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1.
The partitioning of Ni between olivine and garnet in two multi-component compositions was studied as a function of temperature and pressure in a 6–8 type multi-anvil apparatus. Weighted least squares regression of the experimental results for both compositions give a temperature dependence for Ni partitioning between olivine (Ol) and garnet (Gt) of the form: T=–10210(±114)/[lnD Gt/Ol Ni –3.59(±67)] where DGt/Ol/Ni=Ni content of Gt/Ni content of olivine (by weight) and Tis in Kelvin. The pressure effect on Ni exchange between olivine and garnet is estimated to be 0.13 J/bar, and should therefore have a negligible effect on the geothermometer, as is demonstrated in the experiments. The experimentally derived Ni in Gt geothermometer is in agreement with an extant empirical version between 1100 to 900°C, but the two thermometers produce significantly different results outside of this temperature range.  相似文献   

2.
The partitioning of Fe and Mg between coexisting garnet and olivine has been studied at 30 kb pressure and temperatures of 900 ° to 1,400 °C. The results of both synthesis and reversal experiments demonstrate that K D (= (Fe/Mg)gt/(Fe/Mg)OI) is strongly dependent on Fe/Mg ratio and on the calcium content of the garnet. For example, at 1,000 °C/30 kb, K D varies from about 1.2 in very iron-rich compositions to 1.9 at the magnesium end of the series. Increasing the mole fraction of calcium in the garnet from 0 to 0.3 at 1,000 ° C increases K D in magnesian compositions from 1.9 to about 2.5.The observed temperature and composition dependence of K D has been formulated into an equation suitable for geothermometry by considering the solid solution properties of the olivine and garnet phases. It was found that, within experimental error, the simplest kind of nonideal solution model (Regular Solution) fits the experimental data adequately. The use of more complex models did not markedly improve the fit to the data, so the model with the least number of variables was adopted.Multiple linear regression of the experimental data (72 points) yielded, for the exchange reaction: 3Fe2SiO4+2Mg3Al2Si3O12 olivine garnet 2Fe2Al2Si3O12+3Mg2SiO4 garnet olivine H ° (30kb) of –10,750 cal and S ° of –4.26 cal deg–1 mol–1. Absolute magnitudes of interaction parameters (W ij ) derived from the regression are subject to considerable uncertainty. The partition coefficient is, however, strongly dependent on the following differences between solution parameters and these differences are fairly well constrained: W FeMg ol -W FeMg gt 800 cal W CaMg gt -W CaFe gt 2,670 cal.The geothermometer is most sensitive in the temperature and composition regions where K D is substantially greater than 1. Thus, for example, peridotitic compositions at temperatures less than about 1,300 ° C should yield calculated temperatures within 60 °C of the true value. Iron rich compositions (at any temperature) and magnesian compositions at temperatures well above 1,300 °C could not be expected to yield accurate calculated temperatures.For a fixed K D the influence of pressure is to raise the calculated temperature by between 3 and 6 °C per kbar.  相似文献   

3.
In contrast to Ferry (1980) (X Ca)-values in garnet even lower than 0.1 have a significant effect on the calculated equilibrium temperature using the experimental calibration of the Fe and Mg paritioning between garnet and biotite. Garnet compositions and Mg/Fe — distribution coefficients from samples of the Eoalpine staurolite — in zone in the southern Ötztal are related by the quadratic regression equation: InK D= -1.7500 (±0.0226) + 2.978 (±0.5317)X Ca Gt -5.906(±2.359)(X Ca Gt )2 Temperatures derived by the Ferry and Spear (1978) calibration using chemistry — correctedK D values are petrologically realistic.Analysis of our data supports non ideal mixing of grossular with almandine — pyrope solid solution. The derived excess mixing energies are quite small for the almandine — pyrope solution (W FeMg= –133 cal/mole) and about +2775 cal/mole for the difference between pyrope-grossular and almandine-grossular solutions (W MgCa —W FeCa) at metamorphic conditions of 570° C and 5,000 bar. The mixing parameters proposed by Ganguly and Saxena (1984) are not confirmed by our data as they would result in significantly lower temperatures.  相似文献   

