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Perfluoroalkyl acids (PFAAs) are emerging pollutants that endangers food safety. Developing methods for the selective determination of trace PFAAs in complex samples remains challenging. Herein, an ionic liquid modified porous imprinted phenolic resin-dispersive filter extraction-liquid chromatography-tandem mass spectrometry (IL-PIPR−DFE−LC-MS/MS) method was developed for the determination of perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) in eggs. The new IL-PIPR adsorbent was prepared at room temperature, which avoids the disorder and instability of the template at high temperatures. The imprinting factor of IL-PIPR for PFOA and PFOS exceeded 7.3. DFE, combined with IL-PIPR (15 mg), was used to extract PFOA and PFOS from eggs within 15 min. The established method exhibits low limits of detection (0.01–0.02 ng/g) and high recoveries (84.7%–104.7%), which surpass those of previously reported methods. This work offers a new approach to explore advanced imprinted adsorbents for PFAAs, efficient sample pretreatment technique, and analytical method for pollutants in foods. [Display omitted] • Ionic liquid-porous imprinted resin (IL-PIPR) was synthesized at room temperature. • The imprinting factors of IL-PIPR for PFOA and PFOS is 7.3 and 8.9, respectively. • IL-PIPR has fast mass transfer (2 min) and the adsorption capacity exceeds 490 mg/g. • Extraction process (IL-PIPR-DFE) of PFOA and PFOA in egg sample within 15 min. • IL-PIPR-DFE-LC-MS/MS overcomes matrix interference and is accurate and rapid. [ABSTRACT FROM AUTHOR]

This study assessed the occurrence, origins, and potential risks of emerging perfluoroalkyl acids (PFAAs) for the first time in drinking water resources of Khyber Pakhtunkhwa, Pakistan. In total, 13 perfluoroalkyl carboxylic acids (PFCAs) with carbon (C) chains C4-C18 and 4 perfluoroalkyl sulfonates (PFSAs) with C chains C4-C10 were tested in both surface and ground drinking water samples using a high-performance liquid chromatography system (HPLC) equipped with an Agilent 6460 Triple Quadrupole liquid chromatography–mass spectrometry (LC–MS) system. The concentrations of ∑PFCAs, ∑PFSAs, and ∑PFAAs in drinking water ranged from 1.46 to 72.85, 0.30–8.03, and 1.76–80.88 ng/L, respectively. Perfluorobutanoic acid (PFBA), perfluorohexanoic acid (PFHxA), and perfluoropentanoic acid (PFPeA) were the dominant analytes in surface water followed by ground water, while the concentration of perfluorobutane sulfonate (PFBS), perfluorooctanoic acid (PFOA), perfluoroheptanoic acid (PFHpA), perfluorooctane sulfonate (PFOS), perfluorohexane sulfonate (PFHxS), perfluorononanoic acid (PFNA), perfluorodecanoic acid (PFDA), perfluoroundecanoic acid (PFUnDA), and perfluorododecanoic acid (PFDoDA) were greater than long-chain PFOA and PFOS. The correlation statistics, which showed a strong correlation (p < 0.05) between the PFAA analytes, potentially indicated the fate of PFAAs in the area's drinking water sources, whereas the hierarchical cluster analysis (HCA) and principal component analysis (PCA) statistics identified industrial, domestic, agricultural, and commercial applications as potential point and non-point sources of PFAA contamination in the area. From risk perspectives, the overall PFAA toxicity in water resources was within the ecological health risk thresholds, where for the human population the hazard quotient (HQ) values of individual PFAAs were < 1, indicating no risk from the drinking water sources; however, the hazard index (HI) from the ∑PFAAs should not be underestimated, as it may significantly result in potential chronic toxicity to exposed adults, followed by children. [Display omitted] • Twelve perfluoroalkyl acids were detected in drinking water resources of Pakistan. • Perfluorobutanoic acid and Perfluorobutane sulfonate were the most abundant compounds. • Multivariate statistics identified anthropogenic activities as the potential sources. • Perfluoroalkyl acid levels were with in the world risk thresholds. • Perfluoroalkyl acid toxicity was substantially higher in children than in adults. [ABSTRACT FROM AUTHOR]

Perfluoroalkyl acids (PFAAs) are environmentally persistent components of surfactants that consist of fully fluorinated carbon chains and a terminal sulfonate or carboxylate polar head moiety. Due to their unique amphiphilic properties, PFAAs are used in the manufacturing of products such as aqueous film forming foams (AFFF). There is cause for concern for PFAA contamination resulting from runoff and groundwater infiltration of AFFF that were used during fire training. This study analyzed water and sediment samples that were collected over a 13-month sampling period from bayous upstream and downstream of two former fire training areas located near Barksdale Air Force Base (BAFB); the occurrence and magnitude of PFAAs supported an aquatic ecological risk assessment of potential impacts of PFAAs at the site. Liquid chromatography coupled with mass spectrometry was used for determination of 6 PFAAs listed under the third Unregulated Contaminant Monitoring Rule (UCMR 3). Total PFAA concentrations in surface water and sediment samples ranged from 0 (ND) 7.1 ng/mL and 0 (ND)31.4 ng/g, respectively. Perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) were the predominant PFAAs detected. In general, perfluorosulfonates were quantified more frequently and at higher concentrations than perfluorocarboxylates. The perfluoroalkyl chain length of PFAAs also showed significant influence on PFAA concentrations when analyzed by Spearman's rank correlation analysis. Some contamination we observed in surface water and sediment samples from reference locations could be a result of local runoff from the use of commercial products containing per- and poly-fluoroalkyl substances (PFAS), but AFFF appears to be the primary source given the close proximity of the historical fire training areas. [ABSTRACT FROM AUTHOR]

Per‐ and polyfluoroalkyl substances (PFAS) are organic pollutants that may have adverse effects on the ecosystem. Despite the global presence of PFAS, knowledge of PFAS on the African continent is limited because monitoring of PFAS is challenging and often not feasible owing to the lack of analytical capacity and high cost. However, it is necessary to understand the environmental risks posed by these chemicals in developing countries, because increasing urbanization will likely increase PFAS contamination in the environment. Although, as far as is known, PFAS concentrations in the African aquatic environment are generally lower than in more developed countries, exceedances of ecological quality standards (EQS) were reported in a few cases, providing evidence of potential ecological risks to these ecosystems. However, the number of ecosystems at risk will likely increase as urbanization and modernization increase in African countries. Therefore, environmental regulations should be updated and implemented to reduce further contamination of the aquatic environment with these chemicals. In addition, analytical laboratories in Africa should develop their capacity to detect PFAS and related compounds regularly and routinely. Local hot spots need to be identified, the influence of these hot spots on the PFAS burden in the environment should be investigated, and environmental regulations should be implemented for these hot spots to reduce their environmental impact. Therefore, we recommend a more routine monitoring of PFAS, including new PFAS that are currently used as perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) alternatives, which are not regulated and environmentally concerning. Integr Environ Assess Manag 2021;17:726–732. © 2021 SETAC KEY POINTS: PFAS concentrations in the African aquatic environment are generally low compared to developed countries, but they sometimes do exceed ecological quality standard values, providing evidence for potential ecological risks at these ecosystems.Environmental regulations should be updated and implemented, as the number of ecosystems at risks will likely increase due to increasing urbanization and modernization of African countries, to reduce further contamination of the aquatic environment with PFAS.Analytical laboratories in Africa need to develop their capacity to detect PFAS and related compounds regularly and on a routine basis.Local hotspots need to be identified, the influence of these hotspots on the PFAS burden in the aquatic environment should be investigated, and environmental regulations should be implemented for these hotspots to reduce their environmental impact. [ABSTRACT FROM AUTHOR]

