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1.
Twenty-two hornblendes separated from amphibolites and granulites of the Grenville Orogen of Ontario have been quantitatively analyzed for major and minor elements by electron microprobe, for FeO/Fe2O3 by wet chemistry, and for H2O by manometric measurement as H2. Hornblende formulae were calculated on the basis of 24O+OH+Cl+F. Most samples are magnesio-hornblendes, ferroan pargasitic hornblendes and ferroan hastingsitic hornblendes, with weight fractions of Fe3+/(Fe2++Fe3+) ranging from 0.15 to 0.50. An oxy-amphibole component of 0–25 mol%, with an average value of 17 mol%, is obtained for these complete analyses. When compared with structural formulae determined solely from microprobe data, normalization based on 13=Si+Ti+Al+Fe+Mn+Mg cations provides the best approximation to hornblende formulae calculated from the complete analyses. Less satisfactory agreement is obtained from a normalization scheme based on 15=Si+Ti+Al+Fe+Mn+Mg+Ca, while worst agreement is obtained from normalization to 23 oxygens assuming all Fe is Fe2+. No normalization scheme based on microprobe data alone consistently replicates the measured FeO, Fe2O3, and H2O; accurate determination of these values requires complete chemical analysies. Ionic solution models previously have been proposed to evaluate the activity of Ca2Mg5Si8 O22(OH)2(a Trem) in hornblende for use in equilibria that constrain the activity of H2O (a H 2O) in igneous and metamorphic rocks. Application of ionic models to typical hornblendes produces low a Trem (usually<0.01), consequetly yielding extremely low a H 2O. If an oxy-amphibole component is present, the calculated a Trem and H2O is further reduced. An oxy-amphibole component of 25% reduces the calculated H2O activity and that of any hydroxyl-amphibole component by 50% below that calculated with simplified assumptions regarding X OH in the hydroxyl site (i.e., X OH=1, or X OH=1–X Cl–X f). Thus, methods of amphibole normalizations appear to have a substantial effect on calculated amphibole and H2O activites. Before quantitative hornblende thermobarometry can be calibrated and applied, the amounts of FeO, Fe2O3 and H2O must be measured in order to fully characterize hornblende solid solutions.Contribution No. 478 from the Mineralogical Laboratory, University of Michigan  相似文献   

2.
Experimental investigations have been performed at T = 1200°C, P = 200 MPa and fH2 corresponding to H2O-MnO-Mn3O4 and H2O-QFM redox buffers to study the effect of H2O activity on the oxidation and structural state of Fe in an iron-rich basaltic melt. The analysis of Mössbauer and Fe K-edge X-ray absorption nearedge structure (XANES) spectra of the quenched hydrous ferrobasaltic glasses shows that the Fe3+/ΣFe ratio of the glass is directly related to aH2O in a H2-buffered system and, consequently, to the prevailing oxygen fugacity (through the reaction of water dissociation H2O ↔ H2 + 1/2 O2). However, water as a chemical component of the silicate melt has an indistinguishable effect on the redox state of iron at studied conditions. The experimentally obtained relationship between fO2 and Fe3+/Fe2+ in the hydrous ferrobasaltic melt can be adequately predicted in the investigated range by the existing empiric and thermodynamic models. The ratio of ferric and ferrous Fe is proportional to the oxygen fugacity to the power of ∼0.25 which agrees with the theoretical value from the stoichiometry of the Fe redox reaction (FeO + ¼ O2 = FeO1.5). The mean centre shifts for Fe2+ and Fe3+ absorption doublets in Mössbauer spectra show little change with increasing Fe3+/ΣFe, suggesting no significant change in the type of iron coordination. Similarly, XANES preedge spectra indicate a mixed (C3h, Td, and Oh, i.e., 5-, 4-, and sixfold) coordination of Fe in hydrous basaltic glasses.  相似文献   

