A precise and reliable analytical method of high performance liquid chromatography-tandem mass spectrometry(HPLCMS/MS)was developed to measure trace levels of enrofloxacin(ENR)and its major metabolite ciprofloxacin(CI...A precise and reliable analytical method of high performance liquid chromatography-tandem mass spectrometry(HPLCMS/MS)was developed to measure trace levels of enrofloxacin(ENR)and its major metabolite ciprofloxacin(CIP)in carp tissues.Optimized chromatographic separation was obtained on a Waters Xterra MS C_(18) reversed-phase column using gradient elution with methanol and 0.1%formic acid aqueous solution including 5mmolL^(-1) of ammonium acetate.The established method was applied to study the pharmacokinetics and distribution of ENR and CIP in tissues of carp following a single oral administration in feed at a dosage of 40mgkg^(-1) bw(body weight).Data were analyzed using DAS 2.0 dynamics software,and the experimental results suggest that ENR was rapidly absorbed and extensively distributed in carp tissues through systemic circulation,and the pharmacokinetic characteristics can be described with a two-compartment model.The elimination half-lives(t_(1/2β))from muscle,liver,gill,plasma and skin were 131,160,104,132 and 310 h,respectively.The areas under the drug concentration-time curves(AUC)for these tissues were 491,972,750,249 and 706hmgkg^(-1),respectively.The maximum concentration(C_(max))values were 13,29,37,9 and 5mgkg^(-1) with peak times(t_(max))of 8,4,4,2 and 4 h,respectively.Ciprofloxacin,the active metabolite of ENR,was also detected in carp tissues,indicating that only 1.54%of de-ethylation of ENR occurs in carp.At a water temperature of 18℃,the drug withdrawal time was determined to be no less than 24 d while the carp was fed at a single dosage of 40mgkg^(-1).展开更多
The synergetic effect and underlying mechanism of potassium ferrate(PF)with tea saponin(TS,a biosurfactant)in producing short chain fatty acids(SCFAs)from anaerobic fermentation of waste activated sludge(WAS)were expl...The synergetic effect and underlying mechanism of potassium ferrate(PF)with tea saponin(TS,a biosurfactant)in producing short chain fatty acids(SCFAs)from anaerobic fermentation of waste activated sludge(WAS)were explored in this work.Experimental results showed that 0.2 g PF(g TSS)^(-1)(total suspended solid)combined with 0.02 g TS(g TSS)^(-1) could further improve SCFAs’production,and the maximum SCFAs content reached 2008.7 mg COD L^(-1),which is 1.2 and 4.5 times higher than those with PF and TS individually added,respectively,and 5.3 times higher than that of blank WAS on Day 12.In the model substrates experiments,the degradation rates of bovine serum albumin and dextran with combination of PF and TS were 41.3%±0.1% and 48.5%±0.06%,respectively,on Day 3,which are lower than those in blank WAS(with degradation rates of 72.3%±0.5%and 90.3%±0.3%).It was revealed that the oxidative effect of PF and the solubilization of TS caused more organic matters to be dissolved out from WAS,providing a large number of biodegradable substances for subsequent SCFAs production.While WAS pretreated with the combination of PF and TS,the relative abundances of Firmicutes increased from 6.4%(blank)to 38.6%,and that of Proteobacteria decreased from 41.8%(blank)to 21.8%.The combination of PF and TS promoted the hydrolysis process of WAS by enriching Firmicutes,and then increased acetic acid production by inhibiting Proteobacteria that consumed SCFAs.Meanwhile,at the genus level,acidogenesis bacteria(e.g.,Proteiniclasticum and Petrimonas)were enriched whereas SCFAs consuming bacteria(e.g.,Dokdonella)were inhibited.展开更多
Per-and polyfluoroalkyl substances(PFASs)are emerging persistent organic pollutants(POPs).In this study,47 surface sediment samples were collected from the Yellow River Delta wetland(YRDW)to investigate the occurrence...Per-and polyfluoroalkyl substances(PFASs)are emerging persistent organic pollutants(POPs).In this study,47 surface sediment samples were collected from the Yellow River Delta wetland(YRDW)to investigate the occurrence,spatial distribution,potential sources,and ecological risks of PFASs.Twenty-three out of 26 targeted PFASs were detected in surface sediment samples from the YRDW,with totalΣ23PFASs concentrations ranging from 0.23 to 16.30 ng g^(-1) dw and a median value of 2.27 ng g^(-1) dw.Perfluorooctanoic acid(PFOA),perfluorobutanoic