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Paper product production identified as the main source of per- and polyfluoroalkyl substances (PFAS) in a Norwegian lake: Source and historic emission tracking
2021
Langberg, Håkon A. | Arp, Hans Peter H. | Breedveld, Gijs D. | Slinde, Gøril A. | Høiseter, Åse | Grønning, Hege M. | Jartun, Morten | Rundberget, Thomas | Jenssen, Bjørn M. | Hale, Sarah E.
The entirety of the sediment bed in lake Tyrifjorden, Norway, is contaminated by per- and polyfluoroalkyl substances (PFAS). A factory producing paper products and a fire station were investigated as possible sources. Fire station emissions were dominated by the eight carbon perfluoroalkyl sulfonic acid (PFSA), perfluorooctanesulfonic acid (PFOS), from aqueous film forming foams. Factory emissions contained PFOS, PFOS precursors (preFOS and SAmPAP), long chained fluorotelomer sulfonates (FTS), and perfluoroalkyl carboxylic acids (PFCA). Concentrations and profiles in sediments and biota indicated that emissions originating from the factory were the main source of pollution in the lake, while no clear indication of fire station emissions was found. Ratios of linear-to branched-PFOS increased with distance from the factory, indicating that isomer profiles can be used to trace a point source. A dated sediment core contained higher concentrations in older sediments and indicated that two different PFAS products have been used at the factory, referred to here as Scotchban and FTS mixture. Modelling, based on the sediment concentrations, indicated that 42–189 tons Scotchban, and 2.4–15.6 tons FTS mixture, were emitted. Production of paper products may be a major PFAS point source, that has generally been overlooked. It is hypothesized that paper fibres released from such facilities are important vectors for PFAS transport in the aquatic environment.
Afficher plus [+] Moins [-]Per- and polyfluoroalkyl substances display structure-dependent inhibition towards UDP-glucuronosyltransferases
2019
Liu, Yong-Zhe | Zhang, Zhi-Peng | Fu, Zhi-Wei | Yang, Kun | Ding, Ning | Hu, Li-Gang | Fang, Zhong-Ze | Zhuo, Xiaozhen
Per- and polyfluoroalkyl substances (PFASs) are a large group of chemicals and can be detected in environmental and human samples all over the world. Toxicity of existing and emerging PFASs will be a long-term source of concern. This study aimed to investigate structure-dependent inhibitory effects of 14 PFASs towards the activity of 11 UDP-glucuronosyltransferase (UGT) isoforms. In vitro UGTs-catalyzed glucuronidation of 4-methylumbelliferone (4-MU) was employed to determine the inhibition of PFASs towards different UGT isoforms. All the PFASs showed <75% of inhibition or stimulation effects on UGT1A3, UGT1A7, UGT1A9, UGT2B4, UGT2B7 and UGT2B17. However, PFASs showed broad inhibition on the activity of UGT1A1 and UGT1A8. The activity of UGT1A1 was inhibited by 98.8%, 98%, 79.9%, 77.1%, and 76.9% at 100 μmoL/L of perfluorodecanoic acid (PFDA), perfluorooctanesulfonic acid potassium salt (PFOS), perfluorotetradecanoic acid (PFTA), perfluorooctanoic acid (PFOA) and perfluorododecanoic acid (PFDoA), respectively. UGT1A8 was inhibited by 97.6%, 94.8%, 86.3%, 83.4% and 77.1% by PFDA, PFTA, perfluorooctadecanoic acid (PFOcDA), PFDoA and PFOS, respectively. Additionally, PFDA significantly inhibited UGT1A6 and UGT1A10 by 96.8% and 91.6%, respectively. PFDoA inhibited the activity of UGT2B15 by 88.2%. PFDA and PFOS exhibited competitive inhibition towards UGT1A1, and PFDA and PFTA showed competitive inhibition towards UGT1A8. The inhibition kinetic parameter (Kᵢ) were 3.15, 1.73, 13.15 and 20.21 μmoL/L for PFDA-1A1, PFOS-1A1, PFDA-1A8 and PFTA-1A8, respectively. The values were calculated to be 0.3 μmoL/L and 1.3 μmoL/L for the in vivo inhibition of PFDA towards UGT1A1-and UGT1A8-catalyzed metabolism of substances, and 0.2 μmoL/L and 2.0 μmoL/L for the inhibition of PFOS towards UGT1A1 and the inhibition of PFTA towards UGT1A8, respectively. Molecular docking indicated that hydrogen bonds and hydrophobic interactions contributed to the interaction between PFASs and UGT isoforms. In conclusion, exposure to PFASs might inhibit the activity of UGTs to disturb metabolism of endogenous compounds and xenobiotics. The structure-related effects of PFASs on UGTs would be very important for risk assessment of PFASs.
