Tetracycline In Wastewater Research Articles

Efficient degradation of tetracycline in wastewater by novel biochar-based photocatalytic materials: performance, photocatalytic mechanism and degradation pathways

Efficient degradation of tetracycline in wastewater by novel biochar-based photocatalytic materials: performance, photocatalytic mechanism and degradation pathways

Heterogeneous Fenton system driven by magnetic graphene-like biochar for degrading tetracycline

In this study, a novel catalyst with high efficiency and low cost was synthesized from farmland waste peanut shells by one-step pyrolysis modification method via K2FeO4, and employed for the catalytic degradation of tetracycline (TC). The magnetic potassium ferrate modified graphene-like biochar catalyst (PFGB) exhibited a high porosity, a highly graphitized structure, and a large specific surface area (857.09 m2·g-1) which was almost 30 times higher compared with peanut shell biochar, and were found to contain more functional groups. The formation and distribution of Fe3O4 and Fe0 nanoparticles on the surface/pores of PFGB provided more active sites for promoting adsorption and catalytic degradation reactions, and accelerated Fe(II)/Fe(III) recycle. Under the optimal conditions (pH=3.5, catalyst dosage = 0.5g·L-1, H2O2 concentration = 10mmol·L-1), about 98% of TC were degraded within 90min when the initial concentration of TC was 150mg·L-1, and PFGB could perform effectively over a wide pH range of 3-6. Furthermore, PFGB exhibited the advantages of convenient magnetic separation and strong reusability, maintaining a TC removal rate of ~90% after five cycles of experiments. The results of free radical quenching experiment and electron spin resonance analysis revealed that •OH and 1O2 were the main active species in the radical and non-radical pathways, respectively. This study indicated that PFGB, a catalyst developed for heterogeneous Fenton-like systems, possessed high efficiency, stability and reusability, and could be promising for the removal of TC in wastewater and other polluted waters.

Mechanism of enhanced degradation of antibiotic wastewater by three-dimensional electrocatalytic oxidation system: Coconut shell biochar as particle electrode

A porous particle electrode, coconut shell biochar (CBC), was prepared using coconut shell as raw material and applied to the treatment of tetracycline (TC) wastewater. Exploring the three-dimensional electrocatalytic oxidation system using a series of key factors such as pH (2−10), current density (20–60 mA/cm2), CBC particle size (0.88–2.36 mm), CBC dosage (3–13 g/L), electrolyte concentration (5000–10,000 mg/L), and electrode spacing (3–5 cm). The optimal conditions for these parameters were 10, 50 mA/cm2, 1.4–1.7 mm, 7 g/L, 8000 mg/L, and 4 cm. Under these conditions, the degradation of TC conformed to pseudo-first-order kinetics. The chemical oxygen demand (COD) and TC removal rates reached 84.01 % and 99.18 % within 45 min, while the two-dimensional system only achieved 29.27 % and 39.83 %, respectively. The degradation mechanism of TC was determined based on the production of H2O2 and •OH. The adsorbed saturated CBC might be regenerated through electrochemical reactions, inducing further adsorption, and forming numerous micro electrolysis cells to promote the production of free radicals, thereby boosting TC mineralization. Finally, the high-performance liquid chromatography-mass spectrometer was applied to identify the transformation products and degradation pathways of TC. Additionally, the CBC still showed excellent catalytic degradation effect after being reused for 4 times. Therefore, this study makes it possible to prepare an efficient and low-cost electrocatalyst for the treatment of antibiotic wastewater, as well as for further understanding the electrocatalytic mechanism, conversion products, and degradation pathways of TC in wastewater.

