Thesis (MEng)--Stellenbosch University, 2014. / ENGLISH ABSTRACT: The Swartvlei estuary and lake system is situated on the southern coast of the Western Cape Province of South Africa and forms part of the core conservation area of the Wilderness National Park. The Swartvlei system comprises two interlinked water bodies, namely Swartvlei Lake and Swartvlei estuary. SANParks have been monitoring this estuary closely over the past two decades, due to its importance to the ecology and to tourism. There are also low-lying properties on the perimeter of the Swartvlei estuary which run the risk of occasional flooding. Two of the major monitoring issues in this estuary system are the water level required for successful mouth breaching, and the influence of the water level on the low-lying properties. This study presents a preliminary analysis of the sediment budget across the Swartvlei estuary mouth. The objective of this study was to identify the various sediment contributory factors and to estimate the quantities that each individually contributed towards the defined sediment budget. / AFRIKAANSE OPSOMMING: Die Swartvlei meer en see monding is geleë aan die kaapse suidkus van Suid- Afrika. Dit vorm deel van die kern bewarings area van die Wilderness Nationale Park. Die Swartvlei sisteem bestaan uit twee verbinde, kern dele nl: Swartvlei meer en estuarium. Vir die afgelope twee dekades is hierdie area onder die noue toesig van SANParke as gevolg van die belangrikheid van die area met betrekking tot toerisme en ekologie. Daar is ook menigde laag liggende eiendomme aan die oewers, wat baie sensitief is vir watervlak stygings. Die optimum water vlakke benodig vir die uitskuring van die gety monding het ook implikasies vir die laag liggende eiendome en vereis noukeurige monitering. ‘n Voorlopige analise van die sediment begroting rondom die gety monding word deur hierdie studie voorgelê.

The Green Drop Certification Programme, launched in 2008 alongside the Blue Drop Certification Programme, aims to provide the Department of Water Affairs with a national overview of how municipalities and their individual wastewater treatment works (WWTW) are complying with licence conditions set by the National Water Act (NWA) (No. 36 of 1998; DWAF 1998) and the Water Services Act (No. 108 of 1997; DWAF 1998). By publishing the results of each municipality’s performance, the programme aims to ensure continuous improvement in the wastewater treatment sector through public pressure. The programme has been identified by this project as a necessary linking tool between the NWA and the Water Services Act to ensure protection and sustainable use of South Africa’s natural water resources. It does this through assisting municipalities to improve their wastewater treatment operations which in theory will lead to discharged effluent that is compliant with discharge licence conditions. These discharge licences form part of the NWA’s enforcement tool of Source Directed Controls (SDC) which help a water resource meet the ecological goals set for it as part of Resource Directed Measures (RDM). The link between meeting the required SDC and achieving the RDM goals has never been empirically tested. This project aimed to determine the present ecological condition of the Uie River, a tributary of the Sundays River which the Sundays River Valley Municipality (SRVM) discharges its domestic effluent into. It then determined whether the SRVM’s WWTW was complying with the General Standard licence conditions and what the impact of the effluent on the river was through the analysis of monthly biomonitoring, water chemistry and habitat data. Lastly, the project examined the effectiveness of the Green Drop Certification Programme in bringing about change in the SRVM’s wastewater treatment sector, which previously achieved a Green Drop score of 5.6 percent. It wanted to examine the underlying assumption that a WWTW which improves its Green Drop score will be discharging a better quality effluent that will help a water resource meets the RDM goals set for it. The Kirkwood WWTW did not have a discharge licence at the time of assessment and was thus assessed under the General Standard licence conditions. It was found that the Kirkwood WWTW was not complying with the General Standard discharge licence conditions in the Uie River. This was having a negative impact on the river health, mainly through high concentrations of Total Inorganic Nitrogen (TIN-N), orthophosphate and turbidity. The SRVM should see an improvement in its Green Drop score for the Kirkwood WWTW. However, the municipality showed no implementation of necessary programmes. Implementation of these programmes would help the SRVM meet the General Standard licence conditions (part of SDC) which would help the Uie River meet the RDM goals set for it.

