Per- and polyfluoroalkyl substances are a large group of global environmental contaminants. They can be divided into two sub-groups, 1) perfluoroalkyl acids (PFAAs) and 2) so called precursors, i.e. compounds that can potentially be transformed to form PFAAs. PFAAs are today ubiquitous in wildlife and humans. Food and drinking water are assumed to be the dominant human exposure pathways for PFAAs. The main aim of this doctoral thesis was to develop highly sensitive and fully validated analytical methods for the determination of a range of PFAAs and selected precursors in dietary samples. The methods were based on liquid chromatography coupled to mass spectrometry. Samples were extracted by solvent extraction followed by a cleanup step employing solid phase extraction. The cleanup step could at the same time be used as a fractionation of ionic PFAAs and neutral precursors. Paper I and II describe the development of methods for simultaneous analysis of three groups of PFAAs including perfluoroalkyl phosphonic acids (PFPAs) in drinking water and food. Methyl piperidine was used as ion pairing agent, leading to highly sensitive analysis of PFPAs. A first screening of tap water samples and different food items revealed that human dietary exposure to PFPAs in Europe is currently not of concern. A novel method for simultaneous analysis of perfluoroalkyl carboxylic acids (PFCAs) and polyfluoroalkyl phosphate esters (PAPs) in food and packaging materials is described in paper III. Targeted food samples and their packaging were analyzed. The results showed that PAPs may contribute to human exposure to PFCAs. In paper IV temporal trends (1991-2011) of perfluorooctane sulfonic acid (PFOS) and its precursors in herring were investigated. Rapidly decreasing trends were found for precursors, whereas PFOS did not show a significant change over time. Precursors in fish may have played an important role for human exposure to PFOS in the 1990s but are probably negligible today. / <p>At the time of the doctoral defense, the following paper was unpublished and had a status as follows: Paper 4: Manuscript.</p> / PERFOOD project (KBBE-227525)

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.

Per- and polyfluoroalkyl substances (PFASs) are man-made fluorinated compounds that havebeen detected in humans, the environment, and wildlife. The strong C-F bonds contribute tothe high thermal stability of some PFASs and make them extremely resistant to degradationunder normal environmental conditions. The commonly studied classes of PFASs areperfluoroalkyl carboxylic acids and perfluoroalkyl sulfonic acids. Though the phase-out ofperfluorooctane sulfonic acid and perfluorooctanoic acid for some time, they were the mostfrequent compounds measured and detected in biota.In this study, the total oxidisable precursor (TOP) assay, which is a method used to indirectlymeasure and estimate PFAS precursors, was evaluated. Different parameters were studied tounderstand their effects on oxidation of precursor compounds following TOP assay method(e.g., oxidation rate, pH of the oxidation solution and different washing steps during solidphaseextraction)The results from this experiment showed that the target precursors were oxidised and part ofthe proportion of the compounds formed ranged from 37 to 100% (molar ratio). Whenperforming TOP assay, it was shown that some precursors oxidised before 0.5 h while otherprecursors were oxidised after 4 hours. However, it was still unknown what products wereformed when some precursors were oxidised e.g., 7:3 fluorotelomer carboxylic acid (7:3-FTCA) and 10:2 fluorotelomer unsaturated carboxylic acid (10:2- FTUCA) because of animbalance of precursors to degradation products (molar to molar ratio).When the washing steps for solid-phase extraction were evaluated for potential losses ofprecursors, it could be seen that the ammonium acetate and the 20% methanol in Milli-Q waterled to the loss of some precursors. These results showed precautions were needed wheninterpreting the results using TOP assay.

