Enhanced ozonation of vanillin catalyzed by highly efficient magnetic MnFe2O4/ZIF-67 catalysts: Synergistic effects and mechanism insights.

In this study, we synthesized magnetic MnFe2O4/ZIF-67 composite catalysts using a straightforward method, yielding catalysts that exhibited outstanding performance in catalyzing the ozonation of vanillin. This exceptional catalytic efficiency arose from the synergistic interplay between MnFe2O4 and ZIF-67. Comprehensive characterization via x-ray photoelectron spectroscopy (XPS), x-ray diffraction (XRD), Fourier transform infrared spectrometer (FT-IR), Brunauer-Emmett-Teller (BET), field emission scanning electron microscopy (FE-SEM), and energy dispersive spectroscopy (EDS) confirmed that the incorporation of MnFe2O4 promoted the creation of oxygen vacancies, resulting in an increased presence of l adsorbed oxygen (Oads) and the generation of additional ·OH groups on the catalyst surface. Utilizing ZIF-67 as the carrier markedly enhanced the specific surface area of the catalyst, augmenting the exposure of active sites, thus improving the degradation efficiency and reducing the energy consumption. The effects of different experimental parameters (catalyst type, initial vanillin concentration, ozone dosage, initial pH value, and catalyst dosage) were also investigated, and the optimal experimental parameters (300 mg/L1.0-MnFe2O4/ZIF-67, vanillin concentration = 250 mg/L, O3 concentration = 12 mg/min, pH = 7) were obtained. The vanillin removal efficiency of MnFe2O4/ZIF-67 was increased from 74.95% to 99.54% after 30 min of reaction, and the magnetic separation of MnFe2O4/ZIF-67 was easy to be recycled and stable, and the vanillin removal efficiency of MnFe2O4/ZIF-67 was only decreased by about 8.92% after 5 cycles. Additionally, we delved into the synergistic effects and catalytic mechanism of the catalysts through kinetic fitting, reactive oxygen quenching experiments, and electron transfer analysis. This multifaceted approach provides a comprehensive understanding of the enhanced ozonation process catalyzed by MnFe2O4/ZIF-67 composite catalysts, shedding light on their potential applications in advanced oxidation processes. PRACTITIONER POINTS: A stable and recyclable magnetic composite MnFe2O4/ZIF-67 catalyst was synthesized through a simple method. The synergistic effect and catalytic mechanism of the MnFe2O4/ZIF-67 catalyst were comprehensively analyzed and discussed. A kinetic model for the catalytic ozone oxidation of vanillin was introduced, providing valuable insights into the reaction dynamics.

Analyzing toxicological effects of AsIII and AsV to Chlamys farreri by integrating transcriptomic and metabolomic approaches.

Inorganic arsenic (iAs) is a widespread contaminant in marine environments, which is present in two different oxidation states (arsenate (AsV) and arsenite (AsIII)) that have complex toxic effects on marine organisms. The scallop Chlamys farreri (C. farreri) accumulates high levels of As and is a suitable bioindicator of As. In this report, we integrated transcriptomics and metabolomics to investigate genetic and metabolite changes and functional physiological disturbances in C. farreri exposured to inorganic arsenic. Physiological indicators antioxidant factors and cell apoptosis analysis macroscopically corroborated the toxic effects of inorganic arsenic revealed by omics results. Toxic effects of inorganic arsenic on C. farreri were signaling-mediated, causing interference with a variety of cell growth and small molecule metabolism. The results provide evidence that inorganic arsenic disrupts the physiological functions of bivalves, highlighting the correlations between different metabolic pathways and providing new insights into the toxic effects of environmental pollutants on marine organisms.

The Willingness of the Elderly to Choose Nursing Care: Evidence From in China.

With the accelerating aging of the population and the worsening psychological conditions of older people, the traditional mode of family support for the elderly in China does not always meet the physical and psychological needs of the elderly, and more social support modes for the elderly are needed. Based on 3,513 valid questionnaires on the long-term care and protection needs of Chinese residents, this paper uses a logit regression model to analyze the factors influencing the willingness of the elderly to choose nursing care. The results show that intergenerational family support for the elderly is a significant psychological driver on the willingness of the elderly to choose nursing care. Compared with the elderly living with family, empty nesters or older people living alone are more inclined to select nursing care when they have difficulties taking care of themselves. The physical health of the elderly affects their willingness to choose nursing care, and elderly individuals with more hospitalizations are less likely to select nursing care. In addition, elderly females who are relatively young, have a high level of education, have a high income, have a nursing home near the residence, and are already covered by medical insurance are more willing to choose nursing care. The results of this study are of great importance for improving the medical services and aging care services for the elderly and providing theoretical support for alleviating the psychological and social pressure brought by population aging.

