Antigorite-ophicarbonates: Phase relations in a portion of the system CaO-MgO-SiO2-H2O-CO2

The occurrence of critical assemblages among antigorite, diopside, tremolite, forsterite, talc, calcite, dolomite and magnesite in progressively metamorphosed ophicarbonate rocks, together with experimental data, permits the construction of phase diagrams in terms of the variables P, T, and composition of a binary CO₂-H₂O fluid. Equilibrium constants are given for the 30 equilibria that describe all relations among the above phases. Ophicalcite, ophidolomite, and ophimagnesite assemblages occupy partially overlapping fields in the diagram. The upper temperature limit of ophicalcite rocks lies below that of ophidolomite and ophimagnesite. The fluid phase in ophicarbonate rocks has 0.8$$ " align="middle" border="0"> , and there are indications that during their progressive metamorphism is approximately equal to P _total.     

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.     

Synthesis of Ca-tourmaline in the system CaO-MgO-Al2O3-SiO2-B2O3-H2O-HCl

Summary. ?Ca-tourmaline has been synthesized hydrothermally in the presence of Ca(OH)₂ and CaCl₂-bearing solutions of different concentration at T = 300–700 °C at a constant fluid pressure of 200 MPa in the system CaO-MgO-Al₂O₃-SiO₂-B₂O₃-H₂O-HCl. Synthesis of tourmaline was possible at 400 °C, but only above 500 °C considerable amounts of tourmaline formed. Electron microprobe analysis and X-ray powder data indicate that the synthetic tourmalines are essentially solid solutions between oxy-uvite, CaMg₃- Al₆(Si₆O₁₈)(BO₃)₃(OH)₃O, and oxy-Mg-foitite, □(MgAl₂)Al₆(Si₆O₁₈)(BO₃)₃(OH)₃O. The amount of Ca ranges from 0.36 to 0.88 Ca pfu and increases with synthesis temperature as well as with bulk Ca-concentration in the starting mixture. No hydroxy-uvite, CaMg₃(MgAl₅)(Si₆O₁₈)(BO₃)₃(OH)₃(OH), could be synthesized. All tourmalines have < 3 Mg and > 6 Al pfu. The Al/(Al + Mg)-ratio decreases from 0.80 to 0.70 with increasing Ca content. Al is coupled with Mg and Ca via the substitutions Al₂□Mg₋₂Ca₋₁ and AlMg₋₁H₋₁. No single phase tourmaline could be synthesized. Anorthite ( + quartz in most runs) has been found coexisting with tourmaline. Other phases are chlorite, tremolite, enstatite or cordierite. Between solid and fluid, Ca is strongly fractionated into tourmaline ( + anorthite). The concentration ratio D = Ca(fluid)/Ca(tur) increases from 0.20 at 500 °C up to 0.31 at 700 °C. For the assemblage turmaline + anorthite + quartz + chlorite or tremolite or cordierite, the relationship between Ca content in tourmaline and in fluid with temperature can be described by the equation (whereby T = temperature in °C, Ca(tur) = amount of Ca on the X-site in tourmaline, Ca( fluid) = concentration of Ca²⁺ in the fluid in mol/l). The investigations may serve as a first guideline to evaluate the possibility to use tourmaline as an indicator for the fluid composition.

