Maternal or Paternal Antibiotics? Intergenerational Transmission and Reproductive Toxicity in Zebrafish.

Despite the known direct toxicity of various antibiotics to aquatic organisms, the potential chronic impact through intergenerational transmission on reproduction remains elusive. Here, we exposed zebrafish to a mixture of 15 commonly consumed antibiotics at environmentally relevant concentrations (1 and 100 µg L-1) with a cross-mating design. A high accumulation of antibiotics was detected in the ovary (up to 904.58 ng g-1) and testis (up to 1704.49 ng g-1) of F0 fish. The transmission of antibiotics from the F0 generation to the subsequent generation (F1 offspring) was confirmed with a transmission rate (ki) ranging from 0.11 to 2.32. The maternal transfer of antibiotics was significantly higher, relative to paternal transfer, due to a greater role of transmission through ovarian enrichment and oviposition compared to testis enrichment. There were similar impairments in reproductive and developmental indexes on F1 eggs found following both female and male parental exposure. Almost all antibiotics were eliminated in F2 eggs in comparison to F1 eggs. However, there were still reproductive and developmental toxic responses observed in F2 fish, suggesting that antibiotic concentration levels were not the only criterion for evaluating the toxic effects for each generation. These findings unveil the intergenerational transmission mechanism of antibiotics in fish models and underscore their potential and lasting impact in aquatic environments.

Thiamethoxam adsorption by ZnCl2 modified cow manure biochar: Mechanism and quantitative prediction.

The overuse of thiamethoxam (THM) has threatened the survival of living organisms and it is necessary to find an environmentally friendly material to remove THM frequently detected in water. Biochar prepared from cow manure modified with ZnCl2 (Zn-CBC) was used to remove THM. Compared to the unmodified cow manure biochar (CBC), the removal ratio of THM by Zn-CBC was enhanced 35 times. In the mechanistic analysis, SEM and BET showed that Zn-CBC had a good pore structure and its specific surface area (166.502 m2 g-1) increased to 17 times that of CBC, indicating that Zn-CBC had good pore adsorption properties. The adsorption kinetic and isotherm implied that the main mechanism was chemisorption including π-π interaction and H-bonding. Furthermore, the stable graphitized structure of Zn-CBC allowed for efficient adsorption and reusability. In addition, this study constructed an intelligent prediction model using batch experiment data, and the high R2 (0.978) and low RMSE (0.057) implied that the model could accurately and quantitatively predict the adsorption efficiency. This paper provides a novel perspective to simultaneously remove the neonicotinoid insecticides and realize the resource utilization of cow manure.

Combined coagulation and membrane treatment for anaerobically digested manure centrate: Contaminant residuals and membrane fouling.

To realize water and resource recovery from anaerobically digested manure centrate, the effect of combined coagulation and membrane treatment on contaminant residuals and membrane fouling was investigated. Two combined treatments were used to explore the properties of the retention of nutrients and the removal of risk pollutants. Behaviors and reversibility of membrane fouling after combined treatment were also examined. The result showed that the combined treatment significantly improved the water recovery rate by more than 60% and achieved better nutrient enrichment. Meanwhile, the combined treatment had certain removal effects on heavy metals and antibiotics, which promoted the safety of farmland utilization of anaerobically digested manure centrate. Moreover, the combined treatment reduced the membrane fouling by removing most suspended solids in the digested centrate. Combined coagulation and membrane treatment show great potential for practical applications in the treatment of anaerobically digested manure centrate due to the easy operation and excellent effect. This work provides a technical reference for the harmless and resource recovery of anaerobically digested manure centrate.

Synthesis and Photocatalytic Activity of Pt-Deposited TiO2 Nanotubes (TNT) for Rhodamine B Degradation.

