Abstract  Perfluorinated compounds (PFC) in water, sediment, soil, and biota from the coastal industrial area of Tianjin, China, were measured to provide baseline information and to determine possible sources and potential risk to wildlife. Perfluorooctanesulfonate (PFOS) was the predominant PFC with maximum concentrations of 10 ng/L in water, and 4.3, 9.4, and 240 ng/g dw in sediment, soil, and fish, respectively. Perfluorooctanoate (PFOA) concentration in water ranged from 3.0 to 12 ng/L. Perfluoroundecanoate (PFUnA) and Perfluorododecanoate (PFDoA) were detected in solid matrices, respectively, at concentrations of <LOQ to 1.2 ng/g dw and 0.27-0.81 ng/g dw in sediments, and <LOQ to 1.0 ng/g dw and 0.26-0.61 ng/g dw in soils. Concentrations of PFOS, PFUnA, and PFDoA in sediment and soil from this industrialized and urbanized area were greater than those previously reported, while PFOS and PFOA in water and biota were both less than reported threshold concentrations for adverse effects in wildlife.

Abstract  A total of 21 perfluorinated compounds (PFCs) were quantified in water and biota samples collected from Shenyang in North-east China and the Yangtze River Delta area in East China. The human health risk owing to intake of perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) via fish and domestic poultry dietary was evaluated. The total PFC concentration (Sigma PFC) in water samples from the rivers in Shenyang averaged 5.32 ng L(-1), with PFOS and PFOA as the predominant compounds. The urban sewage could be the source of PFOS and perfluorohexane sulfonate (PFHxS) in the surface waters. The total PFCs in water samples from the Yangtze River Delta area ranged from 42.4 to 170 ng L(-1). The highest concentrations of most PFCs were observed in waters from the Shanghai section of the Yangtze River. In the biota samples, PFOS and PFUnDA (perfluoroundecanoic acid) were the most abundant. The acceptable daily intake (ADI) and hazard ratio (HR) values for PFOS and PFOA intake through the diet of fish and poultry in the studied areas were calculated, and showed that the HR values for PFOS and PFOA are all less than 1.0 for both the areas.

Abstract  Perfluorinated compounds (PFCs) are known to biomagnify in temperate and Arctic food webs, but little is known about their behavior in subtropical systems. The environmental distribution and biomagnification of PFCs, extractable organic fluorine (EOF), and total fluorine were investigated in a subtropical food web. Surface water, sediment, phytoplankton, zooplankton, gastropods, worms, shrimps, fishes, and waterbirds collected in the Mai Po Marshes Nature Reserve in Hong Kong were analyzed. Trophic magnification was observed for perfluorooctanesulfonate (PFOS), perfluorodecanoate (PFDA), perfluoroundecanoate (PFUnDA), and perfluorododecanoate (PFDoDA) in this food web. Risk assessment results for PFOS, PFDA, and perfluorooctanoate (PFOA) suggest that current PFC concentrations in waterbird livers are unlikely to pose adverse biological effects to waterbirds. All hazard ratio (HR) values reported for PFOS and PFOA are less than one, which suggests that the detected levels will not cause any immediate health effects to the Hong Kong population through the consumption of shrimps and fishes. However, only 10-12% of the EOF in the shrimp samples was comprised of known PFCs, indicating the need for further investigation to identify unknown fluorinated compounds in wildlife.

Abstract  Spatial trends of concentrations of perfluorinated chemicals (PFCs) were investigated in harbour seal liver tissue from seven locations in Denmark, ranging from the Wadden Sea in the southern North Sea to the Western Baltic. All samples were collected during the phocine distemper epizootic in 2002 which provided access to a large number of comparable samples over a short time period. PFOS was dominating (mean: 92% of ∑PFC) among the PFCs in the samples, followed by considerably lower concentrations of PFHxS (1.8%), PFDA (1.7%), PFNA (1.6%) PFUnA (1.5%), PFOA (0.9%) and PFOSA (0.5%). The concentrations of all the investigated compounds showed significant differences among the seven locations. PFOS showed the highest concentrations in the Wadden Sea, where high burdens have also been recorded in German seals. Most compounds showed a trend towards higher concentrations at one or both extremes of the geographic range. Two different patterns of relative PFC concentrations were detected; one in the inner Danish waters where PFOSA and PFUnA were more prevalent and another in the Wadden Sea and Limfjord where PFOA, PFHxS and PFNA were found in greater proportions. These patterns probably represent Baltic and North Sea contamination sources.