4.
A new mineralogic geothermometer based on the partitioning of Fe and Mn between garnet and ilmenite has been calibrated by reversal experiments in the P-T range 600–900° C, 2 and 5 kbars and for fO2=QFM. The results constitute a sensitive geothermometer applicable over a broad range of composition and conditions. Garnetilmenite thermometry has advantages relative to existing geothermometers because of its accurate calibration, marked temperature sensitivity and the chemical and structural simplicity of the crystalline solutions involved. Application to natural assemblages reveals that the garnet-ilmenite geothermometer yields temperatures that agree well with other estimates. The reactivity of, and relatively rapid Fe-Mn diffusion in ilmenite may lead to retrograde resetting of high temperature partition values, but these factors may be useful for estimating rock cooling rates. Analysis of the experimental data indicates minor positive deviations from ideality for Fe-Mn garnets and ilmenites. Absolute magnitudes of interaction parameters (W AB) derived from a regression analysis are subject to considerable uncertainty. The partition coefficient is, however, strongly dependent on the difference between solution parameters. These differences are well constrained with a magnitude of W FeMn ilm –W FeMn gar 300 cal mol–1. The accuracy and applicability of garnet-ilmenite thermometry will improve with the availability of better thermodynamic data for garnet crystalline solutions.Abbreviations and symbols used in text R universal gas constant (cal/mol/°K) - T absolute temperature (°K or °C) - P pressure (kbars) - V 0 volume change of reaction (1) - H 1, T 0 standard state enthalpy change of reaction (1) at 1 bar and the T of interest, in cal/mole - S T 0 entropy change of reaction (1) at T of interest, in cal/mole/°K - G P,T 0 standard free energy change of reaction (1) at the T and P of interest, in cal/mole - distribution coefficient for Fe-Mn partitioning between garnet and ilmenite - K apparent equilibrium coefficient for reaction (1) - i j activity of component i in phase j - W A-B binary A-B interaction (Margules) parameter - gar garnet - ilm ilmenite - biot biotite - ol olivine - opx orthopyroxene  相似文献   

5.
Compositional zonation in garnets in peridotite xenoliths   总被引：1，自引：0，他引：1  
Garnets in 42 peridotite xenoliths, most from southern Africa, have been analyzed by electron probe to seek correlations between compositional zonation and rock history. Xenoliths have been placed into the following 6 groups, based primarily upon zonation in garnet: I (12 rocks)-zonation dominated by enrichment of Ti and other incompatible elements in garnet rims; II (10 rocks)-garnet nearly homogeneous; III (8 rocks)-rims depleted in Cr, with little or no related zonation of Ti; IV (3 rocks)-slight Ti zonation sympathetic to that of Cr; V (3 rocks)-garnet rims depleted or enriched in Cr, and chromite included in garnet; VI (6 rocks)-garnets with other characteristics. Element partitioning between olivine, pyroxene, and garnet rims generally is consistent with the assumption of equilibrium before eruption. Although one analyzed rock contains olivine and pyroxene that may have non-equilibrated oxygen isotopes, no corresponding departures from chemical equilibrium were noted. Causes of zoning include melt infiltration and changes in temperature and pressure. Zonation was caused or heavily influenced by melt infiltration in garnets of Group I. In Groups III, IV, and V, most compositional gradients in garnets are attributed to changes in temperature, pressure, or both, and gradients of Cr are characteristic. There are no simple relationships among wt% Cr2O3 in garnet, calculated temperature, and the presence of compositional gradients. Rather, garnets nearly homogeneous in Cr are present in rocks with calculated equilibration temperatures that span the range 800–1500 °C. Although the most prominent Cr gradients are found in relatively Cr-rich garnets of rocks for which calculated temperatures are below 1050 °C, gradients are well-defined in a Group IV rock with T1300 °C. The variety of Cr gradients in garnets erupted from a range of temperatures indicates that the zonations record diverse histories. Petrologic histories have been investigated by simulated cooling of model rock compositions in the system CaO–MgO–Al2O3–SiO2–Cr2O3. Proportions and compositions of pyroxene and garnet were calculated as functions of P and T. The most common pattern of zonation in Groups III and IV, a decrease of less than 1 wt% Cr2O3 core-to-rim, can be simulated by cooling of less than 200 °C or pressure decreases of less than 1 GPa. The preservation of growth zonation in garnets with calculated temperatures near 1300 °C implies that these garnets grew within a geologically short time before eruption, probably in response to fast cooling after crystallization of a small intrusion nearby. Progress in interpreting garnet zonations in part will depend upon determinations of diffusion rates for Cr. Zonation formed by diffusion within garnet cannot always be distinguished from that formed by growth, but Ca–Cr correlations unlike those typical of peridotite suite garnets may document diffusion.  相似文献   

