Abstract  The effects of four types of dissolved organic matters (DOM) on the bioconcentration of perfluoroalkyl substances (PFASs) in Chironomus plumosus larvae have been studied. The PFASs included perfluorooctane sulfonate (PFOS), perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), perfluorodecanoic acid (PFDA), perfluoroundecanoic acid (PFUnA), and perfluorododecanoic acid (PFDoA). The DOM included humic acid (HA), fulvic acid (FA), tannic acid (TA), and a protein, peptone (PEP), and their concentrations ranged from 0 to 50 mg L(-1). The results showed that, upon bioconcentration equilibrium, the body burdens of longer perfluoroalkyl chain PFASs (PFOS, PFDA, PFUnA and PFDoA) decreased with PEP and HA concentrations while increased with FA and TA concentrations. When FA and TA concentrations increased from 0 to 50 mg L(-1), body burdens of these PFASs increased by 7.5%-148.8% and 5.7%-37.1%, respectively. However, the DOM had no significant impact on the body burdens of shorter perfluoroalkyl chain PFASs (PFOA and PFNA). All of the four types of DOM lowered not only the uptake rate constants (ku) of PFASs due to the decrease of freely dissolved PFAS concentrations, but also the elimination rate constants (ke) due to the inhibition effect of DOM on the PFAS elimination from the larvae. The reduction in the two constants varied with both DOM and PFAS types. In the presence of PEP and HA with larger molecular weights, the ku values decreased more than ke, leading to the decreased body burdens of longer perfluoroalkyl chain PFASs. As for FA and TA with smaller molecular weights, the ke values decreased more than ku, resulting in increased body burdens of longer perfluoroalkyl chain PFASs. This study suggests that the effects of DOM on PFAS bioconcentration depend not only on the concentration but also on the molecule weight of DOM, which should be considered in the bioavailability assessment of PFASs.

Abstract  Concerns regarding perfluorinated chemicals (PFCs) have grown significantly in recent years. However, regulations and guidelines regarding the emission and treatment of PFCs are still missing in most parts of the world, mostly due to the lack of PFC toxicity data. In the current study, the genotoxic effects of four common PFCs, named perfluorooctanesulfonate (PFOS), perfluoroocanoic acid (PFOA), perfluorononanoic acid (PFNA) and perfluorodecanoic acid (PFDA) were investigated on marine mussels. The effects of exposure time and concentration on the toxic behavior of the compounds were also examined. Genotoxicity of PFCs was assessed in biomarker assays, showing that exposure to the target compounds could damage the organism's genetic material to varying extents, including DNA strand breaks and fragmentation, chromosomal breaks and apoptosis. The adverse effects increased with both exposure concentration and time and were related with the organism burden of PFCs. The integrated biomarker response analysis demonstrated that PFOS exhibited a higher genotoxicity than the other tested compounds. The EC50 values and confidence intervals based on integrative genotoxicity were 33 (29-37), 594 (341-1036), 195 (144-265) and 78 (73-84) μg/L for PFOS, PFOA, PFNA and PFDA respectively, classifying PFOS as a highly genotoxic compound. Although primary DNA damage was shown to be recoverable after exposure ceased, permanent genetic damage caused by elevated PFC concentrations was not restored. This is the first ecotoxicity study of PFCs that focuses on the genotoxic effects of the compounds, clearly indicating the genotoxicity of the tested PFCs and demonstrating that functional groups have a major impact on the compounds' genotoxic behavior.

Abstract  Water, sediment, plankton, and blood and liver tissues of crucian carp (Carassius auratus) and mandarin fish (Siniperca scherzeri) were collected from six major rivers and lakes in South Korea (including Namhan River, Bukhan River, Nakdong River, Nam River, Yeongsan River and Sangsa Lake) and analyzed for perfluorinated alkyl substances (PFASs). Perfluorooctane sulfonate (PFOS) was consistently detected at the greatest concentrations in all media surveyed with the maximum concentration in water of 15 ng L(-1) and in biota of 234 ng mL(-1) (fish blood). A general ascending order of PFAS concentration of water0.80, p<0.001) were observed between PFOS concentration in blood and liver tissues of both crucian carp and mandarin fish. This result suggests that blood can be used for nonlethal monitoring of PFOS in fish. Overall, the rank order of mean bioconcentration factors (BCFs) of PFOS in biota was; phytoplankton (196 L/kg)

