Conversion of perfluoroalkyl acid (PFAA) precursors in the environment has been a hotspot research in recent years. This study firstly determined the spatial distribution of PFAAs and their precursors including 8:2 fluorotelomer unsaturated acid (8:2 FTUCA), perfluorooctane sulfoneamide (FOSA), and diperfluorooctane sulfonamido ethanol-based phosphate (di-SAmPAP), then investigated the conversion of the potential precursors in the seawater and sewage treatment plants (STPs) effluents. The results indicated that the target pollutants showed a typical concentration gradient from nearshore to offshore. And the obviously increased concentration of perfluorinated carboxylic acids (△[PFCAs]) after oxidation treatment can verify the existence of PFAA precursors in the seawater and STP effluents. The concentrations of PFCAs with carbon atom numbers 4-9 (PFCAC4-C9) revealed the most increase. Moreover, the levels of △[PFCAs] and the ratios of △[PFCAs] to their concentration before oxidation (△[PFCA]/[PFCA]before oxidation) indicated obvious spatial variations in the seawater and STP effluents. The higher levels of △[PFCAC4-C12] and the lower ratios of ∑△[PFCAC4-C12]/∑[PFAA]before oxidation were observed in the STP effluents, which implied that precursors might be decomposed during the sewage treatment process. These results suggested the STP effluents might have an important effect on the PFAAs levels of seawater.

Recently, the toxicity of sunscreen has received extensive attention due to their potential endocrine disrupting effect. In the present study, nitrogen and sulfur co-doped multi-walled carbon nanotubes loaded CuFe2O4 (NS-CNTs/CuFe2O4) catalyst was rationally designed and synthesized by co-precipitation method for the degradation of 2-phenylbenzimidazole-5-sulfonic acid (PBSA, a typical sunscreen addition). The catalyst was fully characterized by scanning electron microscope, transmission electron microscope, X-ray diffraction, Fourier transform infrared spectroscopy, nitrogen gas uptake, and X-ray photoelectron spectroscopy. Then the kinetics, pathways and mechanisms of catalytic degradation of PBSA were studied in NS-CNTs/CuFe2O4 activated peroxymonosulfate (PMS) solution. The catalyst showed high catalytic activity, stability and reusability in PBSA removal. The results of electron paramagnetic resonance (EPR) and quenching experiments suggested that sulfate radicals (SO4-) predominated in the activation of PMS by NS-CNTs/CuFe2O4. The synergistic effect between CuFe2O4 and NS-CNTs was proposed in PMS activation. In addition, eight degradation intermediates of PBSA were identified by liquid chromatography mass spectrometry (LC-MS), and degradation pathways were further proposed. Overall, this study provides insights of PBSA removal by NS-CNTs/CuFe2O4 activated PMS at ambient temperature. (C) 2016 Elsevier B.V. All rights reserved.

As one of the first generation of fluoroquinolone antibiotics, flumequine (FLU) has been detected ubiquitously in surface waters and municipal wastewaters. In light of FLU's possible adverse effects on aquatic species, the removal of this antibiotic has received worldwide attention. In this study, the kinetics, transformation products, mechanisms and toxicity variations of the ozonation process for FLU were systematically determined. The possible effects of solution pH, addition of inorganic ions, dissolved organic matter, and tert-butyl-alcohol (a radical scavenger), as well as the type of water matrices on FLU removal by ozonation, were studied from the perspective of the degradation kinetics. The data obtained suggested that ozone can be used as an effective oxidant for the fast removal of FLU from natural waters. Using liquid chromatography-mass spectrometry, a total of thirteen transformation products of FLU during ozonation were identified, and their specific reaction mechanisms were also proposed. The degradation pathways involving the hydroxylation, decarboxylation and defluorination were tentatively proposed. Meanwhile, the generation of three low-molecular-weight carboxylic acids was also observed. In addition, the potential toxicity of the transformation mixtures of FLU by ozone was evaluated. Overall, this paper can be a unique contribution to the systematic elucidation of the ozonation process of this antibiotic in water.

