| 1. |
- Ecke, Frauke, et al.
(författare)
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Spatio-temporal variation of metals and organic contaminants in bank voles (Myodes glareolus)
- 2020
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Ingår i: Science of the Total Environment. - : Elsevier. - 0048-9697 .- 1879-1026. ; 713
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Tidskriftsartikel (refereegranskat)abstract
- Environmental contamination with metals and organic compounds is of increasing concern for ecosystem and human health. Still, our knowledge about spatial distribution, temporal changes and ecotoxicological fate of metals and organic contaminants in wildlife is limited. We studied concentrations of 69 elements and 50 organic compounds in 300 bank voles (Myodes glareolus), Europe's most common mammal, sampled in spring and autumn 2017–2018 in five monitoring areas, representing three biogeographic regions. In addition, we compared measured concentrations with previous results from bank voles sampled within the same areas in 1995–1997 and 2001. In general, our results show regional differences, but no consistent patterns among contaminants and study areas. The exception was for the lowest concentrations of organic contaminants (e.g. perfluorooctane sulfonate, PFOS), which were generally found in the northern Swedish mountain area. Concentrations of metals and organic contaminants in adults varied seasonally with most organic contaminants being higher in spring; likely induced by diet shifts but potentially also related to age differences. In addition, metal concentrations varied between organs (liver vs. kidney), age classes (juveniles vs. adults; generally higher in adults) as well as between males and females. Concentrations of chromium and nickel in kidney and liver in the northernmost mountain area were lower in 2017–2018 than in 1995–1997 and in three of four areas, lead concentrations were lower in 2017–2018 than in 2001. Current metal concentrations (except mercury) are not expected to negatively affect the voles. Concentrations of hexachlorobenzene displayed highest concentrations in 2001 in the mountains, while it was close to detection limit in 2017–2018. Likewise, PFOS concentrations decreased in the mountains and in south-central lowland forests between 2001 and 2017–2018. Our results suggest that season, age class and sex need to be considered when designing and interpreting results from monitoring programs targeting inorganic and organic contaminants in wildlife.
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| 2. |
- Spaan, Kyra M., et al.
(författare)
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Fluorine Mass Balance and Suspect Screening in Marine Mammals from the Northern Hemisphere
- 2020
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Ingår i: Environmental Science and Technology. - : American Chemical Society (ACS). - 0013-936X .- 1520-5851. ; 54:7, s. 4046-4058
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Tidskriftsartikel (refereegranskat)abstract
- There is increasing evidence that the similar to 20 routinely monitored perfluoroalkyl and polyfluoroalkyl substances (PFASs) account for only a fraction of extractable organofluorine (EOF) occurring in the environment. To assess whether PFAS exposure is being underestimated in marine mammals from the Northern Hemisphere, we performed a fluorine mass balance on liver tissues from 11 different species using a combination of targeted PFAS analysis, EOF and total fluorine determination, and suspect screening. Samples were obtained from the east coast United States (US), west and east coast of Greenland, Iceland, and Sweden from 2000 to 2017. Of the 36 target PFASs, perfluorooctane sulfonate (PFOS) dominated in all but one Icelandic and three US samples, where the 7:3 fluorotelomer carboxylic acid (7:3 FTCA) was prevalent. This is the first report of 7:3 FTCA in polar bears (similar to 1000 ng/g, ww) and cetaceans (<6-190 ng/g, ww). In 18 out of 25 samples, EOF was not significantly greater than fluorine concentrations derived from sum target PFASs. For the remaining 7 samples (mostly from the US east coast), 30-75% of the EOF was unidentified. Suspect screening revealed an additional 37 PFASs (not included in the targeted analysis) bringing the total to 63 detected PFASs from 12 different classes. Overall, these results highlight the importance of a multiplatform approach for accurately characterizing PFAS exposure in marine mammals.
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| 3. |
- 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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| 4. |
- 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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| 5. |
- Schultes, Lara, et al.
