氢氧化钡处理-分散液液微萃取结合气相色谱-串联质谱法测定肉制品中9种N-亚硝胺  

Determination of 9 kinds of N-nitrosamines in meat products by gas chromatography-tandem mass spectrometry with barium hydroxide treatment followed dispersive liquid-liquid microextraction

作　　者：李芳芳 梁秀清 王艳丽 陈倩倩 鞠香 陈克云 李洁 田其燕 刘艳明 LI Fang-Fang;LIANG Xiu-Qing;WANG Yan-Li;CHEN Qian-Qian;JU Xiang;CHEN Ke-Yun;LI Jie;TIAN Qi-Yan;LIU Yan-Ming(Shandong Institute for Food and Drug Control,Shandong Research Center of Engineering and Technology for Quality Control of Food for Special Medical Purposes,Shandong Research Center of Engineering and Technology for Safety Inspection of Food and Drug,Jinan 250101,China)

机构地区：[1]山东省食品药品检验研究院,国家市场监管重点实验室(肉及肉制品监管技术),山东省食品药品安全检测工程技术研究中心,济南250101

出　　处：《食品安全质量检测学报》2023年第4期137-144,共8页Journal of Food Safety and Quality

基　　金：山东省药品监督管理局科研项目(SDNMPAFZLS202202);山东省食品药品检验研究院科研项目(SDIFDC-KY-2021011)。

摘　　要：目的建立氢氧化钡碱溶液-分散液液微萃取结合气相色谱-串联质谱法(gaschromatography-tandem massspectrometry,GC-MS/MS)同时测定肉制品中9种N-亚硝胺类化合物的分析方法。方法肉制品样品在80℃水浴中经氢氧化钡碱溶液皂化,去除油脂干扰,进一步将N-亚硝胺提取到水溶液中,再加入甲醇(分散剂)和二氯甲烷(萃取剂)进行高效萃取富集,在多反应监测模式下分析,稳定同位素内标法定量。对影响萃取效率的因素进行考察,如样品提取步骤中的皂化条件,无机盐、萃取剂和分散剂的种类及体积等。通过优化色谱、质谱参数和前处理条件,获得最佳检测结果。结果除了N-亚硝基二甲胺(N-nitrosodimethylamine,NDMA)的线性范围为2.5~50.0 ng,其他8种N-亚硝胺类化合物在1.0~50.0 ng范围内线性关系良好,9种N-亚硝胺类化合物的相关系数(r2)范围为0.9954~0.9999,方法检出限和定量限分别为0.1~0.2μg/kg和0.2~0.5μg/kg。在火腿、五香鸡肉和牛肉样品中分别进行0.5、5.0μg/kg浓度水平的加标实验,所有分析物的平均回收率为78.2%~120.4%,相对标准偏差(relative standard deviations,RSDs)为1.3%~11.2%。结论该方法样品使用量少,前处理操作简单,不需要长时间蒸馏提取,并且有机试剂的使用量也较低,对环境绿色友好。所建立的方法准确、灵敏,可为肉制品中9种N-亚硝胺的同时测定提供技术支持。Objective To develop a method for the simultaneous determination of 9 kinds of N-nitrosamines in meat products by gas chromatography-tandem mass spectrometry(GC-MS/MS) coupled with barium hydroxide alkali solution and dispersive liquid-liquid microextraction. Methods The meat samples were saponified by barium hydroxide alkali solution at 80℃ in a water bath to remove the oil interference, and then the N-nitrosamines were extracted into the aqueous solution, followed by the addition of methanol(dispersant) and dichloromethane(extractant) for efficient extraction and enrichment, which were analyzed in multiple reaction monitoring mode and quantified by stable isotope internal standard method. The factors affecting the extraction efficiency were investigated, such as the saponification conditions in the extraction step, inorganic salts, types and volumes of extractants and dispersants. The chromatographic and mass spectrometric parameters and pre-treatment conditions were optimized to obtain the best detection results. Results In addition to the linear range of N-nitrosodimethylamine(NDMA) of 2.5-50.0 ng, the other 8 kinds of N-nitrosamines had a good linear relationship in the range of 1.0-50.0 ng. The correlation coefficients(r2) of the 9 kinds of N-nitrosamines ranged from 0.9954 to 0.9999, and the limits of detection and limits of quantification were 0.1-0.2 μg/kg and 0.2-0.5 μg/kg, respectively.The average recoveries of all analytes were 78.2%-120.4% with the relative standard deviations(RSDs) of 1.3%-11.2% in ham, spiced chicken and beef samples spiked at the concentration levels of 0.5, 5.0 μg/kg,respectively. Conclusion The method is environmentally green with low sample usage, simple pretreatment operation, no need for long time distillation and extraction, and low usage of organic reagents. The established method is accurate and sensitive, and can provide technical support for the simultaneous determination of 9 kinds of N-nitrosamines in meat products.

关 键 词：碱液处理 分散液液微萃取 气相色谱-串联质谱法 肉制品 N-亚硝胺 

分 类 号：O657.63[理学—分析化学] TS251.7[理学—化学]