Le but de ce travail est de tester une approche multi-traceurs permettant de caractériser l'origine (éléments majeurs, Sr, Br, 87Sr/86Sr, δ18O, δ2H) et les temps de résidence (3H/3He, CFC, SF6) des eaux, pour identifier l'origine et évaluer le devenir des contaminants dans une nappe alluviale superficielle et peu profonde, la nappe de la Vistrenque. Les molécules étudiées sont les triazines, le métolachlore, le diuron, la carbamazépine, le sulfaméthoxazole, le diclofénac et l'ibuprofène. L'aquifère étudié est alimenté par une recharge directe, occasionnant le lessivage des pesticides des sols, et une recharge latérale provenant de l'aquifère karstique adjacent entraînant une dilution des eaux de la nappe en triazines. Localement, une contribution des eaux de surface (cours d'eau locaux, eau importée du Rhône) à la recharge de la nappe est mise en évidence entraînant également une dilution des eaux de la nappe en triazines mais au contraire une contamination en COE, quoique, en faibles concentrations. Les âges apparents des eaux alluviales échantillonnées, déterminés principalement par le couple 3H/3He, varient entre 1.4 et 22 ans. Le couplage de l'âge des eaux à leurs teneurs en triazines montre une persistance de ces molécules dans le milieu souterrain, et une atténuation de leur signal d'entrée soulignant l'efficacité de leur interdiction en 2003. Finalement, les eaux de la nappe alluviale montrent des rapports de dégradation des triazines variant entre 0,3 pour les eaux influencées par les eaux de surface et 4,8 pour celles montrant des âges apparents de 22 ans, suggérant une augmentation de ce rapport avec le temps de transfert des pesticides dans le système. / The aim of this work is to test a multi-tracer approach allowing the characterization of groundwater origin and residence time in a shallow alluvial aquifer, the Vistrenque aquifer, in order to identify the origin and the fate of contaminants therein. The selected compounds for the study are triazines, metolachlor, diuron, carbamazepine, sulfamethoxazole, diclofenac, and ibuprofen. The studied aquifer is mainly fed by 1) a direct recharge inducing pesticides leaching from soil layers and unsaturated zone and 2) by a lateral recharge from the karst adjacent aquifer, which induces triazines dilution in the alluvial aquifer. A local contribution of surface water (local streams and imported Rhône River water) was evidenced in the alluvial groundwater inducing also triazines dilution but EOCs contamination nevertheless at low concentrations. The apparent age of the alluvial groundwater samples varies between 1.4 and 22 years. Linking groundwater age to triazines contents allowed to highlight, first, the persistence of these compounds in the alluvial groundwater and, second, the decreasing of their input signal in relatively recent groundwater samples in accordance with their forbidding in 2003. Finally, the Vistrenque alluvial groundwater showed triazines degradation ratios varying from 0.3 for groundwater influenced by surface water infiltration to 4.8 for groundwater characterized by relatively older apparent residence time on the order of 22 years. This suggests an increasing ratio with the transfer time of these compounds in the alluvial aquifer system.

La gestion des boues de station d'épuration est un problème majeur. Dans ce travail, des charbons préparés à partir de boues de station d'épuration (SC) ont été utilisés comme support de catalyseurs. Les performances de ces catalyseurs ont été évaluées dans trois réactions d'oxydation pour le traitement de l'eau : le procédé Fenton, l'oxydation en voie humide catalytique et l'ozonation catalytique. Le catalyseur à base d'oxyde de fer supporté sur ce charbon (FeSC) est très actif dans le procédé de type Fenton pour la décoloration et la minéralisation de l'acide orange II (AOII). Les impuretés inorganiques présentes dans le charbon (cendres), telles que SiO2 et AI2O3, peuvent jouer le rôle de co-catalyseur. Le catalyseur FeSC est également très performant dans l'oxydation en voie humide catalytique du 2-chlorophénol à 120°C sous 0.9 MPa de pression partielle d'oxygène. Cependant, une lixiviation du fer est observée en cours de réaction du fait de la production de HC1 et de petits acides carboxyliques. La lixiviation du fer peut toutefois être évitée lorsque le pH du mélange réactionnel est maintenu en dessus de 4.5, sans que les performances catalytiques n'en soient affectées. Enfin, un catalyseur Mn-g-C3N4 supporté par un charbon obtenu à partir de boue de station d'épuration obtenu par modification de nitrure de carbone par des nanoparticules de manganèse a été synthétisé. L'activité catalytique de ce catalyseur composite est 1.6 fois supérieure à celle du catalyseur Mn-g-C3N4 non supporté. Ce catalyseur composite présente par ailleurs une bonne résistance à l'oxydation et une bonne stabilité, sans qu'aucune lixiviation du manganèse ne soit observée / The disposal of sewage sludge has become an issue of particular concern. In this thesis, sewage sludge derived carbon (SC) was employed as a catalyst support. The catalytic behavior of the prepared SC-based composite catalysts was investigated in three kinds of typical oxidation reactions, including heterogeneous Fenton-like oxidation, catalytic wet air oxidation (CWAO) and catalytic ozonation. Sewage sludge-derived carbon supported