Hexafluoropropylene Oxide Dimer Acid Research Articles

Occurrence, source apportionment, plant bioaccumulation and human exposure of legacy and emerging per- and polyfluoroalkyl substances in soil and plant leaves near a landfill in China

In this study, 17 legacy and emerging PFASs were investigated in soil and plant leaves near a valley-type landfill, which has been in operation for over 20 years. ΣPFASs concentrations ranged from 5.31 to 108 ng/g dw and 11.9 to 115 ng/g dw in the soil and leaf samples, respectively, and perfluorobutanoic acid (PFBA) was dominant in both soil and leaves. The concentrations of hexafluoropropylene oxide dimer acid (HFPO-DA), 6:2 chlorinated polyfluorinated ether sulfonic acid (F-53B) and 6:2 fluorotelomer sulfonic acid (6:2 FTS) were significantly higher than those of legacy PFOA and PFOS, indicating emerging alternatives were widely applied in the region. The integrated approach of PCA analysis, field investigation of relevant industrial activities in the study area, along with the Unmix model analysis quantitatively revealed that factories producing consumer products and the landfill were the major sources of PFASs in soil, accounting for 57% of total PFASs detected. Bioaccumulation factors (BAFs) of ΣPFASs in leaves varied from 0.37 to 8.59, and higher BAFs were found in camphor leaves. The log10BAFs in all plant leaves showed a linear decrease with increasing carbon chain lengths for individual PFCAs (C4–C8). The BAF values of HFPO-DA, F-53B and 6:2 FTS were 0.01–3.39, 0.04–6.15 and 0.01–6.33, respectively. The human health risk assessment of EDIs showed a decreasing trend with the increasing carbon chain lengths of PFCAs (C4–C9), and the PFASs EDI indicated further study on the human health risk via vegetable consumption be warranted.

Scientists will refine which chemicals are PFAS

This year, an international panel of scientists plans to release a more precise definition of a class of chemicals often found in news headlines—per- and polyfluoroalkyl substances (PFAS). PFAS are a group of synthetic, environmentally stable “forever chemicals” that persist in the environment. They include inert polymers such as polytetrafluoroethylene—used in Teflon—and toxic, biologically active compounds such as the widespread pollutant perfluorooctanoic acid (PFOA). PFAS also include novel compounds that researchers have discovered in the environment near industrial facilities. One is hexafluoropropylene oxide dimer acid (HFPO-DA), a substance formed via hydrolysis from GenX, Chemours’s replacement for PFOA. Others are chloroperfluoropolyether carboxylates , detected in soil near a Solvay plant in New Jersey. The panel, the Global Perfluorinated Chemicals Group , is reviewing “the universe and terminology of PFAS,” says Marie-Ange Baucher, administrator for chemical accidents and risk management of chemicals at the Environment Directorate of the Organisation for Economic Co-operation

Per- and polyfluoroalkyl substances and their alternatives in black-tailed gull (Larus crassirostris) eggs from South Korea islands during 2012–2018

The temporal and spatial trends of sixteen per- and polyfluoroalkyl substances (PFAS) and their three alternatives, chlorinated polyfluoroalkyl ether sulfonic acid (F-53B), hexafluoropropylene oxide dimer acid (GenX), and dodecafluoro-3H-4,8-dioxanonanoate (ADONA) in whole eggs of black-tailed gulls from two South Korean islands, Baengnyeongdo (BLD) and Hongdo (HD), were investigated during 2012–2018. A total of 16 analyzed compounds were detected at concentrations of 21.3–47.8 ng/g ww in BLD and 11.2–40.0 ng/g ww in HD. Meanwhile, the mean levels of perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) were detected at 6.92 ± 4.72 ng/g ww and 0.674 ± 0.993 ng/g ww, respectively. In particular, F-53B, a major alternative to PFOS was detected in each year of the study period with a level of up to 6.66 ng/g ww in all egg samples. Significant increasing temporal trends were observed for PFOS, perfluorononanoic acid (PFNA) and one alternative (F-53B) during the investigated period suggesting continuous use or accumulation of these in the Korean environment. Moreover, distinctive spatial distribution patterns such as a significantly higher F-53B level in HD and an increased PFAS (< C11) in BLD were also observed.

