Further Insight into Extractable (Organo)fluorine Mass Balance Analysis of Tap Water from Shanghai, China.

The ubiquitous occurrence of per- and polyfluoroalkyl substances (PFAS) and the detection of unexplained extractable organofluorine (EOF) in drinking water have raised growing concerns. A recent study reported the detection of inorganic fluorinated anions in German river systems, and therefore, in some samples, EOF may include some inorganic fluorinated anions. Thus, it might be more appropriate to use the term "extractable fluorine (EF) analysis" instead of the term EOF analysis. In this study, tap water samples (n = 39) from Shanghai were collected to assess the levels of EF/EOF, 35 target PFAS, two inorganic fluorinated anions (tetrafluoroborate (BF4-) and hexafluorophosphate (PF6-)), and novel PFAS through suspect screening and potential oxidizable precursors through oxidative conversion. The results showed that ultra-short PFAS were the largest contributors to target PFAS, accounting for up to 97% of ΣPFAS. To the best of our knowledge, this was the first time that bis(trifluoromethanesulfonyl)imide (NTf2) was reported in drinking water from China, and p-perfluorous nonenoxybenzenesulfonate (OBS) was also identified through suspect screening. Small amounts of precursors that can be oxidatively converted to PFCAs were noted after oxidative conversion. EF mass balance analysis revealed that target PFAS could only explain less than 36% of EF. However, the amounts of unexplained extractable fluorine were greatly reduced when BF4- and PF6- were included. These compounds further explained more than 44% of the EF, indicating the role of inorganic fluorinated anions in the mass balance analysis.

Levels and distribution profiles of Per- and Polyfluoroalkyl Substances (PFAS) in a high Arctic Svalbard ice core.

Per- and polyfluoroalkyl substances (PFAS) are a group of persistent organic contaminants of which some are toxic and bioaccumulative. Several PFAS can be formed from the atmospheric degradation of precursors such as fluorotelomer alcohols (FTOHs) as well as hydrochlorofluorocarbons (HFCs) and other ozone-depleting chlorofluorocarbon (CFC) replacement compounds. Svalbard ice cores have been shown to provide a valuable record of long-range atmospheric transport of contaminants to the Arctic. This study uses a 12.3 m ice core from the remote Lomonosovfonna ice cap on Svalbard to understand the atmospheric deposition of PFAS in the Arctic. A total of 45 PFAS were targeted, of which 26 were detected, using supercritical fluid chromatography (SFC) tandem mass spectrometry (MS/MS) and ultra-performance liquid chromatography (UPLC) MS/MS. C2 to C11 perfluoroalkyl carboxylic acids (PFCAs) were detected continuously in the ice core and their fluxes ranged from 2.5 to 8200 ng m-2 yr-1 (9.51-16,500 pg L-1). Trifluoroacetic acid (TFA) represented 71 % of the total mass of C2 - C11 PFCAs in the ice core and had increasing temporal trends in deposition. The distribution profile of PFCAs suggested that FTOHs were likely the atmospheric precursor to C8 - C11 PFCAs, whereas C2 - C6 PFCAs had alternative sources, such as HFCs and other CFC replacement compounds. Perfluorooctanesulfonic acid (PFOS) was also widely detected in 82 % of ice core subsections, and its isomer profile (81 % linear) indicated an electrochemical fluorination manufacturing source. Comparisons of PFAS concentrations with a marine aerosol proxy showed that marine aerosols were insignificant for the deposition of PFAS on Lomonosovfonna. Comparisons with a melt proxy showed that TFA and PFOS were mobile during meltwater percolation. This indicates that seasonal snowmelt and runoff from post-industrial accumulation on glaciers could be a significant seasonal source of PFAS to ecosystems in Arctic fjords.

Per- and polyfluoroalkyl substances (PFAS) in sludge from wastewater treatment plants in Sweden - First findings of novel fluorinated copolymers in Europe including temporal analysis.