3.
New activity–composition (a–x) relations for minerals commonly occurring in metapelites are presented for use with the internally consistent thermodynamic dataset of Holland & Powell ( 2011 , Journal of Metamorphic Geology, 29 , 333–383). The a–x relations include a broader consideration of Fe2O3 in minerals, changes to the formalism of several phases and order–disorder in all ferromagnesian minerals where Fe–Mg mixing occurs on multiple sites. The a–x relations for chlorite, biotite, garnet, chloritoid, staurolite, cordierite, orthopyroxene, muscovite, paragonite and margarite have been substantially reparameterized using the approach outlined in the companion paper in this issue. For the first time, the entire set of a–x relations for the common ferromagnesian minerals in metapelitic rocks is parameterized simultaneously, with attention paid to ensuring that they can be used together to calculate phase diagrams of geologically appropriate topology. The a–x relations developed are for use in the Na2O–CaO–K2O–FeO–MgO–Al2O3–SiO2–H2O–TiO2–O2 (NCKFMASHTO) system for both subsolidus and suprasolidus conditions. Petrogenetic grids in KFMASH and KFMASHTO are similar in topology to those produced with earlier end‐member datasets and a–x relations, but with some notable differences. In particular, in subsolidus equilibria, the FeO/(FeO + MgO) of garnet is now greater than in coexisting staurolite, bringing a number of key staurolite‐bearing equilibria into better agreement with inferences from field and petrographic observations. Furthermore, the addition of Fe3+ and Ti to a number of silicate phases allows more plausible equilibria to be calculated in relevant systems. Pseudosections calculated with the new a–x relations are also topologically similar to equivalent diagrams using earlier a–x relations, although with many low variance fields shifting in P–T space to somewhat lower pressure conditions.  相似文献   

4.
The equilibrium in which hydrous Fe-cordierite breaks down to almandine, sillimanite, quartz, and water was previously experimentally determined by Richardson (1968) and Holdaway and Lee (1977) using QMF buffer and by Weisbrod (1973) using QIF buffer. All these studies yielded similar results — a negative dP/dT slope for the equilibrium curve. However, based on theoretical arguments, Martignole and Sisi (1981), and based on Fe-Mg partitioning experiments on coexisting cordierite and garnet in equilibrium with sillimanite and quartz, Aranovich and Podlesskii (1983) suggested that this equilibrium curve has a positive dP/dT slope and its position depends on the water content of the equilibrium cordierite. We have redetermined this equilibrium using a much improved tecnique of detecting reaction direction, and cordierite starting material that contained virtually no hercynite. Hercynite was present as a contaminant in the cordierites of previous experimental studies and possibly reacted with quartz during the experimental runs to expand the apparent stability field of Fe-cordierite. We synthesized Fe-cordierite from reagent grade oxides at 710°C and 2 kbar (using QMF buffer) with two intermediate stages of grinding and mixing. The cordierite has a unit cell volume of 1574.60 Å3 (molar volume=23.706 J/bar) and no Fe3+ as indicated by X-ray diffraction and room temperature Mössbauer studies respectively. Reaction direction was concluded by noting20% change of the ratios of intensities of two key X-ray diffraction peaks of cordierite and almandine. Our results show that the four-phase equilibrium curve passes through the points 2.1 kbar, 650°C and 2.5 kbar, 750°C. This disagrees with all previous experimental studies. H2O in the Fe-cordierite, equilibrated at 2.2 kbar and 700°C and determined by H-extraction line in the stable isotope laboratory, is 1.13 wt% (n=0.41 moles). H2O content of pure Mg-cordierite equilibrated under identical conditions and determined by thermogravimentric conditions and determined by thermogravimetric analysis is 1.22 wt% (n=0.40). Similar determinations on Fe-cordierite and Mg-cordierite equilibrated at 2.0 kbar and 650°C show 1.27 wt% (n=0.46) and 1.47 wt% (n=0.48) of H2O respectively. Thus, H2O content appears to be independent of Fe/Mg ratio in cordierite, a conclusion which supports previous experimental determinations. The experimentally determined equilibrium curve represents conditions of PH2O=Ptotal. From this we calculated the anhydrous curve representing equilibrium under conditions of X H2O V =0.0. A family of calculated equilibrium curves of constant n H2O Cord cut the experimentally determined curve at a very small angle indicating a slight variation in n H2O Cord in cordierite in equilibrium with almandine, sillimanite, and quartz under the conditions of constant X H2O V . Ancther set of calculated equilibrium curves, each representing constant a H2O V demonstrate that the slopes of the curves vary with X H2O V , and are all positive in the full range of 0.0X H2O V 1.0.  相似文献   

