Simultaneous Determination of Glyphosate, Glufosinate and Aminomethyl Phosphonic Acid Residues in Tea by Modified QuEChERS Method Coupled with UPLC-MS/MS

LI Ziqiang; YANG Mei; ZHANG Xinzhong; LUO Fengjian; LOU Zhengyun; LIANG Shuang

doi:10.13305/j.cnki.jts.2023.02.001

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Journal of Tea Science ›› 2023, Vol. 43 ›› Issue (2) : 263-274. DOI: 10.13305/j.cnki.jts.2023.02.001

Simultaneous Determination of Glyphosate, Glufosinate and Aminomethyl Phosphonic Acid Residues in Tea by Modified QuEChERS Method Coupled with UPLC-MS/MS

LI Ziqiang¹, YANG Mei², ZHANG Xinzhong², LUO Fengjian², LOU Zhengyun², LIANG Shuang^1,*

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Abstract

An analytical method was developed for the simultaneous determination of glyphosate, glufosinate and aminomethyl phosphonic acid residues in black and green tea by ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) coupled with a modified QuEChERS method. The samples were extracted twice with pure water, and the extraction solutions were purified by dispersive solid phase extraction with MWCNT, C₁₈, PVPP and CNT-OH adsorbents. The mass spectrometry was performed in multiple reaction monitoring (MRM) mode and quantified by external standard method. The results show that glyphosate, glufosinate and aminomethyl phosphonic acid had a good linear relationship within a certain concentration range with correlation coefficients (R²) ranging from 0.999 3 to 1.000 0 in black and green tea. The limits of detection ( LOD ) of the method were 0.005 0, 0.030 mg·kg^-1 and 0.030 mg·kg^-1, respectively. The limits of quantitation (LOQ) were 0.050, 0.10 mg·kg^-1 and 0.10 mg·kg^-1, respectively. The average spiked recovery rates and the relative standard deviations (RSD) of pesticides were in the range of 81.6%-120.0% and 0.6%-13.6%, respectively. The method is simple, inexpensive, reproducible, sensitive and suitable for the determination of glyphosate, glufosinate and aminomethyl phosphonic acid in black and green tea.

Key words

aminomethyl phosphonic acid / glufosinate / glyphosate / QuEChERS / tea

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LI Ziqiang, YANG Mei, ZHANG Xinzhong, LUO Fengjian, LOU Zhengyun, LIANG Shuang. Simultaneous Determination of Glyphosate, Glufosinate and Aminomethyl Phosphonic Acid Residues in Tea by Modified QuEChERS Method Coupled with UPLC-MS/MS[J]. Journal of Tea Science. 2023, 43(2): 263-274 https://doi.org/10.13305/j.cnki.jts.2023.02.001

