Mechanistic insights into δ-MnO2/biochar-activated persulfate-treated wastewater containing antibiotics and heavy metals: Nonradical pathway and pivotal role of Cu(⠡) at low temperature.

Herein, we present a high efficiency system based on biochar loaded with layered manganese dioxide to remove tetracycline and heavy metals from livestock wastewater. Under the optimal conditions, the degradation efficiencies of TC in the δ-MnO2/BC/PS system were 85.5% at 25 °C and 38.5% at 5 °C. Radical quenching experiments revealed that radical reactions in the δ-MnO2/BC/PS system were weak under 15 °C. Adsorption degradation experiments showed that the system maintained good adsorption performance at 5 °C. Galvanic cell experiments and cyclic voltammetry showed that the δ-MnO2/BC material had good electrochemical activity and high stability in response to temperature, indicating that TC was degraded by a nonradical pathway that was not limited by temperature, such as electron transfer. Copper ion was important coadsorbent and coactivator of the reaction system. Furthermore, FTIR, XPS, and X-ray diffraction (XRD) analyses showed that Cu(II) in the system was involved in changing the manganese valence state in the δ-MnO2/BC material and increasing the -OH content of BC. Comparison of the different products generated during metabolic testing revealed that the reaction pathway of the system at low temperature (5 °C) differed from that at normal temperature (25 °C). The δ-MnO2/BC material demonstrated good removal ability for antibiotics and heavy metals at normal and low temperatures in actual biogas slurry. The study provides insight for improving the efficiency of environmentally friendly treatments of aquaculture wastewater in cold regions, which is of great significance for resource utilization.

Multi-interface interaction mechanism of pulp reject-based flocculants for the removal of antibiotics and its combined pollutants.

The efficient removal of antibiotics and its combined pollutants is essential for aquatic environment and human health. In this study, a lignin-based organic flocculant named PRL-VAc-DMC was synthesized using pulp reject as the raw material, with vinyl acetate (VAc) and methacryloxyethyltrimethyl ammonium chloride (DMC) as the grafting monomers. A series of modern characterization methods were used to confirm the successful preparation of PRL-VAc-DMC and elucidate its polymerization mechanism. It was found that the Ph-OH group and its contiguous carbon atoms of lignin served as the primary active sites to react with grafting monomers. Flocculation experiments revealed that PRL-VAc-DMC could react with tetracycline (TC) through π-π* interaction, hydrophobic interaction, hydrogen bonding, and electrostatic attraction. With the coexistence of humic acid (HA) and Kaolin, the aromatic ring, hydroxyl, and amide group of TC could react with the benzene ring, hydroxyl group, and carboxyl group of HA, forming TC@HA@Kaolin complexes with Kaolin particles acting as the hydrophilic shell. The increase in particle size, electronegativity, and hydrophily of TC@HA@Kaolin complexes facilitated their interaction with PRL-VAc-DMC through strong interfacial interactions. Consequently, the presence of HA and Kaolin promoted the removal of TC. The synergistic removal mechanism of TC, HA, and Kaolin by PRL-VAc-DMC was systematically analyzed from the perspective of muti-interface interactions. This paper is of great significance for the comprehensive utilization of pulp reject and provides new insights into the flocculation mechanism at the molecular scale.

Seawater Chlorella sp. biofilm for mariculture effluent polishing under environmental combined antibiotics exposure and ecological risk evaluation based on parent antibiotics and transformation products.

