Spatial and temporal trends of perfluorinated compounds in Beluga Whales (Delphinapterus leucas) from Alaska

Wildlife from remote locations have been shown to bioaccumulate perfluorinated compounds (PFCs) in their tissues. Twelve PFCs, consisting of perfluorinated carboxylic (PFCA) and sulfonic (PFSA) acids as well as the perfluorooctane sulfonate (PFOS) precursor perfluorooctane sulfonamide (PFOSA), were measured in livers of 68 beluga whales (Delphinapterus leucas) collected from two subpopulations, Cook Inlet and eastern Chukchi Sea, in Alaska between 1989 and 2006. PFOS and PFOSA were the dominant compounds measured in both beluga stock populations, with overall median concentrations of 10.8 ng/g and 22.8 ng/g, respectively. Long-chain perfluorocarboxylates, PFCAs (9 to 14 carbons), were detected in more than 80% of the samples. Perfluoroundecanoic acid (PFUnA) and perfluorotridecanoic acid (PFTriA) made up a large percentage of the PFCAs measured with median concentrations of 8.49 ng/g and 4.38 ng/g, respectively. To compare differences in location, year, sex, and length, backward stepwise multiple regression models of the individual and total PFC concentrations were used. Spatially, the Cook Inlet belugas had higher concentrations of most PFCAs and PFOS (p < 0.05); however, these belugas had a lower median concentration of PFOSA when compared to belugas from the eastern Chukchi Sea (p < 0.05). Temporal trends indicated most PFCAs, PFHxS, PFOS, and PFOSA concentrations increased from 1989 to 2006 (p < 0.05). Males had significantly higher concentrations of PFTriA, ΣPFCA, and PFOS (p < 0.05). Perfluorononanic acid (PFNA) and PFOS showed a significant decrease in concentration with increasing animal length (p < 0.05). These observations suggest the accumulation of PFCs in belugas is influenced by year, location, sex, and length.     

Temporal trends of perfluoroalkyl concentrations in American Red Cross adult blood donors, 2000-2010

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.     

Trends in exposure to polyfluoroalkyl chemicals in the U.S. Population: 1999-2008

Since 2002, practices in manufacturing polyfluoroalkyl chemicals (PFCs) in the United States have changed. Previous results from the National Health and Nutrition Examination Survey (NHANES) documented a significant decrease in serum concentrations of some PFCs during 1999-2004. To further assess concentration trends of perfluorooctane sulfonate (PFOS), perfluorooctanoate (PFOA), perfluorohexane sulfonate (PFHxS), and perfluorononanoate (PFNA), we analyzed 7876 serum samples collected from a representative sample of the general U.S. population ≥12 years of age during NHANES 1999-2008. We detected PFOS, PFOA, PFNA, and PFHxS in more than 95% of participants. Concentrations differed by sex regardless of age and we observed some differences by race/ethnicity. Since 1999-2000, PFOS concentrations showed a significant downward trend, because of discontinuing industrial production of PFOS, but PFNA concentrations showed a significant upward trend. PFOA concentrations during 1999-2000 were significantly higher than during any other time period examined, but PFOA concentrations have remained essentially unchanged during 2003-2008. PFHxS concentrations showed a downward trend from 1999 to 2006, but concentrations increased during 2007-2008. Additional research is needed to identify the environmental sources contributing to human exposure to PFCs. Nonetheless, these NHANES data suggest that sociodemographic factors may influence exposure and also provide unique information on temporal trends of exposure.     

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.     

Distribution of perfluorooctane sulfonate and other perfluorochemicals in the ambient environment around a manufacturing facility in China

Perfluorinated compounds (PFCs) can be released to the surrounding environment during manufacturing and usage of PFC containing products, which are considered as main direct sources of PFCs in the environment. This study evaluates the release of perfluorooctane sulfonate (PFOS) and other PFCs to the ambient environment around a manufacturing plant. Among the nine PFCs analyzed, only PFOS, perfluorooctanoic acid (PFOA), and perfluorohexane sulfonate (PFHxS) were found in dust, water, soil, and chicken eggs. Very high concentrations of PFOS and PFOA were found in dust from the production storage, raw material stock room, and sulfonation workshop in the manufacturing facility, with the highest value at 4962 μg/g (dry weight) for PFOS and 160 μg/g for PFOA. A decreasing trend of the three PFCs concentrations in soils, water, and chicken eggs with increasing distance from the plant was found, indicating the production site to be the primary source of PFCs in this region. Risk quotients (RQs) assessment for surface water >500 m away from the plant were less than unity. Risk assessment of PFOS using predicted no-effect concentration (PNEC, 3.23 ng/g on a logarithmic scale) indicated no immediate ecological risk of a reduction in offspring survival. PFOS concentrations in most egg samples did not exceed the benchmark concentration derived in setting a reference dose for noncancer health effects (0.025 μg/(kgxd)).     

