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Affinities of six anions (mesylate, acetate, trifluoroacetate, p‐toluenecarboxylate, p‐toluenesulfonate, and perfluorooctanoate) for three related Pt2+‐linked porphyrin nanocages were measured to probe the influence of different noncovalent recognition motifs (e. g. hydrogen bonding, electrostatics, π bonding) on anion binding. Two new hosts of M6L312+ (1b) and M4L28+ (2) composition (M=(en)Pt2+, L=(3‐py)4porphyrin) were prepared in a one‐pot synthesis and allowed comparison of hosts that differ in structure while maintaining similar N−H hydrogen‐bond donor ability. Comparisons of isostructural hosts that differ in hydrogen‐bonding ability were made between 1b and a related M6L312+ nanoprism (1a, M=(tmeda)Pt2+) that lacks N−H groups. Considerable variation in association constants (K1=1.6×103 M−1 to 1.3×108 M−1) and binding mode (exo vs. endo) were found for different host–guest combinations. Strongest binding was seen between p‐toluenecarboxylate and 1b, but surprisingly, association of this guest with 1a was only slightly weaker despite the absence of NH⋅⋅⋅O interactions. The high affinity between p‐toluenecarboxylate and 1a could be turned off by protonation, and this behavior was used to toggle between the binding of this guest and the environmental pollutant perfluorooctanoate, which otherwise has a lower affinity for the host. [ABSTRACT FROM AUTHOR]

Background: Exposures to perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA), environmentally persistent chemicals detectable in the blood of most Americans, have been associated with several health outcomes. To offer insight into their possible biologic effects, we evaluated the metabolomic correlates of circulating PFOS and PFOA among 3,647 participants in eight nested case-control serum metabolomic profiling studies from the Prostate, Lung, Colorectal, and Ovarian Cancer Screening Trial. Methods: Metabolomic profiling was conducted by Metabolon Inc., using ultra high-performance liquid chromatography/tandem accurate mass spectrometry. We conducted study-specific multivariable linear regression analyses estimating the associations of metabolite levels with levels of PFOS or PFOA. For metabolites measured in at least 3 of 8 nested case-control studies, random effects meta-analysis was used to summarize study-specific results (1,038 metabolites in PFOS analyses and 1,100 in PFOA analyses). Results: The meta-analysis identified 51 and 38 metabolites associated with PFOS and PFOA, respectively, at a Bonferroni-corrected significance level (4.8x10-5 and 4.6x10-5, respectively). For both PFOS and PFOA, the most common types of associated metabolites were lipids (sphingolipids, fatty acid metabolites) and xenobiotics (xanthine metabolites, chemicals). Positive associations were commonly observed with lipid metabolites sphingomyelin (d18:1/18:0) (P = 2.0x10-10 and 2.0x10-8, respectively), 3-carboxy-4-methyl-5-pentyl-2-furanpropionate (P = 2.7x10-15, 1.1x10-17), and lignoceroylcarnitine (C24) (P = 2.6x10-8, 6.2x10-6). The strongest positive associations were observed for chemicals 3,5-dichloro-2,6-dihydroxybenzoic acid (P = 3.0x10-112 and 6.8x10-13, respectively) and 3-bromo-5-chloro-2,6-dihydroxybenzoic acid (P = 1.6x10-14, 2.3x10-6). Other metabolites positively associated with PFOS included D-glucose (carbohydrate), carotene diol (vitamin A metabolism), and L-alpha-aminobutyric acid (glutathione metabolism), while uric acid (purine metabolite) was positively associated with PFOA. PFOS associations were consistent even after adjusting for PFOA as a covariate, while PFOA associations were greatly attenuated with PFOS adjustment. Conclusions: In this large metabolomic study, we observed robust positive associations with PFOS for several molecules. Further investigation of these metabolites may offer insight into PFOS-related biologic effects.

Many epidemiology studies have investigated associations of perfluorooctanoate (PFOA) exposures with a variety of adverse health outcomes for participants in the C8 Health Project. The exposure concentrations (i.e., air and groundwater) used in these studies were determined primarily based on participant's residential locations. However, for residential addresses that could not be geocoded to the street level, the exposure concentrations were assigned based on population-weighted ZIP code centroid, which may result in exposure mischaracterization. The aim of this current study is to evaluate the potential impact of mischaracterized exposure concentrations due to geocoding uncertainty on the predicted serum PFOA concentrations and the epidemiological association between PFOA exposure and preeclampsia. For both workplace addresses and incompletely geocoded residential addresses, we used Monte Carlo (MC) simulation to assign alternate geographic locations within the reported ZIP code (instead of population-weighted ZIP code centroids) and the corresponding exposure concentrations. We found that mischaracterization of residential exposure due to population-weighted ZIP code centroid assignment had no significant impact on the serum PFOA concentration predictions and the epidemiological association of PFOA exposure with preeclampsia. In contrast, the uncertainty in workplace exposure moderately impacted the rank exposure among the participants. We observed a 41% increase in the average adjusted odds ratio of preeclampsia occurrence that may be due to differing proportions of cases (64.3%) and controls (54.5%) with workplace address geocodes during pregnancy. This finding suggests that differential exposure mischaracterization can be reduced by obtaining accurate exposure information such as street addresses and tap water consumption, for both workplaces and residences. The analysis we present is one approach for estimating the potential impacts of positional errors in a geocoding-based exposure assessment on exposure estimates and epidemiological study results.

