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    去磷脂PPR固相萃取柱净化-高效液相色谱-串联质谱法测定多种动物源性食品中5种咪唑啉酮类农药的残留量

    Determination of Residues of 5 Imidazolinone Pesticides in Multiple Animal-Derived Foods by High Performance Liquid Chromatography-Tandem Mass Spectrometry with Phospholipid Removal PPR Solid Phase Extraction Column Purification

    • 摘要: 为实现动物源性食品中多种咪唑啉酮类农药的同时测定,提出了题示方法。取鸡蛋、鸡肉、鸡肝、肠衣、罗非鱼、牛肉或牛奶样品5.00 g,加入10 mL含1%(体积分数,下同)乙酸的乙腈溶液(鸡肉、牛肉和罗非鱼等肉类样品需要均质20~30 s,用10 mL含1%乙酸的乙腈溶液清洗残渣并将洗涤液与样品溶液合并),涡旋20 s,加入含4.0 g无水硫酸镁、1.0 g氯化钠、1.0 g二水合柠檬酸钠、0.5 g倍半水合柠檬酸二钠的QuEChERS萃取盐包,迅速混匀后振荡10 min,离心5 min。鸡肉、牛肉和罗非鱼样品需于−18 ℃冷冻2 h,其余样品无需冷冻直接分取2 mL上层酸性乙腈相过去磷脂PPR固相萃取柱,收集流出液,混匀后过0.22 μm有机滤膜,滤液采用高效液相色谱-串联质谱法测定。5种咪唑啉酮类农药(甲氧咪草烟、甲咪唑烟酸、咪唑烟酸、咪唑喹啉酸、咪唑乙烟酸)在Accucore aQ色谱柱上以不同体积比的甲醇和含0.1%(体积分数)甲酸的5 mmol·L−1甲酸铵溶液的混合溶液为流动相进行梯度洗脱分离,以加热电喷雾离子源正离子模式电离,多反应监测模式检测,标准曲线法(鸡蛋和肠衣基质)联合基质匹配工作曲线法(鸡肉、鸡肝、罗非鱼、牛肉和牛奶基质)定量。结果显示,5种咪唑啉酮类农药的质量浓度均在1~100 µg·L−1和对应的峰面积呈线性关系,检出限(3S/N)为0.045~0.332 µg·kg−1。按照标准加入法对上述7种空白基质进行回收试验,回收率为67.8%~120%,测定值的相对标准偏差(n=6)为1.0%~10%。方法用于分析多批进口牛肉、鱼肉,5种咪唑啉酮类农药均未检出。

       

      Abstract: To achieve simultaneous determination of multiple imidazolinone pesticides in animal-derived foods, the method mentioned by the title was proposed. The 5.00 g of sample (eggs, chicken meat, chicken liver, intestines, tilapia, beef or milk) was taken, and 10 mL of acetonitrile solution containing 1% (volume fraction, the same below) acetic acid was added (for meat samples such as chicken meat, beef and tilapia, additional steps were required including homogenizing 20-30 s, taking 10 mL of acetonitrile solution contaning 1% acetic acid to wash the residue and combining the washing solution with the sample extract). The mixture was vortexed for 20 s, then a QuEChERS extraction salt packet containing 4.0 g of magnesium sulfate anhydrous, 1.0 g of sodium chloride, 1.0 g of sodium citrate dihydrate and 0.5 g of trisodium citrate sesquihydrate was added. After immediate vigorous mixing, the mixture was shaken for 10 min and centrifuged for 5 min. The chicken meat, beef and tilapia samples needed to be frozen at −18 ℃ for 2 h, while the other samples could be processed directly without freezing. The 2 mL of the upper acidic acetonitrile phase was taken and passed through a phospholipid removal PPR solid phase extraction column. The eluate was collected, mixed well, and passed through a 0.22 μm organic filter membrane. The resulting filtrate was analyzed by high performance liquid chromatography-tandem mass spectrometry. The 5 imidazolinone pesticides (imazamox, imazapic, imazapyr, imazaquin and imazethapyr) were separated on Accucore aQ column using a mixture consisting of methanol and 5 mmol · L−1 ammonium formate solution containing 0.1% (volume fraction) formic acid at different volume ratios as the mobile phase for gradient elution. Detection was performed using heated electrospray ionization in positive ion mode with multiple reaction monitoring (MRM) mode. Quantitation was conducted using the standard calibration method (for egg and intestine matrices) combined with the matrix-matched working calibration method (for chicken meat, chicken liver, tilapia, beef and milk matrices). As shown by the results, linear relationships between the corresponding peak areas and mass concentrations of 5 imidazolinone pesticides were in the range of 1-100 μg · L−1, with detection limits (3S/N) in the range of 0.045-0.332 µg · kg−1. Tests for recovery were made on the above 7 blank matrices by the standard addition method, giving results in the range of 67.8%-120%, with RSDs (n=6) of the determined values ranging from 1.0% to 10%. The method was applied to analysis of multiple batches of imported beef and fish, and 5 imidazolinone pesticides were not detected.

       

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