液相色谱-串联质谱法检测干熏鱼中的4种非挥发性亚硝胺  

Determination of 4 kinds of non-volatile nitrosamines in dried smoked fish by liquid chromatography-tandem mass spectrometry

作　　者：陈晨 吴建欣 王宗义 张巍青 杨丽华 马小童 董子琦 CHEN Chen;WU Jian-Xin;WANG Zong-Yi;ZHANG Wei-Qing;YANG Li-Hua;MA Xiao-Tong;DONG Zi-Qi(Beijing Key Laboratory of Agricultural Product Detection and Control for Spoilage Organisms and Pesticides,College of Food Sciences and Engineering,Beijing University of Agriculture,Beijing 102206,China;Guangzhou Hexin Instrument Co.,Ltd.,Guangzhou 510535,China)

机构地区：[1]北京农学院食品科学与工程学院,农产品有害微生物及农残安全检测与控制北京市重点实验室,北京102206 [2]广州禾信仪器股份有限公司,广州510535

出　　处：《食品安全质量检测学报》2025年第7期87-93,共7页Journal of Food Safety and Quality

基　　金：北京市都市农林学交叉学科平台建设项目(2023);北京农学院教改重点项目-服务乡村振兴专业能力实训课程体系的构建与教学实践项目(5046516654/149)。

摘　　要：目的建立液相色谱-串联质谱测定干熏鱼中N-亚硝基脯氨酸(N-nitrosoproline,NPRO)、N-亚硝基肌氨酸(N-nitrososarcosine,NSAR)、N-亚硝基-噻唑烷-4-羧酸(N-nitroso-thiazolidine-4-carboxylic acid,NTCA)和N-亚硝基-2-甲基-噻唑烷-4-羧酸(N-nitroso-2-methyl-thiazolidine 4-carboxylic acid,NMTCA)4种非挥发性N-亚硝胺(non volatile N-nitrsoamine,NVNA)的新方法。方法样品经乙腈提取,正己烷脱脂,MORHCHEM Caprisil C18-AQ(4.6 mm×250 mm,5μm)色谱柱分离,采用多反应监测模式进行液相色谱-串联质谱检测,基质标曲,外标法定量。结果4种NVNA在1、4、10、50 ng/mL分别至800 ng/mL的范围内线性良好,r2>0.996,检出限为1.36~56.17μg/kg,定量限为4.52~187.20μg/kg,加标回收率为90.34%~103.60%,相对标准偏差为1.75%~6.47%。实际应用显示,市售干熏鱼样品中均有不同程度、不同种类的NVNA检出,其中具有弱致癌性的NSAR检出率和含量都较高。结论本方法样品前处理简单、准确性好、精密度高,能够满足干熏鱼中4种NVNA的同步测定,为干熏鱼制品中NVNA的污染监测与控制提供了有价值的技术参考。Objective To establish a new method for the determination of 4 kinds of non-volatile N-nitrosamines(NVNA),N-nitrosoproline(NPRO),N-nitrososarcosine(NSAR),N-nitroso-thiazolidine-4-carboxylic acid(NTCA)and N-nitroso-thiazolidine-4-carboxylic acid(NMTCA),in dried smoked fish products by liquid chromatography-tandem mass spectrometry.Methods The samples were extracted by acetonitrile,degreased with n-hexane,separated on a MORHCHEM Caprisil C18-AQ(4.6 mm×250 mm,5μm)column,and detected by liquid chromatography-tandem mass spectrometry(LC-MS/MS)in multiple reaction monitoring(MRM)mode,and quantified by the external standard method of matrix standard curve.Results The linearity of the 4 kinds of NVNA was good in ranges of 1,4,10 or 50–800 ng/mL with r2>0.996,the detection limits were 1.36–56.17μg/kg,the quantification limits were 4.52–187.2μg/kg,and the spiked recoveries of 4 kinds of NVNA ranged from 90.34%–103.60%with the relative standard deviations(RSDs)of 1.75%–6.47%.Practical applications showed that NVNAs were detected in commercially available samples of the dried smoked fish at different levels and in different species,with the weakly carcinogenic NSAR being detected at higher rates and levels.Conclusion This method is simple in sample pretreatment,good in accuracy and high in precision,which can meet the simultaneous determination of 4 kinds of NVNA in dried smoked fish,and provides a valuable technical reference for the regulation and control of the NVNA contamination level in dried smoked fish products.

关 键 词：非挥发性亚硝胺 干熏鱼 液相色谱-串联质谱法 

分 类 号：R28[医药卫生—中药学]