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1.
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
2.
Low-temperature heat capacity measurements for MgCr2O4 have only been performed down to 52 K, and the commonly quoted third-law entropy at 298 K (106 J K−1 mol−1) was obtained by empirical extrapolation of these measurements to 0 K without considering the magnetic or electronic ordering
contributions to the entropy. Subsequent magnetic measurements at low temperature reveal that the Néel temperature, at which
magnetic ordering of the Cr3+ ions in MgCr2O4 occurs, is at ∼15 K. Hence a substantial contribution to the entropy of MgCr2O4 has been missed. We have determined the position of the near-univariant reaction MgCr2O4+SiO2=MgSiO3+Cr2O3. The reaction, which has a small positive slope in P-T space, has been bracketed at 100 K intervals between 1273 and 1773 K by reversal experiments. The reaction is extremely sluggish,
and lengthy run times with a flux (H2O, BaO-B2O3 or K2O-B2O3) are needed to produce tight reversal brackets. The results, combined with assessed thermodynamic data for Cr2O3, MgSiO3 and SiO2, give the entropy and enthalpy of formation of MgCr2O4 spinel. As expected, our experimental results are not in good agreement with the presently available thermodynamic data.
We obtain Δ
f
H
∘
298=−1759.2±1.5 kJ mol−1 and S
∘
298=122.1±1.0 J K−1 mol−1 for MgCr2O4. This entropy is some 16 J K−1 mol−1 more than the calorimetrically determined value, and implies a value for the magnetic entropy of MgCr2O4 consistent with an effective spin quantum number (S') for Cr3+ of 1/2 rather than the theoretical 3/2, indicating, as in other spinels, spin quenching.
Received: 9 May 1997 / Accepted: 28 July 1997 相似文献
3.
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
4.
The giant chromite deposits at Kempirsai, Urals: constraints from trace element (PGE, REE) and isotope data 总被引：6，自引：0，他引：6
The investigation of stable and radiogenic isotopes and of platinum-group (PGE) and rare earth elements (REE) in chromitites
and associated ultramafic rocks of the Kempirsai Massif, southern Urals, gives strong evidence for a multistage formation
of giant ophiolitic-podiform chromite deposits present in the southeastern part of the massif. The Kempirsai ophiolite massif
is divided by a shear zone into two parts: in the northwestern area, small bodies of Al-rich chromite formed from basaltic
melts between 420 to 400 Ma, according to Sm-Nd mineral isochrons of harzburgite, pyroxenite, websterite and gabbro. Harzburgites
and pyroxenites in this area are enriched in light REE and have ɛNd(400) > +6 and ɛSr(400) ∼ +5. Chromitites have scattered PGE distributions (Pd/Ir, 0.4–7.0), being partly enriched in Pd and Pt. γOs(400) of one chromitite is −4.4. The southeastern part of the Kempirsai Massif, well-known for its world-class deposits of
podiform low-Al magnesiochromite, is characterized by harzburgite and dunite enriched in light REE with very low ɛNd(400) (+4.3 to –17.1) and positive ɛSr(400) (>+10) values. Chromitites are strongly enriched in Ir, Os and Ru and depleted in Pd and Pt. γOs(400) of three chromitites is uniform and approaches C1 and DMM compositions. In veins and pods postdating crystallization
of massive chromite, pargasitic amphibole formed in equilibrium with fluid-inclusion-bearing chromite at temperatures close
to 1000 °C. These amphiboles give 40Ar/39Ar stepwise heating ages of 365 to 385 Ma and are characterized by low ɛNd(400) (+0.6 to −4.6) and general enrichment in REE. The cooling ages correspond to a 379.3 ± 1.6 Ma Rb-Sr mineral isochron
produced from amphibole and phlogopite of a pyroxenite vein in the western part of the massif. From these data it is concluded
that parts of the Kempirsai Massif have been pervasively metasomatized by large amounts of fluids and melts derived from a
subducted slab composed of oceanic crust and sediments. Subduction occurred at least 15–35 Ma after a melting event that produced
a typical ophiolitic sequence in the Paleozoic Sakmara Zone. We conclude that large chromite orebodies formed from second-stage
high-Mg melts that interacted with depleted mantle and fluids on their way upward in a suprasubduction zone regime, and in
a fore-arc position to the Magnitogorsk island arc.
Received: 21 January 1998 / Accepted: 24 August 1998 相似文献
5.
