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1.
Fluids at crustal pressures and temperatures   总被引：1，自引：0，他引：1  
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2.
The heat capacity of synthetic andradite garnet (Ca3Fe2Si3O12) was measured between 9.6 and 365.5 K by cryogenic adiabatic calorimetry and from 340 to 990 K by differential scanning calorimetry. At 298.15 K Cop,m and Som are 351.9 ± 0.7 and 316.4 ± 2.0 J/(mol·K), respectively.Andradite has a λ-peak in Cop,m with a maximum at 11.7 ± 0.2 K which is presumably associated with the antiferromagnetic ordering of the magnetic moments of the Fe3+ ions. The Gibbs free energy of formation, ΔfGom (298.15 K) of andradite is −5414.8 ± 5.5 kJ/mol and was obtained by combining our entropy and heat capacity data with the known breakdown of andradite to pseudowollastonite and hematite at ≈ 1410 to 1438 K. From a reexamination of the calcite + quartz = wollastonite equilibrium data we obtained ΔfHom (298.15 K) = − 1634.5 ± 1.8 kJ/mol for wollastonite.Between 300 and 1000 K the molar heat capacity of andradite can be represented by the equation Cop,m = 809.24 - 7.025 × 10−2T− 7.403 × 103T−0.5 − 6.789 × 105T−2. We have also used our thermochemical data for andradite to estimate the Gibbs free energy of formation of hedenbergite (CaFeSi2O6) for which we obtained ΔfGom (298.15 K) = −2674.3 ± 5.8 kJ/mol.  相似文献   

3.
The thermal evolution of 10-Å phase Mg3Si4O10(OH)2·H2O, a phyllosilicate which may have an important role in the storage/release of water in subducting slabs, was studied by X-ray single-crystal diffraction in the temperature range 116–293 K. The lattice parameters were measured at several intervals both on cooling and heating. The structural model was refined with intensity data collected at 116 K and compared to the model refined at room temperature. As expected for a layer silicate on cooling in this temperature range, the a and b lattice parameters undergo a small linear decrease, α a  = 1.7(4) 10?6 K?1 and α b  = 1.9(4) 10?6 K?1, where α is the linear thermal expansion coefficient. The greater variation is along the c axis and can be modeled with the second order polynomial c T  = c 293(1 + 6.7(4)10?5 K?1ΔT + 9.5(2.5)10?8 K?2(ΔT)2) where ΔT = T ? 293 K; the monoclinic angle β slightly increased. The cell volume thermal expansion can be modeled with the polynomial V T  = V 293 (1 + 8.0 10?5 K?1 ΔT + 1.4 10?7 K?2 (ΔT)2) where ΔT = T ? 293 is in K and V in Å3. These variations were similar to those expected for a pressure increase, indicating that T and P effects are approximately inverse. The least-squares refinement with intensity data measured at 116 K shows that the volume of the SiO4 tetrahedra does not change significantly, whereas the volume of the Mg octahedra slightly decreases. To adjust for the increased misfit between the tetrahedral and octahedral sheets, the tetrahedral rotation angle α changes from 0.58° to 1.38°, increasing the ditrigonalization of the silicate sheet. This deformation has implications on the H-bonds between the water molecule and the basal oxygen atoms. Furthermore, the highly anisotropic thermal ellipsoid of the H2O oxygen indicates positional disorder, similar to the disorder observed at room temperature. The low-temperature results support the hypothesis that the disorder is static. It can be modeled with a splitting of the interlayer oxygen site with a statistical distribution of the H2O molecules into two positions, 0.6 Å apart. The resulting shortest Obas–OW distances are 2.97 Å, with a significant shortening with respect to the value at room temperature. The low-temperature behavior of the H-bond system is consistent with that hypothesized at high pressure on the basis of the Raman spectra evolution with P.  相似文献   