References

[1] Du Z X, Cao J Y, Li W T, et al.A method to assess glyphosate, aminomethylphosphonic acid and glufosinate in Chinese herb samples using a derivatization method and LC-MS/MS[J]. Chromatographia, 2022, 85(9): 817-829.
[2] Poiger T, Buerge I J, Bachli A, et al.Occurrence of the herbicide glyphosate and its metabolite AMPA in surface waters in Switzerland determined with on-line solid phase extraction LC-MS/MS[J]. Environmental Science and Pollution Research, 2017, 24(2): 1588-1596.
[3] Wang Y, Gao W J, Li Y Y, et al.Establishment of a HPLC-MS/MS detection method for glyphosate, glufosinate-ammonium, and aminomethyl phosphoric acid in tea and its use for risk exposure assessment[J]. Journal of Agricultural and Food Chemistry, 2021, 69(28): 7969-7978.
[4] Goodwin L, Startin J R, Keely B J, et al.Analysis of glyphosate and glufosinate by capillary electrophoresis-mass spectrometry utilising a sheathless microelectrospray interface[J]. Journal of Chromatography A, 2003, 1004(1/2): 107-119.
[5] Liao Y, Berthion J M, Colet I, et al.Validation and application of analytical method for glyphosate and glufosinate in foods by liquid chromatography-tandem mass spectrometry[J]. Journal of Chromatography A, 2018, 1549: 31-38.
[6] Li H X, Zhong Q, Wang X R, et al.Simultaneous quantitative determination of residues of pyriproxyfen and its metabolites in tea and tea infusion using ultra-performance liquid chromatography-tandem mass spectrometry[J]. Agronomy-Basel, 2022, 12(8): 1829. doi: 10.3390/agronomy12081829.
[7] Huang Y S, Shi T, Luo X, et al.Determination of multi-pesticide residues in green tea with a modified QuEChERS protocol coupled to HPLC-MS/MS[J]. Food Chemistry, 2019, 275: 255-264.
[8] Tong M M, Gao W J, Jiao W T, et al.Uptake, translocation, metabolism, and distribution of glyphosate in nontarget tea plant (Camellia SinensisL.)[J]. Journal of Agricultural and Food Chemistry, 2017, 65(35): 7638-7646.
[9] 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.
[10] European Commission.EU pesticide residue limit standard database [EB/OL]. [2023-01-13].https://ec.europa.eu/food/plant/pesticides/eu-pesticides-database/start/screen/mrls.
[11] The Japan Food Chemical Research Foundation. Maximum Residue Limits (MRLs) List of Agricultural Chemicals in Foods [EB/OL]. [2023-01-13]. http://db.ffcr.or.jp/front.
[12] 李小娟, 孟品佳, 王燕燕, 等. 毛细管电泳-间接紫外法测定饮用水中草甘膦, 草铵膦及其代谢产物[J]. 理化检验-化学分册, 2015, 51(3): 307-311.
Li X J, Meng P J, Wang Y Y, et al.Determination of glyphosate, glufosinate and their metabolites by capillary electrophoresis combined with indirect UV detection[J]. Physical Testing and Chemical Analysis (Part B: Chemical Analysis), 2015, 51(3): 307-311.
[13] Tseng S H, Lo Y W, Chang P C, et al.Simultaneous quantification of glyphosate, glufosinate, and their major metabolites in rice and soybean sprouts by gas chromatography with pulsed flame photometric detector[J]. Journal of Agricultural and Food Chemistry, 2004, 52(13): 4057-4063.
[14] Pires N L, Passos C J S, Morgado M G A, et al. Determination of glyphosate, AMPA and glufosinate by high performance liquid chromatography with fluorescence detection in waters of the santarém plateau, Brazilian amazon[J]. Journal of Environmental Science and Health Part B, 2020, 55(9): 794-802.
[15] Geerdink R B, Hassing M, Ayarza N, et al.Analysis of glyphosate, AMPA, glufosinate and MPPA with ion chromatography tandem mass spectrometry using a membrane suppressor in the ammonium form application to surface water of low to moderate salinity[J]. Analytica Chimica Acta, 2020, 1133: 66-76.
