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.     

Preparation of nZVI embedded modified mesoporous carbon for catalytic persulfate to degradation of reactive black 5

• The MCNZVI is prepared as an interesting material for PS activation. • Graphitized carbon shells facilitate electron transfer from Fe⁰. • The MCNZVI exhibits excellent performance to degrade RB5 by ¹O₂. • The MCNZVI has high stability and reusability in the oxidation system. High-efficiency and cost-effective catalysts with available strategies for persulfate (PS) activation are critical for the complete mineralization of organic contaminants in the environmental remediation and protection fields. A nanoscale zero-valent iron-embedded modified mesoporous carbon (MCNZVI) with a core-shell structure is synthesized using the hydrothermal synthesis method and high-temperature pyrolysis. The results showed that nZVI could be impregnated within mesoporous carbon frameworks with a comparatively high graphitization degree, rich nitrogen doping content, and a large surface area and pore volume. This material was used as a persulfate activator for the oxidation removal of Reactive Black 5 (RB5). The effects of the material dosage, PS concentration, pH, and some inorganic anions (i.e., Cl⁻, SO₄²⁻) on RB5 degradation were then investigated. The highest degradation efficiency (97.3%) of RB5 was achieved via PS (20 mmol/L) activation by the MCNZVI (0.5 g/L). The pseudo-first-order kinetics (k = 2.11 × 10⁻² min⁻¹) in the MCNZVI/PS (0.5 g/L, 20 mmol/L) was greater than 100 times than that in the MCNZVI and PS. The reactive oxygen species (ROS), including ¹O₂, SO₄^·−, HO^·, and ·O₂⁻, were generated by PS activation with the MCNZVI. Singlet oxygen was demonstrated to be the primary ROS responsible for the RB5 degradation. The MCNZVI could be reused and regenerated for recycling. This work provides new insights into PS activation to remove organic contamination.     

Co-present Pb(II) accelerates the oxidation of organic contaminants by permanganate: Role of Pb(III)

• Simultaneous removal of organic contaminants and Pb(II) was achieved by Mn(VII). • Pb(II) enhanced Mn(VII) oxidation performance over a wide pH range. • Pb(II) did not alter the pH-rate profile for contaminants oxidation by Mn(VII). • Mn(VII) alone cannot oxidize Pb(II) effectively at pH below 5.0. • Pb(III) plays important roles on enhancing Mn(VII) decontamination process. The permanganate (Mn(VII)) oxidation has emerged as a promising technology for the remediation and treatment of the groundwater and surface water contaminated with the organic compounds. Nonetheless, only a few studies have been conducted to explore the role of the heavy metals (especially the redox-active ones) during the Mn(VII) oxidation process. In this study, taking Pb(II) as an example, its influence on the Mn(VII) decontamination performance has been extensively investigated. It was found that, with the presence of Pb(II), Mn(VII) could degrade diclofenac (DCF), 2,4-dichlorophenol, and aniline more effectively than without. For instance, over a wide pH range of 4.5–8.0, the dosing of 10 μmol/L Pb(II) accelerated the DCF removal rate from 0.006–0.25 min⁻¹ to 0.05–0.46 min⁻¹ with a promotion factor of 1.9–9.4. Although the UV-vis spectroscopic and high resolution transmission electron microscopy analyses suggested that Mn(VII) could react with Pb(II) to produce Mn(IV) and Pb(IV) at pH 6.0–8.0, further experiments revealed that Pb(II) did not exert its enhancing effect through promoting the generation of MnO₂, as the reactivity of MnO₂ was poor under the employed pH range. At pH below 5.0, it was interesting to find that, a negligible amount of MnO₂ was formed in the Mn(VII)/Pb(II) system in the absence of contaminants, while once MnO₂ was generated in the presence of contaminants, it could catalyze the Pb(II) oxidation to Pb(IV) by Mn(VII). Collectively, by highlighting the conversion process of Pb(II) to Pb(IV) by either Mn(VII) or MnO₂, the reactive Pb(III) intermediates were proposed to account for the Pb(II) enhancement effect.     

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 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.     

