Abstract  Wide application of perfluoroalkyl acids (PFAAs) has raised great concerns on their side-effects on human health. PFAAs have been shown to accumulate mainly in the liver and cause hepatotoxicity. However, PFAAs can also deposit in lung tissues through air-borne particles and cause serious pulmonary toxicity. But the underlying mechanisms are still largely unknown. Autophagy is a type of programmed cell death parallel to necrosis and apoptosis, and may be involved in the lung toxicity of PFAAs. In this study, lung cancer cells, A549, were employed as the model to investigate the effects of three PFAAs with different carbon chain lengths on cell autophagy. Through Western blot analysis on LC3-I/II ratio of cells exposed to non-cytotoxic concentration (200 µM) and cytotoxic concentration (350 µM), we found concentration-dependent increase of autophagosomes in cells, which was further confirmed by TEM examination on ultra-thin section of cells and fluorescence imaging on autophagosomes in live cells. The abundance of p62 increased with the PFAAs concentration indicating the blockage of autophagy flux. Furthermore, we identified the mitochondrial autophagy (mitophagy) and endoplasmic reticulum autophagy (ER-phagy) morphologically as the major types of autophagy, suggesting the disruption on mitochondria and ERs. These organelle damages were confirmed by the overgeneration of ROS, hyperpolarization of mitochondrial membrane potential, as well as the up-regulation of ER-stress-related proteins, ATF4 and p-IRE1. Further analysis on the signaling pathways showed that PFAAs activated the MAPK pathways and inhibited the PI3K/Akt pathway, with potencies following the order of PFDA > PFNA > PFOA. Anti-oxidant (NAC) treatment did not rescue cells from death, indicating that oxidative stress is not the reason of cytotoxicity. Inhibition of autophagy by Atg5 siRNA and chloroquine even increased the toxicity of PFAAs, suggesting that PFAAs-autophagy was induced as the secondary effects of organelle damages and played a protective role during cell death.

Abstract  INTRODUCTION: Perfluoroalkyl substances (PFASs) are fluorinated organic compounds that have been used in a variety of industrial and consumer applications. Menstruation is implicated as a possible route of elimination for PFASs in women. The overall purpose of this study was to examine menstrual cycle characteristics as determinants of plasma PFAS concentrations in women.

METHODS: Our study sample consisted of 1977 pregnant women from the Norwegian Mother and Child Cohort (MoBa) study. The women were asked about menstrual cycle regularity in the year before the pregnancy and typical menstrual cycle length as well as other demographic and reproductive characteristics in a questionnaire completed during the pregnancy. Blood samples were collected around 17-18 weeks gestation and PFAS concentrations were measured in plasma. We examined the association between menstrual cycle characteristics and seven PFASs (perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), perfluorodecanoic acid (PFDA), perfluoroundecanoic acid (PFUnDA), perfluorohexane sulfonate (PFHxS), perfluoroheptane sulfonate (PFHpS), and perfluorooctane sulfonate (PFOS)) using multiple linear regression, adjusted for age, pre-pregnancy body mass index, smoking, education, income, parity, oral contraceptive use, inter-pregnancy interval, and breastfeeding duration.

RESULTS: Irregular cycles were not associated with PFAS concentrations. Overall, we found no evidence of associations between menstrual cycle length and PFAS concentrations. In subgroup analyses we found some evidence, among parous women, of decreased PFHpS and PFOS with short menstrual cycles; we also found, among recent OC users (in the 12 months before the questionnaire) increased PFNA and PFUnDA with long cycle length. Limitations of our study include misclassification of menstrual cycle characteristics, small sample sizes in the sub-group analyses, and a lack of information on duration and volume of menses.

CONCLUSIONS: In the entire study sample, we found little evidence of menstrual cycle characteristics as determinants of PFAS concentrations. However, we observed some associations between cycle length and PFAS concentrations with some select PFAS compounds in subgroup analyses.

Abstract  Perfluoroalkyl acids (PFAAs) have been found extensively in wildlife and human bodies by sources of drinking water and food. In this study, we investigated the effects of three PFAAs, perfluoropentanoic acid (PFPA), perfluorooctanoic acid (PFOA), and perfluorodecanoic acid (PFDA), on the antioxidative defense system and lipid peroxidation in erythrocytes separately. The results demonstrated that they could lead to significant decline trends in the glutathione (GSH) levels together with increases of malondialdehyde (MDA) content, suggesting that three PFAAs induced oxidative stress to erythrocytes. Also PFDA with a longer carbon chain length posed more of a threat than other two PFAAs. Furthermore, the activities of superoxide dismutase (SOD), catalase (CAT), and glutathione peroxidase (GPx) were also altered in the presence of PFAAs upon erythrocytes. The changes of oxidative stress markers and the concomitant alterations of antioxidant enzymes suggest the role of oxidative stress in PFAA-induced damage upon erythrocytes.

