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1.
Iron isotope and major- and minor-element compositions of coexisting olivine, clinopyroxene, and orthopyroxene from eight spinel peridotite mantle xenoliths; olivine, magnetite, amphibole, and biotite from four andesitic volcanic rocks; and garnet and clinopyroxene from seven garnet peridotite and eclogites have been measured to evaluate if inter-mineral Fe isotope fractionation occurs in high-temperature igneous and metamorphic minerals and if isotopic fractionation is related to equilibrium Fe isotope partitioning or a result of open-system behavior. There is no measurable fractionation between silicate minerals and magnetite in andesitic volcanic rocks, nor between olivine and orthopyroxene in spinel peridotite mantle xenoliths. There are some inter-mineral differences (up to 0.2‰ in 56Fe/54Fe) in the Fe isotope composition of coexisting olivine and clinopyroxene in spinel peridotites. The Fe isotope fractionation observed between clinopyroxene and olivine appears to be a result of open-system behavior based on a positive correlation between the Δ56Feclinopyroxene-olivine fractionation and the δ56Fe value of clinopyroxene and olivine. There is also a significant difference in the isotopic compositions of garnet and clinopyroxene in garnet peridotites and eclogites, where the average Δ56Feclinopyroxene-garnet fractionation is +0.32 ± 0.07‰ for six of the seven samples. The one sample that has a lower Δ56Feclinopyroxene-garnet fractionation of 0.08‰ has a low Ca content in garnet, which may reflect some crystal chemical control on Fe isotope fractionation. The Fe isotope variability in mantle-derived minerals is interpreted to reflect subduction of isotopically variable oceanic crust, followed by transport through metasomatic fluids. Isotopic variability in the mantle might also occur during crystal fractionation of basaltic magmas within the mantle if garnet is a liquidus phase. The isotopic variations in the mantle are apparently homogenized during melting processes, producing homogenous Fe isotope compositions during crust formation.  相似文献   

2.
Multiple regression analysis on an extended dataset has been performed to refine the relationship between temperature, pressure, composition and the Fe–Mg distribution between garnet and clinopyroxene. In addition to a significant dependence between the distribution coefficient KD and X GrtCa and X GrtMg#, as shown by the experimental data, the effect of X GrtMn has also been incorporated using data from natural Mn‐rich garnet–clinopyroxene pairs. Multiple regression of data (n=360) covering a large span in pressure, temperature and composition from 27 experimental datasets, combined with 49 natural high‐Mn granulites from Ruby Range, Montana, USA, and Karnataka, India, yields the P–T –compositional relationship (r2=0.98): where KD=(Fe2+/Mg)Grt/(Fe2+/Mg)Cpx, X GrtCa=Ca/(Ca+Mn+Fe2++Mg) in garnet, X GrtMn= Mn/(Ca+Mn+Fe2++Mg) in garnet, and X GrtMg#=Mg/(Mg+Fe2+) in garnet. The Fe2+–Mg equilibrium between garnet and clinopyroxene does not seem to be affected by variations in the sodic content of the co‐existing clinopyroxene in the range X CpxNa=0–0.51. Comparisons between the new and former calibrations of the garnet–clinopyroxene Fe2+–Mg geothermometer clearly demonstrate how the various parameters in each case affect the calculated temperatures. Application of the new expression gives reasonable results for natural garnet–clinopyroxene pairs from various rock types and settings, and should be preferred to previous formulations. Using the new calibration to the self‐consistent dataset of Pattison & Newton (Contributions to Mineralogy and Petrology, 1989, 101, 87–103) suggests a systematic deviation with regard to both temperature and composition between their dataset and the datasets used in the present calibration.  相似文献   

