Fingerprinting and aging of ink by easy ambient sonic-spray ionization mass spectrometry

Using easy ambient sonic-spray ionization mass spectrometry (EASI-MS), fast and non-destructive fingerprinting identification and aging of ballpoint pen ink writings have been performed directly from paper surfaces under ordinary ambient conditions. EASI-MS data obtained directly from the ink lines showed that pens from different brands provide typical ink chemical profiles. Accelerated ink aging has also been monitored by EASI-MS revealing contrasting degradation behaviors for six different common ink dyes. As demonstrated for Basic Violet 3, some dyes display a cascade of degradation products whose abundances increase linearly with time thus functioning as 'chemical clocks' for ink aging. Analysis of questionable documents has confirmed the ink aging capabilities of EASI-MS. The order of superimposition at a crossing point has also been determined by EASI-MS. For two superimposed ink lines, continuous EASI-MS analysis has also shown that the EASI spray is able to penetrate through the layers and therefore both ink layers could be characterized.