Abstract  Perfluoroalkyl substances (PFAS) are persistent bio-accumulative chemicals that impact the health of pregnant women and their children. PFAS derive from environmental and consumer products, which depend on human lifestyle, socioeconomic characteristics, and time variation. Here, we aimed to explore the temporal trends of PFAS in pregnant women and the characteristics related to maternal PFAS concentration. Our study is part of the Hokkaido Study on Environment and Children's Health, the Hokkaido large-scale cohort that recruited pregnant women between 2003 and 2011. Blood samples were acquired from pregnant women during the third trimester to measure PFAS and cotinine concentrations. Maternal basic information was collected with a baseline structured questionnaire. Eleven PFAS were measured from 2123 samples with ultra-performance liquid chromatography coupled with triple quadrupole tandem mass spectrometry. Eight PFAS were above 80% detection rate and were included in the final analysis. We used multivariable linear regression to analyze the association of pregnant women characteristics with the levels of eight PFAS. The temporal trend of PFAS was observed in two periods (August 2003 to January 2006 and February 2006 to July 2012). The concentration of perfluorooctane sulfonate (PFOS) significantly decreased from August 2003 to January 2006 and from February 2006 to July 2012. The concentrations of perfluorododecanoic acid (PFDoDA), perfluoroundecanoic acid (PFUnDA), and perfluorotridecanoic acid (PFTrDA) increased significantly between August 2003 and January 2006, whereas they decreased significantly between February 2006 and July 2012. Women with pre-pregnancy body mass index (BMI) >25 kg/m² had lower PFUnDA, PFDoDA, and PFTrDA levels than did those with normal BMI (18.5⁻24.9 kg/m²). Pregnant women, who were active smokers (cotinine > 11.49 ng/mL), had higher PFOS than the non-smokers (cotinine < 0.22 ng/mL). Lower levels of PFHxS, PFOS, PFOA, PFNA, and PFDA were observed in women, who had given birth to more than one child. There were also significant positive associations between PFAS levels and annual income or maternal education. PFAS levels varied in women with higher pre-pregnancy BMI, active smoking status, higher education level and annual income. The causes of the individual PFAS differences should be explored in an independent study.

Abstract  Serum samples were collected from volunteers of various ages and both genders using a proportionate stratified sampling method, to assess the exposure of the general population in Busan, South Korea to perfluorinated compounds (PFCs). 16 PFCs were investigated in serum samples from 306 adults (124 males and 182 females) and one day composite diet samples (breakfast, lunch, and dinner) from 20 of the serum donors, to investigate the relationship between food and serum PFC concentrations. Perfluorooctanoic acid and perfluorooctanesulfonic acid were the dominant PFCs in the serum samples, with mean concentrations of 8.4 and 13 ng/mL, respectively. Perfluorotridecanoic acid was the dominant PFC in the composite food samples, ranging from

Abstract  The toxicity of individual perfluoroalkyl acids (PFAAs) has been suggested to be determined by the carbon chain length as well as the functional group attached. We tested seven different PFAAs including both sulfonic and carboxylic PFAAs with different chain length to evaluate the developmental toxicity in zebrafish embryos. Generally, the acute toxicity of PFAAs is relatively low to zebrafish embryos. The EC50 values ranged from 1.5 to 2200mg/L. We observed a relationship between higher toxicity with longer carbon chain. In addition, we also observed a higher toxicity for sulfonic PFAAs than for carboxylic PFAAs.

Abstract  Bench- and pilot-scale sorption tests were used to probe the performance of several biochars at removing perfluoroalkyl acids (PFAA) from field waters, compared to granular activated carbon (GAC). Screening tests using organic matter-free water resulted in hardwood (HWC) (Kd = 41 L g(-1)) and pinewood (PWC) (Kd = 49 L g(-1)) biochars having the highest perfluorooctanoic acid (PFOA) removal performance that was comparable to bituminous coal GAC (Kd = 41 L g(-1)). PWC and HWC had a stronger affinity for PFOA sorbed in Lake Mead surface water (KF = 11 mg((1-n)) L(n) g(-1)) containing a lower (2 mg L(-1)) dissolved organic carbon (DOC) concentration than in a tertiary-filtered wastewater (KF = 8 mg((1-n)) L(n) g(-1)) with DOC of 4.9 mg L(-1). A pilot-scale study was performed using three parallel adsorbers (GAC, anthracite, and HWC biochar) treating the same tertiary-filtered wastewater. Compared to HWC, and anthracite, GAC was the most effective in mitigating perfluoropentanoic acid (PFPnA), perfluorohexanoic acid (PHxA), PFOA, perfluorooctane sulfonic acid (PFOS), and DOC (45-67% removed at 4354 bed volumes) followed by HWC, and then anthracite. Based on bench- and pilot-scale results, shorter-chain PFAA [perfluorobutanoic acid (PFBA), PFPnA, or PFHxA] were more difficult to remove with both biochar and GAC than the longer-chain, PFOS and PFOA.