3.
Abstract Sapphirine-bearing rocks occur in three conformable, metre-size lenses in intrusive quartzo-feldspathic orthogneisses in the Curaçà valley of the Archaean Caraiba complex of Brazil. In the lenses there are six different sapphirine-bearing rock types, which have the following phases (each containing phlogopite in addition): A: Sapphirine, orthopyroxene; B: Sapphirine, cordierite, orthopyroxene, spinel; C: Sapphirine, cordierite; D: Sapphirine, cordierite, orthopyroxene, quartz; E: Sapphirine, cordierite, orthopyroxene, sillimanite, quartz; F: Sapphirine, cordierite, K-feldspar, quartz. Neither sapphirine and quartz nor orthopyroxene and sillimanite have been found in contact, however. During mylonitization, introduction of silica into the three quartz-free rocks (which represent relict protolith material) gave rise to the three cordierite and quartz-bearing rocks. Stable parageneses in the more magnesian rocks were sapphirine–orthopyroxene and sapphirine–cordierite. In more iron-rich rocks, sapphirine–cordierite, sapphirine-cordierite–sillimanite, cordierite–sillimanite, sapphirine–cordierite–spinel–magnetite and quartz–cordierite–orthopyroxene were stable. The iron oxide content in sapphirine of the six rocks increases from an average of 2.0 to 10.5 wt % (total Fe as FeO) in the order: C,F–A,D–B,E. With increase in Fe there is an increase in recalculated Fe2O3 in sapphirine. The four rock types associated with the sapphirine-bearing lenses are: I: Orthopyroxene, cordierite, biotite, quartz, feldspar tonalitic to grandioritic gneiss; II: Biotite, quartz, feldspar gneiss; III: Orthopyroxene, clinopyroxene, hornblende, plagioclase meta-norite; IV: Biotite, orthopyroxene, quartz, feldspar, garnet, cordierite, sillimanite granulite gneiss. The stable parageneses in type IV are orthopyroxene–cordierite–quartz, garnet–sillimanite–quartz and garnet–cordierite–sillimanite. Geothermobarometry suggests that the associated host rocks equilibrated at 720–750°C and 5.5–6.5 kbar. Petrogenetic grids for the FMASH and FMAFSH (FeO–MgO–Al2O3–Fe2O3–SiO2–H2O) model systems indicate that sapphirine-bearing assemblages without garnet were stabilized by a high Fe3+ content and a high XMg= (Mg/ (Mg+Fe2+)) under these P–T conditions.  相似文献   

4.
The equilibrium intracrystalline distribution coefficient, k D *, of Fe* (i.e. Fe2+ + Mn) and Mg between the M1 and M2 sites of three natural nearly binary Fe2+-Mg orthopyroxene crystals (Fs14, Fs15 and Fs49) were determined by annealing experiments at several temperatures between 550 and 1000 °C and single crystal X-ray structure refinements. In addition, the X-ray data of an orthopyroxene crystal (Fs23), which were collected earlier by Molin et al. (1991) between 700 and 1000 °C, were re-refined. The data were processed through two different refinement programs (SHELXL-93 and RFINE90) using both unit and individual weights and also both ionic and atomic scattering factors. The calculated site occupancies were found to agree within their estimated standard errors. However, the use of ionic scattering factors led to significantly better goodness of fit and agreement index, and smaller standard deviations of the site occupancies than those obtained from the use of atomic scattering factors. Furthermore, the weighted refinements yielded significantly smaller standard deviations of the site occupancies than the unweighted refinements even when the same set of reflections was used in the two procedures. The site occupancy data from this study were combined with selected published data to develop expressions of k D * as a function of temperature and composition. Calculation of the excess configurational entropy, ΔS XS, suggests that orthopyroxene should be treated as a two parameter symmetric solution instead of as a “simple mixture”. The calculated ΔS XS values and the excess Gibbs free energy of mixing suggested by available cation exchange data lead to a slightly negative enthalpy of mixing in the orthopyroxene solid solution. Received: 25 August 1998 / Accepted: 10 March 1999  相似文献   

5.
A pyralspite garnet from an anomalously magnetic concentrate of a pegmatitic cassiterite ore has been investigated using 57Fe nuclear gamma-ray resonance spectroscopy. The quadrupole splitting and isomer shift values of 3.6 mm/s and 1.4 mm/s, respectively, are among the largest observed for Fe2+ ions and indicate a very low covalency of the dodecahedral Fe2+ — O2-bonds. These data support the more recent and lower value (10.2–10.1 kcal/ mole) of White and Moore (1972) for the CFSE of the dodecahedral Fe2+ ion and suggest that the CFSE should be a useful approximation to the site preference energy of Fe2+ for this site.  相似文献   

