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1.
The thermoelastic behaviour of anthophyllite has been determined for a natural crystal with crystal-chemical formula ANa0.01
B(Mg1.30Mn0.57Ca0.09Na0.04) C(Mg4.95Fe0.02Al0.03) T(Si8.00)O22
W(OH)2 using single-crystal X-ray diffraction to 973 K. The best model for fitting the thermal expansion data is that of Berman
(J Petrol 29:445–522, 1988) in which the coefficient of volume thermal expansion varies linearly with T as α
V,T
= a
1 + 2a
2 (T − T
0): α298 = a
1 = 3.40(6) × 10−5 K−1, a
2 = 5.1(1.0) × 10−9 K−2. The corresponding axial thermal expansion coefficients for this linear model are: α
a
,298 = 1.21(2) × 10−5 K−1, a
2,a
= 5.2(4) × 10−9 K−2; α
b
,298 = 9.2(1) × 10−6 K−1, a
2,b
= 7(2) × 10−10 K−2. α
c
,298 = 1.26(3) × 10−5 K−1, a
2,c
= 1.3(6) × 10−9 K−2. The thermoelastic behaviour of anthophyllite differs from that of most monoclinic (C2/m) amphiboles: (a) the ε
1 − ε
2 plane of the unit-strain ellipsoid, which is normal to b in anthophyllite but usually at a high angle to c in monoclinic amphiboles; (b) the strain components are ε
1 ≫ ε
2 > ε
3 in anthophyllite, but ε
1 ~ ε
2 ≫ ε
3 in monoclinic amphiboles. The strain behaviour of anthophyllite is similar to that of synthetic C2/m
ANa B(LiMg) CMg5
TSi8 O22
W(OH)2, suggesting that high contents of small cations at the B-site may be primarily responsible for the much higher thermal expansion
⊥(100). Refined values for site-scattering at M4 decrease from 31.64 epfu at 298 K to 30.81 epfu at 973 K, which couples with similar increases of those of M1 and M2 sites. These changes in site scattering are interpreted in terms of Mn ↔ Mg exchange involving M1,2 ↔ M4, which was first detected at 673 K. 相似文献
2.
A. Pavese V. Diella V. Pischedda M. Merli R. Bocchio M. Mezouar 《Physics and Chemistry of Minerals》2001,28(4):242-248
The thermoelastic parameters of natural andradite and grossular have been investigated by high-pressure and -temperature
synchrotron X-ray powder diffraction, at ESRF, on the ID30 beamline. The P–V–T data have been fitted by Birch-Murnaghan-like EOSs, using both the approximated and the general form. We have obtained for
andradite K
0=158.0(±1.5) GPa, (dK/dT )0=−0.020(3) GPa K−1 and α0=31.6(2) 10−6 K−1, and for grossular K
0=168.2(±1.7) GPa, (dK/dT)0=−0.016(3) GPa K−1 and α0=27.8(2) 10−6 K−1. Comparisons between the present issues and thermoelastic properties of garnets earlier determined are carried out.
Received: 7 July 2000 / Accepted: 20 October 2000 相似文献
3.
Behavior of epidote at high pressure and high temperature: a powder diffraction study up to 10 GPa and 1,200 K 总被引:1,自引:0,他引:1
G. Diego Gatta Marco Merlini Yongjae Lee Stefano Poli 《Physics and Chemistry of Minerals》2011,38(6):419-428
The thermo-elastic behavior of a natural epidote [Ca1.925 Fe0.745Al2.265Ti0.004Si3.037O12(OH)] has been investigated up to 1,200 K (at 0.0001 GPa) and 10 GPa (at 298 K) by means of in situ synchrotron powder diffraction.