Bedrock islands add variation to the estuarine system that results in deviations from typical unconfined estuarine sediment transport patterns. Limited literature exists regarding the dynamics of seabed morphology, delta formation, sediment divergence patterns, and sedimentary facies classifications of non-fjordic bedrock confined systems. Such knowledge is critical to address coastal management concerns adequately. This research presents insights from the Skeena Estuary, a macrotidal estuary in northwestern Canada with a high fluvial sediment input (21.2-25.5 Mtyr-1). Descriptions on sub-environments, stratification, and sediment accumulation within the Skeena Estuary utilize HydroTrend model outputs of riverine sediment and discharge, Natural Resources Canada radiocarbon-dated sediment cores and grain size samples, and acoustic Doppler current profiler and conductivity-temperature-depth measurements from three field campaigns. Research findings delineate a fragmented delta structure with elongated mudflats and select areas of slope instability. Variations from well-mixed water circulation to lateral stratification, govern the slack tide flow transition and sediment transport pathways within seaward and landward passages of the estuary. Fostering a comprehensive understanding of bedrock confined estuary and delta systems has implications for the assessment of coastal management strategies, the productivity of ecological habitats, and the impacts of climate change within coastal areas. / Graduate

This dissertation integrates a process-based hydrological investigation with an ongoing paired-catchment study to better understand how forest harvest impacts catchment function at multiple scales. We do this by addressing fundamental questions related to the stocks, flows and transit times of water. Isotope tracers are used within a top-down catchment intercomparison framework to investigate the role of geology in controlling streamwater mean transit time and their scaling relationships with the surrounding landscape. We found that streams draining catchments with permeable bedrock geology at the Drift Creek watershed in the Oregon Coast Range had longer mean transit times than catchments with poorly permeable bedrock at the HJ Andrews Experimental Forest in the Oregon Cascades. We also found that differences in permeability contrasts within the subsurface controlled whether mean transit time scaled with indices of catchment topography (for the poorly permeable bedrock) or with catchment area (for the permeable bedrock). We then investigated the process-reasons for the observed differences in mean transit time ranges and scaling behavior using a detailed, bottom-up approach to characterize subsurface water stores and fluxes. We found that the mean transit times in catchments underlain by permeable bedrock were influenced by multiple subsurface storage pools with different groundwater ages, whereas storage in the poorly permeable catchments was limited to the soil profile and that resulted in quick routing of excess water to the stream at the soil bedrock interface, leading to mean transit times that were closely related to flowpath lengths and gradients. Finally, we examined how and where forest trees interacted with subsurface storage during the growing season using a forest manipulation experiment, where we tested the null hypothesis that near-stream trees alone influenced daily fluctuations in streamflow. We felled trees within this zone for two 2.5 ha basins and combined this with isotopic tracing of tree xylem water to test if water sources utilized by trees actively contributed to summer streamflow. We rejected our null hypotheses and found that diel fluctuations in streamflow were not generated exclusively in the near-stream zone. We were unable to link, isotopically, the water sources trees were utilizing to water that was contributing to streamflow. Our results provide new process-insights to how water is stored, extracted, and discharged from our forested catchments in Western Oregon that will help better explain how forest removal influences streamflow across multiple scales and geological conditions. / Graduation date: 2012

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).<p>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.<p>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. / Doctorat en Sciences / info:eu-repo/semantics/nonPublished

Saltmarshes are highly valued habitats but the majority of the Eden Estuary's saltmarsh was buried under sea defences and ad hoc rubbish dumps during the last century. Without saltmarsh, the degraded shoreline may be even more vulnerable to rising sea levels and increased wave and tidal energy. This study investigated planting native saltmarsh species, common in the estuaries of Eastern Scotland, to restore saltmarsh development and sedimentation to the Eden Estuary's shoreline. The survival and growth of the sedge Bolboschoenus maritimus (Sea Club-rush) and the grasses Phragmites australis (Common Reed) and Puccinellia maritima (Common Saltmarsh Grass) were compared in planting trials. These were seeded or transplanted onto unvegetated upper mudflats in front of eroded P. maritima saltmarsh and a disused rubbish dump. The longer term sustainability of this practice was assessed by comparing sediment deposition and surface elevation in the transplant sites, natural saltmarsh and upper unvegetated mudflats. B. maritimus outperformed P. australis and P. maritima. Springtime, high density planting was successful, whereas seeds, planting in autumn and low density planting failed. Growth in the transplanted B. maritimus sites was relatively slow for the first three years but subsequently overtook growth of the seaward edge of natural B. maritimus marsh. Sediment was not deposited on natural P. maritima and was low on upper unvegetated mudflats and in young transplant sites. Most deposition occurred in four year old sites of B. maritimus. Sediment surface elevation in natural P. maritima remained constant throughout the year, but increased in all the other sites during the summer. The upper mudflat was the only site to erode during winter. A significant, positive association was found between tide height and sediment deposition, while winds from the south-east were associated with significantly more deposition than winds from the south-west. The direct planting of saltmarsh vegetation has restored a valuable and rapidly disappearing habitat to the degraded shoreline of the Eden Estuary. The low-cost and simplicity of this restoration practice give it great potential as a sustainable coastal management option that should be explored in other Scottish estuaries. This form of restoration could help to increase the resilience and reduce the vulnerability of degraded shorelines to climate change and rising sea levels.