Data from the National Health and Nutrition Examination Survey (N = 6141) for the years 2003–2016 for US adults were analyzed to evaluate the impact of glomerular hyperfiltration on the observed concentrations of perfluorooctanoic acid (PFOA), perfluorooctane sulfonic acid (PFOS), perfluorodecanoic acid, perfluorohexane sulfonic acid (PFHxS), and perfluorononanoic acid (PFNA) for several disease groups. Hyperfiltrators were defined as having an estimated glomerular filtration rate (eGFR) ≥ 110 mL/min/1.73 m2, and normal filtrators were defined as those having an eGFR between 90 and 110 mL/min/1.73 m2. The seven disease groups for which the data were analyzed were as follows: those (i) without any diseases; (ii) with hypertension only; (iii) with albuminuria only; (iv) with anemia only; (v) with diabetes only; (vi) with hypertension and one or more of diabetes, anemia, and albuminuria; and (vii) with two or more of diabetes, anemia, and albuminuria without hypertension. For almost every PFAA, for all seven disease groups except the albuminuria only group, hyperfiltrators had lower adjusted geometric means (AGM) than normal filtrators. For example, for the disease group with hypertension only, for PFOS, the AGMs for hyperfiltrators and normal filtrators were 8.3 and 10.6 ng/mL, respectively, for the total population. For the group with albuminuria only, normal filtrators were found to have higher AGMs than hyperfiltrators for the total population and males. For example, for PFHxS, the AGMs for normal and hyperfiltrators were 0.98 and 1.05 ng/mL, respectively, for the total population. For females, these AGMs for normal and hyperfiltrators were 0.96 and 0.86 ng/mL respectively. Males usually had higher AGMs than females, but the reverse was also true occasionally. Usually, male–female differences were substantially narrower for normal filtrators than hyperfiltrators. Irrespective of the filtration status, the disease group with hypertension only had the highest AGMs for every PFAA. AGMs for the anemia only group were the lowest for every PFAA as compared with other disease groups among hyperfiltrators. [ABSTRACT FROM AUTHOR]

Perfluoroalkyl substances (PFAS) are surface‐active agents used in diverse industrial and commercial applications. They contaminate both freshwater and marine ecosystems, are highly persistent, and accumulate through trophic transfer. Seabirds are exposed to environmental contaminants due to their high trophic position in food webs and relatively long lifespan. We measured levels of 10 perfluoroalkyl acids (PFAAs) in egg yolks of yellow‐legged gulls (Larus michahellis) breeding in the northern Adriatic Sea (Northeast Italy). We examined variations in PFAAs within clutches (between eggs of different laying order) and among clutches. Perfluorooctane sulfonate (PFOS) was the most abundant yolk PFAA (mean = 42.0 ng/g wet wt), followed by perfluorooctanoic acid (PFOA; 3.8 ng/g wet wt) and perfluorododecanoic acid (PFDoDa; 2.8 ng/g wet wt). The ∑PFAAs averaged 57.4 ng/g wet weight, ranging between 26.5 and 115.0 ng/g wet weight. The PFAA levels varied substantially among clutches (0.29–0.79 of the total variation), whereas the effects of laying order were considerably weaker (0.01–0.13). Egg‐laying order effects were detected for ∑PFAAs, PFOS, perfluorononanoic acid (PFNA), perfluorodecanoic acid (PFDA), perfluoroundecanoic acid (PFUnA), and PFDoDa, whereby the last‐laid eggs exhibited lower PFAA concentrations than early‐laid eggs. Our results indicate that seagulls from the northern Adriatic basin deposit measurable amounts of PFAAs in their eggs. The large among‐clutches differences in PFAAs suggest that exposure of yellow‐legged gull females to these compounds is highly variable. Environ Toxicol Chem 2021;40:744–753. © 2020 SETAC [ABSTRACT FROM AUTHOR]

For decades, perfluoroalkyl acids (PFAAs) have been commonly used for industrial and commercial purposes due to their water- and stain-resistant properties. Persistent pollutants that contain PFAAs have been associated with adverse health effects in humans, and many studies have documented dietary intake, indoor air inhalation, and dermal contact as the potential routes for human exposure to PFAAs. The aim of this study was to assess the level of PFAAs in the serum samples of a general population in a specific region in Malaysia. Using 219 serum samples collected from residents of Klang Valley, Malaysia, the levels of nine PFAAs were analyzed using liquid chromatography-tandem mass spectrometry. In addition, questionnaire surveys on the dietary habits and lifestyles of the subjects were conducted. The results showed that PFAA concentrations of up to 32.57 ng/mL were detected in all serum samples. In 82.6% of the participants, at least seven PFAAs were detected in the serum samples, with perfluorooctanesulfonic acid being the predominant PFAA (median = 8.79 ng/mL). In the adjusted regression model, the concentrations of most PFAAs were higher in men than in women and positively correlated with age, although body mass index and smoking were not significantly associated with the serum PFAA concentrations. Taking into consideration the lifestyle variables, significant associations were found between nonstick cookware and perfluorononanoic acid, between dental floss and cosmetics and perfluorodecanoic acid (PFDA), and between leather sofa and perfluoroundecanoic acid (PFUnDA). Besides, consumption of beef was significantly associated with increased levels of serum PFUnDA, whereas consumption of lamb and chicken eggs was negatively associated with the serum levels of PFUnDA and PFDA, respectively. [ABSTRACT FROM AUTHOR]

Perfluoroalkyl acids (PFAAs) are environmentally and biologically persistent chemicals. In this study, we investigated the concentrations of six PFAAs in dust samples collected from different indoor environments in a college campus in Tainan, Taiwan, and assessed the health risk of PFAAs exposure to college students. We also analyzed the effects of dust characteristics (total organic carbon, moisture content, and dust content) on PFAAs levels. With regard to the space type, the median of total PFAAs concentrations were in the order of laboratories (528.9 μg kg−1) > offices (304.2 μg kg−1) > dormitories (180.1 μg kg−1) > classrooms (105.1 μg kg−1). With regard to the height from the ground, the median total PFAAs concentrations were in the order of dust near the floors (>2 m; 383.6 μg kg−1) > near the ceiling (0–2 m; 202.5 μg kg−1) > on the ground (0 m; 145.6 μg kg−1). The main species of PFAAs, perfluorooctane sulfonate and short-chain perfluoroalkyl carboxylates, accounted for respectively 30%–60% and ∼20%–37% of total PFAAs pollution in the indoor space types and sampling heights under consideration. The average daily intake (ADI) values of six PFAAs for college students were found to be 0.059–0.126 ng kg−1 BW day−1 (BW: body weight), with dormitories and workplaces (i.e., laboratories and offices) accounting for over 40% and ∼50% of the ADI, respectively. The estimated hazard quotient ranged from 0.0029 to 0.0063, three orders of magnitude lower than 1, suggesting relatively low risks for college students exposed to the six PFAAs monitored in indoor dust. The analysis of dust characteristics revealed that total organic carbon did not have a significant effect on PFAAs levels as we expected. In contrast, dust moisture and cation content dominated PFAAs accumulation. [Display omitted] • PFAAs were found with a high detection frequency (98.1%) in indoor dust. • PFAAs median concentrations were found in labs > offices > dorms > classrooms. • PFAAs levels were in the order of near the floors > near the ceiling > on the ground. • The main species of PFAAs in indoor dust were PFOS and short-chain PFCAs. • Moisture and cation content dominate PFAAs accumulation rather than TOC. [ABSTRACT FROM AUTHOR]

Serum perfluoroalkyl acids (PFAAs) have been linked to disruption of maternal thyroid hormone homeostasis, but results have varied between studies which we hypothesized was due to timing of the thyroid hormone measurements, variability in PFAA isomer patterns, or presence of other stressors. In a longitudinal study design, we investigated the time-dependency of associations between PFAA isomers and thyroid hormones during pregnancy and post-partum while considering thyroid peroxidase antibody (TPOAb) status and mercury (Hg) co-exposure. In participants of a prospective Canadian birth cohort (n = 494), free thyroxine (FT4), free triiodothyronine (FT3), thyroid stimulating hormone (TSH) and TPOAb were quantified in maternal plasma collected in each trimester and 3-months postpartum, and 25 PFAAs (15 linear and 10 branched) and Hg were quantified in samples collected during the second trimester. Perfluorohexane sulfonate (PFHxS) and total branched isomers of perfluorooctane sulfonate (PFOS) were positively associated with TSH in mixed-effect models, with strongest associations early in gestation. Throughout pregnancy and post-partum, PFHxS was inversely associated with FT4, consistent with elevated TSH, while Hg was inversely associated with FT3. In TPOAb-positive women, negative associations were found between PFUnA and FT4, and 1 m -PFOS and TSH, supporting previous studies that thyroid disorder could increase susceptibility to PFAA-mediated hormone dysregulation. Hg did not confound associations but was a significant interaction term, revealing further positive associations between PFOS isomers (∑3 m +4 m -PFOS) and TSH. Higher perfluoroalkyl sulfonate exposures were associated with higher TSH and/or lower FT4, strongly suggestive that PFHxS and branched PFOS isomers are risk factors for subclinical maternal hypothyroidism. Isomer-specific analysis is important in future studies, as crude measures of 'total-PFOS' masked the associations of branched isomers. A concerning result was for PFHxS which had consistent negative associations with FT4 at all time points and a positive association with TSH in early pregnancy when fetal development is most sensitive to disruption. • Perfluoroalkyl acids were associated with thyroid hormones during and after pregnancy. • Associations were strongest in early pregnancy, a sensitive stage of neurodevelopment. • Evidence mounting for cause-effect relationship for perfluorohexane sulfonate • Isomer-specific associations for branched perfluorooctane sulfonate, not linear • Associations influenced by mercury co-exposure and thyroid peroxidase antibodies. [ABSTRACT FROM AUTHOR]

