Adsorption characteristics of ciprofloxacin onto g-MoS2 coated biochar nanocomposites

• The g-MoS₂ coated composites (g-MoS₂-BC) were synthesized. • The coated g-MoS₂ greatly increased the adsorption ability of biochar. • The synergistic effect was observed for CIP adsorption on g-MoS₂-RC700. • The adsorption mechanisms of CIP on g-MoS₂-BC were proposed. The g-MoS₂ coated biochar (g-MoS₂-BC) composites were synthesized by coating original biochar with g-MoS₂ nanosheets at 300°C(BC300)/700°C (BC700). The adsorption properties of the g-MoS₂-BC composites for ciprofloxacin (CIP) were investigated with an aim to exploit its high efficiency toward soil amendment. The specific surface area and the pore structures of biochar coated g-MoS₂ nanosheets were significantly increased. The g-MoS₂-BC composites provided more π electrons, which was favorable in enhancing the π-π electron donor-acceptor (EDA) interactions between CIP and biochar. As a result, the g-MoS₂-BC composites showed faster adsorption rate and greater adsorption capacity for CIP than the original biochar. The coated g-MoS₂ nanosheets contributed more to CIP adsorption on the g-MoS₂-BC composites due to their greater CIP adsorption capacity than the original biochar. Moreover, the synergistic effect was observed for CIP adsorption on g-MoS₂-BC700, and suppression effect on g-MoS₂-BC300. In addition, the adsorption of CIP onto g-MoS₂-BC composites also exhibited strong dependence on the solution pH, since it can affect both the adsorbent surface charge and the speciation of contaminants. It was reasonably suggested that the mechanisms of CIP adsorption on g-MoS₂-BC composites involved pore-filling effects, π-π EDA interaction, electrostatic interaction, and ion exchange interaction. These results are useful for the modification of biochar in exploiting the novel amendment for contaminated soils.     

Removal and recovery of toxic nanosized Cerium Oxide using eco-friendly Iron Oxide Nanoparticles

• Eco-friendly IONPs were synthesized through solvothermal method. • IONPs show very high removal efficiency for CeO₂ NPs i.e. 688 mg/g. • Removal was >90% in all synthetic and real water samples. • >80% recovery of CeO₂ NPs through sonication confirms reusability of IONPs. Increasing applications of metal oxide nanoparticles and their release in the natural environment is a serious concern due to their toxic nature. Therefore, it is essential to have eco-friendly solutions for the remediation of toxic metal oxides in an aqueous environment. In the present study, eco-friendly Iron Oxide Nanoparticles (IONPs) are synthesized using solvothermal technique and successfully characterized using scanning and transmission electron microscopy (SEM and TEM respectively) and powder X-Ray diffraction (PXRD). These IONPs were further utilized for the remediation of toxic metal oxide nanoparticle, i.e., CeO₂. Sorption experiments were also performed in complex aqueous solutions and real water samples to check its applicability in the natural environment. Reusability study was performed to show cost-effectiveness. Results show that these 200 nm-sized spherical IONPs, as revealed by SEM and TEM analysis, were magnetite (Fe₃O₄) and contained short-range crystallinity as confirmed from XRD spectra. Sorption experiments show that the composite follows the pseudo-second-order kinetic model. Further R²>0.99 for Langmuir sorption isotherm suggests chemisorption as probable removal mechanism with monolayer sorption of CeO₂ NPs on IONP. More than 80% recovery of adsorbed CeO₂ NPs through ultrasonication and magnetic separation of reaction precipitate confirms reusability of IONPs. Obtained removal % of CeO₂ in various synthetic and real water samples was>90% signifying that IONPs are candidate adsorbent for the removal and recovery of toxic metal oxide nanoparticles from contaminated environmental water samples.     

Synthesis of vinasse-dolomite nanocomposite biochar via a novel developed functionalization method to recover phosphate as a potential fertilizer substitute

• Nanocomposites were prepared by adding dolomite to vinasse at different ratio. • Textural and morphological features of adsorbents were studied in detail. • CCD based RSM was used for investigation of P ion removal by nanocomposite. • The q_m based on Langmuir model for modified vinasse biochar was 178.57 mg/g. • P loaded nanocomposite improved plant growth and could be utilized as P-fertilizer. The effectiveness of phosphate (P) removal from aqueous solutions was investigated by novel low-cost biochars synthesized from vinasse and functionalized with calcined dolomite. The vinasse-derived biochar, synthesized via pyrolysis at different temperatures, showed easy preparation and a large surface area. The novel vinasse biochar nanocomposites were prepared by adding dolomite to the vinasse biochars with different weight percentages (10, 20 and 30%). The characteristics of the prepared materials were identified for further understanding of the inherent adsorption mechanism between P ions and vinasse biochars. Vinasse-dolomite nanocomposite was very effective in the adsorption of P species from aqueous media. The effect of the operational factors on Vinasse-dolomite nanocomposite was explored by applying response surface methodology (RSM). According to RSM results, the optimum condition was achieved to be contact time 90 (min), 250 (mg/L) of P concentration and pH 7. Thermodynamic isotherm and kinetic studies were applied on experimental data to understand the adsorption behavior. The Vinasse-dolomite nanocomposite revealed preferential P species adsorption in the presence of co-existing anions. The P species could be recovered by 1.0 M HCl where the efficiency was not affected up to the fifth cycle. The P-loaded Vinasse-dolomite nanocomposite was successfully tested on a plant; it significantly improved its growth and proved its potency as a P-based fertilizer substitute.     

