Abstract  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.

Abstract  The findings of per- and polyfluoroalkyl substances (PFAS) in humans and the environment all over the world have raised concerns and public awareness for this group of man-made chemicals. In the last three decades, this led to different regulatory restrictions for specific PFAS as well as shifts in the production and usage of these substances. In this study, we analyzed the PFAS levels of 100 human blood plasma samples collected from 2009 to 2019 for the German Environmental Specimen Bank (ESB) to further elucidate the time course of exposure towards this substance group as shown by Schröter-Kermani et al., (2013) with samples from 1982 to 2010. A spectrum of 37 PFAS, including perfluorocarboxylic (PFCA) and -sulfonic acids (PFSA) as well as potential precursors and substitutes like ADONA, GenX or F-53B was analyzed by UHPLC coupled with high-resolution mass spectrometry. Validation was successful for 33 of the substances. The two legacy substances perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS) were detected in every sample of the 2009-2019 dataset and showed the highest concentrations with ranges of 0.27-14.0 ng/mL and 1.21-14.1 ng/mL, respectively. A significant portion of total PFOS analytes was present as branched isomers (mean: 34 ± 7%). High detection frequencies of 95% and 82% were also found for perfluorohexane sulfonic acid (PFHxS) and perfluorononanoic acid (PFNA), respectively, but in lower concentrations (PFHxS:

Abstract  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.

Abstract  The fluoropolymer manufacturing industry is moving to alternative polymerization processing aid technologies with more favorable toxicological and environmental profiles as part of a commitment to curtail the use of long-chain perfluoroalkyl acids (PFAAs). To facilitate the environmental product stewardship assessment and premanufacture notification (PMN) process for a candidate replacement chemical, we conducted acute and chronic aquatic toxicity tests to evaluate the toxicity of ammonium 2,3,3,3-tetrafluoro-2-(heptafluoropropoxy)-propanoate (C6HF11O3.H3N) or the acid form of the substance to the cladoceran, Daphnia magna, the green alga, Pseudokirchneriella subcapitata, and a number of freshwater fish species including the rainbow trout, Oncorhynchus mykiss, In addition, testing with the common carp, Cyprinus carpio, was conducted to determine the bioconcentration potential of the acid form of the compound. Based on the relevant criteria in current regulatory frameworks, the results of the aquatic toxicity and bioconcentration studies indicate the substance is of low concern for aquatic hazard and bioconcentration in aquatic organisms. Evaluation of environmental monitoring data in conjunction with the predicted no effect concentration (PNEC) based on the available data suggest low risk to aquatic organisms.

Abstract  Long-chain per- and polyfluoroalkyl substances (PFASs) are being replaced by short-chain PFASs and fluorinated alternatives. For ten legacy PFASs and seven recently discovered perfluoroalkyl ether carboxylic acids (PFECAs), we report (1) their occurrence in the Cape Fear River (CFR) watershed, (2) their fate in water treatment processes, and (3) their adsorbability on powdered activated carbon (PAC). In the headwater region of the CFR basin, PFECAs were not detected in raw water of a drinking water treatment plant (DWTP), but concentrations of legacy PFASs were high. The U.S. Environmental Protection Agency's lifetime health advisory level (70 ng/L) for perfluorooctanesulfonic acid and perfluorooctanoic acid (PFOA) was exceeded on 57 of 127 sampling days. In raw water of a DWTP downstream of a PFAS manufacturer, the mean concentration of perfluoro-2-propoxypropanoic acid (PFPrOPrA), a replacement for PFOA, was 631 ng/L (n = 37). Six other PFECAs were detected, with three exhibiting chromatographic peak areas up to 15 times that of PFPrOPrA. At this DWTP, PFECA removal by coagulation, ozonation, biofiltration, and disinfection was negligible. The adsorbability of PFASs on PAC increased with increasing chain length. Replacing one CF2 group with an ether oxygen decreased the affinity of PFASs for PAC, while replacing additional CF2 groups did not lead to further affinity changes.

Abstract  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.

Abstract  Per- and polyfluoroalkyl substances (PFAS) represent a group of synthetic compounds widely used in industry plants due to their low grade of degradation, surfactant properties, thermic and flame resistance. These characteristics are useful for the industrial production, however they are also potentially dangerous for human health and for the environment. PFAS are persistent pollutants accumulating in waters and soil and recoverable in foods due to their release by food packaging. Humans are daily exposed to PFAS because these compounds are ubiquitous and, when assimilated, they are difficult to be eliminated, persisting for years both in humans and animals. Due to their persistence and potential danger to health, some old generation PFAS have been replaced by newly synthesized PFAS with the aim to use alternative compounds presumably safer for humans and the environment. Yet, the environmental pollution with PFAS remains a matter of concern worldwide and led to large-scale epidemiological studies both on plants' workers and on exposed people in the general population. In this context, strong concern emerged concerning the potential adverse effects of PFAS on the thyroid gland. Thyroid hormones play a critical role in the regulation of metabolism, and thyroid function is related to cardiovascular disease, fertility, and fetal neurodevelopment. In vitro, ex vivo data, and epidemiological studies suggested that PFASs may disrupt the thyroid hormone system in humans, with possible negative repercussions on the outcome of pregnancy and fetal-child development. However, data on the thyroid disrupting effect of PFAS remain controversial, as well as their impact on human health in different ages of life. Aim of the present paper is to review recent data on the effects of old and new generation PFAS on thyroid homeostasis. To this purpose we collected information from in vitro studies, animal models, and in vivo data on exposed workers, general population, and pregnant women.