Perfluorinated compounds in the Cape Fear Drainage Basin in North Carolina

Concern over perfluorinated organic compounds (PFCs), e.g., perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA), is due to a number of recent studies which show that the PFCs are persistent, bioaccumulative, and toxic in animals. Despite sustained interest in this topic, little information is available concerning the environmental distributions of the compounds. In this study, a new method was developed for the analysis of 10 target PFCs and its performance was examined in a systematic evaluation of surface water in the Cape Fear River Basin in North Carolina. One hundred samples from 80 different locations were collected during the spring of 2006. Detectable levels of the target PFCs were found in all samples, and were comparable to values reported previously, with maximum PFOS at 132 ng/L, PFOA at 287 ng/L, perfluorononanoic acid (C9) at 194 ng/L, and perfluoroheptanoic acid (C7) at 329 ng/L. In general, the lowest concentrations of the PFCs were found in the smallest tributaries while the highest levels were found in middle reaches of the Drainage Basin. Variability of PFC concentrations suggests a series of source inputs throughout the Basin. Seventeen sample sites (22%) had PFOS concentrations greater than 43 ng/L, a conservative safe water concentration estimated to be protective of avian life. In addition, a total of 26 sites (32%) had PFOA concentrations above 40 ng/L.     

Health risks in infants associated with exposure to perfluorinated compounds in human breast milk from Zhoushan, China

Recent studies have reported the ubiquitous distribution of perfluorinated compounds (PFCs), especially perfluorooctanesulfonate (PFOS) and perfluorooctanoic acid (PFOA), in wildlife and human whole blood or serum. In 2003 a solid phase extraction method was developed, which allowed the measurement of PFCs in human breast milk. In the present study, PFCs in samples of human breast milk from 19 individuals from Zhoushan, China, were analyzed by modifying a previously established method, based on weak-anion exchange extraction. PFOS and PFOA were the two dominant chemicals detected in all the milk samples. Concentrations of PFOS and PFOA ranged from 45 to 360 ng/L and 47 to 210 ng/L, respectively. The maximum concentrations of other PFCs were 100 ng/L for perfluorohexanesulfonate (PFHxS), 62 ng/L for perfluorononanoate (PFNA), 15 ng/L for perfluorodecanoate (PFDA) and 56 ng/L for perfluoroundecanoate (PFUnDA). Statistically significant correlations between various PFCs suggested a common exposure source to humans. No statistically significant correlation was found between concentrations of either PFOS or PFOA and maternal age, weight, or infant weight. Rate of consumption of fish was found to be positively correlated with PFNA, PFDA, and PFUnDA concentrations. Daily intake of PFOS for the child via breast milk with greater PFOS concentrations exceeded the predicted conservative reference dose in 1 of 19 samples, indicating that there may be a small potential risk of PFOS for the infants in Zhoushan via the consumption of breast milk.     

Temporal changes in the levels of perfluorinated compounds in California women's serum over the past 50 years

Serum samples collected from California women at different time periods: 1960s (n = 40), 1980s (n = 30), and 2009 (n = 35) were examined for the presence of 12 perfluorinated compounds (PFCs) using an online SPE-HPLC-MS/MS method. At each time period, perfluorooctane sulfonate (PFOS) was present at the highest concentration, followed by perfluorooctanoic acid (PFOA, except in the 1960s). We found the highest levels of PFOS (median = 42.1 ng/mL) and perfluorohexane sulfonate (PFHxS, median = 1.56 ng/mL) in the 1960s samples, possibly reflecting widespread use of precursor PFCs. PFOS showed a statistically significant drop from the 1960s to the 1980s (28.8 ng/mL ) and to 2009 (9.0 ng/mL ), the latter being in agreement with national data. For PFOA, there was an approximately 10-fold increase in median concentrations from the 1960s (0.27 ng/mL) to the 1980s (2.71 ng/mL), and a slight drop in the 2009 samples (2.08 ng/mL). For longer chain perfluorocarboxylic acids (PFCAs), there was a continuous build-up in serum from the 1960s to 2009. To our knowledge, this is the first study to investigate temporal changes of PFCs over the past 50 years.     

