Mössbauer study of iron gall inks on historical documents

Abstract

AbstractIron gall ink was used in the Western world as a permanent writing material already in late Roman times and throughout the Middle Ages, until it became obsolete in the twentieth century. There is much interest in experimental methods to determine the state of the ink and its degradation products on historical documents. Mössbauer spectroscopy with 57Fe is such a method, and it has the particular advantage to be sensitive to the chemical bonding of iron, but this method has only rarely been applied to historical documents. In this paper we present Mössbauer data for two damaged documents from a Library in Granada and a handwritten German book from the eighteenth century. In addition to the inked parts of the manuscripts, ink-free parts were studied to determine the amount and chemical state of the iron in the papers. These new results are discussed in the context of previously published Mössbauer data. In one of the investigated documents Fe(II)-oxalate, FeC2O4·2H2O, was observed. The assignment of the various Fe3+ sites in the different documents is rather difficult and often there is a superposition of various species. Known forms of iron gallate are definitely not present on the inked papers. The observed ferric species can be remains of Fe3+ polyphenol complexes of the ink, complexes of Fe3+ with degradation products of the cellulose of the paper or gum arabic, or very small iron oxide or hydroxide nanoparticles.