Background levels of Persistent Organic Pollutants in humans from Taiwan: Perfluorooctane sulfonate and perfluorooctanoic acid

Perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) have recently received attention due to their widespread contamination of the environment. PFOS and PFOA are stable in the environment and resistant to metabolism, hydrolysis, photolysis and biodegradation. PFOS and PFOA have been found in human blood and tissue samples from both occupationally exposed workers and the general worldwide population. This study aimed to determine the background levels of PFOS and PFOA in the Taiwanese population, investigate related factors, and compare exposure in Taiwan to that in other countries. The concentration of PFOS in the 59 serum samples collected from the general population in Taiwan ranged from 3.45 to 25.65 ng mL⁻¹ (median: 8.52), and the concentration of PFOA ranged from 1.55 to 7.69 ng mL⁻¹ (median: 3.22). There was a significant positive correlation (r = 0.51; p < 0.0001) between PFOS and PFOA concentrations. Males had higher concentrations of PFOA and PFOS than females. PFOS levels in serum increased with age. This study is the first investigation to reveal the PFOS and PFOA levels of serum samples in the general population of Taiwan. The levels of PFOS and PFOA in Taiwanese serum samples were comparable with those from other countries (PFOS: 5.0–35 ng mL⁻¹, PFOA: 1.5–10 ng mL⁻¹).     

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.     

Occurrence and partition of perfluorinated compounds in water and sediment from Liao River and Taihu Lake, China

The concentrations of four perfluorinated sulfonate acids (PFSAs) and 10 perfluorinated carboxylate acids (PFCAs) were measured in water and sediment samples from Liao River and Taihu Lake, China. In the water samples from Taihu Lake, PFOA and PFOS were the most detected perfluorinated compounds (PFCs); in Liao River, PFHxS was the predominant PFC followed by PFOA, while PFOS was only detected in two of the samples. This suggests that different PFC products are used in the two regions. PFOS and PFOA in both watersheds are at similar level as in the rivers of Japan, but significantly lower than in Great Lakes. The contributions of PFOS and long chain PFCAs in sediments were much higher than in water samples of both watersheds, indicating preferential partition of these PFCs in sediment. The concentrations of PFOS and PFOA were three orders of magnitude of lower than that of polycyclic aromatic hydrocarbons in the same sediments. The average sediment-water partition coefficients (log K_oc) of PFHxS, PFOS and PFOA were determined to be 2.16, 2.88 and 2.28 respectively.     

Sorption of perfluoroalkyl substances in sewage sludge

The sorption behaviour of three perfluoroalkyl substances (PFASs) (perfluorooctanesulfonic acid (PFOS), perfluorooctanoic acid (PFOA) and perfluorobutanesulfonic acid (PFBS)) was studied in sewage sludge samples. Sorption isotherms were obtained by varying initial concentrations of PFOS, PFOA and PFBS. The maximum values of the sorption solid–liquid distribution coefficients (K_d,max) varied by almost two orders of magnitude among the target PFASs: 140–281 mL g^?1 for PFOS, 30–54 mL g^?1 for PFOA and 9–18 mL g^?1 for PFBS. Freundlich and linear fittings were appropriate for describing the sorption behaviour of PFASs in the sludge samples, and the derived K_F and K_d,linear parameters correlated well. The hydrophobicity of the PFASs was the key parameter that influenced their sorption in sewage sludge. Sorption parameters and log(K_OW) were correlated, and for PFOS (the most hydrophobic compound), pH and Ca?+?Mg status of the sludge controlled the variation in the sorption parameter values. Sorption reversibility was also tested from desorption isotherms, which were also linear. Desorption parameters were systematically higher than the corresponding sorption parameters (up to sixfold higher), thus indicating a significant degree of irreversible sorption, which decreased in the sequence PFOS?>?PFOA?>?PFBS.     

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.     

