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1.
 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.
 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   

3.
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.
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   

4.
 Infrared absorption spectra of brucite Mg (OH)2 were measured under high pressure and high temperature from 0.1 MPa 25 °C to 16 GPa 360 °C using infrared synchrotron radiation at BL43IR of Spring-8 and a high-temperature diamond-anvil cell. Brucite originally has an absorption peak at 3700 cm−1, which is due to the OH dipole at ambient pressure. Over 3 GPa, brucite shows a pressure-induced absorption peak at 3650 cm−1. The pressure-induced peak can be assigned to a new OH dipole under pressure. The new peak indicates that brucite has a new proton site under pressure and undergoes a high-pressure phase transition. From observations of the pressure-induced peak under various P–T condition, a stable region of the high-pressure phase was determined. The original peak shifts to lower wavenumber at −0.25 cm−1 GPa−1, while the pressure-induced peak shifts at −5.1 cm−1 GPa−1. These negative dependences of original and pressure-induced peak shifts against pressure result from enhanced hydrogen bond by shortened O–H···O distance, and the two dependences must result from the differences of hydrogen bond types of the original and pressure-induced peaks, most likely from trifurcated and bent types, respectively. Under high pressure and high temperature, the pressure-induced peak disappears, but a broad absorption band between 3300 and 3500 cm−1 was observed. The broad absorption band may suggest free proton, and the possibility of proton conduction in brucite under high pressure and temperature. Received: 16 July 2001 / Accepted: 25 December 2001  相似文献   

5.
The low-pressure stability of clinohumite has been investigated in phase-equilibrium experiments on the reaction forsterite + brucite = clinohumite. The reaction was bracketed between 2.45 and 2.84 GPa at 650 °C, extending to between 1.37 and 1.57 GPa at 850 °C. At temperatures above the reaction brucite = periclase + vapour, the reaction clinohumite = forsterite + vapour was bracketed between 1.27 and 1.52 GPa at 900 °C, rising to between 1.90 and 2.00 GPa at 1000 °C. The position of the reaction forsterite + brucite = clinohumite is ∼0.5 GPa below the position determined in previous work, the difference arising either from pressure uncertainties in both studies, from enhanced reaction to clinohumite in this study due to the presence of excess brucite in the starting material, or from different concentrations of defects in the two samples. The brackets on the reaction were combined with other measured and estimated thermodynamic data for clinohumite to determine its enthalpy of formation and entropy, in a revised version of the thermodynamic dataset of Holland and Powell (1998). The values obtained were ΔH f =−9607.29±3.05 kJ mol−1, S=445 J mol−1 K−1. These data were used to calculate positions of other reactions involving clinohumite. The calculations suggest a larger stability field for clinohumite than implied by the results of previous experimental studies, indicating a need for more high-pressure phase-equilibrium studies to provide better thermodynamic data. Received: 30 April 1999 / Accepted: 8 November 1999  相似文献   

6.
 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   

7.
Oxygen and hydrogen stable isotope ratios of eclogite-facies metagabbros and metabasalts from the Cycladic archipelago (Greece) document the scale and timing of fluid–rock interaction in subducted oceanic crust. Close similarities are found between the isotopic compositions of the high-pressure rocks and their ocean-floor equivalents. High-pressure minerals in metagabbros have low δ18O values: garnet 2.6 to 5.9‰, glaucophane 4.3 to 7.1‰; omphacite 3.5 to 6.2‰. Precursor actinolite that was formed during the hydrothermal alteration of the oceanic crust by seawater analyses at 3.7 to 6.3‰. These compositions are in the range of the δ18O values of unaltered igneous oceanic crust and high-temperature hydrothermally altered oceanic crust. In contrast, high-pressure metabasalts are characterised by 18O-enriched isotopic compositions (garnet 9.2 to 11.5‰, glaucophane 10.6 to 12.5‰, omphacite 10.2 to 12.8‰), which are consistent with the precursor basalts having undergone low-temperature alteration by seawater. D/H ratios of glaucophane and actinolite are also consistent with alteration by seawater. Remarkably constant oxygen isotope fractionations, compatible with isotopic equilibrium, are observed among high-pressure minerals, with Δglaucophane−garnet = 1.37 ± 0.24‰ and Δomphacite−garnet = 0.72 ± 0.24‰. For the estimated metamorphic temperature of 500 °C, these fractionations yield coefficients in the equation Δ = A * 106/T 2 (in Kelvin) of Aglaucophane−garnet = 0.87 ± 0.15 and Aomphacite−garnet = 0.72 ± 0.24. A fractionation of Δglaucophane–actinolite = 0.94 ± 0.21‰ is measured in metagabbros, and indicates that isotopic equilibrium was established during the metamorphic reaction in which glaucophane formed at the expense of actinolite. The preservation of the isotopic compositions of gabbroic and basaltic oceanic crust and the equilibrium fractionations among minerals shows that high-pressure metamorphism occurred at low water/rock ratios. The isotopic equilibrium is only observed at hand-specimen scale, at an outcrop scale isotopic compositional differences occur among adjacent rocks. This heterogeneity reflects metre-scale compositional variations that developed during hydrothermal alteration by seawater and were subsequently inherited by the high-pressure metamorphic rocks. Received: 4 January 1999 / Accepted: 7 July 1999  相似文献   

