Interdiffusion of hydrous dacitic and rhyolitic melts and the efficacy of rhyolite contamination of dacitic enclaves

Effective binary diffusion coefficients of Si during the interdiffusion of hydrous, 3 and 6% H₂O, dacitic and rhyolitic melts have been determined at 1.0 GPa, 1100°–1400°C. Water is shown to enhance diffusivities by one to two orders of magnitude above dry Si diffusivities in the same compositional system for SiO₂ compositions 65–75wt%. The effect of silica content on diffusion is small and typically within experimental error. With 3% H₂O in the melts the Arrhenius equation for Si diffusion at 70% SiO₂ is: $${\text{D = }}2.583\operatorname{x} 10^{ - {\text{ }}8} {\text{ }}\exp ( - 126.5/R{\text{T}})$$ where D is the diffusivity in m²/s, the activation energy (126.5) is in kJ/mol, R is in J/mol and T in Kelvin. Although less-well constrained, the Si diffusivity at 70% SiO₂ with 6% H₂O in the melts can be described by: $${\text{D = }}2.692\operatorname{x} 10^{ - {\text{ }}7} {\text{ }}\exp ( - 131.4/R{\text{T}})$$ The activation energies for diffusion are substantially below the activation energy of 236.4kJ/mol measured during anhydrous interdiffusion in the same system (Baker 1990). The decrease in activation energy with the initial addition of 3% water and the relative insensitivity of the activation energy to the additional water is related to the abundance of OH species in the melt, and the reduction of (Si,Al)-O bond strengths due to the interaction of hydroxyls with the (Si,Al)-O network. Changes in the pre-exponential factor of Arrhenius equations are attributed to the abundance of H₂O species in the melts. No decoupling of non-alkalies from SiO₂ during interdiffusion of the two melts was observed, although alkalies diffuse much more rapidly than non-alkalies (but were not measured quantitatively in this study) and can become decoupled. Interdiffusion of Si and all non-alkalies is demonstrated to be predictable, at least to within a factor of ten, by the Eyring equation. Using the diffusion data of this study for nonalkalies and of other studies for alkalies and Sr isotopes the contamination of a host rhyolitic magma by dacitic enclaves, 5 and 50 cm radius, has been modeled for temperatures of 1000°, 900°, and 800° C with water contents of 3 and 6%. Even when the effects of phenocrysts on diffusion in the dacitic enclaves are estimated the results of the modeling demonstrate that significant contamination is possible in the case of small enclaves, and even large enclaves have the potential to affect the composition of their host magma in geologically short times.     

Simultaneous electrokinetic removal of polycyclic aromatic hydrocarbons and metals from a sediment using mixed enhancing agents

The maintenance of harbor waterways generates large amounts of dredged sediments which are often rich in coexisting organic and inorganic contaminants. Electrokinetic remediation treatments have recently been developed for the simultaneous removal of heavy metals and polycyclic aromatic hydrocarbons (PAHs), using various enhancing agents generally tested sequentially. In this study, different processing fluids were tested, alone or mixed, to improve the decontamination of aged model sediment contaminated with cadmium, lead, chromium, copper, zinc, and five PAHs. Nitric acid (NA) and citric acid (CA) were tested to avoid the formation of an alkaline front into the sediment and favor the metals removal, while an anionic surfactant [sodium dodecyl sulfate (SDS)] and a nonionic surfactant (Tween 20) were tested to solubilize and mobilize PAHs. Processing fluids were circulated under a constant voltage gradient of 1 V cm^?1 for 10–14 days. NA showed an excellent potential to remove metals (76.8–99.9 % removal) and PAHs (70.3–89.7 % removal) in a single run. Besides, the mixture of Tween 20 and CA, more environmental friendly, could be considered as a relatively good processing fluid for the simultaneous removal of metals (10.3–90.8 % removal) and PAHs (53.6–61.6 % removal) from the fine-grained sediment, while SDS mixed to CA was not a good candidate for this purpose (0.1–65 % removal for metals and 34.1–41.0 % removal for PAHs).     

