Erika Ribechini

Analytical Methods for the Characterization of Organic Dyes in Artworks and in Historical Textiles

Abstract Dyes are among the most significant components in works of art and archaeological findings. In the scientific examination of historical artefacts, the identification of natural dyestuffs is a challenging task, due to the complexity of their chemical composition and the possible presence of mixtures of chromophores and degradation products. For this reason, in the last few decades, new analytical procedures and techniques have been developed and improved for the characterization of organic dyes and their identification in microsamples. This review looks at the chemical composition of natural organic dyeing materials used in the field of the cultural heritage and focuses on several analytical methods based on spectrometric and chromatographic techniques that have contributed to the study of organic dyes in works of art and archaeological findings.

Analytical Strategies for Characterizing Organic Paint Media Using Gas Chromatography/Mass Spectrometry

Throughout history, artists have experimented with a variety of organic-based natural materials, using them as paint binders, varnishes, and ingredients for mordants in gildings. Artists often use many layers of paint to produce particular effects. How we see a painting is thus the final result of how this complex, highly heterogeneous, multimaterial, and multilayered structure interacts with light. The chemical characterization of the organic substances in paint materials is of great importance for artwork conservation because the organic components of the paint layers are particularly subject to degradation. In addition, understanding the organic content and makeup of paint materials allows us to differentiate between the painting techniques that have been used over history. Applying gas chromatography/mass spectrometry (GC/MS) analysis to microsamples of paint layers is widely recognized as the best approach for identifying organic materials, such as proteins, drying oils, waxes, terpenic resins, and polysaccharide gums. The method provides essential information for reconstructing artistic techniques, assessing the best conditions for long-term preservation, and planning restoration. In this Account, we summarize the more common approaches adopted in the study of the organic components of paint materials. Our progress in developing GC/MS analytical procedures in the field of cultural heritage is presented, focusing on problems that arise from (i) the presence of mixtures of many chemically complex and degraded materials, (ii) the interference of inorganic species, (iii) the small size of the samples, and (iv) the risk of contamination. We outline some critical aspects of the analytical strategy, such as the need to optimize specific wet-chemical sample pretreatments in order to separate the various components, hydrolyze macromolecular analytes, clean-up inorganic ions, and derivatize polar molecules for subsequent GC/MS separation and identification. We also discuss how to interpret the chromatographic data so as to be able to identify the materials. This identification is based on the presence of specific biomarkers (chemotaxonomy), on the evaluation of the overall chromatographic profile, or on the quantitative analysis of significant compounds. GC/MS-based analytical procedures have for 20 years provided important contributions to conservation science, but challenges and opportunities still coexist in the field of organic-based paint materials. We give selected examples and provide case studies showing how a better understanding of the chemical composition of organic paint materials and of their degradation pathways contribute to a better knowledge our cultural heritage, and to its preservation for future generations.

New Insights into the Ageing of Linseed Oil Paint Binder: A Qualitative and Quantitative Analytical Study

This paper presents an analytical investigation of paint reconstructions prepared with linseed oil that have undergone typical 19th century treatments in preparation for painting. The oil was mechanically extracted from the same seed lot, which was then processed by various methods: water washing, heat treatments, and the addition of driers, with and without heat. A modern process lead white (Dutch source, Schoonhoven) and a commercially available vine black were used as pigments. The reconstructions were prepared in 1999, and naturally aged from then onwards. We compared thermogravimetric analysis (TG), which yields macromolecular information, with gas chromatography-mass spectrometry (GC-MS) and direct exposure mass spectrometry (DEMS), which both provide molecular information. The study enabled us to quantitatively demonstrate, for the first time, that the parameters used to identify drying oils are deeply influenced by the history of the paint. In particular, here we show that the ratio between the relative amounts of palmitic and stearic acid (P/S), which is used as an index for differentiating between drying oils, is extremely dependent on the pigments present and the age of the paint. Moreover the study revealed that neither the P/S parameter nor the ratios between the relative amounts of the various dicarboxylic acids (azelaic over suberic and azelaic over sebacic) can be used to trace the sorts of pre-treatment undergone by the oil investigated in this study. The final results represent an important milestone for the scientific community working in the field, highlighting that further research is still necessary to solve the identification of drying oils in works of art.