8.
 A high pressure neutron powder diffraction study of portlandite [Ca(OH)2] has been performed at ISIS facility (U.K.); nine spectra have been collected increasing the pressure by steps, up to 10.9 GPa, by means of a Paris-Edinburgh cell installed on the POLARIS diffractometer. The tensorial formalism of the lagrangian finite strain theory and the Birch-Murnaghan equation of state have been used to determine, independently, two values of the bulk modulus of portlandite, obtaining K 0=38.3(±1.1) GPa [linear incompressibilities: K 0a=188.4(±9.9), K 0c=64.5(±2.5) GPa] and K 0=34.2(±1.4) GPa, respectively. The present results comply with values from previous measurements by X-ray diffraction [K 0=37.8(±1.8) GPa] and Brillouin spectroscopy [K 0=31.7(±2.5) GPa]. Reasonably, Ca(OH)2 has revealed to be bulkly softer than Mg(OH)2 [K 0=41(±2), K 0a=313, K 0c=57 GPa]. The Ca(OH)2 linear incompressibility values reflect the nature of forces acting to stabilize the (001) layer structure and, further, prove that the replacement Ca/Mg mainly affects the elastic properties in the (001) plane, rather than along the [001] direction. Data from a full refinement of the structure at room pressure are reported. Received January 12, 1996/Revised, accepted June 15, 1996  相似文献   

9.
 The incorporation of hydrogen (deuterium) into the coesite structure was investigated at pressures from 3.1 to 7.5 GPa and temperatures of 700, 800, and 1100 °C. Hydrogen could only be incorporated into the coesite structure at pressures greater 5.0 GPa and 1100 °C . No correlation between the concentration of trace elements such as Al and B and the hydrogen content was observed based on ion probe analysis (1335 ± 16 H ppm and 17 ± 1 Al ppm at 7.5 GPa, 1100 °C). The FTIR spectra show three relatively intense bands at 3575, 3516, and 3459 cm−1 (ν1 to ν3, respectively) and two very weak bands at 3296 and 3210 cm−1 (ν4 and ν5, respectively). The band at 3516 cm−1 is strongly asymmetric and can be resolved into two bands, 3528 (ν2a) and 3508 (ν2b) cm−1, with nearly identical areas. Polarized infrared absorption spectra of coesite single-crystal slabs, cut parallel to (0 1 0) and (1 0 0), were collected to locate the OH dipoles in the structure and to calibrate the IR spectroscopy for quantitative analysis of OH in coesite (ɛ i ,tot=190 000 ± 30 000 l mol−1 H2O cm−2). The polarized spectra revealed a strong pleochroism of the OH bands. High-pressure FTIR spectra at pressures up to 8 GPa were performed in a diamond-anvil cell to gain further insight into incorporation mechanism of OH in coesite. The peak positions of the ν1, ν2, and ν3 bands decrease linearly with pressure. The mode Grüneisen parameters for ν1, ν2, and ν3 are −0.074, −0.144 and −0.398, respectively. There is a linear increase of the pressure derivatives with band position which follows the trend proposed by Hofmeister et al. (1999). The full widths at half maximum (FWHM) of the ν1, ν2, and ν3 bands increase from 35, 21, and 28 cm−1 in the spectra at ambient conditions to 71, 68, and 105 in the 8 GPa spectra, respectively. On the basis of these results, a model for the incorporation of hydrogen in coesite was developed: the OH defects are introduced into the structure by the substitution Si4+(Si2)+4O2−= [4]□(Si2) + 4OH−, which gives rise to four vibrations, ν1, ν2a, ν2b, and ν3. Because the OH(D)-bearing samples do contain traces of Al and B, the bands ν4 and ν5 may be coupled to Al and/or B substitution. Received: 19 December 2000 / Accepted: 23 April 2001  相似文献   

