Natrolite,part I: Refinement of high-order data,separation of internal and external vibrational amplitudes from displacement parameters

A single crystal of natrolite, Na₂Al₂Si₃O₁₀·2H₂O, was studied by X-ray diffraction methods at room temperature. The intensities were measured with MoKα radiation (λ = 0.7107 Å) in a complete sphere of reflection up to sin θ/λ = 0.903 Å^?1. The structure was refined in the orthorhombic space group Fdd2 with a = 18.2929 (7) Å, b = 18.6407(9) Å, c = 6.5871(6) Å, V = 2246 ų, Z = 8. A refinement of high-order diffraction data yielded reliability factors of R(F) = 0.9%, R _w(F) = 0.8%, GoF = 1.40 for 1856 high-angle reflections (0.7 ?in θ/λ <0.903 Å^?1) and R(F) = 1.0%, R _W(F) = 1.2%, GoF = 3.07 for all 3471 independent reflections in the complete sphere of reflection. The T-O distances as well as the T-O-T angles were found to be strongly influenced by the different bond strengths received by the individual oxygen atoms. The T O distances calculated using Baur's extended valence rule agree on average within 0.003 Å with the observed values. An analysis of the mean square displacement amplitudes allowed a separation of the external and internal vibrational amplitudes along the T-O bonds as well as along the Na O and H₂O-O bond directions and the calculation of force constants. The internal vibrational amplitudes (ΔU) of the T-O vibrations are in the range of 5 to 11 × 10^-4 Ų, that is about one order of magnitude smaller than the mean square displacement amplitudes of the external vibrations. The corresponding force constants are F = 354 to 824 Nm^?1. The values of the force constants of the motion of the Na-ion and the water molecule against the framework oxygen atoms lie in the range between F = 57 and 293 Nm^?1. This is the first instance where displacement amplitudes from a zeolite structure refinement could be apportioned between contributions from internal and external vibrations for individual bonds.     

http://www.sciencedirect.com/science/article/pii/S167498711100079X

Lower Paleozoic rocks exposed in various regions of Egypt (south central Sinai, north Eastern Desert and southwest Western Desert), in addition to occurring in the subsurface such as north Western Desert and the Gulf of Suez. The Lower Paleozoic rocks in Egypt include surface and subsurface rock units of formational status. The surface rock units are the Taba, Araba and Naqus formations. The subsurface rock units include the Shifa, Kohla and Basur formations. The Infracambrian Taba Formation has been discovered recently in the outcrops of the south eastern Sinai in the Taba-Ras El-Naqab area. It is missing and/or not recognized in the subsurface. The Taba Formation consists mainly of reddish brown, unfossiliferous gravelly fine-to medium-grained sandstones cemented by kaolinite and have subordinate beds of paleosols. The Cambrian Araba Formation and its subsurface equivalent (the Shifa Formation) are essentially composed of reddish brown, fine-grained laminated sandstone and siltstone with abundant Skolithos and Cruziana sp. In contrast, the Ordovician-Silurian Naqus Formation and its subsurface equivalents (Kohla Formation and Basur Formation) are mainly composed of white, unfossiliferous, cross-bedded, medium- to coarse-grained sandstones with haphazardly distributed pebbles and cobbles. Sedimentological analysis indicates that the Araba Formation and its equivalents were deposited in a marginal-marine environment, whereas the Naqus Formation and its equivalents were laid down in a fluvio-glacial environment. Integrated stratigraphic and sedimentological studies of the Lower Paleozoic rocks permit reconstruction of the paleogeography of Egypt at that time. Egypt has been largely controlled since the Cambrian by the pre-existing structural framework of the pre-Phanerozoic basement rocks inherited from the Late Proterozoic Pan-African event. Additionally, sedimentation processes were controlled during Cambro-Ordovician times by tectonic movements, whereas glacio-eustatic control predominated during the Late Ordovician-Silurian Period. These studies suggest that most areas of Egypt were exposed lands with episodically transgression by epicontinental seas related to the paleo-Tethys. These lands formed a part of a stable subsiding shelf at the northern Gondwana margin.     

