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1.
Christian D. Klose 《Natural Hazards》2007,43(3):303-317
Since the last eruption of the Fossa crater in 1888–1890, intense volcanic degassing has been remaining on Vulcano Island
of Sicily (Italy). Toxic sulfur dioxide (SO2) of the solfataric action in this area represents, when inhaled, a permanent natural hazard harming humans. Approximately
500 permanent residents live and 15,000 tourists visit during the summer time the Porto village in the North of Vulcano Island.
A cross-disciplinary fuzzy logic risk assessment has been conducted to evaluate health risks of human individuals exposed
to higher SO2-concentrations C over certain exposure times t. The simple approach, based on fuzzy set theory, explains health risks semantically by words rather than by numbers. Advantages
of this approach are, first, experts, non-experts, decision makers, or the public are able to understand and communicate risk
degrees by words without using numbers. Second, in comparison to other risk definitions, the risk is not equal to the vulnerability;
it is based on the hazard (SO2-gas clouds) and vulnerability (health effects) in combination. Third, risk levels can be still estimated even when limited
or no statistical information is available, e.g., high SO2-concentrations or long exposure times. Moreover, human health risks were determined for C−t-scenarios based on threshold values of the European Union and the World Health Organization. Independently, two additional
methods were used to determine the proportions of the population who are exposed to levels of SO2 at which health effects may be expected and also safety zones for civil protection around the degassing fields. In conclusion,
SO2-gas concentrations in many parts of Vulcano Island go beyond the proclaimed alert threshold of the European Union and the
World Health Organization. For example, the results show that sensitive individuals, such as asthmatics, young children, or
elderly people, should not be exposed at any time to the degassing areas in Porto di Levante and at the NE-rim of the Fossa
crater. In contrast, healthy non-sensitive individuals should be exposed less than 10 min to the SO2-clouds at these degassing areas, while hiking on the crater rim. 相似文献
2.
We present H2O analyses of MgSiO3 pyroxene crystals quenched from hydrous conditions in the presence of olivine or wadsleyite at 8–13.4 GPa and 1,100–1,400°C.
Raman spectroscopy shows that all pyroxenes have low clinoenstatite structure, which we infer to indicate that the crystals
were high clinoenstatite (C2/c) during conditions of synthesis. H2O analyses were performed by secondary ion mass spectrometry and confirmed by unpolarized Fourier transform infrared spectroscopy
on randomly oriented crystals. Measured H2O concentrations increase with pressure and range from 0.08 wt.% H2O at 8 GPa and 1,300°C up to 0.67 wt.% at 13.4 GPa and 1,300°C. At fixed pressure, H2O storage capacity diminishes with increasing temperature and the magnitude of this effect increases with pressure. This trend,
which we attribute to diminishing activity of H2O in coexisting fluids as the proportion of dissolved silicate increases, is opposite to that observed previously at low pressure.
We observe clinoenstatite 1.4 GPa below the pressure stability of clinoenstatite under nominally dry conditions. This stabilization
of clinoenstatite relative to orthoenstatite under hydrous conditions is likely owing to preferential substitution of H2O into the high clinoenstatite polymorph. At 8–11 GPa and 1,200–1,400°C, observed H2O partitioning between olivine and clinoenstatite gives values of D
ol/CEn between 0.65 and 0.87. At 13 GPa and 1,300°C, partitioning between wadsleyite and clinoenstatite, D
wd/CEn, gives a value of 2.8 ± 0.4. 相似文献
3.
