HRTEM-AEM-HAADF-STEM study of platinum-group elements within a mantle-derived Cr spinel (Lherz; North-Eastern Pyrenees, France)

As platinum group elements (PGE) like Ru, Os, Ir and Rh have appropriate charge and ionic radii to substitute the major cations in the spinel structure, Cr-spinel is one of the potential minerals that can fractionate such elements during the partial melting and fractional crystallization. However, whether PGE occur in solid solution or are physically collected as poly-metallic clusters of atoms on spinel grain boundaries is a central issue for PGE geochemistry. A PGE-bearing Cr-spinel separated from one harzburgite sample from Lherz has been analyzed by Transmission, Analytical and Scanning-Transmission Electron Microscopy (TEM-AEM-STEM). Our analyses did not reveal any exsolution/cluster feature at the nanometric scale, except for Ir, which is concentrated as Ir-bearing lamellar rutile, about 100 nm width. Rutile appears to have enhanced unmixing of Ir from the spinel structure. The DCr spinel/silicate melt partition coefficients estimated from the Lherz Cr-spinel (Ir = 32 ± 0.7; Os = 28 ± 6; Ru = 12.5 ± 2; Pt = 1.5 ± 0.2; Pd = 0.2 ± 0.05) may be appropriate for modelling the behavior of PGE in sulfur-undersaturated melting processes of the shallow upper mantle, while being lower than those derived from experiments and natural ultramafic melts.