Tetracycline Pollutants Research Articles

Remediation of tetracycline pollution using microplastics, green materials, membranes and sonocatalysts: a review

Remediation of tetracycline pollution using microplastics, green materials, membranes and sonocatalysts: a review

Dual S-Scheme g-C3N4/Ag3PO4/g-C3N5 photocatalysts for removal of tetracycline pollutants through enhanced molecular oxygen activation

A dual S-scheme g-C3N4/Ag3PO4/g-C3N5 heterojunction was prepared by decomposition methods, and it displayed enhanced performance to degrade tetracycline hydrochloride with the ideal stability under different water substrates and ions. Comparing with three single components, as g-C3N4, g-C3N5, and Ag3PO4, the dual S-scheme g-C3N4/Ag3PO4/g-C3N5 heterojunction displayed 4.4-, 3.4-, and 2.5-times enhancements in the tetracycline hydrochloride removal. Based on the dynamics analyses for charge carriers and band structure calculations, two channels of molecular oxygen activation (MOA) between Ag3PO4 and g-C3N4 (and g-C3N5) were confirmed. More importantly, according to this double consumption process of excited electrons, dual S-scheme g-C3N4/Ag3PO4/g-C3N5 could suppress the charge recombination, which was the key point to boosting photocatalytic activity. Moreover, the determination of intermediates also supported the vital role of MOA during these photocatalytic reactions. this report of two reactive sites in MOA that generate reactive oxygen species in a “V” type band structure. The electronic dynamic in the reaction was also testified by several detections, indicating the enhanced charge separation and migration from internal field effect and electron trapping from dual S-scheme mechanism. This work provides a new research direction for the design and mechanism analysis of dual S-scheme photocatalysts

Laccase surface-display for environmental tetracycline removal: From structure to function

Facing the increasingly prominent tetracycline pollution and the resulting environmental problems, how to find environmental and efficient treatment means is one of the current research hotspots. In this study, the laccase surface-display technology for tetracycline treatment was investigated. Via study, the type of anchoring protein had a minor influence on the laccase ability, while the type of laccase showed a major impact. Bacillus subtilis spore coat protein (CotA) exhibited higher laccase activity, stability, and efficiency in degrading tetracycline than Pleurotus ostreatus laccase 6 (Lacc6). The superiority of bacterial laccase over fungal laccase was elucidated from the perspective of crystal structure. Besides, a variety of technical means were used to verify the success of surface-display. pGSA-CotA surface-displayed bacteria exhibited good tolerance to high temperature, pH, and various heavy metals. Importantly, surface-displayed bacteria showed faster degradation efficiency and better treatment effects than the intracellular expression bacteria in tetracycline degradation. This implies that surface display technology has greater potential for laccase-mediated environmental remediation. Due to the adverse impacts of tetracycline on soil enzyme activity and microorganisms, our study found that pGSA-CotA surface-displayed bacteria can alleviate tetracycline stress in soil and partially activate the soil, thereby increasing soil enzyme activity and certain nitrogen cycling genes.

Enhanced photocatalytic performance of NiFe2O4/ZnIn2S4 p-n heterojunction for efficient degradation of tetracycline

The persistent release of tetracycline into the environment significantly endangers both ecosystems and human health. Zinc indium sulfide (ZnIn2S4) capable to degrade tetracycline pollutants under visible light irradiation has attracted extensive attentions and great effort has been devoted to augment its catalytic efficacy. In this work, we synthesized a p-n heterojunction, NiFe2O4/ZnIn2S4, to enhance the carrier migration rate and explained the intrinsic mechanism by density functional theory. When the heterojunction was formed, carriers traversed from the n-type NiFe2O4 to the p-type ZnIn2S4, instigating the emergence of a built-in electric field to facilitate the separation of carriers. 2 %-NiFe2O4/ZnIn2S4 exhibited excellent photocatalytic efficiency in tetracycline (TC) degradation and total organic carbon (TOC) removal. Compared to pure ZnIn2S4 and NiFe2O4, the TC degradation rates of 2 %-NiFe2O4/ZnIn2S4 were 2.0 times and 16.9 times higher, respectively. Additionally, 2 %-NiFe2O4/ZnIn2S4 had a saturation magnetization intensity of 3.05 emu/g, allowing for rapid recovery of the catalyst under a magnetic field. Superoxide radicals (O2−) and holes (h+) were the primary active species driving the degradation process. Furthermore, potential reaction pathways of tetracycline in this photocatalytic process were determined and bioconcentration factor and developmental toxicity of the intermediate products were accessed. This work held great potentials for wastewater treatment and provided a pathway for the development of magnetic recyclable photocatalysts.

