Unit-cell dimensions and tetrahedral-site ordering in synthetic gallium albite (NaGaSi3O8)

The tetrahedral-site order-disorder transformation in gallium albite (NaGaSi₃O₈) has been investigated using Rietveld structure refinement. Study of gallium-substituted albite (in contrast to pure albite [NaAlSi₃O₈]) is facilitated by a relatively rapid order-disorder transformation and the large difference in X-ray scattering efficiencies of gallium and silicon. High albite-structure NaGaSi₃O₈, grown in a Na₂WO₄ flux, was ordered by hydrothermal annealing below 820° C and dry annealing above 820° C, to avoid melting, using a load pressure of approximately 1 kbar. Equilibration of the order-disorder reaction has been verified by three independent reversals of ordering. The transformation between low gallium albite and high gallium albite occurs over the temperature range 890° C 970° C. The gallium content of the T ₁o site increases continuously with decreasing temperature. The gallium contents of the T ₁m and T ₂m sites decrease smoothly with increasing ordering while the gallium content of the T ₂o site decreases, then increases and then decreases again with decreasing temperature. Unit-cell parameters and the triclinic obliquity vary throughout the order-disorder transformation and undergo abrupt changes at 913±3° C and 937±3° C. These abrupt changes correlate with changes in the gallium content of the T ₂o site, the X and Z ordering parameters and the configurational entropy. The order-disorder transformation in gallium-aluminum albite (NaGa_0.5Al_0.5Si₃O₈) occurs in the temperature range 765° C-850° C, at a temperature intermediate to the transformation in albite (50% order at about 680±20° C) and gallium albite.     

Experimental deformation of sintered albite above and below the order-disorder transition

Abstract

Purified albite powder (44-53 μm) has been sintered to form an albite polycrystal suitable for deformation studies close to the melting temperature. Experiments have been carried out in Griggs solid medium deformation apparatus at 800, 1020 °C and 700 MPa pressure in a dehydrating pyrophyllite confining medium at constant strain rates of 10^?4, 10^?5, 10^?6 and 10^?7/s. At 800 °C the samples were brittle-ductile whereas at 1020 °C they were ductile with a rheology well described by a power law with a stress exponent of 3. The transition from brittle-ductile to ductile also coincided with the order-disorder or low-high albite transition, as indicated by the marked increase in mechanical twinning on the albite law at high temperature. At 1020 °C high dislocation densities (10^?10 - 10^?11/cm² and mechanical twinning characterised the original high albite grains, whereas fine recrystallised grains ( < 5 цm) had low dislocation densities (10⁷ - 10⁸/cm²) and often contained polysynthetic albite and pericline (M-type) twins. It is suggested that the recrystallized grains were monalbite (monoclinic) under test conditions which have inverted to high albite (triclinic) and in so doing produced M-twins, and that the recrystallization mechanism involved grain-boundary bulging to nucleate new high angle boundaries. The implications of the order-disorder transition for twinning and grain boundary migration are discussed and it is suggested that the data cannot be simply extrapolated to natural deformation in the low albite field.     

The ordering behaviour of reedmergnerite,NaBSi3O8

Reedmergnerite (NaBSi₃O₈) has been synthesised hydrothermally from gels containing 10 wt.% excess SiO₂. The degree of B, Si order increases with time at constant temperature and pressure. Complete order is achieved in 250 h at 400° C, P _fluid=1 kbar and in 700 h at 300° C, 1 kbar. Lower pressures and/ or low water contents greatly reduce the rate of ordering. The ordering behaviour of reedmergnerite is insensitive to the composition of the co-existing fluid and this contrasts with the behaviour of albite. It is suggested that ordering takes place by a process of solution and re-precipitation.     

