Sorption-induced reversible oxidation of Fe(2) at the smectite/water interface under strictly anoxic conditions. A Moessbauer spectroscopy study

Previous studies of Fe(II) sorption onto montmorillonite have been performed with the mineral extracted from the MX80 bentonite. These studies have shown that Fe(II) can be sorbed onto clay minerals in cation exchange position. The affinity of montmorillonite for Fe(II) and Ca(II) is identical. Fe(II) may also be specifically adsorbed onto montmorillonite clay edges. Moessbauer spectroscopy confirmed the high affinity of clay surfaces for Fe(II) sorption and showed that this sorption is mainly due to a two step mechanism: Fe(II) specific adsorption, followed by oxidation of the Fe(II) sorbed. The identification of the oxidizing agent was prohibited due to the complex chemistry of the natural MX80 montmorillonite. Thus, synthetic iron-free montmorillonite was used (chemical formula: Ca0.3 (A1.4Mg0.6) (Si4) O10(OH)2 ). 57Fe(II) sorption experiments were conducted in a N2 atmosphere gloves-box, in strictly anoxic conditions. Solid samples were synthesized in order to confirm the clay high affinity for Fe(II), in absence of structural oxidant, and to have a better comprehension of the sorption mechanism. Moessbauer spectra were recorded for each sample. Whereas no Fe(III) is detected in solution as pH was increased and then, a significant amount of surface sorbed Fe(III) was found to be reversibly produced, which amounts for 0-3% of total Fe in the pre-sorption edge acid region, up to 7% of total Fe when all Fe is sorbed in the neutral to alkaline pH range. From pH ≅ 2 to pH ≅ 7, a sorption edge plateau is observed. In this plateau, the sorbed-Fe(III)/sorbed-Fe ratio increases with pH, up to 45% at pH 7. Moessbauer spectra comparison with ferrous hydroxide, synthesized in the same redox conditions at higher pH, show that this oxidation can not be due to the trace amounts Oz in the suspension. The Moessbauer spectra components of both Fe(II) and Fe(III) appears as paramagnetic doublets: iron has not been polymerized, but is present as cations. This result shows that sorption at the clay-water interface occurs in a two steps mechanism: sorption of individual Fe(II) cations, followed by an oxidation of some of them. As a first hypothesis, water could be the oxidizing agent. However in this case, the reversibility of the phenomenon cannot be explained. Thus we proposed, as a second hypothesis, that as pH is increased, protons H+ is removed from the clay surface and, more and more of highly reactive sites acquire steric properties that stabilize Fe(III) relative to Fe(II). This differential affinity induces in turn an Fe-to-clay particle electron transfer. The change in surface site local environment is shown by observed large pH induced change in the sorbed Fe(II) quadrupole splitting distributions. (authors)