Existence of nonpoint source of perfluorinated compounds and their loads in the Tsurumi River basin, Japan

Products containing perfluorinated compounds (PFCs) have been widely used during the last 50 years. As a result, worldwide environmental pollution by PFCs has been reported. The sources of PFC pollution in the aquatic environment have been poorly understood. In this study, river water and sewage treatment plant (STP) effluent were sampled along the stretch of the Tsurumi River and also at a fixed station in the river. The concentrations of perfluorooctanesulfonate (PFOS), perfluorohexanoic acid (PFHxA), perfluoroheptanoic acid (PFHpA), perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA) and perfluorodecanoic acid (PFDA) were measured. With an increase in river flow rate, it was observed that the PFC concentrations in the river water at fixed station were remained the same or increased for PFOS (179.9+/-34.4-179.6+/-69.5 ng l(-1)), PFHxA (5.5+/-0.8-9.0+/-2.6 ng l(-1)), PFHpA (3.1+/-0.3-4.4+/-1.0 ng l(-1)), and PFOA (15.9+/-0.3-13.4+/-2.5 ng l(-1)) whereas the concentration of PFNA (38.0+/-3.3-15.4+/-3.0 ng l(-1)) and PFDA (3.9+/-0.3-2.1+/-0.3 ng l(-1)) were decreased. On the other hand, the loads of every PFC increased with an increase in river flow rate. The loads of PFCs in rain runoff were estimated to be 2-11 times greater than those in STP effluents that are discharged into the river. These results indicate the existence of a PFC nonpoint source (NPS) and its impact to the total PFC load of river is significant.     

Perfluorinated compounds in the Pearl River and Yangtze River of China

A total of 14 perfluorinated compounds (PFCs) were quantified in river water samples collected from tributaries of the Pearl River (Guangzhou Province, south China) and the Yangtze River (central China). Among the PFCs analyzed, perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) were the two compounds with the highest concentrations. PFOS concentrations ranged from 0.90 to 99 ng/l and <0.01–14 ng/l in samples from the Pearl River and Yangtze River, respectively; whereas those for PFOA ranged from 0.85 to 13 ng/l and 2.0–260 ng/l. Lower concentrations were measured for perfluorobutane sulfonate (PFBS), perfluorohexane sulfonate (PFHxS), perfluorooctanesulfoamide (PFOSA), perfluorohexanoic acid (PFHxA), perfluoroheptanoic acid (PFHpA), perfluorononaoic acid (PFNA), perfluorodecanoic acid (PFDA), and perfluoroundecanoic acid (PFUnDA). Concentrations of several perfluorocarboxylic acids, including perfluorododecanoic acid (PFDoDA), perfluorotetradecanoic acid (PFTeDA), perfluorohexadecanoic acid (PFHxDA) and perfluorooctadecanoic acid (PFOcDA) were lower than the limits of quantification in all the samples analyzed. The highest concentrations of most PFCs were observed in water samples from the Yangtze River near Shanghai, the major industrial and financial centre in China. In addition, sampling locations in the lower reaches of the Yangtze River with a reduced flow rate might serve as a final sink for contaminants from the upstream river runoffs. Generally, PFOS was the dominant PFC found in samples from the Pearl River, while PFOA was the predominant PFC in water from the Yangtze River. Specifically, a considerable amount of PFBS (22.9–26.1% of total PFC analyzed) was measured in water collected near Nanjing, which indicates the presence of potential sources of PFBS in this part of China. Completely different PFC composition profiles were observed for samples from the Pearl River and the Yangtze River. This indicates the presence of dissimilar sources in these two regions.     