H2O activities in supercritical fluids in the system KCl-H2O-(MgO) were measured at pressures of 1, 2, 4, 7, 10 and 15 kbar by numerous reversals of vapor compositions in equilibrium
with brucite and periclase. Measurements spanned the range 550–900 °C. A change of state of solute KCl occurs as pressures
increase above 2 kbar, by which H2O activity becomes very low and, at pressures of 4 kbar and above, nearly coincident with the square of the mole fraction
(x
H2O). The effect undoubtedly results primarily from ionic dissociation as H2O density (ρH2O) approaches 1 gm/cm3, and is more pronounced than in the NaCl-H2O system at the same P-T-X conditions. Six values of solute KCl activity were yielded by terminal points of the isobaric brucite-periclase T-x
H2O curves where sylvite saturation occurs. The H2O mole fraction of the isobaric invariant assemblage brucite-periclase-sylvite-fluid is near 0.52 at all pressures, and the
corresponding temperatures span only 100 °C between 1 and 15 kbar. This remarkable convergence of the isobaric equilibrium
curves reflects the great influence of pressure on lowering of both KCl and H2O activities. The H2O and KCl activities can be expressed by the formulas: a
H2O = γH2O[x
H2O+(1 + (1 + α)x
KCl)], and a
KCL = γKCl[(1 + α)x
KCl/(x
H2O +(1 + α)x
KCl)](1 + α), where α is a degree of dissociation parameter which increases from zero at the lowest pressures to near one at high pressures
and the γ's are activity coefficients based on an empirical regular solution parameter W: ln γi = (1 − xi)2W. Least squares fitting of our H2O and KCl activity data evaluates the parameters: α = exp(4.166 −2.709/ρH2O) − 212.1P/T, and W = (−589.6 − 23.10P) /T, with ρH2O in gm/cm3, P in kbar and T in K. The standard deviation from the measured activities is only ± 0.014. The equations define isobaric liquidus curves,
which are in perfect agreement with previous DTA liquidus measurements at 0.5–2 kbar, but which depart progressively from
their extrapolation to higher pressures because of the pressure-induced dissociation effect. The great similarity of the NaCl-H2O and KCl-H2O systems suggests that H2O activities in the ternary NaCl-KCl-H2O system can be described with reasonable accuracy by assuming proportionality between the binary systems. This assumption
was verified by a few reconnaissance measurements at 10 kbar of the brucite-periclase equilibrium with a Na/(Na + K) ratio
of 0.5 and of the saturation temperature for Na/(Na + K) of 0.35 and 0.50. At that pressure the brucite-periclase curves reach
a lowest x
H2O of 0.45 and a temperature of 587 °C before salt saturation occurs, values considerably lower than in either binary. This
double-salt eutectic effect may have a significant application to natural polyionic hypersaline solutions in the deep crust
and upper mantle in that higher solute concentrations and very low H2O activities may be realized in complex solutions before salt saturation occurs. Concentrated salt solutions seem, from this
standpoint, and also because of high mechanical mobility and alkali-exchanging potential, feasible as metasomatic fluids for
a variety of deep-crust and upper mantle processes.
Received: 9 August 1996 / Accepted: 15 November 1996 相似文献
6.
Phase A, Mg7Si2O8(OH)6, is a dense hydrous magnesium silicate whose importance as a host of H2O in the Earth’s mantle is a subject of debate. We have investigated the low-pressure stability of phase A in experiments
on the reaction phase A=brucite+forsterite. Experiments were conducted in piston-cylinder and multi-anvil apparatus, using
mixtures of synthetic phase A, brucite and forsterite. The reaction was bracketed between 2.60 and 2.75 GPa at 500° C, between
3.25 and 3.48 GPa at 600° C and between 3.75 and 3.95 GPa at 650° C. These pressures are much lower than observed in the synthesis experiments of Yamamoto and Akimoto (1977). At 750° C the stability field of brucite + chondrodite was entered. The enthalpy of formation and entropy of phase A at 1 bar (105 Pa), 298 K, were derived from the experimental brackets on the reaction phase A=brucite+forsterite using a modified version
of the thermodynamic dataset THERMOCALC of Holland and Powell (1990), which includes a new equation of state of H2O derived from the molecular dynamics simulations of Brodholt and Wood (1993). The data for phase A are: ΔH
o
f
=−7126±8 kJ mol-1, S
o=351 J K-1 mol-1. Incorporating these data into THERMOCALC allows the positions of other reactions involving phase A to be calculated, for
example the reaction phase A + enstatite=forsterite+vapour, which limits the stability of phase A in equilibrium with enstatite.
