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1.
Liquidus phase relationships in the CaAlAl–SiO6–Mg2SiO4–CaMgSi2O6–CaAlSi2O8 portion of the simplified basalt tetrahedron in the CaO–MgO–SiO2–Al2O3 system have been experimentally determined at 20 kbar pressure. The fo+di ss+sp+li univariant curve, that pierces the fo-di-an join and meets the fo+di ss+ enss+sp+li invariant point in the basalt tetrahedron, extends all the way to and pierces the di-fo-CaTs join, the limit of the simplified basalt tetrahedron toward the silica undersaturated portion.An algebraic method, relying on compositions of two successive liquids on a univariant curve and those of the crystalline phases in equilibrium with the respective liquids, is developed to identify the type of reaction that takes place along an isobarically univariant curve and to detect whether there is a temperature maximum on that curve. Use of this method for the di ss+fo+sp+li univariant equilibria shows that a temperature maximum exists on this curve at the composition Fo11Di56An3CaTs30, very close to and slighthly to the SiO2-rich side of the fo-di-CaTs join. The temperature along the univariant curve continuously decreases from the temperature maximum (1500°C) to the invariant point (1475°C) where the univariant curve is terminated by the appearance of e ss as a member of the equilibrium assemblage. Along this part of the curve, a reaction relationship occurs according to the equation fo+li=di ss+ sp. Compositions of di ss in equilibrium with the liquids from the temperature maximum to the fo+di ss+enss+ sp+li invariant point range from Di66En9CaTs25 to Di36En40CaTs24. Because of the reaction relationship of forsterite with liquid, fractional crystallization of a model alkalic basaltic liquid would cause liquids to move off the fo-di ss-sp-li univariant curve onto the sp-di ss divariant surface. Crystallization of di ss and sp would then lead to silica enrichment of residual liquids. Thus at pressures below 30 kbar, at which pressure the Al2O3–CaSiO3–MgSiO3 plane becomes a new thermal divide cutting through both the tholeiitic and alkalic volumes, alkalic liquids will fractionate toward tholeiitic compositions without crossing a thermal divide. This relationship would be expected to persist at pressures down to about 4 kbar where a maximum on the fo-di-an-li boundary line causes a thermal divide near the fo-di-an plane. Strongly SiO2-undersaturated liquids (e.g. nephelinites, basanites), on the other hand, cannot be derived from SiO2-undersaturated basalts (e.g. alkali olivine basalt) by fractional crystallization at 20 kbar. We also found that no gt primary phase volume cuts the wo-en-Al2O3 join at 20 kbar pressure. The wehrlite, the olivine clinopyroxenite, and the Al-augite group lherzolite xenoliths, containing highly aluminous clinopyroxenes (enriched in Ca-Tschermak), can be interpreted as crystal cumulates from alkalic basalts in the light of this experimental study. This is consistent with the mode of origin of these xenoliths proposed from petrographic, mineralogic, and geochemical studies.Abbreviations and notations di CaMgSi2O6 - fo Mg2SiO4 - an CaAl2Si2O8 - CaTs CaAlAlSiO6 - sp MgAl2O4 - en MgSiO3 - wo CaSiO3 - gt Ca3Al2Si3O12–Mg3Al2Si3O12 - qz SiO2 - li Liquid - gl glass - ss Solid Solution - A An mxn matrix - X A column vector - kbar kilobar  相似文献   

2.
Published phase diagrams for the siliceous carbonate system CaO–MgO–SiO2–CO2–H2O are contradictory because of different estimates of the relative stability of magnesite. Experimental data on magnesite are too ambiguous to determine the validity of these estimates. Therefore, field evidence is used to select the correct phase diagram topology for siliceous carbonate and carbonate ultramafic rocks at pressures of about 2–5 kbar. The primary selection criterion is provided by the existence of the stable assemblage talc+dolomite+forsterite+tremolite+antigorite, which occurs in the Bergell contact aureole and Swiss Central Alps. Field evidence also is used to argue that the reaction magnesite+quartz=enstatite must occur at lower temperature than the reaction dolomite+quartz=diopside. T-X CO 2 and P CO 2-T phase diagrams consistent with these observations are calculated from experimental and thermo-dynamic data. For antigorite ophicarbonate rocks, remarkable agreement is obtained between the spatial distribution of low variance mineral assemblages and the calculated diagrams.  相似文献   

3.
This paper reports measurements of electrical conductivity in Co2SiO4 as a function of temperature in the range from 780 to 1540 K and oxygen fugacity in the range from 5 × 10–8 to 2.6 × 10–5 MPa at 1540 K. From the present data and available literature data on defect concentrations in Co2SiO4, the mobility of the defect responsible for conduction is determined to be 8.6 × 10–7 m2/V-s at 1373 K. On the basis of these data and the observed dependence of conduction on oxygen fugacity, it is concluded that small polarons associated with oxidized cobalt ions is the likely mechanism controlling conduction. The mobility of small polarons in iron-bearing olivine under similar conditions is likely to be of the same order of magnitude.  相似文献   

