Internally-Consistent Thermodynamic Data for Minerals in the System Na2O-K2O-CaO-MgO-FeO-Fe2O3-Al2O3-SiO2-TiO2-H2O-CO2

Internally consistent standard state thermodynamic data arepresented for 67 minerals in the system Na₂O-K₂O-CaO-MgO-FeO-Fe₂O₃-Al₂O₃-SiO₂-TiO₂-H₂O-CO₂.The method of mathematical programming was used to achieve consistencyof derived properties with phase equilibrium, calorimetric,and volumetric data, utilizing equations that account for thethermodynamic consequences of first and second order phase transitions,and temperature-dependent disorder. Tabulated properties arein good agreement with thermophysical data, as well as beingconsistent with the bulk of phase equilibrium data obtainedin solubility studies, weight change experiments, and reversalsinvolving both single and mixed volatile species. The reliabilityof the thermodynamic data set is documented by extensive comparisons(Figs. 4–45) between computed equilibria and phase equilibriumdata. The high degree of consistency obtained with these diverseexperimental data gives confidence that the refined thermodynamicproperties should allow accurate prediction of phase relationshipsamong stoichiometric minerals in complex chemical systems, andprovide a reasonable basis from which activity models for mineralsmay be derived.     

Siderit-Magnesit-Mischkristallbildung im system Mg2+-Fe2+-CO 3 2− -Cl 2 2− -H2O

The formation of the solid solution series MgCO₃-FeCO₃ in the system Mg²⁺-Fe²⁺-CO ₃ ^2? -Cl ₂ ^2? -H₂O has been investigstad between 200° C and 500° C. The experimental results show that the composition of any of these carbonates strongly depends on the temperature: At high temperatures mixed crystals rich in MgCO₃ are formed and low temperatures lead to the formation of FeCO₃-rich carbonates. Thus, at 200° C a Fe-poor (Mg-rich) solution is in equilibrium with a Fe-rich carbonate. At temperatures higher than 350° C a Fe-rich (Mg-poor) solution coexists with a Fe-poor (Mg-rich) solid phase; see Fig. 1. At 350° C a solution with a mole fraction^mFe²⁺/(^mFe²⁺+^mMg²⁺) of 0.20 leads to the formation of magnesite very poor in Fe, whereas at 250° C the same solution is in equilibrium with sideroplesit, containing 80 Mol-% FeCO₃, see Figs. 2 and 3. The importance of the experimental results for the formation of deposits of magnesite and siderite is discussed.     

Electrochemical Evidence for Pentasulfide Complexes with Mn2+, Fe2+, Co2+, Ni2+, Cu2+ and Zn2+

A series of stable pentasulfide complexes of the common base metals, Mn, Fe, Co, Ni, Cu and Zn exist in aqueous solutions at ambient temperatures. Pure sodium pentasulfide was prepared and reacted with the divalent cations of Mn, Fe, Co, Ni, Cu and Zn in aqueous solution at ambient temperature. The S52- complexes were found to exist as determined by voltammetric methods.Pentasulfide complexes with compositions assigned as [M(1-S5)] and [M2(- S5)]2+ occur for Mn, Fe, Co and Ni where only one terminal S atom in the S52- binds to one metal (1 = mono-dentate ligand or M-S-S-S-S-S, = ligand bridging two metal centers or M-S-S-S-S-S-M). Conditional stability constants are similar for all four metals with log 1 between 5.3 and 5.7 and log 2 between 11.0 and 11.6. The constants for these pentasulfide complexes are similar to the tetrasulfide complexes and are approximately 0.4–0.8 log units higher than for comparable bisulfide complexes [M(SH)]+ as expected based on the higher nucleophilicity of S52- compared to HS-. Voltammetric results indicate that these are labile complexes.As with the bisulfide and tetrasulfide complexes, Zn(II) and Cu(II) are chemically distinct from the other metals. Zn(II) reacts with pentasulfide to form a stable monomeric pentasulfide chelate, [Zn(1-S5)] with log = 8.7. Cu(II) reacts with pentasulfide to form a complex with the probable stoichiometry [Cu(S5)]2 with log estimated to be 20.2. As with the other four metals, these complexes are comparable with the tetrasulfide complexes. Discrete voltammetric peaks are observed for these complexes and indicate they are electrochemically inert to dissociation. Reactions of Zn(II) and Cu(II) also lead to significant breakup of the polysulfide.The relative strength of the complexes is Cu > Zn > Mn, Fe, Co, Ni. Cu displaces Zn from [Zn(1- S5)] and both Cu and Zn displace Mn, Fe, Co and Ni from their pentasulfide complexes.     

