Les nanorubans de carbone présentent aujourd’hui un grand intérêt en tant que segments de graphène aux propriétés électroniques modulables. Alors que des techniques de synthèse destructives top down donnent des rubans de très grande taille, d’autres techniques constructives bottom up, par synthèse organique, pourraient former des nanorubans bien définis de géométries contrôlées. Dans cette optique, la réaction de Scholl est un outil chimique précieux car elle permet la graphénisation de longs précurseurs flexibles de type polyphénylène.Etonnamment, des structures distordues peuvent être obtenues majoritairement même si des isomères plans moins encombrés sont a priori favorisés. Nous avons ainsi montré que contre toute attente même un encombrement stérique important n’a aucun effet notoire sur la régiosélectivité et que des composés aromatiques polycycliques courbés sont préférentiellement formés. Ainsi, des structures particulièrement tordues, tel que l’hexabenzotriphénylène (HBTP) peuvent être facilement obtenues à partir de précurseurs de type polyphénylène.Après avoir découvert cette régiosélectivité inattendue, nous en avons tiré parti pour former des composés de type polyhélicène. Plusieurs tentatives de formation de l’hexaphénanthrotriphénylène (HPTP) furent infructueuses à cause de problèmes de réactivité lors des synthèses des précurseurs flexibles correspondants. En mettant au point une stratégie de synthèse versatile fondée sur un précurseur commun, plusieurs substrats flexibles de symétrie C3 ont été synthétisés puis soumis à la réaction de Scholl. Des produits de réarrangement ont cependant été obtenus au détriment des [6]hélicènes attendus. Toutefois, un HBTP fonctionnalisé par des groupements TMS a pu être efficacement préparé, ainsi qu’un hexabenzocoronène (HBC) dont l’exceptionnelle solubilité est due à la distorsion du coeur aromatique sous l’effet des groupements encombrants situés dans les régions baie.Ce fragment [5]hélicène favorisé a enfin été incorporé dans la formulation de nanorubans de carbone tordus, alors composés d’une succession de ce motif. En tant que réactions test, les synthèses du monomère et du dimère correspondants ont été effectuées avec d’excellents rendements et les deux composés entièrement caractérisés. Leurs structures ont été déterminée par diffraction de rayons X sur monocristaux et ont fourni d’intéressantes informations complémentaires quant à leurs configurations. Une stratégie plus générale a enfin été développée et optimisée pour la synthèse systématique d’oligomères plus longs de nanorubans de carbone tordus. En utilisant cette technique les trimère et tétramère correspondants ont été synthétisés et caractérisés par spectrométrie de masse. / Carbon nanoribbons are today of great interest as graphene segments with modulable electronic properties. Whilst top down techniques give giant ribbons, bottom-up organic synthesis may lead to exactly designed nanoribbons of controlled geometries. The Scholl reaction is a precious chemical tool for that purpose since it yields efficiently to the graphitization of long and flexible polyphenylene precursors.Surprisingly, twisted structures may be obtained preferentially even if less crowded isomers are also feasible. It has been shown that, against all expectation, even a strong steric hindrance has no marked effect on regioselectivity and highly twisted polycyclic aromatic hydrocarbons are sometimes preferentially formed, whereas their flat and more symmetrical isomers are only obtained in minority. Highly twisted structures such as hexabenzotriphenylene (HBTP) may then be obtained very easily from flexible polyphenylene precursors.After discovering this unexpected regioselectivity, we used it on purpose to form polyhelicenic species. Attempts to prepared hexaphenanthrotriphenylene (HPTP) were unsuccessful due to reactivity issues when synthesizing the corresponding flexible precursors. By using a new versatile strategy leading to an advanced common precursor, several C3-symmetrical flexible substrates have been synthesized and submitted to Scholl reaction. The expected [6]helicenes were not obtained and rearranged products were formed instead, but TMS-bearing HBTP could be prepared, as well as a hexabenzocoronene (HBC) which exceptionnal solubility is due to the distortion of the aromatic core under the effect of bulky tert-butyl substituents in bay regions.The easily formed [5]helicene fragment has been incorporated in the design of twisted carbon nanoribbons that would be composed of a succession of such motifs. As a test reaction, the corresponding monomer and dimer have been synthesized with an excellent yield and fully characterized. Their X-ray structures have even been determined, giving interesting information about their configuration. A more general strategy has then been developed and optimized for the systematic synthesis of longer oligomers of twisted nanoribbons. Using this technique, the trimer and tetramer have been synthesized and characterized by mass spectrometry.