New method for efficient control of hydrogen sulfide and methane in gravity sewers: Combination of NaOH and nitrite

• The combination of NaOH and nitrite was used to control harmful gas in sewers. • Hydrogen sulfide and methane in airspace were reduced by 96.01% and 91.49%. • Changes in sewage quality and greenhouse effect by chemical dosing were negligible. • The strong destructive effects on biofilm slowed down the recovery of harmful gases. • The cost of the method was only 3.92 × 10⁻³ $/m³. An innovative treatment method by the combination of NaOH and nitrite is proposed for controlling hydrogen sulfide and methane in gravity sewers and overcome the drawbacks of the conventional single chemical treatment. Four reactors simulating gravity sewers were set up to assess the effectiveness of the proposed method. Findings demonstrated hydrogen sulfide and methane reductions of about 96.01% and 91.49%, respectively, by the combined addition of NaOH and nitrite. The consumption of NaNO₂ decreased by 42.90%, and the consumption rate of NaOH also showed a downward trend. Compared with a single application of NaNO₂, the C/N ratio of wastewater was increased to about 0.61 mg COD/mg N. The greenhouse effect of intermediate N₂O and residual methane was about 48.80 gCO₂/m³, which is far lower than that of methane without control (260 gCO₂/m³). Biofilm was destroyed to prevent it from entering the sewage by the chemical additives, which reduced the biomass and inhibited the recovery of biofilm activity to prolong the control time. The sulfide production rate and sulfate reduction rate were reduced by 92.32% and 85.28%, respectively. Compared with conventional control methods, the cost of this new method was only 3.92 × 10⁻³ $/m³, which is potentially a cost-effective strategy for sulfide and methane control in gravity sewers.     

Product identification and toxicity change during oxidation of methotrexate by ferrate and permanganate in water

• Oxidation of methotrexate by high-valent metal-oxo species was first explored. • Fe(VI) presented a higher reactivity to MTX than Mn(VII) at pH 8.0. • Ketonization and cleavage of peptide bond were two initial reaction pathways. • Products of MTX were not genotoxic, neurotoxic, or endocrine-disrupting chemicals. • The less biodegradable products exhibited developmental and acute/chronic toxicity. Accompanying an annual increase in cancer incidence, the global use of anticancer drugs has remarkably increased with their worldwide environmental prevalence and ecological risks. In this study, the oxidation of methotrexate (MTX), a typical anticancer drug with ubiquitous occurrence and multi-endpoint toxicity, by ferrate(VI) (Fe(VI)) and permanganate (Mn(VII))) was investigated in water. Fe(VI) exhibited a higher reactivity with MTX (93.34 M⁻¹ s⁻¹) than Mn(VII) (3.01 M⁻¹ s⁻¹) at pH 8.0. The introduction of Cu(II) and Fe(III) at 1.0 mM improved the removal efficiency of 5.0 μM MTX by 100.0 μM Fe(VI) from 80% to 95% and 100% after 4 min, respectively. Seven oxidized products (OPs) were identified during oxidative treatments, while OP-191 and OP-205 were characterized as specific products for Fe(VI) oxidation. Initial ketonization of the L-glutamic acid moiety and cleavage of the peptide bond of MTX were proposed. Additionally, a multi-endpoint toxicity evaluation indicated no genotoxicity, neurotoxicity, or endocrine-disrupting effects of MTX and its OPs. Particularly, serious developmental toxicity in zebrafish larvae was observed in the treated MTX solutions. Based on the acute and chronic aquatic toxicity prediction, OP-190, OP-192, OP-206, and OP-208 were deemed toxic or very toxic compared to harmful MTX. Furthermore, the reduced biodegradability index from 0.15 (MTX) to −0.5 to −0.2 (OP-192, OP-206, and OP-468) indicated the formation of lower biodegradable OPs. Overall, this study suggests that Fe(VI) and Mn(VII) oxidation are promising treatments for remediating anticancer drug-contaminated water. However, the environmental risks associated with these treatments should be considered in the evaluation of water safety.     