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 contaminants in sediments and aquatic organisms collected from shallow water and tidal flat areas of the Ariake Sea, Japan: environmental fate of perfluorooctane sulfonate in aquatic ecosystems

Perfluorinated compounds (PFCs), such as perfluorooctane sulfonate (PFOS), perfluorooctanoate (PFOA), perfluorononanoate (PFNA), perfluorohexane sulfonate (PFHS), and perfluorooctane sulfonamide (PFOSA) are widely distributed in aquatic ecosystems. Despite studies reporting the occurrence of PFCs in aquatic organisms, the fate of PFCs in tidal flat and marine coastal ecosystems is not known. In this study, we determined concentrations of PFOS, PFOA, PFNA, PFHS, and PFOSA in sediments; benthic organisms, including lugworm, mussel, crab, clam, oyster, and mudskipper fish from tidal flat; and shallow water species, such as filefish, bream, flounder, shark, finless porpoise, gull, and mallard collected from the Ariake Sea, Japan. PFOS and PFOA were detected in most of the samples analyzed, followed by PFNA, PFOSA, and PFHS. In shallow water species, PFOS was the dominant contaminant, and elevated concentrations were found in higher trophic level species, such as marine mammals and omnivorous birds. These results suggest biomagnification of PFOS through the coastal food chain. In contrast, PFOA was the most abundant compound in tidal flat organisms and sediments. PFOA concentrations in sediments, lugworms, and omnivorous mudskippers in tidal flat were approximately 1 order of magnitude greater than the levels of PFOS. This indicates differences in exposure pattern and bioavailability of PFOS and PFOA between shallow water and tidal flat organisms. The accumulation profiles of PFCs were compared with those of organochlorines (polychlorinated biphenyls, PCB), organotin (tributyltin,TBT), and polycyclic aromatic hydrocarbons (PAHs) in tidal flat and shallow water samples collected from the Ariake Sea. Concentrations of PFCs in sediments and in tidal flat organisms were significantly lower than that found for PCBs, TBT, and PAHs. Nevertheless, PFOS concentrations in shallow water species were comparable to and/or significantly greater than those of other classes of contaminants. This implies that the aqueous phase is a major sink for PFCs, which is different from what was observed for nonpolar organic pollutants.     

Contamination and effects of perfluorochemicals in Baikal seal (Pusa sibirica). 1. Residue level, tissue distribution, and temporal trend

Concentrations of perfluorochemicals (PFCs) including perfluoroalkylsulfonates (PFSAs) and perfluoroalkylcarboxylates (PFCAs) were determined in liver and serum of Baikal seals (Pusa sibirica) collected from Lake Baikal, Russia in 2005. Among the 10 PFC compounds measured, perfluorononanoic acid (PFNA, 3.3-72 ng/g wet wt) concentrations were the highest in liver, followed by perfluorooctanesulfonate (PFOS, 2.6-38 ng/g). The accumulation profile of long-chain (C7-C12) PFCAs in particular, the predominance of PFNA, indicated that 8:2 fluorotelomer alcohol or commercially manufactured PFNA is a major local source of PFCs in Lake Baikal. No gender-related differences in the concentrations of individual PFCs or total PFCs were found. Tissues from pups and juveniles contained relatively higher concentrations of PFCs than tissues from subadults and adults, suggesting that maternal transfer of PFCs is of critical importance. Comparison of concentrations of PFCs in livers and sera collected from the same individuals of Baikal seals revealed that residue levels of PFOS, PFNA, perfluorodecanoic acid (PFDA), and perfluoroundecanoic acid (PFUnDA) were significantly higher in liver than in serum. The concentration ratios of PFNA and PFDA between liver and serum were calculated to be 14 and 15, respectively, whereas the ratio of PFOS was 2.4. This suggests preferential retention of both PFNA and PFDA in liver. Concentrations of PFOS, PFNA, and PFDA in liver were significantly correlated with those in serum, whereas concentrations of PFUnDA were not correlated in between the two tissues, suggesting differences in pharmacokinetics among these PFCs. Temporal comparisons of hepatic PFC concentrations in seals collected between 1992 and 2005 showed that the concentrations of PFOS (p = 0.0006), PFNA (p = 0.061) and PFDA (p = 0.017) were higher in animals collected in recentyears, indicating ongoing sources of PFC contamination in Lake Baikal.     

