ABSTRACT
Oxytetracycline Hydrochloride (OTC), a common antibiotic used to treat specific illnesses in humans and animals, is characterized by poor absorption into cells, low volatility, and high hydrophilicity. It is a potent contaminant that poses a serious threat to the ecosystem, particularly the aquatic sources. Adsorption onto natural adsorbents is one of the most successful, economical, and ecologically friendly ways to remove antibiotics from waste water. The present work focuses on the adsorption of OTC utilizing alginate biochar beads (AlBCB) and biochar powder (BC) derived from bagasse. The influence of several factors were studies and optimized through batch studies employing BC and AlBCB. After 50 min BC displayed a removal of 97%, at an initial concentration of 10 ppm. The experimental data was discovered to follow PFO kinetics and fit with the Freundlich isotherm adsorption model. AlBCB, after a contact time of 40 min, indicated a maximum percentage removal of 86% for initial concentration of 10 ppm OTC. Al-biochar beads showed the maximum percentage removal at pH 10. 0.5 g of adsorbent was used to carry out all batch experiments at room temperature. The adsorption fitted Freundlich adsorption isotherm and intraparticle diffusion kinetics.
Subject(s)
Anti-Bacterial Agents , Cellulose , Charcoal , Oxytetracycline , Water Pollutants, Chemical , Charcoal/chemistry , Adsorption , Oxytetracycline/chemistry , Cellulose/chemistry , Water Pollutants, Chemical/chemistry , Kinetics , Anti-Bacterial Agents/chemistry , Powders , Hydrogen-Ion Concentration , Water Purification/methodsABSTRACT
This study investigated the adsorption of Oxytetracycline (OTC) from pharmaceutical wastewater using a kappa carrageenan based hydrogel (KPB). The aim of the present study was to explore the potential of KPB for long-term pharmaceutical wastewater treatment. A sustainable adsorbent was developed to address oxytetracycline (OTC) contamination. The hydrogel's structural and adsorption characteristics were examined using various techniques like Scanning Electron Microscope (SEM), Fourier Transform Infrared (FTIR), X-ray powder diffraction (XRD), and kinetic models. The results revealed considerable changes in the vibrational modes and adsorption bands of the hydrogel, suggesting the effective functionalization of Bentonite nano-clay. Kappa carrageenan based hydrogel achieved the maximum removal (98.5%) of OTC at concerntration of 40 mg/L, pH 8, cotact time of 140 min and adsorbent dose of 0.1 g (KPB-3). Adsorption of OTC increased up to 99% with increasing initial concentrations. The study achieved 95% adsorption capacity for OTC using a KPB film at a concentration of 20 mg/L and a 0.1 g adsorbent dose within 60 min. It also revealed that chemisorptions processes outperform physical adsorption. The Pseudo-Second-Order model, which emphasized the importance of chemical adsorption in the removal process, is better suited to represent the adsorption behavior. Excellent matches were found that R2 = 0.99 for KPB-3, R2 = 0.984 for KPB-2 and R2 = 0.989 for KPB-1 indicated strong chemical bonding interactions. Statisctical analysis (ANOVA) was performed using SPSS (version 25) and it was found that pH and concentration had significant influence on OTC adsorption by the hydrogel, with p-values less than 0.05. The study identified that a Kappa carrageenan-based hydrogel with bentonite nano-clay and polyvinyl alcohol (PVA) can efficiently remove OTC from pharmaceutical effluent, with a p-value of 0.054, but weak positive linear associations with pH, temperature, and contact time. This research contributed to sustainable wastewater treatment and environmental engineering.
