Variation of the oxygen content and point defects in olivines, (Fe x Mg 1−x )2SiO4, 0.2 ≤ x ≤ 1.0     

T.-L. Tsai  R. Dieckmann 《Physics and Chemistry of Minerals》2002,29(10):680-694

 The variation of the oxygen content in olivines, (Fe _x Mg_{1− x} )₂SiO₄, with 0.2 ≤ x ≤ 1.0, was investigated by thermogravimetric measurements. Mass changes occurring upon oxygen activity changes were measured as a function of oxygen activity and cationic composition at 1130 and 1200 °C. During the measurements the samples were in direct contact with gases containing CO, CO₂ and N₂ and, at a few spots at the bottom of the sample stack, also with SiO₂. By fitting experimental data of mass changes to equations derived using point defect thermodynamics, it was shown for olivines with 0.2 ≤ x ≤ 1.0 at 1130 °C and 0.2 ≤ x ≤ 0.7 at 1200 °C within the oxygen activity ranges investigated that the observed variations in the oxygen contents are compatible with cation vacancies and Fe³⁺ ions on M sites and Fe³⁺ ions on silicon sites as majority defects if it is assumed that only three types of point defects occur as majority defects. Different cases were considered, closed systems, taking into account that ξ=[Si]/([Si]+[Fe]+[Mg]) is not necessarily equal to 1/3, and olivines in equilibrium with SiO₂ or pyroxenes. The oxygen content variations observed in this study are significantly smaller than those reported previously in the literature. It is proposed that these differences are related to the dissolution of Fe into noble metal containers used as sample holders in earlier studies and/or to the presence of secondary phases. Received: 1 November 1995 / Accepted: 15 September 2002 Acknowledgements This work was supported by the Cornell Center for Materials Research (CCMR), a Materials Research Science and Engineering Center of the National Science Foundation (DMR-0079992). The authors thank Mr. Daniel M. DiPasquo and Mr. Jason A. Schick for helping in experimental work.  相似文献   

Stability of clinohumite in the system MgO-SiO2-H2O     

Alison Pawley 《Contributions to Mineralogy and Petrology》2000,138(3):284-291

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   

The thermodynamic properties of H2O in magnesium and iron cordierite     

G. B. Skippen  Avril E. Gunter 《Contributions to Mineralogy and Petrology》1996,124(1):82-89

 The equilibrium water content of cordierite has been measured for 31 samples synthesized at pressures of 1000 and 2000 bars and temperatures from 600 to 750° C using the cold-seal hydrothermal technique. Ten data points are presented for pure magnesian cordierite, 11 data points for intermediate iron/magnesium ratios from 0.25 to 0.65 and 10 data points for pure iron cordierite. By representing the contribution of H₂O to the heat capacity of cordierite as steam at the same temperature and pressure, it is possible to calculate a standard enthalpy and entropy of reaction at 298.18° K and 1 bar for, (Mg,Fe)₂Al₄Si₅O₁₈+H₂O ⇄ (Fe,Mg)₂Al₄Si₅O₁₈.H₂O Combining the 31 new data points with 89 previously published experimental measurements gives: ΔH ^° _r =–37141±3520 J and ΔS ^° _r =–99.2±4 J/degree. This enthalpy of reaction is within experimental uncertainty of calorimetric data. The enthalpy and entropy of hydration derived separately for magnesian cordierite (–34400±3016 J, –96.5±3.4 J/degree) and iron cordierite (–39613±2475, –99.5±2.5 J/degree) cannot be distinguished within the present experimental uncertainty. The water content as a function of temperature, T(K), and water fugacity, f(bars), is given by n _H2O=1/[1+1/(K ⋅ f _H2O)] where the equilibrium constant for the hydration reaction as written above is, ln K=4466.4/T–11.906 with the standard state for H₂O as the gas at 1 bar and T, and for cordierite components, the hydrous and anhydrous endmembers at P and T. Received: 2 August 1994/Accepted: 7 February 1996  相似文献   

The high-pressure stability of zoisite and phase relationships of zoisite-bearing assemblages   总被引：5，自引：0，他引：5  

