Stability of almandine in the system FeO-(Fe2O3)-Al2O3-SiO2-(H2O) at elevated pressures

Almandine, although decomposing in the presence of metallic iron into the anhydrous subsolidus assemblage fayalite + ferrocordierite + hercynite solid solution at low pressures, melts incongruently to hercynite_ss + quartz + liquid at 10 kb. At pressures between about 12 and 20 kb the products of incongruent melting are hercynite_ss + liquid only, and at still higher pressures almandine melts congruently. For the intermediate pressures between 2 and 10 kb not investigated a sequence of probable breakdown and melting relations involving the phases ferrocordierite, fayalite, hercynite_ss, quartz, and liquid is derived through Schreinemakers' analyses.The lower temperature stability limit of almandine in the presence of water at low oxygen fugacities and pressures of 15 to 20 kb lies between 550° and 600° C as at low pressures. It is marked, however, by the breakdown to a hydrous assemblage involving chloritoid and the new phase aluminous deerite. Since the anhydrous melting at these pressures occurs between 1300° and 1400° C, the thermal stability range of almandine increases drastically with pressure. Its upper breakdown limit shows in principle a similar behavior as those of other garnet end members.     

Synchrotron radiation study on the high-pressure and high-temperature phase relations of KAlSi3O8

In situ X-ray diffraction study on KAlSi₃O₈ has been performed using the cubic type high pressure apparatus, MAX90, combined with synchrotron radiation. We determined the phase relations of sanidine, the wadeite-type K₂Si₄O₉+kyanite (Al₂SiO₅)+coesite (SiO₂) assemblage, and hollandite-type KAlSi₃O₈, including melting temperatures of potassic phases, up to 11 GPa. Our data on subsolidus phase boundaries are close to the recent data of Yagi and Akaogi (1991). Melting relations of sanidine are consistent with the low pressure data of Lindsley (1966). The breakdown of sanidine into three phases reduces melting temperature, and wadeite-type K₂Si₄O₉ melts first around 1500° C in three phase coexisting region. Melting point of hollandite-type KAlSi₃O₈ is between 1700° C and 1800° C at 11 GPa. If these potassic phases host potassium in the earth's mantle, the true mantle solidus temperature will be much lower than the reported dry solidus temperature of peridotite.     

Synthetic and natural tremolite in equilibrium with forsterite,enstatite, diopside and fluid

The following equilibrium among tremolite forsterite, diopside, and orthorhombic enstatite has been investigated using either synthetic tremolite or natural amphibole in the starting materials: Ca₂Mg₅Si₈O₂₂(OH)₂+Mg₂SiO₄ =2 CaMgSi₂O₆+5MgSiO₃+H₂O A significant increase in the stability of the reactants was observed with natural rather than synthetic tremolite. For example, in nearly pure H₂O with the H₂ content of the fluid buffered by nickel-bunsenite at one kilobar (10⁸ pascals), the breakdown of the assemblage with synthetic amphibole occurs at 708±20° C. The breakdown of the assemblage with natural amphibole, Ca_2.16Mg_4.94Fe_0.03Si_7.92 Al_0.01O₂₂(OH)₂F_0.03 occurs at 841±47° C. The shift in the breakdown curve is attributed to variation in the properties of the amphiboles since all other factors were common in the experiments. The reactions have also been investigated with hydrogen fugacity defined by the methane buffer and the NB, OH (XG, COH) buffer. Analysis of the experimental data by linear programming indicates that the enthalpy of reaction is tightly constrained when the calorimetrically determined entropy of 160.92 joules/degree is used. The resulting enthalpy of reaction is 113.96±1.82 kilojoules with the natural amphibole and 104.83±0.12 kilojoules with synthetic tremolite. Deviation of the natural amphibole from the ideal tremolite formula as well as a greater number of defects and dislocations in the synthetic amphibole may have contributed to the change in stability.     

