Crystalline, Mixed-Valence Manganese Analogue of Prussian Blue: Magnetic, Spectroscopic, X-ray and Neutron Diffraction Studies

The compound of stoichiometry Mn(II)3[Mn(III)(CN)6]2·zH2O (z = 12−16) (1) forms air-stable, transparent red crystals. Low-temperature single crystal optical spectroscopy and single crystal X-ray diffraction provide compelling evidence for N-bonded high-spin manganese(II), and C-bonded low-spin manganese(III) ions arranged in a disordered, face-centered cubic lattice analogous to that of Prussian Blue. X-ray and neutron diffraction show structured diffuse scattering indicative of partially correlated (rather than random) substitutions of [Mn(III)(CN)6] ions by (H2O)6 clusters. Magnetic susceptibility measurements and elastic neutron scattering experiments indicate a ferrimagnetic structure below the critical temperature Tc = 35.5 K.

On the Methyl-Transfer Reaction in Crystalline Methyl 2-(Methylthio)benzenesulfonate: a Thermally Induced Non-Topochemical Solid-State Reaction

The rearrangement of methyl 2-(methylthio)benzenesulfonate (1) to the zwitterionic 2-(dimethyl-sulfonium)benzenesulfonate (2) is known to proceed in solution by intermolecular Me transfers. The same rearrangement has been observed to occur in crystalline 1, but the crystal structure shows that the molecular packing is not conducive to intermolecular Me transfer. The reaction has been carried out with mixed crystals composed of 1 and deuteriomethylated (D6)-l. By fast-atom-bombardment mass spectroscopy, it has been shown that the product consists of a 1:2:1 mixture of the non-, tri-, and hexadeuterated species, the mixture expected, if the solid-state reaction proceeds by intermolecular Me transfers. From this result, together with the slower rates of conversion in the single crystal compared with the melt, it can be concluded that the reaction must occur not topochemically but rather at defects such as microcavities, surfaces, and other irregularities in the ordered crystal arrangement.

Structural, metamorphic and geochronological relations between the Zanskar Shear Zone and the Miyar Shear Zone (NW Indian Himalaya): Evidence for two distinct tectonic structures and implications for the evolution of the High Himalayan Crystalline of Zanskar

The geologic structures and metamorphic zonation of the northwestern Indian Himalaya contrast significantly with those in the central and eastern parts of the range, where the high-grade metamorphic rocks of the High Himalayan Crystalline (HHC) thrust southward over the weakly metamorphosed sediments of the Lesser Himalaya along the Main Central Thrust (MCT). Indeed, the hanging wall of the MCT in the NW Himalaya mainly consists of the greenschist facies metasediments of the Chamba zone, whereas HHC high-grade rocks are exposed more internally in the range as a large-scale dome called the Gianbul dome. This Gianbul dome is bounded by two oppositely directed shear zones, the NE-dipping Zanskar Shear Zone (ZSZ) on the northern flank and the SW-dipping Miyar Shear Zone (MSZ) on the southern limb. Current models for the emplacement of the HHC in NW India as a dome structure differ mainly in terms of the roles played by both the ZSZ and the MSZ during the tectonothermal evolution of the HHC. In both the channel flow model and wedge extrusion model, the ZSZ acts as a backstop normal fault along which the high-grade metamorphic rocks of the HHC of Zanskar are exhumed. In contrast, the recently proposed tectonic wedging model argues that the ZSZ and the MSZ correspond to one single detachment system that operates as a subhorizontal backthrust off of the MCT. Thus, the kinematic evolution of the two shear zones, the ZSZ and the MSZ, and their structural, metamorphic and chronological relations appear to be diagnostic features for discriminating the different models. In this paper, structural, metamorphic and geochronological data demonstrate that the MSZ and the ZSZ experienced two distinct kinematic evolutions. As such, the data presented in this paper rule out the hypothesis that the MSZ and the ZSZ constitute one single detachment system, as postulated by the tectonic wedging model. Structural, metamorphic and geochronological data are used to present an alternative tectonic model for the large-scale doming in the NW Indian Himalaya involving early NE-directed tectonics, weakness in the upper crust, reduced erosion at the orogenic front and rapid exhumation along both the ZSZ and the MSZ.