Afficher plus [+] Moins [-]Bioaccumulation and biomagnification of perfluoroalkyl acids and precursors in East Greenland polar bears and their ringed seal prey
2019
Boisvert, Gabriel | Sonne, Christian | Rigét, Frank F. | Dietz, Rune | Letcher, Robert J.
The bioaccumulation and biomagnification of 22 major perfluoroalkyl substances (PFAS) were investigated in tissues of polar bears (Ursus maritimus) and their major prey species, the ringed seal (Pusa hispida), from the Scoresby Sound region of East Greenland. In polar bear liver the mean Σ4PFSA (perfluoroalkyl sulfonic acid) concentration (C4, C6, C8 and C10) was 2611 ± 202 ng/g wet weight (ww; 99% perfluorooctane sulfonate (PFOS)) and two orders of magnitude higher than the 20 ± 3 ng/g ww (89% PFOS) concentration in fat. The mean Σ4PFSAs in seal liver was 111 ± 5 ng/g ww (98% PFOS) and three orders of magnitude higher relative to the 0.05 ± 0.01 ng/g ww concentration in blubber (100% perfluorohexane sulfonate). Perfluoro-1-octane sulfonamide (FOSA) was quantifiable in bear (mean 10 ± 1.4 ng/g ww) and seal (mean 0.6 ± 0.1 ng/g ww) liver but not in fat or blubber. The mean Σ13PFCAs (C4–C18; perfluoroalkyl carboxylic acids) in bear liver (924 ± 71 ng/g ww) was much greater than in seal liver (74 ± 6 ng/g ww). In bear fat and seal blubber, the mean Σ13PFCAs were 15 ± 1.9 and 0.9 ± 0.1 ng/g ww, respectively. Longer chain C11 to C14 PFCAs dominated in bear fat and seal blubber (60–80% of Σ13PFCA), whereas shorter-chain C9 to C11 PFCAs dominated in the liver (85–90% of Σ13PFCA). Biomagnification factors (BMFs) were orders of magnitude greater for PFHxS and C9 to C13 PFCAs when based on bear liver to seal blubber rather than bear liver to seal liver, and PFCA (C9 to C13) BMFs decreased with increasing chain length. Seal blubber to bear liver BMFs better reflects the dietary exposure relationship of PFAS between bears and seals.
Afficher plus [+] Moins [-]Azo dye biotransformation mediated by AQS immobilized on activated carbon cloth in the presence of microbial inhibitors
2019
Castañon, Daniel | Alvarez, Luis H. | Peña, Karen | García-Reyes, Refugio B. | Martinez, Claudia M. | Pat-Espadas, Aurora
In this work, anthraquinone-2-sulfonate (AQS) was covalently immobilized onto activated carbon cloth (ACC), to be used as redox mediator for the reductive decolorization of reactive red 2 (RR2) by an anaerobic consortium. The immobilization of AQS improved the capacity of ACC to transfer electrons, evidenced by an increment of 3.29-fold in the extent of RR2 decolorization in absence of inhibitors, compared to incubations lacking AQS. Experiments conducted in the presence of vancomycin, an inhibitor of acidogenic bacteria, and with 2-bromoethane sulfonic acid (BES), an inhibitor of methanogenic archaea, revealed that acidogenic bacteria are the main responsible for RR2 biotransformation mediated by immobilized AQS. Nonetheless, the results also suggest that some methanogens are able to maintain their capacity to use immobilized AQS as an electron acceptor to sustain the decolorization process, even in the presence of BES.
Afficher plus [+] Moins [-]Sex differences in the association between perfluoroalkyl acids and liver function in US adolescents: Analyses of NHANES 2013–2016
2019
Attanasio, Roberta
Perfluoroalkyl acids (PFAAs) are persistent in the environment, highly bio-accumulative in the body, and likely hepatotoxic in humans. There is evidence of sex-specific physiological responses to PFAA exposure. However, epidemiological studies seldom stratify the analyses by sex. Given the high prevalence of liver disease in general population adolescents, this study was designed to determine whether or not there is association between exposure to PFAAs and biomarkers of liver function in adolescent participants of the 2013–2016 National Health and Nutrition Examination Survey, and whether or not such association is sex-specific. Multivariate linear regressions were performed to examine the association between single PFAAs [perfluorooctane sulfonic acid (PFOS); linear form of perfluorooctanoic acid (PFOA); perfluorohexane sulfonic acid (PFHxS); perfluorononanoic acid (PFNA)], and biomarkers of liver function — gamma glutamyltransferase (GGT), aspartate aminotransferase (AST), alanine aminotransferase (ALT), and total bilirubin. Multivariate logistic regressions were performed to estimate adjusted odd ratios (aOR) of elevated ALT, AST and GGT. The study results show that, in females, there was a positive association of the highest PFOA quartile with increased ALT, AST and GGT, and the highest PFNA quartile with increased ALT and AST. Conversely, in male adolescents there was an association of the highest linear PFOA quartile with decreased ALT, and the highest PFNA quartile with ALT and AST. Females had higher odds of clinically-defined elevated ALT with increased PFOA (aOR = 1.79; 95% CI: 1.05, 3.04) or PFNA (aOR = 2.28; 95% CI: 1.08, 2.28), whereas males had decreased odds of clinically-defined elevated ALT with increased n-PFOA (aOR = 0.43; 95% CI: 0.20, 0.93) or PFNA (aOR = 0.5; 95% CI: 0.28, 0.89). In conclusion, there were sex differences in the association between serum PFAA levels and biomarkers of liver function. These results may provide support for analyzing sex-based adverse effects of PFAAs.
