Vibrational spectra,lattice dynamics and chemical constitution of oxides

The relationships among lattice dynamics of oxides and their chemical constitution are discussed in terms of the concept of dynamic crystal chemistry. A new approach to the design of a dynamic model of an ionic-covalent crystal combining molecular force constants with explicit treatment of long-range electrostatic forces in a lattice is outlined and its applications exemplified. The conditions of introduction of scaled quantum chemical force constants of a suitable molecular system into the secular equation for lattice vibrations are determined rigorously. The importance of unified treatment of stability conditions and various dynamic properties of crystals including phonon spectra, macroscopic elastic and piezoelectric constants etc., is emphasized. Several results of ab initio quantum chemical SCF computations by the gradient method for molecular species containing silicon-oxygen bonds are presented and are used to explain some empirical regularities in silicate structures.     

Strontium in coral aragonite: 2. Sr coordination and the long-term stability of coral environmental records

We have used X-ray Diffraction (XRD) and Sr K-edge Extended X-ray Absorption Fine Structure (EXAFS) to determine the structural state of Sr in a suite of coral aragonite samples. Our samples encompassed a selection of coral species (Porites lobata, Porites lutea, Pocillopora eydouxi, Montastrea annularis, Pavona gigantea and Pavona clavus) including some commonly used for palaeoenvironmental reconstruction. Aragonite was the only carbonate observed by XRD. We refined the isolated EXAFS against structural models for Sr in aragonite and two-phase strontianite/aragonite mixes. Our data are indistinguishable from Sr ideally substituted in aragonite and strontianite was present below detection levels (estimated at <5% of Sr present). Comparisons of recent and ancient coral aragonite show no sign of exsolution, either by spinodal decomposition or by the direct nucleation of strontianite domains. Published diffusion rates of Sr in ionic solids support the view that exsolution would occur prohibitively slowly. Coral aragonites are metastable materials with slow diffusion kinetics that have the potential to encode environments over timescales of millions of years.     

Analytical derivation of water retention for random monodisperse granular media

The mechanics of water retention in unsaturated granular media is of critical importance to a broad range of disciplines including soil science, geotechnical engineering, hydrology and agriculture. Fundamental to water retention is the relationship between degree of saturation and suction, referred to as the water retention curve (WRC). The majority of WRC models are empirically based and seldom incorporate physically meaningful parameters. This study presents an analytical model for the WRC that considers separate contributions from fully filled pores and partially filled pores containing liquid bridges. A recently established unique k-gamma pore volume distribution function for randomly assembled monodisperse granular materials is adopted to determine the contributions of fully filled pores. Calculation of the contribution of residual pore water retained in partially filled pores is undertaken by representing pores as individual cells shaped as platonic shapes of various sizes and determining the volume of all liquid bridges suspended between particles within the pore cells. Weighting factors for the various cell types are obtained from the pore volume distribution to determine the relative contribution of different pore cell geometries to the total residual pore water. The combined model accurately describes experimental data for monodisperse spherical glass beads for both wetting and drying, even though the underlying assumptions do not reflect exactly the complex, interconnected and highly irregular geometry of the pore space. A single parameter provides the lateral shift between the wetting and drying curves. The results of this study provide a geometric understanding of the mechanisms of water retention in granular media.     

Investigating the scale of structural controls on chlorinated hydrocarbon distributions in the fractured-porous unsaturated zone of a sandstone aquifer in the UK

Contaminant migration behaviour in the unsaturated zone of a fractured porous aquifer is discussed in the context of a study site in Cheshire, UK. The site is situated on gently dipping sandstones, adjacent to a linear lagoon historically used to dispose of industrial wastes containing chlorinated solvents. Two cores of more than 100 m length were recovered and measurements of chlorinated hydrocarbons (CHCs), inorganic chemistry, lithology, fracturing and aquifer properties were made. The results show that selecting an appropriate vertical sampling density is crucial both to providing an understanding of contaminant pathways and distinguishing whether CHCs are present in the aqueous or non-aqueous phase. The spacing of such sampling should be on a similar scale to the heterogeneity that controls water and contaminant movement. For some sections of the Permo-Triassic aquifer, significant changes in lithology and permeability occur over vertical distances of less than 1 m and samples need to be collected at this interval, otherwise considerable resolution is lost, potentially leading to erroneous interpretation of data. At this site, although CHC concentrations were high, the consistent ratio of the two main components of the plume (tetrachloroethene and trichloroethene) provided evidence of movement in the aqueous phase rather than in dense non-aqueous phase liquid (DNAPL).     

The Glarus thrust: excursion guide and report of a field trip of the Swiss Tectonic Studies Group (Swiss Geological Society, 14.–16. 09. 2006)

This excursion guide results form a field trip to the Glarus nappe complex organized by the Swiss Tectonic Studies Group in 2006. The aim of the excursion was to discuss old and recent concepts related to the evolution of the Glarus thrust. The major aspects were (i) the interplay between deformation, fluid flow and geochemical alteration, (ii) episodic versus continuous deformation and fluid flow, and (iii) the link between large-scale structures, microstructures, and geochemical aspects. Despite 150 years of research in the Glarus nappe complex and the new results discussed during the excursion, there exist controversies that still are unsolved.     