Stability range and decomposition of potassic richterite and phlogopite end members at 5–15 GPa

Summary The phase relations of K-richterite, KNaCaMg₅Si₈O₂₂(OH)₂, and phlogopite, K₃Mg₆ Al₂Si₆O₂₀(OH)₂, have been investigated at pressures of 5–15 GPa and temperatures of 1000–1500 °C. K-richterite is stable to about 1450 °C at 9–10 GPa, where the dp/dT-slope of the decomposition curve changes from positive to negative. At 1000 °C the alkali-rich, low-Al amphibole is stable to more than 14 GPa. Phlogopite has a more limited stability range with a maximum thermal stability limit of 1350 °C at 4–5 GPa and a pressure stability limit of 9–10 GPa at 1000 °C. The high-pressure decomposition reactions for both of the phases produce relatively small amounts of highly alkaline water-dominated fluids, in combination with mineral assemblages that are relatively close to the decomposing hydrous phase in bulk composition. In contrast, the incongruent melting of K-richterite and phlogopite in the 1–3 GPa range involves a larger proportion of hydrous silicate melts. The K-richterite breakdown produces high-Ca pyroxene and orthoenstatite or clinoenstatite at all pressures above 4 GPa. At higher pressures additional phases are: wadeite-structured K₂Si^VISi^IV ₃O₉ at 10 GPa and 1500 °C, wadeite-structured K₂Si^VISi^IV ₃O₉ and phase X at 15 GPa and 1500 °C, and stishovite at 15 GPa and 1100 °C. The solid breakdown phases of phlogopite are dominated by pyrope and forsterite. At 9–10 GPa and 1100–1400 °C phase X is an additional phase, partly accompanied by clinoenstatite close to the decomposition curve. Phase X has variable composition. In the KCMSH-system (K₂CaMg₅Si₈O₂₂(OH)₂) investigated by Inoue et al. (1998) and in the KMASH-system investigated in this report the compositions are approximately K₄Mg₈Si₈O₂₅(OH)₂ and K_3.7Mg_7.4Al_0.6Si_8.0O₂₅(OH)₂, respectively. Observations from natural compositions and from the phlogopite-diopside system indicate that phlogopite-clinopyroxene assemblages are stable along common geothermal gradients (including subduction zones) to 8–9 GPa and are replaced by K-richterite at higher pressures. The stability relations of the pure end member phases of K-richterite and phlogopite are consistent with these observations, suggesting that K-richterite may be stable into the mantle transition zone, at least along colder slab geotherms. The breakdown of moderate proportions of K-richterite in peridotite in the upper part of the transition zone may be accompanied by the formation of the potassic and hydrous phase X. Additional hydrogen released by this breakdown may dissolve in wadsleyite. Therefore, very small amounts of hydrous fluids may be released during such a decomposition. Received April 10, 2000; revised version accepted November 6, 2000     

Uvarovite: Stability of uvarovite-andradite solid solutions at low pressure

Uvarovite (Ca₃Cr₂Si₃O₁₂) forms a complete solid solution series with andradite (Ca₃Fe ₂ ⁺³ Si₃O₁₂) below 1,137±5 ° C at a total pressure of 1 atm. Pure uvarovite decomposes to pseudowollastonite (CaSiO₃)+eskolaite (Cr₂O₃) at 1,385 ± 10 ° C. The incorporation of Ca₃Fe ₂ ⁺³ Si₃O₁₂ component in the uvarovite structure lowers the thermal stability of the garnet. The breakdown assemblage is garnet_ss (Ca₃(Cr,Fe⁺³ ₂)Si₃O₁₂)+pseudowollastonite (CaSiO₃)+hemeskolaite_ss(Cr,Fe⁺³O₃). Pure andradite decomposes to pseudowollastonite (CaSiO₃)+hematite (Fe₂O₃) at 1,137±5 °C. Andradite thermal stability is increased by incorporation of Ca₃Cr₂Si₃O₁₂ component by 248 °C.At 1,264±5 °C pseudowollastonite+hematite react to liquid defining a thermal minimum of the CaSiO₃-Cr₂O₃-Fe₂O₃ ternary system. This minimum is located at about 64.5 wt.-% CaSiO₃, 0.5 wt.-% Cr₂O₃, and 35.0 wt.-% Fe₂O₃. Uvarovite and andradite bulk compositions start to melt at 1,420 °C and 1,265 ±5 °C, respectively.The unit-cell parameter for uvarovite is 11.999 (2) Å, the refractive index 1.866 (2). The substitution of Cr⁺³ by Fe⁺³ increases a and n almost linearly toward the andradite end member which displays a unit-cell parameter of 12.059 (3) Å and a refractive index of 1.887 (2).     