Spatial distribution of perfluoroalkyl acids in the Pearl River of Southern China

An intensive campaign was conducted in September 2012 to collect surface water samples along the tributaries of the Pearl River in southern China. Thirteen perfluoroalkyl acids (PFAAs), including perfluorocarboxylates (PFCAs, C4–C11) and perfluorosulfonates (PFSAs, C4, C6–C8, and C10), were determined using high-performance liquid chromatography/negative electrospray ionization–tandem mass spectrometry (HPLC/(-)ESI–MS/MS). The concentrations of total PFAAs (ΣPFAAs) ranged from 3.0 to 52 ng L⁻¹, with an average of 19 ± 12 ng L⁻¹. The highest concentrations of ΣPFAAs were detected in the surface water of the Dong Jiang tributary (17–52 ng L⁻¹), followed by the main stream (13–26 ng L⁻¹) and the Sha Wan stream (3.0–4.5 ng L⁻¹). Perfluorooctanoate (PFOA), perfluorobutane sulfonate (PFBS), and perfluorooctane sulfonate (PFOS) were the three most abundant PFAAs and on average accounted for 20%, 24%, and 19% of ΣPFAAs, respectively. PFBS was the most abundant PFAA in the Dong Jiang tributary, and PFOA was the highest PFAA in the samples from the main stream of the Pearl River. A correlation was found between PFBS and PFOA, which suggests that both of these PFAAs originate from common source(s) in the region. Nevertheless, the slope of PFBS/PFOA was different in the different tributaries sampled, which indicates a spatial difference in the source profiles of the PFAAs.     

Concentrations of perfluoroalkyl compounds in maternal and umbilical cord sera and birth outcomes in Korea

This study analyzed the concentrations of perfluorooctane sulfonate (PFOS), perfluorooctanoic acid (PFOA) and perfluorohexane sulfonate (PFHxS) in maternal and umbilical cord sera at delivery from the general population in Korea. Seventy samples were analyzed with ion-pairing and LC/MS/MS. PFOS, PFOA and PFHxS were detected in both maternal and umbilical cord sera. There was a high correlation of PFC concentrations between maternal and cord serum samples, implying transplacental transport. Ranking of transplacental transfer efficiency was PFOA > PFHxS > PFOS. Student’s t-tests revealed that concentrations of maternal PFOA were related with decreases in birth weight, birth length and ponderal index, suggesting a possible impact on fetal growth. With multiple logistic regression models, maternal PFOS concentration showed a significant inverse association with ponderal index (OR = 0.22; 95% CI, 0.05–0.90). Umbilical cord PFHxS concentration showed a significant inverse association with birth weight (OR = 0.26; 95% CI, 0.08–0.85) or a marginally significant inverse association with birth length (OR = 0.33; 95% CI, 0.09–1.17). This is the first report demonstrating an inverse association of birth outcomes with PFHxS exposure. Concentrations of maternal PFOA were decreased with parity, implying that delivery is one of the major routes for PFOA elimination in women. This study demonstrated prenatal exposure of PFCs through placental transfer which could result in possible developmental effects in the population sampled. Our results may provide data basis to conduct a larger scale investigation into developmental effects of PFCs in the future and contribute to understanding levels of PFC contaminations from a variety of populations in the globe.     

The impact of semiconductor, electronics and optoelectronic industries on downstream perfluorinated chemical contamination in Taiwanese rivers

This study provides the first evidence on the influence of the semiconductor and electronics industries on perfluorinated chemicals (PFCs) contamination in receiving rivers. We have quantified ten PFCs, including perfluoroalkyl sulfonates (PFASs: PFBS, PFHxS, PFOS) and perfluoroalkyl carboxylates (PFCAs: PFHxA, PFHpA, PFOA, PFNA, PFDA, PFUnA, PFDoA) in semiconductor, electronic, and optoelectronic industrial wastewaters and their receiving water bodies (Taiwan's Keya, Touchien, and Xiaoli rivers). PFOS was found to be the major constituent in semiconductor wastewaters (up to 0.13 mg/L). However, different PFC distributions were found in electronics plant wastewaters; PFOA was the most significant PFC, contributing on average 72% to the effluent water samples, followed by PFOS (16%) and PFDA (9%). The distribution of PFCs in the receiving rivers was greatly impacted by industrial sources. PFOS, PFOA and PFDA were predominant and prevalent in all the river samples, with PFOS detected at the highest concentrations (up to 5.4 μg/L).     

