A mapping of the electron localization function for the silica polymorphs: evidence for domains of electron pairs and sites of potential electrophilic attack

The electron localization function, η, evaluated for first-principles geometry optimized model structures generated for quartz and coesite, reveals that the oxide anions are coordinated by two hemispherically shaped η-isosurfaces located along each of the SiO bond vectors comprising the SiOSi angles. With one exception, they are also coordinated by larger banana-shaped isosurfaces oriented perpendicular to the plane centered in the vicinity of the apex of each angle. The hemispherical isosurfaces, ascribed to domains of localized bond-pair electrons, are centered ～0.70 Å along the bond vectors from the oxide anions and the banana-shaped isosurfaces, ascribed to domains of localized nonbonding lone-pair electrons, are centered ～0.60 Å from the apex of the angle. The oxide anion comprising the straight SiOSi angle in coesite is the one exception in that the banana-shaped isosurface is missing; however, it is coordinated by two hemispherically shaped isosurfaces that lie along the bond vectors. In the case of a first-principles model structure generated for stishovite, the oxide anion is coordinated by five hemispherically shaped η-isosurfaces, one located along each of the three SiO bond vectors (ascribed to domains of bonding-electron pairs) that are linked to the anion with the remaining two (ascribed to domains of nonbonding-electron pairs) located on opposite sides of the plane defined by three vectors, each isosurface at a distance of ～0.5 Å from the anion. The distribution of the five isosurfaces is in a one-to-one correspondence with the distribution of the maxima displayed by experimental Δρ and theoretical ??²ρ maps. Isosurface η maps calculated for quartz and the (HO) ₃ SiOSi(OH) ₃ molecule also exhibit maxima that correspond with the (3,?3) maxima displayed by distributions of ??²ρ. Deformation maps observed for the SiOSi bridges for the silica polymorphs and a number of silicates are similar to that calculated for the molecule but, for the majority, the maxima ascribed to lone-pair features are absent. The domains of localized nonbonding-electron pair coordinating the oxide anions of quartz and coesite provide a basis for explaining the flexibility and the wide range of the SiOSi angles exhibited by the silica polymorphs with four-coordinate Si. They also provide a basis for explaining why the SiO bond length in coesite decreases with increasing angle. As found in studies of the interactions of solute molecules with a solvent, a mapping of η-isosurfaces for geometry-optimized silicates is expected to become a powerful tool for deducing potential sites of electrophilic attack and reactivity for Earth materials. The positions of the features ascribed to the lone pairs in coesite correspond with the positions of the H atoms recently reported for an H-doped coesite crystal.     

Future change of climate in South America in the late twenty-first century: intercomparison of scenarios from three regional climate models

Regional climate change projections for the last half of the twenty-first century have been produced for South America, as part of the CREAS (Cenarios REgionalizados de Clima Futuro da America do Sul) regional project. Three regional climate models RCMs (Eta CCS, RegCM3 and HadRM3P) were nested within the HadAM3P global model. The simulations cover a 30-year period representing present climate (1961–1990) and projections for the IPCC A2 high emission scenario for 2071–2100. The focus was on the changes in the mean circulation and surface variables, in particular, surface air temperature and precipitation. There is a consistent pattern of changes in circulation, rainfall and temperatures as depicted by the three models. The HadRM3P shows intensification and a more southward position of the subtropical Pacific high, while a pattern of intensification/weakening during summer/winter is projected by the Eta CCS/RegCM3. There is a tendency for a weakening of the subtropical westerly jet from the Eta CCS and HadRM3P, consistent with other studies. There are indications that regions such of Northeast Brazil and central-eastern and southern Amazonia may experience rainfall deficiency in the future, while the Northwest coast of Peru-Ecuador and northern Argentina may experience rainfall excesses in a warmer future, and these changes may vary with the seasons. The three models show warming in the A2 scenario stronger in the tropical region, especially in the 5°N–15°S band, both in summer and especially in winter, reaching up to 6–8°C warmer than in the present. In southern South America, the warming in summer varies between 2 and 4°C and in winter between 3 and 5°C in the same region from the 3 models. These changes are consistent with changes in low level circulation from the models, and they are comparable with changes in rainfall and temperature extremes reported elsewhere. In summary, some aspects of projected future climate change are quite robust across this set of model runs for some regions, as the Northwest coast of Peru-Ecuador, northern Argentina, Eastern Amazonia and Northeast Brazil, whereas for other regions they are less robust as in Pantanal region of West Central and southeastern Brazil.     