Dual Fe3+/Fe2+ redox cycles boost H2O2 activation and enhance photooxidation behavior for degradation of tetracycline pollutants

Dual Fe3+/Fe2+ redox cycles boost H2O2 activation and enhance photooxidation behavior for degradation of tetracycline pollutants

Magnetic Fe3O4-C@MoS2 composites coordinated with peroxymonosulfate catalysis for enhanced tetracycline degradation

Tetracycline is an organic compound that poses a significant threat to both the ecological environment and human health during its long-term production and use. Advanced oxidation processes based on sulfate radicals (SR-AOP) have been recognized as effective techniques for treating antibiotic contamination. However, The urgent demand for a green, efficient, and recyclable catalyst to effectively facilitate persulfate treatment of tetracycline pollution is evident. Magnetic Fe3O4-C@MoS2 composite were synthesized using hydrothermal and pyrolysis methods. Degradation experiments, free radical quenching experiments, EPR analysis were carried out to investigate the degradation performance and mechanisms of Fe3O4-C@MoS2 composite. Results showed that the degradation efficiency of 100 mL of 20 mg/L tetracycline solution reached up to 97% within 40 mins with the dosage of 20 mg Fe3O4-C@MoS2 and 30.7 mg peroxmonosulfate. Furthermore, this degradation system exhibited excellent efficiency even over a wide pH range of 3–9. The transformation of Mo (IV) and S2-/Sn2- species valence states facilitated the conversion between Fe(III)/Fe(II). Both free radical (SO4⋅−,⋅OHandO2⋅−) as well as non-free radical species (O21) were found to accelerate the catalytic reaction during the tetracycline degradation. The possible pathways of tetracycline degradation were proposed, and the toxicity of the intermediate products were proved to be lower than that of tetracycline. Finally, magnetic Fe3O4-C@MoS2 composites possessed good reusability and stability after 4 cycles of degradation.

Sonochemical fabrication of S-scheme Bi2O2CO3/g-C3N4 heterojunction for enhanced photocatalytic destruction of rhodamine B and tetracycline pollutants under natural solar radiations

Photocatalysis is a promising low cost green technology to efficiently mineralize refractory contaminants from wastewater. In this novel research, S-scheme Bi2O2CO3/g-C3N4 heterojunctions containing (0-25) wt % Bi2O2CO3 were sonochemically fabricated for mitigation of hazardous rhodamine B dye and tetracycline antibiotic under sunlight radiations of 900 W power. The physicochemical properties of the solid specimen were explored by photoluminescence [PL], diffuse reflectance spectrum [DRS], X-ray diffraction [XRD], Mapping, high resolution transmission electron microscope [HRTEM], selected area electron diffraction [SAED], N2–adsorption–desorption isotherms and X–ray photoelectron spectroscopy [XPS] techniques. As elucidated by HRTEM analysis, 15 wt% of spherical Bi2O2CO3 nanoparticles of 12 nm size were deposited on g-C3N4 of 40 m2/g surface area at nearly equidistant from each other. The point of zero charge of g-C3N4 sheets was shifted from pHPZC 6.2 to pHPZC 4.8 with incorporation of 15 wt % Bi2O2CO3 revealing the production of negatively charged surface that strongly destructed cationic rhodamine B dye. The rate of photocatalytic degradation of rhodamine B dye for heterojunction containing 15 wt% Bi2O2CO3 was 0.0168 min−1 which is three fold higher than that of pristine g-C3N4 nanosheets. The radical scavengers experimental results revealed that superoxide radicals and positive holes are the main reactive species in the degradation process. The exceptional photocatalytic reactivity emerged from construction of S-scheme heterojunction with auspicious electron-hole pair separation and transportation electron-hole pairs and significant redox power.

