加速溶剂萃取-超高效液相色谱-串联质谱法测定茶叶中拟除虫菊酯类农药残留
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摘要
建立了加速溶剂萃取(ASE)-超高效液相色谱(UPLC)-串联质谱法(MS/MS)测定茶叶中拟除虫菊酯类农药残留的方法。ASE萃取温度为80℃,萃取压力为10.34 MPa,以正己烷-丙酮(2∶1, v/v)为溶剂静态萃取5 min,循环一次。萃取液浓缩后经GCB/NH_2-Florisil柱净化,UPLC分离,MS/MS正离子扫描(ESI~+)、多反应离子监测(MRM)模式进行分析,外标法定量。线性回归分析表明:10种拟除虫菊酯的浓度与其峰面积的线性关系显著,相关系数(r)均不小于0.999 5,检出限(LOD)在0.5～5.0μg/kg之间,定量限(LOQ)在1.6～16.6μg/kg之间;在定量限、0.4 mg/kg以及最高残留限量(MRL,无MRL的加入1 mg/kg)3个水平进行添加回收试验(n=7),回收率为68.7%～103.8%, RSD为0.8%～13.2%。该方法前处理简单,耗时短,灵敏度和准确度高,可满足茶叶中痕量拟除虫菊酯类农药残留测定的要求。
A method was developed for the determination of pyrethroid pesticides in tea by accelerated solvent extraction(ASE) combined with ultra-performance liquid chromatography-tandem mass spectrometry(UPLC-MS/MS). The target compounds were extracted from tea using n-hexane and acetone(2∶1, v/v) for 5 min at 10.34 MPa and 80 ℃ via a single cycle of accelerated solvent extraction. The extract was purified by GCB/NH_2 and Florisil columns, analyzed by UPLC-MS/MS in positive electrospray ionization(ESI~+) and multiple reaction monitoring(MRM) modes, and quantified by the external standard method. Regression analysis revealed that the linear relationships between mass concentration and peak area are significant for the 10 pyrethroid pesticides, and the correlation coefficients(r) are all not less than 0.999 5. The limits of detection(LOD) of the 10 pyrethroid pesticides ranged from 0.5 μg/kg to 5.0 μg/kg and the limits of quantification(LOQ) ranged from 1.6 μg/kg to 16.6 μg/kg. The recoveries of all the pesticides ranged from 68.7% to 103.8% at the spiked levels of LOQ, 0.4 mg/kg and maximum residue limit(MRL)(added 1 mg/kg without MRL) with RSDs ranging from 0.8% to 13.2%(n=7). The proposed method is simple, rapid, sensitive, and accurate, and could be effective for trace analysis of pyrethroid pesticides in tea.
A method was developed for the determination of pyrethroid pesticides in tea by accelerated solvent extraction(ASE) combined with ultra-performance liquid chromatography-tandem mass spectrometry(UPLC-MS/MS). The target compounds were extracted from tea using n-hexane and acetone(2∶1, v/v) for 5 min at 10.34 MPa and 80 ℃ via a single cycle of accelerated solvent extraction. The extract was purified by GCB/NH_2 and Florisil columns, analyzed by UPLC-MS/MS in positive electrospray ionization(ESI~+) and multiple reaction monitoring(MRM) modes, and quantified by the external standard method. Regression analysis revealed that the linear relationships between mass concentration and peak area are significant for the 10 pyrethroid pesticides, and the correlation coefficients(r) are all not less than 0.999 5. The limits of detection(LOD) of the 10 pyrethroid pesticides ranged from 0.5 μg/kg to 5.0 μg/kg and the limits of quantification(LOQ) ranged from 1.6 μg/kg to 16.6 μg/kg. The recoveries of all the pesticides ranged from 68.7% to 103.8% at the spiked levels of LOQ, 0.4 mg/kg and maximum residue limit(MRL)(added 1 mg/kg without MRL) with RSDs ranging from 0.8% to 13.2%(n=7). The proposed method is simple, rapid, sensitive, and accurate, and could be effective for trace analysis of pyrethroid pesticides in tea.
引文
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[23] GB 2763-2016
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[4] Shukla Y,Arora A,Singh A.Toxicology,2001,163:1
[5] Neelima P,Rao K G,Rao G S,et al.Int J Biol Med Res,2016,7(2):5574
[6] Domingues V,Cabral M,Alves A,et al.Anal Lett,2009,42(4):706
[7] Sun P,Gao Y L,Wang J M,et al.Chinese Journal of Pesticide Science,2016,18(4):497 孙鹏,高玉玲,王金梅,等.农药学学报,2016,18(4):497
[8] Tripathy V,Saha A,Patel D J,et al.J Environ Sci Health,Part B,2016,51(8):508
[9] Chen B,Wu F Q,Wu W D,et al.Microchem J,2016,126:415
[10] Niu Z,Yu C,He X,et al.J Pharm Biomed Anal,2017,143:222
[11] Liu L,Zhang Q,Wang H Y,et al.Chinese Journal of Chromatography,2017,35(8):860 刘丽,张琦,王海雁,等.色谱,2017,35(8):860
[12] Qu L,Li Y,Zeng J,et al.Chinese Journal of Chromatography,2017,35(7):778 曲栗,李优,曾静,等.色谱,2017,35(7):778
[13] Huang W,Li N,Xu R H,et al.Chinese Journal of Chromatography,2018,36(12):1303 黄微,李娜,徐瑞晗,等.色谱,2018,36(12):1303
[14] Fan W,Tang F,Yue Y D.Chinese Agricultural Science Bulletin,2010,26(3):238 樊玮,汤锋,岳永德.中国农学通报,2010,26(3):238
[15] Yu L,Dong L L.Journal of Analytical Science,2016,32(2):218 于玲,董丽丽.分析科学学报,2016,32(2):218
[16] Xing H,Hou D F,Hou C Q,et al.Agrochemicals,2017,56(7):492 邢红,侯德粉,侯春青,等.农药,2017,56(7):492
[17] Yang L,Wen Y Y,Gong Z B.Chinese Journal of Analytical Chemistry,2010,38(7):968 杨琳,温裕云,弓振斌.分析化学,2010,38(7):968
[18] Liu Q,Sun L,Zhang L.Journal of Instrumental Analysis,2010,29(10):1048 刘琪,孙雷,张骊.分析测试学报,2010,29(10):1048
[19] Shao H Y,Xu G,Wu M H,et al.Chinese Journal of Analytical Chemistry,2013,41(9):1315 邵海洋,徐刚,吴明红,等.分析化学,2013,41(9):1315
[20] Chu N M,Meng X,Kang Y Q,et al.Food Science,2016,37(24):239 褚能明,孟霞,康月琼,等.食品科学,2016,37(24):239
[21] Deng M L,Chen J C,Duan Y P,et al.Chinese Journal of Analysis Laboratory,2014,33(3):351 邓美林,陈俊赤,段云鹏,等.分析试验室,2014,33(3):351
[22] Lu X L,Ye M J,Zhou W L.Agrochemicals,2014,53(11):825 陆小磊,叶美君,周卫龙.农药,2014,53(11):825
[23] GB 2763-2016