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Among the artists’ materials of the nineteenth century, pastel crayons merit scientific interest since their early commercial formulations are mostly unknown and, until now, have been considerably less studied with respect to other contemporary painting materials. In this framework, research herein reports the results of a comprehensive multi-analytical study of 44 pastel crayons of two recognized brands (LeFranc and Dr. F. Schoenfeld) from the Munch museum collection of original materials belonging to Edvard Munch. The integrated use of complementary spectroscopic and hyphenated mass-spectrometry techniques allowed the compositional profiles of the crayons to be traced providing the identification of the inorganic and organic pigments, the fillers/extenders and the binders. All crayons resulted to be oil- based and the binder was identified to be a mixture of a drying oil (safflower or linseed oil), palm oil or Japan wax and beeswax. Among others, pigments such as ultramarine, chrome yellows, Prussian blue, manganese violet, viridian and madder lake have been identified. A significant alignment in formulations of the brands was observed with the only exception of the greens which showed distinctive pigment and filler compositions. The analytical information provided for these commercial artists’ materials will be of great interest for academia, museum and other institutions hosting art collections dating from the same period and it will be used by the Munch museum to draw proper conservation strategies of its own artwork collections.

Diamond Green G (CI 42040, Basic Green 1) is a triarylmethane dye mostly employed in the industrial dyeing of miscellaneous natural and artificial textile fibres, in the production of printing inks and as an anti-fungal agent for aquaculture products. Diamond Green (DG) tends to fade under light irradiation, similar to several other dyes and pigments belonging to the triarylmethane family. In this paper, an in-solution degradation study was carried out to shed light on DG photostability. The experiments were performed by artificially irradiating DG in water and dimethyl sulphoxide, and analysing aliquots sampled at different time intervals by ultra-high performance liquid chromatography coupled with diode array detector quadrupole and time of flight tandem mass spectrometry. The degradation products formed were characterised and the product-ion spectra discussed and interpreted. On the basis of the structure of the identified compounds and their kinetic trend in relation to the accelerated ageing time, degradation mechanisms were proposed for DG, taking into account the role played by the solvent. Finally, the dyeing formulation of an historical textile sample, collected from a stage costume worn in a Zeffirelli lyric opera, was determined utilising the information collected from the analysis of irradiated DG solutions.

Synthetic textiles are constituents of heritage objects and garments often displayed in museum collections or preserved in archives, presenting unprecedented and specific conservation challenges. These issues need to be addressed assessing degradation processes, and developing targeted restoration and preventive conservation practices. The present work aims at characterizing the composition of high fashion garments and design textiles by Nanni Strada conserved in the archives of Nanni Strada Design Studio (Milan). To identify the chemical composition of the fibers used for the manufacturing, and to investigate the degradation processes affecting the objects, the materials were investigated by Attenuated Total Reflectance Fourier Transform Infrared Spectroscopy (ATR-FTIR), Evolved Gas Analysis coupled to Mass Spectrometry (EGA-MS), and multi-shot Pyrolysis coupled to Gas Chromatography and Mass Spectrometry (Py-GC/MS). The results will contribute to a better knowledge of the chemical properties of the textiles produced in the 1970s, and to plan conservation and exhibition strategies.

Eosin (Acid Red 87, C.I. 45380) is one of the most brilliant and challenging early synthetic dyes. In this study, an analytical approach based on high-performance liquid chromatography coupled with diode array and fluorescence detector and high resolution mass spectrometry was developed for testing different analytical columns and acids in the mobile phase. The ultra-sensitive approach, based on a chromatographic separation on a solid core and a porous shell Poroshell 120 EC-C18, allowed us to detect and characterize eosin and its synthesis by-products, such as the debrominated and methyl ester forms of eosin, in trace levels (the limit of detection for eosin is 0.13 ppb). The resulting miscellaneous composition of the eosin standard highlights the importance to determine the exact composition of the starting material to deal with, in order to avoid misinterpretations in aged or degraded samples. Finally, the successful identification of eosin in few grains (approximatively 20 x 40 mu m wide) of a faded Van Gogh's painting proved the strengths of our approach.

