Distribution and desorption of perfluorinated compounds in fractionated sediments

This study provides particle-scale understanding of perfluorinated compounds (PFCs) distribution in sediments collected from two locations in Tianjin, China. The sediments were fractionated according to particle size and density. Even though lower density carbonaceous fractions contributed only 17.8-22.3% of the total sediment mass, they displayed stronger affinity to PFCs with much higher PFC concentrations than in the heavy fractions. Hydrophobic interaction predominated the partition of longer chain PFCs while electrostatic interaction could affect the sorption of short chain PFCs in sediment fractions. The individual PFC concentrations increased with increasing perfluorocarbon chain length, and the concentrations of perfluoroalkanesulfonates (PFSAs) in the same sediment fraction were higher than perfluorocarboxylates (PFCAs) with the same chain length. Log K(oc) was in the range of 1.70-3.80 for C5-C12 PFCAs and 1.75-2.97 for C4-C8 PFSAs. Desorption experiments indicated desorption became difficult as the chain length increased, and PFSAs were harder to be desorbed than the corresponding PFCAs.     

Behavior of perfluorinated compounds in soils during leaching experiments

Perfluorinated compounds (PFCs) can be detected worldwide in both, soil and water. In order to study the leaching behavior of this heterogeneous group of compounds in soil, flow-through column experiments have been conducted. Ten perfluoro carboxylates and four perfluoro sulfonates ranging from C4 to C14 in chain length, and contaminated sewage sludge, have been used to spike a standard soil. The aqueous column effluent was analyzed using liquid chromatography tandem mass spectrometry (LC-MS/MS) with direct injection. The observed percolation velocity seems to be strongly correlated with the length of the perfluorinated chain. Other factors that additionally contribute to the leaching behavior are the functional group of the PFC, the organic carbon content of the soil and the presence of other adsorbates. A mass balance calculation showed that perfluorobutanoic acid can adsorb strongly to the soil, when no PFC with longer carbon chain are present. Only about 60% of the added perfluorobutanoic acid could be detected in the percolate water. The missing amount started to elute again when longer chain PFC or stearate were added to the soil. Thus it would appear that larger and more lipophilic molecules can displace shorter PFC from their binding sites in the soil.The results of a monitoring study using 32 surface water samples and 150 groundwater samples confirm that the PFC with the highest concentrations in groundwater are the short chain PFC with less than 7 (fluorinated) carbon atoms. The dominating PFC in surface waters are perfluorooctanoic acid and perfluorooctane sulfonic acid.     

Wet deposition of poly- and perfluorinated compounds in Northern Germany

Twenty precipitation samples were taken concurrently with air samples at a northern German monitoring site over a period of 7 months in 2007 and 2008. Thirty four poly- and perfluorinated compounds (PFC) were determined in rain water samples by solid phase extraction and HPLC-MS/MS analysis. Seventeen compounds were detected in rain water with ΣPFC concentrations ranging from 1.6 ng L⁻¹ to 48.6 ng L⁻¹. Perfluorooctanoate (PFOA) and perfluorobutanate (PFBA) were the compounds that were usually observed in highest concentrations. Calculated ΣPFC deposition rates were between 2 and 91 ng m⁻² d⁻¹. These findings indicate that particle phase PFC are deposited from the atmosphere by precipitation. A relationship between PFC wet deposition and air concentration may be established via precipitation amounts. Trajectory analysis revealed that PFC concentration and deposition estimates in precipitation can only be explained if a detailed air mass history is considered.     

城市污水处理厂中全氟化合物的存在及去除效果研究

建立了一种基于超高效液相色谱/串联质谱的方法,实现了对北京3个污水处理厂污水中12种全氟化合物(PFCs)的快速、灵敏地定量分析.结果表明,城市污水处理厂进水和出水中短链的全氟丁酸(PFBA)、全氟戊酸(PFPA)和全氟丁磺酸(PFBS)是主要污染物,其中出水中PFBs的质量浓度高达253 ng/L.污水生物处理后,出...     

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.     

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.     

First assessment of population exposure to perfluorinated compounds in Flanders, Belgium

With the objective to evaluate exposure of the population in Flanders (Belgium) to perfluorinated compounds (PFCs), we measured perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) in settled dust in homes and offices, in a selection of food items from local origin, in drinking-water and in human serum. We complemented the data with results from a literature survey. Based on this dataset we calculated intake by children and adults from food, drinking-water, settled dust and soil, and air. Dietary exposure dominated overall intake. For adults, average dietary intake equalled 24.2 (P95 40.9) ng PFOS kg⁻¹ d⁻¹ and 6.1 (P95 9.6) ng PFOA kg⁻¹ d⁻¹, whereas for children the dietary intake was about 3 times higher. Predicted intake is high when compared to assessments in other countries, and to serum levels from Flanders, but comparable to the intakes published by The European Food Safety Authority (EFSA) in 2008. Intake of PFOS and PFOA remained below the Tolerable Daily Intake.     

