PFAS are anthropogenic substances used in many different industrial operations and products because of their unique properties. Due to their negative impact on human health and environmental bioaccumulative characteristics different authorities have addressed the issue. In Sweden the limit is4 ng/L for four different PFAS in drinking water. Another risk to human health is elevated concentrations of toxic elements, causing Sweden to include them in the drinking water regulations withlimits such as 5 µg/L for arsenic, 25 µg/L for chromium and 5 µg/L for lead.This study is a continuation of an investigation for PFAS remediation in contaminated water by sorption to pine and spruce bark. The earlier study was a laboratory scale and implied that pine and spruce have some sorption capacity for long-chain PFAS. In this study pine and spruce bark were used as sorbent at an industrial site. The analysis was performed by weak-anion exchange extraction followed bysupercritical fluid chromatography coupled with a tandem mass spectrometer (SFC-MS/MS) and liquid chromatography coupled with tandem mass spectrometer (LC-MS/MS) for instrumental analyses of target ultra-short-chain PFAS, short- and long chain PFAS and branched PFOS isomers. An elemental analysis was executed with inductively coupled plasma mass spectrometry. The obtained results indicated removal for certain long-chain PFAS, potential for sorption of a specific ultra-short-chain PFAS and the elemental analysis implied some reduction of the chromium concentrations.

Per- and polyfluoroalkyl substances (PFASs) are a group of anthropogenic aliphatic compounds, widelyknown for their environmental persistence and toxicity to living beings. While they are ubiquitous in theenvironment, interest has been focused on contaminated soil, which can act as a primary recipient andsource of groundwater contamination. Electrokinetic technology is based on the movement of ionsunder the effect of an electric field. This could be a promising remediation solution, since PFASs areusually present in their anionic form. The contaminants can then be concentrated towards the anode,thus reducing a plume’s volume and possibly extracting the substances from soil. The preliminary aimof the present study was to evaluate the potential of using electrodialysis for the remediation of PFAScontaminatedsoil for the first time. Experiments were run with natural contaminated soil samples,originating from a fire-fighting training site at Arlanda Airport, and at Kallinge, Sweden, as well as inartificially spikedsoil. Electrodes were placed in electrolyte-filled chambers and separated by the soilwith ion-exchange membranes for pH-control. In total, five experiments were conducted. Two differentsetups were tested, a typical 3-compartment EKR cell and a 2-compartment setup, to allow for pHincrease and facilitate PFAS desorption. Two different current densities were tested; 0.19 mA cm-2 and0.38 mA cm-2. After twenty-one days, soil was cut in ten parts lengthwise and triplicate samples wereanalysed for PFAS concentrations, with HPLC-MS/MS. Sixteen out of the twenty-six screened PFASswere detected above MDL in the natural soil samples. The majority of the detected PFASs showed apositive trend of electromigration towards the anode, under both current densities, with only longerchainedcompounds (c>8) being immobile. This can be attributed to the stronger sorption potential oflong-chained PFAS molecules, as has been reported in previous sorption studies. Mass balancedistribution for a high current density (0.38 mA cm-2) experiment revealed that 73.2% of Σ26PFAS wasconcentrated towards the anode, with 59% at the soil closer to the anode, 5.7% at the anion exchangemembrane and 8.5% at the anolyte. It also showed higher mobility for short-chained molecules (c≤6),as they were the only compounds to be extracted from soil and be concentrated in the anolyte. Highercurrent densities were not directly correlated with higher electromigration rates, as to the lack of massbalance data for the low current density experiments. Regardless, electrodialysis could be a viable optionfor PFAS soil remediation and further research to encourage the understanding of the migrationmechanism, as well as combination with other treatment methods is encouraged. / Per- och polyfluoralkylsubstanser (PFAS) är en grupp av antropogena alifatiska föreningar, allmäntkända för sin