超高效液相色谱-串联质谱法同时测定茶鲜叶中79种农药残留

doi:10.13305/j.cnki.jts.2023.02.004

摘要/Abstract

摘要： 建立以超高效液相色谱-串联质谱（UPLC-MS/MS）同时测定茶鲜叶中79种农药残留量的分析方法。以乙腈为提取剂,茶鲜叶样品经高速破壁均质后加入NaCl盐析,离心取上清液经无水硫酸镁、C₁₈、PSA和GCB分散固相萃取净化后上机,多反应监测模式扫描,分段时间窗口采集数据,外标法定量。结果显示,79种目标化合物在0.001~0.400 mg·L^-1质量浓度范围内线性良好,相关系数（R²）为0.990 6~0.999 9,在0.01、0.03、0.05、0.10 mg·kg^-1和0.20 mg·kg^-1等5个添加水平下的平均回收率为70.7%~119.0%,相对标准偏差（RSD）为0.1%~19.8%,方法定量限为0.01~0.05 mg·kg^-1。该方法灵敏度高、准确性好、分析速度快,适用于茶鲜叶中79种农药残留的检测。

关键词: 茶鲜叶, 超高效液相色谱-串联质谱法, 农药残留, 回收率

Abstract: A method for simultaneous determination of 79 pesticides residues in fresh tea leaves by ultra-high performance liquid chromatography-mass spectrometry (UPLC-MS/MS) was establish in this study. The fresh tea leaves were ground by high-speed wall breaking and then extracted by acetonitrile solution with NaCl. The liquid supernatant was centrifuged and purified by solid phase extraction of anhydrous magnesium sulfate, C₁₈, PSA and GCB. The scheduled multiple reaction monitoring mode (sMRM) was used for scanning and determination, and quantitative by external standard method. The results show that the 79 target compounds exhibited good linearity within the concentration range of 0.001~0.400 mg·L^-1 with a correlation coefficient (R²) of 0.990 6 to 0.999 9. The average recoveries at 5 spiked levels (0.01, 0.03, 0.05, 0.10, 0.20 mg·kg^-1) ranged from 70.7% to 119.0%, with the relative standard deviations (RSDs) ranging from 0.1% to 19.8%, and the limits of quantitation (LOQ) for the 79 pesticides ranging from 0.01 mg·kg^-1 to 0.05 mg·kg^-1. The proposed method is high sensitivity, good accuracy and quick, which is suitable for determination of 79 pesticides residues in fresh tea leaves.

Key words: fresh tea leaves, UPLC-MS/MS, pesticide residues, recovery

中图分类号:

S571.1

潘瑛洁, 孟祥河, 钱园凤, 宁建美, 王月圆, 刘齐铭, 唐仕琴, 徐晓安, 叶沁. 超高效液相色谱-串联质谱法同时测定茶鲜叶中79种农药残留[J]. 茶叶科学, 2023, 43(2): 250-262. doi: 10.13305/j.cnki.jts.2023.02.004.

PAN Yingjie, MENG Xianghe, QIAN Yuanfeng, NING Jianmei, WANG Yueyuan, LIU Qiming, TANG Shiqin, XU Xiaoan, YE Qin. Simultaneous Determination of 79 Pesticides Residues in Fresh Tea Leaves by Ultra-high Performance Liquid Chromatography-mass Spectrometry[J]. Journal of Tea Science, 2023, 43(2): 250-262. doi: 10.13305/j.cnki.jts.2023.02.004.

