Non‐mass‐dependent oxygen isotopic fractionation in smokes produced in an electrical discharge     

Yuki Kimura  Joseph A. Nuth  Subrata Chakraborty  Mark H. Thiemens 《Meteoritics & planetary science》2007,42(7-8):1429-1439

Abstract— We report the first production of non‐mass‐dependently fractionated silicate smokes from the gas phase at room temperature from a stream of silane and/or pentacarbonyl iron in a molecular hydrogen (or helium) flow mixed with molecular oxygen (or nitrous oxide). The smokes were formed at the Goddard Space Flight Center (GSFC) at total pressures of just under 100 Torr in an electrical discharge powered by a Tesla coil, were collected from the surfaces of the copper electrodes after each experiment and sent to the University of California at San Diego (UCSD) for oxygen isotopic analysis. Transmission electron microscopy studies of the smokes show that they grew in the gas phase rather than on the surfaces of the electrodes. We hypothesize at least two types of fractionation processes occurred during formation of the solids: a mass‐dependent process that made isotopically lighter oxides compared to our initial oxygen gas composition followed by a mass‐independent process that produced oxides enriched in ¹⁷O and ¹⁸O. The maximum Δ¹⁷O observed is + 4.7‰ for an iron oxide produced in flowing hydrogen, using O2 as the oxidant. More typical displacements are 1–2‰ above the equilibrium fractionation line. The chemical reaction mechanisms that yield these smokes are still under investigation.  相似文献   

Aluminous orthopyroxene: Order-disorder,thermodynamic properties,and petrologic implications     

Jibamitra Ganguly  Subrata Ghose 《Contributions to Mineralogy and Petrology》1979,69(4):375-385

Orthopyroxene has two tetrahedral sites, designated A and B, and two octahedral sites, M1 and M2. Crystallographic studies of synthetic and natural orthopyroxenes (opx) suggest that the tetrahedral Al is ordered nearly completely in the B site, but the octahedral Al disorders between M1 and M2 sites with a preference for M1. If the aluminum avoidance principle is obeyed, then the tetrahedral Si-Al ordering limits the Al substitution in opx to 25 mol%, thus leading to an end-member stoichiometry of Mg₃Al₂Si₃O₁₂ instead of MgAl₂SiO₆.The enthalpy of formation of these two components has been deduced from the available phase equilibrium data. The thermodynamic properties of the opx solid solution approximates ideal solution behavior more closely when treated in terms of the components Mg₄Si₄O₁₂(QEn)-Mg₃Al₂Si₃O₁₂(Py) than when expressed in terms of the components Mg₂Si₂O₆-MgAl₂SiO₆. A model has been developed for the octahedral disordering of Al as function of temperature and composition. These data enable calculation of the configurational entropy and molar entropy of Al-opx; distinction has been made between the cases of completely random mixing of Al and Si in the tetrahedral B site, and of random mixing without violation of the aluminum avoidance principle. The second model yields entropy of the Mg₃Al₂Si₃O₁₂ end member which agrees almost exactly with the value derived from phase equilibrium data. The partial molal entropies of the Orthopyroxene components QEn and Py can be derived from these data; their implications with respect to the P-T slopes of Al₂O₃ isopleths for the equilibrium of Orthopyroxene with forsterite and spinel/garnet have been discussed.  相似文献   

Analbite → monalbite transition in a heat treated twinned amelia albite     

Fujio P. Okamura  Subrata Ghose 《Contributions to Mineralogy and Petrology》1975,50(3):211-216

