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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.
The manuscript Codex germanicus 1 (Cod. germ. 1) of the Staats- und Universitätsbibliothek Hamburg is a fifteenth-century German-language manuscript. It comprises two codicological units and has an especially complex developmental history. To trace this developmental history, neglected until now in the research literature, the manuscript was investigated, for the first time not solely with classical codicological and palaeographical methods, but also with the aid of X-ray fluorescence spectroscopy, in order to determine the composition of the writing materials. These methods made it possible, first, to support and check palaeographic findings and, second, to gain information about the stratigraphy of the manuscript where palaeographic methods find their limits – in regard to short entries, rubrications, and non-alphabetical signs.
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.
Scientific material analysis of the elemental composition of inks from different strata of a manuscript has the potential to complement scholarly observations using palaeography and philology in reconstructing the history of the manuscript’s production, correction and repair.
There are three typologically different classes of black writing inks: soot inks consist of carbon particles.
In 2005, a team of Polish archaeologists discovered three Coptic codices, two on papyrus and one on parchment, in the rubbish dump of a hermitage at Sheik Abd el-Gurna, Egypt. While the parchment codex and the remains of the bindings of the papyrus ones have been conserved, the text blocks of the papyrus codices were opened and disassembled and after being disinfected remained untouched for nearly 15 years, until the current project started. Currently, all three books are stored in the collection of the Coptic Museum in Cairo. Our team undertook the conservation of and archaeometric research on the papyrus codices. The first of the books contains the Canons of Pseudo-Basil, while the second is an Encomium of St. Pisenthios. Both codices have been palaeographically dated to the seventh-eighth centuries CE. In this paper, we describe our project and present the results of the work carried out on the Canons of Pseudo-Basil. Our work involved photography in transmitted light, measurements of the thickness of the papyrus leaves, and digital microscopy under three-light illumination. These measurements allowed us to determine the types of the inks and characterize the papyrus writing substrate. For conservation, we used a novel method developed in the Egyptian Museum in Berlin that comprises suspending papyrus folios on a translucent, extremely thin Japanese paper inside glass frames without the use of adhesives.In 2005, a team of Polish archaeologists discovered three Coptic codices, two on papyrus and one on parchment, in the rubbish dump of a hermitage at Sheik Abd el-Gurna, Egypt. While the parchment codex and the remains of the bindings of the papyrus ones have been conserved, the text blocks of the papyrus codices were opened and disassembled and after being disinfected remained untouched for nearly 15 years, until the current project started. Currently, all three books are stored in the collection of the Coptic Museum in Cairo. Our team undertook the conservation of and archaeometric research on the papyrus codices. The first of the books contains the Canons of Pseudo-Basil, while the second is an Encomium of St. Pisenthios. Both codices have been palaeographically dated to the seventh-eighth centuries CE. In this paper, we describe our project and present the results of the work carried out on the Canons of Pseudo-Basil. Our work involved photography in transmitted light, measurements of the thickness of the papyrus leaves, and digital microscopy under three-light illumination. These measurements allowed us to determine the types of the inks and characterize the papyrus writing substrate. For conservation, we used a novel method developed in the Egyptian Museum in Berlin that comprises suspending papyrus folios on a translucent, extremely thin Japanese paper inside glass frames without the use of adhesives.
This study will present a new approach to distinguishing writing inks that have the same elemental compositions and visual appearances. The approach is based on displaying the intensity of elemental distributions as heat maps that represent data recorded with a scanning μX-ray fluorescence spectrometer. The heat maps present the data so as to facilitate digitally identifying and distinguishing between inks used to produce, correct, and reink two medieval Torah scrolls. As ritual objects, Torah scrolls had to be written in accordance with exacting standards that evolved over time. This requirement led to successive stages of modifications, sometimes over centuries. Both vitriolic and non-vitriolic inks used to modify Torah scrolls can be visually identical to each other. Furthermore, different non-vitriolic inks usually have an identical elemental composition. The solid material analysis evidence and its presentation as heat maps made it possible to discriminate between original and altered portions of text that in some cases would have been impossible. Our interdisciplinary work brought together conservation, material science, paleog-raphy, and philology to enable the identification of complex stratigraphy in multiple stages of production, correction, and reinking. ©2 0 2 2 Published by Elsevier Masson SAS.
