Polychlorinated biphenyls and hydroxylated polychlorinated biphenyls in plasma of bottlenose dolphins (Tursiops truncatus) from the Western Atlantic and the Gulf of Mexico

Polychlorinated biphenyls (PCBs) and hydroxylated metabolic products (OH-PCBs) were measured in plasma collected from live-captured and released bottlenose dolphins (Tursiops truncatus) from five different locations in the Western Atlantic and the Gulf of Mexico in 2003 and 2004. In 2004, the sum (sigma) of concentration of PCBs in plasma of dolphins sampled off Charleston, SC [geometric mean: 223 ng/g of wet weight (w.w.)] was significantly higher (p<0.05) than concentrations detected in animals from the Indian River Lagoon, FL (sigmaPCBs: 122 ng/g w.w.) and the Sarasota Bay, FL (sigmaPCBs: 111 ng/g w.w.). The PCB homolog profiles were similar among locations. Concentrations of OH-PCBs were significantly higher (p<0.05) in plasma of dolphins from Charleston, SC (sigmaOH-PCBs for 2003: 126 ng/g w.w.; 2004: 138 ng/g w.w.) than animals from Florida (sigmaOH-PCBs ranged from 6 to 47 ng/g w.w.) and Bermuda (8.3 ng/g w.w.); however, concentrations in the Charleston samples did not differ from animals captured in Delaware Bay, NJ (57 ng/g w.w.). The sigmaOH-PCBs constituted 2-68% of the total PCB concentrations in plasma. Dichloro- to nonachloro-OH-PCBs were quantified using high-resolution gas chromatography mass spectrometry, but only around 20% of OH-PCBs could be identified by comparison to authentic standards. Results from this study show that OH-PCB are important environmental contaminants in dolphins and suggest that PCBs, decades after their ban, may still constitute a threat to wildlife.     

Biomagnification of perfluoroalkyl compounds in the bottlenose dolphin (Tursiops truncatus) food web

The environmental distribution and the biomagnification of a suite of perfluoroalkyl compounds (PFCs), including perfluorooctane sulfonate (PFOS) and C8 to C14 perfluorinated carboxylates (PFCAs), was investigated in the food web of the bottlenose dolphin (Tursiops truncatus). Surficial seawater and sediment samples, as well as zooplankton, fish, and bottlenose dolphin tissue samples, were collected at two U.S. locations: Sarasota Bay, FL and Charleston Harbor, SC. Wastewater treatment plant (WWTP) effluents were also collected from the Charleston area (n = 4). A solid-phase extraction was used for seawater and effluent samples and an ion-pairing method was used for sediment and biotic samples. PFCs were detected in seawater (range <1-12 ng/L), sediment (range <0.01-0.4 ng/g wet weight (ww)), and zooplankton (range 0.06-0.3 ng/g ww). The highest PFC concentrations were detected in WWTP effluents, whole fish, and dolphin plasma and tissue samples in which PFOS, C8 and C10-PFCAs predominated in most matrices. Contamination profiles varied with location suggesting different sources of PFC emissions. Biomagnification factors (BMFs) ranged from <1 to 156 at Sarasota Bay and <1 to 30 at Charleston. Trophic magnification factors (TMFs) for PFOS and C8-C11 PFCAs indicated biomagnification in this marine food web. The results indicate that using plasma and liver PFC concentrations as surrogate to whole body burden in a top marine predator overestimates the BMFs and TMFs.     

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

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

Is indirect exposure a significant contributor to the burden of perfluorinated acids observed in humans?