10.
 The monoclinic titanite-like high-pressure form of calcium disilicate has been synthesized and quenched to ambient conditions to form the triclinic low-pressure phase containing silicon in four-, five- and sixfold coordination. The enthalpy of formation of the quench product has been measured by high-temperature oxide melt calorimetry. The value obtained from samples from a series of several synthesis experiments is ΔH f = (−26.32 ± 4.27) kJ mol−1 for the formation from the component oxides, or ΔH f  = (−2482.81 ± 4.59) kJ mol−1 for the formation from the elements. The result is identical within experimental error to available estimates, although the previously predicted energy difference between the monoclinic and triclinic phases could not be verified. Received: 16 February 2000 / Accepted: 14 July 2000  相似文献   

11.
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   

12.
The Archean Shawmere anorthosite lies within the granulite facies portion of the Kapuskasing Structural Zone (KSZ), Ontario, and is crosscut by numerous linear alteration veins containing calcite + quartz ± dolomite ± zoisite ± clinozoisite ± margarite ±paragonite ± chlorite. These veins roughly parallel the trend of the Ivanhoe Lake Cataclastic Zone. Equilibria involving clinozoisite + margarite + quartz ± calcite ± plagioclase show that the vein minerals were stable at T < 600 °C, XCO2 < 0.4 at P ≈ 6 kbar. The stabilities of margarite and paragonite in equilibrium with quartz are also consistent with T < 600 °C and XCO2 < 0.4 at 6 kbar. Additional assemblages consisting of calcite + clinochlore + quartz + talc + margarite indicate T < 500 °C with XCO2 > 0.9. Thus, vein formation, while clearly retrograde, spanned a range of temperatures, and fluid compositions evolved from H2O-rich to CO2-rich. The calcite in the retrograde veins has δ18O values that range from 8.4 to 11.2‰ (average = +9.7 ± 0.9‰) and δ13C values that range from −3.9 to −1.6‰ (average = −3.1 ± 0.6‰). These values indicate that the fluids from which calcite precipitated underwent extensive exchange with the anorthosite and other crustal lithologies. The fluids may have been initially derived either from devolatilization of metamorphic rocks or crystallization of igneous rocks in the adjacent Abitibi subprovince. Vein quartz contains CO2-rich fluid inclusions (final melting T = −57.0 to −58.7 °C) that range in size from 5 to 17 μm. Measured homogenization temperatures (T h) range from −44.0 to 14.5 °C, however for most inclusions (46 of S1), T h = −44.0 to −21.1 °C (ρCO2 ≈ 1.13 to 1.05 g/cm3). At 400 to 600 °C, these densities correspond to pressures of 3.5 to 7 kbar, which is the best estimate of pressures of vein formation. It has been argued that some high density CO2-rich fluid inclusions found in the KSZ were formed during peak metamorphism and thus document the presence of a CO2-rich fluid during peak granulite facies metamorphism (Rudnick et al. 1984). The association of high density CO2-rich fluid inclusions with clearly retrograde veins documents the formation of similar composition and density inclusions after the peak of metamorphism. Thus, the coincidence of entrapment pressures calculated from fluid inclusion density measurements with peak metamorphic pressures alone should not be considered strong evidence for peak metamorphic inclusion entrapment. All fluid inclusion results are consistent with an initially semi-isobaric retrograde P–T path. Received: 2 April 1996 / Accepted: 15 November 1996  相似文献   

