Abstract  Self-assemblies of poly(methyl methacrylate)-block-poly(2-perfluorooctylethyl methacrylate)-block copolymers in organic solvents were examined. It was confirmed from light scattering that block copolymers formed aggregates of 410 molecules in acetonitrile and of 26 molecules in chloroform. Spherical morphologies were displayed in cryo-transmission electron-microscope (cryo-TEM) photographs and in atomic-force microscope images. The spherical particles consisted of a core of poly(2-perfluorooctylethyl methacrylate) and a shell (corona) of poly(methyl methacrylate). It was elucidated from molecular geometry that the particles in acetonitrile are typical polymer micelles of approximate to 150 Angstrom core radius and similar to 150 Angstrom corona thickness, while those in chloroform are 'crew-cut' aggregates. The external contrast variation examination of small-angle neutron scattering and cryo-TEM suggested that the solvent penetration into polymer micelles in acetonitrile is less in the core than in the shell. (C) 2000 Elsevier Science B.V. All rights reserved.

Abstract  Eleven perfluorinated alkyl acids (PFAAs) were analyzed in plasma from a total of 600 American Red Cross adult blood donors from six locations in 2010. The samples were extracted by protein precipitation and quantified by using liquid chromatography tandem mass spectrometry (HPLC/MS/MS). The anions of the three perfluorosulfonic acids measured were perfluorobutane sulfonate (PFBS), perfluorohexane sulfonate (PFHxS), and perfluorooctane sulfonate (PFOS). The anions of the eight perfluorocarboxylic acids were perfluoropentanoate (PFPeA), perfluorohexanoate (PFHxA), perfluoroheptanoate (PFHpA), perfluorooctanoate (PFOA), perfluorononanoate (PFNA), perfluorodecanoate (PFDA), perfluoroundecanoate (PFUnA), and perfluorododecanoate (PFDoA). Findings were compared to results from different donor samples analyzed at the same locations collected in 2000-2001 (N = 645 serum samples) and 2006 (N = 600 plasma samples). Most measurements in 2010 were less than the lower limit of quantitation for PFBS, PFPeA, PFHxA, and PFDoA. For the remaining analytes, the geometric mean concentrations (ng/mL) in 2000-2001, 2006, and 2010 were, respectively, PFHxS: (2.25, 1.52, 1.34); PFOS (34.9, 14.5, 8.3); PFHpA (0.13, 0.09, 0.05); PFOA (4.70, 3.44, 2.44); PFNA (0.57, 0.97, 0.83); PFDA (0.16, 0.34, 0.27), and PFUnA (0.10, 0.18, 0.14). The percentage decline (parentheses) in geometric mean concentrations from 2000-2001 to 2010 were PFHxS (40%), PFOS (76%), and PFOA (48%). The decline in PFOS suggested a population halving time of 4.3 years. This estimate is comparable to the geometric mean serum elimination half-life of 4.8 years reported in individuals. This similarity supports the conclusion that the dominant PFOS-related exposures to humans in the United States were greatly mitigated during the phase-out period.

