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Perfluoroalkyl acids (PFASs) are toxic pollutants ubiquitously found in the ecosystem. Recent investigations have focused on describing their environmental behavior and spreading. This includes transportation by water, where groundwater can continue to spread the contaminants a long time after the use has ended. This thesis surveys the existing literature on the reactions in soil that decides the presence and composition of PFASs in groundwater. A chemical groundwater investigation was recently done by Stockholm’s Environmental and Health Administration. The thesis presents a quantitative analysis of the PFASs’ content in Stockholm’s groundwater to verify if it conforms to the literature. A statistical analysis of the ratio between perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) is included to test if the PFAS composition in groundwater is influenced by soil reactions. The literature states that due to the high water solubility, low volatility and moderate adsorption, PFASs are likely to be encountered in groundwater. The adsorption depends on both PFASs’ and soil’s properties. The quantitative analysis confirms the influence of the PFASs’ properties in Stockholm’s groundwater, where both more short-chained PFASs and carboxylates are present. However, the analysis could not confirm the influence of the soil properties in adsorption at normal environmental conditions. The statistical analysis shows that the ratio of PFOS to PFOA is increased in groundwater in comparison to stormwater (p < 0.15). The increase cannot be explained by the hypothesis that the adsorption of PFAS governs this behavior, since PFOS is a sulfonate and longer than PFOA. An explanation is found in the degradation of precursors, which seems to contribute to PFOS concentrations in groundwater. This shows the important contribution of degradation of precursors to PFOS concentrations and motivates further investigations on the matter.

Objectives: This study aimed to examine the association of Per and Polyfluoroalkyl substances (PFAS) and markers of chronic inflammation and oxidative stress. Methods: Using data (n = 6652) from the National Health and Nutrition Examination Survey (NHANES) 2005–2012, generalized linear models were used to examine the association between PFAS and inflammatory (ferritin, alkaline phosphatase, C-reactive protein, absolute neutrophil count and lymphocyte count) and oxidative stress (serum bilirubin, albumin and iron) per unit exposure to PFAS while adjusting for covariates. Study participants were those ≥20 years of age. Outcome variables were markers of chronic inflammation and oxidative stress and exposure variables were PFAS. Resullts: Percentage change in Perfluorohexane sulfonic acid (PFHxS), Perfluorononanoic acid (PFNA), Perfluorooctanoic acid (PFOA), Perfluorooctane sulfonic acid (PFOS), and Perfluorodecanoic acid (PFDA) were all significantly associated with percentage increases in lymphocyte counts, beta (95% confidence interval); 0.04(0.02,0.05), 0.04(0.02,0.05), 0.05(0.03, 0.07), 0.04(0.03,0.05), 0.03(0.13,1.23) and with percentage increases in serum iron 0.07(0.05,0.09), 0.04(0.02,0.07), 0.10(0.07,0.12), 0.05(0.03,0.07), 0.04(0.02,0.06) and increased serum albumin 0.02(0.02,0.02), 0.02(0.02,0.03), 0.03(0.03,0.04), 0.02(0.017, 0.025), 0.01 (0.01, 0.05). Only PFHxS, PFNA, PFOA and PFOS were associated with percentage increases in serum total bilirubin 0.04(0.03,0.05), 0.02(0.00,0.03), 0.06(0.04,0.08), 0.03(0.02,0.05). Similar results were obtained for categorical quintile analysis with PFOA showing a significant trend (P < 0.001) with lymphocyte count, serum iron, serum total bilirubin and serum albumin. Trend for neutrophil count was not significant (p = 0.183). Conclusion: Per and Polyfluoroalkyl substances are associated with markers of chronic inflammation and oxidative stress. Increased exposure leads to increase in serum concentration of these markers meaning these chemicals are associated with both chronic inflammation and oxidative stress.