4.
Mössbauer spectra (MS) of anapaite (Ca2 Fe2+(PO4)2?·?4H2O) and of a sample after being immersed in a 4% H2O2 solution at room temperature (RT) over 12 days (hereafter an4ox) were collected at temperatures in the range 4.2 to 420?K and 11 to 300?K respectively. All MS consist of symmetrical doublets, hence magnetic ordering was not observed. The temperature dependencies of the Fe2+ centre shifts of anapaite and an4ox were analysed with the Debye model for the lattice vibrations. The characteristic Mössbauer temperatures were found as 370?K?±?25?K and 340?K?±?25?K, and the intrinsic isomer shifts as 1.427?±?0.005?mm/s and 1.418?±?0.005?mm/s respectively. From the external-field (60?kOe) MS recorded at 4.2 and 189?K for the non-treated sample, the principal component V zz of the electric field gradient (EFG) is determined to be positive and the asymmetry parameter η?≈?0.2 and 0.4 respectively. The temperature variations of the quadrupole splittings, ΔE Q(T), cannot be interpreted on the basis of the thermal population of the 5 D electronic levels resulting from the tetragonal compression of the O6 co-ordination. The low-temperature linear behaviour of ΔE Q(T) is attributed to a strong orbit-lattice coupling. A field of 60 kOe applied to anapaite at 4.2?K produces magnetic hyperfine splitting with effective hyperfine fields of ?136, ?254 and ?171?kOe along the principal axes Ox, Oy and Oz of the EFG tensor respectively. Additional oxidation treatments in solutions with various H2O2 concentrations up to 20% and subsequent Mössbauer experiments at room temperature, have revealed that the anapaite structure is not sensitive to oxidation since eventually only a small amount of Fe2+ (～6.5%) is converted into Fe3+.  相似文献   

5.
Buddingtonite (NH4)[AlSi3O8] and its deuterated analogue ND4-buddingtonite (ND4)[AlSi3O8] have been synthesised in 150-mg amounts at 500 and 400?°C and 500?MPa in 5-mm-wide, 4-cm-long Au capsules using René metal hydrothermal autoclaves. The resultant product consists of clumps of monoclinic crystals with diameters of 30–60?μm. The ND4-buddingtonite contains minor amounts of NH4-buddingtonite due to H2 migration across the Au membrane. Using this synthesis technique resulted in >99% pure buddingtonite in 20% of the synthesis runs with the remaining synthesis runs containing very minor tobelite and quartz on the order of a few percent. IR spectra obtained from powdered samples are assigned on the basis of T d symmetry for the ammonium molecule. They show triply degenerate vibrational bands (i.e. ν3 and ν4) and some overtones and combination modes from NH4 + and ND4 +. While T d symmetry for NH4 + in buddingtonite is not completely correct due to distortion of the NH4 + molecule, the non-cubic field is not large enough to cause a substantial splitting in the bands. However, this perturbation is documented in the IR spectra by a substantial increase in the FWHH as well as the occurrence of shoulders on the broadened bands. Rietveld analysis indicates that buddingtonite, like orthoclase, has a monoclinic structure with space group symmetry C2/m. Here, the NH4 + molecule replaces the K+ cation on the nine fold coordinated A site which has m symmetry. Due to the larger size of the NH4 + molecule, the N–O interatomic distances are larger than the K–O distances in pure orthoclase and range from 2.95 to 3.16?Å. This results in an increase in the volume of the polyhedron hosting the NH4 + molecule. Also, in contrast to orthoclase, the polyhedron hosting the NH4 + molecule becomes more regular. The rigid Al, Si tetrahedra of the framework adjust to this expansion of the A site by rotation. This results in larger unit cell parameters for buddingtonite when compared to natural and synthesised potassium feldspars. This increase is especially seen with respect to the lattice constants a and b and the monoclinic angle β which also are found to be extremely variable. In contrast, the c direction remains nearly unchanged. Investigations using IR spectroscopy indicate that it is unlikely that this variation in the a, b and β cell dimensions is caused by incorporation of H3O+ or zeolitic water. Instead, it is more likely that substitution of NH4 + for K+ coupled with Al, Si disorder are the chief contributors to these variations in the unit cell parameters for buddingtonite.  相似文献   