Stability of wadeite (Zr2K4Si6O18) under upper mantle conditions: Petrological implications

Wadeite of composition Zr₂K₄Si₆O₁₈, synthesized at 1 atm, is stable between 12–25 kb at 800 °–1,250 ° C; conditions appropriate to those of partial melting of an anomalous K-enriched upper mantle. If published hypotheses for the generation of high potash mafic to ultramafic lavas based on partial melting of such an anomalous mantle are correct, wadeite is a possible K-bearing mineral, in addition to phlogopide and K-richterite, stable under mantle conditions. The restricted occurrence of wadeite to rocks of West Kimberley, Australia and Leucite Hills, Wyoming is believed to be due to their high K/Al and Zr contents relative to other high potash rocks. The cell constants of wadeite of Zr₂K₄Si₆O₁₈ composition are in agreement with those of natural Zr-rich wadeite and with the values predicted from synthetic wadeites with smaller tetravalents ions in the Zr site.     

Synthesis and stability of deerite,Fe 12 2+ Fe 6 3+ [Si12O40](OH)10, and Fe3+⇋Al3+ substitutions at 15–28 kb

Deerite, Fe ₁₂ ²⁺ Fe ₆ ³⁺ [Si₁₂O₄₀](OH)₁₀, thus far known from ten localities in glaucophane schist terranes, was synthesized at water pressures of 20–25 kb and temperatures of 550–600 °C under the of the Ni/NiO buffer. The X-ray powder diagram, lattice constants and infrared spectrum of the synthetic phase are closely similar to those of the natural mineral. A solid solution series extends from this ferri-deerite end member to some 20 mole % of a hypothetical alumino-deerite, Fe ₁₂ ²⁺ Al ₆ ³⁺ [Si₁₂O₄₀](OH)₁₀. The upper temperature breakdown of ferri-deerite to the assemblage ferrosilite +magnetite+quartz+water occurs at about 490 °C at 15 kb, and 610 °C at 25 kb fluid pressure for the of the Ni/NiO buffer. Extrapolation of these data to lower water pressures indicates that deerite can be a stable mineral only in very low-temperature, high-pressure environments.     

Synthesis and stability of micas in the system K2O-MgO-SiO2-H2O and their relations to phlogopite

A series of alumina-free micas was synthesized hydrothermally in the potassium-poor portion of the system K₂O-MgO-SiO₂-H₂O. One end member of this series has the composition KMg_2.5[Si₄O₁₀](OH)₂, which, because of its octahedral occupancy, is intermediate between the dioctahedral and trioctahedral micas.From this end member a series of mica solid solutions extends towards more Mg-rich compositions. Single phase micas were obtained along the substitution line 2Mg for Si which appears to involve incorporation of part of the Mg in tetrahedral sites. It leads to a theoretical end member with a structural formula KMg₃[Si_3.5Mg_0.5O₁₀](OH)₂. Solid solutions containing up to 75 mole % of this theoretical end member could be synthesized. The observed densities, water contents, and a one-dimensional Fourier synthesis are consistent with the assumed substitution.At 1 kb fluid pressure and 620° C the Si-rich end member KMg_2.5[Si₄O₁₀](OH)₂ decomposes to a more Mg-rich mica, the roedderite phase K₂Mg₅Si₁₂O₃₀, liquid, and H₂O-rich vapor. With increasing Mg-content the thermal stability of the mica solid solutions increases up to 860°C at a composition of about K₂O·6.2MgO·7.4SiO₂·2H₂O, i.e. KMg_2.8[Si_3.7Mg_0.3O₁₀](OH)₂. This mica disintegrates directly into forsterite + liquid + H₂O-rich vapor. The mica phase richest in Mg with a composition of about K₂O·6.5MgO·7.25SiO₂·2H₂O, i.e. KMg_2.875 [Si_3.625Mg_0.375O₁₀](OH)₂, breaks down at 765° C into forsterite, a more Si-rich mica, liquid, and H₂O-rich vapor.This binary series of alumina-free micas forms a complete series of ternary solid solutions with normal phlogopite, KMg₃[Si₃AlO₁₀](OH)₂. Analyses of some natural phlogopites showing Si in excess of 3.0 (up to 3.18) per formula unit can be explained through this ternary miscibility range.     