Problematic organic pollutants in industrial and drinking water sources are a leading cause of water scarcity. Among the advanced oxidation processes, sonolytic degradation has received considerable attention because it combines oxidation processes initiated by reactive oxidant species and a pyrolysis processes associated with the high temperatures produced during cavitation. The degradation of the semi-volatile compound, MCHM, was rapid and followed pseudo-first order kinetics. The Freundlich kinetic model for heterogeneous systems was successfully applied to describe the non-uniform distribution of MCHM at the gas-liquid interface during ultrasonic treatment. Two primary products were confirmed by GC-MS. Computational studies were also applied to assist in a better understanding of the conformational effects and the pyrolytic pathways. The first-generation antihistamine, diphenhydramine (DPH), was also readily degraded by ultrasound. The heterogeneous process was best fit to a Langmuir-Hinshelwood kinetic model, which indicated a uniform partitioning at the gas-liquid interface. The degradation of DPH was achieved primarily via the addition reaction with hydroxyl radicals to the aromatic rings. Computational studies supported the observed products and the proposed reaction pathways for the pyrolytic and oxidation degradation pathways. Ultrasound was shown to be a rapid and effective method to remediate cetirizine (CET), a second-generation antihistamine. Addition of different hydroxyl radical scavengers into the solution prior to treatment as the competition studies indicated that CET reacted with hydroxyl radicals at the gas-liquid interface and the bulk solution. When the solution was saturated by O2, CET degraded the most rapidly. Degradation products were confirmed by LC-MS analyses. Treatment of the emerging problematic perfluorinated alkyl substance, “GenX” with steady state gamma-radiation under various conditions did not lead to significant degradation. However, “GenX” does react with eaq- at near diffusion-controlled rate, k = 5×1010 M-1·s-1. Titanium dioxide photocatalysis did not lead to appreciable degradation of “GenX” under a variety of conditions even in the presence of oxalic acid or ethanol as the valence band hole quencher. Sonolysis was a promising method and led to the effective mineralization of “GenX” under argon saturated conditions. A detailed computational study of the pyrolytic degradation pathways was carried out using density function in Gaussian 09.

Per- and polyfluoroalkyl substances (PFASs) have drawn great attention recently, due to their environmental persistence, potential toxicity and global distribution. PFAS is a large family of substances, characterized by a perflourinated carbon chain and a functional group. All PFASs are synthetic and have been widely used since the 1950s due to their unique properties of being both hydrophobic and oleophobic, making them useful for many industries. To be able to predict the fate of PFASs in the environment and to obtain detailed understanding of the transport processes, their partitioning behavior between soil particles and water depending on a range of parameters must be investigated. The aims of this study was to investigate the effects of pH, cation composition, functional group and perfluorocarbon chain length on sorption of PFASs to soil particles, by batch sorption experiment in laboratory scale. The laboratory-scale experiments were combined with modelling of the net charge to evaluate if net charge is a good predictor for sorption of PFASs to soil particles. 