13.
 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   

14.
 The hydrothermal reaction between grossular and 1 molar manganese chloride solution was studied at 2 kbar and 600 °C at various bulk Ca/(Ca+Mn) compositions: Ca3Al2Si3O12+3Mn2+(aq) ⇔ Mn3Al2Si3O12+3Ca2+(aq) The reaction products are garnets of the spessartine-grossular solid-solution series which discontinuously armour the dissolving grossular grains. The first garnet to crystallize is spessartine rich (X gt Mn≥0.95), reflecting the high Mn content of the solution, but as the reaction proceeds more calcium-rich garnets progressively overgrow the initial products. The armouring product layer is detached from the dissolving grossular, which allows the progressive overgrowth to occur on both its external and internal surfaces and results in the development of a two directional Ca/(Ca+Mn) zoning pattern in the product grains. The compositional changes in the run products are consistent with attainment of heterogeneous equilibrium between the external rims of the spessartine-grossular garnets and the bulk solutions in runs of duration ≥24 hours. Plots of ln KD versus X gt Ca maxima show linear variations that are not consistent with the ideal mixing that has been proposed for spessartine-grossular garnets at temperatures of 900 to 1200 °C. The data rather fit a regular solution model with the parameters ΔG° (600 °C, 2 kbar)=−8.0±0.8 kJ/mol and w gt CaMn=2.6±2.0 kJ/mol. Existing solubility measurements and thermodynamic data from other Ca and Mn silicates support the calculated data. Grossular activities calculated using the w gt CaMn parameter indicate that even in manganese-rich metapelites pressure estimates calculated using the garnet-plagioclase-Al2SiO5-quartz barometer will not be increased by more than 0.2 kbar. Received: 18 January 1995/Accepted: 4 June 1996  相似文献   

15.
High temperature stability limit of phase egg, AlSiO3(OH)   总被引：1，自引：1，他引：0  
The stability relations of phase egg, AlSiO3(OH), have been investigated at pressures from 7 to 20 GPa, and temperatures from 900 to 1700 °C in a multi-anvil apparatus. At the lower pressures phase egg breaks down according to the univariant reaction, phase egg = stishovite + topaz-OH, which extends from 1100 °C at 11 GPa to 1400 °C at 13 GPa where it terminates at an invariant point involving corundum. At pressures above the invariant point, the stability of phase egg is limited by the breakdown reaction, phase egg = stishovite + corundum + fluid, which extends from the invariant point to 1700 °C at 20 GPa. Stishovite crystallized in the Al2O3-SiO2-H2O system contains Al2O3, and the amount of Al2O3 increases with increasing temperature. It is inferred that the Al2O3 content is controlled by the charge-balanced substitution of Si4+ by Al3+ and H+. Aluminum-bearing stishovite coexisting with an H2O-rich fluid may contain a certain amount of water. Therefore, phase egg and stishovite in a subducting slab could transport some H2O into the deep Earth. Received: 14 October 1998 / Accepted: 19 May 1999  相似文献   

16.
Water solubility in pyrope to 100 kbar   总被引：14，自引：0，他引：14  
The solubility and incorporation mechanism of water in natural, almost pure pyrope from Dora Maira, Western Alps was investigated. The infrared spectrum of the natural, untreated sample (58 ppm water) shows several exceptionally sharp bands in the OH-stretching region, including a single band at 3601.9 cm−1 and a band system with main components at 3640.5, 3650.8 and 3660.6 cm−1. High-temperature and high-pressure infrared spectra suggest that the two absorption features arise from almost free OH groups in sites with different compressibility and thermal expansivity, with the site causing the 3601.9 cm−1 band being much stiffer. Pyrope samples were annealed in a piston-cylinder or multi-anvil apparatus for several days in the presence of excess water, excess SiO2 and excess Al2SiO5 to determine the equilibrium solubility of water in pyrope to 100 kbar. Total solubility increases with pressure, however, this is exclusively due to the high-frequency band system, while the intensity of the low-frequency band decreases with pressure. At 1000 °C and the oxygen fugacity of the Ni-NiO buffer, the bulk solubility can be described by the equation c OH =Af H2O 0.5exp(−PΔV/RT) with A = 0.679 ppm/bar0.5 and ΔV = 5.71 cm3/mol. This equation implies the incorporation of water in the crystal as isolated OH groups. With increasing temperature, solubility appears to decrease with ΔH = − 14 kJ/mol. At Fe-FeO buffer conditions, solubility is 30 to 50% lower than with the Ni-NiO buffer, suggesting that the incorporation of OH is not coupled to the reduction of Fe3+. Possibly, the 3601.9 cm−1 band is associated with the tetrahedral OH B defect and the high-frequency system with the dodecahedral OH Li defect. Based on the experimentally established solubility model, it is estimated that garnet in a hot subducted slab will transport 170 ppm of water into the mantle beyond the breakdown limit of amphibole. In a cold slab, 470 ppm of water can be incorporated into garnet at the breakdown limit of phengite. These numbers imply that a significant fraction of the total water in the hydrosphere has been recycled into the mantle since the Proterozoic. Received: 6 January 1997 / Accepted: 27 March 1997  相似文献   

