Real-time and in situ monitoring of organosilicon-induced thiram penetration into cabbage leaves by surface-enhanced Raman scattering mapping.

BACKGROUND: Understanding pesticide penetration behavior is important for effective application of pesticides. However, there is a lack of an effective method to monitor pesticide penetration behavior and its changing process. In the present study, a novel surface-enhanced Raman scattering (SERS) mapping method was used for real-time and in situ tracking of the penetration behaviors of thiram and thiram-organosilicon mixture on cabbage leaves. RESULTS: The results suggest that thiram has very weak ability to penetrate into cabbage leaves. However, when the thiram-organosilicon mixture was placed on leaf surfaces, a clear thiram signal was detected inside the leaf after 2 h of exposure, a strong signal was observed after 12 h, and the penetration depth of thiram was approximately 200 µm after 48 h. CONCLUSION: SERS mapping was demonstrated to be a reliable method for in situ monitoring of organosilicon-induced thiram penetration into cabbage leaf over time. The present study provides a new reference for rationally selecting adjuvants, effectively applying pesticides, and reducing pesticides residue in food. © 2022 Society of Chemical Industry.

Distinguishing effects of ultraviolet exposure and chlorination on the horizontal transfer of antibiotic resistance genes in municipal wastewater.

Growing attention has been paid to the dissemination of antibiotic resistance genes (ARGs) in wastewater microbial communities; however, the disinfection processes, as microbial control technologies, have not been evaluated for their impacts on ARGs transfer. In this study, the effects of ultraviolet (UV) disinfection and chlorination on the frequency of ARGs transfer have been explored based on the conjugative transfer model between Gram-negative strains of E. coli. The results indicated that UV disinfection and chlorination exhibit distinct influences on the conjugative transfer. Low UV doses (up to 8 mJ/cm2) had little influence on the frequency of conjugative transfer, and UV exposure only decreased the bacterial number but did not change the cell permeability. By comparison, low chlorine doses (up to 40 mg Cl min/L) significantly promoted the frequency of conjugative transfer by 2-5-fold. The generated chloramine stimulated the bacteria and improved the cell permeability. More pilus were induced on the surface of conjugative cells, which acted as pathways for ARGs transfer. The frequency of ARG transfers was greatly suppressed by high doses of UV (>10 mJ/cm2) or chlorine (>80 mg Cl min/L).

Asymptotic analysis of SPTA-based algorithms for no-wait flow shop scheduling problem with release dates.

We address the scheduling problem for a no-wait flow shop to optimize total completion time with release dates. With the tool of asymptotic analysis, we prove that the objective values of two SPTA-based algorithms converge to the optimal value for sufficiently large-sized problems. To further enhance the performance of the SPTA-based algorithms, an improvement scheme based on local search is provided for moderate scale problems. New lower bound is presented for evaluating the asymptotic optimality of the algorithms. Numerical simulations demonstrate the effectiveness of the proposed algorithms.

Characterization of imidacloprid-induced hepatotoxicity and its mechanisms based on a metabolomic approach in Xenopus laevis.

The toxic effects of imidacloprid are attracting increased concern because of its widespread use in agriculture and its persistence in the aquatic environment. Imidacloprid bioaccumulates and triggers various morphological and behavioral responses in amphibians, but the toxic effects and mechanism of imidacloprid in amphibians remain uncertain. In this study, the acute toxicity and chronic effects of imidacloprid on Xenopus laevis were studied. Acute toxicity for 96 h revealed that imidacloprid had an LC50 value of 74.18 mg/L. After exposure for 28 d under 1/10 and 1/100 LC50, liver samples from X. laevis were employed for biochemical analyses, pathological studies, and nontargeted metabolomics to systematically assess the toxic effects and mechanisms of imidacloprid. The results showed that oxidative stress and hepatic tissue morphology changes were observed in treated X. laevis liver. Twelve metabolites involved in metabolic pathway were altered between the control and high exposure groups and twenty-one metabolites were altered between the control and low exposure group. Eight metabolic pathways exposed to high levels and nine metabolic pathways exposed to low level of imidacloprid were disturbed. These pathways were primarily related to amino acid metabolism, lipid metabolism, and nucleotide metabolism. Our research provides essential information to evaluate the potential toxicity of imidacloprid to nontarget aquatic organisms.