Στην παρούσα εργασία πραγματοποιείται οικολογική αξιολόγηση των εκβολικών οικοσυστημάτων των ποταμών Εύηνου και Πείρου που εκβάλλουν στον Πατραϊκό κόλπο. Αποτελούν συνδυασμό χερσαίων και υγροτοπικών περιοχών με σημαντική οικολογική αξία και λειτουργίες. Ο Εύηνος σχηματίζει τυπικό δέλτα σε αντίθεση με τον Πείρο, στην περιοχή εκβολής του οποίου οι συνθήκες δεν ευνοούν μια τέτοια διαδικασία. Στόχοι της μελέτης ήταν: η καταγραφή και χαρτογράφηση των τύπων οικοτόπων στις επιμέρους περιοχές με τη χρήση των GIS, η μελέτη των ανθρωπογενών δραστηριοτήτων και των επιπτώσεών τους στη δομή των οικοτόπων, η εκτίμηση της κατάστασης τους με τη βοήθεια δεικτών οικολογικής αξιολόγησης και τελικά, η ανάπτυξη κατάλληλου διαχειριστικού σχεδίου. Για την πραγματοποίηση της εργασίας αυτής προηγήθηκαν επισκέψεις και στα δύο εκβολικά οικοσυστήματα, φωτογραφήσεις, καθώς και συλλογή και προσδιορισμός φυτικού υλικού από τους κυριότερους τύπους βλάστησης. Για την αναγνώριση των τύπων οικοτόπων χρησιμοποιήθηκε ο Τεχνικός Οδηγός Χαρτογράφησης του δικτύου NATURA 2000. Για την εκτίμηση της οικολογικής κατάστασης των εξεταζόμενων περιοχών εφαρμόστηκαν τα κριτήρια της ποικιλότητας, φυσικότητας, σπανιότητας, απειλής και δυνατότητας αποκατάστασης στο επίπεδο των οικοτόπων και των συνδυασμών τους σύμφωνα με την Οδηγία 92/43/ΕΟΚ. Επιπλέον, εφαρμόστηκε η ανάλυση DPSIR σε επίπεδο λεκάνης απορροής των υπό μελέτη ποταμών, με έμφαση στα εκβολικά τους συστήματα, με τη χρήση 45 δεικτών. Οι τύποι οικοτόπων, η αξιολόγηση με βάση τα κριτήρια και οι πιέσεις-επιπτώσεις σε κάθε περιοχή μελέτης οπτικοποιήθηκαν σε ψηφιακούς χάρτες με τη χρήση των GIS. Καταγράφηκαν 322 taxa στο δέλτα του Εύηνου και 225 taxa στις εκβολές του Πείρου, εκ των οποίων τα 112 είναι κοινά μεταξύ των περιοχών μελέτης. Πραγματοποιήθηκε περιγραφή και χαρτογράφηση 22 φυσικών και 3 ανθρωπογενών τύπων οικοτόπων. Οι κυριότερες αλλοιώσεις που καταγράφηκαν ως αποτέλεσμα της μακροχρόνιας ανθρώπινης παρουσίας είναι: η έντονη διάβρωση και οπισθοχώρηση της ακτογραμμής, η επέκταση των καλλιεργούμενων εκτάσεων εις βάρος των φυσικών και η έντονη ρύπανση των υδάτων. Από την αξιολόγηση προέκυψε ότι οι οικότοποι στις δύο περιοχές βρίσκονται σε μια μέτρια έως καλή κατάσταση διατήρησης, με την περιοχή του Εύηνου να λαμβάνει την υψηλότερη βαθμολογία ως προς τα κριτήρια. Το πλαίσιο DPSIR ανέλυσε την επικρατούσα κατάσταση και ανέδειξε τη σοβαρή υποβάθμιση που υφίστανται τα εκβολικά συστήματα. Συμπερασματικά, τα GIS αποτέλεσαν ένα σημαντικό διαχειριστικό εργαλείο, καθώς επιτρέπουν τη συνεχή καταγραφή των διαχρονικών αλλαγών και την εκτίμηση του βαθμού αλλοίωσης των δύο εκβολικών οικοσυστημάτων με σκοπό τη διατήρηση και την προστασία τους. / In the present study an ecological evaluation of the estuary ecosystems of the rivers Evinos and Piros flowing into the Gulf of Patras was carried out. They constitute a combination of terrestrial and wetland areas with significant ecological value and functions. Evinos forms a typical delta unlike Piros, in the estuarine region of which the conditions do not favor such a process. The objectives of the study were: the recording and mapping of habitat types in each area with the use of GIS, the study of human activities and their impact on the structure of habitats, the assessment of their state with the use of indicators of ecological value and finally, the development of an appropriate management plan. For the accomplishment of this study visits to both estuarine ecosystems, photography and collection and identification of the plant material from the main vegetation types was performed. For the identification of habitat types the Technical Guide for Mapping of the network NATURA 2000 was used. To assess the ecological status of the areas concerned the criteria of diversity, naturalness, rarity, threat and replaceability were applied, at the level of habitats and their combinations, according to the Directive 92/43/EEC. Moreover, the DPSIR analysis was applied at the basin level of the studied rivers, with emphasis on their estuarine systems. The habitat types, the evaluation based on the criteria and the