Subject(s)
Carrageenan , Hydrogels , Oxytetracycline , Wastewater , Water Pollutants, Chemical , Water Purification , Oxytetracycline/chemistry , Oxytetracycline/isolation & purification , Carrageenan/chemistry , Wastewater/chemistry , Hydrogels/chemistry , Water Pollutants, Chemical/chemistry , Water Pollutants, Chemical/isolation & purification , Adsorption , Water Purification/methods , Kinetics , Hydrogen-Ion Concentration , Spectroscopy, Fourier Transform Infrared , Anti-Bacterial Agents/chemistryABSTRACT
The presence of antibiotics in water sources is a significant concern due to their potential environmental impact and the risks to human health. In the present research, hierarchically mesoporous UiO-66 (HP-UiO-66) with a high surface area (1011 m2/g) and large pore volume was synthesized using the reflux method on the liter scale. The successful synthesis was confirmed by FT-IR, XRD, FESEM/EDS, N2-adsorption/desorption, and zeta potential techniques. The HP-UiO-66 was utilized to remove two large structure antibiotics, chlortetracycline hydrochloride (CTC), and oxytetracycline (OTC). Box Behnken design was used to investigate the factors affecting the removal process and the interactions between them. The maximum adsorption capacities for OTC and CTC antibiotics were 252.9 mg/g and 234.2 mg/g at 35 °C, respectively. The sum of the normalized error method was applied to the analysis of various error functions in the nonlinear fitting of equilibrium and kinetic data. The CTC and OTC adsorption kinetic followed a fractal-like pseudo-second-order model. The Langmuir isotherm fitted well to adsorption data. The results demonstrate that HP-UiO-66 can be used as a recyclable and efficient adsorbent for large molecule antibiotics removal.
Subject(s)
Anti-Bacterial Agents , Wastewater , Water Pollutants, Chemical , Anti-Bacterial Agents/chemistry , Water Pollutants, Chemical/chemistry , Wastewater/chemistry , Adsorption , Kinetics , Water Purification/methods , Oxytetracycline/chemistry , Chlortetracycline/chemistry , Spectroscopy, Fourier Transform Infrared , PorosityABSTRACT
Understanding of energetics of interactions between drug and protein is essential in pharmacokinetics and pharmacodynamics study. The binding affinity (K) helps in investigating how tightly or loosely drug is bound to protein. The binding, displacement, conformational change and stability study of drugs- gentamicin (GM), 5-fluorouracil (5FU), oxytetracycline (OTC) and rolitetracycline (RTC) with bovine serum albumin (BSA) has been carried out in presence of each other drug by fluorescence, UV-visible spectroscopy, molecular docking, circular dichroism techniques and thermal denaturation method. The site marker study and docking methods have confirmed that 5FU and GM are able to bind at site 1 and OTC and RTC at site II of BSA. The order of their binding affinities with BSA for the binary system were as GM <5FU < OTC < RTC with the order of 102 < 103 < 105 < 105-6 M-1. The displacement study has shown that higher affinity drug decreases the equilibrium constant of another drug already in bound state with BSA if both these drugs are having the same binding site. Therefore 5FU, GM (binding site 1) drugs were not able to displace OTC and RTC (binding site 2) and vice-versa as they are binding at two different sites. The binding constant values were found to be decreasing with increasing temperature for all the systems involved which suggests static or mixed type of quenching, however can only confirmed with the help of TCSPC technique. The ΔG0 (binding energy) obtained from docking method were in accordance with the ITC method. From molecular docking we have determined the amino acid residues involved in binding process for binary and ternary systems by considering first rank minimum binding energy confirmation. From CD it has been observed that RTC causes most conformational change in secondary and tertiary structure of BSA due to the presence of pyrrole ring. OTC-RTC with higher affinity showed highest melting temperature Tm values while low affinity drugs in (5FU-GM) combination showed lowest Tm value. 5FU showed large endothermic denaturation enthalpy ΔHd0 due to the presence of highly electronegative fluorine atom in the pyridine analogue.