iron oxide catalyst (FeSC) showed high Fenton-like performances in the discoloration and mineralization of acid orange II (AOII). Inorganic components in the SC, such as SiO2 and AI2O3 may present have a co-catalytic effect upon Fenton-like reaction. FeSC catalyst also performed quite well in the CWAO of 2-CP at 120°C under 0.9 MPa oxygen partial pressure. However, iron leaching was observed due to the generation of HC1 and some small chain organic acids. Iron leaching could be efficiently prevented when the pH of the solution was maintained at values higher than 4.5, while the catalytic activity was only slightly reduced. Finally, Mn2O3 nanoparticles modified g-C3N4 (Mn-g-C3N4) was synthetized as a novel ozonation catalyst. To enlarge the adsorption capacity of the catalyst and improve its performances in the ozonation of sulfamethoxazole, the Mn-g-C3N4 catalyst was further supported over the sewage sludge-based activated carbon (SBAC). The catalytic activity of the composite catalyst was ca. 1.6 times higher compared to the unsupported Mn-g-C3N4 catalyst. The composite catalyst also exhibited very good resistance towards oxidation, limited Mn leaching and high stability

Très appréciés des consommateurs du fait de leur qualité nutritionnelle, les produits de la mer jouent un rôle important dans l'alimentation humaine. Toutefois, la confiance du consommateur vis-à-vis de leur qualité est affectée par les riques associés à une exposition aux contaminants chimiques et à la fraîcheur des produits. Si le premier aspect résulte de la pollution des eaux marines sous l'effet d'une forte anthropisation des littoraux, le second est lié à la haute périssabilité de ces produits. Évaluer les niveaux de contamination chimique et la qualité-fraîcheur des produits de la mer est plus qu'un besoin : c'est aujourd'hui une nécéssité. C'est dans ce contexte que les travaux de cette thèse ont été menés. Deux objectifs principaux ont été visés dans la présente étude. Le premier objectif de ce travail était de faire une évaluation spatiale et saisonnière des niveaux de contamination par les polluants métalliques et organiques (HAPs et PCBs) des zones côtières du Sénégal en s'intéressant aux teneurs en contaminants dans les organismes marins. Nous avons étudié 7 espèces marines représentatives des différents maillons de la chaîne trophique (une macroalgue verte, un mollusque bivalve, un crustacé et 4 espèces de poisson) prélevées le long du littoral au niveau de 5 sites présentant des degrés d'anthropisation différents. Les résultats de cette étude montrent que les teneurs en contaminants chimiques des organismes marins sont variables selon les espèces et soulignent ainsi la nécéssité de l'approche multi-espèces pour l'étude de la contamination chimique du milieu. Des variations inter-sites de la teneur en contaminants chimiques dans les organismes ont été mis en évidence. Les sites les plus anthropisés comme Soubédioune et Rusfisque sont ceux qui présentent les teneurs les plus élevées. Les niveaux de contamination métalliques et organiques dans les organismes marins du littoral sénégalais sont inférieurs ou du même ordre de grandeur que ceux mesurés dans d'autres régions d'Afrique de l'Ouest ou dans d'autres régions du monde. L'évaluation des risques associés à l'ingestion des produits de la mer analysés montre que les teneurs en contaminants chimiques sont faibles et inférieures aux limites maximales admissibles pour la consommation humaine (norme EU). Seuls les sites de Rufisque et Soumbédioune présentent quelques dépassements chez certaines espèces (moules, sardinelles). Le deuxième objectif de cette étude était de développer des méthodes permettant d'évaluer la fraîcheur des filets de poisson et de différencier des filets frais des filets décongelés. Les méthodes retenues sont basées sur la mesure de l'augmentation de la perméabilité cellulaire du muscle de poisson. La conservation des filets de poisson à 4°C va conduire à une perméabilisation des cellules dans le temps qui peut être apréhendée par la mesure de la libération d'enzymes intracytoplasmiques ou par l'augmentation de la perméabilité des cellules à des colorants fluorescents. La mesure de l'activité LDH est intéressante à double titre : elle va permettre d'une part de mesure le niveau de lyse cellulaire, donc le niveau d'altération, des filets de poisson dans le temps. Elle va permettre d'autre part grâce à sa sensibilité à la congélation de mieux cerner les conditions qui permettraient à terme de faire la distinction entre les filets frais et des filets congelés/décongelés. / Much appreciated by consumers for its nutritional qualities, seafood plays an important role in human diet. Consumer confidence in the quality of these foodstuffs is nevertheless affected by concerns about risks associated with exposure to chemical contaminants and the freshness of these products. If the first of these is the result of pollution resulting from increasing human activities along coastlines, the second is linked to the highly perishable nature of these products. An evaluation of the levels of chemical contaminants in seafood and of its freshness is therefore a necessity. It is within this context that the work presented in this thesis was carried out. Two principal objectives were targeted in the present study. The first objective of this work was to evaluate