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Organisationseinheit der BAM
Eingeladener Vortrag
- nein (77)
Recent research has suggested that some of the inks used in Herculaneum papyri do not consist of pure carbon. Starting from this finding, in June 2018 a preliminary campaign of analysis by means of X-Ray fluorescence (XRF) of external portions removed mechanically from their original rolls in the eighteenth century (the so-called scorze) took place at the Biblioteca Nazionale at Naples. Also in this case, the aim of the survey was to investigate the ink composition in order to detect possible traces of metal. This article sums up the results of this survey.
Hundreds of papyrus rolls, carbonized during the 79CE eruption of Mount Vesuvius, were discovered in 1754 at Herculaneum. Sophisticated mechanical methods for unrolling the best-preserved scrolls have been applied, with varying success. However, such processes have been abandoned, to prevent risk from irremediable damage or loss and to preserve the integrity of the extremely fragile rolls. Following the development of X-ray based non-invasive techniques, attempts to virtually unroll the scrolls were made. The most common ink in Antiquity was carbon-based, and the main element of carbonized papyrus is carbon, making these investigations difficult. However, some attempts with synchrotron X-ray phase-contrast tomography (XPCT) were successful. Recently, the identification of antique inks containing metals raised hope that if some of the inks contain metal the rolls can be virtually unrolled using conventional CT- technique. We investigated the inks of a selection of partially unrolled fragments stored at the Biblioteca Nazionale di Napoli with X-ray fluorescence in order to select the best candidates for tomography. Despite the many difficulties (analysis of several layers sticking together, letters barely visible, difficulty to separate contribution from the ink and from the papyrus, inhomogeneity of the support, fragility of the fragments…), encouraging results were found, with a number of inks from Greek fragments found to contain additions to the soot (Fe, Pb, Cu P).
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.
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.
While studying the socio-geographic history of inks, division 4.5 (Analysis of cultural artefacts and assets) of the BAM (Bundesanstalt für Materialforschung und -prüfung) in Berlin 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.
Using this protocol, scientists can assist scholars in addressing a rather broad range of historical questions that cannot be answered unequivocally through scholarly research alone. Among these are investigations on collaboration between scribes and scriptoria, on the usage and annotation of manuscripts and on their path through time and space in general. This research can thus help to reconstruct the circumstances of the production of written heritage as well as their history and transmission.
To facilitate the dialogue between the scholars and the scientists a simple optical tool was developed to allow the scholars to perform preliminary ink analysis required for formulation of the question that in turn can be answered by scientific in-depth investigations. In this paper, ink types and their identification method is accompanied by examples of the recent work conducted on parchment manuscripts in the Austrian National Library.
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 fragments 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 questions of origin, archaeological provenance and correct attribution of the fragments are still hotly debated.
In many cases material characterization of the scroll writing media deliver answers to the questions stated above. Furthermore, issues concerning corrosion pathways, ancient technologies and contemporary conservation activities demand in depth material studies. To obtain a comprehensive picture we use optical and electron microscopy, various X-ray based techniques as well as vibrational spectroscopy. We validated our approach with SY- based studies using the advantages of the synchrotron radiation source with respect to the bench-top devices.
Our laboratory studies showed that often production and storage locality could be distinguished thanks to the specific residues (“fingerprint”) they left on the material. Moreover, we have discovered that different parchment production processes coexisted in the antiquity, and the resulting writing materials can readily be distinguished.
Within our recent studies we tentatively reconstructed the history of the Genesis Apocryphon. Written with a corrosive ink on a tanned parchment, it was found rolled together with an additional layer of non-inscribed non-tanned parchment. Chemical composition of the ink is in agreement with a 1st century AD ink recipe recorded in Materia Medica by a Greek physician, Pedanius Dioscorides. Study of the scroll deterioration as a function of time and exposition to light during the post-discovery period allows us to speculate that the scroll was rather “archived” than hidden in Cave 1. These results confirm the theory of Eliezer Sukenik who believed Cave 1 to be a “geniza”. A similar study of the Temple Scroll, discovered in the cave 11 indicates that the scroll was rather hidden than “archived”.
Tuschenanalyse im P 11702
(2021)
Near-inframed reflectography and imaging X-Ray flourescence analysis reveal that carbon inks of two different compositions were used in the papyrus manuscript Berlin P 11702. in contrast with the writing ink, one of the carbon drawing inks contained a significant addition of iron. This result emphasises the need for routine instrumental ink analysis.
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.
