加速溶剂萃取-气相色谱-三重四极杆串联质谱法测定粮谷中的51 种农药残留

doi:10.7506/spkx1002-6630-201622033

摘要/Abstract

摘要： 为建立用气相色谱-三重四极杆串联质谱仪检测进出口粮谷中51 种农药残留的方法，通过考察不同加速溶剂萃取温度和萃取试剂的实验效果，建立了最优加速溶剂萃取条件，分别以高粱和大麦为研究基质，比较了3 种净化方式的净化效果，通过气相色谱-三重四极杆串联质谱仪有效解决了粮谷中多农药残留检测的问题，在系统优化的基础上建立了高粱中多种农药残留检测方法，并用大麦和燕麦其他的粮谷基质考察检测方法的适应性，同时对3 个添加水平6 个高粱、大麦、燕麦平行样品分析，该方法的回收率为62.4%～119.7%，相对标准偏差为0.5%～17.3%，检出限为0.03～2.07 μg/kg，方法相关指标均满足检测要求，适用于粮谷中农药残留高通量检测需要。

关键词: 气相色谱-三重四极杆串联质谱法, 加速溶剂萃取, 多农药残留, 粮谷

Abstract: A method was developed for detecting 51 pesticide residues in import and export cereals by gas chromatography-triple quadrupole-tandem mass spectrometry (GC-MS/MS). The optimal conditions for accelerated solvent extraction were established by investigating the effect of extraction temperature and solvent on extraction efficiency. The purification efficiencies of three different methods were compared for pesticide residues extracted from sorghum and barley. Multi-pesticide residues in sorghum were detected by GC-MS/MS, and the suitability of the analytical method for determining other cereals including barley and oat was investigated. The detection of six parallel samples of sorghum, barley and oat at three spiked levels showed that the recoveries for all pesticides were between 62.4% and 119.7%, with relative standard deviations (RSDs) varying from 0.5% to 17.3%, and the limits of detection (LODs) of the method were between 0.03 μg/kg and 2.07 μg/kg. This method can meet the analytical requirements and is suitable for high-throughput determination of multi-pesticide residues in cereals.

Key words: gas chromatography-triple quadrupole-tandem mass spectrometry (GC-MS/MS), accelerated solvent extraction, multi-pesticide residues, cereals

中图分类号:

O657.63

孟祥龙,张云清,范广宇,徐文科,唐秀,姚燕林. 加速溶剂萃取-气相色谱-三重四极杆串联质谱法测定粮谷中的51 种农药残留[J]. 食品科学, 2016, 37(22): 216-223.

MENG Xianglong, ZHANG Yunqing, FAN Guangyu, XU Wenke, TANG Xiu, YAO Yanlin. Determination of 51 Pesticide Residues in Cereals Using Accelerated Solvent Extraction and Gas Chromatography-Triple Quadrupole-Tandem Mass Spectrometry[J]. FOOD SCIENCE, 2016, 37(22): 216-223.

