Cation distribution in amphiboles synthesized along the Ga analogue of the tremolite–aluminotschermakite join

 Amphiboles were synthesized from bulk compositions prepared along the join Ca_1.8Mg_5.2Si₈O₂₂(OH)₂–Ca_1.8Mg₃Ga₄Si₆O₂₂(OH)₂ hydrothermally at 750–850 °C and 1.0–1.8 GPa, and along the join Ca₂Mg₅Si₈O₂₂F₂–Ca₂Mg₃Ga₄Si₆O₂₂F₂, anhydrously at 1000 °C and 0.7 GPa to document how closely the tschermak-type substitution is obeyed in these analogues of aluminous amphiboles. Electron-microprobe analyses and Rietveld X-ray diffraction structure refinements were performed to determine cation site occupancies. The extent of Ga substitution was found to be limited in both joins, but with the fluorine series having about twice the Ga content (0.6 atoms per formula unit, apfu) of the hydroxyl-series amphiboles (0.3 apfu). The tschermak-type substitution was followed very closely in the hydroxyl series with essentially equal partitioning of Ga between tetrahedral and octahedral sites. The fluorine-series amphiboles deviated significantly from the tschermak-type substitution and, instead, appeared to follow a substitution that is close to a Ca-pargasite substitution of the type: ^[6]Ga³⁺+2^[4]Ga³⁺+1/2^[A] Ca²⁺ = ^[6]Mg²⁺+2^[4]Si⁴⁺+1/2^[A]□. Infrared spectroscopy revealed an inverse correlation between the intensity of the OH-stretching bands and the Ga content for the hydroxyl- and fluorine-series amphiboles. The direct correlation between the Ga and F content and inverse relationship between the Ga and OH content may be a general phenomenon present in other minerals and suggests, for example, that high F contents in titanite are controlled by the Al content of the host rock and that there may be similar direct Al–F correlations in tschermakitic amphiboles. Evidence for the possibility that Al (Ga) might substitute onto only a subset of the tetrahedral sites in tschermakitic amphiboles was sought but not observed in this study. Received: 5 March 2001 / Accepted: 31 July 2001     

Low-temperature thermodynamic properties of disordered zeolites of the natrolite group

 The heat capacity of paranatrolite and tetranatrolite with a disordered distribution of Al and Si atoms has been measured in the temperature range of 6–309 K using the adiabatic calorimetry technique. The composition of the samples is represented with the formula (Na_1.90K_0.22Ca_0.06)[Al_2.24Si_2.76O₁₀]·nH₂O, where n=3.10 for paranatrolite and n=2.31 for tetranatrolite. For both zeolites, thermodynamic functions (vibrational entropy, enthalpy, and free energy function) have been calculated. At T=298.15 K, the values of the heat capacity and entropy are 425.1 ± 0.8 and 419.1 ±0.8 J K⁻¹ mol⁻¹ for paranatrolite and 381.0 ± 0.7 and 383.2 ± 0.7 J K⁻¹ mol⁻¹ for tetranatrolite. Thermodynamic functions for tetranatrolite and paranatrolite with compositions corrected for the amount of extraframework cations and water molecules have also been calculated. The calculation for tetranatrolite with two water molecules and two extraframework cations per formula yields: C _p (298.15)=359.1 J K⁻¹ mol⁻¹, S(298.15) −S(0)=362.8 J K⁻¹ mol⁻¹. Comparing these values with the literature data for the (Al,Si)-ordered natrolite, we can conclude that the order in tetrahedral atoms does not affect the heat capacity. The analysis of derivatives dC/dT for natrolite, paranatrolite, and tetranatrolite has indicated that the water- cations subsystem within the highly hydrated zeolite may become unstable at temperatures above 200 K. Received: 30 July 2001 / Accepted: 15 November 2001     

Thermal expansion and crystal structure of FeSi between 4 and 1173 K determined by time-of-flight neutron powder diffraction

