To address my first objective, I opportunistically collected road-killed bobcats (n=44) throughout Illinois during 2013-2014, and analyzed their liver tissue for the presence of PCBs, PBDEs, and various other alternative halogenated flame retardants. Concentrations of ∑PCBs ranged from 76.4 ng/g lw to 3782 ng/g lw (median 562.97 ng/g lw). Male bobcats had significantly higher concentrations of PCBs than females (p = 0.04). Concentrations of ∑PBDEs (including all detectable PBDE congeners) ranged from 8.3 to 1920 ng/g lipid weight (median: 50.3 ng/g lw). Among the alternative flame retardants screened, Dechloranes (including anti- and syn-Dechlorane Plus and Dechlorane-602, 603, and 604), tetrabromo-o-chlorotoluene (TBCT), and hexabromocyclododecane (HBCD) were also detected frequently, with median concentrations of 28.7, 5.2, and 11.8 ng/g lw, respectively. Dechlorane analogue compositions in bobcats were different from that reported in other studies, suggesting species- or analogue-dependent bioaccumulation, biomagnification, or metabolism of Dechlorane chemicals in different food webs. My findings, along with previously reported food web models, suggest Dechloranes may possess substantial bioaccumulation and biomagnification potencies in terrestrial mammalian food webs. Thus, attention should be given to these highly bioavailable flame retardants in future environmental biomonitoring and risk assessments in a post-PBDE era. To address my second objective I collected raccoons (n=32) from various sites across Illinois and Missouri during 2013-2015. Liver tissues were analyzed for the presence of PBDEs and Dechloranes. ∑PBDE concentrations ranged from 19.1 ng/g lw to 2124 ng/g lw (median = 98.0 ng/g lw) and did not differ between gender or age of raccoon. Although nonsignificant (p=0.06), adult raccoons appeared to have greater PBDE concentration loads compared to juveniles. These nonsignificant differences are likely due to large variation in contaminant concentrations, possibly reflecting differences in individual raccoon diet and behavior. This is the first study reporting bioaccumulation of halogenated flame retardants in a wild felid in North America, and also the first report of PBDE accumulation in North American raccoons. The wide detection of Dechloranes, HBCD and TBCT in bobcats suggests a broad exposure of these alternative flame retardants in terrestrial apex predators in terrestrial ecosystems. The comparatively high levels of PBDEs in raccoons also suggest that biota in terrestrial habitats are still widely exposed to and susceptible to the bioaccumulation of these flame retardants.

Extraction processes employing emulsion liquid membranes (ELMs), water-in-oil emulsions dispersed in aqueous phase, have been shown to be highly efficient in removing a variety of organic and inorganic contaminants from industrial wastewaters. As a result, they have been considered as alternative technologies to other more common separation processes such as pressure-driven membrane processes. Unfortunately, a widespread use of the ELM process has been limited due to the instability of emulsion globules against fluid shear. Breakup of emulsions and subsequent release of the internal receptor phase to the external donor phase would nullify the extraction process. Numerous studies have been, therefore, made in the past to enhance the stability of ELMs. Examples include adding more surfactants into the membrane phase and increasing the membrane viscosity. However, increased stability has been unfortunately accompanied by loss in extraction efficiency and rate in most reported attempts. The primary objective of this research is to apply the ELMs in a unique contacting device, a Taylor-Couette column, which provides a relatively low and uniform fluid shear that helps maintaining the stability of emulsion without compromising the extraction efficiency of a target compound. The ELM used in this study is made of membrane phase converted into non-Newtonian fluid by polymer addition, which provides additional uncommon remedy for the problem. This innovative ELM process was optimized to treat various types of simulated industrial wastewaters containing selected phenolic compounds and heavy metals. Experiments performed in this study suggested that the newly developed ELM process achieved exceptionally high overall removal efficiencies for the removal of these target compounds in relatively short contact time. Mechanistic predictive models were further developed and verified with the experimental data. Combined with the experimental data and novel mathematical predictive models, this study is expected to have a high impact on immediate practices of emulsion liquid membrane technologies in relevant industries.