M. Zhang G. J. Redhammer E. K. H. Salje M. Mookherjee 《Physics and Chemistry of Minerals》2002,29(9):609-616
Synthetic aegirine LiFeSi2O6 and NaFeSi2O6 were characterized using infrared spectroscopy in the frequency range 50–2000 cm−1, and at temperatures between 20 and 300 K. For the C2/c phase of LiFeSi2O6, 25 of the 27 predicted infrared bands and 26 of 30 predicted Raman bands are recorded at room temperature. NaFeSi2O6 (with symmetry C2/c) shows 25 infrared and 26 Raman bands. On cooling, the C2/c–P21/c structural phase transition of LiFeSi2O6 is characterized by the appearance of 13 additional recorded peaks. This observation indicates the enlargement of the unit
cell at the transition point. The appearance of an extra band near 688 cm−1 in the monoclinic P21/c phase, which is due to the Si–O–Si vibration in the Si2O6 chains, indicates that there are two non-equivalent Si sites with different Si–O bond lengths. Most significant spectral
changes appear in the far-infrared region, where Li–O and Fe–O vibrations are mainly located. Infrared bands between 300 and
330 cm−1 show unusually dramatic changes at temperatures far below the transition. Compared with the infrared data of NaFeSi2O6 measured at low temperatures, the change in LiFeSi2O6 is interpreted as the consequence of mode crossing in the frequency region. A generalized Landau theory was used to analyze
the order parameter of the C2/c–P21/c phase transition, and the results suggest that the transition is close to tricritical.
Received: 21 January 2002 / Accepted: 22 July 2002 相似文献
4.
R. Bianchi A. Forni F. Cámara R. Oberti H. Ohashi 《Physics and Chemistry of Minerals》2007,34(8):519-527
The synthetic LiGaSi2O6 clinopyroxene is monoclinic C2/c at room-T. Its experimental electron density, ρ(r), has been derived starting from accurate room-T single-crystal diffraction data. Topological analysis confirms an intermediate ionic-covalent character for Si–O bonding,
as found by previous electron-density studies on other silicates such as diopside, coesite and stishovite. The non-bridging
Si–O bonds have more covalent character than the bridging ones. The Ga–O bonds have different bonding characters, the Ga–O2
bond being more covalent than the two Ga–O1 bonds. Li–O bonds are classified as pure closed-shell ionic interactions. Similar
to spodumene (LiAlSi2O6), Li has sixfold coordination, but the bond critical points associated to the two longest bonds are characterized by very
low electron density values. Similar to what previously found in spodumene and diopside, O···O interactions were detected
from the topological analysis of ρ(r), and indicate a cooperative interaction among the lone pairs of neighbouring oxygen atoms. In particular, this kind of interaction
has been obtained for the O1···O1 edge shared between two Ga octahedra. Integration over the atomic basins gives net charges
of −1.39(10), 2.82(10), 1.91(10) and 0.82(8) e for O (averaged), Si, Ga and Li atoms, respectively. Periodic Hartree–Fock
and DFT calculations confirm the results obtained by multipole refinement of the experimental data. Moreover, the theoretical
topological properties of the electron density distribution on the Si2O6 group are very similar to those calculated for spodumene.
Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users. 相似文献
5.
CH4 and CO2 fluxes from a high-cold swamp meadow and an alpine meadow on the Qinghai-Tibetan Plateau, subject to different degrees of
degradation, were measured over a 12-month period. Air temperature, soil temperature and moisture, and the depths of the water
table and thawing-freezing layer were determined. For swamp meadows, the greater the degradation, the lesser the carbon efflux.
CH4 emissions at the nondegraded swamp meadow site were 1.09–3.5 and 2.5–11.27 times greater, and CO2 emissions 1.08–1.69 and 1.41–4.43 times greater, respectively, than those from moderately and severely degraded sites. For
alpine meadows, the greater the degradation, the greater the CH4 consumption and CO2 emissions. CH4 consumption at the severely degraded alpine meadow site was 6.6–21 and 1.1–5.25 times greater, and CO2 emissions 1.05–78.5 and 1.04–6.28 times greater, respectively, than those from the nondegraded and moderately degraded sites.
The CH4 and CO2 fluxes at both sites were significantly correlated (R
2 > 0.59, P < 0.05) with air temperature, soil temperature, and topsoil (0–5 cm depth) moisture, indicating these to be the main environmental
factors affecting such fluxes. 相似文献
6.