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Zusammenfassung. ?Synthese von Ca-Turmelin im System CaO-MgO-Al ₂ O ₃ -SiO ₂ -B ₂ O ₃ -H ₂ O-HCl Im System CaO-MgO-Al₂O₃-SiO₂-B₂O₃-H₂O-HCl wurde Ca-Turmalin hydrothermal aus Ca(OH)₂ and CaCl₂-haltigen L?sungen bei T = 300–700 °C und einem konstanten Fluiddruck von 200 MPa synthetisiert. Die Synthese von Turmalin war m?glich ab 400 °C, aber nur oberhalb von 500 °C bildeten sich deutliche Mengen an Turmalin. Elektronenstrahl-Mikrosondenanalysen und R?ntgenpulveraufnahmen zeigen, da? Mischkristalle der Reihe Oxy-Uvit, CaMg₃Al₆(Si₆O₁₈)(BO₃)₃(OH)₃O, und Oxy-Mg-Foitit, □(MgAl₂)Al₆(Si₆O₁₈)(BO₃)₃(OH)₃O gebildet wurden. Der Anteil an Ca variiert zwischen 0.36 und 0.88 Ca pfu und nimmt mit zunehmender Synthesetemperatur und zunehmender Ca-Konzentration im System zu. Hydroxy-Uvit, CaMg₃(MgAl₅) (Si₆O₁₈)(BO₃)₃(OH)₃(OH), konnte nicht synthetisiert werden. Alle Turmaline haben < 3 Mg und > 6 Al pfu. Dabei nimmt das Al/(Al + Mg)- Verh?ltnis mit zunehmendem Ca-Gehalt von 0.80 auf 0.70 ab. Al ist gekoppelt mit Mg und Ca über die Substitutionen Al₂□Mg₋₂Ca₋₁ und AlMg₋₁H₋₁. Einphasiger Turmalin konnte nicht synthetisiert werden. Anorthit (+ Quarz in den meisten F?llen) koexistiert mit Turmalin. Andere Phasen sind Chlorit, Tremolit, Enstatit oder Cordierit. Ca zeigt eine deutliche Fraktionierung in den Festk?rpern Turmalin (+ Anorthit). Das Konzentrationsverh?ltnis D = Ca(fluid)/Ca(tur) nimmt von 0.20 bei 500 °C auf 0.31 bei 700 °C zu. Für die Paragenese Turmalin + Anorthit + Quarz mit Chlorit oder Tremolit oder Cordierit gilt folgende Beziehung zwischen Ca-Gehalt in Turmalin und Fluid und der Temperatur: (wobei T = Temperatur in °C, Ca(tur) = Anteil an Ca auf der X-Position in Turmalin, Ca(fluid) = Konzentration von Ca²⁺ im Fluid in mol/l). Die Untersuchungen dienen zur ersten Absch?tzung, ob Turmalin als Fluidindikator petrologisch nutzbar ist.

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Received July 24, 1998;/revised version accepted October 21, 1999     

Bimetasomatic zoning in the CaO-MgO-SiO2-H2O-CO2 system: Experiments with the use of natural rock samples

Experiments reproducing the development of bimetasomatic zoning in the CaO-MgO-SiO₂-H₂O-CO₂ system were conducted at elevated P-T parameters with the use of samples of naturally occurring quartzdolomite and calcite-serpentinite rocks. In order to maintain mass transfer exclusively via the diffusion-controlled mechanism, we used the method of the ensured compaction of the cylindrical sample surface with a thin-walled gold tube. In the course of the experiments, a single diopside zone ～2.5 × 10^?5 m thick was obtained at the quartz-dolomite interface at T = 600°C, $P_{H_2 O + CO_2 } $ = 200 MPa, and $X_{CO_2 } $ = 0.5 for 25–40 days and a succession of metasomatic zones at T = 750°C, $P_{H_2 O + CO_2 } $ = 300 MPa, and $X_{CO_2 } $ = 0.4 for 48 days. The metasomatic zones were as follows (listed in order from quartz to dolomite): wollastonite ‖ diopside ‖ tremolite ‖ calcite + forsterite; with the average width of the diopside zone equal to ～1.3 × 10^?5 m and the analogous part of the wollastonite zone equal to ～2.6 × 10^?5 m. Two zones (listed in order from calcite to serpentine) diopside and diopside-forsterite (the average widths of these zones were ～6 × 10^?4 and ～8 × 10^?4 m, respectively) were determined to develop at contact between serpentine and calcite during experiments that lasted 124 days at T = 500°C, $P_{H_2 O + CO_2 } $ = 200 MPa, and $X_{CO_2 } $ = 0.2–0.4. In the former and latter situations, the growth rate of the zoning ranged between 3.1 × 10^?12 and 1.2 × 10^?11 m/s and between 5.6 × 10^?11 and 7.5 × 10^?11 m/s, respectively. The higher growth rate in the latter case can be explained by the higher water mole fraction in the fluid, with this water released during serpentinite decomposition in the experiments. The development of the only diopside zone in the experiments modeling the interaction of quartz and dolomite at T = 600–650°C and $P_{H_2 O + CO_2 } $ = 200 MPa is in conflict with theoretical considerations underlain by the Korzhinskii-Fisher-Joesten model. The interaction of quartz and dolomite in the CaO-MgO-SiO₂-CO₂-H₂O system at the P-T- $X_{CO_2 } $ parameters specified above should be attended by the origin of a number of reaction zones consisting of various proportions of talc, forsterite, tremolite, diopside, and calcite. The saturation of the fluid with respect to these minerals was likely not reached, and this resulted in the degeneration of the respective stability fields in the succession of zones. Conceivably, this was related to the insufficient rates of quartz and dolomite dissolution and the relatively low diffusion rates of the dissolved species in the low-permeable medium. In the experiments with interacting calcite and serpentine, the zoning calcite ‖ diopside ‖ diopside + forsterite ‖ serpentine developed in its complete form, in agreement with the theory. Equilibrium was likely achieved in these experiments due to the higher diffusion coefficients.     