Dye wastewater has attracted more and more attention because of its high environmental risk. In this study, a novel TiO2 nanotube (TNT) catalyst was prepared and its morphology and structure were characterized. The synthetic catalyst was used to degrade Rhodamine B (RhB) under UV light and evaluated for the application performance. According to the characterization results and degradation properties, the optimum synthetic conditions were selected as 400°C calcination temperature and 10 wt% Pt deposition. As a result, the degradation efficacies were sequenced as TNT-400-Pt > TNT-500-Pt > TNT-400 > TNT-300-Pt. In addition, the effect of pH and initial concentration of RhB were explored, and their values were both increased with the decreased degradation efficacy. While the moderate volume of 11 mm of H2O2 addition owned better performance than that of 0, 6, and 15 mm. Scavengers such as tertbutanol (t-BuOH), disodium ethylenediaminetetraacetate (EDTA-Na2), and nitroblue tetrazolium (NBT) were added during the catalytic process and it proved that superoxide radical anions ( O 2 - • ) , photogenerated hole (h+) and hydroxyl radical (OH•) were the main active species contributing for RhB removal. For the application, TNT-Pt could deal with almost 100% RhB, Orange G (OG), Methylene blue (MB), and Congo red (CR) within 70 min and still kept more than 50% RhB removal in the fifth recycling use. Therefore, TNT-Pt synthesized in this study is potential to be applied to the dye wastewater treatment.

Electro-activation of peroxymonosulfate by a graphene oxide/iron oxide nanoparticle-doped Ti4O7 ceramic membrane: mechanism of singlet oxygen generation in the removal of 1,4-dioxane.

Electro-activation of peroxymonosulfate (PMS) has been widely investigated for the degradation of organic pollutants. Herein, we employ graphene oxide (GO)/Fe3O4 nanoparticles (NPs) doped into a Ti4O7 reactive electrochemical membrane through strong chemical bonding as the cathode to activate PMS for the degradation of 1,4-dioxane (1,4-D). The strong chemical interaction between GO, Fe3O4-NPs, and Ti4O7 via Fe-O---GO---O-Ti bonds enhances the electron-transfer efficiency and provides catalytically active sites that boost the electro-activation of PMS. As a result, the 1,4-D oxidation rate of the GO/Fe3O4-NPs@Ti4O7 REM cathode is ~3 times higher (7.21 × 10-3 min-1) than those of other Ti4O7 ceramic membranes, and 1O2 plays a key role (59.9%) in the degradation of 1,4-D. The 1O2 generation mechanism in the electro-activation process of PMS was systematically investigated, and we claimed that 1O2 is mainly generated from the precursors H2O2 and O2•-/HO2• rather than by O2 or •OH, as has been reported in previous studies. A flow-through mode test in the PMS electro-activation system is firstly reported, and the 1,4-D decay efficiency is 7.1 times higher than that obtained by a flow-by mode, showing that an improved PMS mass transfer efficiency enhances the conversion to reactive oxygen species.

Sulfur-modified chitosan derived N,S-co-doped carbon as a bifunctional material for adsorption and catalytic degradation sulfamethoxazole by persulfate.

N,S-co-doped carbons were synthesized through the calcination of sulfur-modified chitosan for the first time, and utilized as persulfate activators for sulfamethoxazole (SMX) remediation in water. The chitosan and sulfonyl chloride underwent one-step sulfonylation reaction to generate S-modified chitosan. The catalyst NSC-3 showed both excellent adsorption and catalytic oxidation efficiency, corresponding 98.62% removal and 81.34% mineralization rate within 90 min. The rate constant (kobs) was up to 0.0578 min-1, with 75.60-folders higher than that of sulfur-free catalyst NC (7.6580 ×10-4 min-1). The synergy of N and S contributed to the improvement of removal efficiency. The adsorption and oxidation performance were highly depended on the S/N atomic ratio. At the S/N ratio of 0.18, the maximum adsorption and oxidation capability were obtained. The NSC-3/PS system exhibited outstanding adaptability at the wide pH range from 3.07 to 9.28, while the inhibitory effect occurred at strong basic conditions (pH = 11.01). The thiophene sulfur and structural defects were identified as the catalytic sites in activating PS. Both radical and non-radical pathways were responsible for degradation process, where 1O2 played a major role, SO4·-exerted a minor contribution, and O2·- acts as the precursor for the production of 1O2. Another source of 1O2 was assigned to the activation of PS by structure defects. This work indicates that N,S-co-doped carbon at an optimal S/N atomic ratio effectively catalyzes persulfate, and provides an innovative method to construct bifunctional carbon materials of adsorption and oxidization.

