Phase relations to 3 kbar in the systems edenite + H2O and edenite + excess quartz + H2O

Amphiboles approached edenite (NaCa₂Mg₅Si₇AlO₂₂(OH)₂), richterite (Na₂CaMg₅Si₈O₂₂(OH)₂), tremolite (□Ca₂Mg₅Si₈O₂₂(OH)₂) solid solutions were studied by conventional hydrothermal techniques employing the bulk compositions edenite, and edenite + additional quartz, all with excess H₂O. For the stoichiometric edenite bulk composition + excess H₂O, the equilibrium phase assemblage is diopside + Na-phlogopite + forsterite + fluid at, and just above the amphibole high-temperature limit at 850 ± 5°C, 500 bar, and 880 ± 5°C, 1000 bar. The breakdown temperature of sodic phlogopite is 855 ± 3°C at 500 bar, and 890 ± 5°C at 700 bar, producing nepheline + plagioclase (or melt), additional forsterite and fluid. Diopside and Na-phlogopite solid solution coexist over a broad P_fluid-T region, even within the amphibole field, where they are associated with an edenite-richterite (-tremolite) solid solution of approximate composition Ed₃₅Rc₅₀Tr₁₅.In the system edenite + 4 quartz + excess H₂O, nearly pure tremolite and albite coexist stably between 670° and 830°C at 1000 bar and give way to the possibly metastable assemblage diopside + talc + albite below 670°C. In the presence of albite, tremolite reacts to produce diopside + quartz + enstatite + fluid above 830°C at 1000 bar. For the investigated silica-rich bulk composition, amphibole P_fluid-T stability is divided by the albite melting curve into a tremolite + albite field, and a tremolite + aqueous melt field. Substantial equilibrium solid solution of tremolite towards edenite or richterite was not observed for silica-excess bulk compositions. Metastable edenite-rich amphiboles initially synthesized change to tremolite with increasing run length in the presence of free SiO₂.Edenitic amphibole is stable only over a very limited temperature range in silica-undersaturated environments, thus accounting for its rarity in nature. Na-phlogopite solid solutions are also disfavored by high a_SiO2; even for nepheline-normative lithologies, a hypothesized rapid low-temperature conversion to vermiculite or smectite could partly explain the scarcity of sodic phlogopite in rocks.     

Experimental investigation of the mechanism of the reaction: 1 tremolite+11 dolomite ⇌ 8 forsterite+13 calcite+9 CO2+1H2O

Stoichiometric mixtures of tremolite and dolomite were heated to 50° C above equilibrium temperatures to form forsterite and calcite. The pressure of the CO₂-H₂O fluid was 5 Kb and \(X_{{\text{CO}}_{\text{2}} }\) varied from 0.1 to 0.6. The extent of the conversion was determined by the amount of CO₂ produced. The resulting mixtures of unreacted tremolite and dolomite and of newly-formed forsterite and calcite were examined with a scanning electron microscope. All tremolite and dolomite grains showed obvious signs of dissolution. At fluid compositions with \(X_{{\text{CO}}_{\text{2}} }\) less than about 0.4, the forsterite and calcite crystals are randomly distributed throughout the charges, indicating that surfaces of the reactants are not a controlling factor with respect to the sites of nucleation of the products. A change is observed when \(X_{{\text{CO}}_{\text{2}} }\) is greater than about 0.4; the forsterite and calcite crystals now nucleate and grow at the surface of the dolomite grains, thus indicating a change in mechanism at medium CO₂ concentrations. As the reaction progresses, the dolomite grains become more and more surrounded by forsterite and calcite, finally forming armoured relics of dolomite. Under experimental conditions this characteristic texture can only be formed if the CO₂-concentration is greater than about 40 mole %. These findings make it possible to estimate the CO₂-concentration from the texture of the dolomite+tremolite+forsterite+calcite assemblage. The results suggest a dissolution-precipitation mechanism for the reaction investigated. In a simplified form it consists of the following 4 steps:

1. Dissolution of the reactants tremolite and dolomite.
2. Diffusion of the dissolved constituents in the fluid.
3. Heterogeneous nucleation of the product minerals.
4. Growth of forsterite and calcite from the fluid.