pressures-impacts on each of the studied areas were visualized into digital maps using GIS. 322 taxa were recorded for the Evinos delta and 225 for the mouth of Piros, of which 112 are common among the study areas. Description and mapping of 22 natural and 3 anthropogenic habitat types was carried out. The main alterations that were recorded as a result of long-term human presence are: the intense erosion and retreat of the coastline, the expansion of cultivated land at the expense of natural one and the strong water pollution. Assessment revealed that the habitats in both regions are at a moderate to good conservation status, with the area of Evinos receiving the highest rating concerning the above criteria. The DPSIR framework analysed the present state and highlighted the serious degradation that occurs in estuaries. In conclusion, the GIS are an important management tool, as they allow the continuous recording of the diachronic changes and the evaluation of the degree of deterioration of both estuary ecosystems in order to conserve and protect them.

In this thesis I review how Sargassum muticum (Yendo) Fensholt, an invasive alga from Asia, has spread globally due to human activities and describe how this species can affect seagrass ecosystems. Abiotic factors such as nutrient and substratum availability may facilitate the spread of S. muticum into Zostera marina L. meadows, but analyses of seawater nutrients, and sediment particle size and % organic content revealed no significant differences between experimental quadrats in seagrass meadows either with, or without the presence of S. muticum. Phenolic compounds were examined because they form the basis of defensive mechanisms in plants and algae, therefore any change in phenolic content may affect the ability of Z. marina to protect itself from disease, herbivory and invasive species through allelopathic interactions. Results from a four year field study and multiple annual laboratory experiments showed significant reductions (p = 0.034 and p = 0.002, respectively) in the caffeic and tannic acids equivalents content of Z. marina when in the presence of S. muticum. As the abundance of S. muticum increases, other changes in the physiology of Z. marina may occur including variations in growth rates, nutrient partitioning and chlorophyll fluorescence, but data from multiple laboratory experiments illustrated no significant differences in growth. Chlorophyll fluorescence analyses revealed significant differences between treatments with and without S. muticum (p = 0.008), but pairwise comparisons indicated these differences only occurred in 2008 (p &lt; 0.001). Significant differences were also found in nutrient partitioning amongst functional regions of the shoots (p = 0.024), but pairwise comparisons detected these differences between a biomass control treatment (ZZ: Zostera + Zostera) and the ZS (with S. muticum) and ZM (Z. marina on its own at a lower biomass per replicate) treatments (p = 0.013 and p = 0.019, respectively), but not between ZS and ZM. Previous in situ research has found negative effects of S. muticum presence on densities of kelp and other algae. Results from the long-term field study indicated significantly lower mean in situ Z. marina densities within the ZS treatment (p &lt; 0.001). Epibiota found living on the blades of Z. marina provide food for organisms within seagrass ecosystems and also create microhabitats for other species to occupy. Alterations in the abundances of epibiota and microhabitats formed could further modify seagrass ecosystems through shifts in timing of food availability, food preferences and microhabitats created. The long-term field study data revealed significantly lower epibiota abundances within the ZS treatment (p = 0.019), but differences in biomass between treatments were not detected. Changes in the biochemistry, physiology, vegetative physiognomy and epibiota assemblages of Z. marina revealed during experimental manipulations are presented and considered within the context of long-term seagrass survival in light of increasing S. muticum invasion.