Geranium lake is an eosin-derived organic pigment highly employed by Van Gogh and his contemporaries. Its elusive behavior, observed in a large number of post-impressionism masterpieces, is of current concern for both conservators and heritage scientists. Herein, the lightfastness of Geranium lake within oil matrix has been investigated by means UV–Vis spectroscopic techniques and HPLC-DAD-HRMS with the final aim of understanding the degradation mechanism behind its marked bleaching. Accelerated photo-aging experiments irradiating with mono/polychromatic light have been carried out on oil paint models prepared with lead eosin-based lakes, in-house synthesized for this purpose according to available historical recipes, alone and in admixture with different white pigments namely, zinc oxide and basic lead carbonate. The aging experiment not only reproduced the fugitive nature of Geranium lake but also evidenced a reversible behavior during the preliminary stages of the light exposure. Succeeding targeted experiments employing monochromatic light as well as a simplified eosin-oil system in solution, corroborated by the wide literature regarding the photophysics of xanthene dyes, allowed us to propose a reasonable fading mechanism of eosin-based lakes, based on the key role played by linseed oil and environmental oxygen.

The identification of natural dyes in ancient textiles is a longstanding challenge for scientists; yet, the effort honours the skill and knowledge of master dyers by retracing traditional dyeing methods and assisting in conserving historical treasures for future generations. Here, the main constituents of selected native Japanese extracts from the roots of Lithospermum erythrorhizon and Scutellaria baicalensis, the barks of Phellodendron amurense and Morella rubra, the dried flower bud of Syzygium aromataticum, and the fruit of Terminalia chebula are determined by surface-enhanced Raman spectroscopy following traditional Japanese extraction methods. The analytical amalgamation of data from SERS examinations on crude extracts and on subsequently refiltered and diluted extracts provides further effective and sensitive results for the combined identification of napthoquinones (shikonin and alkanin), alkaloid (berberine), polyhydroxyflavonoids (baicalin/baicalein, myricetin/myricitrin), diarylheptanoids, allylbenzene (eugenol), and tannins (gallic/ellagic acid). The comparison of results from this analytical protocol with those achieved by the more traditional chromatographic and mass spectrometric method provides and questions data regarding generally accepted marker components and enantioselective discriminations that serve to enrich the database of biological sources of colouring materials to be used in determining historically important Japanese colorants and dyestuffs.

The cathedral in Odense, Denmark, has for nine centuries held the relics of the Danish King St Canute the Holy and his brother Benedikt. They were both murdered in the predecessor church at the site in AD 1086, and Canute was sanctified in already in AD 1100. The history of the relics has been that of turmoil at times, varying from initial worship of the Catholic believers, to being walled up and hidden away after the protestant reformation in AD 1536, and since the 19th Century on display as important heritage objects of national importance. In the present work we have characterised some of the textiles and analysed the air inside the glass showcases exhibiting the 11th Century wooden coffins holding the remains of St King Canute the Holy and his brother together with some precious textiles. Contrary to previous belief, we now prove that all the textiles analysed have the same age, which is consistent with the time of the enshrinement of the King and his brother in AD 1100. It is also shown that some of the textiles were treated with paraffin wax, most likely during attempts at conservation at the National Museum in the nineteenth century. The results of the air chemistry analyses show the problematic side of simultaneously storing of slowly decaying wood, fine textiles, and human bones in rather airtight environments. The wood continuously releases organic acids, the soaring concentrations of which are potentially harmful to the 11th Century textiles and probably also to the bones.