Subject(s)
Fluorouracil , Gentamicins , Molecular Docking Simulation , Oxytetracycline , Protein Binding , Serum Albumin, Bovine , Serum Albumin, Bovine/chemistry , Serum Albumin, Bovine/metabolism , Fluorouracil/chemistry , Oxytetracycline/chemistry , Gentamicins/chemistry , Binding Sites , Animals , Cattle , Calorimetry , Thermodynamics , Spectrum Analysis , Circular Dichroism , Biophysical PhenomenaABSTRACT
The increasing presence of oxytetracycline (OTC) in agricultural soils has raised global environmental concerns. We investigated the environmental behavior and fate of OTC in two types of tropical agricultural soils, focusing on the impact of dissolved organic matter (DOM) from biogas slurry. Techniques such as three-dimensional excitation-emission matrix fluorescence spectroscopy (3D-EEM), Fourier Transform Infrared (FTIR), X-ray photoelectron spectroscopy (XPS), and Ultraviolet-visible spectrophotometer (UV-vis) were used to explore the adsorption mechanisms. Our findings revealed that biogas slurry-derived DOM decreased the OTC adsorption on soils and extended the time to reach adsorption equilibrium. Specifically, the equilibrium adsorption of OTC by the two soils decreased by 19.41 and 15.32 %, respectively. These adsorption processes were effectively modelled by Elovich, intraparticle diffusion, linear, and Freundlich thermodynamic models. Thermodynamic parameters suggested that OTC adsorption onto soils was spontaneous and endothermic, with competitive interactions between biogas slurry-derived DOM and OTC molecules intensifying at higher DOM concentrations. The adsorption mechanisms were governed by both physical and chemical processes. Furthermore, the presence of Ca2+ and Na+ ions significantly inhibited OTC adsorption. These insights advanced our understanding of the fate and risk of OTC in soil environments influenced by DOM, contributing to more informed agricultural and environmental management practices.
Subject(s)
Agriculture , Oxytetracycline , Soil Pollutants , Soil , Oxytetracycline/chemistry , Adsorption , Soil/chemistry , Agriculture/methods , Soil Pollutants/chemistry , BiofuelsABSTRACT
Struvite recovery from wastewater offers a sustainable phosphorus and nitrogen source, yet it harbors the challenge of variable antibiotic residues, notably oxytetracycline (OTC), increasing the ecological risk during subsequent use. Despite the need, mechanisms behind these residues and regulatory solutions remain obscure. We characterized OTC in recovered struvite and showed that increased dissolved organic matter (DOM) enhanced OTC accumulation, while PO43- suppressed it. NH4+ modulated OTC levels through the saturation index (SI), with a rise in SI significantly reducing OTC content. Additionally, excess Mg2+ formed complexes with OTC and DOM (humic acid, HA), leading to increased residue levels. Complexation was stronger at higher pH, whereas electrostatic interactions dominated at lower pH. The primary binding sites for antibiotics and DOM were Mg-OH and P-OH groups in struvite. OTC's dimethylamino, amide, and phenolic diketone groups primarily bound to struvite and DOM, with the carboxyl group of DOM serving as the main binding site. Mg2+ complexation was the primary pathway for OTC transportation, whereas electrostatic attraction of PO43- dominated during growth. Controlling magnesium (Mg) dosage and adjusting pH were effective for reducing OTC in recovered products. Our findings provided insights into the intricate interactions between struvite and antibiotics, laying the groundwork for further minimizing antibiotic residues in recovered phosphorus products.
Subject(s)
Anti-Bacterial Agents , Oxytetracycline , Struvite , Wastewater , Water Pollutants, Chemical , Oxytetracycline/chemistry , Oxytetracycline/analysis , Struvite/chemistry , Wastewater/chemistry , Water Pollutants, Chemical/chemistry , Water Pollutants, Chemical/analysis , Anti-Bacterial Agents/chemistry , Anti-Bacterial Agents/analysis , Hydrogen-Ion Concentration , Humic Substances/analysis , Phosphorus/chemistry , Phosphorus/analysisABSTRACT
In this work, a Z-scheme heterostructured BiOCOOH/O-gC3N4 material was synthesized and immobilized on chitosan (CTS) to obtain the BiOCOOH/O-gC3N4/CTS photocatalytic material for photocatalytic degradation of oxytetracycline hydrochloride (CTC).Our findings indicate that the composite material BiOCOOH/O-gC3N4, as well as the BiOCOOH/O-gC3N4/CTS composite membrane, displayed a significantly higher efficiency in photocatalytic degradation of CTC compared to BiOCOOH alone, owing to the synergistic effect of adsorption and photocatalysis. Following four cycles of use, the composite material retained around 96 % of its initial photocatalytic degradation activity. The addition of CTS in the photocatalytic material resolved issues such as aggregation and difficult recovery commonly encountered with powder materials, thereby facilitating effective collision between the photocatalytic active sites and CTC. Experimental and theoretical calculations provided confirmation that the combination of BiOCOOH and O-gC3N4 effectively enhanced the light absorption capacity and photocatalytic performance. Furthermore, we investigated the influence of environmental factors such as pH value and anions on the photocatalytic degradation experiment, which offers valuable insights for the application of composite catalysts in wastewater treatment.
