An efficient method for the determination of glyphosate and its metabolite aminomethyl phosphonic acid (AMPA) in green tea was developed based on gas chromatography-mass spectrometry (GC-MS). Green tea samples were extracted with water, preliminary purified by dichloromethane and followed by purification with PCX and HLB combined solid phase extraction columns, derived with trifluoroacetic anhydride (TFAA) and 2,2,3,3,4,4,4-heptafluoro-1-butanol (HFB), then determined by GC-MS. For glyphosate, the limit of quantification (LOQ) was 0.05 mg·kg-1, showing good linearity with coefficient R2=0.999 3 in the concentration range from 2-100 ng·mL-1. For AMPA, itsLOQ was 0.02 mg·kg-1, showing good linearity with coefficient R2=0.999 2 in the concentration range from 1-100 ng·mL-1. At the spiked levels of 0.25 mg·kg-1 and 0.50 mg·kg-1, the average recoveries of glyphosate in green tea were 90.8% and 93.2%, with relative standard deviation (RSD) of 4.93% and 6.74%. At the spiked levels of 0.10 mg·kg-1 and 0.20 mg·kg-1, the average recoveries of AMPA in green tea were 85.8% and 95.4%, with RSD of 10.5% and 5.16%. The proper impurity purification, small impurity interference and high recovery rate made this method suitable for residue detection of glyphosate and its metabolite APMA in green tea.
[1] 陈世国, 强胜, 毛婵娟. 草甘膦的作用机制和抗性研究进展[J]. 植物保护, 2017, 43(2): 17-24.
Chen S G, Qiang S, Mao C J.Mechanism of action of glyphosate and research advances in glyphosate resistance[J]. Plant Protection, 2017, 43(2): 17-24.
[2] 周垂帆, 李莹, 张晓勇, 等. 草甘膦毒性研究进展[J]. 生态环境学报, 2013, 22(10): 1737-1743.
Zhou C F, Li Y, Zhang X Y, et al.Research advance in ecotoxicity of glyphosate[J]. Ecology and Environmental Sciences, 2013, 22(10): 1737-1743.
[3] 中华人民共和国国家卫生和计划生育委员会. 食品安全国家标准食品中农药最大残留限量: GB 2763—2016[S]. 北京: 中国标准出版社, 2016.
National Health and Family Planning Commission of PRC. National food safety standard—maximum residue limits for pesticides in food: GB 2763—2016 [S]. Beijing: Standards Press of China, 2016
[4] 李国鹏, 周彩荣, 石晓华, 等. 分光光度法测定草甘膦生产废水中草甘膦和甘氨酸的含量[J]. 郑州大学学报(理学版), 2012, 44(2): 81-84.
Li G P, Zhou C R, Shi X H, et al.Determination of the Amount of glyphosate and glycine in the wastewater of glyphosate produced by spectrophotometry[J]. Journal of Zhengzhou University (Natural Science Edition), 2012, 44(2): 81-84.
[5] 王聪, 刘颖超, 庞民好, 等. 高效液相色谱柱后衍生法测定农田沟渠水中草甘膦残留[J]. 植物保护, 2012, 38(5): 96-99.
Wang C, Liu Y C, Pang M H, et al.Determination of glyphosate in the water of farmland ditch by high performance liquid chromatography-post column derivation[J]. Plant Protection, 2012, 38(5): 96-99.
[6] Zhang W D, Feng Y R, Ma L, et al.A method for determining glyphosate and its metabolite aminomethyl phosphonic acid by gas chromatography-flame photometric detection[J]. Journal of Chromatography A, 2019, 1589: 116-121.
[7] You J, Koropchak J A.Condensation nucleation light scattering detection with ion chromatography for direct determination of glyphosate and its metabolite in water[J]. Journal of Chromatography A, 2003, 989(2): 231-238.
[8] 罗彤, 付文雯, 郭卢云, 等. QuEChERS-气相色谱-三重四级杆串联质谱法测定茶叶中草甘膦和氨甲基膦酸残留[J]. 食品研究与开发, 2018, 39(14): 153-158.
Luo T, Fu W W, Guo L Y, et al.Determination of glyphosate and aminomethyl phosphonic acid residues in tea by quechers and gas chromatography-triple quadrupole mass spectrometry[J]. Food Research and Development, 2018, 39(14): 153-158.
