Made available in DSpace on 2015-09-25T12:19:07Z (GMT). No. of bitstreams: 1 Ana Maria Alves da Silva.pdf: 1086889 bytes, checksum: a6694c8372c40371c39baa73bf55c15c (MD5) Previous issue date: 2008-12-19 / Sem resumo

Made available in DSpace on 2016-08-19T12:56:41Z (GMT). No. of bitstreams: 1 Dissertacao Edson Tobias.pdf: 1461674 bytes, checksum: a6907228d63cb84097969b52734d4104 (MD5) Previous issue date: 2013-10-25 / In order to assess the environmental impact and the behavior of phosphorus in the sediments of mangrove Tibiri River on the Maranhão island, five phosphorus fractions were determined (TP, IP, OP, AP) and NAIP in mangrove sediment, through sequential extraction according to the protocol of the European Commission (SMT - standards, measurements and testing Programme). Concentrations of the majority metals were also determined (Ca , Al , Mg , Fe and Mn) by inductively coupled plasma atomic with optic emission spectrometry (ICPAES) in the same extracts of cited above, moreover, mineralogical analysis of the mangrove sediment was made by X-ray diffraction. Sediments form Tibiri River showed phosphorus levels in the order of 341.44 mg.kg-1, characterized as an estuary with inexpressive impact of anthropogenic activities. Most phosphorus is found in the non-apatite inorganic fraction, (NAIP), mean 70%. The inorganic fraction of phosphorus, such as apatite mineral (PA) remained at 29%. Rio Tibiri was classified as unpolluted (PT < 500 mg kg-1), although most phosphorus is found as labile (mean 73.68%). Among the majority metals, Ca stood out by its association with the apatite fraction (AP), Corroboratig the presence of this mineral in the sediment. The main clay minerals found were kaolinite, montmorillonite , illite and quartz. / Com o objetivo de avaliar o impacto ambiental e o comportamento do fósforo nos sedimentos de manguezal do Rio Tibiri, na Ilha do Maranhão, foram determinadas cinco frações de fósforo (PT, PI, PO, PA e PINA) nas amostras de sedimentos de mangue do referido rio, através de extração sequencial de acordo com o protocolo da comissão europeia (SMT - Standards, Measurements and Testing Programme). Foram também determinadas concentrações dos metais majoritários (Ca, Al, Mg, Fe e Mn) por espectrometria de emissão atômica com plasma acoplado indutivamente (ICP OES) nos mesmos extratos de fósforos supracitados, além disso, foi feita análise mineralógica do sedimento de mangue por difração de raio X. Os sedimentos de mangue do Rio Tibiri apresentaram níveis de fósforo na ordem de 341,44 mg.kg-1, caracterizando-se como um estuário com inexpressivo impacto de atividades antropogênicas. O fósforo, em sua maior parte, concentra-se na fração inorgânica não-apatítica (PINA), média 70%. A fração inorgânica do fósforo, como o mineral apatita (PA), permaneceu em 29%. O Rio Tibiri foi classificado como não poluído (PT < 500 mg kg-1), embora o estoque de fósforo esteja em grande parte como lábil (média 73,68%). Entre os metais majoritários, o Ca se destacou pela sua associação com a fração apatítica (PA), corroborando com a presença deste mineral no sedimento. Os principais argilominerais encontrados foram caulinita, montmorilonita, ilita e quartzo.