Particle-bound polycyclic aromatic hydrocarbons in typical urban of Yunnan-Guizhou Plateau: Characterization,sources and risk assessment

• The sampling was conducted in city on the Yunnan-Guizhou Plateau for one year. • The groups of PAHs revealed their different environmental fates and migration paths. • Seasonal biomass burning could affect the concentration by long-distance transport. • Industrial sources and traffic emissions were the main contributor of PAHs. • Living in industrial areas or winter had higher health risk by exposure PAHs in PM_2.5. Monthly particle-phase ambient samples collected at six sampling locations in Yuxi, a high-altitude city on the edge of Southeast Asia, were measured for particle-associated PAHs. As trace substances, polycyclic aromatic hydrocarbons (PAHs) are susceptible to the influences of meteorological conditions, emissions, and gas-particulate partitioning and it is challenging job to precise quantify the source and define the transmission path. The daily concentrations of total PM_2.5-bound PAHs ranged from 0.65 to 80.76 ng/m³, with an annual mean of 11.94 ng/m³. Here, we found that the concentration of PM_2.5-bound PAHs in winter was significantly higher than that in summer, which was mainly due to source and meteorology influence. The increase of fossil combustion and biomass burning in cold season became the main contributors of PAHs, while precipitation and low temperature exacerbated this difference. According to the concentration variation trend of PM_2.5-bound PAHs and their relationship with meteorological conditions, a new grouping of PAHs is applied, which suggested that PAHs have different environmental fates and migration paths. A combination of source analysis and trajectory model supported local sources from combustion of fossil fuel and vehicle exhaust contributed to the major portion on PAHs in particle, but on the Indochina Peninsula the large number of pollutants emitted by biomass burning during the fire season would affect the composition of PAHs through long-range transporting. Risk assessment in spatial and temporal variability suggested that citizens living in industrial areas were higher health risk caused by exposure the PM_2.5-bound PAHs than that in other regions, and the risk in winter was three times than in summer.     

Enhanced enzymatic removal of anthracene by the mangrove soil-derived fungus, Aspergillus sydowii BPOI

• A. sydowii strain bpo1 exhibited 99.8% anthracene degradation efficiency. • Four unique metabolic products were obtained after anthracene degradation. • Ligninolytic enzymes induction played vital roles in the removal of anthracene. • Laccase played a crucial role in comparison with other enzymes induced. The present study investigated the efficiency of Aspergillus sydowii strain bpo1 (GenBank Accession Number: MK373021) in the removal of anthracene (100 mg/L). Optimal degradation efficiency (98.7%) was observed at neutral pH, temperature (30℃), biomass weight (2 g) and salinity (0.2% w/v) within 72 h. The enzyme analyses revealed 131%, 107%, and 89% induction in laccase, lignin peroxidase, and manganese peroxidase respectively during anthracene degradation. Furthermore, the degradation efficiency (99.8%) and enzyme induction were significantly enhanced with the addition of 100 mg/L of citric acid and glucose to the culture. At varying anthracene concentrations (100–500 mg/L), the degradation rate constants (k₁) peaked with increasing concentration of anthracene while the half-life (t_1/2) decreases with increase in anthracene concentration. Goodness of fit (R² = 0.976 and 0.982) was observed when the experimental data were subjected to Langmuir and Temkin models respectively which affirmed the monolayer and heterogeneous nature exhibited by A. sydwoii cells during degradation. Four distinct metabolites; anthracene-1,8,9 (2H,8aH,9aH)-trione, 2,4a-dihydronaphthalene-1,5-dione, 1,3,3a,7a-tetrahydro-2-benzofuran-4,7-dione and 2-hydroxybenzoic acid was obtained through Gas Chromatography-Mass spectrometry (GC-MS). A. sydowii exhibited promising potentials in the removal of PAHs.     

