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

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

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

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

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

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

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

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

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

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

Abstract  This study investigated the occurrence of perfluoroalkyl acids (PFAAs) in surface water from 67 sampling sites along rivers of the Pearl River Delta in southern China. Sixteen PFAAs, including perfluoroalkyl carboxylic acids (PFCAs, C5-14, C16 and C18) and perfluoroalkyl sulfonic acids (PFSAs, C4, C6, C8 and C10) were determined by high performance liquid chromatography-negative electrospray ionization-tandem mass spectrometry (HPLC/ESI-MS/MS). Total PFAA concentrations (∑ PFAAs) in the surface water ranged from 1.53 to 33.5ng·L(-1) with an average of 7.58ng·L(-1). Perfluorobutane sulfonic acid (PFBS), perfluorooctanoic acid (PFOA), and perfluorooctane sulfonic acid (PFOS) were the three most abundant PFAAs and on average accounted for 28%, 16% and 10% of ∑ PFAAs, respectively. Higher concentrations of ∑ PFAAs were found in the samples collected from Jiangmen section of Xijiang River, Dongguan section of Dongjiang River and the Pearl River flowing the cities which had very well-developed manufacturing industries. PCA model was employed to quantitatively calculate the contributions of extracted sources. Factor 1 (72.48% of the total variance) had high loading for perfluorohexanoic acid (PFHxA), perfluoropentanoic acid (PFPeA), PFBS and PFOS. For factor 2 (10.93% of the total variance), perfluorononanoic acid (PFNA) and perfluoroundecanoic acid (PFUdA) got high loading. The sorption of PFCAs on suspended particulate matter (SPM) increased by approximately 0.1logunits for each additional CF2 moiety and that on sediment was approximately 0.8logunits lower than the SPM logKd values. In addition, the differences in the partition coefficients were influenced by the structure discrepancy of absorbents and influx of fresh river water. These data are essential for modeling the transport and environmental fate of PFAAs.

Abstract  Per- and polyfluoroalkyl substances (PFASs) are used in various industries, which results in their ubiquitous occurrence in the environment. This study determined the concentrations of eighteen PFASs in muscle and liver of nine wild freshwater fish species collected from rivers in the Pearl River Delta (PRD) region, South China, and assessed their bioaccumulation and potential health risks to local people. The results showed that eight and twelve PFASs were detected in the fish muscle and liver samples, respectively. Perfluorooctane sulfonate (PFOS) was found to be the predominant PFAS both in muscle and liver with its highest concentrations of 79ng/g wet weight (ww) in muscle and 1500ng/g ww in liver, followed by Perfluoroundecanoic acid (PFUnDA) and Perfluorotridecanoic acid (PFTrDA) with trace concentrations. The mean PFOS concentrations in fish muscle and liver tissues of the nine collected species ranged from 0.40ng/g in mud carp to 25ng/g in snakehead, and from 5.6ng/g in mud carp to 1100ng/g in snakehead, respectively. Significant positive correlations were found among PFASs both in water and fish, indicating a similar pollution source for these PFASs. In tilapia samples, PFOS concentrations showed an increasing trend with increasing length and weight, but no significant difference between genders. Bioaccumulation factors (logBAF) in fish for the PFASs were in the range from 2.1 to 5.0. The calculated hazard ratios (HR) of PFOS for all fishes were in the range of 0.05-2.8, with four out of nine species (tilapia, chub, leather catfish and snakehead) having their HR values more than 1.0. The results suggest that frequent consumption of these four fish species may pose health risks to local population.

Abstract  Background Charleston Harbor has elevated concentrations of PFAS in dolphins, but local human exposure data are limited. Objectives We sought to describe PFAS serum concentrations’ temporal trends among Gullah African American residents of coastal South Carolina. Methods Longitudinal measures of PFAS in blood serum from a Gullah clinical sample, without lupus, were examined using spaghetti plots and visit-to-visit change scores (e.g., differences in concentrations between visits) among the 68 participants with repeated measures available. We also modeled population-level trends among the 71 participants with any data using proportionate percentile models, accounting for clustering through robust standard errors. In a post-hoc analysis we examined heterogeneity of temporal trends by age through mixed-effects models for the log-transformed PFAS compounds. Results Population concentrations of PFOS dropped approximately 9 (95% CI: 8, 10) percent each year over 2003–2013. This was concordant with individual PFOS trajectories (median PFOS change score −21.7 ng/g wet weight, interquartile range of PFOS change scores: −32.8, −14.9) and reports for other populations over this time period. Several other compounds including PFOA, PFHxS, and PFuNDA also showed a population-level decrease. However, examination of individual trajectories suggested substantial heterogeneity. Post-hoc analyses indicated that PFAS trajectories were heterogeneous by age. Conclusions Many PFAS compounds are decreasing in a sample of Gullah African Americans from coastal South Carolina. There may be age differences in the elimination kinetics of PFASs. The possible role of age as a modifier of PFAS serum trends merits further research.

