Activation of peroxymonosulfate by biochar-supported Fe3O4 derived from oily sludge to enhance the oxidative degradation of tetracycline hydrochloride.

Carbon materials used for catalysis in advanced oxidation processes tend to be obtained from cheap and readily available raw materials. We constructed a carbon material, OSC@Fe3O4, by loading Fe3O4 onto the pyrolyzed hazardous waste oily sludge. OSC@Fe3O4 was then used to activate peroxymonosulfate (PMS) for the removal of tetracycline hydrochloride (TTCH) from water. At 298 K, 0.2 g⋅L-1 of catalyst and 0.3 g⋅L-1 of PMS, the reaction rate constant of the OSC@I-2/PMS system reached 0.079 min-1, with a TTCH removal efficiency of 92.6%. The degradation efficiency of TTCH remained at 81% after five cycles. The specific surface area and pore volume of OSC@I-2 were 263.9 m2⋅g-1 and 0.42 cm3⋅g-1, respectively, which improved the porous structure of the carbon material and provided more active points, thus improving the catalytic performance. N and S were doped into the oily sludge carbon due to the presence of N- and S-containing compounds in the raw oily sludge. N and S doping led to more electron-rich sites with higher negative charges in OSC@I-2 and gave the oily sludge carbon a higher affinity to PMS, thereby promoting its ability to activate PMS. Sulfate radicals (SO4•‾) played a dominant role in the degradation of TTCH, with demethylation and the breaking of double bonds being a possible degradation pathway. A biotoxicity test showed that the microbial toxicity of the degradation intermediates was significantly reduced. This work provides a strategy for the application of PMS-based catalysts derived from waste carbon resources.

Repairing of rutin to the toxicity of combined F-53B and chromium pollution on the biofilm formed by Pseudomonas aeruginosa.

The wastewater discharge from the process of chrome plating, which contains 6:2 chlorinated polyfluorinated ether sulfonate (F-53B) and chromium (Cr), may be toxic to biofilm. In this study we found that the biofilm formed by Pseudomonas aeruginosa PAO1 was inhibited by exposure to a combination of F-53B and Cr(VI). The combined pollution damaged the cell membranes and the structure of the biofilm, and inhibited the production of the Pseudomonas quinolone-based signal, which affected biofilm formation. Moreover, the secretion of extracellular polymeric substances decreased as a result of this combined exposure. Exposure to F-53B and Cr(VI) individually or in combination could induce the excessive accumulation of intracellular reactive oxygen species (ROS), and the ROS positive rate of the bacteria increased under the treatment with 0.2 mmol/L of Cr(VI) and 250 nmol/L of F-53B, respectively. In addition, the activities of superoxide dismutase (SOD) and catalase (CAT) were enhanced for scavenging ROS in the bacteria that were exposed to Cr(VI) and F-53B. As an antioxidant, rutin was used to repair the toxicity of Cr(VI) and F-53B towards the biofilm formed by the bacteria. When rutin was added to the bacteria medium, with either Cr(VI) or F-53B as pollutant, or with the combined pollutants, the extracellular protein content of the bacteria recovered to 0.84, 0.94, and 0.85 times that of the control, respectively. Meanwhile, the accumulation of ROS and the activities of SOD and CAT decreased, which indicated that the addition of rutin can alleviate the oxidative stress and promote the antioxidant stress system.

Outer membrane vesicles mediated horizontal transfer of an aerobic denitrification gene between Escherichia coli.

Bacterial genetic material can be horizontally transferred between microorganisms via outer membrane vesicles (OMVs) released by bacteria. Up to now, the application of vesicle-mediated horizontal transfer of "degrading genes" in environmental remediation has not been reported. In this study, the nirS gene from an aerobic denitrification bacterium, Pseudomonas stutzeri, was enclosed in a pET28a plasmid, transformed into Escherichia coli (E. coli) DH5α and expressed in E. coli BL21. The E. coli DH5α released OMVs containing the recombination plasmid pET28a-nirS-EGFP. When compared with the free pET28a-nirS-EGFP plasmid's inability to transform, nirS in OMVs could be transferred into E. coli BL21 with the transformation frequency of 2.76 × 106 CFU/g when the dosage of OMVs was 200 µg under natural conditions, and nirS could express successfully in recipient bacteria. Furthermore, the recipient bacteria that received OMVs containing pET28a-nirS-EGFP could produce 18.16 U/mL activity of nitrite reductase.