6.
Applications of the different formulations of garnet-clinopyroxene geothermometers to crustal granulites and particularly to metamorphosed manganese formations show a wide scatter of estimates. This is primarily related to the uncertainty associated with the formulation of the activity-composition relationship in garnet solid solution besides that in the clinopyroxene solid solution. The largest uncertainty appears to have resulted from the adopted Mg-Mn interaction parameter in garnet which is yet to be experimentally determined. A fresh statistical regression of eleven pairs of garnet and clinopyroxene equilibrated at identical P-T conditions from a manganese formation in India yields W Mg-Mn Gt (=WMn-Mg) value of 1600±500 cal/mols. An extension of the Ellis and Green (1979) geothermometer, known to work well in normal granulites, incorporating terms associated with the activity coefficients of the exchangeable cations, now yields consistent temperature estimation from normal granulites as well as from metamorphosed manganese formations. The geothermometer, however, will not work well for garnet having XFe0.65 and clinopyroxenes containing appreciable Na, Al and/or Fe3+.  相似文献   

7.
Activity-composition relationships for pyrope-grossular garnet   总被引：1，自引：0，他引：1  
Activity coefficients () for grossular in pyrope-grossular garnet have been determined experimentally using the divariant assemblage garnet-anorthite-sillimanite (kyanite)-quartz. Values of for garnets with 10–12 mole % grossular have been obtained at 1000 °, 1100 °, 1200 ° and 1300 ° C at pressures between 15 and 21 Kb. The data are consistent with a symmetrical regular solid model for grossular-pyrope solid solutions. The interaction parameter (W) increases linearly with decreasing temperature and is given by W = 7460-4.3 T cals (T in °K). A solvus in the pyrope-grossular solid solution is predicted with a temperature of critical mixing of 629°C±90 ° C.  相似文献   

8.
Experimental investigations between 800 ° to 1,100 ° C yielded no evidence for extensive substitution of Mn2++Si4+2Mn3+ in braunite, leading to a complete solid solution series between partridgeite (Mn2O3) and braunites with silica contents up to 40 wt. % as proposed by Muan (1959a, b). In the presence of excess manganese braunite of nearly ideal composition coexists at 800 ° C with partridgeite and at T1,000 ° C with hausmannite (Mn3O4). At 800 ° C and 1,000 ° C braunite coexists, in the presence of excess silica, with a SiO2-polymorph and at 1,100 ° C with rhodonite (MnSiO3). Quantitative analysis of the X-ray patterns of coexisting cristobalite and braunite confirms a maximum silica-excess in braunite of only about 2 wt.% over the ideal composition, Mn2+Mn 6 3+ SiO12.  相似文献   

9.
The activity of FeTiO3 in the binary ilmenitepyrophanite (FeTiO3-MnTiO3) solid solution has been determined for the temperature range 1050–1300 K by displacement of the reaction: 2 FeTiO3=2 Fe+2 TiO2+O2 in T-O2 space, using an electrochemical technique with calcia- and yttria-stabilized zirconia solid electrolytes. The activities show small positive deviations from ideality, which, although the data are unusually precise, may be perfectly described by the simple regular solution model, with an interaction parameter, W Fe-Mn ilm , of 2.2±0.3 kJ g-atom–1, which is independent of temperature. This value, together with the experimental data on the partitioning of Fe and Mn between ilmenite and garnet (Pownceby et al. 1987), gives W Fe-Mn gt =1.2±0.5 kJ g-atom–1 for the almandine-spessartine (Fe3Al2Si3O12-Mn3Al2Si3O12) solid solution.  相似文献   

