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.     

Water-dispersible nano-pollutions reshape microbial metabolism in type-specific manners: A metabolic and bacteriological investigation in Escherichia coli

• Water-dispersible nano-pollutions exhibit type-specific toxic effects on E. coli. • Global metabolite profiling was used to characterize metabolic disruption patterns. • Key dysregulated metabolites responsive to nano-pollution exposures were found. • Amino acid metabolism and purine metabolism are perturbed at nano-pollutions. Incomplete separation and recycling of nanoparticles are causing undesirable nanopollution and thus raising great concerns with regard to nanosafety. Since microorganisms are important regulator of physiological processes in many organisms, the interaction between nanopollution and microbial metabolomics and the resultant impact on the host’s health are important but unclear. To investigate how typical nanopollution perturbs microbial growth and metabolism, Escherichia coli (E. coli) in vitro was treated with six water-dispersible nanomaterials (nanoplastic, nanosilver, nano-TiO₂, nano-ZnO, semiconductor quantum dots (QDs), carbon dots (CDs)) at human-/environment-relevant concentration levels. The nanomaterials exhibited type-specific toxic effects on E. coli growth. Global metabolite profiling was used to characterize metabolic disruption patterns in the model microorganism exposed to different nanopollutants. The percentage of significant metabolites (p<0.05, VIP>1) accounted for 6%–38% of the total 293 identified metabolites in each of the nanomaterial-contaminated bacterial groups. Metabolic results also exhibited significant differences between different nanopollutants and dose levels, revealing type-specific and untypical concentration-dependent metabolic responses. Key metabolites responsive to nanopollution exposures were mainly involved in amino acid and purine metabolisms, where 5, 4, and 7 significant metabolic features were included in arginine and proline metabolism, phenylalanine metabolism, and purine metabolism, respectively. In conclusion, this study horizontally compared and demonstrated how typical nanopollution perturbs microbial growth and metabolomics in a type-specific manner, which broadens our understanding of the ecotoxicity of nanopollutants on microorganisms.     

Response of bioaerosol cells to photocatalytic inactivation with ZnO and TiO2 impregnated onto Perlite and Poraver carriers

•ZnO/Perlite inactivated 72% of bioaerosols in continuous gas phase. •TiO₂ triggered the highest level of cytotoxicity with 95% dead cells onto Poraver. •Inactivation mechanism occurred by membrane damage, morphological changes and lysis. •ZnO/Poraver showed null inactivation of bioaerosols. •Catalysts losses at the outlet of the photoreactor for all systems were negligible. Bioaerosols are airborne microorganisms that cause infectious sickness, respiratory and chronic health issues. They have become a latent threat, particularly in indoor environment. Photocatalysis is a promising process to inactivate completely bioaerosols from air. However, in systems treating a continuous air flow, catalysts can be partially lost in the gaseous effluent. To avoid such phenomenon, supporting materials can be used to fix catalysts. In the present work, four photocatalytic systems using Perlite or Poraver glass beads impregnated with ZnO or TiO₂ were tested. The inactivation mechanism of bioaerosols and the cytotoxic effect of the catalysts to bioaerosols were studied. The plug flow photocatalytic reactor treated a bioaerosol flow of 460×1 0⁶ cells/m³_air with a residence time of 5.7 s. Flow Cytometry (FC) was used to quantify and characterize bioaerosols in terms of dead, injured and live cells. The most efficient system was ZnO/Perlite with 72% inactivation of bioaerosols, maintaining such inactivation during 7.5 h due to the higher water retention capacity of Perlite (2.8 mL/g_Perlite) in comparison with Poraver (1.5 mL/g_Perlite). However, a global balance showed that TiO₂/Poraver system triggered the highest level of cytotoxicity to bioaerosols retained on the support after 96 h with 95% of dead cells. SEM and FC analyses showed that the mechanism of inactivation with ZnO was based on membrane damage, morphological cell changes and cell lysis; whereas only membrane damage and cell lysis were involved with TiO₂. Overall, results highlighted that photocatalytic technologies can completely inactivate bioaerosols in indoor environments.     