acid(PFBA)and perfluorooctanesulfonic acid(PFOS)were the main contaminants.The detection frequency and concentration of perfluoroalkyl carboxylic acids(PFCAs)were higher than those of perfluoroal-kanesulfonic acids(PFSAs),while those of long-chain PFASs were higher than those of short-chain PFASs.The emerging PFASs substitutes were dominated by 6:2 chlorinated polyfluoroalkyl ether sulfonic acid(6:2 Cl-PFESA).The distribution of PFASs is significantly influenced by the total organic carbon content in the sediments.The concentration of PFASs seems to be related to human activities,with high concentration levels of PFASs near locations such as beaches and villages.By using a positive matrix factorization model,the potential sources of PFASs in the region were identified as metal plating mist inhibitor and fluoropolymer manufacturing sources,metal plating industry and firefighting foam and textile treatment sources,and food packaging material sources.The risk assessment indicated that PFASs in YRDW sediments do not pose a significant ecological risk to benthic organisms in the region overall,but PFOA and PFOS exert a low to moderate risk at individual stations.展开更多
Lignin serves as one of the most important molecular fossils for tracing Terrestrial Organic Matters (TOMs) in marine environment. Extraction and derivatization of lignin oxidation products (LOPs) are crucial for ...Lignin serves as one of the most important molecular fossils for tracing Terrestrial Organic Matters (TOMs) in marine environment. Extraction and derivatization of lignin oxidation products (LOPs) are crucial for accurate quantification of lignin in marine sediment. Here we report a modification of the conventional alkaline cupric oxide (CuO) oxidation method, the modification consisting in a solid phase extraction (SPE) and a novel on-column derivatization being employed for better efficiency and reproducibility. In spiking blanks, recoveries with SPE for the LOPs are between 77.84% and 99.57% with relative standard deviations (RSDs) ranging from 0.57% to 8.04% (n=3), while those with traditional liquid-liquid extraction (LLE) are from 44.52% to 86.16% With RSDs being from 0.53% to 13.14% (n=3). Moreover, the reproducibility is greatly improved with SPE, with less solvent consumption and shorter processing time. The average efficiency of on-column derivatization for LOPs is 100.8%±0.68%, which is significantly higher than those of in-vial or in-syringe derivatization, thus resulting in still less consumption of derivatizing reagents.Lignin in the surface sediments sampled from the south of Yangtze River estuary, China, was determined with the established method. Recoveries of 72.66% to 85.99% with standard deviation less than 0.01mg/10g dry weight are obtained except for p-hydroxybenzaldehyde. The lignin content ∑8 (produced from 10g dry sediment) in the research area is between 0.231 and 0.587mg. S/V and C/V ratios (1.028 ± 0.433 and 0.192±0.066, respectively) indicate that the TOMs in this region are originated from a mixture of woody and nonwoody angiosperm plants; the high values or (Ad/Al)v suggest that the TOMs has been highly degraded.展开更多
Continued innovation in screening methodologies remains important for the discovery of high-quality multiactive fungi,which have been of great significance to the development of new drugs.Mangrove-derived fungi,which ...Continued innovation in screening methodologies remains important for the discovery of high-quality multiactive fungi,which have been of great significance to the development of new drugs.Mangrove-derived fungi,which are well recognized as prolific sources of natural products,are worth sustained attention and further study.In this study,118 fungi,which mainly included Aspergillus spp.(34.62%)and Penicillium spp.(15.38%),were isolated from the mangrove ecosystem of the Maowei Sea,and 83.1%of the cultured fungi showed at least one bioactivity in four antibacterial and three antioxidant assays.To accurately evaluate the fungal bioactivities,the fungi with multiple bioactivities were successfully evaluated and screened by principal component analysis(PCA),and this analysis provided a dataset for comparing and selecting multibioactive fungi.Among the 118 mangrove-derived fungi tested in this study,Aspergillus spp.showed the best comprehensive activity.Fungi such as A.clavatonanicus,A.flavipes and A.citrinoterreus,which exhibited high comprehensive bioactivity as determined by the PCA,have great potential in the exploitation of natural products and the development of new drugs.This study demonstrated the first use of PCA as a time-saving,scientific method with a strong ability to evaluate and screen multiactive fungi,which indicated that this method can affect the discovery and development of new drugs.展开更多
