QuEChERS-气相色谱-三重四极杆串联质谱法测定水产干制品中9种N-亚硝胺类化合物

Determination of Nine N-nitrosamines in Dried Aquatic Products by QuEChERS Gas Chromatography-triple Quadrupole Tandem Mass Spectrometry

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×0.25μm)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0.30~50.00μg/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0.3μg/kg,定量限为1.0μg/kg。对鱿鱼、虾干、蚝干和干贝4种基质分别添加1.00μg/kg、4.00μg/kg和10.00μg/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。

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×0.25μm).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 50.00μg/L,with linear regression coefficients R2 higher than 0.999.The limits of detection are 0.3μg/kg,and the limits of quantification are 1.0μg/kg.The average recovery rates of the nine N-nitrosamines were between 80.41%and 113.73%when 1.00μg/kg,4.00μg/kg,and 10.00μg/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.