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Sample records for serum perfluoroalkyl chemicals

  1. Perfluoroalkyl chemicals and elevated serum uric acid in US adults

    PubMed Central

    Shankar, Anoop; Xiao, Jie; Ducatman, Alan

    2011-01-01

    Background: Perfluoroalkyl chemicals, including perfluorooctanoic acid and perfluorooctane sulfonate, are man-made chemicals that have been detected in the blood of over 98% of the US population. Serum uric acid is a novel biomarker, even mild elevations of which has been implicated in the development of hypertension, diabetes mellitus, cardiovascular disease, and chronic kidney disease. We examined the relationship of serum perfluoroalkyl chemicals, including perfluorooctanoic acid and perfluorooctane sulfonate, and elevated uric acid levels in a representative sample of US adults. Methods: We examined 3883 participants from the 1999–2000 and 2003–2006 National Health and Nutritional Examination Surveys, a representative, multiethnic population-based survey of noninstitutionalized US adults. Serum perfluorooctanoic acid and perfluorooctane sulfonate were analyzed as quartiles. The main outcome was hyperuricemia. Results: We found that serum levels of perfluoroalkyl chemicals, including perfluorooctanoic acid and perfluorooctane sulfonate, were positively associated with hyperuricemia. This association appeared to be independent of confounders such as age, gender, race-ethnicity, body mass index, diabetes, hypertension, and serum cholesterol. Compared with subjects in quartile 1 (referent), the multivariate odds ratio for hyperuricemia among subjects in quartile 4 was 1.97 (95% confidence interval 1.44–2.70, P < 0.0001) for perfluorooctanoic acid and 1.48% (95% confidence interval 0.99–2.22, P = 0.0433) for perfluorooctane sulfonate. This observed association persisted in subgroup analysis by gender and body mass index. Conclusion: Our results demonstrate that elevated levels of perfluoroalkyl chemicals are associated with hyperuricemia even at low perfluoroalkyl chemical exposure levels as seen in the US general population. PMID:22003309

  2. Positive Association Between Perfluoroalkyl Chemicals and Hyperuricemia in Children

    PubMed Central

    Geiger, Sarah Dee; Xiao, Jie; Shankar, Anoop

    2013-01-01

    Hyperuricemia in children is associated with increased risk of high blood pressure, metabolic syndrome, and future cardiovascular disease. Serum perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) levels have been shown to be positively associated with hyperuricemia in adults, but the association in children remains unexplored. We therefore examined the association between serum PFOA and PFOS levels and hyperuricemia in a representative sample of US children. A cross-sectional study was performed on 1,772 participants ≤18 years of age from the National Health and Nutrition Examination Survey 1999–2000 and 2003–2008. The main outcome of interest was hyperuricemia, defined as serum uric acid levels ≥6 mg/dL. We found that serum levels of PFOA and PFOS were positively associated with hyperuricemia, independent of age, sex, race/ethnicity, body mass index, annual household income, physical activity, serum total cholesterol, and serum cotinine levels. Compared with subjects in quartile 1 (referent), subjects in quartile 4 had multivariable-adjusted odds ratios for hyperuricemia of 1.62 (95% confidence interval: 1.10, 2.37) for PFOA and 1.65 (95% confidence interval: 1.10, 2.49) for PFOS. Our findings indicate that serum perfluoroalkyl chemical levels are significantly associated with hyperuricemia in children even at the lower “background” exposure levels of the US general population. PMID:23552989

  3. Human placental transfer of perfluoroalkyl acid precursors: Levels and profiles in paired maternal and cord serum.

    PubMed

    Yang, Lin; Wang, Zhen; Shi, Yu; Li, Jingguang; Wang, Yuxin; Zhao, Yunfeng; Wu, Yongning; Cai, Zongwei

    2016-02-01

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

  4. Associations between Serum Perfluoroalkyl Acids and LINE-1 DNA Methylation

    PubMed Central

    Watkins, Deborah J.; Wellenius, Gregory A.; Butler, Rondi A.; Bartell, Scott M.; Fletcher, Tony; Kelsey, Karl T.

    2014-01-01

    Perfluoroalkyl acids (PFAAs) are persistent, synthetic compounds that are used in a number of consumer products. Perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) have been associated with cardiovascular risk factors, and changes in gene expression and DNA methylation in animals and cellular systems. However, whether PFAA exposure is associated with LINE-1 DNA methylation, a potential marker of cardiovascular risk, in humans remains unknown. We sought to evaluate the cross-sectional associations between serum PFAAs and LINE-1 DNA methylation in a population highly exposed to PFOA. We measured serum PFAAs twice four to five years apart in 685 adult participants (47% male, mean age ± SD=42 ± 11 years). We measured percent LINE-1 DNA methylation in peripheral blood leukocytes at the second time point (follow-up), and estimated absolute differences in LINE-1 methylation associated with an interquartile (IQR) shift in mean PFAA serum levels. IQR increases in mean serum PFOA, PFOS, perfluorononanoic acid (PFNA), and perfluorohexane sulfonate (PFHxS) were associated with differences of −0.04 (p=0.16), 0.20 (p=0.001), 0.06 (p=0.19), and 0.02 (p=0.57), respectively, in % LINE-1 methylation at follow-up after adjustment for potential confounders. We observed a monotonic increase in LINE-1 DNA methylation across tertiles of PFOS and PFNA (ptrend=0.02 for both associations), but not across tertiles of PFOA or PFHxS (ptrend=0.71 and 0.44, respectively). In summary, serum PFOS was associated with LINE-1 methylation, while serum PFOA, PFHxS, and PFNA were not. Additional research is needed to more precisely determine whether these compounds are epigenetically active. PMID:24263140

  5. Highly elevated serum concentrations of perfluoroalkyl substances in fishery employees from Tangxun lake, china.

    PubMed

    Zhou, Zhen; Shi, Yali; Vestergren, Robin; Wang, Thanh; Liang, Yong; Cai, Yaqi

    2014-04-01

    Increasing production and use of per- and polyfluoroalkyl substances (PFASs) has been reported from China, and a few studies have shown there are subpopulations in China with high and increasing exposure to these chemicals. In this paper, we present a comprehensive exposure assessment of PFASs in fishery employees from Tangxun Lake, China. Exceptionally high serum concentrations of C4 to C12 PFASs were observed in fishery employees (n = 39, median perfluorooctanesulfonic acid (PFOS) 10 400 ng/mL) compared to a reference group from the same city (n = 9, median PFOS 18.7 ng/mL). On the basis of the comparison of different exposure pathways, it was concluded that contaminated fish from Tangxun Lake was the primary source of PFAS exposure to fishery employees, and there was a positive association between serum PFAS concentrations and time of employment in the fishery. PFOS isomer profiles in fishery employees showed a significantly higher proportion of linear PFOS (78.4%) compared to the background-exposed reference group (66.8%), reflecting the highly linear PFOS isomer profile (>90%) of lake fish. Median renal clearance rates (CLrenal) of C4 to C10 perfluoroalkyl carboxylic acids (PFCAs) and perfluoroalkanesulfonic acids (PFSAs) ranged from 0.020 to 16.5 mL/day/kg and 0.013 to 9.43 mL/day/kg, respectively. PFCAs with less than eight perfluoroalkyl carbons were primarily eliminated via urine, whereas other routes of excretion may have contributed to the elimination for long-chain PFCAs and PFSAs. Calculated daily PFOS exposures of fishery employees significantly exceeded tolerable daily intake limits, but clinical blood chemistry parameters were mostly within normal reference ranges. However, additional epidemiological studies are needed to address potential associations between PFAS exposure and health effects in the Tangxun Lake area.

  6. Perfluoroalkyl Chemicals and Asthma among Children 12–19 Years of Age: NHANES (1999–2008)

    PubMed Central

    Humblet, Olivier; Diaz-Ramirez, Ledif Grisell; Balmes, John R.; Pinney, Susan M.

    2014-01-01

    Background: Perfluoroalkyl chemicals (PFCs) are a family of commonly used industrial chemicals whose persistence and ubiquity in human blood samples has led to concern about possible toxicity. Several animal studies and one recent human study have suggested a link between exposure to PFCs and asthma, although few epidemiologic studies have been conducted. Objectives: We investigated children’s PFC serum concentrations and their associations with asthma-related outcomes. Methods: We evaluated the association between serum concentrations of eight PFCs, including perfluorooctanoic acid (PFOA), perfluorooctane sulfonic acid (PFOS), perfluorononanoic acid (PFNA), and perfluorohexane sulfonic acid (PFHxS), with self-reported lifetime asthma, recent wheezing, and current asthma using data from participants 12–19 years of age from the 1999–2000 and 2003–2008 National Health and Nutrition Examination Surveys. Results: In multivariable-adjusted models, PFOA was associated with higher odds of ever having received a diagnosis of asthma [odds ratio (OR) = 1.18; 95% CI: 1.01, 1.39 for a doubling in PFOA], whereas for PFOS there were inverse relationships with both asthma and wheezing (OR = 0.88; 95% CI: 0.74, 1.04, and OR = 0.83; 95% CI: 0.67, 1.02, respectively). The associations were attenuated after accounting for sampling weights. No associations were seen between the other PFCs and any outcome. Conclusions: This cross-sectional study provides some evidence for associations between exposure to PFCs and asthma-related outcomes in children. The evidence is inconsistent, however, and prospective studies are needed. Citation: Humblet O, Diaz-Ramirez LG, Balmes JR, Pinney SM, Hiatt RA. 2014. Perfluoroalkyl chemicals and asthma among children 12–19 years of age: NHANES (1999–2008). Environ Health Perspect 122:1129–1133; http://dx.doi.org/10.1289/ehp.1306606 PMID:24905661

  7. Serum perfluoroalkyl acids concentrations and memory impairment in a large cross-sectional study

    PubMed Central

    Gallo, Valentina; Leonardi, Giovanni; Brayne, Carol; Armstrong, Ben; Fletcher, Tony

    2013-01-01

    Objectives To examine the cross-sectional association between serum perfluorooctanate (PFOA), perfuorooctane sulfonate (PFOS), perfluorononanoic acid (PFNA) and perfluorohexane sulfonate (PFHxS) concentrations with self-reported memory impairment in adults and the interaction of these associations with diabetes status. Design Cross-sectional study. Setting Population-based in Mid-Ohio Valley, West Virginia following contamination by a chemical plant. Participants The C8 Health Project collected data and measured the serum level of perfluoroalkyl acids (PFAAs) of 21 024 adults aged 50+ years. Primary outcome measure Self-reported memory impairment as defined by the question ‘have experienced short-term memory loss?’ Results A total of 4057 participants self-reported short-term memory impairment. Inverse associations between PFOS and PFOA and memory impairment were highly statistically significant with fully adjusted OR=0.93 (95% CI 0.90 to 0.96) for doubling PFOS and OR=0.96 (95% CI 0.94 to 0.98) for doubling PFOA concentrations. Comparable inverse associations with PFNA and PFHxS were of borderline statistical significance. Inverse associations of PFAAs with memory impairment were weaker or non-existent in patients with diabetes than overall in patients without diabetes. Conclusions An inverse association between PFAA serum levels and self-reported memory impairment has been observed in this large population-based, cross-sectional study that is stronger and more statistically significant for PFOA and PFOS. The associations can be potentially explained by a preventive anti-inflammatory effect exerted by a peroxisome proliferator-activated receptor agonist effect of these PFAAs, but confounding or even reverse causation cannot be excluded as an alternative explanation. PMID:23794579

  8. Perfluoroalkyl acid (PFAA) levels and profiles in breast milk, maternal and cord serum of French women and their newborns.

    PubMed

    Cariou, Ronan; Veyrand, Bruno; Yamada, Ami; Berrebi, Alain; Zalko, Daniel; Durand, Sophie; Pollono, Charles; Marchand, Philippe; Leblanc, Jean-Charles; Antignac, Jean-Philippe; Le Bizec, Bruno

    2015-11-01

    One major concern regarding perfluoroalkyl acids (PFAAs) is their potential role in onset of health troubles consecutive to early exposure during the perinatal period. In the present work, the internal exposure levels of 18 targeted PFAAs were determined in ca. 100 mother-newborn pairs recruited in France between 2010 and 2013. In serum, the cumulated concentrations of the 7 most frequently detected compounds were 5.70ng/mL and 2.83ng/mL (median values) in maternal and cord serum, respectively. Perfluorooctanesulfonic acid (PFOS), perfluorooctanoic acid (PFOA), perfluorohexylesulfonic acid (PFHxS) and perfluorononanoic acid (PFNA) contributed to around 90% of the total PFAAs contamination, with concentration levels and contamination profiles in accordance with other published work in Europe. Levels measured in breast milk were far lower (20 to 150 fold) than those determined in serum. Associations between the different monitored substances as well as between levels determined in the different investigated biological matrices mostly do not appear statistically significant. The estimated materno-foetal transfer would be thus substance-dependant, mainly driven by the physico-chemical properties of the different PFAAs (nature of polar group and length of alkylated side chain). We conclude that trans-placental passage and breastfeeding are both significant routes of human exposure to PFAAs. PMID:26232143

  9. Serum levels of perfluoroalkyl compounds in human maternal and umbilical cord blood samples

    SciTech Connect

    Monroy, Rocio; Morrison, Katherine; Teo, Koon; Atkinson, Stephanie; Kubwabo, Cariton; Stewart, Brian; Foster, Warren G.

    2008-09-15

    Perfluoroalkyl compounds (PFCs) are end-stage metabolic products from industrial flourochemicals used in the manufacture of plastics, textiles, and electronics that are widely distributed in the environment. The objective of the present study was to quantify exposure to perfluorooctane sulfonate (PFOS), perfluorooctanoate (PFOA), perfluorodecanoic acid (PFDeA), perfluorohexane sulfonate (PFHxS), perfluoroheptanoic acid (PFHpA), and perfluorononanoic acid (PFNA) in serum samples collected from pregnant women and the umbilical cord at delivery. Pregnant women (n=101) presenting for second trimester ultrasound were recruited and PFC residue levels were quantified in maternal serum at 24-28 weeks of pregnancy, at delivery, and in umbilical cord blood (UCB; n=105) by liquid chromatography-mass spectrometry. Paired t-test and multiple regression analysis were performed to determine the relationship between the concentrations of each analyte at different sample collection time points. PFOA and PFOS were detectable in all serum samples analyzed including the UCB. PFOS serum levels (mean{+-}S.D.) were significantly higher (p<0.001) in second trimester maternal serum (18.1{+-}10.9 ng/mL) than maternal serum levels at delivery (16.2{+-}10.4 ng/mL), which were higher than the levels found in UCB (7.3{+-}5.8 ng/mL; p<0.001). PFHxS was quantifiable in 46/101 (45.5%) maternal and 21/105 (20%) UCB samples with a mean concentration of 4.05{+-}12.3 and 5.05{+-}12.9 ng/mL, respectively. There was no association between serum PFCs at any time point studied and birth weight. Taken together our data demonstrate that although there is widespread exposure to PFCs during development, these exposures do not affect birth weight.

  10. Perfluoroalkyl Acids in Maternal Serum and Indices of Fetal Growth: The Aarhus Birth Cohort

    PubMed Central

    Bach, Cathrine Carlsen; Bech, Bodil Hammer; Nohr, Ellen Aagaard; Olsen, Jørn; Matthiesen, Niels Bjerregård; Bonefeld-Jørgensen, Eva Cecilie; Bossi, Rossana; Henriksen, Tine Brink

    2015-01-01

    Background: Previous studies indicated an association between intrauterine exposure to perfluorooctane sulfonate (PFOS) or perfluorooctanoate (PFOA) and lower birth weight. However, these perfluoroalkyl acids (PFAAs) have to some extent been substituted by other compounds on which little is known. Objectives: We investigated the association between specific PFAAs and birth weight, birth length, and head circumference at birth. Methods: We studied 1,507 mothers and their children from the Aarhus Birth Cohort (2008–2013). Nulliparous women were included during pregnancy, and serum levels of 16 PFAAs were measured between 9 and 20 completed gestational weeks (96% within 13 weeks). For compounds with quantifiable values in > 50% of samples (7 compounds), we report the associations with birth weight, birth length, and head circumference at birth determined by multivariable linear regression. Results: Estimated mean birth weights were lower among women with serum perfluorohexane sulfonate, perfluoroheptane sulfonate, and PFOS concentrations above the lowest exposure quartile, but we found no consistent monotonic dose–response patterns. These associations were stronger when the population was restricted to term births (n = 1,426). For PFOS, the birth weight estimates for the highest versus lowest quartile were –50 g (95% CI: –123, 23 g) in all births and –62 g (95% CI: –126, 3 g) in term births. For the other PFAAs, the direction of the associations was inconsistent, and no overall association with birth weight was apparent. No PFAAs were associated with birth length or head circumference at birth. Conclusions: Overall, we did not find strong or consistent associations between PFAAs and birth weight or other indices of fetal growth, though estimated mean birth weights were lower among those with exposures above the lowest quartile for some compounds. Citation: Bach CC, Bech BH, Nohr EA, Olsen J, Matthiesen NB, Bonefeld-Jørgensen EC, Bossi R, Henriksen TB

  11. 78 FR 62443 - Perfluoroalkyl Sulfonates and Long-Chain Perfluoroalkyl Carboxylate Chemical Substances; Final...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2013-10-22

    ... the Federal Register of August 15, 2012 (77 FR 48924) (FRL-9358- 7), EPA proposed to amend a SNUR at... people and the environment will generally not be exposed to chemical substances in articles (see 49 FR 35014; September 5, 1984). However, as stated in Unit IV. of the proposed rule (77 FR 48928; August...

  12. Serum Biomarkers of Exposure to Perfluoroalkyl Substances in Relation to Serum Testosterone and Measures of Thyroid Function among Adults and Adolescents from NHANES 2011–2012

    PubMed Central

    Lewis, Ryan C.; Johns, Lauren E.; Meeker, John D.

    2015-01-01

    Perfluoroalkyl substances (PFASs) are a group of environmentally-persistent chemicals that have been widely used in many industrial applications. There is human and animal evidence that PFASs may alter levels of reproductive and thyroid-related hormones. However, human studies on the potential age-related effects of PFASs on these outcomes among males and females are limited. We explored the relationship between serum PFASs and serum total testosterone (T), thyroid stimulating hormone (TSH), and free and total triiodothyronine (FT3, TT3) and thyroxine (FT4, TT4) among males and females 12 to 80 years of age from the 2011–2012 cycle of the National Health and Nutrition Examination Survey. Associations were assessed using multiple linear regression models that were stratified on sex and age categories. Effect estimates from the majority of the adjusted models were not statistically significant. However, exposure to PFASs may be associated with increases in FT3, TT3, and FT4 among adult females, but during adolescence, PFASs may be related to increases in TSH among males and decreases in TSH among females. No significant relationships were observed between PFASs and T in any of the models. These findings suggest that exposure to PFASs may disrupt thyroid hormone homeostasis. PMID:26035660

  13. Concentrations of perfluoroalkyl compounds in the serum and milk of lactating North Carolina women

    EPA Science Inventory

    Perfluoroalkyl acids (PFAAs) and their derivatives are ubiquitous environmental contaminants that have been detected in a multitude of terrestrial and aquatic organisms. Some PFAAs bind the human estrogen receptors in vitro. Further, some PFAAs induce estrogen responsive genes a...

  14. The precautionary principle and chemicals management: The example of perfluoroalkyl acids in groundwater.

    PubMed

    Cousins, Ian T; Vestergren, Robin; Wang, Zhanyun; Scheringer, Martin; McLachlan, Michael S

    2016-09-01

    Already in the late 1990s microgram-per-liter levels of perfluorooctane sulfonate (PFOS) were measured in water samples from areas where fire-fighting foams were used or spilled. Despite these early warnings, the problems of groundwater, and thus drinking water, contaminated with perfluoroalkyl and polyfluoroalkyl substances (PFASs) including PFOS are only beginning to be addressed. It is clear that this PFAS contamination is poorly reversible and that the societal costs of clean-up will be high. This inability to reverse exposure in a reasonable timeframe is a major motivation for application of the precautionary principle in chemicals management. We conclude that exposure can be poorly reversible; 1) due to slow elimination kinetics in organisms, or 2) due to poorly reversible environmental contamination that leads to continuous exposure. In the second case, which is relevant for contaminated groundwater, the reversibility of exposure is not related to the magnitude of a chemical's bioaccumulation potential. We argue therefore that all PFASs entering groundwater, irrespective of their perfluoroalkyl chain length and bioaccumulation potential, will result in poorly reversible exposures and risks as well as further clean-up costs for society. To protect groundwater resources for future generations, society should consider a precautionary approach to chemicals management and prevent the use and release of highly persistent and mobile chemicals such as PFASs. PMID:27337597

  15. The precautionary principle and chemicals management: The example of perfluoroalkyl acids in groundwater.

    PubMed

    Cousins, Ian T; Vestergren, Robin; Wang, Zhanyun; Scheringer, Martin; McLachlan, Michael S

    2016-09-01

    Already in the late 1990s microgram-per-liter levels of perfluorooctane sulfonate (PFOS) were measured in water samples from areas where fire-fighting foams were used or spilled. Despite these early warnings, the problems of groundwater, and thus drinking water, contaminated with perfluoroalkyl and polyfluoroalkyl substances (PFASs) including PFOS are only beginning to be addressed. It is clear that this PFAS contamination is poorly reversible and that the societal costs of clean-up will be high. This inability to reverse exposure in a reasonable timeframe is a major motivation for application of the precautionary principle in chemicals management. We conclude that exposure can be poorly reversible; 1) due to slow elimination kinetics in organisms, or 2) due to poorly reversible environmental contamination that leads to continuous exposure. In the second case, which is relevant for contaminated groundwater, the reversibility of exposure is not related to the magnitude of a chemical's bioaccumulation potential. We argue therefore that all PFASs entering groundwater, irrespective of their perfluoroalkyl chain length and bioaccumulation potential, will result in poorly reversible exposures and risks as well as further clean-up costs for society. To protect groundwater resources for future generations, society should consider a precautionary approach to chemicals management and prevent the use and release of highly persistent and mobile chemicals such as PFASs.

  16. Perfluoroalkyl acids in the serum and milk of breastfeeding North Carolina women

    EPA Science Inventory

    Perfluoroalkyl acids (PFAAs) comprise a group of man-made persistent environmental compounds. They are widely used in consumer products such as food packaging material, non-stick cookware and cleaning agents, and have been detected in drinking water. Certain PFAAs tend to bioaccu...

  17. Temporal changes (1997-2012) of perfluoroalkyl acids and selected precursors (including isomers) in Swedish human serum.

    PubMed

    Gebbink, Wouter A; Glynn, Anders; Berger, Urs

    2015-04-01

    Concentrations (including isomer patterns) and temporal changes (1997-2012) of perfluoroalkyl acids (PFAAs) and selected perfluorooctane sulfonate (PFOS) and perfluoroalkyl carboxylic acid (PFCA) precursors were determined in serum samples from Swedish women. Perfluorooctane sulfonamide (FOSA) and perfluorooctane sulfonamidoacetic acid (FOSAA), as well as its N-methyl and N-ethyl derivatives (MeFOSAA and EtFOSAA) were consistently detected. Highest PFOS precursor concentrations were found for EtFOSAA (before year 2000) or MeFOSAA and FOSAA (after 2000). Disappearance half-lives for all PFOS precursors were shorter compared to PFOS. 4:2/6:2 and 6:2/6:2 polyfluoroalkyl phosphate diesters (diPAPs) were detected in <60% of the samples, whereas 6:2/8:2 and 8:2/8:2 diPAPs were detected in >60% of the samples, but showed no significant change in concentrations over time. Linear and sum-branched isomers were quantified separately for three PFAAs and three precursors. Significant changes between 1997 and 2012 in the % linear isomer were observed for PFOA and FOSA (increase) and PFOS (decrease).

  18. Associations of serum perfluoroalkyl acid levels with T-helper cell-specific cytokines in children: By gender and asthma status.

    PubMed

    Zhu, Yu; Qin, Xiao-Di; Zeng, Xiao-Wen; Paul, Gunther; Morawska, Lidia; Su, Ming-Wei; Tsai, Ching-Hui; Wang, Si-Quan; Lee, Yungling Leo; Dong, Guang-Hui

    2016-07-15

    Perfluoroalkyl acids (PFAAs) are a group of common chemicals that ubiquitously exist in wildlife and humans. Experimental data suggest that they may alter T-lymphocyte functioning in situ by preferentially enhancing the development of T-helper 2 (TH2)- and inhibiting TH1-lymphocyte development and might increase allergic inflammation, but few human studies have been conducted. To evaluate the association between serum PFAAs concentrations and T-lymphocyte-related immunological markers of asthma in children, and further to assess whether gender modified this association, 231 asthmatic children and 225 non-asthmatic control children from Northern Taiwan were recruited into the Genetic and Biomarker study for Childhood Asthma. Serum concentrations of ten PFAAs and levels of TH1 [interferon (IFN)-γ, interleukin (IL)-2] and TH2 (IL-4 and IL-5) cytokines were measured. The results showed that asthmatics had significantly higher serum PFAAs concentrations compared with the healthy controls. When stratified by gender, a greater number of significant associations between PFAAs and asthma outcomes were found in males than in females. Among males, adjusted odds ratios for asthma among those with the highest versus lowest quartile of PFAAs exposure ranged from 2.59 (95% CI: 1.14, 5.87) for the perfluorobutanesulfonate (PFBS) to 4.38 (95% CI: 2.02, 9.50) for perfluorooctanesulfonate (PFOS); and serum PFAAs were associated positively with TH2 cytokines and inversely with TH1 cytokines among male asthmatics. Among females, no significant associations between PFAAs and TH2 cytokines could be detected. In conclusion, increased serum PFAAs levels may promote TH cell dysregulation and alter the availability of key TH1 and TH2 cytokines, ultimately contributing to the development of asthma that may differentially impact males to a greater degree than females. These results have potential relevance in asthma prevention. PMID:27060656

  19. Perfluoroalkyl substances in serum from South Korean infants with congenital hypothyroidism and healthy infants--Its relationship with thyroid hormones.

    PubMed

    Kim, Da-Hye; Kim, Un-Jung; Kim, Hee-Young; Choi, Sung-Deuk; Oh, Jeong-Eun

    2016-05-01

    Exposure to perfluoroalkyl substances (PFASs) may disrupt thyroid systems, though the specific effects of PFASs are still being elucidated. Since research regarding exposure in infants is highly limited, our goal was to investigate exposure levels of PFASs in infant serum and correlate these levels with thyroid hormones (THs). This was accomplished by analyzing 16 PFASs in sera from a case group of infants with congenital hypothyroidism and a control group. Total PFAS exposure level was 2.63-44.7ng/mL in the case group and 2.44-22.4ng/mL in the control group. Concentrations of serum perfluorooctanoic acid (PFOA, p<0.01), perfluorononanoic acid (PFNA, p<0.001), perfluorooctanoic acid (PFDA, p<0.005), and perfluoroundecanoic acid (PFUnDA, p<0.005) were significantly higher in the case group than the control group. Levels of certain PFASs (PFOA, perfluorotridecanoic acid [PFTrDA], and perfluorohexane sulfonate [PFHxS]) showed a moderate to weak correlation with relevant antibodies. PMID:26950028

  20. Effects of chemical oxidants on perfluoroalkyl acid transport in one-dimensional porous media columns.

    PubMed

    McKenzie, Erica R; Siegrist, Robert L; McCray, John E; Higgins, Christopher P

    2015-02-01

    In situ chemical oxidation (ISCO) is a remediation approach that is often used to remediate soil and groundwater contaminated with fuels and chlorinated solvents. At many aqueous film-forming foam-impacted sites, perfluoroalkyl acids (PFAAs) can also be present at concentrations warranting concern. Laboratory experiments were completed using flow-through one-dimensional columns to improve our understanding of how ISCO (i.e., activated persulfate, permanganate, or catalyzed hydrogen peroxide) could affect the fate and transport of PFAAs in saturated porous media. While the resultant data suggest that standard ISCO is not a viable remediation strategy for PFAA decomposition, substantial changes in PFAA transport were observed upon and following the application of ISCO. In general, activated persulfate decreased PFAA transport, while permanganate and catalyzed hydrogen peroxide increased PFAA transport. PFAA sorption increased in the presence of increased aqueous polyvalent cation concentrations or decreased pH. The changes in contaminant mobility were greater than what would be predicted on the basis of aqueous chemistry considerations alone, suggesting that the application of ISCO results in changes to the porous media matrix (e.g., soil organic matter quality) that also influence transport. The application of ISCO is likely to result in changes in PFAA transport, where the direction (increased or decreased transport) and magnitude are dependent on PFAA characteristics, oxidant characteristics, and site-specific factors. PMID:25621878

  1. Effects of chemical oxidants on perfluoroalkyl acid transport in one-dimensional porous media columns.

    PubMed

    McKenzie, Erica R; Siegrist, Robert L; McCray, John E; Higgins, Christopher P

    2015-02-01

    In situ chemical oxidation (ISCO) is a remediation approach that is often used to remediate soil and groundwater contaminated with fuels and chlorinated solvents. At many aqueous film-forming foam-impacted sites, perfluoroalkyl acids (PFAAs) can also be present at concentrations warranting concern. Laboratory experiments were completed using flow-through one-dimensional columns to improve our understanding of how ISCO (i.e., activated persulfate, permanganate, or catalyzed hydrogen peroxide) could affect the fate and transport of PFAAs in saturated porous media. While the resultant data suggest that standard ISCO is not a viable remediation strategy for PFAA decomposition, substantial changes in PFAA transport were observed upon and following the application of ISCO. In general, activated persulfate decreased PFAA transport, while permanganate and catalyzed hydrogen peroxide increased PFAA transport. PFAA sorption increased in the presence of increased aqueous polyvalent cation concentrations or decreased pH. The changes in contaminant mobility were greater than what would be predicted on the basis of aqueous chemistry considerations alone, suggesting that the application of ISCO results in changes to the porous media matrix (e.g., soil organic matter quality) that also influence transport. The application of ISCO is likely to result in changes in PFAA transport, where the direction (increased or decreased transport) and magnitude are dependent on PFAA characteristics, oxidant characteristics, and site-specific factors.

  2. A simple and rapid extraction method for sensitive determination of perfluoroalkyl substances in blood serum suitable for exposure evaluation.

    PubMed

    Luque, Noelia; Ballesteros-Gómez, Ana; van Leeuwen, Stefan; Rubio, Soledad

    2012-04-27

    In this work, we propose a microextraction method based on a new supramolecular solvent (SUPRAS) made up of reverse aggregates of hexanoic acid, combined with liquid chromatography/triple quadrupole mass spectrometry (LC/QQQ MS-MS) for the determination of the perfluoroalkyl substances (PFASs) in blood serum. A SUPRAS is a nano-structured liquid made up of surfactant aggregates synthesized through a self-assembly process. The method involved the acidification of 765 μL of blood serum (600 μmol of hydrochloric acid per mL of serum) followed by the addition of hexanoic acid (97 μL) and tetrahydrofuran (THF) (600 μL), conditions under which the supramolecular solvent (∼360 μL) formed in situ after vortex-shaking and centrifugation. Parameters affecting extraction efficiency and concentration factors were studied. The overall sample treatment took only 20 min and several samples (20-30) can be simultaneously analyzed using conventional lab equipments, making additional investments unnecessary. Recoveries for the internal standards in samples ranged from 75 to 89% with relative standard deviations between 1 and 15%. Calibration was based on the use of internal standards. The method was very sensitive with detection limits ranging from 2 to 20 pg mL(-1) for PFASs. The approach developed was successfully applied to the determination of PFASs in different blood serum samples. The concentration of PFASs found in samples of animal origin ranged between 17 and 197.3 pg mL(-1) and between 84 and 5168 pg mL(-1) in samples of human origin. Both the analytical and operational features of this method make it suitable for the evaluation of exposure to PFASs. PMID:22420956

  3. Toxicology of Perfluoroalkyl Acids*

    EPA Science Inventory

    The perfluoroalkyl acids (PFAAs) are a family of organic chemicals consisting of a perfluorinated carbon backbone (4-12 in length) and an acidic functional moiety (carboxylate or sulfonate). These compounds are chemically stable, have excellent surface-tension reducing properties...

  4. Influence of contaminated drinking water on perfluoroalkyl acid levels in human serum--A case study from Uppsala, Sweden.

    PubMed

    Gyllenhammar, Irina; Berger, Urs; Sundström, Maria; McCleaf, Philip; Eurén, Karin; Eriksson, Sara; Ahlgren, Sven; Lignell, Sanna; Aune, Marie; Kotova, Natalia; Glynn, Anders

    2015-07-01

    In 2012 a contamination of drinking water with perfluoroalkyl acids (PFAAs) was uncovered in the City of Uppsala, Sweden. The aim of the present study was to determine how these substances have been distributed from the contamination source through the groundwater to the drinking water and how the drinking water exposure has influenced the levels of PFAAs in humans over time. The results show that PFAA levels in groundwater measured 2012-2014 decreased downstream from the point source, although high ΣPFAA levels (>100ng/L) were still found several kilometers from the point source in the Uppsala aquifer. The usage of aqueous film forming fire-fighting foams (AFFF) at a military airport in the north of the city is probably an important contamination source. Computer simulation of the distribution of PFAA-contaminated drinking water throughout the City using a hydraulic model of the pipeline network suggested that consumers in the western and southern parts of Uppsala have received most of the contaminated drinking water. PFAA levels in blood serum from 297 young women from Uppsala County, Sweden, sampled during 1996-1999 and 2008-2011 were analyzed. Significantly higher concentrations of perfluorobutane sulfonic acid (PFBS) and perfluorohexane sulfonic acid (PFHxS) were found among women who lived in districts modeled to have received contaminated drinking water compared to unaffected districts both in 1996-1999 and 2008-2011, indicating that the contamination was already present in the late 1990s. Isomer-specific analysis of PFHxS in serum showed that women in districts with contaminated drinking water also had an increased percentage of branched isomers. Our results further indicate that exposure via contaminated drinking water was the driving factor behind the earlier reported increasing temporal trends of PFBS and PFHxS in blood serum from young women in Uppsala.

  5. Toxicology of Perfluoroalkyl acids

    EPA Science Inventory

    The Perfluoroalkyl acids(PFAAs) area a family of organic chemicals consisting of a perflurinated carbon backbone (4-12in length) and a acidic functional moiety (Carboxylate or sulfonate). These compounds have excellent surface-tension reducing properties and have numerous industr...

  6. Changes in serum levels of perfluoroalkyl substances during a 10-year follow-up period in a large population-based cohort.

    PubMed

    Stubleski, Jordan; Salihovic, Samira; Lind, Lars; Lind, P Monica; van Bavel, Bert; Kärrman, Anna

    2016-10-01

    Poly- and perfluoroalkyl substances (PFASs) are a group of man-made fluorinated chemicals which have, at background levels, been associated with negative health effects in humans. Thus far, most human biomonitoring studies have evaluated the general change in PFAS concentration over time by continuously testing various individuals. This is one of the few studies to report the longitudinal trend of a range of PFAS concentrations in humans. In addition, this is the first known longitudinal study to include a large background level exposed cohort of both men and women with the same age and location who were repeatedly sampled from 2001 to 2014. The longitudinal change in concentration of eight PFASs detected in serum collected from the Prospective Investigation of the Vasculature in Uppsala Seniors (PIVUS) cohort were determined and compared to results from general population studies. The sex-dependent changes in PFAS concentrations over time were also assessed. Serum was sampled from the same individuals at ages 70 (collection period 2001-2004), 75 (2006-2009) and 80 (2011-2014,). Eight (C6-11) of fourteen (C4-13) analyzed PFASs were usually detected in over 75% of individuals and assessed using a random effects (mixed) model. In the 579 individuals attending all three examinations, PFOSA and PFOS concentrations significantly decreased, while the remaining six PFASs significantly increased between ages 70 and 75. However, between ages 75 and 80 all PFAS concentrations significantly decreased. Overall from age 70 to 80, concentrations of PFHxS, PFUnDA, PFNA, and PFDA showed a significant increase (7% to 34%), whereas concentrations of PFOSA, PFHpA, PFOS, and PFOA (-75% to -27%) significantly decreased. Over time PFHxS concentrations increased more among women, while PFHpA concentrations showed a greater decrease among men. From age 70 to age 80, spanning from 2001-2004 to 2011-2014, the PIVUS cohort showed decreases in circulating levels of some PFASs phased out of

  7. Cross-Sectional Associations of Serum Perfluoroalkyl Acids and Thyroid Hormones in U.S. Adults: Variation According to TPOAb and Iodine Status (NHANES 2007–2008)

    PubMed Central

    Webster, Glenys M.; Rauch, Stephen A.; Marie, Nathalie Ste; Mattman, Andre; Lanphear, Bruce P.; Venners, Scott A.

    2015-01-01

    Background: Perfluoroalkyl acids (PFASs) are suspected thyroid toxicants, but results from epidemiological studies are inconsistent. Objectives: We examined associations between serum PFASs and thyroid hormones (THs) in a representative, cross-sectional sample of U.S. adults. We hypothesized that people with high thyroid peroxidase antibodies and low iodine would be more susceptible to PFAS-induced thyroid disruption. Methods: Our sample included 1,525 adults (≥ 18 years) from the 2007–2008 NHANES study with available serum PFASs and THs. We examined associations between four serum PFASs [perfluorohexane sulfonate (PFHxS), perfluorononanoate (PFNA), perfluorooctanoate (PFOA), and perfluorooctane sulfonate (PFOS)], and serum THs [free triiodothyronine (fT3), free thyroxine (fT4), fT3/fT4, thyroid-stimulating hormone (TSH), total T3 (TT3), and total T4 (TT4)] using multivariable linear regression. We stratified subjects into four groups by two indicators of thyroid “stress”: thyroid peroxidase antibody (TPOAb ≥ 9 IU/mL) and iodine status (< 100 μg/L urine). Results: Of 1,525 participants, 400 (26%) had low iodine only (T0I1), 87 (6%) had high TPOAb only (T1I0), and 26 (2%) had both high TPOAb and low iodine (T1I1). In general, associations were similar among participants in the groups with neither (T0I0) or only one thyroid stressor (T0I1 or T1I0), suggesting that PFAS–TH associations were not modified by high TPOAb or low iodine alone. However, PFHxS and PFOS were negatively associated (p < 0.05) with fT4, and all four PFASs were positively associated (p < 0.05) with fT3, fT3/fT4, TSH, and TT3 in the group with joint exposure to high TPOAb and low iodine (T1I1). Conclusions: We found evidence of PFAS-associated thyroid disruption in a subset of U.S. adults with high TPOAb (a marker of autoimmune hypothyroidism) and low iodine status, who may represent a vulnerable subgroup. However, the small sample size, cross-sectional design, and possibility of

  8. Loss and in situ production of perfluoroalkyl chemicals in outdoor biosolids-soil mesocosms

    PubMed Central

    Venkatesan, Arjun K.; Halden, Rolf U.

    2014-01-01

    An outdoor mesocosm study was conducted in Baltimore, Maryland, to explore the fate of thirteen perfluoroalkyl substances (PFASs) over the course of three years in biosolids/soil mixtures (1:2) exposed to ambient outdoor conditions. Analysis by liquid chromatography tandem mass spectrometry showed perfluorooctanoate (PFOA) to be the most abundant analyte found early in the soil weathering experiment at 24.1 ng/g dry weight (dw), followed by perfluoroundecanoate (PFUnDA) and perfluorodecanoate (PFDA) at 18.4 and 17.4 ng/g dw, respectively. Short-chain perfluorinated carboxylates (PFCAs; C4-C8) showed observable loss from biosolids/soil mixtures, with experimentally determined first-order half-lives in soil ranging from 385 to 866 days. Perfluorooctane sulfonate (PFOS), perfluorononaoate (PFNA) and PFUnDA levels in biosolids/soil mixtures remained stable, while other long-chain PFCAs [PFDA, perfluorododecanoate (PFDoDA)] and perfluorooctane sulfonamide (PFOSA) levels increased over time, presumably due to the breakdown of unidentified precursors in a process analogous to that reported previously for wastewater treatment plants. This study informs risk assessment initiatives by furnishing data on the environmental persistence of PFASs while also constituting the first report on in situ production of long-chained PFASs in terrestrial environments. PMID:24834828

  9. Perfluoroalkyl acids and related chemistries Toxicokinetics and modes of action

    EPA Science Inventory

    The perfluoroalkyl acid salts (both carboxylates and sulfonates, hereafter designated as PFAAs) and their derivatives are important chemicals that have numerous consumer and industrial applications. However, recent discoveries that some of these compounds have global distribution...

  10. Current Understanding of Perfluoroalkyl Acid Toxicology

    EPA Science Inventory

    The perfluoroalkyl acids (PFAAs) are a family of organic chemicals consisting of a perfluorinated carbon backbone (4-14 carbons in length) and an anionic head group (sulfonate, carboxylate or phosphonate). These compounds have excellent surface-tension reducing properties and hav...

  11. Perfluoroalkyl acids : Recent activities and research progress

    EPA Science Inventory

    The perfluoroalkyl acids (PFAAs) are a family of man-made fluorinated organic chemicals consisting of a carbon backbone typically of four to fourteen in length and a charged functional moiety (primarily carboxylate, sulfonate or phosphonate). The two most widely known PFAAs are ...

  12. The influence of a non-aqueous phase liquid (NAPL) and chemical oxidant application on perfluoroalkyl acid (PFAA) fate and transport.

    PubMed

    McKenzie, Erica R; Siegrist, Robert L; McCray, John E; Higgins, Christopher P

    2016-04-01

    One dimensional column experiments were conducted using saturated porous media containing residual trichloroethylene (TCE) to understand the effects of non-aqueous phase liquids (NAPLs) and chemical oxidation on perfluoroalkyl acid (PFAA) fate and transport. Observed retardation factors and data from supporting batch studies suggested that TCE provides additional sorption capacity that can increase PFAA retardation (i.e., decreased mobility), though the mechanisms remain unclear. Treatment with persulfate activated with FeCl2 and citric acid, catalyzed hydrogen peroxide (CHP), or permanganate did not result in oxidative transformations of PFAAs. However, impacts on PFAA sorption were apparent, and enhanced sorption was substantial in the persulfate-treated columns. In contrast, PFAA transport was accelerated in permanganate- and CHP-treated columns. Ultimately, PFAA transport in NAPL contaminated groundwater is likely influenced by porous media properties, NAPL characteristics, and water quality properties, each of which can change due to chemical oxidant treatment. For contaminated sites for which ISCO is a viable treatment option, changes to PFAA transport and the implications thereof should be included as a component of the remediation evaluation and selection process. PMID:26854608

  13. The influence of a non-aqueous phase liquid (NAPL) and chemical oxidant application on perfluoroalkyl acid (PFAA) fate and transport.

    PubMed

    McKenzie, Erica R; Siegrist, Robert L; McCray, John E; Higgins, Christopher P

    2016-04-01

    One dimensional column experiments were conducted using saturated porous media containing residual trichloroethylene (TCE) to understand the effects of non-aqueous phase liquids (NAPLs) and chemical oxidation on perfluoroalkyl acid (PFAA) fate and transport. Observed retardation factors and data from supporting batch studies suggested that TCE provides additional sorption capacity that can increase PFAA retardation (i.e., decreased mobility), though the mechanisms remain unclear. Treatment with persulfate activated with FeCl2 and citric acid, catalyzed hydrogen peroxide (CHP), or permanganate did not result in oxidative transformations of PFAAs. However, impacts on PFAA sorption were apparent, and enhanced sorption was substantial in the persulfate-treated columns. In contrast, PFAA transport was accelerated in permanganate- and CHP-treated columns. Ultimately, PFAA transport in NAPL contaminated groundwater is likely influenced by porous media properties, NAPL characteristics, and water quality properties, each of which can change due to chemical oxidant treatment. For contaminated sites for which ISCO is a viable treatment option, changes to PFAA transport and the implications thereof should be included as a component of the remediation evaluation and selection process.

  14. A rapid method for the determination of perfluoroalkyl substances including structural isomers of perfluorooctane sulfonic acid in human serum using 96-well plates and column-switching ultra-high performance liquid chromatography tandem mass spectrometry.

    PubMed

    Salihovic, Samira; Kärrman, Anna; Lindström, Gunilla; Lind, P Monica; Lind, Lars; van Bavel, Bert

    2013-08-30

    To facilitate high-throughput analysis suitable for large epidemiological studies we developed an automated column-switching ultra-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) method for determination of perfluorocarboxylic acids (PFCAs; C5, C6, C7, C8, C9, C10, C11, C12, and C13), perfluoroalkyl sulfonic acids (PFSAs; C4, C6, C8, and C10), perfluorooctane sulfonamide (PFOSA), and five groups of structural perfluorooctane sulfonic acid (PFOS) isomers in human serum or plasma. The analytical procedure involves rapid protein precipitation using 96-well plates followed by an automated sample clean-up using an on-line trap column removing many potentially interfering sample components while through the mobile phase gradient the target analytes are eluted onto the analytical column for further separation and subsequent mass detection. The method was linear (R(2)<0.995) at concentrations ranging from 0.01 to 60ngmL(-1) with method detection limits ranging between 0.01 and 0.17ngmL(-1) depending on the analyte. The developed method was precise, with repeatability (n=7) and reproducibility (n=103) coefficients of variation between 2% and 20% for most compounds including PFOS (2% and 8%) and its structural isomers (2-6% and 4-8%). The method was in conformity with a standard reference material. The column-switching HPLC-MS/MS method has been successfully applied for the determination of perfluoroalkyl substances including structural PFOS isomers in human plasma from an epidemiological study.

  15. TOXICOGENOMIC STUDY OF TRIAZOLE FUNGICIDES AND PERFLUOROALKYL ACIDS IN RAT LIVERS ACCURATELY CATEGORIZES CHEMICALS AND IDENTIFIES MECHANISMS OF TOXICITY

    EPA Science Inventory

    Toxicogenomic analysis of five environmental chemicals was performed to investigate the ability of genomics to predict toxicity, categorize chemicals, and elucidate mechanisms of toxicity. Three triazole antifungals (myclobutanil, propiconazole, and triadimefon) and two perfluori...

  16. 40 CFR 721.7200 - Perfluoroalkyl aromatic carbamate modified alkyl methacrylate copolymer.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... modified alkyl methacrylate copolymer. 721.7200 Section 721.7200 Protection of Environment ENVIRONMENTAL... alkyl methacrylate copolymer. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as perfluoroalkyl aromatic carbamate modified...

  17. 40 CFR 721.7200 - Perfluoroalkyl aromatic carbamate modified alkyl methacrylate copolymer.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... modified alkyl methacrylate copolymer. 721.7200 Section 721.7200 Protection of Environment ENVIRONMENTAL... alkyl methacrylate copolymer. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as perfluoroalkyl aromatic carbamate modified...

  18. 40 CFR 721.7200 - Perfluoroalkyl aromatic carbamate modified alkyl methacrylate copolymer.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... modified alkyl methacrylate copolymer. 721.7200 Section 721.7200 Protection of Environment ENVIRONMENTAL... alkyl methacrylate copolymer. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as perfluoroalkyl aromatic carbamate modified...

  19. 40 CFR 721.7200 - Perfluoroalkyl aromatic carbamate modified alkyl methacrylate copolymer.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... modified alkyl methacrylate copolymer. 721.7200 Section 721.7200 Protection of Environment ENVIRONMENTAL... alkyl methacrylate copolymer. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as perfluoroalkyl aromatic carbamate modified...

  20. 40 CFR 721.7200 - Perfluoroalkyl aromatic carbamate modified alkyl methacrylate copolymer.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... modified alkyl methacrylate copolymer. 721.7200 Section 721.7200 Protection of Environment ENVIRONMENTAL... alkyl methacrylate copolymer. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as perfluoroalkyl aromatic carbamate modified...

  1. Synthesis of quaternary α-perfluoroalkyl lactams via electrophilic perfluoroalkylation.

    PubMed

    Katayev, D; Václavík, J; Brüning, F; Commare, B; Togni, A

    2016-03-14

    Efficient protocols enabling the rapid installation of trifluoromethyl, as well as further functionalized fluoroalkyl groups by an electrophilic perfluoroalkylation of lactam-derived ketene silyl amides (KSAs) using hypervalent iodine reagents 1 and 2 have been developed. PMID:26893124

  2. TOXICOGENOMIC DISSECTION OF RODENT LIVER TRANSCRIPT PROFILES AFTER EXPOSURE TO PERFLUOROALKYL ACIDS

    EPA Science Inventory

    Exposure to peroxisome proliferator chemicals (PPC) leads to alterations in the balance between hepatocyte growth and apoptosis, increases in liver to body weight ratios and liver tumors. The perfluoroalkyl acids including perfluorooctanoate (PFOA) and perfluorooctane sulfonate (...

  3. Serum chemical values in hypothermic and rewarmed young calves.

    PubMed

    Olson, D P; South, P J; Hendrix, K

    1983-04-01

    Serum chemical values were determined in cold-stressed Holstein bull calves ranging from 1 to 7 days of age. The animals were anesthetized and cold-stressed until their core body temperature (colonic) was lowered 10 C. Animals were then rewarmed in warm water, with heat pads or heat lamps, or were allowed to recover naturally (unassisted) at room temperature. Blood samples were collected at selected intervals during cooling and recovery. Increases (P less than 0.05) were observed in the concentrations of glucose, calcium, phosphorus, iron, alkaline phosphatase, aspartate aminotransferase, lactate dehydrogenase, total protein, albumin, total globulin, serum urea nitrogen, uric acid, total bilirubin, indirect bilirubin, and cholesterol in the cold-stressed calves during cooling. Concentrations of chloride and insulin decreased (P less than 0.05) during the same period. Changes observed in many of the serum chemical values during rewarming were generally the reverse of the respective changes that occurred during cooling, although insulin values became exceedingly high in some cases midway or near the end of recovery. Serum enzyme values also remained high during most of recovery. Data did not indicate a clear advantage of one method of rewarming over the other methods used in terms of return of the serum chemical values to normal.

  4. Aromatic and heterocyclic perfluoroalkyl sulfides. Methods of preparation

    PubMed Central

    2010-01-01

    Summary This review covers all of the common methods for the syntheses of aromatic and heterocyclic perfluoroalkyl sulfides, a class of compounds which is finding increasing application as starting materials for the preparation of agrochemicals, pharmaceutical products and, more generally, fine chemicals. A systematic approach is taken depending on the mode of incorporation of the SRF groups and also on the type of reagents used. PMID:20978611

  5. Perfluoroalkylation of Unactivated Alkenes with Acid Anhydrides as the Perfluoroalkyl Source.

    PubMed

    Kawamura, Shintaro; Sodeoka, Mikiko

    2016-07-18

    An efficient perfluoroalkylation of unactivated alkenes with perfluoro acid anhydrides was developed. Copper salts play a crucial role as a catalyst to achieve allylic perfluoroalkylation with the in situ generated bis(perfluoroacyl) peroxides. Furthermore, carboperfluoroalkylation of alkene bearing an aromatic ring at an appropriate position on the carbon side chain was found to proceed under metal-free conditions to afford carbocycles or heterocycles bearing a perfluoroalkyl group. This method, which makes use of readily available perfluoroalkyl sources, offers a convenient and powerful tool for introducing a perfluoroalkyl group onto an sp(3) carbon to construct synthetically useful skeletons. PMID:27254318

  6. Perfluoroalkyl polytriazines containing pendent iododifluoromethyl groups

    NASA Technical Reports Server (NTRS)

    Rosser, R. W.; Psarras, T. (Inventor)

    1980-01-01

    New perfluoroalkyl polytriazines containing pendent iododifluoromethyl groups are prepared by the reaction of perfluoroalkyl dinitriles with ammonia to form poly(imidoylamidines), followed by the cyclization of the imidoylamidine groups with, e.g., various mixtures of a perfluoroacyl fluoride with an omega iodoperfluoroacyl fluoride. The polytriazines obtained can be cured by heat which causes crosslinking at the iododifluoromethyl groups by elimination of iodine and formation of carbon-to-carbon bonds.

  7. Perfluoroalkyl and polyfluoroalkyl substances in the environment: terminology, classification, and origins.

    PubMed

    Buck, Robert C; Franklin, James; Berger, Urs; Conder, Jason M; Cousins, Ian T; de Voogt, Pim; Jensen, Allan Astrup; Kannan, Kurunthachalam; Mabury, Scott A; van Leeuwen, Stefan P J

    2011-10-01

    The primary aim of this article is to provide an overview of perfluoroalkyl and polyfluoroalkyl substances (PFASs) detected in the environment, wildlife, and humans, and recommend clear, specific, and descriptive terminology, names, and acronyms for PFASs. The overarching objective is to unify and harmonize communication on PFASs by offering terminology for use by the global scientific, regulatory, and industrial communities. A particular emphasis is placed on long-chain perfluoroalkyl acids, substances related to the long-chain perfluoroalkyl acids, and substances intended as alternatives to the use of the long-chain perfluoroalkyl acids or their precursors. First, we define PFASs, classify them into various families, and recommend a pragmatic set of common names and acronyms for both the families and their individual members. Terminology related to fluorinated polymers is an important aspect of our classification. Second, we provide a brief description of the 2 main production processes, electrochemical fluorination and telomerization, used for introducing perfluoroalkyl moieties into organic compounds, and we specify the types of byproducts (isomers and homologues) likely to arise in these processes. Third, we show how the principal families of PFASs are interrelated as industrial, environmental, or metabolic precursors or transformation products of one another. We pay particular attention to those PFASs that have the potential to be converted, by abiotic or biotic environmental processes or by human metabolism, into long-chain perfluoroalkyl carboxylic or sulfonic acids, which are currently the focus of regulatory action. The Supplemental Data lists 42 families and subfamilies of PFASs and 268 selected individual compounds, providing recommended names and acronyms, and structural formulas, as well as Chemical Abstracts Service registry numbers.

  8. Perfluoroalkyl and Polyfluoroalkyl Substances in the Environment: Terminology, Classification, and Origins

    PubMed Central

    Buck, Robert C; Franklin, James; Berger, Urs; Conder, Jason M; Cousins, Ian T; de Voogt, Pim; Jensen, Allan Astrup; Kannan, Kurunthachalam; Mabury, Scott A; van Leeuwen, Stefan PJ

    2011-01-01

    The primary aim of this article is to provide an overview of perfluoroalkyl and polyfluoroalkyl substances (PFASs) detected in the environment, wildlife, and humans, and recommend clear, specific, and descriptive terminology, names, and acronyms for PFASs. The overarching objective is to unify and harmonize communication on PFASs by offering terminology for use by the global scientific, regulatory, and industrial communities. A particular emphasis is placed on long-chain perfluoroalkyl acids, substances related to the long-chain perfluoroalkyl acids, and substances intended as alternatives to the use of the long-chain perfluoroalkyl acids or their precursors. First, we define PFASs, classify them into various families, and recommend a pragmatic set of common names and acronyms for both the families and their individual members. Terminology related to fluorinated polymers is an important aspect of our classification. Second, we provide a brief description of the 2 main production processes, electrochemical fluorination and telomerization, used for introducing perfluoroalkyl moieties into organic compounds, and we specify the types of byproducts (isomers and homologues) likely to arise in these processes. Third, we show how the principal families of PFASs are interrelated as industrial, environmental, or metabolic precursors or transformation products of one another. We pay particular attention to those PFASs that have the potential to be converted, by abiotic or biotic environmental processes or by human metabolism, into long-chain perfluoroalkyl carboxylic or sulfonic acids, which are currently the focus of regulatory action. The Supplemental Data lists 42 families and subfamilies of PFASs and 268 selected individual compounds, providing recommended names and acronyms, and structural formulas, as well as Chemical Abstracts Service registry numbers. Integr Environ Assess Manag 2011;7:513–541. © 2011 SETAC PMID:21793199

  9. High Lipophilicty of Perfluoroalkyl Carboxylate and Sulfonate

    PubMed Central

    Jing, Ping; Rodgers, Patrick J.; Amemiya, Shigeru

    2009-01-01

    Here we report on remarkably high lipophilicity of perfluoroalkyl carboxylate and sulfonate. A lipophilic nature of this emerging class of organic pollutants has been hypothesized as an origin of their bioaccumulation and toxicity. Both carboxylate and sulfonate, however, are considered hydrophilic while perfluroalkyl groups are not only hydrophobic but also oleophobic. Partition coefficients of homologous series of perfluoroalkyl and alkyl carboxylates between water and n-octanol were determined as a measure of their lipophilicity by ion-transfer cyclic voltammetry. Very similar lipophilicity of perfluoroalkyl and alkyl chains with the same length is demonstrated experimentally for the first time by fragment analysis of the partition coefficients. This finding is important for pharmaceutical and biomedical applications of perfluoroalkyl compounds. Interestingly, ∼2 orders of magnitude higher lipophilicity of a perfluoroalkyl carboxylate or sulfonate in comparison to its alkyl counterpart is ascribed nearly exclusively to their oxoanion groups. The higher lipophilicity originates from a strong electron-withdrawing effect of the perfluoroalkyl group on the adjacent oxoanion group, which is weakly hydrated to decrease its hydrophilicity. In fact, the inductive effect is dramatically reduced for a fluorotelomer with an ethylene spacer between perfluorohexyl and carboxylate groups, which is only as lipophilic as its alkyl counterpart, nonanoate, and is 400 times less lipophilic than perfluorononanoate. The high lipophilicity of perfluoroalkyl carboxylate and sulfonate implies that their permeation across such a thin lipophilic membrane as a bilayer lipid membrane is limited by their transfer at a membrane/water interface. The limiting permeability is lower and less dependent on their lipophilicity than the permeability controlled by their diffusion in the membrane interior as assumed in the classical solubility-diffusion model. PMID:19170492

  10. Isomer profiles of perfluoroalkyl substances in water and soil surrounding a chinese fluorochemical manufacturing park.

    PubMed

    Jin, Hangbiao; Zhang, Yifeng; Zhu, Lingyan; Martin, Jonathan W

    2015-04-21

    Despite that China is the largest global manufacturer of perfluoroalkyl substances (PFASs), the manufacturing methods and isomer purity of these chemicals are generally unknown. Here, sampling was conducted around a major fluorochemical manufacturing park in China in 2012, including soil and water collection inside the park, including from a wastewater treatment plant (WWTP), as well as in surrounding rivers and soil (∼15 km radius). Perfluoroalkyl sulfonates (PFSAs) were lower than perfluoroalkyl carboxylates (PFCAs) in all samples, and short-chain (C4-C6) PFCAs were predominant. Perfluoroalkyl phosphonates and phosphate diesters were occasionally detected, but at low detection frequency. Branched isomers of perfluorobutanesulfonate (PFBS) are reported for the first time, accounting for 15-27% of total PFBS in water. An enrichment of isopropyl-PFOA (28%) was found in WWTP influent, suggesting its manufacturing primarily by isopropyl telomerization. More numerous branched isomers were observed for the longer C9-C13 PFCAs (e.g., C12 PFCA had 16 branched isomers), including high proportions of one major branched isomer (likely isopropyl), possibly as impurities from isopropyl-PFOA manufacturing. Overall, short-chain perfluorinated acids were the predominant PFASs being released, but PFOA was still a major chemical in use at this site, primarily from isopropyl telomerization.

  11. Accumulation potentials of perfluoroalkyl carboxylic acids (PFCAs) and perfluoroalkyl sulfonic acids (PFSAs) in maize (Zea mays).

    PubMed

    Krippner, Johanna; Falk, Sandy; Brunn, Hubertus; Georgii, Sebastian; Schubert, Sven; Stahl, Thorsten

    2015-04-15

    Uptake of perfluoroalkyl acids (PFAAs) by maize represents a potential source of exposure for humans, either directly or indirectly via feed for animals raised for human consumption. The aim of the following study was, therefore, to determine the accumulation potential of perfluoroalkyl carboxylic acids (PFCAs) and perfluoroalkyl sulfonic acids (PFSAs) in maize (Zea mays). Two different concentrations of PFAAs were applied as aqueous solution to the soil to attain target concentrations of 0.25 mg or 1.00 mg of PFAA per kg of soil. Maize was grown in pots, and after harvesting, PFAA concentrations were measured in the straw and kernels of maize. PFCA and PFSA concentrations of straw decreased significantly with increasing chain length. In maize kernels, only PFCAs with a chain length ≤ C8 as well as perfluorobutanesulfonic acid (PFBS) were detected. The highest soil-to-plant transfer for both straw and kernels was determined for short-chained PFCAs and PFSAs.

  12. Polyfluoroalkyl Chemicals in the Serum and Milk of Breastfeeding Women.

    EPA Science Inventory

    Polyfluoroalkyl chemicals (PFCs) comprise a group of man-made organic compounds, some of which are persistent contaminants with developmental toxicity shown in laboratory animals. There is a paucity of human perinatal exposure data. The US EPA conducted a pilot study (Methods Adv...

  13. Perfluoroalkyl compounds (PFCs) in wildlife from an urban estuary.

    PubMed

    Sedlak, Margaret D; Greig, Denise J

    2012-01-01

    Previous research has documented the bioaccumulation of perfluoroalkyl compounds (PFCs) in apex predators in remote locations but few studies have evaluated urban estuaries. To assess the importance of PFCs in San Francisco Bay, two apex predators in the San Francisco Bay, double-crested cormorants (Phalacrocorax auritus) and Pacific harbor seals (Phoca vitulina richardii), were sampled. Prey fish (Atherinops affinis and Menidia audens) were also evaluated to better understand potential sources of PFCs to the foodweb. Perfluorooctane sulfonate (PFOS) was the primary PFC detected in cormorant eggs, small fish and harbor seal serum. PFOS detected in San Francisco Bay seal serum was typically an order of magnitude higher than those at the reference site. PFOS concentrations were highest in seals and cormorant eggs from the highly urbanized southern portion of the Bay. PFOS in eggs from the southern part of the Bay remained relatively constant between 2006 and 2009 despite the phase-out of perfluorosulfonyl-based compounds nationally. In addition, these levels exceed the avian predicted no effects concentration of 1.0 μg mL(-1). Concentrations of the remaining PFCs measured were substantially lower than those of PFOS. PMID:22134832

  14. Maternal exposure to perfluoroalkyl acids measured in whole blood and birth outcomes in offspring.

    PubMed

    Callan, A C; Rotander, A; Thompson, K; Heyworth, J; Mueller, J F; Odland, J Ø; Hinwood, A L

    2016-11-01

    Perfluoralkyl and polyfluoralkyl substances have been measured in plasma and serum of pregnant women as a measure of prenatal exposure. Increased concentrations of individual perfluoroalkyl acids (PFAAs), (typically perfluorooctanoic acid (PFOA) and perfluoroctane sulfonate (PFOS) have been reported to be associated with reductions in birth weight and other birth outcomes. We undertook a study of 14 PFAAs in whole blood (including PFOS, PFHxS, PFHpA, PFOA, PFNA, PFDA and PFUnDA) from 98 pregnant women in Western Australia from 2008 to 2011. Median concentrations (in μg/L) were: PFOS 1.99; PFHxS 0.33; PFOA 0.86; PFNA 0.30; PFDA 0.12 and PFUnDA 0.08. Infants born to women with the highest tertile of PFHxS exposure had an increased odds of being <95% of their optimal birth weight (OR 3.5, 95% CI 1.1-11.5). Conversely, maternal blood concentrations of PFUnDA were associated with non-significant increases in average birth weight (+102g, 95% CI -41, 245) and significant increases in proportion of optimal birth weight (+4.7%, 95% CI 0.7, 8.8) per ln-unit change. This study has reported a range of PFAAs in the whole blood of pregnant women and suggests that PFHxS and PFUnDA may influence foetal growth and warrant further attention. Additional studies are required to identify the sources of PFAA exposure with a view to prevention, in addition to further studies investigating the long term health effects of these ubiquitous chemicals. PMID:27387804

  15. Efficient generation of perfluoroalkyl radicals from sodium perfluoroalkanesulfinates and a hypervalent iodine(iii) reagent: mild, metal-free synthesis of perfluoroalkylated organic molecules.

    PubMed

    Sakamoto, Ryu; Kashiwagi, Hirotaka; Selvakumar, Sermadurai; Moteki, Shin A; Maruoka, Keiji

    2016-07-01

    This article describes an efficient method for the introduction of perfluoroalkyl groups into N-acrylamides, 2-isocyanides, olefins, and other heterocycles using perfluoroalkyl radicals that were generated from the reaction between sodium perfluoroalkanesulfinates and a hypervalent iodine(iii) reagent. This approach represents a simple, scalable perfluoroalkylation method under mild and metal-free conditions.

  16. Perfluoroalkyl acids: recent research highlights

    EPA Science Inventory

    Perfluorinated compounds are organic chemicals in which all hydrogen molecules of the carbon-chain are substituted by fluorine molecules. Generally, there are two types of perfluorinated compounds, the perfluoroalkanes that are primarily used clinically for oxygenation and respir...

  17. Perfluoroalkyl substances and thyroid function in older adults.

    PubMed

    Shrestha, Srishti; Bloom, Michael S; Yucel, Recai; Seegal, Richard F; Wu, Qian; Kannan, Kurunthachalam; Rej, Robert; Fitzgerald, Edward F

    2015-02-01

    Current understanding of the thyroid disruptive properties of perfluoroalkyl substances (PFASs), particularly in aging populations, is limited. The objectives of this study were to (i) assess associations between thyroid function, as measured by serum thyrotropin (thyroid stimulating hormone, TSH), free thyroxine (fT4), total thyroxine (T4), and total triiodothyronine (T3), and serum perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) in an aging population and (ii) determine if other persistent organic pollutants with thyroid disruptive properties including polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) modify such associations. We conducted a cross-sectional study of 87 men and women 55 to 74years of age, without clinically-diagnosed thyroid disease, who resided in upper Hudson River communities in New York. Geometric means (standard deviations) of serum PFOS and PFOA were 31.6 (1.7) ng/mL and 9.17 (1.72) ng/mL, respectively. Multivariable linear regression analyses indicated that one interquartile range difference in PFOS corresponded to 4% and 9% increases in fT4 and T4 respectively. We detected statistical interactions between PFOA and age for effects on fT4 and T4; joint increases in PFOA and age were associated with increases in fT4 and T4, of 3% and 7%, respectively. We also detected statistical interactions between PFOS and total PCBs for the effect on T3 and between PFOA and total PBDEs for the effect on TSH. Our results suggest that PFASs are associated with subtle alterations in thyroid hormone levels in this population, and that these associations are likely to vary by age, and levels of PCBs and PBDEs. PMID:25483837

  18. Perfluoroalkyl Substances and Thyroid Function in Older Adults

    PubMed Central

    Shrestha, Srishti; Bloom, Michael S.; Yucel, Recai; Seegal, Richard F.; Wu, Qian; Kannan, Kurunthachalam; Rej, Robert; Fitzgerald, Edward F.

    2014-01-01

    Current understanding of the thyroid disruptive properties of perfluoroalkyl substances (PFASs), particularly in aging populations, is limited. The objectives of this study were to (i) assess associations between thyroid function, as measured by serum thyrotropin (thyroid stimulating hormone, TSH), free thyroxine (fT4), total thyroxine (T4), and total triiodothyronine (T3), and serum perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) in an aging population and (ii) determine if other persistent organic pollutants with thyroid disruptive properties including polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) modify such associations. We conducted a cross-sectional study of 87 men and women 55 to 74 years of age, without clinically-diagnosed thyroid disease, who resided in upper Hudson River communities in New York. Geometric means (standard deviations) of serum PFOS and PFOA were 31.6 (1.7) ng/mL and 9.17 (1.72) ng/mL, respectively. Multivariable linear regression analyses indicated that one interquartile range difference in PFOS corresponded to 4% and 9% increases in fT4 and T4 respectively. We detected statistical interactions between PFOA and age for effects on fT4 and T4; joint increases in PFOA and age were associated with increases in fT4 and T4, of 3% and 7%, respectively. We also detected statistical interactions between PFOS and total PCBs for the effect on T3 and between PFOA and total PBDEs for the effect on TSH. Our results suggest that PFASs are associated with subtle alterations in thyroid hormone levels in this population, and that these associations are likely to vary by age, and levels of PCBs and PBDEs. PMID:25483837

  19. Selected physicochemical aspects of poly- and perfluoroalkylated substances relevant to performance, environment and sustainability-part one.

    PubMed

    Krafft, Marie Pierre; Riess, Jean G

    2015-06-01

    The elemental characteristics of the fluorine atom tell us that replacing an alkyl chain by a perfluoroalkyl or polyfluorinated chain in a molecule or polymer is consequential. A brief reminder about perfluoroalkyl chains, fluorocarbons and fluorosurfactants is provided. The outstanding, otherwise unattainable physicochemical properties and combinations thereof of poly and perfluoroalkyl substances (PFASs) are outlined, including extreme hydrophobic and lipophobic character; thermal and chemical stability in extreme conditions; remarkable aptitude to self-assemble into sturdy thin repellent protecting films; unique spreading, dispersing, emulsifying, anti-adhesive and levelling, dielectric, piezoelectric and optical properties, leading to numerous industrial and technical uses and consumer products. It was eventually discovered, however, that PFASs with seven or more carbon-long perfluoroalkyl chains had disseminated in air, water, soil and biota worldwide, are persistent in the environment and bioaccumulative in animals and humans, raising serious health and environmental concerns. Further use of long-chain PFASs is environmentally not sustainable. Most leading manufacturers have turned to shorter four to six carbon perfluoroalkyl chain products that are not considered bioaccumulative. However, many of the key performances of PFASs decrease sharply when fluorinated chains become shorter. Fluorosurfactants become less effective and less efficient, provide lesser barrier film stability, etc. On the other hand, they remain as persistent in the environment as their longer chain homologues. Surprisingly little data (with considerable discrepancies) is accessible on the physicochemical properties of the PFASs under examination, a situation that requires consideration and rectification. Such data are needed for understanding the environmental and in vivo behaviour of PFASs. They should help determine which, for which uses, and to what extent, PFASs are environmentally

  20. Polymerizable disilanols having in-chain perfluoroalkyl groups

    NASA Technical Reports Server (NTRS)

    Patterson, W. J.; Morris, D. E. (Inventor)

    1973-01-01

    Disilanols containing in-chain perfluoroalkyl and aromatic groups and the process by which they were prepared are discussed. The disilanols, when reacted with a diaminosilane and cured, produce polymeric material resistant to hydrocarbon fuels and stable at elevated temperatures.

  1. THE DEVELOPMENTAL TOXICITY OF PERFLUOROALKYL ACIDS AND THEIR DERIVATIVES

    EPA Science Inventory

    Abstract

    Perfluoroalkyl acids such as perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) have applications in numerous industrial and consumer products. Although the toxicology of some of these compounds has been investigated in the past, the widespread pr...

  2. Developmental Toxicity of Perfluoroalkyl Acid Mixtures in CD-1 Mice

    EPA Science Inventory

    Perfluorooctanoic acid (PFOA), perfluorooctane sulfonate (PFOS) and perfluorononanoic acid (PFNA) belong to a family of fluoro-organic compounds known as perfluoroalkyl acids (PFAAs). PFAAs have been widely used in industrial and commercial applications, and have been found to be...

  3. Determination of polyfluoroalkyl phosphoric acid diesters, perfluoroalkyl phosphonic acids, perfluoroalkyl phosphinic acids, perfluoroalkyl carboxylic acids, and perfluoroalkane sulfonic acids in lake trout from the Great Lakes region.

    PubMed

    Guo, Rui; Reiner, Eric J; Bhavsar, Satyendra P; Helm, Paul A; Mabury, Scott A; Braekevelt, Eric; Tittlemier, Sheryl A

    2012-11-01

    A comprehensive method to extract perfluoroalkyl carboxylic acids, perfluoroalkane sulfonic acids, perfluoroalkyl phosphonic acids, perfluoroalkyl phosphinic acids, and polyfluoroalkyl phosphoric acid diesters simultaneously from fish samples has been developed. The recoveries of target compounds ranged from 78 % to 121 %. The new method was used to analyze lake trout (Salvelinus namaycush) from the Great Lakes region. The results showed that the total perfluoroalkane sulfonate concentrations ranged from 0.1 to 145 ng/g (wet weight) with perfluorooctane sulfonate (PFOS) as the dominant contaminant. Concentrations in fish between lakes were in the order of Lakes Ontario ≈ Erie > Huron > Superior ≈ Nipigon. The total perfluoroalkyl carboxylic acid concentrations ranged from 0.2 to 18.2 ng/g wet weight. The aggregate mean perfluorooctanoic acid (PFOA) concentration in fish across all lakes was 0.045 ± 0.023 ng/g. Mean concentrations of PFOA were not significantly different (p > 0.1) among the five lakes. Perfluoroalkyl phosphinic acids were detected in lake trout from Lake Ontario, Lake Erie, and Lake Huron with concentration ranging from non-detect (ND) to 0.032 ng/g. Polyfluoroalkyl phosphoric acid diesters were detected only in lake trout from Lake Huron, at levels similar to perfluorooctanoic acid.

  4. Phlebotomy Treatment for Elimination of Perfluoroalkyl Acids in a Highly Exposed Family: A Retrospective Case-Series

    PubMed Central

    Genuis, Stephen J.; Liu, Yanna; Genuis, Quentin I. T.; Martin, Jonathan W.

    2014-01-01

    Background Perfluoroalkyl acids (PFAAs) are a family of commonly used synthetic chemicals that have become widespread environmental contaminants. In human serum, perfluorohexane sulfonate (PFHxS), perflurooctane sulfonate (PFOS), and perfluorooctanoate (PFOA) are most frequently detected, in part owing to their long elimination half-lives of between 3.8 yrs (PFOA) and 8.5 yrs (PFHxS). These PFAAs also cross the placenta and have been associated with developmental toxicity, and some are considered likely human carcinogens. Interventions to eliminate PFAAs in highly contaminated individuals would reduce future health risks, but minimal research has been conducted on methods to facilitate accelerated human clearance of these persistent substances. Methods Six patients with elevated serum concentrations from a single family were treated by intermittent phlebotomy over a 4–5 year period at intervals similar to, or less frequent than what is done for routine blood donation at Canadian Blood Services. The apparent elimination half-life (HLapp) for PFHxS, PFOS, and PFOA in this treated population was calculated in each patient and compared to the intrinsic elimination half-lives (HLin) from a literature reference population of untreated fluorochemical manufacturing plant retirees (n = 26, age >55 yrs). Results For all three PFAAs monitored during phlebotomy, HLapp in each of the family members (except the mother, who had a low rate of venesection) was significantly shorter than the geometric mean HL measured in the reference population, and in some cases were even shorter compared to the fastest eliminator in the reference population. Conclusion This study suggests significantly accelerated PFAA clearance with regular phlebotomy treatment, but the small sample size and the lack of controls in this clinical intervention precludes drawing firm conclusions. Given the minimal risks of intermittent phlebotomy, this may be an effective and safe clinical intervention to

  5. Iron-catalyzed 1,2-addition of perfluoroalkyl iodides to alkynes and alkenes.

    PubMed

    Xu, Tao; Cheung, Chi Wai; Hu, Xile

    2014-05-01

    Iron catalysis has been developed for the intermolecular 1,2-addition of perfluoroalkyl iodides to alkynes and alkenes. The catalysis has a wide substrate scope and high functional-group tolerance. A variety of perfluoroalkyl iodides including CF3 I can be employed. The resulting perfluoroalkylated alkyl and alkenyl iodides can be further functionalized by cross-coupling reactions. This methodology provides a straightforward and streamlined access to perfluoroalkylated organic molecules.

  6. Perfluoroalkyl and polyfluoroalkyl substances in consumer products.

    PubMed

    Kotthoff, Matthias; Müller, Josef; Jürling, Heinrich; Schlummer, Martin; Fiedler, Dominik

    2015-10-01

    Perfluoroalkyl and polyfluoroalkyl substances (PFAS) are used in a wide range of products of all day life. Due to their toxicological potential, an emerging focus is directed towards their exposure to humans. This study investigated the PFAS load of consumer products in a broad perspective. Perfluoroalkyl sulfonic acids (C4, C6-C8, C10-PFSA), carboxylic acids (C4-C14-PFCA) and fluorotelomer alcohols (4:2, 6:2; 8:2 and 10:2 FTOH) were analysed in 115 random samples of consumer products including textiles (outdoor materials), carpets, cleaning and impregnating agents, leather samples, baking and sandwich papers, paper baking forms and ski waxes. PFCA and PFSA were analysed by HPLC-MS/MS, whereas FTOH were detected by GC/CI-MS. Consumer products such as cleaning agents or some baking and sandwich papers show low or negligible PFSA and PFCA contents. On the other hand, high PFAS levels were identified in ski waxes (up to about 2000 μg/kg PFOA), leather samples (up to about 200 μg/kg PFBA and 120 μg/kg PFBS), outdoor textiles (up to 19 μg/m(2) PFOA) and some other baking papers (up to 15 μg/m(2) PFOA). Moreover, some test samples like carpet and leather samples and outdoor materials exceeded the EU regulatory threshold value for PFOS (1 μg/m(2)). A diverse mixture of PFASs can be found in consumer products for all fields of daily use in varying concentrations. This study proves the importance of screening and monitoring of consumer products for PFAS loads and the necessity for an action to regulate the use of PFASs, especially PFOA, in consumer products.

  7. Perfluoroalkyl and polyfluoroalkyl substances in consumer products.

    PubMed

    Kotthoff, Matthias; Müller, Josef; Jürling, Heinrich; Schlummer, Martin; Fiedler, Dominik

    2015-10-01

    Perfluoroalkyl and polyfluoroalkyl substances (PFAS) are used in a wide range of products of all day life. Due to their toxicological potential, an emerging focus is directed towards their exposure to humans. This study investigated the PFAS load of consumer products in a broad perspective. Perfluoroalkyl sulfonic acids (C4, C6-C8, C10-PFSA), carboxylic acids (C4-C14-PFCA) and fluorotelomer alcohols (4:2, 6:2; 8:2 and 10:2 FTOH) were analysed in 115 random samples of consumer products including textiles (outdoor materials), carpets, cleaning and impregnating agents, leather samples, baking and sandwich papers, paper baking forms and ski waxes. PFCA and PFSA were analysed by HPLC-MS/MS, whereas FTOH were detected by GC/CI-MS. Consumer products such as cleaning agents or some baking and sandwich papers show low or negligible PFSA and PFCA contents. On the other hand, high PFAS levels were identified in ski waxes (up to about 2000 μg/kg PFOA), leather samples (up to about 200 μg/kg PFBA and 120 μg/kg PFBS), outdoor textiles (up to 19 μg/m(2) PFOA) and some other baking papers (up to 15 μg/m(2) PFOA). Moreover, some test samples like carpet and leather samples and outdoor materials exceeded the EU regulatory threshold value for PFOS (1 μg/m(2)). A diverse mixture of PFASs can be found in consumer products for all fields of daily use in varying concentrations. This study proves the importance of screening and monitoring of consumer products for PFAS loads and the necessity for an action to regulate the use of PFASs, especially PFOA, in consumer products. PMID:25854201

  8. Maternal and Neonatal Levels of Perfluoroalkyl Substances in Relation to Gestational Weight Gain

    PubMed Central

    Ashley-Martin, Jillian; Dodds, Linda; Arbuckle, Tye E.; Morisset, Anne-Sophie; Fisher, Mandy; Bouchard, Maryse F.; Shapiro, Gabriel D.; Ettinger, Adrienne S.; Monnier, Patricia; Dallaire, Renee; Taback, Shayne; Fraser, William

    2016-01-01

    Perfluoroalkyl substances (PFASs) are ubiquitous, persistent pollutants widely used in the production of common household and consumer goods. There is a limited body of literature suggesting that these chemicals may alter metabolic pathways and growth trajectories. The relationship between prenatal exposures to these chemicals and gestational weight gain (GWG) has received limited attention. One objective was to analyze the associations among maternal plasma levels of three common perfluoroalkyl substances (perfluorooctanoate (PFOA), perfluorooctanesulfonate (PFOS), perfluorohexanesulfanoate (PFHxS)) and GWG. Additionally, we explored whether GWG was associated with cord blood PFAS levels. This study utilized data collected in the Maternal-Infant Research on Environmental Chemicals (MIREC) Study, a trans-Canada cohort study of 2001 pregnant women. Our analysis quantified associations between (1) maternal PFAS concentrations and GWG and (2) GWG and cord blood PFAS concentrations. Maternal PFOS concentrations were positively associated with GWG (β = 0.39 95% CI: 0.02, 0.75). Interquartile increases in GWG were significantly associated with elevated cord blood PFOA (OR = 1.33; 95% CI: 1.13 to 1.56) and PFOS (OR = 1.20; 95% CI: 1.03 to 1.40) concentrations. No statistically significant associations were observed between GWG and either measure of PFHxS. These findings warrant elucidation of the potential underlying mechanisms. PMID:26805861

  9. Maternal and Neonatal Levels of Perfluoroalkyl Substances in Relation to Gestational Weight Gain.

    PubMed

    Ashley-Martin, Jillian; Dodds, Linda; Arbuckle, Tye E; Morisset, Anne-Sophie; Fisher, Mandy; Bouchard, Maryse F; Shapiro, Gabriel D; Ettinger, Adrienne S; Monnier, Patricia; Dallaire, Renee; Taback, Shayne; Fraser, William

    2016-01-01

    Perfluoroalkyl substances (PFASs) are ubiquitous, persistent pollutants widely used in the production of common household and consumer goods. There is a limited body of literature suggesting that these chemicals may alter metabolic pathways and growth trajectories. The relationship between prenatal exposures to these chemicals and gestational weight gain (GWG) has received limited attention. One objective was to analyze the associations among maternal plasma levels of three common perfluoroalkyl substances (perfluorooctanoate (PFOA), perfluorooctanesulfonate (PFOS), perfluorohexanesulfanoate (PFHxS)) and GWG. Additionally, we explored whether GWG was associated with cord blood PFAS levels. This study utilized data collected in the Maternal-Infant Research on Environmental Chemicals (MIREC) Study, a trans-Canada cohort study of 2001 pregnant women. Our analysis quantified associations between (1) maternal PFAS concentrations and GWG and (2) GWG and cord blood PFAS concentrations. Maternal PFOS concentrations were positively associated with GWG (β = 0.39 95% CI: 0.02, 0.75). Interquartile increases in GWG were significantly associated with elevated cord blood PFOA (OR = 1.33; 95% CI: 1.13 to 1.56) and PFOS (OR = 1.20; 95% CI: 1.03 to 1.40) concentrations. No statistically significant associations were observed between GWG and either measure of PFHxS. These findings warrant elucidation of the potential underlying mechanisms. PMID:26805861

  10. Serum chemical elements and oxidative status in Alzheimer's disease, Parkinson disease and multiple sclerosis.

    PubMed

    Alimonti, Alessandro; Ristori, Giovanni; Giubilei, Franco; Stazi, Maria Antonia; Pino, Anna; Visconti, Andrea; Brescianini, Sonia; Sepe Monti, Micaela; Forte, Giovanni; Stanzione, Paolo; Bocca, Beatrice; Bomboi, Giuseppe; D'Ippolito, Cristina; Annibali, Viviana; Salvetti, Marco; Sancesario, Giuseppe

    2007-05-01

    The role of some chemical elements in neurodegeneration was suggested by various authors. To obtain a profile of chemical elements and oxidative status in complex neurological diseases, an unbiased "omics" approach, i.e., quantification of 26 elements and oxidative stress parameters (serum oxidative status (SOS) and serum anti-oxidant capacity (SAC)), combined with multivariate statistical procedures (forward discriminant analysis, FDA) to analyse the vast amount of data, was applied to four groups of subjects (53 patients with Alzheimer's disease (AD), 71 with Parkinson disease (PD), 60 with multiple sclerosis (MS) and 124 healthy individuals). Descriptive statistics revealed numerous differences between each disease and healthy status. A concordant imbalance (reduction in Fe, Zn and SAC, and increase in SOS) was shared by AD, PD and MS. The FDA yielded three significant discriminant functions based on age, SOS, Ca, Fe, Si, Sn, V, Zn and Zr, and identified disease-specific profiles of element imbalances, thus showing the appropriateness of the "omics" approach. It may help assess the contribution of chemical elements and oxidative stress to disease causation and may provide complex predictors of disease evolution or treatment response.

