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1.
Mixtures of synthetic crystalline enstatite and diopside were reacted with small water contents in sealed capsules in piston-cylinder apparatus at 30 kb between 1000° C and 1700° C. The compositions of coexisting enstatite and diopside solid solutions were measured with an ARL-EMX electron microprobe between 1000° C and 1500° C. Between 1100° C and 1500° C the pyroxenes coexisted with H2O-undersaturated liquid which quenched to inhomogeneous pyroxene crystals. The presence of liquid facilitated growth of pyroxene crystals suitable for microprobe determinations. The solvus of Davis and Boyd (1966) is generally used in geothermometry; our enstatite solvus limb is a few mol-% richer in Mg2Si2O6 in the temperature range 1000–1400° C; our diopside solvus limb is a few mol-% richer in Mg2Si2O6 below 1100°C, in close agreement between 1100° C and 1200° C, but richer in CaMgSi2O6 between 1200° C and 1500° C. Estimated equilibration temperatures for a diopside with composition 78.7% Di is 1300° C according to our results compared with 1210° C for the Davis and Boyd solvus.  相似文献   

2.
Thermodynamic parameters for the reaction: $$\begin{gathered} Mg_2 Si_2 O_6 = Mg_2 Si_2 O_6 \hfill \\ enstatite clinopyroxene \hfill \\ \end{gathered} $$ in the system CaO-MgO-SiO2 have been deduced from phase equilibrium and enthalpy of solution data. From the regular solution theory, the seventeen currently available reversed experimental compositions of coexisting enstatite and clinopyroxene, presumed to be ordered diopside, lead, by a statistical regression, to the following best fit parameters: ΔH o=6.80 kJ ΔS o=2.75 J/K W H Cpx =24.47 kJ (regular solution enthalpy parameter) W V Cpx =0.105 J/bar (regular solution volume parameter). The derived parameters are not significantly affected by the (necessary) choice of W Opx in the range 20–50 kJ. The above values are in very good agreement with deductions from the solution calorimetry on synthetic CaMgSi2O6-Mg2Si2O6 clinopyroxenes of Newton et al. (1979), which also places bounds on possible departures from the optimal values of these parameters. The calorimetric data may also be interpreted in terms of a Bragg-Williams cooperative-disordering model (Navrotsky and Loucks, 1977), in which diopside-structure clinopyroxene and a ‘relaxed’ low-Ca clinopyroxene (‘Fe-free pigeonite’) approach each other in composition, structural state, and stability with increasing temperature. The ΔH o parameter deduced from the regular solution theory is reinterpreted as the enthalpy change of enstatite to Mg2Si2O6 pigeonite; the ΔH o of the transformation of enstatite to the diopside structure would, in this case, be considerably larger than 6.8 kJ. The curvature of the enthalpy of solution data, explained by the regular solution theory in terms of M2-site energetics (involving W H cpx ), is reinterpreted as due to disordering and ‘relaxation’ in the Navrotsky-Loucks model. Although the regular solution theory with the best-fit parameters accounts for all of the reversed enstatite and diopside compositions to within 18 ° C, and is a convenient representation of the phase equilibria for purposes of geothermometry, the disordering model is, at the present level of knowledge, equally valid and allows for a region of stability of two coexisting clinopyroxenes.  相似文献   