the spatial and seasonal variability of seafood contamination by elements (including metals) and organic pollutants (PAHs and PCBs) along the Senegalese coast. We studied 7 marine species representative of different trophic level (a green macro algae, a bivalve mollusc, a crustacean and 4 species of fish) sampling them along the coastline at 5 sites representing different human activity pressur. The result of this study showed that contamination levels varied with species, underlining the importance of a multi-species approach to study contamination in the marine environment. Variations between sites were also observed. Sites with the greatest human activity, such as Soumbédioune and Rufisque, were also those where the highest levels of contaminants in seafood were found. The levels of contamination measured along the Senegalese coast, of both elements and organic pollutants, were inferior or of the same order of magnitude as those reported from other West African sites or from other regions of the globe. The risks associated with eating theseseafood products were low, with contaminant levels generally below the admissible limits (EU) for human consumption. Only a few samples of certain species (mussels, sardines) exceeded these limits at Soumbédioune and Rufisque. The second objective of this study was to develop methods to evaluate the freshness of fish fillets, and to distinguish fresh fillets from previously frozen ones. The methods developed were based upon a measure of cellular permeability within the fish muscle tissue. The conservation of fish fillets ar 4°C results in increased permeability of cells over time, measurable by studying the liberation of intra-cytoplasmic enzymes or the increasing permeability of cells to fluorescent colouring agents. The measurements of lactate dehydrogenase (LDH) is doubly interesting in this contex : on the one hand it enables a measure of cell lysis, and so the level of alteration of the fillets over time, to be established. It also, thanks to its sensitivity to freezing, to better distinguish fresh fillets from those that have been frozen then thawed.

Chaque année, 65 millions de m3 de sédiments sont extraits par dragage des ports, des canaux, des rivières et des fleuves français. Ces matériaux sont souvent contaminés par des métaux lourds, pesticides et autres polluants organiques accumulés au cours du temps, et doivent être stockés à terre. La valorisation des sédiments contaminés est encadrée par des guides techniques et par la réglementation en vigueur. Ces guides proposent une méthodologie d’évaluation et des valeurs seuils protectrices pour la santé humaine et l’environnement, utilisant les teneurs totales en composé organique hydrophobe (COH). Ce travail évalue le comportement environnemental à long terme de sédiments contaminés et précise quels sont les paramètres et les mécanismes contrôlant la mobilité des polluants organiques, afin de passer dans les études du danger au risque. 5 sédiments de natures différentes ont été suivis au laboratoire pendant 18 mois, et diverses méthodes de mesure des fractions solides, colloïdales et dissoutes ont été pratiquées. La matière organique des sédiments est hétérogène et possède une multitude de sites de sorption. La présence d’origine exogène de suie et de matières organiques condensées (Black Carbon) et d’hydrocarbures est responsable de la forte rétention des COH dans le sédiment (coefficients de partage Kd élevés et cinétiques de désorption très lentes).Une modélisation à partir des coefficients de partage, même avec des estimations très fines, peut largement sous-évaluer le risque environnemental (facteur 1000) car la mobilité des COH au travers des colloïdes ou macromolécules dissoutes n’est pas prise en compte dans les modèles d’émission et de transport classiques. / Each year, 65 million m3 of sediment are removed by dredging of harbors, canals, rivers and French rivers. These materials are often contaminated with heavy metals, pesticides and other organic pollutants accumulated over time, and should be stored ashore. The re-use of contaminated sediments under various scenarii is supervised by technical guidelines and regulations. These guides offer an evaluation methodology and thresholds for protecting human health and the environment, using the total solid concentrations of hydrophobic organic compound (HOC). This work evaluates the long-term environmental behavior of contaminated sediments and precisely what are the parameters and mechanisms controlling the mobility of organic pollutants, to assess risk rather than hazard. 5 sediments were monitored in the laboratory for 18 months, and various methods of measuring solid, colloidal and dissolved fractions were performed. The organic matter in sediments is heterogeneous and has a multitude of sorption sites. The presence of exogenous origin of soot and condensed organic matter (Black Carbon) and hydrocarbons is responsible for the high retention of HOC in the sediment (high partition coefficients Kd and very slow desorption kinetics). Classical modeling of the dissolved phase by partition coefficients, even refined, may significantly under-estimate the environmental risk (factor up to 1000) because the mobility of COH through colloids or dissolved macromolecules is not taken into account in the conventional transmission and transport models.