Abstract  Perfluoroalkyl acids (PFAAs) are a large group of chemicals which are highly persistent in both nature and humans. The use of the most prominent ones, perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA), was reduced in the early 21st century, and since then levels in human matrices have decreased. However, these two compounds have been exchanged by other PFAAs, for which time trends have not been as extensively investigated. By the use of 80 plasma samples collected between 1987 and 2007 from healthy women (n=1-9 yearly for 1987-2001, n=15 from 2006, and n=10 from 2007), possible time trends of six PFAAs were assessed. Time trends were evaluated for the entire study period, as well as for three sub-periods. As seen in previous studies, levels of perfluorohexane sulfonate (PFHxS), PFOS, and PFOA peaked during the middle time period (1990-2000), with medians of 0.98 ng mL(-1), 18.06 ng mL(-1), and 3.73 ng mL(-1), respectively. However, levels of perfluorononanic acid (PFNA), perfluorodecanic acid (PFDA), and perfluoroundecanoic acid (PFUnDA) increased over the whole study period and most markedly so after year 2000, with medians of 0.73 ng mL(-1), 0.28 ng mL(-1), and 0.24 ng mL(-1), respectively, during the last study period.

Abstract  Perfluoroalkyl acids (PFAAs) have been used in various industrial and consumer products for decades, and have consequently been detected in human blood worldwide. In the present study, general adult population in Daegu, Korea (n=140, >20 years of old) was recruited, collected for serum, and analyzed for 13 major PFAAs. The influence of dietary and water consumption on serum PFAA levels was also evaluated. Perfluorooctane sulfonic acid (PFOS), perfluorooctanoic acid (PFOA), and perfluorohexane sulfonic acid (PFHxS) were frequently detected with relatively higher concentrations in blood serum. Most PFAA concentrations except for PFOA were detected in higher concentrations among males, and were positively correlated with age and body mass index (BMI). PFOA concentrations were relatively higher among the female of childbearing age, e.g., 20-49years old, raising concerns on potential impacts on fetus through transplacental transfer or lactation. In addition, the concentrations of PFOA in Daegu population were higher than other areas of Korea, suggesting a presence of distinctive sources in the area. Among food items, potato consumption was identified to be significant contributor to serum PFOA. For PFUnDA and PFTrDA levels, intake of fish/shellfish was positively associated. The results of this study will be useful in developing public health management options for PFAAs.

Abstract  Perfluorinated compounds (PFCs) were detected in sediment core samples collected in Tokyo Bay to reveal their time trends. The core sample deposited during 1950s-2004 was divided into two- to three-year intervals and the concentrations of 24 types of PFCs were determined. Perfluorooctane sulfonate (PFOS) decreased gradually from the early 1990s and its precursor decreased rapidly in the late 1990s, whereas perfluorooctanoic acid (PFOA) increased rapidly. The observed trends were regarded as a reflection of the shift from perfluorooctyl sulfonyl fluoride (PFOSF)-based products to telomer-based products after the phaseout of PFOSF-based products in 2001. The branched isomers of perfluoroundecanoic acid (PFUnDA) and perfluorotridecanoic acid (PFTrDA) were detected in the sample with its ratio of linear-isomer/branched-isomer concentrations decreasing. In this study, we revealed that the sediment core can serve as a tool for reconstructing the past pollution trend of PFCs and can provide interesting evidence concerning their environmental dynamics and time trend.