In order to model the processes of formation of the highly alkaline (potassic) melts during the partial melting of the eclogite
nodules in kimberlites, experiments on the melting of the model and natural eclogites in presence of the H2O-CO2 and H2O-CO2-KCl fluids at 5 GPa and 1200 and 1300°C are performed. A comparative analysis of the phase relations in the systems with
H2O-CO2 and H2O-CO2-KCl demonstrate that KCl in the fluid equilibrated with eclogites intensifies their melting. It is related to both high Cl
concentration in the forming silicate melt (2.0–5.5 wt %) and its enrichment in K2O owing to the K-Na exchange reactions with the immiscible chloride melt. Because of these reactions, the K2O/Cl ratio in the melts increases with the KCl content in the system and reaches 2.5–3.5 in the silicate melts coexisting
with the immiscible chloride liquid. However, the ratio KCl/(H2O + CO2 + KCl) in the fluid does not influence on the ratio K2O/Cl in the melts. Thus, the solubility KCl in the melts, apparently, does not depend on presence of the H2O-CO2 fluid, at least, within the concentration range used in the experiments (up to 20 wt %). The experiments show that the deliberated
chloride liquid is necessary to form the potassium-rich chlorine-bearing silicate melts during the eclogite melting. It corresponds
to the KCl content in the system above 5 wt %. 相似文献
7.
Basalts interbedded with oil source rocks are discovered frequently in rift basins of eastern China, where CO2 is found in reservoirs around or within basalts, for example in the Binnan reservoir of the Dongying Depression. In the reservoirs, CO2 with heavy carbon isotopic composition (δ13C>-10‰ PDB) is in most cases accounts for 40% of the total gas reserve, and is believed to have resulted from degassing of basaltic magma from the mantle. In their investigations of the Binnan reservoir, the authors suggested that the CO2 would result from interactions between the source rocks and basalts. As the source rocks around basalts are rich in carbonate minerals, volcanic minerals, transition metals and organic matter, during their burial history some of the transition metals were catalyzed on the thermal degradation of organic matter into hydrocarbons and on the decomposition of carbonate minerals into CO2, which was reproduced in thermal simulations of the source rocks with the transition metals (Ni and Co). This kind of CO2 accounts for 55%-85% of the total gas reserve generated in the process of thermal simulation, and its δ13C values range from -11‰- -7.2‰ PDB, which are very similar to those of CO2 found in the Binnan reservoir. The co-generation of CO2 and hydrocarbon gases makes it possible their accumulation together in one trap. In other words, if the CO2 resulted directly from degassing of basaltic magma or was derived from the mantle, it could not be accumulated with hydrocarbon gases because it came into the basin much earlier than hydrocarbon generation and much earlier than trap formation. Therefore, the source rocks around basalts generated hydrocarbons and CO2 simultaneously through catalysis of Co and Ni transition metals, which is useful for the explanation of co-accumulation of hydrocarbon gases and CO2 in rift basins in eastern China. 相似文献
8.
Mineral-specific IR absorption coefficients were calculated for natural and synthetic olivine, SiO2 polymorphs, and GeO2 with specific isolated OH point defects using quantitative data from independent techniques such as proton–proton scattering,
confocal Raman spectroscopy, and secondary ion mass spectrometry. Moreover, we present a routine to detect OH traces in anisotropic
minerals using Raman spectroscopy combined with the “Comparator Technique”. In case of olivine and the SiO2 system, it turns out that the magnitude of ε for one structure is independent of the type of OH point defect and therewith
the peak position (quartz ε = 89,000 ± 15,000
\textl \textmol\textH2\textO-1 \textcm-2\text{l}\,\text{mol}_{{\text{H}_2}\text{O}}^{-1}\,\text{cm}^{-2}), but it varies as a function of structure (coesite ε = 214,000 ± 14,000
\textl \textmol\textH2\textO-1 \textcm-2\text{l}\,\text{mol}_{{\text{H}_2}\text{O}}^{-1}\,\text{cm}^{-2}; stishovite ε = 485,000 ± 109,000
\textl \textmol\textH2\textO-1 \textcm-2\text{l}\,\text{mol}_{{\text{H}_2}\text{O}}^{-1}\,\text{cm}^{-2}). Evaluation of data from this study confirms that not using mineral-specific IR calibrations for the OH quantification in
nominally anhydrous minerals leads to inaccurate estimations of OH concentrations, which constitute the basis for modeling
the Earth’s deep water cycle. 相似文献
9.