Made available in DSpace on 2016-08-19T12:56:48Z (GMT). No. of bitstreams: 1 Dissertacao LISANDRA MARIA DA SILVA CARVALHO.pdf: 1316969 bytes, checksum: 74b629e185747db756cae70ea00cf5db (MD5) Previous issue date: 2014-07-31 / FUNDAÇÃO DE AMPARO À PESQUISA E AO DESENVOLVIMENTO CIENTIFICO E TECNOLÓGICO DO MARANHÃO / Mangrove estuaries are subject to amendments provoked by anthropogenic activities. The contamination by metals in estuarine environments is of paramount importance, since these cannot be degraded and, therefore, accumulate in sediments promoting certain toxicity to benthic organisms and humans. This risk is directly linked to the availability and mobility of metals in sediments. Although Cd, Cr, Cu, Pb, Ni and Zn are found at trace levels in the environment, several studies have been made on the basis of their toxic potential. The aim of this study is to determine the distribution and fractionation of trace metals in sediments of mangrove Paciência river, both on the surface and in the depth profile and to estimate the risk of these elements to aquatic life. Metal Fractionation in mangrove sediment (surface and depth profile) of Paciência river in Maranhão Island was conducted using the method of sequential extraction protocol by the European Commission. The metal concentrations were determined using inductively coupled plasma optical emission spectrometry technique (ICPOES). The mobility of metals (sum of the three most mobile fractions F1, F2 and F3) had values approximately 80 %, suggesting that the impact of human activities. The results showed that the total concentration levels of metals were below TEL (Threshold effect level), with the exception of Pb, whose values provide risk to aquatic life. The redox potential (Eh) decreased with depth (-110 mV at the surface to -360 mV at the bottom), and showed high correlation with Fe in fraction F2 (r² = 0,89). Other parameters studied showed no increasing or decreasing along the depth behavior, indicating that other variables may be affecting the distribution and dynamics of metals in sediment. / Os estuários de manguezais estão sujeitos às transformações decorrentes de diversas atividades antrópicas e a sua contaminação por metais é de suma importância, uma vez que estes não podem ser degradados e se acumulam nos sedimentos promovendo certa toxicidade aos organismos bênticos e aos seres humanos. Este risco está diretamente ligado à disponibilidade e mobilidade dos metais em sedimentos. Embora os metais Cd, Cr, Cu, Pb, Ni e Zn sejam encontrados em níveis traço no ambiente, vários estudos têm sido realizado em função do seu potencial tóxico. O objetivo desse trabalho é determinar a distribuição e o fracionamento dos metais traço nos sedimentos de manguezal do rio Paciência, tanto na superfície quanto no perfil de profundidade, bem como estimar o risco desses elementos para vida aquática. O fracionamento de metais no sedimento de mangue (superfície e perfil de profundidade) do rio Paciência, na ilha do Maranhão foi realizado utilizando o método da extração sequencial pelo o protocolo da Comissão Europeia. As concentrações dos metais foram determinadas usando a técnica por espectrometria de emissão ótica de plasma indutivamente acoplado (ICP-OES). A mobilidade dos metais (soma das três frações de maior mobilidade F1, F2 e F3) apresentou valores cerca de 80 %, o que sugere impacto das atividades antropogênicas. Os resultados da concentração total demonstraram que os níveis de metais estavam abaixo do TEL (Threshold effect level), com exceção do Pb, cujos valores oferecem risco para a vida aquática. O potencial redox (Eh) diminuiu com a profundidade (-110 mV na superfície até -360 mV na parte inferior), e mostrou alta correlação com Fe na fração F2 (r² = 0,89). Outros parâmetros estudados não apresentaram um comportamento crescente ou decrescente ao longo da profundidade, indicando que outras variáveis podem estar afetando a distribuição e a dinâmica dos metais em sedimento.

