PCDDs, PCDFs, and coplanar PCBs in albatross from the North Pacific and Southern Oceans: levels, patterns, and toxicological implications

Concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and coplanar polychlorinated biphenyls (coplanar PCBs) were determined in five albatross species collected from the North Pacific and Southern Oceans to assess the north-south differences in residue levels, accumulation patterns, and toxic potential. Black-footed and Laysan albatrosses from the North Pacific Ocean contained higher levels of PCDD/Fs and coplanar PCBs than albatrosses from the Southern Ocean, indicating that emission sources of these contaminants were predominant in the northern hemisphere. Residue levels in albatrosses from the remote North Pacific Ocean far from the point source of pollution were comparable to or higher than those in terrestrial and coastal birds from contaminated areas in developed nations, suggesting the specific exposure and accumulation of PCDD/Fs and coplanar PCBs in albatross. The long life span and ingestion of plastic resin pellets by albatrosses could be the plausible explanations for the elevated accumulation of persistent and lipophilic contaminants including PCDD/Fs and coplanar PCBs in these birds. Relative proportions of PCDFs and coplanar PCBs in albatross were higher than those observed in birds inhabiting terrestrial and coastal areas, suggesting that these toxic chemicals may have higher transportability by air and water than PCDDs. Congener patterns of PCDD/Fs in albatross showed less variability as compared to those in terrestrial species, indicating that contamination patterns of PCDD/Fs were similar within the open ocean environment. Contributions of PCDD/Fs to total TEQs in albatrosses from the open ocean were generally lower than those in terrestrial birds, suggesting different toxic potency of PCDD/Fs and coplanar PCBs on animals inhabiting open ocean and terrestrial environment. Whereas albatrosses from southern oceans retained lower TEQ concentrations, possible adverse effects of PCDD/Fs and coplanar PCBs to black-footed and Laysan albatrosses of the North Pacific Ocean may be suspected from TEQ levels.     

Perfluorooctane sulfonate in fish-eating water birds including bald eagles and albatrosses

Perfluorooctane sulfonate (PFOS) was measured in 161 samples of liver, kidney, blood, or egg yolk from 21 species of fish-eating water birds collected in the United States including albatrosses from Sand Island, Midway Atoll, in the central North Pacific Ocean. Concentrations of PFOS in the blood plasma of bald eagles collected fromthe midwestern United States ranged from 13 to 2,220 ng/mL (mean: 330 ng/mL), except one sample that did not contain quantifiable concentrations of PFOS. Concentrations of PFOS were greater in blood plasma than in whole blood. Among 82 livers from various species of birds from inland or coastal U.S. locations, Brandt's cormorant from San Diego, CA, contained the greatest concentration of PFOS (1,780 ng/g, wet wt). PFOS was also found in the sera of albatrosses from the central North Pacific Ocean at concentrations ranging from 3 to 34 ng/mL. Occurrence of PFOS in birds from remote marine locations suggests widespread distribution of PFOS and related fluorochemicals in the environment.     

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.     

Quantitative determination of perfluorochemicals and fluorotelomer alcohols in plants from biosolid-amended fields using LC/MS/MS and GC/MS

Analytical methods for determining perfluorochemicals (PFCs) and fluorotelomer alcohols (FTOHs) in plants using liquid chromatography/tandem mass spectrometry (LC/MS/MS) and gas chromatography/mass spectrometry (GC/MS) were developed, and applied to quantify a suite of analytes in plants from biosolid-amended fields. Dichloromethane-methanol and ethylacetate were chosen as extracting solutions for PFCs and FTOHs, respectively. Nine perfluorocarboxylic acids (PFCAs), three perfluorosulfonic acids (PFSAs), and ten FTOHs were monitored. Most PFCAs and perfluorooctanesulfonate (PFOS) were quantifiable in plants grown in contaminated soils, whereas PFCs went undetected in plants from two background fields. Perfluorooctanoic acid (PFOA) was a major homologue (～10-200 ng/g dry wt), followed by perfluorodecanoic acid (～3-170 ng/g). [PFOS] in plants (1-20 ng/g) generally was less than or equal to most [PFCAs]. The site-specific grass/soil accumulation factor (GSAF = [PFC](Grass)/[PFC](Soil)) was calculated to assess transfer potentials from soils. Perfluorohexanoic acid had the highest GSAF (= 3.8), but the GSAF decreased considerably with increasing PFCA chain length. Log-transformed GSAF was significantly correlated with the PFCA carbon-length (p < 0.05). Of the measured alcohols, 8:2nFTOH was the dominant species (≤1.5 ng/g), but generally was present at ≥10× lower concentrations than PFOA.     