Insight into degradation mechanism of sulfamethoxazole by metal-organic framework derived novel magnetic Fe@C composite activated persulfate.

Novel Fe@C composites derived from metal-organic framework (MOF) were synthesized. Being subject to pyrolysis under different temperatures endows these Fe@Cs diverse physical-chemical properties, including morphology, crystal structure, defect level, magnetism, and most importantly, iron phase composition. Fe@C-800 consists mainly of Fe3C and α-Fe, thus possesses strong ferromagnetic properties, which imparts the ability to be separated and recycled. Its catalytic activity towards the activation of persulfate (PS) and the decomposition of sulfamethoxazole (SMX) was found to be the best among all the Fe@Cs, and this activity can be regenerated by simple heat treatment. Given the mixed form of iron and N-doped carbon, α-Fe/Fe3C species provide electrons for PS to decompose and generate sulfate radical (SO4·-), hydroxyl radical (·OH), and superoxide radical (O2·-), initiating the radical pathway for partial SMX degradation. The positively charged C atoms on PS bonded Fe@C, as well as the conversion of O2·- give rise to the generation of singlet oxygen (1O2), which was responsible for the non-radical pathway for SMX degradation. As a consequence, SMX was degraded to intermediates through five degradation pathways, and finally mineralized to inorganic molecules. The results indicate that Fe@C-800 has great potential to serve as a promising activator for persulfate-mediated environmental remediation.

Water stable SiO2-coated Fe-MOF-74 for aqueous dimethyl phthalate degradation in PS activated medium.

The poor water stability of metal-organic frameworks (MOFs) significantly hindered their catalytic application in advanced oxidation system. A protective outer layer was an effective strategy to solve this problem. However, the commonly used coating techniques are too complicated or too difficult to accurately control, thus, the applicability was relatively low. In this study, a water stable MOF core-SiO2 shell nanomaterial (Fe-MOF-74@SiO2) was synthesized by a facile hydrothermal method, and applied to activate persulfate (PS) for dimethyl phthalate (DMP) degradation. The catalyst water stability and DMP degradation in the system were investigated, suggesting that the SiO2-coated catalyst was more stable and exhibited higher DMP degradation efficiency over the pure MOF. It was found that pH had negligible effects on Fe-MOF-74@SiO2 + PS system, while, higher temperature facilitated the degradation of DMP. The activation mechanism was studied by quenching experiments combined with electron paramagnetic resonance, indicating that SO4⋅- played a major role in the activation of PS with Fe-MOF-74@SiO2 for DMP removal, while ⋅OH also involved in the catalytic process. Finally, possible DMP degradation pathways were proposed. These findings indicated that the core-shell structured Fe-MOF-74@SiO2 showed promise for DMP degradation by PS advanced oxidation system.

Targeted degradation of dimethyl phthalate by activating persulfate using molecularly imprinted Fe-MOF-74.

Adsorptive removal of dimethyl phthalate (DMP) in water combined with advanced oxidation processes (AOPs) has attracted interest. In this work, the adsorptive and catalytic properties of an Fe-based metal-organic framework (Fe-MOF-74) have been improved by molecular imprinting technique. The adsorption behaviors have been evaluated by the Freundlich and pseudo-second-order model. The results have shown that selective adsorption ability of the material for DMP was highly enhanced and chemisorption was dominating. A 1.5-fold increase in catalytic rate after being modified by molecular imprinting indicated that the selective adsorption is crucial. In the synergy of adsorption and catalysis, DMP was first specifically adsorbed on the surface of the material by hydrogen bonds and electrostatic interactions. Then, hydroxyl radicals and sulfate radicals, which were both generated via activation of persulfate (PS), catalytically oxidized DMP. The degradation rate can rapidly reach around 90% in 30 min and three possible degradation pathways were proposed. The molecular imprinting modified catalyst can be used for DMP effective degradation in water.

The role of carbonate in sulfamethoxazole degradation by peroxymonosulfate without catalyst and the generation of carbonate racial.