Concurrent adsorption and reduction of chromium(VI) to chromium(III) using nitrogen-doped porous carbon adsorbent derived from loofah sponge

• A high-efficiency N-doped porous carbon adsorbent for Cr(VI) was synthesized. • The maximum adsorption capacity of Cr(VI) reached up to 285.71 mg/g at 318K. • The potential mechanism for Cr(VI) adsorption by NHPC was put forward. • DFT analyzed the adsorption energy and interaction between NHPC and Cr(VI). To develop highly effective adsorbents for chromium removal, a nitrogen-doped biomass-derived carbon (NHPC) was synthesized via direct carbonation of loofah sponge followed by alkali activation and doping modification. NHPC possessed a hierarchical micro-/mesoporous lamellar structure with nitrogen-containing functional groups (1.33 at%), specific surface area (1792.47 m²/g), and pore volume (1.18 cm³/g). NHPC exhibited a higher Cr(VI) adsorption affinity than the HPC (without nitrogen doping) or the pristine loofah sponge carbon (LSC) did. The influence of process parameters, including pH, dosage, time, temperature, and Cr(VI) concentration, on Cr(VI) adsorption by NHPC were evaluated. The Cr(VI) adsorption kinetics matched with the pseudo-second-order model (R²≥0.9983). The Cr(VI) adsorption isotherm was fitted with the Langmuir isotherm model, which indicated the maximum Cr(VI) adsorption capacities: 227.27, 238.10, and 285.71 mg/g at 298K, 308K, and 318K, respectively. The model analysis also indicated that adsorption of Cr(VI) on NHPC was a spontaneous, endothermal, and entropy-increasing process. The Cr(VI) adsorption process potentially involved mixed reductive and adsorbed mechanism. Furthermore, computational chemistry calculations revealed that the adsorption energy between NHPC and Cr(VI) (−0.84 eV) was lower than that of HPC (−0.51 eV), suggesting that nitrogen doping could greatly enhance the interaction between NHPC and Cr(VI).     

Fabrication of highly efficient Bi2WO6/CuS composite for visible-light photocatalytic removal of organic pollutants and Cr(VI) from wastewater

• A novel Bi₂WO₆/CuS composite was fabricated by a facile solvothermal method. • This composite efficiently removed organic pollutants and Cr(VI) by photocatalysis. • The DOM could promoted synchronous removal of organic pollutants and Cr(VI). • This composite could be applied at a wide pH range in photocatalytic reactions. • Possible photocatalytic mechanisms of organic pollutants and Cr(VI) were proposed. A visible-light-driven Bi₂WO₆/CuS p-n heterojunction was fabricated using an easy solvothermal method. The Bi₂WO₆/CuS exhibited high photocatalytic activity in a mixed system containing rhodamine B (RhB), tetracycline hydrochloride (TCH), and Cr (VI) under natural conditions. Approximately 98.8% of the RhB (10 mg/L), 87.6% of the TCH (10 mg/L) and 95.1% of the Cr(VI) (15 mg/L) were simultaneously removed from a mixed solution within 105 min. The removal efficiencies of TCH and Cr(VI) increased by 12.9% and 20.4%, respectively, in the mixed solution, compared with the single solutions. This is mainly ascribed to the simultaneous consumption electrons and holes, which increases the amount of excited electrons/holes and enhances the separation efficiency of photogenerated electrons and holes. Bi₂WO₆/CuS can be applied over a wide pH range (2–6) with strong photocatalytic activity for RhB, TCH and Cr(VI). Coexisiting dissolved organic matter in the solution significantly promoted the removal of TCH (from 74.7% to 87.2%) and Cr(VI) (from 75.7% to 99.9%) because it accelerated the separation of electrons and holes by consuming holes as an electron acceptor. Removal mechanisms of RhB, TCH, and Cr(VI) were proposed, Bi₂WO₆/CuS was formed into a p-n heterojunction to efficiently separate and transfer photoelectrons and holes so as to drive photocatalytic reactions. Specifically, when reducing pollutants (e.g., TCH) and oxidizing pollutants (e.g., Cr(VI)) coexist in wastewater, the p-n heterojunction in Bi₂WO₆/CuS acts as a “bridge” to shorten the electron transport and thus simultaneously increase the removal efficiencies of both types of pollutants.     

