Effective adsorbents for polyfluorinated compounds (PFCs) were successfully prepared. And they were tested in the adsorption of perfluorooctanoic and perfluorooctanesulfonic acids. Bridged silsesquioxanes containing secondary and tertiary amino groups were synthesized by sol-gel condensation of bis[3-(trimethoxysilyl)propyl]amine and bis[3-(methylamino)propyl]-trimethoxysilane in acidic media with surfactants. Obtained materials are mesoporous with a high BET surface area. They combine high structural stability with a high concentration of surface amino groups serving as adsorption sites. Batch adsorption tests demonstrated their extremely high adsorption capacity on PFCs: in some experiments, it reached up to 88% of the adsorbent weight. Adsorption of PFCs changed the surfaces of the adsorbent nanoparticles from hydrophilic to hydrophobic thus providing their agglomeration and floatability. Column tests showed fast adsorption of PFCs even at high concentrations and high flow rates. Obtained results can be used in the development of an effective filtration device for clean-up of water contaminated by PFCs.

Cette thèse porte sur l’évaluation de l’impact de certains composés environnementaux sur la fécondité féminine, tel que mesuré par le délai de conception (« time to pregnancy » en anglais, ou TTP). Cette recherche a été réalisée dans le cadre de l’Étude mère-enfant sur les composés chimiques de l’environnement (MIREC), une cohorte de grossesse de 2001 femmes recrutées durant le premier trimestre dans dix villes canadiennes de 2008 à 2011. Les données des questionnaires et les échantillons biologiques ont servi à évaluer l’effet de deux groupes de composés : les persistants [composés perfluorés – perfluorooctanesulfonate (PFOS), perfluorooctanoate (PFOA) et perfluorohexane sulfonate (PFHxS)] et les non persistants (bisphénol A, triclosan et phtalates). Cette thèse comprend également une analyse du potentiel du ratio index-annulaire (2D:4D) comme mesure de sensibilité endocrinienne. À ce jour, des mesures anthropométriques ont été collectées sur environ 800 mères-enfants dans le cadre de l’Étude mère-enfant sur les composés chimiques de l’environnement : biomonitoring et neurodéveloppement à la petite enfance (MIREC CD Plus), un suivi de la cohorte MIREC portant sur la croissance et le développement des enfants jusqu’à 5 ans. Sur l’ensemble, les résultats de cette thèse permettent d’étoffer les preuves concernant les effets adverses potentiels de plusieurs contaminants environnementaux sur la fécondité féminine, telle que mesurée par le TTP. Dans le premier article, nous avons montré une association entre les PFOA et les PFHxS et une baisse de fécondité, ce que d’autres recherches avaient déjà révélé. Dans le deuxième article, nous avons évalué l’effet du triclosan sur le TTP, ce qui n’avait jamais été examiné, pour montrer un délai plus élevé chez les femmes du quartile supérieur d’exposition. De plus, nos résultats sont en accord avec ceux de la seule étude ayant évalué l’effet du Bisphénol A sur la fécondité féminine, qui n’avait pas détecté d’effet. Finalement, nos données semblent indiquer une association entre l’exposition des femmes aux phtalates et un TTP plus court, mais ces résultats ne sont pas statistiquement significatifs. En ce qui a trait au potentiel du ratio index-annuaire (2D:4D) pour mesurer la sensibilité endocrinienne chez les femmes, nos données ne permettent pas d’établir une association entre ce ratio et le TTP. Pour ce qui est des enfants, nous n’avons pas trouvé d’effet adverse entre le tabagisme de la mère durant la grossesse et leur ratio 2D:4D. Par conséquent, nos données ne semblent pas justifier l’utilisation du ratio 2D:4D pour mesurer la sensibilité endocrinienne en lien avec le potentiel reproducteur (basé sur le TTP) ou l’exposition des enfants au tabac durant le premier trimestre de grossesse. / In this thesis, we aimed to evaluate the impact of selected environmental compounds on female fecundity as measured by time to pregnancy (TTP). This research was conducted in the framework of the Maternal-Infant Research on Environmental Chemicals (MIREC) study, a pregnancy cohort of 2001 women recruited during the first trimester of pregnancy in ten cities across Canada between 2008 and 2011. Questionnaire data and biological samples were analyzed to assess the effect of two groups of compounds: persistent [perfluorinated compounds - perfluorooctane sulfonate (PFOS), perfluorooctanoate (PFOA), and perfluorohexane sulfonate (PFHxS)-] and nonpersistent chemicals (Bisphenol A, Triclosan, and phthalates). In addition, this thesis aimed to examine the potential of the second to fourth finger digit ratio (2D:4D) as a sensitive-endocrine endpoint. To this end, anthropometric measurements were obtained in about 800 children and their mothers during the Early Childhood Biomonitoring and Neurodevelopment Study (MIREC-CD Plus), a MIREC follow-up conducted to measure growth and development up to age five. Overall, the results of this thesis have contributed to the evidence regarding the potential adverse effect of several environmental contaminants (ECs) on female fecundity as measured by TTP. In the first article, we found that PFOA and PFHxS were associated with diminished fecundity, supporting previous evidence that suggested a similar effect. In the second article, we assessed for the first time the effect of Triclosan on TTP, presenting evidence of delayed fecundity at the highest quartile of exposure. In addition, our findings agreed with those of the only study that has assessed the effect of Bisphenol A on female fecundity, and which showed no effect. Finally, we found some indication that female exposure to phthalates might be associated with a shorter TTP, although this finding did not reach statistical significance. With regard to the potential of the digit length ratio (2D:4D) as an endocrine-sensitive endpoint in women, our data do not support a strong association between 2D:4D and TTP. In children, we did not find an adverse impact of maternal smoking during pregnancy on children’s 2D:4D. Thus, our data do not support evidence to suggest that 2D:4D could be used as a potential reproductive endocrine-sensitive endpoint in women as measured by TTP, and in their offspring as measured by exposure to maternal smoking during the first trimester of pregnancy.

