QuEChERS-超高效液相色谱-四极杆-飞行时间质谱法同时测定土壤中23种农药
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摘要
[目的]利用QuEChERS前处理法-超高效液相色谱(UHPLC)-四极杆-飞行时间质谱(Q-TOF/MS)法建立了23种农药的快速筛查和定量检测方法。[方法]建立了23种农药的一级精确质量数和二级图谱库数据库。通过谱库信息比对,该方法可实现无标准品情况下23种农药的定性鉴定。土壤样品经过QuEChERS前处理法进行提取,采用C18色谱柱分离,0.1%甲酸10 mmol/L乙酸铵甲醇溶液和0.1%甲酸10 mmol/L乙酸铵水进行梯度洗脱,外标法定量。[结果]在线性范围内,23种农药的线性关系良好,线性相关系数≥0.991。方法的定量限为5μg/kg。23种农药的平均回收率为65.91%～108.6%,相对标准偏差(RSD)为0.07%～16.00%。[结论]该方法操作简单、稳定性好,可满足土壤中23种农药残留的检测要求。
[Aims] A rapid screening and detection method for 23 pesticides in soil was established by combining QuEChERS with ultra high performance liquid chromatography(UPLC)-quadrupole-time of flight mass spectrometry(Q-TOF/MS). [Methods] A database including accurate mass and fragment ions information of 23 pesticides was established. Based on the above database, the qualitative identifications of the 23 pesticides were accomplished without comparison to the standard substances. Soil samples were pretreated by QuEChERS and separated by C18 column.Gradient elution of methanol solution which contained 0.1% formic acid 10 mmol/L ammonium acetate and water solution containing 0.1% formic acid 10 mmol/L ammonium acetate was carried out. External standard method was set for quantitative. [Results] The linear correlation coefficients of 23 pesticides were more than 0.991. The limits of quantitation(LOQs) of the method were 5 μg/kg. The average recoveries at three spiked levels of 23 pesticides were65.91-108.6% with the relative standard deviation(RSD) 0.07-16.00%. [Conclusions] With the advantages of simplicity and good stability, this method is available for the determination of 23 pesticide residues in soil.
[Aims] A rapid screening and detection method for 23 pesticides in soil was established by combining QuEChERS with ultra high performance liquid chromatography(UPLC)-quadrupole-time of flight mass spectrometry(Q-TOF/MS). [Methods] A database including accurate mass and fragment ions information of 23 pesticides was established. Based on the above database, the qualitative identifications of the 23 pesticides were accomplished without comparison to the standard substances. Soil samples were pretreated by QuEChERS and separated by C18 column.Gradient elution of methanol solution which contained 0.1% formic acid 10 mmol/L ammonium acetate and water solution containing 0.1% formic acid 10 mmol/L ammonium acetate was carried out. External standard method was set for quantitative. [Results] The linear correlation coefficients of 23 pesticides were more than 0.991. The limits of quantitation(LOQs) of the method were 5 μg/kg. The average recoveries at three spiked levels of 23 pesticides were65.91-108.6% with the relative standard deviation(RSD) 0.07-16.00%. [Conclusions] With the advantages of simplicity and good stability, this method is available for the determination of 23 pesticide residues in soil.
引文
[1]YU Yong,LIU Xiao-wei,HE Ze-ying,et al.Development of a Multi-residue Method for 58 Pesticides in Soil Using Qu ECh ERSand Gas Chromatography-tandem Mass Spectrometry[J].Anal Methods,2016,8(11):2463-2470.
[2]朱永哲,冯雅男,金正汉.超高效液相色谱-串联质谱法同时测定土壤中239种农药的残留量[J].色谱,2013,31(9):850-861.
[3]PIC魷YOLANDA,FERN譧NDEZ M魷NICA,RUIZ MARIA JOSE,et al.Current Trends in Solid-phase-based Extraction Techniques for the D etermination of Pesticides in Food and Environment[J].J Biochem Biophys Methods,2008,70(2):117-131.
[4]刘红,梅黎小鹏,李文英,等.全自动索氏提取-气相色谱法检测土壤中六六六和滴滴涕农药残留量[J].广东农业科学,2012,39(11):188-190.
