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.     

Linear and branched perfluorooctane sulfonate (PFOS) isomer patterns differ among several tissues and blood of polar bears

Perfluorooctane sulfonate (PFOS) is a globally distributed persistent organic pollutant that has been found to bioaccumulate and biomagnify in aquatic food webs. Although principally in its linear isomeric configuration, 21–35% of the PFOS manufactured via electrochemical fluorination is produced as a branched structural isomer. PFOS isomer patterns were investigated in multiple tissues of polar bears (Ursus maritimus) from East Greenland. The liver (n = 9), blood (n = 19), brain (n = 16), muscle (n = 5), and adipose (n = 5) were analyzed for linear PFOS (n-PFOS), as well as multiple mono- and di-trifluoromethyl-substituted branched isomers. n-PFOS accounted for 93.0 ± 0.5% of Σ-PFOS isomer concentrations in the liver, whereas the proportion was significantly lower (p < 0.05) in the blood (85.4 ± 0.5%). Branched isomers were quantifiable in the liver and blood, but not in the brain, muscle, or adipose. In both the liver and blood, 6-perfluoromethylheptane sulfonate (P6MHpS) was the dominant branched isomer (2.61 ± 0.10%, and 3.26 ± 0.13% of Σ-PFOS concentrations, respectively). No di-trifluoromethyl-substituted isomers were detectable in any of the tissues analyzed. These tissue-specific isomer patterns suggest isomer-specific pharmacokinetics, perhaps due to differences in protein affinities, and thus differences in protein interactions, as well transport, absorption, and/or metabolism in the body.     

Effect of salinity and sediment characteristics on the sorption and desorption of perfluorooctane sulfonate at sediment-water interface

This study investigated the influence of solution salinity, pH and the sediment characteristics on the sorption and desorption of perfluorooctane sulfonate (PFOS). The results showed that the sorption of PFOS onto sediment increased by a factor of 3 as the CaCl₂ concentration increased from 0.005 to 0.5 mol L⁻¹ at pH 7.0, and nearly 6 at pH 8.0. Desorption hysteresis occurred over all salinity. The thermodynamic index of irreversibility (TII) values increased with increasing concentration of CaCl₂. Maximum irreversibility was found in the sorption systems with CaCl₂ in the concentration of 0.5 mol L⁻¹. The results suggested that PFOS can be largely removed from the water with increasing salinity, and get trapped onto sediments irreversibly. These phenomena could be explained by salting-out effect and Ca-bridging effect. Studies also suggested that the content of total organic carbon is the dominant psychochemical properties of sediment controlling the sorption of PFOS.     

Partitioning of perfluorooctanoate (PFOA), perfluorooctane sulfonate (PFOS) and perfluorooctane sulfonamide (PFOSA) between water and sediment

Laboratory partitioning experiments were conducted to elucidate the sorption behaviour and partitioning of perfluoroalkyl compounds (PFCs). Three different sediment types were used and separately spiked with perfluorooctanoate (PFOA), perfluorooctane sulfonate (PFOS) and perfluorooctane sulfonamide (PFOSA) at low environmentally realistic concentrations. PFOA, PFOS and PFOSA were mainly distributed in the dissolved phase at low suspended solid concentrations, indicating their long-range transport potential in the marine environment. In all cases, the equilibrium isotherms were linear and the organic carbon normalised partition coefficients (K_OC) decreased in the following order: PFOSA (log K_OC = 4.1 ± 0.35 cm³ g⁻¹) > PFOS (3.7 ± 0.56 cm³ g⁻¹) > PFOA (2.4 ± 0.12 cm³ g⁻¹). The level of organic content had a significant influence on the partitioning. For the sediment with negligible organic content the density of the sediment became the most important factor influencing the partitioning. Ultimately, data on the partitioning of PFCs between aqueous media and suspended solids are essential for modelling their transport and environmental fate.     

