Ephesite,Na(LiAl2) [Al2Si2O10] (OH)2: I. thermal stability and standard state thermodynamic properties

Ephesite, Na(LiAl₂) [Al₂Si₂O₁₀] (OH)₂, has been synthesized for the first time by hydrothermal treatment of a gel of requisite composition at 300≦T(° C)≦700 and \(P_{H_2 O}\) upto 35 kbar. At \(P_{H_2 O}\) between 7 and 35 kbar and above 500° C, only the 2M₁ polytype is obtained. At lower temperatures and pressures, the 1M polytype crystallizes first, which then inverts to the 2M₁ polytype with increasing run duration. The X-ray diffraction patterns of the 1M and 2M₁ poly types can be indexed unambiguously on the basis of the space groups C2 and Cc, respectively. At its upper thermal stability limit, 2M₁ ephesite decomposes according to the reaction (1) $$\begin{gathered} {\text{Na(LiAl}}_{\text{2}} {\text{) [Al}}_{\text{2}} {\text{Si}}_{\text{2}} {\text{O}}_{{\text{10}}} {\text{] (OH)}}_{\text{2}} \hfill \\ {\text{ephesite}} \hfill \\ {\text{ = Na[AlSiO}}_{\text{4}} {\text{] + LiAl[SiO}}_{\text{4}} {\text{] + }}\alpha {\text{ - Al}}_{\text{2}} {\text{O}}_{\text{3}} {\text{ + H}}_{\text{2}} {\text{O}} \hfill \\ {\text{nepheline }}\alpha {\text{ - eucryptite corundum}} \hfill \\ \end{gathered}$$ Five reversal brackets for (1) have been established experimentally in the temperature range 590–750° C, at \(P_{H_2 O}\) between 400 and 2500 bars. The equilibrium constant, K, for this reaction may be expressed as (2) $$log K{\text{ = }}log f_{{\text{H}}_{\text{2}} O}^* = 7.5217 - 4388/T + 0.0234 (P - 1)T$$ where \(f_{H_2 O}^* = f_{H_2 O} (P,T)/f_{H_2 O}^0\) (1,T), with T given in degrees K, and P in bars. Combining these experimental data with known thermodynamic properties of the decomposition products in (1), the following standard state (1 bar, 298.15 K) thermodynamic data for ephesite were calculated: H _f,298.15 ⁰ =-6237372 J/mol, S _298.15 ⁰ =300.455 J/K·mol, G _298.15 ⁰ =-5851994 J/mol, and V _298.15 ⁰ =13.1468 J/bar·mol.     

Thermodynamic mixing properties of Mg(Al,Cr)2O4 spinel crystalline solution at high temperatures and pressures

Three Al-Cr exchange isotherms at 1,250°, 1,050°, and 796° between Mg(Al, Cr)₂O₄ spinel and (Al, Cr)₂O₃ corundum crystalline solutions have been studied experimentally at 25 kbar pressure. Starting from gels of suitable bulk compositions, close approach to equilibrium has been demonstrated in each case by time studies. Using the equation of state for (Al, Cr)₂O₃ crystalline solution (Chatterjee et al. 1982a) and assuming that the Mg(Al, Cr)₂O₄ can be treated in terms of the asymmetric Margules relation, the exchange isotherms were solved for Δ G ^*, and . The best constrained data set from the 1,250° C isotherm clearly shows that the latter two quantities do not overlap within three standard deviations, justifying the choice of asymmetric Margules relation for describing the excess mixing properties of Mg(Al, Cr)₂O₄ spinels. Based on these experiments, the following polybaric-polythermal equation of state can be formulated: , P expressed in bars, T in K, G _m ^ex and W _G,i ^Sp in joules/mol. Temperature-dependence of G _m ^ex is best constrained in the range 796–1,250° C; extrapolation beyond that range would have to be done with caution. Such extrapolation to lower temperature shows tentatively that at 1 bar pressure the critical temperature, T _c, of the spinel solvus is 427° C, with dT_c/dP≈1.3 K/kbar. The critical composition, X _c, is 0.42 , and changes barely with pressure. Substantial error in calculated phase diagrams will result if the significant positive deviation from ideality is ignored for Al-Cr mixing in such spinels.     

