建立了茶叶中3类11种农药的分散固相萃取–高效液相色谱串联质谱（HPLC-MS-MS）的检测方法。茶叶样品以乙腈–乙酸（体积比99:1）提取,以PSA为净化剂基质固相分散萃取,然后通过C18色谱柱,以甲醇/水（含甲酸铵）溶液进行梯度洗脱,采用电离喷雾电离方式（ESI+）,通过多反应监测（MRM）定量。结果表明：11种农药的分析时间约为20 min,在0~500 ng·mL-1范围内线性相关,相关系数大于0.9995,方法检测限为0.1~1.7 μg·kg-1。测定了茶叶样品中11种农药的残留量,加标回收率为62.4%~114.8%（添加水平分别为10~400 μg·kg-1）,相对标准偏差（RSD）为3.28%~19.34%。选取了5个不同类型的茶叶样品,检测其中11种农药的残留量,检出结果差异较大。其中绿茶中11种农药的检出量为1.7~339.4 μg·kg-1,加标回收率为86.1%~104.1%,相对标准偏差（RSD）均小于20%（n=6）。本方法准确、灵敏、简单、快速、安全,能满足茶叶样品中多种农药残留分析的要求。
A method for rapid determination of 11 kinds of pesticide residues in tea samples by matrix solid-phase disperse extraction and high performance liquid chromatography and tandem mass spectrometry was proposed. The pesticide residues in tea sample were firstly extracted by a mixture of V(acetonitrile):V(acetic acid)=99:1, and the extract was solid-phase disperse purified by PSA and then separated on a Waters Xterra MS C18 column with a gradient system of a mixture of methanol and water with ammonium formate. Multi-reaction monitoring (MRM) was employed for quantitative determination. Eleven pesticide residues could be detected within 20 min. The linear range of 11 pesticide residue was 0-500 ng·mL -1 and the limits of detection were between 0.1-1.7 μg·kg-1. The correlation rate was more than 0.9995. The average recoveries (spiked at the levels of 10-400 μg·kg-1) ranged from 62.4% to 114.8% with relative standard deviation between 3.28% and 19.34%. After extraction and purification, 11 pesticide residues in 5 samples of different kinds of tea with significant variation in content were analyzed. And the residue content of 11 pesticides in green tea sample was 1.7-339.4 μg·kg-1. Recoveries in this sample were ranged from 86.1% to 104.1% with relative standard deviations less than 20%. This method is accurate, sensitive, simple, rapid,safe and suitable for identification and quantification of multiple pesticide residues in tea.
[1] 陈石榕. 对欧盟茶叶农药残留新标准的思考[J]. 世界标准化与质量管理, 2000, 7: 28-29.
[2] Nasreddine L, Parent-Massin D.Food contamination by metals and pesticides in the European Union. Should we worry?[J]. Toxicology Letters, 2002, 127(1): 29-41.
[3] 陈宗懋. 我国出口茶农药残留现状和2003 年国外新标准[J]. 茶叶经济信息, 2003(3): 21.
[4] Huang Z, Li Y, Chen B, et al. Simultaneous determination of 102 pesticide residues in Chinese teas by gas chromatography-mass spectrometry[J]. Journal of Chromatography B, 2007, 853(1): 154-162.
[5] 郭防. 茶叶中农药残留检测的样品前处理研究进展[J]. 微量元素与健康研究, 2012, 29(1): 61-64.
[6] 冯洁, 汤桦, 陈大舟, 等. 茶叶中9种有机氯和拟除虫菊酯农药残留的前处理方法研究[J]. 分析测试学报, 2010, 29(10): 1041-1047.
[7] 刘小文, 吴国星, 高熹, 等. 几种新技术在茶叶农药残留分析样品前处理中的应用[J]. 云南大学学报: 自然科学版, 2008(S1): 210-214.
[8] Bicchi C, Cordero C, Iori C, et al. SBSE-GC-ECD/FPD in the analysis of pesticide residues in Passiflora alata Dryander herbal teas[J]. Journal of Agricultural and Food Chemistry, 2003, 51(1): 27-33.
[9] Hu B, Song W, Xie L, et al. Determination of 33 pesticides in tea by accelerated solvent extraction-gel permeation and solid-phase extraction purification-gas chromatography- mass spectrometry[J]. Chinese Journal of Chromatography, 2008, 26(1): 22.
[10] Chen G, Cao P, Liu R.A multi-residue method for fast determination of pesticides in tea by ultra performance liquid chromatography-electrospray tandem mass spectrometry combined with modified QuEChERS sample preparation procedure[J]. Food Chemistry, 2011, 125(4): 1406-1411.
[11] Anastassiades M, Lehotay S J, Stajnbaher D, et al. Fast and easy multiresidue method employing acetonitrile extraction/partitioning and dispersive solid-phase extraction for the determination of pesticide residues in produce[J]. Journal of AOAC International, 2003, 86(2): 412-431.
[12] 何聿, 陈金泉, 张兰. 有机磷农药残留前处理技术的研究[J]. 福建分析测试, 2007, 16(3): 6-11.
[13] 黄琼辉. 国内外农药残留检测技术研究进展和发展方向[J]. 福建农业学报, 2008, 23(2): 218-222.
[14] 闵光. 基质固相分散萃取在农药残留检测技术中的应用[J]. 现代农业科技, 2010, 9: 169-171.
[15] 蒋迎, 郑平, 鲁成银. 基于基质固相分散萃取的茶叶中拟除虫菊酯多农残气相色谱测定[J]. 茶叶, 2007, 33(3): 147-149.
[16] Chen Z, Wang Y.Chromatographic methods for the determination of pyrethrin and pyrethroid pesticide residues in crops, foods and environmental samples[J]. Journal of Chromatography A, 1996, 754(1): 367-395.
[17] Zhao H, Zhao S, Deng L, et al. Rapid Determination of Organonitrogen, Organophosphorus and Carbamate Pesticides in Tea by Ultrahigh-Performance Liquid Chromatography-Tandem Mass Spectrometry (UPLC-MS/MS)[J]. Food Analytical Methods, 2013, 6(2): 497-505.
[18] Fraser K, Harrison S J, Lane G A, et al. Analysis of low molecular weight metabolites in tea using mass spectrometry-based analytical methods[J]. Critical Reviews in Food Science and Nutrition, 2014, 54(7): 924-937.
[19] Yang X, Qiu J W, Zhang H, et al. Simultaneous determination of 118 pesticide residues in Chinese teas by gas chromatography-mass spectrometry[J]. Chemical Papers, 2009, 63(1): 39-46.
[20] Wan H, Xia H, Chen Z.Extraction of pesticide residues in tea by water during the infusion process[J]. Food Additives & Contaminants, 1991, 8(4): 497-500.
[21] 李云春, 易军, 弓振斌, 等. 反相高效液相色谱法测定茶叶中氯氰菊酯和氰戊菊酯农药残留[J]. 厦门大学学报: 自然科学版, 2003, 42(1): 78-82.
[22] 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): 391-400.
[23] 宋淑玲, 李重九, 马晓东, 等. 蔬菜中残留农药的石墨化碳黑净化和气相色谱-质谱检测方法[J]. 分析化学, 2008, 1526: 1530.
[24] Schenck F J, Lehotay S J.Does further clean-up reduce the matrix enhancement effect in gas chromatographic analysis of pesticide residues in food?[J]. Journal of Chromatography A, 2000, 868(1): 51-61.
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