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.     

Some mineral stability relations in the system CaOMgOSiO2H2OHCl

Mineral-aqueous solution equilibria for the assemblages talc-quartz, tremolite-talc-quartz, diopside-tremolite-quartz, wollastonite-diopside-quartz and wollastonite-quartz have been studied at 2 kb total pressure, 500° to 700°C and chloride concentrations from 0.03 to 6.0 molal. Most work was at 1 m chloride. Both buffered and unbuffered data were obtained and a recalibration of the Ag-AgCl buffer is presented. Log equilibrium quotients at 500°, 600° and 700°C are respectively: Ta-Qz () 2.57, 1.71, 0.73; Tr-Ta-Qz and Di-Tr-Qz () 4.98, 3.99, 2.21 and 7.29, 5.30, 3.56; WoDi-Qz () 3.30, 3.00, 2.79: Wo-Qz () 5.15, 3.95, 2.68. Mineral stability fields plotted in terms of these concentration data more tangibly represent the compositional character of real systems and the mass transfer capabilities of their fluids than do the analogous theoretical activity diagrams.Overall dissociation constants of MgCl₂ and CaCl₂ were calculated from the experimental data using the calculated ionic activity constants for the reactions and the established dissociation constants of HCl. The negative log values are respectively: 3.88. 6.63, 9.20 for CaCl₂ and 4.60, 7.54, 10.37 for MgCl₂ at 500°, 600° and 700°C, 2 kb. The Ca values are about an order of magnitude more positive than the conductance-derived values by Frantz and Marshall (1982).The phase relations developed in this study have application to the genesis of talc, tremolite, and diopside-bearing assemblages in some regional metamorphic rocks, but more specifically to the calcsilicate skarn assemblages of many metasomatic aureoles. The equilibrium fluids are characterized by high concentrations of Ca relative to Mg and increasing $\text{Ca}\text{Mg}$ ratios with decreasing temperatures. The stability fields of talc, tremolite, and quartz expand relative to those of diopside and wollastonite with decreasing temperature, hence their more common appearance as retrograde products in skarn systems.     

Solubility and complexing of Ni in the system NiO-H2O-HCl

The solubility of bunsenite (NiO) in Cl-bearing fluids in the range of 450°–700°C, 1–2 kbar was determined using the Ag + AgCl acid buffer technique. Based on the results of the experiments, it is concluded that the associated NiCl⁰₂ complex is the dominant Ni species in the fluid over the entire temperature-pressure range investigated. The temperature dependence of the equilibrium constant for the reaction NiO(s) + 2HCl⁰(aq) = NiCl⁰₂(aq) + H₂O is given by logK = ?4.17(±0.55) + 4629(±464)/T(K) at 1 kbar, and logK = ?4.75(±0.91) + 5933(±756)/T(K) at 2 kbar. The calculated difference in standard state Gibbs free energy of formation between NiCl⁰₂ and 2HCl⁰ in kcal is G⁰(NiCl⁰₂) ? 2G⁰(HCl⁰) = ?20.77(±2.22) + 0.03264(±0.0026)T(K), at 1 kbar and G⁰(NiCl⁰₂) ? 2G⁰(HCl⁰) = ?25.01(±1.35) + 0.03264(±0.0016)T(K) at 2 kbar. Comparison of the solubilities of Ni end-member minerals with those of Ca, Mn, Fe, and Mg indicates that nickel minerals generally are the least soluble at a given temperature and pressure. The relatively low solubility of Ni end-member minerals, combined with the relatively low concentration of Ni in most rocks, should result in a quite low mobility of Ni in hydrothermal fluids.     

