Wetlands play a vital role in regional and global biogeochemistry by controlling the movement and cycling of nutrients and carbon. While individual wetlands may provide these ecosystem services, high density wetland landscapes, referred to as wetlandscapes, can have far reaching aggregate effects on elemental cycling and solute transport. Here we use forested Delmarva bays or wetlands as a study ecosystem to explore physical and biological controls on wetland chemistry within forested wetlandscapes. The Delmarva wetlandscape consists of thousands of geographically isolated wetlands on the Delmarva Peninsula, United States, which despite their proximity to each other have highly variable sizes, shapes, hydrology, vegetative cover, and biological communities. This physical and biological variation makes the Delmarva wetlandscape an ideal ecosystem to understand spatio-temporal heterogeneity and drivers of biogeochemistry. In this dissertation, I demonstrate that water chemistry within the Delmarva wetlandscape is heterogeneous both within and between surface water and groundwater systems (Chapter 2). Surface water chemistry was primarily influenced by temporal factors (season and month), followed by local hydrology. In contrast, groundwater chemistry was strongly influenced by water level below ground surface and interaction with organic soil layers. These results are important in understanding both internal wetlandscape water chemistry dynamics and export of solutes such as dissolved organic matter (DOM) to adjacent river ecosystems. Further, these results suggest that local biological and hydrological factors strongly affect surface water chemistry in wetlands. To explore these factors, I used an observational approach to determine the role of larval amphibians on wetland biogeochemistry (Chapter 3) and employed high-resolution chemistry sensors to study the effect of hydrological changes on surface water dissolved organic matter concentrations (Chapter 4). Animal waste can contribute substantially to nutrient cycling and ecosystem productivity, yet little is known of the biogeochemical impact of animal excretion in wetland habitats. A common and abundant amphibian in Delmarva wetlands are wood frog (Lithobates sylvaticus) tadpoles. I found that wood frog tadpole aggregations elevated nutrient recycling, microbial metabolism, and carbon cycling in Delmarva wetlands. These results provide evidence for the functional and biogeochemical role of tadpole aggregations in wetland habitats, with important implications for ecosystem processes, biodiversity conservation, and ecosystem management. To further explore the role of hydrology on DOM concentrations, I utilized high-resolution fluorescent dissolved organic matter sensors (fDOM) and applied river solute transport frameworks and metrics to wetland catchments. I found that there was heterogeneity in wetland response to changing hydrology and that seasonality and potentially bathymetry influences fDOM concentrations. Together, these studies inform our understanding of wetlandscape heterogeneity and DOM export, as well as biological and hydrological drivers of biogeochemistry. / Doctor of Philosophy / Wetlands control the movement of nutrients and carbon at local, regional, and global scales. There is a large body of knowledge demonstrating the importance of wetlands to the transport of dissolved water constituents, such as dissolved organic matter (DOM) and nutrients. However, there is little information on what controls surface water chemistry in these wetland landscapes and less is known about belowground water chemistry. In this study I examined the role of water level, wetland shape, and time (i.e., year, month of the year, and season) on surface and groundwater chemistry in wetlands. I found that water chemistry was different between surface and groundwater and that differences were primarily due to seasons or months in surface water wetlands, while water level and flooding of organic matter-rich soil layers controlled groundwater chemistry. These results indicate that there are differences in water chemistry between surface water and groundwater that are controlled by unique drivers. These results also suggested that biological processes such as animal presence may influence wetland chemistry. To understand the role of animals in wetland chemistry, I studied the effect of wood frog (Lithobates sylvaticus) tadpole waste on nutrient concentrations in wetlands and found large tadpole groups are significant recyclers of nitrogen and phosphorous, which were used by microbes as nutrients, leading to enhanced leaf litter break-down in wetlands. These findings imply that tadpoles have an important role in wetland ecosystems by creating locations of enhanced nutrient and carbon cycling and that conservation of amphibian species may also preserve ecosystem processes in wetlands. Additionally, my initial study suggested that hydrology influences DOM concentrations in wetlands. I used high-frequency chemistry sensors to detect fluorescent dissolved organic matter (fDOM) concentrations, which represents a fraction of DOM. I found that relationships and patterns in fDOM concentration were complex, and that season and wetland shape were important in wetland DOM dynamics. Overall, this dynamic behavior across seasons and between wetlands indicates that wetland response to water levels can drive differences in water chemistry between wetlands and is important in our understanding of wetland response to storm events. The information gained from these studies is important in understanding how large wetland landscapes function and control movement of nutrients and carbon. Further, my research has uncovered the role of animal species in controlling nutrient and carbon cycling in wetland environments as well as the complex response of fDOM to water level changes in individual wetlands.