6.
We have determined mineral-melt partition coefficients (D values) for 20 trace elements in garnet-pyroxenite run products, generated in 3 to 7 GPa, 1,425–1,750°C experiments on a high-Fe mantle melt (97SB68) from the Paraná-Etendeka continental-flood-basalt (CFB) province. D values for both garnet (∼Py63Al25Gr12) and clinopyroxene (∼Ca0.2Mg0.6Fe0.2Si2O6) show a large variation with temperature but are less dependent on pressure. At 3 GPa, D cpx/liq values for pyroxenes in garnet-pyroxenite run products are generally lower than those reported from Ca-rich pyroxenes generated in melting experiments on eclogites and basalts (∼Ca0.3–0.5Mg0.3–0.6Fe0.07–0.2Si2O6) but higher than those for Ca-poor pyroxenes from peridotites (∼Ca0.2Mg0.7Fe0.1Si2O6). D grt/liq values for light and heavy rare-earth elements are ≤0.07 and >0.8, respectively, and are similar to those for peridotitic garnets that have comparable grossular but higher pyrope contents (Py70–88All7–20Gr8–14). 97SB68 D LREEgrt/liq values are higher and D HREEgrt/liq values lower than those for eclogitic garnets which generally have higher grossular contents but lower pyrope contents (Py20–70Al10–50Gr10–55). D values agree with those predicted by lattice strain modelling and suggest that equilibrium was closely approached for all of our experimental runs. Correlations of D values with lattice-strain parameters and major-element contents suggest that the wollastonite component and pyrope:grossular ratio exert major controls on 97SB68 clinopyroxene and garnet partitioning, respectively. These are controlled by the prevailing pressure and temperature conditions for a given bulk-composition. The composition of co-existing melt was found to have a relatively minor effect on 97SB68 D values. The variations in D values displayed by different mantle lithologies are subtle and our study confirms previous investigations which have suggested that the modal proportions of garnet and clinopyroxene are by far the most influential factor in determining incompatible trace-element concentrations in mantle melts. The trace-element partition coefficients we have determined may be used to place high-pressure constraints on garnet-pyroxenite melting models.  相似文献   

7.
Applying Fe2+–Mg exchange geothermometers to natural samples may lead to incorrect temperature estimates if significant Fe3+ is present. In order to quantify this effect, high-pressure experiments were carried out in a belt apparatus in a natural system close to CFMAS at 5 GPa and 1,100–1,400 °C. The oxygen fugacity in the experiments was at or below the Re–ReO2 buffer. This is at significantly more oxidized conditions than in previous experiments, and, as consequence, higher Fe3+/Fe2+ ratios were generated. The Fe3+ content of garnet in the experiments was quantified by electron microprobe using the flank method. Making the usual assumption that Fetotal = Fe2+, the two-pyroxene thermometer of Brey and Köhler (J Pet 31:1353–1378, 1990) reproduced the experimental temperature to ±35 °C and the garnet–clinopyroxene Fe2+–Mg exchange thermometer of Krogh (Contrib Miner Pet 99:44–48, 1988) overestimated the temperatures on average by only 25 °C. On the other hand, application of the garnet–olivine (O’Neill and Wood in Contrib Miner Pet 70:59–70, 1979) and garnet–orthopyroxene (Harley in Contrib Miner Pet 86:359–373, 1984) exchange geothermometers yielded an underestimation in calculated temperatures of >200 °C. However, making explicit accounting for Fe3+ in garnet (i.e. using only measured Fe2+) leads to a vast improvement in the agreement between calculated and experimental temperatures, generally to within ±70 °C for the garnet–orthopyroxene geothermometer as well as noticeable improvement of calculated temperatures for the garnet–olivine geothermometer. Our results demonstrate that the two-pyroxene and garnet–clinopyroxene thermometers are rather insensitive to the presence of Fe3+ whilst direct accounting of Fe3+ in garnet is essential when applying the garnet–olivine and garnet–orthopyroxene thermometers.  相似文献   

8.
In this study we use two dimensional chemical patterns and numerical modeling to estimate the relative rates of chemical transport along interphase boundaries (ib) and through grain (s) interiors during retrograde Fe–Mg exchange between garnet and biotite at a garnet–biotite–quartz triple junction. We demonstrate that systematic variations in garnet–rim compositions, which are frequently observed along garnet–quartz interfaces, and deviations from concentric retrograde zoning patterns start to develop when chemical transport along the interphase boundaries becomes slow during cooling. The capacities for chemical transport along an interphase boundary depend on the product D ib K ib/s a, where D ib is the diffusion coefficient of the exchangeable components within the interphase boundary medium, K ib/s is the equilibrium partitioning coefficient between the cation exchange partners and the interphase boundary medium and a is the interphase boundary width. The model is applied to analyze the retrograde zoning patterns in garnets from the Mozambique belt (SE-Kenya), which cooled from 820°C at a rate of ca. 2°C/my. It is found that non-equilibrated compositions in garnet along garnet/quartz interphase boundaries started to develop below 700°C due to insufficient rates of chemical transport along these boundaries. The transport capacities of garnet/quartz interphase boundaries was estimated to have been between about 1E-23 cm3/s (575°C) and 1E-20 cm3/s (700°C) from modeling the observed X Fe pattern in garnet close to a garnet–quartz–biotite triple junction and relying on published data on the diffusivity of Fe2+ in garnet. Similar transport capacities are obtained; when the interphase boundary is assumed to be filled with a material that has the transport properties and chemical composition of a free melt in equilibrium with garnet, biotite and quartz at the respective conditions. In contrast, if the transport properties of the interphase boundary medium are related to the diffusivities and solubility of Fe2+ and FeOH+ within a free aqueous solution, chemical transport along the interphase boundaries would be much more efficient, and exchange equilibrium would have been maintained during the entire cooling history of the rocks. The observation of systematic deviations from local equilibrium along the garnet–quartz interphase boundaries leads us to exclude the presence of an aqueous fluid along the interphase boundary at any time during cooling.  相似文献   