L. Ya. Aranovich I. V. Zakirov N. G. Sretenskaya T. V. Gerya 《Geochemistry International》2010,48(5):446-455
New experimental data on the solubility of NaCl in gaseous CO2 were obtained at pressures (P) of 30–70 MPa and temperatures of 623 and 673 K on experimental equipment making possible to sample a portion of the gas
in the course of the experiment. The new measures have demonstrated that the NaCl solubility increases with increasing temperature
(T) and pressure and is approximately four to five orders of magnitude higher than the saturated vapor pressure of NaCl at the
corresponding temperature. The paper also reports newly obtained experimental data on the equilibrium conditions of the reaction
of talc decomposition into enstatite and quartz at a variable H2O/NaCl ratio in the fluid. The results of the experiments validate the empirical equations previously suggested for H2O and NaCl activities in concentrated aqueous salt solutions that can be used in describing silica-saturated fluids at high
T-P parameters. A new empirical equation is suggested for the Gibbs free mixing energy in the H2O-CO2-NaCl ternary system, with the parameters of the equation calibrated against experimental data on phase equilibria in marginal
binary systems and on the location of the boundary of the region of homogeneous three-component fluid according to data on
synthetic fluid inclusions in quartz. 相似文献
10.
Boris Kolesov 《Physics and Chemistry of Minerals》2008,35(5):271-278
Single-crystal polarized Raman spectra (3,000–4,000 cm−1 at 3 ≤ T ≤ 300 K) were measured for synthetic alkali-free and natural beryl, Be2Al3Si6O18·xH2O, to determine the behavior of H2O molecules of both Type I and Type II in the cavities. At low temperature, the H2O molecules of Type I displace from the center of cavity and give rise to very weak hydrogen bonding with the host lattice.
The H2O Type I translational motion is characterized by substantial anharmonicity and looks like a motion of “a particle in the
box” with a frequency of 6.3 cm−1. Water Type II is characterized by a free rotation with respect to the C
2 molecule axis, and it makes possible the water nuclear isomers (i.e. ortho- and para-) to be observed at low temperature.
相似文献
| Boris KolesovEmail: |
11.