S. Poli  M. W. Schmidt 《Contributions to Mineralogy and Petrology》1998,130(2):162-175

The fluid-absent reaction 12 zoisite = 3 lawsonite + 7 grossular + 8 kyanite + 1 coesite was experimentally reversed in the model system CaO-Al₂O₃-SiO₂-H₂O (CASH) using a multi-anvil apparatus. The upper pressure stability limit for zoisite was found to extend to 5.0 GPa at 700 °C and to 6.6 GPa at 950 °C. Additional experiments both in the H₂O-SiO₂-saturated and in the H₂O-Al₂O₃-saturated portions of CASH provide further constraints on high pressure phase relationships of lawsonite, zoisite, grossular, kyanite, coesite, and an aqueous fluid. Consistency of the present experiments with the H₂O-saturated breakdown of lawsonite is demonstrated by thermodynamic analysis using linear programming techniques. Two sets of data consistent with databases of Berman (1988) and Holland and Powell (1990) were retrieved combining experimental phase relationships, calorimetric constraints, and recently measured elastic properties of solid phases. The best fits result in G _{f ,1,298} ^∘,zoisite=−6,499,400 J and S _1,298 ^∘,zoisite=302 J/K, and G _{f ,1,298} ^{∘,lawsonite}=−4,514,600 J and S _1,298 ^{∘,lawsonite}=220 J/K for the dataset of Holland and Powell, and G _{f ,1,298} ^∘,zoisite=−6,492,120 J and S _1,298 ^∘,zoisite=304 J/K, and G _{f ,1,298} ^{∘,lawsonite}=−4,513,000 J and S _1,298 ^{∘,lawsonite}= 218 J/K for the dataset of Berman. Examples of the usage of zoisite as a geohygrometer and as a geobarometer in rocks metamorphosed at eclogite facies conditions are worked, profiting from the thermodynamic properties retrieved here. Received: 23 December 1996 / Accepted: 29 August 1997  相似文献   

Seeing past the effects of re-equilibration to reconstruct magmatic gradients in plutons: La Gloria Pluton, central Chilean Andes     

P. C. Cornejo  G. A. Mahood 《Contributions to Mineralogy and Petrology》1997,127(1-2):159-175

This study of La Gloria pluton in the Chilean Andes evaluates what information about magmatic conditions can be extracted from minerals in a granitic pluton, despite lower-temperature re-equilibration. The pluton is zoned vertically from granodiorite/quartz monzodiorite to quartz monzonite at the roof, with the uppermost 1500 m showing the strongest modal and compositional trends. This mimics the pattern frequently inferred from zoning in voluminous ignimbrites: a strongly zoned cap overlying a more homogeneous main␣body. The presence of large, euhedral amphibole ± biotite at the chamber margins and roof indicate that water was concentrated there. Biotite and amphibole compositions indicate a roofward increase in magmatic f _HF, f _HCl and F/Cl ratio, analogous to pre-eruptive volatile gradients recorded in zoned ignimbrites. Hornblende that crystallized directly from the melt in the volatile-rich wall and roof zones yields total-Al solidification pressures of ˜1 kbar, consistent with the estimated 4000 m of cover at the time of emplacement. In the core of the pluton, actinolitic amphibole formed by reaction of melt with early-crystallized clinopyroxene. Plag-cpx cumulate clots in the lower level are interpreted as early crystallizing phases entrained in rising granitic magma. Cores of amphibole phenocrysts in mafic enclaves suggest initial crystallization at pressures of 2–3 kbar. Lower Ti and Al contents of rims and acicular groundmass amphibole, overlapping the composition of amphibole in the host granitoid, indicate that the enclaves equilibrated with the host at the present exposure level in the presence of interstitial melt. A roofward relative increase in fO₂ of the magma is recorded by an increasing proportion of Fe-Ti oxides as a fraction of the mafic phases, greater Mn content of ilmenite, and constant or higher Mg/(Mg+Fe) in hornblende and biotite despite declining whole-rock MgO contents. Association␣of subhedral biotite and magnetite with actinolitic amphibole in clots implies a reaction: K-Ti-hb + O₂(gas) = bi + mt + actinolitic amph + titanite. Magnetite coexisting with biotite with Fe/(Fe+Mg) = 0.34– 0.40 implies temperatures of equilibration no lower than about 720–750 °C, i.e., late-magmatic rather than subsolidus. Saturation with respect to a water-rich vapor and subsequent diffusive loss of hydrogen may have caused this oxidation trend, which resulted in the most magnesian mafic phases occurring in the most compositionally evolved rocks, opposite to trends in most zoned ignimbrites, which presumably record conditions nearer the liquidus and prior to exsolution of a water-rich vapor. Two-feldspar and Fe-Ti-oxide geothermometers record subsolidus conditions in the pluton and yield higher temperatures for samples from the roof zone, suggesting that slower cooling at deeper levels allowed these minerals to continue to equilibrate to lower temperatures. Individual minerals span wide ranges in composition at any given level of the pluton, from those appropriate for phenocrysts, to those that record conditions well below the solidus. We suggest that the shallow level and isolated position of the pluton led to rapid escape of magmatic volatiles and rapid cooling, thereby preventing development of a long-lived hydrothermal system. Resulting small water/rock ratios may account for why late-magmatic and subsolidus re-equilibration were not pervasive. Received: 23 August 1996 / Accepted: 18 October 1996  相似文献   