The Belgian Coastal Zone (BCZ) in the Southern Bight of the North Sea is a highly dynamic and optically complex area. This is due to high non-algal particles (NAP) and coloured dissolved organic matter (CDOM) content which in spring adds together with undesirable blooms of the haptophyte Phaeocystis globosa. There is a need for improving the algorithms for chlorophyll a (chl a) retrieval in these highly turbid waters and for developing algorithms for species detection in order to attempt to create an early warning bloom system. This information will contribute to the knowledge of the extent and magnitude of the P. globosa bloom in Belgian waters. In this study, pure cultures of the main taxa present in the BCZ, diatoms and P. globosa, were combined with field measurements of light absorption of total particles, phytoplankton and dissolved material, pigment determination and phytoplankton counts to address the main objectives. Sampling was performed during 8 cruises covering winter, spring, summer and late summer, and along nearshore-offshore gradients from 2003 to 2006. The area is characterised by a high spatio-temporal variability of IOPs due to the high dynamics of the area in terms of currents, salinity gradients and biological production. During spring the presence of P. globosa modulates the IOPs across all the area, the particle absorption is significantly higher than summer and there is no significant coast-offshore variability for phytoplankton and CDOM. The design of chl a retrieval algorithms assumes negligible absorption of NAP and CDOM in the near infrared (NIR) and the use of a fixed value of specific phytoplankton absorption. It is shown that neglecting the NAP and CDOM absorption in the NIR will have a significant overestimation impact in retrieval of chl a. On the other hand, the specific phytoplankton absorption was found to be highly variable (0.015 „b 0.011 m2 mg chl a-1). Both results will affect directly the retrieved chl a. The spatial variability of CDOM was significant varying between 0.20-1.31 m-1 in the marine area and between 1.81-4.29 m-1 in the Scheldt estuary. CDOM was found to be related to salinity with conservative mixing within the Scheldt estuary and during some seasons in the BCZ, however deviations from conservative mixing suggest other inputs to the CDOM pool. Analyses of the spectral slope of the CDOM absorption curve revealed two main CDOM pools in the area, an allochthonous one delivered by the Scheldt estuary and an autochthonous one associated with the phytoplankton spring bloom decomposition. Algorithms for CDOM retrieval will be affected if the variability in the relation between CDOM and salinity is not taken into account. The optical characterisation of diatoms and P. globosa from the BCZ in pure cultures revealed that the main differences in the phytoplankton absorption spectra were found at 467 and 500 nm corresponding to the absorption of the pigments chlorophyll c3 (chl c3) characteristic of P. globosa and fucoxanthin, respectively. Accordingly, both the absorption at 467 nm and the ratio 500/467 nm were successfully used to discriminate the two taxa in cultures and field samples. This latter indicator was not preserved in the reflectance signal due to degradation of the signal when passing from absorption to reflectance, and thus could not be used for algorithm development. The spectral feature at 467 nm was later used as the basis for the development of a flag-type algorithm to detect chl c3 using either absorption or water-leaving reflectance data. Also, the correlation between the algorithm¡¦s retrieved chl c3 and P. globosa cell number allowed the quantification of the bloom. The main findings of this thesis highlight the importance of the IOPs characterisation for the improvement and development of ocean colour retrieval algorithms in these highly complex waters.