The calculated position of this reaction (753° C at 7 GPa to 937° C at 10 GPa) is in excellent agreement with the experimental
brackets of Luth (1995) between 7 and 10 GPa, supporting the choice of equation of state of H2O used in THERMOCALC. Comparison of our results with calculated P-T paths of subducting slabs (Peacock et al. 1994) suggests that, in the system MgO–SiO2–H2O, phase A could crystallise in compositions with Mg/Si>2 at pressures as low as 3 GPa. In less Mg rich compositions phase
A could crystallise at pressures above approximately 6 GPa.
Received: 3 July 1995/Accepted: 14 December 1995 相似文献
7.
Summary The complexation of aluminium(III) and silicon(IV) was studied in a simplified seawater medium (0.6 M Na(Cl)) at 25 °C. The
measurements were performed as potentiometric titrations using a hydrogen electrode with OH
− ions being generated coulometrically. The total concentrations of Si(IV) and Al(III) respectively [Si
tot
] and [Al
t
ot], and −log[H
+] were varied within the limits 0.3 < [Si
tot
] < 2.5 mM, 0.5 < [Al
tot
] < 2.6 mM, and 2 ≤ -log[H
+] ≤ 4.2. Within these ranges of concentration, evidence is given for the formation of an AlSiO(OH)
3
2+
complex with a formation constant log β1,1-1 = −2.75 ± 0.1 defined by the reaction
Al
3++Si (OH)4 ↔ AlOSi(OH)
3
2+
+H
+
An extrapolation of this value to I=0 gives log β1,1-1 = −2.30. The calculated value of log K (Al
3++SiO(OH)
3
−
↔ AlOSi(OH)
3
2+
) = 6.72 (I=0.6 M) can be compared with corresponding constants for the formation of AlF
2+ and AlOH
2+ , which are equal to 6.16 and 8.20. Obviously, the stability of these Al(III) complexes decreases within the series OH
−>SiO(OH)
3
−
> F
− 相似文献
8.
M. Akaogi H. Takayama H. Kojitani H. Kawaji T. Atake 《Physics and Chemistry of Minerals》2007,34(3):169-183
The low-temperature isobaric heat capacities (C
p) of β- and γ-Mg2SiO4 were measured at the range of 1.8–304.7 K with a thermal relaxation method using the Physical Property Measurement System.
The obtained standard entropies (S°298) of β- and γ-Mg2SiO4 are 86.4 ± 0.4 and 82.7 ± 0.5 J/mol K, respectively. Enthalpies of transitions among α-, β- and γ-Mg2SiO4 were measured by high-temperature drop-solution calorimetry with gas-bubbling technique. The enthalpies of the α−β and β−γ
transitions at 298 K (ΔH°298) in Mg2SiO4 are 27.2 ± 3.6 and 12.9 ± 3.3 kJ/mol, respectively. Calculated α−β and β−γ transition boundaries were generally consistent
with those determined by high-pressure experiments within the errors. Combining the measured ΔH°298 and ΔS°298 with selected data of in situ X-ray diffraction experiments at high pressure, the ΔH°298 and ΔS°298 of the α−β and β−γ transitions were optimized. Calculation using the optimized data tightly constrained the α−β and β−γ transition
boundaries in the P, T space. The slope of α−β transition boundary is 3.1 MPa/K at 13.4 GPa and 1,400 K, and that of β−γ boundary 5.2 MPa/K at 18.7 GPa
and 1,600 K. The post-spinel transition boundary of γ-Mg2SiO4 to MgSiO3 perovskite plus MgO was also calculated, using the optimized data on γ-Mg2SiO4 and available enthalpy and entropy data on MgSiO3 perovskite and MgO. The calculated post-spinel boundary with a Clapeyron slope of −2.6 ± 0.2 MPa/K is located at pressure
consistent with the 660 km discontinuity, considering the error of the thermodynamic data. 相似文献
9.
The accepted standard state entropy of titanite (sphene) has been questioned in several recent studies, which suggested a
revision from the literature value 129.3 ± 0.8 J/mol K to values in the range of 110–120 J/mol K. The heat capacity of titanite
was therefore re-measured with a PPMS in the range 5 to 300 K and the standard entropy of titanite was calculated as 127.2
± 0.2 J/mol K, much closer to the original data than the suggested revisions. Volume parameters for a modified Murgnahan equation
of state: V
P,T
= V
298° × [1 + a°(T − 298) − 20a°(T − 298)] × [1 – 4P/(K
298 × (1 – 1.5 × 10−4 [T − 298]) + 4P)]1/4 were fit to recent unit cell determinations at elevated pressures and temperatures, yielding the constants V
298° = 5.568 J/bar, a° = 3.1 × 10−5 K−1, and K = 1,100 kbar. The standard Gibbs free energy of formation of titanite, −2456.2 kJ/mol (∆H°f = −2598.4 kJ/mol) was calculated from the new entropy and volume data combined with data from experimental reversals on the
reaction, titanite + kyanite = anorthite + rutile. This value is 4–11 kJ/mol less negative than that obtained from experimental
determinations of the enthalpy of formation, and it is slightly more negative than values given in internally consistent databases.