Objectives: This study aimed to examine the association of Per and Polyfluoroalkyl substances (PFAS) and markers of chronic inflammation and oxidative stress. Methods: Using data (n = 6652) from the National Health and Nutrition Examination Survey (NHANES) 2005–2012, generalized linear models were used to examine the association between PFAS and inflammatory (ferritin, alkaline phosphatase, C-reactive protein, absolute neutrophil count and lymphocyte count) and oxidative stress (serum bilirubin, albumin and iron) per unit exposure to PFAS while adjusting for covariates. Study participants were those ≥20 years of age. Outcome variables were markers of chronic inflammation and oxidative stress and exposure variables were PFAS. Resullts: Percentage change in Perfluorohexane sulfonic acid (PFHxS), Perfluorononanoic acid (PFNA), Perfluorooctanoic acid (PFOA), Perfluorooctane sulfonic acid (PFOS), and Perfluorodecanoic acid (PFDA) were all significantly associated with percentage increases in lymphocyte counts, beta (95% confidence interval); 0.04(0.02,0.05), 0.04(0.02,0.05), 0.05(0.03, 0.07), 0.04(0.03,0.05), 0.03(0.13,1.23) and with percentage increases in serum iron 0.07(0.05,0.09), 0.04(0.02,0.07), 0.10(0.07,0.12), 0.05(0.03,0.07), 0.04(0.02,0.06) and increased serum albumin 0.02(0.02,0.02), 0.02(0.02,0.03), 0.03(0.03,0.04), 0.02(0.017, 0.025), 0.01 (0.01, 0.05). Only PFHxS, PFNA, PFOA and PFOS were associated with percentage increases in serum total bilirubin 0.04(0.03,0.05), 0.02(0.00,0.03), 0.06(0.04,0.08), 0.03(0.02,0.05). Similar results were obtained for categorical quintile analysis with PFOA showing a significant trend (P < 0.001) with lymphocyte count, serum iron, serum total bilirubin and serum albumin. Trend for neutrophil count was not significant (p = 0.183). Conclusion: Per and Polyfluoroalkyl substances are associated with markers of chronic inflammation and oxidative stress. Increased exposure leads to increase in serum concentration of these markers meaning these chemicals are associated with both chronic inflammation and oxidative stress.

Les substances poly- et per-fluorées (PFAS), exclusivement d’origine anthropique, sont de nos jours largement utilisées dans diverses applications industrielles et domestiques. La synthèse des PFAS engendre leurs rejets dans l’environnement, où ces composés se retrouvent aussi bien dans l’atmosphère que dans les milieux terrestres et aquatiques. Les études de distribution environnementale, relativement récentes, ont montré la bioaccumulation de certains PFAS chez les vertébrés aquatiques. La toxicocinétique (TK) des PFAS est particulière en raison de leurs propriétés physico-chimiques. Même si les études de TK de ces composés sont de plus en plus nombreuses, quelques verrous mécanistiques restent encore à lever chez les vertébrés aquatiques, notamment concernant les processus d’absorption, de distribution et d’élimination. Dans l’optique d’améliorer ces connaissances, un modèle toxicocinétique à base physiologique (PBTK) a été développé pour décrire le devenir de trois PFAS appartenant à la famille des perfluoroalkyles : le perfluorooctane sulfonate (PFOS), le perfluorohexane sulfonate (PFHxS) et l’acide perfluorononanoïque (PFNA). Ce modèle PBTK s’appuie sur les paramètres physiologiques de la truite arc-en-ciel (Oncorhynchus mykiss) et a permis de tester plusieurs hypothèses mécanistiques de la bioaccumulation des PFAS, utile à l’évaluation du risque engendré par l’exposition à ces substances. La croissance et la température de l’eau, facteurs clés dans la TK des poïkilothermes, ont également été intégrées dans le modèle. Les trois expériences d’exposition aux PFOS, PFHxS et PFNA par voie alimentaire à différentes températures (7°C, 11°C et 19°C) réalisées au cours de cette thèse ont permis (i) de mesurer les concentrations dans les organes d’intérêt et (ii) de calibrer et évaluer les prédictions du modèle / Poly- and per-fluorinated substances (PFAS), exclusively derived from anthropogenic activity, are nowadays widely used for industrial and domestic purposes. During their synthesis, PFAS are released in the atmosphere as well as in aquatic and terrestrial compartments. Environmental