Oxidation modes and thermodynamics of Fe oxyhydroxycarbonate green rust: Dissolution-precipitation versus in situ deprotonation

Fe^II-III hydroxycarbonate green rust GR(CO₃²⁻), Fe^II₄ Fe^III₂ (OH)₁₂ CO₃·3H₂O, is oxidized in aqueous solutions with varying reaction kinetics. Rapid oxidation with either H₂O₂ or dissolved oxygen under neutral and alkaline conditions leads to the formation of ferric oxyhydroxycarbonate GR(CO₃²⁻)∗, Fe^III₆ O₁₂ H₈ CO₃·3H₂O, via a solid-state reaction. By decreasing the flow of oxygen bubbled in the solution, goethite α-FeOOH forms by dissolution-precipitation mechanism whereas a mixture of non-stoichiometric magnetite Fe_(3−x)O₄ and goethite is observed for lower oxidation rates. The intermediate Fe^II-III oxyhydroxycarbonate of formula Fe^II_6(1−x) Fe^III_6x O₁₂ H_2(7−3x) CO₃·3H₂O, i.e. GR(x)∗ for which x ? [1/3, 1], is the synthetic compound that is homologous to the fougerite mineral present in hydromorphic gleysol; in situ oxidation accounts for the variation of ferric molar fraction x = [Fe^III]/{[Fe^II]+[Fe^III]} observed in the field as a function of depth and season but limited to the range [1/3, 2/3]. The domain of stability for partially oxidized green rust is observed in the E_h-pH Pourbaix diagrams if thermodynamic properties of GR(x)∗ is compared with those of lepidocrocite, γ-FeOOH, and goethite, α-FeOOH. Electrochemical equilibrium between GR(x)∗ and Fe^II in solution corresponds to E_h-pH conditions close to those measured in the field. Therefore, the reductive dissolution of GR(x)∗ can explain the relatively large concentration of Fe^II measured in aqueous medium of hydromorphic soils containing fougerite.     

High-order Statistics of Spatial Random Fields: Exploring Spatial Cumulants for Modeling Complex Non-Gaussian and Non-linear Phenomena

The spatial distributions of earth science and engineering phenomena under study are currently predicted from finite measurements and second-order geostatistical models. The latter models can be limiting, as geological systems are highly complex, non-Gaussian, and exhibit non-linear patterns of spatial connectivity. Non-linear and non-Gaussian high-order geostatistics based on spatial connectivity measures, namely spatial cumulants, are proposed as a new alternative modeling framework for spatial data. This framework has two parts. The first part is the definition, properties, and inference of spatial cumulants—including understanding the interrelation of cumulant characteristics with the in-situ behavior of geological entities or processes, as examined in this paper. The second part is the research on a random field model for simulation based on its high-order spatial cumulants. Mathematical definitions of non-Gaussian spatial random functions and their high-order spatial statistics are presented herein, stressing the notion of spatial cumulants. The calculation of spatial cumulants with spatial templates follows, including anisotropic experimental cumulants. Several examples of two- and three-dimensional images, including a diamond bearing kimberlite pipe from the Ekati Mine in Canada, are analyzed to assess the relations between cumulants and the spatial behavior of geological processes. Spatial cumulants of orders three to five are shown to capture directional multiple-point periodicity, connectivity including connectivity of extreme values, and spatial architecture. In addition, they provide substantial information on geometric characteristics and anisotropy of geological patterns. It is further shown that effects of complex spatial patterns are seen even if only subsets of all cumulant templates are computed. Compared to second-order statistics, cumulant maps are found to include a wealth of additional information from underlying geological patterns. Further work seeks to integrate this information in the predictive capabilities of a random field model.