Subject(s)
Chitosan , Light , Oxytetracycline , Oxytetracycline/chemistry , Chitosan/chemistry , Catalysis , Water Pollutants, Chemical/chemistry , Adsorption , Photolysis , Bismuth/chemistry , Hydrogen-Ion Concentration , Photochemical Processes , Water Purification/methods , Nitrogen Compounds/chemistry , GraphiteABSTRACT
A unique luminescent lanthanide metal-organic framework (LnMOF)-based fluorescence detection platform was utilized to achieve sensitive detection of vomitoxin (VT) and oxytetracycline hydrochloride (OTC-HCL) without the use of antibodies or biomolecular modifications. The sensor had a fluorescence quenching constant of 9.74 × 106 M-1 and a low detection limit of 0.68 nM for vomitoxin. Notably, this is the first example of a Tb-MOF sensor for fluorescence detection of vomitoxin. We further investigated its response to two mycotoxins, aflatoxin B1 and ochratoxin A, and found that their Stern-Volmer fluorescence quenching constants were lower than those of VT. In addition, the fluorescence sensor realized sensitive detection of OTC-HCL with a detection limit of 0.039 µM. In conclusion, the method has great potential as a sensitive and simple technique to detect VT and OTC-HCL in water.
Subject(s)
Metal-Organic Frameworks , Oxytetracycline , Terbium , Oxytetracycline/analysis , Oxytetracycline/chemistry , Terbium/chemistry , Metal-Organic Frameworks/chemistry , Spectrometry, Fluorescence , Fluorescent Dyes/chemistry , Limit of Detection , Water/chemistry , Fluorescence , Water Pollutants, Chemical/analysisABSTRACT
Introducing carbon quantum dots (CQDs) into photocatalysts is believed to boost the charge transfer rate and reduce charge complexation. Doping heteroatoms such as N, S, or P enable CQDs to have an uplifting electron transfer capability. However, the application of oxygen-doped CQDs to improve the performance of photocatalysts has rarely been reported. Herein, a type of carbon-oxygen quantum dots (COQDs) was in situ embedded into MIL-53(Fe) to aid peroxydisulfate (PDS)-activated degradation of oxytetracycline (OTC) under visible light irradiation. The successful embedding of COQDs was confirmed by XRD, FT-IR, XPS, SEM, and TEM techniques. Photoelectrochemical testing confirmed its better performance. The prepared COQDs1/MIL-53(Fe) showed 88.2% decomposition efficiency of OTC in 60 min, which was 1.45 times higher than that of pure MIL-53(Fe). In addition, the performance of the material was tested at different pH, OTC concentrations, catalyst dosing, and PDS dosing. It was also subjected to cyclic testing to check stability. Moreover, free radical trapping experiments and electron paramagnetic resonance were conducted to explore the possible OTC deterioration mechanism. Our work provides a new idea for the development of MOFs for water treatment and remediation.
Subject(s)
Carbon , Oxygen , Oxytetracycline , Quantum Dots , Oxytetracycline/chemistry , Quantum Dots/chemistry , Carbon/chemistry , Oxygen/chemistry , CatalysisABSTRACT
Tetracyclines are a class of commonly used four-ringed antibiotics. A series of DNA aptamers were recently obtained using the capture-SELEX (systematic evolution of ligands by exponential enrichment) method to bind to oxytetracycline, and one of the aptamers can bind to a few other tetracycline antibiotics as well. Upon binding to the aptamers, the intrinsic fluorescence of tetracycline antibiotics can be enhanced. At least 10 different DNA aptamers were isolated from the previous selection experiment. In this work, a systematic characterization of these ten aptamers was performed. Each of these aptamers shows a different degree of fluorescence enhancement ranging from around 1-fold to over 20-fold. Fluorescence enhancement was boosted in the presence of Mg2+. Isothermal titration calorimetry (ITC) studies were done and showed a great variety in dissociation constant (Kd) from 62â nM to 1.6â µM. Steady-state fluorescence spectroscopy and fluorescence lifetime studies showed a correlation between fluorescence lifetime and degree of fluorescence enhancement. A few aptamers showed slow binding kinetics, although no correlation was found between the kinetics of fluorescence change and degree of fluorescence enhancement. This is the first study of ten different aptamers for the same target, providing fundamental insights into aptamer binding and bioanalytical applications.