The occurrence of benzophenone-4 (BP-4) in water environments may pose a serious public health hazard due to its potential endocrine disrupting effects. In this work, the intermediates, probable degradation pathways and toxicity changes during ozonation of BP-4 in aqueous solution were systematically investigated. Results revealed that alkaline conditions favored the oxidation of BP-4. However, inorganic anions (Cl−, NO3−, SO42−), cations (K+, Ca2+, Mg2+) and humic acid had no remarkable effect on BP-4 removal within the tested concentrations. Ozonation was also effective for the fast removal of BP-4 in real waters. The TOC suggested a low mineralization rate, even after the complete BP-4 removal. Meanwhile, the treated mixtures exhibited an obvious inhibition to the bioluminescent bacteria Photobacterium phosphoreum, indicating the formation of transformation products with higher toxicities. Furthermore, fourteen products were identified by means of liquid chromatography-mass spectrometry. Notably, seven of them have not been reported previously. The quenching test indicated that the degradation processes probably were dominated by OH. Next, possible degradation pathways were proposed and further justified by theoretical calculations of frontier electron densities. This investigation will contribute to the systematic elucidation of the ozonation process of UV filters in aquatic environments.

Eighteen polyfluorinated dibenzo-p-dioxins (PFDDs) were synthesized by pyrolysis of fluorophenols. Using a 500 W Xe lamp as the light source, the PFDDs photodegradation kinetics in n-hexane were investigated. The photolysis reactions obeyed the pseudo-first-order rate equation, and higher fluorinated PFDDs tended to photolyze more slowly. Theoretically calculated parameters reflecting the molecular structural properties were used to develop a new model of PFDDs photolysis rates. The results indicated that the substitution pattern for fluorine atoms and the C-O bond length were major factors in the photolysis of PFDDs. We selected octafluorinated dibenzo-p-dioxin (OFDD) as a representative PFDDs to explore the influence of solvent on the photolysis rate of PFDDs, and the results indicated that neither the polarity nor donor hydrogen of organic solvents are independent influencing factors. Mechanistic pathways for the photolysis of OFDD in n-hexane were first studied. The results indicated that photodegradation of OFDD produces octafluorinated dihydroxybiphenyls, octafluorinated phenoxyphenols, and fluorinated phenols. The major pathway for photodegradation of OFDD was C-O bond cleavage. Defluorination reactions did not occur during the photolysis process.

Experiments were conducted to investigate the effect of four different carbon nanotubes single- and multi-walled carbon nanotubes (SWCNTs and MWCNTs) and hydroxylated and carboxylated multi-walled carbon nanotubes (OH-MWCNTs and COOH-MWCNTs) on Cd toxicity to the aquatic organism Daphnia magna. The acute toxicity results indicated that all CNTs could enhance the toxicity of Cd to D. magna. Furthermore, the filtrate toxicity and adsorption tests showed that the toxicity-increasing effect of SWCNTs and MWCNTs in the overall system was mainly caused by catalysts impurities from the pristine CNTs, whereas the greater adsorption of Cd onto OH-MWCNTs (30.52 mg/g) and COOH-MWCNTs (24.93 mg/g) was the key factor contributing to the enhanced toxicity. This result raised a concern that the metal catalyst impurities, adsorption capacities, and accumulation of waterborne CNTs were responsible for the toxicity of Cd to aquatic organism.