La pollution des eaux est particulièrement problématique pour les pays industrialisés et les pays en développement. Des suivis environnementaux se sont alors avérés nécessaires afin de progresser dans la compréhension des origines et des conséquences de la présence de ces polluants. Parmi les polluants organiques les plus dangereux, les Hydrocarbures Aromatiques Polycycliques (HAP) et les pesticides qui peuvent se retrouver à l’état de traces dans les milieux aquatiques. Leur analyse nécessite des méthodes analytiques à la fois spécifiques et sensibles. L’Extraction sur Phase Solide (SPE) suivi d’une analyse par la Chromatographie Gazeuse couplée à la Spectrométrie de Masse (GC-MS) est la méthode la plus couramment employée. Les travaux de thèse s’inscrivent ainsi dans l’optique généralevisant à développer des nouvelles méthodes analytiques pour l’extraction et l’analyse de cesdeux familles de polluants organiques présents dans l’eau. Afin de pallier les contraintes classiques de la SPE, une nouvelle approche a été développée qui consiste à introduire latechnique de centrifugation dans certaines étapes de la procédure SPE. La nouvelle méthodeélaborée a permis de réduire considérablement le temps de préparation et d’économiserl’utilisation et le rejet des solvants organiques, en réduisant presque 10 fois les volumes nécessaires à l’obtention des rendements de récupération satisfaisants. Une méthoded’analyse par injection à température programmable (PTV) a été optimisée afin d’améliorerles seuils de détection des HAP. Cette étude a permis également d’avoir les informations surla qualité des eaux de pluie, eaux souterraines et eaux de surface au Liban quant au niveau deleur contamination pour les HAP et les pesticides. / Water pollution presents a very critical problem facing industrial and developping countries. The environmental monitoring of the contaminants seems necessary to understand their sources and impacts. Among a wide variety of organic pollutants present in water,polycyclic aromatic hydrocarbons (PAHs) and pesticides are of particular importance as widespread, persistent, and toxic contaminants. They are usually present at trace levels in theacquatic surfaces; therefore their detection and control require selective and sensitiveanalytical procedures. The Solid-Phase Extraction (SPE) followed by the Gas-Chromatography coupled to Mass Spectrometry (GC-MS) are the most commonly usedtechniques for their analysis in water. Thesis objectives are focused on the development of new analytical methods for the extraction and analysis of these two families of pollutants present in water. To overcone the contraints of the traditional SPE, a new approach was developed consisting on the introduction of the centrifugation in several steps of the procedure. The new method showed practical environmental and economical advantages interms of sample preparation time, simplicity, reduction in solvent use, and cost and isparticularly suitable for routine applications requiring a high sample throughput. Aprogrammed temeperature vaporizing (PTV) injection method was also optimized and validated in order to improve the detection limits for the GC-MS analysis of PAHs. The evaluation of the quality of different water systems in Lebanon including rainwater,groundwater, drinking water and surface water was accomplished in this study.

