Peracetic acid (PAA)-based system is becoming an emerging advanced oxidation process (AOP) for effective removal of organic contaminants from water. Various approaches have been tested to activate PAA, while no previous researches reported the application of metal-organic frameworks (MOFs) materials for PAA activation. In this study, zeolitic imidazole framework (ZIF)-67, a representative MOFs, was facile synthesized via direct-mixing method at room temperature, and tested for PAA activation and sulfachloropyridazine (SCP) degradation. The as-synthesized ZIF-67 exhibited excellent performance for PAA activation and SCP degradation with 100% of SCP degraded within 3 min, owing to the specific MOFs structure and abundant Co2+ sites. The pseudo-first-order kinetic model was applied to fit the kinetic data, with rate constant k1 of ZIF-67 activated PAA system 34.2 and 156.5 times higher than those of conventional Co3O4 activated PAA and direct oxidation by PAA. Radical quenching experiments and electron paramagnetic resonance (EPR) analysis indicated that CH3C(O)OO• played a major role in this PAA activation system. Then, the Fukui index based on density functional theory (DFT) calculation was used to predict the possible reaction sites of SCP for electrophilic attack by CH3C(O)OO•. In addition, the degradation pathway of SCP was proposed based on Fukui index values and intermediates detection, which mainly included the S-N bond cleavage and SO2 extrusion and followed by further oxidation, dechlorination, and hydroxylation. Therefore, ZIF-67 activated PAA is a novel strategy and holds strong potential for the removal of emerging organic contaminants (EOCs) from water.
The release of microplastics (MPs) especially those with sizes less than 10 μm from effluent of wastewater treatment plants (WWTPs) is one of the major sources of plastics into aquatic environment. To reduce the discharge of MPs into environment, it is essential to further enhance their removal efficiencies in WWTPs. In present study, to boost the removal performance of MPs in sand filtration systems (units that commonly employed in WWTPs to remove colloidal pollutants), six types of biochar fabricated from three raw biomass materials (i.e. lignin, cellulose, and woodchips) at two pyrolysis temperatures (400 °C and 700 °C) was respectively amended into sand columns as thin permeable layer. We found that adding all six types of biochar into sand columns as thin permeable layer could greatly improve the retention of MPs with the diameter of 1 μm under either slow (4 m/d) or fast flow rates (160 m/d) due to the high adsorption capability of biochar. Woodchip-derived biochar exhibited the highest MPs retention performance, which was followed by cellulose-derived biochar and then lignin-derived biochar. Moreover, for biochar derived from three raw biomasses, increasing pyrolysis temperature could improve MPs retention performance. The direct observation of real-time plastics retention processes on different types of biochar via a visible flow chamber showed that woodchip-derived biochar especially that fabricated at 700 °C exhibited more MPs trapping processes relative to lignin and cellulose-derived biochar due to their more complex surface morphology. Thus, the highest MPs retention performance was achieved in sand columns with amendment by 1 wt% woodchip-derived biochar fabricated at 700 °C. More importantly, we found that for these modified sand filtration column systems, complete MPs removal could be achieved in real river water and actual sewage water, in multiple filtration cycles, longtime filtration process (100 pore volumes injection) as well as with interval flow conditions. Moreover, biochar could be regenerated and reused as thin permeable layer to effectively remove MPs. The results of this study clearly showed that biochar especially woodchip-derived biochar fabricated at 700 °C had the potential to immobilize MPs especially those with small sizes in WWTPs.
Magnetite nanoparticles (MNPs) with varied organic coatings (OCs) which improved their stability have broad environmental applications. However, the adsorbed amounts and layer thickness of varied OCs onto MNPs during the synthesis were generally not or poorly characterized, and their interactions with natural organic matter (NOM) were still in progress. In this study, acetic (HAc), citric (CA), and polyacrylic acid (PAA) were selected as model OCs, the adsorption behaviors of OCs on MNPs were characterized under varied aqueous C/Fe ratios, and the aggregation behaviors of MNPs with varied OCs (OC-MNPs) at neutral pH (7.0 ± 0.2) with NaCl (5–800 mM) in the presence/absence of NOM were systematically investigated. Under low aqueous C/Fe ratio, the adsorbed amounts of model OCs as –COOH/Fe ratio followed the order: CA ≈ PAA >> HAc. With high aqueous C/Fe ratio, the maximum adsorbed masses of OC-MNPs were similar. The adsorbed layer thicknesses of OC-MNPs were thoroughly characterized using three different methods, all showing that the adsorbed layer of PAA was thicker than that of CA and HAc. Derjaguin–Landau–Verwey–Overbeek (DLVO) and extended DLVO (EDLVO) calculations showed that electrostatic and van der Waals forces were dominant for CA-MNPs and HAc-MNPs stabilization; while steric repulsion played major roles in stabilizing PAA-MNPs, probably due to a thicker PAA layer. In the presence of NOM, stability behaviors of all OC-MNPs were similar, ascribing to the much greater amounts of NOM adsorbed than the OCs, causing greater steric repulsion. This study provides new mechanistic insights which could help better understand the effects of varied OCs on MNPs' colloidal stability.
Photocatalysis is an efficient technology for water decontamination and purification. Development of photocatalysts with high activity becomes the key to this research area. In recent years, titanate nanotubes (TNTs), derived from TiO2 nanoparticles through hydrothermal treatment with NaOH/KOH, have been attracting great attention. TNTs are composed of edge-sharing [TiO6] octahedrons as the skeleton and Na+/H+/K+ in the interlayers, which exhibit a uniform tubular microstructure, a large specific surface area, high photoelectric conversion properties, and good stability. Therefore, TNTs and their modified materials are widely used for removal of heavy metals and organic contaminants through photocatalytic oxidation or reduction. In this perspective, we systematically summarize cutting-edge research on the application of TNT-based photocatalysts in the water treatment area, illustrate the challenges for fundamental research and practical applications, and reveal the critical knowledge gaps and research needs for the future. In particular, preparation and specific properties of TNT-based photocatalysts are presented. Modification of TNTs to promote photocatalytic activity is discussed as well as their applications for contaminants removal from water. The latest advances in theoretical calculations on materials and contaminants in this photocatalysis system are clarified. In the future, strategic programs on both fundamental research and practical applications of TNT-based photocatalysts are proposed.