Contributions of adsorption,bioreduction and desorption to uranium immobilization by extracellular polymeric substances

● EPS immobilizes U(VI) via adsorption, bioreduction and desorption. ● This work provides a framework to quantify the three immobilization processes. ● The non-equilibrium adsorption of U follows pseudo-second-order kinetics. ● The equilibrium adsorption of U followed Langmuir and Freundlich isotherms. Hexavalent uranium (U(VI)) can be immobilized by various microbes. The role of extracellular polymeric substances (EPS) in U(VI) immobilization has not been quantified. This work provides a model framework to quantify the contributions of three processes involved in EPS-mediated U(VI) immobilization: adsorption, bioreduction and desorption. Loosely associated EPS was extracted from a pure bacterial strain, Klebsiella sp. J1, and then exposed to H₂ and O₂ (no bioreduction control) to immobilize U(VI) in batch experiments. U(VI) immobilization was faster when exposed to H₂ than O₂ and stabilized at 94% for H₂ and 85% for O₂, respectively. The non-equilibrium data from the H₂ experiments were best simulated by a kinetic model consisting of pseudo-second-order adsorption (k_a = 2.87 × 10⁻³ g EPS·(mg U)⁻¹·min⁻¹), first-order bioreduction (k_b = 0.112 min⁻¹) and first-order desorption (k_d = 7.00 × 10⁻³ min⁻¹) and fitted the experimental data with R² of 0.999. While adsorption was dominant in the first minute of the experiments with H₂, bioreduction was dominant from the second minute to the 50^th min. After 50 min, adsorption was negligible, and bioreduction was balanced by desorption. This work also provides the first set of equilibrium data for U(VI) adsorption by EPS alone. The equilibrium experiments with O₂ were well simulated by both the Langmuir isotherm and the Freundlich isotherm, suggesting multiple mechanisms involved in the interactions between U(VI) and EPS. The thermodynamic study indicated that the adsorption of U(VI) onto EPS was endothermic, spontaneous and favorable at higher temperatures.     

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.     

Diphenylarsinic acid sorption mechanisms in soils using batch experiments and EXAFS spectroscopy

• DPAA sorption data was found to fit the Freundlich equation. • K_f was significantly positive correlated with oxalate-extractable Fe₂O₃. • Ligand exchange was the main mechanism for DPAA sorption on soils. • Bidentate binuclear and monodentate mononuclear DPAA bonds were identified. Diphenylarsinic acid (DPAA) is a phenyl arsenic compound derived from chemical warfare weapons. Macroscopic and microscopic work on DPAA sorption will provide useful information in predicting the partitioning and mobility of DPAA in the soil-water environment. Here, batch experiments and extended X-ray absorption fine structure (EXAFS) spectroscopy were used to investigate the sorption mechanisms of DPAA. The DPAA sorption data from 11 soil types was found to fit the Freundlich equation, and the sorption capacity, K_f, was significantly and positively correlated with oxalate-extractable Fe₂O₃. The K_f values of eight of the 11 untreated soils (1.51–113.04) significantly decreased upon removal of amorphous metal (hydr)oxides (0.51–13.37). When both amorphous and crystalline metal (hydr)oxides were removed from the untreated soils, the K_f values either decreased or slightly increased (0.65–3.09). Subsequent removal of soil organic matter from these amorphous and crystalline metal (hydr)oxide-depleted samples led to further decreases in K_f to 0.02–1.38, with only one exception (Sulfic Aquic-Orthic Halosols). These findings strongly suggest that ligand exchange reactions with amorphous metal (hydr)oxides contribute most to DPAA sorption on soils. EXAFS data provide further evidence that DPAA primarily formed bidentate binuclear (²C) and monodentate mononuclear (¹V) coring-sharing complexes with As-Fe distances of 3.34 and 3.66 Å, respectively, on Fe (hydr)oxides. Comparison of these results with earlier studies suggests that ²C and ¹V complexes of DPAA may be favored under low and high surface coverages, respectively, with the formation of ¹V bonds possibly conserving the sorption sites or decreasing the steric hindrance derived from phenyl substituents.     

