Oxidation and biotoxicity assessment of microcystin-LR using different AOPs based on UV,O3 and H2O2

MC-LR removal performances under different AOPs were compared systematically. Higher removal efficiency and synergistic effects were obtained by combined process. The acute biotoxicity raised in different degrees after oxidation. Microcystin-LR attracts attention due to its high toxicity, high concentration and high frequency. The removal characteristics of UV/H₂O₂ and O₃/H₂O₂ advanced oxidation processes and their individual process for MC-LR were investigated and compared in this study. Both the removal efficiencies and rates of MC-LR as well as the biotoxicity of degradation products was analyzed. Results showed that the UV/H₂O₂ process and O₃/H₂O₂ were effective methods to remove MC-LR from water, and they two performed better than UV-, O₃-, H₂O₂-alone processes under the same conditions. The effects of UV intensity, H₂O₂ concentration and O₃ concentration on the removal performance were explored. The synergistic effects between UV and H₂O₂, O₃ and H₂O₂ were observed. UV dosage of 1800 mJ·cm⁻² was required to remove 90% of 100 mg·L⁻¹ MC-LR, which amount significantly decreased to 500 mJ·cm⁻² when 1.7 mg·L⁻¹ H₂O₂ was added. 0.25 mg·L⁻¹ O₃, or 0.125 mg·L⁻¹ O₃ with 1.7 mg·L⁻¹ H₂O₂ was needed to reach 90% removal efficiency. Furthermore, the biotoxicity results about these UV/H₂O₂, O₃/H₂O₂ and O₃-alone processes all present rising trends with oxidation degree of MC-LR. Biotoxicity of solution, equivalent to 0.01 mg·L⁻¹ Zn²⁺, raised to 0.05 mg·L⁻¹ Zn²⁺ after UV/H₂O₂ or O₃/H₂O₂ reaction. This phenomenon may be attributed to the aldehydes and ketones with small molecular weight generated during reaction. Advice about the selection of MC-LR removal methods in real cases was provided.     

Enhanced catalytic oxidation of 2,4-dichlorophenol via singlet oxygen dominated peroxymonosulfate activation on CoOOH@Bi2O3 composite

• Bi₂O₃ cannot directly activate PMS. • Bi₂O₃ loading increased the specific surface area and conductivity of CoOOH. • Larger specific surface area provided more active sites for PMS activation. • Faster electron transfer rate promoted the generation of reactive oxygen species. • ¹O₂ was identified as dominant ROS in the CoOOH@Bi₂O₃/PMS system. Cobalt oxyhydroxide (CoOOH) has been turned out to be a high-efficiency catalyst for peroxymonosulfate (PMS) activation. In this study, CoOOH was loaded on bismuth oxide (Bi₂O₃) using a facile chemical precipitation process to improve its catalytic activity and stability. The result showed that the catalytic performance on the 2,4-dichlorophenol (2,4-DCP) degradation was significantly enhanced with only 11 wt% Bi₂O₃ loading. The degradation rate in the CoOOH@Bi₂O₃/PMS system (0.2011 min⁻¹) was nearly 6.0 times higher than that in the CoOOH/PMS system (0.0337 min⁻¹). Furthermore, CoOOH@Bi₂O₃ displayed better stability with less Co ions leaching (16.4% lower than CoOOH) in the PMS system. These phenomena were attributed to the Bi₂O₃ loading which significantly increased the conductivity and specific surface area of the CoOOH@Bi₂O₃ composite. Faster electron transfer facilitated the redox reaction of Co (III) / Co (II) and thus was more favorable for reactive oxygen species (ROS) generation. Meanwhile, larger specific surface area furnished more active sites for PMS activation. More importantly, there were both non-radical (¹O₂) and radicals (SO₄⁻•, O₂⁻•, and OH•) in the CoOOH@Bi₂O₃/PMS system and ¹O₂ was the dominant one. In general, this study provided a simple and practical strategy to enhance the catalytic activity and stability of cobalt oxyhydroxide in the PMS system.     

