Crystal structures of Ni2SiO4 and Fe2SiO4 as a function of temperature and heating duration

X-ray structure refinements of Ni₂SiO₄ and Fe₂SiO₄ spinels have been made as a function of temperature and heating duration by intensity measurements at high temperatures and room pressure. The lattice parameters of Ni₂SiO₄ spinel linearly increased with temperature up to 1,000° C. However, Fe₂SiO₄ spinel exhibited a nonlinear thermal expansion and was converted to a polycrystalline mixture of spinel and olivine by heating of less than one-hour at 800° C. The ratios between the octahedral and tetrahedral bond lengths D _oct/D _tetr and between the shared and unshared edge distances (O-O)_sh/(O-O)_unsh in Fe₂SiO₄ spinel were both much larger than those in Ni₂SiO₄. These ratios increase with temperature. The Fe₂SiO₄ spinel more readily approached a activation state which facilitated the transition to the olivine structure than the Ni₂SiO₄ spinel. The lattice parameter of Ni₂SiO₄ spinel decreased with heating period at constant temperatures of 700° C and 800° C. The parameter of the quenched sample after heating for 52 h at 700° C was smaller than that of the nonheated sample. The refinements of the site occupancies at each heating duration indicated an increase in the cation deficiency in both tetrahedral and octahedral sites. Electron microprobe analysis, however, proved no significant difference in the chemical compositions between the quenched and nonheated samples. Si and Ni atoms displaced from normally occupied spinel lattice sites are assumed to settle in vacant sites defined by the cubic close packed oxygen sublattice in a manner which preserves the electric neutrality of the bulk crystal.     

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.     

Calorimetric study of the stability of spinelloids in the system NiAl2O4-Ni2SiO4

Enthalpies of solution in molten 2 PbO · B₂O₃ at 974 K were measured for four spinelloids, phases I (0.75 NiAl₂O₄ · 0.25 Ni₂SiO₄), II (0.60 NiAl₂O₄ · 0.40 Ni₂SiO₄), III and IV (0.50 NiAl₂O₄ · 0.50 Ni₂SiO₄) in the system NiAl₂O₄ · Ni₂SiO₄. The enthalpies (in cal per 4-oxygen mol) of formation from NiAl₂O₄ and Ni₂SiO₄ spinels are: phase I, 945±366; phase II, 1072±360; phase III, 2253±390; phase IV, 3565±544. Using these enthalpy data in combination with phase relations at high pressure at 1373 K, positive entropies of formation of the spinelloids from NiAl₂O₄ and Ni₂SiO₄ spinels were estimated (in cal mol^?1 K^?1): phase I, 1.2; phase II, 1.5; phase III, 2.0–2.3; phase IV, 3.0–3.1. The thermochemical data obtained above suggest that the spinelloids are “entropy-stabilized” phases with partially disordered cation distributions. The configurational entropies of the spinelloids were calculated based on the observed cation distribution in each spinelloid phase. The positive entropies of formation of the spinelloids from the spinel endmembers are due primarily to the configurational entropies although small positive vibrational entropy changes may also exist.     

Ion dynamics studies of liquid and glassy silicates,and gas-in-liquid solutions

We give a brief review of ion dynamics studies of liquid and glassy states of SiO₂ and silicate colutions which have been carried out in recent years in this laboratory. We summarize studies on SiO₂, Na⁺ migration in Na₂O·SiO₂ in the “glassy state”, and ionic coordination in multicomponent framework silicates. We present new results on the coordination of Al³⁺ in albite as a function of pressure and show that it is consistent with results of laboratory studies on albite glasses formed at high pressure. We compare calculated PVT data for jadeite, albite and diopside and relate the behavior of the low pressure compressibility to the spinodal limit at negative pressures. Some preliminary studies of inert gas solution in jadeite and of CO₂ solution in a glass having a composition of approximately Na₂O·3SiO₂ are described.     