Nitrogen and sulfur co-doped watermelon rind as an ordered mesoporous biochar activated peroxymonosulfate (PMS) for efficient tetracycline degradation

The ever-increasing tetracycline pollution and a large amount of watermelon rind waste have caused a double burden on the environment. How to realize the circular economy of treating waste with waste is of great practical significance, but still challenging. In this work, N, S co-doped/biochar (NSBC) with high adsorption and catalytic properties was successfully prepared from watermelon rind waste for the first time, and showed excellent performance in the degradation of tetracycline by activated peroxymonosulfate, with the degradation rate of TC reaching 90.02% in 40 min. The optimal preparation conditions of NSBC were determined by exploring the doping amount of thiourea and the carbonation temperature. On this basis, a series of characterization and experimental analyses demonstrated that suitable thiourea doping not only increased the active sites, defect edges, SSA and electron transfer of NSBC, but also possessed good stability properties. Free radical pathway (•OH, SO4•−, O2•−) combined with non-radical pathway (1O2 and charge transfer) resulted in the TC degradation, in which the non-radical pathway mainly contributed to the degradation process, and the intermediates of the degradation pathway were analyzed. This work provides a great prospect for resource utilization and environmental remediation of watermelon rind waste.

Efficacy and Mechanism of Tetracycline Adsorption by Boron-doped Mesoporous Carbon

Using coconut shell and boric acid as raw materials， a new boron-doped coconut shell mesoporous carbon material （B-CSC） was prepared using a simple one-step pyrolysis method for efficient adsorption and removal of tetracycline pollutants in water. The effects of pyrolysis temperature and boron-carbon mass ratio on the adsorption performance under key preparation conditions were systematically studied， and their microstructure and physicochemical properties were characterized using a specific surface area and pore size analyzer （BET）， field emission scanning electron microscopy （SEM）， X-ray photon spectroscopy （XPS）， Raman spectrometer （Raman）， and Zeta potentiometer （Zeta）. The effects of initial pH， different metal cations， and different background water quality conditions on the adsorption effect were systematically investigated. Combined with material characterization and correlation analysis， the enhanced adsorption mechanism was discussed and analyzed in depth. The results showed that one-step pyrolysis could incorporate boron into the surface and crystal lattice of coconut shell charcoal， resulting in a larger specific surface area and pore volume， and the main forms of boron introduced were H3BO3， B2O3， B， and B4C. The adsorption capacity of B-CSC to tetracycline reached 297.65 mg·g-1， which was 8.9 times that of the original coconut shell mesoporous carbon （CSC）. At the same time， the adsorption capacity of B-CSC for rhodamine B （RhB）， bisphenol A（BPA）， and methylene blue （MB）， common pollutants in aquatic environments， was as high as 372.65， 255.24， and 147.82 mg·g-1， respectively. The adsorption process of B-CSC to tetracycline was dominated by physicochemical interaction， mainly involving liquid film diffusion， surface adsorption， mesoporous and microporous diffusion， and active site adsorption， and H3BO3 was the main adsorption site. The adsorption strengthening mechanism mainly reduced the chemical inertness of the carbon network and enhanced its π-π interaction and hydrogen bonding with tetracycline molecules.

Synergetic impact of copper nanoparticles and polyaniline reinforced graphene oxide nanocomposite on the sequestration of tetracycline antibiotic from milk and wastewaters samples

Tetracycline pollution poses a serious threat to both human and animal health, even at very low concentrations. The removal of these antibiotics from ecosystems has gained significant academic and public attention. Herein, tetracycline (TC) antibiotic in different environmental water samples were successfully extracted using copper nanoparticles immobilized-polyaniline modified graphene oxide (Cu/PANI/GO) nanocomposite. The structure and physicochemical properties of the new fabricated nanocomposite were investigated by various analytical techniques including SEM, TEM, EDX, FTIR, Raman spectra, and zeta-potential. It has been found that TC removal efficiency onto Cu/PANI/GO was greatly improved when compared to the native GO, and that it could even achieve a record-high value of 99.6% with 434.78 mg g−1 adsorption capacity. The synergic effect of the supported Cu-NPs and PANI moieties for the TC removal efficiency is about 51.5 ± 3.9% compared to that for GO. The pseudo-second-order (PSO) kinetic model and the Langmuir model, respectively, can provide excellent fits for the adsorption kinetics and isotherms of TC onto Cu/PANI/GO. Five adsorption-desorption cycles resulted in a 4.1% reduction in the removal effectiveness. Through the surface complexation by the Cu-nanoparticles, in addition to the potent hydrogen bond formation with PANI and GO moieties and the π-π interactions of graphene oxide, TC were firmly trapped in the structure of the Cu/PANI/GO nanocomposite. The Cu/PANI/GO nanocomposite was utilized to remove TCs from samples of milk and wastewater.