Abstract  The widespread occurrence and environmental persistence of perfluorinated compounds (PFCs) received worldwide attention recently. Exhaustive analysis of all fluorinated compounds in an environmental sample can be daunting because of the constraints in the availability of analytical standards and extraction methods. Combustion ion chromatographic technique for trace fluorine analysis was used to assess the concentrations of known PFCs (e.g., PFOS, PFOA) and total fluorine (TF) in the blood of wild rats collected from Japan. The technique was further validated using tissues from PFOA-exposed rats. Six PFCs (PFOS, PFOSA, PFUnDA, PFDA, PFNA, and PFOA) were detected in all of the wild rat blood samples. Concentrations of extractable organic fluorine (EOF) in fraction 1 (Fr1; MTBE extraction) of wild rats ranged 60.9-134 ng F mL(-1), while those in fraction 2 (Fr2; hexane) were below LOQ (32 ng F mL(-1)); TF concentrations in the blood of wild rats ranged from 59.9-192 ng F mL(-1). The contribution of known PFCs in EOF-Fr1 (MTBE) varied from 9% to 89% (56% on average), and known PFC concentrations in TF content were less than 25%. In contrast, TF concentrations in the blood of PFOA-exposed rats ranged from 46900 to 111,000 ng F mL(-1), with PFOA contributing over 90% of TF. A comparison of results from the samples analyzed in this study and the literature revealed three distinct groups with PFOA/known PFC and TF levels (i.e., wild rats and general population, occupationally exposed workers, and PFOA-exposed laboratory rats). The mass balance analysis of the different forms of fluorine in blood suggested the presence of other forms of organic fluorine in addition to known PFCs.

Abstract  Determining maternal concentrations of per- and polyfluoroalkyl substances (PFASs) and the relative impact of various demographic and dietary predictors is important for assessing fetal exposure and for developing proper lifestyle advisories for pregnant women. This study was conducted to investigate maternal PFAS concentrations and their predictors in years when the production and use of several PFASs declined, and to assess the relative importance of significant predictors. Blood from 391 pregnant women participating in The Northern Norway Mother-and-Child Contaminant Cohort Study (MISA) was collected in the period 2007-2009 and serum analyses of 26 PFASs were conducted. Associations between PFAS concentrations, sampling date, and demographic and dietary variables were evaluated by multivariate analyses and linear models including relevant covariates. Parity was the strongest significant predictor for all the investigated PFASs, and nulliparous women had higher concentrations compared to multiparous women (10 ng/mL versus 4.5 ng/mL in median PFOS, respectively). Serum concentrations of PFOS and PFOA of women recruited day 1-100 were 25% and 26% higher, respectively, compared to those women recruited in the last 167 days of the study (day 601-867), and the concentrations of PFNA, PFDA and PFUnDA increased with age. Dietary predictors explained 0-17% of the variation in concentrations for the different PFASs. Significantly elevated concentrations of PFOS, PFNA, PFDA and PFUnDA were found among high consumers of marine food. The concentrations of PFHxS, PFHpS and PFNA were also increased in high consumers of game and elevated concentrations of PFHpS and PFOS were detected in high consumers of white meat. Study subjects with a high intake of salty snacks and beef had significantly higher concentrations of PFOA. The present study demonstrates that parity, sampling date and birth year are the most important predictors for maternal PFAS concentrations in years following a decrease in production and use of several PFASs. Further, dietary predictors of PFAS concentrations were identified and varied in importance according to compound.

Abstract  BACKGROUND, AIM AND SCOPE: Perfluorinated compounds (PFCs) are global environmental pollutants that bioaccumulate in wildlife and humans. Laboratory experiments have revealed toxic effects such as delayed development, humoral suppression, and hepatotoxicity. Although numerous human blood levels have been reported, little is known about distribution in the human body. Knowledge about PFC distribution and accumulation in the human body is crucial to understanding uptake and subsequent effects as well as to conduct risk assessments. The present study reports PFC levels in human liver and breast milk from a general population living in Catalonia, Spain. Liver and milk levels are compared to previously reported levels in blood from the same geographic area as well as to other existing reports on human liver and milk levels in other countries.

MATERIALS AND METHODS: Human liver (n = 12) and milk (n = 10) samples were collected in 2007 and 2008 in Catalonia, Spain. Liver samples were taken postmortem from six males and six females aged 27-79 years. Milk samples were from healthy primipara women (30-39 years old). Both liver and milk were analyzed by solid-phase extraction and ultra-performance liquid chromatography tandem mass spectrometry.

RESULTS: Six PFCs were detected in liver, with perfluorooctanesulfonate (PFOS, 26.6 ng/g wet weight) being the chemical with the highest mean concentration. Other PFCs such as perfluorohexanesulfonate (PFHxS), perfluorooctanoic acid (PFOA), and acids with chain lengths up to C11 were also detected, with mean levels ranging between 0.50 and 1.45 ng/g wet weight. On the other hand, PFOS and PFHxS were the only PFCs detected in human milk, with mean concentrations of 0.12 and 0.04 ng/mL, respectively.