Fate and transport of perfluoro- and polyfluoroalkyl substances including perfluorooctane sulfonamides in a managed urban water body

Transport and fate of perfluoro- and polyfluoroalkyl substances (PFASs) in an urban water body that receives mainly urban runoff was investigated. Water, suspended solids, and sediment samples were collected during the monsoon (wet) and inter-monsoon (dry) season at different sites and depths. Samples were analyzed for C7 to C12 perfluoroalkyl carboxylate homologues (PFCAs) (PFHpA, PFOA, PFNA, PFDA, PFUnA, PFDoA), perfluorohexane, perfluorooctane, and 6:2-fluorotelomer sulfonate (PFHxS, PFOS, and 6:2FtS, respectively), perfluorooctane sulfonamide (FOSA), N-ethyl FOSA (sulfluramid), N-ethyl sulfonamidoethanol (N-EtFOSE), and N-methyl and N-ethyl sulfonamidoacetic acid (N-EtFOSAA and N-MeFOSAA, respectively). Concentrations in wet samples were only slightly higher. The sum total PFAS (ΣPFAS) concentrations dissolved in the aqueous phase and sorbed to suspended solids (SS) ranged from 107 to 253 ng/L and 11 to 158 ng/L, respectively. PFOA, PFOS, PFNA, PFHxS, and PFDA contributed most (approximately 90 %) to the dissolved ΣPFASs. N-EtFOSA dominated the particulate PFAS burden in wet samples. K _D values of PFOA and PFOS calculated from paired SS and water concentrations varied widely (1.4 to 13.7 and 1.9 to 98.9 for PFOA and PFOS, respectively). Field derived K _D was significantly higher than laboratory K _D suggesting hydrophobic PFASs sorbed to SS resist desorption. The ΣPFAS concentrations in the top sedimentary layer ranged from 8 to 42 μg/kg and indicated preferential accumulation of the strongly sorbing long-chain PFASs. The occurrence of the metabolites N-MeFOSAA, N-EtFOSAA and FOSA in the water column and sediments may have resulted from biological or photochemical transformations of perfluorooctane sulfonamide precursors while the absence of FOSA, N-EtFOSA and 6:2FtS in sediments was consistent with biotransformation.     

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.     

Quantitative analysis of perfluorinated chemicals in media for in vitro fertilization and related samples

The actual standard in vitro fertilization (IVF) protocol recommends an overnight gamete co-incubation. All of the culture media used for human IVF are supplemented with serum or albumin. In the present study, we determined the concentrations of perfluorinated chemicals (PFCs) in IVF media (IVFM) and related samples by liquid chromatography with tandem mass spectrometry (LC/MS/MS). The results indicated that the concentrations of PFOS and PFOA in the protein source were higher than those in the IVFM samples. Compared with human plasma concentrations of PFCs, PFCs in all of the IVFM samples, such as PFBS, PFHxS and PFOA, were either not detected or present at only trace levels, even when protein source was added. LC/MS/MS could be used to determine PFCs in IVFM samples in future studies of the effects of PFC exposure on intrauterine insemination.     

Determinants of maternal and fetal exposure and temporal trends of perfluorinated compounds