Construction of novel biochar/g-C3N4/BiOBr heterojunction with S-scheme mechanism for efficient photocatalytic degradation of tetracycline

In this work, a novel biochar/g-C3N4/BiOBr (BCN/BiOBr) S-scheme heterojunction was synthesized for the removal of tetracycline (TC) under visible light. The 0.75-BCN/BiOBr heterojunction exhibited a significantly higher degradation efficiency of TC in wastewater under visible light excitation, achieving about 86.5 % degradation in 72 minutes, which is 2.5 times higher than that of pure g-C3N4. Furthermore, the influence of factors such as pH, dosage of tetracycline and photocatalyst on TC degradation were investigated. Photochemical characterization experiments revealed that the enhanced degradation performance of the BCN/BiOBr heterojunction stemmed from the synergistic effects of adsorption and photocatalysis, providing more active sites to promote the photocatalytic reaction, and accelerating accelerate charge separation and light absorption ability. Meanwhile, the results from the active species indicated that h+, ·OH, and ·O2- play major roles in the degradation process. Additionally, the mechanism research revealed that the photogenerated carriers followed an S-scheme step transfer pathway at the interface of BiOBr and g-C3N4, and the two possible pathways for TC degradation. This provides guidance for improving wastewater treatment using biochar-modified high-efficiency S-scheme photocatalysts.

Phosphorus recovery and tetracycline Mitigation: The role of Bacillus cereus LB-9 in struvite biomineralization from wastewater

Struvite biomineralization is an ecologically sound technology, adept at the efficient recovery and recycling of phosphorus from wastewater. However, the biomineralization process is often perturbed by the presence of antibiotics, notably tetracycline (TC), the impact of which on the biomineralization system has not been elucidated. This study examines the efficacy of Bacillus cereus LB-9 in struvite biomineralization, focusing on the precipitates' composition, morphology, and TC content. LB-9 facilitate an alkaline environment that effectively recovering nitrogen and phosphorus. These findings indicate that TC retards the initial formation of struvite and the concurrent recovery of nitrogen and phosphorus. However, at concentrations below 10 mg/L TC concentrations, TC enhanced struvite production (0.38g) by stimulating LB-9's growth and metabolic activity. Conversely, at a concentration of 10 mg/L TC, the strain's activity was markedly suppressed within the initial four days. This data suggests that TC promotes the strain's proliferation and metabolism, potentially through cellular secretions, thereby augmenting phosphorus recovery from wastewater. Notably, the recovered struvite doesn't contain TC, aligning with regulatory standards for agricultural application. In summary, LB-9-mediated struvite recovery is an effective strategy for producing phosphorus-enriched fertilizers and mitigating TC contamination, offering significant implications for wastewater treatment and industrial process development, particularly in the context of prevalent TC in wastewater.

Photocatalytic Degradation of Tetracycline in Wastewater with Bio-based Matrix Magnetic Heterogeneous Nanocatalyst: Performance and Mechanism Study

Photocatalytic Degradation of Tetracycline in Wastewater with Bio-based Matrix Magnetic Heterogeneous Nanocatalyst: Performance and Mechanism Study

Construction of oxygen-doped g-C3N4/BiOCl (S-scheme) heterojunction: Efficient degradation of tetracycline in wastewater

Graphitic phase carbon nitride (g-C3N4) demonstrates significant promise in the photocatalytic degradation of organic pollutants, but the rapid recombination of photogenerated electron-hole pairs seriously restricts its degradation capacity. In this study, an innovative heterostructural anion regulation strategy based on g-C3N4 was proposed to significantly enhance the degradation performance of tetracycline. Initially, we regulated the electron configuration of g-C3N4 through O doping to optimize the active sites at the reaction interface. Subsequently, the S-scheme heterojunction was constructed by introducing BiOCl to stimulate the pumping effect and form efficient build-in electric field electron channels. The oxygen-doped g-C3N4/BiOCl (OCN/BiOCl) heterojunction material obtained through aforementioned modification exhibited a degradation efficiency of 89.33 % towards 20 mg·L−1 tetracycline (90 min light reaction, 30 min dark reaction), which was 2.5 times that of conventional g-C3N4 catalyst. In particular, density functional theory calculations and ultraviolet photoelectron spectroscopy jointly revealed the unique chemical environment and electronic structure between OCN and BiOCl due to the formation of the build-in electric field, thereby providing enhanced pathways for the migration of photogenerated currents. Meanwhile, the heterostructure significantly reduced the transport distance of photo-induced charge and minimizes the internal transmission resistance. It enhances the efficiency of separating photogenerated electrons and hole pairs, which is the key mechanism for greatly improving the photocatalytic degradation performance of OCN/BiOCl materials. In summary, the hetero-anion regulation strategy proposed in this study addresses the issue of rapid recombination of photogenerated charges in g-C3N4, providing a new perspective for efficient control of organic pollutants in the environment driven by g-C3N4 photocatalyst.