Metasomatic Phase Relations in the System CaO-MgO-SiO2-H2O-NaCl at High Temperatures and Pressures

An equation of state of solute silica in NaCl brines at 500 to 900°C and 4 to 15 kbar is formulated by making use of two experimentally determined properties of quartz solubility: the silica molality decreases in direct proportion to the logarithm of the NaCl mole fraction (X(NaCl)) at pressures approaching 10 kbar, and the relative silica molality (molality at a given NaCl mole fraction, m_x, divided by the molality in pure H₂O at the same P and T, m_o) is independent of temperature in the evaluated range. These two properties are expressed in the relation:

log(m_x/m_o)? = A + BX(NaCI),

where log(m_x/m_o)? denotes the logarithm of the ideal molality ratio, and A and B are functions of pressure, but not temperature or salinity, such that B = ?1.730 ? 1.431 × 10?³P + 5.923 × 10?⁴P² ?9.243 × lO?⁵P³, and A = 0 at P>10 kbar, whereas A = 0.6131 ? 0.1256P + 6.431 × 10?³P² at P≤10 kbar, as derived from fits to experimental data (Newton and Manning, 1999). The parameter A decreases from 0.214 to 0 from 4 to 9.5 kbar, and remains zero to 15 kbar; B decreases from ?1.373 to ?1.571 from 4 to 15 kbar. With the above relationship defining a variable X(NaCl)-T-P standard-state of solute silica, the activity of SiO₂ can be replaced by its molality for calculations of mineral-fluid equilibria over most of the conditions for metasomatism in the deep crust and upper mantle. Significant departures from ideality occur only at the lowest pressures, and low salinities.

Calculations on peridotite mineral stability in the simple system CaO-MgO-SiO₂-H₂O-NaCl at high T and P show that antigorite, brucite, and diopside are stable at 500°C and pressures of 5 to 15 kbar in the presence of concentrated NaCl solutions at low SiO₂ activities. At 700°C, anthophyllite is stable over a wide range of salinities at 5 kbar with tremolite but not with diopside. The presence of anthophyllite buffers silica solubility at a high, salinity-independent value close to quartz saturation. At 10 and 15 kbar and 700°C, talc replaces anthophyllite as the stable hydrate, and talc-trem-olite assemblages buffer SiO₂ fluid concentrations at high values nearly independent of salinity. At 900°C hydrates are unstable and diopside again becomes stable and coexists with enstatite in peridotites. These stability calculations correspond well to the observed progressive metamorphic sequence in peridotite bodies in the Central Alps.

This method of analysis may be useful in interpretation of metamorphosed ultramafic bodies in general, including the basal portions of obducted ophiolitic mantle lithosphere and the mantle wedge above subduction zones. More detailed calculations, including rocks containing feldspars, must take into account the more soluble major components of rocks, especially alkalis, as these will affect the activity coefficient of SiO₂ in NaCl solutions. The solubility of silica in the presence of minerals containing these components must be determined by additional measurements.     

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.     

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     

P CO2 in low-grade metamorphism; zeolite,carbonate, clay mineral,prehnite relations in the system CaO-Al2O3-SiO2-CO2-H2O

Equilibria for several reactions in the system CaO-Al₂O₃-SiO₂-CO₂-H₂O have been calculated from the reactions calcite+quartz=wollastonite+CO₂ (5) and calcite+Al₂SiO₅+quartz=anorthite+CO₂ (19) and other published experimental studies of equilibria in the systems Al₂O₃-SiO₂-H₂O and CaO-Al₂O₃-SiO₂-H₂O.The calculations indicate that the reactions laumontite+CO₂=calcite+kaolinite+2 quartz+2H₂O (1) and laumontite+calcite=prehnite+quartz+3H₂O+CO₂ (3) in the system CaO-Al₂O₃-SiO₂-CO₂-H₂O, are in equilibrium with an H₂O-CO₂ fluid phase having -0.0075 for P _fluid=P _total=2000 bars.These calculations limit the stability of zeolite assemblages to low p CO₂.Using the above reactions as model equilibria, several probelms of p CO₂ in low grade metamorphism are discussed. (a) the problem of producing zeolitic minerals from metasedimentary assemblages of carbonate, clay mineral, quartz. (b) the significance of calcite (or aragonite) associated with zeolite (or lawsonite) in low grade metamorphism and hydrothermal alteration. (c) the reaction of zeolites (or lawsonite) with calcite (or aragonite) to produce dense Ca-Al-hydrosilicates (eg. prehnite, zoisite, grossular).     