A Baixada Santista é um dos locais mais amplamente povoados e explorados do Estado de São Paulo. Nas últimas décadas, devido à intensa industrialização, a Baixada Santista vem sofrendo um acentuado processo de degradação ambiental. Deste contexto, os metais se apresentam de suma importância, podendo refletir a influência do homem no meio ambiente. O presente trabalho tem como principal objetivo a reconstrução ambiental do Estuário de Santos e São Vicente no âmbito da poluição da região, avaliada a partir da análise de metais no sedimento. Para isso, foram analisados nove testemunhos, que permitiram uma visão histórica do reflexo da antropização nesse ambiente costeiro. Distinguiram-se a partir dos resultados dois ambientes distintos: Canal de Bertioga e Alto Estuário Santista. Os testemunhos localizados no Canal de Bertioga apresentaram acúmulos metais mais recentes de metais, com destaque para As, Cu, Pb, Zn e Hg. Os aumentos significativos de concentração nesse ambiente, possivelmente estiveram associados a alguns acidentes ambientais, como o incêndio na Vila de Socó, na década de 1980. Os testemunhos localizados no Alto Estuário Santista apresentaram concentrações elevadas de alguns metais, como é o caso de Cu, Pb, Zn e Hg. Destacaram-se os valores de Hg, que indicaram ambientes contaminados. A concentração de metais nessa região foi coerente com o crescimento industrial e urbano da região. / The Baixada Santista is an important economic region of Sao Paulo State, strongly urbanized and populated, where environmental pressures are increasing due to the local industrialization development. As heavy metal concentrations may indicate human influences in the environment, this study aimed to reconstruct the spatial and temporal trends of pollution in Santos e São Vicente through the last decades, using the concentration of heavy metals and As from nine sliced sediment cores analyzed with ICP-OES. The results pointed two regions of distinct chemical patterns: Bertioga Channel and Santos Estuary. The former presented recent accumulations, mainly of As, Cu, Pb, Zn and Hg, possibly due to environmental incidents as the Vila Socó fire in the 1980s. The latter presented high concentrations of Cu, Pb, Zn and especially Hg, indicating contamination in this region. The concentration of metals in the study area was consistent with the local industrial growth.

Cette thèse traite de la morphodynamique pluri-décennale des environnements sableux soumis à l’action combinée des courants de marée et des vagues. Dans ces travaux, une approche de modélisation numérique basée sur les processus hydro-sédimentaires est utilisée, celle-ci étant combinée à des données collectées au sein du laboratoire LIENSs au cours de ces dernières années sur différents sites ateliers (i.e. données bathymétriques, hydrodynamiques, et sismiques). Afin de réaliser des simulations morphodynamiques de ce type d’environnement côtier, deux principaux développements ont été apportés au modèle : (1) la prise en compte de l’hétérogénéité granulométrique du sédiment, et (2) le calcul de l’évolution du fond suivant un schéma numérique basé sur le formalisme WENO et adapté à un maillage de type non-structuré. La première application du système de modélisation a concerné l'évolution rétrospective du banc de sable estuarien de la Longe de Boyard, situé en baie de Marennes-Oléron, sur la période 1960 à 2000. Les résultats de ce travail ont tout d'abord montré qu'en dépit de la morphologie globale du banc indiquant une dominance de la marée, la contribution des vagues était essentielle pour expliquer son évolution pluri-décennale. La rythmicité de l’accrétion sédimentaire observée et simulée dans la partie sud du banc a ensuite pu être analysée d'un point de vue stratigraphique, grâce à la prise en compte de l'hétérogénéité granulométrique du sédiment dans le modèle. Le lien entre la rythmicité des variations granulométriques du sédiment dans cette zone et la saisonnalité du climat de vagues a ainsi été mis en évidence. La seconde application du système de modélisation a concerné l’évolution de la flèche sableuse d'Arçay, située sur le littoral vendéen. Les résultats de simulation morphodynamique suggèrent que l’évolution de cette flèche, principalement contrôlée par les vagues, présente un comportement combinant allo-cyclicité et auto-cyclicité. / This work considers the pluri-decadal morphodynamic modeling of sandy coastal environments subjected to tides and waves. A process-based numerical model is used, together with a collection of field data from the LIENSs laboratory (i.e. bathymetric, hydrodynamic, and seismic data). To simulate the morphodynamic of these environments, two main numerical developments have been added to the model : (1) the sediment heterogeneity, and (2) the bed evolution computation following a WENO-based scheme adapted to unstructured grids. The first model application concerns the 40-year hindcast (period 1960 to 2000) of a wide estuary mouth sandbank located in the Marennes-Oléron bay : the Longe de Boyard sandbank. Numerical results suggest that this sandbank long-term evolution is strongly controlled by waves, in spite of its global tide-dominated morphology. Rhythmic nature of sediment accretion, which is observed and modeled in the south part of the bank, was then analyzed from a stratigraphic point of view thanks to the integration of sediment heterogeneity into the model. Grain size rhythmic variations in this area appeared to be related to local wave climate seasonality. The second model application considers the Arçay sandspit evolution (Vendée coast). Morphodynamic results suggest that this sandspit evolution, mainly controlled by waves, is characterized by a combination of both autogenic and external-influenced behaviors.