Towards a unified database of the writing materials used in ancient and medieval Hebrew manuscripts
(2014)
Our experimental knowledge about the inks of antiquity and late antiquity rarely goes beyond their visual description. In rare cases, inks typology has been determined by means of microscopy and reflectography, i.e. using their physical and optical properties, respectively. Since carbon, plant and iron gall inks belong to different classes of compounds they could be easily distinguished had only pure inks been used. Even these crude observations suggest that the inks used differed greatly in their composition.
Reconstruction of the ink recipes with the help of advanced non-destructive analytical techniques could serve as a powerful accessory for in the studies of ancient papyri.
The proposed paper will present a short survey of the methods of material analysis and the challenges offered by ancient inks. The examples of the ink studies from the collections of the Israel Museum in Jerusalem and Egyptian Museum in Berlin will conclude the paper.
The miraculously preserved 2000-year-old Dead Sea Scrolls, ancient texts of invaluable historical significance, were discovered in the mid-20th century in the caves of the Judean desert. The texts were mainly written on parchment and exhibit vast diversity in their states of preservation. One particular scroll, the 8-m-long Temple Scroll is especially notable because of its exceptional thinness and bright ivory color. The parchment has a layered structure, consisting of a collagenous base material and an atypical inorganic overlayer. We analyzed the chemistry of the inorganic layer using x-ray and Raman spectroscopies and discovered a variety of evaporitic sulfate salts. This points toward a unique ancient production technology in which the parchment was modified through the addition of the inorganic layer as a writing surface. Furthermore, understanding the properties of these minerals is particularly critical for the development of suitable conservation methods for the preservation of these invaluable historical documents.
The analysis of physical and chemical properties of artefacts provides important data for answering questions that cannot be solved by historical and philological methods alone. In its individual materiality, each manuscript is the result of various influences (e.g. production, storage, restoration, preservation). Given the recent technological developments (e.g. miniaturization of structural units, enlargement of memory capacity), technical diagnostics of art and cultural objects are becoming increasingly sought after in trans-disciplinary research. In this review we present a multi-instrumental approach to the investigation of manuscripts. Several case studies will illuminate our methodology.
Interest in the type of skin used in scriptural materials and preparation methods increased from the nineteenth into the twentieth century. This was due partly to the number of newly discovered fragments and to the invention of new instruments and scientific procedures to identify animal skins and produce qualitative means to demonstrate specific preparation reagents and techniques. The invention of various means of analyzing the DNA of organic materials brought about a revolution in archaeology and in conservation. Difficulties in overcoming contamination of archaeological samples resulted in a number of controversies but also produced advances and improvement in the techniques of ancient DNA analysis and interpretation of results.
The quest for the mixed inks
(2018)
In this article, we would like to share our observations concerning the inks produced by intentionally mixing soot or charcoal with tannin extracts or iron-gall ink. Aside from Zerdoun’s mention in her outstanding review of written sources, “Les encres noires au Moyen-Âge”, this ink category has received little if any attention from scholars and scientists. And yet, if analytically attested, the use of such inks could serve as an additional category to classify and distinguish the writing inks on the historical socio-geographic map of the writing inks we are trying to build.
In an interdisciplinary collaboration, restorers, art historians, and scientists examined Guilio Romano’s The Madonna with the Wash-Basin of 1525 (Dresden State Art Collections). Insights into the painting technique along with art historical comparisons provided the opportunity for a better understanding of the painting’s genesis, in particular concerning an early reworking of the background by the artist. A recovery and reconstruction of the earlier version of the background is now possible. The discovery of zinc in distinct passages of the painting, as well as the grey-black pigment stibnite and glass particles used as a supplement in paint layers are of special interest. The technological investigation initiated a discussion about the circumstances of the revision, as well as the painting’s relation to Vasari’s Lives of Artists.
The Erfurt Hebrew Giant Bible and the Experimental XRF Analysis of Ink and Plummet Composition
(2007)
The aim of the research project 'Typology of
Dutch Drawing' was to establish an interdisciplinary approach
for investigating heterogeneous drawing collections.
To define a type common to a group of drawings, we
determine elements that are common to them based on style
and the use of identical materials. To that end, we investigated
about 750 Dutch drawings from the sixteenth century at the
Dresden Kupferstich-Kabinett using art historical and
scientific methods. In this work, we present a detailed
analysis of 30 drawings ascribed to the Egmont Master.
This paper addresses the role of material analysis in the current discussion on the authenticity of unprovenanced fragments. It will show that material analysis alone, especially its non-destructive variety, cannot prove that the object is genuine. The best material analysis can do, after all appropriate tests have been conducted, is to announce that nothing has been found that contradicts the assumption of genuineness. Moreover, the results of the material analysis can never be used as the only justification of authentication in cases of composite objects such as manuscripts or epigraphs.
