Thermochemistry of the new silica polymorph moganite

Samples of microcrystalline silica varieties containing variable amounts of the new silica polymorph moganite (up to R~82 wt.%) have been studied by a combination of high temperature solution calorimetry using lead borate (2 PbO · B₂O₃) solvent and transposed temperature drop calorimetry near 977 K, in order to investigate the thermochemical stability of this new silica mineral. The enthalpy of solution at 977 K and the heat content (H₉₇₇ — H₂₉₈) of “pure” moganite phase were estimated to be -7.16 ± 0.35 kJ/mol and 43.62 ± 0.50 kJ/mol, respectively. The standard molar enthalpy of formation is-907.3 ± 1.2 kJ/mol. Thus, calorimetry strongly supports results of previous X-ray and Raman spectroscopic studies that moganite is a distinct silica polymorph. Its thermochemical instability relative to quartz at 298 K of 3.4 ± 0.7 kJ/mol is marginally higher than those of cristobalite and tridymite. Structurally, this instability may be related to the presence of distorted 4-membered rings of SiO₄ tetrahedra, which are not found in the quartz structure. The metastability relative to quartz may also explain the apparent scarcity of moganite in altered rocks and in rocks that are older than 130 my.     

The effect of Fe on the crystal structure of wadsleyite β-(Mg1 − x Fe x )2SiO4, 0.00≤x≤0.40

Single crystals of five wadsleyite compositions, β-(Mg,Fe)₂SiO₄ with Fe/(Fe+Mg)=0.00, 0.08, 0.16, 0.25 and 0.40, have been synthesized at high temperature and pressure in a uniaxial, split-sphere apparatus. Crystal structures of these samples, determined by x-ray diffraction techniques, reveal that iron is significantly ordered: Fe is depleted in the M2 octahedron, while it is enriched in M1 and M3. The most iron-rich synthetic sample, which falls well outside previous estimates of wadsleyite stability, raises questions regarding published Mg₂SiO₄-Fe₂SiO₄ phase diagrams at transition zone conditions.     

Enthalpy of formation of sulfate green rusts

As a contribution to the systematic study of iron oxide thermodynamics, this work reports enthalpies of formation of green rust, a double layered (Fe^II, Fe^III) hydroxide with the ideal stoichiometry , with sulfate as the anion in the interlayer. Samples were characterized by X-ray powder diffraction, thermogravimetric analysis, infrared spectroscopy, and Mössbauer spectroscopy. Full chemical analysis was performed. Contents of Fe^II, Fe^III, water, and sulfate were obtained. We report standard enthalpies of formation for green rust with different Fe^II/Fe^III ratios. Enthalpies of formation from single cation compounds, namely, Fe(OH)₂, Fe(OH)₃, FeSO₄ and H₂O show reasonable agreement with Gibbs free energies of formation from single cation compounds recalculated from the reported literature values. These values show that green rust has little stabilization over a mechanical mixture of these single cation compounds and there is no thermodynamic preference for any particular Fe^II/Fe^III ratio.     

Predicting monthly precipitation along coastal Ecuador: ENSO and transfer function models

Theoretical and Applied Climatology - It is well known that El Niño-Southern Oscillation (ENSO) modifies precipitation patterns in several parts of the world. One of the most impacted areas is...     

Late Quaternary climate change record from two long sediment cores from Guaymas Basin,Gulf of California

Modern Guaymas Basin (Gulf of California, Mexico) is a region of high diatom productivity where exceptional preservation factors maintain biannually alternating sediment deposition as annual varves. New sediment cores from Guaymas Basin (MD02‐2512 and MD02‐2515) present the opportunity to construct climate records from below the last glacial period. A low‐resolution age model has been constructed from oxygen isotope analysis, correlation with other dated short piston cores from Guaymas Basin and an estimate of sedimentation rate. MD02‐2512 from eastern Guaymas Basin has an age range from the Holocene to late marine isotope stage 6 (MIS 6); MD02‐2515 from western Guaymas Basin has an age range from ～8000 to 40 000 yr. Shipboard analyses of colour reflectance, magnetic susceptibility and sediment density are combined with continuous X‐ray fluorescence scans to reconstruct a picture of glacial climate in the Gulf of California. Eastern Guaymas Basin is affected by glacial sea level fall, which results in a drastic change in productivity rates and sediment type. The laminated record of MIS 5 allows comparison with the Holocene, showing a similarity of sedimentation patterns during deglaciation and a series of very rapid variations just prior to the last glaciation. In western Guaymas Basin there are a series of Younger Dryas‐like events during the glacial, typified by low productivity and high terrigenous input. Long‐term climate and productivity changes appear to be caused by the southward displacement of the Subtropical High pressure zone. Copyright © 2005 John Wiley & Sons, Ltd.     

