An outdoor aging study to investigate the release of per- and polyfluoroalkyl substances (PFAS) from functional textiles

Schellenberger, S.; Liagkouridis, I.; Awad, R.; Khan, S.; Plassmann, M.; Peters, G.; Benskin, J.P.; Cousins, I.T.
2022 | Environ. Sci. Technol. | 56 (6) (3471-3479)

Combined Use of Total Fluorine and Oxidative Fingerprinting for Quantitative Determination of Side-Chain Fluorinated Polymers in Textiles

Liagkouridis, I.; Awad, R.; Schellenberger, S.; Plassmann, M.M.; Cousins, I.T.; Benskin, J.P.
2022 | Environ. Sci. Technol. Lett. | 9 (1) (30-36)

Development, validation, and application of a new method for the quantitative determination of monohydrogen-substituted perfluoroalkyl carboxylic acids (H-PFCAs) in surface water

Awchi, M; Gebbink, WA; Berendsen, BJA; Benskin, JP; van Leeuwen, SPJ
2022 | Chemosphere | 287
h-pfcas , lc-ms , line , ms , pfas , pfcas , samples , substances , surface water , suspect
Per- and polyfluoroalkyl substances (PFASs) are a large and diverse class of chemicals. While some have been phased out internationally due to concerns over their human and environmental health risks, novel alternative PFASs continue to be manufactured and detected in environmental samples. The occurrence and fate of these alternatives remain poorly understood. The present study investigated the occurrence of an emerging class of PFAS alternative, the monohydrogen-substituted perfluoroalkyl carboxylic acids (H-PFCAs), in conjunction with the more well-known PFCAs. A weak anion exchange solid phase extraction-liquid chromatography tandem mass spectrometry method for quantitative determination of H-PFCAs in surface water was developed, validated, and applied on samples collected from the Netherlands. To improve chromatography, especially for short-chain (H-) PFCAs, an ion-pairing agent, tetrabutylammonium hydrogen sulphate, was used. The method was validated for linearity (R2 > 0.99), instrumental detection limits (0.01-0.09 ng/mL), method detection limits (0.03-0.75 ng/ mL), matrix effects (<20%), percent absolute- and relative recovery (57-121%), trueness (130-80%), repeatability (<20%), and within-lab reproducibility (<20%). Eleven out of fourteen PFASs showed acceptable results. Application of the newly validated method to surface water throughout the Netherlands revealed trace levels of H-PFCAs (including two new H-PFCAs) and high concentrations of PFCAs.

Legacy and emerging organohalogenated compounds in feathers of Eurasian eagle-owls (Bubo bubo) in Norway: Spatiotemporal variations and associations with dietary proxies (delta C-13 and delta N-15)

Monclus, L; Loseth, ME; Persson, MJD; Eulaers, I; Kleven, O; Covaci, A; Benskin, JP; Awad, R; Zubrod, JP; Schulz, R; Wabakken, P; Heggoy, O; Oien, IJ; Steinsvag, MJ; Jaspers, VLB; Nygard, T
2022 | Environ. Res. | 204
arctic marine , biomonitoring tool , bird of prey , feathers , haliaeetus-albicilla nestlings , herring gull eggs , isotopes , laurentian great-lakes , ope , perfluorinated compounds , persistent organic pollutants , pfas , phosphorus flame retardants , polyfluoroalkyl substances , pop , temporal trends
The occurrence of organohalogenated compounds (OHCs) in wildlife has received considerable attention over the last decades. Among the matrices used for OHCs biomonitoring, feathers are particularly useful as they can be collected in a minimally or non-invasive manner. In this study, concentrations of various legacy OHCs -polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs) and polybmminated diphenyl ethers (PBDEs)-, as well as emerging OHCs -per- and polyfluoroalkyl substances (PFAS) and organophosphate ester flame retardants (OPEs)- were determined in feathers of 72 Eurasian eagle-owls (Bubo bubo) from Norway, with the goal of studying spatiotemporal variation using a non-invasive approach. Molted feathers were collected at nest sites from northern, central and southern Norway across four summers (2013-2016). Additionally, two museum-archived feathers from 1979 to 1989 were included. Stable carbon (delta 13C) and nitrogen isotopes (delta 15N) were used as dietary proxies. In total, 11 PFAS (sum range 8.25-215.90 ng g(-1)), 15 PCBs (4.19-430.01 ng g(-1)), 6 OCPs (1.48-220.94 ng g(-1)), 5 PBDEs (0.21-5.32 ng g(-1)) and 3 OPEs (4.49-222.21 ng g(-1)) were quantified. While we observed large variation in the values of both stable isotopes, suggesting a diverse diet of the eagleowls, only delta 13C seemed to explain variation in PFAS concentrations. Geographic area and year were influential factors for delta 15N and delta 13C. Considerable spatial variation was observed in PFAS levels, with the southern area showing higher levels compared to northern and central Norway. For the rest of OHCs, we observed between-year variations; sum concentrations of PCBs, OCPs, PBDEs and OPEs reached a maximum in 2015 and 2016. Concentrations from 1979 to 1989 were within the ranges observed between 2013 and 2016. Overall, our data indicate high levels of legacy and emerging OHCs in a top predator in Norway, further highlighting the risk posed by OHCs to wildlife.

