Raman spectroscopic study of K-lingunite at various pressures and temperatures

K-lingunite is a high-pressure modification of K-feldspar that possesses the tetragonal hollandite structure. Variations of the Raman spectra of K-lingunite were studied up to ~31.5 GPa at room temperature, and in the range 79–823 K at atmospheric pressure. The Raman frequencies of all bands were observed to increase with increasing pressure, and decrease with increasing temperature for K-lingunite. This behavior is in line with those observed for most of other materials. New sharp Raman bands appear at pressures greater than 13–15 GPa, suggesting a phase transition in K-lingunite with increasing pressure. The transition is reversible when pressure was released. The appearance of these new Raman bands may correspond to the phase transition revealed earlier at around 20 GPa by X-ray diffraction studies. Instead of transforming back to its stable minerals, such as orthoclase, microcline or sanidine, K-lingunite became amorphous in the temperature range 803–823 K at atmospheric pressure.     

Geochronology of zircon megacrysts from nepheline-bearing gneisses as constraints on tectonic setting: implications for resetting of the U-Pb and Lu-Hf isotopic systems

Nepheline-bearing gneisses from the 75 km² Tambani body in the Mozambique Belt of southern Malawi, are miaskitic biotite-nepheline monzodiorites, reflecting an absence of K-feldspar, alkali amphiboles or pyroxenes, and contain euhedral zircon megacrysts up to 5 cm across. The zircons contain U = 1–1,860 ppm, Th = 0–2,170 ppm and Y = 400–1,100 ppm, and very low concentrations of all other measured trace elements except Hf (HfO₂ = 0.53–0.92 wt. %). Cathodoluminescence images reveal oscillatory sector growth zoning and no evidence for xenocrystic cores, indicating that the zircons represent primary magmatic crystallization products that have survived amphibolite grade metamorphism. U-Pb isotopic analyses (by TIMS) yield an upper intercept age of 730 ± 4 Ma (MSWD = 1.7), which we interpret as the time of magmatic crystallization of the zircons. This is coincident with 11 SHRIMP spot analyses, which yield a mean age of 729 ± 7 Ma (MSWD = 0.37). Metamorphism, at 522 ± 17 Ma as suggested by monazite, caused partial Pb-loss during local recrystallization of zircon. Lu-Hf isotopic data for three whole-rock samples of nepheline-bearing gneiss are collinear with those for zircon megacrysts, and correspond to an age of 584 ± 17 Ma (MSWD = 0.37. We interpret the Lu-Hf array to represent a mixing line defined by the Hf isotopic signature of primary zircon and that of the rock-forming minerals reset during metamorphic (re-)crystallization; hence the 584 Ma age is likely geologically meaningless. Given the well-defined association of nepheline syenites (and phonolitic volcanic equivalents) with continental rifting, we suggest that the Tambani body represents a magmatic product formed at 730 Ma during the break-up of the Rodinia supercontinent. The 522 Ma age is akin to other Pan-African metamorphic ages that record collisional suturing events during the final assembly of Gondwana. Zircon-bearing nepheline gneisses thus preserve a record of intra-continental rifting and of continental collision in southern Malawi.     

Glauconites from the Late Palaeocene — Early Eocene Naredi Formation,western Kutch and their genetic implications

Glauconitic minerals are considered as one of the valuable input parameters in sequence stratigraphic analysis of a basin. In the present study glauconitic minerals are reported from subtidal green shale facies in the lower part of the Late Paleocene-Early Eocene Naredi Formation of western Kutch. On the basis of the foraminiferal assemblage the glauconite bearing beds are interpreted to have formed in a mid shelf depositional settings of an unstable marine conditions. XRD studies confirm the glauconite mineralogy of the green pellets and provide an estimation of glauconite maturity. Textural attributes of the glauconites confirm their derivation by different degrees of alteration of precursor feldspar grains. Because of the authigenic origin and autochthonous nature, these glauconites hold promise for understanding sequence stratigraphy of the Palaeogene succession of the western Kutch.     

Petrology,geochemistry and geochronology of the Chilka Lake igneous complex,Orissa state,India

The Chilka Lake igneous complex of Orissa, the largest known anortosite massif of the Indian Shield, occurs in a catazonal environment of high-grade metamorphics of the Eastern Ghats Precambrian Orogenic Province. The syntectonic massif consists of the anorthositic Balugaon dome, leuconoritic Rambha lobe and quartz-mangeritic Kallikota cover. A completely gradational suite comprising anorthosite-leuconorite-norite-minor jotunite (the anorthositic suite) constitutes most of the complex. The subordinate of suite of acid rocks spatially associated with this is of a broad quartz-mangeritic lithology with minor granitic rocks (the acidic suite). Geochemical evolution of the complex in the sequence anorthosite-leuconorite-norite-jotunite-acidic rocks shows moderate iron enrichment in the noritic-jotunitic stage and is marked by an overall decrease in Al₂O₃, CaO, MgO, Ni/Co, Sr/Ba, K/Rb and increase in SiO₂, K₂O, V/Ni, K/Ba and Rb/Sr. Such progressive variation in geochemical parameters appears (i) essentially gradual and frequently overlapping in rock members of the intergradational anorthositic suite and (ii) rather abrupt across transition zones between the anorthositic suite and the acidic suite due to near absence of intervening intermediate lithologies. RbSr whole rock isochron studies indicate that the complex was emplaced ca. 1400 Ma ago. The initial ⁸⁷Sr/⁶⁸Sr (0.70661) implies limited hybridisation of the parent magma prior to emplacement. A critical appraisal of all the available evidence suggests that (i) the anorthositic suite of rocks form a perfectly consanguinous and comagmatic assemblage and (ii) the spatially associated acidic suite emerged through a convergence of magmatic and metasomatic processes (the latter brought about by contact anatexis of the host rocks). The complex as well as the host metamorphics are intruded by an atectonic suite of noritic dykes emplaced ca 850 Ma ago.     