17.
Diffusion couples made from homogeneous gem quality natural pyrope and almandine garnets were annealed within graphite capsules under anhydrous conditions at 22–40 kbar, 1057–1400 °C in a piston-cylinder apparatus. The concentration profiles that developed in each couple were modeled to retrieve the self diffusion coefficients [D(I)] of the divalent cations Fe, Mg, Mn and Ca. Because of their usually low concentrations and lack of sufficient compositional change across the interface of the diffusion couples, only a few reliable data can be obtained for D(Ca) and D(Mn) from these experiments. However, nine sets of D(Fe) and D(Mg) data were retrieved in the above P-T range, and cast in the form of Arrhenian relation, D=D 0exp{−[Q(1 bar)+PΔV +]/RT}. The values of the activation energy (Q) and activation volume (ΔV +) depend on whether f O2 is constrained by graphite in the system C-O or held constant. For the first case, we have for Fe:Q(1 bar)=65,532±10,111 cal/mol, D 0=3.50 (±2.30)×10−5 cm2/s, ΔV +=5.6(±2.9) cm3/mol, and for Mg:Q(1 bar)=60,760±8,257 cal/mol, D 0=4.66 (±2.48)×10−5 cm2/s, ΔV +=5.3(±3.0) cm3/mol. Here the ΔV + values have been taken from Chakraborty and Ganguly (1992). For the condition of constant f O2, the Q values are ∼9 kcal lower and ΔV + values are ∼4.9 cm3/mol larger than the above values. Lower temperature extrapolation of the Arrhenian relation for D(Mg) is in good agreement with the Mg tracer diffusion data (D * Mg) of Chakraborty and Rubie (1996) and Cygan and Lasaga (1985) at 1 bar, 750–900 °C, when all data are normalized to the same pressure and to f O2 defined by graphite in the system C-O. The D * Mg data of Schwandt et al. (1995), on the other hand, are lower by more than an order of magnitude than the low temperature extrapolation of the present data, when all data are normalized to the same pressure and to f O2 defined by the graphite buffer. Comparison of the D(Fe), D(Mg) and D(Mn) data in the pyrope-almandine diffusion couple with those in the spessartine-almandine diffusion couple of Chakraborty and Ganguly (1992) shows that the self diffusion of Fe and Mn are significantly enhanced with the increase in Mn/Mg ratio; the enhancement effect on D(Mg) is, however, relatively small. Proper application of the self diffusion data to calculate interdiffusion coefficient or D matrix elements for the purpose of modeling of diffusion processes in natural garnets must take into account these compositional effects on D(I) along with the effects of thermodynamic nonideality, f O2, and pressure. Received: 8 May 1997 / Accepted: 2 October 1997  相似文献   