3.
The enthalpies of solution of several synthetic garnets on the join Mg3Al2Si3O12-Ca3Al2Si3O12 (pyrope-grossular) and of several synthetic clinopyroxenes on the join CaMgSi2O6-CaAl2SiO6 (diopside-Ca-Tschermak's molecule) were measured in a melt of composition 2PbO · B2O3 at 970 K. The determinations were made with sufficient precision so that thermochemical characterizations of the solid solutions could be achieved.The pyrope-grossular solutions show positive enthalpies of mixing. The non-ideality in the range 0–30 mole % grossular is relatively the largest and is in good agreement with the predictions of Ganguly and Kennedy (1974) based largely on cation partitioning of natural high grade metamorphic garnets with biotite, and with the deductions of Hensenet al. (1975) based on measurement of the compositions of synthetic pyrope-rich garnets equilibrated with anorthite, Al2SiO5 and quartz. However, the garnets show smaller excess enthalpies at higher grossular contents. This would lead to an asymmetric solvus with a critical temperature lower than predicted by the symmetrical regular solution model of Ganguly and Kennedy (1974). The composition-dependent non-ideality can be understood by simple ionic size considerations in solid substitution and is analogous to the situations for the calcite-dolomite and enstatite-diopside solvi.The heats of solution of pyropes crystallized in the range 1000–1500°C were all the same, within the precision of measurement, and thus we have found no evidence for temperature-dependent cation disordering as a possible explanation of the high entropy of pyrope, as suggested by Charluet al. (1975). Positional disorder of dodecahedral Mg is a more probable reason.The diopside-CaTs join is also non-ideal, with the larger positive enthalpy deviations near the diopside end. The calorimetric data in the magnesian range are consistemt with the model for completely disordered tetrahedral Si and Al which results from the free energy derivations of wood (1975) based on syntheses of diopside-rich aluminous pyroxenes in the presence of anorthite and quartz. At higher Al concentrations the calorimetric data seem more consistent with the ‘local charge-balance’ model of Wood (1975).No evidence for temperature-dependent disorder was found for either the diopside or CaTs end-members.  相似文献   

4.
Enthalpies of solution in 2PbO · B2O3 at 974 K have been measured for glasses along the joins Ca2Si2O6 (Wo)-Mg2Si2O6 (En) and Mg2Si2O6-MgAl2SiO6 (MgTs). Heats of mixing are symmetric and negative for Wo-En with WH = ?31.0 ± 3.6 kJ mol?. Negative heats of mixing were also found for the En-MgTs glasses (WH = ?33.4 ± 3.7 kJ mol?).Enthalpies of vitrification of pyroxenes and pyroxenoids generally increase with decreasing alumina content and with decreasing basicity of the divalent cation.Heats of mixing along several glassy joins show systematic trends. When only non-tetrahedral cations mix (outside the aluminosilicate framework), small exothermic heats of mixing are seen. When both nontetrahedral and framework cations mix (on separate sublattices, presumably), the enthalpies of mixing are substantially more negative. Maximum enthalpy stabilization near compositions with Al/Si ≈ 1 is suggested.  相似文献   

5.
The enthalpies of solution of petrologically important phases in the system MgO-Al2O3-SiO 2 were measured in a melt of composition 2PbO · B2O3 at 970 ± 2K. The substances investigated included synthetic and natural (meteoritic) enstatite (MgSiO3), synthetic aluminous enstatite (MgSiO30.9Al2O30.1), synthetic and natural cordierite (Mg2Al4Si5O18), synthetic and natural sapphirine (approx. 7MgO·9Al2O3 · 3SiO2), synthetic spinel (MgAl2O4), natural sillimanite (Al2SiO5), synthetic forsterite (Mg2SiO4), synthetic pyrope (Mg3Al2Si3O12), natural quartz (SiO2), synthetic periclase (MgO) and corundum (Al2O3). Improvement in standardization of the calorimeter solvent made possible greater precision in this study than obtainable in former work in this laboratory on some of the same substances.The enthalpies of formation of enstatite, synthetic cordierite, forsterite and spinel are in reasonable agreement with values previously determined by solution calorimetry. The enthalpy of formation of enstatite is about 0.7 kcal less negative than the value for clinoenstatite resulting from the HF calorimetry of Torgesen and Sahama (J. Amer. Chem. Soc.70. 2156–2160, 1948), and is in accord with predictions based on analysis of published pyroxene equilibrium work. Aluminous enstatite with 10 wt.% Al2O3 shows an enthalpy of solution markedly lower than pure MgSiO3: the measurements lead to an estimate of the enthalpy of formation at 970 K for MgAl2SiO6 (Mg-Tschermak) orthopyroxene of + 9.4 ± 1.5 kcal/mole from MgSiO3 and Al2O3.Comparison of the enthalpies of formation of synthetic cordierite and anhydrous natural low-iron cordierite shows that they are energetically quite similar and that the synthetic cordierite is not likely to have large amounts of (Al, Si) tetrahedral disorder. Comparison of the enthalpies of formation of synthetic sapphirine and natural low-iron sapphirine shows, on the other hand, that the former is not a good stability model for the latter. The lower enthalpy of formation of the high-temperature synthetic sample is undoubtedly a consequence of cation disordering.The enthalpy of formation of natural sillimanite is considerably less negative than given by the tables of Robie andWaldbaum (U.S. Geol. Surv. Bull.1259 1968).The measured enthalpy of formation of synthetic pyrope is consistent with that deduced from published equilibrium diagrams in conjunction with the present measured enthalpy of formation of aluminous enstatite. Calculation of the entropy of synthetic pyrope from the present data yields surprisingly high values and suggests that synthetic pyrope is not a good stability model for natural pyrope-rich garnets. Hence, considerable doubt exists about the direct quantitative application of experimental diagrams involving pyropic garnet to discussions of the garnet stability field in the Earth's outer regions.  相似文献   

