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    QuEChERS-超高效液相色谱-三重四极杆复合线性离子阱质谱法测定鸡蛋中34种新型杀虫剂的残留量

    Determination of Residues of 34 Novel Insecticides in Eggs by Ultra-High Performance Liquid Chromatography-Triple Quadrupole Composite Linear Ion Trap Mass Spectrometry with QuEChERS

    • 摘要: 鲜鸡蛋样品经去壳、充分匀浆、搅拌均匀,分取5 g,加入10 mL乙腈、4 mg无水硫酸镁和1 g氯化钠,涡旋振荡20 min,离心3 min。分取5 mL上清液,加入200 mg十八烷基硅烷键合硅胶(C18)、600 mg N-丙基乙二胺(PSA)、10 mg石墨化碳黑(GCB)和800 mg无水硫酸镁,涡旋振荡20 min,离心3 min,取上清液过0.22 μm有机滤膜,滤液采用超高效液相色谱-三重四极杆复合线性离子阱质谱法测定。在色谱分析中,以Shim-pack XR-ODS ⅡC18 色谱柱为固定相,乙腈- 水体系为流动相进行梯度洗脱;在质谱分析中,以电喷雾离子(ESI)源正、负离子模式电离,多反应监测- 信息依赖性采集- 增强子离子(MRM-IDA-EPI)模式检测,构建含有特征子离子及其丰度等信息的标准品质谱库辅助定性,基质匹配外标法定量。结果显示:呋虫胺、氟啶脲、环溴虫酰胺、氟虫脲的质量浓度在1.0~100 μg·L−1,其余目标物的质量浓度在0.5~50 μg·L−1 内和定量离子峰面积呈线性关系,检出限为0.500~5.00 μg·kg−1;对空白样品进行3个浓度水平的加标回收试验,回收率为71.9%~119%,测定值的相对标准偏差(n=6)为1.3%~14%。方法用于90批实际样品的分析,在1批样品中同时检测出了氟虫双酰胺、氟铃脲、氟苯脲、环溴虫酰胺,检出量分别为24.3,12.6,9.54,25.8 μg·kg−1,与标准品质谱库的匹配度分别为73.532%,85.659%,78.168%,93.822%。

       

      Abstract: Fresh egg samples were shelled, thoroughly homogenized, and uniformly mixed. An aliquot (5 g) was taken, to which 10 mL of acetonitrile, 4 mg of anhydrous magnesium sulfate, and 1 g of sodium chloride were added, followed by vortex oscillation for 20 min and centrifugation for 3 min. A portion (5 mL) of the supernatant was taken, to which 200 mg of C18, 600 mg of N-propyl ethylenediamine (PSA), 10 mg of graphitized carbon black (GCB), and 800 mg of anhydrous magnesium sulfate were added, followed by vortex oscillation for 20 min and centrifugation for 3 min. The supernatant was passed through a 0.22 μm organic filter membrane, and the filtrate was analyzed by ultra-high performance liquid chromatography-triple quadrupole composite linear ion trap mass spectrometry. In the chromatographic analysis, Shim-pack XR-ODS Ⅱ C18 column was used as the stationary phase, with acetonitrile-water system as the mobile phase for gradient elution. In the mass spectrometric analysis, electrospray ionization (ESI) source was used in positive and negative ion modes, with multiple reaction monitoring-information dependent acquisition-enhanced product ion (MRM-IDA-EPI) mode for detection. A standard mass spectrometry library containing information such as characteristic daughter ions and their abundance was constructed to aid in qualitative analysis, and matrix matched external standard method was used for quantification. It was shown that linear relationships between the mass concentrations and peak areas of quantitative ions were kept in the ranges of 1.0−100 μg·L−1 (dinotefuran, flufenoxuron, cyclaniliprole, and flubenzimine) and 0.50−50 μg·L−1 (the other target compounds), with detection limits in the range of 0.500−5.00 μg·kg−1. Spike recovery tests at three concentration levels were made on blank samples, giving recoveries in the range of 71.9%−119%, and RSDs (n=6) of the determined values ranged from 1.3% to 14%. The proposed method was applied to the analysis of 90 batches of actual samples, and flubendiamide, hexaflumuron, teflubenzuron, and cyclaniliprole were simultaneously detected in 1 batch of samples with detection amounts of 24.3, 12.6, 9.54, 25.8 μg·kg−1, matching degrees of which with the standard mass spectrometry library were 73.532%, 85.659%, 78.168%, 93.822%, respectively.

       

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