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    QuEChERS净化-液相色谱-串联质谱法测定鱼肉中11种新烟碱类杀虫剂的残留量

    Determination of Residues of 11 Neonicotinoid Insecticides in Fish by Liquid Chromatography-Tandem Mass Spectrometry with QuEChERS Purification

    • 摘要: 提出了QuEChERS净化-液相色谱-串联质谱法(LC-MS/MS)测定鱼肉中11种新烟碱类杀虫剂(氟啶虫酰胺、呋虫胺、烯啶虫胺、噻虫嗪、噻虫啉、环氧虫啶、噻虫胺、吡虫啉、氯噻啉、啶虫脒和氟啶虫胺腈)残留量的方法。取4.00 g鱼肉样品置于50 mL聚丙烯离心管中,加入20 mL含0.4%(体积分数)乙酸的20%(体积分数)乙腈溶液,涡旋1 min,超声20 min,加入1 g硫酸镁,涡旋1 min,离心10 min,取10 mL上清液置于15 mL试管中,于35 ℃氮吹至近干,加入50 mg N-丙基乙二胺、40 mg C18粉和2 mL 25%(体积分数)乙腈溶液,涡旋2 min,取1 mL净化液过0.22 μm有机滤膜,采用LC-MS/MS测定滤液中11种新烟碱类杀虫剂的含量。以ZORBAX SB-AQ色谱柱为固定相,以不同体积比的0.1%(体积分数)甲酸溶液-乙腈混合液为流动相进行梯度洗脱,采用电喷雾离子(ESI)源,在正离子(ESI+)扫描模式下进行多反应监测(MRM)模式质谱分析,以基质匹配的混合标准溶液系列绘制工作曲线。结果表明,11种新烟碱类杀虫剂的质量浓度在一定范围内与对应的峰面积呈线性关系,检出限(3S/N)为0.10~1.0 μg·kg-1。按照标准加入法进行回收试验,回收率为60.3%~113%,测定值的相对标准偏差(n=6)均不大于12%。方法用于分析17份实际鱼肉样品,其中1份黄花鱼样品中检出呋虫胺,检出量为14.6 μg·kg-1

       

      Abstract: A method for determination of residues of 11 neonicotinoid insecticides, including fluazinam, fipronil, imidacloprid, thiamethoxam, thiacloprid, epoxystrobin, thiamethoxam, imidacloprid, chlorothiazide, acetamiprid and flupyradifurone in fish by liquid chromatography-tandem mass spectrometry (LC-MS/MS) with QuEChERS purification was proposed. 4.00 g of fish sample was taken and placed in a 50 mL-polypropylene centrifuge tube, and 20 mL of 20% (volume fraction) acetonitrile solution containing 0.4% (volume fraction) acetic acid was added. The mixture was vortexed for 1 min, and sonicated for 20 min. 1 g of magnesium sulfate was added, and the mixture was vortexed for 1 min and centrifuged for 10 min. 10 mL of supernatant was taken and placed in a 15 mL-test tube, and blown to near dryness by nitrogen at 35 ℃. 50 mg of N-propylethylenediamine, 40 mg of C18 powder, and 2 mL of 25% (volume fraction) acetonitrile solution were added. The mixture was vortexed for 2 min, and 1 mL of purified solution was passed through a 0.22 µm organic filter membrane. 11 neonicotinoid insecticides in the filtrate were determined by LC-MS/MS. ZORBAX SB-AQ column was used as the stationary phase and the mixed solution composed of 0.1% (volume fraction) formic acid solution and acetonitrile at different volume ratios was used as the mobile phase for gradient elution.Electrospray ion (ESI) source was used for mass spectrometry. The targets were analyzed by multiple reaction monitoring (MRM) mode in positive ion (ESI+) scanning mode. Working curves were drawn with the matrix matching mixed standard solution series. As shown by the results, linear relationships between the corresponding peak areas and mass concentrations of 11 neonicotinoid insecticides were kept in definite ranges, with detection limits (3S/N) in the range of 0.10-1.0 μg·kg-1. Test for recovery was made by the standard addition method, giving results in the range of 60.3%-113%, with RSDs (n=6) of the determined values not more than 12%. This method was used to analyze 17 actual fish samples, and fipronil was detected in one yellow croaker sample, with the detection amount of 14.6 μg·kg-1.

       

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