Solid-Fluid Equilibria in the System KAlSi3O8-NaAlSi3O8-Al2SiO5-SiO2-H2O-HCl

Activity diagrams in the system KAlSi₃O₈-NaAlSi₃O₈-Al₂SiO₅-SiO₂-H₂O-HClhave been calculated in terms of a_K+/a_H+ and a_N+/a_H+ from existingexperimental data. They show the effect of temperature, pressure,and a_H2O on the stability fields of the alkali feldspars, micas,and aluminium silicate. These activity diagrams are useful in revealing the bufferingcapacity of mineral assemblages and the chemical potential gradientsestablished by changes in T, P, a_H2O, and mineral assemblage.An analysis of mineral paragenesis in terms of these diagramssuggests that mosaic equilibrium, allowing limited metasomatismand internal buffering of chemical potentials, best describemetamorphic systems. Thus the dehydration reaction: muscovite+quartz=K-feldspar+Al₂SiO₅+H₂O which is most important in closed systems, probably fails todescribe in detail the mechanism of natural muscovite decomposition.Rather the decomposition of muscovite is more likely representedby ionic reactions. The replacement of muscovite by feldspar: muscovite+6 SiO₂+2 K⁺=3 K-feldspar+2 H⁺ muscovite+6 SiO₂+3 Na⁺=3 Albite+K⁺+2 H⁺ is favored at high temperature and low pressure, and may accountfor the crystallization of some feldspars in metamorphic rocks.The reaction involving aluminium silicate replacement of muscovite: 2 muscovite+2 H⁺=3 Al₂SiO₅+3 SiO₂+3 H₂O+2 K⁺ is favored at high temperature and pressure and low a_H2O, andcould contribute to the development of the aluminium silicates.It is concluded that both activity diagrams and AKNa projectionsshould be used together to more completely evaluate mineralparagenesis in terms of mosaic equilibria.     

Phase relations and mineral assemblages in the Ag-Bi-Pb-S system

Phase relations within the Ag-Bi-S, Bi-Pb-S, and Ag-Pb-S systems have been determined in evacuated silica tube experiments. Integration of experimental data from these systems has permitted examination and extrapolation of phase relations within the Ag-Bi-Pb-S quaternary system. — In the Ag-Bi-S system liquid immiscibility fields exist in the metal-rich portion above 597±3°C and in the sulfur-rich portion above 563±3°C. Ternary phases present correspond to matildite (AgBiS₂) and pavonite (AgBi₃S₅). Throughout the temperature range 802±2°C to 343±2°C the assemblage argentite (Ag₂S) + bismuth-rich liquid is stable; below 343°C this assemblage is replaced by the assemblage silver + matildite. — Five ternary phases are stable on the PbS-Bi₂S₃ join above 400°C — phase II (18 mol-% Bi₂S₃), phase III (27 mol-% Bi₂S₃), cosalite (33.3 mol-% Bi₂S₃), phase IV (51 mol-% Bi₂S₃), and phase V (65 mol-% Bi₂S₃). Phase IV corresponds to the mineral galenobismutite and is stable below 750±3°C. Phases II, III, and V do not occur as minerals, but typical lamellar and myrmekitic textures commonly observed among the Pb-Bi sulfosalts and galena evidence their previous existence in ores. Phase II and III are stable from 829±6°C and 816±6°C, respectively, to below 200°C; Phase V, stable only between 730±5°C and 680±5°C in the pure Bi-Pb-S system is stabilized to 625±5°C by the presence of 2% Ag₂S. Experiments conducted with natural cosalites suggest that this phase is stable only below 425±25°C in the presence of vapor. — In the Ag-Pb-S system the silver-galena assemblage is stable below 784±2°C, whereas the argentite + galena mineral pair is stable below 605±5°C. — Solid solution between matildite and galena is complete above 215±15°C; below this temperature characteristic Widmanstätten structure-like textures are formed through exsolution. Schematic phase relations within the quaternary system are presented at 1050°C, at 400°C, and at low temperature.