Abstract Elements and natural radionuclides in the contact zone of two granites with different ages would migrate from one to the other because of the difference in their chemical contents and later water-rock interac...Abstract Elements and natural radionuclides in the contact zone of two granites with different ages would migrate from one to the other because of the difference in their chemical contents and later water-rock interactions. This migration could serve as an analogue for the near-field process of radwastes in a high-level radwaste deep geological disposal repository.展开更多
This study examined levels of polycyclic aromatic hydrocarbons (PAHs) in estuarine sediments in Licun (Qingdao, China) by gas chromatography under optimized conditions for sample pretreatment via ultrasonic extraction...This study examined levels of polycyclic aromatic hydrocarbons (PAHs) in estuarine sediments in Licun (Qingdao, China) by gas chromatography under optimized conditions for sample pretreatment via ultrasonic extraction, column chromatography, and thin layer chromatography. Methanol and dichloromethane (DCM)/methanol (2:1, v/v) were used in ultrasonic extraction, and DCM was used as eluate for column chromatography. The developing system consisted of n-hexane and DCM at a ratio of 9:1 (v/v), with DCM as the extraction solvent for PAHs-containing silica gel scraped off the plate. When the spiking level is 100 ng, total recoveries of spiked matrices for four target PAHs (phenanthrene, anthracene, pyrene and chrysene) were 83.7%, 76.4%, 85.8%, and 88.7%, respectively, with relative standard deviation (RSD) between 5.0% and 6.5% (n = 4). When the spiking level is 1000 ng, associated total recoveries were 78.6%, 72.7%, 82.7% and 85.3%, respectively, with RSD between 4.4% and 5.3% (n = 4). The opti-mized method was advantageous for determination of PAHs in complex matrix due to its effective sample purification.展开更多
The procedures of ultrasonic extraction and clean-up were optimized for the determination of polycyclic aromatic hydrocarbons (PAHs) in marine sediments. Samples were ultrasonically extracted, and the extracts were pu...The procedures of ultrasonic extraction and clean-up were optimized for the determination of polycyclic aromatic hydrocarbons (PAHs) in marine sediments. Samples were ultrasonically extracted, and the extracts were purified with a miniaturized silica gel chromatographic column and analyzed with high performance liquid chromatography (HPLC) with a fluorescence detector. Ultrasonication with methanol-dichloromethane (2:1, v/v) mixture gave higher extraction efficiency than that with dichloromethane. Among the three elution solvents used in clean-up step, dichloromethane-hexane (2:3, v/v) mixture was the most satisfactory. Under the optimized conditions, the recoveries in the range of 54.82% to 94.70% with RSDs of 3.02% to 23.22% for a spiked blank, and in the range of 61.20% to 127.08% with RSDs of 7.61% to 26.93% for a spiked matrix, were obtained for the 15 PAHs studied, while the recoveries for a NIST standard reference SRM 1941b were in the range of 50.79% to 83.78% with RSDs of 5.24% to 21.38%. The detection limits were between 0.75 ng L-1 and 10.99 ng L-1for different PAHs. A sample from the Jiaozhou Bay area was examined to test the established methods.展开更多
The relationship between chemical structures and photodegradation activity of 12 PAHs is studied using DFT and HF methods, and stepwise multiple linear regression analysis method. The equilibrium geometries and vibrat...The relationship between chemical structures and photodegradation activity of 12 PAHs is studied using DFT and HF methods, and stepwise multiple linear regression analysis method. The equilibrium geometries and vibration frequency have been investigated by considering Solvent effects using a selfconsistent reaction field based on the polarizable continuum model. With DFT and HF methods, different quantum chemical structural descriptors are obtained by quantum