Perfluorooctanesulfonate and perfluorooctanoate in raw and treated tap water from Osaka, Japan

Perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) have been recognized as emerging environmental pollutants because of their ubiquitous occurrence in the environment, biota, and humans. PFOS and PFOA have been detected in water in Japan. Nevertheless, occurrence of PFOS and PFOA in potable water from municipal water treatment plants is not clearly known. We analyzed PFOS and PFOA in raw and tap water samples collected from 14 drinking water treatment plants in winter and summer seasons in Osaka to determine the concentrations of PFOS and PFOA in raw and potable tap water samples. PFOS and PFOA were detected in all raw water samples. Concentration ranges of PFOS and PFOA in raw water were 0.26-22 ng/l and 5.2-92 ng/l, respectively. Whereas the concentrations PFOS in raw water from Osaka were similar to those in other areas in Japan, the concentrations of PFOA were higher than in other areas. Concentration ranges of PFOS and PFOA in potable tap water were 0.16-22 ng/l and 2.3-84 ng/l, respectively. There were positive correlations between PFC concentrations in raw water and tap water samples. Therefore, the removal efficiency of PFCs by the present water treatment may be low. Based on the current action value reported by U.S. Environmental Protection Agency, PFOA concentrations found in tap water in Osaka is not expected to pose health risks.     

Preliminary evidence of a decline in perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) concentrations in American Red Cross blood donors

The purpose of this pilot study was to determine whether perfluorooctanesulfonate (PFOS,C(8)F(17)SO(3)(-)) and perfluorooctanoate (PFOA,C(7)F(15)CO(2)(-)) concentrations in American Red Cross blood donors from Minneapolis-St. Paul, Minnesota have declined after the 2000-2002 phase-out of perfluorooctanesulfonyl-fluoride (POSF, C(8)F(17)SO(2)F)-based materials by the primary global manufacturer, 3M Company. Forty donor plasma samples, categorized by age and sex, were collected in 2005, and PFOS and PFOA concentrations were compared to 100 (non-paired) donor serum samples collected in 2000 from the same general population that were analyzed at the time using ion-pair extraction methods with tetrahydroperfluorooctanesulfonate as an internal standard. Eleven of the 100 samples originally collected were reanalyzed with present study methods that involved (13)C- labeled PFOA spiked into the donor samples, original samples, control human plasma, and the calibration curve prior to extraction, and was used as a surrogate to monitor extraction efficiency. Quantification was performed by high performance liquid chromatography tandem mass spectrometry methods. Among the 100 serum samples analyzed for PFOS, the geometric mean was 33.1 ng ml(-1) (95% CI 29.8-36.7) in 2000 compared to 15.1 ng ml(-1) (95% CI 13.3-17.1) in 2005 (p<0.0001) for the 40 donor plasma samples. The geometric mean concentration for PFOA was 4.5 ng ml(-1) (95% CI 4.1-5.0) in 2000 compared to 2.2 ng ml(-1) (95% CI 1.9-2.6) in 2005 (p<0.0001). The decrease was consistent across donors' age and sex. To confirm these preliminary findings, additional sub-sets of year 2000 samples will be analyzed, and a much larger biomonitoring study of other locations is planned.     

Survey of perfluorinated alkyl acids in Finnish effluents, storm water, landfill leachate and sludge

