Cette thèse se consacre à la mise au point de techniques d’échantillonnage suivies d’analyses réalisées au laboratoire pour mettre en évidence les espèces majoritaires en air intérieur et caractériser leurs variations temporelles. Le développement analytique a été effectué pour 52 COVs et pour 16 HAPs associés à la phase particulaire de l’air. Les prélèvements des COVs ont été réalisés au moyen d’un préleveur automatique permettant d’échantillonner l’air sur des tubes extraits par désorption thermique et analysés par chromatographie gazeuse couplée à la détection FID. Pour la quantification des HAPs, le prélèvement des particules est effectué par un impacteur à cascade à trois étages permettant de fractionner l’aérosol en fonction de leur diamètre aérodynamique. Les HAPs sont quantifiés par chromatographie liquide haute performance couplée à la détection par fluorescence. Ces deux techniques ont été mises en application dans le cadre de la 1ère campagne intensive du projet MERMAID. / This work aims at developing rapid and simple air sampling techniques followed by laboratory analyses to highlight the occurrence of the main species in indoor air and to describe their temporal variations. The analytical development was focused on 52 VOCs belonging to a wide variety of chemical families to determine their concentrations. The sampling step was performed using an automatic sampler allowing the sampling of air on adsorbent tubes. These tubes were then thermally desorbed and analyzed by gas chromatography coupled to FID. Another analytical development was conducted to determine the particle bound PAHs concentrations. The sampling of particles was realized by the mean of a 3-stages cascade impactor allowing an aerosol fractionation depending on their aerodynamic diameter. Finally, quantification of PAHs was realized by liquid chromatography coupled to fluorescence detection. These two techniques were applied in a field campaign in the frame of the MERMAID program.

A controllable self-assembly strategy of positively charged polycyclic aromatic hydrocarbons (PCPAH) towards the formation of rectangle sheets and ribbon-like nanostructures has been achieved by choosing divalent anions with different sizes. In contrast, only rod-like nanostructures are obtained from PCPAH with univalent anions. It is revealed that the divalent anions play a key role in guiding the packing of PCPAH, which provides an unprecedented route to fabricate two-dimensional nanostructures.

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.

The microbiome plays a key symbiotic role in maintaining host health and aids in acquiring nutrients, supporting development and immune function, and modulating behavior. However, more research is needed to elucidate the potential impact of environmental pollutants on host microbial communities and how microbiomes can modulate the toxicity of contaminants to the host. Through a literature review of 18 studies that assessed the impacts of various anthropogenic chemicals on fish-associated microbiomes, we found that toxicants generally decrease microbial diversity, which could lead to long-term health impacts if chronically stressed, and can increase the host’s susceptibility to disease as well as the chemical resistance of certain microbes. These findings led us to explore the impacts of one of the reviewed contaminants, polycyclic aromatic hydrocarbons (PAHs), typically found in oil. The Deepwater Horizon disaster of April 2010 was the largest oil spill in U.S. history and had catastrophic effects on several ecologically important fish species in the Gulf of Mexico (GoM). This study tested the hypotheses that exposure to weathered oil would cause significant shifts in fish gut-associated microbial communities, with taxa known for hydrocarbon degradation increasing in abundance and that foraging behavior would decrease, potentially due to microbial dysbiosis via the gut-brain axis. We characterized the gut microbiome (with 16S rRNA gene sequencing) of a native GoM estuarine species, the sheepshead minnow (Cyprinodon variegatus). Fish were exposed to High Energy Water Accommodated Fractions (HEWAF; tPAH = 80.99 ± 12.5 μg/L) of oil over a 7-day period and whole gastrointestinal tracts were sampled for microbiome analyses. A foraging behavioral assay was used to determine feeding efficiency before and after oil exposure. The fish gut microbiome did not experience any significant changes in alpha or beta diversity but known hydrocarbon degrading taxa were noticeably present in oil-exposed communities and were absent in controls. We found the order Pseudomonadales, the family Paenibacillaceae, and Pseudomonas pachastrellae to be among these, with Pseudomonadales increasing in abundance. Foraging behavior was not significantly affected by oil exposure. This work highlights the need for further research to elucidate the functional metagenomic responses of the fish gut-microbiome under oil spill conditions.

