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    针筒式固相萃取管净化-高效液相色谱-串联质谱法测定柑橘类果汁中12种氨基甲酸酯类农药的残留量

    Determination of Residues of 12 Carbamate Pesticides in Citrus Juice by High Performance Liquid Chromatography-Tandem Mass Spectrometry with Syringe Solid Phase Extraction Cartridge Purification

    • 摘要: 取10.00 g柑橘类果汁样品置于50 mL离心管中,加入20.0 mL乙腈,摇匀,涡旋提取3 min,加入萃取盐包(含6 g无水硫酸镁和1.5 g氯化钠),振荡,冷却,离心3 min,用2 mL针筒式固相萃取管(含25 mg N-丙基乙二胺、2.5 mg石墨化碳黑、150 mg无水硫酸镁,连接0.22 μm有机相滤膜)抽取上清液,采用高效液相色谱-串联质谱法测定其中12种氨基甲酸酯类农药(涕灭威亚砜、涕灭威砜、灭多威、三羟基克百威、涕灭威、速灭威、残杀威、克百威、甲萘威、异丙威、混杀威、仲丁威)的残留量。以Agilent ZORBAX Eclipse Plus C18色谱柱为固定相,以不同体积比的甲醇-含0.1%(体积分数)甲酸的5 mmol·L−1乙酸铵溶液的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+)模式下进行多反应监测(MRM)模式质谱分析,基质匹配法定量。结果表明,12种氨基甲酸酯类农药的质量浓度在0.5~10.0 μg·L−1内与对应的定量离子的响应强度呈线性关系,测定下限(10S/N)为1.0 μg·kg−1。按照标准加入法进行回收试验,回收率为86.8%~104%,测定值的相对标准偏差(n=6)为1.2%~7.5%。方法用于分析30份实际柑橘类果汁样品,其中2份样品中检出克百威,检出量分别为1.6,4.2 μg·kg−1

       

      Abstract: The citrus juice sample (10.00 g) was taken and placed in a 50 mL-centrifuge tube, and 20.0 mL of acetonitrile was added. The mixture was shaken well and vortex extracted for 3 min. An extraction salt package (containing 6 g of magnesium sulfate anhydrous and 1.5 g of sodium chloride) was added, and the mixture was shaken, cooled down and centrifuged for 3 min. The supernatant was drawn using a 2 mL syringe solid phase extraction cartridge (containing 25 mg of N-propylethylenediamine, 2.5 mg of graphitized carbon black, 150 mg of magnesium sulfate anhydrous, and connecting with a 0.22 μm organic phase filter membrane), in which the residues of 12 carbamate pesticides, including aldicarb sulfoxide, aldicarb sulfone, methomyl, 3-hydroxycarbofuran, aldicarb, metolcarb, propoxur, carbofuran, carbaryl, isoprocarb, dimethacarb and fenobucarb were determined by high performance liquid chromatography-tandem mass spectrometry. Agilent ZORBAX Eclipse Plus C18 chromatographic column was used as the stationary phase and the mixed solution composed of methanol and 5 mmol · L−1 ammonium acetate solution containing 0.1% (volume fraction) formic acid 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, and matrix matching method was used for quantitative analysis. As shown by the results, linear relationships between the corresponding response intensities of quantitative ions and mass concentrations of 12 carbamate pesticides were kept in the range of 0.5-10.0 μg · L−1, with lower limits of determination (10S/N) of 1.0 μg · kg−1. Test for recovery was made by the standard addition method, giving results in the range of 86.8%-104%, with RSDs (n=6) of the determined values in the range of 1.2%-7.5%. This method was used for analysis of 30 actual citrus juice samples, and carbofuran was detected in 2 samples, with detection amounts of 1.6 and 4.2 μg · kg−1, respectively.

       

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