The thermal expansion and crystal structure of FeSi has been determined by neutron powder diffraction between 4 and 1173?K. No evidence was seen of any structural or magnetic transitions at low temperatures. The average volumetric thermal expansion coefficient above room temperature was found to be 4.85(5)?×?10^?5?K^?1. The cell volume was fitted over the complete temperature range using Grüneisen approximations to the zero pressure equation of state, with the internal energy calculated via a Debye model; a Grüneisen second-order approximation gave the following parameters: θ_D=445(11)?K, V ₀=89.596(8)?ų, K ₀′=4.4(4) and γ′=2.33(3), where θ_D is the Debye temperature, V ₀ is V at T=0?K, K ₀′ is the first derivative with respect to pressure of the incompressibility and γ′ is a Grüneisen parameter. The thermodynamic Grüneisen parameter, γ_th, has been calculated from experimental data in the range 4–400?K. The crystal structure was found to be almost invariant with temperature. The thermal vibrations of the Fe atoms are almost isotropic at all temperatures; those of the Si atoms become more anisotropic as the temperature increases.     

Electrons in feldspar II: a consideration of the influence of conduction band-tail states on luminescence processes

 Most natural feldspars contain many charged impurities, and display a range of bond angles, distributed about the ideal. These effects can lead to complications in the structure of the conduction band, giving rise to a tail of energy states (below the high-mobility conduction band) through which electrons can travel, but with reduced mobility: transport through these states is expected to be thermally activated. The purpose of this article is twofold. Firstly, we consider what kind of lattice perturbations could give rise to both localized and extended conduction band-tail states. Secondly, we consider what influence the band tails have on the luminescence properties of feldspar, where electrons travel through the sample prior to recombination. The work highlights the dominant role that 0.04–0.05-eV phonons play in both the luminescence excitation and emission processes of these materials. It also has relevance in the dating of feldspar sediments at elevated temperatures. Received: 11 May 2001 / Accepted: 6 September 2001     

A three-dimensional parametric study of the use of soil nails for stabilising tunnel faces

Applying an effective nailing system at a tunnel heading, not only improves the stability of the tunnel heading and limits deformation at the tunnel face, but it also reduces volume loss during excavation and hence reduces ground surface settlement. The effectiveness of a soil nail system is affected by many factors such as the diameter and stiffness of the nails. In this paper, a systematic parametric study was conducted to study the axial rigidity of a nail, E_nA_n, for improving the stability of tunnel headings and reducing ground movements in stiff clay. The parametric study involved a series of three-dimensional elasto-plastic coupled-consolidation finite element analyses. The stability of the tunnel face is improved with increasing E_nA_n. For a given nail density applied at the tunnel face, an optimum axial rigidity of the nail (E_nA_n)_opt can be identified. The efficiency of the nailing system diminishes when (E_nA_n)_opt is reached. The use of a soil nailing system reduces the magnitude of stress relief at the tunnel heading during excavation. Thus, this reduction of stress relief minimises the amount of soil yielding and excess pore water pressure generated in the soil around the tunnel heading.     

Petrology of two diamondiferous eclogite xenoliths from the Lahtojoki kimberlite pipe, eastern Finland

Diamondiferous Group A eclogites constitute a minor portion of the mantle-derived xenoliths in the eastern Finland kimberlites. They have been derived from the depth interval 150–230 km where they are inferred to occur as thin layers or small pods within coarse-grained garnet peridotites. The chemical and isotopic composition of minerals suggest that they represent (Proterozoic?) mantle-derived melts or cumulates rather than subducted oceanic lithosphere. During magma ascent and emplacement of the kimberlites, the eclogite xenoliths were mechanically and chemically rounded judging from the types of surface markings. In addition, those octahedral crystal faces of diamonds that were partially exposed from the rounded eclogite xenolith became covered by trigons and overlain by microlamination due to their reaction with the kimberlite magma. The diamonds bear evidence of pervasive plastic deformation which is not, however, evident in the eclogite host. This suggests that annealing at ambient lithospheric temperatures has effectively recrystallised the silicates while the diamond has retained its lattice imperfections and thus still has the potential to yield information about ancient mantle deformation. One of our samples is estimated to contain approximately 90,000 ct/ton diamond implying that some diamonds occur within very high-grade pods or thin seams in the lithospheric mantle. To our knowledge, this is one of the most diamondiferous samples described.     