Simultaneous removal of NOx and chlorobenzene on V2O5/TiO2 granular catalyst: Kinetic study and performance prediction

• A V₂O₅/TiO₂ granular catalyst for simultaneous removal of NO and chlorobenzene. • Catalyst synthesized by vanadyl acetylacetonate showed good activity and stability. • The kinetic model was established and the synergetic activity was predicted. • Both chlorobenzene oxidation and SCR of NO follow pseudo-first-order kinetics. • The work is of much value to design of multi-pollutants emission control system. The synergetic abatement of multi-pollutants is one of the development trends of flue gas pollution control technology, which is still in the initial stage and facing many challenges. We developed a V₂O₅/TiO₂ granular catalyst and established the kinetic model for the simultaneous removal of NO and chlorobenzene (i.e., an important precursor of dioxins). The granular catalyst synthesized using vanadyl acetylacetonate precursor showed good synergistic catalytic performance and stability. Although the SCR reaction of NO and the oxidation reaction of chlorobenzene mutually inhibited, the reaction order of each reaction was not considerably affected, and the pseudo-first-order reaction kinetics was still followed. The performance prediction of this work is of much value to the understanding and reasonable design of a catalytic system for multi-pollutants (i.e., NO and dioxins) emission control.     

Catalytic oxidation of CO over Pt/Fe3O4 catalysts: Tuning O2 activation and CO adsorption

• Strong metal-support interaction exists on Pt/Fe₃O₄ catalysts. • Pt metal particles facilitate the formation of oxygen vacancies on Fe₃O₄. • Fe₃O₄ supports enhance the strength of CO adsorption on Pt metal particles. The self-inhibition behavior due to CO poisoning on Pt metal particles strongly impairs the performance of CO oxidation. It is an effective method to use reducible metal oxides for supporting Pt metal particles to avoid self-inhibition and to improve catalytic performance. In this work, we used in situ reductions of chloroplatinic acid on commercial Fe₃O₄ powder to prepare heterogeneous-structured Pt/Fe₃O₄ catalysts in the solution of ethylene glycol. The heterogeneous Pt/Fe₃O₄ catalysts achieved a better catalytic performance of CO oxidation compared with the Fe₃O₄ powder. The temperatures of 50% and 90% CO conversion were achieved above 260°C and 290°C at Pt/Fe₃O₄, respectively. However, they are accomplished on Fe₃O₄ at temperatures higher than 310°C. XRD, XPS, and H₂-TPR results confirmed that the metallic Pt atoms have a strong synergistic interaction with the Fe₃O₄ supports. TGA results and transient DRIFTS results proved that the Pt metal particles facilitate the release of lattice oxygen and the formation of oxygen vacancies on Fe₃O₄. The combined results of O₂-TPD and DRIFTS indicated that the activation step of oxygen molecules at surface oxygen vacancies could potentially be the rate-determining step of the catalytic CO oxidation at Pt/Fe₃O₄ catalysts. The reaction pathway involves a Pt-assisted Mars-van Krevelen (MvK) mechanism.     

One-pot hydrothermal fabrication of BiVO4/Fe3O4/rGO composite photocatalyst for the simulated solar light-driven degradation of Rhodamine B

• BiVO₄/Fe₃O₄/rGO has excellent photocatalytic activity under solar light radiation. • It can be easily separated and collected from water in an external magnetic field. • BiVO₄/Fe₃O₄/0.5% rGO exhibited the highest RhB removal efficiency of over 99%. • Hole (h⁺) and superoxide radical (O₂^•−) dominate RhB photo-decomposition process. • The reusability of this composite was confirmed by five successive recycling runs. Fabrication of easily recyclable photocatalyst with excellent photocatalytic activity for degradation of organic pollutants in wastewater is highly desirable for practical application. In this study, a novel ternary magnetic photocatalyst BiVO₄/Fe₃O₄/reduced graphene oxide (BiVO₄/Fe₃O₄/rGO) was synthesized via a facile hydrothermal strategy. The BiVO₄/Fe₃O₄ with 0.5 wt% of rGO (BiVO₄/Fe₃O₄/0.5% rGO) exhibited superior activity, degrading greater than 99% Rhodamine B (RhB) after 120 min solar light radiation. The surface morphology and chemical composition of BiVO₄/Fe₃O₄/rGO were studied by scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, UV–visible diffuse reflectance spectroscopy, Fourier transform infrared spectroscopy, and Raman spectroscopy. The free radicals scavenging experiments demonstrated that hole (h⁺) and superoxide radical (O₂^•−) were the dominant species for RhB degradation over BiVO₄/Fe₃O₄/rGO under solar light. The reusability of this composite catalyst was also investigated after five successive runs under an external magnetic field. The BiVO₄/Fe₃O₄/rGO composite was easily separated, and the recycled catalyst retained high photocatalytic activity. This study demonstrates that catalyst BiVO₄/Fe₃O₄/rGO possessed high dye removal efficiency in water treatment with excellent recyclability from water after use. The current study provides a possibility for more practical and sustainable photocatalytic process.     

