Archaeological and Anthropological Sciences (2021) 13:71 https://doi.org/10.1007/s12520-021-01320-5 ORIGINAL PAPER Looking for the missing link in the evolution of black inks Grzegorz Nehring1 & Olivier Bonnerot1,2 & Marius Gerhardt3 & Myriam Krutzsch3 & Ira Rabin1,2 Received: 10 December 2020 /Accepted: 15 March 2021 # The Author(s) 2021 Abstract In the transition from carbon to iron-gall inks, the two documents from the Egyptian Museum and Papyrus Collection in Berlin with shelfmarks P 13500 and P 13501 discussed in this work present an important case. Their inks appear brownish, although they date back to the fourth and third century BCE, when carbon inks are believed to have been commonly if not exclusively used. Using imaging micro-X-ray fluorescence and infrared reflectography, we discovered that the inks in both documents contain a significant amount of copper in addition to carbon. Comparing the extant recipes for black writing inks and the experimental evidence, we suggest that these inks are a transition between the pure carbon and the iron-gall inks. Such inks may have been quite common before the production of iron-gall ink was clearly understood and established. Keywords Black writing ink . Hellenistic . Papyrus . XRF imaging . NIR imaging Introduction the majority of the medieval parchment codices are written with iron-gall ink, at least in Europe, seemed to support the It is customary today to distinguish among three main types of strong correlation between the writing surface and the type of historical black writing inks: carbon, plant, and iron-gall ink. the ink. Interestingly, little attention was paid to the transition The oldest preserved documents are written with carbon inks. period from the carbon inks of Antiquity to the iron-gall inks Such inks were made by mixing soot, a binder of choice, and of the Middle Ages. Zerdoun’s “LesencresnoiresauMoyen water. The second type, plant inks, consists of an aqueous Age: jusqu'à 1600” is the only monograph that offers insight solution of tannins with or without a binding agent. The third into that time, based on the linguistic analysis of the extant kind, iron-gall inks, results from the reaction between tannins sources on writing inks. Apart from this remarkable book, and iron ions usually provided by soluble iron salts, with the there is no systematic overview of the technological evolution addition of a binder. The onset of the use of iron-gall inks, of black writing inks. From this point of view, from the very which are often easily recognized by their corrosive action on first day of its existence, the collaboration of the the substrate, has commonly been associated with the spread Bundesanstalt für Materialforschung und -prüfung (BAM) of parchment as a writing support in the early Middle Ages with the Centre for the Study of Manuscripts Cultures (Diringer 1982, p.531). By contrast, carbon inks, which were (CSMC) of Hamburg University created a unique multidisci- used predominantly on papyri, neither undergo compositional plinary environment perfectly suited to systematically study changes with time nor damage the substrates. The fact that the technological evolution of inks without neglecting histor- most papyri appeared to be penned in carbon ink whereas ical recipes and treatises (Brockmann et al. 2014, 2018). It has to be stressed that the body of experimental work dedicated to various aspects of iron-gall inks focuses mostly * Grzegorz Nehring on the inks of the medieval period or later, rather than their [email protected] early history (see, e.g. the collection of papers in Kolar and Strlič 2006). In the last few decades, destructive sampling of 1 Bundesanstalt für Materialforschung und -prüfung (BAM), Unter historical manuscripts was prohibited, particularly from den Eichen 44-46, 12203 Berlin, Germany inscribed areas. For that reason, a significant portion of the 2 Centre for the Study of Manuscript Cultures (CSMC), University of literature deals with the development of non-destructive Hamburg, Warburgstraße 26, 20354 Hamburg, Germany methods for identifying and classifying ink components (e.g. 3 Ägyptisches Museum und Papyrussammlung, SMB, Budnar et al. 2006;Hahnetal.2004). In addition to articles Geschwister-Scholl-Str. 6, 10117 Berlin, Germany dealing with conservation and analytical techniques, there are 71 Page 2 of 10 Archaeol Anthropol Sci (2021) 13:71 many case studies to help address scholarly questions and gain of X-ray fluorescence (XRF), scanning electron microscope insight into specific writing traditions. The majority of report- with energy dispersive spectroscopy (SEM-EDS), and Raman ed cases, though, deal with parchment and paper but not pa- spectroscopy analysis on inks, they stressed that only “rela- pyrus manuscripts, like the ones presented in this article. For tively low amounts” of copper could be detected in four of this reason, the first appearance and technological develop- them (Christiansen et al. 2017a). Probably intrigued by this ment of iron-gall ink are still obscure. To date, the oldest