A rapid and high-throughput quantum dots bioassay for monitoring of perfluorooctane sulfonate in environmental water samples

Currently HPLC/MS is the state of the art tool for environmental/drinking water perfluorooctane sulfonate (PFOS) monitoring. PFOS can bind to peroxisomal proliferator-activated receptor-alpha (PPARα), which forms heterodimers with retinoid X receptors (RXRs) and binds to PPAR response elements. In this bioassay free PFOS in water samples competes with immobilized PFOS in ELISA plates for a given amount of PPARα-RXRα. It can be determined indirectly by immobilizing PPARα-RXRα-PFOS complex to another plate coated with PPARα antibody and subsequent measuring the level of PPARα-RXRα by using biotin-modified PPARα-RXRα probes-quantum dots-streptavidin detection system. The rapid and high-throughput bioassay demonstrated a detection limit of 2.5 ng L⁻¹ with linear range between 2.5 ng L⁻¹ and 75 ng L⁻¹. Detection results of environmental water samples were highly consistent between the bioassay and HPLC/MS.     

Effect of cationic and anionic surfactants on the sorption and desorption of perfluorooctane sulfonate (PFOS) on natural sediments

Sorption and desorption of PFOS at water-sediment interfaces were investigated in the presence of a cationic surfactant, cetyltrimethylammonium bromide (CTAB), and an anionic surfactant, sodium dodecylbenzene sulfonate (SDBS). CTAB remarkably enhanced the sorption of PFOS on the sediment. In contrast, the influence of SDBS to the sorption of PFOS was concentration dependent. Two contrasting factors were responsible for the phenomenon. One was the sorption of the surfactant itself to the sediment, which enhanced the sorption of PFOS. The other was the increase in solubility of PFOS caused by the adding of surfactants, which decreased the sorption of PFOS. SDBS had a much lower sorption capacity, but rather strong ability to increase the solubility of PFOS. High levels of SDBS remarkably reduced the sorption of PFOS on the sediment. These results imply that cationic and anionic surfactants may have contrast impacts on the distribution and transport of PFOS in the environment.     

Enhanced cytotoxicity of pentachlorophenol by perfluorooctane sulfonate or perfluorooctanoic acid in HepG2 cells

Chlorinated phenols and perfluoroalkyl acids (PFAAs) are two kinds of pollutants which are widely present in the environment. Considering liver is the primary toxic target organ for these two groups of chemicals, it is interesting to evaluate the possible joint effects of them on liver. In this work, the combined toxicity of pentachlorophenol (PCP) and perfluorooctane sulfonate (PFOS) or perfluorooctanoic acid (PFOA) were investigated using HepG2 cells. The results indicated that PFOS and PFOA could strengthen PCP’s hepatotoxicity. Further studies showed that rather than intensify the oxidative stress or promote the biotransformation of PCP, PFOS (or PFOA) might lead to strengthening of the oxidative phosphorylation uncoupling of PCP. By measuring the intracellular PCP concentration and the cell membrane properties, it was suggested that PFOS and PFOA could disrupt the plasma membrane and increase the membrane permeability. Thus, more cellular accessibility of PCP was induced when they were co-exposed to PCP and PFOS (or PFOA), leading to increased cytotoxicity. Further research is warranted to better understand the combined toxicity of PFAAs and other environmental pollutants.     

Enhanced sorption of perfluorooctane sulfonate (PFOS) on carbon nanotube-filled electrospun nanofibrous membranes

Multi-walled carbon nanotube-filled electrospun nanofibrous membranes (MWCNT-ENFMs) were prepared by electrospinning. The addition of MWCNTs (0.5 wt.% vs. ENFMs) doubled the specific surface area and tensile strength of the ENFMs. The MWCNT-ENFMs were used to adsorb perfluorooctane sulfonate (PFOS) in aqueous solutions. The sorption kinetics results showed that the sorption rate of PFOS onto the MWCNT-ENFMs was much higher than the sorption rate of PFOS onto the pure ENFMs control, and the pseudo-second-order model (PSOM) described the sorption kinetics well. The sorption isotherms indicated that the sorption capacity of the MWCNT-ENFMs for PFOS (16.29 ± 0.26 μmol g⁻¹) increased approximately 18 times, compared with the pure ENFMs (0.92 ± 0.06 μmol g⁻¹). Moreover, the solution pH significantly affected the sorption efficiency and sorption mechanism. The MWCNT-ENFMs were negatively charged from pH 2.0–10.0, but the electrostatic repulsion between the MWCNT-ENFMs and PFOS was overcome by the hydrophobic interactions between PFOS and the MWCNTs or nanofibers. The strong hydrophobic interactions between PFOS and the MWCNTs played a dominant role in the sorption process. For the pure ENFMs, the electrostatic repulsion was conquered by the hydrophobic interactions between PFOS and the nanofibers at pH > 3.1. In addition to the hydrophobic interactions, an electrostatic attraction between PFOS and the pure ENFMs was involved in the sorption process at pH < 3.1.     