(författare)
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High Concentrations of Unidentified Extractable Organofluorine Observed in Blubber from a Greenland Killer Whale (Orcinus orca)
- 2020
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Ingår i: Environmental Science and Technology Letters. - : American Chemical Society (ACS). - 2328-8930. ; 7:12, s. 905-915
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Tidskriftsartikel (refereegranskat)abstract
- It is generally accepted that per- and polyfluoroalkyl substances (PFASs) occur primarily in protein-rich tissues such as blood and liver, but few studies have examined the occurrence of legacy and novel PFASs in lipid-rich tissues such as blubber. Here we report the distribution of 24 PFASs, total fluorine, and extractable organic fluorine (EOF) in eight different tissues of a killer whale (Orcinus orca) from East Greenland. The sum of target PFAS concentrations was highest in liver (352 ng/g of wet weight) and decreased in the following order: blood > kidney ≈ lung ≈ ovary > skin ≈ muscle ≈ blubber. Most of the EOF consisted of known PFASs in all tissues except blubber, which displayed the highest concentration of EOF, almost none of which was attributed to targeted PFASs. Suspect screening using high-resolution mass spectrometry revealed the presence of additional PFASs but is unlikely to explain the high concentrations of EOF in blubber. While the identity of this unknown organofluorine and its pervasiveness in marine mammals require further investigation, this work suggests that exposure of killer whales to organofluorine substances may be underestimated by determination of legacy PFASs exclusively in liver or blood.
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| 6. |
- 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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| 7. |
- Fang, Shuhong, et al.
(författare)
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Levels of per- and polyfluoroalkyl substances (PFAS) in ski wax products on the market in 2019 indicate no changes in formulation
- 2020
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Ingår i: Environmental Science. - : Royal Society of Chemistry (RSC). - 2050-7887 .- 2050-7895. ; 22:11, s. 2142-2146
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Tidskriftsartikel (refereegranskat)abstract
- In the summer of 2019, eleven of the best-selling fluorinated ski wax products were purchased from one of Norway's largest sports stores and soon after analysed for a suite of 26 per- and polyfluoroalkyl substances (PFAS). The waxes were shown to contain a wide range of perfluoroalkyl acids, including perfluoroalkyl carboxylic acids with up to 25 carbons. Of particular concern was the finding that perfluorooctanoic acid (PFOA) levels in nine of the eleven ski lubrication products analysed were above the EU limit values of 25 ng g(-1), which came into force on 4(th) July 2020. The ski wax with the highest PFOA levels had a concentration that was 1215 times higher than the EU restrictions. Although some of the ski wax manufacturers have indicated that they have switched to formulations that contain chemistries based on shorter perfluoroalkyl chains, the analytical results show that this is not the case.
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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. |
- Liagkouridis, Ioannis, et al.
(författare)
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Combined Use of Total Fluorine and Oxidative Fingerprinting for Quantitative Determination of Side-Chain Fluorinated Polymers in Textiles
- 2022
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Ingår i: Environmental Science and Technology Letters. - : American Chemical Society. - 2328-8930. ; 9:1, s. 30-
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Tidskriftsartikel (refereegranskat)abstract
- Given their extensive production volumes and potential to form persistent perfluoroalkyl acids (PFAAs), there is concern surrounding the ongoing use of side-chain fluorinated polymers (SFPs) in consumer products. Targeted SFP quantification relies on matrix-assisted laser desorption ionization time-of-flight mass spectrometry, which can suffer from poor accuracy and high detection limits. Alternatively, total fluorine (TF)-based methods may be used, but these approaches report concentrations on a "fluorine equivalent"basis (e.g., fluorine per square meter in the case of textiles) and are incapable of elucidating structure or chain length. Here a new method for comprehensive characterization of SFPs is presented, which makes use of the total oxidizable precursor assay for fingerprint-based structural elucidation and combustion ion chromatography for TF quantification. When used in parallel, quantitative determination of SFPs (in units of mass of CnF2n+1 per square meter of textile) is achieved. Expressing SFP concentrations in terms of the mass of the side chain (as opposed to fluorine equivalents) facilitates estimation of both the structure and quantity of PFAA degradation products. As a proof of principle, the method was applied to six unknown SFP-coated medical textiles from Sweden. Four products contained C6-fluorotelomer-based SFPs (concentration range of 36-188 mg of C6F13/m2), one contained a C4-sulfonamide-based SFP (718 mg of C4F9/m2), and one contained a C8-fluorotelomer-based SFP (249 mg of C8F17/m2). © 2021 The Authors.
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| 10. |
- Miaz, Luc T., et al.