Fabrication and optimization of paper chips from calcinated Fe-MOFs for rapid and in situ visual detection of tetracyclines in water environments.

Antibiotics such as tetracyclines (TCs) have become a major threat to ecosystem safety and human health, as their abuse has caused the occurrence and proliferation of antibiotic-resistant bacteria and genes. Currently, there is still a lack of convenient in situ methods for the detection and monitoring of TC pollution in actual water systems. This research reports a paper chip based on the complexation of iron-based metal organic frameworks (Fe-MOFs) and TCs for rapid and in situ visual detection of representative oxytetracycline (OTC) pollution in water environments. The optimized complexation sample NH2-MIL-101(Fe)- 350 obtained by calcination at 350 °C exhibited the highest catalytic activity and was then used for paper chip fabrication by printing and surface modification. Notably, the paper chip demonstrated a detection limit as low as 17.11 nmol L-1 and good practicability in reclaimed water, aquaculture wastewater, and surface water systems, with OTC recovery rates of 90.6-111.4%. More importantly, the presence of dissolved oxygen (9.13-12.7 mg L-1), chemical oxygen demand (0.52-12.1 mg L-1), humic acid (< 10 mg L-1), Ca2+, Cl-, and HPO42- (< 0.5 mol L-1) had negligible interference on the detection of TCs by the paper chip. Therefore, this work has developed a promising method for rapid and in situ visual monitoring of TC pollution in actual water environments.

Electrochemically Assisted Construction of a La2NiO4+δ@Pt Core-Shell Structure for Enhancing the Performance and Durability of La2NiO4+δ Cathodes.

Ruddlesden-Popper oxide La2NiO4+δ (LNO) has a high ionic conductivity and good thermal match with the electrolyte of solid oxide fuel cells (SOFCs); however, LNO suffers from performance decay owing to the La surface segregation under the operation conditions of SOFCs. Herein, we report an in situ electrochemical decoration strategy to improve the electrocatalytic activity and durability of LNO cathodes. We show that the electrochemical polarization leads to in situ construction of the LNO@Pt core-shell structure, significantly suppressing the detrimental effect of La surface segregation on the LNO cathode. The initial peak power density of a single cell with the LNO cathode is 0.71 W cm-2 at 750 °C, increasing to 1.39 W cm-2 by the in situ construction of the LNO@Pt core-shell structure after polarization at 0.5 A cm-2 for 20 h. The LNO@Pt core-shell structure is also highly durable without noticeable performance degradation over the duration of the test for 180 h. The findings shed light on the design and fabrication of highly active and durable LNO-based cathodes for SOFCs.

Insights of microbial community evolution under benzisothiazolinone exposure in different soil environments.

Benzisothiazolinones (1, 2-benzisothiazoline-3-one; BIT) is widely used to control bacterial and fungal diseases of various crops, and their residues in soil may play an important role in the interaction between soil microorganisms. We studied microbial remediation in five representative soils under different soil conditions (unsterilized, sterilized and flooded) using 16S rRNA gene sequencing to investigate the effect of microorganisms on the degradation of BIT residues in soils to minimize the potentially toxic effects of BIT. High-throughput sequencing data showed that the structure and abundance of bacterial communities in BIT soils changed greatly, which might affect their degradation pathways, while Principal Coordinates Analysis (PCoA) results showed that there was no significant difference in the fungal community in different treatments of the five soils, but the degradation rate of BIT was more influenced by anaerobic microorganisms. Furthermore, Proteobacteria, Firmicutes, Bacteroidetes, Actinobacteria, and Acidobacteria were the predominant bacterial phyla, accounting for 93.74% of all OTUs, which played an important role in the degradation of BIT. Lysinibacillus had a high relative abundance (21.10%) under flooded treatment conditions in Jilin soil, and its bioremediation may be a reason for the rapid degradation of BIT in flooded treatment. Besides, only soil organic matter (SOM) and pH among the soil properties had significant effects on the microbial community. Based on the further analysis of bacterial phenotype, some microorganisms related to the biodegradation of BIT were found, mainly belonging to Proteobacteria, Bacteroidetes and Firmicutes. This study provides a useful theoretical basis for the biodegradation of BIT using isolated microorganisms.

