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1.
Parameterization of sensible heat and momentum fluxes as inferred from an analysis of tower observations archived during MONTBLEX-90 at Jodhpur is proposed, both in terms of standard exchange coefficientsC H andC D respectively and also according to free convection scaling. Both coefficients increase rapidly at low winds (the latter more strongly) and with increasing instability. All the sensible heat flux data at Jodhpur (wind speed at 10 m Ū10 < 8 ms−1) also obey free convection scaling, with the flux proportional to the ‘4/3’ power of an appropriate temperature difference such as that between 1 and 30 m. Furthermore, for Ū10 < 4 ms−1 the momentum flux displays a linear dependence on wind speed.  相似文献   

2.
In the estimation of momentum fluxes over land surfaces by the bulk aerodynamic method, no unique value of the drag coefficient (C D) is found in the literature. The drag coefficient is generally estimated from special observations at different parts of the world. In this study an attempt is made to estimate drag coefficient over the western desert sector of India using data sets of Monsoon Trough Boundary Layer Experiment (MONTBLEX) during the summer monsoon season of 1990. For this purpose, the fast and slow response data sets obtained simultaneously from a 30 m high micro-meteorological tower at Jodhpur are used. All the observations used in this study are confined to a wind speed regime of 2.5–9.0 ms−1. A comparison of momentum fluxes computed by eddy correlation (direct estimation) with profile and bulk aerodynamic (C D = 3.9 × 10−3, Garratt, 1977) methods revealed that though the nature of variation of the fluxes by all these methods is almost similar, both the indirect methods give an under-estimated value of the fluxes. The drag coefficient is estimated as a function of wind speed and surface stability by a multiple regression approach. An average value of the estimated drag coefficient is found to be of the order of 5.43 × 10−3. The estimated value ofC D is validated with a set of independent observations and found to be quite satisfactory. The recomputed momentum fluxes by bulk aerodynamic method using the estimated drag coefficient are in close agreement with the directly estimated fluxes.  相似文献   

3.
As a part of the MONTBLEX-90 observational programme, Kytoon and Doppler sodar observations were taken at Kharagpur. These data are analysed to study the turbulent characteristics of the atmospheric boundary layer in terms of stability, temperature structure function (C T 2 ) and velocity structure function (C v 2 ).C T 2 follows aZ −4/3 law on most of the days, whereas the variation ofC V 2 is not systematic.C V 2 andC T 2 values are found to vary between 10−5−10−1 m4/3s−2 and 10−5−10−2°C2 m−2/3 respectively.  相似文献   

4.
Surface flux parameterization schemes used in current dynamic models are primarily based upon measurements at low and moderate wind speeds. Recent studies show that these parameterization schemes may be incorrect at high wind speeds (e.g., tropical cyclone forecasts). Five high-resolution numerical model experiments are designed to assess the sensitivity of tropical cyclone intensity forecasts to changes in the surface flux parameterization. The sensitivity experiments are conducted by running 48 h forecasts of the Coupled Ocean/Atmosphere Mesoscale Prediction System (COAMPS) for six selected tropical cyclones with individual modifications to surface flux calculation that include: (1) limiting the surface stress for wind speeds greater than 33 m s−1, or 64 knots (kt); (2) computing the stress at the top of the model bottom grid layer (MBGL) by averaging results from surface layer similarity and turbulence mixing parameterization for wind speeds greater than 33 m s−1; (3) increasing the roughness lengths for heat and moisture transfer by a factor of ten; (4) setting the roughness lengths for heat and moisture transfer to 1/10 of the momentum roughness length; and (5) cooling the sea surface temperature (SST) by a prescribed rate at high winds. Averaged responses for the six storms to these sensitivity tests show that: (i) the limit on surface stress at high winds significantly increases the cyclone intensity in 48 h forecasts; (ii) the averaged surface layer stress at high winds increases the cyclone intensity but to a much lesser degree than limiting the surface stress; (iii) large increases in the roughness lengths for heat and moisture transfer are needed to significantly impact the intensity forecast; (iv) the different roughness length formula for surface transfer coefficients notably increases C h/C d ratio from 0.59 to 0.79 for 25 m s−1 and 0.41 to 0.75 for 50 m s−1 that significantly increases the predicted cyclone intensity; and (v) cooling of the SST by −5.8°C in 48 h reduces the maximum surface wind speed by −32 kt, or 16.5 m s−1, at 48 h forecast. These results suggest that a surface flux parameterization scheme suitable for tropical cyclone intensity forecast must correctly model the leveling-off character of surface stress and C h/C d ratio at high winds. All modifications to surface flux calculation have little influence on 48 h track forecasts, even though they may significantly impact the intensity forecasts.
Chi-Sann LiouEmail:
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5.
Thermal diffusivity (D) was measured using laser-flash analysis from oriented single-crystal low-sanidine (K0.92Na0.08Al0.99Fe3+ 0.005Si2.95O8), and three glasses near KAlSi3O8. Viscosity measurements of the three supercooled liquids, in the range 106.8 to 1012.3 Pa s, confirm near-Arrhenian behavior, varying subtly with composition. For crystal and glass, D decreases with T, approaching a constant near 1,000 K: D sat ∼ 0.65 ± 0.3 mm2 s−1 for bulk crystal and ∼0.53 ± 0.03 mm2 s−1 for the glass. A rapid decrease near 1,400 K is consistent with crossing the glass transition. Melt behavior is approximated by D = 0.475 ± 0.01 mm2 s−1. Thermal conductivity (k lat) of glass, calculated using previous heat capacity (C P) and new density data, increases with T because C P strongly increases with T. For melt, k lat reaches a plateau near 1.45 W m−1 K−1, and is always below k lat of the crystal. Melting of potassium feldspars impedes heat transport, providing positive thermal feedback that may promote further melting in continental crust.  相似文献   

