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 to N-nitrosamines under certain circumstances, is concerned as well. Consequently, there are many regulations and standards successively published to restrict N-nitrosamines and N-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 contain N-nitrosamines and N-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 14 N-nitrosamines and N-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 of N-nitrosamines and N-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 14 N-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 14 N-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 of N-nitrosamines in 4 batches of balloon samples and migrations of N-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 of N-nitrosamines and N-nitrosatable substances.