Fe–Mg partitioning between ringwoodite and magnesiowüstite and the effect of pressure, temperature and oxygen fugacity     

D. J. Frost  F. Langenhorst  P. A. van Aken 《Physics and Chemistry of Minerals》2001,28(7):455-470

 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   

H2O activity in concentrated KCl and KCl-NaCl solutions at high temperatures and pressures measured by the brucite-periclase equilibrium     

L. Y. Aranovich  R. C. Newton 《Contributions to Mineralogy and Petrology》1997,127(3):261-271

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 (ρ_H2O) 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 = γ_H2O[x _H2O+(1 + (1 + α)x _KCl)], and a _KCL = γ_KCl[(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 γ_i = (1 − x_i)²W. Least squares fitting of our H₂O and KCl activity data evaluates the parameters: α = exp(4.166 −2.709/ρ_H2O) − 212.1P/T, and W = (−589.6 − 23.10P) /T, with ρ_H2O 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   

Microanalysis of Fe3+/ΣFe in oxide and silicate minerals by investigation of electron energy-loss near-edge structures (ELNES) at the Fe M 2,3 edge     

P. A. van Aken  V. J. Styrsa  B. Liebscher  A. B. Woodland  G. J. Redhammer 《Physics and Chemistry of Minerals》1999,26(7):584-590

The Fe M _2,3-edge spectra of solid solutions of garnets (almandine-skiagite Fe₃(Al_1–xFe_x)₂[SiO₄]₃ and andradite-skiagite (Fe_1–xCa_x)₃Fe₂[SiO₄]₃), pyroxenes (acmite-hedenbergite (Ca_1–xNa_x)(Fe²⁺ _1−xFe³⁺ _x)Si₂O₆), and spinels (magnetite-hercynite Fe(Al_1–xFe_x)₂O₄) have been measured using the technique of parallel electron energy-loss spectroscopy (EELS) conducted in a transmission electron microscope (TEM). The Fe M _2,3 electron energy-loss near-edge structures (ELNES) of the minerals exhibit a characteristic peak located at 4.2 eV and 2.2 eV for trivalent and divalent iron, respectively, prior to the main maximum at about 57 eV. The intensity and energy of the pre-edge feature varies depending on Fe³⁺/ΣFe. We demonstrate a new quantitative method to extract the ferrous/ferric ratio in minerals. A systematic relationship between Fe³⁺/ΣFe and the integral intensity ratio of the main maximum and the pre-edge peak of the Fe M _2,3 edge is observed. Since the partial cross sections of the Fe M _2,3 edges are some orders of magnitude higher than those of the Fe L _2,3 edges, the Fe M _2,3 edges are interesting for valence-specific imaging of Fe. The possibility of iron valence-specific imaging is illustrated by Fe M _2,3-ELNES investigations with high lateral resolution from a sample of ilmenite containing hematite exsolution lamellae that shows different edge shapes consistent with variations in the Fe³⁺/ΣFe ratio over distances on the order of 100 nm. Received: 14 April 1998 / Revised, accepted: 8 March 1999  相似文献   

