Iron-gall inks have been described as complexes of iron ions with gallic or tannic acids, available in gall extracts. To assess this working hypothesis, we have prepared medieval inks using ingredients and methods appropriate to the fifteenth to seventeenth centuries. The five historical inks studied were selected based upon research into Iberian written sources of medieval techniques. Results are supported by comparison with iron complexes with a well-characterized phenol counterpart: gallic, ellagic, and tannic acids as well as digalloyl and pentagalloyl glucose; as either precipitates or prepared as inks by adding gum arabic. Raman and infrared spectroscopies show that medieval writing inks could not have been represented solely by iron complexes with gallic acid. Overall, writing inks display the infrared signature of gallotannins, indicating that complexes of Fe 3+-polygalloyl esters of glucose are also formed. Our results also show that the commercial tannic acid solution is far more complex than the gall extracts, and cannot be used to represent a gall extract (as described in historic written sources). High-performance liquid chromatographyelectrospray ionisation, HPLC-ESI-MS, reveals that the concentration of gallic acid varies in the gall extracts, depending on the extraction method and ink recipe. Importantly, in certain recipes, gallic acid is found as a minor compound, when compared with the galloyl esters of glucose.

The Ajuda Songbook is an exceptional illuminated manuscript being the only surviving codex of Galician-Portuguese secular poetry; it was produced in the end of the thirteenth century, beginning of the fourteenth century. The diversity of colors accentuated by the presence of lapis lazuli blue and brazilwood pink, demonstrates the desire to produce a sumptuous manuscript. Pink is, in this context, a luxury color and its identification attests to one of the earliest known occurrences of brazilwood in artworks. Scientific analysis showed, for the light pinks, a different formulation from that found in fifteenth-century books of hours and from all historical reconstructions of these colors prepared to date. This knowledge was used to further expand a database previously built in our laboratory and applied to the characterization of pink shades in the Ajuda Songbook. Thirteen brazilwood recipes were selected from seven Medieval treatises and reference materials were prepared based on such historical information. Three types of colors were achieved, defined as translucent rose, rose, and red. The translucent rose was obtained from recipes where egg white is used for extraction, and no other additives are present; rose from recipes with calcium carbonate; and red from a wider range of recipes, in which these ingredients are not mentioned. These colors were then prepared as paints, and analytical results were thus compared with data from the light pinks seen in the Ajuda Songbook’s architectural backgrounds. We were able to reproduce the pink very well using infrared spectroscopy, identifying its main ingredients: calcium carbonate as filler; lead white as the pigment that produces light pink; and the binder as a polysaccharide with a fingerprint similar to mesquite gum. For the chromophore color, the application of chemometrics approaches to molecular fluorescence spectra highlighted a high degree of similarity with the paint reconstructions.

The research on manuscripts provides useful information about the artistic/technical production and the scientific development in the past. However, the reproduction of the ancient recipes is difficult because most of them are described generally or they hide essential information to preserve the production secrets. In this study, four different recipes from the medieval Manuscript H‐490 (École de Médicine of Montpellier University, France) were reproduced. The raw materials and the production process of each recipe were discussed from the point of view of the glassmaking, and the final products were characterized. The recipe (31) indicated the preparation of a white glaze, similar to Islamic frits. The recipes (32) and (33) explained the preparation of an “unbreakable” glass; however, the characterization of the final products showed that no changes in the hardness of the glass were obtained. And the recipe (34) described the preparation of a green glass which was successfully obtained.