5.
Cordierite has the ideal formula (Mg,Fe)2Al4Si5O18 .x(H2O,CO2), but it must contain some Fe3+ to account for its blue color and strong pleochroism. The site occupation and concentration of Fe3+ in two Mg-rich natural cordierites have been investigated by EPR and 57Fe Mössbauer spectroscopy. In addition, powder IR spectroscopy, X-ray diffraction, and TEM examination were used to characterize the samples. Single-crystal and powder EPR spectra indicate that Fe3+ is located on T11 in natural cordierites and not in the channels. The amount in Mg-rich cordierites is very small with an upper limit set by Mössbauer spectroscopy giving less than 0.004 cations per formula unit (pfu). Fe3+ in cordierite can, therefore, be considered insignificant for most petrologic calculations. Heat-treating cordierite in air at 1,000?°C for 2?days causes an oxidation and/or loss of Fe2+ on T11, together with an expulsion of Na+ from the channels, whereas heating at the Fe–FeO buffer produces little Fe3+ in cordierite. Heating at 1,000?°C removes all class I H2O, but small amounts of class II H2O remain as shown by the IR measurements. No evidence for channel Fe2+ or Fe3+ in the heat-treated samples was found. The blue color in cordierite arises from a broad absorption band (E//b and weaker with E//a) around 18,000?cm?1 originating from charge-transfer between Fe2+ in the octahedron and Fe3+ in the edge-shared T11 tetrahedron. It therefore appears that all natural cordierites contain some tetrahedral Fe3+. The brown color of samples heated in air may be due to the formation of very small amounts of submicroscopic magnetite and possibly hematite. These inclusions in cordierite can only be identified through TEM study.  相似文献   

6.
A quantitative petrogenetic grid for pelitic schists in the system KFMASH that includes the phases garnet, chlorite, biotite, chloritoid, cordierite, staurolite, talc, kyanite, andalusite, sillimanite, and pyrophyllite (with quartz, H2O and muscovite or K-feldspar in excess) is presented. The grid is based on thermodynamic data of Berman et al. (1985) and Berman (1988) for endmember KFASH and KMASH equilibria and natural Fe-Mg partitioning for the KFMASH system. Calculation of P-T slopes and the change in Fe/(Fe+Mg) along reactions in the KFMASH system were made using the Gibbs method. In addition, the effect on the grid of MnO and CaO is evaluated quantitatively. The resulting grid is consistent with typical Buchan and Barrovian parageneses at medium to high grades. At low grades, the grid predicts an extensive stability field for the paragenesis chloritoid+biotite which arises because of the unusual facing of the reaction chloritoid+biotite + quartz+H2O = garnet+chlorite+muscovite, which proceeds to the right with increasing T in the KFMASH system. However, the reaction proceeds to the left with increasing T in the MnKFASH system so the assemblage chloritoid + biotite is restricted to bulk compositions with high Fe/(Fe+Mg+Mn). Typical metapelites will therefore contain garnet+chlorite at low grades rather than chloritoid + biotite.  相似文献   

7.
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   

8.
Oxidation state of mantle xenoliths from British Columbia,Canada   总被引：3，自引：0，他引：3  
Mössbauer spectra for 17 spinels separated from mantle xenoliths from six different eruptive centers in southern British Columbia, Canada were measured in an effort to accurately determine their Fe3+/total Fe ratios, and to examine lateral and vertical variations in oxygen fugacities (f o2's) calculated for these samples using published thermobarometric methods. Spectra acquired at 298 and 77 K suggest that both Fe2+ and Fe3+ are tetrahedrally coordinated in lherzolite spinels from this alkaline province. Calculatedf o2's for spinel lherzolites from British Columbia range from about 0.5 to 1.5 log units below the fayalite-magnetite-quartz (FMQ) oxygen buffer at 15 kbar using the thermobarometric method of O'Neill and Wall. Thesef o2's are on average more reducing than those reported for the upper mantle beneath the Massif Central and Japanese Arc and fall within the range for fresh MORB glasses and for lherzolite xenoliths from the southwestern United States and Mongolia. Significant variations inf o2 between samples from different eruptive centers with varying ages are absent, indicating that the oxidation state of the upper mantle was not affected by Cenozoic magmatism within this alkaline province.  相似文献   

