Atmospheric pressure MALDI for the non-invasive characterization of carbonaceous ink from Renaissance documents

The analytical methods that are usually appliedto determine the compositions of inks from ancient man-uscripts usually focus on inorganic components, as in thecase of iron gall ink. In this work, we describe the use ofatmospheric pressure/matrix-assisted laser desorption ion-ization–mass spectrometry (AP/MALDI-MS) as a spatial-ly resolved analytical technique for the study of the or-ganic carbonaceous components of inks used in hand-written parts of ancient books for the first time. Largepolycyclic aromatic hydrocarbons (L-PAH) were identi-fied in situ in the ink of XVII century handwritten doc-uments. We prove that it is possible to apply MALDI-MS as a suitable microdestructive diagnostic tool foranalyzing samples in air at atmospheric pressure, thussimplifying investigations of the organic components ofartistic and archaeological objects. The interpretation ofthe experimental MS results was supported by indepen-dent Raman spectroscopic investigations.