Two possible explanations are discussed for the development of the amoured texture at \(X_{{\text{CO}}_{\text{2}} }\) above 0.4. The first is based upon the assumption that dolomite has a lower rate of dissolution than tremolite at high \(X_{{\text{CO}}_{\text{2}} }\) values resulting in preferential calcite and forsterite nucleation and growth on the dolomite surface. An alternative explanation is the formation of a raised CO₂ concentration around the dolomite grains at high \(X_{{\text{CO}}_{\text{2}} }\) values, leading to product precipitation on the dolomite crystals.     

The mechanism of the reaction 1 tremolite+3 calcite+2 quartz =5 diopside+3 CO2+1 H2O: results of powder experiments

The mechanism of the reaction 1 tremolite +3 calcite+2 quartz=5 diopside+3 CO₂+1 H₂O was investigated at 2 and 5 kb, , using powder experiments lasting from 14 to 170 days. Because experiments were at high ratios of fluid to solids, the study identified the mechanism under surface-control conditions and thus establishes which reactant surface determines the kinetics. To achieve a diopside nucleation rate high enough to gain detectable reaction in the time of experimentation, the equilibrium boundary had to be overstepped by 30°–60° C at 5 kb. Experiments in which diopside successfully nucleated show that the reaction proceeds by a dissolution-crystallization mechanism. Experimentally-produced textures are presented in a series of SEM images and demonstrate that diopside nucleates and grows topotactically exclusively on tremolite. The mechanism of the forward reaction is modeled by a simplified scheme consisting of three processes, each comprising formation, transport and incorporation of 1) the Ca-, 2) the Mg-, and 3) the Si-bearing species in the fluid in response to dissolution of the reactants and crystallization of diopside. Using the dependence of the overall-reaction rate on the surface area of the reactants, it was experimentally determined that process 2) (dissolution of tremolite, transport of the Mg-bearing species in the fluid and crystallization of diopside) will be rate-limiting in most cases where metamorphism occurs in an internally controlled system. Due to the experimental design chosen, the dissolution of tremolite at the beginning of process 2) is rate-limiting in the experiments. The magnitude of the probable temperature-overstep necessary to achieve a significant nucleation rate during metamorphism is discussed on the basis of the experimental evidence and a simple nucleation rate model.     

Experimental investigation of the reaction forsterite + H2O ⇌ serpentine + brucite

A new determination of the equilibrium reaction: $$\begin{gathered} 2{\text{ Mg}}_{\text{2}} [{\text{SiO}}_{\text{4}} ] + 3{\text{ H}}_{\text{2}} {\text{O}} \rightleftharpoons {\text{1 Mg}}_{\text{3}} [({\text{OH)}}_{\text{4}} |{\text{Si}}_{\text{2}} {\text{O}}_{\text{5}} ] + 1{\text{ Mg(OH)}}_{\text{2}} \hfill \\ \hfill \\ {\text{ forsterite serpentine brucite}} \hfill \\ \end{gathered} $$ yielded equilibrium temperatures which lie (at identical H₂O-pressures) about 60° C lower than all previously published data (Bowen and Tuttle, 1949; Yoder, 1952; Kitahara et al., 1966; Kitahara and Kennedy, 1967). It has been shown that the above authors have determined not the stable equilibrium curve but instead a metastable “synthesis boundary”. The actual (stable) equilibrium curve is located at 0,5 kb and 350° C 2,0 kb and 380° C 3,5 kb and 400° C 5,0 kb and 420° C 6,5 kb and 430° C.     

Subsolidus and Partial Melting Reactions in the Quartz-excess CaO+MgO+Al2O3+SiO2+H2O System under Water-excess and Water-deficient Conditions to 10 kb: Some Implications for the Origin of Peraluminous Melts from Mafic Rocks