No phase transition has been observed within the temperature and pressure range investigated. P–V data fitted with a third-order Birch–Murnaghan equation of state (BM-EoS) give V
0 = 458.8(1)Å3, K
T0 = 111(3) GPa, and K′ = 7.6(7). The confidence ellipse from the variance–covariance matrix of K
T0 and K′ from the least-square procedure is strongly elongated with negative slope. The evolution of the “Eulerian finite strain”
vs “normalized stress” yields Fe(0) = 114(1) GPa as intercept values, and the slope of the regression line gives K′ = 7.0(4). The evolution of the lattice parameters with pressure is slightly anisotropic. The elastic parameters calculated
with a linearized BM-EoS are: a
0 = 8.8877(7) Å, K
T0(a) = 117(2) GPa, and K′(a) = 3.7(4) for the a-axis; b
0 = 5.6271(7) Å, K
T0(b) = 126(3) GPa, and K′(b) = 12(1) for the b-axis; and c
0 = 10.1527(7) Å, K
T0(c) = 90(1) GPa, and K’(c) = 8.1(4) for the c-axis [K
T0(a):K
T0(b):K
T0(c) = 1.30:1.40:1]. The β angle decreases with pressure, βP(°) = βP0 −0.0286(9)P +0.00134(9)P
2 (P in GPa). The evolution of axial and volume thermal expansion coefficient, α, with T was described by the polynomial function: α(T) = α0 + α1
T
−1/2. The refined parameters for epidote are: α0 = 5.1(2) × 10−5 K−1 and α1 = −5.1(6) × 10−4 K1/2 for the unit-cell volume, α0(a) = 1.21(7) × 10−5 K−1 and α1(a) = −1.2(2) × 10−4 K1/2 for the a-axis, α0(b) = 1.88(7) × 10−5 K−1 and α1(b) = −1.7(2) × 10−4 K1/2 for the b-axis, and α0(c) = 2.14(9) × 10−5 K−1 and α1(c) = −2.0(2) × 10−4 K1/2 for the c-axis. The thermo-elastic anisotropy can be described, at a first approximation, by α0(a): α0(b): α0(c) = 1 : 1.55 : 1.77. The β angle increases continuously with T, with βT(°) = βT0 + 2.5(1) × 10−4
T + 1.3(7) × 10−8
T
2. A comparison between the thermo-elastic parameters of epidote and clinozoisite is carried out. 相似文献
4.
The cation distribution of Co, Ni, and Zn between the M1 and M2 sites of a synthetic olivine was determined with a single-crystal
diffraction method. The crystal data are (Co0.377Ni0.396Zn0.227)2SiO4, M
r
= 212.692, orthorhombic, Pbnm, a = 475.64(3), b = 1022.83(8), and c = 596.96(6) pm, V = 0.2904(1) nm3, Z = 4, D
x
= 4.864 g cm−3, and F(0 0 0) = 408.62. Lattice, positional, and thermal parameters were determined with MoKα radiation; R = 0.025 for 1487 symmetry-independent reflections with F > 4σ(F). The site occupancies of Co, Ni, and Zn were determined with synchrotron radiation employing the anomalous dispersion effect
of Co and Ni. The synchrotron radiation data include two sets of intensity data collected at 161.57 and 149.81 pm, which are
about 1 pm longer than Co and Ni absorption edges, respectively. The R value was 0.022 for Co K edge data with 174 independent reflections, and 0.034 for Ni K edge data with 169 reflections. The occupancies are 0.334Co + 0.539Ni + 0.127Zn in the M1 sites, and 0.420Co + 0.253Ni + 0.327Zn
in the M2 sites. The compilation of the cation distributions in olivines shows that the distributions depend on ionic radii
and electronegativities of constituent cations, and that the partition coefficient can be estimated from the equation: ln [(A/B)M1/(A/B)M2] = −0.272 (IR
A
-IR
B
) + 3.65 (EN
A
−EN
B
), where IR (pm) and EN are ionic radius and electronegativity, respectively.
Received: 8 April 1999 / Revised, accepted: 7 September 1999 相似文献
5.
