| 1. |
- Cioni, Lara, et al.
(författare)
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Fluorine Mass Balance, including Total Fluorine, Extractable Organic Fluorine, Oxidizable Precursors, and Target Per- and Polyfluoroalkyl Substances, in Pooled Human Serum from the Tromsø Population in 1986, 2007, and 2015
- 2023
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Ingår i: Environmental Science and Technology. - 0013-936X .- 1520-5851. ; 57:40, s. 14849-14860
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Tidskriftsartikel (refereegranskat)abstract
- Of the thousands of per- and polyfluoroalkyl substances (PFAS) known to exist, only a small fraction (≤1%) are commonly monitored in humans. This discrepancy has led to concerns that human exposure may be underestimated. Here, we address this problem by applying a comprehensive fluorine mass balance (FMB) approach, including total fluorine (TF), extractable organic fluorine (EOF), total oxidizable precursors (TOP), and selected target PFAS, to human serum samples collected over a period of 28 years (1986, 2007, and 2015) in Tromsø, Norway. While concentrations of TF did not change between sampling years, EOF was significantly higher in 1986 compared to 2007 and 2015. The ∑12PFAS concentrations were highest in 2007 compared to 1986 and 2015, and unidentified EOF (UEOF) decreased from 1986 (46%) to 2007 (10%) and then increased in 2015 (37%). While TF and EOF were not influenced by sex, women had higher UEOF compared to men, opposite to target PFAS. This is the first FMB in human serum to include TOP, and it suggests that precursors with >4 perfluorinated carbon atoms make a minor contribution to EOF (0–4%). Additional tools are therefore needed to identify substances contributing to the UEOF in human serum.
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| 2. |
- Haque, Faiz, et al.
(författare)
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Per- and polyfluoroalkyl substances (PFAS) in white-tailed sea eagle eggs from Sweden: Temporal trends (1969-2021), spatial variations, fluorine mass balance, and suspect screening
- 2023
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Ingår i: Environmental Science. - 2050-7887 .- 2050-7895.
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Tidskriftsartikel (refereegranskat)abstract
- Temporal and spatial trends of 15 per- and polyfluoroalkyl substances (PFAS) were determined in white-tailed sea eagle (WTSE) eggs (Haliaeetus albicilla) from two inland and two coastal regions of Sweden between 1969 and 2021. PFAS concentrations generally increased from ∼1969 to ∼1990s–2010 (depending on target and site) and thereafter plateaued or declined, with perfluorooctane sulfonamide (FOSA) and perfluorooctane sulfonate (PFOS) declining faster than most perfluoroalkyl carboxylic acids (PFCAs). The net result was a shift in the PFAS profile from PFOS-dominant in 1969–2010 to an increased prevalence of PFCAs over the last decade. Further, during the entire period higher PFAS concentrations were generally observed in coastal populations, possibly due to differences in diet and/or proximity to more densely populated areas. Fluorine mass balance determination in pooled samples from three of the regions (2019–2021) indicated that target PFAS accounted for the vast majority (i.e. 81–100%) of extractable organic fluorine (EOF). Nevertheless, high resolution mass-spectrometry-based suspect screening identified 55 suspects (31 at a confidence level [CL] of 1–3 and 24 at a CL of 4–5), of which 43 were substances not included in the targeted analysis. Semi-quantification of CL ≤ 2 suspects increased the identified EOF to >90% in coastal samples. In addition to showing the impact of PFAS regulation and phase-out initiatives, this study demonstrates that most extractable organofluorine in WTSE eggs is made up of known (legacy) PFAS, albeit with low levels of novel substances.
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| 3. |
- Lauria, Mélanie Z., 1993-, et al.
