Action of a clay suspension on an Fe(0) surface under anoxic conditions: Characterization of neoformed minerals at the Fe(0)/solution and Fe(0)/atmosphere interfaces

•Immersion of an Fe(0) foil in a clay suspension at 90 °C and in anoxic conditions.•Magnetite was observed on the atmospheric part.•Iron-rich 7 Å serpentines were observed on the clay suspension part.•A gradient in serpentine cristallochemistry was observed.•A pure Fe-Si phyllosilicate was identified at the Fe(0)/clay suspension contact.

To better understand the reaction mechanisms involved at the Fe(0)/clay minerals interface, we investigate in the present study the reaction between an Fe(0) surface and a clay suspension extracted from the Callovo-Oxfordian claystone (COx). Batch experiments were carried out under anoxic conditions in sealed autoclave, at 90 °C to mimic predicted radioactive waste disposal conditions. An Fe(0) foil was introduced into the autoclave so that the lower part of the foil was immersed in the clay suspension while the upper part was contacted with the atmosphere of the experimental setup. After two months, the mineralogical deposits that precipitated at the surface of the Fe(0) foil were analyzed using multiple techniques, namely X-ray diffraction (XRD), scanning/transmission electron microscopy associated to microanalysis (SEM/TEM-EDXS), and micro-spectroscopic measurements (μ-FTIR and μ-Raman). Both parts of the Fe(0) foil were then shown to react: magnetite was the main resulting mineral formed at the Fe(0) surface in the atmospheric conditions whereas serpentine 1:1 phyllosilicates were the main end-products in the clay suspension. The analyses performed on the immersed part of the foil revealed a spatial heterogeneity in both serpentine cristallochemistry and morphology, with a gradient from the Fe(0) contact point toward the clay suspension. A pure Fe-Si phyllosilicate ring was observed at the direct contact point with the Fe(0) foil and a progressive incorporation of Al instead of Fe into the clay phases was identified as deposit thickness increased from the Fe(0) surface to the clay suspension. Our findings suggest that reaction mechanisms include several steps, corresponding to successive regimes depending on the availability of the main reactive elements at the Fe(0)/solution interface, namely Fe, Si and Al. Thus, our results provide new information to support the understanding of both mineral organization and composition at the clay/Fe(0) interface.

Graphical abstractDownload full-size image