Abstract  Time-series of perfluorinated alkylated substances (PFASs) in East Greenland polar bears and East and West Greenland ringed seals were updated in order to deduce whether a response to the major reduction in perfluoroalkyl production in the early 2000s had occurred. Previous studies had documented an exponential increase of perfluorooctane sulphonate (PFOS) in liver tissue from both species. In the present study, PFOS was still the far most dominant compound constituting 92% (West Greenland ringed seals), 88% (East Greenland ringed seals) and 85% (East Greenland polar bears). The PFOS concentrations increased up to 2006 with doubling times of approximately 6 years for the ringed seal populations and 14 years in case of polar bears. Since then a rapid decrease has occurred with clearing half-lives of approximately 1, 2 and 4 years, respectively. In polar bears perfluorohexane sulphonate (PFHxS) and perfluorooctane sulphonamide (PFOSA) also showed decreasing trends in recent years as do perfluorodecanoic acid (PFDA) and perfluoroundecanoic acid (PFUnA). For the West Greenland ringed seal population perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), PFDA and PFUnA peaked in the mid 2000s, whereas PFNA, PFDA and PFUnA in the East Greenland population have been stable or increasing in recent years. The peak of PFASs in Greenland ringed seals and polar bears occurred at a later time than in Canadian seals and polar bears and considerably later than observed in seal species from more southern latitudes. We suggest that this could be explained by the distance to emission hot-spots and differences in long-range transport to the Arctic.

Abstract  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.

Abstract  Numerous studies have reported on the global distribution, persistence, fate, and toxicity of perfluoroalkyl and polyfluoroalkyl substances (PFASs). However, studies on PFASs in terrestrial mammals are scarce. Rats can be good sentinels of human exposure to toxicants because of their habitat, which is in close proximity to humans. Furthermore, exposure data measured for rats can be directly applied for risk assessment because many toxicological studies use rodent models. In this study, a nationwide survey of PFASs in the blood of wild rats as well as surface water samples collected from rats' habitats from 47 prefectures in Japan was conducted. In addition to known PFASs, combustion ion chromatography technique was used for analysis of total fluorine concentrations in the blood of rats. In total, 216 blood samples representing three species of wild rats (house rat, Norway rats, and field mice) were analyzed for 23 PFASs. Perfluorooctanesulfonate (PFOS; concentration range <0.05-148 ng/mL), perfluorooctane sulfonamide (PFOSA; <0.1-157), perfluorododecanoate (<0.05-5.8), perfluoroundecanoate (PFUnDA; <0.05-51), perfluorodecanoate (PFDA; <0.05-9.7), perfluorononanoate (PFNA; <0.05-249), and perfluorooctanoate (PFOA) (<0.05-60) were detected >80 % of the blood samples. Concentrations of several PFASs in rat blood were similar to those reported for humans. PFSAs (mainly PFOS) accounted for 45 % of total PFASs, whereas perfluoroalkyl carboxylates (PFCAs), especially PFUnDA and PFNA, accounted for 20 and 10 % of total PFASs, respectively. In water samples, PFCAs were the predominant compounds with PFOA and PFNA found in >90 % of the samples. There were strong correlations (p < 0.001 to p < 0.05) between human population density and levels of PFOS, PFNA, PFOA, and PFOSA in wild rat blood.

Abstract  Perfluorinated sulfonates (PFSAs) and perfluorinated carboxylates (PFCAs), as well as selected precursor compounds, were measured in eggs of thick-billed murres (Uria lomvia) and northern fulmars (Fulmarus glacialis) from Prince Leopold Island in the Canadian Arctic between 1975 and 2011 as well as in eggs of three additional species (black guillemot Cepphus grylle, black-legged kittiwake Rissa tridactyla, glaucous gull Larus hyperboreus) sampled in 2008. ΣPFCA concentrations increased significantly from 1975 to 2011 in the murre and fulmar eggs at an average annual rate of 0.56 and 0.91 ng g(-1) ww, respectively, whereas perfluorooctane sulfonate (PFOS) concentrations did not change significantly. The interspecies comparison of eggs sampled in 2008 found that black guillemots had the highest PFOS and lowest ΣPFCA levels, and northern fulmars had the highest ΣPFCA levels. PFUnA (C(11)) and PFTrA (C(13)) were the predominant PFCAs measured in eggs of all five species except for the black guillemot where PFDA (C(10)) contributed almost equally with PFTrA (C(13)) to the PFCA profile. Based on published toxicity thresholds, levels of neither perfluorooctanoate (PFOA) nor PFOS in seabird eggs from the Canadian Arctic are of toxicological concern. These are the first interspecies comparisons for PFASs in seabirds from the Canadian Arctic.