Polycyclic aromatic hydrocarbons (PAHs) and nitrogen-containing polycyclic aromatic compound (N-PAC) are widespread toxic pollutants in environments. The fate of PAHs and N-PACs are of great concern because some of these compounds were identified as caricinogenic, mutagenic and teratogenic compounds. As described in literature, dissolved organic matter (DOM) is an important factor in control of their fate; however, the binding behaviors between these compounds and DOM are still not fully understood. The binding constants (KDOC) between humic substances and one selected N-PAC, benzo[h]quinoline, were measured at varying pH levels using fluorescence quenching (FQ) method. As fluorescence characteristics of benzo[h]quinoline change with pH, determination required two optimum sets of excitation and emission wavelength pairs. A simple mixing model was proposed and used to eliminate the inherent fluorescence interference between benzo[h]quinoline (BQ) and its protonated form, benzo[h]quinolinium (BQH+), and to deduce Kmix which represents the overall binding as the sum of that for the individual analogs. The characteristics of humic substances, especially their hydrophobicity and aromaticity, established by principal components analysis of structural and elemental compositions, were the main determinants of their binding affinity with both benzo[h]quinoline and benzo[h]quinolinium (KBQ and KBQH+) across a range of pH values. Hydrophobic interaction is likely to control the binding between humic substance and benzo[h]quinoline and benzo[h]quinolinium, in lower and higher pH ranges (pH<3, pH>6). In contrast, cation exchange seems to control on the binding affinity of benzo[h]quinolinium in the middle range of pH. Determination of PAH concentration is quite essential for investigating the fate of PAHs in environments. Microwave-assisted headspace solid-phase microextraction (MA-HS-SPME) with a polydimethylsiloxane/divinylbenzene (PDMS/DVB) fiber was applied as a single step prior to determination of PAH concentrations in water using GC-MS. To optimize the extraction efficiency of PAHs by MA-HS-SPME, the influence of various parameters, including temperature, duration of thermal desorption, microwave irradiation power and duration, and the temperature of the circulating cooling water system, was studied. The proposed method was demonstrated applicable to environmental water samples. In addition, DOM matrix effect did not influence the determination and extraction efficiency of PAHs. Although the proposed simple mixing model can eliminate the fluorescent interference of hydrophobic organic compounds with acid-base pair forms, it is still limited in using for correcting the KDOC measurement of more than two fluorescent compounds simultaneously. A new alternative protocol, complexation-flocculation combined with MA-HS-SPME/GC-MS method, was proposed to determine the binding constants of seleted PAHs to humic substances. The results obtained are comparable with KDOC data reported in literatures. CF-MA-HS-SPME/GC-MS provides some advantages over other methods, such as applicable not limited to fluorescent compounds, faster in determination and capable in measuring varieties of compounds simultaneously.

Phanerochaete chrysosporium est un champignon ligninolytique largement étudié pour ses capacités à dégrader la lignine et certains xénobiotiques grâce à un important système d'enzymes extracellulaires. Son génome est entièrement séquencé et constitue un inventaire de séquences protéiques prédites qui a permis la description de nombreuses superfamilles de protéines. Parmi elles, les Glutathion S-transférases sont essentiellement impliquées dans le métabolisme secondaire du champignon. Cependant, malgré les nombreux travaux montrant l'implication de ces enzymes dans la réponse aux stress, le développement cellulaire et plus globalement dans certaines fonctions métaboliques, leurs réelles fonctions restent inconnues à cause de leur grande diversité et le manque de données concernant leurs spécificités catalytiques. P. chrysosporium possède 27 isoformes de GSTs qui se regroupent en 7 classes. Parmi elles, 3 sont étendues chez les champignons saprophytes : les classes Omega, Ure2p et ethérase. Deux membres de la classe Omega ont été caractérisés au niveau biochimique et montrent desspécificités de substrat. En effet, PcGTO1 fait partie d'une nouvelle classe appelée S-glutathionyl-phydroquinone reductase, alors que PcGTO3 est plutôt active avec le phenylacetophenone. La structure tridimensionnelle de PcGTO1 suggère que l'enzyme appartient également à une nouvelle classe structurale que nous avons appelée xi. La deuxième classe majoritaire que nous avons étudiée est la classe des Ure2p qui est composée de 9 isoformes et se regroupent en 2 sous-classes. Trois isoformes ont été étudiées au niveau transcriptionnel, biochimique et physiologique. PcUre2p4 et PcUre2p6 appartenant à la première sous-classe sont spécifiquement exprimés dans des cultures fongiques en présence d'hydrocarbures aromatiques polycycliques et l'activité des protéines recombinantes correspondantes est classique des GSTs à savoir le transfert de glutathion sur un substrat hydrophobe. A l'inverse, PcUre2p1 qui appartient à la deuxième sous-classe est exprimé de manière constitutive au niveau transcriptionnel et la protéine présente une activité thiol transférase comparable aux protéines de la classe Omega. Les analyses physiologiques menées grâce à la complémentation de souche déficience de Saccharomyces cerevisiae ont montré que PcUre2p1, PcUre2p4 et PcUre2p6 n'avaient pas la même fonction que l'isoforme de la levure puisqu'aucune complémentation n'a été détectée en ce qui concerne la résistance au stress ou la régulation du métabolisme azoté. Ces résultats suggèrent que leschampignons, en particulier ceux qui présentent des propriétés saprophytes ont développé des spécificités de fonction de leur GSTs probablement en réponse à des contraintes environnementales. / Phanerochaete chrysosporium is a ligninolytic fungus widely studied because of its capacities to degrade