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Zusammenfassung Die Phasenbeziehungen in den Systemen Ag-Bi-S, Bi-Pb-S und Ag-Pb-S wurden durch Versuche in evakuierten Quarzglasröhrchen bestimmt. Die Auswertung aller experimentellen Daten gestattete eine Extrapolation der Phasenbeziehungen im quaternären System Ag-Bi-Pb-S. — Im System Ag-Bi-S besteht ein Zwei-Schemlzenfeld im metallreichen Teil über 597±3°C und im schwefelreichen Teil über 563±3°C. Die ternären Phasen entsprechen den Mineralien Schapbachit (AgBiS₂) und Pavonit (AgBi₃S₅). Zwischen 802±2°C und 343±2°C ist die Paragenese Silberglanz (Ag₂S) + Bi-reiche Schmelze stabil; unterhalb 343°C wird sie jedoch ersetzt durch die Paragenese Silber + Schapbachit. — Fünf ternäre Phasen sind stabil im Schnitt PbS-Bi₂S₃ oberhalb von 400°C: Phase II (18 Mol-% Bi₂S₃), Phase III (27 Mol-% Bi₂S₃), Cosalite (33.3 Mol-% Bi₂S₃), Phase IV (51 Mol-% Bi₂S₃) und Phase V (65 Mol-% Bi₂S₃). Phase IV entspricht dem Mineral Galenobismutit und ist stabil unterhalb 750±3°C. Die Phasen II, III und V kommen zwar nicht in der Natur vor, jedoch weisen typische myrmekitische und lamellare Gefüge, die man häufig in Pb-Bi-Sulfosalzen und deren Verwachsungen mit Bleiglanz beobachtet, auf die ehemalige Existenz solcher Phasen in diesen Erzen hin. Die Phasen II und III sind stabil von 829±6°C bzw. 816±6°C bis unter 200°C. Die Phase V, die im reinen System Bi-Pb-S zwischen 730±5°C und 680±5°C auftritt, wird in Gegenwart von 2% Ag₂S stabilisiert bis herab zu 625±5°C. Versuche mit natürlichen Cosaliten lassen darauf schließen, daß diese Phase nur unterhalb 425±25°C in Gegenwart einer Gasphase stabil ist. — Im System Ag-Pb-S ist die Paragenese Silber-Bleiglanz unterhalb von 784±2°C stabil, die Paragenese Silberglanz-Bleiglanz dagegen unterhalb 605±5°C. — Die Mischkristallreihe von Schapbachit und Bleiglanz ist vollständig oberhalb 215±15°C; unterhalb dieser Temperatur entstehen charakteristische Entmischungsgefüge ähnlich den Widmannstättenschen Figuren. Für das quaternäre System werden schematische Phasenbeziehungen für 1050°C, 400°C und eine noch tiefere Temperatur gegeben.

     

Melts in the mantle modeled in the system CaO-MgO-SiO2-CO2 at 2.7 GPa

The effect of CO₂ on mantle peridotites is modeled by experimental data for the system CaO-MgO-SiO₂-CO₂ at 2.7 GPa. The experiments provide isotherms for the vapor-saturated liquidus surface, bracket piercing points for field boundaries on the surface, and define the positions and compositions of isobaric invariant liquids on the boundaries (eutectics and peritectics). CO₂-saturated carbonatitic liquids (>80% carbonate) exist through approximately 200 °C above the solidus, with a transition to silicate liquids (>80% silicate) within ∼75 °C across a plateau on the liquidus. Carbonate-rich magmas cannot cross the silicate-carbonate liquidus field boundary, so the carbonate liquidus field is therefore a forbidden volume for liquid magmas. This confirms the fact that rounded, pure carbonates in mantle xenoliths cannot represent original liquids. A P-T diagram is constructed for the carbonation and melting reactions for mineral assemblages corresponding to lherzolite, harzburgite, websterite and wehrlite, with carbonate, CO₂ vapor (V), or both. The changing compositions of liquids in solidus reactions on the P-T diagram are illustrated by the changing compositions of eutectic and peritectic liquids on the liquidus surface. At an invariant point Q (∼2.8 GPa/1230 °C), all peridotite assemblages coexist with a calcite-dolomite solid solution (75 ± 5% CaCO₃) and a dolomitic carbonatite melt [57% CaCO₃ (CC), 33% MgCO₃ (MC), 10% CaMgSi₂O₆ (Di)], with 63% CC in the carbonate component. At higher pressures, dolomite-lherzolite, dolomite-harzburgite-V, and dolomite-websterite-V melt to yield similar liquids. Magnesian calcite-wehrlite is the only peridotite melting to carbonatitic liquids (more calcic) at pressures below Q (∼70 km). Dolomitic carbonatite magma rising through mantle to the near-isobaric solidus ledge near Q will begin to crystallize, releasing CO₂ (enhancing crack propagation), and metasomatizing lherzolite toward wehrlite. Received: 20 March 1998 / Accepted: 7 July 1999     