Abstract  A comparative study on the use of cetyltrimethylammonium bromide (CTAB)-coated silica and sodium dodecyl sulphate (SDS)-coated alumina mixed hemimicelles-based solid-phase extraction (SPE) for the pre-concentration of six perfluorinated compounds (PFCs) in environmental water samples was presented. The six analytes heptafluorobutyric acid (HFBA), perfluoroheptanic acid (PFHeA), perfluorooctanic acid (PFOA), perfluorooctanic sulfonic (PFOS), perfluorononanic acid (PFNA) and perfluorodecanic acid (PFDeA) were quantitatively retained on both sorbent materials. The cationic surfactant (CTAB adsorbed onto silica) was more appropriate for SPE of PFCs. The main factors affecting adsolubilization of PFCs including the amount of surfactant, pH of solution, sample loading volume and desorption were investigated and optimized. Concentration factor of 500 were achieved by SPE of 500 mL of several environmental water samples. The method detection limits obtained for HFBA, PFHeA, PFOA, PFOS, PFNA and PFDeA were 0.10, 0.28, 0.07, 0.20, 0.10 and 0.05 ng/L, respectively. The relative standard deviation of recoveries ranged from 2 to 8%, which indicated good method precision.

Abstract  Per- and polyfluoroalkyl substances (PFAS) are widely found in humans and the environment. Their persistence, bioaccumulation and toxicity make them a source of increasing public health concern. In this study, we analyzed the concentrations and geographical distribution of six PFAS in the serum of 755 Spanish adults aged 18-65. The geometric mean concentrations (and P95 values) for PFOS (perfluoroctane sulfonate), PFOA (perfluorooctanoic acid), PFHxS (perfluorohexane sulfonate), PFNA (perfluorononanoic acid) and PFDA (perfluorodecanoic acid) were 7.67 (19.3), 1.99 (5.48), 0.91 (2.84), 0.96 (2.44) and 0.42 (0.99) μg/L, respectively. N-Methylperfluorooctane sulfonamide (N-MeFOSAA) was detected in only 3.3% of samples. Residents in northeast (Catalonia) and northwest of Spain (Galicia) were found to have the highest serum values, whereas residents in the Canary Islands had the lowest values for almost all PFAS. Men presented higher levels than women, and we confirm that lactation (breastfeeding) contributes to a reduced body burden for all PFAS in women. Our data provide new information on exposure to PFAS in a national cross section sample of Spanish adults, thus providing a proxy for reference values for the Spanish population and forming the base for following temporal trends in the future.

Abstract  Our previous study in 2011 reported the detection of BPA and PFAAs in 20 species of marine and freshwater fishes. With an emerging evidence to suggest the metabolic-disrupting effects of BPA/PFAAs in animals, the present study was aimed to provide a time-trend analysis to determine the current concentrations of PFAAs and BPA in 20 commercially available Hong Kong species of fishes. Since the manufacture and use of BPA is being prohibited in most nations, the introduction of BPA alternatives has recently been incorporated in the markets. Therefore, the concentrations of BPB, BPF and BPS were determined. In the present study, all freshwater and seawater fish samples showed quantified concentrations [>Limit of Quantification (LOQ<0.5ng/g)] of BPA. BPF was detected in some marine (yellow seafin, bigeye, goldspotted rabbitfish, snubnose pompano, tongue sole, Bleeker's grouper and orange-spotted grouper) and freshwater fishes (mud carp, crucian carp, tilapia, catfish, mandarin fish, grass carp, grey mullet and spotted snakehead). Two of the compounds, BPS and BPB could only be identified in the marine fishes (snubnose pompano, yellow seafin). In PFAA analysis, PFOA, PFDA, PFOS, PFUdA and PFDoA were found in most of the marine and freshwater fishes. PFOS and PFOA were shown to be the two predominant PFAAs in fishes. On the basis of the measured concentrations of bisphenols, BPs (BPA, BPB, BPF, BPS) and PFAAs, the average daily intake for BPs (20.5-31.5ng/kgb.w./day) and PFAAs (1.17-1.83ng/kgb.w./day) were calculated and found to be lower than values of tolerable daily intake (TDI) established in Europe. However, as compared with our previous study in 2011, the present study revealed an approximate 10-fold increase in the concentrations of BPA in the fish samples. Although the hazard ratio of consuming fishes for BPA and PFAA exposure is expected to remain low, possible additive metabolic-disrupting effect of BPA and its analogues as well PFAAs should be taken into consideration for human health risk assessment.

