Per- and polyfluoroalkyl substances (PFAS) are synthetic compounds that have beenaround since 1940. They can be used in a variety of products such as fire-fighting foam,food packaging and cosmetic products. Many PFAS have potential toxic effects on bothhumans and animals which poses a problem due to their wide distribution and persistency.Another problem concerns the remediation of PFAS, where the substances ends upcirculating between the different disposal types (landfills, wastewater treatment andincineration). Active methods are therefore needed to remove or retain the contaminants.Some examples of these remediation technologies can be biomaterials, organoclays andmore advanced methods such as activated carbon and ion exchange. The more advancedbeing suited for remediation of drinking water. In this study, the sorption efficiency oftwo pine bark fractions has been studied and also compared to the efficiency of activatedcarbon. The evaluation was done for both target analysis (PFAS-11) and non-specificanalysis of extractable organofluorine (EOF) compounds in contaminated water from ahazardous waste management facility. The two pine bark fractions indicated similarsorption efficiencies, for both the PFAS-11 and the EOF compounds. The sorptionefficiency ranged from 10% up to 75% for perfluorinated sulfonic acids (PFSA) and frombelow zero up to 40% for perfluorinated carboxylic acids (PFCA). A general pattern canbe seen, the sorption efficiency increases with increasing length of the PFAS chain. Theactivated carbon had a higher sorption efficiency, where the majority of PFAS had anaverage sorption of 100%. In comparison, the PFAS-11 and total EOF analysis displayedhigh concentrations of unidentified EOF compounds. These compounds indicated anegative sorption, which might imply that non-targeted PFAS or other fluorinated organic compounds desorb from the bark. Therefore, the pine bark might be suitable as a roughremediation of long-chain PFAS (≥8C), but further studies on the sorption of unidentifiedfluorinated organic compounds are of interest.Keywords:

No description available.

Wastewater reclamation and reuse have been increasingly practiced as sustainable strategies to meet water demands, particularly in regions threatened by water shortages. However, one of the biggest challenges for reusing wastewater effluents (WEs) as irrigation water is to remove emerging organic contaminants such as persistent and potentially bioaccumulated per- and polyfluoroalkyl substances (PFAS), whose presence may result in adverse impacts on crops, soils, aqueous ecosystems, and human health. Photocatalysis is an effective and promising technique to remediate PFAS in aqueous media. This dissertation aims to: i) Develop a novel, environmental-friendly, and low-cost treatment process for PFAS removal and degradation for water reuse; ii) Optimize the experimental conditions and investigate the removal mechanisms of PFAS with different structures in this novel process; iii) Scale up this treatment process and apply it to treatment of WEs in a point-of-use (POU) system. First, ultraviolet (UV) C /nanoscale zero-valent iron (nZVI, Fe0 nanoparticles (NPs)) system is used for the first time to induce PFAS photocatalytic removal from aqueous solution. Oxidative and/or reductive degradation of three representative PFAS - perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), and perfluorooctane sulfonate (PFOS) was achieved using Fe0 NPs under UVC light both with and without presence of oxygen. However, no PFAS removal was observed either under visible light and in the dark, and much lower PFAS degradation was achieved under UVA light. Higher degradation and defluorination efficiencies were obtained for longer chain PFNA compared to PFOA, and higher degradation and defluorination of PFAS were achieved without presence of O2 compared to with O2. The degradation of PFOA and PFOS followed first order reaction kinetics with the highest efficiencies achieved of 97.6, >99.9, and 98.5% without presence of O2 for PFOA, PFNA, and PFOS, respectively. The degradation efficiencies increased with the increase of nZVI concentrations in the range of 1-100 mg/L. The degradation efficiency of PFOA using bare Fe0 NPs was higher than that using 1% PVP-coated Fe0 NPs in the initial 6 h. Second, the removal mechanism of PFAS in UVC/Fe0 NPs system was obtained by testing the concentrations of iron ions (Fe2+/Fe3+), intermediate products, and reactive oxygen species (ROS, e.g., ·O2- and ·OH) generated, and conducting ROS quenching experiments. The proposed degradation pathway of PFCAs (PFNA and PFOA) was initiated from PFOA/PFNA oxidation by transferring an electron of the carboxylate terminal group of PFOA/PFNA to the Fe(III)-carboxylate complex, then followed by decarboxylation−hydroxylation−elimination−hydrolysis (DHEH) pathway and the accompanying CO2 and F− release. The generated shorter chain PFCAs also underwent degradation with time in the system. This proposed degradation pathway was confirmed by the formation of shorter chain PFCAs, e.g. PFHpA, PFHxA, PFPeA, and PFBA, F- ions, and rapid consumption of Fe3+. For PFOS, besides H/F exchange pathway and chain-shortening (DHEH pathway) to form short chain PFAS during PFCA degradation, desulfonation to form PFOA followed by PFOA degradation also happened. These pathways were suggested by the formation of intermediates — trace amount of shorter chain PFCAs, 6:2 FTS, PFHpS, and F- ions. ·O2- and ·OH were not involved in PFOA degradation in the UVC/Fe0 NPs system with presence of O2, while they may be involved in PFOS degradation, e.g., desulfonation to form PFOA, which were suggested by the results of quenching experiments. And introducing H2O2 into the UVC/Fe0 NPs system resulted in lower PFOA degradation efficiency and defluorination efficiency, which also indicated that ·OH may not be involved in PFOA degradation. Hydrated electrons e-aq that can be involved in desulfonation, defluorination, and C-C bond scission processes were likely quenched by the presence of oxygen to reduce the degradation and defluorination efficiencies; plus, presence of Fe0 NPs may promote the generation of hydrated electrons. Last, UVC/Fe0 NPs system was used to degrade PFAS from WEs in both bench scale and in a scale up POU system. The degradation efficiencies of PFAS in WEs from both wastewater treatment plants (WWTP) were lower than that in deionized water, likely reflecting the complex compositions in the environmental media. Optimal degradation efficiencies of 90±1%, 88±1%, and 46±2% were obtained for PFNA, PFOS, and PFOA, respectively, each starting from 0.5 µg/L using bare Fe0 at pH 3.0 after 2 h. PFAS removal and bacterial inactivation were achieved simultaneously in the POU system using Fe0 NPs without and with rGO support under UVC irradiation in WEs, although the PFAS levels were still above the regulation levels for discard. These pilot tests provided more data and experiences for the real applications of UVC/Fe0 NP system to PFAS contaminated wastewater or other water matrix treatment. Overall, this research demonstrated a cost-effective and environment-friendly method — UVC/Fe0 NPs method for PFAS (i.e., PFOA, PFNA, and PFOS) degradation from WEs for water reuse both with and without presence of oxygen. The possible degradation mechanisms of PFAS with different structures were obtained by testing the concentrations of iron ions, intermediate products, and reactive oxygen species (ROS) involved in the reactions. The developed technology can be potentially applied to treat other environmental media (e.g., groundwater, landfill leachate) that are contaminated by PFAS from previous anthropogenic activities.