Experimental studies to 10 kb of the bulk composition tremolite50-tschermakite50+excess H2O

Phase relations for the magnesio-hornblende bulk composition, 2 CaO·4 MgO·Al₂O₃·7 SiO₂+ excess H₂O, have been investigated to 10 kb employing hydrothermal and piston-cylinder techniques. The low-temperature limit of amphibole in this system lies at 519° C, 1,000 bars, 541° C, 2,000 bars, and 718° C, 10 kb. The low-T assemblage consists of an+chl+di+tc(+f), and is related to the adjacent high-T equilibrium assemblage, amph+an+chl+f, by the solid-solid reaction (A): 2 di+tc=tr. Small amounts of aluminum, hypothesized to be preferentially dissolved in the cpx (and in the tc) relative to amph, may account for the broad P-T stability range of the di+tc assemblage in the synthetic work relative to systems involving stoichiometric tr, Ca₂Mg₅Si₈O₂₂(OH)₂, such as are common in natural, Al-poor calc-silicate parageneses. Alternatively, the low-temperature assemblage produced in the experiments may be metastable. For the investigated bulk composition, synthetic tremolitic-cummingtonitic amphibole contains relatively modest amounts of ts, Ca₂Mg₃Al₂ ^IVSi₆-Al₂ ^IVO₂₂(OH)₂; at pressures of 1,000–3,000 bars, solid solution extends from near tremolite only to about cu₁₁tr₆₉ts₂₀, analogous to most analyzed natural magnesio-hornblendic specimens. At 10 kb fluid pressure, the solid solution reaches approximately cu₀₆tr₅₃ts₄₁ for the investigated bulk composition, and appears to be virtually independent of temperature. Amphibole and 14 Å chl react within the amphibole stability field, along curve (B), at about 704° C and 2,000 bars, to produce an, en, fo and f (H=40.9 kcal/ mole); at pressures greater than approximately 7kb, due to the incompatibility of an and fo, the higher temperature assemblage consists of amph, an, en, sp and f. Above P _fluid– T curve (B), the amphibole coexists with an+en+fo+f at low pressures; at higher pressures, the amphibole, which is in equilibrium with an+en+sp+f, is relatively more aluminous. The high-T stability limit of aluminous tr+fo lies approximately 20–25° C below the dehydration curve for stoichiometric tremolite on its own bulk composition. Reaction (C), tr+fo=2 di+5 en+f (H = 39.4 kcal/mole), produces an+di+en+f, the highest temperature subsolidus assemblage investigated for the tr₅₀ts₅₀ bulk composition. Hydrous melt is encountered at temperatures at least as low as 900° C at 10 kb, and at that fluid pressure coexists with amphibole over an interval of more than 60° C. Limited solid solution observed between tr and ts in nature (tr_100-70) is accounted for by the restricted range of amphibole compositions produced in the present study. Such amphiboles, moreover, appear to have both high- and low-temperature stability limits, as demonstrated by the experimental results.Institute of Geophysics and Planetary Physics Publication No. 2811     

Experimental determination of pargasite stability relations in the presence of orthopyroxene

The stability and partial melting of synthetic pargasite in the presence of enstatitic orthopyroxene (opx), forsterite, diopsidic clinopyroxene (cpx), plagioclase (An₅₀), and water has been studied in the range of 0.4–6.0 kb and 750–1000°C in the system Na₂O-CaO-MgO-Al₂O₃-SiO₂-H₂O with a fixed bulk composition of pargasite+5 opx. The addition of orthopyroxene effectively reduces the stability field of pargasite by approximately 200°C at 1 kb. The invariant point involving pargasite coexisting with water-saturated liquid and anhydrous phase shifts from about 0.85 kb and 1025°C to 2.5±0.5 kb and 925±25°C with the addition of opx. Based on the solidus mineral assemblage and direct chemical analysis of quenched glass, the vapor-saturated liquid has a composition close to that of intermediate plagioclase. A layered silicate, interpreted to be Na-phlogopite, has an upper-thermal stability that nearly equals that of pargasite in the field of partial melting and coexists with liquid, pargasite, cpx, and forsterite at 6 kb, 1000°C. These results support the hypothesis that mantle metasomatism could involve formation of pargasitic amphibole from a silicate melt at depths as shallow as 8–10 km.     