Latent, sex-specific metabolic health effects in CD-1 mouse offspring exposed to PFOA or HFPO-DA (GenX) during gestation

BackgroundPerfluorooctanoic acid (PFOA) is an environmental contaminant associated with adverse metabolic outcomes in developmentally exposed human populations and mouse models. Hexafluoropropylene oxide-dimer acid (HFPO-DA, commonly called GenX) has replaced PFOA in many industrial applications in the U.S. and Europe and has been measured in global water systems from <1 to 9350 ng/L HFPO-DA. Health effects data for GenX are lacking. ObjectiveDetermine the effects of gestational exposure to GenX on offspring weight gain trajectory, adult metabolic health, liver pathology and key adipose gene pathways in male and female CD-1 mice. MethodsDaily oral doses of GenX (0.2, 1.0, 2.0 mg/kg), PFOA (0.1, 1.0 mg/kg), or vehicle control were administered to pregnant mice (gestation days 1.5–17.5). Offspring were fed a high- or low-fat diet (HFD or LFD) at weaning until necropsy at 6 or 18 weeks, and metabolic endpoints were measured over time. PFOA and GenX serum and urine concentrations, weight gain, serum lipid parameters, body mass composition, glucose tolerance, white adipose tissue gene expression, and liver histopathology were evaluated. ResultsPrenatal exposure to GenX led to its accumulation in the serum and urine of 5-day old pups (P = 0.007, P < 0.001), which was undetectable by weaning. By 18 weeks of age, male mice fed LFD in the 2.0 mg/kg GenX group displayed increased weight gain (P < 0.05), fat mass (P = 0.016), hepatocellular microvesicular fatty change (P = 0.015), and insulin sensitivity (P = 0.014) in comparison to control males fed LFD. Female mice fed HFD had a significant increase in hepatocyte single cell necrosis in 1.0 mg/kg GenX group (P = 0.022) and 1.0 mg/kg PFOA group (P = 0.003) compared to control HFD females. Both sexes were affected by gestational GenX exposure; however, the observed phenotype varied between sex with males displaying more characteristics of metabolic disease and females exhibiting liver damage in response to the gestational exposure. ConclusionsPrenatal exposure to 1 mg/kg GenX and 1 mg/kg PFOA induces adverse metabolic outcomes in adult mice that are diet- and sex-dependent. GenX also accumulated in pup serum, suggesting that placental and potentially lactational transfer are important exposure routes for GenX.

Per- and Polyfluoroalkyl Substances in the Air Particles of Asia: Levels, Seasonality, and Size-Dependent Distribution.

Information regarding the size-dependent distribution of per- and polyfluoroalkyl substances (PFAS) in atmospheric particulate matter (PM) is very limited. In this study, 248 size-specific PM samples were collected from 9 Asian cities using a portable 4-stage cascade impactor for the analysis of PFAS. Of the 34 investigated PFAS, perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS) were the major compounds. In particular, the emerging PFAS, hexafluoropropylene oxide dimer acid, was quantified in the PM for the first time, with concentrations ranging from <0.086 to 21.5 pg/m3. Spatially, PFOA and PFOS were the predominant compounds in China, while precursors, emerging PFAS, and short-chain PFAS dominated in India, Japan, and South Korea, respectively. Seasonal variations of PFAS may be controlled by regional climate, local or seasonal emission sources, and long-range transport of air masses. Size-dependent distribution was investigated, showing that the majority of PFAS predominantly affiliated in fine particles, while PFOS and its alternatives tended to attach on coarser particles. Moreover, PFOS distributed on specific sizes exhibited seasonal and regional dependency, while no such patterns were observed for PFOA. These findings will provide useful information on the geographical and size-dependent distribution of PFAS in the atmospheric PM.

Hexafluoropropylene oxide-dimer acid (HFPO-DA or GenX) alters maternal and fetal glucose and lipid metabolism and produces neonatal mortality, low birthweight, and hepatomegaly in the Sprague-Dawley rat