We recently utilized a suite of environmental fate and transport models and an integrated exposure and pharmacokinetic model to estimate individual perfluorooctanoate (PFOA) serum concentrations, and also assessed the association of those concentrations with preeclampsia for participants in the C8 Health Project (a cross-sectional study of over 69,000 people who were environmentally exposed to PFOA near a major U.S. fluoropolymer production facility located in West Virginia). However, the exposure estimates from this integrated model relied on default values for key independent exposure parameters including water ingestion rates, the serum PFOA half-life, and the volume of distribution for PFOA. The aim of the present study is to assess the impact of inter-individual variability and epistemic uncertainty in these parameters on the exposure estimates and subsequently, the epidemiological association between PFOA exposure and preeclampsia. We used Monte Carlo simulation to propagate inter-individual variability/epistemic uncertainty in the exposure assessment and reanalyzed the epidemiological association. Inter-individual variability in these parameters mildly impacted the serum PFOA concentration predictions (the lowest mean rank correlation between the estimated serum concentrations in our study and the original predicted serum concentrations was 0.95) and there was a negligible impact on the epidemiological association with preeclampsia (no change in the mean adjusted odds ratio (AOR) and the contribution of exposure uncertainty to the total uncertainty including sampling variability was 7%). However, when epistemic uncertainty was added along with the inter-individual variability, serum PFOA concentration predictions and their association with preeclampsia were moderately impacted (the mean AOR of preeclampsia occurrence was reduced from 1.12 to 1.09, and the contribution of exposure uncertainty to the total uncertainty was increased up to 33%). In conclusion, our study shows that the change of the rank exposure among the study participants due to variability and epistemic uncertainty in the independent exposure parameters was large enough to cause a 25% bias towards the null. This suggests that the true AOR of the association between PFOA and preeclampsia in this population might be higher than the originally reported AOR and has more uncertainty than indicated by the originally reported confidence interval.

Oily wastewater treatment is a global challenge due to the substantial amount of effluent resulted from many industrial and domestic activities. To overcome the challenge of using existing treatment approach and fouling, superoleophobic coatings were fabricated. In this study, a superoleophobic membrane surface was obtained using the sol-gel technique with perfluorooctanoate (PFO), poly (diallyl dimethylammonium chloride) (PDADMAC), and nanoparticles as complex-polymer nanocomposites. The effects of coating cycles on the surface structure, chemical properties, surface chemistry, and oleophobicity of the surface were examined using field emission scanning electron microscopy (FESEM), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and oil contact angle measurement. The results showed that the coated layer successfully adhered to the substrate surface. However, the chemical stability with respect to oil contact angle (OCA) revealed a decline at pH 7 and pH 9 and maintained stability at pH 3. Besides, oil flux at 63.0 L/m2. h was achieved for PDADMAC-Al 2 O 3 /44 wt% PFO and the highest separation efficiency of 98% was obtained. Furthermore, the oil rejection decreases as the oil concentration increases from 1 to 3 g/L. OCA of 155° was obtained after 5 coating cycles. Apart from mitigating substrate fouling, the superoleophobic and superhydrophilic coating can be applied to a ceramic-based hollow fibre membrane and efficiently used for the separation of oil from oily wastewater. [Display omitted] [ABSTRACT FROM AUTHOR]

Among many short-term, subchronic, and chronic toxicology studies with ammonium perfluorooctanoate (PFOA), the gastrointestinal tract has not been identified as a target organ for PFOA-related toxicity in laboratory animals where the corresponding serum PFOA concentrations typically approach several orders of magnitude higher than the general human population. These lack of gastrointestinal tract-related findings were in direct contrast to an epidemiological observation where a positive trend was observed for ulcerative colitis, an idiopathic chronic inflammatory condition of the gut, in a Mid-Ohio River community whose drinking water contained higher levels of PFOA. This study was conducted to perform a histological reevaluation of large intestine sections in laboratory animals from 2 long-term toxicological studies: one was with Sprague Dawley rats that received ammonium PFOA in their diet for 2 years and the other one was with cynomolgus macaques that received daily capsules of ammonium PFOA for 6 months. In both studies, there was a lack of histological evidence of treatment-related inflammatory lesions that was suggestive of the occurrence of ulcerative colitis in these laboratory animals even under the most rigorous treatment schedules. These findings do not offer support for the biological plausibility of the epidemiological associations reported. [ABSTRACT FROM AUTHOR]

Perfluorooctanoate (PFOA) is widely used as a surfactant and has metabolic, immunologic, developmental, and genetic toxicity on marine organisms. However, the effects of PFOA on individual defense functions in mussels in the presence of titanium dioxide nanoparticles (nano-TiO 2) are poorly understood. To investigate the defense strategies and regulatory mechanisms of mussels under combined stressors, the thick-shell mussels Mytilus coruscus were exposed to different PFOA concentrations (0, 2 and 200 μg/L) and nano-TiO 2 (0 and 0.1 mg /L, size: 25 nm) for 14 days. The results showed that, compared to the control group, PFOA and nano-TiO 2 significantly reduced the number of byssal threads (NBT), byssal threads length (BTL), diameter of proximal threads (DPB), diameter of middle threads (DMB), diameter of distal byssal threads (DDB), adhesive plaque area (BPA), and breaking force of byssal threads (N). Under the influence of PFOA and nano-TiO 2 , the morphological surface smoothness of the fractured byssal threads surface increased, concurrently inducing an increased surface roughness in the adhesive plaques. Additionally, under the presence of PFOA and nano-TiO 2 , the foot displayed dispersed tissue organization and damaged villi, accompanied by an increased incidence of cellular apoptosis and an upregulation of the apoptosis gene caspase-8. Expression of the adhesion gene mfp-3 and byssal threads strength genes (preCOL-D, preCOL-NG) was upregulated. An interactive effect on the performance of byssal threads is observed under the combined influence of PFOA and nano-TiO 2. Under co-exposure to PFOA and nano-TiO 2 , the performance of the byssal threads deteriorates, the foot structure is impaired, and the genes mRNA expression of byssal thread secretory proteins have compensated for the adhesion and byssal threads strength by up-regulation. Within marine ecosystems, organic and particulate contaminants exert a pronounced effect on the essential life processes of individual organisms, thereby jeopardizing their ecological niche within community assemblages and perturbing the dynamic equilibrium of the overarching ecosystem. Perfluorooctanoic acid (PFOA) is prone to accumulate in marine organisms. TiO 2 nanoparticles (nano-TiO 2) are emerging environmental pollutants frequently found in marine environment. The effects of PFOA and nano-TiO 2 on marine mussels are not well understood, and their toxic mechanisms remain largely unknown. We investigated the impacts of PFOA and nano-TiO 2 on mussel byssus defense mechanisms. By assessing byssus performance indicators, morphological structures of the byssus, subcellular localization, and changes in byssal secretion-related genes, we revealed the combined effects and mechanisms through which these two types of pollutants may affect the functional capabilities and survival of mussels in the complex marine ecosystem. [Display omitted] • PFOA and nano-TiO 2 induce apoptosis in foot cells of mussels. • The expressions of some mussel foot proteins were up-regulated under PFOA and nano-TiO 2. • PFOA and nano-TiO 2 have negative impacts on the performance of mussel byssal threads. • PFOA and nano-TiO 2 cause damage to the structure of the foot. [ABSTRACT FROM AUTHOR]

Perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) are persistent anthropogenic chemicals that are widely distributed in the environment and pose significant risks to human health. Foam fractionation has emerged as a promising method to recover PFOS/PFOA from water. However, PFOS/PFOA concentrations in wastewater are often inadequate to generate stable foams due to their high critical micelle concentrations and the addition of a cosurfactant is necessary. In this study, we developed whey soy protein (WSP) as a green frother and collector derived from soybean meal (SBM), which is an abundant and cost-effective agro-industrial residue. WSP exhibited excellent foaming properties across a wide pH range and demonstrated strong collection capabilities that enhanced the recovery of PFOS/PFOA. The mechanism underlying this collection ability was elucidated through various methods, revealing the involvement of electrostatic attraction, hydrophobic interaction, and hydrogen bonding. Furthermore, we designed a double plate internal to improve the enrichment of PFOS/PFOA by approximately 2.3 times while reducing water recovery. Under suitable conditions (WSP concentration: 300 mg/L, pH: 6.0, air flowrate: 300 mL/min), we achieved high recovery percentages of 94–98% and enrichment ratios of 7.5–12.8 for PFOS/PFOA concentrations ranging from 5 to 20 mg/L. This foam fractionation process holds great promise for the treatment of PFOS/PFOA and other per- and polyfluoroalkyl substances. [Display omitted] • Whey soy protein (WSP) is developed as a frother and collector. • WSP significantly improves PFOS/PFOA foaming ability and stability. • Interaction mechanism between WSP and PFSO/PFOA is confirmed. • Double plate internal (DPI) have the ability to enhance the foam drainage. • PFOS/PFOA are effectively recovered by foam fractionation with WSP. [ABSTRACT FROM AUTHOR]

Although many studies have evaluated the fate of per‐ and polyfluoroalkyl acids (PFAAs) in aquatic environments, few have observed their fate in terrestrial environments. It has been proposed that ingestion could be a major PFAA exposure route for humans. We determined PFAA uptake in radish, carrot, and alfalfa under a maximum bioavailability scenario. Bioconcentration factors (BCFs) were determined in the edible tissue of radish (perfluorobutanesulfonate [PFBS] = 72; perfluorohexanesulfonate [PFHxS] = 13; perfluoroheptanoate [PFHpA] = 65; perfluorooctanoate [PFOA] = 18; perfluorooctanesulfonate [PFOS] = 2.9; and perfluorononanoate [PFNA] = 9.6), carrot (PFBS = 5.9; PFHxS = 1.1; PFHpA = 29; PFOA = 3.1; PFOS = 1; and PFNA = 1.4), and alfalfa (PFBS = 107; PFHxS = 12; PFHpA = 91; PFOA = 10; PFOS = 1.4; and PFNA = 1.7). Some of these PFAA BCFs are as much as 2 orders of magnitude higher than those measured previously in plants grown in biosolid‐amended soils. Environ Toxicol Chem 2019;38:2497–2502. © 2019 SETAC [ABSTRACT FROM AUTHOR]

Per- and polyfluoroalkyl substances (PFAS) are a class of chemicals that were widely used in manufacturing and are now present in the environment throughout the world. It is known that various PFAS are quantifiable in human in blood, but potential adverse health outcomes remain unclear. Sentinel and non-traditional model species are useful to study potential toxicity of PFAS in order to understand the relationship between environmental and human health. Here, we present a critical review of studies on the neurotoxicity of PFAS in sentinel and non-traditional laboratory model systems, including Caenorhabditis elegans (nematode), Dugesia japonica (planarian), Rana pipiens (frogs), Danio rerio and Oryzias melastigma (fish), and Ursus maritimus (polar bears). PFAS have been implicated in developmental neurotoxicity in non-traditional and traditional model systems as well as sentinel species, including effects on neurotransmitter levels, especially acetylcholine and its metabolism. However, further research on the mechanisms of toxicity needs to be conducted to determine if these chemicals are affecting organisms in a similar manner. Overall, findings tend to be similar among the various species, but bioaccumulation may vary, which needs to be taken into account in future studies by quantifying target organ concentrations of PFAS to better compare different species. Furthermore, data on the majority of PFAS is lacking in neurotoxicity testing, and additional studies are needed to corroborate findings thus far.

Graphical abstract Highlights • Gamma and electron beam irradiation effective under reductive conditions. • Strong effect of dose-rate observed in electron beam (EB) irradiation. • Support of radiolytic decomposition by formate or nitrate in treated PFOA solutions. • EB irradiation decomposes PFOA in seconds at initial ppm level. • A successful kinetic modeling can be carried out based on known rate constants. Abstract It has been demonstrated through the use of both gamma-rays and beam of accelerated electrons (EB) for the radiolytic decomposition of PFOA in diluted aqueous solutions that the most reactive species among the products of water radiolysis are hydrated electrons e aq. The reaction of PFOA with the hydrated electrons takes place with the largest yield in strongly alkaline deaerated solutions. The PFOA decomposition performed at an initial concentration level of 1 mg/L by γ-irradiation requires the use of absorbed doses below 10 kGy, which, depending on the activity of employed 60Co source, requires 2–3 h irradiation time. Similar results were obtained at pH 12 in the presence and also in the absence of t -butanol in the treated solutions. In the case of EB irradiation in a wide range of the absorbed doses (up to 100 kGy), a very pronounced effect of the dose-rate was observed, which can be attributed to various recombination reactions of the products of water radiolysis. A significant improvement in the yield of the PFOA decomposition by EB irradiation can be observed in the presence of trace amounts of nitrate or 100 mM of a formate in the treated solutions. In optimized conditions, about 70–80% decomposition of the initial level of 1 ppm of PFOA can be obtained with an irradiation using 100 kGy absorbed dose, which corresponds to about 5 s treatment with the use of an employed electron accelerator. The acute toxicity measurements and a kinetic modeling are presented, together with a suggestion of the mechanism of radiolytic decomposition of PFOA. [ABSTRACT FROM AUTHOR]