Clicking graphene oxide and Fe3O4 nanoparticles together: an efficient adsorbent to remove dyes from aqueous solutions

Nanohybrid of graphene oxide (GO) and azide-modified Fe₃O₄ nanoparticles (NPs) were fabricated using click reaction. First, Fe₃O₄ NPs were modified by 3-azidopropionic acid. Then, click-coupling of azide-modified Fe₃O₄ NPs with alkyne-functionalized GO was carried out in the presence of CuSO₄·5H₂O and sodium l-ascorbate at room temperature. The attachment of Fe₃O₄ NPs onto the graphene nanosheets was confirmed by Fourier-transform infrared (FTIR) spectroscopy, scanning electron microscopy, thermogravimetric analysis, energy dispersive X-ray spectrometry and X-ray diffraction spectrometry. As the FTIR spectroscopy and energy dispersive X-ray spectrometry analysis showed, the final magnetic graphene nanosheets were also reduced by sodium ascorbate which is a merit for click-coupling reactions. The specific saturation magnetization of the Fe₃O₄-clicked GO was 44.3 emu g^?1. The synthesized hybrid was used in the adsorption of methylene blue and congo red (CR). The adsorption capacities in the studied concentration range were 109.5 and 98.8 mg g^?1 for methylene blue and CR, respectively.     

Petrogenesis of fractionated basaltic lava flows of Poladpur-Mahabaleshwar formation around Mahabaleshwar,Western Ghats,India

Geochemical investigations of Wai sub-group volcanic flows (in and around Mahabaleshwar) have been undertaken to determine the petrogenetic processes involved in the formation of volcanic flows. In comparison to the Ambenali Formation, Mahabaleshwar Formation flows were affected more by crustal materials, which left a signature consisting of enriched levels of K, Rb, Ba, Ti and P. Ratios of Nb/Zr and Ba/Y were sensitive to fractional crystallization; Mahabaleshwar formation flows showed the highest Nb/Zr ratios. Ba was noted as a boundary marker element between the Ambenali (47.3 to 63.9 ppm Ba) and Mahabaleshwar (83.1 to 180 ppm) formations. The general trend of incompatible element concentrations increasing from lower Poladpur to upper Mahabaleshwar flows with increasing Zr and the linear array on the plot are consistent with the fractionation of olivine and clinopyroxene. MgO ranged from 4.8 to 7.1 wt%, TiO₂ from 1.8 to 4.6 wt%, SiO₂ from 47 to 52 wt% and Al₂O₃ from 12 to15.5 wt%. The Mg number (Mg#) was much lower, ranging from 36 to 50. The K₂O/ P₂O₅ ratio showed the role of assimilation in the basaltic flows. TiO₂, Y, Zr, Nb and Mg# were used to determine fractional crystallization, whereas Ba, Rb, K₂O and SiO₂ were used for monitoring the fractional crystallization effects of crustal contamination. The range of Zr/Y and TiO₂ > 1.8 wt% appears to have been generated by fractional crystallization starting from enriched mafic precursors.     

Tchabal Gangdaba massif in the Cameroon Volcanic Line: a bimodal association

Tchabal Gangdaba (TG) volcanic massif, which is a part of the continental sector of the Cameroon Volcanic Line (CVL), is dated between 34.4 and 25.1 Ma. It displays mafic lavas (picrobasalt and basanite, 41–43 wt % SiO₂) and felsic lavas (rhyolite, 68–73 wt % SiO₂). The lack of intermediate rocks evidences a pronounced Daly gap between 43 and 68 wt % SiO₂, which corresponds to an important time span of 3.4 Ma. It is interpreted as due to extensive fractional crystallization under peculiar thermodynamical conditions. Felsic lavas yield strong negative anomalies in Ba, Sr and Eu (0.1?206Pb/²⁰⁴Pb?207Pb/²⁰⁴Pb?208Pb/²⁰⁴Pb?相似文献   