High-pressure,high-temperature stability of surinamite in the system MgO-BeO-Al2O3-SiO2-H2O

The MgAl surinamite end member, (Mg₃Al₃)^[6]O[AlBeSi₃O₁₅], was synthesized in the requisite system with and without water. The new phase is monoclinic, space group P2/n, with a=9.881(1)Å; b=11.311(1) Å; c=9.593(1) Å; =109.52(2)°. Refractive indices are n _x=1.7015(20); n _y=1.7035(20); n _z=1.7055(20). The infrared spectrum shows characteristic differences against the structurally related and optically extremely similar phase sapphirine.Using the seeding technique, the preliminary stability field for MgAl surinamite was found to lie at high temperatures (650 °C) and high pressures (4 kbar). At lower temperatures breakdown takes place to hydrous assemblages of chlorite, talc, and chrysoberyl with kyanite or yoderite; at lower pressures chrysoberyl forms parageneses with sapphirine and cordierite. In crystal chemical terms the underlying principle for the stability of surinamite versus that of the low-pressure assemblages is the higher proportion of octahedrally coordinated Al in surinamite (75%). Following the same principle surinamite itself decomposes at still higher pressures to a paragenesis, in which all Al enters octahedral coordination (pyrope+a chrysoberyl-type phase and some unidentified X-ray peaks).The stability field of synthetic MgAl surinamite is in good agreement with P, T-estimates of some 8–12 kbar, 800°–950° C as taken from the literature for the few occurrences of natural, Fe-bearing surinamite in granulite and upper amphibolite facies environments. The incorporation of iron in surinamite must be limited, because this mineral is known to coexist with its more iron-rich breakdown assemblage almandine-rich garnet+chrysoberyl. As the minimum melting curve of granite under hydrous conditions lies outside the surinamite field up to a water pressure of about 20 kbar, the absence of surinamite in normal granitic pegmatites can already be explained by physical constraints. However, there are probably also chemical constraints in the generally high Fe/Mg bulk chemistry of the pegmatite environments.Now at Institut für Kristallographie, Technische Hochschule, Templergraben 55, D-5100 Aachen, FRG     

The thermodynamic properties and phase relations of some minerals in the system CaO-AI2O3-SiO2-H2O

The heat capacities of lawsonite, margante, prehnite and zoisite have been measured from 5 to 350 K with an adiabatic-shield calorimeter and from 320 to 999.9 K with a differential-scanning calorimeter. At 298.15 K, their heat capacities, corrected to end-member compositions, are 66.35, 77.30, 79.13 and 83.84 cal K^?1 mol^?1; their entropies are 54.98, 63.01, 69.97 and 70.71 cal K^?1 mol^?1, respectively. Their high-temperature heat capacities are described by the following equations (in calories, K, mol): Lawsonite (298–600 K): Cp° = 66.28 + 55.95 × 10^?3T ? 15.27 × 10⁵T^?2 Margarite (298–1000 K): Cp° = 101.83 + 24.17 × 10^?3T ? 30.24 × 10⁵T^?2 Prehnite (298–800 K): Cp° = 97.04 + 29.99 × 10^?3T ? 25.02 × 10⁵T^?2 Zoisite (298–730 K): Cp° = 98.92 + 36.36 × 10^?3T ? 24.08 × 10⁵T^?2 Calculated Clapeyron slopes for univariant equilibria in the CaO-Al₂O₃-SiO₂-H₂O system compare well with experimental results in most cases. However, the reaction zoisite + quartz = anorthite + grossular + H₂O and some reactions involving prehnite or margarite show disagreements between the experimentally determined and the calculated slopes which may possibly be due to disorder in experimental run products. A phase diagram, calculated from the measured thermodynamic values in conjunction with selected experimental results places strict limits on the stabilities of prehnite and assemblages such as prehnite + aragonite, grossular + lawsonite, grossular + quartz, zoisite + quartz, and zoisite + kyanite + quartz. The presence of this last assemblage in eclogites indicates that they were formed at moderate to high water pressure.     