distribution studies are relatively recent and have shown the bioaccumulation of some PFAS in aquatic vertebrates. Physico-chemical properties of PFAS lead to a specific toxicokinetic (TK) profile. Although TK studies on these compounds are becoming more and more abundant, some mechanistic challenges still need to be solved for aquatic vertebrates, particularly for absorption, distribution and elimination processes. In order to improve this knowledge, a physiologically based toxicokinetic (PBTK) model has been developed to describe the fate of three PFAS belonging to the perfluoroalkyl family: perfluorooctane sulfonate (PFOS), perfluorohexane sulfonate (PFHxS) and perfluoronanoic acid (PFNA). This PBTK model was parametrized with rainbow trout (Oncorhynchus mykiss) physiological parameters. Next, it was used to test several mechanistic hypotheses about PFAS bioaccumulation, useful for improving the risk assessment of these chemicals. Fish growth and water temperature are key factors in the TK for poikilotherms. So, they have been integrated in the model. Three experiments of dietary exposure to PFOS, PFHxS and PFNA at different temperatures (7°C, 11°C and 19°C) have been performed. They allowed (i) to measure concentrations in organs of interest and (ii) to calibrate and evaluate the model predictions

Per- and polyfluoroalkyl substances (PFASs) are persistent organic pollutants used in industrial applications and are globally distributed in the environment. A group of PFASs that are difficult to measure with today’s method are perfluoroalkyl acid precursors (PFAA precursors) that, when degraded, serves as indirect sources of PFAAs. This study has optimized a previously developed method for quantification of PFAA precursors in soil; through total oxidizable precursor assay (TOP assay) under alkaline conditions, to be applicable on sewage sludge. To achieve and maintain an alkaline environment during the entire oxidative treatment, several parameters were tested: concentrations of NaOH, persulfate and sample; additional clean-up with graphitized non-porous carbon and reaction time. Solid phase extraction-weak anion exchange (SPE-WAX) was used for clean-up and separation of analytes, and LC-MS/MS was used for quantification. The optimal conditions with the highest levels of PFAAs detected was obtained with 1.33 M NaOH, 60 mM persulfate, 3.57 g/L sludge with a reaction time of 6 hours. The use of graphitized non-porous carbon reduced matrix effects on oxidative conversion resulting in a higher pH as well as a higher degree of oxidation, but with some analyte loss.

Poly- and perfluoroalkyl substances (PFAS) are ubiquitous contaminants across the globe, can bioaccumulate in aquatic taxa, and potentially biomagnify in food webs. Consequently, research examining the influence of PFAS on wildlife is warranted. Amphibians are sensitive to contaminants such as PFAS because of their porous skin and associations with aquatic habitats where contaminants accumulate. Because PFAS tend to bioaccumulate and can adversely affect the endocrine system, there is a need to examine uptake rates to inform ecotoxicology studies, as well as a need to examine sublethal effects. To address these knowledge gaps I conducted two experiments. First, I exposed larval northern leopard frogs (<i>Rana pipiens</i>), American toads (<i>Anaxyrus americanus</i>), and eastern tiger salamanders (<i>Ambystoma tigrinum</i>) to PFAS chemicals perfluorooctanoic acid (PFOA) or perfluorooctane sulfonate (PFOS) at concentrations of 10 or 1000 ppb for 10 days and sampled them every 48 hours during the exposure period. In the next experiment, I examined the effects of PFAS exposure via contaminated substrate on the survival and growth of post metamorphic amphibians of the same species. I found that, for all species, body burdens often reached steady state within 48 to 96 h of exposure. Steady-state body burdens of PFOA ranged from 3,819–16,481 ng/g dry weight among treatments and species (corresponding BCFs of 0.5 to 2.5), while PFOS body burdens ranged from 6,955–489,958 ng/g dry weight (corresponding BCFs of 47–259) among treatments and species. These data suggest that steady state is rapidly