Raman microscopy and x-ray fluorescence analysis of pigments on medieval and Renaissance Italian manuscript cuttings

Abstract

Italian medieval and Renaissance manuscript cuttings and miniatures from the Victoria and Albert Museum were analyzed by Raman microscopy to compile a database of pigments used in different periods and different Italian regions. The palette identified in most manuscripts and cuttings was found to include lead white, gypsum, azurite, lazurite, indigo, malachite, vermilion, red lead, lead tin yellow (I), goethite, carbon, and iron gall ink. A few of the miniatures, such as the historiated capital “M” painted by Gerolamo da Cremona and the Petrarca manuscript by Bartolomeo Sanvito, are of exceptional quality and were analyzed extensively; some contained unusual materials. The widespread usage of iron oxides such as goethite and hematite as minor components of mixtures with azurite is particularly notable. The use of a needle-shaped form of iron gall ink as a pigment rather than a writing material was established by both Raman microscopy and x-ray fluorescence spectroscopy for the Madonna and Child by Franco de’ Russi.

Pigment analysis by Raman microscopy and portable X-ray fluorescence (pXRF) of thirteenth to fourteenth century illuminations and cuttings from Bologna

“…In Fragment 2, azurite was used with an organic red lake and other pigments to achieve a purple-brown (vermilion and carbon-based black; figure 7e) and a pale red (chalk). The ink in Fragment 1 has not been characterized, but is likely to be iron gall [15].…”

“…While this study is primarily an investigation in technical art history, it also has a methodological aim, which is to demonstrate further the combined use of different non-destructive analytical methods for illuminated manuscript analysis which is an established practice in the field [14][15][16][17]. Well established though pXRF is in providing the elemental characterization of pigments, it may be insufficient for analysing small areas or those areas containing light elements as found by Jones [18] in his study of illuminated manuscripts held in the University of Glasgow Library's collection [19].…”

A critical analysis of the application of EDXRF spectrometry on complex stratigraphies

“…When performing scientific studies on works of art, the skill to employ in situ non‐destructive analytical methods is essential because sampling is severely limited and in many cases forbidden at all. For these reasons, energy‐dispersive X‐ray fluorescence (EDXRF) has arguably become one of the most widely employed analytical technique in the scientific examination of works of art1–8 and open architecture air‐path instruments have been developed specifically for the in situ examination 5, 9–11. The nature of artistic and archaeological artefacts often raises particular problems which may affect the interpretation of the results as the objects present a complex shape, irregular morphology, heterogeneous composition and may show surface alterations or present several finishing layers.…”

Raman Spectroscopy of cultural heritage Materials: Overview of Applications and New Frontiers in Instrumentation, Sampling Modalities, and Data Processing

“…First, instead of reporting on isolated case studies, Raman has become a true tool to advance art history, being used, for example, for the systematic investigation of the palette of illuminated medieval manuscripts [45], or for a wide survey, using SERS, of red lake pigments employed by impressionist and post-impressionist painters [247]. Information about the identity of remnants of pigments on stone sculptures has been used to reconstruct their entire scheme of polychrome decoration [110], and, when pigments have faded, to propose re-colorised visualisations of artworks [35].…”