18.
Summary The kinetics of phytoplankton frustule dissolution has generally been studied as the appearance of silicic acid in a batch reactor. Unfortunately, this approach, though often illuminating, has not so far been successful because of the difficulty of parameterising the full reaction curve. This current study shows how the initial rate approach to chemical kinetics offers a way around this bottleneck, thereby allowing much chemical kinetics information about frustule dissolution to be collected. The technique is shown to be flexible and suited to short reaction times which facilitate detailed quantitative kinetics investigation, indeed, as would be expected in a solution phase, kinetics study. The technique is exemplified by a dissolution study of uncleaned frustules of Cyclotella crypticaat 40 °C and above. The frustules were found to yield the same dissolution rate after 5 weeks dark storage, at 4 °C. Meanwhile, log dissolution rate was found to vary linearly with pH, with gradient 0.38 ± 0.01 (r 2=0.990). Linearity was upheld even at pHs as high as 14. Finally, a robust Arrhenius plot was established between 40 and 90 °C yielding an activation energy for dissolution of 84 ± 3 kJ mol −1. Follow through with the Eyring equation yielded an activation enthalpy, ΔH ‡, and an activation entropy, ΔS ‡, of 81 and 85 J mol −1 K −1, respectively. The discussion brings salient aspects of existing knowledge about diatom frustule dissolution kinetics into the wider context of silicate mineral dissolution.  相似文献   

19.
Summary ?The petrology and P-T evolution of mica schists from two regional scale tectonic (shear) zones that separate high grade terrains (“mobile belts”) from cratons are described. These are the 2.4–1.9 Ga Tanaelv Belt, a suture zone that separates the Lapland granulite complex from the Karelian craton (Kola Peninsula–Fennoscandia), and the 2.69 Ga Hout River Shear Zone that separates the > 2.9 Ga Kaapvaal craton from the 2.69 Ga South Marginal Zone of the Limpopo high-grade terrain (South Africa). Two metamorphic zones are identified in strongly deformed mica schists from the 1.9 Ga Korva Tundra Group of the Tanaelv belt: (1) a chlorite-staurolite zone tectonically overlaying gneisses of the Karelian craton, and (2) a kyanite-biotite zone tectonically underlying garnet amphibolites of the Tanaelv Belt, which are in tectonic contact with the Lapland granulite complex. The prograde reaction Chl+St+Ms ↠ Ky+Bt+Qtz+H2O clearly defines a boundary between zones (1) and (2). Rotated garnet porphyroblasts from zone (1) contain numerous inclusions (Otz, Chl, Ms), and show clear Mg/Fe chemical zoning, suggesting garnet growth during prograde metamorphism. The metamorphic peak, T = 650°C and P = 7.5 kbar, is recorded in the kyanite-biotite zone and characterized by unzoned snowball garnet. In many samples of mica schists euhedral garnet porphyroblasts of the retrograde stage are completely devoid of mineral inclusions while N Mg decreases from core to rim, indicating a decrease in P-T from 650°C, 7.5 kbar to 530°C, 5 kbar. The Hout River Shear Zone (South Africa) shows metamorphic zonation from greenschists through epidote amphibolites to garnet amphibolites. Rare strongly deformed mica schists (Chl+Grt+Pl+Ms+Bt+Qtz) occur as thin layers among epidote-amphibolites only. Garnet porphyroblasts in the schists are similar to that of the Tanaelv Belt recording a prograde P-T path with peak conditions of T = 600°C and P∼ 5.5 kbar. The retrograde stage is documented by the continuous reaction Prp+2Ms+Phl ↠ 6Qtz+3East recording a minimum T = 520°C and P ∼ 3.3 kbar. Similar narrow clock-wise P-T loops recorded in mica schists from both studied shear zones suggest similarities in the geodynamic history of both shear zones under consideration.
Zusammenfassung ?P-T Pfade und tektonische Entwicklung von Scherzonen, die hochgradige Terranes von Kratonen trennen: Zwei Beispiele von der Halbinsel Kola (Russland) und der Limpopo-Region (Südafrika) Die Petrologie und P-T Entwicklung von Glimmerschiefern aus zwei regionalen tektonischen Scherzonen, die hochgradige Terranes (“mobile belts”) von Kratonen trennen, werden beschrieben. Diese sind der 2.4−1.9 Ga Tanaev Belt, eine Suturzone, die die Lappland Granulite vom karelischen Pluton (Halbinsel Kola - Fennoskandien) trennt, sowie die 2.69 Ga Hout River Shear Zone, die den > 2.9 Ga Kaapvaal Kraton von der 2.69 Ga South Marginal Zone des hochgradigen Limpopo Terranes (Südafrika) trennt. Zwei metamorphe Zonen sind in stark deformierten Glimmerschiefern der 1.9 Ga Korva Tundra Group zu unterscheiden: (1) eine Chlorit-Staurolith-Zone, die den Gneisen des karelischen Kratons auflagert, und (2) eine Kyanit-Biotit-Zone, die die Granatamphibolite des Tanaev Belt unterlagert und in tektonischem Kontakt mit dem Lappland Granulitkomplex steht. Die prograde Reaktion Chl+St+Ms ↠ Ky+Bt+Qtz+H2O trennt die beiden Zonen. Rotierte Granatporphyroblasten aus der Zone (1) enthalten zahlreiche Einschlüsse (Qtz, Chl, Ms) und zeigen eine Mg/Fe Zonierung, die Granatwachstum w?hrend des prograden Metamorphosestadiums nahelegen. Der Metamorphoseh?hepunkt (650°C, 7.5 kbar) wurde in der Kyanit-Biotit-Zone erreicht und ist durch nicht zonierte Schneeballgranate charakterisiert. In vielen Glimmerschieferproben sind die euhedralen Granatporphyroblasten des retrograden Stadiums vollkommen einschlu?frei und N Mg nimmt vom Kern zum Rand hin ab. Das zeigt eine Abnahme der P-T Bedingungen von 650°C, 7.5 kbar auf 530°C, 5 kbar an. Die Hout River Shear Zone in Südafrika zeigt eine metamorphe Zonierung von Grünschiefern, über Epidotamphibolite zu Granatamphiboliten. Selten kommen stark deformierte Glimmerschiefer (Chl+Grt+Pl+Ms+Bt+Qtz) als dünne Lagen zwischen den Epidotamphiboliten vor. Die Granatporphyroblasten sind ?hnlich wie die aus dem Tanaev Belt und belegen eine prograde P-T Entwicklung mit Peak-Bedingungen von 600°C und ≈ 5.5 kbar. Das retrograde Stadium ist durch die kontinuierliche Reaktion Prp+2Ms+Phl ↠ 6Qtz+3East mit minimal 530°C und ≈ 3.3 kbar dokumentiert. Die sehr ?hnlichen P-T Pfade der Glimmerschiefer belegen ?hnlichkeiten in der geodynamischen Geschichte der beiden bearbeiteten Scherzonen.