chemical calculation and the results with DFT method are better for QSAR model. It is concluded that the photodegradation activity is closely related to its molecular structure. In the regression analysis, the main factors affecting photodegradation rate include the energy of the highest occupied orbital EHOMO and the number of six-carbon benzene ring N1, and the QSAR model successfully established is logkb = 6.046 + 54.830EHOMO + 0.272N1. Statistical evaluation of the developed QSAR shows that the relationships are statistically significant and the model has good predictive ability. EHOMO is the most important factor influcing the photodegradation of PAHs, because the higher EHOMO is, the more easily electron will be excited and the more easily molecular will be degraded. Comparison of the photodegradation of PAHs with their biodegradation shows that the committed step of biodegradation is that the effects of microorganisms make the chemical bond break, while in the committed step of photodegradation PAHs eject electrons.展开更多
The area of East China Sea(ECS)inner shelf is an important sink of suspended particulates from Yangtze River(YR)and materials originated from YR basin.In this study,the parameters of lignin and alkane biomarkers in su...The area of East China Sea(ECS)inner shelf is an important sink of suspended particulates from Yangtze River(YR)and materials originated from YR basin.In this study,the parameters of lignin and alkane biomarkers in surface sediment samples from ECS inner shelf were determined to distinguish the sources and to trace the transport of terrigenous organic matters in the region.Our dataset showed that total alkanes with carbon numbers from 10 to 38(T-alkanes)were significantly correlated to both TAR(terrigenous/aquatic ratio)and HMW/LMW(the ratio of high molecular weight to low molecular weight alkanes)(r=0.88,P<0.05 for both),indicating that the majority of T-alkanes was predominantly originated from terrestrial sources,and T-alkanes are important constituents of terrestrial organic matters in the study area.The area was probably affected by petroleum pollution to a certain degree,as indicated by the values of carbon preference index(CPI),odd-over-even carbon number predominance(OEP)and the ratio of pristane to phytane(Pr/Ph).The values of Pr/n-C_(17) and Ph/n-C_(18) suggested a strong reductive sedimentary condition in the region with no obvious biodegradation.The content of eight lignin phenols(Σ8)decreased from the coast to the open sea,indicative of riverine input and hydrodynamic transport of terrigenous organic matters.Lignin degradation parameters presented an increasing trend from the coastline toward the open sea.The lignin vegetation parameters and alkane index(AI)suggested the predominance of non-woody angiosperms in the YR basin.The obvious correlation betweenΛ8(Σ8 normalized to 100 mg organic carbon),TAR and HMW/LMW reveals the significantly concurrent input of lignin and alkanes from terrestrial sources.展开更多
Solid superacid SO_(4)^(2−)/ZrO_(2)as heterogeneous catalyst was prepared to upgrade the bio-oil in the progress of hydrother-mal liquefaction(HTL)for the represented algae of Chlorella vulgaris and Enteromorpha proli...Solid superacid SO_(4)^(2−)/ZrO_(2)as heterogeneous catalyst was prepared to upgrade the bio-oil in the progress of hydrother-mal liquefaction(HTL)for the represented algae of Chlorella vulgaris and Enteromorpha prolifera.The solid superacid catalyst could obviously adjust the composition of the bio-oil and improve the higher heating values(HHVs).The catalytic performance could be regulated by adjusting the acid amount and acid strength of SO_(4)^(2−)/ZrO_(2).Furthermore,it was explored the catalytic effects of SO_(4)^(2−)/ZrO_(2)by the HTL for algae major model components,including polysaccharides,proteins,lipids,binary mixture and ternary mixture.The results showed that the introducing of SO_(4)^(2−)/ZrO_(2)catalyst could increase the yields of bio-oil from proteins and lipids,and avoid the Maillard reaction between polysaccharides and proteins.Moreover,a possible reaction pathway and mechanisms has proposed for the formation of bio-oils from HTL of algae catalyzed by SO_(4)^(2−)/ZrO_(2)based on the systematic research of the producing bio-oil from major model components.展开更多
基金supported by the Central Public-Interest Scientific Institution Basal Research Fund,CAFS(No.2020TD71).
