Ruijuan Qu

Degradation of flumequine in aqueous solution by persulfate activated with common methods and polyhydroquinone-coated magnetite/multi-walled carbon nanotubes catalysts

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, Fe(2+) and Cu(2+), 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.

Metal accumulation and oxidative stress biomarkers in liver of freshwater fish Carassius auratus following in vivo exposure to waterborne zinc under different pH values

In this study, laboratory experiments were conducted to investigate the combined effect of zinc and pH on metal accumulation and oxidative stress biomarkers in Carassius auratus. Fish were exposed to 0.1 and 1.0mg Zn/L at three pH values (5.0, 7.25, 9.0) for 3, 12, and 30 d. After each exposure, the contents of three trace elements (Zn, Fe and Cu) were determined in liver. Generally, longer exposure to zinc (12d and 30 d) increased hepatic Zn and Cu deposition, but decreased Fe content. Increasing accumulation of Zn in the tissue was also observed with increasing zinc concentration in the exposure medium. Moreover, hepatic antioxidant enzyme activities including superoxide dismutase (SOD), catalase (CAT) and glutathione peroxidase (GPx), together with the level of glutathione (GSH) were measured to evaluate the oxidative stress status. The decreases in the four measured biochemical parameters after 3d exposure might reflect the failure of the antioxidant defense system in neutralizing the ROS generated during the metabolic process, while the recovery of the antioxidants at days 12 and 30 suggested a possible shift toward a detoxification mechanism. With regard to the influence of pH on zinc toxicity, the general observation was that the living environment became more stressful when the water conditions changed from an acidic state toward a near-neutral or alkaline state.

Metal accumulation and antioxidant defenses in the freshwater fish Carassius auratus in response to single and combined exposure to cadmium and hydroxylated multi-walled carbon nanotubes

The effects of cadmium, hydroxylated multi-walled carbon nanotubes, and their mixture on metal accumulation and antioxidant defenses were studied using the goldfish Carassius auratus as the test organism. The fish were exposed to 0.1 mg/L Cd, 0.5 mg/L OH-MWCNTs, or 0.1 mg/L Cd+0.5 mg/L OH-MWCNTs for 3 and 12 days. Then, the Cd concentration was determined in the gill, liver and muscle. Moreover, hepatic antioxidant enzyme activity (superoxide dismutase, catalase and glutathione peroxidase), glutathione level and malondialdehyde content were also measured. A continuous accumulation of Cd was observed throughout the experimental period. Cd accumulation in tissues occurred in the following order: gill>liver>muscle at 3 days and liver>gill>muscle at 12 days. The concentrations of Cd in the livers of fish exposed to the combination of Cd+OH-MWCNTs were significantly higher than those in fish exposed to either single chemical after 12 d of exposure. Meanwhile, the mixture evoked severe oxidative stress in the exposed fish, as indicated by significant inhibition of SOD, CAT and GPx activity, a remarkable decrease in GSH level, and simultaneous elevation of MDA content. These results suggested that the effect of the combined factors on metal accumulation and oxidative stress biomarkers was more obvious than that of single factors at longer exposure durations.

Comparative antioxidant status in freshwater fish Carassius auratus exposed to six current-use brominated flame retardants: A combined experimental and theoretical study

Decabromodiphenyl ether (BDE-209) and several non-polybrominated diphenyl ether (PBDE) brominated flame retardants (BFRs), such as tetrabromobisphenol A (TBBPA), hexabromocyclododecane (HBCD), decabromodiphenyl ethane (DBDPE), hexabromobenzene (HBB) and pentabromotoluene (PBT), are persistent halogenated contaminants ubiquitously detected in aquatic systems. However, data on comparative toxicological effects of these BFRs are lacking for fish. In this study, a combined experimental and theoretical approach was used to compare and analyze the effects of these BFRs on biochemical biomarkers in liver of Carassius auratus injected intraperitoneally with different doses (10 and 100mg/kg) for 7, 14 and 30 days. Oxidative stress was evoked evidently for the prolonged exposure, represented by the significantly altered indices (superoxide dismutase, catalase, glutathione peroxidase, reduced glutathione, and malondialdehyde). The integrated biomarker response (IBR) index ranked biotoxicity as: PBT>HBB>HBCD>TBBPA>BDE-209>DBDPE. Quantum chemical calculations (electronic parameters, frontier molecular orbitals, and Wiberg bond order) were performed for theoretical analysis. Notably, some descriptors were correlated with the toxicity order, probably implying the existence of a potential structure-activity relationship when more BFRs were included. Besides, theoretical calculations also provided some valuable information regarding the molecular characteristics and metabolic pathways of these current-use BFRs, which may facilitate the understanding on their environmental behavior and fate. Overall, this study adopted a combined experimental and theoretical method for the toxicological determination and analysis of the BFRs, which may also be considered in future ecotoxicological studies.