Lithogeochemistry as an indicator of uranium and tin mineralization, South Mountain Batholith, Nova Scotia, Canada

Uranium and tin occurrences in the South Mountain Batholith are preferentially found in or near a para-intrusive rock suite which is characterized by strong granophile element enrichments. Furthermore, bodies which show a Th-enrichment trend with increasing differentiation appear to be more favorable exploration targets than spatially associated bodies in which Th is depleted.     

Experimental and thermodynamic study of heterogeneous and homogeneous equilibria in the system NaAlSiO4-SiO2

Internally consistent thermodynamic datasets available at present call for a further improvement of the data for nepheline (Holland and Powell 1988; Berman 1991). Because nepheline is a common rock-forming mineral, an attempt has been made to improve on the present state of knowledge of its thermodynamic properties. To achieve that goal, two heterogeneous reactions involving nepheline, albite, jadeite and a-quartz in the system NaAlSiO₄-SiO₂ have been reversed bylong duration runs in the range 460 ≤ T(°C) ≤ 960 and 10 ≤ P(kbar) ≤ 22. Given sufficiently long run times, thealbite run products approach internal equilibrium with respect to their Al,Si order-disorder states. Using appropriate thermochemical, thermophysical, and volumetric data, Landau expansion for albite, and the relevant reaction reversals, a refined thermodynamic dataset (Δ_fH_i⁰ and S_i⁰) has been derived for nepheline, jadeite, a-quartz, albite, and monalbite. Our refined data agree very well with theircalorimetric counterparts, but have smaller uncertainties. The refined dataset for Δ_fH_i⁰ and S_i⁰, including their uncertainties and correlation, help generate the NaAlSiO₄-SiO₂ phase diagram including 2a confidence interval for eachP-T curve (Fig. 5). Editorial responsibility: W. Schreyer     

Mildly alkaline basalts from Pavagadh Hill, India: Deccan flood basalts with an asthenospheric origin

Summary Of twelve flows at Pavagadh Hill, the two three-phenocryst-basalt flows with Mg#0.70 and Ni/MgO33 are the most primitive and perhaps as primitive as any basalts in the Deccan province. Scatter on variation diagrams and the occurrence of primitive flows at two different levels in the volcanic sequence implies that most rocks are probably not, strictly speaking, comagmatic. Nevertheless, mass balance calculations indicate a generalized differentiation scheme from primitive basalt to hawaiite that involved removal of olivine, augite, plagioclase and Fe-Ti oxides in the proportions 40:33:22:5 with 50% of the magma remaining. Crustal assimilation had a minimal effect on evolution of the basalts but rhyolites at the top of the volcanic sequence may have been produced by crustal melting following prolonged heat release from alkali basalt pooled along fault zones in the continental crust. Major element based calculations indicate that the most primitive basalts were generated by 7 to 10% melting of mantle peridotite. These low percentages of melting, typical of alkali basalts, are consistent with the steep slopes on chondrite-normalized REE diagrams. Low heavy REE concentrations point to residual garnet in the source region. Incompatible element concentrations (e.g. Rb, Ba, Zr, La) in Pavagadh basalts exceed those in Deccan tholeiitic basalts but are substantially lower than those reported for some other Deccan alkali basalts. Obviously Pavagadh basalts do not reflect the lowest percentages of melting and greatest amount of source region metasomatic enrichment attained in the Deccan province. Deccan tholeiitic and alkali basalts are largely characterized by low La/Nb ratios and high La/Ba ratios similar to those in oceanic island basalts. This indicates minimal involvement of the subcontinental lithospheric mantle in their petrogenesis. Comparison with continental mafic magma provinces where a subcontinental lithospheric mantle imprint is common indicates long periods of extension and/or melting of mantle lithosphere still hot from pre-extension subduction are more likely to produce magmas bearing the lithospheric imprint.