6.
Enthalpies of solution in 2PbO· B2O3 at 712°C have been measured for glasses in the systems albite anorthite diopside, NaAlO2-SiO2, Ca0.5AlO2-SiO2 and albite-anorthite-quartz. The systems albite-anorthite and diopside-anorthite show substantial negative enthalpies of mixing, albite-diopside shows significant positive heats of mixing. For compositions up to NaAlO2 = 0.42 (which includes the subsystem albite-silica) the system NaAlO2-SiO2 shows essentially zero heats of mixing. A negative ternary excess heat of mixing is found in the plagioclase-rich portion of the albite-anorthite-diopside system. The join Si4O8-CaAl2Si2O8 shows small but significant heats of mixing. In albite-anorthite-quartz. ternary glasses, the ternary excess enthalpy of mixing is positive.Based on available heat capacity data and appropriate consideration of the glass transition, the enthalpy of the crystal-glass transition (vitrification) is a serious underestimate of the enthalpy of the crystal-liquid transition (fusion) especially when the melting point, Tf, is many hundreds of degrees higher than the glass transition temperature, Tg. On the other hand, the same heat capacity data suggest that the enthalpies of mixing in albite-anorthite-diopside liquids are calculated to be quite similar to those in the glasses. The enthalpies of mixing observed in general support the structural models proposed by Taylor and Brown (1979a, b) and others for the structure of aluminosilicate glasses.  相似文献   

7.
The system CaMgSi2O6CaAl2SiO6CaFeAlSiO6 has been studied in air at 1 atm. The phase assemblage at subsolidus temperatures in the CaMgSi2O6-rich portion is Cpx + An + Mel and that in the CaMgSi2O6-poor portion Cpx + An + Mel + Sp. At subsolidus temperatures the sigle-phase field of clinopyroxene increases with an increase in the CaFeAlSiO6 component of the system. The Al2O3 content of clinopyroxene, however, continues to increase beyond the single-phase field and attains at least 16.04 wt.% Al2O3 with 3.9 wt.% Fe2O3. The stability field of fassaite in the system over a range of pressures and oxygen fugacities has been estimated from data in the literature as well as the present data. The CaFeAlSiO6 content of fassaite is dependent on oxygen fugacity, but is not influenced by pressure. The stability field is strongly influenced by oxygen fugacity at low and high pressure, and decreases with decreasing oxygen fugacity. Clinopyroxenes in both volcanic and metamorphic rocks from various localities, when plotted on the CaMgSi2O6CaAl2SiO6CaFeAlSiO6 triangle, show that there is no compositional gap between diopside and fassaitic pyroxene in metamorphic rocks, and that the fassaitic pyroxene in alkalic rocks becomes richer in both CaAl2SiO6 and CaFeAlSiO5 components as crystallization proceeds. These results agree with those obtained in the experimental study.  相似文献   