9.
The temperature effect on the exchange reaction Cr2O3(ol)=Cr2O3(px) was studied for coexisting olivine and both clino and ortho pyroxenes. The distribution of Cr between olivine and clinopyroxene in 31 coarse garnet lherzolites and 10 porphyroclastic garnet lherzolites from kinberlites, and in 17 coarse spinel lherzolites from basalts, obeys a van't Hoff relation (c.f. Stosch 1981) with the Wells two-pyroxene temperature: T(Kelvin)=8,787 (In D Cr+ 2.87) where D Cr(opx/ol)=wt.% Cr(clinopyroxene)/Cr(olivine). An analogous exchange for olivine and orthopyroxene with 0.7–1.6 wt.% Al2O3 in 41 garnet lherzolites from kimberlites shows considerable scatter about the following relation: T(Kelvin)=5,540/(ln D cr+1.86) where D cr(opx/ol)= wt.% Cr(orthopyroxene)/Cr(olivine). Spinel lherzolites and a garnet lherzolite from the Malaita alnöite do not obey the second relation. For orthopyroxene with 2.5–5.1 wt.% Al2O3, D cr(opx/ol) is 1.7 to 3 times higher, and for 0.1 wt.% Al2O3 is 2 times lower than for the garnet lherzolites. Experimental calibration is needed, especially to check the possible effect of Al on D cr(opx/ol).  相似文献   

10.
Garnet-biotite gneisses, some of which contain sillimanite or hornblende, are widespread within the Otter Lake terrain, a portion of the Grenville Province of the Canadian Shield. The metamorphic grade is upper amphibolite to, locally, lower granulite facies. The atomic ratio Fe2+/(Fe2++ Fe3+) in biotite ranges from 0.79 to 0.89 (ferrous iron determinations in 10 highly pure separates), with a mean of 0.86. Mg and Fe2+ atoms occupy 67–78% of the octahedral sites, the remainder are occupied by Fe3+, Ti, and Al, and some are vacant. Mg/(Mg + Fe2+), denoted X, in the analysed samples ranges from 0.32 to 0.65. Garnet contains 1–24% grossular, 1–12% spessartine and X ranges from 0.07 to 0.34. Compositional variation in biotite and garnet is examined in relation to three mineral equilibria: (I) biotite + sillimanite + quartz = garnet + K-feldspar + H2O; (II) pyrope + annite = almandine + phlogopite; (III) anorthite = grossular + sillimanite + quartz. Measurements of X (biotite) and X (garnet) are used to construct an illustrative model for equilibrium (I) which relates the observed variation in X to a temperature range of 70°C or a range in H2O activity of 0.6; the latter interpretation is preferred. In sillimanite-free gneisses, the distribution of Mg and Fe2+ between garnet (low in Ca and Mn) and biotite is adequately described by a distribution coefficient (KD) of 4.1 (equilibrium II). The observed increase in the distribution coefficient with increasing Ca in garnet is ln KD= 1.3 + 2.5 × 10?2 [Ca] where [Ca] = 100 Ca/(Mg + Fe2++ Mn + Ca). The distribution coefficient is apparently unaffected by the presence of up to 12% spessartine in garnet. In several specimens of garnet-sillimanite-plagioclase gneiss, the Ca contents of garnet and of plagioclase increase in unison, as required by equilibrium (III). The mean pressure calculated from these data (n= 17) is 5.9 kbar, and the 95% confidence limits are ±0.5 kbar.  相似文献   