The most effective approach for testing suspicious artifacts has been established by forensic science. Not limited to non-invasive analysis, this approach relies on validated techniques that usually require the extraction of samples and comparison with reference materials and are capable of delivering unambiguous results. In contrast, the analysis of suspicious manuscripts has to overcome additional obstacles such as the heterogeneity of historical material, the scarcity of suitable reference standards, and restriction to strictly non-invasive techniques.
We discuss the reliability of the testing protocol based on the non-destructive multi-instrumental approach developed by the BAM for the investigation of writing materials. In the case of the DSS, it relies on comparison with the genuine DSS fragments studied over the last 10 years.
Unilateral and solid-state nuclear magnetic resonance
(NMR) analyses were performed on a parchment
fragment of the Dead Sea Scroll (DSS). The analyzed
sample belongs to the collection of non-inscribed and
nontreated fragments of known archaeological provenance
from the John Rylands University Library in Manchester.
Therefore, it can be considered as original DSS material
free from any contamination related to the post-discovery
period. Considering the paramount significance of the DSS,
noninvasive approaches and portable in situ nondestructive
methods are of fundamental importance for the determination
of composition, structure, and chemicalphysical
properties of the materials under study. NMR studies
reveal low amounts of water content associated with
very short proton relaxation times, T1, indicating a high
level of deterioration of collagen molecules within scroll
fragments. In addition, 13C cross-polarization magicangle-
spinning (CPMAS) NMR spectroscopy shows characteristic
peaks of lipids whose presence we attribute to
the production technology that did not involve liming.
Extraction with chloroform led to the reduction of both
lipid and protein signals in the 13C CPMAS spectrum
indicating probable involvement of lipids in parchment
degradation processes. NMR absorption and relaxation
measurements provide nondestructive, discriminative, and
sensitive tools for studying the deterioration effects on the
organization and properties of water and collagen within
ancient manuscripts.
The investigation of physical properties and chemical composition generates data important for answering cultural-historical questions that cannot be solved by historical and philological methods alone. Due to technological developments, technical diagnostics in art and culture are in ever-greater demand in such fields of transdisciplinary research. Natural sciences play auxiliary role in the studies of manuscripts. The success of their contribution depends strongly on the formulation of the question, the choice of the methods to obtain the requested answer, and appropriate reference databases. First, report was given on the measurements performed on local raw materials, such as, plants, minerals and animals, which constitute the reference session. Then, the first results of the scientific analysis of several fragments from the Malian manuscript collections were present.
The aim of our work was to check whether the assumption that the jar was discovered in Qumran can be substantiated. In order to establish the archaeological provenance of the jar we conducted a series of analytical tests on samples of material collected from the jar in April and June 2009. The samples were either found loose within the jar, these being probably constituted by remnants of its original contents, or were clay detached from the inner and outer surface of the jar. In addition, a portion of sand deposit coating the inside of the jar handles was analysed.
Naturwissenschaftliche Verfahren sind inzwischen fester Bestandteil bei der materialwissenschaftlichen Untersuchung von Kunst- und Kulturgut und bei der Entwicklung von Konservierungskonzepten zum Erhalt des kulturellen Erbes. Insbesondere werden zunehmend bildgebenden Verfahren wie die Computertomographie, die Radiographie oder die Multispektralanalyse verwendet, um die für das menschliche Auge nicht sichtbare Inhalte wie Vorzeichnungen, Pentimenti oder innere Strukturen zu visualisieren. Die entstehenden „neuen Bilder“ verändern jedoch die Sichtweise auf das kulturelle Artefakt, da sie tiefere Einblicke in den Herstellungsprozess, den Aufbau oder den Erhaltungszustand geben können. Weiterhin dokumentieren sie Veränderungen, denen ein Objekt unterworfen wurde. Anhand der Untersuchung von zwei Objekten mit dem Röntgenfluoreszenzportalscanner Jet Stream soll das Verhältnis Original – Digitalisat – Rekonstruktion diskutiert werden.
Ancient papyri are a written heritage of culture that flourished more than 3000 years ago in Egypt. One of the most significant collections in the world is housed in the Egyptian Museum and Papyrus Collection in Berlin, from where the samples for our investigation come. The papyrologists, curators and conservators of such collections search intensely for the analytical detail that would allow ancient papyri to be distinguished from modern fabrications, in order to detect possible forgeries, assess papyrus deterioration state, and improve the design of storage conditions and conservation methods. This has become the aim of our investigation. The samples were studied by a number of methods, including spectroscopic (FTIR, fluorescent-FS, Raman) diffractional (XRD) and chromatographic (size exclusion chromatography-SEC), selected in order to determine degradation parameters: overall oxidation of lignocellulosic material, degree of polymerization and crystallinity of cellulose. The results were correlated with those obtained from carefully selected model samples including modern papyri and paper of different composition aged at elevated temperature in humid air. The methods were classified in the order SEC > FS > FTIR > XRD, based on their effectiveness in discriminating the state of papyri degradation. However, the most trustworthy evaluation of the age of papyri samples should rely on several methods.