Abstract  Perfluoroalkyl substances (PFASs) are highly persistent chemicals that might be associated with asthma and allergy, but the associations remain unclear. Therefore, this study examined whether pre- and postnatal PFAS exposure was associated with childhood asthma and allergy. Measles, mumps, and rubella (MMR) vaccination in early life may have a protective effect against asthma and allergy, and MMR vaccination is therefore taken into account when evaluating these associations. In a cohort of Faroese children whose mothers were recruited during pregnancy, serum concentrations of five PFASs - Perfluorohexane sulfonic acid (PFHxS), perfluorooctane sulfonic acid (PFOS), perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), and perfluorodecanoic acid (PFDA) - were measured at three timepoints (maternal serum in pregnancy week 34-36 and child serum at ages 5 and 13 years) and their association with immunoglobulin E (IgE) (cord blood and at age 7 years) and asthma/allergic diseases (questionnaires at ages 5 and 13 years and skin prick test at age 13 years) was determined. A total of 559 children were included in the analyses. Interactions with MMR vaccination were evaluated. Among 22 MMR-unvaccinated children, higher levels of the five PFASs at age 5 years were associated with increased odds of asthma at ages 5 and 13. The associations were reversed among MMR-vaccinated children. Prenatal PFAS exposure was not associated with childhood asthma or allergic diseases regardless of MMR vaccination status. In conclusion, PFAS exposure at age 5 was associated with increased risk of asthma among a small subgroup of MMR-unvaccinated children but not among MMR-vaccinated children. While PFAS exposure may impact immune system functions, this study suggests that MMR vaccination might be a potential effect-modifier.

Abstract  Perfluorinated compounds (PFCs) have potential health risk to human. In this paper, human serum samples collected from Jiading District, Shanghai aged from 23 to 87 years old (12 male and 33 female) were analyzed for 17 perfluorinated compounds (PFCs). A novel method for the elimination of background contamination of perfluorooctanoic acid (PFOA) generated from instrument by the modification of high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) has also been developed and validated. The limit of detection (LOD) for all monitored PFCs range from 0.02 to 0.18 ng mL(-1). The limit of quantitation (LOQ) for PFOS and PFOA was 2.23 and 1.60 ng mL(-1), respectively, and for other PFCs it ranged from 0.04 to 0.88 ng mL(-1). Of the 17 PFCs analyzed in Shanghai serum, eleven were found. The dominating PFCs in all samples were perfluorooctanesulfonate (PFOS) and PFOA with a fraction of 49.5%, 34.2%, respectively. The median total concentration of each serum samples was 53.43 ng mL(-1) with a range from

Abstract  INTRODUCTION: Perfluorinated alkylated substances (PFAS) are persistent industrial chemicals that have resulted in global environmental exposures. Previous epidemiological studies have reported possible effects on the immune system after developmental PFAS exposure, but the possible impact on childhood infectious disease is unclear.

OBJECTIVES: To investigate the association between prenatal exposure to PFAS and symptoms of infections at age 1-4years.

METHODS: The Odense Child Cohort is an on-going prospective study on children's health, where serum concentrations of perfluorooctane sulfonic acid (PFOS), perfluorooctanoic acid (PFOA), perfluorohexane sulfonic acid (PFHxS), perfluorodecanoic acid (PFDA) and perfluorononanoic acid (PFNA) were measured in 649 pregnant women before gestational week 16. Of these women, 359 reported on symptoms of infection in their child every two weeks for a one-year period. The association between prenatal exposure to PFAS and the symptoms was estimated using a logistic regression model and a negative binomial regression model. For the latter, the outcome was reported as an incidence rate-ratio (IRR), and all models were adjusted for maternal age, educational level, parity and child age.

RESULTS: On average, the children experienced symptoms of infection 23% of the time during one year. PFOS exposure in the high tertile compared to the low tertile was associated with a statistically significant increased proportion of days with fever (IRR: 1.65 (95% CI: 1.24, 2.18), P-trend<0.001) and an increased odds of experiencing days with fever above the median (OR: 2.35 (95% CI: 1.31, 4.11). The latter tendency was also apparent for PFOA (OR: 1.97 (95% CI: 1.07, 3.62). Further, higher concentrations of PFOS and PFOA tended to increase the number of episodes of co-occurrence of fever and coughing and fever and nasal discharge during the one-year study period.

CONCLUSION: We found a positive association between prenatal exposure to PFOS and PFOA and the prevalence of fever, which may be a sensitive marker of infection. This finding is in agreement with an immunotoxic effect of prenatal exposure to PFAS. The wider implications for childhood infectious disease deserve attention.