Abstract  This study examined the effect of five types of carbonaceous materials (CMs) in sediment on bioaccumulation of perfluorochemicals (PFCs) by Chironomus plumosus larvae. The CMs included two multiwalled carbon nanotubes (MWCNT10 and MWCNT50), maize straw- and willow-derived chars, and maize straw-origin ash. The PFCs included perfluorooctane sulfonate (PFOS), perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), perfluorodecanoic acid (PFDA), perfluoroundecanoic acid (PFUnA), and perfluorododecanoic acid (PFDoA). The CMs with different concentrations (0-1.5% dry weight) were amended into sediments spiked with PFCs and aged for 60 d. The uptake rate constants (k(s)) for each PFC to larvae differed with different CM amendments (p < 0.05), while elimination rate did not change significantly (p > 0.05). Decreasing PFC concentration in larvae (C(B)) was found with increasing CM concentration (f(CM)) in the sediments, and a linear positive correlation existed between 1/C(B) and f(CM) (p < 0.05). The effect of CMs on PFC bioaccumulation agreed well with the CM properties; MWCNT10 with the highest specific surface area resulted in the lowest k(s) values and biota-sediment accumulation factors (BSAF), with a BSAF reduction of 66%-97% by a 1.5% amendment. The mechanism was explored by analyzing the aqueous phase concentrations of PFCs and the sorption of PFCs on sediments amended with CMs. The results suggested that the decreasing trend of PFCs in larvae was caused by the decreasing aqueous phase concentration with increasing CM concentration. In the studied conditions with low PFC concentrations, the bioaccumulation of PFCs was a linear partitioning between pore water and biota, and the sorption of PFCs to the sediment/CM mixtures was a two domain linear distribution. This study suggests that both the type and concentration of carbonaceous materials in sediment can affect the bioaccumulation of PFCs to benthic organisms through changing their aqueous phase concentrations.

Abstract  12 perfluorinated compounds (PFCs) in human blood from workers in a textile mill in Shandong province and several barbershops in Tianjin were analyzed in this study. It was found that perfluorooctane-sulfonate (PFOS) and perfluorooctanoate (PFOA) were the most prominent PFCs, with average concentrations of 5.73 mu g/I. and 5.46 mu g/L for textile workers, and 2.55 mu g/L and 2.84 p.g/L for barbers. PFOS and perfluorohexanesulfonate (PFHxS) concentrations revealed a positive correlation in blood samples (p < 0.01), and concentrations among PFOS, perfluorononanoic acid (PFNA) and perfluorodecanoic acid (PFDA) also revealed positive correlations (p < 0.01). The influence of gender and age on PFC concentration in blood was also investigated, and the results showed that there was no statistically significant difference between the male and female samples, as well as in samples from people with different ages. Generally speaking, the textile workers may face a higher exposure of PFCs than barbers. (C) 2014 Zhao-Fu Meng. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.

Abstract  The Fe3O4@SiO2-BiOBr (FSB) magnetic composite was prepared and introduced into the dielectric barrier discharge (DBD) system as a heterogeneous Fenton-like photocatalyst for synergistic degradation of perfluorooctanoic acid (PFOA). The FSB was characterized by X-ray diffraction, UV-vis diffuse reflectance spectra, energy dispersive X-ray spectroscopy and scanning electron microscope. Characterization results demonstrated that BiOBr was successfully coated on Fe3O4@SiO2, forming FSB, and it exhibited good UV & visible response. The presence of FSB accelerated PFOA degradation: PFOA removal efficiency and total organic carbon removal from DBD-FSB system increased from 73.5% to 92.9% and 28.9% to 62.5%, respectively, within 60 min under reaction conditions of 20 mg L-1 PFOA, initial pH 4.28, 100 mg L-1 FSB and 22 kV peak voltage, as compared with DBD system. Accordingly, defluorination efficiency of PFOA and energy efficiency increased from 21% to 32.8% and 46.39 mg kW(-1)h(-1) to 72.47 mg kW(-1)h(-1), respectively. The synergetic mechanism was attributed to the combination of active species such as center dot OH, H2O2, O-3, directly generated from the DBD plasma and a great amount of center dot OH generated from Fenton-like reaction initiated by FSB photocatalyst under light irradiation emitted during discharge. The center dot OH and photogenerated holes played essential roles in the mineralization process. Based on the identified intermediates, possible degradation pathways of PFOA in DBD-FSB system were proposed, and PFOA degradation mainly occurred via the pathway of perfluoroalkyl radical pathway. 2017 Elsevier B.V. All rights reserved.

