气相色谱-三重四极杆质谱法测定染发剂中14种N-亚硝胺类化合物

Determination of 14 N-nitrosamines in hair dyes using gas chromatography-tandem mass spectrometry

建立了气相色谱-三重四极杆质谱法测定染发剂中N-亚硝基乙基异丙胺等14种N-亚硝胺类化合物含量的方法。样品采用QuEChERS法前处理,经聚乙二醇石英毛细管柱HP-INNOWAX(30 m×0.25 mm×0.25μm)程序升温分离,在多反应监测(MRM)模式下分析,含量计算为外标法。结果表明,14种亚硝胺在5~100μg/L范围内线性关系良好(r>0.998),检出限和定量下限分别为0.2~1.5μg/L和0.6~5μg/L。在25,50,100μg/kg加标水平下,染发剂基质的平均回收率为83.8%~122.8%,相对标准偏差(RSD)小于11%(n=6)。采用该方法测定市售染发产品,结果发现1批样品中含有N-甲基-N-亚硝基苯胺,含量为31μg/kg。该方法前处理简单高效,专属性强,灵敏度高,准确性好,可用于染发剂中14种亚硝胺的筛查和含量测定。

A gas chromatography-tandem mass spectrometry(GC-MS/MS)method was established for the simultaneous detection of 14 N-nitrosamines(N-nitrosodimethylamine,N-nitrosoethylmethylamine,N-nitrosodiethylamine,N-nitrosoethylisopropylamine,N-nitrosodiisopropylamine,N-nitrosoethylpropylamine,N-nitrosodipropylamine,N-nitrosodibutylamine,N-nitrosomethylaniline,nitrosoethylphenylamin,N-nitrosopiperidine,N-nitrosopyrrolidine,N-nitrosomorpholine,N-nitrosodiphenylamine)in hair dyes.Pretreating based on QuEChERS method,the analytes were separated by polyethylene glycol quartz capillary gas chromatographic column HP-INNOWAX(30 m×0.25 mm×0.25μm)following the GC temperature program.Mass spectrometric ionization was undertaken in electron impact(EI)ionization mode,and the MS detector was operated in multiple reaction monitoring(MRM)mode including quantitative ion pair and qualitative ion pair for all analytes.The correlation coefficients of the standard calibration curves are greater than 0.998 in the range of 5-100μg/L.The limits of detection are 0.2-1.5μg/L,and the limits of quantification are 0.6-5μg/L,respectively.The average recoveries of 14 N-nitrosamines range from 83.8%to 122.8%at the spiked levels of 25,50 and 100μg/kg,with the relative standard deviations(RSDs)less than 11%(n=6).N-nitroso-n-methylaniline is detected at the level of 31μg/kg in one hair dye sample.The developed method is simple,rapid,exclusive,sensitive,accurate and precise.This method can be applied in the identification and quantitative of 14 N-nitrosamines in hair dyes.