Single crystal raman studies of pyrite-type RuS2, RuSe2, OsS2, OsSe2, PtP2, and PtAs2

Single crystal Raman spectra of pyrite-type RuS₂, RuSe₂, OsS₂, OsSe₂, PtP₂, and PtAs₂ are presented and discussed with reference to the energies of the X-X stretching modes _x-x (A _g, F _g) and the X₂ librations (E, 2F_g). The main results obtained are (i) strong Raman resonance effects, (ii) different sequences for _x-x (A _g) and (E _g), i.e., R_{x_2 } $$ " align="middle" border="0"> for PtP₂ and PtAs₂ and R_{x_2 } $$ " align="middle" border="0"> for OsS₂, owing to the interplay of intraionic and interionic lattice forces, (iii) greater strengths for the intraionic P-P and As-As bonds compared to the S-S and Se-Se bonds, respectively, and (iv) a strong influe_gnce of the metal ions on the strength of the X-X bonds.This is contribution LXI of a series of papers on lattice vibration spectra     

Gehlenite stability in the system CaO-Al2O3-SiO2-H2O-CO2

P, T, \(X_{{\text{CO}}_{\text{2}} }\) relations of gehlenite, anorthite, grossularite, wollastonite, corundum and calcite have been determined experimentally at P _f =1 and 4 kb. Using synthetic starting minerals the following reactions have been demonstrated reversibly

1. 2 anorthite+3 calcite=gehlenite+grossularite+3 CO₂.
2. anorthite+corundum+3 calcite=2 gehlenite+3 CO₂.
3. 3anorthite+3 calcite=2 grossularite+corundum+3CO₂.
4. grossularite+2 corundum+3 calcite=3 gehlenite+3 CO₂.
5. anorthite+2 calcite=gehlenite+wollastonite+2CO₂.
6. anorthite+wollastonite+calcite=grossularite+CO₂.
7. grossularite+calcite=gehlenite+2 wollastonite+CO₂.

In the T, \(X_{{\text{CO}}_{\text{2}} }\) diagram at P _f =1 kb two isobaric invariant points have been located at 770±10°C, \(X_{{\text{CO}}_{\text{2}} }\) =0.27 and at 840±10°C, \(X_{{\text{CO}}_{\text{2}} }\) =0.55. Formation of gehlenite from low temperature assemblages according to (4) and (2) takes place at 1 kb and 715–855° C, \(X_{{\text{CO}}_{\text{2}} }\) =0.1–1.0. In agreement with experimental results the formation of gehlenite in natural metamorphic rocks is restricted to shallow, high temperature contact aureoles.     

Heat capacity of minerals in the system Na2O-K2O-CaO-MgO-FeO-Fe2O3-Al2O3-SiO2-TiO2-H2O-CO2: representation,estimation, and high temperature extrapolation