8.
Our experimental simulations of the exhumation path of mantle peridotites show that high‐temperature (1400 °C) decompression of lherzolite from 14 to 13 and 12 GPa results in exsolution of interstitial blebs of diopside and Mg2SiO4 (wadsleyite) lamellae from majoritic garnet. At lower pressures (from 8 to 5 GPa, at T = 1400 °C) only enstatite exsolves as blebs at garnet boundaries. Continuous high‐temperature decompression from 14 to 7 GPa produces zoned majoritic garnet containing blebs of exsolved pyroxenes inside garnet rims. No intracrystalline precipitation of pyroxene was observed in garnet, although such lamellae are found in some natural garnet peridotites. The explanation appears to be the three orders of magnitude difference in grain size between experimental and natural specimens. Our data suggest that Mg2SiO4 and diopside exsolutions reflect the deepest point of the exhumation path of garnet peridotites, whereas enstatite precipitation may be restricted to garnets with less majoritic component at shallower depths.  相似文献   

9.
An end member of the tourmaline series with a structural formula □(Mg2Al)Al6(BO3)3[Si6O18](OH)4 has been synthesized in the system MgO-Al2O3-B2O3-SiO2-H2O where it represents the only phase with a tourmaline structure. Our experiments provide no evidence for the substitutions Al → Mg + H, Mg → 2H, B + H → Si, and AlAl → MgSi and we were not able to synthesize a phase “Mg-aluminobuergerite” characterized by Mg in the (3a)-site and a strong (OH)-deficiency reported by Rosenberg and Foit (1975). The alkali-free tourmaline has a vacant (3a)-site and is related to dravite by the □ + Al for Na + Mg substitution. It is stable from at least 300°C to about 800°C at low fluid pressures and 100% excess B2O3, and can be synthesized up to a pressure of 20 kbars. At higher temperatures the tourmaline decomposes into grandidierite or a boron-bearing phase possibly related to mullite (“B-mullite”), quartz, and unidentified solid phases, or the tourmaline melts incongruently into corundum + liquid, depending on pressure. In the absence of excess B2O3 tourmaline stability is lowered by about 60°C. Tourmaline may coexist with the other MgO-Al2O3-B2O3-SiO2-H2O phases forsterite, enstatite, chlorite, talc, quartz, grandidierite, corundum, spinel, “B-mullite,” cordierite, and sinhalite depending on the prevailing PTX-conditions.The (3a)-vacant tourmaline has the space group R3m with a =15.90 A?, c = 7.115 A?, and V = 1557.0 A?3. However, these values vary at room temperature with the pressure-temperature conditions of synthesis by ±0.015 A? in a, ±0.010 A? in c, and ±4.0 A?3 in V, probably as a result of MgAl order/disorder relations in the octahedral positions. Despite these variations intensity calculations support the assumed structural formula. Refractive indices are no = 1.631(2), nE = 1.610(2), Δn = 0.021. The infrared spectrum is intermediate between those of dravite and elbaite. The common alkali and calcium deficiencies of natural tourmalines may at least partly be explained by miscibilities towards (3a)-vacant end members. The apparent absence of (3a)-vacant tourmaline in nature is probably due to the lack of fluids that carry boron but no Na or Ca.  相似文献   

10.
Experiments using V2O5 as a high-temperature solvent have produced compositional reversals defining the miscibility gap between enstatite and diopside on the join Mg2Si2O6-CaMgSi2O6 between 925° and 1,175° C at atmospheric pressure. These experiments locate an equilibrium near 1,000° C among diopside, protoenstatite, and orthoenstatite; they verify the stable coexistence of diopside and protoenstatite above 1,000° C and disprove the hypothesis that orthoenstatite has a stability field which is continuous from temperatures below 1,000° C to the solidus. The phase relations suggest that the orthorhombic low-Ca pyroxene on the solidus in this system (formerly identified as orthoenstatite) is a phase distinct from the orthoenstatite stable with diopside at low subsolidus temperatures. Data locating the orthoenstatite-diopside miscibility gap validate the use at low pressures of symmetric orthopyroxene and asymmetric clinopyroxene solution models in this system.  相似文献   

