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Advanced codicological studies of Cod. germ. 6 (Hamburg, Staats- und Universitätsbibliothek): Part 2
(2018)
The work presented here follows the article Combining Codicology and X-Ray Spectrometry to Unveil the History of Production of Codex germanicus 6 (Staats- und Universitätsbibliothek Hamburg), published in 2014.1 It confirms the main result of the previous article: the Artusnotiz, the fourth text in the bound manuscript, must have been introduced as the last one. This paper offers further details of the codex production, based on the composition of the black and red inks collected in four measurement campaigns. Furthermore, using imaging μ-XRF, we succeeded in understanding the strong variation of the composition of the red inks in the initials of all the texts except for Parzival and Jeanne d’Arc.
Typology of Inks
Archives and museums around the world contain a vast number of manuscripts that were written in different inks: carbon inks, plant inks, iron-gall inks and mixed inks. Yet most archaeometric studies of manuscripts focus on the palette of pigments found in illuminated manuscripts whereas identification of the inks is still largely based on cultural-historical studies and visual inspections. One of the reasons of this disproportion in the studies can be explained by the properties of Raman spectroscopy, the technique of choice for identification of pigments. In contrast, this technique is only partially viable when dealing with organic colourants. Brown and Clark discuss these difficulties and the uncertainties of identification of iron-gall inks by Raman spectroscopy in their pioneering work on early medieval Anglo-Saxon manuscripts (K. Brown and R. Clark 2004). To facilitate instrumental analysis of inks, we have developed a protocol that starts with the identification of the inks type (Rabin et al. 2012) which doesn’t require complicated instrumentation and can be carried out by paleographers and codicologists.
Three typological ink classes
The black writing materials used in manuscript production in Antiquity und Middle Ages can be sorted in three typologically different ink classes: soot, plant and iron-gall. Soot ink is a fine dispersion of carbon pigments in a water soluble binding agent; plant-based ink consists of a solution of the tannins extracted from gallnuts or tree bark; iron-gall ink, is produced by mixing a soluble compound of iron (II) with gallic or tannic acid extracted from gallnuts or tree bark. Therefore, iron-gall ink presents a boundary case between solution and dispersion ink, in which a water-soluble preliminary stage oxidizes and evolves into a black, insoluble precipitate similar to the carbon pigments when the writing is exposed to air (Krekel 1999). The additional category of mixed inks, i.e. inks produced by addition of various metals to the soot inks or intentional mixing of iron-gall and soot - based inks started attracting scholarly attention only recently because their significance was established only a short while ago (Brun et al. 2016, Colini 2018, Nehring et al. 2021). We suggest that plant and mixed inks build a bridge from the carbon ink of Antiquity to the properly formulated iron-gall ink that became a standard black ink from the late Middle Ages to the 19th century when it gave way to modern inks.
Our standard protocol for the characterisation of writing materials within advanced manuscript studies has been successfully used to investigate manuscripts written with a pure ink on a homogeneous writing surface. However, this protocol is inadequate for analysing documents penned in mixed inks. We present here the advantages and limitations of the improved version of the protocol, which now includes imaging further into the infrared region (1100−1700 nm).
This work addresses the identification of synthetic organic pigments (SOP) in eight modern reverse paintings on glass (1913–1946) by means of an in-situ multi-analytical approach. We combined the complementary properties of mobile Raman spectroscopy and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) to overcome the main disadvantages of each method: extensive band overlapping in DRIFT spectra and fluorescence problems in Raman spectra. A collection of DRIFTS reference spectra enables a precise pigment identification by DRIFTS and establishes this method as a serious non-destructive alternative for the identification of SOP. The group of β-naphthol pigments yielded valuable results for both methods, whereas synthetic alizarin (PR83) was preferentially detected by DRIFTS. Finally, uncommon triaryl carbonium pigments and two azo group-based yellows were identified in the paintings by means of Raman spectroscopy.