Relaxation mechanisms and effects of motion in albite (NaAlSi3O8) liquid and glass: A high temperature NMR study

The nuclear magnetic relaxation of ²³Na and ²⁹Si in albite glass and liquid has been studied from 800 K to 1400 K. The dominant spin-lattice relaxation mechanism for ²³Na is found to be nuclear quadrupole interaction arising from the Na⁺ diffusion. The activation energy of the Na diffusion is found to be 71±3 kJ/mol, in close agreement with the results on electrical conductivity and on Na self-diffusion from radio-tracer experiments. The correlation time of the Na motion is estimated to be about 8.5×10^?11 s near the melting point (～1390 K). Both nuclear dipole-dipole interaction and chemical shift anisotropy interaction are large enough to contribute to the ²⁹Si relaxation. However, calculations based on a simplified model which employ single correlation time and exponential correlation function, with interactions typical of crystalline silicates, cannot completely account for the experimental data. NMR relaxation data also reveal that the Si motion is correlated to the Na motion and that the Si is relatively immobile. Several possible motions of SiO₄ tetrahedra that can cause ²⁹Si relaxation are suggested. The motion responsible for ²⁹Si relaxation differs from that which is responsible for viscosity: the apparent activation energy for the former is much lower. Measurements of spin-spin relaxation times and linewidths are also presented and the significance of their temperature dependence is discussed.     

Analbite → monalbite transition in a heat treated twinned amelia albite

Amelia albite annealed at > 1080 °C for 3200 hrs by Duba and Piwinskii (1974) shows very fine twin lamellae (～1 μm) after the albite law, suggesting that it once underwent transformation into monalbite. A fragment of this specimen was investigated at 27 °C, 300 °C, 550 °C, 800 °C and 930 °C using the high-temperature precession technique. As the temperature increases, the splitting angle of c ^*-axes (likewise c ^*-axes) of two twin individuals continues to decrease. The photographs taken at 930 °C show that these two splitting angles have converged to 0^o, indicating completion of the transformation into monalbite. The transition point we observe supports the results of MacKenzie (1952) (920±20 °C) and Grundy et al. (1967) (930 °C) rather than those of Sueno et al. (1973) and Prewitt et al. (1974) (> 1080 °C); the discrepancy is most likely due to the differences in the degree of Al-Si disorder of the samples used in the experiments.     

High pressure transitions in the system KAlSi3O8-NaAlSi3O8

Phase relations in the system KAlSi₃O₈-NaAlSi ₃O₈ have been examined at pressures of 5–23 GPa and temperatures of 700–1200° C. KAlSi₃O₈ sanidine first dissociates into a mixture of wadeite-type K₂Si₄O₉, kyanite and coesite at 6–7 GPa, which further recombines into KAlSi₃O₈ hollandite at 9–10 GPa. In contrast, NaAlSi₃O₈ hollandite is not stable at 800–1200° C near 23 GPa, where the mixture of jadeite plus stishovite directly changes into the assemblage of calcium ferrite-type NaAlSiO₄ plus stishovite. Phase relations in the system KAlSi₃O₈-NaAlSi₃O₈ at 1000° C show that NaAlSi₃O₈ component gradually dissolves into hollandite with increasing pressure. The maximum solubility of NaAlSi₃O₈ in hollandite at 1000° C was about 40 mol% at 22.5 GPa, above which it decreases with pressure. Unit cell volume of the hollandite solid solution decreases with increasing NaAlSi₃O₈ component. The hollandite solid solution in this system may be an important candidate as a host mineral of K and Na in the uppermost lower mantle     

Carbon in silicate liquids: the systems NaAlSi3O8-CO2, CaAl2Si2O8-CO2, and KAlSi3O8-CO2