[5]封棣,阎正,赵亚奎,等.固相萃取-毛细管气相色谱法测定中草药及其土壤中多种有机氯农药残留量[J].分析试验室,2005,24(10):8-12.
[6]闫蕊,邵明媛,鞠福龙,等.加速溶剂萃取-高效液相色谱串联质谱法测定土壤中农药残留[J].分析化学,2013,41(2):315-316.
[7]葛谦,姜瑞,赵丹青,等.Qu ECh ERS-HPLC法测定黄瓜和土壤中氟吗啉的残留量[J].农药,2015,54(12):904-905,910.
[8]李艳,滕应,赵玲,等.QuEChERS-高效液相色谱法测定土壤中嘧霉胺和吡唑醚菌酯残留[J].农药,2017,56(8):596-599.
[9]曾凯,孙国泉,唐俊,等.QuEChERS-气质联用法同时测定土壤中16种农药残留[J].农药,2016,55(7):507-509,523.
[10]谭华东,张汇杰,武春媛.QuEChERS/UPLC-MS/MS法快速测定土壤中吡虫啉、啶虫脒与阿维菌素残留[J].农药,2019,58(1):45-49.
[11]尹君,马琳,黄兰淇,等.QuEChERS/超高效液相色谱-串联质谱法同时测定土壤中67种农药残留[J].分析测试学报,2018,37(5):562-569
[12]宫小明,王洪涛,华萌萌,等.Qu ECh ERS-UPLC-HR-MS法测定蔬菜大棚土壤中农药残留[J].检验检疫学刊,2012,39(11):188-190.
[13]张璐,张亚莉,何强,等.超高液相色谱/线性离子阱-静电场轨道阱高分辨质谱法快速筛查土壤中氨基甲酸酯类农药残留量[J].分析试验室,2017,36(1):60-65.
[14]王连珠,周昱,陈泳,等.Qu ECh ERS样品前处理-液相色谱-串联质谱法测定蔬菜中66种有机磷农药残留量方法评估[J].色谱,2012,30(2):146-153.
[15]ZHAO Peng-yue,WANG Lei,JIANG Ya-ping,et al.Dispersive Cleanup of Acetonitrile Extracts of Tea Samples by Mixed Multiwalled Carbon Nanotubes,Primary Secondary Amine,and Graphitized Carbon Black Sorbents[J].Journal of Agricultural&Food Chemistry,2012,60(16):4026-4033.
[16]徐娟,陈捷,叶弘毅,等.QuEChERS提取与高效液相色谱-电喷雾电离串联质谱联用法检测茶叶中的19种农药残留[J].分析测试学报,2011,30(9):990-995.
[17]WANG Jian,LEUNG D.Applications of Ultra-performance Liquid Chromatography Electrospray Ionization Quadrupole Time-of-Flight Mass Spectrometry on Analysis of 138Pesticides in Fruit and Vegetable-based Infant Foods[J].J Agric Food Chem,2009,57(6):2162-2173.
[18]LUCINI LUIGI,PELLEGRINO ROBERTO,CIMINO NICOLA,et al.QqQ an d Q-TOF Liquid Chromatography Mass Spectrometry Direct Aqueous Analysis of Herbicides and their Metabolites in Water[J].International Journal of Mass Spectrometry,2015,392:16-22.
[19]WANG San-yuan,KUO C,TSENG Y.Ion Trace Detection Algorithm to Extract Pure Ion Chromatograms to Improve Untargeted Peak Detection Quality for Liquid Chromatography/Time-of-Flight Mass Spectrometry-based Metabolomics Data[J].Analytical Chemistry,2015,87:3048-3055.
[20]SANTE/11813/2017.Guidance Document on Analytical Quality Control and Method Validation Procedures for Pesticides Residues Analysis in Food and Feed.European Commission Directorate General for Health and Food Safety.
[2]朱永哲,冯雅男,金正汉.超高效液相色谱-串联质谱法同时测定土壤中239种农药的残留量[J].色谱,2013,31(9):850-861.
[3]PIC魷YOLANDA,FERN譧NDEZ M魷NICA,RUIZ MARIA JOSE,et al.Current Trends in Solid-phase-based Extraction Techniques for the D etermination of Pesticides in Food and Environment[J].J Biochem Biophys Methods,2008,70(2):117-131.
