Perfluorinated compounds in whole fish homogenates from the Ohio, Missouri, and Upper Mississippi Rivers, USA

A method for the analysis of 10 perfluorinated compounds (PFCs) in whole fish homogenate is presented and applied to 60 fish samples collected from the Ohio, Missouri, and upper Mississippi Rivers in 2005. Method accuracy ranged between 86 and 125% with limits of quantitation between 0.2 and 10 ng/g wet weight. Intra- and inter-batch precision was generally ±20%. Perfluorooctane sulfonate (PFOS) was the predominant compound identified in these samples, contributing over 80% of total PFC composition in the fish from these rivers, with median PFOS concentrations of 24.4, 31.8, and 53.9 ng/g wet wt in the Missouri, Ohio, and Mississippi Rivers, respectively. Median PFOS levels were significantly (p = 0.01) elevated in piscivorous fish (88.0 ng/g) when compared with non-piscivorous fish (15.9 ng/g). The 10 samples with PFOS concentrations above 200 ng/g were broadly scattered across all three rivers, providing evidence of the widespread presence of this compound in these US waterways.     

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).     

Perfluoroalkyl and polyfluoroalkyl substances (PFASs) in consumer products in Norway - a pilot study

Perfluoroalkyl and polyfluoroalkyl substances (PFAS) are used in numerous industrial and consumer products because of their special chemical properties, for instance the ability to repel both water and oil. A broad variety of PFAS have been introduced into the Norwegian market through industrial use (e.g. via fire fighting foams and paints) as well as in treated customer products such as textiles and coated paper. Our present knowledge of the exact chemical PFAS compositions in preparations using perfluorinated compounds is limited. This lack of knowledge means that it is difficult to provide an accurate assessment of human exposure to these compounds or to the amount of waste that may contain treated products. It is a growing concern that these potentially harmful compounds can now be found throughout the global environment.Samples of consumer products and preparations were collected in Norway, with supplemental samples from Sweden. In 27 of the 30 analyzed consumer products and preparations a number of polyfluorinated substances that were analyzed were detected but this does not exclude the occurrence of unknown PFAS. Notable was that perfluorooctanesulphonate (PFOS), which has been strictly regulated in Norway since 2007, was found in amounts close to or exceeding the EU regulatory level in 4 of the 30 analyzed products, all within the leather or carpet product groups. High amounts of fluorotelomer alcohols (FTOHs) were found in waterproofing agents, carpets and textiles, consistent with earlier findings by Fiedler et al. (2010). The presence of PFAS in a broad range of consumer products can give rise to a constant diffuse human exposure that might eventually result in harm to humans.     

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.     

Temporal trends of polyfluoroalkyl compounds (PFCs) in liver tissue of grey seals (Halichoerus grypus) from the Baltic Sea, 1974-2008

Temporal trends of polyfluoroalkyl compounds (PFCs) were examined in grey seal (Halichoerus grypus) liver from the Baltic Sea over a period of 35 years (1974-2008). In total, 17 of 43 PFCs were found, including the perfluoroalkyl sulfonates (C₄-C₁₀ PFSAs), perfluorooctanesulfinate (PFOSi), long chain perfluoroalkyl carboxylates (C₇-C₁₄ PFCAs), and perfluoroalkyl sulfonamides (i.e., perfluorooctane sulfonamide (FOSA) and N-ethyl perfluorooctane sulfonamide (EtFOSA)), whereas saturated and unsaturated fluorotelomer carboxylates, shorter chain PFCAs and perfluoroalkyl phosphonic acids were not detected. Perfluorooctane sulfonate (PFOS) was the predominant compound (9.57-1444 ng g⁻¹ wet weight (ww)), followed by perfluorononanoate (PFNA, 0.47-109 ng g⁻¹ ww). C₆-C₈ PFSAs, PFOSi and C₇-C₁₃ PFCAs showed statistically significant increasing concentrations between 1974 and 1997, with a peak in 1997 and then decreased or levelled off (except for C₁₂ and C₁₃ PFCAs). FOSA had a different temporal trend with a maximum in 1989 followed by significant decreasing concentrations until 2008. Toxicological implications for grey seals are limited, but the maximal PFOS concentration found in this study was about 40 times lower than the predicted lowest observed effect concentrations (LOEC). The statistically significant decreasing concentrations or levelling off for several PFCs in the relative closed marine ecosystem of the Baltic Sea indicate a rapidly responding to reduced emissions to the marine environment. However, the high concentrations of PFOS and continuing increasing concentrations of the longer chain PFCAs (C₁₂-C₁₄) shows that further work on the reduction of environmental emissions of PFCs are necessary.     

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.     

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.     