Abstract Perfluoroalkyl acids (PFAAs), as a group of industrial chemicals, are characterized by persistence, long-distance transmission, bioaccumulation and toxicity, and have been recognized as persistent organic pollutants. However, PFAAs and their related products have been used daily and in industrially products over the past several decades, which resulting in ubiquitous presence in various environmental medias, biota and even in human body. Numerous studies have investigated the neurobehavioral deficit and molecular mechanism underlying those effects of PFAAs in the last decades. In the present review, we summarized the neurotoxic effects of some PFAAs, especially perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA). The potential molecular mechanism for PFAAs-induced neurotoxicity are mainly described in the following aspects: calcium homeostasis and its related signal pathway, synaptogenesis and synaptic plasticity, neurotransmitters, as well as the neural cells apoptosis. By concluding the current evidences, we hope to provide a further prospective to assess the association of environmental PFAAs exposure and neurotoxiology outcomes. [ABSTRACT FROM AUTHOR]

Highlights • Low PFCs concentration in children living in Sicily. • PFSO concentration is higher in girls. • Maternal parity is significantly associated with PFDA and PFHxS. • Months of breastfeeding is significantly correlated with PFUnDA. Abstract Perfluorinated compounds (PFCs) are a large group of man-made chemicals characterized by a completely fluorinated hydrophobic linear carbon chain attached to a hydrophilic head. The presence of PFCs has been related with various adverse effects on several organs and systems. 61 children (6–11 years of age) living in Sicily underwent medical examination and blood and urine routinary tests, as well as the serum concentration of 16 PFCs. These compounds (∑PFCs = 5.888 ng/mL, range 1.035–12.94 ng/mL) were widely detected in the samples of all children, showing that they had been extensively exposed to PFCs, especially perfluorooctane sulfonate (PFOS), perfluorooctanoic acid (PFOA), perfluorohexanesulfonate (PFHxs) and perfluorodecanoic acid (PFDA). In addition, long-chained PFCs were found in children's blood correlated with short-chained ones. Perfluorodecanoic acid (PFDA) (beta=−0.114) and PFHxS (beta = 0.003) levels were correlated with maternal parity; while the "months of breastfeeding" variable is correlated with perfluoroundecanoic acid (PFUnDA) concentrations (beta = 0.008). Female gender is negatively associated with PFOS (beta = 0.008). The adverse health effects of PFCs on young children should be noted, due to their growing phase. Therefore, further studies are needed to monitor and address adverse health outcomes of PFCs on children, especially those living in industrial regions. [ABSTRACT FROM AUTHOR]

PFOS removal at 6 and 21 days (d) when reacted with palladium coated zero valent iron nanoparticles (Pd 0 /nFe 0 NPs) was quantified as a function of pH (3.6, 5.5, and 8.7) and temperature (22, 45 and 70 °C). PFOS concentrations were measured in aqueous phases and NP extracts. The greatest PFOS removal occurred at 6 d with the lowest pH and highest temperature; however, recovered PFOS increased at 21 d. Furthermore, neither F − nor SO 4 2− (from SO 3 2− cleavage) generation was observed indicating the absence of PFOS transformation. X-ray diffraction analysis of PFOS-reacted NPs at 45 °C revealed generation of FeO(OH) on the NPs at 21 d, which was concomitant with subsequent increases in PFOS recovery. Under anaerobic conditions, strongly adsorbing Fe(OH) 3 is formed which can then transform to less sorptive FeO(OH) via Fe 2+ catalyzed transformation. In the process of exploring causes for apparent PFOS removal with Pd 0 /nFe 0 NPs, PFOS as well as other perfluoroalkyl acids (PFAAs) were found to form aqueous-phase complexes with Fe(II/III) which can reduce their quantifiable levels. PFOS-Fe complexation was greater with Fe(III) and increased with Fe concentration and decreasing pH. Complexation was also greater for longer chain perfluoroalkyl acids and complexation of PFNA was greater than for PFOS. [ABSTRACT FROM AUTHOR]

The occurrence of 17 target PFAA analytes was determined in surface sediments ( n = 37) of the East China Sea and potential influencing factors were examined. ΣPFAAs ranged from 0.41 ng/g dw to 3.06 ng/g dw, with perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) as the most abundant perfluorocarboxylic acid and perfluoroalkyl sulfonate, respectively. PFAAs in the sediments were strongly influenced by terrigenous input. Analysis of the relationship between dynamic influence factors and PFAA concentrations showed that the characteristics of PFAA distribution were rather complex. ΣPFAA concentrations and TOC were positively correlated ( p < 0.0001). Circumfluence also influenced the whole PFAA distribution and seasonal variation. In addition, correlation analysis suggested that log K oc values increased with increasing perfluoroalkyl chain length. Given the rapid economic development of eastern coastal cities of China, the environmental hazards of land source pollution cannot be ignored. [ABSTRACT FROM AUTHOR]

Perfluoroalkyl acids (PFAAs) within the broader class of per- and polyfluoroalkyl substances (PFAS) are present in human serum as isomer mixtures, but epidemiological studies have yet to address isomer-specific associations with child development and behavior. To examine associations between prenatal exposure to 25 PFAAs, including perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) isomers, and child neurodevelopment among 490 mother–child pairs in a prospective Canadian birth cohort, the Alberta Pregnancy Outcomes and Nutrition (APrON) study. To consider the influence of a classic neurotoxicant, total mercury (THg), based on its likelihood of co-exposure with PFAAs from common dietary sources. Maternal blood samples were collected in the second trimester and child neurodevelopment was assessed at 2 years of age using the Bayley Scales of Infant and Toddler Development, 3rd Edition (Bayley-III). Linear or curvilinear multiple regression models were used to examine associations between exposures and neurodevelopment outcomes. Select PFAAs were associated with lower Cognitive composite scores, including perfluoroheptanoate (PFHpA) (β = −0.88, 95% confidence interval (CI): −1.7, −0.06) and perfluorododecanoate (PFDoA) (β = −2.0, 95% CI: −3.9, −0.01). Non-linear relationships revealed associations of total PFOS (β = −4.4, 95% CI: −8.3, −0.43), and linear-PFOS (β = −4.0, 95% CI: −7.5, −0.57) and 1 m -PFOS (β = −1.8, 95% CI: −3.3, −0.24) isomers with lower Language composite scores. Although there was no effect modification, including THg interaction terms in PFAA models revealed negative associations between perfluorononanoate (PFNA) and Motor (β = −3.3, 95% CI: −6.2, −0.33) and Social-Emotional (β = −3.0, 95% CI: −5.6, −0.40) composite scores. These findings reinforce previous reports of adverse effects of maternal PFAA exposure during pregnancy on child neurodevelopment. The unique hazards posed from isomers of PFOS justify isomer-specific analysis in future studies. To control for possible confounding, mercury co-exposure may be considered in studies of PFAAs. [ABSTRACT FROM AUTHOR]

[Display omitted] • COSMO-RS screening of 129 HDES constituents for PFOA/PFOS extraction. • Identification of 55 novel constituents from essential oils and plants. • Top constituents found to be primarily from terpene and terpenoid family. • Toxicity analysis and multicriteria evaluation for sustainable LLE process. • Reported framework can be considered as a robust selection tool. In this study, a molecular modeling approach was used to identify the most effective natural hydrophobic deep eutectic solvents (HDESs) for extracting the emerging pollutants, perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS) from synthetic wastewater. The use of HDESs for this purpose has not been reported in the literature, making this a pioneering contribution to the field. First, an extensive literature search was conducted to generate a list of 74 non-ionic HDES constituents. In the second step, a systematic screening of natural components was conducted to identify 55 new compounds that can be used for the synthesis of HDESs. The Conductor-like Screening Model for Real Solvents (COSMO-RS) was then used to screen the 129 potential HDES constituents based on three key performance indicators: distribution ratio, selectivity, and performance index at infinite dilution compared to the predicted performance of toluene as a benchmark, as the use of molecular solvents or DESs for this purpose has never been reported in the literature. The top 20 HDES constituents with the highest extraction performance were predominantly from the terpene and terpenoid families. The median lethal dose was also used to analyze toxicity. A multicriteria evaluation approach was adopted to evaluate several properties important to liquid–liquid extraction (LLE) processes, including the extraction performance, density, vapor pressure, water solubility, and leachability of DESs. Three HDESs, namely, trioctylphosphine oxide: 2-methylbenzothiazole (1:9), trioctylphosphine oxide: menthyl acetate (1:4), and 1,8-cineole: menthyl acetate (2.5:1), showed promising results. This study provides molecular insights on extracting PFOA/PFOS from wastewater using HDESs and emphasizes the need to evaluate LLE units using multicriteria. In addition, the results may serve as a starting point for further research, including the synthesis and characterization of novel HDES constituents and the development of optimized HDESs for the extraction of PFOA/PFOS from wastewater. [ABSTRACT FROM AUTHOR]

