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Surface oxidation of rhodonite: structural and chemical study by surface scattering and glancing incidence XAS techniques

¹ Department of Earth Sciences, University of Manchester, Manchester M13 9PL, UK
² CLRC Daresbury Laboratory, Warrington, Cheshire WA4 4AD, UK
³ Argonne National Laboratory, APS, GSECARS, Argonne, Illinois 60439, USA

^* E-mail: Roy.Wogelius{at}man.ac.uk

Oxidative dissolution of a primary Mn-silicate phase (rhodonite) was studied via synchrotron X-ray techniques. The study was designed to combine the element-specific chemical technique of Glancing Incidence X-ray Absorption Spectroscopy (GIXAS) with the surface structural technique of X-ray scattering in order to produce the first depth resolved study of Mn-silicate low-temperature reactivity. A chemo-mechanically polished polycrystalline rhodonite sample was characterized and then reacted with pH 3.5 nitric acid. The surface originally had a mosaic structure and 15.5 (±1) Å r.m.s. roughness. Surface composition was not measurably different from bulk rhodonite before reaction, indicating that the surface preparation regimen had not produced an altered surface. After 1 h of reaction, the roughness of the mineral surface decreased and reflectivity oscillations developed, resulting from the formation of a leached layer. This layer was 74.7 (±2) Å thick with an electron density equal to 72% of that of bulk rhodonite (equal to the loss of ~1 in 2 Mn atoms). Both the primary and the buried interfaces had similar roughnesses; 4.9 and 4.5 (±1.0) Å , respectively. Diffuse scatter indicated that the correlation length between surface features also decreased. The GIXAS analysis showed that the Mn remaining in the surface had become oxidized, with the degree of oxidation decreasing as a function of depth. Oxidation penetrated at least 140 Å into the structure. A further 2.5 h of reaction at pH 3.5 caused dissolution of the leached layer and reduced the thickness of this altered region to 16.0 (±2) Å, while surface roughness increased slightly to 6.2 (±1.0) Å. Depletion of Mn in this region increased only slightly relative to the first reaction step; the electron density was 67% that of bulk rhodonite, equivalent to the loss of 2 in 3 Mn atoms. The thickness of the oxidized region however, persisted. Analysis by XPS on the same specimen corroborates the X-ray results.

KEYWORDS: X-ray scattering, X-ray absorption spectroscopy, oxidation, dissolution, rhodonite

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