9.
Abstract Three reactions are calibrated as geothermobarometers for garnet–orthopyroxene–plagioclase–quartz assemblages, namely: 1/2 ferrosilite + 1/3 pyrope ± 1/2 enstatite + 1/3 almandine (A): ferrosilite + anorthite ± 2/3 almandine + 1/3 grossularite + quartz (B); and enstatite + anorthite ± 2/3 pyrope + 1/3 grossularite + quartz (C). The internally consistent geothermobarometers based on reactions (A), (B) and (C) are calibrated from experimental data only. The thermodynamic parameters of reaction (A) are derived from published experimental data in the FMAS system (n= 104) in the range 700–1400°C and 5–50 kbar, while those for reaction (B) are derived by summation of the existing reversed experimental data of the mineral equilibria: ferrosilite ± fayalite + quartz (D) and anorthite + fayalite ± 2/3 almandine + 1/3 grossularite (E). The retrieved thermodynamic parameters for reactions (A), (B) and (C) are, respectively: (ΔH0, cal) -3367 ± 209, -2749 ± 350 and +3985 ± 545; (ΔS0, cal K?1) -1.634 ± 0.163, -8.644 ± 0.298 and -5.376 ± 0.391; and (ΔV01,298, cal bar?1) -0.024, -0.60946 and -0.5614. On a one-cation basis, the derived Margules parameters of the ternary Ca–Fe–Mg in garnet are: WFe–Mg= -1256 + 1.0 (～0.23) T(K), WMg–Fe= 2880 -1.7 (～0.13) T(K), WCa–Mg= 4047 (～77) -1.5 T(K), WMg–Ca= 1000 (～77) -1.5 T(K), WCa–Fe= -723 + 0.332 (～0.02) T(K), WFe–Ca= 1090, (cal) and the ternary constant C123= -4498 + 1.516 (～0.265) T(K) cal (subregular solution model of non-ideal mixing); and Fe–Mg–Al in orthopyroxene: WFe–Mg= 948 (～200) -0.34 (～0.10) T(K), WFe–Al= -1950 (～500) and WMg–Al= 0 (cal) (regular solution model of non-ideal mixing). The anorthite activity in plagioclase is calculated by the ‘Al-avoidance’model of subregular Ca–Na mixing commonly used for geobarometry based on reactions (B) and (C). When the geothermobarometers are applied to garnet–orthopyroxene–plagioclase–quartz assemblages (n= 45) of wide compositional range from the Precambrian South Indian granulites, temperature ranges of 690–860°C (X= 760 ± 45°C) and pressure ranges of 5–10 kbar were obtained. The P–T values were estimated simultaneously and there is no difference in the pressure calculated from PMg (reaction C) and PFe (reaction B). In the existing calibrations this difference is 1 kbar or more. Furthermore, there is no compositional dependence of the ln K of the experimental data in the FMAS (n= 104) and the CFMAS (n= 78) systems at different temperatures and the estimated temperatures of the South Indian granulites.  相似文献   

10.
Hydrothermal synthesis of Fe-pum-pellyites was conducted using high pressure cold-seal apparatus and solid oxygen buffering techniques at temperatures between 250°C and 550°C and 2.0–9.1 kbar Pfluid. Fe-pumpellyites were synthesized from partially crystalline gel mixtures of compositions: 4CaO - 2.1Al2O3_1.5FeO - 0.3MgO - 6SiO2 (II) and 3CaO - 1.5 Al2O3 - 2.7FeO - 0.3MgO - 6SiO2 (III) in the presence of excess H2O at Pfluid of 5–9.1 Kbar, temperatures between 275°C and 325°C, and fO2 defined by the QFM and HM buffers; for both of these compositions (II and III), the condensed synthetic run products included minor 7Å chlorite ± garnet ± Fe-oxide. The cell dimensions and aggregate refractive index (a= 19.13(2)Å, b= 5.940(4)Å, c= 8.847(5)Å, ±= 97.37(6)±, and n= 1.702(2)) of the pum-pellyite synthesized from the bulk composition II mix are compatible with those of natural pumpellyites containing similar total Fe contents. Attempts at synthesizing Fe-pumpellyites from a Mg-free bulk composition were not successful; these results are consistent with the total absence of natural Mg-free pumpellyites. The higher temperature, higher oxygen fugacity assemblages of the equivalent bulk compositions (II and III) consist of epidote ± minor amounts of chlorite, garnet, quartz, hematite, and magnetite. The results of these synthesis experiments accord with the mineral parageneses observed in low-grade metabasites which imply that Fe-pumpellyites are replaced by epidote with increasing temperature and/or fO2 and that Fe3+ is preferentially partitioned into epidote with respect to coexisting pum-pellyite. In addition, these synthesis experiments indicate that Fe-bearing pumpellyites crystallize at and are stable to lower temperatures than more aluminous pumpellyites—a result also consistent with natural systems.  相似文献   

