[关键词]
[摘要]
建立了同时检测干制水产品中9种N-亚硝胺类化合物的气相色谱-三重四极杆串联质谱(GC-MS/MS)方法。采用QuEChERS(quick,easy,cheap,effective,rugged and safe)的前处理方法,样品经乙腈提取后,使用增强型脂质去除产品(Bond Elut EMR-Lipid)基质分散净化,以聚乙二醇石英毛细管柱HP-INNO-WAX(30 m×0.25 mm×0.25 μm)分离化合物,GC-MS/MS采用多反应监测模式(MRM)检测,外标法定量。结果表明,9种N-亚硝胺类化合物在0.30~50.00 μg/L范围内线性关系良好,相关系数(R2)大于0.999,方法的检出限为0.3 μg/kg,定量限为1.0 μg/kg。对鱿鱼、虾干、蚝干和干贝4种基质分别添加1.00 μg/kg、4.00 μg/kg和10.00 μg/kg 3个质量浓度进行加标回收试验,9种N-亚硝胺化合物的回收率为80.41%~113.73%,相对标准偏差(RSD)为1.34%~11.80%(n=6)。市售干制水产品N-二甲基亚硝胺、N-二乙基亚硝胺、N-二丁基亚硝胺、N-亚硝基吡咯烷和N-二苯基亚硝胺均有不同程度的检出。该方法前处理过程简单,节省成本,灵敏度高,稳定性好,定性准确,可快速同时对水产干制品中9种N-亚硝胺类化合物进行定性和定量分析。
[Key word]
[Abstract]
A method for the simultaneous determination of nine N-nitrosamines in dried aquatic products by gas chromatography-tandem mass spectrometry (GC-MS/MS) was established. After quick, easy, cheap, effective, rugged, and safe (QuEChERS) pretreatment, the samples were subjected to acetonitrile extraction, followed by the application of Agilent bond elut enhanced matrix removal-lipid (EMR-Lipid). The compounds of interest were separated by a HP-INNOWAX column (30 m×0.25 mm×0.25 μm). They were subsequently analyzed by GC-MS/MS in the multiple reaction monitoring mode (MRM) and quantified by an external standard method. The experimental results show good linearity for the nine N-nitrosamines in the range from 0.30 to 50.00 μg/L, with linear regression coefficients R2 higher than 0.999. The limits of detection are 0.3 μg/kg, and the limits of quantification are 1.0 μg/kg. The average recovery rates of the nine N-nitrosamines were between 80.41% and 113.73% when 1.00 μg/kg, 4.00 μg/kg, and 10.00 μg/kg of N-nitrosamines were added to dried squids, shrimps, oysters, and scallops. Meanwhile, the relative standard deviations (RSDs) were 1.34% to 11.80% (n=6). Different levels of N-nitrosodimethylamine, N-nitrosodiethylamine, N-nitrosodibutylamine, N-nitrosopyrrolidine, and N-nitrosodiphenylamine were detected in dried aquatic products available in the market. The proposed method enables simple pre-treatment, and it is inexpensive, highly sensitive, reasonably stable, and quantitatively accurate. It can rapidly determine and quantitatively analyze nine N-nitrosamines in dry aquatic products.
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[基金项目]
广东省科技计划项目(2017B020207009;2017A070701039)