Les estuaires sont des systèmes hautement dynamiques où interagissent des processus biogéochimiques complexes qui influent sur le devenir de la matière organique et non organique. La confrontation des eaux fluviales et marines induit des changements rapides des principaux facteurs structurant la distribution des organismes vivants et gouvernant la spéciation de certains éléments traces entre phase particulaire et dissoute, ex : gradient de salinité, teneurs en matières en suspension (MES). Ce travail vise à étudier l’estuaire de la Charente, principal fleuve influançant le bassin de Marennes-Oléron (première zone ostreicole française) afin (i) de caractériser la structure de la communauté zooplanctonique en relation avec les paramètres environnementaux, (ii) le fonctionnement de la base du réseau trophique de l’estuaire (identification des sources de matière organique exploitée par les organismes zooplanctoniques et suprabenthiques) et (iii) d’établir un état de contamination par les métaux des compartiments biotiques. L’estuaire de la Charente se distingue par des concentrations en MES extrêmement élevées, présentant néanmoins une contribution importante de la matière organique (efflorescence phytoplanctonique printanière en zone mésohaline et production microphytobenthique). La zone de turbidité maximale semble correspondre à un écotone qui contrôle les flux de matière organique et la distribution des organismes. Le mélange physique des particules issues des systèmes dulcicoles et marins adjacents à l’estuaire avec cette forte charge de matériel resuspendu conduit à une homogénéisation des signatures isotopiques et métalliques particulaires en été et automne le long du gradient de salinité. Les quatre assemblages zooplanctoniques identifiés sont structurés spatialement par la salinité et la concentration en MES et temporellement par les variations de température et de débit fluvial. Malgré la dominance quantitative du matériel détritique au sein du pool de matière organique particulaire (MOP), il semble que les 5 taxons planctoniques ou suprabenthiques dominants étudiés (Eurytemora affinis, Acartia spp., Daphnia spp., Neomysis integer, Mesopodopsis slabberi) présentent une sélectivité importante vis-à-vis de sources primaires distinctes. Cette succession spatio-temporelle d’espèces sélectives conduit à une multiplication des flux trophiques et semble ainsi optimiser à l’échelle annuelle l’exploitation de la MOP disponible. Les concentrations en Cd, Cu, Hg, Pb, V et Zn ont par ailleurs été mesurées dans près de 40 taxons estuariens (zooplancton, benthos, poissons). Malgré des concentrations en métaux dissous et particulaires plus faibles que dans les grands estuaires européens subissant une pression anthropique importante (Seine, Gironde), les niveaux de contamination mesurés dans les différents compartiments biotiques semblent globalement équivalents. Les évènements brefs (crue hivernale, efflorescence phytoplanctonique printanière) altèrent toutefois fortement ce schéma général en modifiant les sources primaires de matière organique disponibles et les concentrations métalliques particulaires (Cd notamment). / Estuaries are highly dynamic systems where complex biogeochemical greatly affect the fate of organic and non-organic matter. The physical mixing of freshwater and saltwater leads to high variability in the main drivers controlling organisms distribution and trace metals partitioning between the particulate and dissolved phases: eg. salinity gradient, suspended particulate matter concentration (SPM). This work aims thus at studying the Charente estuary, which is the main river discharging into the Marennes-Oléron Bay (first oyster producing area in France) in order to (i) characterize the zooplankton community structure and relate it to the main environmental parameters, (ii) identify the main organic matter sources contributing to the functioning of the planktonic food web and (iii) to characterize contamination of the biological compartment of this estuary. Although being one of the most turbid estuaries in Europe, the Charente estuary displays quite high organic matter contribution, especially through a spring phytoplankton bloom in the mesohaline area and microphytobenthic production. The maximum turbidity zone (MTZ) displays some ecotonal characteristics, controlling both organic matter fluxes and organisms distribution. The physical mixing of terrestrially and marine derived particles within the high load of resuspended estuarine particles leads to quite homogeneous isotopic and metallic signatures in particles all along the salinity gradient during summer and autumn. Salinity and SPM concentration significantly controls the spatial distribution of the four zooplankton assemblages identified while temperature and river discharge controls their temporal variations. Despite the quantitative dominance of terrestrially derived detrital organic matter, the five dominant planktonic and suprabenthic taxa studied (Eurytemora affinis, Acartia spp., Daphnia spp., Neomysis integer, Mesopodopsis slabberi) display strong selectivity toward different organic matter sources. At the annual scale, the exploitation of the available stock of organic matter seems optimized by this spatio-temporal succession of selective species that leads to multiple trophic pathways. In addition, the concentrations of Cd, Cu, Hg, Pb, V and Zn were measured in nearly 40 estuarine taxa (zooplankton, benthos, fishes). Although particulate and dissolved metal concentrations were somewhat low as compared to those measured in highly impacted European estuaries (Seine, Gironde), the contamination levels recorded in these biotic compartments were of the same order of magnitude. Moreover, brief events such as high water levels and phytoplankton blooms greatly affect this overall pattern by modifying the available organic matter sources and particulate trace metals concentrations (especially Cd).

Le but général de ce travail fut de quantifier la silice biogène (BSiO2) dans les sédiments du continuum de l'Escaut (estuaire – zone côtière), ainsi que son taux de recyclage - rétention. Le coefficient de diffusion moléculaire de la DSi a été déterminé pour différentes valeurs de température et deux salinités et une relation empirique reliant le coefficient de diffusion à la température et à la viscosité de la solution a été établie. La distribution longitudinale de la BSiO2 dans les sédiments de surface, ainsi que les profils verticaux de BSiO2 et de silice dissoute ont été déterminés durant différentes saisons en 2004 et 2005. Les flux de DSi ont été également estimés via des expériences d’incubations et par modélisation des profiles verticaux de DSi. Des expériences de dissolution des sédiments ont permis de déterminer (via modélisation) les constantes cinétiques de vitesse de la BSiO2 et une première évaluation du taux de recyclage de la BSiO2 (5 – 70%). Sur base des calculs à partir des profiles de DSi dans l’eau interstitielle, le taux de recyclage de la BSiO2 varie entre 8 et 92% dans l’estuaire, ce qui correspond à une rétention moyenne de la BSiO2 supérieure à 60%, et souligne ainsi l'efficacité du filtre estuarien par rapport à la silice. En revanche, le recyclage de BSiO2 dans la zone côtière apparaît comme très intensif, avec des valeurs souvent supérieures à 40%. Ces résultats montrent l'importance d'inclure les estuaires dans le calcul des budgets globaux de Si. / The general objective of this study was to quantify the BSiO2 in the sediments of the Scheldt continuum, together with its recycling and retention in this area. First an empirical relation linking the diffusion coefficient of DSi to temperature and salinity was determined, via diffusion experiments. The longitudinal BSiO2 distribution in surface sediments and the vertical BSiO2 and DSi profiles in sediment cores where then measured during 2 years and different seasons, together with other parameters characterizing pore waters, such as alkalinity, pH, sulphate… DSi fluxes were also estimated either directly through whole core incubations measurements or via modelling of interstitial water profiles. BSiO2 dissolution experiments allowed the evaluation of the kinetic rate constants also through modelling of the results, and gave preliminary information over the BSiO2 recycling rates (5 – 70%). The recycling rate as obtained from pore water profiles vary between 8 and 92%, with an average value of about 32%, which highlights the importance of the estuarine filter for silica. Recycling is much more intense in the coastal area, with values up to 40%, which we explain by higher salinity and higher sediment permeability. The different experiments and results also indicated that secondary mineral precipitation might be and important process affecting BSiO2 in the Scheldt sediments.<p> / Doctorat en Sciences / info:eu-repo/semantics/nonPublished