An efficient enzyme-assisted extraction procedure was developed and optimized for the extraction of polysaccharides from Flammulina Velutipes (FVPs). Based on the single-factor experiments, Response Surface Methodology (RSM) was used to estimate and optimize the experimental variables. The results showed that the optimal extraction conditions for the polysaccharides were extraction temperature 55.0 degrees C, extraction pH 5.24, and extraction time 3.4 h. Under these conditions, the experimental yield of polysaccharides was 8.60 +/- 0.22%, which was close with the predicted yield value (8.66%). In addition, the radicals scavenging activity of the FVPs were investigated in vitro. The results showed that FVPs possessed significant inhibitory effects on 1,1-Diphenyl-2-Picrylhydrazyl (DPPH) radical, hydroxyl radical and superoxide radical. These results suggested that enzyme-assisted extraction technology is a great extraction technology on the polysaccharides from F. velutipes, and FVPs could be a suitable natural antioxidant and may be the functional foods for humans.

With the increasing applications of carbon nanotubes (CNTs) worldwide, considerable concerns have been raised regarding their inevitable releases into natural waters and ecotoxicity. It was supposed that CNTs may interact with some existing pollutants like zinc in aquatic systems and exhibit different effects when compared with their single treatments. However, data on their possible combined toxicity on aquatic species are still lacking. Moreover, the interactions of Zn with different functionalized CNTs may be distinct and thereby lead to diverse results. It is like that functional groups play a vital role in illustrating the differences in toxicity among various CNTs. In this study, the single and joint effects of multi-walled carbon nanotubes (MWCNTs) and two MWCNTs functionalized with carboxylation (COOH-MWCNTs) or hydroxylation (OH-MWCNTs) in the absence or presence of zinc (Zn) on antioxidant status and histopathological changes in Carassius auratus were evaluated. Synergistic effect was tentatively proposed for joint-toxicity action, which was supported by apparently observed oxidative stress and histopathological changes in joint exposure groups. The integrated biomarker response index was calculated to rank the toxicity order, from which the conclusion of synergistic effect was strengthened. Regarding differences among various CNTs, our data showed that OH-MWCNTs and COOH-MWCNTs were more stressful to fish than raw MWCNTs. This finding sustained that functionalization is an important factor in nanotoxicity, which may serve as clues for future design and application of CNTs. Overall, these results provided some valuable toxicological data on the joint effects of CNTs and heavy metals on aquatic species, which can facilitate further understanding on the potential impacts of other coexisting pollutants in the culture of freshwater fish.

Diethyl phthalate (DEP), a plasticizer widely used in chemical industry, has been classified as an endocrine disruptor. Therefore, it is urgent to develop methods for degradation of DEP to minimize its ecological risk. In this study, copper ferrite decorated multi-walled carbon nanotubes magnetic nanoparticles (CuFe2O4/MWCNTs MNPs) were prepared by sol-gel combustion method as catalysts for the degradation of DEP. The catalysts were characterized by scanning electron microscope, transmission electron microscope, Fourier transform infrared spectroscopy, nitrogen gas uptake, X-ray diffraction, and X-ray photoelectron spectroscopy. Catalytic degradation of DEP by persulfate (PS) was investigated with various influencing factors including catalyst loading, PS concentrations, temperature and pH. Furthermore, the CuFe2O4/MWCNTs MNPs showed high catalytic activity, stability and recyclability in DEP removal. Especially, leaching of metal ions from reused CuFe2O4/MWCNTs was negligible (concentration < 0.4%), indicating the resistance to oxidation. The electron paramagnetic resonance analysis confirmed that the addition of CuFe2O4/MWCNTs into PS system can accelerate the generation of center dot OH and SO4-center dot, and the quenching experiments further certified the catalytic reaction was predominated by SO4-center dot. The degradation intermediates were identified and the pathways were proposed. Overall, this study provides practical knowledge for DEP removal by CuFe2O4/MWCNTs activated PS at ambient temperature. (C) 2016 Elsevier B.V. All rights reserved.