Abstract  Perfluorobutanesulfonate (PFBS) is a surfactant and degradation product of substances based on perfluorobutanesulfonyl fluoride. A two-generation reproductive rat study has been conducted with potassium PFBS (K(+)PFBS). Parental-generation (P) rats were dosed orally by gavage with 0, 30, 100, 300 and 1000mg K(+)PFBS/kg/day for 10 weeks prior to and through mating (males and females), as well as during gestation and lactation (females only). First generation (F1) pups were dosed similarly, beginning at weaning. Second generation (F2) pups were not directly dosed but potentially exposed to PFBS through placental transfer and nursing, and the study was terminated 3 weeks after their birth. Endpoints evaluated included body weight, food consumption, clinical signs, estrus cycling, sperm quality, pregnancy, natural delivery, litter outcomes, and developmental landmarks. The no-observable-adverse effect dose level (NOAEL) in the parental generations (P and F1) was 100mg/kg/day. In the 300 and 1000mg/kg/day dose group rats, there were (1) increased liver weight (absolute or relative) and corresponding increased incidence of adaptive hepatocellular hypertrophy (male only) and (2) increased incidence of minimal to mild microscopic findings in the medulla and papilla of the kidneys (male and female). There were no K(+)PFBS treatment-related effects on fertility or reproduction among the P or the F1 rats. There were no microscopic changes in male or female reproductive organs, and no biologically relevant effects on sperm parameters, mating, estrous cycles, pregnancy, and natural delivery in the P- or F1-generations. There were no K(+)PFBS treatment-related effects on survival of pups in the two-generation study. Litter size and average pup birth weight per litter were not statistically significantly different from controls in any dose group. In the F1-generation, terminal body weight was reduced in males at 1000mg/kg/day. Preputial separation was slightly delayed (approximately 2 days) at this dose, a finding consistent with the body weight reduction. Essentially no effects were observed in the F1 females. F2 pups had normal body weights. The reproductive NOAEL was >1000mg/kg/day in both generations.

Abstract  This work directly compares vapour and liquid aerosol states for the deposition of perfluorocarbon coatings using an atmospheric pressure, non-thermal equilibrium plasma jet system. The objective of the study is to evaluate how the physical state of the precursor (gas or liquid), influences the fragmentation of the monomer molecules in the plasma and the subsequent coating properties. Specifically the effect of gas or liquid aerosol precursor feed on the ability to achieve a soft plasma polymerization (SPP) is assessed with a view to producing a coating that exhibits minimal fragmentation, while being well cross-linked. The precursor (perfluoro-1-decene) was introduced into a helium plasma and coatings deposited at rates of up to 50 nm . min(-1). The deposited coatings were examined using XPS, FTIR, contact angle and ellipsometric measurements. These indicated that a controlled polymerization reaction through the vinyl group of the monomer had taken place in the case of the gas deposited samples with only minor fragmentation of the functional perfluoro chain. Furthermore, a high level of cross-linking was achieved and the perfluorocarbon coatings were stable to a toluene wash. In contrast, while coatings deposited using the liquid deposition technique showed good retention of monomer molecular structure, they exhibited poor stability when immersed in toluene. This is attributed to lower levels of cross-linking of the liquid precursor in the plasma, compared with coatings deposited using the gaseous precursor technique.

Abstract  A Monte Carlo simulation using a diffusion based exposure assessment model was employed to aid forecasting of solvent vapour concentrations in the workspace during wipe cleaning of metal components. Range values for the important variables were chosen so as to be appropriated for wipe cleaning with either highly volatile solvents such as Vertrel-MCA or HFE71DE or with less volatile solvents such as n-propylbromide (nPBr). Emphasis is put on confirming that the range values of variables and the distributions taken are applicable to the workplace environment so that the simulation values obtained are reasonable estimates of the true vapour concentrations. The results obtained using Monte Carlo forecasts are considered most useful when taken in conjunction with the relevant occupational exposure limits for the solvents in question.

Abstract  The toxic Paraphenylenediamine is characterized by infrared spectrophotometry and nuclear magnetic resonance spectroscopy, whereas, high performance liquid chromatography with a refractive index detector was used to determine its purity in the suspect samples using external standardisation. An analytical method for determination of lower traces of paraphenylenediamine in post-mortem biological fluids was developed. This procedure involves deproteneization or hydrolysis followed by liquid-liquid extraction and derivatization with trifluoroacetic anhydride. 1 microL of the extract was then analysed by gas chromatography/iontrap mass spectrometry. Benzidine used as the internal standard for quantification and the extraction recovery test was evaluated to 85%. This method was validated in cases with paraphenylenediamine poisoning.