Phylogenetic Problems in Polynesian Simuliidae (Diptera: Culicomorpha): A progress report

As a basis for eventual control of the vicious anthropophilic and ornithophilic simuliid females of the Marquesas Islands, a taxonomic revision of Polynesian Simuliidae is in progress. Cytotaxonomic studies reveal two simuliid species in Rarotonga, Cook Islands; nine species in Tahiti, Society Islands, and two in the Marquesas Islands. A cytophylogeny is now available. Polynesian Simuliidae are unique in possessing heterogametic females. A reconstructed phylogeny, based mainly on morphological character states of larvae and pupae, agrees well with the cytophylogeny. One of the new species which is closely related to Simulium oviceps Edwards has larvae with highly reduced, non-functional cephalic fans. Ages of the Polynesian islands are discussed in relation to possible dispersal of Simuliidae into Polynesia.     

Modified biomass of Phanerochaete chrysosporium immobilized on luffa sponge for biosorption of hexavalent chromium

Phanerochaete chrysosporium, a white rot basidiomycete, was immobilized over Luffa cylindrica sponge discs, treated with 0.1 N HCl and its potentiality for the removal of hexavalent chromium [Cr(VI)] from water was investigated in both batch and in up-flow fixed-bed bioreactor. The acid treatment of biomass increased the uptake capacity and percentage removal of Cr(VI) from 33.5 to 46.5 mg g^?1 and 67 to 92 %, respectively. Maximum uptake of Cr(VI) was achieved at pH 2, temperature 40 °C after 100 min of contact time. The Cr(VI) sorption on the biomass was better explained by Langmuir isotherm. Thermodynamic studies indicated that the process was spontaneous and endothermic. Sorption kinetic study showed that pseudo-second-order model best correlates the Cr(VI) sorption on the biomass as compare to pseudo-first-order kinetic model. The performance of fixed-bed bioreactor was evaluated at different bed heights (5, 15 and 25 cm) and flow rates (1.66, 4.98 and 8.33 mL min^?1) by using bed depth service time model. Response surface methodology statistical method was applied for optimizing the process parameters. FTIR analysis showed that amino groups were mainly involved in adsorption of Cr(VI).     

Comparative study to evaluate three ground-based optical remote sensing techniques under field conditions by a gas tracer experiment

Today, ground-based optical remote sensing (ORS) has become an intensively used method for quantifying pollutant or greenhouse gas emissions from point or area sources, and for the validation of airborne or satellite remote sensing data. In this study, we present the results of a release experiment using acetylene (C₂H₂) as a tracer gas, where three ORS techniques were simultaneously tested for two main purposes: (1) the detection of emission sources and (2) the quantification of release rates. Therefore, passive and active open-path Fourier transform infrared spectroscopy (OP-FTIR) and open-path tunable diode laser absorption spectroscopy (TDLAS) were applied and evaluated. The concentration results of the active ORS methods are compared to those estimated by a Lagrangian stochastic atmospheric dispersion model. Our results reveal that passive OP-FTIR is a valuable tool for the rapid detection and imaging of emission sources and the spatial tracer gas distribution; while with active OP-FTIR and TDLAS, C₂H₂ concentrations in the sub-ppm range could be quantified that correlated well with the concentration data obtained by our modeling approach.     

Electrical conductivity measurements on olivines and pyroxenes under defined thermodynamic activities as a function of temperature and pressure

Electrical conductivities of Ni₂SiO₄, Fe₂SiO₄, and MgSiO₃ were measured on synthetic powders in the temperature range 340° to 1,100° C and at pressures up to 20 kbars. For ternary compounds such as olivines and pyroxenes the control of two further variables, like the chemical activities of two components are needed, besides temperature and pressure. The activities of the corresponding binary oxides were controlled by equilibrating the samples with their neighbour-phases. Control of the oxygen partial pressure was achieved by buffer techniques. From the slopes of the lg σ vs. 1/T lines the activation energies were calculated for 10 kbar: 0.56 eV and 2.7 eV for Ni₂SiO₄ in equilibrium with SiO₂ and Ni/NiO-buffer for the temperature range 500°–800°C and 800°–1,000°C resp. 0.52 eV for Fe₂SiO₄ in equilibrium with SiO₂ and metallic iron, and 0.38 eV in equilibrium with SiO₂ and magnetite; 1.11 eV for MgSiO₃ in equilibrium with SiO₂, and 1.25 eV in equilibrium with Mg₂SiO₄.     

