HPLC-APCI-MS/MS法测定与口接触玩具及儿童用品中14种可迁移N-亚硝胺及可N-亚硝化物质

建立了高效液相色谱-大气压化学电离-串联质谱（HPLC-APCI-MS/MS）法测定与口接触玩具及儿童用品中14种可迁移N-亚硝胺及可N-亚硝化物质。样品在人工唾液中模拟口腔接触后，一部分迁移液用于可迁移N-亚硝胺的分析，另一部分经亚硝化后用于可迁移N-亚硝化物质的分析。实验还对电离源类型、多重反应监测参数、离子源参数、色谱柱类型、梯度洗脱程序、甲酸浓度等条件进行了优化。结果表明：14种目标物在0.2~100 μg/L范围内的线性关系良好，相关系数R²≥0.999 5，方法检出限为0.32~1.0 μg/kg；在5、50、500 μg/kg加标浓度水平的回收率为82.3%~122%，相对标准偏差为1.1%~13.9%（n=5）。实验抽查了104个批次市场样品，包括橡胶和硅胶奶嘴、气球以及其他橡胶制品，阳性率为7.4%。在抽查分析的8批次气球样品中，有4批次N-亚硝胺迁移量和6批次可N-亚硝化物质迁移量超出了欧盟玩具安全指令2009/48/EC规定的迁移限量，阳性率高达75%，说明气球样品的风险最高。

Determination of 14 Migrations of N-Nitrosamines and N-Nitrosatable Substances in Toys and Children’s Products by HPLC-APCI-MS/MS

N-nitrosamines, known as strong carcinogens, are extensively concerned in safety of consumer products, especially in safety of toys. In the mean time,N-nitrosatable substances, such as secondary amines, which can convert toN-nitrosamines under certain circumstances, is concerned as well. Consequently, there are many regulations and standards successively published to restrictN-nitrosamines andN-nitrosatable substances in many countries. Generally speaking, toys and children’s products that contact with mouth, such as balloons and rubber teats, are more likely to containN-nitrosamines andN-nitrosatable substances. In order to meet the analytical requirements of exit-entry inspection of international regulations concerning toys and children’s products, a method of high performance liquid chromatography-atmospheric pressure chemical ionization-tandem mass spectrometry (HPLC-APCI-MS/MS) was developed to determine the migrations of 14N-nitrosamines andN-nitrosatable substances in toys and children’s products that contact with mouth. Samples were cut into pieces and then migrated in artificial saliva to simulate mouth contact. The migration solution was used for the determination ofN-nitrosamines andN-nitrosatable substances after nitrosation afterwards in the presence of nitrite contained in artificial saliva. The conditions and parameters of liquid chromatography and mass spectrometry were optimized, such as multiple reaction monitoring, source-dependent parameters, chromatographic columns selection, gradient elution program and formic acid concentration. The results show that the linear relationships are good for all 14N-nitrosamines in the range of 0.2-100 μg/L with the correlation coefficient greater than 0.999 5. Method detection limits are 0.32-1.0 μg/kg, and the recoveries of 14N-nitrosamines are 88.0%-122%, 89.0%-106%, 91.0%-109% at the spiked levels of 5, 50, 500 μg/kg, respectively. The relative standard deviations (n=5) are 3.0%-13.9%, 1.9%-6.2%, 1.1%-6.6%, respectively. 104 batches of exit-entry spot-check samples were inspected, and it was found that balloons were high risk samples. There are totally 8 batches of balloon samples among all the inspected samples, migrations ofN-nitrosamines in 4 batches of balloon samples and migrations ofN-nitrosatable substances in 6 batches of balloon samples exceed the limit migrations specified in EU Toy Safety Directive 2009/48/EC. The balloon samples have the highest risk, so we need to give extra concern in terms ofN-nitrosamines andN-nitrosatable substances.