Abstract  Fluorochemical production plants (FPP) are primary emission sources of per- and polyfluoroalkyl substances (PFASs) to the local environment. An FPP located in the Netherlands has historically used perfluorooctanoic acid (PFOA) for fluoropolymer production and is currently using GenX (HFPO-DA; 2,3,3,3-tetrafluoro-2-(heptafluoropropoxy)propionic acid) as a replacement. This study reviewed existing data from open access reports and peer reviewed publications on the environmental presence of PFOA and GenX in environmental matrices such as surface water, groundwater, soil and vegetation. Published data on human exposure to PFOA and GenX (i.e. via drinking water and food as well as blood monitoring) were reviewed in order to assess the influence of the FPP on contamination of the local population. Concentrations in environmental and human exposure samples were compared to (inter)national quality standards or risk limits. The data showed higher PFOA and GenX concentrations in surface water, groundwater, soil and vegetation samples taken close to point sources, and the highest observed concentrations exceeded these standards and limits (except for PFOA in soil). Drinking water and food also contained higher PFOA and GenX concentrations in samples taken close to point sources compared to samples further away. Tolerable daily intake (TDIs) for both PFASs were exceeded, however, only in a maximum exposure scenario. Blood monitoring of the local population near the FPP, and FPP workers, confirmed high exposure can occur as blood concentrations of several individuals exceeded the safe level. This paper provides a comprehensive overview on PFOA and GenX contamination close to point sources in the Netherlands.

Abstract  The dust on indoor and outdoor surfaces of the window glasses were collected using sterile cotton balls in 11 cities from China. Two sampling campaigns were conducted with the time interval of 7 days to investigate the accumulation especially during the Spring festival holidays. Twenty-nine perfluoroalkyl acids (PFAA) were quantified to investigate concentration, composition, and toddlers' exposure. The concentrations of ∑PFAA ranged from no detection (nd) to 43 ng/m2 (mean 8.9 ± 10 ng/m2). Perfluorobutanoic acid (PFBA) was detected in 78% samples and accounted for 55 ± 21% of ∑PFAA concentrations. 6:2 fluorotelomer sulfonic acid (6:2 FTSA) and hexafluoropropylene oxide dimer acid (HFPO-DA) were detected in more than 50% samples indicating the use of alternatives. Fluorotelomer carboxylic acid (FTCA) and fluorotelomer unsaturated acid (FTUCA) were found in the dust, implying the degradation of fluorotelomer alcohols (FTOH). The highest concentration of ∑PFAA (43 ng/m2) was found in outdoor dust from Xinzhou, Shanxi Province. Higher ∑PFAA concentrations were found in indoor dust than outdoor in 6 paired samples (3 from Feb. 14 and 3 from Feb. 21). In Tianjin and Handan, the concentrations of ∑PFAA from outdoor surfaces were higher in sampling campaign I (SC I, Feb. 21) than in sampling campaign II (SC II, Feb. 14), implying intensive outdoor release. The exposure of 2-year-old toddlers to PFAA via hand-to-mouth ingestion and dermal absorption was estimated; the mean values of intake were 2.1 and 1.5 pg/kg body weight, respectively, assuming an exposure time of 1 h.

Abstract  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.

Abstract  In June 2017, local health departments asked the North Carolina Department of Health and Human Services (NCDHHS) to provide health information and guidance regarding 2,3,3,3,-tetrafluoro-2-(1,1,2,2,3,3,3- heptafluoropropoxy)-propanoate (GenX) and other per- and polyfluoroalkyl substances (PFAS) that had been detected in the Cape Fear River, an important drinking water source. PFAS are a group of man-made chemicals that have been used in industry and consumer products worldwide since the 1950s. Most PFAS do not break down in the environment and can accumulate over time, resulting in increased human exposures. Limited studies in humans have indicated that some PFAS might affect reproduction, development, and the immune system and increase the risk for certain types of cancer. The source of GenX and other PFAS contamination in the Cape Fear River was a PFAS chemical manufacturing facility. NCDHHS identified households near the facility with the highest concentrations of GenX in their private drinking water wells.