Efficient Adsorbent Derived from Phytolith-Rich Ore for Removal of Tetracycline in Wastewater.

In recent decades, the tetracycline (TC) concentration in aquatic ecosystems has gradually increased, leading to water pollution problems. Various mineral adsorbents for the removal of tetracyclines have garnered considerable attention. However, efficient adsorbents suitable for use in a wide pH range environment have rarely been reported. Herein, a phytolith-rich adsorbent (PRADS) was prepared by a simple one-step alkali-activated pyrolysis treatment using phytolith as a raw material for effectively removing TC. PRADS, benefiting from its porous structure, which consists of acid- and alkali-resistant, fast-adsorbing macroporous silica and mesoporous carbon, is highly desirable for efficient TC removal from wastewater. The results indicate that PRADS exhibited excellent adsorption performance and stability for TC over a wide pH range of 2.0-12.0 under the coexistence of competing ions, which could be attributed to the fact that PRADS has a porous structure and contains abundant oxygen-containing functional groups and a large number of bonding sites. The adsorption mechanisms of PRADS for TC were mainly attributed to pore filling, hydrogen bonding, π-π electron-donor-acceptor, and electrostatic interactions. This work could offer a novel preparation strategy for the effective adsorption of pollutants by new functionalized phytolith adsorbents.

Synergistic effects of peroxydisulfate on UV/O3 process for tetracycline degradation: Mechanism and pathways

Tetracycline (TC) as a typical emerging pollutant is becoming a serious threat to the environment and human health. A combined advanced oxidation technology of UV/Ozone (O3)/peroxydisulfate (PDS) process was developed to explore an efficient and economic treatment process of TC in wastewater. Furthermore, the reactive sites and transformation pathways of TC were explored and the toxicity of the intermediates was quantified with a quantitative structure-activity relationship (QSAR) assessment. The degradation performance of TC was substantially enhanced in UV/O3/PDS process with a kobs of 0.0949 min−1, which was 2.3 times higher than UV/O3 and 3.2 times than sole UV. The results demonstrated that there was a superior synergistic effect of PDS on UV/O3 processes for the degradation of TC. Electron paramagnetic resonance (EPR) analysis and quenching experiments show that •OH, SO4•−, O2•− and 1O2 all contributed to TC degradation in the UV/O3/PDS process and exhibited a synergistic effect, which inhibited the generation of harmful products. In addition, the UV/O3/PDS system can effectively degrade TC in a wide range of substrate concentrations and pH, and also showed excellent adaptability to various concentrations of anions (Cl− and HCO3−). This study proves the feasibility of UV/O3/PDS process for treating TC contaminated wastewater with complicated water matrix.

Combined effect of amino nitrogen and pyridine nitrogen for tetracycline adsorption on aminopyridine modified MIL-101(Cr)

xApy-MIL-101(Cr) was successfully synthesized by incorporating 4-aminopyridine, and it was employed for adsorption of tetracycline in wastewater.

Automated method for the solid phase extraction of tetracyclines in wastewater followed by fluorimetric determination

This work presents a multisyringe flow injection analysis (MSFIA) system for the automatic extraction and determination of tetracyclines in wastewater samples. The sample was adjusted with Na2EDTA buffer before solid-phase extraction with an Oasis HLB column used for the analyte preconcentration. The europium (Eu3+)-based and citrate-mediated method (using Tris-HCl buffer) was selected for the fluorimetric analysis (λexc/em = 400/612 nm). For fluorescence detection, a low-cost system consisting of an USB 2000 CCD detector and a 3D-printed support that holds a LED light source was used. Under optimized conditions, the proposed method provided low limits of detection (9.4 μg L−1) and quantification (31 μg L−1), and good values for intra-day (<4 %) and inter-day precisions (<6 %). Recoveries of spiked TCs in wastewater samples ranged from 87 to 106 %. The results of this work were in good agreement with the measurements obtained by liquid chromatography coupled to a fluorescence detector.