wood and xenobiotics through an extracellular enzymatic system. Its genome has been sequenced and has provided researchers with a complete inventory of the predicted proteins produced by this organism. This has allowed the description of many protein superfamilies. Among them, Glutathione S-transferases (GSTs) constitute a complex and widespread superfamily classified as enzymes of secondary metabolism. However, despite the numerous associations of GSTs with stress responses, cell development and metabolism in various organisms, the functions of these enzymes remain usually evasive mainly due to their high diversity and also to the lack of knowledge about their catalytic specificities. In P. chrysosporium 27 GST isoforms have been highlighted and clustered into seven classes. Among them three are extended in saprophytic fungi: the Omega, the Ure2p and the etherase classes. Two members of the Omega class have been characterized at the biochemical level showing difference in substrate specificities. Indeed, PcGTO1 is member of a new class of Sglutathionyl- p-hydroquinone reductase, while PcGTO3 is rather active with phenylacetophenone. The three-dimensional structure of PcGTO1 confirms the hypothesis not only of a new biological class, but also of a new structural class that we propose to name GST xi. The second extended class we have studied is the Ure2p one. It is composed of nine isoforms in P. chrysosporium and clusters into two subclasses. Three Ure2p class members have been studied in more details at transcriptional, biochemical and physiological levels. PcUre2p4 and PcUre2p6 of the first subclass are specifically expressed in cultures treated with polycyclic aromatic hydrocarbons and the recombinant proteins are active as typical glutathione transferases. By contrast, PcUre2p1, which belongs to the second subclass is constitutively expressed whatever the condition tested and is active with small molecules as substrate, such as proteins from the Omega class. Physiological studies have revealed that these proteins do not have the same function than the Saccharomyce cerevisiae isoform, concerning both the response to oxidative stress and its involvement in the nitrogen catabolite repression. These results suggest that fungi, especially those with saprophytic capabilities, have developed specificities of GST function as an adaptation to environmental constraints

The efficiency of wastewater treatment systems is commonly measured by the reductions of parameters such as biological oxygen demand (BOD), chemical oxygen demand (COD) and total suspended solids (TSS) and/or reductions in levels of selected macro compounds (e.g. long-chained hydrocarbons and inorganic compounds). Less attention has generally been paid to micropollutants with high potential toxic effects, such as polycyclic aromatic compounds (PACs), including unsubstituted and alkylated polycyclic aromatic hydrocarbons (PAHs) and dibenzothiophenes, polychlorinated biphenyls (PCBs), human pharmaceuticals and by-products formed during the treatment process. These organic micropollutants occur in wastewaters at trace and ultra-trace levels, therefore their detection requires advanced, costly analyses and large sample volumes. Furthermore, concentrations of micropollutants can fluctuate widely both diurnally and between days. Thus, in order to understand the fate of micropollutants in wastewaters there is a need to develop sampling techniques that allow representative samples to be readily collected. In the work underlying this thesis two types of diffusive passive samplers, semipermeable membrane devices (SPMDs) and polar organic chemical integrative samplers (POCISs), were used to monitor non-polar and polar organic micropollutants in wastewaters subjected to various treatment processes. The pollutants sequestered in these samplers represent micropollutants in the dissolved phase that are available for aquatic organisms. Further, since they collect pollutants in an integrative manner, i.e. they sample continuously during the selected exposure time (usually approx. one to ca. three weeks), the results provide time-weighted average (TWA) concentrations. In addition, the effects of various environmental factors on the uptake of analyzed micropollutants in POCISs and SPMDs were investigated using laboratory calibration and in situ calibration with performance reference compounds (PRCs). The results confirm that SPMDs are good sampling tools for investigating the efficacy of wastewater treatment processes for removing non-polar PACs and PCBs, and the effects of varying the process settings. In addition, analyses of process streams in municipal sewage treatment plants demonstrated that conventional sewage treatment processes are not optimized for removing dissolved four-ringed PAHs, some of the five-ringed PAHs, and tri- to hexa-chlorinated biphenyls. The removal of bioavailable PACs was enhanced by adding sorbents with high sorption capacities to the sludge used in the activated sludge treatment step, and a biologically activated carbon system was designed that robustly removed bioavailable PACs, with removal efficiencies of 96.9-99.7 percent across the tested ranges of five varied process parameters. In situ SPMD calibration data acquired show that uptake of PACs, described by SPMD sampling rates (Rs), were four to eight times higher than published laboratory calibrated Rs values, mainly due to strong (bio)fouling and turbulence effects. In addition, the laboratory calibration study demonstrated that temperature affects the POCIS uptake of pharmaceuticals. The uptake of four pharmaceuticals was higher, by 10-56 percent, at 18 °C compared to 5 °C. For two of the pharmaceuticals our data indicate that the uptake was lower by 18-25 percent at 18 °C. Our results also indicate that uptake of the studied pharmaceuticals was in the linear phase throughout the 35 day exposure period at both temperatures. Finally, calibration studies enabled aqueous concentrations of micropollutants to be more accurately estimated from amounts collected in the passive samplers.