Traces of brine and hydrocarbon migration in carbon,oxygen, and sulfur isotopic compositions of reservoir rocks in the Talakan petroleum field,Southwestern Yakutia

Dolomites from the productive Osa horizon (upper subformation of the Lower Cambrian Bilir Formation) in the Talakan petroleum field show a prominent 1–2‰ decrease in δ¹⁸O (from 23–24 to 21–22‰), which presumably marks a zone of relatively high water/rock ratios. Productive boreholes are characterized by moderate δ³⁴S values (from 25.1 to 30.6‰) and negative correlation between δ³⁴S in anhydrite and δ¹⁸O in associated dolomite, which points to a partial sulfate reduction during catagenesis. In nonproductive borehole, δ³⁴S values increase significantly (from 31.4 to 35.6‰) and show positive correlation with δ¹⁸O in dolomite. Rocks recovered by nonproductive borehole possibly recrystallized during early diagenesis, and, correspondingly lost their permeability and capacity to form pores. Limestones and dolomites of the Osa horizon have a carbon isotopic composition within the range of normal marine carbonates (δ¹³C = 0 ± 1 ‰), which does not indicate a significant role of organic matter in postsedimentary recrystallization of carbonate sediments. A positive δ¹³C excursion up to 4.5‰ recorded in the lower subformation of the Bilir Formation presumably occurred at the sedimentation stage under conditions of high rates of bioproductivity and organic matter burial in sediments.     

Stratigraphic status,age, and paleobathymetry of the Grey shale Member,Dalmiapuram Formation,Cauvery Basin,India

Grey shale Member of the Dalmiapuram Formation, Ariyalur Group, Cauvery Basin, India was studied for its stratigraphic position, age, and paleobathymetry with a re-look into the lithological relationship and foraminifer assemblages in the deepened limestone mine excavations at M/s Dalmia Cements, Dalmiapuram. Twenty grey shale samples from Kovandankurchchi (pit-4) and Kallakkudi mines yielded diversified calcareous, benthic, and rare index planktic foraminifera. The foraminiferal assemblages suggest a latest Albian age and middle neritic depositional conditions. The abundance of kaolinite and smectite clay minerals relate to warm/humid climate which corroborate with rising relative sea level during grey shale deposition. The grey shale occurs in patches within the marl bedded limestone member which exhibits cyclic deposition of limestone and marl. The limestone mine sections demonstrate that the grey shale forms part of basal marl bedded limestone, directly overlying the coral algal limestone. The present study demonstrates that the grey shale outcrops in Dalmiapuram Formation should be placed stratigraphically as part of marl bedded limestone. The member status for grey shale which is current usage stands discounted.     

Silicate globules in kyanite from grospydites of the Zagadochnaya kimberlite pipe,Yakutia: The problem of the origin

The results of complex study of silicate globules and α-quartz paramorphs after coesite in kyanite from grospydites from the Zagadochnaya kimberlite pipe, Yakutia, using optical and scanning electron spectroscopy, electron and ion microprobes, LA ICP MS and Raman spectroscopy, are presented. The existence of radial fractures diverging from silicate globules into the matrix (kyanite) attests to the fact that the content of the globules is extremely condensed. A zonal structure is usually typical for globules: a coat and a core, which can be explicitly distinguished under the electron microscope, can be differentiated in them. Compositionally, the coat of the globule corresponds to potassium feldspar (wt %: 66.4 SiO₂; 16.9 Al₂O₃; 0.4 FeO; 0.1 CaO; 0.2 Na₂O; 14.7 K₂O). The globules were also detected in which along with K, a high content of Na and Ca was also ascertained in the silicate coat. The globule coat is considerably enriched with Ba, La, Ce, Nb, and a number of other noncompatible elements as compared with xenolith minerals. The water content in globules is ∼0.6 wt %. As compared with the host mineral (kyanite), the core part of the globules is also enriched with Co, Ni, Zn, and Cu; their content in kyanite is negligibly low. The entire data collection attests to the fact that the formation of silicate globules could have been caused by interaction of the conservated fluid and/or water-silicate melt with the host mineral and crystalline inclusions of clinopyroxene and garnet with decreasing pressure during the transportation of grospydite xenoliths by the kimberlite melt to the Earth’s surface.     