14 PFASs of varying length and functional groups were studied (PFBA, PFPeA, PFHxA, PFHpA, PFOA, PFNA, PFDA, PFUnDA, PFDoDA, PFTeDA, PFBS, PFHxS, PFOS and FOSA). The effect on sorption of Na+, Ca2+ (two different concentrations) and Al3+ were investigated at pH-range 3-6. Modelling of net charge was carried out in the geochemical model Visual MINTEQ. The soil had 45% organic carbon content. The adsorption of PFASs was strongly correlated with perfluorocarbon chain length, showing a stronger adsorption to particles with increasing perfluorocarbon chain length (i.e. more hydrophobic). The relation between sorption (represented by the distribution coefficient log Kd) and perfluorocarbon chain length was linear for all PFSAs and C3 to C10 PFCAs. The PFSAs (sulfonate functional group) sorbed stronger to soil particles than the PFCAs (carboxylic functional group), and FOSA (sulfonamide functional group) sorbed the strongest. For most PFCAs, (C5-C13) there was a trend of decreasing log Kd (i.e. decreased sorption) with increasing pH, due to pH-dependent changes of the soil particle surfaces. For short and intermediate perfluorocarbon chain length PFCAs (C5-C8) and for PFHxS among the PFSAs, cations had a clear effect on sorption. Aluminium ions (trivalent, Al(NO3)3) had the largest effect, followed by calcium (divalent, Ca(NO3)2) where higher concentration resulted in stronger sorption. Sodium (univalent, NaNO3) had the least influence on sorption. The net charge modelled with Visual MINTEQ takes into account many parameters (including pH) that affect the surface charge and sorption of PFASs to soil particles. When comparing log Kd for the different PFASs with pH and net negative charge, net charge was a better predictor of sorption of PFASs to soil particles than solution pH alone. / Per- och polyfluoroalkylsubstanser (PFAS:er) har dragit stor uppmärksamhet till sig på senare tid, på grund av deras persistenta egenskaper, potentiella toxicitet och globala utbredning. PFAS är en stor grupp ämnen, kännetecknad av en perflourinerad kolkedja och en funktionell grupp. Alla PFAS är syntetiska och har använts i stor utsträckning sedan 1950-talet på grund av deras unika egenskaper av att vara både vatten- och fettavstötande, vilket gör dem användbara för många industriella tillämpningar. För att kunna förutsäga var dessa föroreningars hamnar i miljön och få mer detaljerad förstående för transportprocesserna, måste deras fördelningbeteende mellan jordpartiklar och vattenundersökas för en rad olika parametrar. Syftet med denna studie var att undersöka effekterna av förändrat pH, katjonsammansättning, funktionell grupp och perfluorkolkedjelängd på sorption av PFAS:er till jordpartiklar. Detta gjordes med sorptionsexperiment i laboratorieskala. Laboratorieexperimentet kompletterades med modellering av nettoladdning, för att se huruvida detta väl kunde förklara sorptionen till jordpartiklar. 14 PFAS:er av varierande längd och med tre olika funktionella grupper studerades (PFBA, PFPeA, PFHxA, PFHpA, PFOA, PFNA, PFDA, PFUnDA, PFDoDA, PFTeDA, PFBS, PFHxS, PFOS och FOSA). Effekten på sorption av Na+, Ca2+ (två olika koncentrationer) och Al3+ undersöktes vid pH-intervallet 3-6. Modellering av nettoladdning utfördes i den geokemiska modellen Visual MINTEQ. Jorden som användes hade en halt av organiskt kol på 45%. Adsorptionen av PFAS:er var starkt positivt korrelerad med kedjelängden på de perfluorinerade kolkedjan. Ju längre kolkedja (dvs. mer hydrofob), desto starkare adsorption till partiklar. Relationen mellan sorptionen (här uttryckt som partitioneringskofficienten log Kd) och kedjelängd var linjär för alla PFSA och för C3 till C10 för PFCA. PFSA (sulfonat) adsorberade starkare än PFCA (karboxyl), och FOSA (sulfonamid) adsorberades starkast. För de flesta PFCA, (C5-C13) fanns en allmän trend där log Kd (dvs. sorption) minskade med ökande pH, på grund av pH-beroende förändringar på jordpartiklarna. För korta och medellånga PFCA (C5-C8) och för PFHxS hade katjonsammansättningen en tydlig effekt på sorptionen. Aluminiumjoner (trevärd, Al(NO3)3) hade den största effekten, följt av kalcium (tvåvärd, Ca(NO3)2) där den högre koncentrationen resulterade i starkare sorption. Natrium (envärd, NaNO3) hade minst påverkan på sorptionen till jordpartiklar. Visual MINTEQ tar hänsyn till många parametrar (inklusive pH), när nettoladdningen på jordpartiklarnas yta räknas ut. När log Kd för olika PFAS:er jämfördes med endera pH eller negativ nettoladdning, drogs slutsatsen att nettoladdning korrelerade bättre med sorption än pH.