Mariculture effluent polishing with microalgal biofilm could realize effective nutrients removal and resolve the microalgae-water separation issue via biofilm scraping or in-situ aquatic animal grazing. Ubiquitous existence of antibiotics in mariculture effluents may affect the remediation performances and arouse ecological risks. The influence of combined antibiotics exposure at environment-relevant concentrations towards attached microalgae suitable for mariculture effluent polishing is currently lack of research. Results from suspended cultures could offer limited guidance since biofilms are richer in extracellular polymeric substances that may protect the cells from antibiotics and alter their transformation pathways. This study, therefore, explored the effects of combined antibiotics exposure at environmental concentrations towards seawater Chlorella sp. biofilm in terms of microalgal growth characteristics, nutrients removal, anti-oxidative responses, and antibiotics removal and transformations. Sulfamethoxazole (SMX), tetracycline (TL), and clarithromycin (CLA) in single, binary, and triple combinations were investigated. SMX + TL displayed toxicity synergism while TL + CLA revealed toxicity antagonism. Phosphorus removal was comparable under all conditions, while nitrogen removal was significantly higher under SMX and TL + CLA exposure. Anti-oxidative responses suggested microalgal acclimation towards SMX, while toxicity antagonism between TL and CLA generated least cellular oxidative damage. Parent antibiotics removal was in the order of TL (74.5-85.2 %) > CLA (60.8-69.5 %) > SMX (13.5-44.1 %), with higher removal efficiencies observed under combined than single antibiotic exposure. Considering the impact of residual parent antibiotics, CLA involved cultures were identified of high ecological risks, while medium risks were indicated in other cultures. Transformation products (TPs) of SMX and CLA displayed negligible aquatic toxicity, the parent antibiotics themselves deserve advanced removal. Four out of eight TPs of TL could generate chronic toxicity, and the elimination of these TPs should be prioritized for TL involved cultures. This study expands the knowledge of combined antibiotics exposure upon microalgal biofilm based mariculture effluent polishing.

Tetracycline (TC) removal from wastewater with activated carbon (AC) obtained from waste grape marc: activated carbon characterization and adsorption mechanism.

In this study, activated carbons were obtained from grape marc for tetracycline removal from wastewater. Activated carbons were obtained by subjecting them to pyrolysis at 300, 500, and 700 °C, respectively, and the effect of pyrolysis temperature on activated carbons was investigated. The physicochemical and surface properties of the activated carbons were evaluated by SEM, FTIR, XRD, elemental analysis, N2 adsorption/desorption isothermal, thermal gravimetric (TG) and derivative thermogravimetric (DTG), and BET surface area analysis. When the BET surface areas were examined, it was found that 4.25 m2/g for activated carbon was produced at 300 °C, 44.23 m2/g for activated carbon obtained at 500 °C and 44.23 m2/g at 700 °C, which showed that the BET surface areas increased with increasing pyrolysis temperatures. The pore volumes of the synthesized activated carbons were 0.0037 cm3/g, 0.023 cm3/g, and 0.305 cm3/g for pyrolysis temperatures of 300, 500, and 700 °C, respectively, while the average pore size was found to be 8.02 nm, 9.45 nm, and 10.29 nm, respectively. A better adsorption capacity was observed due to the decrease in oxygen-rich functional groups with increasing pyrolysis temperature. It was observed that the activated carbon obtained from grape skins can easily treat hazardous wastewater containing tetracycline due to its high carbon content and surface functional groups. It was also shown that the activated carbon synthesized in this study has a higher pore volume despite its low surface area compared to the studies in the literature. Thanks to the high pore volume and surface active groups, a successful tetracycline removal was achieved.

A systematic review of antibiotics and antibiotic resistance genes (ARGs) in mariculture wastewater: Antibiotics removal by microalgal-bacterial symbiotic system (MBSS), ARGs characterization on the metagenomic.

Antibiotic residues in mariculture wastewater seriously affect the aquatic environment. Antibiotic Resistance Genes (ARGs) produced under antibiotic stress flow through the environment and eventually enter the human body, seriously affecting human health. Microalgal-bacterial symbiotic system (MBSS) can remove antibiotics from mariculture and reduce the flow of ARGs into the environment. This review encapsulates the present scenario of mariculture wastewater, the removal mechanism of MBSS for antibiotics, and the biomolecular information under metagenomic assay. When confronted with antibiotics, there was a notable augmentation in the extracellular polymeric substances (EPS) content within MBSS, along with a concurrent elevation in the proportion of protein (PN) constituents within the EPS, which limits the entry of antibiotics into the cellular interior. Quorum sensing stimulates the microorganisms to produce biological responses (DNA synthesis - for adhesion) through signaling. Oxidative stress promotes gene expression (coupling, conjugation) to enhance horizontal gene transfer (HGT) in MBSS. The microbial community under metagenomic detection is dominated by aerobic bacteria in the bacterial-microalgal system. Compared to aerobic bacteria, anaerobic bacteria had the significant advantage of decreasing the distribution of ARGs. Overall, MBSS exhibits remarkable efficacy in mitigating the challenges posed by antibiotics and resistant genes from mariculture wastewater.