Cathodoluminescence of authigenic albite

Authigenic albites in carbonate rocks typically grow in a high-grade diagenetic to low-grade metamorphic environment and often show Roc-Tourné-twinning sensu Füchtbauer. Based on an investigation of four Middle to South European occurrences, they show Mn²⁺- and Fe³⁺-activated cathodoluminescence (CL), as revealed by combined high resolution spectroscopy of cathodoluminescence emission (HRS-CL), electron paramagnetic resonance (EPR), and proton-induced X-ray emission (μPIXE).     

Intercomparison of IRS-P4-MSMR derived geophysical products with DMSP-SSM/I and TRMM-TMI finished products

In this paper, MSMR geophysical products like Integrated Water Vapour (IWV), Ocean Surface Wind Speed (OWS) and Cloud Liquid Water (CLW) in different grids of 50, 75 and 150 kms are compared with similar products available from other satellites like DMSP-SSM/I and TRMMTMI. MSMR derived IWV, OWS and CLW compare well with SSM/I and TMI finished products. Comparison of MSMR derived CLW with that derived from TMI and SSM/I is relatively in less agreement. This is possibly due to the use of 37 GHz in SSM/I and TMI that is highly sensitive to CLW, while 37 GHz channels are not available on MSMR. Monthly comparison of MSMR geophysical products with those from TMI is all carried out for climatological purpose. The monthly comparisons were much better compared to instantaneous comparisons. In this paper, details of the data analysis and comparison results are presented. The usefulness of the MSMR vis-à-vis other sensors is also discussed.     

Anhydrite-bearing rocks from the Rožná district (Moldanubian zone,Czech Republic): high-grade metamorphosed exhalites?

Several types of anhydrite-bearing rocks have been found in the amphibolite-facies metamorphosed rocks at the north-eastern margin of the Moldanubian Zone. Anhydrite either forms monomineralic bands up to 40 cm thick, or occurs in the form of disseminated grains in surrounding calc-silicate gneiss together with feldspar, scapolite, amphibole, pyroxene, epidote and pyrite. The isotopic composition of sulphur ('³⁴S=30.6 to 32.3‰) and strontium (⁸⁷Sr/⁸⁶Sr=0.70797 to 0.70781) in anhydrite may indicate a marine source of sulphate. The isotopic ratio of strontium is in the same range as that of metamorphosed strata-bound barite-sulphide ores, which have been previously described in the same area. The '³⁴S values of coexisting pyrite range from 21.4 to 22.5‰, the (³⁴S_{anhydrite-pyrite} corresponding to the metamorphic temperature of 600 to 660 °C. In contrast to many submarine-exhalative deposits, the oxygen isotopic compositions of anhydrite ('¹⁸O=9.3 to 10.2‰) are lighter than that of barite ('¹⁸O=10.4 to 13.8‰). This indicates that the both minerals are not in isotopic equilibrium. Therefore, it is probable that anhydrite and barite from the Ro—ná district were deposited from fluids that contained different proportions of seawater and hydrothermal fluids or from hydrothermal fluids that underwent variable extent of oxygen isotope exchange with seafloor rocks. The '¹³C values in calcite ('¹³C=-17.2 to -18.7‰) from anhydrite-bearing rock are lower than those in distant marbles. As graphite is absent in anhydrite- and calcite-bearing rocks, impoverishment in the ¹³C isotope cannot be attributed to the graphite-carbonate isotopic exchange during metamorphism. It is proposed that low '¹³C values in carbonates are caused by pre-metamorphic oxidation of organic matter in course of hydrothermal processes. Anhydrite and anhydrite-bearing calc-silicate gneiss from the north-eastern part of the Moldanubian Zone are interpreted to be the high-grade metamorphosed analogue of anhydrite-rich exhalites commonly found in submarine-exhalative hydrothermal deposits.