Maarten R. van Bommel

Crystal violet: Study of the photo-fading of an early synthetic dye in aqueous solution and on paper with HPLC-PDA, LC-MS and FORS

The photo-fading of crystal violet (CV), one of the earliest synthetic dyes and an ink component, is examined both in solution and on paper. Aqueous solutions of CV were exposed to UV light (365nm) and samples were taken at constant time intervals and analysed with a High Performance Liquid Chromatography-Photo Diode Array (HPLC-PDA) and Liquid Chromatography-Mass Spectroscopy (LC-MS). Demethylation products were positively identified. Also, deamination probably occurred. The oxidation at the central carbon likely generates Michlers ketone (MK) or its derivatives, but still needs confirmation. To study CV on paper, Whatman paper was immersed in CV and exposed to UV light. Before and after different irradiation periods, reflectance spectra were recorded with Fibre Optic Reflectance Spectrophotometry (FORS). A decrease in CV concentration and a change in aggregation type for CV molecules upon irradiation was observed. Colorimetric L*a*b* values before and during irradiation were also measured. Also, CV was extracted from paper before and after different irradiation periods and analysed with HPLC-PDA. Photo-fading of CV on paper produced the same products as in solution, at least within the first 100 hours of irradiation. Finally, a photo-fading of CV in the presence of MK on Whatman paper was performed. It was demonstrated that MK both accelerates CV degradation and is consumed during the reaction. The degradation pathway identified in this work is suitable for explaining the photo/fading of other dyes belonging to the triarylmethane group.

Investigation of crimson-dyed fibres for a new approach on the characterization of cochineal and kermes dyes in historical textiles

The colorant behaviour of cochineal and kermes insect dyes in 141 experimentally-dyed and 28 artificially-aged samples of silk and wool was investigated using ultra-high performance liquid chromatography coupled to photodiode array detector (UHPLC-PDA), liquid chromatography electrospray ionisation mass spectrometry (LC-ESI-MS) and image scanning electron microscopy - energy dispersive X-ray spectroscopy (SEM-EDX). Partial-least squares discriminant analysis (PLS-DA) was then used to model the acquired UHPLC-PDA data and assess the possibility of discriminating cochineal insect species, as well as their correspondent dyed and aged reference fibres. The resulting models helped to characterize a set of 117 red samples from 95 historical textiles, in which UHPLC-PDA analyses have reported the presence of cochineal and kermes insect dyes. Analytical investigation of the experimentally-dyed and artificially-aged fibres has demonstrated that the ratio of compounds in the insects dye composition can change, depending on the dyeing conditions applied and the type of fibres used. Similarities were observed when comparing the UHPLC-MS and SEM-EDX results from the dyed and aged references with the historical samples. This was verified with PLS-DA models of the chromatographic data, facilitating the classification of the cochineal species present in the historical samples. The majority of these samples were identified to contain American cochineal, which is in agreement with historical and dye identification literature that describe the impact of this dyestuff into European and Asian dyeing practices, after the Iberian Expansion in the 16th century. The analytical results emphasize the importance of using statistical data interpretation for the discrimination of cochineal dyes, besides qualitative and quantitative evaluation of chromatograms. Hence, the combination of UHPLC-PDA with a statistical classification method, such as PLS-DA, has been demonstrated to be an advisable approach in future investigations to assess closely related species of natural dyes in historical textile samples. This is particularly important when aiming to achieve more accurate interpretations about the history of works of art, or the application of natural dyes in old textile production.

Characterization of synthetic dyes by comprehensive two-dimensional liquid chromatography combining ion-exchange chromatography and fast ion-pair reversed-phase chromatography.

In the late 19th century, newly invented synthetic dyes rapidly replaced the natural dyes on the market. The characterization of mixtures of these so-called early synthetic dyes is complicated through the occurrence of many impurities and degradation products. Conventional one-dimensional liquid chromatography does not suffice to obtain fingerprints with sufficient resolution and baseline integrity. Comprehensive two-dimensional liquid chromatography (LC×LC) is employed in this study, with ion-exchange chromatography in the first dimension and fast ion-pair liquid chromatography in the second. Retention in the first dimension is largely determined by the number of charges, while the selection of a small ion-pair reagent (tetramethylammonium hydroxide) in the second dimension causes retention to be largely determined by the molecular structure of the dye. As a result, there is a high degree of orthogonality of the two dimensions, similar to the values typically encountered in GC×GC. The proposed LC×LC method shows a theroretical peak capacity of about 2000 in an analysis time of about three hours. Clear, informative fingerprints are obtained that open a way to a more efficient characterization of dyes used in objects of cultural heritage.