[pt] Os hidrocarbonetos policíclicos aromáticos (HPA) são compostos orgânicos de origem petrogênica e pirogênica, ubíquos, persistentes, bioacumuláveis em tecidos adiposos e comprovadamente carcinogênicos. O Monumento Natural do Arquipélago das Ilhas Cagarras (MONA) é uma unidade de conservação de proteção integral localizada a 4,5 km da cidade do Rio de Janeiro, cujas potenciais fontes de HPA para o local incluem o Emissário Ipanema, a Baía de Guanabara, o trânsito de grandes e pequenas embarcações, e a deposição atmosférica proveniente do alto trânsito de veículos e emissões industriais. Considerando que moluscos bivalves são biomonitores efetivos da exposição aos HPA, em fev/22 (C1) e jul/22 (C2) coletou-se cerca de 240 mexilhões da espécie Perna perna em três ilhas do MONA para avaliar o aporte de HPA oriundos de atividades antrópicas. Amostras compostas (3-5 animais) foram extraídas em triplicata utilizando extração acelerada por solvente (ASE) com purificação na célula, e purificação adicional por cromatografia em coluna. A fração de HPA foi determinada por cromatógrafo a gás acoplado a um espectrômetro de massas (GC-MS). As concentrações de (Somatório)39HPA variaram de 236 a 1378 ng g-1 , com os maiores valores encontrados em C1, níveis semelhantes aos de estudos anteriores com P. perna na região da Baía de Guanabara e algumas das ilhas do MONA (68-6271 ng g-1), sendo caracterizado, no entanto, aumento no aporte ao longo dos últimos 10 anos. O perfil geral dos contaminantes demonstra uma mistura de fontes pirolíticas e petrogênicas na região do MONA, sendo fontes prováveis a queima de combustíveis fósseis na região metropolitana e o aporte crônico de óleo, incluindo vazamentos irregulares, pelo trânsito constante de embarcações e fundeios próximos ao MONA. As concentrações de benzo[a]pireno, o (Somatório)4HPA – benz[a]antraceno, benzo[a]pireno, criseno e benzo[b]fluoranteno – e o Quociente de Equivalência Tóxica de Benz[a]pireno (TEQ BaPy) ficaram abaixo dos limiares de 5 ng g-1, 30 ng g-1 e 18 ng g-1, respectivamente, porém mais altos na amostragem realizada no verão, sugerindo um risco potencial para a qualidade de frutos do mar (moluscos) e da população humana. O cenário fornecido por um conjunto de dados limitado (apenas duas amostragens) reforça a necessidade de um programa de biomonitoramento no MONA Cagarras que inclua HPA e outras classes de contaminantes orgânicos, como as bifenilas policloradas (PCB) e pesticidas. / [en] Polycyclic aromatic hydrocarbons (PAH) are organic compounds of petrogenic and pyrogenic origin that are ubiquitous, persistent, bioaccumulative in adipose tissue, and proven to be carcinogenic. The Cagarras Islands Natural Monument (MONA) is a protected area located 4,5 km from the city of Rio de Janeiro, whose potential sources of PAH to the site include the Ipanema Outfall, Guanabara Bay, the transit of large and small vessels, and atmospheric deposition from high traffic of vehicles and industrial emissions. Considering that bivalve mollusks are effective biomonitoring organisms of exposure to PAH, in Feb/22 (C1) and Jul/22 (C2), approximately 240 mussels of the species Perna perna were collected from three MONA islands to assess the input of PAHs from anthropogenic activities. Composite samples (3-5 animals) were extracted in triplicate using accelerated solvent extraction (ASE) with purification in the cell, and additional purification by column chromatography. The PAH fraction was determined by gas chromatography-mass spectrometry (GC-MS). The concentrations of (summation)39PAH ranged from 236 to 1378 ng g-1, with the highest values found in C1, similar to previous studies with P. perna in the region of Guanabara Bay and some of the MONA islands (68-6271 ng g-1), but characterized by an increase in input over the last 10 years. The general profile of contaminants demonstrates a mixture of pyrolytic and petrogenic sources in the MONA region, with probable sources being fossil fuel combustion in the metropolitan region and chronic oil input, including irregular leaks, from the constant traffic of vessels and anchoring near the MONA. The concentrations of Benzo[a]pyrene, the (summation)4PAH – benzo[a]anthracene, chrysene, benz[b]fluoranthene, and benzo[a]pyrene – and the Toxic Equivalent Quotient of Benzo[a]pyrene (TEQ BaPy) were below the thresholds of 5 ng g-1, 30 ng g-1, and 18 ng g-1, respectively, but higher in the sampling performed in summer, suggesting a potential risk to the quality of seafood (mollusks) and the human population. The scenario provided by a limited data set (only two samplings) reinforces the need for a biomonitoring program in the Cagarras Islands Natural Monument that includes PAHs and other classes of organic contaminants, such as polychlorinated biphenyls (PCBs) and pesticides.