(författare)
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Closing the Organofluorine Mass Balance in Marine Mammals Using Suspect Screening and Machine Learning-Based Quantification
- 2024
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Ingår i: Environmental Science and Technology. - 0013-936X .- 1520-5851. ; 58:5, s. 2458-2467
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Tidskriftsartikel (refereegranskat)abstract
- High-resolution mass spectrometry (HRMS)-based suspect and nontarget screening has identified a growing number of novel per- and polyfluoroalkyl substances (PFASs) in the environment. However, without analytical standards, the fraction of overall PFAS exposure accounted for by these suspects remains ambiguous. Fortunately, recent developments in ionization efficiency (IE) prediction using machine learning offer the possibility to quantify suspects lacking analytical standards. In the present work, a gradient boosted tree-based model for predicting log IE in negative mode was trained and then validated using 33 PFAS standards. The root-mean-square errors were 0.79 (for the entire test set) and 0.29 (for the 7 PFASs in the test set) log IE units. Thereafter, the model was applied to samples of liver from pilot whales (n = 5; East Greenland) and white beaked dolphins (n = 5, West Greenland; n = 3, Sweden) which contained a significant fraction (up to 70%) of unidentified organofluorine and 35 unquantified suspect PFASs (confidence level 2–4). IE-based quantification reduced the fraction of unidentified extractable organofluorine to 0–27%, demonstrating the utility of the method for closing the fluorine mass balance in the absence of analytical standards.
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| 4. |
- Pütz, Kerstin Winkens, et al.
(författare)
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Are cosmetics a significant source of PFAS in Europe? product inventories, chemical characterization and emission estimates
- 2022
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Ingår i: Environmental Science. - : Royal Society of Chemistry (RSC). - 2050-7887 .- 2050-7895. ; 24:10, s. 1697-1707
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Tidskriftsartikel (refereegranskat)abstract
- In this study, emission of per- and polyfluoroalkyl substances (PFAS) from the use of cosmetics in the European Economic Area (EEA; not including Lichtenstein and Iceland) was estimated for the first time.Using the European Commission database for information on cosmetic substances and ingredients (CosIng) ~170 structures containing at least –CF2– or –CF3 were identified as ingredients in cosmetics on the European market.These structures were then cross referenced against the Cosmetic Database “CosmEthics” to identify PFAS-containing products. Among these products, polytetrafluoroethylene (PTFE) and C9-15 fluoroalcohol phosphate were the most frequently listed PFAS ingredients.Thereafter,a sample of 45 cosmetics spanning 5 product categories was purchased in Sweden and characterized for total fluorine (TF), extractable organofluorine (EOF), and target PFAS. Using measured concentrations, the share of PFAS-containing products in each product category, sales data from Cosmetics Europe, as well as other parameters and assumptions, the annual emission of PFAS from cosmetics after use was estimated. Annual EEA-wide TF and EOF-based emissions ranged from 17–38 000 kg F per year and 37–5100 kg F per year, respectively, representing combined emission to wastewater and solid waste (low to high emission scenario).Sum perfluoroalkyl carboxylic acid (PFCA) emissions were considerably lower (21 kg PPFCAs per year; high scenario). While TF- and EOF-based emissions are significant, they are considerably lower than estimates of TF emission from washing of PFAS-coated textiles in the EU.This work provides the first estimate of PFAS emissions from cosmetics and highlights the importance of using a multi-platform analytical approach for PFAS emission estimates.
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| 5. |
- Schellenberger, Steffen, 1981-, et al.
(författare)
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An Outdoor Aging Study to Investigate the Release of Per- And Polyfluoroalkyl Substances (PFAS) from Functional Textiles
- 2022
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Ingår i: Environmental Science and Technology. - : American Chemical Society. - 0013-936X .- 1520-5851. ; 56, s. 3471-
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Tidskriftsartikel (refereegranskat)abstract
- The emission of per- and polyfluoroalkyl substances (PFAS) from functional textiles was investigated via an outdoor weathering experiment in Sydney, Australia. Polyamide (PA) textile fabrics treated with different water-repellent, side-chain fluorinated polymers (SFPs) were exposed on a rooftop to multiple natural stressors, including direct sunlight, precipitation, wind, and heat for 6-months. After weathering, additional stress was applied to the fabrics through abrasion and washing. Textile characterization using a multiplatform analytical approach revealed loss of both PFAS-containing textile fragments (e.g., microfibers) as well as formation and loss of low molecular weight PFAS, both of which occurred throughout weathering. These changes were accompanied by a loss of color and water repellency of the textile. The potential formation of perfluoroalkyl acids (PFAAs) from mobile residuals was quantified by oxidative conversion of extracts from unweathered textiles. Each SFP-textile finish emitted a distinct PFAA pattern following weathering, and in some cases the concentrations exceeded regulatory limits for textiles. In addition to transformation of residual low molecular weight PFAA-precursors, release of polymeric PFAS from degradation and loss of textile fibers/particles contributed to overall PFAS emissions during weathering. © 2022 The Authors.