Effects of Salts and Other Contaminants on Ciprofloxacin Removal Efficiency of Green Synthesized Copper Nanoparticles.

Ciprofloxacin (CIP), a broad-spectrum fluoroquinolone antibiotic, is commonly used in aquaculture to prevent and treat bacterial infections in aquatic animals. For this reason, aquatic environments contain CIP and its derivatives, which lead to the development of drug-resistant bacteria. In the present study, copper nanoparticles were prepared using Garcinia mangostana extract (GME-CuNPs) as a reducing agent and evaluated for their CIP removal efficiency (CRE). The results demonstrate that within 20 min, GME-CuNPs at 25 mM possess a CRE of 92.02 ± 0.09% from CIP-containing aqueous media with pH 6-7. The CRE is influenced by both monovalent and divalent salts. A high salt concentration significantly reduces the CRE. Contaminants in fish wastewater can reduce the CRE, but phenolics, flavonoids, tannins, and ammonia do not affect the CRE. Our results reveal that the CRE is controlled by electrostatic attraction between the negatively charged GME-CuNPs and the cationic species of CIP. The CRE is reduced by wastewater with a pH higher than 8.0, in which the CIP molecules have a negative charge, resulting in a repulsive force due to the negative charge of GME-CuNPs. In fish wastewater with a pH lower than 7.0, GME-CuNPs show the potential to achieve a CRE above 80%. Therefore, pH adjustment to a range of 6-7 in fish wastewater before treatment is deemed imperative. It is concluded that the newly developed GME-CuNPs possess excellent activity in CIP elimination from actual fish wastewater samples. Our findings suggest that GME-CuNPs can be a promising tool to effectively eliminate antibiotics from the environment.

Enhancing singlet oxygen production of dioxygen activation on the carbon-supported rare-earth oxide nanocluster and rare-earth single atom catalyst to remove antibiotics.

Singlet oxygen (1O2) is extensively employed in the fields of chemical, biomedical and environmental. However, it is still a challenge to produce high- concentration 1O2 by dioxygen activation. Herein, a system of carbon-supported rare-earth oxide nanocluster and single atom catalysts (named as RE2O3/RE-C, RE=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sc and Y) with similar morphology, structure, and physicochemical characteristic are constructed to activate dissolved oxygen (DO) to enhance 1O2 production. The catalytic activity trends and mechanisms are revealed experimentally and are also proven by theoretical analyses and calculations. The 1O2 generation activity trend is Gd2O3/Gd-C>Er2O3/Er-C>Sm2O3/Sm-C>pristine carbon (C). More than 95.0% of common antibiotics (ciprofloxacin, ofloxacin, norfloxacin and carbamazepine) can be removed in 60 min by Gd2O3/Gd-C. Density functional theory calculations indicate that Gd2O3 nanoclusters and Gd single atoms exhibit the moderate adsorption energy of ·O2- to enhance 1O2 production. This study offers a universal strategy to enhance 1O2 production in dioxygen activation for future application and reveals the natural essence of basic mechanisms of 1O2 production via rare-earth oxide nanoclusters and rare-earth single atoms.

Effect of different concentrations of gibberellins on attenuation of nutrient and antibiotics from aquaculture wastewater using microalgae-bacteria-fungi consortia system.

This study assessed the effect of gibberellins (GAs) concentrations on antibiotic and nutrient removal using diverse microalgal-bacterial-fungal consortia. Five systems (Chlorella vulgaris, T1; C. vulgaris + S395-2 + Clonostachys rosea, T2; C. vulgaris + S395-2 + Ganoderma lucidum, T3; C. vulgaris + S395-2 + Pleurotus pulmonarius, T4; and C. vulgaris + S395-2, T5) were established, and optimal conditions and effective symbiosis were applied to improve antibiotic and nutrient removal. Consortium growth was T2 > T3 > T5 > T4 > T1, while GA impact ranked 50 mg L-1 > 20 mg L-1 > 80 mg L-1 > 0 mg L-1. After 7 days at 50 mg L-1 GAs, total nitrogen (TN), NH4-N, NO3-N, and total phosphorous (TP) removal reached 85.97 %, 78.08 %, 86.59 %, and 94.39 %, respectively. Florfenicol, oxytetracycline hydrochloride, ofloxacin, and sulfamethoxazole removal efficiencies were 67.77 %, 98.29 %, 90.47 %, and 94.92 %, respectively. These findings highlight GAs' significant role in enhancing antibiotic and nutrient removal.