Highlights • PFOS and PFOA levels are suggestive of levels of industrialization and poor environmental awareness. • Concentrations of PFOS and PFOA in porewater were greater than those in surface water. • Results of this study provided additional understanding of PFOS and PFOA partitioning between sediment and porewater. • Field – based fate and partitioning of PFOS and PFOA were highly dependent on salinity gradients. • Adsorption of PFOS and PFOA can be greater than expected due salinity changes in aquatic environment. Abstract Global concern on emerging pollutants such as perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) are well documented. Unfortunately, information is either scarce or non-existing on the presence of these chemicals in most developing nations like Nigeria. The current study examined the distribution pattern and trend of PFOS and PFOA in surface water, porewater (PW) and sediments collected from three geopolitical zones with different levels of industrialization in Nigeria. PFOS and PFOA were concentrated using solid-phase extraction, identified and quantified by high performance liquid chromatography interfaced to a triple quadruple mass spectrometer. Detection of both PFOS and PFOA in all samples suggested wide distribution across Nigeria. Generally, PFOS dominated aqueous concentrations ranging from 3.9 to 10.1 ng L−1 in surface water, 10.9 to 20.4 ng L−1 in PW and 5.1 to 10.4 ng g−1 in bottom sediment. Field-based partition coefficients (K d) for both PFOS and PFOA were significantly correlated with salinity (r 2 = 0.84 and 0.78 respectively, p < 0.01); The K d values increased exponentially as a function of salinity. The enrichment of both PFOS and PFOA on sediment increased with increasing organic matter while in water with increasing salinity. The detection of these chemicals across all samples suggested urgent attention in their risk assessment. [ABSTRACT FROM AUTHOR]

Exposure to perfluoroalkyl substances (PFAS) is associated with a range of adverse health effects. However, it remains unclear whether PFAS at environmentally relevant exposure levels are related to diabetes and metabolite concentrations in adults. Using cross-sectional data from 7904 adults (age ≥ 20 years) in the 2003–2012 National Health and Nutrition Examination Survey (NHANES), we examined the association of PFAS with the prevalence of diabetes and metabolite concentrations. A multivariate logistic regression was applied to investigate the associations of diabetes prevalence with serum perfluorooctanoate (PFOA), perfluorooctane sulfonate (PFOS), perfluorohexane sulfonate (PFHxS) and perfluorononanoate (PFNA) levels. A multivariate generalised linear regression was further performed to investigate the associations between PFAS exposure and some metabolites. We identified a strong positive association between serum PFOA and diabetes prevalence in men with an adjusted model (OR: 2.66, 95% CI: 1.63–4.35; P for trend = 0.001). No significant association between serum PFOA and diabetes prevalence was observed in women (OR: 1.47, 95% CI: 0.88–2.46; P for trend = 0.737). Furthermore, diabetes was not related to PFOS, PFHxS and PFNA, regardless of gender. In the gender-stratified generalised linear models, men and women with the highest PFOA levels demonstrated a 1.43% (95% CI: 0.62%–2.34%) and a 1.07% (95% CI: 0.27%–1.97%) greater increase in serum total cholesterol ( P for trend = 0.006 and 0.001) compared to those with the lowest PFOA levels. There were no significant associations between serum PFOA and other metabolites. These results provide epidemiological evidence that environment-related levels of serum PFOA may be positively associated with the prevalence of diabetes in men and with total cholesterol in adults. Further clinical and animal studies are urgently needed to elucidate putative causal relationships and shed light on the potential mode of action involved. [ABSTRACT FROM AUTHOR]

Understanding sorption of PFOA on soil particles is crucial to evaluate its environmental risk. Here, sorption of PFOA onto ten agricultural soils was examined. The influence of soil physico-chemical properties on PFOA sorption was investigated. The sorption rate of PFOA followed a pseudo-second-order kinetics. Isotherm data of PFOA sorption was fitted with both Freundlich and linear models and the latter fitted better. The sorption-desorption of PFOA onto ten soil samples depended on soil organic carbon content and composition of soil minerals. The sorption and desorption isotherms of PFOA on ten soils were linear, except for the sorption of PFOA onto a few soils, which was described by the Freundlich equation with the parameter N >1. The main sorption mechanism of PFOA was hydrophobic interaction between the perfluorinated carbon chain and the organic matter of soil, as evidenced by the correlation between the solid-liquid distribution coefficient and the fraction of soil organic carbon. The sorption of PFOA in soils was highly irreversible. [ABSTRACT FROM AUTHOR]

Perfluoroalkyl and polyfluoroalkyl substances (PFASs) are found widespread in the environment and humans. The relation of PFASs to fertility has now been examined in a relatively large number of epidemiologic studies and a synthesis is in order. The aim of this study was to assess the current human epidemiologic evidence on the association between exposure to PFASs and measures of human fertility, with particular emphasis on perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA). Systematic literature searches were initially conducted in MEDLINE and EMBASE and subsequently in references and citations of included papers. Studies were included if they assessed exposure to PFASs in biological samples in relation to reproductive hormones, semen characteristics, or time to pregnancy (TTP). Study characteristics and results were abstracted to predefined forms, and the studies were assessed for the risk of bias and confounding. Sixteen studies investigated the association between PFAS exposure in men and semen parameters, reproductive hormone levels, or TTP. There was a lack of consistent results among the numerous investigated exposure-outcome combinations. However, subtle associations between higher PFOS and lower testosterone or abnormal semen morphology cannot be excluded. Eleven studies assessed the association between PFAS exposure in women and TTP or reproductive hormones levels. Four of eight studies found prolonged TTP with higher PFOS or PFOA, but only one study found an association when restricting to nulliparous women. In men, there is little evidence of an association between PFAS exposure and semen quality or levels of reproductive hormones. For PFOS and PFOA, the literature indicates an association with female fecundability in parous women, which is most likely not causal. [ABSTRACT FROM PUBLISHER]

