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  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  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  Perfluorooctanoic acid (PFOA) is an emerging environmental pollutant attracting significant attention due to its global distribution, high persistence, and bioaccumulation properties. In this study, the degradation of aqueous PFOA at different temperatures was examined using heat-activated persulfate. Using this approach, 93.5% of PFOA was degraded after 30 h at 85 degrees C with 43.6% of F- yield, and the shorter chain length compounds (PFHpA (C6F13COOH), PFHxA (C5F11COOH), PFPeA (C4F9COOH), and PFBA (C3F2COOH)) were observed as degradation intermediates. The sequential degradation mechanism of losing one CF2 unit from PFOA and its intermediates on a step-by-step basis were observed. Controlled temperature kinetics studies yielded an activation energy of approximately 60 kJ/mol for the degradation of PFOA by heat-activated persulfate. However, at elevated temperatures, excess persulfate is needed for efficient PFOA degradation, presumably due to more intensive SO4 center dot- scavenging. Lower reaction pH was generally found to inhibit PFOA degradation, presumably due to the more prevalent radical-to-radical interactions. (C) 2011 Elsevier B.V. All rights reserved.

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  We have evaluated the effect of the perfluorinated fatty acids pentadecafluoro-n-octanoic acid (PFOA) and nonadecafluoro-n-decanoic acid (NDFDA) on the ability of a human B-lymphoblastoid cell line to bind the lipid-binding, membrane-impermeant, fluorescent dye merocyanine 540 (MC540). Subtoxic concentrations of perfluorinated fatty acids (0.9 mM PFOA; 0.5 mM NDFDA) greatly diminish binding of MC540 by normal plasma membranes, as determined by fluorescence flow cytometry. When perfluorinated fatty acids are added to cells at toxic or lethal concentrations (1.2 mM PFOA; 0.75 mM NDFDA), MC540 binding increases dramatically, with entrance of dye to internal membrane domains. Neither perfluorinated fatty acid molecule reduces the ability of surface immunoglobulin to migrate laterally and cap on cells. Our data suggest that perfluorinated fatty acids either interact directly with lipid binding sites for MC540, and thereby inhibit dye intercalation, or alter membrane lipid architecture and lipid packing to diminish MC540 binding. Both possibilities support a direct, physical, membrane-altering mechanism for perfluorinated fatty acid toxicity on mammalian cells.

Abstract  Low level chronic exposure to toxicants is associated with a range of adverse health effects. Understanding the various factors that influence the chemical burden of an individual is of critical importance to public health strategies. We investigated the relationships between socioeconomic status (SES) and bio-monitored chemical concentration in five cross-sectional waves of the U.S. National Health and Nutrition Examination Survey (NHANES). We utilised adjusted linear regression models to investigate the association between 179 toxicants and the poverty income ratio (PIR) for five NHANES waves. We then selected a subset of chemicals associated with PIR in 3 or more NHANES waves and investigated potential mediating factors using structural equation modelling. PIR was associated with 18 chemicals in 3 or more NHANES waves. Higher SES individuals had higher burdens of serum and urinary mercury, arsenic, caesium, thallium, perfluorooctanoic acid, perfluorononanoic acid, mono(carboxyoctyl) phthalate and benzophenone-3. Inverse associations were noted between PIR and serum and urinary lead and cadmium, antimony, bisphenol A and three phthalates (mono-benzyl, mono-isobutyl, mono-n-butyl). Key mediators included fish and shellfish consumption for the PIR, mercury, arsenic, thallium and perfluorononanoic acid associations. Sunscreen use was an important mediator in the benzophenone-3/PIR relationship. The association between PIR and cadmium or lead was partially mediated by smoking, occupation and diet. These results provide a comprehensive analysis of exposure patterns as a function of socioeconomic status in US adults, providing important information to guide future public health remediation measures to decrease toxicant and disease burdens within society.

Abstract  A simplified method has been established to simultaneously characterize different neurosteroids in rat brain by gas chromatography/mass spectrometry (GC-MS). Neurosteroids were isolated separately in a two-step procedure using ethyl acetate in the first step to extract the unconjugated steroids and chloroform/2-butanol(50/50,v/v) in the second step to extract sulfated steroids. All steroid fractions were further purified by solid phase extraction (SPE) and the sulfated steroids were solvolyzed. All steroids were derivatized with heptafluorobutyric acid anhydride and analyzed by GC-MS (electrospray ionization) using selected ion monitoring. In male rat brain, the concentrations of pregnenolone (PREG), progesterone (PROG), allo-pregnanolone (AP) and dihydroepiandrosterone (DHEA) were (8.53 +/- 1.11) ng/g, (7.01 +/- 2.60 )ng/g, (1.17 +/- 0.19 )ng/g, and (0.92 +/- 0.20) ng/g, respectively. The concentrations of pregnenolone sulfate (PREGS) and dihydroepiandrosterone sulfate (DHEAS) were (5.94 +/- 2.03) ng/g and (1.93 +/- 0.92) ng/g, respectively. Good linearity and accuracy were observed for each steroid. The procedure was suitable for measuring the concentrations of endogenous neurosteroids, simultaneously including the sulfates in rat brain.

