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Hydrolysis and Atmospheric Oxidation Reactions of Perfluorinated Carboxylic Acid PrecursorsJackson, Derek Andrew 08 August 2013 (has links)
This dissertation explores a number of different environmentally relevant reactions that lead to the production of perfluorocarboxylic acids (PFCAs), a family of environmental pollutants that does not undergo any further degradation pathways.
The compound perfluoro-2-methyl-3-pentanone (PFMP) is a new fire fighting fluid developed by 3M that is designed as a Halon replacement. The environment fate of PFMP with regards to direct photolysis, abiotic hydrolysis and hydration was determined using a combination of laboratory experiments and computational modeling. PFMP was found to undergo direct photolysis giving a lifetime of 4-14 days depending on latitude and time of year. Offline samples confirmed PFCA products and a mechanism was proposed.
Polyfluorinated amides (PFAMs) are a class of chemicals produced as byproducts of polyfluorinated sulfonamide synthesis via electrochemical fluorination (ECF). Using synthesized standards of four model compounds, PFAMs were detected and quantified in a variety of legacy commercial materials synthesized by ECF. PFAMs were hypothesized to undergo biological hydrolysis reactions, suggesting their importance as historical PFOA precursors.
The PFAMs were also investigated with regards to their environmental fate upon atmospheric oxidation. Using a smog chamber, the kinetics and degradation mechanisms of N-ethylperfluorobutyramide (EtFBA) were elucidated. The lifetime of EtFBA to oxidation by OH was found to be approximately 4 days. Using offline sampling, PFAMs were shown to give PFCAs upon atmospheric oxidation and a plausible mechanism was proposed involving an initial N-dealkylation step followed by loss of isocyanic acid to give a perfluorinated radical. The perfluorinated radical then produces PFCAs by a series of known atmospheric reactions.
Finally, the biological hydrolysis of the polyfluoroalkyl phosphate monoesters (monoPAPs) were studied in vitro using a bovine alkaline phosphatase enzyme. Michaelis-Menten kinetic parameters were measured and compared to hexyl phosphate. It was discovered that monoPAPs hydrolyzed on average 100 times faster than hexyl phosphate due to the electron withdrawing fluorine substituents. The results were also used to rationalize the results of a previous in vivo study which suggested monoPAPs were rapidly hydrolyzed in the small intestines of rats following a high dose by oral gavage.
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Hydrolysis and Atmospheric Oxidation Reactions of Perfluorinated Carboxylic Acid PrecursorsJackson, Derek Andrew 08 August 2013 (has links)
This dissertation explores a number of different environmentally relevant reactions that lead to the production of perfluorocarboxylic acids (PFCAs), a family of environmental pollutants that does not undergo any further degradation pathways.
The compound perfluoro-2-methyl-3-pentanone (PFMP) is a new fire fighting fluid developed by 3M that is designed as a Halon replacement. The environment fate of PFMP with regards to direct photolysis, abiotic hydrolysis and hydration was determined using a combination of laboratory experiments and computational modeling. PFMP was found to undergo direct photolysis giving a lifetime of 4-14 days depending on latitude and time of year. Offline samples confirmed PFCA products and a mechanism was proposed.
Polyfluorinated amides (PFAMs) are a class of chemicals produced as byproducts of polyfluorinated sulfonamide synthesis via electrochemical fluorination (ECF). Using synthesized standards of four model compounds, PFAMs were detected and quantified in a variety of legacy commercial materials synthesized by ECF. PFAMs were hypothesized to undergo biological hydrolysis reactions, suggesting their importance as historical PFOA precursors.
The PFAMs were also investigated with regards to their environmental fate upon atmospheric oxidation. Using a smog chamber, the kinetics and degradation mechanisms of N-ethylperfluorobutyramide (EtFBA) were elucidated. The lifetime of EtFBA to oxidation by OH was found to be approximately 4 days. Using offline sampling, PFAMs were shown to give PFCAs upon atmospheric oxidation and a plausible mechanism was proposed involving an initial N-dealkylation step followed by loss of isocyanic acid to give a perfluorinated radical. The perfluorinated radical then produces PFCAs by a series of known atmospheric reactions.