Experimental results up to 10 kb pressure are presented on thestability of amphibole in the quartz-excess CaO+MgO+Al₂O₃ (CMASH)system under H₂O)-excess and H₂O deficient conditions. Amphiboleis stable above the solidus under H₂O-excess conditions whereasunder H₂O-deficient conditions dehydration melting of amphibole-bearingassemblages defines the solidus. The successive appearance ofamphibole, talc, and zoisite with increasing pressure considerablymodifies the plagioclase-pyroxene-garnet-kyanite reactions documentedexperimentally in the CaO+MgO+Al₂O₃+SiO₂ system for gabbro-granulite-eclogitetransitions. Although both clino pyroxene and cordierite (withanorthite+orthopyroxene+quartz) may melt eutectically at oneatmosphere to form diopside-normative and corundum-normativemelts respectively, at higher pressures under H₂O-excess conditionsthe peritectic melting of mafic rock compositions produces corundum-normativeliquids together with either clinopyroxene or amphibole. Dehydrationmelting produces melts which are not corundum-normative. Thesedata are used to discuss the origins and evolution of contrastingbasalt-andesite-dacite-rhyolite volcanic suites and graniticplutons, many of whose silicic variants are corundum-normativein character, such as the Toba luff ignimbrites, Indonesia (Beddoc-Stephenset al., 1983) and I-type granite minimum melts (White &Chappell, 1977). In contrast, it is proposed that for the Cascadesbasalt-andesite-dacite-rhyolite suite the ortho pyroxene-plagioclase-quartzthermal divide was maintained up to rhyolite compositions, therebyprohibiting the derivation of corundum-normative rocks fromdiopside-normative parent magmas. The deduced reaction relations between pyroxenes, amphibole,plagioclase, quartz, and liquid are used to explain the absenceor extreme scarcity of hydrous phases in some hydrous magmas.These phase relations can also explain the development of laterplagioclase overgrowths on resorbed plagioclase cores in graniticintrusives, and the general absence of resorption and overgrowthsin chemically equivalent extrusive rocks. A theoretical analysis of the partial melting of forsterite-bearingassemblages in the CaO+MgO+Al₂O₃+SiO₂+H₂O system shows thatunder H₂O-excess conditions partial melting may generate corundum-normative(but low SiO₂) melts from a peridotite source at shallow depths.     

Experimental determination of the reaction paragonite=jadeite+kyanite+H2O,and internally consistent thermodynamic data for part of the system Na2O−Al2O3−SiO2−H2O,with applications to eclogites and blueschists

Hydrothermal reversal experiments have been performed on the upper pressure stability of paragonite in the temperature range 550–740 ° C. The reaction $$\begin{gathered} {\text{NaAl}}_{\text{3}} {\text{Si}}_{\text{3}} {\text{O}}_{{\text{1 0}}} ({\text{OH)}}_{\text{2}} \hfill \\ {\text{ paragonite}} \hfill \\ {\text{ = NaAlSi}}_{\text{2}} {\text{O}}_{\text{6}} + {\text{Al}}_{\text{2}} {\text{SiO}}_{\text{5}} + {\text{H}}_{\text{2}} {\text{O}} \hfill \\ {\text{ jadeite kyanite vapour}} \hfill \\ \end{gathered}$$ has been bracketed at 550 ° C, 600 ° C, 650 ° C, and 700 ° C, at pressures 24–26 kb, 24–25.5 kb, 24–25 kb, and 23–24.5 kb respectively. The reaction has a shallow negative slope (? 10 bar °C^?1) and is of geobarometric significance to the stability of the eclogite assemblage, omphacite+kyanite. The experimental brackets are thermodynamically consistent with the lower pressure reversals of Chatterjee (1970, 1972), and a set of thermodynamic data is presented which satisfies all the reversal brackets for six reactions in the system Na₂O-Al₂O₃-SiO₂-H₂O. The Modified Redlich Kwong equation for H₂O (Holloway, 1977) predicts fugacities which are too high to satisfy the reversals of this study. The P-T stabilities of important eclogite and blueschist assemblages involving omphacite, kyanite, lawsonite, Jadeite, albite, chloritoid, and almandine with paragonite have been calculated using thermodynamic data derived from this study.     

Die Reaktion Phlogopit + Calcit + Quarz = Tremolit + Kalifeldspat + H2O + C2O

Hydrothermal experiments with mixtures of synthetic minerals have shown the reversibility of the reaction 5 phlogopite + 6 calcite + 24 quartz = 3 tremolite + 5 K-feldspar + 2 H₂O + 6 CO₂. In an isobaric T – diagram the equilibrium curve reaches a maximum at = 0,75. The P, T-values for this maximum are: 2 kb-523°; 4 kb-585°; 6 kb-625°; P±5%, T±10° C. These results give a first approximation of the P, T conditions responsible for a similar mineral reaction which has been recorded from natural metamorphic assemblages.