In comparison to other persistent organic pollutants, human fluorochemical contamination is relatively complicated. This complication arises at least in part from a disparity between the chemicals used commercially and those measured in the environment and humans. Commercial fluorochemical products are dominated by fluorinated polymers used in textile or carpet applications, or fluorosurfactants used in applications ranging from personal care products, leveling and wetting agents, to greaseproofing food-contact materials. Investigations into environmental and human fluorochemical contamination have focused on perfluorinated acids (PFAs), either the perfluorinated carboxylates (PFCAs) or sulfonates (PFSAs). In this review we will present an overview of data related to human fluorochemical exposure including a discussion of fluorochemical production, concentrations in exposure media, biotransformation processes producing PFAs, and trends in human sera. These data will be presented in the context of how they can inform sources of human PFA contamination, specifically whether the contamination results from direct PFA exposure or indirect exposure via the biotransformation of commercial fluorochemicals or their residuals. Concentrations of both perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) began to decrease in human sera around the year 2000, a change that mirrored the 2000-2002 phase-out of perfluorooctane sulfonyl fluoride (POSF) production. These temporal trends suggest exposure to current-use POSF-based materials was a significant source of PFOA and PFOS exposure prior to 2000. Relatively slow PFOA elimination and increasing concentrations of the C9 and C10 PFCAs in human sera suggest continued PFCA exposure, without similar exposure to PFOS, which is consistent with indirect exposure via the biotransformation of fluorotelomer-based materials. Conversely, human exposure models have suggested direct exposure to PFAs present in food items is the major source of human contamination. The data set presented here cannot unequivocally delineate between direct and indirect human exposure, however temporal trends in human sera and exposure media are consistent with indirect exposure representing a significant portion of observed human PFA contamination.     

Tissue distribution of perfluorinated chemicals in harbor seals (Phoca vitulina) from the Dutch Wadden Sea

Perfluorinated acids (PFAs) are today widely distributed in the environment, even in remote arctic areas. Recently, perfluorooctane sulfonate (PFOS) has been identified in marine mammals all over the world, but information on the compound-specific tissue distribution remains scarce. Furthermore, although longer perfluorinated carboxylic acids (PFCAs) are used in industry and were shown to cause severe toxic effects, still little is known on potential sources or their widespread distribution. In this study, we report for the first time on levels of longer chain PFCAs, together with some short chain PFAs, perfluorobutane sulfonate (PFBS) and perfluorobutanoate (PFBA), in liver, kidney, blubber, muscle, and spleen tissues of harbor seals (Phoca vitulina) from the Dutch Wadden Sea. PFOS was the predominant compound in all seal samples measured (ranging from 89 to 2724 ng/g wet weight); however, large variations between tissues were monitored. Although these are preliminary results, it is, to our knowledge, the first time that PFBS could be found at detectable concentrations (2.3 +/- 0.7 ng/g w wt) in environmental samples. PFBS was only detected in spleen tissue. PFCA levels were much lower than PFOS concentrations. The dominant PFCA in all tissues was PFNA (perfluorononanoic acid), and concentrations generally decreased in tissues for all other PFCA homologues with increasing chain length. No clear relationship between PFOS levels in liver and kidney was observed. Furthermore, hepatic PFDA (perfluorodecanoic acid) levels increased with increasing body length, but in kidney tissue, PFDA levels showed an inverse relationship with increasing body length. These data suggest large differences in tissue distribution and accumulation patterns of perfluorinated compounds in marine organisms.     

Perfluorinated acids in air, rain, snow, surface runoff, and lakes: relative importance of pathways to contamination of urban lakes

Concentrations of perfluorinated acids (PFAs) were measured in various environmental matrices (air, rain, snow, surface runoff water, and lake water) in an urban area, to enable identification of sources and pathways of PFAs to urban water bodies. Total PFA concentrations ranged from 8.28 to 16.0 pg/ m3 (mean 11.3) in bulk air (sum of vapor and particulate phases), 0.91 to 13.2 ng/L (6.19) in rainwater, 0.91 to 23.9 ng/L (7.98) in snow, 1.11-81.8 ng/L (15.1 ng/L) in surface runoff water (SRW), and 9.49 to 35.9 ng/L (21.8) in lake water. Perfluorooctanoic acid (PFOA) was the predominant compound, accounting for > 35% of the total PFA concentrations, in all environmental matrices analyzed. Concentrations and relative compositions of PFAs in SRW were similar to those found for urban lakes. SRW contributes to contamination by PFOA in urban lakes. The measured concentration ratios of FTOH to PFOA in air were 1-2 orders of magnitude lower than the ratios calculated based on an assumption of exclusive atmospheric oxidation of FTOHs. Nevertheless, the mass balance analysis suggested the presence of an unknown input pathway that could contribute to a significant amount of total PFOA loadings to the lake. Flux estimates of PFOA at the air-water interface in the urban lake suggest net volatilization from water.     