Decomposition of perfluorocarboxylic acids (PFCAs) is of great significance due to their global distribution, persistence and toxicity to organisms. In this study, the photodegradation of a series of PFCAs (∼C2C12) in water by a medium-pressure mercury lamp was experimentally and theoretically examined. We found that photolysis of PFCAs all follow pseudo-first-order kinetics with the rate constant (kapp) increasing with carbon chain lengths, except for trifluoroacetic acid (TFA) which cannot be degraded by the polychromatic irradiation. Product analysis showed that the PFCAs were mainly decomposed into shorter carbon chain length PFCAs in a stepwise manner, with the accumulation of TFA and fluoride ions as the end products. Moreover, a small amount of perfluoroolefins (CnF2n) was determined as gas-phase products. Wiberg bond order calculations confirmed the cleavage of the CC bond between carboxylic carbon and the adjacent carbon as the first reaction step, and density functional theory-based calculations revealed that kapp value is correlated with some molecular structural parameters. In the case of mixture irradiation, the evolution profiles of individual PFCAs were different from that in single-component systems, due to the dynamic balance between production and degradation. This work reveals the main molecular descriptors controlling the degradation rate of different PFCAs species, and improves the general understanding on the photodegradation mechanisms, which will provide useful information for future researches.

Cadmium (Cd) and Perfluorooctane sulfonate (PFOS) have been detected in aquatic environment. In this study, we investigated the acute effect, bioaccumulation and oxidative stress status in the aquatic oligocheate Limnodrilus hoffmeisteri after exposure to Cd and PFOS at different pH values. In the studied pH range, acute Cd toxicity was significantly enhanced with pH increasing from 6.2 to 8.0, and the 48h-EC50 of Cd was (significantly) decreased in the presence of PFOS. Bioaccumulation analysis results show that the accumulated Cd/PFOS in single exposure group increased with increasing exposure concentrations, and co-exposure makes internal Cd concentration significantly lowered for Cd(0.1) group at pH 8.0. Significant changes in superoxide dismutase activity, glutathione level and malondialdehyde content were observed in single and combined treatments. Based on IBR value, single Cd and PFOS exposure caused largest damage to the antioxidant defense system at pH 8.0 and pH 6.2, respectively, while the harmful effects of joint exposure were always the “compromise” between single Cd and PFOS exposure. This work could provide useful information for the risk assessment of co-exposure to perfluorinated compounds and heavy metals in natural environment.

By using CNTs functionalized by oxygenic functional groups ( COOH or OH) as the carbon source, novel catalysts of nitrogen (N) and sulfur (S) co-doped multi-walled carbon nanotubes (CNTs) were prepared for the first time by thermal decomposition. The obtained CNTs were characterized by SEM, TEM, BET, XPS, XRD, FT-IR and Raman spectroscopy. Additionally, the new material was used as a catalyst for the activation of peroxymonosulfate (PMS) for the degradation of benzophenone-4 (BP-4). Results indicated that the COOH group plays an important role in the S doping process. Moreover, binary (N and S)-doped CNT-COOH (NS-CNT-COOH) exhibited a notably enhanced catalytic activity towards PMS for degrading BP-4. This activity level was approximately five-fold greater than that of singly (N)-doped CNT-COOH and binary (N and S)-doped CNT, and it even exceeded that of the metal catalyst CuFe2O4. The enhanced catalytic performance was attributed to the active sites generated by the introduced pyridinic and pyrrolic N atoms and thiophenic S atoms. The effects of various factors on the catalytic activity of NS-CNT-COOH were studied. Results revealed that the degradation efficiency of BP-4 increased with catalyst load, oxidant concentration and reaction temperature. In contrast, NS-CNT-COOH exhibited no remarkable catalytic activity towards peroxodisulfate (PDS) and H2O2. In the case of the NS-CNT-COOH/PMS system, a possible pathway for BP-4 degradation was proposed and based on detected intermediates. The mechanism was justified by theoretical calculations of the frontier electron densities, which have not been reported previously. Furthermore, mineralization, toxicity, stability and reusability tests suggested that the developed catalyst, NS-CNT-COOH, holds promise for practical application. (C) 2016 Elsevier B.V. All rights reserved.