An experimental investigation on the P-T stability of Mg-staurolite in the system MgO-Al2O3-SiO2-H2O

The pressure-temperature stability field of Mg-staurolite, ideally Mg₄Al₁₈Si₈O₄₆(OH)₂, was bracketed for six possible breakdown reactions in the system MgO-Al₂O₃-SiO₂-H₂O (MASH). Mg-staurolite is stable at water pressures between 12 and 66 kbar and temperatures of 608–918 °C, requiring linear geotherms between 3 and 18 °C/km. This phase occurs in rocks that were metamorphosed at high-pressure, low-temperature conditions, e.g. in subducted crustal material, provided they are of appropriate chemical composition. Mg-staurolite is formed from the assemblage chlorite + kyanite + corundum at pressures <24 kbar, whereas at pressures up to 27 kbar staurolite becomes stable by the breakdown of the assemblage Mg-chloritoid + kyanite + corundum. Beyond 27 kbar the reaction Mg-chloritoid + kyanite + diaspore = Mg-staurolite + vapour limits the staurolite field on its low-temperature side. The upper pressure limit of Mg-staurolite is marked by alternative assemblages containing pyrope + topaz-OH with either corundum or diaspore. At higher temperatures Mg-staurolite breaks down by complete dehydration to pyrope + kyanite + corundum and at pressures below 14 kbar to enstatite + kyanite + corundum. The reaction curve Mg-staurolite = talc + kyanite + corundum marks the low-pressure stability of staurolite at 12 kbar. Mg-staurolite does not coexist with quartz because alternative assemblages such as chlorite-kyanite, enstatite-kyanite, talc-kyanite, pyrope-kyanite, and MgMgAl-pumpellyite-kyanite are stable over the entire field of Mg-staurolite. Received: 16 April 1997 / Accepted: 24 September 1997     

Eifelite,KNa3Mg4Si12O30, a new mineral of the osumilite group with octahedral sodium

Eifelite of variable composition is uniaxial positive withn ₀ near 1.543 andn _e near 1.544, a between 10.14 and 10.15 Å, andc about 14.22 Å, space groupP 6/m 2/c 2/c. There is a complete series of solid solution between the eifelite end member KNa₃Mg₄Si₁₂O₃₀ and roedderite, KNaMg₅Si₁₂O₃₀, following the 2 Na?Mg substitution. Both eifelite and roedderite have milarite-type structures, but Na is always in six-coordinated sites: In roedderite Na occupies solely a newly defined B′^[6]-position which is slightly displaced alongc from the ideal B_[9]-position lying on the (001/2)-mirror plane in K₂Mg₅Si₁₂O₃₀. In eifelite Na is located both inB′^[6] and in theA _[6]-positions, where it partially replaces Mg. Eifelite has the highest cation occupancy of all osumilite group minerals known thus far. Both eifelite and roedderite occur in vesicles of contact metamorphosed basement xenoliths ejected with the leucite tephrite lava of the Quaternary Bellerberg volcano in the Eifel, West Germany. They are considered to be precipitates from highly alkaline, MgSi-rich, but Al-deficient gas phases that originated through interaction of gaseous igneous differentiates with the xenoliths.     

Melting and subsolidus reactions in the system K2O-CaO-Al2O3-SiO2-H2O

Beginning of melting and subsolidus relationships in the system K₂O-CaO-Al₂O₃-SiO₂-H₂O have been experimentally investigated at pressures up to 20 kbars. The equilibria discussed involve the phases anorthite, sanidine, zoisite, muscovite, quartz, kyanite, gas, and melt and two invariant points: Point [Ky] with the phases An, Or, Zo, Ms, Qz, Vapor, and Melt; point [Or] with An, Zo, Ms, Ky, Qz, Vapor, and Melt.The invariant point [Ky] at 675° C and 8.7 kbars marks the lowest solidus temperature of the system investigated. At pressures above this point the hydrated phases zoisite and muscovite are liquidus phases and the solidus temperatures increase with increasing pressure. At 20 kbars beginning of melting occurs at 740 °C. The solidus temperatures of the quinary system K₂O-CaO-Al₂O₃-SiO₂-H₂O are almost 60° C (at 20 kbars) and 170° C (at 2kbars) below those of the limiting quaternary system CaO-Al₂O₃-SiO₂-H₂O.The maximum water pressure at which anorthite is stable is lowered from 14 to 8.7 kbars in the presence of sanidine. The stability limits of anorthite+ vapor and anorthite+sanidine+vapor at temperatures below 700° C are almost parallel and do not intersect. In the wide temperature — pressure range at pressures above the reaction An+Or+Vapor = Zo+Ms+Qz and temperatures below the melting curve of Zo+Ms+Ky+Qz+Vapor, the feldspar assemblage anorthite+sanidine is replaced by the hydrated phases zoisite and muscovite plus quartz. CaO-Al₂O₃-SiO₂-H₂O. Knowledge of the melting relationships involving the minerals zoisite and muscovite contributes to our understanding of the melting processes occuring in the deeper parts of the crust. Beginning of melting in granites and granodiorites depends on the composition of plagioclase. The solidus temperatures of all granites and granodiorites containing plagioclases of intermediate composition are higher than those of the Ca-free alkali feldspar granite system and below those of the Na-free system discussed in this paper.The investigated system also provides information about the width of the P-T field in which zoisite can be stable together with an Al₂SiO₅ polymorph plus quartz and in which zoisite plus muscovite and quartz can be formed at the expense of anorthite and potassium feldspar. Addition of sodium will shift the boundaries of these fields to higher pressures (at given temperatures), because the pressure stability of albite is almost 10kbars above that of anorthite. Assemblages with zoisite+muscovite or zoisite+kyanite are often considered to be products of secondary or retrograde reactions. The P-T range in which hydration of granitic compositions may occur in nature is of special interest. The present paper documents the highest temperatures at which this hydration can occur in the earth's crust.     