Abstract  In 2013 a contamination of drinking water by perfluoroalkylated substances (PFASs) was discovered in areas of the Veneto Region (northern Italy). In this study the exposure to PFASs of people living in the aforesaid areas was characterized: contaminant serum concentrations were measured and compared with those of a control population group living in neighboring areas at background exposure (based on available drinking water data). The enrolled population was also genotyped for the OATP1A2*3 allelic variant, possibly affecting PFAS excretion and hence the internal dose. The difference in PFAS concentrations between exposed and not exposed subjects was significantly larger for nine of the 12 substances analyzed, and confirmed that water contamination had resulted in an appreciable high exposure of the residing population over time. Within the group of exposed subjects, subgroups at different exposure levels were identified. The contamination of drinking water of the residence area was found to be the main factor influencing PFAS serum levels; in addition to water contamination, other relevant influencing factors were sex, the years of residence and raising own livestock. No relationship with the genetic trait for the studied renal transporter was evidenced. These results provide a baseline characterization of PFAS exposure of the monitored population groups for further studies, planned to be carried out in the near future.

Abstract  BACKGROUND: Perfluoroalkyl substances (PFASs) are persistent chemicals with suspected endocrine disrupting abilities applied in consumer products. PFASs have potentially modulating effects on glucose homeostasis. Insulin resistance prevails during third trimester of pregnancy, and this challenge of glucose homeostasis may reveal putative effects of PFAS concentrations on glycemic status.

OBJECTIVE: To investigate associations between five serum PFASs and glucose-related outcomes in pregnant Danish women based on their risk of gestational diabetes mellitus (GDM).

METHODS: In the prospective Odense Child Cohort serum concentrations of five PFASs - perfluorohexane sulfonic acid (PFHxS), perfluorooctane sulfonic acid (PFOS), perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA) and perfluorodecanoic acid (PFDA) - were measured at median gestational week (GW) 11 in pregnant women. An oral glucose tolerance test (OGTT) was performed at GW 28. The statistical analysis was conducted among 158 women with high GDM risk and 160 women with low GDM risk matched by gestational age. Multiple linear regression models were performed to estimate associations between PFAS concentrations and glucose, insulin, C-peptide, homeostatic model of assessment of insulin resistance (HOMA-IR) and beta cell function (HOMA-%β), and insulin sensitivity (Matsuda index) during the 2-h OGTT.

RESULTS: In women with high risk for GDM, a two-fold increase in PFHxS concentration was significantly associated with increased fasting glucose, fasting insulin and HOMA-IR after adjusting for age, parity, educational level and pre-pregnancy BMI. Adjusting for the same confounders, a doubling in PFNA concentration was associated with higher fasting insulin and HOMA-%β. In women with low GDM risk, no associations were found between PFAS concentrations and glucose-related outcomes.

CONCLUSION: PFHxS and PFNA concentrations were associated with impaired glycemic status in metabolically vulnerable pregnant women and might further enhance the risk of developing GDM.