Degradation and effect of 6:2 fluorotelomer alcohol in aerobic composting of sludge.

Perfluoroalkyl carboxylates (PFCAs) is toxic to the environment and human health. However, the degradation characteristics of fluorotelomer alcohols (FTOHs), precursors of PFACAs biodegradation, in the sludge during aerobic composting remain unclear. In this study, the degradation characteristics of 6:2 FTOH in sewage sludge by composting were researched and the influences of 6:2 FTOH on the composting process and microbial communities of the sludge were evaluated. After 52 days of composting, 6:2 FTOH retained only 0.73% of its original concentration, and its half-life was less than 1 d; 6:2 FTOH was degraded finally to perfluorohex unsaturated acid, perfluoropentanoic acid, 5:3 polyfluorinated acid (FTCA), 4:3 FTCA, and perfluorobutanoic acid through two pathways; and 6:2 FTCA and 6:2 fluorotel unsaturated acid were the intermediate products. Notably, dosing with 6:2 FTOH affected the composting process of sewage sludge. Additionally, 50 mg/kg 6:2 FTOH resulted in a decrease in the microbial richness and diversity of sludge compost. When compared with the compost without 6:2 FTOH, the proportion of Proteobacteria had increased, and the proportion of Firmicutes had decreased as the concentration of 6:2 FTOH increased. The negative effect of a dosage of 50 mg/kg 6:2 FTOH was more obvious than the effect of other treatments. This study expanded our understanding of the risk of sludge contaminated by 6:2 FTOH being used as a fertilizer after composting.

New application of rutin: Repair the toxicity of emerging perfluoroalkyl substance to Pseudomonas stutzeri.

Per- and polyfluoroalkyl substances (PFASs) are toxic to microorganisms, thereby affecting microbial communities in sludge and soil, but how to repair the toxicity of microorganisms remains unclear. In this study, rutin, an antioxidant, was added into a culture medium with an aerobic denitrification bacteria, Pseudomonas stutzeri, under the exposure of sodium perfluorononyloxy-benzenesulfonate (OBS) to evaluate the repair mechanisms of rutin to the toxicity of OBS to the bacteria. The results showed that rutin could repair the damage of OBS to cell structures, and reduce the death rates of the bacteria under OBS exposure. The dosage of rutin reduced the effect on the inhibition of denitrification ability of P. stutzeri under OBS exposure. Compared with the bacteria exposed to single OBS, the dosage of rutin resulted in that the death rates recovered from 96.2% to 66.4%, the growth inhibition rate decreased from 46.5% to 15.8%, the total nitrogen removal rate recovered from 66.9% to 100%, and the NO2- content recovered from 34.5 mg/L to 0.22 mg/L. The expressions of key denitrification genes (napA, nirS, norB, nosZ) were recovered after adding rutin under OBS exposure. Rutin changed the positive rate of reactive oxygen species, the relative superoxide dismutase and catalase activities in the bacteria which exposed to OBS. The mechanism by which rutin repaired the toxicity of OBS to P. stutzeri related to inhibiting the activities of antioxidant and denitrification enzymes rather than affecting the expressions of genes involved in these enzymes. This study sheds light on the repair method of micro-organics and reveals the repair mechanisms under PFASs exposure.

Toxic effect of perfluorooctane sulfonate on plants in vertical-flow constructed wetlands.