Reprint of: Temporal trends of polyfluoroalkyl compounds (PFCs) in liver tissue of grey seals (Halichoerus grypus) from the Baltic Sea, 1974-2008

Temporal trends of polyfluoroalkyl compounds (PFCs) were examined in grey seal (Halichoerus grypus) liver from the Baltic Sea over a period of 35 years (1974-2008). In total, 17 of 43 PFCs were found, including the perfluoroalkyl sulfonates (C₄-C₁₀ PFSAs), perfluorooctanesulfinate (PFOSi), long chain perfluoroalkyl carboxylates (C₇-C₁₄ PFCAs), and perfluoroalkyl sulfonamides (i.e., perfluorooctane sulfonamide (FOSA) and N-ethyl perfluorooctane sulfonamide (EtFOSA)), whereas saturated and unsaturated fluorotelomer carboxylates, shorter chain PFCAs and perfluoroalkyl phosphonic acids were not detected. Perfluorooctane sulfonate (PFOS) was the predominant compound (9.57-1444 ng g⁻¹ wet weight (ww)), followed by perfluorononanoate (PFNA, 0.47-109 ng g⁻¹ ww). C₆-C₈ PFSAs, PFOSi and C₇-C₁₃ PFCAs showed statistically significant increasing concentrations between 1974 and 1997, with a peak in 1997 and then decreased or levelled off (except for C₁₂ and C₁₃ PFCAs). FOSA had a different temporal trend with a maximum in 1989 followed by significant decreasing concentrations until 2008. Toxicological implications for grey seals are limited, but the maximal PFOS concentration found in this study was about 40 times lower than the predicted lowest observed effect concentrations (LOEC). The statistically significant decreasing concentrations or levelling off for several PFCs in the relative closed marine ecosystem of the Baltic Sea indicate a rapidly responding to reduced emissions to the marine environment. However, the high concentrations of PFOS and continuing increasing concentrations of the longer chain PFCAs (C₁₂-C₁₄) shows that further work on the reduction of environmental emissions of PFCs are necessary.     

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: -     

Occurrence of per- and polyfluoroalkyl substances (PFAS) in municipal solid waste landfill leachates from western China

Environmental Science and Pollution Research - Landfill leachate has been documented as a significant source of trace organic pollutants, comprising an expansive family of per- and polyfluoroalkyl...     

Spatial distribution and sources of perfluorochemicals in the NW Mediterranean coastal waters (Catalonia, Spain)

This study provides the first evidence of the sources and loads of perfluorochemicals (PFCs) to the NW Mediterranean Sea. Five PFCs were analyzed in 45 seawater samples collected along the Catalan coast. Total PFCs ranged from 0.07 to 13.0 ng/l, being the levels higher in ports than in coastal waters. To determine the sources of PFCs, 8 wastewater treatment plants (WWTPs) effluents and 6 rivers discharging to the sea were also analyzed. WWTP effluents contained total PFCs levels ranging from 3.47 to 132 ng/l but due to the relatively low discharge flows, they contributed to 34.7 g/d to the sea. Total PFCs in rivers ranged from 2.24 to 21.9 ng/l and were the principal PFCs contributors to the sea. Overall, a total load of 190 g/d of PFCs are discharged to the NW Mediterranean coast. The effects and risk of PFCs discharges to the Mediterranean basin are discussed.     

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.     

Biogeochemical dynamics of perfluorinated alkyl acids and sulfonates in the River Seine (Paris, France) under contrasting hydrological conditions

The biogeochemical dynamics of 15 perfluorinated compounds (PFCs) were investigated in a heavily urbanised river (River Seine, Paris, France). The target compounds included C4-C10 sulfonates and C5-C14 acids; eleven PFCs were detected and ∑PFCs ranged between 31 and 91 ng L⁻¹ (median: 47 ng L⁻¹). The molecular pattern was dominated by the perfluoroalkyl sulfonates PFHxS and PFOS (>54% of ∑PFCs), which were the only PFCs quantified in both the dissolved and particulate phases. For these PFCs, the sorbed fraction positively correlated with suspended sediment levels. Total PFC levels negatively correlated with river flow rate, which varied between 150 and 640 m³ s⁻¹. This suggests the predominance of point sources (likely WWTP effluent discharge), but a contribution of non-point sources such as combined sewer overflow could not be excluded. The annual PFC mass flow was estimated at 500 kg, which is less than observed for other large European rivers.     

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.     

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.     

Time trends of perfluorinated compounds from the sediment core of Tokyo Bay, Japan (1950s-2004)

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

Quantification of the interactions between Ca,Hg and extracellular polymeric substances (EPS) of sludge

The interactions between metals (Ca²⁺ and Hg²⁺) and extracellular polymeric substances (EPS) extracted from the aerobic and anaerobic sludge in wastewater treatment reactors were investigated using a combination of zeta potential measurement and 3-dimensional excitation–emission matrix (EEM) fluorescence spectroscopy with parallel factor (PARAFAC) analysis. Results show that Ca²⁺ had no substantial effects on the EEM fluorescence spectra of the EPS, but their zeta potentials increased with the increasing Ca²⁺ dosage. However, Hg²⁺ had a significant effect on the EEM fluorescence spectra of the EPS, while their zeta potentials seemed not to be affected by the dose of Hg²⁺. The interactions between Hg²⁺ and EPS were elucidated using the fluorescence quenching with PARAFAC analysis, while the interactions between Ca²⁺ and EPS were evaluated by the zeta potential technique. The binding constants for Hg²⁺ and EPS were two orders of magnitude higher than those for Ca²⁺ and EPS, suggesting that the binding mechanisms between Ca²⁺ and EPS were different from those between Hg²⁺ and EPS. The results might be useful for understanding the roles of EPS in bacterial self-protection against heavy metals and the aggregate formation mechanisms through ionic bridging interactions.     