Investigation of the adsorption of pymetrozine on the Au@AgNPs surface and its application in the rapid detection of pymetrozine residues in apple.

Pymetrozine is widely used in agriculture to control pests, and its residue may pose a threat to humans. In this study, the adsorption behavior of pymetrozine on Au@AgNPs surfaces in different solutions was investigated by calculation of ACD/Labs, density functional theory, UV-vis spectra, zeta potential and surface-enhanced Raman scattering. Then, a SERS method for detection of pymetrozine residues in apples was established based on the adsorption study. The results showed that pymetrozine was adsorbed on Au@AgNPs surface in different forms in various solutions and high SERS sensitivity of pymetrozine was obtained by the synergistic effect of pymetrozine, Au@AgNPs and NaOH. A simple SERS method has been established to detect pymetrozine in apples with a LOD of 0.038 mg/kg, linear range of 0.05-1.00 mg/kg, recovery of 71.93-117.49 % and RSD low than 11.70 %. This study provides a reference for rapid detection of pymetrozine in agricultural products.

Efficient electro-Fenton catalysis by self-supported CFP@CoFe2O4 electrode.

In this work, the bimetallic iron oxide self-supported electrode was prepared by a simple solvothermal as well as thermal method. CoFe2O4 magnetic nanoparticles were grown in situ on the CFP surface and characterized to reveal the morphology, composition, and electrochemical properties of the electrode. Compared to CFP and CFP@Co-Fe, CFP@CoFe2O4 equipped more efficient mineralization current efficiency and lower energy consumption due to the improved electrocatalytic capacity of CoFe2O4 properly grown on the conductive substrate surface. Further studies showed that the manufactured electrode maintained a high level of stability after continuous operation. According to the free radical trapping experiment, EPR, and liquid mass spectrometry analysis, the rational reaction mechanism of p-nitrophenol was finally proposed, in which ·OH and SO4·- were considered as the main active oxidants. This work demonstrated the great potential of establishing an electro-Fenton system based on CoFe2O4 immobilized self-supporting cathode for environmental remediation.

Growth and repair potential of three species of bacteria in reclaimed wastewater after UV disinfection.

OBJECTIVE: The growth and repair potential of three typical microorganisms in reclaimed water after UV disinfection was investigated to assess the effects of photo-reactivation and dark repair of microorganisms, and the microbial safety of reclaimed water following this procedure. METHODS: The growth and repair potential of Escherichia coli, a fecal coliform strain and Bacillus subtilis in the effluent of a biological wastewater treatment plant disinfected by a low-pressure UV lamp were investigated. RESULTS: Any increase in bacterial numbers in the effluent after UV disinfection was due to damage repair. Exposure to photo-reactivating light for 8-10 h after UV irradiation with a dose of 5 mJ/cm(2), the highest percentage of photo-reactivation observed for E. coli and the fecal coliform strain was 29% and 15% respectively. B. subtilis showed little photo-reactivation under these conditions. The percentage of photo-reactivation was related to the UV dose and the photo-reactivating time, and a function was developed to forecast the final concentrations of E. coli and the fecal coliform strain after UV disinfection with possible photo-reactivation. CONCLUSION: Different species of bacteria displayed different responses to UV light and different repair potentials. The repair of indigenous bacteria in wastewater needs to be investigated in future work.

Antioxidant activities of peptides derived from mutton ham, Xuanwei ham and Jinhua ham.