Amelia albite annealed at > 1080 °C for 3200 hrs by Duba and Piwinskii (1974) shows very fine twin lamellae (～1 μm) after the albite law, suggesting that it once underwent transformation into monalbite. A fragment of this specimen was investigated at 27 °C, 300 °C, 550 °C, 800 °C and 930 °C using the high-temperature precession technique. As the temperature increases, the splitting angle of c ^*-axes (likewise c ^*-axes) of two twin individuals continues to decrease. The photographs taken at 930 °C show that these two splitting angles have converged to 0^o, indicating completion of the transformation into monalbite. The transition point we observe supports the results of MacKenzie (1952) (920±20 °C) and Grundy et al. (1967) (930 °C) rather than those of Sueno et al. (1973) and Prewitt et al. (1974) (> 1080 °C); the discrepancy is most likely due to the differences in the degree of Al-Si disorder of the samples used in the experiments.  相似文献   

Lattice dynamics and inelastic neutron scattering from forsterite,Mg2SiO4: Phonon dispersion relation,density of states and specific heat     

K. R. Rao  S. L. Chaplot  Narayani Choudhury  Subrata Ghose  J. M. Hastings  L. M. Corliss  D. L. Price 《Physics and Chemistry of Minerals》1988,16(1):83-97

Magnesium-rich olivine (Mg_0.9Fe_0.1)₂SiO₄ is considered to be a major constituent of the Earth's upper mantle. Because of its major geophysical importance, the temperature and pressure dependence of its crystal structure, elastic and dielectric constants, long-wavelength phonon modes and specific heat have been measured using a variety of experimental techniques. Theoretical study of lattice dynamics provides a means of analyzing and understanding a host of such experimental data in a unified manner. A detailed study of the lattice dynamics of forsterite, Mg₂SiO₄, has been made using a crystal potential function consisting of Coulombic and short-range terms. Quasiharmonic lattice dynamical calculations based on a rigid molecular-ion model have provided theoretical estimates of elastic constants, long-wavelength modes, phonon dispersion relation for external modes along the three high symmetry directions in the Brillouin zone, total and partial density of states and inelastic neutron scattering cross-sections. The neutron cross-sections were used as guides for the coherent inelastic neutron scattering experiment on a large single crystal using a triple axis spectrometer in the constant Q mode. The observed and predicted phonon dispersion relation show excellent agreement. The inelastically scattered neutron spectra from a powder sample have been analyzed on the basis of a phonon density of states calculated from a rigid-ion model, which includes both external and internal modes. The experimental data from a powder sample show good agreement with the calculated spectra, which include a multiphonon contribution in the incoherent approximation. The computed phonon densities of states are used to calculate the specific heat as a function of temperature using both the rigid molecular-ion and rigid ion models. These results are in very good agreement with the calorimetric measurement of the specific heat. The interatomic potential developed here can be used with some confidence to study physical properties of forsterite as a function of pressure and temperature.  相似文献   

Electron delocalization and magnetic behavior in a single crystal of ilvaite,a mixed valence iron silicate     

D. Ghosh  T. Kundu  S. Dasgupta  Subralā Ghose 《Physics and Chemistry of Minerals》1987,14(2):151-155

Ilvaite, Ca(Fe²⁺, Fe³⁺)Fe²⁺Si₂O₈(OH), a black mixed valence iron silicate shows considerable Fe²⁺?Fe³⁺ electron delocalization above 400 K, reminiscent of magnetite. A crystallographic phase transition from orthorhombic (Pnam) to monoclinic (P2 ₁/a) symmetry takes place on cooling at 343 K induced by electron ordering. In both phases, Fe²⁺ and Fe³⁺ occur in double octahedral chains parallel to the c axis. The thermal characteristics of the magnetic susceptibilities and their anisotropies in different crystallographic planes have been measured in the temperature range 400?21 K. Below 343±1K, a continuous rotation of the molar susceptibility K _∥ in the ab plane down to 90±2 K is observed, where the symmetry of the magnetic ellipsoid remains unchanged. X _a, X _b and X _c increase abruptly below 123±0.5 K, although antiferromagnetic ordering of Fe²⁺ and Fe³⁺ spins on A sites was suggested in previous Mössbauer and neutron powder diffraction studies. In addition, 1/X _a shows an antiferromagnetic maximum at 50±3 K, whereas 1/X _b and 1/X _c at first increase sharply below 123 K, followed by antiferromagnetic curvatures in the lowest temperature region. This behavior is consistent with the antiferromagnetic ordering of Fe²⁺ spins in the B sites. The observed magnetic phenomena suggest charge delocatization effects between adjacent Fe²⁺(A)-Fe³⁺(A) pairs not only along c, but also along a and b directions. The negative sign of the molar anisotropy (K _∥-K_⊥) suggests a singlet ground State ⁵A₁ for the Fe²⁺ ions, in agreement with previous Mössbauer studies.  相似文献   