4.
Three new crystalline phases differing in Si/Al ratio have been synthesized from compositions along the join NiAl2O4-Ni2SiO4. Four reversible univariant equilibria involving these new phases plus Ni2SiO4 (olivine) have been located within the P-T region studied (1 atm–40 kb, 1000–1700° C); an invariant point occurs near 22 kb, 1150°C.All three new phases are orthorhombic. Precession photographs and electron microprobe analyses yield the following information:Phase I: 5NiO·3Al2O3·SiO2 = 3NiAl2O4·Ni2SiO4, Pmma, a=5.67, b=11.51, c=8.10 (Å)Phase II: 7NiO·3Al2O3·2SiO2 = 3NiAl2O4· 2Ni2SiO4, Imma, a=5.66, b=17.32, c=8.11Phase III: 3NiO· Al2O3· SiO2 = NiAl2O4·Ni2SiO4, Imma, a=5.68, b=11.49, c=8.12Comparison with known structures suggests that these three phases plus NiAl2O4 spinel and high pressure Ni2SiO4 spinel belong to a homologous series based on a cubic close oxygen packing of the formula: M2n O n}-1 (T n O3n+1) where M and T are octahedrally and tetrahedrally coordinated cations, respectively. When n=1 the formula for spinel is obtained; n = 2 for phase I and phase III, both similar to the beta-phase of orthosilicates; and n = 3 for phase II which is related to the manganostibite structure.Similar phase equilibria and structural relations may occur on other joins of the aluminateorthosilicate type. Furthermore, the occurrence of such structural modifications between the spinel (aluminate) and olivine (orthosilicate) compositions suggests that there could be a corresponding polymorphic series between the olivine and spinel forms of orthosilicates.  相似文献   

5.
A thermodynamic solution model is developed for minerals whose compositions lie in the two binary systems Mg2SiO4-Fe2SiO4 and Mg2Si2O6-Fe2Si2O6. The formulation makes explicit provision for nonconvergent ordering of Fe2+ and Mg2+ between M1 and M2 sites in orthopyroxenes and non-zero Gibbs energies of reciprocal ordering reactions in both olivine and orthopyroxene. The calibration is consistent with (1) constraints provided by available experimental and natural data on the Fe-Mg exchange reaction between olivine and orthopyroxene ± quartz, (2) site occupancy data on orthopyroxenes including both crystallographic refinements and Mössbauer spectroscopy, (3) enthalpy of solution data on olivines and orthopyroxenes and enthalpy of disordering data on orthopyroxene, (4) available data on the temperature and ordering dependence of the excess volume of orthopyroxene solid solutions, and (5) direct activity-composition determinations of orthopyroxene and olivine solid solutions at elevated temperatures. Our analysis suggests that the entropies of the exchange [Mg(M2)Fe(M1)Fe(M2)Mg(M1)] and reciprocal ordering reactions [Mg(M2)Mg(M1)+ Fe(M2)Fe(M1)Fe(M2)Mg(M1)+Mg(M2)Fe(M1)] cannot differ significantly (± 1 cal/K) from zero over the temperature range of calibration (400°–1300° C). Consideration of the mixing properties of olivine-orthopyroxene solid solutions places tight constraints on the standard state thermodynamic quantities describing Fe-Mg exchange reactions involving olivine, orthopyroxene, pyralspite garnets, aluminate spinels, ferrite spinels and biotite. These constraints are entirely consistent with the standard state properties for the phases-quartz,-quartz, orthoenstatite, clinoenstatite, protoenstatite, fayalite, ferrosilite and forsterite which were deduced by Berman (1988) from an independent analysis of phase equilibria and calorimetric data. In conjunction with these standard state properties, the solution model presented in this paper provides a means of evaluating an internally consistent set of Gibbs energies of mineral solid solutions in the system Mg2SiO4-Fe2SiO4-SiO2 over the temperature range 0–1300° C and pressure interval 0.001–50 kbars. As a consequence of our analysis, we find that the excess Gibbs energies associated with mixing of Fe and Mg in (Fe, Mg)2SiO4 olivines, (Fe, Mg)3Al2Si3O12 garnets, (Fe, Mg)Al2O4 and (Fe, Mg)Fe2O4 spinels, and K(Mg, Fe)3AlSi3O10(OH)2 biotites may be satisfactory described, on a macroscopic basis, with symmetric regular solution type parameters having values of 4.86±0.12 (olivine), 3.85±0.09 (garnet), 1.96±0.13 (spinel), and 3.21±0.29 kcals/gfw (biotite). Applications of the proposed solution model demonstrate the sensitivity of petrologic modeling to activity-composition relations of olivine-orthopyroxene solutions. We explore the consequences of estimating the activity of silica in melts forming in the mantle and we develop a graphical geothermometer/geobarometer for metamorphic assemblages of olivine+orthopyroxene+quartz. Quantitative evaluation of these results suggests that accurate and realistic estimates of silica activity in melts derived from mantle source regions,P-T paths of metamorphism and other intensive variables of petrologic interest await further refinements involving the addition of trace elements (Al3+ and Fe3+) to the thermodynamic formulation for orthopyroxenes.  相似文献   