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| 6. |
- Spaan, Kyra M., et al.
(författare)
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Characterizing the Organohalogen Iceberg : Extractable, Multihalogen Mass Balance Determination in Municipal Wastewater Treatment Plant Sludge
- 2023
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Ingår i: Environmental Science and Technology. - 0013-936X .- 1520-5851. ; 57:25, s. 9309-9320
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Tidskriftsartikel (refereegranskat)abstract
- The large number and diversity of organohalogen compounds(OHCs)occurring in the environment poses a grand challenge to analyticalchemists. Since no single targeted method can identify and quantifyall OHCs, the size of the OHC iceberg may be underestimated.We sought to address this problem in municipal wastewater treatmentplant (WWTP) sludge by quantifying the unidentified fraction of theOHC iceberg using targeted analyses of major OHCs together with measurementsof total and extractable (organo)halogen (TX and EOX, respectively;where X = F, Cl, or Br). In addition to extensive method validationvia spike/recovery and combustion efficiency experiments, TX and/orEOX were determined in reference materials (BCR-461 and NIST SRMs2585 and 2781) for the first time. Application of the method to WWTPsludge revealed that chlorinated paraffins (CPs) accounted for most(similar to 92%) of the EOCl, while brominated flame retardants and per-and polyfluoroalkyl substances (PFAS) accounted for only 54% of theEOBr and 2% of the EOF, respectively. Moreover, unidentified EOF innonpolar CP extracts points to the existence of organofluorine(s)with physical-chemical properties unlike those of target PFAS.This study represents the first multihalogen mass balance in WWTPsludge and offers a novel approach to prioritization of sample extractsfor follow-up investigation. A multihalogenmass balance experiment in WWTP sludge revealedhigh levels of unidentified organofluorine and organobromine. Organochlorinewas characterized mainly by chlorinated paraffins.
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| 7. |
- Dürig, Wiebke, et al.
(författare)
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What is in the fish? Collaborative trial in suspect and non-target screening of organic micropollutants using LC- and GC-HRMS
- 2023
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Ingår i: Environment International. - : Elsevier. - 0160-4120 .- 1873-6750. ; 181
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Tidskriftsartikel (refereegranskat)abstract
- A collaborative trial involving 16 participants from nine European countries was conducted within the NORMAN network in efforts to harmonise suspect and non-target screening of environmental contaminants in whole fish samples of bream (Abramis brama). Participants were provided with freeze-dried, homogenised fish samples from a contaminated and a reference site, extracts (spiked and non-spiked) and reference sample preparation protocols for liquid chromatography (LC) and gas chromatography (GC) coupled to high resolution mass spectrometry (HRMS). Participants extracted fish samples using their in-house sample preparation method and/or the protocol provided. Participants correctly identified 9–69 % of spiked compounds using LC-HRMS and 20–60 % of spiked compounds using GC-HRMS. From the contaminated site, suspect screening with participants’ own suspect lists led to putative identification of on average ∼145 and ∼20 unique features per participant using LC-HRMS and GC-HRMS, respectively, while non-target screening identified on average ∼42 and ∼56 unique features per participant using LC-HRMS and GC-HRMS, respectively. Within the same sub-group of sample preparation method, only a few features were identified by at least two participants in suspect screening (16 features using LC-HRMS, 0 features using GC-HRMS) and non-target screening (0 features using LC-HRMS, 2 features using GC-HRMS). The compounds identified had log octanol/water partition coefficient (KOW) values from −9.9 to 16 and mass-to-charge ratios (m/z) of 68 to 761 (LC-HRMS and GC-HRMS). A significant linear trend was found between log KOW and m/z for the GC-HRMS data. Overall, these findings indicate that differences in screening results are mainly due to the data analysis workflows used by different participants. Further work is needed to harmonise the results obtained when applying suspect and non-target screening approaches to environmental biota samples.