Tetracycline removal from soil by phosphate-modified biochar: Performance and bacterial community evolution

Since the remediation performance of soil tetracycline pollution by original biochar is not ideal, many modified methods have been proposed to improve its performance. Considering the cost, complex modification process and environmental friendliness, many modified biochar are difficult to be used in soil environments. In this work, biochar derived from corn stover was modified using phosphate to increase the adsorption ability of soil tetracycline and alleviate the negative effects caused by tetracycline. The results showed that pyrolysis temperatures and anion types of phosphate (PO43−, HPO42−, H2PO4−) played important roles in the performance of modified biochar. Compared with original biochar, phosphate modified biochar not only improved the adsorption capacity, but also changed the adsorption behavior of tetracycline. Via SEM, BET and FTIR techniques, the intrinsic reasons for the increase of adsorption capacity were explained by the change of morphological structures as well as functional groups of the modified biochar. K3PO4 and high temperature (800 °C) maximally improved the surface morphology, increased the pore structure, changed the surface functional groups of biochar, and then increased the adsorption capacity of tetracycline (124.51 mg/g). Subsequently, the optimal material (K3PO4-800) was selected and applied for tetracycline contaminated soil remediation. Compared to the soil without remediation, K3PO4-800 modified biochar effectively reduced the effective concentration of tetracycline in soil, and improved soil K and P nutrition, and reshaped microbial communities. Our study showed that K3PO4-800 modified biochar was not only a good tetracycline resistant material, but also a good soil amendment.

A novel porous aromatic framework with mesopores for removal of antibiotics from water

Porous aromatic frameworks (PAFs) display high potential for wastewater treatment, due to their high surface area and extreme stability. PAF-134 was synthesized based on a 3-connected non-planar building unit, tris(4-bromophenyl)(phenyl)silane (PBTSi-3-Br), via Yamamoto coupling reaction. PAF-134 exhibited high BET surface area of 865.7 m2/g, large mesopore ratio of 69 % pore volume and excellent stability. Three tetracycline pollutants, tetracycline (TC), oxytetracycline (OTC) and chlortetracycline hydrochloride (CTC), were chosen to study the antibiotics adsorption performance for PAF-134. The adsorption isotherms, kinetics, and thermodynamics were measured and analyzed. Moreover, PAF-134 in removing antibiotics from actual water exhibited high efficiency and possessed outstanding recyclability and stability, thus showing that it is a promising adsorbent for wastewater treatment.

Tetracycline inhibits the nitrogen fixation ability of soybean (Glycine max (L.) Merr.) nodules in black soil by altering the root and rhizosphere bacterial communities

Tetracycline is a widely used antibiotic and may thus also be an environmental contaminant with an influence on plant growth. The aim of this study was to investigate the inhibition mechanisms of tetracycline in relation to soybean growth and ecological networks in the roots and rhizosphere. To this end, we conducted a pot experiment in which soybean seedlings were grown in soil treated with 0, 10, or 25 mg/kg tetracycline. The effects of tetracycline pollution on growth, productivity, oxidative stress, and nitrogenase activity were evaluated. We further identified the changes in microbial taxa composition and structure at the genus and species levels by sequencing the 16S rRNA gene region. The results showed that tetracycline activates the antioxidant defense system in soybeans, which reduces the abundance of Bradyrhizobiaceae, inhibits the nitrogen-fixing ability, and decreases the nitrogen content in the root system. Tetracycline was also found to suppress the formation of the rhizospheric environment and decrease the complexity and stability of bacterial networks. Beta diversity analysis showed that the community structure of the root was markedly changed by the addition of tetracycline, which predominantly affected stochastic processes. These findings demonstrate that the influence of tetracycline on soybean roots could be attributed to the decreased stability of the bacterial community structure, which limits the number of rhizobium nodules and inhibits the nitrogen-fixing capacity. This exploration of the inhibitory mechanisms of tetracycline in relation to soybean root development emphasises the potential risks of tetracycline pollution to plant growth in an agricultural setting. Furthermore, this study provides a theoretical foundation from which to improve our understanding of the physiological toxicity of antibiotics in farmland.