文摘A precise and reliable analytical method of high performance liquid chromatography-tandem mass spectrometry(HPLCMS/MS)was developed to measure trace levels of enrofloxacin(ENR)and its major metabolite ciprofloxacin(CIP)in carp tissues.Optimized chromatographic separation was obtained on a Waters Xterra MS C_(18) reversed-phase column using gradient elution with methanol and 0.1%formic acid aqueous solution including 5mmolL^(-1) of ammonium acetate.The established method was applied to study the pharmacokinetics and distribution of ENR and CIP in tissues of carp following a single oral administration in feed at a dosage of 40mgkg^(-1) bw(body weight).Data were analyzed using DAS 2.0 dynamics software,and the experimental results suggest that ENR was rapidly absorbed and extensively distributed in carp tissues through systemic circulation,and the pharmacokinetic characteristics can be described with a two-compartment model.The elimination half-lives(t_(1/2β))from muscle,liver,gill,plasma and skin were 131,160,104,132 and 310 h,respectively.The areas under the drug concentration-time curves(AUC)for these tissues were 491,972,750,249 and 706hmgkg^(-1),respectively.The maximum concentration(C_(max))values were 13,29,37,9 and 5mgkg^(-1) with peak times(t_(max))of 8,4,4,2 and 4 h,respectively.Ciprofloxacin,the active metabolite of ENR,was also detected in carp tissues,indicating that only 1.54%of de-ethylation of ENR occurs in carp.At a water temperature of 18℃,the drug withdrawal time was determined to be no less than 24 d while the carp was fed at a single dosage of 40mgkg^(-1).
基金supported by the National Natural Science Foundation of China(No.41276067)the Air Liquide(China)R&D Co.,Ltd.(No.20200216).
文摘The synergetic effect and underlying mechanism of potassium ferrate(PF)with tea saponin(TS,a biosurfactant)in producing short chain fatty acids(SCFAs)from anaerobic fermentation of waste activated sludge(WAS)were explored in this work.Experimental results showed that 0.2 g PF(g TSS)^(-1)(total suspended solid)combined with 0.02 g TS(g TSS)^(-1) could further improve SCFAs’production,and the maximum SCFAs content reached 2008.7 mg COD L^(-1),which is 1.2 and 4.5 times higher than those with PF and TS individually added,respectively,and 5.3 times higher than that of blank WAS on Day 12.In the model substrates experiments,the degradation rates of bovine serum albumin and dextran with combination of PF and TS were 41.3%±0.1% and 48.5%±0.06%,respectively,on Day 3,which are lower than those in blank WAS(with degradation rates of 72.3%±0.5%and 90.3%±0.3%).It was revealed that the oxidative effect of PF and the solubilization of TS caused more organic matters to be dissolved out from WAS,providing a large number of biodegradable substances for subsequent SCFAs production.While WAS pretreated with the combination of PF and TS,the relative abundances of Firmicutes increased from 6.4%(blank)to 38.6%,and that of Proteobacteria decreased from 41.8%(blank)to 21.8%.The combination of PF and TS promoted the hydrolysis process of WAS by enriching Firmicutes,and then increased acetic acid production by inhibiting Proteobacteria that consumed SCFAs.Meanwhile,at the genus level,acidogenesis bacteria(e.g.,Proteiniclasticum and Petrimonas)were enriched whereas SCFAs consuming bacteria(e.g.,Dokdonella)were inhibited.
基金financially supported by the National Natural Science Foundation of China(NSFC)(No.42377217)the Cooperation Fund between Dongying City and Universities(No.SXHZ-2023-02-6).