In recent years, some perfluorinated compounds (PFCs) have been identified as potentially hazardous substances which are harmful to the environment and human health. According to limited data, PFC levels in humans could be influenced by several determinants. However, the findings are inconsistent. In the present study, perfluorooctane sulfonate (PFOS), perfluorooctanoic acid (PFOA), and perfluorononanoic acid (PFNA) were measured in paired maternal and cord serum samples (N?=?237) collected between 1978 and 2001 in Southern Sweden to study the relationship between these and to investigate several potential determinants of maternal and fetal exposure to PFCs. Time trends of PFCs in Swedish women were also evaluated. The study is a part of the Fetal Environment and Neurodevelopment Disorders in Epidemiological Research project. PFOS, PFOA, and PFNA levels (median) were higher in maternal serum (15, 2.1, and 0.24 ng/ml, respectively) than in cord serum (6.5, 1.7, and 0.20 ng/ml, respectively). PFC levels were among the highest in women originating from the Nordic countries and the lowest in women from the Middle East, North Africa, and sub-Saharan Africa. Multiparous women had lower serum PFOA levels (1.7 ng/ml) than primiparous women (2.4 ng/ml). Maternal age, body mass index, cotinine levels, and whether women carried male or female fetuses did not affect serum PFC concentrations. Umbilical cord serum PFC concentrations showed roughly similar patterns as the maternal except for the gestational age where PFC levels increased with advancing gestational age. PFOS levels increased during the study period in native Swedish women. In summary, PFOS levels tend to increase while PFOA and PFNA levels were unchanged between 1978 and 2001 in our study population. Our results demonstrate that maternal country of origin, parity, and gestational age might be associated with PFC exposure.     

Radiosynthesis of perfluorooctanesulfonate (PFOS) and perfluorobutanesulfonate (PFBS), including solubility, partition and adhesion studies

Here, we describe for the first time the synthesis of [³⁵S] PFOS and [³⁵S] PFBS with sulfur-35 enriched sulfur dioxide as the radiolabelled reagent, resulting in 2.5 and 2.3 mCi of product, respectively. Basic information concerning the physicochemical properties of perfluorooctanesulfonate (PFOS), perfluorobutanesulfonate (PFBS) and perfluorooctanoic acid (PFOA) are still limited. Hence, we utilized these radiolabelled perfluoroalkanesulfonates (PFSAs), as well as carbon-14 labelled perfluorooctanoic acid ([¹⁴C] PFOA) to determine some basic characteristics of physiological and experimental significance.The solubility of PFOS in buffered aqueous solutions at pH 7.4 was found to be severely reduced in the presence of potassium and sodium ions, which, however, did not reduce the solubility of PFOA or PFBS. PFOS was found to adhere to a small extent to polypropylene and polystyrene, whereas no such adhesion of PFOA or PFBS was detected. The extents of adhesion of PFOS and PFOA to glass were found to be 20% and 10%, respectively. For the first time, the partition coefficients for PFOS, PFBS and PFOA between n-octanol and water were determined experimentally, to be −0.7, −0.3, and 1.4, respectively, reflecting the difference in the amphiphilic natures of these molecules.     

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.     

Perfluorooctanesulfonate and related fluorochemicals in biological samples from the north coast of Colombia

Perfluorinated compounds are widespread pollutants of toxicological importance that have been detected in environmental matrices. However, little is known on their distribution in South America. In this study, distribution of perfluorooctanesulfonate (PFOS), perfluorooctanoic acid (PFOA), perfluorohexanesulfonate (PFHxS), and perfluorooctanesulfonamide (PFOSA) was determined in the bile of mullet, Mugil incilis, and in tissues of pelicans (Pelecanus occidentalis) collected from North Colombia. Analysis was performed by HPLC mass spectrometry after ion-pair extraction. PFOS was found in all bile samples and PFOA and PFHxS were detected at lower frequency. Average concentrations of PFOS, PFOA, and PFHxS in bile of fish from Cartagena Bay, an industrialized site, and Totumo marsh, a reference site, were 3673, 370, 489 and 713, 47.4, 1.27 ng/mL, respectively. PFOS concentrations in pelican organs decreased in the order of spleen>liver>lung>kidney>brain>heart>muscle. These results suggest, for the first time, that perfluorinated compounds are also found in wildlife from Latin American countries.     