The aim of the study was to evaluate antioxidant activity of crude peptides with molecular weight less than 3 KDa extracted from Xuanwei ham, Jinhua ham and mutton ham. UPLC-Q-TOF-MS/MS was used for composition analysis of peptides and homologous protein matching. Further, crude peptide (<3 KDa) was purified using G-15 gel filtration chromatography, and the main antioxidant peptide identified. Analysis showed that mutton ham peptide (MHP) has the highest Fe2+ chelating ability, whereas Jinhua ham peptide (JHP) had the highest ABTS and DPPH free radical scavenging ability (P < 0.05). A total of 346, 203 and 296 peptides were identified in JHP, Xuanwei ham peptides (XHP) and MHP, respectively. Most of the peptides were derived from myosin, accounting for 21.97% in JHP, 18.72% in XHP, and 21.96% in MHP. Myosin, actin, myoglobin, troponin, tropomyosin and pyruvate kinase proteins were the main source of peptide differences in the three types of dry cured ham.

A Sensitive SERS Method for Determination of Pymetrozine in Apple and Cabbage Based on an Easily Prepared Substrate.

Residual pesticides are one of the major food safety concerns around the world. There is a demand for simple and reliable methods to monitor pesticide residues in foods. In this study, a sensitive method for determination of pymetrozine in apple and cabbage samples using surface-enhanced Raman spectroscopy (SERS) based on decanethiol functionalized silver nanoparticles was established. The proposed method performed satisfactorily with the linear detection range of 0.01-1.00 mg/L and limit of detection (LOD) of 0.01 mg/L in methanol. In addition, it was successfully used to detect pymetrozine in apple and cabbage samples, the LOD was 0.02 and 0.03 mg/L, respectively, and the recoveries of spiked cabbage and apple ranged 70.40-104.00%, with relative standard deviations below 12.18% and 10.33% for intra-day and inter-day tests. Moreover, the results of the correlation test with real cabbage samples of liquid chromatography-tandem mass spectrometry showed that they were highly correlated (slope = 0.9895, R2 = 0.9953). This study provides a sensitive approach for detection of pymetrozine in apple and cabbage, which has great potential for determination of pymetrozine residues in food products.

Heterogeneous electro-Fenton catalysis with self-supporting CFP@MnO2-Fe3O4/C cathode for shale gas fracturing flowback wastewater.

Self-supporting electrodes have triggered great interests in improving electro-Fenton (EF) system for degradation of refractory organic pollutants. In this work, a novel self-supporting carbon fiber paper (CFP) electrode modified by transition metals, e.g. Fe and Mn, was fabricated and employed as a heterogeneous EF cathode. The prepared electrode exhibited excellent degradation for a number of typical organic pollutants along with superior stability. Remarkably, a high removal efficiency was achieved in the EF treatment of shale gas fracturing flowback wastewater. Results indicated that 65.2% TOC and 74.8% COD were eliminated after 4 h degradation. The residual COD value of the real wastewater was 80 mg L-1, meeting the emission requirement of the integrated wastewater discharge standard (COD＜100 mg L-1) with a low specific energy consumption of 6.9kWhkg-1COD-1. This work demonstrates a competing alternative for efficient decontamination of real wastewater using an electro-Fenton strategy with a low-cost electrode.

Comparison of low- and medium-pressure ultraviolet lamps: Photoreactivation of Escherichia coli and total coliforms in secondary effluents of municipal wastewater treatment plants.

It has been reported that Medium-Pressure (MP) ultraviolet (UV) lamps have an advantage over low-pressure (LP) lamps for water disinfection in terms of the photoreactivation of pure cultured bacteria. However, few studies have investigated the behavior of microorganisms in wastewater. Hence, in this study, the degree of photoreactivation, after UV exposure using both LP and MP lamps, in municipal wastewater samples was examined under a variety of conditions. Pure cultured Escherichia coli was also used to provide a comparison with previous studies. E. coli was found to undergo photoreactivation after both LP and MP exposure. The Colony Forming Ability (CFA) ratios were 0.60 and 0.32, and the percentage of photoreactivation was 50% and 20%, respectively, for LP and MP lamps with a germicidal UV dose of 5 mJ/cm2. However, the advantage of the MP lamp was diminished for larger UV doses, since no photoreactivation was detected when the UV dose was 15 mJ/cm2 for either LP or MP lamps. The microorganisms present in wastewater showed similar results to those of E. coli, however, no significant difference was found between the use of either a LP or a MP lamp. Also, when a UV dose of 40 mJ/cm2 was applied, the percentage photoreactivation was less than 1%, no matter which type of lamp was used. From this work, it is concluded that the selection of the type of UV lamp for wastewater treatment plants, as regards photoreactivation of total coliforms, is not critical as long as the applied germicidal UV dose is greater than 40 mJ/cm2.