[16] Jansons M, Pugajeva I, Bartkevics V, et al.LC-MS/MS characterisation and determination of dansyl chloride derivatised glyphosate, aminomethylphosphonic acid (AMPA), and glufosinate in foods of plant and animal origin[J]. Journal of Chromatography B, 2021, 1177: 122779. doi: 10.1016/j.jchromb.2021.122779.
[17] Demonte L D, Michlig N, Gaggiotti M, et al.Determination of glyphosate, AMPA and glufosinate in dairy farm water from argentina using a simplified UHPLC-MS/MS method[J]. Science of the Total Environment, 2018, 645: 34-43.
[18] 杨亚琴, 冯书惠, 胡永建, 等. 气相色谱-质谱法测定绿茶中草甘膦和氨甲基膦酸残留量[J]. 茶叶科学, 2020, 40(1): 125-132.
Yang Y Q, Feng S H, Hu Y J, et al.Determination of glyphosate and aminomethyl phosphonic acid residue in green tea by gas chromatography-mass spectrometry[J]. Journal of Tea Science, 2020, 40(1): 125-132.
[19] Zhuang M, Feng X X, Wang J, et al.Method development and validation of seven pyrethroid insecticides in tea and vegetable by modified QuEChERS and HPLC-MS/MS[J]. Bulletin of Environmental Contamination and Toxicology, 2022, 108(4): 768-778.
[20] Botero-Coy A M, Ibanez M, Sancho J V, et al. Direct liquid chromatography-tandem mass spectrometry determination of underivatized glyphosate in rice, maize and soybean[J]. Journal of Chromatography A, 2013, 1313: 157-165.
[21] Li Z M, Kannan K.A method for the analysis of glyphosate, aminomethylphosphonic acid, and glufosinate in human urine using liquid chromatography-tandem mass spectrometry[J]. International Journal of Environmental Research and Public Health, 2022, 19(9): 4966. doi: 10.3390/ijerph19094966.
[22] Ding J J, Jin G H, Jin G W, et al.Determination of underivatized glyphosate residues in plant-derived food with low matrix effect by solid phase extraction-liquid chromatography-tandem mass spectrometry[J]. Food Analytical Method, 2016, 9(10): 2856-2863.
[23] Wang J, Duan H L, Fan L, et al.A magnetic fluorinated multi-walled carbon nanotubes-based QuEChERS method for organophosphorus pesticide residues analysis inLycium ruthenicumMurr[J]. Food Chemistry, 2021, 338: 127805. doi: 10.1016/j.foodchem.2020.127805.
[24] 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.
[25] 冯月超, 马立利, 贾丽, 等. 多壁碳纳米管分散固相萃取-液质联用技术测定茶叶中草甘膦, 草铵膦, 氨甲基膦酸残留量[J]. 食品安全质量检测学报, 2014, 5(4): 1147-1154.
Feng Y C, Ma L L, Jia L, et al.Determination of glyphosate, glufosinate and aminomethylphonic acid residues in tea by liquid chromatography-tandem mass spectrometry using multi-walled carbon nanotubes as dispersive solid-phase extraction sorbent[J]. Journal of Food Safety and Quality, 2014, 5(4): 1147-1154.
[26] 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.
[27] 励炯, 安海娟, 王红青, 等. 改进的固相萃取/高效液相色谱-串联质谱法测定茶叶中草甘膦和氨甲基膦酸残留量[J]. 分析仪器, 2019(1): 102-107.
Li J, An H J, Wang H Q, et al.Determination of glyphosate and aminomethyl phosphonic acid in tea by modified high performance liquid chromatography-tandem mass spectrometry with purification based on solid phase extraction[J]. Analytical Instrumentation, 2019(1): 102-107.
[28] 赵春华, 左于一菲, 孙倩. 高效液相色谱-串联质谱法检测茶叶中痕量草胺膦、草甘膦及其代谢物氨甲基膦酸残留[J]. 化学分析计量, 2018, 27(5): 96-101.
Zhao C H, Zuo-Yu Y F, Sun Q. Determination of trace glufosinate, glyphosate and its metabolites residue in tea by HPLC-MS/MS[J]. Chemical Analysis and Meterage, 2018, 27(5): 96-101.
[29] 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 glufosinate-ammonium 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.
[30] 孙文闪, 章虎, 王川丕, 等. 分散固相萃取净化液质联用测定茶叶中的草铵膦, 草甘膦和氨甲基膦酸残留[J]. 分析试验室, 2020, 39(6): 658-663.
Sun W S, Zhang H, Wang C P, et al.Determination of glufosinate,glyphosate and aminomethyl phosphonic acid in tea by liquid chromatography triple quadrupole mass spectrometry using dispersive solid-phase extraction sorbent[J]. Chinese Journal of Analysis Laboratory, 2020, 39(6): 658-663.
