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.     

Perfluorooctanesulfonate and related fluorochemicals in human blood from several countries

Perfluorooctanesulfonyl fluoride based compounds have been used in a wide variety of consumer products, such as carpets, upholstery, and textiles. These compounds degrade to perfluorooctanesulfonate (PFOS), a persistent metabolite that accumulates in tissues of humans and wildlife. Previous studies have reported the occurrence of PFOS, perfluorohexanesulfonate (PFHxS), perfluorooctanoate (PFOA), and perfluorooctanesulfonamide (PFOSA) in human sera collected from the United States. In this study, concentrations of PFOS, PFHxS, PFOA, and PFOSA were measured in 473 human blood/serum/plasma samples collected from the United States, Colombia, Brazil, Belgium, Italy, Poland, India, Malaysia, and Korea. Among the four perfluorochemicals measured, PFOS was the predominant compound found in blood. Concentrations of PFOS were the highest in the samples collected from the United States and Poland (>30 ng/mL); moderate in Korea, Belgium, Malaysia, Brazil, Italy, and Colombia (3 to 29 ng/mL); and lowest in India (<3 ng/mL). PFOA was the next most abundant perfluorochemical in blood samples, although the frequency of occurrence of this compound was relatively low. No age- or gender-related differences in the concentrations of PFOS and PFOA were found in serum samples. The degree of association between the concentrations of four perfluorochemicals varied, depending on the origin of the samples. These results suggested the existence of sources with varying levels and compositions of perfluorochemicals, and differences in exposure patterns to these chemicals, in various countries. In addition to the four target fluorochemicals measured, qualitative analysis of selected blood samples showed the presence of other perfluorochemicals such as perfluorodecanesulfonate (PFDS), perfluoroheptanoic acid (PFHpA), perfluorononanoic acid (PFNA), perfluorodecanoic acid (PFDA), perfluorododecanoic acid (PFDoA), and perfluoroundecanoic acid (PFUnDA) in serum samples, at concentrations approximately 5- to 10-fold lower than the concentration of PFOS. Further studies should focus on identifying sources and pathways of human exposure to perfluorochemicals.     

Time trends and transplacental transfer of perfluorinated compounds in melon-headed whales stranded along the Japanese coast in 1982, 2001/2002, and 2006

As a result of the phase-out of production of perfluorooctanesulfonyl-based compounds by a major producer, concentrations of perfluorooctanesulfonate (PFOS) in marine mammals from North American and European coastal waters have been declining since the early 2000s. Nevertheless, temporal trends in perfluorochemical (PFC) concentrations in marine mammals from Asian coastal waters have not been examined. In this study, PFCs were determined in livers of melon-headed whales (Peponocephala electra) collected along the coast of Japan, from three mass strandings that occurred during the past 25 years. Concentrations of nine PFCs were determined in livers of 48 melon-headed whales that were collected during strandings in 1982, 2001/2002, and 2006. In addition, concentrations in liver tissues obtained from two pregnant females and their fetuses were compared for determination of transplacental transfer rates of PFCs during gestation. PFOS and perfluorooctanesulfonamide (PFOSA) were the predominant PFCs found in livers of melon-headed whales collected in 1982 (n = 22). PFOS, PFOSA, perfluoroundecanoate (PFUnDA), perfluorododecanoate (PFDoDA), perfluorodecanoate (PFDA), and perfluorononanoate (PFNA) were found in whales collected in 2001/2002 (n = 21) and in 2006 (n = 5). Concentrations of PFOS and PFOSA were approximately 10-fold higher in 2001/2002 than in 1982. Whereas concentrations of PFOSA then declined by 2-fold from 2001/ 2002 to 2006, concentrations of PFOS and perfluorocarboxylates did not decline after 2001/2002. Conversely, concentrations of PFNA and PFDA increased significantly from 2001/2002 to 2006. The proportion of perfluoroalkylsulfonates in total PFC concentrations decreased from 75% in 1982 to 51% in 2006. Conversely, the contribution of perfluorocarboxylates to total PFC concentrations increased from 25% in 1982 to 49% in 2006. PFUnDA was the major perfluorocarboxylate found in whale livers collected after 2000. Analysis of paired samples of mother-fetus demonstrated that the transplacental transfer rates of PFCs were higher than those for PCBs and PBDEs.     