To further our knowledge of the effects of volatile components on phase relationships in aluminosilicate systems, we determined the vapor saturated solidi of albite, anorthite, and sanidine in the presence of CO₂ vapor. The depression of the temperature of the solidus of albite by CO₂ decreases from 30° C at 10 kbar, to 10° C at 20 kbar, to about 0 at 25 kbar, suggesting that the solubility of CO₂ in NaAlSi₃O₈ liquid in equilibrium with solid albite decreases with increasing pressure and temperature. In contrast, CO₂ lowers the temperature of the solidus of anorthite by 30° C at 14 kbar, and by 70dg C at 25 kbar. This contrasting behavior of albite and anorthite is also reflected in the behavior of melting in the absence of volatile components. Whereas albite melts congruently to a liquid of NaAl-Si₃O₈ composition to pressures of 35 kbar, anorthite melts congruently to only about 10 kbar and, at higher pressures, incongruently to corundum plus a liquid that is enriched in SiO₂ and CaO and depleted in Al₂O₃ relative to CaAl₂Si₂O₈.The tendency toward incongruent melting with increasing pressure in albite and anorthite produces an increase in the activity of SiO₂ component in the liquid ( ). We predict that this increases the ratio of molecular CO₂/CO ₃ ^2– in these liquids, but the experimental results from other workers are mutually contradictory. Because of the positive dP/dT of the albite solidus and the negative dP/dT of the anorthite solidus, we propose that a negative temperature derivative of the solubility of molecular CO₂ in plagioclase liquids may partly explain the decrease in solubility of carbon with increasing pressure in near-solidus NaAlSi₃O₈ liquids, which is in contrast to that in CaAl₂Si₂O₈ liquid. Also, reaction of CO₂ with NaAlSi₃O₈ liquid to form CO ₃ ^2– that is complexed with Na⁺ must be accompanied by a change in Al³⁺ from network-former to network-modifier, as Na⁺ is no longer abailable to charge-balance Al³⁺ in a network-forming role. However, when anorthite melts incongruently to corundum plus a CaO-rich liquid, the complexing of CO ₃ ^2– with the excess Ca²⁺ in the liquid does not require a change in the structural role of aluminum, and it may be more energetically favorable.The depression of the temperature of the solidus of sanidine resulting from the addition of CO₂ increases from 50° C at 5 kbar to 170° C at 15 kbar. In marked contrast to the plagioclase feldspars, sanidine melts incongruently to leucite plus a SiO₂-rich liquid up to the singular point at 15 kbar. Above this pressure, sanidine melts congruently, resulting in a decrease in the with increasing pressure in the interval up to 15 kbar. Above this pressure, the congruent melting of sanidine results in a lower and nearly constant relative to those of albite and anorthite, and CO₂ produces a nearly constant freezing-point depression of about 170° C. Because of the low at pressures above the singular point, we infer that most of the carbon dissolves as CO ₃ ^2– , resulting in a low CO₂/ CO ₃ ^2– , but a high total carbon content.The principles derived from the studies of phase equilibria in these chemically simple systems provide some information on the structural and thermal properties of magmas. We propose that the is an important parameter in controlling the speciation of carbon in these feldspathic liquids, but it certainly is not the only factor, and it may be relatively less significant in more complex compositions. In addition, our phase-equilibria approach does not provide direct thermal and structural information as do calorimetry and spectroscopy, but the latter have been used primarily on glasses (quenched liquids) and cannot be used in situ to derive direct information on liquids at elevated pressures, as can our method. Hopefully, the results of all of these approaches can be integrated to yield useful results.Institute of Geophysics and Planetary Physics, Contribution No. 2744     

First-principles calculations of equilibrium fractionation of O and Si isotopes in quartz,albite, anorthite,and zircon

In this study, we used first-principles calculations based on density functional theory to investigate silicon and oxygen isotope fractionation factors among the most abundant major silicate minerals in granites, i.e., quartz and plagioclase (including albite and anorthite), and an important accessory mineral zircon. Combined with previous results of minerals commonly occurring in the crust and upper mantle (orthoenstatite, clinoenstatite, garnet, and olivine), our study reveals that the Si isotope fractionations in minerals are strongly correlated with SiO₄ tetrahedron volume (or average Si–O bond length). The ³⁰Si enrichment order follows the sequence of quartz > albite > anorthite > olivine ≈ zircon > enstatite > diopside, and the ¹⁸O enrichment follows the order of quartz > albite > anorthite > enstatite > zircon > olivine. Our calculation predicts that measurable fractionation of Si isotopes can occur among crustal silicate minerals during high-temperature geochemical processes. This work also allows us to evaluate Si isotope fractionation between minerals and silicate melts with variable compositions. Trajectory for δ³⁰Si variation during fractional crystallization of silicate minerals was simulated with our calculated Si isotope fractionation factors between minerals and melts, suggesting the important roles of fractional crystallization to cause Si isotopic variations during magmatic differentiation. Our study also predicts that δ³⁰Si data of ferroan anorthosites of the Moon can be explained by crystallization and aggregation of anorthite during lunar magma ocean processes. Finally, O and Si isotope fractionation factors between zircon and melts were estimated based on our calculation, which can be used to quantitatively account for O and Si isotope composition of zircons crystallized during magma differentiation.     