(författare)
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Temporal trends of suspect- and target-per/polyfluoroalkyl substances (PFAS), extractable organic fluorine (EOF) and total fluorine (TF) in pooled serum from first-time mothers in Uppsala, Sweden, 1996–2017
- 2020
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Ingår i: Environmental Science. - : Royal Society of Chemistry (RSC). - 2050-7887 .- 2050-7895. ; 22:4, s. 1071-1083
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Tidskriftsartikel (refereegranskat)abstract
- A combined method for quantitative analysis, along with suspect and non-target screening of per- and polyfluoroalkyl substances (PFAS) was developed using ultra-high pressure liquid chromatography-ultra-high resolution (Orbitrap) mass spectrometry. The method was applied together with measurements of total- and extractable organofluorine (TF and EOF, respectively), to pooled serum samples from 1996–2017 from first-time mothers living in the county of Uppsala, Sweden, some of which (i.e. 148 of 472 women sampled 1996–2012) were exposed to drinking water contaminated with perfluorohexane sulfonate (PFHxS) and other PFAS until mid-2012. Declining trends were observed for all target PFAS as well as TF, with homologue-dependent differences in year of onset of decline. Only 33% of samples displayed detectable EOF, and amongst these samples the percentage of EOF explained by target PFAS declined significantly (−3.5% per year) over the entire study period. This finding corroborates prior observations in Germany after the year 2000, and may reflect increasing exposure to novel PFAS which have not yet been identified. Suspect screening revealed the presence of perfluoro-4-ethylcyclohexanesulfonate (PFECHS), which displayed declining trends since the year 2000. Non-target time trend screening revealed 3 unidentified features with time trends matching PFHxS. These features require further investigation, but may represent contaminants which co-occurred with PFHxS in the contaminated drinking water.
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| 11. |
- Miaz, Luc T, et al.
(författare)
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Temporal trends of suspect and target per/polyfluoroalkyl substances (PFASs), Extractable organic fluorine (EOF) and total fluorine (TF) in pooled serum from first-time mothers in Uppsala 1996-2017
- 2020
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Rapport (övrigt vetenskapligt/konstnärligt)abstract
- A combined method for quantitative, suspect, and non-target screening of per- and polyfluoroalkyl substances (PFASs) was developed using ultra-high pressure liquid chromatography-ultra-high resolution (Orbitrap) mass spectrometry. The method was applied together with measurements of total- and extractable organofluorine (TF and EOF, respectively), to pooled serum samples from 1996–2017 from first-time mothers living in the county of Uppsala, Sweden, some of which were exposed to drinking water contaminated with perfluorohexane sulfonate (PFHxS) and other PFASs until mid-2012. Declining trends were observed for all target PFASs as well as TF, with homologue-dependent differences in year of onset of decline. Only 33% of samples displayed detectable EOF, and amongst these samples the percentage of EOF explained by target PFASs declined significantly (−3.5% per year) over the entire study period. This finding corroborates prior observations in Germany after the year 2000, and may reflect increasing exposure to novel PFASs which have not yet been identified. Non-target time trend screening revealed 3 unidentified features with time trends matching PFHxS (Spearman’s ρ > 0.5). These features require further investigation, but may represent contaminants which co-occurred with PFHxS in the contaminated drinking water.
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| 12. |
- Mustafa, Majid, et al.
(författare)
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Fluorine mass balance and suspect screening in first-time mothers from Uppsala, Sweden: Results for years 2018-2021
- 2024
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Rapport (övrigt vetenskapligt/konstnärligt)abstract
- Sedan 1996 har Livsmedelsverket regelbundet samlat in blodprover från förstföderskor i Uppsala för analys av persistenta organiska miljöföroreningar (POP). Poly- och perfluorerade alkylsyror (PFAS) är en sådan substansgrupp. Huvudsyftet med denna studie var att fortsätta de tidigare trenderna för fluormassbalans i serum från förstföderskor i POPUP-kohorten (1996–2017), med ytterligare fyra år (2018-2021). Dessutom gjordes suspect screening med särskild fokus på fluorerade läkemedel och bekämpningsmedel med hjälp av högupplöst masspektrometri. Resultaten visar att halterna för PFAS och totalt fluor (TF) fortsätter att minska under de senaste åren. Även om det inte observerades någon trend för extraherbart organiskt fluor (EOF) visade en jämförelse mellan halterna av summaPFAS och EOF-nivåer en ökning av den procentuella andelen oidentifierad EOF under de senaste åren. En pool år 2019 visade särskilt höga TF och EOF-nivåer, vilket troligtvis kan tillskrivas läkemedlet Escitalopram som utifrån enkätsvar används av en deltagare i denna pool. Suspect screening-analysen identifierade preliminärt 5 nya organofluorämnen som tidigare har rapporterats i fisk och humant serum från Great Lakes-regionen i USA, vilka föreslogs vara av naturligt ursprung. Dessa strukturer kräver bekräftelse med autentiska standarder. Sammantaget visar dessa data att trots minskande PFAS-koncentrationer är den övergripande exponeringen för PFAS sannolikt underskattad på grund av förekomsten av nya, tidigare oidentifierade ämnen.
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| 13. |
- 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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