Abstract  Concern with increasing levels of emerging contaminants exists on a global scale. Three commonly observed emerging environmental contaminants: triclosan (2,4,4-trichloro-2'-hydroxydiphenyl ether), a synthetic, broad-spectrum antibacterial agent, and perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA), used in stain- and water-resistant treatments, have become distributed ubiquitously across ecosystems and have been detected in wildlife and humans. MCF-7 BOS human breast cancer cells were used to investigate the potential for cytotoxicity, estrogenicity and anti-estrogenicity of these three compounds at environmentally relevant concentrations using the 3-(4,5-dimethylthiazol-2-yl)-5-(3-carboxymethoxyphenyl)-2-(4-sulfophenyl)-2H-tetrazolium, inner salt assay (MTS) and the E-SCREEN bioassay. The doses used were 0.002-200 µg ml(-1) for triclosan and 0.03-30 µg ml(-1) for PFOS and PFOA. Quantitative results from the MTS assay revealed no significant cytotoxicity at lower concentrations for any of the test compounds; however, both triclosan and PFOA were cytotoxic at the highest concentrations examined (100-200 and 30 µg ml(-1), respectively), while PFOS showed no significant cytotoxicity at any of the concentrations tested. Positive estrogenic responses (P < 0.05) were elicited from the E-SCREEN at all concentrations examined for triclosan and PFOA and at 30 µg ml(-1) for PFOS. Further, significant anti-estrogenic activity (P < 0.05) was detected for all compounds tested at all concentrations when cells were co-exposed with 10(-9) m 17-β estradiol (E(2)). The overall results demonstrated that triclosan, PFOS and PFOA have estrogenic activities and that co-exposure to contaminants and E(2) produced anti-estrogenic effects. Each of these compounds could provide a source of xenoestrogens to humans and wildlife in the environment. Published 2011. This article is a US Government work and is in the public domain in the USA.

Abstract  For the analysis of perfluorobutane sulfonate (PFBS), perfluorohexane sulfonate (PFHxS) and perfluorooctane sulfonate (PFOS) in shells, an extraction method of mixed inorganic acid digestion coupled with solid phase extraction (SPE) was established. The target compounds were determined by high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). The shell powder was at first digested with the mixture of nitric acid and hydrochloric acid, then the digestion solution was adjusted to pH 6 with sodium hydroxide, and cleaned up with Oasis WAX SPE cartridge. The perfluoro sulfonated chemicals were quantified with HPLC-MS/MS using electrospray ionization in negative ion mode with internal standard method. The limits of detection (LODs) were of 0.28 ng/g for PFBS, 0.42 ng/g for PFHxS and 0.43 ng/g for PFOS, and matrix recoveries of the perfluoro sulfonated chemicals were 94.88%-96.24%. The analytical results for the shells of two bivalves from Bohai Bay showed this pretreatment method is suitable for the determination of perfluoro sulfonated acids (PFSAs) in shells. Concentrations of PFSAs in the shells ranged from < LOD-0.70 ng/g, which were an order of magnitude lower than those in the soft tissues of these bivalves.

Abstract  A new family of porous fluorinated membranes was developed from perfluoropolyethers (PFPEs). The PFFE-dimethacrylate (3) was dispersed in isopropanol to form a clear homogeneous solution, which after UV curing in polypropylene molds formed a porous polymer disk. A series of 10 polymers was prepared with ratios of isopropanol to PFPE ranging from 1.3:1 to 0.2:1. The water content of the membranes after hydration varied from 56 to 7% (w/w) and was directly proportional to the percentage of isopropanol used in the polymerization. However, the tensile elastic modulus, which ranged from 0.17 to 15 MPa, was inversely proportional to the water content. The high water content membranes 152 and 46% (w/w)] had a similar permeability to glucose, inulin, and albumin, while the membranes with lower water contents of 37 and 25% displayed progressively lower permeability. (C) 2001 John Wiley & Sons, Inc.