Per-and polyfluoroalkyl substances (PFASs) can be taken up and bioaccumulated in plants, but the toxic mechanisms of PFASs on wetland plants are still unclear. In present study, the toxic influences of perfluorooctane sulfonate (PFOS) on Eichhornia crassipes (E. crassipes) and Cyperus alternifolius (C. alternifolius) in a vertical-subsurface-flow constructed wetland were evaluated. The results showed that E. crassipes was more tolerant to PFOS stress than C. alternifolius, and the growth and chlorophyll synthesis of the two plants were promoted by low concentration (<0.1 mg/L) of PFOS, and the chlorophyll synthesis was inhibited by high concentration (10 mg/L) of PFOS but the growth did not change obviously. The catalase activity and malondialdehyde content in the leaves of the two plants increased, peroxidase activity decreased under exposure to high concentrations of PFOS, and superoxide dismutase activity did not change. Under PFOS stress, the membrane of plant leaves and the cell structure of the two wetland plants were destroyed, and the mitochondrial contour of root cells became incomplete. Tanscriptomic analysis showed that the expression levels of genes related to cell wall formation, the cell apoptosis pathway, material synthesis, and metabolism in the plants were changed by PFOS. Analysis in fluorogenic quantitative real time polymerase chain reaction (RT-qPCR) also confirmed that the photosynthesis system of E. crassipes was inhibited, while that of C. alternifolius was promoted.

Toxicity of perfluorooctane sulfonate on Phanerochaete chrysosporium: Growth, pollutant degradation and transcriptomics.

As a persistent organic pollutant listed in the Stockholm Convention, perfluorooctane sulfonate (PFOS) is extremely refractory to degradation under ambient conditions. Its potential ecotoxicity has aroused great concerns and research interests. However, little is known about the toxicity of PFOS on fungus. In this study, the white rot fungus Phanerochaete chrysosporium (P. chrysosporium) was adopted to assess the toxicity of PFOS in liquid culture. The addition of 100 mg/L PFOS potassium salt significantly decreased the fungal biomass by up to 76.4% comparing with un-amended control during the incubation period. The hyphostroma of P. chrysosporium was wizened and its cell membrane was thickened, while its vesicle structure was increased, based on the observation with scanning electron microscope (SEM) and transmission electron microscope (TEM). Nevertheless, the PFOS dosage of below 100 mg/L did not show a considerable damage to the growth of P. chrysosporium. The degradation of malachite green (MG) and 2,4-dichlorophenol (2,4-DCP) by P. chrysosporium was negatively affected by PFOS. At the initial dosage of 100 mg/L PFOS, the decolorization efficiency of MG and the degradation efficiency of 2,4-DCP decreased by 37% and 20%, respectively. This might be attributed to the inhibition of PFOS on MnP and LiP activities. The activities of MnP and LiP decreased by 20.6% and 43.4%, respectively. At a high dosage PFOS (100 mg/L), P. chrysosporium could show a high adsorption of MG but lose its pollutant degradation ability. Transcriptome analysis indicated that PFOS contamination could lead to the change of gene expression in the studied white rot fungus, and the genes regulating membrane structure, cell redox process, and cell transport, synthesis and metabolism were impacted. Membrane damage and oxidative damage were the two main mechanisms of PFOS' toxicity to P. chrysosporium.

Simultaneous Decolorization and Biohydrogen Production from Xylose by Klebsiella oxytoca GS-4-08 in the Presence of Azo Dyes with Sulfonate and Carboxyl Groups.

Biohydrogen production from the pulp and paper effluent containing rich lignocellulosic material could be achieved by the fermentation process. Xylose, an important hemicellulose hydrolysis product, is used less efficiently as a substrate for biohydrogen production. Moreover, azo dyes are usually added to fabricate anticounterfeiting paper, which further increases the complexity of wastewater. This study reports that xylose could serve as the sole carbon source for a pure culture of Klebsiella oxytoca GS-4-08 to achieve simultaneous decolorization and biohydrogen production. With 2 g liter-1 of xylose as the substrate, a maximum xylose utilization rate (URxyl) and a hydrogen molar yield (HMY) of 93.99% and 0.259 mol of H2 mol of xylose-1, respectively, were obtained. Biohydrogen kinetics and electron equivalent (e- equiv) balance calculations indicated that methyl red (MR) penetrates and intracellularly inhibits both the pentose phosphate pathway and pyruvate fermentation pathway, while methyl orange (MO) acted independently of the glycolysis and biohydrogen pathway. The data demonstrate that biohydrogen pathways in the presence of azo dyes with sulfonate and carboxyl groups were different, but the azo dyes could be completely reduced during the biohydrogen production period in the presence of MO or MR. The feasibility of hydrogen production from industrial pulp and paper effluent by the strain if the xylose is sufficient was also proved and was not affected by toxic substances which usually exist in such wastewater, except for chlorophenol. This study offers a promising energy-recycling strategy for treating pulp and paper wastewaters, especially for those containing azo dyes.IMPORTANCE The pulp and paper industry is a major industry in many developing countries, and the global market of pulp and paper wastewater treatment is expected to increase by 60% between 2012 and 2020. Such wastewater contains large amounts of refractory contaminants, such as lignin, whose reclamation is considered economically crucial and environmentally friendly. Furthermore, azo dyes are usually added in order to fabricate anticounterfeiting paper, which further increases the complexity of the pulp and paper wastewater. This work may offer a better understanding of biohydrogen production from xylose in the presence of azo dyes and provide a promising energy-recycling method for treating pulp and paper wastewater, especially for those containing azo dyes.

