Experimental evidence of the metastability of ferric smectite

Abstract

The stability of clay minerals, and especially ferric smectites, as a function of time, is of interest for natural environments due to their high capacity to exchange electrons that control a large part of the geochemical cycle of different redox-sensitive organic or inorganic compounds (e.g., elements, nutrients, pollutants). An experimental approach based on hydrothermal synthesis was performed for synthesizing two series of iron-rich smectite (Na-nontronite) at two pH (near 12 and 13) from 1 day to several months at 150 °C. XRD, FTIR, and HRTEM data of the synthetic products confirmed the formation of Na-nontronite for the short time duration experiments. However, the dissolution of Na-nontronite and the concomitant formation of aegirine were observed with the increase of synthesis time. The pH of crystallization fluids clearly influences the rate of the reactions. At highest pH, Na-nontronite disappeared totally after two months and aegirine and hematite were the only crystalline phases observed. The chemical compositions of solutions were over time far from the thermodynamic stability field of nontronite, but very close to that of the aegirine-hematite equilibrium, suggesting that the formation of the nontronite depends on kinetics.The formation of nanoparticular Na-nontronite at the earlier stage of the experiments appears likely due to their specific thermodynamic properties linked to the nanoscale particle size (i.e., high surface energy and high hydration properties). However, Na-nontronites dissolve when they reach a critical size, leading to the formation of the stable assemblage aegirine and hematite.