Chemical fingerprinting of ready-mixed house paints of relevance to artistic production in the first half of the twentieth century. Part I: Inorganic and organic pigments.

This study reports the multi-analytical investigation of ready-mixed house paints used by artists such as Pablo Picasso (1881-1973) in the first half of the twentieth century. The pigment composition of paint swatches on four historic paint sample cards from the Art Institute of Chicago reference collection was characterized by thorough screening using Fourier transform infrared (FT-IR) and X-ray fluorescence (XRF) spectroscopies, followed by Raman spectroscopy when necessary. Spectroscopic investigations highlighted the dominance of zinc-based whites, the consistent choice of particular pigments or their mixtures, as well as the avoidance of others to achieve the various hues on the sample cards. Notable findings included the documentation of strong spectroscopic signatures of metal soaps. Given the similarities in composition of early twentieth century artists' and house paints, the results indicate that the identification of house paints in works by Pablo Picasso and others must be based on a combination of parameters rather than the detection of a single chemical marker. Results have been applied to the case study of Picasso's 1935 sculpture Figure (AIC 1988.428), which incorporates direct evidence of the use of house paint by the artist.

GC-MS identification of proteins in wall painting samples: a fast clean-up procedure to remove copper-based pigment interferences.

A new approach was explored to purify proteins in a multi-step procedure for the characterisation of proteinaceous materials (casein, animal glue, and egg) in artwork samples by gas chromatography-mass spectrometry. High concentrations of inorganic salts, such as azurite, have been found to impair the determination of protein via amino acid analysis. The effect of varying concentrations of copper-based pigments on the quantification of amino acids was evaluated through the analysis of replica paintings prepared with the three types of proteinaceous materials. Glycine, aspartic and glutamic acids are the amino acids most affected by the presence of copper salts. In the case of high concentration of salts, this interference hampers the correct identification of the proteins. To eliminate the inorganic salts, a C18 pipette tip was used to clean-up the ammonia extracts before the acidic hydrolysis step. The clean-up procedure allows us to prevent the influence of the inorganic salts and thus allows correct protein identification, though the quantitative recovery of proteinaceous material is quite low. The effectiveness of the optimised procedure was evaluated by analysing samples from two Italian wall paintings from the 13th and the 14th centuries. Without the clean-up it would not have been possible to detect the presence of a mixture of egg and animal glue in one case, and that of egg in the other one.

Combined GC/MS analytical procedure for the characterization of glycerolipid, waxy, resinous, and proteinaceous materials in a unique paint microsample.

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.