Simultaneous removal of calcium, cadmium and tetracycline from reverse osmosis wastewater by sycamore deciduous biochar, shell powder and polyurethane sponge combined with biofilm reactor.

The treatment of reverse osmosis concentrate generated from urban industrial sewage for resource recovery has been hot. In this research, a biofilm reactor was constructed by combining sycamore deciduous biochar, shell powder, and polyurethane sponge loaded with Zobellella denitrificans sp. LX16. For ammonia nitrogen (NH4+-N), calcium (Ca2+), chemical oxygen demand (COD), cadmium (Cd2+), and tetracycline (TC), the removal efficiencies were 98.69 %, 83.95 %, 97.26 %, 98.34 %, and 69.12 % at a hydraulic retention time (HRT) of 4 h, pH of 7.0, and influent salinity, Ca2+, and TC concentrations of 1.0, 180.0, and 3.0 mg/L, respectively. The biofilm reactor packing has a three-dimensional structure to ensure good loading of microorganisms while promoting electron transfer and metabolic activity of microorganisms and increasing the pollutant tolerance and removal efficiency. The reactor provides a practical reference for the sedimentation of reverse osmosis concentrate to remove Cd2+ and TC by microbial induced calcium precipitation (MICP).

Intrinsic mechanism for the removal of antibiotic pollution by a dual coagulation process from the perspective of the interaction between NOM and antibiotic.

Antibiotics bring potential risks to human health and ecosystem, and their coexistence with natural organic matters (NOMs) could have harmful impacts on the environment. Herein, a polyaluminium chloride (PAC)-polydimethyl diallyl ammonium chloride (PDMDAAC) dual coagulation process was designed to remove the co-pollutants of chlortetracycline (CTC) and humic acid (HA), representing antibiotics and NOMs, respectively. The main research strength was given to understand molecular interactions and their mechanisms associated with the coagulation and flocculation. We found that the co-existing HA and CTC increased the hydrophily and stability of contaminants, and generated HA@CTC complexes with large particles size. The interaction mechanism between CTC and HA was mainly hydrogen bonding, hydrophobic association action, n-π* electron donor-acceptor interaction, and π-π* conjugation. Lewis acid-base interaction was the main force between HA and CTC. The bonding energies of OH…N, OH…O, and hydrophobic association were -12.2 kcal/mol, -13.1 kcal/mol, and -11.4 kcal/mol, respectively, indicating that hydrogen bonding was stronger than hydrophobic association. The interactions between HA and CTC could improve their removal efficiency in the coagulation process. This is due to that the functional groups (COOH and OH) in the HA@CTC could be adsorbed by Al based hydrolysates. Polar interaction dominated the CTC and HA removal, and PAC was more efficient than PDMDAAC to remove HA@CTC complexes due to its higher complexing capacity. Thanks to the low concentration of residual contaminants and the formation of large and loose flocs, the interaction of HA and CTC could alleviate membrane fouling during ultrafiltration process. This study will provide new insight into the efficient removal of combined pollution and membrane fouling control.

Enhancement of anaerobic digestion of ciprofloxacin wastewater by nano zero-valent iron immobilized onto biochar.

The commonly used antibiotic ciprofloxacin (CIP) can significantly inhibit and interfere with the anaerobic digestion (AD) performance. This work was developed to explore the effectiveness and feasibility of nano iron-carbon composites to simultaneously enhance methane production and CIP removal during AD under CIP stress. The results demonstrated that when the nano-zero-valent iron (nZVI) content immobilized on biochar (BC) was 33% (nZVI/BC-33), the CIP degradation efficiency reached 87% and the methanogenesis reached 143 mL/g COD, both higher than Control. Reactive oxygen species analysis demonstrated that nZVI/BC-33 could effectively mitigate microorganisms subjected to the dual redox pressure from CIP and nZVI, and reduce a series of oxidative stress reactions. The microbial community depicted that nZVI/BC-33 enriched functional microorganisms related to CIP degradation and methane production and facilitated direct electron transfer processes. Nano iron-carbon composites can effectively alleviate the stress of CIP on AD and enhance methanogenesis.