Subject(s)
Aptamers, Nucleotide , Oxytetracycline , Spectrometry, Fluorescence , Aptamers, Nucleotide/chemistry , Aptamers, Nucleotide/metabolism , Oxytetracycline/chemistry , Fluorescence , Kinetics , Calorimetry , Anti-Bacterial Agents/chemistry , SELEX Aptamer Technique , Binding Sites , ThermodynamicsABSTRACT
The surface hydrophilicity of a photocatalyst is an important factor that directly influences its interactions with organic pollutants and significantly impacts its degradation. In this study, we investigated the impact of increased hydrophilicity of g-C3N4 (CN) by alkaline solvothermal treatment on the degradations of three antibiotics (oxytetracycline (OTC), oxolinic acid (OA), and sulfamethoxazole (SMX)) with different log Kow values. Scanning electron microscopy (SEM), X-ray diffraction analysis (XRD), and Fourier-transform infrared (FT-IR) spectroscopy showed no significant differences in the morphology, crystalline structure, and surface functional groups of CN after alkaline solvothermal treatment (Nv-HPCN). However, contact angle analysis revealed that Nv-HPCN (31.8°) was more hydrophilic than CN (61.1°). To assess the hydrophilicity of the antibiotics, the log Kow values of SMX (0.77), OA (0.43), and OTC (-0.34) were measured. Nv-HPCN showed faster OTC degradation than CN, whereas the opposite pattern was observed for the degradation of OA. Scavenger tests showed that O2â¢- and h+ mainly contributed to the degradation of these antibiotics. Furthermore, the influences of NOM and coexisting anions on antibiotic degradation were investigated. This study thus offers perspectives on the impact of surface hydrophilicity of photocatalysts on the degradation of antibiotics.
Subject(s)
Graphite , Nitrogen Compounds , Oxytetracycline , Anti-Bacterial Agents/chemistry , Spectroscopy, Fourier Transform Infrared , Oxytetracycline/chemistry , Graphite/chemistry , CatalysisABSTRACT
Oxytetracycline (OTC) in the waste water can be removed by biochar adsorption. How to separate the biochar adsorbed antibiotics from the wastewater was also a problem. The nontoxic magnetic biochar was prepared from Suaeda biochar (800SBC) by mafic bimetal modification, and used for the removal of OTC. The results of XRD and VSM indicated that the main composition of biochar was ferrite. Then through batch adsorption experiments, the adsorption kinetics, isothermal adsorption, thermodynamics, and coexisting ion and adsorbent regeneration experiments were studied. Through the fitting of the adsorption model, it was found that Mg-Fe@800SBC(1:1) and 800SBC belonged to chemisorption. 800SBC was consistent with the Langmuir model, mainly monolayer adsorption, and Mg-Fe@800SBC(1:1) was consistent with the Freundlich model, mainly multilayer adsorption. The adsorption processes of the two materials were spontaneous, endothermic and entropic decreasing processes. The maximum adsorption capacity of the Mg-Fe@800SBC(1:1) for OTC from the Sips L-F model was 82.83 mg/g. Through various characterizations of magnetic biochar, it was found that the adsorption mechanism of the modified biochar included the hydrogen bonds between the oxygen-containing functional group of biochar and the -NH2 group of OTC, π-π EDA interaction, electrostatic attraction and complexation. Coexistence anions (CO32- and PO43-) have a negative effect on the adsorption process.