The removal of 34 per- and polyfluoroalkyl substances (PFAS) were compared in a 1 stagegranular activated carbon (GAC) filtration to a 2 stage GAC filtration in a pilot study at adrinking water treatment plant (DWTP). The PFASs that were present in the water wereperfluorooctanoic acid (PFOA), perfluorooctane sulfonic acid (PFOS), perfluoropentanoic acid(PFPeA), perfluorohexanoic acid (PFHxA), perfluoroheptanoic acid (PFHpA), perfluorobutanesulfonic acid (PFBS), perfluoropentane sulfonic acid (PFPeS) and perfluorohexane sulfonic acid(PFHxS). A cost comparison for the operation of a one stage GAC to a two stage GAC wascompared for PFAS4 (sum of PFOA, PFNA, PFHxS and PFOS) at treatment goals ranging from2 - 10 ng/L. The pilot was operated at three different flows and the three different bed volumes(BV)s resulting in three different empty bed contact times (EBCTs) at three different times.Therefore, the Lin & Huang adsorption model (1999) was used to model the concentrations ateach EBCT. It was found that the model worked good for PFBS, PFPeS, PFHxS, PFOS andPFOA but not for PFPeA, PFHxA and PFHpA (except for PFPeA and PFHxA during EBCT 5min) and did not work for desorbing PFASs. The removal comparison of PFASs was made,partly by comparing removal efficiencies between the first stage and the second stage GAC filterand by comparing the removal per weight of GAC per BV 1 stage and 2 stages. It was found thatthe removal efficiency decreases with decreasing chain length and increasing treated BVs forboth the first stage and the second stage. The short chain PFCAs were also desorbing after anumber of BVs. The removal per weight of GAC showed that the removal does not increasewhen comparing a one stage GAC to a two stage GAC for any the PFAS. The cost comparisonwas made using the adsorption model. It showed that it was cheaper to operate a 2 stage GAC forthe EBCT of 5 minutes and 8 minutes for the whole range of treatment goals. However, for theEBCT of 15 minutes the costs for the second stage was decreasing with decreasing treatmentgoal which is unrealistic result. This was caused by too few data points available for the model topredict reliable results.

