Socio-demographic inequalities influence differences in the chemical exposome among Swedish adolescents.

Relatively little is known about the relationship between socio-demographic factors and the chemical exposome in adolescent populations. This knowledge gap hampers global efforts to meet certain UN sustainability goals. The present work addresses this problem in Swedish adolescents by discerning patterns within the chemical exposome and identify demographic groups susceptible to heightened exposures. Enlisting the Riksmaten Adolescents 2016-17 (RMA) study population (N = 1082) in human-biomonitoring, and using proportional odds ordinal logistic regression models, we examined the associations between concentrations of a diverse array of substances (N = 63) with the determinants: gender, age, participant/maternal birth country income per capita level, parental education levels, and geographic place of living (longitude/latitude). Participant/maternal birth country exhibited a significant association with the concentrations of 46 substances, followed by gender (N = 41), and longitude (N = 37). Notably, individuals born in high-income countries by high-income country mothers demonstrated substantially higher estimated adjusted means (EAM) concentrations of polychlorinated biphenyls (PCBs), brominated flame retardants (BFRs) and per- and polyfluoroalkyl substances (PFASs) compared to those born in low-income countries by low-income country mothers. A reverse trend was observed for cobalt (Co), cadmium (Cd), lead (Pb), aluminium (Al), chlorinated pesticides, and phthalate metabolites. Males exhibited higher EAM concentrations of chromium (Cr), mercury (Hg), Pb, PCBs, chlorinated pesticides, BFRs and PFASs than females. In contrast, females displayed higher EAM concentrations of Mn, Co, Cd and metabolites of phthalates and phosphorous flame retardants, and phenolic substances. Geographical disparities, indicative of north-to-south or west-to-east substance concentrations gradients, were identified in Sweden. Only a limited number of lifestyle, physiological and dietary factors were identified as possible drivers of demographic inequalities for specific substances. This research underscores birth country, gender, and geographical disparities as contributors to exposure differences among Swedish adolescents. Identifying underlying drivers is crucial to addressing societal inequalities associated with chemical exposure and aligning with UN sustainability goals.

Characterization and dermal bioaccessibility of residual- and listed PFAS ingredients in cosmetic products.

As a large group of chemicals with diverse properties, per- and polyfluoroalkyl substances (PFAS) have found extensive application throughout consumer products, including cosmetics. Little is known about the importance of dermal uptake as a human exposure pathway for PFAS. Here we investigate a suite of listed-ingredient and residual PFAS in cosmetic products, along with their dermal bioaccessibility using in vitro incubations with artificial sweat. Concentrations of volatile listed ingredients (including cyclic perfluorinated alkanes, perfluorinated ethers, and polyfluorinated silanes) in three products ranged from 876-1323 µg g-1, while polar listed ingredients (i.e., polyfluoroalkyl phosphate esters [PAPs]) in a single product occurred at up to 2427 µg g-1 (6 : 2/6 : 2 diPAP)). Residual perfluoroalkyl carboxylic acids (PFCAs) were also measured at concentrations ranging from 0.02-29 µg g-1. When listed ingredients were included, our targeted analysis accounted for up to 103% of the total fluorine, while highlighting ambiguous and/or incorrect International Nomenclature of Cosmetic Ingredient (INCI) names used in several products. Bioaccessibility experiments revealed that residual PFCAs readily partitioned to artificial sweat (bioaccessible fractions ranging from 43-76% for detectable substances) while listed ingredients (i.e., PAPs and neutral/volatile PFAS) displayed negligible partitioning. This work provides new insight into the occurrence of PFAS in cosmetic products, while furthering our understanding on their mechanisms of dermal uptake.

Closing the Organofluorine Mass Balance in Marine Mammals Using Suspect Screening and Machine Learning-Based Quantification.

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.

Identification and quantification of fluorinated polymers in consumer products by combustion ion chromatography and pyrolysis-gas chromatography-mass spectrometry.

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.

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.

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.

Low concentrations of perfluoroalkyl acids (PFAAs) in municipal drinking water associated with serum PFAA concentrations in Swedish adolescents.