Thousands of per- and polyfluoroalkyl substances (PFAS) are on the global market, while only a minor proportion is monitored regularly in the environment. Wastewater treatment plants (WWTPs) have been suggested to be a point source for PFAS to the environment due to emission of effluent and sludge. In this study, 81 PFAS including two rarely studied perfluoroalkyl sulfonamide-based (FASA) copolymers were analyzed in sludge samples to understand the usage of PFAS in the society. Sludge samples (n = 28) were collected at four WWTPs in Sweden between 2004 and 2017. The total levels of 79 measured PFAS were between 50 and 1124 ng/g d.w. All sludge samples showed detectable levels of both C8- and C4-FASA-based copolymers. The concentrations of the FASA-based copolymers were proposed to be reported in fluorinated side-chain equivalents (FSC eq.), in order to compare the levels of the copolymers with the other neutral and anionic PFAS, as no authentic standards were available. The concentrations of the FASA-based copolymers in sludge were between 1.4 and 22 ng FSC eq./g d.w. A general predomination of precursor and intermediate compounds was observed. A lower contribution of perfluoroalkyl carboxylic acids was noted for the WWTPs more influenced by domestic emission when compared with more influenced by industrial emission. An overall declining trend in the total PFAS concentration was seen between the years 2004 and 2017. The present study observed a shift from the C8-based chemistry toward shorter chain lengths, included a declining trend for C8-FASA-based copolymer over the entire study period. These findings further demonstrate the occurrence of side-chain fluorinated copolymers in Sweden and that sludge is a useful matrix to reflect the usage of PFAS in society and the potential for environmental exposure.

A pilot study on extractable organofluorine and per- and polyfluoroalkyl substances (PFAS) in water from drinking water treatment plants around Taihu Lake, China: what is missed by target PFAS analysis?

Per- and polyfluoroalkyl substances (PFAS) have raised concerns due to their worldwide occurrence and adverse effects on both the environment and humans as well as posing challenges for monitoring. Further collection of information is required for a better understanding of their occurrence and the unknown fractions of the extractable organofluorine (EOF) not explained by commonly monitored target PFAS. In this study, eight pairs of raw and treated water were collected from drinking water treatment plants (DWTPs) around Taihu Lake in China and analyzed for EOF and 34 target PFAS. Mass balance analysis of organofluorine revealed that at least 68% of EOF could not be explained by target PFAS. Relatively higher total target concentrations were observed in 4 DWTPs (D1 to D4) when compared to other samples with the highest sum concentration up to 189 ng L-1. PFOA, PFOS and PFHxS were the abundant compounds. Suspect screening analysis identified 10 emerging PFAS (e.g., H-PFAAs, H-PFESAs and OBS) in addition to target PFAS in raw or treated water. The ratios PFBA/PFOA and PFBS/PFOS between previous and current studies showed significant replacements of short-chain to long-chain PFAS. The ratios of the measured PFAS concentrations to the guideline values showed that some of the treated drinking water exceeds guideline values, appealing for efforts on drinking water safety guarantee.

Analysis and characterization of novel fluorinated compounds used in surface treatments products.

Side-chain fluorinated polymers are speculated to be potential precursors to other non-polymeric aliphatic per- and polyfluoroalkyl acids (PFAAs). Limited knowledge of environmental occurrence of this compound class is partly due to lack of structural information and authentic standards. In this study, two novel fluorinated compounds, suspected to be side-chain fluorinated copolymers used in two commercial technical mixtures (Scotchgard™ Pre-2002 formulation and Scotchgard™ Post-2002 formulation) were analyzed and characterized in order to provide information to facilitate detection and quantification. The commercial mixtures were analyzed using tandem mass spectrometry and high-resolution mass spectrometry; besides already reported C4- and C8-fluoroalkylsulfonamido (FASA) side-chains, a proposed structure was determined for the perfluorooctane (C8) sulfonamide-urethane copolymer in the Pre-2002 formulation. Structural isomers were also observed for C4- and C8-FASA-based copolymers. Total fluorine analysis revealed that the Scotchgard™ Pre-2002 Formulation contained a fluorine content of 0.5% and 1.8% for the Scotchgard™ Post-2002 Formulation. The equivalent FASA side-chain content was determined to be 0.8% for Pre-2002 and 3.1% for Post-2002. Both C4- and C8-FASA-based copolymers underwent hydrolysis and oxidation and were transformed to their respective perfluoroalkyl side chain, which suggest that transformation products can be analyzed for example after total oxidizable precursor (TOP) assay. Both compounds were shown to strongly sorb to sediment particles, which also gives indications about their environmental fate and transport pathways.