11.
The equilibrium coexistence of sapphirine + quartz is inferred to record temperatures in excess of 980 °C, based on the stability of this assemblage in the simplified chemical system FeO–MgO–Al2O3–SiO2 (FMAS) system. However, the potential for sapphirine to contain significant Fe3+ suggests that the stability of sapphirine + quartz could extend to lower temperatures than those constrained in this ideal system. The Wilson Lake terrane in the Grenville Province of central Labrador preserves sapphirine + quartz‐bearing assemblages in highly oxidized bulk compositions, and provides an opportunity to explore the stability of sapphirine + quartz in such rock compositions within the Na2O–CaO–K2O–FeO–MgO–Al2O3–SiO2–H2O–TiO2–O (NCKFMASHTO) chemical system. Starting with the phase equilibria in FeO–MgO–Al2O3–SiO2–TiO2–O (FMASTO), expansion into K2O–FeO–MgO–Al2O3–SiO2–H2O–TiO2–O (KFMASHTO) allows the effect of the stability of the additional phases, biotite, K‐feldspar and melt, on the stability of sapphirine + quartz to be assessed. These phase relations are evaluated generally using P–T projections, and the ultimate extension into NCKFMASHTO is done with pseudosections. Conditions of peak metamorphism in the Wilson Lake terrane are constrained using P–T pseudosections, and the appropriate H2O and O contents to use in the modelled compositions are investigated using T–MH2O and T–MO pseudosections. The peak P–T estimates from a sapphirine + quartz‐bearing sample are ～960 to 935 °C at ～10 to 8.6 kbar, similar to estimates from orthopyroxene + sillimanite + quartz ± garnet‐bearing samples. Whereas the sapphirine + quartz‐bearing sample is more Fe‐rich than the orthopyroxene + sillimanite‐bearing sample on an all‐Fe‐as‐FeO basis, once the oxidation state is taken into account, the former is effectively more magnesian than the latter, accounting for the sapphirine occurrence.  相似文献   

12.
The paper presents thermodynamic models for mineral solid solutions used in physicochemical simulations with the SELECTOR-C program package (PP) in application to metamorphic mineral-forming processes. It is demonstrated that the simulated FeO and MgO distribution in the mineral pairs garnetbiotite, garnet-orthopyroxene, orthopyroxene-biotite, orthopyroxene-olivine, garnet-cordierite, garnetclinopyroxene, and clinopyroxene-orthopyroxene in the model samples satisfactorily corresponds to available experimental and empirical data. Simulations of naturally occurring mineral associations are employed to demonstrate the capabilities of the new version of the SELECTOR-C PP as a tool for studying the evolution of mineral assemblages at varying P-T conditions and fluid regime, the perfectly mobile and inert behaviors of certain fluid components during the origin of mineral associations are demonstrated, the pseudosection method applied over a broad P-T range is used to trace systematic variations in the composition of mineral associations in granulite-facies metabasites and metapelites, and the upper limit of plagioclase stability is estimated for these rocks at pressures of 11–12 kbar. Principal differences are elucidated in the effect of rocks rich and poor in Fe3+ on the percolation of metamorphic fluid through them: Fe3+-rich rocks retain their own redox potential at a certain level by buffering reactions, whereas Fe3+-poor rocks rapidly exhaust their buffer capacity and acquire the redox potential of the inflowing external fluid. This allowed us to evaluate the logfO2 at no higher than −17 (at T = 700°C and P = 6.8 kbar). Our simulation of the equilibrium of natural rock samples provides good reasons to believe that natural mineral assemblages can be formed at low fluid/rock ratios of no higher than 0.01–0.06.  相似文献   

13.
Reversals for the reaction 2 annite+3 quartz=2 sanidine+3 fayalite+2 H2O have been experimentally determined in cold-seal pressure vessels at pressures of 2, 3, 4 and 5?kbar, limiting annite +quartz stability towards higher temperatures. The equilibrium passes through the temperature intervals 500–540°?C (2?kbar), 550–570°?C (3?kbar), 570–590°?C (4?kbar) and 590–610°?C (5?kbar). Starting materials for most experiments were mixtures of synthetic annite +fayalite+sanidine+quartz and in some runs annite+quartz alone. Microprobe analyses of the reacted mixtures showed that the annites deviate slightly from their ideal Si/Al ratio (Si per formula unit ranges between 2.85 and 2.92, AlVI between 0.06 and 0.15). As determined by Mössbauer spectroscopy, the Fe3+ content of annite in the assemblage annite+fayalite +sanidine+quartz is around 5–7%. The experimental data were used to extract the thermodynamic standard state enthalpy and entropy of annite as follows: H 0 f,?Ann =?5125.896±8.319 [kJ/mol] and S 0 Ann=432.62±8.89 [J/mol/K] (consistent with the Holland and Powell 1990 data set), and H 0 f,Ann =?5130.971±7.939 [kJ/mol] and S 0 Ann=424.02±8.39 [J/mol/K] (consistent with the TWEEQ data base, Berman 1991). The preceeding values are close to the standard state properties derived from hydrogen sensor data of the redox reaction annite=sanidine+magnetite+H 2 (Dachs 1994). The experimental half-reversal of Eugster and Wones (1962) on the annite +quartz breakdown reaction could not be reproduced experimentally (formation of annite from sanidine+fayalite+quartz at 540°?C/1.035?kbar/magnetite-iron buffer) and probable reasons for this discrepancy remain unclear. The extracted thermodynamic standard state properties of annite were used to calculate annite and annite+quartz stabilities for pressures between 2 and 5?kbar.  相似文献   