[9] 诸力, 陈红平, 周苏娟, 等. 超高效液相色谱-串联质谱法测定不同茶叶中草甘膦、氨甲基膦酸及草铵膦的残留[J]. 分析化学, 2015, 43(2): 271-276.
Zhu L, Chen H P, Zhou S J, et al.Determination of glyphosate,aminomethyl phosphonic acid and glufosinate in different teas by ultra performance liquid chromatography-tandem mass spectrometry[J]. Chinese Journal of Analytical Chemistry, 2015, 43(2): 271-276.
[10] 曹丽伟, 梁丝柳, 谭小芳, 等. 毛细管电泳-激光诱导荧光法测定草甘膦、草胺膦及氨甲基膦酸[J]. 色谱, 2012, 30(12): 1295-1300.
Cao L W, Liang S L, Tan X F, et al.Capillary electrophoresis analysis for glyphosate, glufosinate and aminomethylphosphonic acid with laser-induced fluorescence detection[J]. Chinese Journal of Chromatography, 2012, 30(12): 1295-1300.
[11] 张超, 李腾飞, 赵风年, 等. 分子印迹电化学传感器的制备及其快速检测饮水中草甘膦残留的应用研究[J]. 分析测试学报, 2016, 35(12): 1542-1547.
Zhang C, Li T F, Zhao F N, et al.Preparation of an electrochemical sensor based on molecularly imprinted polymer and its application in determination of glyphosate residues in water samples[J]. Journal of Instrumental Analysis, 2016, 35(12): 1542-1547.
[12] 吴晓刚, 陈孝权, 肖海军, 等. 柱前衍生-超高效液相色谱-串联质谱法同时检测茶叶中草甘膦和草铵膦的残留量[J]. 色谱, 2015, 33(10): 1090-1096.
Wu X G, Chen X Q, Xiao H J, et al.Simultaneous determination of glyphosate and glufosinateammonium residues in tea by ultra performance liquid chromatography-tandem mass spectrometry coupled with pre-column derivatization[J]. Chinese Journal of Chromatography, 2015, 33(10): 1090-1096.
[13] 陈磊. HPLC-MS/MS同时检测乌龙茶中草铵膦、草甘膦和氨甲基膦酸残留[J]. 茶叶科学技术, 2014(1): 21-27.
Chen L.Simultaneous detection of glufosinate, glyphosate and (aminomethyl) phosphonic acid in Oolong tea by HPLC-MS/MS[J]. Acta Tea Sinica, 2014(1): 21-27.
[14] 刘正才, 蔡春平, 林永辉, 等. 分散固相萃取/液相色谱-串联质谱法测定茶叶中草甘膦及其代谢物氨甲基膦酸的残留量[J]. 分析测试学报, 2015, 34(3): 335-340.
Liu Z C, Cai C P, Lin Y H, et al.Determination of glyphosate and aminomethylphosphonic acid residues in tea by dispersive solid-phase extraction combined with high performance liquid chromatography-tandem mass spectrometry[J]. Journal of Instrumental Analysis, 2015, 34(3): 335-340.
[15] 叶美君, 陆小磊, 刘相真, 等. 柱前衍生-超高效液相色谱-串联质谱测定茶叶中草甘膦、草铵膦及主要代谢物氨甲基膦酸残留[J]. 色谱, 2018, 36(9): 873-879.
Ye M J, Lu X L, Liu X Z, et al.Determination of glyphosate, glufosinate, and main metabolite aminomethylphosphonic acid residues in dry tea using ultra-high performance liquid chromatography-tandem mass spectrometry[J]. Chinese Journal of Chromatography, 2018, 36(9): 873-879.
[16] 中华人民共和国国家质量监督检验检疫总局. 植物性产品中草甘膦残留量的测定气相色谱-质谱法: GB/T 23750—2009[S]. 北京: 中国标准出版社, 2009.
General Administration of Quality Supervision, Inspection and Quarantine of the People's Republic of China. Determination of glyphosate residues in plant —GC-MS method: GB/T 23750—2009 [S]. Beijing: Standards Press of China, 2009.
[17] Lars C.Schrübbers, Mario Masís-Mora, Elizabeth Carazo Rojas, et al. Analysis of glyphosate and aminomethylphosphonic acid in leaves from Coffeaarabica using high performance liquid chromatography with quadrupole mass spectrometry detection[J]. Talanta, 2016, 146: 609-620.
浙公网安备 33019902000101号 