The first manuscripts from the Qumran caves were found in 1947. Within the following 10 years, clandestine and legal excavations revealed some 900 highly fragmented manuscripts from the late Second Temple period. This collection is generally known as Scrolls of the Judea Desert or Dead Sea Scrolls (DSS). For many years after their discovery, text analysis and fragmeents attribution were the main concern of the scholars dealing with the scrolls. The uncertain archaeological provenance of the larger part of the collection added an additional difficulty to the formidable task of sorting some 19000 fragments. After 60 years of scholar research the question of origin, archaeological provenance and correct attribution of the fragmenst are still hotly debated. To dtermine a possible contribution to the debate from the point of view of writing materials, we used otpical and electron microscopy, various X-ray based techniques as well as vibratiional sprectroscopy. We validated our approach with SY - based studies using the advantages of the synchroton radiation source with respect to the benchtop devices. Our laboratory studies showed that often production and storage locality could be distinguished thenks to the specific residues ("fingerprint") they left on the material. Moreover, we have diescovered that diferrent parchment production processses coexisted in the antiquity, and the resulting writing materials can readily be distinguished.
While studying the socio-geographic history of inks, division 4.5 of the BAM (Bundesanstalt für Materialforschung und Prüfung) together with the Centre for the Study of Manuscript Cultures in Hamburg has developed a protocol for ink analysis.
It consists of a primary screening to determine the type of the ink, and a subsequent in-depth analysis using several spectroscopic techniques. The XRF elemental analysis aims primarily at identifying and characterizing metallic components of inks. Besides the instrumental methods, the paper presents an overview of historic inks in the period of transition from carbon inks of the Antiquity to iron-gall inks commonly used in the Middle Ages.
This chapter offers observations and considerations concerning black writing inks encountered in writing supports transmitting documentary and literary texts of the late Antiquity and early Middle Ages. It discusses different types of inks, the Methods of their detection and their use in different times and geographical areas.
While studying the history of inks, division 4.5 of the BAM (Bundesanstalt für Materialforschung und Prüfung) together with the Centre for the Study of Manuscript Cultures in Hamburg has developed a protocol for ink analysis. It consists of a primary screening to determine the type of the ink, and a subsequent in-depth analysis using several spectroscopic techniques. One of them, X-ray Fluorescence (XRF) aims primarily at establishing the fingerprints of inks containing metals, making it possible to distinguish among different inks.
Our research aims primarily at recreating a socio-geographic history of inks, parchment, and papyrus and includes the comparative analysis of the writing materials of the Dead Sea Scrolls, ink and papyrus in Ancient and Hellenistic Egypt, and inks in documents from various contemporary medieval communities in Fustat (first nucleus of Cairo) as well as other medieval Jewish and Armenian communities.
The presentation shows the panorama of historic inks and our attempt to follow up the transition of the inks from those based on soot to the iron-gall inks commonly used in the Middle Age.
Our study is dedicated to non-destructive characterization of the support and the inks of the DSS.
To that aim we use micro-XRF, 3D- SY-XRF, different IR methods including synchrotron radiation based reflectance spectroscopy, optical and electron microscopy.
The lecture discusses advantages and the shortcomings of the non-destructive testing approach.
Heute stimmen die meisten Gelehrten und Historiker darin überein, dass die Höhlen von Qumran eine Essener-Bibliothek beherberg-ten. Über ihren Ursprung, sowie die Herkunft der einzelnen Schriften, wird noch immer rege debattiert. Der aktuelle Beitrag präsentiert detaillierte Lösungsansätze zu Klärung der Provenienzfrage der Schriftrollen von Qumran.
