QuEChERS-GC/MS法解析枯草芽胞杆菌降解白菜叶际毒死蜱残留特性
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摘要
在中国,毒死蜱作为替代高毒有机磷农药的最佳选择之一,已被广泛用于控制蔬菜生产过程中病虫害,然其带来的食品安全问题引起了人们越来越多的关注,因此建立快速检测毒死蜱残留的新方法显得尤为重要。本研究构建了一种改进的QuEChERS样品预处理和气相色谱-质谱(GC-MS)联用法,以快速测定白菜叶际毒死蜱的残留量。样品用含1%乙酸的乙腈提取,用适量N-丙基乙二胺(PSA)、无水MgSO_4、石墨化炭黑(GCB)和C18填料净化,GC-MS检测,外标法定量。结果表明:毒死蜱在质量浓度为0.20～1.00mg/L时,线性关系良好,R大于0.999;添加水平为0.10～0.50 mg/kg时,平均回收率为72.00%～111.00%,相对标准偏差为1.30%～1.60%,检出限(LOD)为0.005 mg/kg,定量限(LOQ)为0.01 mg/kg。该方法简便、快速、准确、灵敏,能够满足白菜叶际毒死蜱残留的定性和定量分析检测。枯草芽胞杆菌3374对白菜叶际毒死蜱残留具备有效降解能力。
In China, chlorpyrifos, as one of the most suitable pesticides to replace the highly toxic organophosphorus pesticides, has been widely used to control pests and diseases in vegetable production. However, the food safety problems brought by chlorpyrifos have attracted more and more attention. Therefore, it is very important to establish new methods for rapid detection of chlorpyrifos residues. In this study, an improved method, QuEChERS sample pretreatment coupled to gas chromatography-mass spectrometry(GC-MS) has been developed for rapid detection of the residual amount of chlorpyrifos on the phyllosphere of Brassica chinensis. The sample was extracted with acetonitrile containing1% acetic acid, and purified with an appropriate amount of N-propyl Ethylenediamine(PSA), anhydrous magnesium sulfate, graphitized carbon black(GCB) and C18 filler, before analysis by gas chromatography-mass spectrometry and quantification with external standards. The obtained results showed a good linear relationship in the concentration range of 0.20～1.00 mg/L with correlation coefficients greater than 0.999. When the spiked level was 0.10～0.50 mg/kg, the average recoveries of chlorpryrifos were 72.00%～111.00%, with the relative standard deviations as1.30%～1.60%, limit of detection(LOD) as 0.005 mg/kg, and limit of quantitation(LOQ) as 0.01 mg/kg. The established method is simple, rapid,accurate and sensitive, and can meet the requirements for qualitative and quantitative analysis of the residues of chlorpyrifos on the phyllosphere of Brassica chinensis. Bacillus subtilis 3374 could degrade effectively the chlorpyrifos residues on the phyllosphere of Chinese cabbage.
In China, chlorpyrifos, as one of the most suitable pesticides to replace the highly toxic organophosphorus pesticides, has been widely used to control pests and diseases in vegetable production. However, the food safety problems brought by chlorpyrifos have attracted more and more attention. Therefore, it is very important to establish new methods for rapid detection of chlorpyrifos residues. In this study, an improved method, QuEChERS sample pretreatment coupled to gas chromatography-mass spectrometry(GC-MS) has been developed for rapid detection of the residual amount of chlorpyrifos on the phyllosphere of Brassica chinensis. The sample was extracted with acetonitrile containing1% acetic acid, and purified with an appropriate amount of N-propyl Ethylenediamine(PSA), anhydrous magnesium sulfate, graphitized carbon black(GCB) and C18 filler, before analysis by gas chromatography-mass spectrometry and quantification with external standards. The obtained results showed a good linear relationship in the concentration range of 0.20～1.00 mg/L with correlation coefficients greater than 0.999. When the spiked level was 0.10～0.50 mg/kg, the average recoveries of chlorpryrifos were 72.00%～111.00%, with the relative standard deviations as1.30%～1.60%, limit of detection(LOD) as 0.005 mg/kg, and limit of quantitation(LOQ) as 0.01 mg/kg. The established method is simple, rapid,accurate and sensitive, and can meet the requirements for qualitative and quantitative analysis of the residues of chlorpyrifos on the phyllosphere of Brassica chinensis. Bacillus subtilis 3374 could degrade effectively the chlorpyrifos residues on the phyllosphere of Chinese cabbage.