Perfluoroalkyl acids (PFAAs) are highly stable compounds that have been associated with immunotoxicity in epidemiologic studies and experimental rodent models. Lengthy half-lives and resistance to environmental degradation result in bioaccumulation of PFAAs in humans and wildlife. Perfluorooctane sulfonate (PFOS), the most prevalent PFAA detected within the environment, is found at high levels in occupationally exposed humans. We have monitored the environmental exposure of dolphins in the Charleston, SC region for over 10 years and levels of PFAAs, and PFOS in particular, were significantly elevated. As dolphins may serve as large mammal sentinels to identify the impact of environmental chemical exposure on human disease, we sought to assess the effect of environmental PFAAs on the cellular immune system in highly exposed dolphins. Herein, we utilized a novel flow cytometry-based assay to examine T cell-specific responses to environmental PFAA exposure ex vivo and to exogenous PFOS exposure in vitro. Baseline PFOS concentrations were associated with significantly increased CD4+ and CD8+ T cell proliferation from a heterogeneous resident dolphin population. Further analysis demonstrated that in vitro exposure to environmentally relevant levels of PFOS promoted proinflammatory cytokine production and proliferation in a dose-dependent manner. Collectively, these findings indicate that PFOS is capable of inducing proinflammatory interferon-gamma, but not immunoregulatory interleukin-4 production in T cells, which may establish a state of chronic immune activation known to be associated with susceptibility to disease. These findings suggest that PFOS directly dysregulates the dolphin cellular immune system and has implications for health hazards. Copyright © 2017 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

Perfluoroalkyl acids (PFAAs) have been observed in various environmental matrices globally in recent years. In this study, the levels, spatial distribution tendencies, and partitioning characteristics of the target 12 PFAAs were investigated in water and sediment from the coastal regions of Shandong peninsula in China, and two sediment core samples were also collected to study the vertical and historical variation of PFAAs. The ranges (means) of total PFAA concentrations were 23.69-148.48 ng/L (76.11 ng/L) in the water and 1.30-11.17 ng/g (5.93 ng/g) in the surface sediment, respectively. Among the target 12 PFAAs, perfluorooctanoic acid (PFOA) was the dominant component in water, followed by perfluorooctane sulfonate (PFOS) and perfluorohexanoic acid (PFHxA). PFOS, perfluoroundecanoic acid, and PFOA were the dominant components in sediment. For their spatial distribution, higher levels of PFAAs were found at the locations close to much developed cities. The PFAA concentrations showed an overall decreasing tendency with depth increase in the two sediment cores, which indicates that the extent of PFAAs pollution is aggravating trend in recent years. Results of the partition coefficient ( K ) show that the compounds with longer carbon chains ( C ≥ 7) generally had higher K values, which suggest that long-chain PFAAs are prone to be adsorbed by sediment. In addition, the Log K of PFHxA, PFOA, and PFOS were significantly and positively correlated to the salinity of the water. The results of risk assessment suggest appreciable risk of PFAAs to the local ecosystem. [ABSTRACT FROM AUTHOR]

Equivocal findings are reported for perfluoroalkyl and polyfluoroalkyl substances (PFASs) and self-reported pregnancy loss. We prospectively assessed PFASs and pregnancy loss in a cohort comprising 501 couples recruited preconception and followed daily through 7 post-conception weeks. Seven PFASs were quantified: 2-N-ethyl-perfluorooctane sulfonamide acetate (Et-PFOSA-AcOH); 2-N-methyl-perfluorooctane sulfonamido acetate (Me-PFOSA-AcOH); perfluorodecanoate (PFDeA); perfluorononanoate (PFNA); perfluorooctane sulfonamide (PFOSA); perfluorooctane sulfonate (PFOS); and perfluorooctanoate (PFOA). Women used home pregnancy test kits. Loss denoted conversion from a positive to a negative pregnancy test, onset of menses or clinical confirmation (n = 98; 28%). Chemicals were log transformed and rescaled by their standard deviations to estimate adjusted hazard ratios (HRs) and 95% confidence intervals. No significantly elevated HRs were observed for any PFASs suggesting no association with loss: Et-PFOSA-AcOH (1.04; 0.87, 1.23), Me-PFOSA-AcOH (0.79; 0.61, 1.00; p < 0.05), PFDeA (0.83; 0.66, 1.04), PFNA (0.86; 0.70, 1.06), PFOSA (0.74; 0.50, 1.09), PFOS (0.81; 0.65, 1.00), and PFOA (0.93; 0.75, 1.16). [ABSTRACT FROM AUTHOR]

Perfluoroalkyl acids (PFAAs) precursors, the indirect source of PFAA exposure, have been observed in environmental and human samples. However, the maternal–fetal transfer of these chemicals has not been well examined. In this study, 50 paired maternal and cord serum samples collected in Jiangsu province of China were analyzed for fifteen PFAA precursors. Among the detected PFAAs, 6:2 fluorotelomer sulfonate (6:2 FTS), N -methyl- and N -ethyl-perfluorooctanesulfonamidoacetates had comparable detection rate in both maternal and cord sera, while the mean concentrations and detection rates of 8:2 FTS and perfluorooctane sulfonamide (PFOSA) were higher in maternal sera compared to cord sera (Mann–Whitney U test, P < 0.05). Analysis of variance and least significant difference tests showed that the youngest maternal age group (21–24 years old) had the highest concentration of 6:2 FTS in cord sera. Maternal serum PFOSA was found significantly correlated with the cord serum perfluorooctanesulfonate (PFOS) (Spearman test, r = 0.361, P = 0.010), indicating that maternal serum PFOSA might be an indirect source of PFOS in fetuses. The obtained results suggested the potential prenatal exposure and human placental transfer of perfluoroalkyl acid precursors. [ABSTRACT FROM AUTHOR]

In textiles, like outdoor clothing, per- and polyfluoroalkyl substances (PFASs) are often used for durable water repellency (DWR) of the final products. The analytical performance to determine the concentration of these chemicals available for exposure to humans and to the environment need to be established. Here a method for the extraction and analysis of one class of PFASs, namely perfluoroalkyl acids (PFAAs), in outdoor clothing was developed and validated. The PFAAs which were validated, included perfluoroalkyl carboxylic acids (PFCAs) (C 4 –C 14 ), and perfluoroalkane sulfonic acids (PFSAs) (C 4 , C 6 , C 7 , C 8 ). In addition, perfluorooctane sulfonamide (FOSA) was included in this study. The method was based on an organic solvent extraction and analysis by high-performance liquid chromatography–tandem mass spectrometry (LC–MS/MS). No further cleaning was needed. Two commonly used organic solvent compositions were evaluated for the optimal extraction, i.e. methanol and acetone/acetonitrile (80:20, v/v), and the number and duration of the sequential extractions were optimized. Results showed that two sequential extractions with 5 mL methanol and an extraction time of 30 min gave an optimal performance with an extraction efficiency of >90%. The influence of matrix on the quantification of PFAAs was studied. This indicated ion suppression due to different matrix effects or sorption behavior to specific textile samples. Validation of the entire method showed overall recoveries of>80% and relative standard deviations (RSDs) of<9% ( n =3) for repeatability and <20% ( n =3) for reproducibility. This is the first validation of an analytical method for the analysis of extractable PFCAs, PFSAs and FOSA associated to textiles, which is of high importance due to the regulation of PFAAs in textile. [ABSTRACT FROM AUTHOR]