Our research aims primarily at recreating a socio-geographic history of inks, parchment, and papyrus and includes the comparative analysis of the writing materials of the Dead Sea Scrolls, ink and papyrus in Ancient and Hellenistic Egypt, and inks in documents from various contemporary medieval communities in Fustat (first nucleus of Cairo) as well as other medieval Jewish and Armenian communities.
The presentation shows the panorama of historic inks and our attempt to follow up the transition of the inks from those based on soot to the iron-gall inks commonly used in the Middle Age.
While studying the socio-geographic history of inks, division 4.5 of the Bundesanstalt für Materialforschung und Prüfung (BAM) together with the Centre for the Study of Manuscript Cultures (CSMC) in Hamburg has developed a non-invasive protocol for ink analysis. It consists of a primary reflectographic screening to determine the type of the ink (soot, tannin or iron-gall) and a subsequent in-depth analysis using several spectroscopic techniques: X-ray fluorescence (XRF), Infrared and Raman spectroscopies. The first of them, XRF elemental analysis aims at establishing the unique fingerprints of inks containing metals or trace elements in carbon inks. In addition, we use Raman analysis to identify so-called mixed inks, an ink category that received little attention so far. Finally, with the help of IR spectroscopy we obtain information about the ink binders.
The evolution and socio-geographic distribution of writing inks from Late Antiquity to the Middle Ages are one of the foci of our investigative work at the Bundesanstalt für Materialforschung und -prüfung (BAM) in Berlin and the Centre for the Study of Manuscript Cultures, Hamburg University.
This presentation will examine the inks used by Jews in the in different geographical zones try to correlate the results of the material analysis with written records and existing traditions. We will compare the inks proposed by Maimonides, who lived in 12th-century Egypt, with the considerations of Rashi, who lived in 11th-century northern France, and see that they both advocated use of the inks commonly known and produced in their respective regions. It is Maimonides who proposes to add tannins to the soot inks, but rejects the metallic salt, both of which were practices that were well attested in contemporary Arabic recipes for making ink. In contrast, Rashi was favourable to employing the plant inks in use in contemporary Northern Europe.
Natural sciences play auxiliary role in the studies of manuscripts. The success of their contribution depends strongly on the formulation of the question and the choice of the methods to obtain the requested answer. Therefore, one should try to go beyond the understanding of the basic principles of the scientific analysis.
We will start with a glance at the basic principles of the techniques used in the material science for determination of the elemental composition (X-ray emission) and molecular composition (FTIR & Raman). We will move then to the bench and mobile equipment commonly used in the field of cultural heritage. At the end we will choose a question to be answered and design an ideal experiment that will be modified according to the limitations dictated by on-site conditions.
In the ateliers in the afternoon we will
a) compare two XRF devices that differ in their spatial resolution;
b) use a high resolution microscope (Keyence) to obtain a close look at writing surfaces and materials;
c) we will learn to determine the type of the inks with the help of another microscope (DinoLite AD413T-12V), a usb microscope with visible, UV and NIR illumination;
d) we will learn to use FTIR-ATR device for determination of the type of the writing surface;
e) We will use mobile Raman device for identification of pigments.
Parchment
(2019)
This lecture will present history of parchment based on written sources and chemical examination of antique, medieval and modern parchment.
Our studies of the Dead Sea Scrolls writing surfaces show that they can be divided roughly into three groups: leather, parchments of a light tint, and those of various shades of brown. The latter ones are invariably tanned, whereas the middle group is characterized by the presence of various inorganic salts. Some of the pale parchments, among them the Temple Scroll (11Q19), are remarkably similar to medieval European parchment. Therefore we have formulated the working theory that in the Judaea of the Hellenistic period two different parchment-making traditions existed side by side: an ‘eastern’ one (represented by the tanned parchments of Qumran, closely resembling Aramaic documents from the fifth century BC, and a ‘western’ one (represented by the untanned/lightly tanned ones similar to early Christian Greek parchments).