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.     

A comparative study on sorption of perfluorooctane sulfonate (PFOS) by chars, ash and carbon nanotubes

Perfluorooctane sulfonate (PFOS), as one of emerging contaminants, has been attracting increasing concerns in recent years. Sorption of PFOS by maize straw- and willow-derived chars (M400 and W400), maize straw-origin ash (MA) as well as three carbon nanotubes (CNTs) was studied in this work. The sorption kinetics of PFOS by the six adsorbents was well fitted by the pseudo-second-order model. CNTs reached equilibrium in 2 h, much faster than those by chars (384 h) and ash (48 h). According to the sorption isotherms, both single-walled carbon nanotubes (SWCNT) and MA had high sorption capacities (over 700 mg g⁻¹), while the two chars had low sorption capacities (below 170 mg g⁻¹) caused by their small BET surface area. In the case of MA, due to its positively charged surface, both hydrophobic interaction and electrostatic attraction involved in the sorption, and the formation of hemi-micelles further favored the sorption. This study suggested that SWCNT and MA were effective adsorbents for PFOS removal from water. Compared to SWCNT, MA is low cost and easy to obtain, so it could be a preferred adsorbent for PFOS removal.     

Effective sorption of perfluorooctane sulfonate (PFOS) on hexadecyltrimethylammonium bromide immobilized mesoporous SiO2 hollow sphere

The hexadecyltrimethylammonium bromide (HDTMAB) immobilized hollow mesoporous silica spheres were prepared for the efficient removal of perfluorooctane sulfonate (PFOS) from aqueous solution. Besides the traditional sorption behavior including sorption kinetics as well as effect of solution pH and temperature, the effect of increasing volume which simulated the natural river where the rate of solute and solvent was relatively constant and solution volume was always changing was investigated. The result indicated that the residual PFOS concentrations in aqueous phase decreased with increasing solution pH and ionic strength, whereas they increased with increasing temperature. The HDTMAB immobilized material still maintained high efficiency after increasing volume, that is, the removal kept more than 99% after the treatment when the initial PFOS concentration was 1 mg L^?1. The uptake behavior and morphology of spheres which was characterized by transmission electron microscopy (TEM) revealed that the additional HDTMAB and mesoporous shell were responsible for the enhanced sorption of PFOS. It was concluded that electrostatic interaction and Ca-bridge role played an important role in the sorption of PFOS on the mesoporous SiO₂ hollow spheres, whereas, hydrophobic interaction contributed to the nice sorption performance of PFOS on the HDTMAB immobilized sorbent.     

Exposure to perfluorooctane sulfonic acid (PFOS) adversely affects the life-cycle of the damselfly Enallagma cyathigerum

We evaluated whether life-time exposure to PFOS affects egg development, hatching, larval development, survival, metamorphosis and body mass of Enallagma cyathigerum (Insecta: Odonata). Eggs and larvae were exposed to five concentrations ranging from 0 to 10 000 μg/L. Our results show reduced egg hatching success, slower larval development, greater larval mortality, and decreased metamorphosis success with increasing PFOS concentration. PFOS had no effect on egg developmental time and hatching or on mass of adults. Eggs were the least sensitive stage (NOEC = 10 000 μg/L). Larval NOEC values were 1000 times smaller (10 μg/L). Successful metamorphosis was the most sensitive response trait studied (NOEC < 10 μg/L). The NOEC value suggests that E. cyathigerum is amongst the most sensitive freshwater organisms tested. NOEC for metamorphosis is less than 10-times greater than the ordinary reported environmental concentrations in freshwater, but is more than 200-times smaller than the greatest concentrations measured after accidental releases.     