K.-D. Grevel A. Navrotsky W. A. Kahl D. W. Fasshauer J. Majzlan 《Physics and Chemistry of Minerals》2001,28(7):475-487
Calorimetric and P–V–T data for the high-pressure phase Mg5Al5Si6O21(OH)7 (Mg-sursassite) have been obtained. The enthalpy of drop solution of three different samples was measured by high-temperature
oxide melt calorimetry in two laboratories (UC Davis, California, and Ruhr University Bochum, Germany) using lead borate (2PbO·B2O3) at T=700 ∘C as solvent. The resulting values were used to calculate the enthalpy of formation from different thermodynamic datasets;
they range from −221.1 to −259.4 kJ mol−1 (formation from the oxides) respectively −13892.2 to −13927.9 kJ mol−1 (formation from the elements). The heat capacity of Mg5Al5Si6O21(OH)7 has been measured from T=50 ∘C to T=500 ∘C by differential scanning calorimetry in step-scanning mode. A Berman and Brown (1985)-type four-term equation represents
the heat capacity over the entire temperature range to within the experimental uncertainty: C
P
(Mg-sursassite) =(1571.104 −10560.89×T
−0.5−26217890.0 ×T
−2+1798861000.0×T
−3) J K−1 mol−1 (T in K). The P
V
T behaviour of Mg-sursassite has been determined under high pressures and high temperatures up to 8 GPa and 800 ∘C using a MAX 80 cubic anvil high-pressure apparatus. The samples were mixed with Vaseline to ensure hydrostatic pressure-transmitting
conditions, NaCl served as an internal standard for pressure calibration. By fitting a Birch-Murnaghan EOS to the data, the
bulk modulus was determined as 116.0±1.3 GPa, (K
′=4), V
T,0
=446.49 3 exp[∫(0.33±0.05) × 10−4 + (0.65±0.85)×10−8
T dT], (K
T/T)
P
= −0.011± 0.004 GPa K−1. The thermodynamic data obtained for Mg-sursassite are consistent with phase equilibrium data reported recently (Fockenberg
1998); the best agreement was obtained with Δf
H
0
298 (Mg-sursassite) = −13901.33 kJ mol−1, and S
0
298 (Mg-sursassite) = 614.61 J K−1 mol−1.
Received: 21 September 2000 / Accepted: 26 February 2001 相似文献
6.
Benthic nutrient fluxes in the intertidal flat within the Changjiang (Yangtze River) Estuary 总被引:1,自引:0,他引:1
GAO Lei LI Daoji WANG Yanming YU Lihua KONG Dingjiang LI Mei LI Yun and FANG Tao State Key Laboratory of Marine Geology Tongji University Shanghai China State Key Laboratory of Estuarine Coastal Research East China Normal University Shanghai China 《中国地球化学学报》2008,27(1):58-71
In an annual cycle from March 2005 to February 2006, benthic nutrient fluxes were measured monthly in the Dongtan intertidal flat within the Changjiang (Yangtze River) Estuary. Except for NH4^+, there always showed high fluxes from overlying water into sediment for other four nutrients. Sediments in the high and middle marshes, covered with halophyte and consisting of macrofauna, demonstrated more capabilities of assimilating nutrients from overlying water than the low marsh. Sampling seasons and nutrient concentrations in the overlying water could both exert significant effects on these fluxes. Additionally, according to the model provided by previous study, denitrification rates, that utilizing NO3- transported from overlying water (Dw) in Dongtan sediments, were estimated to be from -16 to 193 μmol·h^-1·m^-2 with an average value of 63 μmol·h^-1·m^-2 (n=18). These estimated values are still underestimates of the in-situ rates owing to the lack of consideration of DN, i.e., denitrification supported by the local NO3^- production via nitrification. 相似文献
7.
D. G. Isaak J. D. Carnes O. L. Anderson H. Cynn E. Hake 《Physics and Chemistry of Minerals》1998,26(1):31-43
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
8.
An experimental study has been carried out to determine the partition coefficients of tungsten between aqueous fluids and
granitic melts at 800 °C and 1.5 kb with natural granite as the starting material. The effects of the solutions on the partition
coefficients of tungsten show a sequence of P > CO
3
2−
> B > H2O. The effects are limited (generallyK
D
< 0.3) and the tungsten shows a preferential trend toward the melt over the aqueous fluid. The value ofK
D
increases with increasing concentration of phosphorus; theK
D
increases first and then reduces with the concentration of CO
3
2−
when temperature decreases, theK
D
between the solution of CO
3
2−
and the silicate melt increases, and that between the solution of B4O
7
2−
and the silicate melt decreases. The partition coefficients of phosphorus and sodium between fluids and silicate melts have
been calculated from the concentrations of the elements in the melts. TheK
D
value for phosphorus is 0.38 and that for sodium is 0.56. Evidence shows that the elements tend to become richer and richer
in the melts. 相似文献
9.
