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.     

On eddy diffusion profiles in oceanic bottom boundary layers associated with cold eddies and filaments

The oceanic bottom boundary-layer model of Weatherly and Martin (1978) is used to study the vertical structure of the eddy diffusivity in a region with initially imposed bottom mixed-layer thickness. Because of near-bottom oceanic features, such as the Cold Filament (Weatherly and Kelley, 1982) and cold eddies (Ebbesmeyer et al., 1988), the bottom mixed-layer thickness is not the sole result of boundary-layer mixing; this is the incentive for this study. For a given geostrophic forcing and imposed mixed-layer depth, a formula for the eddy diffusion coefficient is found. This parameterization of the eddy diffusivity improves previous formulas used in oceanic and atmospheric boundary layers in the upper portion of the boundary layer. A simple model of a Cold Filament-like feature demonstrates the structure of the bottom boundary layer, the bottom mixed layer, and the relation between the two. A lens-like cross section of cold blobs, often used in analytical models, may be inappropriate if bottom friction is important.     

阿尔金断裂带附近地壳结构的接收函数成像及其地球动力学意义

利用中法1995年布设在跨过阿尔金断裂剖面上的18个流动三分量地震台站记录到的近5个月的天然地震记录,经筛选得到533个高质量接收函数。通过速度分析和接收函数成像处理,得到了阿尔金断裂附近地壳结构的清晰图像。塔里木盆地的Moho界面非常清楚,近水平地位于~44km深度上。该界面以低缓的角度一直向南延伸到了阿尔金断裂附近的~70km的深度。阿尔金断裂以南柴达木盆地下面的Moho界面也十分清楚,近水平地位于~55km的深度上,在阿尔金断裂附近存在向上挠曲,并抬升到了~45km的深度上。在阿尔金断裂下方,Moho界面存在~15km的错断。塔里木盆地Moho之下还存在另一个震相,我们解释为沉积层多次波与可能来自Hales间断面转换波的复合震相。接收函数成像结果表明阿尔金断裂是一个超壳的岩石圈断裂,具有比较直立的产状和很狭窄的剪切变形带。根据这些结果,我们推测塔里木的下地壳可能要比柴达木的下地壳更硬,柴达木地壳增厚的原因可以部分归结于它有一个相对弱的下地壳,青藏高原隆升没有扩展到塔里木盆地是因为塔里木盆地具有更刚性的下地壳和岩石圈地幔。高原北部地壳变形应该是所谓青藏高原隆升的“硬”变形模式(Tapponnieretal...