学位授与大学：京都大学 ; 取得学位: 博士(工学) ; 学位授与年月日: 2007-09-25 ; 学位の種類: 新制・課程博士 ; 学位記番号: 工博第2850号 ; 請求記号: 新制/工/1419 ; 整理番号: 25535 / Kyoto University (京都大学) / 0048 / 新制・課程博士 / 博士(工学) / 甲第13379号 / 工博第2850号 / 新制||工||1419(附属図書館) / 25535 / UT51-2007-Q780 / 京都大学大学院工学研究科都市環境工学専攻 / (主査)教授 田中 宏明, 教授 藤井 滋穂, 教授 伊藤 禎彦 / 学位規則第4条第1項該当

Perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) are two commonly found contaminants associated with various manufacturing products, such as firefighting foam, non-stick coatings, electronics and water repellants. These compounds are persistent, bioaccumulative, and toxic and may therefore pose a serious health risk to living organisms. Earlier studies have shown that PFOS and PFOA affected the fatty acid β-oxidation, i.e. the energy metabolism in liver. This study evaluates the effects of PFOS and PFOA on fatty acid metabolism in domestic chicken liver cells.  Liver tissues were obtained from chicken embryos treated in ovo with PFOS or with PFOA at low (0.1 µg/g) and high (1.0 and 1.6 µg/g) concentration levels. The fatty acids were extracted and derivatized into fatty acid methyl esters (FAMEs). The analysis was conducted by gas chromatography coupled with mass spectrometry. Results showed that a lower concentration of PFOS and a lower percentage of DMSO significantly affected the concentrations of fatty acids in livers of chicken embryos. PFOA-treated samples also showed some significant elevated fatty acid concentrations. Almost all fatty acid concentrations of treated liver samples exceeded the concentrations of the untreated samples.

PFCs are used in a wide variety of industrial and commercial applications for more than 50 years. Among variation of PFCs, Perfluorooctane sulfonate (PFOS) (CF3(CF2)7SO3-) and perfluorooctanoic acid (PFOA) (CF3(CF2)6COO-) are the most dominant PFCs. In May 2009, PFOS, its salts and perfluorooctane sulfonyl fluoride (PFOSF) are designated as new Persistent Organic Compounds (POPs) which are resistant, bio-accumulating, and having potential of causing adverse effects to humans and environment (IISD, 2009). However, products containing PFCs are still being manufactured and used, which could be the main reason why they are still observed in the environment and biota (Berger et al., 2004; Saito et al., 2003; Sinclair et al., 2004). The study is focused on the PFCs contamination in water and industrial wastewater around the Central and Eastern Thailand, where is one of the major industrialized areas in the country. The samplings were conducted in major rivers, Chao Phraya, Bangpakong and Tachin River. PFCs were contaminated in all rivers. The average total PFCs were 15.10 ng/L, 18.29 ng/L and 7.40 ng/L in Chao Phraya, Bangpakong and Tachin River, respectively. PFOS and PFOA were the predominant PFCs in all samples. The total of 118.6 g/d PFOS and 323.6 g/d PFOA were released from the three rivers to the Gulf of Thailand. The survey was also conducted in small rivers, reservoirs, and coastal water around Eastern Thailand, where many industrial zones (IZ) are located. The geometric mean (GM) concentration of each PFC was ranged from 2.3 to 107.7 ng/L in small rivers, 2.2 to 212.2 ng/L in reservoirs, and 0.8 to 41.1 ng/L in coastal water samples. The higher PFCs contaminations were detected in the surface water around the industrial zones, where might be the sources of these compounds. Field surveys were also conducted in ten industrial zones (IZ1 – IZ10) to identify the occurrences of PFCs from in industries. The recovery rates of PFCs in the samples indicated that the matrix interference or enhancement was an important problem in PFCs analysis. The elevated concentrations were detected in electronics, textile, chemicals and glass making industries. Total PFCs concentrations in the influent of WWTP were ranged from 39.6 to 3, 344.1 ng/L. Ten industrial zones released 188.41 g/d of PFCs. All of the treatment processes inside industrial zones were biological processes, which were reported that they were not effective to remove PFCs. The influence of industrial discharges was affected not only the rivers and reservoirs but also in the coastal water. The PFCs in rivers and reservoirs were discharged to the Gulf of Thailand, which is the important food source for Thai people and exports. Due to the problems in industrial wastewater analysis, several optimizing options were applied in PFCs analytical method especially in Solid Phase Extraction (SPE) procedure. The combination of PresepC-Agri and Oasis®HLB was the better option for analyzing PFCs in water samples. The optimum flow rate for loading the samples was 5 mL/min. Methanol (2 mL) plus Acetronitrile (2 mL) was the effective way to elute PFCs from the cartridges. The specific solvent percentages to elute each PFCs were identified for both water and industrial wastewater samples. The matrix removal methods by using Envi-Carb and Ultrafilter were effective for different types of industrial wastewater samples. PFCs were detected in surface waters, which are the sources of tap and drinking water for the people in Central and Eastern Thailand. The surveys were conducted in Bangkok city. Samples were collected from water treatment plants (WTPs), tap water, and drinking water. PFCs were detected in all tap water and drinking water samples. PFOS and PFOA concentrations in raw water of WTP were found 4.29 ng/L and 16.54 ng/L, respectively. The average PFOS and PFOA concentrations in tap water were detected 0.17 and 3.58 ng/L, respectively. The tap water results also showed that PFOS and PFOA concentrations were not similarly detected in all area in the city. PFOA were detected higher in the western area, while PFOS concentration was quite similar in all areas. Overall, it can be concluded that the current treatment processes were not completely remove PFCs. Nevertheless, PFCs in particulate phase were effectively removed by the primary sedimentation and rapid sand filtration. Elevated PFCs were found in the industrial zones (IZ2 and IZ5). To understand the distribution and fate of PFCs during industrial wastewater process, PFCs mass flows were studied. Higher PFCs in adsorbed phase were detected only in activated sludge and some influent samples. In IZ2, PFOA loading in the dissolved phase increased after activated sludge process by 5%. There was no degradation of PFOA inside the polishing pond. The highest loading to the treatment plant was PFOS with the loading of 2, 382 mg/d and 1, 529 mg/d in dissolved and adsorbed phase, respectively. Unlike PFCAs that showed no removal in the treatment process, PFOS were decreased during the treatment processes with 36% in the activated sludge process and 36% in the polishing pond. The predominant in this IZ5 was PFOS. The increasing of PFOS was also found in this treatment plant dissimilar to IZ2. PFOS was increasing by 45% in dissolved phase and 47% in adsorbed phase. All of PFCs in this industrial zone were detected higher in the effluent, indicated that PFCs’ precursors should be the major effects of this contamination. / Kyoto University (京都大学) / 0048 / 新制・課程博士 / 博士(工学) / 甲第14930号 / 工博第3157号 / 新制||工||1473(附属図書館) / 27368 / UT51-2009-M844 / 京都大学大学院工学研究科都市環境工学専攻 / (主査)教授 田中 宏明, 教授 清水 芳久, 教授 藤井 滋穂 / 学位規則第4条第1項該当