reached in larval amphibians exposed to PFAS, particularly regarding PFOS. This reflects a high potential for trophic transfer of PFAS within food webs because amphibians are often low in trophic position and are important prey for many aquatic and terrestrial species. In post-metamorphic amphibians, there was no influence of PFAS on survival or mass. However, significant effects on snout-vent length were observed in all species, and body condition differences were observed for two of my species. I found that all leopard frogs increased in scaled mass index (SMI) when exposed to a PFAS treatment, indicating an increased body condition. Toads exhibited a more variable SMI pattern across treatments, with no outstanding trends, and tiger salamanders did not differ significantly across treatments. These data suggest that sublethal effects vary greatly depending on the species, possibly due to life history traits. Future research examining biomagnification potential is warranted to determine the influence of PFAS on food webs. Additionally, there is a need to determine the physiological mechanisms underlying the observed effects of PFAS exposure.<br>

Les activités humaines sont responsables de l’apport de nombreux micropolluants vers les systèmes aquatiques parmi lesquels les substances poly- et perfluoroalkylées (PFAS) ont été identifiées. Ces molécules sont utilisées depuis les années 1950 comme tensio-actifs dans de nombreuses applications industrielles et produits d’usage courant. Depuis deux décennies, certaines de ces substances, les acides perfluoroalkylés (PFAA) ont particulièrement attiré l’attention en raison de leur caractère ubiquiste et persistant dans l’environnement. Actuellement, il existe un réel manque de connaissance sur l’intégralité de la contamination environnementale par l’ensemble des PFAS. L’objectif global de ces travaux de thèse est de poursuivre les efforts menés depuis le début des années 2000 pour mieux comprendre la dynamique des PFAS depuis leurs sources en milieu urbain, leurs rejets dans les rivières et leur transfert trophique.La première partie consiste à optimiser une configuration de l’échantillonneur passif POCIS (Polar Organic Chemical Integrative Sampler) pour l’analyse ultra-trace de 25 PFAS dans les eaux de surface. Dans un second temps, il est question d’identifier les sources en PFAS sur la métropole de Bordeaux. L’analyse de 30 PFAS dans les eaux usées collectées en raiseau d’assainissement tend à montrer l’importance des apports industriels par rapport aux rejets domestiques pour la quasi-totalité des PFAS étudiés. A noter que les eaux de ruissellement sont également vectrices de contamination en PFAS. La caractérisation des effluents d’entrée et de sortie des quatre principales stations d’épuration des eaux usées (STEU) de la métropole met en évidence une faible efficacité des filières de traitement. L’utilisation d’une approche d’analyse non ciblée par oxydation, la méthode TOP (Total Oxidizable Precursors) révèle des quantités non négligeables de précurseurs de PFAA aussi bien en réseau d’assainissement que dans les effluents de STEU. L’impact de l’exutoire collectant les eaux de ruissellement en provenance de l’aéroport et d’une portion du périphérique de Bordeaux sur les niveaux en PFAS d’une petite rivière périurbaine est également montré. Enfin, la dernière partie renseigne la bioamplification des PFAS en milieu lotique. L’évaluation des concentrations le long de 5 réseaux trophiques du bassin hydrographique Rhône-Méditerranée permet d’une part de confirmer la bioamplification du perfluorooctane sulfonate (PFOS) et des perfluoroalkyles carboxylates (PFCA) à chaîne longue, et d’autre part d’évaluer la variabilité spatiale des facteurs d’amplification trophique (TMF). Le caractère bioamplifiable de PFAS d’intérêt « plus émergent » tels que les 8:2 et 10:2 fluorotélomères sulfonates est mis en évidence dans une rivière localisée à la périphérie de Paris. L’application de la méthode TOP à différents maillons de cette chaîne trophique permet de soutenir l’hypothèse de l’implication de la biotransformation des précurseurs dans la bioamplification apparente des PFAA. / Human activities are responsible for