L'archéométrie est une discipline riche qui peut nous apporter beaucoup d'informations sur l'étude des manuscrits et qui, conjuguée à la paléographie et la codicologie, peut s'apporter un outil précieux pour mieux appréhender les sociétés qui ont produits ces manuscrits.
Nous verrons ici quelques exemples de techniques scientifiques non destructives, principalement appliqués à la Génizah du Caire, appliquées à l'étude des manuscrits.
Quantifying degradation of collagen in ancient manuscripts: the case of the Dead Sea Temple Scroll
(2013)
Since their discovery in the late 1940s, the Dead Sea Scrolls, some 900 ancient Jewish texts, have never stopped attracting the attention of scholars and the broad public alike, because they were created towards the end of the Second Temple period and the 'time of Christ'. Most of the work on them has been dedicated to the information contained in the scrolls' text, leaving physical aspects of the writing materials unexamined. They are, however, crucial for both historical insight and preservation of the scrolls. Although scientific analysis requires handling, it is essential to establish the state of degradation of these valued documents. Polarized Raman Spectroscopy (PRS) is a powerful tool for obtaining information on both the composition and the level of disorder of molecular units. In this study, we developed a non-invasive and non-destructive methodology that allows a quantification of the disorder (that can be related to the degradation) of protein molecular units in collagen fibers. Not restricted to collagen, this method can be applied also to other protein-based fibrous materials such as ancient silk, wool or hair. We used PRS to quantify the degradation of the collagen fibers in a number of fragments of the Temple Scroll (11Q19a). We found that collagen fibers degrade heterogeneously, with the ones on the surface more degraded than those in the core.
Provenienz und Herstellung der Schriftrollen vom Toten Meer: der Beitrag der Naturwissenschaften
(2010)
In this study, we address the question of the
provenance and origin of the Dead Sea Scrolls manuscripts.
A characteristic low ratio of chlorine to bromine, corresponding
to that of the Dead Sea water, may serve as an indicator for
local production. For this aim we developed a non-destructive
procedure to determine the Cl/Br ratio in the parchment of
these manuscripts. Micro-X-ray fluorescence (µ-XRF) measurements
of a large number of parchment and leather
fragments from the Dead Sea Scrolls were analyzed with a
routine we developed based on fundamental parameter
quantification. This routine takes into account the absorption
of the collagen matrix and the influence of the different sample
thicknesses. To calculate the representative Cl/Br ratio for each
fragment, we investigated the lateral homogeneity and
determined the total mass deposition using the intensity of
the inelastically scattered, characteristic tube radiation. The
distribution of the Cl/Br ratios thus obtained from the µ-XRF
measurements make it possible to distinguish fragments
whose origin lies within the Dead Sea region from those
produced in other locations.
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.
Parchment
(2017)
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.
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 this study we demonstrate the possibility to identify the production area of the scrolls, coupling non-destructive quantitative analysis of race elements to spectroscopic investigation of the inks. This approach, that allowed us to determine the Dead Sea area as origin of 1QHodayot, is of general validity.
The experimental knowledge about the inks of antiquity and late antiquity rarely goes beyond their visual description. In rare cases, inks typology has been determined by means of microscopy and reflectography, i.e. using their physical and optical properties, respectively. Soot, plant, and iron gall inks form different typological classes of historical black writing materials. Soot ink is a fine dispersion of carbon pigments in a water-soluble binding agent; plant-based ink consists of tannin solution; iron gall-ink presents a boundary case between soot and plant ink— a water soluble preliminary stage (similar to inks from the second group) oxidizes and evolves into a black, insoluble material (similar to the carbon pigments of the first group) when the writing is exposed to air. Each ink class has distinct properties that would readily permit their easy differentiation, if only these historical inks always belonged to just one of the classes above. In reality, inks may contain additives that obscure a clear picture.