Tracking historical lead pollution in the coastal area adjacent to the Yangtze River Estuary using lead isotopic compositions

The rapid economic development in the Yangtze River Delta (YRD), China in the last three decades has had a significant impact on the environment of the East China Sea (ECS). Lead isotopic compositions of a ²¹⁰Pb dated sediment core collected from the coastal ECS adjacent to the Yangtze River Estuary were analyzed to track the Pb pollution in the region. The baseline Pb concentration in the coastal ECS sediments before the industrialization in China was 32 μg g⁻¹, and the corresponding ²⁰⁶Pb/²⁰⁷Pb ratio was 1.195. The high-resolution profiles of Pb flux and ²⁰⁶Pb/²⁰⁷Pb ratios had close relationships with the economic development and the history of the use of leaded gasoline in China, and they were clearly different from those of most European countries and United States.     

Characterisation of perfluorooctane sulfonate (PFOS) in a terrestrial ecosystem near a fluorochemical plant in Flanders,Belgium

Bioaccumulation of perfluorooctane sulfonate (PFOS) in a restricted terrestrial food chain was investigated with the omnivorous wood mouse (Apodemus sylvaticus) on top of the studied food chain. The levels detected are very high compared with literature as a result of the presence of fluorochemical plant in the immediate vicinity of the study area. Soil, surface water, fruits of European elder and common blackberry, invertebrates, bank vole and wood mouse were collected at two sites, e.g. Blokkersdijk, adjacent to the fluorochemical plant, and Galgenweel, a reference site 2 km further away. In wood mouse, the highest PFOS concentrations were found in the liver followed by the pancreas, lungs and kidneys, with the spleen having the lowest levels. In the liver, the concentrations ranged from 787 to 22,355 ng/g ww at Blokkersdijk and these were significantly correlated with those detected in the kidneys (13.7–4,226 ng/g ww). If current results are compared to the findings of a previous study conducted in 2002 at the same sites, a significant decrease of PFOS in livers of wood mouse is observed. To the best of our knowledge, so far no studies reported levels of PFOS in terrestrial invertebrates under field conditions. At Blokkersdijk, PFOS was detected in all invertebrate species ranging from 28 to 9,000 ng/g. Soil and water were also contaminated with levels of respectively 68 ng/g and 22 ng/L. Biota-to-soil accumulation factors ranged from 0.11 to 68 for earthworms. Biomagnification factors (BMFs) of liver wood mouse/berries were as high as 302. BMFs for invertebrates were remarkably lower (up to 2).     

Perfluorooctane Sulfonate Increases the Genotoxicity of Cyclophosphamide in the Micronucleus Assay with V79 Cells: Further Proof of Alterations in Cell Membrane Properties Caused by PFOS (3 pp)

Background, Aim and Scope Perfluorooctane sulfonate (PFOS; C8F17SO3-) is a fully fluorinated organic compound which has been manufactured for decades and was used widely in industrial and commercial products. The recent toxicological knowledge of PFOS mainly concerns mono-substance exposures of PFOS to biological systems, leaving the potential interactive effects of PFOS with other compounds as an area where understanding is significantly lacking. However, a recent study, reported the potential of PFOS to enhance the toxicity of two compounds by increasing cell membrane permeability. This is of particular concern since PFOS has been reported to be widely distributed in the environment where contaminants are known to occur in complex mixtures. In this study, PFOS was evaluated alone and in combination with cyclophosphamide (CPP) to investigate whether a presence of PFOS leads to an increased genotoxic potential of CPP towards hamster lung V79 cells. Genotoxicity was investigated using the micronucleus (MN) assay according to the recent draft ISO/DIS 21427-2 method. PFOS alone demonstrated no genotoxicity up to a concentration of 12.5 mg/L. However, PFOS combined with two different concentrations of CPP, with metabolic activation, caused a significant increase in the number of micronucleated cells compared to treatments with CPP only. These results provide a first indication that PFOS has the potential to enhance the genotoxic action of CPP towards V79 cells, suggesting that together with the alterations in cell membrane properties shown previously, that genotoxicity of complex mixtures may be increased significantly by changes in chemical uptake. Together with an earlier study performed by the own working group it can be concluded that PFOS alone is not genotoxic in this bioassay using V79 cells up to 12.5 mg/L, but that further investigations are needed to assess the potential interaction between PFOS and other substances, in particular regarding the impact of membrane alterations on the uptake of toxic substances. Materials and Methods: - Results: - Discussion: - Conclusions: - Recommendations and Perspectives: -     