Objectives: Perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) have been widely used as industrial products, and are persistent organic pollutants due to their chemical stability. Previous studies suggested that PFOS and PFOA might disrupt thyroid hormone (TH) status. Although TH plays an important role in fetal growth during pregnancy, little attention has been paid to the relationships between maternal exposure to perfluorocarbons and TH statuses of mothers and fetuses. We investigated the effects of low levels of environmental PFOS and PFOA on thyroid function of mothers and infants. Methods: Of the eligible subjects in a prospective cohort, 392 mother-infant pairs were selected. Concentration of maternal serum PFOS and PFOA was measured in samples taken during the second and third trimesters or within 1 week of delivery. Blood samples for measuring thyroid stimulating hormone (TSH) and free thyroxine (FT4) levels were obtained from mothers at early gestational stage (median 11.1 weeks), and from infants between 4 and 7 days of age, respectively. Results: Median concentrations of PFOS and PFOA were 5.2 [95 % confidence interval (CI) 1.6-12.3] and 1.2 (95 % CI limitation of detection-3.4) ng/mL, respectively. Maternal PFOS levels were inversely correlated with maternal serum TSH and positively associated with infant serum TSH, whereas maternal PFOA showed no significant relationship with TSH or FT4 among mothers and infants. Conclusions: These findings suggest that PFOS may independently affect the secretion and balances of maternal and infant TSH even at low levels of environmental exposure. [ABSTRACT FROM AUTHOR]

The sorption of perfluorooctanoate (PFOA) onto cyanobacterial biomass is critical to understand its subsequent transport and fate in aqueous environments, but the sorption mechanisms remain largely unknown. This study aimed to investigate the influences of pH, heavy metals, and phosphate on the sorption of PFOA onto cyanobacterial biomass. Results showed that an increase in pH led to a decrease in PFOA sorption, which may be due to electrostatic repulsion. PFOA sorption first decreased, then gradually increased and surpassed the blank in the presence of Pb2+. However, PFOA sorption was suppressed in the presence of Cu2+, Cd2+, and [ABSTRACT FROM AUTHOR]

The consumption of lactic acid bacteria capable of binding or degrading food-borne carcinogens may reduce human exposure to these deleterious compounds. In this study, 25 Lactobacillus strains isolated from human, plant, or dairy environments were investigated for their potential probiotic capacity against perfluorooctanoate (PFOA) toxicity. The PFOA binding, tolerance ability, and acid and bile salt tolerance were investigated and assessed by principal component analysis. Additionally, the effect of different pH levels and binding times was assessed. These strains exhibited different degrees of PFOA binding; the strain with the highest PFOA binding capability was Lactobacillus plantarum CCFM738, which bound to 49.40 ± 1.5 % of available PFOA. This strain also exhibited relatively good cellular antioxidative properties, acid and bile salt tolerance, and adhesion to Caco-2 cells. This study suggests that L. plantarum CCFM738 could be used as a potential probiotic in food applications against PFOA toxicity. [ABSTRACT FROM AUTHOR]

Perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) are persistent organic pollutants in the environment and their occurrence causes toxicological effects on humans. We examined different conventional coagulant treatments such as alum, ferric chloride and polyaluminium chloride in removing these compounds. These were then compared with a natural coagulant (Moringa oleifera). We also investigated the powdered-activated carbon (PAC) and granular-activated carbon (GAC) for removing these compounds. At an initial dose of 5 mg/L, polyaluminium chloride led to a higher reduction of PFOS/PFOA compared with alum which in turn was higher than ferric. The removal efficiency increased with the increase in coagulant dose and decrease in pH.M. oleiferawas very effective in reducing PFOS and PFOA than conventional coagulants, with a reduction efficiencies of 65% and 72%, respectively, at a dose of 30 mg/L. Both PAC and GAC were very effective in reducing these compounds than coagulations. PAC led to a higher reduction in PFOS and PFOA than GAC due to its greater surface area and shorter internal diffusion distances. The addition of PAC (10 min contact time) with coagulation (at 5 mg/L dosage) significantly increased the removal efficiency, and the maximum removal efficiency was forM. oleiferawith 98% and 94% for PFOS and PFOA, respectively. The reduction efficiency of PFOS/PFOA was reduced with the increase in dissolved organic concentration due to the adsorption competition between organic molecules and PFOS/PFOA. [ABSTRACT FROM PUBLISHER]

Background Previous studies on the exposure to perfluoroalkyl acids (PFAAs) and female fertility have provided conflicting results. We aimed to investigate the association between several PFAAs and time to pregnancy among nulliparous women. Methods From 2008 to 2013, we included 1372 women from the Aarhus Birth Cohort, Aarhus University Hospital, Denmark, who provided data on time to pregnancy and a blood sample before 20 gestational weeks. We measured the levels of 16 PFAAs in maternal serum and report data for seven compounds with quantifiable values in at least 50% of samples. Fecundability ratios according to PFAA levels (quartiles or continuous levels) were estimated by discrete-time survival analyses, adjusted for potential confounders. We further investigated the association between PFAAs and infertility (time to pregnancy>12 months or infertility treatment prior to the studied pregnancy) by multivariable logistic regression. Results Median levels of perfluorooctane sulfonate and perfluorooctanoate were 8.3 and 2.0 ng/mL. Overall, no obvious associations were found between any PFAAs and fecundability or infertility. Adjusted fecundability ratios (95% confidence intervals) were 1.09 (0.92–1.29) for perfluorooctane sulfonate and 1.10 (0.93–1.30) for perfluorooctanoate (highest versus lowest quartile). Conclusions We found no evidence of an association between present serum levels of PFAAs and longer time to pregnancy or infertility in nulliparous women. This study further adds to the sparse knowledge on PFAAs besides perfluorooctane sulfonate and perfluorooctanoate. [ABSTRACT FROM AUTHOR]

The distribution and fate of perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) were investigated in the water and sediment of Bohai Bay, China, during 2011–2013. A total of 360 water samples and 60 sediment samples were collected from 20 locations. The median concentrations of PFOS and PFOA were 4.8 and 12.15 ng/L in the water, and 2.65 and 0.62 ng/g-dry in the sediment, respectively. Significant enrichment were observed for PFOS and PFOA in water of sea surface microlayer. The concentrations of these two compounds showed an apparent gradient from nearshore to offshore stations. The correlation analysis and the distribution tendencies indicated that freshwater inflowing to the bay was the main source of PFOS and PFOA. The salinity of seawater and the total organic carbon (TOC) content of sediment heavily affected the spatial distribution and the partitioning of PFOS and PFOA in the sediment-water system. [ABSTRACT FROM AUTHOR]