Dans le contexte de la contamination quasi-généralisée des eaux de surface par les médicaments, les travaux de cette thèse portent sur l’étude des niveaux de concentration et du devenir de ces micropolluants organiques dans la Garonne estuarienne, recevant les effluents traités de l’agglomération bordelaise. Après le développement et la validation des outils analytiques associés à la détection multi-résidus dans les matrices eau et sédiment, la composition et la variabilité des effluents urbains bordelais ont été caractérisées, avant et après traitement en station d’épuration. La contamination globale des compartiments eau, matières en suspension et sédiment a ensuite été évaluée sur une rivière périurbaine de l’agglomération. Par ailleurs, le suivi réalisé en Gironde montre l’importance relative des apports amont et urbains et met en évidence la dégradation in-situ de certains médicaments, par ailleurs confirmée par une expérience d’incubation d’eau estuarienne réalisée in-vitro. / Ubiquitous presence of pharmaceuticals in the environment is of great concern. In this Ph.D. work, occurrence and fate of these organic contaminants were studied in the estuarine Garonne River, receiving treated effluents of the Bordeaux urban area (France). After developing and validating the analytical methods for multi-residue detection of 53 pharmaceuticals in water and sediment, composition and variability of the Bordeaux wastewater treatment plant influents and effluents were characterized. Presence of analytes in river water, suspended solids and sediments was then investigated on a periurban river located in the suburbs of Bordeaux. Besides, a long-term monitoring of estuarine Garonne River revealed the relative importance of local and upstream inputs and clearly showed a seasonal in-situ degradation of certain pharmaceuticals. This degradation was further confirmed and examined through batch experiments simulating the mixing conditions of wastewater and estuarine river water, highlighting the importance of suspended solid concentration in biodegradation rates.

Ce travail présente un premier bilan quantitatif des principaux processus contrôlant le cycle de Hg (distribution, spéciation, dynamique) dans l’estuaire de la Gironde, affecté par une contamination historique. Des extractions sélectives sur des sédiments et des matières en suspension du système Lot-Garonne-Gironde, indiquent que ~70 % du flux en Hg (100-800 kg.an-1) est lié à des phases organiques et sulfurées. L’observation de Hg effectuée dans les différents compartiments (colonne d’eau, air, sédiments) tient compte de la variabilité spatiale et temporelle à multiples échelles ainsi que des gradients géochimiques estuariens. Les profils le long du gradient de salinité (9 profiles) montrent une augmentation (facteur 2 à 5) des concentrations en Hg dissous (niveau de base ~1 ng.L) dans la zone de turbidité maximale (ZTM), attribuée à la dégradation d’une phase porteuse majeure : la matière organique. Les niveaux de methyl-mercure dissous (MeHgD) de la colonne d’eau sont en général faibles (<0,05 ng.L-) mais peuvent atteindre jusqu’à 0,5 ng.L-1 dans les conditions les plus turbides. La relation entre MeHgD et la turbidité s’explique par la dégradation bactérienne de phases porteuses ou par la méthylation in situ de Hg, la photodégradation de MeHg étant négligeable. L’augmentation systématique de MeHg particulaire à l’embouchure suggère son accumulation dans le phytoplancton, particulièrement intense entre Mai et Septembre, période de forte production primaire. Des profils verticaux à haute résolution spatiale dans les sédiments du chenal de navigation, des zones non-draguées et de l’estran ont dévoilé une augmentation des teneurs en Hg dissous, mais surtout en MeHgD (jusqu’à 2 ng.L-1) directement sous l’interface. L’évolution en parallèle des paramètres indiquant la sulfato-réduction (déficit de sulfates) et la ferri-réduction (Fe dissous) suggère des processus de