Crosslinking acrylamide with EDTA-intercalated layered double hydroxide for enhanced recovery of Cr(VI) and Congo red: Adsorptive and mechanistic study

• Functional groups of AM and EDTA in composite increased removal of Cr(VI) and CR. • Removal process reached equilibrium within 30 min and was minimally affected by pH. • Elimination of Cr(VI) was promoted by coexisting CR. • Adsorption process of CR was less influenced by the presence of Cr(VI). • Mechanisms were electrostatic attraction, surface complexation and anion exchange. We prepared ethylenediaminetetraacetic acid (EDTA)-intercalated MgAl-layered double hydroxide (LDH-EDTA), then grafted acrylamide (AM) to the LDH-EDTA by a cross-linking method to yield a LDH-EDTA-AM composite; we then evaluated its adsorptive ability for Congo red (CR) and hexavalent chromium (Cr(VI)) in single and binary adsorption systems. The adsorption process on LDH-EDTA-AM for CR and Cr(VI) achieved equilibrium quickly, and the removal efficiencies were minimally affected by initial pH. The maximum uptake quantities of CR and Cr(VI) on LDH-EDTA-AM were 632.9 and 48.47 mg/g, respectively. In mixed systems, chromate removal was stimulated by the presence of CR, while the adsorption efficiency of CR was almost not influenced by coexisting Cr(VI). The mechanisms involved electrostatic attraction, surface complexation, and anion exchange for the adsorption of both hazardous pollutants. In the Cr(VI) adsorption process, reduction also took place. The removal efficiencies in real contaminated water were all higher than those in the laboratory solutions.     

Hexavalent chromium in drinking water: Chemistry,challenges and future outlook on Sn(II)- and photocatalyst-based treatment

• Wide occurrence of Cr(VI) in US source drinking water. • A strong dependence of occurrence on groundwater sources. • Elucidate Redox and equilibrium chemistry of Cr(VI). • Sn(II)-based and TiO₂-based reductive treatments hold extreme promise. • Key challenges include residual waste, Cr(VI) re-generation and socioeconomic drivers. Chromium (Cr) typically exists in either trivalent and hexavalent oxidation states in drinking water, i.e., Cr(III) and Cr(VI), with Cr(VI) of particular concern in recent years due to its high toxicity and new regulatory standards. This Account presented a critical analysis of the sources and occurrence of Cr(VI) in drinking water in the United States, analyzed the equilibrium chemistry of Cr(VI) species, summarized important redox reaction relevant to the fate of Cr(VI) in drinking water, and critically reviewed emerging Cr(VI) treatment technologies. There is a wide occurrence of Cr(VI) in US source drinking water, with a strong dependence on groundwater sources, mainly due to naturally weathering of chromium-containing aquifers. Challenges regarding traditional Cr(VI) treatment include chemical cost, generation of secondary waste and inadvertent re-generation of Cr(VI) after treatment. To overcome these challenges, reductive Cr(VI) treatment technologies based on the application of stannous tin or electron-releasing titanium dioxide photocatalyst hold extreme promise in the future. To moving forward in the right direction, three key questions need further exploration for the technology implementation, including effective management of residual waste, minimizing the risks of Cr(VI) re-occurrence downstream of drinking water treatment plant, and promote the socioeconomic drivers for Cr(VI) control in the future.     

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.     

Influences and mechanisms of nanofullerene on the horizontal transfer of plasmid-encoded antibiotic resistance genes between E. coli strains