11.
Ferric iron contents of coexisting ortho- and clinopyroxene from spinel lherzolite xenoliths were measured with Mössbauer spectroscopy and found to be significant. In orthopyroxene, the range in Fe3+/Fe is from 0.04 to 0.14; in clinopyroxene, the range is from 0.12 to 0.24. Reactions involving coexisting olivine, orthopyroxene, and clinopyroxene, where either the esseneite (CaFe3+ AlSiO6) or the acmite (NaFe3+Si2O6) component in the clinopyroxene is considered, are used to calculate oxygen fugacities. These oxygen fugacities agree well with those calculated with the olivine-orthopyroxene-spinel oxybarometer. Because these reactions do not involve garnet, spinel, or plagioclase, they may be applied to lherzolites to give internally-consistent oxygen fugacities across the pressure-dependent facies boundaries between plagioclase, spinel, and garnet lherzolite. Another application of this method is to predict the Fe3+/Fe in clinopyroxene coexisting with olivine and orthopyroxene given pressure, temperature, , and the compositions of the coexisting phases in either experimental or natural assemblages. At values of equal to those of the synthetic fayalite-magnetite-quartz buffer, for example, 15–35% of the iron in the clinopyroxenes from these xenoliths would be ferric. The simplifying assumption that all Fe is divalent in silicate phases at geologically — reasonable oxygen fugacities must be re-evaluated.  相似文献   

12.
A mid‐ocean ridge basalt (MORB)‐type eclogite from the Moldanubian domain in the Bohemian Massif retains evidence of its prograde path in the form of inclusions of hornblende, plagioclase, clinopyroxene, titanite, ilmenite and rutile preserved in zoned garnet. Prograde zoning involves a flat grossular core followed by a grossular spike and decrease at the rim, whereas Fe/(Fe + Mg) is also flat in the core and then decreases at the rim. In a pseudosection for H2O‐saturated conditions, garnet with such a zoning grows along an isothermal burial path at c. 750 °C from 10 kbar in the assemblage plagioclase‐hornblende‐diopsidic clinopyroxene‐quartz, then in hornblende‐diopsidic clinopyroxene‐quartz, and ends its growth at 17–18 kbar. From this point, there is no pseudosection‐based information on further increase in pressure or temperature. Then, with garnet‐clinopyroxene thermometry, the focus is on the dependence on, and the uncertainties stemming from the unknown Fe3+ content in clinopyroxene. Assuming no Fe3+ in the clinopyroxene gives a serious and unwarranted upward bias to calculated temperatures. A Fe3+‐contributed uncertainty of ±40 °C combined with a calibration and other uncertainties gives a peak temperature of 760 ± 90 °C at 18 kbar, consistent with no further heating following burial to eclogite facies conditions. Further pseudosection modelling suggests that decompression to c. 12 kbar occurred essentially isothermally from the metamorphic peak under H2O‐undersaturated conditions (c. 1.3 mol.% H2O) that allowed the preservation of the majority of garnet with symplectitic as well as relict clinopyroxene. The modelling also shows that a MORB‐type eclogite decompressed to c. 8 kbar ends as an amphibolite if it is H2O saturated, but if it is H2O‐undersaturated it contains assemblages with orthopyroxene. Increasing H2O undersaturation causes an earlier transition to SiO2 undersaturation on decompression, leading to the appearance of spinel‐bearing assemblages. Granulite facies‐looking overprints of eclogites may develop at amphibolite facies conditions.  相似文献   

13.
Existing data on the temperature and composition dependence of the Fe2+-Mg2+ distribution between Fe-Mg olivine and orthopyroxene, the intra-crystalline distribution of Fe2+ and Mg2+ between M1 and M2 sites in orthopyroxene, and macroscopic activity-composition relations in olivine and orthopyroxene are shown to be inconsistent with generally accepted thermodynamic formulations which assume that the non-configurational Gibbs energy of orthopyroxene is independent of the degree of long-range ordering of Fe2+ and Mg+ between M1 and M2 sites. These data are interpreted in terms of the constraints they provide on the size of Bragg-Williams type energy, entropy, and volume terms for olivine and orthopyroxene. The apparent equilibrium constant for Fe-Mg exchange between olivine and orthopyroxene is shown to be a potentially useful ‘geothermometer’ for olivine-orthopyroxene assemblages with olivines with mole fraction of Fe2SiO4 component less than 0.2 or greater than 0.6. A provisional calibration of this ‘geothermometer’ is presented.  相似文献   