TiO2@palygorskite composite for the efficient remediation of oil spills via a dispersion-photodegradation synergy

• A novel and multi-functional clay-based oil spill remediation system was constructed. • TiO₂@PAL functions as a particulate dispersant to break oil slick into tiny droplets. • Effective dispersion leads to the direct contact of TiO₂ with oil pollutes directly. • TiO₂ loaded on PAL exhibits efficient photodegradation for oil pollutants. • TiO₂@PAL shows a typical dispersion-photocatalysis synergistic remediation. Removing spilled oil from the water surface is critically important given that oil spill accidents are a common occurrence. In this study, TiO₂@Palygorskite composite prepared by a simple coprecipitation method was used for oil spill remediation via a dispersion-photodegradation synergy. Diesel could be efficiently dispersed into small oil droplets by TiO₂@Palygorskite. These dispersed droplets had an average diameter of 20–30 mm and exhibited good time stability. The tight adsorption of TiO₂@Palygorskite on the surface of the droplets was observed in fluorescence and SEM images. As a particulate dispersant, the direct contact of TiO₂@Palygorskite with oil pollutants effectively enhanced the photodegradation efficiency of TiO₂ for oil. During the photodegradation process, •O₂⁻and •OH were detected by ESR and radical trapping experiments. The photodegradation efficiency of diesel by TiO₂@Palygorskite was enhanced by about 5 times compared with pure TiO₂ under simulated sunlight irradiation. The establishment of this new dispersion-photodegradation synergistic remediation system provides a new direction for the development of marine oil spill remediation.     

Dual-functional sites for synergistic adsorption of Cr(VI) and Sb(V) by polyaniline-TiO2 hydrate: Adsorption behaviors,sites and mechanisms

• PANI/Ti(OH)_n^(4–n)+ exhibited excellent adsorption capacity and reusability. • Adsorption sites of Cr(VI) were hydroxyl, amino/imino group and benzene rings. • Sb(V) was adsorbed mainly through hydrogen bonds and Ti-O-Sb. • The formation of Cr-O-Sb in dual system demonstrated the synergistic adsorption. • PANI/TiO₂ was a potential widely-applied adsorbent and worth further exploring. Removal of chromium (Cr) and antimony (Sb) from aquatic environments is crucial due to their bioaccumulation, high mobility and strong toxicity. In this work, a composite adsorbent consisting of Ti(OH)_n^(4–n)+ and polyaniline (PANI) was designed and successfully synthesized by a simple and eco-friendly method for the uptake of Cr(VI) and Sb(V). The synthetic PANI/TiO₂ composites exhibited excellent adsorption capacities for Cr(VI) and Sb(V) (394.43 mg/g for Cr(VI) and 48.54 mg/g for Sb(V)), wide pH applicability and remarkable reusability. The adsorption of Cr(VI) oxyanions mainly involved electrostatic attraction, hydrogen bonding and anion-π interactions. Based on X-ray photoelectron spectroscopy and FT-IR analysis, the adsorption sites were shown to be hydroxyl groups, amino/imino groups and benzene rings. Sb(V) was adsorbed mainly through hydrogen bonds and surface complexation to form Ti-O-Sb complexes. The formation of Cr-O-Sb in the dual system demonstrated the synergistic adsorption of Cr(VI) and Sb(V). More importantly, because of the different adsorption sites, the adsorption of Cr(VI) and Sb(V) occurred independently and was enhanced to some extent in the dual system. The results suggested that PANI/TiO₂ is a promising prospect for practical wastewater treatment in the removal of Cr(VI) and Sb(V) from wastewater owing to its availability, wide applicability and great reusability.     

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.     

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.     

Removal of steroid hormones from mariculture system using seaweed Caulerpa lentillifera