Changes in plasma levels of per- and polyfluoroalkyl substances (PFAS) are associated with changes in plasma lipids - A longitudinal study over 10 years.

BACKGROUND: Associations between per- and polyfluoroalkyl substances (PFAS), mainly PFOS and PFOA, and increased blood lipids have been reported primarily from cross-sectional studies. The aim of the present study was to investigate associations between multiple PFAS and blood lipids in a longitudinal fashion. METHODS: A total of 864 men and women aged 70 years and free from lipid medication were included from the Prospective Investigation of the Vasculature in Uppsala Seniors (PIVUS) study from Uppsala Sweden, 614 and 404 of those were reinvestigated at age 75 and 80. At all three occasions, eight PFAS were measured in plasma using ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). Total cholesterol, triglycerides, low-density lipoprotein cholesterol (LDL-C) and high-density lipoprotein cholesterol (HDL-C) were also measured in plasma at all three occasions. Mixed-effects linear regression models were used to examine the relationship between the changes in PFAS levels and changes in lipid levels. RESULTS: Changes in plasma levels of six out of the eight investigated PFAS were positively associated with changes in plasma lipids after adjustment for sex, change in body mass index (BMI), smoking, physical activity, statin use (age was the same in all subjects), and correction for multiple testing. For example, changes in perfluorodecanoic acid (PFDA) were positively associated with the changes in total cholesterol (ß: 0.23, 95% confidence interval (CI): 0.14 to 0.32), triglycerides (ß: 0.08, 95% CI: 0.04-0.12) and HDL-cholesterol (ß: 0.08, 95% CI: 0.04-0.11). CONCLUSION: In this longitudinal study with three measurements over 10 years of both plasma PFAS and lipids, changes in six out of the eight investigated PFAS were positively associated with changes in plasma lipids, giving further support for a role of PFAS exposure in human lipid metabolism.

Sorption and desorption kinetics of PFOS to pristine microplastic.

The sorption processes of persistent organic pollutants on microplastics particles are poorly understood. Therefore, the present study investigated the sorption processes of perfluorooctanesulfonate (PFOS) on polyethylene (PE) microplastic particles (MPs) which are representing a prominent environmental pollutant and one of the most abundant microplastic polymers in the aquatic environment, respectively. The focus was set on the investigation of the impact of the particle size on PFOS sorption using four different PE MPs size ranges. The sorption kinetics for 6 months was studied with one selected size range of PE MPs. Besides, the desorption of PFOS from PE MPs under simulated digestive conditions was carried out by using artificial gut fluid mimicking the intestinal juice of fish. The investigation of the size effects of particles over 6 months demonstrated a linear increase of PFOS concentration sorbed onto PE with a decrease of the particle size. Thus, our findings implicate efficient sorption of PFOS onto PE MPs of different sizes. The results showed that PFOS desorbed from the PE MPs into the artificial gut fluid with a rate of 70 to 80%. Besides, a longer exposure of PE MPs to PFOS leads to a higher concentration adsorbed by PE MPs, which may favor the ingestion of higher concentration of PFOS, and thus represents a higher risk to transfer relevant concentrations of PFOS during digestion.

Comparison of extraction and clean-up methods for comprehensive screening of organic micropollutants in fish using gas chromatography coupled to high-resolution mass spectrometry.

