Germanium crystal chemistry in hematite and goethite from the Apex Mine, Utah, and some new data on germanium in aqueous solution and in stottite

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At the Apex Mine in southwest Utah, fine-grained hematite contains as much as 1.0 wt. percent Ge, and fine-grained goethite contains as much as 0.7 wt. percent Ge. The mode of Ge incorporation in these minerals was investigated by high-resolution K-edge fluorescence spectroscopy using synchrotron radiation. Analysis of extended fine structure (EXAFS) K-edge data for Ge and Fe shows that Ge substitutes for Fe in the octahedral metal sites of the studied hematite and goethite, with average Ge-ligand bond lengths of 1.88 Å. The solid solution in hematite probably occurs through the coupled substitution 2 Fe ( III ) = Ge ( IV ) + Fe ( II ), similar to the coupled substitution 2 Fe ( III ) = Ti ( IV ) + Fe ( II ) that occurs in the solid solution series hematite-ilmenite. The solid solution in goethite probably occurs by the loss of an H atom from an OH group, through the coupled substitution Fe ( III ) + H ( I ) = Ge ( IV ). In related experiments, EXAFS data indicate that in a neutral aqueous solution containing 790 ppm Ge, the Ge occurs predominately as Ge(OH) 4 , with tetrahedral Ge-OH bond lengths of 1.74 Å. In stottite, FeGe(OH) 6 , Fe(II) and Ge(IV) occur in octahedral sites with average Fe-OH and Ge-OH bond lengths of about 2.20 Å and 1.88 Å.

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