Produced since the 1950’s, per- and polyfluoroalkyl (PFASs) substances are persistent, bioaccumulative and toxic compounds that are ubiquitous in the environment. Being proteinophilic with a tendency to partition to protein-rich tissues, PFASs have been found in human serum worldwide and in wildlife with a predominance of long-chain perfluoroalkyl carboxilic acids (C7-C14 PFCAs) and perfluoroalkyl sulfonic acids (C6-C9 PFSAs). Due to rising concern regarding their hazardous properties, several regulatory actions and voluntary industrial phase-outs have been conducted since early 2000s, shifting the production towards other fluorinated alternatives. This thesis explores the human exposure to long-chain PFASs and their alternatives using different modelling methods and aims to 1) link comprehensively the past and current industrial production with the human body burden and 2) assess the potential hazardous properties of legacy PFASs replacements, on which information is very limited. In Paper I, the historical daily intakes in Australia and USA were reconstructed from cross-sectional biomonitoring data of perfluorooctanesulfonic acid (PFOS), perfluorooctanoic acid (PFOA) andperfluorohexanesulfonic acid (PFHxS). The results indicate that humans experienced similar exposure levels and trends to PFOS and PFOA in both regions, suggesting a common historical exposure possibly dominated by consumer products. The model could not be fitted to PFHxS concentration in serum. In Paper II, the relative contribution of indirect (i.e. subsequent metabolism of precursors into legacy PFASs) versus direct exposure was evaluated on occupationally exposed ski wax technicians. The indirect exposure contributed by up to 45% to the total body burden of PFOA. In Paper III, the physicochemical properties, the persistence and the long-range transport of fluorinated alternatives were predicted using different in silico tools. Findings suggest that fluorinated alternatives are likely similar to their predecessors, in terms of physicochemical properties and environmental fate. Finally, Paper IV compares the toxic potency of PFOS, PFOA and their alternatives as a function of external and internal dose. While alternatives are less potent than their predecessors when considering the administered dose, they become similarly potent when the assessment is based on levels in the target tissue. This thesis demonstrates that pharmacokinetic models are effective tools to comprehensively reconnect the body burden to the exposure of phased-out chemicals. More importantly, the studies on fluorinated alternatives raise the necessity to provide more information and data on the potential hazard of these novel and emerging products. / <p>At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 1: Manuscript. Paper 4: Manuscript.</p>

