chéliff et son affluent Oued Rhiou en période sèche. Cependant, Oued Mina présente des valeurs élevées de Li et de Sr. Les concentrations de types tryptophane, tyrosine et indole montrent des valeurs élevées au niveau des stations de rejets. L’évaluation de la qualité des sédiments de l’Oued Chéliff a montré que l’Oued Chéliff et son affluent Oued Rhiou sont caractérisés par la présence de fortes concentrations de Al, Mn, Fe, Cr, Ni, Pb pendant les deux périodes.Cette étude nous a permis de déduire que la qualité de l’eau et des sédiments de l’Oued Chéliff et de ses deux affluents a été altérée par les activités anthropiques et les phénomènes naturels. / The present thesis was carried out in co-tutelle between University of Mostaganem (Algeria) and University of Perpignan Via Domitia (France), it was partially funded through a PHC TASSILI project (15MDU937). It aims to study the quality of waters and sediments of Cheliff river and its two important tributaries Oued Rhiou and Mina rivers. During this work, seasonal samplings were performed for both water and sediment in 15 different stations along the watercourses during wet and dry.In order to evaluate the water and sediment quality of watercourses, several parameters were analyzed: the physicochemical parameters, fluorescence amino acids and trace metals. The study reveals a significant organic contamination along the watercourses with high concentrations of conductivity, COD, BOD5 during the wet period and Cl-, TSM during the dry period. The results of trace metals showed high concentrations of Al, Fe and Ni, particularly along the Cheliff and Oued Rhiou rivers during the dry period. On the other hand, Mina river presented high concentrations of Sr and Li. The presence of tryptophan like, tyrosine like and indole like in water samples revealed the impact of untreated urban discharges rejected into watercourses. Another part of the work is devoted to assess the quality of sediments of Cheliff river and its tributaries. The results show that the Cheliff river and its tributary Oued Rhiou are characterized through the presence of high concentrations of Al, Mn, Fe, Cr, Ni, Pb, during wet and dry periods. The present study has shown that the Cheliff river and its tributaries were strongly impacted by anthropogenic pollution and natural phenomenon.

Dans la région traversée par le plus important cours d’eau permanent d’Algérie l’Oued Cheliff, les déchets ménagers sont fréquemment mis en décharges à ciel ouvert, constituant une véritable menace environnementale à cause de la contamination causée par les lixiviats. Deux décharges ont été prises pour étude de cas : la première située sur l’Oued Hillil, affluent secondaire de l’Oued Chéliff et la deuxième localisée sur l’Oued Cheliff.Des prélèvements saisonniers d’eau et de sédiments ont été effectués dans les cours d’eau. Au sein de la décharge les lixiviats et les sols ont aussi été prélevés. L’impact des décharges a été évalué par l’analyse des paramètres physico-chimiques dans les liquides et des métaux dans tous les compartiments (eaux, lixiviats, sols et sédiments). L’analyse des traceurs fluorescents dans tous les compartiments est utilisée pour le suivi de la pollution urbaine.Cette étude a mis en évidence l’effet saisonnier important de l’impact des décharges sur les cours d’eau. Au printemps, les lixiviats présentes de fortes teneurs en traceurs fluorescents, Cr, Co, Mn, Ni issus de dépôt importants de déchets verts. En automne, ils reflétaient plutôt une contamination par NO2-, SO42-, PO43-, Fe, Cu, Cr provenant de résidus de produits agricoles (engrais, traitements phytosanitaires). Les eaux des deux cours d’eau sont très chargées en Cl- et Sr en toute saison dû à la nature saline des sols de la région.Les concentrations des métaux dans les sols des décharges sont largement supérieures à celles des sédiments fluviaux et révèlent une contamination métallique élevée (Cd, As, Zn, Cr, Pb), reflétant l’impact de déchets urbains (piles, batteries, plastiques…) / In the region crossed by the largest permanent watercourse of Algeria Oued Cheliff, household waste is frequently put in open dumps, constituting a real environmental threat because of the contamination caused by the leachates. Two landfills were taken for the case study: the first located on Oued Hillil, a secondary tributary of Oued Chéliff and the second located on Oued Cheliff.Seasonal sampling of water and sediment has been conducted in streams. In the landfill, leachates and soils were also collected. The impact of landfills was assessed by analyzing physico-chemical parameters in liquids and metals in all compartments (water, leachate, soils and sediments). The analysis of fluorescent tracers in all compartments is used for monitoring urban pollution.This study has highlighted the important seasonal effect of the impact of landfills on rivers. In the spring, leachates present high levels of fluorescent tracers, Cr, Co, Mn, Ni from large deposits of green waste. In autumn, they reflected rather NO2-, SO42-, PO43-, Fe, Cu, Cr contamination from residues of agricultural products (fertilizer, phytosanitary treatments). The waters of both rivers are heavily loaded with Cl- and Sr in any season due to the saline nature of the soils of the region.The concentrations of metals in landfill soil are much higher than those of river sediments and reveal a high metallic contamination (Cd, As, Zn, Cr, Pb), reflecting the impact of urban waste (batteries, batteries, plastics ...)