A Sm-Nd isotopic study of the South Harris Igneous Complex,the Outer Hebrides

Sm-Nd geochronology may be used to bracket the age of metamorphism in rocks which are difficult to date by other methods. By coupling whole rock Sm-Nd analyses of the principal members of the South Harris Igneous Complex, with Sm-Nd mineral isochrons on two anothositic gabbros, the age of granulite facios metamorphism has been defined. Whole rock analyses of three pairs of closely spaced samples of the anorthosite give consistent ages averaging 2.18±0.06 Gyr, but in general the data from the anorthosite do not define an isochron as a result of variable contamination of the evolving magma chamber. Whole rock data on the tonalite indicate that it is younger than 2.06 Gyr; its mean T_CHUR age is 1.86±0.05 Gyr. Garnet-pyroxene-amphibole-plagioclase mineral isochrons on two anorthosite samples give identical 1.87±0.04 Gyr ages which date cooling after the high pressure granulite facies metamorphism. Together with the tonalite whole rock data this defines the age of that metamorphism and confirms Dearnley's original assignment of an early Laxfordian age.     

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.     

Decomposition of fayalite (Fe2SiO4) in an oxygen potential gradient at 1,418 K

The decomposition of fayalite (Fe₂SiO₄) in oxygen potential gradients is studied at T=1,418 K. The compound will be decomposed into its component oxides wüstite, Fe_1?δO, and silica, SiO₂, by the simultaneous action of two different oxygen partial pressures, exceeding a critical ratio, despite the fact that fayalite is stable at both the lower and the higher oxygen potential. A quantitative analysis of the decomposition process caused by defect fluxes within the bulk Fe₂SiO₄ is given.     

Study of pocyclic aromatic hydrocarbons at a pressure of 6–9 GPa with X-ray diffraction and synchrotron radiation

This work is one of the stages of study of the deep C-O-H fluid and investigates the behavior of polycyclic aromatic hydrocarbons (PAHs) under conditions of the Earth’s mantle. The composition of the C-O-H fluid in the upper mantle is estimated as a mixture of H₂O and CH₄ with a minor amount of H₂ and heavier hydrocarbons. Some theoretical calculations show that the stability of heavy hydrocarbons (alkanes, alkenes, and PAHs) increases with an increase in temperature. This paper presents the results of an XRD study of PAHs stability in multianvil presses on a Spring-8 accelerator (Japan). The primary compositions were chosen according to the abundance of PAHs in nature. In situ diffraction spectrums were recorded to determine the PAHs stability field. It was established that the PAHs become unstable at a pressure of 6–9 GPa and a temperature of 873–1073 K.     

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   

Synthetic Mn3+-kyanite and viridine, (Al2-xMn x 3+ ) SiO5, in the system Al2O3-MnO-MnO2-SiO2

