Calcium isotope fractionation in calcite and aragonite

Calcium isotope fractionation was measured on skeletal aragonite and calcite from different marine biota and on inorganic calcite. Precipitation temperatures ranged from 0 to 28°C. Calcium isotope fractionation shows a temperature dependence in accordance with previous observations: 1000 · ln(α_cc) = −1.4 + 0.021 · T (°C) for calcite and 1000 · ln(α_ar) = −1.9 + 0.017 · T (°C) for aragonite. Within uncertainty the temperature slopes are identical for the two polymorphs. However, at all temperatures calcium isotopes are more fractionated in aragonite than in calcite. The offset in δ^44/40Ca is about 0.6‰. The underlying mechanism for this offset may be related to the different coordination numbers and bond strengths of the calcium ions in calcite and aragonite crystals, or to different Ca reaction behavior at the solid-liquid interface. Recently, the observed temperature dependence of the Ca isotope fractionation was explained quantitatively by the temperature control on precipitation rates of calcium carbonates in an experimental setting (Lemarchand et al., 2004). We show that this mechanism can in principle also be applied to CaCO₃ precipitation in natural environments in normal marine settings. Following this model, Ca isotope fractionation in marine Ca carbonates is primarily controlled by precipitation rates. On the other hand the larger Ca isotope fractionation of aragonite compared to calcite can not be explained by different precipitation rates. The rate control model of Ca isotope fractionation predicts a strong dependence of the Ca isotopic composition of carbonates on ambient CO₃²⁻ concentration. While this model is in general accordance with our observations in marine carbonates, cultured specimens of the planktic foraminifer Orbulina universa show no dependence of Ca-isotope fractionation on the ambient CO₃²⁻ concentration. The latter observation implies that the carbonate chemistry in the calcifying vesicles of the foraminifer is independent from the ambient carbonate ion concentration of the surrounding water.     

DFT study of the cation arrangements in the octahedral and tetrahedral sheets of dioctahedral 2:1 phyllosilicates

Quantum mechanical calculations based on the density functional theory (DFT) are used to study the crystal structures of dioctahedral 2:1 phyllosilicates. The isomorphous cation substitution is investigated by exploring different substitutions of octahedral Al³⁺ by Mg²⁺ or Fe³⁺, tetrahedral substitution of Si⁴⁺ by Al³⁺, and different interlayer cations (IC) (Na⁺, K⁺, Ca²⁺, and Mg²⁺). Samples with different kinds of layer charges are studied: only tetrahedrally charged, only octahedrally charged, or mixed octahedral/tetrahedral charged. The effect of the relative arrangements of these substitutions on the lattice parameters and total energy is studied. The experimental observation of segregation tendency of Fe³⁺ and dispersion tendency of Mg²⁺ in the octahedral sheet is reproduced and explained with reference to the relative energies of the octahedral cation arrangements. These energies are higher than those due to the IC/tetrahedral and IC/octahedral relative arrangements. The tetrahedral and octahedral substitutions that generate charged layers also tend to be dispersed. The octahedral cation exchange potentials change with the IC-charge/ionic radius value.     

Magnetic fabric study of the SE Rhenohercynian Zone (Bohemian Massif): Implications for dynamics of the Paleozoic accretionary wedge

The progressive deformation recorded in the magnetic fabric of sedimentary rocks was studied in the SE Rhenohercynian Zone (RHZ), eastern margin of the Bohemian Massif, Czech Republic. Almost 800 oriented samples of the Lower Carboniferous mudstones and graywackes were collected from the SSE part of the Czech RHZ, so-called the Drahany Upland. The anisotropy of magnetic susceptibility (AMS) is predominantly controlled by the preferred orientation of paramagnetic phyllosilicates, mainly iron-bearing chlorites. A regional distribution of the magnetic fabric within the Drahany Upland revealed an increasing deformation from the SSE to the NNW. In the SE, the magnetic fabric is bedding-parallel with magnetic lineation scattered in the bedding plane or trending N–S to NNE–SSW. Further to the NW, the magnetic foliation rotates from the bedding-parallel orientation to the orientation parallel to the evolving cleavage. This rotation is accompanied by a decrease of the anisotropy degree and the prolate nature of the anisotropy ellipsoids. The magnetic lineation is parallel to the strike of the bedding, bedding/cleavage intersection, pencil structure or the fold axes on a regional scale. In the NW part of the Drahany Upland, the magnetic foliation becomes parallel to the cleavage accompanied by an increase of the anisotropy degree and the oblate nature of the anisotropy ellipsoids. The increasing trend of deformation corresponds to the SSE–NNW increase in the degree of anchimetamorphism; both trends being oblique to the main lithostratigraphic formations as typically observed in the sedimentary rocks of the accretionary wedges. The SSE–NNW increase in deformation and anchimetamorphism continues to the Nízký Jeseník Mts., representing the northern part of the same accretionary wedge. The kinematics of deformation could not be unambiguously assessed. The observed magnetic fabric may reflect either lateral shortening or horizontal simple shear or a combination of both mechanisms. Regarding the subduction process, it seems that the sedimentary sequences of the Drahany Upland were subducted, partly offscraped and accreted frontally or partly underplated as opposed to the Nízký Jeseník Mts. where some return flow must have occurred.     

Borehole image analysis of the Nankai Accretionary Wedge, ODP Leg 196: Structural and stress studies

Electrical images recorded with Resistivity-At-Bit (RAB) from two sites drilled during Ocean Drilling Program (ODP) Leg 196 were analyzed to study the effects of subduction at the Nankai margin. For the first time in the history of scientific deep-sea drilling in ODP, in situ complete borehole images of the décollement zone were obtained. Analyses of all drilling-induced fracture data indicated that the maximum horizontal compressive stress (S_Hmax) axes have an azimuth of 303°, and analyses of breakout data from RAB images indicated an azimuth of 310°. These azimuths approximate the convergence direction of the Philippine Sea plate towards the Eurasian plate. The frontal thrust at Site 808 was encountered at about 389 mbsf. Density, porosity, resistivity, and gamma ray data change across the frontal thrust. The décollement zone at the deformation front was identified between 937 and 965 mbsf. The base of the décollement is sharply defined as the maximum extent of conductive fracturing and is marked by abrupt changes in physical properties [Mikada, H., Becker, K., Moore, J.C., Klaus, A., Austin, G.L., Bangs, N.L., Bourlange, S., Broilliard, J., Brückmann, W., Corn, E.R., Davis, E.E., Flemings, P.B., Goldberg, D.B., Gulick, S.S., Hansen, M.B., Hayward, N., Hills, D.J., Hunze, S., Ienaga, M., Ishiguro, H., Kinoshita, M., Macdonald, R.D., McNeill, L., Obana, S., Hong, O.S., Peacock, S., Pettigrew, T.L., Saito, S., Sawa, T., Thaiprasert, N., Tobin, H.J., Tsurumi, H., 2002. Proc. ODP, Initial Rep., 196, College Station, TX, (Ocean Drilling Program)]. The upper boundary of the décollement is marked by several sets of conductive fractures and by high variability in physical properties. The décollement zone is characterized by intense brittle fracturing. These fractures are considered to be the consequence of cyclic stresses and high fluid pressures in this zone. We analyzed fracture dips and their orientations at both sites and found that they are all consistent with a unique stress field model surrounding the two sites.