From pigments to coloured napkins: comparative analyses of primary aromatic amines in cold water extracts of printed tissues by LC-HRMS and LC-MS/MS.

A collaborative study was conducted to understand the correlation between pigments purity profile (primary aromatic amine content of the pigments) and the behaviour of these PAAs during cold water extraction (CWE) tests according to EN 645. From a selection of organic pigments based on seven colour indexes (PR122, PR184, PO13, PY74, PY111, PY138 and PY155), the pigment purity profile was established according to European Resolution AP (89) 1, then mono-pigmented inks were prepared and napkins printed with these inks. In a second step, cold water extraction and PAA determination were performed by two independent laboratories. In one laboratory, an analytical method based on LC-MS/MS was used, whereas in the other laboratory a method based on LC-HRMS using Orbitrap technology was developed for the simultaneous analysis of 35 PAAs. Good qualitative results were obtained if we consider that at significant levels the PAAs were positively detected in both laboratories, except for 3-amino-4-methoxybenzanilide and 8-amino-2-methyl-quinoline, for which inter-laboratory differences were observed. It was also shown that no contamination from unexpected PAAs was detected. The comparison between pigment analysis and CWE results shows that if the pigment purity profile is of major importance, other parameters such as pigment surface treatment, ink grinding process or ink formulation could have an important influence on the CWE results. For such sensitive applications, for example napkins or other Food Contact Materials (FCM), it is therefore recommended not only to select a pigment with a good purity profile but also to test the pigment in the final application. Finally, this work highlights the difficulty of validating a product on a single analysis and shows the importance of a multilevel global assessment on worst case application.