利用气液微萃取技术联用气相色谱-质谱法检测谷类中27种残留农药
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摘要
目的建立气液微萃取技术(gas-liquid microextraction,GLME)联用气相色谱-质谱法(gas chromatography-mass spectrometry, GC-MS)快速检测谷类中的27种农药残留的方法。方法精确称量0.5 g谷类样品,用0.5 mL二氯甲烷溶剂超声萃取15 min,离心4 min后取上清液100μL,利用气液微萃取(GLME)对27种农残萃取、净化和浓缩,结合内标法确保结果的准确性。结果 27种农药在0.001～1.0mg/kg浓度范围内线性良好,相关系数在0.9990～0.9999,检出限为0.002～0.026 mg/kg,定量限为0.0007～0.086 mg/kg,平均回收率为71.2%～124.4%(n=3),相对标准偏差在0.2%～18.8%之间。结论本方法操作简便方便、准确度高、重现性好,适用于食品安全现场检测和快速检测,对于保障我国食品安全构建完整的食品安全检测体系具有重大意义。
Objective To establish a method for rapid detection of various pesticides in cereal grains by gas-liquid microextraction(GLME) and gas chromatography-mass spectrometry(GC-MS). Methods The 0.5 g cereal sample was accurately weighed and extracted with 0.5 mL dichloromethane solvent for 15 min, after 4 min centrifugation, 100 μL supernatant was taken and 27 kinds of residues were extracted, purified and concentrated by gas-liquid microextraction(GLME). The accuracy of the results was ensured by the internal standard method. Results The 27 kinds of pesticide had good linear relationships in the range of 0.001?1.0 mg/kg, and the correlation coefficients were 0.9990?0.9999. The limits of detection were 0.002?0.026 mg/kg and the limits of quantitation were0.0007?0.086 mg/kg. The average recoveries were 71.2%?124.4%(n=3) with relative standard deviations of0.2%?18.8%. Conclusion This method is simple and rapid, with high accuracy and good repeatability, which is suitable for rapid analysis or field-detection in the food safety industry. It is of great significance to build a complete food safety inspection system to ensure China's food safety.
Objective To establish a method for rapid detection of various pesticides in cereal grains by gas-liquid microextraction(GLME) and gas chromatography-mass spectrometry(GC-MS). Methods The 0.5 g cereal sample was accurately weighed and extracted with 0.5 mL dichloromethane solvent for 15 min, after 4 min centrifugation, 100 μL supernatant was taken and 27 kinds of residues were extracted, purified and concentrated by gas-liquid microextraction(GLME). The accuracy of the results was ensured by the internal standard method. Results The 27 kinds of pesticide had good linear relationships in the range of 0.001?1.0 mg/kg, and the correlation coefficients were 0.9990?0.9999. The limits of detection were 0.002?0.026 mg/kg and the limits of quantitation were0.0007?0.086 mg/kg. The average recoveries were 71.2%?124.4%(n=3) with relative standard deviations of0.2%?18.8%. Conclusion This method is simple and rapid, with high accuracy and good repeatability, which is suitable for rapid analysis or field-detection in the food safety industry. It is of great significance to build a complete food safety inspection system to ensure China's food safety.
引文
[1]张秀玲.中国农产品农药残留成因与影响研究[D].无锡:江南大学,2013.Zhang XL.Studies on the causes and impact of China’s agricultural pesticide residues[D].Wuxi:Jiangnan University,2013.
[2]Han Y,Song L,Zou N,et al.Rapid multi-plug filtration cleanup method for the determination of 124 pesticide residues in rice,wheat,and corn[J].J Separat Sci,2016,40(4):878-884.
[3]吴俐,曹赵云,陈铭学,等.气相色谱-串联质谱测定水稻中10种拟除虫菊酯类杀虫剂农药残留[J].安徽农业科学,2017,45(6):147-150.Wu L,Cao ZY,Chen MX,et al.Determination of 10 pyrethroids pesticide residues in rice by GC-MS-MS[J].J Anhui Agric Sci,2017,45(6):147-150.