Characterization of a thermo-alkali-stable laccase from Bacillus subtilis cjp3 and its application in dyes decolorization.

In this work, a novel bacterial strain exhibiting laccase activity was isolated from black liquor and identified as Bacillus subtilis cjp3. The CotA-laccase gene was cloned from strain cjp3 and expressed in Escherichia coli. The purified recombinant laccase has a maximum activity of 7320 U/L, maintaining high stabilities under a wide pH range and high temperature conditions. Nearly no loss of laccase activity was observed even at pH 9.0 after 10 h of incubation. Reactive blue 19, reactive black 5 and indigo carmine could be efficiently decolorized by the purified laccase in the presence of a mediator ABTS. More than 86% of tested dyes were removed in 4 h at pH = 9.0. The recombinant laccase can work well in a broad range of temperatures of 20-80°C(>80% relative activity). These special properties indicated the potential use of the CotA-laccase in treating wastewater containing synthetic dyes.

Decolorization characteristics of a newly isolated salt-tolerant Bacillus sp. strain and its application for azo dye-containing wastewater in immobilized form.

Strain CICC 23870 capable of decolorization of various azo dyes under high saline conditions was isolated from saline-alkali soil. The oxygen-insensitive azoreductase in crude extracts exhibited a wide substrate adaptively in the presence of NADH as a cofactor. The decolorization process by free cells followed first-order kinetics, with a high Methyl Orange (MO) tolerance concentration up to 100 mg l(-1) estimated by Haldane model. The average decolorization rate of free cell system was 26.30 mg g(-1) h(-1) at initial MO concentration of 32.7 mg l(-1). However, the values for the systems of immobilized cells (4 mm) in alginate, alginate and nano-TiO2, and alginate and powered activated carbon (PAC) were 6.83, 4.64, and 11.34 mg g(-1) h(-1), respectively. The effective diffusion factors in the tree different matrices were calculated by diffusion-based mathematic model. The diffusion step controls the overall decolorization rate, and the effective diffusion coefficients varied with internal structure of the bead matrices. The diffusion coefficients were increased from 4.98 × 10(-9) to 2.25 × 10(-8) cm(2) s(-1) when PAC was added, but decreased to 6.62 × 10(-10) cm(2) s(-1) when nano-TiO2 was added. The immobilized matrices could be reused for at least three cycles but with a decreased decolorization rate, possibly due to the breakage of beads at the end of each cycle, which led to the loss of immobilized bacteria.

Mechanisms of nanoscale zero-valent iron mediating aerobic denitrification in Pseudomonas stutzeri by promoting electron transfer and gene expression.

Aerobic denitrification and its mechanism by P. stutzeri was investigated in the presence of nanoscale zero-valent iron (nZVI). The removal of nitrate and ammonia was accelerated and the nitrite nitrogen accumulation was reduced by nZVI. The particle size and dosage of nZVI were key factors for enhancing aerobic denitrification. nZVI reduced the negative effects of low carbon/nitrogen, heavy metals, surfactants and salts to aerobic denitrification. nZVI and its dissolved irons were adsorbed into the bacteria cells, enhancing the transfer of electrons from nicotinamide adenine dinucleotide (NADH) to nitrate reductase. Moreover, the activities of NADH-ubiquinone reductase involved in the respiratory system, and the denitrifying enzymes were increased. The expression of denitrifying enzyme genes napA and nirS, as well as the iron metabolism gene fur, were promoted in the presence of nZVI. This work provides a strategy for enhancing the biological denitrification of wastewater using the bio-stimulation of nanomaterials.

