溶剂提取/水蒸气蒸馏-分散液液微萃取-稳定同位素稀释-GC-MS/MS测定咸鱼中的挥发性亚硝胺  

Determination of volatile nitrosamines in salted fish by stable isotope dilution-gas chromatography-tandem mass spectrometry with solvent extraction/steam distillation connecting with dispersion liquid-liquid microextraction

作　　者：刘方征 陈晨 王宗义 张丽萍 吴建欣 王玉纯 何世慧 LIU Fang-Zheng;CHEN Chen;WANG Zong-Yi;ZHANG Li-Ping;WU Jian-Xin;WANG Yu-Chun;HE Shi-Hui(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;National Research Center for Enviromental Analysis and Measurement,Beijing 100029,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]国家环境分析检测中心,北京100029

出　　处：《食品安全质量检测学报》2024年第20期271-278,共8页Journal of Food Safety and Quality

基　　金：北京市教委-北京农学院都市农林学交叉学科平台建设项目(2023)。

摘　　要：目的建立一种溶剂提取(solvent extraction,SE)、水蒸气蒸馏(steam distillation,SD)分别与分散液液微萃取(dispersing liquid-liquid microextraction,DLLME)有效组合进行样品前处理、稳定同位素稀释-气相色谱-串联质谱法(gas chromatography-tandem mass spectrometry,GC-MS/MS)检测咸鱼中挥发性亚硝胺(volatile nitrosamine,VNA)的方法。方法样品加入9种VNA稳定同位素标记物,分别进行SE(甲醇-水为溶剂)和SD处理,提取液和蒸馏液分别进行DLLME,以GC-MS/MS多反应监测(multiple reaction monitoring,MRM)模式进行检测。结果方法在1~100 ng/mL范围内各VNA线性良好,相关系数(r2)为0.9920~0.9999;SE-DLLME处理简便快速,二甲基亚硝基胺(nitroso dimethylamine,NDMA)检出限(limit of detection,LOD)为0.79μg/kg、定量限(limit of quantification,LOQ)为2.63μg/kg,其他VNA的LOD为0.03~0.43μg/kg、LOQ为0.10~1.44μg/kg,可满足咸鱼中VNA合格性快筛的需要;SD-DLLME处理,NDMA的LOD为0.06μg/kg、LOQ为0.21μg/kg,其他VNA的LOD为0.01~0.40μg/kg、LOQ为0.03~1.30μg/kg,可满足关注浓度以下VNA定量检测的需要;总体加标回收率分别为89.81%~105.10%,相对标准偏差为2.70%~7.30%。结论该方法样品处理成本低廉、准确性好,为咸鱼VNA的合格性快筛和低含量水平试样的定量提供了有价值的参考方法。Objective To establish a method for the determination of volatile nitrosamine(VNA)in salted fishes by stable isotope dilution-gas chromatography-tandem mass spectrometry(GC-MS/MS)with combing solvent extraction(SE)and steam distillation(SD)to dispersing liquid-liquid microextraction(DLLME)respectively.Methods Nine VNA stable isotope markers were added to the samples and treated with SE(methanol water as solvent)and SD,respectively.The extraction and distillation solutions were subjected to DLLME and detected using GC-MS/MS multiple reaction monitoring(MRM)mode.Results Good linearity for each VNA was obtained within the range of 1–100 ng/mL,r^(2)were ranging from 0.9920 to 0.9999.With SE-DLLME,the limits of detection(LOD)and limit of quantification(LOQ)were 0.79μg/kg and 2.63μg/kg respectively for dimethylnitrosamine(NDMA);LODs were 0.03–0.43μg/kg and LOQs were 0.10–1.44μg/kg for other VNAs;the qualification fast screening could be met with this combined sample pretreatment.With SD-DLLME,the LOD and LOQ were 0.06μg/kg and 0.21μg/kg respectively for NDMA;LODs were 0.01–0.40μg/kg and LOQs were 0.03–1.30μg/kg for other VNAs;quantification for the samples with VNAs concentrations below the concerning concentration with this combined sample pretreatment.Overall recoveries were 89.81%–105.10%with relative standard deviations ranging from 2.70%to 7.30%.Conclusion This method is low cost,accurate and provides a valuable reference for monitoring the VNA risk of salted fish.

关 键 词：挥发性亚硝胺 组合式经典样品前处理 咸鱼 气相色谱-串联质谱法 

分 类 号：O657.63[理学—分析化学] TS254.7[理学—化学]