Acute toxicity of 353-nonylphenol and its metabolites for zebrafish embryos

Background, aim and scope  Nonylphenol (NP) can be detected in the aquatic environment all over the world. It is applied as a technical mixture of isomers of which 353-NP is the most relevant both in terms of abundance (about 20% of total mass) and endocrine potential. 353-NP is metabolised in sewage sludge. The aims of the present study were to determine and to compare the acute toxicity of t-NP, 353-NP and its metabolites as well as to discuss if the toxicity of 353-NP changes during degradation. Materials and methods  353-NP and two of its metabolites were synthesised. The zebrafish embryo test was performed according to standard protocols. Several lethal and non-lethal endpoints during embryonal development were reported. NOEL, LOEL and EC₅₀ were calculated. Results  All tested compounds caused lethal as well as non-lethal malformations during embryo development. 353-NP showed a higher toxicity (EC₅₀ for lethal endpoints 6.7 mg/L) compared to its metabolites 4-(3.5-dimethyl-3-heptyl)-2-nitrophenol (EC₅₀ 13.3 mg/L) and 4-(3,5-dimethyl-3-heptyl)-2-bromophenol (EC₅₀ 27.1 mg/L). Discussion  In surface water, concentrations of NP are far below the NOEC identified by the zebrafish embryo test. However, in soils and sewage sludge, concentrations may reach or even exceed these concentrations. Therefore, sludge-treated sites close to surface waters should be analysed for NP and its metabolites in order to detect an unduly high contamination due to runoff events. Conclusions  The results of the present study point out that the toxicity of 353-NP probably declines during metabolisation in water, sediment and soil, but does not vanish since the major metabolites exhibit a clear toxic potential for zebrafish embryos. Recommendations and perspectives  Metabolites of environmental pollutants should be included in the ecotoxicological test strategy for a proper risk assessment. An erratum to this article can be found at     

Distribution of perfluorinated compounds in surface water from Hanjiang River in Wuhan,China

This study provided the first spatial distribution of perfluorinated compounds (PFCs) in Hanjiang River in Wuhan, China (HR). Surface water samples, collected from 23 sites in HR were analyzed for eight PFCs. The total concentrations of PFCs ranged from 8.90 to 568 ng L⁻¹, while perfluoropentanoic acid (PFOA, <LOQ − 256 ng L⁻¹) and perfluorooctane sulfonate (PFOS, <LOQ − 88.9 ng L⁻¹) dominated. All data were found to be normally distributed in the river. Similar spatial distribution tendencies were found among perfluorocarboxylates (PFCAs) and significant correlations were observed among PFCAs, while no significant correlations were found between PFOS and PFCAs. The distributions of PFCs were highly influenced by the industrial discharge and urban activities. The flux of PFCs from HR to the Yangtze River was estimated in the range of 16.9–127 kg yr⁻¹. More than a half of the samples studied could not meet the drinking water standards and avian wildlife values, suggesting further studies of characterizing PFCs and their potential risk to human were needed.     

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.     

Effects of phytosterols on zebrafish reproduction in multigeneration test

Zebrafish from mixed sex populations were exposed continuously across three generations to two phytosterol preparations both containing -sitosterol. The phytosterols were isolated from wood and soy beans. Blood vitellogenin levels and sex ratio changes were used as intermediate indicators of the reproduction failures. Both sterol preparations caused vitellogenin induction in the exposed fish. The wood sterol changed the sex ratio of the exposed fish. In generation F1, the predominant sex was male, and in generation F2 it was female. The soy sterol in the used test concentration was lethal to the exposed fish in generation F1. This multigeneration test evidenced that phytosterols containing -sitosterol disrupt the reproduction system of zebrafish by changing the sex ratios and by inducing the vitellogenin production in the exposed fish.     

Effects of triclosan on zebrafish early-life stages and adults

Background, aim and scope  

The biocide triclosan (TCS) is commonly used in personal care, acrylic, plastic, and textiles products. TCS has been detected in surface water in several countries, and its ecological impact is largely unknown. In this work, the toxicity of TCS in zebrafish (Danio rerio), embryos and adults was studied. Several lethal and sub-lethal endpoints were analysed in organisms exposed to TCS such as mortality, embryo development and behaviour, hatching, micronuclei and biochemical markers (cholinesterase (ChE), glutathione S-transferase (GST) and lactate dehydrogenase (LDH)).     