Natural sunlight driven degradation of tetracycline in wastewater by dual Z − scheme photocatalyst of hollow nanospherical β–In2S3 decorated g − C3N4/WO3: performance, mechanism and products toxicity

The dual Z–scheme photocatalysts of β–In2S3/g − C3N4/WO3 (ISCNWO) were synthesized with improved light adsorption, carrier separation and specific surface area for tetracycline (TC) degradation by sunlight irradiation. The ISCNWO2 exhibited superior solar photodegradation performance of TC, and the kinetic constant was 2.2, 5.6 and 2.3 times that of g–C3N4, WO3 and In2S3, respectively. According to response surface methodology, the optimum TC removal was 96.4 ± 0.37 % at pH = 3.4 for 140 min irradiation without electrolyte. Even in river, municipal, hospital, frog farming field and tail wastewater, TC degradation efficiencies under solar irradiation for 300 min were > 74 %. As the lower work function of WO3 than that of In2S3 and g–C3N4 calculated by density functional theory (DFT), the electrons migrated from WO3 to In2S3 and g–C3N4 driven by built–in electric field. Under destruction of O2− and OH radicals, TC progressively transformed into 22 intermediates by addition, aromatic ring opening, etc. The toxicity prediction and in vivo experiments towards D. magna, V. fisheri and E. coil suggested that some intermediate products had relative high acute and bioaccumulation toxicity, so it was necessary to control ecological risks. Besides, as the satisfactory reusability of ISCNWO2 with 82.9 % TC removal after 5 cycles, the ISCNWO might had great application prospects in the treatment and remediation of antibiotic contaminated wastewater/natural water.

Ultrasonic degradation of tetracycline combining peroxymonosulfate and BiVO4 microspheres

Tetracycline (TC) has received widespread attention due to the negative impacts of the drug abuse on ecological system and human health. Sonodegradation coupled with catalyst has proven to be an efficient method to treating TC. In this paper, BiVO4 microspheres synthesized by hydrothermal method and peroxymonosulfate (PMS) were used as sonocatalysts. Comparison of the degradation experiments revealed that combination of BiVO4/PMS with ultrasound (US) resulted in the highest degradation rate of TC, and the synergistic factor was calculated to be 6.17, which indicates a very significant synergistic effect. Effects of many factors, such as US power, BiVO4 concentration, dosage of PMS, initial TC concentration and matrix ion, on tetracycline degradation were investigated, and the operating parameters were optimized by response surface methodology, which predicted that TC degradation rate could reach 91.4 % after 60 min by setting initial TC concentration of 20 mg/L, BiVO4 concentration of 1.156 g/L, PMS dosage of 2.331 mM, and US power of 419 W. Active species analysis verified that radicals, such as OH, SO˙4−, h+ and O˙2−, were the primary contributors to TC removal, and ultrasonic cavitation plays a key role in sonocatalysis. The TC degradation rate only decreased by 1.6 % after four reuses of BiVO4. Moreover, the intermediate of TC degradation was detected using a liquid chromatograph-mass spectrometer (LC-MS), and the degradation pathway revealed that deamination, decarbonization and ring-opening reaction eventually result in the decomposition of TC. This work proposes a method for an efficient degradation of TC in waste water.

Titanium‐based MOFs‐derived Cabon‐supported Photocatalysts for the Efficient Degradation of Tetracycline

AbstractIn order to eliminate the public health hazard of tetracycline in a more environmentally friendly and efficient manner, a titanium‐based metal‐organic framework material containing Co ions was synthesised as a precursor by the traditional solvothermal method. Subsequently, a series of titanium‐based MOFs‐derived carbon‐supported photocatalysts were synthesised by calcining the precursor at different temperatures in air. All the prepared catalysts achieved effective degradation of the model pollutant tetracycline (TC). By adjusting the parameters such as TC concentration, catalyst dosage and irradiation time, the optimised composite material (TiCoOC‐800‐1) has a degradation rate of 99.4 % for the model pollutant TC with a concentration of 100 mg/L after under the UV irradiation during 30 min. Radical scavenging experiments showed that the main oxide species responsible for the rapid photodegradation of tetracycline were superoxide radicals (⋅O2−) and holes (h+). Finally, the liquid chromatography mass spectrometry (LC–MS) method was used to detect the molecular degradation intermediates of TC and a possible degradation pathway was proposed. This work will provide new ideas for the development of more efficient photocatalysts for the degradation of TC in wastewater.