The thermal expansion of gehlenite, Ca2Al[AlSiO7], (up to T=830 K), TbCaAl[Al2O7] (up to T=1,100 K) and SmCaAl[Al2O7] (up to T=1,024 K) has been determined. All compounds are of the melilite structure type with space group
Thermal expansion data was obtained from in situ X-ray powder diffraction experiments in-house and at HASYLAB at the Deutsches Elektronen Synchrotron (DESY) in Hamburg (Germany). The thermal expansion coefficients for gehlenite were found to be: α1=7.2(4)×10−6 K−1+3.6(7)×10−9ΔT K−2 and α3=15.0(1)×10−6 K−1. For TbCaAl[Al2O7] the respective values are: α1=7.0(2)×10−6 K−1+2.0(2)×10−9ΔT K−2 and α3=8.5(2)×10−6 K−1+2.0(3)×10−9ΔT K−2, and the thermal expansion coefficients for SmCaAl[Al2O7] are: α1=6.9(2)× 10−6 K−1+1.7(2)×10−9ΔT K−2 and α3=9.344(5)×10−6 K−1. The expansion-mechanisms of the three compounds are explained in terms of structural trends obtained from Rietveld refinements
of the crystal structures of the compounds against the powder diffraction patterns. No structural phase transitions have been
observed. While gehlenite behaves like a ’proper’ layer structure, the aluminates show increased framework structure behaviour.
This is most probably explained by stronger coulombic interactions between the tetrahedral conformation and the layer-bridging
cations due to the coupled substitution (Ca2++Si4+)-(Ln
3++Al3+) in the melilite-type structure.
Electronic Supplementary Material Supplementary material is available for this article at 相似文献
10.
The thermal expansion of gehlenite, Ca2Al[AlSiO7], (up to T=830 K), TbCaAl[Al2O7] (up to T=1100 K) and SmCaAl[Al2O7] (up to T=1024 K) has been determined. All compounds are of the melilite structure type with space group
Thermal expansion data were obtained from in situ X-ray powder diffraction experiments in-house and at HASYLAB at the Deutsches
Elektronen Synchrotron (DESY) in Hamburg (Germany). The thermal expansion coefficients for gehlenite were found to be: α1=7.2(4)×10−6×K−1+3.6(7)×10−9ΔT×K−2 and α3=15.0(1)×10−6×K−1. For TbCaAl[Al2O7] the respective values are: α1=7.0(2)×10−6×K−1+2.0(2)×10−9ΔT×K−2 and α3=8.5(2)×10−6×K−1+2.0(3)×10−9ΔT×K−2, and the thermal expansion coefficients for SmCaAl[Al2O7] are: α1=6.9(2)×10−6×K−1+1.7(2)×10−9ΔT×K−2 and α3=9.344(5)×10−6×K−1. The expansion mechanisms of the three compounds are explained in terms of structural trends obtained from Rietveld refinements
of the crystal structures of the compounds against the powder diffraction patterns. No structural phase transitions have been
observed. While gehlenite behaves like a ‘proper’ layer structure, the aluminates show increased framework structure behavior.
This is most probably explained by stronger coulombic interactions between the tetrahedral conformation and the layer-bridging
cations due to the coupled substitution (Ca2++Si4+)–(Ln
3++Al3+) in the melilite-type structure.
This article has been mistakenly published twice. The first and original version of it is available at . 相似文献
11.
G. Diego Gatta Marco Merlini Hanns-Peter Liermann André Rothkirch Mauro Gemmi Alessandro Pavese 《Physics and Chemistry of Minerals》2012,39(5):385-397
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
12.
P. Comodi G. D. Gatta P. F. Zanazzi D. Levy W. Crichton 《Physics and Chemistry of Minerals》2002,29(8):538-544
Powder diffraction measurements at simultaneous high pressure and temperature on samples of 2M1 polytype of muscovite (Ms) and paragonite (Pg) were performed at the beamline ID30 of ESRF (Grenoble), using the Paris-Edinburgh
cell. The bulk moduli of Ms, calculated from the least-squares fitting of V–P data on each isotherm using a second-order Birch–Murnaghan EoS, were: 57.0(6), 55.1(7), 51.1(7) and 48.9(5) GPa on the isotherms
at 298, 573, 723 and 873 K, respectively. The value of (∂K
T
/∂T)
was −0.0146(2) GPa K−1. The thermal expansion coefficient α varied from 35.7(3) × 10−6 K−1 at P ambient to 20.1(3) × 10−6 K−1 at P = 4 GPa [(∂α/∂P)
T
= −3.9(1) × 10−6 GPa−1 K−1]. The corresponding values for Pg on the isotherms at 298, 723 and 823 K were: bulk moduli 59.9(5), 55.7(6) and 53.8(7) GPa,
(∂K
T
/∂T)
−0.0109(1) GPa K−1. The thermal expansion coefficient α varied from 44.1(2) × 10−6 K−1 at P ambient to 32.5(2) × 10−6 K−1 at P = 4 GPa [(∂α/∂P)
T
= −2.9(1) × 10−6 GPa−1 K−1]. Thermoelastic coefficients showed that Pg is stiffer than Ms; Ms softens more rapidly than Pg upon heating; thermal expansion
is greater and its variation with pressure is smaller in Pg than in Ms.