[4]刘红,梅黎小鹏,李文英,等.全自动索氏提取-气相色谱法检测土壤中六六六和滴滴涕农药残留量[J].广东农业科学,2012,39(11):188-190.
[5]封棣,阎正,赵亚奎,等.固相萃取-毛细管气相色谱法测定中草药及其土壤中多种有机氯农药残留量[J].分析试验室,2005,24(10):8-12.
[6]闫蕊,邵明媛,鞠福龙,等.加速溶剂萃取-高效液相色谱串联质谱法测定土壤中农药残留[J].分析化学,2013,41(2):315-316.
[7]葛谦,姜瑞,赵丹青,等.Qu ECh ERS-HPLC法测定黄瓜和土壤中氟吗啉的残留量[J].农药,2015,54(12):904-905,910.
[8]李艳,滕应,赵玲,等.QuEChERS-高效液相色谱法测定土壤中嘧霉胺和吡唑醚菌酯残留[J].农药,2017,56(8):596-599.
[9]曾凯,孙国泉,唐俊,等.QuEChERS-气质联用法同时测定土壤中16种农药残留[J].农药,2016,55(7):507-509,523.
[10]谭华东,张汇杰,武春媛.QuEChERS/UPLC-MS/MS法快速测定土壤中吡虫啉、啶虫脒与阿维菌素残留[J].农药,2019,58(1):45-49.
[11]尹君,马琳,黄兰淇,等.QuEChERS/超高效液相色谱-串联质谱法同时测定土壤中67种农药残留[J].分析测试学报,2018,37(5):562-569
[12]宫小明,王洪涛,华萌萌,等.Qu ECh ERS-UPLC-HR-MS法测定蔬菜大棚土壤中农药残留[J].检验检疫学刊,2012,39(11):188-190.
[13]张璐,张亚莉,何强,等.超高液相色谱/线性离子阱-静电场轨道阱高分辨质谱法快速筛查土壤中氨基甲酸酯类农药残留量[J].分析试验室,2017,36(1):60-65.
[14]王连珠,周昱,陈泳,等.Qu ECh ERS样品前处理-液相色谱-串联质谱法测定蔬菜中66种有机磷农药残留量方法评估[J].色谱,2012,30(2):146-153.
[15]ZHAO Peng-yue,WANG Lei,JIANG Ya-ping,et al.Dispersive Cleanup of Acetonitrile Extracts of Tea Samples by Mixed Multiwalled Carbon Nanotubes,Primary Secondary Amine,and Graphitized Carbon Black Sorbents[J].Journal of Agricultural&Food Chemistry,2012,60(16):4026-4033.
[16]徐娟,陈捷,叶弘毅,等.QuEChERS提取与高效液相色谱-电喷雾电离串联质谱联用法检测茶叶中的19种农药残留[J].分析测试学报,2011,30(9):990-995.
[17]WANG Jian,LEUNG D.Applications of Ultra-performance Liquid Chromatography Electrospray Ionization Quadrupole Time-of-Flight Mass Spectrometry on Analysis of 138Pesticides in Fruit and Vegetable-based Infant Foods[J].J Agric Food Chem,2009,57(6):2162-2173.
[18]LUCINI LUIGI,PELLEGRINO ROBERTO,CIMINO NICOLA,et al.QqQ an d Q-TOF Liquid Chromatography Mass Spectrometry Direct Aqueous Analysis of Herbicides and their Metabolites in Water[J].International Journal of Mass Spectrometry,2015,392:16-22.
[19]WANG San-yuan,KUO C,TSENG Y.Ion Trace Detection Algorithm to Extract Pure Ion Chromatograms to Improve Untargeted Peak Detection Quality for Liquid Chromatography/Time-of-Flight Mass Spectrometry-based Metabolomics Data[J].Analytical Chemistry,2015,87:3048-3055.
[20]SANTE/11813/2017.Guidance Document on Analytical Quality Control and Method Validation Procedures for Pesticides Residues Analysis in Food and Feed.European Commission Directorate General for Health and Food Safety.