Leveraging anaerobic biodegradation of tetracycline in anaerobic digestion systems with different operational modes

Antibiotics such as tetracycline in wastewater may cause the operation failure of anaerobic digestion systems. With two types of operational modes, continuous-flow reactors (CFRs) and sequencing batch reactors (SBRs) were operated with or without the addition of tetracycline to examine the influence of tetracycline on system performance, tetracycline removal, metabolic activity, and microbial communities. Tetracycline inhibited the removal of chemical oxygen demand (COD) by 23.9% in CFRs and 20.5% in SBRs, and led to the accumulation of volatile fatty acids (VFAs). Also, the maximum methane production rate was inhibited by 24.5% in CFRs and 48.8% in SBRs due to the existence of tetracycline, while the maximum methane production was reduced by 32.8% in CFRs and 13.8% in SBRs. CFRs exhibited a better recovery capacity during COD shock loading and demonstrated superior propionate degradation and methane production capabilities. Moreover, CFRs achieved better tetracycline removal capacity compared to SBRs. Biodegradation was found to be the dominant tetracycline removal pathway, accounting for 88.9% (CFRs) and 82.0% (SBRs). Long-term exposure to tetracycline decreased archaea abundances and inhibited the enrichment of hydrolytic-acidogenic bacteria (Mesotoga and Syner-01). Meanwhile, CFRs provided a more conducive environment for the enrichment of these microorganisms. The presence of Geobacter in conjunction with the detected ethanol in batch experients of CFRs suggested the potential presence of direct interspecies electron transfer, elucidating the enhanced pollutant removal of CFRs. Additionally, Trichococcus, a genus associated with tetracycline removal, was found to be highly enriched with the long-term dosage of tetracycline.

Phyto-mediated hydrothermal synthesis of NiFe2O4 as photocatalyst in tetracycline photodegradation

Tetracycline is one of the most important compounds in pharmaceutical industry, furthermore the controlling tetracycline in wastewater is important aspect for sustainable pharmaceutical industry. This study explores a photocatalytic degradation approach for the tetracycline removal by using magnetic nanomaterial of NiFe2O4 nanoparticles as photocatalyst. As a strategy in green chemistry approach, hydrothermal synthesis by using plant extract of Aloe vera extract was performed. Different techniques such x-ray diffraction (XRD), x-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), scanning electron microscopy (SEM), UV–Visible spectrophotometry (UV-DRS) and magnetism analysis have been performed to characterize the sample. From TEM identification, the irregular shapes of NiFe2O4 NPs with particle size ranging at 5–40 nm was produced, and from XRD analysis, the crystallite size of the sample is 39.2 nm. The material demonstrates superparamagnetic behavior, and has the band gap energy of 1.84 eV. The photocatalytic activity assessment of the NiFe2O4 showed the degradation efficiency of about 75% and 65.53% under UV and visible lights, respectively. The easiness in separation of the rest photocatalyst supports the recoverability and stability until 5th cycle of usage with insignificant change of degradation efficiency.

Bio-derived 1T-MoS2/C-based aerogel by synergistic solar evaporation and tetracyclines removal for efficient freshwater generation

Tetracycline, a broad-spectrum antibiotic, has been widely used in disease treatment and other fields. However, due to the unreasonable use, tetracycline residue remains in water which eventually endangers human health. The green environmental protection, low-cost, and renewability biomass aerogel are highly attractive for the purification of tetracycline wastewater. Here, the flower-like 1T-MoS2 with S vacancies was uniformly grown on the supporting poplar catkin fibers-based biomass carbon matrix, which was constructed 3D porous aerogel by ice template method. The adsorption kinetics and adsorption isotherms model of MoS2/C-based aerogel for tetracycline in wastewater was investigated, revealing a maximum adsorption capacity of 124.4 mg g−1. More notably, the MoS2/C-based aerogel displayed excellent photothermal performance, which could synergistically raise the local temperature. The solar evaporation induced transpiration was able to accelerate the adsorption of tetracycline, owing to the endothermic behavior of tetracycline adsorption process. The MoS2/C-based aerogel attained an excellent water evaporation rate of 2.54 kg m−2 h−1 under one sun illumination, which is 11 times that of pure water. The solar purification prototype-based on MoS2/C-based aerogel could effectively remove tetracycline and generate freshwater. The freshwater production was about 33.6 kg m−2, and the tetracyclines were completed removed in the generation of condensed water on sunny days. The unique bifunctional capability of the MoS2/C-based aerogel paved a new strategy for tetracycline wastewater treatment and alleviated the dilemma of global water.

