固相萃取-液相色谱-飞行时间质谱法快速筛查与确证谷物和果蔬中25种杀菌剂残留

Rapid Determination of 25 Kinds of Fungicides in Cereals,Fruits and Vegetables by Solid Phase Extraction and Liquid Chromatography Coupled with Quadrupole-Time of Flight Mass Spectrometry

利用固相萃取-液相色谱-飞行时间质谱(SPE-LC-Q-TOF/MS)技术建立了谷物、蔬菜和水果中25种杀菌剂农药残留的快速筛查和确证检测方法。样品经1%(V/V)乙酸-乙腈溶液提取,经Crabon/NH_2柱净化,乙腈-甲苯(3∶1,V/V)洗脱,C_(18)色谱柱分离,乙腈和0.1%甲酸溶液(含5 mmol/L乙酸铵)梯度洗脱,采用LC-Q-TOF/MS检测,外标法定量。建立了25种杀菌剂的一级精确质量数据库和二级谱图库,通过化合物的精确质量数、保留时间、同位素峰分布、同位素比例等信息对检测结果进行自动检索,在无对照标准品的情况下实现了25种农药的定性鉴定。结果表明,25种杀菌剂在0.02~200μg/L范围内线性关系良好,相关系数R2≥0.9950,加标回收率在71.8%~114.0%之间,相对标准偏差(RSD)为0.1%~21.3%(n=3)。25种杀菌剂检出限为0.01~5.00μg/kg,定量限为0.02~20.00μg/kg。本方法简便、快速、可靠,可用于谷物、蔬菜、水果中25种杀菌剂的快速筛查。

A method for simultaneous determination of 25 kinds of fungicides in cereals, vegetables and fruits using SPE-LC-Q-TOF/MS technique was developed. The samples were extracted with acetonitrile containing 1% （ V / V） acetic acid, purified by solid phase extraction （SPE） with a Crabon/ NH.cartridge, eluted with acetonitrile-toluene（3：1 , V/ V ） , separated by a reversed phase C｜8 column, gradiently eluted with acetonitrile and 0. 1% formic acid solution （Containing 5 mmol/L ammonium ac etate）,determined by LC-Q-TOF/MS, and quantified by external standard method. A data base of the accurate mass numbers and a library which contains 25 kinds of fungicides were established. The automatic retrieval of detection results was carried on according to the characteristics of the compound, such as accurate mass, retention time, isotope peak distribution, isotopic ratios, and so on. Based on the above results, the qualitative identifications of the 25 new fungicides were accomplished without the contrast of standard substances. The results indicated that 25 fungicides showed good linearity in the range of 0. 0 2 - 2 0 0 滋 g/ L,and the limits of detection （LOD） and the limits of quantification （ LOQ） were 0. 01-5. 00 滋 g/kg and 0. 02-20. 00 滋 g/ kg,respectively. The linear relative coefficients were greater than 0. 995. The recoveries were in the range 71. 8% -114. 0 % and the relative standard deviations （ RSD） were ranged from 0. 1% to 21. 3% （ n = 3）. The method has some advantages such as simplicity, rapidity and high sensitivity, and is suitable for the rapid determination of the common fungicides in cereals,vegetables and fruits.