高效液相色谱-串联质谱法测定蜂蜜中9种农药残留
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摘要
建立了同时测定蜂蜜中9种苯并咪唑类和新烟碱类农药的全自动固相萃取-高效液相色谱-串联质谱检测方法。蜂蜜样品用磷酸盐缓冲液(pH=7. 8)溶解,超声提取,经亲水亲脂平衡(hydrophilic-lipophilic balance,HLB)固相萃取小柱净化,氮吹浓缩,定容,过滤膜后进行高效液相色谱-串联质谱分析,采用多反应监测(MRM)模式测定,以内标法定量。结果表明,在0. 002～0. 05 mg/L范围内9种农药呈现出较好的线性关系(相关系数r2≥0. 99),检出限和定量限分别为0. 1～1. 0μg/kg和0. 3～2. 0μg/kg。对阴性蜂蜜,在5. 0、10. 0、20. 0μg/kg 3个水平下分别进行加标回收试验,测出9种农药的平均回收率在78. 2%～101. 2%之间,相对标准偏差为1. 3%～14. 3%(n=6)。该方法可适用于大批量蜂蜜样品的快速准确测定。
A method is proposed for the simultaneous determination of nine benzimidazole and neonicotinoid pesticides present in honey by employing automatic solid-phase extraction with high performance liquid chromatography-tandem mass spectrometry( HPLC-MS/MS). A honey sample was dissolved in a phosphate buffer( pH = 7. 8) followed by ultrasonic extraction. The extracts were then purified through solid-phase extraction( SPE) with hydrophilic-lipophilic balance( HLB) cartridges. Finally,nitrogen was blown on the obtained mixture,and the mixture was subsequently filtered for conducting HPLC-MS/MS analysis. Nine compounds were detected under the multiple reaction monitoring( MRM) mode,and the corresponding quantification was performed by employing the method of internal standards. The nine detected pesticides demonstrated good linearity in the range of 0. 002-0. 05 mg/L,with the correlation coefficient values( r 2) being higher than 0. 99. The limits of detection( LODs)( S/N = 3) and limits of quantification( LOQs)( S/N = 10) were found to be in the ranges of 0. 1-1. 0 μg/kg and 0. 3-2. 0 μg/kg,respectively. Furthermore,the results indicated that the recoveries of the ninedetected pesticides range from 78. 2%-101. 2% at three spiked levels of 5. 0,10. 0,and 20. 0μg/kg with a relative standard deviation( RSD) range of 1. 3%-14. 3%( n = 6). Hence,the proposed method is rapid and can be employed for accurate determination of pesticide residues in large quantities of honey samples.
A method is proposed for the simultaneous determination of nine benzimidazole and neonicotinoid pesticides present in honey by employing automatic solid-phase extraction with high performance liquid chromatography-tandem mass spectrometry( HPLC-MS/MS). A honey sample was dissolved in a phosphate buffer( pH = 7. 8) followed by ultrasonic extraction. The extracts were then purified through solid-phase extraction( SPE) with hydrophilic-lipophilic balance( HLB) cartridges. Finally,nitrogen was blown on the obtained mixture,and the mixture was subsequently filtered for conducting HPLC-MS/MS analysis. Nine compounds were detected under the multiple reaction monitoring( MRM) mode,and the corresponding quantification was performed by employing the method of internal standards. The nine detected pesticides demonstrated good linearity in the range of 0. 002-0. 05 mg/L,with the correlation coefficient values( r 2) being higher than 0. 99. The limits of detection( LODs)( S/N = 3) and limits of quantification( LOQs)( S/N = 10) were found to be in the ranges of 0. 1-1. 0 μg/kg and 0. 3-2. 0 μg/kg,respectively. Furthermore,the results indicated that the recoveries of the ninedetected pesticides range from 78. 2%-101. 2% at three spiked levels of 5. 0,10. 0,and 20. 0μg/kg with a relative standard deviation( RSD) range of 1. 3%-14. 3%( n = 6). Hence,the proposed method is rapid and can be employed for accurate determination of pesticide residues in large quantities of honey samples.