文摘Per-and polyfluoroalkyl substances(PFASs)are emerging persistent organic pollutants(POPs).In this study,47 surface sediment samples were collected from the Yellow River Delta wetland(YRDW)to investigate the occurrence,spatial distribution,potential sources,and ecological risks of PFASs.Twenty-three out of 26 targeted PFASs were detected in surface sediment samples from the YRDW,with totalΣ23PFASs concentrations ranging from 0.23 to 16.30 ng g^(-1) dw and a median value of 2.27 ng g^(-1) dw.Perfluorooctanoic acid(PFOA),perfluorobutanoic acid(PFBA)and perfluorooctanesulfonic acid(PFOS)were the main contaminants.The detection frequency and concentration of perfluoroalkyl carboxylic acids(PFCAs)were higher than those of perfluoroal-kanesulfonic acids(PFSAs),while those of long-chain PFASs were higher than those of short-chain PFASs.The emerging PFASs substitutes were dominated by 6:2 chlorinated polyfluoroalkyl ether sulfonic acid(6:2 Cl-PFESA).The distribution of PFASs is significantly influenced by the total organic carbon content in the sediments.The concentration of PFASs seems to be related to human activities,with high concentration levels of PFASs near locations such as beaches and villages.By using a positive matrix factorization model,the potential sources of PFASs in the region were identified as metal plating mist inhibitor and fluoropolymer manufacturing sources,metal plating industry and firefighting foam and textile treatment sources,and food packaging material sources.The risk assessment indicated that PFASs in YRDW sediments do not pose a significant ecological risk to benthic organisms in the region overall,but PFOA and PFOS exert a low to moderate risk at individual stations.
基金supported by the National Basic Research Program of China (973 Program, Grant No. 2010CB428901)the National Natural Science Foundation of China (NSFC, Grant No. 41020164005,41276067)the team of 973 Program Grant No. 2010CB428701 for the help during sampling
文摘Lignin serves as one of the most important molecular fossils for tracing Terrestrial Organic Matters (TOMs) in marine environment. Extraction and derivatization of lignin oxidation products (LOPs) are crucial for accurate quantification of lignin in marine sediment. Here we report a modification of the conventional alkaline cupric oxide (CuO) oxidation method, the modification consisting in a solid phase extraction (SPE) and a novel on-column derivatization being employed for better efficiency and reproducibility. In spiking blanks, recoveries with SPE for the LOPs are between 77.84% and 99.57% with relative standard deviations (RSDs) ranging from 0.57% to 8.04% (n=3), while those with traditional liquid-liquid extraction (LLE) are from 44.52% to 86.16% With RSDs being from 0.53% to 13.14% (n=3). Moreover, the reproducibility is greatly improved with SPE, with less solvent consumption and shorter processing time. The average efficiency of on-column derivatization for LOPs is 100.8%±0.68%, which is significantly higher than those of in-vial or in-syringe derivatization, thus resulting in still less consumption of derivatizing reagents.Lignin in the surface sediments sampled from the south of Yangtze River estuary, China, was determined with the established method. Recoveries of 72.66% to 85.99% with standard deviation less than 0.01mg/10g dry weight are obtained except for p-hydroxybenzaldehyde. The lignin content ∑8 (produced from 10g dry sediment) in the research area is between 0.231 and 0.587mg. S/V and C/V ratios (1.028 ± 0.433 and 0.192±0.066, respectively) indicate that the TOMs in this region are originated from a mixture of woody and nonwoody angiosperm plants; the high values or (Ad/Al)v suggest that the TOMs has been highly degraded.