Abstract  Many xenobiotics have been identified as in vitro androgen receptor (AR) antagonists, but information about their ability to produce combined effects at low concentrations is missing. Such data can reveal whether joint effects at the receptor are induced at low levels and may support the prioritisation of in vivo evaluations and provide orientations for the grouping of anti-androgens in cumulative risk assessment. Combinations of 30 AR antagonists from a wide range of sources and exposure routes (pesticides, antioxidants, parabens, UV-filters, synthetic musks, bisphenol-A, benzo(a)pyrene, perfluorooctane sulfonate and pentabromodiphenyl ether) were tested using a reporter gene assay (MDA-kb2). Chemicals were combined at three mixture ratios, equivalent to single components' effect concentrations that inhibit the action of dihydrotesterone by 1%, 10% or 20%. Concentration addition (CA) and independent action were used to calculate additivity expectations. We observed complete suppression of dihydrotestosterone effects when chemicals were combined at individual concentrations eliciting 1%, 10% or 20% AR antagonistic effect. Due to the large number of mixture components, the combined AR antagonistic effects occurred at very low concentrations of individual mixture components. CA slightly underestimated the combined effects at all mixture ratios. In conclusion, large numbers of AR antagonists from a wide variety of sources and exposure routes have the ability of acting together at the receptor to produce joint effects at very low concentrations. Significant mixture effects are observed when chemicals are combined at concentrations that individually do not induce observable AR antagonistic effects. Cumulative risk assessment for AR antagonists should apply grouping criteria based on effects where data are available, rather than on criteria of chemical similarity.

Abstract  Effects of perfluorobutanesulfonic acid (PFBS), perfluorohexanesulfonic acid (PFHxS), perfluorononanoic acid (PFNA), and perfluoroheptanoic acid (PFHpA) on earthworms (Eisenia fetida) in soils contaminated with these compounds at 0.1, 1, 10, 1,000, and 100,000 μg kg-1dry weight, covering concentration levels found in background, biosolid-amended, and facility-surrounding soils, were investigated. Earthworms were exposed to spiked soil for 21 days. Concentrations of these compounds in earthworms after 21-d exposure ranged from below detection to 127 mg kg-1wet weight with the rank order of PFNA > PFHxS > PFHpA > PFBS; no mortality of earthworms was observed in all treatments including controls, except PFBS at 1,000 μg kg-1and all PFASs at 100,000 μg kg-1. The highest weight loss (29%) was observed for earthworms exposed to PFNA at 100,000 μg kg-1, which was significantly different from all other treatments except PFHpA at 100,000 μg kg-1. These results are expected to fill some data gaps in toxicity of PFASs in terrestrial environments and provide helpful information on the potential for trophic transport of PFASs from soil to higher organisms.

Abstract  Perfluorooctane sulfonamide (PFOSA) is a precursor of perfluorooctane sulfonic acid (PFOS) and can be broken down to PFOS in environment and biota. In the present work, PFOSA was spiked in soil and its biodegradation in soil, uptake and metabolism in wheat (Triticum aestivum L.) and earthworms (Eisenia fetida) were investigated. The results indicated that PFOSA could be biodegraded to highly stable PFOS, which has the same perfluorinated carbon chain length as PFOSA, by microbes in soil. PFOSA could be taken up by wheat root and earthworm from soil with higher bioaccumulation ability than PFOS. In both wheat and earthworms, PFOSA also degraded to PFOS. However, other shorter-chain perfluoroalkane sulfonates (PFSAs), including perfluorohexane sulfonate (PFHxS) and perfluorobutane sulfonate (PFBS), were observed in wheat, but not in soil and earthworms, suggesting that wheat displayed distinctly different degradation mechanisms to PFOSA from soil microbes and earthworms.

Abstract  Landfill leachate is often an important source of emerging organic contaminants including perfluoroalkyl and polyfluoroalkyl substances (PFASs) requiring proper treatment to protect surface water and groundwater resources. This study investigated the occurrence of PFASs in the leachate of a capped landfill site in Singapore and the efficacy of PFASs removal during flow through a constructed wetland (CW) treatment system. The CW treatment system consists of equalization tank, aeration lagoons, sedimentation tank, reed beds and polishing ponds. Target compounds included 11 perfluoroalkyl acids (PFAAs) (7 perfluoroalkyl carboxylic acids (PFCAs) and 4 perfluoroalkane sulfonates (PFSAs)) and 7 PFAA precursors. Although total PFASs concentrations in the leachate varied widely (1269 to 7661 ng/L) over the one-year sampling period, the PFASs composition remained relatively stable with PFCAs consistently being predominant (64.0 ± 3.8%). Perfluorobutane sulfonate (PFBS) concentrations were highly correlated with total PFASs concentrations and could be an indicator for the release of PFASs from this landfill. The release of short-chain PFAAs strongly depended on precipitation whereas concentrations of the other PFASs appeared to be controlled by partitioning. Overall, the CW treatment system removed 61% of total PFASs and 50-96% of individual PFASs. PFAAs were removed most efficiently in the reed bed (42-49%), likely due to the combination of sorption to soils and sediments and plant uptake, whereas most of the PFAA precursors (i.e. 5:3 fluorotelomer carboxylate (5:3 acid), N-substituted perfluorooctane sulfonamides (N-MeFOSAA and N-EtFOSAA)) were removed in the aeration lagoon (>55%) by biodegradation. The sedimentation tank and polishing ponds were relatively inefficient, with only 7% PFASs removal.