Abstract  BIOSIS COPYRIGHT: BIOL ABS. RRM ABSTRACT ALUMINUM CLOFIBRATE SIMFIBRATE DIETHYLHEXYL PHTHALATE CARCINOGENESIS 8 HYDROXYDEOXYGUANOSINE PERFLUOROOCTANOIC ACID PERFLUORODECANOIC ACID

Abstract  Elimination in urine and feces was compared between four perfluorinated fatty acids (PFCAs) with different carbon chain length. In male rats, perfluoroheptanoic acid (PFHA) was rapidly eliminated in urine with the proportion of 92% of the dose being eliminated within 120 h after an intraperitoneal injection. Perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA) and perfluorodecanoic acid (PFDA) was eliminated in urine with the proportions of 55, 2.0 and 0.2% of the dose, respectively. By contrast, four PFCAs were eliminated in feces with the proportion of less than 5% of the dose within 120 h after an injection. In female rats, the proportions of PFOA and PFNA eliminated in urine within 120 h were 80% and 51% of the dose, respectively, which were significantly higher compared with those in male rats. There was the tendency that PFCA with longer carbon chain length is less eliminated in urine in both male and female rats. Fecal elimination of PFCAs was not different between PFCAs in female rats and comparable to those in male rats. The rates of biliary excretion of PFCAs in male rats were slower than those in female rats. Sex-related difference in urinary elimination of PFOA was abolished when male rats had been castrated. On the contrary, treatment with testosterone suppressed the elimination of PFOA in urine in both castrated male rats and female rats. The effect of testosterone was in a time- and dose-dependent manner. These results suggest that PFCAs are distinguished by their carbon chain length by a renal excretion system, which is regulated by testosterone.

Abstract  Perfluorinated acids are anthropogenic pollutants with primarily two industrial synthetic routes: electrochemical fluorination (ECF) and telomerization. A mixture of structural isomers is produced by ECF, while telomerization conserves the geometry of its starting materials, which are typically linear. To contribute to a discussion on sources of perfluorinated acid pollution, isomer profiles of perfluorinated carboxylates (PFCAs) were determined in a diverse set of environmental and biotic samples from remote to urban locations. Analysis was conducted on the derivatized extracts using gas chromatography/mass spectrometry. The perfluorooctanoate (PFOA) isomer profile in most samples contained linear and branched isomers congruent with an ECF input, but linear PFOA (n-PFOA) predominated (>90%) greater than in the ECF technical product (78%). The perfluorononanoate (PFNA) isomer pattern varied from only n-PFNA, n- and iso-PFNA (isopropyl isomer), or n-PFNA and multiple branched isomers. At midlatitudes, PFNA isomer profiles containing multiple branched isomers are attributed to ECF sources such as impurities in ECF PFOA. In surface water from Lake Ontario (Canada) and an Arctic lake, only n- and iso-PFNA were observed. Human and dolphin blood contained multiple branched PFNA, consistent with an ECF signature albeit n-isomer enriched. Both n- and isopropyl isomers of longer-chain PFCAs were observed with a distinct pattern for dolphin and Arctic samples compared to those from the Lake Ontario ecosystem. These results support the hypothesis that long-range atmospheric transport of linear volatile precursors, subsequent degradation, and deposition contribute to the presence of n-PFCAs in the Arctic freshwater environment. The presence of longer-chain isopropyl isomers may be preliminary evidence of isopropyl fluorinated organic precursors.