Characterisation of archaeological waterlogged wood by pyrolytic and mass spectrometric techniques

Two techniques based on analytical pyrolysis and mass spectrometry, direct exposure-MS (DE-MS) and pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS), were used to characterise waterlogged archaeological wood and to study degradation patterns of wood in aqueous environments. The two techniques were applied to samples from the excavation of the Site of the Ancient Ships of Pisa San Rossore in Pisa (Italy), and data were compared to those relative to native sound wood of the same species (pine, elm, beech). Both the methods result valuable in the analysis of ancient wood artefacts, avoiding the long wet-chemical procedures that are commonly used in wood analysis, and allowing us to use a minimal sample size. DE-MS achieves a global mass spectral fingerprint of lignin and polysaccharides pyrolysis compounds in few minutes, and the results have been interpreted with the support of principal component analysis (PCA) of mass spectra. Py-GC/MS permits detailed molecular analysis of pyrolysis compounds and highlights some chemical modifications of lignin in archaeological samples, as demethylation of both guaiacyl and syringyl lignin units. Both the techniques demonstrate consistent loss of polysaccharides in archaeological wood.

Py-GC/MS, GC/MS and FTIR investigations on LATE Roman-Egyptian adhesives from opus sectile: New insights into ancient recipes and technologies

An analytical protocol based on optical microscopy, Fourier transforms infrared spectroscopy (FTIR), analytical pyrolysis in the presence of hexamethyldisilazane followed by gas chromatographic/mass spectrometric analysis (Py-GC/MS) and gas chromatography/mass spectrometry after alkaline hydrolysis, solvent extraction and trimethylsilylation (GC/MS) was used in the chemical characterisation of the original adhesives used to fix monochrome and mosaic glass and stone plaques coming from the Late Roman archaeological site of Antinoopolis (Egypt). FTIR analysis demonstrated the presence of calcite fragments, and Py-GC/MS and GC/MS analyses provided detailed molecular compositions, highlighting the presence of a wide range of compound classes including diterpenoid acids, tricyclic abietanes with a high degree of aromatisation, mid- and long-chain monocarboxylic fatty acids, mono- and di-hydroxy acids, alpha,omega-dicaboxylic fatty acids, n-alkanols, and n-alkanes. Characteristic biomarkers and their distribution patterns indicated the presence of pine pitch in all the adhesives, which in some cases was admixed with beeswax and brassicaceae seed oil. The results provided new insights into the complex recipes used by artisans in ancient Egypt in the production of adhesives and in the sophisticated manufacture of opus sectile decorations.

Analytical Instrumental Techniques to Study Archaeological Wood Degradation

Abstract Historically, a very large variety of everyday artifacts were made of wood, which makes them representative of their historical period or social context and valuable for archaeologists and historians. In order to preserve degraded wood and to develop and apply suitable conservation treatments, chemical and physical characterization of archaeological wood is needed. This review provides the reader with a survey on state-of-the-art of instrumental analytical tools available to understand the morphology and the chemical composition of archaeological wood. The focus is on microscopic and spectroscopic techniques such as scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), Raman, nuclear magnetic resonance (NMR) and analytical techniques based on pyrolysis, such as direct exposure–mass spectrometry (DE-MS), pyrolysis–mass spectrometry (Py-MS), pyrolysis–gas chromtography–mass spectrometry (Py-GC/MS), with emphasis on their respective potentialities and limitations. The advantages of techniques based on synchrotron radiation are also discussed. In addition, the applicability of each examined technique is illustrated and discussed through specific examples from the literature.

An integrated analytical approach for characterizing an organic residue from an archaeological glass bottle recovered in Pompeii (Naples, Italy)

Within the framework of an Italian research project aimed at studying organic residues found in archaeological objects from the Roman period, the chemical composition of the contents of several glass vessels recovered from archaeological sites from the Vesuvian area (Naples, Italy) was investigated. In particular, this paper deals with the study of an organic material found in a glass bottle from the archaeological site of Pompeii using a multi-analytical approach, including FT-IR, direct exposure mass spectrometry (DE-MS) and GC-MS techniques. The overall results suggest the occurrence of a lipid material of vegetable origin. The hypothesis that the native lipid material had been subjected to a chemical transformation procedure before being used is presented and discussed.