10.
Experimental tests of garnet peridotite oxygen barometry   总被引：1，自引：0，他引：1  
We have performed experiments aimed at testing the calibration of oxygen barometers for the garnet peridotite [garnet (Gt)-olivine (Ol)-orthopyroxene (Opx)] phase assemblage. These involved equilibrating a thin layer of garnet sandwiched between layers of olivine and orthopyroxene at 1300°C and 23–35 kbar for 1–7 days. Oxygen fugacity was controlled (but not buffered) by using inner capsules of Fe?Pt alloy or graphitc or molybdenum sealed in welded Pt outer capsules. Post-experiment measurement of fO2 was made by determining the compositions of Pt-Fe alloy sensors at the interface between garnet and olivine + orthopyroxene layers. The composition of alloy in equilibrium with olivine + orthopyroxene was approached from Fe-oversaturated and Fe-undersaturated conditions in the same experiment with, in general, excellent convergence. Product phase compositions were determined by electron microprobe and a piece of the garnet layer saved for 57Fe Mössbauer spectroscopy. The latter gave the Fe3+ content of the garnet at the measured P-T-fO2 conditions. Approach to equilibrium was checked by observed shifts in Fe3+ content and by the approach of garnet-olivine Fe?Mg partitioning to the expected value. The compositions of the phases were combined with mixing properties and thermodynamic data to calculate an apparent fO2 from two possible garnet oxybarometers:- (1) $\begin{gathered} 2Ca_3 Fe_2 Si_3 O_{12} + 2Mg_3 Al_2 Si_3 O_{12} + 4FeSiO_3 = 2Ca_3 Al_2 Si_3 O_{12} \hfill \\ Gt Gt Opx Gt \hfill \\ + 8FeSi_{0.5} O_2 + 6MgSiO_3 + O \hfill \\ Ol Opx \hfill \\ \end{gathered} $ and (2) $\begin{gathered} 2Fe_3 Fe_2 Si_3 O_{12} = 8FeSi_{0.5} O_2 + 2FeSi_3 O_2 \hfill \\ Gt Ol Opx \hfill \\ \end{gathered} $ Comparison of calculated fO2s with those measured by the Pt-Fe sensors demonstrated that either barometer gives the correct answer within the expected uncertainty. Data from the first (Luth et al. 1990) has an uncertainty of about 1.6 logfO2 units, however, while that from equilibrium (2) (Woodland and O'Neill 1993) has an error of +/- 0.6 log units, comparable to that of the spinel peridotite oxybarometer. We therefore conclude that equilibrium (2) may be used to calculate the fO2 recorded by garnet peridotites with an uncertainty of about +/- 0.6 log units, providing the potential to probe the oxidation environment of the deep continental lithosphere. Preliminary application based on data from Luth et al. (1990) indicates that garnet peridotite xenoliths from Southern Africa record oxygen fugacities about 3.0 log units below the FMQ (fayalite-magnetite-quartz) buffer. These are substantially more reducing conditions than those recorded by continental spinel lherzolites which typically give oxygen fugacities close to FMQ (Wood et al. 1990).  相似文献   

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

12.
Relationships between mineral/silicate melt partition coefficients and melt structure have been examined by combining Ca and Mn olivine/melt partitioning data with available melt structure information. Compositions were chosen so that melts with olivine on their liquidii range in degree of polymerization, NBO/T, from ∼0.5 to ∼2.5 under near isothermal conditions (1350-1400°C). Olivine/melt Ca-Mn exchange coefficients, Ca(olivine)/CaO(melt)/MnO(olivine)/MnO(melt) (KD Ca-Mnolivine/melt), as a function of melt NBO/T have a parabolic shape with a minimum KD Ca-Mnolivine/melt-value at NBO/T near 1. Notably, published KD Fe2+-Mgolivine/melt versus NBO/T functions are also parabolic with a maximum in KD Fe2+-Mgolivine/melt near 1 (Kushiro and Mysen, 2002).The olivine/melt partitioning data are modeled in terms of structural units (Qn-species) in the melt. The NBO/T-value corresponding to the minimum KD Ca-Mnolivine/melt is near that where the abundance ratio of Qn-species, XQ3/XQ2, has its largest value. Therefore, the activity coefficient ratio in the melt, γCa2+(melt)/γMn2+(melt), attains a minimum where the abundance ratio of XQ3/XQ2 is at maximum. It is inferred from this relationship that Ca2+ in the melts is dominantly bonded to nonbridging oxygen (Ca-NBO) in Q3-species, whereas Mn2+ is bonded to nonbridging oxygen (Mn-NBO) in less polymerized Qn-species such as Q2.  相似文献   