A cause d’une anthropisation toujours plus forte des écosystèmes, de plus en plus de menaces pèsent sur la biodiversité. Parmi celles-ci, l’exposition aux contaminants est particulièrement problématique pour les organismes vivants. Emis et utilisés dans les pays industrialisés, ces contaminants hautement persistants dans l’environnement vont gagner les régions polaires puis se bio-accumuler dans les organismes vivants au cours du temps et se bio-amplifier le long du réseau trophique. Ainsi, les oiseaux marins, longévifs et situés dans les maillons supérieurs de la chaine alimentaire, sont particulièrement exposés et vulnérables à une exposition chronique à ces contaminants. A travers une perturbation endocrinienne, ces contaminants vont pouvoir impacter certains mécanismes physiologiques et traits comportementaux, entrainant in fine des conséquences à long-terme sur la fitness des individus et populations. Ma thèse s’articule autour de trois grandes familles de contaminants : i) les composés perfluoroalkylés (PFASs), encore largement utilisés dans plusieurs secteurs industriels et agricoles et en augmentation dans l’environnement ; (ii) les composés organochlorés dits « d’héritage » (OCs), interdits depuis des années mais entrainants toujours des effets délétères sur la biodiversité et (iii) le mercure (Hg), métal lourd non-essentiel ayant une origine à la fois anthropique et naturelle. Basé sur une approche corrélative in natura, je me suis intéressé aux conséquences physiologiques et comportementales d’une exposition chronique à ces trois grandes familles de contaminants présents chez la mouette tridactyle (Rissa tridactyla) de l’Arctique Norvégien (Svalbard) au cours de son cycle reproducteur (depuis l’accouplement jusqu’à l’élevage des poussins). Spécifiquement, j’ai étudié les relations entre ces contaminants et la fertilité (morphologie et motilité des spermatozoïdes), l’expression des signaux sexuels (visuel : coloration des téguments, olfactif : signature chimique), les comportements de soins parentaux (température d’incubation et rotation de l’œuf), le vieillissement cellulaire (longueur des télomères) et la dépense énergétique (métabolisme de base). Je me suis également penché sur de potentiels mécanismes sous-jacents permettant d’expliquer ces relations. Puisque ces mécanismes physiologiques et comportementaux sont fortement impliqués dans la valeur sélective des individus, les possibles conséquences à long terme de cette exposition sur la reproduction et survie des individus sont discutées. Ce travail permet de souligner la forte toxicité de certains composés organochlorés « historiques » (en particulier les chlordanes) et d’apporter de toutes nouvelles connaissances sur la toxicité très mal connue des PFASs chez la faune sauvage. Fait important, ce travail de thèse révèle que les PFASs et les OCs pourraient agir de manière contrastée sur plusieurs mécanismes physiologiques et traits comportementaux. Spécifiquement, une forte exposition à l’oxychlordane, un métabolite du chlordane, pesticide interdit depuis des décennies, est associée à des télomères plus courts, une réduction du métabolisme de base et à une moindre capacité à incuber les œufs. A l’inverse, on observe une élongation des télomères, une augmentation du métabolisme de base et une rotation des œufs accrue chez les individus les plus exposés aux PFASs. Le Hg, au moins en ce qui concerne les paramètres étudiés, ne semble pas jouer un rôle majeur. Cette étude souligne l'importance de tenir compte de plusieurs groupes de contaminants lorsqu'on étudie les conséquences de l'exposition aux contaminants environnementaux chez la faune sauvage. / Due to increasing human activities, a growing number of threats are challenging the fate of biodiversity. Among them, environmental contamination is particularly concerning for living organisms. Used and released in industrialized countries, these highly persistent contaminants can reach remote areas such as the Arctic ecosystem and will biomagnify though food webs and bioaccumulate in organisms. Long-lived seabirds are located in the upper levels of the food chains and thus particularly exposed and sensitive to a chronic contaminants exposure. Through endocrine disruption, these contaminants can impact physiological mechanisms and behavioural traits, inducing in fine, long-term fitness consequences on individuals and populations. My thesis focuses on three groups of contaminants: (i) poly- and perfluoroalkyl substances (PFASs), still broadly used in a vast array of industrial processes and increasing in the Arctic; (ii) “legacy” organochlorine contaminants (OCs, pesticides and industrial compounds), banned from use but still well present in the Arctic and (iii) mercury (Hg), a non-essential metal coming of both natural and anthropic origins. Based on a correlative approach conducted in natura, I investigated the physiological and behavioural consequences of exposure to these contaminants during the whole breeding cycle (from pre-laying to chick-rearing period) in an Arctic seabird, the black-legged kittiwake (Rissa tridactyla) from Svalbard, Norwegian Arctic. Specifically, I examined the relationships between several PFASs, OCs, Hg and fertility (sperm morphology and motility), sexual signaling (visual: integument coloration and olfactory: chemical signature), parental care behaviors (incubation temperature and egg-turning), ageing (telomere length) and energy expenditure (basal metabolic rate). In addition, some potential underlying mechanisms were also studied to better understand the way through which contaminants can be detrimental for kittiwakes. Furthermore, since physiological mechanisms and behavioral traits investigated here are tightly involved in self maintenance and reproduction, possible effects on fitness are then discussed. This PhD work underlines the major role of certain legacy chlorinated organic compounds (e.g. chlordanes) and significantly contributes at documenting the poorly known toxicological consequences of PFASs exposure in wildlife. Importantly, this PhD shows that PFASs and OCs could impact ageing, energy expenditure and some parental care behaviors in a contrasted manner. Specifically, oxychlordane, a metabolite of a banned organochlorine pesticide was associated with decreased telomere length, lowered metabolic rate and reduced ability to incubate the eggs. Conversely, elongated telomere, increased BMR and enhanced egg rotation were observed in birds bearing the highest concentrations of PFASs. Finally, at least for the considered endpoints, Hg appears as a coming minor threat for kittiwakes. This study highlights the importance of considering several groups of contaminants when investigating the consequences of environmental contaminants exposure in wildlife.