Dissolved organic matter (DOM) is present in all forested catchments and can be important in binding metals, absorbing UV, and the transport of nutrients (C, N, S, P). DOM is extremely heterogeneous in time and space, making it difficult to characterize. New techniques have been developed to determine δ34S and δ18O in DOM. These techniques have been applied to samples from Harp and Plastic Lake catchments (45??23'N, 79?? 08'W, 45??11'N, 78?? 50'W) in order to obtain information about sources and sinks of DOM within forested catchments on the Canadian Shield. In conjunction with sulphate and DOC concentrations, this new data provides valuable insight into sulphur cycling and DOM alteration within these catchments. Data generated for δ34S-DOM and δ18O-DOM appears to be the first data reported in the literature for DOM. The inorganic (δ34S-SO42-) and organic S (δ34S-DOM) differs by environment in both catchments. The range of δ34S-SO42- is between 3. 3‰ and 10. 3‰, and the range of δ34S-DOM is from 3. 4‰ to 8. 7‰. Sulphate in the Harp Lake catchment in most samples is subject to some sort of cycling within the watershed, since δ34S-SO42- differs from precipitation. In the Harp Lake catchment, upland δ34S-SO42- is influenced by historical precipitation. The δ34S-DOM is derived from leaching and microbial activity of DOM from organic horizons in the soil. The δ34S-SO42- and δ34S-DOM of wetland streams is extremely variable, controlled by hydrology. The δ34S-SO42- provides information on oxidation-reduction dynamics in the wetland, and δ34S-DOM provides information about sources of DOS in the wetland. The δ34S-SO42- and δ34S-DOM are possibly related in Harp Lake. Mineralization of DOS as evidenced by δ34S-DOM and DOS concentrations could be a small input of SO42- into Harp Lake. It is possible δ18O-DOM could be an indicator of DOM alteration. The range of δ18O-DOM is between 8. 2‰ and 14. 4‰. The δ18O-DOM in the Harp Lake catchment is highly correlated with relative molecular weight, which has been shown to decrease with increasing alteration. Wetland streams show the largest range in δ18O-DOM, while uplands, groundwater, and Harp Lake are the least varied. The highest δ18O-DOM values are from sources of DOM such as leaf leachates (representative of forest floor litter) and wetlands. The most depleted samples are from groundwater and Harp Lake which typically contain highly altered DOM. The δ34S-DOM and δ18O-DOM can provide valuable information on sources of DOM and DOM alteration within the catchment. The δ18O-DOM could also allow the separation of autochthonous and allochthonous DOM in lakes.

In order to delineate the potential sources and to understand the main controls on the biogeochemical cycling of dissolved and particulate organic matter (DOM, POM) and dissolved inorganic nitrogen (DIN) during estuarine mixing, comprehensive seasonal geochemical and isotopic and surveys across the freshwater-tidal interface were carried out in the Tyne and Tweed Estuaries, NE UK. This study provided a contrast between a relatively pristine system (Tweed) with one that is heavily influenced by anthropogenic activity (Tyne). Geochemical and isotopic (13C, 14C and 15N) analyses demonstrated the predominance of terrigenous organic matter in both these estuaries, with elevated river discharges leading to enhanced terrestrial loading. High pCO2 values in the Tyne (summer) and Tweed (winter) suggested that a significant fraction of this terrestrially-derived organic matter (both DOM and POM pools) is relatively labile and can potentially undergo significant mineralization during estuarine mixing. In both estuaries in situ processing of DIN was relatively minor, with mixing between different sources being the main factor in controlling the distribution of nitrate and ammonium across the salinity gradient. However, anthropogenic ammonium discharges in the Tyne were found to have an enormous direct and indirect impact on estuarine nitrogen cycling. Large, concave removals of terrigenous high molecular weight (HMW) DOC caused by flocculation, biodegradation, and/or photochemical oxidation were associated with a non-conservative 13C-enrichment in d13C signatures. Radiocarbon dates showed an export of young (modern) HMW DOC and old (100-1000s of years), terrigenous POC to the North Sea. 14C-enriched values in coastal North Sea HMW DOC were attributed to anthropogenic discharges originating from within the coastal North Sea environment. In the Tweed, seasonal changes in soil characteristics resulted in an older age for POM during the summer. In the Tyne, decreases in POC% with increasing salinity sometimes coincided with an increase in POC age. This was attributed to mixing with older sediment and to the possible preferential loss of the younger, more labile POC fraction during mineralization. This study has shown that land use patterns, sewage inputs, and freshwater flushing time are the main influences in determining the behaviour and origin of organic matter and DIN entering the coastal North Sea in these two systems.