Floodplain lakes are strongly regulated by river connectivity because floodwaters exert strong influence on the water balance, the physical, chemical and biological limnological conditions, and the influx of contaminants. The Peace-Athabasca Delta (PAD) in northern Alberta (Canada) is a hydrologically complex landscape and is an important node in the upper Mackenzie River Drainage Basin. The ecological integrity of the PAD is potentially threatened by multiple environmental stressors, yet our understanding of the hydroecology of this large floodplain remains underdeveloped. Indeed, ever since the planning and construction of the WAC Bennett Dam (1960s), concerns have grown over the effects of upstream human activities on the lakes of the PAD. More recently, concerns over the health of the PAD have intensified and come to the fore of national and international dialogue due to water abstraction and mining and processing activities by the rapidly expanding oil sands industry centred in Fort McMurray Alberta. Currently, widespread perception is that upstream human activities have reduced water levels and frequency of flooding at the PAD, which have lowered nutrient availability and productivity of perched basin lakes, and have increased supply of pollutants from oil sands. However, these perceptions remain based on insufficient knowledge of pre-impact conditions and natural variability. Current and past relations between hydrology and limnology of PAD lakes are mostly undocumented, particularly during the important spring freshet period when the effects of river flood waters are strongest. Similarly, knowledge of the deposition of oil-sands- related contaminants in the PAD remains insufficient to determine whether anthropogenic activities have increased the deposition of important oil-sands-related contaminants such as polycyclic aromatic compounds (PACs) relative to natural processes. Such knowledge gaps must be filled to achieve effective monitoring, policy and governance concerning impacts of industrial development and the protection of human and environmental health within the PAD and Mackenzie drainage basin. This thesis examines the effects of river flooding (and the lack of) on water clarity, nutrients, chemistry, phytoplankton abundance, epiphyton community composition and the deposition of polycyclic aromatic compounds (PACs) in lakes of the Peace-Athabasca Delta. To determine the role of flooding on contemporary epiphytic diatom communities (an abundant and diverse guild of primary producers in PAD lakes), a field experiment was conducted examining the community composition and abundance of epiphytic diatoms in four PAD lakes. Two of these four lakes had received floodwaters that spring and two had not. Epiphytic diatom communities in each lake were sampled during the peak macrophyte biomass period (summer) from two macrophyte taxa (Potamogeton zosteriformis, P. perfoliatus var. richardsonii) and from polypropylene artificial substrates previously deployed that spring. A two-way analysis of similarity (ANOSIM) test identified that epiphytic diatom community composition differed between lakes that flooded and those that did not flood. From the use of similarity percentage (SIMPER) analysis, diatom taxa were identified that discriminate between flooded and non-flooded lakes. The relative abundance of ‘strong flood indicator taxa’ was used to construct an event-scale flood record spanning the past ~180 years using analyses of sedimentary diatom assemblages from a closed-drainage lake (PAD 5). Results were verified by close agreement with an independent paleo-flood record from a nearby flood-prone oxbow lake (PAD 54) and historical records. Comparison of epiphytic diatoms in flooded and non-flooded lakes in this study provides a promising approach to detect changes in flood frequency, and may have applications for reconstructing other pulse-type disturbances such as hurricanes and pollutant spills. Additionally, this study demonstrates that artificial substrates can provide an effective bio-monitoring tool for lakes of the PAD and elsewhere. To improve our understanding of the hydrolimnological responses of lake in the PAD to flooding, repeated measurements over three years (2003-05) were made on a series of lakes along a hydrological gradient. This allowed the role of river flooding to be characterized on limnological conditions of lakes and to identify the patterns and timescales of limnological change after flooding. River floodwaters elevate lake water concentrations of suspended sediment, total phosphorus (TP), SO4 and dissolved Si (DSi), and reduce concentrations of total Kjeldahl nitrogen (TKN), DOC and most ions. River flooding increases limnological homogeneity among lakes, because post-flood conditions are strongly affected by the river water properties. After floodwaters recede, limnological conditions become more heterogeneous among lakes in response to diversity of