14.
Eclogite boudins occur within an orthogneiss sheet enclosed in a Barrovian metapelite‐dominated volcano‐sedimentary sequence within the Velké Vrbno unit, NE Bohemian Massif. A metamorphic and lithological break defines the base of the eclogite‐bearing orthogneiss nappe, with a structurally lower sequence without eclogite exposed in a tectonic window. The typical assemblage of the structurally upper metapelites is garnet–staurolite–kyanite–biotite–plagioclase–muscovite–quartz–ilmenite ± rutile ± silli‐manite and prograde‐zoned garnet includes chloritoid–chlorite–paragonite–margarite, staurolite–chlorite–paragonite–margarite and kyanite–chlorite–rutile. In pseudosection modelling in the system Na2O–CaO–K2O–FeO–MgO–Al2O3–SiO2–H2O (NCKFMASH) using THERMOCALC, the prograde path crosses the discontinuous reaction chloritoid + margarite = chlorite + garnet + staurolite + paragonite (with muscovite + quartz + H2O) at 9.5 kbar and 570 °C and the metamorphic peak is reached at 11 kbar and 640 °C. Decompression through about 7 kbar is indicated by sillimanite and biotite growing at the expense of garnet. In the tectonic window, the structurally lower metapelites (garnet–staurolite–biotite–muscovite–quartz ± plagioclase ± sillimanite ± kyanite) and amphibolites (garnet–amphibole–plagioclase ± epidote) indicate a metamorphic peak of 10 kbar at 620 °C and 11 kbar and 610–660 °C, respectively, that is consistent with the other metapelites. The eclogites are composed of garnet, omphacite relicts (jadeite = 33%) within plagioclase–clinopyroxene symplectites, epidote and late amphibole–plagioclase domains. Garnet commonly includes rutile–quartz–epidote ± clinopyroxene (jadeite = 43%) ± magnetite ± amphibole and its growth zoning is compatible in the pseudosection with burial under H2O‐undersaturated conditions to 18 kbar and 680 °C. Plagioclase + amphibole replaces garnet within foliated boudin margins and results in the assemblage epidote–amphibole–plagioclase indicating that decompression occurred under decreasing temperature into garnet‐free epidote–amphibolite facies conditions. The prograde path of eclogites and metapelites up to the metamorphic peak cannot be shared, being along different geothermal gradients, of about 11 and 17 °C km?1, respectively, to metamorphic pressure peaks that are 6–7 kbar apart. The eclogite–orthogneiss sheet docked with metapelites at about 11 kbar and 650 °C, and from this depth the exhumation of the pile is shared.  相似文献   

15.
Synthetic spinel harzburgite and lherzolite assemblages were equilibrated between 1040 and 1300° C and 0.3 to 2.7 GPa, under controlled oxygen fugacity (f O 2). f O 2 was buffered with conventional and open double-capsule techniques, using the Fe−FeO, WC-WO2-C, Ni−NiO, and Fe3O4−Fe2O3 buffers, and graphite, olivine, and PdAg alloys as sample containers. Experiments were carried out in a piston-cylinder apparatus under fluid-excess conditions. Within the P-T-X range of the experiments, the redox ratio Fe3+/ΣFe in spinel is a linear function of f O 2 (0.02 at IW, 0.1 at WCO, 0.25 at NNO, and 0.75 at MH). It is independent of temperature at given Δlog(f O 2), but decreases slightly with increasing Cr content in spinel. The Fe3+/ΣFe ratio falls with increasing pressure at given Δlog(f O 2), consistent with a pressure correction based on partial molar volume data. At a specific temperature, degree of melting and bulk composition, the Cr/(Cr+Al) ratio of a spinel rises with increasing f O 2. A linear least-squares fit to the experimental data gives the semi-empirical oxygen barometer in terms of divergence from the fayalite-magnetite-quartz (FMQ) buffer:
  相似文献   

