The elimination of neonicotinoids(NEOs)from water has been a research priority due to their threats to human health and ecosystems.In this study,we established the heterogeneous peroxymonosulfate(PMS)activation system...The elimination of neonicotinoids(NEOs)from water has been a research priority due to their threats to human health and ecosystems.In this study,we established the heterogeneous peroxymonosulfate(PMS)activation system using manganese catalyst(Mn NC)and cobalt catalyst(Co NC)to trigger the nonradical oxidation and synergistic oxidation pathway,respectively to remove NEOs.The results showed that the nonradical oxidation system exhibited superior NEOs degradation capability.The composition of organic pollutants in wastewater significantly impacted subsequent degradation processes.The charge distribution and reaction sites of various NEOs were analyzed using density functional theory(DFT)calculations,and it demonstrated the electron distribution and activity of NEOs were significantly influenced by the type and number of substituents.Nitro group(–NO_(2))and cyanide group(–C≡N)were identified as strong electron-withdrawing groups and prone to be attacked by negatively charged radicals.The transformation of NEOs was analyzed,and result showed that the C and N sites adjacent to the nitro group and cyanide group were more susceptible to oxidation attacks.S and N atoms,which possess strong electronegativity and high electron cloud density,were identified as key active sites in the degradation pathway.The outcomes of this study provide valuable guidance for the oriented regulation of oxidation pathways towards efficient removal of NEOs in water.展开更多
Precise and sensitive methods for the simultaneous determination of different classes of antibiotics, including sulphonamides, fluoroquinolones, macrolides, tetracyclines, and trimethoprim in surface water, sediments,...Precise and sensitive methods for the simultaneous determination of different classes of antibiotics, including sulphonamides, fluoroquinolones, macrolides, tetracyclines, and trimethoprim in surface water, sediments, and fish muscles were developed. In water samples, drugs were extracted with solid-phase extraction （SPE） by passing 1000 mL of water through hydrophilic lipophilic balanced （HLB） SPE cartridges. Sediment samples were solvent-extracted, followed by tandem SPE （strong anion exchange （SAX） ＋ HLB） clean-ups. Fish muscles were extracted by a mixture of acetonitrile and citric buffer （80：20, v/v） solution, and cleaned by SPE. Liquid chromatography-tandem mass spectrometry （LC-MS/ MS） with multiple reaction monitoring （MRM） detection was employed to quantify all compounds. The recoveries for the antibiotics in the spiked water, sediment, and fish samples were 60.2%-95.8%, 48.1%-105.3%, and 59.8%- 103.4%, respectively. The methods were applied to samples taken from Dianchi Lake, China. It showed that concentrations of the detected antibiotics ranged from limits of quantification （LOQ） to 713.6 ng- L1 （ofloxacin） in surface water and from less than LOQ to 344.8 μg·kg-1 （sulphamethoxazole） in sediments. The number of detected antibiotics and the overall antibiotic concentrations were higher in the urban area than the rural area, indicating the probable role of livestock and human activities as important sources of antibiotic contamination. In fish muscles, the concentration of norfioxacin was the highest （up to 38.5 μg·kg-1）, but tetracyclines and macrolides were relatively low. Results showed that the methods were rapid and sensitive, and capable of determining several classes of antibiotics from each of the water, sediment, and fish matrices in a single run.展开更多
This study investigated the presence of 11 abused drugs and their metabolites, including amphetamine, methamphetamine (METH), ketamine, ephedrine (EPH), cocaine, benzoylecgonine, methadone, morphine, heroin, codeine, ...This study investigated the presence of 11 abused drugs and their metabolites, including amphetamine, methamphetamine (METH), ketamine, ephedrine (EPH), cocaine, benzoylecgonine, methadone, morphine, heroin, codeine, and methcathinone in the surface water and sediment samples of Beiyunhe River, a typical urban river flowing through Beijing, Tianjin, and Hebei provinces in North China. An analytical method of determining these abused drugs and their metabolites in water and sediment was developed and validated prior to sample collection in the study area. Results showed that METH and EPH were predominant in water and sediment samples. The total drug concentrations ranged from 26.6 to 183.0 ng/L in water and from 2.6 to 32.4 ng/g dry weight in sediment, and the drugs mainly originated from hospitals and sewage treatment plants. The average field-based sediment water distribution coefficients of abused drugs were calculated between 149.3 and 1214.0 L/kg and corrected by organic carbon. Quotient method was used to assess the risks. The findings revealed that these drugs and their metabolites at determined concentrations in water samples will not impair the aquatic ecosystem biologically, but their potential harmful effect on the function of the ecosystem and human health should not be overlooked.展开更多