A revised equation is proposed to represent and extrapolate the heat capacity of minerals as a function of temperature: C _P=k₀+k₁ T ^–0.5+k₂ T ^–2+k₃ T ^–3 (where k₁, k₂0).This equation reproduces calorimetric data within the estimated precision of the measurements, and results in residuals for most minerals that are randomly distributed as a function of temperature. Regression residuals are generally slightly greater than those calculated with the five parameter equation proposed by Haas and Fisher (1976), but are significantly lower than those calculated with the three parameter equation of Maier and Kelley (1932).The revised equation ensures that heat capacity approaches the high temperature limit predicted by lattice vibrational theory (C _P=3R+²VT/). For 16 minerals for which and have been measured, the average C _Pat 3,000 K calculated with the theoretically derived equation ranges from 26.8±0.8 to 29.3±1.9 J/(afu·K) (afu = atoms per formula unit), depending on the assumed temperature dependence of . For 91 minerals for which calorimetric data above 400 K are available, the average C _Pat 3,000 K calculated with our equation is 28.3±2.0 J/(afu·K). This agreement suggests that heat capacity extrapolations should be reliable to considerably higher temperatures than those at which calorimetric data are available, so that thermodynamic calculations can be applied with confidence to a variety of high temperature petrologic problems.Available calorimetric data above 250 K are fit with the revised equation, and derived coefficients are presented for 99 minerals of geologic interest. The heat capacity of other minerals can be estimated (generally within 2%) by summation of tabulated oxide component C _Pcoefficients which were obtained by least squares regression of this data base.     

Studies in the system KAlSiO4-BaAl2Si2O8-SiO2-H2O

Various members of the KAlSi₃O₈-BaAl₂Si₂O₈ feldspar series are hydrothermally synthesized. Cellparameters of these are calculated from diffractometer patterns and found to be similar to those of Gay and Roy. A variation diagram is constructed correlating Cn-content and values of Δ_FeKα(2θ₍₁₁₁₎CaF₂—2θ₍₀₀₄₎Fs_ss), which gives $${\text{Mol}}\% {\text{ Cn = 229}}{\text{.83}}\Delta {\text{2}}\theta ---{\text{190}}{\text{.81}}$$ by a least square regression fitting. Phase equilibria relation in the solidus-liquidus-region for the KAlSi₃O₈-BaAl₂Si₂O₈-H₂O system at 1000 kg/cm² are investigated. It is found to be a case of simple solid solution in a binary system, with reservations at the potassium-rich side of the system. Goranson (1938) gives a temperature of about 1000°C at 1000 kg/cm² \(P_{{\text{H}}_{\text{2}} {\text{O}}} \) for the incongruent melting of sanidine, but the authors prefer a value around 930°C at the same \(P_{{\text{H}}_{\text{2}} {\text{O}}} \) . Reaction products of starting materials on the join KAlSi₂O₆-BaAl₂Si₂O₈ and KAlSiO₄-BaAl₂Si₂O₈ gave no experimental hint for replacement of K⁺ by Ba⁺⁺.     

Calculated Phase Relations in the System NCKFMASH (Na2O-CaO-K2O-FeO-MgO-Al2O3-SiO2-H2O) for High-Pressure Metapelites

Petrogenetic grids in the system NCKFMASH (Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O)and the subsystems NCKMASH and NCKFASH calculated with the softwareTHERMOCALC 3.1 are presented for the P–T range 7–30kbar and 450–680°C, for assemblages involving garnet,chloritoid, biotite, carpholite, talc, chlorite, kyanite, staurolite,paragonite, glaucophane, jadeite, omphacite, diopsidic pyroxene,plagioclase, zoisite and lawsonite, with phengite, quartz/coesiteand H₂O in excess. These grids, together with calculated compatibilitydiagrams and P–T and T–X_Ca and P–X_Ca pseudosectionsfor different bulk-rock compositions, show that incorporationof Ca into the NKFMASH system leads to many of the NKFMASH invariantequilibria moving to lower pressure and/or lower temperature,which results, in most cases, in the stability of jadeite andgarnet being enlarged, but in the reduction of stability ofglaucophane, plagioclase and AFM phases. The effect of Ca onthe stability of paragonite is dependent on mineral assemblageat different P–T conditions. The calculated NCKFMASH diagramsare powerful in delineating the phase equilibria and P–Tconditions of natural pelitic assemblages. Moreover, contoursof the calculated phengite Si isopleths in P–T and P–X_Capseudosections confirm that phengite barometry in NCKFMASH isstrongly dependent on mineral assemblage. KEY WORDS: phase relations; metapelites; NCKFMASH; THERMOCALC; phengite geobarometry     