• Sub-inhibitory levels of nC₆₀ promote conjugative transfer of ARGs. • nC₆₀ can induce ROS generation, oxidative stress and SOS response. • nC₆₀ can increase cell membrane permeability and alter gene expression. • Results provide evidence of nC₆₀ promoting antibiotic resistance dissemination. The spread and development of antibiotic resistance globally have led to severe public health problems. It has been shown that some non-antibiotic substances can also promote the diffusion and spread of antibiotic resistance genes (ARGs). Nanofullerene (nC₆₀) is a type of nanomaterial widely used around the world, and some studies have discovered both the biological toxicity and environmental toxicity of nC₆₀. In this study, cellular and molecular biology techniques were employed to investigate the influences of nC₆₀ at sub-minimum inhibitory concentrations (sub-MICs) on the conjugation of ARGs between the E. coli strains. Compared with the control group, nC₆₀ significantly increased the conjugation rates of ARGs by 1.32‒10.82 folds within the concentration range of 7.03‒1800 mg/L. This study further explored the mechanism of this phenomenon, finding that sub-MICs of nC₆₀ could induce the production of reactive oxygen species (ROS), trigger SOS-response and oxidative stress, affect the expression of outer membrane proteins (OMPs) genes, increase membrane permeability, and thus promote the occurrence of conjugation. This research enriches our understanding of the environmental toxicity of nC₆₀, raises our risk awareness toward nC₆₀, and may promote the more rational employment of nC₆₀ materials.     

Transport of bacterial cell (E. coli) from different recharge water resources in porous media during simulated artificial groundwater recharge

• The recharge pond dwelling process induced changes in cell properties. • Cell properties and solution chemistry exerted confounding effect on cell transport. • E. coli cells within different recharge water displayed different spreading risks. Commonly used recharge water resources for artificial groundwater recharge (AGR) such as secondary effluent (SE), river water and rainfall, are all oligotrophic, with low ionic strengths and different cationic compositions. The dwelling process in recharge pond imposed physiologic stress on Escherichia coli (E. coli) cells, in all three types of investigated recharge water resources and the cultivation of E. coli under varying recharge water conditions, induced changes in cell properties. During adaptation to the recharge water environment, the zeta potential of cells became more negative, the hydrodynamic diameters, extracellular polymeric substances content and surface hydrophobicity decreased, while the cellular outer membrane protein profiles became more diverse. The mobility of cells altered in accordance with changes in these cell properties. The E. coli cells in rainfall recharge water displayed the highest mobility (least retention), followed by cells in river water and finally SE cells, which had the lowest mobility. Simulated column experiments and quantitative modeling confirmed that the cellular properties, driven by the physiologic state of cells in different recharge water matrices and the solution chemistry, exerted synergistic effects on cell transport behavior. The findings of this study contribute to an improved understanding of E. coli transport in actual AGR scenarios and prediction of spreading risk in different recharge water sources.     

Fate of microplastics in a coastal wastewater treatment plant: Microfibers could partially break through the integrated membrane system

• Fate of microplastics in integrated membrane system for water reuse was investigated. • Integrated membrane system has high removal efficiency (>98%) for microplastics. • Microplastics (>93%) were mainly removed through membrane bioreactor treatment. • Small scale fiber plastics (<200 μm) could break through reverse osmosis (RO) system. • The flux of microplastics maintained at 2.7 × 10¹¹ MPs/d after the RO treatment. Rare information on the fate of microplastics in the integrated membrane system (IMS) system in full-scale wastewater treatment plant was available. The fate of microplastics in IMS in a coastal reclaimed water plant was investigated. The removal rate of microplastics in the IMS system reached 93.2% after membrane bioreactor (MBR) treatment while that further increased to 98.0% after the reverse osmosis (RO) membrane process. The flux of microplastics in MBR effluent was reduced from 1.5 × 10¹³ MPs/d to 10.2 × 10¹¹ MPs/d while that of the RO treatment decreased to 2.7 × 10¹¹ MPs/d. Small scale fiber plastics (<200 μm) could break through RO system according to the size distribution analysis. The application of the IMS system in the reclaimed water plant could prevent most of the microplastics from being discharged in the coastal water. These findings suggested that the IMS system was more efficient than conventional activated sludge system (CAS) for the removal of microplastics, while the discharge of small scale fiber plastics through the IMS system should also not be neglected because small scale fiber plastics (<200 μm) could break through IMS system equipped with the RO system.     