6.
The residual (time-average) salinity and circulation in a numerical ocean model of the Tampa Bay estuary are shown to experience significant temporal variation under realistic forcing conditions. A version of the Estuarine Coastal Ocean Model developed for Tampa Bay with 70 by 100 horizontal grid points and 11 sigma levels is examined for the years 2001–2003. Model output variables are averaged over the entire time of the simulation to generate long-term residual fields. The residual axial current is found to be dominated by the buoyancy-driven baroclinic circulation with an outflow (southwestward) at the surface and to the sides of the shipping channel, and an inflow (northeastward) usually occurring subsurface within or above the shipping channel. Averages over 30 d are used to examine variations in the residual fields. During the simulation the average surface salinity near the head of Tampa Bay varies with the freshwater inflow, from 12‰ to 33%. At the bay mouth salinity varies from 30%. to 36%.. A localized measure of the baroclinic circulation in the shipping channel indicates the residual circulation can vary strongly, attaining a magnitude triple the long-term mean value. The baroclinic circulation can be disrupted, going to near zero or even reversing, when the buoyancy-driven flow is weak and the surface winds are to the northeast. Three time periods, representing different environmental conditions, are chosen to examine these results in detail. A scaling argument indicates the relative strength of buoyancy versus wind as ΔρgH2(LC Dω2)−1, where δρ is head-to-mouth density difference across the bay,g is gravitational acceleration,H is depth,L is bay length,C D is the surface wind drag coefficient, andw is wind speed. Tampa Bay is usually in the buoyancy dominated regime. The importance of winds in the weak-buoyancy case is demonstrated in an additional simulation without wind stress.  相似文献   

7.
 Cation tracer diffusion coefficients, DMe *, for Me=Fe, Mn, Co and Ti, were measured using radioactive isotopes in the spinel solid solution (Ti x Fe 1−x )3−δO4 as a function of the oxygen activity. Experiments were performed at different cationic compositions (x=0, 0.1, 0.2 and 0.3) at 1100, 1200, 1300 and 1400 °C. The oxygen activity dependence of all data for DMe * at constant temperature and cationic composition can be described by equations of the type DMe *=D∘ Me[V]. CV·a O2 2/3+DMe[I] ∘·a O2 −2/3·DMe[V] ∘ and DMe[I] ∘ are constants and CV is a factor of the order of unity which decreases with increasing δ. All log DMe * vs. loga O2 curves obtained for different values of x and for different temperatures go through a minimum due to a change in the type of point defects dominating the cation diffusion with oxygen activity. Cation vacancies prevail for the cation diffusion at high oxygen activities while cation interstitials become dominant at low oxygen activities. At constant values of x, DMe[V] ∘ decreases with increasing temperature while DMe[I] ∘ increases.  相似文献   