6.
The thermo-elastic behaviour of Be2BO3(OH)0.96F0.04 (i.e. natural hambergite, Z = 8, a = 9.7564(1), b = 12.1980(2), c = 4.4300(1) Å, V = 527.21(1) Å3, space group Pbca) has been investigated up to 7 GPa (at 298 K) and up to 1,100 K (at 0.0001 GPa) by means of in situ single-crystal X-ray diffraction and synchrotron powder diffraction, respectively. No phase transition or anomalous elastic behaviour has been observed within the pressure range investigated. P?V data fitted to a third-order Birch–Murnaghan equation of state give: V 0 = 528.89(4) Å3, K T0 = 67.0(4) GPa and K′ = 5.4(1). The evolution of the lattice parameters with pressure is significantly anisotropic, being: K T0(a):K T0(b):K T0(c) = 1:1.13:3.67. The high-temperature experiment shows evidence of structure breakdown at T > 973 K, with a significant increase in the full-width-at-half-maximum of all the Bragg peaks and an anomalous increase in the background of the diffraction pattern. The diffraction pattern was indexable up to 1,098 K. No new crystalline phase was observed up to 1,270 K. The diffraction data collected at room-T after the high-temperature experiment showed that the crystallinity was irreversibly compromised. The evolution of axial and volume thermal expansion coefficient, α, with T was described by the polynomial function: α(T) = α 0 + α 1 T ?1/2. The refined parameters for Be2BO3(OH)0.96F0.04 are: α 0 = 7.1(1) × 10?5 K?1 and α 1 = ?8.9(2) × 10?4 K ?1/2 for the unit-cell volume, α 0(a) = 1.52(9) × 10?5 K?1 and α 1(a) = ?1.4(2) × 10?4 K ?1/2 for the a-axis, α 0(b) = 4.4(1) × 10?5 K?1 and α 1(b) = ?5.9(3) × 10?4 K ?1/2 for the b-axis, α 0(c) = 1.07(8) × 10?5 K?1 and α 1(c) = ?1.5(2) × 10?4 K ?1/2 for the c-axis. The thermo-elastic anisotropy can be described, at a first approximation, by α 0(a):α 0(b):α 0(c) = 1.42:4.11:1. The main deformation mechanisms in response to the applied temperature, based on Rietveld structure refinement, are discussed.  相似文献   

7.
A computer model for cubic sodalite structures, general formula M 8(T 12O24)X 2 where M, X and T are the cavity cation and anion and framework cation respectively, has been devised. It has been used to determine the effect of changing cavity cation and anion radii on the cell edge, tilt angle of the tetrahedra and T-O-T angle for the following sodalite frameworks: (Al6Si6O24)6?, (Be6Si6O24)12?, (Al12O24)12?, and (B12O24)12?. After fixing the T-O distance(s), the cavity cation-framework oxygen distance and taking a value of 1.4 Å for the radius of oxygen the model was used to calculate atomic coordinates and interatomic distances and angles for selected aluminosilicate-sodalites. The structure calculated for Na8(Al6Si6O24)Cl2 agrees closely with that determined for natural sodalite (Löns and Schulz, 1967). The model is also applied to the estimation of the effective radii of the tetrahedrally-coordinated cavity anions which can be accommodated in natural and synthetic sodalites: OH? 1.48–1.51, Cl? 1.78, Br? 1.93, I? 2.14–2.17, SO 4 2? 2.37–2.57, MoO 4 2? 2.70 and WO 4 2? 2.79 Å.  相似文献   

8.
Sediment-water exchanges of ammonium (NH4 +), nitrate + nitrite (NOx ?), filterable reactive phosphorus (FRP, primarily ortho-phosphate), and oxygen (O2) under aphotic (heterotrophic) conditions were determined at 2–5 stations in the Neuse River Estuary, from 1987 to 1989. Shallow (1 m), sandy stations were sampled along the salinity gradient. Fluxes from deep (>2 m) sites were compared to the shallow sites in two salinity zones. Grain size became finer and organic content increased with depth in the oligohaline zone but not in the mesohaline zone. Net release of NH4 + and FRP occurred at all sites. Fluxes varied from slight uptake to releases of 200–500 μmol m?2 h?1 (NH4 +) and 150–900 μmol m?2 h?1 (FRP). Net NOx ? exchange was near zero, but were ±100 μmol m?2 h?1 over the year. Release of NH4 + and FRP from the shallow sandy stations decreased with distance down the estuary, but O2 uptake did not change. The deeper oligohaline site had twofold higher rates of NH4 + and FRP release and O2 uptake than the shallow site, but no differences occurred between depths in the mesohaline zone. Temperature and organic content were important controls for all fluxes, but water column NOx ? concentration was also important in regulating NOx ? exchanges. Ratios of oxygen consumption to NH4 + release were near the predicted ratio (Redfield model) at oligohaline sites but increased down estuary at mesohaline sites. This may be due to greater nitrification rates promoted by autotrophy in the sediments.  相似文献   