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

Les estuaires sont des écosystèmes aquatiques particulièrement soumis au changement global et notamment à la pollution par de nombreux xénobiotiques pouvant présenter un risque écotoxicologique et sanitaire. En toxicologie environnementale et en évaluation des risques la bioaccumulation est un processus fondamental car elle contrôle les doses internes de toxiques potentiels. Or les flux de contamination et de décontamination des organismes dépendent de processus internes (e.g. nutrition, croissance) eux-mêmes dépendant des conditions environnementales (e.g. température, nourriture) qui peuvent être affectées par le changement global.Dans ce contexte, cette thèse se propose de décrire, dans un cadre de modélisation mécaniste, les processus de bioaccumulation de deux familles de polluants organiques persistants (POP) halogénés potentiellement toxiques et bioaccumulables, aux propriétés physico-chimiques contrastées : les polychlorobiphényles (PCB, composés historiques fortement lipophiles) et les substances perfluorées (PFAS, composés émergents amphiphiles). Ce travail se focalise sur l’estuaire de la Gironde dont la fonction de nourricerie est fondamentale pour de nombreuses espèces de poissons marins dont la sole commune (Solea solea), souvent utilisée comme indicatrice de la qualité des nourriceries côtières et estuariennes.Pour permettre de tenir compte des fluctuations des conditions environnementales sur la bioaccumulation, dans la première partie de ce travail, j’ai développé un modèle de toxicocinétique(TK) couplé avec un modèle mécaniste bioénergétique basé sur la théorie DEB (Dynamic Energy Budget). Ce modèle DEB a été paramétré pour la sole commune et calibré pour chaque sexe (package DEB tool). Il permet de prédire les principales évolutions des fonctions physiologiques d’intérêt en bioaccumulation (ingestion, croissance, reproduction...), tout au long du cycle de vie d’un individu, en fonction de conditions environnementales dynamiques. Le modèle TK développé a été complexifié par l’ajout d’un flux d’élimination de contaminants, non considéré dans les précédents modèles DEB-TK.La calibration des paramètres toxicocinétiques (TK) du modèle, pour 4 congénères de PCB, est basée sur une méthode innovante de prise en compte de la variabilité individuelle d’ingestion, appliquée à une expérimentation de contamination de juvéniles de sole via leur nourriture. Ce travail a montré que même en tenant compte de l’ingestion de chaque poisson, l’assimilation efficace de contaminant était très variable et corrélée aux taux de lipides des individus. Dans une seconde partie, ce modèle a été appliqué aux conditions in situ de l’estuaire de la Gironde. Il a permis de mettre en évidence la forte influence de la composition du régime alimentaire sur la variabilité de l’âge à la maturité sexuelle et de la contamination des soles pour les deux familles de contaminant étudiées. La confrontation des prédictions du modèle aux mesures de contaminants dans les juvéniles de sole de l’estuaire a permis de calibrer les paramètres TK du composé majeur de chaque famille dans l’environnement (CB153 et PFOS). Cette calibration a conduit à deux constats dans le cadre de l’évaluation du risque : (1) un manque de connaissances pour extrapoler les calibrations de paramètres TK en conditions contrôlées vers les conditions naturelles ; (2) la différence d’erreur d’évaluation du risque liée à l’utilisation des mêmes paramètres TK «les plus pessimistes » quels que soient les composés. Enfin, des scenarios prospectifs simples ont été développés pour illustrer ces résultats et les possibles applications du modèle développé.In fine, ces prédictions de la contamination, de la croissance et du développement des soles pourront être reliées, lors de travaux ultérieurs, à des effets potentiels sur les fonctions physiologiques de la sole (modèles DEBtox), et aux conséquences sur la dynamique des populations de soles (e.g.modèles matriciels de population). / Estuarine ecosystems are particularly impacted by global change and, specifically, bychemical pollution from numerous xenobiotics that may be associated to ecotoxicological and health risks. In