The objective of the Control of Hazardous Substances in the Baltic Sea (COHIBA) project is to support the implementation of the HELCOM Baltic Sea Action Plan regarding hazardous substances by developing joint actions to achieve the goal of “a Baltic Sea with life undisturbed by hazardous substances”. One aim in the project was to identify the most important sources of 11 hazardous substances of special concern in the Baltic Sea. Among them are perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA). In this study, four perfluorinated alkyl acids (PFAAs) were studied: PFOA, PFOS, perfluorohexanoic acid (PFHxA) and perfluorodecanoic acid (PFDA). The occurrence of PFAAs in municipal and industrial wastewater treatment plant effluents (MWWTP1-3, IWWTP1), target industry effluent, storm water, landfill leachate and sludge was studied. Effluents were analysed six times and storm water, leachate and sludge were analysed twice, once in the warm season and once in the cold, during a 1-year sampling campaign. PFOS prevailed in two municipal effluents (MWWTP1 and 3) and industrial effluent (IWWTP1; 7.8–14, 8.0–640 and 320–1,300 ng/l, respectively). However, in one municipal effluent (MWWTP2) PFOA was, in a majority of sampling occasions, the predominant PFAA (9–15 ng/l) followed by PFOS (3.8–20 ng/l). The highest PFAA loads of the municipal effluents were found in the MWWTP3 receiving the biggest portion of industrial wastewater. In storm water the highest concentration was found for PFHxA (17 ng/l). The highest concentration of PFOS and PFOA were 9.9 and 5.1 ng/l, respectively. PFOS, PFOA and PFHxA were detected in every effluent, storm water and landfill leachate sample, whereas PFDA was detected in most of the samples (77 %). In the target industry, PFOS concentrations varied between 1,400 and 18,000 μg/l. In addition, on one sampling occasion PFOA and PFHxA were found (0.027 and 0.009 μg/l, respectively). For effluents, PFAA mass flows into the Baltic Sea were calculated. For municipal wastewater treatment plants average mass flows per day varied for PFOS between 1,073 and 38,880 mg/day, for PFOA 960 and 2,700 mg/day, for PFHxA 408 and 1,269 mg/day and for PFDA 84 and 270 mg/day. In IWWTP mass flows for PFOS, PFOA, PFHxA and PFDA were 495 mg/d, 28 mg/d, 23 mg/d and 0.6 mg/g, respectively.     

Concentrations of perfluorinated acids in livers of birds from Japan and Korea

Livers of birds collected from Japan and Korea (n = 83) were analyzed to determine the concentrations of perfluorooctanesulfonate (PFOS), perfluorooctanesulfonamide (FOSA), perfluorooctanoic acid (PFOA) and perfluorohexanesulfonate (PFHS). PFOS was found in the livers of 95% of the birds analyzed at concentrations greater than the limit of quantitation (LOQ) of 10 ng/g, wet weight. The greatest concentration of PFOS of 650 ng/g, wet weight, was found in the liver of a common cormorant from the Sagami River in Kanagawa Prefecture. Concentrations of PFOS in bird livers from Japan and Korea were within the ranges of values reported for those from the United States and certain European countries. PFOA and PFHS were found in 5-10% of the samples analyzed. The greatest concentrations of PFOA and PFHS in bird livers were 21 and 34 ng/g, wet weight, respectively. FOSA was found in all the samples (n = 10) of cormorants collected from the Sagami River in Japan. The greatest concentration of FOSA in cormorant liver was 215 ng/g, wet weight. There was no significant correlation between the concentrations of PFOS and FOSA in cormorants collected from the Sagami River. These results suggested that the distribution of FOSA is localized. No age- or gender-specific differences in fluorochemical concentrations could be discerned in birds.     

Historical and geographical aspects of the increasing perfluorooctanoate and perfluorooctane sulfonate contamination in human serum in Japan

Perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) have recently received attention due to their widespread contamination in the environment, as well as in wildlife and humans. We measured the PFOS and PFOA concentrations in historically recorded human serum samples at an age range between 20 and 59 years collected in Kyoto, 20 persons per each time point (n=100), and also the PFOS and PFOA concentrations in human serum samples at an age range between 20 and 59 years from 10 locations throughout Japan (n=200). The historical samples collected from 1983 to 1999 demonstrated that the PFOA concentrations in males and females from Kyoto have increased 4.4-fold and 4.3-fold at a rate of increase of 0.49 ng/ml/year and 0.42 ng/ml/year, respectively. In contrast, serum concentrations of PFOS reached a plateau in the late 1980s. There are also regional differences in both the PFOS and PFOA serum concentrations. The concentrations in serum [geometric mean (geometric standard deviation)] (ng/ml) in 2003-2004 ranged from 7.6(1.6) in the town of Matsuoka in Fukui prefecture to 27.8(1.6) in Kyoto city, and ranged from 2.3(1.5) in Matsuoka to 14.5(1.3) in Osaka city for PFOS and PFOA, respectively.     