The onset of hydrous partial melting in the mantle above the transition zone is dictated by the H2O storage capacity of peridotite, which is defined as the maximum concentration that the solid assemblage can store at P and T without stabilizing a hydrous fluid or melt. H2O storage capacities of minerals in simple systems do not adequately constrain the peridotite water storage capacity because
simpler systems do not account for enhanced hydrous melt stability and reduced H2O activity facilitated by the additional components of multiply saturated peridotite. In this study, we determine peridotite-saturated
olivine and pyroxene water storage capacities at 10–13 GPa and 1,350–1,450°C by employing layered experiments, in which the
bottom ~2/3 of the capsule consists of hydrated KLB-1 oxide analog peridotite and the top ~1/3 of the capsule is a nearly
monomineralic layer of hydrated Mg# 89.6 olivine. This method facilitates the growth of ~200-μm olivine crystals, as well
as accessory low-Ca pyroxenes up to ~50 μm in diameter. The presence of small amounts of hydrous melt ensures that crystalline
phases have maximal H2O contents possible, while in equilibrium with the full peridotite assemblage (melt + ol + pyx + gt). At 12 GPa, olivine and
pyroxene water storage capacities decrease from ~1,000 to 650 ppm, and ~1,400 to 1,100 ppm, respectively, as temperature increases
from 1,350 to 1,450°C. Combining our results with those from a companion study at 5–8 GPa (Ardia et al., in prep.) at 1,450°C,
the olivine water storage capacity increases linearly with increasing pressure and is defined by the relation
C\textH2 \textO\textolivine ( \textppm ) = 57.6( ±16 ) ×P( \textGPa ) - 169( ±18 ). C_{{{\text{H}}_{2} {\text{O}}}}^{\text{olivine}} \left( {\text{ppm}} \right) = 57.6\left( { \pm 16} \right) \times P\left( {\text{GPa}} \right) - 169\left( { \pm 18} \right). Adjustment of this trend for small increases in temperature along the mantle geotherm, combined with experimental determinations
of
D\textH2 \textO\textpyx/olivine D_{{{\text{H}}_{2} {\text{O}}}}^{\text{pyx/olivine}} from this study and estimates of
D\textH2 \textO\textgt/\textolivine D_{{{\text{H}}_{2} {\text{O}}}}^{{{\text{gt}}/{\text{olivine}}}} , allows for estimation of peridotite H2O storage capacity, which is 440 ± 200 ppm at 400 km. This suggests that MORB source upper mantle, which contains 50–200 ppm
bulk H2O, is not wet enough to incite a global melt layer above the 410-km discontinuity. However, OIB source mantle and residues
of subducted slabs, which contain 300–1,000 ppm bulk H2O, can exceed the peridotite H2O storage capacity and incite localized hydrous partial melting in the deep upper mantle. Experimentally determined values
of
D\textH2 \textO\textpyx/\textolivine D_{{{\text{H}}_{2} {\text{O}}}}^{{{\text{pyx}}/{\text{olivine}}}} at 10–13 GPa have a narrow range of 1.35 ± 0.13, meaning that olivine is probably the most important host of H2O in the deep upper mantle. The increase in hydration of olivine with depth in the upper mantle may have significant influence
on viscosity and other transport properties. 相似文献
12.
Adsorption of H2O, NH3 and C6H6 on H- and alkali metal-exchanged structures of mordenite and on corresponding cations on the smectite layer is investigated
by ab initio density-functional calculations. Proton or an alkali metal cation compensates one Al/Si framework substitution
and resides in the extra-framework position of zeolite or above flat smectite layer close to the Al/Si substitution. Pronounced
similarities between zeolite and smectite are observed in changes of the adsorption energies and location of the external
cation with changing character of the external cation. Calculated adsorption energies exhibit the following trend: E(NH3) > E(H2O) > E(C6H6). Because of looser contact with the framework, zeolitic cations are stronger adsorption centers and calculated adsorption
energies of zeolites are by ~20–30% larger than cations of smectites. The highest adsorption energy is calculated for H-exchanged
structures and down the group of alkali metal cations a decrease of the adsorption energy is observed. Deviations from the
smooth variation of the adsorption energy are caused by: (1) formation of strong hydrogen bonds in H-exchanged structures,
(2) adsorption induced migration of the external Li+ cation, and (3) steric hindrances of the flat C6H6 molecule adsorbed on the cation in the cage of zeolite. 相似文献
13.
Planewave pseudopotential calculations of supercell total energies were used as bases for first-principles calculations of
the CaCO3–MgCO3 and CdCO3–MgCO3 phase diagrams. Calculated phase diagrams are in qualitative to semiquantitative agreement with experiment. Two unobserved
phases, Cd3Mg (CO3)4 and CdMg3(CO3)4, are predicted. No new phases are predicted in the CaCO3–MgCO3 system, but a low-lying metastable Ca3Mg(CO3)4 state, analogous to the Cd3Mg(CO3)4 phase is predicted. All of the predicted lowest-lying metastable states, except for huntite CaMg3(CO3)4, have dolomite-related structures, i.e. they are layer structures in which A
m
B
n
cation layers lie perpendicular to the rhombohedral [111] vector.