Magnetic field facilitated electrocatalytic degradation of tetracycline in wastewater by magnetic porous carbonized phthalonitrile resin

Herein, the magnetic field facilitated electrocatalytic degradation of tetracycline is reported for the first time. A magnetic porous carbonized phthalonitrile resin electrocatalyst has been prepared through directly annealing phthalonitrile monomer, polyaniline coated barium ferrite and potassium hydroxide. The tetracycline degradation percentage (DP%) by such electrocatalyst is significantly increased up to 37.42% under magnetic field with the optimal pH value of 5.0 and bias voltage of 1.0 V (vs. SCE). The mechanism of this phenomenon is explained by the spin-selective electron removal process in the reaction between metal-oxygen species and tetracycline on the electrocatalyst. The comparison of degradation pathways for tetracycline with and without magnetic field confirms the improvement of tetracycline DP%. This work opens a new direction for the application of an external magnetic field in the electrocatalytic degradation of antibiotics in wastewater.

Preparation of a high-performance N-defect ZnO@g-C3N4 nanocomposite and its photocatalytic degradation of tetracycline

In this study, pure ZnO and N-deficient g-C3N4 (CN) were synthesized by co-precipitation method and simple calcination method, respectively. In addition, ZnO was impregnated on the surface of CN with mass percentages of 5, 10, 15, 20, 25 and 30 respectively. In addition, these materials were characterized by XRD, UV-Vis-DRS, TEM, SEM, PL and FT-IR. As a prepared material, the catalytic activity of tetracycline in wastewater was tested under visible light irradiation. The results showed that among all these catalysts, 10 wt% ZnO/g-C3N4 (ZN) showed better catalytic activity. When the mass ratio of ZN was 1: 10 and the calcination temperature was 550 ℃, the interlayer spacing, specific surface area and pore volume were larger, and the tetracycline removal rate and catalytic performance were the best. At the initial concentration of 20 mL/L and the addition of 50 mg catalyst, the degradation rate of tetracycline hydrochloride reached 93.47% within 120 min with ZN (0.10). The degradation rate reached nearly 100% at 80 min after adding H2O2. Advanced oxidation process can greatly promote the degradation of wastewater and has guiding significance in large-scale industrial application in the future.

A study on the performance of a novel adsorbent UiO-66 modified by a nickel on removing tetracycline in wastewater

In the present study, Ni-UiO-66 was synthesized to improve the adsorption efficiency of tetracycline (TC) in wastewater treatment. To this end, nickel doping was performed in the preparation process of UiO-66. The synthesized Ni-UiO-66 was characterized by XRD, SEM and EDS, BET, FTIR, TGA, and XPS for obtaining the lattice structure, surface topography, specific surface area, surface functional groups, and thermostability. More specifically, Ni-UiO-66 has a removal efficiency and adsorption capacity of up to 90% and 120 mg g−1, respectively, when used to treat TC. The presence of ions HCO3−, SO42−, NO3− and PO43− slightly affects the TC adsorption. A 20 mg L−1 humic acid reduces the removal efficiency from 80% to 60%. The performed analyses revealed that Ni-UiO-66 had similar adsorption capacity in wastewater with different ion strengths. The variation of adsorption capacity with the adsorption time was fitted using a pseudo-second-order kinetic equation. Meanwhile, it is found that the adsorption reaction occurs only on the monolayer of the UiO-66 surface so the adsorption process can be simulated using the Langmuir isotherm model. The thermodynamic analysis indicates that the adsorption of TC is an endothermic reaction. Electrostatic attraction, hydrogen-bond interaction, and π-π interaction might be the main reasons for the adsorption.The synthesized Ni-UiO-66 has well adsorption capacity and stable structure. Accordingly, it is expected to achieve a good prospect in industrial applications and wastewater treatment plants.