Experiments on the join Al₂SiO₅-“Mn₂SiO₅” of the system Al₂O₃-SiO₂-MnO-MnO₂ in the pressure/temperature range 10–20 kb/900–1050° C with gem quality andalusite, Mn₂O₃, and high purity SiO₂ as starting materials and using /_O2-buffer techniques to preserve the Mn³⁺ oxidation state had following results: At 20 kb/1000°C orange-yellow kyanite mixed crystals are formed. The kyanite solid solubility is limited at about (Al_1.88Mn _0.12 ³⁺ )SiO₅ and, thus, equals approximately that on the join Al₂SiO₅-“Fe₂SiO₅” (Langer and Frentrup, 1973) indicating that there is no Jahn-Teller stabilisation of Mn³⁺ in the kyanite matrix. 5 mole % substitution causes the kyanite lattice constants a _o, b _o, c _o, and V _o to increase by 0.015, 0.009, 0.014 Å, and 1.6 ų, resp., while α, β, γ, remain unchanged. Between 10 and 18 kb/900°C, Mn³⁺-substituted, strongly pleochroitic (emeraldgreen-yellow) andalusite_ss (viridine) was obtained. At 15 kb/900°C, the viridine compositional range is about (Al_1.86Mn _0.14 ³⁺ )SiO₅-(Al_1.56Mn _0,44 ³⁺ )SiO₅. Thus, Al→Mn³⁺ substitutional degrees are appreciably higher in andalusite than in kyanite, proving a strong Jahn-Teller effect of Mn³⁺ in the andalusite structure, which stabilises this structure type at the expense of kyanite and sillimanite and, thus, enlarges its PT-stability range extremely. 17 mole % substitution cause the andalusite constants a _o, b _o, c _o, and V _o to increase by 0.118, 0.029, 0.047 Å and 9.4 ų, resp. At “Mn₂SiO₅”-contents smaller than about 7 mole %, viridine coexists with Mn-poor kyanite. At “Mn₂SiO₅”-concentrations higher than the maximum kyanite or viridine miscibility, braunite (tetragonal, ideal formula Mn²⁺Mn³⁺[O₈/Si0₄]), pyrolusite and SiO₂ were found to coexist with the Mn³⁺-saturated ky _ss or and _ss, respectively. In both cases, braunites were Al-substituted (about 1 Al for 1 Mn³⁺). Pure synthetic braunites had the lattice constants a _o 9.425, c _o, 18.700 Å, V _o 1661.1 ų (ideal compn.) and a _o 9.374, c _o 18.593 ų, V _o 1633.6 ų (1 Al for 1 Mn³⁺). Stable coexistence of the Mn²⁺-bearing phase braunite with the Mn⁴⁺-bearing phase pyrolusite was proved by runs in the limiting system MnO-MnO₂-SiO₂.     

Rainfall input of toxaphene to a South Carolina estuary

Toxaphene concentrations in rainfall over a South Carolina salt marsh were monitored from 1976–1978. This insecticide is toxic to some organisms in the low μg/kg range and causes sublethal effects in the very low ng/kg range. Rainfall was sampled by both continuously exposed collectors and by collectors which were exposed only during actual precipitation. Toxaphene concentrations in individual rainstorms showed a high day-to-day variation, and in general were 10–100 times higher than PCB and DDT levels. Washout ratios for toxaphene were higher than those reported for other chlorinated hydrocarbons, but lower than those of trace metals. During and immediately following the summer use season, toxaphene levels in rain exceeded by several times those concentrations reported to produce bone damage to young fish in laboratory experiments. The estimated aerial input of toxaphene to the 26 km² estuary was 1.2 kg over a 4-month period. Most of this input appeared to be due to rainfall rather than dry deposition. *** DIRECT SUPPORT *** A01BY010 00007     

Some examples of the Middle-Triassic Marine transgression in South-Western Mediterranean Europe

In Southwestern Mediterranean Europe (NE Spain, Sardinia and NW Apennines e. g. Monti Pisani and Punta Bianca) the Middle-Triassic transgression on a margin of an intracratonic basin appears to be controlled by the different morphology and tectonic activity of the margin itself. The analysis of some sequences leads to recognize three different kinds of margins:

1. margin with a narrow shelf sloping toward a very shallow restricted basin (Central and Southwestern Sardinia);
2. margin with a broad shelf gently sloping toward a shallow basin (NE Spain, Monti Pisani, NW Sardinia);
3. margin with a narrow shelf and steep slope marked by tectonic and volcanic activity (Punta Bianca).

     

Polycyclic aromatic hydrocarbons in surface sediments of Binacional Itaipu Lake,Brazil: characteristics,sources and toxicity evaluation

Itaipu Lake, which includes the Itaipu hydroelectric power plant, is one of the largest dams in the world and has a strong relationship with its surroundings. The flooded area has multiple uses such as navigation, recreation, water abstraction for industrial, urban and agricultural irrigation. The lake is located at the frontier between Brazil, Argentina and Paraguay. In this study, superficial sediments collected from nine sampling sites were analysed for grain size, organic matter and 16 priority polycyclic aromatic hydrocarbons (PAHs) using high-performance liquid chromatography (HPLC) with fluorescence detector. The total concentration of PAHs in the dry sediment ranged from 35.21 to 685.37 µg kg^?1. Diagnostic ratios showed that the possible source of PAHs in the Itaipu Lake could be pyrolitic and petrogenic. The potential toxicity of sediment of PAHs varied from not detected to 127.70 µg g^?1, suggesting that some adverse ecological effects would arise due to PAHs in these sediments.     