6.
Shombole, a nephelinite-carbonatite volcano in south Kenya, erupted silicate lavas, carbonatite dikes and tuffs, and pyroclastic rocks similar to those at other East African alkaline centres. Shombole lavas containing cpx + nepheline + accessory minerals range from perovskite-bearing nephelinites (43% SiO2, volatile-free) to sphene-bearing and phonolitic nephelinites (46–49% SiO2) and phonolites (49–56% SiO2) and have low peralkalinity ([Na+K]/Al 1.15) which does not correlate with SiO2. Early fractionation of olivine and clinopyroxene strongly depleted Ni and Cr concentrations (10 ppm); fractionation of perovskite, melanite, sphene, and apatite produced negative correlations of all REE with SiO2. Many lavas contain cognate intrusive xenoliths and xenocrysts and oscillatory zoning is a common feature of clinopyroxene, nepheline, and melanite crystals, indicating recycling of intrusive material. Irregular calcite-rich bodies in many samples are interpreted as quenched immiscible Ca-carbonatite liquid, and [Ca-carbonate]-silicate liquid immiscibility is observed in experiments with one nephelinite. Chemical variation in the Shombole suite can be modeled as a combination of crystal fractionation (clinopyroxene and heavy minor phases) and retention of neutral density nepheline derived from disaggregated xenoliths entrained during emplacement of dike swarms. Six newly analyzed lavas from Oldoinyo L'engai, northern Tanzania, are geochemically similar to Shombole nephelinites except that they have relatively high Na2O+K2O (average 18% vs 12%) and Zr (average 680 ppm vs 400 ppm). They are extremely peralkaline and are not typical of nephelinites from other centres. Three with [Na+K]/Al1.5 contain euhedral wollastonite phenocrysts; three with [Na+K]/Al2.0 contain combeite (Na2Ca2Si3O9) phenocrysts and pseudomorphs after wollastonite. Both types contain abundant sodalite phenocrysts (+nepheline+clinopyroxene+melanite+sphene). Seven other wollastonite nephelinite samples from L'engai have been described, but it is a lava type rarely seen in other centres. Combeite has been described from only two other locations (Mt. Shaheru, Zaire; Mayener Feld, Eifel). The hyperalkaline L'engai nephelinites have compositions similar to those of experimental silicate liquids immiscible with natrocarbonatite. Textural evidence for both carbonate-silicate (as carbonate globules) and silicate-silicate (as two optically discrete glasses with distinct compositions) liquid immiscibility is observed in the samples.  相似文献   

7.
Crystal field stabilization (CFS) plays a significant role in determining equilibrium phase boundaries in olivine→spinel transformations involving transition-metal cations, including Fe2+ which is a major constituent of the upper mantle. Previous calculations for Fe2SiO4 ignored pressure and temperature dependencies of crystal field stabilization enthalpies (CFSE) and the electronic configurational entropy (S CFS). We have calculated free energy changes (ΔG CFS) due to differences of crystal field splittings between Fe2SiO4 spinel and fayalite from: ΔG CFS=?ΔCFSE?TΔS CFS, as functions of P and T, for different energy splittings of t 2g orbital levels of Fe2+ in spinel. The results indicate that ΔG CFS is always negative, suggesting that CFS always promotes the olivine→spinel transition in Fe2SiO4, and expands the stability field of spinel at the expense of olivine. Because of crystal field effects, transition pressures for olivine→spinel transformations in compositions (Mg1?x Fe x )2SiO4 are lowered by approximately 50x kbar, which is equivalent to having raised the olivine→spinel boundary in the upper mantle by about 15 km.  相似文献   