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Herrn Prof. H. G. F. Winkler danke ich für anregende Diskussionen, desgleichen Herrn Dr. D. Puhan für wichtige Hinweise und Mitteilung seiner exp. Daten. Herrn Prof. V. Trommsdorff und Herrn P. H. Thompson bin ich für petrographische Angaben zu Dank verpflichtet. Der Aufbau der Hydrothermalanlage und die Finanzierung der laufenden Untersuchungen wurde aus den Mitteln des Fonds zur Förderung der wissenschaftlichen Forschung ermöglicht. Für diese Unterstützung gilt daher mein besonderer Dank.     

Geothermobarometry in Four-phase Lherzolites I. Experimental Results from 10 to 60 kb

Experiments were carried out on primitive natural lherzoliticcompositions from 10 to 60 kb and to 1400?C. Mineral compositionswere reversed by using mixes of finely ground (<20µm)minerals from natural rock samples with different initial compositions.The minerals were mixed in proportions to give a primitive uppermantle composition. Further starting materials were a syntheticmineral mix and a sintered oxide mix. Equilibrium was thus approachedfrom different chemical directions, and equilibrium mineralcompositions were inferred from the overlap of microprobe analyses.Fe-loss problems were avoided by using single-crystal olivinesas sample containers. Samples were placed into holes drilledinto cylindrically shaped olivine crystals, which in turn werewelded into Pt capsules. A further advantage of this methodis that oxygen fugacities seem to be buffered by the Ni precipitationcurve. This curve lies very close to the iron-w?stite (IW) buffercurve for mantle olivines. Oxygen fugacities calculated fromcompositions of experimentally produced spinels give valuesslightly above the IW buffer curve. Therefore, practically noFe³⁺ should be present in our experimental charges. Ortho- and clinopyroxene compositions were strictly reversedwith respect to Al Cr, and Na (only cpx) contents and theirmutual amounts of enstatite and diopside components. The datashow the fundamental influence of Na in cpx on two-pyroxenethermometry. Garnet compositions were reversed with respectto Ca, Al, Cr, Ti, and Mn. Other than in CMAS, Ca in garnetis mostly dependent on temperature in the natural system andnot so much on pressure. This behaviour of Ca will most stronglyinfluence barometers based on the Al content of orthopyroxenecoexisting with garnet. The mg-numbers of coexisting phaseswere not strictly reversed. The homogeneity of olivine compositionsand internal consistency of the data set give us confidencethat equilibrium values of mg-number have been reached in almostall cases. The experimental results presented in this paperoffer the unique possibility of simultaneously testing manydifferent thermobarometers which are based on dfferent exchangereactions and which were calibrated in different laboratories.     

Genesis of Peraluminous Granites I. Experimental Investigation of Melt Compositions at 3 and 5 kb and Various H2O Activities

Melting experiments have been performed on a peraluminous quartzo-feldspathicgneiss from Northern Portugal. This gneiss occurs as xenolithsin the Tourem anatectic complex and is the most probable sourcerock for the surrounding anatectic granites. On the basis offield, petrological, and geochemical data, it can be shown thatanatexis took place in the stability field of cordierite + biotiteand that the evolution of magmas is the result of processesinvolving segregation of partial melt and separation of restiteminerals. Experiments were performed at 700, 750, and 800 ?C, 3 and 5kb, and various H₂O activities (aH₂O) to clarify the influenceof aH₂O and melt fraction on the composition of the generatedmelts. Biotite and cordierite are the two main ferromagnesianphases observed in the run products. Cordierite is formed byincongment melting of biotite. For relatively low melt fractions (< 30–35 wt. %),the partial melts coexisting with quartz, alkali feldspar, andplagioclase have a minimum or near-minimum melt composition.The melts become richer in potassium with decreasing aH₂O. Thisresult using a natural rock as starting material is in goodagreement with results achieved in the synthetic Qz-Ab-Or system.In the stability field of biotite and cordierite, the influenceof aH₂O on melt composition is at least as important as theeffect of changing P and/or T. For higher melt fractions the composition of the melt is stronglycontrolled by the disappearance of alkali feldspar and the meltsbecome richer in An and poorer in Or with increasing degreeof melting. The wide range of compositions (especially for K₂O, which variesfrom 3.5 to 5.4%) observed in the experimental peraluminousmelts demonstrates that a wide variety of granitoid magmas maybe produced from the same source rocks. The application of theexperimental results to the Tourem anatectic complex shows thatmelting occurred at H2O-undersaturated conditions (4–5wt. % H₂O in the melts, corresponding to aH₂O of {small tilde}0.5at 5 kb). Experimental melts similar in composition to the mostleucocratic granite of the Tourem anatectic complex (consideredto approximate the composition of the generated melt) were obtainedaround 800 ?C, suggesting that this temperature was attainedduring the peak of anatexis.     