Abstract  Benzyl alcohol is commonly used as an antibacterial agent in a variety of pharmaceutical formulations. Several fatalities in neonates have been linked to benzyl alcohol poisoning. Most methods for measuring benzyl alcohol concentrations in serum utilize direct extraction followed by high-performance liquid chromatography. We describe here a novel derivatization of benzyl alcohol using perfluorooctanoyl chloride after extraction from human serum for analysis by gas chromatography-mass spectrometry (GC-MS). The derivative was eluted at a significantly higher temperature respective to underivatized molecule and the method was free from interferences from more volatile components in serum and hemolyzed specimens. Another advantage of this derivatization technique is the conversion of low-molecular-mass benzyl alcohol (Mr 108) to a high-molecular-mass derivative (Mr 504). The positive identification of benzyl alcohol can be achieved by observing a distinct molecular ion at m/z 504 as well as the base peak at m/z 91. Quantitation of benzyl alcohol in human serum can easily be achieved by using 3,4-dimethylphenol as an internal standard. The within run and between run precisions (using serum standard of benzyl alcohol: 25 mg/l) were 2.7% (mean=24.1, S.D.=0.66 mg/l, n = 8) and 4.2% (mean=24.3, S.D.=1.03 mg/l, n = 8), respectively. The assay was linear for the serum benzyl alcohol concentrations of 2 mg/l to 200 mg/l and the detection limit was 0.1 mg/l. We observed no carry-over (memory effect) problem in our assay as when 2 microl ethyl acetate was injected into the GC-MS system after analyzing serum specimens containing 200 mg/l of benzyl alcohol, we observed no peak for either benzyl alcohol or the internal standard in the total ion chromatogram.

Abstract  Human synthetic islet amyloid polypeptide (hIAPP) is rapidly converted to beta-sheet conformation and fibrils in aqueous media. Optimal solubility conditions for hIAPP were determined by circular dichroism spectroscopy and transmission electron microscopy. hIAPP in trifluoroethanol or hexafluoro-2-isopropanol (HFIP) diluted in water or phosphate buffer (PB) exhibited random structure which was converted to beta-sheet and fibrils with time. hIAPP, solubilised in HFIP, filtered and lyophilised remained in stable random structure for up to 7 days in water; in PB, insoluble aggregates precipitated from which protofilaments and fibrils formed with time. This suggests that amorphous aggregates of hIAPP could initiate islet amyloidosis in vivo.

Abstract  Retention data for a set of 69 compounds using rapid gradient elution are obtained on a wide range of reversed-phase stationary phases and organic modifiers. The chromatographic stationary phases studied are Inertsil (IN)-ODS, pentafluorophenyl, fluoro-octyl, n-propylcyano, Polymer (PLRP-S 100), and hexylphenyl. The organic solvent modifiers are 2,2,2-trifluoroethanol (TFE); 1,1,1,3,3,3-hexafluoropropan-2-ol (HFIP); isopropanol; methanol (MeOH); acetonitrile (AcN); tetrahydrofuran; 1,4-dioxane; N,N-dimethylformamide; and mixed solvents of dimethylsulfoxide (DMSO) with AcN and DMSO with MeOH (1:1). A total of 25 chromatographic systems are analyzed using a solvation equation. In general, most of the systems give reasonable statistics. The selectivity of the reversed phase-high-performance liquid chromatographic (HPLC) systems with respect to the solute's dipolarity-polarity, hydrogen-bond acidity, and basicity are reflected in correspondingly large coefficients in the solvation equation. We wanted to find the most orthogonal HPLC systems, showing the highest possible selectivity difference in order to derive molecular descriptors using the gradient retention times of a compound. We selected eight chromatographic systems that have a large range of coefficients of interest (s, a, and b) similar to those found in water-solvent partitions used previously to derive molecular descriptors. The systems selected are IN-ODS phases with AcN, MeOH, TFE, and HFIP as mobile phase, PLRP-S 100 phase with AcN, propylcyano phase with AcN and MeOH, and fluorooctyl phase with TFE. Using the retention data obtained for a compound in the selected chromatographic systems, we can estimate the molecular descriptors with the faster and simpler gradient elution method.