Rapid in-plate screening of biotransformation products in single zebrafish embryos

Ribbenstedt, A; Benskin, JP
2021 | RSC Adv | 11 (45) (27812-27819)
chemicals , danio-rerio , dog , fate , ms/ms , pharmaceuticals , propranolol metabolism , toxicokinetics , urine , water treatment plants
A procedure was developed for rapid screening of xenobiotic biotransformation products (bioTPs) in single zebrafish (ZF; Danio rerio) embryos. Exposure was carried out from 0-120 hours post fertilization (hpf) to 6 different concentrations of the model compound propranolol (PPL). Following in-plate extraction and non-target instrumental analysis by high resolution mass spectrometry, suspected bioTPs were identified using custom data filtration scripts and matching to in silico structural predictions. A total of eight PPL bioTPs were identified (five at a level 1 confidence and one at a level 2-3 confidence). These findings supplement previously generated toxicometabolomic models derived from the same dataset, and were obtained without conducting additional exposure experiments. In addition to facilitating assessments of inter-individual variability in bioTP production in ZF embryos, we demonstrate that bioTPs can be elucidated using extremely small quantities of biomass (i.e. similar to 200 mu g). To the best of our knowledge, this is the first time bioTP elucidation has been carried out in single ZF embryos.

Influence of Water Concentrations of Perfluoroalkyl Acids (PFAAs) on Their Size-Resolved Enrichment in Nascent Sea Spray Aerosols

2021 | Environ. Sci. Technol. | 55 (14) (9489-9497)
adsorption , anionic surfactants , atmosphere , fate , fractionation , inventories , polyfluoroalkyl substances pfass , sulfonate , to-air transfer , transport
Perfluoroalkyl acids (PFAAs) are persistent organic substances that have been widely detected in the global oceans. Previous laboratory experiments have demonstrated effective enrichment of PFAAs in nascent sea spray aerosols (SSA), suggesting that SSA are an important source of PFAAs to the atmosphere. In the present study, the effects of the water concentration of PFAAs on their size-resolved enrichment in SSA were examined using a sea spray simulation chamber. Aerosolization of the target compounds in almost all sizes of SSA revealed a strong linear relationship with their water concentrations (p < 0.05, r(2) > 0.9). The enrichment factors (EF) of the target compounds showed no correlation with their concentrations in the chamber water, despite the concentrations varying by a factor of 500 (similar to 0.3 to similar to 150 ng L-1). The particle surface-area-to-volume ratio appeared to be a key predictor of the enrichment of perfluoroalkyl carboxylic acids (PFCAs) with >= 7 perfluorinated carbons and perfluoroalkanesulfonic acids (PFSAs) with >= 6 perfluorinated carbons in supermicron particles (p < 0.05, r(2) > 0.8), but not in submicron particles. The different enrichment behaviors of PFAAs in submicron and supermicron particles might be a result of the different production mechanisms of film droplets and jet droplets. The results suggest that the variability in seawater concentrations of PFAAs has little influence on EFs and that modeling studies designed to quantify the source of PFAAs via SSA emissions do not need to consider this factor.

Can determination of extractable organofluorine (EOF) be standardized? First interlaboratory comparisons of EOF and fluorine mass balance in sludge and water matrices

Karrman, A; Yeung, LWY; Spaan, KM; Lange, FT; Nguyen, MA; Plassmann, M; De Wit, CA; Scheurer, M; Awad, R; Benskin, JP
2021 | Environ. Sci.-Process Impacts | 23 (10) (1458-1465)
combustion ion chromatography , organic fluorine , perfluoroalkyl substances , polyfluoroalkyl substances , precursors , samples
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 ( n-ary sumation 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).

Emerging per- and polyfluoroalkyl substances (PFAS) in human milk from Sweden and China (vol 22, pg 2023, 2020)

Awad, R; Zhou, YH; Nyberg, E; Namazkar, S; Wu, YN; Xiao, QF; Sun, YJ; Zhu, ZL; Bergman, A; Benskin, JP
2021 | Environ. Sci.-Process Impacts | 23 (1) (188-188)

Bioaccumulation of Per- and polyfluoroalkyl substances (PFASs) in a tropical estuarine food web