local basin influences (geology, slope, vegetation, depth, fetch, and biological communities and processes), and limnological changes occur at two distinct timescales. In the weeks to months after flooding, water clarity increases as suspended sediments and TP settle out of the water column. In the absence of flooding for many years to decades, evaporative concentration leads to an increase in most nutrients (TKN, inorganic N, and dissolved P), DOC and ions. Contrary to a prevailing paradigm, these results suggest that regular flooding is not required to maintain high nutrient concentrations. In light of anticipated declines in river discharge, limnological conditions in the southern Athabasca sector will become increasingly less dominated by the short-term effects of flooding, and resemble nutrient- and solute-rich lakes in the northern Peace sector that are infrequently flooded. To determine the roles of the Athabasca River and atmospheric transport as vectors for the deposition of PACs in the PAD, sediment cores spanning the last ~200 years were collected from three lakes within the delta. A closed-drainage basin elevated well above the floodplain (PAD 18) was selected to determine temporal patterns of change in PAC concentration due to atmospheric deposition and within-basin production of PACs. Known patterns of paleohydrological changes at the other two lakes (PAD 23 and 31) were used to assess the role of the Athabasca River in delivering PACs to the Athabasca Delta during the ~200 year. Well- dated sediment core samples were analysed for 52 alkylated and non-alkylated PACs (method EPA 3540/8270-GC/MS). Sediments deposited in the non-flood prone lake (PAD 18) contained lower concentrations of total PACs compared to sediments deposited during flood-prone periods in the other study lakes, and were dominated by PACs of a pyrogenic rather than bitumen origin. Multivariate analysis of similarity tests identified that the composition of PACs differs between sediments deposited during not flood-prone and flood-prone periods. Subsequent Similarities Percentage (SIMPER) analysis was used and identified seven PACs that are preferentially deposited during flood-prone periods. These seven PACs are bitumen-associated, river-transported and account for 51% of the total PACs found in oil-sands sediment. At PAD 31, which has been flood-prone both before and since onset of Athabasca oil sands development, identified no measureable differences in both the proportion and concentration of the river-transported indicator PACs in sediments deposited pre-1940s versus post-1982. Our findings suggest that natural erosion of exposed bitumen along the banks of the Athabasca River and its tributaries is the main process delivering PACs to the Athabasca Delta, and that the spring freshet is a key period for contaminant mobilization and transport. Such key baseline environmental information is essential for informed management of natural resources and human-health concerns by provincial and federal regulatory agencies and industry, and for designing effective long-term monitoring and surveillance programs for the lower Athabasca River watershed in the face of future oil sands development. Further monitoring activities and additional paleolimnological studies of the depositional history of PACs and other oil-sands- and non-oil-sands-related contaminants is strongly recommended. Overall, results of this research identify that river flooding exerts strong control on physical, chemical and biological conditions of lakes within the PAD. However, contrary to prevailing paradigms, the PAD is not a landscape that has been adversely and permanently affected by regulation of the Peace River and industrial development of the oil sands along the Athabasca River. Instead, data from contemporary and paleolimnological studies identify that natural processes continue to dominate the delivery of water and contaminants to the delta. Regular and frequent flooding is not essential to maintain the supply of nutrients and productivity of delta lakes, which has been a widespread paradigm that developed in the absence of objective scientific data. Instead, nutrient concentrations rise over years to decades after flooding and lake productivity increases. During the thesis research, novel approaches were developed and demonstrated to be effective. Namely, new artificial substrate samplers were designed for aquatic biomonitoring that accrue periphyton and can identify the occurrence of flood events. Also, paleolimnological methods were employed to characterize the composition and concentration of PACs supplied by natural processes prior to oil sands industrial activity, which serves as an important benchmark for assessing industrial impacts. These are effective methods that can be employed to improve monitoring programs and scientific understanding of the factors affecting this world-renowned landscape, as well as floodplains elsewhere.