Temporal trends and pattern of polyfluoroalkyl compounds in Tawny Owl (Strix aluco) eggs from Norway, 1986-2009

Temporal trends of polyfluoroalkyl compounds (PFCs) were examined in tawny owl (Strix aluco) eggs collected in Central Norway over a period of 24 years (1986-2009). Concentrations of 12 PFCs, including C(6)-C(8), C(10) perfluoroalkyl sulfonates (PFSAs), perfluorooctane sulfonamide (PFOSA), and C(8)-C(14) perfluoroalkyl carboxylates (PFCAs), were measured, whereas saturated and unsaturated fluorotelomer carboxylates and shorter chain PFSAs and PFCAs were not detected. Perfluorooctane sulfonate (PFOS) was the predominant compound (geometric mean 10.1 ng/g wet weight (ww)), followed by perfluorotridecanoate (PFTriDA) (0.36 ng/g ww) and perfluoroundecanoate (PFUnDA) (0.19 ng/g ww). Significant decreasing concentrations were found for PFOS with an annual decrease of 1.6% (1986-2009), while, conversely, the C(10)-C(13) PFCA concentrations increase significantly with an annual increase of 4.2-12% (1986-2009). Consequently, the contribution of PFOS to the ∑PFCs decreased, whereas the contribution of the ∑PFCAs increased over the time. Toxicological implications for tawny owls are limited, but the maximal PFOS concentration found in this stu0dy is about 20 times lower than the predicted avian no effect concentration (PNEC) which suggest adverse effects caused by PFOS are unlikely. However, tawny owls are exposed to a mixture of various PFCs, and PFCA concentrations still increase.     

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)).     

Perfluorooctanesulfonate and related fluorinated hydrocarbons in marine mammals,fishes, and birds from coasts of the Baltic and the Mediterranean Seas

Perfluorooctanesulfonate (PFOS; C8F17SO3-), perfluorooctanesulfonamide (FOSA; C8F17SO2NH2), perfluorohexanesulfonate (PFHxS; C6F13SO3-), and perfluorooctanoate (PFOA; C7F15CO2-) were detected in 175 samples of liver and blood of bluefin tuna (Thunnus thynnus), swordfish (Xiphias gladius), common cormorants (Phalacrocorax carbo), bottlenose dolphins (Tursiops truncatus), striped dolphins (Stenella coeruleoalba), common dolphins (Delphinus delphi), fin whales (Balenoptera physalus), and long-finned pilot whales (Globicephala melas) from the Italian coast of the Mediterranean Sea and in livers of ringed seals (Phoca hispida), gray seals (Halichoerus grypus), white-tailed sea eagles (Haliaeetus albicilla), and Atlantic salmon (Salmo salar) from coastal areas of the Baltic Sea. PFOS was detected in all of the wildlife species analyzed. Concentrations of PFOS in blood decreased in order of bottlenose dolphins > bluefin tuna > swordfish. Mean PFOS concentrations (61 ng/ g, wet wt) in cormorant livers collected from Sardinia Island in the Mediterranean Sea were less than the concentrations of PFOA (95 ng/g, wetwt). PFOS concentrations in cormorant livers were significantly correlated with those of PFOA. FOSA was found in 14 of 19 livers or blood samples of marine mammals from the Mediterranean Sea. The highest concentration of 878 ng FOSA/g, wet wt, was found in the liver of a common dolphin. Livers of ringed and gray seals from the Bothnian Bay in the Baltic Sea contained PFOS concentrations ranging from 130 to 1,100 ng/g, wet wt. No relationships between PFOS concentrations and ages of ringed or gray seals were observed. Concentrations of PFOS in livers of seals were 5.5-fold greater than those in corresponding blood. A significant positive correlation existed between the PFOS concentrations in liver and blood, which indicates that blood can be used for nonlethal monitoring of PFOS. Trend analysis of PFOS concentrations in livers of white-tailed sea eagles collected from eastern Germany and Poland since 1979 indicated an increase in concentrations during the 1990s. Livers of Atlantic salmons did not contain quantifiable concentrations of any of the fluorochemicals monitored. PFOS is a widespread contaminant in wildlife from the Baltic and the Mediterranean Seas, while FOSA and PFOA were detected only in certain locations indicating their sporadic spatial distribution.     

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.     