Antibiotic resistant bacteria survived from UV disinfection: Safety concerns on genes dissemination.

Antibiotic resistant bacteria (ARB) and antibiotic resistance genes (ARGs) are the emerging contaminants leading to a serious worldwide health problem. Although disinfection like ultraviolet (UV) irradiation could remove part of ARB and ARGs, there still are residual ARB and ARGs in the effluent of wastewater treatment plants. Conjugative transfer is main concern of the risk of ARGs and little is known about the effects of UV disinfection on the transfer ability of the non-inactivated ARB in the effluent which will enter the environment. Hence the influences of UV irradiation and reactivation on ARB conjugative transfer ability were studied under laboratory condition, focusing on the survival bacteria from UV irradiation and the reactivated bacteria, as well as their descendants. The experimental results imply that even 1 mJ/cm2 UV disinfection can significantly decrease the conjugative transfer frequency of the survival bacteria. However, viable but not culturable state cells induced by UV can reactivate through both photoreactivation and dark repair and retain the same level of transfer ability as the untreated strains. This finding is essential for re-considering about the post safety of UV irradiated effluent and microbial safety control strategies were required.

Impacts on antibiotic-resistant bacteria and their horizontal gene transfer by graphene-based TiO2&Ag composite photocatalysts under solar irradiation.

In recent years, photocatalysis has been considered as a promising method, which provides measures to environmental pollution. Antibiotic resistant bacteria (ARB) and their antibiotic resistance genes (ARGs), as the emerging environmental pollutants, are released into the environment, resulting in antibiotic resistance spread. TiO2-based nanocomposites, as the most common photocatalytic material, may influence ARB and ARGs under photocatalytic conditions. However, the research on this aspect is rare. A novel nanocomposite synthesized from Ag, TiO2 and graphene oxide (GO), was selected as a representative of nanomaterials for investigation. The experimental results indicated that TiO2/Ag/GO nanocomposites significantly affected ARB vitality. 100 mg/L TiO2/Ag/GO will reduce bacterial survival to 12.2% in 10 min under simulated sunlight irradiation. Chloramphenicol as the most representative antibiotic in the water, reduces the effect of ARB inactivation under photocatalytic conditions. The addition of TiO2/Ag/GO could affect tetracycline antibiotic resistance. The level of bacterial tolerance to tetracycline had a significant reduction. The horizontal gene transfer was promoted from 1 to 2 folds with the addition of TiO2/Ag/GO. Even high TiO2/Ag/GO concentration (100 mg/L) sample had a limited promotion, suggesting that TiO2/Ag/GO will not increase the risk of antibiotic resistance spread compared to other nano materials.

Novel sensing platform based on gold nanoparticle-aptamer and Fe-metal-organic framework for multiple antibiotic detection and signal amplification.

The development of a feasible antibiotic detection method is important in water quality analysis. In this study, we developed a metal-organic framework (MOF)-aptamer-3,3',5,5'-tetramethylbenzidine (TMB)-H2O2-based sensing platform composed of the reaction variable of TMB catalytic oxidation as the label (from colorless to blue) and aptamer as the target recognition element for antibiotic detection. The platform works by calculating the relation between the antibiotic concentration and the resultant decrease in MOF's catalytic activity. Basing from the comparison of typical iron-based MOF materials (Fe-MIL-53, Fe-MIL-88A, and Fe-MIL-100), we selected Fe-MIL-53 to obtain an improved signal amplification effect. The outstanding performance of the Fe-MIL-53-based sensing platform can be attributed to its topological flexibility and small electron transfer impedance. In addition, a signal increment of up to 86% was obtained with an intensified gold nanoparticle (AuNP)-supported aptamer. The inhibitory catalytic activity stemmed from the coating of antibiotic-(AuNP-aptamer) conjugates onto the outer surface of the MOF material, which increased the impedance and decreased the electron transfer efficiency. Validation results indicated that the platform showed high selectivity and sensitivity (i.e., wide linearity range of 50-200 nM, detection limit up to 8.1 ng/mL, and recovery rate of 106%-110%) for chloramphenicol detection and universal applicability for other antibiotics, including ampicillin, tetracycline, and oxytetracycline. In general, the detection reliability and easy operation of this platform render it a promising candidate for antibiotic detection in future water quality monitoring practices.