A subsidiary fast-diffusing substitution mechanism of Al in forsterite investigated using diffusion experiments under controlled thermodynamic conditions

Diffusion of Al in synthetic forsterite was studied at atmospheric pressure from 1100 to 1500 °C in air along [100] with activities of SiO₂, MgO and Al₂O₃ (a_SiO2, a_MgO and a_Al2O3) buffered. At low a_SiO2, the buffer was forsterite + spinel + periclase (fo + sp + per) at all temperatures, while at high a_SiO2 and subsolidus conditions a variety of three-phase assemblages containing forsterite and two other phases from spinel, cordierite, protoenstatite or sapphirine were used at 1100–1350 °C. Experiments at high a_SiO2 and 1400 °C used forsterite + protoenstatite + melt (fo + en + melt), and at 1500 °C, fo + melt. The resulting diffusion profiles were analysed by LA–ICP–MS in scanning mode. Diffusion profiles in the high a_SiO2 experiments were generally several hundred microns in length, but diffusion at low a_SiO2 was three orders of magnitude slower than in high a_SiO2 experiments carried out at the same temperature, producing short profiles only a few microns in length and close to the spatial resolution of the analytical method. Interface concentrations of Al in the forsterite, obtained by extrapolating the diffusion profiles to the crystal/buffer interface, were only a fraction of those expected at equilibrium, and varied among the differing buffer assemblages according to (a_Al2O3)^1/2 and (a_SiO2)^3/4, pointing to the substitution of Al in forsterite by an octahedral-site, vacancy-coupled (OSVC) component with the stoichiometry Al _4/3 ³⁺ vac_2/3SiO₄, whereas the main substitution expected from previous equilibrium studies would be the coupled substitution of 2 Al for Mg + Si, giving the stoichiometry MgAl₂O₄. It is proposed that this latter substitution is not seen on the length scales of the present experiments because it requires replacement of Si by Al on tetrahedral sites, and is accordingly rate-limited by the slow diffusivity of Si. Instead, diffusion of Al by the OSVC mechanism is relatively fast, and at high a_SiO2, even faster than Fe–Mg interdiffusion.     

Hydrogeochemical prospecting for porphyry copper deposits in the tropical-marine climate of Puerto Rico

A hydrogeochemical survey utilizing waters from streams and springs was conducted in the area of two known porphyry copper deposits in the tropical-marine climate of westcentral Puerto Rico. The most important pathfinder for regional hydrogeochemical surveys is sulfate which reflects the associated pyrite mineralization. Because of increased mobility due to intense chemical weathering and the low pH environment, dissolved copper can also be used as a pathfinder for regional surveys and has the advantage of distinguishing barren pyrite from pyrite associated with copper mineralization. For follow-up surveys, the most important pathfinders are copper, sulfate, pH, zinc, and fluoride. High concentrations of dissolved copper and moderate concentrations of sulfate is a diagnostic indication of nearby sources of copper minerals.An understanding of the geochemical processes taking place in the streambeds and the weathering environment, such as the precipitation of secondary copper minerals, contributes to the interpretation of the geochemical data and the selection of the most favorable areas for further exploration.     

Structure of Cu-bearing orthopyroxene, Mg(Cu.56,Mg.44)Si2O6, and behavior of Cu2+ in the orthopyroxene structure

Cu-bearing pyroxene, Mg(Cu.₅₆,Mg.₄₄)Si₂O₆, has been synthesized by a flux method and crystal structure refinement has been performed by single crystal X-ray diffraction. It is found that the crystal structure is orthorhombic (space group Pbca) with unit cell dimensions of a=18.221(4), b=8.890(1), c=5.2260(7)Å and the cell volume of 846.5( )3ų. In the M2-site one of the M-O bonds(M-O3B) is extremely expanded from 2.444(2) in enstatite to 2.732(2), thus the coordination polyhedron around M2-site is regarded as square pyramidal rather than square planar or octahedral. It is also found that the M1-site in the pyroxene structure is occupied almost exclusively by Mg, while the M2-site is almost evenly occupied by Mg and Cu. The observed extreme site preference shown by Cu²⁺ is unusual among the divalent cations with similar ionic sizes.     

Graphite in Kupferschiefer (Poland) and its genetic meaning

Graphite forms crystals up to 0.08 mm in size in carbonates or argillaceous carbonates directly under- and overlying black shale. Increased contents of Si, Al, Ca, and K in graphite are related to intercalations of graphite-montmorillonite and less to intercalations of graphite-illite. Quartz and gibbsite are also detected. The formation of graphite was probably a two-stage process:

1. Catalytic oxidation of organic matter. As a result of oxidation original organic matter has been enriched as aromatic hydrocarbons (benzene ring compounds) being most resistant to oxidation.
2. Ordering of conjugated benzene rings on the 001 montmorillonite plane as a matrix. As a result, the c₀ of dry montmorillonite increased to 1.678±0.020 or 2.450±0.050 nm. Primary layers of graphite became themselves matrices for the next layers of conjugated rings producing microscopically visible graphite.

To a less extent the process of dehydrogenesis and conjugation of aromatic rings took place in a reaction with Al, Si, and OH of phyllosilicates producing Al(OH)₃ (gibbsite), former H₄SiO₄ (now quartz), and H₂O.     