miljöpåverkan och toxicitet för levande varelser. Medan de är allestädes närvarande imiljön har intresset varit inriktat på förorenad mark, som kan fungera som primär mottagare och källatill grundvattenförorening. Elektrokinetisk teknik är baserad på jonernas rörelse under effekten av ettelektriskt fält. Detta kan vara en lovande lösningsmedel, eftersom PFAS är vanligtvis närvarande i sinanjoniska form. Föroreningarna kan sedan koncentreras mot anoden, vilket reducerar en plums volymoch eventuellt extraherar ämnena från jorden. Det preliminära målet med den föreliggande studien varatt utvärdera potentialen att använda elektrodialys för sanering av PFAS-förorenad jord för förstagången. Experimenten kördes med naturliga förorenade jordprover, härrörande från enbrandbekämpningsplats vid Arlanda flygplats, och i Kallinge, Sverige, samt i konstgjort spikedsol.Elektroder placerades i elektrolytfyllda kamrar och separerades av jorden med jonbytesmembran förpH-kontroll. Totalt genomfördes fem experiment. Två olika inställningar testades, en typisk 3-facksEKR-cell och en 2-facksinställning, vilket möjliggör pH-ökning och underlättar PFAS-desorption. Tvåolika strömtätheter testades; 0,19 mA cm-2 och 0,38 mA cm-2. Efter tjugo dagar skärs jorden i tio delari längdriktningen och trippelprover analyserades för PFAS-koncentrationer, med HPLC-MS / MS.Sexton av de tjugosex screenade PFAS: erna detekterades över MDL i de naturliga markproverna.Majoriteten av de upptäckta PFAS-värdena visade en positiv trend av elektromigration mot anodenunder båda strömtätheten, varvid endast längre kedjiga föreningar (c> 8) var immobila. Detta kanhänföras till den starkare sorptionspotentialen hos långkedjiga PFAS-molekyler, vilket har rapporteratsi tidigare sorptionsstudier. Massbalansfördelning för ett experiment med hög strömtäthet (0,38 mA cm-2) visade att 73,2% av Σ26PFAS koncentrerades mot anoden, med 59% vid jorden närmare anoden, 5,7%vid anjonbytarmembranet och 8,5% vid anolyten. Det visade också högre rörlighet för kortkedjigamolekyler (c≤6), eftersom de var de enda föreningarna som skulle extraheras från jord och koncentrerasi anolyten. Högre strömtätheter var inte direkt korrelerade med högre elektromigrationshastigheter,avseende bristen på massbalansdata för experimenten med låg strömtäthet. Oavsett elektrodialys kandet vara ett lönsamt alternativ för PFAS-markrening och ytterligare forskning för att uppmuntraförståelsen för migrationsmekanismen, liksom kombinationen med andra behandlingsmetoder främjas.

Per- and polyfluoroalkyl substances (PFASs) are man-made substances that hold unique properties. They are not only oil- and water repellants but also very resistant to degradation. Due to these properties, the applications are endless and PFASs can be found in a wide range of industrial applications and commercial products. The effluents of wastewater treatment plants (WWTPs) have been pointed out as one of the major sources of PFASs in the environment. The main aim of this project was to evaluate the sources and the occurrence of PFASs in a wastewater network in a Swedish city and in the different treatment steps at the connected WWTP. Another objective was to use these data to calculate mass flows and to investigate the fate of PFASs within the WWTP. The city of Uppsala and the WWTP Kungsängsverket were selected as study objects. Both wastewater and sludge were sampled and analyzed. In the wastewater network, a total of 15 pumping stations (PSTs) were sampled for wastewater, and at the WWTP, a total of 10 wastewater and 10 sludge samples were taken. The samples consisted of grab samples (n = 24), time-integrated samples (100 mL every 20 min during 24 hours, n = 2) and flow proportional samples (24 hours, n = 9). The aqueous and sludge samples were prepared for analysis using solid-phase and solid liquid extraction, respectively, and then analyzed by liquid chromatography tandem mass spectrometry (LC/MS/MS). The PFAS concentrations and composition profiles varied greatly in the network. High concentrations of 6:2 fluorotelomer sulfonate (6:2 FTSA) were generally found in the wastewater, which indicates increased usage of 6:2 FTSA in industrial processes and applications as replacement for perfluorooctane sulfonate (PFOS) and/or leaching from fire-training sites. A hot spot was detected (Sågargatan PST: ΣPFAS = 55,000 ng L-1 = 110,000 mg d-1) with elevated discharges of