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.     

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.     

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.     

Enhancement of the electrocatalytic oxidation of antibiotic wastewater over the conductive black carbon-PbO2 electrode prepared using novel green approach

• A novel conductive carbon black modified lead dioxide electrode is synthesized. • The modified PbO₂ electrode exhibits enhanced electrochemical performances. • BBD method could predict optimal experiment conditions accurately and reliably. • The modified electrode possesses outstanding reusability and safety. The secondary pollution caused by modification of an electrode due to doping of harmful materials has long been a big concern. In this study, an environmentally friendly material, conductive carbon black, was adopted for modification of lead dioxide electrode (PbO₂). It was observed that the as-prepared conductive carbon black modified electrode (C-PbO₂) exhibited an enhanced electrocatalytical performance and more stable structure than a pristine PbO₂ electrode, and the removal efficiency of metronidazole (MNZ) and COD by a 1.0% C-PbO₂ electrode at optimal conditions was increased by 24.66% and 7.01%, respectively. Results revealed that the electrochemical degradation of MNZ wastewater followed pseudo-first-order kinetics. This intimates that the presence of conductive carbon black could improve the current efficiency, promote the generation of hydroxyl radicals, and accelerate the removal of MNZ through oxidation. In addition, MNZ degradation pathways through a C-PbO₂ electrode were proposed based on the identified intermediates. To promote the electrode to treat antibiotic wastewater, optimal experimental conditions were predicted through the Box-Behnken design (BBD) method. The results of this study suggest that a C-PbO₂ electrode may represent a promising functional material to pretreat antibiotic wastewaters.     

Low-cost adsorbents for urban stormwater pollution control

• Various low-cost adsorbents are studied for capturing urban stormwater pollutants. • Adsorbents are selected based on both pollutant adsorption and unexpected leaching. • Application modes of adsorbents influence their utilization efficacy in practice. Stormwater represents a major non-point pollution source at an urban environment. To improve the treatment efficacy of stormwater infrastructure, low-cost adsorbents have increasingly gained attention over the past decades. This article aims to briefly discuss several key aspects and principles for utilization of low-cost adsorbents for urban stormwater treatment. To determine whether a low-cost adsorbent is suitable for stormwater treatment, two aspects should be carefully assessed, including: 1) its adsorption mechanisms and behaviors that can influence the binding stre.g.,h, adsorption kinetics, and treatment capacity; and 2) unwanted chemical leaching patterns that can affect the extent of water quality degradation. Furthermore, the application mode of an adsorbent in the system design influences the utilization efficiency. Adsorbents, after dosed to soil media in infrastructure, would eventually become ineffective after oversaturation. In contrast, standalone filters or innovative composite adsorbents (e.g., adsorbent-coated mulch chips) can enable a long-lasting adsorption due to periodic replacement with fresh adsorbents. The aforementioned principles play a key role in the success of urban stormwater treatment with low-cost adsorbents.     

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.     

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.     

In situ synthesis of FeS/Carbon fibers for the effective removal of Cr(VI) in aqueous solution

• FeS/carbon fibers were in situ synthesized with Fe-carrageenan hydrogel fiber. • The double helix structure of carrageenan is used to load and disperse Fe. • Pyrolyzing sulfate groups enriched carrageenan-Fe could easily generate FeS. • The adsorption mechanisms include reduction and complexation reaction. Iron sulfide (FeS) nanoparticles (termed FSNs) have attracted much attention for the removal of pollutants due to their high efficiency and low cost, and because they are environmentally friendly. However, issues of agglomeration, transformation, and the loss of active components limit their application. Therefore, this study investigates in situ synthesized FeS/carbon fibers with an Fe-carrageenan biomass as a precursor and nontoxic sulfur source to ascertain the removal efficiency of the fibers. The enrichment of sulfate groups as well as the double-helix structure in ι-carrageenan-Fe could effectively avoid the aggregation and loss of FSNs in practical applications. The obtained FeS/carbon fibers were used to control a Cr(VI) polluted solution, and exhibited a relatively high removal capacity (81.62 mg/g). The main mechanisms included the reduction of FeS, electrostatic adsorption of carbon fibers, and Cr(III)-Fe(III) complexation reaction. The pseudo-second-order kinetic model and Langmuir adsorption model both provided a good fit of the reaction process; hence, the removal process was mainly controlled by chemical adsorption, specifically monolayer adsorption on a uniform surface. Furthermore, co-existing anions, column, and regeneration experiments indicated that the FeS/carbon fibers are a promising remediation material for practical application.     