[4]Rivera ZH,Oosterink E,Rietveld L,et al.Influence of natural organic matter on the screening of pharmaceuticals in water by using liquid chromatography with full scan mass spectrometry[J].Anal Chim Acta,2011,700(1):114-125.
[5]Garciaac A,Segura PA,Viglino L,et al.On-line solid-phase extraction of large-volume injections coupled to liquid chromatography-tandem mass spectrometry for the quantitation and confirmation of 14 selected trace organic contaminants in drinking and surface water[J].J Chromatogr A,2009,1216(48):8518-8527.
[6]Hernández F,Portolés T,Pitarch E,et al.Target and nontarget screening of organic micropollutants in water by solid-phase microextraction combined with gas chromatography/high-resolution time-of-flight mass spectrometry[J].Anal Chem,2007,79(24):9494-9504.
[7]Guo Q,Xia L V,Tan L,et al.Simultaneous determination of 26 pesticide residues in 5 Chinese medicinal materials using solid-phase extraction and GC-ECD method[J].Chin J Nat Med,2009,7(3):210-216.
[8]赵宇翔.市售蔬果中毒死蜱农药残留风险评估的研究[D].上海:复旦大学,2009.Zhao YX.Study on risk assessment of pesticide residues in commercial fruits and vegetables[D].Shanghai:Fudan University,2009.
[9]李成成.豆类、粮谷类食品中咪唑啉酮类农药残留检测方法的研究[D].保定:河北农业大学,2008.Li CC.Study on the analytical methods of imidazolinone pesticide residues in beans and cereals[D].Baoding:Agricultural University of Hebei,2008.
[10]王洋.氟苯虫酰胺在玉米上的残留动态及最大残留限量标准制定[D].长春:吉林农业大学,2016.Wang Y.Degradation dynamic of flubendiamide in corn and establish the maximum residue limits[D].Changchun:Jilin Agricultural University,2016.
[11]杨精华.稻谷中几种典型农药残留降解规律研究[D].南京:南京财经大学,2016.Yang JH.Research on the degradation of several typical pesticide residues in rice[D].Nanjing:Nanjing University of Finance,2016.
[12]Chunfeng LI,Weijian S,Yuan J,et al.Determination of 20 kinds of pesticide residues in soybeans and corn using gas chromatographynegative chemical ionization mass spectrometry coupled with offline disperse solid-phase extraction[J].Chin J Chromatograph,2009,27(2):176-180.
[13]Shi XM,Chen SH,Zhang Q,et al.Simultaneous determination of organic chlorine and pyrethroid pesticides residues in corn by solid phase extraction-gas chromatography[J].J Food Saf Qual,2015,(4):1122-1127.
[14]金玉善.气流吹扫微注射器萃取与气相色谱质谱联用同时分析人参中的有机氯和有机磷农药[D].延吉:延边大学,2011.Jin YS.Simultaneously analysis of organochlorine pesticides and organophosphorus pesticides residues from ginseng using gas purge microsyringe extraction coupled with gas chromatography-mass spectrometry[D].Yanji:Yanbian University,2011.
[15]Luo Y,Xiangyu LI,Zhu F,et al.Determination of pesticide residues in tobacco by on-line gel permeation chromatography-gas chromatography/tandem mass spectrometry[J].Tobacco Sci Technol,2016,49(7):44-50.
[16]谢飞飞.啶氧菌酯农残检测及其在粮谷物中应用的研究[D].马鞍山:安徽工程大学,2016.Xie FF.Research on detection of pesticide residues of picoxystrobin and its application in food grains[D].Ma'anshan:Anhui Polytechnic University,2016.
[17]Yan H,Guo P,Luo PJ,et al.Determination of chlorpyrifos pesticide residues in rice by NIR spectroscopy coupled with a membrane enrichment technique[J].Mod Food Sci Technol,2017,33(4):289-294.