8.
Tholeiite basalts from 60° N to 65° N on the Mid-Atlantic Ridge were melted and recrystallized at atmospheric pressure in a CO2-H2 gas mixture. Seven basalts are from the Langjokull-Thingvellir volcanic zone and the Reykjanes Peninsula of Iceland and nine are from the Reykjanes Ridge. The crystallization sequence in both Iceland and Reykjanes Ridge basalts with (Total Fe as FeO)/(Total Fe as FeO+ MgO) [F/F + M] less than 0.6 is olivine, plagioclase, clinopyroxene. Chromian spinel crystallizes before plagioclase in one Iceland and one Reykjanes Ridge basalt with F/F+M less than 0.57. Chemical differences of the two groups of basalts (lower SiO2 and higher alkalis in Iceland basalts) can not simply be a result of low pressure fractional crystallization. Liquidus temperatures of the seven Iceland basalts decreases from 1,230° C to 1,170° C as the F/F+M of the rock increases from 0.52 to 0.70. The liquidus temperatures of the Reykjanes Ridge basalts are about 10° C lower than those of the Iceland basalts for the same F/F+M value. The profile of measured liquidus temperatures from 65° N on Iceland to 60° N on the Reykjanes Ridge has a minimum value at 63.2° N on the Reykjanes Ridge just south of Iceland. Model calculations of the pressure of phenocryst crystallization indicate that olivine and plagioclase in Langjokull basalts could have equilibrated between 2.0 and 6.2 kb (200 to 620 MPa). Phenocryst assemblages in Reykjanes Ridge basalts at 60° N could have crystallized together at greater than 2 kb (200 MPa) and probably less than 8 kb (800 MPa). A minimum in the equilibrium pressure of phenocryst crystallization occurs between 62.9° and 64° N and coincides with the minimum in the experimentally determined liquidus temperatures. The more extensive fractionation at low pressure in this area could be related to the shift of the Mid-Atlantic Ridge axis along the leaky transform fault from the Reykjanes Ridge to the Thingvellir volcanic zone.  相似文献   

9.
The nature of the near-liquidus phases for a mantle-derived olivine melilitite composition have been determined at high pressure under dry conditions and with various water contents. Olivine and clinopyroxene occur on or near the liquidus and there are no conditions where orthopyroxene crystallizes in equilibrium with the olivine melilitite. We have determined the effect on the liquidus temperature and liquidus phases of substituting CO2 for H2O on a mole for mole basis at 30 kb, using olivine melilitite + 20 wt% H2O at = 0 and = (CO2)/(H2+CO2) (mole fraction) = 0.25, 0.5, 0.75 and 1.0 (i.e. olivine melilitite + 38 wt% CO2). Experiments were buffered by the MH or NNO buffers. At 30 kb, CO2 is only slightly less soluble than water for <0.5 as judged by the slight increase in liquidus temperature on mole-for-mole substitution of CO2 for H2O and at 30 kb, 1200° C, = = 0.5 the olivine melilitite contains 8.8 wt% H2O and 21 wt% CO2 in solution. For 1 the CO2 saturated liquidus is depressed 70 ° C below the anhydrous liquidus and the magma dissolves approx. 17% CO2 at 30kb, 1400 ° C, 1, 0. Infrared spectra of quenched glasses have absorption bands characteristic of CO 3 = and OH- molecules and no evidence for HCO 3 - . The effect of CO 3 = molecules dissolved in the olivine melilitite at high pressure is to suppress the near-liquidus crystallization of olivine and clinopyroxene and bring orthopyroxene and garnet on to the liquidus. We infer that olivine melilitite magmas may be derived by equilibrium partial melting (<5%) of pyrolite at 30 kb, 1150–1200 ° C, provided that both H2O and CO2 are present in the source region in minor amounts. Preferred conditions are 0< <0.5, 0.5< <1, and at low oxygen fugacities (相似文献   