Selective oxidation behavior based on iron-doped MOF derived carbon-based catalysts: Active site regulation and degradation mechanism analysis.

Selective removal of target organic pollutants in complex water quality of municipal sewage is extremely important for the deep treatment of water quality. Here, energetic MOF and Fe-MOF are doped in electrostatic spinning process to adjust the structure and composition of the catalysts, active oxygen species (ROSs), realizing the selective removal of organic pollutants. Non-azo and azo pollutants are selected as target pollutants. Catalysts PCFe-8 with Fe nanoclusters, EPCFe-8 with Fe-Nx, and EPC-8 without Fe doping are used to activate peroxymonosulfate (PMS) for degrading pollutants. The results show that the PCFe-8/PMS system can produce the most SO4- and exhibit superior removal of azo pollutants, whereas the degradation behavior of non-azo pollutants is more inclined to occur in the EPCFe-8/PMS system and the EPC-8/PMS system. This work provides a reference for elucidating the relationship between catalyst structure and components, types of ROSs, and selective degradation of pollutants.

An in-depth insight into the simultaneous oxidation of sulfamethoxazole and reduction of Cr (VI) by one system of water film DBD plasma: The interaction effect, role of active species, and their dominant to pathways.

This study aims to deeply investigate the simultaneous elimination of sulfamethoxazole (SMZ) and Cr (VI) through one system of water film dielectric barrier discharge (WFDBD) plasma. The interaction effect of SMZ degradation and Cr (VI) reduction and dominant effect of active species were highlighted. Results showed that the oxidation of SMZ and the reduction of Cr (VI) directly promote each other. When the concentration of Cr (VI) raised from 0 to 2 mg L-1, the degradation rate of SMZ enhanced from 75.6% to 88.6%, respectively. Similarly, when the concentration of SMZ improved from 0 to 15 mg L-1, the removal efficiency of Cr (VI) improved from 70.8% to 84.3%, respectively. ·OH, 1O2 and ·O2- play crical roles for SMZ degradation, and e-, ·O2-, ·H and H2O2 dominated to the Cr (VI) reduction. The variations of pH, conductivity and TOC during the removal process were also explored. The removal process was studied by UV-vis spectroscopy and a three-dimensional excitation-emission matrix. Based on DFT calculation and LC-MS analysis, free radicals dominated SMZ degradation pathways in the WFDBD plasma system were clarified. Besides, the influence of Cr (VI) on SMZ degradation pathway was clarified. The ecotoxicity of SMZ and the toxicity of Cr (VI) into Cr (III) were greatly reduced. This study provides a significant reference value for the application and mechanism of plasma simultaneous removal of organic pollutants and heavy metals in wastewater.

A confined expansion pore-making strategy to transform Zn-MOF to porous carbon nanofiber for water treatment: Insight into formation and degradation mechanism.

Electrospinning MOFs nanoparticles derived porous carbon nanofibers with rational structure and design are recently as environmentally friendly and highly efficient catalytic materials for wastewater treatment. However, most of the pore-making strategies are based on precursors structural shrinkage during pyrolysis, which is a challenge to create abundant large pores and open channels. Here, a confined expansion pore-making strategy with active MOF is introduced, where energetic Zn-MOF (Zn2+/triazole) and ZIF-67 (Co2+/dimethylimidazole) are utilized as pore forming additive and precursor of active sites, respectively. The high nitrogen content gives triazole the ability to puff up and realizes N-doped during pyrolysis. Moreover, degradation mechanisms and pathways of pollutants were measured by 3D EEM, LC-MS, quenching experiments, and Fukui function. This pore-making strategy via energetic MOF local contraction and expansion provides a novel method to prepare diversiform function porous carbon materials for environmental remediation.

Selective oxidation of organic pollutants based on reactive oxygen species and the molecular structure: Degradation behavior and mechanism analysis.

