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Exploring Sources of Human and Environmental Fluorochemical ContaminationD'eon, Jessica C. 05 September 2012 (has links)
Perfluorinated carboxylates (PFCAs) and perfluorinated sulfonates (PFSAs) are found almost ubiquitously in the environment, however their direct production and use is limited. The focus of this thesis was to explore connections between observed contamination with the manufacture and/or use of commercial fluorochemical materials. Perfluorinated sulfonamides (PFSAms) are semi-volatile materials used in the manufacture of commercial fluorochemicals. Investigations into the atmospheric fate of a model PFSAm found atmospheric lifetimes that allow transport to remote environments, potentially through a novel N–dealkylation product. A suite of PFCAs, as well as the PFSA from loss of the amide moiety, were also observed. This investigation demonstrated that PFSAm atmospheric oxidation will contribute to PFCA and PFSA contamination in remote locations, including the Arctic.
The perfluorinated phosphonates (PFPAs) were used as defoaming additives in pesticide formulations. Using novel extraction and analysis methods, widespread PFPA contamination was detected in Canadian surface waters and wastewater treatment plant (WWTP) effluent. As fully fluorinated acids, the PFPAs are a new class of perfluorinated acid discovered in the environment. Uptake and elimination parameters determined in the rat demonstrate the potential for human PFPA exposure, as these chemicals are bioavailable.
Processes governing the pharmacokinetics and disposition of perfluorinated acids in the body are poorly understood. Novel heteronuclear nuclear magnetic resonance experiments identified human serum albumin as the major site of interaction. Competitive binding experiments found the PFCAs displaced the endogenous human serum albumin ligand, 13C1-oleic acid, at lower concentrations than established ligands. The strong association observed between the PFCAs and human serum albumin may inform observed human toxic endpoints and long elimination half-lives.
The polyfluoroalkyl phosphates (PAPs) are used in food-contact paper packaging. High PAP concentrations were discovered in human sera, waste paper fibres and WWTP sludge, establishing human exposure to these chemicals. Biotransformation from PAP to PFCA was investigated in a rat model. The serum kinetics and PFCA products observed, suggest PAP exposure may be a significant source of human PFCA contamination.
The concerted approach of environmental monitoring with investigations of atmospheric and biological fate allowed strong associations to be made between commercial fluorochemical sources and observed contamination.
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Perfluoropolyethers: Analytical Method Development for a New Class of Compounds with the Potential to be Long-lived Environmental ContaminantsDi Lorenzo, Robert 21 November 2012 (has links)
Perfluoropolyethers (PFPEs) are used in a remarkably large number of industrial applications including thin-film lubricants, greases, heat transfer fluids, cosmetics, and EPA-approved food contact paper coatings and are marketed for their chemical inertness. Although desired industrially, it is also the property of most environmental concern. The lack of literature concerning the environmental impact of these compounds suggests a need to assess and characterize their environmental fate and transport. This work describes efforts to develop methods to characterize, identify and quantify various congeners of PFPEs through chromatographic, mass spectral and nuclear magnetic resonance techniques. The PFPEs exhibited unusual behavior during ionization by ESI, suggesting the possibility of structural lability during analysis. A preliminary assessment of the environmental degradation of a PFPE-phosphate congener is also described, which showed rapid sorption to sewage sludge particulate matter and the possible presence of multiple PFPEs present in the technical product mixture used for analysis.
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Exploring Sources of Human and Environmental Fluorochemical ContaminationD'eon, Jessica C. 05 September 2012 (has links)
Perfluorinated carboxylates (PFCAs) and perfluorinated sulfonates (PFSAs) are found almost ubiquitously in the environment, however their direct production and use is limited. The focus of this thesis was to explore connections between observed contamination with the manufacture and/or use of commercial fluorochemical materials. Perfluorinated sulfonamides (PFSAms) are semi-volatile materials used in the manufacture of commercial fluorochemicals. Investigations into the atmospheric fate of a model PFSAm found atmospheric lifetimes that allow transport to remote environments, potentially through a novel N–dealkylation product. A suite of PFCAs, as well as the PFSA from loss of the amide moiety, were also observed. This investigation demonstrated that PFSAm atmospheric oxidation will contribute to PFCA and PFSA contamination in remote locations, including the Arctic.
The perfluorinated phosphonates (PFPAs) were used as defoaming additives in pesticide formulations. Using novel extraction and analysis methods, widespread PFPA contamination was detected in Canadian surface waters and wastewater treatment plant (WWTP) effluent. As fully fluorinated acids, the PFPAs are a new class of perfluorinated acid discovered in the environment. Uptake and elimination parameters determined in the rat demonstrate the potential for human PFPA exposure, as these chemicals are bioavailable.
Processes governing the pharmacokinetics and disposition of perfluorinated acids in the body are poorly understood. Novel heteronuclear nuclear magnetic resonance experiments identified human serum albumin as the major site of interaction. Competitive binding experiments found the PFCAs displaced the endogenous human serum albumin ligand, 13C1-oleic acid, at lower concentrations than established ligands. The strong association observed between the PFCAs and human serum albumin may inform observed human toxic endpoints and long elimination half-lives.