Phase relations in the systems Ag2S-Cu2S-PbS and Ag2S-Cu2S-Bi2S3 and their mineral assemblages

Phase relations in the ternary systems Ag₂S-Cu₂S-PbS and Ag₂S-Cu₂S-Bi₂S₃ were studied using the silica vacuum technique. In the system Ag₂S-Cu₂S-Bi₂S₃ the phase relations are dominated by join-lines from galena to f.c.c. (Ag_x Cu_2−xS) and b.c.c. (Cu_x Ag_2−xS) at 500°C. With decreasing temperature, galena can coexist with all the phases on the Ag₂S-Cu₂S join. There are six solid solutions, and one new phase, i.e., “C” whose composition is Ag_1.1 Cu_4.8Bi_5.8S₁₂ in the system Ag₂S-Cu₂S-Bi₂S₃ at 500°C. The pavonite (AgBi₃S₅) contains 14 mole% Cu₂S in solid solution, but only 3.0 mole% Ag₂S in CuBi₃S₅ solid solution. The Cu₃Bi₅S₉ ss and wittichenite (Cu₃BiS₃) ss can form join-lines with pavonite as and have the maximum contents of 9.0 and 18 mole% Ag₂S. The most striking feature is the presence of bejaminite as a stable phase with a chemical formula of Ag₂Bi₄S₇ on the Ag₂S-Bi₂S₃ join. AgBiS₂ of the PbS type occupies a fairly large field with a maximum of 23 mole% Cu₂S.     

The stability of merwinite in the system CaO-MgO-SiO2-H2O-CO2 with CO2-poor fluids

The stability of merwinite (Mw) and its equivalent assemblages, akermanite (Ak)+calcite (Cc), diopside (Di)+calcite, and wollastonite (Wo)+monticellite (Mc)+calcite was determined at T=500–900° C and P _f=0.5–2.0 kbar under H₂O–CO₂ fluid conditions with X _{CO 2}=0.5, 0.1, 0.05, and 0.02. Merwinite is stable at P _f=0.5 kbar with T>700° C and X _{CO 2}<0.1. At P _f=2.0 kbar, the assemblage Di+Cc replaces merwinite at all T and X _{CO 2} conditions. At intermediate P _f=1 kbar, the assemblage Ak+Cc is stable above 707° C and Wo+Mc+Cc is stable below 707° C. The univariant curve for the reaction Di+Cc=Wo+Mc+CO₂ is almost parallel to the T axis and shifts to low P _f with increasing X _{CO 2}, with the assemblage Di+Cc on the high-P _f side. The implications of the experimental results in regard to contact metamorphism of limestone are discussed using the aureole at Crestmore, California as an example.     

Ag_2S-Cu_2S-PbS和Ag_2S-Cu_2S-Bi_2S_3体系相关系及相关矿物共生组合研究

本文用抽空石英管法对三元硫化物体系Ag_2S-Cu_2S-PbS和Ag_2S-Cu_2S-Bi_2S_3在500℃的相图进行了研究。 Ag_2S-Cu_2S-PbS体系500℃相关系,受方铅矿和固溶体f.c.c.(Ag_xCu_(2-x)S)、b.c.c.(Cu_xAg_(2-x)S)所控制。在接近PbS-Cu_2S连线处有一液相区。随温度下降,方铅矿可与Cu_2-Ag_2S二元系上所有各相平衡共存。 Ag_2S-Cu_2S-Bi_2S_3体系在500℃时则包含六个固溶体,即块硫铋银矿、铜银铅铋矿、杂硫铋银矿、硫铋铜矿、CuBi_3S_5、Cu_3Bi_5S_9和新合成“C”(Ag_(1.1)Cu_(4.8)Bi_(5.8)S_(12))。最令人感兴趣的是无铜、无铅的铜银铅铋矿(Ag_2Bi_4S_7)合成成功。 以上二个三元系中矿物稳定性及共生关系也根据相图研究结果进行了讨论。     

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.     

