X-ray Photoelectron Spectroscopy study of so-called “Larimar”, blue pectolite from the Dominican Republic (original) (raw)

2016, Sift Desk Journals

A detailed analysis was undertaken of the X-ray photoelectron spectra of the blue variety of pectolite known by the trade name Larimar from the Dominican Republic in an attempt to elucidate the origin of the blue colour. The survey scan confirmed the chemical composition of pectolite. The O 1s showed a complex set of bands associated with Si-O-Si, Si-O-(Na,Ca) and OH in the crystal structure of pectolite. From the possible elements suspected to cause the colour, such as Cu, Fe, Mn, and V, only Cu and Fe were observed above the detection limit of the XPS instrument. For the first time about 0.02 atom% of Pb was observed in one sample, while another sample from the same block showed the presence of 1.05 atom% Sb. The possible presence of [Pb-Pb] 3+ pairs can act as a chromophore analogous to that observed in the blue-green feldspar variety amazonite. This would explain the till now unexplained optical band at 630 nm as well as part of the high hydroxyl concentration. Though other chromophores cannot be excluded, the observation of Pb adds a new possible explanation for the blue colour of Larimar.

X-ray photoelectron spectroscopy characterization of natural chromite from Mercedita Mine (Eastern Cuba): quantification of the Fe 3+ /Fe 2+ ratio

The quantitative estimation of the Fe 3+ /Fe 2+ ratio has a crucial interest to know the upper-mantle oxidation state. The relative proportions of Fe 3+ and Fe 2+ are usually estimated from electron microprobe analysis (EPMA) assuming chromite stoichiometry. In order to test a new technique to estimate the Fe 3+ /Fe 2+ ratio and to avoid EPMA systematic errors, X-ray photo-electron spectroscopy (XPS) has been used to determine the Fe 3+ /Fe 2+ ratio in four chromite samples from Cuba and the results compared with those obtained by EPMA. Due to the high surface sensitivity of XPS the samples were etched by removing the outermost layers by bombarding with an Ar + ion gun. Therefore, the surface, as well as 8, 16 and 24 nm in-depth levels, were analyzed , revealing that the spectra change significantly with depth. Thus, from the surface down to 24 nm deep, Fe 3+ concentrations decrease from values up to 10 at.% to values below the detection limit of XPS (0.1 at.%). By contrast, a systematic Fe 3+ detection (between 1.32 and 4.04 at.%) was observed by EPMA. Consequently, XPS allows us to calculate ferric iron contents, a key datum for the calculation of the real structural formula of chromite. XPS can therefore be considered a useful tool in evaluating mantle oxidation state.

Chemical Investigation of Coloured Minerals in Natural Stones of Commercial Interest

Mikrochimica Acta, 2004

The economic interest in natural stones provides an interesting input to the study of coloured rock-forming minerals. Generally, the colour of a mineral is attributed either to the presence of intrinsically-coloured constituents or of trace elements substituting major elements in the crystallographic sites, or to physical factors such as crystal lattice defects. We have analysed the blue and blue-green silicate minerals dumortierite and amazonite, coming from Mozambique quartzites, and from Malawi and Brazil granitoids, respectively. This study was performed by a multiple analytical approach including (a) a comparison of different signals (optical light-polarized images, backscattered electron images and X-ray multielemental maps); and (b) a collection of quantitative data obtained by WDS systems for major elements, and by WDS and/or micro-PIXE facility for trace elements. A good correlation between Ti concentration zoning and pleochroism variations was observed in dumortierite. In addition, the blue dumortierite of Mozambique, with its unusual significant amounts of antimony (about 5 wt.% Sb2O3), represents a mineral with an intermediate composition between dumortierite and holtite. In amazonite the aquamarine colour seems to be related to the Pb content on the order of some hundreds of ppm.

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