Temporal trends of perfluoroalkyl contaminants in polar bears (Ursus maritimus) from two locations in the North American Arctic, 1972-2002

Perfluoroalkyl substances are globally distributed anthropogenic contaminants. Their production and use have increased dramatically from the early 1980s. While many recent publications have reported concentrations of perfluorooctane sulfonate (PFOS) and other perfluoroalkyl acids (PFAs) in biotic and abiotic samples, only limited work has addressed temporal trends. In this study we analyzed archived polar bear(Ursus maritimus) livertissue samples from two geographic locations in the North American Arctic, collected from 1972 to 2002. The eastern group, taken from the vicinity of northern Baffin Island, Canada, comprised 31 samples, and the western group, from the vicinity of Barrow, Alaska, comprised 27 samples. Samples were analyzed for perfluorocarboxylic acids (PFCAs) from carbon chain length C8 to C15, perfluorohexane sulfonate, PFOS, the neutral precursor perfluorooctane sulfonamide (PFOSA), as well as 8:2 and 10:2 fluorotelomer acids and their alpha,beta unsaturated acid counterparts. Concentrations of PFOS and PFCAs with carbon chain lengths from C9 to C11 showed an exponential increase between 1972 and 2002 at both locations. Doubling times ranged from 3.6 +/- 0.9 years for perfluorononanoic acid in the eastern group to 13.1 +/- 4.0 years for PFOS in the western group. PFOSA showed decreasing concentrations over time at both locations, while the remaining PFAs showed no significant trends or were not detected in any sample. The doubling time for PFOS was similar to the doubling time of production of perfluoroctylsulfonyl-fluoride-based products during the 1990s.     

Perfluorinated acids in Arctic snow: new evidence for atmospheric formation

Perfluorinated acids (PFAs) are ubiquitously found in water and biota, including remote regions such as the High Arctic. Under environmental conditions, PFAs exist mainly as anions and are not expected to be subject to long-range atmospheric transport in the gas phase. Fluorinated telomer alcohols (FTOHs) are volatile and can be atmospherically oxidized to form perfluorocarboxylic acids. Analogously, fluorosulfamido alcohols can be oxidized to form perfluorooctane sulfonate (PFOS). High Arctic ice caps experience contamination solely from atmospheric sources. By examining concentrations of PFAs in ice cap samples, it is possible to determine atmospheric fluxes to the Arctic. Ice samples were collected from high Arctic ice caps in the spring of 2005 and 2006. Samples were concentrated using solid-phase extraction and analyzed by LC-MS-MS. PFAs were observed in all samples, dating from 1996 to 2005. Concentrations were in the low-mid pg L(-1) range and exhibited seasonality, with maximum concentrations in the spring-summer. The presence of perfluorodecanoic acid (PFDA) and perfluoroundecanoic acid (PFUnA) on the ice cap was indicative of atmospheric oxidation as a source. Ratios of PFAs to sodium concentrations were highly variable, signifying PFA concentrations on the ice cap were unrelated to marine chemistry. Fluxes of the PFAs were estimated to the area north of 65 degrees N for the 2005 season, which ranged from 114 to 587 kg year(-1) for perfluorooctanoic acid (PFOA), 73 to 860 kg year(-1) for perfluorononanoic acid (PFNA), 16 to 84 kg year(-1) for PFDA, 26 to 62 kg year(-1) for PFUnA, and 18 to 48 kg year(-1) for PFOS. The PFOA and PFNA fluxes agreed with FTOH modeling estimations. A decrease in PFOS concentrations through time was observed, suggesting a fast response to changes in production. These data suggest that atmospheric oxidation of volatile precursors is a primary source of PFAs to the Arctic.     