While selected perfluoroalkyl acids/substances (PFAAs) like perfluorooctanoate (PFOA) and perfluorooctane sulfonate (PFOS) have been detected and measured in laboratory, a method to estimate the total concentration of PFAAs (∑PFAA) in serum has not been developed. Because of the health concerns associated with PFAAs and because of the inability of every laboratory to measure every PFAA as well as because of the non-availability of sensitive enough equipment to be able to detect very small amounts of certain PFAAs, it is of interest to know ∑PFAA. We used data from the National Health and Nutrition Examination Survey for the years 2005–2012 to develop regression models to estimate ∑PFAA by using the levels of PFOA and PFOS only. While data for 2005–2008 were used to develop regression models, data for 2009–2012 were used to evaluate the accuracy of the developed models. Over 63% of observed values for evaluation data were found to be within 10% of the predicted values. The model so developed can be used with just the knowledge of the age, gender, and concentrations of PFOA and PFOS. While the data used to develop the model were generated in U.S., the model can be used to estimate ∑PFAA for data collected in North America and Europe and probably elsewhere in the world. [ABSTRACT FROM AUTHOR]

Background: We previously demonstrated an association between plasma perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) and longer time to pregnancy (TTP) in a sample from the Danish National Birth Cohort (DNBC, 1996-2002). In this study we investigated this association in a new sample from the same cohort. Methods: Sample 1 consisted of 440 women, and Sample 2 consisted of 1161 women from whom we previously published the associations between PFOS or PFOA and TTP. We performed sample-specific and pooled analyses using discrete-time survival analyses to estimate fecundability ratios according to PFOS and PFOA quartiles, adjusted for potential confounders chosen guided by a directed acyclic graph. We also estimated odds ratios for infertility (TTP > 12 months or infertility treatment) according to PFOS and PFOA by multivariable logistic regression. Results: In Sample 1 PFOS was not associated with lower fecundability ratios or infertility, and there was a tendency towards longer TTP with increasing PFOA only in parous women. In Sample 2 previously reported associations were again seen. In the pooled analyses including both parous and nulliparous women fecundability ratios were 13-22 % lower for the three higher quartiles of PFOS or PFOA compared to the reference quartile. Conclusions: The pooled analyses were driven by the larger old sample, but we did not corroborate our previous finding of an association between high PFOS and longer TTP in the new sample. The tendency towards an association for PFOA and TTP in parous women may be due to reverse causation. Results from the new sample are more in line with the recent literature. [ABSTRACT FROM AUTHOR]

Perfluorooctanoate (PFOA) is a persistent chemical that has been detected globally in the natural aquatic environment, while the waste discharge of fluoropolymer industry is one of the major sources of PFOA pollution. In this study, the removal and recovery of PFOA by nanofiltration (NF) were investigated with ammonium perfluorooctanoate model solutions under a wide range of PFOA concentrations. Performances of two commercially available NF membranes, namely NF270, NF90, were evaluated. The results show that the NF90 membrane offered a higher PFOA rejection (almost 100% at a PFOA concentration below 800 mg L −1 ). Using NF90 membrane, a model solution with a higher initial PFOA concentration of 1000 mg L −1 was used to further test the membrane performance. Both stable osmotic pressure at membrane surface and high PFOA rejection (99.3%) were obtained when the PFOA concentration was larger than a certain value due to the formation of micelles. Furthermore, membrane operation parameters (i.e. stirring speed, pH, temperature, and permeate flux) on the TMP and the PFOA concentration in permeate were investigated under a much higher initial PFOA concentration (10,000 mg L −1 ). The experimental results clearly confirm that recovery of highly concentrated PFOA of more than 117073.7 mg L −1 could be achieved by one-step NF treatment, while the permeate could be further treated by multi-stage NF to fully recover the PFOA. It was also found that the permeability of membrane could be recovered completely by simple water rinse, suggesting that NF is highly applicable for recovery of PFOA from wastewater in fluoropolymer production. [ABSTRACT FROM AUTHOR]

Perfluorinated compounds (PFCs), such as perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA), are a family of commonly used industrial chemicals whose persistence and ubiquity in blood samples of humans and wildlife have become a growing concern. Despite PFOS and PFOA having been found in human blood and tissue samples from occupationally exposed workers and the general worldwide population, little systematic knowledge has accrued with respect to exposure levels in Uyghurs in the Sinkiang-Uighur Autonomous Region of China, which is predominantly agricultural and pastoral. Our goal was to provide background data for biological monitoring in the general population of this region. In this study, 110 self-reported healthy human serum samples were collected from nonoccupationally exposed Uyghurs volunteers and analyzed by microbore HPLC-electrospray tandem mass spectrometry. Among the 110 blood specimens, PFOS was detected in 102 samples (93 %) and ranged from the lower limit of quantification of 0.01 to 22.63 μg/L with a median of 1.93 μg/L (interquartile range 1.00-3.43 μg/L). The median was higher among males (2.39 μg/L; interquartile range 1.23-4.40 μg/L) than that among females (1.20 μg/L; interquartile range 0.83-2.77 μg/L). No significant difference was observed with respect to age. The concentration of PFOA was lower than that of PFOS and was found only in seven samples (6 %) at concentrations above the limit of quantification. This study is the first investigation to reveal serum PFOS and PFOA levels in the general population of Uyghurs. PFOS and PFOA concentrations found in the present investigation were lower than those found in recent studies consisting of subjects from different geographic locations (PFOS 5.0-44.7 μg/L, PFOA 1.5-10 μg/L). [ABSTRACT FROM AUTHOR]