Surface sediment samples from Taihu Lake in China and its inflow rivers,along with two lake sediment core samples,were collected and analyzed for organophosphate esters(OPEs).The concentrations of total OPEs varied fr...Surface sediment samples from Taihu Lake in China and its inflow rivers,along with two lake sediment core samples,were collected and analyzed for organophosphate esters(OPEs).The concentrations of total OPEs varied from 28.60 ng/g to 158.72 ng/g(median:54.25 ng/g)in river surface sediment and from 62.57 ng/g to 326.84 ng/g(median:86.37 ng/g)in lake sediment.Tributyl phosphate(TnBP)was the predominant compound in river surface sediment,and tris(2-butoxyethyl)phosphate was predominant in lake sediment.High contamination occurred in the north-west region,which was related to the high level of urbanization and high usage of OPEs.The sediment–water partition coefficients of OPEs(log_(Koc))were calculated,showing a significant correlation with logKow(p<0.05).The concentration and composition of OPEs in two sediment cores varied due to the different sampling locations,with more OPE species found in the northern region than in the southern one.Principal component analysis and positive matrix factorization indicated that sewage discharges,vehicle emissions,and atmospheric deposition were the possible sources of OPEs in Taihu Lake sediments.Tris(1-chloro-2-propyl)phosphate,tris(2-chloroethyl)phosphate,and TnBP were the main OPEs causing ecological risks.展开更多
ZnO/TiO_(2)composites were synthesized by using the solvothermal method and ultrasonic precipitation followed by heat treatment in order to investigate their photocatalytic degradation of methyl orange(MO)in aqueous s...ZnO/TiO_(2)composites were synthesized by using the solvothermal method and ultrasonic precipitation followed by heat treatment in order to investigate their photocatalytic degradation of methyl orange(MO)in aqueous suspension under UV irradiation.The composition and surface structure of the catalyst were characterized by X-ray diffraction(XRD),field emission scanning electron microscope(FE-SEM),and transmission electron microscopy(TEM).The degradation efficiencies of MO at various pH values were obtained.The highest degradation efficiencies were obtained before 30 min and after 60 min at pH 11.0 and pH 2.0,respectively.A sample analysis was conducted using liquid chromatography coupled with electrospray ionization ion-trap mass spectrometry.Six intermediates were found during the photocatalytic degradation process of quinonoid MO.The degradation pathway of quinonoid MO was also proposed.展开更多
The adsorption of sulfadiazine onto kaolinite clay as an alternative adsorbent was examined in aqueous solution, hnpacts of the contact time, pH, temperature, ionic strength and coexistent surfactants on the adsorptio...The adsorption of sulfadiazine onto kaolinite clay as an alternative adsorbent was examined in aqueous solution, hnpacts of the contact time, pH, temperature, ionic strength and coexistent surfactants on the adsorption process were evaluated. The pH significantly influenced the adsorption process, with adsorption being promoted at lower pH due to the cation exchange mechanism. Decreasing ionic strength in the solution was favorable for adsorption, and the addition of cationic and anionic surfactants had negative effects on the adsorption capacity of sulfadiazine on kaolinite. Kinetic experiments showed that the adsorption followed the pseudo-second-order model. The equilibrium adsorption was well described by both Freundlich and Dubinin-Radushkevich （DR） models. According to the DR model, the adsorption mechanism was determined by cationic exchange and weak physical forces. The thermodynamic study showed that sulfadiazine adsorption onto kaolinite was a sponta- neous and endothermic reaction.展开更多
Hexahedron-like BiPO4 microcrystals were sucessfully synthesized via a template-free hydrothermal method. The resulting samples were characterized by X- ray diffraction （XRD）, field-emission scanning electron micros...Hexahedron-like BiPO4 microcrystals were sucessfully synthesized via a template-free hydrothermal method. The resulting samples were characterized by X- ray diffraction （XRD）, field-emission scanning electron microscopy （FESEM）, transmission electron microscopy （TEM） and UV-vis spectroscopy. The BiPO4 samples were of pure monoclinic phase, and the initial amount of PO3- during synthesis did not show obvious effect on the phase properties of the materials. The hexahedron-like BiPO4 microcrystal had explicitly cut edges, and its thickness was about 1 gin. The photocatalytic performance of the BiPO4 catalysts was evaluated by photodegradation of RhB under UV light irradiation with commerial Degussa P25 TiO2 as reference. Compared with P25, the BiPO4 catalysts displayed higher photocatalytic activity, with 98.7% of RhB degraded during 60-min experiment. Cost evaluation analysis was adopted to describe the energy consumption of the degradation process, and the results suggested the potential application of this material in the field of dye-contaminated wastewater treatment or environmental matrices remediation.展开更多