Evidence on the associations of perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) with hypertension or blood pressure (BP) levels was limited and inconsistent. The present prospective study aims to evaluate the longitudinal associations of serum levels of PFOA and PFOS with incident hypertension risk and change of blood pressure levels. At baseline 1080 participants (mean age 62 years, 58.9% females) free of hypertension, cardiovascular disease, diabetes, and cancer were followed up for nearly 5 years. Baseline serum levels of PFOA and PFOS were measured with ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS). Hypertension was defined as any of (1) self-reported physician-diagnosed hypertension (2) use of hypotension drugs (3) measured systolic BP ≥ 140 mmHg or diastolic BP ≥ 90 mmHg. Change of BP was evaluated as a difference between twice measurements (BP at follow-up visit－BP at baseline). After adjustment for multiple covariates, serum PFOS levels were negatively correlated with risk of hypertension [RR per lg-unit = 0.94 (95% CI: 0.88, 0.99)] and change of systolic BP [β = −1.48 (95% CI: −2.56, −0.41)]. The highest vs lowest quartiles of PFOS concentration was negatively associated with hypertension risk. Compared with Q1, the RRs (95% CIs) for Q2, Q3, and Q4 were 0.83 (0.67–0.98), 0.81 (0.67–0.97), and 0.81(0.67–0.97), respectively (p for trend = 0.016). The negative associations remained in females but not in males (p for interaction = 0.44). No significant association of PFOA with hypertension risk was observed. Further studies are needed to validate our findings. • Evidences on the associations of PFAS with hypertension risk were inconsistent. •Serum PFOS was negatively related to incident hypertension risk and SBP changes. •The inverse association of PFOS with hypertension remained in female but not male. [ABSTRACT FROM AUTHOR]

The Great Pacific Garbage Patch (GPGP) is a gyre of marine plastic debris in the North Pacific Ocean, and nearby is Midway Atoll which is a focal point for ecological damage. This study investigated 13 C 4 –C 16 perfluorinated carboxylic acids (PFCAs), four (C 4 , C 6 , C 8 and C 10 ) perfluorinated sulfonates and perfluoro-4-ethylcyclohexane sulfonate [collectively perfluoroalkyl acids (PFAAs)] in black-footed albatross tissues (collected in 2011) from Midway Atoll. Of the 18 PFCAs and PFSAs monitored, most were detectable in the liver, muscle and adipose tissues. The concentrations of PFCAs and PFSAs were higher than those in most seabirds from the arctic environment, but lower than those in most of fish-eating water birds collected in the U.S. mainland. The concentrations of the PFAAs in the albatross livers were 7-fold higher than those in Laysan albatross liver samples from the same location reported in 1994. The concentration ranges of PFOS were 22.91–70.48, 3.01–6.59 and 0.53–8.35 ng g −1 wet weight (ww), respectively, in the liver, muscle and adipose. In the liver samples PFOS was dominant, followed by longer chain PFUdA (8.04–18.70 ng g −1 ww), PFTrDA, and then PFNA, PFDA and PFDoA. Short chain PFBA, PFPeA, PFBS and PFODA were below limit of quantification. C 8 –C 13 PFCAs showed much higher composition compared to those found in other wildlife where PFOS typically predominated. The concentrations of PFUdA in all 8 individual albatross muscle samples were even higher than those of PFOS. This phenomenon may be attributable to GPGP as a pollution source as well as PFAA physicochemical properties. [ABSTRACT FROM AUTHOR]

Perfluoroalkyl acids (PFAAs) have been determined in the environment globally. However, studies on the occurrence of PFAAs in marine sediment remain limited. In this study, 16 PFAAs are investigated in surface sediments from the German Bight, which provided a good overview of the spatial distribution. The concentrations of ΣPFAAs ranged from 0.056 to 7.4 ng/g dry weight. The highest concentration was found at the estuary of the River Ems, which might be the result of local discharge source. Perfluorooctane sulfonic acid (PFOS) was the dominant compound, and the enrichment of PFOS in sediment might be strongly related to the compound structure itself. The geographical condition of the German Bight influenced the movement of water and sediment, resulting in complex distribution. Following normalization according to total organic carbon (TOC) content, PFAA distributions showed a different picture. Significant linear relationships were found between total PFAA concentrations and TOC (R 2 = 0.50, p < 0.01). Compared with a previous study conducted in the same area, a declining trend was presented for the concentrations of PFOS and perfluorooctanoic acid (PFOA). Compound structure, geographical condition, and organic carbon in the sediment influence the distribution of PFAAs in the German Bight. Environmental risk assessment indicated that the risk from PFOA is negligible, whereas PFOS in marine sediment may present a risk for benthic organisms in the German Bight. [ABSTRACT FROM AUTHOR]

Background: Exposure to perfluoroalkyl and polyfluoroalkyl substances (PFASs) is ubiquitous in most regions of the world. The most commonly studied PFASs are perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA). Animal studies indicate that maternal PFAS exposure is associated with reduced fetal growth. However, the results of human studies are inconsistent. Objectives: To summarize the evidence of an association between exposure to PFASs, particularly PFOS and PFOA, and human fetal growth. Methods: Systematic literature searches were performed in MEDLINE and EMBASE. We included original studies on pregnant women with measurements of PFOA or PFOS in maternal blood during pregnancy or the umbilical cord and associations with birth weight or related outcomes according to the PFAS level. Citations and references from the included articles were investigated to locate more relevant articles. Study characteristics and results were extracted to structured tables. The completeness of reporting as well as the risk of bias and confounding were assessed. Results: Fourteen studies were eligible. In utero PFOA exposure was associated with decreased measures of continuous birth weight in all studies, even though the magnitude of the association differed and many results were statistically insignificant. PFOS exposure and birth weight were associated in some studies, while others found no association. Conclusions: Higher PFOS and PFOA concentrations were associated with decreased average birth weight in most studies, but only some results were statistically significant. The impact on public health is unclear, but the global exposure to PFASs warrants further investigation. [ABSTRACT FROM AUTHOR]

Highlights: [•] We investigated time trends between 1987 and 2007 in perfluoroalkyl acids. [•] PFDA, PFNA, and PFUnDA increased during the period, but most markedly after 2000. [•] PFOS, PFOA, and PFHxS peaked during the period 1990–2000. [ABSTRACT FROM AUTHOR]

Background Perfluorooctanoate (PFOA) and perfluorooctane sulfonate (PFOS) are persistent environmental contaminants that affect metabolic regulation, inflammation, and other factors implicated in the development and progression of colorectal cancer (CRC). However, the link between these compounds and CRC remains unknown. In this cross-sectional study, we investigated the association of CRC diagnosis to PFOA and PFOS blood levels in a large Appalachian population. Methods Participants were 47,359 adults ≥ 21 years of age and residing in six PFOA-contaminated water districts in the mid-Ohio Valley (N = 47,151 cancer-free adults, 208 cases of primary CRC). All participants completed a comprehensive health survey between 2005 and 2006; serum levels of PFOA, PFOS, and a range of other blood markers were also measured. Medical history was assessed via self report and cancer diagnosis confirmed via chart review. Results CRC showed a strong inverse, dose--response association with PFOS serum levels (odds ratio (OR) adjusted for potential confounders = 0.2, 95% confidence interval (CI) 0.2,0.3) for highest vs. lowest quartile of PFOA, P-trend < 0.00001) and a significant, but more modest inverse association with PFOA (adjusted OR = 0.6 (CI 0.4,0.9) for highest vs. lowest quartile, P-trend = 0.001). These inverse associations were stronger in those diagnosed within the previous 6 years and resident in the same water district for a minimum of 10-15 years preceding assessment. The relationship between PFOA and CRC was also more pronounced in men and leaner adults, and showed a stronger linear trend at lower exposure levels. Conclusions In this large cross-sectional study, we found a strong, inverse association between PFOS and likelihood of CRC diagnosis and a significant, although more modest inverse association between PFOA and CRC. If confirmed in prospective investigations, these findings may aid in identifying new strategies for CRC prevention and treatment and inform future studies regarding mechanisms underlying CRC pathogenesis. [ABSTRACT FROM AUTHOR]