10.
The mineralogy and chemistry of picrites from Mauna Loa and Kilauea have been investigated to evaluate, for Hawaiian tholeiitic picrites, the contrasting genetic models which have been proposed for these Mg-rich volcanics, namely products of direct crystallization of high-Mg melts (20–25% MgO) or the result of accumulation of olivine phenocrysts into less Mg-rich melts. Genetic interpretations rely heavily on Mg-Fe partitioning relations between olivines and their picrite hosts. Although the 100 Mg/(Mg + Fe2+) ratios (M) of picrites are wide-ranging (M=73.6–82.9 for Fe2O3/FeO=0.15), with MgO as high as 27.8%, the average 100 Mg/(Mg+Fe) ratios (mg) of the cores of olivine phenocrysts (megacrysts) show only restricted compositional variation (mg=87.2–89.0). Successive olivine generations are progressively more Fe-rich. Olivine/liquid Mg-Fe partitioning data and the Mn and Ni abundances in olivine phenocrysts collectively indicate that they were precipitated by Mg-rich basaltic melts with 12–14% MgO. Spinel compositions range from liquidus magnesiochromites, occurring mainly as inclusions in olivine phenocrysts, to groundmass titanomagnetites which crystallized at nearsolidus temperatures. The Cr2O3 contents and M values of liquidus magnesiochromites suggest that their parent melts were neither Mg-rich picritic (MgO>20%) nor relatively Mg-poor basaltic types.On MgO variation diagrams (extending from approximately 7% to more than 25% MgO), Mauna Loa and Kilauea picrites and their respective microcrystalline/glassy groundmasses (the major component of quickly-cooled picrites) plot on linear regression lines (olivine control lines). At a given MgO content, Kilauean picrites and tholeiites (M<75) generally contain more TiO2 FeO t , CaO, K2O and P2O5, and less SiO2 and Na2O than Mauna Loan types. The compositions of the groundmasses in picrites and Mg-rich ol-tholeiites equate closely with those of the Mg-poor tholeiites (7–9% MgO) which dominate the petrology of each shield.Low-pressure closed system differentiation of Hawaiian tholeiitic magmas (10–15% MgO) can yield picritic derivatives which differ, however, from the extrusive picrites by virtue of distinctly higher FeO t contents and correspondingly more Fe-rich olivines and Cr-spinels.The calculated Mg-Fe olivine megacryst-liquid partition coefficient K D for individual picrites indicate that lowpressure equilibria (K D =0.30–0.34) are defined only by melts with approximately 12–14% MgO (M 71–74). Assessed in conjunction with Ni-MgO modeling, these data indicate that the more Mg-rich picrites (MgO> 14–15%) are indeed olivine-enriched and do not represent melt compositions. Olivine enrichment resulted from post-eruptive mechanical (flow) differentiation of extruded mushes of intratelluric cognate olivine phenocrysts (mg88) and tholeiitic melts (M60), which are residua of the parental magmas (12–14% MgO), following the crystallization of the olivine phenocrysts. The parental magmas of both picrite suites were generated by 35–40% melting of relatively Fe-rich spinel lherzolites (mg84) containing kaersutitic amphibole as a major primary constituent.  相似文献   

11.
At Medicine Lake Volcano, California, the compositional gap between andesite (57–62 wt.% SiO2) and rhyolite (73–74 wt.% SiO2) has been generated by fractional crystallization. Assimilation of silicic crust has also occurred along with fractionation. Two varieties of inclusions found in Holocene rhyolite flows, hornblende gabbros and aphyric andesites, provide information on the crystallization path followed by lavas parental to the rhyolite. The hornblende gabbros are magmatic cumulate residues and their mineral assemblages are preserved evidence of the phases that crystallized from an andesitic precursor lava to generate the rhyolite lavas. The andesitic inclusions represent samples of a parental andesite and record the early part of the differentiation history. Olivine, plagioclase and augite crystallization begins the differentiation history, followed by the disappearance of olivine and augite through reaction with the liquid to form orthopyroxene and amphibole. Further crystallization of the assemblage plagioclase, amphibole, orthopyroxene, magnetite, and apatite from a high-SiO2 andesite leads to rhyolite. This final crystallization process occurs on a cotectic that is nearly horizontal in temperature-composition space. Since a large amount of crystallization occurs over a limited temperature interval, a compositional gap develops between rhyolite and high SiO2 andesite.Liquidus surfaces with shallow slopes in temperature-composition space are characteristic of several late-stage crystallization assemblages in the andesite to rhyolite compositional range. Experimentally produced plagioclase+ amphibole+orthopyroxene+magnetite and plagioclase+ augite+low-Ca pyroxene+magnetite cotectics have liquidus slopes that are nearly flat. At other calc-alkaline volcanic centers crystallization processes involving large compositional changes over small temperature intervals may also be important in the development of bimodal volcanism (i.e. the existence of a composition gap). At Mt. Mazama and Mt. St. Helens, USA and Aso Caldera and Shikotsu, Japan the amphibole-bearing assemblage was important. At Krakatau, Indonesia and Katmai, USA, an augite+orthopyroxene-bearing assemblage was important. In addition to its role in the production of a compositional gap between intermediate and rhyolitic lavas, the crystallization process increases the H2O content of the residual liquid. This rapid increase in residual liquid volatile content which results from the precipitation of a large proportion of crystalline solids may be an important factor among several that lead to explosive silicic eruptions.  相似文献   