The polyfluoroalkyl phosphates (PAPs) are used in food-contact paper packaging. High PAP concentrations were discovered in human sera, waste paper fibres and WWTP sludge, establishing human exposure to these chemicals. Biotransformation from PAP to PFCA was investigated in a rat model. The serum kinetics and PFCA products observed, suggest PAP exposure may be a significant source of human PFCA contamination.
The concerted approach of environmental monitoring with investigations of atmospheric and biological fate allowed strong associations to be made between commercial fluorochemical sources and observed contamination.
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Perfluoropolyethers: Analytical Method Development for a New Class of Compounds with the Potential to be Long-lived Environmental ContaminantsDi Lorenzo, Robert 21 November 2012 (has links)
Perfluoropolyethers (PFPEs) are used in a remarkably large number of industrial applications including thin-film lubricants, greases, heat transfer fluids, cosmetics, and EPA-approved food contact paper coatings and are marketed for their chemical inertness. Although desired industrially, it is also the property of most environmental concern. The lack of literature concerning the environmental impact of these compounds suggests a need to assess and characterize their environmental fate and transport. This work describes efforts to develop methods to characterize, identify and quantify various congeners of PFPEs through chromatographic, mass spectral and nuclear magnetic resonance techniques. The PFPEs exhibited unusual behavior during ionization by ESI, suggesting the possibility of structural lability during analysis. A preliminary assessment of the environmental degradation of a PFPE-phosphate congener is also described, which showed rapid sorption to sewage sludge particulate matter and the possible presence of multiple PFPEs present in the technical product mixture used for analysis.
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Commercial Fluorosurfactants and their Metabolites in Human BloodRobinson, Shona 19 December 2011 (has links)
Fluorinated chemicals have the advantage of both lipophobic and hydrophobic behaviour, leading to broad industrial and commercial use. Fluorosurfactants, for example, are used in applications, such as grease-proofing food packaging, which result in human exposure. Human blood serum, in this work 100 German serum samples dating from 1982 to 2009, is a common matrix for detection of fluorochemicals. Here the most extensive temporal study to date of one class of fluorosurfactant (polyfluoroalkyl phosphate diesters, diPAPs) in human serum is presented. Additionally, another class of fluorosurfactant (sulfonamide-based PAPs, SAmPAPs) was detected in humans for the first time with temporal trends which echo industrial production. Metabolites of diPAPs and SAmPAPs were also quantified, showing temporal trends that relate to the diPAP and SAmPAP levels. Because diPAP and SAmPAP metabolites are environmentally persistent and raise human health concerns, it is important to understand these indirect sources of exposure.
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Commercial Fluorosurfactants and their Metabolites in Human BloodRobinson, Shona 19 December 2011 (has links)
Fluorinated chemicals have the advantage of both lipophobic and hydrophobic behaviour, leading to broad industrial and commercial use. Fluorosurfactants, for example, are used in applications, such as grease-proofing food packaging, which result in human exposure. Human blood serum, in this work 100 German serum samples dating from 1982 to 2009, is a common matrix for detection of fluorochemicals. Here the most extensive temporal study to date of one class of fluorosurfactant (polyfluoroalkyl phosphate diesters, diPAPs) in human serum is presented. Additionally, another class of fluorosurfactant (sulfonamide-based PAPs, SAmPAPs) was detected in humans for the first time with temporal trends which echo industrial production. Metabolites of diPAPs and SAmPAPs were also quantified, showing temporal trends that relate to the diPAP and SAmPAP levels. Because diPAP and SAmPAP metabolites are environmentally persistent and raise human health concerns, it is important to understand these indirect sources of exposure.
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Alternatives to Conventional Fluorocarbon based Soil Resistant Treatment for Automotive Interior Textiles : An Evaluative StudyBaghaei, Behnaz, Mehmood, Faisal January 2011 (has links)
During the last two decades, the applications of fluorocarbon based chemicals to provide soil resistant or soil release properties for automotive interior and upholstery have increased tremendously. But, recent studies showed that the soil resistant treatment based on fluorochemicals has detrimental effects on the environment as well as on humans due to the presence of perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) content. PFOS and PFOA are toxic, bio accumulative and bio persistent fluoro-organic compounds. This project focus on PFOS and PFOA-free soil resistant chemicals and their application on interior textiles used for automotive. Literature study was done by keeping in mind all the aspects regarding soil and nature of soils, soil resistant mechanism, PFOA and PFOS-free soil resistant chemicals, chemistry of the chemicals, area of the application and the method of application. Experimental application of PFOA and PFOS-free soil resistant chemicals by using different concentrations on 100% Polyester dyed and unfinished fabric was performed with Pad-Dry-Cure method. Experimental application was carried out to evaluate the soil resistant treated samples for soil resistant, clean ability and colour change results. At the end, the comparison of the results of three mentioned evaluations gave us the best possible alternatives. / Program: Magisterutbildning i textilteknologi
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