Subject(s)
Oxytetracycline , Water Pollutants, Chemical , Oxytetracycline/chemistry , Adsorption , Water Pollutants, Chemical/analysis , Wastewater , Kinetics , Magnetic PhenomenaABSTRACT
Due to the adverse effects of long-term oxytetracycline (OTC) residues in aquatic environments, an effective treatment is urgently needed. Immobilized microbial technology has been widely explored in the treatment of various organic pollutants in aquatic environments with its excellent environmental adaptability. Nevertheless, studies on its application in the removal of antibiotics are relatively scarce and not in sufficient depth. Only a few studies have further investigated the final fate of antibiotics in the immobilized bacteria system. In this study, a novel kind of OTC-degrading bacteria Mycolicibacterium sp. was immobilized on straw biochar and magnetic biochar, respectively. Magnetic biochar was proved to be a more satisfactory immobilization carrier due to its superior property and the advantage of easy recycling. Compared with free bacteria, immobilized bacteria had stronger environmental adaptability under different OTC concentrations, pH, and heavy metal ions. After 5 cycles, immobilized bacteria could still remove 71.8% of OTC, indicating that it had a stable recyclability. Besides, OTC in real swine wastewater was completely removed by immobilized bacteria within 2 days. The results of FTIR showed that bacteria were successfully immobilized on biochar and O-H, N-H, and C-N groups might be involved in the removal of OTC. The fate analysis indicated that OTC was removed by simultaneous adsorption and biodegradation, while biodegradation (92.8%) played a dominant role in the immobilized bacteria system. Meanwhile, the amount of adsorbed OTC (7.20%) was rather small, which could effectively decrease the secondary pollution of OTC. At last, new degradation pathways of OTC were proposed. This study provides an eco-friendly and effective approach to remedy OTC pollution in wastewater.
Subject(s)
Oxytetracycline , Animals , Swine , Oxytetracycline/chemistry , Wastewater , Adsorption , Anti-Bacterial Agents , Charcoal/chemistry , Biodegradation, Environmental , Bacteria , Magnetic PhenomenaABSTRACT
The pollution problem of oxytetracycline (OTC) from wastewater becomes more serious, so an efficient, economical, and green adsorption material is urgently explored. In this study, the multilayer porous biochar (OBC) was prepared by coupling carbon nanotubes with iron oxide nanoparticles synthesized by Aquabacterium sp. XL4 to modify corncobs under medium temperature (600 °C) conditions. The adsorption capacity of OBC could reach 72.59 mg g-1 after preparation and operation parameters were optimized. In addition, various adsorption models suggested that OTC removal resulted from the combined effect of chemisorption, multilayer interaction, and disordered diffusion. Meanwhile, the OBC was fully characterized and exhibited a large specific surface area (237.51 m2 g-1), abundant functional groups, stable crystal structure, high graphitization, and mild magnetic properties (0.8 emu g-1). The OTC removal mechanisms mainly included electrostatic interactions, ligand exchange, π-π bonding reactions, hydrogen bonds, and complexation. pH and coexistence substance experiments revealed that the OBC possesses a wide pH adaptation range and excellent anti-interference ability. Finally, the safety and reusability of OBC were confirmed by repeated experiments. In summary, OBC as a biosynthetic material shows considerable potential for application in the field of purifying new pollution from wastewater.
Subject(s)
Nanotubes, Carbon , Oxytetracycline , Water Pollutants, Chemical , Oxytetracycline/chemistry , Wastewater , Adsorption , Magnetic Iron Oxide Nanoparticles , Water Pollutants, Chemical/analysis , KineticsABSTRACT
The pharmaceutical factories of oxytetracycline (OTC) massively produce OTC fermentation residues (OFRs). The high content of residual OTC and antibiotic resistance genes in OFRs must to be considered and controlled at an acceptable level. This study therefore investigated the applicability of Fenton oxidation in OTC degradation and resistant gene inactivation of OFRs. The results revealed that Fe2+ as catalyzer could very rapidly activate H2O2 to produce HOâ¢, leading to instantaneous degradation of OTC. The optimum conditions for OTC removal were 60 mM H2O2 and 140 mg/L Fe2+ under pH 7. After Fenton oxidation treatment, the release of water-soluble polysaccharides, NO3-N, and PO4-P was enhanced, whereas for proteins and NH3-N were reduced. Three soluble fluorescence components (humic, tryptophan-like, and humic acid-like substances) were identified through fluorescence spectra with parallel factor analysis, and their reduction exceeded 50% after Fenton oxidation. There were twelve intermediates and three degradation pathways of OTC in OFRs during Fenton process. According to toxicity prediction, the comprehensive toxicity of OTC in OFRs was alleviated via Fenton oxidation treatment. In addition, Fenton oxidation showed the ability to reduce antibiotic resistance genes and mobile genetic elements, and even tetO, tetG, intI1, and intI2 were eliminated completely. These results suggested that Fenton oxidation treatment could be an efficient strategy for removing OTC and resistance genes in OFRs.