Construction of Z-scheme BiVO4/NaNbO3 piezo-photocatalyst with improved carrier separation for efficient removal of tetracycline

Piezoelectric catalysis combined with photocatalysis could use both solar energy and mechanical energy to degrade tetracycline pollutants, promising for application in environmental remediation but also facing challenges. This paper designed and synthesized a novel Z-scheme BiVO4/NaNbO3 heterojunction to obtain high piezo-photocatalytic activity. Under the co-acting of light radiation and ultrasound, the reaction rate constant (k) of optimal proportion BiVO4/NaNbO3(BV/NN-2) heterostructure on the tetracycline reached 0.028 min−1, which indicates that the piezo-photodecomposition ratio of TC is 1.33 times higher than the BiVO4. In addition, the degradation rate of the BV/NN-2 sample under light irradiation + ultrasonic vibration was 2.6 and 3.7 times higher than that on the condition of light irradiation and ultrasound, respectively. The results further revealed the coupling effect between piezoelectric catalysis and photocatalysis. The morphology observations revealed that the BiVO4 nanoparticles grow on the surface of the NaNbO3 nanorods. Photoluminescence demonstrated that Z-scheme BiVO4/NaNbO3 heterojunction exhibited higher current separation and transfer efficiency than BiVO4 and NaNbO3. BiVO4 produces many photogenerated carriers under visible light, which supplements the free carriers consumed by BiVO4/NaNbO3 piezoelectric catalysis and dramatically improves the catalytic activity. This study provided a promising strategy to enhance piezoelectric catalysis for removing antibiotic contaminants.

Advanced Stimuli-Responsive Structure Based on 4D Aerogel and Covalent Organic Frameworks Composite for Rapid Reduction in Tetracycline Pollution.

Intelligentization of materials and structures is an important trend. Herein, the stimuli-responsive 4D aerogel is used as a smart substrate for rapid reduction in tetracycline (TC) pollution, in which this smart stimuli-responsive substrate is designated as P4D. Its fourth dimension originates from stimuli-responsive characteristics with time evolution. Meanwhile, the covalent organic frameworks (COFs) composite is constructed by BiPO4 and triazine-based sp2 carbon-conjugated g-C18N3-COF (COF-1), which is another key aspect of COF-1/BiPO4@P4D for rapid photocatalytic degradation regarding TC pollution. This emerging smart structure of COFs@P4D can fix programmable temporary state and recover permanent state under thermal or water stimulus without any complicated equipment. Its performance can be tailored by structure, composition, and function. Compared with traditional powder-form photocatalysts, this stimuli-responsive structure provides attractive advantages, such as high permeable framework, self-adaptivity, flexibly customized functional groups, and fast reduction in TC pollution. The predictable development of COFs@P4D could draw much attention for various promising applications in pollution treatment and sensors.

Fabrication of g-C3N4@N-doped Bi2MoO6 heterostructure for enhanced visible-light-driven photocatalytic degradation of tetracycline pollutant

An effective catalyst for the removal of antibiotic pollutants which severely impact water bodies and the environment is most favorable. In this study, g-C3N4 (gCN) and nitrogen-doped Bi2MoO6 (gCN-NBM) heterostructures are developed using a solvothermal process with enhanced photocatalytic degradation of tetracycline (TC) pollutants under visible-light irradiation. The experimental results confirm that nitrogen-doped Bi2MoO6 (NBM) nanomaterials were dispersed on the gCN surface, and a close combination of NBM and gCN leads to the efficient photocatalytic performance of TC. The photocatalytic efficiency of the heterostructure catalysts is four-fold higher than those of the pristine Bi2MoO6 catalysts owing to the excellent photogenerated charge separation and reduced recombination rate. Photocurrent measurements and electrochemical impedance spectra results disclose that the prepared heterostructure catalysts exhibit efficient photo-induced charge transfer. The electron spin resonance spectra and quenching experiments results reveal that superoxide radicals (.O2−) play a major role in TC degradation. This study presents a promising approach for designing efficient visible-light photocatalysts for environmental remediation applications.