Optimization of the O3/H2O2 process with response surface methodology for pretreatment of mother liquor of gas field wastewater

• Real ML-GFW with high salinity and high organics was degraded by O₃/H₂O₂ process. • Successful optimization of operation conditions was attained using RSM based on CCD. • Single-factor experiments in advance ensured optimal experimental conditions. • The satisfactory removal efficiency of TOC was achieved in spite of high salinity. • The initial pH plays the most significant role in the degradation of ML-GFW. The present study reports the use of the O₃/H₂O₂ process in the pretreatment of the mother liquor of gas field wastewater (ML-GFW), obtained from the multi-effect distillation treatment of the gas field wastewater. The range of optimal operation conditions was obtained by single-factor experiments. Response surface methodology (RSM) based on the central composite design (CCD) was used for the optimization procedure. A regression model with Total organic carbon (TOC) removal efficiency as the response value was established (R² = 0.9865). The three key factors were arranged according to their significance as: pH>H₂O₂ dosage>ozone flow rate. The model predicted that the best operation conditions could be obtained at a pH of 10.9, an ozone flow rate of 0.8 L/min, and H₂O₂ dosage of 6.2 mL. The dosing ratio of ozone was calculated to be 9.84 mg O₃/mg TOC. The maximum removal efficiency predicted was 75.9%, while the measured value was 72.3%. The relative deviation was found to be in an acceptable range. The ozone utilization and free radical quenching experiments showed that the addition of H₂O₂ promoted the decomposition of ozone to produce hydroxyl radicals (·OH). This also improved the ozone utilization efficiency. Gas chromatography-mass spectrometry (GC-MS) analysis showed that most of the organic matters in ML-GFW were degraded, while some residuals needed further treatment. This study provided the data and the necessary technical supports for further research on the treatment of ML-GFW.     

Enhanced activation of peroxymonosulfate by CNT-TiO2 under UV-light assistance for efficient degradation of organic pollutants

CNT-TiO₂ composite is used to activate PMS under UV-light assistance. Superior performance is due to the enhanced electron-transfer ability of CNT. SO₄•⁻, •OH and ¹O₂ play key roles in the degradation of organic pollutants. In this work, a UV-light assisted peroxymonosulfate (PMS) activation system was constructed with the composite catalyst of multi-walled carbon nanotubes (CNT) - titanium dioxide (TiO₂). Under the UV light irradiation, the photoinduced electrons generated from TiO₂ could be continuously transferred to CNT for the activation of PMS to improve the catalytic performance of organic pollutant degradation. Meanwhile, the separation of photoinduced electron-hole pairs could enhance the photocatalysis efficiency. The electron spin resonance spectroscopy (EPR) and quenching experiments confirmed the generation of sulfate radical (SO₄•⁻), hydroxyl radical (•OH) and singlet oxygen (¹O₂) in the UV/PMS/20%CNT-TiO₂ system. Almost 100% phenol degradation was observed within 20 min UV-light irradiation. The kinetic reaction rate constant of the UV/PMS/20%CNT-TiO₂ system (0.18 min⁻¹) was 23.7 times higher than that of the PMS/Co₃O₄ system (0.0076 min⁻¹). This higher catalytic performance was ascribed to the introduction of photoinduced electrons, which could enhance the activation of PMS by the transfer of electrons in the UV/PMS/CNT-TiO₂ system.     