the release of multiple micropollutants into aquatic systems, such as poly- and perfluoroalkylated substances (PFASs). These molecules have been used since the 1950s as surfactants in many industrial applications and commonly used products. For two decades, some of these substances, perfluoroalkylated acids (PFAA), have generated a major concern due to their ubiquitous and persistent behavior in the environment. Currently, there is a real lack of knowledge about the full extent of environmental contamination by all PFASs. The overall objective of this thesis is to continue the efforts undertaken since the early 2000s to gain a better understanding of the dynamics of PFASs, from their sources in urban areas, their releases to aquatic systems, to their trophic transfer.The first part consisted in optimizing a configuration of the Polar Organic Chemical Integrative Sampler (POCIS) for the ultra-trace analysis of 25 PFASs in surface water. In a second time, the dynamics of the PFASs on the Bordeaux conurbation is studied. The analysis of 30 PFASs in wastewater collected in the sewerage network tends to show the importance of industrial inputs compared to domestic discharges for almost all the studied PFASs. Note that urban runoff is also a source of PFAS contamination. The characterization of the influents and effluents of the four main wastewater treatment plants (WWTP) in the metropolis shows a low efficiency of treatment channels. The use of a non-targeted analysis approach by oxidation, the TOP method (Total Oxidizable Precursors) reveals significant amounts of PFAA precursors in the sewerage network as well as in WWTP effluents. The impact of urban and airport storm water discharge on the contamination levels of a small peri-urban river has also been shown. The last part dealt with the biomagnification of PFASs in lotic systems. The evaluation of PFAS concentrations along 5 food webs from the Rhone-Mediterranean watershed enables to confirm the biomagnification of perfluorooctane sulfonate (PFOS) and long-chain perfluoroalkyl carboxylates (PFCA) and to evaluate the spatial variability of trophic magnification factors (TMF). The biomagnification character of PFASs of "more emerging" interest, such as the 8:2 and 10:2 fluorotelomer sulfonates, is observed in a river located on the outskirts of Paris. The application of the TOP method to different trophic levels supports the hypothesis of the involvement of the biotransformation of precursors in the apparent biomagnification of PFAAs.

Per- and polyfluoroalkyl substances (PFASs) is a group of man-made, highly persistent chemicals. Due to the specific surface-active attributes of these molecules, applications are numerous and feed an economically important industry. During the last decade, PFASs have been detected globally in the environment, living organisms and tap water. The combination of toxic properties and high bioaccumulative potential, together with the discovery that conventional water treatment methods do not remove PFAS, renders further research on purification methods highly needed.  Three techniques of purifying water from PFASs were examined. Nanofiltration technology (NF) is a membrane filtration technique, which produces a purified product (the permeate) by generating an effluent of high contaminant concentration (the reject water). To decontaminate the reject water, adsorption by granular activated carbon (GAC) or anion exchange (AE) have been proposed. The efficiency of these three technologies was studied at Bäcklösa drinking water treatment plant (DWTP) in Uppsala. A nanofiltration pilot with two 270NF membranes (Dow Filmtech™), connected in series, was used. A high removal efficiency (&gt;90%) was found for all PFASs. Furthermore, it was confirmed that the concentration in the permeate water was a function of the concentration in the incoming raw water; increased PFAS raw water concentration resulted in increased PFAS permeate concentration. Size-exclusion and electrostatic repulsion were deemed important mechanisms. For the comparison of GAC (Filtrasorb 400®) and AE (Purolite® A-600), a column experiment was set up. The perfluoroalkane (-alkyl) sulfonic acids (PFSAs) and