Ce doctorat s'intègre dans les programmes OPUR et Piren-Seine et a eu pour vocation d'améliorer les connaissances actuelles sur l'influence des rejets urbains de temps de pluie sur la spéciation et la biodisponibilité des métaux dans les systèmes sous forte pression urbaine tel que la Seine. En effet l’impact des métaux lourds dans le milieu récepteur sur les organismes vivants dépend d'une part de leurs teneurs totales mais aussi et surtout de leur biodisponibilité. Il est généralement admis que la forme biodisponible des métaux lourds pour les organismes vivants est la forme dissoute libre. Les RUTP vont donc pouvoir considérablement modifier la teneur et la biodisponibilité des métaux lourds dans le milieu naturel dans la mesure où ces rejets sont fortement chargés en matière organique dissoute (MOD) qui va influencer considérablement, avec la MOD déjà présente dans le cours d'eau, la spéciation des métaux dans le milieu étant donnée sa capacité à complexer ces derniers et sa tendance à diminuer leur biodisponibilité. La compréhension de l'influence de la MOD sur la spéciation et la biodisponibilité des métaux suppose en outre que l'on connaisse précisément sa composition chimique ou plus exactement ses groupements fonctionnels. C'est pourquoi une partie de ces travaux est consacrée à la caractérisation de la matière organique dissoute d'origine naturelle et urbaine par son fractionnement selon le critère de polarité. Une caractérisation plus fine a été réalisée à l'aide des analyses fonctionnelles permettant ainsi de mieux aborder l'influence de la MOD sur la spéciation et la biodisponibilité du cuivre. Parallèlement à l'étude de caractérisation de la MOD, ce travail s'attache à mieux cerner le rôle de la MOD d'origine urbaine en particulier de la MOD hydrophile sur la spéciation et la biodisponibilité du cuivre. Dans cet objectif, la technique potentiométrique à l'aide d'électrode ionique spécifique ainsi que des biotests de toxicité aiguë (Daphnia magna) ont permis :- d'étudier la complexation du cuivre par les MOD afin notamment de fournir des paramètres de complexations des MOD hydrophiles peu connues jusqu'à présent et ainsi mieux prédire le transport des métaux en milieu urbain.- d'évaluer le rôle protecteur de la MOD d'origine urbaine sur la biodisponibilité du cuivre. Les résultats ont montré que la MOD issue des rejets urbains et rejetée dans le milieu récepteur présente des caractéristiques originales à savoir un fort pourcentage de MOD hydrophile, c'est à dire une faible hydrophobicité et un degré d'aromaticité peu marqué soulignant le caractère peu réfractaire de cette MOD. En revanche une plus grande diversité fonctionnelle de la MOD d'origine urbaine par rapport à la MOD naturelle a été mise en évidence notamment par un taux de structures protéiques très important. Les résultats obtenus vis-à-vis des MOD d'origine urbaine ont montré une réactivité particulière vis-à-vis du cuivre. En effet les rejets urbains ont montré une teneur en sites complexant plus élevée que ce qu'il est observé pour des matières organiques naturelles. Le rôle particulier de groupements amines dans la complexation du cuivre a été mis en évidence. L'approche utilisée pour évaluer la biodisponibilité du cuivre a révélé pour l'ensemble des MOD un effet protecteur vis-à-vis du cuivre sur les organismes vivants. Une corrélation positive de cet effet avec la teneur en eaux usées été mise en évidence, notamment pour les MOD des RUTP et plus particulièrement pour la fraction hydrophile (HPI), signalant ainsi la forte influence de la MOD d'origine urbaine sur la biodisponibilité et la toxicité du cuivre / This thesis was carried out on the framework of the OPUR and Piren-Seine programs. The main objectives were to improve the current knowledge on the influence of combined sewer overflows (CSO) on metal speciation and bioavailability in urban aquatic system. Indeed, the impact of heavy metals in the receiving environment on the life of microorganisms depends on a portion of their total concentrations but also and especially of their bioavailability. It