<p>Per- and polyfluoroalkyl substances (PFAS) are a group of emerging global contaminants used in a variety of industrial processes and consumer products, such as personal care products and fast-food wrappers. However, due to their carbon-fluorine bonds, these chemicals resist degradation and persist in the environment. PFAS toxicity is driven by a compound’s functional group and chain length with perfluorooctane sulfonate (PFOS), perfluorohexane sulfonate (PFHxS), perfluorooctanoic acid (PFOA), and hexafluoropropylene oxide dimer acid (GenX) being of focal concern due to their toxicity to wildlife and presence in the environment. Despite growing concern regarding these contaminants, inadequate attention has been given to evaluating what organismal characteristics influence uptake and depuration of these chemicals, such as life stage and sex. <em>Xenopus laevis</em> tadpoles are a useful model to assess the influence of sex on PFAS kinetics since they have a life history that includes a gill to lung transition. Previous studies have shown that air-breathing organisms depurate PFAS more slowly than water-breathing organisms, but this relationship has never been directly tested. Sex has been shown to be an important factor in the depuration of PFOA for rats, with female rats depurating PFOA in four hours while males depurate in four days. The early portion of bioaccumulation curves are also understudied even though tadpoles accumulate PFAS rapidly, reaching steady state within 48 hours of exposure. <em>Xenopus laevis</em> are used to study multiple endpoints for endocrine disrupting chemicals including PFAS. Despite this, toxicity reference values (TRVs) have not been described for the uptake and elimination of PFAS using <em>X. laevis</em>. To address these gaps in knowledge, I first developed TRVs for <em>X. laevis</em> tadpoles exposed to PFOA throughout metamorphosis and evaluated the influence of sex on phenotypic endpoints. Results showed a no observed effect concentration (NOEC) of 11.1 ppm for body mass at day 14 and no effect of sex on apical endpoints. Next, I described the early bioaccumulation of four PFAS with differing structure (chain lengths and functional groups). PFOS was the only chemical to bioaccumulate with a log bioconcentration factor (BCF) at 10 and 1,000 ppm of 1.33 and 1.18, respectively. PFHxS, PFOA, and GenX had BCFs less than 0. Finally, I examined the impact of life-stage and sex on <em>X. laevis</em> tadpole and juvenile depuration rates. Larval tadpoles depurated four times faster than juveniles, indicating a significant effect of life stage on elimination rates. Sex had no influence on elimination rates. These are the first studies conducted evaluating the significance of life stage and sex in toxicokinetics of PFAS in amphibians.</p>

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.

Per- and polyfluoroalkyl substances (PFAS) are a large group of anthropogenic compounds with unique properties, including chemical inertness, resistance to many degradation processes and amphiphilic structure. This makes them useful in a range of applications, but also very persistent and bioaccumulative in nature, where PFAS have been linked to adverse health effects in both animals and humans. There are regulations for PFAS, including the REACH regulation and Stockholm Convention, but for now PFAS are monitored individually. This poses a problem since many regulated, long-chain PFAS today are being replaced with unregulated, short-chain homologues with similar hazardous properties.For water remediation of PFAS, a popular and effective sorption technique for their removal is activated carbon (AC), with its close to 100% sorption efficiency. This study focuses on the efficiency of more sustainable materials like bark, steel slag and biochar to sorb eleven different PFAS (PFAS-11) from contaminated water. In this work, contaminated water passed through different constellations of sorbent materials by flow-through experiments, underwent solid-phase extraction (SPE) using a weak anion-exchange (WAX) adsorbent for sample clean-up, and was lastly prepared for analysis using an ultra-performance liquid chromatograph (UPLC) coupled to a quadrupole tandem mass spectrometer (MS/MS).For the different sorbent constellations tested, perfluorooctane sulfonic acid (PFOS) was removed to the highest degree, with an average removal of 70%. When studying the sum of PFAS-11 between the tested sorption constellations, the bark tests sorbed around 20%, the steel slag combinations sorbed between 30-40% and biochar sorbed 43% of the initial PFAS-11 concentration (1 750 ng/L) in the contaminated water. None of these materials achieved an efficient enough sorption to go below the Swedish PFAS-11 drinking water limit value of 90 ng/L, so the results are for the time being suggested more as complementary, low-cost sorption techniques. Further research is recommended to extensively be able to implement more sustainable sorbents with higher sorbing efficiencies.

No description available.