[18]孙玉玉.粮谷中20种农药残留检测方法的研究[D].大连:大连工业大学,2015.Sun YY.Study on detection methods of 20 pesticide residues in grains[D].Dalian:Dalian Polytechnic University,2015.
[19]刘青春.气流吹扫微注射器萃取联用气相色谱-质谱同时检测多种农药[D].延吉:延边大学,2013.Liu QC.Gas purge microsyringe extraction(GP-MSE)combined with gas chromatographic-mass spectrometry(GC-MS)detectsimultaneouslya variety of pesticides[D].Yanji:Yanbian University,2013.
[20]郑伟颖.气-质联用技术在植物花叶挥发性成分分析中的应用[D].哈尔滨:哈尔滨理工大学,2016.Zheng WY.Application of gas-mass-mass spectrometry in analysis of volatile components in plant mosaic[D].Harbin:Harbin University of Science and Technology,2016.
[21]曲琳娟.单级质谱与多级质谱对蔬菜中农药多残留的检测研究[D].济南:山东大学,2010.Qu LJ.Detection of pesticide multi-residues in vegetables by GC-MS and GC-QqQ-MS/MS[D].Jinan:Shandong University,2010.
[22]南京熙,毕程程,金京一,等.超声萃取-气流式液相微萃取-气相色谱质谱在线联用快速检测蔬菜中有机磷农药残留(英文)[J].食品与机械,2014,(5):72-82.Nan JX,Bi CC,Jin JY,et al.Ultrasonic extraction and gas flow liquid phase microextraction coupled with on-line gas chromatography-mass spectrometry:Rapid determination of organophosphorus pesticide residues in vegetables[J].Food Mach,2014,(5):72-82.
[2]Han Y,Song L,Zou N,et al.Rapid multi-plug filtration cleanup method for the determination of 124 pesticide residues in rice,wheat,and corn[J].J Separat Sci,2016,40(4):878-884.
[3]吴俐,曹赵云,陈铭学,等.气相色谱-串联质谱测定水稻中10种拟除虫菊酯类杀虫剂农药残留[J].安徽农业科学,2017,45(6):147-150.Wu L,Cao ZY,Chen MX,et al.Determination of 10 pyrethroids pesticide residues in rice by GC-MS-MS[J].J Anhui Agric Sci,2017,45(6):147-150.
[4]Rivera ZH,Oosterink E,Rietveld L,et al.Influence of natural organic matter on the screening of pharmaceuticals in water by using liquid chromatography with full scan mass spectrometry[J].Anal Chim Acta,2011,700(1):114-125.
[5]Garciaac A,Segura PA,Viglino L,et al.On-line solid-phase extraction of large-volume injections coupled to liquid chromatography-tandem mass spectrometry for the quantitation and confirmation of 14 selected trace organic contaminants in drinking and surface water[J].J Chromatogr A,2009,1216(48):8518-8527.
[6]Hernández F,Portolés T,Pitarch E,et al.Target and nontarget screening of organic micropollutants in water by solid-phase microextraction combined with gas chromatography/high-resolution time-of-flight mass spectrometry[J].Anal Chem,2007,79(24):9494-9504.
[7]Guo Q,Xia L V,Tan L,et al.Simultaneous determination of 26 pesticide residues in 5 Chinese medicinal materials using solid-phase extraction and GC-ECD method[J].Chin J Nat Med,2009,7(3):210-216.
[8]赵宇翔.市售蔬果中毒死蜱农药残留风险评估的研究[D].上海:复旦大学,2009.Zhao YX.Study on risk assessment of pesticide residues in commercial fruits and vegetables[D].Shanghai:Fudan University,2009.
[9]李成成.豆类、粮谷类食品中咪唑啉酮类农药残留检测方法的研究[D].保定:河北农业大学,2008.Li CC.Study on the analytical methods of imidazolinone pesticide residues in beans and cereals[D].Baoding:Agricultural University of Hebei,2008.