  11. The effects of chemically modifying serum apolipoproteins on their ability to activate lipoprotein lipase.

    PubMed Central

    Dodds, P F; Lopez-Johnston, A; Welch, V A; Gurr, M I

    1987-01-01

    Lipoprotein lipase activity was measured in an acetone-dried-powder preparation from rat epididymal adipose tissue using pig serum or pig serum lipoprotein, which had been chemically modified, as activator. Modification of acidic amino acids of lipoproteins with NN-dimethyl-1,3-diamine resulted in a complete loss of ability to activate lipoprotein lipase. Modification of 34% of lipoprotein arginine groups with cyclohexanedione resulted in the loss of 75% of the activation of lipoprotein lipase; approx. 42% of the original activity was recovered after reversal of the modification. This effect was dependent on the cyclohexanedione concentration. Modification of 48% of lipoprotein lysine groups with malonaldehyde decreased the maximum activation by 20%, but three times as much lipoprotein was required to achieve this. Non-enzymic glycosylation of lipoprotein with glucose, under a variety of conditions resulting in up to 28 nmol of glucose/mg of protein, had no effect upon the ability to activate lipoprotein lipase. In contrast non-enzymic sialylation resulted in a time-dependent loss of up to 60% of ability to activate lipoprotein lipase. Reductive methylation and acetoacetylation of serum did not affect the ability to activate lipoprotein lipase. The results are compared to the effects of similar modifications to low density lipoproteins on receptor-mediated endocytosis. PMID:3593262

  12. Chemical concentration measurement in blood serum and urine samples using liquid-core optical fiber Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Qi, Dahu; Berger, Andrew J.

    2007-04-01

    We report measurements of chemical concentrations in clinical blood serum and urine samples using liquid-core optical fiber (LCOF) Raman spectroscopy to increase the collected signal strength. Both Raman and absorption spectra were acquired in the near-infrared region using the LCOF geometry. Spectra of 71 blood serum and 61 urine samples were regressed via partial least squares against reference analyzer values. Significant correlation was found between predicted and reference concentrations for 13 chemicals. Using absorption data to normalize the LCOF enhancement made the results more accurate. The experimental geometry is well suited for high-volume and automated chemical analysis of clear biofluids.

  13. Redesigned and chemically-modified hammerhead ribozymes with improved activity and serum stability

    PubMed Central

    Hendry, Philip; McCall, Maxine J; Stewart, Tom S; Lockett, Trevor J

    2004-01-01

    Background Hammerhead ribozymes are RNA-based molecules which bind and cleave other RNAs specifically. As such they have potential as laboratory reagents, diagnostics and therapeutics. Despite having been extensively studied for 15 years or so, their wide application is hampered by their instability in biological media, and by the poor translation of cleavage studies on short substrates to long RNA molecules. This work describes a systematic study aimed at addressing these two issues. Results A series of hammerhead ribozyme derivatives, varying in their hybridising arm length and size of helix II, were tested in vitro for cleavage of RNA derived from the carbamoyl phosphate synthetase II gene of Plasmodium falciparum. Against a 550-nt transcript the most efficient (t1/2 = 26 seconds) was a miniribozyme with helix II reduced to a single G-C base pair and with twelve nucleotides in each hybridising arm. Miniribozymes of this general design were targeted to three further sites, and they demonstrated exceptional cleavage activity. A series of chemically modified derivatives was prepared and examined for cleavage activity and stability in human serum. One derivative showed a 103-fold increase in serum stability and a doubling in cleavage efficiency compared to the unmodified miniribozyme. A second was almost 104-fold more stable and only 7-fold less active than the unmodified parent. Conclusion Hammerhead ribozyme derivatives in which helix II is reduced to a single G-C base pair cleave long RNA substrates very efficiently in vitro. Using commonly available phosphoramidites and reagents, two patterns of nucleotide substitution in this derivative were identified which conferred both good cleavage activity against long RNA targets and good stability in human serum. PMID:15588292

  14. 77 FR 48924 - Perfluoroalkyl Sulfonates and Long-Chain Perfluoroalkyl Carboxylate Chemical Substances; Proposed...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-08-15

    ..., various types of apparel, home textiles, thread sealant tape, floor wax and other sealants, and food... substances? On October 18, 2000, EPA published in the Federal Register a proposed SNUR (65 FR 62319) (FRL... final rule was published in the Federal Register on March 11, 2002 (67 FR 11008) (FRL-6823-6), for...

  15. Occurrence and sources of perfluoroalkyl acids in Italian river basins.

    PubMed

    Valsecchi, Sara; Rusconi, Marianna; Mazzoni, Michela; Viviano, Gaetano; Pagnotta, Romano; Zaghi, Carlo; Serrini, Giuliana; Polesello, Stefano

    2015-06-01

    This paper presents a survey on the occurrence and sources of 11 perfluoroalkyl acids (PFAA) in the main river basins in Italy, covering about 40% of the Italian surface area and 45% of the Italian population. Total concentrations of PFAA ranged fromchemical plants which produce fluorinated polymers and intermediates, sited in the basin of rivers Po and Brenta, respectively, whose overall emission represents 57% of the total estimated PFAA load. Both rivers flow into the Adriatic Sea, raising concern for the marine ecosystem also because a significant PFOS load (0.3ty(-1)) is still present. Among the remaining activities, tanneries and textile industries are relevant sources of respectively PFBS and PFOA, together with short chain PFCA. As an example, the total PFAA load (0.12ty(-1)) from the textile district of Prato is equivalent to the estimated domestic emission of the whole population in all the studied basins. PMID:25108894

  16. Parameters affecting the formation of perfluoroalkyl acids during wastewater treatment.

    PubMed

    Guerra, P; Kim, M; Kinsman, L; Ng, T; Alaee, M; Smyth, S A

    2014-05-15

    This study examined the fate and behaviour of perfluoroalkyl acids (PFAAs) in liquid and solid samples from five different wastewater treatment types: facultative and aerated lagoons, chemically assisted primary treatment, secondary aerobic biological treatment, and advanced biological nutrient removal treatment. To the best of our knowledge, this is the largest data set from a single study available in the literature to date for PFAAs monitoring study in wastewater treatment. Perfluorooctanoic acid (PFOA) was the predominant PFAA in wastewater with levels from 2.2 to 150ng/L (influent) and 1.9 to 140ng/L (effluent). Perfluorooctanesulfonic acid (PFOS) was the predominant compound in primary sludge, waste biological sludge, and treated biosolids with concentrations from 6.4 to 2900ng/g dry weight (dw), 9.7 to 8200ng/gdw, and 2.1 to 17,000ng/gdw, respectively. PFAAs were formed during wastewater treatment and it was dependant on both process temperature and treatment type; with higher rates of formation in biological wastewater treatment plants (WWTPs) operating at longer hydraulic retention times and higher temperatures. PFAA removal by sorption was influenced by different sorption tendencies; median log values of the solid-liquid distribution coefficient estimated from wastewater biological sludge and final effluent were: PFOS (3.73)>PFDA (3.68)>PFNA (3.25)>PFOA (2.49)>PFHxA (1.93). Mass balances confirmed the formation of PFAAs, low PFAA removal by sorption, and high PFAA levels in effluents. PMID:24691135

  17. Promotion of Hepatocarcinogenesis by Perfluoroalkyl Acids in Rainbow Trout

    PubMed Central

    Benninghoff, Abby D.; Orner, Gayle A.; Buchner, Clarissa H.; Hendricks, Jerry D.; Duffy, Aaron M.; Williams, David E.

    2012-01-01

    Previously, we reported that perfluorooctanoic acid (PFOA) promotes liver cancer in a manner similar to that of 17β-estradiol (E2) in rainbow trout. Also, other perfluoroalkyl acids (PFAAs) are weakly estrogenic in trout and bind the trout liver estrogen receptor. The primary objective of this study was to determine whether multiple PFAAs enhance hepatic tumorigenesis in trout, an animal model that represents human insensitivity to peroxisome proliferation. A two-stage chemical carcinogenesis model was employed in trout to evaluate PFOA, perfluorononanoic acid (PFNA), perfluorodecanoic acid (PFDA), perfluorooctane sulfonate (PFOS), and 8:2 fluorotelomer alcohol (8:2FtOH) as complete carcinogens or promoters of aflatoxin B1 (AFB1)- and/or N-methyl-N′-nitro-N-nitrosoguanidine (MNNG)-induced liver cancer. A custom trout DNA microarray was used to assess hepatic transcriptional response to these dietary treatments in comparison with E2 and the classic peroxisome proliferator, clofibrate (CLOF). Incidence, multiplicity, and size of liver tumors in trout fed diets containing E2, PFOA, PFNA, and PFDA were significantly higher compared with AFB1-initiated animals fed control diet, whereas PFOS caused a minor increase in liver tumor incidence. E2 and PFOA also enhanced MNNG-initiated hepatocarcinogenesis. Pearson correlation analyses, unsupervised hierarchical clustering, and principal components analyses showed that the hepatic gene expression profiles for E2 and PFOA, PFNA, PFDA, and PFOS were overall highly similar, though distinct patterns of gene expression were evident for each treatment, particularly for PFNA. Overall, these data suggest that multiple PFAAs can promote liver cancer and that the mechanism of promotion may be similar to that of E2. PMID:21984479

  18. Environmental-Fate Patterns for Perfluoroalkylates and their Precursors

    EPA Science Inventory

    Two sites with elevated concentrations of perfluoroalkylates (PFAs) and fluorotelomer alcohols (FTOHs) were studied: 1) agricultural fields near Decatur, AL on which sewage sludge had been applied; and 2) the Conasauga River system near Dalton, GA where treated sewage effluent is...

  19. Prenatal Phthalate, Perfluoroalkyl Acid, and Organochlorine Exposures and Term Birth Weight in Three Birth Cohorts: Multi-Pollutant Models Based on Elastic Net Regression

    PubMed Central

    Lenters, Virissa; Portengen, Lützen; Rignell-Hydbom, Anna; Jönsson, Bo A.G.; Lindh, Christian H.; Piersma, Aldert H.; Toft, Gunnar; Bonde, Jens Peter; Heederik, Dick; Rylander, Lars; Vermeulen, Roel

    2015-01-01

    Background Some legacy and emerging environmental contaminants are suspected risk factors for intrauterine growth restriction. However, the evidence is equivocal, in part due to difficulties in disentangling the effects of mixtures. Objectives We assessed associations between multiple correlated biomarkers of environmental exposure and birth weight. Methods We evaluated a cohort of 1,250 term (≥ 37 weeks gestation) singleton infants, born to 513 mothers from Greenland, 180 from Poland, and 557 from Ukraine, who were recruited during antenatal care visits in 2002‒2004. Secondary metabolites of diethylhexyl and diisononyl phthalates (DEHP, DiNP), eight perfluoroalkyl acids, and organochlorines (PCB-153 and p,p´-DDE) were quantifiable in 72‒100% of maternal serum samples. We assessed associations between exposures and term birth weight, adjusting for co-exposures and covariates, including prepregnancy body mass index. To identify independent associations, we applied the elastic net penalty to linear regression models. Results Two phthalate metabolites (MEHHP, MOiNP), perfluorooctanoic acid (PFOA), and p,p´-DDE were most consistently predictive of term birth weight based on elastic net penalty regression. In an adjusted, unpenalized regression model of the four exposures, 2-SD increases in natural log–transformed MEHHP, PFOA, and p,p´-DDE were associated with lower birth weight: –87 g (95% CI: –137, –340 per 1.70 ng/mL), –43 g (95% CI: –108, 23 per 1.18 ng/mL), and –135 g (95% CI: –192, –78 per 1.82 ng/g lipid), respectively; and MOiNP was associated with higher birth weight (46 g; 95% CI: –5, 97 per 2.22 ng/mL). Conclusions This study suggests that several of the environmental contaminants, belonging to three chemical classes, may be independently associated with impaired fetal growth. These results warrant follow-up in other cohorts. Citation Lenters V, Portengen L, Rignell-Hydbom A, Jönsson BA, Lindh CH, Piersma AH, Toft G, Bonde JP

  20. Assessment of serum biomarkers in rats after exposure to pesticides of different chemical classes

    SciTech Connect

    Moser, Virginia C.; McMahen, Rebecca L.; Strynar, Mark J.; Herr, David W.

    2015-01-15

    There is increasing emphasis on the use of biomarkers of adverse outcomes in safety assessment and translational research. We evaluated serum biomarkers and targeted metabolite profiles after exposure to pesticides (permethrin, deltamethrin, imidacloprid, carbaryl, triadimefon, fipronil) with different neurotoxic actions. Adult male Long–Evans rats were evaluated after single exposure to vehicle or one of two doses of each pesticide at the time of peak effect. The doses were selected to produce similar magnitude of behavioral effects across chemicals. Serum or plasma was analyzed using commercial cytokine/protein panels and targeted metabolomics. Additional studies of fipronil used lower doses (lacking behavioral effects), singly or for 14 days, and included additional markers of exposure and biological activity. Biomarker profiles varied in the number of altered analytes and patterns of change across pesticide classes, and discriminant analysis could separate treatment groups from control. Low doses of fipronil produced greater effects when given for 14 days compared to a single dose. Changes in thyroid hormones and relative amounts of fipronil and its sulfone metabolite also differed between the dosing regimens. Most cytokine changes reflected alterations in inflammatory responses, hormone levels, and products of phospholipid, fatty acid, and amino acid metabolism. These findings demonstrate distinct blood-based analyte profiles across pesticide classes, dose levels, and exposure duration. These results show promise for detailed analyses of these biomarkers and their linkages to biological pathways. - Highlights: • Pesticides typical of different classes produced distinct patterns of change in biomarker panels. • Based on the panels used, alterations suggest impacts on immune, metabolism, and homeostasis functions. • Some changes may reflect actions on neurotransmitter systems involved in immune modulation. • Fipronil effects on thyroid and kinetics

  1. Chemo-, regio-, and stereo-selective perfluoroalkylations by a Grignard complex with zirconocene.

    PubMed

    Fujiu, Motohiro; Negishi, Kazuyuki; Guang, Jie; Williard, Paul G; Kuroki, Shigeki; Mikami, Koichi

    2015-12-01

    The synthesis of highly reactive perfluoroalkyl Grignard reagents with early transition metal zirconocene complexes and their new types of highly chemo-, regio-, and stereo-selective perfluoroalkylation reactions are reported with epoxides in particular. The zirconocene complex is advantageous in activating the perfluoroalkyl Grignard species. The zirconocene·Grignard complexes were clarified by DOSY. Both (1)H and (19)F DOSY analyses show that the addition of MAO and dioxane to the mixture of RFMgCl and Cp2ZrCl2 connects Cp2Zr and RFMg to generate the zirconocene/perfluoroalkyl-Grignard/dioxane complex. PMID:26440224

  2. Perfluoroalkylated substances in the global tropical and subtropical surface oceans.

    PubMed

    González-Gaya, Belén; Dachs, Jordi; Roscales, Jose L; Caballero, Gemma; Jiménez, Begoña

    2014-11-18

    In this study, perfluoroalkylated substances (PFASs) were analyzed in 92 surface seawater samples taken during the Malaspina 2010 expedition which covered all the tropical and subtropical Atlantic, Pacific and Indian oceans. Nine ionic PFASs including C6-C10 perfluoroalkyl carboxylic acids (PFCAs), C4 and C6-C8 perfluoroalkyl sulfonic acids (PFSAs) and two neutral precursors perfluoroalkyl sulfonamides (PFASAs), were identified and quantified. The Atlantic Ocean presented the broader range in concentrations of total PFASs (131-10900 pg/L, median 645 pg/L, n = 45) compared to the other oceanic basins, probably due to a better spatial coverage. Total concentrations in the Pacific ranged from 344 to 2500 pg/L (median = 527 pg/L, n = 27) and in the Indian Ocean from 176 to 1976 pg/L (median = 329, n = 18). Perfluorooctanesulfonic acid (PFOS) was the most abundant compound, accounting for 33% of the total PFASs globally, followed by perfluorodecanoic acid (PFDA, 22%) and perfluorohexanoic acid (PFHxA, 12%), being the rest of the individual congeners under 10% of total PFASs, even for perfluorooctane carboxylic acid (PFOA, 6%). PFASAs accounted for less than 1% of the total PFASs concentration. This study reports the ubiquitous occurrence of PFCAs, PFSAs, and PFASAs in the global ocean, being the first attempt, to our knowledge, to show a comprehensive assessment in surface water samples collected in a single oceanic expedition covering tropical and subtropical oceans. The potential factors affecting their distribution patterns were assessed including the distance to coastal regions, oceanic subtropical gyres, currents and biogeochemical processes. Field evidence of biogeochemical controls on the occurrence of PFASs was tentatively assessed considering environmental variables (solar radiation, temperature, chlorophyll a concentrations among others), and these showed significant correlations with some PFASs, but explaining small to moderate percentages of variability

  3. Optimisation of hybridoma cell growth and monoclonal antibody secretion in a chemically defined, serum- and protein-free culture medium.

    PubMed

    Schneider, Y J

    1989-01-01

    Monoclonal antibodies (MAbs), for human use require chemical and biological purity. The best approach seems in vitro cultivation in a serum-, protein-free medium. A basal defined culture medium has been developed to sustain optimal hybridoma cell growth and MAb secretion. It consists of Iscove's Dulbecco's modified, Eagle's, Ham's F12 and NCTC 135 media in a 5:5:1 mixture (v/v/v), to which glucose is added to reach a final concentration of 25 mM, glutamine to 4-6 mM, 2-mercaptoethanol to 50 microM, Pluronic F68 to 0.01-0.1% (w/v), Hepes to 25 mM and NaHCO3 to 3 g/l. Hybridoma cells, derived from Sp 2/0 myeloma and secreting a MAb to a human milk fat globule membrane-associated high molecular weight glycoprotein, were cloned in this medium containing 1% (v/v) fetal calf serum and then sequentially adapted in serum-free medium further supplemented with transferrin and insulin, both at 10 micrograms/ml. Clones producing immunoreactive MAbs secrete a mean of 50 micrograms IgG/ml, i.e., ca. 80% of the concentration reached in Dulbecco's modified Eagle's medium containing 10% serum. When cells were cultured in spinner flasks with a semi-continuous mode of cultivation (with a daily removal of 20% of the volume and its replacement by fresh culture medium), in serum-free medium further supplemented with 10 nM estradiol, a mixture of trace elements and albumin (at 30 micrograms/ml) complexed to linoleic acid, MAb secretion reached 100 micrograms/ml and became equal or higher to that obtained in serum-containing medium. MAb secretion was not decreased and was even significantly increased during the growth phase, when transferrin was replaced by another iron source, i.e., ferric citrate at 500 microM associated with 20 microM ascorbic acid. Finally, deletion of insulin and of albumin-linoleic acid did not affect significantly cell density nor MAb secretion. In conclusion, it appears from this study that semi-continuous cultivation in spinner flasks of hybridoma cells, after

  4. Placental Transfer of Perfluoroalkyl Substances and Associations with Thyroid Hormones: Beijing Prenatal Exposure Study

    NASA Astrophysics Data System (ADS)

    Yang, Lin; Li, Jingguang; Lai, Jianqiang; Luan, Hemi; Cai, Zongwei; Wang, Yibaina; Zhao, Yunfeng; Wu, Yongning

    2016-02-01

    Perfluoroalkyl substances (PFASs) have been detected in wildlife and human samples worldwide. Toxicology research showed that PFASs could interfere with thyroid hormone homeostasis. In this study, eight PFASs, fifteen PFAS precursors and five thyroid hormones were analyzed in 157 paired maternal and cord serum samples collected in Beijing around delivery. Seven PFASs and two precursors were detected in both maternal and cord sera with significant maternal-fetal correlations (r = 0.336 to 0.806, all P < 0.001). The median ratios of major PFASs concentrations in fetal versus maternal serum were from 0.25:1 (perfluorodecanoic acid, PFDA) to 0.65:1 (perfluorooctanoic acid, PFOA). Spearman partial correlation test showed that maternal thyroid stimulating hormone (TSH) was negatively correlated with most maternal PFASs (r = -0.261 to -0.170, all P < 0.05). Maternal triiodothyronin (T3) and free T3 (FT3) showed negative correlations with most fetal PFASs (r = -0.229 to -0.165 for T3; r = -0.293 to -0.169 for FT3, all P < 0.05). Our results suggest prenatal exposure of fetus to PFASs and potential associations between PFASs and thyroid hormone homeostasis in humans.

  5. Placental Transfer of Perfluoroalkyl Substances and Associations with Thyroid Hormones: Beijing Prenatal Exposure Study

    PubMed Central

    Yang, Lin; Li, Jingguang; Lai, Jianqiang; Luan, Hemi; Cai, Zongwei; Wang, Yibaina; Zhao, Yunfeng; Wu, Yongning

    2016-01-01

    Perfluoroalkyl substances (PFASs) have been detected in wildlife and human samples worldwide. Toxicology research showed that PFASs could interfere with thyroid hormone homeostasis. In this study, eight PFASs, fifteen PFAS precursors and five thyroid hormones were analyzed in 157 paired maternal and cord serum samples collected in Beijing around delivery. Seven PFASs and two precursors were detected in both maternal and cord sera with significant maternal-fetal correlations (r = 0.336 to 0.806, all P < 0.001). The median ratios of major PFASs concentrations in fetal versus maternal serum were from 0.25:1 (perfluorodecanoic acid, PFDA) to 0.65:1 (perfluorooctanoic acid, PFOA). Spearman partial correlation test showed that maternal thyroid stimulating hormone (TSH) was negatively correlated with most maternal PFASs (r = −0.261 to −0.170, all P < 0.05). Maternal triiodothyronin (T3) and free T3 (FT3) showed negative correlations with most fetal PFASs (r = −0.229 to −0.165 for T3; r = −0.293 to −0.169 for FT3, all P < 0.05). Our results suggest prenatal exposure of fetus to PFASs and potential associations between PFASs and thyroid hormone homeostasis in humans. PMID:26898235

  6. Placental Transfer of Perfluoroalkyl Substances and Associations with Thyroid Hormones: Beijing Prenatal Exposure Study

    NASA Astrophysics Data System (ADS)

    Yang, Lin; Li, Jingguang; Lai, Jianqiang; Luan, Hemi; Cai, Zongwei; Wang, Yibaina; Zhao, Yunfeng; Wu, Yongning

    2016-02-01

    Perfluoroalkyl substances (PFASs) have been detected in wildlife and human samples worldwide. Toxicology research showed that PFASs could interfere with thyroid hormone homeostasis. In this study, eight PFASs, fifteen PFAS precursors and five thyroid hormones were analyzed in 157 paired maternal and cord serum samples collected in Beijing around delivery. Seven PFASs and two precursors were detected in both maternal and cord sera with significant maternal-fetal correlations (r = 0.336 to 0.806, all P < 0.001). The median ratios of major PFASs concentrations in fetal versus maternal serum were from 0.25:1 (perfluorodecanoic acid, PFDA) to 0.65:1 (perfluorooctanoic acid, PFOA). Spearman partial correlation test showed that maternal thyroid stimulating hormone (TSH) was negatively correlated with most maternal PFASs (r = ‑0.261 to ‑0.170, all P < 0.05). Maternal triiodothyronin (T3) and free T3 (FT3) showed negative correlations with most fetal PFASs (r = ‑0.229 to ‑0.165 for T3; r = ‑0.293 to ‑0.169 for FT3, all P < 0.05). Our results suggest prenatal exposure of fetus to PFASs and potential associations between PFASs and thyroid hormone homeostasis in humans.

  7. Prenatal Perfluoroalkyl Substance Exposure and Child Adiposity at 8 Years of Age: The HOME Study

    PubMed Central

    Braun, Joseph M.; Chen, Aimin; Romano, Megan E.; Calafat, Antonia M.; Webster, Glenys M.; Yolton, Kimberly; Lanphear, Bruce P.

    2015-01-01

    Objective To examine relationships between prenatal perfluoroalkyl substance (PFAS) exposure and adiposity in children born to women who lived downstream from a fluoropolymer manufacturing plant. Methods Data are from a prospective cohort in Cincinnati, OH (HOME Study). We measured perfluorooctanoic (PFOA), perfluorooctane sulfonic (PFOS), perfluorononanoic (PFNA), and perfluorohexane sulfonic (PFHxS) acids in prenatal serum samples. We estimated differences in body mass index z-scores (BMI), waist circumference, and body fat at 8 years of age (n=204) and BMI between 2–8 years of age (n=285) according to PFAS concentrations. Results Children born to women in the top two PFOA terciles had greater adiposity at 8 years than children in the 1st tercile. For example, waist circumference (cm) was higher among children in the 2nd (4.3; 95% CI:1.7, 6.9) and 3rd tercile (2.2; 95% CI:−0.5, 4.9) compared to children in the 1st tercile. Children in the top two PFOA terciles also had greater BMI gains from 2–8 years compared to children in the 1st tercile (p<0.05). PFOS, PFNA and PFHxS were not associated with adiposity. Conclusions In this cohort, higher prenatal serum PFOA concentrations were associated with greater adiposity at 8 years and a more rapid increase in BMI between 2–8 years. PMID:26554535

  8. Distribution of perfluoroalkyl compounds in rats: Indication for using hair as bioindicator of exposure.

    PubMed

    Gao, Bei; He, Xin; Liu, Wei; Zhang, Huanhuan; Saito, Norimitsu; Tsuda, Shuji

    2015-01-01

    Hair analysis is potentially advantageous in exposure assessment of perfluoroalkyl acids (PFAAs) as a non-invasive method, combined with the ability to reflect long-term exposure. The present study aims to assess the feasibility of using hair as an indicator of PFAA exposure. Adult male and female rats were subchronically exposed to selected PFAAs, including perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), and perfluorooctanesulfonate (PFOS), for 90 days. Hair, serum, and other tissues, including liver, kidney, spleen, lung, brain and heart, as well as the urine and feces excretions, were analyzed for PFAA levels. PFOA/PFNA/PFOS were detected in rat hair in a dose-dependent manner, in the order of PFOS>PFNA>PFOA. Hair PFAA concentrations were higher in male rats than the female rats, except for PFOS at low dose. Moreover, significant positive correlations as well as similar PFAA profiles were observed between hair, serum, and other tissues. Besides, hair PFAAs were negatively correlated with the urinary excretion rate. Although the influencing factors in humans still need further investigation, the results suggested that hair is capable of reflecting PFAA exposure, and could be employed as an alternative exposure bioindicator of PFAAs.

  9. Systematic determination of perfluoroalkyl and polyfluoroalkyl substances (PFASs) in outdoor jackets.

    PubMed

    Gremmel, Christoph; Frömel, Tobias; Knepper, Thomas P

    2016-10-01

    Sixteen outdoor jackets were purchased in 2011/12 and analyzed for 23 different perfluoroalkyl and polyfluoroalkyl substances (PFASs). The jackets were selected based on their origin of production, price, market, and textile, such as polyester, nylon, polyamide, and content of poly(tetrafluoroethylene) membranes. Two robust analytical methods based on high pressure liquid chromatography combined with tandem mass spectrometry, as well as two liquid extractions, were developed enabling the analysis of PFASs with widely different physico-chemical properties. The jackets were found to contain PFASs in a range between 0.03 and 719 μg/m(2). Perfluorooctanoic acid (PFOA) was omnipresent (0.02-171 μg/m(2)), although at lower concentrations compared to the precursors of perfluoroalkyl carboxylic acids (PFCAs), namely fluorotelomer alcohols (FTOHs) (<0.001-698 μg/m(2)). Perfluoroalkane sulfonic acids and their putative precursors, in particular perfluoroalkane sulfonamides, were detected much less frequently at concentrations up to 5 μg/m(2). To determine the effect of the volatility of FTOHs, four selected jackets were stored in a sealed bag in the dark at room temperature and re-analyzed after 3.5 years. Only 10%-20% of the initial concentration of 8:2-FTOH and 20%-50% of 10:2-FTOH were found, whereas the concentrations of PFOA and perfluorodecanoic acid increased significantly. This supports the hypothesis that PFAS concentrations in textiles are also strongly dependent on age, and conditions of transport and storage. PMID:27376856

  10. Growth performance, carcass traits, meat chemical composition and blood serum metabolites of broiler chicken fed on diets containing flaxseed oil.

    PubMed

    Lopes, D C N; Xavier, E G; Santos, V L; Gonçalves, F M; Anciuti, M A; Roll, V F B; Del Pino, F A B; Feijó, J O; Catalan, A A S

    2013-01-01

    1. This study evaluated the effects of diets with partial and total substitution of soya bean oil (SO) with flaxseed (linseed) oil (FO) on broiler chicken performance, carcass traits, meat chemical composition and blood serum metabolites. 2. A total of 448 one-d-old Cobb 500 broiler chicken were used. They were allotted among 4 treatments with 8 replications, using a completely randomised design, for 35 d. Four diets were compared: T1 = 100% SO (3%, 1-7 d; 4%, 8-21 d; and 5%, 22-35 d); T2 = 50% SO + 50% FO; T3 = 25% SO + 75% FO and T4 = 100% FO. 3. No significant differences were observed in body weight (BW), body weight gain (BWG), feed intake (FI), feed conversion ratio (FCR) and blood serum metabolites (total triglycerides, TRI; total cholesterol, CHO; high-density lipoprotein, HDL; low-density lipoprotein, LDL; glucose, GLU; albumin, ALB; globulin, GLO; and total proteins, TPs). Significant effects were observed for TRI, CHO, HDL, GLU, HDL, LDL, ALB and GLO with regard to the day of collection. 4. Carcass traits did not show significant differences for the treatments. No significant differences were observed for breast and drumstick chemical compositions, with the exception of drumstick fat concentration (quadratic effect). 5. In conclusion, the partial or total substitution of SO with FO did not affect growth performance, carcass traits, meat chemical composition or blood serum profile in broiler chicken. Therefore, FO can be an alternative to SO in the diet formulation for broiler chicken.

  11. Association of Perfluoroalkyl Substances, Bone Mineral Density, and Osteoporosis in the U.S. Population in NHANES 2009–2010

    PubMed Central

    Khalil, Naila; Chen, Aimin; Lee, Miryoung; Czerwinski, Stefan A.; Ebert, James R.; DeWitt, Jamie C.; Kannan, Kurunthachalam

    2015-01-01

    Background Perfluoroalkyl substances (PFASs), including perfluorooctanoic acid (PFOA), perfluorooctane sulfonic acid (PFOS), perfluorohexane sulfonic acid (PFHxS), and perfluorononanoic acid (PFNA), are detectable in the serum of 95% of the U.S. population. Objective Considering the role of PFASs as endocrine disruptors, we examined their relationships with bone health. Methods The association between serum PFAS concentration and bone mineral density at total femur (TFBMD), femoral neck (FNBMD), lumbar spine (LSBMD), and physician-diagnosed osteoporosis was assessed in 1,914 participants using data from the National Health and Nutritional Examination Survey 2009–2010. Results The mean age of the participants was 43 years. Men had higher serum PFAS concentrations than women (p < 0.001) except for PFNA. In both sexes, serum PFOS concentrations were inversely associated with FNBMD (p < 0.05). In women, significant negative associations were observed for natural log (ln)–transformed PFOS exposure with TFBMD and FNBMD, and for ln-transformed PFOA exposure with TFBMD (p < 0.05). In postmenopausal women, serum PFOS was negatively associated with TFBMD and FNBMD, and PFNA was negatively associated with TFBMD, FNBMD, and LSBMD (all p < 0.05). With one log unit increase in serum PFOA, PFHxS, and PFNA, osteoporosis prevalence in women increased as follows: [adjusted odds ratios (aORs)] 1.84 (95% CI: 1.17, 2.905), 1.64 (95% CI: 1.14, 2.38), and 1.45 (95% CI: 1.02, 2.05), respectively. In women, the prevalence of osteoporosis was significantly higher in the highest versus the lowest quartiles of PFOA, PFHxS, and PFNA, with aORs of 2.59 (95% CI: 1.01, 6.67), 13.20 (95% CI: 2.72, 64.15), and 3.23 (95% CI: 1.44, 7.21), respectively, based on 77 cases in the study sample. Conclusion In a representative sample of the U.S. adult population, serum PFAS concentrations were associated with lower bone mineral density, which varied according to the specific PFAS and bone site assessed

  12. Perfluoroalkyl acids in the Atlantic and Canadian Arctic Oceans.

    PubMed

    Benskin, Jonathan P; Muir, Derek C G; Scott, Brian F; Spencer, Christine; De Silva, Amila O; Kylin, Henrik; Martin, Jonathan W; Morris, Adam; Lohmann, Rainer; Tomy, Gregg; Rosenberg, Bruno; Taniyasu, Sachi; Yamashita, Nobuyoshi

    2012-06-01

    We report here on the spatial distribution of C(4), C(6), and C(8) perfluoroalkyl sulfonates, C(6)-C(14) perfluoroalkyl carboxylates, and perfluorooctanesulfonamide in the Atlantic and Arctic Oceans, including previously unstudied coastal waters of North and South America, and the Canadian Arctic Archipelago. Perfluorooctanoate (PFOA) and perfluorooctanesulfonate (PFOS) were typically the dominant perfluoroalkyl acids (PFAAs) in Atlantic water. In the midnorthwest Atlantic/Gulf Stream, sum PFAA concentrations (∑PFAAs) were low (77-190 pg/L) but increased rapidly upon crossing into U.S. coastal water (up to 5800 pg/L near Rhode Island). ∑PFAAs in the northeast Atlantic were highest north of the Canary Islands (280-980 pg/L) and decreased with latitude. In the South Atlantic, concentrations increased near Rio de la Plata (Argentina/Uruguay; 350-540 pg/L ∑PFAAs), possibly attributable to insecticides containing N-ethyl perfluorooctanesulfonamide, or proximity to Montevideo and Buenos Aires. In all other southern hemisphere locations, ∑PFAAs were <210 pg/L. PFOA/PFOS ratios were typically ≥1 in the northern hemisphere, ∼1 near the equator, and ≤1 in the southern hemisphere. In the Canadian Arctic, ∑PFAAs ranged from 40 to 250 pg/L, with perfluoroheptanoate, PFOA, and PFOS among the PFAAs detected at the highest concentrations. PFOA/PFOS ratios (typically ≫1) decreased from Baffin Bay to the Amundsen Gulf, possibly attributable to increased atmospheric inputs. These data help validate global emissions models and contribute to understanding of long-range transport pathways and sources of PFAAs to remote regions. PMID:22548373

  13. Evidence of remediation-induced alteration of subsurface poly- and perfluoroalkyl substance distribution at a former firefighter training area.

    PubMed

    McGuire, Meghan E; Schaefer, Charles; Richards, Trenton; Backe, Will J; Field, Jennifer A; Houtz, Erika; Sedlak, David L; Guelfo, Jennifer L; Wunsch, Assaf; Higgins, Christopher P

    2014-06-17

    Poly- and perfluoroalkyl substances (PFASs) are a class of fluorinated chemicals that are utilized in firefighting and have been reported in groundwater and soil at several firefighter training areas. In this study, soil and groundwater samples were collected from across a former firefighter training area to examine the extent to which remedial activities have altered the composition and spatial distribution of PFASs in the subsurface. Log Koc values for perfluoroalkyl acids (PFAAs), estimated from analysis of paired samples of groundwater and aquifer solids, indicated that solid/water partitioning was not entirely consistent with predictions based on laboratory studies. Differential PFAA transport was not strongly evident in the subsurface, likely due to remediation-induced conditions. When compared to the surface soil spatial distributions, the relative concentrations of perfluorooctanesulfonate (PFOS) and PFAA precursors in groundwater strongly suggest that remedial activities altered the subsurface PFAS distribution, presumably through significant pumping of groundwater and transformation of precursors to PFAAs. Additional evidence for transformation of PFAA precursors during remediation included elevated ratios of perfluorohexanesulfonate (PFHxS) to PFOS in groundwater near oxygen sparging wells.

  14. Differential accumulation and elimination behavior of perfluoroalkyl Acid isomers in occupational workers in a manufactory in China.

    PubMed

    Gao, Yan; Fu, Jianjie; Cao, Huiming; Wang, Yawei; Zhang, Aiqian; Liang, Yong; Wang, Thanh; Zhao, Chunyan; Jiang, Guibin

    2015-06-01

    In this study, serum and urine samples were collected from 36 occupational workers in a fluorochemical manufacturing plant in China from 2008 to 2012 to evaluate the body burden and possible elimination of linear and branched perfluoroalkyl acids (PFAAs). Indoor dust, total suspended particles (TSP), diet, and drinking water samples were also collected to trace the occupational exposure pathway to PFAA isomers. The geometric mean concentrations of perfluorooctanesulfonate (PFOS), perfluorooctanoate (PFOA), and perfluorohexanesulfonate (PFHxS) isomers in the serum were 1386, 371, and 863 ng mL(-1), respectively. The linear isomer of PFOS, PFOA, and PFHxS was the most predominant PFAA in the serum, with mean proportions of 63.3, 91.1, and 92.7% respectively, which were higher than the proportions in urine. The most important exposure routes to PFAA isomers in the occupational workers were considered to be the intake of indoor dust and TSP. A renal clearance estimation indicated that branched PFAA isomers had a higher renal clearance rate than did the corresponding linear isomers. Molecular docking modeling implied that linear PFOS (n-PFOS) had a stronger interaction with human serum albumin (HSA) than branched isomers did, which could decrease the proportion of n-PFOS in the blood of humans via the transport of HSA.

  15. Major perfluoroalkyl acid (PFAA) concentrations and influence of food consumption among the general population of Daegu, Korea.

    PubMed

    Ji, Kyunghee; Kim, Sunmi; Kho, Younglim; Sakong, Joon; Paek, Domyung; Choi, Kyungho

    2012-11-01

    Perfluoroalkyl acids (PFAAs) have been used in various industrial and consumer products for decades, and have consequently been detected in human blood worldwide. In the present study, general adult population in Daegu, Korea (n=140, >20 years of old) was recruited, collected for serum, and analyzed for 13 major PFAAs. The influence of dietary and water consumption on serum PFAA levels was also evaluated. Perfluorooctane sulfonic acid (PFOS), perfluorooctanoic acid (PFOA), and perfluorohexane sulfonic acid (PFHxS) were frequently detected with relatively higher concentrations in blood serum. Most PFAA concentrations except for PFOA were detected in higher concentrations among males, and were positively correlated with age and body mass index (BMI). PFOA concentrations were relatively higher among the female of childbearing age, e.g., 20-49years old, raising concerns on potential impacts on fetus through transplacental transfer or lactation. In addition, the concentrations of PFOA in Daegu population were higher than other areas of Korea, suggesting a presence of distinctive sources in the area. Among food items, potato consumption was identified to be significant contributor to serum PFOA. For PFUnDA and PFTrDA levels, intake of fish/shellfish was positively associated. The results of this study will be useful in developing public health management options for PFAAs.

  16. Elevated levels of perfluoroalkyl acids in family members of occupationally exposed workers: the importance of dust transfer

    NASA Astrophysics Data System (ADS)

    Fu, Jianjie; Gao, Yan; Wang, Thanh; Liang, Yong; Zhang, Aiqian; Wang, Yawei; Jiang, Guibin

    2015-03-01

    The exposure pathways of perfluoroalkyl acids (PFAAs) to humans are still not clear because of the complex living environment, and few studies have simultaneously investigated the bioaccumulative behaviour of different PFAAs in humans. In this study, serum, dust, duplicate diet, and other matrices were collected around a manufacturing plant in China, and homologous series of PFAAs were analysed. PFAA levels in dust and serum of local residents in this area were considerably higher than those in non-polluted area. Although dietary intake was the major exposure pathway in the present study, dust ingestion played an important role in this case. Serum PFAAs in local residents was significantly correlated with dust PFAAs levels in their living or working microenvironment. Serum PFAAs and dust PFAAs were significantly higher in family members of occupational workers (FM) than in ordinary residents (OR) (p < 0.01). After a careful analysis of the PFAAs exposure pathway, a potential pathway in addition to direct dust ingestion was suggested: PFAAs might transferred from occupational worker's clothes to dinners via cooking processes. The bioaccumulative potential of PFHxS and PFOS were higher than other PFAAs, which suggested a substantial difference between the bioaccumulative ability of perfluorinated sulfonic acids and perfluorinated carboxylic acids.

  17. Elevated levels of perfluoroalkyl acids in family members of occupationally exposed workers: the importance of dust transfer.

    PubMed

    Fu, Jianjie; Gao, Yan; Wang, Thanh; Liang, Yong; Zhang, Aiqian; Wang, Yawei; Jiang, Guibin

    2015-03-20

    The exposure pathways of perfluoroalkyl acids (PFAAs) to humans are still not clear because of the complex living environment, and few studies have simultaneously investigated the bioaccumulative behaviour of different PFAAs in humans. In this study, serum, dust, duplicate diet, and other matrices were collected around a manufacturing plant in China, and homologous series of PFAAs were analysed. PFAA levels in dust and serum of local residents in this area were considerably higher than those in non-polluted area. Although dietary intake was the major exposure pathway in the present study, dust ingestion played an important role in this case. Serum PFAAs in local residents was significantly correlated with dust PFAAs levels in their living or working microenvironment. Serum PFAAs and dust PFAAs were significantly higher in family members of occupational workers (FM) than in ordinary residents (OR) (p < 0.01). After a careful analysis of the PFAAs exposure pathway, a potential pathway in addition to direct dust ingestion was suggested: PFAAs might transferred from occupational worker's clothes to dinners via cooking processes. The bioaccumulative potential of PFHxS and PFOS were higher than other PFAAs, which suggested a substantial difference between the bioaccumulative ability of perfluorinated sulfonic acids and perfluorinated carboxylic acids.

  18. Firefighters' exposure to perfluoroalkyl acids and 2-butoxyethanol present in firefighting foams.

    PubMed

    Laitinen, Juha Ari; Koponen, Jani; Koikkalainen, Janne; Kiviranta, Hannu

    2014-12-01

    The aim of this study was to assess eight firefighters' exposure to Sthamex 3% AFFF (aqueous film forming foam) in the simulation of aircraft accidents at Oulu airport in Finland. Study was conducted in 2010 before limitation for the use of PFOA and PFOS in AFFFs. Due to prospective limitation also eight commercially available AFFFs were evaluated from occupational and environmental point of view to find substitutive AFFFs for future. The firefighters' exposure to twelve perfluoroalkyl acids (PFAS) was analyzed in order to observe the signs of accumulation during three consecutive training sessions. The firefighters' short-term exposure to 2-butoxyethanol (EGBE) was analyzed by urinalysis of 2-butoxyacetic acid (2-BAA). For the background information also the concentration of PFAS in used AFFF-liquid was analyzed. Fire fighters' serum PFHxS and PFNA concentrations seemed to increase during the three training sessions although they were not the main PFAS in used AFFF. The statistical significance for the elevations was not able to test due to limited size of test group. In two training sessions, the average urinary excretions of 2-BAA exceeded the reference limit of the occupationally unexposed population. In the evaluations of the firefighting foams, non-fluorine based products were favored and the alcohol resistance properties of foams were recommended for consideration due to the increasing use of biofuels.

  19. Perfluoroalkyl substances (PFASs) and ovarian hormone concentrations in naturally cycling women

    PubMed Central

    Barrett, Emily S.; Chen, Chongshu; Thurston, Sally W.; Haug, Line Småstuen; Sabaredzovic, Azemira; Fjeldheim, Frøydis Nyborg; Frydenberg, Hanne; Lipson, Susan F.; Ellison, Peter T.; Thune, Inger

    2015-01-01

    Objective To examine associations between environmental exposure to perfluoroalkyl substances (PFASs) and ovarian hormone concentrations in naturally cycling women. Design Estradiol and progesterone were measured in saliva samples collected daily for a single menstrual cycle and concentrations of PFASs (including perfluoroctane sulfonate [PFOS] and perfluoroctanoic acid [PFOA]) were measured in serum samples collected during the same cycle. Setting Tromsø, Norway. Patients 178 healthy, naturally cycling women, ages 25-35. Intervention None. Main outcome measures(s) Mean follicular estradiol (cycle days −7 to −1, where 0 is the day of ovulation); mean luteal progesterone (cycle days +2 to 10). Results Among nulliparous, but not parous women, PFOS concentrations were inversely associated with estradiol (β=−0.025, 95% CI: −0.043, −0.007) and progesterone (β=−0.027, 95% CI: −0.048, −0.007). Similar, but weaker results were observed for perfluorooctanesulfonic acid (PFOSA). No associations were observed between other PFASs (including PFOA) and ovarian steroid concentrations, nor were any associations noted in parous women. Conclusions Our results demonstrate that PFOS and PFOSA may be associated with decreased production of estradiol and progesterone in reproductive age women. These results suggest a possible mechanism by which PFASs affect women's health, and underscore the importance of parity in research on PFASs and women's reproductive health. PMID:25747128

  20. Firefighters' exposure to perfluoroalkyl acids and 2-butoxyethanol present in firefighting foams.

    PubMed

    Laitinen, Juha Ari; Koponen, Jani; Koikkalainen, Janne; Kiviranta, Hannu

    2014-12-01

    The aim of this study was to assess eight firefighters' exposure to Sthamex 3% AFFF (aqueous film forming foam) in the simulation of aircraft accidents at Oulu airport in Finland. Study was conducted in 2010 before limitation for the use of PFOA and PFOS in AFFFs. Due to prospective limitation also eight commercially available AFFFs were evaluated from occupational and environmental point of view to find substitutive AFFFs for future. The firefighters' exposure to twelve perfluoroalkyl acids (PFAS) was analyzed in order to observe the signs of accumulation during three consecutive training sessions. The firefighters' short-term exposure to 2-butoxyethanol (EGBE) was analyzed by urinalysis of 2-butoxyacetic acid (2-BAA). For the background information also the concentration of PFAS in used AFFF-liquid was analyzed. Fire fighters' serum PFHxS and PFNA concentrations seemed to increase during the three training sessions although they were not the main PFAS in used AFFF. The statistical significance for the elevations was not able to test due to limited size of test group. In two training sessions, the average urinary excretions of 2-BAA exceeded the reference limit of the occupationally unexposed population. In the evaluations of the firefighting foams, non-fluorine based products were favored and the alcohol resistance properties of foams were recommended for consideration due to the increasing use of biofuels. PMID:25447453

  1. Perfluoroalkyl substances (PFASs) in food and water from Faroe Islands.

    PubMed

    Eriksson, Ulrika; Kärrman, Anna; Rotander, Anna; Mikkelsen, Bjørg; Dam, Maria

    2013-11-01

    Diet and drinking water are suggested to be major exposure pathways for perfluoroalkyl substances (PFASs). In this study, food items and water from Faroe Islands sampled in 2011/2012 were analyzed for 11 perfluoroalkyl carboxylic acids (PFCAs) and 4 perfluoroalkane sulfonic acids (PFSAs). The food samples included milk, yoghurt, crème fraiche, potatoes, fish, and fish feed, and the water samples included surface water and purified drinking water. In total, nine PFCAs and four PFSAs were detected. Generally, the levels of PFAS were in the lower picogram per gram range. Perfluorobutanoic acid was a major contributor to the total PFASs concentration in water samples and had a mean concentration of 750 pg/L. Perfluoroundecanoic acid (PFUnDA) was predominating in milk and wild fish with mean concentrations of 170 pg/g. Perfluorooctane sulfonic acid (PFOS) was most frequently detected in food items followed by PFUnDA, perfluorononanoic acid, and perfluorooctanoic acid (PFOA). Levels of PFUnDA and PFOA exceeded those of PFOS in milk and fish samples. Prevalence of long-chain PFCAs in Faroese food items and water is confirming earlier observations of their increase in Arctic biota. Predominance of short-chain and long-chain homologues indicates exposure from PFOS and PFOA replacement compounds.

  2. Estrogenic Activity of Perfluoroalkyl Acids in Juvenile Rainbow Trout (Oncorhynchus Mykiss)

    EPA Science Inventory

    The potential estrogenic activity of perfluoroalkyl acids (PFAAs) was determined using separate screening and dose response studies with juvenile rainbow trout (Oncorhynchus mykiss). Results of this study indicate that some PFAAs may act as estrogens in fish.

  3. Treatment of poly- and perfluoroalkyl substances in U.S. full-scale water treatment systems.

    PubMed

    Appleman, Timothy D; Higgins, Christopher P; Quiñones, Oscar; Vanderford, Brett J; Kolstad, Chad; Zeigler-Holady, Janie C; Dickenson, Eric R V

    2014-03-15

    The near ubiquitous presence of poly- and perfluoroalkyl substances (PFASs) in humans has raised concerns about potential human health effects from these chemicals, some of which are both extremely persistent and bioaccumulative. Because some of these chemicals are highly water soluble, one major pathway for human exposure is the consumption of contaminated drinking water. This study measured concentrations of PFASs in 18 raw drinking water sources and 2 treated wastewater effluents and evaluated 15 full-scale treatment systems for the attenuation of PFASs in water treatment utilities throughout the U.S. A liquid-chromatography tandem mass-spectrometry method was used to enable measurement of a suite of 23 PFASs, including perfluorocarboxylic acids (PFCAs) and perfluorosulfonic acids (PFSAs). Despite the differences in reporting levels, the PFASs that were detected in >70% of the source water samples (n = 39) included PFSAs, perfluorobutane sulfonic acid (74%), perfluorohexane sulfonic acid (79%), and perfluorooctane sulfonic acid (84%), and PFCAs, perfluoropentanoic acid (74%), perfluorohexanoic acid (79%), perfluoroheptanoic acid (74%), and perfluorooctanoic acid (74%). More importantly, water treatment techniques such as ferric or alum coagulation, granular/micro-/ultra- filtration, aeration, oxidation (i.e., permanganate, ultraviolet/hydrogen peroxide), and disinfection (i.e., ozonation, chlorine dioxide, chlorination, and chloramination) were mostly ineffective in removing PFASs. However, anion exchange and granular activated carbon treatment preferably removed longer-chain PFASs and the PFSAs compared to the PFCAs, and reverse osmosis demonstrated significant removal for all the PFASs, including the smallest PFAS, perfluorobutanoic acid.

  4. A national discharge load of perfluoroalkyl acids derived from industrial wastewater treatment plants in Korea.

    PubMed

    Kim, Hee-Young; Seok, Hyun-Woo; Kwon, Hye-Ok; Choi, Sung-Deuk; Seok, Kwang-Seol; Oh, Jeong Eun

    2016-09-01

    Levels of 11 perfluoroalkyl acids (PFAAs), including perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS), were measured in wastewater (influent and effluent) and sludge samples collected from 25 industrial wastewater treatment plants (I-WWTPs) in five industrial sectors (chemicals, electronics, metals, paper, and textiles) in South Korea. The highest ∑11PFAAs concentrations were detected in the influent and effluent from the paper (median: 411ng/L) and textile (median: 106ng/L) industries, and PFOA and PFOS were the predominant PFAAs (49-66%) in wastewater. Exceptionally high levels of PFAAs were detected in the sludge associated with the electronics (median: 91.0ng/g) and chemical (median: 81.5ng/g) industries with PFOS being the predominant PFAA. The discharge loads of 11 PFAAs from I-WWTP were calculated that total discharge loads for the five industries were 0.146ton/yr. The textile industry had the highest discharge load with 0.055ton/yr (PFOA: 0.039ton/yr, PFOS: 0.010ton/yr). Municipal wastewater contributed more to the overall discharge of PFAAs (0.489ton/yr) due to the very small industrial wastewater discharge compared to municipal wastewater discharge, but the contribution of PFAAs from I-WWTPs cannot be ignored.

  5. A national discharge load of perfluoroalkyl acids derived from industrial wastewater treatment plants in Korea.

    PubMed

    Kim, Hee-Young; Seok, Hyun-Woo; Kwon, Hye-Ok; Choi, Sung-Deuk; Seok, Kwang-Seol; Oh, Jeong Eun

    2016-09-01

    Levels of 11 perfluoroalkyl acids (PFAAs), including perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS), were measured in wastewater (influent and effluent) and sludge samples collected from 25 industrial wastewater treatment plants (I-WWTPs) in five industrial sectors (chemicals, electronics, metals, paper, and textiles) in South Korea. The highest ∑11PFAAs concentrations were detected in the influent and effluent from the paper (median: 411ng/L) and textile (median: 106ng/L) industries, and PFOA and PFOS were the predominant PFAAs (49-66%) in wastewater. Exceptionally high levels of PFAAs were detected in the sludge associated with the electronics (median: 91.0ng/g) and chemical (median: 81.5ng/g) industries with PFOS being the predominant PFAA. The discharge loads of 11 PFAAs from I-WWTP were calculated that total discharge loads for the five industries were 0.146ton/yr. The textile industry had the highest discharge load with 0.055ton/yr (PFOA: 0.039ton/yr, PFOS: 0.010ton/yr). Municipal wastewater contributed more to the overall discharge of PFAAs (0.489ton/yr) due to the very small industrial wastewater discharge compared to municipal wastewater discharge, but the contribution of PFAAs from I-WWTPs cannot be ignored. PMID:27152994

  6. Perfluoroalkyl Acid Concentrations in Blood Samples Subjected to Transportation and Processing Delay

    PubMed Central

    Bach, Cathrine Carlsen; Henriksen, Tine Brink; Bossi, Rossana; Bech, Bodil Hammer; Fuglsang, Jens; Olsen, Jørn; Nohr, Ellen Aagaard

    2015-01-01

    Background In studies of perfluoroalkyl acids, the validity and comparability of measured concentrations may be affected by differences in the handling of biospecimens. We aimed to investigate whether measured plasma levels of perfluoroalkyl acids differed between blood samples subjected to delay and transportation prior to processing and samples with immediate processing and freezing. Methods Pregnant women recruited at Aarhus University Hospital, Denmark, (n = 88) provided paired blood samples. For each pair of samples, one was immediately processed and plasma was frozen, and the other was delayed and transported as whole blood before processing and freezing of plasma (similar to the Danish National Birth Cohort). We measured 12 perfluoroalkyl acids and present results for compounds with more than 50% of samples above the lower limit of quantification. Results For samples taken in the winter, relative differences between the paired samples ranged between -77 and +38% for individual perfluoroalkyl acids. In most cases concentrations were lower in the delayed and transported samples, e.g. the relative difference was -29% (95% confidence interval -30; -27) for perfluorooctane sulfonate. For perfluorooctanoate there was no difference between the two setups [corresponding estimate 1% (0, 3)]. Differences were negligible in the summer for all compounds. Conclusions Transport of blood samples and processing delay, similar to conditions applied in some large, population-based studies, may affect measured perfluoroalkyl acid concentrations, mainly when outdoor temperatures are low. Attention to processing conditions is needed in studies of perfluoroalkyl acid exposure in humans. PMID:26356420

  7. Prenatal polybrominated diphenyl ether and perfluoroalkyl substance exposures and executive function in school-age children.

    PubMed

    Vuong, Ann M; Yolton, Kimberly; Webster, Glenys M; Sjödin, Andreas; Calafat, Antonia M; Braun, Joseph M; Dietrich, Kim N; Lanphear, Bruce P; Chen, Aimin

    2016-05-01

    Executive function is a critical behavioral trait rarely studied in relation to potential neurotoxicants. Prenatal exposure to polybrominated diphenyl ethers (PBDEs) and perfluoroalkyl substances (PFASs) has been associated with adverse neurodevelopment, but there is limited research on executive function. Data from 256 mother-child pairs in the Health Outcomes and Measures of the Environment Study, a prospective birth cohort (2003-2006, Cincinnati, OH), was used to examine maternal serum PBDEs and PFASs and executive function in children ages 5 and 8 years. Maternal serum PBDEs and PFASs were measured at 16±3 weeks gestation. Executive function was assessed with the parent-rated Behavior Rating Inventory of Executive Function (BRIEF), which yields composite measures: behavioral regulation index, metacognition index, and global executive composite. Higher BRIEF scores indicate executive function impairments. Linear mixed models and generalized estimating equations were used to estimate covariate-adjusted associations between PBDEs and PFASs and executive function. A 10-fold increase in BDE-153 was associated with poorer behavior regulation (β=3.23, 95% CI 0.60, 5.86). Higher odds of having a score ≥60 in behavior regulation (OR=3.92, 95% CI 1.76, 8.73) or global executive functioning (OR=2.34, 95% CI 1.05, 5.23) was observed with increased BDE-153. Each ln-unit increase in perfluorooctane sulfonate (PFOS) was associated with poorer behavior regulation (β=3.14, 95% CI 0.68, 5.61), metacognition (β=3.10, 95% CI 0.62, 5.58), and global executive functioning (β=3.38, 95% CI 0.86, 5.90). However, no association was observed between perfluorooctanoate (PFOA) and executive function. Prenatal exposures to BDE-153 and PFOS may be associated with executive function deficits in school-age children.

  8. Prenatal polybrominated diphenyl ether and perfluoroalkyl substance exposures and executive function in school-age children.

    PubMed

    Vuong, Ann M; Yolton, Kimberly; Webster, Glenys M; Sjödin, Andreas; Calafat, Antonia M; Braun, Joseph M; Dietrich, Kim N; Lanphear, Bruce P; Chen, Aimin

    2016-05-01

    Executive function is a critical behavioral trait rarely studied in relation to potential neurotoxicants. Prenatal exposure to polybrominated diphenyl ethers (PBDEs) and perfluoroalkyl substances (PFASs) has been associated with adverse neurodevelopment, but there is limited research on executive function. Data from 256 mother-child pairs in the Health Outcomes and Measures of the Environment Study, a prospective birth cohort (2003-2006, Cincinnati, OH), was used to examine maternal serum PBDEs and PFASs and executive function in children ages 5 and 8 years. Maternal serum PBDEs and PFASs were measured at 16±3 weeks gestation. Executive function was assessed with the parent-rated Behavior Rating Inventory of Executive Function (BRIEF), which yields composite measures: behavioral regulation index, metacognition index, and global executive composite. Higher BRIEF scores indicate executive function impairments. Linear mixed models and generalized estimating equations were used to estimate covariate-adjusted associations between PBDEs and PFASs and executive function. A 10-fold increase in BDE-153 was associated with poorer behavior regulation (β=3.23, 95% CI 0.60, 5.86). Higher odds of having a score ≥60 in behavior regulation (OR=3.92, 95% CI 1.76, 8.73) or global executive functioning (OR=2.34, 95% CI 1.05, 5.23) was observed with increased BDE-153. Each ln-unit increase in perfluorooctane sulfonate (PFOS) was associated with poorer behavior regulation (β=3.14, 95% CI 0.68, 5.61), metacognition (β=3.10, 95% CI 0.62, 5.58), and global executive functioning (β=3.38, 95% CI 0.86, 5.90). However, no association was observed between perfluorooctanoate (PFOA) and executive function. Prenatal exposures to BDE-153 and PFOS may be associated with executive function deficits in school-age children. PMID:26832761

  9. Exceptionally high serum concentrations of perfluorohexanesulfonate in a Canadian family are linked to home carpet treatment applications.

    PubMed

    Beesoon, Sanjay; Genuis, Stephen J; Benskin, Jonathan P; Martin, Jonathan W

    2012-12-01

    Perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) are normally the dominant perfluoroalkyl substances (PFASs) in human serum, but here a Canadian family of seven was identified with particularly high exposure to perfluorohexanesulfonate (PFHxS). Disproportionately high serum PFHxS concentrations (range 27.5-423 ng/mL) and moderately high PFOS (range 15.2-108 ng/mL) and PFOA (range 2.40-9.23 ng/mL) concentrations were detected in the family members, with all three chemicals being highest in the youngest children. We therefore sought to identify the source(s) and pathway(s) of this unusual exposure, and to study the excretion of PFASs for this family. Serum, urine, and stool were sampled from family members, carpet, dust, and air were sampled in the home, and a questionnaire was administered. Over 15 years, the family's household carpets were treated 8 times with Scotchgard formulations. Elevated concentrations of PFHxS were detected in household dust (2780 ng/g dust) and in family room carpet (2880 ng/g carpet), and the primary mode of excretion for the major PFASs was through urine. The high PFHxS and moderately high PFOS concentrations in serum and household samples are consistent with the known PFAS content of certain Scotchgard formulations, and exposure was likely through dust ingestion and/or inhalation.

  10. Microbial degradation of polyfluoroalkyl chemicals in the environment: a review.

    PubMed

    Liu, Jinxia; Mejia Avendaño, Sandra

    2013-11-01

    Polyfluoroalkyl chemicals containing perfluoroalkyl moieties have been widely used in numerous industrial and commercial applications. Many polyfluoroalkyl chemicals are potential perfluoroalkyl acid (PFAA) precursors. When they are released to the environment, abiotic and microbial degradation of non-fluorinated functionalities, polyfluoroalkyl and perfluoroalkyl moieties can result in perfluoroalkyl carboxylic (PFCAs) and sulfonic acids (PFSAs), such as perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS). These highly persistent and ubiquitously detected PFAAs are the subjects of many regulations and actions due to their toxic profiles. In order to confidently evaluate the environmental fate and effects of these precursors and their links to PFSAs and PFCAs, we present the review into the environmental biodegradability studies carried out with microbial culture, activated sludge, soil and sediment in the past decade. First, we propose that the knowledge gap caused by the lack of direct detection of precursor chemicals in environmental samples can be bridged by laboratory investigations of important precursors such as fluorotelomer-based compounds and perfluoroalkane sulfonamido derivatives. Then we evaluate the experimental setups and methodologies, sampling and sample preparation methods, and analytical techniques that have been successfully applied. Third, we provide the most updated knowledge on quantitative and qualitative relationships between precursors and PFSAs or PFCAs, microbial degradation pathways, half-lives of precursors, defluorination potential, and novel degradation intermediates and products. In the end, we identify knowledge gaps and suggest research directions with regard to future biodegradation studies, environmental monitoring and ecotoxicological assessment of perfluoroalkyl and polyfluoroalkyl chemicals.

  11. Difunctionalization of Styrenes with Perfluoroalkyl and tert-Butylperoxy Radicals: Room Temperature Synthesis of (1-(tert-Butylperoxy)-2-perfluoroalkyl)-ethylbenzene.

    PubMed

    Shi, Erbo; Liu, Jiajun; Liu, Chunmei; Shao, Ying; Wang, Hanghang; Lv, Yuanzheng; Ji, Meishan; Bao, Xiaoguang; Wan, Xiaobing

    2016-07-15

    A novel strategy for the difunctionalization of styrenes was developed. This synthesis includes the use of electrophilic perfluoroalkyl and tert-butylperoxy radicals and produces (1-(tert-butylperoxy)-2-perfluoroalkyl)ethylbenzene at room temperature, which has been traditionally difficult to synthesize. With at least four radical species included in the transformation, its high chemoselectivity was extraordinary; the results were further elucidated using computational studies. The methodology also holds a good potential for application as a result of its mild reaction conditions, ease of further modification, and insensitivity to moisture and air. PMID:27280318

  12. Patterns of clinical bioindicators in rat serum following acute exposure to pesticides of different chemical classes

    EPA Science Inventory

    There is interest in bioindicators of adverse outcomes in safety assessment and translational research. Chemically-induced neurological effects may be reflected in specific neuronal changes and/or by general stress-like responses, and such bioindicators may be useful for measurin...

  13. Are levels of perfluoroalkyl substances in soil related to urbanization in rapidly developing coastal areas in North China?

    PubMed

    Meng, Jing; Wang, Tieyu; Wang, Pei; Zhang, Yueqing; Li, Qifeng; Lu, Yonglong; Giesy, John P

    2015-04-01

    Concentrations of 13 perfluoroalkyl substances (PFASs) were quantified in 79 surface soil samples from 17 coastal cities in three provinces and one municipality along the Bohai and Yellow Seas. The ∑PFASs concentrations ranged from less than limitation of quantification (LOQ) to 13.97 ng/g dry weight (dw), with a mean of 0.98 ng/g dw. The highest concentration was observed along the Xiaoqing River from Shandong province, followed by that from the Haihe River in Tianjin (10.62 ng/g dw). Among four regions, ∑PFASs concentrations decreased in the order of Tianjin, Shandong, Liaoning and Hebei, which was consistent with levels of urbanization. Fluorine chemical industries allocated in Shandong and Liaoning played important roles in terms of point emission and contamination of PFASs, dominated by perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS). Intensive anthropogenic activities involved in urbanization possibly resulted in increasing releases of PFASs from industrial and domestic sources.

  14. Cotton fabric modification for imparting high water and oil repellency using perfluoroalkyl phosphate acrylate via γ-ray-induced grafting

    NASA Astrophysics Data System (ADS)

    Miao, Hui; Bao, Fenfen; Cheng, Liangliang; Shi, Wenfang

    2010-07-01

    The perfluoroalkyl phosphate acrylates were grafted onto a cotton fabric via γ-ray irradiation to improve the hydrophobic and oleophobic properties. The change in chemical structure of grafted cotton fabric was detected by the Fourier transform infrared spectroscopy and the X-ray photoelectron spectroscopy. The contact angles for water and sunflower oil were determined to be over 150° and 140°, respectively, after irradiated with a dose range of 471-5664 Gy. The flame retardancy of the fabric with a grafting ratio of over 13.0 wt% was improved, reaching to 24 compared with 18 of which before grafted, according to the limiting oxygen index measurement. The microstructure of the fabric before and after grafted was observed by the scanning electron microscope.

  15. Sorption of perfluoroalkyl substances to two types of minerals.

    PubMed

    Hellsing, Maja S; Josefsson, Sarah; Hughes, Arwel V; Ahrens, Lutz

    2016-09-01

    The sorption of perfluoroalkyl substances (PFASs) was investigated for two model soil mineral surfaces, alumina (Al2O3) and silica (SiO2), on molecular level using neutron scattering. The PFASs were selected (i.e. perfluorohexanoic acid (PFHxA), perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), and perfluorooctane sulfonic acid (PFOS)) to examine the role of hydrophobic chain length and hydrophilic functional group on their sorption behaviour. All four PFASs were found to sorb to alumina surface (positively charged) forming a hydrated layer consisting of 50% PFASs. The PFAS solubility limit, which decrease with chain length, was found to strongly influence the sorption behaviour. The sorbed PFAS layer could easily be removed by gentle rinsing with water, indicating release upon rainfall in the environment. No sorption was observed for PFOA and PFOS at silica surface (negatively charged), showing electrostatic interaction being the driving force in the sorption process. PMID:27323291

  16. Identification of Chemical Constituents in the Extract and Rat Serum from Ziziphus Jujuba Mill by HPLC-PDA-ESI-MSn

    PubMed Central

    Wang, Shuping; Zhang, Jingze; Zhang, Zhidan; Gao, Wenyuan; Yan, Yanan; Li, Xia; Liu, Changxiao

    2014-01-01

    Chinese jujube (Ziziphus jujuba Mill.) has long been widely used for human consumption and medicinal purposes in China. It has been reported to possess several vital biological activities. However, the systematic study on the chemical constituents absorbed into plasma and their metabolites is still insufficient.A high-performance liquid chromatography-photodiode array detector-electrospray ionization ion-mass spectrometry (HPLC-PDA-ESI-MSn) method was established to analyze the ethanol extract in Ziziphus jujuba Mill and the constituents absorbed into rat serum. In the present study, a dose of 10 mL/Kg of ethanol extract of jujube, which is equivalent to 12.5 g crude dried herb/Kg, was orally administrated to rats. The main components were analyzed in the ethanol extract of Ziziphus jujuba Mill and the parent constituents and metabolites were studied in rat plasma samples after oral administration of the ethanol extract of jujube.D101 macroporous polystyrene resin was a good pretreatment method to obtain better separation and impurity removal effect. Twenty-two compounds were identified in the ethanol extract of Ziziphus jujuba Mill. Four parent compounds and four metabolites were detected in rat serum. Among them, seventeen compounds were reported for the first time. PMID:25276208

  17. Spatio-temporal trends and monitoring design of perfluoroalkyl acids in the eggs of gull (Larid) species from across Canada and parts of the United States.

    PubMed

    Gewurtz, Sarah B; Martin, Pamela A; Letcher, Robert J; Burgess, Neil M; Champoux, Louise; Elliott, John E; Weseloh, D V Chip

    2016-09-15

    A large spatial dataset of perfluoroalkyl acid (PFAA) concentrations in eggs of herring gulls (Larus argentatus or congeneric species) collected from late April to early June between 2009 and 2014 from 28 colonies across Canada and parts of the Unites States was used to evaluate location-specific patterns in chemical concentrations and to generate hypotheses on the major sources affecting PFAA distributions. The highly bioaccumulative perfluorooctane sulfonic acid (PFOS) as well as other perfluoroalkyl sulfonic acids (PFSAs) showed the greatest concentrations in eggs from the lower Great Lakes of southern Ontario as well as from the St. Lawrence River. Despite the 2000 to 2002 phase-out of PFOS and related C8 chemistry by the major manufacturer at the time, ongoing losses from consumer products during use and disposal in urban/industrial locations continue to be major sources to the environment and are influencing the spatial trends of PFOS in Canada. In comparison to PFOS, perfluoroalkyl carboxylic acids (PFCAs) were not as concentrated in eggs in close proximity to urbanized/industrialized centers, but had surprisingly elevated levels in relatively remote regions such as Great Slave Lake, NT and East Bay in Hudson Bay, NU. The present results support the hypothesis that atmospheric transport and degradation of precursor chemicals, such as the fluorotelomer alcohols 8:2 FTOH and 10:2 FTOH, are influencing the spatial trends of PFCAs in Canada. A power analysis conducted on a representative urbanized/industrialized colony in the Toronto Harbour, ON, and a relatively remote colony in Lake Superior, emphasized the importance of consistent and long-term data collection in order to detect the anticipated changes in PFAA concentrations in Canadian gull eggs. PMID:27183458

  18. Perfluoroalkyl acid contamination of follicular fluid and its consequence for in vitro oocyte developmental competence.

    PubMed

    Petro, Evi M L; D'Hollander, Wendy; Covaci, Adrian; Bervoets, Lieven; Fransen, Erik; De Neubourg, Diane; De Pauw, Ingrid; Leroy, Jo L M R; Jorssen, Ellen P A; Bols, Peter E J

    2014-10-15

    Perfluoroalkyl acids (PFAAs) have been shown to induce negative effects in laboratory animals and in vitro experiments. Also, PFAAs have been detected in human tissues and body fluids. The ovarian follicle constitutes a fragile micro-environment where interactions between hormones, growth factors, the oocyte and surrounding somatic cells are essential to generate a fully competent oocyte. In vitro experiments suggest that PFAAs can influence this balance, but very scarce in vivo data are available to confirm this assumption. In fact, the potential PFAA-presence in the follicular micro-environment is currently unknown. Therefore, we investigated if PFAAs are present in human follicular fluid and if their presence could be a risk factor for in vivo exposed developing oocytes. Furthermore, we compared the PFAA-distribution within serum and follicular fluid. PFAAs were analyzed by LC/MS in follicular fluid (n=38) and serum (n=20) samples from women undergoing assisted reproductive technologies (ARTs). Statistical models were used to investigate PFAA-distribution in both body fluids, to compare this behavior with the distribution of lipophilic organic pollutants and to explore the relationship between patient characteristics, ART-results and follicular fluid contamination. Perfluorooctane sulfonate (PFOS) was the PFAA found in the highest concentration in follicular fluid [7.5 (0.1-30.4) ng/mL] and serum [7.6 (2.8-12.5) ng/mL]. A new variable, Principal Component 1, representing the overall PFAA-contamination of the follicular fluid samples, was associated with a higher fertilization rate (p<0.05) and a higher proportion of top embryos relative to the amount of retrieved oocytes (p<0.05), after adjusting for age, estradiol-concentration, BMI, male subfertility and the presence of other organic pollutants as explanatory variables. To conclude, overall higher PFAA-contamination in the follicular micro-environment was associated with a higher chance of an oocyte to develop

  19. Size and age-concentration relationships for perfluoroalkyl substances in stingray livers from eastern Australia.

    PubMed

    Baduel, Christine; Lai, Foon Yin; Townsend, Kathy; Mueller, Jochen F

    2014-10-15

    While the literature has reported a widespread occurrence of perfluoroalkyl substances (PFASs) in marine biota, very limited studies have been dedicated to the southern hemisphere. Hepatic concentrations of nine PFAAs were analysed in 49 stranded stingrays from eastern Australia using liquid chromatograph coupled with tandem mass spectrometry and relationships with biological parameters (i.e. body size, age and sex) were investigated. Perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) were the predominant compounds quantified, with hepatic concentrations varying from 2 to 117 and from 0.2 to 19 ng·g(-1) w.w., respectively. A negative correlation between the concentration of PFASs in the livers of 32 blue-spotted stingrays and the body size/age was found. This relationship was independent of the animal's sex. We postulate that the dependence on body size is related to differing uptake kinetics of the chemicals, after the sting rays were exposed to an increased level of the contaminants in their environment. Such a pollution event could be related to a severe flood event that occurred at this location a few months before the samples' collection. Our results indicate that the influence of the body size/age should be taken into account when estimating bioaccumulation parameters from environmental measurements or exposure levels of biota to PFASs.

  20. Behaviour and fate of perfluoroalkyl and polyfluoroalkyl substances (PFASs) in drinking water treatment: a review.

    PubMed

    Rahman, Mohammad Feisal; Peldszus, Sigrid; Anderson, William B

    2014-03-01

    This article reviews perfluoroalkyl and polyfluoroalkyl substance (PFAS) characteristics, their occurrence in surface water, and their fate in drinking water treatment processes. PFASs have been detected globally in the aquatic environment including drinking water at trace concentrations and due, in part, to their persistence in human tissue some are being investigated for regulation. They are aliphatic compounds containing saturated carbon-fluorine bonds and are resistant to chemical, physical, and biological degradation. Functional groups, carbon chain length, and hydrophilicity/hydrophobicity are some of the important structural properties of PFASs that affect their fate during drinking water treatment. Full-scale drinking water treatment plant occurrence data indicate that PFASs, if present in raw water, are not substantially removed by most drinking water treatment processes including coagulation, flocculation, sedimentation, filtration, biofiltration, oxidation (chlorination, ozonation, AOPs), UV irradiation, and low pressure membranes. Early observations suggest that activated carbon adsorption, ion exchange, and high pressure membrane filtration may be effective in controlling these contaminants. However, branched isomers and the increasingly used shorter chain PFAS replacement products may be problematic as it pertains to the accurate assessment of PFAS behaviour through drinking water treatment processes since only limited information is available for these PFASs.

  1. Degradation and crosslinking of perfluoroalkyl polyethers under X-ray irradiation in ultrahigh vacuum

    NASA Technical Reports Server (NTRS)

    Mori, Shigeyuki; Morales, Wilfredo

    1989-01-01

    Degradation of three types of commercially available perfluoroalkyl polyethers (PFPE)-Demnum S200, Fomblin Z25, and Krytox 16256-by X-ray irradiation was studied by using X-ray photoemission spectroscopy (XPS) and a mass spectrometer under ultra-high-vacuum conditions. The carbons in the polymers were characterized by chemical shifts of Cls binding energies. Gaseous products containing COF2 and low-molecular-weight fluorocarbons were formed. From Fomblin Z25, which has acetal linkages (-OCF2O-), a large quantity of COF2 gas was evolved. Liquid products became tacky after a long irradiation time, and some did not dissolve in Freon. High-pressure liquid chromatography (HPLC) showed that molecular weight distribution became broader and that higher molecular weight polymers were formed from Demnum and Krytox. We concluded from these results that degradation and cross-linking took place simultaneously. Demnum crosslinked more easily than the other fluids. The time dependence of both XPS spectra of Cls and mass spectra showed that C-O-bonded carbons in PFPE'S were removed faster than other carbons. There was no substrate effect on the degradation reaction because the first-order rate constants calculated from the change of gaseous products were similar when stainless steel (440C) and gold-coated surfaces were used. Metal fluorides were formed on stainless steel during the reaction. A mechanism for the degradation of PFPE'S is discussed on the basis of their molecular structures.

  2. Time trends between 1987 and 2007 for perfluoroalkyl acids in plasma from Swedish women.

    PubMed

    Axmon, Anna; Axelsson, Jonatan; Jakobsson, Kristina; Lindh, Christian H; Jönsson, Bo A G

    2014-05-01

    Perfluoroalkyl acids (PFAAs) are a large group of chemicals which are highly persistent in both nature and humans. The use of the most prominent ones, perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA), was reduced in the early 21st century, and since then levels in human matrices have decreased. However, these two compounds have been exchanged by other PFAAs, for which time trends have not been as extensively investigated. By the use of 80 plasma samples collected between 1987 and 2007 from healthy women (n=1-9 yearly for 1987-2001, n=15 from 2006, and n=10 from 2007), possible time trends of six PFAAs were assessed. Time trends were evaluated for the entire study period, as well as for three sub-periods. As seen in previous studies, levels of perfluorohexane sulfonate (PFHxS), PFOS, and PFOA peaked during the middle time period (1990-2000), with medians of 0.98 ng mL(-1), 18.06 ng mL(-1), and 3.73 ng mL(-1), respectively. However, levels of perfluorononanic acid (PFNA), perfluorodecanic acid (PFDA), and perfluoroundecanoic acid (PFUnDA) increased over the whole study period and most markedly so after year 2000, with medians of 0.73 ng mL(-1), 0.28 ng mL(-1), and 0.24 ng mL(-1), respectively, during the last study period.

  3. Covalent triazine-based framework: A promising adsorbent for removal of perfluoroalkyl acids from aqueous solution.

    PubMed

    Wang, Bingyu; Lee, Linda S; Wei, Chenhui; Fu, Heyun; Zheng, Shourong; Xu, Zhaoyi; Zhu, Dongqiang

    2016-09-01

    Perfluoroalkyl acids (PFAAs) are highly stable, persistent, and ubiquitous in the environment with significant concerns growing with regards to both human and ecosystem health. Due to the high stability to both biological and chemical attack, the only currently feasible approach for their removal from water is adsorbent technology. The main objective of this study was to assess a covalent triazine-based framework (CTF) adsorbent for removal from aqueous solutions of perfluoro C4, C6, and C8 carboxylates and sulfonates including the two C8s most commonly monitored, perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS). Adsorption affinity and capacity were quantified and compared to three commonly used sorbents: pulverized microporous activated carbon, single-walled carbon nanotubes, and Amberlite IRA-400 anion-exchange resin. CTF adsorbent exhibited pronouncedly higher adsorption affinity and capacity of PFAAs than other test sorbents. The remarkably strong adsorption to CTF can be attributed to the favored electrostatic interaction between the protonated triazine groups on the inner wall of the hydrophobic CTF pore and the negatively charged head groups of the PFAAs intercalated between the CTF layers. The homogeneous, nanosized pores (1.2 nm) of CTF hindered adsorption of a large-sized dissolved humic acid, thus minimizing the suppression of PFAA adsorption. Additionally, regeneration of CTF was easily accomplished by simply raising pH > 11, which inhibited the electrostatic adsorptive interaction of PFAAs. PMID:27389552

  4. Elevated levels of perfluoroalkyl substances in estuarine sediments of Charleston, SC.

    PubMed

    White, Natasha D; Balthis, Len; Kannan, Kurunthachalam; De Silva, Amila O; Wu, Qian; French, Katherine M; Daugomah, James; Spencer, Christine; Fair, Patricia A

    2015-07-15

    Urban areas are sources of perfluoroalkyl substances (PFASs) in the environment, although little is known about specific point sources and distribution of PFASs. Sentinel species, like bottlenose dolphins, are important indicators of environmental perturbations. The high PFAS levels found in dolphins inhabiting Charleston, South Carolina prompted investigation of these chemicals in this area. This study provides further evidence on the extent of contamination and potential sources of PFASs. In this study, concentrations of 11 PFASs measured in estuarine sediments collected in 2012 from the Charleston Harbor and the Ashley and Cooper Rivers (n=36) in South Carolina revealed higher levels than those reported in any other U.S. urban areas. Detectable levels were found in all sample locations with mean total PFAS concentrations of 3.79ngg(-1) (range 0.22 to 19.2ngg(-1) d.w.). Dominant compounds were perfluorooctane sulfonate (PFOS) (mean 1.52ngg(-1); range 0.09-7.37ngg(-1) d.w.), followed by perfluorodecanoate (PFDA) (mean 0.83ngg(-1); range 0.06-4.76ngg(-1) d.w.) and perfluorooctanoate (PFOA) (mean 0.42ngg(-1); range 0.02-2.52ngg(-1) d.w.). PFOS levels in sediments at 19 of 36 sites (representing 52% of the study area) exceeded the published global median PFOS sediment concentration of 0.54ngg(-1).

  5. Size and age-concentration relationships for perfluoroalkyl substances in stingray livers from eastern Australia.

    PubMed

    Baduel, Christine; Lai, Foon Yin; Townsend, Kathy; Mueller, Jochen F

    2014-10-15

    While the literature has reported a widespread occurrence of perfluoroalkyl substances (PFASs) in marine biota, very limited studies have been dedicated to the southern hemisphere. Hepatic concentrations of nine PFAAs were analysed in 49 stranded stingrays from eastern Australia using liquid chromatograph coupled with tandem mass spectrometry and relationships with biological parameters (i.e. body size, age and sex) were investigated. Perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) were the predominant compounds quantified, with hepatic concentrations varying from 2 to 117 and from 0.2 to 19 ng·g(-1) w.w., respectively. A negative correlation between the concentration of PFASs in the livers of 32 blue-spotted stingrays and the body size/age was found. This relationship was independent of the animal's sex. We postulate that the dependence on body size is related to differing uptake kinetics of the chemicals, after the sting rays were exposed to an increased level of the contaminants in their environment. Such a pollution event could be related to a severe flood event that occurred at this location a few months before the samples' collection. Our results indicate that the influence of the body size/age should be taken into account when estimating bioaccumulation parameters from environmental measurements or exposure levels of biota to PFASs. PMID:25108254

  6. Surface properties of a single perfluoroalkyl group on water surfaces studied by surface potential measurements.

    PubMed

    Shimoaka, Takafumi; Tanaka, Yuki; Shioya, Nobutaka; Morita, Kohei; Sonoyama, Masashi; Amii, Hideki; Takagi, Toshiyuki; Kanamori, Toshiyuki; Hasegawa, Takeshi

    2016-12-01

    A discriminative study of a single perfluoroalkyl (Rf) group from a bulk material is recently recognized to be necessary toward the total understanding of Rf compounds based on a primary chemical structure. The single molecule and the bulk matter have an interrelationship via an intrinsic two-dimensional (2D) aggregation property of an Rf group, which is theorized by the stratified dipole-arrays (SDA) theory. Since an Rf group has dipole moments along many C-F bonds, a single Rf group would possess a hydrophilic-like character on the surface. To reveal the hydration character of a single Rf group, in the present study, surface potential (ΔV) measurements are performed for Langmuir monolayers of Rf-containing compounds. From a comparative study with a monolayer of a normal hydrocarbon compound, the hydration/dehydration dynamics of a lying Rf group on water has first been monitored by ΔV measurements, through which a single Rf group has been revealed to have a unique "dipole-interactive" character, which enables the Rf group interacted with the water 'surface.' In addition, the SDA theory proves to be useful to predict the 2D aggregation property across the phase transition temperature of 19°C by use of the ΔV measurements.