Prevalence of long-chained perfluorinated carboxylates in seabirds from the Canadian Arctic between 1975 and 2004

Temporal trends in perfluoroalkyl compounds (PFCs) were investigated in liver samples from two seabird species, thick-billed murres (Uria lomvia) and northern fulmars (Fulmaris glacialis), from Prince Leopold Island in the Canadian Arctic. Thick-billed murre samples were from 1975, 1993, and 2004, whereas northern fulmars were from 1975, 1987, 1993, and 2003. Between 8 and 10 individuals were analyzed per year. Analytes included C7-C15 perfluorinated carboxylates (PFCAs) and their suspected precursors, the 8:2 & 10:2 fluorotelomer saturated and unsaturated carboxylates (FTCAs, FTUCAs), C6, C8 (perfluorooctane sulfonate, PFOS), C10 sulfonates, and perfluorooctane sulfonamide (PFOSA). Liver samples were homogenized, liquid-liquid extracted with methyl tert-butyl ether, cleaned-up using hexafluoropropanol, and analyzed by LC-MS/ MS. Overall, concentrations in seabirds were lower than those in other marine animals that occupy similar or higher trophic positions. In contrast to most other wildlife samples, PFC profiles were dominated by the PFCAs which comprised 81% and 93% of total PFC profiles in the 2004 thick-billed murre and 2003 northern fulmar samples, respectively. As well, the PFCA profiles were mainly comprised of the C11-C15 PFCAs, which appears to be unique among other wildlife species. PFC concentrations were found to increase significantly from 1975 to 2003/2004. Doubling times in thick-billed murres ranged from 2.3 yrs for perfluoropentadecanoate (PFPA) to 9.9 yrs for perfluorododecanoate (PFDoA), and from 2.5 yrs for PFPA to 11.7 yrs for perfluorodecanoate (PFDA) in northern fulmars. PFCA concentration increases in thick-billed murres were significant for both time periods (1975-1993, 1993-2004), but in northern fulmars appeared to remain steady after 1993. Differences in the temporal trends observed may be the result of differing migratory patterns of the seabirds. Finally, the detection of the 8:2 and 10:2 FTUCAs in seabirds is suggestive of fluorotelomer alcohols as a source of some PFCAs.     

Levels of 12 perfluorinated chemicals in pooled australian serum, collected 2002-2003, in relation to age, gender, and region

Pooled serum samples from 3802 Australian residents were analyzed for four perfluoroalkylsulfonates, seven perfluoroalkylcarboxylates, and perfluorooctanesulfonamide (PFOSA). Serum was collected from men and women of five different age groups and from rural and urban regions in Australia. The highest mean concentration was obtained for perfluorooctane sulfonate (PFOS, 20.8 ng/mL) followed by perfluorooctanoic acid (PFOA, 7.6 ng/mL), perfluorohexane sulfonate (PFHxS, 6.2 ng/mL), perfluorononanoic acid (PFNA, 1.1 ng/mL), and PFOSA (0.71 ng/mL). Additional four PFCs were detected in 5-18% of the samples at concentrations near the detection limits (0.1-0.5 ng/mL). An increase in PFOS concentration with increasing age in both regions and genders was observed. The male pool levels of some of the age groups compared to females were higherfor PFOS, PFOA, and PFHxS. In contrast, PFNA concentrations were higher in the female pools. No substantial difference was found in levels of PFCs between the urban and rural regions. The levels are equal or higher than previously reported serum levels in Europe and Asia but lower compared to the U.S.A. These results suggest that emissions from production in the Northern Hemisphere are of less importance for human exposure.     