8.
The thermoelastic behavior of a natural clintonite-1M [with composition: Ca1.01(Mg2.29Al0.59Fe0.12)Σ3.00(Si1.20Al2.80)Σ4.00O10(OH)2] has been investigated up to 10 GPa (at room temperature) and up to 960°C (at room pressure) by means of in situ synchrotron single-crystal and powder diffraction, respectively. No evidence of phase transition has been observed within the pressure and temperature range investigated. P–V data fitted with an isothermal third-order Birch–Murnaghan equation of state (BM-EoS) give V 0 = 457.1(2) ?3, K T0 = 76(3)GPa, and K′ = 10.6(15). The evolution of the “Eulerian finite strain” versus “normalized stress” shows a linear positive trend. The linear regression yields Fe(0) = 76(3) GPa as intercept value, and the slope of the regression line leads to a K′ value of 10.6(8). The evolution of the lattice parameters with pressure is significantly anisotropic [β(a) = 1/3K T0(a) = 0.0023(1) GPa−1; β(b) = 1/3K T0(b) = 0.0018(1) GPa−1; β(c) = 1/K T0(c) = 0.0072(3) GPa−1]. The β-angle increases in response to the applied P, with: βP = β0 + 0.033(4)P (P in GPa). The structure refinements of clintonite up to 10.1 GPa show that, under hydrostatic pressure, the structure rearranges by compressing mainly isotropically the inter-layer Ca-polyhedron. The bulk modulus of the Ca-polyhedron, described using a second-order BM-EoS, is K T0(Ca-polyhedron) = 41(2) GPa. The compression of the bond distances between calcium and the basal oxygens of the tetrahedral sheet leads, in turn, to an increase in the ditrigonal distortion of the tetrahedral ring, with ∂α/∂P ≈ 0.1°/GPa within the P-range investigated. The Mg-rich octahedra appear to compress in response to the applied pressure, whereas the tetrahedron appears to behave as a rigid unit. The evolution of axial and volume thermal expansion coefficient α with temperature was described by the polynomial α(T) = α0 + α1 T −1/2. The refined parameters for clintonite are as follows: α0 = 2.78(4) 10−5°C−1 and α1 = −4.4(6) 10−5°C1/2 for the unit-cell volume; α0(a) = 1.01(2) 10−5°C−1 and α1(a) = −1.8(3) 10−5°C1/2 for the a-axis; α0(b) = 1.07(1) 10−5°C−1 and α1(b) = −2.3(2) 10−5°C1/2 for the b-axis; and α0(c) = 0.64(2) 10−5°C−1 and α1(c) = −7.3(30) 10−6°C1/2for the c-axis. The β-angle appears to be almost constant within the given T-range. No structure collapsing in response to the T-induced dehydroxylation was found up to 960°C. The HP- and HT-data of this study show that in clintonite, the most and the less expandable directions do not correspond to the most and the less compressible directions, respectively. A comparison between the thermoelastic parameters of clintonite and those of true micas was carried out.  相似文献   

9.
The ambient pressure elastic properties of single-crystal TiO2 rutile are reported from room temperature (RT) to 1800 K, extending by more than 1200 oK the maximum temperature for which rutile elasticity data are available. The magnitudes of the temperature derivatives decrease with increasing temperature for five of the six adiabatic elastic moduli (C ij ). At RT, we find (units, GPa): C 11=268(1); C 33=484(2); C 44=123.8(2); C 66=190.2(5); C 23=147(1); and C 12=175(1). The temperature derivatives (units, GPa K−1) at RT are: (∂C 11/∂T) P =−0.042(5); (∂C 33/∂T) P =−0.087(6); (∂C 44/∂T) P =−0.0187(2); (∂C 66/∂T) P =−0.067(2); (∂C 23/∂T) P =−0.025; and (∂C 12/∂T) P −0.048(5). The values for K S (adiabatic bulk modulus) and μ (isotropic shear modulus) and their temperature derivatives are K S =212(1) GPa; μ=113(1) GPa; (∂K S /∂T) P =−0.040(4) GPa K−1; and (∂μ/∂T) P =−0.018(1) GPa K−1. We calculate several dimensionless parameters over a large temperature range using our new data. The unusually high values for the Anderson-Gròneisen parameters at room temperature decrease with increasing temperature. At high T, however, these parameters are still well above those for most other oxides. We also find that for TiO2, anharmonicity, as evidenced by a non-zero value of [∂ln (K T )/∂lnV] T , is insignificant at high T, implying that for the TiO2 analogue of stishovite, thermal pressure is independent of volume (or pressure). Systematic relations indicate that ∂2 K S /∂T∂P is as high as 7×10−4 K−1 for rutile, whereas ∂2μ/∂T∂P is an order of magnitude less. Received: 19 September 1997 / Revised, accepted: 27 February 1998  相似文献   