Ab initio valence force field calculations for quartz

We have derived valence force constants for the tetrahedral SiO₄ unit and the inter-tetrahedral SiOSi linkage from previous ab initio molecular orbital calculations on H₄SiO₄ and H₆Si₂O₇ using a split-valence polarized Gaussian basis set (6-31G^*), and used these to calculate the infrared and Raman active vibrational modes of α-quartz. The calculation gives frequencies approximately 15% greater than experiment, as expected from harmonic force constants obtained at this level of Hartree-Fock theory, but the calculation gives the correct distribution of modes within each frequency range. Calculated 28–30 Si and 16–18 O isotope shifts and pressure shifts to 6 GPa are also in reasonable agreement with experiment. We have also used our ab initio force field to calculate the vibrational spectrum for β-quartz. The results suggest either that inclusion of a torsional force constant is important for determining the stability of this high temperature polymorph, or that the β-quartz has a disordered structure with lower symmetry (P6₂) domains, as suggested by earlier diffraction studies.     

Stability conditions of polycyclic aromatic hydrocarbons at high pressures and temperatures

The first results of study of stability of diverse polycyclic aromatic hydrocarbons at around 7 GPa and 773–1073 K are reported. Experiments were carried out in hydraulic multi-anvil presses. The run products after quenching were analyzed using a method of matrix-assisted laser desorption-ionization (MALDI). The formation of polymers of starting matters was determined at 7 GPa and 773–883 K. The polymers are characterized by atomic masses up to 5000 Da, that are multiple by masses of starting matters. At higher temperatures (873–1073 K), the selected PAHs and their polymers become unstable. The decomposition temperature of PAHs and their polymers exclude their stability under Earth’s mantle conditions. The studies could be of great significance for the low-temperature near-surface geodynamics of small and large planetary bodies, which supposedly contain hydrocarbon compounds.     

The application of a hierarchical Bayesian spatiotemporal model for forecasting the SAA trapped particle flux distribution

We implement a hierarchical Bayesian spatiotemporal (HBST) model to forecast the daily trapped particle flux distribution over the South Atlantic Anomaly (SAA) region. The National Oceanic and Atmospheric Administration (NOAA)-15 data from 1–30 March 2008 with particle energies as >30 keV (mep0e1) and >300 keV (mep0e3) for electrons and 80–240 keV (mep0p2) and > 6900 keV (mep0p6) for protons were used as the model input to forecast the flux values on 31 March 2008. Data were transformed into logarithmic values and gridded in a 5^°×5^° longitude and latitude size to fulfill the modelling precondition. A Monte Carlo Markov chain (MCMC) was then performed to solve the HBST Gaussian Process (GP) model by using the Gibbs sampling method. The result for this model was interpolated by a Kriging technique to achieve the whole distribution figure over the SAA region. Statistical results of the root mean square error (RMSE), mean absolute percentage error (MAPE), and bias (BIAS) showed a good indicator of the HBST method. The statistical validation also indicated the high variability of particle flux values in the SAA core area. The visual validation showed a powerful combination of HBST-GP model with Kriging interpolation technique. The Kriging also produced a good quality of the distribution map of particle flux over the SAA region as indicated by its small variance value. This suggests that the model can be applied in the development of a Low Earth Orbit (LEO)-Equatorial satellite for monitoring trapped particle radiation hazard.     

Temporal and spatial patterns in abundance and diversity of fish assemblages in Elkhorn Slough,California

Assemblages of ichthyofauna of shallow inshore habitats along Californía’s central coast are described in terms of species composition, abundance, and life-style categories. A total of 22,334 fishes from 65 species and 27 families was collected with otter trawls at six sites in the main channel and tidal creeks of Elkhorn Slough, a tidal embayment and seasonal estuary, and two nearshore ocean stations in Monterey Bay during 44 months between August 1974 and June 1980. Greater than 90% of the catch comprised 10 species. The four dominant species,Cymatogaster aggregata, Leptocottus armatus, Phanerodon furcatus, andEmbiotoca jacksoni, occurred during most or all seasons and were classified as residents or partial residents. Several abundant species were marine immigrants that seasonally use the slough as spawning and nursery grounds; this resulted in higher abundance and species richness during summer. Species collected during winter largely were slough residents. Species compsosition and richness varied with distance from the slough entrance. The ocean assemblage was most different, and its similarity to other stations decreased progressively with distance inland and into the tidal creeks. During our study, 5,074 fishes were collected by beach seine in Bennett Slough, a remote shallow marsh basin adjacent to the entrance of Elkhorn Slough. Species richness was relatively low and three euryhaline species accounted for >80% of the total catch. The species assemblage was most similar to those at the tidal creek and most shallow stations of Elkhorn Slough. Resident species numerically dominated assemblages in Bennett Slough and the most inland areas of Elkhorn Slough. The high relative abundance of marine-related fishes (classified as marine, marine immigrant, and partial resident), entering Elkhorn Slough early in life or as spawning adults indicates the importance of this habitat to nearshore fish assemblages.     

