改进的QuEChERS-气相色谱-质谱联用法测定蔬菜中的氟吗啉和烯酰吗啉残留

建立了同时测定蔬菜中氟吗啉和烯酰吗啉残留的改进的QuEChERS-气相色谱-质谱(GC-MS)联用法。前处理过程以乙腈高速匀浆提取样品,应用改进的QuEChERS方法对样品进行提取、盐析和净化,并采用气相色谱-质谱联用仪在选择离子监测(SIM)模式下测定了多种蔬菜中的氟吗啉和烯酰吗啉残留量,以基质匹配标准溶液外标法定量。选用DB-5 MS石英毛细管柱(30 m×0.25 mm×0.25μm),流速1.1 mL/min,采用电子轰击电离源,选择监测离子氟吗啉为m/z 285、371、165;烯酰吗啉为m/z 301、387、165。结果表明:在优化条件下,氟吗啉和烯酰吗啉在10~1000μg/kg范围内线性关系良好,相关系数不低于0.999,不同基质中的检出限(S/N=3)范围为0.67~2.42μg/kg。对于生姜、番茄、胡萝卜、菠菜、甘蓝和白木耳空白样品,在10、20、100μg/kg共3个水平下氟吗啉和烯酰吗啉的加标回收率为71%~116%,相对标准偏差(RSD)为1.8%~14.7%。同时,本研究对蔬菜中氟吗啉和烯酰吗啉残留检测的裂解机理和基质效应进行了考察。本方法具有操作简便、快速、准确的特点,可用于蔬菜中氟吗啉和烯酰吗啉残留量的日常检测。

Determination of flumorph and dimethomorph residues in vegetables by improved QuEChERS-gas chromatography-mass spectrometry

To determine the residues of flumorph and dimethomorph in vegetables, a method was established with improved QuEChERS-gas chromatography coupled to mass spectrometry (GC-MS). With acetonitrile as the extraction solvent, the samples were pretreated with the improved QuEChERS method including extraction, salting-out and purification processes. Then all the sample extracts were analyzed with GC-MS in selected-ion monitoring (SIM) mode, and quantified by matrix-matched standard solution in external standard method. Under electron ionization conditions, the analysis was carried out with a capillary column (DB-5 MS, 30 m×0.25 mm×0.25 μm) at a flow rate of 1.1 mL/min. The quantitation was performed to detect ions of m/z 285, 371, 165 for flumorph and m/z 301, 387, 165 for dimethomorph. Good linearity was obtained in the range of 10-1000 μg/kg for both pesticides with correlation coefficients greater than 0.999. The recovery experiments were carried out by spiking blank samples of ginger, tomato, carrot, spinach, cabbage and tremella at the three levels of 10, 20 and 100 μg/kg. For both pesticides in different matrices, the limits of detection (S/N=3) were in the range of 0.67-2.42 μg/kg. The average recoveries of flumorph and dimethomorph ranged from 71% to 116% with the relative standard deviations (RSDs) in the range of 1.8%-14.7%. Meanwhile, the pyrolysis mechanism and matrix effect for the determination of flumorph and dimethomorph in vegetables were investigated in this study. The method is simple, rapid and accurate, and can be used for the routine analysis of flumorph and dimethomorph in vegetables.