Studies on the degradation of blue gel pen dyes by ion-pairing high performance liquid chromatography and electrospray tandem mass spectrometry

Ion-pairing high performance liquid chromatography (IP-HPLC) was utilized to monitor the composition changes of blue gel pen ink entries on paper stored in different light conditions and natural environment. The chromatographic conditions were optimized by comparing the separation efficiencies of the blue gel pen inks using a series of ion-pairing reagents, including ammonium carbonate, ammonium acetate, triethylamine acetate, tributylamine acetate, tetrabutylammonium bromide and dihexylammonium acetate. It has been found that tributylamine acetate was a suitable ion-pairing reagent for separation of the inks on the common C18 column. The analysis results of the ink entries on paper in different aging conditions showed that the tendency of composition change in natural aging condition was similar with those in fluorescent light and UV light conditions, respectively. One main component dye of the blue gel pen ink, Acid Blue 9, and its degradation products were identified by ion-pairing high performance liquid chromatography coupled with electrospray tandem mass spectrometry. The results showed that the main degradation products originated from the Acid Blue 9. It gave a reasonable explanation for the changing rules of the relative content of the dyes in the blue gel pen ink. The results obtained can provide scientific evidences for dating of the blue gel pen ink entries on documents.