The correlation between geochemical data and SPOT satellite imagery of lateritic terrain in southern Mali

Detailed geochemical mapping of superficial lateritic formations is compared with recent high-resolution SPOT satellite images in the Dagadamou prospect in southern Mali.The two main landscape features standing out in SPOT images are expressed by thematic indices derived from multispectral data. They reflect the distribution of vegetation cover and the distinction between silty clay soils in the valleys and ferruginous duricrust exposed on the plateaus. Geochemical differentiation factors are closely related to the nature of sampled materials and reflect the relative amounts of major constituent minerals estimated by normative calculation.Duricrust samples with high Fe and Al content are also enriched in trace elements, P, V, Cr, As, Mo, Nb and Cu, immobilized in the weathering profile with secondary oxihydroxide minerals.Soils of flats are composed mainly of quartz and kaolinite; they also concentrate heavy minerals characterized by high contents of Zr, Ti, Ce and Y.Accumulation of detrital material at the periphery of duricrust plateaus is marked by a geochemical halo of higher contents in Zr and quartz at their periphery. This feature is clearly visible on SPOT imagery as a zone of high reflectance, devoid of vegetation.The density of vegetation on duricrust is related to its kaolinite content. Its distribution is characterized by a striped pattern, which is probably controlled by bedrock lithological structures preserved in the lateritic cover.This study shows the relationships, both direct and indirect, existing between spectral reflectance and geochemical composition of superficial lateritic formations. Many other landscape features identified with high resolution on SPOT images provide complementary information, which could be very helpful at various stages of geological and mineral exploration in lateritic terrain.     

Vibrational spectroscopy of beryllium aluminosilicates: Heat capacity calculations from band assignments

Far-infrared, mid-IR, and Raman powder spectra were measured on six phases (bromellite, chrysoberyl, phenakite, bertrandite, beryl, and euclase) in the system BeO-Al₂O₃-SiO₂-H₂O. A single-crystal absorption spectrum of IR fundamentals in beryl is also presented, which more closely resembles the powder absorption spectrum than it does absorption spectra calculated from single-crystal reflection data. Assignments of the SiO₄ and BeO₄ internal vibrations are made in accordance with each mineral's symmetry and composition and by comparison to structural analogs. Heat capacities C _v calculated for these partial band assignments agree with C _v derived from experimental C _p for all six phases, provided that Kieffer's (1979c) model is slightly modified to correctly enumerate both Si-O and Be-O stretching modes in the high frequency region (>750 cm^?1). Si-O stretching bands were found to out-number Be-O stretching modes in the high-energy region of the vibrational spectra with two exceptions: (1) For those phases containing oxygen ions not coordinated to silicon, vibrations occurring at v>1,080 cm^?1 that are attributable to Be-O (H) stretching must be treated separately in the model in order to calculate C _v accurately. (2) Minerals consisting entirely of interlocking Si and Be tetrahedra (i.e., phases without Al or OH) can be modeled by one optic continuum representing all optical modes. These results, along with the occurrence of very low energy lattice vibrations for Be-silicates within Al, suggests that although Be-O bonds are generally weaker than neighboring Si-O bonds, Be mimics the network-forming characteristic of Si to a limited extent.     

On the climate response of the low-latitude Pacific Ocean to changes in the global freshwater cycle

Under global warming, the predicted intensification of the global freshwater cycle will modify the net freshwater flux at the ocean surface. Since the freshwater flux maintains ocean salinity structures, changes to the density-driven ocean circulation are likely. A modified ocean circulation could further alter the climate, potentially allowing rapid changes, as seen in the past. The relevant feedback mechanisms and timescales are poorly understood in detail, however, especially at low latitudes where the effects of salinity are relatively subtle. In an attempt to resolve some of these outstanding issues, we present an investigation of the climate response of the low-latitude Pacific region to changes in freshwater forcing. Initiated from the present-day thermohaline structure, a control run of a coupled ocean–atmosphere general circulation model is compared with a perturbation run in which the net freshwater flux is prescribed to be zero over the ocean. Such an extreme experiment helps to elucidate the general adjustment mechanisms and their timescales. The atmospheric greenhouse gas concentrations are held constant, and we restrict our attention to the adjustment of the upper 1,000 m of the Pacific Ocean between 40°N and 40°S, over 100 years. In the perturbation run, changes to the surface buoyancy, near-surface vertical mixing and mixed-layer depth are established within 1 year. Subsequently, relative to the control run, the surface of the low-latitude Pacific Ocean in the perturbation run warms by an average of 0.6°C, and the interior cools by up to 1.1°C, after a few decades. This vertical re-arrangement of the ocean heat content is shown to be achieved by a gradual shutdown of the heat flux due to isopycnal (i.e. along surfaces of constant density) mixing, the vertical component of which is downwards at low latitudes. This heat transfer depends crucially upon the existence of density-compensating temperature and salinity gradients on isopycnal surfaces. The timescale of the thermal changes in the perturbation run is therefore set by the timescale for the decay of isopycnal salinity gradients in response to the eliminated freshwater forcing, which we demonstrate to be around 10–20 years. Such isopycnal heat flux changes may play a role in the response of the low-latitude climate to a future accelerated freshwater cycle. Specifically, the mechanism appears to represent a weak negative sea surface temperature feedback, which we speculate might partially shield from view the anthropogenically-forced global warming signal at low latitudes. Furthermore, since the surface freshwater flux is shown to play a role in determining the ocean’s thermal structure, it follows that evaporation and/or precipitation biases in general circulation models are likely to cause sea surface temperature biases.     