引文
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[2] Ye M L,Nie J Y,Xu G F,et al. Scientia Agricultura Sinica,2016,49(7):1289叶孟亮,聂继云,徐国锋,等.中国农业科学,2016,49(7):1289
[3] He H L.[MS Dissertation]. Hangzhou:Zhejiang University o f Techno lo gy,2014何华丽.[硕士学位论文].杭州:浙江工业大学,2014
[4] Yu G C,Wang X F. Occupation and Health,2008,24(17):1834于功昌,王筱芬.职业与健康,2008,24(17):1834
[5] Delatour P,Besse S. Ann Rech Vet,1990,21(1):87
[6] Chemical Identification.[2018-07-20]. http://hazard. com/m sds/to x/f/q37/q828.htm l
[7] Lin Z G,Meng F,Zheng H Q,et al. Acta Entomologica Sinica,2014,57(5):607蔺哲广,孟飞,郑火青,等.昆虫学报,2014,57(5):607
[8] Zhang J P. Pesticide Market New s,2017(27):52张金平.农药市场信息,2017(27):52
[9] EU Pesticides Database.[2018-07-20]. http://ec.europa.eu/fo o d/plant/pesticides/eu-pesticides-database/public/? event=pesticide.residue.CurrentMRL&language=EN
[10] Yang G. Pesticide Market New s,2018(12):47杨光.农药市场信息,2018(12):47
[11] Yu Y B,Miao Z J,Wan S W,et al. Physical Testing and Chem ical Analysis Part B:Chem ical Analysis,2005,41(5):353于彦彬,苗在京,万述伟,等.理化检验(化学分册),2005,41(5):353
[12] Wang G X.[MS Dissertation]. Beijing:Chinese Academy o f Agricultural Sciences,2006王国霞.[硕士学位论文].北京:中国农业科学院,2006
[13] Liu Y,Liu Y H,Guo Y R. Production and Characterization o f the Bro ad-Specific Mo no clo nal Antibo dies Against Neo nico tino id Pesticides.(2015-12-07)[2018-07-20]. http://w w w.paper.edu.cn/releasepaper/co ntent/201512-356柳颖,刘毅华,郭逸蓉.新烟碱类农药宽谱单克隆抗体制备与性能鉴定.(2015-12-07)[2018-07-20]. http://w w w. paper.edu.cn/releasepaper/co ntent/201512-356
[14] Shi H,Huang A X,Li Z R,et al. Pesticide Science and Adm inistratio n,2014,35(3):24石慧,黄安香,李洙锐,等.农药科学与管理,2014,35(3):24
[15] Zhang X D,Gong D X,Wu L,et al. Chinese Journal of Pesticide Science,2015,17(5):627张小东,龚道新,吴亮,等.农药学学报,2015,17(5):627
[16] Wang D,Hou C J,Zhao E C,et al. Journal of Instrumental Analysis,2015,34(6):681王东,侯传金,赵尔成,等.分析测试学报,2015,34(6):681
[17] Su Y Z,Li F,Qi X,et al. Journal of Analytical Science,2015,31(2):203粟有志,李芳,齐鑫,等.分析科学学报,2015,31(2):203
[18] Zhao J,He Q,Kong X H,et al. Chinese Journal of Pharm aceutical Analysis,2008,28(1):128赵洁,何强,孔祥虹,等.药物分析杂志,2008,28(1):128
[19] Liu H,Zhang X Y,LüC,et al. Food Safety and Quality Detectio n Techno lo gy,2016,7(11):4490柳菡,张晓燕,吕辰,等.食品安全质量检测学报,2016,7(11):4490
[20] Zhang Y Y,Zhang Z,Chen Z Z,et al. Food Safety and Quality Detectio n Techno lo gy,2014(9):2711张媛媛,张卓,陈忠正,等.食品安全质量检测学报,2014(9):2711