Cu/Cr co-stabilization mechanisms in a simulated Al2O3-Fe2O3-Cr2O3-CuO waste system

• Cu and Cr can be mostly incorporated into CuFe_xAl_yCr_2−x−yO₄ with a spinel structure. • Spinel phase is the most crucial structure for Cu and Cr co-stabilization. • Compared to Al, Fe and Cr are easier to be incorporated into the spinel structure. • ‘Waste-to-resource’ by thermal process at attainable temperatures can be achieved. Chromium slag usually contains various heavy metals, making its safe treatment difficult. Glass-ceramic sintering has been applied to resolve this issue and emerged as an effective method for metal immobilization by incorporating heavy metals into stable crystal structures. Currently, there is limited knowledge about the reaction pathways adopted by multiple heavy metals and the co-stabilization functions of the crystal structure. To study the Cu/Cr co-stabilization mechanisms during thermal treatment, a simulated system was prepared using a mixture with a molar ratio of Al₂O₃:Fe₂O₃:Cr₂O₃:CuO= 1:1:1:3. The samples were sintered at temperatures 600–1300°C followed by intensive analysis of phase constitutions and microstructure development. A spinel phase (CuFe_xAl_yCr_2−x−yO₄) started to generate at 700°C and the incorporation of Cu/Cr into the spinel largely complete at 900°C, although the spinel peak intensity continued increasing slightly at temperatures above 900°C. Fe₂O₃/Cr₂O₃ was more easily incorporated into the spinel at lower temperatures, while more Al₂O₃ was gradually incorporated into the spinel at higher temperatures. Additionally, sintered sample microstructures became more condensed and smoother with increased sintering temperature. Cu / Cr leachability substantially decreased after Cu/Cr incorporation into the spinel phase at elevated temperatures. At 600°C, the leached ratios for Cu and Cr were 6.28% and 0.65%, respectively. When sintering temperature was increased to 1300°C, the leached ratios for all metal components in the system were below 0.2%. This study proposes a sustainable method for managing Cu/Cr co-exist slag at reasonable temperatures.     

Hydroxyl radical intensified Cu2O NPs/H2O2 process in ceramic membrane reactor for degradation on DMAc wastewater from polymeric membrane manufacturer

• Cu₂O NPs/H₂O₂ Fenton process was intensified by membrane dispersion. • DMAc removal was enhanced to 98% for initial DMAc of 14000 mg/L. • Analyzed time-resolved degradation pathway of DMAc under ·OH attack. High-concentration industrial wastewater containing N,N-dimethylacetamide (DMAc) from polymeric membrane manufacturer was degraded in Cu₂O NPs/H₂O₂ Fenton process. In the membrane-assisted Fenton process DMAc removal rate was up to 98% with 120 min which was increased by 23% over the batch reactor. It was found that ·OH quench time was extended by 20 min and the maximum ·OH productivity was notably 88.7% higher at 40 min. The degradation reaction rate constant was enhanced by 2.2 times with membrane dispersion (k = 0.0349 min⁻¹). DMAc initial concentration (C₀) and H₂O₂ flux (J_p) had major influence on mass transfer and kinetics, meanwhile, membrane pore size (r_p) and length (L_m) also affected the reaction rate. The intensified radical yield, fast mass transfer and nanoparticles high activity all contributed to improve pollutant degradation efficiency. Time-resolved DMAc degradation pathway was analyzed as hydroxylation, demethylation and oxidation leading to the final products of CO₂, H₂O and NO₃⁻ (rather than NH₃ from biodegradation). Continuous process was operated in the dual-membrane configuration with in situ reaction and separation. After five cycling tests, DMAc removal was all above 95% for the initial [DMAc]₀ = 14,000 mg/L in wastewater and stability of the catalyst and the membrane maintained well.     

Enhanced triallyl isocyanurate (TAIC) degradation through application of an O3/UV process: Performance optimization and degradation pathways

• UV/O₃ process had higher TAIC mineralization rate than O₃ process. • Four possible degradation pathways were proposed during TAIC degradation. • pH impacted oxidation processes with pH of 9 achieving maximum efficiency. • CO₃^2– negatively impacted TAIC degradation while HCO₃^– not. • Cl^– can be radicals scavenger only at high concentration (over 500 mg/L Cl^–). Triallyl isocyanurate (TAIC, C₁₂H₁₅N₃O₃) has featured in wastewater treatment as a refractory organic compound due to the significant production capability and negative environmental impact. TAIC degradation was enhanced when an ozone(O₃)/ultraviolet(UV) process was applied compared with the application of an independent O₃ process. Although 99% of TAIC could be degraded in 5 min during both processes, the O₃/UV process had a 70%mineralization rate that was much higher than that of the independent O₃ process (9%) in 30 min. Four possible degradation pathways were proposed based on the organic compounds of intermediate products identified during TAIC degradation through the application of independent O₃ and O₃/UV processes. pH impacted both the direct and indirect oxidation processes. Acidic and alkaline conditions preferred direct and indirect reactions respectively, with a pH of 9 achieving maximum Total Organic Carbon (TOC) removal. Both CO₃^2– and HCO₃^– decreased TOC removal, however only CO₃^2– negatively impacted TAIC degradation. Effects of Cl^– as a radical scavenger became more marked only at high concentrations (over 500 mg/L Cl^–). Particulate and suspended matter could hinder the transmission of ultraviolet light and reduce the production of HO· accordingly.     