Fe2⇄Mg2 and TiAl2⇄MgSi2 exchange reactions between clinopyroxenes and silicate melts

The interdependence of the Fe(Mg)_–1 (e.g., FeO-MgO in silicate melt; CaFeSi₂O₆-CaMgSi₂O₆ in pyroxene) and TiAl₂(MgSi₂)_–1 exchange reactions between silicate melts and coexisting Ca-pyroxene has been examined. High-calcium clinopyroxenes were grown in 1 atmosphere melting and crystallization experiments on rock powders spanning the composition range tholeiite to melilitite (1,0922+Mg²⁺ exchange and suggest that at given values of extent of Fe(Mg)_–1 substitution is strongly coupled with the TiAl₂(MgSi₂)_–1 substitution in pyroxenes near the five-component space CaMg(Si₂O₆-CaFe(Si)₂O₆-CaTi(Al)₂O₆-CaFe(Al,Si)₂O₆-CaAl(Al,Si)₂O₆. The inferred stabilization of Ti in iron-rich relative to magnesium pyroxene is consistent with the operation of Fe²⁺Ti⁴⁺ intervalence charge transfer interactions (e.g., Rossman 1980) and observations on zoning in natural titanaugites (e.g., Tracy and Robinson 1977). Although the rims of some pyroxenes grown in some melting experiments exhibit prominent zoning in TiAl₂(MgSi₂)_–1, the average values of inferred from the compositions of these pyroxenes, together with those of the relatively homogeneous pyroxenes produced in crystallization experiments, exhibit a 11 correlation with values of derived from the solution model of Ghiorso et al. (1983) with a standard error of 750 calories. The Ti contents of Ca-rich pyroxenes crystallizing from a wide range of natural silicate liquids can therefore be predicted.     

Relationships between silicate melts and carbonate-precipitating melts in CaO-MgO-SiO2-CO2-H2O at 2 kbar

Summary Phase fields intersected by three joins in the System CaO-MgO-SiO₂-CO₂-H₂O at 2 kbar were investigated experimentally to determine the melting relationships and the sequences of crystallization of liquids co-precipitating silicate minerals and carbonates. These joins connect SiO₂ to three mixtures of CaCO₃-MgCO₃-Mg(OH)₂ with compositions on the primary îield for calcite, between the composition CaCO₃ and the low-temperature (650°C eutectic liquid co-precipitating calcite, dolomite and periclase. In the pseudo-quaternary tetrahedron calcite-magnesite-brucite-diopside, two of the significant reactions found are: (1) a eutectic at 650°C, calcite + dolomite + periclase + forsterite + vapor = liquid, and (2) a peritectic at 1038°Cwhich is either calcite + åkermanite + forsterite + vapor = monticellite + liquid calcite + monticellite + forsterite + vapor = åkermanite + liquid. The eutectic liquid has high MgO/CaO and CO₂/H₂O and only 2–3% SiO₂ (estimated 15–20% MgCO₃, 35–40% CaCO₃, 40–45% Mg(OH)₂, and 5–6% Mg₂SiO₄). The composition joins intersect a thermal maximum for åkermanite + forsterite + vapor = liquid, which separates high-temperature liquids precipitating silicates together with a little calcite, from low-temperature liquids precipitating carbonates with a few percent of forsterite; there is no direct path between the silicate and synthetic carbonatite liquids on these joins, but it is possible that fractionating liquid paths diverging from the joins may connect them. More complex relationships involving the pprecipitatioon off monticellite and åkermanite are also outlined. Magnetite-magnesioferrite may replace periclase in natural magmatic systems. The results indicate that the assemblage calcite-dolomite-magnetite-forsterite represents the closing stages of crystallization of carbonatites, whereas assemblages such as calcite-magnetite-forsterite and dolomite-magnetite-forsterite span the whole range of carbonatite evolution in terms of temperature and composition, and provide the link between liquids precipitating silicates and those precipitating carbonates.