引文
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[14]WU CC.Multiresidue method for the determination of pesticides in Oolong tea using Qu ECh ERS by gas chromatography-triple quadrupole tandem mass spectrometry[J].Food Chemistry,2017,229:580-587
[15]Rossini D,Ciofi L,Ancillotti C,et al.Innovative combination of Qu ECh ERS extraction with on-line solid-phase extract purification and pre-concentration,followed by liquid chromatography-tandem mass spectrometry for the determination of non-steroidal anti-inflammatory drugs and their metabolites in sewage sludge[J].Analytica Chimica Acta,2016,935:269-281
[16]Nantia E A,Mpreno-Gonzalez D,Manfo F,et al.Qu ECh ERS-based method for the determination of carbamate residues in aromatic herbs by UHPLC-MS/MS[J].Food Chemistry,2017,216:334-341
[17]Chahkandi M,Amiri A,Arami Srs.Extraction and preconcentration of organophosphorus pesticides from water samples and fruit juices utilizing hydroxyapatite/Fe3O4nanocomposite[J].Microchemical Journal,2019,144(1):261-269
[18]SKI P K.Large-scale multi-class herbicides analysis in oilseeds by rapid one-step Qu ECh ERS-based extraction and cleanup method using liquid chromatography-tandem mass spectrometry[J].Food Chemistry,2017,230:411-422
[19]田憬若,陈文,张长江,等.不同前处理方法对蔬菜中有机磷农药残留检测的影响[J].现代食品科技,2013,29(3):664-667TIAN Jing-ruo,CHEN Wen,ZHANG Chang-jiang,et al.Effect of different pre-treatment methods on detection results of organophosphorus pesticide residue vegetables[J].Modern Food Science and Technology,2013,29(3):664-667
[20]Rasoulnezhad H,Kavei G,Ahmadi K,et al.Visible light photo-catalytic degradation of paraoxon and parathion pesticides on carbon-doped Ti O2 nanorod thin flms[J].Journal of Materials Science:Materials in Electronics,2017,28(24):18337-18347
[21]Khan S,He X,Khan J A,et al.Kinetics and mechanism of sulfate radical-and hydroxyl radical-induced degradation of highly chlorinated pesticide Lindane in UV/peroxymonosulfate system[J].Chem.Eng.J.,2017,318,135-142
[22]Kumar S,Kaushik G,Dar,M A,et al.Microbial degradation of organophosphate pesticides:A review[J].Pedosphere,2018,28(2):190-208
[23]Xue Zhang,Yugang Gao,Pu Zhang,et al.Study on the simultaneous degradation of fve pesticides by Paenibacillus polymyxa from Panax ginseng and the characteristics of their products[J].Ecotoxicology and Environmental Safety,2019,168:415-422
[2]Katsikantami I,Colosio C,Alegakis A,et al.Estimation of daily intake and risk assessment of organophosphorus pesticides based on biomonitoring data-the internal exposure approach[J].Food and Chemical Toxicology,2019,123:57-71
[3]WANG RY,PAN JP,QIN M,et al.Molecularly imprinted nanocapsule mimicking phosphotriesterase for the catalytic hydrolysis of organophosphorus pesticides[J].European Polymer Journal,2019,110:1-8
[4]Swamam T P,Velmurugan A.Pesticide residues in vegetable samples from the Andaman Islands,India[J].Environmental Monitoring and Assessment,2013,185(7):6119-6127
[5]LIANG WQ,WANG JT,ZANG XH,et al.Barley husk carbon as the fiber coating for the solid-phasemicroextraction of twelve pesticides in vegetables prior to gaschromatography-mass spectrometric detection[J].Journal of Chromatography A,2017,1491:9-15
[6]YU R,LIU Q,LIU JH,et al.Concentrations of organophosphorus pesticides in fresh vegetables and related human health risk assessment in Changchun,Northeast China[J].Food Control,2016,60:353-360
[7]GE J,LU MX,WANG DL,et al.Dissipation and distribution of chlorpyrifos in selected vegetables through foliage and root uptake[J].Chemosphere,2016,144:201-206