Size and shape effects of MnFe2O4 nanoparticles as catalysts for reductive degradation of dye pollutants

• Size and shape-dependent MnFe₂O₄ NPs were prepared via a facile method. • Ligand-exchange chemistry was used to prepare the hydrophilic MnFe₂O₄ NPs. • The catalytic properties of MnFe₂O₄ NPs toward dye degradation were fully studied. • The catalytic activities of MnFe₂O₄ NPs followed Michaelis–Menten behavior. • All the MnFe₂O₄ NPs exhibit selective degradation to different dyes. The magnetic nanoparticles that are easy to recycle have tremendous potential as a suitable catalyst for environmental toxic dye pollutant degradation. Rationally engineering shapes and tailoring the size of nanocatalysts are regarded as an effective manner for enhancing performances. Herein, we successfully synthesized three kinds of MnFe₂O₄ NPs with distinctive sizes and shapes as catalysts for reductive degradation of methylene blue, rhodamine 6G, rhodamine B, and methylene orange. It was found that the catalytic activities were dependent on the size and shape of the MnFe₂O₄ NPs and highly related to the surface-to-volume ratio and atom arrangements. Besides, all these nanocatalysts exhibit selectivity to different organic dyes, which is beneficial for their practical application in dye pollutant treatment. Furthermore, the MnFe₂O₄ NPs could be readily recovered by a magnet and reused more than ten times without appreciable loss of activity. The size and shape effects of MnFe₂O₄ nanoparticles demonstrated in this work not only accelerate further understanding the nature of nanocatalysts but also contribute to the precise design of nanoparticles catalyst for pollutant degradation.     

Hydrophilic/underwater superoleophobic graphene oxide membrane intercalated by TiO2 nanotubes for oil/water separation

GO/TiO₂ membrane was prepared by assembling GO nanosheets and TiO₂ nanotubes. The intercalation of TiO₂ nanotubes enlarged the space of GO interlayers and modified the surface morphology. Hydrophilic/underwater superoleophobic property of GO/TiO₂ membrane was obtained. Water permeability, hydrophilicity, oleophobicity and antifouling ability of GO-based membrane were all enhanced by intercalating TiO₂ nontubes. Membrane technology for oil/water separation has received increasing attention in recent years. In this study, the hydrophilic/underwater superoleophobic membrane with enhanced water permeability and antifouling ability were fabricated by synergistically assembling graphene oxide(GO) nanosheets and titanium dioxide (TiO₂) nanotubes for oil/water separation. GO/TiO₂ membrane exhibits hydrophilic and underwater superoleophobic properties with water contact angle of 62° and under water oil contact angle of 162.8°. GO/TiO₂ membrane shows greater water permeability with the water flux up to 531 L/(m²·h·bar), which was more than 5 times that of the pristine GO membrane. Moreover, GO/TiO₂membrane had excellent oil/water separation efficiency and anti-oil-fouling capability, as oil residual in filtrate after separation was below 5 mg/L and flux recovery ratios were over 80%.The results indicate that the intercalation of TiO₂ nanotubes into adjacent GO nanosheets enlarged the channel structure and modified surface topography of the obtained GO/TiO₂ membranes, which improved the hydrophilicity, permeability and anti-oil-fouling ability of the membranes, enlightening the great prospects of GO/TiO₂ membrane in oil-water treatment.     