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| 8. |
- Kärrman, Anna, 1975-, et al.
(författare)
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Can determination of extractable organofluorine (EOF) be standardized? First interlaboratory comparisons of EOF and fluorine mass balance in sludge and water matrices
- 2021
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Ingår i: Environmental Science. - : Royal Society of Chemistry. - 2050-7887 .- 2050-7895. ; 23:10, s. 1458-1465
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Tidskriftsartikel (refereegranskat)abstract
- The high proportion of unidentified extractable organofluorine (EOF) observed globally in humans and the environment indicates widespread occurrence of unknown per- and polyfluoroalkyl substances (PFAS). However, efforts to standardize or assess the reproducibility of EOF methods are currently lacking. Here we present the first EOF interlaboratory comparison in water and sludge. Three participants (four organizations) analyzed unfortified and PFAS-fortified ultrapure water, two unfortified groundwater samples, unfortified wastewater treatment plant effluent and sludge, and an unfortified groundwater extract. Participants adopted common sample handling strategies and target lists for EOF mass balance but used in-house combustion ion-chromatography (CIC) and liquid chromatography-tandem mass spectrometry (LC-MS/MS) methods. EOF accuracy ranged from 85-101% and 76-109% for the 60 and 334 ng L-1 fluorine (F) - fortified water samples, respectively, with between-laboratory variation of 9-19%, and within-laboratory variation of 3-27%. In unfortified sludge and aqueous samples, between-laboratory variation ranged from 21-37%. The contribution from sum concentrations of 16 individual PFAS (∑PFAS-16) to EOF ranged from 2.2-60% but extended analysis showed that other targets were prevalent, in particular ultra-short-chain perfluoroalkyl acids (e.g. trifluoroacetic acid) in aqueous samples and perfluoroalkyl acid-precursors (e.g. polyfluoroalkyl phosphate diesters) in sludge. The EOF-CIC method demonstrated promising accuracy, robustness and reporting limits but poor extraction efficiency was observed for some targets (e.g. trifluoroacetic acid).
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| 9. |
- Lauria, Mélanie Z., 1993-, et al.
(författare)
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Widespread Occurrence of Non-Extractable Fluorine in Artificial Turfs from Stockholm, Sweden
- 2022
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Ingår i: Environmental Science and Technology Letters. - : American Chemical Society (ACS). - 2328-8930. ; 9:8, s. 666-672
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Tidskriftsartikel (refereegranskat)abstract
- Per- and polyfluoroalkyl substances (PFAS) are frequently used in the production of rubber and plastic, but little is known about the identity, concentration, or prevalence of PFAS in these products. In this study, a representative sample of plastic- and rubber-containing artificial turf (AT) fields from Stockholm, Sweden, was subjected to total fluorine (TF), extractable organic fluorine (EOF), and target PFAS analysis. TF was observed in all 51 AT samples (ranges of 16–313, 12–310, and 24–661 μg of F/g in backing, filling, and blades, respectively), while EOF and target PFAS occurred in <42% of all samples (<200 and <1 ng of F/g, respectively). A subset of samples extracted with water confirmed the absence of fluoride. Moreover, application of the total oxidizable precursor assay revealed negligible perfluoroalkyl acid (PFAA) formation across all three sample types, indicating that the fluorinated substances in AT are not low-molecular weight PFAA precursors. Collectively, these results point toward polymeric organofluorine (e.g., fluoroelastomer, polytetrafluoroethylene, and polyvinylidene fluoride), consistent with patent literature. The combination of poor extractability and recalcitrance toward advanced oxidation suggests that the fluorine in AT does not pose an imminent risk to users. However, concerns surrounding the production and end of life of AT, as well as the contribution of filling and blades to environmental microplastic contamination, remain.
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| 10. |
- Nyström, Jennifer, et al.