10.
Magnesium self-diffusion coefficients were determined experimentally for diffusion parallel to each of the three crystallographic directions in natural orthoenstatite (En88Fs12). Experiments were conducted at 1 atm in CO-CO2 gas mixing furnaces, which provided oxygen fugacities equivalent to the iron-wüstite buffer. Diffusion of 25Mg was induced in polished samples of oriented orthoenstatite using a film of isotopically enriched 25MgO as the source material. Very short (<0.15 μm) diffusional penetration profiles were measured by ion microprobe depth profiling. The diffusion coefficients determined for four temperatures (900, 850, 800, 750 °C) provide the activation energies, E a , and frequency factors, D o, where D = D o exp (−E a /RT) for Mg self-diffusion parallel to each crystallographic direction: a-axis, E a  = 360 ± 52 kJ/mole and D o = 1.10 × 10−4 m2/s; b-axis, E a  = 339 ± 77 kJ/mole and D o = 6.93 × 10−6 m2/s and c-axis, E a  = 265 ± 66 kJ/mole and D o = 4.34 × 10−9 m2/s. In this temperature range, any possible anisotropy of cation diffusion is very small, however the activation energy for diffusion parallel to the c-axis (001) is the lowest and the activation energies for diffusion parallel to the a-axis (100) and b-axis (010) are higher. Application of these diffusion results to the silicate phases of the Lowicz mesosiderite meteorite provides cooling rates for the silicate portion of the meteorite (4–11 °C/100 years) that are similar, although slower, to previous estimates. These silicate cooling rates are still several orders of magnitude faster than the cooling rates (0.1 °C/106 years) for the metal portions. Received: 22 January 1997 / Accepted: 2 October 1997  相似文献   

11.
We estimate, from the moisture budget the bulk aerodynamic coefficient for latent heat flux (C e) during the monsoon season over the central Arabian Sea. The average value ofC eunder active monsoon conditions was found to be 2.25 × 10−3 which is nearly 60% higher than those previously used.  相似文献   

12.
 The heat capacity of paranatrolite and tetranatrolite with a disordered distribution of Al and Si atoms has been measured in the temperature range of 6–309 K using the adiabatic calorimetry technique. The composition of the samples is represented with the formula (Na1.90K0.22Ca0.06)[Al2.24Si2.76O10]·nH2O, where n=3.10 for paranatrolite and n=2.31 for tetranatrolite. For both zeolites, thermodynamic functions (vibrational entropy, enthalpy, and free energy function) have been calculated. At T=298.15 K, the values of the heat capacity and entropy are 425.1 ± 0.8 and 419.1 ±0.8 J K−1 mol−1 for paranatrolite and 381.0 ± 0.7 and 383.2 ± 0.7 J K−1 mol−1 for tetranatrolite. Thermodynamic functions for tetranatrolite and paranatrolite with compositions corrected for the amount of extraframework cations and water molecules have also been calculated. The calculation for tetranatrolite with two water molecules and two extraframework cations per formula yields: C p (298.15)=359.1 J K−1 mol−1, S(298.15) −S(0)=362.8 J K−1 mol−1. Comparing these values with the literature data for the (Al,Si)-ordered natrolite, we can conclude that the order in tetrahedral atoms does not affect the heat capacity. The analysis of derivatives dC/dT for natrolite, paranatrolite, and tetranatrolite has indicated that the water- cations subsystem within the highly hydrated zeolite may become unstable at temperatures above 200 K. Received: 30 July 2001 / Accepted: 15 November 2001  相似文献   