De nombreux sites pollués par des hydrocarbures aromatiques polycycliques (HAP) sont recensés dans les pays industrialisés. Associés aux 16 HAP US-EPA réglementaires, d’autres composés aromatiques polycycliques (CAP), notamment les CAP polaires (oxygénés et azotés) sont présents. Ils proviennent des mêmes sources que les HAP et peuvent être également formés par des processus biotiques ou abiotiques de transformation des HAP (atténuation naturelle ou procédés de dépollution). Ces CAP, plus polaires que les 16 HAP US EPA, sont plus solubles dans l’eau, induisant potentiellement une mobilité accrue dans les sols et de ce fait un risque pour l’Homme et l’environnement. Il est donc indispensable d’enrichir nos connaissances sur la mobilité des CAP polaires dans les sols et leur transfert vers les eaux souterraines. Ainsi l’objectif de ce projet était d’identifier les mécanismes contrôlant la mobilisation des CAP polaires dans les sols en relation avec les 16 HAP US EPA, et leurs modes de transfert en combinant approches laboratoire et in situ. Nos travaux confirment une mobilisation préférentielle des CAP polaires par rapport aux HAP. La mobilisation dans les sols des CAP polaires ainsi que celle des HAP de faible poids moléculaire est essentiellement pilotée par des processus de dissolution des goudrons (loi de Raoult). Néanmoins, alors que les prédictions de mobilisation des CAP polaires sont satisfaisantes dans le cadre de pollutions « fraiches », un paramètre fondamental doit être pris en compte pour les pollutions historiques ayant subi un effet d’aging : la disponibilité. En effet, quelles que soient les conditions de mobilisation (statique-batch ou dynamique-colonne) la teneur en CAP dans les eaux est fortement dépendante de la disponibilité de la pollution. De plus, pour une forte disponibilité des CAP, les autres paramètres testés (force ionique, température) ont une influence limitée sur la mobilisation alors que pour une faible disponibilité, ils peuvent avoir une influence notable. Par ailleurs, la mobilisation des CAP polaires par les colloïdes semble limitée alors qu’elle est prépondérante pour les HAP de hauts poids moléculaires notamment dans le cas d’une eau présentant une force ionique faible. Les essais réalisés sur une colonne lysimétrique (2 m3) remplie avec une terre de cokerie contaminée au 2/3 supérieure et avec une terre prélevée sur le même site mais non contaminée pour le 1/3 inferieur confirment une mobilisation des CAP selon un mécanisme de dissolution des goudrons avec toutefois des concentrations largement inférieures à celles prédites par la loi de Raoult. Aux différentes échelles expérimentales utilisées (batch, colonnes de laboratoire et lysimétrique), il a été clairement mis en évidence que la composante biologique a une influence très forte. Ainsi, une fois sous forme dissoute, les HAP mais également les CAP polaires sont fortement biodégradés sans que des sous-produits (notamment CAP oxygénés) n’aient pu être détectés / In industrial countries, many sites have been diagnosed polluted by polycyclic aromatic hydrocarbons (PAHs). In addition to the regulated 16 US-EPA PAHs, other polycyclic aromatic compounds (PACs), especially polar PACs (oxygenated and nitrogenated) occur. They come from the same sources as PAHs but they may also be formed due to PAH degradation under biotic or abiotic processes (natural attenuation or remediation treatment). These PACs, more polar than the 16 US-EPA PAHs, are more soluble in water, resulting in a potentially increased mobility in soils and a higher risk for Humans and Environment. Thus, there is a need to increase our knowledge on polar PAC mobility in soils and their transfer to the groundwater. Combining laboratory and in situ works, this project aimed at identifying the mechanisms involved in the release and transfer mode of polar PACs in soils compared to the 16 US-EPA PAHs. Our works confirm a preferential release of polar PACs compared with PAHs. Polar PACs and low molecular weight PAHs (LMW-PAHs) are mainly released according to a coal tar dissolution mechanism (Raoult law). While satisfactory predictions are obtained for polar PAC release when the pollution is “fresh”, availability is a major parameter that needs to be taken into account for historical contamination impacted by aging. Indeed, whatever the leaching conditions (static-batch and dynamic-column), the PAC concentration in water is highly dependent on the availability level of the pollution. In addition, for a high level of PAC availability, the other parameters studied in the project (ionic strength and temperature) have a limited impact on the PAC release whereas at low availability level, these parameters can show a greater influence. Moreover, the PAC release in association with colloids seems limited for polar PACs but dominating for high molecular weight PAHs (HMW-PAHs), especially under low ionic strength conditions. Leaching tests performed on a lysimeter column (2 m3) filled with a contaminated soil in the 2/3 upper part and with a non-contaminated soil in the 1/3 lower part, both soils being sampled on a former coking plant site, confirm a release of PACs according to a coal tar dissolution mechanism although PAC concentrations are widely lower compared to those predicted by the Raoult law. Whatever the experimental scale studied (batch, laboratory or lysimeter column), a clear influence of the biological compartment has been evidenced. Once the PAHs and polar PACs are dissolved into water, they are highly biodegraded. No by-products - especially oxygenated PACs - were detected