9.
Synthetic clinopyroxenes of compositions between CaFe3+AlSiO6 and CaFe 0.85 3+ Ti0.15Al1.15Si0.85O6 have been studied by 57Fe Mössbauer spectroscopy. The spectra consist of two doublets assigned to Fe3+ in M1 and T sites. From the area ratios of the doublets the site occupancies of Fe3+ and Al were determined. Si decreases from 1.00 to 0.85 and Al+Fe3+ increases from 1.00 to 1.15 per formula unit with increasing CaTiAl2O6 component of the clinopyroxene. The atomic ratio of Fe3+(T)/Fe3+(total) is 0.11–0.16; 4.5–7.5 percent of the T sites are occupied by Fe3+. Thus the presence of Si-O-Fe3+, Al-O-Fe3+, and Fe3+-O-Fe3+ bonds is expected in addition to Si-O-Si, Si-O-Al and Al-O-Al bonds. However, the possibility of the former bonds being present would be small, because the amount of Fe3+(T) is far less than that of Si and Al. The isomer shift of Fe3+(T) is one of the largest in the values found previously for Fe3+(T) in silicates. It increases with increasing CaTiAl2O6 component and seems to be correlated to the ionic character of the cation — anion bonds calculated from electronegativity. The quadrupole splittings of Fe3+(M1) and Fe3+(T) decrease with the substitution of Fe3+?Ti4+ in the M1 and of Si?Al in the T sites.  相似文献   

10.
Water is an important volatile component in andesitic eruptions and deep-seated andesitic magma chambers. We report an investigation of H2O speciation and diffusion by dehydrating haploandesitic melts containing ?2.5 wt.% water at 743-873 K and 100 MPa in cold-seal pressure vessels. FTIR microspectroscopy was utilized to measure species [molecular H2O (H2Om) and hydroxyl group (OH)] and total H2O (H2Ot) concentration profiles on the quenched glasses from the dehydration experiments. The equilibrium constant of the H2O speciation reaction H2Om+O?2OH, K = (XOH)2/(XH2OmXO) where X means mole fraction on a single oxygen basis, in this Fe-free andesite varies with temperature as ln K = 1.547-2453/T where T is in K. Comparison with previous speciation data on rhyolitic and dacitic melts indicates that, for a given water concentration, Fe-free andesitic melt contains more hydroxyl groups. Water diffusivity at the experimental conditions increases rapidly with H2O concentration, contrary to previous H2O diffusion data in an andesitic melt at 1608-1848 K. The diffusion profiles are consistent with the model that molecular H2O is the diffusion species. Based on the above speciation model, H2Om and H2Ot diffusivity (in m2/s) in haploandesite at 743-873 K, 100 MPa, and H2Ot ? 2.5 wt.% can be formulated as
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11.
We study the phase relations and mineral chemistry in the systems muscovite–NH3–N2-H2O and eclogite + muscovite–NH3–N2-H2O at 6.3–7.8 GPa, 1000–1200 °C, and oxygen fugacity (fO2) from ∼IW (Fe–FeO) to ∼ NNO (Ni–NiO) equilibria. The quenched H2O-bearing fluids differ in nitrogen speciation from NH3-rich to N2–rich, and the respective N2/(NH3+N2) ratio varies from <0.1 to ∼ 1. N-bearing K-cymrite is obtained in association with a kyanite-garnet-jadeite ± muscovite ± corundum assemblage in the muscovite–NH3–N2-H2O system and coexists with pyrope-almandine garnet and omphacite in the eclogite + muscovite–NH3–N2-H2O system. The presence of an N-bearing fluid in the studied systems stabilizes the K-cymrite structure. Muscovite does not convert to K-cymrite in the absence of NH3–N2-bearing fluid up to 7.8 GPa and 1070–1120 °C. According to FTIR and Raman spectroscopy, K-cymrite in equilibrium with an N-rich fluid can capture a huge amount of nitrogen in cages of its framework, mainly as N2 molecules at fO2 ∼NNO and predominantly as NH3 molecules at fO2 ∼IW. The storage capacity of K-cymrite with respect to nitrogen increases from 2.9 to 6.3 wt% with increase of fO2. FTIR spectroscopy of muscovite equilibrated with K-cymrite shows that the clathrate mechanism of nitrogen entrapment by aluminosilicates (as neutral N2 and NH3 molecules) is much more efficient than the K+ → (NH4)+ substitution. The structure of N-bearing K-cymrite (K,(NH4+))[AlSi3O8]·(N2,NH3,H2O) determined using X-ray single-crystal diffraction is very similar to that of H2O-bearing K- and Ba-cymrites. It includes aluminosilicate layers consisting of double six-membered tetrahedral rings and cation sites statistically occupied with K+, Ba2+ and (NH4)+ on the six-fold symmetry axis in interlayer space. The N2 and NH3 molecules are located near the cage centers and, unlike H2O molecules, are included in the coordination environment of the cations. Our study confirms that NH3- and N2-rich K-cymrite may be stable in metapelites and can act as a redox insensitive carrier of nitrogen to >250 km mantle depths in downgoing slabs. The stability field of N-rich K-cymrite in the presence of an N2–H2O–NH3-bearing fluid is inferred to be P ≥ 4 GPa in metasediments rich in K-feldspar and P ≥ 6 GPa in those containing phengite. As the slab material sinks deeper than 250–300 km where N-bearing K-cymrite may lose stability, the releasing nitrogen may migrate to metal-saturated mantle and become stored there in γ−Fe, Fe3C, metal melt, or even iron nitride phases.  相似文献   