Abstract  Several perfluoroalkyl compounds (PFCs) are ubiquitous environmental contaminants that can biomagnify in species at high trophic levels including wild birds. Perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) have been detected in wild birds and are known to reduce hatching success of laboratory-exposed chicken embryos at environmentally relevant concentrations. Limited toxicity data are available regarding avian exposure to PFCs of chain lengths greater than C(8), which are of increasing environmental relevance following the recent phase-out of PFOS and PFOA. In this study, linear PFOA, perfluoroundecanoic acid (PFUdA) and perfluorodecane sulfonate (PFDS) were injected into the air cell of white leghorn chicken eggs (Gallus gallus domesticus) prior to incubation to determine effects on embryo pipping success. Furthermore, mRNA expression of key genes involved in pathways implicated in PFC toxicity was monitored in liver tissue. PFOA, PFUdA or PFDS had no effect on embryonic pipping success at concentrations up to 10 microg/g. All PFCs accumulated in the liver to concentrations greater than the initial whole-egg concentration as determined by HPLC/MS/MS. Hepatic accumulation was highest for PFOA (4.5 times) compared to PFUdA and PFDS. Cytochrome P450 1A4 and liver fatty acid binding protein mRNA expression increased after exposure to PFUdA but was only statistically significant at 10 microg/g; several orders of magnitude higher than levels found in wild bird eggs. Based on the present results for white leghorn chickens, current environmental concentrations of PFOA, PFUdA and PFDS are unlikely to affect the hatching success of wild birds.

Abstract  Concentrations of 19 perfluorochemicals have been quantified in human blood and in some marine food resources from the region of the Gulf of Gdañsk at the Baltic Sea south coast in Poland. We indicate that in addition to PFOS and PFOA, a further 8 perfluorochemicals bioaccumulate in the human body. Food chain is an important route of exposure for all 10 perfluoroalkyl compounds detected in nonoccupationally exposed humans. Individuals who declared to have a high fish intake in their diet (mainly Baltic fish) on average contained the highest load of all 10 fluorochemicals when compared with the other human subpopulations. Baltic seafood has been found to highly influence human body burden of PFHxS, PFOS, PFOSA, PFHxA, PFHpA, PFNA, PFDA, PFUnDA, and PFDoDA, and to a lesser extent PFOA.

Abstract  A time trend study focusing on ski waxing technicians' exposure to perfluorinated chemicals (PFCs) from fluorinated wax fumes was performed in 2007/2008. Levels of eight perfluorocarboxylates and three perfluorosulfonates were analyzed in monthly blood samples from eight technicians. Samples were collected before the ski season, i.e., preseason, then at four FIS World Cup competitions in cross country skiing, and finally during an unexposed 5-month postseason period. The perfluorinated carboxylates perfluoroheptanoic acid (PFHpA), perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), perfluorodecanoic acid (PFDA), and perfluoroundecanoic acid (PFUnDA) bioaccumulate, and continued exposure may contribute to elevated levels in ski technicians compared to the general population. The wax technicians' median blood level of PFOA is 112 ng/mL compared to 2.5 ng/mL in the general Swedish population. A significant correlation was found between number of working years and levels of perfluorocarboxylates. The PFOA levels in three technicians with "low" initial levels of PFOA (<10.0 ng/mL in preseason blood) increased by 254, 134, and 120%, whereas five technicians with "high" initial levels (>100 ng/mL in preseason sample) were at steady state. PFHxA is suggested to have a short half-life in humans relative the other perfluorocarboxylates. The levels of perfluorosulfonates were unaffected by the wax exposure.

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  Biodegradation of fluorinated polymers is of interest to assess them as a potential source of perfluorocarboxylates (PFCAs) in the environment. A fluoroacrylate polymer product test substance was studied in four aerobic soils over two years to assess whether the fluorotelomer alcohol (FTOH) side chains covalently bonded to the polymer backbone may be transformed to form PFCAs. The test substance itself was not directly measured; instead, nine analytes were determined to evaluate biodegradation. Terminal biotransformation products measured included perfluorooctanoate (PFO), perfluorononanoate (PFN), perfluorodecanoate (PFD), perfluoroundecanoate (PFU), and pentadecafluorodecanoate (7-3 acid). The molar concentration of 8-2 fluorotelomer alcohol (8-2 FTOH) in the test substance, fluoroacrylate polymer and residual unreacted raw materials and impurities ("residuals") were compared with the molar concentrations of the terminal biotransformation products for mass balance and kinetic assessments. Over the two year time frame of the experimental study, the fluoroacrylate polymer showed a slight extent of potential biodegradation under the experimental conditions of the study. A biodegradation half-life of 1200-1700 years was calculated for the fluoroacrylate polymer based on the rate of formation of PFO in aerobic soils. When the degradation rates of the fluoroacrylate polymer and residuals were applied to estimated total historic fluoroacrylate polymer production, use and disposal,the biodegradation of fluoroacrylate polymer and residuals is calculated to contribute less than 5 tonnes of PFO per year globally to PFCAs present in the environment.