Experiments on the phase transition calcite+wollastonite+ +epidote=grossular-andraditess+CO2+H2O

The reaction 2 epidote+2 calcite+3 wollastonite3 grossular-andradite_ss+ 2 CO₂+1 H₂O has been explored by hydrothermal experiments at a total fluid pressure of 1000 bars. For a grossular-andradite_ss of andradite ₂₅ composition, the isobaric univariant curve passes through the points 458°C: X_CO2=0.00; 521°C: X_CO2=0.026; 523°C: X_CO2=0.052; 526°C: 0.088; 528°C: X_CO2=0.104. This curve intersects the isobaric univariant curve of the reaction calcite+quartz+[H₂O] wollastonite+CO₂+[H₂O] at the isobaric invariant point around 528°C and X_CO2=0.12. At higher values of X_CO2, this reaction is replaced by another one, namely: 2 epidote+5 calcite+3 quartz3 grossular-andradite_ss+5 CO₂+ 1 H₂O. It is demonstrated that both the reactions do actually take place during the metamorphism of calcareous rocks. The petrologic significance of contrasted sequence of reactions within this system observed by various workers is also discussed.     

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 Stability of Chloritoid Below 10 kb PH2o

The stability of chloritoid, FeAl₂SiO₆H₂O, was investigatedat fluid pressures less than 10 kb. At oxygen fugacities definedby the Ni-NiO buffer, chloritoid reacts to Fe-cordierite andhercynite spinel at 550 and 575 °C at 1 and 2 kb fluid pressure.At pressures between 2.5 and 3.5 kb the assemblage aluminousferro-anthophyllite, staurolite and hercynite spinel appears.The breakdown of chloritoid to this assemblage takes place at625, 650, and 675 °C at 5.5, 7.0, and 8.7 kb, respectively.The aluminous ferro-anthophyllite assemblage is stable onlyover 50 °C, reacting with increasing temperature to almandine,staurolite, and hercynite spinel. Under the QFM buffer, thesame equilibria are displaced to higher temperatures and thealuminous ferro-anthophyllite bearing field is further restrictedwith respect to temperature. The 7 Å chamosite assemblage,previously considered to be the metastable equivalent of chloritoidat low pressures, is shown to be unstable and chloritoid canbe synthesized at pressures as low as 1 kb. An analysis of the equilibria and related experimental datapermits the construction of a schematic P-T grid which outlinesthe stability limits of several important mineral assemblagesin this system. Although the experimental and natural systemsare not strictly analogous, there is an excellent degree ofcorrespondence between the defined upper limit of chloritoidstability and previous estimates of the facies boundaries itserves to define.     

Experimentelle Untersuchung der Reaktion Dolomit + Kalifeldspat + H2O ⇌ Phlogopit + Calcit + CO2

The equilibrium curve for the reaction 3 dolomite + 1 K-feldspar + 1 H₂O=1 phlogopite + 3 calcite + 3 CO₂ was determined experimentally at a total gas pressure of 2000 bars using two different methods.

1. In the first case water alone was added to the reactants. The CO₂ component of the gas phase was producted solely by the reaction under favourable P-T conditions. This manner of carrying out the reaction is called the “water method”. With this method sufficient time must be allowed for the gas phase to attain a constant composition (see Fig. 1). Reverse reactions were carried out using reaction products of the forward reaction.
2. In the second case silver oxalate + water were added to the reactants. Breakdown of the silver oxalate leads to formation of a CO₂-H₂O gasphase of definite composition. At constant temperature and gas pressure the \(X_{{\text{CO}}_{\text{2}} } \) determines whether the reaction products will be phlogopite + calcite or dolomite + K-feldspar. In this case it is not necessary to wait for equilibrium to be attained. This method is abbreviated the “oxalate method”. Reactants for reverse reactions are not identical with the products of the forward reaction.

At high temperatures the results of the two different methods agree well (see Tables 1 and 2). Equilibrium was attained in one case at 490° C and \(X_{{\text{CO}}_{\text{2}} } \) of approximately 0.77, and in the other case at 520° C and \(X_{{\text{CO}}_{\text{2}} } \) of 0.90. At lower temperatures there are considerable differences in the results. With the water method an \(X_{{\text{CO}}_{\text{2}} } \) of about 0.25 was reached at 450° C. With the oxalate method dolomite K-feldspar and water still react with each other at even higher \(X_{{\text{CO}}_{\text{2}} } \) values. Phlogopite, calcite and CO₂ are formed together with metastable talc. There are no criteria to indicate which of the methods is the correct one at lower temperatures and in Fig. 2, therefore, both equilibrium curves are plotted.     