[8]严寒,郭平,骆鹏杰,等.近红外光谱结合膜富集技术测定大米中毒死蜱农药残留[J].现代食品科技,2017,33(4):289-294YAN Han,GUO Ping,LUO Peng-jie,et al.Determination of chlorpyrifos pesticide residues in rice by NIR spectroscopy coupled with a membrane enrichment technique[J].Modern Food Science and Technology,2017,33(4):289-294
[9]LIU J,TAN LM,WANG J,et al.Complete biodegradation of chlorpyrifos by engineered Pseudomonas putida cells expressing surface-immobilized laccases[J].Chemosphere,2016,157:200-207
[10]Utzig L M,Lima R M,Gomes M F,et al.Ecotoxicity response of chlorpyrifos in Aedes aegypti larvae and Lactuca sativa seeds after UV/H2O2 and UVC oxidation[J].Ecotoxicology and Environmental Safety,2019,169(3):449-456
[11]Aznar R,Albero B,Sanchez-Brunete C,et al.Simultaneous determination of multiclass emerging contaminants in aquatic plants by ultrasound-assisted matrix solid-phase dispersion and GC-MS[J].Environonmental Science and Pollution Research,2017,24(9):7911-7920
[12]王辉,段玉瑶,李笑,等.基于纳米四氧化三铁/壳聚糖/石墨烯纳米复合膜修饰的乙酰胆碱酯酶生物传感器检测毒死蜱农药[J].现代食品科技,2016,32(2):276-282WANG Hui,DUAN Yu-yao,LI Xiao,et al.A sensitive acetylcholinesterase biosensor based on nanocomposite films of ferroferric oxide nanoparticle,chitosan,and graphene for the detection of chlorpyrifos pesticide[J].Modern Food Science and Technology,2016,32(2):276-282
[13]Valente N,Tarelho S,Castro Al,et al.Analysis of organophosphorus pesticides in whole blood by GC-MS-m ECD with forensic purposes[J].Journal of Forensic and Legal Medicine,2015,33:28-34
[14]WU CC.Multiresidue method for the determination of pesticides in Oolong tea using Qu ECh ERS by gas chromatography-triple quadrupole tandem mass spectrometry[J].Food Chemistry,2017,229:580-587
[15]Rossini D,Ciofi L,Ancillotti C,et al.Innovative combination of Qu ECh ERS extraction with on-line solid-phase extract purification and pre-concentration,followed by liquid chromatography-tandem mass spectrometry for the determination of non-steroidal anti-inflammatory drugs and their metabolites in sewage sludge[J].Analytica Chimica Acta,2016,935:269-281
[16]Nantia E A,Mpreno-Gonzalez D,Manfo F,et al.Qu ECh ERS-based method for the determination of carbamate residues in aromatic herbs by UHPLC-MS/MS[J].Food Chemistry,2017,216:334-341
[17]Chahkandi M,Amiri A,Arami Srs.Extraction and preconcentration of organophosphorus pesticides from water samples and fruit juices utilizing hydroxyapatite/Fe3O4nanocomposite[J].Microchemical Journal,2019,144(1):261-269
[18]SKI P K.Large-scale multi-class herbicides analysis in oilseeds by rapid one-step Qu ECh ERS-based extraction and cleanup method using liquid chromatography-tandem mass spectrometry[J].Food Chemistry,2017,230:411-422
[19]田憬若,陈文,张长江,等.不同前处理方法对蔬菜中有机磷农药残留检测的影响[J].现代食品科技,2013,29(3):664-667TIAN Jing-ruo,CHEN Wen,ZHANG Chang-jiang,et al.Effect of different pre-treatment methods on detection results of organophosphorus pesticide residue vegetables[J].Modern Food Science and Technology,2013,29(3):664-667
[20]Rasoulnezhad H,Kavei G,Ahmadi K,et al.Visible light photo-catalytic degradation of paraoxon and parathion pesticides on carbon-doped Ti O2 nanorod thin flms[J].Journal of Materials Science:Materials in Electronics,2017,28(24):18337-18347
[21]Khan S,He X,Khan J A,et al.Kinetics and mechanism of sulfate radical-and hydroxyl radical-induced degradation of highly chlorinated pesticide Lindane in UV/peroxymonosulfate system[J].Chem.Eng.J.,2017,318,135-142
[22]Kumar S,Kaushik G,Dar,M A,et al.Microbial degradation of organophosphate pesticides:A review[J].Pedosphere,2018,28(2):190-208
[23]Xue Zhang,Yugang Gao,Pu Zhang,et al.Study on the simultaneous degradation of fve pesticides by Paenibacillus polymyxa from Panax ginseng and the characteristics of their products[J].Ecotoxicology and Environmental Safety,2019,168:415-422