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This work describes the development of an ultra-high-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) method for the determination of 23 primary aromatic amines (PAAs) that can potentially migrate from food contact materials. The chromatographic separation was performed in a pentafluorophenylpropyl (PFPP) column achieving the separation of all PAAs in less than 6.5 min using water to acetonitrile (0.1% acetic acid in both solvents) as mobile phase and a gradient elution. The feasibility of atmospheric pressure chemical ionization (APCI) and atmospheric pressure photoionization (APPI) was evaluated as alternative to electrospray ionization (ESI) for the analysis of PAAs. Results showed that for most of the compounds, better responses were obtained with APCI, which shows the advantage of being less susceptible to matrix effects. Tandem mass spectrometry (MS/MS) fragmentation studies of [M + H] +  allowed for the selection of the two most characteristic and abundant product ions of the 23 PAAs which led to the development of a selective and sensitive UHPLC-APCI-MS/MS method with limits of detection ranging from 0.2 to 2 μg kg −1 . Moreover, intra-day and inter-day precisions of the method in terms of relative standard deviation (RSD%) were lower than 10% and 15%, while trueness as relative error was &lt;15% for most of the compounds. The UHPLC-APCI-MS/MS method was applied to the analysis of twenty black Nylon kitchenware samples that were submitted to migration tests using food simulant B (3% acetic acid,  w/v ), and the presence of PAAs were detected in eighteen samples at concentrations above the legislated limit (2 μg kg −1  of food or food simulants). Graphical abstract

analytical and bioanalytical chemistry/analytical and bioanalytical chemistry

Ultra-high-performance liquid chromatography-atmospheric pressure ionization-tandem mass spectrometry method for the migration studies of primary aromatic amines from food contact materials