The thermal decomposition of Nafion N117 membrane, a typical perfluorosulfonic acid membrane that is widely used in various chemical technologies, was investigated in this study. Structural identification of thermolysis products in water and methanol was performed using liquid chromatography-electrospray ionization-tandem mass spectrometry (LC/ESI-MS/MS). The fluoride release was studied using an ion-chromatography system and the membrane thermal stability was characterized by thermogravimetric analysis. Notably, several types of perfluorinated compounds (PFCs) including perfluorocarboxylic acids were detected and identified. Based on these data, a thermolysis mechanism was proposed involving cleavage of both the polymer backbone and its side chains by attack of radical species. This is the first systematic report on the thermolysis products of Nafion by simulating its high-temperature operation and disposal process via incineration. The results of this study indicate that Nafion is a potential environmental source of PFCs, which have attracted growing interest and concern in recent years. Additionally, this study provides an analytical justification of the LC/ESI-MS/MS method for characterizing the degradation products of polymer electrolyte membranes. These identifications can substantially facilitate an understanding of their decomposition mechanisms and offer insight into the proper utilization and effective management on these membranes.

This study found that decabromodiphenyl ether (BDE 209) could be oxidized effectively by potassium permanganate (KMnO4) in sulfuric acid medium. A total of 15 intermediate oxidative products were detected. The reaction pathways were proposed, which primarily included cleavage of the ether bond to form pentabromophenol. Direct oxidation on the benzene ring also played an important role because hydroxylated polybrominated diphenyl ethers (PBDEs) were produced during the oxidation process. The degradation occurred dramatically in the first few minutes and fitted pseudo-first-order kinetics. Increasing the water content decelerated the reaction rate, whereas increasing the temperature facilitated the reaction. In addition, density functional theory (DFT) was employed to determine the frontier molecular orbital (FMO) and frontier electron density (FED) of BDE 209 and the oxidative products. The theoretical calculation results confirmed the proposed reaction pathways.

Tetrabromobisphenol A (TBBPA) is one of the most widely used brominated flame retardants and has attracted more and more attention. In this work, the parent TBBPA with an initial concentration of 100 mg/L was completely removed after 6 min of ozonation at pH 8.0, and alkaline conditions favored a more rapid removal than acidic and neutral conditions. The presence of typical anions and humic acid did not significantly affect the degradation of TBBPA. The quenching test using isopropanol indicated that direct ozone oxidation played a dominant role during this process. Seventeen reaction intermediates and products were identified using an electrospray time-of-flight mass spectrometer. Notably, the generation of 2,4,6-tribromophenol was first observed in the degradation process of TBBPA. The evolution of reaction products showed that ozonation is an efficient treatment for removal of both TBBPA and intermediates. Sequential transformation of organic bromine to bromide and bromate was confirmed by ion chromatography analysis. Two primary reaction pathways that involve cleavage of central carbon atom and benzene ring cleavage concomitant with debromination were thus proposed and further justified by calculations of frontier electron densities. Furthermore, the total organic carbon data suggested a low mineralization rate, even after the complete removal of TBBPA. Meanwhile, the acute aqueous toxicity of reaction solutions to Photobacterium Phosphoreum and Daphnia magna was rapidly decreased during ozonation. In addition, no obvious difference in the attenuation of TBBPA was found by ozone oxidation using different water matrices, and the effectiveness in natural waters further demonstrates that ozonation can be adopted as a promising technique to treat TBBPA-contaminated waters.