Distribution of perfluorinated alkyl substances in marine shellfish along the Chinese Bohai Sea coast

Perfluorinated alkyl substances (PFASs) are emerging persistent organic pollutants, which pose a threat to human health primarily by dietary exposure, especially through seafood. Bohai Sea (a semi-closed sea located north of China) is an important shellfish aquaculture area that is possibly highly-polluted with PFASs. In this study, we first evaluated contamination by PFASs in a total of 230 samples of marine shellfish from the Bohai Sea. Samples included five important shellfish species, collected from important aquaculture spots distributed around the Bohai Sea. Samples were analyzed by an ultra-fast liquid chromatography-tandem mass spectrometry method, which could simultaneously detect 23 PFASs in shellfish. Our research verified that PFASs have become a threat to the safety of shellfish products in this area. Furthermore, contamination by PFASs in shellfish changed depending on the components of PFASs, the species of shellfish, and the sampling sites. Many of the 23 target compounds contributed to the high detection ratio (>50%) as follows: perfluorooctanoic acid (PFOA)?>?perfluorononanoic acid?>?perfluorodecanesulfonic acid?>?perfluorooctanesulfonic acid (PFOS). Compared with other dominant components, PFOA not only had the highest detection percentage in shellfish samples (98.3%), but its detection level contributed to 87.2% of total PFASs concentrations, indicating that PFOA is the major threat to the safety of shellfish products. The highest level of PFAS was found in clams (62.5?ng?g^?1 wet weight of PFOA). The concentration of total PFAS in different shellfish species showed the following trend: clams?>?mussels?>?scallops?>?whelks?>?oysters. The maximum concentration of total PFAS or PFOA was found in Shouguang. The total concentration of PFOS and its precursor were highest in Cangzhou, possibly due to local industrial activities. The results presented in this paper provide new data on the contamination of marine shellfish along the Bohai Sea coasts in China, and constitute a reference for future monitoring of contamination by emerging contaminants in Bohai coast.     

Occurrence, sources, and inventory of hexabromocyclododecanes (HBCDs) in soils from Chongming Island, the Yangtze River Delta (YRD)

Hexabromocyclododecanes (HBCDs) is a concern due to their large usage combining with physico-chemical properties and toxicity to wildlife and human. However, very limited data were reported on HBCDs in soils, especially from rural area. In this study, 22 soil samples were collected from Chongming Island at estuary of the Yangtze River Delta, to investigate the level, diasteroisomer profile, potential sources, and mass inventory of HBCDs. The total concentrations ranged from not detected to 93.8 pg g⁻¹ dry weight (dw) with a mean of 23.3 pg g⁻¹ dw, which was at the low end of the global levels. The wide distribution of HBCDs in soils suggested that the local emissions of HBCD-containing materials and/or the inputs via atmospheric transport from other regions were two possible sources. Variation of HBCDs levels was observed in different types of soils. Woodland, tideland and road soils contained slightly higher HBCDs than those of farmland and grassland. Overall, γ-HBCD was the dominant diasteroisomer in soils, followed by α-HBCD and β-HBCD. Significant but weak correlations were only found between α-HBCD and β-HBCD versus TOC content in soils. Currently, the mass inventory of HBCDs in soils of Chongming Island was 5.3 kg. Based on these data, we gave perspective on human intake of HBCDs via soil ingestion by age. Local resident’s intakes ranged from 15.5 to 97.8 fg kg body weight⁻¹ d⁻¹, in which children are exposed more than adults.     

Influences of influent carbon source on extracellular polymeric substances (EPS) and physicochemical properties of activated sludge

It is necessary to understand the bioflocculation, settling and dewatering characteristics in the activated sludge process in order to establish more efficient operational strategies. The influences of carbon source on the extracellular polymeric substances (EPS) and flocculation, settling and dewatering properties of the activated sludge were investigated. Laboratory-scale completely mixed activated sludge processes were used to grow the activated sludge with different carbon sources of starch, glucose and sodium acetate. The sludge fed with acetate had highest loosely bound EPS (LB-EPS) and that fed with starch lowest. The amount of tightly bound EPS (TB-EPS), protein content in LB-EPS, polysaccharide content and protein contents in TB-EPS, were independent of the influent carbon source. The polysaccharide content in LB-EPS of the activated sludge fed with sodium acetate was lower slightly than those of starch and glucose. The sludge also had a nearly consistent flocs size and the sludge volume index (SVI) value. ESS content of the sludge fed with sodium acetate was higher initially, although it was similar to those fed with glucose and starch finally. However, the specific resistance to filtration and normalized capillary suction time fluctuated first, but finally were stable at around 5.0 × 10⁸ m kg⁻¹ and 3.5 s L g⁻¹ SS, respectively. Only the protein content in LB-EPS weakly correlated with the flocs size and SVI of the activated sludge. But there was no correlation between any other EPS contents or components and the physicochemical properties of the activated sludge.