Biogenic palladium prepared by activated sludge microbes for the hexavalent chromium catalytic reduction: Impact of relative biomass

• Pd nanoparticles could be reduced and supported by activated sludge microbes. • The effect of biomass on Pd adsorption by microbes is greater than Pd reduction. • More biomass reduces Pd particle size, which is more dispersed on the cell surface. • When the biomass/Pd add to 6, the catalytic reduction rate of Cr(VI) reaches stable. Palladium, a kind of platinum group metal, owns catalytic capacity for a variety of hydrogenations. In this study, Pd nanoparticles (PdNPs) were generated through enzymatic recovery by microbes of activated sludge at various biomass/Pd, and further used for the Cr(VI) reduction. The results show that biomass had a strong adsorption capacity for Pd(II), which was 17.25 mg Pd/g sludge. The XRD and TEM-EDX results confirmed the existence of PdNPs associated with microbes (bio-Pd). The increase of biomass had little effect on the reduction rate of Pd(II), but it could cause decreasing particle size and shifting location of Pd(0) with the better dispersion degree on the cell surface. In the Cr(VI) reduction experiments, Cr(VI) was first adsorbed on bio-Pd with hydrogen and then reduced using active hydrogen as electron donor. Biomass improved the catalytic activity of PdNPs. When the biomass/Pd (w/w) ratio increased to six or higher, Cr(VI) reduction achieved maximum rate that 50 mg/L of Cr(VI) could be rapidly reduced in one minute.     

Visible-light-driven heterostructured g-C3N4/Bi-TiO2 floating photocatalyst with enhanced charge carrier separation for photocatalytic inactivation of Microcystis aeruginosa

• Bi doping in TiO₂ enhanced the separation of photo-generated electron-hole. • The performance of photocatalytic degradation of MC-LR was improved. • Coexisting substances have no influence on algal removal performance. • The key reactive oxygen species were h⁺ and ^•OH in the photocatalytic process. The increase in occurrence and severity of cyanobacteria blooms is causing increasing concern; moreover, human and animal health is affected by the toxic effects of Microcystin-LR released into the water. In this paper, a floating photocatalyst for the photocatalytic inactivation of the harmful algae Microcystis aeruginosa (M. aeruginosa) was prepared using a simple sol-gel method, i.e., coating g-C₃N₄ coupled with Bi-doped TiO₂ on Al₂O₃-modified expanded perlite (CBTA for short). The impact of different molar ratios of Bi/Ti on CBTA was considered. The results indicated that Bi doping in TiO₂ inhibited photogenerated electron-hole pair recombination. With 6 h of visible light illumination, 75.9% of M. aeruginosa (initial concentration= 2.7 × 10⁶ cells/L) and 83.7% of Microcystin-LR (initial concentration= 100 μg/L) could be removed with the addition of 2 g/L CBTA-1% (i.e., Bi/Ti molar ratio= 1%). The key reactive oxygen species (ROSs) in the photocatalytic inactivation process are h⁺ and ^•OH. The induction of the Bi⁴⁺/Bi³⁺ species by the incorporation of Bi could narrow the bandgap of TiO₂, trap electrons, and enhance the stability of CBTA-1% in the solutions with coexisting environmental substances.     

A novel strategy for gas mitigation during swine manure odour treatment using seaweed and a microbial consortium

• Comprehensive mitigation of gas emissions from swine manure was investigated. • Additives addition for mitigation of gas from the manure has been developed. • Sargassum horneri, seaweed masking strategy controlled gas by 90%-100%. • Immediate reduction in emitted gas and improving air quality has been determined. • Microbial consortium with seaweed completely controlled gas emissions by 100%. Gas emissions from swine farms have an impact on air quality in the Republic of Korea. Swine manure stored in deep pits for a long time is a major source of harmful gas emissions. Therefore, we evaluated the mitigation of emissions of ammonia (NH₃), hydrogen sulfide (H₂S) and amine gases from swine manure with biological products such as seaweed (Sargassum horneri) and a microbial consortium (Bacillus subtilis (1.2 × 10⁹ CFU/mL), Thiobacillus sp. (1.0 × 10¹⁰ CFU/mL) and Saccharomyces cerevisiae (2.0 × 10⁹ CFU/mL)) used as additives due to their promising benefits for nutrient cycling. Overall, seaweed powder masking over two days provided notable control of over 98%-100% of the gas emissions. Furthermore, significant control of gas emissions was especially pronounced when seaweed powder masking along with a microbial consortium was applied, resulting in a gas reduction rate of 100% for NH₃, amines and H₂S over 10 days of treatment. The results also suggested that seaweed powder masking and a microbial consortium used in combination to reduce the gas emissions from swine manure reduced odour compared with that observed when the two additives were used alone. Without the consortium, seaweed decreased total volatile fatty acid (VFA) production. The proposed novel method of masking with a microbial consortium is promising for mitigating hazardous gases, simple, and environmentally beneficial. More research is warranted to determine the mechanisms underlying the seaweed and substrate interactions.     

