固相萃取-气相色谱-串联质谱法测定乳胶儿童用品中15种N-亚硝胺及其前体物的迁移量

建立了同时测定乳胶儿童用品中15种N-亚硝胺及其前体物迁移量的固相萃取-气相色谱-串联质谱(SPEGC-MS/MS)分析方法。以人工唾液作为迁移模拟物,以Chromabond Easy固相萃取柱(填料的主要成分是极性修饰的聚乙烯-二乙烯基苯共聚物)对迁移液中的N-亚硝胺分析物进行净化,采用HP-5 MS UI色谱柱分离,MS/MS在多反应监测模式下进行定性及定量分析。15种N-亚硝胺在5~2 000μg/L范围内呈良好的线性关系,相关系数均大于0.998;方法定量限(S/N=10)为0.625~12.50μg/kg,低于欧盟2 009/48/EC指令的限量要求。在低、中、高3个添加水平的回收率为53.8%~116.2%、52.7%~105.1%和49.5%~102.9%;日内精密度分别为1.3%~14.0%(n=6),日间精密度为1.6%~7.6%(n=4)。采用本方法对婴儿奶嘴样品和气球样品进行了测定,其中4件奶嘴和7件气球样品中检出亚硝胺及其前体物,奶嘴和气球中N-亚硝胺的总检出含量分别为0.049 9~0.126mg/kg和0.515~41.2 mg/kg;N-亚硝胺前体物总检出量分别为0.026 4~0.030 0 mg/kg和0.187~12.5mg/kg。

Determination of migration of 15 N-nitrosamines and N-nitrosatable substances from children’s latex articles by gas chromatography-tandem mass spectrometry using solid phase extraction

A method based on gas chromatography-tandem mass spectrometry (GC-MS/MS) using solid phase extraction (SPE) has been developed for the determination of 15 N-nitrosamines from children''s latex articles. Artificial saliva was used as the migration solution to extract N-nitrosamines in children''s latex articles. And then a polar modified polystyrene-divinylbenzene copolymer (Chromabond Easy) was used for the selective SPE of the analytes in the migration solution. The analytes were then separated on an HP-5MS UI GC column and determined by MS/MS in multiple reaction monitoring mode for qualitative and quantitative analysis. Good linearity ranged from 5 μg/L to 2000 μg/L was observed for all the compounds (R² >0.998) and the limits of quantification for the 15 N-nitrosamines were 0.625-12.50 μg/kg (S/N=10), which were lower than the limits required by the EU 2009/48/EC Directive. The average recoveries of the target analytes at low, medium, and high spiked levels were in the ranges of 53.8%-116.2%, 52.7%-105.1% and 49.5%-102.9%, respectively. The average within-day and between-day RSDs were from 1.3% to 14.0% (n=6) and from 1.6% to 7.6% (n=4), respectively. The proposed method was used to monitor N-nitrosamines in baby nipples and balloons, and N-nitrosamines were found in some samples. The total contents of the 15 N-nitrosamines in the analyzed nipples and balloons samples ranged from 0.0499 mg/kg to 41.2 mg/kg. And the total contents of the N-nitrosatable substances in the analyzed samples ranged from 0.0264 mg/kg to 12.5 mg/kg.