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Die Beziehungen zwischen silikarischen Schmelzen und karbonatbildenden Schmelzen im System CaO-MgO-SiO₂-CO₂-H₂O bei 2 kbar

Zusammenfassung Phasenfelder, die durch den Schnitt von drei Verbindungslinien im System CaO-MgO-SiO₂-CO₂-H₂Odefiniert werden, wurden experimentell bei 2 kbar untersucht, um die Schmelzbeziehungen und die Kristallisationsfolge von Schmelzen, die gleichzeitig silikatische und karbonatische Minerale ausscheiden, zu bestimmen. Diese Linien verbinden SiO₂ mit drei Mischungen von CaCO₃-M9CO₃-Mg(OH)₂ mit Zusammensetzungen im primären Calcitfeld, zwischen der Zusammensetzung CaCO₃ und der tieftemperierten (650°C Calcit-, Dolomit- und Periklasbildenden eutektischen Schmelze. Zwei wichtige im ppseudo-quaternären Tetraeder Calcit-Magnetit-Brucit-Diopsid gefundene Reaktionen sind: (1) Ein Eutektikum bei 650°C Calcit + Dolomit + Periklas + Forsterit + Vapor = Liquid und (2) ein Peritektikum bei 1038°C mit entweder Calcit + Åkermanit + Forsterit + Vapor = Monticellit + Liquid oder Calcit + Monticellit + Forsterit + Vapo = Åkermanit + Liquid Die eutektische Schmelze zeigt hohe MgO/CaO und CCO₂H₂O Verhältnisse und nur 2–3% SiO₂(geschätzter Anteil an MgCO₃15–20%, CaCO₃ 35–40%, Mg(OH)₂ 40–50% und Mg₂SiO₄ 5–6%). Die Verbindungslinie schneidet ein thermisches Maximum von Åkermanit + Forsterit + Vapor = Liquid, das höher temperierte Schmelzen, die Silikate gemeinsam mit etwas Clacit ausscheiden, von tiefer temperierten Schmelzen trennt, aus denen sich Karbonate gemeinsam mit wenigen Prozenten Forsterit abscheiden. Es existiert keine direkte Verbindung zwischen silikatischen und synthetischen karbonatitischen Schmelzen entlang dieser Verbindungslinien, es wäre aber möglich, daß Fraktionierungspfade, die von diesen Verbindungslinien ausgehen, sie verbinden. Komplexere Beziehungen, die die Kristallisation von Monticellit und Åkermanit beinhalten, werden ebenfalls aufgezeigt. Magnetit-Magnesioferrit könntean die Stelle von Periklas in nnatürlichenmagmatischen Systemen treten. Die Ergebnisse weisen darauf bin, daß die Vergesellschaftung Calcit-Dolomit-Magnetit-Forsterit das Endstadium der Karbonatitkristallisation repräsentiert, während die Vergesellsschaftungen von Calcit-Magnetit-Forsterit bzw. Dolomit-Magnetit-Forsterit die gesamte Spannweite der Karbonatitevolution hinsichtlich Temperatur und Zusammensetzung umfassen und demnach ein Verbindungsglied zwischen silikat- und karbonatausscheidenden Schmelzen darstellen.

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With 8 Figures     

Calculated Phase Relations in High-Pressure Metapelites in the System NKFMASH (Na2O-K2O-FeO-MgO-Al2O3-SiO2-H2O)