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

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

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

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

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

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

Abstract  This study examined the effect of five types of carbonaceous materials (CMs) in sediment on bioaccumulation of perfluorochemicals (PFCs) by Chironomus plumosus larvae. The CMs included two multiwalled carbon nanotubes (MWCNT10 and MWCNT50), maize straw- and willow-derived chars, and maize straw-origin ash. The PFCs included perfluorooctane sulfonate (PFOS), perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), perfluorodecanoic acid (PFDA), perfluoroundecanoic acid (PFUnA), and perfluorododecanoic acid (PFDoA). The CMs with different concentrations (0-1.5% dry weight) were amended into sediments spiked with PFCs and aged for 60 d. The uptake rate constants (k(s)) for each PFC to larvae differed with different CM amendments (p < 0.05), while elimination rate did not change significantly (p > 0.05). Decreasing PFC concentration in larvae (C(B)) was found with increasing CM concentration (f(CM)) in the sediments, and a linear positive correlation existed between 1/C(B) and f(CM) (p < 0.05). The effect of CMs on PFC bioaccumulation agreed well with the CM properties; MWCNT10 with the highest specific surface area resulted in the lowest k(s) values and biota-sediment accumulation factors (BSAF), with a BSAF reduction of 66%-97% by a 1.5% amendment. The mechanism was explored by analyzing the aqueous phase concentrations of PFCs and the sorption of PFCs on sediments amended with CMs. The results suggested that the decreasing trend of PFCs in larvae was caused by the decreasing aqueous phase concentration with increasing CM concentration. In the studied conditions with low PFC concentrations, the bioaccumulation of PFCs was a linear partitioning between pore water and biota, and the sorption of PFCs to the sediment/CM mixtures was a two domain linear distribution. This study suggests that both the type and concentration of carbonaceous materials in sediment can affect the bioaccumulation of PFCs to benthic organisms through changing their aqueous phase concentrations.

Abstract  Despite the reports of the occurrence of perfluorochemicals (PFCs) in industrialized nations, information on PFCs in less industrialized countries is meager. In the present study, concentrations and profiles of PFCs were investigated in surface waters (rivers, lakes, coastal seas and untreated sewage; n=42) including the Ganges River water, and biota such as shrimp (n=2), fish (n=28), and Ganges River dolphin (Platanista gangetica; n=15). PFOS was the dominant PFC found in most of the samples analyzed including water samples except untreated sewage (water: <0.04-3.91 ng L(-1); biota: 0.248-27.9 ng g(-1) ww). Long-chain (C11-C18) perfluorocarboxylates (PFCAs) were not detected in the water samples (<0.2 ng L(-1)), although PFDA (0.061-0.923 ng g(-1) ww) and PFUnDA (0.072-0.998 ng g(-1) ww) were found in biological samples The arithmetic mean PFOS concentration found in the liver of Ganges River dolphin was 27.9 ng g(-1) ww. Bioconcentration and biomagnifications factors of PFCs were estimated in the Ganges River basin food web. The highest concentration of PFOA, 23.1 ng L(-1), was found in untreated sewage samples. Overall, concentrations of PFCs of water and biological samples from India are lower than the concentrations reported for other countries so far. PFC profiles in Indian waters are dominated by PFOS, followed by PFOA, which is different from the pattern reported for other countries such as Korea, Japan and USA, where PFOA was the predominant compound in waters. The flux estimates for PFOS, PFOA and PFNA from the Ganges River in India to the Bay of Bengal were in the range of several hundreds of kilograms per year.