Sulfur K-edge XANES study of local electronic structure in ternary monosulfide solid solution [(Fe, Co, Ni)0.923S]     

S. P. Farrell  M. E. Fleet 《Physics and Chemistry of Minerals》2001,28(1):17-27

 Synchrotron radiation S K-edge XANES spectra and unit-cell parameters are used to investigate the local electronic structure of non-stoichiometric binary and ternary Fe-Co-Ni monosulfide solid solution (mss; M_0.923S, M = Fe, Co, Ni) quenched from 800 °C and low pressure. The prominent absorption edge feature of the XANES spectra represents transition of S 1s core level electrons to unoccupied S 3p σ* antibonding orbitals hybridized with empty metal 3d(e_g) orbitals. There is a progressive increase in area of the edge peak from Fe_0.923S to Ni_0.923S and Co_0.923S, which correlates with progressive decrease in c and a parameters for the NiAs-type subcell and increase in metallic character, and reflects increase in the number and availability of empty e_g ^β orbitals and covalence of metal-S bonds. More generally, the area of the edge peak exhibits an inverse linear correlation with a, c and unit-cell volume of binary and ternary mss. This inverse linear correlation is attributed to progressive increase in covalence and M-S-M bonding interaction in the c-axis direction, through metal-S [M 3d(e_g) - S 3p (or 3d)] π bonding. However, the area of the edge peak does not correlate very well with the average number of 3d electrons per metal atom in these solid solutions, showing that the absorption of synchrotron radiation reflects the local electronic structure of individual absorber atoms (i.e. the SM₆ cluster), and is not a group (crystal energy band) effect. Received: 21 March 2000 / Accepted: 14 July 2000  相似文献   

Thermal expansion and structural transformations of stuffed derivatives of quartz along the LiAlSiO4–SiO2 join: a variable-temperature powder synchrotron XRD study     

H. Xu  P. J. Heaney  A. Navrotsky 《Physics and Chemistry of Minerals》2001,28(5):302-312

 The structural behavior of stuffed derivatives of quartz within the Li_{1− x} Al_{1− x} Si_{1+ x} O₄ system (0 ≤ x ≤ 1) has been studied in the temperature range 20 to 873 K using high-resolution powder synchrotron X-ray diffraction (XRD). Rietveld analysis reveals three distinct regimes whose boundaries are defined by an Al/Si order-disorder transition at x=∼0.3 and a β–α displacive transformation at x=∼0.65. Compounds that are topologically identical to β-quartz (0 ≤ x < ∼0.65) expand within the (0 0 1) plane and contract along c with increasing temperature; however, this thermal anisotropy is significantly higher for structures within the regime 0 ≤ x < ∼0.3 than for those with compositions ∼0.3 ≤ x < ∼0.65. We attribute this disparity to a tetrahedral tilting mechanism that occurs only in the ordered structures (0 ≤ x < ∼0.3). The phases with ∼0.65 ≤ x ≤ 1 adopt the α-quartz structure at room temperature, and they display positive thermal expansion along both a and c from 20 K to their α–β transition temperatures. This behavior arises mainly from a rotation of rigid Si(Al)-tetrahedra about the <100> axes. Landau analysis provides quantitative evidence that the charge-coupled substitution of Li+Al for Si in quartz dampens the α–β transition. With increasing Li+Al content, the low-temperature modifications exhibit a marked decrease in spontaneous strain; this behavior reflects a weakening of the first-order character of the transition. In addition, we observe a linear decrease in the α–β critical temperature from 846 K to near 0 K as the Li+Al content increases from x=0 to x=∼0.5. Received: 26 June 2000 / Accepted: 1 December 2000  相似文献   

Determination of cation distribution in (Co,Ni,Zn)2SiO4 olivine by synchrotron X-ray diffraction     

K. Tsukimura  S. Sasaki 《Physics and Chemistry of Minerals》2000,27(4):234-241

 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 (Co_0.377Ni_0.396Zn_0.227)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   