Degradation of fluorotelomer alcohols: a likely atmospheric source of perfluorinated carboxylic acids

Human and animal tissues collected in urban and remote global locations contain persistent and bioaccumulative perfluorinated carboxylic acids (PFCAs). The source of PFCAs was previously unknown. Here we present smog chamber studies that indicate fluorotelomer alcohols (FTOHs) can degrade in the atmosphere to yield a homologous series of PFCAs. Atmospheric degradation of FTOHs is likely to contribute to the widespread dissemination of PFCAs. After their bioaccumulation potential is accounted for, the pattern of PFCAs yielded from FTOHs could account for the distinct contamination profile of PFCAs observed in arctic animals. Furthermore, polar bear liver was shown to contain predominately linear isomers (>99%) of perfluorononanoic acid (PFNA), while both branched and linear isomers were observed for perfluorooctanoic acid, strongly suggesting a sole input of PFNA from "telomer"-based products. The significance of the gas-phase peroxy radical cross reactions that produce PFCAs has not been recognized previously. Such reactions are expected to occur during the atmospheric degradation of all polyfluorinated materials, necessitating a reexamination of the environmental fate and impact of this important class of industrial chemicals.     

Detection of a cyclic perfluorinated acid, perfluoroethylcyclohexane sulfonate, in the Great Lakes of North America

Perfluoroethylcyclohexanesulfonate (PFECHS) is a cyclic perfluorinated acid (PFA) mainly used as an erosion inhibitor in aircraft hydraulic fluids. It is expected to be as recalcitrant to environmental degradation as aliphatic PFAs including perfluorooctanoate (PFOA) and perfluorooctane sulfonate (PFOS). For the first time, PFECHS is reported in top predator fish (相似文献   

Circumpolar study of perfluoroalkyl contaminants in polar bears (Ursus maritimus)

Perfluoroalkyl substances were determined in liver tissues and blood of polar bears (Ursus maritimus) from five locations in the North American Arctic and two locations in the European Arctic. Concentrations of perfluorooctane sulfonate (PFOS), perfluorohexane sulfonate, heptadecafluorooctane sulfonamide, and perfluoroalkyl carboxylates with C(8)-C(15) perfluorinated carbon chains were determined using liquid chromatography tandem mass spectrometry. PFOS concentrations were significantly correlated with age at four of seven sampling locations, while gender was not correlated to concentration for any compound measured. Populations in South Hudson Bay (2000-2730 ng/g wet wt), East Greenland (911-2140 ng/g wet wt), and Svalbard (756-1290 ng/g wet wt) had significantly (P < 0.05) higher PFOS concentrations than western populations such as the Chukchi Sea (435-729 ng/g wet wt). Concentrations of perfluorocarboxylic acids (PFCAs) with adjacent chain lengths (i.e., C9:C10 and C10:C11) were significantly correlated (P < 0.05), suggesting PFCAs have a common source within a location, but there were differences in proportions of PFCAs between eastern and western location sources. Concentrations of PFOS in liver tissue at five locations were correlated with concentrations of four polychlorinated biphenyl congeners (180, 153, 138, and 99) in adipose tissue of bears in the same populations, suggesting similar transport pathways and source regions of PFOS or precursors.     

Fine-scale spatial variation of persistent organic pollutants in bottlenose dolphins (Tursiops truncatus) in Biscayne Bay, Florida

Bottlenose dolphins (Tursiops truncatus) are long-term residents and apex predators in southeast U.S. estuaries and are vulnerable to bioaccumulation of persistent organic pollutants (POPs). Dart biopsy samples were collected from 45 dolphins in Biscayne Bay (Miami, FL), 34 of which were matched using fin markings to a photo identification catalogue. Blubber samples were analyzed for 73 polychlorinated biphenyl (PCB) congeners, six polybrominated diphenyl ether (PBDE) congeners, and organochlorine pesticides including dichloro-diphenyl-trichloroethane (DDT) and metabolites, chlordanes, and dieldrin. Total PCBs (sigma 73PCBs) were present in the highest concentrations and were 5 times higher in males with sighting histories in the northern, metropolitan area of Biscayne Bay than males with sighting histories in the southern, more rural area [geometric mean: 43.3 (95% confidence interval: 28.0-66.9) vs 8.6 (6.3-11.9) microg/g wet mass, respectively]. All compound classes had higher concentrations in northern animals than southern. The differences in POP concentrations found on this small geographic scale demonstrate that differential habitat use can strongly influence pollutant concentrations and should be considered when interpreting bottlenose dolphin POP data. The PCB concentrations in northern Bay dolphins are high as compared to other studies of estuarine dolphins and may place these animals at risk of reproductive failure and decreased immune function.     