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.     

Stabilization of hexavalent chromium with pretreatment and high temperature sintering in highly contaminated soil

• Separate reduction and sintering cannot be effective for Cr stabilization. • Combined treatment of reduction and sintering is effective for Cr stabilization. • Almost all the Cr in the reduced soil is residual form after sintering at 1000°C. This study explored the effectiveness and mechanisms of high temperature sintering following pre-reduction with ferric sulfate (FeSO₄), sodium sulfide (Na₂S), or citric acid (C₆H₈O₇) in stabilizing hexavalent chromium (Cr(VI)) in highly contaminated soil. The soil samples had an initial total Cr leaching of 1768.83 mg/L, and Cr(VI) leaching of 1745.13 mg/L. When FeSO₄ or C₆H₈O₇ reduction was followed by sintering at 1000°C, the Cr leaching was reduced enough to meet the Safety Landfill Standards regarding general industrial solid waste. This combined treatment greatly improved the stabilization efficiency of chromium because the reduction of Cr(VI) into Cr(III) decreased the mobility of chromium and made it more easily encapsulated in minerals during sintering. SEM, XRD, TG-DSC, and speciation analysis indicated that when the sintering temperature reached 1000°C, almost all the chromium in soils that had the pre-reduction treatment was transformed into the residual form. At 1000°C, the soil melted and promoted the mineralization of Cr and the formation of new Cr-containing compounds, which significantly decreased subsequent leaching of chromium from the soil. However, without reduction treatment, chromium continued to leach from the soil even after being sintered at 1000°C, possibly because the soil did not fully fuse and because Cr(VI) does not bind with soil as easily as Cr(III).     

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.     

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.     

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.     

Long-term adaptive evolution of Shewanella oneidensis MR-1 for establishment of high concentration Cr(VI) tolerance

• Shewanella oneidensis MR-1 was acclimated to grow with Cr(VI) of 190 mg/L. • Whole genomes from 7 populations at different acclimation stages were sequenced. • Gene mutations mainly related to efflux pumps and transporters. • An adaptation mechanism of MR-1 to high concentration of Cr(VI) was proposed. Acclimation is the main method to enhance the productivity of microorganisms in environmental biotechnology, but it remains uncertain how microorganisms acquire resistance to high concentrations of pollutants during long-term acclimation. Shewanella oneidensis MR-1 was acclimated for 120 days with increasing hexavalent chromium (Cr(VI)) concentrations from 10 to 190 mg/L. The bacterium was able to survive from the highly toxic Cr(VI) environment due to its enhanced capability to reduce Cr(VI) and the increased cell membrane surface. We sequenced 19 complete genomes from 7 populations of MR-1, including the ancestral strain, the evolved strains in Cr(VI) environment on days 40, 80 and 120 and their corresponding controls. A total of 27, 49 and 90 single nucleotide polymorphisms were found in the Cr(VI)-evolved populations on days 40, 80 and 120, respectively. Nonsynonymous substitutions were clustered according to gene functions, and the gene mutations related to integral components of the membrane, including efflux pumps and transporters, were the key determinants of chromate resistance. In addition, MR-1 strengthened the detoxification of Cr(VI) through gene variations involved in adenosine triphosphate binding, electron carrier activity, signal transduction and DNA repair. Our results provide an in-depth analysis of how Cr(VI) resistance of S. oneidensis MR-1 is improved by acclimation, as well as a genetic understanding of the impact of long-term exposure of microorganisms to pollution.