The selective and rapid elimination of refractory organic pollutants from surface water is significant. However, the relationship of between reactive oxygen species (ROSs) and diversified pollutants molecular structures still needs to be further clarified. Here, we utilize polydopamine (PDA)-assisted coating strategy to prepare hollow 2D carbon nanosheet (ZPL-HCNS) and 2D Co3O4 nanosheet (ZPL-Co3O4) by thermolysis of PDA coated ZIF-L (ZIF-L@PDA) precursor under different gas atmosphere, which realizes the controlled generation of radicals and non-radicals. Organic pollutants including bisphenols, sulfonamides, quinolones, tetracyclines, and azo dyes are applied to assess the catalytic performance. Results show that dyes containing azo structure are more likely to be degraded by radical process, which is due to that the energy (ΔE) requirements to break the azo bond is higher than energy released from singlet oxygen to oxygen molecule and lower than that of sulfate radical to sulfate. Frontier molecular orbital theory HOMO-LUMO and Fukui function expounded the possible selectivity mechanism. In addition, the degradation pathway and biotoxicity test are carried out. This work provides a reference to illustrate the selective degradation for ROSs and molecular structure of pollutants.

Construction of a biomimetic core-shell PDA@Lac bioreactor from intracellular laccase as a nano-confined biocatalyst for decolorization.

Enzymes immobilized on the surface of the carriers are difficult to maintain their conformation and high activity due to the influence of the external harsh environments. A biomimetic core-shell PDA@Lac bioreactor was constructed by depositing polydopamine (PDA) on the surface of the recombinant Escherichia coli with CotA laccase gene, and releasing intracellular laccase into the PDA shell using ultrasound to break the cell wall of the bacteria. The bioreactor provided a nano-confined environment for the laccase and accelerated the mass and electron transfer in the volume-confined space, with a 2.77-fold increase in Km compared with the free laccase. Since there was no barrier of the cell wall, the crystal violet dye can enter the bioreactor to participate in the enzymatic reaction. As a result, PDA@Lac achieved excellent decolorization performance even without ABTS as an electron mediator. Moreover, the cytoplasmic solution retained in the PDA shell promoted the enzyme's tolerance to pH, temperature and harsh environments. In addition to PDA encapsulation, carbonyl and -NH2 groups of PDA were bound covalently with -NH2 and -COOH on the laccase in the PDA@Lac, resulting in an extremely high laccase loading of 817.59 mg/g. Also, the relative activity of the bioreactor maintained approximately 75% after 10 cycles of reuse. In addition, the protection of the PDA shell increased the resistance of laccase to UV irradiation. This work provides a novel method of laccase immobilization for application in wastewater treatment.

Interaction mechanism between chlorinated polyfluoroalkyl ether potassium sulfonate (F-53B) and chromium on different types of soil surfaces.

The coexistence of per- and polyfluoroalkyl substances (PFASs) and heavy metals have been found in soils. However, the interaction between the combined pollutants in soils remains unclear. In this study, the adsorption processes of single and combined Cr(VI) and chlorinated polyfluoroalkyl ether potassium sulfonate (F-53 B) in red, yellow and black soils were simulated. When compared with the single F-53 B and Cr(VI), the adsorption amount of the combined F-53 B and Cr(VI) on soils changed with the types of soils. The interactions between F-53 B and Cr(VI) in soils affected their adsorption behavior. The adsorption of the combined F-53 B and Cr(VI) best fit second-order kinetics and the Freundlich equation. Moreover, aluminum and iron oxides are highly correlated with adsorption of F-53 B and Cr(VI). Both F-53 B and Cr(VI) can form complexes with aluminum and iron oxides through electrostatic interactions, but PFOS could be bridged with iron oxides to form an inner sphere complex and with aluminum oxides to form an outer sphere complex. The coexistence of F-53 B and Cr(VI) could change the fluorescent group of dissolved organic matter (DOM) in soils due to the complexation between F-53 B and DOM. In addition, F-53 B increased the acid-soluble portion of Cr and decreased its residual form, which promoted the environmental risk of Cr in soils.

Degradation of tris(1-chloro-2-propanyl) phosphate by the synergistic effect of persulfate and zero-valent iron during a mechanochemical process.