Spatial trends of polyfluorinated compounds in guillemot (Uria aalge) eggs from North-Western Europe

Polyfluorinated alkyl compounds (PFCs) are a group of chemicals of growing concern that have been detected in biological and abiotic samples worldwide. This study reports the concentrations of a suite of PFCs: perfluorooctyl sulfonate (PFOS), perfluorooctyl sulfonamide (PFOSA) and perfluorinated carboxylic acids (PFCAs) in guillemot (Uria aalge) eggs, collected in North-Western Europe, from Iceland, the Faroe Islands, Sweden and two locations in Norway. The highest concentrations of PFOS were found in samples from Sweden (mean 400 ng g(-1) wet weight (w.w.)), which were almost five times higher than concentrations found in Norwegian samples (mean 85 ng g(-1)w.w. from both sample sites). The concentrations found in Icelandic and Faroe samples were lowest (mean 16 and 15 ng g(-1)w.w., respectively). Only Swedish samples differed significantly from the other locations. In general, PFCAs show a different spatial trend than PFOS. Perfluorooctanoic acid (PFOA) was not detected in any sample and perfluorononanoic acid (PFNA) was only detected in samples from Sweden. The most abundant PFCA was perfluoroundecanoic acid (PFUA) with highest concentrations in samples from Sweden (mean 82 ng g(-1)w.w.), samples from the Faroe Islands had the second highest concentration (mean 57 ng g(-1)w.w.) and samples from Iceland and Norway had concentrations ranging between 18 and 30 ng g(-1)w.w. The original hypothesis was based on the idea that PFC concentrations are the highest close to more densely populated and industrialized areas and lower levels in remote areas. However, the geographic pattern is more complicated than predicted and varies among different PFCs.     

Perfluorinated chemicals in selected residents of the American continent

Perfluorinated chemicals (PFCs) are used in multiple consumer products. Perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA), the most widely studied PFCs, may be potential developmental, reproductive, and systemic toxicants. Although PFCs seem to be ubiquitous contaminants found both in humans and animals, geographic differences may exist in human exposure patterns to PFCs. We measured 11 PFCs in 23 pooled serum samples collected in the United States from 1990 through 2002, and in serum samples collected in 2003 from 44 residents from Trujillo, Peru. PFOS and PFOA were detected in all the pooled samples; perfluorohexane sulfonic acid (PFHxS) was detected in 21. Median concentrations were 31.1 micrograms per liter (mug/l, PFOS), 11.6 microg/l (PFOA), and 2 microg/l (PFHxS). The 90th percentile concentrations of PFCs in the 44 Peruvian residents were 0.7 microg/l (PFOS), 0.1 microg/l (PFOA), and <0.3 microg/l (PFHxS). The frequencies of detection were 20% (PFOS), 25% (PFOA), and 9% (PFHxS). The frequent detection of selected PFCs in the pooled samples from the United States and the lack of clear concentration trends based on a year of collection suggest a sustained widespread exposure to these compounds among US residents, at least since the 1990s. By contrast, the much lower frequency of detection and concentration ranges of PFCs in Peru suggest a lower exposure of Peruvians to PFCs compared with North Americans. Genetic variability, diet, lifestyle, or a combination of all these may contribute to the different patterns of human exposure to PFCs in the United States and Peru.     