Perfluorooctanesulfonate and related fluorinated hydrocarbons in mink and river otters from the United States

Mink and otters are good integrators of their aquatic environments and useful sentinel species for determining exposure to environmental contaminants. In this study, perfluorooctanesulfonate (PFOS; C8F17SO3-), perfluorooctanesulfonamide (FOSA; C8F17SO2NH2), perfluorohexanesulfonate (PFHxS; C6F13SO3-), and perfluorooctanoate (PFOA; C7F15CO2-) were measured in livers of mink and river otters collected from various locations in the United States. PFOS was found in all mink livers analyzed. Frequencies of occurrence of FOSA, PFHxS, and PFOA were less. The greatest concentration of PFOS measured in liver of mink was 5140 ng/g, wet weight. Maximum concentrations of FOSA, PFHxS, and PFOA in mink livers were 590, 39, and 27 ng/g, wet weight, respectively. There were no significant positive relationships between concentrations of PFOS and PFHxS or PFOA in mink livers. Concentrations of PFOS were positively correlated with those of FOSA in mink livers from Illinois. There was no significant correlation between concentrations of PFOS and lipid content in mink livers. There were no age- or sex-related differences in the concentrations of fluorochemicals in mink livers. Greater concentrations are associated with those individuals collected near urbanized and/or industrialized areas. PFOS was detected in livers of all river otters collected from Washington and Oregon at concentrations ranging from 25 to 994 ng/g, wet wt.     

Determinants of fetal exposure to polyfluoroalkyl compounds in Baltimore, Maryland

Polyfluoroalkyl compounds (PFCs), such as perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA), are ubiquitous, man-made chemicals. Human data suggest that in utero exposures to these chemicals occur and some evidence of developmental toxicity in animals exists. To assess the distribution and determinants of fetal exposure to PFCs, we analyzed cord serum samples from 299 singleton newborns delivered between 2004 and 2005 in Baltimore, MD for 10 PFCs by employing on-line solid-phase extraction coupled with reversed-phase high-performance liquid chromatography-tandem mass spectrometry. PFOS and PFOA were detected in 99 and 100% of umbilical cord sera, with geometric mean concentrations of 4.9 and 1.6 ng/mL, respectively. PFOS and PFOA concentrations were highly correlated (Pearson's r = 0.64 after natural log transformation, p < 0.01). Eight other PFCs were detected less frequently and at lower concentrations than PFOS and PFOA. Geometric mean concentrations of PFOS for Asians (6.0 ng/mL) and Blacks (5.1 ng/mL) were higher than those for Whites (4.2 ng/mL), while PFOA levels were more evenly distributed by race. Other maternal demographic and socioeconomic characteristics, including age, education, marital status, and living in the city limits were not significantly associated with cord concentrations. Our findings suggest that in utero exposure to PFOS and PFOA is ubiquitous in a population of babies born in Baltimore, MD.     

Perfluorinated compounds in the plasma of loggerhead and Kemp's ridley sea turtles from the southeastern coast of the United States

Perfluorinated compounds (PFCs) have been measured in blood of humans and wildlife and are considered globally distributed contaminants. We examined 12 PFCs in the plasma of 73 loggerhead sea turtles (Caretta caretta) and 6 Kemp's ridley sea turtles (Lepidochelys kempii) captured from inshore waters of Core Sound, North Carolina (NC), and offshore waters of South Carolina, Georgia, and Florida (SC-FL). Perfluorooctanesulfonate (PFOS) and perfluorooctanoic acid (PFOA) were the dominant compounds, with respective mean concentrations of 11.0 ng/mL and 3.20 ng/mL for loggerhead turtles and 39.4 ng/mL and 3.57 ng/mL for Kemp's ridley turtles. Mean PFOS concentrations were 2- to 12-fold higher than typical mean sigmaPCB concentrations (approximately 5 ng/g wet mass) measured previously in sea turtle blood. More than 79% of the samples had detectable levels of perfluorocarboxylates (PFCAs) with 8-12 carbons, whereas only 17% or less of samples had detectable levels of PFCAs with 6 or 7 carbons. No samples had detectable levels of PFCAs with 4 or 5 carbons. In loggerhead turtles, sigmaPFC concentrations were not influenced by sex (p > 0.05), but were higher in turtles captured from inshore waters of NC than in turtles from offshore waters of SC-FL (p = 0.009). A backward stepwise multiple regression model showed that sigmaPFC concentrations were (1) significantly higher in Kemp's ridley turtles than loggerhead turtles (p < 0.0001), (2) higher in larger turtles (p = 0.018; carapace length used as a proxy for age), and (3) higher in turtles captured toward the north (p = 0.006). These findings suggest that bioaccumulation of PFCs in sea turtles is influenced by species, age, and habitat.     