GeO2 vs SiO2: Glass transitions and thermodynamic properties of polymorphs

Relative-enthalpy measurements have been made on the hexagonal, tetragonal, glass and liquid phases of GeO₂. The glass transition is very sensitive to the impurity content, with a T _g ranging from 980 K for a pure product to 780 K for a Li-doped sample with 0.06 mol % Li. The relative C _p change at T _g of about 5% increases with the impurity content as a result of lower glass transition temperatures. Above 298 K the derived heat capacities are similar for all forms, with slightly higher values for the amorphous phases and two C _p cross-overs at 400 and 1000 K between the hexagonal and tetragonal modifications. For both GeO₂ and SiO₂ the coordination state markedly affects C _p and the entropy below 300 K, where the properties are much lower for the tetragonal than for the hexagonal modifications, i.e., S ₂₉₈ = 39.7 vs 55.3 J/mole K and 27.8 vs 41.4 J/ mole K for GeO₂ and SiO₂, respectively. The high-temperature C _p's of coesite and stishovite are likely similar to those of the low-pressure SiO₂ forms. Finally, these results, low-temperature C _p data and enthalpy-of-solution measurements have been used to derive a consistent set of thermodynamic properties for the GeO₂ modifications.     

Sorption of uranyl and arsenate on SiO2, Al2O3, TiO2 and FeOOH

Migration of uranium and arsenic in aquatic environments is often controlled by sorption on minerals present along the water flow path. To investigate the sorption behaviour, batch experiments were conducted for uranium and arsenic as single components and also solutions containing both uranium and arsenic in the presence of SiO₂, Al₂O₃, TiO₂ and FeOOH at a pH ranging from 3 to 9. In solutions containing only U(VI) or As(V) with the minerals, the sorption of U(VI) was low at acidic pH range and increases with increasing pH, whereas As(V) showed opposite sorption behaviour to Al₂O₃, TiO₂ and FeOOH from acidic pH range to alkaline condition. For the As(V)–SiO₂ system, the sorption was low for almost all pH. Sorption of U(VI) and As(V) on SiO₂ and FeOOH is almost similar in solutions containing either U(VI) or As(V) separately, or both together. In the U(VI)–As(V)–Al₂O₃ system, a significant retardation in uranyl sorption and an enhancement in arsenate sorption on Al₂O₃ were observed for a wide range of pH. The sorption behaviour of U(VI) and As(V) was changed when Al₂O₃ was replaced by TiO₂, where an increase in sorption was observed for both elements. The sorption behaviour of uranyl and arsenate in the U(VI)–As(V)–TiO₂ system gives evidence for the formation of uranyl–arsenate complexes. The change in sorption retardation/enhancement of U(VI) and As(V) could be explained by the formation of uranyl–arsenate complexes or due to the competitive sorption between uranyl and arsenate species.     

Sources and history of PAHs in lake sediments from oil-producing and industrial areas,northeast China

Abundance, sources, and historical records of polycyclic aromatic hydrocarbons (PAHs) in sediment cores of three lakes located in northeast China were evaluated. One lake was located in a rural oil field area, one in an industrial urban oil field area, and the third in an urban industrialized area without oil field influence. Cores from each lake were divided into 1-cm sections, dated using ¹³⁷Cs techniques, and 16 priority PAH compounds were measured. Total PAH concentrations were greater in industrial areas than in rural area, regardless of associated oil production. Only petroleum sources of PAHs were identified in lakes near oil fields between 1950s and 1980s, while sources of liquid fossil fuel combustion were persistently identified in the industrial urban lake. From 1990s to 2000s, PAH concentrations, especially high molecular weight PAHs, significantly increased in all lakes, which were consistent with the economic development in China, suggesting a change in energy use from wood burning and petroleum (oil) to liquid fossil fuel combustion. Environmental risk was low to moderate in sediments of the three lakes studied, and increases in high molecular weight PAHs during 1900s–2000s is a concern.     