Using an internally consistent thermodynamic dataset and updatedmodels of activity–composition relation for solid solutions,petrogenetic grids in the system NKFMASH (Na₂O–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O)and the subsystems NKMASH and NKFASH have been calculated withthe software THERMOCALC 3.1 in the P–T range 5–36kbar and 400–810°C, involving garnet, chloritoid,biotite, carpholite, talc, chlorite, kyanite/sillimanite, staurolite,phengite, paragonite, albite, glaucophane, jadeite, with quartz/coesiteand H₂O in excess. These grids, together with calculated AFMcompatibility diagrams and P–T pseudosections, are shownto be powerful tools for delineating the phase equilibria andP–T conditions of Na-bearing pelitic assemblages for avariety of bulk compositions from high-P terranes around theworld. These calculated equilibria are in good agreement withpetrological studies. Moreover, contours of the calculated phengiteSi isopleths in P–T pseudosections for different bulkcompositions confirm that phengite barometry is highly dependenton mineral assemblage. KEY WORDS: phase relations; HP metapelite; NKFMASH; THERMOCALC; phengite geobarometry     

Surinamite analogs in the MgO-Ga2O3-GeO2 and MgO-Al2O3-GeO2 systems

New germanate analogs of the mineral surinamite, Mg₃Al₄BeSi₃O₁₆, have been synthesized with composition Mg₄A₄Ge₃O₁₆ (A=Al, Ga) and have been characterized by powder X-ray diffraction and transmission electron microscopy. The Al surinamite phase crystallizes with a primitive unit-cell (P2/n, a=10.153(1), b=11.708(2), c=9.920(1) Å, β=110.18 (2)° and Z=4) similar to that of the silicate mineral. The Ga surinamite-like phase crystallizes with a larger unit-cell (C2/c, a=10.308(2), b=23.690(5), c=10.057(l) Å, β=110.23 (2)° and Z=8). High-resolution electron microscopy has shown the common formation of intergrowths between the surinamite and sapphirine structures, illustrating the polysomatic structural relationship between them. Observations of disordered microstructures in the Al surinamite suggest the occurrence of a P2/n?C2/c transformation.     

Calculated Phase Relations in the System Na2O-CaO-K2O-FeO-MgO-Al2O3-SiO2-H2O with Applications to UHP Eclogites and Whiteschists

Pressure–temperature grids in the system Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O and its subsystems have been calculatedin the range 15–45 kbar and 550–900°C, usingan internally consistent thermodynamic dataset and new thermodynamicmodels for amphibole, white mica, and clinopyroxene, with thesoftware THERMOCALC. Minerals considered for the grids includegarnet, omphacite, diopside, jadeite, hornblende, actinolite,glaucophane, zoisite, lawsonite, kyanite, coesite, quartz, talc,muscovite, paragonite, biotite, chlorite, and plagioclase. Compatibilitydiagrams are used to illustrate the phase relationships in thegrids. Coesite-bearing eclogites and a whiteschist from Chinaare used to demonstrate the ability of pseudosections to modelphase relationships in natural ultrahigh-pressure metamorphicrocks. Under water-saturated conditions, chlorite-bearing assemblagesin Mg- and Al-rich eclogites are stable at lower temperaturesthan in Fe-rich eclogites. The relative temperature stabilityof the three amphiboles is hornblende > actinolite > glaucophane(amphibole names used sensu lato). Talc-bearing assemblagesare stable only at low temperature and high pressure in Mg-and Al-rich eclogites. For most eclogite compositions, talccoexists with lawsonite, but not zoisite, in the stability fieldof coesite. Water content contouring of pressure–temperaturepseudosections, along with appropriate geotherms, provides newconstraints concerning dehydration of such rocks in subductingslabs. Chlorite and lawsonite are two important H₂O-carriersin subducting slabs. Depending on bulk composition and pressure–temperaturepath, amphibole may or may not be a major H₂O-carrier to depth.In most cases, dehydration to make ultrahigh-pressure eclogitestakes place gradually, with H₂O content controlled by divariantor higher variance assemblages. Therefore, fluid fluxes in subductionzones are likely to be continuous, with the rate of dehydrationchanging with changing pressure and temperature. Further, eclogitesof different bulk compositions dehydrate differently. Dehydrationof Fe-rich eclogite is nearly complete at relatively shallowdepth, whereas Mg- and Al-rich eclogites dehydrate continuouslydown to greater depth. KEY WORDS: dehydration; eclogites; phase relations; THERMOCALC; UHP metamorphism; whiteschists