11.
Phase equilibria determined in high-pressure studies of the systems Mg2Si2O6-CaMgSi2O6 and MgSiO3-Mg3Al2Si3O12 can be used to estimate equilibration conditions of ultramafic rocks containing the assemblage enstatite + diopside + garnet. Garnet lherzolite nodules from kimberlites in northern Lesotho appear to have equilibrated in the upper mantle at depths ranging from 100 to 200 km and at temperatures in the range 900–1400°C. Temperature-depth points for these lherzolites form a trend that is interpreted as a segment of a fossil geotherm. The trend is inflected to higher temperatures at its deep end. Lherzolites that plot on the shallow limb of the geotherm have a granular texture whereas those that plot on the deep limb are intensely sheared. It is suggested that the shearing took place in response to plate movements during the break-up of Gondwanaland and that the sheared lherzolites were stress-heated as much as 300°C above their ambient, preshearing temperatures. The point of inflection of the geotherm may mark the top of the low-velocity zone beneath Lesotho in Late Cretaceous time.  相似文献   

12.
Subsolidus and vapor-saturated liquidus phase relations for a portion of the system CaO-MgO-SiO2-H2O, as inferred from experimental data for the composition regions CaMgSi2O6-Mg2SiO4-SiO2-H2O and CaMgSi2O6-Mg2SiO4-Ca3MgSi2O8 (merwinite)-H2O, are presented in pressure-temperature projection. Sixteen invariant points and 39 univariant reactions are defined on the basis of the 1 atm and 10 kbar (vapor-saturated) liquidus diagrams. Lack of experimental control over many of the reactions makes the depicted relations schematic in part.An invariant point involving orthoenstatite, protoenstatite, pigeonite, and diopside (all solid solutions) occurs at low pressure (probably between 1 and 2 kbar). At pressures below this invariant point, orthoenstatite breaks down at high temperature to the assemblage diopside + protoenstatite; with increasing temperature, the latter assemblage reacts to form pigeonite. At pressures above the invariant point, pigeonite forms according to the reaction diopside + orthoenstatite = pigeonite, and the assemblage diopside + protoenstatite is not stable. At 1 atm, both pigeonite and protoenstatite occur as primary liquidus phases, but at pressures above 6–7 kbar orthoenstatite is the only Ca-poor pyroxene polymorph which appears on the vapor-saturated liquidus surface.At pressures above approximately 10.8 kbar, only diopside, forsterite, and merwinite occur as primary liquidus phases in the system CaMgSi2O6-Mg2SiO4-Ca3MgSi2O8-H2O, in the presence of an aqueous vapor phase. At pressures between 1 atm and 10.2 kbar, both akermanite and monticellite also occur as primary liquidus phases. Comparison of the 1 atm and 10 kbar vapor-saturated liquidus diagrams suggests that melilite basalt bears a low pressure, or shallow depth, relationship to monticellite-bearing ultrabasites.  相似文献   

13.
The solubility of Tio2 in phlogopites has been experimentally determined in the system K2Mg6Al2Si6O20(OH)4-K2Mg4TiAl2Si6O20(OH)4-K2Mg5TiAl4Si4O20(OH)4 between 825–1300°C and 10–30 kbar under vapour absent conditions. Starting compositions lie along the join K2Mg6Al2Si6O20(OH)4-K2Mg4.5TiAl3Si5O20(OH)4 which represents a combination of the Mg[VI]2Si[IV] = Ti[VI]2Al[VI] and 2Mg[VI] = Ti[VI]□[VI] substitution mechanisms for Ti in phlogopites. The results of the experiments indicate a systematic increase in solubility of Ti with increasing temperature and decreasing pressure for given bulk Tio2 content. Under isobaric conditions high temperature Ti-saturated phlogopite breaks down to Ti-deficient phlogopite + rutile + vapour. Mass balance calculations suggest that the vapour phase may contain K2O dissolved in H2O and that the reaction is controlled by the vapour phase. Analyses of phlogopites coexisting with rutile and vapour can be represented in terms of the end-member components phlogopite [K2Mg6Al2Si6O20(OH)4], eastonite [K2Mg5Al4Si5O20(OH)4], an octahedral site deficient Ti-phlogopite (Ti-OSD) of composition K2(Mg4Ti□)Al2Si6)O20(OH)4, and Ti-eastonite [K2Mg5TiAl4Si4O20(OH)4]. With decreasing amounts of Ti in these phlogopites there is a decrease in the Ti-eastonite component and increase in the eastonite component.The general equation for the breakdown of Ti-phlogopite solid solution to Ti-free phlogopite + rutile + vapour is: 14 Ti-eastonite + 7 Ti-OSD ? 16 eastonite + 3 phlogopite + 21 rutile + 4 H2O + 2 K2O. Lack of knowledge of H2O and K2O activities in the vapour phase does not permit evaluation of thermodynamic constants for this reaction. The Ti solubility in phlogopites and hence its potential as a geothermobarometer under lower crustal to upper mantle conditions is likely controlled by common mantle minerals such as forsterite.  相似文献   