The low-pressure stability of phase A,Mg7Si2O8(OH)6     

A. R. Pawley  Bernard J. Wood 《Contributions to Mineralogy and Petrology》1996,124(1):90-97

 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   

The crystal structure of arsentsumebite, Pb2Cu[(As, S)O4]2(OH)     

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, d_calc. = 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   

Experimental determination of activities in FeTiO3-MnTiO3 ilmenite solid solution by redox reversals     

A. Feenstra  Tjerk Peters 《Contributions to Mineralogy and Petrology》1996,126(1-2):109-120

 Solid solutions of (Fe,Mn)TiO₃ were synthesized, mostly at 0.10 X_Mn intervals, at 1 bar, 900°C and log f _{O 2} = –17.50. Analysis by EMP indicate an ideal stoichiometry for the Fe-Mn ilmenites with (Fe+Mn) = Ti = 1.000 when normalized to 3 oxygens. Their unit cell volume increases linearly with X_Mn. The composition of Fe-Mn ilmenite coexisting with metallic Fe and rutile was reversed at 1 bar, 700–900°C and fixed f _{O 2} in a gas-mixing furnace. Oxygen fugacity was controlled by mixing CO₂ and H₂ gas and was continuously monitored with an yttrium-stabilized zirconia electrolyte. Solution properties of Fe-Mn ilmenite were derived from the experimental data by mathematical programming (Engi and Feenstra, in preparation) including notably the results of Fe-Mn exchange experiments between ilmenite and garnet (Feenstra and Engi, submitted) and anchoring the standard state properties to the updated thermodynamic dataset of Berman and Aranovich (1996). The thermodynamic analysis resulted in positive deviations from ideality for (Fe,Mn)TiO₃ ilmenite, which is well described by an asymmetric Margules model with W^H _FeFeMn = –9.703 and W^H _FeMnMn = –23.234 kJ/mol, W^S _FeFeMn = –19.65 and W^S _FeMnMn = –22.06 J/(K·mol). The excess free energy for Fe-Mn ilmenite derived from the redox reversals is larger than in the symmetric ilmenite model (W^G _FeMn = +2.2 kJ/mol) determined by O'Neill et al. from emf measurements on the assemblage iron-rutile-(Fe,Mn)ilmenite. Received: 10 January 1996 / Accepted: 11 July 1996  相似文献   

Experimental and thermodynamic study of the crystallization of diamond and silicates in a metal-silicate-carbon system     

I. I. Fedorov  A. I. Chepurov  V. M. Sonin  A. A. Chepurov  A. M. Logvinova 《Geochemistry International》2008,46(4):340-350

Silicate inclusions are widespread in natural diamonds, which also may contain rare inclusions of native iron. This suggests that some natural diamonds crystallized in metal-silicate-carbon systems. We experimentally studied the crystallization of diamond and silicate phases from the starting composition Fe_0.36Ni_0.64 + silicate glass + graphite and calculated the Fe mole fractions of the silicate phases crystallizing under these conditions. The silicates synthesized together with diamond had low Fe mole fractions [Fe/(Fe + Mg + Ca)] in spite of strong Fe predominance in the system. The Fe mole fractions of the silicates decreased in the sequence garnet-pyroxene-olivine, which is consistent with the results of our thermodynamic calculations. The Fe mole fraction of silicates under various redox conditions under which metal-carbon melts are stable drastically decreases with decreasing fo₂. The low Fe mole fractions of silicate inclusions in diamond from the Earth’s mantle can be explained by the highly reducing crystallization conditions, under which Fe was concentrated as a metallic phase of the magmatic melts and could be only insignificantly incorporated in the structures of silicates.  相似文献   

Complex zoning between super-calcic pigeonite and augite from the Graveyard Point sill, Oregon: a record of the interplay between bulk and interstitial liquid fractionation     

Gregor Markl  Craig White 《Contributions to Mineralogy and Petrology》1999,137(1-2):170-183