12.
Phase relations and mineral chemistry involving the phases garnet (Gt), spinel (Sp), hypersthene (Hy), sapphirine (Sa), cordierite (Cd), sillimanite (Sil) and quartz (Qz) have been experimentally determined in the system FMAS (FeO−MgO−Al2O2−SiO2) under low fO2 and for various H2O/CO2 conditions. Several compositions were studied with 100 (Mg/Mg+Fe) ratio ranging from 64 to 87 with excess quartz and sillimanite. Our data do not show any differences in Gt−Cd stability and composition as a function of H2O, CO2 and H2O−CO2 (±CH4) content, in good agreement with a previous experimental study at lower temperature (Aranovich and Podlesskii 1983). At 1,000° C and 11 kbar, under CO2-saturated conditions, cordierite grew from a crystalline mix unseeded with cordierite. Thus, under water-absent conditions, cordierite will have a high-P stability field in the presence of CO2. If water has a pressure stabilizing effect on cordierite, then our results would indicate that the effects of H2O and CO2 are of the same magnitude at high temperature. Our data support the theoretical P-T grid proposed by Hensen (1986) for high-T metapelites and are largely consistent with the high-temperature experimental data of Hensen and Green (1973). The univariant boundary Gt+Cd=Hy+Sil+Qz, which marks the disappearance of Hy−Sil−Qz assemblages, has a negative dP/dT slope above 1,000° C and a positive one below this temperature. Extrapolation of our data to iron-free systems shows that the high-P breakdown limit of Mg-cordierite has a negative slope in the range 1,025–1,300° C and probably positive below 1,000° C. This indicates a maximum of stability for Mg-cordierite at around 1,000° C and 13 kbar. Because of the curvature of the univariant reactions En+Sil=Py+Qz, Mg−Cd=En+Sil+Qz and Gt+Cd=Hy+Sil+Qz, the iron-free invariant point involving the phases Py, En, Cd, Sil and Qz probably does not exist. Sapphirine—Qz-bearing assemblages are stable only at temperatures above 1,050° C. At 1,075° C, the joint Gt−Sa is stable up to 11 kbar. At higher pressure, garnet, sapphirine and quartz react according to the reaction Gt+Sa+Qz=Hy+Sil. Reequilibrated sapphirines are more aluminous than the theoretical endmember Mg2Al4SiO10 due to AlAl=MgSi substitutions [100(Al2O3/Al2O3+FeO+MgO) in experimental sapphirines ranges from 50.5 to 52.2]. Sapphirine in the assemblage Sa−Cd−Sil−Qz shows a decrease in Al content with decreasing temperature and pressure, such that the alumina isopleths for sapphirine have a slight negative dP/dT slope. A similar decrease in Al content of sapphirine with temperature is also observed in Sa−Sil−Qz assemblages.  相似文献   

13.
Internally consistent thermodynamic computation of equilibria in the FeO-MgO-SiO2 system up to 300 kbar is carried out and phase diagrams and profiles of the elastic properties and density are constructed at the depths of 300–800 km. Comparisons of calculated thermodynamic properties for different petrological models with seismic velocity profiles have been used to constrain the mineralogy of the mantle discontinuities. The 400-km discontinuity may represent the univariant or divariant transition in the olivine component of pyrolite as well as a chemical boundary. For the pyrolite composition at the depth of 650 km there are two different spinel + perovskite + stishovite (640 km) and magnesiowustite + spinel + perovskite (650 km) divariant loops (1–2 km wide) separated by a Invariant zone spinel + perovskite (4–6 km wide). The results indicate that phase changes in pyrolite do not explain the 650-km discontinuity. It is also shown that it is impossible to match the seismic properties observed at the depths of 600–800 km and through the discontinuity with any isochemical petrological model considered in the FMS system. However, increasing the iron content or silica and iron contents across the 650-km discontinuity can produce thermodynamic properties in the lower mantle that are more consistent with those inferred from seismic observations. Constraints on the SiO2 and iron contents in the mantle are inferred from the comparison of thermodynamic and seismological data.  相似文献   

14.
Solution enthalpies of synthetic olivine solid solutions in the system Mg2SiO4-Fe2SiO4 have been measured in molten 2PbO·B2O3 at 979 K. The enthalpy data show that olivine solid solutions have a positive enthalpy of mixing and the deviation from ideality is approximated as symmetric with respect to composition, in contrast to the previous study. Applying the symmetric regular solution model to the present enthalpy data, the interaction parameter of ethalpy (WH) is estimated to be 5.3±1.7 kJ/mol (one cation site basis). Using this Wh and the published data on excess free energy of mixing, the nonideal parameter of entropy (Ws) of olivine solid solutions is estimated as 0.6±1.5 J/mol·K.  相似文献   