  7. Surface properties of a single perfluoroalkyl group on water surfaces studied by surface potential measurements.

    PubMed

    Shimoaka, Takafumi; Tanaka, Yuki; Shioya, Nobutaka; Morita, Kohei; Sonoyama, Masashi; Amii, Hideki; Takagi, Toshiyuki; Kanamori, Toshiyuki; Hasegawa, Takeshi

    2016-12-01

    A discriminative study of a single perfluoroalkyl (Rf) group from a bulk material is recently recognized to be necessary toward the total understanding of Rf compounds based on a primary chemical structure. The single molecule and the bulk matter have an interrelationship via an intrinsic two-dimensional (2D) aggregation property of an Rf group, which is theorized by the stratified dipole-arrays (SDA) theory. Since an Rf group has dipole moments along many C-F bonds, a single Rf group would possess a hydrophilic-like character on the surface. To reveal the hydration character of a single Rf group, in the present study, surface potential (ΔV) measurements are performed for Langmuir monolayers of Rf-containing compounds. From a comparative study with a monolayer of a normal hydrocarbon compound, the hydration/dehydration dynamics of a lying Rf group on water has first been monitored by ΔV measurements, through which a single Rf group has been revealed to have a unique "dipole-interactive" character, which enables the Rf group interacted with the water 'surface.' In addition, the SDA theory proves to be useful to predict the 2D aggregation property across the phase transition temperature of 19°C by use of the ΔV measurements. PMID:27569518

  8. High lipophilicity of perfluoroalkyl carboxylate and sulfonate: implications for their membrane permeability.

    PubMed

    Jing, Ping; Rodgers, Patrick J; Amemiya, Shigeru

    2009-02-18

    Here we report on remarkably high lipophilicity of perfluoroalkyl carboxylate and sulfonate. A lipophilic nature of this emerging class of organic pollutants has been hypothesized as an origin of their bioaccumulation and toxicity. Both carboxylate and sulfonate, however, are considered hydrophilic while perfluroalkyl groups are not only hydrophobic but also oleophobic. Partition coefficients of a homologous series of perfluoroalkyl and alkyl carboxylates between water and n-octanol were determined as a measure of their lipophilicity by ion-transfer cyclic voltammetry. Very similar lipophilicity of perfluoroalkyl and alkyl chains with the same length is demonstrated experimentally for the first time by fragment analysis of the partition coefficients. This finding is important for pharmaceutical and biomedical applications of perfluoroalkyl compounds. Interestingly, approximately 2 orders of magnitude higher lipophilicity of a perfluoroalkyl carboxylate or sulfonate in comparison to its alkyl counterpart is ascribed nearly exclusively to their oxoanion groups. The higher lipophilicity originates from a strong electron-withdrawing effect of the perfluoroalkyl group on the adjacent oxoanion group, which is weakly hydrated to decrease its hydrophilicity. In fact, the inductive effect is dramatically reduced for a fluorotelomer with an ethylene spacer between perfluorohexyl and carboxylate groups, which is only as lipophilic as its alkyl counterpart, nonanoate, and is 400 times less lipophilic than perfluorononanoate. The high lipophilicity of perfluoroalkyl carboxylate and sulfonate implies that their permeation across such a thin lipophilic membrane as a bilayer lipid membrane is limited by their transfer at a membrane/water interface. The limiting permeability is lower and less dependent on their lipophilicity than the permeability controlled by their diffusion in the membrane interior as assumed in the classical solubility-diffusion model. PMID:19170492

  9. High lipophilicity of perfluoroalkyl carboxylate and sulfonate: implications for their membrane permeability.

    PubMed

    Jing, Ping; Rodgers, Patrick J; Amemiya, Shigeru

    2009-02-18

    Here we report on remarkably high lipophilicity of perfluoroalkyl carboxylate and sulfonate. A lipophilic nature of this emerging class of organic pollutants has been hypothesized as an origin of their bioaccumulation and toxicity. Both carboxylate and sulfonate, however, are considered hydrophilic while perfluroalkyl groups are not only hydrophobic but also oleophobic. Partition coefficients of a homologous series of perfluoroalkyl and alkyl carboxylates between water and n-octanol were determined as a measure of their lipophilicity by ion-transfer cyclic voltammetry. Very similar lipophilicity of perfluoroalkyl and alkyl chains with the same length is demonstrated experimentally for the first time by fragment analysis of the partition coefficients. This finding is important for pharmaceutical and biomedical applications of perfluoroalkyl compounds. Interestingly, approximately 2 orders of magnitude higher lipophilicity of a perfluoroalkyl carboxylate or sulfonate in comparison to its alkyl counterpart is ascribed nearly exclusively to their oxoanion groups. The higher lipophilicity originates from a strong electron-withdrawing effect of the perfluoroalkyl group on the adjacent oxoanion group, which is weakly hydrated to decrease its hydrophilicity. In fact, the inductive effect is dramatically reduced for a fluorotelomer with an ethylene spacer between perfluorohexyl and carboxylate groups, which is only as lipophilic as its alkyl counterpart, nonanoate, and is 400 times less lipophilic than perfluorononanoate. The high lipophilicity of perfluoroalkyl carboxylate and sulfonate implies that their permeation across such a thin lipophilic membrane as a bilayer lipid membrane is limited by their transfer at a membrane/water interface. The limiting permeability is lower and less dependent on their lipophilicity than the permeability controlled by their diffusion in the membrane interior as assumed in the classical solubility-diffusion model.

  10. Stability of spermine oxidase to thermal and chemical denaturation: comparison with bovine serum amine oxidase.

    PubMed

    Cervelli, Manuela; Leonetti, Alessia; Cervoni, Laura; Ohkubo, Shinji; Xhani, Marla; Stano, Pasquale; Federico, Rodolfo; Polticelli, Fabio; Mariottini, Paolo; Agostinelli, Enzo

    2016-10-01

    Spermine oxidase (SMOX) is a flavin-containing enzyme that specifically oxidizes spermine to produce spermidine, 3-aminopropanaldehyde and hydrogen peroxide. While no crystal structure is available for any mammalian SMOX, X-ray crystallography showed that the yeast Fms1 polyamine oxidase has a dimeric structure. Based on this scenario, we have investigated the quaternary structure of the SMOX protein by native gel electrophoresis, which revealed a composite gel band pattern, suggesting the formation of protein complexes. All high-order protein complexes are sensitive to reducing conditions, showing that disulfide bonds were responsible for protein complexes formation. The major gel band other than the SMOX monomer is the covalent SMOX homodimer, which was disassembled by increasing the reducing conditions, while being resistant to other denaturing conditions. Homodimeric and monomeric SMOXs are catalytically active, as revealed after gel staining for enzymatic activity. An engineered SMOX mutant deprived of all but two cysteine residues was prepared and characterized experimentally, resulting in a monomeric species. High-sensitivity differential scanning calorimetry of SMOX was compared with that of bovine serum amine oxidase, to analyse their thermal stability. Furthermore, enzymatic activity assays and fluorescence spectroscopy were used to gain insight into the unfolding process. PMID:27295021

  11. Comparison of surface properties of random, block, and graft copolymers having perfluoroalkyl and silicone-containing side chains.

    PubMed

    Kim, Dong-Kwon; Lee, Soo-Bok

    2002-03-15

    Fluorosilicone copolymers of random, block, and graft with both perfluoroalkyl and silicone-containing side chains were synthesized, and their surface properties and surface modification effects on PVC film were compared. It can be confirmed that the fluorosilicone copolymers of random, block, and graft exhibit very low surface free energies of 9-13 dyn/cm, depending on the perfluoroalkyl group content and their molecular structure. The inherent surface free energies of the fluorosilicone copolymers are significantly influenced by their molecular structure and perfluoroalkyl group content. It can also be found that the fluorosilicone copolymers are very effective for lowering surface free energy. The surface free energy of a copolymer/PVC blend strongly varies with perfluoroalkyl group content as well as molecular structure. The molecular structure of a fluorosilicone copolymer is as important as the perfluoroalkyl group content for their inherent surface free energies and surface modification of other polymers.

  12. Characterization of cultured rat oligodendrocytes proliferating in a serum-free, chemically defined medium

    SciTech Connect

    Saneto, R.P.; de Vellis, J.

    1985-05-01

    A serumless, chemically defined medium has been developed for the culture of oligodendrocytes isolated from primary neonatal rat cerebral cultures. Combined together, insulin, transferrin, and fibroblast growth factor synergistically induced an essentially homogeneous population (95-98%) of cells expressing glycerol-3-phosphate dehydrogenase activity to undergo cell division. Proliferating cells were characterized by several criteria: (i) ultrastructural analysis by transmission electron microscopy identified the cell type as an oligodendrocyte; (ii) biochemical assays showed expression of three oligodendrocyte biochemical markers, induction of both glycerol phosphate dehydrogenase and lactate dehydrogenase, and presence of 2',3'-cyclic nucleotide 3'-phosphodiesterase; and (iii) immunocytochemical staining showed cultures to be 95-98% positive for glycerol phosphate dehydrogenase, 90% for myelin basic protein, 60-70% for galactocerebroside, and 70% for A2B5.

  13. Exposure of Norwegian toddlers to perfluoroalkyl substances (PFAS): The association with breastfeeding and maternal PFAS concentrations.

    PubMed

    Papadopoulou, Eleni; Sabaredzovic, Azemira; Namork, Ellen; Nygaard, Unni C; Granum, Berit; Haug, Line S

    2016-09-01

    High exposure to perfluoroalkyl substances (PFASs) has been associated with adverse health effects in children. PFASs exposure pathways of toddlers might differ from those of infants and adults, and the investigations on determinants of PFASs exposure in early childhood are scarce. Our aims were to examine the PFAS blood concentrations in Norwegian toddlers and to assess their relationship with maternal PFAS concentrations in pregnancy and breastfeeding duration. We determined PFAS concentrations in 112 plasma samples of 3-year-old children collected at 2010-2011 and 99 maternal serum samples collected around delivery at 2007-2008. PFAS concentrations in children were regressed on duration of breastfeeding, and the effect modification by maternal prenatal PFAS concentrations was examined in 55 mother-child pairs. Six PFASs were quantifiable in >50% of both maternal and children samples. Positive and significant correlations ranging between 0.50 and 0.66 were found between maternal and child concentrations of the same PFAS congeners. Nevertheless, toddlers had higher total PFAS blood concentrations than their mothers, due to higher concentrations of PFOA, PFNA and PFHxS. Every month of breastfeeding was associated with an increase of 3.3% (95% Confidence Intervals (CI): 0.8-5.8) for PFOS, 4.7% (95%CI: 2.8-6.6) for PFOA and 6.1% (95% CI: 2.6-9.7) for PFHpS in toddlers' plasma and a dose-response association was found, after adjustment for confounders. However, PFNA and PFUnDA concentrations in children were not associated with either maternal concentrations or breastfeeding duration. Our findings suggest that transplacental transfer, prenatally, and breastfeeding, postanatally, are among the main determinants of PFOS, PFOA, PFHxS and PFHpS concentrations in toddlers, while that was not the case for PFNA and PFUnDA. Nevertheless, due to the small number of mother child-pairs in our study, our results should be interpreted with caution. PMID:27453094

  14. Perfluoroalkyl and Polyfluoroalkyl Substances and Indicators of Immune Function in Children Aged 12 – 19 years: NHANES

    PubMed Central

    Stein, Cheryl R.; McGovern, Kathleen J.; Pajak, Ashley M.; Maglione, Paul J.; Wolff, Mary S.

    2016-01-01

    Background Perfluoroalkyl and polyfluoroalkyl substances (PFAS) are immunotoxic in laboratory studies. Humans studies of immune effects are inconsistent. Using the U.S. National Health and Nutrition Examination Survey (NHANES) we examined PFAS serum concentration and indicators of prevalent immune function among 12 to 19 year old children. Methods In this cross-sectional study we examined PFAS serum concentration in relation to measles, mumps, and rubella antibody concentrations in NHANES 1999 – 2000 and 2003 – 2004 (n=1,191) and to allergic conditions and allergic sensitization in NHANES 2005 – 2006 (n=640). Results In adjusted, survey-weighted models, a doubling of perfluorooctane sulfonate (PFOS) concentration among seropositive children was associated with a 13.3% (95% CI −19.9, −6.2) decrease in rubella antibody concentration and a 5.9% decrease in mumps antibody concentration (95% CI −9.9, −1.6). We observed no adverse association between exposure and current allergic conditions, including asthma. Children with higher PFOS concentration were less likely to be sensitized to any allergen (OR 0.74, 95% CI 0.58, 0.95). Conclusion Increased exposure to several PFAS was associated with lower levels to mumps and rubella antibody concentrations, especially among seropositive individuals. These lower antibody concentrations may indicate a less robust response to vaccination or greater waning of vaccine-derived immunity over time. PMID:26492286

  15. Quantification of pharmaceuticals, personal care products, and perfluoroalkyl substances in the marine sediments of Puget Sound, Washington, USA.

    PubMed

    Long, Edward R; Dutch, Margaret; Weakland, Sandra; Chandramouli, Bharat; Benskin, Jonathan P

    2013-08-01

    Concentrations of 119 pharmaceuticals and personal care products (PPCPs) and 13 perfluoroalkyl substances (PFASs) in marine sediments measured throughout Puget Sound (n = 10) and Bellingham Bay (n = 30), Washington, USA, are reported. These data are among the first measurements of PPCPs and PFASs in marine sediments from the Pacific Northwest and provide a comparison to previous measurements of these chemicals in influent, effluent, and biosolids from municipal wastewater treatment plants throughout the region. The concentrations of both PPCPs and PFASs in sediments from Puget Sound and Bellingham Bay ranged from very low to non-detectable for most compounds. Only 14 of the 119 PPCPs and 3 of 13 PFASs were quantifiable in sediments. Diphenhydramine (an antihistamine) was most frequently detected (87.5% of samples), with a maximum concentration of 4.81 ng/g dry weight and an estimated mean detected concentration of 1.68 ng/g. Triclocarban (an antibacterial) was detected in 35.0% of the samples, with a maximum concentration of 16.6 ng/g dry weight. Perfluoroalkyl substances were detected in 2.5% of analyses. Perfluorobutanoate, perfluorooctane sulfonate, and perfluorooctane sulfonamide were detected in 7, 5, and 1 sample(s) each, respectively, with the highest concentrations observed for perfluorooctane sulfonate (1.5 ng/g). Detected concentrations were often highest within the industrial harbor in Bellingham Bay and near the cities of Seattle and Bremerton. Environ Toxicol Chem 2013;32:1701-1710. © 2013 SETAC.

  16. Concentrations and patterns of perfluoroalkyl acids in Georgia, USA surface waters near and distant to a major use source

    USGS Publications Warehouse

    Konwick, B.J.; Tomy, G.T.; Ismail, N.; Peterson, J.T.; Fauver, R.J.; Higginbotham, D.; Fisk, A.T.

    2008-01-01

    Perfluoroalkyl acids (PFAAs) are widespread contaminants emanating from, among other sources, the production/degradation of fluorinated chemicals used in surface repellant applications, such as carpet manufacturing. The goal of the present study was to assess the concentrations of PFAAs, including perfluorooctane sulfonate (PFOS), perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), perfluorodecanoic acid (PFDA), perfluoroundecanoic acid (PFUA), and perfluorooctane sulfonamide (PFOSA), in surface waters both near a wastewater land application system (LAS) in Dalton (GA, USA), home to North America's largest carpet manufacturing site, and distant to this location (Altamaha River, GA, USA) to understand the fate of PFAAs in freshwater. Levels of PFAAs were high in the Conasauga River (GA, USA) downstream of the LAS (PFOA, 253-1,150 ng/L; PFOS, 192-318 ng/L; PFNA, 202-369 ng/L; PFDA, 30.1-113 ng/L; PFUA, 58.0-99.2 ng/L; PFOSA, 162-283 ng/L) and in streams and ponds in Dalton (PFOA, 49.9-299 ng/L; PFOS, 15.8-120 ng/L), and were among the highest measured at a nonspill or directrelease location. Perfluoroalkyl acids in the Altamaha River were much lower (PFOA, 3.0-3.1 ng/L; PFOS, 2.6-2.7 ng/L), but were a source of PFAAs to Georgia's estuaries. A preliminary hazard assessment indicated that concentrations of PFOS at two sites in the Conasauga River exceeded the threshold effect predicted for birds consuming aquatic organisms that are exposed continuously to the PFOS levels at these sites. Assuming that toxicity for all PFAAs quantified is equal to that of PFOS, the sum total PFAAs at two sites within the Conasauga River exceeded PFOS thresholds for aquatic and avian species, warranting additional research. ?? 2008 SETAC Printed in the USA.

  17. Development and validation of a method for the quantification of extractable perfluoroalkyl acids (PFAAs) and perfluorooctane sulfonamide (FOSA) in textiles.

    PubMed

    van der Veen, Ike; Weiss, Jana M; Hanning, Anne-Charlotte; de Boer, Jacob; Leonards, Pim E G

    2016-01-15

    In textiles, like outdoor clothing, per- and polyfluoroalkyl substances (PFASs) are often used for durable water repellency (DWR) of the final products. The analytical performance to determine the concentration of these chemicals available for exposure to humans and to the environment need to be established. Here a method for the extraction and analysis of one class of PFASs, namely perfluoroalkyl acids (PFAAs), in outdoor clothing was developed and validated. The PFAAs which were validated, included perfluoroalkyl carboxylic acids (PFCAs) (C4-C14), and perfluoroalkane sulfonic acids (PFSAs) (C4, C6, C7, C8). In addition, perfluorooctane sulfonamide (FOSA) was included in this study. The method was based on an organic solvent extraction and analysis by high-performance liquid chromatography-tandem mass spectrometry (LC-MS/MS). No further cleaning was needed. Two commonly used organic solvent compositions were evaluated for the optimal extraction, i.e. methanol and acetone/acetonitrile (80:20, v/v), and the number and duration of the sequential extractions were optimized. Results showed that two sequential extractions with 5mL methanol and an extraction time of 30min gave an optimal performance with an extraction efficiency of >90%. The influence of matrix on the quantification of PFAAs was studied. This indicated ion suppression due to different matrix effects or sorption behavior to specific textile samples. Validation of the entire method showed overall recoveries of>80% and relative standard deviations (RSDs) of<9% (n=3) for repeatability and <20% (n=3) for reproducibility. This is the first validation of an analytical method for the analysis of extractable PFCAs, PFSAs and FOSA associated to textiles, which is of high importance due to the regulation of PFAAs in textile.

  18. Effects of chemical modification on the potency, serum stability, and immunostimulatory properties of short shRNAs

    PubMed Central

    Ge, Qing; Dallas, Anne; Ilves, Heini; Shorenstein, Joshua; Behlke, Mark A.; Johnston, Brian H.

    2010-01-01

    Small hairpin RNAs (shRNAs) with 19-base-pair, or shorter, stems (short shRNAs [sshRNAs]) have been found to constitute a class whose mechanism of action appears to be distinct from that of small interfering RNAs (siRNAs) or longer shRNAs. These sshRNAs can be as active as canonical siRNAs or longer shRNAs. Their activity is affected by whether the antisense strand is positioned 5′ or 3′ to the loop (L or R sshRNAs, respectively). Dicer seems not to be involved in the processing of sshRNAs, although the mechanism of target gene suppression by these hairpins is through Ago2-mediated mRNA cleavage. In this study, the effects of chemical modifications on the potency, serum stability, and innate immune response of sshRNAs were investigated. Deoxynucleotide substitution and 2′-O-methyl (2′-OMe) modification in the sense strand and loop did not affect silencing activity, but, unlike with siRNAs, when placed in the antisense strand these modifications were detrimental. Conjugation with bulky groups at the 5′-end of L sshRNAs or 3′-end of R sshRNAs had a negative impact on the potency. Unmodified sshRNAs in dimer form or with blunt ends were immunostimulatory. Some modifications such as 3′-end conjugation and phosphorothioate linkages on the backbone of the sshRNAs could also induce inflammatory cytokine production. However, 2′-OMe substitution of sshRNAs abrogated the innate immune response and improved the serum stability of the hairpins. PMID:19948766

  19. Norepinephrine stimulates progesterone production in highly estrogenic bovine granulosa cells cultured under serum-free, chemically defined conditions

    PubMed Central

    2012-01-01

    Background Since noradrenergic innervation was described in the ovarian follicle, the actions of the intraovarian catecholaminergic system have been the focus of a variety of studies. We aimed to determine the gonadotropin-independent effects of the catecholamine norepinephrine (NE) in the steroid hormone profile of a serum-free granulosa cell (GC) culture system in the context of follicular development and dominance. Methods Primary bovine GCs were cultivated in a serum-free, chemically defined culture system supplemented with 0.1% polyvinyl alcohol. The culture features were assessed by hormone measurements and ultrastructural characteristics of GCs. Results GCs produced increasing amounts of estradiol and pregnenolone for 144h and maintained ultrastructural features of healthy steroidogenic cells. Progesterone production was also detected, although it significantly increased only after 96h of culture. There was a highly significant positive correlation between estradiol and pregnenolone production in high E2-producing cultures. The effects of NE were further evaluated in a dose–response study. The highest tested concentration of NE (10 (−7) M) resulted in a significant increase in progesterone production, but not in estradiol or pregnenolone production. The specificity of NE effects on progesterone productio n was further investigated by incubating GCs with propranolol (10 (−8) M), a non-selective beta-adrenergic antagonist. Conclusions The present culture system represents a robust model to study the impact of intrafollicular factors, such as catecholamines, in ovarian steroidogenesis and follicular development. The results of noradrenergic effects in the steroidogenesis of GC have implications on physiological follicular fate and on certain pathological ovarian conditions such as cyst formation and anovulation. PMID:23171052

  20. Serum-free, chemically defined medium with TGF-beta(3) enhances functional properties of nucleus pulposus cell-laden carboxymethylcellulose hydrogel constructs.

    PubMed

    Reza, Anna T; Nicoll, Steven B

    2010-02-01

    Degeneration of the nucleus pulposus (NP) has been implicated as a major cause of low back pain. Tissue engineering strategies may provide a viable NP replacement therapy; however, culture conditions must be optimized to promote functional tissue development. In this study, a standard serum-containing medium formulation was compared to a chemically defined, serum-free medium to determine the effect on matrix elaboration and functional properties of NP cell-laden carboxymethylcellulose (CMC) hydrogels. Additionally, both media were further supplemented with transforming growth factor-beta 3 (TGF-beta(3)). Glycosaminoglycan (GAG) content increased in both TGF-beta(3)-treated groups and was highest for treated, serum-free constructs (9.46 +/- 1.51 microg GAG/mg wet weight), while there were no quantifiable GAGs in untreated serum-containing samples. Histology revealed uniform, interterritorial staining for chondroitin sulfate proteoglycan throughout the treated, serum-free constructs. Type II collagen content was greater in both serum-free groups and highest in treated, serum-free constructs. The equilibrium Young's modulus was highest in serum-free samples supplemented with TGF-beta(3) (18.54 +/- 1.92 kPa), and the equilibrium weight swelling ratio of these constructs approached that of the native NP tissue (22.19 +/- 0.46 vs. 19.94 +/- 3.09, respectively). Taken together, these results demonstrate enhanced functional matrix development by NP cells when cultured in CMC hydrogels maintained in serum-free, TGF-beta(3) supplemented medium, indicating the importance of medium formulation in NP construct development. PMID:19777586

  1. Perfluoroalkyl-Functionalized Hyperbranched Polyglycerol as Pore Forming Agents and Supramolecular Hosts in Polymer Microspheres

    PubMed Central

    Wagner, Olaf; Zieringer, Maximilian; Duncanson, Wynter J.; Weitz, David A.; Haag, Rainer

    2015-01-01

    Perfluoroalkyl-functionalized, hyperbranched polyglycerols that produce stable microbubbles are integrated into a microfluidic emulsion to create porous microspheres. In a previously-presented work a dendrimer with a perfluorinated shell was used. By replacing this dendrimer core with a hyperbranched core and evaluating different core sizes and degrees of fluorinated shell functionalization, we optimized the process to a more convenient synthesis and higher porosities. The new hyperbranched polyglycerol porogens produced more pores and can be used to prepare microspheres with porosity up to 12% (v/v). The presented preparation forms pores with a perfluoroalkyl-functionalized surface that enables the resulting microspheres to act as supramolecular host systems. The microspheres can incorporate gases into the pores and actives in the polymer matrix, while the perfluoroalkylated pore surface can be used to immobilize perfluoro-tagged molecules onto the pores by fluorous-fluorous interaction. PMID:26343631

  2. Comparison of chemical-activated luciferase gene expression bioassay and gas chromatography for PCB determination in human serum and follicular fluid.

    PubMed Central

    Pauwels, A; Cenijn, P H; Schepens, P J; Brouwer, A

    2000-01-01

    We assessed exposure to dioxin-like compounds using chemical and bioassay analysis in different matrices in a female population. A total of 106 serum and 9 follicular fluid samples were collected from infertile women attending Centers for Reproductive Medicine in Belgium from 1996 to 1998. Major polychlorinated biphenyl (PCB) congeners were quantified by chemical analysis using gas chromatography with electron-capture detection, and the chemical-activated luciferase gene expression (CALUX) bioassay was used to determine the total dioxin-like toxic equivalence (TEQ) of mixtures of polyhalogenated aromatic hydrocarbons present in body fluids, such as serum and follicular fluid. To the best of our knowledge, this is the first investigation to determine TEQ values by the CALUX bioassay in follicular fluid. The TEQ levels in both matrices are well correlated (r = 0.83, p = 0.02). As the chemical and bioassay analysis executed in this study do not cover the same span of polyhalogenated aromatic hydrocarbons, we did not expect totally correlated results. Moreover, the sample workup and quantification of the analytes differed completely. Nonetheless, the TEQ values in human extracts correlated well with the sum of four major PCB congeners chemically determined in both serum and follicular fluid. These results indicate that the CALUX bioassay may serve as a simple, relatively inexpensive prescreening tool for exposure assessment in epidemiologic surveys. Images Figure 1 Figure 2 PMID:10856030

  3. Gold-Catalyzed Highly Selective Photoredox C(sp(2) )-H Difluoroalkylation and Perfluoroalkylation of Hydrazones.

    PubMed

    Xie, Jin; Zhang, Tuo; Chen, Fei; Mehrkens, Nina; Rominger, Frank; Rudolph, Matthias; Hashmi, A Stephen K

    2016-02-18

    The first gold-catalyzed photoredox C(sp(2) )-H difluoroalkylation and perfluoroalkylation of hydrazones with readily available RF -Br reagents is reported. The resulting gem-difluoromethylated and perfluoroalkylated hydrazones are highly functionalized, versatile molecules. A mild reduction of the coupling products can efficiently produce gem-difluoromethylated β-amino phosphonic acids and β-amino acid derivatives. In mechanistic studies, a difluoroalkyl radical intermediate was detected by an EPR spin-trapping experiment, indicating that a gold-catalyzed radical pathway is operating. PMID:26800002

  4. Chemical Immobilization of Sloth Bears (Melursus ursinus) with Ketamine Hydrochloride and Xylazine Hydrochloride: Hematology and Serum Biochemical Values

    PubMed Central

    Veeraselvam, M.; Sridhar, R.; Perumal, P.; Jayathangaraj, M. G.

    2014-01-01

    The present study was conducted to define the physiological responses of captive sloth bears immobilized with ketamine hydrochloride and xylazine hydrochloride and to determine and compare the values of hematology and serum biochemical parameters between sexes. A total of 15 sloth bears were immobilized using combination of ketamine hydrochloride and xylazine hydrochloride drugs at the dose rate of 5.0 milligram (mg) per kg body weight and 2.0 mg per kg body weight, respectively. The use of combination of these drugs was found satisfactory for the chemical immobilization of captive sloth bears. There were no significant differences observed in induction time and recovery time and physiological parameters such as heart rate, respiratory rate, and rectal temperature between sexes. Health related parameters comprising hematological values like packed cell volume (PCV), hemoglobin (Hb), red blood cell count (RBC), erythrocyte indices, and so forth and biochemical values like total protein, blood urea nitrogen (BUN), creatinine, alkaline amino-transferase (ALT), aspartate amino-transferase (AST), and so forth were estimated in 11 (5 males and 6 females) apparently healthy bears. Comparison between sexes revealed significant difference in PCV (P < 0.05) and mean corpuscular hemoglobin concentration (MCHC) (P < 0.05). The study might help to evaluate health profiles of sloth bears for appropriate line treatment. PMID:24876990

  5. Evidence that Chemical Chaperone 4-Phenylbutyric Acid Binds to Human Serum Albumin at Fatty Acid Binding Sites

    PubMed Central

    James, Joel; Shihabudeen, Mohamed Sham; Kulshrestha, Shweta; Goel, Varun; Thirumurugan, Kavitha

    2015-01-01

    Endoplasmic reticulum stress elicits unfolded protein response to counteract the accumulating unfolded protein load inside a cell. The chemical chaperone, 4-Phenylbutyric acid (4-PBA) is a FDA approved drug that alleviates endoplasmic reticulum stress by assisting protein folding. It is found efficacious to augment pathological conditions like type 2 diabetes, obesity and neurodegeneration. This study explores the binding nature of 4-PBA with human serum albumin (HSA) through spectroscopic and molecular dynamics approaches, and the results show that 4-PBA has high binding specificity to Sudlow Site II (Fatty acid binding site 3, subdomain IIIA). Ligand displacement studies, RMSD stabilization profiles and MM-PBSA binding free energy calculation confirm the same. The binding constant as calculated from fluorescence spectroscopic studies was found to be kPBA = 2.69 x 105 M-1. Like long chain fatty acids, 4-PBA induces conformational changes on HSA as shown by circular dichroism, and it elicits stable binding at Sudlow Site II (fatty acid binding site 3) by forming strong hydrogen bonding and a salt bridge between domain II and III of HSA. This minimizes the fluctuation of HSA backbone as shown by limited conformational space occupancy in the principal component analysis. The overall hydrophobicity of W214 pocket (located at subdomain IIA), increases upon occupancy of 4-PBA at any FA site. Descriptors of this pocket formed by residues from other subdomains largely play a role in compensating the dynamic movement of W214. PMID:26181488

  6. Efficient hydrolysis of the chemical warfare nerve agent tabun by recombinant and purified human and rabbit serum paraoxonase 1.

    PubMed

    Valiyaveettil, Manojkumar; Alamneh, Yonas; Biggemann, Lionel; Soojhawon, Iswarduth; Doctor, Bhupendra P; Nambiar, Madhusoodana P

    2010-12-01

    Paraoxonase 1 (PON1) has been described as an efficient catalytic bioscavenger due to its ability to hydrolyze organophosphates (OPs) and chemical warfare nerve agents (CWNAs). It is the future most promising candidate as prophylactic medical countermeasure against highly toxic OPs and CWNAs. Most of the studies conducted so far have been focused on the hydrolyzing potential of PON1 against nerve agents, sarin, soman, and VX. Here, we investigated the hydrolysis of tabun by PON1 with the objective of comparing the hydrolysis potential of human and rabbit serum purified and recombinant human PON1. The hydrolysis potential of PON1 against tabun, sarin, and soman was evaluated by using an acetylcholinesterase (AChE) back-titration Ellman method. Efficient hydrolysis of tabun (100 nM) was observed with ∼25-40 mU of PON1, while higher concentration (80-250 mU) of the enzyme was required for the complete hydrolysis of sarin (11 nM) and soman (3 nM). Our data indicate that tabun hydrolysis with PON1 was ∼30-60 times and ∼200-260 times more efficient than that with sarin and soman, respectively. Moreover, the catalytic activity of PON1 varies from source to source, which also reflects their efficiency of hydrolyzing different types of nerve agents. Thus, efficient hydrolysis of tabun by PON1 suggests its promising potential as a prophylactic treatment against tabun exposure.

  7. Determination of perfluoroalkyl carboxylic, sulfonic, and phosphonic acids in food.

    PubMed

    Ullah, Shahid; Alsberg, Tomas; Vestergren, Robin; Berger, Urs

    2012-11-01

    A sensitive and accurate method was developed and validated for simultaneous analysis of perfluoroalkyl carboxylic acids, sulfonic acids, and phosphonic acids (PFPAs) at low picograms per gram concentrations in a variety of food matrices. The method employed extraction with acetonitrile/water and cleanup on a mixed-mode co-polymeric sorbent (C8 + quaternary amine) using solid-phase extraction. High-performance liquid chromatographic separation was achieved on a C18 column using a mobile phase gradient containing 5 mM 1-methyl piperidine for optimal chromatographic resolution of PFPAs. A quadrupole time-of-flight high-resolution mass spectrometer operating in negative ion mode was used as detector. Method detection limits were in the range of 0.002 to 0.02 ng g(-1) for all analytes. Sample preparation (extraction and cleanup) recoveries at a spiking level of 0.1 ng g(-1) to a baby food composite were in the range of 59 to 98 %. A strong matrix effect was observed in the analysis of PFPAs in food extracts, which was tentatively assigned to sorption of PFPAs to the injection vial in the solvent-based calibration standard. The method was successfully applied to a range of different food matrices including duplicate diet samples, vegetables, meat, and fish samples.

  8. Perfluoroalkyl Acids Inhibit Reductive Dechlorination of Trichloroethene by Repressing Dehalococcoides.

    PubMed

    Weathers, Tess S; Harding-Marjanovic, Katie; Higgins, Christopher P; Alvarez-Cohen, Lisa; Sharp, Jonathan O

    2016-01-01

    The subsurface recalcitrance of perfluoroalkyl acids (PFAAs) derived from aqueous film-forming foams could have adverse impacts on the microbiological processes used for the bioremediation of co-mingled chlorinated solvents such as trichloroethene (TCE). Here, we show that reductive dechlorination by a methanogenic, mixed culture was significantly inhibited when exposed to concentrations representative of PFAA source zones (>66 mg/L total of 11 PFAA analytes, 6 mg/L each). TCE dechlorination, cis-dichloroethene and vinyl chloride production and dechlorination, and ethene generation were all inhibited at these PFAA concentrations. Phylogenetic analysis revealed that the abundances of 65% of the operational taxonomic units (OTUs) changed significantly when grown in the presence of PFAAs, although repression or enhancement resulting from PFAA exposure did not correlate with putative function or phylogeny. Notably, there was significant repression of Dehalococcoides (8-fold decrease in abundance) coupled with a corresponding enhancement of methane-generating Archaea (a 9-fold increase). Growth and dechlorination by axenic cultures of Dehalococcoides mccartyi strain 195 were similarly repressed under these conditions, confirming an inhibitory response of this pivotal genus to PFAA presence. These results suggest that chlorinated solvent bioattenuation rates could be impeded in subsurface environments near PFAA source zones. PMID:26636352

  9. Perfluoroalkyl acids in urban stormwater runoff: influence of land use.

    PubMed

    Xiao, Feng; Simcik, Matt F; Gulliver, John S

    2012-12-15

    Perfluoroalkyl acids (PFAAs) are persistent organic pollutants in the environment and have been reported to have nonpoint sources. In this study, six PFAAs with different chain lengths were monitored in stormwater runoff from seven storm events (2009-2011) at various outfall locations corresponding to different watershed land uses. We found PFAA(s) in 100% of stormwater runoff samples. Monitoring results and statistical analysis show that PFAAs in stormwater runoff from residential areas mainly came from rainfall. On the other hand, non-atmospheric sources at both industrial and commercial areas contributed PFAAs in stormwater runoff. The mass flux of PFAAs from stormwater runoff in the Twin Cities (Minneapolis and St. Paul, MN) metropolitan area is estimated to be about 7.86 kg/year. In addition, for the first time, we monitored PFAAs on the particles/debris in stormwater runoff and found high-level PFOS on the particulate matter in runoff collected from both industrial and commercial areas; the levels were so high that the finding could not be explained by the solid-water partitioning or adsorption. PFOS on the particulate matter is suspected to have originated from industrial/commercial products, entering the waste stream as PFOS containing particles.

  10. Nanofiltration and granular activated carbon treatment of perfluoroalkyl acids.

    PubMed

    Appleman, Timothy D; Dickenson, Eric R V; Bellona, Christopher; Higgins, Christopher P

    2013-09-15

    Perfluoroalkyl acids (PFAAs) are of concern because of their persistence in the environment and the potential toxicological effects on humans exposed to PFAAs through a variety of possible exposure routes, including contaminated drinking water. This study evaluated the efficacy of nanofiltration (NF) and granular activated carbon (GAC) adsorption in removing a suite of PFAAs from water. Virgin flat-sheet NF membranes (NF270, Dow/Filmtec) were tested at permeate fluxes of 17-75 Lm(-2)h(-1) using deionized (DI) water and artificial groundwater. The effects of membrane fouling by humic acid on PFAA rejection were also tested under constant permeate flux conditions. Both virgin and fouled NF270 membranes demonstrated >93% removal for all PFAAs under all conditions tested. GAC efficacy was tested using rapid small-scale columns packed with Calgon Filtrasorb300 (F300) carbon and DI water with and without dissolved organic matter (DOM). DOM effects were also evaluated with F600 and Siemens AquaCarb1240C. The F300 GAC had <20% breakthrough of all PFAAs in DI water for up to 125,000 bed volumes (BVs). When DOM was present, >20% breakthrough of all PFAAs by 10,000 BVs was observed for all carbons.

  11. Occurrence of perfluoroalkyl acids in environmental waters in Vietnam.

    PubMed

    Duong, Hanh Thi; Kadokami, Kiwao; Shirasaka, Hanako; Hidaka, Rento; Chau, Hong Thi Cam; Kong, Lingxiao; Nguyen, Trung Quang; Nguyen, Thao Thanh

    2015-03-01

    This is the first nationwide study of perfluoroalkyl acids (PFAAs) in environmental waters in Vietnam. Twenty-eight river water and 22 groundwater samples collected in four major cities and 14 river water samples from the Red River were screened to investigate the occurrence and sources of 16 PFAAs. Perfluorooctane sulfonic acid (PFOS), perfluorooctanoic acid (PFOA), and perfluorononanoic acid (PFNA) were the most prevalent of 11 detected PFAAs with maximum concentrations in urban river water of 5.3, 18 and 0.93ngL(-1), respectively, and in groundwater of 8.2, 4.5 and 0.45ngL(-1), respectively. PFAAs in the Red River water were detected at low levels. PFAA concentrations in river water were higher in the rainy season than in the dry season, possibly due to storm water runoff, a common phenomenon in Southeast Asian countries. The highest concentrations of PFAAs in river water were observed in samples from highly populated and industrialized areas, perhaps sourced from sewage. The PFAA concentrations observed were similar to those in other Southeast Asian countries, but lower than in developed nations. From the composition profiles of PFAAs, industrial products containing PFAAs imported from China and Japan might be one of the major sources of PFAAs in the Vietnamese aquatic environment. According to the health-based values and advisory issued by the United States Environmental Protection Agency (USEPA), the concentrations of detected PFAAs in this study do not pose an immediate health risk to humans and aquatic organisms.

  12. Diminution of phagocytosed perfluorocarbon emulsions using perfluoroalkylated polyethylene glycol surfactant.

    PubMed

    Hsu, Y C; Peng, C A

    2001-05-18

    Perfluorocarbon emulsions have been considered as potential blood substitutes for years due to their high capacity of dissolving respiratory oxygen and carbon dioxide. However, they have been reported to associate with side effects (e.g., flu-like syndrome) after being injected into animal's bloodstream. The cause of these side effects is related to the phagocytosis of perfluorocarbon emulsions by cells (e.g., macrophages). Inspired by the approach of using polyethylene glycol (PEG) to camouflage liposomes, we synthesized a perfluoroalkylated PEG (R(F)-PEG) surfactant to provide steric hindrance for decreasing phagocytosis of perfluorocarbon emulsions. The R(F)-PEG surfactant along with Pluronic F-68 and egg yolk phospholipid mediated perfluorocarbon emulsions were incubated individually with J774A.1 macrophages to examine the degree of phagocytosis. 19F NMR studies were used to quantitatively determine the amount of perfluorocarbon emulsions phagocytosed by macrophages. Results showed that the degree of phagocytosis was diminished to a large extent for perfluorocarbon microparticles emulsified by the R(F)-PEG surfactant. PMID:11350051

  13. Perfluoroalkyl Substances, Sex Hormones, and Insulin-like Growth Factor-1 at 6–9 Years of Age: A Cross-Sectional Analysis within the C8 Health Project

    PubMed Central

    Lopez-Espinosa, Maria-Jose; Mondal, Debapriya; Armstrong, Ben G.; Eskenazi, Brenda; Fletcher, Tony

    2016-01-01

    Background: Exposure to some perfluoroalkyl substances (PFAS), such as perfluorohexane sulfonate (PFHxS), perfluorooctanoate (PFOA), perfluorooctane sulfonate (PFOS), and perfluorononanoic acid (PFNA), may alter levels of sex hormones and insulin-like growth factor-1 (IGF-1) in animals. Human studies on this topic are scarce, and none have been conducted in young children. Objectives: We investigated the relationship between levels of PFAS and estradiol, total testosterone, and IGF-1 in 2,292 children (6–9 years of age) from the C8 Health Project who lived near a chemical plant in the Mid-Ohio Valley (USA) with local contamination from PFOA. Methods: Serum samples were collected in 2005–2006 and analyzed for PFAS, sex hormones, and IGF-1. Results from regression models were expressed as the adjusted percentage difference (95% CI) per sex-specific interquartile range (IQR) increment of each PFAS serum concentration. Analyses by PFAS quartiles were also conducted. Results: Median concentrations of PFHxS, PFOA, PFOS, and PFNA were 8, 35, 22, and 1.7 ng/mL in boys and 7, 30, 21, and 1.7 ng/mL in girls. In boys, PFOA concentrations were significantly associated with testosterone levels (–4.9%; 95% CI: –8.7, –0.8%); PFOS with estradiol (–4.0%; 95% CI: –7.7, –0.1%), testosterone (–5.8%; 95% CI: –9.4, –2.0%), and IGF-1 (–5.9%; 95% CI: –8.3, –3.3%); and PFNA with IGF-1 (–3.5%; 95% CI: –6.0, –1.0%). In girls, significant associations were found between PFOS and testosterone (–6.6%; 95% CI: –10.1, –2.8%) and IGF-1 (–5.6%; –8.2, –2.9%); and PFNA and IGF-1 (–3.8%; 95% CI: –6.4, –1.2%). In both sexes, the magnitudes of the associations decreased monotonically across quartiles for both testosterone and IGF-1 in relation to PFOS, and for IGF-1 and PFNA in girls. Conclusions: To our knowledge, this is the first study suggesting that PFAS are associated with lower levels of IGF-1 and sex hormones in young children. Citation: Lopez

  14. Persistence of perfluoroalkyl acid precursors in AFFF-impacted groundwater and soil.

    PubMed

    Houtz, Erika F; Higgins, Christopher P; Field, Jennifer A; Sedlak, David L

    2013-08-01

    Several classes of polyfluorinated chemicals that are potential precursors to the perfluorinated carboxylates and sulfonates are present in aqueous film-forming foams (AFFF). To assess the persistence of these AFFF-derived precursors, groundwater, soil, and aquifer solids were obtained in 2011 from an unlined firefighter training area at a U.S. Air Force Base where AFFF was regularly used between 1970 and 1990. To measure the total concentration of perfluorinated carboxylate and sulfonate precursors in archived AFFF formulations and AFFF-impacted environmental samples, a previously developed assay that uses hydroxyl radical to oxidize precursors to perfluorinated carboxylates was adapted for these media. This assay was employed along with direct measurement of 22 precursors found in AFFF and a suite of other poly- and perfluoroalkyl substances (PFASs). On a molar basis, precursors accounted for 41-100% of the total concentration of PFASs in archived AFFF formulations. In the training area, precursors measured by the oxidation assay accounted for an average of 23% and 28% of total PFASs (i.e., precursors and perfluorinated carboxylates and sulfonates) in groundwater and solids samples, respectively. One precursor in AFFF, perfluorohexane sulfonamide amine, was observed on several highly contaminated soil and aquifer solids samples, but no other precursors present in AFFF formulations were detected in any samples at this field site. Suspected intermediate transformation products of precursors in AFFF that were directly measured accounted for approximately half of the total precursor concentration in samples from the training site. The fraction of PFASs consisting of perfluorinated carboxylates and sulfonates was greater in groundwater and solid samples than in any archived AFFF formulations, suggesting that much of the mass of precursors released at the site was converted to perfluorinated carboxylates and sulfonates. The precursors that have persisted at this site

  15. Evaluation of Perfluoroalkyl Acid Activity Using Primary Mouse and Human Hepatocytes.

    EPA Science Inventory

    While perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) have been studied at length, less is known about the biological activity of other perfluoroalkyl acids (PFAAs) in the environment. Using a transient transfection assay developed in COS-1 cells, our group h...

  16. EVALUATION OF PERFLUOROALKYL ACID ACTIVITY USING PRIMARY MOUSE AND HUMAN HEPATOCYTES

    EPA Science Inventory

    While perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) have been studied at length, less is know about the biological activity of other environmental perfluoroalkyl acids (pFAAs). Using a transient transfection assay developed in COS-l cells, our group has previ...

  17. Testing for departures from additivity in mixtures of perfluoroalkyl acids (PFAAs)

    EPA Science Inventory

    This study is a follow-up to a paper by Carr, et al. that determined a design structure to optimally test for departures from additivity in a fixed ratio mixture of four perfluoroalkyl acids (PFAAs) using an in vitro transiently-transfected COS- 1 PPARa reporter model with an NHA...

  18. Exposure and effects of perfluoroalkyl substances in tree swallows nesting in Minnesota and Wisconsin, USA

    EPA Science Inventory

    The exposure and effects of perfluoroalkyl substances (PFASs) were studied at eight locations in Minnesota and Wisconsin between 2007 and 2011 using tree swallows (Tachycineta bicolor) as sentinel species. These eight sites covered a range of possible exposure pathways and ecolog...

  19. Perfluoroalkyl substances in the Ebro and Guadalquivir river basins (Spain).

    PubMed

    Lorenzo, María; Campo, Julián; Farré, Marinella; Pérez, Francisca; Picó, Yolanda; Barceló, Damià

    2016-01-01

    Mediterranean rivers are characteristically irregular with changes in flow and located in high population density areas. This affects the concentration of pollutants in the aquatic environments. In this study, the occurrence and sources of 21 perfluoroalkyl substances (PFASs) were determined in water, sediment and biota of the Ebro and Guadalquivir river basins (Spain). In water samples, of 21 analytes screened, 11 were found in Ebro and 9 in Guadalquivir. In both basins, the most frequents were PFBA, PFPeA and PFOA. Maximum concentration was detected for PFBA, up to 251.3 ng L(-1) in Ebro and 742.9 ng L(-1) in Guadalquivir. Regarding the sediments, 8 PFASs were detected in the samples from Ebro and 9 in those from Guadalquivir. The PFASs most frequently detected were PFBA, PFPeA, PFOA and PFOS. Maximum concentration in Ebro samples was, in dry weight, for PFOA (32.3 ng g(-1)) and in Guadalquivir samples for PFBA (63.8 ng g(-1)). For biota, 12 PFASs were detected in fish from the Ebro River and only one (PFOS) in that from Guadalquivir. In the Ebro basin, the most frequents were PFBA, PFHxA, PFOA, PFBS, PFOS and PFOSA. Maximum concentration in Ebro samples was, in wet weight, for PFHxA with 1280.2 ng g(-1), and in Guadalquivir samples for PFOS with 79.8 ng g(-1). These compounds were detected in the whole course of the rivers including the upper parts. In some points contamination was due to point sources mostly related to human activities (e.g. ski resorts, military camps, urban areas.). However, there are also some areas clearly affected by diffuse sources as atmospheric deposition. PMID:26250865

  20. Occurrence of perfluoroalkyl acids in environmental waters in Vietnam.

    PubMed

    Duong, Hanh Thi; Kadokami, Kiwao; Shirasaka, Hanako; Hidaka, Rento; Chau, Hong Thi Cam; Kong, Lingxiao; Nguyen, Trung Quang; Nguyen, Thao Thanh

    2015-03-01

    This is the first nationwide study of perfluoroalkyl acids (PFAAs) in environmental waters in Vietnam. Twenty-eight river water and 22 groundwater samples collected in four major cities and 14 river water samples from the Red River were screened to investigate the occurrence and sources of 16 PFAAs. Perfluorooctane sulfonic acid (PFOS), perfluorooctanoic acid (PFOA), and perfluorononanoic acid (PFNA) were the most prevalent of 11 detected PFAAs with maximum concentrations in urban river water of 5.3, 18 and 0.93ngL(-1), respectively, and in groundwater of 8.2, 4.5 and 0.45ngL(-1), respectively. PFAAs in the Red River water were detected at low levels. PFAA concentrations in river water were higher in the rainy season than in the dry season, possibly due to storm water runoff, a common phenomenon in Southeast Asian countries. The highest concentrations of PFAAs in river water were observed in samples from highly populated and industrialized areas, perhaps sourced from sewage. The PFAA concentrations observed were similar to those in other Southeast Asian countries, but lower than in developed nations. From the composition profiles of PFAAs, industrial products containing PFAAs imported from China and Japan might be one of the major sources of PFAAs in the Vietnamese aquatic environment. According to the health-based values and advisory issued by the United States Environmental Protection Agency (USEPA), the concentrations of detected PFAAs in this study do not pose an immediate health risk to humans and aquatic organisms. PMID:25496738

  1. U.S. Domestic Cats as Sentinels for Perfluoroalkyl Substances: Possible Linkages with Housing, Obesity and Disease

    EPA Science Inventory

    Perfluoroalkyl substances (PFAS), such as perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) , are persistent, globally distributed, anthropogenic compounds. The primary source(s) for human exposure are not well understood although within home exposure is likely i...

  2. Photocatalytic/Cu-Promoted C-H Activations: Visible-light-Induced ortho-Selective Perfluoroalkylation of Benzamides.

    PubMed

    Chen, Xiang; Tan, Ze; Gui, Qingwen; Hu, Liang; Liu, Jidan; Wu, Jing; Wang, Guangwei

    2016-04-25

    A visible-light-induced and copper-promoted perfluoroalkylation of benzamides was successfully developed under the assistance of an 8-aminoquinoline directing group. It provides a straightforward method for the synthesis of ortho-perfluoroalkyl-substituted benzoic acid derivatives. The reaction employs a cheap organic dye eosin Y as the photoredox catalyst and is run under the irradiation of a 26 W fluorescent LED light bulb. PMID:26933840

  3. Chemical conversion of benzo(e)pyrene by aqueous serum albumin to pyrene-like product: fluorescence method

    SciTech Connect

    Srinivasan, B.N.; Fujimori, E.

    1980-01-01

    The interaction of benzo(e)pyrene, an atmospheric pollutant formed during the burning of organic materials, and bovine serum albumin (BSA) was studied to determine a pyrene-type metabolite is formed. (ACR)

  4. Fluorinated alternatives to long-chain perfluoroalkyl carboxylic acids (PFCAs), perfluoroalkane sulfonic acids (PFSAs) and their potential precursors.

    PubMed

    Wang, Zhanyun; Cousins, Ian T; Scheringer, Martin; Hungerbühler, Konrad

    2013-10-01

    Since 2000 there has been an on-going industrial transition to replace long-chain perfluoroalkyl carboxylic acids(PFCAs), perfluoroalkane sulfonic acids (PFSAs) and their precursors. To date, information on these replacements including their chemical identities, however, has not been published or made easily accessible to the public, hampering risk assessment and management of these chemicals. Here we review information on fluorinated alternatives in the public domain. We identify over 20 fluorinated substances that are applied in [i] fluoropolymer manufacture, [ii] surface treatment of textile, leather and carpets, [iii] surface treatment of food contact materials,[iv] metal plating, [v] fire-fighting foams, and [vi] other commercial and consumer products.We summarize current knowledge on their environmental releases, persistence, and exposure of biota and humans. Based on the limited information available, it is unclear whether fluorinated alternatives are safe for humans and the environment.We identify three major data gaps that must be filled to perform meaningful risk assessments and recommend generation of the missing data through cooperation among all stakeholders (industry, regulators, academic scientists and the public).

  5. Prenatal Exposure to Perfluoroalkyl Substances and Behavioral Development in Children

    PubMed Central

    Quaak, Ilona; de Cock, Marijke; de Boer, Michiel; Lamoree, Marja; Leonards, Pim; van de Bor, Margot

    2016-01-01

    Background: In recent years, prevalence rates of behavioral disorders in children have increased. One factor possibly implied in the etiology of behavioral disorders is exposure to perfluoroalkyl substances (PFASs). The use of PFASs is highly integrated into everyday life, and exposure is ubiquitous. Exposure to PFASs during early life may be particularly harmful, as it represents a critical time window for brain development. However, research in the area is limited, especially among preschool children. The objective of the current study was to explore the relationship between prenatal exposure to several PFASs and behavioral development at the age of 18 months. Methods: Data from the Dutch cohort LINC (Linking Maternal Nutrition to Child Health) were used. Perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) were measured in cord plasma. The total exposure of PFASs was also calculated (ΣPFASs). Behavioral development was assessed with the Child Behavior Checklist 1.5–5 (CBCL 1.5–5). The CBCL scales “Attention Deficit Hyperactivity Disorder” (ADHD) and “Externalizing problems” were used for further analysis. Separate regression models were composed for each combination, in which exposure levels were classified in tertiles. Both whole population and sex-stratified analyses were performed. A family history of ADHD, the educational level, smoking or using alcohol or illicit drugs during pregnancy were considered as confounders. In total, data from 76 mother-child pairs was included. Results: No significant associations were found between prenatal PFAS exposure and ADHD scores in the whole population and in the sex-stratified analyses. With regard to externalizing behavior, a significant negative association was found between the highest levels of ΣPFAS exposure and externalizing problem behavior in the whole population, but only in the crude model. After stratifying for sex, boys in the second and third tertile of exposure to PFOA

  6. New approach for assessing human perfluoroalkyl exposure via hair.

    PubMed

    Alves, Andreia; Jacobs, Griet; Vanermen, Guido; Covaci, Adrian; Voorspoels, Stefan

    2015-11-01

    In the recent years hair has been increasingly used as alternative matrix in human biomonitoring (HBM) of environmental pollutants. Sampling advantages and time integration of exposure assessment seems the most attractive features of hair matrix. In the current study, a novel miniaturized method was developed and validated for measuring 15 perfluoroalkyl substances (PFAS), including perfluoro n-butanoic acid (PFBA), perfluoro n-pentanoic acid (PFPeA), perfluoro n-hexanoic acid (PFHxA), perfluoro n-heptanoic acid (PFHpA), perfluor n-octanoic acid (PFOA), perfluoro n-nonanoic acid (PFNA), perfluoro tetradecanoic acid (PFTeDA), perfluorobutane sulfonic acid (PFBS), perfluoro pentane sulfonic acid (PFPeS), perfluorohexane sulfonic acid (PFHxS), perfluoroheptane sulfonic acid (PFHpS), perfluorooctane sulfonic acid (PFOS), perfluorononane sulfonic acid (PFNS), perfluorodecane sulfonic acid (PFDS) and perfluorododecane sulfonic acid (PFDoS) in human hair by liquid chromatography tandem mass spectrometry (LC-MS/MS). After extraction using ethyl acetate, dispersive ENVI-Carb was used for clean-up. Good intra- and inter-day precision for low (LQ 5 ng/g hair) and high spike (HQ 15n g/g) levels were achieved (in general RSD <10%). The accuracy was assessed using recoveries (%), which ranged between 68-118% (LQ) and 70-121% (HQ). The instrumental limit of detection (LODi) and limit of quantification (LOQi) were between 1-4 pg/g hair and 3-13 pg/g hair, respectively. The method limit of quantification (LOQm) ranged between 6 and 301 pg/g hair. The PFAS levels were measured in 30 human hair samples indicating that the levels are low (14-1534 pg/g hair). Some PFAS were not present in any hair sample (e.g. PFHpA, PFTeDA, PFNA, PFPeS, PFHpS, PFOS and PFNS), while other PFAS were frequently detected (PFBA, PFPeA, PFHxA, PFOA, PFBS, PFHxS, PFOS, PFDS and PFDoS) in human hair. Although levels in general were low, there is evidence of higher human exposure to some analytes, such as PFBA

  7. New approach for assessing human perfluoroalkyl exposure via hair.

    PubMed

    Alves, Andreia; Jacobs, Griet; Vanermen, Guido; Covaci, Adrian; Voorspoels, Stefan

    2015-11-01

    In the recent years hair has been increasingly used as alternative matrix in human biomonitoring (HBM) of environmental pollutants. Sampling advantages and time integration of exposure assessment seems the most attractive features of hair matrix. In the current study, a novel miniaturized method was developed and validated for measuring 15 perfluoroalkyl substances (PFAS), including perfluoro n-butanoic acid (PFBA), perfluoro n-pentanoic acid (PFPeA), perfluoro n-hexanoic acid (PFHxA), perfluoro n-heptanoic acid (PFHpA), perfluor n-octanoic acid (PFOA), perfluoro n-nonanoic acid (PFNA), perfluoro tetradecanoic acid (PFTeDA), perfluorobutane sulfonic acid (PFBS), perfluoro pentane sulfonic acid (PFPeS), perfluorohexane sulfonic acid (PFHxS), perfluoroheptane sulfonic acid (PFHpS), perfluorooctane sulfonic acid (PFOS), perfluorononane sulfonic acid (PFNS), perfluorodecane sulfonic acid (PFDS) and perfluorododecane sulfonic acid (PFDoS) in human hair by liquid chromatography tandem mass spectrometry (LC-MS/MS). After extraction using ethyl acetate, dispersive ENVI-Carb was used for clean-up. Good intra- and inter-day precision for low (LQ 5 ng/g hair) and high spike (HQ 15n g/g) levels were achieved (in general RSD <10%). The accuracy was assessed using recoveries (%), which ranged between 68-118% (LQ) and 70-121% (HQ). The instrumental limit of detection (LODi) and limit of quantification (LOQi) were between 1-4 pg/g hair and 3-13 pg/g hair, respectively. The method limit of quantification (LOQm) ranged between 6 and 301 pg/g hair. The PFAS levels were measured in 30 human hair samples indicating that the levels are low (14-1534 pg/g hair). Some PFAS were not present in any hair sample (e.g. PFHpA, PFTeDA, PFNA, PFPeS, PFHpS, PFOS and PFNS), while other PFAS were frequently detected (PFBA, PFPeA, PFHxA, PFOA, PFBS, PFHxS, PFOS, PFDS and PFDoS) in human hair. Although levels in general were low, there is evidence of higher human exposure to some analytes, such as PFBA

  8. Short- and long-chain perfluoroalkyl substances in the water, suspended particulate matter, and surface sediment of a turbid river.

    PubMed

    Zhao, Pujun; Xia, Xinghui; Dong, Jianwei; Xia, Na; Jiang, Xiaoman; Li, Yang; Zhu, Yuemei

    2016-10-15

    Perfluoroalkyl substances (PFASs) have attracted attentions all around the world. However, little is known about their distribution among water, suspended particulate matter (SPM), and sediment phases in rivers, especially for the short-chain PFASs. In this work, the Yellow River, the largest turbid river in the world, was selected as a case to study eleven kinds of PFASs in the three phases of rivers. These PFASs included C4-C12 perfluorinated carboxylates (PFCAs), perfluorobutyl sulfonate (PFBS), and perfluorooctansulfonate (PFOS), among which C4-C7 PFCAs and PFBS belong to short-chain PFASs, while C8-C12 PFCAs and PFOS belong to long-chain PFASs. The results showed that the total PFAS concentration ranged from 44.7ngL(-1) to 1.52μgL(-1) in the water, from 8.19 to 17.4ngg(-1) in the sediment, and from 3.44 to 14.7ngg(-1) in the SPM. Short-chain PFASs predominated in the water and could reach up to 88.8% of the total PFAS concentration in water, while long-chain PFASs prevailed in the sediment and SPM. The PFAS concentration in SPM showed a significant negative correlation with SPM concentration in river water (p<0.01). The distribution coefficients (Kd) of PFASs between sediment/SPM and water increased with their chain length and there was a positive correlation between logKd and logKow (octanol-water partition coefficients). The total annual flux of all the eleven PFASs was estimated at 3.88tons for the Yellow River into the Bohai Sea, among which the PFOA flux was the highest (0.90tons). The widely occurrence and high concentrations of short-chain PFASs in the Yellow River indicates the shift of manufacturing focus of perfluoroalkyl chemicals from traditional long-chain ones to short-chain ones. Further studies should be conducted to evaluate the eco-environmental risks of these short-chain PFASs in water environments.

  9. Perfluoroalkyl substances in the Daling River with concentrated fluorine industries in China: seasonal variation, mass flow, and risk assessment.

    PubMed

    Zhu, Zhaoyun; Wang, Tieyu; Meng, Jing; Wang, Pei; Li, Qifeng; Lu, Yonglong

    2015-07-01

    In the present study, we investigated concentrations and composition profiles of perfluoroalkyl substances (PFASs) in surface water from the Daling River in different seasons. The highest concentration of ΣPFASs (9540 ng L(-1)) and dominant homologues were found in surface water collected in summer. Perfluorobutanoic acid (PFBA), perfluorobutane sulfonate (PFBS), and perfluorooctanoic acid (PFOA) were the dominant PFASs in four seasons with a total contribution of over 90%. The discharge of two fluorine chemical industry parks was predicted to be the main contamination source of PFASs in the study area. The daily and annual mass flows were calculated according to data of detected PFAS concentrations and water discharge, and the annual mass loading of PFASs into the Bohai Sea from the Daling River reached to 461 kg year(-1). Hazard assessment indicated that concentrations of PFASs in study area had little risk to aquatic organisms and wildlife. However, the multiple health risk would be relatively high if the water was served as drinking water in the study area.

  10. Emission, Dynamics and Transport of Perfluoroalkyl Substances from Land to Ocean by the Great East Japan Earthquake in 2011.

    PubMed

    Yamazaki, Eriko; Yamashita, Nobuyoshi; Taniyasu, Sachi; Miyazawa, Yasumasa; Gamo, Toshitaka; Ge, Hui; Kannan, Kurunthachalam

    2015-10-01

    Water samples collected along the Japanese coast and in the open Pacific Ocean in 2010, 2011, and 2012 were analyzed for perfluoroalkyl substances (PFASs) to evaluate the effect of Great East Japan Earthquake (EQ 3.11), which occurred on March 11, 2011, on the dispersion of chemical pollutants. Ultratrace analysis of PFASs in water, a super computer simulation, and an inventory analysis from industrial records revealed the sources and dynamics of PFASs during the EQ 3.11 disaster. In this respect, EQ 3.11 destroyed solid infrastructure on land, and within minutes, PFASs stocked therein were released into the open environment. The historically significant tsunami backwash swept them away from their origin to the coastal water within several hours. It was estimated that from 0.8 to 1.0 tons of perfluorooctanesulfonate (PFOS) and 4.8 to 5.1 tons of PFOA were discharged into the coastal waters after EQ 3.11 and the tsunami that followed. The reconstruction of EQ 3.11 also traced the influence of this pollution in open ocean water until March 2012, and a statistical and finger printing analysis revealed that there were different distribution mechanisms in coastal regions than in the open ocean for PFOS, other shorter chain perfluorinated sulfonic acids and perfluorinated carboxylic acids.

  11. Emission, Dynamics and Transport of Perfluoroalkyl Substances from Land to Ocean by the Great East Japan Earthquake in 2011.

    PubMed

    Yamazaki, Eriko; Yamashita, Nobuyoshi; Taniyasu, Sachi; Miyazawa, Yasumasa; Gamo, Toshitaka; Ge, Hui; Kannan, Kurunthachalam

    2015-10-01

    Water samples collected along the Japanese coast and in the open Pacific Ocean in 2010, 2011, and 2012 were analyzed for perfluoroalkyl substances (PFASs) to evaluate the effect of Great East Japan Earthquake (EQ 3.11), which occurred on March 11, 2011, on the dispersion of chemical pollutants. Ultratrace analysis of PFASs in water, a super computer simulation, and an inventory analysis from industrial records revealed the sources and dynamics of PFASs during the EQ 3.11 disaster. In this respect, EQ 3.11 destroyed solid infrastructure on land, and within minutes, PFASs stocked therein were released into the open environment. The historically significant tsunami backwash swept them away from their origin to the coastal water within several hours. It was estimated that from 0.8 to 1.0 tons of perfluorooctanesulfonate (PFOS) and 4.8 to 5.1 tons of PFOA were discharged into the coastal waters after EQ 3.11 and the tsunami that followed. The reconstruction of EQ 3.11 also traced the influence of this pollution in open ocean water until March 2012, and a statistical and finger printing analysis revealed that there were different distribution mechanisms in coastal regions than in the open ocean for PFOS, other shorter chain perfluorinated sulfonic acids and perfluorinated carboxylic acids. PMID:26321264

  12. Perfluoroalkylated Substance Effects in Xenopus laevis A6 Kidney Epithelial Cells Determined by ATR-FTIR Spectroscopy and Chemometric Analysis

    PubMed Central

    2016-01-01

    The effects of four perfluoroalkylated substances (PFASs), namely, perfluorobutanesulfonate (PFBS), perfluorooctanoic acid (PFOA), perfluorooctanesulfonate (PFOS), and perfluorononanoic acid (PFNA) were assessed in Xenopus laevis A6 kidney epithelial cells by attenuated total reflection Fourier-transform infrared (ATR-FTIR) spectroscopy and chemometric analysis. Principal component analysis–linear discriminant analysis (PCA-LDA) was used to visualize wavenumber-related alterations and ANOVA-simultaneous component analysis (ASCA) allowed data processing considering the underlying experimental design. Both analyses evidenced a higher impact of low-dose PFAS-treatments (10–9 M) on A6 cells forming monolayers, while there was a larger influence of high-dose PFAS-treatments (10–5 M) on A6 cells differentiated into dome structures. The observed dose–response PFAS-induced effects were to some extent related to their cytotoxicity: the EC50-values of most influential PFAS-treatments increased (PFOS < PFNA < PFOA ≪ PFBS), and higher-doses of these chemicals induced a larger impact. Major spectral alterations were mainly attributed to DNA/RNA, secondary protein structure, lipids, and fatty acids. Finally, PFOS and PFOA caused a decrease in A6 cell numbers compared to controls, whereas PFBS and PFNA did not significantly change cell population levels. Overall, this work highlights the ability of PFASs to alter A6 cells, whether forming monolayers or differentiated into dome structures, and the potential of PFOS and PFOA to induce cell death. PMID:27078751

  13. Serum sickness

    MedlinePlus

    Drug allergy - serum sickness; Allergic reaction - serum sickness; Allergy - serum sickness ... penicillin, cefaclor, and sulfa) can cause a similar reaction. Injected proteins such as antithymocyte globulin (used to ...

  14. Bioaccumulation of perfluoroalkyl carboxylates (PFCAs) and perfluoroalkane sulfonates (PFSAs) by earthworms (Eisenia fetida) in soil.

    PubMed

    Zhao, Shuyan; Zhu, Lingyan; Liu, Li; Liu, Zhengtao; Zhang, Yahui

    2013-08-01

    Earthworms were exposed to artificially contaminated soils with ten perfluoroalkyl substances (PFASs). PFASs with longer perfluorinated carbon chain displayed higher uptake rate coefficients (k(u)), longer half-life (t(½)) and time to steady-state (t(ss)) but lower elimination rate coefficients (k(e)) than the shorter ones. Similarly, perfluorosulfonates acids (PFSAs) displayed higher ku, longer t(½) and tss but lower ke than perflurocarboxylic acids (PFCAs) with the same perfluorinated chain length. All the studied PFASs, including those with seven or less perfluorinated carbons, were bioaccumulated in the earthworms and the biota-to-soil accumulation factors (BSAFs) increased with perfluorinated carbon chain length and were greater for PFSAs than for PFCAs of equal perfluoroalkyl chain length. The BSAFs were found to be dependent on the concentrations of PFASs in soil and decreased as the level of PFASs in soil increased.

  15. Perfluoroalkyl substances detected in the world's southernmost marine mammal, the Weddell seal (Leptonychotes weddellii).

    PubMed

    Routti, Heli; Krafft, Bjørn A; Herzke, Dorte; Eisert, Regina; Oftedal, Olav

    2015-02-01

    This study investigates concentrations of 18 perfluoroalkyl substances (PFAS) in blood plasma of adult lactating Weddell seals (Leptonychotes weddellii) (n = 10) from McMurdo Sound, Antarctica. Perfluoroundecanoic acid (PFUnDA) was detected in all samples at concentrations ranging from 0.08 to 0.23 ng/ml. Perfluorooctane sulfonate (PFOS), perfluorohexanoate (PFHxA) and perfluorotridecanoate (PFTriDA) were sporadically detected, while the remaining compounds were below the limit of detection. This is the first report of detectible concentrations of PFASs in an endemic Antarctic marine mammal species. We suggest that the pollutants have been subjected to long range atmospheric transportation and/or derive from a local source. A review of these and published data indicate that perfluoroalkyl carboxylates (PFCAs) dominate in biotic PFAS patterns in species feeding south of the Antarctic Circumpolar Current (ACC), whereas PFOS was the major PFAS detected in species feeding predominantly north of the current.

  16. Tribological reactions of perfluoroalkyl polyether oils with stainless steel under ultrahigh vacuum conditions at room temperature

    NASA Technical Reports Server (NTRS)

    Mori, Shigeyuki; Morales, Wilfredo

    1989-01-01

    The reaction between three types of commercial perfluoroalkyl polyether (PFPE) oils and stainless steel 440C was investigated experimentally during sliding under ultrahigh vacuum conditions at room temperature. It is found that the tribological reaction of PFPE is mainly affected by the activity of the mechanically formed fresh surfaces of metals rather than the heat generated at the sliding contacts. The fluorides formed on the wear track act as a boundary layer, reducing the friction coefficient.

  17. Toxicokinetics of seven perfluoroalkyl sulfonic and carboxylic acids in pigs fed a contaminated diet.

    PubMed

    Numata, Jorge; Kowalczyk, Janine; Adolphs, Julian; Ehlers, Susan; Schafft, Helmut; Fuerst, Peter; Müller-Graf, Christine; Lahrssen-Wiederholt, Monika; Greiner, Matthias

    2014-07-16

    The transfer of a mixture of perfluoroalkyl acids (PFAAs) from contaminated feed into the edible tissues of 24 fattening pigs was investigated. Four perfluoroalkyl sulfonic (PFSAs) and three perfluoroalkyl carboxylic acids (PFCAs) were quantifiable in feed, plasma, edible tissues, and urine. As percentages of unexcreted PFAA, the substances accumulated in plasma (up to 51%), fat, and muscle tissues (collectively, meat 40-49%), liver (under 7%), and kidney (under 2%) for most substances. An exception was perfluorooctanesulfonic acid (PFOS), with lower affinity for plasma (23%) and higher for liver (35%). A toxicokinetic model is developed to quantify the absorption, distribution, and excretion of PFAAs and to calculate elimination half-lives. Perfluorohexanoic acid (PFHxA), a PFCA, had the shortest half-life at 4.1 days. PFSAs are eliminated more slowly (e.g., half-life of 634 days for PFOS). PFAAs in pigs exhibit longer elimination half-lives than in most organisms reported in the literature, but still shorter than in humans.

  18. Distribution of perfluoroalkyl compounds in seawater from northern Europe, Atlantic Ocean, and Southern Ocean.

    PubMed

    Ahrens, Lutz; Xie, Zhiyong; Ebinghaus, Ralf

    2010-02-01

    The global distribution of perfluoroalkyl compounds (PFCs) were investigated in surface water samples collected onboard the Polarstern in Northern Europe, Atlantic and Southern Ocean (52 degrees N-69 degrees S) in 2008. The water samples were solid-phase extracted with Oasis WAX cartridges and analysed using the high-performance liquid chromatography interfaced to tandem mass spectrometry. Concentrations of various PFCs, including C(4), C(6), C(8) perfluoroalkyl sulfonates (PFSAs), perfluorooctane sulfinate (PFOSi), C(5)-C(12) perfluoroalkyl carboxylic acids (PFCA) and perfluorooctane sulfonamide (FOSA) were quantified. Perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) were the predominant compounds with a maximum concentration of 232 and 223pgL(-1), respectively. Results indicate that industrial areas like the European Continent act as source of PFCs, while ocean water is an important as a sink as well as the transport medium of these compounds. Interestingly, in the equator area the summation operatorPFC concentration increased, which indicates that there exists an atmospheric or other unknown input source of PFCs. In the Southern Ocean only PFOS was detected which could be caused by atmospheric transport of its precursors.

  19. Cu-Catalyzed Multicomponent Reaction of Styrenes, Perfluoroalkyl Halide, Alcohol, and tert-Butyl Hydroperoxide: One-Pot Synthesis of (Z)-β-Alkoxyperfluoroalkenone.

    PubMed

    Luo, Qiang; Liu, Chunmei; Tong, Jingjing; Shao, Ying; Shan, Wenyu; Wang, Hanghang; Zheng, Hao; Cheng, Jiang; Wan, Xiaobing

    2016-04-15

    An efficient synthesis of Z-perfluoroalkyl-substituted enones by a multicomponent reaction strategy has been described. A variety of elusive perfluoroalkylated enones are furnished under mild reaction conditions in good yields with unique chemo- and stereoselectivity. A sequence of radical-mediated Kornblum-DeLaMare reaction, Michael addition, and HF elimination is proposed for the mechanism. PMID:26980724

  20. LC-MS analysis of estradiol in human serum and endometrial tissue: Comparison of electrospray ionization, atmospheric pressure chemical ionization and atmospheric pressure photoionization.

    PubMed

    Keski-Rahkonen, Pekka; Huhtinen, Kaisa; Desai, Reena; Harwood, D Tim; Handelsman, David J; Poutanen, Matti; Auriola, Seppo

    2013-09-01

    Accurate measurement of estradiol (E2) is important in clinical diagnostics and research. High sensitivity methods are critical for specimens with E2 concentrations at low picomolar levels, such as serum of men, postmenopausal women and children. Achieving the required assay performance with LC-MS is challenging due to the non-polar structure and low proton affinity of E2. Previous studies suggest that ionization has a major role for the performance of E2 measurement, but comparisons of different ionization techniques for the analysis of clinical samples are not available. In this study, female serum and endometrium tissue samples were used to compare electrospray ionization (ESI), atmospheric pressure chemical ionization (APCI) and atmospheric pressure photoionization (APPI) in both polarities. APPI was found to have the most potential for E2 analysis, with a quantification limit of 1 fmol on-column. APCI and ESI could be employed in negative polarity, although being slightly less sensitive than APPI. In the presence of biological background, ESI was found to be highly susceptible to ion suppression, while APCI and APPI were largely unaffected by the sample matrix. Irrespective of the ionization technique, background interferences were observed when using the multiple reaction monitoring transitions commonly employed for E2 (m/z 271 > 159; m/z 255 > 145). These unidentified interferences were most severe in serum samples, varied in intensity between ionization techniques and required efficient chromatographic separation in order to achieve specificity for E2.

  1. Perfluoroalkyl compounds in relation to life-history and reproductive parameters in bottlenose dolphins (Tursiops truncatus) from Sarasota Bay, Florida, U.S.A.

    PubMed

    Houde, Magali; Balmer, Brian C; Brandsma, Sicco; Wells, Randall S; Rowles, Teri K; Solomon, Keith R; Muir, Derek C G

    2006-09-01

    Perfluoroalkyl compounds (PFCs) were determined in plasma, milk, and urine of free-ranging bottlenose dolphins (Tursiops truncatus) from Sarasota Bay (FL, USA) during three winter and two summer capture-and-release programs (2002-2005). Plasma and urine samples were extracted using an ion-pairing method. Perfluoroalkyl compounds were extracted from milk samples using acetonitrile, and extracts were cleaned with graphitized nonporous carbon. All extracts were analyzed by high-performance liquid chromatography-tandem mass spectrometry. Mean seasonal sum of PFCs (sigma PFCs) detected in dolphin plasma ranged from 530 to 927 ng/g wet weight. No significant differences (p > 0.05) were found in concentrations between seasons, suggesting a constant exposure to PFCs. Overall, blubber thickness of dolphins did not correlate with PFC concentrations in plasma, suggesting an absence of PFC sequestration in blubber. Sexually immature calves (age, <10 years; mean sigma PFCs, 1,410 +/- 780 ng/ g wet wt) were significantly more contaminated (p < 0.001) than their mothers (mean sigma PFCs, 366 +/- 351 ng/g wet wt). The reproductive history of females had a significant role in the burden of PFC contamination; PFC concentrations in nulliparous females (females that have not been observed with calves) were significantly greater than those detected in uniparous females (females that have been observed with one calf), suggesting an off-loading of PFCs during or after parturition. To investigate this hypothesis, PFCs were analyzed in milk samples (n=10; mean sigma PFCs, 134 +/- 76.1 ng/g wet wt), confirming a maternal transfer of PFCs through lactation in dolphins. Results from the present study showed that young and developing bottlenose dolphins are highly exposed to PFCs. These chemicals also were detected in urine (mean sigma PFCs, 26.6 +/- 79 ng/g wet wt), indicating that the urinary system is an important pathway of PFC depuration in dolphins. PMID:16986796

  2. Spatial distribution and importance of potential perfluoroalkyl acid precursors in urban rivers and sewage treatment plant effluent--case study of Tama River, Japan.

    PubMed

    Ye, Feng; Tokumura, Masahiro; Islam, Md Saiful; Zushi, Yasuyuki; Oh, Jungkeun; Masunaga, Shigeki

    2014-12-15

    Production and use of perfluorooctane sulfonate (PFOS) is regulated worldwide. However, numerous potential precursors that eventually decompose into PFOS and other perfluoroalkyl acids (PFAAs) such as perfluorooctanoic acid (PFOA) are still being used and have not been studied in detail. Therefore, knowledge about the levels and sources of the precursors is essential. We investigated the total concentration of potential PFAA precursors in the Tama River, which is one of the major rivers flowing into the Tokyo Bay, by converting all the perfluorinated carboxylic acid (PFCA) and perfluoroalkyl sulfonic acid (PFSA) precursors into PFCAs by chemical oxidation. The importance of controlling PFAA precursors was determined by calculating the ratios of PFCAs formed by oxidation to the PFAAs originally present (ΣΔ[PFCAC4-C12]/Σ[PFAAs]before oxidation) (average = 0.28 and 0.69 for main and tributary branch rivers, respectively). Higher total concentrations of Δ[PFCAs] were found in sewage treatment plant (STP) effluents. However, the ratios found in the effluents were lower (average = 0.21) than those found in the river water samples, which implies the decomposition of some precursors into PFAAs during the treatment process. On the other hand, higher ratios were observed in the upstream water samples and the existence of emission sources other than the STP effluents was indicated. This study showed that although the treatment process converting a part of the PFAA precursors into PFAAs, STPs were important sources of precursors to the Tama River. To reduce the levels of PFAAs in the aquatic environment, it is necessary to reduce the emission of the PFAA precursors as well.

  3. Iodinated (Perfluoro)alkyl Quinoxalines by Atom Transfer Radical Addition Using ortho-Diisocyanoarenes as Radical Acceptors.

    PubMed

    Leifert, Dirk; Studer, Armido

    2016-09-12

    A simple method for the preparation of functionalized quinoxalines is reported. Starting from readily accessible ortho-diisocyanoarenes and (perfluoro)alkyl iodides, the quinoxaline core is constructed during (perfluoro)alkylation by atom transfer radical addition (ATRA), resulting in 2-iodo-3-(perfluoro)alkylquinoxalines. The radical cascades are readily initiated either with visible light or by using α,α'-azobisisobutyronitrile (AIBN). The heteroarene products are obtained in high yields (up to 94 %), and the method can be readily scaled up. Useful follow-up chemistry documents the value of the novel radical quinoxaline synthesis.

  4. Iodinated (Perfluoro)alkyl Quinoxalines by Atom Transfer Radical Addition Using ortho-Diisocyanoarenes as Radical Acceptors.

    PubMed

    Leifert, Dirk; Studer, Armido

    2016-09-12

    A simple method for the preparation of functionalized quinoxalines is reported. Starting from readily accessible ortho-diisocyanoarenes and (perfluoro)alkyl iodides, the quinoxaline core is constructed during (perfluoro)alkylation by atom transfer radical addition (ATRA), resulting in 2-iodo-3-(perfluoro)alkylquinoxalines. The radical cascades are readily initiated either with visible light or by using α,α'-azobisisobutyronitrile (AIBN). The heteroarene products are obtained in high yields (up to 94 %), and the method can be readily scaled up. Useful follow-up chemistry documents the value of the novel radical quinoxaline synthesis. PMID:27510610

  5. Chemical composition of defatted strawberry and raspberry seeds and the effect of these dietary ingredients on polyphenol metabolites, intestinal function, and selected serum parameters in rats.

    PubMed

    Kosmala, Monika; Zduńczyk, Zenon; Juśkiewicz, Jerzy; Jurgoński, Adam; Karlińska, Elżbieta; Macierzyński, Jakub; Jańczak, Rafał; Rój, Edward

    2015-03-25

    Strawberry and raspberry seeds were chemically analyzed and added as dietary ingredients to investigate the physiological response of rats. In both cases the main component was dietary fiber and the main polyphenols were ellagitannins (ET). The strawberry ET were mainly constituted by monomers and a dimer, agrimoniin, whereas raspberry ET were mainly constituted by a dimer, sanguiin-H-6, and a trimer, lambertianin-C. The lower content and the less polymerized structure of strawberry ET resulted in a higher cecal metabolites concentration (mainly nasutin and urolithin-A) in comparison to rats fed diet containing raspberry seeds. Dietary raspberry seeds, a source of dietary fiber, despite being richer in polyphenol compounds, were better utilized in fermentation processes, resulting in enhanced production of short-chain fatty acids. As opposed to strawberry seeds, the treatment with raspberry seeds beneficially improved the atherogenic index of a diet, mainly due to reduced triacylglycerol concentration in the serum.

  6. Restricted access molecularly imprinted polymers obtained by bovine serum albumin and/or hydrophilic monomers' external layers: a comparison related to physical and chemical properties.

    PubMed

    Santos, Mariane Gonçalves; Moraes, Gabriel de Oliveira Isac; Nakamura, Maurício Gustavo; dos Santos-Neto, Álvaro José; Figueiredo, Eduardo Costa

    2015-11-21

    Molecularly imprinting polymers (MIPs) can be modified with external layers in order to obtain restricted access molecularly imprinted polymers (RAMIPs) able to exclude macromolecules and retain low weight compounds. These modifications have been frequently achieved using hydrophilic monomers, chemically bound on the MIP surface. Recently, our group proposed a new biocompatible RAMIP based on the formation of a bovine serum albumin coating on the surface of MIP particles. This material has been used to extract drugs directly from untreated human plasma samples, but its physicochemical evaluation has not been carried out yet, mainly in comparison with RAMIPs obtained by hydrophilic monomers. Thus, we proposed in this paper a comparative study involving the surface composition, microscopic aspect, selectivity, binding kinetics, adsorption and macromolecule elimination ability of these different materials. We concluded that the synthesis procedure influences the size and shape of particles and that hydrophilic co-monomer addition as well as coating with BSA do not alter the chemical recognition ability of the material. The difference between imprinted and non-imprinted polymers' adsorption was evident (suggesting that imprinted polymers have a better capacity to bind the template than the non-imprinted ones). The Langmuir model presents the best fit to describe the materials' adsorption profile. The polymer covered with hydrophilic monomers presented the best adsorption for the template in an aqueous medium, probably due to a hydrophilic layer on its surface. We also concluded that an association of the hydrophilic monomers with the bovine serum albumin coating is important to obtain materials with higher capacity of macromolecule exclusion.