参考文献

[1] 钱传范, 刘丰茂, 潘灿平. 农药残留分析原理与方法[M]. 北京: 化学工业出版社, 2011: 284.
[2] HUANG Z Q, ZHANG Y, WANG L B, et al. Simultaneous determination of 103 pesticide residues in tea samples by LC-MS/MS[J]. Journal of Separation Science, 2009, 32(9): 1294-1301. DOI:10.1002/jssc.200800605.
[3] CHO S K, el ATY A M, PARK Y S, et al. A multiresidue method for the analysis of pesticide residues in polished rice (Oryza sativa L.) using accelerated solvent extraction and gas chromatography and confirmation by mass spectrometry[J]. Biomedical Chromatography, 2007, 21(6): 602-609. DOI:10.1002/bmc.792.
[4] ARIEL R F, ALEJANDRA C, LUIS D M, et al. Dispersive solid-phase extraction as a simplified clean-up technique for biological sample extracts. determination of polybrominated diphenyl ethers by gas chromatography-tandem mass spectrometry[J]. Journal of Chromatography A, 2011, 1218(18): 2490-2496. DOI:10.1016/j.chroma.2011.02.058.
[5] 李蓉, 卢俊文, 杨芳, 等. 基质固相分散萃取-气相色谱-串联质谱法同时测定蔬菜中195 种农药残留[J]. 食品科学, 2014, 35(24): 301-307. DOI:10.7506/spkx1002-6630-201424058.
[6] WANG J H, CAI F, WANG Y L, et al. Pesticide multiresidue analysis of peanuts using automated gel permeation chromatography clean-up/gas chromatography-mass spectrometry[J]. Journal of AOAC International, 2004, 87(4): 333-339. DOI:10.1080/02652030802350672.
[7] 孟祥龙, 王海涛, 范广宇, 等. 气相色谱-负化学电离离子化-质谱法测定出口泥鳅中的硫丹及其代谢物[J]. 理化检验: 化学分册, 2015, 51(4): 458-461.
[8] 王立. 色谱分析样品处理[M]. 北京: 化学工业出版社, 2006: 2.
[9] 田丽梅, 孙志勇, 向明, 等. 固相萃取.气相色谱法检测金银花中9 种拟除虫菊酯农药残留[J]. 食品科学, 2015, 36(20): 239-241. DOI:10.7506/spkxl002-6630-201520046.
[10] 丁立平, 蔡春平, 王丹红. 双重净化/气相色谱法测定水产品中指示性多氯联苯[J]. 分析测试学报, 2014, 33(10): 1178-1183. DOI:10.3969/j.issn.1004-4957.2014.10.18.
[11] CASTILLO M, GONZáLEZ C, MIRALLES A. et al. An evaluation method for determination of non-polar pesticide residues in animal fat samples by using dispersive solid-phase extraction clean-up and GC-MS[J]. Analytical and Bioanalytical Chemistry, 2011, 400(5): 1315-1328. DOI:10.1007/s00216-011-4656-5.
[12] 李萍萍, 程景, 乐渊. 气相色谱-三重四极杆串联质谱法测定含硫蔬菜中46 种农药残留量[J]. 分析测试学报, 2015, 34(4): 421-427. DOI:10.3969/j.issn.1004-4957.2015.04.008.
[13] 李岩, 郑锋, 王明林, 等. 液相色谱-串联质谱法快速筛查测定浓缩果蔬汁中的156 种农药残留[J]. 色谱, 2009, 27(2): 127-137. DOI:10.3321/j.issn:1000-8713.2009.02.001.
[14] 沈伟健, 余可垚, 桂茜雯, 等. 分散固相萃取-气相色谱-串联质谱法测定蔬菜中107 种农药的残留量[J]. 色谱, 2009, 27(4): 391-396. DOI:10.3321/j.issn:1000-8713.2009.04.003.
[15] 谢文, 钱艳, 丁慧瑛, 等. 液相色谱-电喷雾电离三级四极杆质谱法测定茶叶中6 种烟碱类农药残留[J]. 分析化学, 2009, 37(4): 495-499. DOI:10.3321/j.issn:0253-3820.2009.04.004.
[16] 闫蕊, 邵明媛, 鞠福龙. 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. DOI:10.3724/SP.J.1096.2013.20965.
[17] 郝昀. 加速溶剂萃取-高效液相色谱法检测磺胺类、氟喹诺酮类及鼠药类药物残留[D]. 保定: 河北大学, 2014: 6-17.
[18] 胡贝贞, 宋伟华, 谢丽萍, 等. 加速溶剂萃取/凝胶渗透色谱-固相萃取净化/气相色谱-质谱法测定茶叶中残留的33 种农药[J]. 色谱, 2008, 26(1): 22-28. DOI:10.3321/j.issn:1000-8713.2008.01.005.
[19] 吴刚, 鲍晓霞, 王华雄, 等. 加速溶剂萃取-凝胶渗透色谱净化-气相色谱快速分析动物源性食品中残留的多种有机磷农药[J]. 色谱, 2008, 26(5): 577-582. DOI:10.3321/j.issn:1000-8713.2008.05.010.
[20] 杨琳, 温裕云, 弓振斌. 加速溶剂萃取-液相色谱-串级质谱法测定近岸及河口沉积物中的拟除虫菊酯农药[J]. 分析化学, 2010, 38(7): 968-972. DOI:10.3724/SP.J.1096.2010.00968.
[21] 欧阳运富, 唐宏兵, 吴英, 等. 加速溶剂萃取-在线凝胶渗透色谱-气相色谱-质谱联用法快速测定蔬菜和水果中多农药残留[J].色谱, 2012, 30(7): 654-659. DOI:10.3724/SP.J.1123.2012.03039.
[22] 王敬, 艾连峰, 马育松, 等. 气相色谱/三重四极杆串联质谱法测定牛奶及奶粉中213 种农药多残留[J]. 色谱, 2015, 33(11): 1175-1178.
[23] 陈小华, 汪群杰. 固相萃取技术及应用[M]. 北京: 科学出版社, 2010: 300. DOI:10.3724/SP.J.1123.2015.07012.
[24] 吕冰, 陈达炜, 苗虹. 凝胶渗透色谱-固相萃取净化/气相色谱-串联质谱法测定动物性食品中167 种农药残留[J]. 分析测试学报, 2015, 34(6): 639-645. DOI:10.3969/j.issn.1004-4957.2015.06.002.
[25] 郭新东, 冼燕萍, 罗海英, 等. 气相色谱-三重串联四极杆质谱法测定粮谷中169 种农药的残留量[J]. 现代食品科技, 2012, 28(6): 695-702. DOI:10.3969/j.issn.1673-9078.2012.06.025.