参考文献 29

[1]	江婷婷, 方亚丽. 一叶茶青托起致富梦[J]. 当代贵州, 2017(11): 26-27.Jiang T T, Fang Y L.A leaf of tea holds up the dream of wealth[J]. Guizhou Today, 2017(11): 26-27.
[2]	曹春霞, 黄大野, 吴琼, 等. 茶叶农药残留检测分析方法研究进展[J]. 湖北农业科学, 2019, 58(17): 5-8, 12.Cao C X, Huang D Y, Wu Q, et al.Research progress of determination methods of pesticide residues in tea[J]. Hubei Agricultural Sciences, 2019, 58(17): 5-8, 12.
[3]	祝愿, 李俊, 蔡滔, 等. 高效液相色谱-串联质谱法检测茶青中124种农药残留[J]. 食品安全质量检测学报, 2019, 10(8): 2317-2329.Zhu Y, Li J, Cai T, et al.Determination of 124 pesticide residues in tea green by high performance liquid chromatograph-mass spectrometry[J]. Journal of Food Safety and Quality, 2019, 10(8): 2317-2329.
[4]	侯如燕, 宛晓春, 朱旭君. 茶鲜叶中拟除虫菊酯类农药残留的检测方法[J]. 食品与发酵工业, 2008, 34(8): 137-140.Hou R Y, Wan X C, Zhu X J.A novel method for determination pyrethroid pesticides in fresh tea leaves with GC-μECD[J]. Food and Fermentation Industries, 2008, 34(8): 137-140.
[5]	Sun R, Yang W Q, Li Y X, et al.Multi-residue analytical methods for pesticides in teas: a review[J]. European Food Research and Technology, 2021, 247(8): 227-234.
[6]	Chen H P, Wang X L, Liu P X, et al.Determination of three typical metabolites of pyrethroid pesticides in tea using a modified QuEChERS sample preparation by ultra-high performance liquid chromatography tandem mass spectrometry[J]. Foods, 2021, 10(1): 102-107.
[7]	中华人民共和国农业农村部. 食品安全国家标准茶叶中448种农药及相关化学品残留量的测定液相色谱-质谱法: GB 23200.13—2016[S]. 北京: 中国标准出版社, 2016.Ministry of Agriculture and Rural Affairs of the People’s Republic of China. National food safety standards-determination of 448 pesticide residues in tea: liquid chromatography-mass spectrometry: GB 23200.13—2016 [S]. Beijing: China Standards Press, 2016.
[8]	中华人民共和国农业农村部. 食品安全国家标准植物源性食品中331种农药及其代谢物残留量的测定液相色谱-质谱联用法: GB 23200.121—2021[S]. 北京: 中国农业出版社, 2021.Ministry of Agriculture and Rural Affairs of the People’s Republic of China. National food safety standards-Determination of 331 pesticides and metabolites residues in food of plant origin: liquid chromatography-tandem mass spectrometry method: GB 23200.121—2021 [S]. Beijing: China Agriculture Press, 2021.
[9]	黄敏. 茶叶或茶青中有机磷和氨基甲酸酯类农药残留快速检测方法[J]. 福建分析测试, 2018, 27(3): 1-5.Huang M.Method for rapid determination of organophosphorus and carbamate pesticide residues in fresh and processed tea leaves[J]. Fujian Analysis & Testing, 2018, 27(3): 1-5.
[10]	肖文敏, 唐小燕, 任志红, 等. 基于电子鼻技术的茶鲜叶农残快速诊断[J]. 茶叶通讯, 2021, 48(3): 484-493.Xiao W M, Tang X Y, Ren Z H, et al.Rapid diagnosis of pesticide residue in fresh tea leaves based on electronic nose technology[J]. Journal of Tea Communication, 2021, 48(3): 484-493.
[11]	王兴进. 气相色谱法测定茶青中有机氯农药残留量[J]. 茶叶科学技术, 2006(2): 39-40.Wang X J.Determination of organochlorine pesticide residues in tea green by gas chromatography[J]. Tea Science and Technology, 2006(2): 39-40.
[12]	刘腾飞, 杨代凤, 董明辉, 等. 分散固相萃取-气相色谱法测定茶鲜叶中7种拟除虫菊酯类农药残留[J]. 农药学学报, 2015, 17(5): 571-578.Liu T F, Yang D F, Dong M H, et al.Determination of pyrethroid residues in fresh tea leaves by dispersive solid phase extraction and gas chromatography[J]. Chinese Journal of Pesticide Science, 2015, 17(5): 571-578.
[13]	李俊, 蔡滔, 杜楠, 等. QuEChERS-气相色谱-串联质谱法测定茶青中28种农药残留[J]. 农药学学报, 2017, 19(3): 366-373.Li J, Cai T, Du N, et al.Determination of 28 pesticide residues in fresh tea leaves using QuEChERS-gas chromatography-tandem mass spectrometry[J]. Chinese Journal of Pesticide Science, 2017, 19(3): 366-373.
[14]	罗先锟, 何江, 黄义彬. 基于QuEChERs-GC-MS/MS法同时测定茶青中38种农药残留[J]. 食品安全导刊, 2021(29): 71-74.Luo X K, He J, Huang Y B.Simultaneous determination of 38 pesticide residues in tea green by QuEChERs-GC-MS/MS method[J]. China Food Safety Magazine, 2021(29): 71-74.
[15]	张艳侠, 张婷, 薛霞, 等. QuEChERS/超高效液相色谱-串联质谱法测定茶叶中17种氨基甲酸酯类农药及其代谢物残留[J]. 分析试验室, 2019, 38(1): 13-18.Zhang Y X, Zhang T, Xue X, et al.Simultaneous determination of 17 carbamate pesticides residues in tea by QuEChERS-UPLC-MS/MS[J]. Chinese Journal of Analysis Laboratory, 2019, 38(1): 13-18.