Rapid response of Arctic ringed seals to changes in perfluoroalkyl production

Temporal trends in perfluoroalkyl compounds (PFCs) were investigated in liver samples from two ringed seal (Phoca hispida) populations in the Canadian Arctic, Arviat (Western Hudson Bay) (1992, 1998, 2004, 2005) and Resolute Bay (Lancaster Sound) (1972, 1993, 2000, 2004, 2005). PFCs analyzed included C7-C15 perfluorinated carboxylates (PFCAs) and their suspected precursors, the 8:2 and 10:2 fluorotelomer saturated and unsaturated carboxylates (FTCAs, FTUCAs), C4, C6, C8, C10 sulfonates, and perfluorooctane sulfonamide (PFOSA). Liver samples were homogenized, liquid-liquid extracted with methyl tert-butyl ether, cleaned up using hexafluoropropanol, and analyzed by liquid chromatography with negative electrospray tandem mass spectrometry (LC-MS/MS). C9-C15 PFCAs showed statistically significant increasing concentrations during 1992-2005 and during 1993-2005 at Arviat and Resolute Bay, respectively. Doubling times ranged from 19.4 to 15.8 years for perfluorododecanoate (PFDoA) to 10.0-7.7 years for perfluorononanoate (PFNA) at Arviat and Resolute Bay but were shorter when excluding the 2005 samples. Conversely, perfluorooctane sulfonate (PFOS) and PFOSA concentrations showed maximum concentrations during 1998 and 2000 at Arviat and Resolute Bay, with statistically significant decreases from 2000 to 2005. In the case of Arviat, two consecutive decreases were measured from 1998 to 2003 and from 2003 to 2005. PFOS disappearance half-lives for seals at Arviat and Resolute Bay were 3.2 and 4.6 years. These results indicate that the ringed seals and their food web are rapidly responding to the phase out of perfluorooctane sulfonyl fluoride based compounds by 3M in 2001. Further, the relatively short doubling times of the PFCAs and PFOS disappearance half-lives support the hypothesis of atmospheric transport as the main transport mechanism of PFCs to the arctic environment.     

Long-term environmental fate of perfluorinated compounds after accidental release at Toronto airport

Perfluorooctane sulfonate (PFOS; a perfluorinated compound or PFC), its salts, and perfluorooctane sulfonyl fluoride have recently been listed in Annex B of the Stockholm Convention due to their widespread presence, persistence, and toxicity. Because of the persistent nature of PFCs, it is generally presumed that the impact of direct discharges of these chemicals on a receiving environment would be long-lasting. However, long-term environmental fate studies based on field measurements are rare. We examined spatial and long-term (9 year) temporal trends of PFCs in water, sediment, fish, and fish liver collected in 2003, 2006, and 2009 from 10 locations spanning ～20 km in Etobicoke and Spring Creeks, where an accidental release of fire fighting foam containing PFOS from nearby Toronto International Airport occurred in 2000. Even a decade after the spill, sediment PFOS concentrations are still elevated in Spring Creek Pond which received the foam discharge; however, the major impact is relatively localized likely due to the stormwater management nature of the pond and the diluting effect of Etobicoke Creek. Fish and fish liver PFOS concentrations at a Spring Creek location downstream of Spring Creek Pond declined by about 70 and 85%, respectively, between 2003 and 2009. PFOS in water at locations further downstream in Etobicoke Creek have declined by >99.99% since the spill; however, the 2009 water and fish levels were ～2-10 times higher than upstream locations likely due to the long-term impact of the spill as well as urbanization. The decrease in the upstream PFOS concentrations likely reflects the reduction of PFOS sources due to phased out production by 3M and regulations on the use of PFOS in fire fighting foams. Field-based sediment/water distribution coefficients (K(D)) and bioaccumulation factors (BAF) were calculated from environmental measurements. Log K(D) values were 0.54-1.65 for perfluoroalkyl sulfonates (PFASs) and 1.00-1.85 for perfluorocarboxylates (PFCAs). Log BAF(fish) ranged from 1.85 to 3.24 for PFASs and 0.88-3.47 for PFCAs, whereas log BAF(fish liver) ranged from 2.1-4.3 for PFASs and 1.0-5.0 for PFCAs.     