13.
Diffusion profiles in minerals are increasingly used to determine the duration of geological events. For this purpose, the distinction between growth and diffusion zoning is critical; it requires the understanding of complex features associated with multicomponent diffusion. Seed-overgrowth interdiffusion experiments carried out in the range 1,050–1,250°C at 1.3 GPa have been designed to quantify and better understand Fe–Mg–Ca interdiffusion in garnet. Some of the diffusion profiles measured by analytical transmission electron microscope show characteristic features of multicomponent diffusion such as uphill diffusion, chemical solitary waves, zero-flux planes and complex diffusion paths. We implemented three different methods to calculate the interdiffusion coefficients of the D matrix from the experimental penetration curves and determined that with Ca as the dependent component, the crossed coefficients of the D matrix are negative. Experiments and numerical simulations indicate that: (1) uphill diffusion in garnet can be observed indifferently on the three components Fe, Mg and Ca, (2) it takes the form of complementary depletion/repletion waves and (3) chemical waves occur preferentially on initially flat concentration profiles. Derived D matrices are used to simulate the fate of chemical waves in time, in finite crystals. These examples show that the flow of atoms in multicomponent systems is not necessarily unidirectional for all components; it can change both in space along the diffusion profile and in time. Moving zero-flux planes in finite crystals are transitory features that allow flux reversals of atoms in the diffusion zone. Interdiffusion coefficients of the D matrices are also analyzed in terms of eigenvalues and eigenvectors. This analysis and the experimental results show that depending on the composition of the diffusion couple, (1) the shape of chemical waves and diffusion paths changes; (2) the width of the diffusion zone for each component may or may not be identical; and (3) the width of diffusion calculated at a given D and duration may greatly vary. D matrices were retrieved from thirteen sets of diffusion profiles. Data were cast in Arrhenius relations. Linear regressions of the data yield activation energies equal to 368, 148, 394, 152 kJ mol−1 at 1 bar and frequency factors Do equal to 2.37 × 10−6, −4.46 × 10−16, −1.31 × 10−5, 9.85 × 10−15 m2 s−1 for [(D)\tilde]FeFeCa \tilde{D}_{FeFe}^{Ca} , [(D)\tilde]FeMgCa \tilde{D}_{FeMg}^{Ca} , [(D)\tilde]MgFeCa \tilde{D}_{MgFe}^{Ca} , [(D)\tilde]MgMgCa \tilde{D}_{MgMg}^{Ca} , respectively. These values can be used to calculate interdiffusion coefficients in Fe–Mg–Ca garnets and determine the duration of geological events in high temperature metamorphic or magmatic garnets.  相似文献   

14.
The heat capacity of gadolinium orthophosphate (GdPO4) measured in the temperature range 11.15–344.11 K by adiabatic calorimetry and available literature data were used to calculate its thermodynamic functions at 0–1600 K. At 298.15 K, these functions are as follows: C p 0(298.15 K) = 101.85 ± 0.05 J K−1 mol−1, S 0(298.15 K) = 123.82 ± 0.18 J K−1 mol−1, H 0(298.15 K)–H 0(0) = 17.250 ± 0.012 kJ mol−1, and Φ 0(298.15 K) = 65.97 ± 0.18 J K−1 mol−1 The calculated Gibbs free energy of formation from the elements of GdPO4 is Δ f G 0 (298.15 K) = −1844.3 ± 4.7 kJ mol−1.  相似文献   

15.
To understand partitioning of hydrogen between hydrous basaltic and andesitic liquids and coexisting clinopyroxene and garnet, experiments using a mid-ocean ridge basalt (MORB) + 6 wt.% H2O were conducted at 3 GPa and 1,150–1,325°C. These included both isothermal and controlled cooling rate crystallization experiments, as crystals from the former were too small for ion microprobe (SIMS) analyses. Three runs at lower bulk water content are also reported. H2O was measured in minerals by SIMS and in glasses by SIMS, Fourier Transform infrared spectroscopy (FTIR), and from oxide totals of electron microprobe (EMP) analyses. At 3 GPa, the liquidus for MORB with 6 wt.% H2O is between 1,300 and 1,325°C. In the temperature interval investigated, the melt proportion varies from 100 to 45% and the modes of garnet and clinopyroxene are nearly equal. Liquid composition varies from basaltic to andesitic. The crystallization experiments starting from above the liquidus failed to nucleate garnets, but those starting from below the liquidus crystallized both garnet and clinopyroxene. SIMS analyses of glasses with >7 wt.% H2O yield spuriously low concentrations, perhaps owing to hydrogen degassing in the ultra-high vacuum of the ion microprobe sample chamber. FTIR and EMP analyses show that the glasses have 3.4 to 11.9 wt.% water, whilst SIMS analyses indicate that clinopyroxenes have 1,340–2,330 ppm and garnets have 98–209 ppm H2O. D H cpx−gt is 11 ± 3, D H cpx−melt is 0.023 ± 0.005 and D H gt−melt is 0.0018 ± 0.0006. Most garnet/melt pairs have low values of D H gt−melt, but D H gt−melt increases with TiO2 in the garnet. As also found by previous studies, values of D H cpx−melt increase with Al2O3 of the crystal. For garnet pyroxenite, estimated values of D H pyroxenite−melt decrease from 0.015 at 2.5 GPa to 0.0089 at 5 GPa. Hydration will increase the depth interval between pyroxenite and peridotite solidi for mantle upwelling beneath ridges or oceanic islands. This is partly because the greater pyroxene/olivine ratio in pyroxenite will tend to enhance the H2O concentration of pyroxenite, assuming that neighboring pyroxenite and peridotite bodies have similar H2O in their pyroxenes. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.  相似文献   