Experimental determination of REE fractionation between liquid and vapour in the systems NaCl–H2O and CaCl2–H2O up to 450 °C

Fractionation of selected REE between brine and vapour was experimentally determined using a large-volume rocking Ti-autoclave that allowed quasi-isobaric sampling of liquid-vapour pairs. Samples were extracted along the 350, 400 and 450 °C-isotherms of the H₂O-NaCl system, and along the 400 °C isotherm of the CaCl₂ system. Total salt concentrations were either 6.6 and 10 wt% NaCl or CaCl₂, respectively, and total REE concentrations were about 2 ppm of each REE. Starting pH at room temperature was 1.8, added as HCl. In another series of experiments, REEs were added in amounts of 312 ppm. Here, the starting pH at room temperature was 0.5, added as HNO₃:HCl=1:2. Liquid-vapour pairs (L-V) were analysed for REE by ICP-MS methods. L-V-partitioning of REE along a particular isotherm follows broadly the partitioning of the main salt components, NaCl or CaCl₂. D_REE=REE^V/REE^L decrease rapidly from the critical point with decreasing pressure (equivalent to increasing salinity of the liquid) as the solvus opens. This is independent of the total amount of the added REE. Log D_REE values show approximately linear correlations with decreasing pressure from the critical point to salt-saturated conditions where the L-V curve meets the liquid + vapour + solid boundary. At given P and T, we found a systematic variation of D_REE along the La-Lu suite. HREE are enriched in the vapour phase relative to LREE. Fractionation coefficients K_D=(HREE^V/HREE^L)/(LREE^V/LREE^L) increase linearly with (P=P_crit-P along a particular isotherm. At the 450 °C isotherm, K_D (Lu/La) at the critical point (425 bar and 10 wt% NaCl) is 1; about 2.5 at 350 bar (33 wt% NaCl in the liquid); and about 5 if extrapolated to salt-saturation (250 bar and 52 wt% NaCl in the liquid). The REE fractionation behaviour is similar along the CaCl₂-H₂O solvus boundaries. Existing equations of state and thermodynamic databases of REE species cannot predict this behaviour at L-V-equilibrium conditions. That HREE are preferentially fractionated over LREE into the vapour phase has important petrogenetic consequences. In boiling hydrothermal systems, brines will be depleted in HREE relative to LREE. Isobaric cooling is ineffective for fractionation because the solvus closes and the system eventually shifts into the one-phase field. Fractionation is most effective in systems undergoing isothermal or adiabatic decompression. In an open system, where vapour may escape through cavities, fractionation is probably controlled by a Rayleigh fractionation process, resulting in larger overall fractionation effects. Similar fractionations probably occur during magma degassing at very shallow intrusion levels.     

铝酸钡-钙矿相体系的实验研究

以碳酸钡、碳酸钙和氧化铝为原料,设计配方在不同温度下煅烧,制备了铝酸钡-钙复相水泥.运用X射线粉末衍射(XRD)和扫描电子显微镜(SEM)等手段,对铝酸钡与铝酸钙在不同温度下的固溶过程及相转变进行了分析.结果表明:在升温过程中,首先形成大量的铝酸钡,随着温度升高,铝酸钙含量增多.同时,还出现了少量七铝酸十二钙、铝酸二钙和铝酸三钙.铝酸钡呈柱状,铝酸钡-钙固溶相主要由板状六角形或钝圆状小晶体堆积而成.     