Degradation of refractory organics in concentrated leachate by the Fenton process: Central composite design for process optimization

• 90% total COD, 95.3% inert COD and 97.2% UV₂₅₄ were removed. • High R² values (over 95%) for all responses were obtained with CCD. • Operational cost was calculated to be 0.238 €/g COD_removed for total COD removal. • Fenton oxidation was highly-efficient method for inert COD removal. • BOD₅/COD ratio of leachate concentrate raised from 0.04 to 0.4. The primary aim of this study is inert COD removal from leachate nanofiltration concentrate because of its high concentration of resistant organic pollutants. Within this framework, this study focuses on the treatability of leachate nanofiltration concentrate through Fenton oxidation and optimization of process parameters to reach the maximum pollutant removal by using response surface methodology (RSM). Initial pH, Fe²⁺ concentration, H₂O₂/Fe²⁺ molar ratio and oxidation time are selected as the independent variables, whereas total COD, color, inert COD and UV₂₅₄ removal are selected as the responses. According to the ANOVA results, the R² values of all responses are found to be over 95%. Under the optimum conditions determined by the model (pH: 3.99, Fe²⁺: 150 mmol/L, H₂O₂/Fe²⁺: 3.27 and oxidation time: 84.8 min), the maximum COD removal efficiency is determined as 91.4% by the model. The color, inert COD and UV₂₅₄ removal efficiencies are determined to be 99.9%, 97.2% and 99.5%, respectively, by the model, whereas the total COD, color, inert COD and UV₂₅₄ removal efficiencies are found respectively to be 90%, 96.5%, 95.3% and 97.2%, experimentally under the optimum operating conditions. The Fenton process improves the biodegradability of the leachate NF concentrate, increasing the BOD₅/COD ratio from the value of 0.04 to the value of 0.4. The operational cost of the process is calculated to be 0.238 €/g COD_removed. The results indicate that the Fenton oxidation process is an efficient and economical technology in improvement of the biological degradability of leachate nanofiltration concentrate and in removal of resistant organic pollutants.     

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 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.     

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.     

Evolution of humic substances in polymerization of polyphenol and amino acid based on non-destructive characterization

• Humification evolution was identified with non-destructive characterization method. • Humification process from precursors to fulvic and humic acid was confirmed. • MnO₂ alone had limited oxidation ability to form HA. • MnO₂ played a key role as a catalyst to transform FA to HA in the presence of O₂. • MnO₂ could affect the structure of the humification products. Abiotic humification is important in the formation and evolution of organic matter in soil and compost maturing processes. However, the roles of metal oxides in abiotic humification reactions under micro-aerobic remain ambiguous. The aim of this study was to use non-destructive measurement methods to investigate the role of MnO₂ in the evolution of humic substances (HSs) during oxidative polymerization of polyphenol-amino acid. Our results suggested a synergistic effect between MnO₂ and O₂ in promoting the polymerization reaction and identified that MnO₂ alone had a limited ability in accelerating the transformation of fulvic acid (FA) to humic acid (HA), whereas O₂ was the key factor in the process. Two-dimensional correlation spectroscopy (2D-COS) showed that the evolution in the UV-vis spectra followed the order of 475–525 nm>300–400 nm>240–280 nm in the humification process, indicating the formation of simple organic matter followed by FA and then HA. ¹³C nuclear magnetic resonance (¹³C NMR) analysis revealed that the products under both air and N₂ conditions in the presence of MnO₂ had greater amounts of aromatic-C than in the absence of MnO₂, demonstrating that MnO₂ affected the structure of the humification products. The results of this study provided new insights into the theory of abiotic humification.     

