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.     

Nitrogen and oxygen isotopic compositions of water-soluble nitrate in Taihu Lake water system, China: implication for nitrate sources and biogeochemical process

The stable isotope nitrogen-15 (¹⁵N) is a robust indicator of nitrogen (N) source, and the joint use of δ¹⁵N and δ¹⁸O–NO₃ ^? values can provide more useful information about nitrate source discrimination and N cycle process. The δ¹⁵N and δ¹⁸O–NO₃ ^? values, as well as major ion tracers, from Taihu Lake in east China were investigated to identify the primary nitrate sources and assess nitrate biogeochemical process in the present study. The results show that the nitrate concentration in West Taihu Lake (WTL) was generally higher than those in East Taihu Lake (ETL) and its upstream inflow rivers. The NO₃ ^?/Cl^? value combined with mapping of δ¹⁵N–NO₃ ^? and NO₃ ^? concentration suggest that the mixing process should play a major effect in WTL, and denitrification was the dominant N transformation process in WTL. A linear relationship of close to ~1: 2 was observed between δ¹⁵N–NO₃ ^? and δ¹⁸O–NO₃ ^? values in WTL, confirming the occurrence of denitrification in WTL. The δ¹⁵N–NO₃ ^? data imply that sewage and manure were the principal nitrate sources in WTL and its feeder rivers, while the nitrate in ETL might derive from soil organic nitrogen and atmospheric deposition. The δ¹⁸O–NO₃ ^? data indicate most of nitrate from microbial nitrification of organic nitrogen matter possibly make a significant contribution to the lake.     

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.     

Rock composition and origin of the Duwi Formation calcareous rocks, Upper Egypt

Upper Cretaceous phosphorite beds of the Duwi Formation, Upper Egypt, are intercalated with limestone, sandy limestone, marl, calcareous shales, and calcareous sandstone. Calcareous intercalations were subjected to field and detailed petrographic, mineralogical and geochemical investigations in order to constrain their rock composition and origin. Mineralogically, dolomite, calcite, quartz, francolite and feldspars are the non-clay minerals. Smectite, kaolinite and illite represent the clay minerals. Major and trace elements can be classified as the detrital and carbonate fractions based on their sources. The detrital fraction includes the elements that are derived from detrital sources, mainly clay minerals and quartz, such as Si, Al, Fe, Ti, K, Ba, V, Ni, Co, Cr, Zn, Cu, Zr, and Mo. The carbonate fraction includes the elements that are derived from carbonates, maily calcite and dolomite, such as Ca, Mg and Sr. Dolomite occurs as being dense, uniform, mosaic, very fine-to-fine, non-ferroan, and non-stoichiometrical, suggesting its early diagenetic formation in a near-shore oxidizing shallow marine environment. The close association and positive correlation between dolomite and smectite indicates the role of clay minerals in the formation of dolomite as a source of Mg^2＋ -rich solutions. Calcareous rocks were deposited in marine, oxidizing and weakly alkaline conditions, marking a semi-arid climatic period. The calcareous/argillaceous alternations are due to oscillations in clay/carbonate ratio.     

Petrology and geochemistry of xenoliths from the Northern Baltic shield: evidence for partial melting and metasomatism in the lower crust beneath an Archaean terrane

Lower crustal xenoliths entrained in a Paleozoic ultramafic lamprophyre breccia pipe on Elovy island, Kola peninsula, Russia, represent some of the oldest lower crustal material yet investigated from Europe. The xenoliths vary from feldspar-poor, garnetrich rocks which resemble eclogites, to feldspar-rich garnet granulites. Quartz-rich felsic granulites, as well as pyroxenites and amphibole-rich rocks are also present.

The mafic granulites/eclogites represent a suite of gabbros and norites that is related by olivine fractionation. The igneous protoliths may have formed in a manner analogous to lower crustal rocks from most other European xenolith localities, i.e. by basaltic underplating, but magmatic cumulates are not in evidence.

The Kola lower crust was subjected to one or more metasomatic events which introduced up to 45% phlogopite and/or amphibole into both eclogites/granulites and pyroxenites. The resulting rocks have strong enrichments in Rb, Ba, and K, indicating that the lower crust is not uniformly depleted in LIL and heat-producing elements. Siliceous (65% SiO₂) and mafic (< 50% SiO₂) lithologies coexist in migmatitic xenoliths, which provide evidence for partial melting processes and restite formation in mafic metaigneous lower crust. The relationship, if any, between partial melting and metasomatism is unclear.     

Phase relations of biotite and stilpnomelane in the greenschist facies

Phase relations of biotite and stilpnomelane and associated silicate minerals have been studied in rocks of the greenschist facies, chiefly from Otago, New Zealand and western Vermont, but also from Scotland, Minnesota-Michigan iron range, and northwest Washington. That stilpnomelane in the greenschicht facies crystallizes initially with nearly all iron in the ferrous state is indicated by chemical analyses, high p-T experiments, and phase relationships. Alteration of stilpnomelane after metamorphism not only oxidizes iron but leaches potassium; corrections for both effects must be made in using analyses of brown stilpnomelane in studies of phase relations. Two discontinuous reactions which produce biotite at the biotite isograd have been identified:

1. muscovite+stilpnomelane+actinolite→ biotite+chlorite+epidote
2. chlorite+microcline→ biotite+muscovite. Biotite produced by the first of these reactions has a limited range of variation in Fe/Mg. As grade advances within the biotite zone more magnesian and ferruginous biotites become stable in consequence of the two continuous reactions:
3. muscovite+actinolite+chlorite→ biotite (Mg-rich)+epidote
4. muscovite+stilpnomelane→ biotite (Fe-rich)+chlorite.

Stilpnomelane is stable in muscovite-free rocks throughout the biotite zone, and even up to the grade at which hornblende becomes stable. Phengitic muscovite is stable throughout the biotite zone in New Zealand and thus apparently does not contribute to the formation of biotite until a higher grade is reached.     

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.     

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.