15.
Bowen's petrogenetic grid was based initially on a series of decarbonation reactions in the system CaO-MgO-SiO2-CO2 with starting assemblages including calcite, dolomite, magnesite and quartz, and products including enstatite, forsterite, diopside and wollastonite. We review the positions of 14 decarbonation reactions, experimentally determined or estimated, extending the grid to mantle pressures to evaluate the effect of CO2 on model mantle peridotite composed of forsterite(Fo)+orthopyroxene(Opx)+clinopyroxene(Cpx). Each reaction terminates at an invariant point involving a liquid, CO2, carbonates, and silicates. The fusion curves for the mantle mineral assemblages in the presence of excess CO2 also terminate at these invariant points. The points are connected by a series of reactions involving liquidus relationships among the carbonates and mantle silicates, at temperatures lower (1,100–1,300° C) than the silicate-CO2 melting reactions (1,400–1,600° C). Review of experimental data in the bounding ternary systems together with preliminary data for the system CaO-MgO-SiO2-CO2 permits construction of a partly schematic framework for decarbonation and melting reactions at upper mantle pressures. The key to several problems in the peridotite-CO2 subsystem is the intersection of a subsolidus carbonation reaction with a melting reaction at an invariant point near 24 kb and 1,200°C. There is an intricate series of reactions between 25 kb and 35 kb involving changes in silicate and carbonate phase fields on the CO2-saturated liquidus surfaces. Conclusions include the following: (1) Peridotite Fo+Opx+Cpx can be carbonated with increasing pressure, or decreasing temperature, to yield Fo+Opx+Cpx+Cd (Cd=calcic dolomite), Fo+Opx+Cd, Fo+Opx+Cm (Cm=calcic magnesite), and finally Qz+Cm. (2) Free CO2 cannot exist in subsolidus mantle peridotite with normal temperature distributions; it is stored as carbonate, Cd. (3) The CO2 bubbles in peridotite nodules do not represent free CO2 in mantle peridotite along normal geotherms. (4) CO2 is as effective as H2O in causing incipient melting, our preferred explanation for the low-velocity zone. (5) Fusion of peridotite with CO2 at depths shallower than 80 km produces basic magmas, becoming more SiO2-undersaturated with depth. (6) The solubility of CO2 in mantle magmas is less than about 5 wt% at depths to 80 km, increasing abruptly to about 40 wt% at 80 km and deeper. (7) Deeper than 80 km, the first liquids produced are carbonatitic, changing towards kimberlitic and eventually, at considerably higher temperatures, to basic magmas. (8) Kimberlite and carbonatite magmas rising from the asthenosphere must evolve CO2 at depths 100-80 km, which contributes to their explosive emplacement. (9) Fractional crystallization of CO2-bearing SiO2-undersaturated basic magmas at most pressures can yield residual kimberlite and carbonatite magmas.  相似文献   

16.
An experiment conducted in a 2000-ton uniaxial split-sphere apparatus (USSA-2000) utilizes large sample volume and a substantial temperature gradient to synthesize intergrowths of the olivine and spinel polymorphs of Co2SiO4. The olivine starting material consists of a finegrained fraction (<20μm) which records the stable polymorphs along the length of the sample plus large olivine grains (100–500 μm) which help decipher the mechanism of the phase transformation. At conditions near equilibrium, the olivine-spinel transformation in the large grains occurs by inward growth of a few large single crystals of spinel nucleated on the surfaces of the olivine. The overall rate of transformation is governed by the mobility of the interphase boundary, whose morphology is crystallographically controlled by the spinel. No renucleation of spinel is observed in the host olivine crystal, even in the region immediately adjacent to the olivine/spinel interface; analysis of this region with transmission electron microscopy reveals an extremely high density of dislocations induced by plastic flow accommodating the volume change associated with the phase transformation.  相似文献   