Subject(s)
Oxytetracycline , Oxytetracycline/chemistry , Fermentation , Hydrogen Peroxide/chemistry , Anti-Bacterial Agents/pharmacology , Oxidation-ReductionABSTRACT
The surge in the use of antibiotics, especially in aquaculture, has led to development of antibiotic resistance genes, which will harm environmental and public health. One of the most commonly used antibiotics in aquaculture is oxytetracycline (OTC). Employing photocatalysis, this study compared OTC degradation efficiency of two different types of common photocatalysts, TiO2 and graphitic carbon nitride (GCN) in terms of their photochemical properties and underlying photocatalytic mechanism. For reference purpose, self-synthesized GCN from urea precursor (GCN-Urea) and commercial GCN (GCN-Commercial) were both examined. OTC adsorption-photocatalysis removal rates in pure OTC solution by TiO2, GCN-Urea and GCN-Commercial were attained at 95%, 60% and 40% respectively. Photochemical properties evaluated included light absorption, band gap, valence and conduction band positions, photoluminescence, cyclic voltammetry, BET surface area and adsorption capability of the photocatalysts. Through the evaluations, this study provides novel insights towards current state-of-the-art heterogeneous photocatalytic processes. The electron-hole recombination examined by photoluminescence is not the key factor influencing the photocatalytic efficacies as commonly discussed. On the contrary, the dominating factors governing the higher OTC degradation efficiency of TiO2 compared to GCN are the high mobility of electrons that leads to high redox capability and the high pollutant-photocatalyst affinity. These claims are proven by 86% and 40% more intense anodic and cathodic cyclic voltammetry curve peaks of TiO2 as compared to both GCNs. OTC also demonstrated 1.7 and 2.3 times higher affinity towards TiO2 than GCN-Urea and GCN-Commercial. OTC removal by TiO2 in real aquaculture wastewater only achieved 50%, due to significant inhibition effect by dissolved solids, dissolved organic matters and high ionic contents in the wastewater.
Subject(s)
Oxytetracycline , Oxytetracycline/chemistry , Anti-Bacterial Agents/chemistry , Wastewater , Titanium/chemistry , AquacultureABSTRACT
In this work, magnetic CuFe2O4 was prepared for the removal of oxytetracycline (OTC) by a self-propagating combustion synthesis method. Almost complete degradation (99.65%) of OTC was achieved within 25 min at [OTC]0 = 10 mg/L, [PMS]0 = 0.05 mM, CuFe2O4 = 0.1 g/L under pH = 6.8 at 25 °C for deionized water. Specially, the addition CO32- and HCO3- induced the CO3â¢- appearance enhancing the selective degradation to electron-rich OTC molecule. The prepared CuFe2O4 catalyst exhibited desirable OTC removal rate (87.91%) even in hospital wastewater. The reactive substances were analyzed by free radical quenching experiments and electron paramagnetic resonance (EPR), and the results demonstrated that 1O2 and â¢OH were the main active substances. Liquid chromatography-mass spectrometry (LC-MS) was used to analyze the intermediates produced during the degradation of OTC and thus to speculate on the possible degradation pathways. Ecotoxicological studies were conducted to unveil large-scale application prospect.