Hexafluoropropylene oxide dimer acid (HFPO-DA or GenX) is an industrial replacement for the straight-chain perfluoroalkyl substance (PFAS), perfluorooctanoic acid (PFOA). Previously we reported maternal, fetal, and postnatal effects from gestation day (GD) 14-18 oral dosing in Sprague-Dawley rats. Here, we further evaluated the perinatal toxicity of HFPO-DA by orally dosing rat dams with 1–125 mg/kg/d (n = 4 litters per dose) from GD17-21 and with 10–250 mg/kg/d (n = 5) from GD8 – postnatal day (PND) 2. Effects of GD17-21 dosing were similar to those previously reported for GD14-18 dosing and included increased maternal liver weight, altered maternal serum lipid and thyroid hormone concentrations, and altered expression of peroxisome proliferator-activated receptor (PPAR) pathway genes in maternal and fetal livers. Dosing from GD8-PND2 produced similar effects as well as dose-responsive decreased pup birth weight (≥30 mg/kg), increased neonatal mortality (≥62.5 mg/kg), and increased pup liver weight (≥10 mg/kg). Histopathological evaluation of newborn pup livers indicated a marked reduction in glycogen stores and pups were hypoglycemic at birth. Quantitative gene expression analyses of F1 livers revealed significant alterations in genes related to glucose metabolism at birth and on GD21. Maternal serum and liver HFPO-DA concentrations were similar between dosing intervals, indicating rapid clearance, however dams dosed GD8 – PND2 had greater liver weight and gestational weight gain effects at lower doses than GD17-21 dosing, indicating the importance of exposure duration. Comparison of neonatal mortality dose–response curves between HFPO-DA and previously published perfluorooctane sulfonate (PFOS) data indicated that, based on serum concentration, the potency of these two PFAS are similar in the rat. Overall, HFPO-DA is a developmental toxicant in the rat and the spectrum of adverse effects is consistent with prior PFAS toxicity evaluations, such as PFOS and PFOA.

Cationic covalent organic framework for efficient removal of PFOA substitutes from aqueous solution

Perfluorooctanoic acid (PFOA) substitutes such as hexafluoropropylene oxide dimer acid (GenX) and hexafluoropropylene oxide trimer acid (HFPO-TA) are toxic as environmental contaminants, and efficient adsorbents are required to remove them from waters. In this study, the novel cationic covalent organic framework (COF) was developed via an imine condensation reaction for efficient removal of GenX and HFPO-TA from aqueous solution. The prepared COFs exhibited a 2D ordering hexagonal structure with AA stacking and two classes of pores (mesopore and micropore). The introduction of quaternary ammonium on COF exhibited little effect on its morphology and crystal structure. The cationic COF with quaternary ammonium showed high adsorption capacity for GenX (2.06 mmol/g) and HFPO-TA (2.16 mmol/g), more efficient than conventional activated carbons and resins. The effects of pH and natural organic matter on the removal efficiency of GenX and HFPO-TA on COF were also investigated. Interestingly, the previously adsorbed GenX on the cationic COF was replaced by the longer-chain HFPO-TA, and the underlying competitive mechanism was further clarified by performing a density functional theory calculation. This study highlights the exceptional potential of COFs through topology structural design for the efficient removal of per- and polyfluoroalkyl substances from aqueous solution.

An assessment of serum-dependent impacts on intracellular accumulation and genomic response of per- and polyfluoroalkyl substances in a placental trophoblast model.

Per- and polyfluoroalkyl substances (PFAS), a class of environmental contaminants, have been detected in human placenta and cord blood. The mechanisms driving PFAS-induced effects on the placenta and adverse pregnancy outcomes are not well understood. This study investigated the impact of perfluorooctanesulfonic acid (PFOS), perfluorooctanoic acid (PFOA), and a replacement PFAS known as hexafluoropropylene oxide dimer acid (HFPO-DA, tradename GenX) on placental trophoblasts in vitro. Several key factors were addressed. First, PFAS levels in cell culture reagents at baseline were quantified. Second, the role of supplemental media serum in intracellular accumulation of PFAS in a human trophoblast (JEG3) cell line was established. Finally, the impact of PFAS on the expression of 96 genes involved in proper placental function in JEG3 cells was evaluated. The results revealed that serum-free media (SFM) contained no detectable PFAS. In contrast, fetal bovine serum-supplemented media (SSM) contained PFNA, PFUdA, PFTrDA, and 6:2 FTS, but these PFAS were not detected internally in cells. Intracellular accumulation following 24 hr treatments was significantly higher when cultured in SFM compared to SSM for PFOS and PFOA, but not HFPO-DA. Treatment with PFAS was associated with gene expression changes (n = 32) in pathways vital to placental function, including viability, syncytialization, inflammation, transport, and invasion/mesenchymal transition. Among the most robust PFAS-associated changes were those observed in the known apoptosis-related genes, BAD and BAX. These results suggest a complex relationship between PFAS, in vitro culture conditions, and altered expression of key genes necessary for proper placentation.