Monitoring the vast number of micropollutants in the environment by using comprehensive chemical screening is a major analytical challenge. The aim of this study was to evaluate a comprehensive analysis method for screening purposes of fish muscle samples by comparing sample preparation methods for a broad range of mid-to non-polar contaminants. Five extraction and three clean-up methods were evaluated for the analysis of 60 compounds with a log Kow range between 0.8 and 8.3 in fish. Both fresh and freeze-dried muscle tissue and extraction sodium sulphate blanks were included to assess recoveries and matrix effects. The performance of the different methods was evaluated using both comprehensive target and nontarget analysis using high resolution mass spectrometry (HRMS). The results showed that open-column and ultrasonication extractions (recoveries mostly between 20 and 160 %) resulted in higher recoveries than accelerated solvent extraction (ASE) (recoveries mostly between 20 and 80 %) and bead mixer homogenization extractions (recoveries between 0 and 50 % for the whole Kow range). Multilayer silica was the clean-up method resulting in the lowest matrix effects and highest recoveries, however some compounds (mostly pesticides) were denatured under the acidic conditions used. The convenient and time efficient ultrasonication extraction followed by deactivated silica clean-up proved to be promising for both target and nontarget approaches. The large difference in recoveries and number of detected peaks using target and nontarget approaches between fresh and freeze-dried fish seen for all methods calls for careful consideration, and further studies are needed to improve performance for screening of mid-to non-polar compounds in freeze-dried fish.

Perfluoroalkyl substances in circum-ArcticRangifer: caribou and reindeer.

Livers of caribou and reindeer (Rangifer tarandus) from Canada (n = 146), Greenland (n = 30), Svalbard (n = 7), and Sweden (n = 60) were analyzed for concentrations of eight perfluoroalkyl carboxylic acids and four perfluoroalkane sulfonic acids. In Canadian caribou, PFNA (range < 0.01-7.4 ng/g wet weight, ww) and PFUnDA (<0.01-5.6 ng/g ww) dominated, whereas PFOS predominated in samples from South Greenland, Svalbard, and Sweden, although the highest concentrations were found in caribou from Southwest Greenland (up to 28 ng/g ww). We found the highest median concentrations of all PFAS except PFHxS in Akia-Maniitsoq caribou (Southwest Greenland, PFOS 7.2-19 ng/g ww, median 15 ng/g ww). The highest concentrations of ΣPFAS were also found in Akia-Maniitoq caribou (101 ng/g ww) followed by the nearby Kangerlussuaq caribou (45 ng/g ww), where the largest airport in Greenland is situated, along with a former military base. Decreasing trends in concentrations were seen for PFOS in the one Canadian and three Swedish populations. Furthermore, PFNA, PFDA, PFUnDA, PFDoDA, and PFTrDA showed decreasing trends in Canada's Porcupine caribou between 2005 and 2016. In Sweden, PFHxS increased in the reindeer from Norrbotten between 2003 and 2011. The reindeer from Västerbotten had higher concentrations of PFNA and lower concentrations of PFHxS in 2010 compared to 2002. Finally, we observed higher concentrations in 2010 compared to 2002 (albeit statistically insignificant) for PFHxS in Jämtland, while PFNA, PFDA, PFUnDA, PFDoDA, and PFTrDA showed no difference at all.

Extractable organofluorine analysis: A way to screen for elevated per- and polyfluoroalkyl substance contamination in humans?

The ubiquitous occurrence of a few per- and polyfluoroalkyl substances (PFAS) in humans and the environment has been previously reported. However, the number of PFAS humans and the environment are potentially exposed to is much higher, making it difficult to investigate every sample in detail. More importantly, recent studies have shown an increasing fraction of potentially unknown PFAS in human samples. A screening tool for identifying samples of concern that may contain high PFAS levels, to be studied more thoroughly, is needed. This study presents a simplified workflow to detect elevated PFAS levels using extractable organofluorine (EOF) analysis. A fluorine mass balance analysis on samples with high EOF, targeting 63 PFAS, can then confirm the PFAS contamination. Whole blood samples from a cohort of individuals with historical drinking water contamination from firefighting foams (n = 20) in Ronneby (Sweden) and a control group (n = 9) with background exposure were used as a case study. The average EOF concentration in the Ronneby group was 234 ng/mLF (<107-592 ng/mLF) vs 24.8 ng/mLF (17.6-37.8 ng/mL F) in the control group. The large difference (statistically significant, p < 0.05) in the EOF levels between the exposed and control groups would have made it possible to identify samples with high PFAS exposure only using EOF data. This was confirmed by target analysis, which found an average ∑PFAS concentration of 346 ng/mL in the exposed group and 7.9 ng/mL in the control group. The limit of quantification for EOF analysis (up to 107 ng/mLF using 0.5 mL whole blood) did not allow for the detection of PFAS levels in low or sub parts per billion (ng/mL) concentrations, but the results indicate that EOF analysis is a suitable screening method sensitive enough to detect elevated/significant/exposure above background levels by known or unknown PFAS.