16.
The dependence of water concentration in synthetic (Mg, Fe2+)-cordierite on the composition of the solid solution was examined in experiments that lasted for 10 days at = 200–230 MPa, t = 600–700°C, and oxygen fugacity corresponding to the Fe-FeO buffer. Mass spectrometric data indicate that the dependence of water concentration in cordierite on its Fe mole fraction Fe2+/(Fe2+ + Mg) has maxima at compositions with F = 0.2–0.3. IR diffuse reflectance spectroscopic data and data on the structural setting of H2O molecules in the structural channels of alkali-free (Mg, Fe2+)-cordierite indicate that the H-H vector of some H2O molecules (H2O-II) is perpendicular to [001] of the crystal. The dependence of the magnetic properties of synthetic (Mg, Fe2+)-cordierite was studied by static magnetization technique at 5–300 K in an external magnetic field up to 20 kOe in strength.  相似文献   

17.
In P - T - logfO2 space, the stability of annite (ideally KFe 3 2+ (OH)2AlSi3O10) at high fO2 (low fH2) is limited by the reaction: annite = sanidine + magnetite + H2. Using the hydrogen-sensor technique, the equilibrium fH2 of this reaction was measured between 500 and 800° C at 2.8 kbar in 50° C intervals. Microbrobe analyses of the reacted annite+sanidine+magnetite mixtures show that tetrahedral positions of annite have a lower Si/Al ratio than the ideal value of 3/1. Silicon decreases from 2.9 per formula unit at low temperatures to 2.76 at high temperatures. As determined by Mössbauer spectroscopy in three experimental runs, the Fe3+ content of annite in the equilibrium assemblage is 11%±3. A least squares fit to the hydrogensensor data gives H R 0 = 50.269 ± 3.987 kJ and S R 0 = 83.01 ± 4.35 J/K for equilibrium (1). The hydrogene-sensor data are consistent with temperature half brackets determined in the classical way along the nickel-nickel oxide (NNO) and quartz-fayalite-magnetite (QFM) buffers with a mixture of annite+sanidine+magnetite for control. Compared to published oxygen buffer reversals, agreement is only found at high temperature and possible reasons for that discrepancy are discussed. The resulting slope of equilibrium (1) in logfO2 – T dimensions is considerably steeper than previously determined and between 400 and 800°C only intersects with the QFM buffer curve. Based on the hydrogen-sensor data and on the thermodynamic dataset of Berman (1988, and TWEEQ data base) for sanidine, magnetite and H2, the deduced standard-state properties of annite are: H f 0 =-5127.376±5.279 kJ and S 0=422.84±5.29 J/(mol K). From the recently published unit cell refinements of annites and their Fe3+ contents, determined by Mössbauer spectroscopy (Redhammer et al. 1993), the molar volume of pure annite was constrained as 15.568±0.030 J/bar. A revised stability field for annite is presented, calculated between 400 and 800°C.  相似文献   

18.
Using a previously published, internally consistent thermodynamic dataset and updated models of activity–composition relations for solid solutions, petrogenetic grids in the model system KFMASH (K2O–FeO–MgO–Al2O3–SiO2–H2O) and the subsystems KMASH and KFASH have been calculated with the software THERMOCALC 3.1 in the P–T range 5–36 kbar and 400–810 °C, involving garnet, chloritoid, biotite, carpholite, talc, chlorite, staurolite and kyanite/sillimanite with phengite, quartz/coesite and H2O in excess. These grids, together with calculated AFM compatibility diagrams and pseudosections, are shown to be powerful tools for delineating the phase equilibria and P–T conditions of pelitic high-P assemblages for a variety of bulk compositions. The calculated equilibria and mineral compositions are in good agreement with petrological observation. The calculation indicates that the typical whiteschist assemblage kyanite–talc is restricted to the rocks with extremely high XMg values, decreasing XMg in a bulk composition favoring the stability of chloritoid and garnet. Also, the chloritoid–talc paragenesis is stable over 19–20 kbar in a temperature range of ca. 520–620 °C, being more petrologically important than the previously highlighted assemblage talc–phengite. Moreover, contours of the calculated Si isopleths in phengite in P–T and P–X pseudosections for different bulk compositions extend the experimentally derived phengite geobarometers to various KFMASH assemblages.  相似文献   