methylation biotique de Hg et/ou de libération de MeHg par dissolution des oxy-hydroxydes de Fe. Des expérimentations d’incubation de sédiments non perturbés avec traçage isotopique 199 Hg) ont permis d’estimer la vitesse de méthylation à 0,012 %-Hg méthylé.h-1. Les flux vers la colonne d’eau par diffusion ont été évalués à 0,1 pour HgD et 0,08 kg.an-1pour MeHgD, ce qui est très inférieur aux apports fluviaux (35 kg.an-1 et 1,4 kg.an1). Les activités de dragages déplacent et remettent en suspension ~1100 kg.an-1 de Hg et 3,2 kg.an-1de MeHg, associés aux sédiments réduits dragués. Si cette activité peut localement et temporairement modifier les distributions de Hg dans la colonne d’eau, leur impact sur le bilan global de l’estuaire semble faible. Dans les eaux de surface, des cycles diurnes de concentration en Hg gazeux dissous (DGM) ont été attribués à la photo-réduction de Hg(II) en Hg°. Au-delà de la variabilité du rayonnement solaire, la turbidité contrôle la pénétration de la lumière dans eau, et par conséquent, le cycle de Hg° dissous est fortement lié à l’ampleur et la position de la ZTM. Les flux journaliers vers l’atmosphère indiquent que la surface de l’estuaire est une source de Hg° en été, et un puits en hiver en période de forte turbidité. A l’échelle annuelle, l’évasion de Hg° à l’interface eau-atmosphère (~ 4 kg.an-1), est compensée par la déposition (5-8 kg.an-1). / This study presents a first quantitative assessment of the main processes controlling the Hg cycle in the Gironde Estuary (speciation, distribution, fluxes, dynamics) affected by historical polymetallic pollution. Selective extractions on sediments and suspended solids showed that in the Lot-Garonne-Gironde fluvial-estuarine system ~70% of total Hg fluxes (100-800 kg yr-1) are associated with organic matter and/or sulphides. Sampling of the different environmental compartments (water, air, sediments) addresses spatial and temporal variability at multiple scales, covering the major estuarine geochemical gradients. Longitudinal profiles (9 cruises) over the salinity gradient showed a 2-5 times increase in dissolved Hg concentrations (baseline ~1 ng L-1) in the Maximum Turbidity Zone (MTZ), mainly attributed to microbial degradation of particulate organic matter, a major Hg carrier phase. Dissolved MeHg (MeHgD)levels are generally low (<0,05 ng L-1) but may reach up to 0.5 ng L-1 under very turbid conditions. The relation between MeHgD and turbidity was attributed to dissolution of particulate carrier phases and/or in situ methylation of Hg (sediment or water column), MeHg photodegradation being negligible due to turbidity. A systematic increase in particulate MeHg near the estuary mouth suggests uptake and accumulation by phytoplankton, especially from May to September when light conditions allow intense primary production. In surface sediment (0-20 cm; dredged and non-dredged; subtidal and intertidal), MeHgD concentrations increased parallel to diagenetic reduction of Fe-phases and sulphate, suggesting biotic Hg methylation and/or MeHg release by Fe oxyhydroxyde dissolution. Incubation experiments in undisturbed sediment using stable isotope (199Hg) spikes suggest an average methylation rate of 0.012 %-Hg methylated.h-1. Diffusive exportation of dissolved Hg and MeHg into the water column at the whole estuary scale has been evaluated to 0.1 kg.yr-1and 0.08 kg.yr-1,respectively. These fluxes are negligible compared to fluvial inputs (35 kg.yr-1 and 1.4 yr.an-1). Dredging-related re-suspension of reduced sediment and pore water may recycle ~1100 kg of Hg and 3.2 kg of MeHg in the water column. This may locally and temporarily modify Hg distribution in the water column, but does not seem to modify the estuarine Hg balance. Diurnal cycles of dissolved gaseous mercury (DGM; mostly Hg°) concentration in surface water have been attributed to photo-reduction of Hg(II). However, turbidity may efficiently reduce light penetration and DGM production. Therefore, the DGM cycle in turbid estuaries depends on seasonal variations in MTZ intensity and position. The Gironde Estuary is a Hg° source to atmosphere in summer, but may turn into a sink during turbid periods in winter. The annual Hg° evasion (~4 kg.yr-1) is counterbalanced by dry and wet deposition (5-8 kg.yr -1).