Transport of Legacy Perfluoroalkyl Substances and the Replacement Compound HFPO-DA through the Atlantic Gateway to the Arctic Ocean-Is the Arctic a Sink or a Source?

The spatial distribution of 29 per- and polyfluoroalkyl substances (PFASs) in seawater was investigated along a sampling transect from Europe to the Arctic and two transects within Fram Strait, located between Greenland and Svalbard, in the summer of 2018. Hexafluoropropylene oxide-dimer acid (HFPO-DA), a replacement compound for perfluorooctanoic acid (PFOA), was detected in Arctic seawater for the first time. This provides evidence for its long-range transport to remote areas. The total PFAS concentration was significantly enriched in the cold, low-salinity surface water exiting the Arctic compared to warmer, higher-salinity water from the North Atlantic entering the Arctic (260 ± 20 pg/L versus 190 ± 10 pg/L). The higher ratio of perfluoroheptanoic acid (PFHpA) to perfluorononanoic acid (PFNA) in outflowing water from the Arctic suggests a higher contribution of atmospheric sources compared to ocean circulation. An east-west cross section of the Fram Strait, which included seven depth profiles, revealed higher PFAS concentrations in the surface water layer than in intermediate waters and a negligible intrusion into deep waters (>1000 m). Mass transport estimates indicated a net inflow of PFASs with ≥8 perfluorinated carbons via the boundary currents and a net outflow of shorter-chain homologues. We hypothesize that this reflects higher contributions from atmospheric sources to the Arctic outflow and a higher retention of the long-chain compounds in melting snow and ice.

The analysis of perfluoroalkyl substances at ppt level in milk and egg using UHPLC-MS/MS

ABSTRACT Per- and poly-fluorinated substances (PFASs) are man-made chemicals that have been used for a variety of applications and can end up in the food chain. New opinions on the risk assessment were recently published by the European Food Safety Authority, emphasising the need for more sensitive methods. From this, minimum required LOQs for the analytical method for analysis of milk and egg have been calculated for perfluorooctanoic acid (PFOA) and GenX (hexafluoropropylene oxide dimer acid, HFPO-DA). A fully validated method is described for analysis of 13 PFASs, including PFOA and HFPO-DA, in milk and egg. All compounds, except perfluorodecane sulphonate (PFDS), can be quantitatively determined in these matrices with a trueness ranging from 87% to 119% and a relative within-laboratory reproducibility between 12% and 41%. Also the method proved suitable for confirmation of the identity of the individual PFASs. The LOQ for HFPO-DA in milk and egg is 0.05 ng g−1, well below the calculated required LOQ. For PFOA in egg the determined LOQ is 0.025 ng g−1, nicely below the required level of 0.03 ng g−1. In milk the required LOQ was not achieved: 0.005 instead of 0.003 ng g−1. However, on six out of eight days an LOQ of 0.0025 ng g−1 was demonstrated. It is concluded that the required LOQs are achievable when instrument performance is optimal. The current method can be expanded with long chain PFASs by using a cellulose filter instead of the PTFE filter vials. The presented method was applied for a small-scale study in The Netherlands.

Photodegradation of Hexafluoropropylene Oxide Trimer Acid under UV Irradiation

As a novel alternative to traditional perfluoroalkyl substances (PFASs), including perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS), hexafluoroproplyene oxide trimer acid (HFPO-TA) has been detected worldwide in surface water. Moreover, recent researches have demonstrated that HFPO-TA has stronger bioaccumulation potential and higher hepatotoxicity than PFOA. To treat these contaminants e.g. PFOA and PFOS, some photochemical techniques by adding exogenous substances had been reported. However, there is still no report for the behavior of HFPO-TA itself under direct UV irradiation. The current study investigated the photo-transformation of HFPO-TA under UV irradiation in aqueous solution. After 72 hr photoreaction, 75% degradation ratio and 25% defluorination ratio were achieved under ambient condition. Reducing active species, i.e., hydrated electrons and active hydrogen atoms, generated from water splitting played dominant roles in degradation of HFPO-TA, which was confirmed by different effects of reaction atmospheres and quenching experiments. A possible degradation pathway was proposed based on the products identification and theoretical calculations. In general, HFPO-TA would be transformed into shorter-chain PFASs, including hexafluoropropylene oxide dimer acid (HFPO-DA), perfluoropropionic acid (PFA) and trifluoroacetate (TFA). This research provides basic information for HFPO-TA photodegradation process and is essential to develop novel remediation techniques for HFPO-TA and other alternatives with similar structures.