This study revealed a dual pathway for the degradation of tris(1-chloro-2-propanyl) phosphate (TCPP) by zero-valent iron (ZVI) and persulfate as co-milling agents in a mechanochemical (MC) process. Persulfate was activated with ZVI to degrade TCPP in a planetary ball mill. After milling for 2 h, 96.5% of the TCPP was degraded with the release of 63.16, 50.39, and 42.01% of the Cl-, SO42-, and PO43-, respectively. In the first degradation pathway, persulfate was activated with ZVI to produce hydroxyl (·OH) radicals, and ZVI is oxidized to Fe(II) and Fe(III). A substitution reaction occurred as a result of the attack of ·OH on the P-O-C bonds, leading to the successive breakage of the three P-O-C bonds in TCPP to produce PO43-. In the second pathway, a C-Cl bond in part of the TCPP molecule was oxidized by SO4·- to carbonyl and carboxyl groups. The P-O-C bonds continued to react with ·OH to produce PO43-. Finally, the intermediate organochloride products were further reductively dechlorinated by ZVI. However, the synergistic effect of the oxidation (·OH and SO4·-) and the reduction reaction (ZVI) did not completely degrade TCPP to CO2, resulting in a low mineralization rate (35.87%). Moreover, the intermediate products still showed the toxicities in LD50 and developmental toxicant. In addition, the method was applied for the degradation of TCPP in soil, and high degradations (> 83.83%) were achieved in different types of soils.

Regulation of the formation and structure of biofilms by quorum sensing signal molecules packaged in outer membrane vesicles.

Quorum sensing signal molecules can be used to regulate the formation of biofilm, but it has not been reported that outer membrane vesicles (OMVs) can package and mediate signal molecules to regulate biofilm. We isolated and purified OMVs packaged with Pseudomonas quinolone signal (PQS) released by Pseudomonas aeruginosa and studied the effects of OMV-mediated PQS on the formation and structure of biofilms. OMV-mediated PQS promoted the growth of biofilm, and the cells in the biofilm were stretched, deformed and "bridged" with the surrounding cells. Raman spectrometry showed that the structure and components of the extracellular polymeric substances of P. aeruginosa changed; moreover extracellular proteins rather than polysaccharides played the dominant role in the formation of P. aeruginosa biofilms when regulated by OMV-mediated PQS. In the combination biofilm formed by P. aeruginosa and Staphylococcus aureus, the mediation of OMVs enhanced the inhibitory effect of PQS to the growth of S. aureus, resulting a decrease in EPS produced by the two bacteria. OMV-mediated PQS led to changes in the biodiversity, richness and structure of the microbial community in biofilms formed by active sludge. This work reveals the mechanism of OMVs mediated signal molecules regulating biofilm, which lays a new theoretical and practical foundation for guiding the operation of low-level of biofouling MBRs.

Efficient removal of emerging contaminant sulfamethoxazole in water by ozone coupled with calcium peroxide: Mechanism and toxicity assessment.

Sulfamethoxazole (SMX) is a widely distributed emerging contaminant, which will bring serious harm to ecology and human health. Herein, evaluation of ozone (O3) coupled with calcium peroxide (CaO2) for SMX elimination was carried out. The results showed that CaO2 could promote SMX elimination in O3 system. The removal efficiency was improved from 65.6% to 73.9% when the CaO2 dosage was 0.06 g L-1. O3 dosage of 0.55 g h-1 was beneficial to SMX degradation. With decrease of initial SMX concentration, the removal of SMX firstly enhanced and then declined. Compared with alkaline, acidic and neutral conditions were favorable for SMX degradation. ROS including ·OH, ·O2- and 1O2 play critical role for SMX degradation. Synergetic effect could be established between O3 and CaO2, which encouraged formation of ·OH and accelerated SXM decomposition. The total organic carbon (TOC) and chemical oxygen demand (COD) were all declined after O3/CaO2 treatment. According to results of liquid chromatography-mass spectrometry (LC-MS) and references, four major pathways were proposed. The O3/CaO2 technology was also suitable for practical wastewater treatment. QSAR calculation and seed germination experiment showed that toxicity of the treatment solution was alleviated after O3/CaO2 treatment.