Finally, the biological hydrolysis of the polyfluoroalkyl phosphate monoesters (monoPAPs) were studied in vitro using a bovine alkaline phosphatase enzyme. Michaelis-Menten kinetic parameters were measured and compared to hexyl phosphate. It was discovered that monoPAPs hydrolyzed on average 100 times faster than hexyl phosphate due to the electron withdrawing fluorine substituents. The results were also used to rationalize the results of a previous in vivo study which suggested monoPAPs were rapidly hydrolyzed in the small intestines of rats following a high dose by oral gavage.
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Åtgärder mot förhöjda halter av per- och polyfluorerade alkylsubstanser (PFAS) i dagvatten : Styrande mål och riktvärden / Measures against elevated levels of per- and polyfluoroalkyl substances (PFAS) in stormwaterHagberg, Felicia January 2024 (has links)
Stormwater is a significant transport medium for pollutants to recipients located near cities. Substances commonly found in stormwater include nutrients, metals, organic substances and particles. A group of pollutants detected in stormwater are per- och polyfluoroalkyl substances (PFAS). PFAS is a group of chemicals which have been proven to have harmful effects on health, such as endocrine disruptive effects. The most sensitive considered parameter today is effects on the immune system, but a few of these substaces are also classified as carcinogenic or potentially carcinogenic. The distribution of PFAS to the environment is significant from both new and historical uses and sources, which continue to contribute to the environment due to high persistence of PFAS. The most significant point sources of PFAS in stormwater are industrial processes and manufacturing of PFAS-containing products, firefighting foam and hydraulic oil. Atmospheric deposition, building materials and traffic also contribute but in a smaller scale. This thesis is based on a case study of a Swedish stormwater system and is aimed to evaluate which concentrations that can be classified as elevated in the stormwater system. Another aim is to investigate various remedial measures against the elevated levels of PFAS in the stormwater system. This was accomplished by a literature study of remediation techniques for PFAS applicable to a case study of an investigated stormwater system. The case study was carried out in different parts to estimate the risks and possible measures. The parts were action levels, site-specific guideline values, sampling, requirements for actions or remediation, and possible remediations techniques. Action targets and site-specific guideline values were developed based on literature and results obtained using a conceptual model. The action target was stated as follow: Stormwater must not contribute to the distribution of per- och polyfluoroalkyl substances which in a long term can result in levels in surface water that pose a risk to human health. The site-specific guideline value of 4,4 ng/L PFOA-equivalents at the outlet of the storwater, was developed based on background levels and environmental quality standards from EU:s water directive for surface water. Sampling and analysis of 22 different PFAS compounds was carried out at 10 different sampling locations in the actual stormwater system of the case study. The measured levels were compared to the site-specific guideline value, and an assessment of requirements for actions or remediation was carried out. The measured levels in the stormwater system were calculated, 5,76 ng/L PFOA-equivalents. Finally, an investigation was done of possible remedial actions and suitable remediations techniques. The stormwater system needed further investigations to make a legitimate decision about the need for stormwater treatment of PFAS. Investigations of potential point sources were suggested as adequate in order to apply the most resource efficient remedial action. Various remedial techniques were also considered for the stormwater system. The techniques were evaluated based on the criterias's; remedial capacity, water matrix, estimations of captial- and operating costs, energy requirements and availability on the market.