14.
One petrogenetic grid for plagioclase-, spinel- and garnet-lherzolite analogues in the system CaO-MgO-Al2O3-SiO2 is presented from 1 bar to 30 kbar and 400 to 1500°C. Another grid for olivine-gabbro, spinel-gabbro and garnet-pyroxenite analogues in the same system is presented from 1 bar to 25 kbar and 500 to 1500°C. Both grids show the distribution of the mineral assemblages and the variations in the composition of clinopyroxene with temperature and pressure. They were developed by applying simple thermodynamic mixing models of clinopyroxene to experimentally determined clino-pyroxene compositions.Calcium tschermak's pyroxene (CaAl2SiO6) in complex CaMgSi2O6-CaAl2SiO6-Mg2Si2O6 clinopyroxenes is best represented by a local charge balance mixing model where aCaAl2SiO6? (XCaM2)(XAlM1) Enthalpy and entropy changes of subsolidus reactions involving variations in the CaAl2SiO6 and Mg2Si2O6 content of clinopyroxene are interdependent due to nonideal mixing of these two end-members. CaAl2SiO6 can strongly reduce the mutual solubility of clinopyroxene and orthopyroxene at moderate pressures and high temperatures. Failure to take this into account can result in temperature underestimates (up to 150°C) of spinel-lherzolites, garnet-pyroxenites, low pressure garnet-lherzolites, spinel-gabbros, and high pressure plagioclase-lherzolites and olivine-gabbros. However, at temperatures and pressures where the Al2O3 content of clinopyroxene is low (e.g. garnet-lherzolite nodules in kimberlite), the mutual solubility is adequantely represented by experimental results in the system CaO-MgO-SiO2.  相似文献   

15.
Kosmochlor (NaCrSi2O6) was synthesized by the flux method from melts along the join Na2O·2 SiO2-Na2O·Cr2O3·4 SiO2 at 1000° C in air, and isolated by dissolving the glassy matrix with hydrofluoric and perchloric acids. The join CaMgSi2O6-NaCrSi2O6 was studied at 1 atmosphere in air by the quenching technique at temperatures between 900° and 1450° C, using mixtures of kosmochlor and diopside crystals or diopside glass as starting materials. The phases are diopside solid solution, kosmochlor, spinel (Mg-chromite), eskolaite (Cr2O3) and glass. The maximum solubility of kosmochlor in diopside is 24 wt percent at 1140° C, while diopside is not soluble at all in kosmochlor, resulting in the existence of a wide range of immiscibility. Petrologic significance of the results is discussed.  相似文献   