BACKGROUND: Perfluorinated compounds (PFCs) have been used as durable water and oil repellent treatments in clothing for more than 50 years. The reason for its popularity is related to the chemical structure, which also makes these compounds persistent in the environment. Numerous studies have shown negative environmental and health effects related to high concentrations of perfluorinated compounds in blood serum. Due to these studies, this paper aimed to find out if perfluorinated compounds could be replaced by non-perfluorinated without compromising performance related to water and oil repellency. METHODOLOGY: A reference sample impregnated with fluorocarbons was compared with the following non-perfluorinated treatments, aliphatic polyurethane (comb polymer) organic silicone and acid (comb polymer) and hydrocarbon (dendrimer). Impregnations were subjected to abrasion, UV-radiation and washing and after each destructive treatment; oil and water repellency tests were conducted. The environmental and health effect of all treatments were examined in a theoretical study. RESULTS: Due to difficulties with the impregnation process, comparable results could only be concluded with the perfluorinated and the hydrocarbon compound. The hydrocarbon was superior the perfluorinated compound to abrasion but for usage simulation methods that allowed chemical reactions, hence UV-radiation and washing, the fluorocarbons showed better resistance. CONCLUSION: Results show that the hydrocarbon treatment could replace perfluorinated treatments commercially when only water and not oil repellency is required. The alternative treatments in this study are not yet sufficiently examined with respect to environmental and health and can therefore not be called greener with certainty. / Program: Textilingenjörsutbildningen

The most important substances of the group of perfluorinated compounds are perfluorooctyl sulfonate (PFOS), perfluorooctanoic acid (PFOA) and perfluorooctane sulphonamide (FOSA). Perfluorinated compounds have special physical and chemical properties, which make them valuable for usage in different industrial branches. These properties, which make them so useful are also the reason, why they are so harmful for the environment. The target of theoretical part of the diploma thesis was processing of literature searche on the topic: Evaluation of environmental load by perfluorinated compounds. In the experimental part was developed and optimized a method that was used for the identification and quantification of selected pollutants contained in real soil samples.

The City of Cape Town's (CoCT) wastewater management system discharges effluent from households, industries and other sources into the Atlantic Ocean through deep-water marine outfalls in Green Point, Camps Bay and Hout Bay. At total capacity, these three outfalls discharge 55.3 megalitres (Ml) into marine receiving environments daily. With minimal pre-treatment that amounts to screening and sieving, this results in microbial and chemical pollution of the sea (including chemicals of emerging concern), marine organisms, recreational beaches, and Marine Protected Areas (MPAs). This research focuses on contestations over evidence of that pollution in Hout Bay. The study documents the work of independent scientists seeking to provide evidence of coastal pollution obtained via microbial and chemical analyses of water (coastal and inland) and marine organisms (Mytilus galloprovincialis) samples. It also presents accounts of pollution obtained via ethnographic research with local residents, fishers, frequent water users and river activists who have observed and experienced poor coastal water quality. However, the form of evidence that is considered and informs decision-making processes by the CoCT has consistently sought to invalidate these forms of evidence, from both independent scientists and the public. Debates around knowledge of water and contests over evidence that highlight the entanglements of science, politics, and ways of knowing make visible a consistent pattern in coastal water-quality governance by the City, which results in inaction regarding the ever-growing issue of coastal pollution in Cape Town.

In the presented PhD. thesis, problems covering occurrence of polybrominated diphenyl ethers (PBDE) and perfluorinated compounds in the environment were solved. The study was focused on identification and further verification of optimal methods in order to determine PBDEs and perfluorinated compounds sampled from the aquatic ecosystem. Polybrominated diphenyl ethers belong to persistent compounds classified as main pollutants; within the environmental constituents, they have been observed particularly in the last decade. For these studies, there were selected surface water matrices and sediments taken in various localities within the river Svratka basin. The analyses were to demonstrate whether they accumulate and remain in these specific matrices for longer time. There we assessed the congeners of polybrominated diphenyl ethers as follows: BDE-28, 47, 66, 85, 99, 100, 153, 154 and 183. In order to isolate them from matrices, various extraction techniques were used, i.e., ultrasonic extraction, microwave extraction, and pressure solvent extraction. Gas chromatography method with electron capture detection (GC/ECD) was selected for determination. The accomplished studies also assessed basic chemical, physical and environmental characteristics of diphenyl ethers in the environmental constituents. The attention was also paid to perfluorooctanoic compounds (PFOA), (PFOS) and (FOSA); physico-chemical properties of these organic pollutants were characterised and their toxicological and environmental aspects were evaluated. Usability of extraction techniques (ultrasonic extraction, pressure solvent extraction, solid phase extraction) applied to PFCs isolation from sediments samples was assessed. Identification and quantification of these analytes were performed using a high performance liquid chromatography/mass spectrometry method (HPLC/MS). After that, the optimized methods applied to real samples. Surface water and sediments were sampled within the river Svratka basin, in particular, from 19 sampling localities. PBDE occurrence was confirmed in sediments samples from the Svratka river (g.kg-1), PBDE were not detected in the surface water samples, their concentrations were below the detection limit, resp.; perfluorinated compounds were not detected in sediments and water samples at all.