While highly contaminated drinking water (DW) is a major source of exposure to perfluoroalkyl acids (PFAAs), the contribution of low-level contaminated DW (i.e. < 10 ng/L of individual PFAAs) to PFAA body burdens has rarely been studied. To address this knowledge gap, we evaluated the association between concentrations of perflurooctanoic acid (PFOA), perfluorononanoic acid (PFNA), perfluorohexane sulfonic acid (PFHxS) and perfluorooctane sulfonic acid (PFOS), and their sum (∑4PFAAs) in DW and serum in Swedish adolescents using weighted least squares regression. We paired serum PFAA concentrations in adolescents (age 10-21 years, n = 790) from the dietary survey Riksmaten Adolescents 2016-17 (RMA) with mean PFAA concentrations in water samples collected in 2018 from waterworks (n = 45) supplying DW to the participant residential and school addresses. The median concentrations of individual PFAAs in DW were < 1 ng/L. Median concentrations of PFNA and PFHxS in serum were < 1 ng/g, while those of PFOA and PFOS were 1-2 ng/g. Significant positive associations between PFAA concentrations in DW and serum were found for all four PFAAs and ∑4PFAAs, with estimated serum/DW concentration ratios ranging from 210 (PFOA) to 670 (PFHxS), taking exposure from sources other than DW (background) into consideration. The mean concentrations of PFHxS and ∑4PFAA in DW that would likely cause substantially elevated serum concentrations above background variation were estimated to 0.9 ng/L and 2.4 ng/L, respectively. The European Food Safety Authority has determined a health concern concentration of 6.9 ng ∑4PFAAs/mL serum. This level was to a large degree exceeded by RMA participants with DW ∑4PFAA concentrations above the maximum limits implemented in Denmark (2 ng ∑4PFAAs/L) and Sweden (4 ng ∑4PFAAs/L) than by RMA participants with DW concentrations below the maximum limits. In conclusion, PFAA exposure from low-level contaminated DW must be considered in risk assessment for adolescents.

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.

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.

Exposure of Swedish adolescents to elements, persistent organic pollutants (POPs), and rapidly excreted substances - The Riksmaten adolescents 2016-17 national survey.

Adolescence is a period of significant physiological changes, and likely a sensitive window to chemical exposure. Few nation-wide population-based studies of chemical body burdens in adolescents have been published. In the national dietary survey Riksmaten Adolescents (RMA) 2016-17, over 13 chemical substance groups, including elements, chlorinated/brominated/fluorinated persistent organic pollutants (POPs) were analysed in blood, and in urine metabolites of phthalates/phthalate alternatives, phosphorous flame retardants, polycyclic aromatic hydrocarbons (PAHs), and pesticides, along with bisphenols and biocide/preservative/antioxidant/UV filter substances (N = 1082, ages 11-21). The aim was to characterize the body burdens in a representative population of adolescents in Sweden, and to compare results with human biomonitoring guidance values (HBM-GVs). Cluster analyses and Spearman's rank order correlations suggested that concentrations of substances with known common exposure sources and similar toxicokinetics formed obvious clusters and showed moderate to very strong correlations (r ≥ 0.4). No clusters were formed between substances from different matrices. Geometric mean (GM) concentrations of the substances were generally less than 3-fold different from those observed among adolescents in NHANES (USA 2015-16) and GerES V (Germany 2014-17). Notable exceptions were brominated diphenyl ethers (PBDEs) with >20-fold lower GM concentrations, and the biocide triclosan and ultraviolet (UV) filter benzophenone-3 with >15-fold lower mean concentrations in RMA compared to NHANES. Exceedance of the most conservative HBM-GVs were observed for aluminium (Al, 26% of subjects), perfluorooctanesulfonic acid (PFOS, 19%), perfluorooctanoic acid (PFOA, 12%), lead (Pb, 12%), MBP (dibutyl phthalate metabolite, 4.8%), hexachlorobenzene (HCB, 3.1%) and 3-phenoxybenzoic acid (PBA, pyrethroid metabolite, 2.2%). Males showed a higher proportion of exceedances than females for Pb, HCB and PFOS; otherwise no gender-related differences in exceedances were observed. A higher proportion of males than females had a Hazard Index (HI) of substances with liver and kidney toxicity and neurotoxicity >1. Industrialized countries with similarly high standards of living, with some exceptions, show comparable average body burdens of a variety of toxic chemicals among adolescents from the general population. The exceedances of HBM-GVs and HIs strongly suggests that further efforts to limit chemical exposure are warranted.

Characterizing the Organohalogen Iceberg: Extractable, Multihalogen Mass Balance Determination in Municipal Wastewater Treatment Plant Sludge.