13.
The effect of sulfur dissolved as sulfide (S2−) in silicate melts on the activity coefficients of NiO and some other oxides of divalent cations (Ca, Cr, Mn, Fe and Co) has been determined from olivine/melt partitioning experiments at 1400 °C in six melt compositions in the system CaO-MgO-Al2O3-SiO2 (CMAS), and in derivatives of these compositions at 1370 °C, obtained from the six CMAS compositions by substituting Fe for Mg (FeCMAS). Amounts of S2− were varied from zero to sulfide saturation, reaching 4100 μg g−1 S in the most sulfur-rich silicate melt. The sulfide solubilities compare reasonably well with those predicted from the parameterization of the sulfide capacity of silicate melts at 1400 °C of O’Neill and Mavrogenes (2002), although in detail systematic deviations indicate that a more sophisticated model may improve the prediction of sulfide capacities.The results show a barely discernible effect of S2− in the silicate melt on Fe, Co and Ni partition coefficients, and also surprisingly, a tiny but resolvable effect on Ca partitioning, but no detectable effect on Cr, Mn or some other lithophile incompatible elements (Sc, Ti, V, Y, Zr and Hf). Decreasing Mg# of olivine (reflecting increasing FeO in the system) has a significant influence on the partitioning of several of the divalent cations, particularly Ca and Ni. We find a remarkably systematic correlation between and the ionic radius of M2+, where M = Ca, Cr, Mn, Fe, Co or Ni, which is attributable to a simple relationship between size mismatch and excess free energies of mixing in Mg-rich olivine solid solutions.Neither the effect of S2− nor of Mg#ol is large enough by an order of magnitude to account for the reported variations of obtained from electron microprobe analyses of olivine/glass pairs from mid-ocean ridge basalts (MORBs). Comparing these MORB glass analyses with the Ni-MgO systematics of MORB from other studies in the literature, which were obtained using a variety of analytical techniques, shows that these electron microprobe analyses are anomalous. We suggest that the reported variation of with S content in MORB is an analytical artifact.Mass balance of melt and olivine compositions with the starting compositions shows that dissolved S2− depresses the olivine liquidus of haplobasaltic silicate melts by 5.8 × 10−3 (±1.3 × 10−3) K per μg g−1 of S2−, which is negligible in most contexts. We also present data for the partitioning of some incompatible trace elements (Sc, Ti, Y, Zr and Hf) between olivine and melt. The data for Sc and Y confirm previous results showing that and decrease with increasing SiO2 content of the melt. Values of average 0.01 with most falling in the range 0.005-0.015. Zr and Hf are considerably more incompatible than Ti in olivine, with and about 10−3. The ratio / is well constrained at 0.611 ± 0.016.  相似文献   

14.
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   

15.
The partitioning of Fe2+ and Mn2+ between (Fe, Mn)TiO3 and (Fe, Mn)2SiO4 solid solutions in the system FeO-MnO-TiO2-SiO2 has been experimentally investigated at 1100 ∘C and pressures of 1 bar and 25 kbar, over a wide range of Fe/Mn ratios, using electron microprobe analysis of quenched run products. The ilmenite solid solution in this system is within analytical uncertainty a simple binary between FeTiO3 and MnTiO3, but the olivine solid solution appears to contain up to 2.5 wt% TiO2. The Fe-Mn partitioning results constrain precisely the difference in the thermodynamic mixing properties of the two solid solutions. If the mixing properties of (Fe, Mn)2SiO4 solid solutions are assumed to be ideal, as experimentally determined by Schwerdtfeger and Muan (1966), then the ilmenite is a regular, symmetric solution with W ilm Fe-Mn=1.8±0.1 kJ mol−1. The quoted uncertainty does not include the contribution from the uncertainty in the mixing properties of the olivine solution, which is estimated to be ±1.8 kJ mol−1, and which therefore dominates the uncertainty in the present results. Nevertheless, this result is in good agreement with the previous experimental study of O'Neill et al. (1989), who obtained W ilm Fe-Mn=2.2±0.3 kJ mol−1 from an independent method. The results provide another item of empirical evidence supporting the proposition that solid solutions between isostructural end-members, in which order-disorder effects are not important, generally have simple thermodynamic mixing properties, with little asymmetry, modest excess entropies, and excess enthalpies approximately proportional to the difference in the molar volumes of the end-members. Received: 11 February 1998 / Accepted: 29 June 1998  相似文献   

16.
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   

17.
The exchage equilibrium has been used to measure activity-composition relations along the olivine join FeSi0.5O2−MgSi0.5O2 at 1400 K and 1 atm pressure. Equilibrium Fe−Mg partitioning between the two phases was determined by reversing the compositions of olivine coexisting with oxide and matallic iron over the composition range Fo23 to Fo92. A detailed study of the thermodynamic properties of the oxide phase has recently been made by Srečec et al. and we have confirmed their results in the composition range of interest. Application of the oxide data to the exchange equilibrium enables the properties of olivine to be determined. Within experimental uncertainly (Fe, Mg)Si0.5O2 olivine can, at 1400 K, be treated as a symmetric solution with W Fe-Mg o1 of 3.7±0.8 kJ/mol. The data permit the presence of only very slight asymmetry in the series. The data do not support recent assertions that olivine is highly non-ideal (W≈10 kJ/mol) under these conditions.  相似文献   