Environmental risks of ZnO nanoparticle exposure on Microcystis aeruginosa: Toxic effects and environmental feedback.

The vast majority of studies measure the toxic effect of organisms exposed to nanoparticles (NPs) while there is still a lack of knowledge about the influence of NPs on the aquatic environment. It is unknown whether or not the interaction between NPs and algae will result in the variation of algal organic matter (AOM) and stimulate the production of more algal toxins. In this study, zinc oxide nanoparticles (nano-ZnO) as a typical representative of metal oxide NPs were used to evaluate the toxic effects and environmental feedback of Microcystis aeruginosa. Reactive oxygen species (ROS) and malondialdehyde (MDA) were measured to explain the toxicity mechanism. Changes of AOM, including the production of toxins, the molecular weight distribution and the excitation-emission matrices of algal solution were also studied as environmental feedback indicators after nano-ZnO destroyed the algae. As the nano-ZnO exceeded the comparable critical concentration (1.0 mg/L), the algae were destroyed and intracellular organic matters were released into the aquatic environment, which stimulated the generation of microcystin-LR (MC-LR). However, it is worth noting that the concentration of nano-ZnO would need to be high (at mg/L range) to stimulate more MC-LR production. These findings are expected to be beneficial in interpreting the toxicity and risks of the releasing of NPs through the feedback between algae and the aquatic environment.

Graphene oxide in the water environment could affect tetracycline-antibiotic resistance.

In recent years, the influence of new materials like nanoparticles in the water environment on biological substances has been widely studied. Antibiotic resistance genes (ARGs) represent a new type of pollutant in the environment. Graphene oxide (GO), as a nano material, because of its unique structure, may have an impact on antibiotic resistance bacteria (ARB) and ARGs; however the research in this area is rarely reported. Therefore, this study mainly investigated the effects of GO on bacterial antibiotic resistance. The results showed that GO had a limited effect on ARB inactivation. A high concentration of GO (>10 mg/L) can damage resistant plasmids to reduce bacterial resistance to antibiotics, but low concentrations of GO (<1 mg/L) led to almost no damage to the plasmid. However, all tested concentrations of GO promoted the conjugative transfer from 1to over 3 folds, with low concentrations and high concentration (1-10 and 100 mg/L) of GO samples the least promoted. The overall effect of GO on antibiotic resistance needs further investigation.

Reductions of bacterial antibiotic resistance through five biological treatment processes treated municipal wastewater.

Wastewater treatment plants are hot spots for antibiotic-resistant bacteria (ARB) and antibiotic resistance genes (ARGs). However, limited studies have been conducted to compare the reductions of ARB and ARGs by various biological treatment processes. The study explored the reductions of heterotrophic bacteria resistant to six groups of antibiotics (vancomycin, gentamicin, erythromycin, cephalexin, tetracycline, and sulfadiazine) and corresponding resistance genes (vanA, aacC1, ereA, ampC, tetA, and sulI) by five bench-scale biological reactors. Results demonstrated that membrane bioreactor (MBR) and sequencing batch reactor (SBR) significantly reduced ARB abundances in the ranges of 2.80∼3.54 log and 2.70∼3.13 log, respectively, followed by activated sludge (AS). Biological filter (BF) and anaerobic (upflow anaerobic sludge blanket, UASB) techniques led to relatively low reductions. In contrast, ARGs were not equally reduced as ARB. AS and SBR also showed significant potentials on ARGs reduction, whilst MBR and UASB could not reduce ARGs effectively. Redundancy analysis implied that the purification of wastewater quality parameters (COD, NH4 (+)-N, and turbidity) performed a positive correlation to ARB and ARGs reductions.