Afficher plus [+] Moins [-]Spatial distribution and source tracing of per- and polyfluoroalkyl substances (PFASs) in surface water in Northern Europe
2017
Nguyen, Minh A. | Wiberg, Karin | Ribeli, Erik | Josefsson, Sarah | Futter, Martyn | Gustavsson, Jakob | Ahrens, Lutz
The impact of point and diffuse sources for 26 per- and polyfluoroalkyl substances (PFASs) in northern Europe were investigated by studying Swedish rivers (n = 40) and recipient seawater (Baltic Sea and Kattegat; n = 18). Different composition profiles were observed in the rivers, with ten rivers having a remarkably high fraction of perfluoroalkane sulfonic acids (PFSAs; 65% of the ƩPFASs) as compared to other rivers (19%) suggesting major impact of one or several source types dominated by PFSAs. Population density and low latitude (south) were strongly correlated to the widely used perfluorooctanesulfonic acid (PFOS), perfluorooctanoic acid (PFOA) as well as to perfluorohexanesulfonic acid (PFHxS). Significant relationships between several PFCAs and PFSAs (i.e. perfluorobutanoic acid (PFBA), perfluoroheptanoic acid (PFHpA), PFOA, perfluorobutanesulfonic acid (PFBS), and PFHxS) and dissolved organic carbon (DOC) were detected (p < 0.05), indicating chemical binding and co-transport with DOC in fresh water and seawater. Partial least squares regression analysis showed that perfluoroalkyl carboxylic acids (PFCAs) were related to latitude according to their perfluorocarbon chain length (C3, C7, C8, C9, C10 and C11), with longer chains associated with higher latitudes. This suggests the presence of mechanisms promoting higher prevalence of longer chained PFCAs in the north, e.g. precursor degradation, and/or aerosol associated stabilization of PFCAs and their precursors.
Afficher plus [+] Moins [-]Characterization of occurrence, sources and sinks of perfluoroalkyl and polyfluoroalkyl substances (PFASs) in a tropical urban catchment
2017
Chen, Huiting | Reinhard, Martin | Nguyen, Tung Viet | You, Luhua | He, Yiliang | Gin, Karina Yew-Hoong
Understanding the sources, occurrence and sinks of perfluoroalkyl and polyfluoroalkyl substances (PFASs) in the urban water cycle is important to protect and utilize local water resources. Concentrations of 22 target PFASs and general water quality parameters were determined monthly for a year in filtered water samples from five tributaries and three sampling stations of an urban water body. Of the 22 target PFASs, 17 PFASs were detected with a frequency >93% including PFCAs: C4-C12 perfluoroalkyl carboxylates, C4, C6, C8, and C10 perfluoroalkane sulfonates, perfluorooctane sulfonamides and perfluorooctane sulfonamide substances (FOSAMs), C10 perfluoroalkyl phosphonic acid (C10 PFPA), 6:2 fluorotelomer sulfonic acid (6:2 FTSA) and C8/C8 perfluoroalkyl phosphinic acid (C8/C8-PFPIA). The most abundant PFASs in water were PFBS (1.4–55 ng/L), PFBA (1.0–23 ng/L), PFOS (1.5–24 ng/L) and PFOA (2.0–21 ng/L). In the tributaries, PFNA concentrations ranged from 1.2 to 87.1 ng/L except in the May 2013 samples of two tributaries, which reached 520 and 260 ng/L. Total PFAS concentrations in the sediment samples ranged from 1.6 to 15 ng/g d.w. with EtFOSAA, PFDoA, PFOS and PFDA being the dominant species. Based on water and sediment data, two types of sources were inferred: one-time or intermittent point sources and continuous non-point sources. FOSAMs and PFOS released continually from non-point sources, C8/C8 PFPIA, PFDoA and PFUnA was released from point sources. The highly water soluble short-chain PFASs including PFBA, PFPeA and PFBS remained predominantly in the water column. The factors governing solution phase concentrations appear to be compound hydrophobicity and sorption to suspended particles. Correlation of the dissolved phase concentrations with precipitation data suggested stormwater was a significant source of PFBA, PFBS, PFUnA and PFDoA. Negative correlations with precipitation indicated sources feeding FOSAA and FOSA directly into the tributaries.