Abstract  This study aimed to quantify concentrations of fifteen perfluoroalkyl acids (PFAAs) in the plasma of American alligators (Alligator mississippiensis) inhabiting wetlands surrounding the Kennedy Space Center (KSC) in Florida, USA located at Merritt Island National Wildlife Refuge (MINWR). Approximately 10 male and 10 female alligators (ntotal = 229) were sampled each month during 2008 and 2009 to determine if seasonal or spatial trends existed with PFAA burden. PFOS represented the highest plasma burden (median 185 ng/g) and PFHxS the second highest (median 7.96 ng/g). While no significant seasonal trends were observed, unique spatial trends emerged. Many of the measured PFAAs co-varied strongly together and similar trends were observed for PFOS, PFDA, PFUnA, and PFDoA, as well as for PFOA, PFHxS, PFNA, PFTriA, and PFTA, suggesting more than one source of PFAAs at MINWR. Higher concentrations of PFOS and the PFAAs that co-varied with PFOS were collected from animals around sites that included the Shuttle Landing Facility (SLF) fire house and the Neil Armstrong Operations and Checkout (O&C) retention pond, while higher concentrations of PFOA and the PFAA that co-varied with PFOA were sampled from animals near the gun range and the old fire training facility. Sex-based differences and snout-vent length (SVL) correlations with PFAA burden were also investigated.

Abstract  In the Odense child cohort, serum concentrations of perfluorooctanesulfonic acid (PFOS), perfluorooctanoic acid (PFOA), perfluorohexane sulfonic acid (PFHxS), perfluorononanoic acid (PFNA), and perfluorodecanoic acid (PFDA) were measured in 638 pregnant women. Birth weight, head and abdominal circumferences and gestational age were determined. Anogenital distance (AGD), the distance from the anus to the genital organs, and penile width were measured 3 months after expected date of birth in 511 children. PFOS, PFHxS, PFNA and PFDA were associated with a decreased AGD in girls (p-trend<0.05) after adjusting for age and weight-for-age standard deviation score. PFOS in the highest quartile was associated with a 2.8mm (95% confidence intervals -4.5; -1.1) reduction in AGD in girls. No such tendencies were seen in boys. However, a tendency toward increased birth weight in girls and reduced birth weight in boys suggests that sex-dimorphic effects may occur from endocrine disrupting effects of these substances.

Abstract  Sewage sludge can be a relevant source of perfluoroalkyl acids (PFAAs) for the environment. In order to reduce emissions from this source, Bavarian authorities enforced in 2008 an analysis of PFAAs from sewage sludge derived from municipal wastewater treatment plants (WWTPs). 4981 sludge samples from 1165 different WWTPs were analyzed between 2008 and 2013 for 11 PFAAs compounds. During this period, 71 WWTPs exceeded the precautionary limit of 125 μg kg(-1) dm of total PFAAs in sludge samples at least once with a decreasing tendency. The yearly exceedances of the investigated WWTPs decreased from 6% in 2008 to 0.8% in 2013. At the same time, the percentage of uncontaminated WWTPs increased from 33% to 65%. Perfluorooctane sulfonic acid (PFOS) was the predominant compound found in 41% of all sludge samples. Perfluorodecanoic acid (PFDA) was detected in 19% and Perfluorooctanoic acid (PFOA) in 7%. Very high PFAAs concentrations (>500 μg kg(-1) dm) in sewage sludge were generally caused by firefighting foams containing PFAAs or emissions from PFAAs-using industries including metal plating, textile, leather or paper industries. Trend analyses of the six year period show that PFAAs contamination in sewage sludge clearly decreased for 47% of the WWTPs. However, for 16% of the WWTPs an increasing trend was detected, even though the concentration levels were below the precautionary limit. During the six years of investigation the load of total PFAAs in sewage sludge was reduced by more than 90%, from 17 t a(-1) in 2008 to 1.5 t a(-1) in 2013.

Abstract  The usage of amorphous solids in practical applications, such as in medication, is commonly limited by the poor long-term stability of this state, because unwanted crystalline transitions occur. In this study, three different polymeric coatings are investigated for their ability to stabilize amorphous films of the model drug clotrimazole and to protect against thermally induced transitions. For this, drop cast films of clotrimazole are encapsulated by initiated chemical vapor deposition (iCVD), using perfluorodecyl acrylate (PFDA), hydroxyethyl methacrylate (HEMA), and methacrylic acid (MAA). The iCVD technique operates under solvent-free conditions at low temperatures, thus leaving the solid state of the encapsulated layer unaffected. Optical microscopy and X-ray diffraction data reveal that at ambient conditions of about 22 °C, any of these iCVD layers extends the lifetime of the amorphous state significantly. At higher temperatures (50 or 70 °C), the p-PFDA coating is unable to provide protection, while the p-HEMA and p-MAA strongly reduce the crystallization rate. Furthermore, p-HEMA and p-MAA selectively facilitate a preferential alignment of clotrimazole and, interestingly, even suppress crystallization upon a temporary, rapid temperature increase (3 °C/min, up to 150 °C). The results of this study demonstrate how a polymeric coating, synthesized directly on top of an amorphous phase, can act as a stabilizing agent against crystalline transitions, which makes this approach interesting for a variety of applications.

