气相色谱-质谱法测定玩具中单甲基锡迁移量及其假阳性的确证方法  

Determination of monomethyltin migration from toys by gas chromatography-mass spectrometry and confirmation of its false positive

作　　者：李函珂 蚁乐洲[1] 谭智贤 丁志勇[1] 黄宁姗 黄理纳[1] 马彤梅 LI Hanke;YI Lezhou;TAN Zhixian;DING Zhiyong;HUANG Ningshan;HUANG Lina;MA Tongmei(Guangdong Inspection and Quarantine Technology Center,Guangzhou 510623,China;School of Chemistry and Chemical Engineering,South China University of Technology,Guangzhou 510640,China)

机构地区：[1]广东检验检疫技术中心,广东广州510623 [2]华南理工大学化学与化工学院,广东广州510640

出　　处：《色谱》2018年第11期1181-1188,共8页Chinese Journal of Chromatography

基　　金：国家重点研发计划课题(2016YFF0203705);广东出入境检验检疫局科技计划项目(2017GDK33)~~

摘　　要：基于欧盟玩具安全标准EN 71-3∶2013/A2∶2017中胃液迁移程序,建立了测定玩具中单甲基锡迁移量的气相色谱-质谱法(GC-MS),并首次针对由此引起的单甲基锡假阳性问题建立了确证方法。经优化迁移条件、衍生步骤及色谱条件,单甲基锡在0. 02～1. 0 mg/L范围内呈现良好线性关系,相关系数(R^2)为0. 999 2,方法检出限和定量限分别为0. 11 mg/kg和0. 32 mg/kg。单甲基锡在不同加标水平(0. 1、0. 5和1. 5μg)下的回收率为86. 2%～104. 2%,相对标准偏差为3. 1%～8. 2%(n=6)。实际样品测定表明,马口铁(锡铁合金)材质玩具表面涂层中检出了单甲基锡,迁移量为0. 44～0. 67 mg/kg,并以甲醇和丙酮为迁移溶剂对结果进行确证,经证实其为假阳性结果。Based on migration procedures using simulated gastric juice specified in the EU toy Safety Standard EN 71-3∶2013/A2∶2017,a method was developed for the determination of monomethyltin(MMT)migration from toys by gas chromatography-mass spectrometry(GC-MS).Further,a reliable confirmation method for judgement of a false positive for MMT obtained by GC-MS,was established.After optimizing the migration conditions,derivatization steps and chromatographic parameters,the method yielded a linear range from 0.02 to 1.0 mg/L with a correlation coefficient(R 2)of 0.999 2.The limits of detection and quantification of the method were 0.11 and 0.32 mg/kg,respectively.The recoveries were 86.2%-104.2%under different spiked levels(0.5,1.0 and 1.5μg),and the relative standard deviations were 3.1%-8.2%(n=6).MMT migration ranging from 0.44 to 0.67 mg/kg was detected in the surface coating of tin-plating(Sn-Fe alloy)toy materials,which was subsequently confirmed to be false positive.Therefore,a novel confirmative approach using methanol or acetone as the migration solvent was proposed,aiming at verifying the false positive of MMT.The results showed that the previously positive MMT detected by GC-MS could no longer be detected when treated by these migration solvents.Hence,this approach can be used to confirm false positive detected for MMT after GC-MS detection.

关 键 词：气相色谱-质谱法 假阳性 确证 单甲基锡迁移 玩具 

分 类 号：O658[理学—分析化学]