12.
The phonon dispersions and vibrational density of state (VDoS) of the K2SiSi3O9-wadeite (Wd) have been calculated by the first-principles method using density functional perturbation theory. The vibrational frequencies at the Brillouin zone center are in good correspondence with the Raman and infrared experimental data. The calculated VDoS was then used in conjunction with a quasi-harmonic approximation to compute the isobaric heat capacity (C P ) and vibrational entropy ( $S_{298}^{0}$ ), yielding C P (T) = 469.4(6) ? 2.90(2) × 103  T ?0.5 ? 9.5(2) × 106  T ?2 + 1.36(3) × 109  T ?3 for the T range of 298–1,000 K and $S_{298}^{0}$  = 250.4 J mol?1 K?1. In comparison, these thermodynamic properties were calculated by a second method, the classic Kieffer’s lattice vibrational model. On the basis of the vibrational mode analysis facilitated by the first-principles simulation result, we developed a new Kieffer’s model for the Wd phase. This new Kieffer’s model yielded C P (T) = 475.9(6) ? 3.15(2) × 103  T ?0.5 – 8.8(2) × 106  T ?2 + 1.31(3) × 109  T ?3 for the T range of 298–1,000 K and $S_{298}^{0}$  = 249.5(40) J mol?1 K?1, which are in good agreement both with the results from our first method containing the component of the first-principles calculation and with some calorimetric measurements in the literature.  相似文献   

13.
In an attempt to more fully understand the dissolved inorganic nitrogen dynamics of the Neuse River estuary, 15NH4 + and 15NO3 ? uptake rates were measured and daily depth-integrated rates calculated for seven stations distributed along the salinity gradient. Measurements were made at 2–3-wk intervals from March 1985 to February 1989. Significant dark NH4 + uptake occurred and varied both spatially and seasonally, accounting for as much as 95% of light uptake with the median being 33%. Apparent NH4 + uptake ranged from 0.001 μmol N 1?1 h?1 to 4.2 μmol N 1?1 h?1, with highest rates occurring during late summer-fall in the oligohaline estuary. Apparent NH4 + uptake was significantly related to NH4 + concentration (p<0.01); however, the regression explained <3% of the variation. Daily-integrated NH4 + uptake ranged from 0.1 mmol N m?2 d?1 to 133 mmol N m?2 d?1 and followed the trend of apparent uptake. Annual NH4 + uptake of the estuary was significantly lower in 1988 than for any other year. Dark uptake of NO3 ? was only 14% of maximum light uptake. Apparent NO3 ? uptake rates ranged from 0.001 μmol N 1?1 h?1 to 1.84 μmol N 1?1 h?1 with highest rates occurring in the oligohaline estuary. Apparent NO3 ? uptake was significantly related to NO3 ? concentration (p<0.01); however, the regression explained <5% of the variation. In general, NO3 ? uptake was only 20% of total dissolved inorganic nitrogen (DIN) uptake. Daily-integrated NO3 ? uptake ranged from 0.1 mmol N m?2 d?1 to 53 mmol N m?2 d?1 and followed similar patterns of apparent uptake. Annual NH4 + uptake was 11.39 mol N m?2 yr?1, 10.28 mol N m?2 Yr?1, 10.93 mol N m?2 yr?1, and 7.38 mol N m?2 yr?1, and 1.84 mol N m?2 yr?1, with the 4-yr mean being 10.0. Annual NO3 ? uptake was 3.12 mol N m?2 yr?1, 3.40 mol N m?2 yr?1, 1.96 mol N m?2 yr?1, and 1.84 mol N m?2 yr?1, with the 4-yr mean being 2.6. The total annual DIN uptake was more than twice published estimates of phytoplankton DIN demand, indicating that there is an important heterotrophic component of DIN uptake occurring in the water column. The extrapolation of nitrogen demand from primary productivity results in serious underestimates of estuarine nitrogen demand for the Neuse River estuary and may be true for other estuaries as well.  相似文献   

