Direct Analysis of Xanthine Stimulants in Archaeological Vessels by Laser Desorption Resonance Enhanced Multiphoton Ionization.

Resonance enhanced multiphoton ionization spectroscopy (REMPI) generates simultaneous vibronic spectroscopy and fragment free mass spectrometry to identify molecules within a complex matrix. We combined laser desorption with REMPI spectroscopy to study organic residues within pottery sherds from Maya vessels (600-900 CE) and Mississippian vessels (1100-1200 CE), successfully detecting three molecular markers, caffeine, theobromine, and theophylline, associated with the use of cacao. This analytical approach provides a high molecular specificity, based on both wavelength and mass identification. At the same time, the high detection limit allows for direct laser desorption from sherd scrapings, avoiding the need for extracting organic constituents from the sherd matrix.