Abstract  This study reports the effect of a nonionic perfluorinated surfactant, N-polyoxyethylene-N-propyl perfluorooctane sulfonamide (PFOSA), as additive of background electrolyte on capillary electrophoresis (CE) of common inorganic cations. The association constants (K sub(ass)) for PFOSA estimated from the electrophoretic mobility of analyte cations were the order of Mg super(2+) > Ca super(2+) > Sr super(2+) >> K super(+) approximately NH super(+) sub(4) > Na super(+) approximately Li super(+). The K sub(ass) values were larger than those for zwitterionic and nonionic surfactants with hydrocarbon moiety. Use of PFOSA made another essential contribution to the determination of inorganic cations in a protein-containing sample. This was considered because high solubility of PFOSA for proteins functioned as suppressor for protein adsorption to the capillary wall. Four inorganic cations, Na super(+), K super(+), Mg super(2+), and Ca super(2+), in human saliva sample were successfully determined by sample injection without any pretreatments except for filtration and dilution.

Abstract  Perfluorinated compounds (PFCs) are negatively charged and have low pK(a) values in water; therefore, a laboratory-scale electro-microfiltration (EMF) unit that applies a direct-current electrical field across its membrane can greatly enhance their removal from aqueous systems. We examined the effects of an aqueous inorganic matrix (pH: 4, 7, or 10; ionic strength: 0.4-4.8 mM; ionic composition: Na(2)SO(4), NaCl, NH(4)Cl or CaCl(2)) and an organic matrix such as dissolved organic matter (DOM) on the ability of EMF to remove perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS). Decreased removal of PFOX (X = A or S) was observed when the proton concentration and the ionic strength increased. When the applied electrical field strength was less than the critical electrical field strength (E(critical, HA)), PFOX removal was lower in the presence of DOM. We hypothesize that these matrices affect PFOX rejection by altering membrane zeta potential during filtration in the presence of an electrical field. In addition, EMF was found to remove three other PFCs effectively (perfluorodecanoic acid, perfluorohexane sulfonate, and perfluorohexanoic acid), and was also able to remove 70% PFOX and 80% DOC from real industrial wastewaters.

Abstract  Zifrosilone (1-(3-trimethylsilylphenyl)-2 2,2-trifluoroethanone) (3) is a cholinesterase inhibitor that has been studied for the treatment of Alzheimer's disease. Process research has been carried out on a route to convert phenyltrimethylsilane to 3 by Friedel-Crafts acylation using trifluoroacetic anhydride. Kinetics and products analyses suggest that the optimal conditions for this reaction are noncatalytic amounts of aluminum chloride, dichloromethane solvent and as low a temperature as can be practically used in a scaled-up process. Significant separation challenges to isolate 3 from the isomer byproduct 1-(4-trimethylsilylphenyl -2,2,2-trifluoroethanone) (4) remain. These challenges were investigated using vapor-liquid equilibrium studies.

Abstract  The mechanism and kinetics of 2,2,3,3,3-pentafluoropropanol (CF3CF2CH2OH) reaction with Chlorine atom (Cl) is investigated in this work. Two hydrogen abstraction channels of the title reaction are identified. The geometries of all the stationary points in the potential energy surface are obtained at the BHandHLYP/6-311G** level, and the energies of the selected points along the minimum energy path (MEP) are improved by the CCSD(T) method. A dual-level direct dynamics method is employed to study the kinetic nature of the hydrogen-abstraction reaction channels. The calculated rate coefficients show that the hydrogen abstraction from the CH2 group is the primary channel. The calculated total rate coefficients are in best agreement with the experimental values. The four-parameter rate coefficients expression of the title reaction between the temperatures 200 K and 1000 K is provided.