Abstract  A sensitive method was established for the separation and determination of nine perfluorinated compounds (PFCs) in blood samples. Perfluorohexane sulfonate (PFHxS), perfluorohetanoic acid (PFHpA), perfluorooctanoate (PFOA), perfluorooctane sulfonat (PFOS), perfluorononanoic acid (PFNA), perfluorodecanoic acid (PFDA), perfluoroundecnaoic acid (PFUnDA), perfluorododecanoic acid (PFDoDA) and perflouorotetradodecanoic acid(PFTA) were detected by high performance liquid chromatography/electrospray tandem mass spectrometry (HPLC ESI MS/MS) with C(18) reversed phase column in 15 min, using (13)C(4) labeled PFOS (MPFOS) as the internal standard. PFCs in the blood samples were further extracted with solid phase extraction cartridges after traditional MTBE extraction before injection. Four kinds of cartridges were tested, including RP, P, C(18) and HLB, then HLB cartridge was selected as the efficient adsorbent. A comparative study of two C(18) columns, Acclaim 120 (50 mm x 4.6 min, 3 mu m) and Acclaim 120 (250 mm x 4.6 mm, 5 mu m) column, were also performed. Both columns provided similar sensitivities, with the detection limits of 0.03 -0.8 mu g/L for real blood samples. The relative standard deviation of recoveries ranged from 3% to 11%. Finally, Acclaim 120 (250 mm x 4.6 mm, 5 mu m) column was chosen for its superiority of column capacity. With the optimal conditions, the recoveries of PFCs in blood samples ranged from 74.2% to 118.1%, with the exception of PFTA, which was only about 60%.

Abstract  A novel method was developed for solid-phase extraction (SPE) of perfluorinated compounds (PFCs) from environmental water samples using cetyltrimethylammonium bromide (CTAB) coated Fe3O4 nanoparticles (Fe3O4 NPs) as an adsorbent. The magnetic nanosized adsorbent has a large surface area and superparamagnetic properties. This gives it a high extraction capacity and allows for convenient isolation by a magnetic field. Compared with other SPE methods and our previous work on PFCs, this method exhibited a fairly good analytical performance and required a small amount of sorbent (50 mg) and short pretreatment times (30 min) for 800 mL environmental water samples. Seven PFCs, including perfluorooctane sulfonic acid (PFOS), perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), perfluorodecanoic acid (PFDA), perfluoroundecanoic acid (PFUnDA), perfluorododecanoic acid (PFDoDA), and perfluorotetradecanoic acid (PFTA), extracted by the optimized method were determined by high-performance liquid chromatography-electrospray tandem mass spectrometry (HPLC/ESI-MS/MS). A concentration factor of 1600 was achieved when extracting 800 mL of several environmental water samples. Detection limits obtained for PFOA, PFOS, PFNA, PFDA, PFUnDA, PFDoDA and PFTA were 0.14, 0.022, 0.31, 0.23, 0.11, 0.16, 0.091 ng/L, respectively. The relative standard deviations of recoveries ranged from 1 to 8%, indicating good method precision. (C) 2011 Elsevier B.V. All rights reserved.

Abstract  The structural characterization of polyion complex LB films of perfluoroundecanoic acid-polyethyleneimine was studied using Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. From these results, it was found that the fluorocarbon chains in the LB films are located close to the LB film-air interface and are considerably tilted with respect to the surface normal.

Abstract  Midge larvae (Chironomus riparius) were exposed to sediments from a deposition sampled at a site along the Rhône River (France) downstream of an industrial site releasing various perfluorinated chemicals. This sediment is characterized by high concentrations of perfluoroundecanoic acid (PFUnA) and perfluorotridecanoic acid (PFTrDA) and a low perfluorooctane sulfonate (PFOS) concentration. Concentrations of 23 perfluoroalkyl compounds, including C4-C14 carboxylate acids, C4-C10 sulfonates, and seven precursors, were analyzed in overlying and pore water, sediment, and larvae. Midge larvae accumulated carboxylate acids (C11-C14), PFOS, and two precursors (perfluorooctane sulfonamide: FOSA and 6:2 fluorotelomer sulfonic acid, 6:2 FTSA). These substances accumulated mainly during the fourth instar larvae exponential growth phase. Accumulation of 6:2 FTSA, PFUnA, and PFOS occured via trophic and tegumentary routes. Other compounds mainly accumulated from food. Kinetics followed a partition model, from which uptake and elimination constants were derived.

Abstract  BACKGROUND: Perfluoroalkyl substances (PFASs) are pollutants that tend to accumulate in the environment and organisms. The animal and human studies to date have focused on thyroid function, but the results are inconsistent.

METHODS: A sample of 118 mother-infant pairs was obtained from the Taiwan Birth Panel Study (TBPS). Cord blood PFASs levels were evaluated using the Waters ACQUITY UPLC system coupled with a Waters Quattro Premier XE triple quadrupole mass spectrometer, and cord blood thyroid hormones were assessed using a Roche Analytics E170 modular analyser (Roche Diagnostics, Mannheim, Germany). PFASs concentrations were analysed in the final models to examine the associations between cord blood PFASs levels and thyroid hormone concentrations.