Serum concentrations of polyfluoroalkyl compounds in Faroese whale meat consumers

To learn the extent of human exposure to polyfluoroalkyl compounds (PFCs) in a remote fishing population, we measured, in Faroese children and pregnant women, the serum concentrations of nine PFCs, including perfluorooctane sulfonate (PFOS), perfluorooctanoate (PFOA), and perfluorononanoate (PFNA), by using online solid-phase extraction coupled to isotope dilution high-performance liquid chromatography-tandem mass spectrometry. The serum samples analyzed had been collected between 1993 and 2005 from 103 children 7 years of age, 79 of these children at 14 years of age, and from 12 pregnant women and their children 5 years later. PFOS was detected in all samples analyzed, and both PFOA and PFNA were detected in all but one of the samples. The concentrations found are comparable tothose reported elsewhere. Correlations between paired concentrations were poor. However, PFOS and PFNA concentrations correlated well with the frequency of pilotwhale dinners and with concentrations of mercury and polychlorinated biphenyls. One whale meal every two weeks increased the PFOS concentration in 14-year-olds by about 25% and PFNA by 50%. The high frequency of detection of most PFCs suggests widespread exposure in the Faroe Islands already by the early 1990s, with whale meat being an important source.     

Association of Perfluorooctanoic Acid with HDL Cholesterol and Circulating miR-26b and miR-199-3p in Workers of a Fluorochemical Plant and Nearby Residents

Perfluoroalkyl chemicals (PFCs) are stable man-made compounds with many industrial and commercial uses. Concern has been raised that they may exert deleterious effects, especially on lipid regulation. We aimed to assess exposure to perfluorooctanoic acid (PFOA), perfluorooctane sulfonic acid (PFOS), and seven other PFCs in occupational workers from a fluorochemical plant and nearby community residents, and to investigate the association between PFOA and serum biomarkers. Serum biomarkers included not only biochemical parameters, such as lipids and enzymes, but also circulating microRNAs (miRNAs). Samples were analyzed by high-pressure liquid chromatography/tandem mass spectrometry (HPLC-MS/MS). Circulating miRNA levels were detected by quantitative polymerase chain reaction (PCR). Analyses were conducted by correlation and linear regression. We detected PFOS, PFOA, perfluorohexane sulfonate (PFHxS), perfluorononanoic acid (PFNA), and perfluorodecanoic acid (PFDA) in all samples. The median levels of serum PFOA and PFOS were 284.34 ng/mL and 34.16 ng/mL in residents and 1635.96 ng/mL and 33.46 ng/mL in occupational participants, respectively. To our knowledge, we found for the first time that PFOA was negatively associated with high-density lipoprotein cholesterol (HDL-C) in workers using linear regression after adjusting for potential confounders. Circulating miR-26b and miR-199a-3p were elevated with serum concentration of PFOA. Although the limitations of small sample size and the cross-sectional nature of the current study constrained causal inferences, the observed associations between PFOA and these serum biomarkers warrant further study.     

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.     

Perfluorooctanesulfonate and related fluorochemicals in human blood samples from China

Perfluorooctanesulfonylfluoride (POSF)-based compounds have been manufactured and used in a variety of industrial applications. These compounds degrade to perfluorooctanesulfonate (PFOS) which is regarded as a persistent end-stage metabolite and is found to accumulate in tissues of humans and wildlife. PFOS, perfluorohexanesulfonate (PFHxS), perfluorooctanoate (PFOA), and perfluorooctanesulfonamide (PFOSA) have been found in human sera from the United States. In this study, concentrations of PFHxS, perfluorobutanesulfonate (PFBS), PFOS, perfluorohexanoic acid (PFHxA), PFOA, perfluorononanoic acid (PFNA), perfluorodecanoic acid (PFDA), perfluoroundecanoic acid (PFUnDA), perfluorododecanoic acid (PFDoDA), and PFOSA were measured in 85 samples of whole human blood collected from nine cities (eight provinces) in China, including Shenyang (Liaoning), Beijing (Hebei), Zhengzhou (Henan), Jintan (Jiangsu), Wuhan (Hubei), Zhoushan (Zhejiang), Guiyang (Guizhou), Xiamen (Fujian), and Fuzhou (Fujian). Among the 10 perfluorinated compounds (PFCs) measured, PFOS was the predominant compound. The mean concentration of PFOS was greatest in samples collected from Shenyang (79.2 ng/mL) and least in samples from Jintan (3.72 ng/mL). PFHxS was the next most abundant perfluorochemical in the samples. No age-related differences in the concentrations of PFOA, PFOS, PFOSA, and PFHxS were observed. Gender-related differences were found,with males higher for PFOS and PFHxS, and females higher in PFUnDA. Concentrations of PFHxS were positively correlated with those of PFOS, while concentrations of PFNA, PFDA, and PFUnDA were positively correlated with those of PFOA. There were differences in the concentration profiles (percentage composition) of various PFCs in the samples among the nine cities.