Composition and spectroscopic properties of historic Cr logwood inks

A basic recipe for making a Cr logwood ink dating to 1847 was adapted in order to obtain hues varying from orange to dark brown. The inks synthesized were characterized by Raman spectroscopy, Fourier transform infrared spectroscopy, liquid chromatography-diode array detection-quadrupole time-of-flight-mass spectrometry, and liquid chromatography-inductively coupled plasma-mass spectrometry to gain insight into the spectroscopic properties of the compounds responsible for the inks colors and to obtain Raman spectra that can be used for their non-invasive identification in works of art and in historic documents. It was observed that hematein and logwood oxidation products are present in the inks and that their relative proportions determine the inks hues. It was also found that relatively small variations in the basic recipe, such as in the temperature that the logwood and K2CrO4 mixture were heated at, gave inks with different hues. The Raman spectra acquired in the laboratory samples were used to characterize the ink used by Vincent van Gogh in Street in Saintes-Maries-de-la-Mer.