A dynamical model for the I\bar 1 - P\bar 1 phase transition in anorthite,CaAl2Si2O8     

Dorian M. Hatch  Subrata Ghose 《Physics and Chemistry of Minerals》1989,16(6):614-620

The non-ferroic triclinic to triclinic \(I\bar 1 - P\bar 1\) phase transition in anorthite is described in terms of the spontaneous onset of an order parameter η. A triclinic to triclinic phase transition can be driven by order parameters (representations) arising from the Γ, Z, X, U, V, R, Y, and T points of symmetry of the Brillouin zone. Each point leads to a set of two inequivalent representations and thus there is a total of sixteen inequivalent order parameters. However, only the R ₁ ⁺ representation is consistent with the change from the body-centered to primitive cell (increase of primitive cell size of two) and also with the origin of the two space groups (inversion center) being at the same position. The R ₁ ⁺ order parameter of the high symmetry triclinic phase \(P\bar 1_0\) (or equivalently \(I\bar 1\) ) causes a reciprocal lattice change and, in terms of the lower symmetry reciprocal lattice, the order parameter corresponds to the b^* point. This is consistent with experimentally observed x-ray diffuse scattering. Using induced representation theory, microscopic distortions compatible with the R ₁ ⁺ order parameter are obtained. Assuming a distortion in an arbitrary direction at the general 2(i) Wyckoff position (x₀,y₀,z₀) of \(P\bar 1_0\) (the higher symmetry phase) induced representation theory demands an opposite displacement at the position (x₀, y₀, z₀), an opposite displacement at (x₀+1,y₀+1,z₀+1), and the same displacement at ( \(\bar x\) ₀+1, \(\bar y\) ₀+1, \(\bar z\) ₀+1) of \(P\bar 1_0\) . This is also consistent with experiment. The presence of the weak c-type reflections above the transition is attributed to the fluctuating lower symmetry antiphase domains related by the translation (1/2, 1/2, 1/2).  相似文献   

The α-β phase transition in AlPO4 cristobalite: Symmetry analysis,domain structure and transition dynamics     

Dorian M. Hatch  Subrata Ghose  John L. Bjorkstam 《Physics and Chemistry of Minerals》1994,21(1-2):67-77