environmental toxicology and risk assessment, bioaccumulation is a fundamental process as it controls the internal doses of potential toxicants in organisms. However, the contamination and decontamination flows depend on internal processes thatare themselves dependent on environmental conditions (e.g. temperature, food) and thus on the other variables of global change.In this context, this manuscript aims at describing, within a mechanistic modelling framework, the bioaccumulation processes of two families of potentially toxic and bioaccumulable halogenated persistent organic pollutants (POPs) with contrasting physicochemical properties: the polychlorinated biphenyls (PCBs, highly lipophilic historical compounds) and the perfluorinated substances (PFAS, amphiphilic emerging compounds).This work focuses on the Gironde estuary whose nursery function is fundamental for many species of marine fish including the common sole (Solea solea), often used as an indicator of the quality of coastal and estuarine bursary grounds. In order to account for the influence of environmental conditions on bioaccumulation, the first part of this work consisted in developing a toxicokinetic model (TK) coupled with a mechanistic bioenergetic model based on the theory DEB (Dynamic Energy Budget). This DEBmodel has been parameterized for common sole and calibrated for each sex (packageDEBtool). It allows predicting the main evolution of the physiological functions of interest forbioaccumulation (ingestion, growth, reproduction...) throughout the life cycle of an individualaccounting for dynamic environmental conditions. The developed TK model was first calibrated for some PCBs, under controlled conditions, using an innovative method to take into account individual ingestion variability. This work showed that even if the individual ingestion of each fish is accounted for, the effective assimilation of contaminant is very variable and correlated with the lipid levels of the individuals. The application of the model tothe in situ conditions of the Gironde estuary led to identify that, whatever the contaminant family, the composition of the soles diet had a strong influence on the variability of soles contamination and age at sexual maturity. The comparison of model predictions with measurements made in juveniles of the estuary allowed calibrating the TK parameters values for the major compound of each family in the environment (CB153 and PFOS). This calibration led to two observations in the context of a risk assessment: (1) a lack of knowledge to extrapolate calibrations of TK parameters under controlled conditions to natural conditions;(2) the difference in risk assessment error related to the use of the same "worst case" TK parameters regardless of the compounds. Lastly, simple prospective scenarios have beendeveloped to illustrate these results and the possible applications of the model developed.Ultimately, these predictions of soles contamination, growth and development may be related in future work to potential effects on the physiological functions of sole (DEBtox models), and to consequences on soles population dynamics (e.g. matrix population models).

Perfluoroalkyl substances (PFASs) are global environmental contaminants and a need for monitoring levels has arisen due to their persistency and their ability to bioaccumulate. One relatively novel method of monitoring for both long and short time intervals and generating time-weighted average (TWA) concentrations is passive sampling for which no power, maintenance and supervision is required. The polar organic compound integrative sampler (POCIS) with a weak anion exchange (WAX) sorbent and the POCIS with a hydrophilic-lipophilic balance (HLB) adsorbent were calibrated for PFASs in a laboratory uptake experiment, and applied at a drinking water treatment plant (DWTP) in Stockholm, Sweden.   