Experimental determination of the solubility of the assemblage paragonite,albite, and quartz in supercritical H2O

The concentrations of Na, Al, and Si in an aqueous fluid in equilibrium with natural albite, paragonite, and quartz have been measured between 350°C and 500°C and 1 to 2.5 kbar. Si is the dominant solute in solution and is near values reported for quartz solubility in pure H₂O. At 1 kbar the concentrations of Na and Al remain fairly constant from 350°C to 425°C but then decrease at 450°C. At 2 kbar, Na increases slightly with increasing temperature while Al remains nearly constant. Concentrations of Si, Na, and Al all increase with increasing pressure at constant temperature.The molality of Al is close to that of Na and is nearly a log unit greater than calculated molalities assuming Al(OH)⁰₃ is the dominant Al species. This indicates a Na-Al complex is the dominant Al species in solution as shown by Anderson and Burnham (1983) at higher temperature and pressure. The complex can be written as NaAl(OH)⁰₄ ± nSiO₂ where n is the number of Si atoms in the complex. The value of n is not well constrained but appears to be less than or equal to 3.The results indicate Al can be readily transported in pure H₂O solutions at temperatures and pressures as low as 350°C and 1 kbar.     

The structure of freedite,Pb8Cu(AsO3)2O3Cl5

Summary The structure of freedite, Pb₈Cu(AsO₃)₂O₃Cl₅, [a = 13.578(2),b = 20.099(3),c = 7.465(1)Å; = 105.73(1)°; space group C2/m; Z = 4] was determined by direct methods and Fourier summations. The refinement of the atomic coordinates and thermal parameters-the metal atoms anisotropic, the remaining atoms isotropic-yielded anR value of 0.086 (R _w = 0.061). The five crystallographically independent Pb atoms are each surrounded by three resp. four O atoms and four Cl atoms. The novel feature of this structure are formal [(AsO₃)₂(CuCl)₂(AsO₃)₂] groups, in which the Cu atoms are tetrahedrally coordinated to two Cl and two As atoms [Cu-Cl = 2.43(8)Å2 × , Cu-As = 2.32(1)Å2 ×]. The mineral is considered to contain Cu(I) and As(III) atoms linked together by covalent Cu-As bonds. The formal groups mentioned are bound to the Pb atoms via Cl and O atoms.

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Die Struktur des Freedits, Pb₈Cu(AsO₃)₂O₃Cl₅

Zusammenfassung Die Struktur des Freedits, Pb₈Cu(AsO₃)₂O₃Cl₅, [a = 13,578(2),b = 20,099(3),c = 7,465(1)Å; = 105,73(1); Raumgruppe C2/m;Z = 4] wurde anhand direkter Methoden und Fouriersummationen bestimmt. Die Verfeinerung der Ortskoordinaten und der Temperaturparameter - Metallatome anisotrop, übrige Atome isotrop -ergab einenR-Wert von 0,086 (R _w = 0,061). Die fünf kristallographisch verschiedenen Pb-Atome werden von drei bzw. vier O-Atomen sowie jeweils vier Cl-Atomen umgeben. Ein neues Bauprinzip dieser Struktur sind formale [(AsO₃)₂(CuCl)₂(AsO₃)₂]-Gruppen, in denen die Cu-Atome durch zwei Cl- und zwei As-Atome tetraedrisch umgeben sind [Cu-Cl= 2,43(8)Å2 ×, Cu-As = 2,32(1)Å2 x]. Es wird angenommen, daß in diesem Mineral Cu(I)- und As(III)-Atome vorliegen, die über kovalente Bindungen verknüpft sind. Diese formalen Gruppen sind über die Cl- und O-Atome an die Pb Atome gebunden.