Abstract  BACKGROUND: Perfluoroalkyl substances (PFAS) are an emerging class of contaminants. Certain PFAS are regulated or voluntarily limited due to concern about environmental persistence and adverse health effects, including thyroid disease and to dyslipidemia. The major source of PFAS exposure in the general population is seafood.

OBJECTIVES: In this analysis we examine PFAS levels and their determinants, as well as associations between PFAS levels and self-reported health outcomes, in a group of older male anglers in Wisconsin with high fish consumption.

METHODS: A biomonitoring study of male anglers aged 50 and older living in Wisconsin collected detailed information on fish consumption, demographics and self-reported health outcomes, along with hair and blood samples for biomarker analysis. Sixteen different PFAS were extracted from serum samples. Regression models were used to identify factors (demographic characteristics and fish consumption habits) associated with PFAS biomarker levels in blood, as well as associations between PFAS and self-reported health outcomes, adjusting for potential confounders.

RESULTS: Seven PFAS were detected in at least 30% of participants and were used in subsequent analyses (PFDA, PFHpS, PFHxS, PFNA, PFOA, PFOS, PFuDA). The PFAS with the highest levels were PFOS, followed by PFOA, PFHxS and PFNA (medians of 19.0, 2.5, 1.8 and 1.4ng/mL). In general, increasing age was associated with higher PFAS levels, while increasing BMI were associated with lower PFAS levels. Greater alcohol consumption was associated with higher levels of PFHpS, PFHxS and PFOA. Associations with smoking and employment did not show a consistent pattern. Associations between fish consumption and PFAS were generally weak, with the exception of notably higher PFDA and PFHpS with both other locally-caught fish, and restaurant-purchased fish. Regarding associations with health outcomes, PFuDA, PFNA and PFDA were all associated with increased risk of pre-diabetes and/or diabetes. PFHpS was associated with a significantly increased risk of high cholesterol; PFDA and PFuDA also showed notable, though non-significant associations. All PFAS evaluated were associated with lower risk of hypertension although the only significant odds ratio was that for PFNA. There were no associations between any of the PFAS examined and either coronary heart disease, or the grouped outcome of any cardiovascular condition.

CONCLUSIONS: PFAS are emerging contaminants with widespread exposure, persistence, and potential for adverse health effects. In this study population, demographic patterns may reflect differences in exposure sources, or possibly differences in adsorption and metabolism. PFAS were associated mainly with endocrine related outcomes, with a general trend towards increased risk of glucose intolerance and high cholesterol. Continued research on the risks and benefits of fish consumption is important due to potential exposure to PFAS and noted associations with highly prevalent adverse health outcomes.

Abstract  The effects of four types of dissolved organic matters (DOM) on the bioconcentration of perfluoroalkyl substances (PFASs) in Chironomus plumosus larvae have been studied. The PFASs included perfluorooctane sulfonate (PFOS), perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), perfluorodecanoic acid (PFDA), perfluoroundecanoic acid (PFUnA), and perfluorododecanoic acid (PFDoA). The DOM included humic acid (HA), fulvic acid (FA), tannic acid (TA), and a protein, peptone (PEP), and their concentrations ranged from 0 to 50 mg L(-1). The results showed that, upon bioconcentration equilibrium, the body burdens of longer perfluoroalkyl chain PFASs (PFOS, PFDA, PFUnA and PFDoA) decreased with PEP and HA concentrations while increased with FA and TA concentrations. When FA and TA concentrations increased from 0 to 50 mg L(-1), body burdens of these PFASs increased by 7.5%-148.8% and 5.7%-37.1%, respectively. However, the DOM had no significant impact on the body burdens of shorter perfluoroalkyl chain PFASs (PFOA and PFNA). All of the four types of DOM lowered not only the uptake rate constants (ku) of PFASs due to the decrease of freely dissolved PFAS concentrations, but also the elimination rate constants (ke) due to the inhibition effect of DOM on the PFAS elimination from the larvae. The reduction in the two constants varied with both DOM and PFAS types. In the presence of PEP and HA with larger molecular weights, the ku values decreased more than ke, leading to the decreased body burdens of longer perfluoroalkyl chain PFASs. As for FA and TA with smaller molecular weights, the ke values decreased more than ku, resulting in increased body burdens of longer perfluoroalkyl chain PFASs. This study suggests that the effects of DOM on PFAS bioconcentration depend not only on the concentration but also on the molecule weight of DOM, which should be considered in the bioavailability assessment of PFASs.