Effects of H2O on the Disequilibrium Breakdown of Muscovite+Quartz

We have examined in detail the effect of H₂O on the texturesand mechanisms produced during the breakdown of muscovite+quartzunder experimental disequilibrium conditions using low-porosityrock samples. Under H₂O conditions (1 wt.% H₂O added) muscovitereacts completely in <5 months at 757?C to a metastable assemblageof peraluminous meltmullite+biotite, a reaction which delaysthe formation of the stable equilibrium assemblage. In contrast,muscovite in the H₂O undersaturated experiments breaks downby both the stable dehydration reaction producing K feldspar+sillimanite+biotiteand by metastable melting reactions in the same sample. Thecom position of the metastable melt is controlled by a numberof kinetic factors which change as a function of time and reactionprogress. Early melts are highly siliceous and sodic due tothe rapid dissolution of quartz relative to muscovite, coupledwith the incongruent melting of the paragonite component ofmuscovite and crystallization of biotite. The delayed nucleationof mullite results in Al supersaturation of the melt, whichinhibits the rate of the melting reaction. Once mullite nucleatesthe degree of Al melt supersaturation is decreased and the rateof muscovite dissolution increases. After complete reactionof muscovite the melt chemistry continues to change as Si diffusesinto the pseudomorphs from adjacent quartz. Even after 5 monthsat 757?C large compositional gradients in Si and Al still persistwithin the melt. In the H₂O experiments metastable melting occursinitially, catalysed by traces of grain boundary fluid or byfluid released from the dehydration of muscovite. However, oncemelting starts any fluid is strongly fractionated into the meltphase, reducing µH₂O Under these conditions further meltingis inhibited and the stable dehydration reaction will continue.Examination of examples of natural muscovite reacted under disequilibriumconditions in xenolithic and contact metamorphic rocks at lowpressures suggests that metastable melting is an important processunder certain geological conditions. It is possible that itis widespread in contact metamorphic rocks, but the texturesindicative of metastable melting reactions are obscured duringthe extended cooling histories of such rocks.     

(斜长石 + 黑云母 + 石英 ) NaCl(NaHCO3) H2O 矿物蚀变与金矿化反应研究 : 450～ 250 ℃和 50 MPa

采用（斜长石＋黑云母＋石英）这三种单矿物组合与1mol/L NaCl或0．5mol/L NaCl 0.5mol/L NaHCO3溶液在450－250℃和50MPa条件下反应7d。实验表明，反应后流体pH值发生了变化，NaCl介质向酸性变化，N aCl NaHCO3介质向中性转化。溶液中K,Ca,Mg,Fe和Au量也随之发生变化。矿物表面发生溶解和离子置换等反应。斜长石表面形成钠长石反应边，黑云母变色，石英重结晶，反应器皿金管中的金被溶解后在金管壁和黑云母表面重结晶，黑云母周边出现红色Fe2O3，在450℃的NaCl介质中，金含量可达1070μg/g，但随温度下降迅速减低，在NaCl NaHCO3介质中，金含量较低，显著，金的活化迁移和富集与Cl,pH,Fe^3 /Fe^2 密切相关，这中金起到示踪作用，显示出金在水／岩反应中的原电池效应。     

Polarized electronic absorption spectra of Co2+ ions in the kieserite-type compounds CoSO4 · H2O and CoSeO4 · H2O

Polarized electronic absorption spectra of the kieserite-type compounds CoSO₄ · H₂O and CoSeO₄ · H₂O have been obtained at room temperature (spectral range 35 000-5000 cm^-1) and at liquid nitrogen temperature (visible spectral region), using microscope-spectrometric techniques. The spectra are interpreted and evaluated in terms of a tetragonal crystal field formalism for the d⁷ configuration, in regard to the pseudotetragonal elongation of the CoO₄(H₂O)₂ octahedra, known from previous X-ray structure investigations, employing the tetragonal parameters Dq, Dt, and Ds, and the Racah parameters B and C. The observed and calculated energy levels are in good agreement for the following parameter sets: CoSO₄ · H₂O: Dq=826, Dt=40, Ds=350, B=856, C=3580 cm^-1; CoSeO₄· H₂O: Dq=817, Dt=44, Ds=406, B=841, C=3490 cm^-1; corresponding ‘cubic’ crystal field strengths Dq_cub are 803 and 792 cm^-1, respectively. The values of Dq_(cub), Racah B and C are in the common range for Co²⁺ ions in (pseudo) octahedral fields of oxygen ligands, and their differences in CoSO₄· H₂O compared to CoSeO₄ · H₂O are consistent with somewhat different mean Co-O bond lengths and with a slightly higher covalent contribution to Co-O bonding in the selenate compound. The values found for the parameter Dt, which is directly correlated to the extent of tetragonal distortion, are much lower than expected from purely geometrical considerations, thus confirming a significantly higher position of H₂O ligands in the spectrochemical series compared to oxygen ligands belonging to SO₄ or SeO₄ groups.