Elimination of antibiotic resistance genes and control of horizontal transfer risk by UV-based treatment of drinking water: A mini review

Antibiotic-resistant bacteria and antibiotic resistance genes are in water bodies. UV/chlorination method is better to remove ARGs than UV or chlorination alone. Research on UV/hydrogen peroxide to eliminate ARGs is forthcoming. UV-based photocatalytic processes are effective to degrade ARGs. Antibiotic-resistant bacteria (ARB) and antibiotic resistance genes (ARGs) have been recognized as one of the biggest public health issues of the 21st century. Both ARB and ARGs have been determined in water after treatment with conventional disinfectants. Ultraviolet (UV) technology has been seen growth in application to disinfect the water. However, UV method alone is not adequate to degrade ARGs in water. Researchers are investigating the combination of UV with other oxidants (chlorine, hydrogen peroxide (H₂O₂), peroxymonosulfate (PMS), and photocatalysts) to harness the high reactivity of produced reactive species (Clž·, ClOž·ž, Clž₂·ž⁻, žž·OH, and SOž₄ž·⁻€) in such processes with constituents of cell (e.g., deoxyribonucleic acid (DNA) and its components) in order to increase the degradation efficiency of ARGs. This paper briefly reviews the current status of different UV-based treatments (UV/chlorination, UV/H₂O₂, UV/PMS, and UV-photocatalysis) to degrade ARGs and to control horizontal gene transfer (HGT) in water. The review also provides discussion on the mechanism of degradation of ARGs and application of q-PCR and gel electrophoresis to obtain insights of the fate of ARGs during UV-based treatment processes.     

Catalytic urea hydrolysis by composite metal oxide catalyst towards efficient urea-based SCR process: performance evaluation and mechanism investigation

● Bimetallic oxide composite catalyst was designed for the urea-based SCR process. ● Surface chemical state and typical microstructure of catalyst was determined. ● Reaction route was improved based on intermediates and active site identification. ● TiO₂@Al₂O₃ presents an obvious promotion for urea hydrolysis. As a promising option to provide gaseous NH₃ for SCR system, catalytic urea hydrolysis has aroused great attention, and improving surface area and activity of catalysis are the crucial issues to be solved for efficient urea hydrolysis. Therefore, a composite metal oxide (TiO₂@Al₂O₃) catalyst was prepared by a simple hydrothermal method, with mesoporous alumina (γ-Al₂O₃) as substrate. The results verify the mesoporous structure and submicron cluster of TiO₂@Al₂O₃, with exposed crystal faces of (101) and (400) for TiO₂ and γ-Al₂O₃, respectively. The electronegativity difference of Ti⁴⁺ and Al³⁺ changes the charge distribution scheme around the interface, which provides abundant acid/base sites to boost the urea hydrolysis. Consequently, for an optimal proportioning with nano TiO₂ content at 10 wt.%, the hydrolysis efficiency can reach up to 35.2 % at 100 °C in 2 h, increasing by ~7.1 % than that of the blank experiment. ¹³C NMR spectrum measurements provide the impossible intermediate species during urea hydrolysis. Theoretical calculations are performed to clarify the efficient H₂O decomposition at the interface of TiO₂@Al₂O₃. The result offers a favorable technology for energy-efficiency urea hydrolysis.     

One-step ball milling-prepared nano Fe2O3 and nitrogen-doped graphene with high oxygen reduction activity and its application in microbial fuel cells

• Nano Fe₂O₃ and N-doped graphene was prepared via a one-step ball milling method. • The maximum power density of Fe-N-G in MFC was 390% of that of pristine graphite. • Active sites like nano Fe₂O₃, pyridinic N and Fe-N groups were formed in Fe-N-G. • The improvement of Fe-N-G was due to full exposure of active sites on graphene. Developing high activity, low-cost and long durability catalysts for oxygen reduction reaction is of great significance for the practical application of microbial fuel cells. The full exposure of active sites in catalysts can enhance catalytic activity dramatically. Here, novel Fe-N-doped graphene is successfully synthesized via a one-step in situ ball milling method. Pristine graphite, ball milling graphene, N-doped graphene and Fe-N-doped graphene are applied in air cathodes, and enhanced performance is observed in microbial fuel cells with graphene-based catalysts. Particularly, Fe-N-doped graphene achieves the highest oxygen reduction reaction activity, with a maximum power density of 1380±20 mW/m² in microbial fuel cells and a current density of 23.8 A/m² at –0.16 V in electrochemical tests, which are comparable to commercial Pt and 390% and 640% of those of pristine graphite. An investigation of the material characteristics reveals that the superior performance of Fe-N-doped graphene results from the full exposure of Fe₂O₃ nanoparticles, pyrrolic N, pyridinic N and excellent Fe-N-G active sites on the graphene matrix. This work not only suggests the strategy of maximally exposing active sites to optimize the potential of catalysts but also provides promising catalysts for the use of microbial fuel cells in sustainable energy generation.     

