Celadonite

Abstract: ‘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 © 2008 John Wiley & Sons, Ltd.

Abstract: Analyses of glauconites and celadonites from continental sedimentary rocks and sea-floor basalts using X-ray diffraction, electron probe microanalysis, infra-red spectroscopy, and X-ray fluorescence spectroscopy are reported. The minerals are shown to be distinct species; each an isomorphous replacement series, glauconite having an average half unit cell of K0·85(Fe3+, Al3+)1·34 (Mg2+, Fe2+)0·66(Si3·76Al0·24)O10(OH)2 whereas celadonite approaches the ideal half unit cell of K(Fe3+, Al3+)(Mg2+, Fe2+)Si4O10(OH)2. Considerable Fe3+Alvi interchangeability occurs in the octahedral layer in both minerals and considerable substitution of aluminium in the tetrahedral layer of glauconites results in the more disordered 1Md type of structure compared with the more highly ordered 1M structure of celadonites. Some mixed layer glauconite-smectites and celadonites were also examined and could be distinguished from true glauconites and celadonites by chemical analysis, XRD, and IR techniques. It is proposed that the terms ‘glauconite’ and ‘celadonite’ should be used only for those minerals containing less than 5% interlayering.

Abstract: Several finely dispersed low-temperature dioctahedral micas and micaceous minerals that form solid solutions from (Mg, Fe)-free illite to aluminoceladonite via Mg-rich illite, and from Fe3+-rich glauconite to celadonite have been studied by X-ray diffraction and chemical analysis. The samples have 1 M and 1 Md structures. The transitions from illite to aluminoceladonite and from glauconite to celadonite are accompanied by a consistent decrease in the mica structural-unit thickness (2:1 layer + interlayer) or c sinβ. In the first sample series c sinβ decreases from 10.024 to 9.898 A, and in the second from 10.002 to 9.961 A. To reveal the basic factors responsible for these regularities, structural modeling was carried out to deduce atomic coordinates for 1 M dioctahedral mica based on the unit-cell parameters and cation composition. For each sample series, the relationships among c sinβ, maximum and mean thicknesses of octahedral and tetrahedral sheets and of the 2:1 layer, interlayer distance, and variations of the tetrahedral rotation angle, α, and the degree of basal surface corrugation, Δ Z , have been analyzed in detail. The transitions from illite to aluminoceladonite and from glauconite to celadonite are accompanied by a slight increase in the mean thickness of the 2:1 layers and a steady decrease in the α angles, whereas the interlayer distance becomes smaller. These results are consistent with the generally accepted model where tetrahedral rotation is the main factor for the interlayer contraction in muscovite-phengite structures: the smaller the rotation angle (α) the larger the ditrigonal ring of the tetrahedral sheet and the interlayer pseudo-hexagonal cavity, allowing the interlayer cation to sink and thus shorten the c parameter. A new insight into the interpretation of the contraction of the mica layer thickness in dioctahedral micas has been achieved with the discovery that micas with the same or close mean interlayer distance, on one hand, have the same or nearly the same substitution of Al for Si; and on the other hand, they may have significantly different parameters of the interlayer structure, such as tetrahedral rotation, basal surface corrugation, Δ Z , and minimum and maximum interlayer distance. These results show that in dioctahedral 1 M micas, the mean interlayer distance is determined by the amount of tetrahedral Al because the higher the Al for Si substitution, the stronger the repulsion between the basal O atoms and the larger the interlayer distance and c sinβ parameter.