•Steroid hormones could be removed efficiently from mariculture system using seaweed; • Caulerpa lentillifera was the most efficient seaweed for removal of steroid hormones; • More than 90% of E₂ or EE₂ were removed within 12 h using Caulerpa lentillifera; • The removal included the rapid biosorption and the slow bio-accumulation; •The hormones and nutrients in mariculture wastewater could be simultaneously removed. The removal of steroid hormones from the mariculture system using seaweeds (Caulerpa lentillifera, Ulva pertusa, Gracilaria lemaneiformis, and Codium fragile) was investigated. The results illustrated that both 17β-estradiol (E₂) and 17α-ethinylestradiol (EE₂) could be removed by the seaweeds at different levels, and the Caulerpa lentillifera was the most efficient one. More than 90% of E₂ or EE₂ at concentration of 10 μg/L was removed by Caulerpa lentillifera within 12 h. Processes including initial quick biosorption, the following slow accumulation, and biodegradation might explain the removal mechanisms of E₂/EE₂ by Caulerpa lentillifera. E₂/EE₂ removal was positively related to the nutrient level and the initial concentration of steroid hormone. A significant linear relationship for E₂ and EE₂ existed between the initial pollutant concentration and the average removal rate. The highest removal kinetic constant (k) value was obtained at 30°C as 0.34 /h for E₂ and at 20°C as 0.28 /h for EE₂, demonstrating the promising application potential of Caulerpa lentillifera in the water purification of the industrialized mariculture system with relatively high water temperature. Simultaneous and efficient removal of E₂ and EE₂ by Caulerpa lentillifera was still achieved after 3 cycles in the pilot-scale experiment. The steroid hormones and nutrients in mariculture wastewater could also be simultaneously removed using Caulerpa lentillifera. These findings demonstrated that Caulerpa lentillifera was the promising seaweed for the removal of steroid hormones in mariculture systems.     

Enhanced hydrogen production in microbial electrolysis through strategies of carbon recovery from alkaline/thermal treated sludge

• High hydrogen yield is recovered from thermal-alkaline pretreated sludge. • Separating SFL by centrifugation is better than filtration for hydrogen recovery. • The cascaded bioconversion of complex substrates in MECs are studied. • Energy and electron efficiency related to substrate conversion are evaluated. The aim of this study was to investigate the biohydrogen production from thermal (T), alkaline (A) or thermal-alkaline (TA) pretreated sludge fermentation liquid (SFL) in a microbial electrolysis cells (MECs) without buffer addition. Highest hydrogen yield of 36.87±4.36 mgH₂/gVSS (0.026 m³/kg COD) was achieved in TA pretreated SFL separated by centrifugation, which was 5.12, 2.35 and 43.25 times higher than that of individual alkaline, thermal pretreatment and raw sludge, respectively. Separating SFL from sludge by centrifugation eliminated the negative effects of particulate matters, was more conducive for hydrogen production than filtration. The accumulated short chain fatty acid (SCFAs) after pretreatments were the main substrates for MEC hydrogen production. The maximum utilization ratio of acetic acid, propionic acid and n-butyric acid was 93.69%, 90.72% and 91.85%, respectively. These results revealed that pretreated WAS was highly efficient to stimulate the accumulation of SCFAs. And the characteristics and cascade bioconversion of complex substrates were the main factor that determined the energy efficiency and hydrogen conversion rate of MECs.     

Electricity-driven ammonia oxidation and acetate production in microbial electrosynthesis systems

• MES was constructed for simultaneous ammonia removal and acetate production. • Energy consumption was different for total nitrogen and ammonia nitrogen removal. • Energy consumption for acetate production was about 0.04 kWh/g. • Nitrate accumulation explained the difference of energy consumption. • Transport of ammonia and acetate across the membrane deteriorated the performance. Microbial electrosynthesis (MES) is an emerging technology for producing chemicals, and coupling MES to anodic waste oxidation can simultaneously increase the competitiveness and allow additional functions to be explored. In this study, MES was used for the simultaneous removal of ammonia from synthetic urine and production of acetate from CO₂. Using graphite anode, 83.2%±5.3% ammonia removal and 28.4%±9.9% total nitrogen removal was achieved, with an energy consumption of 1.32 kWh/g N for total nitrogen removal, 0.45 kWh/g N for ammonia nitrogen removal, and 0.044 kWh/g for acetate production. Using boron-doped diamond (BDD) anode, 70.9%±12.1% ammonia removal and 51.5%±11.8% total nitrogen removal was obtained, with an energy consumption of 0.84 kWh/g N for total nitrogen removal, 0.61 kWh/g N for ammonia nitrogen removal, and 0.043 kWh/g for acetate production. A difference in nitrate accumulation explained the difference of total nitrogen removal efficiencies. Transport of ammonia and acetate across the membrane deteriorated the performance of MES. These results are important for the development of novel electricity-driven technologies for chemical production and pollution removal.