BACKGROUND:The widespread utilization of organic compounds in modern society and their dispersion through wastewater have resulted in extensive contamination of source and drinking waters. The vast majority of these compounds are not regulated in wastewater outfalls or in drinking water while trace amounts of certain compounds can impact aquatic wildlife. Hence it is prudent to monitor these contaminants in water sources until sufficient toxicological data relevant to humans becomes available. A method was developed for the analysis of 36 trace organic contaminants (TOrCs) including pharmaceuticals, pesticides, steroid hormones (androgens, progestins, and glucocorticoids), personal care products and polyfluorinated compounds (PFCs) using a single solid phase extraction (SPE) technique with ultra-high performance liquid chromatography coupled to tandem mass spectrometry (UHPLC-MS/MS). The method was applied to a variety of water matrices to demonstrate method performance and reliability.RESULTS:UHPLC-MS/MS in both positive and negative electrospray ionization (ESI) modes was employed to achieve optimum sensitivity while reducing sample analysis time (<20min) compared with previously published methods. The detection limits for most compounds was lower than 1.0 picogram on the column while reporting limits in water ranged from 0.1 to 15ng/L based on the extraction of a 1L sample and concentration to 1mL. Recoveries in ultrapure water for most compounds were between 90-110%, while recoveries in surface water and wastewater were in the range of 39-121% and 38-141% respectively. The analytical method was successfully applied to analyze samples across several different water matrices including wastewater, groundwater, surface water and drinking water at different stages of the treatment. Among several compounds detected in wastewater, sucralose and TCPP showed the highest concentrations.CONCLUSION:The proposed method is sensitive, rapid and robust / hence it can be used to analyze a large variety of trace organic compounds in different water matrixes.

Mixtures of chlorinated organic pollutants can be found in the soils at chlorophenol-contaminated sawmill, including (inter alia) polychlorinated phenols (CPs), phenoxyphenols (PCPPs), diphenyl ethers (PCDEs), dibenzofurans (PCDFs) and dioxins (PCDDs). These hydrophobic compounds have low water solubility and hence low mobility as truly dissolved compounds. However, they may migrate through the soil at significant rates via co-transport with dissolved organic matter (DOM) and colloids of fine, waterborne particulate matter. In the work underlying this thesis the distribution of chlorinated hydrophobic pollutants between these two mobile fractions in soil samples from five sawmill sites was studied Soils at five sites at which CPs were formerly used were characterized, and found to have complex profiles of chlorinated hydrophobic pollutants. CPs, PCPPs, PCDEs and PCDD/Fs were present at up to ppm-levels. Furthermore, the relative proportions of the pollutants differed from their relative proportions in the preservatives used at the sites, indicating that they have been transported from, and/or degraded in, the soil at different rates. These organic pollutants have low water solubility and strong affinity for soil organic matter (SOM). The importance of SOM for the fate of CPs, PCPPs, PCDEs, PCDFs and PCDDs in soil was investigated by examining the distribution of compounds between the mobile DOM and the immobile particulate organic matter (POM). The partitioning of CPs between DOM and POM was found to be approximately equal. However, the relative strength of association with POM of groups of chlorinated organic pollutants was positively correlated with their hydrophobicity, and thus increased in the order CP &lt; PCPP &lt; PCDE &lt; PCDF &lt; PCDD. Despite the weak association of PCDD/Fs with DOM our investigations found that considerable concentrations of these pollutants were bound to mobile fractions (DOM and colloids, &gt;0.2 µm) in both a groundwater analysis and a leaching test. CPs and PCPP were present at up to ppm- and ppb-levels, respectively, and PCDEs and PCDD/Fs at up to ppt-levels. The importance of transport in association with the mobile fraction (DOM and colloids) increased with increasing hydrophobicity e.g. PCDDs were almost entirely associated with fine particulate matter, while CPs were largely found in the water phase and only minor proportions were associated with colloids.