Evidence of Air Dispersion: HFPO-DA and PFOA in Ohio and West Virginia Surface Water and Soil near a Fluoropolymer Production Facility.

Perfluorooctanoic acid (PFOA) was used as a fluoropolymer manufacturing aid at a fluoropolymer production facility in Parkersburg, WV from 1951 to 2013. The manufacturer introduced a replacement surfactant hexafluoropropylene oxide dimer acid (HFPO-DA) that has been in use at this site since 2013. Historical releases of PFOA and related epidemiological work in this area has been primarily focused on communities downstream. To provide an update on the ongoing impacts from this plant, 94 surface water samples and 13 soil samples were collected mainly upstream and downwind of this facility. PFOA was detected in every surface water sample with concentrations exceeding 1000 ng/L at 13 sample sites within an 8 km radius of the plant. HFPO-DA was also found to be widespread with the highest levels (>100 ng/L) found in surface water up to 6.4 km north of the plant. One sample site, 28 km north of the plant, had PFOA at 143 ng/L and HFPO-DA at 42 ng/L. Sites adjacent to landfills containing fluorochemical waste had PFOA concentrations ranging up to >1000 ng/L. These data indicate that downwind atmospheric transport of both compounds has occurred and that the boundaries of the impact zone have yet to be fully delineated.

Solvent Suitability for HFPO-DA ("GenX" Parent Acid) in Toxicological Studies.

Per- and polyfluorinated alkyl substances (PFAS) are of significant interest because of their prevalence and environmental persistence. Further, for many PFAS, including fluorinated ethers, such as hexafluoropropylene oxide dimer acid (HFPO-DA, or the parent acid of "GenX"), toxicological data are sparse. In general, in vitro testing frequently uses dimethyl sulfoxide (DMSO) as a carrier solvent due to its low toxicity, solubility across vast chemical space, and permeation across biological barriers. For PFAS, laboratory practice has assumed that the materials are stable across a wide range of solvents, pHs, and temperatures. In this study, HFPO-DA stability was evaluated with DMSO and other commonly used solvents to determine each solvent's suitability for use in toxicity assays. The formation of HFPO-DA's degradation product, heptafluoropropyl 1,2,2,2-tetrafluoroethyl ether (Fluoroether E-1), was monitored by headspace gas chromatography-mass spectrometry (GC-MS) over time. These experiments revealed degradation of HFPO-DA to Fluoroether E-1 in DMSO and other aprotic, polar solvents, with half-lives on the order of hours (1 h, 1.25 h, and 5.2 h for DMSO, acetone, and acetonitrile, respectively). This rapid degradation suggests the need for caution when performing or using data from toxicity assessments on HFPO-DA and closely related PFAS compounds.

Multicompartment occurrence and partitioning of alternative and legacy per- and polyfluoroalkyl substances in an impacted river in China

Per- and polyfluoroalkyl substances (PFASs) are emerging global environmental contaminants. Exploring the occurrence and environmental behavior of PFASs in the aquatic environment is a key step in solving global fluorine chemical pollution problems. In this study, surface water, pore water, and sediment were collected from the main tributary and the middle and lower reaches of the Daling River, adjacent to the Fuxin fluorochemical manufacturing facilities in Liaoning Province in China, to elucidate the occurrence and partition behavior of PFASs. The total concentrations of PFASs ranged from 48.4 to 4578 ng/L in the overlying water, from 173 to 9952 ng/L in the pore water, and from 2.16 to 40.3 ng/g dw in the sediment fraction. Generally, perfluorobutanoic acid (PFBA) and perfluorobutane sulfonate (PFBS) were the predominant congeners in the samples, with the mean relative content fractions being almost consistently >40% in the dissolved phase and >25% in the sediment. Hexafluoropropylene oxide dimer acid (HFPO-DA) and chlorinated polyfluorinated ether sulfonic acid (6:2 Cl-PFESA) were detected, albeit at low levels. In addition, the detection frequency and the contribution of legacy long-chain PFASs in sediment were higher than those in the overlying water and pore water. Except for perfluorohexane sulfonate (PFHxS), the concentrations of the alternative PFASs in the pore water were higher than in the overlying water. The organic carbon fraction was a more important controlling factor for PFAS sediment levels than cations content. As with legacy long-chain PFASs, HFPO-DA and 6:2 Cl-PFESA tended to partition into the solid phase, whereas short-chain PFASs were readily distributed in the aqueous phase. Such research results will be helpful in modeling the transport and fate of PFASs released by point sources into coastal waters through rivers and in developing effective risk assessment and management strategies for the control of PFAS pollution.