The ichthyofauna of three small Natal estuaries, the Mhlanga, Damba and Zotsha was sampled over a period of two years. A total of 68 kinds of fishes representing 24 families, 39 genera and 56 species were captured during this study. Forty seven kinds of fishes were recorded in the Mhlanga of which Gilchristella aestuaria,Oreochromis mossambicus, Valamugil cunnesius, Valamugil sp. and juvenile mugilids numerically dominated. In terms of biomass, O. mossambicus, V. cunnesius, Liza alata, Myxus capensis and Mugil cephalus dominated the ichthyofauna of the Mhlanga. In the Damba, 24 kinds of fishes were recorded. The most abundant fishes captured were Glossogobius callidus, M. capensis and O. mossambicus. M. capensis, M. cephalus, O. mossambicus and G. callidus dominated the fish biomass captured in the Damba. A total of 56 kinds of fishes were recorded in the Zotsha during this study. The ichthyofauna of the Zotsha was numerically dominated by juvenile mugilids, G. aestuaria, O. mossambicus, Rhabdosargus holubi, Terapon jarbua, Ambassis productus and G. callidus. The species which dominated the fish biomass in the Zotsha were O. mossambicus, L. alata, Valamugil robustus, Valamugil buchanani, M. capensis, M. cephalus and V. cunnesius. Classifying the species captured according to whether they were resident estuarine species, freshwater species, estuarine-dependent marine species and marine species revealed that the first three groups were all well represented in the systems. The only system in which marine species made any significant contribution to the ichthyofauna was the Zotsha. Oreochromis mossambicus was the dominant freshwater species in all three estuaries during this study. Gilchristella aestuaria and Glossogobius callidus were the principal estuarine species in the Mhlanga and the Damba respectively. Both G. aestuaria and G. callidus were the dominant estuarine species captured in the Zotsha. The principal estuarine-dependent marine fishes captured in the Mhlanga were V. cunnesius, Valamugil sp., juvenile mugilids, M. capensis, M. cephalus and L. alata. In the Damba, M. capensis and M. cephalus were the dominant estuarine-dependent marine species and in the Zotsha juvenile mugilids, R. holubi, T. jarbua, A . productus, M. capensis, V. cunnesius, V. robustus, M. cephalus and L. alata predominated. The results of this study indicate that the estuaries are dominated at different periods by different assemblages of fishes. This is linked to the spawning and migration patterns of the various species as well as the hydrological regime of each estuary. During the winter these systems are normally closed with relatively deep waters and high food resource and habitat availability. Freshwater and estuarine species mainly inhabit the upper reaches of the systems while estuarine-dependent marine species mainly occupy the middle and lower reaches and dominate the fish community. When these systems open with the onset of the spring/summer rains, adult and sub-adult estuarine-dependent marine species emigrate to the marine environment and juveniles begin recruiting into the systems. Spring is also the peak breeding period of resident estuarine and freshwater species, resulting in an increase in the contribution of these fishes to the overall population during this period. When closed estuaries open many of them drain and this results in the fishes concentrating in the lower reaches of the system where moderate water depths are present, thus further contributing to an increase in the proportion of freshwater and estuarine species in this region. The breaching of closed estuaries also results in a slump in food resources and habitat availability. Competition and possible increased vulnerability to avian predation (due to the shallow nature of the systems), may contribute to a decrease in the proportion of estuarine and freshwater species in summer. The prolonged spawning and recruitment of 0+ juveniles of estuarine-dependent marine species results in an increase in the proportion of these fishes present in the estuaries during summer. In autumn, these systems normally close, water levels rise and available food resources and habitat increase. This allows the redistribution of freshwater and estuarine species upstream, leaving estuarine-dependent marine species to dominate the middle and lower reaches. Although temporarily open/closed estuaries along the Natal coast may not be as diverse as permanently open estuaries in terms of their ichthyofauna, their importance must not be underestimated since by providing a continuous sequence of sheltered habitats along the coast they may contribute significantly to the viability of estuarine-dependent marine fish stocks.