The displacement of most calculated phase equilibria involving titanite is not large except for reactions with small ∆S. Re-calculated baric estimates for several metamorphic suites yield pressure differences on the order of 2 kbar in eclogites
and 10 kbar for ultra-high pressure titanite-bearing assemblages. 相似文献
10.
N. V. Zubkova D. Yu. Pushcharovsky G. Giester E. Tillmanns I. V. Pekov D. A. Kleimenov 《Mineralogy and Petrology》2002,75(1-2):79-88
Summary
The crystal structure of arsentsumebite, ideally, Pb2Cu[(As, S)O4]2(OH), monoclinic, space group P21/m, a = 7.804(8), b = 5.890(6), c = 8.964(8) ?, β = 112.29(6)°, V = 381.2 ?3, Z = 2, dcalc. = 6.481 has been refined to R = 0.053 for 898 unique reflections with I> 2σ(I). Arsentsumebite belongs to the brackebuschite group of lead minerals with the general formula Pb2
Me(XO4)2(Z) where Me = Cu2+, Mn2+, Zn2+, Fe2+, Fe3+; X = S, Cr, V, As, P; Z = OH, H2O. Members of this group include tsumebite, Pb2Cu(SO4)(PO4)(OH), vauquelinite, Pb2Cu(CrO4)(PO4)(OH), brackebuschite, Pb2 (Mn, Fe)(VO4)2(OH), arsenbracke buschite, Pb2(Fe, Zn)(AsO4)2(OH, H2O), fornacite, Pb2Cu(AsO4)(CrO4)(OH), and feinglosite, Pb2(Zn, Fe)[(As, S)O4]2(H2O). Arsentsumebite and all other group members contain M = M–T chains where M = M means edge-sharing between MO6 octahedra and M–T represents corner sharing between octahedra and XO4 tetrahedra. A structural relationship exists to tsumcorite, Pb(Zn, Fe)2(AsO4)2 (OH, H2O)2 and tsumcorite-group minerals Me(1)Me(2)2(XO4)2(OH, H2O)2.
Received June 24, 2000; revised version accepted February 8, 2001 相似文献
11.
C. O'Reilly G. R. T. Jenkin M. Feely D. H. M. Alderton A. E. Fallick 《Contributions to Mineralogy and Petrology》1997,129(2-3):120-142
Fluid inclusions in granite quartz and three generations of veins indicate that three fluids have affected the Caledonian
Galway Granite. These fluids were examined by petrography, microthermometry, chlorite thermometry, fluid chemistry and stable
isotope studies. The earliest fluid was a H2O-CO2-NaCl fluid of moderate salinity (4–10 wt% NaCl eq.) that deposited late-magmatic molybdenite mineralised quartz veins (V1) and formed the earliest secondary inclusions in granite quartz. This fluid is more abundant in the west of the batholith,
corresponding to a decrease in emplacement depth. Within veins, and to the east, this fluid was trapped homogeneously, but
in granite quartz in the west it unmixed at 305–390 °C and 0.7–1.8 kbar. Homogeneous quartz δ18O across the batholith (9.5 ± 0.4‰n = 12) suggests V1 precipitation at high temperatures (perhaps 600 °C) and pressures (1–3 kbar) from magmatic fluids. Microthermometric data
for V1 indicate lower temperatures, suggesting inclusion volumes re-equilibrated during cooling. The second fluid was a H2O-NaCl-KCl, low-moderate salinity (0–10 wt% NaCl eq.), moderate temperature (270–340 °C), high δD (−18 ± 2‰), low δ18O (0.5–2.0‰) fluid of meteoric origin. This fluid penetrated the batholith via quartz veins (V2) which infill faults active during post-consolidation uplift of the batholith. It forms the most common inclusion type in
granite quartz throughout the batholith and is responsible for widespread retrograde alteration involving chloritization of
biotite and hornblende, sericitization and saussuritization of plagioclase, and reddening of K-feldspar. The salinity was
generated by fluid-rock interactions within the granite. Within granite quartz this fluid was trapped at 0.5–2.3 kbar, having
become overpressured. This fluid probably infiltrated the Granite in a meteoric-convection system during cooling after intrusion,