Mass Balance of Perfluoroalkyl Acids, Including Trifluoroacetic Acid, in a Freshwater Lake.

Perfluoroalkyl acids (PFAAs) are highly persistent chemicals that are ubiquitously found in the environment. The atmospheric degradation of precursor compounds has been identified as a source of PFAAs and might be an important pathway for contamination. Lake Vättern is one of Sweden's largest lakes and is an important source for drinking water. In addition to contamination via atmospheric deposition, the lake is subject to several potential contamination sources via surface water inflow. The relevance of different sources is not well understood. A mass balance of selected PFAAs was assembled based on measured concentrations in atmospheric deposition, surface water from streams that constitute the main inflow and outflow, and surface water in the lake. The largest input was seen for trifluoroacetic acid (150 kg/year), perfluoropropanoic acid (1.6 kg/year), perfluorobutanoic acid (4.0 kg/year), and perfluoro-octanoic acid (1.5 kg/year). Both atmospheric deposition and surface water inflow was found to be important input pathways. There was a positive correlation between the input of most perfluoroalkyl carboxylic acids via atmospheric deposition and global radiation and between the input via surface water inflow and catchment area. These findings highlight the importance of atmospheric oxidation of volatile precursor compounds for contamination in surface waters.

Levels and Seasonal Trends of C1-C4 Perfluoroalkyl Acids and the Discovery of Trifluoromethane Sulfonic Acid in Surface Snow in the Arctic.

C1-C4 perfluoroalkyl acids (PFAAs) are highly persistent chemicals that have been found in the environment. To date, much uncertainty still exists about their sources and fate. The importance of the atmospheric degradation of volatile precursors to C1-C4 PFAAs were investigated by studying their distribution and seasonal variation in remote Arctic locations. C1-C4 PFAAs were measured in surface snow on the island of Spitsbergen in the Norwegian Arctic during January-August 2019. Trifluoroacetic acid (TFA), perfluoropropanoic acid (PFPrA), perfluorobutanoic acid (PFBA), and trifluoromethane sulfonic acid (TFMS) were detected in most samples, including samples collected at locations presumably receiving PFAA input solely from long-range processes. The flux of TFA, PFPrA, PFBA, and TFMS per precipitation event was in the ranges of 22-1800, 0.79-16, 0.19-170, and 1.5-57 ng/m2, respectively. A positive correlation between the flux of TFA, PFPrA, and PFBA with downward short-wave solar radiation was observed. No correlation was observed between the flux of TFMS and solar radiation. These findings suggest that atmospheric transport of volatile precursors and their subsequent degradation plays a major role in the global distribution of C2-C4 perfluoroalkyl carboxylic acids and their consequential deposition in Arctic environments. The discovery of TFMS in surface snow at these remote Arctic locations suggests that TFMS is globally distributed. However, the transport mechanism to the Arctic environment remains unknown.

Organofluorine Mass Balance Analysis of Whole Blood Samples in Relation to Gender and Age.

Studies have highlighted the increasing fraction of unidentified organofluorine (UOF) compounds in human blood, whose health effects are not known. In this study, 130 whole blood samples from the Swedish general population were analyzed for extractable organofluorine (EOF) and selected per- and polyfluoroalkyl substances (PFAS). Organofluorine mass balance analysis revealed that 60% (0-99%) of the EOF in female samples could not be explained by the 63 monitored PFAS; in males, 41% (0-93%) of the EOF was of unidentified origin. Significant differences between both age groups and gender were seen, with the highest fraction of UOF in young females (70% UOF, aged 18-44), which is contrary to what has been reported in the literature for commonly monitored compounds (e.g., perfluorooctane sulfonic acid, PFOS). Increasing the number of monitored PFAS did not lead to a large decrease of the UOF fraction; the seven highest PFAS (C8-C11 PFCAs, C6-C8 PFSAs) accounted for 98% of sum 63 PFAS. The high fraction of UOF in human samples is of concern, as the chemical species of these organofluorine compounds remain unknown and thus their potential health risks cannot be assessed.