14.
Barium-, Cl- and Ti-rich biotite occurs together with garnet, plagioclase and amphibole within narrow shear zones in 1800 Ma old noritic granulites in the Flakstadøy Basic Complex, Lofoten, north Norway. The granulite facies assemblage, plagioclase, clinopyroxene, orthopyroxene, biotite and ilmenite, was replaced by an amphibolite facies mineral assemblage including Ba-, Cl- and Ti-rich biotite during ductile deformation. Biotite shows complex compositional variations with respect to the contents of Ba, K, Cl, Ti, Al, Fe, Mg and Si. There are correlations between Si, AlIV, K, Ba and Cl and between AlVI and Ti. Titanium and Cl are uncorrelated. The Fe and Mg are correlated to both Cl and Ti. Multivariate analysis shows that most of the compositional variation of biotite can be described by two exchange reactions. This indicates that most of the variation in biotite composition was controlled by two chemical variables of the system. The content of the first exchange component (Ti1.0 Fe0.6 Al -1.1 VI Mg-0.8) in biotite can be related to the original distribution of Ti-bearing minerals in the igneous protolith. The content of the second exchange component (Al 0.4 IV Fe0.8 Ba0.5 Cl1.0 Si-0.4 Mg-1.0 K-0.5 OH-1.0) is related to compositional variations of an externally derived Ba- and Cl-bearing fluid in equilibrium with biotite.The initially low Cl-content of the externally derived fluid was increasing during bioite forming reactions, because OH was preferentially incorporated, relative to Cl, into biotite. Continued hydration/chloridisation reactions resulted in a gradual consumption of the free fluid phase, resulting in local fluid-absent conditions. The composition of biotite reflects the composition of the last fluid in equilibrium with the mineral, i.e. the composition of the fluid immediately before the grain boundaries were fluid-undersaturated. Thus, the variations in biotite composition reflect how the fluid was gradually consumed throughout the shear zone rock. The correlations between Fe, Mg, Ba, K and Cl can be attributed to differences between the structure of the crystal lattices and the sizes of the cation sites of OH-phlogopite and Cl-annite. The dependency of the Fe/Mg ratios of biotite on the Cl-and Ti-content has a strong effect on the Fe–Mg partitioning between biotite and garnet. The relationship between lnKD, X Ti Bt and X Cl Bt can be expressed by the regression equation: lnK D =-1.82+2.60X Ti Bt +5.67X Cl Bt  相似文献   

15.
Clinopyroxene and orthopyroxene megacrysts containing garnet lamellae up to 1.2 mm thick as an exsolved phase are found rarely in kimberlites from Frank Smith and Bellsbank. Chemically the clinopyroxenes are characteristically subcalcic, being within the range of 100 Ca/Ca + Mg + Fe = 27 to 36, and the orthopyroxenes are characterized by high Al2O3 and Cr2O3. Immediately after crystallization during very slow cooling, clinopyroxene and orthopyroxene exsolve wide-spaced orthopyroxene and clinopyroxene phases parallel to (100) of the host phases, respectively, then both host and exsolved phases exsolve garnet lamellae. Topotactic relations between pyroxenes and garnet are determined by X-ray for the first time. Partitioning of major and minor elements among the coexisting clinopyroxene, orthopyroxene and garnet in pyroxene megacrysts is the same as that of the granular-type garnet peridotite xenoliths in Lesotho and South African kimberlies. Mineralogy and chemistry indicate that subcalcic clinopyroxene and orthopyroxene megacrysts contain respectively about 10 and 3 mole % of the garnet molecule in solid solution.  相似文献   

16.
 The crystal chemical response of basalt clinopyroxene to increasing pressure was investigated by means of crystal-structure simulation (a procedure that enables modeling of the structural parameters of a clinopyroxene of known chemistry without requiring direct X-ray diffraction analysis) using available experimental chemical data. Pressure proved the main physical variable governing clinopyroxene behavior in a magmatic environment. The general internal consistency of the simulation data permitted construction of an empirical geobarometer based on the relationship of cell volume (Vc) vs M1-site volume (VM1). The straightforward geobarometric formulation in the absence of direct X-ray analysis is: P(kbar)=698.443+4.985⋅AlT−26.826⋅Fe2+ M1−3.764⋅Fe3+ +53.989⋅AlM1+3.948⋅Ti+14.651⋅Cr −700.431⋅Ca−666.629⋅Na−682.848⋅MgM2−691.138⋅Fe2+ M2−688.384⋅Mn−6.267⋅(MgM2)2−4.144⋅(Fe2+ M2 where: (Fe2+ M1⋅MgM2)/(Fe2+ M2⋅MgM1)=e**(0.238⋅R3++0.289⋅CNM−2.315), CNM=Ca+Na+Mn, and R3+=AlM1+Fe3++Ti+Cr, with cations in atoms per formula unit. The geobarometer reproduces experimental pressures within ±2 kbar (=1σ; max. dev. ≤5 kbar; N=29) in the range 0–24 kbar and is applicable to near-liquidus C2/c clinopyroxenes crystallized from basaltic melts in the absence of garnet (excepting high-Al2O3 basalts). It is therefore suitable for many natural clinopyroxenes occurring as mega- or phenocrysts or forming well-preserved cumulate pyroxenites. If the above restrictions are not wholly satisfied, the Vc vs VM1 plot can also be used qualitatively to deduce the relative pressure conditions of clinopyroxenes forming from similar batches of magma. The structural simulation of experimental data also provided insight into the influence of minor chemical changes of the parental magma on the crystal chemistry of clinopyroxene at high pressure. Within the considered compositional space at given P-T, a CaO and a SiO2 in the melt have opposite effects on M2- and T-site cation populations. As a result, under similar physical conditions, clinopyroxenes from higher-CaO or more undersaturated basalts have higher VM2, VT and Vc and lower VM1. For basalts with normal contents of Al2O3 (<18 wt %), variations of major elements in the melt do not reduce the accuracy of the geobarometer. Received: 3 April 1994 / Accepted: 23 December 1995  相似文献   