Enhanced 4-chlorophenol biodegradation by integrating Fe2O3 nanoparticles into an anaerobic reactor: Long-term performance and underlying mechanism

• 4-chlorophenol biodegradation could be enhanced in Fe₂O₃ coupled anaerobic system. • Metabolic activity and electron transport could be improved by Fe₂O₃ nanoparticles. • Functional microbial communities could be enriched in coupled anaerobic system. • Possible synergistic mechanism involved in enhanced dechlorination was proposed. Fe₂O₃ nanoparticles have been reported to enhance the dechlorination performance of anaerobic systems, but the underlying mechanism has not been clarified. This study evaluated the technical feasibility, system stability, microbial biodiversity and the underlying mechanism involved in a Fe₂O₃ nanoparticle-coupled anaerobic system treating 4-chlorophenol (4-CP) wastewater. The results demonstrated that the 4-CP and total organic carbon (TOC) removal efficiencies in the Fe₂O₃-coupled up-flow anaerobic sludge blanket (UASB) were always higher than 97% and 90% during long-term operation, verifying the long-term stability of the Fe₂O₃-coupled UASB. The 4-CP and TOC removal efficiencies in the coupled UASB increased by 42.9±0.4% and 27.5±0.7% compared to the control UASB system. Adding Fe₂O₃ nanoparticles promoted the enrichment of species involved in dechlorination, fermentation, electron transfer and acetoclastic methanogenesis, and significantly enhanced the extracellular electron transfer ability, electron transport activity and conductivity of anaerobic sludge, leading to enhanced 4-CP biodegradation performance. A possible synergistic mechanism involved in enhanced anaerobic 4-CP biodegradation by Fe₂O₃ nanoparticles was proposed.     

Mechanism of dichloromethane disproportionation over mesoporous TiO2 under low temperature

• Mechanism of DCM disproportionation over mesoporous TiO₂ was studied. • DCM was completely eliminated at 350℃ under 1 vol.% humidity. • Anatase (001) was the key for disproportionation. • A competitive oxidation route co-existed with disproportionation. • Disproportionation was favored at low temperature. Mesoporous TiO₂ was synthesized via nonhydrolytic template-mediated sol-gel route. Catalytic degradation performance upon dichloromethane over as-prepared mesoporous TiO₂, pure anatase and rutile were investigated respectively. Disproportionation took place over as-made mesoporous TiO₂ and pure anatase under the presence of water. The mechanism of disproportionation was studied by in situ FTIR. The interaction between chloromethoxy species and bridge coordinated methylenes was the key step of disproportionation. Formate species and methoxy groups would be formed and further turned into carbon monoxide and methyl chloride. Anatase (001) played an important role for disproportionation in that water could be dissociated into surface hydroxyl groups on such structure. As a result, the consumed hydroxyl groups would be replenished. In addition, there was another competitive oxidation route governed by free hydroxyl radicals. In this route, chloromethoxy groups would be oxidized into formate species by hydroxyl radicals transfering from the surface of TiO₂. The latter route would be more favorable at higher temperature.     

Effect of 2-butenal manufacture wastewater to methanogenic activity and microbial community