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

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).

Combustion ion chromatography for extractable organofluorine analysis.

Combustion ion chromatography (CIC) has found a role in environmental analytical chemistry for fluorine content analysis. It is used for extractable organofluorine (EOF) analysis to evaluate perfluoroalkyl and polyfluoroalkyl substances (PFASs) and other organofluorine burden. The prevailing assumption has been that all PFASs are incinerated in CIC and matrix components have no impact on this process, but this has not been experimentally evaluated. In this work, the combustion efficiencies of 13 different PFASs were determined (66-110%). A notable difference was observed between calibrating the CIC with inorganic fluorine or organofluorine. Potential interferences from cations and coextracted matrix components from whole blood and surface water samples were evaluated. These observations should be acknowledged when performing EOF analysis using CIC, overlooking either non-100% combustion efficiencies or the differences in calibrating the CIC with inorganic fluorine or organofluorine could lead to underestimating EOF content and through that to misguide policy decisions.

Fluorine mass balance analysis of selected environmental samples from Norway.

The presence of unidentified organofluorine compounds (UOF) has been investigated in recent publication, but their environmental occurrence is still poorly understood. Fluorine mass balance analysis was performed on environmental samples from lake Mjøsa and river Alna (surface water (n = 9), sediment (n = 5) and fish liver (n = 4)) and sewage samples from Oslo (n = 5), to reveal to the fraction of UOF. In samples that had extractable organofluorine (EOF) concentrations above the limit of detection (LoD), more than 70% of their EOF could not be accounted for by the 37 PFAS monitored in this study. The surface water samples from lake Mjøsa had EOF concentrations several times higher than what has been reported elsewhere in Nordic nations. The flux of EOF in river Alna and selected sewage pipes revealed that it was 1-2 orders of magnitude higher than the flux of the measured PFAS. The elevated concentrations of EOF in all samples pose a potential health and environmental hazard, as their composition remains mostly unknown.

Extractable Organofluorine Analysis in Pooled Human Serum and Placental Tissue Samples from an Austrian Subpopulation-A Mass Balance Analysis Approach.

Embryos and fetuses are of major concern due to their high vulnerability. Previous studies demonstrated that human exposure to per- and polyfluoroalkyl substances (PFAS) may be underestimated because only a limited number of known PFAS can be measured. This investigation studied the total PFAS exposure by measuring the extractable organofluorine (EOF) in pooled maternal serum, placental tissue, and cord serum samples (total number of pooled samples: n = 45). The EOF was analyzed using combustion ion chromatography, and the concentrations of known PFAS were determined using ultraperformance liquid chromatography coupled with a tandem mass spectrometer. Using a mass balance analysis approach, the amount of unknown PFAS was estimated between the levels of known PFAS and EOF. The EOF levels ranged from 2.85 to 7.17 ng F/mL (21 PFAS were quantified) in the maternal serum, from 1.02 to 1.85 ng F/g (23 PFAS were quantified) in the placental tissue, and from 1.2 to 2.10 ng F/mL (18 PFAS were quantified) in the cord serum. An average of 24, 51, and 9% of EOF is unidentified in the maternal serum, placental tissue, and cord serum, respectively. The results show that the levels of unidentified EOF are higher in the placental tissue, suggesting accumulation or potential transformation of precursors in the placenta.

Quantification of Biodriven Transfer of Per- and Polyfluoroalkyl Substances from the Aquatic to the Terrestrial Environment via Emergent Insects.

