| 1. |
- Benskin, Jonathan P., et al.
(författare)
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Perfluorinated Acid Isomer Profiling in Water and Quantitative Assessment of Manufacturing Source
- 2010
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Ingår i: Environmental Science and Technology. - : American Chemical Society (ACS). - 0013-936X .- 1520-5851. ; 44:23, s. 9049-9054
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Tidskriftsartikel (refereegranskat)abstract
- A method for isomer profiling of perfluorinated compounds (PFCs) in water was developed and applied to quantitatively assess the contributions from electrochemical (ECF) and telomer manufacturing processes around source regions of North America, Asia, and Europe. With the exception of 3 sites in Japan, over 80% of total perfluorooctanoate (PFOA, C7F15COO -) was from ECF, with the balance attributable to strictly linear (presumably telomer) manufacturing source(s). Comparing PFOA isomer profiles in samples from China, with PFOA obtained from a local Chinese manufacturer, indicated <3% difference in overall branched isomer content; thus, exclusive contribution from local ECF production cannot be ruled out. In Tokyo Bay, ECF, linear-telomer, and isopropyl-telomer sources contributed to 33%, 53%, and 14% of total PFOA, respectively. Perfluorooctane sulfonate (PFOS, C 8F17SO3-) isomer profiles were enriched in branched content (i.e., >50% branched) in the Mississippi River but in all other locations were similar or only slightly enriched in branched content relative to historical ECF PFOS. Isomer profiles of other PFCs are also reported. Overall, these data suggest that, with the exception of Tokyo Bay, ECF manufacturing has contributed to the bulk of contamination around these source regions, but other sources are significant, and remote sites should be monitored.
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| 2. |
- 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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| 3. |
- 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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| 4. |
- 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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| 5. |
- 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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| 6. |
- 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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| 7. |
- Skedung, Lisa, et al.
(författare)
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Identification and quantification of fluorinated polymers in consumer products by combustion ion chromatography and pyrolysis-gas chromatography-mass spectrometry
- 2024
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Ingår i: Environmental Science. - 2050-7887 .- 2050-7895. ; 26
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Tidskriftsartikel (refereegranskat)abstract
- Total fluorine was determined in 45 consumer product samples from the Swedish market which were either suspected or known to contain fluorinated polymers. Product categories included cookware (70–550 000 ppm F), textiles (10–1600 ppm F), electronics (20–2100 ppm F), and personal care products (10–630 000 ppm F). To confirm that the fluorine was organic in nature, and deduce structure, a qualitative pyrolysis-gas chromatography-mass spectrometry (pyr-GC/MS) method was validated using a suite of reference materials. When applied to samples with unknown PFAS content, the method was successful at identifying polytetrafluoroethylene (PTFE) in cookware, dental products, and electronics at concentrations as low as 0.1–0.2 wt%. It was also possible to distinguish between 3 different side-chain fluorinated polymers in textiles. Several products appeared to contain high levels of inorganic fluorine. This is one of the few studies to quantify fluorine in a wide range of consumer plastics and provides important data on the concentration of fluorine in materials which may be intended for recycling, along with insights into the application of pyr-GC/MS for structural elucidation of fluorinated polymers in consumer products.
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| 8. |
- 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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| 9. |
- 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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| 10. |
- 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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