Abstract: In Canada, perfluoroalkyl acids (PFAAs) have been the focus of several monitoring programs and research and surveillance studies. Here, we integrate recent data and perform a multi-media assessment to examine the current status and ongoing trends of PFAAs in Canada. Concentrations of perfluorooctane sulfonate (PFOS), perfluorooctanoate (PFOA), and other long-chain perfluorocarboxylates (PFCAs) in air, water, sediment, fish, and birds across Canada are generally related to urbanization, with elevated concentrations observed around cities, especially in southern Ontario. PFOS levels in water, fish tissue, and bird eggs were below their respective Draft Federal Environmental Quality Guidelines, suggesting there is low potential for adverse effects to the environment/organisms examined. However, PFOS in fish and bird eggs tended to exceed guidelines for the protection of mammalian and avian consumers, suggesting a potential risk to their wildlife predators, although wildlife population health assessments are needed to determine whether negative impacts are actually occurring. Long-term temporal trends of PFOS in suspended sediment, sediment cores, Lake Trout (Salvelinus namaycush), and Herring Gull (Larus argentatus) eggs collected from Lake Ontario increased consistently from the start of data collection until the 1990s. However, after this time, the trends varied by media, with concentrations stabilizing in Lake Trout and Herring Gull eggs, and decreasing and increasing in suspended sediment and the sediment cores, respectively. For PFCAs, concentrations in suspended sediment, sediment cores, and Herring Gulls generally increased from the start of data collection until present and concentrations in Lake Trout increased until the late 1990s and subsequently stabilized. A multimedia comparison of PFAA profiles provided evidence that unexpected patterns in biota of some of the lakes were due to unique source patterns rather than internal lake processes. High concentrations of PFAAs in the leachate and air of landfill sites, in the wastewater influent/effluent, biosolids, and air at wastewater treatment plants, and in indoor air and dust highlight the waste sector and current-use products (used primarily indoors) as ongoing sources of PFAAs to the Canadian environment. The results of this study demonstrate the utility of integrating data from different media. Simultaneous evaluation of spatial and temporal trends in multiple media allows inferences that would be impossible with data on only one medium. As such, more co-ordination among monitoring sites for different media is suggested for future sampling, especially at the northern sites. We emphasize the importance of continued monitoring of multiple-media for determining future responses of environmental PFAA concentrations to voluntary and regulatory actions. [Copyright &y& Elsevier]

Abstract: The sources and pathways of human exposure to perfluoroalkyl acids (PFAAs) are not well characterized, particularly in China where many perfluorinated substances are now manufactured. Here, isomer-specific PFAA analysis was used for the first time to evaluate exposure sources for Chinese people, by applying the method to 129 serum samples collected in two typical cities (Shijiazhuang and Handan) in North China. Among all samples, total perfluorooctanesulfonate (∑PFOS, mean 33.3ng/ml) was the predominant PFAA followed by perfluorohexanesulfonate (2.95ng/ml), total perfluorooctanoate (∑PFOA, 2.38ng/ml), and perfluorononanoate (0.51ng/ml). The level of ∑PFOS was higher than in people from North America in recent years. The mean concentrations of ΣPFAAs in the participants living in urban Shijiazhuang (59.0ng/ml) and urban Handan (35.6ng/ml) were significantly higher (p<0.001 and p=0.041, respectively) than those living in the rural district of Shijiazhuang (24.3ng/ml). The young female sub-population had the lowest ΣPFAA concentrations compared with older females and all males. On average, the proportion of linear PFOS (n-PFOS) was only 48.1% of ∑PFOS, which is much lower than what was present in technical PFOS from the major historical manufacturer (ca. 70% linear), and which is also lower than data reported from any other countries. Moreover, the proportion of n-PFOS decreased significantly with increasing ∑PFOS concentration in the serum samples (r=−0.694, p<0.001). Taken together, the data lend weight to previous suggestions that i) high branched PFOS content in serum is a biomarker of exposure to PFOS-precursors, and ii) that people with the highest ∑PFOS concentrations are exposed disproportionately to high concentrations of PFOS-precursors. On average, linear PFOA (n-PFOA) contributed 96.1% of ∑PFOA, significantly higher than in technical PFOA (ca. 75–80% linear), but lower than in Americans, suggesting higher exposure to electrochemically fluorinated PFOA than in other countries, including the United States. [Copyright &y& Elsevier]

Per- and polyfluoroalkyl substances (PFAS) have received continuous attention; however, there is limited understanding of their sources in the atmosphere and related human exposure risks. This study measured PFAS in the atmospheric total suspended particles collected from Karachi, Pakistan, during the winter. Among the quantified PFAS, perfluorobutanoic acid (PFBA) showed the highest average concentration (3.11 ± 2.64 pg/m3), accounting for 32% of the total PFAS. Wind speed was positively correlated with perfluorohexanoic acid (PFHxA) and N- ethyl perfluorooctanesulfonamide (N -EtFOSA), while relative humidity was negatively correlated with perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA). Weighted potential source contribution function (WPSCF) and concentration weighted trajectory (WCWT) analyses suggested that northwestern Pakistan and western Afghanistan areas were highly associated with the long-range atmospheric transport of PFAS. We also calculated the daily intake of PFAS via inhalation, which were in the range of 0.07–3.98 and 0.01–0.33 pg/kg bw/d for children and adults, respectively. The calculated hazard quotient (HQ) of PFOS and PFOA was significantly lower than 1, indicating less or unlikely to cause non-carcinogenic effect via inhalation exposure. Overall, this study contributes to the understanding of geographic origins and human inhalation risks of airborne PFAS on a regional scale. [Display omitted] • Atmospheric PFAS were measured in the TSP of Karachi in Pakistan. • PFBA was the principal compound and contributed to 32% of the total PFAS. • Modeling analyses were used to identify the potential sources and geographic origins. • The estimated daily intake of particle-bound PFAS via inhalation was considerably low. [ABSTRACT FROM AUTHOR]

Per- and polyfluoroalkyl substances (PFAS) represent a large class of structurally diverse chemicals of increasing public concern, mostly due to their chemical stability and undetermined toxicity profiles. In laboratory animals, adverse effects implicated for certain PFAS, perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) in particular, include liver toxicity and the associated metabolic dysregulation, immune and thyroid alterations, reproductive toxicity, and selected tumors. The broad commercialization and environmental distribution of PFAS has drawn attention to the need for understanding risks associated with combined exposure to multiple PFAS in complex mixtures. The purpose of this investigation is to determine whether binary combinations of PFAS elicit a molecular response that is either greater than or less than the sum of the individual responses. Exposure of FaO rat hepatoma cells for 24 h to 25 μM–200 μM of the 4- and 8-carbon perfluorocarboxylic acids (PFBA and PFOA) or the 4, 6, and 8-carbon perfluorosulfonic acids (PFBS, PFHxS, and PFOS, respectively) individually caused a dose-dependent increase in PPARα-regulated expression of peroxisomal bifunctional enzyme (Ehhadh). Potency increased with carbon number, with the carboxylates eliciting a greater transcriptional response than the corresponding sulfonates. Combined exposure to PFOA and PFBA produced an effect that was significantly less than the sum of the individual responses. The response to the combination of PFOA and PFOS produced a summative effect at concentrations that were not cytotoxic. Combined exposures to PFOS and either PFBS or PFHxS at low noncytotoxic concentrations produced a transcriptional effect that was significantly less than the sum of the individual effects. The results demonstrate that among the five structurally related perfluoroalkyl acids included in this investigation, PPARα transcriptional activation in response to combined binary exposures is consistently at or below that predicted by the sum of the individual effects. [ABSTRACT FROM AUTHOR]

BACKGROUND: The widespread detection of perfluoroalkyl acids and their derivatives in wildlife and humans, and their entry into the immature brain, raise increasing concern about whether these agents might be developmental neurotoxicants. OBJECTIVES: We evaluated perfluorooctane sulfonate (PFOS), perfluorooctanoic acid (PFOA), perfluorooctane sulfonamide (PFOSA), and perfluorobutane sulfonate (PFBS) in undifferentiated and differentiating PC12 cells, a neuronotypic line used to characterize neurotoxicity. METHODS: We assessed inhibition of DNA synthesis, deficits in cell numbers and growth, oxidative stress, reduced cell viability, and shifts in differentiation toward or away from the dopamine (DA) and acetylcholine (ACh) neurotransmitter phenotypes. RESULTS: In general, the rank order of adverse effects was PFOSA > PFOS > PFBS ≈ PFOA. However, superimposed on this scheme, the various agents differed in their underlying mechanisms and specific outcomes. Notably, PFOS promoted differentiation into the ACh phenotype at the expense of the DA phenotype, PFBS suppressed differentiation of both phenotypes, PFOSA enhanced differentiation of both, and PFOA had little or no effect on phenotypic specification. CONCLUSIONS: These findings indicate that all perfluorinated chemicals are not the same in their impact on neurodevelopment and that it is unlikely that there is one simple, shared mechanism by which they all produce their effects. Our results reinforce the potential for in vitro models to aid in the rapid and cost-effective screening for comparative effects among different chemicals in the same class and in relation to known developmental neurotoxicants. [ABSTRACT FROM AUTHOR]