but a later age cannot be ruled out. The final fluid to enter the Granite and its host rocks was a H2O-NaCl-CaCl2-KCl fluid with variable salinity (8–28 wt% NaCl eq.), temperature (125–205 °C), δD (−17 to −45‰), δ18O (−3 to + 1.2‰), δ13CCO2 (−19 to 0‰) and δ34Ssulphate (13–23‰) that deposited veins containing quartz, fluorite, calcite, barite, galena, chalcopyrite sphalerite and pyrite (V3). Correlations of salinity, temperature, δD and δ18O are interpreted as the result of mixing of two fluid end-members, one a high-δD (−17 to −8‰), moderate-δ18O (1.2–2.5‰), high-δ13CCO2 (> −4‰), low-δ34Ssulphate (13‰), high-temperature (205–230 °C), moderate-salinity (8–12 wt% NaCl eq.) fluid, the other a low-δD (−61 to −45‰), low-δ18O (−5.4 to −3‰), low-δ13C (<−10‰), high-δ34Ssulphate (20–23‰) low-temperature (80–125 °C), high-salinity (21–28 wt% NaCl eq.) fluid. Geochronological evidence suggests V3 veins are late Triassic; the high-δD end-member is interpreted as a contemporaneous surface fluid, probably mixed meteoric
water and evaporated seawater and/or dissolved evaporites, whereas the low-δD end-member is interpreted as a basinal brine
derived from the adjacent Carboniferous sequence. This study demonstrates that the Galway Granite was a locus for repeated
fluid events for a variety of reasons; from expulsion of magmatic fluids during the final stages of crystallisation, through
a meteoric convection system, probably driven by waning magmatic heat, to much later mineralisation, concentrated in its vicinity
due to thermal, tectonic and compositional properties of granite batholiths which encourage mineralisation long after magmatic
heat has abated.
Received: 3 April 1996 / Accepted: 5 May 1997 相似文献
12.
Summary
Low-temperature phase transitions of leonite-type compounds, K2Me2+(SO4)2 · 4H2O (Me = Mg, Mn, Fe), are investigated by temperature dependent measurements of single-crystal X-ray reflection intensities
and lattice parameters. The transition temperatures and the progress of the transitions are determined by birefringence data
and differential scanning calorimetry. The cause for the phase transitions of leonite-type compounds is a dynamic disorder
of sulphate groups at room temperature (C2/m), that freezes in to an ordered structure (I2/a) at −4(1) °C in leonite, K2Mg(SO4)2 · 4H2O. At −153(1) °C the crystal structure switches to another ordered phase (P21/a). The Mn analogue shows the same succession with transition temperatures at −68(1) °C and −104(1) °C. The disordered room
temperature structure of the isotypic mineral mereiterite, K2Fe(SO4)2 · 4H2O, transforms directly to the ordered P21/a structure at 3(2) °C.
Analysis of X-ray intensities and of excess birefringence reveals that the displacive I2/a ⇔ P21/a phase transition of leonite and Mn-leonite is first order. According to Landau theory the C2/m ⇔ I2/a (leonite, Mn-leonite) and C2/m ⇔ P21/a (mereiterite) order-disorder transitions are almost tricritical.
Received March 7, 2001; revised version accepted June 27, 2001 相似文献
13.
Summary. ?Ca-tourmaline has been synthesized hydrothermally in the presence of Ca(OH)2 and CaCl2-bearing solutions of different concentration at T = 300–700 °C at a constant fluid pressure of 200 MPa in the system CaO-MgO-Al2O3-SiO2-B2O3-H2O-HCl. Synthesis of tourmaline was possible at 400 °C, but only above 500 °C considerable amounts of tourmaline formed. Electron
microprobe analysis and X-ray powder data indicate that the synthetic tourmalines are essentially solid solutions between
oxy-uvite, CaMg3- Al6(Si6O18)(BO3)3(OH)3O, and oxy-Mg-foitite, □(MgAl2)Al6(Si6O18)(BO3)3(OH)3O. The amount of Ca ranges from 0.36 to 0.88 Ca pfu and increases with synthesis temperature as well as with bulk Ca-concentration
in the starting mixture. No hydroxy-uvite, CaMg3(MgAl5)(Si6O18)(BO3)3(OH)3(OH), could be synthesized. All tourmalines have < 3 Mg and > 6 Al pfu. The Al/(Al + Mg)-ratio decreases from 0.80 to 0.70
with increasing Ca content. Al is coupled with Mg and Ca via the substitutions Al2□Mg−2Ca−1 and AlMg−1H−1. No single phase tourmaline could be synthesized. Anorthite ( + quartz in most runs) has been found coexisting with tourmaline.
Other phases are chlorite, tremolite, enstatite or cordierite.