This work includes two unrelated areas of research. The first portion of this work involved combusting densified refuse derived fuel (dRDF) with coal and studying the effect that Ca(0H)2 binder had on reducing polycyclic aromatic hydrocarbon (PAH) and polychlorinated biphenyl (PCB) emissions. The second area of work was directed at developing nondestructive infrared techniques in order to aid in the analysis of postage stamp adhesives. With Americans generating 150-200 million tons a year of Municipal Solid Waste (MSW) and disposing of nearly ninety percent of it in landfills, it is easy to understand why American landfills are approaching capacity. One alternative to landfilling is to process the MSW into RDF. There are technical and environmental problems associated with RDF. This work provides some answers concerning the amount of PAH and PCB emissions generated via the combustion of RDF with coal. It was found that the Ca(OH)2 binder greatly reduced both the PAH and the PCB emissions. In fact, PAH emissions at the ten-percent level were reduced more by using the binder than by the pollution control equipment. If the Ca(0H)2 binder can reduce not only PAH and PCB emissions, but also other noxious emissions, such as acid gases or dioxin, RDF technology could soon be the answer to the current landfill problems. The second portion of this work focused on developing a method to analyze stamp adhesives nondestructively. Using this method, it was fairly easy to differentiate among the three different types of adhesives that have been used by the United States Postal Service: gum arabic, dextrin, and polyvinyl alcohol. Differences caused by changes in chemicals added to the adhesives were also detected. Also, forgeries were detected with as much success, if not more, than by conventional methods. This work also led to the construction of equipment that allows large samples to be analyzed by reflectance infrared methods.

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

This dissertation presents experimental and instrumentation developments that take full advantage of the multidimensional nature of line narrowing spectroscopy at liquid nitrogen (77 K) and liquid helium (4.2 K) temperatures. The inconvenience of sample freezing procedures is eliminated with the aid of cryogenic fiber optic probes. Rapid collection of multidimensional data formats such as wavelength time matrices, excitation emission matrices, time-resolved excitation emission matrices and time resolved excitation emission cubes is made possible with the combination of a pulsed tunable dye laser, a spectrograph and an intensifier-charged coupled device. These data formats provide unique opportunities for processing vibrational luminescence data with second order multivariate calibration algorithms. The use of cryogenic fiber optic probes is extended to commercial instrumentation. An attractive feature of spectrofluorimeters with excitation and emission monochromators is the possibility to record synchronous spectra. The advantages of this approach, which include narrowing of spectral bandwidth and simplification of emission spectra, were demonstrated with the direct analysis of highly toxic dibenzopyrene isomers. The same is true for the collection of steady-state fluorescence excitation-emission matrices. These approaches provide a general solution to unpredictable spectral interference, a ubiquitous problem for the analysis of organic pollutants in environmental samples of unknown composition. Since commercial spectrofluorimeters are readily available in most academic institutions, industrial settings and research institutes, the developments presented here should facilitate the widespread application of line-narrowing spectroscopic techniques to the direct determination, no chromatographic separation, of highly toxic compounds in complex environmental matrixes of unknown composition.