DISCUSSION: While milk concentrations were similar to reported levels from other countries, liver samples contained more PFCs above quantification limits and higher PFOS concentrations compared to the only two other reports found in the literature. Differences between the results of the present study and those concerning previous investigations can be due to declining levels of some PFCs, which have been reported for the USA. The relationship between PFC concentrations in human liver, milk, and blood was assessed using blood concentrations previously determined in Catalonia. Those levels resulted in liver/serum ratios of 1.7:1, 1.4:1, and 2.1:1 for PFOS, perfluorodecanoic acid, and perfluoroundecanoic acid, respectively. Accumulation in liver is suggested for PFOS and the perfluorocarboxylic acids with carbon chain lengths C9, C10, and C11. For PFOA and PFHxS, fivefold and 14-fold higher concentrations, respectively, were seen in serum as compared to liver. The mean concentration of PFOS and PFHxS in milk was only 0.8% and 0.6% of the reported mean serum level, respectively.

CONCLUSIONS: The results of the present study show that several PFCs could be detected in human liver samples of subjects living in Tarragona. Concerning human milk, the mechanism by which PFCs are transferred from mother's blood to breast milk is still unclear. Considering that PFCs are strongly bound to the protein fraction in blood, the possibility of PFCs entering the milk and accumulating to levels observed in maternal plasma is limited.

RECOMMENDATIONS AND PERSPECTIVES: Interestingly, the potential accumulation difference for PFCs with different chain lengths might be of great importance for risk assessment. Continuing studies on the distribution of different PFCs in human tissue are therefore justified.

Abstract  Perfluorooctane sulfonate (PFOS) and other perfluorinated alkylated substances (PFAS) were determined in liver, kidney, muscle, brain, and blubber samples of 31 harbor porpoises (Phocoena phocoena relicta) of different age and sex stranded along the Ukrainian coast of the Black Sea. In all individuals and in all tissues, PFOS was the predominant PFAS, accounting for on average 90% of the measured PFAS load. PFOS concentrations were the highest in liver (327+/-351 ng/g wet wt) and kidney (147 +/-262 ng/g wet wt) tissue, and lower in blubber (18+/-8 ng/g wet wt), muscle (41+/-50 ng/g wet wt), and brain (24 +/-23 ng/g wetwt). No significant differences could be determined between males and females, nor between juvenile and adult animals (p > 0.05). Perfluorononanoic acid, perfluorodecanoic acid, perfluoroundecanoic acid, and perfluorododecanoic acid could be detected in liver tissue of approximately 25% of the individuals. Perfluorobutane sulfonate, perfluorobutanoic acid, and perfluorooctanoic acid were not detected in any of the porpoise livers. Although we investigated a potential intraspecies segregation according to the source of prey, using stable isotopes, no statistically significant correlation between PFOS concentrations and stable isotopes could be determined. It is, however, noteworthy that the contamination by PFOS in the Black Sea harbor porpoises is comparable to levels found in porpoises from the German Baltic Sea and from coastal areas near Denmark and, therefore, might pose a threat to this population.