In the calibration study, all of the 14 studied PFASs were taken up by both passive samplers. Two and three out of the 14 studied PFASs had reached equilibrium after 28 days using POCIS WAX (PFBA and PFTeDA) and POCIS HLB (PFBA, PFPeA and PFTeDA), respectively. The sampling rate (Rs), which is the extracted water in liters per day, ranged between 0.003 and 0.10 L day-1 for the POCIS WAX and between 0.00052 and 0.13 L day-1 for the POCIS HLB. In general, Rs increased with increasing perfluorocarbon chain-length (C4 to C8) and for a perfluorocarbon chain-length longer than C8, Rs decreased with increasing perfluorocarbon chain-length (C8 to C13) for both passive samplers. FOSA had the highest Rs-value (0.10 and 0.13 L day-1) for both POCIS WAX and POCIS HLB, respectively. The POCIS WAX had a higher uptake for the short-chained PFASs PFBA (134 ng after 28 days), PFPeA (410 ng) and PFHxA (834 ng), compared to the POCIS HLB (0.5 ng, 58 ng, and 373 ng, respectively). For all other compounds, the accumulated amounts in the POCIS HLB were in the same range as in the POCIS WAX.   The application of the passive samplers at the DWTP showed that both passive samplers could detect ultra-trace (pg to ng L-1) levels of PFASs. A comparison of the TWA concentration showed that the two passive samplers had a good linear correlation (R2 = 0.63), but the TWA concentrations derived by POCIS WAX was approximately 40% higher compared to POCIS HLB. A comparison between the passive samplers and the grab samples did not show a correlation (R2 = 0.24 for POCIS WAX and R2 = 0.10 for POCIS HLB). The application also included a comparison of the removal efficiency in the conventional DWTP and a pilot plant with additional treatments steps of granulated activated carbon (GAC) and nanofiltration (NF). For the full-scale DWTP the average removal efficiency was 32% and high removal efficiency was observed for PFBA (81%). For the pilot plant, the removal efficiency was 100% for all the detected PFASs in the raw water. / Perfluoroalkylsubstanser (PFAS) har blivit uppmärksammade som globala miljöföroreningar, och ett behov av att övervaka dessa ämnens förekomst i miljön har uppkommit på grund av hög persistens i kombination med hög förmåga att bioackumulera. En relativt ny metod för tidsintegrerad provtagning är så kallad passiv provtagning. En adsorbent placeras i fält och ackumulerar PFAS från vattnet. Tillgång till elektricitet behövs inte, och behov av övervakning och underhåll är minimalt. I denna studie kalibrerades en så kallad ’polar organic compound integrative sampler’ (POCIS) för mätning av PFAS genom upptagsexperiment med två olika adsorbenter: en svag anjons adsorbent (WAX) och en hydrofil-lipofil balanserad adsorbent (HLB). Metodiken tillämpades sedan på vatten från ett dricksvattenverk i Stockholm, Sverige.   Upptagsexperimenten utfördes med 14 PFAS och samtliga togs upp av båda adsorbenterna. Två respektive tre av de studerade PFAS uppnådde jämvikt efter 28 dagar för WAX (PFBS och PFTeDA) samt HLB (PFBA, PFPeA och PFTeDA). Upptagshastigheten (Rs), det vill säga den volym som extraheras per dag, varierade mellan 0,003 och 0,1 L dag-1 för WAX och mellan 0,00052 och 0,13 L dag-1 för HLB. Generellt ökade Rs med en ökande längd på kedjan av perfluorerade kol upp till C8, för att sedan avta med ökande kedjelängd. FOSA hade det högsta Rs-värdet (0,10 och 0,13 L dag-1) för både WAX och HLB. WAX hade ett högre upptag (upp till 134, 410 och 834 ng) för PFAS med kort perfluorerad kolkedja (PFBA, PFPeA respektive PFHxA) jämfört med HLB (upp till 0,5, 58, och 373 ng). Den ackumulerade mängden för alla andra PFAS överensstämde väl mellan de båda provtagarna.   Mätning av PFAS halter i dricksvattenverket med hjälp av POCIS WAX och POCIS HLB visade att även PFAS kunde detekteras även vid miljörelevanta halter. En jämförelse mellan de båda passiva provtagarna visade på ett linjärt samband (R2 = 0,63), men där POCIS WAX hade en tendens att överskatta koncentrationen med ca 40%. En jämförelse mellan de passiva provtagarna och traditionell uppsamlingsprovtagning visade på låg överrensstämmelse (R2 = 0.24 för POCIS WAX och 0.10 för POCIS HLB). Vid tillämpningen gjordes även en beräkning för reningseffektiviteten av PFAS i dricksvattenverket och i en pilotanläggning där ytterligare rening med granulerat aktivt kol (GAC) och nanofiltration (NF) används. I dricksvattenverket var den genomsnittliga reningen 32%, med den högsta reningseffektiviteten för PFBA (81%). I pilotanläggningen var reningen 100% för alla upptäckta PFAS i råvattnet.