Between solid and fluid, Ca is strongly fractionated into tourmaline ( + anorthite). The concentration ratio D = Ca(fluid)/Ca(tur) increases from 0.20 at 500 °C up to 0.31 at 700 °C. For the assemblage turmaline + anorthite + quartz + chlorite or tremolite
or cordierite, the relationship between Ca content in tourmaline and in fluid with temperature can be described by the equation
(whereby T = temperature in °C, Ca(tur) = amount of Ca on the X-site in tourmaline, Ca( fluid) = concentration of Ca2+ in the fluid in mol/l). The investigations may serve as a first guideline to evaluate the possibility to use tourmaline as
an indicator for the fluid composition.
Received July 24, 1998;/revised version accepted October 21, 1999 相似文献
Zusammenfassung. ?Synthese von Ca-Turmelin im System CaO-MgO-Al 2 O 3 -SiO 2 -B 2 O 3 -H 2 O-HCl Im System CaO-MgO-Al2O3-SiO2-B2O3-H2O-HCl wurde Ca-Turmalin hydrothermal aus Ca(OH)2 and CaCl2-haltigen L?sungen bei T = 300–700 °C und einem konstanten Fluiddruck von 200 MPa synthetisiert. Die Synthese von Turmalin war m?glich ab 400 °C, aber nur oberhalb von 500 °C bildeten sich deutliche Mengen an Turmalin. Elektronenstrahl-Mikrosondenanalysen und R?ntgenpulveraufnahmen zeigen, da? Mischkristalle der Reihe Oxy-Uvit, CaMg3Al6(Si6O18)(BO3)3(OH)3O, und Oxy-Mg-Foitit, □(MgAl2)Al6(Si6O18)(BO3)3(OH)3O gebildet wurden. Der Anteil an Ca variiert zwischen 0.36 und 0.88 Ca pfu und nimmt mit zunehmender Synthesetemperatur und zunehmender Ca-Konzentration im System zu. Hydroxy-Uvit, CaMg3(MgAl5) (Si6O18)(BO3)3(OH)3(OH), konnte nicht synthetisiert werden. Alle Turmaline haben < 3 Mg und > 6 Al pfu. Dabei nimmt das Al/(Al + Mg)- Verh?ltnis mit zunehmendem Ca-Gehalt von 0.80 auf 0.70 ab. Al ist gekoppelt mit Mg und Ca über die Substitutionen Al2□Mg−2Ca−1 und AlMg−1H−1. Einphasiger Turmalin konnte nicht synthetisiert werden. Anorthit (+ Quarz in den meisten F?llen) koexistiert mit Turmalin. Andere Phasen sind Chlorit, Tremolit, Enstatit oder Cordierit. Ca zeigt eine deutliche Fraktionierung in den Festk?rpern Turmalin (+ Anorthit). Das Konzentrationsverh?ltnis D = Ca(fluid)/Ca(tur) nimmt von 0.20 bei 500 °C auf 0.31 bei 700 °C zu. Für die Paragenese Turmalin + Anorthit + Quarz mit Chlorit oder Tremolit oder Cordierit gilt folgende Beziehung zwischen Ca-Gehalt in Turmalin und Fluid und der Temperatur: (wobei T = Temperatur in °C, Ca(tur) = Anteil an Ca auf der X-Position in Turmalin, Ca(fluid) = Konzentration von Ca2+ im Fluid in mol/l). Die Untersuchungen dienen zur ersten Absch?tzung, ob Turmalin als Fluidindikator petrologisch nutzbar ist.
Received July 24, 1998;/revised version accepted October 21, 1999 相似文献
14.
The polarized single-crystal Raman spectra of synthetic H2O-containing alkali-free beryl were recorded at room and low temperatures, and the polarized single-crystal IR spectra at
room temperature. The H2O molecule in the channel cavities is characterized by a Raman-active symmetric stretching vibration (ν1) at 3607 cm−1 and an IR-active asymmetric stretch (ν3) at 3700 cm−1 at room temperature. At low temperatures this ν3 mode is observed in the Raman. Weak ν1 and ν3 modes of a second type of H2O are also observed in the Raman spectra but only at 5 K. The H⋯·H vector of the most abundant type of H2O is parallel to the channel axis of beryl along [0 0 0 1]. The components of the polarizability tensor of the ν1 mode of H2O are similar to, but not exactly the same as, those of a free H2O molecule. The Raman measurements indicate that the H2O molecule is rotationally disordered around [0 0 0 1]. External translation and librational modes of H2O could be observed as overtones with the internal H2O-stretching modes. In the case of the librational motions, normal modes could also be observed directly in the Raman spectra
at ∼200 cm−1. The energies of the translational modes can be determined from an analysis of the overtones and are about 9 cm−1 in energy (i.e., Tz). The energies of the librational modes are about 210 cm−1 for Rx and 190 cm−1 for Ry.
