A Mass Spectrometry-Based Approach for Characterization of Red, Blue, and Purple Natural Dyes.

Effective analytical approaches for the identification of natural dyes in historical textiles are mainly based on high-performance liquid chromatography coupled with spectrophotometric detection and tandem mass spectrometric detection with electrospray ionization (HPLC-UV-Vis-ESI MS/MS). Due to the wide variety of dyes, the developed method should include an adequate number of reference color compounds, but not all of them are commercially available. Thus, the present study was focused on extending of the universal analytical HPLC-UV-Vis-ESI MS/MS approach to commercially unavailable markers of red, purple, and blue dyes. In the present study, HPLC-UV-Vis-ESI MS/MS was used to characterize the colorants in ten natural dyes (American cochineal, brazilwood, indigo, kermes, lac dye, logwood, madder, orchil, Polish cochineal, and sandalwood) and, hence, to extend the analytical method for the identification of natural dyes used in historical objects to new compounds. Dye markers were identified mostly on the basis of triple quadrupole MS/MS spectra. In consequence, the HPLC-UV-Vis-ESI MS/MS method with dynamic multiple reaction monitoring (dMRM) was extended to the next 49 commercially unavailable colorants (anthraquinones and flavonoids) in negative ion mode and to 11 (indigoids and orceins) in positive ion mode. These include protosappanin B, protosappanin E, erythrolaccin, deoxyerythrolaccin, nordamnacanthal, lucidin, santalin A, santalin B, santarubin A, and many others. Moreover, high-resolution QToF MS data led to the establishment of the complex fragmentation pathways of α-, ß-, and γ- aminoorceins, hydroxyorceins, and aminoorceinimines extracted from wool dyed with Roccella tinctoria DC. The developed approach has been tested in the identification of natural dyes used in 223 red, purple, and blue fibers from 15th- to 17th-century silk textiles. These European and Near Eastern textiles have been used in vestments from the collections of twenty Krakow churches.

It's Only a Part of the Story: Analytical Investigation of the Inks and Dyes Used in the Privilegium Maius.

The Privilegium maius is one of the most famous and spectacular forgeries in medieval Europe. It is a set of charters made in the 14th century upon commitment by Duke Rudolf IV, a member of the Habsburg family, to elevate the rank and the prestige of his family. These five charters, now kept at the Österreichisches Staatsarchiv in Vienna, have been subjected to a thorough interdisciplinary study in order to shed light on its controversial story. The charters are composed of pergamenaceous documents bound to wax seals with coloured textile threads. The present contribution concerns the characterisation of the inks used for writing and of the dyes used to colour to the threads: Are they compatible with the presumed age of the charters? Though showing only a part of the whole story of the charters, dyes analysis could contribute in assessing their complex history from manufacturing to nowadays. The dyes were characterised with non-invasive in situ measurements by means of fibre optic (FORS) and with micro-invasive measurements by means of Surface Enhanced Raman Spectroscopy (SERS) and High-Performance Liquid Chromatography with Mass Spectrometry (HPLC-MS) analysis. The results showed that the threads of four of the charters (three dyed with madder, one with orchil) were apparently coloured at different dyeing stages, then re-dyed in the 19-20th century.

The Vienna Genesis: An Example of Late Antique Purple Parchment.

The investigation and conservation of the Vienna Genesis, a Late Antique manuscript on purple parchment, included the study of parchment production and purple dyeing in the sixth century. The process of parchment making and of purple dyeing was recreated and compared with the Vienna Genesis and other manuscripts from the sixth and eighth centuries. Parchment made from the hides of young lambs and dyed with orchil resembled the folios of the Vienna Genesis. The results of material analysis and the study of parchment technology influenced decisions for the conservation and storage of the manuscript. Fragile areas of ink and parchment were stabilised with strips of adhesive coated Japanese tissue paper. The single folios are stored in folders of Japanese paper and museum matboard within a sink mat.

Mythic dyes or mythic colour? New insight into the use of purple dyes on codices.

The traditional knowledge concerning the use of Tyrian purple in Late Antique and Medieval purple codices - those precious biblical texts written with noble metal inks on parchment dyed or painted with purple colourants - is here updated in view of new analytical evidence. Recent literature reports the analysis carried out on some purple codices, suggesting that Tyrian purple has not, if ever, been used in their making. A large number of purple codices has been considered in this work to elucidate the nature of the purple colour. Results have been discussed within the frame of previous information, thus covering a vast majority of the purple codices presently identified. In most of the instances the use of less expensive dyes such as folium or orchil is suggested. Moreover, analytical results from a non-invasive spectroscopic approach have been definitely confirmed by micro-invasive surface-enhanced Raman analysis performed on micro samples of purple parchment taken from two 6th century codices.

On the identification of folium and orchil on illuminated manuscripts.

The identification of the two purple dyes folium and orchil has rarely been reported in the analysis of painted artworks, especially when analysing illuminated manuscripts. This is not consistent with the fact that ancient literary sources suggested their use as substitutes for the more expensive Tyrian purple dye. By employing non-invasive spectroscopic techniques, the present work demonstrates that these dyes were actually widely used in the production of ancient manuscripts. By employing UV-visible diffuse reflectance spectrophotometry with optic fibres (FORS) and spectrofluorimetry, the abundant identification of both dyes on medieval manuscripts was performed by comparing the spectra recorded on ancient codices with those obtained on accurate replicas of dyed or painted parchment. Moreover, examples are also reported whereby the considered purple dyes were used in mixtures with other colourants. The overall information obtained here allowed us to define new boundaries for the time range in which orchil and folium dyes were used which is wider than previously thought, and to focus on their particular uses in the decoration of books.

Analytical investigations on the Coronation Gospels manuscript.