Poly- och perfluorerade alkylsubstanser (PFAS) är samlingsnamnet för en stor grupp kemikalier som det senaste årtiondet tilldelats världsomfattande uppmärksamhet med anledning av frekventa förekomster i vattenmiljö, djurliv och människor. Samtliga PFAS som uppträder i miljön är antropogena och har blivit industriellt framtagna och tillämpade i över 60 år. På grund av deras fysiska och kemiska stabilitet och ytaktiva egenskaper är PFAS eftertraktade inom en rad olika industriella och kommersiella produkter, från filmbildande brandskum till vatten-, smuts- och fettavvisande ytbeläggningar. De omfattande möjligheterna för användning har resulterat i utsläpp av PFAS i miljön, antingen av direkta källor (~80 %) som tillverkning och tillämpning av PFAS-innehållande produkter, eller indirekta källor (~20 %) som nedbrytning och transport av prekursorer. Åtgärder har därför tagits på nationell, regional och global nivå för att begränsa användningen och spridningen av selekterade PFAS-ämnen. En av de mest uppmärksammade föroreningsproblemen med PFAS i Sverige är utsläppen av filmbildande brandsläckningsskum (AFFF) från brandövningsplatser. Som en konsekvens av flera decenniers användning och okontrollerat utsläpp till miljön har koncentrationerna av PFAS uppmätts att vara som högst i anslutning till övningsplatserna. Ämnenas mobilitet och höga vattenlöslighet gör att risken för transport till kringliggande områden är stor, vilket ökar risken att förorena närliggande grundvattentäkter. Flera exempel på PFAS-haltigt dricksvatten i svenska hushåll har bland annat upptäckts i kommuner såsom Uppsala, Ronneby, Halmstad, Botkyrka. Två före detta brandövningsplatser i Bodens kommun har brukat AFFF i övningssyfte i samband med brandövningar då platserna var aktiva. NIRAS Sweden AB har på uppdrag av Försvarsmaktens miljöprövningsenhet utrett området med avseende på PFAS och konstaterade förhöjda nivåer av ämnena i grundvattenmiljö. Eftersom flera ytvattenförekomster gränsar till brandövningsområdet finns det en oro för ämnenas spridningsbenägenhet och potential att påverka närmsta dricksvattentäkt. Syftet med examensarbetet har av den anledningen varit att kartlägga spridningen av PFAS i grundvatten från de två före detta brandövningsstationerna i Boden. Tillvägagångssättet har gått ut på att upprätta en grundvattenmodell i modelleringsprogrammet Visual MODFLOW Classic. Den hydrogeologiska modellen har tillämpats för att utföra föroreningstransport med hjälp av insticksmodulerna MODPATH och MT3DMS. Transport av det mest framträdande PFAS-ämnet i området, PFOS, modellerades från båda brandövningsplatserna och föroreningsplymens utveckling har visualiserats i flera tidssteg. Resultatet från grundvattenmodelleringen visade att grundvattnet från brandövningsområdena i det övre grundvattenmagasinet rör sig i nordvästlig till nordöstlig riktning, men även mot Luleälven. I det undre grundvattenmagasinet rör sig vattnet i nordvästlig, men har också tendens att röra sig mot Luleälven. Föroreningstransporten visade att PFOS har benägenhet att röra sig mot Luleälven i en sydvästlig riktning. Transporttiden av PFOS från brandövningsplatserna till Luleälven beräknades med MODPATH till sex respektive 7 år för den kalibrerade modellen och område 13/24. Visualisering av PFOS-plymen med MT3DMS visade att det tar cirka 100 år för ämnena att nå Luleälven. / Poly- and perfluoroalkyl substances (PFASs) is the collective name for a large group of organic chemicals which in the past decade have gained global attention due to their frequent occurence within the aquatic environment, wildlife and humans. All PFAS that occur in the environment are man-made and have been industrially created and used for over 60 years. Due to their physical and chemical stability and surface active attributes, PFAS are coveted within an array of industrial and commercial products, such as film-forming fire foam to water, dirt and grease-repellent coatings. The many possibilities to use PFAS have led to environmental emissions, either through direct sources (~80%) like manufacturing and application of PFAS-containing products, or indirect sources (~20%), through decomposition and transport of precursors. Within the PFAS-family, perfluoroctanesulfonat (PFOS) and perfluoroctaneacid (PFOA) are the most well-known and studied chemicals which have gained particular attention due to their persistence and high frequency in the environment, in turn leading them to be easily detected in humans and animals globally. PFOS and PFOA have further shown bioaccumulative and toxic traits and have thus increased the regulatory interest in the chemicals in questions of environmental and human health. Measures have therefore been taken on national, regional and global levels to restrict the use and dispersion of selected PFAS-substances affiliated with negative effects. One of the contamination issues to have gained most attention in Sweden is the emission of film-forming fire foam from fire drill locations. The PFAS-containing foam has been used throughout the country for practicing extinguishing fires related to class B: liquid fires, and has been predominantly used by military, airports and industries. As a consequence from the multi decennial