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.     

Association between perfluorinated compounds and pathological conditions in southern sea otters

Concentrations of four perfluorinated contaminants, including perfluorooctanesulfonate (PFOS) and perfluorooctanoic acid (PFOA), were measured in liver tissue from 80 adult female sea otters collected from the California coast during 1992-2002. Concentrations of PFOS and PFOA were in the ranges of <1-884 and <5-147 ng/g, wet wt, respectively. Concentrations of PFOA in the livers of these sea otters were among the highest values reported for marine mammals to date. Liver tissue from 6 male sea otters also was analyzed and contained significantly higher concentrations of PFOS than did tissues from female otters. To examine the association between exposures and potential effects, concentrations of PFOS and PFOA were compared among the adult female otters that died from infectious diseases, noninfectious causes, and from apparent emaciation. Concentrations of both PFOA and PFOS were significantly higher in sea otters in the infectious disease category than in the noninfectious category. Concentrations of PFOS and PFOA were not significantly different between noninfectious and emaciated otters, suggesting that the poor nutritive (body) status of emaciated otters did not affectthe concentrations of perfluorochemicals in livers. Concentrations of PFOA increased significantly from 1992 to 2002, whereas PFOS concentrations increased from 1992to 1998 and then decreased after 2000. Significant association between infectious diseases and elevated concentrations of PFOS/PFOA in the livers of sea otters is a cause for concern and suggests the need for further studies.     

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.     

Occurrence of perfluoroalkyl compounds in surface waters from the North Pacific to the Arctic Ocean

Perfluoroalkyl compounds (PFCs) were determined in 22 surface water samples (39-76°N) and three sea ice core and snow samples (77-87°N) collected from North Pacific to the Arctic Ocean during the fourth Chinese Arctic Expedition in 2010. Geographically, the average concentration of ∑PFC in surface water samples were 560 ± 170 pg L(-1) for the Northwest Pacific Ocean, 500 ± 170 pg L(-1) for the Arctic Ocean, and 340 ± 130 pg L(-1) for the Bering Sea, respectively. The perfluoroalkyl carboxylates (PFCAs) were the dominant PFC class in the water samples, however, the spatial pattern of PFCs varied. The C(5), C(7) and C(8) PFCAs (i.e., perfluoropentanoate (PFPA), perfluoroheptanoate (PFHpA), and perfluorooctanoate (PFOA)) were the dominant PFCs in the Northwest Pacific Ocean while in the Bering Sea the PFPA dominated. The changing in the pattern and concentrations in Pacific Ocean indicate that the PFCs in surface water were influenced by sources from the East-Asian (such as Japan and China) and North American coast, and dilution effect during their transport to the Arctic. The presence of PFCs in the snow and ice core samples indicates an atmospheric deposition of PFCs in the Arctic. The elevated PFC concentration in the Arctic Ocean shows that the ice melting had an impact on the PFC levels and distribution. In addition, the C(4) and C(5) PFCAs (i.e., perfluorobutanoate (PFBA), PFPA) became the dominant PFCs in the Arctic Ocean indicating that PFBA is a marker for sea ice melting as the source of exposure.     

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.     

Spatial distribution of perfluoroalkyl contaminants in lake trout from the Great Lakes