16.
 The lattice constants of paragonite-2M1, NaAl2(AlSi3)O10(OH)2, were determined to 800 °C by the single-crystal diffraction method. Mean thermal expansion coefficients, in the range 25–600 °C, were: αa = 1.51(8) × 10−5, αb = 1.94(6) × 10−5, αc = 2.15(7) ×  10−5 °C−1, and αV = 5.9(2) × 10−5 °C−1. At T higher than 600 °C, cell parameters showed a change in expansion rate due to a dehydroxylation process. The structural refinements of natural paragonite, carried out at 25, 210, 450 and 600 °C, before dehydroxylation, showed that the larger thermal expansion along the c parameter was mainly due to interlayer thickness dilatation. In the 25–600 °C range, Si,Al tetrahedra remained quite unchanged, whereas the other polyhedra expanded linearly with expansion rate proportional to their volume. The polyhedron around the interlayer cation Na became more regular with temperature. Tetrahedral rotation angle α changed from 16.2 to 12.9°. The structure of the new phase, nominally NaAl2 (AlSi3)O11, obtained as a consequence of dehydroxylation, had a cell volume 4.2% larger than that of paragonite. It was refined at room temperature and its expansion coefficients determined in the range 25–800 °C. The most significant structural difference from paragonite was the presence of Al in fivefold coordination, according to a distorted trigonal bipyramid. Results confirm the structural effects of the dehydration mechanism of micas and dioctahedral 2:1 layer silicates. By combining thermal expansion and compressibility data, the following approximate equation of state in the PTV space was obtained for paragonite: V/V 0 = 1 + 5.9(2) × 10−5 T(°C) − 0.00153(4) P(kbar). Received: 12 July 1999 / Revised, accepted: 7 December 1999  相似文献   

17.
We determined experimentally the Nernst distribution coefficient between orthopyroxene and anhydrous silicate melt for trace elements i in the system Na2O–CaO–MgO–Al2O3–SiO2 (NCMAS) along the dry model lherzolite solidus from 1.1 GPa/1,230°C up to 3.2 GPa/1,535°C in a piston cylinder apparatus. Major and trace element composition of melt and orthopyroxene were determined with a combination of electron microprobe and ion probe analyses. We provide partitioning data for trace elements Li, Be, B, K, Sc, Ti, V, Cr, Co, Ni, Rb, Sr, Y, Zr, Nb, Cs, Ba, La, Ce, Sm, Nd, Yb, Lu, Hf, Ta, Pb, U, and Th. The melts were chosen to be boninitic at 1.1 and 2.0 GPa, picritic at 2.3 GPa and komatiitic at 2.7 and 3.2 GPa. Orthopyroxene is Tschermakitic with 8 mol% Mg-Tschermaks MgAl[AlSiO6] at 1.1 GPa while at higher pressure it has 18–20 mol%. The rare earth elements show a continuous, significant increase in compatibility with decreasing ionic radius from D Laopx−melt ∼ 0.0008 to D Luopx−melt ∼ 0.15. For the high-field-strength elements compatibility increases from D Thopx−melt ∼ 0.001 through D Nbopx−melt ∼ 0.0015, D Uopx−melt ∼ 0.002, D Taopx−melt ∼ 0.005, D Zropx−melt ∼ 0.02 and D Hfopx−melt ∼ 0.04 to D Tiopx−melt ∼ 0.14. From mathematical and graphical fits we determined best-fit values for D 0M1, D 0M2, r 0M1, r 0M2, E 0M1, and E 0M2 for the two different M sites in orthopyroxene according to the lattice strain model and calculated the intracrystalline distribution between M1 and M2. Our data indicate extreme intracrystalline fractionation for most elements in orthopyroxene; for the divalent cations D i M2−M1 varies by three orders of magnitude between D CoM2−M1 = 0.00098–0.00919 and D BaM2−M1 = 2.3–28. Trivalent cations Al and Cr almost exclusively substitute on M1 while the other trivalent cations substitute on M2; D LaM2−M1 reaches extreme values between 6.5 × 107 and 1.4 × 1016. Tetravalent cations Ti, Hf, and Zr almost exclusively substitute on M1 while U and Th exclusively substitute on M2. Our new comprehensive data set can be used for polybaric-polythermal melting models along the Earth’s mantle solidus. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.  相似文献   