Fluorotelomer acids are more toxic than perfluorinated acids

Saturated and unsaturated fluorotelomer carboxylic acids have been identified as intermediates in the degradation of fluorotelomer alcohols to perfluorinated carboxylic acids (PFCAs). Although surface waters are the likely environmental sink for telomer acids, no fate or toxicity data exist for this matrix. We assessed the acute toxicity of the 4:2, 6:2, 8:2, and 10:2 saturated (FTCA) and unsaturated (FTUCA) fluorotelomer carboxylic acids to Daphnia magna, Chironomus tentans, and Lemna gibba. In general, toxicity increased with increasing fluorocarbon (FC) chain length, particularly for telomer acids of > or =8 FCs. In addition, the FTCAs were generally more toxic than the corresponding FTUCAs. Acute EC50s ranged from 0.025 mg/L (0.04 micromol/L) for D. magna (10:2 FTCA, immobility) to 63 mg/L (167 micromol/L) for C. tentans (6:2 FTCA, growth). While chain-length trends observed in the current study agree with those previously reported for PFCAs, the toxicity thresholds generated here are up to 10,000 times smaller. Our data provide the first evidence that PFCA precursors are more toxic than the PFCAs themselves.     

Concentrations, distribution, and persistence of perfluoroalkylates in sludge-applied soils near Decatur, Alabama, USA

Sludges generated at a wastewater treatment plant (WWTP) in Decatur, Alabama have been applied to agricultural fields for more than a decade. Waste-stream sources to this WWTP during this period included industries that work with fluorotelomer compounds, and sludges from this facility have been found to be elevated in perfluoroalkylates (PFAs). With this knowledge, the U.S. Environmental Protection Agency collected soil samples from sludge-applied fields as well as nearby "background" fields for PFA analysis. Samples from the sludge-applied fields had PFAs at much higher concentrations than in the background fields; generally the highest concentrations were perfluorodecanoic acid (≤ 990 ng/g), perfluorododecanoic acid (≤ 530 ng/g), perfluorooctanoic acid (≤ 320 ng/g), and perfluorooctane sulfonate (≤ 410 ng/g). Contrasts in PFA concentration between surface and deeper soil samples tended to be more pronounced in long-chain congeners than shorter chains, perhaps reflecting relatively lower environmental mobilities for longer chains. Several PFAs were correlated with secondary fluorotelomer alcohols (sec-FTOHs) suggesting that PFAs are being formed by degradation of sec-FTOHs. Calculated PFA disappearance half-lives for C6 through C11 alkylates ranged from about 1 to 3 years and increase with increasing chain-length, again perhaps reflecting lower mobility of the longer-chained compounds.     

Analysis for perfluorocarboxylic acids/anions in surface waters and precipitation using GC--MS and analysis of PFOA from large-volume samples

The presence of perfluorocarboxylates (PFCAs) in the environment is of increasing concern, following the discovery of perfluoroalkyl acids (PFAs) in wildlife and human samples. Here we report a method forthe determination of (C2-C9) PFCAs by preparing the 2,4-difluoroanilides of the acids and analyzing by using GC-MS. Detector response was linear over the range 0.1 -1000 pg of each perfluoroalkyl anilide. A complete suite of PFCAs can be analyzed in an individual sample with the PFCAs detected at levels similar to or lower than those determined by other methods. For a comparison between the present method and the more common LC-MS/MS method, 10 replicates of a sewage treatment plant discharge were analyzed for perfluoro-octanoic acid (PFOA) using both methods. Results were nearly identical with low standard deviation (GC-MS 30.9 +/- 1.88 ng/L; while the LC-MS/MS 34.7 +/- 3.05 ng/L). PFCA concentrations for water samples collected from depth profiles in mid-Lake Ontario were analyzed by GC-MS with most PFCAs (C2-C8) present above the detection limit (0.5 ng/L). Major PFCAs were trifluoroacetate (TFA) (100 ng/L) and perfluorobutanoate (PFBA) (> 5 ng/L). Results for PFOA (2.5 ng/L) were in good agreement with recent analyses by LC-MS/MS. PFCAs were also detected in the precipitation samples at concentrations lower than those of the samples from the lake profiles or sewage treatment plants (STPs) effluent. Since PFOA levels may be less than the lower detection limit (<0.5 ng/L) in 1 L samples, a method for large volumes using XAD-7 resin was developed that allows detection to 0.01 ng/L. This method was applied to Lake Superior samples which produced good agreement for C6-C9 PFCAs between regular analysis (GC-MS) and the XAD-7 followed by GC-MS analysis.     