14.
Benthic macroinvertebrate biomass and ammonium excretion rates were measured at four stations in the Gulf of Mexico near the Mississippi River mouth. Calculated areal excretion rates were then compared to sediment-water nitrogen fluxes measured in benthic bottom lander chambers at similar stations to estimate the potential importance of macroinvertebrate excretion to sediment nitrogen mineralization. Excretion rates for individual crustaceans (amphipods and decapods) was 2–21 nmoles NH4 + (mg dry weight)?1 h?1. The mean excretion rates for the polychaetes, Paraprionaspio pinnata [6–12 nmoles NH4 + (mg dry weight)?1h?1] and Magelona sp. [27–53 nmoles NH4 + (mg dry weight)?1h?1], were comparable or higher than previous measurements for similar size benthic or pelagic invertebrates incubated at the same temperature (22±1°C). Although the relatively high rates of excretion by these selective feeders may have been partially caused by experimental handling effects (e.g., removal from sediment substrates), they probably reflected the availability of nitrogen-rich food supplies in the Mississippi River plume. When the measured weight-specific rates were extrapolated to total areal biomass, areal macroinvertebrate excretion estimates ranged from 7 μmole NH4 + m?2h?1 at a 40-m deep station near the river mouth to 18 μmole NH4 + m?2h?1 at a shallower (28-m deep) station further from the river mouth. The net flux of ammonium and nitrate from the sediments to the water measured in bottom lander chambers in the same region were 15–53 μmole NH4 + m?2h?1 and ?25–21 μmole NO3 ? m?2h?1. These results suggest that excretion of NH4 + by macroinvertebrates could be a potentially important component of benthic nitrogen regeneration in the Mississippi River plume-Gulf shelf region.  相似文献   

15.
Tobelite (NH4) Al2 [AlSi3O10] (OH)2, the ammonium analogue of muscovite, and its deuterated form ND4-tobelite (ND4) Al2 [AlSi3O10] (OD)2 have been synthesised at 600?°C and 200 and 500 Mpa using a well homogenised, stoichiometric SiO2-Al2O3 oxide mix with Al2O3 in excess of 5 mol% and a 25% NH3 solution whose relative abundance was such that the amount of NH4 + stoichiometrically available was in excess of 50%. Characterisation of both tobelite and ND4-tobelite using IR-spectroscopy, Rietveld refinement of X-ray powder diffraction data, and electron microprobe analysis indicate that, similar to K+ in muscovite, the NH4 + or ND4 + molecule occupies the interlayer site. IR absorption bands caused by NH4 + and ND4 + can be explained, to a very good approximation, on the basis of Td symmetry. Nevertheless, substantial line broadening and the occurrence of shoulders indicate a deviation from ideal Td symmetry. However, even at 77?K, no discrete splitting of the degenerate states could be confirmed. The OH stretching frequencies observed for synthetic tobelite are quite similar to those for muscovite, indicating that the replacement of K+ by NH4 + has no effect. The low FWHH of the OH bands indicate that the hydroxyl groups are well ordered within the structure. Rietveld refinement of tobelite and ND4-tobelite indicates that all samples synthesised consist of the 3 different mica polytypes which are typical of muscovite – namely 1M (C2/m), 2M 1 (C2/c) and 2M 2 (C2/c). Tobelite and ND4-tobelite synthesised at 500 Mpa principally contain the 1M polytype, whereas the principle polytype for ND4-tobelite synthesised at 200 Mpa, is 2M 2. Rietveld refinement of X-ray diffraction spectra for tobelite synthesised at 200 Mpa was problematic due to the very broad FWHH of the X-ray peaks indicating poor crystallinity. In comparision to synthetic muscovite, the cell dimensions observed for tobelite and its deuterated analogue are quite similar except for the lattice constant c. Due to the larger radius of NH4 + or ND4 + compared to K+ cation, the c-direction is expanded form 10.275 Å in muscovite to approximately 10.540 Å in tobelite and ND4-tobelite.  相似文献   