Os setores sul e norte do complexo estuarino lagunar de Cananéia-Iguape, sujeitos a diferentes pressões antrópicas, foram estudados quanto às características hidrológicas e hidroquímicas das águas de superfície e fundo, com ênfase às concentrações de zinco, cádmio e chumbo dissolvidos. A amostragem contou com coletas espaciais e temporais, em dois períodos sazonais (outono e primavera) de 2007. Os metais estudados foram: o zinco, devido ação tóxica ou como micronutriente, dependendo de sua concentração, o cádmio e o chumbo, considerados sem função biológica positiva conhecida e com alto grau de toxicidade para a biota. A metodologia utilizada na determinação da concentração dos metais traço foi a voltametria por redissolução anódica. No setor sul, a variação da salinidade foi característica de um sistema estuarino não impactado. Os teores dos metais traço encontrados sofreram variação entre 0,040 e 0,509 ?g L-1 para o zinco, 0,001 e 0,024 ?g L-1 para o cádmio e entre 0, 030 e 0,175 ?g L-1 para o chumbo. No setor norte, a variação salinidade mostrou forte influência de água doce. O zinco sofreu variação entre 0,097 e 0,257 ?g L-1, o cádmio entre 0,004 e 0,024 ?g L-1 e o chumbo 0,033 e 0,259 ?g L-1. Nos dois setores, as concentrações dos metais traço estiveram sempre abaixo dos limites propostos pela legislação ambiental brasileira (CONAMA) e norte-americana (EPAUSA). O presente estudo mostrou um maior do impacto antrópico na região norte, com potencial de exportação para o setor sul e plataforma. As maiores concentrações dos metais traço estudados ocorreram nas águas de fundo, mais próximas à interface com o sedimento. O setor sul, sujeito a uma variação da salinidade mais definida, mostrou maior potencial para a remobilização dos metais traço para a coluna de água com o movimento de maré. O estudo dos ciclos biogeoquímicos dos metais traço deve ser incentivado no monitoramento ambiental da região. / The south and north regions of Cananeia-Iguape estuarine-lagoon system submitted to different anthropic pressures were studied to evaluate their hydrological and hydrochemical characteristics mainly considering the concentrations of dissolved zinc, cadmium and lead. The sampling included spatial and temporal samples obtained in two seasons (autumn and spring) of 2007. The metals studied were zinc as a toxic agent and micronutrient depending on the concentration and cadmium and lead with no biological positive relevance and high toxicity to the biota. The methodology used in the trace metals determination was anodic stripping voltammetry. In the south portion the salinity variation was characteristic of non-impacted estuaries. The zinc concentrations ranged from 0,040 to 0,509 ?g L-1. The cadmium ranged from 0,001 to 0,024 ?g L-1. The lead content ranged from 0,030 to 0,175 ?g L-1. In the north portion, the salinity variation showed high influence of fresh water. The zinc concentrations ranged from 0,097 to 0,257 ?g L-1. The cadmium concentrations ranged from 0,004 to 0,024 ?g L-1. The lead values ranged from 0,033 to 0,259 ?g L-1. The concentration of trace metals on both portions were below the limits proposed by the Brazilian environmental law (CONAMA) and North American (EPAUSA) legislation. The present study revealed higher anthropic impact in the north region with exporting potential to the south and to the continental shelf. Higher trace metals concentrations were observed in the bottom waters near to the sediment interface. The south region, submitted to most defined tide movements, showed an important potential for trace metals remobilization to the water column. The trace metals biogeochemistry cycles study should be enhanced for better environmental monitoring.