Tetracycline’s accumulation in the environment poses threats to human health and the ecological balance, necessitating efficient and rapid removal methods. Novel porous metal–organic framework (MOF) materials have garnered significant attention in academia due to their distinctive characteristics. This paper focuses on studying the adsorption and removal performance of amino-modified MIL-101(Fe) materials towards tetracycline, along with their adsorption mechanisms. The main research objectives and conclusions are as follows: (1) NH2-MIL-101(Fe) MOF materials were successfully synthesized via the solvothermal method, confirmed through various characterization techniques including XRD, FT-IR, SEM, EDS, XPS, BET, and TGA. (2) NH2-MIL-101(Fe) exhibited a 40% enhancement in tetracycline adsorption performance compared to MIL-101(Fe), primarily through chemical adsorption following pseudo-second-order kinetics. The adsorption process conformed well to Freundlich isotherm models, indicating multilayer and heterogeneous adsorption characteristics. Thermodynamic analysis revealed the adsorption process as a spontaneous endothermic reaction. (3) An increased adsorbent dosage and temperature correspondingly improved NH2-MIL-101(Fe)’s adsorption efficiency, with optimal performance observed under neutral pH conditions. These findings provide new strategies for the effective removal of tetracycline from the environment, thus holding significant implications for environmental protection.
Advanced oxidation technology represented by hydroxyl radicals has great potential to remove residual antibiotics. In this study, we systematically compared the metronidazole (MTZ) degradation behavior and mechanism in the UV and UV/H2O2 systems at pH 3.00 condition. The results show that the initial reaction rates were 0.147 and 1.47 µM min−1 in the UV and UV/H2O2 systems, respectively. The main reason for the slow direct photolysis of MTZ is the relatively low molar absorption coefficient (2645.44 M−1 cm−1) and quantum yield (5.9 × 10−3 mol Einstein−1). Then, we measured as 2.79 (±0.12) × 109 M−1 s−1 by competitive kinetics, and calculated and as 2.43 (±0.11) × 109 M−1 s−1 and 2.36 × 10−13 M by establishing a kinetic model based on the steady-state hypothesis in our UV/H2O2 system. The contribution of direct photolysis and •OH to the MTZ degradation was 9.9% and 90.1%. •OH plays a major role in the MTZ degradation, and •OH was the main active material in the UV/H2O2 system. This result was also confirmed by MTZ degradation and radicals’ identification experiments. MTZ degradation increases with H2O2 dosage, but excessive H2O2 had the opposite effect. A complex matrix has influence on MTZ degradation. Organic matter could inhibit the degradation of MTZ, and the quenching of the radical was the main reason. promoted the MTZ degradation, while and Cl− had no effect. These results are of fundamental and practical importance in understanding the MTZ degradation, and to help select preferred processes for the optimal removal of antibiotics in natural water bodies, such as rivers, lakes, and groundwater
At present, the application of phytoremediation technology in the ecological remediation of heavy metal tailings is receiving more and more attention. In this study, the physiological and biochemical response and tolerance mechanism of woody plant Nerium indicum to Pb and Zn under different proportions of inorganic modifier calcium carbonate (C1: 5%, C2: 10%, C3: 15%) and organic modifier mushroom residue (M1: 10%, M2: 20%, M3: 30%) was compared. The results showed that the pH value has a trend of C group > M group > CK group and organic matter has a trend of M group > CK group > C group. Phosphatase activity and catalase activity has a trend of M group > C group > CK group, but catalase was more vulnerable to the calcium carbonate concentration. Both modifiers can promote the transformation of Pb, Zn, Cu, and Cd in tailings to more stable organic bound and residual states. However, the stabilization effect of mushroom residue is better, and its stability is Pb, Zn > Cd, Cu. Both modifiers can increase the biomass of Nerium indicum and the modification effect of mushroom residue is better than calcium carbonate. Pb/Zn content and accumulation in Nerium indicum organs showed root > stem > leaf in all groups. Compared with the CK group, the enrichment coefficient of Pb/Zn in C1 and M1 groups decreased, while the translocation factor of Pb/Zn in C1 and M1 groups increased. With the increase in modifier concentration, the enrichment coefficient increases about 1.75~52.94%, but the translocation factor decreases rapidly (20.01~64.46%). Clearly, both the calcium carbonate and mushroom residue amendment could promote the growth ability of Nerium indicum in lead–zinc tailings and strengthen the phytoremediation potential.
Phytoremediation could be an alternative strategy for lead (Pb) contamination. K. paniculata has been reported as a newly potential plant for sustainable phytoremediation of Pb-contaminated soil. Physiological indexes, enrichment accumulation characteristics, Pb subcellular distribution and microstructure of K. paniculata were carefully studied at different levels of Pb stress (0–1200 mg/L). The results showed that plant growth increased up to 123.8% and 112.7%, relative to the control group when Pb stress was 200 mg/L and 400 mg/L, respectively. However, the average height and biomass of K. paniculata decrease when the Pb stress continues to increase. In all treatment groups, the accumulation of Pb in plant organs showed a trend of root > stem > leaf, and Pb accumulation reached 81.31%~86.69% in the root. Chlorophyll content and chlorophyll a/b showed a rising trend and then fell with increasing Pb stress. Catalase (CAT) and peroxidase (POD) activity showed a positive trend followed by a negative decline, while superoxide dismutase (SOD) activity significantly increased with increasing levels of Pb exposure stress. Transmission electron microscopy (TEM) showed that Pb accumulates in the inactive metabolic regions (cell walls and vesicles) in roots and stems, which may be the main mechanism for plants to reduce Pb biotoxicity. Fourier transform infrared spectroscopy (FTIR) showed that Pb stress increased the content of intracellular -OH and -COOH functional groups. Through organic acids, polysaccharides, proteins and other compounds bound to Pb, the adaptation and tolerance of K. paniculata to Pb were enhanced. K. paniculata showed good phytoremediation potential and has broad application prospects for heavy metal-contaminated soil.
Antibiotic residues in water environments have garnered widespread attention. Metal-organic frameworks (MOFs) have found extensive applications in water purification. This study investigates the use of a cobalt-based MOF material, zeolitic imidazolate framework-67(ZIF-67)(Co), for activating persulfate (PMS) to remove residual antibiotic ciprofloxacin (CIP) from aqueous environments. The main findings are as follows: ZIF-67(Co) exhibits insignificant adsorption capacity for CIP, and PMS alone does not degrade CIP effectively. However, ZIF-67(Co)-activated PMS demonstrates the efficient degradation of CIP, following pseudo-second-order reaction kinetics. Under optimal conditions of the catalyst dosage (15 mg) and PMS concentration (1.0 mM), the removal efficiency reaches 88% after 60 min. Comparative analysis of CIP degradation at different initial pH levels shows that the highest efficiency is reached under mildly acidic conditions, with an 86% removal rate achieved within 60 min under these conditions. Investigation into the impact of various inorganic anions on the ZIF-67(Co)-catalyzed PMS degradation of CIP reveals significant inhibition by chloride ions (), whereas nitrate () and sulfate () ions have minor effects on the degradation efficiency. The system demonstrates a consistent performance across different water matrices, highlighting ZIF-67(Co)/PMS as effective for ciprofloxacin removal in environmental waters. This study provides technical support for the efficient removal of antibiotic residues.