Despite their crystallographic differences, the mechanisms of the α-β phase transitions in the cristobalite phases of SiO₂ and AlPO₄ are very similar. The β→α transition in AlPO₄ cristobalite is from cubic ( $\left( {F\bar 43m} \right)$ ) to orthorhombic (C222₁), whereas that in SiO₂ cristobalite is from cubic ( $\left( {Fd\bar 3m} \right)$ ) to tetragonal (P4₃2₁2 or P4₁2₁2). These crystallographic differences stem from the fact that there are two distinct cation positions in AlPO₄ cristobalite as opposed to one in SiO₂ cristobalite and the ordered (Al,P) distribution is retained through the phase transition. As a result, there are significant differences in their crystal structures, domain configurations resulting from the phase transition and Landau free energy expressions. A symmetry analysis of the “improper ferroelastic” transition from $F\bar 43m \to C222_1$ in AlPO₄ cristobalite has been carried out based on the Landau formalism and the projection operator methods. The six-component order parameter, η driving the phase transition transforms as the X₅ representation of $F\bar 43m$ and corresponds to the simultaneous translation and rotation of the [AlO₄] and [PO₄] tetrahedra coupled along 110. The Landau free energy expression contains a third order invariant, the minimization of which requires a first-order transition, consistent with experimental results. The tetrahedral configurations of twelve α phase domains resulting from the β→α transition in AlPO₄ cristobalite are of two types: (1) transformation twins from a loss of the 3-fold axis, and (2) antiphase domains from the loss of the translation vectors 1/2[101] and 1/2[011] (F→C). In contrast to α-SiO₂ cristobalite, the α-AlPO₄ cristobalite (C222₁) does not have chiral elements (4₃, 4₁) and hence, enantiomorphous domains are absent. These transformation domains are essentially macroscopic and static in the α phase and microscopic and dynamic in the β phase. The order parameter, η couples with the strain components, which initiates the structural fluctuations causing the domain configurations to dynamically interchange in the β phase. An analysis of the MAS NMR data (²⁹Si, ¹⁷O, ²⁷Al) on the α α-β transitions in SiO₂ and AlPO₄ cristobalites (Spearing et al. 1992, Phillips et al. 1993) essentially confirms the dynamical model proposed earlier for SiO₂ cristobalite (Hatch and Ghose 1991) and yields a detailed picture of the transition dynamics. In both cases, small atomic clusters with the configuration of the low temperature α phase persist considerably above the transition temperature, T₀. The NMR data on the β phases above T₀ cannot be explained by a softening of the tetrahedral rotational and translational modes alone, but require the onset of an order-disorder mechanism resulting in a dynamic averaging due to rapidly changing domain configurations considerably below T₀.  相似文献   

Groundwater resources management through flow modeling in lower part of Bhagirathi — Jalangi interfluve,Nadia, West Bengal     

Sudhir Kumar  Subrata Halder  D. C. Singhal 《Journal of the Geological Society of India》2011,78(6):587-598

Groundwater utilization in Nadia district, West Bengal has been subjected to rapid exploitation in the wake of increasing urbanization and production of agricultural commodities. It is, therefore, necessary to evaluate the existing trend and availability of groundwater in time and space and its movement for proper planning in future. In the present study, an attempt has been made develop a groundwater management model using Visual MODFLOW software. The groundwater flow model for the study area was formulated by using input hydrogeological data and appropriate boundary conditions. The groundwater flow pattern of the study area indicates the occurrence of base flow which feed both the Rivers Bhagirathi and Jalangi throughout the year. The computed hydraulic heads were calibrated by comparing with observed groundwater level data for years 2004 to 2006 and were verified with the data of 2007. The outcome of modeling shows that this model can be used for prediction purpose in the future by updating input boundary conditions and hydrologic stresses during the preceding year. The model optimized unit draft for deep tube well as 556.5 m³/day and the same for shallow tube well as 41 m³/day keeping the existing tube well structures in running condition and maintaining the present and recent past trends of groundwater level. The model can be further improved if more spatial and temporal input parameters are available and can be incorporated into the model for more realistic characterization of groundwater flow.  相似文献   

Radon as seismic precursor: new data with well water of Jalpaiguri,India     

Dipak Ghosh  Argha Deb  Swarup Ranjan Sahoo  Subrata Haldar  Rosalima Sengupta 《Natural Hazards》2011,58(3):877-889

This paper reports the measurement of radon concentration in well water at the site of Jalpaiguri (26°32′N, 88°46′E) near the active fault zone of West Bengal, India. Radon concentration has been measured in well water with the help of solid-state nuclear track detectors (SSNTD). The study indicates a positive correlation between radon anomaly and earthquake. The data of radon content in well water have been compared with that in soil gas at the same site.  相似文献   

Lattice dynamics and raman spectroscopy of protoenstatite,Mg2Si2O6     

Subrata Ghose  Narayani Choudhury  S. L. Chaplot  C. Pal Chowdhury  S. K. Sharma 《Physics and Chemistry of Minerals》1994,20(8):625-625

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