Magmatic evolution of Late Cenozoic volcanic rocks of the Lau Ridge,Fiji

Three main groups of lavas are exposed on islands of the Lau Ridge: the Lau Volcanic Group (LVG), 14.0–5.4 Ma, are predominantly andesite; Korobasaga Volcanic Group (KVG), 4.4–2.4 Ma, are predominantly basalt and Mago Volcanic Group (MVG), 2.0–0.3 Ma, are basalt-hawaiite. LVG and KVG lavas are mostly medium-K tholeiitic rocks with high LILE/HFSE ratios characteristic of islands ares, while MVG lavas are ne-normative alkalic rocks with high LILE and HFSE, characteristic of ocean island basalts. LVG lavas have high ?_Nd (+8.0–+8.4) and low ⁸⁷Sr/⁸⁶Sr (0.70273–0.70349) similar to N-MORB, whereas KVG lavas have slightly more radiogenic values (?_Nd=+7.5?+8.4; ⁸⁷Sr/⁸⁶Sr=0.70323-0.70397). MVG lavas form an isotopically distinct group having lower ?_Nd (+4.6–+4.9) and (⁸⁷Sr/⁸⁶Sr ranging from 0.70347–0.70375). LVG lavas were erupted in a primary oceanic island arc (Vitiaz arc) during the Miocene. Basaltic lavas were derived by approximately 19% partial melting of mantle wedge peridotite with only minor subduction component. Andesites and dacites were produced by low-pressure plagioclase-pyroxene-titanomagnetite dominated crystal fractionation. KVG lavas were erupted during the period immediately prior to or during the initial stages of rifting in the Lau Basin, and, like LVG lavas, show significant chemical differences at the northern and southern ends of the Lau Ridge. Lavas at the northern end (type (ii)) appear to be derived from a more depleted source than LVG but with a greater amount of subduction component. Those at the southern end (type (i)) probably came from a slightly more enriched source with less subduction component. MVG basalts and hawaiites were derived from an enriched mantle with little or no subduction input. The hawaiites (type (i)) could not have been derived from the basalts (type (ii)), and the two magma types must have come from different sources, indicating mantle heterogeneity. The lack of subduction influence indicates the MVG lavas are tectonically unrelated to the present-day Tonga arc, and the lack of depletion indicators suggests they have tapped a different (new?) part of the mantle wedge. This may reflect introduction of sub-Pacific mantle through the present Tonga-Lau subduction system.     

Experimental evidence for the coexistence of two liquids in the H2O-SiO2-NaF-Na2SO4 System at T = 700°C and P = 2 kbar

The phase state of fluid in the H₂O-NaF-Na₂SO₄ system in the presence of silicates (quartz and albite) was experimentally explored using the method of synthetic fluid inclusions in quartz at 700°C and pressures of 1 and 2 kbar. Parallel experiments were conducted under identical conditions with either two silicates (quartz and albite) or quartz only. The presence of albite affects heterogeneous fluid equilibria both at different pressures and at different solution compositions. This indicates high solubilities of silicates in a saltwater fluid containing NaF and Na₂SO₄. The absence of inclusions homogenizing to a gas phase in the experimental products provides compelling evidence that liquid-liquid rather than liquid-vapor equilibria are characteristic of the H₂O-SiO₂-NaF-Na₂SO₄ and H₂O-SiO₂-NaF-Na₂SO₄-NaAlSi₃O₂ systems in the heterogeneous region. It can be concluded that critical equilibria in saturated solutions can exist in these systems. In addition, it was shown that the phase diagrams of these systems are complicated by the formation of immiscible liquids in the presence of vapor. This allowed us to conclude that there are two critical curves describing equilibria with two different salts. Fluids containing two salts (NaF and Na₂SO₄) are similar to fluids containing only one of these salts: (a) two liquids are in equilibrium under the parameters of the upper heterogeneous region, (b) each of them can in turn undergo unmixing at decreasing temperature and pressure, and (c) owing to chemical interaction between silicate and fluid components, a glassy phase can be formed and trapped in inclusions.     