基金the Key R&D Program of Shandong Province(No.2020CXGC010703)the Key Project of the Natural Science Foundation of Shandong Province(No.ZR2020 KB021)。
文摘Continued innovation in screening methodologies remains important for the discovery of high-quality multiactive fungi,which have been of great significance to the development of new drugs.Mangrove-derived fungi,which are well recognized as prolific sources of natural products,are worth sustained attention and further study.In this study,118 fungi,which mainly included Aspergillus spp.(34.62%)and Penicillium spp.(15.38%),were isolated from the mangrove ecosystem of the Maowei Sea,and 83.1%of the cultured fungi showed at least one bioactivity in four antibacterial and three antioxidant assays.To accurately evaluate the fungal bioactivities,the fungi with multiple bioactivities were successfully evaluated and screened by principal component analysis(PCA),and this analysis provided a dataset for comparing and selecting multibioactive fungi.Among the 118 mangrove-derived fungi tested in this study,Aspergillus spp.showed the best comprehensive activity.Fungi such as A.clavatonanicus,A.flavipes and A.citrinoterreus,which exhibited high comprehensive bioactivity as determined by the PCA,have great potential in the exploitation of natural products and the development of new drugs.This study demonstrated the first use of PCA as a time-saving,scientific method with a strong ability to evaluate and screen multiactive fungi,which indicated that this method can affect the discovery and development of new drugs.
文摘Abstract Elements and natural radionuclides in the contact zone of two granites with different ages would migrate from one to the other because of the difference in their chemical contents and later water-rock interactions. This migration could serve as an analogue for the near-field process of radwastes in a high-level radwaste deep geological disposal repository.
基金supported by the National Natural Science Foundation of China (NSFC project 20775074)
文摘This study examined levels of polycyclic aromatic hydrocarbons (PAHs) in estuarine sediments in Licun (Qingdao, China) by gas chromatography under optimized conditions for sample pretreatment via ultrasonic extraction, column chromatography, and thin layer chromatography. Methanol and dichloromethane (DCM)/methanol (2:1, v/v) were used in ultrasonic extraction, and DCM was used as eluate for column chromatography. The developing system consisted of n-hexane and DCM at a ratio of 9:1 (v/v), with DCM as the extraction solvent for PAHs-containing silica gel scraped off the plate. When the spiking level is 100 ng, total recoveries of spiked matrices for four target PAHs (phenanthrene, anthracene, pyrene and chrysene) were 83.7%, 76.4%, 85.8%, and 88.7%, respectively, with relative standard deviation (RSD) between 5.0% and 6.5% (n = 4). When the spiking level is 1000 ng, associated total recoveries were 78.6%, 72.7%, 82.7% and 85.3%, respectively, with RSD between 4.4% and 5.3% (n = 4). The opti-mized method was advantageous for determination of PAHs in complex matrix due to its effective sample purification.
基金supported by the National Natural Science Foundation of China (Grant No.20775074)
文摘The procedures of ultrasonic extraction and clean-up were optimized for the determination of polycyclic aromatic hydrocarbons (PAHs) in marine sediments. Samples were ultrasonically extracted, and the extracts were purified with a miniaturized silica gel chromatographic column and analyzed with high performance liquid chromatography (HPLC) with a fluorescence detector. Ultrasonication with methanol-dichloromethane (2:1, v/v) mixture gave higher extraction efficiency than that with dichloromethane. Among the three elution solvents used in clean-up step, dichloromethane-hexane (2:3, v/v) mixture was the most satisfactory. Under the optimized conditions, the recoveries in the range of 54.82% to 94.70% with RSDs of 3.02% to 23.22% for a spiked blank, and in the range of 61.20% to 127.08% with RSDs of 7.61% to 26.93% for a spiked matrix, were obtained for the 15 PAHs studied, while the recoveries for a NIST standard reference SRM 1941b were in the range of 50.79% to 83.78% with RSDs of 5.24% to 21.38%. The detection limits were between 0.75 ng L-1 and 10.99 ng L-1for different PAHs. A sample from the Jiaozhou Bay area was examined to test the established methods.