Many polycyclic aromatic compounds (PACs) are toxic, carcinogenic, and mutagenic. As a result, their effects on aquatic biota and ecosystems are of great concern. Research on PACs in aquatic biota often overlooks the role of amphibians, alkylated PACs, and sediment as an uptake route. In order to study the accumulation and toxicokinetics of PACs following sediment and aqueous exposure, and to compare the bioaccumulation potentials of parent and alkyl PACs, two accumulation-elimination experiments using wood frog tadpoles (Lithobates sylvaticus) of Gosner stage 28-32 were conducted (one evaluating exposure to contaminated sediment and water, and the other to contaminated water alone). A complementary field study was then conducted near Fort McMurray, Alberta to assess PAC body burdens in field-collected amphibian larvae, and to determine whether PAC body burdens are related to exposure to sediment and/or water in the field. The results of our studies showed that PAC concentrations and uptake rates in wood frog tadpoles were highest when they were exposed to PAC-contaminated sediment. Consequently, we determined that the dominant route of exposure of wood frog tadpoles to PACs is sediment rather than water. This finding supports other studies that have shown dietary uptake to be an important route of PAC exposure in other aquatic organisms. In both the laboratory and field study, alkyl PAC concentrations exceeded those of parent PACs in wood frog tadpoles, which also demonstrated petrogenic PAC profiles. Interestingly, parent PACs seemed to have greater bioaccumulation potential than alkyl PACs in the laboratory-exposed wood frog tadpoles (in relation to sediment), possibly due to greater bioavailability or lower metabolism of parent PACs or alternatively, due to a saturation in uptake of alkyl PACs. Nevertheless, only a few compounds, including anthracene, fluoranthene, retene, and C1-benzofluoranthenes/benzopyrenes, were found to have higher bioaccumulation potentials. Lithobates sylvaticus tadpoles seemed to be efficient at eliminating and metabolizing both parent and alkyl PACs. However, the elimination of some compounds, such as C4-naphthalenes, was not as efficient. Furthermore, C3-fluorenes and C2-dibenzothiophenes were isolated as potential markers of amphibian larvae exposure to PAC-contaminated sediment due to their positive correlation with the wetland sediment concentrations. Additional field collections in the Athabasca oil sands are warranted to verify the utility of these markers in the natural environment. Evidently, this thesis highlights the importance of including sediment exposure and alkylated PACs in toxicological and field studies of benthic and epibenthic organisms. The results of this study are the largest, most comprehensive set of toxicokinetic and bioaccumulation information of PACs (52 analytes) in the amphibian larvae Lithobates sylvaticus obtained to date.

De nombreuses friches héritées d’activités industrielles révolues présentent des pollutions organiques persistantes (charbon, goudron…). Alors que la réglementation impose un une évaluation du degré de contamination de ces sites, elle ne prend pas en compte les sous-produits de transformation tels que les composés polaires, peu considérés. Pourtant ils se solubilisent dans la phase aqueuse par percolation des eaux météoriques à travers ces surfaces contaminées. Bien que la littérature ciblant la matière organique dissoute (MOD) d’origine naturelle soit abondante, elle n’est pas directement transposable à la MOD issues des friches contaminées, qui reste à définir pour une meilleure compréhension du devenir de la pollution dans ces sites anthropisés. Une approche multi-techniques a été appliquée pour appréhender le plus précisément possible la MOD issue de terres d’anciennes cokeries et usines à gaz, par le biais d’expériences en laboratoire et des dispositifs de terrain (lysimètres). L’étude de ces derniers montre qu’ils contiennent une forte teneur en MOD aromatique, dont les composés aromatiques polycycliques ne représentent qu’une faible proportion de la MOD totale. Des expériences complémentaires ciblant l’influence de certains paramètres (pH et hydrophobicité) suggèrent un lien fort entre le pH et l’organisation spatiale de la MOD, ainsi qu’une diminution de la masse moléculaire apparente avec l’augmentation de l’hydrophobicité. Des expériences de vieillissement artificiel ont montré un enrichissement en produits polaires condensés entraînant leur forte mobilisation par l’eau / A large amount of wastelands inherited from former industrial activities contains persistent organic contamination (coal, coal tar…). While the regulation requires an evaluation of the contamination degree of these soils, it doesn’t take into account the transformation by-products such as polar compounds, poorly studied. Yet they solubilize in aqueous phase by percolation of meteoric waters through these contaminated sites. Despite the fact that literature targeting the fresh DOM is abundant, it is not directly transposable to the anthropogenic DOM coming from wastelands, which still need to be more precisely defined to improve our knowledge of this specific DOM and its evolution over time. A multi-technical approach was developed to comprehend the anthropogenic DOM coming from former coking and gas plant soils, thanks to a combination of laboratory experiments (under controlled conditions) and on field devices (lysimeters). Their study show that they contained high polycyclic aromatic compound (PAC) contents, whose proportions in polar PACs exceed the ones in soil measurements. However, these PACs only consist of a low proportion of the total DOM. Complementary experiences targeting the influence of some parameters (pH, hydrophobicity) show a major hydrophobic characteristic and suggest a strong link between the pH and the spatial DOM organization. Artificial aging experiences show an enrichment in polar compounds leading to their water mobilization