Received: 8 April 1999 / Accepted: 5 April 2000 相似文献
15.
Enthalpies of drop solution (ΔH
drop-sol) of CaGeO3, Ca(Si0.1Ge0.9)O3, Ca(Si0.2Ge0.8)O3, Ca(Si0.3Ge0.7)O3 perovskite solid solutions and CaSiO3 wollastonite were measured by high-temperature calorimetry using molten 2PbO · B2O3 solvent at 974 K. The obtained values were extrapolated linearly to the CaSiO3 end member to give ΔH
drop-sol of CaSiO3 perovskite of 0.2 ± 4.4 kJ mol−1. The difference in ΔH
drop-sol between CaSiO3, wollastonite, and perovskite gives a transformation enthalpy (wo → pv) of 104.4 ± 4.4 kJ mol−1. The formation enthalpy of CaSiO3 perovskite was determined as 14.8 ± 4.4 kJ mol−1 from lime + quartz or −22.2 ± 4.5 kJ mol−1 from lime + stishovite. A comparison of lattice energies among A2+B4+O3 perovskites suggests that amorphization during decompression may be due to the destabilizing effect on CaSiO3 perovskite from a large nonelectrostatic energy (repulsion energy) at atmospheric pressure. By using the formation enthalpy
for CaSiO3 perovskite, phase boundaries between β-Ca2SiO4 + CaSi2O5 and CaSiO3 perovskite were calculated thermodynamically utilizing two different reference points [where ΔG(P,T )=0] as the measured phase boundary. The calculations suggest that the phase equilibrium boundary occurs between 11.5 and
12.5 GPa around 1500 K. Its slope is still not well constrained.
Received: 20 September 2000 / Accepted: 17 January 2001 相似文献
16.
Near-infrared (NIR) absorption bands related to total water (4000 and 7050 cm−1), OH groups (4500 cm−1) and molecular H2O (5200 cm−1) were studied in two polymerised glasses, a synthetic albitic composition and a natural obsidian. The water contents of the
glasses were determined using Karl Fischer titration. Molar absorption coefficients were calculated for each of the bands
using albitic glasses containing between 0.54 and 9.16 wt.% H2O and rhyolitic glasses containing between 0.97 and 9.20 wt.% H2O. Different combinations of baseline type and intensity measure (peak height/area) for the combination bands at 4500 and
5200 cm−1 were used to investigate the effect of evaluation procedure on calculated hydrous species concentrations. Total water contents
calculated using each of the baseline/molar absorption coefficient combinations agree to within 5.8% relative for rhyolitic
and 6.5% relative for albitic glasses (maximum absolute differences of 0.08 and 0.15 wt.% H2O, respectively). In glasses with water contents >1 wt.%, calculated hydrous species concentrations vary by up to 17% relative
for OH and 11% relative for H2O (maximum absolute differences of 0.33 and 0.43 wt.% H2O, respectively). This variation in calculated species concentrations is typically greater in rhyolitic glasses than albitic.
In situ, micro-FTIR analysis at 300 and 100 K was used to investigate the effect of varying temperature on the NIR spectra of the
glasses. The linear and integral molar absorption coefficients for each of the bands were recalculated from the 100 K spectra,
and were found to vary systematically from the 300 K values. Linear molar absorption coefficients for the 4000 and 7050 cm−1 bands decrease by 16–20% and integral molar absorption coefficients by up to 30%. Depending on glass composition and baseline
type, the integral molar absorption coefficients for the absorption bands related to OH groups and molecular H2O change by up to −5.8 and +7.4%, respectively, while linear molar absorption coefficients show less variation, with a maximum
change of ∼4%. Using the new molar absorption coefficients for the combination bands to calculate species concentrations at
100 K, the maximum change in species concentration is 0.08 wt.% H2O, compared with 0.39 wt.% which would be calculated if constant values were assumed for the combination band molar absorption
coefficients. Almost all the changes in the spectra can therefore be interpreted in terms of changing molar absorption coefficient,
rather than interconversion between hydrous species.
Received: 17 December 1998 / Revised, accepted 8 July 1999 相似文献
17.
