The question for discriminating iron gall inks is addressed by correlating their infrared (IR) spectra in liquid and dried states with the materials used in their formulations and considering their possible interactions. A series of laboratory inks were prepared according to historic recipes, mainly found in 19th-century documents, and were accordingly studied using Fourier transform infrared (FT-IR) spectroscopy. All ink formulations were based on Aleppo galls, ferrous sulfate, and gum arabic at variable proportions, with various added components, such as alum, vinegar, glycerol, sugar, silver nitrate, cloves, and white wine. Ingredients of the corresponding inks were recognized by means of their IR fingerprints in both their liquid and dried states, respectively. Although a few inks of distinct formulations showed discernible differences in their spectra, the majority showed quite similar absorptions. Principal component analysis and discriminant analysis were employed to successfully discriminate inks, based on their IR peaks. Spectra recorded in the liquid state, despite their broad absorption features, led to satisfactory discrimination of certain types of inks as most of their ingredients are reflected in their IR peaks. Spectra from dried inks contained similar information, which equally worked in a sufficient discriminatory way. Key IR peaks in the recorded spectra of inks made with the addition of special ingredients, such as vinegar, wine, alum, glycerol, and sugar, as well as those prepared with specific tannin-enhancing procedures, such as gall boiling, were located and used in the discrimination basis.