18.
Self-diffusion of Si under anhydrous conditions at 1 atm has been measured in natural zircon. The source of diffusant for experiments was a mixture of ZrO2 and 30Si-enriched SiO2 in 1:1 molar proportions; experiments were run in crimped Pt capsules in 1-atm furnaces. 30Si profiles were measured with both Rutherford backscattering spectrometry (RBS) and nuclear reaction analysis with the resonant nuclear reaction 30Si(p,γ)31P. For Si diffusion normal to c over the temperature range 1,350–1,550°C, we obtain an Arrhenius relation D = 5.8 exp(−702 ± 54 kJ mol−1/RT) m2 s−1 for the NRA measurements, which agrees within uncertainty with an Arrhenius relation determined from the RBS measurements [62 exp(−738 ± 61 kJ mol−1/RT) m2 s−1]. Diffusion of Si parallel to c appears slightly faster, but agrees within experimental uncertainty at most temperatures with diffusivities for Si normal to c. Diffusion of Si in zircon is similar to that of Ti, but about an order of magnitude faster than diffusion of Hf and two orders of magnitude faster than diffusion of U and Th. Si diffusion is, however, many orders of magnitude slower than oxygen diffusion under both dry and hydrothermal conditions, with the difference increasing with decreasing temperature because of the larger activation energy for Si diffusion. If we consider Hf as a proxy for Zr, given its similar charge and size, we can rank the diffusivities of the major constituents in zircon as follows: D Zr < D Si << D O, dry < D O, ‘wet’.  相似文献   

19.
The unite cell parameters and heat capacities of a series of synthetic clinopyroxenes on the join Ca-Tschermak (CaTs)−diopside (Di) were measured using X-ray powder diffraction and calorimetric methods, respectively. The volume of mixing at 298 K shows a negative asymmetric deviation from ideality. A two-parameter Margules fit to the data yields W CaTs−Di V = −0.29 ± 0.11 cm3 mol−1 and W Di−CaTs V = −1.14 ± 0.14 cm3 mol−1. Heat capacities were determined between 5 and 923 K by heat-pulse at 5−302 K and differential-scanning calorimetry at 143−923 K. The precision of the low and high temperature C p data is better than ±1%. Polynomials of the form C p = a + bT −1/2 + cT −2 + dT −3 were fitted to the C p data in the temperature range between 250 and 925 K. Thermal entropy values [S 298 − S 0] and [S 900 −S 0] as well as enthalpies [H 298 − H 0] and [H 900 − H 0] were calculated for all members of the solid solution series. No significant deviation from ideal mixing behavior was observed.  相似文献   

20.
The unit cell parameters, extracted from Rietveld analysis of neutron powder diffraction data collected between 4.2 K and 320 K, have been used to calculate the temperature evolution of the thermal expansion tensor for gypsum for 50 ≤ T ≤ 320 K. At 300 K the magnitudes of the principal axes are α 11  = 1.2(6) × 10−6 K−1, α 22  = 36.82(1) × 10−6 K−1 and α 33  = 25.1(5) × 10−6 K−1. The maximum axis, α 22 , is parallel to b, and using Institution of Radio Engineers (IRE) convention for the tensor orthonormal basis, the axes α 11 and α 33 have directions equal to (−0.979, 0, 0.201) and (0.201, 0, 0.979) respectively. The orientation and temperature dependent behaviour of the thermal expansion tensor is related to the crystal structure in the I2/a setting. Received 12 February 1998 / Revised, accepted 19 October 1998  相似文献   

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