The blue pigment smalt, a synthetic potash glass tinted with cobalt, was widely used between the sixteenth and the eighteenth centuries. As part of a study on the alteration of smalt and the reconstitution of its original color, the painting: Woman doing a Libation or Artemisia (Fontainebleau school, 1570) was examined in which the artist used smalt as a blue pigment, which is now degraded. Noninvasive imaging was performed using macro-2D X-ray fluorescence and reflectance imaging spectroscopy to get an overview of the artist’s palette and its distribution. Samples prepared as cross sections were also analyzed by scanning electron microscopy coupled with energy dispersive spectroscopy, micro-X-ray absorption near-edge structure spectroscopy and synchrotron micro-X-ray diffraction imaging to determine the preservation state of the smalt as well as structural information on other pigments adjacent to smalt grains in individual paint layers, which could play a role in the degradation process. On the one hand, the study conducted on the alteration of smalt has shown that it is very weathered and mixed with hydrocerussite, which could be a factor that would facilitate the alteration. On the other hand, these analyses have made it possible to identify and locate the pigments used, which will be the basis for the virtual reconstruction of the color of the painting.

Caspar David Friedrich (1774–1840), one of the most famous German 19th c. painters, created paintings throughout his artistic life using different paint palettes, including many new pigments from the turn from the 18th to the 19th century. In that regard especially blue and yellow pigments are the focus of this non-invasive chemical study using X-ray fluorescence imaging, as these are a landscape painter's major colours. Four paintings from the collection of the Alte Nationalgalerie, Staatliche Museen zu Berlin-Stiftung Preußischer Kulturbesitz, spanning over two important decades of Friedrich's artistic career, were investigated in situ to determine the chemical composition of the blue pigments used in the sky and the yellow hues used in the sunsets and moonlight. The results indicate the use of iron based yellow pigments as well as smalt based blue pigments in Friedrich's early works, while chromium-based yellow pigments and cobalt blue are used in later paintings. The finding of cadmium sulphide in a painting dated in 1817, probably as a historical retouching, is interesting and requires further research. This in situ non-invasive imaging study, although limited to one analytical technique, shows Friedrich's introduction of new synthetic pigments into his paint palette, which varies over the time. These results are important to better understand the painting technique of Caspar David Friedrich and his contemporaries.