Subject(s)
Nanoparticles , Oxytetracycline , Oxytetracycline/chemistry , Carbon/chemistry , Water , Peroxides/chemistry , Magnetic PhenomenaABSTRACT
The abuse of tetracycline antibiotics (TCs) has caused serious environmental pollution and risks to public health. Degradation of TCs by cold atmospheric plasmas (CAPs) is a high efficiency, low energy consumption and environmentally friendly method. In this study, a reactive molecular dynamics (MD) simulation is applied to study the interactions of reactive oxygen species (ROS) produced in CAPs and TCs (including tetracycline (TC), oxytetracycline (OTC), chlortetracycline (CTC) and demeclocycline (DMC)). As revealed by the simulation data at the atomic level, the main reaction sites on TCs are the C2 acylamino, the C4 dimethylamine, the C6 methyl group, the C8 site on the benzene ring and the C12a tertiary alcohol. The interaction between ROS and TCs is usually initiated by H-abstraction, followed by the breaking and formation of the crucial chemical bonds, such as the breaking of C-C bonds, C-N bonds and C-O bonds and the formation of C=C bonds and C=O bonds. Due to the different structures of TCs, when the ROS impact OTC, CTC and DMC, some specific reactions are observed, including carbonylation at the C5 site, dechlorination at the C7 site and carbonylation at the C6 site, respectively. Some degradation products obtained from the simulation data have been observed in the experimental measurements. In addition, the dose effects of CAP on TCs by adjusting the number of ROS in the simulation box are also investigated and are consistent with experimental observation. This study explains in detail the interaction mechanisms of degradation of TCs treated by CAPs with the final products after degradation, provides theoretical support for the experimental observation, then suggests optimization to further improve the efficiency of degradation of TCs by CAPs in applications.
Subject(s)
Chlortetracycline , Oxytetracycline , Molecular Dynamics Simulation , Reactive Oxygen Species , Anti-Bacterial Agents/pharmacology , Anti-Bacterial Agents/chemistry , Tetracycline/chemistry , Oxytetracycline/chemistry , Chlortetracycline/chemistryABSTRACT
The effective removal of oxytetracycline hydrochloride (OTC) from the water environment is of great importance. Adsorption as a simple, stable, and cost-effective technology is regarded as an important method for removing OTC. Herein, a low-cost biochar with a developed mesoporous structure was synthesized via pyrolysis of poplar leaf with potassium bicarbonate (KHCO3) as the activator. KHCO3 can endow biochar with abundant mesopores, but excessive KHCO3 cannot continuously promote the formation of mesoporous structures. In comparison with all of the prepared biochars, PKC-4 (biochar with a poplar leaf to KHCO3 mass ratio of 5:4) shows the highest adsorption performance for OTC as it has the largest surface area and richest mesoporous structure. The pseudo-second-order kinetic model and the Freundlich equilibrium model are more consistent with the experimental data, which implies that the adsorption process is multi-mechanism and multi-layered. In addition, the maximum adsorption capacities of biochar are slightly affected by pH changes, different metal ions, and different water matrices. Moreover, the biochar can be regenerated by pyrolysis, and its adsorption capacity only decreases by approximately 6% after four cycles. The adsorption of biochar for OTC is mainly controlled by pore filling, though electrostatic interactions, hydrogen bonding, and π-π interaction are also involved. This study realizes biomass waste recycling and highlights the potential of poplar leaf-based biochar for the adsorption of antibiotics.
Subject(s)
Oxytetracycline , Water Pollutants, Chemical , Oxytetracycline/chemistry , Adsorption , Water Pollutants, Chemical/chemistry , Charcoal/chemistry , Kinetics , WaterABSTRACT
In this study, an adsorbent with mesoporous structure and PO/PO bonds is prepared by hydrothermal and phosphoric acid activation from industrial alkali lignin for the adsorption of oxytetracycline (OTC). The adsorption capacity is 598 mg/g, which is three times higher than that of the adsorbent with microporous structure. The rich mesoporous structure of the adsorbent provides adsorption channels and filling sites, and π-π attraction, cation-π interaction, hydrogen bonds, and electrostatic attraction provide adsorption forces at the adsorption sites. The removal rate of OTC exceeds 98 % over a wide range of pH values (3-10). It has high selectivity for competing cations in water, with higher than 86.7 % removal rate of OTC from medical wastewater. After 7 consecutive adsorption-desorption cycles, the removal rate of OTC remains as high as 91 %. This efficient removal rate and excellent reusability indicate the strong potential of the adsorbent for industrial applications. This study prepares a highly efficient, environmentally friendly antibiotic adsorbent that can not only efficiently remove antibiotics from water but also recycle industrial alkali lignin waste.