[31] 王如坤, 方爱琴, 赵海英, 等. 超高效液相色谱-四极杆/静电场轨道阱高分辨质谱法快速检测茶叶中草甘膦、草铵膦及其代谢物残留[J]. 食品安全质量检测学报, 2021, 12(10): 3954-3959.
Wang R K, Fang A Q, Zhao H Y, et al.Rapid determination of glyphosate, glufosinate-ammonium and their metabolite residues in tea by ultra performance liquid chromatography-quadrupole electrostatic field orbital trap high resolution mass spectrometry[J]. Journal of Food Safety and Quality, 2021, 12(10): 3954-3959.
[32] 杨梅, 孙思, 刘文锋, 等. 超高效液相色谱-串联质谱法测定茶叶中草甘膦和草铵膦的残留量[J]. 食品科学, 2019, 40(10): 337-343.
Yang M, Sun S, Liu W F, et al.Determination of glyphosate and glufosinate-ammonium residues in tea by UPLC-MS/MS[J]. Food Science, 2019, 40(10): 337-343.
[33] 蒋瑞东, 金戈辉. 气相色谱法测定果蔬中5种拟除虫菊酯类农药残留[J]. 化学分析计量, 2009, 18(5): 55-58.
Jiang R D, Jin G H.Determination of 5 pyrethroid pesticide residues in fruits and vegetables by gas chromatography[J]. Chemical Analysis and Meterage, 2009, 18(5): 55-58
[34] 邓爱华, 冯国金. 植物性食品中有机氯农药残留量检测的前处理方法研究[J]. 分析测试学报, 2010, 29(9): 958-961.
Deng A H, Feng G J.Investigation on different pretreatment methods for determination of residual organochlorine pesticides in phytogenic foodstuff[J]. Journal of Instrumental Analysis, 2010, 29(9): 958-961.
[35] 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.
[36] Guan Y Q, Tang H, Chen D Z, et al.Modified QuEChERS method for the analysis of 11 pesticide residues in tea by liquid chromatography-tandem mass spectrometry[J]. Analytical Methods, 2013, 5(12): 3056-3067.
[37] Huo F F, Tang H, Wu X, et al. Utilizing a novel sorbent in the solid phase extraction for simultaneous determination of 15 pesticide residues in green tea by GC/MS [J]. Journal of Chromatography B, 2016, 1023/1024: 44-54.
[38] Han Y T, Song L, Zou N, et al.Multi-residue determination of 171 pesticides in cowpea using modified QuEChERS method with multi-walled carbon nanotubes as reversed-dispersive solid-phase extraction materials[J]. Journal of Chromatography B, 2016, 1031: 99-108.
[39] Wang C, Chen H P, Zhu L, et al.Accurate, sensitive and rapid determination of perchlorate in tea by hydrophilic interaction chromatography-tandem mass spectrometry[J]. Analytical Methods, 2020, 12(28): 3592-3599.
[40] Zhang M L, Ma G C, Zhang L, et al.Chitosan-reduced graphene oxide composites with 3d structures as effective reverse dispersed solid phase extraction adsorbents for pesticides analysis[J]. Analyst, 2019, 144(17): 5164-5171.
[41] 彭晓俊, 伍长春, 梁伟华, 等. 气相色谱-质谱法测定陈皮及其制品中的三氯杀螨醇和拟除虫菊酯残留量[J]. 理化检验-化学分册, 2019, 53(7): 848-854.
Peng X J, Wu C C, Liang W H, et al.GC-MS determination of residual amounts of dicofol and pyrethroids in dried orange peel and its products[J]. Physical Testing and Chemical Analysis (Part B: Chemical Analysis), 2019, 53(7): 848-854.
[42] Zhao P Y, Wang L, Jiang Y P, 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 and Food Chemistry, 2012, 60(16): 4026-4033.
[43] Wang Z H, Wang X R, Wang M, et al.Establishment of a QuEChERS-UPLC-MS/MS method for simultaneously detecting tolfenpyrad and its metabolites in tea[J]. Agronomy, 2022, 12(10): 2324. doi: 10.3390/agronomy12102324.
[44] Rutkowska E, Lozowicka B, Kaczynski P.Three approaches to minimize matrix effects in residue analysis of multiclass pesticides in dried complex matrices using gas chromatography tandem mass spectrometry[J]. Food Chemistry, 2019, 279: 20-29.
[45] 曹慧, 郑军科, 黄丽英, 等. QuEChERS-UPLC/MS/MS快速测定茶叶中的草甘膦和氨甲基磷酸[J]. 食品与机械, 2016, 32(4): 84-87.
Cao H, Zheng J K, Huang L Y, et al.Fast determination of glyphosate and aminomethyl phosphonic acid residues in tea QuEChERs and UPLC/MS/MS[J]. Food and Machinery, 2016, 32(4): 84-87.