The large number and diversity of organohalogen compounds (OHCs) occurring in the environment poses a grand challenge to analytical chemists. Since no single targeted method can identify and quantify all OHCs, the size of the OHC "iceberg" may be underestimated. We sought to address this problem in municipal wastewater treatment plant (WWTP) sludge by quantifying the unidentified fraction of the OHC iceberg using targeted analyses of major OHCs together with measurements of total and extractable (organo)halogen (TX and EOX, respectively; where X = F, Cl, or Br). In addition to extensive method validation via spike/recovery and combustion efficiency experiments, TX and/or EOX were determined in reference materials (BCR-461 and NIST SRMs 2585 and 2781) for the first time. Application of the method to WWTP sludge revealed that chlorinated paraffins (CPs) accounted for most (∼92%) of the EOCl, while brominated flame retardants and per- and polyfluoroalkyl substances (PFAS) accounted for only 54% of the EOBr and 2% of the EOF, respectively. Moreover, unidentified EOF in nonpolar 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 WWTP sludge and offers a novel approach to prioritization of sample extracts for follow-up investigation.

Lithium-ion battery recycling: a source of per- and polyfluoroalkyl substances (PFAS) to the environment?

Recycling of lithium-ion batteries (LIBs) is a rapidly growing industry, which is vital to address the increasing demand for metals, and to achieve a sustainable circular economy. Relatively little information is known about the environmental risks posed by LIB recycling, in particular with regards to the emission of persistent (in)organic fluorinated chemicals. Here we present an overview on the use of fluorinated substances - in particular per- and polyfluoroalkyl substances (PFAS) - in state-of-the-art LIBs, along with recycling conditions which may lead to their formation and/or release to the environment. Both organic and inorganic fluorinated substances are widely reported in LIB components, including the electrodes and binder, electrolyte (and additives), and separator. Among the most common substances are LiPF6 (an electrolyte salt), and the polymeric PFAS polyvinylidene fluoride (used as an electrode binder and a separator). Currently the most common LIB recycling process involves pyrometallurgy, which operates at high temperatures (up to 1600 °C), sufficient for PFAS mineralization. However, hydrometallurgy, an increasingly popular alternative recycling approach, operates under milder temperatures (<600 °C), which could favor incomplete degradation and/or formation and release of persistent fluorinated substances. This is supported by the wide range of fluorinated substances detected in bench-scale LIB recycling experiments. Overall, this review highlights the need to further investigate emissions of fluorinated substances during LIB recycling and suggests that substitution of PFAS-based materials (i.e. during manufacturing), or alternatively post-treatments and/or changes in process conditions may be required to avoid formation and emission of persistent fluorinated substances.

Uptake of Ultrashort Chain, Emerging, and Legacy Per- and Polyfluoroalkyl Substances (PFAS) in Edible Mushrooms (Agaricus spp.) Grown in a Polluted Substrate.

Uptake of 19 per- and polyfluoroalkyl substances (PFAS), including C3-C14 perfluoroalkyl carboxylic acids (PFCAs), C4, C6, and C8 perfluoroalkyl sulfonates (PFSAs), and four emerging PFAS, was investigated in two mushroom species (Agaricus bisporus and Agaricus subrufescens) cultivated in a biogas digestate-based substrate. Accumulation of PFAS in mushrooms was low and strongly chain-length dependent. Among the different PFCAs, bioaccumulation factors (log BAFs) decreased from a maximum of -0.3 for perfluoropropanoic acid (PFPrA; C3) to a minimum of -3.1 for perfluoroheptanoate (PFHpA; C7), with only minor changes from PFHpA to perfluorotridecanoate (PFTriDA; C13). For PFSAs, log BAFs decreased from perfluorobutane sulfonate (PFBS; -2.2) to perfluorooctane sulfonate (PFOS; -3.1) while mushroom uptake was not observed for the alternatives 3H-perfluoro-3-[(3-methoxy-propoxy)propanoic acid] (ADONA) and two chlorinated polyfluoro ether sulfonates. To the best of our knowledge, this is the first investigation of the uptake of emerging and ultra-short chain PFAS in mushrooms, and generally the results indicate very low accumulation of PFAS.

Quantitative relationships of perfluoroalkyl acids in drinking water associated with serum concentrations above background in adults living near contamination hotspots in Sweden.