presence of copper, Christiansen and other colleagues con- documents in which iron-gall ink was experimentally identi- ducted a micro-X-ray absorption near edge structure fied date back to the third or fourth century CE (Aceto et al. (XANES) experiment on another set of papyri at the 2008; Ghigo 2020), although ancient recipes provide hints European Synchrotron Radiation Facility (ESRF), whose re- that the reaction between tannins and vitriol, responsible for sults were published in the same year1 (Christiansen et al. the black colour of iron-gall ink, was already known at an 2017b). The authors claimed that copper was present in the earlier date (Zerdoun Bat-Yehuda 1983,p.91-94). form of cuprite, together with azurite and malachite, and sug- In contrast to the huge number of publications dealing with gested that these originate from the soot used. Indeed, in an- medieval inks, the published examples of inks from Antiquity other publication (Christiansen 2017), Christiansen cited sev- that contain metals are rather sporadic and do not offer a ho- eral recipes for magical ink (from the third and fourth centu- mogeneous picture. The discovery exactly thirty years ago of ries CE) that mention specific sources of soot, such as “gold- Hellenistic inks containing metals attracted our attention and smith soot” (αἰθάλη χρυσοχοϊκή)or“coppersmith soot” initiated this line of work. In 1990, Delange and co-authors (αἰθάλη χαλκέως). “Coppersmith soot” might refer to soot published a Particle-Induced X-ray Emission (PIXE) study of collected from copper or bronze vessels, resembling the de- five bilingual papyri (Greek and Egyptian demotic, scription by Pliny the Elder in the first century CE (Pliny shelfmarks N2433, N2429, N2416, N2410, and N2422) and Naturalis Historia XXXV 25.43).2 Christiansen also touched one Greek papyrus (shelfmark N2331) from the Louvre col- upon the “painter’ssoot” (ἀσβόλη ζωγραφική) mentioned lection and dating from 253 to 98 BCE (Delange et al. 1990). by Dioscorides in his De Materia Medica, which is soot col- No metal was found in the demotic text, but copper, some- lected from glassworks (Dioscorides De Materia Medica V times associated with traces of lead or iron, was found in the 161). While cuprite was indeed probably used in ancient glass ink of the Greek text on four of the five bilingual papyri and on manufactures, in particular to obtain red or orange glass the Greek papyrus. In the absence of reflectographic analysis, (Barber et al. 2009), it is unlikely that azurite and malachite it is not clear whether the inks also contained elemental carbon were used in the coloured-glass-making industry, for which and belong to the category of mixed ink discussed here. More the main source of copper was probably scraps of bronze recently, Rabin et al. published the analysis of an ink contain- (Freestone 2008). ing an elevated amount of copper in a section of P. Laur. Inv. Besides these examples from Antiquity, copper and carbon 19655 from the second century CE in the Biblioteca Medicea have been reported in the inks of three Coptic fragments from in Florence, whose ink has visual aspects similar to the ones the Roca Puig collection (inv. 345, 357, 399) originating from discussed in this article. This time, elemental carbon was also the monastery of Apa Apollo in Bawit and paleographically identified, using near infrared (NIR) reflectography (Rabin dated to the seventh–eighth centuries. The inks from these et al. 2019). Bonnerot et al. also recently detected copper in documents visually strongly resemble the ones discussed in inks from several fragments detached from Herculaneum the present article (Ghigo 2020). The presence of other metals scrolls (Bonnerot et al. 2020). On these fragments, carbon- like iron or lead is sometimes also mentioned (Bonnerot et al. based pigment is clearly visible in the infrared images collect- 2020;Brunetal.2016;Christiansenetal.2020). It is clear ed by Booras and his team (MacFarlane et al. 2007). However, from this short overview that there is a lack of understanding we cannot determine the ink’s original visual aspects because of the transition from carbon to iron-gall inks. the rolls were carbonized by the eruption of Mount Vesuvius In the present work, combining conservation, papyrology, in 79 CE. Nir-El and Broshi reported the presence of copper in and natural sciences, we focused our attention on the transition the carbon inks of the Genesis Apocryphon (1QGenAp) and from carbon-based to metal-based inks, in which inks contain- several other fragments from Qumran, which they attributed ing copper seem to play a crucial role. Two Greek documents to contamination coming from bronze inkwells (Nir-El and from Elephantine that date back to the early Hellenistic period, Broshi 1996). In the case of the Genesis Apocryphon, no signs preserved in the Egyptian Museum and the Papyrus of metallic presence could be seen other than a corrosive ac- Collection in Berlin, are inscribed with a corrosive ink that tion that practically destroyed the parchment of the scroll.