17.
Summary The crystal structure of Ca5(PO4)2SiO4 (silico-carnotite) has been determined from 3358 x-ray diffraction data collected by a counter method and has been refined toR w =0.038,R=0.045, in space group Pnma. The unit cell parameters area=6.737 (1) Å,b=15.508 (2) Å andc=10.132 (1) Å at 24°C;Z=4. The observed density is 3.06 and the calculated density is 3.03 g · cm–3. The crystal contains about 2.5% V2O5 as an impurity. The bond lengths within the tetrahedral anions suggest that substitution or disorder of PO4 3–, SiO4 4– and possibly VO4 3– occurs among the anion sites. The structure has some relationship to that of Ca5(PO4)3OH, the predominant inorganic phase in the human body, but suggests that the Ca5(PO4)3OH type structure may not be stable without some of the OH positions being filled. Ca5(PO4)2SiO4 is more closely related to K3Na(SO4)2 (glaserite) if it is considered that there are systematic cation vacancies in Ca5(PO4)2SiO4.This type of structure is consistent with the view that cation vacancies in the glaserite-type structure account for solid solutions between Ca2SiO4 and Ca3(PO4)2 and between Ca3(PO4)2 and CaNaPO4.
Die Kristallstruktur vonCa 5(PO 4)2 SiO 4 (Silicocarnotit)
Zusammenfassung Die Kristallstruktur von Ca5(PO4)2SiO4 (Silicocarnotit) wurde aus 3358 Röntgendiffraktometer-Daten bestimmt und in Raumgruppe Pnma aufR w =0,038,R=0,045 verfeinert. Die Gitterkonstanten (bei 24° C) sind:a=6,737 (1) Å,b=15,508 (2) Å undc=10,132 (1) Å,Z=4; Dobs.=3,06 g · cm–3, Dexp.=3,03 g · cm–3. Der Kristall enthält etwa 2,5% V2O5 als Verunreinigung. Die Bindungslängen in den tetraedrischen Anionen legen nahe, daß unter den Anionenplätzen gegenseitige Vertretung oder Unordnung von PO4 3–, SiO4 4– und möglicherweise VO4 3– auftritt. Die Struktur zeigt einige Verwandtschaft zu der von Ca5(PO4)3OH, der wichtigsten anorganischen Substanz im menschlichen Körper, weist aber darauf hin, daß eine Struktur vom Ca5(PO4)3OH-Typ ohne Besetzung eines Teiles der OH-Position nicht stabil ist. Ca5(PO4)2SiO4 zeigt engere Beziehungen zu K3Na(SO4)2 (Glaserit), wenn man berücksichtigt, daß in Ca5(PO4)3SiO4 systematische Kationen-Leerstellen sind. Dieser Strukturtyp ist mit derAuffassung in Übereinstimmung, daß Kationenleerstellen für die festen Lösungen zwischen Ca2SiO4 und Ca3(PO4)2 und zwischen Ca3(PO4)2 und CaNaPO4 verantwortlich sind.

With 9 Figures  相似文献   

18.
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   

19.
The new, greatly expanded internally-consistent dataset of Holland and Powell includes thermodynamic data for a wide range of mineral end-members in common rock-forming minerals, in particular, including FeMg-1 substitutions in glaucophane, garnet, chloritoid and carpholite, and FeMg-1 and MgSiAl-1Al-1 substitutions in talc and chlorite. Moreover, we have the uncertainties and correlations for these data. With the data, we have calculated the full pressure-temperature phase diagram for the system Na2O–FeO–MgO–Al2O3–SiO2–H2O (NFMASH) for quartz (or coesite) and H2O in excess, in the range 300°–800°C and 5–50 kbars. By solving the set of non-linear equations formed by the equilibrium relationships for an independent set of equations between the end-members in an assemblage in NFMASH, the compositions of the minerals (and PT) can be calculated. Thus the changes in MgSiAl-1Al-1 along NMASH reactions, and FeSiAl-1Al-1 along NFASH reactions, are calculated, and the changes in FeMg-1 and MgSiAl-1Al-1 along NFMASH reactions are calculated. From this information it is straightforward to generate PT diagrams for specific rock compositions. Mineral assemblages and mineral compositional changes in the phase diagram are discussed in relation to greenschist, blueschist and eclogite facies assemblages in metapelitic rocks. It is found that the correspondence between the predictions of the phase diagrams and the observations on rocks is remarkably good. When semiquantitative extensions of the phase diagram to include Ca(MgFe)-1, NaSiCa-1Al-1, Fe3+Al-1 and KNa-1 substitutions are taken into account the agreement is essentially complete.  相似文献   

20.
X-ray structure refinements of Ni2SiO4 and Fe2SiO4 spinels have been made as a function of temperature and heating duration by intensity measurements at high temperatures and room pressure. The lattice parameters of Ni2SiO4 spinel linearly increased with temperature up to 1,000° C. However, Fe2SiO4 spinel exhibited a nonlinear thermal expansion and was converted to a polycrystalline mixture of spinel and olivine by heating of less than one-hour at 800° C. The ratios between the octahedral and tetrahedral bond lengths D oct/D tetr and between the shared and unshared edge distances (O-O)sh/(O-O)unsh in Fe2SiO4 spinel were both much larger than those in Ni2SiO4. These ratios increase with temperature. The Fe2SiO4 spinel more readily approached a activation state which facilitated the transition to the olivine structure than the Ni2SiO4 spinel. The lattice parameter of Ni2SiO4 spinel decreased with heating period at constant temperatures of 700° C and 800° C. The parameter of the quenched sample after heating for 52 h at 700° C was smaller than that of the nonheated sample. The refinements of the site occupancies at each heating duration indicated an increase in the cation deficiency in both tetrahedral and octahedral sites. Electron microprobe analysis, however, proved no significant difference in the chemical compositions between the quenched and nonheated samples. Si and Ni atoms displaced from normally occupied spinel lattice sites are assumed to settle in vacant sites defined by the cubic close packed oxygen sublattice in a manner which preserves the electric neutrality of the bulk crystal.  相似文献   

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