Exposure to perfluoroalkyl substances (PFASs) is of public concern due to their persistent exposure and adverse health effects. Placental transfer of PFASs is an important excretion pathway of these chemicals in pregnant women and exposure route in fetuses. We measured PFAS concentrations in maternal, paternal, and umbilical cord serum collected from 62 pregnant Korean women and matched biological fathers of the fetuses. Placental transfer rates (cord to maternal serum ratio) of PFASs were also calculated. Demographics and pregnancy-related factors determining the placental transfer rates were identified using linear regression models. Maternal, paternal, and cord serum showed different PFASs compositions. Among the PFASs, perfluorooctane sulfonate (PFOS) showed the highest concentrations in maternal and paternal serum, while perfluorooctanoic acid (PFOA) showed the highest concentration in cord serum. There was a higher proportion of perfluoroalkyl carboxylic acids (PFCAs) with 9–12 carbon chains than those with 13–14 carbon chains in maternal and paternal serum, but this proportion was in the opposite direction in cord serum. PFOA and perfluorohexane sulfonate (PFHxS) had higher placental transfer rates (means of 0.32 and 0.36, respectively) than PFOS (mean of 0.12), which is in line with the results of previous studies. Gestational age and birth weight were positively associated with placental transfer rate of PFOA, PFHxS, and PFOS, while pre-pregnant BMI and weight were inversely associated with PFOS. This study showed that placental transfer of PFASs differs by compounds and is associated with pregnancy-related factors. Further studies on novel PFASs are warranted for Korean pregnant women. [ABSTRACT FROM AUTHOR]

Exposure to perfluoroalkyl acids (PFAAs) is known to be associated with metabolic disorders. However, whether PFAAs isomers are associated with metabolic syndrome (MetS) still remains unknown. To explore the associations between serum PFAAs isomers and MetS. We recruited 1,501 adults from a cross-sectional study, the "Isomers of C8 Health Project in China" to investigate the associations between PFAAs isomers and MetS. A total of 20 PFAAs including the isomers of PFOS and PFOA were detected. Logistic regression models and restricted cubic spline models were used to evaluate the relationship of serum PFAAs isomers exposure with MetS and its components as well after adjusting for covariates. The MetS prevalence in our study was 43.0%. The serum levels of both PFOS and PFOA isomers were higher in participants with MetS than that with non-MetS (p < 0.05). We found positive associations for per natural log-transformed ng/mL of branched perfluorooctane sulfonate (br-PFOS) (odds ratio (OR) = 1.18, 95% confidence interval (CI): 1.01, 1.38)) linear perfluoronanoic acid (n-PFOA) (OR = 1.35, 95% CI: 1.16, 1.58) and perfluoro-6-methylpheptanoic acid (6 m-PFOA) (OR = 1.32, 95% CI: 1.11, 1.57) with higher odds of MetS after covariates adjustment, while null association was observed for linear isomers of PFOS (OR = 1.09, 95% CI: 0.94, 1.25). We found a nonlinear dose-response relationship with a "threshold" effect in serum br-PFOS isomers with MetS, in which the odds of MetS increased quickly with increasing serum br-PFOS isomers under low exposure (p for nonlinearity = 0.030). We report new evidence of associations between PFAAs isomers and MetS and the nonlinearity of dose-response relationship with br-PFOS isomers. Our findings indicate that more attention is needed to pay on the nonlinearity of dose-response relationship when investigate the association of PFAAs isomers with human health. • We provided evidence on isomeric-specific associations between serum PFAAs and metabolic syndrome in adults. • Branched PFOS isomers were associated with metabolic syndrome with an apparent "threshold" effect. • Both serum PFOS and PFOA were associated with elevated fasting blood glucose. [ABSTRACT FROM AUTHOR]

• Prenatal perfluoroalkyl acid (PFAS) exposure increases the risk of hospitalization. • Maternal PFOS concentration was associated with higher risk of any infection. • Maternal PFOS and PFOA increased the risk of lower respiratory tract infections. The immunosuppressive properties of PFASs are widely recognized. Early-life exposure to PFAS has been linked to reduced immune response to childhood vaccinations and increased rates of common infectious diseases, but implications for hospitalizations are unclear. To investigate the association between maternal serum concentrations of five PFASs during pregnancy and the child's rate of hospitalization due to common infectious diseases between birth and 4 years of age. Serum samples from first trimester pregnant women from the Odense Child Cohort (OCC) collected in 2010–2012 were analyzed for concentrations of perfluorooctanesulfonic acid (PFOS), perfluorooctanoic acid (PFOA) and three other PFASs. Data on child hospitalizations with an ICD-10 code for infectious disease was obtained from the Danish National Patient Register. The following were identified: upper respiratory tract infections (URTI), lower respiratory tract infections (LRTI), gastrointestinal infections (GI), and other infections. The Andersen-Gill Cox proportional hazard model for recurrent events was used to investigate the association between PFAS exposure and hospitalizations. The resulting estimates were hazard ratios (HRs), which express the relative change in the instantaneous risk of hospitalization with a doubling in maternal PFAS concentration. A total of 1,503 mother–child pairs were included, and 26% of the children were hospitalized at least once for infectious disease. A doubling in maternal PFOS concentration was associated with a 23% increase in the risk of hospitalization due to any infection (HR: 1.23 (95% CI: 1.05, 1.44). There was indication of an interaction between child sex and PFOS (p = 0.07) and PFDA (p = 0.06), although in opposite directions. Further, every doubling of PFOA or PFOS increased the risk of LRTI by 27% (HR: 1.27 (1.01, 1.59)) and 54% (HR: 1.54 (1.11, 2.15)), respectively. Similar tendencies were seen for URTI and the group of other infections. For GIs, the opposite pattern of association was seen as HR's were consistently below 1 (PFOA, HR: 0.55 (0.32, 0.95)). We found an association between PFOS and the overall risk of infectious disease, and between PFOS and PFOA exposures and the risk of LRTI's. These results are in agreement with previous findings from the OCC, in which maternal PFOS and PFOA concentrations were positively associated with the number of days that the children experienced fever, thereby suggesting that PFOS and PFOA may affect the prevalence of both mild and more severe infectious diseases even in a rather low-exposed population. [ABSTRACT FROM AUTHOR]

Data for US adults aged ≥20 years from National Health and Nutrition Examination Survey for the years 2003–2014 were analyzed to evaluate how adjusted (N = 8481) and unadjusted (N = 9080) levels of selected perfluoroalkyl acids (PFAA) vary across the different stages of glomerular function (GF) among those who did not have diabetes, anemia, or albuminuria as compared to those who had diabetes only, anemia only, and albuminuria only. PFAAs selected for analyses were: perfluorooctanoic acid (PFOA), perfluorooctane sulfonic acid (PFOS), perfluorodecanoic acid (PFDA), perfluorohexane sulfonic acid (PFHxS), and perfluorononanoic acid (PFNA). Irrespective of GF stage, there was no noticeable evidence to suggest that adjusted levels of PFAA for those with diabetes only are any lower than those with no diabetes, no anemia, and no albuminuria. Those who had anemia only were found to have lower adjusted levels of at least PFOA, PFOS, PFDA, and PFHxS than those who had no diabetes, no anemia, and no albuminuria. These results were seen in the presence (eGFR < 60 mL/min/1.73 m2) as well as the absence of chronic kidney disease. For GF-1 (eGFR > 90 mL/min/1.73 m2), GF-2 (60 ≤ eGFR ≤ 90 mL/min/1.73 m2), and GF-3B/4 (15 < eGFR ≤ 45 mL/min/1.73 m2), those who had albuminuria only had lower adjusted levels of PFOA, PFOS, and PFHxS than those who had no diabetes, no anemia, and no albuminuria. In general, adjusted levels of those who had albuminuria only were lower than those who had anemia only at GF-3 and more often than not at GF-1 and GF-2. Rise in adjusted levels of PFAA from GF-1 to GF-3A (45 < eGFR < 60 mL/min/1.73 m2) was faster for those with anemia only than any other comparison group for the total population and females. • Those with anemia only had among the lowest levels of PFAAs. • Those with albuminuria only had among the lowest levels of PFAAs. • Rise in adjusted levels of PFAA from GF-1 to GF-3A was fastest for those with anemia only. [ABSTRACT FROM AUTHOR]