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With 2 Figures     

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.     

The effect of fluorine, boron and excess sodium on the critical curve in the albite–H2O system

Experiments to define the critical curve for a series of silicate melts in equilibrium with a hydrous fluid were carried out in a hydrothermal diamond anvil cell. Silicate compositions studied were albite with several wt% excess Na₂O, B₂O₃ and F₂O_-1. Complete miscibility between melt and water was observed at lower pressure and temperature conditions compared to pure albite for all compositions. For albite + excess Na₂O, the critical curve had been lowered by 143 and 247 °C at 10 kbar for 5 and 10 wt% excess Na. For albite +5 and 10 wt% F, the difference at 10 kbar was 147 and 246 °C respectively, and for albite +5 and 10 wt% B differences of 168 and 262 °C were found. These results are likely to be additive, with the presence of more than one of the components depressing the critical curve to even lower temperatures and pressures. The results suggest that in complex pegmatitic systems, complete miscibility between melt and fluid may be important in the final stages of crystallisation. The unusual properties of fluid phases under conditions close to the critical curve in a silicate melt-water system may be essential for the enrichment of trace elements in pegmatites as well as for the formation of typical pegmatite textures.     

Phase relations in the system NaAlSi3O8-KAlSi3O8-CaAl2Si2O8-SiO2 at 1 kilobar water vapour pressure

Crystal-melt relations at a water vapour pressure of 1 kilobar have been determined for planes at 3, 5, 7.5, and 10 weight per cent anorthite in the system NaAlSi₃O₈KAlSi₃O₈-CaAl₂Si₂O₈-SiO₂. The ratio of the silicate components in the liquids which are in univariant equilibrium with plagioclase, alkali feldspar, quartz and gas are Ab₃₁Or₂₈Q₃₈An₃ (weight per cent) at 730°±5–10° C, Ab₂₁Or₃₄Q₄₀An₅ at 745°±5–10° C and Ab₁₀Or₃₉ Q_43.5An_7.5 at 780°±10° C. The univariant curve on which the above compositions lieoriginates on the H₂O-saturated Or-An-Q plane at a composition containing less than 10 weight per cent An and terminates within 1.5 weight per cent An of the H₂O-saturated Or-Ab-Q plane. Experimental data for the synthetic system have been used to illustrate a discussion on the partial melting of metasediments and the possible significance of such a process with respect to the genesis of granitic rocks. Data taken from the literature (Winkler and v. Platen, 1960, 1961a) have been used to illustrate that the normative salic composition of a sediment has a strong influence on the composition of any melt which form when such a rock is subjected to high temperatures and pressures.     

Das System KFeSi3O8−KAlSi3O8−H2O mit Untersuchungen über die Mikroklin-Sanidin-Beziehungen

Zusammenfassung Im System KFeSi₃O₈–KAlSi₃O₈ wird eine Mischungslücke gefunden, welche den Bereich von 10–60 Mol. % K-Fe-Feldspat umfaßt. Die Mischkristalle links und rechts der Mischungslücke verhalten sich ähnlich wie ihre benachbarten Endglieder. Das Fehlen von intermediären Phasen auf der Eisenseite und die Mischungslücke machen es wahrscheinlich, daß das Verhalten des K-Fe-Feldspates nicht auf das Verhalten des K-Al-Feldspates extrapoliert werden darf.

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Summary In the system KFeSi₃O₈–KAlSi₃O₈ a miscibility-gap is found from 10 to 60 Mol.% K-Fe-felspar. The mixed crystals on the right and left side of the miscibility-gap show a behaviour similar to the corresponding end-members. The lack of intermediate phases on the iron-side and the miscibility-gap make probable that one cannot extrapolate the behaviour of the K-Fe-felspar to the behaviour of the K-Al-felspar.