18.
Data from experimentally-induced diffusion profiles at approximately 40 Kbar, 1,300–1,500° C in spessartine-almandine couples and a pyrope-almandine couple at 40 Kbar, 1,440° C, described in Part I, were used to derive tracer diffusion coefficients (D *) of Fe, Mn and Mg in garnet. The experimental data were fitted by numerical simulations that model multicomponent, compositionally-dependent difussion, including the effects of nonideal thermodynamic mixing. The simulations use the formalism of irreversible thermodynamics and an eigenvector technique of solution. We were able to fit the asymmetrical spessartine-almandine profiles using constant D * and either the Darken/Hartley-Crank or Manning-Lasaga models relating D * and interdiffusion coefficients, and both models yielded D Mg * consistent with the direct measurement of D Mg * in by Cygan and Lasaga (1985) at lower temperatures (750–900° C). The results (equations 4.1–4.3 and Table 1) indicate that D Fe * D Mg * <D Mn * and Q FeQ Mg>Q Mn, where Q is the activation energy. In contrast, the asymmetry of pyrope-almandine profiles is too great to fit with either tracer model assuming constant D * and indicates that D Mg * is similar to its value in spessartine-almandine couples but D Fe * is an order of magnitude less. The fit also suggests that D Ca * < D Fe * Mg * in pyrope-almandine couples. Synthesis of data from the two types of diffusion couples suggests that D Mg * is insensitive to compositional changes, whereas D Fe * is affected by Mn/Mg and Fe/Mg ratios and probably by other factors. These compositional effects on tracer coefficients are compatible with those documented by Morioka (1983) for cation diffusion in olivine.  相似文献   

19.
Crystalline primary inclusions in diamonds from the Argyle and Ellendale lamproites have been analyzed for Mn, Ni, Cu, Zn, Ga, Pb, Rb, Sr, Y, Zr, Nb, Ta, Ba and Mo by proton microprobe. Eclogite-suite inclusions dominate at Argyle and occur in equal proportions with peridotite-suite inclusions at Ellendale. Eclogitic phases present include garnet, omphacitic clinopyroxene, coesite, rutile, kyanite and sulfide. Eclogitic clinopyroxenes are commonly rich in K and contain 300–1060 ppm Sr and 3–70 ppm Zr: K/Rb increases with K content up to 1400 at 0.7–1.1% K. Rutiles have high Zr and Nb contents with Zr/Nb=1.5–4 and Nb/Ta 16. Of the peridotite-suite inclusions, olivine commonly contains > 10 ppm Sr and Mo; Cr-pyropes are depleted in Sr, Y and Zr, and enriched in Ni, relative to eclogitic garnets.Eclogite-suite diamonds grew in host rocks that were depleted in Mn, Ni and Cr, and enriched in Sr, Zn, Cu, Ga and Ti, relative to Type I eclogite xenoliths from the Roberts Victor Mine. Crystallization temperatures of the eclogite-suite diamonds, as determined by coexisting garnet and clinopyroxene from single diamonds, range from 1085 to 1575° C. Log K D (C i cpx /C i gnt ) varies linearly with 1/T for Zr, Sr and Ga in most of the same samples. This supports the validity of the temperature estimates; Argyle eclogite-suite diamonds have grown over a T range 400° C. Comparison with data from eclogite xenoliths in kimberlites suggests that K D Sr and K D Zr are mainly T-dependent, while K D Ga may be both temperature-and pressuredependent. K D Ni , K D Cu and K D Zn show no T dependence in these samples.In several cases, significant major-and/or trace-element disequilibrium is observed between different grains of the same mineral, or between pyroxene and garnet, within single diamonds. This implies that these diamonds grew in an open system; inclusions trapped at different stages of growth record changes in major and trace-element composition occurring in the host rock. Diamond growth may have been controlled by a fluid flux which introduced or liberated carbon and modified the composition of the rock. The wide range of equilibration temperatures and the range of composition recorded in the inclusions of single diamonds suggest that a significant time interval was involved in diamond growth.  相似文献   

20.
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   

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