17.
High-grade metamorphic rocks were used to explore oxygen isotope fractionations between pyroxene and garnet, and to investigate the effects on fractionation factors of the cation substitutions Fe3+Al?1 and Ca(Fe,Mg)?1. Recrystallized, granulite facies (725 °C) wollastonite ores from the northern Adirondack highlands contain essentially only the minerals clinopyroxene (a Di–Hd solid solution)+garnet (a Grs–Adr solid solution)±wollastonite, and exhibit a systematic dependence of measured fractionations on the Fe3+ content of calcic garnet: Δ(Cpx–CaGrt)=(0.14±0.12)+(0.78±0.20)XAdr and Δ(Wo–CaGrt)=(0.15±0.22)+(0.57±0.33)XAdr. In eclogites formed at T ≤650 °C, measured compositions of Ca-poor garnet and omphacite combined with experimental data indicate that Ca-poor, Fe-rich garnet is enriched in 18O compared to both diopside and grossular: extrapolating to 1000 K, Δ(Alm–Di)≈c. 0.2 and Δ(Alm–Grs)≈c. 0.5. Orthopyroxene and clinopyroxene from Gore Mountain, New York, show a constant fractionation that is independent of rock type, as expected if they have the same closure temperature. These data imply Δ(Opx-Cpx)≈c. 0.7 at 1000 K. Measured fractionations among Ca-poor garnet, orthopyroxene, clinopyroxene and hornblende in the Gore Mountain rocks further indicate an 18O enrichment in Ca-poor garnet over Grs (≈c. 0.5 at 1000 K). The new measurements are indistinguishable from expected equilibrium values based on experiments for the minerals enstatite, diopside, grossular, wollastonite and feldspar, but consistently indicate a significant isotope effect for the simple octahedral cation substitutions Fe3+Al?1 (Grs vs. Adr) and Ca(Fe,Mg)?1 (Ca-poor garnet vs. Grs; Opx vs. Cpx). Neither cation substitution has been directly investigated for its effect on 18O/16O fractionation with experiments in silicates. Chemical characterization of minerals is required prior to petrological interpretation of oxygen isotope trends.  相似文献   

18.
Published experimental data including garnet and clinopyroxene as run products were used to develop a new formulation of the garnet–clinopyroxene geothermometer based on 333 garnet–clinopyroxene pairs. Only experiments with graphite capsules were selected because of difficulty in estimating the Fe3+ content of clinopyroxene. For the calibration, a published subregular‐solution model was adopted to express the non‐ideality of garnet. The magnitude of the Fe–Mg excess interaction parameter for clinopyroxene (WFeMgCpx), and differences in enthalpy and entropy of the Fe–Mg exchange reaction were regressed from the accumulated experimental data set. As a result, a markedly negative value was obtained for the Fe–Mg excess interaction parameter of clinopyroxene (WFeMgCpx = ? 3843 J mol?1). The pressure correction is simply treated as linear, and the difference in volume of the Fe–Mg exchange reaction was calculated from a published thermodynamic data set and fixed to be ?120.72 (J kbar?1 mol?1). The regressed and obtained thermometer formulation is as follows: where T = temperature, P = pressure (kbar), A = 0.5 Xgrs (Xprp ? Xalm ? Xsps), B = 0.5 Xgrs (Xprp ? Xalm + Xsps), C = 0.5 (Xgrs + Xsps) (Xprp ? Xalm), Xprp = Mg/(Fe2+ + Mn + Mg + Ca)Grt, Xalm = Fe/(Fe2+ + Mn + Mg + Ca)Grt, Xsps = Mn/(Fe2+ + Mn + Mg + Ca)Grt, Xgrs = Ca/(Fe2+ + Mn + Mg + Ca)Grt, XMgCpx = Mg/(Al + Fetotal + Mg)Cpx, XFeCpx = Fe2+/(Al + Fetotal + Mg)Cpx, KD = (Fe2+/Mg)Grt/(Fe2+/Mg)Cpx, Grt = garnet, Cpx = clinopyroxene. A test of this new formulation to the accumulated data gave results that are concordant with the experimental temperatures over the whole range of the experimental temperatures (800–1820 °C), with a standard deviation (1 sigma) of 74 °C. Previous formulations of the thermometer are inconsistent with the accumulated data set; they underestimate temperatures by about 100 °C at >1300 °C and overestimate by 100–200 °C at <1300 °C. In addition, they tend to overestimate temperatures for high‐Ca garnet (Xgrs ≈ 0.30–0.50). This new formulation has been tested against previous formulations of the thermometer by application to natural eclogites. This gave temperatures some 20–100 °C lower than previous formulations.  相似文献   