16.
The electrical conductivity of monocrystalline triphylite, Li(Fe2+,Mn2+)PO4, with the orthorhombic olivine-type structure was measured parallel (∥) to the [010] direction and ∥ [001] (space group Pnma), between ～400 and ～700 K. Electrical measurements on triphylite are of technological interest because LiFePO4 is a promising electrode material for rechargeable Li batteries. Triphylite was examined by electron microprobe, ICP atomic emission spectroscopy, X-ray diffraction, Mössbauer spectroscopy and microscopic analysis. The DC conductivity σDC was determined from AC impedance data (20 Hz–1 MHz) extrapolating to zero frequency. Triphylite shows σDC with activated behavior measured ∥ [010] between ～500 and ～700 K during the first heating up, with activation energy of E A = 1.52 eV; on cooling E A = 0.61 eV was found down to ～400 K and extrapolated σDC (295 K) ～10?9 Ω?1cm?1; ∥ [001] E A = 0.65 eV and extrapolated σDC(295 K) ～10?9 to 10?10 Ω?1cm?1, measured during the second heating cycle. The enhanced AC conductivity relative to σDC at lower temperatures indicates a hopping-type charge transport between localized levels. Conduction during the first heating up is ascribed to ionic Li+ hopping. DC polarization experiments showed conduction after the first heating up to be electronic related to lowered activation energy. Electronic conduction appears to be coupled with the presence of Li+ vacancies and Fe3+, formed by triphylite alteration. For comparison, σDC was measured on the synthetic compound LiMgPO4 with olivine-type structure, where also an activated behavior of σDC with E A ～1.45 eV was observed during heating and cooling due to ionic Li+ conduction; here no oxidation can occur associated with formation of trivalent cations.  相似文献   

17.
Near-surface atmospheric dust in Changsha city of China was analyzed in terms of morphological and geochemical composition. Morphological and chemical composition of the dust particles were analyzed by environmental scanning electron microscopy coupled with an energy-dispersive X-ray analyzer. Results indicated that the atmospheric dusts were mainly composed of spherule, plate, irregularly shaped and agglomerate, which contains variable sizes and amounts of particles. The dust particles could be categorized into five groups based on their chemical characteristic: Al-, Si-, Ca-, C-rich particles and aggregate. These particles and aggregate could be directly related to nearby polluting activities, such as building construction, traffic emission and coal combustion. The X-ray diffraction results show that the main minerals for atmospheric dust are gypsum, quartz and calcite. Mica, halloysite, montmorillonite, hematite, brushite, zeolite, sepiolite, feldspar, alite, dickite, SiS2, Fe6(OH)2CO3, FeSO4, CdSO4, Pb(NO)2O3, Al2SO4(OH)4, As2O3SO3, (NH4)2SO4, NH4Cl, K(NH4)·Ca(SO4)2·H2O are also detected in samples. The identification of heavy metals shows that the concentrations of Cr (403.5?mg?kg?1), Cu (126?mg?kg?1), Zn (1541.5?mg?kg?1), Cd (2.5?mg?kg?1) and Pb (348?mg?kg?1) in the atmospheric dust are much higher compared to background value of soil. It indicates that the heavy metal (Cr, Cu, Zn, Cd and Pb) in the atmospheric dust is mainly due to human activities. The identification of main sources of atmospheric dust collected in typical areas can help to control the polluting sources in urban area.  相似文献   