Les rejets d’argent (Ag) dans l’environnement liés à l’exploitation minière aux diverses applications industrielles (e.g. bijouterie, médecine, photographie, électronique et plus récemment les nanotechnologies) font de Ag un polluant historique et émergent, dont les transferts et les effets dans les milieux aquatiques sont largement sous-documentés. Ce travail présente un premier bilan des sources, du transfert et de la bioaccumulation de Ag dans le système fluvio-estuarien de la Gironde. Le continuum Lot-Garonne-Gironde, connu pour une pollution polymétallique (e.g. Cd, Zn) provenant du bassin de Decazeville, est un système modèle pour l’étude des transferts métalliques du continent à l’océan. Les enregistrements des signaux historiques (~50 ans) de Ag dans les sédiments du Lot en amont (Ag : 0,3 mg/kg) et en aval (Ag : jusqu’à 7 mg/kg) du bassin de Decazeville sont similaires à ceux de Cd, indiquant des sources et des processus de transport/dépôt communs liés à l’histoire minière et industrielle jusqu’en 1986. Le lessivage et l’érosion actuels des terrils provoquent localement des concentrations en Ag particulaire (AgP : 260 mg/kg) et dissous (AgD : 1260 ng/l) dans la rivière Riou-Mort qui sont 2 à 3 ordres de grandeur supérieures aux valeurs typiques. Malgré ces fortes concentrations, la contribution du Riou-Mort aux flux de Ag de la Garonne (AgD : 0,008 à 0,041 t/an ; AgP : 0,306 à 2,44 t/an ; 1999-2009) reste faible (AgP : <11% ; AgD : <6%). La Garonne transporte l’essentiel (63-83%) des apports en Ag à l’estuaire principalement sous forme particulaire (96±2%). La détermination du bruit de fond géochimique régional (AgP/ThP=0,026) a permis d’évaluer (i) la contribution naturelle (20% à 65%) aux flux totaux en AgP et (ii) les flux anthropiques spécifiques de AgP (15±10 g/km²/an et 0,24±0,16 g/hab/an) à l’échelle du bassin versant de la Garonne (La Réole). Dans l’estuaire salin, la désorption par les ions chlorures libère ~60% de AgP vers la colonne d’eau (addition), provoquant des concentrations maximales en AgD (6-8 ng/l) à salinité 15-25. La fraction en Ag désorbé correspond à la fraction potentiellement biodisponible ou réactive (i.e. extractible par HCl 1 M). Ainsi, les premières estimations des flux nets indiquent que l’export annuel de Ag vers le domaine côtier est à 50-80% lié à la phase dissoute (0,64 à 0,89 t/an en 2008 et 0,56 à 0,77 t/an en 2009). Bien que plus biodisponible sous forme ionique Ag+ (dominante en eau douce), l’accumulation de Ag dans les organismes estuariens (huîtres, crevettes et anguilles) reflète la pression d’exposition supérieure en eau saumâtre. L’exposition in situ d’anguilles européennes, espèce recommandée pour la biosurveillance du milieu dans le cadre de la Directive Cadre sur l’Eau, dans des cages à différents sites clé de l’estuaire pendant 3 mois, a mis en évidence les voies directes et trophiques de la contamination en Ag à des niveaux de contamination environnementaux. L’enregistrement historique de la contamination en Ag des huîtres de la Gironde (1979-2007, RNO, Ifremer) indique que le bassin de Decazeville a été la source majoritaire en Ag jusqu’en ~1988. Cependant, l’accumulation maximale de Ag dans ces bivalves après 1993 (de ~40 à plus de 100 mg/kg, poids sec) révèle une contribution croissante de sources additionnelles et contemporaines en Ag comme la photographie, l’ensemencement des nuages (30 à 63 kg/an) ou encore les rejets des eaux usées urbaines de Toulouse et de Bordeaux (42 et 57 kg/an). Ce travail constitue une base nécessaire à l’étude