Emerging evidence suggests associations between Perfluoroalkyl substances (PFASs) exposure and asthma, but the findings are inconsistent. The current study sought to investigate whether perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) could contribute to asthma exacerbation and to clarify the underlying biological mechanisms. The objectives are a) to determine whether PFOS or PFOA could aggravate the mouse asthma and pulmonary inflammation b) to investigate whether PFOS and PFOA regulate the balance of Th1/Th2 through the JAK-STAT signaling pathway and aggravated asthma. Ovalbumin (OVA) induced asthmatic mice were exposed to PFOS or PFOA by gavage. PFOS and PFOA serum level and toxicity in organs were assessed; and the impacts on respiratory symptoms, lung tissue pathology, T helper cell (Th2) response, and STAT6 pathway activity were also evaluated. In vitro Jurkat cells were used to study the mechanisms of PFOS and PFOA mediated Th1 and Th2 responses. Both PFOS and PFOA exacerbated lung tissue inflammation (greater number of eosinophils and mucus hyperproduction), upregulated Th2 cytokine production (IL-4 and IL-13), and promoted Th2 cells and STAT6 activation. Furthermore, PFOS and PFOA enhanced the Th2 response in Jurkat cells via STAT6 activation; and the effect of PFOS exposure on GATA-3, IL-4 and IFN-γ was blocked after the expression of STAT6 was suppressed in Jurkat cells, however, the effects of PFOA exposure were only partially blocked. PFOS and PFOA aggravated inflammation among OVA-induced asthmatic mice, by promoting the Th2 response in lymphocytes and disturbing the balance of Th1/Th2 through the JAK-STAT signaling pathway. Unlabelled Image • PFOS and PFOA exacerbated lung tissue inflammation, upregulated Th2 cytokine production, aggravated asthma in asthmatic mice. • PFOS and PFOA regulated the balance of Th1/Th2 through the JAK-STAT signaling pathway and aggravated asthma. • PFOS induced Th1/Th2 imbalance through up-regulation of p-STAT6 level, while PFOA through another pathway. [ABSTRACT FROM AUTHOR]

Micellization and microstructure of mixed micelles from mixtures of an anionic fluorocarbon surfactant sodium perfluorooctanoate (NaPFO) and cationic alkylmethyl-imidazolium based non-amphiphilic and amphiphilic ionic liquids (ILs) with different alkyl chain length (C 4 , C 6 , C 8, C 10 and C 12) and anions viz. chloride (Cl−), tetrafluoroborate (BF 4 −), hexaflurophosphate (PF 6 −), octylsulphate (C 8 SO 4 −) and trifluoromethane-sulphonate (CF 3 SO 3 −) were examined extensively by surface tension and small-angle neutron scattering (SANS) measurements. Low critical micelle concentration (CMC) and large negative value of interaction parameter (β) showed synergism in all the mixed systems and it depends on the molecular characteristics of ILs. Thermodynamic parameters for mixed monolayers and mixed micelles were evaluated and discussed. Micellar growth, shape changes and micelle to vesicle transitions obtained from these oppositely charged mixed systems depend on the surface activity of ILs (alkyl chain and counter ions). Influence of ILs which differ in counter ions with similar chain length and similar counter ions with different chain lengths on aggregation patterns of NaPFO micelles have been examined using SANS. The data for size, shape and aggregation number for aggregates formed by these mixed systems evaluated from the fitted SANS data are reported and discussed in terms of their distinct interaction with NaPFO micelles. The present study is a significant addition to existing knowledge on ionic liquid induced morphological changes of sodium perfluorooctanoate micelles. Unlabelled Image • Oppositely charged systems of NaPFO and ILs showed strong synergism. • ILs show concentration-dependent structural transition of NaPFO micelles. • Aggregate morphology depends upon the alkyl chain length and counter ions of ILs. [ABSTRACT FROM AUTHOR]

Aminosilane materials, with their low cost and ease of modification, have exhibited great potential for the adsorption of perfluorinated compounds (PFCs) from water. However, this kind of material may be facing two drawbacks during its application: low resistance to hydrolysis and difficulties in separation from the water matrix. This work proposed a strategy of grafting N-(2-aminoethyl) aminopropyltrimethoxysilane (AE-APTMS) on the surface of magnetic γ-Fe 2 O 3 nanoparticles by full utilization of the sorption sites provided by the aminosilane and the magnetism by γ-Fe 2 O 3. The FTIR and XRD results verified the formation of the magnetic AE-APTMS nanocomposite. The core-shell nanocomposite showed a superparamagnetic property and an isoelectric point at pH = 8.2. Particularly, compared to the aminopropyltriethoxysilane (APTES) nanocomposite, the AE-APTMS nanocomposite exhibited improved hydrolytic stability with 60% less loss of the amine groups during the 48 h adsorption process, as the longer alkyl chain hindered the aminosilane detachment. The AE-APTMS nanocomposite exhibited a rapid adsorption with the removal efficiency of 78% for perfluorooctane sulfonate (PFOS) and 65% for perfluorooctanoate (PFOA) due to the electrostatic interaction and hydrophobic interaction. The regeneration and reuse of the magnetic AE-APTMS nanocomposite were conveniently realized with the removal efficiency higher than 70% for both PFOS and PFOA even after 15 adsorption-desorption cycles. The stable magnetic aminosilane nanocomposite with the ease of separation may provide a new strategy to achieve the economical and effective removal of typical PFCs from water. Image 1 • Magnetic aminosilane nanocomposite was prepared with enhanced hydrolytic stability. • The AE-APTMS could discourage the amine-catalyzed detachment of functional amines. • γ-Fe 2 O 3 as the core with magnetism, and aminosilane as the shell with sorption sites. • Magnetic nanocomposite achieved rapid adsorption for PFOS/A. • Magnetic nanocomposite were regenerated and reused in 15 successive cycles. [ABSTRACT FROM AUTHOR]

Per- and polyfluoroalkyl substances (PFAS) are a class of chemicals that were widely used in manufacturing and are now present in the environment throughout the world. It is known that various PFAS are quantifiable in human in blood, but potential adverse health outcomes remain unclear. Sentinel and non-traditional model species are useful to study potential toxicity of PFAS in order to understand the relationship between environmental and human health. Here, we present a critical review of studies on the neurotoxicity of PFAS in sentinel and non-traditional laboratory model systems, including Caenorhabditis elegans (nematode), Dugesia japonica (planarian), Rana pipiens (frogs), Danio rerio and Oryzias melastigma (fish), and Ursus maritimus (polar bears). PFAS have been implicated in developmental neurotoxicity in non-traditional and traditional model systems as well as sentinel species, including effects on neurotransmitter levels, especially acetylcholine and its metabolism. However, further research on the mechanisms of toxicity needs to be conducted to determine if these chemicals are affecting organisms in a similar manner. Overall, findings tend to be similar among the various species, but bioaccumulation may vary, which needs to be taken into account in future studies by quantifying target organ concentrations of PFAS to better compare different species. Furthermore, data on the majority of PFAS is lacking in neurotoxicity testing, and additional studies are needed to corroborate findings thus far. [ABSTRACT FROM AUTHOR]