Occurrence and fate of antibiotics in swine waste treatment: An industrial case.

This study mapped the fate of antibiotics in a swine farm with integrated waste treatment including anoxic stabilization, fixed-film anaerobic digestion, anoxic-oxic (A/O), and composting. Results show the prevalent and consistent occurrence of 12 antibiotics in swine waste. Mass balance of these antibiotics was calculated to track their flow and evaluate their removal by different treatment units. The integrated treatment train could effectively reduce antibiotic loading to the environment by 90% (measured as combined mass of all antibiotic residues). Within the treatment train, anoxic stabilization as the initial treatment step, accounted for the highest contribution (43%) to overall antibiotic elimination. Results also show that aerobic was more effective than anaerobic regarding antibiotic degradation. Composting accounted for an additional of 31% removal of antibiotics while anaerobic digestion contributed to 15%. After treatment, antibiotic residues in the treated effluent and composted materials were 2 and 8% of the initial antibiotic loading in raw swine waste, respectively. Ecological risk assessment showed negligible or low risk quotient associated with most individual antibiotics released into the aquatic environment or soil from swine farming. Nevertheless, antibiotic residues in treated water and composted materials together showed significant ecological risk to water and soil organisms. Thus, further work to improve treatment performance or develop new technologies is necessary to reduce the impact of antibiotics from swine farming.

Antibiotic removal by microalgae-bacteria consortium: Metabolic pathways and microbial responses.

The proliferation of antibiotic-resistance genes is a result of the rise in the discharge of residual antibiotics into waterbodies from a variety of sources. Antibiotic removal by microalgae-bacteria consortium has been shown to be effective, therefore, there is a need to understand the involved microbial processes. This review summarizes the microbiological removal mechanisms of antibiotics by the microalgae-bacteria consortium, such as biosorption, bioaccumulation, and biodegradation. Factors that influence antibiotic removal are discussed. Co-metabolism of nutrients and antibiotics in the microalgae-bacteria consortium and the metabolic pathways revealed by omics technologies are also highlighted. Furthermore, the responses of microalgae and bacteria to antibiotic stress are elaborated, including reactive oxidizing species (ROS) generation and its effects on photosynthesis machinery, antibiotic stress tolerance, microbial community shift, and the emergence of antibiotic resistance genes (ARGs). Finally, we offer a prospective solutions for the optimization and applications of microalgae-bacteria symbiotic systems for antibiotic removal.

Tetracycline Removal through the Synergy of Catalysis and Photocatalysis by Novel NaYF4:Yb,Tm@TiO2-Acetylacetone Hybrid Core-Shell Structures.

Novel hybrid core-shell structures, in which up-converting (UC) NaYF4:Yb,Tm core converts near-infrared (NIR) to visible (Vis) light via multiphoton up-conversion processes, while anatase TiO2-acetylacetonate (TiO2-Acac) shell ensures absorption of the Vis light through direct injection of excited electrons from the highest-occupied-molecular-orbital (HOMO) of Acac into the TiO2 conduction band (CB), were successfully synthesized by a two-step wet chemical route. Synthesized NaYF4:Yb,Tm@TiO2-Acac powders were characterized by X-ray powder diffraction, thermogravimetric analysis, scanning and transmission electron microscopy, diffuse-reflectance spectroscopy, Fourier transform infrared spectroscopy, and photoluminescence emission measurement. Tetracycline, as a model drug, was used to investigate the photocatalytic efficiencies of the core-shell structures under irradiation of reduced power Vis and NIR spectra. It was shown that the removal of tetracycline is accompanied by the formation of intermediates, which formed immediately after bringing the drug into contact with the novel hybrid core-shell structures. As a result, ~80% of tetracycline is removed from the solution after 6 h.

Developing a Slow-Release Permanganate Composite for Degrading Aquaculture Antibiotics.