Perfluorochemicals in water reuse

Faced with freshwater shortages, water authorities are increasingly utilizing wastewater reclamation to augment supplies. However, concerns over emerging trace contaminants that persist through wastewater treatment need to be addressed to evaluate potential risks. In the present study, perfluorinated surfactant residues were characterized in recycled water from four California wastewater treatment plants that employ tertiary treatment and one that treats primary sewage in a wetland constructed for both treatment and wildlife habitat. Effluent concentrations were compared with surface and groundwater from a creek where recycled water was evaluated as a potential means to augment flow (Upper Silver and Coyote Creeks, San Jose, CA). In the recycled water, 90-470 ng/l perfluorochemicals were detected, predominantly perfluorooctanoate (PFOA; 10-190 ng/l) and perfluorooctanesulfonate (PFOS; 20-190 ng/l). No significant removal of perfluorochemicals was observed in the wetland (total concentration ranged 100-170ng/l across various treatment stages); in this case, 2-(N-ethylperfluorooctanesulfonamido) acetic acid (N-EtFOSAA), perfluorodecanesulfonate (PFDS), and PFOS were dominant. Though there is currently no wastewater discharge into the creeks, perfluorochemicals were found in the surface water and underlying groundwater at a total of 20-150 ng/l with PFOS and PFOA again making the largest contribution. With respect to ecotoxicological effects, perfluorochemical release via recycled water into sensitive ecosystems requires evaluation.     

PFOS and PFC releases and associated pollution from a PFC production plant in Minnesota (USA)

Perfluorooctane sulfonate (PFOS) and PFOS-related substances have been listed as persistent organic pollutants in the Stockholm Convention. From August 2012, Parties to the Convention needed to address the use, storage, and disposal of PFOS—including production sites and sites where PFOS wastes have been deposited—in their national implementation plans. The paper describes the pollution in Minnesota (USA) caused by the 3M Company at one of the largest per/polyfluorinated chemical (PFC) production facilities. From early 1950s until the end of 2002, when 3M terminated PFOS and perfluorooctanoic acid (PFOA) production, PFOS, PFOA, and other PFC production wastes were disposed around the plant and in local disposal sites. Discharges from the site and releases from deposits caused widespread contamination of ground and surface waters including local drinking water wells. Fish in the river downstream were contaminated with PFOS to levels that led to fish consumption advisories. Human exposures resulted from ingesting contaminated drinking water, requiring installation of water treatment facilities and alternate water supplies. The critical evaluation of the assessments done revealed a range of gaps in particular of human exposure where relevant exposure pathways including the entire exposure via food have not been taken into consideration. Currently, the exposure assessment of vulnerable groups such as children or Hmong minorities is inadequate and needs to be improved/validated by epidemiological studies. The assessment methodology described for this site may serve—with highlighted improvements—as a model for assessment of other PFOS/PFC production sites in the Stockholm Convention implementation.     

Extraction procedure optimization for perfluorooctane sulfonate and perfluorooctanoic acid in food packaging determination by LC-MS/MS

This research aimed to optimize the extraction method parameters for sample pretreatment and determine the levels of perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) contamination in food packaging made of paper. Techniques used were pressurized liquid extraction (PLE) followed by liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS). Influence parameters of PLE were carefully evaluated for extracted concentration of samples in low level (ng g^?1). The study found that the optimal conditions for PLE were 30 min static extraction time with a flush volume of 100% cell volume and one extraction cycle at 80°C and 1,000 psi. The extraction technique validated the absolute recovery from PFOS and PFOA fortified control samples at three different levels (5, 50, and 200 ng g^?1), with seven repeats at each fortification level. The average recoveries were 79% or higher, with relative standard deviation (RSD) less than 11%. Optimization of the PLE method was established based on recovery data, accuracy, precision, and repeatability of the method. Using optimal PLE technique, PFOS and PFOA were extracted from 34 food-packaging samples collected in Thailand. PFOS and PFOA were detected in all kinds of collected samples, with average concentrations of 4.89 and 2.87 ng g^?1, respectively. The concentrations of PFOS and PFOA were highest in fast-food container samples: 36.99 and 9.99 ng g^?1, respectively.     

Levels of perfluorochemicals in water samples from Catalonia,Spain: is drinking water a significant contribution to human exposure?