The possible hydrologic effects of the proposed lignite open‐cast mining in Drama lignite field,Greece

The present study investigates the possible hydrologic effects of the proposed lignite open‐cast mining in Drama lignite field (north Greece). Recent years have seen a rapid increase in surface mining. This activity has generated a growing concern for the potential environmental impacts associated with large scale surface mining. In order to achieve a safe mine operation and allow extraction of lignite to considerable depths, extensive dewatering by pumping will be necessary, while at the same time it is desirable to avoid presence of overpumping conditions in the broader area. Based on stratigrafic, hydrologic and hydrogeologic data, a three‐dimensional finite difference model was developed in order to simulate the dewatering process of the western part of the lignite open‐cast mine in Drama and to predict both spatially and temporally the decline of ground water level down to the lignite surface. The dewatering of the part of the aquifer which underlies the mine area will influence the hydrological conditions of the broader region. The most important anticipated effects will be the abandonment of shallow wells as well as the decrease of ground water pumping rates of deep wells. Aquifer discharge towards the ditches of the study area will cease and there will be an inversion of ground water flow from the ditches towards the underlying aquifer. Dewatering activities will probably result in minor subsidence of the nearby peat deposits of Drama Philippi marshes. Moreover, sand pumping as well as the presence of gasses is likely to cause local subsidence phenomena, mainly in the pit slopes. Copyright © 2007 John Wiley & Sons, Ltd.     

A preliminary study of habitat and resource partitioning among co-occurring tropical dolphins around Mayotte, southwest Indian Ocean

Mayotte in the southwest Indian Ocean is characterized by high dolphin diversity. They may coexist within a fairly small area around the island because they exploit neither the same preferential habitats nor the same resources. This preliminary study aimed to investigate ecological niche segregation among these delphinid communities: the Indo-Pacific bottlenose dolphin, Tursiops aduncus, the pantropical spotted dolphin, Stenella attenuata, the spinner dolphin, Stenella longirostris, and the melon-headed whale, Peponocephala electra. Two approaches were used. Habitat preferences were investigated by analysing dolphin sighting data and associated physiographical characteristics. Resource partitioning was explored by analysing C and N stable isotopes in skin and blubber biopsies. Only T. aduncus, which showed clear association with coastal habitats in the lagoon, differed from the others in terms of habitat preferences, characterised by shallow depth and slope, and proximity to the coast. All other species shared similar oceanic habitats immediately outside the lagoon, these being of higher depth and slope, greater distance from the coast and were not discernable by discriminant analysis. The two Stenella species and the melon-headed whale displayed very high overlap in habitat physiographic variables. The analysis of stable isotopes confirmed the ecological isolation of T. aduncus and revealed a clear segregation of P. electra compared to the two Stenella that was not apparent in the habitat analysis. This may reflect ecological differences that were not observable from diurnal surface observations.     

Dissolved uranium, vanadium and molybdenum behaviours during contrasting freshwater discharges in the Gironde Estuary (SW France)

Understanding trace metal behaviour in estuarine environments requires sampling strategies and analytical methods adapted to strong physical and geochemical gradients. In this study, we present a specific sampling strategy covering a wide range of hydrological conditions during nine cruises in 2003–2007 to characterise the behaviour of three dissolved metals (uranium, vanadium and molybdenum) in surface and bottom water along the salinity gradient of the highly turbid macrotidal Gironde Estuary using a solid–liquid extraction. Uranium behaved conservatively whatever the water discharges observed. The slight dissolved U depletion compared to the theoretical dilution line between the fluvial and marine end-members occasionally observed in the low salinity range (0–3) was attributed to the mixing of different water bodies of the Gironde tributaries. In contrast, dissolved V behaviour was largely influenced by the hydrological conditions, showing increasingly pronounced addition with decreasing freshwater discharges, (i.e. increasing residence times of water and particles in the estuary). This addition of dissolved V in the low- to mid-salinity range was attributed to desorption processes observed in the Maximum Turbidity Zone (MTZ). The distribution of dissolved Mo concentrations along the salinity gradient was highly variable. Apparent conservative, and non-conservative behaviours were observed and were related to the concomitance of desorption from SPM, inputs from sediments for additive distribution and biological uptake and removal into sediments for subtractive distribution. Based on the whole database (2003–2007), annual net fluxes to the coastal ocean were estimated for dissolved U (15.5–16.6 t yr⁻¹) and V (31.3–36.7 t yr⁻¹).