Abstract  A series of perfluorobutane sulfonate (PFBS)-related substances are produced as the alternatives to corresponding perfluorooctane sulfonate (PFOS). However, there is little reliable information about PFBS available for the whole ecotoxicology compartments. At present, its ecotoxicity of perfluorobutane sulfonate potassium (PFBSK) was selected as a typical PFBS chemical to investigate and evaluate its aquatic, terrestrial, microorganism and sediment toxicity according to the Organization for Economic Cooperation and Development (OECD) guideline under the framework of the REACH regulation. Meanwhile, the ecotoxicology hazard and risk for PFBSK and PFOS were compared comprehensively.

PFBSK did not show acute and chronic aquatic, microorganisms and terrestrial animal toxicity, while exhibited some terrestrial plants toxicity. The ecotoxicology of PFBSK decreased sharply except for terrestrial plants compared with PFOS. Especially, for acute and chronic aquatic ecotoxicity, PFBSK is lower than 100 times those of PFOS.

Although the similar terrestrial plants toxicity level was observed for PFBSK and PFOS, the lower risk of PFBSK was deduced for the reason that there was far less chances to be exposed and retained in the soil and sediment for its high water solubility and low adsorption.

In conclusion, PFBSK showed lower ecotoxicity hazard and risk than those of PFOS. PFBSK could be an environmental friendly alternative to PFOS.

Abstract  The environmental behavior of antimony (Sb) in soils is often considered to be similar to that of arsenic (As). Comparing the adsorption behavior of these two elements on soil minerals is important because both elements coexist in contamination areas. In this study, the differences in antimonate (Sb(V)) and arsenate (As(V)) adsorption reaction kinetics and isotherm characteristics on a poorly crystalline phyllomanganate (delta-MnO2) were studied. The potential mechanisms were identified using zeta potential, Fourier transform infrared spectrometry (FTIR), and X-ray photoelectron spectroscopy (XPS) analyses. The adsorption isotherm results indicated that the maximum adsorption capacity for As(V) was 1.5 times higher than that for Sb(V). The adsorption kinetics of Sb(V) and As(V) were well fitted using pseudo-first-order model, and the adsorption rate of Sb(V) and As(V) significantly depended on delta-MnO2 dosage and pH. At all tested pH values (3.0-9.0), the adsorption rate of As(V) was 4.0-7.7 times faster than that of Sb(V) at the same delta-MnO2 dosage and pH conditions. FTIR and XPS analysis confirmed that M (metal)-O was bonded with Sb(V) and As(V). The adsorption capacity and rate of As(V) were significantly higher than those of Sb(V), suggesting that delta-MnO2 had higher affinity toward As(V). The different adsorption behaviors of Sb(V) and As(V) onto delta-MnO2 should be considered in soils. (C) 2017 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

Abstract  Perfluorinated chemicals (PFASs) stem from a wide range of sources and have been detected in aquatic ecosystems worldwide, including the upper Midwest and the state of Minnesota in the USA. This study investigated whether fish with high body burden levels of PFASs in the Twin Cities Metro Areas showed any evidence of adverse effects at the level of the transcriptome. We hypothesized that fish with higher body burden levels of PFASs would exhibit molecular responses in the liver and testis that were suggestive of oxidative and general stress, as well as impaired reproduction. Concentrations of PFASs in largemouth bass varied significantly across the sampled lakes, with the lowest concentrations of PFASs found in fish from Steiger and Upper Prior Lakes and the highest concentrations found in fish from Calhoun and Twin Lakes. Largemouth bass with high PFAS concentrations exhibited changes in the expression of genes related to lipid metabolism, energy production, RNA processing, protein production/degradation and contaminant detoxification, all of which are consistent with biomarker responses observed in other studies with PFASs. However, given the wide range of genes that were differentially expressed across the lakes and the variability observed in the mechanisms through which biological processes were affected, it is unlikely that PFASs are the only stressors affecting largemouth bass in the Twin Cities Metro Areas lakes. Indeed, Twin Lake is affected by the Joslyn superfund site which contains polycyclic aromatic hydrocarbons, pentachlorophenol, polychlorinated biphenyls, and dioxins. These compounds are also expected to drive the transcriptomics responses observed, but to what degree is difficult to ascertain at this time.