[16]	徐春奎, 李艳, 侯莉莉, 等. 破壁处理与改进QuEChERS结合UPLC-MS/MS快速检测蔬菜中52种农药残留[J]. 安徽农业科学, 2019, 47(22): 200-205, 260.Xu C K, Li Y, Hou L L, et al.Rapid determination of 52 pesticide residues in vegetables by ultra performance liquid chromatography-tandem mass spectrometry with wall-breaking treatment and improved-QuEChERS[J]. Journal of Anhui Agricultural Science, 2019, 47(22): 200-205, 260.
[17]	郭立群, 徐军, 董丰收, 等. 分散固相萃取-超高效液相色谱-串联质谱法同时检测玉米及其土壤中烟嘧磺隆、莠去津及氯氟吡氧乙酸残留[J]. 农药学学报, 2012, 14(2): 177-184.Guo L Q, Xu J, Dong F S, et al.Simultaneous determination of nicosulfuron, atrazine and fluroxypyr in soil and corn by ultraperformance liquid chromatography-mass spectrometry[J]. Chinese Journal of Pesticide Science, 2012, 14(2): 177-184.
[18]	吴燕梅, 邓华阳, 杨钦沾, 等. 优化的QuEChERS/超高液相色谱-串联质谱法测定鲜茶叶中21种氨基甲酸酯类农药残留[J]. 化学研究与应用, 2018, 30(3): 437-443.Wu Y M, Deng H Y, Yang Q Z, et al.Determination of 21 carbamate pesticide residues in fresh tea by modified-QuEChERS combined with ultra high performance liquid chromatography-tandem mass spectrometry[J]. Chemical Research and Application, 2018, 30(3): 437-443.
[19]	Liu T F, Dong M H, Zhou F J, et al.Development and validation of an analytical method for detecting chlorantraniliprole residues in fresh tea leaves[J]. Food Science and Human Wellness, 2019, 8(4): 362-367.
[20]	Huang T T, Tang H, Dong X Q, et al.Determination of 23 organophosphorus pesticide residues in tea by QuEChERS extraction with multi-walled carbon nanotubes (MWCNTs) coupled to gas chromatography[J]. Food Science, 2018, 39(6): 315-321.
[21]	尹鹏, 陈红平, 刘新, 等. 5种分散吸附剂对茶叶乙腈提取液组分的吸附作用研究[J]. 分析试验室, 2013, 32(6): 54-58.Yin P, Chen H P, Liu X, et al.Study on effect of five dispersive solid adsorbents on the components of tea extracts by acetonitrile[J]. Chinese Journal of Analysis Laboratory, 2013, 32(6): 54-58.
[22]	李自强, 杨梅, 张新忠, 等. 超高效液相色谱-串联质谱法检测绿茶中16种农药残留[J]. 茶叶科学, 2022, 42(4): 537-548.Li Z Q, Yang M, Zhang X Z, et al.Residue determination of sixteen pesticides in green tea by UPLC-MS/MS[J]. Journal of Tea Science, 2022, 42(4): 537-548.
[23]	Pang G F, Fan C L, Chang Q Y, et al.Matrix effect for determination of pesticide residues in tea[M]//Pang G F, Fan C L, Chang Q Y, et al. Analysis of pesticide in tea: chromatography-mass spectrometry methodology. Amsterdam: Elsevier Inc., 2018: 535-595.
[24]	Stahnke H, Reemtsma T, Alder L.Compensation of matrix effects by post column infusion of a monitor substance in multiresidue analysis with LC-MS/MS[J]. Analytical Chemistry, 2009, 81(6): 2185-2192.
[25]	王立琦, 贺利民, 曾振灵, 等. 液相色谱-串联质谱检测兽药残留中的基质效应研究进展[J]. 质谱学报, 2011, 32(6): 321-332.Wang L Q, He L M, Zeng Z L, et al.Progress in matrix effect of veterinary drug residues analysis by high-performance liquid chromatograph tandem mass spectrometry[J]. Journal of Chinese Mass Spectrometry Society, 2011, 32(6): 321-332.
[26]	史君, 吕永恒. 如何消除食品质谱分析的基质效应[J]. 中国食品工业, 2022(1): 54-55.Shi J, Lü Y H.How to eliminate matrix effect of food mass spectrometry[J]. Chinese Food Industry, 2022(1): 54-55.
[27]	中华人民共和国国家卫生健康委员会. 食品安全国家标准食品中农药最大残留限量: GB 2763—2021[S]. 北京: 中国农业出版社, 2021.National Health Commission of the People’s Republic of China. National food safety standard-maximum residue limits for pesticides in food: GB 2763—2021 [S]. Beijing: China Agriculture Press, 2021.
[28]	赵平, 严秋旭, 李新, 等. 双酰胺类杀虫剂的现状与展望[J]. 农药科学与管理, 2015, 36(11): 23-29.Zhao P, Yan Q X, Li X, et al.Status and perspective of diamide insecticides[J]. Pesticide Science and Administration, 2015, 36(11): 23-29.
[29]	陈小平, 柳爱平, 关少飞, 等. 双酰胺类杀虫剂及其应用市场与防治刺吸式口器害虫前景[J]. 世界农药, 2021, 43(11): 1-12.Chen X P, Liu A P, Guan S F, et al.Diamide insecticides and their application market and prospect of controlling sucking pests[J]. World Pesticide, 2021, 43(11): 1-12.