abstract: Per- and polyfluoroalkyl substances (PFAS) are a group of man-made chemicals that are detected ubiquitously in the aquatic environment, biota, and humans. Human exposure and adverse health of PFAS through consuming impacted drinking water is getting regulatory attention. Adsorption using granular activated carbon (GAC) and ion exchange resin (IX) has proved to be efficient in removing PFAS from water. There is a need to study the effectiveness of commercially available sorbents in PFAS removal at the pilot-scale with real PFAS contaminated water, which would aid in efficient full-scale plant design. Additionally, there is also a need to have validated bench-scale testing techniques to aid municipalities and researchers in selecting or comparing adsorbents to remove PFAS. Rapid Small-Scale Column Tests (RSSCTs) are bench-scale testing to assess media performance and operational life to remove trace organics but have not been validated for PFAS. Different design considerations exist for RSSCTs, which rely upon either proportional diffusivity (PD) or constant diffusivity (CD) dimensionless scaling relationships. This thesis aims to validate the use of RSSCTs to simulate PFAS breakthrough in pilot columns. First, a pilot-scale study using two GACs and an IX was conducted for five months at a wellsite in central Arizona. PFAS adsorption capacity was greatest for a commercial IX, and then two GAC sources exhibited similar performance. Second, RSSCTs scaled using PD or CD relationships, simulated the pilot columns, were designed and performed. For IX and the two types of GAC, the CD–RSSCTs simulated the PFAS breakthrough concentration, shape, and order of C8 to C4 compounds observed pilot columns better than the PD-RSSCTs. Finally, PFAS breakthrough and adsorption capacities for PD- and CD-RSSCTs were performed on multiple groundwaters (GWs) from across Arizona to assess the treatability of PFAS chain length and functional head-group moieties. PFAS breakthrough in GAC and IX was dictated by chain length (C4>C6>C8) and functional group (PFCAs>PFSAs) of the compound. Shorter-chain PFAS broke through earlier than the longer chain, and removal trends were related to the hydrophobicity of PFAS. Overall, single-use IX performed superior to any of the evaluated GACs across a range of water chemistries in Arizona GWs. / Dissertation/Thesis / Masters Thesis Chemical Engineering 2020

A relatively unexplored source of pollution is fire stations and their usage of aqueous film forming foam (AFFF) containing per- and polyfluorinated substances (PFAS). It is well documented that these were used at fire drill sites that contaminated surrounding surface water, sediments and groundwater. The aim of this study was to assess whether fire stations could be a source of pollution and spread of PFAS and if the industry should be given priority for further investigations. Four fire stations were selected for the assessment, which were carried out by using part one of the Method of Surveying Contaminated Sites (Acronym in Swedish: MIFO). This included studies of maps, archives and field visits where fire fighters were interviewed to gather information about activities that had taken place historically on the specific sites. All of the fire stations were classified as level 2, meaning they pose a high risk for the enviroment and human health accordning to MIFO. In conjunction to the assessment, existing testing results of PFAS in soil and water from other fire stations in Sweden are submitted in purpose of showing the general situation of pollution linked with the results of this evaluation. The conclusion of this study was that various activities at fire stations possibly have polluted ground -and surface waters and that the industry should be given priority for further investigations.

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No description available.

Indiana University-Purdue University Indianapolis (IUPUI) / Perfluorooctanoic acid (PFOA) is a synthetic organic chemical that consists of an 8 carbon alkyl chain with a terminal carboxyl group in which the carbon-hydrogen bonds have been replaced with carbon-fluorine bonds except at the terminal carboxyl end. This perfluoralkyl carboxylate is a contemporary synthetic chemical that does not occur naturally in the environment and has only seen widespread use within the last 50 years. PFOA is environmentally persistent and is ubiquitously found in human serum. PFOA has been shown to induce a tumor triad consisting of liver adenomas, Leydig cell adenomas and pancreatic acinar cell tumors in male Spraque-Dawley rats. The ability of PFOA to produce tumors in rodents compounded by the fact that PFOA is accumulating not only in those occupationally exposed, but also in the general population, justifies concern about the carcinogenic potential of PFOA in humans. This paper reviews the data from current published research and reveals that some carcinogenic pathways identified in the tumors produced by PFOA in experimental animals may provide a plausible mode of action for human carcinogenesis.

Water contamination through substances called per- and polyfluoroalkyl substances (PFAS) is a worldwide problem. Being able to measure the concentrations of PFAS in water is a first step towards beating this contamination. One alternative is to use a field test kit instead of extensive lab equipment to monitor the contaminated areas. This thesis has investigated the possibility of using amine-functionalized mesoporous carbon as adsorbent to develop a detection method based on adsorbing first PFAS and then dye in aqueous solutions. The non-adsorbed dye concentrations are depending on the amount of PFAS, and hence the colour intensity in the remaining solution is proportional to PFAS concentration. Mesoporous carbon with amine functional groups were chosen as specific adsorbents for PFAS because of its large surface area and high adsorption capacity. It has been shown that some colorants would react in a similar way as PFAS on sorbents and thus can be used as an indicator for the user. In the study, the two most common PFAS, PFOA and PFOS, were studied and Rose Bengal was the dye. The adsorbent’s morphology, pore structure and pore size was verified with scanning electron microscopy (SEM), transmission electron microscopy (TEM) and nitrogen sorption before being tested. Adsorption tests were performed using different PFAS concentrations and a dye solution range in order to find three things: the detection range, the ratio powder/solution in order to see a difference, and the adsorption or saturation time for both PFAS and dye. This thesis concluded that even though the adsorbent was not as efficient as predicted, this method could be used for detecting PFAS concentrations down to at least 0.1 pg/ml and could be a possible approach for quick field tests in the future.