The dominating factors affecting sorption of per- and polyfluoroalkyl substances (PFAS) remain subject of research and debate. Traditionally, distribution coefficients (e.g., Kd and KOC) are used to calculate the fractionation of the contaminant between soil and water, to estimate leaching and subsequently the risks it imposes reaching water reservoirs. Research has aimed to establish the sorption mechanisms for PFAS but, due to the complexity of interactions between the substance specific physiochemical properties and geochemical sorbent characteristics, it has shown to be a complicated task. For PFOS, one of the most commonly encountered PFAS, the Swedish Geotechnical Institute (SGI) recommends using the 10th percentile of a small data set for the organic carbon-water distribution coefficient KOC (500 L/kg) and multiply this with the organic content of the in-situ soil to obtain the soil-water distribution coefficient (Kd). The result of this study shows that this method is insufficient to obtain a good approximation of the mobility of PFOS at a contaminated site. With a review of recent research on PFAS sorption and a case study performed at Stockholm Arlanda Airport, this study concludes that as of today, and due to PFAS potent mobility, well measured field coefficients for each soil type present in the soil profile and an elaborate geohydrological model is necessary to estimate PFAS environmental transport, fate and associated risks. It also concludes that parameters such as anionic exchange capacity and soil protein content may be highly relevant to estimate PFAS sorption.

Using a comparative spatial and temporal analysis on sediment cores from 8 lakes in the Mackenzie River Delta uplands region, NT, Canada, this study assessed how persistent organic pollutant (POP) deposition to lake sediments was affected by: (1) the presence of retrogressive thaw slumps on lake shores; and (2) changes occurring with increased autochthonous primary productivity. POPs examined included polychlorinated biphenyls (PCBs), penta- and hexachlorobenzenes (CBzs), and dichlorodiphenyltrichloroethane and metabolites (DDTs). Surface sediments of slump-affected lakes contained higher total organic carbon (TOC)-normalized POP concentrations than nearby reference lakes unaffected by thaw slumps. Inorganic sedimentation rates were positively related to contaminant concentrations, suggesting that the influx of siliciclastic material reducing organic carbon in slump-affected lake water indirectly results in higher concentrations of POPs on sedimentary organic matter. This explanation was corroborated by an inverse relationship between sedimentary POP concentrations and TOC content of the lake water. Deposition proxies of autochthonous carbon were not significantly correlated to POP fluxes of surface sediments, and historical profile fluctuations did not coincide with variation in POP deposition. Thus this study does not support the contention that algal-derived organic carbon increases the delivery of organic pollutants to sediments (the algal-scavenging hypothesis), as previously proposed for mercury. Higher POP concentrations observed in surface sediments of slump-affected lakes are best explained by simple solvent switching processes of hydrophobic contaminants onto a lower pool of available organic carbon when compared to neighbouring lakes unaffected by thaw slump development.

Using a comparative spatial and temporal analysis on sediment cores from 8 lakes in the Mackenzie River Delta uplands region, NT, Canada, this study assessed how persistent organic pollutant (POP) deposition to lake sediments was affected by: (1) the presence of retrogressive thaw slumps on lake shores; and (2) changes occurring with increased autochthonous primary productivity. POPs examined included polychlorinated biphenyls (PCBs), penta- and hexachlorobenzenes (CBzs), and dichlorodiphenyltrichloroethane and metabolites (DDTs). Surface sediments of slump-affected lakes contained higher total organic carbon (TOC)-normalized POP concentrations than nearby reference lakes unaffected by thaw slumps. Inorganic sedimentation rates were positively related to contaminant concentrations, suggesting that the influx of siliciclastic material reducing organic carbon in slump-affected lake water indirectly results in higher concentrations of POPs on sedimentary organic matter. This explanation was corroborated by an inverse relationship between sedimentary POP concentrations and TOC content of the lake water. Deposition proxies of autochthonous carbon were not significantly correlated to POP fluxes of surface sediments, and historical profile fluctuations did not coincide with variation in POP deposition. Thus this study does not support the contention that algal-derived organic carbon increases the delivery of organic pollutants to sediments (the algal-scavenging hypothesis), as previously proposed for mercury. Higher POP concentrations observed in surface sediments of slump-affected lakes are best explained by simple solvent switching processes of hydrophobic contaminants onto a lower pool of available organic carbon when compared to neighbouring lakes unaffected by thaw slump development.