The toxicity of cadmium to three aquatic organisms (Photobacterium phosphoreum, Daphnia magna and Carassius auratus) under different pH levels

This study investigated the effect of pH on cadmium toxicity to three aquatic organisms: Photobacterium phosphoreum, Daphnia magna and Carassius auratus. The acute toxicity of Cd(2+) to P. phosphoreum and D. magna at five pH values (5.0, 6.0, 7.0, 8.0, and 9.0) was assessed by calculating EC50 values. We determined that Cd(2+) was least toxic under acidic conditions, and D. magna was more sensitive to the toxicity of Cd than P. phosphoreum. To evaluate Cd(2+)-induced hepatic oxidative stress in C. auratus at three pH levels (5.0, 7.25, 9.0), the activity of antioxidant enzymes (superoxide dismutase, catalase and glutathione peroxidase), the level of glutathione and the malondialdehyde content in the liver were measured. Oxidative damage was observed after 7d Cd exposure at pH 9.0. An important finding of the current research was that Cd(2+) was generally more toxic to the three test organisms in alkaline environments than in acidic environments.

Oxidative Degradation of Decabromodiphenyl Ether (BDE 209) by Potassium Permanganate: Reaction Pathways, Kinetics, and Mechanisms Assisted by Density Functional Theory Calculations

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.

Development of a model to predict the effect of water chemistry on the acute toxicity of cadmium to Photobacterium phosphoreum

Cadmium (Cd) compounds are widely distributed toxic environmental and industrial pollutants, and they may bring danger to growth and development of aquatic organisms. The effects of Ca(2+) (as CaCl2), Mg(2+) (as MgSO4), K(+) (as KCl), pH and complexants (EDTA, the commercial DOM, and three homemade DOMs) on Cd toxicity to Photobacterium phosphoreum were evaluated in standardized 15 min acute toxicity tests. Increases in Ca(2+) concentration resulted in higher EC50 values, indicating the competition between the two ions for uptake sites at the biotic ligand. Increased waterborne Mg(2+) also reduced Cd toxicity, but to a slightly lesser degree compared with Ca(2+). The overall decline in EC50 data with increasing K(+) in test solutions suggested that Cd toxicity was enhanced at larger K(+) concentration. The toxicity alleviation by H(+) was observed over the tested pH range of 5.0-9.0. Additions of complexing agents into the exposure water reduced Cd bioavailability via complexation of Cd(2+), and complexants from different sources displayed different protective effect. The influence of these toxicity modifying factors was finally incorporated into a model that can predict acute cadmidum toxicity for Photobacterium phosphoreum. After validation with laboratory and natural waters, the developed model could support efforts to improve the ecological relevance of presently applied risk assessment procedures.

Toxicity assessment on three direct dyes (D-BLL, D-GLN, D-3RNL) using oxidative stress bioassay and quantum parameter calculation

Textile dyes and dye industrial effluents are widely known for esthetic and toxicity problems. The toxicity of three direct dyes, Direct Blending Rebine (D-BLL), Direct Blending Scarlet (D-GLN), and Direct Blending Yellow (D-3RNL), were examined by the antioxidase and lipid peroxide index. Fish (Carassius auratus) were exposed to 100mg/L test compounds or injected with 200μg/kg corresponding dyes, and then samples of liver were collected at different times (0.5, 1, 3, 5, 7, 10, 13, 17 and 22d ) for analysis of superoxide dismutase (SOD), catalase (CAT), and contents of malondialdehyde (MDA). There is an obvious difference between two poisoning conditions and results indicated injection pattern have a more sensitive response. Besides, SOD, CAT and MDA levels displayed different variation trend following the prolonged duration, implying that dye metabolism generated less toxic or more active substance. The comparison among their intensity of enzyme inhibition showed that the toxicity order is D-BLL>D-GLN>D-3RNL. Additionally, three direct dye molecules were optimized based on the quantum mechanical charge density of a solute molecule interacting with a continuum description of the solvent (SMD) of Self-consistent Reaction Field Theory (SCRF) on B3LYP/LAN2BM level and the stable configurations were obtained. Wiberg bond orders were analyzed and atom in molecule (AIM) 2000 program was employed to estimate the interaction between atoms. The possible degradation pathways and toxicities were speculated based on the computations. The calculation is consistent with the experimental results and analysis.

Effect of different carbon nanotubes on cadmium toxicity to Daphnia magna: The role of catalyst impurities and adsorption capacity.

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.

Rapid Removal of Tetrabromobisphenol A by Ozonation in Water: Oxidation Products, Reaction Pathways and Toxicity Assessment.

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.