地气法－找深部金矿的新方法

介绍一种八十年代发展起来的找深部金矿的新方法一地气法。文中讨论了地气法的找矿机理，认为是地壳中上升气流将成矿元素微粒携带至地表而造成多元素异常。对工作方法着重讨论了地气采样与测试的系统，以及比较了积累式取样的效果。最后列出山东招远地区大尹格庄金矿８０号勘探线的地气测量多元素异常图。     

Enrichment of Rare Earth Elements during magmatic and post-magmatic processes: a case study from the Loch Loyal Syenite Complex, northern Scotland

Concern about security of supply of critical elements used in new technologies, such as the Rare Earth Elements (REE), means that it is increasingly important to understand the processes by which they are enriched in crustal settings. High REE contents are found in syenite-dominated alkaline complexes intruded along the Moine Thrust Zone, a major collisional zone in north-west Scotland. The most northerly of these is the Loch Loyal Syenite Complex, which comprises three separate intrusions. One of these, the Cnoc nan Cuilean intrusion, contains two mappable zones: a Mixed Syenite Zone in which mafic melasyenite is mixed and mingled with leucosyenite and a Massive Leucosyenite Zone. Within the Mixed Syenite Zone, hydrothermal activity is evident in the form of narrow altered veins dominated by biotite and magnetite; these are poorly exposed and their lateral extent is uncertain. The REE mineral allanite is relatively abundant in the melasyenite and is extremely enriched in the biotite–magnetite veins, which have up to 2 % total rare earth oxides in bulk rock analyses. An overall model for development of this intrusion can be divided into three episodes: (1) generation of a Light Rare Earth Element (LREE)-enriched parental magma due to enrichment of the mantle source by subduction of pelagic carbonates; (2) early crystallisation of allanite in melasyenite, due to the saturation of the magma in the LREE; and (3) hydrothermal alteration, in three different episodes identified by petrography and mineral chemistry, generating the intense enrichment of REE in the biotite–magnetite veins. Dating of allanite and titanite in the biotite–magnetite veins gives ages of c. 426 Ma, overlapping with previously published crystallisation ages for zircon in the syenite.     

Mean flow-transient perturbation interaction in the Southern Hemisphere: a simulation using a variable-resolution GCM

The ability of an atmospheric general circulation model to reproduce fundamental features of the wintertime extratropical Southern Hemisphere (SH) circulation is evaluated with emphasis on the daily variability of the SH mean flow and the mean flow-transient perturbations interaction. Two 10-year simulations using a new version of the LMDZ GCM with a stretched grid scheme centered at 45 °S and forced by climatological SST are performed: a high (144Ꮡ) and low (64Ꭹ) horizontal resolution runs. The performance of both simulations was determined by comparing several simulated fields (zonal wind, temperature, kinetic energy, transient eddy momentum and heat fluxes, Eliassen-Palm fluxes, Eady growth rate and baroclinic conversion term) against the European Centre for Medium Range Weather Forecast reanalyses (ERA). High and low-resolution simulations are similar in many respects; in particular, both experiments reproduce the main patterns of the southern extratropical large-scale circulation satisfactorily. Increasing resolution does not improve universally some spurious aspects of the low resolution simulation (e.g. the cold bias in the high polar troposphere, the debilitated subtropical jet, the low baroclinic conversion rate). Those aspects present little sensitivity to the model resolution. The interaction between transient eddies and zonal mean flow are examined. The low-resolution experiment is able to qualitatively represent the acceleration/deceleration of the mean flow by transient perturbations, south/north of 30 °S with an accuracy similar to that of the high-resolution experiment. Although both experiments represent the baroclinic structure of the mean flow satisfactorily, the model underestimates some transient properties due to the underestimation of the baroclinic conversion term in middle latitudes. Such misrepresentation does not improve with increasing resolution and is related to the relatively weak meridional temperature gradient and the inadequate geographical distribution of the eddy heat fluxes. In particular, the eddy kinetic energy is always underestimated. Eddy kinetic energy does not improve convincingly with increasing resolution, suggesting that the adequate representation of the storm tracks is highly influenced by the physical parametrizations.     

On characteristics of wind direction fluctuations in the surface layer

It is shown that the ratio of standard deviation of lateral velocity to the friction velocity, /u _*, and therefore wind direction fluctuations, are sensitive to mesoscale terrain properties. Under neutral conditions, /u _* is almost 40% larger in rolling terrain than over a horizontal surface. In the lee of a low mountain, the fluctuations may be 2.5 times as strong as over horizontal terrain. In contrast, vertical velocity fluctuations are little influenced by mesoscale terrain features.Now with Air Weather Service, Offutt AFB, Omaha, Nebraska.