A modeling of the structure and favorable H-docking sites and defects for the high-pressure silica polymorph stishovite

Employing first-principles methods, the docking sites for H were determined and H, Al, and vacancy defects were modeled with an infinite periodic array of super unit cells each consisting of 27 contiguous symmetry nonequivalent unit cells of the crystal structure of stishovite. A geometry optimization of the super-cell structure reproduces the observed bulk structure within the experimental error when P1 translational symmetry was assumed and an array of infinite extent was generated. A mapping of the valence electrons for the structure displays mushroom-shaped isosurfaces on the O atom, one on each side of the plane of the OSi₃ triangle in the nonbonded region. An H atom, placed in a cell near the center of the super cell, was found to dock upon geometry optimization at a distance of 1.69 Å from the O atom with the OH vector oriented nearly perpendicular to the plane of the triangle such that the OH vector makes a angle of 91° with respect to [001]. However, an optimization of a super cell with an Al atom replacing Si and an H atom placed nearby in a centrally located cell resulted in an OH distance of 1.02 Å with the OH vector oriented perpendicular to [001] as observed in infrared studies. The geometry-optimized position of the H atom was found to be in close agreement with that (0.44, 0.12, 0.0) determined in an earlier study of the theoretical electron density distribution. The docking of the H atom at this site was found to be 330 kJ mol^–1 more stable than a docking of the atom just off the shared OO edge of the octahedra as determined for rutile. A geometry optimization of a super cell with a missing Si generated a vacant octahedra that is 20% larger than that of the SiO₆ octahedra. The valence electron density distribution displayed by the two-coordinate O atoms that coordinate the vacant octahedral site is very similar to those displayed by the bent SiOSi angles in coesite. The internal distortions induced by the defect were found to diminish rather rapidly with distance, with the structure annealing to that observed in the bulk crystal to within about three coordination spheres.     

Green synthesis of magnetic mesoporous silica nanocomposite and its adsorptive performance against organochlorine pesticides

Green synthesis of nanomaterials has received increasing attention as an eco-friendly technology in materials science. Here, we have used two types of extractions from green tea leaf (i.e., total extraction and tannin extraction) as reducing agents for a rapid, simple and one-step synthesis method of mesoporous silica nanoparticles/iron oxide nanocomposite based on deposition of iron oxide onto mesoporous silica nanoparticles. Mesoporous silica nanoparticles/iron oxide nanocomposite were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, energy-dispersive X-ray, vibrating sample magnetometer, N₂ adsorption and high-resolution transmission electron microscopy. Mesoporous silica nanoparticles/iron oxide nanocomposite was used as a solid adsorbent for removal of lindane pesticide from aqueous solutions. The developed system possesses the advantages of silica as core that include large surface area and advantages of iron oxide (shell) that include the capability to interact with chlorinated compounds and ability to release by using external magnetic field. UV-Vis technique was used as a simple and easy method for monitoring the removal of lindane. Effects of pH and temperature on the removal efficiency of the developed mesoporous silica nanoparticles/iron oxide nanocomposite toward lindane pesticide were also investigated. Fourier transform infrared spectroscopy, high-performance liquid chromatography and gas chromatography techniques were used to confirm the high ability of mesoporous silica nanoparticles/iron oxide nanocomposite for sensing and the capture of lindane molecules with high sorption capacity (about 99%) that could develop a new eco-friendly strategy for detection and removal of pesticide and as a promising material for water treatment.     

Development of Tide–Surge Interaction Model for the Coastal Region of Bangladesh

In this paper, a two-dimensional, vertically integrated hydrodynamic model is developed taking into account entrained air bubbles during storm surges as well as incorporating inverted barometer, and river and land dynamics. The model is specifically designed for the coastal region of Bangladesh. A nested scheme method with a fine mesh scheme (FMS), capable of incorporating the complex coastline and all major offshore islands accurately, nested into a coarse mesh scheme (CMS) covering up to 15° N latitude in the Bay of Bengal is used. To incorporate the small and big offshore islands in the Meghna estuarine region with its complex coastline accurately, a very fine mesh scheme (VFMS) is again nested into the FMS. Along the northeast corner of the VFMS, the Meghna river discharge is taken into account. The coastal and island boundaries are approximated through proper stair steps. The model equations are solved by a semi-implicit finite difference technique using a staggered C-grid. A stable appropriate tidal condition over the model domain is generated by applying tidal forcing with the four major tidal constituents M ₂, S ₂, K ₁, and O ₁ along the southern open boundary of the CMS. This tidal regime is introduced as the initial state of the sea for nonlinear interaction of tide and surge. The model is applied to simulate water levels due to the interaction of tide and surge associated with the cyclones April 1991 and Aila at different coastal and island locations along the coast of Bangladesh. The results are found to be quite satisfactory with root mean square error of ～0.50 m as calculated for both the storm events. Tests of sensitivities on water levels are carried out for air bubbles, offshore islands, river discharge, inverse barometer, and grid resolution. The presence of air bubbles increases simulated water levels a little bit in our model, and the contribution of air bubbles in increasing water level is found around 2 %. Further, water levels are found to be influenced by offshore islands, river discharge, inverse barometer as well as grid resolution.