固相微萃取-气相色谱质谱联用法测定苹果中4种有机氯类农药残留
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摘要
[目的]建立固相微萃取气相色谱质谱联用法同时检测苹果中五氯硝基苯、六氯苯、七氯和百菌清4种有机氯类农药残留量的方法。[方法]采用正交试验优化萃取头类型、萃取时间、萃取温度、萃取搅拌速度和NaCl浓度,确定最优萃取条件,结合气相色谱质谱联用法对目标分析物进行分离和检测。[结果]固相微萃取(SPME)正交试验最优的萃取条件:65μm PDMS/DVB萃取头,50℃下萃取50 min,萃取搅拌速度为600 r/min,NaCl浓度为10%。4种目标分析物在线性范围内(0.02~2.00 mg/L)呈现良好的线性关系,相关系数均大于0.9992,回收率为83.3%~93.4%,相对标准偏差为2.5%~8.4%(n=6)。[结论]该方法快速简便,回收率、精密度均符合检测要求,适合苹果中多种有机氯类农药残留量的快速测定。
[Aims] A method was developed for the simultaneous determination of four organochlorine pesticides pentachloronitrobenzene, hexachlorobenzene, heptachlor and chlorothalonil residues in apple by solid phase microextraction coupled with gas chromatography-mass spectrometry. [Methods] The optimum extraction conditions such as fiber type, extraction time, extraction temperature, stirring speed and sodium chloride concentration, were determined by orthogonal design, and the pesticide residues were separated and determined by gas chromatographic-mass spectrometry. [Results] The optimal extraction conditions of SPME was carried out at 50 ℃ for 50 min using 65 μm PDMS/DVB fiber with a constant stirring speed of 600 r/min and 10% NaCl. In 0.02-2.00 mg/L, all the four targets could be completely separated with an excellent linear relationship, the correlation coefficients were all above 0.9992.The recoveries and RSD ranged from 83.3 to 93.4% and 2.5 to 8.4%, respectively. [Conclusions] The developed method is simple and rapid, both recoveries and precision can be used in determination of various organochlorine pesticide residues in apple.
[Aims] A method was developed for the simultaneous determination of four organochlorine pesticides pentachloronitrobenzene, hexachlorobenzene, heptachlor and chlorothalonil residues in apple by solid phase microextraction coupled with gas chromatography-mass spectrometry. [Methods] The optimum extraction conditions such as fiber type, extraction time, extraction temperature, stirring speed and sodium chloride concentration, were determined by orthogonal design, and the pesticide residues were separated and determined by gas chromatographic-mass spectrometry. [Results] The optimal extraction conditions of SPME was carried out at 50 ℃ for 50 min using 65 μm PDMS/DVB fiber with a constant stirring speed of 600 r/min and 10% NaCl. In 0.02-2.00 mg/L, all the four targets could be completely separated with an excellent linear relationship, the correlation coefficients were all above 0.9992.The recoveries and RSD ranged from 83.3 to 93.4% and 2.5 to 8.4%, respectively. [Conclusions] The developed method is simple and rapid, both recoveries and precision can be used in determination of various organochlorine pesticide residues in apple.
引文
[1]中国科学院中国植物志编委会.中国植物志:第14卷[M].北京:科学出版社,1994.
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[4]STEINBACH P,SCHWACK W.Comparison of Different Solidphase-extraction Cartridges for a Fatty Acid Cleanup of the Ethyl Acetate/Cyclohexane Based Multi-pesticide Residue Method EN 12393[J].Journal of Chromatography A,2014,1323:28-38.
[5]DONKOR A,OSEI-FOSU P,NYARKO S,et al.Validation of Qu ECh ERS Method for the Determination of 36 Pesticide Residues in Fruits and Vegetables from Ghana,using Gas Chromatography with Electron Capture and Pulsed Flame Photometric Detectors[J].Journal of Environmental Science and Health,2015,50(8):560-570.
[6]曾凯,孙国泉,唐俊,等.Qu ECh ERS-气质联用法同时测定土壤中16种农药残留[J].农药,2016,55(7):507-509.
[7]SERGIANE S C,CáTIA MARIAN B,JAIME M E,et al.AVortex-assisted MSPD Method for the Extraction of Pesticide Residues from Fish Liver and Crab Hepatopancreas with Determination by GC-MS[J].Talanta,2013(112):63-68.
[8]OUYANG Y F,TANG H B,WU Y,et al.Rapid Determination of Pesticide Multiresidues in Vegetables and Fruits by Accelerated Solvent Extraction Coupled with Online Gel Permeation Chromatography-gas Chromatography-mass Spectrometry[J].Chinese Journal of Chromatography,2012,30(7):654-659.