  7. Restricted access molecularly imprinted polymers obtained by bovine serum albumin and/or hydrophilic monomers' external layers: a comparison related to physical and chemical properties.

    PubMed

    Santos, Mariane Gonçalves; Moraes, Gabriel de Oliveira Isac; Nakamura, Maurício Gustavo; dos Santos-Neto, Álvaro José; Figueiredo, Eduardo Costa

    2015-11-21

    Molecularly imprinting polymers (MIPs) can be modified with external layers in order to obtain restricted access molecularly imprinted polymers (RAMIPs) able to exclude macromolecules and retain low weight compounds. These modifications have been frequently achieved using hydrophilic monomers, chemically bound on the MIP surface. Recently, our group proposed a new biocompatible RAMIP based on the formation of a bovine serum albumin coating on the surface of MIP particles. This material has been used to extract drugs directly from untreated human plasma samples, but its physicochemical evaluation has not been carried out yet, mainly in comparison with RAMIPs obtained by hydrophilic monomers. Thus, we proposed in this paper a comparative study involving the surface composition, microscopic aspect, selectivity, binding kinetics, adsorption and macromolecule elimination ability of these different materials. We concluded that the synthesis procedure influences the size and shape of particles and that hydrophilic co-monomer addition as well as coating with BSA do not alter the chemical recognition ability of the material. The difference between imprinted and non-imprinted polymers' adsorption was evident (suggesting that imprinted polymers have a better capacity to bind the template than the non-imprinted ones). The Langmuir model presents the best fit to describe the materials' adsorption profile. The polymer covered with hydrophilic monomers presented the best adsorption for the template in an aqueous medium, probably due to a hydrophilic layer on its surface. We also concluded that an association of the hydrophilic monomers with the bovine serum albumin coating is important to obtain materials with higher capacity of macromolecule exclusion. PMID:26460233

  8. Development of a new chemically modified carbon paste electrode for selective determination of urinary and serum oxalate concentration.

    PubMed

    Soleymanpour, Ahmad; Shafaatian, Bita; Mirfakhraei, Homeira Sadat; Rezaeifard, Abdolreza

    2013-11-15

    The construction and evaluation of a novel modified carbon paste electrode with high selectivity toward oxalate ion are described. The constructed carbon paste potentiometric sensor for oxalate ion is based on the use of a zirconium salan complex as a good ionophore in the carbon paste matrix. The electrode exhibits a Nernstian slope of 29.1 mV/decade to oxalate ion over a wide concentration range from 1.5×10(-6) to 3.9 ×10(-2) mol L(-1) with a low detection limit of 7.0×10(-7) mol L(-1). The electrode possesses fast response time, satisfactory reproducibility, appropriate lifetime, and most importantly, good selectivity toward C2O4(2-) relative to a variety of common anions. The potentiometric response of the electrode is independent of the pH of the test solution in the pH range 2.5-8.0. The modified carbon paste electrode was successfully applied as an indicator electrode in potentiometric titration and potentiometric determination of oxalate ion in mineral water, blood serum and urine samples.

  9. TOXICOGENOMIC STUDY OF TRIAZOLE FUNGICIDES AND PERFLUOROALKYL ACIDS

    EPA Science Inventory

    Toxicogenomic analysis of five environmental contaminants was performed to investigate the ability of genomics to categorize chemicals and elucidate mechanisms of toxicity. Three triazole antifungals (myclobutanil, propiconazole and triadimefon) and two perfluorinated compounds (...

  10. Design and chemical synthesis of iodine-containing molecules for application to solar-pumped I* lasers

    NASA Technical Reports Server (NTRS)

    Shiner, C. S.

    1985-01-01

    This work is directed toward the design and chemical synthesis of new media for solar-pumped I* lasers. In view of the desirability of preparing a perfluoroalkyl iodide absorbing strongly at 300 nm, the relationship betwen perfluoroalkyl iodide structure and the corresponding absorption wavelength was reexamined. Analysis of existing data suggests that, in this family of compounds, the absorption maximum shifts to longer wavelength, as desired, as the C-I bond in the lasant is progressively weakened. Weakening of the C-I bond correlates, in turn, with increasing stability of the perfluoroalkyl radical formed upon photodissociation of the iodide. The extremely promising absorption characteristics of perfluoro-tert-butyl iodide can be accounted for on this basis. A new technique of diode laser probing to obtain precise yields of I* atoms in photodissociation was also developed.

  11. Contamination profiles of perfluoroalkyl substances in five typical rivers of the Pearl River Delta region, South China.

    PubMed

    Pan, Chang-Gui; Ying, Guang-Guo; Liu, You-Sheng; Zhang, Qian-Qian; Chen, Zhi-Feng; Peng, Feng-Jiao; Huang, Guo-Yong

    2014-11-01

    A survey on contamination profiles of eighteen perfluoroalkyl substances (PFASs) was performed via high performance liquid chromatography-tandem mass spectrometry for surface water and sediments from five typical rivers of the Pearl River Delta region, South China in summer and winter in 2012. The total concentrations of the PFASs in the water phase of the five rivers ranged from 0.14 to 346.72 ng L(-1). The PFAS concentrations in the water phase were correlated positively to some selected water quality parameters such as chemical oxygen demand (COD) (0.7913) and conductivity (0.5642). The monitoring results for the water samples showed significant seasonal variations, while those for the sediment samples showed no obvious seasonal variations. Among the selected 18 PFASs, perfluorooctane sulfonic acid (PFOS) was the dominant PFAS compound both in water and sediment for two seasons with its maximum concentration of 320.5 ng L(-1) in water and 11.4 ng g(-1) dry weight (dw) in sediment, followed by perfluorooctanoic acid (PFOA) with its maximum concentration of 26.48 ng L(-1) in water and 0.99 ng g(-1) dw in sediment. PFOS and PFOA were found at relatively higher concentrations in the Shima River and Danshui River than in the other three rivers (Xizhijiang River, Dongjiang River and Shahe River). The principal component analysis for the PFASs concentrations in water and sediment separated the sampling sites into two groups: rural and agricultural area, and urban and industrial area, suggesting the PFASs in the riverine environment were mainly originated from industrial and urban activities in the region.

  12. In situ fate and partitioning of waterborne perfluoroalkyl acids (PFAAs) in the Youngsan and Nakdong River Estuaries of South Korea.

    PubMed

    Hong, Seongjin; Khim, Jong Seong; Park, Jinsoon; Kim, Minhee; Kim, Woong-Ki; Jung, Jinho; Hyun, Seunghun; Kim, Jeong-Gyu; Lee, Hyojin; Choi, Heeseon J; Codling, Garry; Giesy, John P

    2013-02-15

    Concentrations, distributions, fate, and partitioning of perfluoroalkyl acids (PFAAs) were investigated in surface water (n=34) collected from the Youngsan and Nakdong River Estuaries of South Korea. Thirteen individual PFAAs in water and suspended solids (SS) were quantified by use of HPLC-MS/MS. PFAAs were detected in all samples, which indicated that they were widely distributed in the study area. Greater concentrations of PFAAs were found at some inland sites which seemed to be affected by direct input from point sources, such as wastewater treatment plants, and/or indirect diffusive sources, such as surface runoff. Spatial distributions of PFAAs in estuaries along transects toward the open sea demonstrated that these chemicals were transported to the outer region primarily by water discharged during the rainy season. Field-based partition coefficients (K(d)) for long-chain PFAAs (C≥8) were significantly correlated with salinity (r(2)=0.48 to 0.73, p<0.01); K(d) values increased exponentially as a function of salinity. Due to the 'salting-out' effect, PFAAs were largely scavenged by adsorption onto SS and/or sediments in estuarine environments. In addition, values for K(d) of those PFAAs were directly proportional to the number of carbon atoms in the PFAAs. Salting constants of selected PFAAs were notably greater than those of other environmental organic contaminants, which indicated that adsorption of PFAAs is largely associated with salinity. Overall, the results of the present study will provide better understanding of the fate and transport of PFAAs in the zone of salinity boundary that can be used for developing fate models of PFAAs in the coastal marine environment.

  13. Evaluating the additivity of perfluoroalkyl acids (PFAAs) in binary combinations on peroxisome proliferator-activated receptor-a(PPARa) activation

    EPA Science Inventory

    Perfluoroalkyl acids (PFAAs) are found globally in the environment, detected in humans and wildlife, and are typically present as mixtures of PFAA congeners. Mechanistic studies have found that responses to PFAAs are mediated in part by PPARa. Our previous studies showed that ind...

  14. Determining a Robust D-Optimal Design for Testing for Departure from Additivity in a Mixture of Four Perfluoroalkyl Acids.

    EPA Science Inventory

    Our objective is to determine an optimal experimental design for a mixture of perfluoroalkyl acids (PFAAs) that is robust to the assumption of additivity. PFAAs are widely used in consumer products and industrial applications. The presence and persistence of PFAAs, especially in ...

  15. Bioavailability and bioconcentration potential of perfluoroalkyl-phosphinic and -phosphonic acids in zebrafish (Danio rerio): Comparison to perfluorocarboxylates and perfluorosulfonates.

    PubMed

    Chen, Fangfang; Gong, Zhiyuan; Kelly, Barry C

    2016-10-15

    Currently, information regarding bioavailability and bioconcentration potential of perfluoroalkyl phosphinic acids (PFPiAs) in aquatic organisms does not exist. The main objective of the present study was to assess uptake and elimination kinetics of PFPiAs in zebrafish (Danio rerio) following aqueous exposure. The results showed that PFPiA exposure can result in very high steady-state bioconentration factors (BCFss), compared to perfluorocarboxylates and perfluorosulfonates.C6/C10 PFPiA exhibited the highest BCFss, ranging between 10(7) and 10(10), orders of magnitude higher than those for long-chain perfluorocarboxylates. Strong positive relationships were observed between BCFss versus the membrane-water distribution coefficient (Dmw) and the protein-water partition coefficient (Kpw) of the studied perfluoroalkyl substances. However, BCFss exhibited a substantial drop for the very hydrophobic PFPiAs (C8/C10 and C6/C12 PFPiAs). The reduced BCFss of these long-chain PFPiAs (perfluoroalkyl chain length=18; Dmw=10(9)) is likely the result of reduced bioavailability due to interaction with solute molecules/organic matter present in the water phase and/or reduced gill membrane permeability. While PFPiAs can be metabolized to perfluoroalkyl phosphonic acids, the metabolic transformation rate seems insufficient to counteract the high degree of uptake across gill membranes. These findings help to better understand exposure pathways and bioaccumulation behavior of these important perfluorinated acids in aquatic systems. PMID:27285794

  16. Tissue-specific concentrations and patterns of perfluoroalkyl carboxylates and sulfonates in East Greenland polar bears.

    PubMed

    Greaves, Alana K; Letcher, Robert J; Sonne, Christian; Dietz, Rune; Born, Erik W

    2012-11-01

    Several perfluoroalkyl carboxylates (PFCAs) and perfluoroalkyl sulfonates (PFSAs) of varying chain length are bioaccumulative in biota. However, wildlife reports have focused on liver and with very little examination of other tissues, and thus there is a limited understanding of their distribution and potential effects in the mammalian body. In the present study, the comparative accumulation of C(6) to C(15) PFCAs, C(4), C(6), C(8) and C(10) PFSAs, and select precursors were examined in the liver, blood, muscle, adipose, and brain of 20 polar bears (Ursus maritimus) from Scoresby Sound, Central East Greenland. Overall, PFSA and PFCA concentrations were highest in liver followed by blood > brain > muscle ≈ adipose. Liver and blood samples contained proportionally more of the shorter/medium chain length (C(6) to C(11)) PFCAs, whereas adipose and brain samples were dominated by longer chain (C(13) to C(15)) PFCAs. PFCAs with lower lipophilicities accumulated more in the liver, whereas the brain accumulated PFCAs with higher lipophilicities. The concentration ratios (±SE) between perfluorooctane sulfonate and its precursor perfluorooctane sulfonamide varied among tissues from 9 (±1):1 (muscle) to 36 (±7):1 (liver). PFCA and PFSA patterns in polar bears indicate that the pharmacokinetics of these compounds are to some extent tissue-specific, and are the result of several factors that may include differing protein interactions throughout the body.

  17. Survey of perfluoroalkyl acids (PFAAs) and their precursors present in Japanese consumer products.

    PubMed

    Ye, Feng; Zushi, Yasuyuki; Masunaga, Shigeki

    2015-05-01

    Perfluoroalkyl acids (PFAAs) and their precursors have been used in various consumer products. However, limited information regarding their occurrence and concentration levels in products is available. In this study, we investigated 18 PFAAs and 14 PFAA precursors in various categories of consumer products purchased in Japan. Relatively high total concentrations of PFAAs and their precursors were found in sprays for fabrics and textiles (perfluoroalkyl carboxylic acids (PFCAs) (carbon chain length⩾7) were also detected in greater concentrations than short chain PFCAs (⩽6). This result suggests that consumer products are one of the important sources of long-chain PFCAs in the environment.

  18. Bioconcentration of perfluoroalkyl substances by Chironomus plumosus larvae in water with different types of dissolved organic matters.

    PubMed

    Wen, Wu; Xia, Xinghui; Chen, Xi; Wang, Haotian; Zhu, Baotong; Li, Husheng; Li, Yang

    2016-06-01

    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. PMID:26925752

  19. Development and comparison of three liquid chromatography-atmospheric pressure chemical ionization/mass spectrometry methods for determining vitamin D metabolites in human serum.

    PubMed

    Bedner, Mary; Phinney, Karen W

    2012-06-01

    Liquid chromatographic methods with atmospheric pressure chemical ionization mass spectrometry were developed for the determination of the vitamin D metabolites 25-hydroxyvitamin D₂ (25(OH)D₂), 25-hydroxyvitamin D₃ (25(OH)D₃), and 3-epi-25-hydroxyvitamin-D₃ (3-epi-25(OH)D₃) in the four Levels of SRM 972, Vitamin D in Human Serum. One method utilized a C18 column, which separates 25(OH)D₂ and 25(OH)D₃, and one method utilized a CN column that also resolves the diastereomers 25(OH)D₃ and 3-epi-25(OH)D₃. Both methods utilized stable isotope labeled internal standards for quantitation of 25(OH)D₂ and 25(OH)D₃. These methods were subsequently used to evaluate SRM 909c Human Serum, and 25(OH)D₃ was the only vitamin D metabolite detected in this material. However, SRM 909c samples contained matrix peaks that interfered with the determination of the [²H₆]-25(OH)D₃ peak area. The chromatographic conditions for the C18 column were modified to remove this interference, but conditions that separated the matrix peaks from [²H₆]-25(OH)D₃ on the CN column could not be identified. The alternate internal standard [²H₃]-25(OH)D₃ did not suffer from matrix interferences and was used for quantitation of 25(OH)D₃ in SRM 909c. During the evaluation of SRM 909c samples, a third method was developed using a pentafluorophenylpropyl column that also separates the diastereomers 25(OH)D₃ and 3-epi-25(OH)D₃. The 25(OH)D₃ was measured in SRM 909c using all three methods, and the results were compared.

  20. Gas chromatography/atmospheric pressure chemical ionization/mass spectrometry for the analysis of organochlorine pesticides and polychlorinated biphenyls in human serum.

    PubMed

    Geng, Dawei; Jogsten, Ingrid Ericson; Dunstan, Jody; Hagberg, Jessika; Wang, Thanh; Ruzzin, Jerome; Rabasa-Lhoret, Rémi; van Bavel, Bert

    2016-07-01

    A method using a novel atmospheric pressure chemical ionization source for coupling gas chromatography (GC/APCI) to triple quadrupole mass spectrometry (MS/MS) for the determination of organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) regulated by the Stockholm Convention is presented. One microliter injection of a six-point calibration curve of native PCBs and OCPs, ranging from 0.04 to 300pg/μL, was performed. The relative standard deviation (RSD) of the relative response factors (RRFs) was less than 15% with a coefficient of determination (r(2))>0.995. Meanwhile, two calibration solutions (CS), CS 2 (0.4pg/μL) and CS 3 (4pg/μL) were analyzed to study the repeatability calculated for both area and RRFs. The RSD for RRF ranged from 3.1 to 16% and 3.6 to 5.5% for CS 2 and CS 3, respectively. The limits of detection (LOD) determined by peak-to-peak signal-to-noise ratio (S/N) of 3 were compared between the GC/APCI/MS/MS and a GC coupled to high resolution mass spectrometry (GC/HRMS) system. GC/APCI/MS/MS resulted in lower LOD for most of the compounds, except for PCB#74, cis-chlordane and trans-chlordane. GC/APCI/MS/MS and GC/HRMS were also compared by performing analysis on 75 human serum samples together with eight QA/QC serum samples. The comparison between GC/APCI/MS/MS system and GC/HRMS system for 16 of the targeted compounds was carried out. No statistically significant difference was discovered. Due to increased sensitivity and user friendly operation under atmospheric pressure, GC/APCI/MS/MS is a powerful alternative technique that can easily meet the specification of GC/HRMS.

  1. Persistent organic pollutants measured in maternal serum and offspring neurodevelopmental outcomes--a prospective study with long-term follow-up.

    PubMed

    Strøm, Marin; Hansen, Susanne; Olsen, Sjúrður Fróði; Haug, Line Småstuen; Rantakokko, Panu; Kiviranta, Hannu; Halldorsson, Thorhallur Ingi

    2014-07-01

    Fetal exposure to persistent organic pollutants (POPs) has been linked to adverse neurodevelopment, but few studies have had follow-up beyond childhood. The purpose of this study was to examine the association of maternal serum concentrations of two perfluoroalkyl acids (perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS)), polychlorinated biphenyls (PCBs), dichlorodiphenyldichloroethylene (p,p'-DDE) and hexachlorobenzene (HCB) with offspring behavioural and affective disorders and scholastic achievement in a prebirth cohort study with 20 years of follow up. Between 1988 and 1989 pregnant women (n=965) were recruited for the prebirth Danish Fetal Origins 1988 (DaFO88) Cohort in Aarhus, Denmark. Perfluoroalkyl acids, PCBs, p,p'-DDE, and HCB were quantified in serum from week 30 of gestation (n=876 for perfluoroalkyl acids/872 for PCBs, p,p'-DDE, HCB). Offspring were followed up through national registries until 2011. We evaluated associations between maternal serum concentrations of these POPs and offspring neurodevelopmental outcomes, defined as: first admission diagnosis or prescription of medication until age >20 for (1) ADHD; (2) depression; and (3) scholastic achievement defined as mean grade on a standardized written examination given in the 9th grade (final exams of compulsory school in Denmark). Maternal concentrations of organochlorine substances and perfluoroalkyl acids were higher than present day levels. During the follow-up period there were 27 (3.1%) cases of ADHD and 104 (11.9%) cases of depression; the mean scholastic achievement was 6.7 (SD 2.3). Overall we found no association for maternal levels of any of the measured pollutants with offspring behavioural and affective disorders or with scholastic achievement. Our analyses based on biomarkers from a cohort of over 800 pregnant women with long-term close to complete follow-up through national registries showed little evidence of a programming effect of PFOA, PFOS, PCBs, p,p'-DDE, and

  2. 40 CFR 721.10536 - Long-chain perfluoroalkyl carboxylate chemical substances.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ...: Carpet means a finished fabric or similar product intended to be used as a floor covering. This... of carpets or to treat carpets (e.g., for use in the carpet aftercare market), except as noted in... carpet cleaning products shall not be considered a significant new use subject to reporting under...

  3. Specific estrogen-induced cell proliferation of cultured Syrian hamster renal proximal tubular cells in serum-free chemically defined media

    SciTech Connect

    Oberley, T.D.; Lauchner, L.J.; Pugh, T.D.; Gonzalez, A.; Goldfarb, S. ); Li, S.A.; Li, J.J. )

    1989-03-01

    It has long been recognized that the renal proximal tubular epithelium of the hamster is a bona fide estrogen target tissue. The effect of estrogens on the growth of proximal tubule cell explants and dissociated single cells derived from these explant outgrowths has been studied in culture. Renal tubular cells were grown on a PF-HR-9 basement membrane under serum-free chemically defined culture conditions. At 7-14 days in culture, cell number was enhanced 3-fold in the presence of either 17{beta}-estradiol or diethylstilbestrol. A similar 3-fold increase in cell number was also seen at 1 nM 17{beta}-estradiol in subcultured dissociated single tubular cells derived from hamster renal tubular explant outgrowths at 21 days in culture. Concomitant exposure of tamoxifen at 3-fold molar excess in culture completely abolished the increase in cell number seen with 17{beta}-estradiol. The proliferation effect of estrogens on proximal tubular cell growth appears to be species specific since 17{beta}-estradiol did not alter the growth of either rat or guinea pig proximal tubules in culture. In addition, at 7-10 days in culture in the presence of 17{beta}-estradiol, ({sup 3}H)thymidine labeling of hamster tubular cells was enhanced 3-fold. These results clearly indicate that estrogens can directly induce primary epithelial cell proliferation at physiologic concentrations and provide strong additional evidence for an important hormonal role in the neoplastic transformation of the hamster kidney.

  4. Simultaneous determination of perfluoroalkyl phosphonates, carboxylates, and sulfonates in drinking water.

    PubMed

    Ullah, Shahid; Alsberg, Tomas; Berger, Urs

    2011-09-16

    A trace analytical method based on high performance liquid chromatography coupled to quadrupole time-of-flight high resolution mass spectrometry was developed for simultaneous determination of perfluoroalkyl phosphonates (PFPAs, carbon chain lengths C6,8,10), perfluoroalkyl carboxylates (PFCAs, C5-12), and perfluoroalkyl sulfonates (PFSAs, C4,6,8,10) in drinking water (tap water). Analytes were enriched on a mixed mode co-polymeric sorbent (C8+quaternary amine) using solid phase extraction. Chromatographic separation was achieved on a Zorbax Extend C18 reversed phase column using a mobile phase gradient consisting of water, methanol, and acetonitrile containing 2mM ammonium acetate and 5 mM 1-methyl piperidine. The mass spectrometer was operated in electrospray negative ion mode. Use of 1-methyl piperidine in the mobile phase resulted in a significant increase in instrument sensitivity for PFPAs through improved chromatographic resolution, background suppression, and increased ionization efficiency. Method detection limits for extraction of 500 mL tap water were in the ranges of 0.095-0.17 ng/L, 0.027-0.17 ng/L, and 0.014-0.052 ng/L for PFPAs, PFCAs, and PFSAs, respectively. Whole method recoveries at a spiking level of 0.5 ng/L to 500 mL HPLC grade water were 40-56%, 56-97%, and 55-77% for PFPAs, PFCAs, and PFSAs, respectively. A matrix effect (signal enhancement) was observed in the detection of PFPAs in tap water extracts, leading to calculated recoveries of 249-297% at a 0.5 ng/L spiking level. This effect resulted in an additional improvement of method sensitivity for PFPAs. To compensate for the matrix effect, PFPAs in tap water were quantified using matrix-matched and extracted calibration standards. The method was successfully applied to the analysis of drinking water collected from six European countries. PFPAs were not detected except for perfluorooctyl phosphonate (PFOPA) at close to the detection limit of 0.095 ng/L in two water samples from Amsterdam

  5. Determination of C(5)-C(12) perfluoroalkyl carboxylic acids in river water samples in the Czech Republic by GC-MS after SPE preconcentration.

    PubMed

    Dufková, Veronika; Čabala, Radomír; Ševčík, Václav

    2012-04-01

    A method employing solid phase extraction followed by gas chromatography-mass spectrometry with negative chemical ionization has been developed for determination of ultratrace concentrations of perfluoroalkyl carboxylic acids in river water. The effects of the experimental parameters, such as the pH, additions of NaCl and an ion-pairing agent (tetraethylammonium bromide) and the kind of the elution agent, on the efficiency of the test acid extraction have been studied. The analyte extraction recoveries and the limits of detection and determination have been found. The method developed has been tested on determinations of perfluoroalkyl carboxylic acids in the waters of the two largest Czech rivers, Vltava and Labe (Elbe). The best extraction results have been attained without any alteration of the sample pH, with an addition of tetrabutylammonium bromide (a concentration of 50 μg mL(-1) in the sample) and using methanol as the elution agent. Under these conditions, the recoveries of the test acids in the spiked real samples are within ranges from 60% to 104% and 53% to 111% for analyte concentration levels of 1.40 ng mL(-1) and 0.14 ng mL(-1), respectively, depending on the lengths of the perfluorinated chains of the acids. In general, the recovery decreases with increasing length of this chain. The method developed exhibits very low limits of detection and determination and the results are fully comparable with those obtained when using more expensive HPLC-MS/MS instrumentation. Typical values amount to tenths to tens of pg mL(-1) and units to one hundred pg mL(-1) for the limits of detection and determination, respectively; the measuring sensitivity increases with increasing length of the analyte chain. The analyzes of real samples from the Vltava and Elbe rivers have demonstrated that the results obtained are similar to the values published for contamination of the Elbe and other rivers in western and central Europe. The concentrations determined are of the

  6. Preliminary investigation of perfluoroalkyl substances in exploited fishes of two contaminated estuaries.

    PubMed

    Taylor, Matthew D; Johnson, Daniel D

    2016-10-15

    Perfluoroalkyl substances (PFASs) are being increasingly detected in a range of aquatic and terrestrial ecosystems, often resulting from the use of legacy fire-fighting foams. This study conducted an initial investigation of the concentrations of PFASs in the commercially and recreationally exploited species Dusky Flathead, Mud Crab, School Prawn, Sea Mullet, Yellowfin Bream, Eastern King Prawn and Sand Whiting, across two contaminated estuaries. All samples contained perfluoro-n-octane sulfonate (PFOS) except four Yellowfin Bream samples (two from each estuary). Perfluoro-n-octanoic acid (PFOA) was detected only in School Prawn samples from Fullerton Cove, while perfluoro-n-hexane sulfonate (PFHxS) was detected in prawn muscle and in fish liver samples from both estuaries. This study presents one of the first surveys of PFAS in a range of edible saltwater fish and crustaceans in Australia, and these baseline levels of contamination will prove useful for informing future surveys of these emerging contaminants. PMID:27289281

  7. Perfluoroalkyl acids in various edible Baltic, freshwater, and farmed fish in Finland.

    PubMed

    Koponen, Jani; Airaksinen, Riikka; Hallikainen, Anja; Vuorinen, Pekka J; Mannio, Jaakko; Kiviranta, Hannu

    2015-06-01

    In this study, the concentration of perfluoroalkyl acids (PFAAs) in various edible Finnish Baltic Sea, freshwater, and farmed fish species were analysed. PFAAs were present in all the Baltic and freshwater species, but were not observed in any farmed fish. The most abundant compound in each species was perfluorooctane sulfonate (PFOS), comprising 41-100% of the total concentration. The total PFAA concentration varied considerably from 0.31 to 46ngg(-1) fresh weight. A notable variation in the PFAA concentrations implies that a single fish species alone is not suitable for monitoring PFAA contamination in a certain area. Our results confirm that wild domestic fish is one of the PFAA source in the Finnish diet.

  8. Occurrence of perfluoroalkyl substances in fish and water from the Svitava and Svratka rivers, Czech Republic.

    PubMed

    Kovarova, Jana; Marsalek, Petr; Blahova, Jana; Jurcikova, Jana; Kasikova, Barbora; Svobodova, Zdenka

    2012-03-01

    Perfluoroalkyl substances (PFHxS, FHUEA, PFOA, PFOS, FOSA, N-methyl FOSA and PFNA) from seven sites on the Svitava and Svratka rivers in the Brno conurbation (Czech Republic) were determined in fish blood plasma and water. Concentrations of PFHxS, FHUEA, FOSA, and N-methyl FOSA were below detection limits. Major compound in fish blood was PFOS (38.9-57.8 ng mL(-1)), followed by PFNA and PFOA. In water, the major compound detected was PFOA (1.7-178.0 ng mL(-1)), followed by PFOS and PFNA. A significant (p < 0.05) correlation for PFOA concentration in blood plasma and water was found (r = 0.74).

  9. Perfluoroalkyl substances in Daling River adjacent to fluorine industrial parks: implication from industrial emission.

    PubMed

    Meng, Jing; Wang, Tieyu; Wang, Pei; Zhu, Zhaoyun; Li, Qifeng; Lu, Yonglong

    2015-01-01

    The pollution level and source of perfluoroalkyl substances (PFASs) in mainstream and tributary of Daling River in northeast China were investigated in present study. Concentrations of PFASs in surface water and sediment ranged from 4.6 to 3,410 ng/L and from 0.08 to 2.6 ng/g dry weight, respectively. The lowest levels of PFASs were found in vicinity of a drinking water source located in upstream of Daling River. Xihe tributary, which is adjacent to two local fluorine industrial parks, contained the highest level of PFASs. Short-chain PFASs, including perfluorobutanoic acid and perfluorobutane sulfonate, were of higher levels due to their emerging as alternative products for perfluorooctane sulfonate. High level of perfluorooctanoic acid was also found in Daling River. Based on these results, it can be concluded that the relatively severe pollutions of Xihe tributary were caused by long-term development of the two local fluorine industry parks.

  10. Occurrence of perfluoroalkyl compounds in surface waters from the North Pacific to the Arctic Ocean.

    PubMed

    Cai, Minghong; Zhao, Zhen; Yin, Zhigao; Ahrens, Lutz; Huang, Peng; Cai, Minggang; Yang, Haizhen; He, Jianfeng; Sturm, Renate; Ebinghaus, Ralf; Xie, Zhiyong

    2012-01-17

    Perfluoroalkyl compounds (PFCs) were determined in 22 surface water samples (39-76°N) and three sea ice core and snow samples (77-87°N) collected from North Pacific to the Arctic Ocean during the fourth Chinese Arctic Expedition in 2010. Geographically, the average concentration of ∑PFC in surface water samples were 560 ± 170 pg L(-1) for the Northwest Pacific Ocean, 500 ± 170 pg L(-1) for the Arctic Ocean, and 340 ± 130 pg L(-1) for the Bering Sea, respectively. The perfluoroalkyl carboxylates (PFCAs) were the dominant PFC class in the water samples, however, the spatial pattern of PFCs varied. The C(5), C(7) and C(8) PFCAs (i.e., perfluoropentanoate (PFPA), perfluoroheptanoate (PFHpA), and perfluorooctanoate (PFOA)) were the dominant PFCs in the Northwest Pacific Ocean while in the Bering Sea the PFPA dominated. The changing in the pattern and concentrations in Pacific Ocean indicate that the PFCs in surface water were influenced by sources from the East-Asian (such as Japan and China) and North American coast, and dilution effect during their transport to the Arctic. The presence of PFCs in the snow and ice core samples indicates an atmospheric deposition of PFCs in the Arctic. The elevated PFC concentration in the Arctic Ocean shows that the ice melting had an impact on the PFC levels and distribution. In addition, the C(4) and C(5) PFCAs (i.e., perfluorobutanoate (PFBA), PFPA) became the dominant PFCs in the Arctic Ocean indicating that PFBA is a marker for sea ice melting as the source of exposure.

  11. Spatial distribution of perfluoroalkyl substances in surface sediments of five major rivers in China.

    PubMed

    Pan, Chang-Gui; Ying, Guang-Guo; Zhao, Jian-Liang; Liu, You-Sheng; Liu, Shuang-Shuang; Du, Jun; Kookana, Rai S

    2015-04-01

    Perfluoroalkyl substances (PFASs) have received great attention from the public and scientific community due to their potential adverse impacts on the ecosystem and human health. We investigated the occurrence and distribution of 16 PFASs from 2 classes of PFASs-perfluoroalkyl carboxylic acids and perfluoroalkane sulfonic acids-in the archived surface sediments of five major rivers (Yellow River, Hai River, Liao River, Zhujiang River, and Dongjiang River) in northern and southern China. The study was also performed during the wet and dry seasons. Perfluorooctanoic acid and perfluorooctane sulfonic acid were the most frequently detected (detection frequency = 100 and 63 %, respectively) in the sediments of the five rivers; the concentrations ranged from 0.08 to 0.99 ng/g dry weight (dw) and were lower than the limit of detection (

  12. Bioaccumulation of perfluoroalkyl acids by earthworms (Eisenia fetida) exposed to contaminated soils.

    PubMed

    Rich, Courtney D; Blaine, Andrea C; Hundal, Lakhwinder; Higgins, Christopher P

    2015-01-20

    The presence of perfluoroalkyl acids (PFAAs) in biosolids-amended and aqueous film-forming foam (AFFF)-impacted soils results in two potential pathways for movement of these environmental contaminants into terrestrial foodwebs. Uptake of PFAAs by earthworms (Eisenia fetida) exposed to unspiked soils with varying levels of PFAAs (a control soil, an industrially impacted biosolids-amended soil, a municipal biosolids-amended soil, and two AFFF-impacted soils) was measured. Standard 28 day exposure experiments were conducted in each soil, and measurements taken at additional time points in the municipal soil were used to model the kinetics of uptake. Uptake and elimination rates and modeling suggested that steady state bioaccumulation was reached within 28 days of exposure for all PFAAs. The highest concentrations in the earthworms were for perfluorooctane sulfonate (PFOS) in the AFFF-impacted Soil A (2160 ng/g) and perfluorododecanoate (PFDoA) in the industrially impacted soil (737 ng/g). Wet-weight (ww) and organic carbon (OC)-based biota soil accumulation factors (BSAFs) for the earthworms were calculated after 28 days of exposure for all five soils. The highest BSAF in the industrially impacted soil was for PFDoA (0.42 goc/gww,worm). Bioaccumulation factors (BAFs, dry-weight-basis, dw) were also calculated at 28 days for each of the soils. With the exception of the control soil and perfluorodecanoate (PFDA) in the industrially impacted soil, all BAF values were above unity, with the highest being for perfluorohexanesulfonate (PFHxS) in the AFFF-impacted Soil A (139 gdw,soil/gdw,worm). BSAFs and BAFs increased with increasing chain length for the perfluorocarboxylates (PFCAs) and decreased with increasing chain length for the perfluoroalkyl sulfonates (PFSAs). The results indicate that PFAA bioaccumulation into earthworms depends on soil concentrations, soil characteristics, analyte, and duration of exposure, and that accumulation into earthworms may be a potential

  13. Bioaccumulation of perfluoroalkyl acids by earthworms (Eisenia fetida) exposed to contaminated soils.

    PubMed

    Rich, Courtney D; Blaine, Andrea C; Hundal, Lakhwinder; Higgins, Christopher P

    2015-01-20

    The presence of perfluoroalkyl acids (PFAAs) in biosolids-amended and aqueous film-forming foam (AFFF)-impacted soils results in two potential pathways for movement of these environmental contaminants into terrestrial foodwebs. Uptake of PFAAs by earthworms (Eisenia fetida) exposed to unspiked soils with varying levels of PFAAs (a control soil, an industrially impacted biosolids-amended soil, a municipal biosolids-amended soil, and two AFFF-impacted soils) was measured. Standard 28 day exposure experiments were conducted in each soil, and measurements taken at additional time points in the municipal soil were used to model the kinetics of uptake. Uptake and elimination rates and modeling suggested that steady state bioaccumulation was reached within 28 days of exposure for all PFAAs. The highest concentrations in the earthworms were for perfluorooctane sulfonate (PFOS) in the AFFF-impacted Soil A (2160 ng/g) and perfluorododecanoate (PFDoA) in the industrially impacted soil (737 ng/g). Wet-weight (ww) and organic carbon (OC)-based biota soil accumulation factors (BSAFs) for the earthworms were calculated after 28 days of exposure for all five soils. The highest BSAF in the industrially impacted soil was for PFDoA (0.42 goc/gww,worm). Bioaccumulation factors (BAFs, dry-weight-basis, dw) were also calculated at 28 days for each of the soils. With the exception of the control soil and perfluorodecanoate (PFDA) in the industrially impacted soil, all BAF values were above unity, with the highest being for perfluorohexanesulfonate (PFHxS) in the AFFF-impacted Soil A (139 gdw,soil/gdw,worm). BSAFs and BAFs increased with increasing chain length for the perfluorocarboxylates (PFCAs) and decreased with increasing chain length for the perfluoroalkyl sulfonates (PFSAs). The results indicate that PFAA bioaccumulation into earthworms depends on soil concentrations, soil characteristics, analyte, and duration of exposure, and that accumulation into earthworms may be a potential

  14. GC-MS analysis of amino acid enantiomers as their N(O,S)-perfluoroacyl perfluoroalkyl esters: application to space exploration

    NASA Astrophysics Data System (ADS)

    Zampolli, M.; Sternberg, R.; Szopa, C.; Pietrogrande, M. C.; Buch, A.; Dondi, F.; Raulin, F.

    The search for optical activity in extraterrestrial sample is an important key for the study of the origin of life With this aim detection of chemical biomarkers i e of organic molecules which play an important role in biochemistry will be one of the main goals of future space missions To reach this goal an investigation of a GC-MS method based on the derivatization of amino acids by using a mixture of perfluorinated alcohols and perfluorinated anhydrides has been performed Amino acids are converted in their N O S -perfluoroacyl perfluoroalkyl esters in a single step procedure using different combinations of the derivatization reagents trifluoroacetic anhydride TFAA - 2 2 2-trifluoro-1-ethanol TFE TFAA-2 2 3 3 4 4 4-heptafluoro-1-butanol HFB heptafluorobutyric anhydride HFBA -HFB The obtained derivatives are analyzed using two different chiral columns a Chirasil-L-Val and a gammat cyclodextrin Rt- gamma -DEXsa stationary phases which show different and complementary enantiomeric selectivity The mass spectra of the derivatized compounds are studied and mass fragmentation patterns are proposed significant fragment ions can be identified to detect amino acid derivatives The obtained results are compared in terms of the enantiomeric separation achieved and mass spectrometric response Linearity studies and the measurement of the limit of detection LOD prove that the proposed method is suitable for a quantitative determination of several amino acids enantiomers 1 The use of a PTV Programmed Temperature Vaporiser

  15. Hazard assessment of fluorinated alternatives to long-chain perfluoroalkyl acids (PFAAs) and their precursors: status quo, ongoing challenges and possible solutions.

    PubMed

    Wang, Zhanyun; Cousins, Ian T; Scheringer, Martin; Hungerbuehler, Konrad

    2015-02-01

    Because of concerns over the impact of long-chain perfluoroalkyl acids (PFAAs) on humans and the environment, PFAAs and their precursors are being substituted by alternative substances including fluorinated alternatives that are structurally similar to the substances they replace. Using publicly accessible information, we aimed to identify the status quo of the hazard assessment of identified fluorinated alternatives, to analyze possible systemic shortcomings of the current industrial transition to alternative substances, and to outline possible solutions. Fluorinated alternatives, particularly short-chain PFAAs and perfluoroether carboxylic and sulfonic acids (PFECAs and PFESAs), possess high environmental stability and mobility implying that they have a high global contamination potential. In addition to their potential for causing global exposures, certain fluorinated alternatives have been identified as toxic and are thus likely to pose global risks to humans and the environment. Various factors, particularly the information asymmetry between industry and other stakeholders, have contributed to the current lack of knowledge about the risks posed by fluorinated alternatives. Available cases show that a non-fluorinated substitution strategy (employing either chemical or functionality substitutions) can be a possible long-term, sustainable solution and needs to be further developed and assessed.

  16. Quantitative analysis of poly- and perfluoroalkyl compounds in water matrices using high resolution mass spectrometry: optimization for a laser diode thermal desorption method.

    PubMed

    Munoz, Gabriel; Vo Duy, Sung; Budzinski, Hélène; Labadie, Pierre; Liu, Jinxia; Sauvé, Sébastien

    2015-06-30

    An alternative analysis technique for the quantitation of 15 poly- and perfluoroalkyl substances (PFASs) in water matrices is reported. Analysis time between each sample was reduced to less than 20s, all target molecules being analyzed in a single run with the use of laser diode thermal desorption atmospheric pressure chemical ionization (LDTD/APCI) coupled with high resolution accurate mass (HRMS) orbitrap mass spectrometry. LDTD optimal settings were investigated using either one-factor-at-a-time or experimental design methodologies, while orbitrap parameters were optimized simultaneously by means of a Box-Behnken design. Following selection of an adequate sample concentration and purification procedure based on solid-phase extraction and graphite clean-up, the method was validated in an influent wastewater matrix. Environmentally significant limits of detection were reported (0.3-4ngL(-1) in wastewater and 0.03-0.2ngL(-1) in surface water) and out of the 15 target analytes, 11 showed excellent accuracies (±20% of the target values) and recovery rates (75-125%). The method was successfully applied to a selection of environmental samples, including wastewater samples in 7 locations across Canada, as well as surface and tap water samples from the Montreal region, providing insights into the degree of PFAS contamination in this area. PMID:26041525

  17. Cumulative health risk assessment of 17 perfluoroalkylated and polyfluoroalkylated substances (PFASs) in the Swedish population.

    PubMed

    Borg, Daniel; Lund, Bert-Ove; Lindquist, Nils-Gunnar; Håkansson, Helen

    2013-09-01

    Humans are simultaneously exposed to a multitude of chemicals. Human health risk assessment of chemicals is, however, normally performed on single substances, which may underestimate the total risk, thus bringing a need for reliable methods to assess the risk of combined exposure to multiple chemicals. Per- and polyfluoroalkylated substances (PFASs) is a large group of chemicals that has emerged as global environmental contaminants. In the Swedish population, 17 PFASs have been measured, of which the vast majority lacks human health risk assessment information. The objective of this study was to for the first time perform a cumulative health risk assessment of the 17 PFASs measured in the Swedish population, individually and in combination, using the Hazard Index (HI) approach. Swedish biomonitoring data (blood/serum concentrations of PFASs) were used and two study populations identified: 1) the general population exposed indirectly via the environment and 2) occupationally exposed professional ski waxers. Hazard data used were publicly available toxicity data for hepatotoxicity and reproductive toxicity as well as other more sensitive toxic effects. The results showed that PFASs concentrations were in the low ng/ml serum range in the general population, reaching high ng/ml and low μg/ml serum concentrations in the occupationally exposed. For those congeners lacking toxicity data with regard to hepatotoxicity and reproductive toxicity read-across extrapolations was performed. Other effects at lower dose levels were observed for some well-studied congeners. The risk characterization showed no concern for hepatotoxicity or reproductive toxicity in the general population except in a subpopulation eating PFOS-contaminated fish, illustrating that high local exposure may be of concern. For the occupationally exposed there was concern for hepatotoxicity by PFOA and all congeners in combination as well as for reproductive toxicity by all congeners in combination, thus a

  18. Brain region distribution and patterns of bioaccumulative perfluoroalkyl carboxylates and sulfonates in east greenland polar bears (Ursus maritimus).

    PubMed

    Greaves, Alana K; Letcher, Robert J; Sonne, Christian; Dietz, Rune

    2013-03-01

    The present study investigated the comparative accumulation of perfluoroalkyl acids (PFAAs) in eight brain regions of polar bears (Ursus maritimus, n = 19) collected in 2006 from Scoresby Sound, East Greenland. The PFAAs studied were perfluoroalkyl carboxylates (PFCAs, C(6) -C(15) chain lengths) and sulfonates (C(4) , C(6) , C(8) , and C(10) chain lengths) as well as selected precursors including perfluorooctane sulfonamide. On a wet-weight basis, blood-brain barrier transport of PFAAs occurred for all brain regions, although inner regions of the brain closer to incoming blood flow (pons/medulla, thalamus, and hypothalamus) contained consistently higher PFAA concentrations compared to outer brain regions (cerebellum, striatum, and frontal, occipital, and temporal cortices). For pons/medulla, thalamus, and hypothalamus, the most concentrated PFAAs were perfluorooctane sulfonate (PFOS), ranging from 47 to 58 ng/g wet weight, and perfluorotridecanoic acid, ranging from 43 to 49 ng/g wet weight. However, PFOS and the longer-chain PFCAs (C(10) -C(15) ) were significantly (p < 0.002) positively correlated with lipid content for all brain regions. Lipid-normalized PFOS and PFCA (C(10) -C(15) ) concentrations were not significantly (p > 0.05) different among brain regions. The burden of the sum of PFCAs, perfluoroalkyl sulfonates, and perfluorooctane sulfonamide in the brain (average mass, 392 g) was estimated to be 46 µg. The present study demonstrates that both PFCAs and perfluoroalkyl sulfonates cross the blood-brain barrier in polar bears and that wet-weight concentrations are brain region-specific.

  19. Compositional effects on leaching of stain-guarded (perfluoroalkyl and polyfluoroalkyl substance-treated) carpet in landfill leachate.

    PubMed

    Kim, Minhee; Li, Loretta Y; Grace, John R; Benskin, Jonathan P; Ikonomou, Michael G

    2015-06-01

    Perfluoroalkyl and polyfluoroalkyl substances (PFASs) from stain-guard treated carpets in landfills continue to be released into the environment. To understand the leaching of PFASs from carpets to landfill leachate as a function of environmental factors, leaching concentrations of ten perfluoroalkyl carboxylic acids and four perfluoroalkyl sulfonic acids were quantified for different pHs, contact times, mixing speeds, and temperatures. Partitioning from carpet to leachate and distilled water at different pHs showed negligible differences. The total concentration of leaching PFASs in distilled water was approximately 1 ng L(-1) higher than in landfill leachate, indicating that the presence of multivalent cations in leachate could have a negative effect on leaching of PFASs. For all PFASs monitored, leaching increased with increasing contact time and temperature. Perfluorohexanoic and perfluoroheptanoic acids experienced the largest increases with contact time and temperature. Gibbs free energy (ΔG > 0), enthalpy (ΔH > 0), and entropy energy (ΔS < 0) indicated that PFAS leaching from carpet was dominantly controlled by entropy-driven processes and did not differ significantly among individual PFASs. PFAS concentrations in leachate with rotation of an end-over-end contactor were higher than under static conditions, but otherwise, varying the rotation speed had negligible influence. The results provide useful information for management of discarded stain-guard carpets in landfills.

  20. Compositional effects on leaching of stain-guarded (perfluoroalkyl and polyfluoroalkyl substance-treated) carpet in landfill leachate.

    PubMed

    Kim, Minhee; Li, Loretta Y; Grace, John R; Benskin, Jonathan P; Ikonomou, Michael G

    2015-06-01

    Perfluoroalkyl and polyfluoroalkyl substances (PFASs) from stain-guard treated carpets in landfills continue to be released into the environment. To understand the leaching of PFASs from carpets to landfill leachate as a function of environmental factors, leaching concentrations of ten perfluoroalkyl carboxylic acids and four perfluoroalkyl sulfonic acids were quantified for different pHs, contact times, mixing speeds, and temperatures. Partitioning from carpet to leachate and distilled water at different pHs showed negligible differences. The total concentration of leaching PFASs in distilled water was approximately 1 ng L(-1) higher than in landfill leachate, indicating that the presence of multivalent cations in leachate could have a negative effect on leaching of PFASs. For all PFASs monitored, leaching increased with increasing contact time and temperature. Perfluorohexanoic and perfluoroheptanoic acids experienced the largest increases with contact time and temperature. Gibbs free energy (ΔG > 0), enthalpy (ΔH > 0), and entropy energy (ΔS < 0) indicated that PFAS leaching from carpet was dominantly controlled by entropy-driven processes and did not differ significantly among individual PFASs. PFAS concentrations in leachate with rotation of an end-over-end contactor were higher than under static conditions, but otherwise, varying the rotation speed had negligible influence. The results provide useful information for management of discarded stain-guard carpets in landfills. PMID:25985932

  1. Tissue specific uptake and elimination of perfluoroalkyl acids (PFAAs) in adult rainbow trout (Oncorhynchus mykiss) after dietary exposure.

    PubMed

    Falk, Sandy; Failing, Klaus; Georgii, Sebastian; Brunn, Hubertus; Stahl, Thorsten

    2015-06-01

    Tissue specific uptake and elimination of perfluoroalkyl acids (PFAAs) were studied in rainbow trout (Oncorhynchus mykiss). Adult trout were exposed to perfluorobutane sulfonic acid (PFBS), perfluorohexane sulfonic acid (PFHxS), perfluorooctane sulfonic acid (PFOS), perfluorooctanoic acid (PFOA) and perfluorononanoic acid (PFNA) via food over a time period of 28d. In the following 28-d depuration period the fish were fed PFAA-free food. At defined sampling times four animals were removed from the experimental tank, euthanized and dissected. Muscle, liver, kidneys, gills, blood, skin and carcass were examined individually. At the end of the accumulation phase between 0.63% (PFOA) and 15.5% (PFOS) of the absolute, applied quantity of PFAAs was recovered in the whole fish. The main target organ was the liver with recovery rates between 0.11% (PFBS) and 4.01% (PFOS) of the total amount of ingested PFAAs. Perfluoroalkyl sulfonic acids were taken up more readily and had longer estimated elimination half-lives than perfluoroalkyl carboxylic acids of the same chain length. The longest estimated elimination half-lives were found to be for PFOS between 8.4d in muscle tissue and 20.4d in the liver and for PFNA between 8.2d in the blood and 11.6d in the liver.

  2. Contribution of selected perfluoroalkyl and polyfluoroalkyl substances to the adsorbable organically bound fluorine in German rivers and in a highly contaminated groundwater.

    PubMed

    Willach, Sarah; Brauch, Heinz-Jürgen; Lange, Frank T

    2016-02-01

    Due to the lack of analytical standards the application of surrogate parameters for organofluorine detection in the aquatic environment is a complementary approach to single compound target analysis of perfluoroalkyl and polyfluoroalkyl chemicals (PFASs). The recently developed method adsorbable organically bound fluorine (AOF) is based on adsorption of organofluorine chemicals to activated carbon followed by combustion ion chromatography. This AOF method was further simplified to enable measurement of larger series of environmental samples. The limit of quantification (LOQ) was 0.77 μg/L F. The modified protocol was applied to 22 samples from German rivers, a municipal wastewater treatment plant (WWTP) effluent, and four groundwater samples from a fire-fighting training site. The WWTP effluent (AOF = 1.98 μg/L F) and only three river water samples (AOF between 0.88 μg/L F and 1.47 μg/L F) exceeded the LOQ. The AOF levels in a PFASs plume at a heavily contaminated site were in the range of 162 ± 3 μg/L F to 782 ± 43 μg/L F. In addition to AOF 17 PFASs were analyzed by high performance liquid chromatography-tandem mass spectrometry. 32-51% of AOF in the contaminated groundwater samples were explained by individual PFASs wheras in the surface waters more than 95% remained unknown. Organofluorine of two fluorinated pesticides, one pesticide metabolite and three fluorinated pharmaceuticals was recovered as AOF by >50% from all four tested water matrices. It is suggested that in the diffusely contaminated water bodies such fluorinated chemicals and not monitored PFASs contribute significantly to AOF.

  3. Coating morphology and surface composition of acrylic terpolymers with pendant catechol, OEG and perfluoroalkyl groups in varying ratio and the effect on protein adsorption.

    PubMed

    Zhong, Jun; Ji, Hua; Duan, Jiang; Tu, Haiyang; Zhang, Aidong

    2016-04-01

    This work aims at developing versatile low-biofouling polymeric coatings by using acrylic terpolymers (DOFs) that bear pendant catechol (D), oligo(ethylene glycol) (O), and perfluoroalkyl (F) groups in varying ratios. The polymers were endowed with the ability to form firmly coatings on virtually any surfaces and undergo surface microphase separation and self-assembly, as revealed by the surface enrichment of F pendants and the morphology variation from irregular solid domains to discrete crater-type aggregates of different size. The effect on protein adsorption was investigated using bovine serum albumin (BSA) and adhesive fibrinogen (Fib) as model proteins. The coating of DOF164 (low F content), which has morphology of discrete crater-type aggregates of ∼ 400 nm in size, adsorbed a least amount of protein but with a highest protein unit activity as determined by SPR and immunosorbent assay; whereas the coating of DOF1612 (high F content) showed a 12.3-fold higher adsorption capacity toward Fib. Interestingly, a 2.2-fold lower adsorption amount but with a 1.8-fold higher unit activity was found for Fib adsorbed on the DOF164 surface than on DOF250 (without F fraction), whose OEG segments being a widely recognized protein compatible material. The features of the DOF164 terpolymer presenting a robust coating ability and a minimal protein adsorption capacity while with a high protein unit activity suggest its potential application as a non-fouling surface-modifier for medical antifouling coatings and as a matrix material for selective protein immobilization and activity preservation in biosensor construction. PMID:26764109

  4. Occurrence of select perfluoroalkyl substances at U.S. Air Force aqueous film-forming foam release sites other than fire-training areas: Field-validation of critical fate and transport properties.

    PubMed

    Anderson, R Hunter; Long, G Cornell; Porter, Ronald C; Anderson, Janet K

    2016-05-01

    The use of aqueous film-forming foam (AFFF) to extinguish hydrocarbon-based fires is recognized as a significant source of environmental poly- and perfluoroalkyl substances (PFASs). Although the occurrence of select PFASs in soil and groundwater at former fire-training areas (FTAs) at military installations operable since 1970 has been consistently confirmed, studies reporting the occurrence of PFASs at other AFFF-impacted sites (e.g. emergency response locations, AFFF lagoons, hangar-related AFFF storage tanks and pipelines, and fire station testing and maintenance areas) are largely missing from the literature. Further, studies have mostly focused on a single site (i.e., FTAs at military installations) and, thus, lack a comparison of sites with diverse AFFF release history. Therefore, the purpose of this investigation was to evaluate select PFAS occurrence at non-FTA sites on active U.S. Air Force installations with historic AFFF use of varying magnitude. Concentrations of fifteen perfluoroalkyl acids (PFAAs) and perfluorooctane sulfonamide (PFOSA), an important PFOS precursor, were measured from several hundred samples among multiple media (i.e., surface soil, subsurface soil, sediment, surface water, and groundwater) collected from forty AFFF-impacted sites across ten installations between March and September 2014, representing one of the most comprehensive datasets on environmental PFAS occurrence to date. Differences in detection frequencies and observed concentrations due to AFFF release volume are presented along with rigorous data analyses that quantitatively demonstrate phase-dependent (i.e., solid-phase vs aqueous-phase) differences in the chemical signature as a function of carbon chain-length and in situ PFOS (and to a slightly lesser extent PFHxS) formation, presumably due to precursor biotransformation. PMID:26786021

  5. Occurrence of select perfluoroalkyl substances at U.S. Air Force aqueous film-forming foam release sites other than fire-training areas: Field-validation of critical fate and transport properties.

    PubMed

    Anderson, R Hunter; Long, G Cornell; Porter, Ronald C; Anderson, Janet K

    2016-05-01

    The use of aqueous film-forming foam (AFFF) to extinguish hydrocarbon-based fires is recognized as a significant source of environmental poly- and perfluoroalkyl substances (PFASs). Although the occurrence of select PFASs in soil and groundwater at former fire-training areas (FTAs) at military installations operable since 1970 has been consistently confirmed, studies reporting the occurrence of PFASs at other AFFF-impacted sites (e.g. emergency response locations, AFFF lagoons, hangar-related AFFF storage tanks and pipelines, and fire station testing and maintenance areas) are largely missing from the literature. Further, studies have mostly focused on a single site (i.e., FTAs at military installations) and, thus, lack a comparison of sites with diverse AFFF release history. Therefore, the purpose of this investigation was to evaluate select PFAS occurrence at non-FTA sites on active U.S. Air Force installations with historic AFFF use of varying magnitude. Concentrations of fifteen perfluoroalkyl acids (PFAAs) and perfluorooctane sulfonamide (PFOSA), an important PFOS precursor, were measured from several hundred samples among multiple media (i.e., surface soil, subsurface soil, sediment, surface water, and groundwater) collected from forty AFFF-impacted sites across ten installations between March and September 2014, representing one of the most comprehensive datasets on environmental PFAS occurrence to date. Differences in detection frequencies and observed concentrations due to AFFF release volume are presented along with rigorous data analyses that quantitatively demonstrate phase-dependent (i.e., solid-phase vs aqueous-phase) differences in the chemical signature as a function of carbon chain-length and in situ PFOS (and to a slightly lesser extent PFHxS) formation, presumably due to precursor biotransformation.

  6. Monitoring of perfluoroalkyl substances in the Ebro and Guadalquivir River basins (Spain)

    NASA Astrophysics Data System (ADS)

    Lorenzo, Maria; Campo, Julian; Andreu, Vicente; Pico, Yolanda; Farre, Marinella; Barcelo, Damia

    2015-04-01

    Relevant concentrations of a broad range of pollutants have been found in Spanish Mediterranean River basins, as consequence of anthropogenic pressures and overexploitation (Campo et al., 2014). In this study, the occurrence and sources of 21 perfluoroalkyl substances (PFASs) were determined in water and sediment of the Ebro and Guadalquivir River basins (Spain). PFASs are persistent, bio-accumulative and toxic, which make them a hazard to human health and wildlife. The Ebro and Guadalquivir Rivers are the two most important rivers of Spain. They are representative examples of Mediterranean rivers heavily managed, and previous researches have reported their high pesticide contamination (Masiá et al., 2013). Analytes were extracted by solid phase extraction (SPE) and determined by liquid chromatography coupled to tandem mass spectrometry (LC/MS-MS). In water samples, from 21 analytes screened, 11 were found in Ebro samples and 9 in Guadalquivir ones. In both basins, the most frequents were PFBA, PFPeA, PFHxS and PFOS. Maximum concentration was detected for PFBA, with 251.3 ng L-1 in Ebro and 742.9 ng L-1 in Guadalquivir. Regarding the sediment samples, 8 PFASs were detected in those coming from Ebro basin and 9 in those from Guadalquivir. The PFASs most frequently detected were PFBA, PFPeA, PFOS and PFBS. Maximum concentration in Ebro samples was detected for PFOA, with 32.4 ng g-1 dw, and in Guadalquivir samples for PFBA with 63.8 ng g-1 dw. Ubiquity of these compounds in the environment was proved with high PFAS concentration values detected in upper parts of the rivers. Results confirm that most of the PFASs are only partially eliminated during the secondary treatment suggesting that they can be a focal point of contamination to the rivers where they can bio-accumulate and produce adverse effects on wildlife and humans. Acknowledgment The Spanish Ministry of Economy and Competitiveness has supported this work through the projects SCARCE-CSD2009-00065, CGL2011

  7. Prenatal exposure to perfluoroalkyl substances and the risk of congenital cerebral palsy in children.

    PubMed

    Liew, Zeyan; Ritz, Beate; Bonefeld-Jørgensen, Eva Cecilie; Henriksen, Tine Brink; Nohr, Ellen Aagaard; Bech, Bodil Hammer; Fei, Chunyuan; Bossi, Rossana; von Ehrenstein, Ondine S; Streja, Elani; Uldall, Peter; Olsen, Jørn

    2014-09-15

    Perfluoroalkyl substances (PFASs) are persistent pollutants and endocrine disruptors that may affect fetal brain development. We investigated whether prenatal exposure to PFASs increases the risk of congenital cerebral palsy (CP). The source population for this study includes 83,389 liveborn singletons and mothers enrolled in the Danish National Birth Cohort during 1996-2002. We identified 156 CP cases by linking the cohort to the Danish National Cerebral Palsy Register, and we randomly selected 550 controls using a case-cohort design. We measured 16 PFASs in maternal plasma collected in early or midpregnancy, and 6 PFASs were quantifiable in more than 90% of the samples. We found a higher risk of CP in boys with higher maternal PFAS levels; per 1-unit (natural-log ng/mL) increase, the risk ratios were 1.7 (95% confidence interval: 1.0, 2.8) for perfluorooctane sulfonate and 2.1 (95% confidence interval: 1.2, 3.6) for perfluorooctanoic acid. We also observed a dose-response pattern of CP risk in boys per quartile of maternal level of perfluorooctane sulfonate and perfluorooctanoic acid (P for trend < 0.01). PFASs were associated with both unilateral and bilateral spastic CP subphenotypes. No association between PFASs and CP was found in girls. Prenatal exposures to PFASs may increase the risk of CP in boys, but the finding is novel and replication is needed.

  8. Micropatterning of perfluoroalkyl self-assembled monolayers for arraying proteins and cells on chips

    NASA Astrophysics Data System (ADS)

    Kira, Atsushi; Okano, Kazunori; Hosokawa, Yoichiroh; Naito, Akira; Fuwa, Koh; Yuyama, Jyunpei; Masuhara, Hiroshi

    2009-06-01

    Organosilane self-assembled monolayers (SAMs) with perfluoroalkyl groups ( Rf) on glass surfaces were used for arraying proteins and cells on chips. Quartz crystal microbalance measurements confirmed the inhibition of protein adsorption on Rf-SAM-modified surfaces and showed efficient adsorption on hydroxyl-, carboxyl-, and amino group-modified surfaces. The characteristics of Rf-modified surfaces were evaluated using solvent contact angle measurement and Fourier transform infrared (FTIR) spectroscopy. The Rf surface was highly water- and oil-resistant, as inferred from the contact angles of water, oleic acid, and hexadecane. Specific peaks of IR spectra were detected in the region from 1160 to 1360 cm -1. Etching with dry plasma completely exfoliated the Rf-SAM, exposing the underlying intact glass surface. Modification conditions were optimized using contact angle and FTIR measurements. After dry plasma processing, the contact angles of all solvents became undetectable, and the IR peaks disappeared. Micrometer scale protein and cell patterns can be fabricated using the proposed method. Protein adsorption on micropatterned Rf-SAM-modified chips was evaluated using fluorescence analysis; protein adsorption was easily controlled by patterning Rf-SAM. PC12 and HeLa cells grew well on micropatterned Rf-SAM-modified chips. Micropatterning of Rf-SAM by dry plasma treatment with photolithography is useful for the spatial arrangement of proteins and cells.

  9. Perfluoroalkyl acid contamination and polyunsaturated fatty acid composition of French freshwater and marine fishes.

    PubMed

    Yamada, Ami; Bemrah, Nawel; Veyrand, Bruno; Pollono, Charles; Merlo, Mathilde; Desvignes, Virginie; Sirot, Véronique; Oseredczuk, Marine; Marchand, Philippe; Cariou, Ronan; Antignac, Jean-Phillippe; Le Bizec, Bruno; Leblanc, Jean-Charles

    2014-07-30

    In this study, French marine and freshwater fish perfluoroalkyl acid (PFAA) contamination are presented along with their fatty acid (FA) composition to provide further elements for a risk/benefit balance of fish consumption to be assessed. The 29 most consumed marine fish species were collected in four metropolitan French coastal areas in 2004 to constitute composite samples. Geographical differences in terms of consumed species and contamination level were taken into account. Three hundred and eighty-seven composite samples corresponding to 16 freshwater fish species collected between 2008 and 2010 in the six major French rivers or their tributaries were selected among the French national agency for water and aquatic environments freshwater fish sample library. The raw edible parts were analyzed for FA composition and PFAA contamination. Results show that freshwater fishes are more contaminated by PFAAs than marine fishes and do not share the same contamination profile. Freshwater fish contamination is mostly driven by perfluorooctane sulfonate (PFOS) (75%), whereas marine fish contamination is split between perfluorooctanoic acid (PFOA) (24%), PFOS (20%), perfluorohexanoic acid (PFHxA) (15%), perfluoropentanoic acid (PFHpA) (11%), and perfluorobutanoic acid (PFBA) (11%). Common carp, pike-perch, European perch, thicklip grey mullet, and common roach presented the most unfavorable balance profile due to their high level of PFAAs and low level of n-3 long-chain polyunsaturated fatty acids (LC-PUFAs). These data could be used, if needed, in an updated opinion on fish consumption that takes into account PFAA contamination.

  10. Perfluoroalkyl substances in a firefighting training ground (FTG), distribution and potential future release.

    PubMed

    Baduel, Christine; Paxman, Christopher J; Mueller, Jochen F

    2015-10-15

    The present study investigates the occurrence and fate of 15 perfluoroalkyl substances (PFASs) and one fluorotelomer sulfonate from a firefighting training ground (FTG) that was contaminated by intensive use of aqueous film forming foams (AFFF). The contamination levels and their spatial and vertical distribution are assessed in the structure. At the surface of the pad, perfluorooctane sulphonate (PFOS) is the dominant PFASs measured, with concentration varying from 10 to 200 μg g(-1). PFASs were also detected in a concrete core at up to 12 cm depth, suggesting the vertical movement and higher transport potential of shorter chain compounds. The estimated mass load of linear PFOS in this specific pad was >300 g with a total of 1.7 kg for the sum of all PFASs analyzed. The kinetics of desorption of PFOS, PFOA and 6:2FTS from the concrete into an overlaying static water volume has been measured under field conditions at two constant temperatures. Fitting the desorption data and estimated rainfall/runoff to a kinetic model suggests that this and similar firefighting training pads will likely remain a source of PFASs for many decades (t0.5=25 years for PFOS).

  11. The first 1-alkyl-3-perfluoroalkyl-4,5- dimethyl-1,2,4-triazolium salts.

    PubMed

    Xue, Hong; Twamley, Brendan; Shreeve, Jean'ne M

    2004-02-20

    Syntheses of quaternary 1-alkyl-3-perfluoroalkyl-4,5-dimethyl-1,2,4-triazolium iodides have led to a variety of new quaternary salts via metathesis reactions. 1,4,5-Trimethyl-3-trifluoro-methyl-1,2,4-triazolium iodide (6) with LiN(SO(2)CF(3))(2), KSO(3)CF(3), AgClO(4), AgBF(4); 1-(3-fluoropropyl)-3-trifluoromethyl-4,5-dimethyl-1,2,4-triazolium iodide (7) with LiN(SO(2)CF(3))(2); and 1,4,5-trimethyl-3-perfluorooctyl-1,2,4-triazolium iodide (8) with LiN(SO(2)CF(3))(2), AgClO(4), AgBF(4) gave excellent yields of new thermally stable and relatively low melting quaternary salts. The structure of 1,4,5-trimethyl-3-perfluorooctyl-1,2,4-triazolium tetrafluoroborate (11c) was confirmed by single-crystal X-ray analysis. Although the molecular weight of 11c (cation) is 3-fold greater than that of the 3-trifluoromethyl derivative 9d, its melting point is 32 degrees C lower.

  12. A review of sources, multimedia distribution and health risks of perfluoroalkyl acids (PFAAs) in China.

    PubMed

    Wang, Tieyu; Wang, Pei; Meng, Jing; Liu, Shijie; Lu, Yonglong; Khim, Jong Seong; Giesy, John P

    2015-06-01

    Perfluoroalkyl acids (PFAAs) have been recognized as emerging pollutants because of their ubiquitous occurrence in the environment, biota and humans. In order to investigate their sources, fate and environmental effects, a great number of surveys have been carried out over the past several years. In the present review, we summarized the status of sources and emission, concentration, distribution and risks of PFAAs in China. Concentrations of PFAAs, especially perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) in various environmental media including water, sediment, soil, rain, snow and organisms, as well as human tissues are summarized based on the available data. Concentrations of PFAAs in aquatic systems are higher in relatively more industrialized and urbanized areas than those from the less populated and remote regions in China, indicating that their emission and distribution are closely related to regional urbanization and industrialization. PFAAs and related products have been widely used over the past several decades, which have brought about high concentrations detected in environmental matrixes, biota and even local residents. Ecological risk assessment of PFAAs is still less developed in China. Most existing studies compared concentrations of PFAAs to guideline values derived for single species to evaluate the risk. In order to reveal the transport, partitioning and degradation of PFAAs in the environment, further studies on their behavior, fate, bioaccumulation and adverse effects in different trophic levels should be conducted.

  13. Longitudinal and latitudinal distribution of perfluoroalkyl compounds in the surface water of the Atlantic Ocean.

    PubMed

    Ahrens, Lutz; Barber, Jonathan L; Xie, Zhiyong; Ebinghaus, Ralf

    2009-05-01

    Perfluoroalkyl compounds (PFCs) were determined in 2 L surface water samples collected in the Atlantic Ocean onboard the research vessels Maria S. Merian along the longitudinal gradient from Las Palmas (Spain) to St. Johns (Canada) (15 degrees W to 52 degrees W) and Polarstern along the latitudinal gradient from the Bay of Biscay to the South Atlantic Ocean (46 degrees N to 26 degrees S) in spring and fall 2007, respectively. After filtration the dissolved and particulate phases were extracted separately, and PFC concentrationswere determined using high-performance liquid chromatography interfaced to tandem mass spectrometry. No PFCs were detected in the particulate phase. This study provides the first concentration data of perfluorooctanesulfonamide (FOSA), perfluorohexanoic acid, and perfluoroheptanoic acid from the Atlantic Ocean. Results indicate that trans-Atlantic Ocean currents caused the decreasing concentration gradient from the Bay of Biscay to the South Atlantic Ocean and the concentration drop-off close to the Labrador Sea. Maximum concentrations were found for FOSA, perfluorooctanesulfonate, and perfluorooctanoic acid at 302, 291, and 229 pg L(-1), respectively. However, the concentration of each single compound was usually in the tens of picograms per liter range. South of the equator only FOSA and below 4 degrees S no PFCs could be detected.

  14. Approaches to prepare perfluoroalkyl and pentafluorophenyl copper couples for cross-coupling reactions with organohalogen compounds.

    PubMed

    Kremlev, Mikhail M; Mushta, Aleksej I; Tyrra, Wieland; Yagupolskii, Yurii L; Naumann, Dieter; Schäfer, Mathias

    2015-12-01

    The reactions of iodoperfluoroalkanes CnF2n+1I (n = 2, 3, 4) and n-BuLi at low temperatures give NMR spectroscopic evidence for LiCnF2n+1 which were converted into LiCu(CnF2n+1)2 derivatives upon treatment with 0.5 mol copper(i) bromide, CuBr. An alternative route to obtain perfluoroorgano copper couples, Cu(Rf)2Ag (Rf = n-C3F7, n-C4F9, C6F5) was achieved from the reactions of the corresponding perfluoroorgano silver(i) reagents, AgRf, and elemental copper through redox transmetallations. The composition of the resulting reactive intermediates was investigated by means of (19)F NMR spectroscopy and ESI mass spectrometry. Perfluoro-n-propyl and perfluoro-n-butyl copper-silver reagents prepared by the oxidative transmetallation route exhibited good properties in C-C bond formation reactions with acid chlorides even under moderate conditions. Substitution of bromine directly bound to aromatics for perfluoroalkyl groups was achieved at elevated temperatures, while success in halide substitution reactions using lithium copper couples remained poor. PMID:26488228

  15. Effects of perfluoroalkyl acids on the function of the thyroid hormone and the aryl hydrocarbon receptor.

    PubMed

    Long, Manhai; Ghisari, Mandana; Bonefeld-Jørgensen, Eva Cecilie

    2013-11-01

    Perfluoroalkyl acids (PFAAs) are perfluorinated compounds that widely exist in the environment and can elicit adverse effects including endocrine disruption in humans and animals. This study investigated the effect of seven PFAAs on the thyroid hormone (TH) system assessing the proliferation of the 3,3',5-triiodo-L-thryonine (T3)-dependent rat pituitary GH3 cells using the T-screen assay and the effect on the aryl hydrocarbon receptor (AhR) transactivation in the AhR-luciferase reporter gene bioassay. A dose-dependent impact on GH3 cells was observed in the range 1×10(-9)-1×10(-4) M: seven PFAAs (perfluorooctane sulfonate (PFOS), perfluorohexane sulfonate (PFHxS), perfluorooctanoic acid, perfluorononanoic acid (PFNA), perfluorodecanoic acid (PFDA), perfluoroundecanoic acid (PFUnA), and perfluorododecanoic acid (PFDoA)) inhibited the GH3 cell growth, and four PFAAs (PFOS, PFHxS, PFNA, and PFUnA) antagonized the T3-induced GH3 cell proliferation. At the highest test concentration, PFHxS showed a further increase of the T3-induced GH3 growth. Among the seven tested PFAAs, only PFDoA and PFDA elicited an activating effect on the AhR. In conclusion, PFAAs possess in vitro endocrine-disrupting potential by interfering with TH and AhR functions, which need to be taken into consideration when assessing the impact on human health. PMID:23539207

  16. Exposure and effects of perfluoroalkyl substances in tree swallows nesting in Minnesota and Wisconsin, USA

    USGS Publications Warehouse

    Custer, Christine M.; Custer, Thomas W.; Dummer, Paul; Etterson, Matthew A.; Thogmartin, Wayne E.; Wu, Qian; Kannan, Kurunthachalam; Trowbridge, Annette; McKann, Patrick C.

    2013-01-01

    The exposure and effects of perfluoroalkyl substances (PFASs) were studied at eight locations in Minnesota and Wisconsin between 2007 and 2011 using tree swallows (Tachycineta bicolor). Concentrations of PFASs were quantified as were reproductive success end points. The sample egg method was used wherein an egg sample is collected, and the hatching success of the remaining eggs in the nest is assessed. The association between PFAS exposure and reproductive success was assessed by site comparisons, logistic regression analysis, and multistate modeling, a technique not previously used in this context. There was a negative association between concentrations of perfluorooctane sulfonate (PFOS) in eggs and hatching success. The concentration at which effects became evident (150–200 ng/g wet weight) was far lower than effect levels found in laboratory feeding trials or egg-injection studies of other avian species. This discrepancy was likely because behavioral effects and other extrinsic factors are not accounted for in these laboratory studies and the possibility that tree swallows are unusually sensitive to PFASs. The results from multistate modeling and simple logistic regression analyses were nearly identical. Multistate modeling provides a better method to examine possible effects of additional covariates and assessment of models using Akaike information criteria analyses. There was a credible association between PFOS concentrations in plasma and eggs, so extrapolation between these two commonly sampled tissues can be performed.

  17. Investigation of the excited state iodine lifetime in the photodissociation of perfluoroalkyl iodides

    NASA Technical Reports Server (NTRS)

    Cobb, Stephen H.

    1991-01-01

    An evaluation of prospective laser materials for a space-based solar pumped laser system over the past decade has resulted in the identification of the iodine photodissociation laser as that system best suited to solar-pumped high energy operation. The active medium for the solar-pumped iodine photodissociation laser is from the family of perfluoroalkyl iodides. These lasants have the general form C(n)F(2n + 1)I, often abbreviated as RI. These iodides are known to exhibit photodissociaiton of the C-I bond when irradiated by near UV photons. The focus was on the experimental determination of the lifetime of the excited iodine atom following photodissociation of C4F9I, and also to monitor fluorescence from the iodine molecule at 500 nm to determine if I2 is being produced in the process. Photodissociation is achieved using an XeCl excimer laser with an output wavelength of 308 nm. The XeCl beam is focused into the middle of a cylindrical quartz cell containing the lasant. The laser pulse is detected with a fast risetime photomultiplier tube as it exits the cell. Other aspects of the investigation are discussed.

  18. Spatial distribution of perfluoroalkyl acids in surface sediments of the German Bight, North Sea.

    PubMed

    Zhao, Zhen; Xie, Zhiyong; Tang, Jianhui; Zhang, Gan; Ebinghaus, Ralf

    2015-04-01

    Perfluoroalkyl acids (PFAAs) have been determined in the environment globally. However, studies on the occurrence of PFAAs in marine sediment remain limited. In this study, 16 PFAAs are investigated in surface sediments from the German Bight, which provided a good overview of the spatial distribution. The concentrations of ΣPFAAs ranged from 0.056 to 7.4 ng/g dry weight. The highest concentration was found at the estuary of the River Ems, which might be the result of local discharge source. Perfluorooctane sulfonic acid (PFOS) was the dominant compound, and the enrichment of PFOS in sediment might be strongly related to the compound structure itself. The geographical condition of the German Bight influenced the movement of water and sediment, resulting in complex distribution. Following normalization according to total organic carbon (TOC) content, PFAA distributions showed a different picture. Significant linear relationships were found between total PFAA concentrations and TOC (R2=0.50, p<0.01). Compared with a previous study conducted in the same area, a declining trend was presented for the concentrations of PFOS and perfluorooctanoic acid (PFOA). Compound structure, geographical condition, and organic carbon in the sediment influence the distribution of PFAAs in the German Bight. Environmental risk assessment indicated that the risk from PFOA is negligible, whereas PFOS in marine sediment may present a risk for benthic organisms in the German Bight.

  19. Acids and alkali resistant sticky superhydrophobic surfaces by one-pot electropolymerization of perfluoroalkyl alkyl pyrrole.

    PubMed

    Nicolas, Mael

    2010-03-15

    Over the past few years, electropolymerization of semifluorinated monomers like thiophene or pyrrole has been used as a gentle and effective method to generate, in one step, stable superhydrophobic surfaces. The synthetic route mostly involves the coupling reaction between a carboxylic acid and an alcohol, using a carboxy group-activated reagent and a catalyst. As a consequence, the electroformed surfaces present high liquid repellency due to the concomitant effect of roughness and low surface energy. Nevertheless, the ester connector can be cleaved under acidic and basic conditions, preventing its use under a range of environmental conditions. To overcome this drawback, a new perfluoroalkyl alkyl pyrrole has been synthesized, the fluorinated segment being connected to the electropolymerizable part via an alkyl chain, and electropolymerized, leading to surfaces that exhibit a static contact angle with water superior to 150 degrees and no sliding angle, over a wide pH range and with a long lifetime. This represents the first example of a pure conducting polymer surface with sticky superhydrophobicity not only in pure water but also in corrosive solutions such as acids and bases, giving rise to new prospects in practical applications. PMID:20060984

  20. Perfluoroalkyl contaminants in plasma of five sea turtle species: comparisons in concentration and potential health risks.

    PubMed

    Keller, Jennifer M; Ngai, Lily; Braun McNeill, Joanne; Wood, Lawrence D; Stewart, Kelly R; O'Connell, Steven G; Kucklick, John R

    2012-06-01

    The authors compared blood plasma concentrations of 13 perfluoroalkyl contaminants (PFCs) in five sea turtle species with differing trophic levels. Wild sea turtles were blood sampled from the southeastern region of the United States, and plasma was analyzed using liquid chromatography tandem mass spectrometry. Mean concentrations of perfluorooctane sulfonate (PFOS), the predominant PFC, increased with trophic level from herbivorous greens (2.41 ng/g), jellyfish-eating leatherbacks (3.95 ng/g), omnivorous loggerheads (6.47 ng/g), to crab-eating Kemp's ridleys (15.7 ng/g). However, spongivorous hawksbills had surprisingly high concentrations of PFOS (11.9 ng/g) and other PFCs based on their trophic level. These baseline concentrations of biomagnifying PFCs demonstrate interesting species and geographical differences. The measured PFOS concentrations were compared with concentrations known to cause toxic effects in laboratory animals, and estimated margins of safety (EMOS) were calculated. Small EMOS (<100), suggestive of potential risk of adverse health effects, were observed for all five sea turtle species for immunosuppression. Estimated margins of safety less than 100 were also observed for liver, thyroid, and neurobehavorial effects for the more highly exposed species. These baseline concentrations and the preliminary EMOS exercise provide a better understanding of the potential health risks of PFCs for conservation managers to protect these threatened and endangered species.

  1. Quantifying diffuse and point inputs of perfluoroalkyl acids in a nonindustrial river catchment.

    PubMed

    Müller, Claudia E; Spiess, Nora; Gerecke, Andreas C; Scheringer, Martin; Hungerbühler, Konrad

    2011-12-01

    Recently, the role of diffuse inputs of perfluoroalkyl acids (PFAAs) into surface waters has been investigated. It has been observed that river loads increased during rain and that street runoff contained considerable loads of PFAAs. This study aims at quantifying these diffuse inputs and identifying the initial sources in a small nonindustrial river catchment. The river was sampled in three distinct subcatchments (rural, urban, and wastewater treatment plant) at high temporal resolution during two rain events and samples were analyzed for perfluorocarboxylates and perfluorosulfonates. Additionally, rain, stormwater runoff, wastewater effluent, and drinking water were sampled. PFAA concentrations in river water were all low (e.g., < 10 ng/L for perfluorooctanoate, PFOA), but increased during rainfall. PFAA concentrations and water discharge data were integrated into a mass balance assessment that shows that 30-60% of PFAA loads can be attributed to diffuse inputs. Rain contributed 10-50% of the overall loads, mobilization of dry deposition and outdoor release of PFAA from products with 20-60%. We estimated that within a year 2.5-5 g of PFOA originating from rain and surface runoff are emitted into this small catchment (6 km(2), 12,500 persons).

  2. Bioaccumulation characteristics of perfluoroalkyl acids (PFAAs) in coastal organisms from the west coast of South Korea.

    PubMed

    Hong, Seongjin; Khim, Jong Seong; Wang, Tieyu; Naile, Jonathan E; Park, Jinsoon; Kwon, Bong-Oh; Song, Sung Joon; Ryu, Jongseong; Codling, Garry; Jones, Paul D; Lu, Yonglong; Giesy, John P

    2015-06-01

    Year-round monitoring for perfluoroalkyl acids (PFAAs) along the west coast of South Korea targeting long-term changes in water and coastal organisms has been conducted since 2008. In this study, we present the most recent 5-years of accumulated data and scrutinize the relationship between concentrations in water and biota highlighting bioaccumulation characteristics. Twelve individual PFAAs in samples of water (n=43) and biota (n=59) were quantified by use of HPLC-MS/MS after solid phase extraction. In recent years, concentrations of PFAAs in water have been generally decreasing, but profiles of relative concentrations of individual PFAAs vary among location and year. Bioaccumulation of PFAAs in various organisms including fishes, bivalves, crabs, gastropods, shrimps, starfish, and polychaetes varied among species. However, overall bioaccumulation of PFAAs was dependent on corresponding concentrations of PFAAs in water within an area. In organ-specific distributions of PFAAs, greater concentrations of PFAAs were found in intestine of fish (green eel goby). This result suggests that PFAAs are mainly accumulated via dietary exposure, while greater concentrations were found in gill and intestine of bivalve (oyster) which suggests both waterborne and dietary exposures to these organisms. Concentrations of PFAAs in biota did not decrease over time (2008-2010), indicating that continuing bioaccumulation followed by slow degradation or excretion of PFAAs accumulated in biota. Overall, spatio-temporal distributions of PFAAs in water and bioaccumulation characteristics seemed to be associated with recent restrictions of PFOS-based products and uses of PFBS-based substitutes.