The 150 m thick late Miocene Graveyard Point sill (GPS) is situated at the Idaho-Oregon border near the southwestern edge of the western Snake River Plain. It records from bottom to top continuous fractional crystallization of a tholeiitic parent magma (lower chilled border, FeO/(FeO+MgO) = 0.59, Ni = 90 ppm) towards granophyres (late pods and dikes, FeO/(FeO+MgO) = 0.98, 78 wt% SiO₂ 3.5 wt% K₂O, <4 ppm Ni) showing a typical trend of Fe and P enrichment. Fractionating minerals are olivine (Fo₇₉-Fo₂), augite (X _Fe = 0.18−0.95), feldspars (An₈₀Or₁-An₁Or₆₂), Fe-Ti oxides (Ti-rich magnetite and ilmenite), apatite and in two samples super-calcic pigeonite (Wo_18–28 Fs_41–54). The granophyres may bear some quartz. Compositionally zoned minerals record a large interval of the fractionation process in every single sample, but this interval changes with stratigraphic height. In super-calcic pigeonite-bearing samples, olivine is scarce or lacking and because super-calcic pigeonite occurs as characteristic overgrowths on augite, its formation is interpreted to be related to the schematic reaction: augite + olivine (component in melt) + SiO₂ (in melt) = pigeonite, that defines the cotectic between augite and pigeonite in olivine-saturated basaltic systems. Line measurements with the electron microprobe reveal that the transition from augite to super-calcic pigeonite is continuous. However, some crystals show an abrupt “reversal” towards augite after super-calcic pigeonite growth. Two processes compete with each other in the GPS: fractional crystallization of the bulk liquid (the bulk melt separates from solids and interstitial liquids in the solidification front) and fractional crystallization of interstitial melt in the solidification front itself. Interplay between those two processes is proposed to account for the observed variations in mineral chemistry and mineral textures. Received: 25 November 1998 / Accepted: 14 June 1999  相似文献   

P -T paths from anatectic pelites   总被引：2，自引：1，他引：1  

Frank S. Spear  Matthew J. Kohn  John T. Cheney 《Contributions to Mineralogy and Petrology》1999,134(1):17-32

A relatively simple petrogenetic grid for partial melting of pelitic rocks in the NCKFMASH system is presented based on the assumption that the only H₂O available for melting is through dehydration reactions. The grid includes both discontinuous and continuous Fe-Mg reactions; contours of Fe/(Fe+Mg) for continuous reactions define P-T vectors along which continuous melting will occur. For biotite-bearing assemblages (garnet+biotite + sillimanite + K-feldspar + liquid and garnet + biotite + cordierite + K-feldspar + liquid), Fe/(Fe+Mg) contours have negative slopes and melting will occur with increasing temperature or pressure. For biotite-absent assemblages (garnet + cordierite + sillimanite + K-feldspar + liquid or garnet + cordierite + orthopyroxene + K-feldspar + liquid) Fe/(Fe + Mg) contours have flat slopes and melting will occur only with increasing pressure. The grid predicts that abundant matrix K-feldspar should only be observed if rocks are heated at P < 3.8 kbar, that abundant retrograde muscovite should only be observed if rocks are cooled at P > 3.8 kbar, and that generation of late biotite + sillimanite replacing garnet, cordierite, or as selvages around leu- cosomes should be common in rocks in which melt is not removed. There is also a predicted field for dehydration melting of staurolite between 5 and 12 kbar. Textures in migmatites from New Hampshire, USA, suggest that prograde dehydration melting reactions are very nearly completely reversible during cooling and crystallization in rocks in which melt is not removed. Therefore, many reaction textures in “low grade” migmatites may represent retrograde rather than prograde reactions. Received: 5 March 1998 / Accepted: 7 August 1998  相似文献   

The determination of partial melt compositions of peridotitic systems by melt inclusion synthesis     