Afficher plus [+] Moins [-]Coupled production and emission of short chain perfluoroalkyl acids from a fast developing fluorochemical industry: Evidence from yearly and seasonal monitoring in Daling River Basin, China
2016
Wang, Pei | Lü, Yonglong | Wang, Tieyu | Zhu, Zhaoyun | Li, Qifeng | Meng, Jing | Su, Hongqiao | Johnson, Andrew C. | Sweetman, A. J. (Andrew J.)
Short chain perfluoroalkyl acids (PFAAs) have been developed since 2002 by the major manufacturers to replace the conventional C8 and higher homologues, with much of the world production shifted to China in recent years. In this study, we conducted a continuous monitoring program over the period 2011–2014 with seasonal monitoring in 2013 for PFAAs emitted from two rapidly developing fluorochemical industry parks located in the Daling River Basin, Northern China. The trend of PFAA contamination was identified, dominated by perfluorobutane sulfonic acid (PFBS), perfluorobutanoic acid (PFBA) and perfluorooctanoic acid (PFOA), with the maximum concentrations of 3.78 μg/L, 3.70 μg/L, and 1.95 μg/L, respectively. Seasonal monitoring uncovered the occasional emission of perfluorooctane sulfonic acid (PFOS). Construction trends of new facilities and associated manufacturing capacity of the main products were also analyzed to assess correlations with PFAA emissions. An assessment of the data over the period 2011–2014 found a positive correlation with fluorocarbon alcohol (FCA) production and emission of PFAAs. Groundwater and tap water around the main source indicated that the dominant PFAAs had different diffusion behaviors. PFBS levels were higher in surface water, while PFBA was dominant in groundwater and tap water, with PFOA levels being higher in downstream groundwater. Considering the continuous expansion and development of fluorochemical industry in the Daling River Basin, this study will provide abundant information on the effectiveness of risk assessment and management.
Afficher plus [+] Moins [-]Transport of perfluoroalkyl acids in a water-saturated sediment column investigated under near-natural conditions
2014
Vierke, Lena | Möller, Axel | Klitzke, Sondra
The aim of this study was to gain an understanding of the transport of C4–10 perfluoroalkyl carboxylic acids (PFCAs) and C4,6,8 perfluoroalkyl sulfonic acids (PFSAs) in a water-saturated sediment column representing a riverbank filtration scenario under near-natural conditions. Short-chain PFCAs and PFSAs with up to six C-atoms showed complete tracer-like breakthrough. Longer chain ones were retarded due to sorption to the sediment or due to other processes in the aqueous phase. The study reports the first column derived sediment–water partition coefficients ranging from 0.01 cm3 g−1 to 0.41 cm3 g−1 for C4,6 PFSAs and from 0.0 cm3 g−1 to 6.5 cm3 g−1 for C4,5,6,8,9 PFCAs. The results clearly indicate that short-chain PFCAs and PFSAs may pose a problem if contaminated surface waters are used for drinking water production via riverbank filtration.
Afficher plus [+] Moins [-]Temporal trends (1999–2010) of perfluoroalkyl acids in commonly consumed food items
2014
Johansson, Jana H. | Berger, Urs | Vestergren, Robin | Cousins, Ian T. | Bignert, Anders | Glynn, Anders | Darnerud, Per Ola
The aim of this study was to determine how dietary exposure to PFAAs has changed over the period when major production changes occurred. Archived samples (1999–2010) of eggs, milk and farmed rainbow trout were analyzed by ultra performance liquid chromatography coupled to tandem mass spectrometry. Statistically significant decreasing trends were observed for concentrations of perfluorooctane sulfonic acid (PFOS) and perfluorohexane sulfonic acid (PFHxS) in fish (p < 0.002 and p < 0.032, respectively) and eggs (p < 0.001 for both compounds). Concentrations of PFOS in fish and eggs decreased by a factor of 10 and 40, respectively. In eggs there was also a statistically significant decreasing trend in concentrations of perfluorooctanoic acid (PFOA). The results of this study demonstrate that PFAA concentrations in food items from agricultural food chains and aquatic food chains close to sources respond rapidly to changes in environmental emissions. Implications for the overall understanding of human exposure are discussed.
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