Understanding the pivotal role of ubiquitous Yellow River suspend sediment in efficiently degrading metronidazole pollutants in water environments.

Sulfite-based advanced oxidation technology has received considerable attention for its application in organic pollutants elimination. However, the potential of natural sediments as effective catalysts for sulfite activation has been overlooked. This study investigates a novel process utilizing suspended sediment/sulfite (SS/S(IV)) for degradation of metronidazole (MNZ). Our results demonstrate that MNZ degradation efficiency can reach to 93.1 % within 90 min with 12.0 g SS and 2.0 mM sulfite. The influencing environmental factors, including initial pH, SS dosage, S(IV) concentration, temperature, and co-existing substances were systematically investigated. Quenching experiments and electron paramagnetic resonance analyses results indicate that SO3•- is the primary active substance responsible for MNZ degradation, with involvement of SO4•-, SO5•-, and •OH. X-ray photoelectron spectroscopy and Mössbauer spectra reveal that Fe (III)-silicates play a crucial role in activating S(IV). Furthermore, analysis of degradation intermediates and pathways of MNZ is conducted using liquid chromatography with mass spectrometry (LC -MS). The toxicity of MNZ and its intermediates were also systematically evaluated by the T.E.ST. program and wheat seeds germination test. This study offers valuable insight into the activation of sulfite by natural sediments and could contribute to the development of SS-based advanced oxidation processes (AOPs) for the in-situ remediation of antibiotics-contaminated water environments.

Study of the adsorption behavior of tetracycline onto suspended sediments in the Yellow River, China: Insights into the transportation and mechanism.

The increasing usage of household drugs has contributed to the widespread distribution of antibiotic pollutants in the aquatic environment. Although previous studies have proven that sediments could act as an important transport vector of antibiotic pollutants, the crucial impact of suspended sediments (SS) on the migration and fate of antibiotics in water bodies remains unclear. This study systematically investigated the performance and potential mechanism of adsorption of tetracycline (TC) on SS in the Yellow River. The results show that physisorption (pore filling, hydrogen bonding) and chemisorption (π-π interaction, surface complexation, and electrostatic interaction) activities contributed to the adsorption of TC onto SS. The mineral components (SiO2, Fe2O3, and Al2O3) of SS were found to be the main active sites for TC adsorption. The contribution of SiO2, Fe2O3, and Al2O3 to the overall TC adsorption could reach up to 5.6 %, 0.4 %, and 73.3 %, respectively. Interestingly, the DFT results suggesting that SiO2 tends to form intermolecular hydrogen bonds with TC, while Fe-O and Al-O play predominant roles in TC adsorption on SS. The MIKE simulations showed that river temperature, initial pH, and SS concentration would significantly affect the concentration of dissolved TC during SS transport. In addition, the presence of humic acid and more acidic environments favored the adsorption of TC on SS. Conversely, the introduction of inorganic cations inhibited the adsorption of TC on SS. This study provides new insights into the adsorption mechanism and migration of antibiotics in rivers with high SS content.

Synthesis and Peroxide Activation Mechanism of Bimetallic MOF for Water Contaminant Degradation: A Review.

Metal-organic framework (MOF) materials possess a large specific surface area, high porosity, and atomically dispersed metal active sites, which confer excellent catalytic performance as peroxide (peroxodisulfate (PDS), peroxomonosulfate (PMS), and hydrogen peroxide (H2O2)) activation catalysts. However, the limited electron transfer characteristics and chemical stability of traditional monometallic MOFs restrict their catalytic performance and large-scale application in advanced oxidation reactions. Furthermore, the single-metal active site and uniform charge density distribution of monometallic MOFs result in a fixed activation reaction path of peroxide in the Fenton-like reaction process. To address these limitations, bimetallic MOFs have been developed to improve catalytic activity, stability, and reaction controllability in peroxide activation reactions. Compared with monometallic MOFs, bimetallic MOFs enhance the active site of the material, promote internal electron transfer, and even alter the activation path through the synergistic effect of bimetals. In this review, we systematically summarize the preparation methods of bimetallic MOFs and the mechanism of activating different peroxide systems. Moreover, we discuss the reaction factors that affect the process of peroxide activation. This report aims to expand the understanding of bimetallic MOF synthesis and their catalytic mechanisms in advanced oxidation processes.

