中药化橘红的106种农药残留量测定研究

Determination of 106 Pesticide Residues in Citrus Grandis Exocarpium

目的建立中药材化橘红农药多残留的检测方法。方法以乙腈为溶剂,涡旋提取,经prime-HLB SPE小柱净化。检测方法:气相色谱-串联质谱法,采用DB17MS弹性石英毛细管柱(30 m×0. 25 mm,0. 25μm),电子轰击电离源(EI);液相色谱-串联质谱法,采用十八烷基硅烷键合硅胶柱(Phenomenex Kinetex C18,2. 1 mm×100 mm,2. 6μm),以水(含5 mmol·L^-1甲酸铵和0. 1%甲酸)溶液和95%乙腈(含5 mmol·L^-1甲酸铵和0. 1%甲酸)溶液为流动相进行梯度洗脱,电喷雾电离源(ESI),正离子模式下多反应监测(MRM)。结果 106种农药线性关系良好,相关系数均大于0. 990 9,平均回收率57. 6%~134. 4%,RSD小于15%。结论本方法能快速有效地检测化橘红中的农药多残留,为芸香科果实、果皮类中的农药残留测定提供借鉴。20批次样品共检出禁用农药7种,限用及常用农药25种,主要为除虫、杀螨及杀菌剂。

OBJECTIVE To establish a method for determination of pesticide residues in Citrus Grandis Exocarpium by mass spectrometry. METHODS After vortex extraction with acetonitrile,the samples were purified with prime-HLB SPE. GC-MS/MS analysis was performed on a DB17 MS( 30 m × 0. 25 mm,0. 25 μm) capillary column with electron impact( EI) source. LC-MS/MS analysis was performed on a Phenomenex Kinetex C18( 2. 1 mm × 100 mm,2. 6 μm) column with gradient elution using water( containing 5 mmol·L^-1 ammonium formate and 0. 1% formic acid) and 95% acetonitrile( containing 5 mmol·L^-1 ammonium formate and0. 1% formic acid). Electrospray ionization( ESI) source was applied by positive ionization in multiple reaction monitoring( MRM)mode. RESULTS The calibration curves of 106 pesticide residues showed good linearity with correlation coefficients above 0. 990 9.The average recoveries for all target compounds fell in the range of 57. 6%-134. 4%,with RSDs below 15%. Seven kinds of prohibited pesticides and 25 strictly restricted and commonly used ones were detected in 20 batches of samples,which mainly belong to insecticide,acaricide and fungicide. CONCLUSION The method is fast,accurate and highly sensitive for the screening and confirmation of pesticide residues in Citrus Grandis Exocarpium,which provides a basis for the control of pesticide residues in similar mattrix medicinal plants.