Background, aim, and scope  In recent years, due to a high persistence, biomagnification in food webs, presence in remote regions, and potential toxicity, perfluorochemicals (PFCs) have generated a considerable interest. The present study was aimed to determine the levels of perfluorooctane sulfonate (PFOS), perfluorooctanoic acid (PFOA), and other PFCs in drinking water (tap and bottled) and river water samples from Tarragona Province (Catalonia, Spain). Materials and methods  Municipal drinking (tap) water samples were collected from the four most populated towns in the Tarragona Province, whereas samples of bottled waters were purchased from supermarkets. River water samples were collected from the Ebro (two samples), Cortiella, and Francolí Rivers. After pretreatment, PFC analyses were performed by HPLC-MS. Quantification was done using the internal standard method, with recoveries between 68% and 118%. Results  In tap water, PFOS and PFOA levels ranged between 0.39 and 0.87 ng/L (0.78 and 1.74 pmol/L) and between 0.32 and 6.28 ng/L (0.77 and 15.2 pmol/L), respectively. PFHpA, PFHxS, and PFNA were also other detected PFCs. PFC levels were notably lower in bottled water, where PFOS could not be detected in any sample. Moreover, PFHpA, PFHxS, PFOA, PFNA, PFOS, PFOSA, and PFDA could be detected in the river water samples. PFOS and PFOA concentrations were between <0.24 and 5.88 ng/L (<0.48 and 11.8 pmol/L) and between <0.22 and 24.9 ng/L (<0.53 and 60.1 pmol/L), respectively. Discussion  Assuming a human water consumption of 2 L per day, the daily intake of PFOS and PFOA by the population of the area under evaluation was calculated (0.78–1.74 and 12.6 ng, respectively). It was found that drinking water might be a source of exposure to PFCs as important as the dietary intake of these pollutants. Conclusions  The contribution of drinking water (tap and bottled) to the human daily intake of various PFCs has been compared for the first time with data from dietary intake of these PFCs. It was noted that in certain cases, drinking water can be a source of exposure to PFCs as important as the dietary intake of these pollutants although the current concentrations were similar or lower than those reported in the literature for surface water samples from a number of regions and countries. Recommendations and perspectives  Further studies should be carried out in order to increase the knowledge of the role of drinking water in human exposure to PFCs.     

Distribution and sources of polyfluoroalkyl substances (PFAS) in the River Rhine watershed

The concentration profile of 40 polyfluoroalkyl substances (PFAS) in surface water along the River Rhine watershed from the Lake Constance to the North Sea was investigated. The aim of the study was to investigate the influence of point as well as diffuse sources, to estimate fluxes of PFAS into the North Sea and to identify replacement compounds of perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA). In addition, an interlaboratory comparison of the method performance was conducted. The PFAS pattern was dominated by perfluorobutane sulfonate (PFBS) and perfluorobutanoic acid (PFBA) with concentrations up to 181 ng/L and 335 ng/L, respectively, which originated from industrial point sources. Fluxes of ΣPFAS were estimated to be ∼6 tonnes/year which is much higher than previous estimations. Both, the River Rhine and the River Scheldt, seem to act as important sources of PFAS into the North Sea.     

EU-wide survey of polar organic persistent pollutants in European river waters

This study provides the first EU-wide reconnaissance of the occurrence of polar organic persistent pollutants in European river waters. More than 100 individual water samples from over 100 European rivers from 27 European Countries were analysed for 35 selected compounds, comprising pharmaceuticals, pesticides, PFOS, PFOA, benzotriazoles, hormones, and endocrine disrupters. Around 40 laboratories participated in this sampling exercise. The most frequently and at the highest concentration levels detected compounds were benzotriazole, caffeine, carbamazepine, tolyltriazole, and nonylphenoxy acetic acid (NPE₁C). Only about 10% of the river water samples analysed could be classified as “very clean” in terms of chemical pollution. The rivers responsible for the major aqueous emissions of PFOS and PFOA from the European Continent could be identified. For the target compounds chosen, we are proposing “indicative warning levels” in surface waters, which are (for most compounds) close to the 90th percentile of all water samples analysed.     