  3. Aqueous phase hydration and hydrate acidity of perfluoroalkyl and n:2 fluorotelomer aldehydes.

    PubMed

    Rayne, Sierra; Forest, Kaya

    2016-01-01

    The SPARC software program and comparative density functional theory (DFT) calculations were used to investigate the aqueous phase hydration equilibrium constants (Khyd) of perfluoroalkyl aldehydes (PFAlds) and n:2 fluorotelomer aldehydes (FTAlds). Both classes are degradation products of known industrial compounds and environmental contaminants such as fluorotelomer alcohols, iodides, acrylates, phosphate esters, and other derivatives, as well as hydrofluorocarbons and hydrochlorofluorocarbons. Prior studies have generally failed to consider the hydration, and subsequent potential hydrate acidity, of these compounds, resulting in incomplete and erroneous predictions as to their environmental behavior. In the current work, DFT calculations suggest that all PFAlds will be dominantly present as the hydrated form in aqueous solution. Both SPARC and DFT calculations suggest that FTAlds will not likely be substantially hydrated in aquatic systems or in vivo. PFAld hydrates are expected to have pKa values in the range of phenols (ca. 9 to 10), whereas n:2 FTAld hydrates are expected to have pKa values ca. 2 to 3 units higher (ca. 12 to 13). In order to avoid spurious modeling predictions and a fundamental misunderstanding of their fate, the molecular and/or dissociated hydrate forms of PFAlds and FTAlds need to be explicitly considered in environmental, toxicological, and waste treatment investigations. The results of the current study will facilitate a more complete examination of the environmental fate of PFAlds and FTAlds. PMID:26980678

  4. Developing QSPR model of gas/particle partition coefficients of neutral poly-/perfluoroalkyl substances

    NASA Astrophysics Data System (ADS)

    Yuan, Quan; Ma, Guangcai; Xu, Ting; Serge, Bakire; Yu, Haiying; Chen, Jianrong; Lin, Hongjun

    2016-10-01

    Poly-/perfluoroalkyl substances (PFASs) are a class of synthetic fluorinated organic substances that raise increasing concern because of their environmental persistence, bioaccumulation and widespread presence in various environment media and organisms. PFASs can be released into the atmosphere through both direct and indirect sources, and the gas/particle partition coefficient (KP) is an important parameter that helps us to understand their atmospheric behavior. In this study, we developed a temperature-dependent predictive model for log KP of PFASs and analyzed the molecular mechanism that governs their partitioning equilibrium between gas phase and particle phase. All theoretical computation was carried out at B3LYP/6-31G (d, p) level based on neutral molecular structures by Gaussian 09 program package. The regression model has a good statistical performance and robustness. The application domain has also been defined according to OECD guidance. The mechanism analysis shows that electrostatic interaction and dispersion interaction play the most important role in the partitioning equilibrium. The developed model can be used to predict log KP values of neutral fluorotelomer alcohols and perfluor sulfonamides/sulfonamidoethanols with different substitutions at nitrogen atoms, providing basic data for their ecological risk assessment.

  5. Acids and alkali resistant sticky superhydrophobic surfaces by one-pot electropolymerization of perfluoroalkyl alkyl pyrrole.

    PubMed

    Nicolas, Mael

    2010-03-15

    Over the past few years, electropolymerization of semifluorinated monomers like thiophene or pyrrole has been used as a gentle and effective method to generate, in one step, stable superhydrophobic surfaces. The synthetic route mostly involves the coupling reaction between a carboxylic acid and an alcohol, using a carboxy group-activated reagent and a catalyst. As a consequence, the electroformed surfaces present high liquid repellency due to the concomitant effect of roughness and low surface energy. Nevertheless, the ester connector can be cleaved under acidic and basic conditions, preventing its use under a range of environmental conditions. To overcome this drawback, a new perfluoroalkyl alkyl pyrrole has been synthesized, the fluorinated segment being connected to the electropolymerizable part via an alkyl chain, and electropolymerized, leading to surfaces that exhibit a static contact angle with water superior to 150 degrees and no sliding angle, over a wide pH range and with a long lifetime. This represents the first example of a pure conducting polymer surface with sticky superhydrophobicity not only in pure water but also in corrosive solutions such as acids and bases, giving rise to new prospects in practical applications.

  6. Uptake of perfluoroalkyl acids in the leaves of coniferous and deciduous broad-leaved trees.

    PubMed

    Zhang, Huanhuan; Liu, Wei; He, Xin; Wang, Yu; Zhang, Qian

    2015-07-01

    Analytical methods for determining perfluoroalkyl acids (PFAAs) in leaves were developed to quantify a suite of analytes in both coniferous and deciduous broad-leaved trees. Sodium hydroxide-methanol and solid-phase extraction was selected as the extracting and cleanup strategy for PFAA analysis. Ten perfluorocarboxylic acids (PFCAs) and 4 perfluorosulfonic acids (PFSAs) were monitored in 7 kinds of leaves grown in the urban areas of Dalian, China. The results show that coniferous tree leaves take up more PFAAs than broad-leaved tree leaves, with the highest amount of 150 ng/g in pine needles. Leaf PFCA levels were much higher than PFSAs level. Short carbon-chain PFCAs with 3 to 6 perfluorinated carbons account for approximately 40% to 80% of the total leaf PFAAs, where uptake decreased with increasing carbon chain length. Temporal observation of leaf PFAAs revealed no significant variation of concentrations in the leaves over a weekly interval and the absence of significant seasonal change in pine needles and sophora. The present study provides some evidence for the accumulation of PFAAs in leaves, which is valuable for understanding their environmental behavior and the development of alternative bioindicator.

  7. Quantifying diffuse and point inputs of perfluoroalkyl acids in a nonindustrial river catchment.

    PubMed

    Müller, Claudia E; Spiess, Nora; Gerecke, Andreas C; Scheringer, Martin; Hungerbühler, Konrad

    2011-12-01

    Recently, the role of diffuse inputs of perfluoroalkyl acids (PFAAs) into surface waters has been investigated. It has been observed that river loads increased during rain and that street runoff contained considerable loads of PFAAs. This study aims at quantifying these diffuse inputs and identifying the initial sources in a small nonindustrial river catchment. The river was sampled in three distinct subcatchments (rural, urban, and wastewater treatment plant) at high temporal resolution during two rain events and samples were analyzed for perfluorocarboxylates and perfluorosulfonates. Additionally, rain, stormwater runoff, wastewater effluent, and drinking water were sampled. PFAA concentrations in river water were all low (e.g., < 10 ng/L for perfluorooctanoate, PFOA), but increased during rainfall. PFAA concentrations and water discharge data were integrated into a mass balance assessment that shows that 30-60% of PFAA loads can be attributed to diffuse inputs. Rain contributed 10-50% of the overall loads, mobilization of dry deposition and outdoor release of PFAA from products with 20-60%. We estimated that within a year 2.5-5 g of PFOA originating from rain and surface runoff are emitted into this small catchment (6 km(2), 12,500 persons). PMID:22035097

  8. A review of sources, multimedia distribution and health risks of perfluoroalkyl acids (PFAAs) in China.

    PubMed

    Wang, Tieyu; Wang, Pei; Meng, Jing; Liu, Shijie; Lu, Yonglong; Khim, Jong Seong; Giesy, John P

    2015-06-01

    Perfluoroalkyl acids (PFAAs) have been recognized as emerging pollutants because of their ubiquitous occurrence in the environment, biota and humans. In order to investigate their sources, fate and environmental effects, a great number of surveys have been carried out over the past several years. In the present review, we summarized the status of sources and emission, concentration, distribution and risks of PFAAs in China. Concentrations of PFAAs, especially perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) in various environmental media including water, sediment, soil, rain, snow and organisms, as well as human tissues are summarized based on the available data. Concentrations of PFAAs in aquatic systems are higher in relatively more industrialized and urbanized areas than those from the less populated and remote regions in China, indicating that their emission and distribution are closely related to regional urbanization and industrialization. PFAAs and related products have been widely used over the past several decades, which have brought about high concentrations detected in environmental matrixes, biota and even local residents. Ecological risk assessment of PFAAs is still less developed in China. Most existing studies compared concentrations of PFAAs to guideline values derived for single species to evaluate the risk. In order to reveal the transport, partitioning and degradation of PFAAs in the environment, further studies on their behavior, fate, bioaccumulation and adverse effects in different trophic levels should be conducted. PMID:25262946

  9. Perfluoroalkyl acids (PFAAs) with isomer analysis in the commercial PFOS and PFOA products in China.

    PubMed

    Jiang, Weiwei; Zhang, Yifeng; Yang, Liping; Chu, Xiaolong; Zhu, Lingyan

    2015-05-01

    Perfluoroalkyl acids (PFAAs) have been widely used in consumer and industrial products for decades and are widely detected in the environment and humans all over the world. The information on the isomeric profiles of commercial products is important to identify the manufacturing origins of PFAAs in the environment. For the first time, the PFAA compositions and isomeric profiles of perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) were reported in three PFOS and five PFOA commercial products manufactured in China. The purity of the three PFOS products was 76.7-80.6%. The major impurity in the PFOS products is PFOA, which contributes more than 10%. Other impurities include perfluorohexanesulfonate (PFHxS), perfluorohexanoate (PFHxA) and perfluoroheptanoate acids (PFHpA). The percentage of linear PFOS (n-PFOS) in the three products was 66.2-71.9%, similar to that in the product manufactured by 3M (70.3%). The purity of the five PFOA products was relatively high (94.0-95.8%), and the major impurity was PFOS (2.06-3.09%). The percentage of n-PFOA in the five PFOA products was 76.4-77.9%, which was similar to that in the 3M PFOA (78%). Although it is widely accepted that telomerization is currently the predominant manufacturing method for PFOA, yielding an isomerically pure and linear product, the results in the present study suggest that electrochemical fluorination is still used by some manufacturers in China.

  10. Effect of dietary supplementation on the prognostic value of urinary and serum 8-isoprostaglandin F2α in chemically-induced mammary carcinogenesis in the rat

    PubMed Central

    2011-01-01

    Backround The aim of the present study was to assess the effects of zinc or copper and polyphenolic compounds on the 8-isoprostaglandin F2α concentration in the serum and urine of rats with mammary cancer (adenocarcinoma) induced with 7,12-dimethylbenz[a]antracene. The research focused on the kinetics of alterations in urinary 8-isoPGF2α at the early stage of carcinogenesis as well as the influence of dietary factors on the process. The impact of selected compounds on the intensity of DMBA - induced carcinogenesis was also assessed. Result and conclusions Administration of DMBA, a compound that inducers mammary tumors in experimental animals, increased the serum and urinary 8-isoPGF2α levels in study rats. In the rat model, diet supplementation with zinc, combined with selected polyphenolic compounds (resveratrol or genistein) yielded a statistically significant decrease in the rat serum and urinary biomarker concentration with a simultaneously significant stimulation of carcinogenesis. The results indicate that there is an inverse correlation between the intensity of DMBA-induced carcinogenicity and the level of 8-isoPGF2α in urine and serum of rats. PMID:21371291

  11. A spectroscopic study on interaction between bovine serum albumin and titanium dioxide nanoparticle synthesized from microwave-assisted hybrid chemical approach.

    PubMed

    Ranjan, Shivendu; Dasgupta, Nandita; Srivastava, Priyanka; Ramalingam, Chidambaram

    2016-08-01

    The use of nanoparticles in food or pharma requires a molecular-level perceptive of how NPs interact with protein corona once exposed to a physiological environment. In this study, the conformational changes of bovine serum albumin (BSA) were investigated in detail when exposed to different concentration of titanium dioxide nanoparticle by various techniques. To analyze the effects of NPs on proteins, the interaction between bovine serum albumin and titanium dioxide nanoparticles at different concentrations were investigated. The interaction, BSA conformations, kinetics, and adsorption were analyzed by dynamic light scattering, Fourier transform infrared spectroscopy and fluorescence quenching. Dynamic light scattering analysis confirms the interaction with major changes in the size of the protein. Fluorescence quenching analysis confirms the side-on or end-on interaction of 1.1 molecules of serum albumin to titanium dioxide nanoparticles. Further, pseudo-second order kinetics was determined with equilibrium contact time of 20min. The spectroscopic analysis suggests that there is a conformational change both at secondary and tertiary structure levels. A distortion in both α-helix and β-sheets was observed by Fourier transform infrared (FTIR) spectroscopy. Fluorescence quenching analysis confirms the interaction of a molecule of bovine serum albumin to the single TiO2 nanoparticle. Further, pseudo-second order kinetics was determined with equilibrium contact time of 20min. The data of the present study determines the detailed evaluation of BSA adsorption on TiO2 nanoparticle along with mechanism and adsorption kinetics.

  12. A spectroscopic study on interaction between bovine serum albumin and titanium dioxide nanoparticle synthesized from microwave-assisted hybrid chemical approach.

    PubMed

    Ranjan, Shivendu; Dasgupta, Nandita; Srivastava, Priyanka; Ramalingam, Chidambaram

    2016-08-01

    The use of nanoparticles in food or pharma requires a molecular-level perceptive of how NPs interact with protein corona once exposed to a physiological environment. In this study, the conformational changes of bovine serum albumin (BSA) were investigated in detail when exposed to different concentration of titanium dioxide nanoparticle by various techniques. To analyze the effects of NPs on proteins, the interaction between bovine serum albumin and titanium dioxide nanoparticles at different concentrations were investigated. The interaction, BSA conformations, kinetics, and adsorption were analyzed by dynamic light scattering, Fourier transform infrared spectroscopy and fluorescence quenching. Dynamic light scattering analysis confirms the interaction with major changes in the size of the protein. Fluorescence quenching analysis confirms the side-on or end-on interaction of 1.1 molecules of serum albumin to titanium dioxide nanoparticles. Further, pseudo-second order kinetics was determined with equilibrium contact time of 20min. The spectroscopic analysis suggests that there is a conformational change both at secondary and tertiary structure levels. A distortion in both α-helix and β-sheets was observed by Fourier transform infrared (FTIR) spectroscopy. Fluorescence quenching analysis confirms the interaction of a molecule of bovine serum albumin to the single TiO2 nanoparticle. Further, pseudo-second order kinetics was determined with equilibrium contact time of 20min. The data of the present study determines the detailed evaluation of BSA adsorption on TiO2 nanoparticle along with mechanism and adsorption kinetics. PMID:27318604

  13. Spatial distribution and partition of perfluoroalkyl acids (PFAAs) in rivers of the Pearl River Delta, southern China.

    PubMed

    Liu, Baolin; Zhang, Hong; Xie, Liuwei; Li, Juying; Wang, Xinxuan; Zhao, Liang; Wang, Yanping; Yang, Bo

    2015-08-15

    This study investigated the occurrence of perfluoroalkyl acids (PFAAs) in surface water from 67 sampling sites along rivers of the Pearl River Delta in southern China. Sixteen PFAAs, including perfluoroalkyl carboxylic acids (PFCAs, C5-14, C16 and C18) and perfluoroalkyl sulfonic acids (PFSAs, C4, C6, C8 and C10) were determined by high performance liquid chromatography-negative electrospray ionization-tandem mass spectrometry (HPLC/ESI-MS/MS). Total PFAA concentrations (∑ PFAAs) in the surface water ranged from 1.53 to 33.5 ng·L(-1) with an average of 7.58 ng·L(-1). Perfluorobutane sulfonic acid (PFBS), perfluorooctanoic acid (PFOA), and perfluorooctane sulfonic acid (PFOS) were the three most abundant PFAAs and on average accounted for 28%, 16% and 10% of ∑ PFAAs, respectively. Higher concentrations of ∑ PFAAs were found in the samples collected from Jiangmen section of Xijiang River, Dongguan section of Dongjiang River and the Pearl River flowing the cities which had very well-developed manufacturing industries. PCA model was employed to quantitatively calculate the contributions of extracted sources. Factor 1 (72.48% of the total variance) had high loading for perfluorohexanoic acid (PFHxA), perfluoropentanoic acid (PFPeA), PFBS and PFOS. For factor 2 (10.93% of the total variance), perfluorononanoic acid (PFNA) and perfluoroundecanoic acid (PFUdA) got high loading. The sorption of PFCAs on suspended particulate matter (SPM) increased by approximately 0.1 log units for each additional CF2 moiety and that on sediment was approximately 0.8 log units lower than the SPM logKd values. In addition, the differences in the partition coefficients were influenced by the structure discrepancy of absorbents and influx of fresh river water. These data are essential for modeling the transport and environmental fate of PFAAs.

  14. Understanding of the intrinsic difference between normal- and perfluoro-alkyl compounds toward total understanding of material properties

    NASA Astrophysics Data System (ADS)

    Hasegawa, Takeshi

    2015-05-01

    Molecular interaction of perfluoroalkyl (Rf) compounds has long been discussed on an extended theory of normal alkyl compounds. When Rf-specific bulk properties depending on the molecular packing structure are taken into account, however, the conventional polarizability theory has a big inconsistency especially with the high melting point. Here, we present a new viewpoint to totally uniform the conventional theories for systematically accounting for the bulk properties of Rf compounds. With the organized theoretical framework, the conventional understanding based on polarizability proves to be partly true, but it misses the molecular orientation effect, which is specifically necessary for the Rf compounds.

  15. Identification of Novel Perfluoroalkyl Ether Carboxylic Acids (PFECAs) and Sulfonic Acids (PFESAs) in Natural Waters Using Accurate Mass Time-of-Flight Mass Spectrometry (TOFMS).

    PubMed

    Strynar, Mark; Dagnino, Sonia; McMahen, Rebecca; Liang, Shuang; Lindstrom, Andrew; Andersen, Erik; McMillan, Larry; Thurman, Michael; Ferrer, Imma; Ball, Carol

    2015-10-01

    Recent scientific scrutiny and concerns over exposure, toxicity, and risk have led to international regulatory efforts resulting in the reduction or elimination of certain perfluorinated compounds from various products and waste streams. Some manufacturers have started producing shorter chain per- and polyfluorinated compounds to try to reduce the potential for bioaccumulation in humans and wildlife. Some of these new compounds contain central ether oxygens or other minor modifications of traditional perfluorinated structures. At present, there has been very limited information published on these "replacement chemistries" in the peer-reviewed literature. In this study we used a time-of-flight mass spectrometry detector (LC-ESI-TOFMS) to identify fluorinated compounds in natural waters collected from locations with historical perfluorinated compound contamination. Our workflow for discovery of chemicals included sequential sampling of surface water for identification of potential sources, nontargeted TOFMS analysis, molecular feature extraction (MFE) of samples, and evaluation of features unique to the sample with source inputs. Specifically, compounds were tentatively identified by (1) accurate mass determination of parent and/or related adducts and fragments from in-source collision-induced dissociation (CID), (2) in-depth evaluation of in-source adducts formed during analysis, and (3) confirmation with authentic standards when available. We observed groups of compounds in homologous series that differed by multiples of CF2 (m/z 49.9968) or CF2O (m/z 65.9917). Compounds in each series were chromatographically separated and had comparable fragments and adducts produced during analysis. We detected 12 novel perfluoroalkyl ether carboxylic and sulfonic acids in surface water in North Carolina, USA using this approach. A key piece of evidence was the discovery of accurate mass in-source n-mer formation (H(+) and Na(+)) differing by m/z 21.9819, corresponding to the

  16. High levels of perfluoroalkyl acids in sport fish species downstream of a firefighting training facility at Hamilton International Airport, Ontario, Canada.

    PubMed

    Gewurtz, Sarah B; Bhavsar, Satyendra P; Petro, Steve; Mahon, Chris G; Zhao, Xiaoming; Morse, Dave; Reiner, Eric J; Tittlemier, Sheryl A; Braekevelt, Eric; Drouillard, Ken

    2014-06-01

    A recent study reported elevated concentrations of perfluorooctane sulfonic acid (PFOS) and other perfluoroalkyl acids (PFAAs) in surface water, snapping turtles, and amphipods in Lake Niapenco, downstream of Hamilton International Airport, Ontario, Canada. Here, our goals were to 1) determine the extent of PFAA contamination in sport fish species collected downstream of the airport, 2) explore if the airport could be a potential source, and 3) compare fish PFOS concentrations to consumption advisory benchmarks. The PFOS levels in several sport fish collected from the three locations closest to the airport (<40km) were among the highest previously published in the peer-reviewed literature and also tended to exceed consumption benchmarks. The only other fish that had comparable concentrations were collected in a region affected by inputs from a major fluorinated chemical production facility. In contrast, PFOS concentrations in the two most downstream locations (>70km) were comparable to or below the average concentrations in fish as observed in the literature and were generally below the benchmarks. With regards to perfluorocarboxylates (PFCAs), there was no significant decrease in concentrations in fish with distance from the airport and levels were comparable to or below the average concentrations observed in the literature, suggesting that the airport is not a significant source of PFCAs in these fish species. PFOS-based aqueous film-forming foam (AFFF) was used at a firefighting training facility at the airport in the 1980s to mid-1990s. Taken together, our results provide evidence that the historical use of AFFF at the airport has resulted in fish PFOS concentrations that exceed the 95th percentile concentration of values reported in the literature to date.

  17. Perfluoroalkyl contaminants in window film: indoor/outdoor, urban/rural, and winter/summer contamination and assessment of carpet as a possible source.

    PubMed

    Gewurtz, Sarah B; Bhavsar, Satyendra P; Crozier, Patrick W; Diamond, Miriam L; Helm, Paul A; Marvin, Chris H; Reiner, Eric J

    2009-10-01

    Window film concentrations of ionic perfluoroalkyl contaminants (PFCs) were determined indoors and outdoors at urban, suburban, and rural sites in or near Toronto, Ontario, Canada, to identify locations of relatively elevated concentrations and the nature of potential sources. The role of carpet installation and floor wax application as possible sources was also evaluated by sampling indoor window films at five sites before and after new carpet installations, at one site before and after a floor wax application, and at two carpet stores. Low concentrations were found in all outdoor window films, with comparable relative proportions of individual PFCs among sites, suggesting similar sources to the outdoor environment and rapid air mixing. PFCs in indoor window film were up to 20-fold greater than outdoor, providing some evidence that a significant proportion of PFCs originate from the indoor environment, although precipitation wash-off of outdoor window film may be confounding these results. For both indoor and outdoor film, PFC concentrations generally changed between the summer and winter but the chemical profiles were similar between seasons. Concentrations of PFCs in window films increased one month post carpet installation at three of the five sites, suggesting that some of the carpets may have been a source to the indoor environment. Indoor window films from two carpet stores (sigmaPFC = 16 and 7 pg/cm2) contained higher concentrations than the other indoor locations (sigmaPFC = < MDL to 4.3 pg/cm2), which may reflect the carpets stored within these buildings. The use of window film allowed collection of a wide range of samples and the results can be used to focus the efforts of more traditional air sampling campaigns.

  18. High levels of perfluoroalkyl acids in sport fish species downstream of a firefighting training facility at Hamilton International Airport, Ontario, Canada.

    PubMed

    Gewurtz, Sarah B; Bhavsar, Satyendra P; Petro, Steve; Mahon, Chris G; Zhao, Xiaoming; Morse, Dave; Reiner, Eric J; Tittlemier, Sheryl A; Braekevelt, Eric; Drouillard, Ken

    2014-06-01

    A recent study reported elevated concentrations of perfluorooctane sulfonic acid (PFOS) and other perfluoroalkyl acids (PFAAs) in surface water, snapping turtles, and amphipods in Lake Niapenco, downstream of Hamilton International Airport, Ontario, Canada. Here, our goals were to 1) determine the extent of PFAA contamination in sport fish species collected downstream of the airport, 2) explore if the airport could be a potential source, and 3) compare fish PFOS concentrations to consumption advisory benchmarks. The PFOS levels in several sport fish collected from the three locations closest to the airport (<40km) were among the highest previously published in the peer-reviewed literature and also tended to exceed consumption benchmarks. The only other fish that had comparable concentrations were collected in a region affected by inputs from a major fluorinated chemical production facility. In contrast, PFOS concentrations in the two most downstream locations (>70km) were comparable to or below the average concentrations in fish as observed in the literature and were generally below the benchmarks. With regards to perfluorocarboxylates (PFCAs), there was no significant decrease in concentrations in fish with distance from the airport and levels were comparable to or below the average concentrations observed in the literature, suggesting that the airport is not a significant source of PFCAs in these fish species. PFOS-based aqueous film-forming foam (AFFF) was used at a firefighting training facility at the airport in the 1980s to mid-1990s. Taken together, our results provide evidence that the historical use of AFFF at the airport has resulted in fish PFOS concentrations that exceed the 95th percentile concentration of values reported in the literature to date. PMID:24632327

  19. Chemical etching of bovine serum albumin-protected Au25 nanoclusters for label-free and separation-free detection of cysteamine.

    PubMed

    Shu, Tong; Su, Lei; Wang, Jianxing; Li, Chenzhong; Zhang, Xueji

    2015-04-15

    This study describes a novel Au nanocluster-based fluorescent sensor for label-free, separation-free and selective detection of cysteamine (CSH). The sensing mechanism is based on CSH etching-induced fluorescence quenching of the bovine serum albumin-protected Au25 nanoclusters (BSAGNCs). A series of characterizations is carried out towards a better understanding of the CSH-induced fluorescence quenching of the BSAGNCs. It is found that CSH can etch the Au25 nanoclusters, exhibiting the potent etching activity. Other thiol-containing compounds such as glutathione and cysteine and other 19 natural amino acids do not interfere with such CSH-induced etching process. The decreases in fluorescence intensity of the BSAGNCs allow sensitive detection of free CSH in the range of 500-10,000nM. The detection limit for CSH is 150nM (S/N=3). The spiked human serum samples can be analyzed with satisfactory results.

  20. Evaluation of additivity of binary mixtures of perfluoroalkyl acids (PFAAs) on peroxisome proliferator-activated receptor-alpha (PPARa) activation in vitro

    EPA Science Inventory

    Perfluoroalkyl acids (PFAAs) are found globally in the environment and in animal tissues, and are present as mixtures of PFAA congeners. Mechanistic studies have found that in vivo effects of PFAAs are mediated by PPARL. Our previous studies showed that individual PFAAs activate ...

  1. Interaction of perfluoroalkyl acids with human liver fatty acid-binding protein.

    PubMed

    Sheng, Nan; Li, Juan; Liu, Hui; Zhang, Aiqian; Dai, Jiayin

    2016-01-01

    Perfluoroalkyl acids (PFAAs) are highly persistent and bioaccumulative, resulting in their broad distribution in humans and the environment. The liver is an important target for PFAAs, but the mechanisms behind PFAAs interaction with hepatocyte proteins remain poorly understood. We characterized the binding of PFAAs to human liver fatty acid-binding protein (hL-FABP) and identified critical structural features in their interaction. The binding interaction of PFAAs with hL-FABP was determined by fluorescence displacement and isothermal titration calorimetry (ITC) assay. Molecular simulation was conducted to define interactions at the binding sites. ITC measurement revealed that PFOA/PFNA displayed a moderate affinity for hL-FABP at a 1:1 molar ratio, a weak binding affinity for PFHxS and no binding for PFHxA. Moreover, the interaction was mainly mediated by electrostatic attraction and hydrogen bonding. Substitution of Asn111 with Asp caused loss of binding affinity to PFAA, indicating its crucial role for the initial PFAA binding to the outer binding site. Substitution of Arg122 with Gly caused only one molecule of PFAA to bind to hL-FABP. Molecular simulation showed that substitution of Arg122 increased the volume of the outer binding pocket, making it impossible to form intensive hydrophobic stacking and hydrogen bonds with PFOA, and highlighting its crucial role in the binding process. The binding affinity of PFAAs increased significantly with their carbon number. Arg122 and Asn111 played a pivotal role in these interactions. Our findings may help understand the distribution pattern, bioaccumulation, elimination, and toxicity of PFAAs in humans.

  2. Temporal trends of perfluoroalkyl substances in limed biosolids from a large municipal water resource recovery facility.

    PubMed

    Armstrong, Dana L; Lozano, Nuria; Rice, Clifford P; Ramirez, Mark; Torrents, Alba

    2016-01-01

    While the recycling of wastewater biosolids via land-application is a sustainable practice for nutrient recovery and soil reclamation that has become increasingly common worldwide, concerns remain that this practice may become a source of toxic, persistent organic pollutants to the environment. This study concentrates on assessing the presence and the temporal trends of 12 perfluoroalkyl substances (PFASs), pollutants of global consequence, in limed Class B biosolids from a municipal water resource recovery facility (WRRF), also know as a wastewater treatment plant. PFASs are of significant concern due to their extensive presence and persistence in environmental and biotic samples worldwide, most notably human blood samples. Class B biosolids were collected from the WRRF, prior to land-application, approximately every two to three months, from 2005 to 2013. Overall, this study found that concentrations of the 7 detectable PFAS compounds remained unchanged over the 8-year period, a result that is consistent with other temporal studies of these compounds in sewage sludges. From these analyzed compounds, the highest mean concentrations observed over the study period were 25.1 ng/g dw, 23.5 ng/g dw, and 22.5 ng/g dw for perfluorononanoic acid (PFNA), perfluorooctanoic acid (PFOA), and perfluorooctanesulfonic acid (PFOS), respectively, and these compounds were detected at concentrations 2.5-5 times higher than the remaining, detectable PFASs. Furthermore, it was observed that PFOS, while demonstrating no overall change during the study, exhibited a visible spike in concentration from late 2006 to early 2007. This study indicates that concentrations of PFASs in WRRFs have been stagnant over time, despite regulation. This study also demonstrates that the use of glass jars with polytetrafluoroethylene-lined lids, a common storage method for environmental samples, will not influence PFOA and PFNA concentrations in archived biosolids samples. PMID:26413802

  3. Trophic magnification and isomer fractionation of perfluoroalkyl substances in the food web of Taihu Lake, China.

    PubMed

    Fang, Shuhong; Chen, Xinwei; Zhao, Shuyan; Zhang, Yifeng; Jiang, Weiwei; Yang, Liping; Zhu, Lingyan

    2014-02-18

    Biomagnification of perfluoroalkyl substances (PFASs) are well studied in marine food webs, but related information in fresh water ecosystem and knowledge on fractionation of their isomers along the food web are limited. The distribution, bioaccumulation, magnification, and isomer fractionation of PFASs were investigated in a food web of Taihu Lake, China. Perfluorooctanesulfonate (PFOS) and perfluorocarboxylates (PFCAs) with longer carbon chain lengths, such as perfluorodecanoate (PFDA) and perfluoroundecanoate (PFUnA), were predominant in organisms, while perfluorohexanoate (PFHxA) and perfluorooctanoate (∑PFOA) contributed more in the water phase. The consistent profile signature of PFOA isomers in water phase with 3M electrochemical fluorination (ECF) products suggests that ECF production of PFOA still exists in China. Linear proportions of PFOA, PFOS and perfluorooctane sulfonamide (PFOSA) in the biota were in the range of 91.9-100%, 78.6-95.5%, and 72.2-95.5%, respectively, indicating preferential bioaccumulation of linear isomers in biota. Trophic magnification factors (TMFs) were estimated for PFDA (2.43), perfluorododecanoate (PFDoA) (2.68) and PFOS (3.46) when all biota were included, suggesting that PFOS and long-chained PFCAs are biomagnified in the fresh water food web. The TMF of PFOS isomers descended in the order: n-PFOS (3.86) > 3+5m-PFOS (3.35) > 4m-PFOS (3.32) > 1m-PFOS (2.92) > m2-PFOS (2.67) > iso-PFOS (2.59), which is roughly identical to their elution order on a FluoroSep-RP Octyl column, suggesting that hydrophobicity may be an important contributor for isomer discrimination in biota.

  4. Biomagnification and tissue distribution of perfluoroalkyl substances (PFASs) in market-size rainbow trout (Oncorhynchus mykiss).

    PubMed

    Goeritz, Ina; Falk, Sandy; Stahl, Thorsten; Schäfers, Christoph; Schlechtriem, Christian

    2013-09-01

    The present study investigated the biomagnification potential as well as the substance and tissue-specific distribution of perfluoroalkyl substances (PFASs) in market-size rainbow trout (Oncorhynchus mykiss). Rainbow trout with an average body weight of 314 ± 21 g were exposed to perfluorobutane sulfonate (PFBS), perfluorohexane sulfonate (PFHxS), perfluorooctane sulfonate (PFOS), perfluorooctanoic acid (PFOA), and perfluorononanoic acid (PFNA) in the diet for 28 d. The accumulation phase was followed by a 28-d depuration phase, in which the test animals were fed with nonspiked trout feed. On days 0, 7, 14, 28, 31, 35, 42, and 56 of the present study, fish were sampled from the test basin for PFAS analysis. Biomagnification factors (BMFs) for all test compounds were determined based on a kinetic approach. Distribution factors were calculated for each test compound to illustrate the disposition of PFASs in rainbow trout after 28 d of exposure. Dietary exposure of market-size rainbow trout to PFASs did not result in biomagnification; BMF values were calculated as 0.42 for PFOS, >0.23 for PFNA, >0.18 for PFHxS, >0.04 for PFOA, and >0.02 for PFBS, which are below the biomagnification threshold of 1. Liver, blood, kidney, and skin were identified as the main target tissues for PFASs in market-size rainbow trout. Evidence was shown that despite relative low PFAS contamination, the edible parts of the fish (the fillet and skin) can significantly contribute to the whole-body burden.

  5. Perfluoroalkyl acids in the egg yolk of birds from Lake Shihwa, Korea.

    PubMed

    Yoo, Hoon; Kannan, Kurunthachalam; Kim, Seong Kyu; Lee, Kyu Tae; Newsted, John L; Giesy, John P

    2008-08-01

    Concentrations of perfluoroalkyl acids (PFAs) were measured in egg yolks of three species of birds, the little egret (Egretta garzetta), little ringed plover (Charadrius dubius), and parrot bill (Paradoxornis webbiana), collected in and around Lake Shihwa, Korea, which receives wastewaters from an adjacent industrial complex. Mean concentrations of perfluorooctanesulfonate (PFOS) ranged from 185 to 314 ng/g ww and were similar to those reported for bird eggs from other urban areas. Long-chain perfluorocarboxylic acids (PFCAs) were also found in egg yolks often at great concentrations. Mean concentrations of perfluoroundecanoic acid (PFUnA) ranged from 95 to 201 ng/g ww. Perfluorooctanoic acid was detected in 32 of 44 egg samples, but concentrations were 100-fold less than those of PFOS. Relative concentrations of PFAs in all three species were similar with the predominance of PFOS (45-50%). There was a statistically significant correlation between PFUnA and perfluorodecanoic acid in egg yolks (p < 0.05), suggesting a common source of PFCAs. Using measured egg concentrations and diet concentrations, the ecological risk of the PFOS and PFA mixture to birds in Lake Shihwa was evaluated using two different approaches. Estimated hazard quotients were similar between the two approaches. The concentration of PFOS associated with 90th centile in bird eggs was 100-fold less than the lowest observable adverse effect level determined for birds, and those concentrations were 4-fold less than the suggested toxicity reference values. On the basis of limited toxicological data, current concentrations of PFOS are less than what would be expected to have an adverse effect on birds in the Lake Shihwa region.

  6. Bioaccumulation of perfluoroalkyl substances by Daphnia magna in water with different types and concentrations of protein.

    PubMed

    Xia, Xinghui; Rabearisoa, Andry H; Jiang, Xiaoman; Dai, Zhineng

    2013-10-01

    Perfluoroalkyl substances (PFASs) are sometimes regarded as proteinophilic compounds, however, there is no research report about the effect of environmental protein on the bioaccumulation of PFASs in waters. In the present study we investigated influences of protein on the bioaccumulation of six kinds of PFASs by Daphnia magna in water; it included perfluorooctane sulfonate, perfluorooctanoic acid, perfluorononanoic acid, perfluorodecanoic acid, perfluoroundecanoic acid, and perfluorododecanoic acid. Two types of protein including bovine albumin from animal and soy peptone from plant were compared and the effects of protein concentration were investigated. Both types of protein at high concentrations (10 and 20 mg L(-1)) suppressed the bioaccumulation of PFASs. When protein concentration increased from 0 to 20 mg L(-1), the decreasing ratios of the PFAS body burden (35.3-52.9%) in Daphnia magna induced by bovine albumin were significantly higher than those (22.0-36.6%) by soy peptone. The dialysis bag experiment results showed that the binding of PFASs to protein followed the Freundlich isotherm, suggesting it is not a linear partitioning process but an adsorption-like process. The partition coefficients of PFASs between bovine albumin and water were higher compared to soy peptone; this resulted in higher reducing rates of freely dissolved concentrations of PFASs with increasing bovine albumin concentration, leading to a stronger suppression of PFAS bioaccumulation. However, the presence of both types of protein with a low concentration (1 mg L(-1)) enhanced the bioaccumulation of PFASs. Furthermore, the water-based bioaccumulation factor based on the freely dissolved concentrations of PFASs even increased with and the depuration rate constants of PFASs from Daphnia magna decreased with protein concentration, suggesting that protein would not only reduce the bioavailable concentrations and uptake rates of PFASs but also lower the elimination rates of PFASs in

  7. Distribution and fate of perfluoroalkyl substances in Mediterranean Spanish sewage treatment plants.

    PubMed

    Campo, Julian; Masiá, Ana; Picó, Yolanda; Farré, Marinella; Barceló, Damià

    2014-02-15

    The concentrations of 21 perfluoroalkyl substances (PFASs: C4-C14, C16, C18 carboxylates, C4, C6-C8 and C10 sulfonates and C8 sulfonamide) were determined in influent, effluent and sludge from 16 different sewage treatment plants (STPs) located in the Ebro (6), Guadalquivir (5), Jucar (2) and Llobregat (3) Rivers, in two consecutive years (2010 and 2011). The analytes were extracted by solid phase extraction (SPE) and determined by Liquid Chromatography triple Quadrupole Mass Spectrometer (LC-QqQ-MS). All samples, except two sludges from Guadalquivir River STPs, were contaminated with at least one PFAS. Perfluorobutanoate (PFBA), perfluoropentanoate (PFPeA) and perfluorooctane sulfonate (L-PFOS) were the most frequently detected. The highest concentration in water was determined in 2010 in a Guadalquivir River STP (perfluorohexanoate, PFHxA: 5.60μgL(-1)) and, in 2011, in an Ebro River STP (perfluorobutane sulfonate, L-PFBS: 0.31μgL(-1)). In sludge samples, the maximum concentration in 2010 was 1.79μgg(-1)dry weight (dw) (L-PFOS, in a Llobregat River STP), and in 2011, 1.88μgg(-1)dw (PFBA, in one Guadalquivir River STP). High PFAS values in sludge could be related to positive removal efficiencies, and can be attributed to their adsorption. Distribution coefficients (Kd) were determined ranging between 0.32Lkg(-1) (perfluorohexane sulfonate, L-PFHxS) and 36.6 10(3)Lkg(-1) (PFBA). The total PFAS loads discharged into the basins showed high values for the Ebro River STPs (66.9gday(-1)) while in the others, the loads were between 3.97gday(-1), in the Jucar STPs, and 32.2gday(-1), in the Guadalquivir STPs. PMID:24342098

  8. Short communication: Monitoring the presence of perfluoroalkyl substances in Italian cow milk.

    PubMed

    Barbarossa, Andrea; Gazzotti, Teresa; Zironi, Elisa; Serraino, Andrea; Pagliuca, Giampiero

    2014-01-01

    Perfluoroalkyl substances (PFAS) are fully fluorinated compounds widely used during the last 60 yr in the production of multiple industrial and consumer applications, such as food packaging, nonstick cookware, cleaning agents, and many more. These emerging contaminants have recently become of concern for human health because of their potential negative effects. The risk of exposure to PFAS for humans is mainly related to diet, and the increasing interest in food safety has led the European Commission to call Member States to monitor these contaminants in food matrices. The purpose of the present work was to perform the first monitoring on the presence of perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA), the 2 main and most widely investigated molecules of this family, in cow milk commercially available in Italy. We used an analytical protocol consisting of liquid-liquid extraction followed by 2 purification steps through solid-phase extraction cartridges and injection on an ultra-performance liquid chromatography-tandem mass spectroscopy system. The analysis of 67 samples of different types of cow milk from Italy demonstrated that contamination by PFOS was often present, although at relatively low concentrations (up to 97 ng/L), whereas PFOA was rarely found. On the basis of these results and data reported in the literature on this matrix, milk does not seem to be a major source of PFAS compared with other food categories such as fish and seafood. However, variability among different types of milk must be taken into account, and surveys of milk-derived products would be helpful to better define the risk for consumers. PMID:24704228

  9. Determination of perfluoroalkylated substances (PFASs) in drinking water from the Netherlands and Greece.

    PubMed

    Zafeiraki, Effrosyni; Costopoulou, Danae; Vassiliadou, Irene; Leondiadis, Leondios; Dassenakis, Emmanouil; Traag, Wim; Hoogenboom, Ron L A P; van Leeuwen, Stefan P J

    2015-01-01

    In the present study 11 perfluoroalkylated substances (PFASs) were analysed in drinking tap water samples from the Netherlands (n = 37) and from Greece (n = 43) by applying LC-MS/MS and isotope dilution. PFASs concentrations above the limit of quantification, LOQ (0.6 ng/l) were detected in 20.9% of the samples from Greece. Total PFAS concentrations ranged between 8) were only rarely detected. In the drinking water samples from the eastern part of the Netherlands, where drinking water is sourced from groundwater reservoirs, no PFASs were detected. This demonstrates that exposure to PFASs through drinking water in the Netherlands is dependent on the source. Additionally, five samples of bottled water from each country were analysed in the current study, with all of them originating from ground wells. In these samples, all PFASs were below the LOQ.

  10. Perfluoroalkylated substances (PFASs) in home and commercially produced chicken eggs from the Netherlands and Greece.

    PubMed

    Zafeiraki, Effrosyni; Costopoulou, Danae; Vassiliadou, Irene; Leondiadis, Leondios; Dassenakis, Emmanouil; Hoogenboom, Ron L A P; van Leeuwen, Stefan P J

    2016-02-01

    Dietary intake is a major route of human exposure to perfluoroalkylated substances (PFASs). However, the available information on PFAS levels in food, including chicken eggs, is limited. In the present study, home produced and commercially produced eggs (organic, battery and free range eggs) were collected from the Netherlands (n = 95) and Greece (n = 76). The egg yolks were analysed for 11 PFASs by liquid chromatography-tandem mass spectrometry using isotope dilution. PFAS levels in yolk were higher in home produced eggs from the Netherlands (median 3.1, range < LOQ - 31.2 ng g(-1)) and Greece (median 1.1, range < LOQ - 15.0 ng g(-1)) compared to the eggs collected from supermarkets. In these eggs, all PFAS levels were below the LOQ of 0.5 ng g(-1), except for a small amount of perfluorooctane sulfonate (PFOS) in 1 sample in each country (1.1 ng g(-1) and 0.9 ng g(-1) for the Netherlands and Greece respectively). PFOS was the predominant PFAS, making up on average 85% of ∑PFASs. The highest PFOS concentration was detected in a Dutch home produced egg sample (24.8 ng g(-1)). The contamination pattern was similar in both countries with the long-chain PFASs (C ≥ 8) being most frequently detected, while short-chain PFASs were rarely found. The most likely cause of the contamination of home produced eggs is ingestion of soil through pecking. Although regular consumption of home produced eggs will lead to an increased PFOS exposure, it is not expected that it will lead to exceedance of the tolerable daily intake established by EFSA.

  11. Determination of perfluoroalkylated substances (PFASs) in drinking water from the Netherlands and Greece.

    PubMed

    Zafeiraki, Effrosyni; Costopoulou, Danae; Vassiliadou, Irene; Leondiadis, Leondios; Dassenakis, Emmanouil; Traag, Wim; Hoogenboom, Ron L A P; van Leeuwen, Stefan P J

    2015-01-01

    In the present study 11 perfluoroalkylated substances (PFASs) were analysed in drinking tap water samples from the Netherlands (n = 37) and from Greece (n = 43) by applying LC-MS/MS and isotope dilution. PFASs concentrations above the limit of quantification, LOQ (0.6 ng/l) were detected in 20.9% of the samples from Greece. Total PFAS concentrations ranged between 8) were only rarely detected. In the drinking water samples from the eastern part of the Netherlands, where drinking water is sourced from groundwater reservoirs, no PFASs were detected. This demonstrates that exposure to PFASs through drinking water in the Netherlands is dependent on the source. Additionally, five samples of bottled water from each country were analysed in the current study, with all of them originating from ground wells. In these samples, all PFASs were below the LOQ. PMID:26366629

  12. Getting on with persistent pollutants: Decreasing trends of perfluoroalkyl acids (PFAAs) in sewage sludge.

    PubMed

    Ulrich, Hanna; Freier, Korbinian P; Gierig, Michael

    2016-10-01

    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. PMID:27472434

  13. Accumulation of perfluoroalkyl compounds in tibetan mountain snow: temporal patterns from 1980 to 2010.

    PubMed

    Wang, Xiaoping; Halsall, Crispin; Codling, Garry; Xie, Zhiyong; Xu, Baiqing; Zhao, Zhen; Xue, Yonggang; Ebinghaus, Ralf; Jones, Kevin C

    2014-01-01

    The use of snow and ice cores as recorders of environmental contamination is particularly relevant for per- and polyfluoroalky substances (PFASs) given their production history, differing source regions and varied mechanisms driving their global distribution. In a unique study perfluoroalkyl acids (PFAAs) were analyzed in dated snow-cores obtained from high mountain glaciers on the Tibetan Plateau (TP). One snow core was obtained from the Mt Muztagata glacier (accumulation period of 1980-1999), located in western Tibet and a second core from Mt. Zuoqiupo (accumulation period: 1996-2007) located in southeastern Tibet, with fresh surface snow collected near Lake Namco in 2010 (southern Tibet). The higher concentrations of ∑PFAAs were observed in the older Mt Muztagata core and dominated by perfluorooctanesulfonic acid (PFOS) (61.4-346 pg/L) and perfluorooctanoic acid (PFOA) (40.8-243 pg/L), whereas in the Mt Zuoqiupu core the concentrations were lower (e.g., PFOA: 37.8-183 pg/L) with PFOS below detection limits. These differences in PFAA concentrations and composition profile likely reflect the upwind sources affecting the respective sites (e.g., European/central Asian sources for Mt Muztagata and India sources for Mt Zuoqiupu). Perfluorobutanoic acid (PFBA) dominated the recent surface snowpack of Lake Namco which is mainly associated with India sources where the shorter chain volatile PFASs precursors predominate. The use of snow cores in different parts of Tibet provides useful recorders to examine the influence of different PFASs source regions and reflect changing PFAS production/use in the Northern Hemisphere.

  14. Perfluoroalkyl acids (PFAAs) in indoor and outdoor dusts around a mega fluorochemical industrial park in China: Implications for human exposure.

    PubMed

    Su, Hongqiao; Lu, Yonglong; Wang, Pei; Shi, Yajuan; Li, Qifeng; Zhou, Yunqiao; Johnson, Andrew C

    2016-09-01

    The manufacture of fluorochemicals can lead to high levels of perfluoroalkyl acids (PFAAs) contaminating the surrounding environment and consequently elevated exposure to the local residents. In this study, measurements of PFAAs associated with indoor and outdoor dusts around a mega fluorochemical industrial park (FIP) were made. Perfluorooctanoic acid (PFOA) and short-chain perfluoroalkyl carboxylic acids (C4-C7 PFCAs) were the predominant forms in all samples. The signature of the PFAAs in dusts in the local area matched that found within the FIP complex. The contamination plume in the local area could be linked to the prevailing wind direction starting from the FIP. The dust concentrations decreased exponentially with distance from the FIP (noticeably in the first 5km). PFAAs contamination could be detected at the furthest location, 20km away from the FIP. The concentrations of PFAAs were higher in indoor dust (73-13,500ng/g, median: 979ng/g) than those in outdoor dust (5-9495ng/g, median: 62ng/g) at every location. The highest estimated daily intake of PFOA via dust ingestion (26.0ng/kg·bw/day) was for toddlers (2-5years) living 2km away from the FIP, which is posing human health risk, though exposure remains within the provisional tolerable daily intake values. PMID:27393120

  15. Synthesis of novel polymethacrylates with siloxyl bridging perfluoroalkyl side-chains for hydrophobic application on cotton fabrics

    NASA Astrophysics Data System (ADS)

    Cai, Lu; Dai, Li; Yuan, Yanhua; Liu, Anqi; Zhanxiong, Li

    2016-05-01

    Three novel fluorinated methacrylate monomers with siloxyl bridging perfluoroalkyl groups were synthesized and characterized. Afterwards, the corresponding polymethacrylate latexes, namely monofluoroalkylsiloxyl polymethacrylate (PMFSMA), bisfluoroalkylsiloxyl polymethacrylate (PBFSMA) and trisfluoroalkylsiloxyl polymethacrylate (PTFSMA), were prepared and coated onto cotton fabrics to make them water-repellent. Particle size, particle size distribution, zeta potential and high-resolution transmission electron microscope (TEM) were tested to assess the emulsion stability and particle morphology. Thermal properties of PTFSMA were evaluated by thermal-gravimetric analysis (TGA). Surface properties of the coated cotton fabrics were characterized by Fourier transform infrared spectroscopy (FT-IR), scanning electron microscope (SEM), water contact angle (WCA), adhesive force and X-ray photoelectron spectroscopy (XPS). It was found that the incorporation of more perfluoroalkyl chains and the annealing process could decrease the surface free energy of polymer film to 13.7 mN/m. Furthermore, the EDS spectra of PTFSMA film after annealing showed an enrichment of fluorine in the film-air interface.

  16. A Comparison of RIA and LC-MS/MS Methods to Quantify Steroids in Rat Serum and Urine Following Exposure to an Endocrine Disrupting Chemical

    EPA Science Inventory

    Commercially available radio immunoassays (RIM) are frequently used in toxicological studies to evaluate effects of endocrine disrupting chemicals (EDCs) on steroidogenesis in rats. Currently there are limited data comparing steroid concentrations in rats as measured by RIM to th...

  17. Probing the binding of an endocrine disrupting compound-Bisphenol F to human serum albumin: Insights into the interactions of harmful chemicals with functional biomacromolecules

    NASA Astrophysics Data System (ADS)

    Pan, Fang; Xu, Tianci; Yang, Lijun; Jiang, Xiaoqing; Zhang, Lei

    2014-11-01

    Bisphenol F (BPF) as an endocrine disrupting compounds (EDCs) pollutant in the environment poses a great threat to human health. To evaluate the toxicity of BPF at the protein level, the effects of BPF on human serum albumin (HSA) were investigated at three temperatures 283, 298, and 308 K by multiple spectroscopic techniques. The experimental results showed that BPF effectively quenched the intrinsic fluorescence of HSA via static quenching. The number of binding sites, the binding constant, the thermodynamic parameters and the binding subdomain were measured, and indicated that BPF could spontaneously bind with HSA on subdomain IIA through H-bond and van der Waals interactions. Furthermore, the conformation of HSA was demonstrably changed in the presence of BPF. The work provides accurate and full basic data for clarifying the binding mechanisms of BPF with HSA in vivo and is helpful for understanding its effect on protein function during its transportation and distribution in blood.

  18. Environmental influences on reproductive health: the importance of chemical exposures.

    PubMed

    Wang, Aolin; Padula, Amy; Sirota, Marina; Woodruff, Tracey J

    2016-09-15

    Chemical exposures during pregnancy can have a profound and life-long impact on human health. Because of the omnipresence of chemicals in our daily life, there is continuous contact with chemicals in food, water, air, and consumer products. Consequently, human biomonitoring studies show that pregnant women around the globe are exposed to a variety of chemicals. In this review we provide a summary of current data on maternal and fetal exposure, as well as health consequences from these exposures. We review several chemical classes, including polychlorinated biphenyls, perfluoroalkyl substances, polybrominated diphenyl ethers, phenols, phthalates, pesticides, and metals. Additionally, we discuss environmental disparities and vulnerable populations, and future research directions. We conclude by providing some recommendations for prevention of chemical exposure and its adverse reproductive health consequences. PMID:27513554

  19. Poly- and perfluoroalkyl substances (PFASs) in raw and drinking water - current situation in Sweden, Denmark and Germany

    NASA Astrophysics Data System (ADS)

    Banzhaf, Stefan; Bester, Kai; Filipovic, Marko; Lewis, Jeffrey; Licha, Tobias; Sparrenbom, Charlotte; Barthel, Roland

    2016-04-01

    Poly- and perfluoroalkyl substances (PFASs) are a group of anthropogenic environmental pollutants which have been used and produced for more than 60 years. PFASs are used for multiple industrial purposes, e.g. as water repellent on clothing, leather, and paper and as firefighting foam. The most well studied PFASs subgroup are perfluoroalkyl acids (PFAA). Two PFAAs of particular interest are perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA). These are the most studied homologues which are ubiquitously detected in the aquatic environment, wildlife and humans. Some PFASs are recognized as being potentially toxic for both animals and humans (e.g. PFOS), whereas the majority has not been thoroughly studied yet regarding their toxicity. PFAAs are highly mobile once present in the aquatic environment. Currently, they are not eliminated during conventional wastewater or drinking water treatment and therefore pose a severe threat for drinking water supply. We reviewed the current occurrence of PFAAs in the surface and groundwater and legal situation of PFAAs in Sweden, Denmark and Germany. Although first detections of PFAAs were reported in the early 2000s, PFASs only recently attracted huge media attention raising public concern. In Sweden, for instance, several public waterworks needed to cease operation due to high PFASs concentrations in drinking water. Moreover, threshold values for drinking water are under discussion and a first preliminary guiding value for PFOS was recently presented as a first step (Pettersson et al., 2015). Germany only defined a guiding value for the sum of PFOS and PFOA in drinking water so far (Dieter, 2011). Limits of 0.3 μg/L PFOA and 0.1 μg/L PFOS and PFOSA each have been suggested in Denmark (MST, 2015). In summary, none of the three countries has defined a clear threshold value for any PFAS compound in drinking water so far. This is of huge concern as PFASs are detected at increasing rates while it remains unclear when

  20. Reliability of perfluoroalkyl substances in plasma of 100 women in two consecutive pregnancies

    PubMed Central

    Papadopoulou, Eleni; Haug, Line S.; Sabaredzovic, Azemira; Eggesbø, Merete; Longnecker, Matthew P.

    2015-01-01

    The potential toxicity of background exposure to perfluoroalkyl substances (PFASs) is currently under active investigation. Such investigations typically rely on a single measure of PFAS concentration, yet the longer-term reliability of a single measure has not been well characterized, especially among reproductive-aged women. Our aim was to investigate the association between PFAS plasma concentrations of 100 women in two consecutive pregnancies and explore changes in plasma concentration related to reproductive factors. The women in our study were enrolled in the Norwegian Mother and Child Cohort Study (MoBa) from 2003 to 2009. About half of them breastfed exclusively for 6 months and the rest of the participants did not breastfeed between the two consecutive pregnancies (median time between pregnancies: 18 months). Maternal blood was collected at mid-pregnancy and plasma was analyzed for 10 PFASs. Statistical analyses were restricted to 6 PFASs that were quantifiable in more than 80% of the samples. We estimated the correlation between repeated PFAS measurements, the percentage change between pregnancies and the effect of several reproductive factors in multivariate linear regression models of PFAS concentration in the second pregnancy. The Pearson correlation coefficient between repeated PFAS measurements was, for perfluorooctane sulfonate (PFOS), 0.80; perfluorooctanoate (PFOA), 0.50; perfluorohexane sulfonate (PFHxS), 0.74; perfluorononanoate (PFNA), 0.39; perfluoroundecanoate (PFUnDA), 0.71; and perfluorodecanoate (PFDA), 0.60. Adjustment for maternal age, delivery year, and time and breastfeeding between pregnancies did not substantially affect the observed correlations. We found 44-47% median reductions in the concentrations of PFOS, PFOA and PFHxS between pregnancies, while the change in concentrations between pregnancies was smaller and more variable for PFNA, PFUnDA and PFDA. The variation in plasma concentrations in the second pregnancy was mainly

  1. Infrared spectroscopy of bis[(perfluoroalkyl)sulfonyl] imide ionomer membrane materials.

    PubMed

    Byun, Chang Kyu; Sharif, Iqbal; Desmarteau, Darryl D; Creager, Stephen E; Korzeniewski, Carol

    2009-05-01

    Structural properties of the proton-exchanged forms of bis[(perfluoroalkyl)sulfonyl] imide (PFSI) ionomer materials were investigated. The hydration and dehydration of samples prepared as thin films and freestanding membrane were probed by applying transmission infrared spectroscopy. Spectral bands were assigned and effects of water incorporation into membrane pores and channels were understood by drawing upon results from related measurements performed on the structurally similar, perfluorosulfonic acid ionomer, Nafion. Both PFSI and Nafion membrane materials display a prominent infrared absorbance band near 1060 cm(-1) that arises from a vibrational mode of the ionizable group present on the side chains that extend from the poly(tetrafluoroethylene) backbone on the polymers. The mode can be traced to symmetric stretching of the -SO(3)(-) (sulfonate) group in Nafion and to antisymmetric S-N-S stretching within the sulfonyl imide end group (-SO(2)(N(-))SO(2)CF(3)) in the PFSI materials. For Nafion samples, the position and width of the band near 1060 cm(-1) are strongly sensitive to membrane hydration, whereas the band position and shape change only slightly during hydration and dehydration of PFSI materials. The possibility for greater charge delocalization over the sulfonyl imide moiety and shielding of hydrophilic species by the terminal -CF(3) group are suggested to explain the differences. These effects also likely influence the stretching modes of the side chain C-O-C groups. A pair of bands, sensitive to hydration and traceable to different C-O-C groups in a side chain, is present in the 970-990 cm(-1) region of Nafion. However, the two features are not well resolved and are less sensitive to hydration in spectra of PFSI samples. The most intense ionomer spectral bands arise from modes involving C-F stretching motion and appear between 1150 and 1250 cm(-1). Toward the high energy side of the envelope, there is substantial overlap with features of sulfonate

  2. Perfluoroalkyl acids in the Canadian environment: multi-media assessment of current status and trends.

    PubMed

    Gewurtz, Sarah B; Backus, Sean M; De Silva, Amila O; Ahrens, Lutz; Armellin, Alain; Evans, Marlene; Fraser, Susan; Gledhill, Melissa; Guerra, Paula; Harner, Tom; Helm, Paul A; Hung, Hayley; Khera, Nav; Kim, Min Gu; King, Martha; Lee, Sum Chi; Letcher, Robert J; Martin, Pamela; Marvin, Chris; McGoldrick, Daryl J; Myers, Anne L; Pelletier, Magella; Pomeroy, Joe; Reiner, Eric J; Rondeau, Myriam; Sauve, Marie-Claude; Sekela, Mark; Shoeib, Mahiba; Smith, Daniel W; Smyth, Shirley Anne; Struger, John; Spry, Doug; Syrgiannis, Jim; Waltho, Jasmine

    2013-09-01

    In Canada, perfluoroalkyl acids (PFAAs) have been the focus of several monitoring programs and research and surveillance studies. Here, we integrate recent data and perform a multi-media assessment to examine the current status and ongoing trends of PFAAs in Canada. Concentrations of perfluorooctane sulfonate (PFOS), perfluorooctanoate (PFOA), and other long-chain perfluorocarboxylates (PFCAs) in air, water, sediment, fish, and birds across Canada are generally related to urbanization, with elevated concentrations observed around cities, especially in southern Ontario. PFOS levels in water, fish tissue, and bird eggs were below their respective Draft Federal Environmental Quality Guidelines, suggesting there is low potential for adverse effects to the environment/organisms examined. However, PFOS in fish and bird eggs tended to exceed guidelines for the protection of mammalian and avian consumers, suggesting a potential risk to their wildlife predators, although wildlife population health assessments are needed to determine whether negative impacts are actually occurring. Long-term temporal trends of PFOS in suspended sediment, sediment cores, Lake Trout (Salvelinus namaycush), and Herring Gull (Larus argentatus) eggs collected from Lake Ontario increased consistently from the start of data collection until the 1990s. However, after this time, the trends varied by media, with concentrations stabilizing in Lake Trout and Herring Gull eggs, and decreasing and increasing in suspended sediment and the sediment cores, respectively. For PFCAs, concentrations in suspended sediment, sediment cores, and Herring Gulls generally increased from the start of data collection until present and concentrations in Lake Trout increased until the late 1990s and subsequently stabilized. A multimedia comparison of PFAA profiles provided evidence that unexpected patterns in biota of some of the lakes were due to unique source patterns rather than internal lake processes. High

  3. Association between thyroid profile and perfluoroalkyl acids: Data from NHNAES 2007–2008

    SciTech Connect

    Jain, Ram B.

    2013-10-15

    The effect of six perfluoroalkyl acids (PFAAs), namely, perfluorooctane sulfonate (PFOS), perfluorooctanoic acid (PFOA), perfluorodecanoic acid (PFDE), perfluorohexane sulfonic acid (PFHxS), 2-(N-methyl-perfluorooctane sulfonamide) acetic acid (MPAH), and perfluorononanoic acid (PFNA) on the levels of six thyroid function variables, namely, thyroid stimulating hormone (TSH), free and total thyroxine (FT4, TT4), free and total triiodothyronine (FT3, TT3), and thyroglobulin (TGN) was evaluated. Data from National Health and Nutrition Examination Survey for the years 2007–2008 were used for this evaluation. TSH levels increased with increase in levels of PFOA (p<0.01). There were no statistically significant associations between the levels of FT3, and FT4 with the levels of any of the six PFAAs. Levels of TT3 were found to increase with the levels of PFOA (p=0.01) and TT4 levels were found to increase with increase in PFHxS levels (p<0.01). Males had statistically significantly higher levels of FT3 than females and females had statistically significantly higher levels of TT4 than males. As compared to non-Hispanics whites and Hispanics, non-Hispanic blacks had lower levels of TSH, FT3, TT3, and TT4 but Hispanics had the lowest levels of TGN. Age was negatively associated with FT3 and TT3 but positively associated with FT4 and TT4. Non-smokers had higher levels of TSH and TT4 than smokers and smokers had higher levels of FT3 and TGN than non-smokers. Iodine deficiency was associated with increased levels of TSH, TT3, TT4, and TGN. -- Highlights: • Levels of total triiodothyronine were found to increase with the levels of PFOA. • Total thyroxine increased with increase in levels of perfluorohexane sulfonic acid. • There was a positive association between the levels of PFOA and TSH. • Iodine deficiency was associated with elevated levels of TSH, total T3 and T4. • Iodine deficiency was associated with elevated levels of thyroglobulin.

  4. Perfluoroalkyl contaminants in an Arctic marine food web: trophic magnification and wildlife exposure.

    PubMed

    Kelly, Barry C; Ikonomou, Michael G; Blair, Joel D; Surridge, Blair; Hoover, Dale; Grace, Richard; Gobas, Frank A P C

    2009-06-01

    To better understand the bioaccumulation behavior of perfluoroalkyl contaminants (PFCs), we conducted a comparative analysis of PFCs and lipophilic organohalogens in a Canadian Arctic marine food web. Concentrations of perfluorooctane sulfonic acid (PFOS), perfluorooctansulfoamide (PFOSA), and C7-C14 perfluorocarboxylic acids (PFCAs) ranged between 0.01 and 0.1 ng x g(-1) dry wt in sediments and 0.1 and 40 ng x g(-1) wet wt in biota, which was equivalent to or higher than levels of PCBs, PBDEs, and organochlorine pesticides. In beluga whales, PFOS and PFCA concentrations were higher (P < 0.05) in protein-rich compartments (liver and blood), compared to other tissues/fluids (milk, blubber, muscle, and fetus). In the marine mammalian food web, concentrations of PFOSA and lipophilic organochlorines (ng x g(-1) lipid equivalent) and proteinophilic substances (i.e., PFOS and C8-C14 PFCAs, ng x g(-1) protein) increased significantly (P < 0.05) with trophic level. Trophic magnification factors (TMFs) of organochlorines ranged between 5 and 14 and exhibited significant curvilinear relationships (P < 0.05) with octanol-water and octanol-air partition coefficients (KOW, KOA). TMFs of perfluorinated acids (PFAs) ranged between 2 and 11 and exhibited similar correlation (P < 0.05) with protein-water and protein-air partition coefficients (KPW, KPA). PFAs did not biomagnify in the aquatic piscivorous food web (TMF range: 0.3-2). This food web specific biomagnification behavior was attributed to the high aqueous solubility and low volatility of PFAs. Specifically, the anticipated phase-partitioning of these proteinophilic substances, represented by their protein-water (KPW) and protein-air (KPA) partition coefficients, likely results in efficient respiratory elimination in water-respiring organisms but very slow elimination and biomagnification in air-breathing animals. Lastly, the results indicate that PFOS exposure in nursing Hudson Bay beluga whale calves (CI95 range = 2.7 x

  5. Determinants of plasma concentrations of perfluoroalkyl substances in pregnant Norwegian women

    PubMed Central

    Whitworth, KW; Ydersbond, TA; Haug, LS; Haugen, M; Knutsen, HK; Thomsen, C; Meltzer, HM; Becher, G; Sabaredzovic, A; Hoppin, JA; Eggesbø, M; Longnecker, MP

    2013-01-01

    Background Perfluoroalkyl substances (PFASs) are widespread pollutants that have been associated with adverse health effects although not on a consistent basis. Diet has been considered the main source of exposure. The aim of the present study was to identify determinants of four plasma PFASs in pregnant Norwegian women. Methods This study is based in the Norwegian Mother and Child Cohort Study (MoBa) conducted by the Norwegian Institute of Public Health. Our sample included 487 women who enrolled in MoBa from 2003–2004. A questionnaire regarding sociodemographic, medical, and reproductive history was completed at 17 weeks gestation and a dietary questionnaire was completed at 22 weeks gestation. Maternal plasma samples were obtained around 17 weeks of gestation. Plasma concentrations of four PFASs (perfluorooctane sulfonate (PFOS), perfluorooctanoate (PFOA), perfluorohexane sulfonate (PFHxS), and perfluorononanoate (PFNA)) were examined in relation to demographic, lifestyle, dietary, and pregnancy-related covariates. Predictors were identified by optimizing multiple linear regression models using Akaike’s information criterion (AIC). Results Parity was the determinant with the largest influence on plasma PFAS concentrations, with r2 between 0.09 and 0.32 in simple regression models. In optimal multivariate models, when compared to nulliparous women, parous women had 46%, 70%, 19%, and 62% lower concentrations of PFOS, PFOA, PFHxS, and PFNA respectively (p<0.001 except for PFHxS, p<0.01). In all these models, duration of breastfeeding was associated with reduced PFAS levels. PFOA showed the largest reduction from breastfeeding, with a 2–3% reduction per month of breastfeeding in typical cases. Levels of PFOS, PFOA, and PFNA increased with time since most recent pregnancy. While pregnancy-related factors were the most important predictors, diet was a significant factor explaining up to 4% of the variance. One quartile increase in estimated dietary PFAS intake

  6. Development of a gas phase source for perfluoroalkyl acids to examine atmospheric sampling methods.

    PubMed

    MacInnis, John J; VandenBoer, Trevor C; Young, Cora J

    2016-06-21

    An inability to produce environmentally relevant gaseous mixing ratios of perfluoroalkyl acids (PFAAs), ubiquitous global contaminants, limits the analytical reliability of atmospheric chemists to make accurate gas and particulate measurements that are demonstrably free of interferences due to sampling artefacts. A gas phase source for PFAAs based on the acid displacement mechanism using perfluoropropionate (PFPrA), perfluorobutanoate (PFBA), perfluorohexanoate (PFHxA), and perfluorooctanoate (PFOA) has been constructed. The displacement efficiency of gas phase perfluorocarboxylic acids (PFCAs) is inversely related to chain length. Decreasing displacement efficiencies for PFPrA, PFBA, PFHxA, and PFOA were 90% ± 20%, 40% ± 10%, 40% ± 10%, 9% ± 4%, respectively. Generating detectable amounts of gas phase perfluorosulfonic acids (PFSAs) was not possible. It is likely that lower vapour pressure and much higher acidity play a role in this lack of emission. PFCA emission rates were not elevated by increasing relative humidity (25%-75%), nor flow rate of carrier gas from 33-111 sccm. Overall, reproducible gaseous production of PFCAs was within the error of the production of hydrochloric acid (HCl) as a displacing acid (±20%) and was accomplished using a dry nitrogen flow of 33 ± 2 sccm. A reproducible mass emission rate of 0.97 ± 0.10 ng min(-1) (n = 8) was observed for PFBA. This is equivalent to an atmospheric mixing ratio of 12 ppmv, which is easily diluted to environmentally relevant mixing ratios of PFBA. Conversely, generating gas phase perfluorononanoic acid (PFNA) by sublimating the solid acid under the same conditions produced a mass emission rate of 2800 ng min(-1), which is equivalent to a mixing ratio of 18 ppthv and over a million times higher than suspected atmospheric levels. Thus, for analytical certification of atmospheric sampling methods, generating gas phase standards for PFCAs is best accomplished using acid displacement under dry conditions

  7. Perfluoroalkyl acid uptake in lettuce (Lactuca sativa) and strawberry (Fragaria ananassa) irrigated with reclaimed water.

    PubMed

    Blaine, Andrea C; Rich, Courtney D; Sedlacko, Erin M; Hyland, Katherine C; Stushnoff, Cecil; Dickenson, Eric R V; Higgins, Christopher P

    2014-12-16

    Using reclaimed water to irrigate food crops presents an exposure pathway for persistent organic contaminants such as perfluoroalkyl acids (PFAAs) to enter the human food chain. This greenhouse study used reclaimed water augmented with varying concentrations (0.2-40 μg/L) of PFAAs, including perfluorocarboxylates (C3F7COO(-) to C8F17COO(-)) and perfluorosulfonates (C4F9SO2O(-), C6F13SO2O(-), C8F17SO2O(-)), to investigate potential uptake and concentration-response trends in lettuce (Lactuca sativa) and strawberry (Fragaria ananassa). In addition, studies were conducted to evaluate the role of soil organic carbon concentrations on plant uptake of PFAAs. PFAA concentrations in lettuce leaves and strawberry fruit were measured for each aqueous PFAA concentration applied. PFAA plant concentrations increased linearly with the aqueous concentration for all PFAAs, with PFCAs bioaccumulating to a greater degree than PFSAs in the edible portions of the tested plants. Chain-length-dependency trends were evident in both lettuce shoot and strawberry fruit, with decreasing concentrations associated with increasing chain length. Perfluorobutanoate (PFBA) and perfluoropentanoate (PFPeA), both short-chain PFAAs (<8 carbon chain length), accumulated the most compared with other PFAAs tested in the edible parts of both lettuce and strawberry. PFAA concentrations in strawberry root and shoot were also measured at selected PFAA aqueous concentrations (0.4, 4, and 40 μg/L). Short-chain perfluorocarboxylates were the dominant fraction in the strawberry fruit and shoot compartments, whereas a more even distribution of all PFAAs appeared in the root compartment. Lettuce grown in soils with varying organic carbon contents (0.4%, 2%, 6%) was used to assess the impact of organic carbon sorption on PFAA bioaccumulation. The lettuce grown in soil with the 6% organic carbon content had the lowest bioaccumulation of PFAAs. Bioaccumulation factors for lettuce were correlated to carbon chain

  8. Polypeptides with nonsuppressible insulin-like and cell-growth promoting activities in human serum: isolation, chemical characterization, and some biological properties of forms I and II.

    PubMed

    Rinderknecht, E; Humbel, R E

    1976-07-01

    Serum contains a polypeptide with insulin-like activity not suppressible by insulin antibodies (NSILA). A large-scale isolation procedure for NSILA is described, starting from an acid ethanol extract of a Cohn fraction (precipitate B) obtained from human plasma. Two homogenous polypeptides with insulin-like and cell-growth promoting activities could be isolated by gel filtration, ion exchange chromatography, and preparative polyacrylamide gel electrophoresis. Both components are slightly basic polypeptides with a minimal molecular weight of 5800 +/- 400. Both are single-chain molecules with two intrachain disulfide bridges each and no free sulfhydryl groups. NSILA I and II differ, however, in their amino acid compositions. The N-terminal amino acid sequences are Gly-Pro-Glu- in NSILA I, and Ala-Tyr-Arg- and Tyr-Arg- in NSILA II. Both NSILA I and II enhance net gas exchange in adipose tissue with a specific activity 60 times lower than that of insulin. In the range of 1-50 ng/ml, both substances stimulate [3H]thymidine incorporation into DNA of chick embryo fibroblasts. The same effect can be obtained with insulin but only at concentrations 50-100 times higher than those of NSILA. These results suggest that NSILA I and II are two forms of an insulin-like hormone with predominating effects on cell and tissue growth parameters.

  9. Exposure and effects of perfluoroalkyl compounds on tree swallows nesting at Lake Johanna in east central Minnesota, USA

    USGS Publications Warehouse

    Custer, Christine M.; Custer, Thomas W.; Schoenfuss, Heiko L.; Poganski, Beth H.; Solem, Laura

    2012-01-01

    Tree swallow (Tachycineta bicolor) samples were collected at a reference lake and a nearby lake (Lake Johanna) in east central Minnesota, USA contaminated with perfluorinated carboxylic and sulfonic acids. Tissues were analyzed for a suite of 13 perfluoroalkyl compounds (PFCs) to quantify exposure and to determine if there was an association between egg concentrations of PFCs and reproductive success of tree swallows. Concentrations of perfluoroocatane sulfonate (PFOS) were elevated in all tree swallow tissues from Lake Johanna compared to tissues collected at the reference lake. Other PFCs, except for two, were elevated in blood plasma at Lake Johanna compared to the reference lake. PFOS was the dominant PFC (>75%) at Lake Johanna, but accounted for <50% of total PFCs at the reference lake. There was a negative association between concentrations of PFOS in eggs and hatching success. Reduced hatching success was associated with PFOS levels as low as 150 ng/g wet weight.

  10. Estimating dry deposition and gas/particle partition coefficients of neutral poly-/perfluoroalkyl substances in northern German coast.

    PubMed

    Wang, Zhen; Xie, Zhiyong; Möller, Axel; Mi, Wenying; Wolschke, Hendrik; Ebinghaus, Ralf

    2015-07-01

    Dry deposition fluxes of 12 neutral poly-/perfluoroalkyl substances (PFASs) were estimated at Büsum located in northern German coast, and their gas/particle partition coefficients were predicted by employing the polyparameter linear free energy relationships (PP-LFERs). The gas deposition flux, particle deposition flux and total (gas + particle) flux of the 12 PFASs during sampling periods were 1088 ± 611, 189 ± 75 and 1277 ± 627 pg/(m(2) d), respectively. The gas deposition of PFASs played a key role during deposition to marine ecosystem. Sensitivity analysis showed that wind speed was the most sensitive parameter for gas deposition fluxes. Good agreements (within 1 log unit) were observed between the measured gas/particle partitioning data of PFASs and the predicted partition coefficients using PP-LFERs, indicating the model can reliably predict the gas/particle partitioning behaviors of atmospheric neutral PFASs.

  11. Mutual impacts of wheat (Triticum aestivum L.) and earthworms (Eisenia fetida) on the bioavailability of perfluoroalkyl substances (PFASs) in soil.

    PubMed

    Zhao, Shuyan; Fang, Shuhong; Zhu, Lingyan; Liu, Li; Liu, Zhengtao; Zhang, Yahui

    2014-01-01

    Wheat and earthworms were exposed individually and together to soils contaminated with 11 perfluoroalkyl substances (PFASs). Wheat accumulated PFASs from soil with root concentration factors and bioconcentration factors that decreased as the number of perfluorinated carbons in the molecule increased. Earthworms accumulated PFASs from soil with biota-to-soil accumulation factors that increased with the number of carbons. Translocation factors (TF) of perfluorinated carboxylates (PFCAs) in wheat peaked at perfluorohexanoic acid and decreased significantly as the number of carbons increased or decreased. Perfluorohexane sulfonate produced the greatest TF of the three perfluorinated sulfonates (PFSAs) examined. Wheat increased the bioaccumulation of all 11 PFASs in earthworms and earthworms increased the bioaccumulation in wheat of PFCAs containing seven or less perfluorinated carbons, decreased bioaccumulation of PFCAs with more than seven carbons, and decreased bioaccumulation of PFSAs. In general, the co-presence of wheat and earthworms enhanced the bioavailability of PFASs in soil.

  12. Ombrotrophic peat bogs are not suited as natural archives to investigate the historical atmospheric deposition of perfluoroalkyl substances.

    PubMed

    Dreyer, Annekatrin; Thuens, Sabine; Kirchgeorg, Torben; Radke, Michael

    2012-07-17

    As ombrotrophic peat bogs receive only atmospheric input of contaminants, they have been identified as suitable natural archives for investigating historical depositions of airborne pollutants. To elucidate their suitability for determining the historical atmospheric contamination with perfluoroalkyl substances (PFAS), two peat cores were sampled at Mer Bleue, a bog located close to Ottawa, Canada. Peat cores were segmented, dried, and analyzed in duplicate for 25 PFASs (5 perfluororalkyl sulfonates (PFSAs), 13 perfluoroalkyl carboxylates (PFCAs), 7 perfluororalkyl sulfonamido substances). Peat samples were extracted by ultrasonication, cleaned up using a QuEChERS method, and PFASs were measured by HPLC-MS/MS. Twelve PFCAs and PFSAs were detected regularly in peat samples with perfluorooctane sulfonate (85-655 ng kg(-1)), perfluorooctanoate (150-390 ng kg(-1)), and perfluorononanoate (45-320 ng kg(-1)) at highest concentrations. Because of post depositional relocation processes within the peat cores, true or unbiased deposition fluxes (i.e., not affected by post depositional changes) could not be calculated. Apparent or biased deposition rates (i.e., affected by post depositional changes) were lower than measured/calculated deposition rates for similar urban or near-urban sites. Compared to PFAS production, PFAS concentration and deposition maxima were shifted about 30 years toward the past and some analytes were detected even in the oldest segments from the beginning of the 20th century. This was attributed to PFAS mobility in the peat profile. Considerable differences were observed between both peat cores and different PFASs. Overall, this study demonstrates that ombrotrophic bogs are not suited natural archives to provide authentic and reliable temporal trend data of historical atmospheric PFAS deposition.

  13. Effect of sucrose on chemically and thermally induced unfolding of domain-I of human serum albumin: Solvation dynamics and fluorescence anisotropy study.

    PubMed

    Yadav, Rajeev; Sengupta, Bhaswati; Sen, Pratik

    2016-04-01

    The present study is devoted to understand the effect of sucrose on the hydration dynamics and rotational relaxation dynamics within the domain-I of HSA during chemically as well as thermally induced unfolding. It has been observed that the average solvation time become slower in the presence of sucrose for the lower concentrations of GnHCl, however at higher concentrations of GnHCl the effect of sucrose is almost negligible. From the time resolved fluorescence anisotropy it has been observed that in the lower concentration region of GnHCl the sucrose induced stabilization is small as compared to the higher concentrations of GnHCl. We have concluded that the hydration dynamics plays an important role in the sucrose induced stabilization process at the low concentration region; whereas environmental restriction is responsible at the higher concentration of GnHCl. However, we have observed a negligible stabilizing effect of sucrose towards the temperature induced unfolding.

  14. Perfluoroalkyl substances assessment in drinking waters from Brazil, France and Spain.

    PubMed

    Schwanz, Thiago G; Llorca, Marta; Farré, Marinella; Barceló, Damià

    2016-01-01

    Human exposure to perfluoroalkyl substances (PFASs) occurs primarily via dietary intake and drinking water. In this study, 16 PFASs have been assessed in 96 drinking waters (38 bottled waters and 58 samples of tap water) from Brazil, France and Spain. The total daily intake and the risk index (RI) of 16 PFASs through drinking water in Brazil, France and Spain have been estimated. This study was carried out using an analytical method based on an online sample enrichment followed by liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS). The quality parameters of the analytical method were satisfactory for the analysis of the 16 selected compounds in drinking waters. Notably, the method limits of detection (MLOD) and method limits of quantification (MLOQ) were in the range of 0.15 to 8.76ng/l and 0.47 to 26.54ng/l, respectively. The results showed that the highest PFASs concentrations were found in tap water samples and the more frequently found compound was perfluorooctanesulfonic acid (PFOS), with mean concentrations of 7.73, 15.33 and 15.83ng/l in French, Spanish and Brazilian samples, respectively. In addition, PFOS was detected in all tap water samples from Brazil. The highest level of PFASs contamination in a single sample was 140.48ng/l in a sample of Spanish tap water. In turn, in bottled waters the highest levels were detected in a French sample with 116ng/l as the sum of PFASs. Furthermore, the most frequent compounds and those at higher concentrations were perfluoroheptanoic acid (PFHpA) with a mean of frequencies in the three countries of 51.3%, followed by perfluorobutanesulfonic acid (PFBS) (27.2%) and perfluorooctanoic acid (PFOA) (23.0%). Considering that bottled water is approximately 38% of the total intake, the total PFASs exposure through drinking water intake for an adult man was estimated to be 54.8, 58.0 and 75.6ng/person per day in Spain, France and Brazil, respectively. However, assuming that the water content in other beverages

  15. Perfluoroalkyl substances assessment in drinking waters from Brazil, France and Spain.

    PubMed

    Schwanz, Thiago G; Llorca, Marta; Farré, Marinella; Barceló, Damià

    2016-01-01

    Human exposure to perfluoroalkyl substances (PFASs) occurs primarily via dietary intake and drinking water. In this study, 16 PFASs have been assessed in 96 drinking waters (38 bottled waters and 58 samples of tap water) from Brazil, France and Spain. The total daily intake and the risk index (RI) of 16 PFASs through drinking water in Brazil, France and Spain have been estimated. This study was carried out using an analytical method based on an online sample enrichment followed by liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS). The quality parameters of the analytical method were satisfactory for the analysis of the 16 selected compounds in drinking waters. Notably, the method limits of detection (MLOD) and method limits of quantification (MLOQ) were in the range of 0.15 to 8.76ng/l and 0.47 to 26.54ng/l, respectively. The results showed that the highest PFASs concentrations were found in tap water samples and the more frequently found compound was perfluorooctanesulfonic acid (PFOS), with mean concentrations of 7.73, 15.33 and 15.83ng/l in French, Spanish and Brazilian samples, respectively. In addition, PFOS was detected in all tap water samples from Brazil. The highest level of PFASs contamination in a single sample was 140.48ng/l in a sample of Spanish tap water. In turn, in bottled waters the highest levels were detected in a French sample with 116ng/l as the sum of PFASs. Furthermore, the most frequent compounds and those at higher concentrations were perfluoroheptanoic acid (PFHpA) with a mean of frequencies in the three countries of 51.3%, followed by perfluorobutanesulfonic acid (PFBS) (27.2%) and perfluorooctanoic acid (PFOA) (23.0%). Considering that bottled water is approximately 38% of the total intake, the total PFASs exposure through drinking water intake for an adult man was estimated to be 54.8, 58.0 and 75.6ng/person per day in Spain, France and Brazil, respectively. However, assuming that the water content in other beverages

  16. QUANTIFICATION OF FLUOROTELOMER-BASED CHEMICALS IN MAMMALIAN MATRICES BY MONITORING PERFLUOROALKYL CHAIN FRAGMENTS WITH GC/MS

    EPA Science Inventory

    Perfluorocarboxylic acids (PFCAs), namely perfluorooctanoic acid (PFOA) and perfluorononanoic acid (PFNA), have been identified as persistent, bioaccurnulative and potentially toxic compounds. The structural analog, 8-2 fluorotelomer alcohol (8-2 FTOH) is considered the probable ...

  17. Mechanisms of perfluoroalkyl acid (PFAA) toxicity: Involvement of peroxisome proliferator activator receptor alpha (PPAR) molecular signals.

    EPA Science Inventory

    Perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) are members of a family of environmentally persistent perfluorinated compounds and are found in the serum of wildlife and humans. PFOS and PFOA are developmentally toxic in rats and mice. Exposure in utero reduces...

  18. Seasonal variations and spatial distributions of perfluoroalkyl substances in the rivers Elbe and lower Weser and the North Sea.