N. W. A. Odling  D. H. Green  B. Harte 《Contributions to Mineralogy and Petrology》1997,129(2-3):209-221

An experimental method of melt inclusion synthesis within olivine crystals has been developed to determine the composition of the melt present in a partially molten peridotite assemblage. Trace element doped peridotite was equilibrated with 5 wt% of a C-O-H volatile source at 20 kbar/1175 °C in a piston-cylinder apparatus under buffered oxygen and sulphur fugacity conditions [log(f _O2) ∼ IW +1 log unit, log (f _S2) ∼ Fe/FeS > +1 log unit]. A single crystal of olivine, which had been cut to a disc shape, was included in the sample capsule. At run conditions the peridotite charge formed olivine, orthopyroxene, clinopyroxene, Fe-Ni sulphide and a volatile-bearing melt. The melt phase is preserved as homogeneous glass inclusions up to 50 μm in size, trapped in situ in the olivine disc. The major element composition of the glass inclusions showed them to be of broadly basaltic character, but with a low Mg/(Mg + ΣFe), which is associated with precipitation of olivine from the melt inclusion onto the walls of the olivine disc during quenching. Thus the equilibrium melt composition has been calculated from the glass inclusion composition by addition of olivine component using the Fe/Mg exchange coefficient of Roeder and Emslie (1970); the desired Mg/(Mg + ΣFe) being determined from the composition of olivine formed at run conditions in the peridotite section of the charge. The melt composition obtained is close to the trend for dry melting established by Falloon and Green (1988), and it is evident that although the reduced volatiles in this case have induced a liquidus depression of some 250 °C, there has been only a small shift in melt composition. Trace element, carbon and hydrogen contents of thirteen melt inclusions have been determined by secondary ion mass spectrometry (SIMS). The trace element signature is consistent with ∼29% melting in equilibrium with a lherzolitic assemblage. The equilibrium melt has a C/H of 0.48 by weight. Carbon solubility in partial melts is thus significant under reducing conditions in the presence of dissolved “water components” and establishes a major melt fluxing role for carbon in the upper mantle. The ubiquitous presence of carbon and hydrogen in basaltic magmas underscores the importance of determining both the position of vapour-present solidi and the composition of melts generated, when developing petrogenetic models. Received: 1 July 1996 / Accepted: 25 June 1997  相似文献   

Ca–Mn exchange between grossular and MnCl2 solutions at 2 kbar and 600°°C: reaction mechanism and evidence for non-ideal mixing in spessartine-grossular garnets     

I. Gavrieli  Alan Matthews  J. B. Holland 《Contributions to Mineralogy and Petrology》1996,125(2-3):251-262

 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 K_D 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   

An empirical model for the calculation of spinel-melt equilibria in mafic igneous systems at atmospheric pressure: 2. Fe-Ti oxides     

Alexi A. Ariskin  Galina S. Barmina 《Contributions to Mineralogy and Petrology》1999,134(2-3):251-263

In order to develop models simulating the crystallization of Fe-Ti oxides in natural lavas, we have processed published experimental data on magnetite-melt and ilmenite-melt equilibria. These data include 62 Mt-melt and 75 Ilm-melt pairs at temperatures 1040–1150 °C, oxygen fugacities from IW to NNO+2, and bulk compositions ranging from ferrobasalts to andesites and dacites. Five major cations (Fe³⁺, Fe²⁺, Ti⁴⁺, Mg²⁺ and Al³⁺) were considered for the purpose of describing Fe-Ti oxide saturation as a function of melt composition, temperature and oxygen fugacity at 1 atmosphere pressure. The empirically calibrated mineral-melt expression based on multiple linear regressions is: ln D _i  = a/T + blog f _O2 + c + d ₁ X _Na + d ₂ X _K + d ₃ X _P, where D _i represents molar distribution coefficients of the given cations between Mt/Ilm and melt; X _Na, X _K, and X _P are the molar fractions of Na, K, and P in the melt. The empirically calibrated Mt-melt and Ilm-melt equilibria equations allowed us to develop two models for calculating crystallization temperatures of the Fe-Ti oxides in the melts with an accuracy of 10–15 °C, and compositions with an accuracy of 0.5–2 mol%. These models have been integrated into the COMAGMAT-3.5 program, improving our ability to study numerically the effects of temperature and oxygen fugacity on the stability and phase equilibria of Fe-Ti oxides. Application of this approach to the tholeiitic series of Chazhma Sill from Eastern Kamchatka (Russia) indicates oxygen fugacity conditions near NNO + 0.5. Numerical simulation of fractional crystallization of an iron-enriched basaltic andesite parent at these oxidizing conditions accurately reproduces the FeO-SiO₂ relations observed in the Chazhma suite. Received: 3 March 1998 / Accepted: 7 August 1998  相似文献