Perfluorinated compounds affect the function of sex hormone receptors

Perfluorinated compounds (PFCs) are a large group of chemicals used in different industrial and commercial applications. Studies have suggested the potential of some PFCs to disrupt endocrine homeostasis, increasing the risk of adverse health effects. This study aimed to elucidate mechanisms behind PFC interference with steroid hormone receptor functions. Seven PFCs [perfluorohexane sulfonate (PFHxS), perfluorooctane sulfonate (PFOS), perfluorooctanoate (PFOA), perfluorononanoate (PFNA), perfluorodecanoate (PFDA), perfluoroundecanoate (PFUnA), and perfluorododecanoate (PFDoA)] were analyzed in vitro for their potential to affect estrogen receptor (ER) and androgen receptor (AR) transactivity as well as aromatase enzyme activity. The PFCs were assessed as single compounds and in an equimolar mixture. PFHxS, PFOS and PFOA significantly induced the ER transactivity, whereas PFHxS, PFOS, PFOA, PFNA and PFDA significantly antagonized the AR activity in a concentration-dependent manner. Moreover, PFDA weakly decreased the aromatase activity at a high test concentration. A mixture effect more than additive was observed on AR function. We conclude that five of the seven PFCs possess the potential in vitro to interfere with the function of the ER and/or the AR. The observed mixture effect emphasizes the importance of considering the combined action of PFCs in future studies to assess related health risks.     

Structure-activity relationship assessment of four perfluorinated chemicals using a prolonged zebrafish early life stage test

Perfluorinated compounds (PFCs) are a group of anthropogenic chemicals containing diverse functional groups and chain lengths. They are known to be persistent and bioaccumulative explaining their worldwide environmental presence. The toxicological information on these chemicals is still incomplete and insufficient to assess their environmental impact and structure-activity relationship. In the present study, the developmental effects of PFOS (perfluorooctane sulfonate, C8), PFOA (perfluorooctanoic acid, C8), PFBS (perfluorobutane sulfonate, C4) and PFBA (perfluorobutanoic acid, C4) were evaluated in zebrafish embryos (Danio rerio). The different chain lengths and functional groups of the selected chemicals made it possible to determine the structure-activity relationship of these compounds. PFCs with longer chain lengths (C8) tend to be more toxic than PFCs with shorter chain lengths (C4). Comparison based on the functional groups of compounds with the same chain length indicates that PFCs with a sulfonate group have a larger toxic potential than the ones with a carboxyl group. Furthermore, exposure to the different PFCs resulted in some general effects, such as deformations of the tail and an uninflated swim bladder, as well as in more specific effects which might be related to the structure of the tested chemicals. Oedemas and effects on length could only be detected in 8-carbon PFCs while malformations of the head were a more specific action of the sulfonated PFCs. Effects on hatching rate and success were found in PFOA exposed embryos and heart rates were affected after exposure to PFOS, PFOA and PFBS.     

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.     

Estimation of contribution from non-point sources to perfluorinated surfactants in a river by using boron as a wastewater tracer

The contribution of non-point sources to perfluorinated surfactants (PFSs) in a river was evaluated by estimating their fluxes and by using boron (B) as a tracer. The utility of PFSs/B as an indicator for evaluating the impact of non-point sources was demonstrated. River water samples were collected from the Iruma River, upstream of the intake of drinking water treatment plants in Tokyo, during dry weather and wet weather, and 13 PFSs, dissolved organic carbon (DOC), total nitrogen (TN), and B were analyzed. Perfluorohexane sulfonate (PFHxS), perfluorooctane sulfonate (PFOS), perfluoroheptanoate (PFHpA), perfluorooctanoate (PFOA), perfluorononanoate (PFNA), perfluorodecanoate (PFDA), perfluoroundecanoate (PFUA), and perfluorododecanoate (PFDoDA) were detected on all sampling dates. The concentrations and fluxes of perfluorocarboxylates (PFCAs, e.g. PFOA and PFNA) were higher during wet weather, but those of perfluoroalkyl sulfonates (PFASs, e.g. PFHxS and PFOS) were not. The wet/dry ratios of PFSs/B (ratios of PFSs/B during wet weather to those during dry weather) agreed well with those of PFS fluxes (ratios of PFS fluxes during wet weather to those during dry weather), indicating that PFSs/B is useful for evaluating the contribution from non-point sources to PFSs in rivers. The wet/dry ratios of PFOA and PFNA were higher than those of other PFSs, DOC, and TN, showing that non-point sources contributed greatly to PFOA and PFNA in the water. This is the first study to use B as a wastewater tracer to estimate the contribution of non-point sources to PFSs in a river.     

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.