Received: 28 January 2002 / Accepted: 5 April 2002 相似文献
13.
Maik Pertermann Alan G. Whittington Anne M. Hofmeister Frank J. Spera John Zayak 《Contributions to Mineralogy and Petrology》2008,155(6):689-702
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
14.
The partitioning of Mg and Fe between magnesiowüstite and ringwoodite solid solutions has been measured between 15 and 23 GPa
and 1200–1600 ∘C using both Fe and Re capsule materials to vary the oxidation conditions. The partitioning results show a clear dependence
on the capsule material used due to the variation in Fe3+ concentrations as a consequence of the different oxidation environments. Using results from experiments performed in Fe capsules,
where metallic Fe was also added to the starting materials, the difference in the interaction parameters for the two solid
solutions (W
FeMg
mw−W
FeMg
ring) is calculated to be 8.5±1 kJ mol−1. Similar experiments performed in Re metal capsules result in a value for W
FeMg
mw−W
FeMg
ring that is apparently 4 kJ higher, if all Fe is assumed to be FeO. Electron energy-loss near-edge structure (ELNES) spectroscopic
analyses, however, show Fe3+ concentrations to be approximately three times higher in magnesiowüstite produced in Re capsules than in Fe capsules and
that Fe3+ partitions preferentially into magnesiowüstite, with K
D
Fe3+
ring/mw estimated between 0.1 and 0.6. Using an existing activity composition model for magnesiowüstite, a least–squares fit to the
partitioning data collected in Fe capsules results in a value for the ringwoodite interaction parameter (W
FeMg
ring) of 3.5±1 kJ mol−1. The equivalent regular interaction parameter for magnesiowüstite (W
FeMg
mw) is 12.1±1.8 kJ mol. These determinations take into account the Fe3+ concentrations that occur in both phases in the presence of metallic Fe. The free energy change in J mol−1 for the Fe exchange reaction can be described, over the range of experimental conditions, by 912 + 4.15 (T−298)+18.9P with T in K, P in kbar. The estimated volume change for this reaction is smaller than that predicted using current compilations of equation
of state data and is much closer to the volume change at ambient conditions. These results are therefore a useful test of
high pressure and temperature equation of state data. Using thermodynamic data consistent with this study the reaction of
ringwoodite to form magnesiowüstite and stishovite is calculated from the data collected using Fe capsules. Comparison of
these results with previous studies shows that the presence of Fe3+ in phases produced in multianvil experiments using Re capsules can have a marked effect on apparent phase relations and determined
thermodynamic properties.
Received: 13 September 2000 / Accepted: 25 March 2001 相似文献
15.
A barrier system based on the hydraulic trap design concept for a landfill was proposed. To study the field scenario in which
a clay liner is underlain by a granular layer functioning as a secondary leachate drain layer, a laboratory advection–diffusion
test was performed to investigate factors controlling the transport of contaminants in a two-layer soil system. The soils
used for this study were Ariake clay and, the underlying layer, Shirasu soil from the Kyushu region of Japan. Potassium (K+) was selected as the target chemical species with an initial concentration of 905 mg L−1. The effective diffusion coefficients (D
e) of K+ for Ariake clay and Shirasu soil were back-calculated using an available computer program, Pollute
V 6.3. Values of D
e derived from this experiment are consistent with previously published ones. The Ariake clay has lower D
e than the Shirasu soil. The hypothesis that mechanical dispersion can be considered negligible is reasonable based on both
the observation that the predicted values well fit the experimental data and the analyses of two dimensionless parameters.
Parametric analyses show that transport of K+ through soils is controlled by advection–diffusion rather than diffusion only, whereas at low Darcy velocity (i.e., ≤10−9 m s−1), transport of K+ will be controlled by diffusion. Applications of the test results and parametric analysis results in practical situations
were reviewed. 相似文献
16.
