盐析辅助液液萃取交联聚维酮净化-靶向单一离子监测/高分辨质谱法测定蜂蜜中新烟碱类农药残留

Determination of Neonicotinoid Residues in Honey by Target Single Ion Monitoring/High Resolution Mass Spectrometry Combined with Salting-out Assisted Liquid-Liquid Extraction and PVPP Cleanup

基于盐析辅助液液萃取(LLE)交联聚维酮(PVPP)净化技术,建立了蜂蜜中7种新烟碱类农药的靶向单一离子监测(TSIM)/高分辨质谱检测方法。样品用乙腈基于盐析辅助LLE-PVPP提取净化,采用BEH C18色谱柱为分析柱,甲醇-水体系(两相均含0.1%甲酸和5 mmol/L甲酸铵)作为流动相,梯度洗脱,采用高分辨质谱TSIM模式检测目标化合物,内标法定量。结果表明,盐析辅助LLE-PVPP净化技术可实现提取净化一步式样品制备,TSIM扫描模式则显示了更宽的线性动态范围和更高的灵敏度与准确度。7种新烟碱类农药在0.01~100μg/L或0.02~100μg/L范围内具有良好的线性关系(r2>0.999);方法检出限为0.03~0.07μg/kg,定量下限为0.1~0.2μg/kg。在0.2、2、20μg/kg 3种加标水平下,7种新烟碱类农药在蜂蜜中的平均回收率为84.8%~112.7%,日内精密度(RSDr)为0.9%~5.7%,日间精密度(RSDR)为3.7%~9.7%。该方法前处理简单快速、成本较低,灵敏度高、重现性好,可广泛应用于蜂蜜中新烟碱类农药残留的快速检测。

Based on salting-out assisted liquid-liquid extraction（ LLE） and polyvinylpolypyrrolidone（ PVPP） cleanup,a method was developed for the determination of seven neonicotinoid pesticides in honey by target single ion monitoring（ TSIM）/high-resolution mass spectrometry. The samples were extracted and cleaned up with acetonitrile by salting-out assisted LLE-PVPP method. The chromatographic separation was conducted on a BEH C18 column using methanol-water containing 0. 1% formic acid and 5 mmol/L ammonium formate in two phases,as mobile phase by gradient elution. The analysis was performed by high-resolution mass spectrometry in TSIM mode,and the quantitation was carried out by the internal standard method. The result showed that salting-out assisted LLE-PPVP cleanup method allowed one-step sample preparation,while TSIM mode showed a wide linear dynamic range with higher sensitivity and accuracy. There existed good linearities（ r2 0. 999） for seven neonicotinoid pesticides in the concentration ranges of 0. 01-100 μg/L or 0. 02-100 μg/L. The limits of detection（ LODs） and quantitation（ LOQs） were in the ranges of 0. 03-0. 07 μg/kg and 0. 1-0. 2 μg/kg,respectively. At three spiked levels of 0. 2,2,20 μg/kg,the average recoveries forthe analytes in honey were between 84. 8% and 112. 7%,with the intra-day precision（ RSDr） and the inter-day precision（ RSDR） of 0. 9%-5. 7% and 3. 7%-9. 7%,respectively. With the advantages of a rapid and simple pretreatment,low-cost,high sensitivity and good reproducibility,this method was suitable for the determination of neonicotinoid pesticides in honey.