Novel and legacy poly- and perfluoroalkyl substances (PFASs) in indoor dust from urban, industrial, and e-waste dismantling areas: The emergence of PFAS alternatives in China

With the phase out of perfluorooctanesulfonate (PFOS) and perfluorooctanoic acid (PFOA), the composition profiles of poly- and perfluoroalkyl substance (PFAS) in our living environment are unclear. In this study, 25 PFASs were analyzed in indoor dust samples collected from urban, industrial, and e-waste dismantling areas in China. PFOS alternatives, including 6:2 chlorinated polyfluorinated ether sulfonate (6:2 Cl-PFESA) (median: 5.52 ng/g) and 8:2 chlorinated polyfluorinated ether sulfonate (8:2 Cl-PFESA) (1.81 ng/g), were frequently detected. By contrast, PFOA alternatives, such as hexafluoropropylene oxide dimer acid (HPFO-DA, Gen-X) and ammonium 4,8-dioxa-3H-perfluorononanoate (ADONA), were not found in any of the dust samples. As expected, all legacy PFASs were widely observed in indoor dust, and 4 PFAS precursors were also detected. Dust concentrations of 6:2 Cl-PFESA were strongly correlated (p < 0.05) with those of 8:2 Cl-PFESA regardless of sampling sites. 6:2 Cl-PFESA was also significantly associated with that of PFOS in industrial and e-waste (p < 0.01) areas. Association analysis suggested that the sources of PFOS and its alternatives are common or related. Although ∑Cl-PFESA concentration was lower than that of PFOS (17.4 ng/g), industrial areas had the highest 6:2 Cl-PFESA/PFOS ratio (0.63). Composition profiles of PFASs in the industrial area showed the forefront of fluorine change. Thus, the present findings suggested that Cl-PFESAs are widely used as PFOS alternatives in China, and high levels of human Cl-PFESA exposure are expected in the future. Short-chain PFASs (C4–C7) were the predominant PFASs found in dust samples, contributing to over 40% of ∑total PFASs. Furthermore, perfluoro-1-butanesulfonate/PFOS and perfluoro-n-butanoic acid (PFBA)/PFOA ratios were 2.8 and 0.72, respectively. These findings suggested shifting to the short-chain PFASs in the environment in China. To the authors knowledge this is the first study to document the levels of 6:2 Cl-PFESA, 8:2 Cl-PFESA in indoor dust.

Emerging and legacy per- and polyfluoroalkyl substances in water, sediment, and air of the Bohai Sea and its surrounding rivers