In recent years, flumequine (FLU) has been ubiquitously detected in surface waters and municipal wastewaters. In light of its potential negative impacts to aquatic species, growing concern has been arisen for the removal of this antibiotic from natural waters. In this study, the kinetics, degradation mechanisms and pathways of aqueous FLU by persulfate (PS) oxidation were systematically determined. Three common activation methods, including heat, Fe2+ and Cu2+, and a novel heterogeneous catalyst, namely, polyhydroquinone-coated magnetite/multi-walled carbon nanotubes (Fe3O4/MWCNTs/PHQ), were investigated to activate PS for FLU removal. It was found that these three common activators enhanced FLU degradation obviously, while several influencing factors, such as solution pH, inorganic ions (especially HCO3- at 5 mmol/L) and dissolved organic matter extracts, exerted their different effects on FLU removal. The catalysts were characterized, and an efficient catalytic degradation performance, high stability and excellent reusability were observed. The measured total organic carbon levels suggested that FLU can be effectively mineralized by using the catalysts. Radical mechanism was studied by combination of the quenching tests and electron paramagnetic resonance analysis. It was assumed that sulfate radicals predominated in the activation of PS with Fe3O4/MWCNTs/PHQ for FLU removal, while hydroxyl radicals also contributed to the catalytic oxidation process. In addition, a total of fifteen reaction intermediates of FLU were identified, from which two possible pathways were proposed involving hydroxylation, decarbonylation and ring opening. Overall, this study represented a systematical evaluation regarding the transformation process of FLU by PS, and showed that the heterogeneous catalysts can efficiently activate PS for FLU removal from the water environment. (C) 2015 Elsevier Ltd. All rights reserved.

Tetrabromobisphenol A (TBBPA) is a well-known brominated flame retardant. It has been detected in the environment and shows high acute toxicity to different organisms at high concentrations. In this work, the effects of pH and dimethyl sulfoxide (DMSO) on the acute toxicity of TBBPA to Daphnia magna and Limnodrilus hoffmeisteri were tested, and the oxidative stress induced by TBBPA in livers of Carassius auratus was assessed using four biomarkers. The integrated biomarker response (IBR) was applied to assess the overall antioxidant status in fish livers. Moreover, fish tissues (gills and livers) were also studied histologically. The results showed that low pH and DMSO enhanced the toxicity of TBBPA. Furthermore, changes in the activity of antioxidant enzymes and glutathione level suggested that TBBPA generates oxidative stress in fish livers. The IBR index revealed that fish exposed to 3mg/L TBBPA experienced more serious oxidative stress than exposed to acidic or alkaline conditions. The histopathological analysis revealed lesions caused by TBBPA. This study provides valuable toxicological information of TBBPA and will facilitate a deeper understanding on its potential toxicity in realistic aquatic environments.

Aldose reductase (ALR2) inhibitors are promising agents for chronic diabetic complication therapy by pre?venting the reduction of glucose in the polyol pathway,which promotes to develop novel ALR2 inhibitors. Two kinds of techniques ,comparative molecular field analysis (CoMFA) and comparative molecular similarity indices analysis (CoMSIA),were employed for studying a series of 5-arylidene-2,4-thiazolidinediones as aldose reductase inhibitors. With the strategies of common substructure-based alignment and field-fit alignment ,the lowest energy conforma?tions were used to develop the ligand-based models of three-dimensional quantitative structure-activity relationship (3D-QSAR). The bioactive conformation obtained by docking all 5-arylidene-2,4-thiazolidinediones derivatives into the active site of aldose reductase (PBD ID:1ah3) was applied for the development of receptor-based model. Statistically sig?nificant model of ligand-based 3D-QSAR from the common substructure-based alignment exhibited the best predictive power (CoMFA r2=0.922,q2=0.707;CoMSIA r2=0.917,q2=0.762). The model was further confirmed by analyzing 12 sets of compounds with diverse structure. The results showed high predictive r2 values of 0.824 for CoMFA and 0.883 for CoMSIA respectively. The molecular docking analysis revealed that both CoMFA and CoMSIA contour maps for steric,electrostatic,hydrophobic,and hydrogen-bonding interactions matched well. The combination of CoMFA and CoMSIA with molecular docking is helpful to understand the interaction and the structure-activity relationship between ALR2 and its inhibitor. The present results provide a valuable guidance for rationally designing ARL2 inhibitors.