The inhibition ratio sharply increased with the increasing COD. The absorbance of UV-vis at 420 nm showed a linear correlation with the SMA. The molecular structure of EPS has changed when COD was 9585 mg/L. Illumina Miseq sequencing was employed to reveal the microbial composition. The synthesis of 2-butenal, which is a vital raw material for the production of sorbic acid as a food preservative, generates some toxic by-products, so it is urgent to seek better detoxification strategies for the treatment of 2-butenal manufacture wastewater. In this study, batch experiments were carried out to investigate the inhibition effect of wastewater on the methanogenic activity. To understand the wastewater toxicity to anaerobic granular sludge, variations of the specific methanogenic activity (SMA) and extracellular polymeric substance (EPS) constituents at various wastewater CODs were investigated. Ultraviolet-visible (UV-vis) spectra and Fourier transform infrared (FT-IR) spectra were employed to analyze the structure of the EPS. The results showed that the inhibitory ratio of 2-butenal manufacture wastewater was less than 8.4% on the anaerobic granular sludge when the CODs were less than 959 mg/L. However, the inhibitory ratio increased from 36.4% to 93.6% when CODs increased from 2396 mg/L to 9585 mg/L, with the SMA decreasing from 39.1 mL CH₄/(gVSS·d) to 3.2 mL CH₄/(gVSS·d). The diversity of the microbial community under various CODs was researched by Illumina 16S rRNA Miseq sequencing and the results demonstrated that Proteiniphilum、Petrimonas and Syntrophobacter were the dominant bacteria genera in all sample. Regarding archaea, Methanobacterium was the most dominated archaea genera, followed by the Methanosaeta group in all samples. Moreover, the bacterial communities had changed obviously with increasing CODs, which indicated high CODs played a negative impact on the richness and diversity of bacterial community in the sludge samples.     

Statistical modeling of radiolytic (60Co g) degradation of Ofloxacin,antibiotic: Synergetic effect,kinetic studies & assessment of its degraded metabolites

Linear, interactive and quadratic effects of process parameters were studied. Degradation of Ofloxacin (Ofx) was related with G value of irradiation process. The synergistic effect of H₂O₂ on lower dose of g-irradiation was established. The process follows pseudo first order with dose constant (d = 0.232 kGy^–1). The impact of human activities in the past few decades has paved the way for the release of pollutants due to the improper effluent treatment. Recent studies revealed that, Ofloxacin, an antibiotic as one of the major pollutant affecting surface water and ground water. In this study, the radiolytic potential of Ofloxacin was investigated. The effects of pH, dose and concentration of Ofloxacin were analyzed using One Factor At a Time (OFAT) and the interactive effects between the parameters were studied using Face Centered Central Composite Design. The statistically optimised developed model shows 30% degradation at initial antibiotic concentration of 1mM at pH 3.0 and at 2 kGy dose of gamma ray. The process efficiency was evaluated in terms of G value and its correlation with the concentration of antibiotic was also established. The process of degradation was augmented by the addition of H₂O₂ (1.5 mM). The reaction kinetics for the process was evaluated, the dose rate constant and the rate of degradation for the augmented process was found to be 0.232 kGy^-1 and 0.232 mM/kGy, respectively. The degraded metabolites of the radiolytic degradation of Ofloxacin were analyzed through change in pH, reduction in TOC and GC-MS spectrum.     

How aerosol direct effects influence the source contributions to PM2.5 concentrations over Southern Hebei,China in severe winter haze episodes

The aerosol direct effects result in a 3%–9% increase in PM_2.5 concentrations over Southern Hebei. These impacts are substantially different under different PM_2.5 loadings. Industrial and domestic contributions will be underestimated if ignoring the feedbacks. Beijing-Tianjin-Hebei area is the most air polluted region in China and the three neighborhood southern Hebei cities, Shijiazhuang, Xingtai, and Handan, are listed in the top ten polluted cities with severe PM_2.5 pollution. The objective of this paper is to evaluate the impacts of aerosol direct effects on air quality over the southern Hebei cities, as well as the impacts when considering those effects on source apportionment using three dimensional air quality models. The WRF/Chem model was applied over the East Asia and northern China at 36 and 12 km horizontal grid resolutions, respectively, for the period of January 2013, with two sets of simulations with or without aerosol-meteorology feedbacks. The source contributions of power plants, industrial, domestic, transportation, and agriculture are evaluated using the Brute-Force Method (BFM) under the two simulation configurations. Our results indicate that, although the increases in PM_2.5 concentrations due to those effects over the three southern Hebei cities are only 3%–9% on montly average, they are much more significant under high PM_2.5 loadings (~50 μg·m⁻³ when PM_2.5 concentrations are higher than 400 μg m⁻³). When considering the aerosol feedbacks, the contributions of industrial and domestic sources assessed using the BFM will obviously increase (e.g., from 30%–34% to 32%–37% for industrial), especially under high PM_2.5 loadings (e.g., from 36%–44% to 43%–47% for domestic when PM_2.5>400 μg·m⁻³). Our results imply that the aerosol direct effects should not be ignored during severe pollution episodes, especially in short-term source apportionment using the BFM.