All the black inks of the DSS have been hitherto identified as soot inks. Yet some manuscripts, with 1QapGen ar among them, display ink corrosion that is incompatible with the pure soot ink. This type of corrosion commonly observed in medieval manuscripts written with iron gall inks, results from the catalytic action of metallic component in the ink. Early analysis of this ink conducted by Nir El and Broshi in 1996 found copper in the corrosive inks and attributed its presence to the use of bronze inkwells. Re-investigation of the 1QapGen ar ink suggests, however, that the ink composition, soot + copper, agrees well with the ink recipe recorded in the 1st century CE by Dioscorides. Similar inks have been already attested on contemporary Egyptian papyri. The first part of the paper is dedicated to the new results on the inks and corrosion pattern of the 1QapGen ar.
In the second part of the presentation I will focus on the luxury scrolls, a distinct codicological type introduced by E. Tov. Our studies show that the preparation of the writing materials cannot supplement the list of codicological criteria offered by Tov. Therefore, one can divorce the writing material production from its inscription in contrast with the medieval scriptoria practices that included parchment production and copying of the manuscripts.
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.
The Dead Sea Scrolls belong to the most important cultural assets of mankind. Their long term preservation and study is a challenge that demands an interdisciplinary approach. As early as the 1950s natural scientists assisted the scholars in studying the scrolls. It was at this time that the first extensive study of the scroll material took place. It was found that most fragments were written not on leather but on parchment. In addition, a method for determining the age of the parchment was developed which is still of value today. In the 1990s the AMS-C14 method confirmed the palaeographic determination of the age of the manuscripts. The use of carbon ink throughout the scrolls is also consistent with the known scribal practices of that time. There are, however, manuscripts, and among them the famous Genesis Apocryphon Scroll, which exhibit ink corrosion, normally associated with iron-gall inks.
Today, 60 years after their discovery, a community of scientists from the Jewish National and University Library (JNUL), the Technical University of Berlin (TU Berlin), the Federal Institute for Materials Research and Testing (BAM) and Fritz-Haber-Institute of the MPG (FHI) set out to scientifically investigate the finds of Qumran using the most modern methods. The results of the study will be used to determine the provenance of the texts as well as to contribute to their long-term preservation. A considerable part of the non-destructive investigation is taking place in the Berlin State Library and at the Berliner Elektronenspeicherring-Gesellschaft für Synchrotronstrahlung , BESSY II.
Preliminary investigations, performed at the BAM on some fragments, were used to evaluate the extent to which X-ray analytical methods can provide information regarding the geographical origin of the fragments and match the individual pieces. The interpretation of the measurement results is made more difficult by age and storage of the objects. It is believed that ageing processes as well as conservation methods have altered the samples in addition to the changes caused by environmental influences.
In collaboration with the TU Berlin, the samples from the parchments found in the caves near Qumran were tested by means of three-dimensional synchrotron based X-ray fluorescence analysis (3D-SyXRF). The aim of this non-destructive investigation was the identification of the inorganic material used in the manufacture of the parchments.
The XRF experiments are supported by the non-destructive analysis by means of synchrotron based infrared spectroscopy (SyFTIR) in collaboration with BESSY II as well as optical and electron microscopy in collaboration with Fritz-Haber-Institute (FHI).
This work presents the non-destructive spectroscopic characterisation of original Dead Sea Scrolls (DSS)parchment fragments from Ronald Reed collection. The fragments are of paramount importance becausethey have never been subjected to any treatment of preservation and restoration, this allows to investi-gate the manufacturing method of real original Jewish parchments. The manufacture of “sacred” Jewishparchments, in fact, is traditionally supposed to use a superficial tannin treatment. To study the DSS frag-ments, it was necessary both to analyse mock-up samples, especially manufactured in order to reproduceancient Oriental Jewish ritual parchments, and to compare the results with those obtained in the analysisof modern and ancient Western Jewish ritual parchments, in order to test the effectiveness of the selectedspectroscopic techniques. Traditionally, the main difference between Oriental and Western traditionalparchment preparation consisted in the dehairing method: enzymatic for Oriental and lime-based forWestern. Moreover, a finishing treatment with tannin was supposed to be applied on ritual Jewish parch-ments. The need of reference samples derives from the knowledge that each parchment preparation,treatment and degradation can induce structural modifications that affect the spectral features. FourierTransform Infrared Spectroscopy by Attenuated Total Reflection (ATR-FTIR), FT-Raman and m-Ramanwere used in this study. The experimental results allowed us to recognise, with different sensitivity, thepresence of tannin by using m-Raman and IR spectroscopies and to prove that not all the archaeologicalsamples were manufactured in the same way with vegetal extracts. Many salts (tschermigite, dolomite,calcite, gypsum and iron carbonate) were found on the surface of DSS fragments. They can derive fromthe degradation processes and storage environment before the discovery or from the manufacture. More-over, the different sensitivities and instrumental characteristics of the used techniques permitted us toestablish an analytical protocol, useful for further studies of similar materials.