is generally recognized that the bioavailable heavy metals to microorganisms is dissolved free. The CSO's will be able to significantly change the content and bioavailability of heavy metals in the environment in so far as these discharges are heavily loaded with dissolved organic matter (DOM) which will considerably influence with the DOM already present in course of water the speciation of metals in the environment given its ability to complex metals and its tendency to decrease their bioavailability. The understanding of the influence of DOM on trace metal speciation and bioavailability required that the chemical composition of DOM, more exactly its binding sites should be well understood. Therefore, one part of this research focused on the characterization of DOM of natural and urban origin by fractionation according to the criteria of polarity. A finer characterization was performed using functional analyses that were of prime importance to better understand the influence of DOM on copper speciation and bioavailability. Alongside the characterization study of the DOM, this work aims to better understand the role of urban DOM in particular hydrophilic fraction on the speciation and bioavailability of copper. To accomplish these objectives, the technique such as potentiometry with ionic selective electrode and bioassay such as an acute toxicity test (Daphnia magna) were performed in order to: - Study the copper binding by DOM in order to give some binding parameters of hydrophilic DOM and to better predict the fate of the trace metal. - Evaluate the protective role of urban DOM on copper bioavailability. Results showed some particular characteristics of urban DOM such as a high proportion of hydrophilic DOM, i.e. a low hydrophobicity and a low degree of aromaticity underlying the low refractory character of this DOM. Nevertheless a higher content of various functional groups was determined in urban DOM than in natural DOM. A very high content of proteinaceous structures was particularly identified in urban DOM. Binding experiments revealed a higher content of binding sites in urban discharges than in natural DOM and these sites are strongly correlated to amino groups. The approach used to evaluate copper bioavailability depicted a protective role of DOM to the organisms Daphnia magna(...)

Master of Science / Department of Geology / Saugata Datta / Mass poisoning of arsenic (As) has affected roughly 60 million people in the Bengal Basin (Bangladesh and West Bengal, India) and 43 million people alone in West Bengal. Elevated levels of Manganese (Mn) is another alarming issue in the groundwaters of this region (MCLs: As<10µg/L and Mn< 0.4mg/L). Four locations in Murshidabad district (south-central part of Bengal Basin) were chosen for this current study. Among the 4 locations, two of them showed high concentration of As (>50 - 4622µg/L; 2009 survey) and they are Beldanga: 23° 56'N& 88°15'E and Hariharpara: 24°3.68'N & 88° 21.63'E. On the other hand: Nabagram (24°12.08'N & 88°13.29'E) and Kandi (23°58.6'N & 88°6.68'E) demonstrated less dissolved As (<10µg/L) in groundwaters. Study areas were located to the west (Nabagram, Kandi) and east (Beldanga, Hariharpara) of the river Bhagirathi, a tributary of the river Ganges, flowing N-S through the district of Murshidabad. Eastern side of the river is occupied by grey colored Holocene sediments and western side has more oxidized orangish-brown Pleistocene sediments. Comparative study of major water quality parameters between these sites revealed high As (10-1263µg/L) and low Mn (0.1-1.3mg/L) in the areas like Beldanga, Hariharpara while low As (0-15µg/L) and higher Mn (0.2-4.2mg/L) in Nabagram and Kandi. The pH range for high and low As areas were 4.5-7.8 and 5.1-8.2 respectively. Phosphates showed values <0.04-2.21mg/L in high As areas and <0.08-2.52mg/L in low areas whereas Cl- values were higher within low As areas (29-200mg/L) and lower within high As areas (3.9-78.4mg/L). Fe(t) and Fe2+ values at high and low As areas were 0-13.5mg/L, 0.01-0.11mg/L and 0-1.4mg/L, 