Abstract  In this study we report the human plasma concentrations of some common endocrine disrupting chemicals (EDCs) in the Hong Kong population. We have analyzed 153 plasma samples for the contaminants by methods involving labeled standards spiked into the samples. Quantification was performed using high performance liquid chromatography tandem mass spectrometry for bisphenol-A (BPA) and perfluorinated compounds (PFCs), and gas chromatography mass spectrometry methods for phthalates. We found BPA, several types of PFCs and phthalates in over 90% of the plasma samples. Perfluorooctane sulfonate (PFOS) was the dominant PFC, followed by perfluroroctanoic acid (PFOA) and perfluorohexane sulfonate (PFHxS). Eight out of ten phthalates were detected, with bis(2-ethylhexyl) phthalate (DEHP) as the most abundant, followed by bis(2-methoxyethyl) phthalate (DMEP) and dioctyl phthalate (DnOP). The levels of PFOS, PFOA, PFHxS and perfluorohexanoic acid (PFHxA) were significantly higher in the male plasma samples (p<0.05), while the mean plasma levels of DEHP and n-butyl benzyl phthalate (BBP) were significantly higher in the young age group (p<0.02). The presence of the selected EDCs in human blood plasma indicates common exposure routes among different population cohorts. Although the plasma levels of the EDCs were comparable to other countries, regular monitoring of human blood EDC contamination levels is necessary to provide a time-trend database for the estimation of exposure risk and to formulate appropriate public health policy.

Abstract  A single ip injection of perfluoro-n-decanoic acid (PFDA) to male Wistar rats resulted in an initially rapid, then gradual decrease in food consumption and a parallel loss of body weight. Body temperatures and resting heart rates were significantly depressed by PFDA treatment. As early as 12 h following a single dose of PFDA, serum thyroxine (T4) levels were significantly reduced and remained depressed throughout the 8 day study. Serum triiodothyronine (T3) was reduced by 35% 12 h following PFDA treatment and remained at that level throughout the study. These preliminary data suggest that an action on the thyroid axis may be an early primary response to PFDA and that some of the observed subsequent effects may in part be secondary to the change in thyroid hormone levels.

Abstract  BIOSIS COPYRIGHT: BIOL ABS. This meeting contains abstracts of 42 papers, written in English, covering chemical studies of toxic substances and experimental studies in animals and tissue culture, including enzymology.

Abstract  Organic fluorochemicals are used in multiple commercial applications including surfactants, lubricants, paints, polishes, food packaging, and fire-retarding foams. Recent scientific findings suggest that several perfluorochemicals (PFCs), a group of organic fluorochemicals, are ubiquitous contaminants in humans and animals worldwide. Furthermore, concern has increased about the toxicity of these compounds. Therefore, monitoring human exposure to PFCs is important. We have developed a high-throughput method for measuring trace levels of 13 PFCs (2 per-fluorosulfonates, 8 perfluorocarboxylates, and 3 perfluorosulfonamides) in serum and milk using an automated solid-phase extraction (SPE) cleanup followed by high-performance liquid chromatography-tandem mass spectrometry. The method is sensitive, with limits of detection between 0.1 and 1 ng in 1 mL of serum or milk, is not labor intensive, involves minimal manual sample preparation, and uses a commercially available automated SPE system. Our method is suitable for large epidemiologic studies to assess exposure to PFCs. We measured the serum levels of these 13 PFCs in 20 adults nonoccupationally exposed to these compounds. Nine of the PFCs were detected in at least 75% of the subjects. Perfluorooctanesulfonate (PFOS), perfluorohexanesulfonate (PFHxS), 2-(N-methylperfluorooctanesulfonamido)acetate (Me-PFOSA-AcOH), perfluorooctanoate (PFOA), and perfluorononanoate (PFNA) were found in all of the samples. The concentration order and measured levels of PFOS, PFOA, Me-PFOSA-AcOH, and PFHxS compared well with human serum levels previously reported. Although no human data are available for the perfluorocarboxylates (except PFOA), the high frequency of detection of PFNA and other carboxylates in our study suggests that human exposure to long-alkyl-chain perfluorocarboxylates may be widespread. We also found PFOS in the serum and milk of rats administered PFOS by gavage, but not in the milk of rats not dosed with PFOS. Furthermore, we did not detect most PFCs in two human milk samples. These findings suggest that PFCs may not be as prevalent in human milk as they are in serum. Additional studies are needed to determine whether environmental exposure to PFCs can result in PFCs partitioning into milk. Large epidemiological studies to determine the levels of PFCs among the U.S. general population are warranted.

Abstract  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 with health effects in humans, our findings raise concern on the potential health effects of PFASs in polar bears from Svalbard. Effort should be made to examine the potential health effects of PFASs in polar bears.