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Alkalische Basalte von Pavagadh Hill, Indien: Deccan-Flutbasalte von Astenosphärischer Herkunft

Zusammenfassung Im Gebiet von Pavagadh Hill, Indien, treten 12 Spät-Deccan und rhyolithische alkalibasaltische Ergüsse und Intrusiva auf. Variationsdiagramme zeigen, daß die Abfolge nicht komagmatisch ist. Zusammen mit Berechnungen der Massenbilanz unterstützen sie vielmehr ein Zwei-Stadienmodell für die Entstehung von Hawaiiten aus sehr primitiven (i.e. Mg#=Mg/(Mg+.(0.9*Fe_totat)) at.%0.70) Basalten. Olivin und Augit dominierten die frühe Fraktionierung während Augit vorherrschte als der Magmaanteil von 65% auf 50% sank. Die Entfernung von Plagioklas spielte bei der Differentiation nur eine geringe Rolle. Niedrige Th/Nb (0,2), Rb/Sr(<0,12) und K/NbVerhältnisse geben keine Hinweise auf signifikante Assimilation von Krustenmaterial. Die Seltene-Erd-Verteilungsmuster (SEE), niedrige Gehalte an schweren SEE sowie die Hauptelementspektren der Alkalibasalte weisen auf eine granatführende Ursprungsregion und auf einen Aufschmelzungsgrad von nur 7% bis 10% hin. Es gibt jedoch auch stärker alkalische (höhere Rb, Zr etc.) Deccanbasalte (i.e. Rajpipla). Die Assoziation von Deccanalkalibasalten, Rhyolithen und Störungszonen zeigt, daß letztere die Extraktion von Magma aus dem Mantel erleichterten und dazu führten, daß Magma aus Magmenkammern Krustenschmelzen (Rhyolithe) produzierte. Deccanbasalte tendieren zu hohen La/Ba und niedrigen La/Nb-Verhältnissen; dies weist auf eine asthenosphärische Herkunft hin, selbst wenn die Gesteine verhältnismäßig spät gebildet wurden (i.e. Pavagadh). Längere Perioden von Krustenextension oder von Subduktion, die der Extension vorhergeht, führt offensichtlich zur Entstehung von Magmen mit einer lithosphärischen Komponente.

     

Radiation condensation instability in a plasma with ionization and recombination

In this work, we consider radiation (thermal) instability in a weakly ionized plasma with continuous ionization and recombination. The situation can be visualized in the case of envelopes of planetary nebulae, which are envelopes of ionized plasmas surrounding red giant stars. Various observations report continuous photoionization of these plasmas by the highly energetic streams of photons emanating from the parent star. Recently, it has been shown that thermal instability can be a probable candidate in such plasmas for the existence of small scale structures (viz., striations) whose kinematic age is much smaller than that of the parent nebula. We therefore report a systematic study of these plasmas with photoionization and determine the instability domain. We have shown that the continuous ionization and recombination may lead to modification of the underlying instability, which may limit the size of the small structures that are believed to form from these instabilities, and may thus provide an explanation of the physical processes responsible for the existence of these structures. We further show that in many cases the system bifurcates to an ovserstable (growing wave) state from a condensation instability (monotonic) and vice versa.     

An internally consistent set of thermodynamic data for twentyone CaO-Al2O3-SiO2- H2O phases by linear parametric programming

The technique of linear parametric programming has been applied to derive sets of internally consistent thermodynamic data for 21 condensed phases of the quaternary system CaO-Al₂O₃-SiO₂-H₂O (CASH) (Table 4). This was achieved by simultaneously processing:

1. calorimetric data for 16 of these phases (Table 1), and
2. experimental phase equilibria reversal brackets for 27 reactions (Table 3) involving these phases.