Abstract  Concerns regarding perfluorinated chemicals (PFCs) have grown significantly in recent years. However, regulations and guidelines regarding the emission and treatment of PFCs are still missing in most parts of the world, mostly due to the lack of PFC toxicity data. In the current study, the genotoxic effects of four common PFCs, named perfluorooctanesulfonate (PFOS), perfluoroocanoic acid (PFOA), perfluorononanoic acid (PFNA) and perfluorodecanoic acid (PFDA) were investigated on marine mussels. The effects of exposure time and concentration on the toxic behavior of the compounds were also examined. Genotoxicity of PFCs was assessed in biomarker assays, showing that exposure to the target compounds could damage the organism's genetic material to varying extents, including DNA strand breaks and fragmentation, chromosomal breaks and apoptosis. The adverse effects increased with both exposure concentration and time and were related with the organism burden of PFCs. The integrated biomarker response analysis demonstrated that PFOS exhibited a higher genotoxicity than the other tested compounds. The EC50 values and confidence intervals based on integrative genotoxicity were 33 (29-37), 594 (341-1036), 195 (144-265) and 78 (73-84) μg/L for PFOS, PFOA, PFNA and PFDA respectively, classifying PFOS as a highly genotoxic compound. Although primary DNA damage was shown to be recoverable after exposure ceased, permanent genetic damage caused by elevated PFC concentrations was not restored. This is the first ecotoxicity study of PFCs that focuses on the genotoxic effects of the compounds, clearly indicating the genotoxicity of the tested PFCs and demonstrating that functional groups have a major impact on the compounds' genotoxic behavior.

Abstract  Water, sediment, plankton, and blood and liver tissues of crucian carp (Carassius auratus) and mandarin fish (Siniperca scherzeri) were collected from six major rivers and lakes in South Korea (including Namhan River, Bukhan River, Nakdong River, Nam River, Yeongsan River and Sangsa Lake) and analyzed for perfluorinated alkyl substances (PFASs). Perfluorooctane sulfonate (PFOS) was consistently detected at the greatest concentrations in all media surveyed with the maximum concentration in water of 15 ng L(-1) and in biota of 234 ng mL(-1) (fish blood). A general ascending order of PFAS concentration of water0.80, p<0.001) were observed between PFOS concentration in blood and liver tissues of both crucian carp and mandarin fish. This result suggests that blood can be used for nonlethal monitoring of PFOS in fish. Overall, the rank order of mean bioconcentration factors (BCFs) of PFOS in biota was; phytoplankton (196 L/kg)

Abstract  Time-series of perfluorinated alkylated substances (PFASs) in East Greenland polar bears and East and West Greenland ringed seals were updated in order to deduce whether a response to the major reduction in perfluoroalkyl production in the early 2000s had occurred. Previous studies had documented an exponential increase of perfluorooctane sulphonate (PFOS) in liver tissue from both species. In the present study, PFOS was still the far most dominant compound constituting 92% (West Greenland ringed seals), 88% (East Greenland ringed seals) and 85% (East Greenland polar bears). The PFOS concentrations increased up to 2006 with doubling times of approximately 6 years for the ringed seal populations and 14 years in case of polar bears. Since then a rapid decrease has occurred with clearing half-lives of approximately 1, 2 and 4 years, respectively. In polar bears perfluorohexane sulphonate (PFHxS) and perfluorooctane sulphonamide (PFOSA) also showed decreasing trends in recent years as do perfluorodecanoic acid (PFDA) and perfluoroundecanoic acid (PFUnA). For the West Greenland ringed seal population perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), PFDA and PFUnA peaked in the mid 2000s, whereas PFNA, PFDA and PFUnA in the East Greenland population have been stable or increasing in recent years. The peak of PFASs in Greenland ringed seals and polar bears occurred at a later time than in Canadian seals and polar bears and considerably later than observed in seal species from more southern latitudes. We suggest that this could be explained by the distance to emission hot-spots and differences in long-range transport to the Arctic.