[10]王洋.氟苯虫酰胺在玉米上的残留动态及最大残留限量标准制定[D].长春:吉林农业大学,2016.Wang Y.Degradation dynamic of flubendiamide in corn and establish the maximum residue limits[D].Changchun:Jilin Agricultural University,2016.
[11]杨精华.稻谷中几种典型农药残留降解规律研究[D].南京:南京财经大学,2016.Yang JH.Research on the degradation of several typical pesticide residues in rice[D].Nanjing:Nanjing University of Finance,2016.
[12]Chunfeng LI,Weijian S,Yuan J,et al.Determination of 20 kinds of pesticide residues in soybeans and corn using gas chromatographynegative chemical ionization mass spectrometry coupled with offline disperse solid-phase extraction[J].Chin J Chromatograph,2009,27(2):176-180.
[13]Shi XM,Chen SH,Zhang Q,et al.Simultaneous determination of organic chlorine and pyrethroid pesticides residues in corn by solid phase extraction-gas chromatography[J].J Food Saf Qual,2015,(4):1122-1127.
[14]金玉善.气流吹扫微注射器萃取与气相色谱质谱联用同时分析人参中的有机氯和有机磷农药[D].延吉:延边大学,2011.Jin YS.Simultaneously analysis of organochlorine pesticides and organophosphorus pesticides residues from ginseng using gas purge microsyringe extraction coupled with gas chromatography-mass spectrometry[D].Yanji:Yanbian University,2011.
[15]Luo Y,Xiangyu LI,Zhu F,et al.Determination of pesticide residues in tobacco by on-line gel permeation chromatography-gas chromatography/tandem mass spectrometry[J].Tobacco Sci Technol,2016,49(7):44-50.
[16]谢飞飞.啶氧菌酯农残检测及其在粮谷物中应用的研究[D].马鞍山:安徽工程大学,2016.Xie FF.Research on detection of pesticide residues of picoxystrobin and its application in food grains[D].Ma'anshan:Anhui Polytechnic University,2016.
[17]Yan H,Guo P,Luo PJ,et al.Determination of chlorpyrifos pesticide residues in rice by NIR spectroscopy coupled with a membrane enrichment technique[J].Mod Food Sci Technol,2017,33(4):289-294.
[18]孙玉玉.粮谷中20种农药残留检测方法的研究[D].大连:大连工业大学,2015.Sun YY.Study on detection methods of 20 pesticide residues in grains[D].Dalian:Dalian Polytechnic University,2015.
[19]刘青春.气流吹扫微注射器萃取联用气相色谱-质谱同时检测多种农药[D].延吉:延边大学,2013.Liu QC.Gas purge microsyringe extraction(GP-MSE)combined with gas chromatographic-mass spectrometry(GC-MS)detectsimultaneouslya variety of pesticides[D].Yanji:Yanbian University,2013.
[20]郑伟颖.气-质联用技术在植物花叶挥发性成分分析中的应用[D].哈尔滨:哈尔滨理工大学,2016.Zheng WY.Application of gas-mass-mass spectrometry in analysis of volatile components in plant mosaic[D].Harbin:Harbin University of Science and Technology,2016.
[21]曲琳娟.单级质谱与多级质谱对蔬菜中农药多残留的检测研究[D].济南:山东大学,2010.Qu LJ.Detection of pesticide multi-residues in vegetables by GC-MS and GC-QqQ-MS/MS[D].Jinan:Shandong University,2010.
[22]南京熙,毕程程,金京一,等.超声萃取-气流式液相微萃取-气相色谱质谱在线联用快速检测蔬菜中有机磷农药残留(英文)[J].食品与机械,2014,(5):72-82.Nan JX,Bi CC,Jin JY,et al.Ultrasonic extraction and gas flow liquid phase microextraction coupled with on-line gas chromatography-mass spectrometry:Rapid determination of organophosphorus pesticide residues in vegetables[J].Food Mach,2014,(5):72-82.
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