Närvaron av PFAS (per- och polyfluorerade alkylsubstanser) i miljön och i vårt dricksvatten blir alltmer uppmärksammad i Sverige och världen. Denna undersökning gick dels ut på att undersöka föroreningssituationen av bland annat PFAS på brandövningsplatsen i Vetlanda enligt Naturvårdsverkets metodik för inventering av förorenade områden (MIFO) fas 2 och utfördes av Njudung Energi på uppdrag av Höglandets räddningstjänstförbund och Vetlanda kommun. En andra del utgjordes av ett laborationsförsök där reningskapaciteten för PFAS med fyra olika adsorbenter jämfördes. Vetlanda brandövningsplats påvisade kraftigt förhöjda halter PFOS (perfluoroktansulfonsyra) och ∑PFAS11 i grundvatten (8,9 µg/l och 27,2 µg/l respektive) och i jord (0,82 mg/kg TS PFOS). Halten PFOS i grundvatten var över 45 ng/l och i jord översteg halten 0,02 mg/kg TS som är SGI:s preliminära riktvärden för PFOS (Pettersson et al. 2015). I ytvattenrecipienten var halten PFOS över det rekommenderade årsmedelvärdet enligt EU:s miljökvalitetsnorm för inlandsvatten (65 ng/l). Ytvattenrecipienten anses särskild skyddsvärd då den mynnar ut i Emån, som har höga naturvärden och används som vattentäkt. Halten koppar och bly i jord översteg Naturvårdsverkets generella riktvärden för mindre känslig markanvändning (200 mg/kg TS och 400 mg/kg TS respektive). Objektet Vetlanda brandövningsplats bedöms utgöra riskklass 1 enligt MIFO fas 2, vilket innebär en mycket stor risk. Som åtgärd föreslås grundvattenpumpning och behandling för att åtgärda föroreningsnivån med avseende på PFAS i grundvattnet, fortsatt provtagning för att avgränsa föroreningen i jord samt schaktsanering av de förorenade jordmassorna för att förhindra fortsatt urlakning till grundvattnet. I laborationsförsöket jämfördes de två konventionella filtermaterialen granulärt aktivt kol (GAC) och jonbytarmassa (AE) med grillkol och torv, två relativt billiga material. Labbförsöket utfördes som ett kolonnförsök med varierande pH-värden samt som ett försök med förlängd exponeringstid. Resultatet visar att AE och torv gynnas av ett sänkt pH-värde och av en förlängd exponeringstid. GAC uppvisade bäst reningsgrad under samtliga försök, med fullständig adsorption av PFOS och ∑PFAS11 för kolonnförsöken. Torv avlägsnade 65% PFOS vid 10 dagars exponeringstid och grillkol avlägsnade omkring 50% PFOS i kolonnförsöken. Försöket innehåller endast ett fåtal provtagningspunkter och ytterligare studier med grillkol och torv krävs för att fastställa deras eventuella potential som adsorbenter för att rena PFAS i grundvatten.

Water pollution is a profound ecological concern, exerting detrimental effects on human well-being, ecological systems, and animal life. Among the emerging contaminants that critically influence water quality and have garnered substantial scientific interest in recent times are per- and polyfluoroalkyl substances (PFAS). It is crucial to investigate the de- velopment of an easy technique for PFAS detection and measurement that can be used for quick analysis. This thesis explores the possibility to use amine-functionalized mesoporous carbon as an adsorbent to develop a detection method based on sequential adsorption of per- and polyfluoroalkyl substances (PFAS) and a dye, Rose Bengal, onto the adsorbent. The hypothesis is that the concentration of non-adsorbed dye is dependent on the amount of PFAS present, making the color intensity of the remaining solution proportional to the PFAS concentration. Mesoporous carbon was chosen as the adsorbent due to their high specific surface area, providing a high adsorption capacity, and the potential to functionalize the surface with amine groups which will attract the PFAS. Rose Bengal was selected as a concentration indicator as it has been shown that it can be used as a proxy for PFAS. In this study, the most prevalent PFAS compounds, namely PFOA and PFOS, were investigated. Prior to testing, the adsorbent underwent characterization using diverse techniques to show the porosity and particle morphology. The adsorption experiments encompassed varying PFAS concentrations and a range of dye solutions to determine the detection range, the powder-to-solution ratio necessary for discernible differentiation, and the adsorption or saturation time for both PFAS and dye. This thesis concludes that it was not possible to detect neither PFOA nor PFOS in the range of 0.1 pg/mL to 1 μg/mL with the setup, even though Rose Bengal adsorption could be detected down to 0.6 μg/mL. It was further observed that amine-functionalized hard templated mesoporous carbon has a higher adsorption capacity compared to the soft templated material.