(författare)
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Demographic, life-style and physiological determinants of serum per- and polyfluoroalkyl substance (PFAS) concentrations in a national cross-sectional survey of Swedish adolescents
- 2022
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Ingår i: Environmental Research. - : Elsevier BV. - 0013-9351 .- 1096-0953. ; 208
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Tidskriftsartikel (refereegranskat)abstract
- Per: and polyfluoroalkyl substances (PFAS) may affect adolescent health, yet factors related to PFAS concentrations in serum are poorly understood. We studied demographic, life-style and physiological determinants of serum PFAS concentrations in Swedish adolescents from a nation-wide survey, Riksmaten Adolescents 2016–17 (RMA, age 10–21 years, n = 1098). Serum samples were analyzed for 42 PFAS, using liquid chromatography-tandem mass spectrometry. The cumulative probability model was used to estimate associations between serum PFAS and determinants, using ordinal logistic regression. Legacy linear (lin-) perfluorooctanoic acid (PFOA), perfluorononaoic acid (PFNA), perfluorodecanoic acid (PFDA), perfluoroundecanoic acid (PFUnDA), lin-perfluorohexanesulfonic acid (PFHxS) and lin-/branched (br-) perfluorooctanesulfonic acid (PFOS) were quantifiable in ≥70% of the samples. The emerging PFAS 9-chlorohexanedecafluoro-3-oxanone-1-sulfonic acid (9Cl-PF3ONS) was quantified in 5.4% of the samples, suggesting initiation of long-range transport far from production sites. Median concentrations of all legacy PFAS were <2 ng/g serum, with a few participants having very high (>100 ng/g serum) lin-PFHxS and lin-/br-PFOS concentrations due to previous high exposure from PFAS-contaminated drinking water. Legacy PFAS exposure was strongly associated with birth country of the participants and their mothers. 2-fold higher estimated adjusted mean (EAM) concentrations were seen among high income country participants with mothers from high income countries than among low/lower-middle income country participants with mothers from the same category. Menstruating females had lower br-PFOS EAM concentrations than those who were not. Iron status (plasma ferritin) among females may be a marker of intensity of menstrual bleeding, but it was not significantly associated with legacy PFAS concentrations among females. Further studies are needed to determine how physiological changes occurring around menstruation affect the toxicokinetics of PFAS in females. In conclusion, PFAS are pollutants of the industrialized world and some of the identified determinants may be overlooked confounders/effect modifiers that should be included in future PFAS/health studies among adolescents.
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| 11. |
- Nyström, Jennifer, et al.
(författare)
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Healthy eating index and diet diversity score as determinants of serum perfluoroalkyl acid (PFAA) concentrations in a national survey of Swedish adolescents
- 2022
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Ingår i: Environmental Research. - : Elsevier BV. - 0013-9351 .- 1096-0953. ; 212, Part A
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Tidskriftsartikel (refereegranskat)abstract
- Food is an important source of perfluoroalkyl acid (PFAA) exposure for the general adult population, but few data exist for adolescents. Healthy food habits established during adolescence may positively influence health later in life. Associations between serum PFAA concentrations and a healthy eating index (SHEIA15), as well as a diet diversity score (RADDS), were determined in a nationally representative adolescent population from Sweden (Riksmaten Adolescents 2016–2017, RMA). Using consumption data from food registrations and frequency questionnaires, we additionally analyzed associations with commonly consumed food groups. Associations were analyzed by fitting a cumulative probability model using ordinal regression. Among the seven PFAAs detected in ≥70% of the 1098 participants (age 10–21 years), median concentrations ranged from <1 ng/g serum of perfluorononanoic acid (PFNA), perfluorodecanoic acid (PFDA), perflurorundecanoic acid (PFUnDA), linear (lin-) perfluorohexanesulfonic acid (PFHxS) and branched (br-) perfluorooctanesulfonic acid (PFOS) to 1–2 ng/g serum of lin-perfluorooctanoic acid (PFOA) and lin-PFOS. PFNA, PFDA, PFUnDA and lin-PFOS concentrations were positively associated with both SHEIA15 and RADDS, a finding most likely driven by higher consumption of seafood. PFDA, PFUnDA and lin-PFOS concentrations were positively related to commonly consumed fish/shellfish groups, such as lean marine fish and shellfish. Inverse associations between PFAA concentrations and dairy consumption suggest an underlying factor behind dairy consumption that similarly affects adolescent exposure to the different PFAAs. Isomeric differences in dietary exposure between lin-PFOS and br-PFOS were suggested, as br-PFOS concentrations, in contrast to lin-PFOS, were not associated with SHEIA15, RADDS and consumption of different food groups. We conclude that Swedish adolescents, adhering to a diverse and healthy diet, appears to be more highly exposed to legacy PFAAs than those eating less healthy. Additional research is necessary for a better understanding of the health implications of healthy eating from a PFAA exposure perspective.