生物滞留池对地表径流中常规污染物及全氟化合物的去除效果

生物滞留系统是实现城市地表径流水量调控和水质净化的新型绿色生态系统,但其对全氟化合物的去除效能尚不清楚。本文构建了将传统填料与2~4 mm沸石(体积占比10%)或2~4 mm的改良煤质颗粒活性炭(体积占比10%)混合的2种柱形生物滞留系统,通过动态实验探究了此系统对地表径流中常规污染物和全氟化合物去除效果,分析了系统近1 a的运行效果。结果表明,生物滞留系统的水量削减率随运行时间的增长呈现下降的趋势,平均削减率为(29.8±8.2)%。改良煤质颗粒活性炭生物滞留池对COD、TN、TP、TOC、$ {\mathrm{N}\mathrm{H}}_{4}^{+} $-N的平均去除率分别为67.49%、84.78%、76.43%、80.28%、65.43%,优于以沸石为填料的滞留池。6种目标全氟化合物PFPeA、PFHxA、PFHpA、PFOA、PFOS、PFNA的去除率保持在80%以上。滞留池内污染物空间分布特征表明,PFBA主要集中于种植层,而PFPeA、PFHxA、PFHpA、PFOA、PFOS、PFNA则更集中于填料层。     

Pilot scale application of a method for the analysis of perfluorinated compounds in surface soils

A growing number of studies now indicate that perfluorinated compounds (PFCs) are globally distributed in the environment. Their widespread distribution and presence in remote locations has led to questions about the importance of atmospheric and oceanic transport. Describing their distribution in surface soils is also an essential but neglected element in developing a comprehensive understanding of their occurrence in the environment. Soils are the critical link between global atmospheric and hydrologic processes where both local and distant contaminants can accumulate and be released into aquatic and terrestrial communities. Because PFC concentrations in soils will influence ground and surface water, wildlife, and crops, methods to accurately measure PFCs in soil are clearly needed. To help answer this need, we developed a method for the analysis of nine perfluorinated carboxylic acids and four perfluorinated sulfonic acids in soil. Samples from six nations (n = 10 per nation) were analyzed by LC-MS/MS to demonstrate the method performance parameters and to make preliminary observations about the occurrence of the PFCs in soils in different parts of the world. The resulting method shows acceptable performance characteristics for the target compounds in most soils while documenting the widespread occurrence of PFCs in surface soils.     

Effects of 4-methylbenzylidene camphor (4-MBC) on neuronal and muscular development in zebrafish (<Emphasis Type="Italic">Danio rerio</Emphasis>) embryos

The negative effects of overexposure to ultraviolet (UV) radiation in humans, including sunburn and light-induced cellular injury, are of increasing public concern. 4-Methylbenzylidene camphor (4-MBC), an organic chemical UV filter, is an active ingredient in sunscreen products. To date, little information is available about its neurotoxicity during early vertebrate development. Zebrafish embryos were exposed to various concentrations of 4-MBC in embryo medium for 3 days. In this study, a high concentration of 4-MBC, which is not being expected at the current environmental concentrations in the environment, was used for the purpose of phenotypic screening. Embryos exposed to 15 μM of 4-MBC displayed abnormal axial curvature and exhibited impaired motility. Exposure effects were found to be greatest during the segmentation period, when somite formation and innervation occur. Immunostaining of the muscle and axon markers F59, znp1, and zn5 revealed that 4-MBC exposure leads to a disorganized pattern of slow muscle fibers and axon pathfinding errors during the innervation of both primary and secondary motor neurons. Our results also showed reduction in AChE activity upon 4-MBC exposure both in vivo in the embryos (15 μM) and in vitro in mammalian Neuro-2A cells (0.1 μM), providing a possible mechanism for 4-MBC-induced muscular and neuronal defects. Taken together, our results have shown that 4-MBC is a teratogen and influences muscular and neuronal development, which may result in developmental defects.     