Polyzyklische aromatische Kohlenwasserstoffe (PAK) sind eine Klasse krebserregender Schadstoffe. Aufgrund ihres weit verbreiteten Vorkommens und der toxischen Risiken für die menschliche Gesundheit und das Ökosystem ist es unerlässlich, durch systematische Forschung wirksame Minderungsstrategien auf verschiedenen Ebenen zu etablieren. In dieser Dissertation wurden Quellenzuordnung, Multimedia-Schicksal, Schlüsselemis-sionssektoren und globale gesundheitliche Auswirkungen von PAK-Belastungen unter-sucht. Diese Forschung wurde durchgeführt, um Daten zur Verfügung zu stellen, die po-tenzielle Minderungsstrategien unterstützen, um PAK-Verschmutzungen und damit ver-bundene gesundheitliche Auswirkungen auf regionaler, nationaler und globaler Ebene zu reduzieren. Zunächst wurde die Quellenzuordnung von Langzeit-PAH in acht Flüssen untersucht. Diese Studie untersuchte systematisch die zeitlichen und saisonalen Trends, die peri-odische Oszillation, die Quellenzuordnung und die Risikobewertung von PAKs für die menschliche Gesundheit in acht Flüssen, die eine quellenorientierte PAK-Minderung in der Region unterstützen können. Zweitens ist das Multimedia-Schicksal von PAKs entscheidend für eine bessere Umwelt-politik. Diese Studie bewertete systematisch die räumlich-zeitliche Verteilung, die Quellenzuordnung, den multimedialen Transport und den Verbleib von PAK, die an Schwebstaub (SPM) in Rhein und Elbe adsorbiert sind, was die Stadtplanung unterstützen kann, um PAK in den Regionen zu lindern. Drittens wurden in dieser Studie die wichtigsten Emissionssektoren von PAK bestimmt, indem die langfristigen verkörperten und ermöglichten PAK-Emissionen in verschiedenen Sektoren abgeschätzt und die Beiträge sozioökonomischer Determinanten quantifiziert wurden. Die Ergebnisse können wirksame Strategien zur Verringerung der PAK-Emissionen in verschiedenen Sektoren aus der Perspektive des Endverbrauchs und des primären Inputverhaltens auf nationaler Ebene unterstützen. Schließlich wurden in dieser Studie die globalen Triebkräfte der gesundheitlichen Auswir-kungen von PAH untersucht, indem ein integrierender Rahmen angewendet wurde, der das globale PAH-Emissionsinventar, das um die Umwelt erweiterte multiregionale Input-Output-Modell, das GEOS-Chem-Chemikalientransportmodell und das lebenslange Lung-enkrebsrisiko verknüpfte Bewertung und Analyse der Strukturzerlegung. Die Ergebnisse können politische Entscheidungen zur Optimierung von Minderungsstrategien aus verschiedenen Perspektiven unterstützen, um PAK-Emissionen und gesundheitliche Aus-wirkungen weltweit effektiv zu reduzieren. / Polycyclic aromatic hydrocarbons (PAHs) are a class of carcinogenic pollutants. Due to their widespread occurrence and toxic risks to human health and ecosystem, it is essen-tial to establish effective mitigation strategies at different scales through systematic re-search. In this dissertation, source apportionment, multimedia fate, key emission sectors and global health impacts of PAH pollutions have been investigated. This research was conducted to provide data to assist potential mitigation strategies to reduce PAH pollu-tions and related health impacts at regional, national, and global scales. Firstly, the source apportionment of long-term PAHs in eight rivers were investigated. This study systematically investigated the temporal and seasonal trends, periodic oscilla-tion, source apportionment, and human health risk assessment of PAHs in eight rivers, which can assist source-oriented PAH mitigation in the region. Secondly, the multimedia fate of PAHs is critical for achieving better environmental poli-cies. This study systematically evaluated the spatiotemporal distribution, source appor-tionment, multimedia transport and fate of PAHs adsorbed on suspended particulate matter (SPM) in Rhine and Elbe Rivers, which can assist urban planning to alleviate PAHs in the regions. Thirdly, the key emission sectors of PAHs were determined in this study through estimat-ing the long-term embodied and enabled PAH emissions in various sectors and quantify-ing the contributions of socioeconomic determinants. The results can assist effective strategies for mitigating PAH emissions in different sectors from the perspectives of final consumption and primary input behaviors at a national scale. Finally, the global driving forces of PAH health impacts were investigated in this study through applying an integrating framework, linking global PAH emission inventory, envi-ronmentally extended multi-regional input-output model, GEOS-Chem chemical transport model, lifetime lung cancer risk assessment, and structure decomposition analysis. The results can assist policy decisions to optimize mitigation strategies from different per-spectives for effectively reducing PAH emissions and health impacts in the world.

The Deepwater Horizon oil spill released millions of barrels of oil into the Gulf of Mexico, impacting economically and ecologically important fishes. Polycyclic aromatic hydrocarbons (PAHs) present in the oil have been shown to cause developmental impairments in early life stage fishes, such as morphological and behavioral changes related to eye formation and visual processing following PAH exposure. Prior research reported reduced eye growth in open water, pelagic species, as well as reduced photoreceptor-specific transcription factors associated with eye development following exposure to crude oil. Though changes in transcriptomic-level pathways associated with vision and visual processing have been reported, it has yet to be determined how these changes relate to physiological or behavioral-level effects in fish. Therefore, the present studies evaluated the effect of weathered crude oil on eye development and visual function in mahi-mahi, red drum, sheepshead minnow, and zebrafish larvae. Fish were assessed through several visually-mediated behavioral assays, analyzed histologically and immunohistologically, along with subsequent transcriptomic analyses and associated gene expression changes. Larvae exposed to crude oil experienced significantly reduced abilities to exhibit optomotor or optokinetic responses relative to controls, with associated reductions in retinal development. Furthermore, genes associated with eye development and phototransduction were downregulated, with subsequent decreases in the immunofluorescence of neurological connections within the retina and a choroid-specific increase in apoptotic activity. We related oil-induced transcriptomic-level effects to morphological, physiological, and behavioral-level impairments in larval teleost fishes.

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