Metabolomic Alterations in the Digestive System of the Mantis Shrimp Oratosquilla oratoria Following Short-Term Exposure to Cadmium.

Mantis shrimp Oratosquilla oratoria is an economically critical aquatic species along the coast of China but strongly accumulates marine pollutant cadmium (Cd) in its digestive system. It is necessary to characterize the toxicity of Cd in the digestive system of mantis shrimp. The metabolic process is an essential target of Cd toxicity response. In this work, we used ultra-performance liquid chromatography coupled with time-of-flight mass spectrometry (UPLC-TOF-MS) for untargeted metabolomics to characterize the metabolic changes in the digestive system of O. oratoria, exposed to 0.05 mg/L for 96 h. The aim of this study was to further investigate the effect of O. oratoria on Cd response to toxicity and develop biomarkers. Metabolomics analysis showed the alteration of metabolism in the digestive system of mantis shrimp under Cd stress. A total of 91 metabolites were differentially expressed and their main functions were classified into amino acids, phospholipids, and fatty acid esters. The enrichment results of differential metabolite functional pathways showed that biological processes such as amino acid metabolism, transmembrane transport, energy metabolism, and signal transduction are significantly affected. Based on the above results, the Cd-induced oxidative stress and energy metabolism disorders were characterized by the differential expression of amino acids and ADP in mantis shrimp, while the interference of transmembrane transport and signal transduction was due to the differential expression of phospholipids. Overall, this work initially discussed the toxicological response of Cd stress to O. oratoria from the metabolic level and provided new insights into the mechanism.

Metabolomics comparison of metabolites and functional pathways in the gills of Chlamys farreri under cadmium exposure.

The biological processes of Chlamys farreri (C. farreri), an economically important shellfish, are affected when exposed to Cd2+. In this study, changes to biological processes and metabolite levels in C. farreri were examined when exposed to Cd2+. Ultra-performance liquid chromatography-tandem TOF mass spectrometry (UPLC-TOF/MS)-based untargeted metabolomics was used to examine changes in the metabolism of C. farreri gill tissue exposed to 0.050 mg/L Cd2+ for 96 h in a natural environment. Sixty-eight metabolites with significant differences were screened by multivariate statistical analysis. Eleven enriched functional pathways displayed significant changes in inactivity. Differential metabolites, mainly C00157 and C00350, have a significant impact on functional pathways and can be used as potential major biomarkers. Lipid phosphorylation, disruption of signal transduction, and autophagy activation were observed to change in C. farreri when exposed to Cd. The metabolome information supplements research on C. farreri exposure to heavy metals and provides a platform for further multi-omics analysis.

Analysis of amantadine in Laminaria Japonica and seawater of Daqin Island by ultra high performance liquid chromatography with positive electrospray ionization tandem mass spectrometry.

A sensitive and validated method for determination of amantadine in Laminaria Japonica and seawater was established using ultra high performance liquid chromatography with positive electrospray ionization tandem spectrometry (UHPLC-ESI-MS/MS). Laminaria Japonica was extracted with acetonitrile containing formic acid (1%), then purified with 10.0 g anhydrous sodium sulfate, 0.50 g C18 and 0.50 g PSA powder. Seawater added 10.0 mL 0.20 mol/L hydrochloric acid was purified with MCX solid phase extraction (SPE) cartridge. After extraction and purification, the supernatant of Laminaria Japonica and eluate of seawater were evaporated to nearly dry under a gentle stream of nitrogen at 40 °C. Acetonitrile-0.1% formic acid in water (3/7, v/v) was adjusted to 1.00 mL final volume. An aliquot (10 µL) was injected into the C18 column for separation with the mobile phase of acetonitrile and 0.1% formic acid in water at 0.25 mL·min-1. Calibration curves were linear ranged from 1.00 ng/mL to 20.0 ng/mL. Mean recoveries were 73.5% to 95.8%, and limit of detection (LOD) and quantification (LOQ) were 0.50 µg/kg and 1.00 µg/kg for Laminaria Japonica. Mean recoveries were 75.8% to 93.4%, and LOD and LOQ were 0.50 ng/L and 1.00 ng/L for seawater. Based on the method above, Laminaria Japonica and seawater in Daqin Island were analyzed in February to June continuously, lgBAF3.71 (bioaccumulation factor), indicating a bioenrichment effect.