River water contaminated with perfluorinated compounds potentially posing the greatest risk to young children

Although, humans are exposed to perflourinated compounds (PFCs) from various media, water consumption could be an important source for the residents living near to contaminated areas. Since comprehensive multimedia exposure model has not been developed for PFCs, assessment of the potential risk due to exposure to PFCs through direct water consumption could be a conservative estimate. The human health risks derived from the exposure to PFCs through water consumption were assessed for different age groups of general population in Taiwan using probabilistic approach. Based on available data on concentrations of PFCs in river water, exposure to PFOS, PFOA and PFDA via water consumption for different age groups were calculated using deterministic and probabilistic risk assessment methods. The oral non-cancer risks from PFOS, PFOA and their combination, expressed as a Hazard Index (HI), was determined by comparing oral exposure dose (through water intake) with the oral Reference Dose (RfD). The average exposure to PFOS, PFOA and PFDA via water consumption for adults ranged from 0.16 to 220.15, 0.43 to 12.5 and 0.43 to 2.36 ng kg-bw^?1 d^?1 and for children 0.13–354.3, 0.35–20.17 and 0.35–3.79 ng kg-bw^?1 d^?1, respectively. Probabilistic values of total HIs for all age groups reside near to Keya River exceed the RfD 2.4–4.8 times, corresponding mainly to PFOS with a percentage of 97%. In conclusions, children aged 1–3 years old and the residents reside near to Keya River are at the highest risk of exposure to PFCs via water consumption.     

Effects of cyanobacterium Fischerella ambigua isolates and cell free culture media on zebrafish (Danio rerio) embryo development

The toxic effects of several species of fresh water cyanobacteria, notably Microcystis species and associated toxins, the microcystins, Anabaena species (anatoxin), Nodularia sp. (nodularin), and Cylindrospermopsis raciborskii (cylindrospermopsin), are well known. Little, however, is known about the effects of secondary metabolites other than alkaloids. Early life stage tests with zebrafish (Danio rerio) were used to detect bioactive properties of compounds released by healthy cyanobacteria (Fischerella ambigua), particularly on the early developmental stages of fish. This approach, using F. ambigua is probably most valuable as it shows the toxicity of healthy growing cyanobacteria. The effects of cyanobacterial secondary metabolites on the embryonic stages of fish are of considerable interest as many aquatic creatures, particularly fish, are unable to avoid the potential toxins that may be released by undesirable algal blooms or as a result of allelopathic effects. In the current study, the zebrafish (D. rerio) was used as a model experimental system to investigate the effects of ambigols A and C, tjipanazole D and C, 2,4-dichlorobenzoic acid, cell free culture media, and media extracts of a terrestrial/fresh water strain of the cyanobacterium F. ambigua on embryo development. Fish embryo tests performed with the cell free culture medium showed that after 3h of exposure to undiluted culture medium all fish embryos died. At a tenfold dilution the process of epiboly (formation of the gastrula) was retarded in all embryos, lesions were observed, and their general development was significantly arrested, finally followed by death. The same tests performed with extracts (dichloromethane, n-butanol, and residual cell free culture medium) of the cell free culture medium, ambigol A, ambigol C, 2,4-dichlorobenzoic acid and tjipanazole D showed only ambigol A to have an influence on zebrafish development at concentrations>or=1 mg/l (2.06 microM). After 55 h all embryos showed pectoral oedema, irregularly shaped fin folds, bent tails, and unusual circular neoplasms in the dorsal tail fin fold. Due to the high concentration of ambigol A used in this assay these effects were considered to be of minor importance when compared to those of the culture medium.     

Bioaccumulation and effects of perfluorinated compounds (PFCs) in zebra mussels (Dreissena polymorpha)

Perfluorinated chemicals (PFCs) have been used for many years in numerous industrial products and are known to accumulate in organisms. A recent survey showed that tissue levels of PFCs in aquatic organisms varied among compounds and species being undetected in freshwater zebra mussels Dreissena polymorpha. Here we studied the bioaccumulation kinetics and effects of two major PFCs, perfluorooctane sulfonic acid compound (PFOS) and perfluorooctanoic acid (PFOA), in multixenobiotic transporter activity (MXR) and filtration and oxygen consumption rates in zebra mussel exposed to a range of concentrations of a PCF mixture (1–1,000 μg/L) during 10 days. Results indicate a low potential of the studied PFCs to bioaccumulate in zebra mussel tissues. PFCs altered mussel MXR transporter activity being inhibited at day 1 but not at day 10. Bioaccumulation kinetics of PFCs were inversely related with MXR transporter activity above 9 ng/g wet weight and unrelated at tissue concentration lower than 2 ng/g wet weight suggesting that at high tissue concentrations, these type of compounds may be effluxed out by MXR transporters and as a result have a low potential to be bioaccumulated in zebra mussels. Oxygen consumption rates but not filtering rates were increased in all exposure levels and periods indicating that at environmental relevant concentrations of 1 μg/L, the studied PFCs enhanced oxidative metabolism of mussels. Overall, the results obtained in this study confirm previous findings in the field indicating that an important fraction of PFC accumulated in mussel tissues is eliminated actively by MXR transporters or other processes that are metabolically costly.