19.
To understand partitioning of hydrogen between hydrous basaltic and andesitic liquids and coexisting clinopyroxene and garnet, experiments using a mid-ocean ridge basalt (MORB) + 6 wt.% H2O were conducted at 3 GPa and 1,150–1,325°C. These included both isothermal and controlled cooling rate crystallization experiments, as crystals from the former were too small for ion microprobe (SIMS) analyses. Three runs at lower bulk water content are also reported. H2O was measured in minerals by SIMS and in glasses by SIMS, Fourier Transform infrared spectroscopy (FTIR), and from oxide totals of electron microprobe (EMP) analyses. At 3 GPa, the liquidus for MORB with 6 wt.% H2O is between 1,300 and 1,325°C. In the temperature interval investigated, the melt proportion varies from 100 to 45% and the modes of garnet and clinopyroxene are nearly equal. Liquid composition varies from basaltic to andesitic. The crystallization experiments starting from above the liquidus failed to nucleate garnets, but those starting from below the liquidus crystallized both garnet and clinopyroxene. SIMS analyses of glasses with >7 wt.% H2O yield spuriously low concentrations, perhaps owing to hydrogen degassing in the ultra-high vacuum of the ion microprobe sample chamber. FTIR and EMP analyses show that the glasses have 3.4 to 11.9 wt.% water, whilst SIMS analyses indicate that clinopyroxenes have 1,340–2,330 ppm and garnets have 98–209 ppm H2O. D H cpx−gt is 11 ± 3, D H cpx−melt is 0.023 ± 0.005 and D H gt−melt is 0.0018 ± 0.0006. Most garnet/melt pairs have low values of D H gt−melt, but D H gt−melt increases with TiO2 in the garnet. As also found by previous studies, values of D H cpx−melt increase with Al2O3 of the crystal. For garnet pyroxenite, estimated values of D H pyroxenite−melt decrease from 0.015 at 2.5 GPa to 0.0089 at 5 GPa. Hydration will increase the depth interval between pyroxenite and peridotite solidi for mantle upwelling beneath ridges or oceanic islands. This is partly because the greater pyroxene/olivine ratio in pyroxenite will tend to enhance the H2O concentration of pyroxenite, assuming that neighboring pyroxenite and peridotite bodies have similar H2O in their pyroxenes. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.  相似文献   

20.
Complex multivariant reactions involving Fe-Ti oxide minerals, plagioclase and olivine have produced coronas of biotite, hornblende and garnet between ilmenite and plagioclase in Adirondack olivine metagabbros. Both the biotite (6–10% TiO2) and the hornblende (3–6% TiO2) are exceptionally Titanium-rich. The garnet is nearly identical in composition to the garnet in coronas around olivine in the same rocks. The coronas form in two stages:
  1. Plagioclase+Fe-Ti Oxides+Olivine+water =Hornblende+Spinel+Orthopyroxene±Biotite +more-sodic Plagioclase
  2. Hornblende+Orthopyroxene±Spinel+Plagioclase =Garnet+Clinopyroxene+more-sodic Plagioclase
The Orthopyroxene and part of the clinopyroxene form adjacent to olivine. Both reactions are linked by exchange of Mg2+ and Fe2+ with the reactions forming pyroxene and garnet coronas around olivine in the same rocks. The reactions occur under granulite fades metamorphic conditions, either during isobaric cooling or with increasing pressure at high temperature.  相似文献   

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