A multi-analytical approach to studying binding media in oil paintings

This article presents a multi-analytical approach to investigating the drying, polymerisation and oxidative degradation of linseed oil, which had undergone various treatments known to be undertaken during the nineteenth century in preparation for painting. The oil was mechanically extracted from the same seed lot then processed by different methods: water washing, heat treatments, and the addition of driers, with and without heat. The oil was prepared in 1999 within the framework of the MOLART project. We compared thermogravimetric analysis (TG), which yields macromolecular information, with gas-chromatography mass-spectrometry (GC/MS) and direct exposure mass spectrometry (DE-MS), which provide molecular information. This comparison enabled us to elucidate the role of pre-treatment on the composition of the oil. TG and oxygen uptake curves registered at a constant temperature helped us to identify the different physical behaviour of the oil samples, thus highlighting the presence of hydrolysed, oxidised and crosslinked fractions, as a consequence of the different pre-treatments. GC/MS was used to characterise the soluble and non-polymeric fraction of the oil, to calculate the ratios of palmitic to stearic acid (P/S), and azelaic to palmitic acid (A/P), and to further evaluate the effects of oil pre-treatments. DE-MS using chemical ionisation with CH4, enabled us to establish the chemical composition of the oil in different stages of ageing. DE-MS proved to be a useful tool for a simultaneous semi-quantitative characterisation of the free fatty acids, monoglycerids, diglycerides and triglycerides present in each sample. The combination of thermal analysis with GC/MS and DE-MS enabled a model to be developed, which unravelled how oil pre-treatments produce binders with different physical–chemical qualities.

Gas chromatography/mass spectrometry and pyrolysis-gas chromatography/mass spectrometry for the chemical characterisation of modern and archaeological figs (Ficus carica)

Gas chromatography/mass spectrometry (GC/MS) after alkaline hydrolysis, solvent extraction and trimethylsilylation, and analytical pyrolysis using hexamethyldisilazane (HMDS) for in situ derivatisation followed by gas chromatographic/mass spectrometric analysis (Pyrolysis-silylation-GC/MS) were used to investigate the hydrolysable and soluble constituents, and the polymerised macromolecules of an archaeological fig (Ficus carica) recovered in Zaragoza (Spain), as well as of modern figs. The main aim was to study the compositional alterations undergone by the fig tissues in a particular archaeological environment: the fig was in a vessel and covered by a layer of a mixture of orpiment and gypsum. A comparison between the GC/MS results from modern and archaeological figs revealed that degradative reactions took place, leading to the disappearance/depletion of reactive (unsaturated fatty acids) and sensitive compounds (phytosterols and triterpenes). Py-silylation-GC/MS data provided evidence of a significant degradation of the saccharide and lipid components of the fig tissue, which left a residue enriched in polyphenols and polyesters.

Ingredients of a 2,000-y-old medicine revealed by chemical, mineralogical, and botanical investigations.

In archaeology, the discovery of ancient medicines is very rare, as is knowledge of their chemical composition. In this paper we present results combining chemical, mineralogical, and botanical investigations on the well-preserved contents of a tin pyxis discovered onboard the Pozzino shipwreck (second century B.C.). The contents consist of six flat, gray, discoid tablets that represent direct evidence of an ancient medicinal preparation. The data revealed extraordinary information on the composition of the tablets and on their possible therapeutic use. Hydrozincite and smithsonite were by far the most abundant ingredients of the Pozzino tablets, along with starch, animal and plant lipids, and pine resin. The composition and the form of the Pozzino tablets seem to indicate that they were used for ophthalmic purposes: the Latin name collyrium (eyewash) comes from the Greek name κoλλυ´ρα, which means “small round loaves.” This study provided valuable information on ancient medical and pharmaceutical practices and on the development of pharmacology and medicine over the centuries. In addition, given the current focus on natural compounds, our data could lead to new investigations and research for therapeutic care.