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A novel GC/MS analytical procedure for the identification of lipids, waxes, proteins, and resinous materials in the same microsample from painted works of art has been optimized. It is based on a sample multistep chemical pretreatment (solvent extractions and microwave-assisted chemolysis) that is able to separate the various organic components into different fractions, which are suitably treated and derivatized before analysis. In particular, the procedure allows the complete saponification of wax esters and the completeness of the Cannizzaro type reaction of shellac acids in conditions that are suitable also for glycerides saponification. The method was tested on reference materials for the identification of proteinaceous binders (egg, collagen, casein) on the basis of the quantitative determination of the amino acid profile and the identification of glycerolipids (linseed oil, poppy seed oil, walnut oil, and egg), plant resins (Pinaceae resins, sandarac, mastic, and dammar), animal resins (shellac), tars or pitches, and natural waxes (beeswax, carnauba wax) on the basis of the determination of fatty acid, alcohol, and hydrocarbon profiles and of significant terpenic molecular markers. The procedure was applied to the characterization of three old paint microsamples. Animal glue, egg, linseed oil, beeswax, Pinaceae resin, dammar, and shellac were the identified materials found in mixtures and recognized as original and/or restoration substances.

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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.

This work presents the results of a diagnostic survey on the shipwrecks from the archaeological site of the ancient harbour of San Rossore (Pisa, Italy). The original waterproofing, caulking and painting materials were characterized by Fourier transform infrared spectroscopy (FTIR), gas chromatography -mass spectrometry (GC-MS), energy-dispersive X-ray microanalysis (EDX) and X-ray diffraction (XRD). The major constituents of the waterproofing and caulking materials detected on the planks were tricyclic abietanes showing a high degree of aromatization. These compounds are indicative of a pitch obtained from the wood of trees of the Pinaceae family.The analysis of the organic components of the paint samples revealed diterpenoid acids characteristic of Pinaceae resins together with linear long-chain alcohols and fatty acids, highlighting the presence of beeswax. Noticeably, the characteristic odd carbon number alkanes that are normally present in beeswax were not detected. The EDX and XRD analyses showed that hematite, calcite, cerussite and kaolinite were employed as pigments to paint the ships' hulls.

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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.