Nancy L. Ross 《Physics and Chemistry of Minerals》1998,25(8):597-602
The crystal structure of orthorhombic (Pbnm) ScAlO3 perovskite has been refined to 5 GPa using single-crystal X-ray diffraction. The compression of the structure if anisotropic
with β
a
=1.39(3)×10−3 GPa−1, β
b
=1.14(3)×10−3 GPa−1 and β
c
=1.84(3)×10−3 GPa−1. The isothermal bulk modulus of ScAlO3, K
T
, determined from fitting a Birch-Murnaghan equation of state (K
′
T
=4) to the volume compression data is 218(1) GPa. The interoctahedral angles to not vary significantly with pressure, and
the compression of the structure is entirely attributable to compression of the AlO6 octahedra. The compressibilities of the constituent AlO6 and ScO12 are well matched: βAl−O=1.6×10−3 GPa−1 and βSc−O=1.5×10−3 GPa−1. Therefore the distortion of the structure shows no significant change with increasing pressure.
Received: 18 August 1997 / Revised, accepted: 11 November 1997 相似文献
17.
J. Zhang 《Physics and Chemistry of Minerals》2000,27(3):145-148
Isobaric volume measurements for MgO were carried out at 2.6, 5.4, and 8.2 GPa in the temperature range 300–1073 K using
a DIA-type, large-volume apparatus in conjunction with synchrotron X-ray powder diffraction. Linear fit of the thermal expansion
data over the experimental pressure range yields the pressure derivative, (∂α/∂P)
T
, of −1.04(8) × 10−6 GPa−1 K−1 and the mean zero-pressure thermal expansion α0,
T
= 4.09(6) × 10−5 K−1. The α0,
T
value is in good agreement with results of Suzuki (1975) and Utsumi et al. (1998) over the same temperature range, whereas
(∂α/∂P)
T
is determined for the first time on MgO by direct measurements. The cross-derivative (∂α2/∂P∂T) cannot be resolved because of large uncertainties associated with the temperature derivative of α at all pressures. The
temperature derivative of the bulk modulus, (∂K
T/∂T)
P
, of −0.025(3) GPa K−1, obtained from the measured (∂α/∂P)
T
value, is in accord with previous findings.
Received: 2 April 1999 / Revised, accepted: 22 June 1999 相似文献
18.
Lars Chresten Lund-Hansen Thorbjørn Joest Andersen Morten Holtegaard Nielsen Morten Pejrup 《Estuaries and Coasts》2010,33(6):1442-1451
Optical constituents as suspended particulate matter (SPM), chlorophyll (Chl-a), colored dissolved organic matter (CDOM),
and grain sizes were obtained on a transect in the arctic fjord-type estuary Kangerlussuaq (66°) in August 2007 along with
optical properties. These comprised diffuse attenuation coefficient of downwelling PAR (K
d(PAR)), upwelling PAR (K
u(PAR)), particle beam attenuation coefficient (c
p), and irradiance reflectance R(−0, PAR). PAR is white light between 400 and 700 nm. The estuary receives melt water from the Greenland Inland Ice and stations
covered a transect from the very high turbid melt water outlet to clear marine waters. Results showed a strong spatial variation
with high values as for suspended matter concentrations, CDOM, diffuse attenuation coefficient K
d(PAR), particle beam attenuation coefficients (c
p), and reflectance R(−0, PAR) at the melt water outlet. Values of optical constituents and properties decreased with distance from the melt water
outlet to a more or less constant level in central and outer part of the estuary. There was a strong correlation between inorganic
suspended matter (SPMI) and diffuse attenuation coefficient K
d(PAR) (r
2 = 0.92) and also for particle beam attenuation coefficient (c
p; r
2 = 0.93). The obtained SPMI specific attenuation—K
d*(PAR) = 0.13 m2 g−1 SPMI—and the SPMI specific particle beam attenuation—c
p* = 0.72 m2 g−1—coefficients were about two times higher than average literature values. Irradiance reflectance R(−0, PAR) was comparatively high (0.09−0.20) and showed a high (r
2 = 0.80) correlation with K
u(PAR). Scattering dominated relative to absorption—b(PAR)/a(PAR) = 12.3. Results strongly indicated that the high values in
the optical properties were related to the very fine particle sizes (mean = 2–6 μm) of the suspended sediment. Data and results
are discussed and compared to similar studies from both temperate and tropical estuaries. 相似文献
19.