Abstract  A well-defined subsample of 128 subadult (3-5 years) polar bears (Ursus maritimus) from 19 sampling years within the period 1984-2006 was investigated for perfluoroalkyl contaminants (PFCs), Linear regression analysis of logarithmic-transformed median concentrations showed significant annual increases for PFOS (4.7%), PFNA (6.1%), PFUnA (5.9%), PFDA (4.3%), PFTrA (8.5%), PFOA (2.3%), and PFDoA (5.2%). For four of the PFCs, a LOESS smoother model provided significantly better descriptions, revealing steeper linear annual increases for PFOSA of 9.2% after 1990 and between 18.6 and 27.4% for PFOS, PFDA, and PFTrA after 2000. Concentrations of Sigma PFCs, by 2006, exceeded the concentrations of all conventional OHCs (organohalogen compounds), of which several have been documented to correlate with a number of negative health effects. If the PFC concentrations in polar bears continue to increase with the steepest observed trends, then the lowest no-adverse-effect level (NOAEL) and lowest-adverse-effect level (LOAEL) detected for rats and monkeys will be exceeded in 2014-2024. In addition, the rapidly increasing concentrations of PFCs are likely to cause cumulative and combined effects on the polar bear, compounding the already detected threats from OHCs.

Abstract  In 2006, California passed legislation establishing the first State Biomonitoring Program in the USA. The main goals are to: 1) Determine levels of environmental chemical contaminants in a representative sample of Californians; 2) Establish trends in the levels of these chemicals over time; 3) Assess the effectiveness of public health efforts and regulatory programs to decrease exposures to specific chemicals.

As part of the Biomonitoring Program, our laboratory will be conducting analyses for Persistent Organic Pollutants (POPs) such as organochlorine pesticides (OCPs), PCBs, polybrominated diphenyl ethers (PBDEs), perfluorinated chemicals (PFCs), triclosan, phenols, OH-PCBs and OH-PBDEs. Prior to this program, we had conducted a number of epidemiologic studies using specimens collected from the 1960s to the present and analysing them for POPs. Serum, milk and adipose samples were extracted and the neutral fractions were cleaned up using deactivated Florisil column chromatography, and analyzed for PCBs, OCPs and PBDEs by dual column GC-ECD and/or High Resolution Mass Spectrometry. Online Solid Phase Extraction - HPLC- Turbo ion Spray Tandem Mass Spectrometry was used to analyze PFCs. Following standard conventions, results are expressed on a lipid basis (PCBs, PBDEs, OCPs), or on a volume basis (PFCs, Triclosan, Phenols, OH-PCBs, OH-PBDEs). A Quality Management system tracks all laboratory work.

We had first reported the absence of PBDEs in serum samples from 1960s California populations as opposed to their presence in samples collected in the 1990s. We confirmed this observation with the analysis of over 1500 samples from the 1960s. In contemporary serum, the abundance of PBDE congeners was in the order of BDE-47>153>99>100, while BDE-209 was measurable in only a few of the samples. We could trace the increase of PFOA from the1960s to the 1980s, followed by a slight decrease in 2009. On the other hand, PFOS and PFHxS were highest in the 1960s, with similar decreasing trends from the1980s to 2009.

In addition to addressing the research hypotheses of each epidemiologic study, data compiled across studies can show trends such as the emergence of PBDEs, and the decline in PCBs, phenols, OCPs and some PFCs over time. In addition, determinants of exposures (age, country of birth, ethnicity and reproductive history) can be identified, allowing for optimal sampling designs to account for the population diversity in California and can also be used in questionnaires to assess exposures. These data help establish a baseline before the new Biomonitoring Program launches its state-wide surveys.

Abstract  Short-chain perfluoroalkyl acids (PFAAs), which have less than seven fluorinated carbons, have been introduced as substitutes for eight-carbon homologue products. In this study, water, sediment, and biological samples (fish and plant) were collected from Tangxun Lake, which is located near a production base of the fluorochemical industry in Wuhan, China. Perfluorobutane sulfonate (PFBS) and perfluorobutanoic acid (PFBA) were the predominant PFAAs in surface water, with average concentrations of 3660 ng/L and 4770 ng/L, respectively. However, perfluorooctane sulfonate (PFOS) was the most abundant PFAA in sediments, with an average concentration of 74.4 ng/g dw. The organic carbon normalized distribution coefficients (KOC) indicated that short-chain PFAAs (CF2 < 7) tended to have lower adsorption potentials than PFOS, perfluorooctanoic acid (PFOA), and longer perfluoroalkyl chain compounds. PFBS and PFBA could transport to a farther distance in the horizontal direction along the water flow and infiltrate into deeper depths in the vertical direction. However, levels of PFOS and PFOA in water dropped exponentially along the current, and their proportions were decreased gradually with the increasing depth in sediment cores. Furthermore, values of log bioconcentration factor (BCF) of the short-chain PFAAs were all relatively low (<1), indicating no bioaccumulation potentials for short-chain PFAAs in aquatic species. [PUBLICATION ABSTRACT]