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Screening of endocrine disrupting compounds in Swedish rivers : with focus on organic flame retardants and perfluoroalkylated substancesRibeli, Erik January 2014 (has links)
The occurrence of chemical contaminants in the environment is one of the key issues the world isfacing today. Special effort has been put on the screening of endocrine disrupting compounds(EDCs), substances that have been shown to have adverse effects on the endocrine system. EDCs are mainly found in pharmaceuticals and personal care products (PPCPs), but also other products covering almost all categories of our daily life. EDCs can be both organic, such as the persistent organic pollutants (POPs), and inorganic, e.g. heavy metals. Today, all kinds of EDCs are currently being investigated on a large scale. Two EDC sub-categories that have gained increased public attention during the last years are organic flame retardants (FRs) and per- and polyfluoroalkylated substances (PFASs). Both categories have shown to be bioaccumulating, persistent and toxic, which has led to banning of several substances in both categories. However, as both FRs and PFASs are considered to be emerging POPs, their fate and behaviour in the environment are still in great need of research. FRs and PFASs often end up in surface waters due to their disinclination of getting removed in waste water treatment plants (WWTPs) and their persistence. Thus, the objective of this project was to provide a snapshot of the current situation of FRs and PFASs in Swedish rivers, including both smaller streams and bigger rivers. Grab water samples were taken at 25 sites for FRs and 44 for PFASs in rivers all over Sweden. The results showed that sparsely populated areas such as the northern part of Sweden generally showed lower concentrations of PFASs in the water than the southern part did. The summarised concentrations of FRs ranged from 37 ng L-1 to 4.6 μg L-1, and from 0.59 ng L-1 to 59 ng L-1 for the detected PFASs, which was in good comparison to previous studies carried out on surface water in Europe. The percentile composition, the so-called fingerprint, showed significant differences between the southern part and the northern part for both FRs and PFASs, but also great similarities between some of the rivers with the highest measured PFASs concentrations. The highest loads of both FRs and PFASs were detected in Delångersån, which is one of the smaller rivers screened and likely to be affected by a nearby industrial point source. The European environmental quality standard of 0.65 ng L-1 of perfluorooctane sulfonic acid (PFOS) was exceeded in 12 of all 44 sampled rivers.
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Contribution of polyfluoroalkyl phosphate esters (PAPs) and other precursor compounds to perfluoroalkyl carboxylates (PFCAs) in humans and the environmentEriksson, Ulrika January 2016 (has links)
Per-and polyfluoroalkyl substances (PFAS) are anthropogenic compounds that have been spread all over the world. The use of fluorotelomer compounds, short-chained homologues, and other PFASs with perfluorinated moieties has emerged recent years. One of these emerging compound classes is polyfluoroalkyl phosphate esters (PAPs), which have the ability to degrade into persistent PFCAs. The aim of this thesis was to assess the contribution of PAPs and other precursors to the exposure of PFCAs to humans and the environment. The main objective was to analyze a wide range of PFAS in human serum, wild bird eggs, indoor dust, waste water, and sludge. There was a significant contribution from selected precursors to the total amount of PFASs in the abiotic compartments indoor dust, waste water, and sludge. Levels of PAPs found in house dust exceeded those of PFCAs and perfluorosulfonic acids (PFSAs), revealing PAPs as a world-wide important exposure source. A net increase was during waste water treatment was observed for several PFASs in Swedish waste water treatment plants. Together with presence of precursor compounds and intermediates in the influent water and the sludge, this suggest that degradation of PFCA precursors contributed to the increase of PFCAs. Detection of precursors in human serum, together with slow declining trends of PFCAs, revealed an ongoing exposure of PFCAs to the general population of Australia. The diPAPs and the FTSAs were also detected in raptor bird eggs from Sweden from both the terrestrial and the freshwater environment. The precursors concentrations and patterns observed reveal that current regulatory measures are insufficient for the purpose of protecting humans and the environment from PFASs exposure.