Devitrite (Na2Ca3Si6O16)—structural, spectroscopic and computational investigations on a crystalline impurity phase in industrial soda-lime glasses

Single crystals of devitrite (Na₂Ca₃Si₆O₁₆) were synthesized as pale-yellow transparent needle shaped crystals using a Na₂MoO₄-flux. Experiments aiming to prepare the K-equivalent of devitrite from the corresponding K₂MoO₄-flux were unsuccessful. The crystal structure of devitrite was determined from single-crystal X-ray diffraction data (Mo-K_α radiation, 2θ_max.?=?25.34°, R_int?=?2.66%) and refined in space group P $ \bar{1} $ (no. 2) to R(|F|)?=?3.08% using 2,513 observed reflections with I?>?2σ(I). Unit-cell parameters are: a?=?7.2291(8), b?=?10.1728(12), c?=?10.6727(12) Å, α?=?95.669(9), β?=?109.792(10), γ?=?99.156(9)°, V?=?719.19(14) ų, Z?=?2. The structure belongs to the group of multiple chain silicates consisting of dreier quadruple chains, i.e. the crystallochemical formula can be written as $ {\hbox{N}}{{\hbox{a}}_2}{\hbox{C}}{{\hbox{a}}_3}\left\{ {{\mathbf{uB}}{,4}_\infty^1} \right\}\left[ {^3{\hbox{S}}{{\hbox{i}}_6}} \right.\left. {{{\hbox{O}}_{16}}} \right\} $ . Linkage between the bands running along [100] is provided by double chains of edge sharing CaO₆-octahedra as well as additional more irregularly coordinated Na- and Ca-cations located in the tunnel-like cavities of the mixed tetrahedral-octahedral framework. Structural investigations were completed by Raman and infrared spectroscopical studies. The allocation of the bands to certain vibrational species was aided by density functional theory (DFT) calculations.     

Earthquake swarms preceding the 2000 eruption of Miyakejima volcano, Japan

The first sign of magma accumulating beneath Miyakejima, an island volcano in the northern Izu islands, Japan, came at around 18:00 on 26 June 2000, when a swarm of earthquakes was detected by a volcano seismic network on the island. Earthquakes occurred initially beneath the southwest flank near the summit and gradually migrated west of the island, where a submarine eruption occurred the next morning. Earthquakes then migrated further to the northwest between Miyakejima and Kozushima, another volcanic island and developed to the most intense earthquake swarm ever observed in and around Japanese archipelago. To better image how the initial magma intrusion occurred, we relocated hypocenters by using a station-correction method and a double-difference method. The relocated epicenters are generally concentrated near the upper bound of dyke intrusions inferred from geodetic studies throughout the initial stages of the 2000 eruption at Miyakejima from 26 to 27 June 2000. As for seismic activity westward off Miyakejima in the morning on 27 June, hypocenters from both a nationwide seismic network that were relocated by the double-difference method, and those from the volcano seismic network relocated by the station-correction method, formed a very shallow cluster that ascended slowly with time as it propagated northwestward from Miyakejima. This suggests that the dykes have both a radial and upward component of movement.Editorial responsibility: S. Nakada, T. Druitt     

Effects of historical and projected land use/cover change on runoff and sediment yield in the Netravati river basin,Western Ghats,India

In this study, the effects of changes in historical and projected land use land cover (LULC) on monthly streamflow and sediment yield for the Netravati river basin in the Western Ghats of India are explored using land use maps from six time periods (1972, 1979, 1991, 2000, 2012, and 2030) and the soil and water assessment tool (SWAT). The LULC for 2030 is projected using the land change modeller with the assumption of normal growth. The sensitivity analysis, model calibration, and validation indicated that the SWAT model could reasonably simulate streamflow and sediment yield in the river basin. The results showed that the spatial extent of the LULC classes of urban (1.80–9.96%), agriculture (31.38–55.75%), and water bodies (1.48–2.66%) increased, whereas that of forest (53.04–27.03%), grassland (11.17–4.41%), and bare land (1.09–0.16%) decreased from 1972 to 2030. The streamflow increased steadily (7.88%) with changes in LULC, whereas the average annual sediment yield decreased (0.028%) between 1972 and 1991 and increased later (0.029%) until 2012. However, it may increase by 0.43% from 2012 to 2030. The results indicate that LULC changes in urbanization and agricultural intensification have contributed to the increase in runoff, amounting to 428.65 and 58.67 mm, respectively, and sediment yield, amounting to 348 and 43 ton/km², respectively, in the catchment area from 1972 to 2030. The proposed methodology can be applied to other river basins for which temporal digital LULC maps are available for better water resource management plans.