Perfluorinated Surfactants in Surface and Drinking Waters (9 pp)

Background, Aim and Scope In this paper recent results are provided of an investigation on the discovery of 12 perfluorinated surfactants (PS) in different surface and drinking waters (Skutlarek et al. 2006 a, Skutlarek et al. 2006 b). In the last years, many studies have reported ubiquitous distribution of this group of perfluorinated chemicals, especially perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) in the environment, particularly in wildlife animal and human samples (Giesy and Kannan 2001, Houde et al. 2006, Prevedouros et al. 2006). Perfluorinated surfactants (e.g. PFOS and PFOA) have shown different potentials for reproductory interference and carcinogenity in animal experiments as well as partly long half-lives in humans (Guruge et al. 2006, FSA UK 2006a, FSA UK 2006b, 3M 2005, OECD 2002, Yao and Zhong 2005). They possess compound-dependent extreme recalcitrance against microbiological and chemical degradation and, in addition, they show variable potentials for bioaccumulation in animals and humans (Houde et al. 2006). Materials and Methods: Surface and drinking water samples were collected from different sampling sites: - Surface waters: samples taken from the rivers Rhine, Ruhr, Moehne and some of their tributaries. Further samples were taken from the Rhine-Herne-Canal and the Wesel-Datteln-Canal. - Drinking waters: samples taken in public buildings of the Rhine-Ruhr area. After sample clean-up and concentration by solid-phase extraction, the perfluorinated surfactants were determined using HPLC-MS/MS. Results: All measured concentrations (sum of seven mainly detected components) in the Rhine river and its main tributaries (mouths) were determined below 100 ng/L. The Ruhr river (tributary of the Rhine) showed the highest concentration (94 ng/L), but with a completely different pattern of components (PFOA as major component), as compared with the other tributaries and the Rhine river. Further investigations along the Ruhr river showed remarkably high concentrations of PS in the upper reaches of the Ruhr river and the Moehne river (tributary of the Ruhr) (Ruhr: up to 446 ng/L, Moehne: up to 4385 ng/L). The maximum concentration of all drinking water samples taken in the Rhine-Ruhr area was determined at 598 ng/L with the major component PFOA (519 ng/L). Discussion: The surface water contaminations most likely stem from contaminated inorganic and organic waste materials (so-called 'Abfallgemisch'). This waste material was legally applied to several agricultural areas on the upper reaches of the Moehne. Perfluorinated surfactants could be detected in some suchlike soil samples. They contaminated the river and the reservoir belonging to it, likely by superficial run-off over several months or probably years. Downstream, dilution effects are held responsible for decreasing concentrations of PS in surface waters of the Moehne and the Ruhr river. In analogy to the surface water samples, PS (major component PFOA) can be determined in many drinking water samples of the Rhine-Ruhr area where the water supplies are mainly based on bank filtration and artificial recharge. Conclusions: The concentrations found in drinking waters decreased with the concentrations of the corresponding raw water samples along the flow direction of the Ruhr river (from east to west) and were not significantly different from surface water concentrations. This indicates that perfluorinated surfactants are at present not successfully removed by water treatment steps. Recommendations and Perspectives: Because of their different problematic properties (persistence, mobility, toxicity, bioaccumulation), the concentrations of specific perfluorinated surfactants and their precursors in drinking waters and food have to be minimised. Therefore, it is of utmost importance to take the initiative to establish suitable legal regulations (limitations/ban) concerning the production and use of these surfactants and their precursors. Furthermore, it is indispensable to protect water resources from these compounds. A discussion on appropriate limit values in drinking water and foodstuffs is urgently needed. Concerning the assumed soil contamination, the corresponding regulation (Bioabfall-Verordnung 1998 – Regulation on Organic Waste 1998) should be extended to allow the control of relevant organic pollutants.     