des rejets du cycle de Ag (y compris les nanoparticules) dans le milieu aquatique (quantification, transfert et toxicité) et des risques associés. / Silver (Ag) emissions into the environment from former mining activities and various industrial applications (e.g. jewellery, medicine, photography, electronic products and more recently nanotechnology) make Ag both a historic and an emergent pollutant for which information on its transfer and toxicity in aquatic system are scarce. This work provides a first assessment of Ag sources, transfer and bioaccumulation in the Gironde fluvial-estuarine system. The Lot-Garonne-Gironde River continuum, known for its polymetallic pollution (e.g. Cd, Zn) derived from the Decazeville basin, is a model system for studies on metal transfer from watersheds to the ocean. The relationship between historical records (~50 years) of Ag concentrations in sediment cores from the Lot River, upstream (Ag: 0.3 mg/kg) and downstream (Ag: up to 7 mg/kg) of the Decazeville basin and those of Cd constitutes evidence of a common source and transport/settlement processes due to industrial activities until 1986. High particulate Ag (AgP: 260 mg/kg) and dissolved Ag (AgD: 1,260 ng/l) concentrations in the Riou-Mort River were attributed to current leaching and erosion of slag heaps by rainwater. Those concentrations were 2 to 3 orders of magnitude greater than typical values in the Gironde watershed. However, the Riou-Mort River contribution to the Garonne River Ag fluxes (AgD: 0.008-0.041 t/a; AgP: 0.306-2.44 t/an; 1999-2009) remained low (AgP: <11%; AgD: <6%). The Garonne River provided the quasi totality (63-83%) of Ag inputs to the estuary, mainly in its particulate form (96±2%). The regional geochemical background (AgP/ThP=0.026) was useful to estimate (i) the natural contribution (20-65%) to total AgP fluxes and (ii) the anthropogenic specific fluxes of AgP (15±10 g/km²/a and 0.24±0.16 g/hab/a) in the Garonne watershed (La Réole). In the estuarine salinity, chloro-complexation desorbed ~60% of AgP, causing maximalum AgD concentrations (6-8 ng/l) at salinity 15-25 (addition to the dissolved phase). This quantity was similar to the potentially bioavailable or reactive fraction (i.e. extracted by HCl 1 M). The first estimations of net fluxes suggested that 50-80% of the Ag annual export to the coast occurred in the dissolved phase (0.64-0.89 t/a in 2008 and 0.56-0.77 t/a in 2009). Even if the ionic form Ag+ (the main form in freshwater) is considered as the most bioavailable form, Ag accumulation in estuarine organisms (oysters, shrimps and eels) reflected the higher exposition pressure in brackish water. In-situ caging of European Eels (recommended species for the biosurvey of aquatic systems; European Water Framework Directive) in key sites of the Gironde Estuary during 3 months, highlighted the direct and trophic pathways of Ag contamination at the environmental level. The historical record of Ag contamination of the Gironde Estuary oysters (1979-2007, French Mussel Watch, RNO) indicated that the Decazeville basin was a major Ag source until ~1988. However, the maximum Ag accumulation in oysters after 1993 (from ~40 to more than 100 mg/kg, dry weight) suggested an increasing contribution of additional and contemporary Ag sources like photography, cloud seeding (30-63 kg/a) or Toulouse and Bordeaux wastewater effluents (42-57 kg/a). This work is a basis for future work on Ag (including nanoparticles) cycles and related risks in aquatic systems (quantification, transfer and toxicity).