PM-support interfacial effect and oxygen mobility in Pt,Pd or Rh-loaded (Ce,Zr,La)O2 catalysts

• Pt/CZL exhibits the optimum catalytic performance for HC and NO_x elimination. • The strong PM-Ce interaction favors the oxygen mobility and DOSC. • Pd/CZL shows higher catalytic activity for CO conversion due to more O_latt species. • Great oxygen mobility at high temperature broadens the dynamic operation window. • The relationship between DOSC and catalytic performance is revealed. The physicochemical properties of Pt-, Pd- and Rh- loaded (Ce,Zr,La)O₂ (shorted for CZL) catalysts before/after aging treatment were systematically characterized by various techniques to illustrate the relationship of the dynamic oxygen storage/release capacity and redox ability with their catalytic performances for HC, NO_x and CO conversions. Pt/CZL catalyst exhibits the optimum catalytic performance for HC and NO_x elimination, which mainly contribute to its excellent redox ability and dynamic oxygen storage/release capacity (DOSC) at lower temperature due to the stronger PM (precious metals)-support interaction. However, the worse stability of Pt-O-Ce species and volatile Pt oxides easily result in the dramatical decline in catalytic activity after aging. Pd/CZL shows higher catalytic activity for CO conversion by reason of more O_latt species as the active oxygen for CO oxidation reaction. Rh/CZL catalyst displays the widest dynamic operation window for NO_x elimination as a result of greater oxygen mobility at high temperature, and the ability to retain more Rh-O-Ce species after calcined at 1100°C effectively restrains sintering of active RhO_x species, improving the thermal stability of Rh/CZL catalyst.     

Zero-valent manganese nanoparticles coupled with different strong oxidants for thallium removal from wastewater

• Nano zero-valent manganese (nZVMn, Mn⁰) is synthesized via borohydrides reduction. • Mn⁰ combined with persulfate/hypochlorite is effective for Tl removal at pH 6-12. • Mn⁰ can activate persulfate to form hydroxyl and sulfate radicals. • Oxidation-induced precipitation and surface complexation contribute to Tl removal. • Combined Mn⁰-oxidants process is promising in the environmental field. Nano zero-valent manganese (nZVMn, Mn⁰) was prepared through a borohydride reduction method and coupled with different oxidants (persulfate (S₂O₈²⁻), hypochlorite (ClO⁻), or hydrogen peroxide (H₂O₂)) to remove thallium (Tl) from wastewater. The surface of Mn⁰ was readily oxidized to form a core-shell composite (MnO_x@Mn⁰), which consists of Mn⁰ as the inner core and MnO_x (MnO, Mn₂O₃, and Mn₃O₄) as the outer layer. When Mn⁰ was added alone, effective Tl(I) removal was achieved at high pH levels (>12). The Mn⁰-H₂O₂ system was only effective in Tl(I) removal at high pH (>12), while the Mn⁰-S₂O₈²⁻ or Mn⁰-ClO⁻ system had excellent Tl(I) removal (>96%) over a broad pH range (4–12). The Mn⁰-S₂O₈²⁻ oxidation system provided the best resistance to interference from an external organic matrix. The isotherm of Tl(I) removal through the Mn⁰-S₂O₈²⁻ system followed the Freundlich model. The Mn⁰ nanomaterials can activate persulfate to produce sulfate radicals and hydroxyl radicals. Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy suggested that oxidation-induced precipitation, surface adsorption, and electrostatic attraction are the main mechanisms for Tl(I) removal resulting from the combination of Mn⁰ and oxidants. Mn⁰ coupled with S₂O₈²⁻/ClO⁻ is a novel and effective technique for Tl(I) removal, and its application in other fields is worthy of further investigation.     

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.     

Ceramic water filter for point-of-use water treatment in developing countries: Principles,challenges and opportunities

• CWF is a sustainable POU water treatment method for developing areas. • CWF manufacturing process is critical for its filtration performance. • Simultaneous increase of flow rate and pathogen removal is a challenge. • Control of pore size distribution holds promises to improve CWF efficiency. • Novel coatings of CWFs are a promising method to improve contaminant removal. Drinking water source contamination poses a great threat to human health in developing countries. Point-of-use (POU) water treatment techniques, which improve drinking water quality at the household level, offer an affordable and convenient way to obtain safe drinking water and thus can reduce the outbreaks of waterborne diseases. Ceramic water filters (CWFs), fabricated from locally sourced materials and manufactured by local labor, are one of the most socially acceptable POU water treatment technologies because of their effectiveness, low-cost and ease of use. This review concisely summarizes the critical factors that influence the performance of CWFs, including (1) CWF manufacturing process (raw material selection, firing process, silver impregnation), and (2) source water quality. Then, an in-depth discussion is presented with emphasis on key research efforts to address two major challenges of conventional CWFs, including (1) simultaneous increase of filter flow rate and bacterial removal efficiency, and (2) removal of various concerning pollutants, such as viruses and metal(loid)s. To promote the application of CWFs, future research directions can focus on: (1) investigation of pore size distribution and pore structure to achieve higher flow rates and effective pathogen removal by elucidating pathogen transport in porous ceramic and adjusting manufacture parameters; and (2) exploration of new surface modification approaches with enhanced interaction between a variety of contaminants and ceramic surfaces.