In situ Mössbauer spectroscopy: Evidence for green rust (fougerite) in a gleysol and its mineralogical transformations with time and depth

A miniaturized Mössbauer spectrometer, adapted to the Earth’s conditions from the instrument developed for Mars space missions, has been used for the first time to study in situ variations with depth and transformations with time of iron minerals in a gleysol. The instrument is set into a PVC tube and can be moved up and down precisely (±1 mm) at the desired depth. Mössbauer spectra were obtained from 15 to 106 cm depth and repeated exactly at the same point at different times to follow mineralogical transformations with time. X-ray diffraction (XRD) and selective extraction techniques were performed on soil samples. The piezometric level of the water table was measured and the composition of the soil solution was monitored in situ and continuously, with a multiparametric and automatic probe. All the Mössbauer spectra obtained are characteristic of Fe(II)-Fe(III) green rust-fougerite, a natural mineral of the meixnerite group, that is, whose structural formula is: [Fe_{1 − x}^II Mg_y Fe_x^III (OH)_2+2y]^x+[xA, mH₂O]^x−, where x is the ratio Fe³⁺/Fe_tot. and A the intercalated anion. The name of fougerite has been formally approved by the Commission on New Minerals and Mineral Names of IMA (number 2003-057), on January 29, 2004. No other iron phases have been found by this way or by XRD. About 90% of total iron is extractible by dithionite-citrate-bicarbonate, and 60% by citratebicarbonate. In the horizons showing oximorphic properties that are in the upper part of the studied soil profile, x ratio in fougerite, deduced from Mössbauer spectra, is approximately 2/3. In the deepest horizons that show reductomorphic properties, x ratio is only 1/3. Fast mineralogical transformations were observed at well-defined points in soil, as evidenced by x ratio variations observed when Mössbauer spectra were acquired at different times at the same depth. Variations of the level of the water table and of pe and pH of the soil solution were simultaneously observed and could explain these mineralogical transformations. A ternary solid solution model previously proposed for OH-fougerite has been extended to chloride, sulphate, and carbonate green rusts to estimate the Gibbs free energies of formation of fougerite, providing for possible anions other than OH⁻ in the interlayer and for Mg substitution. Soil solutions appear as largely oversaturated with respect to OH-fougerite, either oversaturated or undersaturated to “carbonate-fougerite” and “sulphate-fougerite”, and largely undersaturated with respect to “chloro-fougerite”. Fougerite forms most likely from oversaturated solutions by coprecipitation of Fe³⁺ with Fe²⁺ and Mg²⁺. Oxidation and reduction are driven by pH and pe variations, with both long timescale variations and short duration events. Exactly as synthetic green rusts are very reactive compounds in the laboratory, fougerite is thus a very reactive mineral and readily forms, dissolves, or evolves in soils.     

Évaluation de la mobilité des métaux dans les sédiments fluviaux du bassin de la Vire (Normandie,France) par extractions simples ou séquentielles

This work compares the quantities of labile metals removed from the Vire River (Normandy) sediments by a sequential extraction procedure to those liberated by single leaches (Mg(NO₃)₂, HCl and EDTA). Compared to the other extractions, Mg(NO₃)₂ underestimated the mobility results. The sequential procedure was the most aggressive, except for Ca and Pb. The hypothetic correlation between quantities of an element removed by single leaches and its fractionation in the sediment according to the sequential procedure was not satisfying. Finally, it should be underlined that enrichments of Cd, Pb and Zn were noticed in the Vire sediments. To cite this article: L. Leleyter, F. Baraud, C. R. Geoscience 337 (2005).     

Structure of fougerite and green rusts and a thermodynamic model for their stabilities

Fougerite is a new iron oxide, a mixed M(II)–M(III) hydroxide, a member of the green rust group. Its structure consists of a brucitic layer of Fe(III)–Fe(II)–Mg(II), where the excess of the positive charge due to Fe³⁺ is compensated in the interlayer by anions. The limits of composition are structurally and geochemically constrained, and the stabilities of the mineral and green rusts are obtained by a thermodynamic model of a regular solid solution, for different compensating anions and for any allowed composition of the brucitic layer.     

Thermodynamic properties of chlorite and berthierine derived from calorimetric measurements

In the context of the deep waste disposal, we have investigated the respective stabilities of two iron-bearing clay minerals: berthierine ISGS from Illinois [USA; (Al_0.975FeIII_0.182FeII_1.422Mg_0.157Li_0.035Mn_0.002)(Si_1.332Al_0.668)O₅(OH)₄] and chlorite CCa-2 from Flagstaff Hill, California [USA; (Si_2.633Al_1.367)(Al_1.116FeIII_0.215Mg_2.952FeII_1.712Mn_0.012Ca_0.011)O₁₀(OH)₈]. For berthierine, the complete thermodynamic dataset was determined at 1 bar and from 2 to 310 K, using calorimetric methods. The standard enthalpies of formation were obtained by solution-reaction calorimetry at 298.15 K, and the heat capacities were measured by heat-pulse calorimetry. For chlorite, the standard enthalpy of formation is measured by solution-reaction calorimetry at 298.15 K. This is completing the entropy and heat capacity obtained previously by Gailhanou et al. (Geochim Cosmochim Acta 73:4738–4749, 2009) between 2 and 520 K, by using low-temperature adiabatic calorimetry and differential scanning calorimetry. For both minerals, the standard entropies and the Gibbs free energies of formation at 298.15 K were then calculated. An assessment of the measured properties could be carried out with respect to literature data. Eventually, the thermodynamic dataset allowed realizing theoretical calculations concerning the berthierine to chlorite transition. The latter showed that, from a thermodynamic viewpoint, the main factor controlling this transition is probably the composition of the berthierine and chlorite minerals and the nature of the secondary minerals rather than temperature.