0.04-0.06mg/L respectively. δ18O and δD results revealed that monsoonal precipitation is the major recharge source in this area with some input from the surficial waterbodies as ponds in shallower depths within high As areas. The total As extracted from core sediments in these areas do not show much difference: total As in high and low As areas ranges from 6.4-18 mg/kg. Sequential extraction results revealed that majority of the sediment bound As is present in residual phases (>40%). DOC in groundwaters in high and low As areas were 1.5-3.2 and 0.5-1.3mg/L respectively and they had positive correlation with As within the depth profiles. Dissolved organic matter (DOM) characterization studies indicated that microbial proteins (Tyrosine and Tryptophan) are the major components in the groundwaters in the low As region, whereas high As area groundwaters tend to have higher content of humic DOM (A and C). Cl/Br molar ratio of high As wells were low compared to the low As wells. Current study revealed the importance of organic matters (and not the mineralogy of the sediments) both in sediments and groundwaters in controlling the release of As from sediment, at least in the shallow parts of Bengal delta aquifer and microbial mediated reductive dissolution of FeOOH in the presence of organic matter is the major mechanisms by which sediment bound As (<50m depth) is released into the groundwater. The darker organic matter rich sediments (OM both sediment bound and anthropogenically derived) existing at the depth range 20m-50m with reducing environment persisting in both high and low As areas are possible reasons for elevated levels of As in this region.

Doctor of Philosophy / Department of Civil Engineering / David R. Steward / Groundwater contamination with arsenic (As), a naturally occurring metalloid, is a worldwide problem. Over 100 million people are at health risk due to arsenic contaminated groundwater, especially in the Bengal Basin in south-east Asia. Dissolved organic matter (DOM), geology and geomicrobiology are important factors affecting arsenic mobility. This study focuses on interactions of different aspects of natural organic matter in arsenic-contaminated environments. A literature review specifically includes past studies done on fundamentals of arsenic geology, geomicrobiology, DOM characterization and relevant analytical methods and tools. Based on background information already collected, this research is focused on specific research questions and corresponding hypotheses. The overarching goal of this investigation is to better understand the mechanisms by which DOM influences arsenic mobilization. The specific goals of this research are: 1) to evaluate role of oxidized humic quinones in reductive dissolution of Fe-As minerals and subsequent arsenic mobilization via electron shuttling, 2) to quantify the rate of microbially mediated reductive dissolution in the presence of oxidized humic quinones, 3) to evaluate DOM-Fe-As ternary complex formation and its influence on arsenic mobility and 4) to characterize DOM in the arsenic-contaminated aquifers of West Bengal, India and evaluate its role in arsenic mobilization using groundwater flow and contaminant transport modeling approach. Results of this study revealed that oxidized quinone like moieties (such as fulvic acids) serve as an electron shuttle and enhance the reductive dissolution process under reducing conditions, hence mobilize the arsenic in groundwater. Another key result from this study suggested that arsenic binds with non-aromatic portion of the humic-like DOM under reducing conditions and increases its solution concentration. A field study conducted in West Bengal, India revealed that the mechanisms studied in the laboratory exists in reducing aquifer. A groundwater flow and reactive transport model was created to explain multiple interactions of DOM and arsenic spatial scales. Broader impacts of this study include significant addition to scientific knowledge about subsurface biogeochemistry and the role of DOM in biogeochemical reactions in the subsurface.