C3 – C8 perfluoroalkyl carboxylates (PFCAs). The studied WWTP was ineffective in removing C4, C6, C8 perfluoroalkyl sulfonates (PFSAs), C3 – C8 PFCAs and 6:2 FTSA from wastewater. Longer chained C9 – C17 PFCAs tended to partition to sludge more effectively than shorter chained C3 – C8 PFCAs, where PFCAs with an even amount of perfluorated carbon atoms had a higher affinity for sludge than those with an odd amount. The PFAS concentrations and mass flows tended to increase across the second clarifier in both wastewater and sludge, probably due to precursor degradation. PFSAs and PFCAs tended to be at similar or lower concentrations in the effluent compared to the influent. This shows that these substances enter the WWTP from an upstream source and are not formed or added in the WWTP. The transformation of precursors is therefore not the most important source of PFASs in Kungsängsverket. PFASs in wastewater at a large scale municipal WWTP may origin to a large extent from both industrial applications and domestic sources, such as daily life products. The new knowledge generated within this project will help Uppsala Vatten to protect drinking water supplies and the receiving aquatic environment from PFAS contamination. / Per- och polyfluoroalkylerade substanser (PFAS) är konstgjorda ämnen som har unika egenskaper. De är inte bara fett- och vattenavvisande utan är även mycket resistenta mot nedbrytning. På grund av dessa egenskaper är applikationerna med PFAS oändliga, och de används i en lång rad industriella applikationer och kommersiella produkter. Renat vatten från avloppsreningsverk har pekats ut som en av de största källorna av PFAS i miljön. Syftet med det här projektet var att undersöka källorna och uppkomsten av PFAS i ett ledningsnät i en svensk stad och även före/efter de olika reningsstegen i det största reningsverket. Ett annat mål var att använda dessa data för att beräkna massflöden och att studera ödet för PFAS i reningsverket. Uppsala stad och reningsverket Kungsängsverket valdes som studieobjekt. Både avloppsvatten och slam provtogs och analyserades. I ledningsnätet provtogs totalt 15 pumpstationer (PST) med avseende på avloppsvatten och i reningsverket togs det totalt 10 avloppsvatten- och 10 slamprover. Proverna bestod av stickprover (n = 24), tidsintegrerade prover (100 mL var 20 min under 24 timmar, n = 2) och flödesproportionerliga prov (24 timmar, n = 9). Vatten- och slamproverna preparerades för analys med hjälp av fastfas- respektive fast-vätske-extraktion, och analyserades därefter med vätskekromatografi kopplat till tandem-mass-spektrometri (LC/MS/MS). PFAS koncentrationerna och sammansättningsprofilerna varierade mycket i ledningsnätet. Koncentrationerna av 6:2 fluorotelomersulfonsyra (6:2 FTSA) var generellt höga i avloppsvattnet, vilket tyder på en ökad användning av 6:2 FTSA i industriella processer och applikationer som ersättningssubstans för perfluorooktansulfonsyra (PFOS) och/eller urlakning från brandövningsplatser. En så kallad hot spot detekterades i ledningsnätet (Sågargatan PST: ΣPFAS = 55 000 ng L-1 = 110 000 mg d-1) med punktutsläpp av C3 – C8 perfluoroalkylerade karboxylsyror (PFCA). Det studerade reningsverket var inte effektivt för rening av C4, C6, C8 perfluoroalkyl-sulfonsyror (PFSAs), C3 – C8 PFCAs och 6:2 FTSA. PFAS av typen C9 – C17 PFCA (långa kolkedjor) tenderade att fördela sig till slamfasen mer än C3 – C8 PFCA (kortare kedjor), där PFCA med ett jämnt antal perfluorerade kolatomer hade större affinitet för slam än de med udda. PFAS koncentrationerna och massflödena tenderade att öka från första till andra sedimentations-tanken, både i avloppsvatten och i slam, troligtvis som en följd av degradering av prekursorer. PFSA och PFCA tenderade att ha likvärdiga eller lägre koncentrationer i ut- jämfört med inflöde. Detta tyder på att huvudkällorna för dessa substanser i avloppsvatten finns uppströms och uppkommer inte genom bildning eller tillsats i reningsverket. Nedbrytning av prekursorer är därför inte den viktigaste källan av PFAS i Kungsängsverket. Det visades tydligt att PFAS i ett kommunalt avloppsvatten kan ha sitt ursprung såväl i både industriella produkter och processer som produkter från hushåll, som t.ex. dagligvaruprodukter. Den nya kunskapen som genererats i detta projekt kommer att hjälpa Uppsala Vatten att skydda dricksvattentäkter och den mottagande akvatiska miljön för PFAS förorening.