    PubMed

    Zhao, Zhen; Xie, Zhiyong; Tang, Jianhui; Sturm, Renate; Chen, Yingjun; Zhang, Gan; Ebinghaus, Ralf

    2015-06-01

    The spatial distributions and seasonal variations of perfluoroalkyl substances (PFASs) in surface waters were investigated for the German rivers Elbe and lower Weser, and the North Sea. ∑PFAS concentrations ranged from 4.1 to 250ngL(-1) in the River Elbe, from 3.8 to 16ngL(-1) in the lower Weser, and from 0.13 to 10ngL(-1) in the North Sea. The most abundant compound was perfluorobutanesulfonate (PFBS) with a proportion of 24% in river water and 31% in seawater samples. The concentrations of perfluorohexanoic acid (PFHxA) and perfluorooctanoic acid (PFOA) in Elbe River water showed significant seasonal variation in 2011. The seasonal variations might be related to the variations of water discharge. The highest concentrations of PFOA and PFHxA were detected in August. Pearson correlations showed that perfluorobutanoic acid (PFBA) and PFBS had different sources from other PFASs, and the current manufacturing and use of C4-based products could explain the distinction. The estimated fluxes of individual substances and ∑PFASs in the River Elbe showed no significant seasonal variation. The annual fluxes of PFASs to the North Sea were estimated to be 335±100kgyear(-1) from the River Elbe and 102±22kgyear(-1) from the River Weser.

  19. Efficient Sorption and Removal of Perfluoroalkyl Acids (PFAAs) from Aqueous Solution by Metal Hydroxides Generated in Situ by Electrocoagulation.

    PubMed

    Lin, Hui; Wang, Yujuan; Niu, Junfeng; Yue, Zhihan; Huang, Qingguo

    2015-09-01

    Removal of environmentally persistent perfluoroalkyl acids (PFAAs), that is, perfluorooctanesulfonate (PFOS) and perfluorocarboxylic acids (PFCAs, C4 ∼ C10) were investigated through sorption on four metal hydroxide flocs generated in situ by electrocoagulation in deionized water with 10 mM NaCl as supporting electrolyte. The results indicated that the zinc hydroxide flocs yielded the highest removal efficiency with a wide range concentration of PFOA/PFOS (1.5 μM ∼ 0.5 mM) at the zinc dosage <150 mg L(-1) with the energy consumption <0.18 Wh L(-1). The sorption kinetics indicated that the zinc hydroxide flocs had an equilibrium adsorbed amount (qe) up to 5.74/7.69 mmol g(-1) (Zn) for PFOA/PFOS at the initial concentration of 0.5 mM with an initial sorption rate (v0) of 1.01 × 10(3)/1.81 × 10(3) mmol g(-1) h(-1). The sorption of PFOA/PFOS reached equilibrium within <10 min. The sorption mechanisms of PFAAs on the zinc hydroxide flocs were proposed based on the investigation of various driving forces. The results indicated that the hydrophobic interaction was primarily responsible for the PFAAs sorption. The electrocoagulation process with zinc anode may have a great potential for removing PFAAs from industrial wastewater as well as contaminated environmental waterbody.

  20. Levels and spatial distribution of perfluoroalkyl substances in China Liaodong Bay basin with concentrated fluorine industry parks.

    PubMed

    Chen, Hong; Zhang, Can; Han, Jianbo; Sun, Ruijun; Kong, Xiangyun; Wang, Xiaomeng; He, Xin

    2015-12-30

    Eighteen different perfluoroalkyl substances (PFASs) were investigated in 35 river water samples and 34 sediment samples collected from rivers in the Liaodong Bay basin containing two fluorine industry parks. Perfluorooctanoate (PFOA) and perfluorooctane sulfonate (PFOS) were the predominant PFASs in freshwater, with median concentrations of 26.5 ng/L and 1.87 ng/L, respectively. However, perfluorobutane sulfonate (PFBS) had the highest maximum concentration (up to 124.1 ng/L, approximately two orders of magnitude higher) in water at a site which is the nearest to the industrial source of PFASs. Total PFASs in water at this site were also the highest. In contrast, PFOA and perfluorooctadecanoate (PFOcDA) were the most abundant PFASs in sediment, with median concentrations of 1.19 ng/g and 0.35 ng/g, respectively. Total PFAS concentrations in sediment from the site near to the industrial park were significantly higher than the other rivers. Mass loading of total PFASs from the rivers flowing into Liaodong Bay was estimated to be 506 kg/year.

  1. Distribution of perfluoroalkyl substances (PFASs) with isomer analysis among the tissues of aquatic organisms in Taihu Lake, China.

    PubMed

    Fang, Shuhong; Zhao, Shuyan; Zhang, Yifeng; Zhong, Wenjue; Zhu, Lingyan

    2014-10-01

    The distribution of perfluoroalkyl substances (PFASs) and the isomers of perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) was investigated among various tissues (including muscle, gill, kidney, liver) and eggs, in aquatic organisms in Taihu Lake, China. Highest concentration of ΣPFASs was mostly found in liver (278-685 ng/g ww) and eggs (66.0-467 ng/g ww) while the lowest was in muscle (40.6-165 ng/g ww). n-PFOS was the predominant PFOS isomer in most of the tissues with a proportion of 46.3-96.5%. Ratios of PFAS concentrations in eggs to those in liver (E/L) increased positively with the protein-water partition coefficient. The E/L of PFOS isomers descended in the order: linear > monomethyl > diperfluoromethyl isomers. The liver/muscle and kidney/muscle ratios of n-PFOS were higher than branched isomers, suggesting that n-PFOS has higher binding affinity with hepatic proteins or branched isomers are preferentially excreted though liver and kidney.

  2. Footprints of Urban Micro-Pollution in Protected Areas: Investigating the Longitudinal Distribution of Perfluoroalkyl Acids in Wildlife Preserves.

    PubMed

    Rodriguez-Jorquera, Ignacio A; Silva-Sanchez, Cecilia; Strynar, Mark; Denslow, Nancy D; Toor, Gurpal S

    2016-01-01

    Current approaches to protect biodiversity by establishing protected areas usually gloss over water pollution as a threat. Our objective was to determine the longitudinal and seasonal distribution of perfluoroalkyl acids (PFAAs) in water column and sediments from a wastewater dominated stream that enters preservation areas. Water samples were collected along the longitudinal section (six sites, 1000 m away from each other) of the stream during the dry and wet seasons. Sediments were collected from three sites along the stream from three depths. Water and sediments were analyzed for PFAAs using high performance liquid chromatography-tandem mass spectrometry. Eleven PFAAs with 5 to 14 carbon atoms were detected in the water column at all sampling points, with a minor reduction at the last point suggesting a dilution effect. The most detected PFAAs was PFOS, followed by perfluorooctanoic acid (PFOA), and perfluorohexanoic acid (PFHxA). Seasonal differences in PFAAs concentrations suggested contribution of stormwater runoff during the wet season. All analyzed PFAAs in sediments were under the limit of quantification, likely due to the high proportion of sand and low organic matter. However, high concentrations of PFAAs were detected in the water column inside the protected areas, which includes PFOS in concentrations considered not safe for avian wildlife. Water samples appear to be more relevant than sediments to determine PFAAs micro-pollution in water bodies with sandy sediments. Inclusion of a management plans on micro-pollution research, monitoring, and mitigation is recommended for protected areas. PMID:26909512

  3. Estimating dry deposition and gas/particle partition coefficients of neutral poly-/perfluoroalkyl substances in northern German coast.

    PubMed

    Wang, Zhen; Xie, Zhiyong; Möller, Axel; Mi, Wenying; Wolschke, Hendrik; Ebinghaus, Ralf

    2015-07-01

    Dry deposition fluxes of 12 neutral poly-/perfluoroalkyl substances (PFASs) were estimated at Büsum located in northern German coast, and their gas/particle partition coefficients were predicted by employing the polyparameter linear free energy relationships (PP-LFERs). The gas deposition flux, particle deposition flux and total (gas + particle) flux of the 12 PFASs during sampling periods were 1088 ± 611, 189 ± 75 and 1277 ± 627 pg/(m(2) d), respectively. The gas deposition of PFASs played a key role during deposition to marine ecosystem. Sensitivity analysis showed that wind speed was the most sensitive parameter for gas deposition fluxes. Good agreements (within 1 log unit) were observed between the measured gas/particle partitioning data of PFASs and the predicted partition coefficients using PP-LFERs, indicating the model can reliably predict the gas/particle partitioning behaviors of atmospheric neutral PFASs. PMID:25818091

  4. Perfluoroalkyl acids and their precursors in Swedish food: The relative importance of direct and indirect dietary exposure.

    PubMed

    Gebbink, Wouter A; Glynn, Anders; Darnerud, Per Ola; Berger, Urs

    2015-03-01

    We analyzed food market basket samples obtained in Sweden from 1999, 2005, and 2010 for perfluoroalkyl acids (PFAAs) and a range of precursor compounds. Perfluorooctane sulfonic acid (PFOS) precursors were detected in all food year pools with the highest concentrations in 1999. Six polyfluoroalkyl phosphate diesters (diPAPs, 4:2/6:2, 6:2/6:2, 6:2/8:2, 8:2/8:2, 6:2/10:2, and 10:2/10:2) were detected in the year pools with the highest ∑diPAP concentrations in 1999 and 2005. All precursors were predominantly found in meat, fish, and/or eggs based on analysis of individual food groups from 1999. Based on year pools, PFOS precursors contributed between 4 and 1% as an indirect source to total dietary PFOS intakes between 1999 and 2010. Perfluorohexanoic acid (PFHxA) exposure originated entirely from diPAPs, whereas for perfluorooctanoic acid (PFOA) and perfluorodecanoic acid (PFDA), diPAPs contributed between 1 and 19% to total exposure. The lowest precursor contributions were generally seen in food samples from 2010.

  5. Perfluoroalkyl acids in municipal landfill leachates from China: Occurrence, fate during leachate treatment and potential impact on groundwater.

    PubMed

    Yan, Hong; Cousins, Ian T; Zhang, Chaojie; Zhou, Qi

    2015-08-15

    Raw and treated landfill leachate samples were collected from 5 municipal landfill sites in China to measure the concentrations and contamination profile of perfluoroalkyl acids (PFAAs) in leachate during different steps of treatment. The total concentration of PFAAs (∑PFAAs) ranged from 7280 to 292,000 ng L(-1) in raw leachate and from 98.4 to 282,000 ng L(-1) in treated leachate. The dominant compounds measured were PFOA (mean contribution 28.8% and 36.8% in raw and treated leachate, respectively) and PFBS (26.1% and 40.8% in raw and treated leachate, respectively). A calculation of mass flows during the leachate treatment processes showed that the fate of individual PFAAs was substance and treatment-specific. The Chinese national leakage of ∑PFAAs to groundwater from landfill leachate was estimated to be 3110 kg year(-1), which is a significant environmental release that is potentially threatening the sustainable use of groundwater as a drinking water source.

  6. Role of ingestion route in the perfluoroalkyl substance bioaccumulation by Chironomus plumosus larvae in sediments amended with carbonaceous materials.

    PubMed

    Zhai, Yawei; Xia, Xinghui; Zhao, Xiuli; Dong, Haiyang; Zhu, Baotong; Xia, Na; Dong, Jianwei

    2016-01-25

    The role of ingestion route in the bioaccumulation of six types of perfluoroalkyl substances (PFASs) by Chironomus plumosus larvae in sediments amended with four types of carbonaceous materials (CMs) was studied. The results showed that the body burden of PFASs decreased in the presence of CMs at mass ratios of 0.2-2%, regardless of ingestion. PFASs accumulated by the larvae with ingestion exposure were higher than those without ingestion, and the role of ingestion route was altered in the presence of CMs. The contribution of ingestion route to PFAS bioaccumulation was 2.7-31.6% without CMs, and it increased to more than 61.4% in the presence of fullerene at mass ratios of 0.2-2%. The enhancement of the ingestion route contribution caused by CMs is due to the fact that the CMs can be ingested and CM-associated PFASs can be partly desorbed in larvae. The maximum desorption efficiency of perfluorooctanoic acid was 20.8% from fullerene by the larval digestive juice. This study suggests that CM-associated PFASs could be accumulated partly by organisms, and the ecological risk of PFASs might increase in some cases with the presence of CMs. This should be considered when applying CMs in PFAS and other hydrophobic organic compound pollution remediation. PMID:26489915

  7. Bioaccumulation of emerging organic compounds (perfluoroalkyl substances and halogenated flame retardants) by earthworm in biosolid amended soils.

    PubMed

    Navarro, Irene; de la Torre, Adrián; Sanz, Paloma; Pro, Javier; Carbonell, Gregoria; Martínez, María de Los Ángeles

    2016-08-01

    In the present work, the bioaccumulation behavior of 49 target emerging organic compounds (20 perfluoroalkyl substances, PFASs, and 29 halogenated flame retardants, HFRs) was studied in soil invertebrates (Eisenia andrei). Multi species soil systems (MS·3) were used to assess the fate and the effects associated with the application of four biosolids in agricultural soil on terrestrial soil organisms. Biosolid amendment increased concentrations 1.5-14-fold for PFASs, 1.1-2.4-fold for polybrominated diphenyl ethers, PBDEs, and 1.1-3.6-fold for chlorinated flame retardants, CFRs. Perfluorooctanesulfonate, PFOS, (25%) and BDE-209 (60%) were the predominant PFAS and HFR compounds, respectively, in biosolids-amended soils. Total concentrations (ng/g dry weight) in earthworms from biosolid-amended soils ranged from 9.9 to 101 for PFASs, from 45 to 76 for PBDEs and 0.3-32 for CFRs. Bioaccumulation factors (BAFs) were calculated to evaluate the degree of exposure of pollutants in earthworms. The mean BAF ranged from 2.2 to 198 for PFASs, 0.6-17 for PBDEs and 0.5-20 for CFRs. The relationship of PFAS and PBDE BAFs in earthworms and their log Kow were compared: PFAS BAFs increased while PBDE BAFs declined with increasing log Kow values. The effect of the aging (21 days) on the bioavailability of the pollutants in amended soils was also assessed: the residence time affected differently to the compounds studied. PMID:27174781

  8. Footprints of Urban Micro-Pollution in Protected Areas: Investigating the Longitudinal Distribution of Perfluoroalkyl Acids in Wildlife Preserves

    PubMed Central

    Rodriguez-Jorquera, Ignacio A.; Silva-Sanchez, Cecilia; Strynar, Mark; Denslow, Nancy D.; Toor, Gurpal S.

    2016-01-01

    Current approaches to protect biodiversity by establishing protected areas usually gloss over water pollution as a threat. Our objective was to determine the longitudinal and seasonal distribution of perfluoroalkyl acids (PFAAs) in water column and sediments from a wastewater dominated stream that enters preservation areas. Water samples were collected along the longitudinal section (six sites, 1000 m away from each other) of the stream during the dry and wet seasons. Sediments were collected from three sites along the stream from three depths. Water and sediments were analyzed for PFAAs using high performance liquid chromatography-tandem mass spectrometry. Eleven PFAAs with 5 to 14 carbon atoms were detected in the water column at all sampling points, with a minor reduction at the last point suggesting a dilution effect. The most detected PFAAs was PFOS, followed by perfluorooctanoic acid (PFOA), and perfluorohexanoic acid (PFHxA). Seasonal differences in PFAAs concentrations suggested contribution of stormwater runoff during the wet season. All analyzed PFAAs in sediments were under the limit of quantification, likely due to the high proportion of sand and low organic matter. However, high concentrations of PFAAs were detected in the water column inside the protected areas, which includes PFOS in concentrations considered not safe for avian wildlife. Water samples appear to be more relevant than sediments to determine PFAAs micro-pollution in water bodies with sandy sediments. Inclusion of a management plans on micro-pollution research, monitoring, and mitigation is recommended for protected areas. PMID:26909512

  9. Effect of perfluoroalkyl chain length on monolayer behavior of partially fluorinated oleic acid molecules at the air-water interface.

    PubMed

    Baba, Teruhiko; Takai, Katsuki; Takagi, Toshiyuki; Kanamori, Toshiyuki

    2013-01-01

    A series of oleic acid (OA) analogs containing terminal perfluoroalkyl groups (CF3, C2F5, n-C3F7, n-C4F9 or n-C8F17) was synthesized to clarify how the fluorinated chain length affects the stability and molecular packing of liquid-expanded OA monolayers at the air-water interface. Although the substitution of terminal CF3 group for CH3 in OA had no effect on monolayer stability, further fluorination led to a gradual increase in monolayer stability at 25 °C. Surface pressure-area isotherm revealed that partially fluorinated OA analogs form more expanded monolayers than OA at low surface pressures, and that the monolayer behavior of OA analogs with the even-carbon numbered fluorinated chain is almost the same as that of OA upon monolayer compression, whereas the behavior of OA analogs with the odd-carbon numbered fluorinated chain significantly differs from that of OA. These results indicate: (i) the terminal short part (at least C2 residue) in OA predominantly determines the liquid-expanded monolayer stability; (ii) the molecular packing state of OA may be perturbed by the substitution of a short odd-carbon numbered fluorinated chain; (iii) hence, OA analogs with even-carbon numbered chain are considered to be preferable as hydrophobic building blocks for the synthesis of fluorinated phospholipids.

  10. Physical and Biological Release of Poly- and Perfluoroalkyl Substances (PFASs) from Municipal Solid Waste in Anaerobic Model Landfill Reactors.

    PubMed

    Allred, B McKay; Lang, Johnsie R; Barlaz, Morton A; Field, Jennifer A

    2015-07-01

    A wide variety of consumer products that are treated with poly- and perfluoroalkyl substances (PFASs) and related formulations are disposed of in landfills. Landfill leachate has significant concentrations of PFASs and acts as secondary point sources to surface water. This study models how PFASs enter leachate using four laboratory-scale anaerobic bioreactors filled with municipal solid waste (MSW) and operated over 273 days. Duplicate reactors were monitored under live and abiotic conditions to evaluate influences attributable to biological activity. The biologically active reactors simulated the methanogenic conditions that develop in all landfills, producing ∼140 mL CH4/dry g refuse. The average total PFAS leaching measured in live reactors (16.7 nmol/kg dry refuse) was greater than the average for abiotic reactors (2.83 nmol/kg dry refuse), indicating biological processes were primarily responsible for leaching. The low-level leaching in the abiotic reactors was primarily due to PFCAs ≤C8 (2.48 nmol/kg dry refuse). Concentrations of known biodegradation intermediates, including methylperfluorobutane sulfonamide acetic acid and the n:2 and n:3 fluorotelomer carboxylates, increased steadily after the onset of methanogenesis, with the 5:3 fluorotelomer carboxylate becoming the single most concentrated PFAS observed in live reactors (9.53 nmol/kg dry refuse).

  11. National inventory of perfluoroalkyl substances in archived U.S. biosolids from the 2001 EPA National Sewage Sludge Survey

    PubMed Central

    Venkatesan, Arjun K.; Halden, Rolf U.

    2013-01-01

    Using liquid chromatography tandem mass spectrometry, we determined the first nationwide inventories of 13 perfluoroalkyl substances (PFASs) in U.S. biosolids via analysis of samples collected by the U.S. Environmental Protection Agency in the 2001 National Sewage Sludge Survey. Perfluorooctane sulfonate [PFOS; 403 ± 127 ng/g dry weight (dw)] was the most abundant PFAS detected in biosolids composites representing 32 U.S. states and the District of Columbia, followed by perfluorooctanoate [PFOA; 34 ± 22 ng/g dw] and perfluorodecanoate [PFDA; 26 ± 20 ng/g dw]. Mean concentrations in U.S. biosolids of the remaining ten PFASs ranged between 2 and 21 ng/g dw. Interestingly, concentrations of PFOS determined here in biosolids collected prior to the phase-out period (2002) were similar to levels reported in the literature for recent years. The mean load of ΣPFASs in U.S. biosolids was estimated at 2749–3450 kg/year, of which about 1375–2070 kg is applied on agricultural land and 467–587 kg goes to landfills as an alternative disposal route. This study informs the risk assessment of PFASs by furnishing national inventories of PFASs occurrence and environmental release via biosolids application on land. PMID:23562984

  12. Semiautomated solid-phase extraction followed by derivatisation and gas chromatography–mass spectrometry for determination of perfluoroalkyl acids in water.

    PubMed

    Jurado-Sánchez, Beatriz; Ballesteros, Evaristo; Gallego, Mercedes

    2013-11-29

    This paper describes a sensitive approach for the determination of 6 perfluoroalkyl carboxylic acids and perfluorooctane sulfonic acid in water. Samples were preconcentrated using an automatic solid-phase extraction module and then manually derivatised and determined by gas chromatography–mass spectrometry. The analytes were derivatised with a isobutyl chloroformate/isobutanol mixture, using 3% N,N-dicyclohexylcarbodiimide in pyridine as the catalyst. From a systematic comparison of several reversed-phase and anion-exchange sorbent materials for the retention of perfluoroalkyl acids, the high-est retention efficiencies (∼100%) were achieved with LiChrolut EN and Discovery DSC-SAX columns.LiChrolut EN was the sorbent selected due to several advantages (sample pH ∼1; sample flow rate,5.5 mL/min; breakthrough volume, 300 mL) over Discovery DSC-SAX (sample pH ∼6; sample flow rate,3.0 mL/min; breakthrough volume, 45 mL), for the retention of the studied compounds. Detection and quantification limits within the range of 0.1–0.5 ng/L and 0.4–1.7 ng/L, respectively, were obtained for a sorbent column of 70 mg of LiChrolut EN and 250 mL of sample, the relative standard deviation being lower than 7%. The method was applied both to the analysis of water collected at the intake (raw) and atthe exit (treated) of two drinking water treatment plants, as well as to various types of water. Few samples were positive for perfluoroalkyl acids and only one acid (perfluoroheptanoic or perfluorooctanoic) was found in each treatment plant. The highest number and concentration of analytes (perfluoroheptanoic,perfluorooctanoic and perfluorodecanoic acid) were found in one wastewater.

  13. Preliminary assessment of developmental toxicity of Perfluorinated Phosphonic Acid in mice

    EPA Science Inventory

    Perfluorinated phosphonic acids (PFPAs) are a third member of the perfluoroalkyl acid (PFAA) family, and are structurally similar to the perfluoroalkyl sulfonates and perfluoroalkyl carboxylates. These emerging chemicals have recently been detected in the environment, particularl...

  14. Effects of Perfluorinated Phosphonic Acid Exposure during pregnancy in the mouse

    EPA Science Inventory

    Perfluorinated phosphonic acids (PFPAs) are a member of the perfluoroalkyl acid (PFAA) family, and are structurally similar to the perfluoroalkyl sulfonates and perfluoroalkyl carboxylates. These chemicals have recently been detected in the environment, particularly in surface wa...

  15. A North American and global survey of perfluoroalkyl substances in surface soils: Distribution patterns and mode of occurrence.

    PubMed

    Rankin, Keegan; Mabury, Scott A; Jenkins, Thomas M; Washington, John W

    2016-10-01

    The distribution of 32 per/polyfluoroalkyl substances (PFASs) in surface soils was determined at 62 locations representing all continents (North America n = 33, Europe n = 10, Asia n = 6, Africa n = 5, Australia n = 4, South America n = 3 and Antarctica n = 1) using ultra performance liquid chromatography tandem mass spectrometry (UPLC-MS/MS) systems. Quantifiable levels of perfluoroalkyl carboxylates (PFCAs: PFHxA-PFTeDA) were observed in all samples with total concentrations ranging from 29 to 14,300 pg/g (dry weight), while perfluoroalkane sulfonates (PFSAs: PFHxS, PFOS and PFDS) were detected in all samples but one, ranging from

  16. Occurrence of perfluoroalkyl carboxylates and sulfonates in drinking water utilities and related waters from the United States.

    PubMed

    Quiñones, Oscar; Snyder, Shane A

    2009-12-15

    The prevalence and persistence of perfluoroalkyl compounds (PFCs) in environmental and biological systems has been well documented, and a rising number of reports suggest that certain PFCs can result in adverse health effects in mammals. As traditional water sources become increasingly impacted by waste discharge and the demand for planned potable reuse grows, there is recent interest in determining PFC occurrence in drinking water supplies. Here we report monitoring results from drinking water treatment facility samples collected across the United States, and from associated surface, ground, and wastewater sources. Using automated solid phase extraction (SPE) and isotope-dilution liquid chromatography/tandem mass spectrometry (LC/MS-MS), samples were screened for perfluorohexanoic acid (PFHxA), perfluorohexanesulfonate (PFHxS), perfluorooctanoic acid (PFOA), perfluorooctanesulfonate (PFOS), perfluorononanoic acid (PFNA) perfluorodecanoic acid (PFDA), perfluoroundecanoic acid (PFUdA), and perfluorododecanoic acid (PFDoA). Method reporting limits (MRLs) were established at 1.0 ng/L for all monitored PFCs except PFOA, for which the MRL was set at 5.0 ng/L given elevated procedural and instrumental background levels. PFOS was the only investigated PFC detected in minimally impacted surface waters, with individual site averages of 2.0 ng/L and lower. Conversely, wastewater treatment plant (WWTP) effluents and other highly impacted waters had almost 100% detection frequency for all PFCs except PFUdA and PFDoA, which were not detected above MRL in any samples. Of the investigated PFCs, PFOA averaged the highest overall concentration at any site at 115 ng/L. Substantial impacts from treated wastewater generally caused increased summed PFC concentrations at downstream drinking water facilities, although levels and distribution suggest geographical variability. No discernible differences between influent and effluent PFC levels were observed for drinking water facilities

  17. Comparing humic substance and protein compound effects on the bioaccumulation of perfluoroalkyl substances by Daphnia magna in water.

    PubMed

    Xia, Xinghui; Dai, Zhineng; Rabearisoa, Andry Harinaina; Zhao, Pujun; Jiang, Xiaoman

    2015-01-01

    The influence of humic substances and protein compounds on the bioaccumulation of six types of perfluoroalkyl substances (PFASs) in Daphnia magna was compared. The humic substances included humic acid (HA) and fulvic acid (FA), the protein compounds included chicken egg albumin (albumin) and peptone, and the PFASs included perfluorooctane sulfonate (PFOS), perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), perfluorodecanoic acid, perfluoroundecanoic acid, and perfluorododecanoic acid. Four concentrations (0, 1, 10, and 20 mg L(-1)) of the four dissolved organic matter (DOM) types were investigated. At the 1 mg L(-1) level, HA and albumin enhanced all tested PFAS bioaccumulation, whereas FA and peptone only enhanced the bioaccumulation of shorter-chain PFASs (PFOS, PFOA, and PFNA). However, all four DOM types decreased all tested PFAS bioaccumulation at the 20 mg L(-1) level, and the decreasing ratios of bioaccumulation factors caused by FA, HA, albumin, and peptone were 1-49%, 23-77%, 17-58%, and 8-56%, respectively compared with those without DOM. This is because DOM not only reduced the bioavailable concentrations and uptake rates of PFASs but also lowered the elimination rates of PFASs in D. magna, and these opposite effects would change with different DOM types and concentrations. Although the partition coefficients (L kg(-1)) of PFASs between HA and water (10(4.21)-10(4.98)) were much lower than those between albumin and water (10(4.92)-10(5.86)), their effects on PFAS bioaccumulation were comparable. This study suggests that although PFASs are a type of proteinophilic compounds, humic substances also have important effects on their bioavailability and bioaccumulation in aquatic organisms.

  18. Temporal trends of perfluoroalkyl acids in plasma samples of pregnant women in Hokkaido, Japan, 2003-2011.

    PubMed

    Okada, Emiko; Kashino, Ikuko; Matsuura, Hideyuki; Sasaki, Seiko; Miyashita, Chihiro; Yamamoto, Jun; Ikeno, Tamiko; Ito, Yoichi M; Matsumura, Toru; Tamakoshi, Akiko; Kishi, Reiko

    2013-10-01

    Perfluoroalkyl acids (PFAAs) are persistent organic pollutants that are used in a wide range of consumer products. Recent epidemiological studies have shown that prenatal exposure to toxic levels of PFAAs in the environment may adversely affect fetal growth and humoral immune response in infants and children. Here we have characterized levels of prenatal exposure to PFAA between 2003 and 2011 in Hokkaido, Japan, by measuring PFAA concentrations in plasma samples from pregnant women. The study population comprised 150 women who enrolled in a prospective birth cohort study conducted in Hokkaido. Eleven PFAAs were measured in maternal plasma samples using simultaneous analysis by ultra-performance liquid chromatography coupled to triple quadrupole tandem mass spectrometry. At the end of the study, in 2011, age- and parity-adjusted mean concentrations of perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), perfluorodecanoic acid (PFDA), perfluoroundecanoic acid (PFUnDA), perfluorododecanoic acid (PFDoDA), perfluorotridecanoic acid (PFTrDA), perfluorohexane sulfonate (PFHxS), and perfluorooctane sulfonate (PFOS) were 1.35ng/mL, 1.26ng/mL, 0.66ng/mL, 1.29ng/mL, 0.25ng/mL, 0.33ng/mL, 0.28ng/mL, and 3.86ng/mL, respectively. Whereas PFOS and PFOA concentrations declined 8.4%/y and 3.1%/y, respectively, PFNA and PFDA levels increased 4.7%/y and 2.4%/y, respectively, between 2003 and 2011. PFUnDA, PFDoDA, and PFTrDA were detected in the vast majority of maternal samples, but no significant temporal trend was apparent. Future studies must involve a larger population of pregnant women and their children to determine the effects of prenatal exposure to PFAA on health outcomes in infants and children.

  19. Perfluoroalkyl compounds in dust from Asian, Australian, European, and North American homes and UK cars, classrooms, and offices.

    PubMed

    Goosey, Emma; Harrad, Stuart

    2011-01-01

    Perfluoroalkyl compounds (PFCs) were measured in dust from Australian, Canadian, French, German, Kazahkstani, Thai, UK, and US homes, and UK cars, classrooms, and offices. Most PFCs were significantly lower in Kazahkstan and Thailand than elsewhere; 2-(N-methylperfluoro-1-octanesulfonamido)-ethanol (MeFOSE) and 2-(N-ethylperfluoro-1-octanesulfonamido)-ethanol (EtFOSE) were significantly lower in Canada than in the UK and the US; perfluoro-1-hexanesulfonate (PFHxS) was significantly lower in Canada than in the UK, and N-ethylperfluoro-1-octanesulfonamide (EtFOSA) was significantly higher in Australia than in the UK. High EtFOSA concentrations in some samples may be consistent with its use as an insecticide. Perfluorooctane sulfonate (PFOS), perfluorooctanoic acid (PFOA), PFHxS, and MeFOSE were significantly higher in classrooms than in cars, homes, and offices; N-methylperfluoro-1-octanesulfonamide (MeFOSA) was significantly lower in classrooms than in homes and offices, and perfluoro-1-octanesulfonamide (FOSA) was significantly lower in classrooms than in cars, homes, and offices. While homes are usually the most important vector of dust exposure (typically > 60%), offices and classrooms make important contributions. While diet is usually the main exposure pathway for UK adults and children (~1-6 years) for PFOS, PFOA, and PFHxS; dust ingestion can be significant under high dust ingestion scenarios. Even under high-end exposure scenarios for dust and diet, PFOS and PFOA exposures are well within the European Food Safety Authority tolerable daily intakes.

  20. Occurrence of perfluoroalkyl carboxylates and sulfonates in drinking water utilities and related waters from the United States.

    PubMed

    Quiñones, Oscar; Snyder, Shane A

    2009-12-15

    The prevalence and persistence of perfluoroalkyl compounds (PFCs) in environmental and biological systems has been well documented, and a rising number of reports suggest that certain PFCs can result in adverse health effects in mammals. As traditional water sources become increasingly impacted by waste discharge and the demand for planned potable reuse grows, there is recent interest in determining PFC occurrence in drinking water supplies. Here we report monitoring results from drinking water treatment facility samples collected across the United States, and from associated surface, ground, and wastewater sources. Using automated solid phase extraction (SPE) and isotope-dilution liquid chromatography/tandem mass spectrometry (LC/MS-MS), samples were screened for perfluorohexanoic acid (PFHxA), perfluorohexanesulfonate (PFHxS), perfluorooctanoic acid (PFOA), perfluorooctanesulfonate (PFOS), perfluorononanoic acid (PFNA) perfluorodecanoic acid (PFDA), perfluoroundecanoic acid (PFUdA), and perfluorododecanoic acid (PFDoA). Method reporting limits (MRLs) were established at 1.0 ng/L for all monitored PFCs except PFOA, for which the MRL was set at 5.0 ng/L given elevated procedural and instrumental background levels. PFOS was the only investigated PFC detected in minimally impacted surface waters, with individual site averages of 2.0 ng/L and lower. Conversely, wastewater treatment plant (WWTP) effluents and other highly impacted waters had almost 100% detection frequency for all PFCs except PFUdA and PFDoA, which were not detected above MRL in any samples. Of the investigated PFCs, PFOA averaged the highest overall concentration at any site at 115 ng/L. Substantial impacts from treated wastewater generally caused increased summed PFC concentrations at downstream drinking water facilities, although levels and distribution suggest geographical variability. No discernible differences between influent and effluent PFC levels were observed for drinking water facilities

  1. Perfluoroalkyl carboxylic acids with up to 22 carbon atoms in snow and soil samples from a ski area.

    PubMed

    Plassmann, Merle M; Berger, Urs

    2013-05-01

    The use of fluorinated ski waxes as a direct input route of perfluoroalkyl carboxylic acids (PFCAs) to the environment was investigated. PFCA homologues with 6-22 carbon atoms (C6-22 PFCAs) were detected in fluorinated ski waxes and their raw materials by liquid chromatography coupled to tandem mass spectrometry. Snow and soil samples from a ski area in Sweden were taken after a skiing competition and after snowmelt, respectively. In both snow and soil samples C6-22 PFCAs were detected, representing the first report of PFCAs with up to 22 carbon atoms in environmental samples. Single analyte concentrations in snow (analyzed as melt water) and soil ranged up to 0.8μgL(-1) and 5ngg(-1) dry weight, respectively. ∑PFCA concentrations in snow and soil decreased from the start to the finish of the ski trail. Distinct differences in PFCA patterns between snow (prevalence of C14-20 PFCAs) and soil samples (C6-14 PFCAs dominating) were observed. Additionally, a PFCA pattern change from the start to about two third of the distance of the ski trail was found both for snow and soil, with a larger fraction of longer chain homologues present in samples from the start. These observations are probably a result of differences in PFCA homologue patterns present in different types of waxes. The calculated PFCA input from snow affected by the skiing competition was smaller than the PFCA inventory in soil for all chain lengths and markedly smaller for C6-15 PFCAs, presenting evidence for long-term accumulation in soil.

  2. Occurrence and distribution of perfluoroalkyl substances (PFASs) in surface water and bottom water of the Shuangtaizi Estuary, China.

    PubMed

    Shao, Mihua; Ding, Guanghui; Zhang, Jing; Wei, Lie; Xue, Huanhuan; Zhang, Nannan; Li, Yang; Chen, Guanqun; Sun, Yeqing

    2016-09-01

    Perfluoroalkyl substances (PFASs) have been recognized as emerging environmental pollutants. However, there is limited information on the contamination level and spatial distribution of PFASs in the Shuangtaizi Estuary, where the Shuangtaizi Hekou Nature Reserve is located. In the present study, the contamination level and spatial distribution of PFASs in surface water (approximately 0.5 m below the surface) and bottom water (about 0.5 m above the bottom) of the Shuangtaizi Estuary were investigated. The data indicated that the Shuangtaizi Estuary was commonly contaminated by PFASs. The total concentration of PFASs in surface and bottom water of the Shuangtaizi Estuary ranged from 66.2 to 185 ng L(-1) and from 44.8 to 209 ng L(-1), respectively. The predominant PFASs were perfluorobutanoic acid (PFBA), perfluoropentanoic acid, perfluorooctanoic acid, perfluorohexanoic acid and perfluorobutane sulfonate (PFBS). In general, PFAS concentrations in surface water samples were lower than those in bottom water samples. The spatial distribution of PFASs in the Shuangtaizi Estuary was mainly affected by particular landform, tide and residual currents in Liaodong Bay. The total mass flux of 15 PFASs from the Shuangtaizi River to Liaodong Bay was estimated to be 352 kg year(-1), which was lower than the total flux from the Daling River and the Daliao River. As short-chain PFASs, such as PFBS and PFBA, have been the prevalent compounds in some places and are continuously produced and used, long-term monitoring and effective pollution controls are suggested. PMID:27344086

  3. Congener-specific organic carbon-normalized soil and sediment-water partitioning coefficients for the C1 through C8 perfluoroalkyl carboxylic and sulfonic acids.

    PubMed

    Rayne, Sierra; Forest, Kaya

    2009-11-01

    Organic carbon-normalized soil and sediment-water partitioning coefficients (K(oc)) were estimated for all C(1) through C(8) perfluoroalkyl carboxylic (PFCA) and sulfonic (PFSA) acid congeners. The limited experimental K(oc) data set for the straight chain C(7) through C(10) PFCAs and C(8) and C(10) PFSAs was correlated to SPARC and ALOGPS computationally estimated octanol-water partitioning/distribution constants and used to predict K(oc) values for both branched and linear C(1) through C(8) isomers. Branched and linear congeners in this homologue range are generally expected to have K(oc) values > 1, leading to their accumulation in organic matter on sediments and soils, retardation during ground and pore water flow, and the preferential association with dissolved organic matter in aquatic systems. Both increasing perfluoroalkyl chain length and linearity increase K(oc) values with substantial intra- and inter-homologue variation and interhomologue mixing. Variability in K(oc) values among the PFCA and PFSA congeners will likely lead to an enrichment of more linear and longer-chain isomers in organic matter fractions, resulting in aqueous phases fractionated towards shorter-chain branched congeners. The expected magnitude of fractionation will require inclusion in source apportionment models and risk assessments. A comparison of representative established quantitative structure property relationships for estimating K(oc) values from octanol-water partitioning constants suggests that these equilibrium partitioning frameworks may be applicable towards modeling PFCA and PFSA environmental fate processes. PMID:20183495

  4. Perfluoroalkyl Acids (PFAAs) and Selected Precursors in the Baltic Sea Environment: Do Precursors Play a Role in Food Web Accumulation of PFAAs?

    PubMed

    Gebbink, Wouter A; Bignert, Anders; Berger, Urs

    2016-06-21

    The present study examined the presence of perfluoroalkyl acids (PFAAs) and selected precursors in the Baltic Sea abiotic environment and guillemot food web, and investigated the relative importance of precursors in food web accumulation of PFAAs. Sediment, water, zooplankton, herring, sprat, and guillemot eggs were analyzed for perfluoroalkane sulfonic acids (PFSAs; C4,6,8,10) and perfluoroalkyl carboxylic acids (PFCAs; C6-15) along with six perfluoro-octane sulfonic acid (PFOS) precursors and 11 polyfluoroalkyl phosphoric acid diesters (diPAPs). FOSA, FOSAA and its methyl and ethyl derivatives (Me- and EtFOSAA), and 6:2/6:2 diPAP were detected in sediment and water. While FOSA and the three FOSAAs were detected in all biota, a total of nine diPAPs were only detected in zooplankton. Concentrations of PFOS precursors and diPAPs exceeded PFOS and PFCA concentrations, respectively, in zooplankton, but not in fish and guillemot eggs. Although PFOS precursors were present at all trophic levels, they appear to play a minor role in food web accumulation of PFOS based on PFOS precursor/PFOS ratios and PFOS and FOSA isomer patterns. The PFCA pattern in fish could not be explained by the intake pattern based on PFCAs and analyzed precursors, that is, diPAPs. Exposure to additional precursors might therefore be a dominant exposure pathway compared to direct PFCA exposure for fish.

  5. High levels of perfluoroalkyl acids in eggs and embryo livers of great cormorant (Phalacrocorax carbo sinensis) and herring gull (Larus argentatus) from Lake Vänern, Sweden.

    PubMed

    Nordén, Marcus; Berger, Urs; Engwall, Magnus

    2013-11-01

    In the eggs and developing chick livers in the two wild bird species, great cormorant and herring gull, the concentrations of a range of 15 perfluoroalkyl acids (PFAAs) were determined. Eggs of the two species were collected from Lake Vänern, Sweden, and analysed either as undeveloped egg (whole egg or separated into yolk and albumen) or incubated until start of the hatching process when the chick liver was removed and analysed. High levels of PFAAs were found in all matrixes except albumen. The predominant PFAA was perfluorooctane sulfonate (PFOS), which was found in the μg/g wet weight (ww) range in some samples of cormorant whole egg, yolk and liver and herring gull egg yolk and liver. The average concentration in yolk was 1,506 ng/g ww in cormorant and 589 ng/g ww in herring gull. The average liver concentrations of PFOS were 583 ng/g ww in cormorant and 508 ng/g ww in herring gull. At these concentrations, biochemical effects in the developing embryo or effects on embryo survival cannot be ruled out. For perfluoroalkyl carboxylates (PFCAs), the liver/egg and liver/yolk concentration ratios increased with PFCA chain length in cormorant but not in herring gull, indicating that chain length could possibly affect egg-to-liver transfer of PFCAs and that species differences may exist.

  6. Perfluoroalkyl Acids (PFAAs) and Selected Precursors in the Baltic Sea Environment: Do Precursors Play a Role in Food Web Accumulation of PFAAs?

    PubMed

    Gebbink, Wouter A; Bignert, Anders; Berger, Urs

    2016-06-21

    The present study examined the presence of perfluoroalkyl acids (PFAAs) and selected precursors in the Baltic Sea abiotic environment and guillemot food web, and investigated the relative importance of precursors in food web accumulation of PFAAs. Sediment, water, zooplankton, herring, sprat, and guillemot eggs were analyzed for perfluoroalkane sulfonic acids (PFSAs; C4,6,8,10) and perfluoroalkyl carboxylic acids (PFCAs; C6-15) along with six perfluoro-octane sulfonic acid (PFOS) precursors and 11 polyfluoroalkyl phosphoric acid diesters (diPAPs). FOSA, FOSAA and its methyl and ethyl derivatives (Me- and EtFOSAA), and 6:2/6:2 diPAP were detected in sediment and water. While FOSA and the three FOSAAs were detected in all biota, a total of nine diPAPs were only detected in zooplankton. Concentrations of PFOS precursors and diPAPs exceeded PFOS and PFCA concentrations, respectively, in zooplankton, but not in fish and guillemot eggs. Although PFOS precursors were present at all trophic levels, they appear to play a minor role in food web accumulation of PFOS based on PFOS precursor/PFOS ratios and PFOS and FOSA isomer patterns. The PFCA pattern in fish could not be explained by the intake pattern based on PFCAs and analyzed precursors, that is, diPAPs. Exposure to additional precursors might therefore be a dominant exposure pathway compared to direct PFCA exposure for fish. PMID:27192404

  7. High levels of perfluoroalkyl acids in eggs and embryo livers of great cormorant (Phalacrocorax carbo sinensis) and herring gull (Larus argentatus) from Lake Vänern, Sweden.

    PubMed

    Nordén, Marcus; Berger, Urs; Engwall, Magnus

    2013-11-01

    In the eggs and developing chick livers in the two wild bird species, great cormorant and herring gull, the concentrations of a range of 15 perfluoroalkyl acids (PFAAs) were determined. Eggs of the two species were collected from Lake Vänern, Sweden, and analysed either as undeveloped egg (whole egg or separated into yolk and albumen) or incubated until start of the hatching process when the chick liver was removed and analysed. High levels of PFAAs were found in all matrixes except albumen. The predominant PFAA was perfluorooctane sulfonate (PFOS), which was found in the μg/g wet weight (ww) range in some samples of cormorant whole egg, yolk and liver and herring gull egg yolk and liver. The average concentration in yolk was 1,506 ng/g ww in cormorant and 589 ng/g ww in herring gull. The average liver concentrations of PFOS were 583 ng/g ww in cormorant and 508 ng/g ww in herring gull. At these concentrations, biochemical effects in the developing embryo or effects on embryo survival cannot be ruled out. For perfluoroalkyl carboxylates (PFCAs), the liver/egg and liver/yolk concentration ratios increased with PFCA chain length in cormorant but not in herring gull, indicating that chain length could possibly affect egg-to-liver transfer of PFCAs and that species differences may exist. PMID:23463275

  8. Occurrence and distribution of perfluoroalkyl acids (PFAAs) in surface water and sediment of a tropical coastal area (Bay of Bengal coast, Bangladesh).

    PubMed

    Habibullah-Al-Mamun, Md; Ahmed, Md Kawser; Raknuzzaman, Mohammad; Islam, Md Saiful; Negishi, Junya; Nakamichi, Shihori; Sekine, Makoto; Tokumura, Masahiro; Masunaga, Shigeki

    2016-11-15

    This study reports the first evidence of perfluoroalkyl acids (PFAAs) in surface waters and sediments collected from the coastal area of Bangladesh. Fifteen target PFAAs, including C4-14-PFCAs (perfluoroalkyl carboxylates) and C4, C6, C8, and C10-PFSAs (perfluoroalkyl sulfonates), were quantified by HPLC-MS/MS. The ΣPFAAs in surface water and sediment samples were in the range of 10.6 to 46.8ng/L and 1.07 to 8.15ng/gdw, respectively. PFOA in water (3.17-27.8ng/L) and PFOS in sediment samples (0.60-1.14ng/gdw) were found to be the most abundant PFAAs, and these concentrations were comparable to or less than most other reported values, particularly those recorded from the coastal areas of China, Japan, Korea and Spain. The majority of the monitored PFAAs did not show clear seasonal variation. The southeastern part (Cox's Bazar and Chittagong) of the Bangladeshi coastal area was more contaminated with PFAAs than the southern (Meghna Estuary) and southwestern parts (Sundarbans). Industrial and municipal wastewater effluents, ship breaking and port activities were identified as potential sources of the PFAA contamination in this region. Field-based sediment water distribution coefficients (KD) were calculated and corrected for organic carbon content (KOC), which reduced the variability between samples. The values of log KD (1.63-2.88) and log KOC (4.02-5.16) were higher than previously reported values, which may indicate that the partitioning of PFAAs in a tropical coastal ecosystem is different from other ecosystems, such as temperate and sub-tropical regions. Although a preliminary environmental hazard assessment indicated that PFOA or PFOS levels do not currently exceed the acute safety thresholds, we should keep in mind that they are bioavailable and can accumulate in the food chain. Therefore, the ubiquity of PFAAs in the coastal area of Bangladesh warrants further studies characterizing their specific sources and the potential long-term risks they present to both

  9. Occurrence and distribution of perfluoroalkyl acids (PFAAs) in surface water and sediment of a tropical coastal area (Bay of Bengal coast, Bangladesh).

    PubMed

    Habibullah-Al-Mamun, Md; Ahmed, Md Kawser; Raknuzzaman, Mohammad; Islam, Md Saiful; Negishi, Junya; Nakamichi, Shihori; Sekine, Makoto; Tokumura, Masahiro; Masunaga, Shigeki

    2016-11-15

    This study reports the first evidence of perfluoroalkyl acids (PFAAs) in surface waters and sediments collected from the coastal area of Bangladesh. Fifteen target PFAAs, including C4-14-PFCAs (perfluoroalkyl carboxylates) and C4, C6, C8, and C10-PFSAs (perfluoroalkyl sulfonates), were quantified by HPLC-MS/MS. The ΣPFAAs in surface water and sediment samples were in the range of 10.6 to 46.8ng/L and 1.07 to 8.15ng/gdw, respectively. PFOA in water (3.17-27.8ng/L) and PFOS in sediment samples (0.60-1.14ng/gdw) were found to be the most abundant PFAAs, and these concentrations were comparable to or less than most other reported values, particularly those recorded from the coastal areas of China, Japan, Korea and Spain. The majority of the monitored PFAAs did not show clear seasonal variation. The southeastern part (Cox's Bazar and Chittagong) of the Bangladeshi coastal area was more contaminated with PFAAs than the southern (Meghna Estuary) and southwestern parts (Sundarbans). Industrial and municipal wastewater effluents, ship breaking and port activities were identified as potential sources of the PFAA contamination in this region. Field-based sediment water distribution coefficients (KD) were calculated and corrected for organic carbon content (KOC), which reduced the variability between samples. The values of log KD (1.63-2.88) and log KOC (4.02-5.16) were higher than previously reported values, which may indicate that the partitioning of PFAAs in a tropical coastal ecosystem is different from other ecosystems, such as temperate and sub-tropical regions. Although a preliminary environmental hazard assessment indicated that PFOA or PFOS levels do not currently exceed the acute safety thresholds, we should keep in mind that they are bioavailable and can accumulate in the food chain. Therefore, the ubiquity of PFAAs in the coastal area of Bangladesh warrants further studies characterizing their specific sources and the potential long-term risks they present to both

  10. Perfluoroalkyl substances in polar bear mother-cub pairs: a comparative study based on plasma levels from 1998 and 2008.

    PubMed

    Bytingsvik, Jenny; van Leeuwen, Stefan P J; Hamers, Timo; Swart, Kees; Aars, Jon; Lie, Elisabeth; Nilsen, Else Mari Espseth; Wiig, Oystein; Derocher, Andrew E; Jenssen, Bjørn M

    2012-11-15

    Perfluoroalkyl substances (PFASs) are protein-binding blood-accumulating contaminants that may have detrimental toxicological effects on the early phases of mammalian development. To enable an evaluation of the potential health risks of PFAS exposure for polar bears (Ursus maritimus), an exposure assessment was made by examining plasma levels of PFASs in polar bear mothers in relation to their suckling cubs-of-the-year (~4 months old). Samples were collected at Svalbard in 1998 and 2008, and we investigated the between-year differences in levels of PFASs. Seven perfluorinated carboxylic acids (∑₇PFCAs: PFHpA, PFOA, PFNA, PFDA, PFUnDA, PFDoDA, and PFTrDA) and two perfluorinated sulfonic acids (∑₂PFSAs: PFHxS and PFOS) were detected in the majority of the mothers and cubs from both years. In mothers and cubs, most PFCAs were detected in higher concentrations in 2008 than in 1998. On the contrary, levels of PFOS were lower in 2008 than in 1998, while levels of PFHxS did not differ between the two sampling years. PFOS was the dominating compound in mothers and cubs both in 1998 and in 2008. Concentration of PFHpA did not differ between mothers and cubs, while concentrations of PFOA, PFNA, PFDA, PFUnDA, PFDoDA, PFTrDA, PFHxS, and PFOS were higher in mothers than in their cubs. Except from PFHpA, all compounds correlated significantly between mothers and their cubs. The mean cub to mother ratios ranged from 0.15 for PFNA to 1.69 for PFHpA. On average (mean±standard error of mean), the levels of ∑₇PFCAs and ∑₂PFSAs in cubs were 0.24±0.01 and 0.22±0.01 times the levels in their mothers, respectively. Although maternal transfer appears to be a substantial source of exposure for the cubs, the low cub to mother ratios indicate that maternal transfer of PFASs in polar bears is relatively low in comparison with hydrophobic contaminants (e.g. PCBs). Because the level of several PFASs in mothers and cubs from both sampling years exceeded the levels associated

  11. Assessing the relationship between perfluoroalkyl substances, thyroid hormones and binding proteins in pregnant women; a longitudinal mixed effects approach.

    PubMed

    Berg, Vivian; Nøst, Therese Haugdahl; Hansen, Solrunn; Elverland, Astrid; Veyhe, Anna-Sofía; Jorde, Rolf; Odland, Jon Øyvind; Sandanger, Torkjel Manning

    2015-04-01

    The mechanisms involved in thyroid homeostasis are complex, and perfluoroalkyl substances (PFASs) have been indicated to interfere at several levels in this endocrine system. Disruption of the maternal thyroid homeostasis during early pregnancy is of particular concern, where subclinical changes in maternal thyroid hormones (THs) may affect embryonic and foetal development. The present study investigated associations between THs, thyroid binding proteins (TH-BPs) and PFAS concentrations in pregnant women from Northern Norway. Women participating in The Northern Norway Mother-and-Child contaminant Cohort Study (MISA) donated a blood sample at three visits related to their pregnancy and postpartum period (during the second trimester, 3 days and 6 weeks after delivery) in the period 2007-2009. Participants were assigned to quartiles according to PFAS concentrations during the second trimester and mixed effects linear models were used to investigate potential associations between PFASs and repeated measurements of THs, TH-BPs, thyroxin binding capacity and thyroid peroxidase antibodies (anti-TPOs). Women within the highest perfluorooctane sulfonate (PFOS) quartile had 24% higher mean concentrations of thyroid stimulating hormone (TSH) compared to the first quartile at all sampling points. Women within the highest quartiles of perfluorodecanoate (PFDA) had 4% lower mean concentrations of triiodothyronine (T3) and women within the highest quartile of perfluoroundecanoate (PFUnDA) had 3% lower mean concentrations of free triiodothyronine (FT3). Further, the difference in concentrations and the changes between three time points were the same for the PFAS quartiles. Thyroxin binding capacity was associated with all the THs and TH-BPs, and was selected as a holistic adjustment for individual changes in TH homeostasis during pregnancy. Finally, adjusting for maternal iodine status did not influence the model predictions. Findings in the present study suggest modifications of

  12. Perfluoroalkyl substances in polar bear mother-cub pairs: a comparative study based on plasma levels from 1998 and 2008.

    PubMed

    Bytingsvik, Jenny; van Leeuwen, Stefan P J; Hamers, Timo; Swart, Kees; Aars, Jon; Lie, Elisabeth; Nilsen, Else Mari Espseth; Wiig, Oystein; Derocher, Andrew E; Jenssen, Bjørn M

    2012-11-15

    Perfluoroalkyl substances (PFASs) are protein-binding blood-accumulating contaminants that may have detrimental toxicological effects on the early phases of mammalian development. To enable an evaluation of the potential health risks of PFAS exposure for polar bears (Ursus maritimus), an exposure assessment was made by examining plasma levels of PFASs in polar bear mothers in relation to their suckling cubs-of-the-year (~4 months old). Samples were collected at Svalbard in 1998 and 2008, and we investigated the between-year differences in levels of PFASs. Seven perfluorinated carboxylic acids (∑₇PFCAs: PFHpA, PFOA, PFNA, PFDA, PFUnDA, PFDoDA, and PFTrDA) and two perfluorinated sulfonic acids (∑₂PFSAs: PFHxS and PFOS) were detected in the majority of the mothers and cubs from both years. In mothers and cubs, most PFCAs were detected in higher concentrations in 2008 than in 1998. On the contrary, levels of PFOS were lower in 2008 than in 1998, while levels of PFHxS did not differ between the two sampling years. PFOS was the dominating compound in mothers and cubs both in 1998 and in 2008. Concentration of PFHpA did not differ between mothers and cubs, while concentrations of PFOA, PFNA, PFDA, PFUnDA, PFDoDA, PFTrDA, PFHxS, and PFOS were higher in mothers than in their cubs. Except from PFHpA, all compounds correlated significantly between mothers and their cubs. The mean cub to mother ratios ranged from 0.15 for PFNA to 1.69 for PFHpA. On average (mean±standard error of mean), the levels of ∑₇PFCAs and ∑₂PFSAs in cubs were 0.24±0.01 and 0.22±0.01 times the levels in their mothers, respectively. Although maternal transfer appears to be a substantial source of exposure for the cubs, the low cub to mother ratios indicate that maternal transfer of PFASs in polar bears is relatively low in comparison with hydrophobic contaminants (e.g. PCBs). Because the level of several PFASs in mothers and cubs from both sampling years exceeded the levels associated

  13. Serum bactericidal test.

    PubMed Central

    Stratton, C W

    1988-01-01

    The serum bactericidal test represents one of the few in vitro tests performed in the clinical microbiology laboratory that combines the interaction of the pathogen, the antimicrobial agent, and the patient. Although the use of such a test antedates the antimicrobial era, its performance, results, and interpretation have been subject to question and controversy. Much of the confusion concerning the serum bactericidal test can be avoided by an understanding of the various factors which influence bactericidal testing. In addition, the methodologic aspects of the serum bactericidal test have recently been addressed and should place this test on firmer ground. New information on the clinical utility of this test is becoming available; additional data are needed to establish more clearly the usefulness of the serum bactericidal test in specific infections. Such clinical trials from multiple centers will enable firmer recommendations for the future use of the serum bactericidal test. PMID:3060242

  14. Occurrence and distribution of brominated flame retardants and perfluoroalkyl substances in Australian landfill leachate and biosolids.

    PubMed

    Gallen, C; Drage, D; Kaserzon, S; Baduel, C; Gallen, M; Banks, A; Broomhall, S; Mueller, J F

    2016-07-15

    The levels of perfluroalkyl substances (PFASs), polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCDDs) were studied in Australian landfill leachate and biosolids. Leachate was collected from 13 landfill sites and biosolids were collected from 16 wastewater treatment plants (WWTPs), across Australia. Perfluorohexanoate (PFHxA) (12-5700ng/L) was the most abundant investigated persistent, bioaccumulative and toxic (PBT) chemical in leachate. With one exception, mean concentrations of PFASs were higher in leachate of operating landfills compared to closed landfills. Polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane isomers (HBCDDs) were detected typically at operating landfills in comparatively lower concentrations than the PFASs. Decabromodiphenyl ether (BDE-209) (<0.4-2300ng/g) and perfluoroctanesulfonate (PFOS) (

  15. Oxadiazolyl-pyridines and perfluoroalkyl-carboxylic acids as building blocks for protic ionic liquids: crossing the thin line between ionic and hydrogen bonded materials.

    PubMed

    Pibiri, I; Pace, A; Buscemi, S; Causin, V; Rastrelli, F; Saielli, G

    2012-11-01

    A series of 18 samples has been prepared in order to obtain fluorinated materials as Protic Ionic Liquids (PILs). These were synthesized by appropriately mixing 1,2,4-oxadiazoles derivatised with two pyridines, or one pyridine and a fluorinated chain, and perfluoroalkyl-carboxylic acids, either mono- or dicarboxylic, leading to symmetric and non-symmetric materials. Many of them showed low melting points. However, the possibility of classifying the synthesized materials as PILs is discussed in terms of effective ionicity of the systems by the combination of Density Functional Theory (DFT) calculation and IR spectroscopy. The important outcome of our investigation is that the complete proton transfer reaction cannot be taken for granted. The thermal behaviour of the new fluorinated materials was also studied by Differential Scanning Calorimetry (DSC) and Thermogravimetric analysis (TGA).

  16. Nickel-Catalyzed Alkyl–Alkyl Cross-Couplings of Fluorinated Secondary Electrophiles: A General Approach to the Synthesis of Compounds that Bear a Perfluoroalkyl Substituent**

    PubMed Central

    Liang, Yufan

    2015-01-01

    Fluorinated organic molecules are of interest in fields ranging from medicinal chemistry to polymer science. Herein, we describe a mild, convenient, and versatile method for the synthesis of compounds that bear a perfluoroalkyl group attached to a tertiary carbon, via an alkyl–alkyl cross-coupling. Thus, a nickel catalyst derived from commercially available components (NiCl2·glyme and a pybox ligand) achieves the coupling of a wide range of fluorinated alkyl halides with alkylzinc reagents at room temperature. A broad array of functional groups (e.g., alkyne, aryl iodide, carbamate, furan, ketone, nitrile, phosphonate, primary alkyl bromide, and primary alkyl tosylate) are compatible with the reaction conditions, and highly selective couplings can be achieved on the basis of differing levels of fluorination. A mechanistic investigation has established that the presence of TEMPO inhibits cross-coupling under these conditions and that a TEMPO–electrophile adduct can be isolated. PMID:26073669

  17. Risk assessment and source identification of perfluoroalkyl acids in surface and ground water: Spatial distribution around a mega-fluorochemical industrial park, China.

    PubMed

    Liu, Zhaoyang; Lu, Yonglong; Wang, Tieyu; Wang, Pei; Li, Qifeng; Johnson, Andrew C; Sarvajayakesavalu, Suriyanarayanan; Sweetman, Andrew J

    2016-05-01

    Perfluoroalkyl acids (PFAAs) can be released to water bodies during manufacturing and application of PFAA-containing products. In this study, the contamination pattern, attenuation dynamics, sources, pathways, and risk zoning of PFAAs in surface and ground water was examined within a 10km radius from a mega-fluorochemical industrial park (FIP). Among 12 detected PFAAs, perfluorooctanoic acid (PFOA) dominated, followed by shorter-chained perfluoroalkyl carboxylic acids (PFCAs). PFAA-containing waste was discharged from the FIP, with levels reaching 1.86mg/L in the nearby rivers flowing to the Bohai sea together with up to 273μg/L in the local groundwater in the catchment. These levels constitute a human health risks for PFOA and other shorter-chained PFCAs within this location. The concentrations of ∑PFAAs in surface water strongly correlated with the local groundwater. The dominant pollution pathways of PFAAs included (i) discharge into surface water then to groundwater through seepage, and (ii) atmospheric deposition from the FIP, followed by infiltration to groundwater. As the distance increased from the source, PFAAs levels in groundwater showed a sharp initial decrease followed by a gentle decline. The contamination signal from the FIP site on PFAAs in groundwater existed within a radius of 4km, and at least 3km from the polluted Dongzhulong River. The major controlling factor in PFAA attenuation processes was likely to be dilution together with dispersion and adsorption to aquifer solids. The relative abundance of PFOA (C8) declined while those of shorter-chained PFCAs (C4-C6) increased during surface water seepage and further dispersion in groundwater.

  18. Perfluoroalkyl substances in the blood of wild rats and mice from 47 prefectures in Japan: use of samples from nationwide specimen bank.

    PubMed

    Taniyasu, Sachi; Senthilkumar, Kurunthachalam; Yamazaki, Eriko; Yeung, Leo W Y; Guruge, Keerthi S; Kannan, Kurunthachalam; Yamashita, Nobuyoshi

    2013-07-01

    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. PMID:23494483

  19. Liquid chromatography mass spectrometry determination of perfluoroalkyl acids in environmental solid extracts after phospholipid removal and on-line turbulent flow chromatography purification.

    PubMed

    Mazzoni, M; Polesello, S; Rusconi, M; Valsecchi, S

    2016-07-01

    An on-line TFC (Turbulent Flow Chromatography) clean up procedures coupled with UHPLC-MS/MS (Ultra High Performance Liquid Chromatography Mass Spectrometry) multi-residue method was developed for the simultaneous determination of 8 perfluroalkyl carboxylic acids (PFCA, from 5 to 12 carbon atoms) and 3 perfluoroalkyl sulfonic acids (PFSA, from 4 to 8 carbon atoms) in environmental solid matrices. Fast sample preparation procedure was based on a sonication-assisted extraction with acetonitrile. Phospholipids in biological samples were fully removed by an off-line SPE purification before injection, using HybridSPE(®) Phospholipid Ultra cartridges. The development of the on-line TFC clean-up procedure regarded the choice of the stationary phase, the optimization of the mobile phase composition, flow rate and injected volume. The validation of the optimized method included the evaluation of matrix effects, accuracy and reproducibility. Signal suppression in the analysis of fortified extracts ranged from 1 to 60%, and this problem was overcome by using isotopic dilution. Since no certified reference materials were available for PFAS in these matrices, accuracy was evaluated by recoveries on spiked clam samples which were 98-133% for PFCAs and 40-60% for PFSAs. MLDs and MLQs ranged from 0.03 to 0.3ngg(-1) wet weight and from 0.1 to 0.9ngg(-1) wet weight respectively. Repeatability (intra-day precision) and reproducibility (inter-day precision) showed RSD from 3 to 13% and from 4 to 27% respectively. Validated on-line TFC/UHPLC-MS/MS method has been applied for the determination of perfluoroalkyl acids in different solid matrices (sediment, fish, bivalves and bird yolk). PMID:27237594

  20. [Cold sterilization of serums with peracetic acid].

    PubMed

    Sprössig, M; Wutzler, P; Schweizer, H; Mücke, H

    1976-01-01

    On the basis of broad antimicrobic effect including also bacterial spores, mycoplasmas and viruses, the peracetic acid suits to sterilize in cold. By means of the final 0,1 to 0.02% concentration of the peracetic acid acting for 30 min. up to 5 days, it succeeded in sterilizing the serum used to prepare culture medium for bacteria, mycoplasmas and tissue cultures. Growth controls shown at least as good results as were those in using filtered sera. Chemical sterilization by means of the peracetic acid leads to significant diminution of neutralization and complementfixation antibodies in serum. PMID:823257

  1. Is the fact of parenting couples cohabitation affecting the serum levels of persistent organohalogen pollutants?

    PubMed

    Góralczyk, Katarzyna; Struciński, Paweł; Wojtyniak, Bogdan; Rabczenko, Daniel; Lindh, Christian H; Jönsson, Bo A G; Toft, Gunnar; Lenters, Virissa; Czaja, Katarzyna; Hernik, Agnieszka; Bonde, Jens Peter; Pedersen, Henning S; Zvyezday, Valentyna; Ludwicki, Jan K

    2015-06-01

    Organohalogen compounds constitute one of the important groups of persistent organic pollutants (POPs). Among them, due to their long-term health effects, one should pay attention on organochlorine pesticides, polychlorinated biphenyls (PCBs) and perfluoroalkylated substances (PFASs). This paper is an attempt to answer the question about relation between the fact of cohabitation by couples expecting a child and the level of the organohalogen compounds in the blood serum of both parents. The study was done on a population of parent couples from Greenland, Poland and Ukraine, from whom blood samples were collected in order to establish the levels of marker organohalogen compounds. We selected, as the representative of these compounds, the most persistent metabolite of DDT, i.e. p,p'-DDE, the most frequently detected PCB congener - CB-153, and PFOS and PFOA as the representatives of PFASs. The results show that in case of all compounds under study the highest concentrations were present always in men in relation to the levels detected in the blood serum of their female partners, regardless of the country of origin of the couple. A positive correlation was noted between the concentrations of the studied compounds in the blood serum of men and women in parenting couples. In some cases these correlations were statistically significant, e.g. for concentrations of p,p'-DDE in pairs from Greenland and Ukraine, of CB-153 in pairs from Poland and Ukraine, and of PFOS for parents from Greenland and Poland, while for PFOA - only for couples from Greenland. The concentrations of the compounds included in the study were similar to the levels found in general population in other countries. Our results show that the exposure to POPs resulting from cohabitation plays a role in the general exposure to these compounds.

  2. Temporal trends of perfluoroalkyl substances (PFAS) in eggs of coastal and offshore birds: Increasing PFAS levels associated with offshore bird species breeding on the Pacific coast of Canada and wintering near Asia.

    PubMed

    Miller, Aroha; Elliott, John E; Elliott, Kyle H; Lee, Sandi; Cyr, Francois

    2015-08-01

    Perfluoroalkyl substances (PFAS) such as perfluoroalkyl carboxylates (PFCAs) and perfluoroalkyl sulfonates (PFSAs) have become virtually ubiquitous throughout the environment, and, based on laboratory studies, have known toxicological consequences. Various national and international voluntary phase-outs and restrictions on these compounds have been implemented over the last 10 to 15 years. In the present study, we examine trends (1990/1991-2010/2011) in aquatic birds (ancient murrelet, Synthliboramphus antiquus [2009 only]; Leach's storm-petrels, Oceanodroma leucorhoa; rhinoceros auklets, Cerorhinca monocerata; double-crested cormorants, Phalacrocorax auritus; and great blue herons, Ardea herodias). The PFCA, PFSA, and stable isotope (δ(15) N and δ(13) C) data collected from these species from the Pacific coast of Canada, ranging over 20 to 30 years, were used to investigate temporal changes in PFAS coupled to dietary changes. Perfluorooctane sulfonic acid (PFOS), the dominant PFSA compound in all 4 species, increased and subsequently decreased in auklet and cormorant eggs in line with the manufacturing phase-out of PFOS and perfluorooctanoic acid (PFOA), but concentrations continuously increased in petrel eggs and remained largely unchanged in heron eggs. Dominant PFCA compounds varied between the offshore and coastal species, with increases seen in the offshore species and little or variable changes seen in the coastal species. Little temporal change was seen in stable isotope values, indicating that diet alone is not driving observed PFAS concentrations. PMID:25989421

  3. Temporal trends of perfluoroalkyl substances (PFAS) in eggs of coastal and offshore birds: Increasing PFAS levels associated with offshore bird species breeding on the Pacific coast of Canada and wintering near Asia.

    PubMed

    Miller, Aroha; Elliott, John E; Elliott, Kyle H; Lee, Sandi; Cyr, Francois

    2015-08-01

    Perfluoroalkyl substances (PFAS) such as perfluoroalkyl carboxylates (PFCAs) and perfluoroalkyl sulfonates (PFSAs) have become virtually ubiquitous throughout the environment, and, based on laboratory studies, have known toxicological consequences. Various national and international voluntary phase-outs and restrictions on these compounds have been implemented over the last 10 to 15 years. In the present study, we examine trends (1990/1991-2010/2011) in aquatic birds (ancient murrelet, Synthliboramphus antiquus [2009 only]; Leach's storm-petrels, Oceanodroma leucorhoa; rhinoceros auklets, Cerorhinca monocerata; double-crested cormorants, Phalacrocorax auritus; and great blue herons, Ardea herodias). The PFCA, PFSA, and stable isotope (δ(15) N and δ(13) C) data collected from these species from the Pacific coast of Canada, ranging over 20 to 30 years, were used to investigate temporal changes in PFAS coupled to dietary changes. Perfluorooctane sulfonic acid (PFOS), the dominant PFSA compound in all 4 species, increased and subsequently decreased in auklet and cormorant eggs in line with the manufacturing phase-out of PFOS and perfluorooctanoic acid (PFOA), but concentrations continuously increased in petrel eggs and remained largely unchanged in heron eggs. Dominant PFCA compounds varied between the offshore and coastal species, with increases seen in the offshore species and little or variable changes seen in the coastal species. Little temporal change was seen in stable isotope values, indicating that diet alone is not driving observed PFAS concentrations.

  4. Serum globulin electrophoresis

    MedlinePlus

    ... may indicate: Acute infection Bone marrow cancer called multiple myeloma Chronic inflammatory disease (for example, rheumatoid arthritis and ... test Hemoglobin Hyperimmunization Immunoelectrophoresis - ... electrophoresis - serum Rheumatoid arthritis Systemic lupus erythematosus ...

  5. Serum free hemoglobin test

    MedlinePlus

    Blood hemoglobin; Serum hemoglobin ... Hemoglobin (Hb) is the main component of red blood cells. It is a protein that carries oxygen. ... people may contain up to 5 mg/dL hemoglobin. Normal value ranges may vary slightly among different ...

  6. Regulation of serum phosphate

    PubMed Central

    Lederer, Eleanor

    2014-01-01

    The regulation of serum phosphate, an acknowledged risk factor for chronic kidney disease and cardiovascular mortality, is poorly understood. The discovery of fibroblast growth factor 23 (FGF23) as a key regulator of renal phosphate handling and activation of vitamin D has revolutionized our comprehension of phosphate homeostasis. Through as yet undetermined mechanisms, circulating and dietary phosphate appear to have a direct effect on FGF23 release by bone cells that, in turn, causes renal phosphate excretion and decreases intestinal phosphate absorption through a decrease in vitamin D production. Thus, the two major phosphaturic hormones, PTH and FGF23, have opposing effects on vitamin D production, placing vitamin D at the nexus of phosphate homeostasis. While our understanding of phosphate homeostasis has advanced, the factors determining regulation of serum phosphate level remain enigmatic. Diet, time of day, season, gender, age and genetics have all been identified as significant contributors to serum phosphate level. The effects of these factors on serum phosphate have major implications for what is understood as ‘normal’ and for studies of phosphate homeostasis and metabolism. Moreover, other hormonal mediators such as dopamine, insulin-like growth factor, and angiotensin II also affect renal handling of phosphate. How the major hormone effects on phosphate handling are regulated and how the effect of these other factors are integrated to yield the measurable serum phosphate are only now beginning to be studied. PMID:24973411

  7. [The National Serum Bank].

    PubMed

    Magos-López, C; Sánchez-Villarreal, F; Gutiérrez, G; Tapia-Conyer, R

    1992-01-01

    A National Serum Bank was established to store sera obtained during the National Seroepidemiological Survey performed in Mexico in 1987. More than 70,000 serum samples were obtained from subjects of either sex 1-99 years of age in each of the 32 states of the country. The current collection of sera includes 28,704 male samples and 40,629 female samples. This paper describes the procedures for handling serum samples, including reception registry, storage and distribution to several laboratories for detection of measles, rubella, poliomyelitis, AIDS, diphtheria, pertussis, tetanus, brucella, salmonella, amoeba, toxoplasma, American trypanosomiasis and cysticercus. Determinations of total cholesterol were also made in order to describe its distribution and to identify the prevalence of hypercholesterolemia.

  8. Attention Deficit/Hyperactivity Disorder and Childhood Autism in Association with Prenatal Exposure to Perfluoroalkyl Substances: A Nested Case–Control Study in the Danish National Birth Cohort

    PubMed Central

    Liew, Zeyan; Ritz, Beate; von Ehrenstein, Ondine S.; Bech, Bodil Hammer; Nohr, Ellen Aagaard; Fei, Chunyuan; Bossi, Rossana; Henriksen, Tine Brink; Bonefeld-Jørgensen, Eva Cecilie

    2014-01-01

    Background: Perfluoroalkyl substances (PFASs) are persistent pollutants found to be endocrine disruptive and neurotoxic in animals. Positive correlations between PFASs and neurobehavioral problems in children were reported in cross-sectional data, but findings from prospective studies are limited. Objectives: We investigated whether prenatal exposure to PFASs is associated with attention deficit/hyperactivity disorder (ADHD) or childhood autism in children. Methods: Among 83,389 mother–child pairs enrolled in the Danish National Birth Cohort during 1996–2002, we identified 890 ADHD cases and 301 childhood autism cases from the Danish National Hospital Registry and the Danish Psychiatric Central Registry. From this cohort, we randomly selected 220 cases each of ADHD and autism, and we also randomly selected 550 controls frequency matched by child’s sex. Sixteen PFASs were measured in maternal plasma collected in early or mid-pregnancy. We calculated risk ratios (RRs) using generalized linear models, taking into account sampling weights. Results: Perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) were detected in all samples; four other PFASs were quantified in ≥ 90% of the samples. We did not find consistent evidence of associations between mother’s PFAS plasma levels and ADHD [per natural log nanograms per milliliter increase: PFOS RR = 0.87 (95% CI: 0.74, 1.02); PFOA RR = 0.98 (95% CI: 0.82, 1.16)] or autism [per natural log nanograms per milliliter increase: PFOS RR = 0.92 (95% CI: 0.69, 1.22); PFOA RR = 0.98 (95% CI: 0.73, 1.31)]. We found positive as well as negative associations between higher PFAS quartiles and ADHD in models that simultaneously adjusted for all PFASs, but these estimates were imprecise. Conclusions: In this study we found no consistent evidence to suggest that prenatal PFAS exposure increases the risk of ADHD or childhood autism in children. Citation: Liew Z, Ritz B, von Ehrenstein OS, Bech BH, Nohr EA, Fei CY

  9. Associations of Perfluoroalkyl Substances (PFAS) with Lower Birth Weight: An Evaluation of Potential Confounding by Glomerular Filtration Rate Using a Physiologically Based Pharmacokinetic Model (PBPK)

    PubMed Central

    Loccisano, Anne E.; Morken, Nils-Halvdan; Yoon, Miyoung; Wu, Huali; McDougall, Robin; Maisonet, Mildred; Marcus, Michele; Kishi, Reiko; Miyashita, Chihiro; Chen, Mei-Huei; Hsieh, Wu-Shiun; Andersen, Melvin E.; Clewell, Harvey J.; Longnecker, Matthew P.

    2015-01-01

    Background Prenatal exposure to perfluoroalkyl substances (PFAS) has been associated with lower birth weight in epidemiologic studies. This association could be attributable to glomerular filtration rate (GFR), which is related to PFAS concentration and birth weight. Objectives We used a physiologically based pharmacokinetic (PBPK) model of pregnancy to assess how much of the PFAS–birth weight association observed in epidemiologic studies might be attributable to GFR. Methods We modified a PBPK model to reflect the association of GFR with birth weight (estimated from three studies of GFR and birth weight) and used it to simulate PFAS concentrations in maternal and cord plasma. The model was run 250,000 times, with variation in parameters, to simulate a population. Simulated data were analyzed to evaluate the association between PFAS levels and birth weight due to GFR. We compared simulated estimates with those from a meta-analysis of epidemiologic data. Results The reduction in birth weight for each 1-ng/mL increase in simulated cord plasma for perfluorooctane sulfonate (PFOS) was 2.72 g (95% CI: –3.40, –2.04), and for perfluorooctanoic acid (PFOA) was 7.13 g (95% CI: –8.46, –5.80); results based on maternal plasma at term were similar. Results were sensitive to variations in PFAS level distributions and the strength of the GFR–birth weight association. In comparison, our meta-analysis of epidemiologic studies suggested that each 1-ng/mL increase in prenatal PFOS and PFOA levels was associated with 5.00 g (95% CI: –21.66, –7.78) and 14.72 g (95% CI: –8.92, –1.09) reductions in birth weight, respectively. Conclusion Results of our simulations suggest that a substantial proportion of the association between prenatal PFAS and birth weight may be attributable to confounding by GFR and that confounding by GFR may be more important in studies with sample collection later in pregnancy. Citation Verner MA, Loccisano AE, Morken NH, Yoon M, Wu H, Mc

  10. High-temperature and photochemical syntheses of C[subscript 60] and C[subscript 70] fullerene derivatives with linear perfluoroalkyl chains

    SciTech Connect

    Shustova, Natalia B.; Kareev, Ivan E.; Kuvychko, Igor V.; Whitaker, James B.; Lebedkin, Sergey F.; Popov, Alexey A.; Dunsch, Lothar; Chen, Yu-Sheng; Seppelt, Konrad; Strauss, Steven H.; Boltalina, Olga V.

    2012-04-30

    New experimental results on perfluoroalkylation of C{sub 60} and C{sub 70} with the use of R{sub f}I (R{sub f} = CF{sub 3}, C{sub 2}F{sub 5}, n-C{sub 3}F{sub 7}, n-C{sub 4}F{sub 9}, and n-C{sub 6}F{sub 13}), along with a critical overview of the existing synthetic methods, are presented. For the selected new fullerene (R{sub f}){sub n} compounds we report spectroscopic, electrochemical and structural data, including improved crystallographic data for the isomers of C{sub 70}(C{sub 2}F{sub 5}){sub 10} and C{sub 60}(C{sub 2}F{sub 5}){sub 10}, and the first X-ray structural data for the dodecasubstituted perfluoethylated C{sub 70} fullerene, C{sub 70}(C{sub 2}F{sub 5}){sub 12}, which possesses unprecedented addition pattern.

  11. Long-chain perfluoroalkyl carboxylic acids in Pacific cods from coastal areas in northern Japan: a major source of human dietary exposure.

    PubMed

    Fujii, Yukiko; Sakurada, Tsukasa; Harada, Kouji H; Koizumi, Akio; Kimura, Osamu; Endo, Tetsuya; Haraguchi, Koichi

    2015-04-01

    This study investigates perfluoroalkyl carboxylic acids (PFCAs) contamination of edible fish muscle from Japanese coastal waters. The concentrations of PFCAs with 8-14 carbon atoms (C8-C14) in Pacific cods in Hokkaido, Japan were 51 (median: pg/g-wet weight) for C8, 93 for C9, 99 for C10, 746 for C11, 416 for C12, 404 for C13, and 93 for C14. The levels of C9-C14 PFCAs in fish were strongly correlated to each other, but not to C8 and the other chlorinated persistent organic pollutants, indicating that C9-C14 PFCAs have a different emission source and/or bioaccumulation mechanism. The relative ratios between estimated PFCAs intake through fish consumption and the reported total dietary exposure of PFCAs were less than 1 for C8 to C9, but were more than 1 for C10 to C14. This result strongly suggests that fish consumption is a significant source of human dietary exposure to C10-C14 PFCAs.

  12. Orthogonal zirconium diol/C18 liquid chromatography-tandem mass spectrometry analysis of poly and perfluoroalkyl substances in landfill leachate.

    PubMed

    Allred, B McKay; Lang, Johnsie R; Barlaz, Morton A; Field, Jennifer A

    2014-09-12

    Leachates coming from landfills contain a myriad of compounds of potential environmental and human health concern, including per- and polyfluorinated alkyl substances (PFASs). Micro liquid-liquid extraction was combined with a 900μl large volume injection (LVI) for the analysis of 70 PFASs in landfill leachate by orthogonal LC-MS/MS. The LVI approach introduced 7 times more extract than conventional injection approaches. Two zirconium-modified diol guard columns effectively retained PFASs from the organic leachate extract and an analytical C18 column was used for separation. Method accuracy and precision for PFASs with analytical grade reference materials ranged from 81-120% and 5.5-33%, respectively. Estimated method detection limits in the low to sub-ng/L. Seven landfill leachates were analyzed by the optimized analytical method for the purposes of method demonstration. Leachates were characterized by a wide variety of PFASs, reporting on 36 previously-unanalyzed PFASs in leachate. Perfluoroalkyl carboxylates were the most abundant class detected while phosphorous-containing PFASs, present in all leachates, were at low concentrations. The 3-perfluoropentyl propanoate (5:3 FTCA) was the most concentrated analyte in most samples and constitutes a previously unreported but significant component of landfill leachate.

  13. Detection of Poly- and Perfluoroalkyl Substances (PFASs) in U.S. Drinking Water Linked to Industrial Sites, Military Fire Training Areas, and Wastewater Treatment Plants

    PubMed Central

    2016-01-01

    Drinking water contamination with poly- and perfluoroalkyl substances (PFASs) poses risks to the developmental, immune, metabolic, and endocrine health of consumers. We present a spatial analysis of 2013–2015 national drinking water PFAS concentrations from the U.S. Environmental Protection Agency’s (US EPA) third Unregulated Contaminant Monitoring Rule (UCMR3) program. The number of industrial sites that manufacture or use these compounds, the number of military fire training areas, and the number of wastewater treatment plants are all significant predictors of PFAS detection frequencies and concentrations in public water supplies. Among samples with detectable PFAS levels, each additional military site within a watershed’s eight-digit hydrologic unit is associated with a 20% increase in PFHxS, a 10% increase in both PFHpA and PFOA, and a 35% increase in PFOS. The number of civilian airports with personnel trained in the use of aqueous film-forming foams is significantly associated with the detection of PFASs above the minimal reporting level. We find drinking water supplies for 6 million U.S. residents exceed US EPA’s lifetime health advisory (70 ng/L) for PFOS and PFOA. Lower analytical reporting limits and additional sampling of smaller utilities serving <10000 individuals and private wells would greatly assist in further identifying PFAS contamination sources. PMID:27752509

  14. Estimation of the acid dissociation constant of perfluoroalkyl carboxylic acids through an experimental investigation of their water-to-air transport.

    PubMed

    Vierke, Lena; Berger, Urs; Cousins, Ian T

    2013-10-01

    The acid dissociation constants (pKas) of perfluoroalkyl carboxylic acids (PFCAs) have been the subject of discussion in the literature; for example, values from -0.2 to 3.8 have been suggested for perfluorooctanoic acid (PFOA). The dissociated anionic conjugate bases of PFCAs have negligible air-water partition coefficients (KAWs) and do not volatilize from water. The neutral acids, however, have relatively high KAWs and volatilization from water has been demonstrated. The extent of volatilization of PFCAs in the environment will depend on the water pH and their pKa. Knowledge of the pKas of PFCAs is therefore vital for understanding their environmental transport and fate. We investigated the water-to-air transfer of PFCAs in a novel experimental setup. We used ∼1 μg L(-1) of PFCAs in water (above environmental background concentrations but below the concentration at which self-association occurs) at different water pH (pH 0.3 to pH 6.9) and sampled the PFCAs volatilized from water during a 2-day experiment. Our results suggest that the pKas of C4-11 PFCAs are <1.6. For PFOA, we derived a pKa of 0.5 from fitting the experimental measurements with a volatilization model. Perfluoroalkane sulfonic acids were not volatilized, suggesting that their pKas are below the investigated pH range (pKa <0.3).

