Maria Perla Colombini

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.

Novel application of liquid chromatography/mass spectrometry for the characterization of drying oils in art: Elucidation on the composition of original paint materials used by Edvard Munch (1863-1944).

Modern oil paints, introduced at the beginning of the 20th century, differ from those classically used in antiquity in their chemical and compositional features. The main ingredients were still traditional drying oils, often used in mixtures with less expensive oils and added with several classes of additives. Consequently, detailed lipid profiling, together with the study of lipid degradation processes, is essential for the knowledge and the conservation of paint materials used in modern and contemporary art. A multi-analytical approach based on mass spectrometry was used for the study of original paint materials from Munchs atelier, owned by the Munch Museum in Oslo. The results obtained in the analysis of paint tubes were compared with those obtained by characterizing a paint sample collected from one of the artists sketches for the decoration of the Festival Hall of the University of Oslo (1909-1916). Py-GC/MS was used as screening method to evaluate the presence of lipid, proteic or polysaccaridic materials. GC/MS after hydrolysis and derivatization allowed us to determine the fatty acid profile of the paint tubes, and to evaluate the molecular changes associated to curing and ageing. The determination of the fatty acid profile is not conclusive for the characterization of complex mixtures of lipid materials, thus the characterization of the triglyceride profiles was performed using an analytical procedure based on HPLC-ESI-Q-ToF. This paper describes the first application of HPLC-ESI-Q-ToF for the acquisition of the triglyceride profile in a modern paint sample, showing the potentialities of liquid chromatography in the field of lipid characterization in modern paint materials. Moreover, our results highlighted that the application of this approach can contribute to address dating, authenticity and conservation issues relative to modern and contemporary artworks.

Model study of modern oil-based paint media by triacylglycerol profiling in positive and negative ionization modes.

Lipid binders have traditionally been determined in paintings by using gas chromatography/mass spectrometry (GC/MS) to identify the characteristic profiles and ratios of fatty acids . However, the presence of mixtures in contemporary and modern oil paints makes the GC/MS determination of fatty acids insufficient to fully characterize the lipid binding media. In this study we prove that triacylglycerol (TAG) profiling by high-performance liquid chromatography with high-resolution tandem mass spectrometry, using ESI in positive and negative ionization modes is highly effective. We exploited this analytical approach to study the curing and degradation processes undergone by six plant oils used in the formulation of media in modern paints, using both natural and artificial ageing experiments. We believe that is the first time that a negative ionization mode has been applied for this purpose and that a survey with HPLC-ESI-Q-ToF has been carried out to study the ageing kinetics of plant oils. TAG profiling enabled us to study the evolution over time of the constituents of modern oils, with respect to curing and ageing. The data analyzed in this study demonstrate that our approach is efficient to study the oxidation of TAGs during ageing. The data also improve current knowledge on the properties of vegetable oils, which could lead to the development of new paint materials and conservation treatments for modern and contemporary works of art.

Industrial alkyd resins: characterization of pentaerythritol and phthalic acid esters using integrated mass spectrometry

RATIONALE Alkyd resins are synthetic polyesters used as paints and coatings. Current approaches for their analysis do not allow the characterization of pentaerythritol and phthalic acid esters, whose detection is interesting to fully characterize the materials, e.g. for forensic or cultural heritage applications. METHODS A combined analytical approach based on Gas Chromatography/Mass Spectrometry (GC/MS), High-Performance Liquid Chromatography (HPLC)/MS and flow injection analysis (FIA)/MS was adopted. GC/MS was used to characterize the fatty acid profile and the polybasic acids in extracts from industrial alkyd resins. HPLC/MS and FIA/MS were used for the characterization of the triglyceride profile of the oil used to manufacture the resin and for the identification of reaction products deriving from the synthesis process. RESULTS The multi-analytical approach was applied on two different industrial alkyd resins produced from two different oils. The GC/MS analysis was successful in characterizing the fatty acid profile and the aromatic fraction of the resin. The HPLC/MS analysis allowed us to characterize the pentaerythritol and phthalic acid ester and the triglycerides residues from the synthesis process, by studying their high-resolution tandem mass spectra. CONCLUSIONS The application of liquid chromatography coupled with high-resolution tandem mass spectrometry to the study of industrial alkyd resins allowed us to characterize for the first time the esters formed by the transesterification reactions involving pentaerythritol, phthalic acid and triglycerides.

GC/MS and proteomics to unravel the painting history of the lost Giant Buddhas of Bāmiyān (Afghanistan)

A chemical investigation of the organic paint binders of the Giant Buddhas of Bāmiyān was performed using an analytical approach based on mass spectrometry, combining traditional gas chromatography/mass spectrometry protocols with advanced proteomics methodologies. The research was carried out on a selection of rescued fragments. The data revealed the use of egg proteins as the paint binders of the original layers, in accordance with the traditional use of this proteinaceous medium in antiquity, spanning from the Mediterranean basin to the Far East, and already in the Bronze Age. Egg tempera was thus known to artists of the region in the first centuries AD, probably also due to the position of the Bāmiyān valley, which was connected to the Silk Road. Milk was found in the first historical overpaintings. A new proteomics approach was used, which was able to identify the source of the milk proteins present in the restoration layers, despite their age and degradation. In particular cow’s and goats milk were both found, in agreement with the documented presence of rich pastures in the Bāmiyān valley when the historical restorations were carried out. Investigating the materials of the Giant Buddhas not only enabled us to obtain isolated data on these invaluable works of art, which are now lost, but contributes to understanding the big “puzzle” of our past and the development of our culture, by implementing and supporting written sources, stylistic and anthropological studies with molecular data.