The Coronation Gospels or Krönungsevangeliar is a manuscript kept in Vienna at the Kunsthistorisches Museum Wien, datable to the end of VIII century A.D. and produced at Charlemagne court. It is an example of a purple codex, i.e. its parchment is coloured in purple. It has to be considered as one of the most important medieval codices, according to its use to take oath in the coronation ceremony of kings and emperors of the Holy Roman Empire up to 1792. In order to gather information of the manufacture of the manuscript and its present conservation state, a diagnostic investigation campaign has been carried out in situ with totally non-invasive techniques. X-ray Fluorescence Spectrometry (XRF), UV-visible diffuse reflectance spectrophotometry with optical fibres (FORS), spectrofluorimetry, optical microscopy and multispectral analysis have been applied in order to identify the colourants used in the decoration of the manuscript, with the main concern to the dye used to impart the purple hue to the parchment. The information collected was useful in order to address some of the questions raised by art historians concerning its history.

Organic dyes in illuminated manuscripts: a unique cultural and historic record.

In this study, we successfully addressed the challenges posed by the identification of dyes in medieval illuminations. Brazilwood pigment lakes and orcein purple colours were unequivocally identified in illuminated manuscripts dated by art historians to be from the thirteenth to the fifteenth centuries and in the Fernão Vaz Dourado Atlas (sixteenth century). All three works were on a parchment support. This was possible by combining Raman microscopy and surface-enhanced Raman spectroscopy with microspectrofluorimetry. To the best of our knowledge, this is the first time that brazilein, the main chromophore in brazilwood lake pigments, has been unequivocally identified by surface-enhanced Raman spectroscopy in an illuminated work (the Dourado Atlas). Complementing this identification, through microspectrofluorimetry and micro-Fourier transform infrared spectroscopy, it was possible to propose a complete paint formulation by comparison with our database of references; the dark pink hues, in the three case studies, were produced by combining brazilwood pigment lakes and gypsum in a protein- and gum arabic-based tempera. Orcein purple, also known as orchil dye, has been previously identified in medieval manuscripts, dated from the sixth to the ninth centuries. Our findings in fourteenth-sixteenth century manuscripts confirm the hypothesis that this dye was lost during the High Middle Ages, to be later rediscovered.This article is part of the themed issue 'Raman spectroscopy in art and archaeology'.

A diagnostic study on folium and orchil dyes with non-invasive and micro-destructive methods.

Folium and orchil are dyes of vegetal origin. Folium is obtained from Chrozophora tinctoria (L.) A. Juss., whereas orchil is obtained from Roccella and other genera of lichens. These dyes were used in the past to impart purple hue to paintings and textiles as substitutes for the more prised Tyrian purple dye, obtained from shellfish. Despite several citations in ancient technical treatises dating back at least to the Greek-Roman age, the identification of these dyes in artworks is rare. In the case of folium, an additional drawback is that its composition is presently unknown. In this work different non-invasive (FT-IR, FT-Raman, fibre optic reflectance spectrophotometry, spectrofluorimetry, X-ray fluorescence spectrometry) and micro-invasive (surface enhanced Raman spectroscopy, matrix assisted laser desorption ionisation-time of flight-mass spectrometry, inductively coupled plasma-mass spectrometry) techniques were used in order to increase the diagnostic information available on these dyes. Measurements were carried out on the dyes extracted from raw materials and on painted or dyed parchments. The possibility to distinguish between folium and orchil by chemical analysis is discussed.

Non-invasive investigation on a VI century purple codex from Brescia, Italy.

Purple codices are among the most relevant and prestigious book productions of Late Antique and Medieval age. They usually contained texts from Holy Writings written with golden or silver inks on parchment dyed in a purple hue. According to the tradition, the colour of parchment was obtained by the well renowned Tyrian purple dye. From the material point of view, however, very little is known about the compounds actually used in the manufacture of these manuscripts. Presently, the information available is limited to the ancient art treatises, with very few diagnostic evidences supporting them and, moreover, none confirming the presence of Tyrian purple. It is more than apparent, then, the need to have at disposal larger and more complete information at the concern, in order to verify what came to us from the literary tradition only. In this study, preliminary results are presented from non-invasive investigation on a VI century purple codex, the so-called CodexBrixianus, held in the Biblioteca Civica Queriniana at Brescia (Italy). Analyses were carried out with XRF spectrometry, UV-visible diffuse reflectance spectrophotometry, molecular spectrofluorimetry and optical microscopy. The results suggest the hypothesis that Tyrian purple had been used as a minor component mixed with other less precious dyes such as folium or orchil.

The Book of Kells: a non-invasive MOLAB investigation by complementary spectroscopic techniques.

This paper highlights the efficacy of non-invasive portable spectroscopy for assessing the execution technique and constituent materials in one of the most important medieval manuscripts, the Book of Kells. An aimed campaign of in situ measurements by the MObile LABoratory (MOLAB) has analyzed its elemental composition and vibrational and electronic molecular properties. The ample analytical toolbox has afforded complementary diagnostic information of the pigment palette permitting the characterization of both inorganic and organic materials as pigments and dyes in the white, purple, blue, red, orange, green and black areas. In particular, the novel widespread use of calcinated gypsum (anhydrite) as both a white pigment and in correlation to the organic dyes in this manuscript has been noted. The non-invasive identification of the organic dye orchil is significant considering its rare non invasive detection in medieval manuscripts. Finally the occurrence of particular alterations of the organic black areas giving rise to calcium carboxylate and calcium oxalate has been specifically highlighted. Importantly, this work elaborates complex aspects of the employed painting materials which have given rise to numerous significant points of interest for a more elaborate understanding of this Irish treasure.