use and uncontrolled emissions, the PFAS concentration, mainly PFOS and PFOA, has been measured to be highest in connection with the exercise sites. The substances mobility and high water solubility has increased the risk for their transportation to nearby areas and they may through rainfall infiltrate the ground to potentially reach the groundwater where they risk contaminating nearby groundwater sources. In Sweden, contaminated PFAS-areas are a particularly debatable issue, as about 50% of Swedish drinking water comes from groundwater-related water sources and for that reason, they have increased the general concern for human exposure. Several examples of PFAS-rich drinking water in Swedish households have been found in municipalities as Botkyrka, Halmstad, Ronneby and Uppsala and have in some cases been so high that related water resources have been withdrawn. Even if the intake of drinking water containing large quantities of PFAS substances is not considered to give rise to acute health effects, awareness of the long-term effects of exposure to PFAS is still very limited. A number of experimental and epidemiological studies focusing on PFOS and PFOA, on the other hand, have documented that both high and low doses of the substances can cause a number of adverse health effects. More recently, regulations on legislation for PFAS have reduced the scope of application, preferably for PFOS, but in accordance with this, products such as PFOS-containing fire foams have been substituted with other PFAS which have continued to be used at fire drill locations in Sweden. Continuous emissions of PFAS at these sites are thus still an up-to-date and forthcoming issue, as the substances - together with already existing pollutants - will remain for a long time to come. There are therefore reasons to limit the use further, but due to the lack of data for most PFAS pollutants, there is currently no benchmark value issued by the EU for PFAS other than PFOS. However, the National Food Agency has issued limit values based on the presence of 11 PFAS substances (PFBS, PFHxS, 6:2 FTSA, PFBA, PFPeA, PFHxA, PFHpA, PFNA, PFDA, PFOA och PFOS) with an action threshold of 90 ng·L-1and a health-based limit value for 900 ng·L-1. The values ​​should give an indication that levels of PFAS which are larger in scope than the recommendation are too high and that measures should be taken to minimize the risk of spreading and unhealthy exposure to humans. For this reason, fire drill locations using fire-containing foam containing PFAS in Sweden are a high priority for mapping PFAS distribution in the country and identifying potential areas that are at risk of being affected by the spread of the pollutants in soil and water. As a result, two closed fire drill locations in Boden municipality - as part of a nationwide survey - have been investigated with regard to the fire extinguishing foam that has historically been used and caused pollution in the area. The PFAS-based fire foam is assumed to have had historical application to two exercise sites that operated between 1940 – 1985 and 1987 – 2005, respectively. In 2016, an environmental technical soil survey was carried out with regard to the presumed PFAS occurrence for the area. The investigation was based on sampling of soil and groundwater at four and eight different points respectively, centered around the two fire drill locations, and the results showed that the current contamination in the area was clearly noticeable and that the levels were higher than the Swedish Food Agency's recommended action threshold. Findings of PFOS that exceeded SGI's preliminary target value in groundwater (45 ng·L-1) and in soil (10 µg/kgTS) were also measured in connection with the two fire drill sites, which increased the interest in broadening the mapping of the current pollution situation with the aim of creating a better understanding of the extent of the pollution and potential spreading potential. Because the knowledge of the groundwater flow direction is limited, a hydrogeological model over the fire drill location can lead to a better understanding of the groundwater flow direction and thus the possible spreading direction of the present PFAS substances. The model can also be used as a tool for calculating the time required for the potential of the pollutants to affect the nearest protection object and thereby estimate and prevent the risks for human exposure in the area at the conceivable start of construction work in the now discontinued area. The results from the groundwater modelling showed that the groundwater from the fire drill areas in the upper groundwater reservoir moves in a northwesterly to northeasterly direction, but also towards the Lule River. In the lower groundwater reservoir, the water moves to the northwest and towards the Lule River. The contamination transport showed that PFOS tends to move toward the Lule River in a southwesterly direction. The transport time of PFOS from the fire training sites to the Lule River was estimated with MODPATH to 6 and 7 years respectively for the calibrated model and area 13/24. Visualization of the PFOS plume with MT3DMS showed that it takes about 100 years for the substances to reach the Lule River.