Per- and polyfluoroalkyl substances (PFASs) are a group of toxic and persistent organic compounds. Their properties make them extremely resistant and they have been shown to have bioaccumulation and toxic properties in the environment and also to biomagnify in both aquatic and terrestrial food webs. This study has analysed different PFASs in African Darter (Anhinga rufa) eggs from five sites along Vaal River; Orange River, South Africa. Sixteen of 23 analysed PFASs were detected and quantified, and the homologue profiles were studied from all five sites. Total perfluorooctane sulfonic acid (PFOS) (all structural isomers) was the predominated compound of all PFASs, accounting for 88-98% for all sites, with a median concentration range of 58 ng/g ww to 2473 ng/g ww. The second highest concentration was found for perfluorodecanoic acid (PFDA) (1.9-42 ng/g ww), followed by perfluorononanoic acid (PFNA) (1.1-14 ng/g ww) and perfluorohexane sulfonate (PFHxS) (0.68-6.0 ng/g ww). The results showed significantly that the three up-stream sites (Welverdiend, Schoemansdrift and Orkney East) had similar patterns and that eggs from Schoemansdrift had the highest levels of PFASs. This may indicate the same source of origin for these three sites and that Schoemansdrift are closest to the contamination source. The three sites (Welverdiend, Schoemansdrift and Orkney East) with similar pattern is closest to Gauteng, which can be where the emission source is located, because it is an industrial area. Perfluoroalkyl carboxylic acids (PFCAs) and PFOS might originate from different sources and the source for PFCAs could be degradation of fluorotelomer-based precursors. Structural isomer profiles of PFOS showed similar results as the PFAS homologue patterns, which give further indication of the source of origin. The contribution of linear PFOS (L-PFOS) to the total amount of PFOS was between the range of 94 and 97%. Bloemhof had the highest concentration of branched isomers among all sites. The L-PFOS concentrations in Bloemhof were also significantly differ from Schoemansdrift. This indicate two different sources between Bloemhof and the three up-steam sites, or an effect of environmental fractionation.