基金supported by the National Natural Science Foundation of China(Nos.40976041 and 20775074)
文摘The relationship between chemical structures and photodegradation activity of 12 PAHs is studied using DFT and HF methods, and stepwise multiple linear regression analysis method. The equilibrium geometries and vibration frequency have been investigated by considering Solvent effects using a selfconsistent reaction field based on the polarizable continuum model. With DFT and HF methods, different quantum chemical structural descriptors are obtained by quantum chemical calculation and the results with DFT method are better for QSAR model. It is concluded that the photodegradation activity is closely related to its molecular structure. In the regression analysis, the main factors affecting photodegradation rate include the energy of the highest occupied orbital EHOMO and the number of six-carbon benzene ring N1, and the QSAR model successfully established is logkb = 6.046 + 54.830EHOMO + 0.272N1. Statistical evaluation of the developed QSAR shows that the relationships are statistically significant and the model has good predictive ability. EHOMO is the most important factor influcing the photodegradation of PAHs, because the higher EHOMO is, the more easily electron will be excited and the more easily molecular will be degraded. Comparison of the photodegradation of PAHs with their biodegradation shows that the committed step of biodegradation is that the effects of microorganisms make the chemical bond break, while in the committed step of photodegradation PAHs eject electrons.
基金This study was financially supported by the National Natural Science Foundation of China(Nos.41276067,41020164005)the National Basic Research Program of China(973 Program,No.2010CB428901).
文摘The area of East China Sea(ECS)inner shelf is an important sink of suspended particulates from Yangtze River(YR)and materials originated from YR basin.In this study,the parameters of lignin and alkane biomarkers in surface sediment samples from ECS inner shelf were determined to distinguish the sources and to trace the transport of terrigenous organic matters in the region.Our dataset showed that total alkanes with carbon numbers from 10 to 38(T-alkanes)were significantly correlated to both TAR(terrigenous/aquatic ratio)and HMW/LMW(the ratio of high molecular weight to low molecular weight alkanes)(r=0.88,P<0.05 for both),indicating that the majority of T-alkanes was predominantly originated from terrestrial sources,and T-alkanes are important constituents of terrestrial organic matters in the study area.The area was probably affected by petroleum pollution to a certain degree,as indicated by the values of carbon preference index(CPI),odd-over-even carbon number predominance(OEP)and the ratio of pristane to phytane(Pr/Ph).The values of Pr/n-C_(17) and Ph/n-C_(18) suggested a strong reductive sedimentary condition in the region with no obvious biodegradation.The content of eight lignin phenols(Σ8)decreased from the coast to the open sea,indicative of riverine input and hydrodynamic transport of terrigenous organic matters.Lignin degradation parameters presented an increasing trend from the coastline toward the open sea.The lignin vegetation parameters and alkane index(AI)suggested the predominance of non-woody angiosperms in the YR basin.The obvious correlation betweenΛ8(Σ8 normalized to 100 mg organic carbon),TAR and HMW/LMW reveals the significantly concurrent input of lignin and alkanes from terrestrial sources.
基金supported by the Shandong Provincial Natural Science Foundation,China(No.ZR2019BB 033)the Fundamental Research Funds for the Central Universities of Ocean University of China(No.201813031).
文摘Solid superacid SO_(4)^(2−)/ZrO_(2)as heterogeneous catalyst was prepared to upgrade the bio-oil in the progress of hydrother-mal liquefaction(HTL)for the represented algae of Chlorella vulgaris and Enteromorpha prolifera.The solid superacid catalyst could obviously adjust the composition of the bio-oil and improve the higher heating values(HHVs).The catalytic performance could be regulated by adjusting the acid amount and acid strength of SO_(4)^(2−)/ZrO_(2).Furthermore,it was explored the catalytic effects of SO_(4)^(2−)/ZrO_(2)by the HTL for algae major model components,including polysaccharides,proteins,lipids,binary mixture and ternary mixture.The results showed that the introducing of SO_(4)^(2−)/ZrO_(2)catalyst could increase the yields of bio-oil from proteins and lipids,and avoid the Maillard reaction between polysaccharides and proteins.Moreover,a possible reaction pathway and mechanisms has proposed for the formation of bio-oils from HTL of algae catalyzed by SO_(4)^(2−)/ZrO_(2)based on the systematic research of the producing bio-oil from major model components.