A feasible biochar derived from biogas residue and its application in the efficient adsorption of tetracycline from an aqueous solution.

The recovery of carbon materials from biogas residue (BR) could efficiently promote the efficient utilization of waste and the preparation of novel materials. In this study, a green and feasible reagent of citric acid was introduced and applied in the modification of biogas residue biochar (BRC). The modified biogas residue biochar (CABRC) showed a superior adsorption ability due to its higher specific surface area (approximately 6 times that of the BRC). Additionally, the adsorption capacities of CABRC and BRC for TC were 58.25 mg/g and 20.77 mg/g, respectively, while the TC adsorption performance of CABRC was 2.8 times that of BRC. The adsorption of TC by both BRC and CABRC was primarily controlled by physical adsorption and chemical adsorption (including pore filling, hydrogen bonding, π-π DEA interaction, and electrostatic interaction). Therefore, CABRC should be considered an environmentally friendly material due to its higher adsorption performance, which could expand its application in wastewater treatment.

Synthesis of core-heteroshell structure for ZIF-67/VTM and its efficient activation of peroxymonosulfate in treatment of levofloxacin from an aqueous solution.

A core-heteroshell structural magnetic composite of ZIF-67/Vanadium-titanium magnetite (VTM) was successfully synthesized through a feasible solvothermal method and efficiently used in activation of peroxymonosulfate (PMS) for the treatment of levofloxacin (LVF) in an aqueous solution. The catalytic activity of the ZIF-67/VTM composite in LVF degradation was thoroughly evaluated, demonstrating the LVF removal rate could reach up to 93.3% within 60 min at ZIF-67/VTM composite dosage of 100 mg/L, PMS concertation of 75 mg/L, and the natural pH of 6.4. It is quite interesting that the carbon organic skeleton (in the ZIF-67 shell) have accelerated the internal electron transformation rate of the ZIF-67/VTM composite, thus efficiently promoting the O-O band (in PMS) breakage and the redox cycle of cobalt, further favoring the free radicals generation. The quenching experiments and EPR analysis results demonstrated that ·SO4- would play a crucial role in the LVF degradation process. Surprisingly, we have found that the introduction of Cl- (at some certain dosage) would not always decrease the LVF degradation ratio, for a new reactive oxygen species (singlet oxygen) was emerged in this system. What's more, the ZIF-67 (as the wrapping structure) could stabilize the VTM (the inner structure) in changing reaction conditions, prompting a good adaptability at a wider pH range (3-10) for inhibiting the leaching of various metal ions into the aqueous solution. This novel ZIF-67/VTM composite could provide new ideas and routes for the removal of emerging pollutants from an aqueous solution.

The potential of green biochar generated from biogas residue as a heterogeneous persulfate activator and its non-radical degradation pathways: Adsorption and degradation of tetracycline.

Advanced oxidation aided by sulfate radicals (SO4-) is an effective option for the treatment of refractory pollutants from aqueous solutions. In this work, a metal-free biochar catalyst was prepared using pyrolyzed biogas residue as the raw material. The biogas residue carbon (BRC) obtained at 800 °C showed excellent catalytic activity and adsorption capacity for the removal of tetracycline (TC) with 97.9% of removal efficiency. Such performance is accounted for by the rich pores and accelerated electron transformability conferred by its defect structure with the crucial role of pyrolysis temperature in regulating catalyst properties. The BRC-800/peroxymonosulfate (PMS) system worked predominantly through non-radical pathways with high stability/recyclability without being interfered by organic/inorganic compounds in an actual water environment. The exceelent removal performance is also supported by the kinetic reaction rate of the BRC-800/PMS system as estimated to be 0.03017 min-1. This work provides a simple and effective path for modifying biogas residue waste for versatile applications.