Peroxymonosulfate (PMS) can be activated by various catalysts to degrade organic contaminants in wastewater treatment processes. In this research, the co-activation of PMS by sulfamethoxazole (SMX) and carbonate is investigated. The results show that SMX can be degraded in situ, and the main reactive oxygen species are singlet oxygen and carbonate radicals. Only singlet oxygen is detected when SMX is degraded by PMS without carbonate. However, both carbonate radicals and hydroxyl radicals are measured in the presence of carbonate. Among which, hydroxyl radicals are identified by electron paramagnetic resonance spectroscopy method, and carbonate radicals are confirmed by radical quenching experiments, as well as the variation of SMX degradation kinetic and the appreance of carbonyldioxy derivatives by-products in the presence of carbonate anions. Based on this phenomenon, it is proposed that carbonate can enhance the decomposition of PMS and the generation of secondary free radicals (carbonate radicals). Thus carbonate radicals can enhance the oxidizability for sulfonamide antibiotics in the PMS-based advanced oxidation systems. These results suggest that the addition of carbonate is an important enhancement method for the treatment of sulfonamide antibiotics in water.

ZSM-5-(C@Fe) activated peroxymonosulfate for effectively degrading ciprofloxacin: In-depth analysis of degradation mode and degradation path.

In this work, ZSM-5-(C@Fe), as a peroxymonosulfate (PMS) heterogeneous activator, was synthesized, characterized, and evaluated for activating PMS to degrade ciprofloxacin (CIP) in wastewater. Zeolite Socony Mobil-5 (ZSM-5) was utilized to enhance structural stability and provided a scaffold to graft Fe doping C nanocomposites activator. Pyrolytic metal-organic frameworks (MOFs) can use crystal structure to construct stable carbon-encapsulated Fe nanocomposites. The formation of C-O-Si, C-O-Al and C-Fe was the key to the stability of catalysts. Fe doping in ZSM-5-(C@Fe) formed non-radical degradation pathway was the key to improve the degradation efficiency. The experimental data indicated ZSM-5-(C@Fe) could completely remove 20 mg L-1 CIP within 15 min and achieve good results in the experiments of treating actual wastewater, which could reduce 40% COD of the paper mill aerobic pond effluent. The Fukui function calculation and UHPL C-H RMS/MS analysis elucidated that the 1O2-dominated electrophilic reaction and the ZSM-5-(C@Fe) complex PMS-dominated nucleophilic reaction were the main pathways for CIP degradation and the radical degradation pathway (·OH and SO4-˙) plays auxiliary role. In addition, two new degradation pathways of the N29 and C27 in quinolone ring and the N22 in piperazine ring were discovered. This finding had important implications for the removal of N from organic pollutants.

Ferrous metal-organic frameworks with strong electron-donating properties for persulfate activation to effectively degrade aqueous sulfamethoxazole.

Three novel persulfate activators, Fe(II)-based metal-organic frameworks (MOFs) were synthesized for the degradation of sulfamethoxazole (SMX). The degradation experiment results showed that all the Fe(II)MOFs could effectively activate persulfate and degrade more than 97% SMX within 180 min, with higher than 77% persulfate decomposition efficiencies. It was found by Mössbauer spectra that the variation of organic ligands for synthesis have an influence on the content of Fe(II) of these MOFs, thus resulted in the order of activation capacities: Fe(Nic) > Fe(PyBDC) > Fe(PIP). It was demonstrated that the activation of persulfate was mainly ascribed to the heterogeneous process that accomplished by surface-bounded Fe(II) acted as the main active site to provided electrons for persulfate or dissolved oxygen. EPR and molecular probe studies confirmed the coexistence of SO4·-, ·OH, and O2·-, and differentiated their contributions in SMX degradation. Possible degradation pathways of SMX were proposed based on the detection results of intermediates by UPLC-MS/MS. This work provides a new prospect into the synthesis of high-performance MOFs with strong electron-donating properties as efficient persulfate activators, which may encourage the employ of MOFs in the wastewater treatment process.

Synthesis of iron-based metal-organic framework MIL-53 as an efficient catalyst to activate persulfate for the degradation of Orange G in aqueous solution.