Reconstruction of in-situ porosity and porewater compositions of low-permeability crystalline rocks: Magnitude of artefacts induced by drilling and sample recovery

Geological site characterisation programmes typically rely on drill cores for direct information on subsurface rocks. However, porosity, transport properties and porewater composition measured on drill cores can deviate from in-situ values due to two main artefacts caused by drilling and sample recovery: (1) mechanical disruption that increases porosity and (2) contamination of the porewater by drilling fluid. We investigated the effect and magnitude of these perturbations on large drill core samples (12–20 cm long, 5 cmdiameter) of high-grade, granitic gneisses obtained from 350 to 600 m depth in a borehole on Olkiluoto Island (SW Finland). The drilling fluid was traced with sodium–iodide. By combining out-diffusion experiments, gravimetry, UV-microscopy and iodide mass balance calculations, we successfully quantified the magnitudes of the artefacts: 2–6% increase in porosity relative to the bulk connected porosity and 0.9 to 8.9 vol.% contamination by drilling fluid. The spatial distribution of the drilling-induced perturbations was revealed by numerical simulations of 2D diffusion matched to the experimental data. This showed that the rims of the samples have a mechanically disrupted zone 0.04 to 0.22 cm wide, characterised by faster transport properties compared to the undisturbed centre (1.8 to 7.7 times higher pore diffusion coefficient). Chemical contamination was shown to affect an even wider zone in all samples, ranging from 0.15 to 0.60 cm, inwhich iodide enrichmentwas up to 180 mg/kgwater, compared to 0.5 mg/kgwater in the uncontaminated centre. For all samples in the present case study, it turned out that the magnitude of the artefacts caused by drilling and sample recovery is so small that no correction is required for their effects. Therefore, the standard laboratory measurements of porosity, transport properties and porewater composition can be taken as valid in-situ estimates. However, it is clear that the magnitudes strongly depend on site- and drilling-specific factors and therefore our results cannot be transferred simply to other locations. We recommend the approach presented in this study as a route to obtain reliable values in future drilling campaigns aimed at characterising in-situ bedrock properties.

(Table 2) Chemical composition of ice-rafted brecciated crystalline schist and biotite-garnet crystalline schist from the Kara Sea

Composition and distribution.of ice-rafted coarse debris from the Kara Sea bottom were investigated. This material was obtained on 42 stations in Cruise 49 of R/V Dmitry Mendeleev by Sigsby trawls, box corers, grabs, and gravity corers. Existence of two main petrographic provinces is suggested: (1) West Kara and (2) East Kara. They differ in composition and sources of debris material. It is supposed that debris was transported mainly by floating ice. In Upper Pleistocene time rafting by glaciers and icebergs was also very possible.

(Table 1.4) Ratios of petrogenic components in glassy and crystalline basalts from the north part of the Bougault anomaly, Mid-Atlantic Ridge 15°N

Structure and composition of sub-surface bottom sediments from the southwest Barents Sea have been under study. The study has revealed heterogeneity of sediment structure resulted from temporal irregularity and variability of sedimentation processes. The study of the heavy minerals from 0.1-0.01 mm grain size fraction has shown prevalence of green hornblende, epidote, garnet, and ilmenite in all types of sediments; these minerals are the basis of terrigenous-mineralogical province. At the same time in different areas local terrigenous-mineralogical associations have been identified. Clay mineral composition of in the sediments was quite uniform: biotite, chlorite, hydromica, smectite. Despite this, a number of features indicating initial stages of clay mineral transformation has been identified. Differences in material composition and structure of the studied sediments are associated with rapid change in paleogeographic situation on the land - ice cover melting on the Kola Peninsula and subsequent Holocene climatic situation.

Mass-accumulation rates for the non-authigenic, inorganic, crystalline, eolian component of sediments recovered at DSDP Sites 62-464 to 62-466

The mass-accumulation rate (MAR) of the non-authigenic, inorganic, crystalline component of deep-sea sediments from the Pacific aseismic rises apparently reflects influx of eolian sediment. The eolian sediment usually is dominated by volcanic material, except during glacial times. Sediments from Hess Rise provide a discontinuous record of eolian MARs. During Albian to Cenomanian time, the influx of volcanic material was fairly high (0.35-0.6 g/cm**2/10**3 yr), recording the latest stages of the Albian volcanism that formed Hess Rise. From the Campanian through the Paleocene, influx of eolian sediment was low, averaging 0.03 g/cm**2/10**3 yr. None of the four Hess Rise drill sites show evidence of the Late Cretaceous volcanic episode recorded at many sites now in the equatorial to subtropical Pacific. Pliocene to Pleistocene samples record a peak in volcanic influx about 4 to 5 m.y. ago, which has been well documented elsewhere. The several-fold increase in eolian accumulation rates elsewhere which are correlated with the onset of severe northernhemisphere glaciation 2.5 m.y. ago is not obvious in the Hess Rise data.