Temporal and spatial trends of perfluorinated compounds in ringed seal (Phoca hispida) from Greenland

Perfluorinated compounds (PFCs), such as perfluorooctane sulfonate (PFOS) and related compounds, have been identified as global pollutants and have shown their bioaccumulation into higher trophic levels in the food chain. PFCs have been found in remote areas far from sources, such as the Arctic. In this study spatial and temporal trends in the concentrations of selected PFCs were measured using archived liver samples of ringed seal (Phoca hispida) from East and West Greenland. The samples were collected in four different years at each location, between 1986 and 2003 in East Greenland and between 1982 and 2003 in West Greenland. PFOS was the major contributor to the burden of PFCs in samples, followed by perfluoroundecanoic acid (PFUnA). Perfluorononanoic acid (PFNA) and perfluorodecanoic acid (PFDA) were also detected in most samples. Perfluorohexane sulfonate (PFHxS) and perfluorooctane sulfonamide (PFOSA) were only found sporadically. Perfluorooctanoic acid was not found in detectable concentrations in any sample. Regression analysis of logarithmic transformed PFOS, PFDA, and PFUnA median concentrations indicated a significant temporal trend with increasing concentrations at both locations. A spatial trend in PFOS concentrations (ANOVA, p < 0.0001) was observed between the two sampling locations, with significantly higher concentrations in seals from East Greenland.     

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.     

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.     

Is fish a major source of fluorinated surfactants and repellents in humans living on the Baltic Coast?

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

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.     

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.     

Mass loading and fate of perfluoroalkyl surfactants in wastewater treatment plants

Wastewater treatment plants have recently been identified as a significant pathway for the introduction of perfluoroalkyl surfactants (PASs) to natural waters. In this study, we measured concentrations and fate of several PASs in six wastewater treatment plants (WWTPs) in New York State. We also monitored and measured matrix effects (ionization suppression and enhancement) by postcolumn infusion and standard additions. Concentrations of perfluorooctanoate (PFOA) in effluents of the six WWTPs ranged from 58 to 1050 ng/L. Perfluorooctanesulfonate (PFOS) was also ubiquitous in effluents of these WWTPs, albeit at much lower concentrations (3-68 ng/L). Two of these WWTPs employed identical treatment processes, with similar hydraulic retentions, but differed only in that Plant B treated domestic and commercial waste, whereas Plant A had an additional industrial influence. We found that this industrial influence resulted in significantly greater mass flows of all of the PASs analyzed. Primary treatment was found to have no effect on the mass flows of PASs. Secondary treatment by activated sludge in Plant A significantly increased (p < 0.05) the mass flows of PFOS, PFOA, perfluorononanoate (PFNA), perfluorodecanoate (PFDA), and perfluoroundecanoate (PFUnDA). However, in Plant B, only the mass flow of PFOA was significantly increased. The observed increase in mass flow of several PASs may have resulted from biodegradation of precursor compounds such as fluorotelomer alcohols, which is supported by significant correlations in the mass flow of PFOA/PFNA and PFDA/PFUnDA. Furthermore, the masses of PFDA and PFUnDA were significantly correlated only after the secondary treatment. In Plant A, concentrations of odd-number PFCAs were greater than those of even-number PFCAs, and concentration decreased with increasing chain length (from C8 to C12). A different pattern was observed in sludge samples, in which the dominance of PFOA decreased, and PFDA and PFUnDA increased, suggesting preferential partitioning of longer-chain PFCAs to sludge.     

Trophic magnification of poly- and perfluorinated compounds in a subtropical food web

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

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.     

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.     