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     

PT-diagram of the system SiO2-H2O

The high-temperature and medium-pressure part of the PT-diagram of the system SiO₂-H₂O has been investigated experimentally. The equilibrium diagram is discussed in the light of Schreinemakers general theory of PT-diagrams. The triple invariant point cristobalite + tridymite + quartz lies at 1190°C and 1430 atm. Neither cristobalite nor tridymite are stable at high pressure. Quartz may precipitate from the melt at a very high temperature (1360°C and higher), if the pressure is great enough, and if the water content is low. Using new experimental and published data a PT-diagram of the system SiO₂-H₂O in the large PT-region is given.     

The heat capacity of a natural monticellite and phase equilibria in the system CaO-MgO-SiO2-CO2

The heat capacity of a natural monticellite (Ca_1.00Mg_.09Fe_.91Mn_.01Si_0.99O_3.99) measured between 9.6 and 343 K using intermittent-heating, adiabatic calorimetry yields C_p⁰(298) and S₂₉₈⁰ of 123.64 ± 0.18 and 109.44 ± 0.16 J · mol⁻¹K⁻¹ respectively. Extrapolation of this entropy value to end-member monticellite results in an S⁰₂₉₈ = 108.1 ± 0.2 J · mol⁻¹K⁻¹. High-temperature heat-capacity data were measured between 340–1000 K with a differential scanning calorimeter. The high-temperature data were combined with the 290–350 K adiabatic values, extrapolated to 1700 K, and integrated to yield the following entropy equation for end-member monticellite (298–1700 K): S_T⁰(J · mol⁻¹K⁻¹) = S₂₉₈⁰ + 164.79 In T + 15.337 · 10⁻³T + 22.791 · 10⁵T⁻² − 968.94. Phase equilibria in the CaO-MgO-SiO₂ system were calculated from 973 to 1673 K and 0 to 12 kbar with these new data combined with existing data for akermanite (Ak), diopside (Di), forsterite (Fo), merwinite (Me) and wollastonite (Wo). The location of the calculated reactions involving the phases Mo and Fo is affected by their mutual solid solution. A best fit of the thermodynamically generated curves to all experiments is made when the S⁰₂₉₈ of Me is 250.2 J · mol⁻¹ K⁻¹ less than the measured value of 253.2 J · mol⁻¹ K⁻¹.A best fit to the reversals for the solid-solid and decarbonation reactions in the CaO-MgO-SiO₂-CO₂ system was obtained with the ΔG⁰₂₉₈ (kJ · mole⁻¹) for the phases Ak(−3667), Di(−3025), Fo(−2051), Me(−4317) and Mo(−2133). The two invariant points − Wo and −Fo for the solid-solid reactions are located at 1008 ± 5 K and 6.3 ± 0.1 kbar, and 1361 ± 10 K and 10.2 ± 0.2 kbar respectively. The location of the thermodynamically generated curves is in excellent agreement with most experimental data on decarbonation equilibria involving these phases.     

Stability of clinohumite in the system MgO-SiO2-H2O

The low-pressure stability of clinohumite has been investigated in phase-equilibrium experiments on the reaction forsterite + brucite = clinohumite. The reaction was bracketed between 2.45 and 2.84 GPa at 650 °C, extending to between 1.37 and 1.57 GPa at 850 °C. At temperatures above the reaction brucite = periclase + vapour, the reaction clinohumite = forsterite + vapour was bracketed between 1.27 and 1.52 GPa at 900 °C, rising to between 1.90 and 2.00 GPa at 1000 °C. The position of the reaction forsterite + brucite = clinohumite is ∼0.5 GPa below the position determined in previous work, the difference arising either from pressure uncertainties in both studies, from enhanced reaction to clinohumite in this study due to the presence of excess brucite in the starting material, or from different concentrations of defects in the two samples. The brackets on the reaction were combined with other measured and estimated thermodynamic data for clinohumite to determine its enthalpy of formation and entropy, in a revised version of the thermodynamic dataset of Holland and Powell (1998). The values obtained were ΔH _f =−9607.29±3.05 kJ mol⁻¹, S=445 J mol⁻¹ K⁻¹. These data were used to calculate positions of other reactions involving clinohumite. The calculations suggest a larger stability field for clinohumite than implied by the results of previous experimental studies, indicating a need for more high-pressure phase-equilibrium studies to provide better thermodynamic data. Received: 30 April 1999 / Accepted: 8 November 1999