In this article, we present two Coptic papyri, P 11934 and P 11935 from the Berlin collection excavated in Ashmunein (ancient Hermopolis) by Otto Rubensohn in 1906. We employ a multi-disciplinary approach that takes into account both their materiality – writing support as well as ink – and their content, as has become ‘best practice’. 1 Material aspects of written documents have traditionally been the purview of papyrologists. Recently developed methods of scientific analysis generate sets of archaeometric data with the potential to improve understanding of the materiality of ancient document production, as well as to yield new evidence for genuine papyrological research questions. To achieve this, a large corpus of comparative data needs to be built. Our contribution offers a first step in this direction. We aim at presenting the papyri, which were selected because of the ink corrosion during conservation work at the Berlin collection, in a format that is exhaustive both for material and textual aspects. The inks from both papyri were analysed using a combination of techniques, contributing to our better understanding of the development of ink technology in Late Antiquity.
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.
Material study of inks
(2016)
Our experimental knowledge about the inks of antiquity and late antiquity rarely goes beyond their visual description. In rare cases, inks typology has been determined by means of microscopy and reflectography, i.e. using their physical and optical properties, respectively. Soot, plant, and iron gall inks form different typological classes of historical black writing materials. Soot ink is a fine dispersion of carbon pigments in a water-soluble binding agent; plant-based ink consists of tannin solution; iron gall-ink presents a boundary case between soot and plant ink— a water soluble preliminary stage (similar to inks from the second group) oxidizes and evolves into a black, insoluble material (similar to the carbon pigments of the first group) when the writing is exposed to air. Each ink class has distinct properties that would readily permit their easy differentiation, if only these historical inks always belonged to just one of the classes above. In reality, inks may contain additives that obscure a clear picture.
Even crude observations suggest that the inks of antiquity differed greatly in their composition. We believe, that reconstructing the ink recipes with the help of advanced non-destructive analytical techniques could serve as a powerful accessory in the studies of ancient papyri.
The proposed paper will present a short survey of the methods of material analysis and the challenges offered by ancient inks. (Two) examples of ink studies from the collections of the Israel Museum in Jerusalem and Egyptian Museum in Berlin will conclude the paper.
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.
Material studies of inks
(2017)
The course presents panorama of historic writing inks, their use the methods of their identification. First, we discuss the possible types of the inks and show how one can determine these types using very simple instrumentation.
The change of the inks from those based on soot to the iron-gall inks commonly used in the Middle Age constitutes the second half of the course.
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.
This paper addresses the sensitive issue of authentication of the un-provenanced manuscripts of high monetary value if certified to be genuine.
Over the last decade the popularity of material studies of manuscripts using non-destructive technologies (NDT) has increased enormously. In the case of suspicious writings these studies are held in especially high esteem due to the methodological rigor they are reputed to contribute to debate. Moreover, audiences from a humanities background often tend to disregard the technical details and treat any published interpretation of instrumental analysis as an objective finding.
The paper will discuss the currently available methods and testing protocols for writing materials stressing the advantages and limitations of the non-invasive analysis. As an example we will consider the recent announcement of the possibility of non-invasive dating of carbon inks focusing on the validation required for a testing method.
We will make clear that material analysis alone cannot prove that the object is genuine. We should rather adopt the effective approach for testing suspicious artifacts that has been established by the forensic science. Here, not the authentication, but the determination of the forgery stands in the focus of the work.
The lecture will discuss the sensitive issue of authentication of the objects of cultural heritage of immense cultural and monetary value if certified to be genuine. It will be made clear that material analysis alone, especially its non-destructive variety conducted by specialists in a single technique, can not prove that the object is genuine. The best material analysis can do, after all appropriate tests have been conducted, is to announce that nothing has been found that contradicts the assumption of genuineness. Moreover, the results of the natural analysis can never be used as the only justification of the authentication in the cases of composite objects such as manuscripts or epigraphs. A certification always requires the expertise of the specialist in the field (be it a historian, paleographer, epigrapher, etc.), whose judgment can be at the most supported by appropriate material analysis.