Characterisation of chemical components for identifying historical Chinese textile dyes by ultra high performance liquid chromatography – photodiode array – electrospray ionisation mass spectrometer

This research makes the first attempt to apply Ultra High Performance Liquid Chromatography (UHPLC) coupled to both Photodiode Array detection (PDA) and Electrospray Ionisation Mass Spectrometer (ESI-MS) to the chemical characterisation of common textile dyes in ancient China. Three different extraction methods, respectively involving dimethyl sulfoxide (DMSO)-oxalic acid, DMSO and hydrochloric acid, are unprecedentedly applied together to achieve an in-depth understanding of the chemical composition of these dyes. The first LC-PDA-MS database of the chemical composition of common dyes in ancient China has been established. The phenomena of esterification and isomerisation of the dye constituents of gallnut, gardenia and saffron, and the dye composition of acorn cup dyed silk are clarified for the first time. 6-Hydroxyrubiadin and its glycosides are first reported on a dyed sample with Rubia cordifolia from China. UHPLC-PDA-ESI-MS with a C18 BEH shield column shows significant advantages in the separation and identification of similar dye constituents, particularly in the cases of analysing pagoda bud and turmeric dyed sample extracts.

Indigo carmine: Understanding a problematic blue dye

Abstract The history, analysis, and use of the semi-synthetic dye indigo carmine is described by means of a study of historical sources including patents, dye identification using high performance liquid chromatography (HPLC), and the examination of dyed textiles. Indigo carmine, the acid dye ‘Saxon Blue’, was invented by Johann Christian Barth in 1743. Indigo carmine is a water-soluble blue acid dye with the advantage of an easy dyeing process. Its disadvantages are poor lightfastness and washfastness. For the identification of indigo carmine by HPLC, a gradient using water, methanol, and 0.5 mM tertiary butyl ammonium hydroxide can be used to give an unambiguous analytical result. Analyses of dated textile objects prove that indigo carmine was in use after 1770 until the beginning of the twentieth century. This study provides practising conservators with chemical, technological, and historical information which can help in the identification of textiles dyed with indigo carmine, and suggests ways of responding to poor washfastness.

Surface Acoustic Wave Nebulisation Mass Spectrometry for the Fast and Highly Sensitive Characterisation of Synthetic Dyes in Textile Samples

AbstractSurface acoustic wave nebulisation (SAWN) mass spectrometry (MS) is a method to generate gaseous ions compatible with direct MS of minute samples at femtomole sensitivity. To perform SAWN, acoustic waves are propagated through a LiNbO3 sampling chip, and are conducted to the liquid sample, which ultimately leads to the generation of a fine mist containing droplets of nanometre to micrometre diameter. Through fission and evaporation, the droplets undergo a phase change from liquid to gaseous analyte ions in a non-destructive manner. We have developed SAWN technology for the characterisation of organic colourants in textiles. It generates electrospray-ionisation-like ions in a non-destructive manner during ionisation, as can be observed by the unmodified chemical structure. The sample size is decreased by tenfold to 1000-fold when compared with currently used liquid chromatography–MS methods, with equal or better sensitivity. This work underscores SAWN-MS as an ideal tool for molecular analysis of art objects as it is non-destructive, is rapid, involves minimally invasive sampling and is more sensitive than current MS-based methods. Graphical Abstractᅟ

Textilreste aus einem spätbronzezeitlichen Bergbaurevier bei Radfeld in Nordtirol – Sekundärnutzung von Stoffen zur Abdichtung

Zusammenfassung: Im traditionsreichen Bergbaugebiet von Schwaz/Brixlegg im Nordtiroler Unterinntal fand während der späten Bronzezeit und frühen Eisenzeit ein umfangreicher Bergbau auf Kupfererze statt, der zahlreiche Spuren im Gelände hinterlassen hat. Montanarchäologische Forschungsprojekte der Universität Innsbruck, gefördert vom österreichischen Wissenschaftsfonds FWF und vom Tiroler Wissenschaftsfonds TWF, untersuchen seit den 1990er Jahren das prähistorische Montanwesen in diesem Raum. Zu den Forschungszielen gehören die Rekonstruktion der metallurgischen Produktionskette vom Erzabbau über die Aufbereitung bis hin zur Erzverhüttung und Gewinnung von Rohkupfer sowie der Arbeits- und Lebenswelt der prähistorischen Berg- und Hüttenleute. Die bislang prospektierten und in Ausschnitten archäologisch untersuchten Befunde belegen einen zeitlichen Schwerpunkt der Bergbauaktivitäten im 12. bis 8. Jh. v. Chr. Auf einem Verhüttungsplatz bei Radfeld (Mauk A) fanden sich 1997 bei der Freilegung einer „Waschrinne“ zur nassmechanischen Aufbereitung von Schlacken einige gut erhaltene Textilfragmente. Der archäologische Befund sowie die Textilfunde, Analysen zu Textiltechnik, Fasermaterial und Farbstoffen werden im folgenden Beitrag vorgestellt. Zudem werden die funktionelle Interpretation und kulturgeschichtliche Einordnung der Textilfunde diskutiert.

One hundred boys, one hundred challenges: The examination and conservation of two Viennese folding screens decorated with a Chinese silk embroidery

1 Austrian Museum of Applied Arts/Contemporary Art, Vienna, Austria, 2 Cultural Heritage Agency of the Netherlands, Department Research Movable Heritage, Amsterdam, The Netherlands, 3 Institute of Art and Technology/Archaeometry, University of Applied Arts Vienna, Vienna, Austria, 4 Romisch-Germanisches Zentralmuseum/Research Institute for Archaeology, Expositur Xi’an, Shaanxi Archaeological Institute, Xi’an, China 中國西安陝西省考古研究院