‘Indicator’ carbonaceous phyllite/graphitic schist in the Archean Kundarkocha gold deposit,Singhbhum orogenic belt,eastern India: Implications for gold mineralization vis-a-vis organic matter

Carbonaceous rocks in the form of graphitic schist and carbonaceous phyllite are the major host rocks of the gold mineralization in Kundarkocha gold deposit of the Precambrian Singhbhum orogenic belt in eastern India. The detection of organic carbon, essentially in the carbonaceous phyllite and graphitized schist within the Precambrian terrain, is noted from this deposit. A very close relationship exists between gold mineralization and ubiquitous carbonaceous rocks containing organic carbon that seems to play a vital role in the deposition of gold in a Precambrian terrain in India and important metallogenetic implications for such type of deposits elsewhere. However, the role played by organic matter in a Precambrian gold deposit is debatable and the mechanism of precipitation of gold and other metals by organic carbon has been reported elsewhere. Fourier transform infrared spectroscopy (FTIR) results and total organic carbon (TOC) values suggest that at least part of the organic material acted as a possible source for the reduction that played a significant role in the precipitation of gold. Lithological, electron probe analysis (EPMA), fluid inclusions associated with gold mineralization, Total Carbon (TC), TOC and FTIR results suggest that the gold mineralization is spatially and genetically associated with graphitic schist, carbonaceous phyllite/shale that are constituted of immature organic carbon or kerogen. Nano-scale gold inclusions along with free milling gold are associated with sulfide mineral phases present within the carbonaceous host rocks as well as in mineralized quartz-carbonate veins. Deposition of gold could have been facilitated due to the organic redox reactions and the graphitic schist and carbonaceous phyllite zone may be considered as the indicator zone.     

Carbon on surfaces of magnesium oxide and olivine single crystals. Diffusion from the bulk or surface contamination?

We have conducted detailed studies of the behavior of carbon on the surfaces of MgO and olivine single crystals using various surface analytical techniques: viz. secondary ion mass spectrometry (SIMS), Auger electron spectrometry (AES) and X-ray photoelectron spectrometry (XPS). In order to distinguish without ambiguity the effect of diffusion of carbon from the bulk to the surface and the effect of surface contamination by carbon-containing species, the experiments were conducted in ultrahigh vacuum, i.e. 10^?11–10^?9 torr. In addition to MgO and olivine single crystals, we have conducted the same studies on TiO₂, MnO, SiO₂ and Ta₂O₅ which serve as blank samples. The MgO and olivine samples were also intentionally implanted with known doses of carbon and the mobility of this particular carbon was investigated in detail. Our results show that the bulk carbon content in MgO is around 40 wt. ppm, considerably lower than the quantities quoted by Freund and co-workers in the past. We also show that the carbon in both MgO and olivine does not display any rapid diffusion behaviour leading to surface segreation in the temperature range 78–723 K, in contrast to the previous findings of Freund and co-workers.     

Infrared vibrational spectra of Beta-Phase Mg2SiO4 and Co2SiO4 to Pressures of 27 GPa

Infrared absorption spectra of the high-pressure polymorphs β-Mg₂SiO₄ and β-Co₂SiO₄ have been measured between 0 and 27 GPa at room temperature. Grüneisen parameters determined for 11 modes of β-Mg₂SiO₄ (frequencies of 300 to 1,050 cm^?1) and 5 modes of β-Co₂SiO₄ (490 to 1,050 cm^?1) range between 0.8 and 1.9. Averaging the mid-infrared spectroscopic data for β-Mg₂SiO₄ yields an average Grüneisen parameter of 1.3 (±0.1), in good agreement with the high-temperature thermodynamic value of 1.35. Similarly, we find a value of 1.05 (±0.2) for the average spectroscopic Grüneisen parameter of β-Co₂SiO₄.