AbstractPrimary aromatic amines (PAAs) may be found in food contact materials and can potentially migrate from packaging material into the packed foodstuffs. Certain members of this substance class are of particular concern due to their toxicological properties. Legislators and authorities require a risk assessment regarding the transfer of PAAs into food. The evaluation of PAAs’ migration into food relies on migration or extraction tests using aqueous and acidic food simulants or solvents. However, PAAs exhibit stability issues in acidic media, which could lead to an underestimation of migration. Therefore, a systematic stability study was conducted for 28 PAAs in 3% acetic acid and water at different storage conditions. Standard solutions of 2 and 10 ng/ml of the amines in these media were prepared and stored under the following conditions: 2 h at 40 °C, 70 °C, and 100 °C, and 10 days at − 20 °C, 4 °C, 20 °C, 40° C, and 60 °C. The test solutions were analyzed using liquid chromatography coupled to mass spectrometry, and recovery was calculated against freshly prepared standard solutions. It was found that several PAAs undergo a loss of recovery under the investigated conditions; 7 of the substances were identified to be the most unstable: 3,3ʹ-dimethoxybenzidine, 3,3ʹ-dimethylbenzidine, 6-methoxy-m-toluidine, 4-methoxy-m-phenylendiamine, 2,6-toluenediamine, benzidine and 2,4-toluenediamine. It was concluded that both time and storage temperature play a pivotal role in the stability of PAAs. The experiments also demonstrated that PAAs exhibit greater stability in water than in 3% acetic acid.