基金funded by National Natural Science Foundation of China(No.42177382)。
文摘The elimination of neonicotinoids(NEOs)from water has been a research priority due to their threats to human health and ecosystems.In this study,we established the heterogeneous peroxymonosulfate(PMS)activation system using manganese catalyst(Mn NC)and cobalt catalyst(Co NC)to trigger the nonradical oxidation and synergistic oxidation pathway,respectively to remove NEOs.The results showed that the nonradical oxidation system exhibited superior NEOs degradation capability.The composition of organic pollutants in wastewater significantly impacted subsequent degradation processes.The charge distribution and reaction sites of various NEOs were analyzed using density functional theory(DFT)calculations,and it demonstrated the electron distribution and activity of NEOs were significantly influenced by the type and number of substituents.Nitro group(–NO_(2))and cyanide group(–C≡N)were identified as strong electron-withdrawing groups and prone to be attacked by negatively charged radicals.The transformation of NEOs was analyzed,and result showed that the C and N sites adjacent to the nitro group and cyanide group were more susceptible to oxidation attacks.S and N atoms,which possess strong electronegativity and high electron cloud density,were identified as key active sites in the degradation pathway.The outcomes of this study provide valuable guidance for the oriented regulation of oxidation pathways towards efficient removal of NEOs in water.
基金This work was financially supported by the National Natural Science Foundation of China （Grant No. 51178438） and the National Basic Research Program of China （No. 2008CB418201）.
文摘Precise and sensitive methods for the simultaneous determination of different classes of antibiotics, including sulphonamides, fluoroquinolones, macrolides, tetracyclines, and trimethoprim in surface water, sediments, and fish muscles were developed. In water samples, drugs were extracted with solid-phase extraction （SPE） by passing 1000 mL of water through hydrophilic lipophilic balanced （HLB） SPE cartridges. Sediment samples were solvent-extracted, followed by tandem SPE （strong anion exchange （SAX） ＋ HLB） clean-ups. Fish muscles were extracted by a mixture of acetonitrile and citric buffer （80：20, v/v） solution, and cleaned by SPE. Liquid chromatography-tandem mass spectrometry （LC-MS/ MS） with multiple reaction monitoring （MRM） detection was employed to quantify all compounds. The recoveries for the antibiotics in the spiked water, sediment, and fish samples were 60.2%-95.8%, 48.1%-105.3%, and 59.8%- 103.4%, respectively. The methods were applied to samples taken from Dianchi Lake, China. It showed that concentrations of the detected antibiotics ranged from limits of quantification （LOQ） to 713.6 ng- L1 （ofloxacin） in surface water and from less than LOQ to 344.8 μg·kg-1 （sulphamethoxazole） in sediments. The number of detected antibiotics and the overall antibiotic concentrations were higher in the urban area than the rural area, indicating the probable role of livestock and human activities as important sources of antibiotic contamination. In fish muscles, the concentration of norfioxacin was the highest （up to 38.5 μg·kg-1）, but tetracyclines and macrolides were relatively low. Results showed that the methods were rapid and sensitive, and capable of determining several classes of antibiotics from each of the water, sediment, and fish matrices in a single run.
基金funded by the Major Science and Technology Program for Water Pollution Control and Treatment (No. 2017ZX07302001)National Natural Science Foundation of China (Grant No. 41673120).
文摘This study investigated the presence of 11 abused drugs and their metabolites, including amphetamine, methamphetamine (METH), ketamine, ephedrine (EPH), cocaine, benzoylecgonine, methadone, morphine, heroin, codeine, and methcathinone in the surface water and sediment samples of Beiyunhe River, a typical urban river flowing through Beijing, Tianjin, and Hebei provinces in North China. An analytical method of determining these abused drugs and their metabolites in water and sediment was developed and validated prior to sample collection in the study area. Results showed that METH and EPH were predominant in water and sediment samples. The total drug concentrations ranged from 26.6 to 183.0 ng/L in water and from 2.6 to 32.4 ng/g dry weight in sediment, and the drugs mainly originated from hospitals and sewage treatment plants. The average field-based sediment water distribution coefficients of abused drugs were calculated between 149.3 and 1214.0 L/kg and corrected by organic carbon. Quotient method was used to assess the risks. The findings revealed that these drugs and their metabolites at determined concentrations in water samples will not impair the aquatic ecosystem biologically, but their potential harmful effect on the function of the ecosystem and human health should not be overlooked.