Hongwu Xu Alexandra Navrotsky M. Lou. Balmer Yali Su 《Physics and Chemistry of Minerals》2005,32(5-6):426-435
Wadeite K2ZrSi3O9 and its analogues K2TiSi3O9 and Cs2ZrSi3O9, synthesized by high-temperature solid-state sintering, have been investigated using powder X-ray diffraction coupled with
Rietveld analysis and high-temperature oxide melt solution calorimetry. The crystal chemistry and energetics of these phases,
together with K2SiVISi3
IVO9, a high-pressure wadeite analogue containing both tetrahedral and octahedral Si, are discussed in term of ionic substitutions.
As the size of the octahedral framework cation increases, Si4+ → Ti4+ → Zr4+, the cell parameter c increases at a much higher rate than a. In contrast, increasing the interstitial alkali cation size (K+ → Cs+) results in a higher rate of increase in a compared with c. This behavior can be attributed to framework distortion around the interstitial cation. The enthalpies of formation from
the constituent oxides (ΔHf,ox0) and from the elements (ΔHf,el0) have been determined from drop-solution calorimetry into 2PbO·B2O3 solvent at 975 K. The obtained values (in kJ/mol) are as follows: ΔHf,ox0 (K2TiSi3O9) = −355.8 ± 3.0, ΔHf,el0 (K2TiSi3O9) = −4395.1 ± 4.8, ΔHf,ox0 (K2ZrSi3O9) = −374.3 ± 3.3, ΔHf,el0 (K2ZrSi3O9) = −4569.9 ± 5.0, ΔHf,ox0 (Cs2ZrSi3O9) = −396.6 ± 4.4, and ΔHf,el0 (Cs2ZrSi3O9) = −4575.0 ± 5.5. The enthalpies of formation for K2SiVISi3
IVO9 were calculated from its drop-solution enthalpy of an earlier study (Akaogi et al. 2004), and the obtained ΔHf,ox0 (K2SiSi3O9) = −319.7 ± 3.4 and ΔHf,el0 (K2SiSi3O9) = −4288.7 ± 5.1 kJ/mol. With increasing the size of the octahedral framework cation or of the interstitial alkali cation,
the formation enthalpies become more exothermic. This trend is consistent with the general behavior of increasing energetic
stability with decreasing ionic potential (z/r) seen in many oxide and silicate systems. Further, increasing the size of the octahedral framework cation appears to induce
more rapid increase in stability than increasing the interstitial alkali cation size, suggesting that framework cations play
a more dominant role in wadeite stability. 相似文献
20.
Elastic wave velocities for dense (99.8% of theoretical density) isotropic polycrystalline specimens of synthetic pyrope (Mg3Al2Si3O12) were measured to 1,000 K at 300 MPa by the phase comparison method of ultrasonic interferometry in an internally heated
gas-medium apparatus. The temperature derivatives of the elastic moduli [(∂Ks/∂T)
P
= −19.3(4); (∂G/∂T)
P
= −10.4(2) MPa K−1] measured in this study are consistent with previous acoustic measurements on both synthetic polycrystalline pyrope in a
DIA-type cubic anvil apparatus (Gwanmesia et al. in Phys Earth Planet Inter 155:179–190, 2006) and on a natural single crystal by the rectangular parallelepiped resonance (RPR; Suzuki and Anderson in J Phys Earth 31:125–138,
1983) method but |(∂Ks/∂T)
P
| is significantly larger than from a Brillouin spectroscopy study of single-crystal pyrope (Sinogeikin and Bass in Phys Earth
Planet Inter 203:549–555, 2002). Alternative approaches to the retrieval of mixed derivatives of the elastic moduli from joint analysis of data from this
study and from the solid-medium data of Gwanmesia et al. in Phys Earth Planet Inter 155:179–190 (2006) yield ∂2
G/∂P∂T = [0.07(12), 0.20(14)] × 10−3 K−1 and ∂2
K
S
/∂P∂T = [−0.20(24), 0.22(26)] × 10−3 K−1, both of order 10−4 K−1 and not significantly different from zero. More robust inference of the mixed derivatives will require solid-medium acoustic
measurements of precision significantly better than 1%. 相似文献