18.
A possible structure for hydrous modified olivine (HyM-α) has been obtained by the subtraction of Mg3SiO5 from forsterite by crystallographic shear along a direction parallel to the [010] direction of olivine. The subtraction of Mg3SiO5 results in the subtraction of MgO from bulk chemistry (?Mg3SiO5=?Mg2SiO4?MgO). A possible structure for HyM-α thus obtained has the chemical formula Mg9Si5H2O20 (= 5 × Mg1.8SiH0.4O4) with monoclinic unit cell a=4.754 Å, b=10.19 Å, c=29.90 Å, ρ=3.126 g cm?3, and space group=Ac2m (no. 39). Since the X-ray powder diffraction pattern of HyM-α proposed in this study is very close to that of clinohumite, there is the possibility of this phase having been undiscovered. The humite group minerals and HyM-α proposed in this study make a homologous series as recombination structures: Mg(2 m + n )Si m H2 n O2(2 m + n ) for the humite group and Mg(2 m + n )Si( m + n )H2 n O4( m + n ) for HyM-α A characteristic feature is that Mg/Si > 2 for the humite group and Mg/Si < 2 for HyM-α. Forsterite specimens containing around 100 ppm H2O reported in mantle xenoliths might be the disordered case with n=1 and m=1200 of the humite group or HyM-α.  相似文献   

19.
Reports of the high ion content of steam and low-density supercritical fluids date back to the work of Carlon [Carlon H. R. (1980) Ion content of air humidified by boiling water.J. Appl.Phys.51, 171-173], who invoked ion and neutral-water clustering as mechanism to explain why ions partition into the low-density aqueous phase. Mass spectrometric, vibrational spectroscopic measurements and quantum chemical calculations have refined this concept by proposing strongly bound ion-solvent aggregates and water clusters such as Eigen- and Zundel-type proton clusters H3O+·(H2O)m and the more weakly bound water oligomers (H2O)m. The extent to which these clusters affect fluid chemistry is determined by their abundance, however, little is known regarding the stability of such moieties in natural low-density high-temperature fluids. Here we report results from quantum chemical calculations using chemical-accuracy multi-level G3 (Curtiss-Pople) and CBS-Q theory (Peterson) to address this question. In particular, we have investigated the cluster structures and clustering equilibria for the ions and H3S+·(H2O)m(H2S)n, where m ? 6 and n ? 4, at 300-1000 K and 1 bar as well as under vapor-liquid equilibrium conditions between 300 and 646 K. We find that incremental hydration enthalpies and entropies derived from van’t Hoff analyses for the attachment of H2O and H2S onto H3O+, and H3S+ are in excellent agreement with experimental values and that the addition of water to all three ions is energetically more favorable than solvation by H2S. As clusters grow in size, the energetic trends of cluster hydration begin to reflect those for bulk H2O liquids, i.e. calculated hydration enthalpies and entropies approach values characteristic of the condensation of bulk water (ΔHo = −44.0 kJ mol−1, ΔSo = −118.8 J K mol−1). Water and hydrogen sulfide cluster calculations at higher temperatures indicate that a significant fraction of H3O+, and H3S+ ions exists as solvated moieties.  相似文献   

20.
Wadeite-type K2Si4O9 was synthesized with a cubic press at 5.4 GPa and 900 °C for 3 h. Its unit-cell parameters were measured by in situ high-T powder X-ray diffraction up to 600 °C at ambient P. The T–V data were fitted with a polynomial expression for the volumetric thermal expansion coefficient (αT = a 0 + a 1 T), yielding a 0 = 2.47(21) × 10?5 K?1 and a 1 = 1.45(36) × 10?8 K?2. Compression experiments at ambient T were conducted up to 10.40 GPa with a diamond-anvil cell combined with synchrotron X-ray radiation. A second-order Birch–Murnaghan equation of state was used to fit the P–V data, yielding K T = 97(3) GPa and V 0 = 360.55(9) Å3. These newly determined thermal expansion data and compression data were used to thermodynamically calculate the P–T curves of the following reactions: 2 sanidine (KAlSi3O8) = wadeite (K2Si4O9) + kyanite (Al2SiO5) + coesite (SiO2) and wadeite (K2Si4O9) + kyanite (Al2SiO5) + coesite/stishovite (SiO2) = 2 hollandite (KAlSi3O8). The calculated phase boundaries are generally consistent with previous experimental determinations.  相似文献   

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