基金funded by the Special Fund for Basic Scientific Research of Central Public Research Institutes(2019YSKY-022,2020YSKY-018).
文摘Surface sediment samples from Taihu Lake in China and its inflow rivers,along with two lake sediment core samples,were collected and analyzed for organophosphate esters(OPEs).The concentrations of total OPEs varied from 28.60 ng/g to 158.72 ng/g(median:54.25 ng/g)in river surface sediment and from 62.57 ng/g to 326.84 ng/g(median:86.37 ng/g)in lake sediment.Tributyl phosphate(TnBP)was the predominant compound in river surface sediment,and tris(2-butoxyethyl)phosphate was predominant in lake sediment.High contamination occurred in the north-west region,which was related to the high level of urbanization and high usage of OPEs.The sediment–water partition coefficients of OPEs(log_(Koc))were calculated,showing a significant correlation with logKow(p<0.05).The concentration and composition of OPEs in two sediment cores varied due to the different sampling locations,with more OPE species found in the northern region than in the southern one.Principal component analysis and positive matrix factorization indicated that sewage discharges,vehicle emissions,and atmospheric deposition were the possible sources of OPEs in Taihu Lake sediments.Tris(1-chloro-2-propyl)phosphate,tris(2-chloroethyl)phosphate,and TnBP were the main OPEs causing ecological risks.
基金the Doctoral Fund of Ministry of Education of China(Grant No.200800550011)the Chinese Academy for Environmental Planning(Grant No.2008AW01).
文摘ZnO/TiO_(2)composites were synthesized by using the solvothermal method and ultrasonic precipitation followed by heat treatment in order to investigate their photocatalytic degradation of methyl orange(MO)in aqueous suspension under UV irradiation.The composition and surface structure of the catalyst were characterized by X-ray diffraction(XRD),field emission scanning electron microscope(FE-SEM),and transmission electron microscopy(TEM).The degradation efficiencies of MO at various pH values were obtained.The highest degradation efficiencies were obtained before 30 min and after 60 min at pH 11.0 and pH 2.0,respectively.A sample analysis was conducted using liquid chromatography coupled with electrospray ionization ion-trap mass spectrometry.Six intermediates were found during the photocatalytic degradation process of quinonoid MO.The degradation pathway of quinonoid MO was also proposed.
基金Acknowledgements This work was financially supported by the National Basic Research Program of China （No. 2008CB418201）, National Science Foundation of China （Grant Nos. 20977051 and 51178438） and the Public Welfare Project of Basic Scientific Research for S＆R Institutes （No. 2010KYYW03）.
文摘The adsorption of sulfadiazine onto kaolinite clay as an alternative adsorbent was examined in aqueous solution, hnpacts of the contact time, pH, temperature, ionic strength and coexistent surfactants on the adsorption process were evaluated. The pH significantly influenced the adsorption process, with adsorption being promoted at lower pH due to the cation exchange mechanism. Decreasing ionic strength in the solution was favorable for adsorption, and the addition of cationic and anionic surfactants had negative effects on the adsorption capacity of sulfadiazine on kaolinite. Kinetic experiments showed that the adsorption followed the pseudo-second-order model. The equilibrium adsorption was well described by both Freundlich and Dubinin-Radushkevich （DR） models. According to the DR model, the adsorption mechanism was determined by cationic exchange and weak physical forces. The thermodynamic study showed that sulfadiazine adsorption onto kaolinite was a sponta- neous and endothermic reaction.
文摘Hexahedron-like BiPO4 microcrystals were sucessfully synthesized via a template-free hydrothermal method. The resulting samples were characterized by X- ray diffraction （XRD）, field-emission scanning electron microscopy （FESEM）, transmission electron microscopy （TEM） and UV-vis spectroscopy. The BiPO4 samples were of pure monoclinic phase, and the initial amount of PO3- during synthesis did not show obvious effect on the phase properties of the materials. The hexahedron-like BiPO4 microcrystal had explicitly cut edges, and its thickness was about 1 gin. The photocatalytic performance of the BiPO4 catalysts was evaluated by photodegradation of RhB under UV light irradiation with commerial Degussa P25 TiO2 as reference. Compared with P25, the BiPO4 catalysts displayed higher photocatalytic activity, with 98.7% of RhB degraded during 60-min experiment. Cost evaluation analysis was adopted to describe the energy consumption of the degradation process, and the results suggested the potential application of this material in the field of dye-contaminated wastewater treatment or environmental matrices remediation.