16.
The dielectric constants and dissipation factors of LiAlSi2O6, CaAl2Si2O8 and CaMgSi2O6 in both the crystalline (α-spodumene, anorthite, and diopside) and amorphous forms were determined at 1 MHz using a two-terminal method and empirically determined edge corrections. The results are: spodumene κ′ 11=7.30 tan δ= 0.0007 κ′22=8.463 tan δ= 0.0002 κ′33 =11.12 tan δ= 0.0007 anorthite κ′ a *=5.47 tan δ= 0.0009 κ′b *=8.76 tan δ= 0.0010 κ′c *=7.19 tan δ= 0.0013 diopside κ′11=9.69 tan δ= 0.0016 κ′22 = 7.31 tan δ= 0.0007 κ′33=7.29 tan δ= 0.00019 LiAlSi2O6 κ′=8.07 tan δ= 0.047 amorphous CaAl2Si2O8 κ′=7.50 tan δ= 0.0024 amorphous CaMgSi2O6 κ′=8.89 tan δ= 0.0021 amorphous The dielectric properties of a spodumene glass, progressively crystallized at different conditions, were also determined. As the crystallization temperature was increased from 720 to 920° C, κ′ increased from 6.22 to 6.44. The dissipation factor, tan δ, remained constant at 0.020. Similarly, as the crystallization time at 750° C increased from 0.5 hr to 6.0 hr, κ′ increased from 6.28 to 6.35. The deviations of the measured dielectric polarizabilities as determined from the Clausius-Mosotti equation from those calculated from the sum of oxide polarizabilities according to α D(mineral, glass) = σ α D(oxides) are +7.4% for α-spodumene, +1.2% for diopside, and +28.0, +19.6 and +15.9% for amorphous spodumene, anorthitie and diopside compositions, respectively. Positive deviations in α-spodumene and anorthite are consistent with lower than normal apparent cation bond valence sums and are believed to be evidence for loosely bonded “rattling” Li and Ca ions. Diopside, with Ca and Mg ions having normal bond valence sums, exhibits no abnormal deviation from additivity. Larger positive deviations in amorphous SiO2, LiAlSi2O6, CaAl2Si2O8 and CaMgSi2O6 are postulated to arise from a combination of loosely bonded cations and disordered O= ions where the oxygen dielectric polarizability increased from its normal value of 2.0 Å3 in well-behaved oxides to 2.2–3.0 Å3 in the amorphous phases.  相似文献   

17.
The pyroxene saturation surface in the system diopside-albite-anorthite may be calculated to ±10°C from thermochemical data over most of its composition range. The thermochemical data used are the experimentally determined enthalpies of mixing of the ternary liquids and the enthalpy of fusion of diopside. These are combined with a mixing model for the configurational entropy in the melt and the activity of CaMgSi2O6 in the clinopyroxene, which is less than unity due to departures from CaMgSi2O6 stoichiometry. The ‘two-lattice’ melt model appears to work satisfactorily throughout the pyroxene primary phase field but probably needs modification at more anorthite-rich compositions.  相似文献   

18.
 Melting relations on the enstatite−diopside (En, Mg2Si2O6−Di, CaMgSi2O6) join, including the compositions of crystalline phases and melts coexisting along the solidi, were experimentally determined in the pressure range 70–224 kbar with a split-sphere anvil apparatus (USSA-2000). Melting is peritectic in enstatite-rich compositions at 70–124 kbar (1840–2100° C) and eutectic at higher pressures, while the diopside-rich clinopyroxene melts azeotropically at 70–165 kbar and up to 300° C lower temperatures than the eutectic. Orthopyroxene is replaced with enstatite-rich clinopyroxene at 120 kbar and 2090°C. First garnet with 17 mol% Di forms on the solidus at 158 kbar and 2100° C. Two garnets coexist on the solidus at 165–183 kbar and 2100° C, garnet coexists with CaSiO3 perovskite at 183–224 kbar (2100–2230° C) and two coexisting perovskites are stable at higher pressures. The melting curve of diopside was determined at 80–170 kbar; the slope becomes negative at 140 kbar and 2155° C. At 170 kbar and 2100° C, diopside with 96% Di breaks down to garnet with 89% Di and CaSiO3 perovskite. The new data were used to calculate an improved temperature-pressure phase diagram for the CMAS system, which can be useful for estimating the mineralogy of the Earth's upper mantle. Received: 15 October 1994 / Accepted: 15 October 1995  相似文献   