Abstract  The emerging classes of perfluorinated alkyl substances (PFAS) (e.g., Perfluorobutanoic acid (PFBA), perfluorobutane sulfonic acid (PFBS), GenX, ADONA, and F-53B) are persistent and recalcitrant to removal by conventional treatment techniques. Herein, we report on poly (N-[3-(dimethylamino)propyl]acrylamide, methyl chloride quaternary, DMAPAA-Q) hydrogel matrix as an effective sorbent for sequestering PFAS from different water matrices. The selective removal of 16 PFAS from different classes using DMAPAA-Q polymer was confirmed in surface waters and treated wastewater at environmentally relevant concentration (i.e., <1000 ng/L). The results showed fast removal kinetics with equilibrium time of 60-120 min and a higher removal of sulfonated than carboxylic PFAS, regardless of their chain lengths. These observations were in agreement with adsorption energy calculations of short- and long-chain PFAS on poly DMAPAA-Q hydrogel using density functional theory (DFT). No desorption was observed when the experimental time was extended to 24 h, which gives an added advantage of poly DMAPAA-Q hydrogel over previously reported adsorbents in the literature. In addition, the removal efficiency was not affected under a varying pH range of 4-10. The impact of background anions on PFAS removal by poly DMAPAA-Q hydrogel was tested and found to follow an order of SO42- > Cl- > NO3-. The performance of poly DMAPAA-Q hydrogel was maintained in six consecutive adsorption/regeneration cycles to remove PFAS. The unique fast kinetics and high adsorption activity of poly DMAPAA-Q hydrogel towards PFAS exhibits a great potential for being a promising material for PFAS control.

Abstract  OBJECTIVES: A shift in the microbiota of chronic rhinosinusitis has been described after radiotherapy to the sinonasal cavity and skull base. There is a paucity of literature characterizing the bacteriology of post radiation sinusitis using next-generation gene sequencing techniques. This study aims to describe and compare the microbial flora of rhinosinusitis after radiotherapy using both culture and molecular techniques for microbial DNA detection.

METHODS: The medical records of patients treated with external beam radiation for sinonasal, nasopharyngeal, or skull base malignancy were reviewed at a tertiary care facility. Patients' sinonasal cavities were swabbed for routine culture or brushed for molecular gene sequencing. Swab specimens were processed for standard microbial culture, and brush specimens were sent for gene sequencing at Micro GenX Laboratory (Lubbock, Texas, USA).

RESULTS: Twenty-two patients were diagnosed with chronic sinusitis after undergoing radiotherapy. Staphylococcus aureus was the most common organism identified by both culture and gene sequencing, followed by Pseudomonas aeruginosa. Several additional organisms were detected by gene sequencing that were not isolated by routine culture techniques. Gene sequencing identified pathogens differing from culture results in 50% of patients examined.

CONCLUSION: The bacteriology of post radiation sinusitis appears to resemble the microorganisms responsible for chronic sinusitis in healthy adults. Next generation gene sequencing techniques may reveal additional organisms responsible for sinusitis and provide complementary results that may impact the medical treatment of post radiation sinusitis.

Abstract  FRD-902 was applied as a single 0.5-mL dermal dose to the shaved intact skin of a single New Zealand White rabbit. Since no corrosion occurred, 2 additional rabbits were treated. The test substance was applied to a 6 cm² area of skin. The application area was covered with a 2-ply gauze square which was held in place with non-irritating tape and covered with porous tape for a semi-occlusive dressing. The rabbits were exposed to the test substance for 4 hours after which the test substance was removed. Test sites were evaluated and scored by the method of Draize for signs of dermal irritation approximately 60 minutes, and 24, 48/50, and 72 hours after test substance removal. The rabbit that was initially treated was also examined immediately after test substance removal. Erythema (score of 1 or 2) but no edema was observed in the 3 rabbits on the day of dosing. No dermal irritation was observed at 24, 48/50, or 72 hours after removal of the test substance. No clinical signs were observed, and no body weight loss occurred. Under the conditions of this study, FRD-902 produced erythema, which cleared by 24 hours, when applied to the skin of rabbits. In accordance with the provisions of Directive 67/548/EEC, classification is not required based on the results of this study.

Abstract  STUDY: Determination of the Water Solubility and Vapor Pressure ofH-28307 SPONSOR: E.I. du Pont de Nemours and Company WILDLIFE INTERNATIONAL, LTD. PROJECT NUMBER: 112C-133 TEST DATES: Experimental Start (OECD) - February 11, 2008 Experimental Start (EPA)- February 18, 2008 Experimental Termination-February 21, 2008 RESULTS: H-28307 was determined to be infinitely soluble in HPLC-grade bottled reagent water at 20°C. The vapor pressure of H-28307 at 20°C was 306 ± 13.7 Pa (N = 3, CV = 4.48%).