This division has found support during our studies of the Geniza fragments, in which Babylonian and Palestinian traditions seem to follow the “eastern” and “western” technologies, respectively.
Inks and pigments
(2019)
The writing materials used in various cultures and epochs can be divided into two groups. The first comprises materials that write themselves, producing script by rubbing their own material off onto the writing surface. It includes charcoal, graphite, chalk, raddle, and metal styluses. Depending on the material and consistency, these are cut or pressed to make styluses and then used for writing.
The second group comprises all coloring liquids that are applied to the writing surface with a quill, pen, or printing block. It includes inks made from dye solutions (for example, tannin inks) and those made from pigment dispersions (for example, sepia, soot, and bister inks). The latter are sometimes also rubbed as pastes into letters incised into the writing surface, where they increase visual contrast.
Due to the variety of recipes and the natural origin of raw materials, there is a wide range of different components and impurities in writing materials.
Soluble inks (Tinten)
Soluble inks are based mainly on dyes forming a water solution. Colored inks were manufactured with different plant or insect dyes (e.g. Brazil wood, kermes). To stabilize the volatile material, the dyes were mixed with a mordant (e.g., alum).
Brown plant inks – best-known as blackthorn or Theophilus’ inks – are usually produced from the blackthorn bark and wine. In the early European Middle Ages, inks of this kind were widely used in the production of manuscripts in monasteries. Usually, they are light brown, so sometimes small amounts of iron sulfate were added, which led to what was called an “imperfect” iron gall ink. The difference between “classic” iron gall ink and such imperfect ink is therefore not clear: the distinction is not possible, especially with the naked eye.
Dispersion inks (Tuschen)
According to its generic recipe, one of the oldest black writing materials is produced by mixing soot with a binder dissolved in a small amount of water. Thus, along with soot, binders such as gum arabic (ancient Egypt) or animal glue (China) are among the main components of soot inks. From Pliny’s detailed account of the manufacture of various soot-based inks, we learn that, despite its seeming simplicity, producing pure soot of high quality was not an easy task in Antiquity. Therefore, we expect to find various detectable additives that might be indicative of the time and place of production. One such carbon ink requires the addition of copper sulfate . The experimental discovery of this ink in 1990 led to a misleading expression “metal ink” that is sometimes found in the literature.
Colored dispersion inks based on pigments such as orpiment, cinnabar, or azurite have been known since Antiquity. Natural or artificially produced minerals are finely ground and dispersed in a binding medium. As in soot inks, water-soluble binders such as gum arabic or egg white were used.
Iron gall ink (Eisengallustinten)
Iron gall inks are a borderline case between these two groups. They are produced from four basic ingredients: galls, vitriol as the main source of iron, gum arabic as a binding media, and an aqueous medium such as wine, beer, or vinegar. By mixing gallic acid with iron sulfate, a water-soluble ferrous gallate complex is formed; this product belongs to the type “soluble inks”. Due to its solubility, the ink penetrates the writing support’s surface, making it difficult to erase. Exposure to oxygen leads to the formation of insoluble black ferric gallate pigment, i.e., “dispersion ink”.
Natural vitriol consists of a varying mixture of metal sulfates. Since for ink making it was obtained from different mines and by various techniques, inks contain many other metals, like copper, aluminum, zinc, and manganese, in addition to the iron sulfate. These metals do not contribute to color formation in the ink solution, but possibly change the chemical properties of the inks.
Physico-chemical analyses of writing materials offer insight into various questions associated with historical, cultural, and conservational aspects of manuscript studies. The catalogue of questions that can be addressed with these methods includes authenticity, dating, the attribution of various parts of the text to different scribes and the relation between the primary and secondary texts. Similarly, preservation of the manuscripts requires knowledge of the composition of the original materials versus old repairs, identification of damage, as well as recognition of natural aging and degradation processes. The material sciences can contribute data about the chemical compositions of the writing materials, elucidation of the techniques of their production and the absolute age of organic components, as well as characterization of corrosion effects, evaluation of conservation treatment, and monitoring of the preservation state.