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PFAS i lakvatten från deponi : Sammanställning av mätdata från Gärstad avfallsanläggning Tekniska verken / PFAS in leachate from landfill : Compilation of measurement data from Gärstad waste facility Tekniska verkenRylow, Sara January 2023 (has links)
Tidigare studier har visat på höga halter av per- och polyfluorerade alkylsubstanser (PFAS) ilakvatten från avfallsanläggningar. Avfallsanläggningar i Sverige har idag inga krav på attrena bort PFAS från lakvatten, och anläggningarna har generellt inte ett reningssystem som äranpassat för att rena den typen av ämnen. EU stramar hela tiden åt kraven kring utsläpp ochanvändning av PFAS och det kan därför vara bra för en avfallsanläggning att ha översikt påhur mycket PFAS det släpps ut från deponi- och avfallsverksamheten och vilka eventuellaåtgärder som skulle kunna vidtas för detta problem. I denna uppsats används analysresultat av22 PFAS ämnen från nio provtagningspunkter på Gärstad avfallsanläggning, för attundersöka avfallsanläggningens utsläpp av PFAS. Resultaten för studien visar att deuppmätta värdena för summa PFAS 22 för provpunkterna ligger mellan 410 ng/l – 58 000ng/l. PFAS ämnen med kortare kedja (4 – 8 kol) har uppmätts i högre halter än de med längrekedja (9 – 13 kol). Resultaten visade även högre halter av perfluorerade karboxylater (PFCA)än perfluorerade sulfonsyror (PFSA). / Previous studies have shown high levels of per- and polyfluorinated alkyl substances (PFAS)in leachate from waste facilities. Waste facilities in Sweden currently have no requirements topurify PFAS from leachate, and the facilities generally do not have a treatment system that isadapted to purify this type of substances. The EU is constantly tightening the requirementsregarding the release and use of PFAS, and it can therefore be good for a waste facility tokeep track of how much PFAS is released from landfill and waste operations and whatpossible measurements could be taken for this problem. In this essay, analysis results of 22PFAS substances from nine sampling points at Gärstad waste facility have been used, toinvestigate the waste facility's discharge of PFAS. The results of studies show that themeasured values for total PFAS 22 at the sampling spots are between 410 ng/l - 58,000 ng/l.PFAS substances with a shorter chain (4 – 8 carbons) have been measured at higherconcentrations than those with a longer chain (9 – 13 carbons). The results also showedhigher levels of perfluorinated carboxylic acids (PFCAs) than perfluorinated sulfonic acids(PFSAs).
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Analytical Method Development of Fluorinated Silanes using Mass SpectrometryEklundh Odler, Tea January 2018 (has links)
The aim of this study was to develop an analytical method for fluorinated silanes. Furthermore, as a secondary aim, to explore if there would be possible to detect 1H,1H,2H,2H-perfluorooctyl triethoxysilane (6:2 PTrEtSi) and 1H,1H,2H,2H-perfluorodecyl triethoxysilane (8:2 PTrEtSi) in two different matrices, sludge and cosmetic extract. The method development included experiments using LC-MS, LC-MS/MS, UPC2, GC-MS and APGC-MS/MS and was carried out using standards containing 6:2 PTrEtSi and 8:2 PTrEtSi. The analytical method that worked best for the compounds was GC-MS/MS and an analytical method using APGC-MS/MS was developed for fluorinated silanes. The IDL for 6:2 PTrEtSi was 0.0012 μg/mL and 1.32 μg/mL for 8:2 PTrEtSi. This makes the developed method suitable for high contaminated samples, such as extracts from cosmetic products. It was concluded that a method using LC as the analytical instrument would not work for the two target compounds since they were too reactive with the mobile phase. However, LC could be a good choice for siloxanes, compounds that are formed from hydrolysis and condensation of fluorinated silanes. The samples analyzed in this study were three sludge extracts and one extract from a cosmetic product. 6:2 PTrEtSi was expected to be detected in the cosmetic sample since the compound was stated on the table of contents of the cosmetic product. No detection of 6:2 TrEtSi or 8:2 TrEtSi could be made in either of the samples. The reason for this was suspected to be transformation or degradation of the compounds into other compounds. Therefore, a full scan of the cosmetic sample using LC-MS/MS was included in the experiment as an addition to verify the suspicions that compounds such as siloxanes could have been formed. An interesting peak was discovered with m/z 947 which could be a disiloxane of 6:2 PTrEtSi.
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