Abstract  Significant evidence supports that many endocrine disrupting chemicals could affect female reproductive health. Aim of this study was to compare the internal exposure to bisphenol A (BPA), perfluorooctane sulphonate (PFOS), perfluorooctanoic acid (PFOA), monoethylhexyl phthalate (MEHP), and di(2-ethylhexyl) phthalate (DEHP) in serum samples of 111 infertile women and 44 fertile women. Levels of gene expression of nuclear receptors (ER α , ER β , AR, AhR, PXR, and PPAR γ ) were also analyzed as biomarkers of effective dose. The percentage of women with BPA concentrations above the limit of detection was significantly higher in infertile women than in controls. No statistically significant difference was found with regard to PFOS, PFOA, MEHP and DEHP. Infertile patients showed gene expression levels of ER α , ER β , AR, and PXR significantly higher than controls. In infertile women, a positive association was found between BPA and MEHP levels and ER α , ER β , AR, AhR, and PXR expression. PFOS concentration positively correlated with AR and PXR expression. PFOA levels negatively correlated with AhR expression. No correlation was found between DEHP levels and all evaluated nuclear receptors. This study underlines the need to provide special attention to substances that are still widely present in the environment and to integrate exposure measurements with relevant indicators of biological effects.

Abstract  We analysed polychlorinated dibenzo-p-dioxins and furans (PCDD/F, dioxins), and polychlorinated biphenyls (PCB) in 13 fish meal, five fish oil, and seven fish feed samples. Polybrominated diphenyl ethers (PBDE), organotin compounds (OTC), and perfluoroalkylated substances (PFAS) were analysed in ten fish meal, two fish oil, and two fish feed samples. All measured TEQ concentrations of PCDD/F and PCB were below the maximum levels set by Directive 2002/32/EC. There was no correlation between concentrations of WHOPCDD/F-TEQ and indicator PCB in our samples. The most common congeners among PBDEs were BDE-47 and BDE-100. BDE-209 was present in five fish meals of the ten analysed. Tributyltin (TBT) was the predominant congener in all samples except in three fish meals, where monobutyltin (MBT) was the major congener. Perfluorooctane sulphonate (PFOS) was the predominant congener in six fish meals of the ten analysed. There was large variation in concentrations and congener distributions of the studied compounds between our samples. Our results underline a need to pay special attention to the origin and purity of feed raw material of marine origin.

Abstract  The persistent nature of perfluorochemicals (PFCs) has attracted global concern in recent years. Perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) are the most commonly found PFC compounds, and thus their fate and transport play key roles in PFC distribution in the natural environment. As most solid phases in natural water contain alumina, an investigation of PFOS and PFOA adsorption behavior on alumina should prove useful in evaluating the environmental impact of this type of persistent pollutant. Systematic experiments were carried out in this study to investigate the adsorption behavior of PFOS and PFOA onto alumina. The results of adsorption kinetics on alumina show that it takes 48 h to reach equilibrium. The adsorption isotherms reveal maximum adsorption capacities of 0.252 μg/m(2) for PFOS and 0.157 μg/m(2) for PFOA at pH = 4.3, with the difference primarily due to their different functional groups. An increase in pH leads to a decrease in PFOS and PFOA adsorption on alumina, which may be attributed to the reduction in electrostatic interaction. The adsorption of both PFOS and PFOA decreases with an increase in ionic strength for all four types of cations (Na(+), K(+), Mg(2+), and Ca(2+)), due to the compression of the electrical double layer. Furthermore, the results also indicate that both Ca(2+) and Mg(2+) can form bridges with PFOA anions in solution, whereas only PFOS can be bridged by Ca(2+) due to the higher covalent nature of magnesium.