Abstract  A pre-sampling isotope dilution-direct injection-liquid chromatography tandem mass spectrometry (DI-LC/MS/MS) analytical method for the analysis of perfluorinated compounds (PFCs) in water is presented. This pre-sampling isotope dilution method incorporates stable isotope internal standards (ISs) and surrogate recovery standards (SRSs) added to sample bottles prior to sample collection. Pre-sampling isotope dilution corrects for PFC adsorption losses and enables a simple quantitative DI-LC/MS/MS water method with a 28 day sample holding time. Method analytes include perfluorinated carboxylic acids (PFCAs) (C4-C12), perfluorinated sulfonic acids (PFSAs) (C4, C6, and C8), perfluorooctane sulfonamide (PFOSA), and four SRSs ([2,3,4-C-13(3)]PFBA, [1,2,3,4-C-13(4)]PFOA, [1,2,3,4-C-13(4)]PFOS, and [1,2-C-13(2)]PFUnA). At 28 day sample holding times, mean recoveries of laboratory reagent water samples (Milli-Q (TM) water containing hardness at 165 mg equivalent CaCO3 L-1) fortified with the PFC method analytes at 0.2-40 ng mL(-1) (0.1-1 ng mL(-1) SRSs) are 94.9-115% with relative standard deviations of 0.97-7.9%. At 28 day sample holding times in fortified laboratory reagent water samples, single laboratory lowest concentration minimum reporting levels of 0.010-0.020 ng mL(-1) (0.075 ng mL(-1) PFBA) are demonstrated for method analytes and SRSs. Method applications to synthetic chlorinated drinking water samples and three environmental sample matrices are presented that demonstrate method ruggedness. Mean recoveries of synthetic chlorinated drinking water samples fortified with the PFC method analytes at 0.1-10 ng mL(-1) and SRSs at 0.1-1 ng mL(-1) are 97.8-113% with relative standard deviations of 2.0-18%. Mean recoveries and relative standard deviations in environmental groundwater samples, production facility non-contact cooling water effluent samples, and production facility wastewater treatment effluent samples fortified with the PFC method analytes at 0.25-2.5 ng mL(-1), 0.25-10 ng mL(-1), 0.25-50 ng mL(-1) respectively and SRSs at 0.1 ng mL(-1) are 100 +/- 7.7% (RSD +/- 12%, PFBA +/- 23%), 100 +/- 5.5% (RSD +/- 11%), 100 +/- 5.2% (RSD +/- 11%) respectively. Excellent method correlation was obtained with USEPA Method 537 in a comparative analysis of synthetic chlorinated drinking water samples aged 7 days and fortified with C6-C12 PFCAs and C4, C6, and C8 PFSAs, and three SRSs [C-13(4)] PFOA, [C-13(2)] PFUnA, and [C-13(4)] PFOS at 0.1 ng mL(-1). The average absolute difference between the EPA Method 537 and DI-LC/MS/MS measurements for the method analytes and SRSs was 8%.

Abstract  Twenty poly- and perfluorinated compounds (PFCs) were investigated in four red-throated divers (Gavia stellata) from the German Baltic Sea sampled in 2005. Concentrations of perfluoroalkyl sulfonates (PFSAs), perfluoroalkyl carboxylates (PFCAs), alkylated perfluoroalkyl sulfonamides, alkylated perfluoroalkyl sulfonamidoethanols and perfluorooctane sulfonamides were determined in blood, brain, fatty tissue, gall bladder, heart, kidney, liver, lung, muscle and spleen by high-performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS). For quantification standard addition was applied. Twelve compounds were detected with average total PFC concentrations ranging from 42 ng g(-1) in muscle to 220 ng g(-1) in liver samples. Perfluorooctane sulfonate (PFOS) was the major compound in each of the 40 tissue samples. Except for brain, perfluoroundecanoate was the dominant PFCA. In brain samples preferential enrichment of long-chain PFSAs and PFCAs was observed. The total PFC body burden was estimated to 100 +/- 39 mu g. Multivariate statistical analyses supported the identification of the preferred accumulation 'location' of individual PFCs in the birds' body.

Abstract  Per- and polyfluoroalkyl substances (PFASs) are a class of compounds with unique chemical properties that have been shown useful in a wide variety of applications because they provide materials with reduced surface tension and exceptional non-stick properties. PFASs are commonly found in impregnation materials, coatings of papers and textiles, fire-fighting foams, pesticides, and cleaning agents. The potential for human exposure to PFASs is high because of their widespread distribution. The aim of this study was to investigate levels of PFASs in men and women from Sweden and to assess the influence of gender and parity among women. Levels of 13 PFASs were determined in plasma samples collected during 2001-2004 from 1016 (507 women) 70year-old participants from the population-based Prospective Study of the Vasculature in Uppsala Seniors (PIVUS). The PFASs studied were nine perfluorinated carboxylic acids (PFCAs), four perfluorinated sulfonic acids (PFSAs) and perfluorooctane sulfonamide (PFOSA). In addition, structural isomers of perfluorooctane sulfonic acid (PFOS) were determined in a subset of 398 individuals. The detection rates were high and the majority of the studied compounds were detected in more than 75% of the participants. Levels of the selected analytes were found to be similar to other studies of non-occupationally exposed populations. Gender differences were observed in levels of PFHpA which was higher in men, while PFHxS was higher in women. Parity among women was shown to have a minor effect on PFAS concentrations and we found primi- and multiparous women to have slightly lower levels of PFUnDA when compared to nulliparous women.

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