Blood serum concentrations of perfluorinated compounds in men from Greenlandic Inuit and European populations

Perfluorinated compounds (PFCs), such as perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA), are used in large quantities. They are persistent and found in measurable levels in human serum around the world. They have been associated with developmental, hepatic, and carcinogenic effects in animal studies. The aim of the present study was to describe levels of PFCs in serum among Inuits from Greenland and inhabitants from Warsaw, Poland and Kharkiv, Ukraine. Furthermore, the aim was to define social- and lifestyle related determinants of exposure for these compounds. Serum levels of seven PFCs were analyzed by liquid chromatography/tandem mass spectrometry (LC/MS/MS). The concentrations of PFOS and PFOA were the highest of all PFCs in all three populations with a total amount of almost 90% of the PFCs. The mean levels of PFOS and PFOA were in the Greenlandic Inuits 52 and 4.8 ng mL(-1), in Poland 19 and 5.2 ng mL(-1), and in Ukraine 8.1 and 1.9 ng mL(-1), respectively. Thus, levels of PFCs in the serum of Inuits on Greenland were among the highest described in a general population whereas the levels in Poland were similar to other industrialized countries. The exposure in Ukraine was rather low. In the Greenlandic Inuit population, intake of seafood, tea, age and area of living were significant determinants of PFOS concentrations and explained about 22% of the variation. For the other populations no strong determinants were found.     

Perfluoroalkyl substances (PFASs) in food and water from Faroe Islands

Diet and drinking water are suggested to be major exposure pathways for perfluoroalkyl substances (PFASs). In this study, food items and water from Faroe Islands sampled in 2011/2012 were analyzed for 11 perfluoroalkyl carboxylic acids (PFCAs) and 4 perfluoroalkane sulfonic acids (PFSAs). The food samples included milk, yoghurt, crème fraiche, potatoes, fish, and fish feed, and the water samples included surface water and purified drinking water. In total, nine PFCAs and four PFSAs were detected. Generally, the levels of PFAS were in the lower picogram per gram range. Perfluorobutanoic acid was a major contributor to the total PFASs concentration in water samples and had a mean concentration of 750 pg/L. Perfluoroundecanoic acid (PFUnDA) was predominating in milk and wild fish with mean concentrations of 170 pg/g. Perfluorooctane sulfonic acid (PFOS) was most frequently detected in food items followed by PFUnDA, perfluorononanoic acid, and perfluorooctanoic acid (PFOA). Levels of PFUnDA and PFOA exceeded those of PFOS in milk and fish samples. Prevalence of long-chain PFCAs in Faroese food items and water is confirming earlier observations of their increase in Arctic biota. Predominance of short-chain and long-chain homologues indicates exposure from PFOS and PFOA replacement compounds.     

Accumulation of perfluorinated compounds in captive Bengal tigers (Panthera tigris tigris) and African lions (Panthera leo Linnaeus) in China

The accumulation of perfluorinated compounds (PFCs) in the sera of captive wildlife species Bengal tigers (Panthera tigris tigris) and African lions (Panthera leo Linnaeus) from Harbin Wildlife Park, Heilongjiang Province, in China were analyzed by high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). Perfluorooctanesulfonate (PFOS) was the predominant contaminant with a mean serum concentration of 1.18 ng mL(-1) in tigers and 2.69 ng mL(-1) in lions. Perfluorononanoic acid (PFNA) was the second most prevalent contaminant in both species. The composition profiles of the tested PFCs differed between tigers and lions, and the percentages of perfluorooctanoic acid (PFOA) were greater in lions than in tigers, indicating different exposures and/or metabolic capabilities between the two species. Assessments of the risk of PFC contamination to the two species were obtained by comparing measured concentrations to points of departure or toxicity reference values (TRVs). Results suggest no risk of PFOS exposure or toxicity for the two species.     

Perfluorooctanoic acid and perfluorooctane sulfonate in the sediment of the Roter Main river, Bayreuth, Germany

Perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) are widely distributed in aquatic ecosystems. Their sources are known but few studies about their accumulation potential in river sediments exist. The aim of this study is to assess the concentrations of PFOA and PFOS in sediments in relation to their levels in river water receiving effluent from a waste water treatment plant (WWTP). PFOS accumulates by a factor of about 40 relative to river water, PFOA only up to threefold. In contrast to previous suggestions, in this case the enrichment on sediment is not correlated to the total organic carbon contents.