The hydrothermal synthesis of low albite

Glasses on the join NaAlSi₃O₈-Na₂Si₂O₅ were devitrified hydrothermally at pressures of 1 to 10 kb and at temperatures in the range 200 to 700° C to define more adequately the physical and chemical environments which favor crystallization of the fully ordered polymorph of albite. The presence of Na₂Si₂O₅ allows the synthesis of low albite with an obliquity of 1.140° (Cu K radiation) in runs of relatively short duration. The effect of increasing total pressure and time, and of decreasing temperature and amount of water down to critical values, is to favor the synthesis of ordered albite. Excess sodium is the chemical constituent necessary for ordering to proceed at a relatively rapid rate; this rate seems to vary with the ratio aNa⁺/aH⁺, and hence with the peralkalinity of the aqueous fluid attending recrystallization. The chemical environment of recrystallization thus seems as important as temperature in determining the ultimate degree of Si-Al order attained in albite.This paper is taken from a Ph. D. dissertation submitted to the Department of Geology, Stanford University, Stanford, California.     

Stability of manganocordierite and related phase equilibria in part of the system MnO-Al2O3-SiO2-H2O

The pressure temperature stability of the phase Mn-cordierite hitherto not recorded as a mineral has been determined at temperatures ranging from 400° C up to the melting mainly using standard hydrothermal techniques at the oxygen fugacities provided by the buffering power of the bomb walls. Manganocordierite is a pronounced low-pressure phase with a maximum pressure stability of about 1 kb near 400° C and decreasing pressure limits at higher temperatures. Throughout the temperature range investigated the stable high-pressure breakdown assemblage of Mn-cordierite is spessartine, an Al-silicate, and a SiO₂-polymorph. Due to the variable water contents of Mn-cordierite and spessartine there is a pronounced curvature in the negative dP/dT-slope of the requisite upper pressure breakdown curve of Mn-cordierite. Only theoretical deductions were possible concerning the stable hydrous low-temperature breakdown assemblage of Mn-cordierite below about 400° C.The manganocordierites synthesized are orthorhombic low-cordierites with distortion indices increasing with temperature, water pressure, and duration of heating. Their mean refractive indices increase with rising contents of absorbed water in the structural channels. Based on experiments with natural material the upper temperature stability limit of the mineral carpholite must lie at temperatures below about 400° C for water pressures up to 2.5 kb.The absence of Mn-cordierite from natural rocks studied thus far cannot be explained on chemical grounds, but must be due to its narrow pressure temperature stability range. The phase may yet be discovered as a mineral in manganiferous metasediments formed by lowpressure contact metamorphism.     