Abstract  Decomposition of C5-C9 perfluorocarboxylic acids (PFCAs) and perfluoroether carboxylic acids (alternatives to PFCA-based surfactants) in hot water in a sealed reactor was investigated. Although PFCAs showed almost no decomposition in hot water at 80 degrees C in the absence of persulfate (S2O8(2-)), the addition of S2O8(2-) to the reaction system led to efficient decomposition, even at this relatively low temperature. The major products in the aqueous and gas phases were F- ions and CO2, respectively, and short-chain PFCAs were also detected in the aqueous phase. For example, when an aqueous solution containing perfluorooctanoic acid (PFOA, 374 microM) and S2O8(2-) (50.0 mM) was heated at 80 degrees C for 6 h, PFOA concentration in the aqueous phase fell below 1.52 microM (detection limit of HPLC with conductometric detection), and the yields of F- ions [i.e., (moles of F- formed) /(moles of fluorine content in initial PFOA)] and CO2 [i.e, (moles of CO2 formed) /(moles of carbon content in initial PFOA)] were 77.5% and 70.2%, respectively. This method was also effective in decomposing perfluoroether carboxylic acids, such as CF3OC2F4OCF2COOH, CF3OC2F4OC2F4OCF2COOH, and C2F5OC2F4OCF2COOH, which are alternatives to PFCA-based surfactants, producing F- and CO2 with yields of 82.9-88.9% and 87.7-100%, respectively, after reactions at 80 degrees C for 6 h. In addition, the method was successfully used to decompose perfluorononanoic acid in a floor wax solution. When PFOAwastreated at a higher temperature (150 degrees C), other decomposition reactions occurred: the formation of F- and CO2 was dramatically decreased, and 1H-perfluoroalkanes (C(n)F(2n+1)H, n = 4-7) formed in large amounts. This result clearly indicates that treatment with high-temperature water was not suitable for the decomposition of PFCAs to F-: surprisingly, the relatively low temperature of 80 degrees C was preferable.

Abstract  Perfluorooctanoate (PFOA) has been detected in surface water all over the world, and little is known of its removal by coagulation in water treatment plants. In this study, polyaluminium chloride (PACl) was used to remove PFOA from surface water, and the effects of coagulant dose, solution pH, temperature, and initial turbidity on the removal of both PFOA and suspended solids (SS) from water were investigated. Since the SS had high sorption affinity for PFOA, most PFOA was adsorbed on the particles and removed via the SS removal in the coagulation process. PFOA concentrations in aqueous phase decreased with increasing initial turbidity and PACl dose, while they increased with increasing solution pH and temperature. Other perfluorinated compounds (PFCs) with different C-F chain lengths and functional groups were also compared with PFOA. It was proved that hydrophobic interaction played an important role in the adsorption of PFOA on the SS. The addition of powdered activated carbon (PAC) before the coagulation process significantly enhanced the removal efficiency of PFOA in water, and the residual PFOA concentrations in water were less than 1 μg/L after the addition of 1-16 mg/L PAC and subsequent coagulation when the initial PFOA concentrations were in the range of 0.5-3 mg/L.

Abstract  BACKGROUND: Immune suppression may be a critical effect associated with exposure to perfluorinated compounds (PFCs), as indicated by recent data on vaccine antibody responses in children. Therefore, this information may be crucial when deciding on exposure limits. METHODS: Results obtained from follow-up of a Faroese birth cohort were used. Serum-PFC concentrations were measured at age 5 years, and serum antibody concentrations against tetanus and diphtheria toxoids were obtained at ages 7 years. Benchmark dose results were calculated in terms of serum concentrations for 431 children with complete data using linear and logarithmic curves, and sensitivity analyses were included to explore the impact of the low-dose curve shape. RESULTS: Under different linear assumptions regarding dose-dependence of the effects, benchmark dose levels were about 1.3 ng/mL serum for perfluorooctane sulfonic acid and 0.3 ng/mL serum for perfluorooctanoic acid at a benchmark dose response of 5%. These results are below average serum concentrations reported in recent population studies. Even lower results were obtained using logarithmic dose--response curves. Assumption of no effect below the lowest observed dose resulted in higher benchmark dose results, as did a benchmark response of 10%. CONCLUSIONS: The benchmark dose results obtained are in accordance with recent data on toxicity in experimental models. When the results are converted to approximate exposure limits for drinking water, current limits appear to be several hundred fold too high. Current drinking water limits therefore need to be reconsidered.