Les activités anthropiques ont apporté des changements majeurs à notre système global. Par ailleurs, la matière organique dissoute(MOD) du littoral a une grande influence sur le cycle global du carbone et donc sur le changement climatique. L'apport côtier enMOD représente la matière organique terrestre. Les rivières urbanisées sont fortement impactées par la MOD anthropiqueprovenant des usines de traitement des eaux usées. La MOD chromophorique est un sous-groupe de la MOD qui peut absorber lalumière. La MOD fluorescente est à son tour un sous-groupe de la MOD chromophore. Le signal de fluorescence de la MODanthropogénique dans la zone côtière n'est pas bien caractérisé et évalué dans la littérature. Les dégradations induites parphotochimie et les changements au niveau moléculaire sont peuvent de plus influencer la MOD. Dans la présente étude, plusieursexpériences d'irradiation solaire ont été menées avec plusieurs modes de filtration de mélange d’eau de rivière, d’eau de mer et d'uneffluent de station de traitement des eaux usées dans le but de trouver un signal spécifique de fluorescence comme un traceur de laMOD anthropique en utilisant les matrices d'émission d'excitation de la spectroscopie de fluorescence (EEMs) couplées à latechnique statistique chimiométrique de l'analyse factorielle parallèle CP/PARAFAC. Un modèle de régression multilinéaire a étédéveloppé entre la contribution des composantes CP/PARAFAC et la composition du mélange. La cinétique des paramètres derégression multilinéaire a également été étudiée. Des suivis géographiques de l'évolution du signal de fluorescence dans la rivièreGapeau jusqu'à la mer ont été menées ainsi qu’une étude temporelle du signal de fluorescence. Le modèle de régressionmultilinéaire développé a été appliqué pour modéliser les résultats des expériences de champs géographiques et temporelles. Lesrésultats ont montré que le modèle de régression multilinéaire est excellent. Par contre la recherche d'un signal ou d'une signaturede fluorescence spécifique pour l'eau de rivière, les stations d'épuration des eaux usées ou l'eau de mer n'a pas pu être réalisée dansce travail. Dans la zone côtière affectée par l'homme, les matières organiques fluorescentes résiduelles proviennent principalementsinon uniquement de l'usine de traitement des eaux usées, et aucun signal spécifique provenant de l'eau de mer n'a pu être détectéprès de la côte. / Anthropogenic activities have done major changes to our global system. The coastal dissolved organic matter has great influenceon the global carbon cycle and hence climate change. The riverine input of dissolved organic matter represents the terrestrialorganic matter. Urbanized rivers is greatly impacted by the anthropogenic dissolved organic matter coming from wastewatertreatment plants . Chromophoric dissolved organic matter is a subgroup of the dissolved organic matter which can absorb light.Fluorescent dissolved organic matter in turn is a subgroup of the chromophoric dissolved organic matter .The fluorescence signalof the anthropogenic dissolved organic matter in the coastal zone is not well characterized and evaluated in the literature.Photochemically induced degradations and changes at the molecular level is considered to be a great process which could influencethe dissolved organic matter . In the present study, Laboratory mixing experiments several sunlight irradiation experiments wereconducted with several modes of filtration of three endmember mixing components ( River water, Sea water , wastewater treatmentplant effluent discharge) with the objective of finding a specific signal of fluorescence which could be a tracer of the anthropogenicdissolved organic matter through using the fluorescence spectroscopy excitation emission matrices (EEMs) coupled with thechemometric statistical technique of Parallel Factor analysis CP/PARAFAC. Moreover, multilinear regression model between thecontribution of CP/PARAFAC components and two content fraction of River water and Seawater endmember was developed. Inaddition the kinetics of the multilinear regression parameters were investigated. On top of that , geographical investigations of theevolution of fluorescence signal in the Gapeau river till the sea were conducted. Furthermore, Temporal investigation of thefluorescence signal for four water points in the pathway of Gapeau river were done. The multilinear regression model developedwas applied to model the results of the geographical and temporal field experiments. Results have shown that Multilinearregression model for contribution of CP/PARAFAC components is excellent and could be done for the three endmembers. Inaddition the search for specific fluorescence signal or signature for river water, wastewater treatment plants and sea water couldn’tbe done in this work. In human impacted coastal zone, residual fluorescent organic matter come from wastewater treatment plant,and no specific signal from sea water could be detected near the coast.