Contaminated drinking water (DW) is a major source of exposure to per- and polyfluoroalkyl substances (PFAS) at locations around PFAS production/use facilities and military airports. This study aimed to investigate quantitative relationships between concentrations in DW and serum of nine perfluoroalkyl acids (PFAAs) in Swedish adult populations living near contamination hotspots. Short-chained (PFPeA, PFHxA, PFHpA, and PFBS) and long-chained PFAAs (PFOA, PFNA, PFDA, PFHxS and PFOS) were measured in DW and serum. We matched DW and serum concentrations for a total of 398 subjects living or working in areas receiving contaminated DW and in one non-contaminated area. Thereafter, linear regression analysis with and without adjustments for co-variates was conducted. This enabled to derive (i) serum concentrations at background exposure (CB) from sources other than local DW exposure (i.e. food, dust and textiles) at 0 ng/L DW concentration, (ii) population-mean PFAA serum:water ratios (SWR) and (iii) PFAA concentrations in DW causing observable elevated serum PFAA concentrations above background variability. Median concentrations of the sum of nine PFAAs ranged between 2.8 and 1790 ng/L in DW and between 7.6 and 96.9 ng/mL in serum. DW concentration was the strongest predictor, resulting in similar unadjusted and adjusted regression coefficients. Mean CB ranged from <0.1 (PFPeA, PFHpA, PFBS) to 5.1 ng/mL (PFOS). Serum concentrations increased significantly with increasing DW concentrations for all PFAAs except for PFPeA with SWRs ranging from <10 (PFHxA, PFHpA and PFBS) to 111 (PFHxS). Observed elevated serum concentrations above background variability were reached at DW concentrations between 24 (PFOA) and 357 ng/L (PFHxA). The unadjusted linear regression predictions agreed well with serum concentrations previously reported in various populations exposed to low and high DW levels of PFOA, PFHxS and PFOS. The quantitative relationships derived herein should be helpful to translate PFAA concentrations in DW to concentrations in serum at the population level.

Widespread Occurrence of Non-Extractable Fluorine in Artificial Turfs from Stockholm, Sweden.

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.

Are cosmetics a significant source of PFAS in Europe? product inventories, chemical characterization and emission estimates.

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 ∑PFCAs 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.

Healthy eating index and diet diversity score as determinants of serum perfluoroalkyl acid (PFAA) concentrations in a national survey of Swedish adolescents.

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.

An Outdoor Aging Study to Investigate the Release of Per- And Polyfluoroalkyl Substances (PFAS) from Functional Textiles.

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.

Toxicometabolomics and Biotransformation Product Elucidation in Single Zebrafish Embryos Exposed to Carbamazepine from Environmentally-Relevant to Morphologically Altering Doses.

Toxicometabolomics and biotransformation product (bioTP) elucidation were carried out in single zebrafish (ZF) embryos exposed to carbamazepine (CBZ). Exposures were conducted in 96-well plates containing six CBZ concentrations ranging from 0.5 µg/L to 50 mg/L (n = 12 embryos per dose). In the 50 mg/L dose group, 33% of embryos developed edema during the exposure (120 hpf), while hatching was significantly delayed in three of the lower-dose groups (0.46, 3.85, and 445 µg/L) compared to the control at 48 hpf. Toxicometabolomic analysis together with random forest modeling revealed a total of 80 significantly affected metabolites (22 identified via targeted lipidomics and 58 via nontarget analysis). The wide range of doses enabled the observation of both monotonic and nonmonotonic dose responses in the metabolome, which ultimately produced a unique and comprehensive biochemical picture that aligns with existing knowledge on the mode of action of CBZ. The combination of high dose exposures and apical endpoint assessment in single embryos also enabled hypothesis generation regarding the target organ for the morphologically altering insult. In addition, two CBZ bioTPs were identified without additional exposure experiments. Overall, this work showcases the potential of toxicometabolomics and bioTP determination in single ZF embryos for rapid and comprehensive chemical hazard assessment.

Demographic, life-style and physiological determinants of serum per- and polyfluoroalkyl substance (PFAS) concentrations in a national cross-sectional survey of Swedish adolescents.

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.

Legacy and emerging organohalogenated compounds in feathers of Eurasian eagle-owls (Bubo bubo) in Norway: Spatiotemporal variations and associations with dietary proxies (δ13C and δ15N).

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 polybrominated 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 (δ13C) and nitrogen isotopes (δ15N) 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 eagle-owls, only δ13C seemed to explain variation in PFAS concentrations. Geographic area and year were influential factors for δ15N and δ13C. 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.

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

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.