[9]MATSADIQ G,HAI Li-hua,HAI Bo-ren,et al.Quantification of Multi-residue Levels in Peach Juices,Pulps and Peels Using Dispersive Liquid-liquid Micro Extraction Based on Floating Organic Droplet Coupled with Gas Chromatography-electron Capture Detection[J].Journal of Chromatography B,2011,879(22):2113-2118.
[10]郭晓辰,饶竹,高冉.气相色谱法测定地下水中拟除虫菊酯有机氯百菌清等24种农药残留[J].岩矿测试,2014,33(3):406-412.
[11]TIAN Ming-ming,ZHANG Qing,SHI Hai-yan,et al.Simultaneous Determination of Chiral Pesticide Flufiprole Enantiomers in Vegetables,Fruits,and Soil by High-performance Liquid Chromatography[J].Analytical and Bioanalytical Chemistry,2015,407(12):3499-3507.
[12]GUAN Hong-xia,BREWER W E,GARRIS S T,et al.Disposable Pipette Extraction for the Analysis of Pesticides in Fruit and Vegetables Using Gas Chromatography/Mass Spectrometry[J].Journal of Chromatography A,2010,1217(12):1867-1874.
[13]刘一军,赖克强,戴月,等.分散液液微萃取-气质联用检测葡萄酒中的有机氯农药残留[J].光谱实验室,2013,30(1):228-233.
[14]陈军,张宗祥,杨文武,等.固相萃取-气质联用法测定水中有机氯农药和氯苯类化合物[J].环境监测管理与技术,2015,27(1):46-49.
[15]BRUCE D M,RICHARD B S.Development of an Automated Column Solid-phase Extraction Clean up of Qu ECh ERS Extracts,Using a Zirconia-based Sorbent,for Pesticide Residue Analyses by LC-MS/MS[J].Journal of Agricultural and Food Chemistry,2015,63(21):5107-5119.
[16]GONG Ling-ping,SHI Feng,JIANG Shu-yin,et al.Determination of Nine Pesticide Residues in Vegetables by Matrix Solidphase Dispersion-ultra Performance Liquid Chromatographytandem Mass Spectrometry[J].Chinese Journal of Chromatography,2015,33(4):408-412.
[17]ARUTHER C L,KILLAM L M.Analysis of Substituted Benzene Compounds in Groundwater Using Solid-phase Micro Extraction[J].Environmental Science and Technology,1992,26:979.
[18]彭华,李贝,张军,等.固相微萃取-气相色谱法测定水中硝基氯苯类化合物[J].中国环境监测,2015,31(5):124-128.
[19]刘海芳,马军辉,冯海强,等.固相微萃取法(SPME)在茶叶农残检测上的应用[J].茶叶,2007,33(3):136-139.
[20]裴永强,樊占春,赵静,等.顶空固相微萃取-气相色谱法测定水中氯苯类化合物[J].环境监测管理与技术,2014,26(6):39-45.
[21]赵英莲,牟德华,李艳,等.顶空固相微萃取联合气相色谱-质谱检测葡萄酒中2,4,6-三氯苯甲醚[J].食品科学,2016,37(10):219-225.
[22]刘潇威,买光熙,李凌云,等.NY/T 761-2008蔬菜和水果中有机磷、有机氯、拟除虫菊酯和氨基甲酸酯类农药多残留的测定[S].北京:中华人民共和国农业部,2008.
[23]CHUN Zhou-dong,ZHAO Rui-zeng,XIU Juan-li.Determination of Organochlorine Pesticides and Their Metabolites in Radish after Headspace Solid-phase Microextraction Using calix[4]Arene Fiber[J].Talanta,2005,66:721-727.
[2]华南农学院.植物化学保护[M].北京:农业出版社,1979:412.
[3]张曙明,郭怀忠,陈建民.甘草中有机氯类农药残留量的毛细管气相色谱测定[J].药学学报,2000,35(8):596-600.
[4]STEINBACH P,SCHWACK W.Comparison of Different Solidphase-extraction Cartridges for a Fatty Acid Cleanup of the Ethyl Acetate/Cyclohexane Based Multi-pesticide Residue Method EN 12393[J].Journal of Chromatography A,2014,1323:28-38.
[5]DONKOR A,OSEI-FOSU P,NYARKO S,et al.Validation of Qu ECh ERS Method for the Determination of 36 Pesticide Residues in Fruits and Vegetables from Ghana,using Gas Chromatography with Electron Capture and Pulsed Flame Photometric Detectors[J].Journal of Environmental Science and Health,2015,50(8):560-570.