Two oceanographic cruises were conducted during September 2003 and March 2004 in the eastern half of the Cariaco Basin. Specific objectives were to examine the hydrography of the seasonal upwelling plume characteristic of this region, the spatial distribution of particles in the area, and to help determine the source and relative importance of in situ particle production vs. terrigenous particles delivered laterally from the coast. During September 2003, average surface salinities within the basin were higher (36.6) relative to Caribbean Sea waters outside the basin (35.6). Salinity patterns indicated that the Orinoco and Amazon River plumes did not enter or influenced the basin directly. The upwelling plume in March 2004 stimulated primary productivity. Beam attenuation and CDOM fluorescence profiles showed marked vertical structure in biomass of microbial populations, particularly near the oxic-anoxic interface typically located between about 250 and 300 m. There is an increasing difference in temperature and salinity between the Cariaco Basin and the adjacent Caribbean Sea below 200 m. Inside the Basin temperatures and salinities were higher by 4oC and 0.5. The influence of local rivers on the Cariaco Basin was evident during September 2003. Low salinity plumes with high beam attenuation (1m-1) lined the southern margin of the Basin. The primary rivers that affected the basin were the Unare and Neverí Their sediment input affected the shelf near the river mouths, and a surrounding radius of up to 40 Km. Their low salinity plumes were carried northwestward toward the CARIACO time series station. In March 2004, there was minimal or no terrigenous input from local rivers. Near the Manzanares River, off the city of Cumaná and near Cubagua Island, located south of Margarita Island, attenuation due to suspended particles (0.09 m-1) was observed at depth (70-150 m) during both cruises (0.09-0.15 m-1). Therefore, sediment transport from the shelf into the basin seems to occur year-round. More observations are necessary to determine the nature and origin of these particles. In March 2004, there was minimal or no terrigenous input

In Sweden, utilisation of incinerator residues outside disposal areas is restricted by environmental concerns, as such residues commonly contain greater amounts of potentially toxic trace elements than the natural materials they replace. On the other hand, utilisation can also provide environmental benefits by decreasing the need for landfill and reducing raw material extraction. This thesis provides increased knowledge and proposes better approaches for environmental assessment of incinerator residue utilisation, particularly bottom ash from municipal solid waste incineration (MSWI).A life cycle assessment (LCA) based approach was outlined for environmental assessment of incinerator residue utilisation, in which leaching of trace elements as well as other emissions to air and water and the use of resources were regarded as constituting the potential environmental impact from the system studied. Case studies were performed for i) road construction with or without MSWI bottom ash, ii) three management scenarios for MSWI bottom ash and iii) three management scenarios for wood ash. Different types of potential environmental impact predominated in the activities of the system and the scenarios differed in use of resources and energy. Utilising MSWI bottom ash in road construction and recycling of wood ash on forest land saved more natural resources and energy than when these materials were managed according to the other scenarios investigated, including dumping in landfill. There is a potential for trace element leaching regardless of how the ash is managed.Trace element leaching, particularly of copper (Cu), was identified as being relatively important for environmental assessment of MSWI bottom ash utilisation. CuO is suggested as the most important type of Cu-containing mineral in weathered MSWI bottom ash, whereas in the leachate Cu is mainly present in complexes with dissolved organic matter (DOM). The hydrophilic components of the DOM were more important for Cu binding than previously understood. Differences were also observed between MSWI bottom ash DOM and the natural DOM for which the geochemical speciation models SHM and NICA-Donnan are calibrated. Revised parameter values for speciation modelling are therefore suggested. Additions of salt or natural DOM in the influent did not change the leachate concentration of Cu. Thus, although Cl and natural DOM might be present in the influent in the field due to road salting or infiltration of soil water, this is of minor importance for the potential environmental impact from MSWI bottom ash.This thesis allows estimates of long-term leaching and toxicity to be improved and demonstrates the need for broadening the system boundaries in order to highlight the trade-offs between different types of impact. For decisions on whether incinerator residues should be utilised or landfilled, the use of a life cycle perspective in combination with more detailed assessments is recommended. / QC 20100914