Received: 6 May 2002 / Accepted: 23 October 2002
Acknowledgements This work was partially supported by NSF contract DMR-0080766 and NIST. 相似文献
14.
Jennifer L. Lewicki George E. Hilley Laura Dobeck Lee Spangler 《Environmental Earth Sciences》2010,60(2):285-297
A field facility located in Bozeman, Montana provides the opportunity to test methods to detect, locate, and quantify potential
CO2 leakage from geologic storage sites. From 9 July to 7 August 2008, 0.3 t CO2 day−1 were injected from a 100-m long, ~2.5-m deep horizontal well. Repeated measurements of soil CO2 fluxes on a grid characterized the spatio-temporal evolution of the surface leakage signal and quantified the surface leakage
rate. Infrared CO2 concentration sensors installed in the soil at 30 cm depth at 0–10 m from the well and at 4 cm above the ground at 0 and
5 m from the well recorded surface breakthrough of CO2 leakage and migration of CO2 leakage through the soil. Temporal variations in CO2 concentrations were correlated with atmospheric and soil temperature, wind speed, atmospheric pressure, rainfall, and CO2 injection rate. 相似文献
15.
Mangrove ecosystems play an important, but understudied, role in the cycling of carbon in tropical and subtropical coastal
ocean environments. In the present study, we examined the diel dynamics of seawater carbon dioxide (CO2) and dissolved oxygen (DO) for a mangrove-dominated marine ecosystem (Mangrove Bay) and an adjacent intracoastal waterway
(Ferry Reach) on the island of Bermuda. Spatial and temporal trends in seawater carbonate chemistry and associated variables
were assessed from direct measurements of dissolved inorganic carbon, total alkalinity, dissolved oxygen (DO), temperature,
and salinity. Diel pCO2 variability was interpolated across hourly wind speed measurements to determine variability in daily CO2 fluxes for the month of October 2007 in Bermuda. From these observations, we estimated rates of net sea to air CO2 exchange for these two coastal ecosystems at 59.8 ± 17.3 in Mangrove Bay and 5.5 ± 1.3 mmol m−2 d−1 in Ferry Reach. These results highlight the potential for large differences in carbonate system functioning and sea-air CO2 flux in adjacent coastal environments. In addition, observation of large diel variability in CO2 system parameters (e.g., mean pCO2: 390–2,841 μatm; mean pHT: 8.05–7.34) underscores the need for careful consideration of diel cycles in long-term sampling regimes and flux estimates. 相似文献
16.
Dmytro M. Trots Alexander Kurnosov Leonid Vasylechko Marek Berkowski Tiziana Boffa Ballaran Daniel J. Frost 《Physics and Chemistry of Minerals》2011,38(7):561-567
A single crystal X-ray diffraction study on lithium tetraborate Li2B4O7 (diomignite, space group I41
cd) has been performed under pressure up to 8.3 GPa. No phase transitions were found in the pressure range investigated, and
hence the pressure evolution of the unit-cell volume of the I41
cd structure has been described using a third-order Birch–Murnaghan equation of state (BM-EoS) with the following parameters:
V
0
= 923.21(6) Å3, K
0
= 45.6(6) GPa, and K′ = 7.3(3). A linearized BM-EoS was fitted to the axial compressibilities resulting in the following parameters a
0
= 9.4747(3) Å, K
0a
= 73.3(9) GPa, K′
a
= 5.1(3) and c
0
= 10.2838(4) Å, K
0c
= 24.6(3) GPa, K′
c
= 7.5(2) for the a and c axes, respectively. The elastic anisotropy of Li2B4O7 is very large with the zero-pressure compressibility ratio β
0c
/β
0a
= 3.0(1). The large elastic anisotropy is consistent with the crystal structure: A three-dimensional arrangement of relatively
rigid tetraborate groups [B4O7]2− forms channels occupied by lithium along the polar c–axis, and hence compression along the c axis requires the shrinkage of the lithium channels, whereas compression in the a direction depends mainly on the contraction of the most rigid [B4O7]2− units. Finally, the isothermal bulk modulus obtained in this work is in general agreement with that derived from ultrasonic
(Adachi et al. in Proceedings-IEEE Ultrasonic Symposium, 228–232, 1985; Shorrocks et al. in Proceedings-IEEE Ultrasonic Symposium, 337–340, 1981) and Brillouin scattering measurements (Takagi et al. in Ferroelectrics, 137:337–342, 1992). 相似文献
17.