Copious use of antibiotics in aquaculture farming systems has resulted in surface water contamination in some countries. Our objective was to develop a slow-release oxidant that could be used in situ to reduce antibiotic concentrations in discharges from aquaculture lagoons. We accomplished this by generating a slow-release permanganate (SR-MnO4-) that was composed of a biodegradable wax and a phosphate-based dispersing agent. Sulfadimethoxine (SDM) and its synergistic antibiotics were used as representative surrogates. Kinetic experiments verified that the antibiotic-MnO4- reactions were first-order with respect to MnO4- and initial antibiotic concentration (second-order rates: 0.056-0.128 s-1 M-1). A series of batch experiments showed that solution pH, water matrices, and humic acids impacted SDM degradation efficiency. Degradation plateaus were observed in the presence of humic acids (>20 mgL-1), which caused greater MnO2 production. A mixture of KMnO4/beeswax/paraffin (SRB) at a ratio of 11.5:4:1 (w/w) was better for biodegradability and the continual release of MnO4-, but MnO2 formation altered release patterns. Adding tetrapotassium pyrophosphate (TKPP) into the composite resulted in delaying MnO2 aggregation and increased SDM removal efficiency to 90% due to the increased oxidative sites on the MnO2 particle surface. The MnO4- release data fit the Siepmann-Peppas model over the long term (t < 48 d) while a Higuchi model provided a better fit for shorter timeframes (t < 8 d). Our flow-through discharge tank system using SRB with TKPP continually reduced the SDM concentration in both DI water and lagoon wastewater. These results support SRB with TKPP as an effective composite for treating antibiotic residues in aquaculture discharge water.

New chitosan-biochar composite derived from agricultural waste for removing sulfamethoxazole antibiotics in water.

This study aims to develop a new chitosan-biochar composite derived from agricultural waste for removing sulfamethoxazole (SMX) antibiotics in water. Biochar was prepared from orange peel (OB) and spent coffee grounds (SCB). To fabricate chitosan-biochar composites, chitosan and biochar were crosslinked with glutaraldehyde. Results showed that pH, adsorbent dosage, time, temperature, and initial concentrations have a significant impact on the SMX adsorption. The adsorption data was better described by Langmuir (with good regression) than Freundlich model. The highest adsorption capacity (Qmax) of SMX on OB, SCB, CTS-OB, and CTS-SCB were 3.49, 7.65, 7.24, and 14.73 mg/g, respectively. The Freundlich constant (KF) values for adsorption capacity were 1.66, 1.91, 2.57, and 5.57 (mg1-nLn/g), respectively, for OB, SCB, CTS-OB, and CTS-SCB. Ion exchange, π bonding, hydrogen bonding and pore filling, were proposed as dominant mechanisms of SMX removal process.

An Eco-Friendly Adsorbent Based on Bacterial Cellulose and Vermiculite Composite for Efficient Removal of Methylene Blue and Sulfanilamide.

In this work, a novel composite of bacterial cellulose (BC) and expanded vermiculite (EVMT) composite was used to adsorb dyes and antibiotics. The pure BC and BC/EVMT composite were characterized using SEM, FTIR, XRD, XPS and TGA. The BC/EVMT composite exhibited a microporous structure, providing abundant adsorption sites for target pollutants. The adsorption performance of the BC/EVMT composite was investigated for the removal of methylene blue (MB) and sulfanilamide (SA) from an aqueous solution. The adsorption capacity of BC/ENVMT for MB increased with increasing pH, while the adsorption capacity for SA decreased with increasing pH. The equilibrium data were analyzed using the Langmuir and Freundlich isotherms. As a result, the adsorption of MB and SA by the BC/EVMT composite was found to follow the Langmuir isotherm well, indicating a monolayer adsorption process on a homogeneous surface. The maximum adsorption capacity of the BC/EVMT composite was found to be 92.16 mg/g for MB and 71.53 mg/g for SA, respectively. The adsorption kinetics of both MB and SA on the BC/EVMT composite showed significant characteristics of a pseudo-second-order model. Considering the low cost and high efficiency of BC/EVMT, it is expected to be a promising adsorbent for the removal of dyes and antibiotics from wastewater. Thus, it can serve as a valuable tool in sewage treatment to improve water quality and reduce environmental pollution.

Combined toxicity of erythromycin and roxithromycin and their removal by Chlorella pyrenoidosa.

