'Green earths': vibrational and elemental characterization of glauconites, celadonites and historical pigments

'Green earths' are employed since antiquity as pigments in the creation of artworks. The minerals responsible for the colour belong to four groups: (1) the clayey micas celadonite and glauconite, undoubtedly the most common; (2) smectites; (3) chlorites; (4) serpentines. Whereas there have been several studies on clayey materials, mineralogical analyses in the field of cultural heritage are mainly limited to the identification of the green earth without specific characterization of the mineralogical species. This work shows a preliminary characterization by the multi-techniques approach of some raw minerals (glauconite, celadonite and ferroceladonite). Vibrational analyses have been correlated with elemental analyses, thanks to the hyphenated instrumentation of scanning electron microscopy with EDS and Raman structural and chemical analyser (SEM-EDS-SCA) probes, which permitted collection of EDS and Raman spectra on the same microscopic area. Micro-Raman and Fourier transform infrared attenuated total reflectance (FTIR-ATR) spectroscopies were able to distinguish between celadonite and glauconite. The use of different lasers revealed resonance effects in the Raman spectra. In addition to pure minerals, archaeological samples and commercial green earths were also analysed, thereby enabling a more precise classification of the green pigments in heterogeneous samples such as wall paintings. Some commercially available green earths were found to contain organic dyes. Copyright (c) 2008 John Wiley & Sons, Ltd.