19.
The short term (2–40 days) dissolution of enstatite, diopside, and tremolite in aqueous solution at low temperatures (20–60°C) and pH 1–6 has been studied in the laboratory by means of chemical analyses of reacting solutions for Ca2+, Mg2+, and Si(OH)4 and by the use of X-ray photoelectron spectroscopy (XPS) for detecting changes in surface chemistry of the minerals. All three minerals were found to release silica at a constant rate (linear kinetics) providing that ultrafine particles, produced by grinding, were removed initially by HF treatment. All three also underwent incongruent dissolution with preferential release of Ca and/or Mg relative to Si from their outermost surfaces. The preferential release of Ca, but not Mg for diopside at pH 6 was found by both XPS and solution chemistry verifying the theoretical prediction of greater mobility of cations located in M2 structural sites. Loss mainly from M2 sites also explains the degree of preferential loss of Mg from enstatite at pH 6; similar structural arguments apply to the loss of Ca and Mg from the surface of tremolite. In the case of diopside and tremolite initial incongruency was followed by essentially congruent cation-plus-silica dissolution indicating rapid formation of a constant-thickness, cation-depleted surface layer. Cation depletion at elevated temperature and low pH (~ 1) for enstatite and diopside was much greater than at low temperature and neutral pH, and continued reaction resulted in the formation of a surface precipitate of pure silica as indicated by solubility calculations, XPS analyses, and scanning electron microscopy.From XPS results at pH 6, model calculations indicate a cation-depleted altered surface layer of only a few atoms thickness in all three minerals. Also, lack of shifts in XPS peak energies for Si, Ca, and Mg, along with undersaturation of solutions with respect to all known Mg and Ca silicate minerals, suggest that cation depletion results from the substitution of hydrogen ion for Ca2+ and/or Mg2+ in a modified silicate structure and not from the precipitation of a new, radically different surface phase. These results, combined with findings of high activation energies for dissolution, a non-linear dependence on aH+ for silica release from enstatite and diopside, and the occurrence of etch pitting, all point to surface chemical reaction and not bulk diffusion (either in solution or through altered surface layers) as the rate controlling mechanism of iron-free pyroxene and amphibole dissolution at earth surface temperatures.  相似文献   

20.
Enthalpies of solution in eutectic (Li, Na)2B2O4 melts at 1023 K were measured for five synthetic orthopyroxenes on the join MgSiO3-FeSiO3. The pyroxenes were synthesized at 1120°C and 20 kbar and thus were presumed to be highly disordered. The measurements indicate a small positive enthalpy of mixing, with WH = 950 cal/MSiO3.Enthalpy of solution measurements were made on a natural, well-ordered orthopyroxene near the composition En52.5Fs47.5 and on this material after heat-treatment at 1150°C and 20 kbar. Irreversible expansion of the unit-cell constants of the natural pyroxene after heat-treatment at various temperatures was used to characterize the degree of M-site disorder. The observed enthalpy of solution decrement of 0.85 kcal/MSiO3 between the natural En52.5 and the same material heated at 1150° corresponds to about half of the maximum possible disordering, or ΔXFeM1? 0.25, which leads to a ΔH of 7.5 kcal/M2Si2O6, for the exchange reaction: Fe(M2) + Mg(Ml) = Fe(Ml) + Mg(M2) if M-site interaction energy terms are ignored. This ΔH is larger than inferred from any of the analyses of site-occupancy data except that of Besancon (1981), who gave a very similar value. The measured ΔH of disorder and the WH of mixing together indicate a large ΔH as great as 3.2 kcal for the reciprocal reaction: Fe2Si2O6 + Mg2Si2O6 = Fe(M2)Mg(M1)Si2O6 + Fe(M1)Mg(M2)Si2O6 as anticipated by Sack (1980).As a consequence of the inferred magnitudes of ΔHof the exchange and reciprocal reactions, departures from ideality of Gibbs energy of mixing of orthopyroxene are very small at 700°–1000°C. Activities of MgSiO3 and FeSiO3 may be replaced by their mol fractions at all temperatures in most petrologic calculations.  相似文献   

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