Miranda, DA; Benskin, JP; Awad, R; Lepoint, G; Leonel, J; Hatje, V
2021 | Sci. Total Environ. | 754
biomagnification , brazil , os-santos bay , perfluorinated compounds , perfluoroalkyl acids pfaas , perfluorooctane sulfonate , persistent organic pollutants , pfos precursors , pops , sulfluramid use , tissue distribution , todos os santos bay , trace-metal contamination , trophic magnification factors , tropical food web
The biomagnification of per- and polyfluoroalkyl substances (PFASs) was investigated in a tropical mangrove food web from an estuary in Bahia, Brazil. Samples of 44 organisms (21 taxa), along with biofilm, leaves, sediment and suspended particulate matter were analyzed. Sum (Sigma) PFAS concentrations in biota samples were dominated by perfluorooctane sulfonate (PFOS, 93% detection frequency in tissues; 0.05 to 1.97 ng g(-1) ww whole-body (wb)), followed by perfluorotridecanoate (PFTrDA, 57%; 0.01 to 0.28 ng g(-1) ww wb). PFOS precursors such as perfluorooctane sulfonamide (FOSA, 54%; 0.01 to 0.32 ng g(-1) ww wb) and N-ethyl perfluorooctane sulfonamide (EtFOSA; 30%; 0.01 to 0.21 ng g(-1) ww wb) were also detected. PFAS accumulation profiles revealed different routes of exposure among bivalve, crustacean and fish groups. Statistics for left-censored data were used in order to minimize bias on trophic magnification factors (TMFs) calculations. TMFs >1 were observed for PFOS (linear + branched isomers), EtFOSA (linear + branched isomers), and perfluorononanoate (PFNA), and in all cases, dissimilar accumulation patterns were observed among different trophic positions. The apparent biodilution of some long-chain PFCAs through the food chain (TMF < 1) may be due to exposure from multiple PFAS sources. This is the first study investigating bioaccumulation of PFASs in a tropical food web and provides new insight on the behavior of this ubiquitous class of contaminants. (C) 2020 The Authors. Published by Elsevier B.V.

Suspect and non-target screening of ovarian follicular fluid and serum – identification of anthropogenic chemicals and investigation of their association to fertility

Hallberg, I; Plassmann, M; Olovsson, M; Holte, J; Damdimopoulou, P; Sjunnesson, YCB; Benskin, JP; Persson, S
2021 | Environ. Sci.-Process Impacts | 23 (10) (1578-1588)
bisphenol-a concentrations , contaminants , embryo score , exposure , infertility , mass spectrometry , perfluorinated chemicals , perfluoroalkyl , polychlorinated biphenyls , women
In this work, ultra-high performance liquid chromatography-high resolution (Orbitrap) mass spectrometry-based suspect and non-target screening was applied to follicular fluid (n = 161) and serum (n = 116) from women undergoing in vitro fertilization in order to identify substances that may be associated with decreased fertility. Detected features were prioritized for identification based on (i) hazard/exposure scores in a database of chemicals on the Swedish market and an in-house database on per- and polyfluoroalkyl substances (PFAS); (ii) enrichment in follicular fluid relative to serum; and (iii) association with treatment outcomes. Non-target screening detected 20 644 features in follicular fluid and 13 740 in serum. Two hundred and sixty-two features accumulated in follicular fluid (follicular fluid: serum ratio >20) and another 252 features were associated with embryo quality. Standards were used to confirm the identities of 21 compounds, including 11 PFAS. 6-Hydroxyindole was associated with lower embryo quality and 4-aminophenol was associated with higher embryo quality. Overall, we show the complexity of follicular fluid and the applicability of suspect and non-target screening for discovering both anthropogenic and endogenous substances, which may play a role in fertility in women.

Hyporheic exchange in recirculating flumes under heterogeneous bacterial and morphological conditions

Betterle, A; Jaeger, A; Posselt, M; Coll, C; Benskin, JP; Schirmer, M
2021 | Environ. Earth Sci. | 80 (6)
biodegradation , hyporheic exchange , hyporheic zone , modelling , pollutants , surface water porewater interaction
Hyporheic exchange (HE) contributes to the biogeochemical turnover of macro- and micro-pollutants in rivers. However, the spatiotemporal complexity and variability of HE hinder understanding of its role in the overall functioning of riverine ecosystems. The present study focuses on investigating the role of bacterial diversity and sediment morphology on HE using a multi-flume experiment. A fully coupled surface-subsurface numerical model was used to highlight complex exchange patterns between surface water and the underlying flow field in the sediments. Under the experimental conditions, the surface water flow induced by bedforms has a prominent effect on both local trajectories and residence time distributions of hyporheic flow paths, whereas mean hyporheic retention times are mainly modulated by average surface flowrates. In case of complex bedform morphologies, the numerical model successfully reproduces the HE estimated by means of salt dilution tests. However, the 2D numerical representation of the system falls short in predicting HE in absence of bedforms, highlighting the intrinsic complexity of water circulation patterns in real scenarios. Finally, results show that higher bacterial diversities in the stream sediments can significantly reduce hyporheic fluxes. This work provides a framework to interpret micropollutants turnover in light of the underlying physical transport processes in the hyporheic zone. The study emphasizes the importance of better understanding the tradeoff between physically driven transport processes and bacterial dynamics in the hyporheic zone to quantify the fate of pollutants in streams and rivers.

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