Phase equilibria in the system K2O-FeO-MgO-Al2O3-SiO2-H2O-CO2 and the stability limit of stilpnomelane in metamorphosed Precambrian iron-formations

The phase relations of Al- and Fe-bearing silicates in the system K₂O-FeO-MgO-Al₂O₃-SiO₂-H₂O-CO₂, in the presence of quartz and magnetite, are discussed on the basis of mineralogic and petrologic data from Precambrian iron-formations and blueschist facies meta-ironstone from the Franciscan Formation, California. These relations allow an estimation of the physiochemical conditions during low-grade metamorphism of iron-formations. Petrologic data together with available experimental and predicted thermodynamic data on the associated minerals place the upper stability limit of stilpnomelane in iron-formations at about 430–470° C and 5–6 kilobars. Fe-end member stilpnomelane can persist to a maximum temperature of 500° C and pressures up to 6–7 kilobars, although it is unlikely to occur in metamorphosed iron-formations. In iron-formation occurrences the stilpnomelane stability field is bordered by four equilibrium reactions with the assemblages stilpnomelane-zussmanite-chlorite-minnesotaite, stilpnomelane-zussmanite-chlorite-grunerite, stilpnomelane-biotite-chlorite-grunerite, and stilpnomelane-biotite-almandine-grunerite. The stability field is reduced by increasing X(CO₂) and X _Mg ^Stil , and is also a function of a(K ⁺)/ a(H ⁺) in the metamorphic fluid. If the value of a(K ⁺)/ a(H ⁺) is smaller than that defined by the above assemblages, stilpnomelane decomposes to chlorite, but if larger, it is replaced by biotite. At pressures less than 4 kilobars, the zussmanite field is restricted to a very high value of a(K ⁺)/a(H ⁺) (> 5.0 in log units at 1.0 kilobar) where iron-formation assemblages are not stable.     

Effect of KCl on melting in the Mg<Subscript>2</Subscript>SiO<Subscript>4</Subscript>–MgSiO<Subscript>3</Subscript>–H<Subscript>2</Subscript>O system at 5 GPa

To examine the effect of KCl-bearing fluids on the melting behavior of the Earth’s mantle, we conducted experiments in the Mg₂SiO₄–MgSiO₃–H₂O and Mg₂SiO₄–MgSiO₃–KCl–H₂O systems at 5 GPa. In the Mg₂SiO₄–MgSiO₃–H₂O system, the temperature of the fluid-saturated solidus is bracketed between 1,200–1,250°C, and both forsterite and enstatite coexist with the liquid under supersolidus conditions. In the Mg₂SiO₄–MgSiO₃–KCl–H₂O systems with molar Cl/(Cl + H₂O) ratios of 0.2, 0.4, and 0.6, the temperatures of the fluid-saturated solidus are bracketed between 1,400–1,450°C, 1,550–1,600°C, and 1,600–1,650°C, respectively, and only forsterite coexists with liquid under supersolidus conditions. This increase in the temperature of the solidus demonstrates the significant effect of KCl on reducing the activity of H₂O in the fluid in the Mg₂SiO₄–MgSiO₃–H₂O system. The change in the melting residues indicates that the incongruent melting of enstatite (enstatite = forsterite + silica-rich melt) could extend to pressures above 5 GPa in KCl-bearing systems, in contrast to the behavior in the KCl-free system.     

Experimental study of the K2ZrSi3O9 (wadeite)–K2TiSi3O9 and K2(Zr,Ti)Si3O9–phlogopite systems at 2–3 GPa

Experiments ranging from 2 to 3 GPa and 800 to 1300 °C and at 0.15 GPa and 770 °C were performed to investigate the stability and mutual solubility of the K₂ZrSi₃O₉ (wadeite) and K₂TiSi₃O₉ cyclosilicates under upper mantle conditions. The K₂ZrSi₃O₉–K₂TiSi₃O₉ join exhibits complete miscibility in the P–T interval investigated. With increasing degree of melting the solid solution becomes progressively enriched in Zr, indicating that K₂ZrSi₃O₉ is the more refractory end member. At 2 GPa, in the more complex K₂ZrSi₃O₉–K₂TiSi₃O₉–K₂Mg₆Al₂Si₆O₂₀(OH)₄ system, the presence of phlogopite clearly limits the extent of solid solution of the cyclosilicate to more Zr-rich compositions [Zr/(Zr + Ti) > 0.85], comparable to wadeite found in nature, with TiO₂ partitioning strongly into the coexisting mica and/or liquid. However, at 1200 °C, with increasing pressure from 2 to 3 GPa, the partitioning behaviour of TiO₂ changes in favour of the cyclosilicate, with Zr/(Zr + Ti) of the K₂(Zr,Ti)Si₃O₉ phase decreasing from ∼0.9 to ∼0.6. The variation in the Ti content of the coexisting phlogopite is related to its degree of melting to forsterite and liquid, following the major substitution ^VITi+^VI□=2^VIMg. Received: 26 January 1999 / Accepted: 10 January 2000     