Abstract  Gondogeneia antarctica is widely distributed off the western Antarctic Peninsula and is a key species in the Antarctic food web. In this study, we performed Illumina sequencing to produce a total of 4,599,079,601 (4.6Gb) nucleotides and a comprehensive transcript dataset for G. antarctica. Over 46 million total reads were assembled into 20,749 contigs, and 12,461 annotated genes were predicted by Blastx. The RNA-seq results after exposure to three pollutants showed that 658, 169 and 367 genes that were potential biomarkers of responses to pollutants for this species were specifically upregulated after exposure to PCBs (Polychlorinated biphenyls), PFOS (Perfluorooctanesulfonic acid) and PFOA (Perfluorooctanoic acid), respectively. These data represent the first transcriptome resource for the Antarctic amphipod G. antarctica and provide a useful resource for studying Antarctic marine species.

Abstract  A quantitative risk ranking model was developed for human exposure to emerging contaminants (EC) following treated municipal sewage sludge (biosolids) application to Irish agricultural land. The model encompasses the predicted environmental concentration (PEC) in soil, surface runoff, groundwater, and subsequent drinking water ingestion by humans. Human exposure and subsequent risk was estimated for 16 organic contaminants using a Monte Carlo simulation approach. Nonylphenols ranked the highest across three environmental compartments: concentration in soil (PECsoil), runoff (PECrunoff), and groundwater (PECgroundwater), which had mean values of 5.69mg/kg, 1.15x 10(-2) mu g/l, and 2.22x 10(-1) mu g/l, respectively. Human health risk was estimated using the LC50 (chemical intake toxicity ratio, (RR)) as a toxicity endpoint combined with PECrunoff and PECgroundwater. NP ranked highest for LC50 combined with PECrunoff and PECgroundwater (mean RR values 1.10x 10(-4) and 2.40x 10(-3), respectively). The model highlighted triclocarban and triclosan as ECs requiring further investigation. A sensitivity analysis revealed that soil sorption coefficient and soil organic carbon were the most important parameters that affected model variance (correlation coefficient -0.89 and -0.30, respectively), highlighting the significance of contaminant and soil properties in influencing risk assessments. This model can help to prioritize emerging contaminants of concern requiring vigilance in environmental compartments.

Abstract  The present study was aimed at the development of a strategy for removing and degrading perfluorohexanoic acid (PFHxA) from industrial process waters at concentrations in the range 60-200 mg L(-1). The treatment train consisted of nanofiltration (NF) separation followed by electrochemical degradation of the NF concentrate. Using a laboratory-scale system and working in the total recirculation mode, the DowFilm NF270 membrane provided PFHxA rejections that varied in the range 96.6-99.4% as the operating pressure was increased from 2.5 to 20 bar. The NF operation in concentration mode enabled a volume reduction factor of 5 and increased the PFHxA concentration in the retentate to 870 mg L(-1). Results showed that the increase in PFHxA concentration and the presence of calcium sulfate salts did not induce irreversible membrane fouling. The NF retentate was treated in a commercial undivided electrochemical cell provided with two parallel flow-by compartments separated by bipolar boron doped diamond (BDD) electrode, BDD counter anode, and counter cathode. Current densities ranging from 20 to 100 A m(-2) were examined. The electrochemical degradation rate of PFHxA reached 98% and was accompanied by its efficient mineralization, as the reduction of total organic carbon was higher than 95%. Energy consumption, which was 15.2 kWh m(-3) of treated NF concentrate, was minimized by selecting operation at 50 A m(-2). While most of the previous research on the treatment of perfluoroalkyl substances (PFASs) focused on the removal of perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS), these compounds have been phased out by chemical manufacturers. Our findings are relevant for the treatment of PFHxA, which appears to be one of the present alternatives to long-chain PFASs thanks to its lower bioaccumulative potential than PFOA and PFOS. However, PFHxA also behaves as a persistent pollutant. Moreover, our results highlight the potential of combining membrane separation and electrochemical oxidation for the efficient treatment of PFAS-impacted waters.