  15. Increasing concentrations of perfluoroalkyl acids in Scandinavian otters (Lutra lutra) between 1972 and 2011: a new threat to the otter population?

    PubMed

    Roos, Anna; Berger, Urs; Järnberg, Ulf; van Dijk, Jiska; Bignert, Anders

    2013-10-15

    Liver samples from 140 otters (Lutra lutra) from Sweden and Norway were analyzed for 10 perfluoroalkyl carboxylic acids (PFCAs; C6-C15), 4 perfluoroalkane sulfonic acids (PFSAs; C4,C6,C8,C10) and perfluorooctane sulfonamide (FOSA). Perfluorooctane sulfonic acid (PFOS) was the dominant compound accounting for approximately 80% of the fluorinated contaminants and showing concentrations up to 16 μg/g wet weight. Perfluorononanoic acid (PFNA) was the dominant PFCA (up to 640 ng/g wet weight) closely followed by the C10 and C11 homologues. A spatial comparison between otters from southwestern Norway, southern and northern Sweden sampled between 2005 and 2011 revealed that the samples from southern Sweden had generally the largest contaminant load, but two PFCAs and FOSA were higher concentrated in the Norwegian samples. A temporal trend study was performed on otters from southern Sweden collected between 1972 and 2011. Seven PFCAs (C8-C14), PFOS and perfluorodecane sulfonic acid (PFDS) showed significantly increasing trends with doubling times between 5.5 and 13 years. The PFCAs also showed significantly increasing trends over the period 2002 to 2011. These findings together with the exceptionally high liver concentrations of PFOS are of great concern for the Scandinavian otter populations.

  16. Are perfluoroalkyl acids in waste water treatment plant effluents the result of primary emissions from the technosphere or of environmental recirculation?

    PubMed

    Filipovic, Marko; Berger, Urs

    2015-06-01

    Wastewater treatment plants (WWTP) have been suggested to be one of the major pathways of perfluoroalkyl acids (PFAAs) from the technosphere to the aquatic environment. The origin of PFAAs in WWTP influents is either from current primary emissions or a result of recirculation of PFAAs that have been residing and transported in the environment for several years or decades. Environmental recirculation can then occur when PFAAs from the environment enter the wastewater stream in, e.g., tap water. In this study 13 PFAAs and perfluorooctane sulfonamide were analyzed in tap water as well as WWTP influent, effluent and sludge from three Swedish cities: Bromma (in the metropolitan area of Stockholm), Bollebygd and Umeå. A mass balance of the WWTPs was assembled for each PFAA. Positive mass balances were observed for PFHxA and PFOA in all WWTPs, indicating the presence of precursor compounds in the technosphere. With regard to environmental recirculation, tap water was an important source of PFAAs to the Bromma WWTP influent, contributing >40% for each quantified sulfonic acid and up to 30% for the carboxylic acids. The PFAAs in tap water from Bollebygd and Umeå did not contribute significantly to the PFAA load in the WWTP influents. Our results show that in order to estimate current primary emissions from the technosphere, it may be necessary to correct the PFAA emission rates in WWTP effluents for PFAAs present in tap water, especially in the case of elevated levels in tap water.

  17. An On-Line Solid Phase Extraction-Liquid Chromatography-Tandem Mass Spectrometry Method for the Determination of Perfluoroalkyl Acids in Drinking and Surface Waters

    PubMed Central

    Mazzoni, Michela; Rusconi, Marianna; Valsecchi, Sara; Martins, Claudia P. B.; Polesello, Stefano

    2015-01-01

    An UHPLC-MS/MS multiresidue method based on an on-line solid phase extraction (SPE) procedure was developed for the simultaneous determination of 9 perfluorinated carboxylates (from 4 to 12 carbon atoms) and 3 perfluorinated sulphonates (from 4 to 8 carbon atoms). This work proposes using an on-line solid phase extraction before chromatographic separation and analysis to replace traditional methods of off-line SPE before direct injection to LC-MS/MS. Manual sample preparation was reduced to sample centrifugation and acidification, thus eliminating several procedural errors and significantly reducing time-consuming and costs. Ionization suppression between target perfluorinated analytes and their coeluting SIL-IS were detected for homologues with a number of carbon atoms less than 9, but the quantitation was not affected. Total matrix effect corrected by SIL-IS, inclusive of extraction efficacy, and of ionization efficiency, ranged between −34 and +39%. The percentage of recoveries, between 76 and 134%, calculated in different matrices (tap water and rivers impacted by different pollutions) was generally satisfactory. LODs and LOQs of this on-line SPE method, which also incorporate recovery losses, ranged from 0.2 to 5.0 ng/L and from 1 to 20 ng/L, respectively. Validated on-line SPE-LC/MS/MS method has been applied in a wide survey for the determination of perfluoroalkyl acids in Italian surface and ground waters. PMID:25834752

  18. Perfluoroalkyl Substances (PFASs) in Marine Mammals from the South China Sea and Their Temporal Changes 2002-2014: Concern for Alternatives of PFOS?

    PubMed

    Lam, James C W; Lyu, Jinling; Kwok, Karen Y; Lam, Paul K S

    2016-07-01

    Perfluorinated sulfonic acids (PFSAs) and perfluorinated carboxylic acids (PFCAs), as well as the replacement for the phase-out C8 PFSAs were determined in the liver samples of Indo-Pacific humpback dolphins (Sousa chinensis) and finless porpoises (Neophocaena phocaenoides) from the South China Sea between 2002 and 2014. Levels of total perfluoroalkyl substances (PFASs) in samples ranged from 136-15,300 and 30.5-2,720 ng/g dw for dolphin and porpoise, respectively. Significant increasing trends of several individual PFCAs and perfluorobutane sulfonate (PFBS) were found in cetacean samples from 2002 to 2014, whereas no significant temporal trends of ∑PFASs appeared over the sampling period. This pattern may be attributed to the increasing usage of PFCAs and C4-based PFSAs following the restriction/voluntary withdrawal of the production and use of perfluorooctane sulfonate (PFOS) related products. In addition, significantly increasing temporal shifting trends of PFOS to PFBS were observed in the dolphin liver samples. This pattern may be attributed to the substitution of PFOS by its alternative, PFBS. The highest levels of PFOS were observed in the liver samples of dolphin as compared with other marine mammal studies published since 2006, indicating high contamination of PFAS in the South China region. An assessment of relatively high concentrations of C8-based PFASs in the liver samples of cetaceans predicted that concentrations of PFOS would be expected to affect some proportion of the cetacean populations studied, based on the toxicity thresholds derived. PMID:26889942

  19. Perfluoroalkyl Substances (PFASs) in Marine Mammals from the South China Sea and Their Temporal Changes 2002-2014: Concern for Alternatives of PFOS?

    PubMed

    Lam, James C W; Lyu, Jinling; Kwok, Karen Y; Lam, Paul K S

    2016-07-01

    Perfluorinated sulfonic acids (PFSAs) and perfluorinated carboxylic acids (PFCAs), as well as the replacement for the phase-out C8 PFSAs were determined in the liver samples of Indo-Pacific humpback dolphins (Sousa chinensis) and finless porpoises (Neophocaena phocaenoides) from the South China Sea between 2002 and 2014. Levels of total perfluoroalkyl substances (PFASs) in samples ranged from 136-15,300 and 30.5-2,720 ng/g dw for dolphin and porpoise, respectively. Significant increasing trends of several individual PFCAs and perfluorobutane sulfonate (PFBS) were found in cetacean samples from 2002 to 2014, whereas no significant temporal trends of ∑PFASs appeared over the sampling period. This pattern may be attributed to the increasing usage of PFCAs and C4-based PFSAs following the restriction/voluntary withdrawal of the production and use of perfluorooctane sulfonate (PFOS) related products. In addition, significantly increasing temporal shifting trends of PFOS to PFBS were observed in the dolphin liver samples. This pattern may be attributed to the substitution of PFOS by its alternative, PFBS. The highest levels of PFOS were observed in the liver samples of dolphin as compared with other marine mammal studies published since 2006, indicating high contamination of PFAS in the South China region. An assessment of relatively high concentrations of C8-based PFASs in the liver samples of cetaceans predicted that concentrations of PFOS would be expected to affect some proportion of the cetacean populations studied, based on the toxicity thresholds derived.

  20. Serum Albumin Domain Structures in Human Blood Serum by Mass Spectrometry and Computational Biology*

    PubMed Central

    Belsom, Adam; Schneider, Michael; Fischer, Lutz; Brock, Oliver; Rappsilber, Juri

    2016-01-01

    Chemical cross-linking combined with mass spectrometry has proven useful for studying protein-protein interactions and protein structure, however the low density of cross-link data has so far precluded its use in determining structures de novo. Cross-linking density has been typically limited by the chemical selectivity of the standard cross-linking reagents that are commonly used for protein cross-linking. We have implemented the use of a heterobifunctional cross-linking reagent, sulfosuccinimidyl 4,4′-azipentanoate (sulfo-SDA), combining a traditional sulfo-N-hydroxysuccinimide (sulfo-NHS) ester and a UV photoactivatable diazirine group. This diazirine yields a highly reactive and promiscuous carbene species, the net result being a greatly increased number of cross-links compared with homobifunctional, NHS-based cross-linkers. We present a novel methodology that combines the use of this high density photo-cross-linking data with conformational space search to investigate the structure of human serum albumin domains, from purified samples, and in its native environment, human blood serum. Our approach is able to determine human serum albumin domain structures with good accuracy: root-mean-square deviation to crystal structure are 2.8/5.6/2.9 Å (purified samples) and 4.5/5.9/4.8Å (serum samples) for domains A/B/C for the first selected structure; 2.5/4.9/2.9 Å (purified samples) and 3.5/5.2/3.8 Å (serum samples) for the best out of top five selected structures. Our proof-of-concept study on human serum albumin demonstrates initial potential of our approach for determining the structures of more proteins in the complex biological contexts in which they function and which they may require for correct folding. Data are available via ProteomeXchange with identifier PXD001692. PMID:26385339

  1. Serum Albumin Domain Structures in Human Blood Serum by Mass Spectrometry and Computational Biology.

    PubMed

    Belsom, Adam; Schneider, Michael; Fischer, Lutz; Brock, Oliver; Rappsilber, Juri

    2016-03-01

    Chemical cross-linking combined with mass spectrometry has proven useful for studying protein-protein interactions and protein structure, however the low density of cross-link data has so far precluded its use in determining structures de novo. Cross-linking density has been typically limited by the chemical selectivity of the standard cross-linking reagents that are commonly used for protein cross-linking. We have implemented the use of a heterobifunctional cross-linking reagent, sulfosuccinimidyl 4,4'-azipentanoate (sulfo-SDA), combining a traditional sulfo-N-hydroxysuccinimide (sulfo-NHS) ester and a UV photoactivatable diazirine group. This diazirine yields a highly reactive and promiscuous carbene species, the net result being a greatly increased number of cross-links compared with homobifunctional, NHS-based cross-linkers. We present a novel methodology that combines the use of this high density photo-cross-linking data with conformational space search to investigate the structure of human serum albumin domains, from purified samples, and in its native environment, human blood serum. Our approach is able to determine human serum albumin domain structures with good accuracy: root-mean-square deviation to crystal structure are 2.8/5.6/2.9 Å (purified samples) and 4.5/5.9/4.8Å (serum samples) for domains A/B/C for the first selected structure; 2.5/4.9/2.9 Å (purified samples) and 3.5/5.2/3.8 Å (serum samples) for the best out of top five selected structures. Our proof-of-concept study on human serum albumin demonstrates initial potential of our approach for determining the structures of more proteins in the complex biological contexts in which they function and which they may require for correct folding. Data are available via ProteomeXchange with identifier PXD001692.

  2. The Human Serum Metabolome

    PubMed Central

    Psychogios, Nikolaos; Hau, David D.; Peng, Jun; Guo, An Chi; Mandal, Rupasri; Bouatra, Souhaila; Sinelnikov, Igor; Krishnamurthy, Ramanarayan; Eisner, Roman; Gautam, Bijaya; Young, Nelson; Xia, Jianguo; Knox, Craig; Dong, Edison; Huang, Paul; Hollander, Zsuzsanna; Pedersen, Theresa L.; Smith, Steven R.; Bamforth, Fiona; Greiner, Russ; McManus, Bruce; Newman, John W.; Goodfriend, Theodore; Wishart, David S.

    2011-01-01

    Continuing improvements in analytical technology along with an increased interest in performing comprehensive, quantitative metabolic profiling, is leading to increased interest pressures within the metabolomics community to develop centralized metabolite reference resources for certain clinically important biofluids, such as cerebrospinal fluid, urine and blood. As part of an ongoing effort to systematically characterize the human metabolome through the Human Metabolome Project, we have undertaken the task of characterizing the human serum metabolome. In doing so, we have combined targeted and non-targeted NMR, GC-MS and LC-MS methods with computer-aided literature mining to identify and quantify a comprehensive, if not absolutely complete, set of metabolites commonly detected and quantified (with today's technology) in the human serum metabolome. Our use of multiple metabolomics platforms and technologies allowed us to substantially enhance the level of metabolome coverage while critically assessing the relative strengths and weaknesses of these platforms or technologies. Tables containing the complete set of 4229 confirmed and highly probable human serum compounds, their concentrations, related literature references and links to their known disease associations are freely available at http://www.serummetabolome.ca. PMID:21359215

  3. Photoaffinity labeling of human serum vitamin D binding protein and chemical cleavage of the labeled protein: Identification of an 11. 5-kDa peptide containing the putative 25-hydroxyvitamin D sub 3 binding site

    SciTech Connect

    Ray, R.; Holick, M.F. ); Bouillon, R.; Baelen, H.V. )

    1991-07-30

    In this paper, the authors describe photoaffinity labeling and related studies of human serum vitamin D binding protein (hDBP) with 25-hydroxyvitamin D{sub 3} 3{beta}-3{prime}-(N-(4-azido-2-nitrophenyl)amino)propyl ether (25-ANE) and its radiolabeled counterpart, i.e., 25-hydroxyvitamin D{sub 3} 3{beta}-3{prime}-(N-(4-azido-2-nitro-(3,5-{sup 3}H)phenyl)amino)propyl ether ({sup 3}H-25-ANE). They have carried out studies to demonstrate that (1) 25-ANE competes with 25-OH-D{sub 3} for the binding site of the latter in hDBP and (2) {sup 3}H-25-ANE is capable of covalently labeling the hDBP molecule when exposed ot UV light. Treatment of a sample of purified hDBP, labeled with {sup 3}H-25-ANE, with BNPS-skatole produced two Coomassie Blue stained peptide fragments, and the majority of the radioactivity was assoicated with the smaller of the two peptide fragments (16.5 kDa). On the other hand, cleavage of the labeled protein with cyanogen bromide produced a peptide (11.5 kDa) containing most of the covalently attached radioactivity. Considering the primary amino acid structure of hDBP, this peptide fragment (11.5 kDa) represents the N-terminus through residue 108 of the intact protein. Thus, the results tentatively identify this segment of the protein containing the binding pocket for 25-OH-D{sub 3}.

  4. Maternal Exposure to Synthetic Chemicals and Obesity in the Offspring: Recent Findings.

    PubMed

    Liu, Yun; Peterson, Karen E

    2015-12-01

    Experimental studies suggest perinatal exposures to synthetic chemicals may be associated with early onset obesity, although this hypothesis has not been extensively examined in humans. This article summarizes the evidence relating maternal perinatal exposure to common persistent organic compounds (polychlorinated biphenyl, dichlorodiphenyldichloroethylene, dichlorodiphenyltrichloroethane, hexachlorobenzene, hexachlorocyclohexane), perfluoroalkyls, perfluorooctane sulfonate, polybrominated diphenyl ethers and tributyltin, and nonpersistent compounds (phthalates, bisphenol A) on child obesity during sensitive developmental periods. Twenty-two epidemiologic studies published from 2011 to 2015 offer inconsistent support for the obesogenic effects of most substances and are limited by relatively small sample sizes and indirect measures of adiposity. The clearest findings suggest an influence of maternal dichlorodiphenyldichloroethylene exposure on offspring overweight and obesity. Recommendations for future epidemiological research include longer follow-up of effects of pre- and postnatal exposures in large samples; utilization of direct measures of adiposity; and consideration of effect modification by sex, birth weight, dietary fat, and maternal weight status.

  5. Structure of Serum Albumin

    NASA Technical Reports Server (NTRS)

    Carter, Daniel C.; Ho, Joseph X.

    1994-01-01

    Because of its availability, low cost, stability, and unusual ligand-binding properties, serum albumin has been one of the mst extensively studied and applied proteins in biochemistry. However, as a protein, albumin is far from typical, and the widespread interest in and application of albumin have not been balanced by an understanding of its molecular structure. Indeed, for more than 30 years structural information was surmised based solely on techniques such as hydrodynamics, low-angle X-ray scattering, and predictive methods.

  6. Interpreting serum risperidone concentrations.

    PubMed

    Boerth, Joel M; Caley, Charles F; Goethe, John W

    2005-02-01

    Risperidone is an atypical antipsychotic commonly used for treatment of schizophrenia and other psychotic disorders. Although therapeutic drug monitoring is not routine for any of the atypical antipsychotics, serum antipsychotic concentrations are measured routinely to assess treatment nonadherence. In humans, risperidone is metabolized by cytochrome P450 2D6 to 9-hydroxyrisperidone; together these constitute the active moiety. Dose-proportional increases in serum concentrations have not been reported for the parent drug, but have been reported for 9-hydroxyrisperidone and the active moiety (i.e., the combined concentrations of risperidone and 9-hydroxyrisperidone). We describe a 34-year-old Caucasian man of Sicilian descent with a history of schizophrenia, disorganized type. He was suspected to be noncompliant with his risperidone therapy. Initially, active moiety risperidone concentrations increased linearly with prescribed dosage increases. However, with continued increases, active moiety concentrations adjusted downward and remained 17-36% below anticipated levels. We propose a method for estimating target active moiety concentrations of risperidone based on dosage-a method that may be used to guide clinicians in assessing nonadherence to risperidone treatment.

  7. ACTIVATION ASSAY FOR PEROXISOME PROLIFERATOR-ACTIVATED RECEPTOR- ALPHA (PPARÁ) BY PERFLUOROALKYL ACIDS (PFAAS) IN COS-1 CELLS

    EPA Science Inventory

    PFAAs have been found to elicit various physiological effects including peroxisome proliferation, indicating the mechanism of action for these chemicals could involve PPAR. This study investigates the ability of PFAAs to bind and activate mouse and human PPARα in COS-1 cell...

  8. Analysis of the presence of perfluoroalkyl substances in water, sediment and biota of the Jucar River (E Spain). Sources, partitioning and relationships with water physical characteristics.

    PubMed

    Campo, Julian; Lorenzo, María; Pérez, Francisca; Picó, Yolanda; Farré, Marinel la; Barceló, Damià

    2016-05-01

    The presence, sources and partitioning of 21 perfluoroalkyl substances (PFASs: C4-C14, C16, C18 carboxylate, C4, C6-C10 sulfonates and C8 sulfonamide) were assessed in water, sediment, and biota of the Jucar River basin (E Spain). Considering the three matrices, perfluoropentanoate (PFPeA) and perfluorooctane sulfonate (PFOS) were the most frequent compounds, being remarkable the high occurrence of short-chain PFASs (C≤8), which are intended to replace the long-chain ones in several industrial and commercial applications. In general, all samples were contaminated with at least one PFAS, with the exception of three fish samples. Mean concentrations detected in sediments (0.22-11.5ng g(-1)) and biota (0.63-274µgkg(-1)) samples were higher than those measured in water (0.04-83.1ngL(-1)), which might suggest (bio) accumulation. The occurrence of PFAS is related to urban and industrial discharges (Cuenca city in the upper part of basin, and car's factory, and effluents of the sewage treatment plant (STP) of Alzira, in the lower part). Increasing pollution gradients were found. On the other hand, higher contamination levels were observed after regulation dams of the catchment pointing out their importance in the re-distribution of these contaminants. None of the hazard quotients (HQ) calculated indicate potential risk for the different tropic levels considered (algae, Daphnia sp. and fish). PFAS concentrations found in this study can be considered in acceptable levels if compared to existing Regulatory Legislation and, consequently, they do not pose an immediate human health risk. PMID:26974364

  9. High levels, partitioning and fish consumption based water guidelines of perfluoroalkyl acids downstream of a former firefighting training facility in Canada.

    PubMed

    Bhavsar, Satyendra P; Fowler, Craig; Day, Sarah; Petro, Steve; Gandhi, Nilima; Gewurtz, Sarah B; Hao, Chunyan; Zhao, Xiaoming; Drouillard, Ken G; Morse, Dave

    2016-09-01

    High levels of perfluoroalkyl acids (PFAAs), especially perfluorooctane sulfonic acid (PFOS), have been observed at locations in/around/downstream of the sites where PFOS-based firefighting foam was used repeatedly for a prolonged period. In this study, we conducted a detailed investigation of PFAA contamination in the Lake Niapenco area in Ontario, Canada, where among the highest ever reported levels of PFOS were recently measured in amphipods, fish and snapping turtle plasma. Levels and distribution of PFAAs in water, sediment and fish samples collected from the area varied widely. An upstream pond beside a former firefighting training area (FFTA) was confirmed as the source of PFAAs even 20years after the last use of the foam at the FFTA. Recent PFOS concentration in water (~60ng/L) at Lake Niapenco, about 14km downstream of the pond, was still 3-7× higher than the background levels. For PFOS, Log KD ranged 1.3-2.5 (mean±SE: 1.7±0.1), Log BAFs ranged 2.4-4.7 (3.4±0.05), and Log BSAFs ranged 0.7-2.9 (1.7±0.05). Some fish species-specific differences in BAF and BSAF were observed. At Log BAF of 4.7, fish PFOS levels at Lake Niapenco could reach 15,000ng/g, 100× greater than a "do not eat" advisory benchmark, without exceeding the current drinking water guideline of 300ng/L. A fish consumption based water guideline was estimated at 1-15ng/L, which is likely applicable worldwide given that the Log BAFs observed in this study were comparable to those previously reported in the literature. It appears that PFAA in the downstream waters increased between 2011 and 2015; however, further monitoring is required to confirm this trend.

  10. Perfluoroalkyl substances in soft tissues and tail feathers of Belgian barn owls (Tyto alba) using statistical methods for left-censored data to handle non-detects.

    PubMed

    Jaspers, Veerle L B; Herzke, Dorte; Eulaers, Igor; Gillespie, Brenda W; Eens, Marcel

    2013-02-01

    Perfluoroalkyl substances (PFASs) were investigated in tail feathers and soft tissues (liver, muscle, preen gland and adipose tissue) of barn owl (Tyto alba) road-kill victims (n=15) collected in the province of Antwerp (Belgium). A major PFAS producing facility is located in the Antwerp area and levels of PFASs in biota from that region have been found to be very high in previous studies. We aimed to investigate for the first time the main sources of PFASs in feathers of a terrestrial bird species. Throughout this study, we have used statistical methods for left-censored data to cope with levels below the limit of detection (LOD), instead of traditional, potentially biased, substitution methods. Perfluorooctane sulfonate (PFOS) was detected in all tissues (range: 11ng/g ww in muscle-1208ng/g ww in preen oil) and in tail feathers (<2.2-56.6ng/g ww). Perfluorooctanoate (PFOA) was measured at high levels in feathers (<14-670ng/g ww), but not in tissues (more than 50%

  11. Perfluoroalkyl Sulfonates and Carboxylic Acids in Liver, Muscle and Adipose Tissues of Black-Footed Albatross (Phoebastria nigripes) from Midway Island, North Pacific Ocean

    PubMed Central

    Chu, Shaogang; Wang, Jun; Leong, Gladys; Woodward, Lee Ann; Letcher, Robert J.; Li, Qing X.

    2015-01-01

    The Great Pacific Garbage Patch (GPGP) is a gyre of marine plastic debris in the North Pacific Ocean, and nearby is Midway Atoll which is a focal point for ecological damage. This study investigated 13 C4-C16 perfluorinated carboxylic acids (PFCAs), four (C4, C6, C8 and C10) perfluorinated sulfonates and perfluoro-4-ethylcyclohexane sulfonate [collectively perfluoroalkyl acids (PFAAs)] in black-footed albatross tissues (collected in 2011) from Midway Atoll. Of the 18 PFCAs and PFSAs monitored, most were detectable in the liver, muscle and adipose tissues. The concentrations of PFCAs and PFSAs were higher than those in most seabirds from the arctic environment, but lower than those in most of fish-eating water birds collected in the U.S. mainland. The concentrations of the PFAAs in the albatross livers were 7-fold higher than those in Laysan albatross liver samples from the same location reported in 1994. The concentration ranges of PFOS were 22.91-70.48, 3.01-6.59 and 0.53-8.35 ng g-1 wet weight (ww), respectively, in the liver, muscle and adipose. In the liver samples PFOS was dominant, followed by longer chain PFUdA (8.04-18.70 ng g-1 ww), PFTrDA, and then PFNA, PFDA and PFDoA. Short chain PFBA, PFPeA, PFBS and C16 PFODA were below limit of quantification. C8-C13 PFCAs showed much higher composition compared to those found in other wildlife where PFOS typically predominated. The concentrations of PFUdA in all 8 individual albatross muscle samples were even higher than those of PFOS. This phenomenon may be attributable to GPGP as a pollution source as well as PFAA physicochemical properties. PMID:26037817

  12. Use of strong anion exchange resins for the removal of perfluoroalkylated substances from contaminated drinking water in batch and continuous pilot plants.

    PubMed

    Zaggia, Alessandro; Conte, Lino; Falletti, Luigi; Fant, Massimo; Chiorboli, Andrea

    2016-03-15

    In recent years abnormally high levels of perfluoroalkylated substances (PFAS) have been detected both in surface and underground water sampled in an area covering approximately 150 square kilometers in the Veneto region (Italy) indicating the presence of a pollution point source (fluorochemicals production plant). Adsorption on granular activated carbon is an emergency measure which is poorly effective requiring frequent replacement. This work focuses on the application of three strong anion exchange resins (Purolite® A520E, A600E and A532E) for the removal of traces of PFOA, PFOS, PFBA and PFBS (concentration of hundreds of ng L(-1)) from drinking water. This technology is attractive for the possibility of reusing resins after an in-situ regeneration step. A strong relationship between the hydrophobicity of the exchange functional group of the resin and its capacity in removing PFAS exists. A600E (non hydrophobic) and A520E (fairly hydrophobic) show a reduced sorption capacity compared to A532E (highly hydrophobic). While A600E and A520E can be regenerated with solvent-less dilute solutions of non-toxic NH4Cl and NH4OH, A532E requires concentrated solutions of methanol or ethanol and 1% NH4Cl and for the sake of this work it was regarded as non-regenerable. The volume of regeneration effluents requiring incineration can be efficiently reduced by more than 96.5% by using reverse osmosis coupled with under-vacuum evaporation. Transmission electron analysis on saturated resins showed that large molecular macro-aggregates of PFAS can form in the intraparticle pores of resin indicating that ion exchange is not the only mechanism involved in PFAS removal. PMID:26774262

  13. Perfluoroalkyl sulfonates and carboxylic acids in liver, muscle and adipose tissues of black-footed albatross (Phoebastria nigripes) from Midway Island, North Pacific Ocean.

    PubMed

    Chu, Shaogang; Wang, Jun; Leong, Gladys; Woodward, Lee Ann; Letcher, Robert J; Li, Qing X

    2015-11-01

    The Great Pacific Garbage Patch (GPGP) is a gyre of marine plastic debris in the North Pacific Ocean, and nearby is Midway Atoll which is a focal point for ecological damage. This study investigated 13 C4-C16 perfluorinated carboxylic acids (PFCAs), four (C4, C6, C8 and C10) perfluorinated sulfonates and perfluoro-4-ethylcyclohexane sulfonate [collectively perfluoroalkyl acids (PFAAs)] in black-footed albatross tissues (collected in 2011) from Midway Atoll. Of the 18 PFCAs and PFSAs monitored, most were detectable in the liver, muscle and adipose tissues. The concentrations of PFCAs and PFSAs were higher than those in most seabirds from the arctic environment, but lower than those in most of fish-eating water birds collected in the U.S. mainland. The concentrations of the PFAAs in the albatross livers were 7-fold higher than those in Laysan albatross liver samples from the same location reported in 1994. The concentration ranges of PFOS were 22.91-70.48, 3.01-6.59 and 0.53-8.35 ng g(-1) wet weight (ww), respectively, in the liver, muscle and adipose. In the liver samples PFOS was dominant, followed by longer chain PFUdA (8.04-18.70 ng g(-1) ww), PFTrDA, and then PFNA, PFDA and PFDoA. Short chain PFBA, PFPeA, PFBS and PFODA were below limit of quantification. C8-C13 PFCAs showed much higher composition compared to those found in other wildlife where PFOS typically predominated. The concentrations of PFUdA in all 8 individual albatross muscle samples were even higher than those of PFOS. This phenomenon may be attributable to GPGP as a pollution source as well as PFAA physicochemical properties. PMID:26037817

  14. Use of strong anion exchange resins for the removal of perfluoroalkylated substances from contaminated drinking water in batch and continuous pilot plants.

    PubMed

    Zaggia, Alessandro; Conte, Lino; Falletti, Luigi; Fant, Massimo; Chiorboli, Andrea

    2016-03-15

    In recent years abnormally high levels of perfluoroalkylated substances (PFAS) have been detected both in surface and underground water sampled in an area covering approximately 150 square kilometers in the Veneto region (Italy) indicating the presence of a pollution point source (fluorochemicals production plant). Adsorption on granular activated carbon is an emergency measure which is poorly effective requiring frequent replacement. This work focuses on the application of three strong anion exchange resins (Purolite® A520E, A600E and A532E) for the removal of traces of PFOA, PFOS, PFBA and PFBS (concentration of hundreds of ng L(-1)) from drinking water. This technology is attractive for the possibility of reusing resins after an in-situ regeneration step. A strong relationship between the hydrophobicity of the exchange functional group of the resin and its capacity in removing PFAS exists. A600E (non hydrophobic) and A520E (fairly hydrophobic) show a reduced sorption capacity compared to A532E (highly hydrophobic). While A600E and A520E can be regenerated with solvent-less dilute solutions of non-toxic NH4Cl and NH4OH, A532E requires concentrated solutions of methanol or ethanol and 1% NH4Cl and for the sake of this work it was regarded as non-regenerable. The volume of regeneration effluents requiring incineration can be efficiently reduced by more than 96.5% by using reverse osmosis coupled with under-vacuum evaporation. Transmission electron analysis on saturated resins showed that large molecular macro-aggregates of PFAS can form in the intraparticle pores of resin indicating that ion exchange is not the only mechanism involved in PFAS removal.

  15. Uptake of 8:2 perfluoroalkyl phosphate diester and its degradation products by carrot and lettuce from compost-amended soil.

    PubMed

    Bizkarguenaga, E; Zabaleta, I; Prieto, A; Fernández, L A; Zuloaga, O

    2016-06-01

    The present work studied the uptake of 8:2 perfluoroalkyl phosphate diester (diPAP) by two different crops (lettuce and carrot) and two different amended soils. Firstly, the possible degradation of 8:2 diPAP in the absence of crop was studied and 8:2 monoPAP (monophosphate), 8:2 FTCA (saturated fluorotelomer carboxylate), 8:2 FTUCA (unsaturated fluorotelomer carboxylate), 7:3 FTCA (saturated fluorotelomer carboxylate), PFHpA (perfluoroheptanoic acid), PFHxA (perfluorohexanoic acid) and PFOA (perfluorooctanoic acid) were detected. In the presence of crops, different degradation products were detected in the soil and, while PFNA (perfluorononanoic acid), PFHpA, PFHxA, PFPeA (perfluoropentacoic acid), PFBA (perfluorobutanoic acid), 7:3 FTCA and PFOA were determined in the cultivation media when carrot was grown, PFOA was the only degradation product detected in the case of lettuce experiments. Regarding the uptake in carrot, all the degradation products except 7:3 FTCA were translocated from the soil to the carrot. Carrot core, peel and leaves bioconcentration factors, BCFs, were determined for 8:2 diPAP and its degradation products. Values lower than method detection limits for core and low BCFs in peel (0.025-0.042) and leaves (0.028-0.049) were achieved for 8:2 diPAP. Regarding to the degradation products, the higher their water solubility, the higher the plant translocation. In this sense, the lower the carbon chain length of PFCAs, the higher the BCFs determined (PFBA > PFHxA > PFHpA > PFOA > PFNA). In general, lower total BCFs were achieved when the total organic carbon of the soils increased. For lettuce experiments, 8:2 diPAP (0.04-0.18) and PFOA (0.28-1.57) were only determined in lettuce heart. PMID:26991379

  16. Analysis of the presence of perfluoroalkyl substances in water, sediment and biota of the Jucar River (E Spain). Sources, partitioning and relationships with water physical characteristics.

    PubMed

    Campo, Julian; Lorenzo, María; Pérez, Francisca; Picó, Yolanda; Farré, Marinel la; Barceló, Damià

    2016-05-01

    The presence, sources and partitioning of 21 perfluoroalkyl substances (PFASs: C4-C14, C16, C18 carboxylate, C4, C6-C10 sulfonates and C8 sulfonamide) were assessed in water, sediment, and biota of the Jucar River basin (E Spain). Considering the three matrices, perfluoropentanoate (PFPeA) and perfluorooctane sulfonate (PFOS) were the most frequent compounds, being remarkable the high occurrence of short-chain PFASs (C≤8), which are intended to replace the long-chain ones in several industrial and commercial applications. In general, all samples were contaminated with at least one PFAS, with the exception of three fish samples. Mean concentrations detected in sediments (0.22-11.5ng g(-1)) and biota (0.63-274µgkg(-1)) samples were higher than those measured in water (0.04-83.1ngL(-1)), which might suggest (bio) accumulation. The occurrence of PFAS is related to urban and industrial discharges (Cuenca city in the upper part of basin, and car's factory, and effluents of the sewage treatment plant (STP) of Alzira, in the lower part). Increasing pollution gradients were found. On the other hand, higher contamination levels were observed after regulation dams of the catchment pointing out their importance in the re-distribution of these contaminants. None of the hazard quotients (HQ) calculated indicate potential risk for the different tropic levels considered (algae, Daphnia sp. and fish). PFAS concentrations found in this study can be considered in acceptable levels if compared to existing Regulatory Legislation and, consequently, they do not pose an immediate human health risk.

  17. Emission of perfluoroalkyl carboxylic acids (PFCA) from heated surfaces made of polytetrafluoroethylene (PTFE) applied in food contact materials and consumer products.

    PubMed

    Schlummer, Martin; Sölch, Christina; Meisel, Theresa; Still, Mona; Gruber, Ludwig; Wolz, Gerd

    2015-06-01

    Polytetrafluoroethylene (PTFE) has been widely discussed as a source of perfluorooctanoic acid (PFOA), which has been used in the production of fluoropolymers. PTFE may also contain unintended perfluoroalkyl carboxylic acids (PFCAs) caused by thermolysis of PTFE, which has been observed at temperatures above 300°C. Common PTFE coated food contact materials and consumer goods are operated at temperatures above 200°C. However, knowledge on possible emissions of PFCAs is limited. Therefore, it was the aim of this study to investigate and evaluate the emission of PFCAs from PTFE coated products with both, normal use and overheating scenarios. Four pans, claimed to be PFOA free, and nine consumer products were investigated. At normal use conditions (<230°C), emissions from PTFE surfaces were trapped for 1h. Overheating scenarios (>260°C) recorded emissions during a 30min heating of empty pans on a stove. Emissions were analyzed by LC-ESI-MS. Results indicate the emission of PFCAs, whereas no perfluorinated sulfonic acids were traced. At normal use conditions total emissions of PFCAs accounted for 4.75ng per hour. Overheated pans, however, released far higher amounts with up to 12190ng PFCAs per hour at 370°C. Dominating contributors where PFBA and PFOA at normal use and PFBA and PFPeA during overheating. Temperature seems to be the main factor controlling the emission of PFCAs. A worst case estimation of human exposure revealed that emissions of PFCAs from heated PTFE surfaces would be far below the TDI of 1500ng PFOA per kg body weight.

  18. Perfluoroalkyl sulfonates and carboxylic acids in liver, muscle and adipose tissues of black-footed albatross (Phoebastria nigripes) from Midway Island, North Pacific Ocean.

    PubMed

    Chu, Shaogang; Wang, Jun; Leong, Gladys; Woodward, Lee Ann; Letcher, Robert J; Li, Qing X

    2015-11-01

    The Great Pacific Garbage Patch (GPGP) is a gyre of marine plastic debris in the North Pacific Ocean, and nearby is Midway Atoll which is a focal point for ecological damage. This study investigated 13 C4-C16 perfluorinated carboxylic acids (PFCAs), four (C4, C6, C8 and C10) perfluorinated sulfonates and perfluoro-4-ethylcyclohexane sulfonate [collectively perfluoroalkyl acids (PFAAs)] in black-footed albatross tissues (collected in 2011) from Midway Atoll. Of the 18 PFCAs and PFSAs monitored, most were detectable in the liver, muscle and adipose tissues. The concentrations of PFCAs and PFSAs were higher than those in most seabirds from the arctic environment, but lower than those in most of fish-eating water birds collected in the U.S. mainland. The concentrations of the PFAAs in the albatross livers were 7-fold higher than those in Laysan albatross liver samples from the same location reported in 1994. The concentration ranges of PFOS were 22.91-70.48, 3.01-6.59 and 0.53-8.35 ng g(-1) wet weight (ww), respectively, in the liver, muscle and adipose. In the liver samples PFOS was dominant, followed by longer chain PFUdA (8.04-18.70 ng g(-1) ww), PFTrDA, and then PFNA, PFDA and PFDoA. Short chain PFBA, PFPeA, PFBS and PFODA were below limit of quantification. C8-C13 PFCAs showed much higher composition compared to those found in other wildlife where PFOS typically predominated. The concentrations of PFUdA in all 8 individual albatross muscle samples were even higher than those of PFOS. This phenomenon may be attributable to GPGP as a pollution source as well as PFAA physicochemical properties.

  19. Historical usage of aqueous film forming foam: a case study of the widespread distribution of perfluoroalkyl acids from a military airport to groundwater, lakes, soils and fish.

    PubMed

    Filipovic, Marko; Woldegiorgis, Andreas; Norström, Karin; Bibi, Momina; Lindberg, Maria; Österås, Ann-Helen

    2015-06-01

    Historical usage of aqueous film forming foams (AFFFs) at military airports is a potential source of perfluoroalkyl acids (PFAAs) to the nearby environment. In this study, the distribution of perfluorohexanoic acid (PFHxA), perfluorooctanoic acid (PFOA), perfluorohexane sulfonate (PFHxS) and perfluorooctane sulfonate (PFOS) in soil, groundwater, surface water, tap water well, and fish muscle was investigated at a closed down military airfield (F18) and its surroundings in Stockholm, Sweden. The presence of PFOS at AFFF training sites was inventoried. One major finding of the study is that a former airfield, abandoned since 1994, may still be a point source of PFAAs to nearby recipients. PFOS and PFOA were ubiquitous in the soil samples at former AFFF training sites with concentrations ranging from 2.18 to 8520ngg(-1) dry weight and <0.12-287ngg(-1) dry weight respectively. The sum of PFAAs in the groundwater and surface waters ranged from 738 to 51000ngL(-1) and

  20. Na+/Taurocholate Cotransporting Polypeptide and Apical Sodium-Dependent Bile Acid Transporter Are Involved in the Disposition of Perfluoroalkyl Sulfonates in Humans and Rats

    PubMed Central

    Zhao, Wen; Zitzow, Jeremiah D.; Ehresman, David J.; Chang, Shu-Ching; Butenhoff, John L.; Forster, Jameson; Hagenbuch, Bruno

    2015-01-01

    Among the perfluoroalkyl sulfonates (PFASs), perfluorohexane sulfonate (PFHxS), and perfluorooctane sulfonate (PFOS) have half-lives of several years in humans, mainly due to slow renal clearance and potential hepatic accumulation. Both compounds undergo enterohepatic circulation. To determine whether transporters involved in the enterohepatic circulation of bile acids are also involved in the disposition of PFASs, uptake of perfluorobutane sulfonate (PFBS), PFHxS, and PFOS was measured using freshly isolated human and rat hepatocytes in the absence or presence of sodium. The results demonstrated sodium-dependent uptake for all 3 PFASs. Given that the Na+/taurocholate cotransporting polypeptide (NTCP) and the apical sodium-dependent bile salt transporter (ASBT) are essential for the enterohepatic circulation of bile acids, transport of PFASs was investigated in stable CHO Flp-In cells for human NTCP or HEK293 cells transiently expressing rat NTCP, human ASBT, and rat ASBT. The results demonstrated that both human and rat NTCP can transport PFBS, PFHxS, and PFOS. Kinetics with human NTCP revealed Km values of 39.6, 112, and 130 µM for PFBS, PFHxS, and PFOS, respectively. For rat NTCP Km values were 76.2 and 294 µM for PFBS and PFHxS, respectively. Only PFOS was transported by human ASBT whereas rat ASBT did not transport any of the tested PFASs. Human OSTα/β was also able to transport all 3 PFASs. In conclusion, these results suggest that the long half-live and the hepatic accumulation of PFOS in humans are at least, in part, due to transport by NTCP and ASBT. PMID:26001962

  1. High levels, partitioning and fish consumption based water guidelines of perfluoroalkyl acids downstream of a former firefighting training facility in Canada.

    PubMed

    Bhavsar, Satyendra P; Fowler, Craig; Day, Sarah; Petro, Steve; Gandhi, Nilima; Gewurtz, Sarah B; Hao, Chunyan; Zhao, Xiaoming; Drouillard, Ken G; Morse, Dave

    2016-09-01

    High levels of perfluoroalkyl acids (PFAAs), especially perfluorooctane sulfonic acid (PFOS), have been observed at locations in/around/downstream of the sites where PFOS-based firefighting foam was used repeatedly for a prolonged period. In this study, we conducted a detailed investigation of PFAA contamination in the Lake Niapenco area in Ontario, Canada, where among the highest ever reported levels of PFOS were recently measured in amphipods, fish and snapping turtle plasma. Levels and distribution of PFAAs in water, sediment and fish samples collected from the area varied widely. An upstream pond beside a former firefighting training area (FFTA) was confirmed as the source of PFAAs even 20years after the last use of the foam at the FFTA. Recent PFOS concentration in water (~60ng/L) at Lake Niapenco, about 14km downstream of the pond, was still 3-7× higher than the background levels. For PFOS, Log KD ranged 1.3-2.5 (mean±SE: 1.7±0.1), Log BAFs ranged 2.4-4.7 (3.4±0.05), and Log BSAFs ranged 0.7-2.9 (1.7±0.05). Some fish species-specific differences in BAF and BSAF were observed. At Log BAF of 4.7, fish PFOS levels at Lake Niapenco could reach 15,000ng/g, 100× greater than a "do not eat" advisory benchmark, without exceeding the current drinking water guideline of 300ng/L. A fish consumption based water guideline was estimated at 1-15ng/L, which is likely applicable worldwide given that the Log BAFs observed in this study were comparable to those previously reported in the literature. It appears that PFAA in the downstream waters increased between 2011 and 2015; however, further monitoring is required to confirm this trend. PMID:27302846

  2. Perfluoroalkyl substances (PFAS) in river and ground/drinking water of the Ganges River basin: Emissions and implications for human exposure.

    PubMed

    Sharma, Brij Mohan; Bharat, Girija K; Tayal, Shresth; Larssen, Thorjørn; Bečanová, Jitka; Karásková, Pavlína; Whitehead, Paul G; Futter, Martyn N; Butterfield, Dan; Nizzetto, Luca

    2016-01-01

    Many perfluoroalkyl substances (PFAS) are ubiquitous environmental contaminants. They have been widely used in production processes and daily-use products or may result from degradation of precursor compounds in products or the environment. India, with its developing industrialization and population moving from traditional to contemporary lifestyles, represents an interesting case study to investigate PFAS emission and exposure along steep environmental and socioeconomic gradients. This study assesses PFAS concentrations in river and groundwater (used in this region as drinking water) from several locations along the Ganges River and estimates direct emissions, specifically for PFOS and PFOA. 15 PFAS were frequently detected in the river with the highest concentrations observed for PFHxA (0.4-4.7 ng L(-1)) and PFBS (

  3. Hair: A Diagnostic Tool to Complement Blood Serum and Urine.

    ERIC Educational Resources Information Center

    Maugh, Thomas H., II

    1978-01-01

    Trace elements and some drugs can be identified in hair and it seems likely that other organic chemicals will be identifiable in the future. Since hair is so easily collected, stored, and analyzed it promises to be an ideal complement to serum and urine analysis as a diagnostic tool. (BB)

  4. Consumer Product Chemicals in Indoor Dust: A Quantitative Meta-analysis of U.S. Studies

    PubMed Central

    2016-01-01

    Indoor dust is a reservoir for commercial consumer product chemicals, including many compounds with known or suspected health effects. However, most dust exposure studies measure few chemicals in small samples. We systematically searched the U.S. indoor dust literature on phthalates, replacement flame retardants (RFRs), perfluoroalkyl substances (PFASs), synthetic fragrances, and environmental phenols and estimated pooled geometric means (GMs) and 95% confidence intervals for 45 chemicals measured in ≥3 data sets. In order to rank and contextualize these results, we used the pooled GMs to calculate residential intake from dust ingestion, inhalation, and dermal uptake from air, and then identified hazard traits from the Safer Consumer Products Candidate Chemical List. Our results indicate that U.S. indoor dust consistently contains chemicals from multiple classes. Phthalates occurred in the highest concentrations, followed by phenols, RFRs, fragrance, and PFASs. Several phthalates and RFRs had the highest residential intakes. We also found that many chemicals in dust share hazard traits such as reproductive and endocrine toxicity. We offer recommendations to maximize comparability of studies and advance indoor exposure science. This information is critical in shaping future exposure and health studies, especially related to cumulative exposures, and in providing evidence for intervention development and public policy. PMID:27623734

  5. Circulating serum xenoestrogens and mammographic breast density

    PubMed Central

    2013-01-01

    Introduction Humans are widely exposed to estrogenically active phthalates, parabens, and phenols, raising concerns about potential effects on breast tissue and breast cancer risk. We sought to determine the association of circulating serum levels of these chemicals (reflecting recent exposure) with mammographic breast density (a marker of breast cancer risk). Methods We recruited postmenopausal women aged 55 to 70 years from mammography clinics in Madison, Wisconsin (N = 264). Subjects completed a questionnaire and provided a blood sample that was analyzed for mono-ethyl phthalate, mono-butyl phthalate, mono-benzyl phthalate, butyl paraben, propyl paraben, octylphenol, nonylphenol, and bisphenol A (BPA). Percentage breast density was measured from mammograms by using a computer-assisted thresholding method. Results Serum BPA was positively associated with mammographic breast density after adjusting for age, body mass index, and other potentially confounding factors. Mean percentage density was 12.6% (95% confidence interval (CI), 11.4 to 14.0) among the 193 women with nondetectable BPA levels, 13.7% (95% CI, 10.7 to 17.1) among the 35 women with detectable levels below the median (<0.55 ng/ml), and 17.6% (95% CI, 14.1 to 21.5) among the 34 women with detectable levels above the median (>0.55 ng/ml; Ptrend = 0.01). Percentage breast density was also elevated (18.2%; 95% CI, 13.4 to 23.7) among the 18 women with serum mono-ethyl phthalate above the median detected level (>3.77 ng/ml) compared with women with nondetectable BPA levels (13.1%; 95% CI, 11.9 to 14.3; Ptrend = 0.07). No other chemicals demonstrated associations with percentage breast density. Conclusions Postmenopausal women with high serum levels of BPA and mono-ethyl phthalate had elevated breast density. Further investigation of the impact of BPA and mono-ethyl phthalate on breast cancer risk by using repeated serum measurements or other markers of xenoestrogen exposure are needed. PMID:23710608

  6. Serum vitamin c and iron levels in oral submucous fibrosis

    PubMed Central

    Guruprasad, R; Nair, Preeti P; Singh, Manika; Singh, Manishi; Singh, MP; Jain, Arpit

    2014-01-01

    Background: In this study Serum Vitamin C and Iron levels in Oral submucous fibrosis (OSMF) were estimated. The objective was to evaluate the correlation between Serum Vitamin C and Iron levels in OSMF individuals. Serum Iron content can be a predictor for the progression of this condition. OSMF is basically a disorder of collagen metabolism where Vitamin C gets utilized in conversion of proline into hydroxyproline, this hydroxylation reaction requires ferrous Iron and Vitamin C. Many studies regarding micronutrients and other antioxidants levels have been emphasized, but very few studies are done on the Serum levels of Vitamin C and its correlation with Iron in OSMF patients. Methods: Thirty five OSMF patients and 50 deleterious habit free healthy individuals (controls) were selected. Two ml of venous blood was collected from each individual. Vitamin C level in serum was estimated by 2-4 dinitrophenylhydrazine method and Iron estimated by Tripyridyl method. Results: The level of Serum Vitamin-C and Iron was significantly decreased in OSMF patients when compared to controls which were statistically significant. Conclusion: On the basis of these observations, it seems possible that the chemical, thermal and/or mechanical factors associated with the use of areca nut may act in conjunction with the Vitamin C and Iron deficiency leading to the development of OSMF. Therapeutic substitution of vitamin C and Iron may be recommended in the management of OSMF PMID:25565730

  7. Production and EPR characterization of exohedrally perfluoroalkylated paramagnetic lanthanum metallofullerenes: (La@C 82)-(C 8F 17) 2

    NASA Astrophysics Data System (ADS)

    Tagmatarchis, Nikos; Taninaka, Atsushi; Shinohara, Hisanori

    2002-04-01

    A strategy to chemically derivatize the outer sphere of endohedral metallofullerenes by using a fluorous synthesis-partitioning approach has been developed. The newly synthesized materials were found to be paramagnetic species and were characterized by electron paramagnetic resonance spectroscopy (EPR), laser desorption time-of-flight spectrometry (LD-TOF) and electronic absorption spectroscopy (UV-VIS-NIR). The fluorous-phase partitioning method (or liquid-liquid extraction), successfully applied for the first time in fullerene chemistry, aided by multi-stage recycling high performance liquid chromatography (HPLC) resulted in their isolation in isomer-free form. The present study opens the way to organic transformations of fullerene-based materials as a powerful separation technique.

  8. Sequences Of Amino Acids For Human Serum Albumin

    NASA Technical Reports Server (NTRS)

    Carter, Daniel C.

    1992-01-01

    Sequences of amino acids defined for use in making polypeptides one-third to one-sixth as large as parent human serum albumin molecule. Smaller, chemically stable peptides have diverse applications including service as artificial human serum and as active components of biosensors and chromatographic matrices. In applications involving production of artificial sera from new sequences, little or no concern about viral contaminants. Smaller genetically engineered polypeptides more easily expressed and produced in large quantities, making commercial isolation and production more feasible and profitable.

  9. [Serum sterilization in the cold with peracetic acid].

    PubMed

    Sprössig, M; Wutzler, P; Schweizer, H; Mücke, H

    1976-01-01

    On the basis of broad antimicrobic effect including also bacterial spores, mycoplasmas and viruses, the peracetic acid suits to sterilize in cold. By means of the final 0,1 to 0.02% concentration of the peracetic acid acting for 30 min. up to 5 days, it succeeded in sterilizing the serum used to prepare culture medium for bacteria, mycoplasmas and tissue cultures. Growth controls shown at least as good results as were those in using filtered sera. Chemical sterilization by means of the peracetic acid leads to significant diminution of neutralization and complementfixation antibodies in serum. PMID:987107

  10. 19F NMR-, ESR-, and vis-NIR-spectroelectrochemical study of the unconventional reduction behaviour of a perfluoroalkylated fullerene: dimerization of the C70(CF3)10– radical anion†

    PubMed Central

    Zalibera, Michal; Machata, Peter; Clikeman, Tyler T.; Rosenkranz, Marco; Strauss, Steven H.; Boltalina, Olga V.; Popov, Alexey A.

    2016-01-01

    The most abundant isomer of C70(CF3)10 (70-10-1) is a rare example of a perfluoroalkylated fullerene exhibiting electrochemically irreversible reduction. We show that electrochemical reversibility at the first reduction step is achieved at scan rates higher than 500 V s-1 Applying ESR-, vis-NIR-, and 19F NMR- spectroelectrochemistry, as well as mass spectrometry and DFT calculations, we show that the (70-10-1)- radical monoanion is in equilibrium with a singly-bonded diamagnetic dimeric dianion. This study is the first example of 19F NMR spectroelectrochemistry, which promises to be an important method for the elucidation of redox mechanisms of fluoroorganic compounds. Additionally, we demonstrate the importance of combining different spectroelectrochemical methods and quantitative analysis of the transferred charge and spin numbers in the determination of the redox mechanism. PMID:26359514

  11. Simultaneous determination of perfluoroalkyl iodides, perfluoroalkane sulfonamides, fluorotelomer alcohols, fluorotelomer iodides and fluorotelomer acrylates and methacrylates in water and sediments using solid-phase microextraction-gas chromatography/mass spectrometry.

    PubMed

    Bach, Cristina; Boiteux, Virginie; Hemard, Jessica; Colin, Adeline; Rosin, Christophe; Munoz, Jean-François; Dauchy, Xavier

    2016-05-27

    Here, we developed and validated a headspace-solid-phase microextraction-gas chromatography/mass spectrometry (HS-SPME-GC/MS) method for the determination of 14 volatile perfluorinated alkylated substances (PFASs) in water and sediment samples according to SANTE 11945/2015 guidelines. Three fluorotelomer alcohols (FTOHs), two perfluoroalkyl iodides (PFIs), three fluorotelomer iodides (FTIs), four fluorotelomer acrylates and methacrylates (FTACs and FTMACs) and two perfluoroalkyl sulfonamides (FASAs) were analysed simultaneously to assess the occurrence of these compounds from their emission sources to the outlets in water treatment plants. Several SPME parameters were optimised for both water and sediment to maximise responses and keep analysis time to a minimum. In tap water, the limits of quantification (LOQs) were found to be between 20ng/L and 100ng/L depending on the analyte, with mean recoveries ranging from 76 to 126%. For sediments, LOQs ranged from 1 to 3ng/g dry weight depending on the target compound, with mean recoveries ranging from 74 to 125%. SPME considerably reduced sample preparation time and its use provided a sensitive, fast and simple technique. We then used this HS-SPME-GC/MS method to investigate the presence of volatile PFASs in the vicinity of an industrial facility. Only 8:2 FTOH and 10:2 FTOH were detected in a few water and sediment samples at sub-ppb concentration levels. Moreover, several non-target fluorotelomers (12:2 FTOH, 14:2 FTOH and 10:2 FTI) were identified in raw effluent samples. These long-chain fluorotelomers have high bioaccumulative potential in the aquatic environment compared with short-chain fluorotelomers such as 6:2 FTOH and 6:2 FTI. PMID:27125188

  12. Isolation of human anti-serum albumin Fab antibodies with an extended serum-half life.

    PubMed

    Kang, Hyeon-Ju; Kim, Hye-Jin; Cha, Sang-Hoon

    2016-01-01

    The serum albumin (SA) has been exploited to generate long-acting biotherapeutics by taking advantage of the FcRn-mediated recycling mechanism in a direct or an indirect way. Since Fab fragments have been proven to be clinically safe for human usage, we assumed that human anti-SA Fab antibodies could have a great potential as a carrier molecule to extend the serum half-life of therapeutic proteins. We, herein, had attempted to isolate anti-SA Fab antibodies from HuDVFab-8L antibody library via a phage display technology, and identified eight discrete human Fab antibodies. One of the Fab antibodies, SL335, showed the strongest binding reactivity to human SA with nM range of affinity at both pH 6 and pH 7.4, and cross-reacted to SAs from various species including rat, mouse, canine and monkey. The in vivo pharmacokinetic assay using a rat model indicated that SL335 has approximately 10 fold longer serum half-life and 26 to 44-fold increase in AUC0 → ∞ compared to the negative control Fab molecule in both intravenous and subcutaneous administrations. Knowing that Fabs have proven to be safe in clinics for a long time, SL335 seems to have a great potential in generating long-acting protein drugs by tagging effector molecules with either chemical conjugation or genetic fusion.

  13. Effects of serum-isolated vs synthetic bilirubin-albumin complexes on dye-binding methods for estimating serum albumin.

    PubMed

    Ihara, H; Nakamura, H; Aoki, Y; Aoki, T; Yoshida, M

    1991-07-01

    Bush and Reed reported (Clin Chem 1987;33:821-3) that the reaction of albumin with bromcresol purple but not with bromcresol green underestimated the concentration of albumin in synthetically obtained bilirubin-albumin (Bd) by 29%. Their unproven assumption was that chemically synthesized Bd behaved in a manner indistinguishable from the natural Bd in icteric serum. Here we verify that Bd, whether synthetically obtained or isolated from serum, causes an underestimation of albumin in the bromcresol purple but not in the bromcresol green method. The molar ratio of Bd from either source to underestimated albumin approximates 1.0, suggesting that one molecule of Bd would react equivalently to a molecule of albumin in the bromcresol purple method. This underestimation might falsely suggest hypoalbuminemia in patients with increased serum Bd. PMID:1855300

  14. Brain region-specific perfluoroalkylated sulfonate (PFSA) and carboxylic acid (PFCA) accumulation and neurochemical biomarker responses in east Greenland polar bears (Ursus maritimus).

    PubMed

    Eggers Pedersen, Kathrine; Basu, Niladri; Letcher, Robert; Greaves, Alana K; Sonne, Christian; Dietz, Rune; Styrishave, Bjarne

    2015-04-01

    Perfluoroalkyl substances (PFASs) is a growing class of contaminants in the Arctic environment, and include the established perfluorinated sulfonates (PFSAs; especially perfluorooctane sulfonate (PFOS)) and carboxylic acids (PFCAs). PFSAs and PFCAs of varying chain length have been reported to bioaccumulate in lipid rich tissues of the brain among other tissues such as liver, and can reach high concentrations in top predators including the polar bear. PFCA and PFSA bioaccummulation in the brain has the potential to pose neurotoxic effects and therefore we conducted a study to investigate if variations in neurochemical transmitter systems i.e. the cholinergic, glutaminergic, dopaminergic and GABAergic, could be related to brain-specific bioaccumulation of PFASs in East Greenland polar bears. Nine brain regions from nine polar bears were analyzed for enzyme activity (monoamine oxidase (MAO), acetylcholinesterase (AChE) and glutamine synthetase (GS)) and receptor density (dopamine-2 (D2), muscarinic cholinergic (mAChR) and gamma-butyric acid type A (GABA-A)) along with PFSA and PFCA concentrations. Average brain ∑PFSA concentration was 25ng/g ww where PFOS accounted for 91%. Average ∑PFCA concentration was 88ng/g ww where PFUnDA, PFDoDA and PFTrDA combined accounted for 79%. The highest concentrations of PFASs were measured in brain stem, cerebellum and hippocampus. Correlative analyses were performed both across and within brain regions. Significant positive correlations were found between PFASs and MAO activity in occipital lobe (e.g. ∑PFCA; rp=0.83, p=0.041, n=6) and across brain regions (e.g. ∑PFCA; rp=0.47, p=0.001, ∑PFSA; rp=0.44, p>0.001; n=50). GABA-A receptor density was positively correlated with two PFASs across brain regions (PFOS; rp=0.33, p=0.02 and PFDoDA; rp=0.34, p=0.014; n=52). Significant negative correlations were found between mAChR density and PFASs in cerebellum (e.g. ∑PFCA; rp=-0.95, p=0.013, n=5) and across brain regions (e.g.

  15. Brain region-specific perfluoroalkylated sulfonate (PFSA) and carboxylic acid (PFCA) accumulation and neurochemical biomarker responses in east Greenland polar bears (Ursus maritimus).

    PubMed

    Eggers Pedersen, Kathrine; Basu, Niladri; Letcher, Robert; Greaves, Alana K; Sonne, Christian; Dietz, Rune; Styrishave, Bjarne

    2015-04-01

    Perfluoroalkyl substances (PFASs) is a growing class of contaminants in the Arctic environment, and include the established perfluorinated sulfonates (PFSAs; especially perfluorooctane sulfonate (PFOS)) and carboxylic acids (PFCAs). PFSAs and PFCAs of varying chain length have been reported to bioaccumulate in lipid rich tissues of the brain among other tissues such as liver, and can reach high concentrations in top predators including the polar bear. PFCA and PFSA bioaccummulation in the brain has the potential to pose neurotoxic effects and therefore we conducted a study to investigate if variations in neurochemical transmitter systems i.e. the cholinergic, glutaminergic, dopaminergic and GABAergic, could be related to brain-specific bioaccumulation of PFASs in East Greenland polar bears. Nine brain regions from nine polar bears were analyzed for enzyme activity (monoamine oxidase (MAO), acetylcholinesterase (AChE) and glutamine synthetase (GS)) and receptor density (dopamine-2 (D2), muscarinic cholinergic (mAChR) and gamma-butyric acid type A (GABA-A)) along with PFSA and PFCA concentrations. Average brain ∑PFSA concentration was 25ng/g ww where PFOS accounted for 91%. Average ∑PFCA concentration was 88ng/g ww where PFUnDA, PFDoDA and PFTrDA combined accounted for 79%. The highest concentrations of PFASs were measured in brain stem, cerebellum and hippocampus. Correlative analyses were performed both across and within brain regions. Significant positive correlations were found between PFASs and MAO activity in occipital lobe (e.g. ∑PFCA; rp=0.83, p=0.041, n=6) and across brain regions (e.g. ∑PFCA; rp=0.47, p=0.001, ∑PFSA; rp=0.44, p>0.001; n=50). GABA-A receptor density was positively correlated with two PFASs across brain regions (PFOS; rp=0.33, p=0.02 and PFDoDA; rp=0.34, p=0.014; n=52). Significant negative correlations were found between mAChR density and PFASs in cerebellum (e.g. ∑PFCA; rp=-0.95, p=0.013, n=5) and across brain regions (e.g.

  16. CADASTER QSPR Models for Predictions of Melting and Boiling Points of Perfluorinated Chemicals.

    PubMed

    Bhhatarai, Barun; Teetz, Wolfram; Liu, Tao; Öberg, Tomas; Jeliazkova, Nina; Kochev, Nikolay; Pukalov, Ognyan; Tetko, Igor V; Kovarich, Simona; Papa, Ester; Gramatica, Paola

    2011-03-14

    Quantitative structure property relationship (QSPR) studies on per- and polyfluorinated chemicals (PFCs) on melting point (MP) and boiling point (BP) are presented. The training and prediction chemicals used for developing and validating the models were selected from Syracuse PhysProp database and literatures. The available experimental data sets were split in two different ways: a) random selection on response value, and b) structural similarity verified by self-organizing-map (SOM), in order to propose reliable predictive models, developed only on the training sets and externally verified on the prediction sets. Individual linear and non-linear approaches based models developed by different CADASTER partners on 0D-2D Dragon descriptors, E-state descriptors and fragment based descriptors as well as consensus model and their predictions are presented. In addition, the predictive performance of the developed models was verified on a blind external validation set (EV-set) prepared using PERFORCE database on 15 MP and 25 BP data respectively. This database contains only long chain perfluoro-alkylated chemicals, particularly monitored by regulatory agencies like US-EPA and EU-REACH. QSPR models with internal and external validation on two different external prediction/validation sets and study of applicability-domain highlighting the robustness and high accuracy of the models are discussed. Finally, MPs for additional 303 PFCs and BPs for 271 PFCs were predicted for which experimental measurements are unknown.

  17. Chemical Reactors.

    ERIC Educational Resources Information Center

    Kenney, C. N.

    1980-01-01

    Describes a course, including content, reading list, and presentation on chemical reactors at Cambridge University, England. A brief comparison of chemical engineering education between the United States and England is also given. (JN)

  18. Evaluation of potential health effects associated with serum polychlorinated biphenyl levels

    SciTech Connect

    Stehr-Green, P.A.; Welty, E.; Steele, G.; Steinberg, K.

    1986-12-01

    In late 1983, we conducted a cross-sectional epidemiologic study to evaluate persons at risk of exposure to three chemical waste sites by comparing clinical disease end points and clinical chemistry parameters with serum polychlorinated biphenyls (PCB) levels. A total of 106 individuals participated in the study. The only statistically significant finding in regard to self-reported, physician-diagnosed health problems was a dose-response relationship between serum PCB levels and the occurrence of high blood pressure; however, this association failed to achieve statistical significance when we controlled for possible confounding effects of both age and smoking. Serum triglyceride and cholesterol levels were also higher in the group with elevated serum PCBs; additionally, there were isolated statistically significant correlations of serum aspartate aminotransferase (SGOT) with serum lipid fraction-adjusted PCB level and serum albumin and total bilirubin with serum PCB level. Although the ranges of serum levels reported herein from exposures to PCBs in the general environment are lower than those that have been associated with acute symptoms or illness in other studies, whether these levels are associated with long-term health risks is not known. Associations of such chronic, low-dose exposures with observable health effects as suggested by this study must be evaluated further before any final conclusions can be drawn.

  19. Chemical sensor

    NASA Technical Reports Server (NTRS)

    Rauh, R. David (Inventor)

    1990-01-01

    A sensor for detecting a chemical substance includes an insertion element having a structure which enables insertion of the chemical substance with a resulting change in the bulk electrical characteristics of the insertion element under conditions sufficient to permit effective insertion; the change in the bulk electrical characteristics of the insertion element is detected as an indication of the presence of the chemical substance.

  20. Piezoelectric microcantilever serum protein detector

    NASA Astrophysics Data System (ADS)

    Capobianco, Joseph A.

    The development of a serum protein detector will provide opportunities for better screening of at-risk cancer patients, tighter surveillance of disease recurrence and better monitoring of treatment. An integrated system that can process clinical samples for a number of different types of biomarkers would be a useful tool in the early detection of cancer. Also, screening biomarkers such as antibodies in serum would provide clinicians with information regarding the patient's response to treatment. Therefore, the goal of this study is to develop a sensor which can be used for rapid, all-electrical, real-time, label-fee, in-situ, specific quantification of cancer markers, e.g., human epidermal receptor 2 (Her2) or antibodies, in serum. To achieve this end, piezoelectric microcantilever sensors (PEMS) were constructed using an 8 mum thick lead magnesium niobate-lead titanate (PMN-PT) freestanding film as the piezoelectric layer. The desired limit of detection is on the order of pg/mL. In order to achieve this goal the higher frequency lateral extension modes were used. Also, as the driving and sensing of the PEMS is electrical, the PEMS must be insulated in a manner that allows it to function in aqueous solutions. The insulation layer must also be compatible with standardized bioconjugation techniques. Finally, detection of both cancer antigens and antibodies in serum was carried out, and the results were compared to a standard commercialized protocol. PEMS have demonstrated the capability of detecting Her2 at a concentration of 5 pg/mL in diluted human serum (1:40) in less than 1 hour. The approach can be easily translated into the clinical setting because the sensitivity is more than sufficient for monitoring prognosis of breast cancer patients. In addition to Her2 detection, antibodies in serum were assayed in order to demonstrate the feasibility of monitoring the immune response for antibody-dependent cellular cytotoxicity (ADCC) in patients on antibody therapies

  1. Relationships of Perfluorooctanoate and Perfluorooctane Sulfonate Serum Concentrations between Mother–Child Pairs in a Population with Perfluorooctanoate Exposure from Drinking Water

    PubMed Central

    Lopez-Espinosa, Maria-Jose; Armstrong, Ben; Stein, Cheryl R.; Fletcher, Tony

    2012-01-01

    Background: There are limited data on the associations between maternal or newborn and child exposure to perfluoroalkyl acids (PFAAs), including perfluorooctanoate (PFOA) and perfluorooctane sulfonate (PFOS). This study provides an opportunity to assess the association between PFAA concentrations in mother–child pairs in a population exposed to PFOA via drinking water. Objectives: We aimed to determine the relationship between mother–child PFAA serum concentrations and to examine how the child:mother ratio varies with child’s age, child’s sex, drinking-water PFOA concentration, reported bottled water use, and mother’s breast-feeding intention. Methods: We studied 4,943 mother–child pairs (children, 1–19 years of age). The child:mother PFAA ratio was stratified by possible determinants. Results are summarized as geometric mean ratios and correlation coefficients between mother–child pairs, overall and within strata. Results: Child and mother PFOA and PFOS concentrations were correlated (r = 0.82 and 0.26, respectively). Up to about 12 years of age, children had higher serum PFOA concentrations than did their mothers. The highest child:mother PFOA ratio was found among children ≤ 5 years (44% higher than their mothers), which we attribute to in utero exposure and to exposure via breast milk and drinking water. Higher PFOS concentrations in children persisted until at least 19 years of age (42% higher than their mothers). Boys > 5 years of age had significantly higher PFOA and PFOS child:mother ratios than did girls. Conclusion: Concentrations of both PFOA and PFOS tended to be higher in children than in their mothers. This difference persisted until they were about 12 years of age for PFOA and at least 19 years of age for PFOS. PMID:22271837

  2. Serum bile acids in hepatobiliary disease.

    PubMed Central

    Bouchier, I A; Pennington, C R

    1978-01-01

    We review the estimation of total and individual serum bile acids to detect the presence and nature of hepatobiliary disease. The different methods for measuring serum bile acids are discussed. PMID:355064

  3. [Chemical weapons and chemical terrorism].

    PubMed

    Nakamura, Katsumi

    2005-10-01

    Chemical Weapons are kind of Weapons of Mass Destruction (WMD). They were used large quantities in WWI. Historically, large quantities usage like WWI was not recorded, but small usage has appeared now and then. Chemical weapons are so called "Nuclear weapon for poor countrys" because it's very easy to produce/possession being possible. They are categorized (1) Nerve Agents, (2) Blister Agents, (3) Cyanide (blood) Agents, (4) Pulmonary Agents, (5) Incapacitating Agents (6) Tear Agents from the viewpoint of human body interaction. In 1997 the Chemical Weapons Convention has taken effect. It prohibits chemical weapons development/production, and Organization for the Prohibition of Chemical Weapons (OPCW) verification regime contributes to the chemical weapons disposal. But possibility of possession/use of weapons of mass destruction by terrorist group represented in one by Matsumoto and Tokyo Subway Sarin Attack, So new chemical terrorism countermeasures are necessary.

  4. Serum Dioxin Concentrations and Age at Menopause

    PubMed Central

    Eskenazi, Brenda; Warner, Marcella; Marks, Amy R.; Samuels, Steven; Gerthoux, Pier ario; Vercellini, Paolo; Olive, David L.; Needham, Larry; Patterson, Donald G.; Mocarelli, Paolo

    2005-01-01

    2,3,7,8-Tetrachlorobenzo-p-dioxin (TCDD), a halogenated compound that binds the aryl hydrocarbon receptor, is a by-product of numerous industrial processes including waste incineration. Studies in rats and monkeys suggest that TCDD may affect ovarian function. We examined the relationship of TCDD and age at menopause in a population of women residing near Seveso, Italy, in 1976, at the time of a chemical plant explosion. We included 616 of the women who participated 20 years later in the Seveso Women’s Health Study. All women were premenopausal at the time of the explosion, had TCDD levels measured in serum collected soon after the explosion, and were ≥ 35 years of age at interview. Using proportional hazards modeling, we found a 6% nonsignificant increase in risk of early menopause with a 10-fold increase in serum TCDD. When TCDD levels were categorized, compared with women in the lowest quintile (< 20.4 ppt), women in quintile 2 (20.4–34.2 ppt) had a hazard ratio (HR) of 1.1 (p = 0.77), quintile 3 (34.3–54.1 ppt) had an HR of 1.4 (p = 0.14), quintile 4 (54.2–118 ppt) had an HR of 1.6 (p = 0.10), and quintile 5 (> 118 ppt) had an HR of 1.1 (p = 0.82) for risk of earlier menopause. The trend toward earlier menopause across the first four quintiles is statistically significant (p = 0.04). These results suggest a nonmonotonic dose-related association with increasing risk of earlier menopause up to about 100 ppt TCDD, but not above. PMID:16002373

  5. Chemical microsensors

    DOEpatents

    Li, DeQuan; Swanson, Basil I.

    1995-01-01

    An article of manufacture is provided including a substrate having an oxide surface layer and a selective thin film of a cyclodextrin derivative chemically bound upon said substrate, said film is adapted for the inclusion of a selected organic compound therewith. Such an article can be either a chemical sensor capable of detecting a resultant mass change from inclusion of the selected organic compound or a chemical separator capable of reversibly selectively separating a selected organic compound.

  6. Immunological basis of serum resistance of Neisseria gonorrhoeae.

    PubMed

    Schneider, H; Griffiss, J M; Williams, G D; Pier, G B

    1982-01-01

    The immunological basis for resistance of certain strains of Neisseria gonorrhoeae to the bactericidal action of normal human serum was studied by investigating the potential role of factors which are known to interfere with each of the sequential steps that result in immune lysis of Gram-negative bacteria. Strains of N. gonorrhoeae were characterized as serum-sensitive (sers) or serum-resistant (serr) on the basis of their sensitivity to lysis by the sera of six normal individuals. Neither intrinsic resistance to the lytic action of activated human complement nor inaccessibility of the cell membrane to C5b accounted for serr. Outer membrane lipopolysaccharide (LPS) was the target antigen for lytic antibody in normal human sera. The gross chemical composition and molecular size of the LPS of the strains were heterogeneous and no consistent patterns of differences between those extracted from serr and from sers strains were found. Neither IgA nor IgG 'blocking' antibody in normal human serum was responsible for serr. We conclude that serr results from the absence from the LPS of the strains of antigenic loci for the lytic antibody in most normal human sera, or, expressed as a function of the host, the absence from the sera of most normal humans of lytic antibody directed against LPS antigenic loci for immune lysis.

  7. Serum Survivin Increases in Prolactinoma

    PubMed Central

    Dellal, Fatma Dilek; Niyazoglu, Mutlu; Gorar, Suheyla; Ademoglu, Esranur; Candan, Zehra; Bekdemir, Handan; Hacioglu, Yalcin; Kaya, Fatih Oner

    2015-01-01

    Background Prolactinoma is the most common adult pituitary adenoma. Survivin is a member of the family of inhibitors of apoptosis proteins. Its expression is observed in many tumors. Survivin expression has shown in prolactinoma tissue before but no study exists showing serum survivin level. The aim of the present study was to investigate serum survivin levels in patients with prolactinoma and demonstrate its value in diagnosis of the disease. Methods The group of patients consisted of 25 women, aged from 17 to 51 years. As a control group, 21 healthy women, aged from 22 to 45 years were included. Twenty patients had microprolactinoma, while five patients had macroprolactinoma. All patients had received dopamine agonist treatment. Serum survivin levels were measured in all of the groups. Results Survivin levels were significantly higher in prolactinoma patients compared to controls (19.04 (10 - 38) pg/mL; 15.05 (8 - 22) pg/mL; P = 0.042). There was no difference between microadenoma and macroadenoma patients in survivin levels (19.22 (10 - 38) pg/mL; 18.40 (16 - 22) pg/mL; P = 0.914). In correlation analysis, survivin was not correlated with other parameters. Conclusions We consider that higher survivin levels might be a molecular marker predicting the presence of prolactinoma and may be useful for the diagnosis. But large-scale research is needed to clarify its role in diagnosis of prolactinoma patients. PMID:25699121

  8. Chemical sensors

    DOEpatents

    Lowell, J.R. Jr.; Edlund, D.J.; Friesen, D.T.; Rayfield, G.W.

    1991-07-02

    Sensors responsive to small changes in the concentration of chemical species are disclosed. The sensors comprise a mechanochemically responsive polymeric film capable of expansion or contraction in response to a change in its chemical environment. They are operatively coupled to a transducer capable of directly converting the expansion or contraction to a measurable electrical response. 9 figures.

  9. Chemical Peels

    MedlinePlus

    ... the complications or potential side effects of a chemical peel? Temporary or permanent change in skin color, particularly for women on birth control pills, who subsequently become pregnant or have a history of brownish facial ... after having a chemical peel? All peels require some follow-up care: ...

  10. Chemical preconcentrator

    DOEpatents

    Manginell, Ronald P.; Frye-Mason, Gregory C.

    2001-01-01

    A chemical preconcentrator is disclosed with applications to chemical sensing and analysis. The preconcentrator can be formed by depositing a resistive heating element (e.g. platinum) over a membrane (e.g. silicon nitride) suspended above a substrate. A coating of a sorptive material (e.g. a microporous hydrophobic sol-gel coating or a polymer coating) is formed on the suspended membrane proximate to the heating element to selective sorb one or more chemical species of interest over a time period, thereby concentrating the chemical species in the sorptive material. Upon heating the sorptive material with the resistive heating element, the sorbed chemical species are released for detection and analysis in a relatively high concentration and over a relatively short time period. The sorptive material can be made to selectively sorb particular chemical species of interest while not substantially sorbing other chemical species not of interest. The present invention has applications for use in forming high-sensitivity, rapid-response miniaturized chemical analysis systems (e.g. a "chem lab on a chip").

  11. Chemical sensors

    DOEpatents

    Lowell, Jr., James R.; Edlund, David J.; Friesen, Dwayne T.; Rayfield, George W.

    1991-01-01

    Sensors responsive to small changes in the concentration of chemical species are disclosed, comprising (a) a mechanochemically responsive polymeric film capable of expansion or contraction in response to a change in its chemical environment, operatively coupled to (b) a transducer capable of directly converting said expansion or contraction to a measurable electrical response.

  12. Chemical Emergencies

    MedlinePlus

    ... agents such as sarin and VX. Many hazardous chemicals are used in industry - for example, chlorine, ammonia, and benzene. Some can be made from everyday items such as household cleaners. Although there are no guarantees of safety during a chemical emergency, you can take actions to protect yourself. ...

  13. Chemical threats.

    PubMed

    Fry, Donald E

    2006-06-01

    The use of chemical agents as military weapons has been recognized for many centuries but reached the most feared and publicized level during World War I. Considerable political effort has been exercised in the twentieth century to restrict military strategies with chemicals. However, considerable concern currently exists that chemical weapons may be used as agents in civilian terrorism. The distribution of acetaminophen tablets contaminated with potassium cyanide and the release of sarin in the Tokyo sub-way system show that larger-scale deployment of chemical agents can be a reality. This reality makes it necessary for civilian disaster-planning strategies to incorporate an understanding of chemical agents, their effects, and the necessary treatment.

  14. Hematology and serum chemistry of the island spotted skunk on Santa Cruz Island.

    PubMed

    Crooks, Kevin R; Garcelon, D K; Scott, Cheryl A; Wilcox, Jeffery T; Timm, Steven F; Van Vuren, Dirk H

    2003-04-01

    We determined serum biochemistry and hematologic values for island spotted skunks (Spilogale gracilis amphiala) on Santa Cruz Island (California, USA). Samples were collected from island spotted skunks chemically restrained with ketamine hydrochloride and acepromazine in August 1999 (dry season) and from skunks manually restrained in August 2000 (dry season) and January 2001 (wet season). One parameter, glucose, significantly differed with season, with higher levels during the wet season. Serum chemistry and hematologic profiles suggest that method of restraint (manual or chemical), as well as other methodologic details, may influence blood characteristics in the island spotted skunk.

  15. [Serum sclerostin levels and metabolic bone diseases].

    PubMed

    Yamauchi, Mika; Sugimoto, Toshitsugu

    2013-06-01

    Serum sclerostin levels are being investigated in various metabolic bone diseases. Since serum sclerostin levels are decreased in primary hyperparathyroidism and elevated in hypoparathyroidism, parathyroid hormone (PTH) is thought to be a regulatory factor for sclerostin. Serum sclerostin levels exhibit a significant positive correlation with bone mineral density. On the other hand, a couple of studies on postmenopausal women have shown that high serum sclerostin levels are a risk factor for fracture. Although glucocorticoid induced osteoporosis and diabetes are both diseases that reduce bone formation, serum sclerostin levels have been reported to be decreased in the former and elevated in the latter, suggesting differences in the effects of sclerostin in the two diseases. Serum sclerostin levels are correlated with renal function, and increase with reduction in renal function. Serum sclerostin level may be a new index of bone assessment that differs from bone mineral density and bone metabolic markers.

  16. A hybrid fluorous monolithic capillary column with integrated nanoelectrospray ionization emitter for determination of perfluoroalkyl acids by nano-liquid chromatography-nanoelectrospray ionization-mass spectrometry/mass spectrometry.

    PubMed

    Zhang, Haiyang; Ou, Junjie; Wei, Yinmao; Wang, Hongwei; Liu, Zhongshan; Zou, Hanfa

    2016-04-01

    A hybrid fluorous monolithic column was simply prepared via photo-initiated free radical polymerization of an acrylopropyl polyhedral oligomeric silsesquioxane (acryl-POSS) and a perfluorous monomer (2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl acrylate) in UV-transparent fused-silica capillaries within 5min. The physical characterization of hybrid fluorous monolith, including scanning electron microscopy (SEM), Fourier transform infrared (FT-IR) spectroscopy, mercury intrusion porosimetry (MIP) and nitrogen adsorption/desorption measurement was performed. Chromatographic performance was also evaluated by capillary liquid chromatography (cLC). Due to the fluorous-fluorous interaction between fluorous monolith and analytes, fluorobenzenes could well be separated, and the column efficiencies reached 86,600-92,500plates/m at the velocity of 0.87mm/s for alkylbenzenes and 51,900-76,000plates/m at the velocity of 1.10mm/s for fluorobenzenes. Meanwhile, an approach to integrate nanoelectrospray ionization (ESI) emitter with hybrid fluorous monolithic column was developed for quantitative determination of perfluoroalkyl acids by nanoHPLC-ESI-MS/MS. The integration design could minimize extracolumn volume, thus excluding undesirable peak broadening and improving separation performance. PMID:26916593

  17. Fluorine-Decoupled Carbon Spectroscopy for the Determination of Configuration at Fully Substituted, Trifluoromethyl- and Perfluoroalkyl-Bearing Carbons: Comparison with 19F–1H Heteronuclear Overhauser Effect Spectroscopy

    PubMed Central

    2016-01-01

    The synthesis of a series of α-trifluoromethylcyclohexanols and analogous trimethylsilyl ethers by addition of the Ruppert–Prakash reagent to substituted cyclohexanones is presented. A method for the assignment of configuration of such compounds, of related α-trifluoromethylcyclohexylamines and of quaternary trifluoromethyl-substituted carbons is described based on the determination of the 3JCH coupling constant between the fluorine-decoupled 13CF3 resonance and the vicinal hydrogens. This method is dubbed fluorine-decoupled carbon spectroscopy and abbreviated FDCS. The method is also applied to the configurational assignment of substances bearing mono-, di-, and perfluoroalkyl rather than trifluoromethyl groups. The configuration of all substances was verified by either 19F−1H heteronuclear Overhauser spectroscopy (HOESY) or X-ray crystallography. The relative merits of FDCS and HOESY are compared and contrasted. 2JCH, 3JCH, and 4JCH coupling constants to 19F decoupled CF3 groups in alkenes and arenes have also been determined and should prove to be useful in the structural assignment of trifluoromethylated alkenes and arenes. PMID:25561269

  18. Fluorine-decoupled carbon spectroscopy for the determination of configuration at fully substituted, trifluoromethyl- and perfluoroalkyl-bearing carbons: comparison with 19F-1H heteronuclear Overhauser effect spectroscopy.