Priority organic and emerging contaminants are a growing concern for drinking water treatment due to their increasing presence in the environment. This study developed a predictive model for the sorption of anionic organic contaminants from drinking water on three anion exchange resins: a strong polystyrenic (IRA-910), weak polystyrenic (IRA-96), and a strong polacrylic (A860). The model quantifies the individual mechanisms of sorption using poly-parameter linear free energy relationships (pp-LFERs) and the feasibility of phase conversion (e.g., an ideal gas phase as the reference state) for ionic species was examined. To develop the model, a training set of isotherms was obtained using aliphatic and aromatic carboxylates, phenols, anilines, nitrobenzene, and ibuprofen. These compounds were chosen as model organic contaminants in the environment. The training set and 1-3 test compounds (3-methyl-2-nitrobenzoate, phenol, and 4-nitroaniline) were accurately predicted using the created model for each resin. An understanding of the effects of resin structure on sorption interactions was also developed that focused on ionic functional groups, resin matrix, and hydrophilicity (i.e. water content). It was shown that greater sorption efficiency was achieved when electrostatic (ion exchange) and nonelectrostatic (adsorption) interactions were present together to create a synergistic addition. However, sorption on ion exchangers was poor if the pH of the system approached levels lower than the sorbate pKa. Additionally, weak base exchanges lose exchange capacity as pH levels approach resin pKa (IRA-96 pKa = 6.0). Additional contributions to the sorption mechanisms were observed by studying various electron donating/withdrawing functional groups on the contaminants. It was concluded that π-π and H-bonding interactions contributed a greater amount to the nonelectrostatic mechanisms than cavity formation forces and nonspecific forces. A comparison between the three resins showed that IRA-96 (weak base polystyrenic) had a greater removal capacity than IRA-910 (strong base polystyrenic), followed far behind by A860 (strong base polyacrylate). This is due to differences between the resins, such as the hydrophilicity, the density of the ion exchange group, and the presence of aromatic rings within the matrix structure. Although the modeling method accurately predicted the phase change from aqueous to sorbent phases, it was shown that the SPARC calculated aqueous-gas ion transfer energies were poor estimations of the transfer energy to the ideal gas phase and further study is necessary to accurately determine this value. This modeling methodology is believed to be applicable to emerging contaminants such as pharmaceuticals in water systems and helps further new water treatment technologies while developing a mechanistic understanding of electrostatic and nonelectrostatic interactions in general. This can be applied to additional separation processes such as chemical purification and chromatographic separation. / Civil Engineering

Passive sampling, as opposed to the conventional spot or bottle water sampling technique, has shown to be reliable and efficient in monitoring the toxicologically relevant, freely dissolved (e.g. bioavaialable) concentrations of a wide range of organic contaminants in water. At the same time, partitioning controlled delivery (passive dosing; PD) techniques promise to overcome many of the challenges associated with toxicity testing of hydrophobic substances that may bias the interpretation of toxicity data. The present study investigated the feasibility of coupling silicone rubber passive sampling devices (SR-PSDs) with bioassay techniques for both chemical and ecotoxicological assessment of complex mixtures of organic contaminants in the aquatic environment. SR-PSDs were deployed in water at various locations within the Ythan catchment (north east, Scotland, UK), Forth estuary and the Firth of Forth (east coast of central Scotland, UK) for 7 to 9 weeks. Following retrieval, extracts from the SR-PSDs were analysed for dissolved concentrations of a variety of organic contaminants including PAHs and PCBs using GC-MS and GC-ECD respectively and were screened for a wide range of pesticides using GC-MS/MS and LC-MS/MS. The extracts were further evaluated for acute cytotoxicity (i.e. neutral red uptake assay) and EROD induction potential using rainbow trout liver cell line (Oncorhynchus mykiss; RTL-W1) and for phytotoxicity and developmental toxicity potential using algal growth inhibition test (with a marine phytoplankton, Diacronema lutheri) and fish embryo toxicity test (with embryos from zebrafish Danio rerio) respectively. Overall, the individual and total dissolved concentrations of PAHs (ΣPAH40; parent and branched) and PCBs (ΣPCB32; ortho and mono-ortho) measured in water from the Ythan, Forth estuary and Firth of Forth were relatively low compared with other studies using PSDs. A number and level of pesticides, including insecticides, herbicides and fungicides of varying hydrophobicity (log KOWs ~2.25 to ~5.31) were detected in the silicone rubber (SR) extracts from the Ythan catchment, the Forth estuary and the Firth of Forth, suggesting input mainly from agricultural run-off and possibly from direct discharges. No statistically significant (p<0.05) acute cytotoxicity was observed following 48 h exposure of RTL-W1 cells to SR extracts from the Ythan catchment. But, on a sublethal level, for every site, statistically significant EROD activity was observed to some degree following 72 h exposure. In addition, developmental and algal toxicities on embryos of D. rerio and D. lutheri respectively, were measured in all the deployed samples compared with the procedural controls (undeployed samples). Interestingly, extracts of SR-PSDs from the Forth estuary and the Firth of Forth exhibited growth inhibitions on D. lutheri that were similar to those of extracts from the Ythan, even though, fewer numbers of pesticides were detected in the Forth estuary and Firth of Forth than the Ythan. This suggests that pesticides were not solely responsible for the observed effects in the Ythan catchment. To further improve data from toxicity testing of hydrophobic substances, the study identified the use of SR O-rings as a suitable passive dosing format in in vitro toxicity tests and was partially validated through their use in dosing RTL-W1 cells with two individual PAHs and subsequently determining cytotoxicity and EROD-activity.