Abstract  The objective of the Control of Hazardous Substances in the Baltic Sea (COHIBA) project is to support the implementation of the HELCOM Baltic Sea Action Plan regarding hazardous substances by developing joint actions to achieve the goal of "a Baltic Sea with life undisturbed by hazardous substances". One aim in the project was to identify the most important sources of 11 hazardous substances of special concern in the Baltic Sea. Among them are perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA). In this study, four perfluorinated alkyl acids (PFAAs) were studied: PFOA, PFOS, perfluorohexanoic acid (PFHxA) and perfluorodecanoic acid (PFDA). The occurrence of PFAAs in municipal and industrial wastewater treatment plant effluents (MWWTP1-3, IWWTP1), target industry effluent, storm water, landfill leachate and sludge was studied. Effluents were analysed six times and storm water, leachate and sludge were analysed twice, once in the warm season and once in the cold, during a 1-year sampling campaign. PFOS prevailed in two municipal effluents (MWWTP1 and 3) and industrial effluent (IWWTP1; 7.8-14, 8.0-640 and 320-1,300 ng/l, respectively). However, in one municipal effluent (MWWTP2) PFOA was, in a majority of sampling occasions, the predominant PFAA (9-15 ng/l) followed by PFOS (3.8-20 ng/l). The highest PFAA loads of the municipal effluents were found in the MWWTP3 receiving the biggest portion of industrial wastewater. In storm water the highest concentration was found for PFHxA (17 ng/l). The highest concentration of PFOS and PFOA were 9.9 and 5.1 ng/l, respectively. PFOS, PFOA and PFHxA were detected in every effluent, storm water and landfill leachate sample, whereas PFDA was detected in most of the samples (77%). In the target industry, PFOS concentrations varied between 1,400 and 18,000 μg/l. In addition, on one sampling occasion PFOA and PFHxA were found (0.027 and 0.009 μg/l, respectively). For effluents, PFAA mass flows into the Baltic Sea were calculated. For municipal wastewater treatment plants average mass flows per day varied for PFOS between 1,073 and 38,880 mg/day, for PFOA 960 and 2,700 mg/day, for PFHxA 408 and 1,269 mg/day and for PFDA 84 and 270 mg/day. In IWWTP mass flows for PFOS, PFOA, PFHxA and PFDA were 495 mg/d, 28 mg/d, 23 mg/d and 0.6 mg/g, respectively.

Abstract  Numerous studies have reported on the global distribution, persistence, fate, and toxicity of perfluoroalkyl and polyfluoroalkyl substances (PFASs). However, studies on PFASs in terrestrial mammals are scarce. Rats can be good sentinels of human exposure to toxicants because of their habitat, which is in close proximity to humans. Furthermore, exposure data measured for rats can be directly applied for risk assessment because many toxicological studies use rodent models. In this study, a nationwide survey of PFASs in the blood of wild rats as well as surface water samples collected from rats' habitats from 47 prefectures in Japan was conducted. In addition to known PFASs, combustion ion chromatography technique was used for analysis of total fluorine concentrations in the blood of rats. In total, 216 blood samples representing three species of wild rats (house rat, Norway rats, and field mice) were analyzed for 23 PFASs. Perfluorooctanesulfonate (PFOS; concentration range <0.05-148 ng/mL), perfluorooctane sulfonamide (PFOSA; <0.1-157), perfluorododecanoate (<0.05-5.8), perfluoroundecanoate (PFUnDA; <0.05-51), perfluorodecanoate (PFDA; <0.05-9.7), perfluorononanoate (PFNA; <0.05-249), and perfluorooctanoate (PFOA) (<0.05-60) were detected >80 % of the blood samples. Concentrations of several PFASs in rat blood were similar to those reported for humans. PFSAs (mainly PFOS) accounted for 45 % of total PFASs, whereas perfluoroalkyl carboxylates (PFCAs), especially PFUnDA and PFNA, accounted for 20 and 10 % of total PFASs, respectively. In water samples, PFCAs were the predominant compounds with PFOA and PFNA found in >90 % of the samples. There were strong correlations (p < 0.001 to p < 0.05) between human population density and levels of PFOS, PFNA, PFOA, and PFOSA in wild rat blood.

Abstract  Perfluorinated sulfonates (PFSAs) and perfluorinated carboxylates (PFCAs), as well as selected precursor compounds, were measured in eggs of thick-billed murres (Uria lomvia) and northern fulmars (Fulmarus glacialis) from Prince Leopold Island in the Canadian Arctic between 1975 and 2011 as well as in eggs of three additional species (black guillemot Cepphus grylle, black-legged kittiwake Rissa tridactyla, glaucous gull Larus hyperboreus) sampled in 2008. ΣPFCA concentrations increased significantly from 1975 to 2011 in the murre and fulmar eggs at an average annual rate of 0.56 and 0.91 ng g(-1) ww, respectively, whereas perfluorooctane sulfonate (PFOS) concentrations did not change significantly. The interspecies comparison of eggs sampled in 2008 found that black guillemots had the highest PFOS and lowest ΣPFCA levels, and northern fulmars had the highest ΣPFCA levels. PFUnA (C(11)) and PFTrA (C(13)) were the predominant PFCAs measured in eggs of all five species except for the black guillemot where PFDA (C(10)) contributed almost equally with PFTrA (C(13)) to the PFCA profile. Based on published toxicity thresholds, levels of neither perfluorooctanoate (PFOA) nor PFOS in seabird eggs from the Canadian Arctic are of toxicological concern. These are the first interspecies comparisons for PFASs in seabirds from the Canadian Arctic.