UPLC-MS/MS Method for Simultaneous Determination of Three Major Metabolites of Mequindox in Holothurian.

This study developed an ultraperformance liquid chromatography tandem mass spectrometry (UPLC-MS/MS) method for the detection of three major metabolites of mequindox, including 3-methyl-quinoxaline-2-carboxylic acid, 1-desoxymequindox, and 1,4-bisdesoxymequindox (MQCA, 1-DMEQ, and BDMEQ), in holothurian. Target analytes were simplified with ultrasound-assisted acidolysis extracted without complicated enzymolysis steps. After that, each sample was centrifuged and purified by an Oasis MAX cartridge. Then, the processed samples were separated and monitored by UPLC-MS/MS. This developed method has been validated according to FDA criteria. At fortified levels of 2, 10, and 20 µg/kg, recoveries ranged from 82.5% to 93.5% with the intraday RSD less than 7.27% and interday RSD less than 11.8%. The limit of detection (LOD) of all the three metabolites ranged from 0.21 to 0.48 µg/kg, while the limit of quantification (LOQ) ranged from 0.79 to 1.59 µg/kg. On application to commercial samples, 14 of 20 samples were detected positive for the three target analytes, with positive rate at 70 percentage. The result indicated that this method was specific, sensitive, and suitable for the quantification and conformation of the three major metabolites of MEQ in holothurian.

Environmental status and early warning value of the pollutant Semicarbazide in Jincheng and Sishili Bays, Shandong Peninsula, China.

A verified method for measuring Semicarbazide (SEM) in seawater, sediments, and shellfish was developed based on ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). A total of 30 stations were radially distributed in Jincheng and Sishili Bays in the Bohai and Yellow Seas, and 1025 monitoring data were collected in 41 voyages, 615 seawater samples, 320 sediment samples and 90 shellfish samples. The concentration ranged from 0.011µg/L to 0.093µg/L and 0 to 0.75µg/kg in seawater and shellfish respectively, but SEM in sediment was all below the limit of detection. Temporal and spatial distribution of SEM was investigated using multivariate analysis to estimate the degree of SEM pollution. Based on the SEM concentration in the three sample types, together with our previous findings, early warning values were deduced for SEM in seawater, and the developed method overcame shortcomings with existing technologies. The results may be helpful to draft national baseline values for SEM in seawater and sediments, and provide a scientific basis for assessing the impacts of SEM on marine ecology and human health.

Temporal and spatial distribution of semicarbazide in western Laizhou Bay.

Semicarbazide (SEM), an industrial raw material and the marker residue of nitrofurazone as a veterinary drug, has become a new type of marine pollutant. A standard method (ultra-performance liquid chromatography-tandem mass spectrometry, UPLC-MS/MS) was used to analyze SEM in seawater, sediment, and shellfish. A series of sections and stations were set up in radical distribution in western Laizhou Bay, with six voyages and 150 monitoring samples. The concentrations of SEM in seawater and shellfish were 10-11 and 10-10kg/L, respectively, and no SEM was detected in the sediment. Distribution characteristics at each state, temporal and spatial trends, multivariate analyses, and the causes were analyzed to assess the pollution level, which aimed to offer a database for drafting the national baseline values of SEM in seawater and sediment in future. The data obtained could be used for integrated watershed management of marine environment and economic activities for constructing a blue economic zone of Shandong Peninsula in China.

Risk assessment of butyltins based on a fugacity-based food web bioaccumulation model in the Jincheng Bay mariculture area: II. Risk assessment.

A fugacity-based food web bioaccumulation model was constructed, and the biotic concentrations of butyltins in the food web of the Jincheng Bay mariculture area were estimated accordingly, using the water and sediment concentrations described in the accompanying paper (Part I). This paper presents an ecological risk assessment (ERA) and a human health risk assessment (HHRA) of the butyltins, based on the estimated tissue residues in the marine life in this area. The results showed that the ecological risk probability was greater than 0.05. At this level, management control is critical since sensitive marine species would be profoundly endangered by butyltin contamination. Few if any detrimental effects, however, would be generated for humans from exposure to butyltins through seafood consumption. The fugacity-based model can refine the ERA and HHRA of pollutants in marine areas, provide a basis for protecting marine ecology and the security of fishery products, and thus help determine the feasibility of a proposed aquaculture project.