Chloritization and its bearing on uranium mineralization in Madyalabodu area,Cuddapah district,Andhra Pradesh

Uranium mineralization in Madyalabodu area, Cuddapah district, Andhra Pradesh, is spatially related to chloritized and brecciated quartzite of the Gulcheru Formation in the immediate vicinity of E-W to ESE-WNW trending basic dyke. Chloritization transgresses the lithological boundaries. Whole-rock geochemical data indicate enrichment of MgO and Al₂O₃ coupled with depletion of SiO₂, Na₂O, K₂O, CaO and TiO₂ in the chlorite-rich zone. Fe₂O₃ and FeO do not vary significantly in the altered and the unaltered zones. Electron Probe Microanalysis (EPMA) data reveal that the chlorites in contact with uranium minerals are enriched in MgO and depleted in FeO than in the others. Considering the petrological evidence, geochemical signature and structural constraints, it appears that chlorite acted more as an adsorbent rather than as a reductant in facilitating uranium mineralization. Uraninite crystallized later from the uranium originally adsorbed on chlorites. Chloritization might also have facilitated mineralization through the generation of nascent hydrogen, H₂S and lowering pH of uranium-bearing solution.     

Main issues of an evacuation in case of volcanic crisis: social stakes in Guadeloupe (Lesser Antilles Arc)

The last major eruption of La Soufrière volcano in Guadeloupe (Lesser Antilles) in 1976–1977 caused the mass evacuation of part of the population, whereby a total of 76,000 people were displaced for a period of 3–6 months. This evacuation has left a bitter memory among the inhabitants who believed that the political authorities of the time had not anticipated the possibility of an eruption crisis and that decisions were taken in haste. La Soufrière remains active, and future eruptions could once again lead to partial or even total evacuation of the population if there were a major Plinian eruption. This article offers an investigation of future evacuation procedures, questioning different aspects of Guadeloupe’s current territorial and social challenges (the multi-risk context, the reporting to the scientists and to the authorities, the importance of local solidarity). In order to do so, we used the Focus Group Discussion method, making it possible to identify resources and gaps in crisis management on the basis of previous event history.     

Solution behavior of C-O-H volatiles in FeO-Na2O-Al2O3-SiO2 melts in equilibrium with liquid iron alloy and graphite at 4 GPa and 1550°C

In order to elucidate the solution behavior of carbon and hydrogen in iron-bearing magmatic melts in equilibrium with a metallic iron phase and graphite at oxygen fugacity (fO₂) values 2–5 orders of magnitude below the iron-wustite buffer equilibrium, fO₂ (IW), experiments were carried out at 4 GPa and 1550°C with melts of FeO-Na₂O-SiO₂-Al₂O₃ compositions. Melt reduction in response to an fO₂ decrease was accompanied by a decrease in FeO content. The values of fO₂ in the experiments were determined on the basis of equilibrium between Fe-C-Si alloy and silicate liquid. Infrared and Raman spectroscopy showed that carbon compounds are formed in FeO-Na₂O-SiO₂-Al₂O₃ melts: CH₄ molecules, CH₃ complexes (Si-O-CH₃), and complexes with double C=O bonds. The content of CO₂ molecules and carbonate ions (CO ₃ ^2? ) is very low. In addition to carbon-bearing compounds, dissolved hydrogen occurs in melt as H₂ and H₂O molecules and OH^? groups. The spectral characteristics of FeO-Na₂O-SiO₂-Al₂O₃ glasses indicate the occurrence of redox reactions in the melt, which are accompanied at decreasing fO₂ by a significant decrease in H₂O and OH^?, a slight decrease in H₂, and a significant concomitant increase in CH₄ content. The content of species with the double C=O bond increases considerably at decreasing fO₂ and reaches a maximum at ΔlogfO₂(IW) = ?3. According to the obtained IR spectra, the total water content (OH^? + H₂O) in the glasses is 1.2–5.8 wt % and decreases with decreasing fO₂. The high H₂O contents are due largely to oxygen release related to FeO reduction in the melt. The total carbon content at high H₂O (4.9–5.8 wt %) is approximately 0.4 wt %. The carbon content in liquid iron alloys depends on silicon content and, probably, oxygen solubility and ranges from 0.3 to 3.65 wt %. Low carbon contents were observed at a significant increase in Si content in liquid iron alloy, which may be as high as ～13 wt % at fO₂ values 4–5 orders of magnitude below fO₂(IW).     