Depuis plusieurs dizaines d’années, la population des anguilles européennes a souffert d’un dramatique déclin et est classée parmi les espèces hors de leurs limites biologiques depuis 1998. Différents phénomènes, tels que la pêche, les obstacles aux migrations, ou le réchauffement climatique, en sont à l’origine. Cependant, les perturbations environnementales, telles que les contaminations métalliques et organiques ou les épisodes d’hypoxie, participent probablement à la vulnérabilité de cette espèce. Or, l’estuaire de la Gironde est soumis à des contaminations poly-métalliques historiques, ainsi qu’à des contaminations organiques de différentes origines, et à des épisodes hypoxiques réguliers. Les travaux menés au cours de cette thèse, se sont donc composés d’études de terrain visant à identifier les contaminants majeurs chez les anguilles jaunes de l’estuaire de la Gironde, ainsi que leur voie de bio-accumulation et leurs impacts au niveau physiologique, biochimique et moléculaire. Ces études ont nécessité la mise en place d’expériences préliminaires ayant pour objectifs de vérifier les impacts de certaines procédures, telles que l’anesthésie et la mise en cage des anguilles jaunes. D’autre part, les impacts des deux principaux contaminants métalliques et organiques des anguilles européennes de l’estuaire de la Gironde, ont été testés, de façon individuelle et combinée, ainsi que ceux de l'hypoxie sur des anguilles pré-contaminées ou non, lors d’une étude expérimentale.Ainsi, ces travaux ont mis en évidence que les anguilles européennes installées dans la zone avale de l’estuaire, étaient susceptibles d’être soumises à des contaminations poly-métalliques plus importantes, essentiellement d’origine trophique, responsables d’une croissance pondérale moins élevée et de perturbations transcriptionnelles hépatiques et cérébrales. De plus, bien que les contaminations métalliques de ces anguilles ne mettent pas ne danger la santé humaine, les contaminations en PCB sont, en revanche, supérieures aux normes de consommation. D’autre part, ces travaux ont également mis en évidence des dérèglements mitochondriaux ainsi qu’un stress oxydant, au niveau branchial et cérébral chez des anguilles contaminées au Cd, et au niveau cérébral, branchial, hépatique et rénal chez les anguilles contaminées aux PCB. Enfin, la concomitance de ces deux contaminants et/ou d’un épisode d’hypoxie, réduit et/ou retarde les capacités de réponses transcriptionnelles de ces anguilles. Il semble donc que les différentes perturbations chimiques subies par les anguilles européennes au stade jaune au sein de l’estuaire de la Gironde participent de façon non négligeable à la vulnérabilité de cette espèce. / For several decades, the European eel has been suffering from a dramatic decline and has been classified among species beyond their biological limit since 1998. Different phenomena, as fishing, migration barriers, or global warming, are to blame. Environmental perturbations, as metallic and organic contaminations, or hypoxic episodes, probably take part to the vulnerability of this species. The Gironde estuary has been submitted to historic poly-metallic contaminations, to organic contaminations from different origins, and to regular hypoxic episodes. This thesis work is composed of field studies aimed to identify the main contaminants in yellow eel living in the Gironde estuary, their major bioaccumulation way and impacts on physiological, biochemical and molecular parameters. These studies needed preliminary experiments aimed to verify whether some field and handling procedures are consistent with ecotoxicological analyses. Moreover, impacts of the two main contaminants in European eels from the Gironde estuary have been assessed individually or combined, with those of hypoxia on pre-contaminated eels.Thus, these studies have demonstrated that European eels installed in the downstream area of the estuary, were likely to be subject to largest poly-metallic contaminations, mostly by food web, and responsible for a less weight gain and high liver and brain transcriptional disturbances. Furthermore, although the metal contamination of eels does not endanger human health, PCB contaminations are higher than consumption standards. On the other hand, these studies have also revealed oxidative stress and mitochondrial disorders in gills and brain of Cd-contaminated eels, and in brain, gills, liver and kidneys of PCB-contaminated eels. The combination of these two contaminants and/or an episode of hypoxia, reduces and/or delays the transcriptional responses ability of these eels. It seems that the different chemical disturbances, suffered by the yellow eels in the estuary of the Gironde, participate significantly to this species vulnerability.