The object of this study is a wide selection of dyed cotton and camelid samples from an important collection of 2000-year-old Paracas textiles, now at the Museo Nacional de Arqueología, Antropología e Historia del Perú (MNAAHP; Lima; Peru) and at the National Museum of World Culture (NMWC; Gothenburg; Sweden). The threads, chosen as representative of the whole palette, were selected from eighteen different textiles. A combined spectroscopic and spectrometric analytical approach was selected to characterize the organic and inorganic composition of this wide set of samples. In particular, technical photography was used to gain a general overview of the samples, X-ray fluorescence (XRF) was employed for identifying the mordants and mapping the elemental distribution in the threads, while liquid chromatography coupled with diode array detector and with high-resolution mass spectrometry (HPLC–DAD, HPLC–HRMS) were used for characterizing organic dye composition. This study provides fundamental information on the mordants or other inorganic auxiliaries used in the dyeing processes, rarely investigated up to now, and to the varieties of vegetal sources employed in Paracas textiles. The widening of the Andean dyestuff database is highly important not only to acquire knowledge on Paracas culture, but also to ease the dye characterization of archaeological textiles from the Peruvian region and South American area in general.

Triarylmethine dyes, such as Methyl and Crystal Violets, Diamond green and Magentas, produced since the late nineteenth century, consist of complex mixtures of homologous compounds, often differing only for the presence or position of the same substituent on the aromatic rings. In this paper, Liquid Chromatography-High Resolution Mass Spectrometry (HPLC-HRMS) was used for the characterization of the profile of three dyes: Methyl Blue, Methyl Violet and Fuchsine. The comprehension of dye synthesis and production strategies was often achieved by analyzing the single components by diode array detector. Nevertheless, the nature of the individual components needs to be confirmed by tandem mass spectrometric techniques through the solving of the structural issues. The analysis of standards and reference materials by tandem high resolution mass spectrometry allowed us to identify peculiar fragmentation pathways for the components of magentas and methyl violet dyes. The results highlighted the importance to undertake the measurements both in negative and positive ionization mode. The elucidation of specific fragmentation patterns allows the discrimination between different classes of compounds, while the identification of specific fragment ions allows one to distinguish isomers belonging to the same series.

Modern art materials introduced since the end of XIX century include a large number of formulations of synthetic polymers and pigments, whose degradation processes and best preservation conditions are a major issue in heritage science. Analytical pyrolysis coupled with gas chromatography and mass spectrometry (Py-GC/MS) is widely used for the characterisation of polymeric materials and organic pigments, however the interpretation of the pyrograms obtained from samples containing different analytes is not straightforward. To improve our understanding on how these materials behave in complex matrices, we used evolved gas analysis coupled with mass spectrometry (EGA-MS) and multi shot Py-GC/MS to highlight and analyse the different fractions in a sample from a pop-art made of painted polyurethane (PU) foam. The study represents a proof of concept to evaluate EGA-MS potential in studying composite modern art materials in combination with multi-shot pyrolysis. The aim of the investigation was establishing the composition of the PU formulation, the paint binder and the pigments, thereby contributing to planning the stabilisation and conservation of the object. The polymers and the class of synthetic organic pigments present in the paint were assessed by determining their specific pyrolysis products and through comparisons with data in the literature. EGA-MS analysis provided both thermal and chemical information in one analytical run, so that we could select four temperatures for use in multi-shot Py-GC/MS analysis and thus to selectively study the different fractions evolved at different temperatures. Information on the various components of the mixture was obtained, including additives and organic pigments, separating them on the basis of their different thermal degradation temperatures. The multianalytical approach included also non-destructive ATR-FTIR and enabled us to characterize in detail different synthetic materials: polyether-based polyurethane produced by the

Eosin is a xanthenic synthetic organic dye/pigment synthesized by Caro in 1873. It was precipitated with lead and aluminum salts and commercialized as geranium lake and it was one of the most brilliant hues in the palette of the Impressionist painter Vincent van Gogh. Unfortunately, the high photosensitivity of eosin has caused the evident fading of the intense pink colorations of his canvas paintings into lighter ones. This work aims at underlying the contribution of several complementary different analytical techniques in disclosing a very complex and still little-known topic such as the degradation process of eosin.