A series of MIL-53(Fe) materials were synthesized using a solvothermal method under different temperature and time conditions and were used as catalysts to activate persulfate and degrade Orange G (OG). Influences of the above conditions on the crystal structure and catalytic behavior were investigated. Degradation of OG under different conditions was evaluated, and the possible activation mechanism was speculated. The results indicate that high synthesis temperature (larger than 170 °C) leads to poor crystallinity and low catalytic activity, while MIL-53(Fe) cannot fully develop at low temperature (100 or 120 °C). The extension of synthesis time from 5 h to 3 d can increase the crystallinity of the samples, but weakened the catalytic activity, which was caused by the reduction of BET surface area and the amount of Fe (II)-coordinative unsaturated sites. Among all the samples, MIL-53(Fe)-A possesses the best crystal structure and catalytic activity. In optimal conditions, OG can be totally decolorized after degradation for 90 min, and a removal rate of 74% for COD was attained after 120 min. The initial solution pH had great influence on OG degradation, with the greatest removal in acidic pH environment. ESR spectra showed that sulfate radical (SO4- ·), hydroxyl radical (OH·), persulfate radical (S2O8- ·), and superoxide radical (O2·) exist in this system under acidic conditions. Furthermore, with the increase of pH, the relative amount of O2· increases while that of OH· and SO4- · decreases, resulting in a reduced oxidizing capacity of the system.

Activation performance and mechanism of a novel heterogeneous persulfate catalyst: Metal Organic Framework MIL-53(Fe) with FeII/FeIII mixed-valence coordinative unsaturated iron center.

In this work, a novel effective heterogeneous catalyst metal-organic framework MIL-53(Fe) has been synthesized for the purpose of activating persulfate (PS). Catalytic performance of MIL-53(Fe) activated under different vacuum conditions was investigated; stability and reusability of the catalyst were evaluated, and the activation mechanism was also investigated. The results indicated that vacuum activation could cause variation of the FeII/FeIII relative amount ratio of the catalyst, and thus would change the catalytic activities of MIL-53(Fe), because FeII or FeIII CUS (coordinative unsaturated metal site) are alternative active sites. It was found that MIL-53(Fe)-2 exhibits good performance for PS activation and could be used for multiple cycles. A removal rate of 98% for Orange G was obtained within 120min (95.7% mineralization efficiency), and 94.3% was attained in the fifth cycle. The mechanism of the activation of PS by MIL-53(Fe) was also suggested, which involves a predominant heterogeneous reaction and an auxiliary homogeneous reaction. The findings of this study provide new insight into the application of the reactive metal-organic frameworks in activating persulfate for the degradation of environmental contaminants.

Fe/S doped granular activated carbon as a highly active heterogeneous persulfate catalyst toward the degradation of Orange G and diethyl phthalate.

Fe/S doped granular activated carbon (Fe/SGAC) was synthesized with ferric nitrate, Na2S2O3 and (NH4)2S2O8 via an impregnation-precipitation, reduction-oxidation combining with aqueous-phase synthesis method treatment. Surface density of functional groups, surface area changes as well as the chemical state inside Fe/SGAC catalyst were studied by Boehm titration, N2 adsorption and X-ray photoelectron spectroscopy (XPS). The reactivity of the catalysts was tested by degrading Orange G (OG) and diethyl phthalate (DEP). The Fe/SGAC catalysts could significantly enhance the removal rate of OG as compared to persulfate alone and PS/GAC. And the catalytic capacity was also enhanced by S doping. But the degradation of DEP under the similar condition was inhibited by adsorption process because of the different hydrophobicities of OG and DEP molecule. Fe2O3/FeOOH (Fe(3+)) (represents ferrihydrite) together with FeO/Fe3O4 (Fe(2+)) and Fe2O3-satellite, which provide the new active site for persulfate catalyst was found to be the major components of iron element in Fe/SGAC catalyst; the existence of FeS2(S(-)) for sulfur element verified the assumption that the doped S element promoted the electron transfer between the persulfate species and iron oxide at the interface. COD removal experiment further confirmed that mostly contaminant removal was owed to the Fe/SGAC catalytic persulfate oxidation process.