Per- and polyfluorinated substances (PFAS) are compounds that consist of a carbon chainbackbone that is partially or entirely fluorinated, with an addition of a functional group. SomePFAS are known as persistent organic pollutants (POPs) and have therefore been drawing a lot ofattention as well as increased concerns. PFAS have been detected in humans, wildlife and theenvironment and some have exhibited toxic effects such as hepatotoxicity, immunotoxicity,reproductive toxicity and endocrine disruption as well as being persistent and bioaccumulative.Serum, plasma and whole blood have been used as biomonitoring matrices in many studies toevaluate human exposure to PFAS. Restrictions have been applied to some PFAS, but thesecompounds are still ubiquitous. This study will investigate the performance (recovery, matrixeffect (ME) in terms of intra-/inter-day repeatability) of ion-pair extraction (IPE) and solid phaseextraction with weak anion exchange (SPE-WAX). The extraction methods were adapted fromliterature and 13 PFAS were selected for this work based on prior biomonitoring studies. Thetarget PFAS content was analyzed with liquid chromatography coupled with tandem massspectrometry (LC-MS/MS). The extraction methods were also compared for extractableorganofluorine (EOF) extraction in terms of blank levels as well as the amount extracted withdifferent methods; the EOF content was measured with combustion ion chromatography (CIC).The EOF levels were used to estimate the amount of unidentified organofluorine (UOF), to avoidunderestimating potential health hazards. Samples extracted using IPE had an average ionizationenhancement of 9%, while SPE-WAX showed an average ionization suppression of -1%. SPEWAXshowed higher average recoveries for procedural blanks (78%), horse serum (96%) andhuman serum (95%) in comparison to IPE (69%, 36%, 88%, respectively). The CIC analysis forEOF content was observed to be below MDL (<50 ng/mL F) with some contaminations observedin the procedural blanks.

Contexte : Les produits de soins personnels contiennent plusieurs substances chimiques dont l'exposition est préoccupante pour les jeunes vu leur plus grande susceptibilité aux expositions chimiques. Aucune revue publiée n’a étudié l'exposition des jeunes aux substances chimiques dans ces produits. Objectif : Cette revue de la portée vise à synthétiser des études de biosurveillance décrivant les concentrations de parabènes, phénols, phtalates et substances per- et polyfluoroalkylées (PFAS) après l'utilisation de produits de soins personnels chez les jeunes âgés de 5 à 19 ans. Méthodes : La recherche a été effectuée dans MEDLINE, Embase et Global Health. L’éligibilité des articles a été évaluée. Les résultats des études éligibles ont été résumées et décrites. Résultats : Trente-sept études ont été incluses, la première étant publiée en 2013. La majorité des études étaient transversales (n=35) et incluaient plus de 100 participants (n=27). Les substances chimiques les plus fréquemment étudiées étaient les phtalates (n=23), suivies des parabènes et des phénols (chacun n=18), puis des PFAS (n=1). La matrice biologique principalement utilisée était l'urine (n=36). Plusieurs études (n=31) ont rapporté au moins une association positive entre les produits de soins personnels et certaines classes chimiques, comme entre le maquillage et les parabènes; la lotion et les phénols; et le parfum et les phtalates. Conclusion : Plus d'études sur ce sujet sont nécessaires pour documenter l'importance relative de l'utilisation des produits de soins personnels par rapport à l'exposition totale aux substances chimiques. L’uniformisation des questionnaires de collecte de données pourrait aider à réduire l'hétérogénéité des résultats. / Background: Personal care products (PCPs) contain a variety of chemicals including parabens, phenols, phthalates, and per- and polyfluoroalkyl substances (PFAS). Exposure to these chemicals is of concern for children and adolescents, as they are known possess an increased susceptibility to chemical exposures. To date, no published review has explored youth exposure to chemicals found in PCPs. Objective: This scoping review aimed to provide an overview of biomonitoring studies that describe the concentrations of parabens, phenols, phthalates, and PFAS following PCP use among children and adolescents of any age from 5 to 19 years old. Methods: The search was conducted in MEDLINE, Embase, and Global Health. Articles were screened and assessed for eligibility. From eligible studies, data were extracted to summarize and describe the findings. Results: Thirty-seven studies were included, the first of which appeared in 2013. The majority of studies were cross-sectional (n=35) and included more than 100 participants (n=27). The most frequently studied chemicals were phthalates (n=23), followed by parabens and phenols (each n=18), and then PFAS (n=1). The biological matrix mainly used was urine (n=36). Thirty-one studies reported at least one positive association between personal care products and certain chemical classes, such as between makeup and parabens; lotion and phenols; and perfume and phthalates.