Emergent aquatic insects are important food subsidies to riparian food webs but can also transfer waterborne contaminants to the terrestrial environment. This study aimed to quantitatively assess this biodriven transfer for per- and polyfluoroalkyl substances (PFAS). Aquatic insect larvae, emergent aquatic insects, terrestrial consumers, sediment, and water were collected from a contaminated lake and stream and an uncontaminated pond, and analyzed for PFAS and stable isotopes of carbon and nitrogen. Top predators in this study were spiders, which showed the highest average ∑24PFAS concentration of 1400 ± 80 ng g-1 dry weight (dw) at the lake and 630 ng g-1 dw at the stream. The transfer of PFAS from the lake to the riparian zone, via deposition of emergent aquatic insects, was 280 ng ∑24PFAS m-2 d-1 in 2017 and only 23 ng ∑24PFAS m-2 d-1 in 2018. Because of higher production of emergent aquatic insects, the lake had higher PFAS transfer and higher concentrations in terrestrial consumers compared to the stream, despite the stream having higher PFAS concentration in water and aquatic insect larvae. Our results indicate that biodriven transfer of PFAS from the aquatic systems and subsequent uptake in terrestrial food webs depend more on emergence amounts, i.e., aquatic prey availability, rather than on PFAS concentrations in water and aquatic prey.

Characterization of an AFFF impacted freshwater environment using total fluorine, extractable organofluorine and suspect per- and polyfluoroalkyl substance screening analysis.

The vast number of per- and polyfluoroalkyl substances (PFASs) that are in global commerce (n > 4700) pose immense challenges for environmental monitoring. The large discrepancy between this large number and the few PFASs usually monitored suggest that environmental exposure might be substantially underestimated. This study applied a workflow, which included analysis of total fluorine (TF), extractable organofluorine (EOF), 24 target PFASs and suspect screening. The workflow aimed to close the organofluorine mass balance and to tentatively identify overlooked PFASs in various matrices from an aqueous film forming foam (AFFF) contaminated pond and its adjacent riparian zone. PFAS target analysis revealed that water, aquatic invertebrates as well as emergent aquatic insects had high concentrations with up to 2870 ng L-1, 9230 ng g-1 dry weight (dw) and 1470 ng g-1 dw ∑24PFASs, respectively. The EOF mass balance could be explained by target PFAS analysis for most biota samples such as aquatic invertebrates, emergent aquatic insects and terrestrial spiders and earthworms (i.e. EOF ≈ ∑24PFASs). In the pond surface water, 42-58% of the EOF was not explained by target PFASs. However most new tentatively identified PFASs (n = 25) were detected in water, which could contribute to the unknown EOF. Nine suspects could be further identified, which where perfluoroalkyl sulfonamide-based compounds and derivatives that all have been found in historical AFFFs produced by electrochemical fluorination. One suspect, F5S-PFOS, was also detected for the first time in aquatic and terrestrial invertebrates.

Comprehensive chemical characterization of indoor dust by target, suspect screening and nontarget analysis using LC-HRMS and GC-HRMS.

Since humans spend more than 90% of their time in indoor environments, indoor exposure can be an important non-dietary pathway to hazardous organic contaminants. It is thus important to characterize the chemical composition of indoor dust to assess the total contaminant exposure and estimate human health risks. The aim of this investigation was to perform a comprehensive chemical characterization of indoor dust. First, the robustness of an adopted extraction method using ultrasonication was evaluated for 85 target compounds. Thereafter, a workflow combining target analysis, suspect screening analysis (SSA) and nontarget analysis (NTA) was applied to dust samples from different indoor environments. Chemical analysis was performed using both gas chromatography and liquid chromatography coupled with high resolution mass spectrometry. Although suppressing matrix effects were prominent, target analysis enabled the quantification of organophosphate/brominated flame retardants (OPFRs/BFRs), liquid crystal monomers (LCMs), toluene diisocyanate, bisphenols, pesticides and tributyl citrate. The SSA confirmed the presence of OPFRs but also enabled the detection of polyethylene glycols (PEGs) and phthalates/parabens. The combination of hierarchical cluster analysis and scaled mass defect plots in the NTA workflow confirmed the presence of the above mentioned compounds, as well as detect other contaminants such as tetrabromobisphenol A, triclocarban, diclofenac and 3,5,6-trichloro-2-pyridinol, which were further confirmed using pure standards.