The ecological effects of antibiotics in surface water have attracted increasing research attention. In this study, we investigated the combined ecotoxicity of erythromycin (ERY) and roxithromycin (ROX) on the microalgae, Chlorella pyrenoidosa, and the removal of ERY and ROX during the exposure. The calculated 96-h median effect concentration (EC50) values of ERY, ROX, and their mixture (2:1 w/w) were 7.37, 3.54, and 7.91 mg∙L-1, respectively. However, the predicted EC50 values of ERY+ROX mixture were 5.42 and 1.51 mg∙L-1, based on the concentration addition and independent action models, respectively. This demonstrated the combined toxicity of ERY+ ROX mixture showed an antagonistic effect on Chlorella pyrenoidosa. During the 14-d culture, low-concentration (EC10) treatments with ERY, ROX, and their mixture caused the growth inhibition rate to decrease during the first 12 d and increase slightly at 14 d. In contrast, high-concentration (EC50) treatments significantly inhibited microalgae growth (p < 0.05). Changes in the total chlorophyll contents, SOD and CAT activities, and MDA contents of microalgae suggested that individual treatments with ERY and ROX induced higher oxidative stress than combined treatments. After the 14-d culture time, residual Ery in low and high concentration Ery treatments were 17.75% and 74.43%, and the residual Rox were 76.54% and 87.99%, but the residuals were 8.03% and 73.53% in ERY+ ROX combined treatment. These indicated that antibiotic removal efficiency was higher in combined treatments than that in individual treatments, especially at low concentrations (EC10). Correlation analysis suggested that there was a significant negative correlation between the antibiotic removal efficiency of C. pyrenoidosa and their SOD activity and MDA content, and the enhanced antibiotic removal ability of microalgae benefited from increased cell growth and chlorophyll content. Findings in this study contribute to predicting ecological risk of coexisting antibiotics in aquatic environment, and to improving biological treatment technology of antibiotics in wastewater.

3D porous carbon-embedded nZVI@Fe2O3 nanoarchitectures enable prominent performance and recyclability in antibiotic removal.

Overcoming the instability and poor recyclability during the practical applications of contaminant scavengers is a challenging topic. Herein, a three-dimensional (3D) interconnected carbon aerogel (nZVI@Fe2O3/PC) embedding a core-shell nanostructure of nZVI@Fe2O3 was elaborately designed and fabricated via an in-situ self-assembly process. The porous carbon with 3D network architecture exhibits strong adsorption towards various antibiotic contaminants in water, where the stably embedded nZVI@Fe2O3 nanoparticles not only serve as magnetic seeds for recycling, but also avoid the shedding and oxidation of nZVI in the adsorption process. As a result, nZVI@Fe2O3/PC efficiently captures sulfamethoxazole (SMX), sulfamethazine (SMZ), ciprofloxacin (CIP), tetracycline (TC) and other antibiotics in water. In particular, an excellent adsorptive removal capacity of 329 mg g-1 and a rapid capture kinetics (99% of removal efficiency in 10 min) under a wide pH adaptability (2-8) are achieved using nZVI@Fe2O3/PC as an SMX scavenger. nZVI@Fe2O3/PC displays exceptional long-term stability given that it shows excellent magnetic property after it is stored in water solution for 60 d, making it an ideal stable scavenger for contaminants in an etching-resistant and efficient manner. This work would also provide a general strategy to develop other stable iron-based functional architectures for efficient catalytic degradation, energy conversion and biomedicine.

Facile synthesis of nanostrip-structured pseudo-boehmite "nest" for nano-TiO2/γ-Al2O3construction to remove tetracycline hydrochloride in water.

A particular bird's nest-like pseudo-boehmite (PB) composed of cohesive nanostrips was prepared by a novel and facile approach based on the reaction of Al-Ga-In-Sn alloy and water, together with ammonium carbonate. The PB possesses a large specific surface area (465.2 m2g-1), pore volume (1.0 cm3g-1), and pore diameter (8.7 nm). Subsequently, it was utilized as a precursor to form the TiO2/γ-Al2O3nanocomposite for tetracycline hydrochloride removal. The removal efficiency can reach above 90% at TiO2:PB = 1:1.5 under the Sunlight irradiation simulated by a LED lamp. Our results indicate that the nest-like PB is a promising carrier precursor for efficient nanocomposite catalysts.