The most effective approach for testing suspicious artifacts has been established by the forensic science. Here, not the authentication, but the determination of the forgery stands in the focus of the work. Investigation protocols developed within 150 years and constantly improved include a clear statement of the analysis purpose and the definition of plausibility criteria for the possible outcome. The younger sister of the forensics, archaeometry has to overcome additional obstacles such as the heterogeneity of historic material coupled with the scarcity of suitable reference material. Over the last two decades the popularity of archaeometric studies has increased enormously, with the industry-driven development of so-called non-destructive technologies (NDT) that do not require sampling. Further technological developments led to the appearance of NDT methods with extremely small interaction windows (µm range). Each of these methods has limitations that have to be carefully considered when planning the tests of a heterogeneous and often partially degraded historical material. This approach is inherently multi-instrumental, therefore archaeometric and forensic departments unite a number of specialists who work together defining the tasks and the methods involved for their successful completion.
The International Qumran project conducted at the BAM Federal Institute for Materials Research and Testing in 2007–10 aimed at establishing an optimal methodology for an accurate characterization of the Dead Sea Scrolls to address such questions as archaeological provenance, origin, and attribution of fragments to a specific sheet (Rabin 2013). Using equipment of various degrees of complexity we have shown that part of the historic information stored in the material can be revealed by proper characterization of the material. The on-site investigation of the Dead Sea Scrolls fragments from The Schøyen Collection in October 2012 offered the first chance to test this methodology in a field study. For the first time, we used mobile and non-invasive technology exclusively, since we could not transport all of our laboratory equipment to Norway for this project. Moreover, besides the technical limitations dictated by the available equipment, we had to cope with limited time: it was impossible to perform the number of scans required for optimal characterization of over 30 fragments within the fourteen days available. Nevertheless this study presents an important step in the material analysis of the Dead Sea Scrolls, since the devices we used are easily transportable, well known, and easily accessible throughout the world.
This article presents the findings resulting from the material analysis of several Sanskrit palm-leaf manuscripts from a corpus partly preserved in Nepal, viz. in the National Archives, Kathmandu (NAK), and in the Kaiser Library (KL), which is likewise situated in Kathmandu. The analysis was undertaken in March 2013. The colleagues of the NAK allocated a room in their precincts to us, where we could set up our mobile laboratory, and gave us access to the required manuscripts from their holdings. The officials of the KL, in turn, allowed us to take some of their valuable and ancient manuscripts to the NAK. In this way, we were enabled to conduct multi-instrumental studies on writing materials of great antiquity and interest.
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.
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 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.
The course presents panorama of historic writing inks, their use the methods of their identification. First, we discuss the possible types of the inks and show how one can determine these types using very simple instrumentation.
The change of the inks from those based on soot to the iron-gall inks commonly used in the Middle Age constitutes the second half of the course.
The Scythica Vindobonensia, the new fragments on Gothic incursions into Roman provinces in the Balkans in the middle of the third century AD that were revealed some years ago in a Greek palimpsest at the Austrian National Library in Vienna (ÖNB), are commonly considered as one of the most important additions of the last decades to the corpus of texts from classical Antiquity. Tere is a high degree of confdence among scholars in supposing that the fragments come from the lost work Scythica written in Greek by the third-century historian P. Herennius Dexippus (Δέξιππος) of Athens. The new fragments have hence also been called Dexippus Vindobonensis. In his Scythica, Dexippus recorded wars of the Romans with the Goths (and other tribes) whom he called Scythians.
The work had been hitherto known only from excerpts and quotes by later authors. Eight pages of a Byzantine manuscript copy of the ancient text have survived hidden underneath the visible surface of the last four parchment folios of the Vienna manuscript Historicus graecus 73, f. 192r -195v4. The copy is written in a Greek calligraphic minuscule which has been estimated by palaeographers to be of the middle or the second half of the eleventh century. In the thirteenth century, the text (on each of the eight pages arranged in one column, with 30 lines per page) was washed of the parchment and the valuable material made from animal skin was re-used for Christian texts. The new writing largely covered the faded remnants of the original text. It thus became hidden from the human eye for more than seven hundred years. Its discovery by Jana Grusková, a classical philologist specialized in the transmission of Greek texts, resulted from a systematic review of all Greek palimpsests kept at the Austrian National Library in Vienna at the beginning of the twenty-first century and a detailed examination of the four folios in 2007-20097.
The Nepal-German Manuscript Preservation Project (NGMPP) microfilmed two sets of the rNying margyud 'bum: in 1989 the set stored in the National Archives in Kathmandu (NAK) and in 1992 another set during an expedition to Nubri, Samagaon. Both microfilming were carried out under the local director of the Nepal Research Centre (NRC) in Kathmandu, and who has also discussed the two (and other) rNying ma rgyud 'bum sets on several occasions.2 The NAK and Nubri rNying ma rgyud 'bum sets were extensively studied and catalogued (Almogi) within the framework of the Tibetology sub-project "The Manuscript Collections of supervision of Franz-Karl Ehrhard, who was at the time the the Ancient Tantras (rNying ma rgyud 'bum): An Examination of Variance," conducted at the Researcher Group "Manuscript Cultures in Asia and Africa," University of Hamburg (2008-2011).