perfluorooctanesulfonamide (FOSA) had similar removal efficiencies using both GAC and AE, and the efficiency increased with increasing chain length. AE was found to have a higher average removal efficiency of perfluoroalkyl carboxylic acid (PFCAs) (62-95%) than GAC (49-81%). In conclusion, longer chain length PFASs were removed more effectively than shorter-chained, and the PFSAs and FOSA showed higher removal efficiency compared to the PFCAs. Furthermore, linear isomers were removed more effectively than branched for GAC and AE. In contrast, the opposite was found for the NF membrane, where branched isomers were better retained. / Per- och polyfluorerade alkylsubstanser (PFAS) är en grupp syntetiska, ytterst persistenta kemikalier. På grund av deras ytaktiva egenskaper är de lämpliga för användning i många produkter och tillverkningsprocesser, och är således viktiga för en ekonomiskt betydande industri. Under det senaste årtiondet har PFAS påträffats i miljön, levande organismer och kranvatten världen över.  Kombinationen av toxiska egenskaper, en hög bioackumuleringspotential och upptäckten att konventionella reningsmetoder inte avlägsnar substanserna från vatten, gör att vidare forskning av reningsmetoder för PFAS är mycket angelägen. Tre reningsteknikers förmåga att rena vatten från PFAS undersöktes. Nanofiltrering (NF) är en membranfiltreringsteknik som utöver den renade produkten, permeatet, även framställer en biprodukt av hög föroreningsgrad, rententatet. För att rena rententatet har adsorption till granulärt aktivt kol (GAC) eller jonbytarmassa (AE) föreslagits. Teknikerna utvärderades på Bäcklösa Vattenverk i Uppsala.  Nanofiltreringen undersöktes i en pilotanläggning där två 270NF (Dow Filmtech™) membran var seriekopplade. En hög reningsgrad (&gt;90%) konstaterades för alla typer av PFAS. Vidare visades PFAS-koncentrationen i permeatet vara en funktion av PFAS-koncentrationen i råvattnet; en ökad råvattenkoncentration gav en ökad permeatkoncentration. Storleksseparation och elektrostatisk repulsion befanns vara viktiga mekanismer som påverkade reningsgraden. För att undersöka de mekanismer som påverkar PFAS-adsorption jämfördes GAC (Filtrasorb 400®) och AE (Purolite® A-600) i ett kolonnexperiment. Reningsgraden för GAC och AE av perfluorerade sulfonsyror (PFSA) och perfluorooktan sulfonamider (FOSA) var lika hög och reningseffektiviteten ökade med ökande kolkedjelängd. AE återfanns ha en högre genomsnittlig reningsgrad av perfluorkarboxylsyror (PFCA) (62-95%) än GAC (49-81%). Sammanfattningsvis avlägsnades PFAS av längre kolkedjelängd mer effektivt än kortare kolkedjor, och PFAS med sulfonsyror och sulfonamider som funktionella grupper uppvisade en högre reningsgrad än karboxylsyrorna. Vidare renades linjära isomerer mer effektivt än grenade både genom GAC och AE. Däremot konstaterades det motsatta för NF-membranen, där grenade isomerer renades mer effektivt. / SafeDrink

Diploma work focuses on the determination of selected representatives of perfluoroalkyl substances in complex matrices, particularly, in sewage sludge and feed. In case of sewage sludge, samples were extracted into methanol and three extractions techniques were compared: accelerated Soxhlet, pressurized liquid extraction and Powley method. Powley method showed sufficient efficiency, the lowest matrix effect and minimal background. Perfluorooctane sulfonate was present in all tested samples of sewage sludge (0.74–38.02 ng.g-1). Other detected compounds were perfluorodecanoic acid and perfluorooctanoic acid. Three extraction techniques were tested on feed samples (QuEChERS, fast methanol extraction and Powley method into acetonitrile). Powley method provided the cleanest extracts and showed simultaneously the highest recovery of native perfluoroalkyl substances and the lowest matrix effects. Perfluorooctane sulfonate and perfluorooctanoic acid were rarely present in samples of complete and supplemental feeds, while other perfluoroalkyl substances were found at levels below limit of quantification or they were not detected at all. Perfluorooctane sulfonate (0.100–2.768 ng.g-1), perfluoroundecanoic acid and perfluorotridecanoic acid were determined in all fish meal samples.