Per- and polyfluoroalkyl substances (PFASs) contamination in the Bohai Sea and its surrounding rivers has attracted considerable attention in recent years. However, few studies have been conducted regarding the distribution of PFASs in multiple environmental media and their distributions between the suspended particles and dissolved phases. In this study, surface water, surface sediment, and air samples were collected at the Bohai Sea to investigate the concentration and distribution of 39 targeted PFASs. Moreover, river water samples from 35 river estuaries were collected to estimate PFAS discharge fluxes to the Bohai Sea. The results showed that total ionic compound (Σi-PFASs) concentrations ranged from 19.3 to 967 ng/L (mean 125 ± 152 ng/L) in the water and 0.70–4.13 ng/g dw (1.78 ± 0.76 ng/g) in surface sediment of the Bohai Sea, respectively. In the estuaries, Σi-PFAS concentrations were ranged from 10.5 to 13500 ng/L (882 ± 2410 ng/L). In the air, ΣPFAS (Σi-PFASs + Σn-PFASs) concentrations ranged from 199 to 678 pg/m3 (462 ± 166 pg/m3). Perfluorooctanoic acid (PFOA) was the predominant compound in the seawater, sediment, and river water; in the air, 8:2 fluorotelomer alcohol was predominant. Xiaoqing River discharged the largest Σi-PFAS flux to the Bohai Sea, which was estimated as 12,100 kg/y. Some alternatives, i.e., 6:2 fluorotelomer sulfonate acid (6:2 FTSA), hexafluoropropylene oxide dimer acid (HFPO-DA), and chlorinated 6:2 polyfluorinated ether sulfonic acid (Cl-6:2 PFESA), showed higher levels than or comparable concentrations to those of the C8 legacy PFASs in some sampling sites. The particle-derived distribution coefficient in seawater was higher than that in the river water. Using high resolution mass spectrometry, 29 nontarget emerging PFASs were found in 3 river water and 3 seawater samples. Further studies should be conducted to clarify the sources and ecotoxicological effects of these emerging PFASs in the Bohai Sea area.

Elevated levels of per- and polyfluoroalkyl substances in Cape Fear River Striped Bass (Morone saxatilis) are associated with biomarkers of altered immune and liver function

Per- and polyfluoroalkyl substances (PFAS) are anthropogenic chemicals of concern that persist in the environment. Environmental monitoring revealed high concentrations of hexafluoropropylene oxide dimer acid (HFPO-DA) and other novel PFAS in the lower Cape Fear River; however, there is limited information on PFAS exposures and effects of this contamination on aquatic biota. Serum concentrations of 23 PFAS in Striped Bass (Morone saxatilis) from the Cape Fear River (n = 58) and a reference population from an aquaculture laboratory on the Pamlico/Tar watershed (n = 29) were quantified using liquid chromatography and high-resolution mass spectrometry, and correlations between PFAS concentrations and health-related serum biomarkers were evaluated. Perfluorooctane sulfonate, the predominant PFAS in Cape Fear River Striped Bass serum, was detectable in every sample with serum concentrations reaching 977 ng/mL. Perfluorononanoic and perfluorodecanoic acid were also detected in all samples, with perfluorohexanesulfonic acid present in >98% of the samples. HFPO-DA (range <0.24–5.85 ng/mL) and Nafion byproduct 2 (range <0.2–1.03 ng/mL) were detected in 48% and 78% of samples, respectively. The mean total PFAS concentration found in domestic Striped Bass raised in well-water under controlled aquaculture conditions was 40 times lower, with HPFO-DA detected in 10% of the samples, and Nafion byproduct 2 was not detected. The elevated PFAS concentrations found in the Cape Fear River Striped Bass were associated with biomarkers of alterations in the liver and immune system.

Evaluation of Maternal, Embryo, and Placental Effects in CD-1 Mice following Gestational Exposure to Perfluorooctanoic Acid (PFOA) or Hexafluoropropylene Oxide Dimer Acid (HFPO-DA or GenX).

Background:Perfluorooctanoic acid (PFOA) is a poly- and perfluoroalkyl substance (PFAS) associated with adverse pregnancy outcomes in mice and humans, but little is known regarding one of its replacements, hexafluoropropylene oxide dimer acid (HFPO-DA, referred to here as GenX), both of which have been reported as contaminants in drinking water.Objectives:We compared the toxicity of PFOA and GenX in pregnant mice and their developing embryo–placenta units, with a specific focus on the placenta as a hypothesized target.Methods:Pregnant CD-1 mice were exposed daily to PFOA (0, 1, or ) or GenX (0, 2, or ) via oral gavage from embryonic day (E) 1.5 to 11.5 or 17.5 to evaluate exposure effects on the dam and embryo–placenta unit. Gestational weight gain (GWG), maternal clinical chemistry, maternal liver histopathology, placental histopathology, embryo weight, placental weight, internal chemical dosimetry, and placental thyroid hormone levels were determined.Results:Exposure to GenX or PFOA resulted in increased GWG, with increase in weight most prominent and of shortest latency with GenX exposure. Embryo weight was significantly lower after exposure to PFOA (9.4% decrease relative to controls). Effect sizes were similar for higher doses ( PFOA and GenX) and lower doses ( PFOA and GenX), including higher maternal liver weights, changes in liver histopathology, higher placental weights and embryo–placenta weight ratios, and greater incidence of placental abnormalities relative to controls. Histopathological features in placentas suggested that PFOA and GenX may exhibit divergent mechanisms of toxicity in the embryo–placenta unit, whereas PFOA- and GenX-exposed livers shared a similar constellation of adverse pathological features.Conclusions:Gestational exposure to GenX recapitulated many documented effects of PFOA in CD-1 mice, regardless of its much shorter reported half-life; however, adverse effects toward the placenta appear to have compound-specific signatures. https://doi.org/10.1289/EHP6233