Tellurium,selenium and cobalt enrichment in Neoproterozoic black shales,Gwna Group,UK: Deep marine trace element enrichment during the Second Great Oxygenation Event

Black shales of the late Neoproterozoic Gwna Group (570–580 Ma), UK, contain enrichments of tellurium (Te), selenium (Se) and cobalt (Co) relative to average shale compositions. The Te and Co enrichments bear comparison with those of ferromanganese crusts in the modern deep ocean. Gwna Group deposition coincides with the Second Great Oxidation Event, which had a significant effect on trace element fixation globally. Selenium and Te concentrations within these black shales indicate increased continental weathering rates, high biological productivity and corresponding increases in atmospheric O₂ concentrations. Cobalt, nickel (Ni) and arsenic (As) enrichments in this succession are secondary mineralisation phases. Demand for many of the trace elements found enriched in the Gwna Group black shales make their mechanisms of accumulation, and variations through the geological record, important to understand, and suggests that new resources may be sought based on black shale protoliths from this period.     

Seismic stratigraphy, buried beach ridges and contourite drifts: the Late Quaternary history of the closed Lago Cardiel basin, Argentina (49°S)

The results of a seismic stratigraphic analysis of a closed lake basin, Lago Cardiel, in southernmost South America are reported. Very few high-resolution, continental records spanning the Late Quaternary have been obtained from this region. Seismic sequence stratigraphic analysis allows a reconstruction of lake level variations. Two major hiatuses of unknown age occurred during the early evolution of the basin with the deposition of an alluvial fan in a restricted area in the intervening time period. Following the development of a relatively shallow lake during the late Pleistocene and a short desiccation pulse around 11 220 ¹⁴C yr BP, a transgression of over 135 m occurred at the beginning of the Holocene. The transgression was associated with the formation of beach ridges preserved in the lake stratigraphy on the floor of the modern Lago Cardiel at four different elevations. The preservation of largely unreworked beach ridges indicates a stepwise rise in the lake level. There is no seismic evidence of a major lowering of the lake below modern level during the entire Holocene. Deposition since the mid-Holocene is marked by strong lateral differences in sediment accumulation with a depocentre slightly to the north of the basin midpoint and a pronounced mounded distribution. Seismic reflection geometries, as well as sedimentological characteristics indicate a lacustrine contourite drift covering an area of 80–100 km². As Lago Cardiel is under the influence of westerly winds, these most likely drove lake circulation. The identification of drowned beach ridges and of contourite drifts illustrates that high-resolution seismic stratigraphy is not only a powerful tool in reconstructing past lake level elevations for closed lake basins, but it can also provide information about the rate of lake level changes and the presence and strength of lake currents.     

Trace element compositions of submicroscopic inclusions in coated diamond: A tool for understanding diamond petrogenesis

Trace element compositions of submicroscopic inclusions in both the core and the coat of five coated diamonds from the Democratic Republic of Congo (DRC, formerly Zaire) have been analyzed by Laser Ablation Inductively Coupled Mass Plasma Spectrometry (LA-ICP-MS). Both the diamond core and coat inclusions show a general 2-4-fold enrichment in incompatible elements relative to major elements. This level of enrichment is unlikely to be explained by the entrapment of silicate mantle minerals (olivine, garnet, clinopyroxene, phlogopite) alone and thus submicroscopic fluid or glass inclusions are inferred in both the diamond coat and in the gem quality diamond core. The diamond core fluids have elevated High Field Strength Element (Ti, Ta, Zr, Nb) concentrations and are enriched in U relative to inclusions in the diamond coats and relative to chondrite. The core fluids are also moderately enriched in LILE (Ba, Sr, K). Therefore, we suggest that the diamond cores contain inclusions of silicate melt. However, the Ni content and Ni/Fe ratio of the trapped fluid are very high for a silicate melt in equilibrium with mantle minerals; high Ni and Co concentrations in the diamond cores are attributed to the presence of a sulfide phase coexisting with silicate melt in the diamond core inclusions. Inclusions in the diamond coat are enriched in LILE (U, Ba, Sr, K) and La over the diamond core fluids and to chondrite. The coats have incompatible element ratios similar to natural carbonatite (coat fluid: Na/Ba ≈0.66, La/Ta≈130). The coat fluid is also moderately enriched in HFSE (Ta, Nb, Zr) when normalized to chondritic Al. LILE and La enrichment is related to the presence of a carbonatitic fluid in the diamond coat inclusions, which is mixed with a HFSE-rich hydrous silicate fluid similar to that in the core. The composition of the coat fluid is consistent with a genetic link to group 1 kimberlite.