Mössbauer spectrometry applied to the study of laboratory samples made of iron gall ink

Abstract

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Mössbauer Spectroscopic Investigation of FeII and FeIII 3,4,5‐Trihydroxybenzoates (Gallates) – Proposed Model Compounds for Iron‐Gall Inks

“…Fe III gallate(W) seems to form only under alkaline conditions, while ferrogallic inks are usually acidic, which renders it improbable as the black dye in such inks. A reaction of GA and Fe II sulfate in a ratio of 1:1 has been carried out in water at pH 7 by Burgaud et al9 Their RT Mössbauer spectrum does not agree with our spectrum of Fe III gallate(W). Unfortunately, these authors have not measured a spectrum at 4.2 K. Therefore, one cannot be completely certain, but it is considered as highly improbable that the sample obtained by Burgaud et al under conditions of ink formation is Fe III gallate(W).…”

“…Fe III gallate(W) and related compounds, on which is reported herein, are studied in the course of a more comprehensive Mössbauer study of iron gall inks and the compounds they give rise to when written on paper. The spectra of this compound shall serve as a reference material to test the suggestion that Fe III gallate(W) is the color‐carrying component of the iron gall inks 7,9,10…”

“…. Mössbauer spectra of model inks and historical documents have been published,9,11,12 but an assignment to defined chemical species was not possible mainly because well characterized reference materials were missing. The results presented in this work, however, rule out the presence of Fe III gallate(W) in model inks as well as on historical documents.…”

Raman microscopy and x-ray fluorescence analysis of pigments on medieval and Renaissance Italian manuscript cuttings

“…Medieval recipes for iron gall ink utilised iron(II) sulfate (green vitriol) and sometimes also copper(II) sulfate (blue vitriol) along with gallotannic acid (from galls) and a gum Arabic binder (48). These sulfate salts were probably not pure and may have been mixed with other metal salts including zinc(II) sulfate (or white vitriol) as it is known that some pre18th century historical inks contained more zinc than iron (47,(49)(50)(51). In the carnation areas lead (from lead white) is the predominant element, but small amounts of iron and zinc can also be detected (Fig.…”

Determination of the Fe(II)/Fe(III) ratio in iron gall inks by potentiometry: A preliminary study

“…The association of vitriol and tannins leads to the formation of ironbased solids and results in a dark colour which is characteristic of these inks. Such a compound was recently identified and characterised by Mössbauer and Raman spectroscopy [2][3][4]. A binder is generally associated in the recipes.…”