Poly- and perfluoroalkyl substances (PFAS) are manmade synthetic chemicals which have been in existence for over 70 years. Though they are currently being phased out, their persistence in the environment is widespread. There is increasing evidence linking PFAS exposure to health effects, an issue of concern since PFAS such as perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) bioaccumulate in humans, with a half-life of years. Many epidemiological studies suggest that, worldwide, semen quality has decreased over the past several decades. One of the most worrying effects of PFOS and PFOA is their associations with lower testosterone levels, similar to clinical observations in infertile men. This review thus focuses on PFOS/PFOA-associated effects on male reproductive health. The sources of PFAS in drinking water are listed. The current epidemiological studies linking increased exposure to PFAS with lowered testosterone and semen quality, and evidence from rodent studies supporting their function as endocrine disruptors on the reproductive system, exhibiting non-monotonic dose responses, are noted. Finally, their mechanisms of action and possible toxic effects on the Leydig, Sertoli, and germ cells are discussed. Future research efforts must consider utilizing better human model systems for exposure, using more accurate PFAS exposure susceptibility windows, and improvements in statistical modeling of data to account for the endocrine disruptor properties of PFAS.

Perfluorooctanoate (PFOA) has been used extensively in the manufacture of both commercial and household products. PFOA serum concentrations have been associated with adverse health effects, including lower body mass in children and infants. To determine if there is an association between serum PFOA concentration and body mass, serum insulin and lipid profile in exposed young girls. We conducted a cross-sectional study of PFAS environmental biomarkers and insulin resistance in 6 to 8 year-old girls from Greater Cincinnati (n=353). In 2004–2006, blood samples were obtained to measure polyfluoroalkyl substances (PFAS), fasting insulin, glucose and lipids. Clinical exams included anthropometric measurements and pubertal maturation staging. Linear regression and mediation analyses, specifically structural equation modeling (SEM), were used to determine the strength and direction of the relationships between PFAS, pubertal maturation status, body mass index (BMI), cholesterol and insulin resistance. The median PFOA (7.7ng/ml) was twice the National Health and Nutrition Examination Survey (2005–2006). Only PFOA, a PFAS sub-species, showed statistically significant relationships with the outcomes. In regression models, PFOA was associated with decreased BMI and waist-to-height ratio (p=0.0008; p=0.0343), HDL-cholesterol (p=0.0046) and had a borderline inverse association with the HOMA Index of insulin resistance (p=0.0864). In SEM, PFOA retained an inverse relationship with BMI (p<0.0001) but the relationships with HOMA and HDL-cholesterol were no longer statistically significant. Pubertal initiation (Tanner breast or pubic stage 2 or greater) and BMI were associated with increased HOMA Index (p<0.0001). These findings suggest PFOA exposure in young girls affects both BMI and ultimately insulin resistance. In mediation analysis with puberty in the model, the direct effects of PFOA on insulin resistance and were reduced. • PFAS chemicals are commonly used in manufacturing and are widely detected in humans due to a half-life of 3-4 years. • Studies have shown PFAS exposure during developmental windows results in decreased weight and changes in the lipid profile. • Median serum levels of PFOA in a population of girls, exposed through drinking water, were almost twice the NHANES level. • A strong linear relationship was found between PFOA and BMI, PFOA and HDL cholesterol. • Structural equation modeling revealed that the PFOA exposure effect of decreasing BMI consequently decreased insulin resistance. [ABSTRACT FROM AUTHOR]

This data article includes details on the simple and efficient analytical methods used to measure perfluoroalkyl substances (PFASs) in water, soil, and produce from home gardens in Minnesota. PFASs in water were analyzed via direct injection. PFASs were extracted from homogenized soil using sonication, and from produce using dispersive solid phase extraction. Isotope dilution was used for quantitation in all methods. The method performance parameters and quality control measures are described. The methods described are applicable for a PFAS ranging from C4-C8 and the produce method was used on a wide variety of produce. For further details and experimental findings, please refer to the article "Occurrence of perfluoroalkyl substances (PFAS) in garden produce at homes with a history of PFAS-contaminated drinking water" The key benefits of this method are: •This method adapts dispersive solid phase extraction for the analysis of PFAS in produce.•The method can be used to analyze PFAS ranging from 4 to 8 carbons in a variety of produce types.

High-dose exposure of mice to perfluorooctanoate (PFOA) induces both hepatotoxicity and immunotoxicity. Here, we characterized the effects of 10-day dietary treatment with PFOA (0.002-0.02%, w/w) on the liver and complement system of male C57BL/6 mice. At all four doses, this compound caused hepatomegaly and reduced the serum level of triglycerides (an indicator for activation of the peroxisome proliferator-activated receptor-alpha (PPARα)). At the highest dose (0.02%, w/w), this hepatomegaly was associated with the hepatic injury, as reflected in increased activity of alanine aminotranferase (ALAT) in the serum, severe hepatocyte hypertrophy and hepatocellular necrosis. PFOA-induced hepatic injury was associated with in vivo activation of the complement system as indicated by (i) significant attenuation of the serum activities of both the classical and alternative pathways; (ii) a marked reduction in the serum level of the complement factor C3; and (iii) deposition of the complement factor C3 fragment (C3a) in the hepatic parenchyma. PFOA did not activate the alternative pathway of complement in vitro. At doses lower than 0.02%, PFOA induced hepatocyte hypertrophy without causing liver injury or activating complement. These results reveal substantial involvement of activation of complement in the pathogenesis of PFOA-induced hepatotoxicity., (Copyright © 2014 Elsevier Ltd. All rights reserved.)