Al-containing MgSiO3 perovskites of four different compositions were synthesized at 27 GPa and 1,873 K using a Kawai-type high-pressure apparatus:
stoichiometric compositions of Mg0.975Si0.975Al0.05O3 and Mg0.95Si0.95Al0.10O3 considering only coupled substitution Mg2+ + Si4+ = 2Al3+, and nonstoichiometric compositions of Mg0.99Si0.96Al0.05O2.985 and Mg0.97Si0.93Al0.10O2.98 taking account of not only the coupled substitution but also oxygen vacancy substitution 2Si4+ = 2Al3+ + VO¨. Using the X-ray diffraction profiles, Rietveld analyses were performed, and the results were compared between the stoichiometric
and nonstoichiometric perovskites. Lattice parameter–composition relations, in space group Pbnm, were obtained as follows. The a parameters of both of the stoichiometric and nonstoichiometric perovskites are almost constant in the X
Al range of 0–0.05, where X
Al is Al number on the basis of total cation of two (X
Al = 2Al/(Mg + Si + Al)), and decrease with further increasing X
Al. The b and c parameters of the stoichiometric perovskites increase linearly with increasing Al content. The change in the b parameter of the nonstoichiometric perovskites with Al content is the same as that of the stoichiometric perovskites within
the uncertainties. The c parameter of the nonstoichiometric perovskites is slightly smaller than that of the stoichiometric perovskites at X
Al of 0.10, though they are the same as each other at X
Al of 0.05. The Si(Al)–O1 distance, Si(Al)–O1–Si(Al) angle and minimum Mg(Al)–O distance of the nonstoichiometric perovskites
keep almost constant up to X
Al of 0.05, and then the Si(Al)–O1 increases and both of the Si(Al)–O1–Si(Al) angle and minimum Mg(Al)–O decrease with further
Al substitution. These results suggest that the oxygen vacancy substitution may be superior to the coupled substitution up
to X
Al of about 0.05 and that more Al could be substituted only by the coupled substitution at 27 GPa. The Si(Al)–O1 distance and
one of two independent Si(Al)–O2 distances in Si(Al)O6 octahedra in the nonstoichiometric perovskites are always shorter than those in the stoichiometric perovskite at the same
Al content. These results imply that oxygen defects may exist in the nonstoichiometric perovskites and distribute randomly. 相似文献
18.
Lukáš Ackerman Jiří Zachariáš Marta Pudilová 《International Journal of Earth Sciences》2007,96(4):623-638
Fluid inclusions, mineral thermometry and stable isotope data from two types of mineralogically and texturally contrasting
pegmatites, barren ones and lithium ones, from the Moldanubian Zone of the Bohemian Massif were studied in order to constrain
P–T conditions of their emplacement, subsolidus hydrothermal evolution and to estimate composition of the early exsolved fluid
and that of the parental melt. Despite the fact that the lithium pegmatites are abundant throughout the crystalline units
of the Bohemian Massif, data similar to this paper have not been published yet. The studied pegmatites are hosted by iron-rich
calcic skarn bodies. This specific setting allowed scavenging of calcium, fluorine and some other elements from the host rocks
into the pegmatitic melts and post-magmatic fluids. Such contamination process was important namely in the case of barren
pegmatites, as can be deduced from the variation in anorthite contents in plagioclase and from the presence of fluorite, hornblende
(with F content) or garnet in the contact zones of pegmatite dykes. Fluid inclusions were studied mostly in quartz, but also
in fluorite, titanite and apatite. Early aqueous–carbonic and late aqueous fluids were identified in both pegmatite types.