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| 12. |
- Plassmann, Merle M., 1981-
(författare)
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Environmental occurrence and fate of semifluorinated n-alkanes and perfluorinated alkyl acids present in ski waxes
- 2011
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Highly fluorinated organic compounds are emerging environmental contaminants of concern, due to their persistence, ubiquitous distribution, bioaccumulation potential and toxicity. Ski waxes are sources of highly fluorinated chemicals to the environment that have not been investigated so far. Some contain fluorinated additives such as semifluorinated n-alkanes (SFAs). This thesis investigated the fate of SFAs after abrasion onto snow through skiing activities. Furthermore, perfluorinated alkyl acids (PFAAs) were found to be present in fluorinated ski waxes. A lot of attention has been paid to elucidating the environmental fate of PFAAs during the past decade. However, nothing was known so far about their release from melting snow packs. Analytical methods for quantification of SFAs in different environmental matrices were developed. The methods were used to investigate the fate of SFAs during snow melt and to study their occurrence in ski areas. Laboratory snow melt experiments and model-based fate simulations suggested that SFAs will sorb to the snow grain surface and particles in the bulk snow and, after snowmelt, will end up on the underlying (soil) surface. SFAs were detected and quantified for the first time in snow and soil samples taken from a ski area in Sweden. Comparison of concentrations in snow and soil did not give any evidence for long-term accumulation of SFAs in surface soil, but suggested volatilization of shorter chain homologues during snow melt. Such a volatilization could also explain an observed SFA pattern difference between snow and soil samples. Laboratory scale snow melt experiments were also used to investigate the behavior of PFAAs during snowmelt. PFAAs were released with the melt water from the snow pack in pulses. The pulses occurred early, late or with a so far unknown peak elution in the middle of the snowmelt, depending on the hydrophobicity of the PFAAs. These peak releases were further influenced by the age of the snow pack and thus the snow surface area and to a lesser extent by pH and ion concentrations.
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| 13. |
- Spaan, Kyra M., et al.
(författare)
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Pharmaceuticals Account for a Significant Proportion of the Extractable Organic Fluorine in Municipal Wastewater Treatment Plant Sludge
- 2023
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Ingår i: Environmental Science and Technology Letters. - : American Chemical Society (ACS). - 2328-8930. ; 10:4, s. 328-336
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Tidskriftsartikel (refereegranskat)abstract
- Fluorine mass balance studies have shown that monomeric per- and polyfluoroalkyl substances (PFAS) with perfluoroalkyl chain lengths of ∼5–14 carbon atoms (i.e., “conventional” PFAS) account for a fraction (∼2%) of the extractable organic fluorine (EOF) in municipal wastewater treatment plant (WWTP) sludge. The identity of the remaining EOF has thus far been unclear but may be partly attributable to fluorine-containing pharmaceuticals and pesticides used throughout society. To test this hypothesis, we applied high resolution mass spectrometry-based suspect screening to samples of municipal WWTP sludge which had been previously subjected to a fluorine mass balance. Sixteen pharmaceutical substances (including transformation products [TPs]), one pesticide, and thirteen conventional PFAS were confirmed at confidence levels 1–4 and (semi)quantified, revealing concentrations ranging from 0.07 to 155 ng/g dw. Notably, eight pharmaceutical substances did not meet the OECD definition of PFAS. When converted to fluorine equivalents, the newly detected organofluorine substances increased the percentage of known EOF from ∼2% to ∼27%, of which ∼22% was attributed to pharmaceutical and pesticide substances, with the greatest contributions from ticagrelor TP (4.0%), ezetimibe (3.9%), and bicalutamide (3.5%). These data highlight the importance of considering both unconventional and non-PFAS organofluorine substances in addition to conventional PFAS when closing the organofluorine mass balance in WWTP sludge.
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