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Mit 3 Textabbildungen

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Herrn Professor Dr.F. Machatschki zum 70. Geburtstag gewidmet.     

Liquidas phase relationships in the system CaAl2Si2O8-NaAlSi3O8-KAlSi3O8-NaAlSiO4-KAlSiO4 atP(H2O)=5 kb

Liquidus phase equilibria have been determined in the system CaAl₂Si₂O₈-NaAlSi₃O₈-KAlSi₃O₈-NaAlSiO₄-KAlSiO₄ (An-Ab-Or-Ne-Ks) at a pressure of water of 5 kb, for low anorthite contents. The main effects of increasing anorthite content on phase relationships in the system Ab-Or-Ne-Ks include the expansion of the plagioclase stability field towards the potassium-rich part of the system, and an accompanying contraction of the alkali feldspar, leucite, nepheline and kalsilite stability fields; and an increase in liquidus temperatures throughout most of the compositional range. Two quaternary invariant points have been identified in the system, one a reaction point between the fields of alkali feldspar, plagioclase, nepheline and kalsilite at approximately An₄, and the other probably a quaternary eutectic between the fields of alkali feldspar, plagioclase, leucite and kalsilite at approximately An₆. A shallow minimum trough in liquidus temperatures occurs on the two-feldspar surface, and this would be expected to control the paths of liquids cooling under equilibrium conditions. Phase relationships in this quaternary system have been applied to the interpretation of the histories of the potassium-rich rocks of the Roman Volcanic Region, Italy. Differentiation of the phonolitic series in this region may have occurred by two-feldspar fractionation.     

The Phase Relations of Aluminous Iron Biotites in the System KAISi3O8-KAISiO4-AI2O3-Fe-O-H

The experimental work on biotites has primarily involved compositionsalong the annite-phlogopite join, but most natural biotitescontain significantly larger amounts of aluminum. At the sametime, the aluminum content of natural biotites varies considerably.The available evidence indicates that these variations in thealuminum content of biotite depend on the conditions of formationand the whole rock chemistry. Experiments on the phase relations of aluminous iron biotitesin the silica deficient system KAlSiO₄-KAlSi₃O₈-Al₂O₃-Fe-O-H(pfluid = 2 kb) indicate that compositions up to Ann₇₅ can besynthesized on the join annite [K₂Fe₆Al₂Si₆O₂₀(OH)₄]-aluminumbiotite [K₂Al₆Al₂Al₆O₂₀(OH)₄]. The aluminous biotites are stableto higher temperatures than annite. An isobaric divariant equilibrium,Bio_ss-Mt_ss-Sa-Lc-V, extends to higher oxygen fugacities fromthe Ann-Mt-Sa-Lc-V curve of Eugster & Wones (1962). Compositioncontours on this surface indicate that both the magnetite andbiotite become more aluminous with increasing temperature and/oroxygen fugacity. The Bio_ss-Mt_ss-Sa-Lc-V reaction surface isterminated by equilibria involving the additional phases muscovite,corundum, and hercynite respectively as the conditions becomemore reducing. At 2 kb fluid pressure; aluminum-rich iron biotiteis stable to 555 °C on the HM buffer, 763 °C on theMt-Hc-Cor buffer, 820 °C on NNO, and about 860 °C onQFM. The data obtained can be applied to a number of biotitesyenites and appears to explain why iron-rich aluminum biotitesoccur in these rocks.     

Das System NaAlSi3O8-BaAl2Si2O8-H2O bei 1 Kbar

The system albite-celsian-water was investigated at isothermal sections of 670, 760, 800, 900, 1000 and 1100° C at 1 Kbar. At temperatures above about 950° C the existence of a solid solution series could be shown. In the condensed part of the 930° C/1 Kbar section the partition of barium between melt and coexisting crystals was measured using an electron probe microanalyzer. The barium content of crystals grown in equilibrium with a melt is always higher than the barium content of the starting composition, so albite-celsian shows an ascending type solid solution series at low total water pressures. In the subsolidus region two types of solvi are existent, which show different ways of phase unmixing. The relatively low barium contents of natural albites are interpreted as being due to geochemical reasons rather than crystalchemical reasons.