K. S. Gavrichev M. A. Ryumin A. V. Tyurin V. M. Gurevich L. N. Komissarova 《Geochemistry International》2010,48(9):932-939
The heat capacity of xenotime YPO4(c) was measured by adiabatic calorimetry at 4.78–348.07 K. Our experimental and literature data on H
0(T)-H
0(298.15 K) of Y orthophosphate were utilized to derive the C
p
0(T) function of xenotime at 0–1600 K, which was then used to calculate the values of thermodynamic functions: entropy, enthalpy
change, and reduced Gibbs energy. These functions assume the following values at 298.15 K: C
p
0 (298.15 K) = 99.27 ± 0.02 J K−1 mol−1, S
0(298.15 K) = 93.86 ± 0.08 J K−1 mol−1, H
0(298.15 K) − H
0(0) = 15.944 ± 0.005 kJ mol−1, Φ0(298.15 K) = 40.38 ± 0.08 J K−1 mol−1. The value of the free energy of formation Δ
f
G
0(YPO4, 298.15 K) is −1867.9 ± 1.7 kJ mol−1. 相似文献
18.
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
19.
Detlef W. Fasshauer Niranjan D. Chatterjee Ladislav Cemic 《Contributions to Mineralogy and Petrology》1998,133(1-2):186-198
Heat capacity, thermal expansion, and compressibility data have been obtained for a number of selected phases of the system
NaAlSiO4-LiAlSiO4-Al2O3-SiO2-H2O. All C
p
measurements have been executed by DSC in the temperature range 133–823 K. The data for T ≥ 223 K have been fitted to the function C
p
(T) = a + cT
−2 + dT
−0.5 + fT
−3, the fit parameters being The thermal expansion data (up to 525 °C) have been fitted to the function V
0(T) = V
0(T) [1 + v
1 (T−T
0) + v
2 (T−T
0)2], with T
0 = 298.15 K. The room-temperature compressibility data (up to 6 GPa) have been smoothed by the Murnaghan equation of state.
The resulting parameters are These data, along with other phase property and reaction reversal data from the literature, have
been simultaneously processed by the Bayes method to derive an internally consistent thermodynamic dataset (see Tables 6 and
7) for the NaAlSiO4-LiAlSiO4-Al2O3-SiO2-H2O quinary. Phase diagrams generated from this dataset are compatible with cookeite-, ephesite-, and paragonite-bearing assemblages
observed in metabauxites and common metasediments. Phase diagrams obtained from the same database are also in agreement with
the cookeite-free, petalite-, spodumene-, eucryptite-, and bikitaite-bearing assemblages known to develop in the subsolidus
phase of recrystallization of␣lithium-bearing pegmatites. It is gratifying to note that the cookeite phase relations predicted
earlier by Vidal and Goffé (1991) in the context of the system Li2O-Al2O3-SiO2-H2O agree with our results in a general way.
Received: 19 May 1998 / Accepted: 25 June 1998 相似文献
20.
To interpret the degassing of F-bearing felsic magmas, the solubilities of H2O, NaCl, and KCl in topaz rhyolite liquids have been investigated experimentally at 2000, 500, and ≈1 bar and 700° to 975 °C.
Chloride solubility in these liquids increases with decreasing H2O activity, increasing pressure, increasing F content of the liquid from 0.2 to 1.2 wt% F, and increasing the molar ratio
of ((Al + Na + Ca + Mg)/Si). Small quantities of Cl− exert a strong influence on the exsolution of magmatic volatile phases (MVPs) from F-bearing topaz rhyolite melts at shallow
crustal pressures. Water- and chloride-bearing volatile phases, such as vapor, brine, or fluid, exsolve from F-enriched silicate
liquids containing as little as 1 wt% H2O and 0.2 to 0.6 wt% Cl at 2000 bar compared with 5 to 6 wt% H2O required for volatile phase exsolution in chloride-free liquids. The maximum solubility of Cl− in H2O-poor silicate liquids at 500 and 2000 bar is not related to the maximum solubility of H2O in chloride-poor liquids by simple linear and negative relationships; there are strong positive deviations from ideality
in the activities of each volatile in both the silicate liquid and the MVP(s). Plots of H2O versus Cl− in rhyolite liquids, for experiments conducted at 500 bar and 910°–930 °C, show a distinct 90° break-in-slope pattern that
is indicative of coexisting vapor and brine under closed-system conditions. The presence of two MVPs buffers the H2O and Cl− concentrations of the silicate liquids. Comparison of these experimentally-determined volatile solubilities with the pre-eruptive
H2O and Cl− concentrations of five North American topaz and tin rhyolite melts, determined from melt inclusion compositions, provides
evidence for the exsolution of MVPs from felsic magmas. One of these, the Cerro el Lobo magma, appears to have exsolved alkali
chloride-bearing vapor plus brine or a single supercritical fluid phase prior to entrapment of the melt inclusions and prior
to eruption.
Received: 6 November 1995 / Accepted: 29 January 1998 相似文献