M. Tech. (Department of Chemical Engineering, Faculty of Engineering and Technology), Vaal University of Technology / Water pollution caused by organic and inorganic contaminants represents an important ecological and health hazard. Simultaneous treatment of organic and inorganic contaminants had gradually gained great scientific interest. Advanced oxidation processes such as photocatalysis, using TiO2 as a photocatalyst, have been shown to be very robust in the removal of biorecalcitrant pollutants. These methods offer the advantage of removing the pollutants, in contrast to conventional techniques. At present, the main technical challenge that hinder its commercialization remained on the post-recovery of the photocatalyst particles after water treatment. Supporting of the photocatalyst on the adsorbent surface is important as it assists during the filtration step, reducing losses of the materials and yielding better results in degrading pollutants. To overcome this challenge, in this study composite photocatalysts of TiO2/zeolite and TiO2/silica were prepared and investigated to explore the possible application in the simultaneous removal of organic and inorganic compounds from contaminated water. The main objective of this study was to investigate the heterogeneous photocatalytic degradation of organic compounds in the presence of metal ions using composite photocatalysts. The Brunauer–Emmett–Teller (BET), Scanning Electron Microscopy and Energy Dispersive X-ray (SEM-EDX), Raman spectroscopy (RS) and zeta potential (ZP) analyses were used to characterize the prepared composite photocatalysts. The successive composite photocatalysts were used in a semi-batch reactor under an irradiation intensity of 5.5 mW/m2 (protected by a quartz sleeve) at 25 ± 3°C for the photocatalytic degradation of synthetic textile (methyl orange) and agricultural (atrazine) wastewater in the presence of ions. The effect of operating parameters such as TiO2 composition on supporting material, particle size, composite photocatalyst loading, initial pollutant concentration and pH were optimized. The effects of inorganic salts and humic acid on dye and pesticides degradation were also studied, respectively. The performance of the photocatalyst reactor was evaluated on the basis of color removal, metal ion reduction, total organic carbon (TOC) reduction, intermediates product analysis and modeling of kinetics and isotherms. Different kinetic and isotherm models were introduced and applied in this work. Important aspects such as error functions with the optimal magnitude were used for the selection of the best suitable model. / European Union. City of Mikkeli, Finland. Water Research Commission (RSA)

Η ορυκτολογική σύσταση του αργιλικού υλικού που χρησιμοποιείται σε ένα χώρο υγειονομικής ταφής απορριμμάτων είναι καθοριστικής σημασίας όσον αφορά την πιθανή διαφυγή και μετανάστευση ρύπων στο περιβάλλον. Ο προσδιορισμός των αργιλικών ορυκτών που συμμετέχουν στο αργιλικό υλικό, θεωρείται βασική παράμετρος όσον αφορά την εκτίμηση της ικανότητας τους για συγκράτηση οργανικών και ανόργανων ρύπων. Για το σκοπό αυτό η αναγνώριση των ορυκτολογικών συστατικών του αργιλικού υλικού που χρησιμοποιήθηκε στο χώρο υγειονομικής ταφής της Ν. Ζακύνθου κρίθηκε απαραίτητη. Από τα αποτελέσματα της περιθλασιμετρίας ακτίνων Χ προέκυψε ότι στο αργιλικό υλικό που χρησιμοποιήθηκε μέσα στο χώρο υγειονομικής ταφής, διακρίθηκε μία ομάδα δειγμάτων πλούσια σε σμεκτίτη (μοντμοριλλονίτη) και μία δεύτερη πλούσια σε χλωρίτη και βερμικουλίτη. Παράλληλα, η χρήση της περιθλασιμετρίας ακτίνων Χ σε συνδυασμό με την ηλεκτρονική μικροσκοπία και τις γεωχημικές αναλύσεις έδωσαν πληροφορίες για την προέλευση των ιζημάτων, καθώς και για τη παρουσία ρύπων και τον τρόπο συγκράτησης τους στις ορυκτές φάσεις που τα απαρτίζουν. Η μελέτη των φασμάτων NMR στα εκχυλίσματα των δειγμάτων έδειξε την ύπαρξη κορυφών απορροφήσεως από πρωτόνια που σχετίζονται με ομάδες πολυσακχαριτών, πεπτιδίων/πρωτεϊνών, αλκοολών, αμινοξέων, ομάδων που περιέχουν –Cl, σουλφιδίων και μεθυλενίων –CH2– παρακείμενων σε ομάδες αιθέρων ή και εστέρων τα οποία παράγονται ως αποτέλεσμα υδρόλυσης και αναερόβιας ζύμωσης στα διαλύματα στραγγισμάτων. Επιπλέον, οι μικροαναλύσεις έδειξαν την παρουσία χλωρίου και θείου σε κρυστάλλους απατίτη, καθώς και χλωρίου, θείου και φωσφόρου σε αργιλικά ορυκτά στα δείγματα που βρίσκονταν