    PubMed

    Mandhapati, Appi Reddy; Kato, Takayuki; Matsushita, Takahiko; Ksebati, Bashar; Vasella, Andrea; Böttger, Erik C; Crich, David

    2015-02-01

    The synthesis of a series of α-trifluoromethylcyclohexanols and analogous trimethylsilyl ethers by addition of the Ruppert-Prakash reagent to substituted cyclohexanones is presented. A method for the assignment of configuration of such compounds, of related α-trifluoromethylcyclohexylamines and of quaternary trifluoromethyl-substituted carbons is described based on the determination of the (3)J(CH) coupling constant between the fluorine-decoupled (13)CF3 resonance and the vicinal hydrogens. This method is dubbed fluorine-decoupled carbon spectroscopy and abbreviated FDCS. The method is also applied to the configurational assignment of substances bearing mono-, di-, and perfluoroalkyl rather than trifluoromethyl groups. The configuration of all substances was verified by either (19)F-(1)H heteronuclear Overhauser spectroscopy (HOESY) or X-ray crystallography. The relative merits of FDCS and HOESY are compared and contrasted. (2)J(CH), (3)J(CH), and (4)J(CH) coupling constants to (19)F decoupled CF3 groups in alkenes and arenes have also been determined and should prove to be useful in the structural assignment of trifluoromethylated alkenes and arenes.

  19. A hybrid fluorous monolithic capillary column with integrated nanoelectrospray ionization emitter for determination of perfluoroalkyl acids by nano-liquid chromatography-nanoelectrospray ionization-mass spectrometry/mass spectrometry.

    PubMed

    Zhang, Haiyang; Ou, Junjie; Wei, Yinmao; Wang, Hongwei; Liu, Zhongshan; Zou, Hanfa

    2016-04-01

    A hybrid fluorous monolithic column was simply prepared via photo-initiated free radical polymerization of an acrylopropyl polyhedral oligomeric silsesquioxane (acryl-POSS) and a perfluorous monomer (2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl acrylate) in UV-transparent fused-silica capillaries within 5min. The physical characterization of hybrid fluorous monolith, including scanning electron microscopy (SEM), Fourier transform infrared (FT-IR) spectroscopy, mercury intrusion porosimetry (MIP) and nitrogen adsorption/desorption measurement was performed. Chromatographic performance was also evaluated by capillary liquid chromatography (cLC). Due to the fluorous-fluorous interaction between fluorous monolith and analytes, fluorobenzenes could well be separated, and the column efficiencies reached 86,600-92,500plates/m at the velocity of 0.87mm/s for alkylbenzenes and 51,900-76,000plates/m at the velocity of 1.10mm/s for fluorobenzenes. Meanwhile, an approach to integrate nanoelectrospray ionization (ESI) emitter with hybrid fluorous monolithic column was developed for quantitative determination of perfluoroalkyl acids by nanoHPLC-ESI-MS/MS. The integration design could minimize extracolumn volume, thus excluding undesirable peak broadening and improving separation performance.

  20. Perfluoroalkylated substances (PFASs) and legacy persistent organic pollutants (POPs) in halibut and shrimp from coastal areas in the far north of Norway: Small survey of important dietary foodstuffs for coastal communities.

    PubMed

    Carlsson, Pernilla; Crosse, John D; Halsall, Crispin; Evenset, Anita; Heimstad, Eldbjørg S; Harju, Mikael

    2016-04-15

    Halibut (Hippoglossus hippoglossus) and shrimps (Pandalus borealis) are regular foodstuffs for communities in northern Norway and important species for the coastal fishing industry. This is the first study to present a comprehensive overview of the contaminant status of these species, with emphasis on unregulated perfluoroalkylated substances (PFAS). The contaminant concentrations were low and within tolerable levels for human dietary exposure. Median Σpolychlorinated biphenyls (PCB) were 4.9 and 2.5ng/g ww for halibut and unpeeled shrimps, respectively. Concentrations of perfluorooctane sulfonate (PFOS) - the most abundant PFASs - were 0.9 and 2.7ng/g ww in halibut and shrimp, respectively. The halibut fillets were dominated by PCBs, which contributed to 50% of the total POPs load, followed by ΣDDTs; 26% and PFASs (18%), whereas shrimps were dominated by PFASs (74%). ΣPBDEs (polybrominated diphenyl ethers) contributed to 1-4% of the total POP load. Local sources are not contributing significantly to the contaminant burden in these species. PMID:26948293

  1. Host and environmental determinants of polychlorinated aromatic hydrocarbons in serum of adolescents.

    PubMed Central

    Nawrot, Tim S; Staessen, Jan A; Den Hond, Elly M; Koppen, Gudrun; Schoeters, Greet; Fagard, Robert; Thijs, Lutgarde; Winneke, Gerhard; Roels, Harry A

    2002-01-01

    This study investigated host factors and environmental factors as potential determinants of polychlorinated aromatic hydrocarbons (PCAHs) in serum of adolescents. We recruited 200 participants (80 boys and 120 girls), with a mean age of 17.4 years (SD, 0.8), in Belgium from a rural control area (Peer) and from two polluted suburbs of Antwerp where a nonferrous smelter (Hoboken) and waste incinerators (Wilrijk) are located. We quantified polychlorinated biphenyls (PCBs; congeners 138, 153, and 180) in serum by gas chromatography and obtained the toxic equivalents (TEQs) of PCAHs in serum with the chemically activated luciferase gene expression bioassay (CALUX). Serum PCB concentration was higher in boys than in girls (1.67 vs. 1.02 nmol/L or 377 vs. 210 pmol/g serum lipids; p< 0.001). In the whole adolescent group, multiple regression showed that serum PCB concentration decreased 0.06 nmol/L per 1% increase in body fat content (p< 0.001) and increased 0.39 nmol/L and 0.14 nmol/L per 1 mmol/L increase in serum concentrations of triglycerides (p < 0.001) and cholesterol (p = 0.002), respectively. Host factors explained 44% of the serum PCB variance. In the same model, serum PCB concentration increased 0.14 nmol/L with 10 weeks of breast-feeding (p< 0.001) and 0.06 nmol/L with intake of 10 g animal fat per day (p < 0.001), and was associated with residence in the waste incinerator area (9% higher; p = 0.04); 11% of the variance could be explained by these environmental factors. The geometric mean of the serum TEQ value was similar in boys and girls (0.15 TEQ ng/L or 33.0 pg/g serum lipids). In multiple regression, TEQ in serum decreased 0.03 ng/L per centimeter increase in triceps skinfold (p = 0.006) and was 29% higher in subjects living close to the nonferrous smelter (p < 0.001). This study showed that in 16- to 18-year-old teenagers host factors are important determinants of serum concentrations of PCAHs, whereas environmentally related determinants may to some

  2. SERUM PROTEIN PROFILES IN COCCIDIOIDOMYCOSIS

    PubMed Central

    Reed, William B.; Heiskell, Charles L.; Holeman, Charles W.; Carpenter, Charles

    1962-01-01

    Serum protein analysis is a valuable addition to the present methods for evaluating the status of the individual patient with coccidioidomycosis. The albumin protein and albumin glycoprotein decrease and gamma protein increases in relation to severity of infection. In 40 patients with coccidioidomycosis, changes in individual protein fractions could be significantly correlated with conventional laboratory tests, such as the complement fixation test, erythrocyte sedimentation rate and hematocrit. Changes in the alpha, glycoprotein concentration, the erythrocyte sedimentation rate and the hematocrit value appear to be related to the degree of inflammation, while the changes in the gamma protein and the beta, glycoprotein appear to be related to the specific antibody response. PMID:13973566

  3. Serum protein profiles in coccidioidomycosis.

    PubMed

    REED, W B; HEISKELL, C L; HOLEMAN, C W; CARPENTER, C

    1962-12-01

    Serum protein analysis is a valuable addition to the present methods for evaluating the status of the individual patient with coccidioidomycosis. The albumin protein and albumin glycoprotein decrease and gamma protein increases in relation to severity of infection. In 40 patients with coccidioidomycosis, changes in individual protein fractions could be significantly correlated with conventional laboratory tests, such as the complement fixation test, erythrocyte sedimentation rate and hematocrit. Changes in the alpha, glycoprotein concentration, the erythrocyte sedimentation rate and the hematocrit value appear to be related to the degree of inflammation, while the changes in the gamma protein and the beta, glycoprotein appear to be related to the specific antibody response.

  4. Reduction of blood serum cholesterol

    NASA Technical Reports Server (NTRS)

    Winitz, M. (Inventor)

    1974-01-01

    By feeding a human subject as the sole source of sustenance a defined diet wherein the carbohydrate consists substantially entirely of glucose, maltose or a polysaccharide of glucose, the blood serum cholesterol level of the human subject is substantially reduced. If 25 percent of the carbohydrate is subsequently supplied in the form of sucrose, an immediate increase from the reduced level is observed. The remainder of the defined diet normally includes a source of amino acids, such as protein or a protein hydrolysate, vitamins, minerals and a source of essential fatty acid.

  5. Neptunium uptake by serum transferrin.

    PubMed

    Llorens, Isabelle; Den Auwer, Christophe; Moisy, Philippe; Ansoborlo, Eric; Vidaud, Claude; Funke, Harld

    2005-04-01

    Although of major impact in terms of biological and environmental hazards, interactions of actinide cations with biological molecules are only partially understood. Human serum transferrin (Tf) is one of the major iron carriers in charge of iron regulation in the cell cycle and consequently contamination by actinide cations is a critical issue of nuclear toxicology. Combined X-ray absorption spectroscopy (XAS) and near infrared absorption spectrometry were used to characterize a new complex between Tf and Np (IV) with the synergistic nitrilotriacetic acid (NTA) anion. Description of the neptunium polyhedron within the iron coordination site is given.

  6. Serum enzyme activities after cardioversion

    PubMed Central

    Mandecki, Tadeusz; Giec, Leszek; Kargul, Włodzimierz

    1970-01-01

    Serum aspartate aminotransferase (SGOT), alanine aminotransferase (SGPT), creatinine phosphokinase (CPK), and butyric acid dehydrogenase (BDH) were determined in 94 patients before, 1½ hours, and 24 hours after cardioversion. An increase in SGOT and CPK activity was observed 24 hours after cardioversion in the group of patients treated with two or more DC shocks. The importance of this enzyme activity increase is discussed. It originates in the skeletal muscles and probably has no clinical significance, as no other signs of myocardial damage were observed simultaneously in a large group of patients. PMID:5470040

  7. Chemical peeling.

    PubMed

    Forte, R; Hack, J; Jackson, I T

    1993-01-01

    This article explores the wide range of chemical facial peels, which include phenol, trichloroacetic acid, and alpha-hydroxy acids. The application of these substances will be described in addition to the contraindications to this type of treatment.

  8. Unnecessary Chemicals

    ERIC Educational Resources Information Center

    Johnson, Anita

    1978-01-01

    Discusses the health hazards resulting from chemical additions of many common products such as cough syrups, food dyes, and cosmetics. Steps being taken to protect consumers from these health hazards are included. (MDR)

  9. Assessment of infant exposure to food chemicals: the French Total Diet Study design.

    PubMed

    Hulin, M; Bemrah, N; Nougadère, A; Volatier, J L; Sirot, V; Leblanc, J C

    2014-01-01

    As part of the previous French Total Diet Studies (TDS) focusing on exposure to food chemicals in the population aged 3 years and older, the French Agency for Food, Environmental and Occupational Health & Safety (ANSES) launched a specific TDS on infants to complete its overall chemical food safety programme for the general population. More than 500 chemical substances were analysed in food products consumed by children under 3 years old, including nutrients, several endocrine disruptors resulting from human activities (polychlorinated biphenyls, dioxins and furans, brominated flame retardants, perfluoroalkyl acids, pesticide residues, etc.) or migrating from food contact materials such as bisphenol A or phthalates, but also natural substances such as mycotoxins, phytoestrogens and steroids. To obtain a representative and general view of infant food consumption, food items were selected based on results of a national consumption survey conducted specifically on this population. Moreover, a specific study on food was conducted on 429 households to determine which home-cooking practices are employed to prepare food consumed by infants. Overall, the targeted chemical substances were analysed in more than 450 food samples, representing the purchase and home-cooking practices of over 5500 food products. Foods included common foods such as vegetables, fruit or cakes as well as specific infant foods such as infant formula or jarred baby food. The sampling plan covered over 80% of the total diet. Specificities in infant food consumption and habits were therefore considered to define this first infant TDS. This study, conducted on a large scale and focusing on a particularly sensitive population, will provide accurate information on the dietary exposure of children under 3 years to food chemicals, especially endocrine disruptors, and will be particularly useful for risk assessment analysis under the remit of ANSES' expert committees.

  10. Chemical sensors

    DOEpatents

    Lowell, J.R. Jr.; Edlund, D.J.; Friesen, D.T.; Rayfield, G.W.

    1992-06-09

    Sensors responsive to small changes in the concentration of chemical species are disclosed, comprising a mechanicochemically responsive polymeric film capable of expansion or contraction in response to a change in its chemical environment, either operatively coupled to a transducer capable of directly converting the expansion or contraction to a measurable electrical or optical response, or adhered to a second inert polymeric strip, or doped with a conductive material. 12 figs.

  11. Chemical sensors

    DOEpatents

    Lowell, Jr., James R.; Edlund, David J.; Friesen, Dwayne T.; Rayfield, George W.

    1992-01-01

    Sensors responsive to small changes in the concentration of chemical species are disclosed, comprising a mechanicochemically responsive polymeric film capable of expansion or contraction in response to a change in its chemical environment, either operatively coupled to a transducer capable of directly converting the expansion or contraction to a measurable electrical or optical response, or adhered to a second inert polymeric strip, or doped with a conductive material.

  12. International Reference Preparation of Rheumatoid Arthritis Serum

    PubMed Central

    Anderson, S. G.; Bentzon, M. W.; Houba, V.; Krag, P.

    1970-01-01

    The National Institute for Medical Research, London, England, was requested by the WHO Expert Committee on Biological Standardization to arrange a collaborative study of the serum pool they had obtained, to determine its suitability to serve as an international reference preparation of rheumatoid arthritis serum. A batch of this serum was assayed by 11 laboratories in 7 countries against 30 test preparations. On the basis of the results obtained, the serum has been established as the International Reference Preparation of Rheumatoid Arthritis Serum and the International Unit of Rheumatoid Arthritis Serum has been defined as the activity contained in 0.171 mg of the international reference preparation. A description is also given of the British reference preparation of rabbit antibody to sheep red blood cells (amboceptor) and this material was also tested in the collaborative study. PMID:5310143

  13. Effect of Pregnancy Serum on Experimental Inflammation

    PubMed Central

    Persellin, R. H.; Vance, S. E.; Peery, A.

    1974-01-01

    Experimental inflammation induced in the rat by injection of carrageenin was suppressed by prior administration of pooled serum obtained from pregnant human females. Inflammatory oedema in the rat hind paw measured by a plethysmograph was inhibited 81% by 10 ml of pregnancy serum pool and the effect was dose related. Non-pregnant female serum was inhibitory to a lesser degree and no anti-inflammatory action was detected using cord serum. Although adrenal corticosteroid hormones could modify this inflammatory model, their presence in the serum pools could not account for the effects observed. Since carrageenin is sequestered within phagolysosomes and provokes release of their inflammation-inducing contents, it is suggested that the protective effect of pregnancy serum on carrageenin inflammation is mediated via lysosomal stabilization. PMID:4835795

  14. Effect of cord blood serum on ex vivo human limbal epithelial cell culture.

    PubMed

    Chakraborty, Anindita; Dutta, Jayanta; Das, Sumantra; Datta, Himadri

    2012-12-01

    Limbal cell transplantation is an efficacious procedure for rehabilitation of visual acuity in patients with severe ocular surface disorders. Cultivation of limbal epithelial stem cell with fetal bovine serum for transplantation has been a promising treatment for reconstructing the ocular surface in severe limbal stem cell deficiency caused by Steven Johnson syndrome, chemical or thermal injury. This technique of "cell therapy" has been accepted worldwide but the cost of cultivating the cells for transplantation is high. The objective of this study was to investigate the effect of cord blood serum in place of fetal bovine serum on the growth of human limbal epithelial cell culture. Our group has experimented with human cord blood serum which was obtained free of cost from willing donors. The use of human cord blood serum in place of fetal bovine serum for ex vivo culture of limbal stem cell has helped us in reducing the cost of culture. Fresh human limbal tissues from donor cadavers were cultured on intact and denuded amniotic membrane. Cells were proliferated in vitro with cell culture media containing human cord blood serum. Reverse transcription-polymerase chain reaction and immunofluorescence cytochemistry of cultured human limbal epithelial stem cell was done for characterization of the cells.

  15. Chemical sensors

    SciTech Connect

    Hubbard, C.W.; Gordon, R.L.

    1987-05-01

    The revolution in analytical chemistry promised by recent developments in the field of chemical sensors has potential for significant positive impact on both research and production activities conducted by and for the Department of Energy. Analyses which were, in the past, performed only with a roomful of expensive equipment can now be performed with miniature solid-state electronic devices or small optical probes. Progress in the development of chemical sensors has been rapid, and the field is currently growing at a great rate. In accordance, Pacific Northwest Laboratory initiated a survey of recent literature so that contributors to active programs in research on analytical methods could be made aware of principles and applications of this new technology. This report presents the results of that survey. The sensors discussed here are divided into three types: micro solid-state devices, optical sensors, and piezoelectric crystal devices. The report is divided into three corresponding sections. The first section, ''Micro Solid-State Devices,'' discusses the design, operation, and application of electronic sensors that are produced in much the same way as standard solid-state electronic devices. The second section, ''Optrodes,'' covers the design and operation of chemical sensors that use fiber optics to detect chemically induced changes in optical properties. The final section, ''Piezoelectric Crystal Detectors,'' discusses two types of chemical sensors that depend on the changes in the properties of an oscillating piezoelectric crystal to detect the presence of certain materials. Advantages and disadvantages of each type of sensor are summarized in each section.

  16. Chemical networks

    NASA Astrophysics Data System (ADS)

    Thi, Wing-Fai

    2015-09-01

    This chapter discusses the fundamental ideas of how chemical networks are build, their strengths and limitations. The chemical reactions that occur in disks combine the cold phase reactions used to model cold molecular clouds with the hot chemistry applied to planetary atmosphere models. With a general understanding of the different types of reactions that can occur, one can proceed in building a network of chemical reactions and use it to explain the abundance of species seen in disks. One on-going research subject is finding new paths to synthesize species either in the gas-phase or on grain surfaces. Specific formation routes for water or carbon monoxide are discussed in more details. 13th Lecture of the Summer School "Protoplanetary Disks: Theory and Modelling Meet Observations"

  17. The Effects of Perfluorinated Chemicals on Adipoctye Differentiation In Vitro

    EPA Science Inventory

    The 3T3-L1 preadipocyte culture system has been used to examine numerous compounds that influence adipocyte differentiation or function. The perfluoroalkyl acids (PFAAs), used as surfactants in a variety of industrial applications, are of concern as environmental contaminants tha...

  18. Chemical Mahjong

    ERIC Educational Resources Information Center

    Cossairt, Travis J.; Grubbs, W. Tandy

    2011-01-01

    An open-access, Web-based mnemonic game is described whereby introductory chemistry knowledge is tested using mahjong solitaire game play. Several tile sets and board layouts are included that are themed upon different chemical topics. Introductory tile sets can be selected that prompt the player to match element names to symbols and metric…

  19. Delicious Chemicals.

    ERIC Educational Resources Information Center

    Barry, Dana M.

    This paper presents an approach to chemistry and nutrition that focuses on food items that people consider delicious. Information is organized according to three categories of food chemicals that provide energy to the human body: (1) fats and oils; (2) carbohydrates; and (3) proteins. Minerals, vitamins, and additives are also discussed along with…

  20. Chemical Indicators.

    ERIC Educational Resources Information Center

    Prombain, Dorothy R.; And Others

    This science sourcebook was written for intermediate grade teachers to provide guidance in teaching a specially developed unit on chemical indicators. Directions and suggestions for guiding student science activities are given. Some of the activities concern soil testing, crystals, and household powders such as sugar and salt. A list of necessary…

  1. Amorphous fluorocarbon polymer (a-C:F) films obtained by plasma enhanced chemical vapor deposition from perfluoro-octane (C8F18) vapor I: Deposition, morphology, structural and chemical properties

    NASA Astrophysics Data System (ADS)

    Biloiu, Costel; Biloiu, Ioana Arabela; Sakai, Yosuke; Suda, Yoshiyuki; Ohta, Akitsugu

    2004-01-01

    The method of obtaining amorphous fluorocarbon polymer (a-C:F) films by plasma enhanced chemical vapor deposition in a capacitively coupled, 13.56 MHz reactor, from a new monomer, namely perfluoro-octane (C8F18) vapor, is presented. For monomer pressure ranging from 0.2 to 1 Torr and input power density from 0.15 to 0.85 W/cm3, the maximum deposition rate reached 300 nm/min, while 10% monomer dilution with argon led to a deposition rate of 200 nm/min. The film surface and bulk morphologies, chemical and structural compositions were investigated using scanning electron microscopy, x-ray photoelectron spectroscopy, and Fourier transform infrared spectroscopy. It was revealed that the films have a dense and compact structure. The fluorine to carbon ratio (F/C) of the films was between 1.57 and 1.75, and the degree of cross-linking was between 55% and 58%. The relative amount of perfluoroalkyl (CF2) groups in the films was 29%. The FTIR spectra showed absorption bands corresponding to the different vibrational modes of CF, CF2, and CF3 moieties. .

  2. Predictors of Serum Chlorinated Pesticide Concentrations among Prepubertal Russian Boys

    PubMed Central

    Williams, Paige L.; Burns, Jane S.; Sergeyev, Oleg; Korrick, Susan A.; Lee, Mary M.; Birnbaum, Linda S.; Revich, Boris; Altshul, Larisa M.; Patterson, Donald G.; Turner, Wayman E.; Hauser, Russ

    2013-01-01

    Background: Few studies have evaluated predictors of childhood exposure to organochlorine pesticides (OCPs), a class of lipophilic persistent chemicals. Objectives: Our goal was to identify predictors of serum OCP concentrations—hexachlorobenzene (HCB), β-hexachlorocyclohexane (β-HCH), and p,p-dichlorodiphenyldichloroethylene (p,p´-DDE)—among boys in Chapaevsk, Russia. Methods: Between 2003 and 2005, 499 boys 8–9 years of age were recruited in a prospective cohort. The initial study visit included a physical examination; blood collection; health, lifestyle, and food-frequency questionnaires; and determination of residential distance from a local factory complex that produced HCB and β-HCH. Fasting serum samples were analyzed for OCPs at the U.S. Centers for Disease Control and Prevention. General linear regression models were used to identify predictors of the boys’ serum HCB, β-HCH, and p,p´-DDE concentrations. Results: Among 355 boys with OCP measurements, median serum HCB, β-HCH, and p,p´-DDE concentrations were 158, 167, and 284 ng/g lipid, respectively. Lower body mass index, longer breastfeeding duration, and local dairy consumption were associated with higher concentrations of OCPs. Boys who lived < 2 km from the factory complex had 64% (95% CI: 37, 96) and 57% (95% CI: 32, 87) higher mean HCB and β-HCH concentrations, respectively, than boys who lived ≥ 5 km away. Living > 3 years in Chapaevsk predicted higher β-HCH concentrations, and having parents who lacked a high school education predicted higher p,p´-DDE concentrations. Conclusions: Among this cohort of prepubertal Russian boys, predictors of serum OCPs included consumption of local dairy products, longer local residence, and residential proximity to the local factory complex. Citation: Lam T, Williams PL, Burns JS, Sergeyev O, Korrick SA, Lee MM, Birnbaum LS, Revich B, Altshul LM, Patterson DG Jr, Turner WE, Hauser R. 2013. Predictors of serum chlorinated pesticide concentrations

  3. Serum fluoride and sialic acid levels in osteosarcoma.

    PubMed

    Sandhu, R; Lal, H; Kundu, Z S; Kharb, S

    2011-12-01

    Osteosarcoma is a rare malignant bone tumor most commonly occurring in children and young adults presenting with painful swelling. Various etiological factors for osteosarcoma are ionizing radiation, family history of bone disorders and cancer, chemicals (fluoride, beryllium, and vinyl chloride), and viruses. Status of fluoride levels in serum of osteosarcoma is still not clear. Recent reports have indicated that there is a link between fluoride exposure and osteosarcoma. Glycoproteins and glycosaminoglycans are an integral part of bone and prolonged exposure to fluoride for long duration has been shown to cause degradation of collagen and ground substance in bones. The present study was planned to analyze serum fluoride, sialic acid, calcium, phosphorus, and alkaline phosphatase levels in 25 patients of osteosarcoma and age- and sex-matched subjects with bone-forming tumours other than osteosarcoma and musculo-skeletal pain (controls, 25 each). Fluoride levels were analyzed by ISE and sialic acid was analyzed by Warren's method. Mean serum fluoride concentration was found to be significantly higher in patients with osteosarcoma as compared to the other two groups. The mean value of flouride in patients with other bone-forming tumors was approximately 50% of the group of osteosarcoma; however, it was significantly higher when compared with patients of group I. Serum sialic acid concentration was found to be significantly raised in patients with osteosarcoma as well as in the group with other bone-forming tumors as compared to the group of controls. There was, however, no significant difference in the group of patients of osteosarcoma when compared with group of patients with other bone-forming tumors. These results showing higher level of fluoride with osteosarcoma compared to others suggesting a role of fluoride in the disease.

  4. Interaction between human serum esterases and environmental metal compounds.

    PubMed

    Hernández, Antonio F; Gil, Fernando; Leno, Esther; López, Olga; Rodrigo, Lourdes; Pla, Antonio

    2009-07-01

    Paraoxonase-1 (PON1) and cholinesterase (BChE) are two of the major human serum esterases. Although most of variation in PON1 activity results from genetic factors, there is growing evidence that environmental chemicals also modulate its activity. The aim of this study was to investigate whether environmental exposure to metal compounds has any influence on those esterases. A cross-sectional study was conducted in a representative sample of the general population of Andalusia, South of Spain. PON1 activity against different substrates (paraoxon, phenylacetate, diazoxon and dihydrocoumarin) and BChE were measured in serum from 536 healthy subjects. Potential associations of these esterases with metal compounds, age, sex and body mass index as well as life-style habits (smoking, alcohol drinking and food habits) were explored. Multiple linear regression analysis showed that blood lead levels were significantly associated with increased PON1 in serum regardless of the substrate used for the assay. Mercury also showed a significant and direct association with PON1 towards paraoxon and phenylacetate. In turn, cadmium and zinc levels were significantly associated with a decreased PON1 activity (zinc was associated with all PON1 activities and cadmium with PON1 towards paraoxon and diazoxon). Arsenic, nickel and manganese failed to be significantly associated with any of the PON1 activities assayed. PON1 192R alloform predicted significantly higher levels of arsenic and lead. BChE, however, was inversely associated with serum levels of manganese and zinc. These results suggest that PON1 and BChE activities are modulated by background exposure to metal compounds, which may have implications in public health given the defensive role played by both enzyme proteins against environmental toxicants. The potential underlying mechanisms merit further investigation.

  5. Pediatric bupropion-induced serum sicknesslike reaction.

    PubMed

    Hack, Sabine

    2004-01-01

    This reports the first 2 cases of serum sicknesslike reaction to bupropion in children (age 12 and 14). Serum sicknesslike reactions are an example of immune-complex medicated disease. The cardinal symptoms of serum sickness are fever, lymphadenopathy, arthralgias or arthritis, and urticaria. Symptoms usually resolve without long-term sequela following discontinuation of the exogenous antigen. It is likely that serum sicknesslike reactions to bupropion are either relatively rare or underrecognized and underreported. Between May 1998 and May 2001, GlaxoSmith Kline received 172 reports of seizures (a well-known adverse drug reaction) and only 37 reports of serum sicknesslike reactions (Wooltorton 2002). We do not know if children and adolescents are more prone than adults to develop serum sicknesslike reactions to bupropion. Luckily, the reported cases of serum sicknesslike reactions to bupropion have not caused irreversible morbidity or mortality. Nevertheless, the symptoms are painful, temporarily disfiguring and disabling, and warrant prompt medical attention. Parents and patients should be educated about this potential side effect at the onset of treatment, because symptoms are similar to many infectious childhood illnesses, and the treatment of serum sicknesslike reactions to bupropion should include the discontinuation of bupropion.

  6. Serum Protein Profile Alterations in Hemodialysis Patients

    SciTech Connect

    Murphy, G A; Davies, R W; Choi, M W; Perkins, J; Turteltaub, K W; McCutchen-Maloney, S L; Langlois, R G; Curzi, M P; Trebes, J E; Fitch, J P; Dalmasso, E A; Colston, B W; Ying, Y; Chromy, B A

    2003-11-18

    Background: Serum protein profiling patterns can reflect the pathological state of a patient and therefore may be useful for clinical diagnostics. Here, we present results from a pilot study of proteomic expression patterns in hemodialysis patients designed to evaluate the range of serum proteomic alterations in this population. Methods: Surface-Enhanced Laser Desorption/Ionization Time-of-Flight Mass Spectrometry (SELDI-TOFMS) was used to analyze serum obtained from patients on periodic hemodialysis treatment and healthy controls. Serum samples from patients and controls were first fractionated into six eluants on a strong anion exchange column, followed by application to four array chemistries representing cation exchange, anion exchange, metal affinity and hydrophobic surfaces. A total of 144 SELDI-TOF-MS spectra were obtained from each serum sample. Results: The overall profiles of the patient and control samples were consistent and reproducible. However, 30 well-defined protein differences were observed; 15 proteins were elevated and 15 were decreased in patients compared to controls. Serum from one patient exhibited novel protein peaks suggesting possible additional changes due to a secondary disease process. Conclusion: SELDI-TOF-MS demonstrated dramatic serum protein profile differences between patients and controls. Similarity in protein profiles among dialysis patients suggests that patient physiological responses to end-stage renal disease and/or dialysis therapy have a major effect on serum protein profiles.

  7. Smoking, alcohol drinking and serum carotenoids levels.

    PubMed

    Aoki, K; Ito, Y; Sasaki, R; Ohtani, M; Hamajima, N; Asano, A

    1987-10-01

    Serum carotenoids concentrations in healthy inhabitants, aged 40-79 years, of a community were measured. The results are as follows. 1. The alpha- and beta-carotene and lycopene levels in serum were significantly higher in females than males. The alpha- and beta-carotene concentrations tended to increase with advancing age, this being especially marked for serum beta-carotene levels in males. However, beta-carotene levels were high in females throughout the age range of 50-69 years. There was no significant change in serum level of lycopene with age. 2. There was no significant difference in intake frequency of foods containing large amounts of carotenoids among the groups with or without smoking and drinking, as serum alpha- and beta-carotene levels were closely associated with intake frequency of green-yellow vegetables. 3. Regular alcohol drinkers or current smokers showed lower serum beta-carotene concentrations, and the effect of alcohol drinking on serum carotene level seemed to be larger than that of smoking. A synergistic lowering action of smoking and drinking on serum beta-carotene level was suggested. Among the alcohol drinkers, the more cigarettes consumed per day, the lower the serum beta-carotene level was, but this was not the case among the non-drinkers. Ex-smokers showed intermediate values between current smokers and non-smokers. The results suggest that alcohol drinking and smoking habit might be associated with lower serum beta-carotene level, which in turn may be related to excess incidence of cancer among smokers or drinkers.

  8. Role of Rabbit Lysozyme in In Vitro Serum and Plasma Serum Bactericidal Reactions Against Bacillus subtilis

    PubMed Central

    Carroll, Stephen F.; Martinez, Rafael J.

    1979-01-01

    The antibacterial activity of purified rabbit lysozyme was kinetically investigated at concentrations comparable to those in normal rabbit serum and plasma serum. The bactericidal capability, lysozyme content, and electrophoretic composition of “purified β-lysin,” fractionated from normal rabbit serum, were also examined. In contrast to the extensive antibacterial activity of dilute normal rabbit serum observed in vitro, rabbit lysozyme was only weakly bactericidal for Bacillus subtilis. Inhibition of lysozyme enzymatic and bactericidal activities in normal rabbit serum by antilysozyme immunoglobulin G slightly reduced the initial rate of killing. The addition of neutralizing antibody or histamine (another lysozyme inhibitor) to partially purified bactericidal serum fractions had no effect on killing kinetics. Increasing the ionic strength of reaction mixtures containing normal serum or partially purified bactericidal fractions to levels which completely inhibited lysozyme activity resulted in stimulation of their respective killing kinetics. The addition of inhibitors to normal rabbit plasma serum completely eliminated its bactericidal activity. With regard to the killing of B. subtilis by rabbit and human blood fractions, these analyses clearly demonstrated that (i) although lysozyme is not a significant antibacterial component of normal rabbit serum, it represents the principal factor in normal rabbit plasma serum; (ii) different primary bactericidal mechanisms which are not detectable by singlepoint analyses operate in the sera of different species; and (iii) purified β-lysin isolated from normal rabbit serum by the classical procedure is a heterogenous mixture of components. Images PMID:115789

  9. [Serum iron and serum copper balance in the early diagnosis of metastases of breast cancer].

    PubMed

    Wöllgens, P; Kuhne-Velte, H J; Franke-Lompa, C

    1980-02-01

    In a study made in the follow-up clinic on 684 patients with mammary carcinoma it was found that there were 64 cases of local recurrence and 244 cases of distant metastases. In both groups the serum iron and the serum copper balance in blood tests, in relation to the clinical proof of local recurrence and/or distant metastases, was investigated. It was found that there were 43.7% pathological serum iron and serum copper findings with local recurrences and 62.7% with distant metastases. The drift apart tendency of the blood serum values in patients with distant metastases could be proved in 78.7% of the cases and in 77.5% of the cases before any clinical proof. Thus, these observations allow the statement that the blood serum iron and serum copper imbalance in blood tests is of very real value in the early diagnosis of distant metastases.

  10. Neural differentiation of pluripotent mouse embryonal carcinoma cells by retinoic acid: inhibitory effect of serum.

    PubMed

    Pacherník, J; Bryja, V; Esner, M; Kubala, L; Dvorák, P; Hampl, A

    2005-01-01

    In both embryonal carcinoma (EC) and embryonic stem (ES) cells, the differentiation pathway entered after treatment with retinoic acid (RA) varies as it is based upon different conditions of culture. This study employs mouse EC cells P19 to investigate the effects of serum on RA-induced neural differentiation occurring in a simplified monolayer culture. Cell morphology and expression of lineage-specific molecular markers document that, while non-neural cell types arise after treatment with RA under serum-containing conditions, in chemically defined serum-free media RA induces massive neural differentiation in concentrations of 10(-9) M and higher. Moreover, not only neural (Mash-1) and neuroectodermal (Pax-6), but also endodermal (GATA-4, alpha-fetoprotein) genes are expressed at early stages of differentiation driven by RA under serum-free conditions. Furthermore, as determined by the luciferase reporter assay, the presence or absence of the serum does not affect the activity of the retinoic acid response element (RARE). Thus, mouse EC cells are able to produce neural cells upon exposure to RA even without culture in three-dimensional embryoid bodies (EBs). However, in contrast to standard EBs-involving protocol(s), neural differentiation in monolayer only takes place when complex signaling from serum factors is avoided. This simple and efficient strategy is proposed to serve as a basis for neurodifferentiation studies in vitro. PMID:15717849

  11. Serum and Urinary NGAL in Septic Newborns

    PubMed Central

    Suchojad, Anna; Majcherczyk, Malgorzata; Jadamus-Niebroj, Danuta; Owsianka-Podlesny, Teresa; Brzozowska, Aniceta

    2014-01-01

    Neutrophil gelatinase-associated lipocalin (NGAL) is postulated to be a potentially new and highly specific/sensitive marker of acute kidney injury (AKI). The aim of this study was to assess the impact of inflammation on serum and urine NGAL in newborns that were treated due to infection. We determined serum and urine NGAL concentrations in 73 infants (51 with sepsis; 22 with severe sepsis) admitted to the Intensive Care Unit in the first month of life, for three consecutive days during the course of treatment for infection. 29 neonates without infection served as the control group. Septic patients, in particular, severe sepsis patients, had increased serum and urinary NGAL levels in the three subsequent days of observation. Five septic patients who developed AKI had elevated serum and urinary NGAL values to a similar extent as septic neonates without AKI. A strong correlation was found between the concentration of serum and urinary NGAL and inflammatory markers, such as CRP and procalcitonin. Serum and urinary NGAL levels were also significantly associated with NTISS (neonatal therapeutic intervention scoring system) values. We conclude that increased serum and urinary NGAL values are not solely a marker of AKI, and more accurately reflect the severity of inflammatory status. PMID:24579085

  12. Polybrominated Diphenyl Ethers in Maternal Serum, Breast Milk, Umbilical Cord Serum, and House Dust in a South Korean Birth Panel of Mother-Neonate Pairs.

    PubMed

    Shin, Mi-Yeon; Lee, Sunggyu; Kim, Hai-Joong; Lee, Jeong Jae; Choi, Gyuyeon; Choi, Sooran; Kim, Sungjoo; Kim, Su Young; Park, Jeongim; Moon, Hyo-Bang; Choi, Kyungho; Kim, Sungkyoon

    2016-01-01

    Polybrominated diphenyl ethers (PBDEs) have been used as flame retardants. Although many reports have indicated an association between exposure to PBDEs and developmental neurotoxicity, the relative contributions of different sources of dust PBDE congeners to the levels in various tissues of mother-baby pairs is not well understood. The aims of this study were thus to measure the quantitative relationship between the level of PBDEs in house dust and tissues of mother-neonate pairs, and to investigate the chemical sources of the PBDEs. Forty-one mother-neonate pairs were recruited and provided samples of maternal serum (n = 29), umbilical cord serum (n = 25), breast milk (n = 50), and house dust (n = 41), where PBDEs were determined with high-resolution gas chromatography coupled with high-resolution mass spectrometry. While deca- (e.g., BDE 209, detected 100%), nona- (BDE 206/207, 95.1%), octa- (BDE 183, 100%), penta- (BDE 99/153, 100%, 98%) and tetra-BDEs (BDE 47, 100%) were detected abundantly in dust, penta- (BDE 99, 76%, 92%) and tetra-BDEs (BDE 47, 84%, 98%) were detected abundantly in umbilical cord serum and breast milk, respectively; tetra-BDEs (BDE 47, 86%) were detected more often relative to other congeners in maternal serum. Spearman's pairwise comparison showed that the levels of BDE 47 (ρ = 0.52, p < 0.001) and -99 (ρ = 0.64, p < 0.01) in umbilical cord serum were associated with BDE 209 levels in dust; BDE 47 in maternal serum also showed correlation with BDE 99 in cord serum (ρ = 0.48, p < 0.01) but there was no significant correlation between maternal BDE 47 and dust BDE 209. On the other hand, a comparison of the distribution among congeners suggested probable associations of BDE 47 in maternal serum, breast milk, and umbilical cord serum with BDE 209 in dust; and of BDE 99 in maternal and umbilical cord serum, breast milk, and dust with BDE 209 in dust. Although further studies are needed, a radar chart-based distributional comparison among

  13. Polybrominated Diphenyl Ethers in Maternal Serum, Breast Milk, Umbilical Cord Serum, and House Dust in a South Korean Birth Panel of Mother-Neonate Pairs

    PubMed Central

    Shin, Mi-Yeon; Lee, Sunggyu; Kim, Hai-Joong; Lee, Jeong Jae; Choi, Gyuyeon; Choi, Sooran; Kim, Sungjoo; Kim, Su Young; Park, Jeongim; Moon, Hyo-Bang; Choi, Kyungho; Kim, Sungkyoon

    2016-01-01

    Polybrominated diphenyl ethers (PBDEs) have been used as flame retardants. Although many reports have indicated an association between exposure to PBDEs and developmental neurotoxicity, the relative contributions of different sources of dust PBDE congeners to the levels in various tissues of mother–baby pairs is not well understood. The aims of this study were thus to measure the quantitative relationship between the level of PBDEs in house dust and tissues of mother-neonate pairs, and to investigate the chemical sources of the PBDEs. Forty-one mother-neonate pairs were recruited and provided samples of maternal serum (n = 29), umbilical cord serum (n = 25), breast milk (n = 50), and house dust (n = 41), where PBDEs were determined with high-resolution gas chromatography coupled with high-resolution mass spectrometry. While deca- (e.g., BDE 209, detected 100%), nona- (BDE 206/207, 95.1%), octa- (BDE 183, 100%), penta- (BDE 99/153, 100%, 98%) and tetra-BDEs (BDE 47, 100%) were detected abundantly in dust, penta- (BDE 99, 76%, 92%) and tetra-BDEs (BDE 47, 84%, 98%) were detected abundantly in umbilical cord serum and breast milk, respectively; tetra-BDEs (BDE 47, 86%) were detected more often relative to other congeners in maternal serum. Spearman’s pairwise comparison showed that the levels of BDE 47 (ρ = 0.52, p < 0.001) and −99 (ρ = 0.64, p < 0.01) in umbilical cord serum were associated with BDE 209 levels in dust; BDE 47 in maternal serum also showed correlation with BDE 99 in cord serum (ρ = 0.48, p < 0.01) but there was no significant correlation between maternal BDE 47 and dust BDE 209. On the other hand, a comparison of the distribution among congeners suggested probable associations of BDE 47 in maternal serum, breast milk, and umbilical cord serum with BDE 209 in dust; and of BDE 99 in maternal and umbilical cord serum, breast milk, and dust with BDE 209 in dust. Although further studies are needed, a radar chart-based distributional comparison

  14. Polybrominated Diphenyl Ethers in Maternal Serum, Breast Milk, Umbilical Cord Serum, and House Dust in a South Korean Birth Panel of Mother-Neonate Pairs.

    PubMed

    Shin, Mi-Yeon; Lee, Sunggyu; Kim, Hai-Joong; Lee, Jeong Jae; Choi, Gyuyeon; Choi, Sooran; Kim, Sungjoo; Kim, Su Young; Park, Jeongim; Moon, Hyo-Bang; Choi, Kyungho; Kim, Sungkyoon

    2016-07-28

    Polybrominated diphenyl ethers (PBDEs) have been used as flame retardants. Although many reports have indicated an association between exposure to PBDEs and developmental neurotoxicity, the relative contributions of different sources of dust PBDE congeners to the levels in various tissues of mother-baby pairs is not well understood. The aims of this study were thus to measure the quantitative relationship between the level of PBDEs in house dust and tissues of mother-neonate pairs, and to investigate the chemical sources of the PBDEs. Forty-one mother-neonate pairs were recruited and provided samples of maternal serum (n = 29), umbilical cord serum (n = 25), breast milk (n = 50), and house dust (n = 41), where PBDEs were determined with high-resolution gas chromatography coupled with high-resolution mass spectrometry. While deca- (e.g., BDE 209, detected 100%), nona- (BDE 206/207, 95.1%), octa- (BDE 183, 100%), penta- (BDE 99/153, 100%, 98%) and tetra-BDEs (BDE 47, 100%) were detected abundantly in dust, penta- (BDE 99, 76%, 92%) and tetra-BDEs (BDE 47, 84%, 98%) were detected abundantly in umbilical cord serum and breast milk, respectively; tetra-BDEs (BDE 47, 86%) were detected more often relative to other congeners in maternal serum. Spearman's pairwise comparison showed that the levels of BDE 47 (ρ = 0.52, p < 0.001) and -99 (ρ = 0.64, p < 0.01) in umbilical cord serum were associated with BDE 209 levels in dust; BDE 47 in maternal serum also showed correlation with BDE 99 in cord serum (ρ = 0.48, p < 0.01) but there was no significant correlation between maternal BDE 47 and dust BDE 209. On the other hand, a comparison of the distribution among congeners suggested probable associations of BDE 47 in maternal serum, breast milk, and umbilical cord serum with BDE 209 in dust; and of BDE 99 in maternal and umbilical cord serum, breast milk, and dust with BDE 209 in dust. Although further studies are needed, a radar chart-based distributional comparison among

  15. Killing of Brucella abortus by bovine serum.

    PubMed

    Corbeil, L B; Blau, K; Inzana, T J; Nielsen, K H; Jacobson, R H; Corbeil, R R; Winter, A J

    1988-12-01

    Studies of the serum bactericidal system in bovine brucellosis were undertaken to investigate the role of the humoral immune response in protection of cattle against the facultative intracellular parasite Brucella abortus. Fresh sera from normal control cattle, infected cattle, and cattle immunized with B. abortus cell envelopes were collected before treatment and during the course of immunization or infection. Normal fresh bovine serum or fresh agammaglobulinemic serum from colostrum-deprived calves was effective in killing smooth virulent B. abortus 2308, but rough strains RB51 (a rough mutant of strain 2308) and 45/20 were much more sensitive to serum. The difference in susceptibility to serum was shown to be correlated with differences in lipopolysaccharide chemotype, with the more resistant strain 2308 having O polysaccharide and the more susceptible strains 45/20 and RB51 lacking O side chains. By treatment of fresh serum with MgCl2 and EGTA [ethylene glycol-bis(beta-aminoethyl ether)-N,N,N',N'-tetraacetic acid] killing was shown to occur via the classical pathway of complement activation. When antibody to B. abortus was present, killing of strain RB51 increased but killing of smooth strain 2308 decreased. The earliest antibody response in serum from infected animals did not interfere with killing. When affinity-purified bovine immunoglobulins specific for B. abortus smooth lipopolysaccharide were added to fresh normal bovine serum, immunoglobulin G1 (IgG1) and IgG2 isotypes blocked killing but IgM and IgA isotypes did not. Thus, it appears that serum from previously unexposed animals or animals early during infection can kill smooth B. abortus, an appropriate defense mechanism before the organism becomes intracellular. At later stages of infection, blocking antibodies predominate.

  16. Serum bile acids in patients with hyperlipidaemia.

    PubMed Central

    Pennington, C R; Ross, P E; Bateson, M C; Bouchier, I A

    1978-01-01

    Individual serum bile acids were analysed by an improved gas liquid chromatography method in 12 patients with primary hyperlipidaemia. Total serum bile acid concentrations were raised in 10 subjects. Ursodeoxycholic acid was found in all 12 patients. It was present in significantly greater concentrations, accounted for a greater proportion of the total serum bile acids, and occurred more frequently than in patients with various forms of hepatobiliary disease. Patients with hyperlipidaemia had proportionately less deoxycholic acid than controls but more than patients with liver disease. There was proportionately less chenodeoxycholic acid in patients with hypercholesterolaemia, in whom the primary bile acid ratio was raised. PMID:627619

  17. Serum nickle estimation in acute myocardial infarction.

    PubMed

    Narang, N K; Goyal, R K; Gupta, A K; Balwani, S

    1989-11-01

    Serum nickle was estimated by atomic absorption spectrometer in 20 healthy controls and in 25 cases of acute myocardial infarction at 12 hourly intervals upto 48 hours, after the onset of chest pain. The mean serum nickel was 0.27 micrograms/dl in healthy controls and 0.40,050,049 and 0.30 micrograms/dl in patients of acute myocardial infarction. The serum nickel values were significantly (P less than 0.001) raised upto 36 hours in acute myocardial infarction when compared with controls.

  18. Improved ultraviolet spectrophotometry of serum theophylline.

    PubMed

    Carter, P; Wallace, J E; Blum, K

    1978-02-01

    We present an improved method for ultraviolet spectrophotometry of theophylline in serum. We studied various extraction techniques aimed at eliminating interferences from co-extractable serum constituents. In the resulting modified procedure, 1 ml of serum is required and a salt-solvent pair of ammonium sulfate and chloroform/hexane is used for extraction. The solvent forms the top phase after extraction, the lower phase after back-extraction, thereby permitting easy removal of the appropriate phase from culture tubes. The use of ammonium sulfate coupled with the added specificity of the extraction solvent results in an extract with low background absorption and a well-defined spectrum for the extracted theophylline.

  19. Enzymatically Modified Starch Ameliorates Postprandial Serum Triglycerides and Lipid Metabolome in Growing Pigs

    PubMed Central

    Metzler-Zebeli, Barbara U.; Eberspächer, Eva; Grüll, Dietmar; Kowalczyk, Lidia; Molnar, Timea; Zebeli, Qendrim

    2015-01-01

    Developing host digestion-resistant starches to promote human health is of great research interest. Chemically modified starches (CMS) are widely used in processed foods and although the modification of the starch molecule allows specific reduction in digestibility, the metabolic effects of CMS have been less well described. This short-term study evaluated the impact of enzymatically modified starch (EMS) on fasting and postprandial profiles of blood glucose, insulin and lipids, and serum metabolome in growing pigs. Eight jugular-vein catheterized pigs (initial body weight, 37.4 kg; 4 months of age) were fed 2 diets containing 72% purified starch (EMS or waxy corn starch (control)) in a cross-over design for 7 days. On day 8, an 8-hour meal tolerance test (MTT) was performed with serial blood samplings. Besides biochemical analysis, serum was analysed for 201 metabolites through targeted mass spectrometry-based metabolomic approaches. Pigs fed the EMS diet showed increased (P<0.05) immediate serum insulin and plasma glucose response compared to pigs fed the control diet; however, area-under-the-curves for insulin and glucose were not different among diets. Results from MTT indicated reduced postprandial serum triglycerides with EMS versus control diet (P<0.05). Likewise, serum metabolome profiling identified characteristic changes in glycerophospholipid, lysophospholipids, sphingomyelins and amino acid metabolome profiles with EMS diet compared to control diet. Results showed rapid adaptations of blood metabolites to dietary starch shifts within 7 days. In conclusion, EMS ingestion showed potential to attenuate postprandial raise in serum lipids and suggested constant alteration in the synthesis or breakdown of sphingolipids and phospholipids which might be a health benefit of EMS consumption. Because serum insulin was not lowered, more research is warranted to reveal possible underlying mechanisms behind the observed changes in the profile of serum lipid

  20. The Second International Standard for Serum Gonadotrophin*

    PubMed Central

    Bangham, D. R.; Woodward, Patricia M.

    1966-01-01

    In 1961 the WHO Expert Committee on Biological Standardization asked the National Institute for Medical Research, London, to collect and study material to replace the first International Standard for Serum Gonadotrophin, stocks of which were running low. This paper describes the material that was contributed, its distribution into ampoules and the international collaborative assay to compare its biological activity with that of the first International Standard. On the basis of the results obtained the material has been established as the second International Standard for Serum Gonadotrophin, with a potency of 1600 International Units per ampoule. The International Unit for Serum Gonadotrophin is thus defined as the activity contained in 0.003569 mg of the second International Standard for Serum Gonadotrophin. PMID:5297810

  1. Computational Modeling of Thyroid Hormone Regulated Neurodevelopment for Chemical Prioritization (SOT)

    EPA Science Inventory

    Thyroid hormones (TH) are critical for normal brain development. Environmental chemicals may disrupt TH homeostasis through a variety of physiological systems including membrane transporters, serum transporters, synthesis and catabolic enzymes, and nuclear receptors. Current comp...

  2. Refractory intraoperative hypotension with elevated serum tryptase

    PubMed Central

    Larson, Kelly J.; Divekar, Rohit D.; Butterfield, Joseph H.; Schwartz, Lawrence B.; Weingarten, Toby N.

    2015-01-01

    Severe intraoperative hypotension has been reported in patients on angiotensin-converting enzyme inhibitors and angiotensin II receptor subtype 1 antagonists. We describe a patient on lisinopril who developed refractory intraoperative hypotension associated with increased serum tryptase level suggesting mast cell activation (allergic reaction). However, allergology workup ruled out an allergic etiology as well as mastocytosis, and hypotension recalcitrant to treatment was attributed to uninterrupted lisinopril therapy. Elevated serum tryptase was attributed to our patient's chronic renal insufficiency. PMID:25653920

  3. Serum ferritin in juvenile chronic polyarthritis.

    PubMed Central

    Craft, A W; Eastham, E J; Bell, J I; Brigham, K

    1977-01-01

    Six children with juvenile chronic polyarthritis were studied and their disease activity correlated with haematological values including serum ferritin. The latter is often raised above reference values, but even when within them appears to fluctuate significantly and correlates more closely with disease activity than any of the other parameters measured. We conclude that the serial measurement of serum ferritin may be a useful guide to the management of such children. PMID:879866

  4. Moving past serology: Diagnostic options without serum.

    PubMed

    Reichel, Michael P; Lanyon, Sasha R; Hill, Fraser I

    2016-09-01

    Detecting antibodies formed in serum in response to infection is the traditional function of serology. Diagnostic modalities have included complement fixation tests, agar gel immune-diffusion, radioimmunoassay, ELISA and immunofluorescence. More recent technology now allows for the direct detection of pathogens by PCR. This review details the options for diagnostic testing using specimen types other than serum, identifying the advantages and disadvantages of these options and providing evidence for more widespread use of these techniques and specimen types. PMID:27160006

  5. [Pu(IV) behavior in the serum].

    PubMed

    Surova, Z I

    1984-01-01

    This paper presents the results of studies of the hydrolysis and polymerization of Pu(IV) in blood serum. With nitrite Pu(IV) solutions incubated with blood serum 20-34% of the nuclide were precipitated as hydroxide and 11-36% converted into polymeric forms bound by high molecular weight proteins. For citrate solutions, these values were 3.8 and 3.0%, respectively. PMID:6505160

  6. Photothermal Measurements on Human Serum and Plasma

    NASA Astrophysics Data System (ADS)

    Bernal-Alvarado, J.; Sosa, M.; Hernández, L. C.; Hernández-Cabrera, F.; Mayén-Mondragón, R.; Yánez-Limón, J. M.; Flores-Farías, R.; Palomares, P.; Juárez, P.; Ramírez, R.

    2003-09-01

    Using a thermal lens experimental set up, the thermal diffusivity of serum and plasma was measured. Several samples were studied and the results are reported as the average with the standard deviation. The serum and plasma were obtained by aleatory sampling of healthy adult donors at the Guanajuato State Transfusion Center, Mexico; the donors were free of hepatitis and other diseases, clinically tested. The parameters reported were obtained using the thermal lens aberrant model with the lasers operating in the mismatched mode.

  7. Serum vitamin B12 in renal failure

    PubMed Central

    Matthews, D. M.; Beckett, A. Gordon; Maxwell, Patricia

    1962-01-01

    The serum vitamin B12 level was abnormally high in 14 out of 32 cases of renal failure. This was probably due to impaired excretion of the vitamin, but the results of measurements of the rate of excretion of radioactive vitamin B12 did not provide unequivocal evidence on this point; other possible explanations are discussed. Renal failure must be added to the causes of high serum B12 levels. PMID:13933867

  8. (PCG) Protein Crystal Growth Horse Serum Albumin

    NASA Technical Reports Server (NTRS)

    1995-01-01

    Horse Serum Albumin crystals grown during the USML-1 (STS-50) mission's Protein Crystal Growth Glovebox Experiment. These crystals were grown using a vapor diffusion technique at 22 degrees C. The crystals were allowed to grow for nine days while in orbit. Crystals of 1.0 mm in length were produced. The most abundant blood serum protein, regulates blood pressure and transports ions, metabolites, and therapeutic drugs. Principal Investigator was Edward Meehan.

  9. Serum Biochemical Phenotypes in the Domestic Dog.

    PubMed

    Chang, Yu-Mei; Hadox, Erin; Szladovits, Balazs; Garden, Oliver A

    2016-01-01

    The serum or plasma biochemical profile is essential in the diagnosis and monitoring of systemic disease in veterinary medicine, but current reference intervals typically take no account of breed-specific differences. Breed-specific hematological phenotypes have been documented in the domestic dog, but little has been published on serum biochemical phenotypes in this species. Serum biochemical profiles of dogs in which all measurements fell within the existing reference intervals were retrieved from a large veterinary database. Serum biochemical profiles from 3045 dogs were retrieved, of which 1495 had an accompanying normal glucose concentration. Sixty pure breeds plus a mixed breed control group were represented by at least 10 individuals. All analytes, except for sodium, chloride and glucose, showed variation with age. Total protein, globulin, potassium, chloride, creatinine, cholesterol, total bilirubin, ALT, CK, amylase, and lipase varied between sexes. Neutering status significantly impacted all analytes except albumin, sodium, calcium, urea, and glucose. Principal component analysis of serum biochemical data revealed 36 pure breeds with distinctive phenotypes. Furthermore, comparative analysis identified 23 breeds with significant differences from the mixed breed group in all biochemical analytes except urea and glucose. Eighteen breeds were identified by both principal component and comparative analysis. Tentative reference intervals were generated for breeds with a distinctive phenotype identified by comparative analysis and represented by at least 120 individuals. This is the first large-scale analysis of breed-specific serum biochemical phenotypes in the domestic dog and highlights potential genetic components of biochemical traits in this species. PMID:26919479

  10. Serum Biochemical Phenotypes in the Domestic Dog

    PubMed Central

    Chang, Yu-Mei; Hadox, Erin; Szladovits, Balazs; Garden, Oliver A.

    2016-01-01

    The serum or plasma biochemical profile is essential in the diagnosis and monitoring of systemic disease in veterinary medicine, but current reference intervals typically take no account of breed-specific differences. Breed-specific hematological phenotypes have been documented in the domestic dog, but little has been published on serum biochemical phenotypes in this species. Serum biochemical profiles of dogs in which all measurements fell within the existing reference intervals were retrieved from a large veterinary database. Serum biochemical profiles from 3045 dogs were retrieved, of which 1495 had an accompanying normal glucose concentration. Sixty pure breeds plus a mixed breed control group were represented by at least 10 individuals. All analytes, except for sodium, chloride and glucose, showed variation with age. Total protein, globulin, potassium, chloride, creatinine, cholesterol, total bilirubin, ALT, CK, amylase, and lipase varied between sexes. Neutering status significantly impacted all analytes except albumin, sodium, calcium, urea, and glucose. Principal component analysis of serum biochemical data revealed 36 pure breeds with distinctive phenotypes. Furthermore, comparative analysis identified 23 breeds with significant differences from the mixed breed group in all biochemical analytes except urea and glucose. Eighteen breeds were identified by both principal component and comparative analysis. Tentative reference intervals were generated for breeds with a distinctive phenotype identified by comparative analysis and represented by at least 120 individuals. This is the first large-scale analysis of breed-specific serum biochemical phenotypes in the domestic dog and highlights potential genetic components of biochemical traits in this species. PMID:26919479

  11. Chemical locomotion.

    PubMed

    Paxton, Walter F; Sundararajan, Shakuntala; Mallouk, Thomas E; Sen, Ayusman

    2006-08-18

    Research into the autonomous motion of artificial nano- and microscale objects provides basic principles to explore possible applications, such as self-assembly of superstructures, roving sensors, and drug delivery. Although the systems described have unique propulsion mechanisms, motility in each case is made possible by the conversion of locally available chemical energy into mechanical energy. The use of catalysts onboard can afford nondissipative systems that are capable of directed motion. Key to the design of nano- and micromotors is the asymmetric placement of the catalyst: its placement in an environment containing a suitable substrate translates into non-uniform consumption of the substrate and distribution of reaction products, which results in the motility of the object. These same principles are exploited in nature to effect autonomous motion.

  12. Serum concentrations of haptoglobin and serum amyloid A in water buffaloes (Bubalus bubalis) with abomasal ulcer.

    PubMed

    Tajik, Javad; Nazifi, Saeed; Heidari, Mahdi; Babazadeh, Marzieh

    2012-01-01

    To evaluate the serum concentrations of haptoglobin (Hp) and serum amyloid A (SAA) in water buffaloes with abomasal ulcers, the abomasums of 100 randomly selected water buffaloes were examined after slaughter. Type I abomasal ulcers were found in 56 out of 100 buffaloes. Serum concentrations of Hp and SAA were measured. There was no significant difference between affected and non-affected buffaloes in the serum concentrations of Hp and SAA. The serum concentrations of Hp and SAA had no significant correlation with age and the serum SAA revealed no significant correlation with the number of abomasal ulcers. A significant correlation was found between the serum Hp and the number of abomasal ulcers (r =0.29, p = 0.04). There was no significant difference in the serum concentrations of Hp and SAA between buffaloes with different ulcer locations in the abomasums. Although more work on a larger number of animals is required in this area, it seems that the measurement of the serum Hp can be used to predict the abundance of type I abomasal ulcers.

  13. Role of capsule and O antigen in resistance of Klebsiella pneumoniae to serum bactericidal activity.

    PubMed Central

    Tomás, J M; Benedí, V J; Ciurana, B; Jofre, J

    1986-01-01

    The ability of Klebsiella pneumoniae strains to resist the bactericidal activity of serum was quantitated. The K. pneumoniae strains tested included mutants lacking the capsular polysaccharide and mutants having a modified lipopolysaccharide structure. The last mutants were obtained as phage-resistant mutants, and their lipopolysaccharide was characterized by sodium dodecyl sulfate-polyacrylamide gel electrophoresis and chemical analysis. Serum-resistant mutants derived from phage-resistant mutants (lipopolysaccharide mutants) were also characterized. Resistance to the bactericidal activity of complement was mediated by the lipopolysaccharide, especially by the O-antigen polysaccharide chains. The capsular polysaccharide seemed not to play any important role in resistance to serum bactericidal activity in this bacterium. Images PMID:3531020

  14. A novel immunoassay for quantitative drug abuse screening in serum.

    PubMed

    Schumacher, Sarah; Seitz, Harald

    2016-09-01

    An immunoassay was established which enables a reliable quantification of serological drug samples. The assay is based on a competitive ELISA. In total nine drugs (amphetamine, methamphetamine, 3,4-methylenedioxy-methamphetamine (MDMA), tetrahydrocannabinol (THC), phencyclidine (PCP), methadone, morphine, cocaine and benzoylecgonine) were tested. All reagents had to pass through a stringent validation process. Within the established test for three out of the nine drugs no cross-reactivity with any tested compounds, e.g. serum, other antibodies or chemically related molecules was detectable for the tested antibodies. Furthermore, a sensitive and selective detection was possible, even in the presence of up to 9 drugs or of various anti-drug antibodies. After exclusion of cross-reactivities antibodies against three drugs (methadone, MDMA, benzoylecgonine) were validated, which allowed a specific and sensitive quantification. For the competitive measurements CVs in the range of 2-17% could be reached with LLOQs of 10ng/mL and LODs of 150ng/mL for methadone, 250ng/mL for MDMA and 400ng/mL for benzoylecgonine. Anonymized serum samples (n=10) provided by the office of criminal investigation Berlin were analyzed for verification purposes. Evaluation of these data showed a correlation (CV) of ≈0.9 with standard GC-MS methods. A miniaturization on microarray was possible by using the anti-MDMA antibody for the detection of MDMA in serum. The microarray increased the through-put drastically and enabled the simultaneous quantification of various drugs. PMID:27343723

  15. Influence of in vitro biomimicked stem cell 'niche' for regulation of proliferation and differentiation of human bone marrow-derived mesenchymal stem cells to myocardial phenotypes: serum starvation without aid of chemical agents and prevention of spontaneous stem cell transformation enhanced by the matrix environment.

    PubMed

    Kim, Jae Hyung; Shin, Sang-Hyun; Li, Tian Zhu; Suh, Hwal

    2016-01-01

    Niche appears important for preventing the spontaneous differentiation or senescence that cells undergo during in vitro expansion. In the present study, it was revealed that human bone marrow-derived mesenchymal stem cells (hBM-MSCs) undergo senescence-related differentiation into the myocardial lineage in vitro without any induction treatment. This phenomenon occurred over the whole population of MCSs, much different from conventional differentiation with limited frequency of occurrence, and was accompanied by a change of morphology into large, flat cells with impeded proliferation, which are the representative indications of MSC senescence. By culturing MSCs under several culture conditions, it was determined that induction treatment with 5-azacytidine was not associated with the phenomenon, but the serum-starvation condition, under which proliferation is severely hampered, caused senescence progression and upregulation of cardiac markers. Nevertheless, MSCs gradually developed a myocardial phenotype under normal culture conditions over a prolonged culture period and heterogeneous populations were formed. In perspectives of clinical applications, this must be prevented for fair and consistent outcomes. Hence, the biomimetic 'niche' was constituted for hBM-MSCs by cultivating on a conventionally available extracellular matrix (ECM). Consequently, cells on ECM regained a spindle-shape morphology, increased in proliferation rate by two-fold and showed decreased expression of cardiac markers at both the mRNA and protein levels. In conclusion, the outcome indicates that progression of MSC senescence may occur via myocardial differentiation during in vitro polystyrene culture, and this can be overcome by employing appropriate ECM culture techniques.

  16. Evaluating the impact of a fluoropolymer plant on a river macrobenthic community by a combined chemical, ecological and genetic approach.

    PubMed

    Rusconi, Marianna; Marziali, Laura; Stefani, Fabrizio; Valsecchi, Sara; Bettinetti, Roberta; Mazzoni, Michela; Rosignoli, Federica; Polesello, Stefano

    2015-12-15

    Effect-based monitoring is a recommended approach suggested in European Guidelines to assess the response of ecosystem affected by a pollution source, considering the effects at community, population, individual but also at suborganism level. A combined chemical, ecological and genetic approach was applied in order to assess the impact of a fluoropolymer plant on the macrobenthic community of the Northern Italian river Bormida (Piedmont region). The macrobenthic community living downstream of the industrial discharge was chronically exposed to a mixture of perfluoroalkyl substances (PFAS), with perfluorooctanoic acid as the main compound, at concentrations up to several μgL(-1). Ecological assessment proved that the downstream community was not substantially different from that living upstream of the pollution source. The impact on community is not quantifiable with the traditional monitoring methods used for ecological classification under European regulation because macrobenthic communities showed only slight differences in their structure. In order to highlight effects on genetic variability of the native population, a subcellular analysis by using the AFLP (Amplified Fragment Length Polymorphism) genetic technique was applied to genotype of individuals of a selected species (Hydropsyche modesta, Trichoptera) collected in the two sampling sites. Percentage of variation between the two populations was 6.8%, a threshold compatible with a genetic drift induced in the downstream population. The genetic study carried out in field identified a significant divergence between exposed and non-exposed populations, but at present it is not possible to associate this divergence to a specific effect induced by PFAS.

  17. Concentrations and trends of perfluorinated chemicals in potential indoor sources from 2007 through 2011 in the US.

    PubMed

    Liu, Xiaoyu; Guo, Zhishi; Krebs, Kenneth A; Pope, Robert H; Roache, Nancy F

    2014-03-01

    Certain perfluorinated chemicals (PFCs) in consumer products used indoors are potential indoor PFCs sources and have been associated with developmental toxicity and other adverse health effects in laboratory animals (Lao et al., 2007). The concentrations of selected PFCs including perfluorooctanoic acid (PFOA) and other perfluorocarboxylic acids (PFCAs), in 35 selected consumer products that are commonly used in indoors were measured from the year of 2007 through 2011. The products collected included carpet, commercial carpet-care liquids, household carpet/fabric-care liquids, treated apparel, treated home textiles, treated non-woven medical garments, floor waxes, food-contact paper, membranes for apparel, and thread-sealant tapes. They were purchased from retail outlets in the United States between March 2007 and September 2011. The perfluorocarboxylic acid (PFCA) contents in the products have shown an overall downward trend. However, PFOA (C8) could still be detected in many products that we analyzed. Reductions of PFCAs were shown in both short-chain PFCAs (sum of C4 to C7) and long-chain PFCAs (sum of C8 to C12) over the study period. There were no significant changes observed between short-chain PFCAs and long-chain PFCAs. Fourteen products were analyzed to determine the amounts of perfluoroalkyl sulfonates (PFASs) they contained. These limited data show the pronounced increase of perfluoro-butane sulfonate (PFBS), an alternative to perfluorooctanoic sulfonate (PFOS), in the samples. A longer and wider range of study will be required to confirm this observed trend. PMID:24268172

  18. Serum Prolactin Level of Subfertile Women.

    PubMed

    Anwary, S A; Fatima, P; Alfazzaman, M; Mahzabin, Z; Rahman, M M; Bari, N

    2016-01-01

    Subfertility is a major reproductive health problem all over the world as well as Bangladesh, and the problem is increasing day by day. This study was done to estimate the serum prolactin concentration in primary and secondary subfertile women. Laboratory investigation included serum prolactin level, as well as LH, FSH, TSH blood glucose (2 hours after 75 gm glucose load) of 50 women who attended infertility unit, Department of Obstetrics and Gynaecology, Bangabandhu Sheikh Mujib Medical University (BSMMU), Dhaka, Bangladesh from March 2009 and February 2010. In most cases, common age group 26-30 years (52%), primary subfertility (74%), duration of marriage >5 years (60%), trying to conceive duration ≤5 years (54%), BMI >25 kg/m² (60%), menstrual cycle regular (58%), history of abortion absent (90%), and history of menstrual regulation absent (94%). Common investigation findings was normal serum follicle stimulating hormone (FSH) 1.0-10.0 mIU/ml in 82%, normal serum luteinizing hormone (LH) 1.0-10.0 mIU/ml in 50%, normal serum prolactin 1.9-25.0 ng/ml in 36%, normal serum thyroid stimulating hormone (TSH) 0.4-4.0 μIU/ml in 56%, and normal blood glucose level (2 hours after breakfast) (<7.8 mmol/) in 66% women. Ultrasonographic finding of lower abdomen was normal in 14% women. Common finding of semen analysis husbands of the study women was normozoospermia in 88% cases. Serum prolactin concentration may have role to play in subfertility of women.

  19. Synchronization of mammalian cell cultures by serum deprivation.

    PubMed

    Langan, Thomas J; Chou, Richard C

    2011-01-01

    Mammalian cells are amenable to study the regulation of cell cycle progression in vitro by shifting them into the same phase of the cycle. Procedures to arrest cultured cells in specific phases of the cell cycle may be termed in vitro synchronization. The procedure described here was developed for the study of primary astrocytes and a glioma cell line, but is applicable to other mammalian cells. Its application allows astrocytes to reenter the cell cycle from a state of quiescence (G(0)), and then, under carefully defined experimental conditions, to move together into subsequent phases such as the G(1) and S phases. A number of methods have been established to synchronize mammalian cell cultures, which include physical separation by centrifugal elutriation and mitotic shake off or chemically induced cell cycle arrest. Yet, there are intrinsic limitations associated with these methods. In the present protocol, we describe a simple, reliable, and reversible procedure to synchronize astrocyte and glioma cultures from newborn rat brain by serum deprivation. The procedure is similar, and generally applicable, to other mammalian cells. This protocol consists essentially of two parts: (1) proliferation of astrocytes under optimal conditions in vitro until reaching desired confluence; and (2) synchronization of cultures by serum downshift and arrested in the G(0) phase of the cell cycle. This procedure has been extended to the examination of cell cycle control in astroglioma cells and astrocytes from injured adult brain. It has also been employed in precursor cloning studies in developmental biology, suggesting wide applicability.

  20. In vitro synchronization of mammalian astrocytic cultures by serum deprivation.

    PubMed

    Chou, Richard C; Langan, Thomas J

    2003-07-01

    The study of the regulation of cell division cycle in vitro requires cell cultures growing in the same phase of the cycle. The procedure by which cells are arrested in specific phases of the cell cycle is termed synchronization. Synchronization is particularly important in the study of astrocyte biology, as its application allows astrocytes to re-enter the cell cycle from a state of quiescence (G(0)), and, under carefully defined experimental conditions, move together into subsequent phases such as the G(1) and S phases. A number of methods have been established to synchronize mammalian cell cultures, including centrifugal elutriation, mitotic shake-off, and chemically induced cell cycle arrest. Yet there are intrinsic limitations associated with these methods. In the present protocol, we describe a simple, reliable, and reversible procedure to synchronize astrocytic cultures from newborn rat brains by serum deprivation. This protocol consists essentially of two parts: (1) proliferation of astrocytes under optimal conditions in vitro until reaching desired confluence; and (2) synchronization of cultures by serum down-shift and arrested in the G(0) phase of the cell cycle. This procedure has recently been extended toward the study of cell cycle control in astroglioma cells and astrocytes from injured adult brains. Since it was also employed in recent precursor cloning studies in developmental biology, this procedure will certainly find increasing use in future research.

  1. [Changes in serum enzymes in rats treated with sodium bisulfite].

    PubMed

    Alarcón-Corredor, O M; Ramirez de Fernández, M; Bastardo de Castañeda, G; Silva, T; Alarcón, A O

    2000-01-01

    Inorganic sulfites are chemical compounds with antioxidative, antibacterial and antimycotic properties diffusely employed in agro-food and pharmaceutical industries. In spite of their continuous use there still are many questions regarding their safety, and their possible influence in several nutrients and enzymatic systems, as according to reports in the literature cited. In this study it is determined the effect of increasing doses of sodium bisulphite, 10 to 50 mg/kg/day, injected intramuscularly during seven days on the activity of the following serum enzymes: phosphohexoseisomerase (PHI), gamma-glutamyltranspeptidase (gamma-GT), cholinesterase (CHE), arginase, acid maltase (AM), alkaline phosphatase (AIP), lactic dehydrogenase (LDH), transaminases (GOT and GPT) and 5'-nucleotidase (5'-N) on male Wistar rats (treated groups). The results indicate that in rats treated with sodium bisulphite there is a significant increase (p < 0.05) in the activity of PHI, gamma-GT, arginase, AIP, GOT, GPT and 5'-N as well as an equally significant decrease (p < 0.05) in the activity of LDH, AM and CHE; these variations are proportional to the doses of the compound applied. These findings indicate there is cellular damage to rat liver, kidney or others organs as a result of bisulphite injected or by its metabolic derivatives. It is suggested that measurements of serum levels of LDH, AM and CHE are particularly helpful in the clinical assessment of pathologies caused by sulfites in allergology.

  2. Heme-based catalytic properties of human serum albumin

    PubMed Central

    Ascenzi, P; di Masi, A; Fanali, G; Fasano, M

    2015-01-01

    Human serum albumin (HSA): (i) controls the plasma oncotic pressure, (ii) modulates fluid distribution between the body compartments, (iii) represents the depot and carrier of endogenous and exogenous compounds, (iv) increases the apparent solubility and lifetime of hydrophobic compounds, (v) affects pharmacokinetics of many drugs, (vi) inactivates toxic compounds, (vii) induces chemical modifications of some ligands, (viii) displays antioxidant properties, and (ix) shows enzymatic properties. Under physiological and pathological conditions, HSA has a pivotal role in heme scavenging transferring the metal-macrocycle from high- and low-density lipoproteins to hemopexin, thus acquiring globin-like reactivity. Here, the heme-based catalytic properties of HSA are reviewed and the structural bases of drug-dependent allosteric regulation are highlighted. PMID:27551458

  3. Predictors of Serum Dioxin, Furan and PCB Concentrations among Women from Chapaevsk, Russia

    PubMed Central

    Humblet, Olivier; Williams, Paige L.; Korrick, Susan A.; Sergeyev, Oleg; Emond, Claude; Birnbaum, Linda S.; Burns, Jane S.; Altshul, Larisa; Patterson, Donald G.; Turner, Wayman E.; Lee, Mary M.; Revich, Boris; Hauser, Russ

    2011-01-01

    INTRODUCTION Dioxins, furans and polychlorinated biphenyls (PCBs) are persistent and bioaccumulative toxic chemicals that are ubiquitous in the environment. We assessed predictors of their serum concentrations among women living in a Russian town contaminated by past industrial activity. METHODS Blood samples from 446 mothers aged 23–52 years were collected between 2003–2005 as part of the Russian Children’s Study. Serum dioxin, furan and PCB concentrations were quantified using high-resolution gas chromatography-mass spectrometry. Potential determinants of exposure were collected through interviews. Multivariate linear regression models were used to identify predictors of serum concentrations and toxic equivalencies (TEQs). RESULTS AND DISCUSSION The median total PCB concentrations and total TEQs were 260 ng/g lipid and 25 pg TEQ/g lipid, respectively. In multivariate analyses, both total PCB concentrations and total TEQs increased significantly with age, residential proximity to a local chemical plant, duration of local farming, and consumption of local beef. Both decreased with longer breastfeeding, recent increases in body mass index, and later blood draw date. These demographic and lifestyle predictors showed generally similar associations with the various measures of serum dioxins, furans, and PCBs. PMID:20578718

  4. Influence of bottle-feeding on serum bisphenol a levels in infants.

    PubMed

    Rhie, Young-Jun; Nam, Hyo-Kyoung; Oh, Yeon Joung; Kim, Ho-Seong; Lee, Kee-Hyoung

    2014-02-01

    Exposure to endocrine disrupting chemicals (EDCs), particularly during developmental periods, gives rise to a variety of adverse health outcomes. Bisphenol A (BPA) is a well-known EDC commonly found in plastic products including food and water containers, baby bottles, and metal can linings. This study investigates infant exposure to BPA and the effect of bottle-feeding on serum BPA levels in infants. Serum BPA levels in normal healthy infants 6 to 15 months of age (n=60) were evaluated by a competitive ELISA. BPA was detected in every study sample. Serum BPA levels of bottle-fed infants (n=30) were significantly higher than those of breast-fed infants (n=30) (96.58±102.36 vs 45.53±34.05 pg/mL, P=0.014). There were no significant differences in serum BPA levels between boys (n=31) and girls (n=29). No significant correlations were found between serum BPA levels and age, body weight, birth weight, and gestational age. Bottle-feeding seems to increase the risk of infant exposure to BPA. Establishment of health policies to reduce or prevent BPA exposure in infants is necessary.

  5. Determination of silicon in serum and urine by electrothermal atomic absorption spectrometry

    NASA Astrophysics Data System (ADS)

    Huang, Zhuo-er

    1995-09-01

    A sensitive, simple and accurate method for the routine determination of trace silicon in serum and urine by Zeeman electrothermal atomic absorption spectrometry is described. The samples are directly determined after 20-fold dilution of serum and 100-fold dilution of urine. No L'vov platform is used. The signal enhancement of silicon atomization in pyrolytic graphite coated graphite tubes is achieved by using a mixture of calcium chloride and lanthanum nitrate as chemical modifier. The interferences arising from the biological matrices have been eliminated by the addition of ammonium dihydrogenphosphate in the sample solutions. The aqueous calibration curve is linear to at least 300 μg l -1, the characteristic mass is 37 pg (integrated absorbance signal), whereas the detection limit (3SD) is 1.5 μg l -1 for silicon in both diluted serum and urine samples. The recoveries of silicon added to the diluted samples are 101 ± 1.8% for sera and 98.2 ± 3.5% for the urine specimens, independent of the dilution ratio. The silicon measurement results for the serum and urine from healthy adults and for the serum from the patients with chronic renal failure on hemodialysis are presented.

  6. Peptidomic Identification of Serum Peptides Diagnosing Preeclampsia

    PubMed Central

    Wu, Shuaibin; Stevenson, David K.; Sheng, Guojun; Butte, Atul J.; Ling, Xuefeng B.

    2013-01-01

    We sought to identify serological markers capable of diagnosing preeclampsia (PE). We performed serum peptide analysis (liquid chromatography mass spectrometry) of 62 unique samples from 31 PE patients and 31 healthy pregnant controls, with two-thirds used as a training set and the other third as a testing set. Differential serum peptide profiling identified 52 significant serum peptides, and a 19-peptide panel collectively discriminating PE in training sets (n = 21 PE, n = 21 control; specificity = 85.7% and sensitivity = 100%) and testing sets (n = 10 PE, n = 10 control; specificity = 80% and sensitivity = 100%). The panel peptides were derived from 6 different protein precursors: 13 from fibrinogen alpha (FGA), 1 from alpha-1-antitrypsin (A1AT), 1 from apolipoprotein L1 (APO-L1), 1 from inter-alpha-trypsin inhibitor heavy chain H4 (ITIH4), 2 from kininogen-1 (KNG1), and 1 from thymosin beta-4 (TMSB4). We concluded that serum peptides can accurately discriminate active PE. Measurement of a 19-peptide panel could be performed quickly and in a quantitative mass spectrometric platform available in clinical laboratories. This serum peptide panel quantification could provide clinical utility in predicting PE or differential diagnosis of PE from confounding chronic hypertension. PMID:23840341

  7. Serum growth factors in asbestosis patients.

    PubMed

    Li, Yongliang; Karjalainen, Antti; Koskinen, Heikki; Vainio, Harri; Pukkala, Eero; Hemminki, Kari; Brandt-Rauf, Paul W

    2009-02-01

    Various growth factors, including platelet-derived growth factor (PDGF) and transforming growth factor (TGF)-beta, have been implicated in the pathogenesis of asbestos-induced disease. PDGF and TGF-beta levels were determined by enzyme-linked immunosorbent assays in the banked serum samples of a cohort of workers with asbestosis, and the relationships of the growth factor levels to the subsequent development of cancer and to the radiographic severity and progression of asbestosis in the cohort were examined. Serum levels of PDGF and TGF-beta were found to be unrelated to the development of cancer, and serum levels of PDGF were found to be unrelated to the severity and progression of asbestosis. However, serum levels of TGF-beta were found to be statistically significantly related to disease severity (p = 0.01), increasing approximately 2.4-fold from ILO radiographic category 0 to category 3, and they were marginally related to disease progression (p = 0.07), in multivariate analysis controlling for other contributory factors including cumulative asbestos exposure. This suggests that serum TGF-beta may be a useful biomarker for asbestos-induced fibrotic disease. PMID:19283526

  8. Serum albumin and risk of venous thromboembolism

    PubMed Central

    Folsom, Aaron. R.; Lutsey, Pamela L.; Heckbert, Susan R.; Cushman, Mary

    2010-01-01

    Summary The incidence of venous thromboembolism (VTE) is increased in patients with albuminuria. However, whether a low serum albumin concentration is associated with increased risk of VTE has been a matter of controversy. We determined the association of serum albumin with VTE incidence in two large, prospective, population-based cohorts: the Atherosclerosis Risk in Communities (ARIC) Study (n = 15,300) and the Cardiovascular Health Study (CHS) (n = 5,400). Validated VTE occurrence (n=462 in ARIC and n=174 in CHS) was ascertained during follow-up. In both studies, after adjustment for age, sex, race, use of hormone replacement therapy, estimated GFR, history of cancer, and diabetes, serum albumin tended to be associated inversely with VTE. The adjusted hazard ratio per standard deviation lower albumin was 1.18 (95% CI = 1.08, 1.31) in ARIC and 1.10 (95% CI = 0.94, 1.29) in CHS. The hazard ratio for albumin below (versus above) the fifth percentile was 1.28 (95% CI = 0.90, 1.84) in ARIC and 1.80 (95% CI = 1.11, 2.93) in CHS. In conclusion, low serum albumin was a modest marker of increased VTE risk. The observed association likely does not reflect cause and effect, but rather that low serum albumin reflects a hyperinflammatory or hypercoagulable state. Whether this association has clinical relevance warrants further study. PMID:20390234

  9. Radioimmunoassy for phencyclidine (PCP) in