To Örebro University

Per- and polyfluoroalkyl substances (PFAS) are anthropogenic contaminants commonly found in drainage water from waste management facilities. Within the European Union, these facilities either treat the water locally or transfer it to wastewater treatment plants to reduce harmful emissions. However, PFAS are a broad class of compounds with varying physicochemical properties, leading to different removal efficiencies for adsorbents. Activated carbon and ion exchange resins are effective but costly, and they can become saturated with other contaminants. Therefore, this study aims to explore inexpensive, abundant alternatives for reducing PFAS concentrations in the environment. In Sweden, bark is a by-product of forestry activities, primarily used as fuel in heat and power plants. This study evaluates the ability of pine and spruce bark to remove PFAS from contaminated drainage water. Initial laboratory experiments employed liquid-to-solid ratios of 10 and 20 to assess the performance of both materials. Results indicated that pine bark exhibited better removal efficiencies, particularly when a layered column with pine bark followed by spruce bark was utilized. The overall removal efficiencies for short-chain PFAS (perfluorinated carbons: PFCA C3-C6 and PFSA C4-C5) and long-chain PFAS (PFCA > C7 and PFSA > C6) were below 20%, except for perfluorooctane sulfonic acid (PFOS), which showed reductions of 40% to 80%. The pH of the treated water decreased from 7 to 4 (pine bark) and 5 (spruce bark) after treatment. In a larger-scale trial, a combination of 50% pine bark and 50% spruce bark was tested, achieving similar reductions for PFOS. Although the removal efficiencies were insufficient for exclusive treatment, these materials may be useful in specific applications targeting long-chain PFAS or in conjunction with other treatment methods.

Per- and polyfluoroalkyl substances (PFAS) have been used for decades in a broad range of consumer products and industrial applications. A variety of waste and products containing PFAS inevitably end up at waste management facilities when they are no longer considered useful. Drainage water samples (n = 157) were collected from eight subsections at a waste management facility in Sweden and analyzed for 23 PFAS and extractable organofluorine (EOF). Two different sampling methods were used, grab sampling (n = 32, without filtration) and composite sampling (n = 8, produced by pooling 16 filtered samples taken at the same subsection). Although PFAS have been studied at waste sites, the information is scarce regarding how the concentrations and homologue profiles could differ within the sites. In this study, we investigated if composite sampling could be an alternative to grab sampling for PFAS monitoring purposes. Herein, the PFAS concentrations ranged from <1 to 22 μg/L; the grab samples showed systematic higher concentrations than their corresponding composite sample. Short-chain perfluoroalkyl sulfonic acids (C4 and C5) were the largest contributing sub-class, followed by short-chain perfluoroalkyl carboxylic acids (C4 to C6). EOF was measured up to approximately 140 μg/L F with 99% being unexplained by the fluorine mass balance analysis. The results from this study showed that both sampling methods were comparable for target analysis and that 11 compounds represented most of the PFAS concentrations. However, the discrepancy between the sampling methods was greater for EOF analysis and may be due to the preparation of composite samples and/or due to fluctuating discharges during the sampling period. Composite sampling was observed to be comparable to grab sampling for target analysis.

Per- and polyfluorinated substances (PFAS) are man-made chemicals with a widespread environmental occurrence around the globe. This group of compounds has been associated with negative effects on human health and the environment. A recent estimation on the number of PFAS using the revised PFAS definition from the OECD in 2021 reached over 7 million compounds in the PubChem database. PFAS monitoring usually aims towards a small number of compounds in comparison to the potential total number of PFAS. In this thesis, target analysis for short- and long-chain PFAS, extractable organofluorine (EOF) analysis, target analysis after oxidative conversion was performed for a comprehensive assessment of PFAS in drainage water from different sections within a waste management facility. Other, not as common fluorinated compounds were also analyzed. For water remediation purposes, the ability to reduce PFAS concentrations using pine and spruce barks was also assessed. The drainage water contained PFAS in the magnitude of low μg/L with minor contribution from precursor compounds. Interestingly, the inorganic fluoride anions tetrafluoroborate (BF4) and hexafluorophosphate (PF6) were detected. The composition of 50% pine and 50% spruce demonstrated the greatest ability to remove PFAS with 100 μg/kg sorbent. Addition of calcium hydroxide (Ca(OH)2) was not observed to be beneficial when the bark material was thermally treated.

Waste management facilities are a known source for per- and polyfluoroalkyl substances (PFAS) to the environment. In this study, water samples from seven subsections within a waste management facility in Sweden were analyzed for PFAS and extractable organofluorine (EOF). Oxidative conversion was used to investigate how much PFAS precursors could contribute to the EOF. Out of the 23 analyzed PFAS, ten compounds accounted for a major proportion of the concentrations. Before oxidative conversion the ∑10PFAS were between 0.44 μg/L and 17 μg/L. The EOF ranged from 2 μg/L F up to 79 μg/L F. There was a greater difference in concentrations and profiles between the subsections in comparison to the four sampling dates at respective sampling point, suggesting different sources of PFAS from the waste. Oxidative conversion revealed presence of precursors by elevated concentrations of perfluoroalkyl acids after oxidation, which increased the explained EOF up to 25%. Seven samples from one sampling date were selected to investigate if other fluorinated compounds (inorganic anions, ultra-short-chain PFAS, and zwitterions) could be a part of the unexplained EOF fraction. The contribution of fluorine from tetrafluoroborate and hexafluorophosphate were equal or higher proportions than the ∑10PFAS. The presence of the ionic liquids tetrafluoroborate and hexafluorophosphate could originate from battery waste, due to their use as counter ions in batteries. Ultra-short-chain PFAS increased the explained EOF by an average of 8%, with trifluoroacetic acid and trifluoromethane sulfonic acid being the main contributors. However, the reported concentrations of ultra-short-chain PFAS, were underestimated due to low recovery by the additional washing step to remove inorganic fluoride for EOF analysis. The concentrations of zwitterions were low and increased the explained EOF by < 1%. Our results suggest that EOF, selected PFAS, oxidative conversion and anionic fluorinated substances give a better picture of PFAS contamination.