Oxidative conversion as a means of detecting precursors to perfluoroalkyl acids in urban runoff

A new method was developed to quantify concentrations of difficult-to-measure and unidentified precursors of perfluoroalkyl carboxylic (PFCA) and sulfonic (PFSA) acids in urban runoff. Samples were exposed to hydroxyl radicals generated by thermolysis of persulfate under basic pH conditions and perfluoroalkyl acid (PFAA) precursors were transformed to PFCAs of related perfluorinated chain length. By comparing PFCA concentrations before and after oxidation, the concentrations of total PFAA precursors were inferred. Analysis of 33 urban runoff samples collected from locations around the San Francisco Bay, CA indicated that PFOS (2.6-26 ng/L), PFOA (2.1-16 ng/L), and PFHxA (0.9-9.7 ng/L) were the predominant perfluorinated compounds detected prior to sample treatment. Following oxidative treatment, the total concentrations of PFCAs with 5-12 membered perfluoroalkyl chains increased by a median of 69%, or between 2.8 and 56 ng/L. Precursors that produced PFHxA and PFPeA upon oxidation were more prevalent in runoff samples than those that produced PFOA, despite lower concentrations of their corresponding perfluorinated acids prior to oxidation. Direct measurements of several common precursors to PFOS and PFOA (e.g., perfluorooctanesulfonamide and 8:2 fluorotelomer sulfonate) accounted for less than 25% of the observed increase in PFOA, which increased by a median value of 37%. Exposure of urban runoff to sunlight, advanced oxidation processes, or microbes could result in modest, but measurable, increases in concentrations of PFCAs and PFSAs.     

Perfluorinated alkyl substances in plasma, liver, brain, and eggs of glaucous gulls (Larus hyperboreus) from the Norwegian arctic

Recent environmental surveys have ascertained the widespread occurrence of perfluorinated alkyl substances (PFAS) in tissues of wildlife from the Arctic. In the present study, we investigated the distribution of a suite of PFAS in plasma, liver, brain, and egg samples from adult glaucous gulls (Larus hyperboreus), an apex scavenger-predator seabird breeding in the Norwegian Arctic. Perfluorooctane sulfonate (PFOS) was the predominant PFAS in all samples and was present at concentrations that are the highest reported thus far in any arctic seabird species and populations. Among the body compartment/ tissue samples analyzed, PFOS was highest in plasma (48.1-349 ng/g wet weight (ww)), followed by liver approximately equal to egg > brain. Perfluorocarboxylic acids (PFCAs) with 8-15 carbon (C) atoms were found, with the highest concentrations determined in plasma (sum PFCA: 41.8-262 ng/g ww), whereas 5C- and 6C-PFCAs were below the limits of detection. Perfluorobutane sulfonate, perfluorooctane sulfonamide, and four saturated (8:2 FTCA and 10:2 FTCA) and unsaturated (8:2 FTUCA and 10:2 FTUCA) fluorotelomer carboxylic acids were not detected in any samples. Perfluorohexane sulfonate was measured at concentrations up to 2.71 ng/g ww. The accumulation profiles of PFCAs were characterized by high proportions of the long and odd-numbered carbon-chain-length compounds, namely perfluoroundecanoic (11C) and perfluorotridecanoic acid (13C), although their individual contribution differed between the matrixes analyzed. Current PFAS concentrations suggest a bioaccumulation potential in Norwegian arctic glaucous gulls that needs to be assessed as part of a broad organohalogen contaminant cocktail with potential for mediating biological processes in this vulnerable top-predator marine species.     

