Background: The important trecento Florentine artist Giotto (c. 1266-1337) is renowned for his naturalistic and realistic works in tempera and fresco. His innovative paintng style involved painting expressive, emotive faces and use of pictorial devices for depicting space. This report focuses on the analysis of the materials and methods used in a panel in the collection of the National Gallery of Art, Madonna and Child (1310/1315). Results: Giotto used inky washes under thin layers of egg tempera paint. Yellow iron earth and lead tin yellow are present in the paint used to depict the lining of the Virgin’s mantle. SEM-EDX of one of the yellow pigments confirmed it is lead tin yellow type II, PbSn_1-xSi_xO₃. The ratio of colorant to the glassy phase indicates this material was produced for use as a pigment rather than as a glass. Ultramarine was not used in this painting, azurite is the blue pigment. The azurite used here does not contain elemental impurities, however malachite and the rare green–blue mineral mixite, BiCu₆(OH)₆(AsO₄)₃(H₂O)₃, are found in the blue paint. Conclusions: We do not know if Giotto intentionally used mixite as a green–blue pigment or if it was adventitious with the azurite, though given the rarity of the mineral, the latter is more probabale. Nevertheless, the artist’s choice of color was deliberate and the presence of mixite and the clear-hued lead tin yellow pigment attest to his coloristic decisions, in this case opting for cool hues rather than the warm blue of ultramarine which we typically associate with paintings of the Madonna from this time period.

Following a brief overview of the history of analysis of artists' pigments, I discuss the illustrative example of lead-tin yellow. Recent advances in our knowledge of artists' use of red lakes, glassy pigments, and metallic pigments in works of cultural heritage, particularly European paintings, as determined from chemical analyses are described.

Background: Color change in artworks has been commented on for centuries. Fading of watercolor pigments is a notable alteration. Pigments based on carminic acid are among those particularly prone to color loss, but the mechanism and factors are not well understood. Results: We painted out three pigments prepared from the aqueous extract of carminic acid (CA) from Dactylopius coccus: the uncomplexed, and aluminium- and tin-complexed lakes. These were applied in a 2% gum Arabic solution to papers that were acidic, neutral or alkaline pH and exposed to accelerated light aging in a weatherometer. The comparative rate of fading was dependent on the complexation and on the pH of the substrate. On alkaline paper, the Al complex was least light stable, on neutral paper the three colorants responded similarly, and on acidic paper the tin complex was the least light stable. This is discussed in light of the published information on reactions and mechanism of color loss of CA.

To investigate soap formation in drying oils in historic paints, the reaction between metal acetates (K⁺, Zn²⁺, Pb²⁺) and ethyl linoleate (EL) was studied using optical microscopy, X-ray powder diffraction, and electron microscopy. Pb(II) and Zn(II) react rapidly with EL to form highly structured, spherulitic, luminescent crystallites that aggregate. Evidence from Fourier transform infrared (FTIR) and scanning electron microscopy/energy dispersive X-ray analysis and high-resolution synchrotron powder X-ray diffraction indicates that these are organic–inorganic hybrid complexes or coordination polymers. FTIR absorbance peaks at ca. 1540 cm^–1 for Pb(II) and ca. 1580 cm^–1 for Zn(II) are consistent with the formation of carboxylate complexes. The complexes formed offer insight into the degradation processes observed in oil paint films, suggesting that soap formation is rapid when metal ions are solubilized and can occur with unsaturated fatty acids that are present in fresh oils. These complexes may account for the atypical luminescence observed in lead-containing cured oil paint films.