The scribe of ‘Erfurt 7’, a thirteenth-century Torah scroll now kept in Berlin, initially left blank spaces for the divine appellations Elohim ( אלהים ) and YHWH Elohim ( ,(יהוה אלהים which were filled in during a second stage of writing. The appearance of the ink employed to write the appellations was significantly darker than that of the surrounding ink.
X-ray fluorescence analysis (XRF) has shown that the light and dark brown inks had similar elemental compositions, but contained different ratios of iron to potassium, which could be explained by the use of different batches of ink.
According to some medieval sources, the divine appellations were sometimes filled in during a second stage of writing in the presence of ten men from the Jewish community. In Erfurt 7, the two-stage procedure was only performed in the first 1.5 columns of the original sheets, suggesting it may have been part of a public ceremony inaugurating the writing of the divine names in the scroll. Erfurt 7 emerges from this study not only as a ritual object used for liturgy, but as a rallying point for the Jews of Erfurt to come together as a community to express their reverence for the written form of God’s name. The divine name YHWH ( יהוה ) was written in a smaller script than the surrounding text on three replacement sheets using the same two-stage procedure. The ink used on the replacement sheets contained zinc, which is characteristic of other Erfurt manuscripts as well. This suggests that Erfurt was the place where the scroll was used, cherished and eventually repaired.
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.
We have obtained a minute amount of dry ink scratched from the bronze inkwell MS 1655/2. The powder was stored between two glass slides to minimize contamination. For micro analysis by FTIR a sample of the ink powder was transferred into a diamond cell while for confocal Raman spectroscopy a micro sample was placed onto sticky tape. The same portion of the sample was also investigated by scanning electron microscopy, where the elements distribution was determined by EDX.
In the recent years multispectral imaging and X-ray Fluorescence element mapping have established themselves as a well working two step approach, when dealing with faded, erased or overwritten text in iron gall ink. During the last years a lot was done to improve the mere technical side of the techniques. Especially in the case of XRF mapping experiments the acquisition speed needed to be increased to allow mapping in the high resolution demanded by the challenges at hand. High resolution in moderate times can now be achieved, but with the price of proportionally increased amount of data that needs to be processed ideally in parallel to the measurement. The classical approach in XRF spectroscopy of elemental fitting of the spectral data does not even come close to fulfill any on the fly processing time constraints and will consume too much processing time in the foreseeable future. In this paper we will discuss the applicability of modern statistical data processing methods to XRF mapping of iron gall ink palimpsests. We will present a comparison of a new approach based on principle and independent component analysis (PCA and ICA) and the standard element mapping method. We will show that a reduction in processing time of almost two orders of magnitude can easily be achieved.
Hidden history of the DSS
(2010)
An interdisciplinary approach to the study of manuscript traditions is here applied to the analysis of the leaves from the White Monastery, one of the greatest centres of literary production in Late Antique Egypt. In the framework of the ‘PAThs’ project, archaeometric analyses complement the information pieced together by a range of disciplines in the field of humanities. The use of different complementary analytical techniques provides information on the type of ink used and its elemental composition, unveiling interesting details regarding the materials and methodology of manufacturing of writing media. Moreover, this contribution takes a step forward and discusses the possible existence of a regional arrangement in the elemental composition revealed in the inks studied.
In this work, we applied scanning electron
microscopy (SEM), microanalysis and Raman spectroscopy
to study the fungi inhabiting a richly illuminated parchment
document and the damage induced by their activity. To that
aim, we collected samples of fungal mycelium from the
deteriorated areas on a removable adhesive tape specifically
intended for lifting fungi without damaging the support.
SEM analysis of the adhesive tape samples showed the cooccurrence
of several species of fungi. One strain closely
resembling Acremonium species was observed only in the
tape micrographs but no agar cultures were obtained. Its
fungal structures showed the production of abundant
oxalates with an outstanding leaching of the calciumbased
materials of parchment (typically manufactured with
gypsum and lime). Needle-like crystals of calcium oxalate
produced by the fungus forming a uniform and quite
regular grid around conidial slimy heads were documented.
As a result, the areas affected by moulds were weakened,
stained and characterised by a powdery patina rich in
calcium. Confocal µ-Raman confirmed the presence of
oxalates while EDS showed the presence of calcium in
crystals. We conclude that the defacement of the parchment
was due to both collagenolytic activity, and to the
biotransformation of calcium-based minerals by fungi.