Serum composition of PFAAs congeners in Nunavik pregnant women from the NQN study in 2016–2017 compared to women from the Canadian general population who participated in the Canadian Health Measure Survey (CHMS) cycle 5. • In pregnant women from Nunavik, exposure to long-chain PFAAs is increasing. • Nunavimmiut women exposure to PFOS, PFNA, PFDA and PFuDA was higher than in the Canadian general population. • The results suggest that 8:2 FTOH contributes to the exposure profile in the Arctic. • Marine country food consumption is associated with higher exposure to PFAAs. Perfluoroalkyl acids (PFAAs) are persistent and ubiquitous environmental contaminants that potentially disrupt endocrine system functions. While some PFAAs (perfluorooctane sulfonate (PFOS), perfluorooctanoic acid (PFOA)) are regulated, currently used fluorotelomer alcohols (FTOHs) can be transported to the Arctic and are degraded in a number of PFAAs which biomagnify in Arctic wildlife (e.g. perfluorononanoic acid (PFNA), perfluorodecanoic acid (PFDA), perfluoroundecanoic acid (PFUdA)). From 2004 to 2017, 279 pregnant Inuit women were recruited as part of biomonitoring projects in Nunavik. Our goal was to evaluate: (i) time-trends in plasma/serum PFAAs levels in pregnant Nunavimmiut women between 2004 and 2017; (ii) compare plasma/serum PFAAs levels in Nunavimmiut women in 2016–2017 to those measured in women of childbearing age in the Canadian Health Measure Survey (CHMS); and (iii) evaluate the associations of PFAAs levels with the consumption of country foods and pregnancy and maternal characteristics during pregnancy in the 97 participants recruited in 2016–2017. Individual blood sample were collected for serum or plasma PFAAs (PFOS, PFOA, pentafluorobenzoic acid (PFBA), perfluorohexanoic acid (PFHxA), perfluorobutanesulfonic acid (PFBS), perfluorohexane-1-sulfonic acid (PFHxS), PFNA, PFDA, PFUdA) analyses. Socio-demographic data, pregnancy and maternal characteristics and country foods consumption were documented using a questionnaire. Omega-3 and −6 polyunsaturated fatty acids (PUFA) were measured in red blood cell membranes and their ratio used as a biomarker of marine country foods consumption. Time-trends in PFAAs levels were evaluated using ANCOVA models adjusted for relevant co-variables. Serum/plasma levels of PFAAs in the 97 pregnant women aged 16 to 40 years old and recruited in 2016–2017 were compared to those measured in women aged 18 to 40 years old from the CHMS cycle 5 (2016–2017) using the geometric means (GM) and 95% confidence intervals (95% CI). Multivariate regression analyses were performed to examine associations between concentrations of PFAAs and country foods consumption data. Statistically-significant downward time trends were noted for concentrations of PFOS, PFOA and PFHxS in pregnant Nunavik women between 2004 and 2017. Conversely, between 2011 and 2016–2017, PFNA, PFDA and PFUdA maternal serum levels increased by 19, 13 and 21% respectively. Among participants in 2016–2017, mean concentrations for PFNA (GM: 2.4 μg/L), PFDA (0.53 μg/L) and PFUdA (0.61 μg/L) were higher than those measured in women aged 18–40 years old in the Cycle 5 (2016–2017) of the CHMS. PFOA (0.53 μg/L) and PFHxS (0.26 μg/L) were lower than in CHMS, whereas PFBA, PFHxA and PFBS were not detected in 2016–2017. Ratios of serum/plasma levels of PFNA/PFOA, PFNA/PFOS, PFNA/PFHxS and PFUdA/PFDA were significantly higher in the 97 pregnant women from Nunavik recruited in 2016–2017 compared to CHMS, highlighting their distinct exposure profile. In multivariate models, PFHxS, PFOS, PFNA, PFDA and PFUdA levels in 2016–2017 were strongly associated with the omega-3/omega-6 PUFA ratio, indicating a positive association between marine country foods consumption and higher exposure to PFAAs. The exposure of pregnant women to long-chain PFAAs (PFNA, PFDA and PFUdA) increased from 2004 to 2017 in Nunavik. Associations noted between PFAAs levels and the omega-3/omega-6 ratio highlights the importance of implementing additional strict regulations on PFAAs and their precursors to protect the high nutritional quality and cultural importance of country foods in Nunavik. [ABSTRACT FROM AUTHOR]

Previous epidemiological and experimental studies have shown that legacy perfluoroalkyl acids (PFAAs) are immunotoxic. However, whether the immunosuppressive effects in PFAA alternatives which recently have been widely detected in the environment are unknown. To address this knowledge gap, we investigated the relationship of serum legacy PFAAs and PFAA alternatives with the antibody of hepatitis B virus in adults. We recruited 605 participants from a cross-sectional study, the Isomer of C8 Health Project in China. We measured two representative legacy PFAAs (perfluorooctane sulfonate, PFOS and perfluorooctanoic acid, PFOA), and three PFAA alternatives (two chlorinated polyfluorinated ether sulfonic acids, Cl-PFESAs and perfluorobutanoic acid, PFBA) in serum using ultra-performance liquid chromatograph-tandem mass spectrometry (UPLC-MS/MS). We applied linear and logistic regression models to analyze associations between serum PFAAs and hepatitis B surface antibody (HBsAb) with multivariable adjustments. We found negative associations between serum PFAAs concentrations and HBsAb. Lower serum HBsAb levels (log mIU/mL) were observed for each log-unit increase in linear PFOS (β = −0.31, 95% confidential interval: 0.84, −0.18), 6:2 PFESA (β = −0.81, 95% CI: 1.20, −0.42), 8:2 PFESA (β = −0.29, 95% CI: 0.43, −0.14) and PFBA (β = −0.18, 95% CI: 0.28, −0.08). The association between PFAAs and HBsAb seronegative seemed to be higher for 6:2 PFESA (odds ratio = 3.32, 95% CI: 2.16, 5.10) than its predecessors, linear PFOS (OR = 1.96, 95% CI: 1.37, 2.81) and branched PFOS isomers (OR = 1.64, 95% CI: 1.05, 2.56). We report new evidence that exposure to PFAA alternatives are associated with lower HBsAb in adults. This association seems to be stronger in 6:2 PFESA than PFOS. Our results suggest that more studies are needed to clarify the potential toxicity of PFAA alternatives in human which will facilitate better chemical regulations for PFAAs. Image 1 • Legacy perfluoroalkyl acids and PFAA alternatives were widely detected in serum. • Higher serum PFAAs were associated with lower hepatitis B virus antibody levels. • The observed association was stronger for a chlorinated PFAA alternative. [ABSTRACT FROM AUTHOR]

Rivers can receive the input of treated or untreated sewage effluents from wastewater treatment plants, urban and industrial discharges and agricultural run-off, becoming an important pathway for the transport and mobilization of pollutants to the oceans. In the present study, the occurrence of 20 PFAAs was determined in the water of Tagus River basin (Spain). PFAAs were detected in 76 out of 92 water samples collected during 5 years (2013–2018), being perfluorooctanesulfonic acid (PFOS) the predominant compound (<0.01–34 ng/L). The annual average PFOS concentrations (2.9–11 ng/L) detected in Tagus River were above the annual average environmental quality standards (AA-EQS) established in the Directive, 2013/39/EU (0.65 ng/L for inland surface waters) but below the maximum allowable concentration (MAC-EQS; 36000 ng/L). The levels of PFAAs detected in urban and industrial areas were statistically higher (p < 0.01) than those at background or remote areas. The mass flow rates amounted to <0.01–46 kg/y for PFOS and <0.01–22 kg/y for perfluorooctanoic acid (PFOA). A quantitative ecotoxicological risk assessment was conducted to evaluate the environmental potential risk related to PFAAs in the aquatic ecosystem. Risk characterization ratios (RCR water , RCR sed and RCR oral, fish) were below 1 in all cases. Image 1 • PFOS was the predominant compound in Tagus River basin. • ΣPFAA levels were statistically higher at urban/industrial areas than remote areas. • The mass flow rates associated the PFAA discharge with industrial/urban sources. • RCR water , RCR sed and RCR oral, fish estimated were <1 (negligible risk). The occurrence of 20 PFAAs has been determined in the surface water from Tagus River basin. Mass flow rates amounted to <0.01–88 kg/y for total PFAAs. [ABSTRACT FROM AUTHOR]