The structural role of Al2O3 and TiO2 in immiscible silicate liquids in the system SiO2-MgO-CaO-FeO-TiO2-Al2O3

The effects of the addition of Al₂O₃ on the large stable two liquid field in the SiO₂-TiO₂-CaO-MgO-FeO system were experimentally determined. The increase of Al₂O₃ content in the starting composition results in the decrease of critical temperature, phase separation and liquidus temperature of the two liquid field until it is rendered completely metastable. The shrinkage of the two liquid field indicates that Al₂O₃ is acting in the role of a network former and homogenizes the structure of the two melts. In this alkali-free system Al⁺³ utilizes the divalent cations, Ca⁺² and Mg⁺², for local charge balance with a preference for Ca⁺² over Mg⁺². Thus, AlO₄ tetrahedra combine with SiO₄ tetrahedra to form an aluminosilicate framework which polymerizes the SiO₂-poor melt and makes it structurally more similar to the SiO₂-rich melt. However, Ca⁺² and Mg⁺² are not as efficient in a charge balancing capacity as the monovalent K⁺ and Na⁺ cations. The lack of alkalis in this system limits the stability of AlO₄ tetrahedra in the highly polymerized SiO₂-rich melt and results in the preference of Al₂O₃ for the SiO₂-poor melt. The partitioning systematics of Ti are virtually identical to those of Al. It is concluded that Ti occurs in tetrahedral coordination as a network forming species in both the high — and low — SiO immiscible melts.     

Towards hydrological and geochemical understanding of an ephemeral palustrine perched water table “wetland” (Lanseria Gneiss,Midrand, South Africa)

Wetland delineation is commonly based on terrain unit, soil form, soil wetness and vegetation indicators which along with the shallow groundwater or proximate surface water are often absent in many ephemeral inland South African areas due to, for instance, prolonged dry periods (seasons to years) which mask these indicators, as well as disruption of surface materials due to construction, agricultural activities and field fires. Furthermore, many “wetlands” in South Africa comply with the four indicators, but the notable absent requirement for wetlands is missing, namely the shallow groundwater table, as many of these systems form in hillslope seeps, catenas or from perched water tables. A 200-m-long excavation through one such a system is being studied in Midrand (Gauteng, South Africa). The site is underlain by Lanseria Gneiss and is waterlogged after long and intense periods of intense rainfall. Frequent downslope soil profiling, horizon-specific laboratory analyses for grading and Atterberg Limits, X-Ray Diffraction and X-Ray Fluorescence Spectroscopy data are interpreted together with soil percolation tests to generate a conceptual model of the system. The results are discussed in terms of the need to consider these temporary systems that do not have a shallow groundwater table and that are not in direct contact with surface drainage features as a possible special type of wetlands, notably in arid regions where they play a very important role in biodiversity and should, therefore, be protected.     

Vibrational spectra of olivine composition glasses: The Mg-Mn join

The vibrational frequencies of a series of splatquenched, olivine glasses spanning the compositional range from Mg₂SiO₄ to Mn₂SiO₄ have been determined using both infrared and Raman spectroscopies. The spectra of all glasses show evidence of tetrahedral coordination of silicon (possibly with some slight distortions), and largely octahedral coordination of magnesium. Spectra of Mn-rich glasses indicate that there is some manganese in 4 or 5-fold coordination. The frequencies observed for the fundamental vibrations of the silica tetrahedra are similar to those previously observed for SiO₄ groups in both crystalline and glassy orthosilicates. Additionally, there is evidence for a small amount of silicate polymerization in all glasses characterized: vibrations attributable to Si₂O₇ groups are visible in both infrared and Raman spectra.