σε επαφή με στραγγίσματα, ενισχύοντας την άποψη ότι οι παραπάνω ομάδες προέρχονται από την αλληλεπίδραση με τα στραγγίσματα. Η διαφορετική ορυκτολογική σύσταση του αργιλικού υλικού που χρησιμοποιήθηκε στο χώρο απόθεσης απορριμμάτων (χλωρίτης-μοντμοριλλονίτης) φαίνεται να ευνοεί την εκλεκτική προσρόφηση των διαφορετικών οργανικών ρύπων που συμμετέχουν στα στραγγίσματα και κατά συνέπεια θεωρείται επιθυμητή. Προς την κατεύθυνση αυτή εστιάστηκε το ενδιαφέρον της διατριβής οπότε και προέκυψε ότι ο χλωρίτης παρουσιάζει εκλεκτική προσρόφηση για τις αρωματικές ενώσεις σε αντίθεση με τον μοντμοριλλονίτη, ο οποίος επιδεικνύει εκλεκτική προσρόφηση εκείνων των αλειφατικών ομάδων που εκχυλίζονται από υδατικά διαλύματα. Επιπλέον, οι αρωματικές ενώσεις δεν εκχυλίζονται από υδατικά διαλύματα και κατά συνέπεια από ύδατα επιφανειακών απορροών με αποτέλεσμα να επιδεικνύουν περιορισμένη κινητικότητα. Αντίθετα, οι αλειφατικές ομάδες εκχυλίζονται από υδατικά διαλύματα ενώ η παρουσία τους ευνοεί το σχηματισμό ευδιάλυτων συμπλόκων με μέταλλα, γεγονός που οδηγεί τελικά σε κινητοποίηση τους μέσω των επιφανειακών απορροών. Τέλος, η προσρόφηση αμινομάδων από τα αργιλικά ορυκτά φαίνεται ότι οδηγεί μέσω μιας διαδικασίας φυσικής οργανοφιλίωσης στην μετατροπή των υδρόφιλων επιφανειών των αργιλικών ορυκτών σε υδρόφοβες και κατά συνέπεια την προσρόφηση των υδρόφοβων οργανικών συστατικών που περιέχονται στα διαλύματα στραγγισμάτων. Το γεγονός αυτό είναι ιδιαίτερα σημαντικό εφόσον δείχνει την δυνατότητα για in situ μετατροπή των αργίλων σε οργανόφιλες αργίλους δημιουργώντας νέες προοπτικές στην διαχείριση των μη πολικών οργανικών ρύπων. / The mineralogy of a clay liner used in a landfill may influence the mobility of contaminants. Therefore, the determination of the types of clay minerals that are present in the landfill is of great importance for the assessment of their efficiency in the retention of organic and inorganic pollutants. In the present work, clay materials from an operating waste disposal facility in Zakynthos Island, Western Greece were collected in order to determine the different clay minerals present and their pollutant retention potential. Mineralogical analyses by XRD of the clay material collected from the landfill revealed a smectite (montmorillonite) rich and a chlorite/vermiculite rich material. The information obtained from X-ray Diffraction and SEM-EDS combined with chemical analyses provided valuable information concerning the provenance of the sediments and their retention potential. 1H NMR revealed that some of the organic components which are present in the samples are aliphatics, polysaccharides, alcohols, esters, Cl halogens, sulphides, amines, peptide/protein groups, amide and aromatics which are produced in the landfill as a result of several complex phenomena involving solubilization, hydrolyzation and anaerobic biological processes. SEM-EDS analyses showed the presence of chlorine and sulphur in apatite crystals, and of chlorine, sulphur and phosphorus in clay minerals suggesting the interaction of these minerals with leachate. The different clay mineralogy of the material used in the landfill, smectite (montmorillonite) rich and chlorite/vermiculite rich material facilitated the adsorption of different organic compounds, which is significant for the retention of pollutants. NMR analyses showed that aromatic moieties are preferentially adsorbed on chlorite than on montmorillonite, while those aliphatic moieties that are water soluble are preferentially adsorbed on montmorillonite. Aromatics are not accessible to rainwater and therefore hardly migrate. The aliphatic chains that are water accessible can be released to the environment through natural leaching by rainwater and since they are known to form soluble metal-organic complexes, supervision of the landfill is considered essential. Moreover, the interaction of amine groups with clay minerals in an aqueous system is favoured by the formation of an "insoluble" hydrophobic product leading to the formation of naturally organically modified clays. Thus clays become organophilic and capable of removing non ionic organic contaminants. This is of great importance for environmental applications since it demonstrates the in situ formation of organophilc clays in landfills, hence enabling effective containment and immobilisation of toxic organic compounds.