Received January 29, 1999;/revised version accepted August 10, 1999  相似文献   

20.
The hydration state of Na- and K-exchanged clinoptilolite from Castle Creek (Idaho, U.S.A.) has been measured by a pressure titration method to 300 °C and P H2O<30 bars. The water content of clinoptilolite can be predicted as a function of water activity and temperature with the equation: a H2O = [exp[[−ΔH h ∘/nRT] + [ΔS h ∘/nR] − 1/nRT· [W1 X h + W2 X h 2]− ln(X a/X h)]]−1 where T is degrees in Kelvin, ΔH h ∘ is the standard molal enthalpy of hydration, ΔS h ∘ is the entropy of hydration, X h and X a are, respectively, the mole fractions of the hydrous and anhydrous components of the solid solution, W 1 and W 2 are interaction parameters, n is the maximum number of moles of H2O per formula unit (based on 12 oxygens), and R is the gas constant. This equation can be used to locate clinoptilolite-H2O isohydrons in a H2O-T space below the liquid-vapor equilibrium curve of water. The standard molal Gibbs free energy of hydration is −47.62 ± 5.52 kJ/mol H2O and −5.40 ± 2.71 kJ/mol H2O for the Na- and K-clinoptilolite, respectively. These standard-state thermodynamic properties of clinoptilolite hydration are in good agreement with previous data at low H2O pressures. The experiments indicate that clinoptilolite progressively dehydrates with increasing temperature at pressures along the liquid-vapor equilibrium curve. Kinetic data above 150 °C show that clinoptilolite dehydration and hydration reactions are fast and reversible and that steady-state hydration states are attained in minutes. Received: 19 June 1998 / Revision, accepted 14 December 1998  相似文献   

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