RESULTS: The cord blood perfluorooctane sulfonate (PFOS) concentration was negatively associated with the cord blood thyroxine (T4) concentration [per ln unit: adjusted β (95% confidence interval, CI) = -0.458(-0.916, -0.001)]. Moreover, the level of cord blood thyroid stimulating hormone (TSH) was positively associated with the cord blood PFOS concentration [per ln unit: adjusted β (95% confidence interval, CI) = 0.346(0.101, 0.592)]. The sex stratified effects of PFOS on T4 were suggestive of differential effects in high-exposure groups compared with low-exposure group in boys.

CONCLUSIONS: We found that cord blood thyroid hormone levels are affected by PFASs, with a negative association between T4 and PFOS and a positive association between TSH and PFOS. The causal associations of thyroid hormones and PFASs require further exploration.

Abstract  BACKGROUND: The link among perfluoroalkyl and polyfluoroalkyl substances (PFASs), abnormal glucose homeostasis and the risk of diabetes has been intensively debated with conflicting evidence.

OBJECTIVES: We evaluated the associations among PFASs, oral glucose tolerance testing (OGTT) curves and diabetes prevalence in 571 working-aged Taiwanese participants.

METHODS: Exposure measures included serum perfluorooctanoic acid (PFOA), perfluorooctane sulfonic acid (PFOS), perfluorononanoic acid (PFNA), and perfluoroundecanoic acid (PFUA). Outcomes were OGTT curves and prevalent diabetes defined by fasting blood glucose (FBG) ≥126mg/dL, 2-h glucose ≥200mg/dL, or glycated hemoglobin ≥6.5%. Analyses were performed with multiple logistic regression and functional data analysis.

RESULTS: A total of 39 participants (6.8%) had diabetes in this study. After full adjustment, the increase in the geometric means of FBG, 2-h glucose concentrations, and area under the OGTT curve (AUC120) with a doubling increase in PFOS was 3% (95% CI 1-4), 8% (5-12), and 6% (4-9), respectively. Compared to the lowest-quartile of PFOS concentrations (<2.4ng/ml), the OGTT trajectories were significantly steeper in participants of the highest-quartile PFOS exposure (>4.8ng/ml) and the vertical shifting of the mean curve for each PFOS quartile showed a dose-response pattern. The adjusted odds ratio for diabetes comparing the highest to lowest quartile was 3.37 (95% CI 1.18-9.65). For PFOA, PFNA, and PFUA, the opposite pattern of OGTT trajectory and the opposite risk profile for diabetes were observed.

CONCLUSIONS: Chronic PFOS exposure was associated with impaired glucose homeostasis and the increased prevalence of diabetes. However, PFOA, PFNA, and PFUA showed a potential protective effect against glucose intolerance and the risk of diabetes. Future research focusing on clarifying possible differential effects of different species of PFASs on glucose homeostasis and establishing the prospective associations between PFASs and diabetes is needed.

Abstract  Polyfluorinated alkyl compounds (PFCs) are a group of chemicals of growing concern that have been detected in biological and abiotic samples worldwide. This study reports the concentrations of a suite of PFCs: perfluorooctyl sulfonate (PFOS), perfluorooctyl sulfonamide (PFOSA) and perfluorinated carboxylic acids (PFCAs) in guillemot (Uria aalge) eggs, collected in North-Western Europe, from Iceland, the Faroe Islands, Sweden and two locations in Norway. The highest concentrations of PFOS were found in samples from Sweden (mean 400 ng g(-1) wet weight (w.w.)), which were almost five times higher than concentrations found in Norwegian samples (mean 85 ng g(-1)w.w. from both sample sites). The concentrations found in Icelandic and Faroe samples were lowest (mean 16 and 15 ng g(-1)w.w., respectively). Only Swedish samples differed significantly from the other locations. In general, PFCAs show a different spatial trend than PFOS. Perfluorooctanoic acid (PFOA) was not detected in any sample and perfluorononanoic acid (PFNA) was only detected in samples from Sweden. The most abundant PFCA was perfluoroundecanoic acid (PFUA) with highest concentrations in samples from Sweden (mean 82 ng g(-1)w.w.), samples from the Faroe Islands had the second highest concentration (mean 57 ng g(-1)w.w.) and samples from Iceland and Norway had concentrations ranging between 18 and 30 ng g(-1)w.w. The original hypothesis was based on the idea that PFC concentrations are the highest close to more densely populated and industrialized areas and lower levels in remote areas. However, the geographic pattern is more complicated than predicted and varies among different PFCs.