Accumulation of perfluorooctane sulfonate (PFOS) in the food chain of the Western Scheldt estuary: Comparing field measurements with kinetic modeling

The environmentally persistent perfluorooctane sulfonate (PFOS) is a perfluoroalkylated acid (PFA), which has been found to accumulate and biomagnify through food webs all over the world. In the present investigation, the accumulation kinetics of PFOS was explored using the bioaccumulation model OMEGA. As accumulation behavior of PFOS may show similarities to fatty acids as well as to neutral organic compounds, different modeling approaches were used. Accumulation kinetics of PFOS was modeled similar to (1) moderately and (2) highly hydrophobic compounds, (3) metals and (4) as a combination of hydrophobic compounds and metals. Modeled elimination and uptake rate constants were compared to empirical rate constants from literature. Subsequently, model predictions were compared to field-based biota-suspended solids accumulation ratios (BSAF) in the estuarine food chain of the Western Scheldt, The Netherlands. Results show that uptake of PFOS is comparable to moderately hydrophobic compounds and elimination is best described by elimination kinetics of metals. These observations indicate that the accumulation behavior of PFOS is comparable to that of short and medium chained fatty acids.     

Environmental contamination, human exposure and body loadings of perfluorooctane sulfonate (PFOS), focusing on Asian countries

Perfluorinated compounds (PFCs) are man-made fluorinated hydrocarbons, which are very persistent in the environment. Since the early 1980s, the usage of PFCs has sharply increased for a wide array of industrial and commercial applications. Being the most important PFC, perfluorooctane sulfonate (PFOS) has received much attention. In the past decades, increasing surveys have been focused on this compound, to study its sources, fates and effects in the environment. According to the large production volume and wide usage in industrial and commercial products in the past, PFOS can be detected in various environmental media and matrix, even in human tissues. This article attempted to review the current status of PFOS contaminations in Asia, focusing on water systems, sediments, wide animals and human tissues. A special section is devoted to examine the pathways of human exposure to this compound, as well as human body loadings of PFOS and their possible association with diseases.     

Occurrence and dietary exposure assessment of PFOS and PFOA in cultured Trachinotus ovatus in China

In this study, investigation was conducted into concentrations of perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) in Chinese farmed Trachinotus ovatus between 2014 and 2015 using a modified QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) and ultra fast liquid chromatography-tandem mass spectrometry (UFLC-MS/MS) method. The tissue distribution (muscle, skin, liver, kidney and gill) in Trachinotus ovatus was also assessed. The detection frequencies of PFOS and PFOA in fish were 92% and 3%, respectively, and the mean concentrations were 0.392 and 0.015 μg/kg wet weight. The analysis of PFOS distribution in different tissues in Trachinotus ovatus showed the following trend: skin> gill> kidney> liver> flesh. Results revealeded farmed Trachinotus ovatus in China to generally be contaminated with PFOS. Moreover, the average daily intake for Chinese urban residents calculated on the basis of pollution content was 0.268 ng/kg body weight/d (PFOS) and 0.014 ng/kg body weight /d (PFOA), respectively. Both hazard ratio values were less than 1, indicating that exposure levels of PFOS and PFOA through Trachinotus ovatus consumption may not lead to adverse health effects in the Chinese population.     

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.