Im ersten Teil wurde Probenvorbereitungs-Methoden und instrumentelle Methoden zur Organofluor-Bestimmung verglichen, um Vor- und Nachteile bei der Summenparameter-Analytik von per- und polyfluorierten Alkylverbindungen (PFAS) zu identifizieren. Daher wurden Oberflächenwasserproben aus der Spree in Berlin und Industrieabwasserproben mit zwei PFAS-Summenparametern analysiert – dem extrahierbaren (EOF) und dem adsorbierbaren organisch gebundenen Fluor (AOF). Beide PFAS-Summenparameter wurden mit zwei fluorsensitiven Detektionssystemen analysiert – Hochauflösender Kontinuumstrahler-Graphitofen Molekülabsorptionsspektrometrie (HR-CS-GFMAS) und combustion Ionenchromatographie (CIC). HR-CS-GFMAS erwies sich im Vergleich zu CIC als der empfindlichere und schnellere Ansatz mit höherer Präzision. Im zweiten Teil wurde eine neue Methode zur PFAS-Summenparameteranalyse und EOF-Bestimmung in Bodenproben auf Basis von HR-CS-GFMAS entwickelt und optimiert. EOF-Massenanteile wurden bei mehrfacher Extraktion und Nutzung der Festphasenextraktion (SPE) zur Entfernung anorganischen Fluors untersucht. Bei einem Vergleich der optimierten Methode mit und ohne SPE zeigte sich eine drastische Diskriminierung von Organofluor-Verbindungen mittels SPE. Im dritten Teil wurden Organofluor-Massenbilanzen in aquatischen Systemen anhand von Oberflächenwasser- und Schwebstoffproben (SPM) untersucht. SPM-Proben wurden mit vier komplementären Analysemethoden analysiert – target und non-target, direct total oxidizable precursor assay (dTOPA) und EOF. Daher wurden drei Organofluor-Massenbilanzansätze für die räumlich und zeitaufgelöste SPM-Probenanalyse verwendet: (I) Identifizierung von oxidierbaren PFAS-Vorläufer, (II) Identifizierung des Anteils der identifizierten und nicht identifiziertes EOF und (III) PFAS-target, PFAS dTOPA, non-target-Screening und EOF-Analyse, um das nicht identifizierte EOF aus Ansatz (II) weiter zu entschlüsseln. / In the first part, a comparison of sample preparation and instrumental methods for organofluorine determination was used to identify advantages and disadvantages in sum parameter analysis of per- and polyfluoroalkyl substances (PFASs). Therefore, surface water samples from the Spree River in Berlin, Germany and industrial effluent samples were analyzed using two PFAS sum parameters – the extractable (EOF) and adsorbable organically bound fluorine (AOF). Both PFAS sum parameters were analyzed using two fluorine sensitive detection systems – high-resolution-continuum source-graphite furnace molecular absorption spectrometry (HR-CS-GFMAS) and combustion ion chromatography (CIC). HR-CS-GFMAS turned out to be the more sensitive and faster approach accompanied with higher precision compared to CIC. In the second part, a new method for PFAS sum parameter analysis and EOF determination in soil samples based on HR-CS-GFMAS was developed and optimized. EOF mass fractions were investigated upon multiple extraction and utilization of solid phase extraction (SPE) for inorganic fluorine removal. In a comparison of the optimized method with and without SPE, a highly biased discrimination of organofluorines using SPE was shown. In the third part, organofluorine mass balances were investigated in aquatic systems using surface water and suspended particulate matter (SPM) samples. SPM samples were analyzed using 4 complementary analytical methods – target and non-target HRMS, direct total oxidizable precursor assay (dTOPA) and EOF. Therefore, 3 organofluorine mass balance approaches were used for SPM sample analysis in spatial and time resolved manner: (I) Identification of oxidizable PFAS precursors, (II) Identification of the proportion of identified and unidentified EOF and (III) PFAS target, PFAS dTOPA, non-target screening and EOF analysis to further unravel the unidentified EOF from approach (II).