Risk assessment of butyltins based on a fugacity-based food web bioaccumulation model in the Jincheng Bay mariculture area: I. Model development.

A fugacity-based model was developed to simulate the bioaccumulation of butyltins in the food web of the Jincheng Bay mariculture area. The predicted biological tissue residues of tributyltin (TBT), dibutyltin (DBT), and monobutyltin (MBT) were 0.04-17.09, 0.14-53.54, and 0.27-108.77 ng-Sn g(-1), respectively, and the predicted values in six mollusca agreed well with the measured ones. The lipid-normalized concentrations did not significantly increase across trophic levels, indicating no biomagnification across aquatic food webs. These results were highly consistent with those observed both in the laboratory and field, which had been reported in numerous references. The explanation, from calculating their flux equilibrium in the food web, was that butyltins were primarily taken in via respiration from the water column by marine organisms. The sensitivities of the model parameters were analyzed, revealing that the hydrophobicity of butyltins played the dominant role in their bioaccumulation phenomena. The verified model predictions of the biotic tissue concentrations of the butyltins could be readily applied to perform internal ecological risk and human health risk assessments in this area.

Analysis of colistin A and B in fishery products by ultra performance liquid chromatography with positive electrospray ionization tandem mass spectrometry.

A rapid and simple method for the determination of colistin A and B in fishery products by reversed phase ultra performance liquid chromatography with positive electrospray ionization tandem spectrometry (UPLC-ESI-MS/MS) method was described. The samples were extracted with 1.0 mol/L of hydrochloric acid in methanol-water and then purified on the PLS solid phase extraction columns. Then the eluate was evaporated to less than 1 mL under a gentle stream of nitrogen at 40 °C and formic acid-acetonitrile-water (0.2/10/90, v/v/v) was added to adjust volume to 1 mL final volume. An aliquot (10 µL) was injected onto the LC column for analysis with the mobile phase of 0.2% formic acid in acetonitrile and 0.2% formic acid in water at 0.20 mL min⁻¹. Multiple reaction monitoring was performed using precursor-product ion combinations. Calibration curves were linear from 200 ng/mL to 2000 ng/mL for colistin A and B. Mean recoveries were between 72.9% and 82.9%. The LOD was 10.0 µg/kg and LOQ was 40.0 µg/kg. The intra-day assay precision values for QC samples were between 2.17% and 9.00%, and inter-day values were between 2.80% and 6.97%. The method has merits of simplicity, sensitivity and rapidity, and it can be used for the determination of colistin A and B in fishery products.

Simultaneous determination of malachite green, crystal violet, methylene blue and the metabolite residues in aquatic products by ultra-performance liquid chromatography with electrospray ionization tandem mass spectrometry.

This work describes solid-phase extraction-ultra-performance liquid chromatography with electrospray ionization tandem spectrometry for determination of malachite green and metabolite leucomalachite green, crystal violet and metabolite leucocrystal violet, methylene blue and metabolites including azure A, azure B and azure C in aquatic products. Samples were extracted with acetonitrile and ammonium acetate buffer and purified by liquid extraction with dichloromethane, and then on MCAX solid-phase extraction cartridges. Then the extract was evaporated at 45°C by nitrogen blow. The residue was dissolved and separated by an Acquity BEH C18 column. The mobile phase was acetonitrile (A) and 5 mmol/L of ammonium acetate containing 0.1% formic acid (B). Analytes were confirmed and quantified using a tandem mass spectrometry system in multiple reaction mode with triple quadrupole analyzer using positive polarity mode. The limits of detection of malachite green, leucomalachite green, crystal violet and leucocrystal violet were 0.15 µg/kg, the limits of quantification were 0.50 µg/kg, and the average recoveries were more than 75% with spiked residues from 0.5 to 10 µg/kg. The relative standard deviations were less than 13%. The limits of detection of methylene blue, azure A, azure B and azure C were 0.3 µg/kg, the limits of quantification were 1.0 µg/kg, the average recoveries were more than 70% with spiked residues from 1.0 to 10 µg/kg and the relative standard deviations were less than 15%. The method has the merits of simplicity, sensitivity and rapidity, and can be used for simultaneous determination of the analytes in aquatic products.