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Meinem hochverehrten Lehrer, Herrn Prof. Dr. K. Jasmund, danke ich für sein lebhaftes Interesse während der Durchführung dieser Arbeit und für die kritische Durchsicht des Manuskripts. Mein Dank gilt ferner Herrn Dr. H. A. Seck für die Einarbeitung in die experimentellen Methoden der Hydrothermalsynthese und für kritische Anmerkungen zum Manuskript. Fräulein Dr. M. Corlett danke ich für wertvolle Informationen zur Messung mit der Elektronenstrahl-Mikrosonde.

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Die Untersuchung wurde mit Hilfe von Personal- und Sachmitteln durchgeführt, die Herrn Professor Dr. K. Jasmund von der Deutschen Forschungsgemeinschaft zur Verfügung gestellt worden waren.     

The temperature dependence of the speciation of water in NaAlSi3O8-KAlSi3O8 melts: an application of fictive temperatures derived from synthetic fluid-inclusions

 The speciation of water dissolved in glasses along the join NaAlSi₃O₈-KAlSi₃O₈ has been investigated using infrared spectroscopy. Hydrous melts have been hydrothermally synthesized by chemical equilibration of cylinders of bubble-free anhydrous start glasses with water at 1040^° C and 2 kbar. These melts have been isobarically and rapidly (200^° C/s) “drop”-quenched to room temperature and then subsequently depressurized. The speciation of water in the quenched glasses reflects the state of water speciation at a temperature (the so-called fictive temperature) where the quenched-in structure of the glasses closely corresponds to the melt structure at equilibrium. This fictive temperature is detectable as the macroscopically measureable glass transition temperature of these melt compositions. A separate set of experiments using vesicular samples of the same chemistry has precisely defined the glass transition temperature of these melts (±5^° C) on the basis of homogenization temperatures for water-filled fluid inclusions (Romano et al. 1994). The spectroscopic data on the speciation of water in these quenched glasses has been quantified using experimentally determined absorptivities for OH and H₂O for each individual melt composition. The knowledge of glass transition temperatures, together with quantitative speciation data permits an analysis of the temperature dependence of the water speciation over the 113^° C range of fictive temperatures obtained for these water-saturated melts. The variation of water speciation, cast as the equilibrium constant K where K = [H₂O] [O _m ]/[OH]² is plotted versus the fictive temperature of the melt to obtain the temperature dependence of speciation. Such a plot describes a single linear trend of the logarithm of the equilibrium constant versus reciprocal temperature, implying that the exchange of K for Na has little influence on melt speciation of water. The enthalpy derived from temperature dependence is 36.5(±5) kJ/mol. The results indicate a large variation in speciation with temperature and an insensitivity of the speciation to the K–Na exchange. Received: 8 March 1995/Accepted: 6 June 1995     

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.     

On the theory of Al,Si ordering in albite

Calculations of the equilibrium distribution of Al, Si in the albite framework based on quasi-chemical theories of order, disorder transformations (Yang 1945; Yang and Li 1947; Li 1949) were made for a two-dimensional framework model. The ordering is caused by the energy of Al, Si interchange between sites of different crystal-chemical types and the energy of nearest neighbour interaction. By taking into account the decrease in the energy of interchange between sites with increasing disordering and with increasing temperature, and by examining different relationships for site-to-site interchange energy and the nearest neighbour interaction, it is possible to understand the basic characteristics of the transformation from low (essentially ordered) to high (essentially disordered) albite as revealed by experiment. These characteristics are: (1) abrupt variation of the equilibrium degree of order within a narrow temperature range and possible first order phase transformation for the transition from low-albite to high-albite, (2) hysteresis of the synthetic high albite transformation path and of the low albite hydrothermal “annealing” path, (3) presence of a temperature range where high albite is stable and has a continually changing equilibrium degree of order.