Cymrite: new occurrence and stability

The rare mineral cymrite, BaAl₂Si₂O₈·H₂O, was discovered in Nevada in a Cambrian bedded barite sequence that exhibits low-grade metamorphism. The mineral occurs exclusively in thin-bedded siliceous rock containing anhedral pyrite crystals up to 1 cm. Cymrite forms rectangular grains ca 40 m across, distributed throughout the chalcedonic quartz matrix. An SEM image of one such blocky grain shows that it is filled by tiny aggregates, instead of a single crystal of cymrite. This cymrite may have replaced a pre-existing rectangular mineral, most likely barite. The Nevada occurrence of cymrite prompted a restudy of its stability relations. Conventional hydrothermal techniques were adopted in the experimental work with run durations up to 7 months. The univariant curve for the dehydration reaction: BaA1₂Si₂O₈· H₂O -BaA1₂Si₂O₈ +H₂O passes the following reversed brackets: 300–315° C at 3 kbar, 290–300° C at a 2 kbar, 270–285° C at 1 kbar, and 240–270° C at 0.5 kbar. These results indicate that cymrite can be stable at much lower pressures than those previously reported. The replacement of barite by cymrite was experimentally demonstrated with an alkaline solution as depicted by the reaction: BaSO₄+2OH^-+A1₂O₃-2SiO₂=BaA1₂Si₂O₈·H₂O+SO ₄ ² Such replacement failed to take place when an acidic solution was used instead.     

Experimental study of aluminum speciation in fluoride-rich supercritical fluids

The solubility of the albite-paragonite-quartz mineral assemblage was measured as a function of NaCl and fluorine concentration at 400°C, 500 bars and at 450°C, 500 and 1000 bars. Decreasing Al concentrations with increasing NaCl molality in F-free fluids of low salinity (mNaCl < 0.01) demonstrates that Al(OH)₄⁻ dominates Al speciation and is formed according to the reaction 0.5 NaAl₃Si₃O₁₂H_2(cr)+2 H₂O = 0.5 NaAlSi₃O_8(cr)+Al(OH)₄⁻+H⁺. Log K results for this reaction are −11.28 ± 0.10 and −10.59 ± 0.10 at 400°C, 500 bars and 450°C, 1000 bars, respectively. Upon further salinity increase, Al concentration becomes constant (at 400°C, 500 bars) or even rises (at 450°C, 1000 bars). The observed Al behavior can be explained by the formation of NaAl(OH)₄⁰_(aq) or NaAl(OH)₃Cl_(aq)⁰. The calculated constant for the reaction Al(OH)₄⁻+Na⁺=NaAl(OH)₄⁰_(aq) expressed in log units is equal to 2.46 and 2.04 at 400°C, 500 bars and 450°C, 1000 bars, respectively. These values are in good agreement with the predictions given in Diakonov et al. (1996). Addition of fluoride at m(NaCl) = const = 0.5 caused a sharp increase in Al concentration in equilibrium with the albite-paragonite-quartz mineral assemblage. As fluid pH was also constant, this solubility increase indicates strong aluminum-fluoride complexation with the formation of NaAl(OH)₃F_(aq)⁰ and NaAl(OH)₂F₂⁰_(aq), according to 0.5 NaAl₃Si₃O₁₂H_2(cr)+Na⁺+HF_(aq)⁰+H₂O = 0.5 NaAlSi₃O_8(cr)+ NaAl(OH)₃F_(aq)⁰+H⁺, log K = −5.17 and −5.23 at 400°C and 450°C, 500 bars, respectively, and 0.5 NaAl₃Si₃O₁₂H_2(cr)+Na⁺+2 HF_(aq)⁰ = 0.5 NaAlSi₃O_8(cr)+NaAl(OH)₂F₂⁰_(aq)+H⁺, log K = −2.19 and −1.64 at the same P-T conditions. It was found that temperature increase and pressure decrease promote the formation of Na-Al-OH-F species. Stability of NaAl(OH)₂F₂⁰_(aq) in low-density fluids also increases relative to NaAl(OH)₃F_(aq)⁰. These complexes, together with Al(OH)₂F_(aq)⁰ and AlOHF₂⁰_(aq), whose stability constants were calculated from the corundum solubility measured by Soboleva and Zaraisky (1990) and Zaraisky (1994), are likely to dominate Al speciation in metamorphic fluids containing several ppm of fluorine.