Dietary Uptake and Depuration Kinetics of Perfluorooctane Sulfonate, Perfluorooctanoic Acid, and Hexafluoropropylene Oxide Dimer Acid (GenX) in a Benthic Fish.

Per- and poly-fluoroalkyl substances (PFAS) are ubiquitously distributed throughout aquatic environments and can bioaccumulate in organisms. We examined dietary uptake and depuration of a mixture of 3 PFAS: perfluorooctanoic acid (PFOA; C8 HF15 O2 ), perfluorooctane sulfonate (PFOS; C8 HF17 SO3 ), and hexafluoropropylene oxide dimer acid (HPFO-DA; C6 HF11 O3 ; trade name GenX). Benthic fish (blue spot gobies, Pseudogobius sp.) were fed contaminated food (nominal dose 500 ng g-1 ) daily for a 21-d uptake period, followed by a 42-d depuration period. The compounds PFOA, linear-PFOS (linear PFOS), and total PFOS (sum of linear and branched PFOS) were detected in freeze-dried fish, whereas GenX was not, indicating either a lack of uptake or rapid elimination (<24 h). Depuration rates (d-1 ) were 0.150 (PFOA), 0.045 (linear-PFOS), and 0.042 (linear+branched-PFOS) with corresponding biological half-lives of 5.9, 15, and 16 d, respectively. The PFOS isomers were eliminated differently, resulting in enrichment of linear-PFOS (70-90%) throughout the depuration period. The present study is the first reported study of GenX dietary bioaccumulation potential in fish, and the first dietary study to investigate uptake and depuration of multiple PFASs simultaneously, allowing us to determine that whereas PFOA and PFOS accumulated as expected, GenX, administered in the same way, did not appear to bioaccumulate. Environ Toxicol Chem 2020;39:595-603. © 2019 SETAC.

Occurrence and source apportionment of novel and legacy poly/perfluoroalkyl substances in Hai River basin in China using receptor models and isomeric fingerprints

A variety of fluorinated alternatives are being manufactured and applied as a consequence of stringent regulations on legacy poly/perfluoroalkyl substances (PFASs). In this study, 26 emerging and legacy PFASs were measured in the surface water (including dissolved phase and suspended particulate matter) and sediments taken from Hai River basin, China. The total concentrations of PFASs (∑PFASs) ranged from 1.74 to 172 ng/L, with perfluorooctanonate (PFOA) as the dominant compound (15.2% of the ∑PFASs, median value). Emerging PFASs, such as dimer acid of hexafluoropropylene oxide dimer acid (HFPO-DA) and trimer acid (HFPO-TA), were widely detected in the water samples. Specifically, chlorinated polyfluorinated ether sulfonate (F–53B) was observed to be predominant in some sediment samples. A receptor model, Unmix, was introduced to identify the sources of PFASs in the surface water, and the results indicated that fire-fighting foam/fluoropolymer processing aids (36.6%) were the dominant source. The field-based sediment-water (organic carbon normalized) coefficients, Koc, were correlated to the carbon chain lengths of the PFASs. A technique coupling one-way analysis of variance with chemical mass balance model was developed to trace the manufacturing sources of PFOA. Electrochemical fluorination (ECF) was the major PFOA manufacturing source with considerable contribution by telomerization. For the first time, the isomers of perfluorooctane sulfonamide (PFOSA) were quantified in the environmental samples. The lower proportion of branched (br-) PFOSA isomers and higher percentage of br-perfluorooctane sulfonate (PFOS) isomers in the water samples relative to their corresponding commercial products, provided more direct evidences that br-PFOSA isomers were biotransformed more easily than n-PFOSA, explaining the observed enrichment of br-PFOS in the aquatic environment.