La contamination en composés aromatiques polycycliques (CAP) a été suivie entre 2014 et 2015 au cours de six campagnes d’échantillonnage sur 8 sites différents entre Auboué et Richemont. Cette section du cours d’eau correspond à la partie aval de la vallée de l’Orne profondément affectée par plus d’un siècle d’activités minières et sidérurgiques qui ont cessé entre 1968 et 2009. L’Orne a donc été le réceptacle de rejets industriels et urbains et a été profondément perturbée dans son hydrodynamisme avec la construction de plusieurs barrages. Dans ce contexte, l’occurrence des 16 hydrocarbures aromatiques polycycliques réglementaires (HAP), de 11 CAP oxygénés (O-CAP) et de 5 CAP azotés (N-CAP) et leur distribution dans les fractions dissoute et particulaire des eaux de l’Orne ont été étudiées en mettant en place des protocoles d’échantillonnage et d’analyse adaptés. Le premier objectif de ce travail a été de comparer les méthodes d’échantillonnage des matières en suspension par filtration et par centrifugation à flux continu sur le terrain. Des différences significatives ont pu être identifiées entre les deux techniques, la filtration amenant à des concentrations en CAP plus élevées du fait d’une plus grande abondance des CAP de bas poids moléculaire. Nous avons pu mettre en évidence le rôle de la fraction fine (< 5µm) et/ou colloïdale plus ou moins retenue par les filtres et qui, de part sa réactivité, piège des CAP. La comparaison des deux méthodes dans différentes situations hydrologiques nous montre que cette rétention n’est pas systématique mais plutôt corrélée à des situations de fort hydrodynamisme. Les deux méthodes d’échantillonnage des matières en suspension ne sont donc pas comparables mais complémentaires. Le suivi saisonnier et multi-sites des eaux de l’Orne montre que la concentration en CAP varie entre 1.6 et 223.7 ng L-1 dans la fraction dissoute et entre 1.5 et 105.5 µg g-1 dans la fraction particulaire avec des variations spatiales de ±35% et ±45% respectivement. Les variations de concentration des CAP dans la fraction dissoute sont importantes d’un site à l’autre lorsque le débit est faible (de 0.5 à 34 m3.s-1). Les concentrations en CAP sont faibles autour de 20 ng.L-1 et spatialement homogènes en périodes de haut débit (> 50 m3.s-1) du fait de la dilution. Les concentrations en CAP dans les matières en suspension varient entre 2.8 to 36.3 µg g-1, et montrent des concentrations stables quelles que soient les situations hydrologiques lorsqu’elles sont collectées par la centrifugeuse de terrain. La fraction dissoute est enrichie en HAP de bas poids moléculaire dans les périodes d’étiage et est marquée par l’occurrence des HAP à 5 et 6 cycles aromatiques au cours des épisodes de crue. Les CAP polaires sont au moins aussi abondants que les HAP dans la fraction dissoute et évoluent de la même façon que les HAP. La part des CAP polaires dans la fraction particulaire est significativement plus basse (de 10 à 20% de l’ensemble des CAP) / The spatio-temporal variations of the concentration and distribution of dissolved and particulate polycyclic aromatic compounds (PACs), namely 16 polycyclic aromatic hydrocarbons (PAHs), 11 oxygenated PACs (O-PACs) and 5 nitrogen PACs (N-PACs), were studied in the Orne, a river impacted for more than one century by iron mining and steel-making industry. The first objective of this work was to compare the influence of two different methods of separation of suspended particulate matter (SPM), filtration (FT) and field continuous flow centrifuge (CFC). Results showed that in half of the sampling campaigns, PAC concentrations were 2 to 8 times higher for PAHs and 2 to 10 times higher for O-PAC when SPM were collected by filtration. These differences that were not observed systematically over the six sampling campaigns could be explained by the retention of colloidal matter on glass-fiber filters that appeared as a very reactive phase particularly enriched in low molecular PACs. The two methods were then considered as complementary methods to study SPM. The second objective of this work was to perform a long term monitoring of PAC concentrations and distributions in dissolved and particulate fractions. The results from the six sampling campaigns between May 2014 and September 2015 in eight different sites showed that the PAC concentrations ranged between 1.6 to 223.7 ng L-1 in the dissolved fraction (?PACTD), and between 1,55 to 105,5 µg g-1 in the total particulate fraction, with maximum spatial variation of ±35% and ±45% respectively. The dissolved PACs spatial variations were strongly influenced by the hydrological conditions and less spatial variation was observed during high flow events as the result of dilution and homogenization of pollutants. During low flow events, particulate PACSPM-CFC concentrations were more stable and equivalent in values and distribution to the corresponding PACSPM-FT samples. Overall it was in a range between 2.8 to 36.3 µg g-1. The dominance of dissolved low molecular weight PAHTD in the low flow events decreased during high flow events due to the appearance of penta- and hexa-cyclic PAHs. The dissolved polar PACs were as high as the PAHs contribution and also subjected to seasonal changes, the O-PACs ranged between 5.6 to 90.3 ng L-1 and N-PAHs from 1.0 to 42.5 ng L-1. The particulate polar PACs concentrations and contribution were significantly lower, the highest concentrations of 8,76 µg g-1 and 29,41 µg g-1 was observed during high flow event for O-PACs and during low flow event for N-PAH respectively