Abstract  Graphene-coated cobalt nanoparticles surface-functionalized with benzylamine groups (CoC-NH(2) nanomagnets) were shown to effectively enrich analytes for surface-assisted laser desorption/ionization mass spectrometry (affinity SALDI-MS) analysis. These CoC-NH(2) nanomagnets are highly suited for use with affinity SALDI-MS because their mean diameter of 30 nm, high specific surface area of 15 m(2) g(-1), and high-strength saturation magnetization of 158 emu g(-1) led to efficient extraction of analytes by magnetic separation, which in turn enabled excellent SALDI-MS performance. Surface modification of CoC nanomagnets with benzylamine groups increased the yield of peptide ions and decreased fragmentation of benzylpyridinium ions, so-called "thermometer ions" formed through soft ionization. The CoC-NH(2) nanomagnets were used to extract perfluorooctanesulfonate from large volumes of aqueous solutions by magnetic separation, which was identified directly by SALDI-MS analysis with high sensitivity even at the sub-part-per-trillion level (∼0.1 ng/L). The applicability of CoC-NH(2) nanomagnets in conjunction with SALDI-MS for the enrichment and detection of pentachlorophenol, bisphenol A, and polyfluorinated compounds (PFCs) with varying chain length, which are environmentally significant compounds, as well as small drugs, was also evaluated.

Abstract  Following recent rapid industrialization, China is now one of the largest producers and consumers of organic chemicals in the world. This is compounded by variable regulatory oversight with respect to storage, use and waste management of these chemicals and their byproducts. This review synthesizes the data on the distribution of selected persistent organic pollutants (POPs) in waters in China. Surface water heavily polluted with POPs is distributed in the Yangtze River Estuary, Pearl River Delta, Minjiang River Estuary, Jiulongjiang Estuary, Daya Bay, Taihu Lake, and the waterways of Zhejiang Province, where concentrations of Polycyclic aromatic hydrocarbons (PAHs), organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) frequently exceed both international and Chinese guideline values. These areas are mainly distributed along the southeast coast of China, within or downstream of major manufacturing districts, intensive agricultural basins, and other industrial centers. A comparison of the levels of OCPs in the aquatic environment of China with other indicative regions worldwide shows comparable levels of pollution (overall range from below detection limit (BDL) to 5104.8ng/L and regional means from 2.9-929.6ng/L). PAHs and PCBs pollution appear to be particularly serious in China (PAHs overall ranging from BDL to 474,000ng/L with regional means from 15.1-72,400ng/L; PCBs from BDL to 3161ng/L with regional means ranging from 0.2-985.2ng/L). There is as yet limited evidence of serious perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) pollution. We discuss major sources and processes responsible for high POP occurrence using a range of measures (including diagnostic ratios of different compounds), regulatory oversight and policy gaps in the control of POPs in China, and potential long-term health and ecological effects. We argue that water quality guidelines, pollution control measures and cleanup strategies for POPs in China should be urgently improved.

Abstract  Measurements of the surface tension, density and viscosity of aqueous solutions of n-oktyl-β-D-glucopiranoside (OGP) were made at 293 K. From the obtained results the Gibbs surface excess concentration of OGP at the water-air interface and its critical micelle concentration were determined. The Gibbs surface excess concentration of OGP used in the Gu and Zhu isotherm equation allowed us to determine the Gibbs standard free energy of OGP adsorption at the water-air interface. The Gibbs standard free energy of OGP adsorption was also determined on the basis of the Langmuir, Szyszkowski, Gamboa and Olea equations as well the surface tension of "hydrophobic" part of OGP and "hydrophobic" part-water interface tension. It appeared that there is an agreement between the values of Gibbs standard free energy of OGP adsorption at the water-air interface determined by using all the above mentioned methods. It also proved that standard free energy of OGP micellization determined from CMC is consistent with that obtained on the basis of the free energy of the interactions between the "hydrophobic" part of the OPG through the water phase.