Calculation of equilibrium P-T curves of several arbitrarily picked reactions employing the preferred set of internally consistent thermodynamic data from Table 4 shows that the input brackets are invariably satisfied by the calculations (Fig. 2a). By contrast, the same equilibria calculated on the basis of a set of thermodynamic data derived by applying statistical methods to a large body of comparable input data (Haas et al. 1981; Hemingway et al. 1982) do not necessarily agree with the experimental reversal brackets. Prediction of some experimentally investigated phase relations not included into the linear programming input database also appears to be remarkably successful. Indications are, therefore, that the thermodynamic data listed in Table 4 may be used with confidence to predict geologic phase relations in the CASH system with considerable accuracy. For such calculated phase diagrams and their petrological implications, the reader's attention is drawn to the paper by Chatterjee et al. (1984).     

Optimum merger time-scales and binary evolution

A study of galaxy mergers, on the basis of the collisional theory, using galaxy models without halos and considering the evolution of the proginator galaxies only from a time when the gravitational interaction between them is physically significant, indicates that most of the mergers are affected in 2 to 3 orbital periods for progenitors of comparable mass: shorter and longer time-scales being underabundant. These results have a bearing on the evolution of binary galaxies; indicating that once the relative orbit of a binary is circularized, the components will merge during the subsequent orbit or the next one (in a time-scale ~ 10⁸ years). These results are also indicative of the fact that binary evolution is very likely to cause a gradual evolution of the fundamental plane occupied by paired ellipticals from that of isolated ellipticals. After the merger, the remnant is very likely to define a fundamental plane with a slightly different slope.     

Bayes estimation: A novel approach to derivation of internally consistent thermodynamic data for minerals,their uncertainties,and correlations. Part II: Application

Internally consistent thermodynamic data, including their uncertainties and correlations, are reported for 22 phases of the quaternary system CaO-Al₂O₃-SiO₂-H₂O. These data have been derived by simultaneous evaluation of the appropriate phase properties (PP) and reaction properties (RP) by the novel technique of Bayes estimation (BE). The thermodynamic model used and the theory of BE was expounded in Part I of this paper. Part II is the follow-up study illustrating an application of BE. The input for BE comprised, among others, the a priori values for standard enthalpy of formation of the i-th phase, Δ_f H _i ⁰ , and its standard entropy, S _i ⁰ , in addition to the reaction reversal constraints for 33 equilibria involving the relevant phases. A total of 269 RP restrictions have been processed, of which 107 turned out to be non-redundant. The refined values for Δ_f H _i ⁰ and S _i ⁰ obtained by BE, including their 2σ-uncertainties, appear in Table 4; the Appendix reproduces the corresponding correlation matrix. These data permit generation of computed phase diagrams with 2σ-uncertainty envelopes based on conventional error propagation; Fig. 3 depicts such a phase diagram for the system CaO-Al₂O₃-SiO₂. It shows that the refined dataset is capable of yielding phase diagrams with uncertainty envelopes narrow enough to be geologically useful. The results in Table 4 demonstrate that the uncertainties of the prior values for Δ_f H _i ^Emphasis>0 , given in Table 1, have decreased by up to an order of magnitude, while those for S _i ⁰ improved by a factor of up to two. For comparison, Table 4 also lists the refined Δ_f H _i ⁰ and S _i ⁰ data obtained by mathematical programming (MAP), minimizing a quadratic objective function used earlier by Berman (1988). Examples of calculated phase diagrams are given to demonstrate the advantages of BE for deriving internally consistent thermodynamic data. Although P-T curves generated from both MAP and BE databases will pass through the reversal restrictions, BE datasets appear to be better suited for extrapolations beyond the P-T range explored experimentally and for predicting equilibria not constrained by reversals.