The P–T conditions of crystallization as well as the detailed composition of exsolved magmatic fluid, however, particularly differ.
The magmatic fluids associated with barren pegmatites correspond to H2O–CO2 low salinity fluids, composition of which evolved from 20 to 23 to <5 mol% CO2, and from 2 to 4–6 mol% NaCl eq. Sudden decrease in the CO2 content of the post-magmatic fluids (<5 mol% CO2) seems to coincide with the enrichment of the fluid in calcium (from the contamination process) and resulted in precipitation
of calcites (frequently found as trapped solid phases in fluid inclusions). The fluids associated with lithium pegmatites
are more complex (H2O–CO2/N2–H3BO3–NaCl). The CO2 content of early exsolved fluid is 26–20 mol% CO2 and remains the same in the next fluid generation. The main difference between the magmatic and the first post-magmatic fluids
is the presence of 7–9 wt% of H3BO3 (identified as daughter mineral sassolite) in the former. The second post-magmatic fluids are again CO2-poor (∼4 mol%) and more saline (∼4 mol% NaCl eq.). The composition of exsolved fluid was further used to constrain volatile
composition and content of the parental melts. Finally, P–T conditions of pegmatite crystallization are constrained: 600–640°C and 420–580 MPa for the barren pegmatites and 500–570°C
and 310–430 MPa for the lithium pegmatite. While the emplacement of the former occurred in thermal equilibrium with the Moldanubian
host rock environment, the emplacement of the later suggests substantial thermal disequilibrium. 相似文献
19.
A pristine magnetite (Fe3O4) specimen was studied by means of Neutron Powder Diffraction in the 273–1,073 K temperature range, in order to characterize
its structural and magnetic behavior at high temperatures. An accurate analysis of the collected data allowed the understanding
of the behavior of the main structural and magnetic features of magnetite as a function of temperature. The magnetic moments
of both tetrahedral and octahedral sites were extracted by means of magnetic diffraction up to the Curie temperature (between
773 and 873 K). A change in the thermal expansion coefficient around the Curie temperature together with an increase in the
oxygen coordinate value above 700 K can be observed, both features being the result of a change in the thermal expansion of
the tetrahedral site. This anomaly is not related to the magnetic transition but can be explained with an intervened cation
reordering, as magnetite gradually transforms from a disordered configuration into a partially ordered one. Based on a simple
model which takes into account the cation-oxygen bond length, the degree of order as a function of temperature and consequently
the enthalpy and entropy of the reordering process were determined. The refined values are ΔH0 = −23.2(1.7) kJ mol−1 and ΔS0 = −16(2) J K−1 mol−1. These results are in perfect agreement with values reported in literature (Mack et al. in Solid State Ion 135(1–4):625–630,
2000; Wu and Mason in J Am Ceramic Soc 64(9):520–522, 1981). 相似文献
20.
The temperature (T) evolution of the barium carbonate (BaCO3) structure was studied using Rietveld structure refinements based on synchrotron X-ray diffraction and a powdered synthetic
sample. BaCO3 transforms from an orthorhombic, Pmcn, α phase to a trigonal, R3m, β phase at 811°C. The orthorhombic BaCO3 structure is isotypic with aragonite, CaCO3. In trigonal R3m BaCO3, the CO3 group occupies one orientation and shows no rotational disorder. The average <Ba–O> distances increase while the <C–O> distances
decrease linearly with T in the orthorhombic phase. After the 811°C phase transition, the <Ba–O> distances increase while C–O distances decrease.
There is also a significant volume change of 2.8% at the phase transition. 相似文献