Individual whole body homogenates of 4 year old lake trout (Salvelinus namaycush) samples collected in 2001 from each of the Great Lakes were extracted using a novel fluorophilicity cleanup step and analyzed for perfluoroalkyl compounds (PFCs). Standard addition and internal standardization were used for quantification. Results were reported (+/- SE) for perfluorinated carboxylates (PFCAs), perfluorinated sulfonates (PFSAs), and unsaturated fluorotelomer carboxylates (8:2 and 10:2 FTUCA). The lowest average concentration of sigmaPFC was found in samples from Lake Superior (13+/-1 ng g(-1)), while the highest average concentration was found in samples from Lake Erie (152+/-14 ng g(-1)). Samples from Lake Ontario (60+/-5 ng g(-1)) and Lake Huron (58 +/-10 ng g(-1)) showed similar average sigmaPFC concentrations, although the perfluorinated sulfonate/carboxylate ratios were different. The major perfluoroalkyl contaminant observed was perfluorooctane sulfonate (PFOS) with the highest concentration found in samples from Lake Erie (121+/-14 ng g(-1)), followed by samples from Lake Ontario (46+/-5 ng g(-1)), Lake Huron (39 +/-10 ng g(-1)), Lake Michigan (16+/-3 ng g(-1)), and Lake Superior (5+/-1 ng g(-1)). Perfluorodecane sulfonate (PFDS) was detected in 89% of the samples, with the highest concentration in Lake Erie samples (9.8+/-1.6 ng g(-1)), and lowest concentration in samples from Lake Superior (0.7 +/- 0.1 ng g(-1)). Statistically significant correlations were observed between PFOS and PFDS concentrations, and PFOS concentration and body weight, respectively. The PFCAs were detected in all samples, with the highest total average concentration in samples from Lake Erie (19 ng g(-1)), followed by samples from Lake Huron (16 ng g(-1)), Lake Ontario (10 ng g(-1)), Lake Michigan (9 ng g(-1)) and Lake Superior (7 ng g(-1)). The compounds with significant contributions to the sigmaPFCA concentrations were PFOA and C9-C13-PFCAs. The 8:2 FTUCA was detected at concentrations ranging between 0.1 and 0.2 ng g-1, with the highest level in samples showing also elevated concentrations of PFOA (4.4 ng g(-1) for Lake Michigan vs 1.5 ng g(-1) for all other samples). The 10:2 FTUCA was detected only in 9% of all samples (nd, 45 pg g(-1)). For those PFCs where we determined lake water concentrations, the highest log BAFs were calculated for PFOS (4.1), PFDA (3.9), and PFOSA (3.8).     

Temporal trends of PFOS and PFOA in guillemot eggs from the Baltic Sea, 1968--2003

Perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) have recently been identified as ubiquitous environmental contaminants. Although they have been produced for 50 years, little is known about when they first appeared in the environment and how their concentrations have changed over time, particularly in response to the phase-out of PFOS, which began in 2000. In this study temporal trends in the concentrations of PFOS and PFOA in the Baltic Sea marine environmentwere measured using archived guillemot eggs. Samples collected from Stora Karls? (Sweden) between 1968 and 2003 were received from an environmental specimen bank and concentrations of PFOS and PFOA were analyzed using HPLC coupled to ESI-MS/MS. PFOA was not detected in any of the samples (LOD 3 ng/g), but there was an almost 30-fold increase in PFOS concentrations in the guillemot eggs during the time period, from 25 ng/g in 1968 to 614 ng/g in 2003 (wet weight). Regression analysis indicated a significant trend, increasing on average between 7 and 11% per year. A sharp peak in PFOS concentrations was observed in 1997 followed by decreasing levels up to 2002, but this cannot be linked to the PFOS phase-out, which occurred at the end of this period.     

Dietary intake estimate for perfluorooctanesulphonic acid (PFOS) and other perfluorocompounds (PFCs) in UK retail foods following determination using standard addition LC–MS/MS

The analysis of 252 food samples (UK-produced and imported) purchased from a variety of retail outlets in the UK was undertaken for the presence of perfluorooctanesulphonic acid (PFOS), perfluorooctanoic acid (PFOA) and nine other perfluorocompounds (PFCs). A limit of quantification (LOQ) of 1 µg/kg was achieved for all target analytes, in all samples. Standard addition was used for quantification of PFC levels. All 11 of the targeted PFCs were detected in 75 individual food items. In 70% of the samples, including all meat other than offal, none of the analytes were present above the LOD. The highest levels found were 59 µg/kg perfluorooctanesulphonic acid (PFOS) and 63 µg/kg total PFCs (ΣPFCs) in an eel sample, and 40 µg/kg PFOS (62 µg/kg ΣPFCs) in a whitebait sample. The highest level in an offal sample was 10 µg/kg, in a wild roe deer liver. There were six samples with ΣPFCs >15 µg/kg (fish, shellfish, crustaceans), a further seven samples with ΣPFCs ranging 11–15 µg/kg (including a liver), nine with ΣPFCs ranging 6–10 µg/kg (fish and livers), 31 with ΣPFCs in the range 2–5 µg/kg (including kidneys, popcorn and processed peas) and a further 22 with ΣPFCs close to the LOD of 1 µg/kg (including eggs and potatoes). These concentrations indicate that UK consumers are being exposed to a low level of PFC contamination from food. The estimated upper bound dietary intake of 10 ng/kg bodyweight (bw)/day of PFOS for average adult consumers is well below the 0.15 µg (150 ng)/kg bw tolerable daily intake (TDI) set by the European Food Safety Authority. The lower bound adult dietary intake estimate of 1 ng/kg bw/day is similar to estimates undertaken and reported in countries such as Canada, Germany and Spain.