Use of newborn screening program blood spots for exposure assessment: declining levels of perluorinated compounds in New York State infants

Temporal biomonitoring studies can assess changes in population exposures to contaminants, but collection of biological specimens with adequate representation and sufficient temporal resolution can be resource-intensive. Newborn Screening Programs (NSPs) collect blood as dried spots on filter paper from nearly all infants born in the United States (U.S.). In this study, we investigated the use of NSP blood spots for temporal biomonitoring by analyzing perfluorooctane sulfonate (PFOS), perfluorooctane sulfonamide (PFOSA), perfluorohexane sulfonate (PFHxS), perfluorooctanoic acid (PFOA), and perfluorononanoic acid (PFNA) in 110 New York State (NYS) NSP blood spot composite specimens collected between 1997 and 2007, representing a total of 2640 infants. All analytes were detected in > or =90% of the specimens. Concentrations of PFOS, PFOSA, PFHxS, and PFOA exhibited significant exponential declines after the year 2000, coinciding with the phase-out in PFOS production in the U.S. Calculated disappearance half-lives for PFOS, PFHxS, and PFOA (4.4, 8.2, and 4.1 years, respectively) were similar to biological half-lives reported for retired fluorochemical workers. Our results suggest sharp decreases in perinatal exposure of NYS infants to PFOS, PFOSA, PFHxS, and PFOA and demonstrate, for the first time, the utility of NSP blood spots for assessment of temporal trends in exposure.     

基于液相色谱-串联质谱法的纺织品中痕量全氟化合物的测定

采用超声法提取纺织品中的全氟化合物。以C18为分析柱,甲醇-5 mmol/L乙酸铵为梯度洗脱淋洗液, 13 min内即可分离全氟己酸(PFHxA),全氟辛酸(PFOA),全氟壬酸(PFNA),全氟癸酸(PFDA),全氟十一酸(PFuDA),全氟十二酸(PFDoA), 全氟丁烷磺酸(PFBS),全氟己烷磺酸(PFHxS),全氟辛烷磺酸(PFOS),全氟癸烷磺酸(PFDS) 10种分析物。以313.1/268.9,412.9/368.9,462.9/418.9,512.7/468.9,562.7/518.9,612.8/568.9,298.8/99,399.2/99,498.8/99,599/99分别对PFHxA,PFOA,PFNA,PFDA,PFuDA,PFDoA,PFBS,PFHxS,PFOS,PFDS进行监控和定量分析。利用同位素内标法进行定量,线性范围和添加回收率分别为0.5～10 µg/m2、84.6%～111.8%,检出限为0.5 µg/m2,低于欧盟指定针对纺织品1 µg/m2 的限定。结果表明,本方法准确、快速,并成功用于20种纺织品实样的检测。     

Automated solid-phase extraction and measurement of perfluorinated organic acids and amides in human serum and milk

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

Serum concentrations of 11 polyfluoroalkyl compounds in the u.s. population: data from the national health and nutrition examination survey (NHANES)

We measured the concentrations of 11 polyfluoroalkyl compounds (PFCs), including perfluorooctane sulfonic acid (PFOS), perfluorooctanoic acid (PFOA), and perfluorohexane sulfonic acid (PFHxS) in 1562 serum samples collected from a representative U.S. population 12 years of age and older in the 1999-2000 National Health and Nutrition Examination Survey. Participants represented both sexes, three race/ethnicities (non-Hispanic blacks, non-Hispanic whites, and Mexican-Americans), and four age categories (12-19 years, 20-39 years, 40-59 years, and 60 years and older). PFCs were extracted from 100 microL of serum using on-line solid-phase extraction coupled to isotope dilution-high performance liquid chromatography-tandem mass spectrometry; limits of detection ranged from 0.05 to 0.2 ng/ mL. PFOS, PFOA, PFHxS, and perfluorooctane sulfonamide were detected in all samples analyzed; 2-(N-ethyl-perfluorooctane sulfonamido) acetic acid, 2-(N-methyl-perfluorooctane sulfonamido) acetic acid, and perfluorononanoic acid were detected in more than 90% of samples, which suggests prevalent exposures to several PFCs in the U.S. population. The concentrations of most PFCs were similar regardless of the participants' ages but were higher in males than in females. Mexican Americans had lower concentrations than non-Hispanic blacks and non-Hispanic whites, whose concentrations were similar. Higher education was associated with higher concentrations of PFOS and PFOA. These data will serve as a nationally representative baseline of the U.S. population's exposure to PFCs to which other populations can be compared, and will play an important role in public health by helping set research priorities, ranging from health effects studies to defining sources and pathways of exposure.     

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.     

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.