[6]曾凯,孙国泉,唐俊,等.Qu ECh ERS-气质联用法同时测定土壤中16种农药残留[J].农药,2016,55(7):507-509.
[7]SERGIANE S C,CáTIA MARIAN B,JAIME M E,et al.AVortex-assisted MSPD Method for the Extraction of Pesticide Residues from Fish Liver and Crab Hepatopancreas with Determination by GC-MS[J].Talanta,2013(112):63-68.
[8]OUYANG Y F,TANG H B,WU Y,et al.Rapid Determination of Pesticide Multiresidues in Vegetables and Fruits by Accelerated Solvent Extraction Coupled with Online Gel Permeation Chromatography-gas Chromatography-mass Spectrometry[J].Chinese Journal of Chromatography,2012,30(7):654-659.
[9]MATSADIQ G,HAI Li-hua,HAI Bo-ren,et al.Quantification of Multi-residue Levels in Peach Juices,Pulps and Peels Using Dispersive Liquid-liquid Micro Extraction Based on Floating Organic Droplet Coupled with Gas Chromatography-electron Capture Detection[J].Journal of Chromatography B,2011,879(22):2113-2118.
[10]郭晓辰,饶竹,高冉.气相色谱法测定地下水中拟除虫菊酯有机氯百菌清等24种农药残留[J].岩矿测试,2014,33(3):406-412.
[11]TIAN Ming-ming,ZHANG Qing,SHI Hai-yan,et al.Simultaneous Determination of Chiral Pesticide Flufiprole Enantiomers in Vegetables,Fruits,and Soil by High-performance Liquid Chromatography[J].Analytical and Bioanalytical Chemistry,2015,407(12):3499-3507.
[12]GUAN Hong-xia,BREWER W E,GARRIS S T,et al.Disposable Pipette Extraction for the Analysis of Pesticides in Fruit and Vegetables Using Gas Chromatography/Mass Spectrometry[J].Journal of Chromatography A,2010,1217(12):1867-1874.
[13]刘一军,赖克强,戴月,等.分散液液微萃取-气质联用检测葡萄酒中的有机氯农药残留[J].光谱实验室,2013,30(1):228-233.
[14]陈军,张宗祥,杨文武,等.固相萃取-气质联用法测定水中有机氯农药和氯苯类化合物[J].环境监测管理与技术,2015,27(1):46-49.
[15]BRUCE D M,RICHARD B S.Development of an Automated Column Solid-phase Extraction Clean up of Qu ECh ERS Extracts,Using a Zirconia-based Sorbent,for Pesticide Residue Analyses by LC-MS/MS[J].Journal of Agricultural and Food Chemistry,2015,63(21):5107-5119.
[16]GONG Ling-ping,SHI Feng,JIANG Shu-yin,et al.Determination of Nine Pesticide Residues in Vegetables by Matrix Solidphase Dispersion-ultra Performance Liquid Chromatographytandem Mass Spectrometry[J].Chinese Journal of Chromatography,2015,33(4):408-412.
[17]ARUTHER C L,KILLAM L M.Analysis of Substituted Benzene Compounds in Groundwater Using Solid-phase Micro Extraction[J].Environmental Science and Technology,1992,26:979.
[18]彭华,李贝,张军,等.固相微萃取-气相色谱法测定水中硝基氯苯类化合物[J].中国环境监测,2015,31(5):124-128.
[19]刘海芳,马军辉,冯海强,等.固相微萃取法(SPME)在茶叶农残检测上的应用[J].茶叶,2007,33(3):136-139.
[20]裴永强,樊占春,赵静,等.顶空固相微萃取-气相色谱法测定水中氯苯类化合物[J].环境监测管理与技术,2014,26(6):39-45.
[21]赵英莲,牟德华,李艳,等.顶空固相微萃取联合气相色谱-质谱检测葡萄酒中2,4,6-三氯苯甲醚[J].食品科学,2016,37(10):219-225.
[22]刘潇威,买光熙,李凌云,等.NY/T 761-2008蔬菜和水果中有机磷、有机氯、拟除虫菊酯和氨基甲酸酯类农药多残留的测定[S].北京:中华人民共和国农业部,2008.
[23]CHUN Zhou-dong,ZHAO Rui-zeng,XIU Juan-li.Determination of Organochlorine Pesticides and Their Metabolites in Radish after Headspace Solid-phase Microextraction Using calix[4]Arene Fiber[J].Talanta,2005,66:721-727.