Remediation of tetracycline pollution using MXene and nano-zero-valent iron materials: a review

Remediation of tetracycline pollution using MXene and nano-zero-valent iron materials: a review

Integrated Multiomics and Synergistic Functional Network Revealed the Mechanism in the Tolerance of Different Ecotypes of Salvia miltiorrhiza Bge. to Doxycycline Pollution.

Tetracycline pollution in soil irreversibly damages the biosafety of plants by inhibiting the mitochondrial function. Some traditional Chinese medicine (TCM) plants, such as Salvia miltiorrhiza Bunge, have a strong tolerance to mitochondrial damage. We comprehensively compared the doxycycline (DOX) tolerances of two ecotypes of S. miltiorrhiza in the Sichuan and Shandong provinces and found that the Sichuan ecotype had a lower yield reduction, more stable accumulation of medicinal ingredients, higher mitochondrial integrity, and a more robust antioxidant system. The synergetic response networks under DOX pollution of both ecotypes were constructed using RNA sequencing and ultrahigh-performance liquid chromatography-tandem mass spectrometry. The differentiation of the downstream pathways of aromatic amino acids (AAAs) produced variations in the DOX tolerance of S. miltiorrhiza in different regions. The Sichuan ecotype maintained redox homeostasis and xylem development by activating salvianolic acid and indole biosynthesis, while the Shandong ecotype balanced chemical and mechanical defenses by regulating the flavonoid biosynthesis. Rosmarinic acid, a downstream AAA molecule, maintains the mitochondrial homeostasis of plant seedlings under DOX pollution by targeting the ABCG28 transporter. We also highlight the significance of downstream AAA small molecules in guiding the development of bio-based environmental pollution remediation agents.

The process of free radical generation in contact electrification at solid-liquid interface

Solid-liquid interfaces are ubiquitous in nature and widely used in various applications such as catalysis, sensing, batteries, etc. Recently, we found the existence of electron transfer at the interface in solid-liquid contacting, and proposed a “two-step” theory for the formation of solid-liquid electric double layer (EDL). In this work, we found that hydroxyl radical (·OH) was generated when the droplet contact with the tube inner wall without external interference, and the concentration of·OH was increased with increasing pH, demonstrating that the·OH was generated from hydroxide ions (OH-) by electron transfer during contact electrification. This can be further supported by the fact that capillaries made of materials with stronger electron-withdrawing ability could generate more·OH. Interestingly, superoxide anion radical (·O2-) was not generated at the solid-liquid interface if no external energy is provided. However, if ultrasonic was applied,·O2- could be generated at the solid-liquid interface, because ultrasonication provides transition energy for the electron to transfer from the solid to O2 at the interface. Based on the generation of reactive oxygen species (·OH and·O2-), we demonstrated a proof-of-concept for degradation of tetracycline pollution. This work provides an excellent strategy to study the solid-liquid interface and also provides a new insight into the free radical generation at the interface in solid-liquid contacting.

Change of tetracycline speciation and its impacts on tetracycline removal efficiency in vermicomposting with epigeic and endogeic earthworms

Tetracycline pollution is common in Chinese arable soils, and vermicomposting is an effective approach to accelerate tetracycline bioremediation. However, current studies mainly focus on the impacts of soil physicochemical properties, microbial degraders and responsive degradation/resistance genes on tetracycline degradation efficiencies, and limited information is known about tetracycline speciation in vermicomposting. This study explored the roles of epigeic E. fetida and endogeic A. robustus in altering tetracycline speciation and accelerating tetracycline degradation in a laterite soil. Both earthworms significantly affected tetracycline profiles in soils by decreasing exchangeable and bound tetracycline but increasing water soluble tetracycline, thereby facilitating tetracycline degradation efficiencies. Although earthworms increased soil cation exchange capacity and enhanced tetracycline adsorption on soil particles, the significantly elevated soil pH and dissolved organic carbon benefited faster tetracycline degradation, attributing to the consumption of soil organic matter and humus by earthworms. Different from endogeic A. robustus which promoted both abiotic and biotic degradation of tetracycline, epigeic E. foetida preferently accelerated abiotic tetracyline degradation. Our findings described the change of tetracycline speciation during vermicompsiting process, unraveled the mechanisms of different earthworm types in tetracycline speciation and metabolisms, and offered clues for effective vermiremediation application at tetracycline contaminated sites.