19.
 H2O activities in concentrated NaCl solutions were measured in the ranges 600°–900° C and 2–15 kbar and at NaCl concentrations up to halite saturation by depression of the brucite (Mg(OH)2) – periclase (MgO) dehydration equilibrium. Experiments were made in internally heated Ar pressure apparatus at 2 and 4.2 kbar and in 1.91-cm-diameter piston-cylinder apparatus with NaCl pressure medium at 4.2, 7, 10 and 15 kbar. Fluid compositions in equilibrium with brucite and periclase were reversed to closures of less than 2 mol% by measuring weight changes after drying of punctured Pt capsules. Brucite-periclase equilibrium in the binary system was redetermined using coarsely crystalline synthetic brucite and periclase to inhibit back-reaction in quenching. These data lead to a linear expression for the standard Gibbs free energy of the brucite dehydration reaction in the experimental temperature range: ΔG° (±120J)=73418–134.95T(K). Using this function as a baseline, the experimental dehydration points in the system MgO−H2O−NaCl lead to a simple systematic relationship of high-temperature H2O activity in NaCl solution. At low pressure and low fluid densities near 2 kbar the H2O activity is closely approximated by its mole fraction. At pressures of 10 kbar and greater, with fluid densities approaching those of condensed H2O, the H2O activity becomes nearly equal to the square of its mole fraction. Isobaric halite saturation points terminating the univariant brucite-periclase curves were determined at each experimental pressure. The five temperature-composition points in the system NaCl−H2O are in close agreement with the halite saturation curves (liquidus curves) given by existing data from differential thermal analysis to 6 kbar. Solubility of MgO in the vapor phase near halite saturation is much less than one mole percent and could not have influenced our determinations. Activity concentration relations in the experimental P-T range may be retrieved for the binary system H2O-NaCl from our brucite-periclase data and from halite liquidus data with minor extrapolation. At two kbar, solutions closely approach an ideal gas mixture, whereas at 10 kbar and above the solutions closely approximate an ideal fused salt mixture, where the activities of H2O and NaCl correspond to an ideal activity formulation. This profound pressure-induced change of state may be characterized by the activity (a) – concentration (X) expression: a H 2O=X H 2O/(1+αX NaCl), and a NaCl=(1+α)(1+α)[X NaCl/(1+αX NaCl)](1+α). The parameter α is determined by regression of the brucite-periclase H2O activity data: α=exp[A–B/ϱH 2O ]-CP/T, where A=4.226, B=2.9605, C=164.984, and P is in kbar, T is in Kelvins, and ϱH 2O is the density of H2O at given P and T in g/cm3. These formulas reproduce both the H2O activity data and the NaCl activity data with a standard deviation of ±0.010. The thermodynamic behavior of concentrated NaCl solutions at high temperature and pressure is thus much simpler than portrayed by extended Debye-Hückel theory. The low H2O activity at high pressures in concentrated supercritical NaCl solutions (or hydrosaline melts) indicates that such solutions should be feasible as chemically active fluids capable of coexisting with solid rocks and silicate liquids (and a CO2-rich vapor) in many processes of deep crustal and upper mantle metamorphism and metasomatism. Received: 1 September 1995 / Accepted: 24 March 1996  相似文献   

20.
Garnet-bearing mineral assemblages are commonly observed in pelitic schists regionally metamorphosed to upper greenschist and amphibolite facies conditions. Modelling of thermodynamic data for minerals in the system Na2O–K2O–FeO–MgO–Al2O3–SiO2–H2O, however, predicts that garnet should be observed only in rocks of a narrow range of very high Fe/Mg bulk compositions. Traditionally, the nearly ubiquitous presence of garnet in medium- to high-grade pelitic schists is attributed qualitatively to the stabilizing effect of MnO, based on the observed strong partitioning of MnO into garnet relative to other minerals. In order to quantify the dependence of garnet stability on whole-rock MnO content, we have calculated mineral stabilities for pelitic rocks in the system MnO–Na2O–K2O–FeO–MgO–Al2O3–SiO2–H2O for a moderate range of MnO contents from a set of non-linear equations that specify mass balance and chemical equilibrium among minerals and fluid. The model pelitic system includes quartz, muscovite. albite, pyrophyllite, chlorite, chloritoid, biotite, garnet, staurolite, cordierite, andalusite, kyanite. sillimanite, K-feldspar and H2O fluid. In the MnO-free system, garnet is restricted to high Fe/Mg bulk compositions, and commonly observed mineral assemblages such as garnet–chlorite and garnet–kyanite are not predicted at any pressure and temperature. In bulk compositions with XMn= Mn/(Fe + Mg + Mn) > 0.01, however, the predicted garnet-bearing mineral assemblages are the same as the sequence of prograde mineral assemblages typically observed in regional metamorphic terranes. Temperatures predicted for the first appearance of garnet in model pelitic schist are also strongly dependent on whole-rock MnO content. The small MnO contents of normal pelitic schists (XMn= 0.01–0.04) are both sufficient and necessary to account for the observed stability of garnet.  相似文献   

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