Perfluorinated carboxylic acids in directly fluorinated high-density polyethylene material

Perfluorinated carboxylic acids (PFCAs) are ubiquitous in the environment and have been detected in human blood worldwide. One potential route is direct exposure to PFCAs through contact with polymers that have been fluorinated through a process referred to as direct fluorination. PFCAs are hypothesized to be reaction byproducts of direct fluorination when trace amounts of oxygen are present. The objective of this research was to investigate whether PFCAs could be measured in directly fluorinated high-density polyethylene (HDPE) bottles. PFCAs were quantified using Soxhlet extraction with methanol, followed by LC-MS/MS analysis. Total concentrations of PFCAs ranged from 8.5 ± 0.53 to 113 ± 2.5 ng/bottle (1 L), with the short-chain PFCAs, perfluoropropanoic, perfluorobutanoic, perfluoropentanoic, and perfluorohexanoic acids, being the dominant congeners observed. Relative PFCA concentrations varied depending on fluorination level. Structural isomers were detected using (19)F NMR and are hypothesized to have formed during the fluorination process; NMR data revealed the linear isomer typically comprised 55% of the examined sample. Internally branched, isopropyl branched, and t-butyl PFCA isomers of varying chain length were also identified. Electrochemical fluorination was previously thought to be the only source of branched PFCA isomers. The observation here of branched isomers suggests direct fluorination may be an additional source of exposure to these chemicals. The purpose of this study was to measure PFCAs in directly fluorinated material, serving as a previously unidentified source contributing to the environmental load of PFCAs, with potential for human exposure.     

High accumulation of perfluorooctane sulfonate (PFOS) in marine tucuxi dolphins (Sotalia guianensis) from the Brazilian coast

Perfluorooctane sulfonate (PFOS) and other perfluoroalkyl compounds (PFCs) were measured in liver samples from 29 marine tucuxi dolphins from Rio de Janeiro state (RJ), Brazil. PFC measurement combined liquid chromatography and mass spectrometry, using a CapLC system connected to a Quadrupole-LIT mass spectrometer. PFOS was the only PFC detected and it was so in all samples. PFOS concentrations (ng x g(-1) dw) of dolphins (n=23) from the highly contaminated Guanabara Bay (in RJ) varied between 43 and 2431 as well as between 76 and 427 from areas of RJ other than the quoted bay (n=6). Concentrations of three fetuses and one neonate varied between 664 and 1590. Fetus/mother ratios were calculated in two situations (2.75 and 2.62). It seems that mother-to-calf transference plays important role for relationships between PFOS and age. When a one-year-old male calf presenting 2431 ng x g(-1) dw was excluded from the test, significant correlations were observed between PFOS concentrations and both age and total length. Despite the placental transference, PFOS concentrations were not significantly lower in females than in males. PFOS levels in marine tucuxi dolphins from Guanabara Bay are among the highest detected to date in cetaceans, and this may represent a threat to the small population concerned.     

Fluorotelomer carboxylic acids and PFOS in rainwater from an urban center in Canada

A method based on LC/MS/MS analysis of fluorotelomer carboxylic acids (FTCAs: CnF2n+1CH2COOH, n = 6, 8, and 10) and fluorotelomer unsaturated carboxylic acids (FTUCAs: CnF2nCHCOOH, n = 6, 8, and 10) in rainwater using negative ionization electrospray multiple reaction monitoring conditions is described. These compounds are thought to be oxidative products of atmospherically transported fluorotelomer alcohols (FTOHs: CnF2n+1CH2CH2CH2OH). Preconcentration from rainwater samples collected in Winnipeg, Manitoba, Canada, was achieved using solid-phase extraction on C18 sorbent. Low parts per trillion levels of the C10- and C12-FTCAs and FTUCAs were detected, suggesting that one possible pathway of removing FTOHs from the atmosphere is through oxidation and wet deposition. Perfluorocarboxylic acids (PFCAs) and perfluorooctane sulfonate (PFOS) were simultaneously analyzed in the rainwater samples using established LC/MS/MS methods. PFOS was deposited in rainwater with a concentration of 0.59 ng/L while PFCAs were not detected above their respective method detection limits.