Abstract  Exposure of mice to perfluorooctanoate (PFOA) evokes pronounced hepatomegaly along with significant alterations in both the histological structure and immune status of the liver. The present study was designed to evaluate the effects of this perfluorochemical on immune-mediated liver damage. In this connection, the influence of both sub-acute (10 days), moderate-dose (0.002% w/w=3±0.7mg/kg body weight/day) and short-term (28 days), low-dose (0.00005% w/w=70±2μg/kg body weight/day) dietary pretreatment with PFOA on the development of concanavalin A (Con A)-induced liver damage in mice was examined. With sub-acute, moderate, but not short-term, low-dose exposure, PFOA aggravated the acute liver damage caused by Con A, i.e., elevated serum levels of transaminases and led to more pronounced damage of hepatic tissue. This aggravation was associated with significantly enhanced hepatic level of interleukin-6 (IL-6), but unaltered hepatic levels of tumor necrosis factor-alpha (TNF-α), interferon-gamma (IFN-γ) and interleukin-4 (IL-4). Moreover, hepatic DNA fragmentation was not changed by sub-acute exposure to the moderate-dose. Our findings imply that exposure to PFOA may sensitize hepatic parenchymal cells to other toxicants that activate the hepatic immune system and thereby aggravate liver injury during acute inflammation.

Abstract  In the present study, we have used salmon embryos whose continuous exposure to waterborne PFOA or PFOS at 100 μg/L started as freshly fertilized eggs, and lasted for a total of 52 days. PFOS and PFOA were dissolved in methanol (carrier vehicle) whose concentration never exceeded 0.01% of total tank volume. Samples were collected at day 21, 28, 35, 52, 49 and 56 after the start of the exposure. Note that days 49 and 56 represent end of exposure and 1 week after a recovery period, respectively. Tissue bioaccumulations were determined by HPLC/MS/MS, steroid hormones, fatty acids (FAs) and lipids were determined by GC-MS, while mRNA expression levels of genes were determined by qPCR in whole body homogenate. We observed that PFOS and PFOA showed a steady increase in whole body burden during the exposure period, with a slight decrease after the recovery period. Calculated somatic indexes showed that PFOA produced increases in heart-, thymus-, liver- and kidney somatic indexes (HSI, TSI, LSI and KSI). PFOA and PFOS exposure produced significant decreases in whole body dehydroepiandrosterone (DHEA), estrone and testosterone at sampling day 21 and a strong increase of cortisol and cholesterol at the end of recovery period (day 56). PFOA and PFOS effects differed with DHEA and estrone. While PFOS decreased DHEA levels, PFOA produced an increase at day 49, and while PFOS decreased estrone, PFOA produced a slight increase at day 56. We observed changes in FA composition that predominantly involved increases in FA methyl esters (FAMEs), mono- and poly-unsaturated FA (MUFA and PUFA) and a decrease in n-3/n-6 PUFA ratio by both PFOA and PFOS. Particularly, an increase in - pentadecenoic MUFA (15:1), two n-3 PUFAs α-linolenic acid [ALA: 18:3 n3] and eicosapentaenoic acid [EPA: 20:5 n-3] and n-6 PUFA: arachidonic acid [ARA: 20:4 n6], docosapentaenoic acid (DPA) by PFOA and PFOS were observed. These effects were associated with changes in mRNA expression of FA elongase (FAE), Δ5-desaturase (FAD5) and Δ6-desaturase (FAD6) genes. In summary, the changes in hormonal and FA profiles may represent cellular and/or physiological adaptation to continuous PFOS and PFOA exposure by increasing membrane fluidity, and/or overt developmental effects. The present findings provide some potential insights and basis for a better understanding on the possible mechanisms of PFCs toxicity in fish.